CHEMISTRY

6
Biology Class
FEZALAR EDUCATIONAL INSTITUTIONS
CHEMISTRY DEPARTMENT
Copyright © South Fezalar Educational Institutions

All rights reserved.

No part of this book may be reproduced, stored in a retrieval system or trans-

mitted in any form without the prior written permission of the publisher.

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Fezalar Educational Institutions / Chemistry Department

6th Edition, 2018

 CONTENTS
INTRODUCTION 1

CHAPTER 1 - THERMODYNAMICS 9

CHAPTER 2 - CHEMICAL EQUILIBRIUM 43

CHAPTER 3 - IONIC EQUILIBRIUM 79

CHAPTER 4 - REDOX REACTIONS &

ELECTROCHEMISTRY 123

CHAPTER 5 - COORDINATION CHEMISTRY 157

CHAPTER 6 - CHEMICAL ANALYSIS 182

CHAPTER 7 - ORGANIC CHEMISTRY FOR

SUBSTITUTED HYDROCARBONS 213

CHAPTER 8 - BIOCHEMISTRY 249

 PREFACE
Chemistry is an interesting and fundamental branch of science because it gives us the

chance to explain the secrets of nature.

What is water? What do we use in our cars as fuel? What is aspirin? What are perfumes

made of? These kinds of questions and their answers are all part of the world of chem-

istry. Chemists work everyday to produce new compounds to make our lives easier

with the help of this basic knowledge. All industries depend upon chemical substances,

including the petroleum, pharmaceuticals, garment, aircraft, steel, and electronics indus-

tries, etc.

This book helps everyone to understand nature. However, one does not need to be a

chemist or scientist to understand the simplicity within the complexity around us. The

aim was to write a modern, up-to-date book where students and teachers can get concise

information about chemical reactions and inorganic compounds. Sometimes reactions

are given in detailed form, but, in general, excessive detail has been omitted. Through-

out the book, different figures, colourful tables, important reactions are used to help

explain ideas.

We hope that after studying this book, you will find chemistry in every part of your

life.

The Author
 Introduction

INTRODUCTION

ACHIEVEMENTS
After studying this chapter, students can perform the following:

*They can calculate the molar mass of molecules.

*They know the relationship between number of moles, mass and molar mass and they can calculate those functions.

*They can define molarity and calculate it through number of moles and volume of solution.

*They can define the common logarithm (the logarithm to base 10) and natural logarithm and also the relationship be-
tween them and rules about them.

*They can calculate the common logarithm of numbers and also their natural logarithm using calculator.

FEZALAR EDUCATIONAL INSTITUTIONS 1

 Chemistry 6

Review of Information
In chemical calculations, pupils need to use some mathematical relation-
ships, symbols and terms which they have learnt before. All those are used
throughout this book in examples and exercises especially in analytical and
physical chemistry.

A- The International System of Units, (SI)

In the following table, basic units and symbols in SI system are shown.
Quantity Base Unit Symbol
Length meter m
Mass kilogram kg
Time second s
Electric Current ampere A
Temperature Kelvin K
Light Intensity candela cd
Amount of Substance mole mol
While calculating, some units as grams (g) or centimeter (cm) derived from
those above can be used.

B- Some Mathematical Formula used in this book

1- Molar mass (M)
Molar mass is defined as the weight of 1 mole of molecule in gram unit and
shown with M and its unit is (g/mol). Molar mass is equal to the multiplication
of number of atoms of elements with their atomic masses in a molecule. Molar
mass is calculated as shown in the following example:

Example -1
Calculate the molar masses of compounds sodium carbonate Na2CO3 and cal-
cium phosphate Ca3(PO4)2.
Exercise 1
Atomic weights of elements:
Calculate the molar masses of
the following compounds: Na=23, C=12, 0=16, Ca=40, P=31
NaOH, KMnO4 , H2SO4 , Solution:
K2Cr2O7 , MgCl2
M (Na2CO3) = 2 × 23 + 1 × 12 + 3 × 16 = 106 g/mol
You can find the atomic masses
of elements in the chart at the M [Ca3(PO4)2] = 3 × 40 + 2 × 1 × 31 + 2 × 4 × 16 = 310 g/mol
end of the book.
2- Calculating Number of Moles, n
In order to calculate number of moles, we use the following equation which
we have used in the previous years.
Mass (m) gram
Number of moles = ___________________
Molar mass (M) g/mol
m (g)
n (mol) = __________
M (g/mol)

2 FEZALAR EDUCATIONAL INSTITUTIONS

 Introduction

Example -2 Exercise 2
Calculate the number of moles of 22 g of potassium carbonate K2CO3 com- Calculate the number of moles of
pound. 14.2 grams of Na2SO4 compound.
Solution: Answer: 0.1 mole
We calculate the molar mass of K2CO3.
M (K2CO3) = 2 × 39 + 1 × 12 + 3 × 16 = 138 g/mol
Using the following equation, we calculate the number of moles.
m (g) 22 (g)
n (mol) = __________ = __________ = 0.16 mol
M (g/mol) 138 (g/mol)
By re-arranging the mole equation, we can calculate mass of compounds.
Exercise 3
m (g) = n (mol) × M (g/mol)
Calculate the following:
Example - 3 1-The number of moles of 72 g of
Calculate how many grams of NaCl make 0.15 moles? H3PO4 compound
(Na = 23 g/mol, Cl = 35.5 g/mol) 2-How many grams are 0.75 moles
of Na3PO4 compound?
Solution:
1-Molar mass of NaCl is calculated. Answers:
M(NaCl) = 1 × 23 + 1 × 35.5 = 58.5 g/mol 1) 0.73 mol
2-Using the following relationship, m is calculated. 2) 123 g
m (g) = n (mol) × M (g/mol)
m (g) = 0.15 (mol) × 58.5 (g/mol) = 8.78 g
3- Molarity, M
Molarity is an expression of concentration. It is defined as the mole number of
substance dissolved in 1 liter solution. We use the following formula to calcu- Attention:
late molarity:
Number of moles Volume is expressed with liter (L),
Molarity (M) = _________________ milliliter (mL) or cubic centimeter
Number of volume (cm3) units. The relationships be-
n (mol) tween them are as follows:
M (mol/L) = _______
V (L) 1L= 1000 mL

m (g) 1L =1000 cm3

m (g) M (g/mol)
n (mol) = __________ ⇒ M (mol/L) = ____________
1mL = 1 cm3
M (g/mol) V (mL)
1000 (mL/L)

Symbol of molarity, M, is different from molar mass.

As you know, number of moles are found through the following formula:
After we simplify this formula, we can use the final version of it.

FEZALAR EDUCATIONAL INSTITUTIONS 3

 Chemistry 6

Exercise 4 Example -4
After dissolving 15 g of acetic acid A 5 liters solution is prepared by dissolving 53 g of sodium carbonate
CH3COOH in 150 mL water, it was
transferred to a half liter container (Na2CO3) salt. Calculate the molarity of this solution.
and it was filled to the brim. Calcu- m (g) × 1000 (mL/L)
late the molarity of this solution. M (mol/L) = __________________
M(g/mol) × V (mL)
Answer: 0.5 M
Solution:
1. We calculate molar mass of Na2CO3 compound:
Exercise 5
M (Na2CO3) = 2 × 23 + 1 × 12 + 3 × 16 = 106 g/mol
4 g of NaOH (M= 40 g/mol) was
dissolved in a certain volume of wa- 2. We calculate the mole number:
ter. As the molarity of the solution m (g) 53 (g)
is 0.05 mol/L, calculate the volume n (mol) = __________ = __________ = 0.5 mol
M (g/mol) 106 (g/mol)
of water.
Answer: 2 L 3. We calculate the molarity:
n (mol) 0.5 (mol)
M (mol/L) = __________ = __________ = 0.1 mol/L
V (L) 5 (L)
Example -5
How many grams of Ca(OH)2 is necessary to prepare a solution of 0.1 M and
250 mL?

Solution:
1. We calculate the molar mass of Ca(OH)2 compound:
M [Ca(OH)2] = 1 × 40 + 2 × 16 + 2 × 1 = 74 g/mol
2. We calculate the molarity using the following relationship:
m (g) × 1000 (mL/L)
M (mol/L) = __________________
M(g/mol) × V (mL)

3. We can find the mass by re-arranging the equation:

M (mol/L) × M (g/mol) × V (mL)
m (g) = ____________________________
1000 (mL/L)

0.1 (mol/L) × 74 (g/mol) × 250 (mL)

m (g) = _______________________________
1000 (mL/L)

m (g) = 1.85 g

4- The relationship between Mole, Molecules and Atoms

Avogadro’s Number is the number of particles (molecules or atoms) that a
mole includes. Avogadro’s number is shown with NA symbol.
NA= 6.023×1023 atoms or molecules

4 FEZALAR EDUCATIONAL INSTITUTIONS

 Introduction

The relationship between number of moles (n) and Avogadro’s number and
number of atoms or molecules is as follows:
Number of atoms or molecules = number of moles (n) × Avogadro’s number
The relationship is expressed as follows:
No. (atoms or molecules) = n (mol) × NA (atoms or molecules/mol)

Example - 6 Exercise- 6
Calculate the number of atoms and molecules in 0.1 mole hydrogen gas, H2. Calculate number of atoms and
molecules in 0.16 moles of oxygen
Solution: gas, O2.
We use the following relationship to calculate number of molecules: Answer: 0.96×1023 molecules
Number of molecules = n (mol) × NA (molecules / mol) 1.92×1023 atoms
= 0.1 (mol) × 6.023 × 1023 (molecules / mol)
= 6.023 × 1022 molecules
As each hydrogen molecule is made up of 2 atoms, number of atoms:
Number of Atoms = Number of molecules × 2
Number of Atoms = 6.023×1022 × 2 = 12.046 × 1022 atoms

5- Logarithms
There are two types of logarithms in mathematics. The first type is the loga-
rithm to base 10. It is also called as the common logarithm and its base 10 isn’t
written. For example, log10 y is written as log y. This logarithm is defined as
follows:
log y = x ⇒ y = 10x
For example, log10 7 is written as log 7 and log10 0.05 is written as log 0.05.
According to log 10n = n rule, it is useful to remember integer logarithms of
base 10:
For positive exponents log10 107 =7 and log10 104 = 4 etc.
For negative exponents log 0.01=log 10-2 and log 0.00001= log 10-5 etc.
The second type of logarithm is called as natural logarithm and shown with
lne y symbol. The value of base e is 2.718 and it is defined with the relationship
below:
In y = x ⇒ y = ex
The following rules are applied to both types of logarithms:
1. The logarithm of multiplication of two numbers is equal to the multiplication
of logarithms of both numbers.
log Z × Y = log Z + log Y
log 5 × 6 = log 5 + log 6

FEZALAR EDUCATIONAL INSTITUTIONS 5

 Chemistry 6

2. The logarithm of division of two numbers is equal to the difference between

logarithms of both numbers.
Z
log ___ = log Z - log Y
Y
8
log ___ = log 8 - log 3
3
3. The logarithm of an exponential expression is equal to the multiplication of
the logarithm of number with its exponent.
log ZY = Y × log Z
log 29 = 9 × log 2
After the summary of the common and natural logarithms and their rules, we
will learn how to use a calculator to calculate the logarithm and antilogarithm
of a number.

A- To find the Logarithm of a number using a calculator

1. The Common Logarithm
We type the number which we want to find its logarithm and press log key on
the calculator and see the result.
Exercise -7 Example -7
Calculate the following using a cal- Calculate the following:
culator.
a) log 7 b) log 13 c) log 0.08 d) log 1.5
a) log 26.7
b) log 0.89
Solution:
a) First, we type 7 and then press log key. The result is shown as 0.84509804.
c) ln 93
That means:
d) ln 0.02
log 7 = 0.84509804
b) First, we type 13 and then press log key. The result is 1.11394335.
c) First, we type 0.08 and then press log key. The result is – 1.096910013.
d) First, we type 1.5 and then press log key. The result is 0.176091259.

2. Natural Logarithms (ln)

We type the number which we want to calculate its logarithm and then press
ln key.

Example -8
Calculate the following:
a) ln 7 b) ln 13 c) ln 0.08 d) ln 1.5

Solution:
a) We type 7, and then press ln key. The result is 1.94510149.
b) We type 13, and then press ln key. The result is 2.564949357.
c) We type 0.08, and then press ln key. The result is -2.525728644.

6 FEZALAR EDUCATIONAL INSTITUTIONS

 Introduction

d) We type 1.5, and then press ln key. The result is 0.405465108.

B- To find the Antilogarithm of a number using a calculator

1. Common Logarithms
We type the given logarithm value. Then we press 2ndF key. This key is some
other color (yellow, blue, etc.) instead of black. Then we press log key and get
the number.
Example - 9 Exercise - 8
Find the numbers which of their logarithms are given below: Find the value of y (antilogarithm)
a) 0.8450804 in the following relationships using a
b) 1.113943352 calculator.

c) -1.096910013 a) log y = 2.6

d) 0.176091259 b) log y = -1.2

c) ln y = 0.7
Solution:
d) ln y = -3.9
a) We type 0.8450804, then press 2ndF key and log key. The result is shown
as 7.
b) We type 1.113943352, then press 2ndF key and log key. The result is shown
as 12.99999999˜13.
c) We type -1.096910013 then press 2ndF key and log key. The result is shown
as 0.08.
d) We type 0.176091259 then press 2ndF key and log key. The result is shown
as 1.5.

2. Natural Logarithms
We type the given logarithm value. Then we press 2ndF key. This key is some
other color (yellow, blue, etc.) instead of black. Then we press ln key and the
result is shown.

Example -10
Calculate the numbers which of their natural logarithms are given below: Attention: You can use the rela-
a) 3.22 b) -1.78 tionship In x = 2.303 log x while
solving questions.
Solution:
a) We type 3.22, and then we press 2ndF key and ln key. The result is shown
as 25.
b) We type -1.78, and then we press 2ndF key and ln key. The result is shown
as 0.17.
Note: You can use the relationship In x = 2.303 log x while solving
questions.

FEZALAR EDUCATIONAL INSTITUTIONS 7

 Chemistry 6

BASIC EQUATIONS
The relationship between number of moles and molar mass:
m (g)
n (mol) = __________
M (g/mol)

Molarity (M)
n (mol)
M (mol/L) = _______
V (L)

Number of atoms or molecules

Number of atoms or molecules = n (mol) × NA (atoms or molecules/mol)

BASIC CONCEPTS
Molar Mass (M)
It is the mass of 1 mole of compound. It is equal to the sum of multiplications of atomic masses of elements
and their numbers in the formula of the compound.
Molarity (M)
It is the mole number of substance dissolved in 1 liter of solution.
Avogadro’s Number (NA)
It is the number of atoms, ions or molecules in 1 mole and it is equal to 6.023x1023 mol-1 value.

8 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

THERMODYNAMICS CHAPTER-1

ACHIEVEMENTS
After studying this chapter, students can do the following:
* They can define thermodynamics, energy, units of energy, system, environment, universe, types of systems, dynamics,
heat, heat capacity, and specific heat concepts. They try to define the heat of reaction measured at constant pressure.
* They learn what enthalpy means and its relationship with heat of reaction and also units of enthalpy.
* They decide whether the reaction is endothermic (heat absorbing) or exothermic (heat releasing) with respect to the
sign of enthalpy.
* They can write the heat equation with respect to rules and tell its difference from chemical equation.
* They can differentiate standard enthalpy of reaction, standard enthalpy of formation and standard enthalpy of combus-
tion concepts.
* They learn the methods to calculate enthalpy of reaction.
* They learn entropy and free energy concepts.
* They define absolute entropy, standard entropy of formation and learn how to calculate Gibbs free energy.
* They understand Gibbs free energy equation and decide the direction of reaction depending on enthalpy and entropy
values.

FEZALAR EDUCATIONAL INSTITUTIONS 9

 Chapter - 1

1-1-PREFACE
During our studies, we have encountered a few types of energy. For example,
heat energy, electric energy, mechanical energy, light energy, nuclear energy,
chemical energy, etc. These different types of energy are stored inside all mat-
ter and they are released when the matter changes form. Although types of en-
ergy are different, a type of energy isn’t independent of another. Under certain
conditions, a type of energy can be transformed into another.
Thermodynamics is the branch of science which studies energy and its trans-
formation. For example, it studies the transformation of heat energy from com-
bustion of fuel into mechanical energy which runs the engines. Thermodynam-
ics explains many phenomena. The most significant of those are:
1-The reason of occurrence of chemical reactions
2-Estimates the chemical and physical changes that one or more substances
undergo under certain conditions
3-The reason why some reactions occur spontaneously while some don’t under
the same conditions.
4-The reason why the energy accompanying reactions is sometimes given to
reaction while sometimes it is released as a result of the reaction.
On the other hand, thermodynamics isn’t interested in time factor in which
reactions occur. It only studies if a certain reaction (or more generally, if any
change will occur) will occur or not. The rate of change is in the field of kinet-
ics.
We can generally divide energy into two. One is potential energy, the other is
kinetic energy. Potential energy includes chemical energy stored in all sub-
stances and fuels. Kinetic energy is the energy which molecules, moving water,
cars, planes, missiles and others have due to their movement. For example, the
potential energy in water is transformed into kinetic energy if its movement
starts from the top of a fall. Resulting energy can move blades of a turbine to
produce electric energy. Therefore, the first law of thermodynamics states the
following: “Energy can be neither created nor destroyed, but can change form.”

1-2-UNITS OF ENERGY AND TEMPERATURE

According to International System of Units (SI), the unit which defines energy,
joule (its symbol J) is shown as follows:

1J = 1 kg.m2/s2
Kg is kilogram, m is meter, s is second.
Definition of kinetic energy: It is the product of half of mass in kg unit with the
square of velocity (V (m/s).
1
KE = ___ m.v2
2

10 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

If an object which has 2 kg of mass travels 1 meter (1m) of distance in 1 second water vapor
(1s), it has a kinetic energy of 1 joule (1J).
In thermodynamics, unit of temperature is Kelvin (K). This unit is converted to
centigrade (°C) according to the following equation:
T(K) = t(°C) + 273

1-3-SOME THERMODYNAMICS TERMS

The most important thermodynamics term is thermodynamic system. This is
a part of the universe we are studying. System consists of substance or sub- Heat
stances which participate in limited physical and chemical changes within cer-
tain boundaries. The area outside these boundaries is called as surroundings.
System and its surroundings are called as universe. Here we will use the term
cluster.
Cluster = System + Surroundings Energy and matter
interaction occur
We can divide system into three accord-
ing to the relationship between system
and surroundings. These are:

1-Open System
If the boundaries allow matter and energy
interaction between system and surround-
ings, system is called as an open system.
For example, boiling water in a metal
container. Water is distributed around sur-
roundings as vapor. Besides, heat of water Heat
is also released. That means there is an interaction of matter and energy.

2-Closed System
If boundaries allow only energy interaction but not matter, it is a closed sys-
tem. A metal container which is tightly closed is a good example. In this case, Only energy interaction occur
although heat of water is released through surroundings, the amount of water
remains unchanged.

3-Isolated System
If system boundaries allow neither energy nor matter interaction with its sur-
roundings, it is called as an isolated system. Thermoses are good examples as
they prevent heat and amount of matter being released from system.
Physical states of matter as number of moles of substances in the system, phys-
ical variables of system which can be observed and measured, volume, pres-
sure and temperature are called as system properties.
1-4-HEAT
Heat is one of the common energy types in our daily lives. We show heat with
(q). Heat is the energy change between two objects with different degrees of
temperature. Temperature is a measurement of heat energy. Lost or gained heat
energy of any object is directly proportional to change in degrees of tempera- No energy or matter
ture. Change is shown with (∆). interaction occur

FEZALAR EDUCATIONAL INSTITUTIONS 11

 Chapter - 1

ΔT = Tf - Ti
Tf is final temperature. Ti is initial temperature. The relationship between heat
and temperature can be written as follows:

(1) q ∝ ∆T
In order to convert this ratio to an equation, ∆T is multiplied with a ratio con-
stant called as heat capacity (C).

(2) q = C × ∆T
Heat capacity is the amount of heat necessary to increase the temperature of m
gram m(g) of substance by 1 °C. Its unit is (J/°C). Heat capacity is related to
specific heat ς with the following relationship:

(3) C = ς × m
Table 1-1
Specific Heat values of some Specific heat is the amount of heat necessary to increase the temperature of 1
substances at 25 °C gram of substance by 1 °C. Its unit is (J/g.°C). By inserting value of C in Equa-
Substances Specific Heat tion 3 into equation 2, we get the following relationship.

Water(liquid) 4.18 q (J) = ς (J/g.°C) × m (g) × ∆T (°C)

Ethyl alcohol 2.44 Example 1-1
Water (solid) 2.03
What is the amount of heat necessary to increase the temperature of 870 g of
Water (gas) 2.01 piece of iron from 5 °C to 95 °C? (specific heat of iron 0.45 J/g.°C)
Beryllium 1.83
Magnesium 1.023 Solution:
Aluminum 0.90 Change in degree of temperature:
Calcium 0.65 ΔT = (Tf - Ti) °C = (95 - 5) °C = 90 °C
Iron 0.45
Heat q is calculated using the following equation.
Strontium 0.30
Silver 0.24 q (J) = ς (J/g.°C) × m (g) × ∆T (°C)
Barium 0.20 q (J) = 0.45 (J/g.°C) × 870 (g) × 90 (°C) = 35235 J
Lead 0.13
The amount of heat consumed by piece of iron is calculated as kJ:
Gold 0.13
1(kJ)
q(kJ) = q (J) × _______
1000 (J)
Exercise 1-1
1(kJ)
205 J of heat was given to 10 q(kJ) = 35235 (J) ×_______ = 35.2 kJ
g of magnesium metal. The 1000 (J)
temperature was raised from
1-5-ENTHALPY CHANGE
25°C to 45°C. Calculate the
Most of the chemical reactions occur under constant pressure. Few reactions
specific heat of magnesium.
occur at constant volume. Therefore, constant pressure is preferred to constant
Answer: 1.03 J/g.°C volume while measuring heat accompanying chemical reaction. Under con-
stant pressure, the change in heat of reaction is called as heat of reaction or en-
thalpy change or simply enthalpy of reaction. Enthalpy is shown with (H) and
enthalpy change is shown with ∆H. This value is equal to the heat of reaction
under constant pressure. In other words

12 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

∆H = qp
qp shows measured heat under constant pressure.
When a chemical reaction is considered as a system, enthalpy change shows if
the reaction is endothermic (heat absorbing) or exothermic (heat releasing). If
enthalpy of reaction is shown with ∆Hr, we can express the following:
-If ∆Hr is less than zero (∆Hr< 0) or (∆Hr = -), the reaction is exothermic.
-If ∆Hr is greater than zero (∆Hr > 0) or (∆Hr = +), the reaction is endothermic.
It seems that change in enthalpy of reaction is equal to the following equation:
The reaction occurring during
∆Hr = ∆H (Products) - ∆H (Reactants) explosion of fireworks is exother-
mic.
1-6-STATE FUNCTION
Without considering the path followed, the property or amount which depends
on the difference between initial state of system before change and final state of
system after change is called as state function. As an example for state func-
tion, enthalpy can be given. Later we will see other functions as entropy, free
Gibbs energy, etc. (Figure 1-1)

Figure 1-1
State function depends only
on the initial and final states
of the system. It doesn’t
depend on the path the sys-
tem follows. In the picture,
both climbers consumed
the same amount of ener-
gy although they followed
different paths.

Values of heat or work change with respect to the conditions of experiment

change. Therefore it isn’t accepted as a state function. Heat and work is related
to the path followed and steps during change occurs. It is impossible to mea-
sure their state functions. But the amount of change (∆) of these functions can
be measured. For example, we can’t measure absolute value of enthalpy but we
can only measure enthalpy change. Thus:

∆H = ∆Hf - ∆Hi
f means final and i means initial.

FEZALAR EDUCATIONAL INSTITUTIONS 13

 Chapter - 1

1-7-GENERAL PROPERTIES OF SUBSTANCES

General properties of substances are divided into two:

1-Extensive Properties:
It includes all properties related to amount of substance in the system as mass,
volume, heat capacity, enthalpy, entropy, free energy, etc.

2-Intensive Properties:
It includes all properties which are independent of amount of substance in the
system as pressure, degree of temperature, density, specific heat, etc.
It is understood from above that enthalpy is a state function. It is an extensive
property as it depends on amount of substance. Thus, the enthalpy change of
2 moles of a substance is twice the enthalpy change of 1 mole of the same
substance.

1-8-THERMOCHEMISTRY

Thermochemistry is the branch of science which studies energy change (ab-

sorbed heat or evolved heat) that results from physical and chemical chang-
es. In simpler words, thermochemistry deals with calculation of enthalpies of
chemical reactions and physical changes. As we have mentioned before, if the
value of ∆Hr are negative, reaction is exothermic; if the value of ∆Hr are posi-
tive, reaction is endothermic. If we assume a reaction as a system, an exother-
mic reaction releases its energy from system to surroundings. This is shown in
the following chemical reaction and physical change.

2H2(g) + O2(g) → 2H2O(l) + Energy Chemical Reaction

H2O(g) → H2O(l) + Energy Physical Change

In an endothermic reaction, system absorbs energy from surroundings. The

following chemical reaction and physical change can be given as examples.

2HgO(s) + Energy → 2Hg(l) + O2(g) Chemical Reaction

H2O(s) + Energy → H2O(l) Physical Change
If we write the word “energy” beside reactants, reaction is endothermic; if we
write it beside products, reaction is exothermic.

14 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

1-9-MEASUREMENT OF ENTHALPY OF REACTION

In a chemical reaction under constant pressure, an instrument called as calo-

rimeter is used in order to measure the heat of reaction (enthalpy of reaction)
which is absorbed or released. In this container, enough amounts of substanc-
es to react are placed. A calorimeter is a container which contains water with a
known mass. Water is placed in a very well isolated container. Fig 1-2 shows
a calorimeter which measures enthalpies of reaction. As the released heat in-
creases the temperature of water and calorimeter, if the heat capacity and
content of calorimeter is known, heat can be measured through increase in
temperature.

Example 1-2
3 g of glucose C6H12O6 was placed inside a calorimeter in Figure 1-2. Then
interaction vessel was filled with oxygen gas. This vessel was placed in the beaker
isolated container. Isolated container was filled with 1200 g of water. Initial
temperature was 21°C. After burning the mixture, the temperature of the cal-
Calorimeter vessel which is used to
orimeter and its content was raised to 25.5 °C at the end of the reaction. Cal- measure enthalpies of reaction.
culate the amount of heat released as a result of burning 1 mole of glucose in Figure 1-2
kJ unit. (Heat capacity of the calorimeter can be neglected). (Molecular mass
of glucose is 180 g/mol) (Specific heat of water is 4.2 J/g.°C)

FEZALAR EDUCATIONAL INSTITUTIONS 15

 Chapter - 1

Exercise 1-2 Solution:

When 3 g of hydrazine (N2H4) was Difference in degrees of temperature
burnt in a calorimeter containing
1000 g of water, the temperature was
ΔT = (Tf - Ti) °C = (25.5 - 21) °C = 4.5 °C
raised from 24.6°C to 28.2°C. By ne- As heat capacity of calorimeter was neglected, the amount of heat can be cal-
glecting the heat capacity, calculate culated using the following relationship.
the released heat from burning of 1 q (J) = ς (J/g.°C) × m (g) × ∆T (°C)
mole of hydrazine in kJ unit. (Molar
mass of N2H4 = 32 g/mol) (Specific q (J) = 4.2 (J/g.°C) × 1200 (g) × 4.5 (°C) = 22680 J
heat of water = 4.2 J/g.°C)
As we would like to calculate the amount of released heat, this must have a
Answer: -161 kJ/mol negative sign. That is equal to (-22680 J). This is the amount of heat released
through burning 3 g of glucose. To find out the amount of heat released from
burning of 1 mole of glucose, we use the following relationship between num-
ber of moles (n) and mass (m).
m (g) 3 (g)
n (mol) = _______ = ___________ = 0.017 mol
M (g/mol) 180 (g/mol)
Therefore, the amount of heat released from burning of 1 mole of glucose is:
-22680 J
q = _________ = -1334118 J/mol
0.017 mol
As this heat was measured in a calorimeter under constant pressure, it shows
the enthalpy of reaction.
∆H = qP = -1334118 J/mol
The unit of enthalpy is J/mol. In order to find out the value of enthalpy in kJ
unit, it is converted as follows:
1(kJ)
ΔH(kJ/mol) = ΔH(J/mol) × _______
1000 (J)
1(kJ)
ΔH(kJ/mol) = -1334118 (J/mol) × _______
1000 (J)
= -1334 kJ/mol
Therefore, the amount of heat which was released through burning of 1 mole
of glucose : -1334 kJ/mol

1-10-THERMOCHEMICAL EQUATION
Writing of a thermochemical equation (which defines a chemical reaction and
a physical change) is different from writing other chemical equations. The fol-
lowing rules must be followed while writing a thermochemical equation:
1-The sign of change in enthalpy which accompanies a chemical reaction or
a physical change must be written. The positive sign of enthalpy shows that
reaction or change is endothermic. For example, the melting process of ice is
shown as follows:

16 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

H2O(s) → H2O(l) ΔH = 6 kJ/mol

That means to melt 1 mole of ice under 1 atm pressure and 25°C, 6 kJ/mol of
heat is absorbed. Absorbed heat can be written along with reactants (left hand
side of the reaction) and inserted into the thermochemical equation:
H2O(s) + 6 kJ/mol → H2O(l)
If the sign of enthalpy is negative, it shows the reaction is exothermic. The
following reaction is an example:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔH = -890 kJ/mol

That means when 1 mole of methane gas is burnt at 25°C and under 1 atm
pressure, 890 kJ/mol heat is released. Released heat can be written along with
products if it is released during thermal reaction. Therefore, the reaction above
can be rewritten as follows:

Melting of ice is endothermic

phenomenon, whereas burning
of methane gas is an exother-
mic reaction

2- Physical states of reactants and products need to be written. For this purpose,
some letters are used. These are: s (solid), l (liquid), g (gas), aq (aqueous). The
reason for this is that absorbed or released heat can change with physical states
of reactants and products. The following example shows this clearly:
1
H2(g) + 2 O2(g) → H2O(l) ΔH = -286 kJ/mol

1
H2(g) + 2 O2(g) → H2O(g) ΔH = -242 kJ/mol

3- If the reaction (chemical reaction or physical change) is written reversely, Attention: Item 3 is one of ap-
the sign of enthalpy of reaction changes (from negative to positive or vice plications of Laplace’s Law.
versa).
H2O(s) → H2O(l) ΔH = 6 kJ/mol
H2O(l) → H2O(s) ΔH = -6 kJ/mol

FEZALAR EDUCATIONAL INSTITUTIONS 17

 Chapter - 1

4- If two sides of the reaction are multiplied or divided with a certain coeffi-
cient, the same process needs to be done with the value of enthalpy.
H2O(s) → H2O(l) ΔH = 6 kJ/mol
2H2O(s) → 2H2O(l) ΔH = 2 × 6 kJ/mol = 12 kJ/mol

1-11-STANDARD ENTHALPY OF REACTION

The value found under standard conditions which are 25°C and 1atm pressure
is called as standard enthalpy of reaction and shown with ∆Hr° symbol. These
conditions are different from standard conditions (STP) which is 0°C and 1 atm
pressure while dealing with gases.
Let’s write a thermal reaction which includes all properties mentioned above.

C5H12(l) + 8O2(g) → 5CO2(g) + 6H2O(l) ΔHr° = -3523 kJ/mol

We can read this as follows:
1 mole of liquid pentane (C5H12) was burnt with 8 moles of oxygen gas. As a
result of the burning process, 5 moles of carbon dioxide gas, 6 moles of liquid
water and 3523 kJ of heat were released under standard conditions, 25°C and
1atm pressure.

1-12-TYPES OF ENTHALPY

1-12-1-Standard Enthalpy of Formation

The heat which is necessary to form 1 mole of compound from its compo-
nents under standard conditions is called as standard enthalpy of formation.
It is shown with ∆Hf° symbol. Here, the most stable forms of elements under
standard conditions are taken. According to this, the most stable form of hydro-
gen is gas, whereas mercury in liquid and magnesium in solid forms. These are
measured at 25°C and 1atm pressure (standard conditions).

For example, carbon element can be found in graphite and diamond forms.
But graphite is its most stable form. Sulfur is found two stable forms: rhombic
sulfur (Srhombic) and orthorhombic sulfur (Sorthorhombic). But rhombic sulfur is the
most stable form.

According to IUPAC system, standard enthalpy of formation of all elements is

equal to 0 kJ/mol in their standard forms (the most stable form of an element).

ΔHf° (Element) = 0 kJ/mol

Oxygen in gas form is the most stable. In this case, the following relationship
can be written.
ΔHf° (O2) = 0 kJ/mol

18 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

In the same manner, if graphite is more stable than diamond, the following Table 1-2
relationship will be correct. Standard Enthalpies forma-
ΔHf° (Cgraphite) = 0 kJ/mol tion of Some compounds
The formation equations of some substances are given below:
1
H2(g) + 2 O2(g) → H2O(l) ΔHf°(H2O(l)) = -286 kJ/mol Compound
3 1
2
H2(g) + 2O2(g) + 4 P4(s)→ H3PO4(s) ΔHf°(H3PO4(s)) = -1279 kJ/mol

Mg(s) + Cl2(g) → MgCl2(s) ΔHf°(MgCl2(s)) = -642 kJ/mol

C(graphite) + O2(g) → CO2(g) ΔHf°(CO2(g)) = -394 kJ/mol

Table 1-2 shows ∆Hf° values of some compounds. While writing thermal equa-
tions, rational numbers are used to show formation of 1 mole of sought com-
pound. Therefore, we change the mole numbers of reacting substances.
∆Hf° is the enthalpy of 1 mole of compound by taking most stable forms of
elements under standard conditions. But ∆Hr° standard heat of reaction of any
compound might not be equal to ∆Hf° standard enthalpy of formation. For ex-
ample, ∆Hr° of the following reaction is equal to -72 kJ.
H2(g) + Br2(g) → 2HBr(g) ΔHr° = -72 kJ
If we consider this equation, 2 moles of HBr was formed at the end of the reac-
tion. Therefore, the half of this heat -36 kJ is the heat released when 1 mole of
HBr is formed from its most stable elements. The standard enthalpy of forma-
tion of HBr compound is as follows:
1 - 72
ΔHf°(HBr) = 2 ΔHr° = 2 kJ/mol = -36 kJ/mol

This is obtained by dividing the both sides of equation by two.

1 1
2
H2(g) + 2 Br2(g) → HBr(g)

Example 1-3
As the standard enthalpy of formation of benzene ∆Hf0(C6H6)= 49 kJ/mol,
write down the thermochemical equation to make ∆Hr0 = ∆Hf0(C6H6)
Solution:
1 mole of (C6H6) must be formed from the most stable form of its elements at
25°C and 1 atm pressure.

6C(graphite) + 3H2(g) → C6H6(l) ΔHr° = ΔHf° (C6H6) = 49 kJ/mol

FEZALAR EDUCATIONAL INSTITUTIONS 19

 Chapter - 1

Exercise 1-3 Example 1-4

As standard enthalpy of formation Which of the following reactions has a standard enthalpy of reaction ∆Hr°
ΔHf˚of sulfuric acid (H2SO4) is which is equal to standard enthalpy of formation ∆Hf° of formed compounds?
(-811kJ/mol), write down the ther-
mochemical equation to make 1) 4Fe(s) + 3O2(g) → 2Fe2O3(s) ΔHr° = 1625 kJ
ΔHr˚ = ΔHf˚(H2SO4).
2) C(graphite) + O2(g) → CO2(g) ΔHr° = -394 kJ
1
3) CO(g) + 2 O2(g) → CO2(g) ΔHr° = -283 kJ

Exercise 1-4 Solution:

As standard enthalpy of forma- Reaction 1: Standard enthalpy of reaction isn’t equal to standard enthalpy of
tion of hydrogen fluoride (HF) is formation of Fe2O3 compound, because 2 moles of substance have been formed
∆Hf˚(HF) = -271 kJ/mol, at the end.
calculate standard enthalpy of Reaction 2: Standard enthalpy of reaction of CO2 compound is equal to its
reaction ∆Hr° of the following standard enthalpy of formation. Because 1 mole of CO2 has been formed from
reaction. the most stable form of its elements.
H2(g) + F2(g) → 2HF(g)
Reaction 3: ∆Hr° isn’t equal to ∆Hf° CO2, because the reactants aren’t in the
Answer: -542 kJ most stable form.

1-12-2-Standard Enthalpy of Combustion

Combustion reactions include reactions of substances (fuels) with oxygen. In
biological systems, food is accepted as fuel. When food is decomposed (com-
busted) in body, carbohydrates are transformed to glucose sugar. One of the
methods of heating houses or cooking is via combustion of butane gas. Com-
bustion of 1 mole of butane gas yields -2873 kJ of energy according to the
Exercise 1-5 following equation:
As standard enthalpy of formation
13
aluminum oxide is ∆Hf° (Al2O3) = C4H10(g) + 2 O2(g) → 4CO2(g) + 5H2O(l) ΔHr° = -2873 kJ/mol
-1670 kJ/mol, calculate standard
Most cars run via combustion of gasoline in their engines. Gasoline is usually
enthalpy of reaction of the follow-
shown as octane (C8H18). As a result of combustion of 1 mole of octane, 5471
ing reaction?
kJ of energy is released.
4Al(s) + 3O2(g) → 2Al2O3(s) 25
C8H18(l) + 2 O2(g) → 8CO2(g) + 9H2O(l) ΔHr° = -5471 kJ/mol
∆Hr˚ = ?kJ
Another example of combustion reactions is the reaction between hydrogen
Answer: -3340 kJ and oxygen.
1
H2(g) + 2 O2(g) → H2O(l) ΔHr° = -286 kJ/mol
Combustion of hydrogen supplies energy to space shuttles.
Standard enthalpy of combustion is shown with ∆Hc° symbol. Standard com-
bustion is defined as the heat released through combustion of 1 mole of any
substance under standard conditions (25°C temperature, 1 atm pressure). In
Table 1-3, standard enthalpy of combustion values for some elements and com-
pounds are shown.

20 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics
Table 1-3 Standard enthalpy of
Elements oxides are formed from combustion of elements with oxygen. combustion values ∆Hc° for some
Through combustion of organic substances, carbon dioxide gas, liquid water elements and compounds.
and heat is released. For example, combustion of glucose (C6H12O6) in body
supplies necessary energy for biological functions of body. Substances
C6H12O6(s) + 6O2(g) → 6CO2(g) + 6H2O(l) ΔHr° = -2808 kJ/mol
The main condition to make sure that standard enthalpy of reaction ∆Hr° be-
come equal to standard enthalpy of combustion ∆Hc° is combustion of 1 mole
of substance with enough oxygen. All combustion reactions are exothermic
reactions.
Example 1-5
Write down the chemical reaction of combustion of liquid ethyl alcohol
(C2H5OH) using the following data. ∆Hc0 (C2H5OH(l) ) = -1367 kJ/mol

Solution:
To yield -1367 kJ/mol of heat, 1 mole of liquid ethyl alcohol (C2H5OH) is com-
busted with enough O2.

1-12-3-Enthalpy of Physical Changes

Matter is in a cycle of changing states. The process of transformation from liq-
uid to gas form is called as vaporization. The heat necessary for vaporization of
1 mole of any substance is called as enthalpy of vaporization. It is shown with
∆Hvap symbol. For example, 1 mole of liquid water absorbs 44 kJ of heat while
transformed into water vapor. The equation for the reaction is given below: Exercise 1-6
As ∆Hc0 (C3H8) = - 2219 kJ/mol,
vaporization write down the combustion reac-
H2O(l) → H2O(g) ΔHvap = 44 kJ/mol tion of propane gas (C3H8).
The opposite of this reaction that is the transformation of water vapor to liquid
water is called as condensation. The symbol of enthalpy of condensation is
∆Hcond. As vaporization is the reverse of condensation, the value of ∆Hcond is the
same as ∆Hvap and with an opposite sign.
condensation
H2O(g) → H2O(l) ΔHcond = -44 kJ/mol

One of the physical changes is the transformation of substances from solid to

liquid. This is called as fusion. The heat necessary to transform 1 mole of solid
substance to liquid is called as enthalpy of fusion and shown with ∆Hfus.
For example, the process of transformation of 1 mole of ice to water occurs
through absorption of 6 kJ/mol heat.
fusion
H2O(s) → H2O(l) ΔHfus = 6 kJ/mol
The opposite of fusion is crystallization. The enthalpy of crystallization is
shown with ∆Hcryst symbol. Transformation of 1 mole of water from liquid to
solid is shown in the following equation.

FEZALAR EDUCATIONAL INSTITUTIONS 21

 Chapter - 1

crystallization
H2O(l) → H2O(s) ΔHcryst = -6 kJ/mol
As a summary of what is mentioned above can be given in the following rela-
tionship:

ΔHvap = - ΔHcond and ΔHfus = - ΔHcryst

The sign of enthalpies of vaporization and fusion is positive. In other words,

heat is absorbed (endothermic) to realize these reactions. The sign of enthalp-
ies of condensation and crystallization is negative. That means heat is released
(exothermic) during these reactions.

Exercise 1-7 Example 1-6

As enthalpy of vaporization of liquid ammonia is 23 kJ/mol, what is the value
As enthalpy of fusion of solid of enthalpy of condensation?
acetic acid (CH3COOH) is 5.11
kJ/mol, calculate the enthalpy of Solution:
crystallization of this acid? The vaporization equation of ammonia is as follows:
Answer: -5.11 kJ/mol
vap.
NH3(l) → NH3(g) ΔHvap = 23 kJ/mol

As condensation is reverse of vaporization:

cond.
NH3(g) → NH3(l)

ΔHcond = - ΔHvap = - 23 kJ/mol

1-13- METHODS OF CALCULATING STANDARD

ENTHALPY OF REACTION

1-13-1-Hess’s Law
It isn’t possible to form some compounds from their elements directly, be-
cause either the reaction occurs so slowly or some unwanted side products are
formed. Therefore, the values of ∆Hr° of this kind of reactions are measured
indirectly. This method depends on Hess’s Law . According to this law, the en-
thalpy of a chemical reaction is equal to the sum of enthalpies of intermediate
reactions which makes up of the main reaction.

In other words, if we can divide the reaction into a series of reactions, the value
of ∆Hr° of the main reaction can be calculated. Because ∆Hr° depends on the
initial and final states of the system. It doesn’t depend on the path the reaction
follows. Hess’s law is similar to the ascension of an elevator in an apartment
building from the 1st floor to the 6th floor either directly or stopping at each
floor. The result is the same in both situations.
For example, in the reaction of carbon (graphite) and oxygen and forming car-
bon monoxide, the released heat can’t be measured directly.
1
C(graphite) + 2 O2(g) → CO(g) ΔHr° = ?

22 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

The reason is that the formation of CO2 can’t be prevented. But the heat re-
leased during full combustion of carbon (graphite) with oxygen and the heat re-
leased during combustion of CO and forming CO2 can be calculated as shown
in the following equations.
1) C(graphite) + O2(g) → CO2(g) ΔHr° = -393.5 kJ/mol
1
2) CO(g) + 2 O2(g) → CO2(g) ΔHr° = -283 kJ/mol

The formation of CO from graphite C and O2 doesn’t contain CO2. Therefore,

we need to eliminate CO2. For this, we can reverse Equation 2.

1
3) CO2(g) → CO(g) + 2 O2(g) ΔHr° = +283 kJ/mol

As chemical equations and values of enthalpies can be summed just as algebra-

ic equations, we can get the following by summing (1) and (3)
1) C(graphite) + O2(g) → CO2(g) ΔHr° = -393.5 kJ/mol
1
3) CO2(g) → CO(g) + 2 O2(g) ΔHr° = +283 kJ/mol
___________________________________________________________ We can divide the enthalpy of forma-
1 tion reaction of 1 mole of CO from
4) C(graphite) + 2
O2(g) → CO(g) ΔHr° = -110.5 kJ/mol
the reaction between Cgraphite and O2
This equation is the same as the reaction equation between C(graphite) and O2(g) (gas) into two according to Hess
whose ∆Hr° value is wanted. That means this reaction occurs along with 110.5 Law.
kJ/mol of heat release. Figure 1-3 shows what has been told above. Figure 1-3

Example 1-7
Calculate standard enthalpy of formation of main elements of CS2 (l) compound
from its most stable forms.
C(graphite) + 2S(rhombic) → CS2(l) ΔHf°(CS2(l)) = ? kJ/mol

Thermal equations and values of enthalpies are given below.

1) C(graphite) + O2(g) → CO2(g) ΔHr° = -394 kJ/mol
2) S(rhombic) + O2(g) → SO2(g) ΔHr° = -296 kJ/mol
3) CS2(l)+ 3O2(g) → CO2(g) + 2SO2(g) ΔHr° = -1072 kJ/mol

Solution:
If we examine the equation which we want to find out the value of
∆Hf°(CS2 ), CS2 (l) is on the products’ side. But in Equation 3 it is on the reac-
tants’ side. Therefore, we reverse Equation 3.
4) CO2(g) + 2SO2(g) → CS2(l)+ 3O2(g) ΔHr° = + 1072 kJ/mol

The equation in which the value of ∆Hf° (CS2) is wanted, it contains 2 moles of
S. Therefore, we need to multiply Eq. 2 by 2.
5) 2S(rhombic) + 2O2(g) → 2SO2(g) ΔHr° = 2 × -296 kJ/mol = -592 kJ

FEZALAR EDUCATIONAL INSTITUTIONS 23

 Chapter - 1

Exercise 1-8 If we add Equation 4 and 5 with Equation 1:

Calculate the standard enthalpy of 1) C(graphite) + O2(g) → CO2(g) ΔHr° = -394 kJ/mol
formation of the reaction in which 4) CO2(g) + 2SO2(g) → CS2(l)+ 3O2(g) ΔHr° = + 1072 kJ/mol
acetylene (C2H2 (g)) is formed from 5) 2S(rhombic) + 2O2(g) → 2SO2(g) ΔHr° = -592 kJ/mol
its main elements. _______________________________________________________
2C(graphite) + H2(g) → C2H2(g)
C(graphite) + 2S(rhombic) → CS2(l) ΔHf°(CS2(l)) = ? kJ/mol
ΔHf° (C2H2(g)) = ? kJ
This equation is the same as the equation which we want to find out the value
The following thermal equations are of ∆Hf° (CS2(l)). Therefore:
given:
∆Hf° (CS2(l)) = -394 kJ + 1072 kJ + (-592 kJ) = 86 kJ
1) C (graphite) + O2(g) → CO2(g)
1-13-2-Using The Values of Standard Enthalpy of Formation
ΔHr° = -394 kJ/mol
In order to calculate (∆Hr°) enthalpy of reaction, the ∆Hf° values of compounds
1 can be used.
2) H2(g) + O2(g) →H2O(1)
2 aA + bB → gG + hH
ΔHr° = -286 kJ/mol
We use the following relationship to calculate the ∆Hr° value of this reaction.
3) 2C2H2(g)+5O2(g) →
∆Hr° = Ʃ n ∆Hf° (Products) - Ʃ n ∆Hf° (Reactants)
4CO2(g) +2H2O(1)
n is number of moles of reactants and products. Ʃ means total. The calculation
ΔHr° = -2599 kJ/mol of ∆Hr° value of the thermal reaction above can be done as follows:

∆Hr° = [g∆Hf° (G) + h∆Hf° (H)] - [a∆Hf° (A) + b∆Hf° (B)]

Answer: 225.5 kJ/mol Here what we will pay attention is that the enthalpy of formation ∆Hf° of the
most stable form of any element is equal to zero. As mentioned before,

∆Hf° (Element) = 0 kJ/mol

Exercise 1-9 Example 1-8
When benzene (C6H6 ) is burnt in air, The formation reaction of termite compound from aluminum and iron (III)
it yields carbon dioxide gas and liquid oxide occurs as follows:
water. Calculate the ∆Hr° value of this
reaction according to the following. 2Al(s) + Fe2O3(s) → Al2O3(s) + 2Fe(l) ΔHr° = ? kJ
ΔHf° ( C6H6(1)) = 49 kJ/mol ,
Calculate the standard enthalpy of reaction using the following.
ΔHf° ( CO2(g)) = -394 kJ/mol ,
ΔHf° ( H2O(1)) = -286 kJ/mol , ΔHf° (Al2O3(s)) = -1670 kJ/mol

ΔHf° (Fe2O3(s)) = -822 kJ/mol

Answer: -3271 kJ/mol
ΔHf° (Fe(l) ) = 12 kJ/mol

Solution:
The following can be written using the relationship above.

∆Hr° = Ʃ n ΔHf° (Products) - Ʃ n ΔHf° (Reactants)

24 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

∆Hr° = [ΔHf° (Al2O3(s)) + 2ΔHf° (Fe(l) )] - [2ΔHf° (Al(s)) + ΔHf° (Fe2O3(s))]

∆Hf0 (Al(s) ) = 0 because the most stable form of aluminum is the solid form.
However, under standard conditions, iron is in solid form, the liquid form is
not stable. Therefore, ∆Hf̊ (Fe(l)) is not zero.

∆Hr° = [(-1670) + 2 (12 )]kJ/mol - [2 (0) + (-822)]kJ/mol

= -824 kJ/mol
1-14-SPONTANEOUS PROCESSES
These are physical and chemical reactions occurring by themselves without
any outside factor under certain conditions. The reactions occurring autono-
mously at a certain temperature, pressure or concentration are called as spon-
taneous reactions.
The following can be given as examples for physical and chemical sponta- Spontaneous and Non- Sponta-
neous processes. neous Processes
-Water drops from a fall downward but the opposite is impossible.
-Flow of heat from a hot object to a cold one, the opposite doesn’t occur.
-Lump of sugar dissolves in coffee spontaneously, but dissolved sugar can’t
solidify by itself.
-Freezing of water at 0°C spontaneously, melting of ice at 0°C and 1 atm.
-Rusting of iron spontaneously when objected to oxygen and moisture; but
rust of iron can’t transform into iron.
-While a piece of Na forms NaOH and hydrogen by reacting with water, H2
and NaOH can’t form water and sodium by reacting.
-While gas in a vacuumed container expands spontaneously, gas molecules
can’t accumulate in a container spontaneously. Figure 1-4
As seen in these examples, while some processes occur spontaneously in a
direction, they can’t occur spontaneously in the opposite direction.
Why do some processes occur spontaneously?
One of the most suitable answers which can be given for this question is that
along with spontaneous processes, a decrease occurs in the energy of all sys-
tem (less energy means more stability). In other words, final energy of system
is less than the initial energy. This case explains the fact that heat flows from a
hot object to a cold one and water drops from top of a fall.
Most reactions which cause decrease in energy are exothermic reactions. For
example, combustion of methane under standard conditions:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ΔHr° = -890 kJ
Acid-Base Neutralization Reactions:
H+(aq) + OH-(aq) → H2O(l) ΔHr° = -56 kJ
A) Self- Expansion of gas in a vacu-
With respect to given examples, can it be said that spontaneous processes are umed container
always exothermic reactions? B) All gas Molecules can not accu-
Answer: mulate in a container.
It isn’t possible to generalize this hypothesis for a very simple reason, because
there are some spontaneous physical and chemical changes despite being en- Figure 1-4
dothermic.

FEZALAR EDUCATIONAL INSTITUTIONS 25

 Chapter - 1

For example:
Dissolution of ammonium chloride (NH4Cl) in water is an endothermic process
and it occurs spontaneously.
NH4Cl(s) → NH4+(aq) + Cl-(aq) ΔHr° = +14 kJ
Decomposition of mercury oxide (HgO) occurs spontaneously and it is endo-
thermic.
2HgO(s) → 2Hg(l) + O2(g) ΔHr° = 91 kJ
Melting of ice is an endothermic process but it occurs spontaneously.
H2O(s) → H2O(l) ΔHfus = 6 kJ/mol
Vaporization of water is an endothermic process and it is spontaneous.
H2O(l) → H2O(g) ΔHvap = 44 kJ/mol
With respect to examples above, we can say that an endothermic process can
be spontaneous. But we can’t generalize this statement, because there are many
reactions despite being endothermic they don’t occur spontaneously.
In other words, we can’t decide if a reaction occurs spontaneously or not by just
looking at it being endothermic or exothermic. To decide this, we need a new
thermodynamic function called as entropy.

1-15-ENTROPY
Entropy is a thermodynamic function which is used to estimate if a reaction oc-
curs spontaneously or not. Its symbol is (S). The disorder in all reactions-wheth-
er spontaneous or not-is called as entropy.
It shows to which extent the disorder of system has reached. As the disorder
increases in the system, the value of entropy increases. As the system becomes
more ordered (disorder decreases), the value of entropy decreases.
Entropy is a thermodynamic function which is similar to enthalpy and its abso-
lute value can’t be measured. Only change in entropy can be measured.
∆S = Sf - Si
Here, Sf is final entropy and Si is initial entropy.
In all spontaneous reactions and physical processes, disorder increases. For
example, ammonium chloride dissolves in water spontaneously.
NH4Cl(s) → NH4+(aq) + Cl-(aq) ΔHr° = +14 kJ
In this dissolution reaction, the salt decomposes to its ions. These ions are more
disordered than ammonium chloride molecules. When liquid water vaporizes,
vapor molecules become more disordered than liquid water molecules. Liquid
water molecules are also more disordered than ice molecules. Generally, the
entropy of gas state is always bigger than the entropy of liquid state. The en-
tropy of liquid state has a bigger value than the entropy of solid state. Fig. 1-5
The increase in the entropy of system occurs with an increase in distribution of
energy. A change in physical states of the system changes its entropy.

26 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

In solid state, molecules are ordered and closely packed. When fusion starts,
these atoms or molecules start moving and they get out of crystal lattice and
disorder increases. Thus, a shift from order to disorder occurs. As a result,
entropy increases too. Similarly, entropy of system increases in vaporization.

This increase is greater than that of melting process. The reason is that atoms
and molecules in gas state distribute more to fill all the space they are inside.
Entropy always increases in reactions occurring in solutions. For example,
when sugar crystals are dissolved in water, the ordered structure of sugar is dis-
rupted. Therefore, disorder of solution is greater than that of pure solvent and
pure solute. When an ionic solid as sodium chloride is dissolved, the increase
in entropy depends on two factors. These are:
A- Preparation of solution (Mixing solute and solvent)
B- Ionization of solid compound
Heating increases entropy of system. Because heating does not only increase
displacement motion of molecules but also increases rotational motion and vi-
bration. Besides, with temperature increase, all energy types which depend on
molecular motion also increase. Therefore, heating increases disorder of sys-
tem and its entropy.

Entropy of gases is greater than

that of liquids. Similarly, entro-
py of liquids is greater than that
of solid substance.
Figure 1-5

FEZALAR EDUCATIONAL INSTITUTIONS 27

 Chapter - 1

Some reactions in which entropy

increases.
Figure 1-6

Exercise 1-10 Example 1-9

How do the entropies of the fol- For the following processes, estimate if change in entropy (∆S) is greater or
lowing systems change? smaller than zero.
A- Condensation of water vapor A- Freezing of ethyl alcohol
B- Formation of sugar crystals in B- Vaporization of liquid bromide
supersaturated solution
C- Dissolution of glucose in water
C- Heating H2 gas from 20°C to
80°C D- Cooling of nitrogen gas from 80°C to 20°C

D- Sublimation of solid iodine Solution:

A- Freezing means transformation of liquid ethyl alcohol to solid ethyl alco-
hol. As molecules are more ordered in solid than liquid, change in entropy is
smaller than zero (∆S<0).
B- While liquid bromide is transformed to bromide vapor, the disorder of mol-
ecules increases. Therefore, change in entropy is greater than zero (∆S>0).

28 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

C- Because solid glucose molecules distribute in water, disorder increases. Table 1-4
That means change in entropy is greater than zero(∆S>0). Absolute entropy values
D- Cooling of nitrogen gas from 80°C to 20°C decreases disorder of nitrogen for some element and
molecules. As a result, entropy decreases and change of entropy is smaller than compound
zero (∆S<0). Substances S°(J/K.mol)
1-15-1-Calculation of Standard Entropy in Chemical Reac-
tions
Thermodynamics allows calculation of value of absolute entropy (S°) in all
chemical elements and compounds. Using this value, we can measure change
of standard entropy of reaction (∆Sr°) in a chemical reaction. We use the fol-
lowing relationship for this:
∆Sr° = Ʃ n S° (Products) - Ʃ n S° (Reactants)
n means number of moles of reactants and products, Ʃ means total.
For the following general chemical reaction:
aA + bB → gG + hH
The change of standard entropy of this reaction (∆Sr°) can be written using the
relationship above as follows:
∆Sr° = [g S° (G) + h S° (H)] - [a S° (A) + b S° (B)]
Table 1-4 shows standard absolute entropy values for some elements and chem-
ical compounds. According to International System of Units, unit of entropy is
J/K.mol.
Example 1-10
Calculate change of standard entropy of reaction (∆Sr°) of the following reac-
tion at 25°C and 1 atm standard conditions.
2CO(g) + O2(g) → 2CO2(g)
S°(CO) = 198 J/K.mol, S°(CO2) = 214 J/K.mol,
S°(O2) = 205 J/K.mol

Solution: Exercise 1-11

∆Sr° = Ʃ n S° (Products) - Ʃ n S° (Reactants) Calculate change of standard entro-
py of reaction (∆Sr°) of the fol-
∆Sr° = [2S° (CO2)] - [2S° (CO) + S° (O2)] lowing reaction at 25°C and 1 atm
standard conditions.
∆Sr° = [2 × 214 J/K.mol] - [(2×198 + 205) J/K.mol]
4Fe(s) + 3O2(g) → 2Fe2O3(s)
∆Sr° = -173 J/K.mol
According to;
S°(Fe2O3) = 87 J/K.mol,
1-16-GIBBS FREE ENERGY S°(O2) = 205 J/K.mol,

In 1800, a scientist named Gibbs developed a relationship between enthalpy S°(Fe) = 27 J/K.mol
(H) and entropy (S). This relationship enables us to estimate whether a reaction
occurs spontaneously or not by using enthalpy or entropy values. Gibbs pro- Answer: -549 J/K.mol
posed a new thermodynamic function which is called as “Gibbs free energy.”

FEZALAR EDUCATIONAL INSTITUTIONS 29

 Chapter - 1

Table 1-5 The symbol of this function is G. It defines the maximum energy which can be
Values of Standard Free Gibbs obtained from measurement of ∆H and ∆S at constant temperature and pres-
sure. Change in Gibbs free energy ∆G is defined as follows:
Energy of Formation Of some
Compounds (at constant temperature and pressure) ∆G = ∆H - T∆S
Free Gibbs Energy (sometimes called as free energy for ease) is a function just
like enthalpy and entropy. It is a real function which shows if physical changes
or chemical reactions occur spontaneously or not. The sign of Gibbs Free En-
ergy is commented as follows:
-If value of ∆G is negative (∆G<0), reaction or physical change occurs spon-
taneously.
-If value of ∆G is positive (∆G > 0), reaction or physical change doesn’t occur
spontaneously (the change or reaction occurs spontaneously at opposite direc-
tion).
-If value of ∆G is zero (∆G = 0), reaction or physical change is at equilibrium.

1-16-1-Standard Gibbs Free Energy of Reaction

Standard Gibbs Free Energy of Reaction which is shown with ∆Gr° symbol is
the change in value of free energy if a reaction occurs under standard condi-
tions (25°C temperature and 1 atm pressure). In order to calculate ∆Gr° for any
reaction, values of Standard Gibbs Free Energy of Formation ∆Gf° are used.
Standard Gibbs Free Energy of Formation is the amount of change in free en-
ergy when 1 mole of any compound is formed from most stable forms of its
elements under standard conditions (25°C temperature and 1 atm pressure.)
It is possible to calculate value of ∆Gr° by a similar equation to standard en-
thalpy of reaction from standard enthalpy of formation values. It is as follows:
∆Gr° = Ʃ n ΔGf° (Products) - Ʃ n ΔGf° (Reactants)
n is number of moles of reactants and products and Ʃ is total.
For the following general reaction:
aA + bB → gG + hH
The change of standard free Gibbs energy of this reaction is as follows:
∆Gr° = [g ΔGf° (G) + h ΔGf° (H)] - [a ΔGf° (A) + b ΔGf° (B)]
Table 1-5 shows values of standard free Gibbs energy of formation of some
compounds. Here what needs attention is that ∆Gf° values of most stable forms
of elements are equal to zero.
∆Gf° (Element) = 0 kJ/mol
Unit of standard free energy is (J/mol) according to International System of
Units.

30 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

Example 1-11 Exercise: 1-12

Calculate standard free Gibbs energy of the following reaction under standard
conditions, 25°C and 1 atm pressure. Also tell if the reaction occurs sponta- Calculate standard Gibbs free ener-
neously or not under these conditions. gy of the following reaction under
standard conditions, 25°C and 1 atm
2C6H6(l) + 15O2(g) → 12CO2(g) + 6H2O(l)
pressure. Also tell if the reaction
Givens: occurs spontaneously or not under
∆Gf°(C6H6(l)) = 173 kJ/mol, ∆Gf°(CO2(g)) = -394 kJ/mol these conditions.
2NO(g) + O2(g)→ 2NO2(g)
∆Gf°(H2O(l)) = -237 kJ/mol
Givens:
ΔGf° (NO) = 87 kJ/mol,
Solution: ΔGf° (NO2 ) = 52 kJ/mol
∆Gr° = Ʃ n ΔGf° (Products) - Ʃ n ΔGf° (Reactants)
Answer : -70 kJ/mol
∆Gr = [12 ΔGf (CO2) + 6 ΔGf (H2O)] - [2 ΔGf (C6H6) + 15 ΔGf (O2)]
° ° ° ° ° Spontaneous

∆Gr° = [12 × (-394 kJ/mol) + 6 × (-237 kJ/mol)]

- [2 × 173 kJ/mol + 15 × 0]

∆Gr° = -6496 kJ/mol

As the result is negative, the reaction occurs spontaneously.

As the result is negative, the reaction occurs spontaneously.

1-16-2-Application of Gibbs Equation and Direction of

Chemical Reactions
Gibbs equation is accepted as a very important equation which enables us to
understand properties of chemical reactions. The equation is also related to
changes which occurs in properties of system.

∆G = ∆H - T ∆S
Because using ∆G values saves us from calculation of changes in enthalpy
and entropy. According to Gibbs equation, change in free energy (∆G) in-
cludes two important factors which affect if a chemical reaction can occur
spontaneously or not.
First Factor:
Reactions mostly work towards the direction with the lowest energy (enthal-
py). If value of ∆H is negative, in other words exothermic, the possibility of
spontaneous occurrence of reaction increases.
Second Factor:
Reactions mostly work towards the direction with the highest entropy. If val-
ue of ∆S is positive (if disorder increases), the possibility of spontaneous oc-
currence of reaction increases. Positive value of ∆S causes value of ∆G being
negative.

FEZALAR EDUCATIONAL INSTITUTIONS 31

 Chapter - 1

If we put aside temperature, there must be a relationship as follows between

two factors mentioned above for a reaction occur spontaneously. (∆H < 0 and
∆S > 0)
Generally, ∆H and ∆S symbols affect values of ∆G in 4 ways:
1-If ∆H and ∆S have positive values, when T∆S is bigger than ∆H, ∆G will
be negative. This condition occurs when T is high.
2-If ∆H is positive and ∆S is negative, value of ∆G will be always positive
independent of the effect of temperature T.
3-If value of ∆H is negative and ∆S is positive, value of ∆G will be negative
independent of the effect of temperature T.
4-If both values of ∆H and ∆S are negative and if value of T∆S is less than
∆H, value of ∆G will be negative. This condition occurs only when T is low.
The temperature which causes negative ∆G values in Situation 1 and 2 de-
pends on real values of ∆H and ∆S of system. Table 1-6 summarizes possible
effects defined below.
Table 1-6

Factors effecting sign of ∆G in ∆G=∆H-T∆S

∆H ∆S ∆G

+ + Reaction occurs spontaneously at high tempera-

ture. It occurs spontaneously in the opposite
direction at low temperatures.

+ - ∆G is always positive. Reaction doe not occur

spontaneously at all temperature. It occurs spon-
taneously in opposite direction.

- +
∆G is always negative. Reaction occurs sponta-
neously at all temperature.

- - Reaction occurs spontaneously at low tempera-

tures. It occurs spontaneously in opposite direc-
tion at high temperature.

Under standard conditions 25°C and 1 atm pressure, when ∆Hr° and ∆Sr° are
measured, Gibbs equation can be used as follows:

∆Gr0 = ∆Hr0 - T∆Sr0

32 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

Example 1-12 Exercise-1-13

According to the following data, Calculate the value of ΔGr° of the
C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l) following reaction under standard con-
ditions, 25°C and 1 atm pressure.
Substance ∆Hf° kJ/mol S° J/K.mol C5H12(1)+ 8O2(g) → 5CO2(g) + 6H2O(1)
C2H5OH(l) -278 161 Under standard conditions, the value
O2(g) 0 205 of enthalpy of reaction ΔHr° was cal-
CO2(g) -394 214 culated and the following result was
H2O(l) -286 70 obtained:
ΔHr° = -3536 kJ/mol
Calculate the following values for the reaction under standard conditions.
A) ∆Hr° Besides, ΔSr° was calculated and the
B) ∆Sr° following result was obtained:
C) ∆Gr° ΔSr° = 374 J/K.mol

Solution: Answer: -3647.5 kJ/mol.

A) Calculation of ∆Hr°
∆Hr° = Ʃ n ΔHf° (Products) - Ʃ n ΔHf° (Reactants)
Attention:
∆Hr° = [2 ΔHf° (CO2) + 3 ΔHf° (H2O)] - [ΔHf° (C2H5OH) + 3 ΔHf° (O2)]
While solving this kind of questions,
∆Hr° = [2 × (-394 kJ/mol) + 3 × (-286 kJ/mol)] - [-278 kJ/mol + 3 × 0] we shouldn’t forget that units of ∆Hr°
and ∆Sr° aren’t the same. Therefore, we
∆Hr° = -1368 kJ/mol need to convert unit of entropy from
J/K.mol to enthalpy unit kJ/K.mol.
B) Calculation of ∆Sr°
∆Sr° = Ʃ n S° (Products) - Ʃ n S° (Reactants)
Exercise 1-14
∆Sr° = [2S° (CO2) + 3S° (H2O) ] - [S° (C2H5OH) + 3S° (O2)]
Calculate the value of change in stan-
∆Sr° = [2 × 214 J/K.mol + 3 × 70 J/K.mol] - [161 J/K.mol + 3 × 205 J/K.mol]
dard free energy of the following reac-
∆Sr° = -138 J/K.mol tion under standard conditions, 25°C
and 1 atm pressure.
1(kJ) HCOOH(1) → CO(g) + H2O(1)
∆Sr°(kJ/K.mol) = ∆Sr°(J/K.mol) × _______
1000 (J) Does the reaction occur spontaneously?
(ΔHr°= 16 kJ/mol and change in entro-
1(kJ)
∆Sr°(kJ/K.mol) = -138(J/K.mol) × _______ py (ΔSr˚) = 234 J/K.mol)
1000 (J)
∆Sr°(kJ/K.mol) = -0.138 kJ/K.mol Answer: -53.7 kJ/mol
Spontaneous
C) Calculation of ∆Gr°
Let’s change temperature from centigrade (°C) unit to Kelvin (K) unit.

T(K) = t(°C) + 273 = 25 + 273 = 298 K

As the value of ∆Gr° is negative, the reaction occurs spontaneously at 25 °C
and 1 atm pressure.

FEZALAR EDUCATIONAL INSTITUTIONS 33

 Chapter - 1

∆Gr° = ∆Hr° - T∆Sr°

∆Gr° = -1368 kJ/mol - ( -0.138 kJ/K.mol) x 298 K
∆Gr° = -1327 kJ/mol

1-17-CALCULATION OF ENTROPIES OF PHYSICAL

CHANGES
In the previous chapters, we have defined standard enthalpies of physical
changes as enthalpy of vaporization ∆Hvap and enthalpy of fusion ∆Hfus. Be-
sides, we know that substances change from solid to liquid at melting tem-
perature Tm. Substances change from liquid to gas at boiling temperature Tb.
Melting and boiling temperatures are at equilibrium between solid or liquid
vapor and atmospheric pressure. That means value of ∆G at these tempera-
tures is equal to zero. Therefore, Gibbs relationship can be written as follows:

∆G = ∆H - T∆S
0 = ∆Htr - Ttr∆Str
We get the following from this relationship:
ΔHtr
∆Str = _______
Ttr
tr means transition. For example, substances changes from solid to liquid at
melting temperature. Therefore, melting equation will be as follows:
Attention:
ΔHfus
Here, there is another physical ∆Sfus = _______
change which isn’t mentioned. It Tm
is the change of state of substance fus means fusion. Substances change from liquid to gas at boiling tempera-
directly from solid to gas. This is ture. Therefore, the vaporization equation above can be rewritten as follows:
called as sublimation. As enthalpy
ΔHvap
of sublimation is a state function, it ∆Svap = _______
is equal to the sum of enthalpies of Tb
melting and vaporization. vap means vaporization. We need to highlight that these equations are only
valid when system is at equilibrium (for example melting, vaporization and
sublimation).

Trouton’s Rule
A scientist called Trouton found out that the values of ∆S of most liquids is
equal to a constant number (85 J/K.mol). Therefore, the final equation can be
rearranged as follows:
ΔHvap
∆Svap = 85 J/K.mol = _______
Tb
This equation is called as Trouton’s equation. This equation is used in calcula-
tion of enthalpy of vaporization starting from boiling points of liquids.

34 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

Example 1-13 Exercise 1-15

As the boiling point of hexane is 69°C, calculate the enthalpy of vaporization
(∆Hvap) in kJ/mol unit. Calculate change of entropy for wa-
ter boiling at 100°C (boiling point).
Solution: H2O(l) H2O(g )
We convert the temperature from °C to Kelvin (K) unit.
∆Hvap = 44 kJ/mol
T (K)= t (̊C) + 273 = 69 + 273 = 342 K
From Trouton’s equation
ΔHvap Answer: 118 J/K.mol
∆Svap = _______ = 85 J/K.mol
Tb
ΔHvap = 85 J/K.mol × Tb(K) = 85 J/K.mol × 342 K

= 29070 J/mol
We convert J/mol unit to kJ/mol unit as follows:
1(kJ)
∆Hvap(kJ/mol) = ∆Hvap(J/mol) × _______
1000 (J)
1(kJ)
∆Hvap(kJ/mol) = 29070(J/mol) × _______
1000 (J)

∆Hvap(kJ/mol) = 29 kJ/mol

FEZALAR EDUCATIONAL INSTITUTIONS 35

 Chapter - 1

BASIC EQUATIONS

- The relationship between Kelvin (K) and centigrade () units of temperature

T (K)= t ( ̊C ) + 273

- The relationship between amount of heat and specific heat

q (J) = ς (J/g.°C) × m (g) × ∆T (°C)

- The relationship between amount of heat and heat capacity

q = C × ∆T

- The change in standard enthalpy of reaction

∆Hr° = Ʃ n ∆Hf° (Products) - Ʃ n ∆Hf° (Reactants)
- The change in standard entropy of reaction
∆Sr° = Ʃ n S° (Products) - Ʃ n S° (Reactants)

- The change in free energy at constant temperature

∆G = ∆H - T∆S

- The change in standard free energy of reaction

∆Gr° = Ʃ n ΔGf° (Products) - Ʃ n ΔGf° (Reactants)

- Trouton’s relationship
ΔHvap
∆Svap = 85 J/K.mol = _______
Tb

36 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

BASIC CONCEPTS
Joule Unit: It is an energy unit. It is shown with (J) in International System of Units.
Kelvin Temperature: It is a temperature unit. It is shown with (K) in International System of Units.
System: Thermodynamic system is the part of universe which we study. When a chemical reaction or a physical change
occurs, it consists of substance or substances which participate in the change.
Surroundings: All physical and chemical changes surrounding and affecting system.
Group: It is the sum of system and surroundings.
Group = System + Surroundings
Open System: If substance and energy interaction occurs between system and surroundings, this is called as an open
system. e.g., an open pot containing boiling water
Closed System: If there is only energy interaction between system and surroundings, and substance interaction isn’t
allowed, this is called as a closed system. For example, a closed metal container with boiling water.
Isolated System: If there is neither energy nor substance interaction between system and surroundings, it is called as an
isolated system. For example, a thermos.
Heat Capacity: The amount of heat necessary to raise temperature of m gram of any substance by 1 centigrade.
Specific Heat: The amount of heat necessary to raise temperature of 1 gram of substance by 1 centigrade.
State function: The property or amount which depends on initial state before change and final state after change with no
respect to path followed
Extensive Properties: Properties such as volume and mass which depend on amount of substance.
Intensive Properties: Properties such as pressure, density and temperature which don’t depend on amount of substance
Enthalpy: A thermodynamic state function. It is extensive. It shows amount of absorbed and released heat under constant
pressure. Its symbol is H. As it is a state function, its absolute value can’t be measured. Its change ∆H can be measured.
Exothermic Reaction: They are reactions which produces heat at the end. The sign of enthalpy change is negative.
Endothermic Reaction: They are reactions which need heat to occur. The sign of enthalpy change is positive.
Standard Enthalpy of Reaction: Its symbol is ∆Hr°. It is defined as heat which depends on reaction under standard
conditions.
Standard Enthalpy of Formation: Its symbol is ∆Hf°. It is the heat necessary to form 1 mole of compound from most
stable and standard forms of elements.
Standard Enthalpy of Combustion: Its symbol is ∆Hc°. The heat released from combustion of 1 mole of any substance
with plenty of oxygen at standard temperature and pressure.
Hess’s Law: The enthalpy of main reaction is equal to sum of enthalpies of intermediate steps.
Spontaneous and Non-spontaneous Reactions: Physical and chemical changes which occur by themselves without any
outside factor are called as spontaneous changes under certain conditions. But processes which can’t occur by themselves
under the same conditions are called as non-spontaneous conditions.
Entropy: Its symbol is S. It is a thermodynamic state function. It is accepted as a measure of thermodynamic disorder.
Gibbs Free Energy: Its symbol is G. It is a thermodynamic state function. It helps us to estimate if physical or chemical
processes occur spontaneously or not. It shows the maximum energy which can be obtained from enthalpy and entropy
change.
Standard Gibbs Free Energy of Formation: It symbol is ∆Gf°. It is the amount of change in free energy to form 1 mole
of any compound from its most stable elements under standard conditions, 25°C and 1 atm pressure.

FEZALAR EDUCATIONAL INSTITUTIONS 37

 Chapter - 1

QUESTIONS OF CHAPTER-1
1-1- Define the following terms:
System, surroundings, group, open system, state function, isolated system, joule, closed system, 1st law of
thermodynamics
1-2- What are the units of the following according to International System of Units (SI)?
Enthalpy, entropy, free Gibbs energy
1-3- What are the meanings of the following terms?
Thermochemistry, exothermic, endothermic
1-4- What does state function mean? Tell two concepts as examples for state function. Tell a process which is
not a state function but process function.
1-5- Tell the reason for the necessity of writing physical state while writing thermal reactions.
1-6- What is the difference between specific heat and heat capacity? Tell the units of each concept.
1-7- What is the difference between intensive and extensive properties? Give examples for each.
1-8- Tell about the calorimeter which is used to measure absorbed or released heat where pressure (qp) that is
enthalpy (∆H) is constant.
1-9- Calculate the specific heat of a piece of silver which has a mass of 360 g and heat capacity of 86 J/°C.
Answer: 0.24 J/g.°C
1-10- 6 g of copper was heated from 21°C to 124°C. As specific heat of copper is 0.39 J/g.°C, calculate the
amount of heat in kJ unit.
Answer: 0.241 kJ
1-11- 350 g of mercury was cooled from 77°C to 12°C. Calculate the released heat in kJ unit.
Specific heat of mercury = 0.14 J/g.°C
Answer: -3.2 kJ
1-12- The temperature of 34 g of ethanol was raised to 79°C from 25°C. Calculate the amount of absorbed
heat. Specific heat of ethanol = 2.44 J/g.°C
Answer: 4479.8 J
1-13- 155 g of sample taken from an unknown substance was heated from 25°C to 40°C. 5700 J of heat was
applied during the process. Calculate the specific heat of this substance.
Answer: 2.45 J/g.°C
1-14- While heating 4.5 g of gold pieces, 276 J of heat was applied. If the initial temperature was 25°C, what
is the final temperature? Specific heat of gold = 0.13 J/g.°C
Answer: 496.8°C

38 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

1-15- Find the value of ∆Gr° in the following reaction:

2CO(g) + O2(g) → 2CO2(g)
Givens:
ΔHf°(CO) = -110.5 kJ/mol, ΔHf°(CO2) = -393.5 kJ/mol,
S°(O2) = 205 J/K.mol, S°(CO) = 198 J/K.mol, S°(CO2) = 214 J/K.mol,

Answer : -514.4 kJ

1-16- As a result of the reaction in the calorimeter which has a total heat capacity of 2.4 kJ/°C, the tempera-
ture of the calorimeter was raised by 0.12°C. Calculate the change in the enthalpy of reaction.
Answer : -288 J
1-17- When 1.5 g of acetic acid (CH3COOH) was burnt in the calorimeter which had 750 g of water, the
temperature of the calorimeter and its content was raised from 24°C to 28°C. Calculate the amount of heat
released from combustion of 1 mole of acetic acid by neglecting the heat capacity of the calorimeter. (Molar
mass of acid= 60 g/mol) (Specific heat of water= 4.2 J/g.°C)
Answer: -504000 J/mol
1-18- What are the standard reaction conditions in thermochemistry? What are the differences between those
and standard conditions used for gases?
1-19- 2.6 g of acetylene C2H2 (M= 26 g/mol.) was put in a calorimeter. After burning the substance, 130 kJ
heat was released. Calculate the standard enthalpy of formation of acetylene. The following data is given.

ΔHf°(CO2) = -393.5 kJ/mol, ΔHf°(H2O) = -286 kJ/mol

Answer: 227 kJ/mol

1-20- Calculate the change in standard enthalpy of formation ∆Hf° (Al2O3) and standard enthalpy of combus-
tion ∆Hc°(Al) for the following reaction.
4Al(s) + 3O2(g) → 2Al2O3(s) ΔH ₒ = -3340 kJ
r

Answer: -1670 kJ/mol; -835 kJ/mol

1-21- Apply Hess’s Law in the following thermal equations at 25°C and 1 atm pressure and tell its use in
chemistry.

1) H2(g) + Cl2(g) → 2HCl(g) ΔHrₒ = -185 kJ

2) 2H2(g) + O2(g) → 2H2O(g) ΔHrₒ = -484 kJ
Calculate the ΔHrₒ of the following reaction.
4HCl(g) + O2(g) → 2Cl2(g) + 2H2O(g) ΔHrₒ = ? kJ
Answer: -114 kJ

FEZALAR EDUCATIONAL INSTITUTIONS 39

 Chapter - 1

1-22- If the following thermal equations were given at 25°C and 1 atm pressure:
1) 1 N2(g) + O2(g) → NO2(g) ΔH ₒ = 33 kJ
r
2
2) N2(g) + 2O2(g) → N2O4(g) ΔHrₒ = 11 kJ

Calculate ΔHrₒ for the following reaction

2NO2 (g) → N2O4(g) ΔHrₒ = ? kJ

Answer: -55 kJ

1-23- In the following equation givens at 25ₒC and 1 atm pressure.

1) FeO(s) + H2(g) → Fe(s) + H2O(g) ΔHrₒ = 25 kJ

ₒ
2) 3FeO(s) + 1 O2 (g) → Fe3O4(s) ΔHr = -318 kJ
2
3) H2(g) + 1
O2 (g) → H2O(g) ΔHrₒ = -242 kJ
2
Calculate ΔHrₒ for the following reaction;

3Fe(s) + 4H2O(g) → Fe3O4(s) + 4H2(g) ΔHrₒ = ? kJ

Answer: -151 kJ

1-24- Calcium carbonate decomposes according to the following reaction.

CaCO3(s) → CaO(s) + CO2(g)
Standard enthalpy of formation of each of CaO, CO2, CaCO3 is (-635, -393.5, -1207) kJ/mol respectively. As
∆Sr˚ is 160 J/K.mol, Calculate;
1) ∆Hr˚ then draw its energy diagram.
2) ∆Gr˚
3) At which temperature does the reaction occur spontaneously?
Answer: 1) 178.5 kJ 2) 130.8 kJ/mol 3) Greater than 1115.6 K

1-25- Using the following data;

ΔHfₒ (NH3) = -46 kJ/ mol, ΔHfₒ (CH4) = -75 kJ/ mol
ΔHfₒ (HCN) = 135kJ/ mol, ΔHfₒ (H2O) = -242 kJ/ mol
Calculate ΔHrₒ for the following reaction at 25ₒC and 1 atm pressure.
2NH3(g) + 3O2(g) + 2CH4(g) → 2HCN(g) + 6H2Og)

Answer: -940 kJ

40 FEZALAR EDUCATIONAL INSTITUTIONS

 Thermodynamics

1-26- Calculate standard enthalpy of formation of HPO3(s) compound using the following data.

P4O10(s) + 4HNO3(1) → 4HPO3(s) + 2N2O5(g) ΔHrₒ = -180 kJ

ΔHfₒ values of the compound are following.

ΔHfₒ (P4O10) = -2984 kJ/mol, ΔHfₒ (N2O5) = -43 kJ/mol

ΔHfₒ (HNO3) = -174 kJ/mol
Answer: -943.5 kJ/mol
1-27- Calculate the ΔSrₒ of the following reaction at 25ₒC and 1 atm pressure;

N2(g) + 3H2(g) → 2NH3(g)

Using the following data.
Sₒ (N2) = 192 J/K.mol, Sₒ (H2) = 131 J/ K.mol
Sₒ (NH3) = 193 J/K.mol
Answer: -199 J/K.mol
1-28- What does spontaneous process mean? Give two examples for spontaneous and non-spontaneous pro-
cesses.
1-29- Which of the following processes occurs spontaneously? Which not?
A- Dissolution of table salt in water
B- Climbing Mount Everest
C- After opening the cap of perfume bottle, spread out of perfume in the room
D- Separating helium and neon gas mixture
1-30- Define entropy. What are the units of entropy according to International System of Units (SI)?
1-31- Calculate value of ΔSr⁰ in J/K.mol for the following reaction.
2H2(g) + O2(g) → 2H2O(g)
Givens: ΔH ₒ (H O) = -242 kJ/mol, ΔG ₒ (H O) = -228 kJ/mol
f 2 f 2

Answer: -94 J/K.mol

1-32- Calculate ΔSrₒ of the following reaction at 25ₒC and 1 atm pressure;

SiH4(g) + 2O2(g) → SiO2 (s) + 2H2O (l)

Use the following data;
Sₒ(SiH4) = 206 J/K.mol, Sₒ(O2) = 205 J/K.mol
Sₒ(SiO2) = 42 J/K.mol, Sₒ(H2O) = 70 J/K.mol
Answer: -434 J/K.mol

FEZALAR EDUCATIONAL INSTITUTIONS 41

 Chapter - 1

1-33- As the value of ∆Sr° of the following reaction is 137 J/K.mol at 25°C and 1 atm pressure, and S°(O2) is
205 J/K.mol, what is the value of S° of (O3) ozone?
2O3(g) → 3O2(g)
Answer: 239 J/K.mol
1-34- Define standard free Gibbs Energy of formation and tell its units.
1-35- Calculate the ∆Hr˚ for the following reaction by using Hess’s law.
CO + 2H2 → CH3OH
Standard enthalpy of combustion of each of CO, H2, CH3OH is (-284, -286, -727) kJ/mol.
Answer: -129 kJ
1-36- If the ∆H and ∆S values of the following reactions are known, find out the temperatures at which those
reactions occur spontaneously.
Reaction A: ∆S = +48 J/K.mol and ∆H = +126 kJ/mol
Reaction B: ∆S = -105 J/K.mol and ∆H = -12kJ/mol
Answer: A: Greater than 2625 K
B: Less than 114.3 K
1-37- Estimate which of the following two reactions occurs spontaneously by looking at ∆S and ∆H values
measured at 25°C and 1 atm pressure.
Reaction A: ∆S = 30 J/K.mol and ∆H = 11 kJ/mol
Reaction B: ∆S = 113 J/K.mol and ∆H = 2 kJ/mol
If both reactions don’t occur spontaneously at 25°C and 1 atm pressure, at which temperature do they occur
spontaneously?
Answer: A: Don’t occur spontaneously. If temperature is greater than 366.7 K, it is spontaneous.
B: Occurs spontaneously.

1-38- Explain the following processes starting from Gibbs equation (∆G = ∆H - T∆S).
1- Melting of ice under standard conditions.
2- Non –decomposition of water to its elements under standard conditions
3- Self-dissolution of sulfur dioxide gas in water with releasing heat.
4- Calcium carbonate does not decompose at room temperature.
5- Decomposition of mercury (II) oxide is always spontaneous at high temperature.
6- Water does not freeze under standard conditions.

42 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

CHEMICAL EQUILIBRIUM CHAPTER-2

ACHIEVEMENTS
The student can perform those below after completing this chapter:
* He/she can differentiate reversible and irreversible reactions.
* He/she can understand how a reaction reaches equilibrium state.
* He/she can discover the relationship between Kc and Kp which are equilibrium constants.
* He/she learns the importance of equilibrium constants in order to tell way the reaction goes.
* He/she learns the relationship between the equilibrium constants and equation writing method.
* He /she learns the result and the importance of the reaction.
* He/she understands the Le Chatelier Law, equilibrium state and the factors affecting equilibrium constants and
applies all those information to problems.

FEZALAR EDUCATIONAL INSTITUTIONS 43

 Chapter - 2

2-1 REVERSIBLE AND IRREVERSIBLE REACTIONS

The interaction of two or more substances yields one or more new substance/s.
This process is defined as a chemical reaction. Chemical reactions are shown
through chemical equations. Chemical equations demonstrate the changes
which substances undergo in order to produce new materials via formulas. The
arrow sign in the equation shows the way the reaction works.

Chemical equations are divided into two: Reversible reactions and irre-
versible reactions. During irreversible reactions one or two of the reactants are
used up. This is shown with a single arrow . For example, when the
fuel in a car is fully combusted, carbon dioxide and water are produced. This
event is irreversible. Because transformation of carbon dioxide and water into
fuel is extremely difficult or in other words impossible. These kinds of changes
are called one-way reactions. These kinds of reactions are irreversible. Below
are some examples for those.
The formation of sodium sulfate salt and water with addition of sulfuric acid
into sodium hydroxide
H2SO4(aq) + 2NaOH(aq) Na2SO4(aq) + 2H2O(l)
The formation of carbon dioxide through addition of hydrochloric acid into
sodium carbonate.
Na2CO3(s) + 2HCl(aq) 2NaCl(aq) + H2O(l) + CO2(g)

The definition of irreversible reactions: These are chemical reactions in

which under certain conditions one or all of the reactants are depleted. Yielding
substances under the same conditions cannot change back into the substances
forming them.
The other type of reactions is called reversible reactions.
During these reactions, yielding substances can reform the reactants while only
some of the reactants turn into products. In other words, reversible reactions
cannot be completed however long time passes by under suitable conditions.
Some reactants always remain in the reaction chamber. This situation is shown
by two reverse arrows in the equation.⇌

There are many reversible chemical reactions. Respiration is an example. This

event occurs by gas change. The blood coming to lungs carry water and carbon
dioxide. The blood leaves these substances and loads up oxygen. Then through
inner-respiration, it leaves oxygen and reloads water and carbon dioxide. Some
other examples are given below.

1- The formation of ethyl acetate and water through the reaction of acetic acid
with ethyl alcohol.
CH3COOH(l) + CH3CH2OH(l) ⇌ CH3COOCH2CH3(l) + H2O(l)

2- In order to form hydrogen iodide gas in a closed system, the reaction of hy-
drogen gas and iodine vapor. H2(g) + I2(g) ⇌ 2HI(g)

3- In a closed system the decomposition of calcium carbonate salt into calcium

oxide and carbon dioxide. CO2(g)

CaCO3(s) ⇌ CaO(s) + CO2(g)

44 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

4- Some physical changes like vaporization of water in a closed system.

ˆ ˆˆ †ˆ H O
H2O(l) ‡ 2 (g)

The definition of reversible reactions: These are reactions in which

products are changed back into reactants. Products have the capability of
reacting in order to reform the substances yielding them.

2-2 REVERSIBLE REACTIONSAND EQUILIBRIUM STATE:

As stated above, most of the reversible reactions continue in opposite ways
under the same reaction conditions. For example, H2 gas reacts with N2 under
suitable conditions and forms ammonia (NH3) gas. In the beginning, the for-
ward reaction is fast in the way of producing ammonia, having Rf value (Rf Figure 2-1
is rate of forward reaction.) By the time, under the same conditions, as the
concentration of ammonia increases, the forming ammonia decomposes into Reversible reaction reaches equilibrium
H2 and N2 at Rb rate (Rb is the rate of the backward reaction.) Both reactions after a while.
continue until the rates of the reactions become equal (Rf = Rb) Thus, the
reaction reaches chemical equilibrium.
kf
N2(g) + 3H2(g) ⇌ 2NH3(g)
kb

2-3 HOMOGENEOUS AND HETEROGENEOUS REVERSIBLE

REACTIONS:
Reversible reaction
Reversible homogeneous reactions are reactions in which reactants and prod-
ucts are at the same physical conditions. The examples for those are given
below (Keep in mind that all the reactions occur in a closed system)

1- Equilibrium reaction between gases:

N2O4(g) ⇌ 2NO2(g)
2- Equilibrium reaction in a solution:
Equilibrium

HCOOH(l) + CH3OH(l) ⇌ HCOOCH3(l) + H2O(l)

3- Equilibrium reaction between solids:
Zn(s) + S(s) ⇌ ZnS(s)

Regarding the reversible heterogeneous reaction are that reactions that in-
clude the reactants and the products in more than one phase and their exam-
ples in closed system;

H2O(l) ⇌ H2O(g)
2NaHCO3(s) ⇌ Na2CO3(s) + H2O(g) + CO2(g)
2Hg(l) + O2(g) ⇌ 2HgO(s)
Reversible reaction reaches equilib-
rium after a while.

FEZALAR EDUCATIONAL INSTITUTIONS 45

 Chapter - 2

2-4 EQUILIBRIUM STATE AND LAW OF MASS ACTION:

At 445 °C, 2 moles of hydrogen iodide must be formed when a mole of hydrogen
gas and a mole of iodine gases are mixed in order to form hydrogen iodide gas.
H2(g) + I2(g) ⇌ 2HI(g)
But, when this mixture reaches equilibrium, the analysis shows that 78% of HI
gas and 11% of iodine gas and 11% of hydrogen gas is found. Similarly, at the
same temperature, if pure HI gas is heated, it decomposes into hydrogen and
iodine gases. The mixture always contains 78% HI gas and 11% iodine and 11%
of hydrogen at equilibrium.
The relationship between chemical reaction rate and reactions of substances is
called Law of Mass Action. According to the law, the rate of a chemical reaction
is directly proportional to the molecular concentrations of the reacting substanc-
es. The mole numbers in a balanced equation are used as exponents for these
concentrations.
When the law of mass action mentioned above is applied:

According to law of mass action, the Rf and Rb rates can be shown mathemati-
cally as:

2-5 EQUILIBRIUM CONSTANT:

Consider a reversible equilibrium reaction.

In the equation, A, B, G and H are reactants and products.

a, b, g, h are the mole numbers in the equation.

According to the forward reaction, when we apply the law of mass action, the
Reaction Rate

equation below is acquired.

(1)

But, according to the backward reaction, when we apply the law of mass action,
Forward kf reaction rate the equation below is acquired.
backward kb reaction rate (2)

Figure 2-2
The equilibrium state graphics kf and kb is the rate constants for the forward and backward reactions respective-
for a gas mixture: It shows forma- ly. When the equilibrium is reached, the rate of the forward reaction is equal to
tion, decomposition and the rate of the backward reaction rate.
reaching equilibrium. Rf = Rb. Figure 2-2. Thus we get:

46 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

(3)

If we arrange equation 3, we get the relationship below:

(4)

By the ratio of rate constants of forward and reverse reactions (kf and kb ), a
new equilibrium constant is obtained which is called as equilibrium constant
Keq. Therefore, Equation 4 becomes as follows.

(5)

Equilibrium is the ratio of rate constant of forward reaction (kf) to rate constant
of reverse reaction (kb). Therefore, The Equilibrium Constant is obtained by the
ratio of concentrations of products over reactants for a reaction that is at equi-
librium. This value remains constant as long as the temperature doesn’t change.

At equilibrium, when the concentrations of reactants and products are mea-

sured as molarity (M), equilibrium constant Keq is shown with Kc. Letter c is
taken from the word concentration. Equilibrium constant doesn’t have a certain
unit. As equation 5 shows the molar concentrations of reactants and products,
its equilibrium constant is expressed with Kc and written as follows:

(6)

Example 2-1 Exercise 2-1

Calculate the equilibrium constant for the following reaction.
In an equilibrium reaction, the
equilibrium constant Keq is 4.24.
As the rate constant of reverse re-
action kb is 0.02, calculate the rate
constant of forward reaction.
The rate constant of forward reaction kf is 0.11 and the rate constant of reverse
reaction kb is given as 0.05. Answer: 0.0848
Solution:

FEZALAR EDUCATIONAL INSTITUTIONS 47

 Chapter - 2

If all the reactants and products are in gaseous form, with respect to their molar
concentrations, their partial pressures are measured more easily. Therefore, it
is more suitable to tell the concentration of a gas using its partial pressure (P).
Thus, equilibrium constant Keq is shown as Kp (equilibrium constant in partial
pressure form). The amounts of the reacting gases are told as their partial pres-
sures, so in equation 5, the equilibrium constant of the gases is shown as below:

(7)

The definition of equilibrium constant in terms of partial pressures is the multi-

plication of partial pressures of products over multiplication of partial pressures
of reactants and the coefficients of all gaseous species in the reaction are used
as a power. This value does not change at constant temperature. It is constant.

There is a point here needs some consideration: In homogeneous reactions

where all reactants and products are in gaseous state, the equilibrium constant
is found through dividing multiplication of partial pressures of products only
in gas form to multiplication of partial pressures of reactants only in gas form.
(As shown in eq. 7)
In equilibrium reactions which contain substances in different physical states,
pure solid and liquid substances are not considered while writing equilibrium
constant. e.g as in sodium bicarbonate’s thermal decomposition reaction below:

Heterogeneous reactions also reach equilibrium just as homogenous reactions.

For example, if sodium bicarbonate is heated in a closed container, the reaction
reaches equilibrium at a certain time.

The equilibrium constant for this reaction is written as follows:

Figure 2-3
In spite of the changes in the
amounts of CaCO3 and CaO, the pres-
sure of CO2 at equilibrium remained
Constant at the same temperature. In equilibrium constant relationship, the concentrations of solid and liquid
substances are not written. Therefore, while writing equilibrium constant for
heterogeneous reactions, concentrations of pure solids and liquids are not con-
sidered. Thus, the equilibrium constant for thermal decomposition of sodium
bicarbonate is written as follows:

48 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

Or the equilibrium constant in partial pressures (Kp) is as below:

Another example is the equilibrium constant for thermal decomposition of cal-

cium carbonate when the reaction reaches equilibrium:

The equilibrium constant in terms of molar concentrations is written as follows:

In terms of partial pressures it is written as:

The pressure of CO2 at equilibrium is not affected from the change in the
amounts of CaCO3 and CaO and remained constant at the same temperature.
figure 2-3.

Example 2-2
For the reactions below, write down the equilibrium constants in terms of con-
centrations:

Solution :

FEZALAR EDUCATIONAL INSTITUTIONS 49

 Chapter - 2

Exercise 2-2 Example 2-3

For the reactions below, write For the reactions below, write down the equilibrium constants in terms of par-
down the equilibrium constants tial pressures:
in terms of partial pressures Kp
and molar concentrations Kc .

Solution:
2

2-6 CALCULATION OF EQUILIBRIUM CONSTANT Keq :

When the reaction reaches equilibrium, the value of the equilibrium constant
can be calculated through the measurement of the concentrations of all reac-
tants and products. These values are inserted in the formula to write the equilib-
rium constant at a constant temperature. Because at constant temperature, for
any reaction at equilibrium state, the value of Keq remains constant independent
of the amounts of the reactants and products.

Example 2-4
Assume that the equilibrium reaction at a given temperature is:

At certain temperature and at equilibrium, the concentrations are

given below. Calculate Keq for the reaction.

Solution:
As the molar concentrations at equilibrium are given, we can write
the equilibrium constant relationship in terms of Kc as below:

50 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

Besides that, some questions may be asked in which the initial partial pressures Exercise 2-3
of reactants or concentrations and the equilibrium constants are given. (Here, When the system reaches equilibri-
students should see the difference between the initial concentrations um, the concentrations of reactants
The table consists of three steps. The first step is the concentrations or partial are:
pressures of reactants before reaction (initial), the second step is the changes
occurring in the concentrations or partial pressures of substances during re-
action (change) and the final step is the concentrations or partial pressures of
substances after the reaction reaches equilibrium (equilibrium).
For the reaction below, calculate
See the example below. At the equation below, Keq at 100 0C
H2(g) + I2(g) ⇌ 2HI(g)
Example 2-5
In a 1-liter container at 430°C, 0.5 mole of H2 and 0.5 mole of I2 reacts. The
equilibrium constant is found as Kc= 5.29, when the equilibrium is reached. Answer: 6.92
Calculate the concentrations of substances in mixture at equilibrium.
H2(g) + I2(g) ⇌ 2HI(g)

Solution:
The initial concentrations of the reactants are calculated through the relation-
ship below using the volume of the mixture and mole number.

FEZALAR EDUCATIONAL INSTITUTIONS 51

 Chapter - 2

Exercise 2-4 Taking the square root of the equation, we get the x value.
For the reaction below, x = 0.267 mol/L
H2(g) + Br2(g) ⇌ 2HBr(g) Therefore, the concentrations at equilibrium are:

0.4 moles of H2 and Br2 gases each

are put in a 1 liter-container at
425 °C. As the Kc value is 0.25,
calculate the concentrations of
substances in equilibrium mixture. In some problems, the partial pressures or concentrations of the reactants and
after equilibrium, the concentration or partial pressure of one of the reactants’
Answer: or products’ are given. Then the equilibrium constant is asked to be calculated.
Example 2-6
In an experiment, 0.625 moles N2O4 gas was decomposed in a 5 liters-contain-
er at a given temperature. When the equilibrium is reached, remaining N2O4
concentration is observed as 0.025 mol/L. Calculate the Kc value of the reac-
tion. N2O4(g) ⇌ 2NO2(g)

Solution:
We convert the mole number in 5 liters to the mole number in 1 liter. In other
words, we calculate the initial molar concentration of N2O4 gas.

N2O4 concentration at equilibrium is equal to 0.025 mol/L. So,

The equilibrium constant relationship,

52 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

Example 2-7 Exercise 2-5

For the gas equilibrium reaction below,
For the reaction below:
2SO3(g) ⇌ 2SO2(g) + O2(g)
2CO2(g) ⇌ 2CO(g) + O2(g)
In a 1 liter- closed container at a given temperature, the pressure of SO3 gas be-
fore decomposition is 3 atm. After the reaction comes to equilibrium, the total In a 1 liter-container, the reaction
pressure of the gas mixture is found 4 atm. Calculate Kp value of the reaction began with 0.8 moles CO2 at a giv-
en temperature. When the reaction
at equilibrium.
reached equilibrium, the half of the
Solution: gas decomposed. Calculate the value
of Kc.
Answer: 0.2

Exercise 2-6
As the reaction’s equilibrium constant
is Kc =200, in the gas reaction below,

According to Dalton’s Law, total pressure is equal to the sum of partial pres-
sures of gases in the mixture. If we assume the total pressure is PT at equilibri- Different amounts of H2 and N2 were
um, pressure is: put in a 1 liter-container. When the re-
action reaches equilibrium, 0.3 moles
of H2 was used and 0.2 moles of N2 re-
mained. What are the mole numbers of
H2 and N2 before reaction?
Answer:
n = 0.3 mol
N2
n = 0.4 mol
H2

2-7-THE RELATIONSHIP BETWEEN KP AND KC

Warning! ∆ng shows the difference
EQUILIBRIUM CONSTANTS:
between mole numbers of reactants and
products only in gaseous form. There-
There is a relationship between equilibrium constants in terms of partial pres-
fore, g subscript is used.
sures Kp and in terms of molar concentrations Kc with respect to two equations
below:

FEZALAR EDUCATIONAL INSTITUTIONS 53

 Chapter - 2

Attention: In this kind of ∆ng symbol is defined with respect to the following relationship:
problems, we use the ∆ng = Ʃ ng(Products) - Ʃ ng(Reactants)
R = 0.082 L.atm/K.mol.
The relationship between Kc and Kp is as below:
1- If ∆ng is equal to 0, Kc = Kp
2- If ∆ng is a positive value, Kp > Kc
3- If ∆ng is a negative value, Kp < Kc
Exercise 2-7
Example 2-8
For the following reaction
In an equilibrium reaction at 227°C, if ∆ng= -1, Kc= 4.1, what is the value of
3H2(g) + N2(g) ⇌ 2NH3(g) Kp?
Kp=1.5×10-5 at 500 °C, calculate Kc Solution:
for the equilibrium reaction at the Firstly, we convert temperature from °C to K unit.
same temperature.

Answer: 0.06

Example 2-9
The following reaction reaches equilibrium at 300 K.

Exercise 2-8
The partial pressures of two gases are 0.3 atm when the equilibrium is set.
In the following reaction, Kc =1.6 at Calculate Kp and Kc.
1000 °C.
Solution:
C(s)+ CO2(g) ⇌ 2CO(g)
Kp = PNH3 × PH2S = (0.3) × (0.3) = 0.09
When the partial pressure of CO2
∆ng = Ʃ ng(Products) - Ʃ ng(Reactants) = 2 - 0 = 2
is 0.6 atm at equilibrium, calculate
the partial pressure of CO at equi- Kc = Kp (RT)-∆ng = 0.09 (0.082 × 300)-2 = 1.5 × 10-4
librium.

Answer: 10 atm 2-8 THE SIGNIFICANCE OF THE EQUILIBRIUM CONSTANT

Learning the value of the equilibrium constant is very important. If we know
the value of the equilibrium constant, we can estimate the following properties
of the reaction:
A- To determine the direction of the reaction
B- To determine the relationship between the equilibrium constant and the
method of writing equation.

2-8-1 Finding direction of Reactions by using Equilibrium

Constant
If we take the simple example below:

54 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

A ⇌ B
If Kc = 100, that means:

From the last mathematical relationship, we conclude that [B]’s concentration

is 100 times bigger than [A]’s concentration. Therefore, the equilibrium shifts
to the direction where substance [B] is produced, or to the direction of prod-
ucts. This is especially preferred in industrial production.
But, if Kc = 0.01 for the same reaction:

Here, at equilibrium, the concentration of substance [A] is 100 times bigger

than the concentration of substance [B]. So the equilibrium shifts to the direc-
tion of substance [A], or to the reactants. As a general rule:

1- If the value of the equilibrium constant is very big, the concentration of the
products are very big. Hence, the reaction functions forward.

K >> 1
Reactants Products
ˆ ˆˆ †ˆ
‡
2- If the value of the equilibrium constant is very small, the concentration
of the products are very small at equilibrium. Hence, the reaction functions
backward.

K << 1
Reactants ˆ ˆˆ †ˆ Products
‡

3- If the equilibrium constant is exactly 1 or a value close to 1, the concentra-

tions of the reactants and products are equal or very close to being equal.

If the value of K is much bigger than 1 (K>>1), at equilibrium, the concen-

tration of the products will be much bigger than that of reactants. Thus, the
equilibrium shifts towards the products.

If the value of K is much less than 1 (K<<1), the concentration of the reactants
will be much bigger than of products. Thus, the equilibrium shifts towards the
reactants.

FEZALAR EDUCATIONAL INSTITUTIONS 55

 Chapter - 2

Example 2-10
Using the equilibrium constants for the following reactions, estimate the equi-
librium state.

Exercise 2-9
Estimate the equilibrium states for the
Solution:
following reactions considering the 1- The equilibrium constant for the first reaction is too small. In other words,
equilibrium constants. the amounts of F2 and H2 at equilibrium are so little that practically this kind of
reaction does not occur.
2- The equilibrium constant for the second reaction is too big. That means the
reactants produce nearly 100% SO3 at equilibrium. The amount of O2 and SO2
that enters the reaction but does not interact is too little. Therefore practically
this reaction occurs completely.
3- The equilibrium constant for the third reaction is almost 1. Therefore, at
equilibrium, the concentrations of the reactants (H2 and N2 gases) and products
(NH3) are close to each other.

2-8-2-The Relationship between writing Equations and Kc

Whatever the direction of equilibrium, the relationship in any equilibrium con-
stant depends on the equation for the equilibrium reaction. Here, we will assign
3 rules for writing equations.
Rule: 1
When a reaction’s direction is reversed, the new equilibrium constant is the
reciprocal of the first equilibrium constant.
For example, in the equilibrium reaction below:

The equilibrium constant for this reaction is:

When we reverse this reaction

56 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

The equilibrium constant for this reaction is written as follows: Exercise 2-10
The equilibrium constant for the
following gaseous reaction is
Kp = 0.39 at 227 °C,
When we look at the two reactions above, the relationship between Kc1 and
Kc2values is as follows:

What is the value of Kc in the

following reaction at same con-
dition.
Rule : 2
When a reaction equation is multiplied with a coefficient (e.g a number), the Answer: 0.0625
new equilibrium constant is found as that coefficient is used as the exponent of
the first equilibrium constant. Let’s explain that rule with the following exam-
ple. Take the previous equilibrium reaction:

Exercise 2-11
The following reaction contains
0.02M NH3 and 0.1 M of each of
The equilibrium constant is: N2 and H2 gases at equilibrium
state.
If this reaction is multiplied with ½ , the equation becomes as follows: 3H2(g) + N2(g) ⇌ 2NH3(g)
What is the value of Kc of the
following reaction at the same
conditions?
3 1
NH3(g) ⇌ H2(g) + N2(g)
The equilibrium constant for the last equation is shown as: 2 2
Answer: 0.5

If we examine Kc1 and Kc2values, the new equilibrium constant Kc2 is equal to
the ½ exponent of the first equilibrium constant. Thus,

Rule: 3
If the reaction is a sum of a series of reactions, the total reaction’s equilibrium
constant is equal to the multiplication of all reactions’ equilibrium constants.
For example, take the 2 equilibrium reactions below:

FEZALAR EDUCATIONAL INSTITUTIONS 57

 Chapter - 2

Exercise 2-12 If we sum up 2 reactions, we get the following reaction:

1 mole of HBr gas was put in a 1 liter
closed container. When the gas reac-
tion reached equilibrium at a given
temperature, according to the equa-
tion below, 0.2 moles of Br2 gas was
Thus, the third reaction’s equilibrium constant Kc3 is equal to the multiplication
produced.
of equilibrium constants Kc1 and Kc2 : Kc3= Kc1 × Kc2
2HBr ⇌ H2 + Br2
In another 1 liter-container, calculate
Example 2-11
the mole number of HBr gas at equi- The equilibrium constant for the following reaction is 0.36 at 100 °C,
librium state from reaction of 2 moles
N2O4(g) ⇌ 2NO2(g)
of Br2 and 2 moles of H2 according to
the reaction below. At the same temperature, what are the equilibrium constants for the reactions
below?
H2 + Br2 ⇌ 2HBr
2NO2(g) ⇌N2O4(g)
Answer: 2.4 moles. 1
2 N2O4(g) ⇌ NO2(g)

Exercise 2-13
For the following reactions at Solution:
2000K, the equilibrium constants in The equilibrium constant for the first reaction:
terms of partial pressures are given.

As the following equation,

2NO2(g) ⇌N2O4(g) is the reverse of the first equation, Kc2 value is the recipro-
cal of Kc1.
Calculate the equilibrium constant
Kc for the reaction below:

Answer: 0.366 The following equation,

1
2 N2O4(g) ⇌ NO2(g) is as same as the first equation, but it is multiplied by
1
2 . Therefore, the equilibrium constant for this equation is ½ exponent of the
first equilibrium constant.

58 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

2-9-REACTION QUOTIENTS
If the concentrations of reactants and products are known at any time during a
reaction, reaction’s direction or equilibrium state for that time can be estimated.
For this, a reaction quotient is calculated which is shown with Qc. This is an
imaginary value for the equilibrium constant. It is used to determine if the reac-
tion, at any time, has reached equilibrium or not. The same relationship used to
define Kc is also used for Qc. The most important difference between the two is
the concentrations used in Qc do not necessarily have the values at equilibrium
state. By the help of the relationship between Kc and Qc, the equilibrium state
or reaction’s direction can be estimated as follows:
1- If Kc = Qc, the system is at equilibrium. The concentrations of the reactants
and products are at equilibrium, thus they will remain constant.
2- If Qc is bigger than Kc (Qc> Kc), the reaction is not at equilibrium. The
concentrations of the products are higher than their concentrations at equilib-
rium. Hence, they need to decrease in order to reach equilibrium. For this, the
reaction shifts from right (products) to left (reactants).
3- If Qc is smaller than Kc (Qc< Kc), reaction is not at equilibrium. The con-
centrations of the products are less than their concentrations at equilibrium.
Hence, they need to increase in order to reach equilibrium. For this, the reac-
tion shifts from left (reactants) to right (products).

Reactants ← Products Reactants → Products Equilibrium: No change in

concentrations of reactants
or products
Example 2-12
For the following gaseous reactions;
3H2 + N2 ⇌ 2NH3
At 500 °C, the equilibrium constant of the reaction is 0.06. Study the data be-
low and determine the direction of the reaction.

FEZALAR EDUCATIONAL INSTITUTIONS 59

 Chapter - 2

Exercise 2-14 Solution:

For the following reaction Kc= 9.0
In order to determine the direction of the reaction, for each step Q value is
found and compared with Kc.

1) In a 1 liter closed container, a

mixture of 2.0 moles of NH3, N2 and
H2 gases each is prepared.
Is the mixture at equilibrium? Ex- As Q is bigger than Kc, the reaction proceeds backward. In other words, the
plain the reason. reaction shifts to left (reactants) until the system reaches a new equilibrium.

2) If we assume the mixture is not

at equilibrium, what should be
the volume of the container for Q = Kc, so the reaction is at equilibrium and the concentrations are constant.
equilibrium?

Answer: 6 L.

Q< Kc, so the reaction is not at equilibrium. It should proceed forward. In other
Exercise 2-15 words, it shifts to right (products) until it reaches a new equilibrium.
In a 2 L container, a mixture of 1.4
moles of each of HBr, H2 and Br2 is
heated at a given temperature. 2-10 THE RELATIONSHIP BETWEEN ∆G, FREE
H2(g) + Br2(g) ⇌ 2HBr(g) ENERGY AND REACTION QUOTIENT:
If value of Kp= 0.25 to produce 1 In the following reaction,
mole of HBr from H2 and Br2 gas-
es, what are the number of moles of
products and reactants at equilibri-
um state? Non-standard free energy (∆G) is related to standard free energy ∆G° with
Answer: respect to the general relation below:
nH = nBr = 1.866 mol
2 2
nHBr= 0.468 mol

R is gas constant and R= 8.314 J/K.mole. T is temperature in Kelvin unit. We

can rearrange the equation 1 as below:

When the reaction reaches equilibrium, free energy value ∆G becomes equal
to 0.
∆G = 0
The value of Q becomes equal to Keq. Thus, the equation 2 can be re-written
as follows:

60 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

If gases interact in this reaction, as partial pressure terms are used, we use Kp. Attention:
If the reaction is in solution, as molar concentration terms are used, we use Kc.
ln symbol is the natural logarithm
This equation is one of the most important equations in thermodynamics. Be- under base e. In order to find Keq, it
cause it allows us to learn the change in standard free energy ∆G° as we know can be calculated by taking the recip-
equilibrium constant value Keq. Also the opposite of this is valid. This relation- rocal of ln with a calculator.
ship is shown in Table 2-1.

Table 2-1 Keq and ΔG° relationship according to ΔG° = -RTInKeq

Keq InKeq ΔG° Notes
>1 Positive Negative Reaction occurs spontaneously.
=1 0 0 Reaction at equilibrium
Reaction does not occur spontaneously.
<1 Negative Positive But products transform into reactants
spontaneously.

Example 2-13
At 25 °C and under 1 atm pressure, for the following reaction
∆G° = -104 kJ/mol
CCl4(l) + H2(g) ⇌ HCl(g) + CHCl3(l)
Under same conditions calculate Keq?

Solution:
Firstly, we convert temperature from °C to K unit.
T(K) = t (°C) + 273 = 25 + 273 = 298 K Exercise 2-16
As standard free energy for the for-
R = 8.314 J/K.mol
mation of water,
Here, attention is required to use both R and ∆G° in Joule unit. As ∆G° is kJ, it
∆Gf° (H2O) = -237 kJ/mol, for the
needs to be converted to J unit.
reaction below at 25 °C and under 1
1000 J atm pressure, calculate Kp.
ΔG° (J/mol) = ΔG° (kJ/mol) × ______
1 kJ

1000 J Does this reaction occur sponta-

ΔG° (J/mol) = -104 (kJ/mol) × ______ = -104000 J/mol neously?
1 kJ
Answer: 8×10-84
ΔG° = -RTInKeq Keq < 1, it does not occur sponta-
neously.
-104000 (J/mol) = -8.314 (J/K.mol) 298 (K) InKeq

FEZALAR EDUCATIONAL INSTITUTIONS 61

 Chapter - 2

As a result of calculation, Keq=1.7×1018. This value is too big. That means

the concentrations of the reactants are too small. In other words, the reaction
occurred nearly 100% to yield products.
2-11 LE CHATELIER’S PRINCIPLE
The change in equilibrium position is defined as the shift of equilibrium towards
reactants or products in an equilibrium reaction. French scientist Le Chatelier’s
examined the external factors on equilibrium position and defined the follow-
ing rule: “If a chemical system at equilibrium is disturbed by a change in con-
centration, temperature, volume or partial pressure, then the equilibrium shifts
to minimize the imposed change and a new equilibrium is established.” This
principle is similar to Newton’s Principle in mechanical systems. “Every action
has got a reaction in same magnitude but opposite in direction.”
External factors disturbing equilibrium position are given below:

2-11-1- The Effect of Changing Concentration

In the following reaction known as The Haber process for ammonia production,

N2(g) + 3H2(g) ⇌ 2NH3(g)

We can estimate the change occur at equilibrium using Le Chatelier’s Princi-
ple. If some addition or extraction is made from one of the reactants or prod-
ucts, equilibrium will be disturbed and as a result the equilibrium will shift.
For example, if more hydrogen is added to the equilibrium mixture, equilib-
rium position will try to reduce the added hydrogen and it will shift to the
direction of producing ammonia. In other words, the forward reaction’s rate
will increase. As a result, more ammonia will be produced. This will continue
until a new equilibrium is reached. More nitrogen gas addition makes a similar
effect. However, if more ammonia is added to equilibrium mixture, direction
of the reaction will shift to the way to reduce the added amount that will cause
ammonia to decompose to N2 and H2.
To summarize, the equilibrium shifts from right to left (from products to re-
actants) until a new equilibrium is set. Decrease in one of the substances will
cause the equilibrium shift to the direction to compensate the loss. According
to this, if some ammonia is withdrawn from equilibrium mixture, the reaction
will shift from left to right (from reactants to products). But if N2 or H2 or both
is withdrawn, the reaction will shift from right to left (from products to reac-
tants.)
Increasing or decreasing concentrations in equilibrium reactions are methods
applied at industry or laboratories. For this, either the substance in question
is reduced or the concentration of reactants is increased some. In the Haber
process mentioned above, produced ammonia is constantly withdrawn from
mixture in order to promote ammonia production. This process depends on Le
Chatelier’s Principle. To sum up what is told above for the equilibrium reac-
tions:
1- Upon addition to products, the reaction shifts to left (to reactants).
2- Upon addition to reactants, the reaction shifts to right (to products).
3- Decrease in products causes the reaction shift to right (to products).
4- Decrease in reactants causes the reaction shift to left (to reactants).

62 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

addition of
N2O4
System shifts to right System shifts to left.

2-11-2-The Effects of Pressure or Reaction Container’s on

Equilibrium
In a closed system at constant temperature, for an equilibrium reaction, any
change in pressure or in the volume of the reaction container will cause a shift
to the direction which compensates the changes. This can be explained as:
1- If a decrease in volume occurs in the equilibrium system; in the following
gas reaction:

2SO2(g) + O2(g) ⇌ 2SO3(g)

We observe that ∆ng value is equal to (-1). In other words, the total volume of
the reaction has decreased. (The volume of the products is less than the volume
of the reactants.) If the pressure of the equilibrium system increases (or if the
volume of the container decreases), the equilibrium will shift to the products
As a result of the increase in the vol-
which are less in volume. It will shift to the direction in which SO3 is produced. ume of the container (the decrease in
In case of decrease in pressure or increase in the volume of the container, the pressure), the reaction will shift to left.
equilibrium will shift to the reactants which are bigger in volume. That means
SO3 will decompose to produce O2 and SO2. In other words, system will shift to
the direction with bigger mole numbers.
2- If the volume of the equilibrium reaction increases, in the following reaction:

2NO2(g) ⇌ 2NO(g) + O2(g)

The value of ∆ng is equal to (1). The total volume of the reaction has Increased.
(This happens when the volume of the products are bigger than the volume of
the reactants.) In such an equilibrium reaction, the pressure increases as the
volume decreases. In this situation system shifts to the direction where less
volume results. Thus, the equilibrium shifts to NO2 direction with less mole
number. If the pressure applied to the system decreases, the reaction will shift
to the direction in which substances with bigger volume is produced. In short,
the reaction will proceed towards the direction in which NO2 decomposes to
NO and O2.

FEZALAR EDUCATIONAL INSTITUTIONS 63

 Chapter - 2

3- If there is no volume change in the system, for the following reaction:

C(s) + O2(g) ⇌ CO2(g)
The value of ∆ng is equal to 0. Therefore, it means there is no volume change
in the reaction. In this situation, either pressure change or change in the volume
of the container does not affect the amounts of substances in the mixture and
equilibrium position remains constant. To sum up what is told above:

Changing Shift in equilibrium

Increase in pressure towards gaseous substances with less mole no.
Decrease in pressure towards gaseous substances with bigger mole no.
Increase in volume towards gaseous substances with bigger mole no.
As a result of the decrease in the Decrease in volume towards gaseous substances with less mole no.
volume of the container (the in-
crease in pressure), the reaction
will shift to right 2-11-3-The Effect of Temperature
According to laws of thermodynamics, chemical reactions are divided into two
with respect to their heat absorbing and heat releasing properties:

1- The reactions in which the energies of reactants are higher than the energies
of products are heat absorbing reactions (endothermic reactions). Their enthal-
py change value is positive (∆H = +)

2- The reactions in which the energies of reactants are less than the energies
of products are heat releasing reactions (exothermic reactions) The value of
enthalpy change is negative (∆H = -)

The temperature change in a reaction at equilibrium can be estimated as

follows:

A- Heat Absorbing Reactions (Endothermic Reactions):

In the following reaction;
CaCO3(s) + Energy ⇌ CaO(s) + CO2(g)
If the energy is written next to the reactants, it means this is an endothermic
reaction (∆H > 0). When the temperature in this kind of reactions is raised, the
equilibrium shifts to right. Because, here, the calcium carbonate uses some of
this heat to yield products. When it is cooled, the reaction will shift to left (to
reactants) to produce CaCO3. The released heat is equal to the heat at the time
of temperature raise.
In the endothermic reaction below,

N2O4(g) ⇌ 2NO2(g)
colorless brown
Figure 2-7
The increase in temperature causes the reac- B- Heat Releasing Reactions (Exothermic Reactions)
tion shift to direction where brown NO2 gas
is produced. (Figure 2-7 A) In the following reaction,
But cooling the reaction causes the reaction 2CO(g) + O2(g) ⇌ 2CO2(g) + Energy
shift to direction where colorless N2O4 gas is
produced. (Figure 2-7 B)

64 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

If the energy is written next to products, it means that the reaction is an exo-
thermic reaction (∆H < 0).
In this kind of reactions, an increase in temperature causes the equilibrium shift
to left (reactants). As a result, CO2 will decompose as it uses the given heat.
When the reaction is cooled, an equal amount of heat to the heat at the time of
the temperature raise will be released. The equilibrium shifts to right (products)
to produce CO2.
The effect of temperature on equilibrium constant Keq can be summarized as
below:

Change Exothermic Reaction Endothermic Reaction

Increase in The equilibrium shifts to reactants. The equilibrium shifts to products.
Temperature The value of Keq decreases. The value of Keq increases.
Decrease in The equilibrium shifts to products. The equilibrium shifts to reactants.
Temperature The value of Keq increases. The value of Keq decreases.

2-11-4-Addition of Catalyst
Addition of catalyst to reversible reactions causes only change in the rate of the
reaction. When we add catalyst to an equilibrium reaction, this process does
not affect the concentrations of the substances in the system, but it only chang- Do you know this?
es the activation energy. And this only affects the reaction rate. It increases the
A catalyst is a substance that speeds
average of forward (Rf) and backward (Rb) reactions’ rates at the same level.
up a chemical reaction without itself
As a result, the equilibrium is reached at a higher rate. Therefore, addition of being affected.
catalyst does not affect the equilibrium position. The catalyst only accelerates
reaching this position.
2-12-FACTORS AFFECTING THE EQUILIBRIUM CONSTANT
Changes in the concentrations, pressure or volume of reactants and products at
constant temperature affects the equilibrium position. But the ratio of reactants
and products remain constant. Therefore, these changes do not affect the equi-
librium constant. The value of the chemical equilibrium constant changes only
with temperature change.

Example 2-14
For the following equilibrium reaction; Exercise 2-17
For the following equilibrium reac-
tion;

2BrF5(g) ⇌ Br2(g) + 5F2(g)

At 298 K, the value of ∆H is equal to -181 kJ. Kp is given as 3.2×1020. When
the temperature is raised to 500 K, is the value of Kp bigger or smaller than its At 1000 K, the value of ∆H is equal
value at 298 K for the same reaction? to 858 kJ. Kp is given as 7.4×10-16..
Solution: When the temperature is raised to
1500 K, is the value of Kp bigger or
The reaction is an exothermic reaction. When the temperature is raised, the smaller than its value at 1000 K for
reaction shifts to left in order to compensate excessive heat. Therefore, the
the same reaction?
concentrations of the products decrease at equilibrium. The concentrations of
the reactants increase. As a result, at 500 K the value of Kp decreases.

FEZALAR EDUCATIONAL INSTITUTIONS 65

 Chapter - 2

Exercise 2-18 Example 2-15

For the equilibrium reaction below, For the given equilibrium reaction below, what are the effects of following
factors on the equilibrium position and equilibrium constant?
3O2(g) ⇌ 2O3(g) ∆H = 428 kJ/mol
N2F4(g) ⇌ 2NF2(g) ∆H = 38.5 kJ/mol
What are the effects of the follow-
ing factors on the equilibrium posi- 1- Heating the equilibrium mixture in a closed container
tion and the equilibrium constant? 2- Removing some N2F4 from the equilibrium mixture at constant temperature
and volume
1- By decreasing the volume of the
reaction container, increasing the 3- Decreasing pressure on the equilibrium mixture at constant temperature
pressure on the reaction. 4- Adding catalyst to the equilibrium mixture
2- Increasing pressure by adding Solution:
more O2 to the system.
1- The value of ∆H shows that the reaction is an endothermic reaction. There-
3- Decreasing temperature. fore, when the reaction is heated, the equilibrium will shift to right (to prod-
4- Adding a catalyst. ucts) in order to lessen the excessive heat. The equilibrium constant will in-
crease. The reason is that while the concentration of NF2 is increasing, the
concentration of N2F4 is decreasing. Because the Keq is directly proportion-
al to the amount of products as it is inversely proportional to the amount of
reactants. If the reaction proceeds to the direction of products, some of the
reactants will transform to products. In other words, as the concentration of
the reactants decreases, the concentration of the products increases. Thus, the
Exercise 2-19 equilibrium constant will increase. But here attention is required that, as long
As seen in the following reaction, as the temperature is constant, the equilibrium constant does not change and
remains constant. But with temperature change it also changes. If the reaction
C2H4(g) + H2(g) ⇌ C2H6(g)
shifts to right, the equilibrium constant will increase. If the reaction shifts to
+ 137 kJ/mol left, it will decrease.
The mixture of C2H4, H2 , C2H6 2- When some N2F4 is removed; its concentration in the equilibrium mixture
gases reached equilibrium at will decrease. Therefore, the system will try to compensate the loss of N2F4. For
25°C. Explain how you can in- this, the reaction will shift to left. In other words, some of NF2 will transform
crease the amount of C2H6. into N2F4. Here the equilibrium constant is not affected from this change.

3- After decreasing the pressure on the equilibrium mixture, the system will
shift to the direction with higher mole number. In the reaction equation, we see
that the value of ∆ng is 1. Therefore, the reaction will shift to right. Here the
equilibrium constant will not be affected from pressure change or any change
in the volume of the container.

4- Addition of a catalyst only decreases the activation energy. In other words,

catalysts increase the reaction rate. Therefore, a catalyst affects neither the
equilibrium position nor the value of the equilibrium constant.

66 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

BASIC EQUATIONS
Equilibrium constant in terms of concentration:

[G]g [H]h
_________
Kc =
[A]a [B]b

Equilibrium constant in terms of partial pressure:

P Gg xP Hh
KP = a b
P A xP B
The relationship between Kp and Kc
Kp = Kc(RT)Δng
The change in mole numbers of gaseous substances in the reaction
Δng = Ʃng(products) - Ʃng(reactants)
Free energy and the relationship between standard free energy and non-standard free energy:

[G]g [H]h
__________
ΔG = ΔG° + RT ln
[A]a [B]b

The relationship between standard free energy and equilibrium constant:

ΔG° = -RTInKeq

FEZALAR EDUCATIONAL INSTITUTIONS 67

 Chapter - 2

BASIC CONCEPTS
Chemical Equilibrium: It is a dynamic state but not a static one. It is a situation which most reversible re-
actions with reaction rates equal at both directions. Here, the concentrations of reactants and products remain
constant as long as reaction conditions do not change. Therefore, a reaction at equilibrium seems to be as
stopped.
Irreversible Reactions: Under certain conditions, these are the chemical reactions in which one or all of the
reactants are used up completely. Under same conditions, the products do not have the capability to interact in
order to re-form the reactants.
Reversible Reactions: These are the reactions in which reactants transform into products. The products have
the capability to re-form the reactants.
Reversible Homogeneous Reactions : These are the reactions in which all reactants and products are in the
same physical state.
Reversible Heterogeneous Reactions: These are the reactions in which reactants and products are in different
physical states.
Writing the Equilibrium Constant : The equilibrium constant expression is the ratio of the concentrations
of a reaction at equilibrium. At constant temperature in an equilibrium reaction, the mole numbers of the prod-
ucts are written as exponents and multiplied. The mole numbers of the reactants are also written as exponents
and multiplied. The equilibrium constant is found by the ratio of those.
Reaction Quotient : It is an imaginary value for the equilibrium constant. It is the equilibrium constant at any
moment to estimate whether the reaction has reached equilibrium or not. It is calculated the same way as the
equilibrium constant. But the concentrations do not have to be the ones at equilibrium. Concentrations at any
moment can be used.
Le Chatelier’s Principle : When an external factor such as concentration, volume, pressure or temperature
change affects a reaction, the system counteracts this change. That means if the change is an increase, the
system shifts to the direction in which it is decreased or if the change is a decrease, it shifts to the direction in
which it is increased until the equilibrium is reached.

68 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

QUESTIONS OF CHAPTER-2
2-1- Fill in the blanks.

1- In the following equilibrium reaction:

N2(g) + 3H2(g) ⇌ 2NH3(g) + 92 kJ
Decrease in temperature causes increase in the concentrations of ………..………...

2- For a reaction at equilibrium, the equilibrium constant Kc is 2×10-15 at 500 °C. If its value at 200 °C is
4×10-12, this is an …………….……….. reaction.

3- In the following equilibrium reaction,

CO(g) + 2H2(g) ⇌ CH3OH(g) + 127 kJ
If hydrogen gas is added to this equilibrium reaction, the reaction ……………..……..

4- In an exothermic equilibrium reaction, if the temperature is ………………………, the equilibrium posi-

tion shifts to products.

5- In the following equilibrium reaction;

CO2(g) + C(s) ⇌ 2CO(g)
………….... in pressure increases consumption of CO2 gas.

6- In the following equilibrium reaction

N2(g) + O2(g) + 180 kJ ⇌ 2NO(g)
increase in the temperature of reaction container …………………………… the Kc value of the reaction.

7- A change in the ……………………….… doesn’t affect the equilibrium position of the following reaction.
N2(g) + O2(g) + 180 kJ ⇌ 2NO(g)

8- In the following equilibrium reaction

Cl2(g) + H2(g) ⇌ 2HCl(g) +Energy
the concentration of HCl can be increased by …………..………….…. the reaction temperature.

9- In the following equilibrium reaction;

N2O4(g) ⇌ 2NO2(g)
the partial pressure of NO2 gas is given as 3 atm at a given temperature. If the Kp value of the reaction is 3, the
partial pressure of N2O4 gas is equal to …………..

10- In the following equilibrium reaction;

4NH3(g) + 3O2(g) ⇌ 2N2(g) + 6H2O(1)
The equilibrium constant of the reaction is Kc=1×1028 at a certain temperature. This relationship shows that
the equilibrium position is in ………………….…..…. direction.

FEZALAR EDUCATIONAL INSTITUTIONS 69

 Chapter - 2

11- If Kp is smaller than Kc, the sum of number of moles of reactants is …………………… than the sum of
number of moles of products.

12- For a reaction at equilibrium, if the equilibrium constant at a certain moment (false equilibrium) is
smaller than the equilibrium constant Kc, the reaction shifts to …………………..

13- If the total pressure is increased on a reaction in which the mole numbers of reactant gases are smaller
than the mole numbers of product gases, the equilibrium position shifts to ………………………….

14- The relationship between equilibrium constant Kc and the concentrations of products is ……….

15- In an equilibrium mixture, where ∆ng = -1, if the pressure of mixture is decreased, the reaction shifts to
………….….. The equilibrium constant Kc ……………

16- In a reaction with Kc= 4, if products are withdrawn from the equilibrium mixture, the equilibrium con-
stant ……….……..

17- When ∆ng = …………………….., the pressure doesn’t affect the gas reaction at equilibrium.

18- In an endothermic reaction, if the reaction container is cooled, ………..………………. are produced
more.

19- In an endothermic reaction at dynamic equilibrium, the concentrations of products increase at ……….
temperatures.

Kp
20- In an equilibrium reaction, it is observed that Kc = According to this, the sum of mole numbers of
RT
gas products are ..................... than sum of mole numbers of gas reactants.

2-2- Circle the correct answer.

1- The equilibrium constant of equilibrium reaction 2SO2(g) + O2(g) ⇌ 2SO3(g) at 727 °C is 4.17×10-2. After
0.4 M SO3 , 0.1 M O2 , 0.02M SO2 are mixed, the direction of the reaction is:

A- towards reactants. B- towards products.

C- at a dynamic equilibrium. D- all answers are wrong.

2- For the equilibrium reaction occurring in a closed container,

CaCO3(s) ⇌ CO2(g)+CaO(s)
when does the amount of CaCO3 increase by applying one of the following?

A- by eliminating some CO2 gas at equilibrium

B- by increasing total pressure
C- by adding some CaO to the equilibrium mixture
D- all above is incorrect.

70 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

3- For the equilibrium reaction I2(g) + F2(g) ⇌ 2IF(g) the equilibrium constant Kc= 1 × 106 at 200 K. If the partial
pressures of IF gas is 0.2 atm and F2 gas is 4×10-3 atm at equilibrium, what is the partial pressure of I2 gas?

A- 5×104 atm B- 1×10-5 atm C- 1×105 atm D- All options are incorrect.

1
4- As the equilibrium constant Kc is 640.3 at 300 K for the reaction Li(g) + I2(g) ⇌ LiI(g). What is the
2
equilibrium constant Kc for the reaction 2LiI(g) ⇌ 2Li(g) + I2(g) at the same temperature?

A- 25.3 B- 41 × 104 C- 15.6 × 105 D- All are incorrect.

5- When K2CrO4 and HCl solutions are mixed, they reach equilibrium according to the following ionic equa-
tion.
2CrO42-(aq) + 2H+(aq) ⇌ Cr2O72-(aq) + H2O(1)
yellow orange
If we want orange color to be dominant in the container, which of the following should we do?

A- we add more water.

B- we add more HCl.
C- we add more K2Cr2O7.
D- all are incorrect.

6- When NaOH solution is added to the mixture in the previous question, which of the following is expected
to happen?

A- increase in Cr2O72- concentration

B- increase in H2O concentration
C- decrease in Cr2O72- concentration
D- all are incorrect

7- N2(g) + 3H2(g) ⇌ 2NH3(g) + 92 kJ Kp value of the equilibrium reaction is given as 5.5×10-5 at 25 °C. What is
the Kc value of the reaction?

A- 22513.3 B- 9×10-4 C- 0.03 D- all are incorrect

8- For the equilibrium reaction Br2(g) ⇌ 2Br(g), Kp value is 2558.4 , kf value is 1.56 at 4000 K. Which of the
following is value of kb?

A-0.2 B-20 C-7.8 D-All are incorrect.

FEZALAR EDUCATIONAL INSTITUTIONS 71

 Chapter - 2

9- For the equilibrium reaction; H2(g) + I2(g) ⇌ 2HI(g) , the equilibrium constant Kp is 2. What should be the
concentrations (mol/L) of reactants and products for the equilibrium shift towards products?

A- [HI]= 0.1 mol/L , [I2]= 0.05 mol/L; [H2]= 0.05 mol/L

B- [HI]= 0.4 mol/L , [I2]= 0.1 mol/L; [H2]= 0.2 mol/L
C- [HI]= 0.001 mol/L , [I2]= 0.0002 mol/L; [H2]= 0.0025 mol/L
D- All are incorrect.

2-3- Write down reasons for the following.

1- In equilibrium reactions of gases, Δng (Products) < Δng (Reactants), increasing the volume of container
causes decrease in products.

2- In the imaginary equilibrium reaction, A(g) ⇌ B(g) + Energy, increase in total pressure doesn’t change the
temperature of the reaction container.

3- The value of equilibrium constants of irreversible reactions are big.

4- When Kc is 0.3 and Q = 1, the temperature of the endothermic reaction increases.

5- When the temperature of reaction increases while value of Kc decreases, the reaction is accepted as an
exothermic one.

6- In endothermic reactions, the value of Kc increases with temperature.

7- As a result of pressure increase on the equilibrium mixture in which ∆ng = +1, the equilibrium shifts to
reactants.

8- As some reactions really stop, some reactions seem to be stopped.

9- In the equilibrium reaction, SO2Cl2(g) + Energy ⇌ SO2(g) + Cl2(g), if SO2 is added to the equilibrium mixture,
the temperature of the reaction increases.

2-4- Define the following terms.

1- Law of Mass Action 2- Chemical Equilibrium State 3- Le Chatelier’s Principle

2-5- In the gas equilibrium reaction, 2NO2(g) ⇌ N2O4(g), is exothermic.

After the following changes are applied on the equilibrium reaction, how does the equilibrium position
change? Why?

1- Increase in the pressure

2- Increase in the temperate of the container
3- Withdrawal of some N2O4 from the equilibrium reaction.

72 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

2-6- In the gas equilibrium reaction, PCl5(g) ⇌ PCl3(g) + Cl2(g), the value of enthalpy is equal to 92.5 kJ/mol.
What are the effects of the following factors on equilibrium position and the equilibrium constant?

1- Increase in temperature
2- Addition of more Cl2 to the equilibrium mixture
3- Withdrawal of PCl3 from the equilibrium mixture
4- Increase in the pressure on the equilibrium mixture
5- Addition of catalyst

2-7- The enthalpy of the reaction, 2SO2(g) + O2(g) ⇌ 2SO3(g) is equal to -198.2 kJ. After applying the follow-
ing processes, what will be the concentrations of SO2 , O2 and SO3.

1- Increase in the reaction temperature

2- Decrease in the pressure on the reaction
3- Increase in the concentration of SO2 in the equilibrium mixture.
4- Addition of a catalyst.

2-8- Does the increase in temperature of a reaction at equilibrium always cause an increase in concentrations
of products? If your answer is no, what are the factors which cause an increase in concentrations of products?
Explain with examples.

2-9- The following gas equilibrium reaction is exothermic.

2PbS(s) + 3O2(g) ⇌ 2PbO(s) + 2SO2(g)
Clarify the effect of the following factors on the equilibrium state and the value of equilibrium constant.

1- Decrease in the applied pressure on the container

2- Cooling the container of the reaction.

2-10- An endothermic reaction in a closed container is given. CaCO3(s) ⇌ CO2(g) + CaO(s)

After the following changes are applied, what is the position of equilibrium reaction?

1- Decrease in the volume of the container

2- Addition of more CaO to the equilibrium mixture
3- Withdrawal of some CaCO3 from the equilibrium mixture
4- Addition of more CO2 to the equilibrium mixture
5- Increase in temperature

2-11- If pure NOCl gas is heated to 240 °C in a closed container; it decomposes according to the following
equation. 2NOCl(g) ⇌ 2NO(g) + Cl2(g)
When the reaction reaches equilibrium, the total pressure of equilibrium mixture is measured as 1 atm and
partial pressure of NOCl gas is measured as 0.64 atm. Thus, calculate the following:
1- Partial pressures of Cl2 and NO gases at equilibrium
2- The equilibrium constant Kc at the same temperature

Answer:
1) 0.12 atm, 0.24 atm
2) 4×10-4

FEZALAR EDUCATIONAL INSTITUTIONS 73

 Chapter - 2

2-12- For the reaction, N2O4(g) ⇌ 2NO2(g), which occurs without any catalyst, partial pressures were measured
as PN O = 0.377 atm and PNO = 1.56 atm at 100 °C at equilibrium. Calculate the following:
2 4 2

1- Kc and Kp of the reaction.

2- How do the partial pressures of gases in the equilibrium mixture change upon addition of catalyst?

Answer: 6.46; 0.21

2-13- For the equilibrium reaction; A(g) ⇌ 2B(g)

Calculate Kc and Kp values at different temperatures using the following table. Then tell if the reaction is an
endothermic or an exothermic one.
ₒC/ Temperature B/(mole/L) A/(mole/L)
1) 200 0.843 0.0125
2) 300 0.764 0.171
3) 400 0.724 0.250

2-14- The gaseous reaction, N2(g) + 3H2(g) ⇌ 2NH3(g), reaches equilibrium at 377 °C. The equilibrium constant
is given as Kc =1.96. Calculate the equilibrium constants for the following reactions at the same temperature.

A) 2NH3(g) ⇌ N2(g) + 3H2(g)

1 3
B) N2(g) + H2(g) ⇌ NH3(g)
2 2
1 3
C) NH3(g) ⇌ N2(g) + H2(g)
2 2
Answer: A) 0.51 B) 1.4 C) 0.7

2-15- The equilibrium constant of the following reactions is given.

CO2(g) + H2O(1) ⇌ H+ + HCO3- Kc = 4.2×10-7
CaCO3(s) ⇌ CO32- + Ca2+
Kc = 4.7×10-9

HCO3- ⇌ H+ + CO32-
Kc = 4.8×10-11
According to those above, what is Kc for the following equilibrium reaction?
CO2 + CaCO3(s) + H2O ⇌ Ca2+ + 2HCO3-

Answer: 4.1×10-5

2-16- In the following imaginary gaseous reaction;

2A+B ⇌ 3C
In a 1 liter container 3 moles of B was put with different mole numbers of A and C. When reaction reached
equilibrium state it was found that the container contains 6 moles of each of C and A. If Kc of the reaction is
1.5, what is the mole number of each of A and C before the reaction started?

Answer: A = 4 mol, C = 9 mol

74 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

2-17- The equilibrium constant of the following reaction is given as Kc =19.9 at 2500 K temperature.
Cl2(g) + F2(g) ⇌ 2ClF(g)
If the concentrations of the substances in the mixture are [ClF]= 1.2 M , [F2]= 1 M , [Cl2]= 0.2 M,
how will be the equilibrium position?

2-18- For the equilibrium reaction, A2(g) ⇌ 2A(g), the reaction started with 1 mole of A2 in a 1 liter container
at standard temperature and pressure (STP). At equilibrium, 1% of A2 decomposed. What is the value of Kc
in the reaction? Under the same conditions for the reaction above, what is the concentration of A with 0.01
M A2 at equilibrium?

Answer: 4×10-4 ; 0.002 M

2-19- For the equilibrium reaction, 3A(g) ⇌ aB(g), the equilibrium constant Kc is given as 147.6. Kp value is
equal to 6 at 27 °C. Find out the value of “a” in the equation.

Answer: 2

2-20- The following reaction;

NiO(s) + CO(g) ⇌ Ni(s) + CO2(g)
is at equilibrium at 727°C. At this temperature the pressure of CO gas is equal to 304 Torr. What is Kc when
total pressure is 1 atm?
(Note: 1 atm = 760 Torr)

Answer: 1.5

2-21- In the equilibrium reaction in a closed container, PCl3(g)+ Cl2(g) ⇌ PCl5(g)

the partial pressure of PCl3 is twice the partial pressure of Cl2. After the reaction reached equilibrium at a
certain temperature, the partial pressure of Cl2 was measured as 1 atm. As Kp=1/6, what are the partial pres-
sures of PCl3 and Cl2 gases before the reaction started?

Answer: 2.8 atm; 1.4 atm

2-22- In the exothermic reaction, 2HI(g) ⇌ H2(g) + I2(g), equal number of moles of H2 and I2 gases and HI gas
with twice those mole numbers were placed in a 1 liter container. The temperature of the container decreased
until equilibrium was reached. At equilibrium, there were 1 mole of HI, 2 moles of I2 and 2 moles of H2 in
the container. According to those, calculate the following:

1- The concentrations of components in the mixture before the reaction started.

2- The equilibrium constant Kc.

Answer: 1- [H2] =[I2] = 1.25 mol/L ; [HI]= 2.5 mol/L ,

2- 4

FEZALAR EDUCATIONAL INSTITUTIONS 75

 Chapter - 2

2-23- Give four procedures that lead to increase amount of products in the following gas equilibrium reac-
tion which is exothermic.
N2(g) + 3H2(g) ⇌ 2NH3(g)

2-24- According to the following reaction,

CO2(g) + H2(g) ⇌ CO(g) + H2O(g)
equal number of moles of CO2 and H2 were mixed in a 1-litre container. When the reaction reached equilib-
rium at 2000 K, there were 3 moles of gas in the mixture. As the equilibrium constant Kc is 4, what are the
concentrations of substances in the equilibrium mixture?

Answer: [CO]=[H2O] = 1 mol/L ; [CO2] =[H2] = 0.5 mol/L

2-25- For the heterogeneous equilibrium reaction; CaO(s) + CO2(g) ⇌ CaCO3(s) the partial pressure of CO2 is
0.235 atm at 800 °C. Calculate Kc at the same temperature.

Answer: 374.8

2-26- 4 g of HF gas was placed in a 2 liter closed container at 27 °C and left to decompose until equilibri-
um was reached according to the following equation.
2HF(g) ⇌ H2(g) + F2(g)
As Kp is 1.21, calculate the partial pressure of HF gas at equilibrium. (MHF =20 g/mol)

Answer: 0.76 atm

2-27- 20% of 1 mole of N2O4 gas decomposed to NO2 gas in a 1-litre container at 1 atm pressure at
27 °C. Calculate Kp value of the reaction. N2O4(g) ⇌ 2NO2(g)

Answer: 4.92
kf
2-28- In a 1 liter container, the following reaction occurs H2(g) + I2(g) ⇌ 2HI(g).
kb
The rate constant of forward reaction kf is 0.6256 and the rate constant of backward (reverse) reaction kb is
0.0136 at 490 °C. At 872K, the equilibrium constant of the reaction is 59. Tell how the number of moles of
HI changes at equilibrium after the following applications.

A- Addition of more H2
B- Decrease in temperature
C- Withdrawal of some I2

76 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Equilibrium

2-29- For the following reactions at 1000 K, the equilibrium constants Kp depending on pressure were
given.
1
C(s) + O ⇌ CO(g) Kp = 2.9×1010
2 2(g)
C(s) + O2(g) ⇌ CO2(g) Kp = 5×1020
Calculate the equilibrium constant Kc of the following reaction.
2CO(g) + O2(g) ⇌ 2CO2(g)

Answer: 2.4×1022

2-30- As a result of reaction of CO gas with water vapor in a 1-litre closed container at 700K, CO2 and
H2 gases were formed. What is the concentration of gas mixture at equilibrium as equilibrium constant
Kc is 5.29 and 1 mole of each of reactants and products were placed in the container?

Answer: [CO] =[H2O] = 0.606 mol/L ; [CO2] =[H2] = 1.394 mol/L

2-31- The equilibrium constant of the following reaction;

N2O4(g) ⇌ 2NO2(g)
is Kc = 6×10-3 at 298 K but it is 1.5×10-2 at 35 °C. Is the decomposition reaction of dinitrogen tetroxide
endothermic or exothermic?

2-32- For the equilibrium reaction,

2SO3(g) ⇌ 2SO2(g) + O2(g)
it was observed that the equilibrium mixture at 25 °C contained [O2]= 0.01 mol/L, [SO2]= 0.08 mol/L,
[SO3]= 0.002 mol/L. When the temperature was decreased to 10 °C, the equilibrium constant Kc was
found as 4. Tell if the reaction is endothermic or exothermic.

2-33- Explain the difference between ∆G and ∆G0, write down the relationship between them. When
does the value of ∆G become equal to ∆G0 ? Explain.

2-34- As ionization constant of water is 1×10-14 at 25 °C and 1 atm, calculate the ∆G0 value of the ioniza-
tion reaction.
H2O(l) ⇌ H+(aq) + OH-(aq)

Answer: 79881 J/mol

FEZALAR EDUCATIONAL INSTITUTIONS 77

 Chapter - 2

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78 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

IONIC EQUILIBRIUM CHAPTER-3

ACHIEVEMENTS

After studying this chapter, the student can understand the following:
*He/she can identify electrolytes and non-electrolytes.
*He/she can differ strong electrolytes and weak electrolytes.
*He/she can calculate Kc for weak electrolytes and the relationship obtained by partial ionization of these electro-
lytes.
*He/she can understand ionization of water and the amphoteric behavior of water.
*He/she can calculate acidity value of solutions.
*He she can understand solubility and hydrolysis and notice how they change with respect to the type of salt.
*He/she can understand common ion effect and how this effect is used to prepare buffer solutions.
*He/she can differ completely soluble and slightly soluble salts and he/she learns the factors affecting solubility of
slightly soluble salts.

FEZALAR EDUCATIONAL INSTITUTIONS 79

 Chapter - 3

3-1- INTRODUCTION
Chemical reactions mostly occur in solutions. Therefore solutions are very im-
portant in chemistry. In order to prepare solutions, water and organic solvents are
used abundantly. But in this chapter, we will focus on water-soluble substances
(aqueous solutions). The behavior of a substance solved in water depends on
the structure of the substance and the medium it is inside. Therefore, we need to
understand the principles controlling the behaviors of substances.

Substances like sodium chloride and potassium chromate which behave as elec-
trolytes in water may not show the same behavior when they are solved in sol-
vents like ether or hexane.
3-2- ELECTROLYTES AND NON-ELECTROLYTES
An aqueous solution is a homogeneous mixture which results when a substance
(solute) dissolves in water (solvent). We can divide the aqueous solutions of
substances into two with respect to their conductibility of electric current: The
first type is the solutions which have the ability to conduct electricity. These
types of solutions are called electrolytes. We can give the sodium chloride solu-
tion as an example. The second type is the solutions which do not conduct elec-
tricity. These are called non-electrolytes. Sugar solution is an example. (Figure
3-1) Not only aqueous solutions of salts but also molten salts (liquid salts) show
electrolytic properties.
Figure 3-1
The experiment that shows the 3-2-1-Electrolytes
effects of ion presence in a solu- All ionic and polarized (non-ionic) compounds dissociate into their ions when
tion. In the beaker, a bulb is con- dissolved in water. Therefore these are accepted as electrolytes. They can be
nected to two immersed copper salts, acids or bases. The most important properties of electrolytes are as follows:
electrodes. The substances in the 1- The capability of conducting electricity in the molten form or in aqueous solu-
solution are: tions.
a- The aqueous solution of potas- 2- The resultant electrical charge of electrolytic solutions is equal to zero. In
sium chromate. (The bulb lights other words, these solutions are electrically neutral.
strongly as many ions are present 3- In aqueous solutions of electrolytes, cations and anions are formed.
in strong electrolyte.) 4- The electrical conductibility of electrolytic solution depend on the structures
b- The aqueous solution of acetic and concentrations of ions and temperature of solution.
acid. (The bulb lights weakly as
few ions are present in weak elec-
trolyte.)
c- Sugar solution in pure wa-
ter. (The bulb does not light as
non-electrolytic substance is in
the solution.)

water molecule Sugar molecule H+ CH3COOH CH3COO- K+ CrO42-

Figure 3-1

80 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

A- Strong Electrolytes
Upon dissolution of these electrolytes in water, the resulting solution conducts
electricity well. The reason for this is the dissociation of these electrolytes to
their ions completely or almost completely in water. The examples for strong
electrolytes are hydrochloric acid HCl, sodium chloride NaCl, sodium sulfate
Na2SO4 , potassium nitrate KNO3 , sulfuric acid, H2SO4 and ammonium chlo- Attention: When water is
ride, NH4Cl. We can show the dissolution of these substances (strong electro- used as solvent, Kc of water is
lytes) in water through the following chemical equations: not written. Because it’s a fixed
value and shown in equilibrium
constant.

Generally there are three types of strong electrolytes.

1- Strong acids, 2- Strong bases, 3- Most of the water-soluble salts. This kind
of substances dissociate into ions completely or almost completely in dilute
aqueous solutions. In Table 3-1, examples for electrolytes and non-electrolytes
are given. As shown in the following example, the concentrations of ions in the Exercise 3-1
solutions of strong electrolytes are calculated directly using the concentration
of the electrolyte. Calculate the ion concentra-
tions for the following strong
Example 3-1 electrolytes with given concen-
trations.
Calculate the molar concentrations of Ba2+ and OH- ions in 0.03 M barium
hydroxide solution. A) HBr = 0.25M
B) KOH = 0.055M
Solution:
C) CaCl2 = 0.155M
The ionization chemical equation of strong base Ba(OH)2 is written.

Initial Concentrations
Change in
Concentrations

Final Concentrations

It means that the [Ba2+] ion concentration in the solution is equal to 0.03 M. The
[OH-] concentration is equal to 0.06 M.

B- Weak Electrolytes
Upon dissolution of these electrolytes in water, solutions with low conduct-
ing properties form. The reason for that is their partial ionization in aqueous
solutions. We can give following examples for weak electrolytes. Acetic acid
CH3COOH, ammonia NH3, carbonic acid H2CO3 , and silver chloride AgCl.
We can show the dissolution of these substances (weak electrolytes) into their

FEZALAR EDUCATIONAL INSTITUTIONS 81

 Chapter - 3

ions in water through the following chemical equations:

As seen in the equations above, the dissolution of these substances in water

is possible only through reaching ionic equilibrium. Each chemical reaction
representing the processes are defined as reversible reactions. This is shown
with two arrows opposite to each other. ‡ ˆ ˆˆ †ˆ .As mentioned in chemical
equilibrium chapter, reversible reactions are different from irreversible reac-
tions. Reversible reactions do not reach any end. This reaction system reaches
equilibrium when two reactions in opposite directions (forward and backward)
occur at the same time and rate.
This state is defined as a dynamic equilibrium. The average rates of forward
and backward reactions are equal. Components of the reactions react constant-
ly and for fixed temperature the concentrations of components remain constant
and the system reaches equilibrium. For example, acetic acid CH3COOH (weak
acid) molecules decompose in aqueous solution to hydrogen (H+(aq)) and acetate
(CH3COO-(aq)) ions. Forward reaction occurs. At the same time, hydrogen ions
combine with acetate ions and form acetic acid (backward reaction). When this
acid solution reaches equilibrium at some temperature, decomposition and for-
mation reaction rates become equal. Therefore, all ion concentrations
(CH3COO-(aq), H+(aq), CH3COOH) remain unchanged.
Ionic equilibrium is shown with equilibrium constant Kc just as in chemical
equilibrium. It is the ratio of multiplication of concentrations of products to the
multiplication of concentrations of reactants at equilibrium. It should be kept
in mind that the mole numbers of components in equilibrium reaction equation
are written as exponents. The equation for acetic acid decomposition to ions in
aqueous solution is shown as below:

At equilibrium, the molar concentrations of components in solution are shown

with square brackets “[ ]”. The numeric value of Kc is a constant at a given
temperature and does not change.

Example 3-2
Write the mathematical equation to calculate Kc value of aqueous solution of
dilute ammonia.

82 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

Solution: Table 3-1

As shown in the equilibrium equation, water molecules react with ammonia Examples for strong and weak
and equilibrium is reached. But, as water is used as solvent, the concentration electrolytes and Non-Electrolytes
of water molecules is much bigger than the other components’ concentrations. Strong Electrolytes
Therefore, in order to reach equilibrium, the concentration of water remains
constant. The molar concentration of water can be combined with equilibrium Strong Acids
constant. The resulting value is a constant number shown with Kc. The molar HCl Hydrochloric acid
concentration of water in dilute solutions can be calculated as pure water’s mo- HNO3 Nitric acid
lar concentration. (The density of pure water =1kg/L, 1kg =1000g) HClO4 Perchloric acid
H2SO4 Sulfuric acid

From definition of molarity, M, Strong Bases

NaOH Sodium hydroxide
M KOH Potassium hydroxide
Ca(OH)2 Calcium hydroxide

Soluble Salts
NaCl Sodium chloride
KNO3 Potassium Nitrate
K2SO4 Potassium Sulfate

Weak Electrolytes
Weak Acids
HF Hydrofluoric acid
HCN Hydrocyanic acid
H2CO3 Carbonic acid
HCOOH Formic acid

Weak Bases
NH3 Ammonia
CH3NH2 Methyl amine

Slightly Soluble Salts

3-3 DECOMPOSITION OF WEAK ELECTROLYTES
According to Bronsted-Lowry acid-base theory, the substance which donates AgCl Silver chloride
proton in order to form its conjugate base is defined as an acid. CaF2 Calcium fluoride
Acid ⇌ proton + conjugate base
Non-Electrolytes
Acids are neutral molecules such as HCl, H2SO4, CH3COOH or a positive ion CH3OH Methyl alcohol
like NH4+ and C6H5NH3+ or a negative ion like HSO4- and H2PO4-. C12H22O11 Sucrose
A base, according to Bronsted-Lowry acid-base theory, is a substance which CH3COOCH3 Methyl acetate
accepts a proton in order to form its conjugate acid.
Base + proton ⇌ Conjugate acid
The following bases can be given as examples of neutral molecule, positive ion
or negative ion bases.
OH- , CH3COO-, Fe(H2O)5(OH)2+, C6H5NH2, NH3

FEZALAR EDUCATIONAL INSTITUTIONS 83

 Chapter - 3

According to this theory, the strength of an acid or a base depends on acid’s

proton donation capability and bases’ proton accepting capability.
As it can be understood from the examples above, each acid has got a conjugate
base with different strength. This is also valid for bases. According to the the-
ory, if the acid is strong, its conjugate base is weak and vice versa. In aqueous
solutions, if the reaction shifts to right and the value of (HCl) is close to zero,
the Bronsted acid (e.g HCl) is strong. The same is valid for the Bronsted base.

Acids can be classified with respect to their reactions with water molecule. All
strong acids (or strong bases) decompose to ions in water nearly 100%. But
weak acids (or bases) decompose to ions in water only partially. For example,
a reaction like acetic acid’s decomposition (ionization) shifts to right in an
incomplete way.

3-3-1-Weak Acids
Weak acids are weak electrolytes. Therefore, in their aqueous solutions, ioniza-
tion equation can be shown as an equilibrium state.

By applying the special relationship of equilibrium constant;

Ka is the equilibrium constant of weak formic acid or the ionization constant

of this acid at constant temperature. As mentioned before, the concentration of
water can be assumed as constant and a general equation for acidity equilibri-
um constant can be written for weak acid (HA).

84 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

The most important point here which requires attention is that this relationship
can only be written for weak acids. Ionization reactions of strong acids do not Attention: While solving prob-
occur as equilibrium reactions. lems about chemical equilibrium,
for changes in concentrations
On the other hand, the equilibrium constant values of weak acids are accepted
of common substances in equi-
as a measurement of their strength. As the acidity constant of an acid increases
(amount of ionization increases), acidity strength increases. In Table 3.1, some librium reactions, reactants are
weak acids and their acidity constants are given as example. If the concentra- shown with negative, products
tion of weak acid and acidity constant are known, mathematical relationship are shown with positive.
for ionization equilibrium state of the acid can be used to calculate the hydro- In this chapter, initial and fi-
gen ion concentration in water.
nal concentration values only in
Example 3-3 equilibrium will be used.
Calculate the hydrogen ion concentration H+, percent ionization of acetic acid
and degree of ionization for 0.1 M aqueous solution of acetic acid. Ionization
constant of acetic acid (acidity constant) is 1.8x10-5

Solution:
Chemical equation for acid’s ionization equilibrium is written. Then, the rela-
tionship that shows acidity constant of acid is written

Here, it needs to be kept in mind that in the mathematical equation above, the
concentration which are shown with [ ] symbol are only the concentrations of
ions at equilibrium. Those, as shown in the equation below, are different from
initial concentrations of ions.

Initial concentration

Concentration at
equilibrium

As seen above, the amount of decomposed weak acid is (x mol/L). According

to equilibrium reaction, when x mole acetic acid decomposes, x mole of each
of hydrogen and acetate ions are produced. Then, equilibrium concentrations
are inserted in the mathematical relationship for acidity constant of weak acid.

When we re-arrange the equation above, we get the following relationship:

FEZALAR EDUCATIONAL INSTITUTIONS 85

 Chapter - 3

The relationship above is a second-order equation. We need to use general

Attention:
mathematics rules to solve it. But we will use a different method in this exam-
If degree of ionization is less than
ple. Because the Ka value of acid is an extremely small number. The amount of
5%, method of negligence is used ionized acid is too small when compared to acid’s initial concentration. There-
while calculating. But if degree of fore we can write the relationship below. We conclude the following in acidity
ionization is bigger than 5%, cal- constant equation (x is neglected in the solution):
culations are made through qua-
dratic equation.
Using this value in the ionization constant equation,
In a quadratic equation
(ax2+bx+c), a, b, and c show the
exponents of the equation. The
roots of quadratic equation is
found through the following for-
mula:

At equilibrium, when we compare the smaller amount of hydrogen ion

(1.3×10-3 mol/L) with initial concentration of acid (0.1 mol/L), it proves that
this negligence method is correct (x is neglected). Therefore, generally method
of negligence can be used if the acidity (or basicity) value of the acid (or the
base) is small (i.e. 10-7, 10-6, 10-5). If the value of Ka is big (bigger than 10-4,
10-3, 10-2) this method cannot be used. Because the results will not be correct.
Then the equation must be solved through general mathematics rules. Degree
of ionization is calculated from the equation below:
Concentration of ionized part of
the substance at equilibrium
Degree of ionization = Initial concentration of substance

Percent ionization is found through the following equation.

Concentration of ionized part of
the substance at equilibrium
Percent ionization = Initial concentration of substance × 100%

Percent ionization = Degree of ionization ×100

Example 3-3
The concentration of hydrogen
ions at equilibrium 1.3 × 10-3
Degree of ionization of acid = = 0.1 = 0.013
Initial concentration of the acid

ion at equilibrium
Decomposition percentage of acid = × 100%
Initial concentration of the acid

1.3 × 10-3
Decomposition percentage of acid = × 100%
0.1

Decomposition percentage = 1.3% acid

As the percentage of ionization is under 5%, method of negligence can be used.

86 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

Example 3-4 Exercise 3-2

Calculate the percentage of ionization and the degree of ionization of hydroflu- Calculate the concentration of hy-
oric acid (HF) which has an aqueous solution with concentrations; drogen ions in the aqueous solution
of 0.2 M of hydrocyanic acid.
A- 0.1 M
Ka= 4.9×10-10
B- 0.01 M.
Answer: 1×10-5M
(Ka= 6.8×10-4) Explain the relationship between percent ionization and the con-
centration of solution.

Solution:
A- For the solution with 0.1 M concentration:

The Ka value of hydrofluoric acid is much bigger than the acetic acid’s. There-
fore its percent decomposition is expected to be bigger than 5%. Thus, the
method of negligence which we used in acetic acid example may not be valid
here. So we will solve this question using both methods.

Rounding up method:

In the equation above, if x is neglected, we get the following one.

The concentration of hydrogen

ions at equilibrium 8.25 × 10-3
Degree of ionization of acid = = 0.1 = 0.0825
Initial concentration of the acid

FEZALAR EDUCATIONAL INSTITUTIONS 87

 Chapter - 3

ion at equilibrium
Decomposition percentage of acid = × 100%
Initial concentration of the acid

8.25 × 10-3
Decomposition percentage of acid = × 100% = 8.25%
0.1

The acid’s percent ionization is bigger than 5%. The reason for this is the
acidity constant is bigger than 10-5. Therefore this method cannot be used for
solution. We will solve it through quadratic equation.

Through solving this equation, there are two roots. One is positive and the
other is negative. The negative value is neglected as it is meaningless. (A
concentration value can never be negative.)

The hydrogen ion concentrations in hydrofluoric acid solution at equilibrium

are calculated using both methods. It seems that there is a very big difference
between results. Since it gives a wrong result, we cannot use method of neg-
ligence.
Degree of ionization = The concentration of hydrogen ion at equilibrium
Initial concentration of acid

7.91 × 10-3
Degree of ionization of the acid = 0.1 = 0.079

ion at equilibrium
Percent ionization = × 100%
Initial concentration of the acid

7.91 × 10-3
Percent ionization of hydrofluoric acid = × 100% = 7.91%
0.1

88 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

B- For the solution with 0.01 M concentration Exercise 3-3

The second-order equation for this solution is as follows: Calculate the concentration of
hydrogen ions in the aqueous solu-
tion of phenol, C6H5OH with con-
centrations;
x value is obtained through solution of the mathematical equation. A- 0.2 M,
B- the solution diluted by 100
times.
Degree of ionization = The concentration of hydrogen ion at equilibrium (Ka= 1.3×10-10)
Initial concentration of acid
Answer: A- 0.51×10-5 M
B- 0.51×10-6 M

Percent ionization = The concentration of hydrogen ion at equilibrium ×100%

Initial concentration of acid

Attention: Strong acid produces

weak conjugate base or vice versa.
As weak acid’s acidity equilibrium
The most significant point here which needs attention is that when we dilute constant increases, acid’s strength
acid solution by 100 times, degree of decomposition (or degree of ionization) increases.
increases by nearly 3 times (from 0.079 to 0.229). This result is expected ac-
cording to Le Chatelier’s Principle. Because diluting the solution is an external
factor and the system will determine a new equilibrium state in order to com-
pensate this effect. For this, the substance will dissolve (ionize). As a result of
this process, the amount of acid molecules decreases whereas the ions in the
solution increase. Thus the solution reaches equilibrium once more.

Monoprotic and Polyprotic Weak Acids

Monoprotic weak acids have only one hydrogen atom which can ionize (single
acid proton).Therefore those has only one acidity constant. But there are many
acids which have more than one acid proton. These acids are called as poly-
protic weak acids, i.e. oxalic acid (H2C2O4) . This acid is a substance that has
two protons with different acidity equilibrium constants. Therefore the aqueous
solution of the acid has 2 ionization reactions and 2 acidity equilibrium con-
stants. These are respectively, Ka1 , Ka2:

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 Chapter - 3

Phosphoric acid (H3PO4) has 3 ionization reactions and 3 acidity equilibrium

constants. (Ka1,Ka2,Ka3)

Do you know that?

If we examine the values of acid-
ity equilibrium constants, the or-
der is as follows.

Ka1>Ka2>Ka3

The reason for that is the electro-

static attraction power is strong
between different charged ions.
So the negative charged substanc-
es have a low capability of losing
positive proton.

3-2-2-Weak Bases
According to Bronsted acid-base theory, weak base is the substance which has
ability to accept proton from solution. It has basicity equilibrium constant Kb.
For example, the ionization reaction of ammonia in water is shown as follows:

Note that the writing method of Ka and Kb are the same. Generally, the ioniza-
tion reaction of weak base is written as ionic equilibrium as follows:

90 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

Example 3-5
Calculate [OH-] ions concentration, degree of ionization and percent ionization
for 0.2 M aqueous ammonia solution. Kb(NH3)=1.8 × 10-5
Solution:

The ionization reaction equation is written for ammonia, and molar concentra-
Attention: While solving problems
tions of substances are shown in the equation. Then those concentration values
about weak bases, whether method
are inserted in the basicity equilibrium constant relationship.
of negligence is used or not depends
on the rules which are valid for weak
Degree of ionization = The concentration of hydroxide ion at equilibrium acids.
Initial concentration of base

Exercise 3-4
Percent ionization = The concentration of hydroxide ion at equilibrium ×100% Calculate degree of ionization of
Initial concentration of base
0.1 M aqueous solution of aniline,
C6H7N. (Kb = 3.8×10-10)
Answer: 6.2×10-5

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 Chapter - 3

3-4- SELF-IONIZATION OF WATER

(AUTO-IONIZATION OF WATER)
Self-ionization of water or auto-ionization of water is formation of hydronium
H3O+ and hydroxide ion OH- in its solution. A proton can be transferred from
one water molecule to another in self-ionization of water or in other aqueous
solutions of different substances. Self-ionization of water is a process in which
a proton is transferred to other molecule by itself. This process gives water
amphoteric property.
Scientific experiments have shown that water can conduct electricity. Pure wa-
ter can ionize very slightly.

Or in a simpler way,

Equilibrium state can be defined with a value called as ionization constant and
shown with Kw.

Hydroxide ion (OH-) always combines a hydronium ion H3O+ (or simply hy-
drogen ion H+). Therefore, concentration of hydrogen ion is always equal to
concentration of hydroxide ion in pure water. Measurements in pure water at
25 °C have shown that;

Those experimental values measured at 25 °C can be used to calculate ioniza-

tion constant of water Kw.

Kw value of pure water at 25 °C can also be used successfully for dilute aque-
ous solutions.
Pure water is a neutral medium. That means it is neither acid nor base. There-
fore, in any neutral solution, concentration of hydrogen ion is equal to concen-
tration of hydroxide ion in the same solution ([OH-]=1.0×10-7 M). But when
we add some acid to pure water, according to ionization equilibrium reaction
of water, the concentration of hydrogen ion increases and the concentration of
hydroxide ion decreases (Le Chatelier’s Principle.)
H2O(l) ⇌ H+(aq) + OH-(aq)
In a system at equilibrium, the ionization constant of water, Kw is always a
constant value (1.0×10-14). Therefore any increase in the concentration of H+
causes a decrease in the concentration of OH- or vice versa. By the same meth-
od, if we add some base to water (or to any neutral solution), the concentration
of OH- ions increases and as a result, the concentration of H+ ions decreases. In
the following solutions the concentrations of H+ and OH- ions are given:

92 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

Solution General Situation

Example 3-6
Calculate the concentrations of H+ and OH- ions in 0.05 M nitric acid, HNO3
solution.

Solution:
The ionization equation of nitric acid is written. On it, the molar concentrations
of H+ and NO3- ions are shown. Then, to find out the concentration of OH- ions
in solution, the following relationship is used.

Initial Concentration

Final Concentration

The Value of (OH-) can be calculated by constant ionization of water with Kw

Exercise 3-5
Calculate the concentrations of hy-
drogen ions in aqueous solutions
which contain;
A- 0.01 M [OH-]
B- 2.0 ×10-9 M [OH-] ions.
Answer: A- 1×10-12 M
Depending on what we have learnt recently, the value of x (the concentration B- 5×10-6 M
of H+ formed through ionization of water) is much smaller than concentration
of H+ formed through complete ionization of acid. Therefore, by neglecting x
(x+0.05) we can accept its value as 0.05. If we solve the equation;

FEZALAR EDUCATIONAL INSTITUTIONS 93

 Chapter - 3

WARNING: [OH-] and [H+]

concentrations which are released
during water ionization always
neglect in strong base and strong
acid solutions.

When the concentration of OH- ion in this solution is examined, it is seen that
the value of x (the concentration of OH- ion) is much smaller than 0.05 and this
proves the method of negligence.

3-5-THE HYDROGEN ION EXPONENT IN AQUEOUS

SOLUTIONS
Making calculations with too small concentrations of H+ and OH- ions is dif-
ficult and risk of mistake is high. A scientist named Sorensen suggested using
pH (acid scale) to express acidity of a solution in 1909. According to this, the
concentration is defined with respect to the following relationship.

One of the advantages of this method is that when the molar concentrations of
H+ and OH- ions are known, the acidity or basicity values of solutions can be
expressed with positive numbers between 0-14. Besides, the concentrations of
hydroxide ions are found with the same method:

Example 3-7
Exercise 3-6 Calculate pH value of solution which has 0.05 mol/L H+ ion.
Calculate the pH value of the follow-
Solution:
ing solutions.
In order to find pH value of solution, negative logarithm of H+ ion concentra-
A) Hydrochloric acid 6×10-4 M tion needs to be calculated as follows:
B) Sulfuric acid 0.03 M
Answer: A) 3.22
B) 1.22

94 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

Example 3-8
If pH of a solution is 3.301, what is the concentration of H+ ion in the solution?

Solution:
In pH= -log [H+] relationship, pH is inserted in its place and equation is solved.

By taking the logarithm of both sides of the relationship, we get the following
result:

pH values of some substances

The relationship between pH and pOH values in a dilute solution at 25 °C is
used. Substance pH Value
Content of human stom-
ach 1.6-3.0
Fizzy drinks 2.0-4.0
By taking the logarithm of both sides of the relationship, the equation below
Lemon 2.2-2.4
is reached.
Vinegar 2.4-3.4
Tomato 4.0-4.4
Human urine 4.8-8.4
By multiplying both sides by (-1), we get the following:
Cow milk 6.3-6.6
Human saliva 6.5-7.5
Human blood plasm 7.3-7.5
White of egg 7.6-8.0
Anti acid 10.5
Dilute ammonia
This relationship shows that if pH and pOH values in a solution are both lower 11-12
solution
than 14, they are both positive, but if one of both is bigger than 14, the other
one is negative. Generally, pH and pOH values of dilute solutions at 25 °C are
as follows:

Exercise 3-7
What is the molarity of the solution
if pH of nitric acid solution is 3.32?
Neutral
Answer: 4.79×10-4 M

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 Chapter - 3

Exercise 3-8 Nowadays, in order to express concentrations of other ions, “p” term is used.
Generally with a “p” before symbol, it means the negative logarithm of the
By using the table below, find out pH symbol. According to this, pH means negative logarithm of the concentration
and pOH values of each solution and of H+ and pOH is negative logarithm of the concentration of OH-. pK is nega-
complete the table. Explain the rela- tive logarithm of ionization constant. In the same manner, the negative loga-
rithm of ionization constant of water is shown as pKw = -logKw
tionship among them.
Example 3-9
Calculate pOH, [OH-], pH and [H+] values for 0.015 M hydrochloric acid solu-
tion.

Solution:
The ionization equation of HCl is written. We calculate the concentration of
hydrogen ions. Then we calculate pH value. According to mathematical rela-
tionships mentioned before, pOH and [OH-] are found out.

As HCl is a strong acid, it ionizes completely. That means:

As it is known, pH + pOH = 14. Therefore,

The pH value of fizzy drinks is cal- As , [OH-] can be easily calculated.
culated by a pH meter. Many fizzy
drinks show acidic property due to
dissolved CO2 and some other ingre-
dients they contain.

Exercise 3-9 3-6 SOLVOLYSIS

The term “solvolysis” means a substance dissociates homogeneously by inter-
Calculate the values of [H+],[OH-],
acting with a suitable solvent. The important solvolysis reactions in our scope
pH and pOH of 0.015 M of Ca(OH)2
are the aqueous ones (water is used as solvent.) The interaction of a substance
aqueous solution. Is solution acidic
with water is called as hydrolysis. Hydrolysis reactions include interactions
or basic? Why?
with H+ and OH- ions. For example, the interaction of the negative conjugate
Answer: of a weak acid with water in order to yield non-ionized weak acid is a kind of
[H+]= 3.3×10-13 hydrolysis. As a result, H+ and OH- ions in water produce base solution and
[OH-]= 0.03 M weak HA acid. The reaction is shown as follows:

pOH= 1.52 A-(aq) + H2O(l) ⇌ HA(aq) + OH-(aq)

pH= 12.48 Conjugate water weak acid As OH- ion concentration
of weak acid increases, solution becomes basic.

The interaction of acetate ion CH3COO- with water can be given as an example.
CH3COO-(aq) + H2O(l) ⇌ CH3COOH(aq) + OH-(aq)

96 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

In a similar way, the interaction of the positive cation of weak base (conjugate
acid) with water is an example. Here the resulting solution is acidic.
NH4+(aq) + H2O ⇌ NH3(aq) + H3O+(aq)
According to Bronsted acid-base theory, the conjugate base of strong acid
shows a very weak base property. Similarly, the conjugate base of a weak acid
shows a strong base property. All those properties are also valid for bases.
With respect to interactions of salts in aqueous solutions, we can divide them
into for parts:
1- Salts of strong base-strong acid
2- Salts of strong base-weak acid
3- Salts of weak base-strong acid
4- Salts of weak base- weak acid
Now we will study each of those separately.

3-6-1-Salts of Strong Base-Strong Acid

These salts are formed from positive ion of strong base and negative ion of
strong acid. The solution of this kind of salts is neutral. Because neither pos-
itive ions nor negative ions interact with water molecules significantly. For
example, in dilute solution of NaCl (the salt formed from NaOH base and HCl
acid) salt decomposes (dissolves) to its ions. Besides, water molecules also
ionize.

H2O
NaCl(s) → Na+(aq) + Cl-(aq)
H2O(l) ⇌ H+(aq) + OH-(aq)

Salt of strong acid

and strong base

Neutral Aqueous
Solution

The aqueous solution of this salt includes 4 types of ions. These are OH-, H+,
Cl- and Na+. Na+ is a weak acid and it does not react with water at a significant
level. Also the negative ion of salt Cl- is a weak base and it does not react with
water at a significant level. As a result, it can be said that the aqueous solutions
of salts formed from strong bases and strong acids are neutral.
Because neither ions (positive or negative) have the capability to react with
water and disrupt the equilibrium between H+ and OH- ions.

FEZALAR EDUCATIONAL INSTITUTIONS 97

 Chapter - 3

3-6-2-Salts of Strong Base - Weak Acid

When a salt formed from a strong base and a weak acid dissolves in water, the
resulting solution is always basic. The reason is that the negative ion (which
belongs to weak acid) interacts with water in order to form OH- ion. For exam-
ple, sodium acetate salt, CH3COONa (the salt formed from NaOH strong base
and CH3COOH weak acid) does not ionize completely when dissolved in water
as below:

H2O
CH3COONa(s) → Na+(aq) + CH3COO-(aq)
H2O(l) ⇌ OH-(aq) + H+(aq)
→
The Position of Equilibrium Shifts
⇅
The solution which
CH 3
COOH
has more OH- ions

Salt of strong base

and weak acid

Basic Aqueous
Solution

The acetate ion represents the conjugate base of weak acid CH3COOH. There-
fore, these acetate ions interact with H+ ions in order to form CH3COOH. As a
result, the amount of H+ ions in the solution decreases. H2O molecules ionize to
compensate the decrease. Thus the amount of OH- ions increases and the solu-
tion becomes basic. In order to define the hydrolysis of acetate ions, the total of
equations above can be expressed with a single equation as follows:

The equilibrium constant of this reaction is called as hydrolysis constant. It is

shown with Kh.

98 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

Generally, the value of hydrolysis constant of a salt formed from strong base
and weak acid can be expressed as follows:

In the equation, [HA] represents the concentration of weak acid, [OH-] the con-
centration of strong base and [A-] the concentration of unhydrolysed salt (ini-
tial concentration of salt). Strong base and unhydrolysed salt ionize complete-
ly. But weak acid ionizes only slightly. The value of Kh hydrolysis constant can
be calculated through relationships known beforehand. For this, numerator and
denominator are multiplied with [H+]:

Example 3-10
What is the value of hydrolysis constant (Kh) of sodium acetate salt? The acid-
ity constant of acetic acid Ka(CH3COOH)= 1.8×10-5, the ionization constant of
water, K =1.0×10-14
w

Note: As Kw is not given in such questions, students need to know it by

heart.

Solution:
Sodium acetate salt is formed from strong base NaOH and weak acid
CH3COOH. Therefore, if the acidity constant Ka of weak acid and ionization
constant of water Kw is known, the hydrolysis constant of salt is calculated as
follows:

In short, the hydrolysis constant of any salt formed from strong base and weak
acid is calculated through the following relationship:

or

FEZALAR EDUCATIONAL INSTITUTIONS 99

 Chapter - 3

Ka is the acidity constant of weak acid that forms salt, pKh ,

pKw, pKa, are the negative logarithms of Kh, Kw, Ka, values respectively. The
concentrations of H+ ion can be calculated easily for this kind of solutions.
Because the amounts of HA and OH- ions formed as a result of hydrolysis are
equal. Therefore, in salt solution [HA]=[OH]. The molar concentration of salt
in the solution is cM.

[HA] [OH-] [OH-]2 Kw

Kh = = =
[A-] c Ka

Kw
[OH-] = c× or
Ka
Attention: If pH and [H+] is
asked to be calculated, students Kw
can choose which equation to be [H+] =
[OH-]
used. Any of the two relation-
ships can be used in calculation.
Kw × Ka
[H+] =
c

1
pH = [pKw + pKa + logc]
2

Exercise 3-10 Example 3-11

Calculate the concentration of hydrox- Calculate pH value of 0.01 M sodium acetate salt at 25 °C.
ide ions in 0.1 mol/L potassium cya- Ka(CH3COOH) =1.8×10-5
nide, KCN, salt aqueous solution.
Solution:
Ka(HCN) = 4.9×10-10
We use the following relationship to calculate pH of this salt solution.
Answer: 1.43×10-3 M

100 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

3-6-3-Salts of Weak Base-Strong Acid

In the second type of hydrolysis reactions, positive ions of salt (which belong
to weak base) react with OH- ions in water. This reaction disrupts the equilib-
rium between H+ and OH- ions. As a result, [H+] ion increases and the solution
becomes acidic. Therefore, ammonium chloride salt NH4Cl (salt formed from
weak base NH3 and strong acid HCl) decomposes completely when dissolved
in water as follows;

H 2O
NH4Cl(s) → NH4+(aq) + Cl-(aq) The solution which
H2O(l) ⇌ OH (aq) + H - + has more H+ ions
(aq)
→
The Position of
Equilibrium Shifts ⇅
NH3 + H2O

Ammonium ion (the conjugate acid of weak base NH3) reacts with OH- to
produce non-ionized NH3and H2O molecules. This reaction consumes OH- ions
in the medium. Therefore, to compensate this decrease and establish a new
equilibrium, H2O molecules ionize. As a result, the amount of H+ increases and
the solution becomes acidic.
In order to define the hydrolysis of ammonium ion NH4+ , a final equation rep-
resenting all of the reactions above can be written.

Salt of strong acid

and weak base

Acidic Aqueous
Solution

NH4+(aq) + H2O ⇌ NH3 + H3O+

[NH3] [H3O+] Kw
Kh = =
[NH4+] Kb

Kw
K h = K Relationship can be proved. Kb is the ionization constant of weak
b
base. Besides a general equation expressing hydrolysis of this kind of salts can
be written as follows:

FEZALAR EDUCATIONAL INSTITUTIONS 101

 Chapter - 3

[MOH] represents the concentration of weak base, [H+] for strong acid and
[M+] for unhydrolysed salt. As [MOH] and [H+] are formed through hydrolysis
of salt molecules, their concentrations in the salt solution are equal.
For the solution with cM molar concentration:

We get the following relationship from above equation:

Kw
[H+] = c×
Kb
By taking negative logarithm of both sides:
1
pH = [pKw - pKb - logc]
2
Kb represents the basicity constant of the weak base which the salt is formed
from.
Exercise 3-11
Example 3-12
Calculate pOH value of 0.5 M ammo-
nium nitrate (NH4NO3) solution. Is the What is the pH of 0.2 mol/L ammonium chloride solution?
solution acidic or basic? Kb(NH3)= 1.8×10-5
(pKb (NH3) = 4.74) Solution:
Answer: 9.22, The solution is acidic. We need to know the basicity constant of weak base and the ionization con-
stant of water to find pH of solution. Then the following relationship is used to
calculate pH:
1
pH = [pKw - pKb - logc]
2

102 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

3-7 COMMON ION EFFECT

We have studied the aqueous solutions of weak electrolytes and their behav-
iors. In this chapter, we will study the behaviors of aqueous solutions with two
electrolytes (one is weak). The similarity of these two electrolytes is that they
have a common ion. The concentration of an ion in any solution can increase
as a result of decomposition of added compound into its ions. The ion which is
present in the solution and added compound is called as common ion.

At this level, we will focus on the situation which the electrolyte in solution
is weak and added compound is strong. As a result of addition, a significant
amount of increase occurs in the concentration of common ion. This increase
can be understood when the concentration of weak electrolyte is compared
to the concentration after addition. Disequilibrium results from this process.
Therefore, the solution forms a new equilibrium.

When some amount of ion is added to weak electrolyte solution, the ionization
of weak electrolyte decreases. This phenomena result from the establishment
of ionic equilibrium again in electrolyte solution. This is called as common ion
effect. This situation is a result of Le Chatelier’s Principle.

Example 3-13
How does the concentration of H+ ion change when 8.2 grams (0.1 mol) sodi-
um acetate salt, CH3COONa, is added to 1 liter 0.1 mol/L acetic acid solution
at 25 °C? Ka(CH3COOH) = 1.8×10-5

Solution:
The ionization equations of weak electrolyte and added salt are written. On
them, the molar concentrations at equilibrium are shown.

CH3COOH(aq) ⇌ H+(aq) + CH3COO-(aq)

Initial concentration 0.1 M 0 0
Concentration (0.1- x) M xM xM
at equilibrium

CH3COONa(s) → Na +
(aq)
+ CH3COO-(aq)

Initial concentration 0.1 M 0 0

Final concentration 0 0.1 M 0.1 M
Common ion

Ionization equations show that common ion in that solution is acetate ion. Be-
cause it has two sources: One is acetic acid (weak electrolyte), the other is
sodium acetate (strong electrolyte). The concentration of common ion is found
by addition of concentrations result from ionization of both compounds.

In order to calculate the effect of common ion, the concentration of H+ ion in

0.1 M acetic acid solution is calculated as below before the addition of sodium
acetate:

FEZALAR EDUCATIONAL INSTITUTIONS 103

 Chapter - 3

[H +
] [CH3COO-] ________
(x) (x)
_____________
Ka = 1.8 × 10 =-5
=
[CH3COOH] (0.1 - x)

We get the following and apply the method of negligence

(x) (x)
Ka = 1.8 × 10-5 = _______
(0.1)

x2 = (0.1) × (1.8 × 10-5 ) = 1.8 × 10-6

x2 = 1.8 x 10 -6 = 1.3 × 10-3

[H+] = 1.3 × 10-3 mol/L

Then, after adding sodium acetate (common ion effect), the concentration of
H+ ion in acid solution is calculated as follows:

[H +
] [CH3COO-]
_____________
Ka = 1.8 × 10 =-5
[CH3COOH]
Exercise 3-12
How does the ionization degree of (xʹ) (0.1 + xʹ) (xʹ) (0.1)
base change when 26.75 grams (0.5 = ___________ = _________
mol) ammonium chloride salt is add- (0.1 - xʹ) (0.1)
ed to 0.1 M 1 liter ammonia solution?
xʹ = 1.8 × 10-5 mol/L = [H+]
Kb(NH3)=1.8×10-5
Answer: Ionization of the base is When we compare the concentrations of H+ ion before and after (common ion
effect) addition of salt, we see that the concentration decreases to 1.8 × 10-5
greater than 360 times.
mol/L from 1.3 × 10-3 mol/L. The reason for that due to a common ion (acetate)
presence between two compounds, the ionization of acetic acid decreases by
addition of sodium acetate salt.

3-8 BUFFER SOLUTIONS

pH values of strong acid and base solutions can be calculated easily through
their molar concentrations. According to this, the pH value of 10-4 M hydro-
chloric acid is equal to 4. But this value changes considerably even a small
amount of basic substance is added to acid solution. The same is also valid for
base solutions. For example, the pH value of 1 M ammonium acetate salt and
sodium chloride salt solution is approximately equal to 7 (Why?). But when
a small amount of strong acid or base is added to this solution, its behavior
changes. Because when 1.0 M 1 mL HCl solution is added to 1 liter salt solu-
tion, the pH of NaCl solution becomes 3.0, but the pH of CH3COONH4 chang-
es very slightly.

In many solutions, common ion effect is observed. But there are two very com-
mon situations:

104 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium
1- A solution formed from a weak acid and the salt of this acid (e.g. CH3COO-
Na and CH3COOH)

2- A solution formed from a weak base and the salt of this base (e.g. NH3 and
NH4Cl)

There are some reactions occurring in scientific laboratories or in industrial

processes or in bodies of living beings which need the pH value to remain con-
stant upon addition of small amounts of acid or base. For example, most of the
metabolic activities occurring inside human body are sensitive to pH values of
body liquids. Transportation of oxygen and activities of enzymes in cells can
be given as examples. Therefore, our bodies use a compound mixture called
buffer solution (the system preserves from pH change) that preserves pH value
between certain limits. When a small amount of strong acid or a base is added
to a solution, the resistance of H+ ion to change is called as buffer effect or buf-
fer action, and solutions which have this property is called as buffer solutions.

In buffer solutions, generally two interactions occur. First one neutralizes added
base by interacting with it. The other one neutralizes the added acid. This way
the buffer effect of solution occurs. This kind of solutions are generally formed
by mixing a weak acid and its derived salt or a weak base and its derived salt.
The buffer solution formed from mixing acetic acid (weak acid) and sodium
acetate (salt derived from acetic acid) is an example. In order to observe how
such a solution resists to pH change, we will examine the effects of addition of
some strong HCl into buffer solution and into pure water.

As a result of addition of some strong acid into water, a big increase occurs
in the concentration of H+ ion and a big decrease in the pH value of solution.
But an addition of same amount of acid into acetic acid-sodium acetate mix-
ture does not result in a significant amount of increase in H+ ion concentra-
tion. Because this ion does not remain free in the solution but interacts with
CH3COO- ion from sodium acetate in order to form acetic acid. Thus the pH
value of solution does not decrease but remain almost constant.

When some amount of strong base as NaOH is added to water, as a result of

complete decomposition of base, the concentration of OH- ions will increase.
Therefore, the pH value of solution will increase. If the same amount of base
is added to buffer solution (CH3COONa and CH3COOH), the OH- ions cannot
remain in the solution but react instantly with H+ ions from decomposition of
acetic acid and form water.

As a result, the pH value of this mixture does not change significantly. With
respect to what is mentioned above, buffer solution neutralizes as it reacts with
components of added strong acid or base.

Thus the pH value of the solution remains constant. But in fact, when HCl is
added, the concentration of acetic acid increases a bit. This is a weak acid.
The increase in the concentration of solution causes a slight decrease in pH of
solution. On the other hand, the addition of NaOH to buffer solution causes
formation of sodium acetate. The increase in the amount of this salt results in a
slight increase in pH of solution. (Why?)

FEZALAR EDUCATIONAL INSTITUTIONS 105

 Chapter - 3

We will examine the equilibrium position of weak acid HA (or weak base)
solution and the reactions of weak acid’s salt.

Here the equilibrium position is as follows:

or

If we assume the [H+] in solution as very small (as a result of common ion
effect which works to decrease weak acid’s decomposition), we can simpli-
fy this relationship (after applying method of negligence). In equilibrium, the
concentration of unionized acid will be equal to initial acid concentration. The
concentration of [A-] in equilibrium will be only equal to salt’s concentration.
Therefore we can rewrite previous relationship as follows:

[acid] represents the concentration of acid, whereas [salt] is the concentration

of salt. We can re-arrange the equation by taking the logarithm of both sides:

By the same method, it is possible to derive a relationship that defines the equi-
librium position of a mixture formed from weak base and its salt.
(A)

In the equation, [base] is the concentration of base and [salt] is the concentra-
tion of salt.
A- When respiration stops, the amount of CO2 in blood increases.
As a result, the amount of carbonic acid increases and the pH value of blood
decreases.
B- During breathing heavily, the amount of CO2 in veins decreases.
As a result, the amount of carbonic acid in blood decreases and the pH value
of blood increases.
(B)

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 Ionic Equilibrium

Example 3-14 Exercise 3-13

Calculate the concentration of H+ ions and pH value of the solution of 0.1 M Calculate the pH of 0.15 mol/L NH3
acetic acid and 0.2 M sodium acetate. Ka(CH3COOH)=1.8×10-5 and 0.3 mol/L NH4Cl solutions. Com-
Solution: pare the result with the pH of 0.15 M
ammonia solution. (pKb =4.74)
We can use the mathematical relationship above to calculate the concentration
of H3+ ions and pH value of the mixture of weak acid and its salt. The mixture
Answer: 8.96; 11.22
has got buffer solution property. Therefore:

[acid]= 0.1M , Ka(CH3COOH) =1.8×10-5 and [salt]=0.2M

We get the result below:

We can calculate the pH of solution using the following relationship:

or using the following equation directly:

As pKa = -logKa

Here we can compare the concentration of H+ ions and pH value of the solution
(buffer solution) with the calculated values of 0.1 M acetic acid. This compar-
ison is ([H+] =1.35×10-3 M) and (pH = 2.87) respectively.

Example 3-15
What should be the concentration of ammonium chloride in order to have a pH
of 9.0 for 0.1 M ammonia solution? pKb = 4.74

Solution:

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 Chapter - 3

Exercise 3-14 The pOH value of the solution with a pH value of 9.0 is equal to 5.0. The solu-
tion of ammonia and ammonium chloride is a buffer solution. Therefore we
0.3 M sodium acetate salt forms can calculate using the previous mathematical relationships. We can use the
a buffer solution with acetic acid. following relationship for the solution of weak base and its salt.
What should be the concentration of
acetic acid for the solution to have a
pH value of 4.31? Ka =1.8×10-5
Answer: 0.81 M

Example 3-16
Calculate the pH value of new solution formed after addition of 1 mL of 10M
hydrochloric acid solution into 1 liter 0.1 M acetic acid and 0.1 M sodium ace-
tate buffer solution. pKa = 4.74
(Note: While solving the question, ignore the volume change in solution occurs
after addition of strong acid or base.)

Solution:
The buffer solution formed by acetic acid and sodium acetate can be expressed
by following equations:

1- The amounts (mole numbers) of sodium acetate and acetic acid in solution
before addition of strong acid is calculated as follows:
Mole number of acetic acid in 1 liter solution = MCH3COOH × V(L)
0.1 mol/L × 1 L = 0.1 mol
Mole Number of salt in 1liter solution = MCH3COONa × V(L)
0.1 mol/L × 1 L = 0.1 mol
2- HCl acid decomposes completely as in the following equation

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 Ionic Equilibrium

In order to produce H+ ions equal to the added amount of acid: Exercise 3-15
MHCl × V (L) (Mol number of H ions equals to the added amount of acid:
+ Calculate values of pH of the fol-
lowing;

A- 1 liter buffer solution is formed

from 0.1M ammonia, NH3, and
0.1M ammonium chloride NH4Cl.
H+ ions produced from decomposition of HCl combine with the same amount
of acetate ions to produce the same amount of acetic acid. B- Calculate the change in value
3- The amounts and concentrations of acetate ions and acetic acid are calculat- of pH of the same solution after
ed as follows after addition: adding 10M of 1mL sulfuric acid,
H2SO4. Discuss the results.
The amount of produced H+ ions + the amount of acetic acid before addition = pKb= 4.74
The amount of acetic acid after addition
Answer:
A) 9.26
B) 9.08
ΔpH = -0.18

The amount of produced H+ ions - the amount of sodium acetate before addi-
tion = The amount of sodium acetate after addition

4- The special equation to calculate pH value in buffer solution is applied as

follows:

3-9-SOLUBILITY AND SOLUBILITY PRODUCT

Dissolution of solids in water is accepted as one of the important procedures in
chemistry. Because solubility of any ionic substance depends on the difference
between the amounts of energy necessary to break the bonds between ions
constituting the matter and energy released during ionization and hydration.
Therefore solubility of substances in water differ.
In this chapter, we have studied the behaviors of substances dissolved in water.
But there are many substances which are slightly soluble in water. The solu-
bility of these substances depends on an equilibrium state between the solid

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 Chapter - 3

Do you know? part of the substance and produced ions (between the decomposed and non-de-
When ammonium sulfide solution is composed). This solution is called as saturated solution. The dissolution of a
mixed with cadmium nitrate solution, a slightly water soluble substance can be defined as follows:
sediment called cadmium sulfide forms.

The equilibrium constant (Keq) of this equilibrium reaction is shown with the
following relationship.

Cadmium sulfide, which is a slightly sol-

uble salt, is used in production of yellow
dye used in paintings.

We assume that the concentration of [AB] remains constant as the compound

dissolves slightly in water and only a very small part of it decomposes. Be-
sides, as the solvent is water, the concentration of [H2O] is assumed as con-
stant. Therefore, the previous relationship can be re-arranged as follows:

Because:

The value of Ksp is called as solubility product constant. This value remains
constant at a certain temperature. Solubility product constant is used to express
(or measure) the solubility of slightly soluble salts in water. The solubility of
a compound is directly proportional to its solubility product. Generally, the
solubility product of a slightly soluble ionic compound is calculated through
the molar concentrations of ions making up of the compound at equilibrium (in
saturated solutions molar solubility is shown with –s-). When writing solubility
product constant in equilibrium chemical equation, the concentrations of ions
formed from decomposition of compounds are multiplied. Mole numbers are
written as exponents. The molar solubility of slightly soluble salts –s- is de-
fined as the molar concentration of ions formed from decomposition of salt in
solution at equilibrium.
The solubility product constant of salts like AgCl, BaSO4 and PbSO4 which
have two moles of ions in their solutions is expressed as follows:

The solubility product constant of salts like Zn(OH)2 or CaF2 which have
three moles of ions in their solutions is expressed as follows:

The solubility product constant of a salt like Ca3(PO4)2 which have 5 moles of
ions in its solution is expressed as follows:

110 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

These rules are applied only when a saturated solution of a slightly soluble
salt is at equilibrium.

Example 3-17
As the solubility product constant of lead sulfate salt PbSO4 is Ksp =1.6×10-8,
what is the molar solubility of PbSO4?

Solution:
First, the chemical equilibrium equation for dissolution of PbSO4 is written.

Let’s assume that the molar solubility of PbSO4 salt is s mol/L. As seen in the
equation, when 1 mole of PbSO4 is dissolved, 1 mole of Pb+2 and 1 mole of SO4
ions are formed in the solution. Depending on this, solubility constant Ksp is
written mathematically as follows:
Exercise 3-16
Calculate the solubility product
constant of Ag2CrO4 salt, as the
saturated solution of 1 liter silver
chromate, contains 0.0215 g salt.
(M=332 g/mol)
Answer: 1.09×10-12

Example 3-18
Calculate the solubility product constant Ksp of BaSO4 salt as 1 liter saturated Exercise 3-17
solution of BaSO4 contains 0.0025 g/L BaSO4 (M = 233 g/mol).
Calculate the solubility (g/L) and
Solution: molar solubility of silver chloride,
First, chemical equilibrium equation for dissolution of BaSO4 salt is written. AgCl, salt in equilibrium.
Then, the mathematical expression for solubility product constant Ksp is writ-
ten. From the solubility value of salt (0.0025 g/L), the molar solubility (mol/L) (M=143.5 g/mol)
and the concentrations of ions in solution can be calculated. An equilibrium is
Ksp(AgCl) =1.8×10-10,
established between the decomposed and non-decomposed parts of this salt in
its saturated solution as follows. Answer: 1.3 × 10-5 mol/L
1.93 × 10-3 g/L

-s- molar solubility (M = 233 g/mol) of BaSO4 is calculated depending on its

solubility.:

Molar solubility of BaSO4 = solubility of BaSO4 (g/L)

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 Chapter - 3

Ba2+ and SO42- ions are formed from dissolution of BaSO4 as shown in the
equilibrium equation. Therefore,

That means, in the saturated solution of this salt, [Ba2+] = [SO42-] = 1.1×10-5M.
These values are inserted in the mathematical relationship for solubility prod-
uct constant Ksp.

Solubility product constant Ksp is accepted as a measurement of solubility of

compounds which are slightly water soluble. Knowing the solubility value en-
ables us to make sure if precipitation of the substance is completed or not in a
precipitation process. If the product (multiplication) of concentrations of ions
of a precipitate in a solution is greater than the solubility product constant of
the precipitate, precipitation starts. In this process, the ions of the precipitate
accumulate and form unionized molecules. But if the product of concentrations
of ions of precipitate is less than the solubility product constant of the precipi-
tate, the molecules of precipitate start dissolving. When the solubility product
constant is equal to the product of ions, the solution becomes saturated. There-
fore, an equilibrium is established between the dissolution and precipitation of
Exercise 3-18 the precipitate.
What is the pH value of ferric hydrox-
ide, Fe(OH)3, precipitate when it starts
Example 3-19
to form in a solution that contains As the fluoride ion F- concentration in a solution is 2×10-2 M, what should be
ferric (III) ion with a concentration of the minimum calcium ion concentration in the solution for CaF2 salt to pre-
2×10-10 M? cipitate? (Ksp = 4.9 × 10-11 )

Ksp(Fe(OH)3) = 5×10-38 Solution:

Answer: 4.8 First, the precipitation equation for the calcium fluoride salt is written. Then,
the mathematical relationship for the solubility constant is written.
CaF2(s) ⇌ Ca2+(aq) + 2F-(aq)
As known, the precipitation starts when the product of concentrations of ions
of precipitate is equal to/greater than solubility constant. As the concentration
of fluoride ion in solution is 2×10-2 M, the concentration of calcium ion can be
calculated through inserting this value in the following equation.

112 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

Ksp = (xM) × (2 × 10-2 M)2

4.9 × 10-11 = (x) × (2 × 10-2 M)2
x = 1.23 × 10-7 M = [Ca2+]

3-9-1- Factors Affecting Solubility

There are many factors causing solubility of precipitates to increase or decrease.
The most important of those are temperature, common ion effect and pH effect.
1- The effect of temperature
In order to dissolve a substance in a solution, the solute needs to gain the energy to
break the bonds between the molecules. The substance obtains this energy through
hydration. In the end, the difference between absorbed and released energy (Study
the Thermodynamics chapter) defines the temperature of solution. Practically, the
solubility of slightly soluble substances increases with temperature. But this in-
crease changes from substance to substance.
2- Common Ion Effect
As we have studied before, according to Le Chatelier’s Principle, the solubility of
any weak electrolyte (e.g. slightly soluble salt) decreases when a substance with a
common ion is added to solution. Practically this phenomenon is used to control
the dissolution of precipitates.

Example 3-20
Calculate the molar concentration of barium iodate salt Ba(IO3)2,
A- In pure water,
B- In 0.02 mol/L potassium iodate, KIO3, solution. Then, make a comparison be-
tween results. Ksp = 1.57×10-9

Solution:
First, the dissolution equilibrium equation for Ba(IO3)2 is written. Then, the math-
ematical relationship for solubility product constant is written. The problem is
solved following the steps we have seen in the previous examples.
A-If we assume the molar concentration of Ba(IO3)2 as s,

By solving the equation, s value is obtained.

s = 7.3×10-4 mol/L
The molar solubility of in Ba(IO3)2 pure water is to equal 7.3×10-4 mol/L.
B- KIO3 is accepted as a strong salt which dissolves completely. Therefore, the
concentration of (IO3)- ion is calculated as follows:

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 Chapter - 3

Exercise 3-19 KIO3 → K+ + IO3-

The solubility product constant of 0.02M 0.02M 0.02M

magnesium fluoride, MgF2, salt is We take the molar concentration of Ba(IO3)2 in 0.02 M KIO3 solution as y.
equal to Ksp = 6.5×10-9.

A- Calculate the molar solubility of

this salt in pure water.

B- Calculate its molar solubility in 0.1 As IO3- is the common ion, the concentration of [IO3-] is equal to the sum of
mol/L sodium fluoride, NaF, (strong concentrations of IO3- ions from the ionization of Ba(IO3)2 and KIO3 salts. That
electrolyte) and compare both results. is (0.02 + 2y) mol/L. Therefore,
Answer: A- 1.18×10-3 M
B- 6.5×10-7 M
We can assume the concentration of IO3- ion obtained from Ba(IO3)2 is too
Solubility decreases. small in comparison with IO3- ion obtained from KIO3. That is 2y < 0.02.
Therefore;
Exercise 3-20 (0.02 + 2y) ≈ 0.02 mol/L
A 1L solution contains 0.001 mole Ksp = [Ba2+][IO3-]2 = (y) × (0.02)2 = 1.57 × 10-9
of both of Fe3+ and Al3+ ions. Certain
y = 3.9 × 10-6 mol/L
amount of NaOH solution is added to
it. Show mathematically, which one The molar solubility of Ba(IO3)2 salt in 0.02 mol/L potassium iodate KIO3
of Al(OH)3 and Fe(OH)3 precipitates solution is equal to 7.3×10-4 M. When we compare the results, it is seen that
first and why? the solubility of Ba(IO3)2 salt in pure water is much greater than its solubility in
KIO3 solution (common ion effect). The percentage of solubility of this salt in
Ksp(Al(OH)3) = 3.5×10-34 two different medium can be calculated as follows:
Ksp(Fe(OH)3) = 5×10-38 Molar solubility in pure water
____________________________ 7.3×10-4 mol/L
_______________ 187
____
= ≈
Answer: Fe(OH)3 precipitates first Molar solubility in KIO3 solution 3.9 × 10 mol/L
-6
1
because it needs less amount of OH- In other words, the molar solubility of Ba(IO3)2 salt in 0.02 mol/L KIO3 solu-
ions to precipitate. tion is 187 times less than its solubility in pure water.
3- The pH Effect
Exercise 3-21
The concentrations of many substances depend on the concentration of H+ ion
A solution of 0.01M, 20 mL silver ni-
in solution. The substances which contain hydrogen or hydroxide ions in their
trate (AgNO3) is added to a solution components can be given as examples. e.g Mg(OH)2. The concentrations of
of 0.05M, 80 mL potassium chromate these substances do not change with common ion effect when the pH of solu-
(K2CrO4). Will silver chromate precip- tion changes.
itate?

Ksp(Ag2CrO4) = 1.1×10-12
Answer: Yes, it will precipitate. When an acid is added to the saturated solution of this compound, hydrogen
and hydroxide ions react to yield water molecules and this causes the disrup-
tion of equilibrium shown in the equation. The compound ionizes more (in
other words its solubility increases) in order to compensate the decrease in OH-
ion concentration. When a base is added to the solution in equilibrium of this
compound, its solubility decreases as a result of common ion effect.

114 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

Example 3-21 Exercise 3-22

Calculate the molar solubility of magnesium hydroxide solution with a Calculate the solubility of zinc hy-
pH= 10.5. (Ksp =1.8×10-11) droxide in solutions;

Solution: A- pH=6,

First, the concentration of H+ ion in solution with pH = 10.5 is calculated. B- pH=9.0, then discuss the results.
Then the hydroxide ion concentration in solution is found. Ksp(Zn(OH)2) = 1.2×10-17
Answer: A- 0.12 M,
B- 1.2×10-7 M
Solubility decreases.

That means the concentration of hydroxide ion in solution is equal to 3.1×10-4 Exercise 3-23
mol/L. After writing chemical equation showing dissolution of Mg(OH)2 , we
Two saturated solutions of Mg(OH)2
find the value of s by using molar solubility of Mg(OH)2 in the solution with
pH 10.5. and Zn(OH)2 are put in 1 L contain-
ers separately. How many moles of
NaOH must be added to one of the
solutions in order to equalize the solu-
bility of two solutions?
Ksp(Zn(OH)2) = 1.2×10-17
Then we insert the values above in the mathematical equation showing solu- Ksp(Mg(OH)2) = 1.8×10-11
bility constant as follows: Answer: 1.28×10-5 mole must be add-
ed to Mg(OH)2 solution.

The molar solubility of Mg(OH)2 in solution with pH = 10.5 is equal to

1.9×10-4 M.

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 Chapter - 3

BASIC EQUATIONS

116 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

BASIC CONCEPTS
Electrolyte: A substance which has the capability of conducting electricity through ions it contains.

Weak Electrolyte: A substance whose dilute aqueous solution has a weak conducting capability.

Weak Acid: An acid which cannot ionize completely in aqueous solution.

Weak Base: A base which cannot ionize completely in aqueous solution.

Monoprotic Acid: This is an acid which produces only a single proton from each of its molecules. This acid can be either
strong or weak. Shortly, each of its molecules contains only a single proton which can react.

Polyprotic Acid: An acid which produces one or more protons in different steps. Most of the time, the proton produced
at the final step is weaker than protons produced in previous steps.

Self-ionization of water: This is a chemical reaction. During reaction, a proton is transferred from one water molecule to
another. At the end of this process in pure water, equal numbers of hydronium H3O+ and hydroxide OH- ions are formed.

pH value: This is a method used to express and measure the hydrogen ion concentration. Especially it is found by taking
the negative logarithm of concentrations of hydrogen ions which are equal to 1 M or less. The numeric results of these
values are shown with pH.

Solvolysis: The interaction of solute with solvent molecules.

Hydrolysis: The interaction of solute with water molecules when water is used as solvent.

Common Ion: The phenomenon of decrease in the concentration of a weak electrolyte when a strong electrolyte with
one ion common with the weak electrolyte is added to its solution.

The degree of decomposition: The ratio of the ionized part to the total amount of dissolved part at equilibrium.

Buffer Solution: The aqueous solution of a weak acid and its salt or a weak base and its salt. This mixture has the capa-
bility of resisting pH change when a small amount of strong acid or base is added to solution.

Dissolution: Formation of 1 liter saturated solution from a solvent and a solute (the equilibrium state between solid
substance and solution)

Solubility Product: The product of molar concentrations of ions formed from ionization of a slightly soluble substance
(at equilibrium). (Mole numbers of each ions are taken as exponents.)

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 Chapter - 3

QUESTIONS OF CHATER-3
3-1- In the following equation, equilibrium state is shown between molecules and ions of water:
2H2O(1) ⇌ H3O+(aq) + OH-(aq)
A- Does the equilibrium changes with temperature change?
B- What is the value of solubility constant of water at 25°C? What are the concentrations of hydrogen
and hydroxide ions in pure water?
Answer: B- Kw= 1 × 10-14, [H+] = [OH-] = 1×10-7M
3-2- Find the change in pH value of water after the addition of the following solutions to 1 liter of water.
1. 10 M HCl with 1 mL volume
2. 10 M NaOH with 1 mL volume
Answer: 1. ΔpH= -5 , 2. ΔpH= 5
3-3- Say if the following substances are acidic, basic, neutral and why?
A) NH4Cl B) Na2SO4 C) CH3COOK D) CaF2 E) MgSO4 F) KCl
3-4- How many grams of CH3COOH (M=60g/mol) should be added to 250 mL of water in order to make val-
ue of pH of the solution 2.7? Ka= 1.8 × 10-5
Answer: 3 g
3-5- Circle the correct answer:
1- Find number of mg of barium iodide, BaI2, dissolved in 150 mL of distilled water. (Ksp=1.57×10-9 and
M=487g/mol)
A- 34.4 mg B- 44.4 mg C- 53.4 mg
2- What are the molar concentrations of Na+ and SO42- ions in aqueous solution of 0.4 M sodium sulfate?
A) [Na+]= 0.4M, [SO42-]= 0.4M
B) [Na+]= 0.2M, [SO42-]= 0.4M
C) [Na+]=0.8M, [SO42-]= 0.4M
3- Find the pH and pOH values of 0.05 M sodium hydroxide solution:
A) pH= 1.3, pOH= 12.7
B) pH= 7.0, pOH= 7.0
C) pH= 12.7, pOH= 1.3
4- Find the pOH value of 0.5 M aqueous solution of ammonium nitrate, NH4NO3: (pKb= 4.74)
A- 7.00
B- 9.22
C- 4.78

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 Ionic Equilibrium

3-6- What is the value of pH of the resultant solution after addition of 0.1 M of 10 mL HCl to the following
solutions? Kb(NH3)= 1.8×10-5 , pKb= 4.74
1. 0.1M of 10 mL NaOH
2. 0.1M of 15 mL NaOH
3. 0.1M of 10 mL NH3
4. 0.1M of 15 mL NH3
Answer: 1. pH= 7 , 2. pH= 12.3, 3. pH= 5.28 , 4. pH= 8.96
3-7- Complete the blanks in the following table.
Strength Solution POH PH [OH-] [H3O+]
Strong acid 0.15M HI

Weak acid 0.15M HF

Strong base 0.06M RbOH

Strong base 0.05M Ca(OH)2

Weak base 0.75M NH4OH

Kb(NH4OH)= 1.8×10-5, Ka(HF)= 6.5×10-4

3-8- Complete the blanks in the following table.
Number POH [OH-] [PH] [H3O+]
1 3.84

2 12.61

3 2.90

4 9.47

3-9- Complete the blanks in the following table.

Salt Solubility Ksp pKsp
Ag2S (mol/L) 6.0×10-50

MgC2O4 (g/L) 4.06

Sb2S3 1.35×10-19(mol/L)

ZnSO4 0.02 (g/L)

3-10- As Ka value of propanoic acid (C2H5COOH) is 1.3×10-5, what is the percentage of decomposition of
acid in 0.65 M aqueous solution?
Answer: 0.45%

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 Chapter - 3

3-11- What is the concentration of ammonia [NH3] in a solution in which [NH4+]=0.01 M and [OH-]=1.2×10-5
M at equilibrium? Kb= 1.8×10-5
Answer: 6.67×10-3 M
3-12- Calculate the mass of sodium acetate salt needed to be added into 1 liter 0.125 M acetic acid
(M=82 g/mol) solution to obtain a buffer solution with a pH value of 4.74. pKa= 4.74
Answer: 10.25 g
3-13- Answer the following question.
A- What is the pH value of a buffer solution which is made up of 0.15 M sodium nitrite, NaNO2, and 0.12 M
nitrous acid, HNO2? Ka(HNO2)= 4.5×10-4 .
B- Calculate the pH value of solution after 1.0 g of sodium hydroxide (M= 40 g/mol) added to 1 liter same
buffer solution above.
Answer: A- 3.45, B- 3.62

3-14- What should be the ratio in order to prepare a buffer solution with pH= 9.0 by mixing NH3
and NH4Cl? pKb=4.74
Answer: 1.82
3-15- What is the molar solubility of BaSO4 in its aqueous saturated solution? What is its molar solubility after
adding 1mL 10M H2SO4 to 1L of the same saturated solution? Ksp(BaSO4) = 1.6 × 10-10, 1.6 = 1.26
Answer: 1.6 × 10-8 mol/L, 1.26 × 10-5 mol/L
3-16- Calculate pH and [OH-] values of the following salt solutions: Ka(HCN) = 4.9×10-10 and
Kb(NH3)= 1.8×10-5.
1- 0.1 M sodium cyanide NaCN
2- 0.25 M ammonium nitrate NH4NO3
3- 0.5 M sodium nitrate NaNO3
3-17- If 0.01 M acetic acid ionizes in aqueous solution to 4.2%, calculate the acidity constant of it.
Answer: 1.76×10-5
3-18- In order to make the pH value of 0.15 M 500 mL ammonia solution 9.0, what should be the mass of am-
monium chloride (M=53.5 g/mol)? Kb (NH3) =1.8×10-5
Answer: 7.22 g
3-19- Calculate the molar solubility (mol/L) and solubility (g/L) of silver sulfate, Ag2SO4, salt in the following
solutions.
A- Distilled water,
B- 0.15 M potassium sulfate, K2SO4 (pKsp =4.92 and M= 314 g/mol)
Answer: A) 0.014 M ; 4.396 g/L B) 4.4 × 10-3 M; 1.38 g/L

120 FEZALAR EDUCATIONAL INSTITUTIONS

 Ionic Equilibrium

3-20- As Ksp =1.1×10-12, what is the number of grams of silver chromate, Ag2CrO4 (M=332 g/mol) dissolved in
100 mL distilled water?
Answer: 2.161×10-3 g
3-21- What is the molar solubility of barium chromate, BaCrO4 in 0.1M barium chloride, BaCl2 (strong elec-
trolyte) solution? Ksp (BaCrO4)=1.2×10-10
Answer: 1.2×10-9 M
3-22- What will be the pH value of resulting solution when 20 mL 0.2 M sodium hydroxide, NaOH and 50 mL
0.1 M acetic acid, CH3COOH are mixed? Ka (CH3COOH) = 1.8×10-5
Answer: 5.34
3-23- What will be the pH of the new solution formed when 25 mL 0.2 M sodium hydroxide, NaOH and 50 mL
0.1 M acetic acid, CH3COOH are mixed? Ka (CH3COOH) = 1.8×10-5
Answer: 8.78
3-24- Calculate the pH of the solution obtained from mixing 26 mL 0.2 M sodium hydroxide and 50 mL 0.1
M hydrochloric acid.
Answer: 11.42
3-25- What should be the mass of potassium hydroxide (M=56 g/mol) needed to be added into 200 mL of water
to get a solution with a pH value of 11?
Answer: 0.0112 g
3-26- As percent ionization of 0.1 M hydrocyanic acid, HCN is 0.01%, what is the ionization constant of this
acid?
Answer: 1×10-9
3-27- As Ksp (Zn(OH)2) = 1.2×10-17 , calculate the solubility of zinc hydroxide (M = 99.4 g/mol) in g/L unit and
molar solubility mol/L (molar concentrations of ions from decomposition of salt).
Answer: 1.43×10-6 M, 1.42×10-4 g/L
3-28- Calculate the pH value of solution obtained from diluting 1 mL 13.6 M hydrochloric acid with 1 liter of
water.
Answer: 1.866
3-29- The concentration of calcium (M=40 g/mol) ion in blood plasma is 0.1 g/L. If the concentration of oxa-
late ion in blood plasma is 1×10-7 M, do you expect calcium oxalate CaC2O4 to precipitate?
pKsp = 8.64
Answer: No precipitation occurs.

FEZALAR EDUCATIONAL INSTITUTIONS 121

 Chapter - 3

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122 FEZALAR EDUCATIONAL INSTITUTIONS

 Redox Reactions & Electrochemistry

REDOX REACTIONS and CHAPTER-4

ELECTROCHEMISTRY

ACHIEVEMENTS
After studying this chapter, students
*can define oxidation number and learn to calculate oxidation number in compounds and chemical radicals.
*know the meaning of reduction and oxidation, reducing agent and oxidizing agent; know how to balance
chemical equations including these concepts.
*know the meaning of the following terms:
pole, anode, cathode, electric current, Nerst equation, galvanic cell, electrolytic cell.
*learn the standard cell structure of hydrogen; understand hydrogen standard cell voltage as a criterion to
measure other standard cell voltages.
*understand dissociation and electrolysis processes.
*can describe the structure of cells; write the equations for reactions occurring at poles of cells when they
produce electric current.
*can find out the weight of elements freed by electrolysis at poles and the relationship between the amount of
electric current passing the electrolytic cell.
*describe the relationship between standard cell current and non-standard cell current, and the relationship
between standard free energy change and equilibrium constant.

FEZALAR EDUCATIONAL INSTITUTIONS 123

 Chapter - 4

4-1 PREFACE
Electrochemistry is one of the branches of chemistry. It deals with the chang-
es between chemical energy and electrical energy. During the pass of electric
current, some chemical changes occur and also some chemical reactions cause
production of electric current. Electrochemical processes are reduction and
oxidation reactions. During spontaneous reactions (reactions occur by itself,
without an external force) energy is released. Then this energy is converted to
electrical energy or non-spontaneous reactions can be realized using electrical
energy.
Besides designing different types of cells, dyeing and electrolysis processes
have been derived from electrochemistry. Electrochemical principles are pres-
ent in every part of daily life. Cars, radios, music players, watches, electrical
appliances use chemical reactions in order to supply their energy. The dyeing
of utensils, electrical hardware and appliances; production of electric circuits,
purification of metals and production of some elements are other examples for
reactions that use electrical energy.

4-2 OXIDATION NUMBER

Reduction and oxidation numbers are used to define redox reactions. These
numbers are written over the symbols of the elements which take place in re-
actions. These are called oxidation numbers or oxidation steps. The oxidation
number of each atom in a compound represents the electrical charge (number
of electrons) that this atom gains or loses. The rules for calculation of oxidation
numbers are given below:
1- The oxidation number of free elements is equal to zero.
Na, Be, K, Pb, H2, O2, P4 = 0

2- The oxidation number of a monoatomic ion is equal to the charge on this ion.
Li+, Li = +1, Fe3+, Fe = +3, O2-, O = -2
3- The oxidation number of hydrogen is equal to (+1), the oxidation number of
hydrides is (-1).
The oxidation number of hydrogen in H2O is (+1).
The oxidation number of hydrogen in sodium hydride NaH is (-1).
4- The oxidation number of oxygen is (-2). The oxidation number of oxygen in
peroxides is (-1).
The oxidation number of oxygen in H2O is (-2). The oxidation number of oxy-
gen in hydrogen peroxide H2O2 is (-1).

124 FEZALAR EDUCATIONAL INSTITUTIONS

 Redox Reactions & Electrochemistry

5- A-The oxidation number of Group IA element in a compound is +1.

Li, Na, K, Rb = +1

B- The oxidation number of Group IIA element in a compound is +2.

Be, Mg, Ca, Sr = +2
Cr2+ Cr3+
C- The oxidation number of Group IIIA element in a compound is +3.
B, Al, Ga, In = +3

6- The oxidation number of halogens Group VIIA element in a compound is -1.

F, Cl, Br, I = -1
For the atoms which are not mentioned above, the following rules can be used:
Rule 1: The sum of the oxidation numbers of all of the atoms in a neutral com-
pound is 0.
Na = +1 and Cl = -1 in NaCl
According to this rule, (+1) + (-1) = 0
Rule 2: The sum of the oxidation numbers in a polyatomic ion is equal to the Cr6+
charge of the ion.
Cr4+
In H2PO compound O = -2 and P = P and H= +1
4
-

According to the rule; {2×(+1)}+(P)+{4×(-2)}= -1

Here we find that the oxidation number of phosphorus is P=+5. Atoms which have
more than one oxidation numbers show different colors for different oxidation
numbers (Figure 4-1). Table 4-1 shows the oxidation numbers of elements.
Example 4-1
Figure 4-1
Find out the oxidation numbers of atoms in the following compounds, ions and The color of solutions which
elements. have different chromium salts
SO2 , KCl , Mg2+ , PO43- , BaO , F2 are different depending on the
oxidation number of the chro-
Solution: mium.
F2 : F=0 (According to Rule 1)
BaO: We can find out the oxidation number. of Ba according to Rule 1. O = -2,
thus (Ba) + (-2) = 0 so Ba = +2
PO43- :We can find out the oxidation number of (P) according to Rule 2. O = -2
(P) + {4×(-2)} = -3 thus P = +5.
Mg2+ : Mg = +2 (According to Rule 2)
KCl : Cl = - 1 and K = +1 (According to Rule 2)
SO2 : We can find out the oxidation number of S according to Rule1. Exercise 4-1
O = -2, (S) + {2×(-2)} = 0 thus S = +4. Find the oxidation number which
are in red following ion and com-
pounds.
4-3 REDUCTION AND OXIDATION (REDOX) REACTIONS MnO4-, K2Cr2O7, NaIO3 ,H2SO4,
Reduction and oxidation reactions are one of the most important types of reac- H2CO3, HPO42-
tions. The energy released from combustibles, electric current from batteries and
oxidation of iron are examples for these reactions (Figure 4-2).

FEZALAR EDUCATIONAL INSTITUTIONS 125

 Chapter - 4

Table 4-1
Redox reactions occur via transfer of electrons. The first definition of redox
reactions was made as “loss or gain of oxygen”. This definition is correct but
incomplete as it is true for only a number of compounds. Today redox reactions
are defined as follows:
Oxidation:
It is the chemical change following loss of electrons of an atom. As a result of
this, an increase occurs in oxidation numbers. Below, the exothermic reaction
of Na and Cl ions in which crystal latticed solid forms is given.
2Na(s) + Cl2(g) → 2NaCl(s)
The formation of sodium ions is a result of oxidation process. Because each
sodium atom loses an electron in order to become sodium ion. Oxidation state
is shown by writing oxidation number on the atom or ion.

126 FEZALAR EDUCATIONAL INSTITUTIONS

 Redox Reactions & Electrochemistry

Na0 → Na+ + e-
By this equation, we see that the oxidation number of sodium in free state has
changed from 0 to (+1). In other words, sodium atom was oxidized to sodium
ion and its oxidation number has increased by (+1).
Reduction:
It’s a chemical change. An atom or group of atoms gain/s electrons. At the end
of reaction, the oxidation number of the element decreases. According to this,
in the reaction above, during interaction of sodium and chloride each chlorine
atom gains an electron and the oxidation number decreases to (-1). The process
is accepted as a reduction reaction.
Cl20 + 2e- → 2Cl-
Reduction occurs in the reaction in which oxidation number is reduced. Chlo-
rine atom whose oxidation number decreases from 0 to -1 is reduced to chlo-
ride ion. In a reaction, reduction does not realize without oxidation. Because
along with a reduced atom there must be an oxidized one. The number of elec-
trons which are gained during reduction is equal to the number of electrons
lost during oxidation. As shown in the equation below, the general equation of
redox reaction is obtained from sum of reduction and oxidation reaction equa-
tions. As the number of lost and gained electrons must be equal, electrons are
not shown in the total equation. This reaction is called as oxidation-reduction
(redox) reaction. During this reaction electrons are transferred from one atom
to another. According to this, the atom that loses electron is a reducing agent,
the atom that gains electron is an oxidizing agent. Therefore, in this reaction,
Figure 4-2
sodium atom is the reducing agent, whereas chlorine atom is the oxidizing
A) Combustion reaction of meth-
agent. ane gas is a redox reaction.
2Na + Cl2 → 2Na + 2Cl+ -
CH4(g) + 2O2(g) →
If we sum up what is told above, knowing oxidation numbers allows us to CO2(g) + 2H2O(l) + Energy
know if a reaction is a redox reaction. Let us take a look at the reaction between
phosphorus pentachloride and water: B) Oxidation reaction of iron (rust-
P5+ Cl5- + 4H2+ O2- → H3+ P5+ O42- + 5H+ Cl- ing of iron) is an oxidation-reduc-
As there is no change occurs in the oxidation numbers of elements, this re- tion reaction.
action cannot be called as a redox reaction. But in the following reaction of 4Fe(s) + 3O2(g) → 2Fe2O3(s) + Energy
copper and nitric acid, we can make some comments:
Cu0 + 4H+N5+O32- → Cu2+ (N5+ O32-)2 + 2N4+ O22- + 2H2+ O2-
From the change in oxidation numbers of copper and nitrogen, we can easily
say that this is a redox reaction. The oxidation number of copper atom has
changed from 0 to +2. Therefore it has been oxidized by losing 2 electrons.
Meanwhile, the oxidation number of nitrogen atom has been changed from
(+5) to (+4). That means it has been reduced by gaining 1 electron. Carbon and
sulfur react in order to yield carbon sulfide. In this reaction, as seen at the side,
carbon is oxidized and sulfur is reduced.
In redox equations, we can explain the loss or gain of electrons by dividing it in

FEZALAR EDUCATIONAL INSTITUTIONS 127

 Chapter - 4

two parts: The half of the reaction is oxidation and the other half is reduction.
Therefore, we can divide the reaction of sodium and chlorine into two:
2Na0 + Cl20 → 2Na+ + 2Cl-

Na0 → Na+ + e- is oxidation half reaction.

Cl20 + 2e- → 2Cl- is reduction half reaction.
When two halves of the reaction is added up, firstly the number of electrons
lost need to be equal to the number of electrons gained. According to this, in
order to obtain the following equations, the half oxidation reaction is multi-
plied by 2:
2Na0 → 2Na+ + 2e-
Cl20 + 2e- → 2Cl-
After eliminating equal numbers of electrons on both sides, by adding two
equations, we get the general reaction below:
2Na0 + Cl20 → 2Na+ + 2Cl-
The oxidation number of sodium has increased from 0 to +1. Therefore, the
process is called as oxidation. The oxidation number of chlorine has decreased
from 0 to (-1). So the reaction is called as reduction. Thus, the total reaction is
called as an oxidation-reduction reaction, shortly a redox reaction.

Example 4-2
In the following reactions, specify the reduced and oxidized atoms. Also
write down the reduction and oxidation half reactions.
1) Cl2 + 2l- → 2Cl- + l2
2) Mg + Fe2+ → Mg2+ + Fe

Solution:
1) Cl2 + 2l- → 2Cl- + l2

2l- → l2 + 2e- is oxidation half reaction.

Cl20 + 2e- → 2Cl- is reduction half reaction.

When both sides of the reaction are added up, the number of lost and gained
electrons must be equal. We can only write down the general reaction (total
reaction) when number of electrons are equal.
Cl2 + 2l- → 2Cl- + l20

The oxidation number of iodine has increased from (-1) to 0. Therefore this
is called oxidation. The oxidation number of chlorine has decreased from 0 to
(-1). This is called reduction. Thus, this reaction is a redox reaction.

128 FEZALAR EDUCATIONAL INSTITUTIONS

 Redox Reactions & Electrochemistry

2) Mg + Fe2+ → Mg2+ + Fe
Mg0 → Mg2+ + 2e- is oxidation half reaction.
Fe2+ + 2e- → Fe0 is reduction half reaction.
Firstly we need to make sure the number of electrons lost and gained must be equal Exercise 4-2
In the following reactions,
when they are summed up, we get the general reaction:
specify the reduced and oxi-
Mg + Fe2+ → Mg2+ + Fe dized atoms. Also write down
The oxidation number of magnesium has increased from 0 to (+2). This process is the reduction and oxidation half
called oxidation. As the oxidation number of iron has decreased from (+2) to 0, this reactions.
is a reduction. Therefore this reaction is a reduction reaction.
1) Zn + Cu2+ → Zn2+ + Cu
4-4 REDUCING AND OXIDIZING AGENTS
2) Mg + 2HCl → MgCl2 + H2

4-4-1 Reducing Agent

A reducing agent is a substance which can reduce another substance. It loses elec-
tron/s and its oxidation number increases. Therefore the reducing agent is oxidized.
For example, in the reaction of copper element with concentrated nitric acid:

Cu0 + 4HN5+O3 → Cu2+ (NO3)2 + 2N4+ O2 + 2H2O

Copper is the reducing agent as it has been oxidized by losing 2 electrons. The ox-
idation number increases by from 0 to +2.

4-2-2 Oxidizing Agent

An oxidizing agent is a substance which can oxidize another substance. An oxi-
dizing agent gains electron/s. During redox reactions, their oxidation numbers de-
crease. Therefore the oxidizing agent is reduced. In the example above, nitric acid
is the oxidizing agent. Because the oxidation number of nitrogen in the acid is
reduced to 4 from 5 in nitrogen dioxide by gaining an electron. In the same manner,
the substance in a reduction reaction is the oxidizing agent.

The Oxidizing Agent The Reducing Agent

A substance which takes place in re- A substance which takes place in
duction reaction and causes another oxidation reaction but causes another
substance to oxidize. substance to reduce.

Example 4-3
Specify the oxidizing and reducing agents in the following reactions:
1) Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s)
2) Cu(s) + 2AgNO3(aq) → Cu(NO3)2(aq) + 2Ag(s)

FEZALAR EDUCATIONAL INSTITUTIONS 129

 Chapter - 4

Exercise 4-3 Solution:

Specify the oxidizing and reducing 1) Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s)
agents in the following reactions:
Zn → Zn2+ + 2e- Zn: It has undergone oxidation so it’s reducing agent.
1) 2C(s) + O2(g) → 2CO(g) Cu2+ + 2e- → Cu Cu: It has undergone reduction so it’s oxidizing agent.
2) Mg(s) + Cl2(g) → MgCl2(s) 2) Cu(s) + 2AgNO3(aq) → Cu(NO3)2(aq) + 2Ag(s)
3) Mg(s) + Fe2+(aq) → Mg2+(aq) + Fe(s) Cu → Cu2+ + 2e- Cu: It has undergone oxidation so it’s reducing agent.
Ag + e → Ag
+ -
Ag: It has undergone reduction so it’s oxidizing agent.

4-5 ELECTROCHEMICAL CELLS

When we study redox reactions, we see that some of those occur sponta-
neously. For example, in the reaction of a piece of solid magnesium and dilute
hydrochloric acid, a salt forms and hydrogen gas evolves.
Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)
However, some redox reactions do not occur spontaneously. For example, wa-
ter dissociates to its components, hydrogen and oxygen, only when energy giv-
en from outside. Therefore, what is the relationship between electrical energy
and reactions that occur spontaneously or non-spontaneously? And what is the
relationship between these reactions and electrochemical cells? Electrochemi-
cal cells are made up of two poles: One is positive pole or anode. This pole is
the source of electrons that undergo oxidation. The second pole is the negative
one which is called cathode. This pole is the place that reduction occurs and
electrons are transferred from positive pole via outer circuit. Both poles are
inside solution. The components of solution take place in the reduction and
oxidation reactions occur at the surfaces of poles.
Electrochemical cells are divided into two: Galvanic cells and concentration
cells

4-6 GALVANIC CELLS

These are cells where chemical energy is transformed into electrical energy
during spontaneous chemical reaction. This kind of cells is called galvanic or
voltaic cells. These names are taken from two Italian scientists. One is Luigi
Galvani and the other is Alessandro Volta. These two scientists were the first
people who designed these cells. Batteries are one of the types of galvanic cells.
Let’s study the following example before we go into what is going on inside
galvanic cells. When a zinc rod is dipped into copper sulfate solution, it starts
to corrode and disappear. The concentration of zinc ions increases. That means
a spontaneous reaction occurs. At the same time, brownish copper element
starts plating zinc rod as a spongy layer. Some of the copper settles at the bot-
tom. The blue color of the solution starts to disappear due to the decrease in the
concentration of copper ions and finally it becomes colorless (Fig. 4-3)as in the
following reaction.
Zn(s) + Cu2+SO42-(aq) → Zn2+SO42-(aq) + Cu(s)

As it seems SO4-2 ions hasn’t changed at all during oxidation (in other words
they haven’t joined the reaction) Therefore we can simply rewrite the reaction
above as follows: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

130 FEZALAR EDUCATIONAL INSTITUTIONS

 Redox Reactions & Electrochemistry

Zinc

Copper(II)
Sulfate Solution

Figure 4-3
The reaction that occurs when
zinc dipped into copper sul-
fate solution.

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

The most famous and simplest Galvanic cells are Daniell cells (Figure 4-4 ).
A zinc rod is dipped into zinc sulfate ZnSO4 solution. The cell depends on Zn,
Zn+2 oxidation and Cu+2 , Cu reduction. This event occurs in two different con-
tainers. Electrons are displaced between two poles through an external wire.
Zinc and copper rods are called electrodes. The poles of cell are the immersed
or the contacting pole with ions in the solution. The battery cell formed with
copper and zinc rods dipped into ZnSO4 and CuSO4 solutions is called the Dan-
iell cell. According to the definition above, positive pole (zinc rod) is called as
anode. This pole is the place where oxidation occurs. Negative pole is called
as cathode.

Figure 4-4
Daniell Galvanic Cell

FEZALAR EDUCATIONAL INSTITUTIONS 131

 Chapter - 4

At this pole reduction occurs. During this process, electrons are observed to be
transferred through external wire from anode to cathode (copper rod). These
electrons cause copper atoms accumulate over negative pole’s surface by react-
ing with copper ions Cu+2 in solution. The reduction and oxidation reactions
occurring in the Daniell cell are called half cell reactions at poles. These are:
Zn(s) → Zn2+(aq) + 2e- Half cell reaction / Zn pole (anode) oxidation
Cu2+(aq) + 2e- → Cu(s) Half cell reaction / Cu pole (cathode) reduction
We see that each zinc atoms have lost 2 electrons (undergone oxidation) to
yield Zn+2 ion whereas each Cu+2 ions have gained 2 electrons (undergone
reduction) to yield Cu atom. The general reaction of the cell is obtained by
adding both half reactions after making equal the number of gained and lost
electrons. (Here we see that the numbers of gained and lost electrons are equal.)
General reaction: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
The most important point here that needs attention is if copper sulfate and zinc
sulfate solutions were not in different containers, Cu2+ ions would react with
zinc rod directly, as mentioned above. In this case, there would be no electricity
produced. In order to complete the electric circuit, a conducting medium that
allows negative and positive ions to be transferred from one pole to the other is
required. This conducting medium is called as salt bridge. The bridge is formed
from a turned down U-shaped glass tube. Inside the tube there is an inert solu-
tion which does not change chemically during the process. The solution con-
tains ager substance. (Ager is a natural, sticky substance. It has different uses.
When heated it liquefies, it solidifies at room temperature.) The compounds
which are used while filling the salt bridge are K2SO4, KNO3, KCl. A cell re-
action starts spontaneously and continues until zinc rod or the concentration of
copper ions is used up completely. As a result of zinc atoms change into Zn2+
ions, electrons are transferred from positive zinc pole (zinc atoms) to copper
pole through external wire. Here ions undergo reduction. The SO42- sulfate ions
remaining in the solution pass to the zinc sulfate solution through salt bridge
(because of increase in the number of positive charges in solution) Potassium
K+ ions pass to copper sulfate through salt bridge (in simple terms, negative
ions pass to positive pole anode. Positive ions pass to negative pole cathode.)
Conduct of electricity occurs by transfer of electrons at external circuit (wire).
It occurs at inner circuit (salt bridge) through transfer of ions.

Example 4-4
As the following reaction occurs spontaneously at the given galvanic cell,

Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)

A- Write down both half cell reactions.

B- Explain the direction of ion flow along outer wire and direction of ion
movement through salt bridge which is full of KNO3 solution.

132 FEZALAR EDUCATIONAL INSTITUTIONS

 Redox Reactions & Electrochemistry

Solution:
A)
Cu(s) → Cu2+(aq) + 2e- Half cell reaction / Cu pole (anode) oxidation
2Ag+(aq) + 2e- → 2Ag(s) Half cell reaction / Ag pole (cathode) reduction

B) Electrons flow from anode (copper rod) towards cathode (silver rod) via
outer wire. Positive ions K+ move towards negative pole “cathode” while nega-
tive ions NO3- move towards positive pole “anode” through salt bridge.

4-7 POTENTIAL OF GALVANIC CELL

Electric current flows from anode to cathode due to the potential difference be-
tween poles. This flow of electric current is similar to fall of water at a waterfall
because of its potential or similar to flow of gas from high-pressure region to
low-pressure region. This potential occurs between electrodes and the ions of
solution. It is divided into two:
1-Oxidation Potential: The tendency of matter losing its electrons
2-Reduction Potential: The tendency of matter gaining electrons
The potential between two poles of galvanic cell is called as cell potential and
shown with E. Cell potential is also called as electromotive force and shown
with emf. Contrary to the meaning of the term, here potential is named instead Figure 4-5
of force. The cell potential is measured by a voltmeter (Fig. 4-5). As we will A voltmeter is used measure cell
study later, cell potential depends not only on the properties of electrodes or potential or electromotive force.
ions but also on concentrations of ions and temperature at which cell works.
Cell potential is defined as the electrical potential difference between elec-
trodes in a galvanic cell. Cell potential is shown with Ecell symbol. Therefore,
cell potential is a measurement of motive force of the reaction which occurs
in a cell. Cell potential depends on the potential of poles at which oxidation
(anode) and reduction (cathode) occurs. If we show oxidation potential with
Eox and reduction potential with Ered, cell potential is the sum of oxidation and
reduction potentials of the cell.
1) Ecell = Eox + Ered

FEZALAR EDUCATIONAL INSTITUTIONS 133

 Chapter - 4

As oxidation occurs at anode, we can use Eanode symbol instead of Eox. Similarly,
reduction occurs at cathode, so for reduction potential we can use Ecathode instead
of Ered. Therefore, we can rewrite equation 1 above as follows:
2) Ecell = Eanode + Ecathode

Under standard conditions, 25°C and 1 atm pressure, when cell potential is
measured for the concentrations of solution at two poles are the same (1 M or 1
mol/L), this measured value is called as standard cell potential. It is shown with
E°cell. Under same conditions, the potentials measured at electrodes are called
standard electrode potential and shown with E°cathode and E°anode symbols. Thus,
equation 2 can be rewritten under standard conditions.

3) E°cell = E°anode + E°cathode

Electrical potential unit is volt and its symbol is (V).

4-7-1 Measurement of Cell Potential

As we studied above, in order to measure standard cell potential (E°cell), anode
and cathode potentials need to be measured under standard conditions.
The question is how the potential of a single electrode can be measured as a cell
cannot be set up with a single electrode and its potential cannot be measured.
Therefore, a reference electrode is necessary. A reference electrode is used to
measure other electrode potentials. There are different types of electrodes used
as reference. The most important of those is standard hydrogen electrode.

4-7-2 Standard Hydrogen Electrodes

Standard hydrogen electrode is chosen as a reference electrode (with a known
standard potential). Hydrogen electrode is chosen from other elements with
respect to its chemical activity. Therefore, it can be used as anode or cathode
pole. Standard hydrogen electrode is made up of a glass tube. Into 1M solution
(as HCl) containing H+ ions, hydrogen gas is pumped under 1 atm pressure
and 25°C. At the bottom of the glass tube, a piece of platinum is placed. That
piece of platinum is attached to a platinum wire. The reason why platinum is
used with this kind of electrodes is that it never oxidizes or reduces under any
conditions. But platinum performs two duties:
A- It supplies a surface on which hydrogen molecules can dissociate.
B- It supplies a method to conduct electricity through outer circuit.
Figure 4-6 shows a standard hydrogen electrode. It is shown with (SHE) sym-
Figure 4-6 bol. According to IUPAC, the potential of standard hydrogen electrode is ac-
Standard hydrogen electrode cepted as (E°H2 = 0.0 V). If standard hydrogen electrode is used as anode (oxi-
dation), the reaction which occurs on it is as follows:
H2(g) → 2H+(aq) + 2e- E°anode = 0.0 V
But if it is used as cathode, the reaction is as follows:
2H+(aq) + 2e- → H2(g) E°cathode = 0.0 V

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 Redox Reactions & Electrochemistry

4-7-3 The Potentials of Standard Electrodes

We can use standard hydrogen electrode to measure standard potentials of oth-
er electrodes. When this electrode is connected with any other electrode to set
up a cell, the standard cell potential is equal to the sum of element’s standard
electrode potential and standard hydrogen electrode potential. As (SHE) poten-
tial is equal to zero that means element’s standard electrode potential is equal to
cell potential. Over this fundamental, standard oxidation potentials of elements
were measured. These potentials were put in a chart named as Standard Reduc-
tion Potentials Chart. Table 4-2 shows reduction half reactions and standard
reduction potentials of different electrodes.
E°cell = E°anode + E°cathode
It is observed that E°cell value of this cell is +0.763 V. As (SHE) potential
is equal to zero, then:
E°cell = E°anode + E°cathode
0.763 V = E°anode + 0.0 V
E°anode = + 0.763 V

That means standard oxidation potential of zinc is equal to +0.763 V. There-

fore, standard reduction potential of this electrode is equal to -0.763 V. In other
words, standard cell potential is equal to standard potential of zinc electrode.
Because the other electrode is (SHE).
Standard Oxidation Potentials Table of elements is used to compare potentials
when elements are used as oxidizing and reducing agents. Because reduction
potential values are accepted practically as a measurement of reduction and
oxidation capabilities. We need to learn following important points about the
table to use it in calculations. Exercise 4-4
The cell consists of anode which is
1- Standard Potential Values of electrodes in table 4-2 show their standard re- hydrogen pole and cathode which is
duction potentials. copper pole. Calculate the standard
reduction potential of copper pole.
2- Standard reduction potentials reduce as we scroll down the table. This means Standard cell potential= +0.337 V
their oxidation properties increase. In other words, their strength as reducing
agents increase. At the top, fluorine element is placed with the highest reduc-
tion potential that is +2.87 V
+ -
F2(g) + 2e → 2F (aq)
- -
E°cathode = +2.87 V
For Lithium element -3.04 \ Reduction potential decreases downwards
the table
Li+(aq) + e- → Li(s) E°cathode = -3.04 V

Therefore, as lithium is the hardest reduced substance, Li+ is accepted as the

weakest oxidizing agent.
Contrary to this, as fluorine is the least oxidized substance, it is the weakest Answer: +0.337V
reducing agent.

FEZALAR EDUCATIONAL INSTITUTIONS 135

 Chapter - 4
Table 4-2 Standard Reduction Potentials of elements in volt unit measured
Potentials increase in oxidizing agents at 1M concentration at 25 0C

Potential of reducing agents increase

136 FEZALAR EDUCATIONAL INSTITUTIONS

 Redox Reactions & Electrochemistry

3-The standard cell potential of any cell of which one of its poles is standard
hydrogen electrode, equals to element’s standard electrode potential as in the
example above.
4-The potential of an oxidation reduction (loss of electron) is the negative of
the potential for a reduction potential (gain of electron). For example, the po-
tential of reduction half reaction of lithium electrode is -3.04 V. Therefore,
potential of oxidation half reaction of this electrode is +3.04V.
Li+(aq) + e- → Li(s) E°cathode = -3.04 V
Li(s) → Li+(aq) + e- E°anode = +3.04 V

4-7-4 Standard Cell Potential

The following points must be considered while calculating standard cell po-
tential:

1- The element which has the lowest standard reduction potential is chosen as
anode pole. Similarly, the element with the highest reduction potential is cho-
sen as cathode pole.

2- The number of electrons lost at anode (oxidation) must be equal to the num-
ber of electrons gained at cathode (reduction). When they are not equal, they
need to be made equal by taking least common multiple of number of electrons.
Then by eliminating electrons from both sides of half reactions, general cell Attention:
reaction is written. Characteristic property does not
depend on amount of substance.
3- If the number of electrons lost in reduction is not equal to the number of
electrons gained in oxidation; both sides of equations are multiplied with a
certain number. But standard electrode potentials remain unchanged. Because
potential is a characteristic property which does not depend on the amount of
substance. Potential depends only on the concentrations of ions in electrode
solutions. For example:
I2(s) + 2e- → 2I-(aq) E°I /I = 0.53 V
-
2

2I2(s) + 4e- → 4I-(aq) E°I /I = 0.53 V

-
2

4- Both half cell reactions are reversible reactions. Each electrode can be used
as anode or cathode depending on the conditions they are used.

5- In order to find out standard cell potential value E°cell, both half-cell reactions
at electrodes are written. At the end of the reactions, standard cell potential val-
ues are written. Then while calculating E°cell, the following relationship is used.
E°cell = E°anode + E°cathode
If standard reduction potentials are given directly taken from the table, they
must be used as is;
E°cell = E°cathode - E°anode
That means standard cell potential describes oxidation potentials of both elec-
trodes.

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 Chapter - 4

6- If the value of standard cell potential is positive (E°cell = +), the reactions
at poles occur spontaneously. But if the value of E°cell is negative (E°cell= -),
the reactions at poles do not occur spontaneously and energy must be given
externally.

Example 4-5
Write down both Daniell cell half reactions and calculate standard cell poten-
tial. As standard reduction potentials E°Cu2+/Cu= +0.34V and E°Zn2+/Zn= -0.76

Note: To show standard potential is a reduction potential E°Cu2+/Cu symbol is

used.
Solution
When we examine standard reduction potential values, we see that we need
to choose copper pole as cathode because this pole has the highest standard
reduction potential. We need to use zinc pole as anode because this electrode
has the lowest standard reduction potential.

Zn(s) → Zn2+(aq) + 2e- E°anode = +0.76V

Cu2+(aq) + 2e- → Cu(s) E°cathode = +0.34V

Here what needs attention is that when we use zinc as anode, we have to
reverse the sign of standard reduction potential. If the number of lost elec-
trons is equal to the number of gained electrons, from the sum of two half cell
reactions, we get the general cell reaction as follows:

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 Redox Reactions & Electrochemistry

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Exercise 4-5
E°cell = E°anode + E°cathode Calculate the standard cell potential
E°cell = (+0.76 V) + (+0.34 V) = 1.10 V which consists of Cd pole dipped
in 1M solution of Cadmium nitrate
and Cr pole is dipped in 1M solution
Note: To calculate standard Daniell cell potential, we can use the following of chromium nitrate. If you know
relationship: standard reduction potential;
E°cell = E°cathode - E°anode E°Cd2+/Cd= -0.40 V
E°Cr3+/Cr= -0.74 V
If we take the standard reduction potentials from the chart directly, If we take
the standard reduction potentials from the chart directly, Answer: +0.34 V

E°cell = (+0.34 V) - ( - 0.76 V) = 1.10 V

4-7-5 Types of Electrodes

Here we will mention types of electrodes widely used in setting up galvanic
cells.

1- Metal Electrodes and Metal Ion

Exercise 4-6
Do the oxidation and reduction reac-
This kind of electrodes are obtained by dipping a metal rod into the solution
tions expressed with equations below
containing the metal’s ions. For example, zinc electrode which is dipped into
occur spontaneously?
zinc sulfate solution. The interaction of (Zn/Zn+2) electrode as anode or cathode
Standard reduction potentials:
is as follows:
E°Co2+/Co= -0.28 V
E°Ni2+/Ni= -0.25 V
Zn2+(aq) + 2e- → Zn(s) Reduction (cathode) E°Fe2+/Fe= -0.44 V
Zn(s) → Zn2+(aq) + 2e- Oxidation (anode) E°Au3+/Au= +1.50 V

1) Ni(s) + Co2+(aq) → Ni2+(aq) + Co(s)

2- Gas Electrodes
They are set up by pumping gas into a glass tube filled with solution containing 2) 3Fe(s) + 2Au3+(aq) →
the ions of the gas under a certain pressure. As gas does not conduct electricity, 3Fe2+(aq) + 2Au(s)
this electrode will supply a conducting medium for electricity. Generally, plat- Answer:
inum strip which does not have tendency to react is used inside the glass tube. 1- Ni-Co reaction does not occur
For example, into the solution like HCl which has H+ ions, hydrogen gas is spontaneously.
pumped under 1 atm pressure. The anode reaction of hydrogen electrode over 2- Fe-Au reaction occurs sponta-
the piece of platinum is as follows: neously.

H2(g) → 2H+(aq) + 2e- Oxidation (anode)

In a different way, chlorine gas is pumped into a solution of NaCl or HCl
which has chloride ions. The reaction of chlorine cathode reaction over the
piece of platinum is as follows:

Cl2(g) + 2e- → 2Cl-(aq) Reduction (cathode)

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 Chapter - 4

3- Electrodes used in Reduction and Oxidation Reactions

They are set up by dipping a graphite rod or platinum strip into a solution
containing ions of an element which has double oxidation state. For example,
it is set up by dipping platinum strip into the solution containing Fe2+ and Fe3+
(or Sn4+ and Sn2+ ) ions. When this electrode is used as anode, oxidation reac-
tions can be written as follows:
Fe2+(aq)→ Fe3+(aq) + e-
4-7-6 Line Notation of Galvanic Cells
Generally, in order to express a galvanic cell, notation method is used. There-
fore, we need to symbolize the poles. Later, they will be used to express the
cell. The electrode is written as element electrode/element ion. For example,
let’s consider zinc electrode which is dipped into zinc sulfate solution where
reduction reaction occurs. It is expressed as follows:
Zn2+(aq) + 2e- → Zn(s) Reduction (Cathode)
It is expressed as seen in half cell equation. Firstly, the symbol of metal ion
is written. Next to it, in parentheses, its molar concentration is written then a
vertical line is drawn and symbol of metal is written. It is as follows:
Zn2+ (1M) ǀ Zn

or for oxidation reaction:

Zn(s) → Zn2+(aq) + 2e-
For this situation, firstly the symbol of the metal is written. Then a vertical line
is drawn and the symbol metal ion is written. Next to it, its molar concentration
is written in parentheses. All these are as seen in half cell reaction.
Zn ǀ Zn2+ (1M)

Vertical line shows the phase boundary. If attention is given, zinc is in solid
phase and zinc ions in aqueous solution are in liquid phase. Therefore, in order
to divide two phases, a vertical line is drawn. The concentration of the solution
is written after the sign of the ion. Because 1M shows the standard concentra-
tion.
As an example for expressing gas electrodes by notation, we can give the nota-
tion of hydrogen electrode.
In the following oxidation reaction:
H2(g) → 2H+(aq) + 2e- Oxidation (anode)

In order to express the electrode, as in the order in the equation, half

cell components are placed. Firstly hydrogen gas and next to it the value
of gas pressure is written (this is for gases only). Then the symbol of gas
ion and next to it, its molar concentration is written.
Pt ǀ H2 (1atm) ǀ H+ (1M)
As gas cannot conduct electricity, to conduct it, platinum strip is used.
If it is used as anode, it is written in the beginning of the notation, if it is
used as cathode, it is written in the end. In the electrodes used in

140 FEZALAR EDUCATIONAL INSTITUTIONS

 Redox Reactions & Electrochemistry

reduction and oxidation reactions, for the oxidation reaction, the nota-
tion of the electrode containing Fe+2, Fe+3 ions will be as follows:
Fe2+(aq)→ Fe3+(aq) + e- Oxidation reaction (anode)

Pt ǀ Fe2+ (1M) ; Fe3+ (1M)

In this kind of reactions, as they do not conduct electricity just like gases, plati-
num strip needs to be dipped into the solution. While the electrode is expressed
by writing, the symbol of platinum, Pt is written just as the gas electrode is
expressed. As both ions are found in the same solution, a semicolon is put be-
tween symbols of two ions.
As we have learnt expressing electrodes by notation, we can easily express
a cell. For this, we join anode (oxidation) and cathode (reduction) poles. To
express by notation, on the left hand side, the reaction in anode is written. The
reaction in cathode is written on the right hand side. Between those two parallel
vertical lines are drawn to express salt bridge in the cell.
As an example, we express the Daniell cell with general reaction given:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
We can express the cell as follows:
Zn ǀ Zn2+ (1M) ǀǀ Cu2+ (1M) ǀ Cu
Oxidation reaction in anode II Reduction reaction in cathode
(Two vertical lines between expresses the salt bridge.)

Example 4-6
Express the cell in the figure by notation. Then write down both half cell
reactions.
Solution
The sum of two half cell reactions gives general reaction and it is as follows:
Zn(s) → Zn2+(aq) + 2e- Oxidation reaction (anode)

2H+(aq) + 2e- → H2(g) Reduction reaction (cathode)

The sum of two half cell reactions gives general reaction and it is as
follows:
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)
The notation of this cell is below:
Zn ǀ Zn2+ (1M) ǀǀ H+ (1M) ǀ H2 (1atm) ǀ Pt

4-7-7 The Cell Potential E, Gibbs Free Energy (∆G) and

Equilibrium Constant
As we know, galvanic cells transform chemical energy into electrical energy.
The electrical energy (joule unit) the cell produces is equal to the multiplication
of cell potential E°cell (volt unit) with total charge that passes through cell (C)
(coulomb unit).

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 Chapter - 4

Electrical Energy (J) = Cell potential(V) × Total Charge(C)

Attention: Therefore, joule unit is equal to the multiplication of Volt unit (V) with electri-
Unit of coulomb (C) multiple cal charge unit (C).
unit of Volt (V) equals to Unit 1J = 1V × 1C
of Joule (J) The total charge passing through the cell is equal to the multiplication of mole
number of electrons (n) and charge of 1 mole of electron which called Faraday
(and shown with F). In other words, the total charge passing through the cell
is equal to (n×F). As known, 1 mole contains as many charges as Avogadro
number (NA). Therefore, Faraday (F) is equal to the multiplication of electron
Exercise 4-7 charge and Avogadro number.
The general reaction of a galvanic F = electron charge (e-) × Avogadro number (NA)
cell is as follows: F = NA (mol-1) × e- (C)
Cl2(g) + 2Ag(s) → 2Cl-(aq)+ 2Ag+(aq) Value of Avagodros’ number (NA ) = 6.023×1023
If we insert e- =1.6×10-19 (C) in the equation, we get the following:
Express the cell by notation under F = 6.023×1023 (mol-1) × 1.6×10-19(C) = 96478 C/mol.e-
standard conditions. Later, write In chemical calculations, this value is taken as 96500 C/mol.e-. Therefore, elec-
down the oxidation and reduction trical energy is equal to:
reactions. Electric charge(J) = Total charge (nF) × Cell potential (E°cell) = nFE°cell
Electrical energy produced in Galvanic cells (nFE°cell) is equal to reverse sign
of free Gibbs energy ∆G°.

Therefore:
1) ∆G° = -nFE°cell
As known, when the free energy is negative, reaction occurs spontaneously. In
the relationship (1) above, to have a negative free energy ∆G°, the sign of E°cell
needs to be positive. According to this, as long as the sign of E°cell is positive,
the reactions occurring at poles have a higher possibility of being spontaneous.
Besides, if we examine relationship (1), we see that it does not include con-
centration and pressure units. Also the temperature values are also missing.
Therefore, standard cell potential E°cell and standard Gibbs free energy ∆G° can
Exercise 4-8 be shown as follows:
Standard reduction potential of sil- 2) ∆G° = -nFE°cell
ver is E°Ag+/Ag= +0.80 V. Can HCl
Previously, in Chemical Equilibrium chapter, we have written the rela-
solution dissolve silver metal found
tionship between standard free energy ∆G° and equilibrium constant
in the following cell containing a
Keq.
solution with 1 M Ag+ ion? (Note:
Dissolution of metal in solution 3) ∆G° = -RTInKeq
means that reaction occurs sponta- If we exchange the ∆G° in (3) with the one in (2):we get
neously.) 4) -RTInKeq = -nFE°cell
Ag ǀ Ag+(1M) ‖ H+(1M)
ǀ H2(1atm) ǀ Pt If we re-arrange (4):
5) RT
Answer: HCl does not dissolve the E°cell = _____ InKeq
nF
metal.

At 25 0C (298K), If we insert temperature C, F and R values in Equation

(5), we get the following equation:

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 Redox Reactions & Electrochemistry

F = 96500 C/mol.e-, R = 8.314(J/K.mol)

8.314 (J/K.mol) × 298 (K)

E°cell = ______________________ InKeq
n × 96500 (C/mol.e-)

0.026 (V)
E°cell = ________ InKeq
n
(n) is the mole number of electron taken or given (in oxidation and reduction
Reaction under E0cell Keq ∆G0
reactions) when we add both half cell reactions to get the general reaction. This
standard condi-
equation is only used for a certain temperature. tions
Table 4-3 explains the relationship among ∆G° standard free energy, E°cell stan- Products are positive Keq>1 negative
dard cell potential and equilibrium constant. preferred
Reactants and null Keq =1 zero
products equal- (zero)
Example 4-7 ly preferred
Reactants are negative Keq <1 Pozitive
The reaction equation of a galvanic cell is as follows: preferred
2Ag+(aq) + Pb(s) → 2Ag(s) + Pb2+(aq) Table 4-3
Explains the relationship among
Calculate ∆G° and equilibrium constant (Keq) values at 25°C. ∆G° standard free energy, E°cell
standard cell potential and equilib-
Standard reduction potential : E°Ag+/Ag= +0.80 V, E°Pb2+/Pb= -0.13 V rium constant.

Solution: Attention:
This reaction occurs only at 25 °C
We write down anode (oxidation) and cathode (reduction) half cell reactions.
(298 K) temperature.
Pb(s) → Pb2+(aq)+ 2e- E°Pb2+/Pb= +0.13 V
2Ag+(aq) + 2e- → 2Ag(s) E°Ag+/Ag= +0.80

When we add both half cell reactions, we get a general reaction equation as Exercise 4-9
below: Calculate ∆G° standard Gibb’s free
2Ag +
(aq)
+ Pb(s) → 2Ag(s) + Pb 2+
(aq)
energy in Standard Cell reaction at
25 0C.
We can calculate standard cell potential E°cell. 3Hg22+(aq) + 2Cr(s) → 6Hg(1) + 2Cr3+(aq)
E°cell = E°anode + E°cathode
Standard reduction potential of
E°cell = (+0.13 V) + (+0.80 V) = 0.93 V E0Hg22+/Hg = +0.85 V
We can calculate ∆G° standard Gibb’s free energy using the relationship be- E0Cr3+/Cr = - 0.74 V
tween ∆G° and standard cell potential E°cell.
∆G° = -nFE°cell ⇒ ∆G° = -2 × 96500 (C/mol.e-) × 0.93 V Answer: -920610 J/mol
∆G° = -179490 J/mol

We use the formula below to calculate equilibrium constant Keq:

RT
E°cell = _____ InKeq
nF

FEZALAR EDUCATIONAL INSTITUTIONS 143

 Chapter - 4

Exercise 4-10 The number of electrons lost or gained in two half cells is n= 2 and
The reaction equation of a standard reaction occurs at 25 °C therefore:
cell at 25°C is as follows:
0.026 (V)
2Fe3+(aq) + -
2I (aq) → 2Fe2+(aq) + I2(s) 0.93 V = ________ InKeq
2
When we insert the values in the equation, Keq is as follows:
Standard reduction potential: Keq = 1.2 × 1031
E I2/I- = +0.53 V
0

E Fe3+/Fe2+ = + 0.77 V
0

4-7-8 The Effect of Concentration on Cell Potential

Calculate the followings; (The Nernst Equation)
A) Standard cell potential So far, we have examined reactants and products in reduction and oxidation
B) Standard Gibb’s free energy reactions only under standard conditions that is their concentrations are equal
C) Equilibrium Constant (Keq) to 1M. But sometimes we need different concentrations. Therefore, we need to
know the relationship between non-standard cell potential and concentrations
Answer: of cell components.
A) +0.24 V In Thermodynamics, we have learnt the relationship between standard free
B) -46320 J/mol Gibbs energy ∆G° and non-standard Gibbs energy ∆G.
C) 1×108 aA + bB → gG + hH
The relationship between Gibbs energy ∆G and standard free Gibbs energy
∆G° is shown in the formula below:

[G]g[H]h
1) ΔG = ΔG° + RTln _______
[A]a[B]b

∆G° standard free Gibbs energy, R is gas constant (8.314 J/K.mol). T is tem-
perature in Kelvin unit and ∆G non-standard free Gibbs energy.
The result of quotient is shown with Q.
[G]g[H]h
_______
[A]a[B]b
We can rewrite Equation (1) as follows:
2) ∆G = ∆G° + RTInQ

From the relationship between standard and non-standard free energy and cell
potential, we get the following equations:
3) ∆G = -nFEcell
4) ∆G° = -nFE°cell

We get Equation (5) when we insert ∆G and ∆°G value from (2) and (4)
in (2).
5) -nFEcell = -nFE°cell + RTInQ
When we divide equation (5) with -nF, we get equation 6:

RT
6) E cell = E° cell - ___ ln Q
nF
144 FEZALAR EDUCATIONAL INSTITUTIONS
 Redox Reactions & Electrochemistry

Equation 6 is called as the Nernst Equation. It relates division of cell potential

and standard cell potential with Q. If the substances in mixture are under stan-
dard conditions that is 1M, Q is equal to 1, so lnQ is equal to zero. The second
part of Equation (6) is equal to zero therefore, we get Ecell= E°cell.
We can simplify Equation (6) by inserting 25°C (298K), mole number and
F = 96500C/mol.e- in their places:

0.026 (V)
7) E cell = E° cell - ________ ln Q
n
This equation can be used only at 25°C (298K).
2Ag+(aq) + Pb(s) → 2Ag(s) + Pb2+(aq)
At 25°C, for the cell with standard potential 1.10 V, we can write Nernst
equation as follows:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Here attention is needed as the concentration values of solid substances

[Zn]=1, [Cu] =1, they are not written in the quotient.

0.026 V [Zn2+ ]
E cell = E° cell - ln
n [Cu2+ ]

Example 4-8 Exercise 4-11

Calculate cell potential Ecell of the following equation at 25°C. In the galvanic cell shown below,
2Ag+(aq) + Cu(s) → 2Ag(s) + Cu2+(aq) Ecell = 0.73V, [Zn2+ ]=0.l M, and
pressure of hydrogen gas (PH2) is 1
atm at 250C. Calculate the molar con-
The concentrations of ions: [Ag+]= 0.01 M, [Cu2+]= 0.01M and
centration of H+ ions.
Standard reduction potential: E°Ag+/Ag = +0.80 V, E°Cu2+/Cu = +0.34 V E0Zn2+/Zn = -0.76V

Solution:
We write reaction equations at anode or cathode.
Cu(s) → Cu2+(aq)+ 2e- E°anode= -0.34 V
2Ag+(aq) + 2e- → 2Ag(s) E°cathode= +0.80

2Ag+(aq) + Cu(s) → 2Ag(s) + Cu2+(aq)

Standard cell potential:

Answer: 0.1mol/L
E°cell = E°anode + E°cathode

E°cell = (-0.34 V) + ( +0.80 V) = 0.46 V

FEZALAR EDUCATIONAL INSTITUTIONS 145

 Chapter - 4

Exercise 4-12 We calculate Ecell from Nernst Equation:

Calculate the E , E° and ΔG values
[Cu2+ ]
cell cell

for the following cell. 0.026 V

E cell = E° cell - ln
Mg | Mg2+(0.05M) || Sn2+(0.04M) | Sn n [Ag+ ]2
0.026 V 0.01
Standard reduction potential: E cell = 0.46 V - ln
E°Sn2+/Sn = -0.14 V 2 (0.01)2
E°Mg2+/Mg = -2.37 V E cell = 0.40 V

Answer:
E = 2.227 V
cell
4-8 ELECTROLYTIC CELLS
E° = 2.23V
cell
These cells consume electrical energy. They convert electrical energy into
ΔG = - 429811 J/mol chemical energy. Reactions do not occur spontaneously. Electrical energy is
given in order to start reactions. That means free energy has got a positive sign
(∆G= +). Electrolytic cells have many applications in industry. For example, in
purification of metals and in electrical appliances, this method is used. In this
part, we will explain some electrolytic cells.

4-8-1-Electrolytic cell of sodium chloride solution:

The reactions in electrolytic cells occur using electrical energy. Sodium chlo-
ride solution contains sodium and chloride ions in free state. In Fig. 4-7, the
electrolytic cell of sodium chloride solu-
tion is shown. Carbon and platinum elec-
trodes are dipped into sodium chloride
solution in the cell. In electrolysis reac-
tion, reduction occurs at cathode. Sodium
ions are reduced to sodium metal. The re-
action at cathode is as follows:
Na+ + e- → Na
Oxidation occurs at anode. Chloride ions
oxidize to chlorine atom. Later atoms
combine and form chlorine gas.
Reaction at anode:
2Cl- → Cl2+ 2e-

Figure 4-7 To make number of electrons equal, reduction half reaction is multiplied by 2
Electrolytic cell of sodium and electrons are omitted from both cell equations. Then both half cell equa-
chloride solution tions are added.
2Na+ + 2e- → 2Na Reduction half reaction (cathode)
2Cl- → Cl2+ 2e- Oxidation half reaction (anode)
_____________________

2Na+ + 2Cl- → 2Na + Cl2 Total net reaction

Sodium and chlorine need to be collected at different containers to

avoid them reacting again and forming sodium chloride.

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 Redox Reactions & Electrochemistry

4-8-2-Electroplating Cell
Electroplating is plating of a metal with another metal as a thin layer by elec-
trolysis. This process is very important as it is used to protect metals from
corrosion.
Electroplating cell consists of anode and cathode poles. Anode includes metals
like gold or silver which we choose as plating material. Cathode is formed from
spoon or alike which we want to plate.
Salt solutions of plating metal as AgNO3 silver nitrate or gold nitrate Au(NO3)3
is filled into the cell. Fig 4-8 shows a plating cell which uses silver to plate a
fork. Figure 4-8
The quality of plating depends on the voltage of electric current and the con- Electroplating Cell
centration of the plating metal.
4-9 FARADAY’S LAW
In the early 19th century, English scientist Faraday formulated electrolysis
laws known with his name through experiments.
These laws:
First Law:
The amount of substance formed or lost at electrodes are directly proportional
to the amount of electric current passing through the electrolysis circuit.
Second Law:
When equal amount of electric current passes, the mass of each substance at
electrodes is directly proportional to their equivalent masses.
To understand those laws, we need to learn reactions occurring at electrodes
well.
Reactions at Cathode:
A- At cathode, ions reduce to their atoms and deposits.
B- At cathode, positive gas ions evolve as a gas as H2.
Reactions at Anode:
A- At anode, metals dissolve in electrolyte solution. Attention:
B- At anode, negative gas ions evolve gases like Cl2 and O2. Don not confuse Q with the sym-
Before we apply Faraday’s Laws, let’s learn terms and units in this law: bol of amount of electric charge
1- Electric current is represented with (I). Its unit is ampere and shown with (Q) as a division
(A).
2-The symbol of electrical charge is (Q) and its unit is coulomb and shown
with (C). F= 96500 C/mol.e-, F is Faraday constant. Q, electrical charge is ob-
(mol.e-)= mole number of elec-
tained from multiplication of current (ampere) and time (second).
trons
Q (C) = I (A) × t (s)
In order to convert electrical charge into mole number of electrons, Q is
divided by Faraday constant.
I(A) × t (s)
Q (mol.e-) =
96500 (C/mol.e-)
Let’s explain calculation of Faraday’s Law here. The mass of substances that
gathered at cathode or dissolved at anode or evolved as gas is directly propor-
tional to their equivalent masses. The pass of 1 mole of electron 96500 C or 1
Faraday current from circuit means evolution of 1 equaivalent-gram substance
or dissolution at anode or evolution of gas at electrode. If we do not want to use
equivalent-gram unit, we can convert mole number of electrons to mole num-
ber of according to number of electrons gained or lost electrons in reduction

FEZALAR EDUCATIONAL INSTITUTIONS 147

 Chapter - 4

or oxidation. We follow the steps in Table 4-1 while solving problems about
Faraday.
Q (C)=I (A) × t (s) 1- We can convert electrical charge to mole electron (Q (mol.e-)) by using
following equation.
I(A) × t (s)
Q (mol.e-) =
96500 (C/mol.e-)
2- We get the mole number by using number of gained or lost electrons in two
I(A) × t (s) half cell reactions.
Q (mol.e-) = 3- Using the formula below, mole number of evolved or deposited substance is
96500 (C/mol.e-)
found after passing electric current through cells.
1 mol
n = Q×
deposit or cell Q
evolved cell half reaction
1 mol 4- Using the formula below, by multiplying number of mole (n (mole)) with
n=Q×
deposit or cell Q molar mass M (g/mol), we convert to mass of substance deposited at cathode
evolved cell half reaction or dissolved at anode.
m (g) = n (mol) × M (g/mol)
Or using the following formula, we convert number of mole to volume of
evolved gas.
PV = nRT
V(L) × 1 mol While solving some mathematical questions, the atom numbers of elements
n= in electrolysis or molecule numbers or number of electrons gained or lost
22.4 L in the cell might be needed. We can solve these questions by assuming that
atom, electron or molecule number of any substance in cell is equal to Avoga-
dro’s number.

evolved number
of molecules
Example 4-9
n= The half cell reaction is as follows:
Avogadro’s number
Mg2+(aq) + 2e- → Mg(s)
How many grams of magnesium are obtained in an electrolysis cell in which
25 A current passes in an hour?
Atomic mass of magnesium is 24. Calculate the number of magnesium atoms
transferred number of accumulating at the cathode under same conditions.
Q=
electrons
Solution:
Avogadro’s number In the Faraday’s Law, the time unit is second. Therefore, we convert hour to
second:
3600 (s) 3600 (s)
Table 4-1 Table showing steps t (s) =t (hr) ×
1 (hr)
⇒ t (s) = 1 (hr) ×
1 (hr)
= 3600 s
to be followed while solving
problems about Faraday’s law
With respect to number of moles of electrons, we calculate the amount of
electricity passing through the cell:

I(A) × t (s)
Q (mol.e-) =
96500 (C/mol.e-)
25(A) × 3600 (s)
Q (mol.e-) = = 0.9 mol.e-
96500 (C/mol.e-)

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 Redox Reactions & Electrochemistry

According to the magnesium’s reduction equation, we can say that Exercise 4-13
when 1 mole of magnesium deposits, 2 mole of electrons pass through Calculate the electric current
the cell. Therefore, the mole number of magnesium is as follows: we need to supply in 200 sec-
1 mol
n= Q× onds in order to deposit 3 grams
Q of gold at the cathode in gold
chloride, AuCl3, solution.
(Au = 197 g/mol)
From the following equation, we can get the mass in gram unit:
Answer: 21.7 A

Exercise 4-14
In order to find the number of Mg atoms depositing at the cathode, we need
96.5 A of electric current was giv-
to know that 1 mole consists of as many atoms as Avogadro’s number.
en to the copper sulfate, CuSO4,
m (g) = n (mol) × M (g/mol)
m (g) = 0.45 (mol) × 24 (g/mol) = 10.8 g solution with 0.2 M concentration
Number of atoms = number of moles x Avogadro’s number and 600 mL volume. Calculate
N = NA (atoms /mol)× n (mol) the length of time needed to
N = 6.02×1023 (atoms/mol) × 0.45 (mol) remain 0.03 mole of copper ion,
Cu2+, in the solution.
N = 2.7×1023 atoms
Answer: 180 s
4-10- BATTERIES AND FUEL CELLS
Generally galvanic cells are called as batteries and divided into two:
Rechargeable and non-rechargeable batteries.
A battery generally consists of a few galvanic cells that are connected one af-
ter another. The total charge is equal to the sum of the charges of these cells.
Let’s talk about these batteries we often use in our daily lives.

4-10-1 Lead Storage Batteries (Accumulator)

This type of battery is used in industry and to supply energy for many applianc-
es and vehicles. It consists of lead galvanic cells that have potentials less than
2V. Every cell has got two poles one of which is made up of lead and works
as anode and the other is made up of lead oxide and works as cathode. These
two poles are dipped in sulfuric acid solution which is an electrolysis solution
and has a density between 1.2 g/mL and 1.3 g/mL. This battery consists of 3 or
more cells and works as a galvanic cell with a potential of 6 V or 12 V. Fig 4-9 Figure 4-9
Reaction at the anode: Lead Storage Batteries (Accumu-
Pb(s) + SO42-(aq) → PbSO4(s) + 2e- lator)
PbO2 is reduced in the reaction at the cathode:
PbO2(s) + 4H+(aq) + SO42-(aq) + 2e- → PbSO4(s) + 2H2O(l)
The total reaction:
Pb(s) + PbO2(s) + 2H2SO4(l) → 2PbSO4(s) + 2H2O(l)

As long as the battery works, lead sulfate deposits as a solid on both

poles. While sulfuric acid is consumed as ions, the amount of water in-
creases and therefore, the density of acid solution decreases. When the
car starts moving, with voltage effect battery half reactions are reversed.

FEZALAR EDUCATIONAL INSTITUTIONS 149

 Chapter - 4

Pb, PbO2 and H2SO4 are formed again. By supplying an electric current
opposite to the reaction in the battery, it can be recharged again. In this
case, it becomes a battery that consists of a group of electrolysis cells.
PbSO4 solution decomposes at two poles and the density of acid returns
to the original state.

4-10-2 Dry Cell Batteries:

This type of battery is made up of a zinc box which works as anode
filled with MnO2, carbon (graphite) and ammonium chloride (NH4Cl)
wet paste. Fig. 4-10
Zinc atoms oxidize at the anode.
Zn(s) + 2OH-(aq) → Zn(OH)2(s) + 2e-

Owing to carbon cathode, electrons move and with the help of water, MnO2 is
reduced.
2MnO2(s) + 2H2O(l) + 2e- → 2MnO(OH)(s) + 2OH-(aq)

The total reaction:

Figure 4-10 Zn(s) + 2MnO2(s) + 2H2O(l) → Zn(OH)2(s) + 2MnO(OH)(s)
Dry cell

Properties: They have a potential of 1.48V and they are used in many
appliances like radios, calculators, toys, etc., and they are not recharge-
able.

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 Redox Reactions & Electrochemistry

BASIC EQUATIONS

Calculation of standard cell potential

The relationship between free energy change

and cell potential

The relationship between standard free en-

ergy change and standard cell potential

The relationship between standard cell po-

tential and equilibrium constant

The relationship between standard cell po-

tential and equilibrium constant at 25 °C

Nernst formula for the calculation of

non-standard cell potential

Nernst formula for the calculation of

non-standard cell potential at 25 °C

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 Chapter - 4

BASIC CONCEPTS
Oxidation: A chemical change which causes loss of electrons from an atom or atom group and increasing
oxidation number.

Reduction: A chemical change which causes gain of electrons to an atom or atom group and decreasing oxi-
dation number.

Oxidizing agent: A substance that causes another substance to oxidize.

Reducing agent : A substance that causes another substance to reduce.

Anode: The electrode at which oxidation reaction occurs and is source of electrons.

Cathode: The electrode at which reduction reaction occurs and attracts electrons from the anode.

Electrochemical Cell: Electrochemical cells consist of two electrodes of which one is positive and called as
anode and the other is negative and called as cathode. Both electrodes are dipped into an electrolyte solution
which includes substances to help reduction and oxidation reactions.

Galvanic Cell: The cells in which chemical energy is transformed into electrical energy during spontaneous
chemical reactions occur to produce electricity.

Electrolysis Cells: These are cells which consume electricity. In these cells, electrical energy is transformed
into chemical energy. Their reactions do not occur spontaneously. They are widely used in industry. Electrol-
ysis cells are used to purify metals and in electroplating.

Electromotive Force: It is shown (emf) symbol. It describes the potential between electrodes. It is expressed
as cell potential (E0 cell). But here it does not refer to the measurement of force but potential.

Nernst Equation: It is the equation that relates non-standard cell potential Ecell (in which ingredient substances
have concentrations different from 1M and at different temperatures) to standard cell potential, E0 cell.

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 Redox Reactions & Electrochemistry

QUESTIONS OF CHAPTER-4
4-1- Explain the following terms:
Anode, electromotive force, standard reduction potential, salt bridge

4-2- Explain Faraday’s equations and tell their units.

4-3- Under standard conditions, which of the following pairs are preferred as oxidizing agents?
Standard reduction potentials E0Ag+/Ag = +0.80 V, E0Au3+/Au = +1.50 V, E0Br /Br = +1.07 V,
2
-

E0Cr3+/Cr = -0.74 V, E0 2+ = -0.40 V

Cd /Cd
a) Au3+ or Br2 b) H2 or Ag+ c) Cd2+or Cr3+

4-4- Write down the equation depending on the relationship between ∆G0, Keq and E0cell and all their symbols.

4-5- In an aqueous solution containing Fe2+, Fe3+, Ce3+ and Ce4+ ions under standard conditions 250C and 1 atm pres-
sure, the reaction occurs spontaneously. Calculate the ΔG0 and Keq values of this reaction. (In-1(32.3)=1.1×1014)
Standard reaction potentials: E0Fe3+/Fe2+ = +0.77 V and E0Ce4+/Ce3+ = +1.61 V
Answer: -81080 J/mol, 1.1 × 1014

4-6- Write down the Nernst Equation with all its symbols.

4-7- Calculate the ΔG, E0cell and Ecell for the following cell reaction. (In1.25= 0.2, In10-5= -11.5)
a) Mg(s) + Sn2+(aq) → Mg2+(aq)→ Sn(s) [Mg2+] = 0.05M, [Sn2+] = 0.04M
b) 3Zn(s) + 2Cr3+(aq) → 3Zn2+(aq) + 2Cr(s) [Cr3+] = 0.01M, [Zn2+] = 0.001M
Standard reduction potentials:
E0Mg2+/Mg = -2.37 V, E0Sn2+/Sn = -0.14 V, E0Zn2+/Zn = -0.76 V and E0Cr3+/Cr = -0.74 V
Answer: a) +2.23 V; +2.227 V ; -429811 J/mol b) +0.02 V; +0.07 V; -40530 J/mol

4-8- Calculate the potential of Ecell and E0cell of the cell formed from SHE and Zn/Zn2+ half cell.
[H+] = 1.8M, PH = 1 atm, [Zn2+] = 0.45M, E0Zn2+/Zn = -0.76 V, In0.14 = -2
2
Answer: +0.79V; +0.76V

4-9- Tell the differences between a galvanic cell and an electrolytic cell.

4-10- In the electrolytic cell, one of the half cell reaction is as follow.
2H2O(1) →O2 (g) + 4H+(aq) + 4e-
At 250C an 755 mmHg pressure, 0.08L of O2 gas was accumulated at the electrode. Calculate the number of mole elec-
tron to pass the circuit during electrolysis. (1 atm = 760 mmHg)
Answer : 0.012 mol.e-

4-11- In the electrolysis circuit which consists of AgNO3 and CuCl2 solutions connected in series, electric current was
applied for 3.75 hours. At the end of this time, 2 g of silver accumulated at the first cell.
(Ag = 108 g/mol, Cu = 63.5 g/mol)
a) How many grams of copper accumulated at the second cell?
b) Calculate the amount of electricity given in amperes.
Answer: a) 0.64 g, b) 0.14 A

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 Chapter - 4

4-12- Which of the two different solution containing aluminum and gold ions produce hydrogen gas?
Standard reduction potential of gold E0Au /Au = +1.50 V, standard reduction potential of aluminum E0Al
3+ 3+/Al
= -1.66V
Answer: Hydrogen gas is released from aluminum.

4-13- In the following cell, can iron ion oxidize (Fe2+) to (Fe3+) ion?
Standard cell potential E0 = +1.07 V, E0
-
= +0.77 V,
3+ 2+
Br2/Br Fe /Fe
Pt ǀ Fe (1M) ; Fe (1M) ǁ Br (1M) ǀ Br2 (1atm) ǀ Pt
2+ 3+ -

Answer: Iron ion can oxidize.

4-14- Calculate potential of the hydrogen gas (H2) pole in an electrolytic solution which is pH = 1 at 1 atm and 25°C?
Answer: -0.0592 V

4-15- Specify the reducing and oxidizing agents in the following equation.
AgNO2 + Cl2 + 2KOH → AgNO3 + 2KCl + H2O

4-16- Can we keep the solution of the table salt in copper cup.
Standard reduction potential. E0 2+
= +0.34 V, E0 = -2.70 V, +
,
Cu /Cu Na /Na
Answer: Yes

4-17- Can we keep copper sulfate (CuSO4) solution in a nickel cup? Tell the reason.
Standard reduction potential: E0 2+
= -0.24 V, E0 = + 0.34 V2+
Ni /Ni Cu /Cu
Answer: No

4-18- How many amperes of electric current must be passed through the solution containing gold salt in order to accu-
mulate 5 g of gold at the cathode in one hour? Oxidation number of gold is +3. (Au: 197 g/mol)
Answer: 2.01 A

4-19- What are the anode and cathode of dry cell made up of? Write down both half cell reactions and the net reaction
equation of the cell and explain its properties.

4-20- Why must the potential of a galvanic cell be positive?

4-21- Calculate the concentration of zinc ions in the solution of zinc electrode. Non-standard zinc reduction potential is
(-0.82 V). Standard Zinc reduction potential: E0 = -0.76 V, ln-1(4.6) = 100
2+
Zn /Zn
Answer: 0.01 mol/L

4-22- Calculate the Daniell cell potential as the concentration of zinc sulfate, ZnSO4, solution is 0.1M and the concen-
tration of copper sulfate, CuSO4, solution is 0.01M at 25 ₒC. Standard cell potential is (1.10 V), ln10= 2.3
Answer: +1.07V

4-23- Which of the following is an oxidation-reduction reaction?

1) Al2O3 + 6HCl → 2AlCl3 + 3H2O
2) 2Na + Cl2 → 2NaCl
3) 2KClO3 → 2KCl + 3O2
4) SiBr4 + 3H2O → H2SiO3 + 4HBr
5) Zn + CuSO4→ ZnSO4 + Cu

154 FEZALAR EDUCATIONAL INSTITUTIONS

 Redox Reactions & Electrochemistry

4-24- Calculate free energy change of a galvanic cell which has a standard potential of +0.74 V at 25 ₒC. (In10=2.3)
Cu2+(aq) (0.01M) + Cd(s) → Cu(s) + Cd2+(aq) (0.1M)
Answer: -137030 J/mol

4-25- Calculate the free energy change of the following cell which has a standard reduction of E0Br2/Br- = +1.07 V,
E0Mg2+/Mg = -2.37 V, (In0.01 = -4.6)
Mg | Mg2+ (1M) || Br- (0.1M) | Br2 (1atm) | Pt

4-26- Calculate the free energy change in the cell with Keq = 2.3×104 at 25 ₒC. The full reaction is given below.
2H+(aq) (1M) + Pb(s) → H2(g) + Pb2+(aq) (0.01M) (In23000 = 10, In0.01 = -4.6)
Answer: -36515 J/mol

4-27- The following reaction occurs in a voltaic cell at 25 ₒC.

Sn2+(aq) + Ni(s) → Sn(s) + Ni2+(aq)
E°Ni /Ni = -0.25V, E°Sn /Sn = -0.14V and the non - standard potential of the cell is +0.17 calculate the concentration of
2+ 2+

nickel ions. Sn electrode is under standard conditions with 1M solution. (ln-1 (- 4.62)=0.01)
Answer: 0.01 mol/L

4-28- In this reaction; Al Al 3+ (1M) Cd 2+ (1M) Cd Calculate the reduction potential of aluminum as standard cell
potential is 1.26 V and standard reduction potential of cadmium: E0 2+
= -0.40 V
Cd /Cd
Answer: -1.66V

4-29- In a galvanic cell at 25ₒC at one pole there is hydrogen gas at 1 atm pressure and at the other pole there is 0.01 M
solution containing nickel ions.
Calculate the PH of this cell as free energy for the cell reaction is -48.25 kJ/mol and the potential of standard nickel
electrode is -0.25 V.
Answer: 1

4-30- If the potential of the following cell is 0.9992 V at 25 ₒC, calculate the concentration of tin (Sn2+) ions in the
electrode solution.
Sn Sn 2+ (?M) Ag + (1M) Ag
Silver electrode is under standard conditions. Standard reduction potential: E0Ag+/Ag = +0.80 V, E0Sn2+/Sn = -0.14 V
Answer: 0.01 mol/L

4-31- 10A of electric current is passed through an electrolysis cell containing copper sulfate, CuSO4, solution for 965
seconds. Calculate the mass and number of atoms of copper accumulated at the electrode. (MCu = 63 g/mol)
Answer: 3.15 g; 0.3×1023 atoms

4-32- As a result of passing 3A of electric current through a metal salt with single valence for 3 min 13 seconds, 0.648
g of metal accumulated at the cathode. Calculate the atomic mass of the metal.
Answer: 108 g

4-33- In order to release 2 times of molar volume of oxygen gas under standard conditions (STP), what is the number
of electrons needed. (Molar volume of a gas under standard conditions (STP) is 22.4 L)
Answer: 48.16×1023 e-

4-34- What is the amount of electric current to be passed through (in ampere) an electrolysis cell for 2 hours 520 sec-
ond necessary to release 36.12×1021 hydrogen and oxygen molecules at two poles?
Answer: 1A

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 Chapter - 4

4-35- A jeweler applied 10A of electric current through an electroplating cell containing gold salt in order to plate a
ring. As 75% of electric current was consumed in 9.65 seconds, what is the mass of gold used in plating? Atomic mass
of gold = 197 g/mol. (Oxidation number of Au is +3)
Answer: 0.05g

4-36- After we passed 0.2 mole of e- through copper sulfate, CuSO4, solution under standard conditions (STP) and all
copper precipitated and 0.448 L of hydrogen gas was released. Calculate the mass of copper.
(Atomic mass of copper = 63 g/mol)
Answer: 5.04g

4-37- Calculate the equilibrium constant of the following reaction.

Sn(s) + Pb2+(aq) → Sn2+(aq) + Pb(s)
Standard reduction potential = E0 2+
= -0.13 V, E0 2+
= -0.14 V , (ln-1(0.769) = 2.16)
Pb /Pb Sn /Sn
Answer: 2.16

4-38- In water electrolysis cell at STP, electrical current was applied for 3 minutes and 13 seconds, hydrogen and oxy-
gen gases were released at the cell electrodes. The volume of the two released gases equals 0.0672 L. Write down the
equation of the two halves, and total equation, find out the volume of each gas and the electric current intensity.
Answer: 2 A

4-39- Standard cathode solution of daniell cell was diluted with water, the potential of electrode decreased by 0.0592 V
than its standard potential, calculate the concentration of electrode ions. (e4.6 = 100 )
Answer: 0.01 M

4-40- As the reduction potentials: E° 2+

= -0.76 V and E° +
= 0.80 V
Zn /Zn Ag /Ag
Answer the following questions;
1- A voltaic (galvanic) cell consists of zinc and silver plates in their electrolytic solution with 1M concentration for
each of them, which mass of plate will increase, which mass of plate will decrease? Why?
2- What is the value of free energy of voltaic cell which consists of standard zinc and silver electrodes in 0.1M silver
ions?
Answer: 1) Mass of zinc plate decreases and mass of silver plate increases.
2) -289500 J

156 FEZALAR EDUCATIONAL INSTITUTIONS

 Coordination Chemistry

COORDINATION CHEMISTRY CHAPTER-5

ACHIEVEMENTS
After studying this chapter, students can perform the following:
* They can differentiate double salts and complex compounds.
* They learn the properties of coordination compounds and how coordination chemistry has developed.
* They can calculate primary and secondary valences of coordination compounds.
* They learn special terms about coordination chemistry.
* They learn about different types of ligands.
* They learn central atom, ligands and they can calculate coordination numbers.
* They learn the theories describing the properties of bonds in complex coordination compounds and they
can apply valence bond theory on coordination compounds.
* They can find coordination numbers of coordination compounds and decide their geometrical shapes.

FEZALAR EDUCATIONAL INSTITUTIONS 157

 Chapter - 5

5-1 PREFACE
Coordination (complex) compounds have become one of main subjects of inor-
ganic chemistry as in addition to different colors and magnetic properties they
have, they also participate in many chemical structures and reactions. These
compounds have an increasing importance in industry, agriculture, medicine,
pharmacy, modern life and clean energy production. Hemoglobin, B12 vitamin
and chlorophyll are examples for these compounds.
Most of the elements in periodic table form complex compounds. But in this
chapter, we will study mainly the complex compounds that transition elements
form.
Elements that are situated between IIa and IIIa groups are called as transition
elements (Figure 5-1). If d and f orbitals of an element have valence electrons,
Hemoglobin it is accepted as a transition element. Transition elements are divided into two:
1- d group elements are called as main transition elements. They are found in
3 rows and each row consists of 10 elements. These are called as first, second
and third transition chains.
2- f group elements are called as inner transitions elements. This group con-
sists of 2 rows, each row includes 14 elements. These elements are called as
lanthanides and actinides.

Properties of Transition Elements

1- They have more than one oxidation steps (valence).
2- In the last orbits of transition elements there are d and f orbitals. Those have
unshared electrons. These single electrons give paramagnetism to atoms (at-
traction property in magnetic field).
3- Most of their compounds are colored.
4- They can form many ions and complex compounds.
Chlorophyll
5-2 DOUBLE SALTS AND COORDINATION COMPOUNDS
When two stable and simple salt solutions (ammonium sulfate and iron (III)
sulfate) are mixed in mole amounts and if the resulting solution is vaporized, a
new compound called as addition compound is obtained. This process is shown
in the following equation:

Mohr’s salt
When copper sulfate, CuSO4, is dissolved in a certain solution and with addi-
tion of ammonia, the following addition compound is obtained:

or

Cage structure of hemoglobin

158 FEZALAR EDUCATIONAL INSTITUTIONS

 Coordination Chemistry
Figure 5-1

Therefore, we can divide addition compounds into two:

A- Double Salts
These are stable salts of coordination compounds. When they dissolve in water, they de-
compose to ions that form them. For example, Mohr’s salt, prepared in the first equation
above, gives Fe2+, NH4+, SO42- ions to the solution when it dissolves in water.

B- Complex Salts (Coordination Compounds)

These are stable coordination compounds. But they don’t decompose to ions which form
them completely when they dissolve in water. For example, the coordination compound
CuSO4.4NH3 in the second equation above doesn’t give Cu2+ ion to solution when it dis-
solves in water, but it gives only SO42- ion. Cu2+ ion takes place in [Cu(NH3)4]2+ complex
ion according to the following equation:

Therefore, there is only SO42- ion in the solution, but not Cu2+ ion. Thus, this complex salt
is written as [Cu(NH3)4]SO4. This coordination compound is formed from [Cu(NH3)4]2+
positive complex ion and simple negative SO42- ion. Coordination compounds can be
formed from a complex negative ion and a simple positive ion or complex negative and
complex positive ions, as shown in the following examples:

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 Chapter - 5

Coordination compound Positive simple ion Negative complex ion

Coordination compound Positive complex ion Negative simple ion

Some coordination compounds don’t dissolve in water as they don’t ionize

completely. e.g. [Ni(CO)4] and [Ni(dmg)2] (dmg = dimethylglyoxime) and
[Co(NH3)3Cl3]
.
Example 5-1
Whereas Fe(NH4)2(SO4)2 is classified as a double salt, K3[Fe(CN)6] is accept-
ed as a complex compound. Tell the reason for that.
Solution:
Fe(NH4)2(SO4)2 compound is formed from the mixture of iron (II) sulfate and
ammonium sulfate solutions according to the equation below:

The resulting compound is anhydrous(without water molecules) Mohr’s salt.

It gives Fe2+, NH4+, SO42 - ions to solution when it dissolves in water. In order
to make sure that those ions are present in the solution, each ion can be deter-
mined through known analysis methods.
When K3[Fe(CN)6] compound dissolves in water, the following equation
occurs:

As seen here, Fe3+ ions in free state have disappeared and these ions partici-
pated in the structure of [Fe(CN)6]3- complex ion. Therefore, when dissolves
in water, only K+ ions are present in the solution but not Fe3+ or CN- ions. That
means whereas Fe(NH4)2(SO4)2 is a double salt, K3[Fe(CN)6] is a complex
compound (complex salt.)

5-3 DEVELOPMENT OF COORDINATION CHEMISTRY

The preparation of hexaammine cobalt (III) chloride (CoCl3. 6NH3), in 1798
is accepted as the real beginning of coordination chemistry. The preparation of
this compound was big news owing to its unprecedented properties. The reason
is that forming a stable compound from two stable compounds (from mixture
of ammonia and CoCl3) could be explained only 100 years later. Within this
time period, many theories were proposed upon formation of these compounds.
But none of those theories were able to explain practical results.

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 Coordination Chemistry

One of those theories is the Chain Theory. The theory was submitted by a Swiss
scientist.
The method followed in this theory is the same as the chain formation between
carbon atoms in organic chemistry. Due to the general idea that atoms had only
one valence (oxidation state) at that time, this scientist claimed that cobalt (III)
formed 3 bonds in complex compounds. Therefore, chain structure was used in
order to explain the shape where 6 ammonia molecules are bonded in CoCl3.
6NH3{Formula I} compound. According to this, chloride ions aren’t bonded to
cobalt directly, when silver nitrate solution is added to aqueous solution of this
compound, it precipitates as silver chloride. This theory explains the structure
of CoCl3.5NH3 {Formula II}. According to this, one single chloride ion that
does not precipitate is directly-bonded to cobalt when silver nitrate is added.
Meanwhile, other two chloride ions precipitate easily.

CoCl3.4NH3 compound is shown with {Formula III} that is compatible with

scientific experiments. According to this formula, there are two ions which are
bonded to cobalt directly. But third chloride ion is not bonded to cobalt directly.
CoCl3.3NH3 compound is shown with Formula (IV).

We might expect that the behavior of chloride ions in Formula (IV) is similar
to that of CoCl3.4NH3 compound. But it is observed that there is no precipita-
tion occurs when silver nitrate solution is added. Because of this and for other
reasons, this theory couldn’t explain all properties of this kind of compounds.

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5-3-1 Werner’s Coordination Theory

Do you know that? Werner proposed his theory which prepared a basis for modern theories
based on the following hypotheses:
Today we can understand
the properties of complex 1- Most of the elements have two kinds of valences. One is primary ion-
compounds owing to the ization valence and it defines oxidation state that is shown with (----). The
perfect theory of Werner. other is unionized valence. It is the coordination number that is shown with
He was 26 when he pro- (_____) .
posed his theory. He was
the first chemist in inorgan- 2- Each element which reacts to form a complex compound tries to satisfy
ic chemistry field who won both valences. First valence is satisfied with a negative ion, second valence
Nobel Prize in 1913. is satisfied with negative ions or molecules.
3- Second valence is oriented to the fixed locations in the space called co-
ordination sphere around the metal ion. This forms the basis of metal com-
plex compounds (stereochemistry.)
Werner showed (CoCl3. 6NH3) compound with formula (V). This can be
shown with the molecular formula of [Co(NH3)6]Cl3. Here, the oxidation
state of cobalt is (+3). Therefore, 3 chloride ions try to satisfy the first
valence (balancing of cobalt ion charge). Second valence or coordination
number is satisfied with 6 ammonia molecules. According to this, second
valence of cobalt (III) is 6 which is shown with coordination number.
Six (6 ) ammonia molecules in this situation are called as ligands. Accord-
ing to this theory, ligands are bonded to metal with coordinate covalent
bonds. Chloride ions aren’t accepted as ligands. Because these form ionic
bonds with metal out of coordination area and all precipitate when silver
nitrate solution is added.
Werner showed (CoCl3. 5NH3) compound with formula (VI). Here, one of
the chloride ions satisfies both first and second valences. One of the bonds
which attaches metal and ion is shown with dashed lines (-----) and the oth-
er is with (-----). Therefore, the chloride ion doesn’t precipitate easily when
silver nitrate solution is added as it is directly-bonded with cobalt atom in-
side coordination area.
Meanwhile, the charge of positive complex ion [Co(NH3)5Cl]2+ is (+2). The
reason is that Co3+ + Cl- = (+3) + (-1 )= +2. Therefore, the compound which
is shown with (CoCl3.5NH3) is with the following molecular formula:
[Co(NH3)5Cl]Cl2
According to this theory, (CoCl3.4NH3) compound is shown with formula
(VII). According to this, two chloride ions satisfy both first and second
valences. Therefore, these are bonded strongly in coordination area. When
silver nitrate solution is added, only one chloride ion which is out of coor-
dination area precipitates. As this compound decomposes to Cl- and
[Co(NH3)4Cl2]+ ions, its molecular is shown as [Co(NH3)4Cl2]Cl.

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According to the theory, the compound (CoCl3. 3NH3) shown with formula
(VIII) doesn’t precipitate when silver nitrate solution is added and it can be
shown with the chemical formula [Co(NH3)3Cl3].
The absence of precipitation means that this compound doesn’t ionize in this
solution. This is the opposite of what is expected in the chain theory. Accord-
ing to practical results, this kind of compounds doesn’t ionize in solution.
This proved that the chain theory isn’t correct and it supported the hypotheses
of coordination theory.

Example 5-2
A- K4[Fe(CN)6]
B- [Cr(NH3)6](NO3)3
What are the first (oxidation state) and second (coordination number) valenc-
es of the central metal atom in the two following compounds?
(Note: Cyanide ion (CN- ) in K4[Fe(CN)6] compound behaves like a ligand.)
Solution:
A- We know that each potassium ion has +1 charge. Therefore, the negative
ion is [Fe(CN)6]4- which carries (-4) charge.

Thus: Fe (x) + (CN-)6= - 4 Therefore, primary valence of iron is

equal to (+2) and second valence is equal
x + 6 × (-1) = - 4 to 6. Thus, this is the number of ligands
x = +2 which are directly related to metal and
shown in brackets.

B- Each nitrate ion has (-1) charge and ammonia is neutral. Therefore, as pos-
itive ion is bonded to ammonia molecules it has +3 charge. [Cr(NH3)6]3+
Cr(x)+ (NH30)6= +3
Therefore, primary valence of chromium is
x + 0 × 6 = +3
+3 and second valence is equal to 6.
x = +3

Exercise 5-1
What are the primary and second-
ary valences of iron in K3[Fe(CN)6]
compound?
Answer: +3; 6

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5-3-2 Lewis Acids and Bases

According to Lewis structure, methane (CH4) and ammonia (NH3) molecules
are shown with the following formulas.

Methane Ammonia

Lewis structures of methane and ammonia molecules show that there is a very
important difference between them. This difference is that nitrogen atom has a
pair of electrons which don’t form a bond with hydrogen atom. As a result of
this, ammonia molecule can react with other atoms using this electron pair. As
in nitrogen atom, this pair of electrons is shared with another atom which has
an empty orbital and a coordinate covalent bond is formed. This bond is shown
with an arrow (→) showing the direction from donor atom to acceptor atom.
As an example to this reaction, interaction of ammonia with proton in order to
produce ammonium ion can be given.

Ammonia, can share this electron pair on nitrogen with other atoms just as
with hydrogen. The following example reactions show using electron pair on
nitrogen with metals.

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These reactions are accepted as acid-base reactions according to Lewis struc-

ture. Ammonia is accepted as electron donor. Therefore, it is a base according
to Lewis theory. The metal ion which accepts electron pair is an acid accord-
ing to Lewis theory. As a result of this reaction, a coordinate covalent bond is
formed. The resulting compounds are called as coordination complexes.
To summarize, this reaction occurs between a Lewis base which is called as a
ligand and a Lewis acid which is called as central atom (metal).
As mentioned above, some terms are used about coordination compounds.
Let’s learn some other terms which we will see in this chapter later.

1- Ligands
They are negative charged molecules or ions which are bonded to a central
atom through one or more atom. A ligand is called as a monodentate ligand if it
donates a pair of electrons, it is called a bidentate ligand if it donates two pairs
of electrons and if it donates more than two pairs of electrons, it is called as a
multidentate ligand.

2- Central Atom
One of the properties of coordination compounds is that they have an atom
which is an electron pair acceptor. This atom is bonded to a ligand with a coor-
dinate covalent bond. This atom is called as the central atom.

3- Coordination Complex
The compound which results from bonding of central atom and ligand mole-
cules with coordinate covalent bonds.

4- Coordination Number
This number is the multiplication of number of ligands bonded to central atom
with the number of dentate of ligand. In other words, it is equal to the number
of covalent bonds. Most occurring coordination numbers are 2, 4 and 6. Odd
coordination numbers are rarely seen. In coordination complexes, central atom
has two valences. One is oxidation state and the other is coordination number.
In simple compounds, there is only oxidation state. For example, the oxidation
state of iron in [Fe(CN)6]4- is (+2) and coordination number is 6. The sum of
charges in the complex molecule gives the charge of it. Here, the charge of the
complex ion is (-4). The charge of Fe(II) is (+2) and the sum of charges of six
cyanide ions (CN-) is (-6).

5- Complex Ion
They are compounds charged with positive or negative charges. They have a
central metal atom and suitable number of ligands around metal atom bonded
to it with covalent bonds. Central atom has an oxidation state as neutral, posi-
tive or negative. Ligands are usually neutral or negative or both.
For example: [Co(NH3)6]3+ [Ni(CN)4]4- [Fe(CN)6]4-
Neutral ligand Negative ligand Negative Ligand

[Co(NH3)5Cl]2+
Negative and Neutral ligand

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 Chapter - 5

Monodentate ligand 6- Neutral Complex Compounds

They don’t ionize in water. Following compounds are examples for neutral
complexes.
[Co3+(NH3)3Cl3] ; [Ni0(CO)4]
[Pt2+(NH3)2Cl2] ; [Ni2+(dmg)2]

7- Coordination Sphere
While writing complex compounds, central atom and ligands are shown
in brackets. These brackets show the coordination field and it is called
as inner sphere. The part out of these brackets are called as ionization
sphere or outer sphere. For example, inner sphere of [Co(NH3)5Cl]Cl2
complex compound consists of central ion Co3+ and 6 ligands. These ligands
are 5 ammonia molecules and one chloride ion Cl-. The part which consists
of 2 chloride ions is the outer sphere. Therefore, ions written inside ioniza-
tion sphere can ionize in water. These ions can be precipitated through using
suitable agents. Ions inside inner sphere cannot ionize thus, they cannot be
precipitated. For example:
[Co(NH3)5Cl]Cl2 
→ [Co(NH3)5Cl]2+ + 2Cl-
2Ag+ + 2Cl- 
→ 2AgCl
Bidentate ligand White precipitate

Two (2) Cl- ions inside ionization sphere can be precipitated as silver chlo-
ride(AgCl) (white precipitate) through addition of silver nitrate (AgNO3). But
Cl- ion inside inner sphere doesn’t ionize in water and therefore it cannot be
precipitated.

8- Coordination Chemistry
It is the branch of inorganic chemistry which studies coordination compounds
and their properties.

Multidentate ligand 5-4 TYPES OF LIGAND

A- Monodentate Ligands
Most of those ligands are negative ions or neutral molecules which can do-
nate an electron pair to positive metal ion. In ligand chemical structure, there
is a single atom which is bonded to central metal atom. For example, CN-,
Br- ,F- , and Cl- ions and ammonia (NH3), alkyl amine (RNH2) and pyridine
(C5H5N) and water (H2O) molecules.

B- Bidentate Ligands
Many ions or molecules form complex compounds through more than one
atom (they have two pairs of electrons which don’t take place in reaction).
For example, oxalate ion C2O42-, and ethylene di amine NH2–CH2 CH2 –NH2
are bidentate ligands.

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C- Multidentate Ligands
These are ligands which have 3, 4 or more atoms that can form covalent
bonds. For example, ethylene diamine tetraacetic acid (EDTA).
EDTA is called as hexadentate ligand as it has six atoms which can form
covalent bonds.
Ligands which are bonded to the same metal atom by two or more regions
are called as chelating ligand. In Table 5-1 some examples are given for
mono or bidentate ligand types.

Table 5-1 Types and Names of Some Mono and Bidentate Ligands
Structure of ligand Name of Ligand Structure of ligand Name of Ligand
Monodentate ligands
NO nitrosyl CO carbonyl
NH3 ammine H 2O aqua
C5H5N pyridine CH3NH2 methyl amine
N3- azido CH3COO- acetato
{(NH2)2CO} urea CN -
cyano
Br- bromo Cl- chloro
Bidentate ligands
NH2NH2 hydrazine NH2CH2CH2NH2 ethylenediamine (en)
CO32- carbonato C2O42- oxalato
-
C4N2O2H7 dimethylglyoximato (dmg) NO3- nitrato

5-5 EFFECTIVE ATOMIC NUMBER RULE (EAN RULE)

The first attempt which explains the stable structures of complex compounds
was made by Sidgwick who expanded Lewis’ Theory. Sidgwick explained
the stability of these compounds by their similarity to noble gas electron con-
figuration. According to this theory, if the numbers of electrons donated by
central ion or ligands is equal to atomic number of one of the noble gases ;
36
Kr, 54Xe, or 86Rn, the complex compound will be stable. The total number
of electrons on the central atom which are donated by ligands are called as
effective atomic number (EAN). This rule is called as effective atomic num-
ber rule. Through this rule, the structure of many complex compounds could
be explained.

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Exercise 5-2 Example 5-3

Calculate EAN for the following What is the effective atomic number of [Co(NH3)6]3+ compound? Is EAN
compounds. Then specify if EAN rule valid in this compound? (Atomic number of cobalt = 27)
rule is valid for them.
(46Pd, 26Fe, 28Ni)
Solution: Calculation is as follows:
[Pd(NH3)6]4+ Co = 27 e-

[Fe(CN)6]3- Co3+ = 24 e-

[Ni(en)3]2+ 6 NH3 = 12 e-
________________
Answer: 35 not valid; 54 valid; [Co(NH3)6]3+ = 36 e-
38 not valid
Here, the effective atomic number is 36. This number is equal to the atomic
number of noble gas Krypton. Therefore, the complex compound is stable as
it follows the EAN rule.
Exercise 5-3
Calculate EAN of [Ag(NH3)4]+ and
Example 5-4
[Ni(NH3)6]2+ complex compounds. What is the EAN of [CoCl4]2- compound? Is EAN rule valid for it? (Atomic
(Atomic number of Ni = 28, atomic number of Cobalt = 27)
number of Ag = 47). Is EAN rule val-
Solution:
id for these compounds?
Co = 27 e-
Answer: 38 not valid; 54 valid
Co2+ = 25 e-
4 Cl- = 8 e-
------------------
[CoCl4]2- = 33 e-
Here, the EAN is 33. This number isn’t equal to atomic number of any noble
gases. Therefore, it doesn’t follow EAN rule. But despite the fact that it is a
stable complex compound.
There are many exceptions of this rule. Although the rule explains the struc-
ture of metal carbonyl complex compounds, it is useful for only a limited
Attention: part of coordination chemistry. For example:
Some complex com-
pounds do not follow Cr = 24 e- Fe = 26 e- Ni = 28 e-
EAN rule; but they are 6 CO = 12 e- 5CO = 10 e- 4CO = 8 e-
stable complexs com-
--------------- ------------------ ---------------
pound.
[Cr(CO)6] = 36 e- [Fe(CO)5] = 36 e- [Ni(CO)4] = 36 e-

These complex compounds seem to follow EAN rule. On the other hand,
metals with odd atomic numbers which make compounds with ligands like
above don’t follow EAN rule. Because the result is always an odd electron
number. Therefore, whatever the added carbonyl number is, effective atomic
number will never be equal to 36, 54 or 86. This kind of compounds are in
dimer molecular or polymer structure.

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The following two complex compounds [Co2(CO)8], [Mn2(CO)10] can be giv-

en as examples. EAN’s of these compounds are calculated as follows:

Mn = 25 e- Co = 27 e-
Mn – Mn = 1 e- Co – Co = 1 e- Exercise 5-4
5CO = 10 e- 4CO = 8 e- Calculate EAN of [Re2(CO)10] com-
plex compounds. Is EAN rule valid
-------------------- ------------------- for this compound? (Atomic number
[Mn2(CO)10] = 36 e- [Co2(CO)8] = 36 e- of Re = 75)
Answer: Valid ;86

5-6 NOMENCLATURE OF COORDINATION COMPOUNDS

Rules assigned by (IUPAC) are as follows:
1- While naming an ionic compound, positive ion is named first and neg-
ative ion second. e.g. naming simple salt NaCl sodium chloride, complex
compound [Cr(NH3)6]Cl3 hexaamminechromium(III) chloride.
2- In coordination compounds, ligands are named first, then the metal
comes. If there are more than one ligands, naming is done in alphabetical
(English) order. For example:
[Cr(H2O)4Cl2]Cl Tetraaquadichlorochromium(III) chloride
3- Negative ligands’ names finish with –o suffix. But neutral ligands assume
molecule name without any change. As exceptions, water becomes aqua
and ammonia becomes ammine. In order to differentiate ammonia from
other amines, double m is used. Other amines are written with single m.
Attention: While writ-
ing IUPAC names of pos-
Positive ligands (which are rare) finish with –ium suffix. In Table 5-2 , some
itive or negative ions, no
positive and negative ligands are given.
blank is left. But a blank
is left between positive
and negative ions.

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 Chapter - 5

Table 5-2 Name of ligands Symbol of ligands

4- If there are more than one of the same ligands in a complex compound, pre-
fixes di-, tri-, tetra- etc. are mentioned before ligand name. But before complex
ligands as ethylenediamine (en) and ethylenediaminetetraacetic acid (EDTA),
prefixes bis-, tris- are used.
Exercise 5-5
Name the following coordination For example: [Co(en)2Cl2]2SO4 Dichlorobis(ethylenediamine)cobalt(III)
compounds. sulfate.
1- [Co(NH3)5H2O]Cl3 5- The oxidation state of central atom is mentioned right after the name of
the metal with Roman numerals. If the oxidation state is zero, “0” number is
2- Na[Co(NH3)4 Cl2] used.

3- K2[PtCl6] For example: [Ni(CO)4] tetracarbonylnickel (0)

6- If complex compound is a negative ion, name of central atom finishes with
4- [Cr(NH3)6](NO3)3 suffix –ate. Most of the time, Latin names are used for metals (For example:
iron = ferrum, lead= plumbum, etc.) But in positive ionic or neutral complex
5- [Cu(en)2]Cl2 compounds, name of central metal atom remains unchanged. For example:

6- (NH4)2[Cr(SCN)6] Ca2[Fe(CN)6] Calcium hexacyanoferrate (II)

[Fe(H2O)6]SO4 Hexaaquairon (II) Sulphate
[Ni(dmg)2] Bis(dimethylglyoximato)nickel (II)

5-7 BONDING THEORIES IN COORDINATION COMPOUNDS

Werner’s chain theory and coordination theory were just simple introduction
to understand the structures of coordination compounds. Today, there have
been three theories proposed to explain the bond structures of coordination
compounds. These are:
1- Valence Bond Theory (VBT)
2- Crystal Field Theory (CFT)
3- Molecular Orbital Theory (MOT)

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At this level, we will only give a simple explanation of Valence Bond Theory.
You can study Crystal Field Theory and Molecule Orbital Theory at university.
Exercise 5-6
5-7-1 Valence Bond Theory Show electron configura-
This theory explains the bond structure of coordination compounds success- tion of metal and ligand in
fully. This theory is related to hybridization and geometrical shape of central [Cu(CN)2]- complex com-
atom. According to this theory, complex structure is formation of coordinate pound according to Valence
covalent bond between Lewis base (ligand) and Lewis acid (metal) reaction. In Bond Theory. (29Cu)
this theory, orbitals of metal are shown with squares (sometimes with circles).
They show the electron configuration of metal in outer shell and also electrons
of ligands. We will apply this theory to compounds with coordination number
of 2, 3 or 4. We will leave the application of this theory to compounds with
bigger coordination numbers to upper classes.
For example, in diamminesilver (I) complex ion [Ag(NH3)2]+, electron configu-
ration in outer shell of silver and electron configuration of complex compound
is as follows:

- 4 electrons from 2 ligands

- Hybridization type is sp (while forming a bond, one s orbital and one p or-
bital are used).
- The shape of complex ion is linear.
- As there are no unpaired electrons, complex ion shows diamagnetic property
(all electrons are paired).

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 Chapter - 5

In [HgI3 ]- triiodomercurate (II) complex compound, the configuration of

electrons in outer shell and electron configuration of complex compound is as
follows:

- 6 electrons from 3 ligands

- Hybridization type is sp2 (in bond formation one s orbital and 2 p orbitals
are used).
- Geometrical shape is trigonal planar.
- It shows diamagnetic property as all electrons are paired.
The electron configuration of outer shell nickel and complex compound in
tetrachloronickelate (II) [Ni(Cl)4]2- complex ion is as follows:

- 8 electrons from 4 ligands

- Hybridization type is sp3 (In bond formation, one s orbital and 3 p orbitals
are used).
- Geometrical shape is tetrahedral.
- It is paramagnetic as it has 2 unpaired electrons.

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The electron configuration of outer shell of nickel and complex compound in

tetracyanonickelate [Ni(CN)4]2- complex compound is as follows:

- 8 electrons from 4 ligands

- Hybridization type is dsp2 (in bond formation, one d orbital, one s orbital
and 2p orbitals are used).
- Geometrical shape is square planar.
- It shows diamagnetic property as all electrons are paired.

As it is seen in the previous 2 examples, single d electrons remained as they

are in [Ni(CN)4]2- compound. But in [Ni(Cl)4]2- compound, it (d electron) be-
came an electron pair. In formation of complex compound, type of ligand has
an important role. CN- is accepted as a strong ligand. Because it causes un-
paired single electrons to become paired in forming complex. But Cl- doesn’t
have such capability. Therefore it is accepted as a weak ligand. Ligands are
accepted as weak or strong according to chemical spectrum. Table 5-3 shows
those weak and strong ligands.

Table 5-3 SOME STRONG AND WEAK LIGANDS

Weak Ligands Strong Ligands
Symbol Name Symbol Name
I- Iodine ion CN -
Cyanide ion
Br- Bromine ion NH3 Ammine (ammonnia)
Cl- Chlorine ion NH2CH2CH2NH2 Ethylene diamine
F- Fluorine ion NO2 -
Nitrite ion
OH- Hydroxide ion CO Carbonyl
H 2O Aqua C5H5N pyridine

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 Chapter - 5

If complex compound undergoes dsp2 hybridization, ligand’s geometrical

shape is square planar, no matter ligand is strong or weak. The reason for
that is volume expansion after hybridization. Therefore, the configuration of
electrons in outer shell of platinum metal and complex compound in [PtCl4]2-
compound.

- 8 electrons from 4 ligands.

- Hybridization type is dsp2. In bond formation, one d orbital, one s orbital
and 2p orbitals are used.
- Geometrical shape is square planar.
- It shows diamagnetic property as there are no single electrons (all electrons
are paired).

To learn the geometrical shape of complex compounds with single central atom
due to hybridization is possible by calculating their number of single electrons
(unpaired electrons). This calculation is made by the following equation. It
depends on magnetic momentum resulting from electron movement.
Exercise 5-7
Why [NiCl4]2- complex com- μ (B.M)= [e(e+2)]1/2
pound is paramagnetic while In this equation, e = number of single electrons. B.M= Bohr Magneton (mag-
[PtCl4]2- complex compound netic momentum unit).
is diamagnetic. Explain the Let’s study Example 5-5 to explain this equation.
reason according to Valence
Bond Theory. (28Ni, 78Pt) Example 5-5
If “L” is a monodentate ligand in [Co(L)4]2+ complex ion of cobalt (II), ex-
plain the type of hybridization of the complex compound.

Solution:
Hybridization can be decided as follows:
1- First Case
The electron configuration in outer shell of cobalt element and complex com-
pound is as follows:

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 Coordination Chemistry

If we consider this configuration, we see that the number of unpaired elec-

trons is 3. Therefore, magnetic moment is as follows:
μ = [e(e+2)]1/2
μ = [3 (3 + 2) ]1/2
= 3.87 B.M
Exercise 5-8
2- Second Case According to Valence Bond Theory,
The electron configuration of the complex is as follows: [Co(L)4] 2+ what are the types of hybridizations,
geometrical shapes and magnetic
properties of the following two
complex compounds? (46Pd, 27Co)

[PdCl4]2-, [Co(H2O)4]2+

After that calculate the magnetic

According to this configuration, the number of unpaired (single) electrons is
moment (μ) of each.
1. Therefore, magnetic moment is as follows:
μ = [1(1 + 2 )]1/2 = 1.73 B.M Answer:
dsp2, diamagnetic, square planar
sp3, tetrahedral, paramagnetic
If we know magnetic moment, we can guess the type of hybridization. In
this complex compound, if magnetic moment were 3.87 BM, the type of
hybridization would be sp3 as in the first example. But its magnetic moment
is 1.73 B.M, therefore its hybridization type is dsp2.

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 Chapter - 5

5-8 COORDINATION NUMBERS AND EXPECTED

GEOMETRICAL SHAPES
Previously, we have learnt that coordination number shows the number of
atoms directly bonded to the central metal atom. Besides, we have learnt this
number is related to the expected geometrical shape of complex compound.
The values of coordination numbers are between 2 and 9. The most common
ones are 4 and 6. Now, we will mention coordination numbers from 2 to 4 in
coordination compounds. Besides, we will tell the most common geometrical
shape of each number.

1- Coordination Number 2
Compounds with coordination number 2 is rare. The best example to this
complex compound [Ag(NH3)2]+. As expected, this complex ion has a linear
structure, [H3N-Ag-NH3]+. This coordination number is seen in complex com-
pounds of copper (I), silver(I) and gold(I) as in the following examples.
[NC-Ag- CN ]- ; [Cl – Au – Cl]- ; [CN – Cu – CN]-

2- Coordination Number 3
This type of compounds are also rare. Examples of them are few. Negative
complex ion [HgI3]- is the best example of this. In this kind of complexes,
two geometrical shapes are expected. The first is trigonal planar and the other
is trigonal pyramid shape. [HgI3]- has trigonal planar shape whereas
SnCl3- is trigonal pyramid.

3- Coordination Number 4
This is the most common coordination number. Coordination compounds with
this number have great importance in coordination chemistry. This coordina-
tion number causes formation of coordination compounds in which ligands
are coordinated around the central metal atom in tetrahedral or square planar
shapes. Examples of tetrahedral complex compounds are:
[CoBr4]2- ; [FeCl4]-

[HgI3]-

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 Coordination Chemistry

Square planar shaped complex compounds are formed by especially

ions. For example,
Au3+ , Pt2+, Pd2+, Cu2+, Ni2+, [PtCl4]2- , [Pd(CN)4]2- , [Ni(CO)4]2+

Do you know that?

The compound diamminedichloro
platinum (II) [Pt(NH3)2Cl2](II) is an
effective drug against some cancer
types. While this compound is mak-
ing bond with nucleic acid DNA,
two chloride ions replace 2 nitrogen
atoms on DNA molecule. This caus-
es a mutation which means a fault
in order of repeating amino acids in
DNA and this destroys cancer cells.

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 Chapter - 5

BASIC EQUATIONS
Angular momentum : μ (B.M)= [e(e+2)]1/2

BASIC CONCEPTS
Double Salts and Coordination Compounds: When two simple salt solutions are mixed, two types of compounds are
obtained. These are double salts and coordination compounds. A double salt is a stable compound and it ionizes to
its components when it dissolves in water. Each ion retains its specific property. Although coordination compounds
are stable, they don’t ionize completely when they dissolve in water. In other words, some ions lose their specific
properties.
Chain Theory: It is a theory which explains the formation of coordination compounds in which ligands are bonded
to each other just as carbon atoms do and form chains. According to this theory, ligands are bonded to central atom
in order to satisfy single type of valence.
Werner’s Theory: It is another theory explaining formation of coordination compounds. According to this theory,
most of the elements have two kinds of valences. The first is the oxidation state and the second is the coordination
number. Each element that participates to form coordination compound tries to satisfy both valences. First valence
is satisfied by negative ions whereas second valence is satisfied by negative ions or neutral molecules.
Ligand: They are negative charged atoms or molecules. They are bonded to central atom with electrons. If a ligand
donates a pair of electrons, it is called as a monodentate ligand, if it donates two pairs of electrons, it is called as a
bidentate ligand, if it donates more than two pairs of electrons, it is called as a multidentate ligand.
Effective Atomic Number Rule: According to this theory, formation of coordination compounds is accepted as a
reaction between a Lewis acid (metal) and a Lewis base (ligand) by forming coordinate covalent bond. This theory
closely relates hybridization and geometrical shapes of coordination compounds. In this theory, in order to show
configuration of electrons from ligands and electrons in outer shell of metal , orbitals of metal are shown with
squares (sometimes with circles.)
Coordination Numbers and Geometrical Shapes: Coordination number is related to geometrical shape of complex
compounds. According to this, if coordination number is 2, the expected geometrical shape is linear. If coordination
number is 3, the expected geometrical shape is either trigonal planar or trigonal pyramid. But if coordination num-
ber is 4, the expected geometrical shape is either tetrahedral or square planar.

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QUESTIONS OF CHAPTER-5
5-1- What are the distinctive properties of transition elements?
5-2- What is the difference between double salts and complex compounds?
5-3- When FeSO4 and (NH4)2SO4 solutions are mixed in 1:1 mole ratio, Fe2+ ion appears in the resulting solution.
But when CuSO4 solution is mixed with ammonia solution in 4:1 ratio, no Cu2+ ion is observed. Explain this by
giving reason(s).
5-4- Define effective atomic number. Then calculate this number in the following complexes:
1- [PtCl6]2-
2- [Pt(NH3)6]
3- [FeCl4]-
4- [Cr(NH3)6]3+
5- [Ag(NH3)2]+
Answers: 1) 86, 2) 90, 3) 31 ,4) 33 , 5) 50
5-5- What are the oxidation states (first valence) of iron in the following compounds?
1- [Fe(CO)5]
2- [Fe(C2O4)3]3-
3- K3[Fe(CN)6]
4- [Fe(H2O)5(NO)]SO4
Answers: 1) 0 2) (+3) 3) (+3) 4) (+2)
5-6- Name the following complex compounds:
1- [Fe(H2O)5(NO)]2+
2- Na2[Fe(CN)5(NO)]
3- [Co(N3)(NH3)5]SO4
4- K4[Ni(CN)4]
5- [Cr(H2O)4Cl2]+
6- [Ni(en)2Cl2]2+
7- [Co(NO2)3(NH3)3]
8- K2[PtCl6]
5-7- Write down structural formulas for the following complex compounds:
A- Tris(ethylenediamine)cobalt(III) nitrate
B- Potassium tetracyanonickelate(0)
C- Aquabis(oxalato)chromate(III) ion
D- Potassium tetrachloronickelate (II)
E- Potassium tetrachloromanganate (II)
F- Hexaaquatitanium(III) chloride
G- Tetracarbonylnickel (0)

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 Chapter - 5

H- (Ethylenediamine)tetraiodochromate (III) ion

I- Aquacyanobis(ethylenediamine)cobalt (III) ion
J- Tetraamminecopper (II) ion
5-8- Answer the following questions for the 3 given coordination compounds.
[ Cr(H2O)5Cl]Cl2.H2O, [Cr(H2O)6]Cl3 , [Cr(H2O)4Cl2]Cl.2H2O
A- What is the oxidation state (first valence) of chromium in each compound?
B- What is the coordination number of chromium in each compound?
C- What are the names of these compounds?
5-9- Circle the right answer in the following questions.
1- What is the oxidation state (first valence) of [Cr(H2O)4Cl2]+ ?
A) 3 B) 1 C) 6 D) 5
2- What is the oxidation state of [Pt(C2H4)Cl3]- ion?
A) 1 B) 2 C) 3 D) 4
3- What is the structural formula for dichlorobis(urea)copper(II) compound?
A) [Cu{(NH2)2CO}2]Cl2
B) [Cu{(NH2)2CO}Cl]Cl
C) [CuCl2{(NH2)2CO}2]
D) None of the above
4- According to IUPAC system, what is the name of the [Pt(NH3)3Br(NO2)Cl]Cl compound?
A) triamminechlorobromonitroplatinum(IV) chloride
B) chlorotriamminebromonitroplatinum(IV) chloride
C) triamminebromochloronitroplatinum(IV) chloride
D) triamminenitrochlorobromoplatinum(IV) chloride
5-10- Reply the questions about the following coordination compounds according to Valence Bond Theory (VBT).
[PtCl4]2- ; [Pd(CN)4]2- ;[Ni(dmg)2] ;[CoCl4]2-; [Zn(CN)4]2- ; [Co(CN)4]2- ; [ZnCl2(NH3)2]
A- What is the type of hybridization of central atom?
B- What is the geometrical shape of complex compound?
C- What is the magnetic property of complex compound? Why?
5-11- What are the numbers of single (unpaired) electrons in the following coordination compounds according to
Valence Bond Theory? What is the value of magnetic moment value ( μ ) in each?
[Ni(H2O)4]2+ ; [Ni(NH3)4]2+
5-12- As the magnetic moment value of [MnL4]2- compound is 5.9 B.M, what is the type of hybridization of Mn (II)
which has L monodentate ligand? What is the geometrical shape of this ion according to Valence Bond Theory?
Answer: sp3, tetrahedral

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5-13- Suppose that [NiL4]2- complex ion contains Ni (II) and L monodentate ligand which is weak. Answer the
following questions according to the complex ion. (28Ni)
1- What is the charge of the ligand?
2- What is the hybridization type of the central atom?
3- What is the value of magnetic momentum (μ)?
5-14- Define the following terms:
Coordination compound, ligand, donor atom, coordination number, chelating ligand

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 Chapter - 6

CHEMICAL ANALYSIS CHAPTER-6

ACHIEVEMENTS
After studying this chapter, students can perform the following:
* They learn different methods of chemical analysis.
* They can differentiate qualitative and quantitative analysis.
* They will have information about some positive ions.
* They understand the importance of quantitative analysis method in determining the amounts of unknown
compounds.
* They learn steps of quantitative analysis and how to do it.
* They can perform necessary calculations in quantitative analysis.
* They understand the importance of volumetric analysis in determining the amount of substance dissolved
and concentration of unknown solution.
* They learn calculation of equivalent mass of different substances and relationship between chemical reac-
tions.
* They learn some laboratory equipments which are used in volumetric analysis.
* They can determine end point and equivalent point by using indicators in volumetric analysis.

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6-1 PREFACE
Chemical analysis has wide applications in industry, chemistry, biology, geolo-
gy and in other science fields. For example, while analyzing air pollution, it is
necessary to measure the amounts of hydrocarbons, nitrogen oxides and carbon
monoxide from exhaust fumes. To diagnose goiter illness, it is necessary to
find out calcium amount in human blood. The amount of nitrogen from food
we consume gives the amount of protein. In industry, by regular mass analysis,
the strength of iron and its resistance to corrosion can be checked. As it is un-
derstood from those examples, chemical analysis has an important place in life.
The chemical analysis which is used to find out the components (elements or
compounds) which form a substance is called as qualitative analysis and the
analysis which is used to find out the percentage of the components of a sub-
stance is called as quantitative analysis.

6-2 METHODS OF QUALITATIVE ANALYSIS

The aim of qualitative analysis of a sample is to find out what the component(s)
is/are in a mixture or solution and how these components (elements or a group
of elements) are bonded to each other. The substance which is wanted to be
analyzed is usually transformed to a known compound by a substance called
as detector.
For example, a mixture of common positive ions can be analyzed. In this case,
qualitative analysis is a two-step process. In the first step, ions are separated.
In the second step, through some certain chemical reactions, ions are detected.
To apply qualitative analysis, the sample is divided into groups. The reaction of
each group against different precipitants is examined. When the right precipi-
tant is added to solution, it precipitates the target ion and the resulting solid is
extracted from other ions by filtering method.
Common positive ions in nature are divided into 5 groups according to the
precipitation factor (Table 6-1). In other words, the ions in the same group
are precipitated with the same substance. The analysis process starts from the
first group and continues to the last group by addition of precipitant until the
precipitate is formed.
First, dilute hydrochloric acid (HCl) is added to solution and (Ag+, Pb2+, Hg22+)
from 1st group ions are separated from the solution in the form of chlorides
of these ions with filter paper. In order to precipitate 2nd group ions
(Hg2+,Cu2+,Bi3+,Cd2+,Pb2+,Sn2+ , As3+,Sb3+) hydrogen sulfide gas (H2S) is passed
through the solution. In the remaining solution, upon addition of ammonium
chloride (NH4Cl) and ammonium hydroxide (NH4OH) solution, IIIA group
positive ions are precipitated. Separation process goes on like this.
After positive ions are separated according to their groups, precipitate of each
group is analyzed to learn the presence of ions.
In the following experiment, the separation of first group ions from other
groups and methods of detection will be given.

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 Chapter - 6

Table Group of positive ions, precipitants and chemical formula of

6-1 precipitates
Group Precipitants Ions Precipitates
I Dilute Hydrochloric acid (HCl) Ag+, Hg22+, Pb2+ AgCl, Hg2Cl2, PbCl2
Dilute Hydrochloric acid upon
Hg2+, Cu2+, Bi3+, Cd2+, HgS, CuS, Bi2S3, CdS,
II addition of hydrogen sulfide gas
(H2S) Pb2+, Sn2+, As3+, Sb3+ PbS, As2S3, Sb2S3, SnS
Ammonium hydroxide + ammo- Al(OH)3, Cr(OH)3,
A Al3+, Cr3+, Fe3+
nium chloride (NH4Cl, NH4OH) Fe(OH)3
III
By passing hydrogen sulfide gas
B (H2S) into (NH4Cl, NH4OH)
Ni2+, Zn2+, Co2+, Mn2+ NiS, ZnS, CoS, MnS

Addition of (NH4)2CO3 into

IV NH4Cl, NH4OH
Ca2+, Ba2+, Sr2+ CaCO3, BaCO3, SrCO3

Substance remaining in final

V solution without precipitation
Mg2+, Na+, K+, NH4+

Attention: 6-2-1 Separation of Group I Ions and Detection

Pb+2 is in both groups I and II, be- As mentioned above, first group positive ions (Ag+, Pb2+, Hg22+) are separated
cause solubility of lead ion is high from solution by precipitation as chloride compounds. In the second step, each
and some may not precipitate when positive ion is detected according to the following principles.
dilute HCl is added.
1. PbCl2 precipitate dissolves in hot water but AgCl and Hg2Cl2 don’t dissolve
in hot water. Dissolved PbCl2 is separated by filtering from other precipitates
upon addition of hot water. In order to detect lead, K2CrO4 detector is added to
the filtered substance. If there is lead, yellowish PbCrO4 precipitates according
to the following equation.
PbCl2 + K2CrO4 → PbCrO4 ↓ + 2KCl
Yellow precipitate

2. After separation of lead chloride, dilute ammonia solution is added to the re-
maining solution (Hg2Cl2, AgCl). Silver chloride AgCl forms a complex com-
pound diamminesilver(I) chloride [Ag(NH3)2]Cl which dissolves in ammonia
solution and passes filter. To detect silver, dilute nitric acid (HNO3) is added
and a white precipitate forms or potassium iodide (KI) solution is added and a
yellow precipitate forms.
AgCl + 2NH3 → [Ag(NH3)2]Cl
diamminesilver(I) chloride

[Ag(NH3)2]Cl + 2HNO3 → AgCl ↓ + 2NH4NO3

White precipitate

[Ag(NH3)2]Cl + KI → Agl ↓ + KCl + 2NH3

Yellow precipitate

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 Chemical Analysis
Mercury (I) chloride (Hg2Cl2) reacts with ammonia solution and forms a black
precipitate according to the following equation.
Exercise 6-1
Complete the following reactions.
Hg2Cl2 + 2NH3 → Hg(NH2)Cl ↓ + Hg ↓ + NH4Cl
Hg22+ + HCl →
White precipitate Black precipitate
dilute

Upon addition of king’s water (HNO3+3HCl), a soluble salt HgCl2 is

HCl
formed. To detect mercury, tin (II) chloride (SnCl2) is added to the solu- Bi3+ + H2S →
dilute
tion and a precipitate is obtained which is white in the beginning then
turns into black.
NH Cl
Al3+ + NH4OH →4

2HgCl2 + SnCl2 → SnCl4 + Hg2Cl2 ↓

White precipitate NH OH
Mn2+ + H2S →4

NH4Cl
Hg2Cl2 + SnCl2 → SnCl4 + Hg ↓
Black precipitate

Example 6-1
How are silver, cadmium and iron (III) ions separated?
Solution:
Silver (Ag+) ion is in Group I, cadmium (Cd2+) is Group II and iron (III) (Fe3+)
is in Group III. Therefore, we need to add precipitants in order.

1. When dilute hydrochloric acid solution is added, only silver ion precipitates
as AgCl. Cadmium and iron ions remain as dissolved. We can separate silver
chloride from other components of solution by filtering.

2. H2S gas is passed through the solution. As a result, cadmium ions precipitate
as cadmium sulfide and are separated from solution by filtering method.

3. Only iron (III) ions remain in the solution. We can precipitate iron in iron(III)
hydroxide (Fe(OH)3) form by adding ammonium hydroxide and ammonium
chloride solutions.

6-3 QUANTITATIVE ANALYSIS

Quantitative analysis aims to determine the amount of target substance in a
sample. For example, calculation of percentage of iron in a rock is an appli-
cation of quantitative analysis. The amount of substance can be expressed as
percentage and also in a ratio of thousand, million or even billion. Besides, the
amount of substance is expressed as the mass or volume of matter found in a
certain volume of the sample or described as molar ratio.

Quantitative analysis process is applied through two measurements. The first is

the amount of the subject sample, and the second is the amount of the compo-
nent which we want to measure in the sample. Mass, volume, strength of col-
or, absorption intensity, electric intensity or any physical or chemical property
about the amount of matter can be given as examples to measurements during
analysis. But, in this book, we will cover measurements of number of moles,
equivalent mass, mass and volume which show amount of matter.

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 Chapter - 6

Before applying quantitative analysis, the following are the steps to be made.
1. Exemplifying: It is the method of obtaining the sample which represents the
substance in a right way. This method is used especially when the sample isn’t
homogeneous.
2. Preparing the sample: The sample undergoes a preparation process for
analysis in laboratory. It includes processes as grinding the solid sample, mix-
ing, making it homogeneous and removing the moisture in it.
3. Measuring the sample: In order to determine the amount of matter cor-
rectly, the mass and volume of the sample to be analyzed needs to be known
precisely.
4. Dissolving the sample: Chemical analysis is usually made on solutions.
Therefore, a solution of the sample needs to be prepared. This solution is pre-
pared with a solvent which can dissolve not only the target component in the
sample but all of the components. The solvent normally doesn’t change the
amount of the sample.
5. Separating the mixed substances: There are certain substances which have
physical and chemical properties with which correct measurement processes
can be made in quantitative analysis. In this case, measurements can be es-
timated directly. But in many cases, by measuring one of properties directly,
it may not be possible to identify the substance. To make measurements in
quantitative analysis, chemical reactions with the target compound are neces-
sary. Those reactions used in chemical analysis and measured properties may
be common for some elements and compounds in the sample. This situation
affects results of analysis and some problems may arise in chemical analysis
processes. For this reason, the target substance needs to be separated from oth-
er components in the sample which affect analysis. The other elements in the
sample which affect the results of the target substance are called as interferents.
Separating those before measurement is important for analysis.
Practically, the person working in quantitative analysis field may apply many
different analysis methods to get results. In order to choose the most suitable
method, many factors need to be considered. The urgency of analysis, suitabil-
ity and degree of correctness, supplying tools and devices, number of samples,
amount of samples and concentration of target substance in sample, cost of
analysis are some of those factors. Therefore, the success of analysis depends
on choosing the suitable method.
Quantitative analysis includes many methods with respect to their uses and
significance. Those are usually considered in two titles:

6-3-1-Quantitative Chemical Analysis

Under this title, classical analysis methods are placed. Those are:
1- Gravimetric analysis methods: They depend on measurement of mass.
2- Volumetric analysis methods: They depend on measurement of volume.

6-3-2-Instrumental Analysis
Different instruments are used in analysis. In this chapter, classical analysis
methods will be studied.

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6-4-GRAVIMETRIC ANALYSIS
In gravimetric analysis, a substance related to another substance with a known
chemical structure is separated and its mass is measured correctly. Separation
process is made from a sample with a known amount. In gravimetric analysis,
the target substance is usually transformed into a pure and a chemically stable
compound. This compound has a shape and formula which enables measuring
its weight precisely. After measurement, as the chemical formula of the sub-
stance is known, its mass can be calculated.
In gravimetric analysis, the target substance is separated through different
methods. The most important of those are:
1- Volatilization method
2- Precipitation method
3- Electrical precipitation method
4- Other physical methods

6-4-1-Volatilization Methods
These methods depend on removal of the volatile substance in the sample. This
process is applied through different methods below:
A- Burning method in air at high temperature
B- The method in which the sample undergoes reactions with chemical indi-
cators and volatilize its components and target substance residues. Afterwards,
volatilized substances are collected in a suitable medium and their mass is cal-
culated. This method is called direct volatilization. In indirect volatilization,
the mass of volatile substance is calculated through the loss in mass of the sam-
ple. For example, we can determine the percentage of crystal water in aqueous
barium chloride
(BaCl2 .2H2O) by direct volatilization method through heating.

Sample
Electric oven

Catalyst

To prevent gas interfer-

To absorb water
to absorb CO2 gas on ence from outside on
P4O10
asbestos NaOH asbestos P4O10 + NaOH

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 Chapter - 6
The vapor is absorbed on a suitable medium and its weight is measured. To
determine crystal water in aqueous barium chloride by indirect volatilization
method, it is heated in open air and this causes water to vaporize. The mass of
residue BaCl2 is measured and the mass of crystal water is determined by sub-
tracting this mass from the sample’s mass.
In another example, to determine the mass of carbon dioxide CO2 in calcium
carbonate sample, hydrochloric acid HCl is added to it.

CaCO3 + 2HCl → CaCl2 + CO2 ↑ + H2O

volatile substance

Carbon dioxide gas is passed through a drying substance to remove its mois-
ture, and then it is absorbed by a suitable medium (asbestos immersed in sodi-
um hydroxide solution). The mass of carbon dioxide is calculated through the
mass increase in absorbent medium.

Example 6-2
1.451 g of aqueous barium chloride (BaCl2.2H2O) sample was analyzed
through indirect volatilization method to determine the mass of crystal water.
The sample was heated at 125 °C for some time and then it was cooled in a dry
medium. As the mass of solid substance is 1.236 g, what is the mass percentage
of crystal water in the sample?

Solution:
Mass of crystal water
Percentage of crystal water = Mass of the sample × 100%

The mass of crystal water lost during volatilization is calculated through the
following equation:
heating
BaCl2.2H2O → BaCl2 + 2H2O
before heating after heating volatile substance

Mass of crystal water = mass of the sample before heating - mass of the

sample after heating

m H O (g) = m BaCl .2H O - m BaCl

2 2 2 2

m H O (g) = 1.451 (g) - 1.236 (g) = 0.215 g

2

Percentage of crystal water:

m H O (g)
H 2O % = × 100%
2

m BaCl .2H O (g)

2 2

0.215 (g)
H 2O % = × 100% = 14.81%
1.451 (g)

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 Chemical Analysis

Example 6-3 Exercise 6-2

A sample of organic matter was analyzed through direct volatilization meth- A mixture containing nickel, chro-
od to determine its carbon percentage. 15.24 mg sample was burnt in aerobic mium and a small amount of car-
conditions and CO2 gas was absorbed on a suitable medium. As the mass of bon was analyzed gravimetrically
carbon dioxide is 22.36 mg, calculate the percentage of carbon element in the by volatilization method. 1.4 g of
compound. mixture was burnt in aerobic con-
ditions and emitted CO2 gas was
Solution: collected. As the mass of CO2 gas
is 2.2 mg, find the percentage of
Mass of carbon
_________________
Percentage of carbon = × 100% carbon in the mixture.
Mass of the sample
(C:12 g/mol, CO2: 44 g/mol)

We can calculate the mass of carbon from evolved CO2 gas. Because this gas Answer: 0.043%
was emitted through burning of carbon in the sample.

C CO2↑
MC (g/mol)
____________
mC = mCO2 (mg) ×
MCO2 (g/mol)

12 (g/mol)
___________
mC = 22.36 (mg) × = 6.1 mg
44 (g/mol)

mC
______ 6.1 (mg)
__________
C%= × 100% = × 100% = 40%
msample 15.24 (mg)

6-5 PRECIPITATION METHODS

Gravimetric analysis method which depends on precipitation reactions consist
of some steps that need to be made quantitatively (that means in a way without
any increase or decrease in amount of matter).
These steps are as follows:
1- Dissolving a known, net mass in a suitable solvent. Weighing is done with
different scales with different sensitivity. Some scales are sensitive to the ten
thousandth of a gram while some are only sensitive to the tenth of a gram.
2- To precipitate a sample in a solution as in the form of a compound which is
slightly-soluble and with a known chemical formula. By using a suitable pre-
cipitant, a precipitate is formed with a known chemical formula.
3- Separating and removing precipitate from a solution by filtering.
Some scales (micro-balances) to
weigh samples

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 Chapter - 6

4- Washing the precipitate: The precipitate separated from its solution remains
on the filter paper. To remove the impurities on the precipitate, it needs to be
washed with a suitable solvent. The solvent used for washing needs to have
some properties. These are:
a- It shouldn’t affect the solubility of the precipitate; it should only help to
dissolve impurities.
b- It shouldn’t form a volatile compound with the precipitate.
c- It should be volatile to be removed from the precipitate easily.

5- Drying the precipitate: This step means that precipitation formula (the chem-
ical formula of the formed precipitate) is transformed to a suitable mass for-
Addition of reactant to the sam- mula. This process is done through drying (sometimes at a temperature over
ple solution and formation of the 100 °C) or burning (temperature reaching 1000 °C.)
precipitate
Thus, the precipitate is removed from any type of moisture (base water, re-
tained water, crystal water)

drying at 130 °C
CaC2O4.H2O → CaC2O4 + H2O ↑
precipitate formula mass formula

drying at 130 °C
Al2O3.xH2O → Al2O3 + xH2O ↑
precipitate formula mass formula

Burning process causes removal of water from the structure of the precipitate
and also decomposition of the precipitate through thermal reactions.

drying burning
CaC2O4.H2O → CaC2O4 + H2O →
130 - 225 °C 400 - 490 °C

burning at 840 °C

Removal of substance by pre- CaCO3+ CO ↑ → CaO + CO2 ↑

cipitation and then washing
with a suitable solvent.
6- The precipitate is weighed for correct calculation of its mass through mass
formula. To achieve mass analysis and get correct results, the following points
need attention:
1- In order to prevent loss of mass in precipitate, it should have a very slight
solubility.
2- The precipitate needs to have some physical properties to be separated from
solution and removed from impurities. The crystals of the precipitate must be
at suitable sizes. Thus, impurity possibility is low, the precipitate cannot pass
through the filter paper and the size of the particles isn’t affected from washing
process.
3- The precipitate must be suitable to be dried, burnt or to be processed with
suitable chemical reactants in order to be converted to a pure substance with a
stable chemical formula.

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6-5-1- Separating the precipitate by filtering and purifying

Separating the precipitate principally depends on the particle size of the precip-
itate. The precipitates with bigger particle sizes can be separated fully, quickly
and easily. If the precipitate has a small particle size, a filter paper with smaller
pores needs to be used for separation. In this case, separation takes more time
and it is more difficult. On the other hand, the relationship between particle size
and purity of the precipitate isn’t clear. But, generally precipitates with bigger
particle sizes can be obtained in a purer form.

6-5-2- The factors affecting the particle size of the precipitate

There are some factors affecting the size of particles of the precipitate during
precipitation process. Some of those depend on the type of the precipitate while
some depend on the conditions under which precipitation is made. If the pre-
cipitate is in the form of colloidal form (the volume of the particles in this Drying oven: It is used to dry
precipitate is nearly 10-4 -10-6 mm.) this kind of particles cannot be separated precipitates at hight temperature. (It
by filtering. The other type of precipitate has comparably bigger sized particles. can reach 100°C temperature)
These particles can be separated from solution easily. The aim of the precipi-
tation process is to have a crystallized precipitate. This is a preferred property
for a precipitate. The most significant conditions affecting the precipitation are
as follows:
1- The characteristic and chemical structure of the precipitate: Compounds like
BaSO4 dissolve slightly. This kind of substances form crystallized precipitates
when they are mixed with substances as AgCl.
2- Solubility of the precipitate: During precipitation, solutions with high solu-
bility form crystallized precipitates and vice versa.
3- Temperature: During precipitation, generally the solubility of most precipi-
tates increases with temperature and a crystallized precipitate forms as a result
of precipitation at high temperatures. Because, by slowing the precipitation
process, necessary time for crystallization is supplied.
4- The concentrations of substances involved in precipitation process: In pre-
cipitation process, dilute solutions (valid for the target component and the sol-
vent) are preferred. During the process, the solvent must be added slowly and
solution must be mixed continuously. Under these conditions, necessary time
for the formation of precipitate crystals is supplied and therefore a crystallized
precipitate is formed.

6-5-3- Chemical structure of precipitate and calculations

in Gravimetric Analysis Muffle furnace: It is used to burn
After drying and burning steps, the last step in gravimetric analysis is weigh- precipitates over 1000 °C tempera-
ing the precipitate correctly. Because the resulting substance isn’t exactly the ture.
substance to be measured itself but usually another substance containing it. For
example, in order to measure barium in a sample by gravimetric analysis, it is
precipitated as BaSO4. At the end of the precipitation process, the precipitate
is weighed as BaSO4 after separation, washing and drying processes finished.
(mass formula):

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 Chapter - 6

separation and drying

Ba2+ + SO42- ⇌ BaSO4 → BaSO4
precipitating agent precipitating formula mass formula

In the following example, calcium is weighed as calcium oxide:

separation and drying

Ca2+ + C2O42- ⇌ CaC2O4 → CaO + CO ↑ + CO2 ↑
precipitating agent precipitating formula mass formula

Therefore, at the end of each gravimetric analysis, after determining the net
weight of mass formula by a micro-balance, some calculations are necessary
to learn the amount of substance to be measured (sought substance). These
calculations depend basically on equilibrium reactions (or reaction groups) and
include application of percentage and ratio rules.

Molar mass of sought substance

(atomic or molecular) Mass of sought substance
_______________________ _______________________
=
Molar mass of gravimetric Mass of gravimetric formula
formula (mass of precipitate)

The ratio of molar mass of the sought substance to molar mass of gravimetric
formula is called as Gravimetric factor, Gf (G: First letter of word gravimetric
and F: first letter of word factor.) (For the component in mass formula)
But in both formulas, atoms or molecules need to be found for same number
of components.
a Msought substance (g/mol)
Gf = ×
b MMass formula (g/mol)

In this formula, a and b shows the lowest numbers for two compounds to have
the same sought substance in numerator and denominator. Below are examples
on how gravimetric factor is calculated.

Example 6-4
Calculate the gravimetric factor of chloride (sought substance) in AgCl (mass
formula) precipitate. (MAgCl= 143.5 g/mol), (MCl= 35.5 g/mol)

Solution:
In this example, chloride is the sought substance. AgCl is accepted as gravi-
metric formula.
a MCl (g/mol)
Gf = ×
b MAgCl (g/mol)

As both formulas contain the same number of chloride atoms, a and b are both
equal to 1. Therefore, Gf which is gravimetric factor of silver chloride is calcu-
lated as follows:

192 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Analysis

Exercise 6-3
1 35.5 (g/mol) Complete the following table.
Gf = × = 0.25 Substance to
1 143.5 (g/mol) Gravimet-
be measured
mass formula ric Factor
(sought sub-
(Gf )
stance)
If the result is examined, it is seen that gravimetric formula is a numeric value AgI I
and therefore, it doesn’t have a unit. Ni(C4H7N2O2)2 Ni

Gravimetric factor is used in calculating the mass of the sought component. Fe2O3 Fe3O4

This is done practically by the mass of precipitate as shown in the following AgI MgI2
formula. For this, gravimetric factor is multiplied by mass of precipitate (mass Al2O3 NH4Al(SO4)2
formula). Molar masses of the substances:
AgI: 235, I: 127, Ni(C4H7N2O2)2 : 289,
Ni: 59, Fe2O3: 160, Fe3O4: 232,
AgI: 235, MgI2: 278, Al2O3: 102,
(1) msought substance (g) = Gf × m mass formula (g)
NH4Al(SO4)2 : 237

Or the following equation is used to calculate the percentage of the sought Answer:
substance found in sample. 0.54, 0.203, 0.967, 0.592, 4.647

Msought substance (g/mol)

(2) Percentage of sought substance % = × 100%
Msample (g/mol)
Exercise 6-4
Calculate gravimetric factor of iron
If we insert m from Equation 1 in Equation 2, we get the following:
in Fe2O3 compound. (MFe= 56 g/
mol; MFe2O3=160 g/mol)
Gf × mmass formula (g) Answer: 0.7
Percentage of sought substance % = × 100%
msample (g)

Example 6-5
What is the mass of calcium oxide (CaO) formed by complete burning of
3.164 g of calcium oxalate (CaC2O4) ?

Solution:
Firstly, the equilibrium reaction showing the burning is written.
burning
CaC2O4(solid) → CaO(solid) + CO2 ↑ + CO ↑

Then, gravimetric factor of CaO (M = 56 g/mol) in calcium oxalate CaC2O4

(M=128 g/mol) is calculated. a and b is determined as 1. (Because the number
of calcium atoms in both formulas are equal)

FEZALAR EDUCATIONAL INSTITUTIONS 193

 Chapter - 6

Exercise 6-5 Gf =
a
×
MCaO
b MCaC2O4
120 mg of an organic substance
was treated with nitric acid. Then,
in order to precipitate the chloride 1 56 g/mol
content of the compound quantita- Gf = × = 0.4375
1 128 g/mol
tively as silver chloride, some sil-
ver nitrate was added to the result-
ing solution above. As the mass of In order to get the mass of CaO, gravimetric factor is multiplied with mass of
the precipitated silver chloride is CaC2O4 according to the following equation:
153 mg, calculate the percentage
of chloride (MCl =35.5 g/mol) in
the sample. mCaO (g) = Gf × m CaC2O4 (g)
(AgCl: 143.5 g/mol) The mass of calcium oxide is found as follows:

Answer: 31.5% mCaO (g) = 0.4375 × 3.164 g = 1.384 g

Exercise 6-6
6-6 VOLUMETRIC ANALYSIS
After 0.764 g of sample was dis-
solved, plenty of dilute ammoni- Volumetric analysis is a quantitative analysis method. It is based on the volume
um hydroxide (NH4OH) was used measurement of a chemical reagent with unknown concentration with the help
to precipitate the aluminum in the of another solution with known concentration. The solution with known con-
sample as Al2O3xH2O. After wash- centration is called as standard solution. Therefore, this solution is defined as
ing the formed precipitate, it is follows: It is a solution which contains a known and certain amount of reagent
dried as Al2O3. in a certain volume. (Equivalent grams, number of moles or grams etc.) After
volumetric analysis process is finished, from the volume of standard solution,
1- Determine the precipitation and the amount of sought component can be calculated according to chemical va-
mass formulas. lence rules.
2- Can the precipitation formula In order to obtain standard solutions, direct preparation method of solution is
be used as mass formula? used. This is done through dissolving a certain amount of standard substance
in a certain volume of solvent (distilled water is usually used as solvent.) The
3- Calculate the percentage of
solution prepared through this method is called as primary standard solution.
Al2O3 (M=102 g/mol) in the sam-
ple as mass formula is 0.127 g. On the other hand, most of the time standard solutions are prepared through
standardization method. In this method, it is done through precise measure-
Answer: 16.62 % ment of volume of solution which reacts with a certain amount of standard
4- Calculate the percentage of substance in order to determine precise concentration of solution. In this case,
aluminum (M=27 g/mol) in the standard solution is called as secondary standard solution.
sample. As known, not all chemical substances which are used to prepare solutions are
standard substances. Standard substances to be used must have the conditions
Answer: 8.8 % listed below:
1- They need to be pure.
2- They mustn’t react with air.
3- They must have a big equivalent mass in order to minimize mistakes which
can occur at weighing process while preparing solution.

194 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Analysis

4- They need to have the capability of dissolving in the solvent (mostly distilled
water) which is used in analysis.
5- Non-poisonous substances are preferred.
6- Preferably, they need to be cheap and found abundantly.

6-6-1 Titration
Most of the time, volumetric analysis is done at laboratory. This is done through
quantitative volume measurement of one of the solutions (e.g. standard solu-
tion) which is necessary to react with a certain amount of unknown solution.
Then, the concentration of the unknown solution is calculated. This process is
performed by sending standard solution drop by drop from a burette to a flask
which contains the unknown solution. (Figure 6-2)
This addition process which continues until the reaction between chemical re-
actant and sought component completes is called as titration. In titration pro-
cess, the point at which the reactions end is called as equivalent point. This
point is practically can be observed with naked eye easily through a change in
a property of the solution (e.g. change in the color of solution or formation of
precipitate.) For this purpose, usually chemical substances called as indicators
are added to the solution. Indicators are substances whose colors or one of
their physical properties change clearly at/near equivalent point although they
don’t take place in the reaction. Therefore, this point at which change occurs
and addition from burette is stopped is called as end point. This point needs
to coincide with equivalent point. But between two points (theoretically and
practically) a small difference can occur. This is a result of an error in titration.
As titration is the most common and most used process, mostly, instead of the
volumetric analysis term, the titration analysis term is used. But the volumet-
ric analysis term is more extensive. Because it includes quantitative processes
used in analysis of gases in addition to titration analysis.
The reactions between standard reagents and compounds to be measured need
to follow some conditions.
1- The reactions need to be expressed with chemical equations. They need to be
one way but not equilibrium reactions.
2- The reaction need to be complete and fast. In some cases, a catalyst can be
used to increase the reaction rate.
3- Practically, the end point of the reaction needs to be determined. This is pos-
sible via a change in a property of solution at or near equivalent point.
According to this, we can divide chemical reactions which have the conditions
above and can be used successfully in titration processes into 4.
These are:

1-Neutralization Reactions:
These reactions include titration of a strong base with a standard solution of a
strong acid or the opposite as the titration of a strong acid solution with a stan-
dard solution of a strong base. Because hydrogen ion reacts with hydroxide ion
and water is formed.

FEZALAR EDUCATIONAL INSTITUTIONS 195

 Chapter - 6

Figure 6-2 2-Oxidation and Reduction Reactions:

This includes the reactions of all substances of which a change occurs in oxi-
dation numbers. The standard solution in these reactions is either a reducing or
an oxidizing agent.

3-Precipitation Reactions:
These reactions include interaction of ions (except H+ and OH-) to form simple
precipitates. For example, the reaction between silver and chloride ions.

4-The Formation Reactions of Complex Ions:

In these reactions, polyatomic anions or cations are bonded to other ions or
molecules and they form coordination compounds. These compounds dissolve
in solutions but as shown below, they decompose little.

6-6-2-Methods of Defining Concentrations of Solutions Used

in Titration:
As we have studied before, standard solution is a solution formed by dissolving
a certain amount of reactant in a certain volume of solution. There are many
methods which define the concentration of solution. The following are the most
A) Instruments used in titration commonly used in volumetric analysis:

B) Colorless phenolphthalein turns

Molarity (M):
into pink at pH = 10 point A solution with 1 molar concentration is formed by dissolving 1 mole of sub-
stance in 1 liter solution. In other words:

Attention: In the following chapters,

we will study the hydrolysis of salts de-
rived from weak acids and bases. Besides, M
we will study what oxidation and reduc-
tion reactions are and how they are used in
chemical analysis.
The symbols in the equation are: n is number of moles; M is molar mass of
dissolved substance; V is volume of solution.

Normality (N):
You have seen different ways to define the concentration of a dissolved sub-
stance in a solution. Now you will see a new method called as normality to
define concentration. Also there are other terms you will meet later.
1 normal solution is formed by dissolving 1 equivalent gram of substance in 1
liter of solution.

196 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Analysis

Attention: Here, as you can see,

instead of molar mass M, equiva-
lent mass EM (g/eq) is used.

eq in the equation is equivalent gram, EM is equivalent mass.

As known, the molar mass of any substance is equal to the sum of atomic mass-
es forming this substance. This amount is constant and shown as gram/mol (g/
mol). Equivalent mass of any substance is the mass of substance which pro-
duces or consumes 1 mole of active component (reactant). This amount isn’t
constant. It can change with respect to the reaction type in which the substance
participates. According to this, a single compound may have more than one
equivalent mass with respect to the reaction type in which it takes place. This
value is shown with (g/eq) unit.
Standard concentration is usually used to prevent confusion which may arise
as in one mole of substance, one or more moles of active (reactant) substance
is found. Therefore, it is preferred in calculations of quantitative analysis meth-
ods which depend on titration.

6-6-3-Calculation of Equivalent Mass (EM)

Calculation of equivalent mass of any compound changes with respect to the
reaction type in which the compound participates. These calculations are:

1-Balancing Equation:
The equivalent mass of an acid is defined as the mass of acid which has one
mole of hydrogen atom (1.008 g hydrogen) that can change (participate) in the
reaction. We can define this mathematically as follows:
Molar mass of acid
_______________________
Equivalent mass of acid =
Number of ionized H+ ions
Ma
_______________________
EM =
Number of ionized H+ ions

a in the equation is the first letter of the word acid.

The equivalent mass of a base is defined as the mass of base which has one
mole of hydroxide group (17.0081 g of ionized hydroxide group) that can
change (participate) in the reaction.

Mb
_______________________
EM =
Number of ionized OH- ions

b in the equation is the first letter of the word base.

When salts obtained from hydrolysis of weak acids and strong bases or vice
versa participate in this kind of reactions, their equivalent masses can be cal-
culated. For this, a balanced chemical equation of acid-base reaction is written.

FEZALAR EDUCATIONAL INSTITUTIONS 197

 Chapter - 6

The mole number which is equivalent to acid or base is found and this number
is used to calculate equivalent mass as shown in the following example.

Na2CO3 + 2HCl → 2NaCl + H2O + CO2 ↑

Salt of weak acid

Molar mass of Na2CO3 Molar mass of Na2CO3

Equivalent mass of Na2CO3 = _______________________ = _____________
Mole number of active part of acid 2
Number of moles of H+

MNa2CO3
EMNa2CO3 = ________
2

2-Precipitation and Complex Component Reactions

The equivalent mass of a substance which participates a precipitation reaction
is equal to a substance which includes a mole of single positive ion (equivalent
to 1.008 g hydrogen) or a substance which reacts with it.
Molar mass of substance
Equivalent mass = ______________________________
Positive ion × number of valence

M
EM = ___________________________
Positive ion× number of valence
The equivalent mass of a substance which participates a reaction to form a
complex component (which has electron pairs as active part) shows the mass
of the substance which donates or takes electron pair.

M
EM = ___________________________________
Number of donated or taken electrons pairs

3-Oxidation and Reduction Reactions:

The equivalent mass of oxidation or reduction factor is the mass of the reagent
which includes or reacts with 1.008 g hydrogen or 8.000 g oxygen. For exam-
ple, equivalent masses of potassium permanganate and potassium dichromate
which participate oxidation and reduction reactions can be calculated.
In order to calculate the equivalent masses of potassium permanganate
(KMnO4) and potassium dichromate (K2Cr2O7), virtual reactions are written to
determine amount of oxygen in each molecule.

According to those above, 2 molecules of potassium permanganate yield 5 ox-

ygen atoms. Therefore, the equivalent mass of this substance can be calculated
through the following equation.

198 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Analysis

Molar mass × 2
Equivalent mass of KMnO4 = ______________
10
With the same method, the equivalent mass of K2Cr2O7 is calculated as fol-
lows:
Molar mass
Equivalent mass of K2Cr2O7 = ___________
6

In order to simplify the subject, we can calculate the equivalent mass of any
substance which participate oxidation and reduction reactions according to the
following 2 reactions.
Molar mass
Equivalent mass of reduction factor = ______________________
Number of taken electrons
Molar mass
Equivalent mass of oxidation factor = ______________________
Number of donated electrons

As stated above, the equivalent mass of a substance is equal to the ratio of

molar mass of substance to ɳ (eta) number. This number shows the number of
moles of active part (the part participating reaction) of the substance. There-
fore, number of ɳ can be determined while deciding the active part of the sub-
stance (according to the reaction type that substance undergoes). Because this
value is ≥ 1. We can write the general relationship between equivalent mass of
substance with its molar mass. Attention: In order to dif-
ferentiate number of moles
of active part of substance
from number of moles, ɳ (eta)
symbol is used.

Example 6-6
Calculate equivalent mass of each substance which participate reactions below.
1. Pb(NO3)2(aq) + 2KI(aq) → PbI2(s) + 2K+(aq) + 2NO3-(aq)

2. H2SO4(aq) + 2NaOH(aq) → 2H2O(l) + 2Na+(aq) + SO42-(aq)

3. 5Fe2+(aq) + MnO4-(aq) 8H3O+(aq) → 5Fe3+(aq) + Mn2+(aq) + 12H2O(l)

4. AgNO3(aq) + 2KCN(aq) ⇌ [Ag(CN)2]-(aq) + 2K+(aq) + NO3-(aq)

FEZALAR EDUCATIONAL INSTITUTIONS 199

 Chapter - 6

Exercise 6-7 Solution:

Calculate the M, ɳ and equivalent 1- In order to calculate equivalent mass of a substance with respect to the type
mass (EM) of the following sub- of the reaction, value of molar mass and ɳ are needed to be known.
stances.
A- AgNO3 in the following precipita-
tion reaction:
Ag+(aq) + Br-(aq) → AgBr(s)
Answer: 1; 170 To calculate molar mass of Pb(NO3)2, atomic masses of atoms forming this
substance are summed up.
B- BaCl2 in the following precipita-
tion reaction:
Ba2+(aq) + SO42-(aq) → BaSO4(s)
Answer: 2; 104
C- Fe2(SO4)3 in the following precip- Then, according to the reaction equation below, value of ɳ is calculated.
itation reaction: Pb(NO3)2(aq) + 2KI(aq) → PbI2(s) + 2K+(aq) + 2NO3-(aq)
Fe2(SO4)3(aq) + Pb2+(aq) → The equation shows that Pb(NO3)2 participated a precipitation reaction as PbI2
2PbSO4(s) + 2Fe3+
(aq)
salt was formed. Therefore, the value of ɳ is calculated as follows:
Answer: 6; 66.7 ɳ = valence of positive ion x number of positive ions = 2x1 = 2 eq/mol
D- Na2CO3 in acid-base neutraliza-
tion reaction:
Na2CO3 + 2H+(aq) →
2Na+(aq) + CO2(g) + H2O(l)
Answer: 2; 53 With the same method, equivalent mass of KI salt is calculated.
E- BaI2 in the following complex ion
formation reaction:
ɳ = valence of positive ion x number of positive ions =1x1=1 eq/mol
2BaI2 + Hg2+
(aq)
→ HgI4(aq)
2-
+ 2Ba2+
(aq)

Answer: 2; 195.5
F- Na2S2O3 in oxidation reduction
reaction:
2- The following is an acid-base reaction.
2S2O32-(aq) → S4O62-(aq)
H2SO4(aq) + 2NaOH(aq) → 2H2O(l) + 2Na+(aq) + SO42-(aq)
Answer: 1; 158

Equivalent mass of sulfuric acid

ɳ = number hydrogen ions = 2 eq/mol

200 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Analysis

The equivalent mass of sodium hydroxide Exercise 6-8

In order to prepare a solution of 2L
volume and 0.12 N concentrations,
ɳ = number of hydroxide ions = 1 eq/mol how many grams of potassium di-
chromate K2Cr2O7 is needed ac-
cording to the following oxidation
reduction reaction? (M=294 g/mol)

3- The following is an oxidation and reduction reaction. Cr2O72- + 14H+ + 6Fe2+ ⇌

2Cr3+ + 7H2O + 6Fe3+
5Fe2+(aq) + MnO4-(aq) 8H3O+(aq) → 5Fe3+(aq) + Mn2+(aq) + 12H2O(l)
The equivalent mass of Fe2+ ion is (This ion is the reducing agent in this reac-
Answer: 11.76 g
tion)
MFe = 56 g/mol
ɳ = number of donated electrons = 1 eq/mol
Number of lost electrons is calculated from the difference between oxidation
states (valences) of Fe2+ and Fe3+ ions. Exercise 6-9
What is the mass of sodium
hydroxide, NaOH (M= 40 g/mol),
necessary to prepare a solution of
0.2 M 500 mL?
Answer: 4 g
The equivalent mass of MnO4- ion (This ion is the oxidizing agent in the reac-
tion.)
Exercise 6-10
Calculate the mass of dissolved sub-
ɳ = number of taken electrons = 5 eq/mol stance in each of the following solu-
tions.
Number of accepted (taken) electrons are calculated from the difference be-
tween the oxidation states of Mn+2 and MnO4- 1- 350 mL, 0.125 M silver nitrate,
AgNO3 (M = 170 g/mol)
2- 250 mL, 0.1 N borax,
Na2B4O7.10H2O, (M=381 g/mol)
solution according to the following
4- The following is a complex ion formation reaction. reaction.
B4O72- + 2H3O+ + 3H2O → 4H3BO3
AgNO3(aq) + 2KCN(aq) ⇌ [Ag(CN)2]-(aq) + 2K+(aq) + NO3-(aq)
Answer:
1) 7.44 g
The equivalent mass of silver nitrate AgNO3
2) 4.76 g

FEZALAR EDUCATIONAL INSTITUTIONS 201

 Chapter - 6

ɳ = number of accepted electron pair = 2 eq/mol

The equivalent mass of potassium cyanide KCN

ɳ = number of donated electrons= 1x1 = 1 eq/mol

Volumetric flask
Example 6-7
ɳ value of 0.23 mol/L sulfuric acid is found to be 2 eq/mol in a neutralization
reaction. Calculate the normality of this acid solution.

Solution:
If we consider the two mathematical equations about standardization of solu-
tions and their molarities, with the condition of their molarities and ɳ (eq/mol)
values are known, it is possible to calculate its standardization (normality) by
the following equation.

6-6-4-Instruments Used in Volumetric Analysis

We should express that liter (L) is a principal unit to measure volumes of solu-
tions used in volumetric analysis processes. Also milliliter which is a thou-
sandth of liter is used in volumetric analysis. While making sensitive measure-
ments with solutions, only some glass instruments are used. These are:
1- Beaker: It is used to measure the volume of solution during its preparation.

Pipettes Burette 2- Burette: During titration, it is used to measure the volume of consumed
solution correctly.
Figure 6-3 3- Pipette: It is used to transfer a certain volume of solution from one contain-
Laboratory equipment used to er to another.
measure volumes of solution
6-6-5-Calculation of Volumetric Analysis Results
The aim of any volumetric analysis with titration method is to add chemically
equivalent amount of standard solution on the substance with an unknown
amount. This condition occurs in titration process. (Equivalent point is the
point at which the amount of standard substance becomes equivalent with the
202 FEZALAR EDUCATIONAL INSTITUTIONS
 Chemical Analysis

amount of substance which is to be guessed in titration process.) Practically,

this point is determined at the end of the reaction (practical equivalent point).
At this point, one of the properties of the solution changes (e.g. color change).
In titration processes, chemists usually use standard concentration to define
concentrations during preparation of solutions.
Therefore; As we have mentioned before, standard concentration (normality)
is basically used to calculate the equivalent masses of substances in volumetric
analysis calculations.
The following titration experiment shows the calculations necessary to find
out the mass of barium hydroxide Ba(OH)2 (M=171 g/mol) using volumetric
analysis processes. For this, we follow the steps below:
1- We dissolve the sample in distilled water. Then, we complete the volume of
the solution to 25 mL by adding distilled water in a flask.
2- By a pipette, 20 mL from sample solution is taken. It is transferred to a
beaker.
3- A few drops of organic indicator methyl red is added to the solution. This
substance doesn’t participate in the reaction. But, at the end point of the reac-
tion, as a result of change in the pH value of solution, its color turns red from
yellow. Therefore, the solution turns red at the end point.
4- With the barium hydroxide solution in the beaker, titration starts against
standard hydrochloric acid (with 0.098 M or 0.098 N concentration) solution.
For this, acid solution in the burette is added drop by drop to the sample solu-
tion in the beaker. Meanwhile, the solution in the beaker is swirled continuous-
ly. At the end, for the color change from yellow to red (at the end point), 22.4
mL of acid solution is measured to be added.

First reading
of volume

Definite
reading of
volumes as
(22.4 mL)

Attention: The unit mmol/mL is

equivalent of mol/L. Both are molari-
ty (M) units.

Solution be-
fore titration
(yellow)

FEZALAR EDUCATIONAL INSTITUTIONS 203

 Chapter - 6

Attention: In titration process, 5- Calculations: As known, at the end point of the reaction (practically equiv-
the amounts of solutions are pre- alent point), the amount of unknown substance (substance to be measured) is
pared in molar concentration. But equal to the amount of standard substance. In order to calculate the amount
determining the equivalent mass of (amount of substance is defined with number of moles or equivalent grams etc.)
solution with standard solution de- of substance dissolved in a solution, the volume of solution (mL) is multiplied
pends on writing the reaction equa- with the concentration of solution (mol/L or eq/L respectively).
tion. But, if substances with equal
Amount of substance
number of moles react, without (mmol) = Vsolution(mL) × M (mmol/mL)
need to write a chemical equation, dissolved in solution
the following relationship can be or
applied at the end point.
Amount of substance
N1× V1=N2 × V2 (meq) = Vsolution(mL) × N (meq/mL)
dissolved in solution
Thus, to define the concentrations
of solutions used in titration pro- Generally, the following relationship can be written when reaction has reached
cesses, molar concentration expres- end point in any titration process.
sion is preferred. Amount of unknown substance = Amount of standard substance
Amount of equivalent grams of unknown substance (meq) = amount of equiv-
alent grams of standard substance(meq) (N × V)HCl = (N × V)Ba(OH)2

Exercise 6-11 NHCl × VHCl = NBa(OH)2 × VBa(OH)2

Potassium permanganate, KMnO4, 0.098 (meq/mL) × 22.4 (mL) = NBa(OH)2 × 20 (mL)

is a widely used substance in re- From this relationship, standard concentration (normality) of Ba(OH)2 solution
duction-oxidation reactions. What can be calculated.
is the ɳ value of a chemical reaction 0.098 (meq/mL) × 22.4 (mL)
________________________
in which potassium permanganate NBa(OH)2 = = 0.1097 meq/mL = 0.1097 eq/L
20 (mL)
is used to produce MnO2? What is
the normality of the solution with a In order to calculate the amount of dissolved substance in a certain volume of
molarity of 0.05M? solution (25 mL), equivalent mass of barium hydroxide is calculated as fol-
lows:
Answer: 3; 0.15 eq/L The reaction is used in titration;
Ba(OH)2 + 2HCl → BaCl2 + 2H2O
According to this reaction, ɳ = 2 eq/mol. Therefore,
MBa(OH)2 ___________
________ 171 (g/mol)
EMBa(OH)2 = = = 85.5 g/eq
ɳ 2 (eq/mol)

m (g)
_________

Eq (eq)
________ EM (g/eq)
___________
N (eq/L) = =
V (L) V (mL)
__________

1000 (mL/L)
We get the following formula if we re-arrange the equation:
N (eq/L) × V (mL) × EM (g/eq)
__________________________
m (g) =
1000 (mL/L)
0.1097 (eq/L) × 25 (mL) × 85.5 (g/eq)
________________________________
m (g) =
1000 (mL/L)
m (g) = 0.235 g
204 FEZALAR EDUCATIONAL INSTITUTIONS
 Chemical Analysis

Example 6-8 Exercise 6-12

0.1743 g of impure oxalic acid (H2C2O4) (M=90 g/mol) was titrated with sodi- The amount of nickel was measured
um hydroxide solution. 39.82 mL of 0.09 M base solution was used at the end in a sample with titration process ac-
point. What is the percentage of oxalic acid in the sample? cording to the reaction below.
Ni2+ + 4CN- → Ni(CN)42-
Solution: 160 mg of sample was titrated against
The reaction equation: 0.137 N KCN standard solution. As
2NaOH + H2C2O4 → Na2C2O4 + 2H2O 38.3 mL of KCN was used when the
end point was reached, calculate the
percentage of Ni2O3 (M = 165 g/mol)
According to the neutralization reaction, 1 mole of acid reacted with 2 moles of in the sample.
base. That means, at the end point of the reaction;
1
___
(mmol) H2C2O4 = × (mmol) NaOH Answer: 67.5%
2
The amount (mmol) of used sodium hydroxide is calculated:
(mmolNaOH) = Vsolution(mL) × M (mmol/mL)
mmolNaOH = 39.82 (mL) × 0.09 (mmol/mL)

mmolNaOH = 3.584 mmol

From the amount of sodium hydroxide, the amount of reacting oxalic acid can
be calculated.
At the end point of the reaction (practically the equivalent point)
Half of the amount of sodium hydroxide = the amount of oxalic acid
the amount of reacting sodium hydroxide
__________________________________
(mmol) H2C2O4 =
2 Exercise 6-13
3.584 mmol
__________ 0.958 g of a sample containing acetic
= 1.79 mmol = 1.79 × 10-3 mol acid, CH3COOH, (M = 60 g/mol) was
2
standardized with titration of 0.225 N
m (g)
_________ standard sodium hydroxide solution.
As the volume of solution needed to
M (g/mol)
_________
M (mol/L) = reach the end point was 33.6 mL,
V (L) calculate the percentage of acetic acid
From the re-arrangement of the equation, the following formula is obtained. in the sample.
m (g) = M (mol/L) × V (L) × M (g/mol) Answer: 47.34%
In this equation, into the result of multiplication of volume and molarity, the
amount of acid defined with number of moles is inserted.
m (g) = 1.79 × 10-3 (mol) × 90 (g/mol) = 0.16 g
Then, the percentage of impure oxalic acid in the sample is calculated accord-
ing to the following relationship.
mH2C2O4 (g)
___________
H2C2O4% = × 100
msample (g)
0.16 (g)
_________
H2C2O4% = × 100 = 91.8%
0.1743 (g)

FEZALAR EDUCATIONAL INSTITUTIONS 205

 Chapter - 6

BASIC EQUATIONS

Gravimetric Factor

Molar Concentration (Molarity)

Standard Concentration (Normality)

206 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Analysis

BASIC CONCEPTS
Qualitative Analysis Methods: A group of chemical analysis methods which is used to determine from which compo-
nents a substance or a mixture is made up.
Quantitative Analysis Methods: A group of chemical analysis methods which is used to determine the amounts of each
component forming a substance.
Gravimetric Analysis Methods: A method in which substances in a chemical mixture are precipitated through some
reagents, then after separation the sought compound is weighed.
Volatilization Methods: A group of analysis methods which depend on extraction of volatile component in a sample and
then determining its mass with direct or indirect methods.
Precipitation Methods: A group of mass analysis methods which depend on transforming the substance to be measured
in a sample into a weighable pure component with a definite chemical formula through precipitation reactions.
Gravimetric Factor: The ratio of molar mass of sought substance to the molar mass of weighed (precipitate) substance.
Titration: It is the process of drop by drop addition of standard solution in a burette with a known concentration into the
solution in a beaker with an unknown concentration. This addition continues until the end point is reached. The aim of
this process is to determine the unknown concentration via the concentration of standard solution by measuring volumes
of used up solutions during process.
Equivalent Point: It is the theoretical point at which the amount of standard substance in burette is equal to the amount
of unknown substance in beaker.
End Point: It is the point at which the reaction between standard substance and unknown substance completes. The point
is determined practically (experimentally) by using one of the suitable indicators.
Titration Error: It is the difference (in volumes) between equivalent point (theoretical) and end point that is measured
practically in titration process.
Indicator: It is a substance which is added to titration process; although it doesn’t participate in the reaction, one of its
physical properties (e.g. color change) changes clearly.
Neutralization Reaction: It is a reaction which takes place between an acid and base and yields salt and water as prod-
ucts (Hydrogen and hydroxide react in order to form water molecules.)
Precipitation Reaction: It is a reaction in which a slightly soluble solid substance (precipitate) is formed.
Oxidation-Reduction Reaction: It is a reaction in which reactants undergo oxidation and reduction.
Salt: It is a compound which is formed by the combination of a positive ion (except H+) and a negative ion (except OH-
or O-2).
Equivalent Mass: It is the mass of a substance equivalent of substances as 1.008 g of hydrogen or 17.008 g of hydroxide
or 8.000 g of oxygen in a reaction. Equivalent mass isn’t a constant value, but it changes according to the type of the
reaction.

FEZALAR EDUCATIONAL INSTITUTIONS 207

 Chapter - 6

QUESTIONS OF CHAPTER-6
6-1- How can we separate common positive ions (cations) from each other?
6-2- Name the positive ions in the second group of the table 6-1. Name the factors causing those to precipi-
tate. How can copper ion and iron ion in the same solution be separated? Explain.

6-3- Complete the following reactions and tell the properties of products.
K2CrO4 and hot water
PCl2 _________________ →
________ NH3 HNO3
________
AgCl → →
2+ ______
dilute HCl NH3
______ ______
King’s water SnCl2
______ SnCl2
______
Hg2 → → → → →
6-4- How is the separation process of Hg2+ and Hg22+ ions made?
6-5- Fill in the blanks.
1- Cr3+ is one of……………..group of positive ions and it precipitates as .........................form after addition
of ……………………and ………………… precipitants.
2- Precipitants of IV group positives ions are …………………… , ……………………….. and
…………………….
3- Molarity of 0.3 N Al2(SO4)3 solution is ………………..
4- Value of ɳ of a solution which is 0.2M and 1N is ……………
5- If 15.675 mg of carbon dioxide, CO2, gas is released from combustion of 5.7 mg of a hydrocarbon of or-
ganic compound, ratio of hydrogen in the compound is …………..(MC = 12 g /mol, MO = 32 g/mol) 2

6-6- In order to precipitate 1.67 g of lead iodate Pb(IO3)2, how many grams of potassium iodate KIO3 is needed?
(KIO3 = 214 g/mol, Pb(IO3)2 = 557 g/mol)
Answer: 1.283 g
6-7- 14.4 mg of carbon dioxide gas and 2.5 mg of water vapor were produced from burning of an 5.7 mg or-
ganic compound . Calculate the percentages of carbon and hydrogen in the compound.
(C:12 g/mol, O:16 g/mol, H:1 g/mol)
Answer: 68.9%; 4.9%
6-8- As 36.7 mL hydrochloric acid solution is equivalent to 43.2 mL 0.236 M sodium hydroxide solution, what
is the molarity of hydrochloric acid?
Answer: 0.278 M
6-9- 2 L solution of 9.5 g of barium hydroxide is prepared to be used in an acid-base reaction. What is the mo-
larity and normality of barium hydroxide Ba(OH)2? (Ba(OH)2: 171 g/mol)
Answer: 0.027 M; 0.054 eq/L
6-10- What is concentration of sodium chloride formed in the following processes?
A- Mixing 10 mL, 0.15 M sodium chloride with 10 mL distilled water.
B- Mixing 10 mL, 0.15 M sodium chloride with 10 mL, 0.3 M sodium chloride.
Answer: A) 0.075 M; B) 0.225 M

208 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Analysis

6-11- What is the volume of 0.2 M potassium permanganate solution which is necessary to titrate (oxidation
-reduction reaction) 40 mL 0.1 M iron (II) sulfate in acidic conditions? Titration reaction equation is given
below. 10FeSO4 + 2KMnO4 + 8H2SO4 → 5Fe2(SO4)3 + 2MnSO4 + K2SO4 + 8H2O
Answer: 4 mL
6-12- Circle the correct answer in the following questions.
1- What is the ɳ value of iron (III) sulfate, Fe2(SO4)3, salt used to precipitate lead ion?
A- 4 eq/mol
B- 5 eq/mol
C- 6 eq/mol
2- How can Cu2+ ion be separated from Ca2+ ion by addition of one of the following?
A- Dilute HCl acid
B- passing H2S gas in NH4OH and NH4Cl through solution
C- passing H2S gas in dilute HCl through solution
3- What percent of 0.74 g of impure pesticide C14H9Cl5 (DDT) is pure which is needed to obtain 0.253 g of
AgCl?
A- 17%
B- 19%
C- 21%
4- What is the name of the gravimetric method which is used to determine the mass of a volatile component
from mass difference occurring after a certain amount of sample is heated or burnt in open air?
A- Direct volatilization method
B- Indirect volatilization method
C- Precipitation Method
5- In gravimetric analysis processes which depend on precipitation reactions,
A- formation of colloidal precipitate is preferred.
B- formation of crystallized precipitate is preferred.
C- type of precipitate has no significance.
6- What does the ratio of molecular mass of sought substance to molecular mass of gravimetric formula show
(with the condition of both formulas contain the sought element or molecules)?
A- Precipitation formula
B- Molar mass
C- Gravimetric factor

FEZALAR EDUCATIONAL INSTITUTIONS 209

 Chapter - 6
7- What is the definition of mass of the substance which produces or consumes 1 mole of active component?
A- Equivalent Mass
B- Molar Mass
C- Standard Mass
8- The normality of solution obtained by dissolving 13 g of K2Cr2O7 in 500 mL of distilled water:
Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O
A- 0.53 mol/L
B- 0.53 eq/L
C- 3.18 eq/L
6-13- Calculate the gravimetric factor of Na5P3O10 (M=368 g/mol) in Mg2P2O7 (M=222 g/mol).
Answer: 1.11
6-14- 50 mL HIO3 (M = 176 g/mol) acid solution was titrated against 0.145 N standard sodium hydroxide
solution. As the volume of the base solution added from burette to reach end point was 45.8 mL, calculate the
following :
A- Normality of HIO3 acid
B- According to the following reaction, if the same acid was used to obtain iron, what would be the normality
of the acid? HIO3 + 4FeCl2 + 5H3O + + 6Cl- → 4FeCl3 + ICl2- + 8H2O
Answer: A: 0.13 N; B: 0.52 N
6-15- In order to find the concentration of 25 mL NaOH solution, it was titrated against 0.08 M sulfuric acid,
47.1 mL of acid was added to reach the end point. Calculate the molar concentration of sodium hydroxide
solution, and then find out the mass of NaOH dissolved in 500 mL of this solution. (NaOH = 40 g/mol).
Answer: 0.3 M; 6 g
6-16- In order to analyze one of barium halide salts BaX2.2H2O gravimetrically, 0.266 g of barium salt was
dissolved in 200 mL of water. Then, to precipitate barium (M = 137 g/mol) as barium sulfate, BaSO4 (M=233
g/mol), enough amount of sulfuric acid, H2SO4, was added to the solution. As the mass of the precipitate was
0.254 g, what is the halide shown with X in barium salt?
Answer: Chlorine
6-17- 0.5 g of impure sodium iodide, Nal, (M = 150 g/mol) salt was dissolved in water. To precipitate io-
dide ions, silver nitrate, AgNO3, solution was added to the solution. At the end of the reaction, 0.744 g of
silver iodide Agl (M = 235 g/mol) precipitate was obtained. Calculate the percentage of sodium iodide
found in impure salt.
Answer: 95%
6-18- 4.29 g of sodium carbonate crystals Na2CO3.xH2O is dissolved in pure water then the volume is com-
pleted to 250 mL. 15 mL of 0.2N HCl solution is needed to neutralize 25 mL of the same solution completely.
What is the number of water molecule (x) in the formula of Na2CO3.xH2O? (Na: 23 g/mol, C: 12 g/mol, O: 16
g/mol, H: 1 g/mol)
Answer: Na2CO3.10H2O

210 FEZALAR EDUCATIONAL INSTITUTIONS

 Chemical Analysis

6-19- Calculate the equivalent mass and normality of 6.0 M phosphoric acid H3PO4 (M=98 g/mol) solution
when it is used in the following reactions.

A- H3PO4(aq) + 3OH-(aq) PO43-(aq) + 3H2O(1)

B- H3PO4(aq) + 2NH3(aq) HPO42-(aq) + 2NH4+(aq)
C- H3PO4(aq) + F-(aq) H2PO4-(aq) + HF(aq)

Answer: A) 32.7 g/eq; 18 N

B) 49 g/eq; 12 N
C) 98 g/eq; 6 N

6-20- 2 .5 g of a pure metal (M) carbonate (MCO3) which donates 2 ions to solution was added to 0.6 N 100
mL acid solution. At the end of the reaction, to neutralize the obtained solution, 0.2 N 50 mL of sodium hy-
droxide, NaOH, solution was added. Determine the element by finding the molar mass of it.
Answer: 40 g/mol; Ca
6-21- Potassium iodide solution was added to 0.3 N 20 mL potassium permanganate (KMnO4) solution in
acidic conditions. At the end of the reaction, some iodine (I2) was produced. Produced iodine was titrated
with sodium thiosulfate, Na2S2O3 (M=158 g/mol).
I2 + 2Na2S2O3 2Nal + Na2S4O6

To reach the end point, 25 mL of Na2S2O3 was consumed. According to this, calculate the following:
A- The normality of Na2S2O3 solution
B- How many grams of sodium thiosulfate is needed to prepare 1 L solution?
Answer: A) 0.24 N; B) 37.92 g
6-22- What is the mass of barium sulfate, BaSO4, (M=233 g/mol) that precipitates completely when a sufficient
amount of barium chloride, BaCl2, (M=208 g/mol) is mixed with 100 mL of sulfuric acid solution, H2SO4,
(M=98 g/mol). 16 mL of 0.10 M NaOH is needed to neutralize 20 mL of sulfuric acid.
Answer: 0.932 g

FEZALAR EDUCATIONAL INSTITUTIONS 211

 Chapter - 6

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212 FEZALAR EDUCATIONAL INSTITUTIONS
 Organic Chemistry

ORGANIC CHEMISTRY FOR CHAPTER-7

SUBSTITUTED HYDROCARBONS

ACHIEVEMENTS
After studying this chapter, student can perform the following:
* He/she can differentiate the class of a compound from its structural formula.
* He/she can apply the IUPAC system to name organic compounds (hydrocarbons).
* He/she learns the physical and chemical properties and reactions of aromatic hydrocarbons.
* He/she learns methods of production of these compounds.
* He/she separates alcohols, ketones and aldehydes using analysis methods.
* He/she learns the significance of these compounds in our daily lives and their usages.

FEZALAR EDUCATIONAL INSTITUTIONS 213

 Chapter - 7

7-1 PREFACE
Previously, we have learnt that one of the branches of chemistry is or-
ganic chemistry which studies properties and reactions of some com-
pounds that have carbon as the basic element besides other elements.
Hydrocarbons are considered as the simplest part of organic chemistry as
they consist of carbon and hydrogen elements. Hydrocarbon compounds
Methane are divided into two as aliphatic hydrocarbons and aromatic hydrocar-
(saturated hydrocarbon) single bons. In hydrocarbons, covalent bonds which are formed by electron
bond sharing exist between carbon atoms. If there is one bond between two
carbon atoms, the compound is called as ALKANE. Alkanes are satu-
rated aliphatic hydrocarbon compounds. If there are two bonds between
carbons, the compound is an ALKENE, if there are three bonds, it is an
ALKYNE. Alkenes and alkynes are unsaturated aliphatic hydrocarbons.
Ethylene or ethene They can be either in open-chain structure or in cyclic structure. Ben-
(Unsaturated hydrocarbon zene and its derivatives form aromatic hydrocarbons. These compounds
double bond) have cyclic structures.
The compounds which have the same molecular formulas but different
structural formulas are called as isomeric compounds. They have differ-
ent physical properties such as different boiling and melting points. We
have learnt how to differentiate this kind of compounds.
Acethylene
(unsaturated hydrocarbon triple bond) Example 7-1
Write down the structural formulas of n-butane and 2-methylpropane
(isobutane) which have the same molecular formula C4H10 .
H
Solution: |
H-C-H
H H H H
| | | |
H
| | H
|

H - C - C -C -C -H H-C -C- C-H

| | | | | | |
H H H H H H H
Benzene
(aromatic cyclic, unsaturated n-butane 2-methylpropane
hydrocarbon)
As you see, although these two compounds have the same molecular
formula, they have different physical and chemical properties.
Table 7-1 Example 7-2
IUPAC Nomenclature of Hydrocarbons Name the following compounds according to IUPAC.
Number Name in Alkane Alkene Alkyne
of carbon Latin -ane -ene -yne
1 meth methane - -

2 eth ethane ethene ethyne

3 prop propane propene propyne
4 but butane butene butyne
5 pent pentane pentene pentyne

Solution:
6 hex hexane hexene hexyne
7 hept heptane heptene heptyne
8 oct octane octene octyne (1) 3-ethyl-2-methylpentane
9 non nonane nonene nonyne (2) 2,4,4 –trimethylhexane
10 dec decane - -
(3) 2-methyl-1-butene

214 FEZALAR EDUCATIONAL INSTITUTIONS

 Organic Chemistry

The basic structure of all hydrocarbons consist of carbon and hydrogen. But Exercise 7-1
many hydrocarbon compounds also include oxygen, nitrogen, halogens, sulfur Write down structural formulas for
and other elements. What are those compounds? What are their properties?
C5H12 compound
What are the differences between those and hydrocarbons?
The presence of elements other than carbon and hydrogen in hydrocarbon com-
pounds give them some distinctive properties. These elements and element
groups which give organic compound distinctive properties are called as func-
tional groups.
Functional groups are attached to carbon atoms. Table 7-2 shows those func-
tional groups.

Table 7-2 Functional Groups

General Name of
Example Suffix Active Group General structure
Formula Compound
CH3Br R-X
CnH2n+1X yl -X Alkyl Halides
Methyl bromide (X= Cl, Br, I)
CH3CH2-OH
CnH2n+2O ol -OH R-OH Alcohols
Ethanol
CH3 - O - CH3 -OR
CnH2n+2O ether R-O-R Ethers
Dimethyl ether alkoxide
O O
O
|| ||
CnH2nO al || Aldehydes
CH3 - C - H -C-
R-C-H
Ethanal carbonyl
O O
O
|| ||
CnH2nO one || Ketones
CH3 - C - CH3 -C-
R-C-R
Propanone carbonyl
O O
O
|| || Carboxylic
CnH2nO2 oic ||
CH3 - C - OH - C - OH acid
R - C - OH
Ethanoic acid carboxyl
O O
O
|| Alkyle + ||
CnH2nO2 || Esters
CH3 - C - O - CH3 oate -C-O-R
R -C-O-R
Methyl ethanoate Ester

H
|
Primary R- N -H
H
CH3CH2 - NH2 |
CnH2n+3N Amine - NH2 Amines
Ethyl amine Secondary R- N -R

R
|
Tertiary R- N -R

FEZALAR EDUCATIONAL INSTITUTIONS 215

 Chapter - 7

Exercise 7-2 7-2 ALKYL HALIDES

Name the following compounds By cleavage of one hydrogen atom from an alkane, an alkyl group forms.
according to IUPAC. Table 7-3 shows some alkyl groups derived from alkanes.

1) CH3
| Table 7-3 Some Alkyl Groups derived from Alkanes
CH3 — CH — CH2 — C ≡ C — CH3 Name of group Alkyls Formula Alkane
2) CH3 CH3 Methyl CH3 — CH4 Methane
| | Ethyl C2H5 — C2H6 Ethane
CH3—CH — CH = CH — CH — CH3
n-propyl CH3 - CH2 -CH2 - C3H8 Propane
3) CH3 |
Isopropyl C3H8 Propane
| CH3 - CH -CH3
CH3 — C — CH3
|
CH3 When a halogen atom is bonded to an alkyl group, the resulting com-
pound is called as an alkyl halide.

These compounds are derivatives of alkanes. The functional groups in

Attention: those compounds are or R X groups.
mono = one
Primary = the carbon is attached to Here, R represents alkyl group and X represents halogens as I, Br, Cl.
one other carbon.
Secondary = the carbon atom is at- H H H
tached to two other carbon atoms. | | |
Tertiary = the carbon atom is attached H — C — Cl H— C —— C — Br
to three other carbon atoms. | | |
H H H

Methyl chloride Ethyl bromide

Alkyl halides are divided into three according to the carbon atom that
halogen is attached to: primary (1°), secondary (2°) and tertiary (3°)

Primary carbon atom Secondary carbon atom Tertiary carbon atom

H R R
| | |
R — C — X R — C — X R— C—X
| | |
H H R

Primary alkyl halide Secondary alkyl halide Tertiary alkyl halide

(1°) (2°) (3°)

While forming alkyl halides, halogen atoms can replace more than one
hydrogen atoms either on the same carbon or different ones.

216 FEZALAR EDUCATIONAL INSTITUTIONS

 Organic Chemistry

7-2-1 The Nomenclature of Alkyl Halides

Alkyl halides are named according to IUPAC nomenclature system as
follows:
1- The longest carbon chain which has halogen atom is chosen. It is num-
bered starting from the halogen atom.
I
2- Firstly, the number of the carbon atom attached to halogen atom is |
written. Then, following the (-) hyphen symbol, halogen’s name is writ- H—C—I
ten with –o suffix added (chloro, bromo, iodo). If there are other halo- |
I
gens, first the (-) symbol, then the names of those halogens are written in Triiodomethane
the same way. Halogens’ names are written in alphabetical order in the Iodoform
compound. For example, bromo, chloro, iodo respectively. You can see
those orders in Table 7-4.
Cl Cl Cl Br Br
| | | | |
Cl — C — Cl H — C — Cl H — C — Cl H—C—C—H
| | | | |
H H
Cl Cl H
1,2-dibromoethane
Tetrachloromethane trichloromethane dichloromethane
Chloroform
Table 7-4 Systematic Names of Some Alkyl halides
Compound Systemic name of compound
Attention:
While writing name of compound,
does not leave space.

Exercise 7-3
1- Write down the structural formu-
las for the following compounds:
a- 1,1- dichloroethane
b- 2-bromo-2-iodohexane
c- 2-iodo-2-methylbutane

2- Write down the systematic names

of the following compounds.
a) CHCl3
b) Br Cl
| |
CH2 — CH — CH3
7-2-2 The Synthesis of Alkyl Halides
Alkyl halides are synthesized through many methods in industry and laborato-
ries. We will explain some of those laboratory methods.

Addition of Hydrogen Halides to Alkenes

In case of the reaction of hydrogen halides with an alkene, hydrogen atom is
attached to one of the carbons around the double bond, halide is attached to the
other carbon and alkyl halide is obtained. This reaction is called electrophilic
addition reaction.

FEZALAR EDUCATIONAL INSTITUTIONS 217

 Chapter - 7

This kind of reactions occur in compounds which have double or triple bonds
between carbon atoms. The reaction of hydrobromic acid with ethylene and

2-butene can be given as examples.

CH2 = CH2 + HBr → CH2 - CH2

| |

H Br
Ethylene Ethyl bromide
Br
|
CH3 - CH = CH - CH3 + HBr → CH3 - CH - CH2 - CH3
2-butene 2-bromobutane

Attention: The mechanism of the reaction is as follows:

As nucleophile groups are free
electron-rich (they have two or 1- Hydrobromic acid contains positive proton (H+) and negative bromide
more electrons), they are named (Br -) ions.
as nucleus loving. As electrophile
groups have empty orbitals, they
are named as electron loving. The
steps of this mechanism apply to 2- Proton is added to the double bond of ethylene and carbonium ion forms.
all alkenes which are symmetrical
around the double bond. There-
fore, it does not matter which
carbon atom adds hydrogen and
halide. The result is always the
same, the same compound is
obtained. 3- Negative bromide ion adds to positive carbonium ion and forms ethyl bro-
mide (alkyl halide).

The steps of this mechanism apply to all alkenes which are symmetrical around
the double bond. Therefore, it does not matter which carbon atom adds hydro-
gen and halide. The result is always the same, the same compound is obtained.

But if the groups around the double bond are not symmetrical, the reaction
mechanism follows Markovnikov’s rule.

218 FEZALAR EDUCATIONAL INSTITUTIONS

 Organic Chemistry

Exercise 7-4
According to Markovnikov’s rule, 2-bromopropane is favored instead of 1-bro- Write down the reactions of the
mopropane. following with HCl.
Vladimir Markovnikov assigned the following rule after so many experiments. a- 1-butene
When a compound is added to a double bonded compound with asymmetric b- 2-butene
groups, the positive ion of the compound adds to the carbon with greater num-
ber of hydrogen atoms around the double bond. Negative ion adds to the other
carbon (with less hydrogen) of the double bond.
Tertiary (3°) carbonium ion the most stable among the secondary (2°) and pri-
mary (1°) carbonium ions, whereas secondary carbonium is more stable than
the primary one.
In the example above, Compound A is more stable therefore it is formed more
than Compound B.
H-Br → H+ + Br-

Example 7-3
Prepare the compounds below: Exercise 7-5
1) ethyl chloride (chloroethane) from ethylene Write down the chemical formu-
2) 2-iodopropane from propene las for the following reactions:
1- Prepare 2-bromobutane using
Solution: proper alkene and acid halide.
1) CH2 = CH2 + HCl → CH3 - CH2 - Cl 2- Add HCl to 2-methyl-1-butene.
Ethylene Chloroethane
2) CH3 - CH = CH2 + HI → CH3 - CH - CH3
|
I
Propene 2-iodopropane

FEZALAR EDUCATIONAL INSTITUTIONS 219

 Chapter - 7

7-2-3-Properties of Alkyl Halides

1- Physical Properties
Alkyl halides like CH3CH2Cl, CH3Br, CH3Cl are in gas form at room tempera-
ture. Alkyl halides up to C18 are in liquid form and colorless. Alkyl halides that
have more than 18 carbons are colorless and solid. They do not dissolve in
water but dissolve in organic solvents. The reason for their water-insolubility is
that they cannot form hydrogen bonds with water.

2- Chemical Properties
On the carbon which halogen is attached, the bond between carbon and hydro-
gen atoms is polarized as the halogen of alkyl halides has more electrons than
carbon. The poles of this bond vary according to the type of halogen atom. For
example, in alkyl iodide, the polarization is very low. The carbon which has the
halogen atom becomes the nucleophile group. The most significant reactions of
alkyl halides are nucleophilic substitution reactions.

Do you know that? For this type of reactions, the following can be given as examples:
Some alkyl halides such as
CCl4 are used in fire-extin- A- The reaction of alkyl halides with aqueous potassium hydroxide
guishers. Because they are so (KOH) solution
dense that they form a layer In this reaction, as shown in the following equation, halogen atom substitutes
over fire. But due to the pollu- with hydroxyl group (-OH) and alcohol is formed.
tion they cause, they are used H 2O
less nowadays. Alkyl halides CH3I + KOH → CH3OH + KI
Δ
are also used as pesticides, e.g methyl iodide methyl alcohol
DDT. But they were banned
because they are dangerous. H 2O
CH3CH2Br + KOH →Δ
CH3CH2OH + KBr
ethyl bromide ethyl alcohol

B- The reaction of alkyl halides with alcoholic potassium hydroxide

(KOH)
When an alkyl halide reacts with alcoholic KOH, an alkene is obtained. In this
reaction, HX molecule is lost from alkyl halide. This is a method of production
of alkenes. For example:

C2H5OH
CH3CH2CH2Br + KOH → Δ
CH3CH=CH2 + KBr + H2O
1-bromopropane propene

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C- The reaction of alkyl halide with magnesium metal in dry ether Exercise 7-6
Alkyl halides react with Mg metal to form methyl magnesium iodide (electro- Write down chemical equations for
phile). For example: the following reactions:
dry ether
CH3I + Mg → CH3MgI 1- The reaction of 2-chloro-2-meth-
ylpropane with aqueous KOH solu-
methyl iodide methyl magnesiumiodide
tion
dry ether
CH3CH2Br + Mg → CH3CH2MgBr 2- The reaction of
ethyl bromide ethyl magnesiumbromide 1-bromo-3-ethylpentane with KOH
in alcohol

7-3 ALCOHOLS
Alcohols are hydrocarbon compounds which have hydroxyl group bonded to sat-
urated carbon atom. (-OH) is defined as the functional group in these compounds.
Their general formula is R-OH or (CnH2n+ 2O).

Alcohols are classified according to the hydroxyl group that is attached to carbon
atom. If the carbon atom with hydroxyl group is attached to another carbon atom,
it is a primary (1°) alcohol; if the carbon with the hydroxyl group is attached to
two carbon atoms, it’s a secondary (2°) alcohol; if the carbon with the hydroxyl
group is attached to three carbon atoms, it is called as a tertiary (3°) alcohol.

Primary carbon atom Secondary carbon atom Tertiary carbon atom

H R R
| | |
R — C — OH R — C — OH R — C — OH
| | |
H H R

Primary alcohol Secondary alcohol Tertiary alcohol

(1°) (2°) (3°)

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 Chapter - 7

Do you know that? 7-3-1 Nomenclature of Alcohols

Alcohols also include compounds Alcohols are named according to IUPAC system as follows:
that have 2 hydroxyl groups such 1- The longest chain which has the hydroxyl group is chosen. The carbon with
as ethylene glycol or three hy- the hydroxyl group is given the lowest number.
droxyl groups such as glycerine.
2- Naming is done according to the number of carbons. The –ol suffix is added
These compounds are called as
polyalcohols. to the end of the corresponding alkane.
3- The number and place of the alkyl groups on the chain is mentioned.

CH3 OH CH3
| | |
CH3 - CH2 - CH2 -OH CH3 - C - CH - CH - CH3
1- propanol |
CH3

2,2,4-trimethyl-3-pentanol

Ethylene glycol
CH3
Di-hidroxide |
CH3 - CH -OH Cl - CH2 - CH2 - CH2 - OH
2- propanol 3-chloro-1- propanol

7-3-2 Synthesis of Alcohols

Alcohols can be synthesized through many methods in industry and laborato-
ries. Here we will explain one of the laboratory methods.
Glycerine
Tri-hidroxide Addition of Water to Alkenes
Addition of water to alkenes is achieved via hot concentrated sulfuric acid used
Exercise 7-7
A- Name the following compounds as a catalyst. Alkene reacts first to produce alkyl sulfonic acid (Markovnikov’s
systematically: rule). This compound reacts with water and forms alcohol and sulfuric acid
again. OH
1) OH |
H2SO4
| CH3 - CH = CH2 + H-OH → CH - CH - CH3
CH3 — CH— CH — CH2 — CH3 Δ 3
1-propene 2- propanol
|
CH3 According to reaction mechanism;
2) CH3 — CH — CH3
|
OH

3) CH3
|
CH3 — C — OH
|
CH3
B- Write down the structural for-
mulas for the compounds below:
1) 2-methyl-2-hexanol
2) 2,2-dimethyl-1-butanol Example 7-4
3) 3-methyl-3-pentanol What are the probable structural formulas for alcohols that have a molecular
weight of 74 g/mol?

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Solution: Attention:
General formula for alcohols (CnH2n+2O)
OH- group replaces OSO3H- in transi-
CnH2n+2O = (n × 12) + [(2n + 2) × 1] + (1 × 16) tion compound because OH- is more
CnH2n+2O = 12n + 2n + 2 + 16 = 74 g/mol basic and concentrated than OSO3H-.
14n = 74 - 18 ⇒ n = 4 This method is used in preparation of
alcohols in industry.
Molecular formula is C4H10O
CH3
| Exercise 7-8
CH3 - CH2 - CH2 - CH2 -OH CH3 - CH - CH2 - OH
1- butanol 2-methyl-1- propanol What are the probable formulas for
alcohols with a molar mass of 88 g/
Primary alcohol Primary alcohol mol?

OH OH
| |
CH3 - CH2 - CH -CH3 CH3 - C - CH3
2- butanol |
Secondary alcohol CH3
Exercise 7-9
2-methyl-2-propanol Prepare the following compounds:
Tertiary alcohol 1) 2-butanol from 1-butene
2) ethanol from ethylene
7-3-3 Properties of Alcohols

1- Physical Properties
Alcohols have got low molecular weights. They are poisonous and they have
sharp odors. They have strong intermolecular bonds. Therefore, their boiling
points are much higher than of alkynes (Figure 7-1). Besides, alcohols can form
hydrogen bonds between their molecules and with water molecules. Therefore,
alcohols between (C1-C3) dissolve in water very well. Figure 7-1
A) hydrogen bonds between alco-
hol molecules
B) hydrogen bonds between water
and alcohol molecules

2- Chemical Properties
Alcohols are compounds that tend to react. They react with polarized or ionic
compounds. Some important reactions of alcohols are given below:
A) Alcohols react with sodium or potassium metals and produce hydro-
gen gas.

2CH3 - CH2 - OH + 2Na → 2CH3 - CH2 - O- Na+ + H2 ↑

Ethanol Sodium ethylate

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 Chapter - 7

B) They react with phosphorous trichloride (PCl3) or phosphorous pen-

tachloride (PCl5) and form alkyl halides.
pyridine
CH3 - CH2 - OH + PCl5 → CH3 - CH2 - Cl + POCl3 + HCl
ethanol ethyl chloride
pyridine
3CH3 - OH + PCl3 → 3CH3 - Cl + H3PO3
methanol methyl chloride

C) Reactions of Alcohols with Acids

Alcohols react with acid halides (HX) and form alkyl halides.

OH Cl
| |
CH3 - CH - CH3 + HCl → CH3 - CH - CH3 + H2O
2-propanol 2- chloropropane

This reaction occurs fast with tertiary alcohols especially when concentrated
hydrochloric acid is used. But with primary and secondary alcohols, it is quite
slow. And the reaction rate also depends on the type of acid.

HI > HBr > HCl

In the reaction, solution of zinc chloride in hydrochloric acid is used. This mix-
Attention: As alcohols
-
cannot
ture is called as Lucas’ reagent. It is used to differentiate primary, secondary
donate hydroxyl OH ion to the
solution, they are not accepted as and tertiary alcohols. Tertiary alcohols readily react with this cation and form
strong bases.
alkyl halides which does not dissolve in the solution. While secondary alcohols
react with Lucas’ reagent after 5 minutes, primary alcohols do no react with it
at room temperature.

Example 7-5
Differentiate 1-propanol, 2-propanol and 2-methyl-2-propanol chemically.

Solution:
We can differentiate those compounds using dry ZnCl2/HCl Lucas’ reagent.
In this process, it is mixed with 2-propanol (secondary alcohol) and 5 minutes
later, a layer of 2-propane chloride forms. While it reacts with 2-methyl-2-pro-
panol (tertiary alcohol) readily, 1-propanol (primary alcohol) does not react
with Lucas’ reagent at room temperature.

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ZnCl2
1) CH3 - CH2 - CH2 -OH + HCl → N.R
1-propanol

CH3 CH3
| ZnCl2
|
2) CH3 - CH - OH + HCl → CH3 - CH - Cl + H2O
2-propanol 2- chloropropane

CH3 CH3
| ZnCl2
|
3) CH3 - C - OH + HCl → CH3 - C - Cl + H2O
| |
CH3 CH3
2-methyl-2-propanol 2-chloro-2-methylpropane

This way we can differentiate primary, secondary and tertiary alcohols using
Lucas’ reagent.
1- For primary alcohols to react with Lucas’ reagent, high temperature is neces-
sary and they do not react at room temperature. Therefore, no turbidity is visible
in solution.
2- In secondary alcohols, turbidity appears 2-5 minutes later.
3- Through reaction of tertiary alcohol with Lucas’ reagent, slightly water solu-
ble alkyl halide forms and it causes turbidity in solution.
D) Synthesis of water from Alcohol
Ethyl alcohol reacts with concentrated sulfuric acid at 170 °C and ethylene
forms.
H2SO4 Cond.
CH3 - CH2 - OH → CH2 = CH2 + H2O
(170°C)
Ethanol Ethylene
Mechanism:
The mechanism of the reaction above follows the following steps:
1- Addition of proton to alcohol molecule:

2- The cleavage of water molecule from the compound above and formation of
more stable carbonium ion:

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 Chapter - 7

3- The cleavage of proton from carbonium ion and formation of double bond
and cation:

According to Saytzeff’s rule, OH- group leaves carbon atom and hydrogen
atom leaves adjacent carbon atom which has fewer hydrogen.
Exercise 7-10 E) Oxidation
When water molecule is removed
from 2-butanol, why 2-butene is The structure of products which form when alcohols are oxidized depends on
formed instead of 1-butene? the type of alcohol and reaction conditions. Substances widely used in oxida-
tion reactions are K2Cr2O7 /H2SO4 or KMnO4/ H2SO4 mixtures. This reaction is
a method used to differentiate alcohols.
Primary alcohols (1°) oxidize to aldehydes first then to carboxylic acids.

O O
[O] || [O] ||
RCH2OH R- C- H R - C - OH
Primary alcohol Aldehyde Organic compound

O O
K2Cr2O7/H+ || [O] ||
CH3CH2OH CH3 - C - H CH3 - C - OH
[O]
Exercise 7-11 Ethanol Ethanal Ethanoic acid

Write the oxidation reaction of fol-

lowing compounds. Secondary alcohols (2°) oxidize to ketones.
1) 1- butanol
2) 2- butanol OH O
| K2Cr2O7/H+ ||
3) 2- methyl -2- butanol CH3-CH-CH3 CH3 - C - CH3
[O]
2-propanol propanone (asetone)
Secondary alcohol

Tertiary alcohols (3°) do not oxidize as the carbon atom which carries the
OH- group does not have any hydrogen atoms.

OH
| K2Cr2O7/H+
CH3-C -CH3 N.R (N.R means no reaction.)
Exercise 7-12 |
An organic compound which has 4 CH3
carbon atoms responses with Lucas’
reagent. As a result of oxidation, 2-methyl-2-propanol
a ketone compound forms. Write Tertiary alcohol
down the reaction equation. Guess
the organic compound.

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7-4 ETHERS
Ethers are shown as R'-O-R. Although they have a general formula as (CnH2n+2O)
that is similar to that of alcohols, ethers have two alkyl groups and an oxygen
atom. If alkyl groups are the same (R=R'), they are called as simple ethers, if
alkyl groups are different (R≠R'), they are called as complex ethers. The func-
tional group of ether is C-O-C.

CH3 - O - CH3 CH3 - O - CH2 CH3

dimethyl ether ethyl methyl ether

7-4-1 Nomenclature of Ethers

Ethers (alkoxy alkanes) are named according to IUPAC system as shown in the
following steps:
1- From alkyl groups which are bonded to oxygen atom, one with the longer
chain is chosen and accepted as the main chain.
2- Main chain is numbered starting from the closest carbon to oxygen with the
lowest number.
3- The –oxy suffix is added to name of the main chain.
4- Other alkyl groups are written with their numbers mentioned.
Number of branches number of carbon atoms bonded to name of the alkane corresponding to
+
- + name of the RO group +
-
name of the branch RO group the longest chain

You can see the names of some –oxy (RO-) groups below:
Exercise 7-13
1) Methoxy CH3O- A) Write down systematic names for
2) Ethoxy CH3CH2O- the following compounds.
3) Propoxy CH3CH2 CH2O-
1) CH3 — O — CH3
4) 2-propoxy 2) CH3
|
CH3 — O — C — CH3
Example 7-6 |
Write down systematic names for the following compounds: CH3
Solution: B) Write down structural formulas
Cl OCH3 OCH2CH3 for the following compounds.
| | |
1) 2,2-diethylmethoxyhexane
CH3-O - CH2- CH - CH3
1 2 3
CH3 - CH - CH3
3 2 1
CH3 - CH- 3CH2 -4CH3
1 2

2-chloromethoxypropane 2-methoxypropane 2-ethoxybutane

2) 2-chloro-2-methylpropoxypen-
tane

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 Chapter - 7

7-4-2 Synthesis of Ethers

Ethers can be synthesized through many methods in industry and laboratories.
We will explain one of the laboratory methods here.
Williamson Method
Ethers are prepared by the method which took the name of the scientist Wil-
liamson. In this method, sodium alcoholate forms from mixing of sodium met-
al with a suitable alcohol.
ROH + Na RONa + 1/2H2
sodium alcoholate
Then alkyl halide and sodium alcoholate reacts and target ether is obtained.
R-ONa + R´ - X R-O-R´ + NaX
Sodium alcoholate alkyl halide ether

In order to synthesize methoxyethane and ethoxyethane, sodium reacts with

Exercise 7-14 methanol and ethanol. Formed sodium methylate and sodium ethylate react
1) Write the synthesis reaction of with bromoethane and following ethers are produced:
ethoxybutane from ethanol.
2) Write the produce of the following
CH3-ONa + C2H5 - Br CH3-O- C2H5 + NaBr
Sodium methylate bromoethane methoxyethane
reaction.
CH3CH2CH2-Br + CH3-ONa
C2H5-ONa + C2H5 - Br C2H5-O- C2H5 + NaBr
Sodium ethylate bromoethane ethoxyethane
In these reactions, always primary alcohols are used. Secondary and tertiary
alcohols cause formation of unwanted compounds.

7-4-3 Properties of Ethers

1-Physical Properties
Methoxymethane and ethoxymethane are in gas form at room temperature.
Ignition and boiling points are too low. Therefore, they vaporize readily. They
are colorless and they have pleasant odors. As they don’t have hydrogen bonds
between their molecules, they have lower boiling points than alcohols. Ethers
do not dissolve in water as they cannot form hydrogen bonds with water. But
Note: those with small alkyl groups dissolve partially in water.
Through reaction of ethers with
oxygen in air, epoxides are formed.
While purifying ethers, peroxides
accumulate somewhere and at the
end of the process, this causes
explosions with elevated tem-
peratures. Therefore, prolonged
exposure of ethers with air must be
definitely prevented.

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2- Chemical Properties
Ethers are stable compounds, thus they don’t react with bases and active met-
als, they don’t undergo oxidation reactions. Ethers can only undergo following
reactions:
Exercise 7-15
A- They form alcohols when they are heated with dilute sulfuric acid. How can you differentiate
H2SO4 methoxymethane and ethane?
CH3CH2-O-CH2CH3 + H2O → Δ 2CH3CH2OH
Tip: Consider the reaction of
ethoxyethane ethanol
ethers with water in presence of
concentrated sulfuric acid.
But when they react with concentrated sulfuric acid or HCl, ethers donate a air
of electrons to hydrogen ion and form oxonium salts which can dissolve in acid-
ic solutions. Ethers can be obtained again when oxonium salts are mixed with
water. This reaction is used to differentiate alkanes and ethers as alkanes don’t
react with concentrated acids. For example:

B- Reaction with PCl5

Do you know that
The organic compound used to re-
Ethers react with phosphorus pentachloride and form alkyl chloride. move nail polish is the simplest form
of ketones that is acetone (propa-
Δ
R-O-R´ + PCl5 R-Cl + R´-Cl+ POCl3 none)?
Δ
CH3CH2-O-CH2CH3 + PCl5 2CH3CH2-Cl + POCl3
Ethoxyethane Ethyl chloride

7-5 ALDEHYDES AND KETONES

Aldehydes and ketones have the same functional group. Its name is carbonyl
group. This group is formed by oxygen atom attached with a double bond to
carbon atom. Compounds which include this functional group are called
as carbonyl compounds. Their general formula is CnH2nO. In aldehydes, the car- Do you know that
bon of carbonyl is bonded to a hydrogen and an alkyl group, whereas in ketones, The substance which is used in autop-
carbon of carbonyl group is bonded to the same or different two alkyl groups. sy and to preserve bodies is the sim-
plest form of aldehydes that is form-
aldehyde?

O O
|| ||
R - C - H R - C - R´
General formula of aldehydes General formula of ketones

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 Chapter - 7

7-5-1 Nomenclature of Aldehydes and Ketones

Aldehydes and ketones are named according to IUPAC nomenclature system as
in the following steps:

A) Nomenclature of Aldehydes
1- The longest carbon chain is chosen. The carbon atom of carbon group is
numbered with 1.
2- -al suffix is added to the end of the name of the corresponding alkane.
3- Alkyl groups are mentioned with their numbers.
As numbering starts from the side of carbonyl group, the number of carbonyl
group doesn’t need to be mentioned. For example:

O O Cl O O
|| || | || ||
CH3 - C - H H - C- H CH3 - CH - C - H CH3 - CH2 - C - H
Ethanal Methanal 2-chloropropanal Propanal

B) Nomenclature of Ketones
We apply the steps in nomenclature of aldehydes.
1- We choose the longest carbon chain and start numbering from the closest
carbon to the carbonyl group.
2- We add –one suffix to the end of the corresponding alkane.
3- If there is branching, alkyl groups are mentioned with their numbers.
O O CH3 O
|| || | ||
CH3 - CH2 - C - CH2 - CH3 CH3 - CH2 - C - CH3 CH3 - CH - C - CH3
3-pentanone 2-butanone 3-methyl-2-butanone
Exercise 7-16
1- Write down systematic names
7-5-2 Preparation of Aldehydes and Ketones
Aldehydes and ketones are synthesized through many methods in industry and
for the following compounds:
laboratories. Here, we will explain one of the laboratory methods.
a) O
||
CH3 - CH - CH2 - C - H Oxidation of Alcohols
| Aldehydes and ketones are prepared by oxidation of primary (1°) and secondary
Cl (2°) alcohols with acidic solution of potassium dichromate (K2Cr2O7 ) or potas-
b) CH3 sium permanganate (KMnO4 ).
| Primary alcohols form aldehydes as shown in the following equation.
O CH 2 H H
|| | | K2Cr2O7/H+ |
CH3 — C — CH — CH3 R—C—O—H R—C = O + H2O
| [O]
H
2- Write down formulas for the Primary alcohol Aldehyde
following compounds.
a) 3-methylbutanal
b) 2-hexanone O
K2Cr2O7/H+ ||
CH3CH2OH CH3 - C - H + H2O
[O]
Ethanol Ethanal

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 Organic Chemistry

The aldehyde remaining in the reaction mixture above is readily oxidized and it
forms carboxylic acid.

Therefore, oxidation reaction must be controlled.

H O O
| K2Cr2O7/H+ || K Cr O /H2
||
2 7
+

R—C—O—H R—C — H R—C —O—H

| [O]
H Do you know that
Primary alcohol Aldehyde Carboxylic acid Some aldehydes and ketones are ob-
tained from plants.
Ketones are prepared through oxidation of secondary (20) alcohols. Benzaldehyde is obtained from al-
H R monds and some ketones are obtained
| K2Cr2O7/H+ | from cinnamon.
R—C—O—H R—C = O
| [O]
R
Secondary alcohol Ketone
For example:
OH O
| K2Cr2O7/H+ ||
CH3 - CH - CH3 CH3 - C - CH3
[O]
2-propanol Propanone

Tertiary alcohols cannot be oxidized.

Example7-7
Write down oxidation products of the following compounds.
1) 1-propanol
2) 2-pentanol
Exercise 7-17
Prepare the following compounds
Solution: using suitable alcohols.
1) O 1) ethanal
K2Cr2O7/H+ || [O] 2) 2-butanone
CH3 - CH2 - CH2-OH CH3 - CH2 - C - H + H2O
[O]
1-propanol propanal

O
[O] ||
CH3 - CH2 - C -O - H
propanoic acid

2) OH O
| K2Cr2O7/H+ ||
CH3 - CH2 - CH2- CH -CH3 CH3 - CH2 - CH2- C - CH3
[O]
2-pentanol 2-pentanone

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 Chapter - 7

7-5-3 Properties of Aldehydes and Ketones

1- Physical Properties
All aldehydes and ketones are in liquid form at room temperature except matha-
nal (formaldehyde, in gas form).
Although ketones have pleasant odors, aldehydes have unplaeasant odors.
Densities of ketones are lower than that of water. Owing to the polar property
of carbonyl group, these compounds are accepted as polarized. They can dis-
solve in water and organic solvents like ether. Boiling points of aldehydes and
ketones are higher than those of alkanes, but lower than alcohols which have
the same molecular weight with them. For example:
O
||
CH3 - CH3 H- C - H CH3 - OH
Ethane Formaldehyde Methyl alcohol
Aldehydes can dissolve in water M= 30, bp = -89 °C M= 30, bp = -21 °C M= 32, bp = 64.5 °C
because of hydrogen ion in their
molecules. CH3 O OH
| || |
CH3 - CH- CH3 CH3 - C- CH3 CH3 - CH- CH3
Isobutane Acetone Isopropyl alcohol
M= 58, bp = -12 °C M= 58, bp = 56 °C M= 60, bp = 82.5 °C

(M = molecular weight and b.p = boiling point)

2- Chemical Properties
The carbonyl group in aldehydes and ketones has high ionization property as
shown below:

Carbon in the carbonyl group is positive charged, as nucleophile approaches it,

electrophile approaches to negative charged oxygen.

Aldehydes and ketones can undergo two-step nucleophilic reactions. These are:

A) 1st step: Nucleophile approaches carbon of carbonyl group and forms a

new bond. This bond breaks double bond between oxygen and carbon and
pushes a pair of electrons to oxygen atom.

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Exercise 7-18
Complete following equations:
a) O
|| [Red]
C2H5 - C - CH3
H2/Pt

B) 2nd step: approach of an electrophile such as H+ ion:
b)
O
|| [Red]
C2H5 - C - H
H2/Ni

Reactions of Aldehydes and Ketones:

a) Reduction with hydrogen

Aldehydes are reduced to primary alcohols and ketones are reduced to second-
ary alcohols when they react with H2 with Ni and Pt as catalysts.
O
||
Ni
CH3 - C - H + H2 CH3 - CH2 -OH
[Red]
Ethanal Ethanol
O OH
|| |
Ni
CH3 - C - CH3 + H2 CH3 - CH -CH3
[Red]
Propanone 2-propanol
(Red means reduction)

b) Reduction to Alkanes
Aldehydes and ketones are reduced to alkanes via Clemmensen reduction
method. In this method, solution of zinc and mercury in hydrochloric acid is
used as catalyst.
O
||
Zn/Hg
R - C - R´ R - CH2 - R´
HCl

O
||
Zn/Hg
CH3 - C - C2H5 CH3 - CH2 - C2H5
HCl
2-butanone butane

O
||
Zn/Hg
R- C- H R - CH3
HCl

O
||
Zn/Hg
CH3 - C - H CH3 - CH3
HCl
Ethanal Ethane

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 Chapter - 7

c) Reaction with Hydrazine

Exercise 7-19 Aldehydes and ketones react with hydrazine (H2N-NH2) and produce
1- Prepare propane from propanal.
hydrazone which is known as Schiff base.
2- Write down the reaction of
propanal with hydrazine. H H
| |
Δ
CH3—C = O + H2N-NH2 CH3—C =N-NH2 + H2O
Hydrazine Acetaldehyde hydrazone

CH3 CH3
| |
Δ
CH3—C = O + H2N-NH2 CH3—C =N-NH2 + H2O
Acetone Hydrazine acetone hydrazone

This reaction is used to examine the presence of carbonyl group in aldehydes

and ketones. Hydrazone (orange or yellow color) shows the presence of the
carbonyl group.

d) Oxidation
Presence of hydrogen bonded to carbonyl group in aldehydes causes some re-
actions different from those of ketones. The most important reactions of alde-
hydes and ketones are oxidation reactions.
Aldehydes are oxidized into carboxylic acids by the help of some oxidizing
Do you know that agents. But in ketones, this does not occur. We can differentiate aldehydes and
The accumulation of silver on test ketones using following reactions:
tube as a result of the reaction of
aldehydes with Tollens’ Reagent 1-Tollens’ Reagent
enabled chemists to produce many In order to differentiate aldehydes, silver ammonium hydroxide is used. In this
types of mirrors? reaction, silver ion is reduced in solution and silver metal covers the tube’s sur-
face as mirror showing the presence of aldehyde. This reaction is shown below:

O O
|| ||
R- C - H + 2Ag(NH3)2OH → R- C - O- NH4+ + 2Ag↓ + H2O + 3NH3
aldehyde silver ammonium hydroxide salt of carboxylic acid Silver mirror

Tollens’ Reagent
O
||
R - C - R + 2Ag(NH3)2OH → N.R.

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e) Reaction with Fehling’s Solution

Fehling’s solution is a solution of copper sulfate salt. It’s basic and dark blue.
It is used in oxidation of aldehydes. In this reaction, copper (II) ions transforms
into red copper (I) oxide. This red copper (I) oxide precipitate shows presence
of aldehyde in mixture. As shown below, ketones do not react with this reagent.

O O
|| || Fehling’s Solution
R- C - H + 2Cu 2+
+ 5OH → R- C - O + Cu2O↓ + 3H2O
- -

aldehyde in a complex red precipitate

O Exercise 7-20
|| How can you differentiate
R - C - R + 2Cu2+ + 5OH- → N.R propanal and propanone com-
pounds using the following
practically?
7-6 CARBOXYLIC ACIDS a) Fehling’s solution
The functional group of all carboxylic acids is carboxyl group (-COOH) or b) Tollens’ Reagent
O
||
( - C - OH). This group consists of hydroxyl and carbonyl groups.
O
||
The structural formula of carboxylic acids is R - C - OH. (R) represents alkyl
group or hydrogen atom. Their general formula is (CnH2nO2).

7-6-1 Nomenclature of Carboxylic Acids

Carboxylic acids are named according to IUPAC system as shown in the fol-
lowing steps:

1- The longest carbon chain that includes carboxyl group is chosen and num-
bered. Carboxyl group is given number 1.
2- Branched groups are written in alphabetical order and with their numbers Ethanoic acid
mentioned. (vinegar)
3- The word “acid” is added.
4- The name of the alkane which corresponds to the longest carbon chain is
written and suffix (-oic) is added in the end. Exercise 7-21
1) Write the name of the following
Br compound.
| Cl O
CH3COOH HCOOH 3
CH3 - 2CH - 1COOH | ||

Ethanoic acid Methanoic acid 2-bromopropanoic acid CH3 - CH2 - C - C - OH

|
CH3
CH3 CH3 2) Write the structure formula of
| |
the following compounds.
6
CH3-5CH2-4CH -3CH -2CH2-1COOH a) 2- methylbutanoic acid
3,4-dimethylhexanoic acid b) 3-chloropropanoic acid

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 Chapter - 7

7-6-2 Preparation of Carboxylic Acids

Carboxylic acids are prepared through many methods. As we have mentioned
before, they are prepared by oxidation of primary (1°) alcohols or aldehydes.
We will explain preparation of carboxylic acids using Grignard reagent. In this
reaction, firstly, alkyl halide is used then CO2. As shown below, in order to pre-
pare wanted carboxylic acid, hydrolysis (reaction with water) in acidic medium
is realized.
dry ether
R - X + Mg RMgX
Lemons contain citric acid Grignard reagent
which is a carboxylic acid.
O O
|| ||
H2O/H +

RMgX + CO2 R- C - O - MgX R- C - O - H

Grignard compound carboxylic acid
O O
Exercise 7-22 ||
H2O/H + ||

Prepare propanoic acid from CH3MgBr + CO2 CH3- C - O - MgBr CH3- C - O - H

Methyl magnesium bromide ethanoic acid
the following:
1) ethyl bromide The carboxylic acid prepared through this method has one extra carbon than
2) propanal the alkyl group of Grignard compound.

7-6-3-General Properties of Carboxylic Acids

1-Physical Properties:
The carboxylic acids with low molecular weights (lower than C10) are liquids
with pungent and unpleasant odors. As their molecular weights increase, their
boiling points also go up and the boiling points are higher than those of alco-
hols with the same number of carbons. The reason is that carbonyl and hydrox-
yl group in acid molecule ionize at a high rate and hydrolysis occurs (more than
alcohols) between acid molecules.

Carboxylic acids with low molecular weights are highly-soluble in water. As

their molecular weights increase, their solubilities decrease.

2-Chemical Properties:
A) Acidity of Carboxylic Acids:
Hydrogen bond Carboxylic acids assume acid property by carboxyl group’s donation of proton.
Therefore, they react with bases readily and form water and salt.
O O
|| || +
-
R- C - O - H + NaOH R- C - O Na + H2O
Carboxylic acid Salt of Carboxylic acid

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B) Reactions of carboxylic acid with carbonates and bicarbonates Exercise 7-23

When carboxylic acids react with carbonates and bicarbonates, CO2 gas is Write down the reaction of acetic
formed. This reaction is one the important reactions to differentiate carbonyl acid with sodium bicarbonate,
group in carboxylic acids. (NaHCO3).

RCOOH + NaHCO3 RCOONa + CO2 + H2O

C) Reaction of carboxylic acid with alcohols (esterification reaction)

Carboxylic acids react with alcohols along with HCl or H2SO4 catalysts and
form esters. This reaction is reversible as seen below and called as esterifica-
tion.
O O
|| H+ ||
R- C - O - H + H - OR´ ⇌ R- C - O- R´ + H2O
Carboxylic acid Ester
O O
|| H+ ||
CH3- C - O - H + H - OC2H5 ⇌ CH3- C - O- C2H5 + H2O
Acetic acid Ethanol Ethyl ethanoate

D) Reduction of Carboxylic Acids

Carboxylic acids are reduced by reducing agents such as lithium aluminum hy-
dride (LiAlH4) and form primary alcohols. But they cannot be reduced with
H2/Ni.
O
||
LiAlH4
CH3- C - OH ether
CH3- CH2-OH
Acetic acid Ethanol Do you know that
Aspirin which has been used as
Example 7-8 painkiller is one of the most important
Prepare propanoic acid starting from ethanal. carboxylic acids?

O O
|| ||
CH3- C - H CH3- CH2- C -OH

Solution:
The equations of the reactions are as follows:
O
||
Pt PCl3 Mg
R - C - H + H2 R - CH2-OH dry ether
R - CH2-X


CO2 HX
R - CH2-MgX R - CH2-COOMgX R - CH2-COOH + MgX2

1. step
O
||
Pt
CH3 - C - H + H2 CH3- CH2-OH
Ethanal Ethanol

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 Chapter - 7

Exercise 7-24 2. step

Prepare butanoic acid starting from 3CH3- CH2-OH + PCl3 3CH3- CH2-Cl + H3PO3
propanal. Ethanol Ethyl chloride
3. step
dry ether
CH3- CH2-Cl + Mg CH3- CH2-MgCl
Exercise 7-25 Ethyl chloride Grignard reagent
Prepare butanoic acid starting from 4. step
1-butanol. CH3- CH2-MgCl + CO2 CH3- CH2-COOMgCl
Intermediate compound
5. step
CH3- CH2-COOMgCl + HCl CH3- CH2-COOH + MgCl2
Propanoic acid
Example 7-9
Prepare propanoic acid starting from ethyl chloride.

Solution:
In this method, a carboxylic acid is obtained with one more extra carbon than
the number of carbons of the starting alkyl.

dry ether
CH3- CH2-Cl + Mg CH3- CH2-MgCl
Ethyl chloride Grignard reagent

CH3- CH2-MgCl + CO2 CH3- CH2-COOMgCl

Intermediate compound

CH3- CH2-COOMgCl + HCl CH3- CH2-COOH + MgCl2
Propanoic acid

(Vitamin C ), C which is known as ascorbic acid is a carboxylic acid which is

found in citrus fruits most. It has an important place in our lives. Vitamin C
helps improving defense of body by strengthening immune system. It is given
as pills to patients.

7-7 ESTERS
Vitamin C is found in many Esters have got the same functional group with carboxylic acids. They both
fruits. have molecule. The structural formula of esters is

and general formula is CnH2nO2. Here R´=R or R´≠R.

Besides, R can never be a hydrogen atom as in carboxylic acids.

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7-7-1 Nomenclature of Esters Do you know that

Esters which are found in fruits
As esters are made up of two groups, one is from carboxylic acid and vegetables have pleasant odors
and therefore they are used as
and the other is from alcohol , so they are named after they are di-
sweetener in foods, perfumes and
vided into two groups as follows:
kids’ foods?
1- The first name of ester belongs to the alkyl group bonded to the oxygen atom
in alcohol group.
2- The remaining name is written by adding –oate suffix to the alkane part of
the carboxylic acid.
Exercise 7-26
Cl O O 1- Write down systematic names
| || ||
3
CH3 - 2CH - 1C - O - C2H5 2
CH3 - 1C - O - CH3 of the following compounds.
Ethyl 2-chloropropanoate Methyl ethanoate A) O
||
CH3 - CH - C - O - C2H5
7-7-2-Preparation of Esters |
Esters can be synthesized through many methods such as the reaction of alco- CH3
hols and carboxylic acids. Besides, by adding pyridine to produce HCl, car- B) O
boxylic acid chloride is obtained and with its reaction with alcohol, esters are ||
prepared. H - C - O - CH3
O O
|| pyridine || 2- Write down structural formula
R- C - Cl + H - OR´ R- C - O- R´ + HCl
for the following compound.
O O Propyl 2,3-dimethylhexanoate
|| pyridine ||
CH3- C - Cl + CH3OH CH3- C - O- CH3 + HCl
Acetyl chloride Methanol Methyl ethanoate

7-7-3 General Properties

1- Physical Properties of Esters
Esters can ionize. They don’t form hydrogen bonds between their molecules.
Therefore, their boiling points are lower than those of carboxylic acids with the
same number of carbons. Most esters don’t dissolve in water but dissolve in
many organic solvents. Besides, these substances are used as good solvents for
many organic compounds.

2- Chemical Properties of Esters

Esters undergo following reactions.
a) Reaction of Esters with Water in Acidic Solution
This reaction is the opposite of esterification reaction which is synthesis of
esters from alcohols and carboxylic acids. Here H2SO4 and HCl are used as
catalysts. Esters react with water and form carboxylic acids and alcohols.
O O
|| .. H+ ||
R- C - O - R´ + H2O ⇌ R- C - OH + R´ - OH
Ester Carboxylic acid Alcohol
O O
|| H+ ||
CH3 - C - O - CH2 CH3 + H2O ⇌ CH3- C - OH + CH3 CH2 - OH
Ethyl ethanoate Ethanoic acid Ethanol

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 Chapter - 7

b) Reaction of Esters with Water in Basic Medium

Esters react with water molecules in basic solution such as NaOH. At the end
of the reaction, sodium salt of carboxylic acid and alcohol are formed. This
reaction is very important as it is used in soap production. Therefore, it is also
known as saponification reaction. Besides, it is used to differentiate esters as
Apples and beeswax contains esters. shown in the following reaction:

O O
Exercise 7-27 ||
CH3 - C - O - CH2 CH3 + NaOH
H2O || - +
CH3- C - O Na + CH3 CH2 - OH
1- Prepare ethyl methanoate starting Δ
Ethyl ethanoate Sodium ethanoate Ethanol
from methanol.

2- Prepare methyl propanoate starting 7-8 AMINES

from ethanol. Amines are compounds which are formed by substitution of hydrogen atoms
in ammonia NH3 by one or more alkyl groups. Therefore, amines are named
3- Prepare ethyl ethanoate starting according to the number of alkyl groups they contain. If an alkyl group replaces
from acetyl chloride. one hydrogen of ammonia, it is called as a primary amine RNH2 ; if two alkyl
groups replace two hydrogen atoms, it is called as a secondary amine R2NH ; if
three alkyl groups replace three hydrogen atoms, it is called as a tertiary amine
Exercise 7-28 R3N. For example:
Write down the reactions of ethyl
methanoate with water in acidic and H R´ R´
basic solutions. | | |
R — N — H R — N — H R — N — R´´
Primary amine Secondary amine Tertiary amine
(1°) (2°) (3°)

7-8-1-Nomenclature of Amines
a) Special (Common) Nomenclature
1- In this method, firstly, the alkyl group bonded to nitrogen atom is written
then the word amine.

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 Organic Chemistry

For example:

CH3 - NH2 CH3 CH2- NH2 CH3 CH2 CH2 - NH2

Methyl amine Ethyl amine n-propyl amine

2- If there are two or three alkyl groups bonded to nitrogen atom, di- or tri- pre-
fixes are added to the word amine.

CH3 CH3
| |
CH3 - N - H CH3 - N - CH3
dimethyl amine trimethyl amine

3- If the alkyl groups are different, they are written in alphabetical order.
Amines cause odor of rotten fish.
H CH3
| |
CH3 - N - CH2 -CH3 CH3 - CH2 - N - CH (CH3)2
ethyl methyl amine ethyl isopropyl methyl amine

b) Amines are named according to IUPAC system as in the

following steps:
1- The longest carbon chain which carries the amine (-NH2) group is chosen
and numbered. Amine group acts as the functional group.

2- Previous rules are valid in naming amines.

CH3 NH2 NH2 CH3

| | | |
CH3 - C - CH3 CH3 - CH - COOH CH3 - CH2 - CH -CH2 - CH -CH3
|
NH2 2-aminopropanoic acid 3-amino-5-methylhexane
2-amino-2-methylpropane

7-8-2 Preparation of Amines

There are many methods to prepare amines. We will explain only two of them
here.

1- Reaction of Ammonia and Alkyl Halide

Using ammonia, we can prepare three types of amines.
For this, as in the example below, alcoholic ammonia solution and alkyl halide
are mixed and heated.
+ - NaOH
CH3 I + NH3 CH3-NH3 I CH3-NH2 + NaI + H2O
Methyl iodide (1°) methyl amine

This is not a successful laboratory method as a mixture of primary, secondary

and tertiary amines which are difficult to separate are prepared. We only prepare
primary amines with this method.

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 Chapter - 7

Exercise 7-29 2- Ammonia-Alcohol Reactions

Prepare ethyl amine using suitable Primary amines are prepared when ammonia and alcohol react with aluminum
alkyl halides. oxide as catalyst at 400°C. In this reaction, just like the reaction above, a mix-
ture of primary, secondary and tertiary amines is obtained. But when a great
amount of ammonia is used, we get mainly primary amine.

Δ
CH3 OH + HNH2 CH3-NH2 + H 2O
Al2O3
Methanol ammonia (1°) methyl amine

7-2-3-General Properties
1- Physical Properties
Molecular weights of amines are small and their odors are like ammonia’s.
They are in gas form at room temperature. These compounds form hydrogen
bonds due to their ionization property. Therefore, their boiling points are high-
er than those of compounds which cannot ionize. Figure 7-2
Amines can dissolve in water as they can form hydrogen bonds with water
molecules. Besides, they can dissolve in organic solvents such as benzene and
ether.
Figure 7-2
a- Hydrogen bonds between water
2- Chemical Properties
and amine molecules.
Amines are accepted as bases as nitrogen atom has a pair of electrons which
b- Hydrogen bonds between
can make bond with protons or Lewis acids.
amine molecules
-
R - NH2 + HCl R-NH3+ Cl
amine amine salt
Exercise 7-30
Prepare propyl amine using alcohol. This salt can be transformed into amine again when it reacts with a strong base.
NaOH
-
R-NH3+ Cl R-NH2 + NaCl + H2O

Besides, amines form compounds known as amides when they react with acid
chlorides.

O H O H
|| | || |
CH3- C - Cl + H - N - CH3 CH3- C - N- CH3 + HCl
Acetyl chloride Methyl amine N-methylacetamide

Amine is a base.

242 FEZALAR EDUCATIONAL INSTITUTIONS

 Organic Chemistry

BASIC CONCEPTS
Organic Chemistry: It is one of the branches of chemistry. Along with other elements, it studies compounds which
have carbon as main element.
Hydrocarbons: They are the simplest organic compounds which contain only carbon and hydrogen. If carbon atoms
form single bonds, they form alkanes which are saturated hydrocarbons; if there is a double bond between carbons, they
form alkenes; if there is a triple bond, they form alkynes. Both alkenes and alkynes are unsaturated hydrocarbons. Ben-
zene and derivatives are cyclic, unsaturated hydrocarbons. They are called as aromatic hydrocarbons.
Isomers: They are organic compounds which have the same general formulas but different structural formulas, physical
and chemical properties.
Functional Group: They are atoms or atom groups which are bonded to the carbon atom that differentiate organic
compounds and give them different physical and chemical properties.
Markovnikov’s Rule: When we add unsymmetrical double-ion carrying compounds to double bonded compounds
which have unsymmetrical alkyl groups, positive ion (hydrogen ion) attaches to the carbon atom with more hydrogen
atoms and carbonium ion is formed. Negative ion is attached to the carbon atom with less hydrogen atoms.
Electrophile Reagent: These are electron-loving atoms, molecules or ions which can accept a pair of electrons due
to their empty orbitals. Lewis bases as NO2+ , X+ , R+ , and Lewis acids as carbonyl group and aluminum chloride AlCl3
are examples.
Nucleophile Reagent: These are nucleus-loving atoms, molecules or ions which can donate a pair of electrons as they
have extra electrons. Lewis bases as OH- , X-, and H-, carbonium ion, R-, double or triple ions and ammonia are examples.
Alcohols: They are organic compounds which have hydroxyl group attached to a saturated carbon atom. Their structur-
al formula is R-OH, and their general formula is CnH2n+2O, their functional group is C-OH.
Ethers: They are organic compounds which have oxygen atom bonded to two alkyl groups. Their structural formula is
R-O-R, their general formula is CnH2n+2O, and their functional group is C-O-C.

Aldehydes: They are organic compounds which have hydrogen on one side of the carbonyl group and hy-

drogen or alkyl group on the other side. Their structural formula is , general formula is CnH2nO and their

functional group is carbonyl group.

Ketones: They are organic compounds which have alkyl groups on both sides of carbonyl group. Their structural for-

mula is , general formula is CnH2nO, and their functional group is carbonyl group.

Carboxylic acids:Their functional group is carboxyl group –COOH, their general formula is R-COOH and their

closed formula is CnH2nO2.

Esters: They are derivatives of carboxylic acids. They have carboxyl group as carboxylic acids . In esters,
oxygen of the carboxyl group is attached to alkyl group. Their structural formula is , and general formula
is CnH2nO2.

Amines: They are derivatives of ammonia. Alkyl groups replace one or more hydrogen atoms in ammonia. They are
divided into three groups as primary amines RNH2, secondary amines R2NH and tertiary amines R3N. Their structural
formula is R-NH2 and general formula is CnH2n+3N.

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 Chapter - 7

QUESTIONS OF CHAPTER-7
7-1- Prepare a table containing names, group names and names of functional groups in the following compounds.

7-2- There are two colorless liquids in two different test tubes. One is hexane, the other is 1-hexanol. How can you dif-
ferentiate these two liquids?

7-3- Write down the preparation processes of the following compounds from the starting substances.
a) 1-propanol from 1-chloropropane b) ethanol from ethene
c) ethanal from ethanol d) sodium ethanoate from methyl ethanoate

7-4- We have 1-chlorobutane and 1-butene compounds in laboratory. Which one do you use to prepare 1-butanol?

7-5- Supply names for the following organic compounds according to IUPAC system.

1) O 3) CH3CH2CH2CH2CH2Br 6) O
|| ||
CH3(CH2)3 C - OH 4) CH3CH2CH2CH2NH2 CH3CH2CH2CCH2CH3

2) CH3 5) O 7) O
| || ||
CH3CH2 C - CH2OH CH3(CH2)2 C - OCH3 CH3(CH2)4 C - H
| 8) O
CH3 ||
CH3(CH2)2 C - CH3

7-6- Supply structural formulas for the following organic compounds.
1) 2,3-dimethylhexanoic acid 2) butyl butanoate 3) 3-ethyl-1-heptanol
4) 3-methyl-4-heptanone 5) 2-methyl-2-pentanol 6) 3-ethyl-2-aminohexane
7) 3-chlorohexane 8) 2-amino-2-methylbutane 9) dibutyl ether
10) 3-methylpentanoic acid

7-7- Write down structural formulas, functional groups and IUPAC names for the following compounds.
(Students can refer to Table 7-2 to answer this question.)
a) C4H8O2 b) C4H8O c) C4H9OH

7-8- Write the equations showing the following reactions.

1) Preparation of ethanoic acid starting from methanal.
2) Preparation of ethanol starting from methanol.
3) Preparation of propanoic acid starting from 1-bromopropane.

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7-9- An organic compound which has general formula CnH2n+2O with molar mass of 60 g/mol does not react with Lucas
reagent. But it undergoes oxidation completely. Write the molecular and structural formulas of the compound. After that
write its reactions and then write general formulas and names of its products.
7-10- Circle the correct answers.
1- Which compound is obtained by heating ethanol and sulfuric acid?
O
||
a) CH3 - C - H b) CH2 = CH2 c) CH3COOH d) CH3-CH3

2- What is the compound obtained from oxidation of 2-propanol with the help of K2Cr2O7 in acidic conditions?
a) propanal b) propanone c) propene d) propanoic acid

3- The compound obtained from reduction of propanal by addition of Ni and H2:

a) propanoic acid b) 1-propanol c) 2-propanol d) propane

4- The gas obtained from the reaction of ethanol with sodium metal:

a) CO2 b) O2 c) CO d) H2

5- The substance obtained from the reaction of ethanal with HCl:

a) Primary alcohols b) Secondary alcohols c) Tertiary alcohols d) Alkane

6- The gas obtained from the reaction of ethanoic acid with carbonate:

a) H2 b) CO2 c) O2 d) CO

7- For which of the following is Lucas’ reagent (HCl/ZnCl2 ) used to differentiate?

a) primary, secondary and tertiary alcohols b) aldehydes and ketones c) primary and secondary amines

8- The number of structural formulas of C3H6Br2 compound:

a) 2 b) 3 c) 4 d) 5

9- In order to form silver mirror, with which of the following should silver ammonium hydroxide react?

a) ketone b) aldehyde c) tertiary alcohol d) alkane

10- Which of the following compounds reacts with Fehling’s solution?

O O O O
|| || || ||
a) CH3 - C - OCH3 b) CH3 - C - H c) CH3 - C - OH d) CH3 - C - CH3

11- What is the reaction which transforms propanone to 2-propanol?

a) oxidation b) cleavage c) reduction d) substitution

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 Chapter - 7

7-11- Write down the synthesis equation of butanoic acid from suitable alkyl halide with Grignard reagent.

7-12- Write down the names of organic compounds from A to E in the chain reactions starting with ethylene
(CH2=CH2).
CH2 = CH2 + HCl A
H2O
A + KOH B
K2Cr2O7/H+ K2Cr2O7/H+
B C D

D + NaHCO3 E + CO2 + H2O

7-13- How can you differentiate the following compound pairs experimentally?
1) propanal and propanone 2) 1-pentanol and pentane
3) butanal and butanoic acid 4) 2-methyl-2-propanol and 1-propanol
5) ethanol and ethanoic acid 6) ethylamine and ethane

7-14- Explain the following changes via chemical equations:

a) CH3 CH3
| |
CH3 - C- CH3 CH3 - C- CH3
| |
Cl OH
b) O
||
CH3 - C- CH3 CH3 - CH = CH2
c) 1-butene → 2-butanol

7-15-The following compounds are formed from result of oxidation reactions of alcohols. Write down their reactions and
structural formulas and names of alcohols.

a) Ethanal b) 2-methylpropanal c) 2-butanone

7-16- Study the following equations and answer the questions.

OH- K2Cr2O7 Fehling’s Solution
C4H9Br C4H9OH C4H8O N.R.
A B C
a) Write down the structural formulas of A, B and C.
b) Write down the names of A, B and C.
c) Which of B and C has higher boiling point?
d) Write down other structural formulas of compound B which doesn’t oxidize with K2Cr2O7 in acidic conditions.

7-17- Two of the following compounds were mixed in acidic conditions. At the end of the reaction, pleasant-smelling
C4H8O2 compound formed. Find out those two compounds and write down the equation:

CH3 CH3 , CH3 CH2OH , CH3CHO, CH3COOH, CH3CH2OCH3

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7-18- Write down the synthesis equations of the following compounds starting from ethanol.

a) ethanoic acid CH3COOH b) ethyl ethanoate CH3COOCH2CH3

c) chloroethane CH3CH2Cl d) ethyl magnesium chloride CH3CH2MgCl

7-19- Obtain the following compounds starting from ethylene (CH2=CH2). Write down the equations.
a) ethanal b) ethyl magnesium chloride c) ethyl hexanoate

7-20- As A has three carbon atoms, write down the formulas of the following A, B, C, D, E organic compounds in the
following equation chain.

HCl Mg CO2 HCl
A B C D E
dry ether

7-21- Write down structural formulas and chemical reactions of the following.
1) Hydration of propene with presence of sulfuric acid and then oxidation reaction of the product.
2) Preparation of ethane and ethylamine starting from ethanal.

7-22- A is an organic compound which has 3 carbon atoms. It forms compound B when it is oxidized. This substance
doesn’t react with Fehling’s solution. When sodium metal reacts with compound A, compound C is obtained. But when
B is reduced, it yields compound A.
a) Write down the structural formulas of A, B, and C.
b) Write down the formation equations of compounds A, B and C.

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 Chapter - 87

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248 FEZALAR EDUCATIONAL INSTITUTIONS

 Biochemistry

BIOCHEMISTRY CHAPTER-8

ACHIEVEMENTS
After studying this chapter, students can do the following:
* They can differentiate different types of carbohydrates.
* They learn types of sugars and their differences.
* They can differentiate starch.
* They learn lipids.
* They learn how soap is produced and the ingredients used in soap production.

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 Chapter - 8

8-1 PREFACE
Biochemistry is the branch of science which studies chemistry of biosynthe-
sis in living beings. This branch of science explains biological phenomena in
bodies of living beings in terms of chemistry by studying chemical changes in
human body and in other creatures. In this chapter, we will study the properties
and reactions of two important chemical substances which we take into our
bodies from foods. These are carbohydrates and proteins.

8-2 CARBOHYDRATES
Have you ever thought about carbohydrates which make up of most of our food
as bread and rice?
Do you know why honey, banana, apple, grapes and some other fruits are
sweet?
In the structure of these foods, chemical substances as carbohydrates, starch,
sugar are found.
What are carbohydrates? What are their properties and how many kinds of
carbohydrates are there?

8-2-1- Structure of Carbohydrates

Carbonhydrates,starch and sugar are If we examine the structures of the foods mentioned above, we see that they
fundemental foods for humans. are made up of oxygen, hydrogen and carbon. But the ratio of oxygen is high-
er than others. In the structural formula of most carbohydrates, carbon atom
forms bonds with atoms of water molecule. These are (CH2O)n and Cn(H2O)n.
Therefore, this kind of molecules are called as carbohydrates as they originate
from water and carbon.
Carbohydrates are divided into two groups as simple and complex carbohy-
drates. They can be in long carbon chains which can rotate plane polarized light
(optically active) or in cyclic structure. Both structures are stable.

8-2-2-Classification of Carbohydrates
Carbohydrates are classified as follows:
1-Monosaccharides: e.g. Glucose and fructose
2-Disaccharides: e.g. sucrose, maltose and lactose
3-Polysaccharides: e.g. Starch and cellulose
We will mention some important properties of each group.
1-Monosaccharides:
They are the simplest form of carbohydrates. We can give glucose and fructose
as examples.
a) Glucose (Grape sugar):
Glucose is found in grapes and blood in nature. It is especially important as
a nutrient for patients who cannot be fed through mouth and also in surgical
operations. Its molecular formula is C6H12O6 or C6 (H2O)6. The molecular struc-
ture and geometrical shape of glucose are given below.

250 FEZALAR EDUCATIONAL INSTITUTIONS

 Biochemistry

Closed structure formula of glucose

In open structure formula glucose

molecule, functional groups are
attached to long carbon chain.

-In cyclic structure, it is an ether containing hydroxyl groups.

-In open structure, it is an aldehyde containing hydroxyl groups.
We can explain the properties of glucose with respect to its molecular structure.
The molecular structure also helps us understand its reactions. It doesn’t hy-
drolyze when dissolved in water. Glucose has a crystalline structure. Its boiling
point is high. It dissolves in water. When we study the structural formula of
glucose, we can see that hydrogen bonds form between hydroxyl groups and
hydrogen atoms and glucose molecules. These hydrogen bonds cause boiling
point elevation.
When we examine the open structural formula of glucose, we see that it is
formed from an aldehyde group and many hydroxyl groups. Therefore, it has
some properties similar to those of alcohols and aldehydes. Therefore, they are
oxidized in Tollens’ Reagent and Fehling’s Solution.

b) Fructose (Fruit sugar)

Fructose is found in honey and most fruits. Its molecular formula is C6H12O6
and it is same as the molecular formula of glucose. But their structural formu-

las are different. In Figure. a and b these formulas are shown. . As its
structure is similar to that of glucose, their physical properties are also similar.
They both contain hydroxyl groups (-OH) and carbonyl groups. In their open
formulas. In cyclic structure,
they have (-OH) and groups which raise both boiling point and
water solubility.
In open structural formula, there are (1) carbonyl group of ketone which gives
properties similar to carbonyl and ketones and (2) hydroxyl groups. Therefore,
fructose can be oxidized. Contrary to ketones, fructose is oxidized with Tollens
Reagent and Fehling’s Solution. Therefore, although fructose is a ketone, it is
accepted as among reducing sugars.

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2) Disaccharides
They are formed through cleavage of one water molecule from similar or dif-
ferent two monosaccharides.
Sucrose
Sucrose and sugar cane are examples. Sucrose is sweet. It is produced from
sugar cane. After refining, purification and crystallization, we get white sugar.
Its molecular formula is C12H22O11. In sucrose molecule, through cleavage of
one water molecule from one glucose and fructose molecule, glycoside bonds
are formed between them. But this bond dissolves during digestion in our bod-
ies.
Sucrose → Fructose + Glucose

A) Cyclic formula of fructose

B) Open formula of fructose

3) Polysaccharides
They are large molecules formed through bonding of many monosaccharides
together. Starch and cellulose are examples.

a) Starch
When we consume potato, we get carbohydrates formed from small glucose
units. This substance is a polymer called as starch. Its basic unit is glucose.
Between them, there are double carbonyl bonds.

b) Cellulose
Cellulose is a large molecule formed from glucose polymer. Although basic
units of cellulose and starch are the same, they have different shapes and prop-
erties depending on number of glucose. The main source of cellulose is wood
fibers and besides peel of some fruits as date palm have cellulose. Some en-
zymes or some acid solutions dissolve those big molecules. A similar event to
this occurs in digestive system in our bodies.

White sugar is disaccharide that is

Cellulose → Glucose
sucrose.

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8-2-3- Decomposition of Starch

Starch molecules form bonds with iodine molecules in iodine solution and pro-
duce a blue compound. The iodine solution is obtained by dissolving iodine
crystal in potassium iodate solution.
Thus, to differentiate starch, a few drops of iodine solution in potassium iodate
is added to starch solution. If blue color is observed, that shows the presence
of starch. Cellulose

8-3 PROTEINS
Protein is from Greek. It means “primary”, “in the lead” or “standing in front”.
It is the main building block of of our bodies. It is found in all living beings.
It carries great importance as it is the biggest source of amino acids which are
necessary for growing of living beings.
What are the chemical structures of these substances? What are the similarities
and differences between molecules?
What are the shapes of their molecules? Can we prepare them in laboratory?

8-3-1 Elements making up of protein molecules

As a result of many experiments, it is shown that protein is made up of carbon, Starch
hydrogen and oxygen elements. In addition to those elements, protein may
contain sulfur and phosphorus.
corboxyl group
8-3-2 Amino acids amino group

They are the most important units in protein structure. They are shown with the
formula below:

Examine general structural formula for amino acids and answer the questions.
1-What is the functional group common in all amino acids?
2-What are the chemical effects of each functional group? Formula for
All differences between amino acids depend on alkyl R groups. alkyl group
amino acid

8-3-3-Formation of Proteins
Protein is formed from bonding of many amino acids with peptide (amide)
bonds. These bonds make long chains with big molecular weights containing
from 40,000 to 40,000,000 molecules.

Egg is source of protein.

peptide bond (amide bond)

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 Chapter - 8

Protein has a carboxyl group on one side and an amine group on the other side.
There are amide groups at the place where the bond is formed.

8-3-4-Significant Reactions of Proteins

The most significant reactions of proteins occur in cells of living beings. At the
end of most reactions, protein decomposes to one or more amino acid units.
In laboratories, proteins can be decomposed to amino acids forming them by
addition of inorganic acid (HCl). These reactions occur by the breaking of am-
ide bond as in digestion. Besides, by addition of inorganic base (NaOH), pro-
teins can be decomposed to amino acids.
Proteins show some differences with respect to the type of amino acids they
contain and also with the numbers and order of those amino acids. There are
more than 20 amino acids in nature. The functions of protein in body depend
on the amino acid and its sequence. Therefore, scientists have tried to produce
amino acids in laboratories in order to make use for living beings when neces-
sary and learn their sequence.
Proteins play a vital role in lives of living beings. They have many different
types which have the same chemical formula and same bonds but due to their
sizes, they have different functions.

For example:
* those in fibrous shape as keratin in hair and wool.
* those in semi spherical shape as in egg.
Proteins assume important roles in bodies of living beings with respect to their
shapes. Any effect changing the shapes of proteins interrupts their functions
and affects the life of the living being. The most important proteins in our bod-
ies are enzymes, hormones and hemoglobin in blood.

8-4-ENZYMES
They are some kind of proteins. They are found in all cells of living beings.
They function independently. They play vital roles in events like digestion and
respiration.
Enzymes are produced in bodies of living beings. They are constantly renewed
Structure of protein during vital reactions as they lose their effects by time. They function at a cer-
tain pH value. High temperatures disrupts their structures and prevents their
functions.
Enzymes supply the necessary energy for reactions.
Exercise 8-1 There are two types of enzymes:
Proteins show either basic or acid- 1- Internal enzymes: They enable oxidation reactions inside cells and they
ic property (amphoteric). Say the don’t get out of cell membrane.
reasons for this. 2- External enzymes: They perform their duties out of cells after they are se-
creted as digestive fluids.

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8-5-LIPIDS
There are plenty of lipids in nature. Vegetable oils are found in cores of plants
as cotton, corn, and fruits like olive and coconut. Animal fats are found in all
cells of animals. They are stored for energy to be used when necessary. In
digestion and oxidation reactions, plenty of energy is obtained. Lipids repre-
sent energy potential in living beings. They are very important in soap, paint
and candle industries. Lipids don’t dissolve in water. They dissolve in organic
solvents like ether and chloroform. Animal fats are solid at room temperature Triglyceride
whereas vegetable oils are in liquid form.
Lipids are formed through esterification reaction of fatty acids with glycerol.
They are also called as triglycerides and formed from long hydrocarbon chains
(C12-C23) with carboxyl group at one side.

Ester bond

Soap

glycerol fatty acid

8-6-SOAPS
Soap production is the oldest industry that humans have been doing. Soap is
sodium or potassium salt of fatty acids. Soap is obtained by addition of strong
bases as sodium or potassium hydroxide followed by adding sodium chloride
solution and finally by precipitating a thick layer on a cloth. The reaction oc-
curs here is called as saponification reaction. At the final step, it is washed with
water to remove salt.

Sodium palmitate

glyceryl tripalmitate
Shape and quality of soaps depend on the type of base and oil used in sapon-
Steps of soap production
ification. When sodium hydroxide is used as base, we get soap bars we use in
daily life. If we use potassium hydroxide, we get soft soaps as liquid soaps and
shaving foams.
Similarly, quality of soap depends on the type of oil used.
Exercise 8-2
Why aren’t calcium or magnesium
hydroxides used instead of sodium
and potassium hydroxides in soap
production?

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BASIC CONCEPTS
Biochemistry: It studies the chemistry of vital compounds in living beings. It explains functional biological properties
of living beings chemically by studying chemical changes in human body and living beings.
Carbohydrates: They are compounds which are formed from oxygen, hydrogen and carbon. The rate of oxygen in
hydrocarbons is higher than of others. When we examine the structural formula of (CH2O)n, we see that each carbon atom
is bonded to water molecules. Therefore, carbohydrate name is given to those compounds.
Glucose: It is a kind of monosaccharide. It is in form of hard crystals. Its boiling points is high. It is found abundantly in
grapes and also in blood in nature. Therefore it is also called as grape sugar. Its formula is C6H12O6 or C6(H2O)6. Its open
formula contains many hydroxyl groups and an aldehyde group.
Fructose: It is a type of monosaccharide. It is found in honey and fruits abundantly. Therefore, it is called as fruit sug-
ar. Its physical properties are similar to those of sucrose. Its open formula contains many hydroxyl groups and a ketone
group.
Sucrose: It is a type of disaccharide. It is obtained from sugar cane and it is also called as cane sugar. Its molecular
formula is C12H22O11. Each fructose molecule is formed from a glucose and a fructose molecule with a glycoside bond
between them. These molecules can dissolve in our bodies during digestion.
Starch: It is a type of polysaccharide. It is obtained by breaking the double bond of carbonyl in glucose and then forming
polymers by bonding glucose molecules to each other.
Cellulose: It is a kind of polysaccharide. It is big molecule formed from polymerization of glucose. Starch and cellulose
show different properties and shapes due to the difference in the number of glucose molecules they have and bonds they
make. Fibers of plants and skins of some fruits are natural sources of cellulose.
Protein: It is formed from carbon, hydrogen, oxygen and sometimes sulfur and phosphorus. Its main source is living
beings especially living organs. Protein is from Greek. It means “primary”, “in the lead” or “standing in front”. It carries
great importance in lives of living beings. Proteins are obtained by bonding many amino acids together and removal of
water during this process. On one side of protein molecule is carboxyl group and on the other side is amine group. As
bonds, amide group are present.

Amino acids: They are the main units of proteins. Its formula is . Amino acids show difference

with respect to alkyl group which is between carboxyl group and amino group.
Enzymes: They are some kind of proteins. In all living beings, they are produced by the organism. They are found in
all cells of body. They function independently. They play vital roles in events as digestion and respiration. They are con-
stantly renewed during vital reactions as they lose their effects by time. They function only at a certain pH value. High
temperature disrupts their structure and their functions.
Lipids: They are the main substances which body stores to supply energy when necessary. Great amount of energy is
obtained from animal fats during digestion and oxidation reactions. They are also found in cores of plants like cotton and
corn.
Soaps: Soaps are organic compounds of sodium or potassium salts of fatty acids. Soap is obtained from mixture of
strong bases as sodium or potassium hydroxide with oils. The shape and quality of soaps depend on the base and the
quality of fats.

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QUESTIONS OF CHAPTER-8
8-1- Circle the correct answer in the following questions.
1) Which of the following isn’t a protein?
a) A compound which is made up of carbon, oxygen, hydrogen and sulfur.
b) A compound whose molecules are made up of carbon, hydrogen and nitrogen.
c) A compound which reacts with acids and bases.
2) Sucrose molecule consists of units. These are:
a) glucose b) fructose c) glucose and fructose
3) Which of the following elements isn’t found in amino acids?
a) nitrogen b) phosphorus c) oxygen d) carbon
4) Which polymers are formed by fatty acids?
a) proteins b) carbohydrates c) oils
8-2- Tell reasons for the following:
a) Fructose is assumed as a reducing sugar.
b) Proteins react with acids and bases.
c) Separation of proteins with simple methods isn’t easy.
8-3- How can you differentiate starch and glucose?
8-4- Complete the following table:

Subject of comparison Glucose Fructose

Molecular formula
Open Formula
Functional group in open formula
Functional group in cyclic formula

8-5- What are the differences between starch and glucose?

8-6- Write the function of enzymes after that explain its types.

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 Chapter - 8

List of Elements
ATOMIC NUMBER NAME SYMBOL RELATIVE ATOMIC GROUP PERIOD
MASS
1 Hydrogen H 1.00794 1 / IA 1
2 Helium He 4.002602 18 / VIIIA 1
3 Lithium Li 6.941 1 / IA 2
4 Beryllium Be 9.012182 2 / IIA 2
5 Boron B 10.811 13 / IIIA 2
6 Carbon C 12.0107 14 / IVA 2
7 Nitrogen N 14.0067 15 / VA 2
8 Oxygen O 15.9994 16 / VIA 2
9 Fluorine F 18.9984032 17 / VIIA 2
10 Neon Ne 20.1797 18 / VIIIA 2
11 Sodium (Natrium) Na 22.98976928 1 / IA 3
12 Magnesium Mg 24.3050 2 / IIA 3
13 Aluminium (Alumi- Al 26.9815386 13 / IIIA 3
num)
14 Silicon Si 28.0855 14 / IVA 3
15 Phosphorus P 30.973762 15 / VA 3
16 Sulfur S 32.065 16 / VIA 3
17 Chlorine Cl 35.453 17 / VIIA 3
18 Argon Ar 39.948 18 / VIIIA 3
19 Potassium (Kalium) K 39.0983 1 / IA 4
20 Calcium Ca 40.078 2 / IIA 4
21 Scandium Sc 44.955912 3 / IIIB 4
22 Titanium Ti 47.867 4 / IVB 4
23 Vanadium V 50.9415 5 / VB 4
24 Chromium Cr 51.9961 6 / VIB 4
25 Manganese Mn 54.938045 7 / VIIB 4
26 Iron (Ferrum) Fe 55.845 8 / VIII 4
27 Cobalt Co 58.933195 9 / VIII 4
28 Nickel Ni 58.6934 10 / VIII 4
29 Copper (Cuprum) Cu 63.546 11 / IB 4
30 Zinc Zn 65.39 12 / IIB 4
31 Gallium Ga 69.723 13 / IIIA 4
32 Germanium Ge 72.64 14 / IVA 4
33 Arsenic As 74.92160 15 / VA 4
34 Selenium Se 78.96 16 / VIA 4
35 Bromine Br 79.904 17 / VIIA 4
36 Krypton Kr 83.798 18 / VIIIA 4
37 Rubidium Rb 85.4678 1 / IA 5
38 Strontium Sr 87.62 2 / IIA 5

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 Biochemistry

Yttrium Y 88.90585 3 / IIIB 5

39
40 Zirconium Zr 91.224 4 / IVB 5
41 Niobium Nb 92.906 38 5 / VB 5
42 Molybdenum Mo 95.94 6 / VIB 5
43 Technetium Tc 97.9072* 7 / VIIB 5
44 Ruthenium Ru 101.07 8 / VIII 5
45 Rhodium Rh 102.905 50 9 / VIII 5
46 Palladium Pd 106.42 10 / VIII 5
47 Silver (Argentum) Ag 107.8682 11 / IB 5
48 Cadmium Cd 112.411 12 / IIB 5
49 Indium In 114.818 13 / IIIA 5
50 Tin (Stannum) Sn 118.710 14 / IVA 5
51 Antimony (Stibium) Sb 121.760 15 / VA 5
52 Tellurium Te 127.60 16 / VIA 5
53 Iodine I 126.904 47 17 / VIIA 5
54 Xenon Xe 131.293 18 / VIIIA 5
55 Caesium (Cesium) Cs 132.9054519 1 / IA 6
56 Barium Ba 137.327 2 / IIA 6
57 Lanthanum La 138.90547 - 6
58 Cerium Ce 140.116 - 6
59 Praseodymium Pr 140.90765 - 6
60 Neodymium Nd 144.242 - 6
61 Promethium Pm 144.9127 - 6
62 Samarium Sm 150.36 - 6
63 Europium Eu 151.964 - 6
64 Gadolinium Gd 157.25 - 6
65 Terbium Tb 158.92535 - 6
66 Dysprosium Dy 162.500 - 6
67 Holmium Ho 164.930 32 - 6
68 Erbium Er 167.259 - 6
69 Thulium Tm 168.93421 - 6
70 Ytterbium Yb 173.04 - 6
71 Lutetium Lu 174.967 3 / IIIB 6
72 Hafnium Hf 178.49 4 / IVB 6
73 Tantalum Ta 180.94788 5 / VB 6
74 Tungsten (Wolfram) W 183.84 6 / VIB 6
75 Rhenium Re 186.207 7 / VIIB 6
76 Osmium Os 190.23 8 / VIII 6
77 Iridium Ir 192.217 9 / VIII 6
78 Platinum Pt 195.084 10 / VIII 6
79 Gold (Aurum) Au 196.966569 11 / IB 6

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 Chapter - 8

80 Mercury (Hydrargy- Hg 200.59 12 / IIB 6

rum)
81 Thallium Tl 204.3833 13 / IIIA 6
82 Lead (Plumbum) Pb 207.2 14 / IVA 6
83 Bismuth Bi 208.98040 15 / VA 6
84 Polonium Po 208.9824* 16 / VIA 6
85 Astatine At 209.9871* 17 / VIIA 6
86 Radon Rn 222.0176* 18 / VIIIA 6
87 Francium Fr 223.0197* 1 / IA 7
88 Radium Ra 226.0254* 2 / IIA 7
89 Actinium Ac 227.0277* - 7
90 Thorium Th 232.03806* - 7
91 Protactinium Pa 231.03588* - 7
92 Uranium U 238.02891 - 7
93 Neptunium Np 237.0482* - 7
94 Plutonium Pu 244.0642* - 7
95 Americium Am 243.0614* - 7
96 Curium Cm 247.0704* - 7
97 Berkelium Bk 247.0703* - 7
98 Californium Cf 251.0796* - 7
99 Einsteinium Es 252.0830* - 7
100 Fermium Fm 257.0951* - 7
101 Mendelevium Md 258.0984* - 7
102 Nobelium No 259.1010* - 7
103 Lawrencium Lr 262.1097* 3 / IIIB 7
104 Rutherfordium Rf 261.1088* 4 / IVB 7
105 Dubnium Db 262 5 / VB 7
106 Seaborgium Sg 266 6 / VIB 7
107 Bohrium Bh 264 7 / VIIB 7
108 Hassium Hs 277 8 / VIII 7
109 Meitnerium Mt 268 9 / VIII 7
110 Darmstadtium Ds 271 10 / VIII 7
111 Roentgenium Rg 272 11 / IB 7
112 Ununbium Uub 285 12 / IIB 7
113 Ununtrium Uut 284 13 / IIIA 7
114 Ununquadium Uuq 289 14 / IVA 7
115 Ununpentium Uup 288 15 / VA 7
116 Ununhexium Uuh 292 16 / VIA 7
117 Ununseptium Uus - 17 / VIIA 7
118 Ununoctium Uuo 294 18 / VIIIA 7

*Relative atomic mass of the isotope of the element with the longest known half-life.

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