UNIT-5

CHEMICAL REACTIONS AND STOICHIOMETRY

5.1 INTRODUCTION

Chemical reactions are the basis of chemistry. Chemical reactions occur around us all the time.
For example, the burning of fuel, the souring of milk, metabolic processes of our body and the
decay of plants are some familiar chemical reactions in daily life.

A chemical reaction is the process in which reacting substances, called reactants, are converted
to new substances, called products. The characteristics of the products are completely different
from those of the reactants. The conversion process is a chemical change.

Reactants Products

For example, if you burn magnesium with oxygen, the magnesium and oxygen are completely
converted to magnesium oxide. Magnesium oxide is a soft, white, crumbling powder. These
characteristics of magnesium oxide are completely different from the characteristics of the
original substances, magnesium and oxygen. Magnesium and oxygen are no longer present in the
elemental form.

In summary, a chemical reaction has occurred in which the reactants, magnesium and oxygen,
underwent a complete chemical change, giving the product magnesium oxide. All chemical
reactions include three types of changes in the original substances. These are changes in
composition, properties and energy.

Note that, in daily life, we use different terms for the same process of chemical change. For
example ―the souring of milk‖ occurs due to the process of fermentation. In scientific discussion
we generally have a single term for each process.

5.2. LAWS OF CHEMICAL REACTIONS

While investigating the quantitative relations between substances in chemical reactions,

scientists formulated the three basic laws of chemical combination.

These are: i) The law of conservation of mass

ii) The law of definite proportions

iii) The law of multiple proportions

i) The Law of Conservation of Mass

In 1774, the French chemist Antoine Lavoisier performed an experiment in which he heated a
sealed glass container that held a sample of tin in air. He measured the mass of the substances
before and after heating and found them to be the same. This and other similar experimental
observations became the basis of the law of conservation of mass.

The law of conservation of mass states that matter is neither created nor destroyed in a chemical
reaction. In other words, the mass of the reactants is exactly equal to the mass of the products,
within the limits of experimental error. This law is also known as the law of indestructibility of
matter.

Mass of reactants = Mass of products

There is no loss or gain of substances during a chemical reaction, and mass is conserved. For
example, consider the decomposition of mercury (II) oxide. When 100 g of mercury (II) oxide
decomposes by heat, 92.6 g of mercury and 7.4 g of oxygen are formed. Note that the total mass
of mercury and oxygen after decomposition is 100 g:

ii. The law of definite proportions

The law of definite proportions states that a compound always contains the same elements in the
same proportion by mass. This means that all pure samples of a compound have the same
composition regardless of the source of sample. This law is also known as the law of constant
composition. For example, sample of water could be obtained from different sources, such as
from a river, the ground, or the ocean. But whatever the original source, all forms of pure water
contains 11.2% hydrogen and 88.8% oxygen by mass. These percentages represent a ratio of 1.0
to 8.0 (1:8), by mass, of hydrogen to oxygen. This ratio is constant (fixed) for water. In other
words, a compound with a different ratio of hydrogen and oxygen is not water. Similarly, in
forming the compound ZnO, 65.0 g of zinc combines with 16.0 g of oxygen. This is 80.2% zinc
and 19.8% oxygen, by mass. As is the case for water, the composition of ZnO is constant. In
forming ZnO, zinc combines with oxygen in a definite proportion.

iii) The Law of Multiple Proportions

The law of multiple proportions states that when two elements combine to form more than one
compound, the masses of one element combined with a fixed mass of the second element are in
the ratio of small whole numbers. This law can be illustrated by the two oxides of carbon. The
two oxides of carbon are carbon monoxide (CO) and carbon dioxide (CO2). In CO2, 1.0 g of
carbon is combined with 2.67 g of oxygen; whereas in CO, 1.0 g of carbon is combined with
1.33 g of oxygen. By comparing 2.67 g of oxygen with 1.33 g of oxygen, it is found that the
masses of oxygen in the two compounds that combine with the same mass of carbon are in the
simple whole number ratio, 2:1.

5.3 ENERGY CHANGES IN CHEMICAL REACTIONS

Almost all chemical reactions are accompanied by energy changes. These energy changes could
be in the form of heat energy, light energy, electrical energy, and so on. On the basis of energy
changes, chemical reactions can be divided into exothermic and endothermic reactions

5.3.1 Exothermic and Endothermic Reactions

Can heat energy be considered as a reactant or product?

Exothermic Reaction

A chemical reaction that releases heat energy to the surroundings is known as an exothermic
reaction. During an exothermic process, heat is given out from the system to its surroundings and
this heat energy is written on the right side of the equation as shown below.

Reactants Products + Heat

For example, the burning of carbon with oxygen produces carbon dioxide and heat is released
during the reaction. Thus, the reaction is exothermic and written as:

C + O2 CO2 + Heat

Endothermic Reaction

A chemical reaction which absorbs heat energy from the surroundings is known as an
endothermic reaction. During an endothermic process, heat flows into the system from its
surroundings and the heat is written on the left side of the equation.

Reactants + Heat → products

For example, the reaction between carbon and sulphur to form carbon disulphide is an
endothermic reaction because heat is absorbed in the reaction.

C + 2S + Heat CS2

The amount of heat energy liberated or absorbed by a chemical reaction is called heat of reaction
or change in enthalpy for the reaction. It is symbolized as ∆H. Its unit is expressed in kilojoules
per mol(kJ/mol). The change in enthalpy (∆H) is the difference between the energy of the
products and the energy of the reactants.

∆H = Hp – Hr ; where Hp is the heat content (energy) of the product, Hr is the heat content
(energy) of the reactant.

5.3.2 Energy Diagrams

For endothermic reactions,∆H is positive because the energy of the product is higher than the
energy of the reactant. As a result, the enthalpy of the system increases as shown in Figure 5.1
since, Hp > Hr , ∆H = positive (∆H > 0) For example, when nitrogen reacts with oxygen to form
nitrogen dioxide, 66.4 kJ of heat energy is absorbed (i.e., ∆H = + 66.4 kJ/mol) and thus the
reaction is endothermic.

N2 (g) + 2O2 (g) 2NO2 (g); ∆H = + 66.4 kJ/mol

 Figure 5.1 Energy diagram for an endothermic reaction

For exothermic reactions, ∆H is negative because the energy of the reactants is greater than the
energy of the products. Thus, the enthalpy of the system decreases, as shown in Figure 5.2

Hp < Hr, ∆H = negative (∆H < 0)

For example, when carbon burns in oxygen to produce carbon dioxide, 393.5 kJ of heat energy is
liberated and hence the reaction is exothermic (∆H = –393.5 kJ/mol).

Figure 5.2 Energy diagram for an exothermic reaction.

Chemical reactions bring about chemical changes. All chemical changes are accompanied by
energy changes. This energy is usually in the form of heat, light, or electricity.

Energy changes produced by chemical reactions have many practical applications (uses). For
example, energy lifts rockets, runs cars, and extracts metal from compounds.
Many applications involve the energy produced by fuel combustion, which liberates large
amounts of heat. The energy can be converted from one form to another. For example, the
energy that fuel combustion produces can convert water to steam. The steam can run a turbine
that creates electricity.

Respiration (breathing) creates energy for our bodies. Breathing releases the energy our living
cells produce by oxidizing glucose. This energy helps to maintain our body temperature and
body exercises.

C6H12O6 + 6O2 6CO2 + 6H2O + Energy

Exercise

In each of the following cases, determine the sign of ∆H. State whether the reaction is
exothermic or endothermic, and draw an enthalpy diagram.

a H2(g) + ½O2(g) → H2O(l) + 285.8 kJ

b H2O(I) + 40.7 kJ → H2O(g)

5.4 TYPES OF CHEMICAL REACTIONS

Chemical reactions are classified into four categories. These are combination, decomposition,
single displacement and double displacement reactions

i) Combination Reactions

A reaction in which two or more substances combine to form a single substance is called a
combination reaction. In a combination reaction, two elements, two compounds, or an element
and a compound react to form a single compound. Combination reactions can be represented by
the following general form of equation.

A+B AB;

where the reactants A and B are elements or compounds, the product AB is a compound. Such
type of reaction is also known as synthesis or composition reaction.
Examples

• Magnesium burns in oxygen to form magnesium oxide.

2Mg + O2 2MgO

element element

• Water and carbon dioxide combine to form carbonic acid.

H2O + CO2 H2CO3

element element

Exercise

Complete and balance the following combination reactions.

1. CO + O2 →

2. H2O + SO2 →

3. Na2O + H2O →

4. CaO + CO2 →

ii) Decomposition Reactions

A decomposition reaction is a reaction that involves the breaking down of a single compound
into two or more elements or simpler compounds. A decomposition reaction can be carried out
using heat, light, electricity or a catalyst. But most decomposition reactions are carried out when
heat is supplied and this heat energy is indicated by a ‗delta‘ (∆) symbol above the arrow. The
general form of equation for a decomposition reaction is:

AB A+B

where the reactant AB must be a compound and the products A and B could be elements or
compounds
Examples

• Water is decomposed to hydrogen and oxygen gases when electricity is passed through it.

2H2O 2H2 + O2

• When sodium bicarbonate is heated, it decomposes to give sodium carbonate, carbon dioxide,
and water.

2NaHCO3 → Na2CO3 + CO2 + H2O

Let us consider the decompositions of nitrates and carbonates:

1. Decomposition of Metallic Nitrates

a) Decomposition of group IA nitrates produces nitrites and oxygen
Examples
2NaNO3 → 2NaNO2 + O2
2KNO3 → 2KNO2 + O2
b) Decomposition of all metal nitrates, except group IA metals, gives nitrogen dioxide, metal
oxide and oxygen gas.
Examples
2Ca(NO3)2 → 2CaO + 4NO2 + O2
2Zn(NO3) 2 → 2ZnO + 4NO2 + O2
2Pb(NO3)2 → 2PbO + 4NO2 + O2
2. Decomposition of Metallic Carbonates
All metal carbonates, except sodium and potassium, decompose when heated to form the
metal oxide and carbon dioxide.
Examples
ZnCO3 → ZnO + CO2
CuCO3 → CuO + CO2

iii) Single Displacement Reactions

A reaction in which one element displaces another element from its compound is known as
single displacement or replacement reaction. Such a reaction is represented by the following two
general forms.
 A + BC B + AC

If A is a metal, it will displace B to form AC, provided A is a more active metal than B.

A + BC BA + C

If A is a non-metal, it will displace C to form BA, provided A is a more active non-metal than C.

In general, a more reactive element displaces a less reactive element from a compound.
Examples of single-displacement reactions

a. Active metals displace hydrogen from acids.

Reactive metals such as potassium, calcium, sodium, and zinc displace hydrogen gas from
dilute acids.

For example, zinc is an active metal, and it displaces hydrogen from hydrochloric acid; but
copper metal cannot do so.

Zn + 2HCl ZnCl2 + H2

Au + HCl No reaction

b Reactive metals, such as potassium, calcium, and sodium react vigorously with water to
displace hydrogen:

2Na + 2H2O 2NaOH + H2

Ca + 2H2O Ca(OH)2 + H2

Exercise

Complete and balance the following single displacement reactions:

1. Zn + CuSO4 —→

2. Cu + Zn(NO3)2 —→

3. F2 + CaCl2 —→
4. Br2 + NaCl —→

iv) Double Displacement Reactions

Double displacement reaction is a reaction in which two compounds react together to form two
new compounds by exchange of the positive and negative ions of each reactant. Such a reaction
is also known as double replacement reaction or metathesis. This type of reaction can be written
in the following general form of equation.

AB + CD AD + CB

Examples

• The two soluble compounds AgNO3 and NaCl react to produce an insoluble precipitate of
AgCl and a soluble NaNO3 solution.

AgNO3 + NaCl AgCl ↓ + NaNO3

Insoluble Soluble

• When aqueous solutions of BaCl2 and Na2SO4 react, a precipitate of BaSO4 is formed.

BaCl2 + Na2SO4 BaSO4 ↓ + 2NaCl

Insoluble Soluble

5.5 STOICHIOMETRY (Balanced Chemical Equation)

The quantitative relationship between reactants and products in a balanced chemical equation is
known as stoichiometry. In other words, stoichiometry is the study of the amount or ratio of
moles, mass, energy and volumes (for gases) of reactants and products. Stoichiometric
calculations are based on the following two major principles.

i) The composition of any substance in the chemical equation should be expressed by a definite
formula.

ii) The law of conservation of mass must be obeyed (the mass of reactants equals the mass of
products).
5.5.1 Molar Ratios in Balanced Chemical Equation

From a balanced chemical equation, it is possible to determine the:

• number of moles of each reactant and product; and

• relative mass of each of the reactants and products For example, in the reaction of hydrogen
with oxygen to produce water, 2 moles of H2 combines with 1 mole of O2 to yield 2 moles of
H2O. The equation also tells us 4 g of hydrogen reacts with 32 g of oxygen to produce 36 g of
water. This can be further interpreted as follows

5.6 Calculation with Chemical Formula and Equation

Calculations based on chemical equations (stoichiometric problems) are classified into mass-mass
problem, volume-volume problems and mass-volume problems.

5.6.1 Mass–Mass Relationships

In mass-mass problems, the mass of one substance is given, and the mass of the second
substance is determined from the same reaction. There are two methods for solving such types of
problems:

i) Mass-ratio method
ii) Mole-ratio method

Let us see each method by using the necessary steps

i) The mass-ratio method

In this type of stoichiometric calculation, the mass of one substance is determined from the given
mass of the other substance using the following steps.

Step 1: Write the balanced chemical equation.

Step 2: Place the given mass above the corresponding formula, and x above the formula of the substance
whose mass is to be determined.

Step 3: Write the total molar mass of the substances below the formula of each substance. (Total molar
mass is the molar mass of the substance multiplied by its coefficient).

Step 4: Set up the proportion.

Step 5: Solve for the unknown mass, x.

Example

1. How many grams of calcium chloride are formed when 15 g of calcium metal reacts with hydrochloric
acid?

Solution:

Step 1: Ca + 2HCl CaCl2 + H2

15g x

Step 2: Ca + 2HCl CaCl + H 2

15g

Step 3: Ca + 2HCl CaCl + H2

40g 111g

Step 4: 15 g/ 40 g =x/111g

Step 5: x = 41.63 g

Therefore, 41.63 g of CaCl2 is produced.

2. How many grams of oxygen are produced by the decomposition of 145 grams of potassium chlorate?

Solution: Step 1: 2KClO3 2KCl + 3O2

145 g x

Step 2: 2KClO3 2KCl + 3O2

 145g x

Step 3: 2 KClO3 2KCl + 3O2

(2x122.5)g (3x32)g

Step 4: 145 g /245 g = x/96g

Step 5: x = 56.8 g

ii. The mole-ratio method

The mole ratio is the ratio between the numbers of moles of any two substances in a given
reaction. In this method, the given mass is converted into moles, and the number of moles for the
required substance is calculated. If needed, convert the obtained moles back to mass. Follow the
steps given below to solve problems of mass-mass relationships by the mole ratio method:

Step 1: Write the balanced chemical equation.

Step 2: Convert the given mass to moles and write the obtained moles and the required quantity,
x, above the formulas of the respective substances.

Step 3: Place the coefficients as the number of moles under the formula of each substance
involved.

Step 4: Set up the proportion.

Step 5: Solve for the unknown value, x; and convert the moles obtained into mass.

Example

1.How many grams of sodium metal are needed to react with 10.0 g of water?

Solution: Step 1: 2Na + 2H2O 2NaOH + H2

Step 2: moles of H2O = given mass /molar mass= 10.0 g/18 g/mol = 0.56 mol

x 0.56mol

2 Na + 2H2O 2NaOH + H2
 x 0.56mol

Step 3: 2Na + 2H2O 2NaOH + H2

2mol 2mol

Step 4: x/2mol = 0.56mol/2mol

Step 5: x = 0.56 mol of Na

Now, convert 0.56 mole of Na to grams

mass of Na = mole × molar mass

= 0.56 mol × 23 g/mol

= 12.88g

Therefore, 12.88 g of sodium metal is needed to react with 10 g of water.

2. What mass of nitrogen dioxide is produced by the decomposition of 182 g of magnesium

nitrate?

Solution: Step 1: 2Mg (NO3)2 2MgO + 4NO2 + O2

Step 2: moles of Mg (NO3)2 = 182 g /148 g/mol = 1.23 mol

1.23mol x
2 Mg(NO3 2 MgO + 4NO2 + O2

Step 3: 2 Mg(NO3)2 2MgO + 4 NO2 + O2

Step 4: 1.23 mol/2 mol=x/ 4 mol

Step 5: x = 2.46 moles of NO2

Mass of NO2 = 2.46 mol × 46 g/mol = 113.2 g
Therefore, 113.2 g of NO2 is produced.
Exercise

1. How many grams of CaCO3 are needed to react with 15.2 g of HCl in according to the following
equation? CaCO3 + 2HCl CaCl2 + CO2 + H2O
2. How many grams of NaOH are needed to neutralize 50 grams of H2SO4 ?

3. Calculate the mass of CaCl2 formed when 5 moles of chlorine reacts with calcium metal.

5.6.2 Volume-Volume Relationships

In reactions involving gases, the volume of gases can be determined on the principle that 1 mole
of any gas occupies a volume of 22.4 litres at STP (standard temperature and pressure, STP, the
temperature is 0°C and the pressure is 1 atm). It is also known that 22.4 L of any gas weighs
exactly its molecular mass at STP. This volume, 22.4 litres, of a gas is known as the molar
volume

At STP, 1 mole of any gas = 22.4 L = gram volume mass of the gas

The relationship between the volume of a gas and its number of molecules was explained by
Avogadro. Avogadro's law states that equal volumes of different gases, under the same
conditions of temperature and pressure, contain equal number of molecules. This law can also be
stated as the volume of a gas is proportional to the number of molecules (moles) of the gas at
STP.

Example: What a volume of oxygen react with CO to produce 20 liter of CO2 at STP?

Solution

Step 1: write the balanced chemical equation

2CO + O2 2CO2

Step 2: Place the given volume and the required volume, x, above the corresponding formulas

X 20L

2CO + O2 2CO2

Step 3 : Write the total molar volume (22.4 L multiplied by any coefficient) below the formulas
 X 20L

2CO + O2 2CO2

22.4L 2 (22.4L)

Step 4: Set up the proportion

x/22.4L=20L/44.8L

Step 5 : Solve for the unknown volume, x

x= 10L of O2 needed

Exercise

1. What volume of nitrogen reacts with 33.6 litres of oxygen to produce nitrogen dioxide?

2. How many litres of sulphur trioxide are formed when 4800 cm3 of sulphur dioxide is burned
in air?

3. How many litres of ammonia are required to react with 145 litres of oxygen according to the
following reaction?

4NH3 + 5O2 4NO + 6H2O

4. Calculate the volume of oxygen produced in the decomposition of 5 moles of KClO3 at STP?

5. How many moles of water vapor are formed when 10 liters of butane gas, C 4H10 is burned in
oxygen at STP?

5.6.3 Mass–Volume Relationships

In mass-volume problems, either the mass of one substance is given and the volume of the other
is required or the volume of one substance is given and the mass of the other one is required. The
steps to solve such type of problems are the same as the previous steps except putting the masses
on one side and the volumes on the other side of the equality sign.

Example
1. How many grams of calcium carbonate are decomposed to produce 11.2 L of carbon dioxide
at STP?

Solution

Step 1: CaCO3 CaO + CO2

X 11.2L

Step 2: CaCO3 CaO + CO2

X 11.2L

Step 3: CaCO3 CaO + CO2

22.4L

Step 4 : x/100g = 11.2L/22.4L

2. How many liters of oxygen at STP react with 72 g of aluminum to produce aluminum oxide?

Solution:

Step 1: 4Al + 3O2 2Al2O3

72g x

Step 2: 4Al + 3O2 2Al2O3

72g x

Step 3: 4Al + 3O2 2Al2O3

(4x27)g (3x22.4)g

Step 4: 72g/108g= x/67.2L

Step 5: x=44.8 L of O2

Hence, 44.8 liters of oxygen is required at STP to react with 72 g of aluminium.

Exercise
1. How many liters of oxygen are required to react with 23 g of methane according to the
following equation?

CH4 + 2O2 CO2 + 2H2O

2. What mass of aluminium would be completely oxidized by 44.8 L of oxygen to produce Al2O3
at STP?

3. Calculate the mass of calcium carbide that is needed to produce 100 cm3 of acetylene
according to the following equation.

CaC2 + 2H2O C2H2 + Ca(OH)2

5.6.4 Limiting and Excess Reactants

When all the reactants are completely consumed in a chemical reaction, then such reactants are
said to be in stoichiometric proportions. But, practically these types of chemical reactions do not
always occur. In many cases, an excess of one or more reactants is encountered in the reaction
and the other reactant is completely converted into products. Thus, the reactant that is completely
consumed in the reaction is known as the limiting reactant, because it limits or determines the
amount of products that can be formed.

For example, consider the following reaction:

H2 + Cl2 2HCl

1 mole 1 mole 2 moles

According to the equation, 1 mole of H2 reacts with 1 mole of chlorine to produce 2 mole of
HCl. Thus, all the reactants are completely consumed and only products appear. However if 1
mole of H2 reacts with 1.5 mole of Cl2, there is insufficient H2 to react with all of the Cl2.
Therefore, Cl2 will be in excess and H2 will be the limiting reactant. Only 2 moles of HCl are
formed and at the end of the reaction 0.5 mole of Cl2 remains unreacted.

Example

How much ammonia is produced if 10 g of hydrogen reacts with 18 g of nitrogen?

Solution: 3H2(g) + N2(g) 2NH3(g)

First determine the number of moles;

Moles of H2= = 5mol

Moles of N2 = =0.64mol

Now, calculate the number of moles or masses of the product that would be formed by each
reactant. The reactant that gives the smallest amount of product is the limiting reactant.

i. Using the quantity of H2 ii. Using the quantity of N2

5mol x 3H2 + N2 2NH3

3H2 + N2 2NH3 (1mol)(0.64mol) x(2mol)

3mol 2mol 0.64mol/1mol= x/ 2mol

5mol/3mol= x/2mol x= 1.28mol NH3

x= 3.33 mol NH3 Mass of NH3 = 1.28 mol × 17 g /mol

Mass of NH3 = 3.33 mol × 17 g /mol =21.8g

= 56.6 g

Therefore, the limiting reactant is nitrogen, because it gives less amount of NH3, i.e., 21.8 g NH3.
In the reaction, 0.64 mole (18 g) of N2 is consumed. Hydrogen is in excess. The amount of
hydrogen consumed will be:

X 18g x 0.64mol

3H2 + N2 2NH3 or 3H2 + N2 2NH3

6g 28g 3mole 1mole

x/6 = 18/28 x/3mol= 0.64mol/1mol

x = 3.86 g of H2 x = 1.92 mol of H2

Therefore, 3.86 g or 1.92 moles of H2 is used in the reaction, and 6.14 g or 3.08 moles of H2 is left
unreacted.

Example 9 In the chemistry laboratory, a student performed a displacement reaction by adding 9.5 g of
zinc into 9.5 g of HCl in a beaker. What weight of ZnCl2 will be produced?

Solution: Zn + 2HCl ZnCl2 + H2

Moles of Zn = 9.5 g/ 65 g/mol = 0.15 mol

Moles of HCl = 9.5 g /36.5 g/mol = 0.26 mol

Even though the given masses of the two reactants are the same, they are not mixed in equimolar
ratio as shown above. Thus, the limiting reactant must be determined first

i. Using the quantity of Zn ii. Using the quantity of HCl

0.15mol x 0.26mol x

Zn + 2HCl ZnCl2 + H2 Zn + 2HCl ZnCl2 + H2

1mol 1 mol 2mol 1mol

x = 0.15 mol ZnCl2 x = 0.13 mol ZnCl2

Hence, the limiting reactant is HCl. Mass of ZnCl2 = 0.13 mol × 136 g/mol = 17.68 g ZnCl
Exercise
1. If 6.5 g of zinc reacts with 5.0 g of HCl, according to the following reaction.
Zn + 2HCl ZnCl2 + H2
a. Which substance is the limiting reactant?
b. How many grams of the reactant remains unreacted?
c. How many grams of hydrogen would be produced?
2. What mass of Na2SO4 is produced if 49 g of H2SO4 reacts with 80 g of NaOH?
3. If 20 g of CaCO3 and 25 g of HCl are mixed, what mass of CO2 is produced?
CaCO3 + 2HCl CaCl2 + CO2 + H2O
4. If 3 moles of calcium reacts with 3 moles of oxygen, then
 a Which substance is the limiting reactant?
b How many moles of calcium oxide are formed?
5. For the reaction:
2Al + 3H2SO4 Al2(SO4)3 + 3H2
How many grams of hydrogen are produced if 0.8 mole of aluminium reacts with 1.0 mole
of sulphuric acid?
5.6.5 Theoretical, Actual and Percentage Yields
The measured amount of product obtained in any chemical reaction is known as the actual yield.
The theoretical yield is the calculated amount of product that would be obtained if the reaction
proceeds completely. The actual yield (experimentally determined yield) of a product is usually
less than the theoretical yield (calculated yield).
The percentage yield is the ratio of the actual yield to the theoretical yield multiplied by 100.

Example : 25 grams of methane gas (CH4 ) burns in oxygen according to the following reaction:
CH4 + 2O2 CO2 + 2H2O
What is the percentage yield if 60.3 grams of carbon dioxide is produced?
Solution: The actual yield is 60.3 g of CO2.
Determine the theoretical yield using mass-mass relationship
x = 68.75 g of CO2 (theoretical yield)
Percentage yield =Actual yield/Theoretical yield x 100%
= 60.3 g /68.75 g × 100% = 87.7 %
Exercise.
1. When 20 g of sulphur dioxide reacts with oxygen, 23 g of sulphur trioxide is formed. What is
the percentage yield?
2. When 14.5 g of SO2 reacts with 21 g of O2, what will be the theoretical yield and percentage
yield of the reaction if the actual yield is 12 g?
3. In the reaction:
2C8H18 + 25O2 16CO2 + 18H2O
When 52.7 g of octane (C8H18) burns in oxygen, the percentage yield of carbon dioxide is 82.5%.
What is the actual yield in grams?

5.7 RATE OF REACTION

Every chemical reaction proceeds at different rates or speed. Some reactions proceed very slowly
and may take a number of days to complete; while others are very rapid, requiring only a few
seconds. The rate of a chemical reaction measures the decrease in concentration of a reactant or
the increase in concentration of a product per unit time. This means that the rate of a reaction
determines how fast the concentration of a reactant or product changes with time. The rate of a
reaction is obtained by determining the concentration of reactants or products during the
reaction. Methods for determining the concentration of reactants or products depend on the type
of reactions. Some of the methods are:

a Colour (changes in colour)

b Pressure (increase or decrease in pressure, particularly in gases)

c Volume (increase or decrease in size, particularly in gases)

d Mass (gain or loss in weight)

e Amount of precipitate formed

Generally, the rate of a reaction can be obtained by measuring either one of the above changes in
properties of substances and consequently relating to changes in their concentrations during the
course of the reaction.

From this expression, it follows that the rate of a reaction is inversely proportional to the time
taken by the reaction.
Figure 5.3 illustrates the changes of the rate of a chemical reaction with time. A reaction
becomes slower as reactants are consumed. The reaction rate curve becomes less steep until it
becomes a horizontal straight line. No more reactant is used up at this point

Note that the rate of a reaction is the slope of the tangent to the curve at any particular time.

Figure 5.3 The change in concentration of product with time.

Rate of reaction is the change in concentration of a reactant or a product over a given period of

time. During the course of a reaction, the concentrations of the reactants decrease while those of
the products increase. Thus, the rate of a reaction is calculated by dividing the change in the
concentrations of reactants or products by the time taken for the change to occur.

Pre-conditions for a Chemical Reaction

Chemical reactions are usually explained by the collision theory. The assumption of the collision
theory is that chemical reactions take place due to the collision between molecules.

1.Collisions between reactants

The first precondition for a reaction to occur is the direct contact of the reacting substance with
each other. However, all collisions between molecules are not necessarily effective in bringing a
reaction.

2Activation energy

If the collisions between the reactant molecules do not have sufficient energy, then no reaction
will occur. Therefore, for the reaction to take place collision must always occur with sufficient
energy to break the bonds in the reactants and form new bonds in the product. Thus, minimum
amount of energy needed for the reaction is known as activation energy.

3.Proper Orientation

Collision of molecules with sufficient activation energy will not bring a reaction if the reacting
molecules are poorly oriented. Thus, the collision between molecules should have the proper
orientation

Consider the reaction between H2 and Cl2 molecules: H2 + Cl2 2HCl For the reaction to occur,
first H2 and Cl2 molecules must collide with each other. For the collision to be effective, these
colliding molecules (H2 and Cl2 ) must have sufficient energy to break the H – H and Cl – Cl
bonds and consequently to form new H – Cl bonds.

Unless, the H2 and Cl2 molecules are oriented in proper positions, there is no product formed.
Therefore, as shown in Figure 5.6(c) the H2 and Cl2 molecules rearrange themselves so as to
form a new H – Cl molecule

Figure 5.4 Molecular collisions and chemical reactions.

Factors Affecting the Rates of Chemical Reaction

The rate of a chemical reaction depends on nature of reactants, temperature, and concentration of
reactants, surface area and catalysts.
The collision theory assumes that the rate of a reaction depends on the number (frequency) of
collisions of particles and those factors which affect the frequency of collisions will also affect
the rate of a reaction. Now let us discuss each factor.

1. Nature of the reactants

The rate of a reaction is influenced by the type and nature of the reacting substances. For
example, the following reactions have different rates due to the nature of the reactants, Mg, Fe
and Cu

Mg + 2HCl MgCl2 + H2 ... (very fast reaction)

Fe + 2HCl FeCl2 + H2 ... (slow reaction)

Cu + HCl No reaction

2. Temperature

An increase in temperature increases the rate of a reaction. This is because as the temperature
increases, the average kinetic energy of the particles increases which in turn increases the
number of effective collisions.

In general, for many chemical reactions, the rate of a reaction doubles for every 10°C rise in
temperature.

3. Concentration of reactants

The number of collisions is proportional to the concentration of reactants. The higher the
concentration of the reactants, the more collisions between the reacting particles and thus the
higher the rate of the reaction.

For example, if you heat a piece of steel wool in air (21% oxygen by volume) it burns slowly.
But in pure oxygen (100% oxygen by volume) it bursts in to a dazzling white flame. This
indicates that the rate of burning increases as the concentration of oxygen is higher.
4.Surface area

When the reactants are in different phases, be it solid, liquid or gas, then the surface area of the
substances affect the rate of the reaction. The higher the surface area of reactants, the faster is the
rate of the reaction. This is because more contact results in more collisions between each small
particle of reactants

5. Catalysts

A catalyst is a substance that changes the rate of a chemical reaction without itself being
consumed in the reaction. For example, the decomposition of potassium chlorate, KClO3 into
KCl and O2 is made faster in the presence of MnO2 catalyst.

Figure 5.5 Activation energy and catalysts

A catalyst speeds up the rate of a reaction by providing an alternative reaction path with lower
activation energy. Lower activation energy for a reaction corresponds to the higher reaction rate.
Figure 5.5 illustrates how the presence of catalysts speeds up a reaction.

For a simple reaction,

A B

the rate of reaction is expressed in terms of a reactant concentration as

where r is rate of reaction, A is a reactant, B is a product, [A]i and [A]f are initial and final
concentration of A respectively, ∆[A] is change in concentration of A and ∆t is the change in
time. Note that concentration is usually expressed in mole per liter.

The rate of a reaction can be expressed in units of mol L–1 s–1. The final concentration of the
reactant, [A]f , is smaller than the initial concentration of the reactant, [A]i Thus, the difference,
∆[A] = [A]f – [A]i , is negative. This indicates that the reactant is being consumed. However, the
rate of a reaction is a positive quantity. Thus, a negative sign is introduced in the rate expression
to make the rate positive. Can you write a rate of reaction in terms of concentration of a product?
In terms of product concentration, the rate of a reaction is given by:

where [B] is the molar concentration of a product in moles per litre, mol L–1. For a given product,
the final concentration of B, [B]f , is greater than the initial concentration of B, [B]i . Thus, the
difference, ∆B = [B]f – [B]i is positive, and the rate of a reaction is also positive. Therefore, there
is no need to introduce a negative sign to the rate expression when rate of a reaction is calculated
by using product concentration. This change can be shown using a graph.

Reaction Rate and Stoichiometry You have seen that, for stoichiometrically simple reactions of
the type A —→ B, the rate of reaction can be expressed either in terms of the decrease in
reactant concentration over time, –[A] / ∆t, or in terms of the increase in product concentration
with time, ∆[B]/∆t. For more complex reactions, you must be careful in writing the rate
expressions. Consider, for example, the reaction

2A B

For two moles of A that disappear one mole of B is formed. That is, the rate of disappearance of
A is twice as the rate of appearance of B. The reaction rate may be written as:
In general, for the reaction

aA + bB → cC + dD

The rate of reaction is given by:

where r is the rate of reaction, A and B are reactants, C and D are products, and a, b, c, d are
stoichiometric coefficients

Example 5.7

1. Write the rate expressions for the following reactions, in terms of the disappearance of
the reactants and the appearance of the products:
a I–(aq) + OCl–(aq) → Cl–(aq) + OI–(aq)
b 3O2(g) → 2O3(g)

a Since all of the stoichiometric coefficients are equal,

r= - = = =

b Here, the coefficients are 3 and 2, so,

r= - =

2. In the reaction of nitric oxide with hydrogen, 2NO(g) + 2H2(g) → N2(g) + 2H2O(g) If the rate
of disappearance of NO is 5.0 × 10–5 mol L–1s–1, What is the rate of reaction for the formation of
N2?

Solution: The rate of reaction for the formation of N2

r= = == ½ (5.0 x 10–5 mol L–1s–1)

Exercise 5.7
1. Define the rate of reaction.

2. For the reaction: 2HI(g) → H2(g) + I2(g) express rate of reaction in terms of the concentration
of: a) H2 b) HI

3. For the reaction

2NOCl(g) → 2NO(g) + Cl2(g)

a) express the rate of reaction in terms of the concentration of NOCl.

b) relate the rate of reaction of NOCl with the rate of reaction of NO and Cl2.

4. The reaction for the formation of ammonia is given as: N2(g) + 3H2(g) 2NH3(g)

Write the rate reaction for:

a) the formation of NH3.

b) the disappearance of N2 and H2

5.7.1 Determination of Rate of Reaction

The rate of reaction can be determined both quantitatively and qualitatively. Qualitatively, an
idea about the rate of reaction can be obtained by observing either the speed of disappearance of
the reactants or the speed of appearance (formation) of the products.

Example

In aqueous solutions, molecular bromine reacts with formic acid (HCOOH) as follows:

Br2(aq) + HCOOH(aq) → 2Br–(aq) + 2H+(aq) + CO2(aq)

Molecular bromine is reddish-brown in colour. All the other species in the reaction are
colourless. As the reaction progresses, the concentration of Br2 steadily decreases and the colour
fades. Measuring the change (decrease) in bromine concentration over time measuring at some
initial time and then again at some final time) allows us to determine the average rate of the
reaction during that interval
 r= - = [Br2]final –[Br2] intial /tfinal-tintial

where r is the average rate.

Now, you can calculate the average rate at the end of the first 50-second (s) time interval, as
follows:

r= =3.80 x 10-5 M / s

If the first 100 s is chosen as the time interval, the average rate will be given by:

r= = 3.54 x10-5 M / s

The above calculations demonstrate that the average rate of reaction depends on the time interval
we choose. Thus, in general, the rate of reaction at the beginning is fast and it decreases as the
reaction proceeds.

5.7.1 THEORIES OF REACTION RATES

5.7.1.1 Collision Theory
Have you ever played billiards? Certain collisions result in scoring points while others are not
fruitful enough as they lack in either power of impact or lack in angle placement.
Concentration and Collision Theory
The fundamental concept of the collision theory of rate of reaction is that, in order for a reaction
to occur between reacting species (atoms, ions or molecules), they must first collide (come in
contact). The rate of reaction is directly proportional to the number of collisions per second (the
frequency of collision).

According to collision theory, the more collisions there are, and the faster the rate of reaction
would be. However, not all collisions between reacting species result in a reaction. This is
because collisions between reactants can be either effective or ineffective. Effective collisions
are collisions that result in a reaction to form the desired products. Ineffective collisions are
collisions that do not result in a reaction to form the desired products.
In order for a collision between reactants to be effective, the reacting species must be in proper
orientation to each other at the time of collision, they must collide with sufficient energy to
break or rearrange bonds. The minimum energy required for a reaction to occur during a
collision of reacting species is called the activation energy, Ea.
Postulates of collision theory are summarized below.
For a reaction to occur between reactants:
1. The particles of the reacting substances must collide.
2. The particles of the reacting species must have proper orientation.
3. The particles of the reactants must collide with energy greater than or equal to the energy of
activation.
According to collision theory, only collisions with proper orientation of reacting species
possessing sufficient energy result in a reaction. The collision can either be linear or non-linear
(bent).

Figure 5.6 Orientation of molecules.

Generally, Ea for activated complex formed in linear orientation is less than that is formed in
bent orientation. Hence, orientation (a) is favored over orientation (b).

Concentration is one of the factors that influence the rate of reaction of a chemical reaction.
Collision theory accounts for the observed increase in the rate of any reaction when the
concentrations of reactants are increased. Increasing the concentrations of the reacting species
results in higher number of collisions per unit time, and the reaction rate is correspondingly
higher.

Temperature and Collision Theory

According to the kinetic molecular theory, the average kinetic energy of the particles of a
substance is directly proportional to the absolute temperature. As the temperature of the reacting
species is raised, the average kinetic energy of the reacting particles increases considerably. This
causes the particles of the reactants to collide more frequently and with greater energy. This
results in an increase in reaction rate.

5.7.1.2 Transition State Theory

Transition-state theory was developed in 1935 simultaneously by Henry Eyring, Meredith

Gwynne Evans and Michael Polanyi. It is also referred to as ―activated-complex theory‖.
According to transition-state theory, the collision between two reacting species results in the
formation of an activated complex or transition state. An activated complex or transition state is
a short-lived, high energy state species that is temporarily formed by the collision of reactant
molecules before they form products. These species can either form products or fall apart to give
the original reactants. In the activated complex, the original bonds are lengthened and
weakened, and the new bonds are only partially formed. Remember that chemical reactions
involve the formation and breaking of chemical bonds and are accompanied by changes in
potential energy, which is related to bond energy. Let us consider the reaction:

A2 + B2 → 2AB

Where A2 and B2 are the reactants, and AB is a the product. Refer to Figure 5.8. As the
reactants, A2 and B2, approach each other and collide, they begin climbing up the left side of
the potential-energy hill, or barrier. If they have less energy than the energy of activation, Ea ,
they fail to climb the barrier and, instead, roll back down its left side. In this case, no reaction
occurs.

If, however, they have energy that is at least equal to the energy of activation, they climb the
barrier, roll down the other side, and convert to product. In this concept, the level of activation
energy required for a reaction is seen as the height of a barrier between the reactants and
products. To convert from the reactant condition to the product condition, particles must climb
the barrier. The potential-energy curves in Figure 5.8 include representations of the barrier.

The potential-energy curves in Figure 5.7 include representations of the barrier.

Figure 5.7 Reaction energy diagrams for a) exothermic and b) endothermic reactions.

The formation of an activated complex in the form of an equation can be shown as,

Where A2B2 ‡ is the activated complex or transition state.

As shown in Figure 5.7, the activated complex corresponds to the peak of the energy barrier.
According to transition-state theory, the rate of reaction depends on the rate at which reactants
can climb to the top of the barrier and form an activated complex. On the other hand, the
activation energy, Ea , is the energy that must be absorbed by the reactants to allow them to
reach the transition state or the activated complex and cross the energy barrier.

For the exothermic reaction illustrated in Figure 5.9(a), the products have lower energy than the
reactants and the standard reaction enthalpy is less than zero ∆H or < O.

In Figure 5.7 (b), the thus energy of the products is higher than that of the reactants, thus for an
endothermic reaction, ∆H°r > 0

Exercise

1. Define activation energy?

2. Describe transition-state theory.

3. How does a catalyst affect the rate of a reaction?

4. During a course of reaction , can only one activated complex be formed for a particular type of
reaction?

5. Discuss the relationship between collision and rate of chemical reaction.

5.7.2 RATE EQUATION OR RATE LAW

5.7.1 Order of Reaction and Rate Constant

The rate law or rate equation for a chemical reaction is an equation which links the reaction rate
with the concentrations or pressures of reactants and certain constant parameters (normally rate
coefficients and partial reaction order). To determine the rate equation for a particular system,
one combines the reaction rate with a mass balance for the system. For a simple reaction

A→B

Where A is reactant and B is the product. The rate law or rate equation for this reaction is written
as:

where [A] expresses the concentration of A (usually in moles per liter) and k is the rate constant
of the reaction, and ―x‖ is the order of the reaction. Note that ―x‖ is not stoichiometric coefficient
in the balanced equation and it is determined experimentally. The order of reaction is the power
to which the reactant's concentration is raised in the rate law expression.

For reactions involving more than one reactant, the order of a reaction is the sum of the powers
to which all concentrations are raised in the rate law expression. For the general reaction.

we can write the rate law expression as:

r = k[A]x [B]y ...

The reaction is xth order in A, yth order in B, and (x + y) th order overall. Note that the order of a
reaction is not necessarily the same as the stoichiometric coefficients in the balanced equation for
the reaction. The value of the rate constant, k, depends on conditions such as temperature,
concentration and surface area of the adsorbent or light irradiation. Consider a reaction with the
rate equation

The reaction with the rate equation given above is described as ―second-order in A‖ and ―first-
order in B.‖ The overall reaction order is described as a third-order reaction overall, because the
sum of the exponents on [A] and [B] is 3.

Some examples of the order of generalized rate equations for simple reactions are given in Table
5.1

Table 5.1 Rate equation and reaction order for simple reaction rate

Rate equation Overall reaction order

k[A]o zero
k[A] first
k[A]2 second
k[A][B] second
k[A]3 third
k[A]2[B] third
k[A][B][C] third
k[A]3/2[B] 5/2

Example. The rate equation for the oxidation of SO2 to SO3 in excess O2 is

2SO2 (g) + O2 (g) → 2SO3 (g)

Rate = k[SO2] [SO3] –½

a. What is the order of the reaction with respect to each substance in the rate equation?

b.What happens to the rate of reaction as [SO3] increases?

Solution:

a The reaction is first-order with respect to SO2, and is negative one-half order with respect to
SO3.

b As the concentration of SO3 increases, the rate of reaction decreases.

To find the experimental rate equation by the method of initial rates, it is necessary to gather
concentration-time data in a series of separate experiments. Each experiment must have a
different initial concentration of one or more reactants. The experiments must be performed at
the same temperature. The initial rate for each experiment can be found from the concentration-
versus-time curve

Suppose a reaction of the type,

A → products

is under study. The data are inspected to find how the initial rate varies with the initial
concentration of A, [A]o. The objective is to find the value of the exponent in the rate equation,
rate = k [A]m, where m is the order of the reaction. For a first-order reaction, m = 1, and the rate
varies directly with [A]o. If [A]o is doubled, the rate is doubled; if [A]o is tripled, the rate is
tripled; and so on (see Table 5.2). For a second-order reaction, m = 2 and the rate is increased by
a factor of 22, or 4, if [A]o is doubled, and so on. If the reaction is zero-order in A, changes in the
concentration of A have no effect on the reaction rate. The order for each of several reactants can
be found by varying one initial concentration at a time, while keeping the others constant.

Table 5.2 Change in initial rate with change in [A]o for rate = k [A]m

For a reaction of If [A]0 is doubled If [A]0 is tripled

Zero-order (m = 0) rate is unchanged rate is unchanged

First-order (m = 1) rate is doubled rate is tripled

Second-order (m = 2) rate is quadrupled (x 22) rate is 9 times greater (x 32)

The kinetics of the reaction, 2NO(g) + O2(g) → 2NO2(g) was studied at 80 K by varying the
initial pressures of the reactants individually and finding the initial reaction rates. The following
data are typical of such a study.

Experiment pinit(NO) (Torr) Pinit(O2) (Torr) Rate of NO2 formation

(Torr/s)
A 1630 1630 6.13 × 10–8
B 3260 1630 24.5 × 10–8

C 1630 3260 12.2 × 10–8

a What is the order of reaction with respect to each reactant?

b What is the value of the rate constant?

Solution:

a Order of reaction with respect to each reactant can be determined as follows. Holding the O 2
pressure constant, while doubling the NO pressure, quadrupled the rate, indicating that the
reaction is second order in NO. With constant NO pressure, doubling the O2 pressure caused the
rate to double, showing that the reaction is first-order in O2. The rate equation for the formation
of NO2 becomes

Rate of NO2 formation = kp2 NO pO2

b The value of the rate constant. The experimental data can be used in the rate equation to find
the value of k. For the data from experiment a, for example:

k=

k= = 1.42 x 10-17 Torr-2 s-1

The best value for k is taken as an average of the k values calculated for each run: in this case, it
is 1.42 x 10-17 Torr-2 s-1
From experimental observations, in 1889, Svante Arrhenius, observed that a mathematical
relationship connects activation energy, temperature, and the rate constant. This relationship is
known as the Arrhenius equation and is written as:

k = Ae–Ea/RT …………………(5.1)

where, k is a rate constant at temperature T, A is a constant, R is an ideal-gas constant, and Ea =

activation energy.

Equation (5.1) shows the fraction of collisions in an elementary reaction in which the particles
have enough energy to react. The constant A corrects for the frequency of collisions, the
necessity for the proper orientation in effective collisions, and all factors other than activation
energy that are significant in effective collisions. Taking logarithms of both sides, the equation
(5.1) becomes

………………..(5.2)

The above equations show that reactions with larger activation energies have smaller values of k
and are, therefore, slower. The equation also shows that, for a given value of activation energy,
as the temperature increases, the value of rate constant increases. This indicates that the reaction
is faster, because at higher temperatures more molecules can collide effectively.

Equation (5.2 ) is the equation for a straight line. The value of Ea can be found from the slope of
a plot of log k versus 1/T, Ea = – 2.303 R × slope. Also, by combining the equations for the
values of k at two different temperatures T1 and T2 for the same reaction, a relationship is
obtained that allows for the calculation of Ea :

………(5.3)
Alternatively, if Ea and three of the four values k1, k2, T1, and T2 are known, the fourth can be
found. In using the Arrhenius equation, the energy is customarily expressed in joules,
temperature must be in kelvin, and R is 8.314 J/ (K mol).

Example

The thermal decomposition of CH3N=NCH3 in the gas phase to give nitrogen and methyl
radicals

CH3N = NCH3(g) → N2(g) + 2 •CH3 (g)

has an activation energy of 2.14 × 105 J/mol, at 600 K, at the given temperature, k = 1.99 × 108
s-1. Does the reaction rate double with a ten-degree rise in temperature hold for this reaction?

Solution: To answer the question, we must calculate k at 610 K, using the appropriate form of
the Arrhenius equation. The known are Ea and k1 at T1 = 600 K, and T2 = 610 K. The unknown is
k2 at 610 K.

Taking antilogarithms of both sides gives:

Therefore, k2 = (2.0) (1.99 ×108 s–1) = 4.0 × 108 s–1 Comparison of k1 with k2 shows that, for this
reaction, the rate constant is doubled by a ten-degree rise in temperature. (This is not always the
case.)

Exercise

1.Given that Ea for the hydrolysis of sucrose is 108 × 103 kJ / mol, compare the rate constant of
this reaction at 37°C (T1 ) with the rate constant of the same reaction at 27°C (T2).

2. Calculate the rate constant for the above reaction at 47°C and compare it to the rate constant at
37°C.
3. Plot a graph of log k versus 1/T to calculate the activation energy.

5.7.3 Concentration-Time Equation (Integrated Rate Law)

A rate law tells us how the rate of reaction depends on the concentration of the reactants at a
particular moment. But, often we would like to have a mathematical relationship that shows how
a reactant concentration changes over a period of time. A rate law can be transformed into a
mathematical relationship between concentration and time using calculus. Therefore, an
integrated law relates concentration to reaction time.

1. Zero Order Reaction

A zero-order reaction is a reaction whose rate of reaction does not depend on the reactant
concentration. For the general reaction
A → Product
the zero order rate law is written as the equation

……………………..(5.4)
Using calculus, it can be shown from equation (5.4) that
[A]t = – kt + [A]o …………………………..(5.5)

where [A] is concentration of A at t = t; [A]o is the concentration of A is at t = 0. Now,

zero-order reactions can be written as follows:

Integrated rate equation for 0th order reaction……………….(5.6)

This is a linear equation with the form of y = mx + b. For a zero-order reaction, a plot of
[A] versus-time is a straight line, whose slope is – k.
 Figure 5.8 A plot of [A] versus t for a zero-order reaction.

Example The decomposition of HI into hydrogen and iodine on a gold surface is

zeroorder in HI. The rate constant for the reaction is 0.050s–1. If you begin with a 0.500
M concentration of HI, what is the concentration of HI after 5 seconds? Solution: Use the
integrated rate
[HI] = [HI]0 – kt
The initial concentration is [A]0 = 0.500 M, and the reaction runs for 5 seconds.
[HI] = 0.500 M – 0.050 M s–1 x 5s = 0.250 M
2. First-Order Reactions
A first-order reaction is a reaction whose rate of reaction depends on the reactant
concentration raised to the first power. In a first-order of the type
A → Product the rate is

……………………….(5.7)

………………………..(5.8)
To obtain the units of k for this rate law, we write

Combining equations (5.7) and (5.8) for the rate, we get

 ………………..(5.9)
Using calculus, it can be shown from equation (5.9) that

…………………(5.10)
where ln is the natural logarithm, and [A]o and [A] are the concentrations of A at times
t = 0 and t = t, respectively. It should be understood that t = 0 need not correspond to the
beginning of the experiment. It can be any time at which we choose to start monitoring
the change in the concentration of A,
Equation (5.10) can be rearranged as follows

…Integrated rate equation for 1st order reaction(5.11)

Equation (5.11) has the form of the linear equation y = mx + b, in which m is the slope of
the line that is the graph of the equation. Thus, a plot of ln [A] versust gives a straight
line with a slope of k (or m). This graphical analysis allows us to calculate the rate
constant k. Figure 5.11 shows the characteristics of first-order reactions.

Figure 5.9 Plot for a reaction that is first-order with respect to A, first-order overall.

Note! The observation that plot of ln[A] versus time is a straight line confirms that the reaction is
first-order in A and first-order overall, i.e., Rate = k[A]. The slope is equal to –k.
In the following example, we apply equation (5.11) to a reaction.

Example: The conversion of cyclopropane in the gas phase is a first-order reaction with a rate
constant of 6.7 × 10–4 s at 500°C.

C3H6 → CH3 – CH = CH2

cyclopropane propene

a If the initial concentration of cyclopropane is 0.25 M, what is the concentration after 8.8
minutes?

b How long does it take for the concentration of cyclopropane to decrease from 0.25 M to 0.15
M?

c How long does it take to convert 74 % of the starting material?

Solution : a Applying equation (5.11),

ln =kt

Solving the equation, we obtain

ln =0.354

e0.354=1.42

[A]= 0.18M

b. Again using equation (5.11), we have

ln = (6.7×10–4s–1) t

t = 7.6×102

s = 13 minutes
c In a calculation of this type, we do not need to know the actual concentration of the starting
material. If 74% of the starting material has reacted, the amount left after time t is (100% –
74%), or 26%. Thus, [A] /[A]o = 26/100 = 0.26.we write

t= ln

= 1/6.7×10–4s–1ln1.0M/0.26M

=2.0 × 103 s

= 33 minutes

3. Second-Order Reactions

A second order reaction is a reaction whose rate depends either on the concentration of one
reactant raised to the second power or on the concentrations of two different reactants, each
raised to the first power. The simpler type of reaction involves one kind of reactant molecule

2 A → Product

Where ……………………….(5.12)

From the rate law r= k [A] 2 ………………………..(5.13)

As before, we can determine the units of k by writing

……………………….(5.14)

For simplicity, we will consider a second order reaction with a rate law of the following type

2A —→ product

r= k [A] 2

By using calculus, use can obtain the expression

 Integrated rate equation for 2nd order reaction ……….. (5.15)

The graph of 1/[A]O versus time gives a straight line with a slope of k as shown in Figure 5.10.

Figure 5.10 Plots for a reaction that is second-order with respect to A and overall a second-
order reaction.

Another type of second-order reaction is A + B —→ product

and the rate equation is given by

r = k[A][B] ……………….(5.16)

where the reaction is first-order in A and first-order in B. Thus, this reaction has an overall
reaction order of 2. The corresponding integrated rate equation for such type of second order-
reaction is too complex for our discussion and beyond the scope of this text book.

Example: Nitrosyl chloride, NOCl, decomposes slowly to NO and Cl2 as shown in the equation
below. 2NOCl —→ 2NO + Cl2

r = k[NOCl]2
The rate constant, k equals 0.020 L mol–1 s–1 at a certain temperature. If the initial concentration
0.050 M, what will the concentration be after 30 minutes?

Solution: [NOCl] = 0.050 M k = 0.020 L mol–1 s–1

[NOCl]t = ? M t = 30 min = 1800 s

The integrated rate equation for this reaction is given by:

1/ [NOCl]t = kt + 1/[NOCl]o

= (0.020 L mol–1 s–1) (1800 s) +1/0.50mol-1

= 50 L mol–1

∴ [NOCl]t = 0.018 L mol–1 = 0.018 M

5.7.4 The Half-life of a Reaction

The half-life of a reaction is defined as the time required for the concentration of a reactant to
decrease to half of its initial concentration. This means that half-life is the time it takes for the
concentration of A to fall from [A]o to ½[A]o, i.e [A] = ½[A]o. The half-life of a reaction is
designated by the symbol, t½.

The mathematical expression for the half-life of a first-order reaction is determined by

substituting t = t ½ and [A] = ½[A]o in equation

This gives us

…………………………(5.17)

And solving for t ½ gives,

From the relation, it can be noted that, for a first-order reaction, the half-life is independent of the initial
concentration of A, [A]o. For second-order reactions, half-life depends on the initial concentration, [A]o,
and the rate constant, k. For a second-order reaction, the half-life expression is given by the equation

………………………….(5.18)

Rearranging and solving for t ½, we get the expression,

…………………………..(5.19)

Summary of equations for 1st and 2nd order reactions is given in Table 5.3.

Table 5.3 Summary of the kinetics of first-order and second order reactions

Order Rate equation Concentration-time equations Half-life

1st rate = k[A] In[A]o/[A] 0.693/k

2nd rate = k[A]2 1/[A]o= 1/[A]o +kt 1/k[A]o

Example: The decomposition of N2O5 in CCl4 at 45 °C is first order reaction with k = 6.32 × 10–
4 –1
s . If the initial concentration of N2O5, is 0.40 mol/L:

a Calculate t ½.

b Find the concentration of N2O5 remaining after t ½.

Solution: a. t ½=0.693/k=0.693/6.32 × 10–4 s–1

b The equation relating time and concentration for a first-order reaction is used with [N2O5] o =
0.40 mol/L and t = 1097 s to find [N2O5].

ln[N2O5] = – kt + ln[N2O5]o

(6.32 × 10–4 s–1) (1097 s) + ln (0.40)

= (– 0.693) + (– 0.9163) = – 1.6096

Taking the inverse of the natural logarithms of both sides gives the concentration of N2O5
remaining after 1.0 hour,

[N2O5] = 0.1996 mol/L ≅ 0.20 mol/L.

Exercise.

1 If a certain first-order reaction has a half-life of 30.0 minutes, a Calculate the rate constant for
this reaction. b How much time is required for this reaction to be 35% complete?

2.The rate constant for the formation of hydrogen iodide from the elements,

H2 (g) + I2 (g) → 2HI (g) is 2.7 × 10–4 L/(mol.s) at 600 K and 3.5 × 10–3 L/(mol.s) at 650 K.

a Find the activation energy Ea .

b Calculate the rate constant at 700 K.

3.The rate constant for the decomposition of N2O5 in chloroform,

2N2O5 4NO2 + O2

Was measured at two different temperatures, T1 = 25 °C, k1 = 5.54 ×10–5 s–1 and T2 = 67 °C, k2 =
9.30 × 10–3 s–1. Find the activation energy for this reaction.

5.7.5. REACTION MECHANISM

An overall balanced chemical equation does not give any information about how a reaction
actually takes place. In many cases, it merely represents the sum of several elementary steps, or
elementary reactions, a series of simple reactions that represents the progress of the overall
reaction at the molecular level. The term for the sequence of elementary steps that leads to
product formation is reaction mechanism. The reaction mechanism is comparable to the simplest
description you might give of the route of a trip you plan to take. The overall chemical equation
specifies only the origin and destination, while the reaction mectanim describes the stopovers
also.
As an example of a reaction mechanism, let us consider the reaction between nitric oxide and
oxygen

2NO(g) + O2(g) → 2NO2(g)

We know that the products are not formed directly from the collision of two NO molecules with
an O2 molecule, because N2O2 is detected during the course of the reaction. Let us assume that
the reaction actually takes place via two elementary steps as follows:

2NO(g) → N2O2(g)

N2O2(g) + O2(g) → 2NO2(g)

In the first elementary step, two NO molecules collide to form a N2O2 molecule. This event is
followed by the reaction between N2 O2 and O2 to give two molecules of NO2. The net chemical
equation, which represents the overall change, is given by the sum of the elementary steps.

Elementary step: NO + NO → N2O2

Elementary step: N2O2 + O2 → 2NO2

Overall reaction 2NO + O2 → 2NO2

Species such as N2O2 are called intermediates because they appear in the mechanism of the
reaction (that is, the elementary steps) but not in the overall balanced equation.

5.7.5.1 Molecularity of an Elementary Reaction

The minimum number of reacting particles (molecules, atoms or ions) that come together or
collide in a rate determining step to form product or products is called the molecularity of a
reaction. It is the number of reactant molecules taking part in a single step of the reaction.

Example

a PCl5 → PCl3 + Cl2 (Unimolecular)

b 2HI → H2 + I2 (Bimolecular)

c 2SO2 + O2 → 2SO3 (Termolecular)

d NO + O3 → NO2 + O2 (Bimolecular)

e 2CO + O2 → 2CO2 (Termolecular)

f 2FeCl3 + SnCl2 → SnCl2 + 2FeCl2 (Termolecular)

In the reaction that involve sequence of steps rate is determined by the lowest step

Example : Decomposition of H2O2 takes place in the following two steps:

Step 1: H2O2 → H2O + [O] (Slow)

Step 2: [O] + [O] → O2 (fast)

H2O2 → H2O + 1/2O2 (overall reaction)

The slowest step is rate-determining. Thus, from step 1, reaction appears to be unimolecular

It may be noted that molecularity is a theoretical concept and it cannot be zero, negative,
fractional, infinite and imaginary.

Exercise

1. Give the meanings of each of the following terms:

a Elementary steps
b Unimolecular reaction
c Bimolecular reaction
d Termolecular reaction

2. Determine the molecularity of the following reactions:

a NH4NO2 —→ N2 + 2H2O
b O3 + NO —→ NO2 + O2
c 2NO + O2 —→ 2NO2

5.7.5.1 Rate-Determining Step

In a multi-step reaction, all the elementary reactions do not necessarily proceed at equal rates.
One of them might be very rapid, moderate or very slow. The reactants can be converted to
products only as fast as they can complete the slowest step. The slowest step in the sequence of
steps leading to the formation of products is called the ratedetermining step. In other words, the
slowest step in the mechanism determines the overall rate of the reaction.

Because the rate-determining step limits the rate of the overall reaction, its rate law represents
the rate law for the overall reaction. For example, the reaction of NO2 with F2 is given by the
equation:

2NO2 (g) + F2 (g) → 2NO2F (g)

The experimentally determined rate law is: Rate = k[NO2][F2], the proposed reaction mechanism
is:

Let us check whether the proposed mechanism agrees with the experimental rate law or not.
First, the sum of these reaction steps must give the overall balanced equation:

Overall reaction

So, the first requirement is satisfied. The formation of •F in the first step occurs more slowly than
its reaction with NO2 to form NO2F in the second step. Thus, the rate of formation of NO2F in
the second step is controlled by the rate of formation of •F in the first step. The overall rate
cannot be faster than that of the slowest step. Overall rate = the rate of the slowest step

Overall rate = the rate of the slowest step

The rate law agrees with experimentally determined rate law. So, the proposed mechanism is
acceptable because it satisfies both requirements.
Exercise

Answer each of the following questions.

1. Describe the term molecularity of a reaction.

2. How do you identify the rate determining step for a reaction that involves more than one step?
3. The reaction

NO2(g) + CO(g) → NO(g) + CO2(g) can be thought of as occurring in two elementary steps:

a NO2 + NO2 → NO + NO3 (slow step)

b NO3 + CO → NO2 + CO2 (fast step) Identify the rate determining step and determine
the molecularity of this reaction.