JINKA UNIVERSITY

Analytical Chemistry
BY: Abdulkerim A. (MSc.)

1 1/31/2023
1.1 Definition of Analytical Chemistry
Analytical chemistry is a science concerned with development of
the theoretical foundations and methods of chemical analysis. It deals
with the different kinds of methods used for
 identification,
separation and determination of the chemical composition of
samples of matter.
It is the Science that seeks ever improved means of measuring the
chemical composition of natural and artificial materials.
Is a sub discipline of chemistry that has the broad mission of
understanding the chemical composition of all matter and developing
the
2 tools to elucidate such compositions. 1/31/2023
 Cont’d...

Analytical chemistry is particularly concerned with the questions of

"what chemicals are present,
what are their characteristics and
in what quantities are they present?“
Although there are probably as many descriptions of the analytical
approach as there are analytical chemists, it is convenient to treat it as
a five-step process:
1. Identify and define the problem
2. Design the experimental procedure
3. Conduct an experiment, and gather data
3 1/31/2023
 Cont’d...
4. Analyze the experimental data
5. Propose a solution to the problem; i.e.; analytical chemistry
begins with a problem and ends up by proposing a solution to
the intended problem.

1.2 The Role of Analytical Chemistry

Chemical analysis is an indispensable servant of modern
technology whilst it partly depends on that modern technology for its
operation.
In modern technology, it is impossible to over-estimate the
importance of analysis. Some of the major areas of application are
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listed below.
Cont…
 Analytical chemists work to improve existing techniques to meet the
demands of for Faster, Cheaper, More Sensitive chemical measurements
 It plays a vital role in many research areas in viz.:
o Pharmacy :
- provides knowledge of Cpds. Identification , Separation And Quantification
that can be useful for measuring bioavailability of drugs, purifying drugs
during synthesis, and identifying drug metabolic pathways.
o Environmental Sciences :
-to determine the concentration of harmful pollutants in the
environment
o Medical science and the other sciences : ?
*Chemists devote a significant part of their time in the lab. to
gathering quantitative information about systems of interest to
them.

5
 Fundamental Research
 The first steps in unraveling the details of an unknown system frequently

involve the identification of its constituents by qualitative chemical

analysis.

 Follow-up investigations usually require structural information and

quantitative measurements.

 Product Development

 The design and development of a new product will often depend upon

establishing a link between its chemical composition and its physical

properties or performance.

 Typical examples are the development of alloys and of polymer

composites.
6
Product Quality Control
 Most manufacturing industries require a uniform product quality.

 To ensure that this requirement is met, both raw materials and

finished products are subjected to extensive chemical analysis.

 On the one hand, the necessary constituents must be kept at the

optimum levels; while on the other impurities such as poisons in

foodstuffs must be kept below the maximum allowed by law.

7
Medical and Clinical Studies

 The levels of various elements and compounds in body fluids are

important indicators of physiological disorders.
 High sugar content in urine indicating a diabetic condition and lead in
blood are probably the most well-known examples.

Assay
 In commercial dealings with raw materials such as ores, the value of
the ore is set by its metal content.
 Large amounts of material are often involved, so that taken overall
small differences in concentration can be of considerable commercial
significance. Accurate and reliable chemical analysis is thus essential.

8
Contn’d role of anal ….

9 1/31/2023
 Cont…
1.3.Classification of Analytical Chemistry
There are two categories of analytical chemistry . These are:
1.Qualitative analysis
2.Quantitative analysis
1.What is it? Identification of elements, ions and compounds
present in a sample. Therefore qualitative analysis deals with
identification of the chemical identity of the sample.

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Quantitative analysis is how much. Qualitative analysis is what.

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 Example:
solid salts Flame test

NaCl Yellow

KCl Violet
CaCl2 Brick-red

2. How much? Quantitative analysis–it deals with estimation of an amount.

Scope and Applications of Analytical chemistry

Important areas of application include the following
Quality control in the process industries of
Starting materials
Inter mediates
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12 products
 Cont’d….

 Confirmation of purity
 Identification of impurities
1.4 Methods of Analytical Analysis
 Different analytical methods are used for analyzing samples.
 Analytical methods can be categorized in to two sub groups:
I. Classical Techniques and
II. Instrumental Techniques.

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i. Classical Techniques
It is known as chemical methods of qualitative analysis.
It involves analytical reaction.
The analyte to be determined can be anion or an element is
changed/ converted to a given compound which has its own
characteristic properties.
The chemical change involved is known as an analytical reaction
and the substance responsible for the change is a reagent.

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 I. Gravimetric method determination
The constituent is converted to a form that can be precisely weighed;
e.g.; electroplating, Precipitation, loss by volatilization.
The mass of the analyte or some compound chemically related to it is
determined.
II. Titrimetric/ Volumetric method determination
The volume of a solution containing sufficient reagent to react
completely with the analyte is measured.

Limitations:
A) Sensitivity-amount of a sample used for the analysis; large amount
of a sample-less sensitive and small amount of a sample–high 1/31/2023
sensitive.
15
 Cont’d…..
Therefore existing chemical method do not always satisfy the
increasing demand of science and technology as to sensitivity
i.e. the suitability for detection and determination of traces of
various limitations.
B) Speed of analysis-low speed.

ii). Instrumental Techniques

It is known as physical (physico-chemical) method.
Use instruments for the analysis.
Measure some physical properties which can be related with the
amount of the analyte, such as conductivity, electrode potential, light
1/31/2023
16
absorption or emission, etc.
 i. Spectroscopic determination
The constituent is made to absorb or to emit electromagnetic
radiation;
e.g.; visible and Ultraviolet absorption, infrared absorptions, atomic
absorptions, flame, etc.
ii. Chromatographic determination
The constituent is separated by passage through a selectively
absorbing column and then sensed by a detector;
e.g.; gas chromatography, liquid chromatography, etc.
iii. Electro chemical determination
The constituent affects a red-ox equilibrium at a suitable electrode;
1/31/2023
e.g.; Potentiometry, coulometer, and polarography
17
 vi. Mass spectroscopy:- used to determine the mass to mass
charge ratio of the molecule.
Table.1.Comparison of the two techniques
Classical analysis Instrumental analysis
Involves analytical reaction use instruments for the analysis
Sensitivity is low sensitivity is high
Speed is low speed is high

Use classical tools Use classical and modern

(test tube, beakers, flasks…) tools and procedures
Use classical procedure Costive (its disadvantage)
like filtration, Decantation, crystallization…
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1.5 Steps in Quantitative Chemical Analysis
1. Selecting a Method of Analysis
- A vital first step in quantitative analysis is the Selection of a
method.
 An important consideration in selection is the level of accuracy
required.
- The method that is selected ordinarily represents a compromise
between accuracy and economy.
 A second consideration related to economic factors is the no. of
samples to be analyzed.
- Many samples, we can give to spend a good deal of time in such
preliminary operation as assembling and calibrating instruments and
equipment as well as preparing standard solution.
- A single sample or a few samples at most, we may find it more
expedient to select a procedure that avoids or minimizes such
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preliminary steps.
 2. Sampling

o Sampling is the process of Selecting a Representative Bulk Sample

From The Lot.
- Where the bulk is large and inhomogeneous, great effort
is required to get a representative sample.
3. Preparing a Laboratory Sample
o Sample preparation is the process that converts a bulk
sample into a homogeneous lab. sample.
- A solid lab. sample is ground to decrease particle size to
assure homogeneity.
- If water is absorbed during each of these steps, depending
up on the humidity of the environment, any loss or gain of
water changes the chemical composition of solids.
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...drying solid samples typically at 110oC at atmospheric pressure to
remove adsorbed water prior to analysis.
 Temperature-sensitive samples may simply be stored in an
environment that brings them to a constant, reproducible moisture
level.
4. Defining Replicate Samples
Most chemical analysis are performed on replicate samples whose
masses or volumes have been determined by careful measurements
with an analytical balance or with a precise volumetric device.
- Replication improves the quality of results and provides a
measure of their reliability.
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Eg. Consider the no. of replicate a ground water sample in the analysis of
Ag by AAS.
Reading S11 S11in ppm ReadingS12 S12in ppm ReadingS13 S13in ppm
1st 0.01 0.13983 0.01 0.13983 0.011 0.15415
2nd 0.01 0.13983 0.011 0.15415 0.009 0.1255
3rd 0.011 0.15415 0.011 0.15415 0.012 0.16848
4th 0.009 0.1255 0.009 0.1255 0.012 0.16848
0.01 0.13983 0.01025 0.14341 0.011 0.15415
Mean of the readings 0.01042 0.1458ppm
5. Preparing Solutions of the Samples
Most analysis are performed on solution of the sample.
-the solvent should dissolve the entire sample rapidly and
completely.
- The conditions of dissolutions should be sufficiently mild that
loss of the analyte cannot occur.

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 Cont’d…
- Unfortunately, many materials that must be analyzed are insoluble
in common solvent.
- Conversation of the analyte in such materials into a soluble
form can be difficult and time-consuming task.
- It involves heating the sample with aqueous solutions of strong
acids, strong bases, oxidizing agents, reducing agents, or some
combination of such reagents; ignition of the sample in air or
oxygen; or high-temperature fusion of the sample in the presence of
various fluxes.

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 6. Eliminating Interferences

- Interferences are species other than the analyte that affect

the final measurement.

- the analyte should be free from interferences before the final

measurement is made.

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 7. Calibration and Measurement

To determine, check, or rectify (to correct) the

graduation of any instrument giving
quantitative measurements

Instrument calibration is one of the primary processes used to

maintain instrument accuracy.

Calibration is the process of configuring an instrument to provide

a result for a sample within an acceptable range.

Eliminating or minimizing factors that cause inaccurate

measurements is a fundamental aspect of instrumentation design.

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 8. Calculating Results

- Computing analyte concentrations from experimental

data is ordinarily a simple and straightforward task,
particularly with modern calculators or computers.
- Such computations are based on the raw experimental data
collected in the measurement step, the stoichiometry of the
chemical reaction up on which the analysis is based, and
instrumental factors.
9. Evaluating Results from Estimating Their Reliability
- Analytical results are incomplete without an estimate of
their reliability.
- The experimenter must provide some measure of the
uncertainties associated with computed results if the data are to have
any value. 1/31/2023
26
Unit Two
Ionic Equilibria
2.1 Acid-base Equilibria
2.1.1. Theories of Acids and Bases
i. The Arrhenius Theory
 An acid is a substance that contains ionizable hydrogen atom/s and
produces H+ in aqueous solution.
- HA + H2O  A- + H3O+
- HCN + H2O  H3O+ + CN-
 A base is a substance that contains the OH (hydroxyl) group and
produces hydroxide ions, OH- in aqueous solution.
- BOH  B+ + OH-
- NaOH  Na+ + OH-
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ii. The Bronsted–Lowry Theory
o Acids are proton (H+) donors, or any hydrogen-containing molecule or
ion capable of releasing a proton, H+
- Acid  H+ + Base
HCl + H2O  H3O+(aq) + Cl- (aq)
eg. HCl, HNO3, H2SO4, HCOOH, HCN

o Bases are proton(H+) acceptors, or any molecule or ion that can accept a
proton
- Base + H+  Acid
eg. CH3COOH(aq) + NH3(aq)  CH3COO–(aq) + NH4+(aq)
acid base
HCO3- + H2O  CO32- + H3O+
Acid Base
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 Cont’d Bronsted–Lowry ….
o Conjugate acid-base pairs
- Conjugate base : a substance formed when an acid loses a proton.
- Conjugate acid : the one that formed when the base accepts proton.
- Acid1 + Base2  C. Base1 + C. Acid2
eg. HNO2 + H2O  NO2- + H3O+
Acid1 base2 base1 acid2
HNO2 (acid1) and NO2- (base1) are one conjugate acid–base pair,
H2O (base2) and H3O+ (acid2) are the other conjugate acid–base pair.
*** The stronger the acid, the weaker is its conjugate base;
the weaker the acid, the stronger is its conjugate base.

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 Cont’d Bronsted–Lowry ….
o Amphiprotic substances:- are substances which posses both acidic
and basic properties, i.e., act as acid in the presence of base and base
in the presence of acid.
eg. H2O, NH3, CH3OH, HCO3-, HS-, H2PO4-, HPO42-, etc.
- HCl + H2O  Cl- + H3O+
acid base
- NH3 + H2O  NH4+ + OH-
base acid
- NH3 + OH-  NH2- + H2O
acid base
o Autoionization: self ioniztion of a substance to form a pair of ionic
species.
eg. -H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
-NH3(l) + NH3(l) NH4+(aq) + NH2-(aq)
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iii. Lewis theory
o Acid is a substance that can accept an electron pair
Abase is a substance that can donate an electron pair
o Lewis Base can be :
- Molecules containing an atom with lone pair of electrons(s)
- All atoms attain stable electronic configuration
- It may contain substances which contain electronegative atoms- O,
N, etc.
- It includes anions
o Lewis acid can be
- Molecules having a central atom with an incomplete octet or
containing multiple bonds.

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 Contn’d Lewis theory…
AlCl3 + NH3  H3N-AlCl3
L. acid L. base
SO3 + O2-  SO42-
L. acid L. base
- Molecules with a central atom capable of expanding its outer octet by
using empty d- orbitals.
SnCl4 + 2Cl-  SnCl62-
L. acid L. base
- Simple cations
Fe3+ + 6H2O  Fe(H2O)63+
acid base

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2.1.2. Dissociation of acids and bases
Acids:
o 1. Monoprotic acids
are acids which contain only one ionizable hydrogen atom per molecule.
HA  H+ + A-
eg. HCl, HNO3, HClO4, CH3COOH, HF, HCN, etc
o 2. Diprotic acids
are acids which contain two ionizable hydrogen atoms per mole of an acid.
H2A  2H+ + A-
eg. H2S, H2SO4, H2CO3, etc
H2S  2H+ + S2-
o 3. Polyprotic acids
are acids which contain more than two ionizable hydrogen atoms per
mole of an acid.
eg. H3PO4 + H2O  3H+ + PO43-
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 Cont’nd Dissociation of acids and …
o i. Strong acids
Are acids which dissociate completely in a particular solvent without
leaving undissociated acids in a solution.
The most common strong acids are:
HClO4, HCl, HNO3 and H2SO4.
HA(aq) + H2O(l)  H3O+(aq) + Cl–(aq)
HCl(aq) + H2O(l)  H3O+(aq) + Cl–(aq)
o ii. Weak acids
Are acids which dissociate partially in to their respective ions in soln.
A solution of weak acids contains ionized molecules (ions) and unionized
molecules.
HA(l) + H2O(l) H3O+(aq) + A–(aq)
eg. CH3COOH, HF, HCN, HNO2, HOOCH, etc
34 HF + H2O F –(aq) + H3O +(aq) 1/31/2023
 Contn’d Dissociation of acids and …
o i. Strong bases
Are substances that dissociate completely in a particular solvent, or it has a
strong tendency to accept proton.
eg. LiOH, NaOH, Ca(OH)2, CsOH, and Sr(OH)2
B(aq) + H2O(l)  BH+(aq) + OH–(aq)
base(s) acid(s) acid(w) base(w)
*Strong bases have weak conjugate acids.
o ii. Weak Bases
Are bases which dissociate partially in to their respective ions in aqueous
solution.
B(aq) + H2O(l) BH+(aq) + OH–(aq)

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 Contn’d Dissociation of acids and …
o Dissociation constant
Ka or Kb is used to describe the equilibrium exists between the weak
acid/ base and its conjugate base/ acid in a dilute solution.
HA(aq) + H2O(l) H3O+(aq) + A–(aq)
The equilibrium constant for the weak acid is called an acid
dissociation constant, Ka, and is written as:
o Ka = [H3O+] [A–]
[HA]
Polyprotic acids are described by a series of acid dissociation steps,
each characterized by its own acid dissociation constant.

36
 Contn’d Dissociation of acids and …
eg.1 i. H3PO4 + H2O H3O+ + H2PO4-

Ka1 = [H3O+] [H2PO4-] = 7.11x10-3

[H3PO4]

ii. H2PO4- + H2O H3O+ + HPO42-

Ka2 = [H3O+] [HPO42-] = 6.32x10-8

[H2PO4-]

iii. HPO42- + H2O H3O+ + PO43-

Ka3 = [H3O+] [PO43-] 4.5x10-13

[HPO42-]

o Kb : B(aq) + H2O(l) BH+ + OH-(aq)

eg. NH3(aq + H2O(l) NH4+ + OH-(aq)

Kb = [NH4+][OH-]
37 [NH3]
 Contn’d Dissociation of acids and …

38
 Contn’d Dissociation of acids and …

 Calculate the concentration of each species at equilibrium

a) 0.01 M HNO3 b) 0.01 M CH3COOH (Ka =1.8x10-5)
% percent of ionization = conc. of ionized molecules x 100
conc. of unionized molecules

Soln: a)0.01M HNO3

HNO3(aqu) + H2O(l) H3O+ + NO3-
0.01 M 0.01M 0.01 M
[H3O+] = [NO3-] = 0.01 M

39
 Contn’d Dissociation of acids and …
b) 0.01 M CH3COOH (Ka =1.8x10-5)
CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq)
Ini. Conc. 0.01 M 0 0
Equi. Con. C-x(0.01-x) x x
Ka = [H3O+][CH3COO-]
[CH3COOH-]
= x2/(0.01-x) = 1.8x10-5
- Assume 0.01-x~0.01
if the error ±0.05 no need of quadratic equation
= [H3O+] = [CH3COO-] = 1.34x10-4 M
c) 0.01 M HCN (Ka = 6.2x10-10)
Answer = 2.49x10-6 M
40
 Exercise
Arrange the following species according to their strengths as
bases: H2O, F-, Cl-, NO2 and CN-
Remember that water is a stronger base than the conjugate base of
a strong acid but a weaker base than the conjugate base of a weak
acid. This leads to the following order:

Cl- < H2O < conjugate bases of weak acids

Weakest bases Strongest bases
Cl- < H2O < F- < NO2- < CN-

41 1/31/2023
2.1.3 Dissociation of water and pH/pOH of aqueous solution
 H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
- Kw = [H3O+] [OH-],
- at 25oC, Kw = 1.0 X 10-14
- [H3O+] = [OH-] = 1.0x10-7
o pH = -log [H3O+] or [H3O+] = 10-pH
pOH = -log [OH-] or [OH-] = 10-pOH
 In aqueous soln. at 25oC, pKW = pH + pOH = 14
o In a solution:
- in neutral soln. [H3O+] = [OH-], pH = pOH = 7
- in acidic soln. [H3O+] > [OH-], pH< pOH
- in basic soln. [H3O+]< [OH-], pH > pOH

42
 Fig. 2

Fig-1
1/31/2023
43
44 1/31/2023
 Contn’d Dissociation of water and pH/…
eg. Calculate the concentration of H3O+and OH- and pH and POH
a) 0.005 M HCl
b) 0.005 M HCN( Ka = 6.2x10–10 )
c) Calculate the pH for a 0.20 M aqueous NH3 soln.
K(NH3)=1.75x10-5.
Soln.: a) HCl is a strong acid and completely dissociate
HCl → H3O+ + Cl-
0.005 M 0.005M 0.005M

pH = -log [H3O+]
= -log 0.005 M
= 2.3
pH + pOH =14
pOH =14 – 2.3
45 = 11.7
 Contn’d Dissociation of water and pH/…
b) 0.005 M HCN (Ka = 6.2x10–10)
HCN H3O+ + CN-
Initial conc. 0.005 M 0 0
Equil.conc. 0.005 M - x x x

Ka = [H3O+] [CN-] = 6.2x10–10

[HCN]
6.2x10–10 = X2 suppose 0.005-x  0.005
0.005M-X
x2 = (6.2x10–10 ) (0.005M) = 0.031x10-4
x = 0.176 x10-5 M = [H3O+] = [CN-]
pH = -log [H3O+] = -log 0.176x10-5 M = 5.75
[OH-] = Kw/[H3O+] = 5.68x10-9 M
46 pOH = 8.24
 Contn’d Dissociation of water and pH/…
o Calculate the pH for a 0.20 M aqueous NH3 soln. Kb(NH3) =1.75x10-5.
The equation for the ionization of aqueous ammonia is
NH3 + H2O NH4+ + OH-
Initi. 0.2 0 0
Equi. 0.2 –x x x
Substitute into the ionization constant, Kb expression gives
Kb = [NH4+][OH-]
[NH3]
1.75x10-5 = (x)(x)
0.20-x

47
48 1/31/2023
 Cont’d…

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2.1.4 The Common ion Effect and Buffer Solutions
If a solution is made in which the same ion is produced by two
different compounds the common ion effect is exhibited and
decreasing the dissociation of a weak electrolyte.

A buffer solution is defined as a solution whose pH

remains practically constant even when small amounts of
the acid or the base are added to it.
A buffer solution is a mixture of an acid and its conjugate base
that resists slight changes in pH when H3O+ (a strong
acid) or OH- ions (a strong base) are added.

50
  Types of Buffer solutions. There are two types of buffer solutions.
These are:

(i) Solutions of single substances: The solution of the salt of a weak acid
and a weak base e.g. ammonium acetate (CH COONH ) acts as a
3 4
buffer.

(ii)Solutions of Mixtures: These are further of two types:

 (a) Acidic Buffer. It is the solution of a mixture of a weak acid and
a salt of this weak acid with a strong base (e.g. CH COOH +
3
CH COONa).
3
(b)Basic Buffer. It is the solution of a mixture of a weak base and a salt
of this weak base with a strong acid. (e.g. NH OH + NH Cl).
4 4

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 Cont……….
Kinds of Buffer solution:
o i. Solutions from a weak acid plus a soluble ionic salt of the
weak acid.
Example:
CH3COOH - CH3COO-, HCN - CN-, HNO2 - NO2-,
HF - F-.
o ii. Solutions from a weak base plus a soluble ionic salt of
the weak base.
o Example: NH3 - NH4+

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 Contn’d the Common ion Effect and …
 i. Solutions made of weak acids plus a soluble ionic salt of the weak acid
Example :
The weak acid - HCN
- The soluble ionic salt - NaCN
- NaCN + H2O  Na+ + CN- ⇒ 100%
- HCN + H2O H3O+ + CN- ⇒ Ka = 6.2x10-10
o The pH of the buffer solution (weak acid + salt of weak acid) is less acidic than a
solution just comprised of the weak acid alone.
Why ?
- eg. HCN + H2O H3O+ + CN-
- Adding additional CN- ion(from NaCN) to a solution that is in
equilibrium will cause the increase of CN- to react with H3O+ and shift
the equilibrium to reform HCN.

53
 Contn’d the Common ion Effect and …
o a. addition of a strong acid
CN- combines with H3O+(added acid) to form non ionized HCN and
H2O, so long as we do not exceed the amount of buffer reserve.
CN- + H3O+ HCN + H2O
B/s the added H3O+ is consumed by CN- ion; there is very little
changes in the pH.
o b. addition of a strong base
When a strong base is added to the buffer, the OH- is neutralized by
HCN, which results a little change in the pH.
OH- + HCN CN- + H2O

54
 Contn’d the Common ion Effect and …
o HA + H2O H3O+ + A-
Ka = [H3O+] [A-]
[HA]
[H3O+] = Ka[HA]
[A-]
-log [H3O+] = -log Ka - logacid  Multiplying both sides by ‘-log’
base
pH = pKa + logsalt or pH = pKa + loganion
acid  acid 
This equation is known as the Henderson–Hasselbalch equation.
eg. HF + H2O H3O+ + F-
pH = pKa + log [F-]
[HF]

55
 Contn’d Common ion Effect and …
 ii. A buffer solution containing a weak base and its salt
- NH4Cl + H2O  NH4+ + Cl- ⇒ 100%
added to
- NH3 + H2O NH4+ + OH- ⇒ Kb = 1.8x10-5
o B + H 2O BH+ + OH-
Kb = [BH+] [OH–]
[B]
BH  
salt
pOH = pKb + log B  or, pOH = pKb + log
base
Henderson–Hasselbalch equation
After calculating the pOH of the solution, pH can be determined as:
pH = pKa + log B 
BH 
56
 Contn’d Common ion Effect and …
- a. Calculate the pH of solution that is 0.01 M in HNO2
- b. the above solution that contains 0.05 M in NaNO2 (Ka = 4.6x10-4)
Solution
a. The pH of the solution in the absence of common ion effect
HNO2 + H2O H3O+ + NO2-
initial conc. 0.01 M 0 0M
at equilibrium 0.01 – x x x
Ka = [H3O+] [NO2–] = 4.6x10–4
[HNO2]
4.6x10–4 = (x) (x) assume that 0.01–x 0.01
0.01-x
4.6x10–4 = x2
0.01
x2 = 4.6 x10-6 M
[H3O+] = [NO2–] = 2.1x10-3
pH = -log 2.1x10-3 = 2.7
57
 Contn’d Common ion Effect and …
b, Henderson–Hasselbalch equation are
pKa = -log Ka = -log 4.6x10-4 = 3.35
NaNO2 + H2O → Na+ + NO2-
0.05 0.05 0.05
HNO2 + H2O H3O+ + NO2-
initial conc. 0.01 M 0M 0.05 M
at equil (0.01 – x)M xM (0.05+x)

Ka = [H3O+] [NO2–] = 4.6x10–4

[HNO2]
4.6x10–4 = (x) (x+0.05) assume that x+0.05  0.05 and 0.01–x 0.01
0.01-x
4.6x10–4 = 0.05x
0.01
X = 0.92 x10-4 M = [H3O+]
[NO2–] = x+0.05M = 0.92 x10-4 + 0.05  0.05M
[HNO2] = 0.01-x = 0.1- 0.92 x10-4  0.1
pH = pKa + log [NO2-] = 3.35 + log((0.05)/(0.01)) = 4.05
[HNO2]
in the presence of common ion, NO2– the pH increases from 2.7 to 4.05
58
 Examples
1. Find the pH and pOH of 0.050 M HA. Ka =1.59 x10-10
HA + H2O H3O+ + A-
0.05 0 0
0.05 - x x x
x2 = 1.59 x10-10
0.050-x
x = 2.8x10-6 M;
pH = -log[H3O+] = 5.55
2. If the concentration of a base is 0.0372 M with its Kb = 2.6x10-6
a. Calculate the conc. of the species
b. the pH, pOH
B + H2O BH+ + OH-
0.0372 0 0
0.0372 - x x x
Solution
a. x2 = 2.6x10-6; x= 3.1x10-4M
0.0372 - x
[H+] = Kw/[OH-]= 1.0x10-14/3.1x10-4 = 3.2x10-11
b. pH = -log[H+] = 10.49
59
 contn’d Examples
4. What is the pH of a solution that is 0.20 M HF when 0.10 M NaF is
added?
NaF (S) + H2O → Na+(aq) + F-(aq)
0.1 0.1 0.1
HF + H2O H3O+ + F-
Initial. 0.2 0 0.1
Equili. 0.2-x x 0.1+ x
Answer pH = 1.92
5.What is the [H3O+], [OH-] and pH of 0.225M of CH3OOH when
ionized in water; at 25oC
Ka(CH3OOH) is 1.8x10-5. and when 0.125M NaCH3OO is added.
60
 2.1.5. Hydrolysis of Salts
 Hydrolysis is the reaction of a substance with water.
Hydrolysis of salts involves the reaction between the ions of
the salt with H3O+ or OH- ions of water.
o This reactions can disturb the H3O+/OH- balance in water
and produce acidic or basic solutions.
o Identification of salts based on the strength of acids and
bases:
o i. Salts of strong bases and strong acids
- No hydrolysis
-The solution is neutral(neither ion of such a salt reacts to
disturb the H3O+/OH- balance in water).
pH = 7
e.g. NaCl, K2SO4

61
 Contn’dHydrolysis of Salts…
o ii. Salts of strong bases and weak acids
- The anion hydrolyzed
- The solution is basic
- pH is greater than 7
eg. NaF, NaCN, KHNO2
Calculate pH and the percent hydrolysis for 0.10 M solution of sodium cyanide, NaCN.
CN- + H2O HCN + OH-
innitialy 0.1 0 0
at equili 0.1-x x x
Ka of HCN 6.2x10–10, from the relationship Ka x Kb = Kw,
Kb = [HCN][OH-]
[CN-]
1.6x10-5 = (x)(x)
0.1-x
x = 1.27x10-3 M = [OH-]
pOH = 2.89 and pH = 11.10
% hydrolysis = [HCN] x100 = 1.27x10-3 x100 = 1.27 % .
[CN-] 0.1

62
 Contn’dHydrolysis of Salts…
o iii. Salts of weak bases and strong acids
- The cation hydrolyzed
- The solution is acidic
- pH < 7
- eg. NH4Cl
Calculate the pH of 0.03 M NH4Cl. (Kb = 1.75x10-5)
Solution
NH4+ + H2O NH3 + H3O+
0.03-x x x
Ka = [NH3][H3O+] = 5.71x10-10
[NH4+]
5.71x10-10 = (x)(x)
0.03-x
x2 = (5.71x10-10 ) (0.03)
x = 4.13x10-6 M = [H3O+]
pH = - log[H3O+] = -log (4.13x10-6 M)
= 5.38
63
 Contn’d Hydrolysis of Salts…
o iv. Salts of weak bases and weak acids
- the cation and anion hydrolyzed
- the solution can be basic or acidic
i. if Ka = Kb, neutral eg. CH3COONH4
ii. if Ka > Kb, acidic eg. NH4F
(ka= 7.2 X 10-4, Kb= 1.8 X 10-5 )
iii. if Ka < Kb, Basic e.g. NH4CN

64
2.2 Solubility product constants
2.2.1 Solubility and Solubility product
o Solubility :
- is
the amount of the compound that dissolves in a specified volume
of soln.
- it is usually expressed as either g/L or g/1000 mL.
o Solubility product :
- is the equilibrium constant for the reaction in which a solid
salt dissolves to give its constituent ions in solution.
- its physical meaning is if an aqueous soln is left in contact
with excess solid, the solid will dissolve until the condition
[Ay+]x[Bx-]y = Ksp is satisfied there after the amount of
undissolved solid remain constant. In general, for a reaction,
AxBy(s) xAy+(aq) + yBx-(aq)

Ksp = [Ay+]x[Bx-]y
.
65
 Cont’d…

In general, the solubility product of a compound is the product of

the molar concentrations of the constituent ions, each raised to the
power of its stoichiometric coefficient in the equilibrium equation.

66 1/31/2023
 molar solubility, which is the number of moles of solute in 1 L of
a saturated solution (moles per liter), and
solubility, which is the number of grams of solute in 1 L of a
saturated solution (grams per liter).

Figure 1 Sequence of steps (a) for calculating K sp from solubility data and
67
(b) for calculating solubility from Ksp data. 1/31/2023
68 1/31/2023
 Cont’d…

1/31/2023
69
 Cont’d Solubility product constants…
eg. Calculate the molar solubility of lead iodate, Ksp = 2.5 x10–13
Pb(IO3)2(s)  Pb2+(aq) + 2IO3–(aq)
Ksp = [Pb2+][IO3–]2 = 2.5 x10–13
Pb(IO3)2(s)  Pb2+(aq) + 2IO3–(aq)
Initial conc. solid 0 0
Equil.conc. solid x 2x
Substituting the equilibrium concentrations into Ksp
2.5x10–13 = (x)(2x)2
4x3 = 2.5 x10–13
x = 3.97x10–5 M
The equilibrium concentrations of Pb2+ and IO3–, therefore, are
[Pb2+] = x = 3.97x10–5 M; [IO3–] = 2x = 7.9x10–5 M
The molar solubility of Pb(IO3)2 is 3.97x10–5 M
The solubilty in g/l = 3.97x10–5 mol/lx458 g/mol
= 1.82x10-2 g/l
Ex.2. Calculate the solubility of 0.02 M Cu2S (Ksp = 3x10-49)
70
 Calculate the solubility of copper(II) hydroxide, Cu(OH)2 in g/L.
Ksp = 2.2x10-20

71 1/31/2023
 Cont’d…

72 1/31/2023
 The Common Ion Effect and Solubility

1/31/2023
73
 Cont’d…

74 1/31/2023
Practice Exercise Calculate the solubility in g/L of AgBr in
(a) pure water and in
(b) 0.0010 M NaBr. Ksp=7.7x10-13

75 1/31/2023
2.3 Complexation equilibria
 2.3.1 Complexation and Ligand formations
o Complex: a combination of separate groups of atoms/molecules/ions
join together to form a single or large molecule.
- Complex ion: a charged species formed by a combination of central
metal atom (CMA) ion and the ligand.
- CMA accept electron(s);
the formation of complex is dative
bond(coordinate covalent bond) type.
- The charge of the complex ion is depend on:
i. The central ion
if the ligand is neutral, the charge on the
complex ion & CMA are the same as the metal.
e.g. Fe3+ + 6NH3 [Fe(NH3)6]3+ Fig.1 Shows complex
ii. The ligand formed by CA and ligand
if the ligand is charged, the charge of the complex is the sum of
CMA and the ligand
e.g. Fe3+ + 6 SCN- [Fe(SCN)6]2-
76
 Contn’d complexation and Ligand ...
o Ligands are Lewis base that binds with a metal ion.
- Types of ligands:
a. Depending on charge:
- i. Neutral ligand e.g. H2O, NH3, EDTA etc.
- ii. Charged ligand e.g. CN- , SO42-, CO32- etc.
b. Depending on the no of coordination sites:
o i. Unidentate: have one coordination site for complexation rxn
- e.g. Cl-, NH3, and CN-.
- are not analytically use full:
- do not react more completely with metal ion
- their single step reaction will result poor complexation
therefore their formation constant < multidentate ligand.
e.g. Cd2+(aq) + 4(:NH3)4(aq) [Cd(NH3)4]2+(aq)

Lewis acid Lewis base (ligand) complex ion

Kf = [Cd(NH3)42+] = 5.5x107; Kd = [Cd2+][NH3]4 =1.82x10-8
[Cd2+][NH3]4 [Cd(NH3)42+]
77
 Contn’d Complexation and Ligand forma ...
o ii.Multidentate Ligands:
- have more than one a coordination site for complexation rxn, stabilized
1:1 with metal ions in a step.
- eg. EDTA: - has six binding sites

2.3.2 Complex formation with Ligands

The formation of a metal ligand MLn
M + L ML K1 =
ML + L ML2 K2 =
MLn-1 + L MLn K3 =
M + nL MLn ; βn = K1xK2x . . .x Kn
78 Over all formation constant
 Contn’d Complexation and Ligand forma ...
 Cd2+(aq) + NH3(aq) Cd(NH3)2+
Cd(NH3)2+(aq) + NH3(aq) Cd(NH3)22+
Cd(NH3)22+ + NH3(aq) Cd(NH3)32+
Cd(NH3)32+ + NH3(aq) Cd(NH3)42+
Over all Cd2+(aq) + 4NH3(aq) Cd(NH3)42+
Kf = Cd(NH3)42+ = 5.5x107; Kdiss = 1/ Kf = 1.82x10-8
[Cd2+][NH3]4
 Formation constant(Kf)/Stability constant(Ks) is the equilibrium constant
for a reaction in which a metal and a ligand bind to form a metal–ligand complex.
e.g. Cd2+(aq) + 4(:NH3)4(aq) Cd(NH3)42+(aq)
Kf = Kstable = [Cd(NH3)4]2+ = 5.5x107
[Cd2+][NH3)4]4
o Dissociation constant(Kd) is the equilibrium constant for a reaction in which a
metal–ligand complex dissociates to form un-complexed metal ion and ligand .
o Kd = 1/ Kf = [Cd2+][NH3)4]4 = 1.82x10-8
o [Cd(NH3)4]2+
79
2.3.3 Factors affecting stability of complexes
 Factors affecting stability of complexes:
- i. Nature of the ligand
- The more basic the ligand the easier to donate its electron to the acceptor
thus it forms the more stabile complex.
- eg. Consider [Fe(NH3)6]+3 and [Fe(H2O)6]+3
more stable less stable
- ii. The nature of the central metal atom (CMA) ion:
-The more the charge density on the CMA the more readily the
electron accepted.
- As the charge increases the ionic size decreases i.e. the smaller the size the
larger charge density resulting the more stable complex formation.
e.g. Fe[(NH3)6]+3 > Fe(NH3)6]+2
80
 Contn’d Factors affecting stability of ...
- iii. Nature of the complex formed
- Whether the complex is chelated(binds to a metal via more than one
atom ring form) or open chain can affect the stability of the complex
i.e. chelated complex is more stable than open chain complex.
-

- a) chelated complex b) open chain complex.

81
2.4 Oxidation–Reduction (Redox) reactions
2.4.1 Redox Reactions, Reducing and Oxidizing agents
 Oxidation is an increase in oxidation number

- corresponds to the loss, or apparent loss, of electrons.

 Reduction is a decrease in oxidation number

- corresponds to a gain, or apparent gain, of electrons.

 They are referred to as oxidation–reduction, or redox reaction.

b/s oxidation and reduction occur simultaneously,

 Oxidizing agents (also called an oxidant) are species that:
- oxidize other substance
- contain atoms that are reduced
- gain electron(s).

82
 Contn’d Redox Reactions, Reducing and …

 Reducing agents (a reductant) are species that:

- reduce other substances,

- contain atoms that are oxidized,

- lose electrons.

o Example 1 2[Fe(CN)6]4− + Cl2 → 2[Fe(CN)6]3− + 2Cl−

- Reducing agent [Fe(CN)6]4− it donates an electron to chlorine to

form chloride.

- Oxidizing agent chlorine b/s it converts Fe(II) to Fe(III)

83
 Contn’d Redox Reactions, Reducing and …
 Example 2
- 2Fe3+(aq) + H2C2O4(aq) + 2H2O(l) 2Fe2+(aq) +2CO2(g) + 2H3O+(aq)
- Iron is reduced since its oxidation state changes from
Fe3+ to Fe2+.
- Oxalic acid, on the other hand, is oxidized since the oxidation
state for carbon increases from +3 in H2C2O4 to +4 in CO2.
- The separate half-reactions that individually describe the
oxidation and the reduction processes.
- H2C2O4(aq) + 2H2O(l) → 2CO2(g) + 2H3O+(aq) + 2e-
- Fe3+(aq) + e- → Fe2+(aq)

84
2.4.2. Redox reactions in electrochemical cells and electrode
potential
 Electrochemistry involves:
- Electron transfer b/n physically separated oxidizing and
reducing agents
- Interconversions b/n chemical energy and electrical energy.
o All electrochemical reactions are a redox reactions.
o An electrochemical cell is composed of two compartments
or half-cells, each composed of an electrode dipped in a
solution of electrolyte.
- Oxidation half reaction
- Reduction half reaction

85
 note:

86 1/31/2023
 Contn’d Redox reactions in electrochemical …
Types of electrochemical cells:
i. Electrolytic cells
o Are those in which electrical energy from an external
source causes non spontaneous chemical reactions to
occur.
i.e. Electrical energy  chemical energy
 ii. Voltaic /Galvanic cells
o Spontaneous chemical reactions produce electricity and
supply it to an external circuit.
- Chemical reaction → electrical energy (electricity)
- Spontaneous reaction occurs
- Galvanic cells are commonly used as batteries.
87
 Contn’d Redox reactions in electrochemical …
o Electrodes:
- Electrodes are conducting materials in which electron(s)
transfer in to or from the surrounding solution.
o Classification :
- Cathode is the electrode at which reduction occurs as
electrons are gained by some species.
- Anode is the electrode at which oxidation occurs as
electrons are lost by some species.
o Electrode Electrochemical cell
Galvanic cell Electrolytic cell
Anode negative Positive
Cathode positive negative
88
89 1/31/2023
 Contn’d Redox reactions in electrochemical …
Voltaic cells are driven by a spontaneous chemical reaction that
produces an electric current through an outside circuit.
These cells are important because they are the basis for the
batteries that fuel modern society. But they are not the only kind of
electrochemical cell.
The reverse reaction in each case is non-spontaneous and requires
electrical energy to occur.
The general form of the reaction can be written as:
Spontaneous ⟶
Reactants ⇌ Products + Electrical Energy
90
⟵ Non spontaneous
 Electrolytic cells are very similar to voltaic (galvanic) cells in the
sense that both require
a salt bridge,
both have a cathode and anode side, and
both have a consistent flow of electrons from the anode to the
cathode.
However, there are also striking differences between the two cells.
The main differences are outlined below:

91
92
 Figure : Electrochemical Cells. A galvanic cell (left)
transforms the energy released by a spontaneous redox reaction
into electrical energy that can be used to perform work.
The oxidative and reductive half-reactions usually occur in
separate compartments that are connected by an external
electrical circuit; in addition, a second connection that allows
ions to flow between the compartments (shown here as a vertical
dashed line to represent a porous barrier) is necessary to maintain
electrical neutrality.
The potential difference between the electrodes (voltage) causes
electrons to flow from the reductant to the oxidant through the
93
external circuit, generating an electric current.
In an electrolytic cell (right), an external source of electrical
energy is used to generate a potential difference between the
electrodes that forces electrons to flow, driving a nonspontaneous
redox reaction; only a single compartment is employed in most
applications.
 In both kinds of electrochemical cells,
the anode is the electrode at which the oxidation half-reaction
occurs, and
the cathode is the electrode at which the reduction half-reaction
occurs.
94
Galvanic Cell Electrolytic cell
 converts chemical energy into electrical  An electrolytic cell converts electrical
energy energy into chemical energy

 the redox reaction is spontaneous and is  The redox reaction is not spontaneous
responsible for the production of electrical and electrical energy has to be supplied to
energy. initiate the reaction
 The two half-cells are set up in different  Both the electrodes are placed in a same
containers, being connected through the container in the solution of molten
salt bridge or porous partition. electrolyte.
 the anode is negative and cathode is the  the anode is positive and cathode is the
positive electrode. The reaction at the negative electrode. The reaction at the
anode is oxidation and that at the cathode is anode is oxidation and that at the cathode
reduction. is reduction.
 The electrons are supplied by the species  The external battery supplies the
getting oxidized. They move from anode to electrons. They enter through the cathode
the cathode in the external circuit. and come out through the anode.

95
96
 Contn’d Redox reactions in electrochemical …
o The oxidized and the reduced agents are separated from one another by
salt bridge.
 salt bridge:
-Separate or connect the two solutions;
allows the movement of current in the
form of ionic charge.
-Contains inert electrolyte as:
KNO3, KCl,
-its ends fixed with porous frits,
allowing ions to move freely between
the half-cells and the salt bridge.
o Use of Salt bridge:
- prevents the spontaneous mixing
of the aqueous solutions in each
compartment. Fig.2 shows anode, cathode salt bridge.
- allows the migration of ions in both directions to maintain electrical neutrality. This
movement of ions in the salt bridge completes the electric circuit.
97
 Contn’d Redox reactions in electrochemical …
Conventionally:
- Consider figure 3
 The electrode on the left is
the anode/oxidation to occur
Cd(s)  Cd2+(aq) + 2e-
 The electrode on the right
is the cathode/reduction
to occur.
2Ag+(aq) + 2e-  2Ag(s)
o Electron travels through
the external wire from
the anode to the cathode.
o The over all reaction:
2Ag+(aq) + Cd(s)  Cd2+(aq) + 2Ag(s) Fig.3 galvanic cell
- Cd is oxidized and is the reducing agent
- Ag is reduced and the oxidizing agent
98
 Contn’d redox reactions in electrochemical …

Fig.5 galvanic cell

o Shorthand representation:
Cd(s) | Cd(NO3 )2(C1) || AgNO3 (C2) | Ag(s)
Anode cathode
- (||): the salt bridge, the contents of w/c are normally not indicated
- A vertical slash (|): a phase boundary where a potential developed.
- C1 and C2 represent the concentration of the ionic species at the
99
anode and cathode respectively.
 Contn’d redox reactions in electrochemical …
 Write the overall rxn and expressed as in short hand
representation:
 At the anode: Zn(s) Zn2+(aq) + 2e-
At the cathode : Ag+(aq) + e- Ag(s)
Over all reaction: Zn(s) + 2Ag+(aq) 2Ag(s) + Zn2+(aq)
o Zn(s) | ZnCl2 (C1) || AgNO3 (C2) | Ag(s)

100
 Contn’d Redox reactions in electrochemical …
 The standard hydrogen electrode:
o In a redox reaction there is a migration of electron hence, it is
impossible to determine experimentally the potential of any
single electrode.
- The conventional reference electrode is the standard hydrogen
electrode (SHE).
- It contains a piece of metal coated with a grainy black surface of
inert platinum metal, immersed in a 1 M H+ solution.
- Hydrogen/H2, is bubbled at 1 atmospheric pressure through a
glass envelope over the platinized electrode.
o Convention, internationally the SHE is arbitrarily assigned a
potential of exactly 0.000 volt.
- SHE as anode: H2 - 2e- → 2H+ exactly 0.000 V
- SHE as cathode: 2H+ + 2e- → H2 exactly 0.000 V

101
 Contn’d Redox reactions in electrochemical …
o By coupling SHE with another electrode it is possible to
determine the electrode potential.
Because the defined electrode potential of the SHE
contributes exactly 0 volt to the sum, the voltage of the
overall cell then determines the standard electrode
potential of the other half-cell.
-This is its potential with respect to the SHE, measured at
25°C, in 1 M solution and in 1 atmospheric pressure .
o By agreement, the standard cell potential is for a half-cell
as a reduction process.

102
Fig. (a) A cell consisting of a zinc electrode and a hydrogen electrode.
(b) A cell consisting of a copper electrode and a hydrogen electrode.
Both cells are operating under standard-state conditions. Note that in
103 (a) the SHE acts as the cathode, but in (b) it is the anode. 1/31/2023
 Contn’d Redox reactions in electrochemical …
 Electrodes with positive Eoreduction
-Reduction occurs more readily than the reduction of 2H+ + 2e- →H2
-Electrode acts as a cathode versus the SHE.
 Electrodes with negative Eoreduction
-Reduction occurs more difficult than reduction of 2H+ + 2e → H2
- Electrode acts as anode versus the SHE.
o The more +ve the standard state potential favors the more
reduction.
o Example Cu2+ + 2e- → Cu (+0.34V) favors reduction
H2 - 2e- → 2H+ (0.000 v) favors oxidation
Zn2+ + 2e- → Zn (-0.76V) favors oxidation
2H+ + 2e → H2 (0.000 v) favors reduction
 If : - Eocell > 0, spontaneous process (galvanic cell)
104 - Eocell < 0, non spontaneous (electrolytic cell)
 Contn’d Redox reactions in electrochemical …
Standard electrode potentials
o Electrode potential is a measure of the tendency of the ions
to give off or take on electron.
o negative electrode potential indicates that the electrode has a
greater tendency to undergoes oxidation than SHE.
o positive electrode potential indicates that the electrode has a
greater tendency to undergoes reduction(the more positive
the value, the better the oxidizing agent) than SHE.
o Standard state cell potential for redox reaction(Eoredox) can be
calculated as:
Eoredox = Eored – Eo oxd = Eo cathod – Eo anode
- Where: - Eored -standard state cell potential for reduction
- Eo oxd -standard state cell potential for oxidation
- Eo cathod - standard state cell potential for cathode
105 - Eo anode - standard state cell potential for anode
 Contn’d Redox reactions in electrochemical …

106
 1/31/2023
107
 Contn’d Redox reactions in electrochemical …
 Examples:1. Calculate the cell potential for the reaction
Zn(s) /Zn2+(aq) //Cu2+(aq)/ Cu (s)
- The reaction: Cu2+(aq) + Zn(s)  Cu(s) + Zn2+(aq)
- The standard reduction potential for each half reaction is
Zn 2+(aq) + 2e-  Zn(s) E º = -0.76 V
Cu2+(aq) + 2e-  Cu (s) E º = 0.34 V
o From the above electrochemical reaction, zinc is oxidized
and copper reduced, therefore
E°redox = E°red – E°oxd
E°red = 0.34 V and E°oxd = - 0.76 V
E°reac = (0.34 V) – (-0.76 V) = 1.1 V
- Since the potential is positive, the reaction is spontaneous
and carried out in galvanic cell.

108
 Contn’d Redox reactions in electrochemical …
 Examples:3.
What is the standard emf of a galvanic cell made of a Cd electrode
in a 1.0 M Cd(NO3)2 solution and a Cr electrode in a 1.0 M
Cr(NO3)3 solution?
o Solution:
Standard reduction potential
Cr3+(aq) + 3e-  Cr(s) Eº = -0.74 V
Cd2+(aq) + 2e-  Cd(s) Eº = -0.40 V
From the given standard potential, the one with more negative
-0.74V has a higher tendency to oxidize than other in galvanic cell.
Therefore, the reaction of the galvanic cell will be
2Cr(s) + 3Cd2+(aq)  2Cr3+(aq) + 3Cd(s)
Cr(s)/ Cr3+ // Cd2+ /Cd(s)
E°reac = E°red – E°ox = (-0.40 V) – (-0.74 V) = + 0.34 V
109
 2.4.3 Dependence of electrode potential on concentration
 The equilibrium redox reaction equation involving A, B, C, and D
with stoichiometric coefficients a, b, c, and d.
aA + bB cC + dD Note: the superscript ‘o’ signifies
a species expressed by a
The reaction quotient:
c d
unit concentration.
Q = [C] [D] E.g. E°, ΔGo
[A]a[B]b
o The relationship between electrochemical potential and the concentrations of
reactants and products can be determined by
ΔG = –nFEcell .……1
ΔGo = –nFEocell ……2
ΔG = ΔGo + RT ln Q . .……3
–nFEcell = –nFEocell + RT ln Q Where: ΔG – change in free energy
ΔGo – standard free energy change
Nernst equation E° - is the electrochemical potential under
E = E° - RT ln Q standard state conditions.
nF E – Potential of the cell
= E° - RT ln [C]c[D]d F- Faraday’s constant 96485 C mol-1,
nF [A]a[B]b T- temprature 25Co (298K)
Q - the reaction quotient; ln = 2.301log
R – the gas constant 8.314 J mol-1 K-1
110
n- no. electrons involved in the half reaction
 Contn’d Dependence of electrode potential on …
o Substituting appropriate values for R = 8.314 J mol-1 k-1 and
F = 96,485 C mol–1 assuming a temperature of 25 °C (298 K),
and switching from ln to log form gives the potential in volts as
E = Eo – 0.0592 log Q
n
o In general, half-reactions for standard reduction potentials are
written
XOx + ne_  YRed
o The Nernst equation for any cathode half-cell (reduction half-
reaction) is
E = Eo – 0.0592 log [Red]Y
n [Ox]X

111
 Contn’d Dependence of electrode potential on …
 Example:
Zn2+ + 2e-  Zn(s); E0 = -0.763 V
the corresponding Nernst equation is
E = Eo – 0.0592 log 1 (for reduction half reaction)
2 [Zn2+]
We substitute the E0 value into the equation to obtain
E = -0.763 V - 0.0592 log 1
2 [Zn2+]

112
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113
 Contn’d Dependence of electrode potential on …
 Example3
A zinc electrode is submerged in an acidic 0.80 M Zn2+ solution which is
connected by a salt bridge to a 1.30 M Ag+ solution containing a silver
electrode. Determine the cell potential for the electrochemical cell
Zn(s) + 2Ag+(1.3 M) Zn2+(0.80 M) + 2Ag(s) at 298K.
Solution
The standard reduction potential for the half reactions is:
Zn2+ + 2e- → Zn(s) x1 E0red = -0.76 V
Ag+ + e- → Ag (s) x2 E0red = +0.80 V
Ecell = E0cell – (0.0592/n)log Q where, Q = [Zn2+]/[Ag+]2
E0cell = E0red - E0ox = 0.80 V – (-0.76 V) = 1.56 V
Ecell = 1.56 V – 0.0592log ([Zn2+]/[Ag+]2 )
2
Ecell = 1.57V .
114 The reaction proceeds spontaneously (takes place in galvanic cell).
115 1/31/2023
 1/31/2023
116
 Exercise
1

117 1/31/2023
2.4.4. Calculating equilibrium constant from electrode potential
The standard-state electrochemical cell potential, E°
provides an alternative way of expressing the
equilibrium constant for a redox reaction.
-RTlnK = -nFEo

Eo = RTlnK = 0.0592logK
nF n

logK = n Ecell = n ( Eored - Eoox)

0.0592 0.0592

where K is an equilibrium constant that defines the

reaction’s equilibrium position.
118
 Contn’d Calculating equilibrium constant from …
 Example: 1. Cu2+(aq) + Zn(s)  Cu (s) + Zn2+(aq)
E Zn2+/Zn = EoZn2+/Zn - 0.0592 log 1 ----------------------------(1)
2 [Zn2+]
E Cu2+/Cu = Eo Cu2+/Cu - 0.0592 log 1 -------------------------(2)
2 [Cu2+]
At equilibrium equation (1) and (2) are equal, i.e.

EoZn2+/Zn - 0.0592 log 1 = Eo Cu2+/Cu - 0.0592 log 1

2 [Zn2+] 2 [Cu2+]
Eo Cu2+/Cu - EoZn2+/Zn = 0.059 log [Zn2+]
2 [Cu2+]
[Zn2+] = K
[Cu2+]
log [Zn2+] = 2(EoCu2+ - EoZn2+ )
[Cu2+] 0.0592

logK = 2(EoCu2+ - EoZn2+ ) = 2(1.1) = 37.16

0.0592 0.0592
K = 1.4x1037
119

 Contn’d Calculating equilibrium constant from …
Example2.
Ni + Cr3+  Ni2+ +Cr
Cr3+ +3e-  Cr x2; Eo = -0.49 V
Ni2+ + 2e-  Ni x3; Eo = 0.25 V
logK = 2x3(EoCr3+ - EoNi2+ ) = 6(-0.49-0.25) = -75
0.0592 0.0592

K = 1075
Example3.
Calculate K for the reaction
2Fe3+ + 3I-  2Fe2+ + I3-
From the standard reduction potential, we find that

2Fe3+ + 2e  2Fe2+ ; 0.771 V

I3- + 2e  3I- ; 0.536 V

log K = 2(EoFe3+ - EoI-) = 2 (0.771 – 0.536 ) = 7.939

0.0592 0.0592
K = 8.7x107
120
 Contn’d Calculating equilibrium constant from …
 In general for a reaction
Aox + ae-  Ared (1)
Box +be-  Bred (2)
To balance the reaction multiply (1) by b and (2) by a
bAred + aBox bAox + aBred
logK = ab(EoB - EoA)
0.0592
 Exercise
Find the electrode potential equilibrium constant for the reaction
Cu(s) + 2Fe3+ 2Fe2+ + Cu2+ ; Eored = 0.771; Eooxd = 0.339
Answer: Eo = 0.432 V; K = 4x1014

121
Unit Three
STATISTICAL EVALUATION OF ANALYTICAL DATA

 Since analytical chemistry is the science of making quantitative

measurements, understanding the d/ce b/n accuracy and precision is vital.
Also it is important that raw data is manipulated and reported correctly to
give a realistic estimate of the uncertainty in a result.
3.1. Mean, Standard deviation and Variance
 Two common ways estimate of central tendency are the mean and median.
o Mean (X)
- Mean is the numerical average obtained by dividing the sum of the individual
measurements by the number of measurements.
n
X  i 1 X i
3.1
n
- where: - Xi is the individual values of X making up the set of n replicate
measurements.
122 - n number of replicate measurments.
 Contn’d Mean, Standard deviation and Variance
 Standard deviation and Variance
o Two common measures of spread are standard deviation and variance.
o Standard deviation (s):
- measures how closely the data are clustered about the mean.
i.e. the smaller s the more closely the data about the mean.

s

 n i 1 Xi  X 
2
3.2
n 1

o Relative standard deviation (sr ) or coefficient of variation(CV):

s 3.3
sr 
x
o Percent relative standard deviation (%Sr): %Sr = Sr x 100
- Useful in the lab because you can see how wide the distribution is compared to the
mean.
o Variance (S2):
- It is a measure of spread, which is the square of the standard deviation.
- Variance = s 2
123
 Contn’d Mean, Standard deviation and Variance
 Example
o Consider the following results that are obtained for seven replicate
measurements for the mass of iron in a sample.
o Measurement 1 2 3 4 5 6 7
Mass (g) 3.080 3.094 3.107 3.056 3.112 3.174 3.198
Calculate the: a. mean b. standard deviation
c. % relative standard deviation d. variance.
Solution:
a) To calculate the mean, we add the results for all measurements
together as:
3.080 + 3.094 + 3.107 + 3.056 + 3.112 + 3.174 + 3.198 = 21.821
and divide by the number of measurements.
= 21.821/7
124
= 3.117 g
 Contn’d Mean, Standard deviation and …
o b) To calculate the standard deviation, we obtain the
difference between the mean value and each measurement,
square the resulting differences, and add them to
determine the sum of the squares.
(3.080 – 3.117)2 = (–0.037)2 = 0.00137
(3.094 – 3.117)2 = (–0.023)2 = 0.00053
(3.107 – 3.117)2 = (–0.010)2 = 0.00010
(3.056 – 3.117)2 = (–0.061)2 = 0.00372 +
(3.112 – 3.117)2 = (–0.005)2 = 0.00003
(3.174 – 3.117)2 = (+0.057)2 = 0.00325
(3.198 – 3.117)2 = (+0.081)2 = 0.00656
0.01556
o The standard deviation is calculated by dividing the sum of the
squares by n – 1(7-1), where n is the number of measurements,
and taking the square root.
s = 0.051

125
 Contn’d Mean, Standard deviation and:
c) The percent relative standard deviation is
sr = 0.051/3.117
= 0.016
sr (%) = 0.016 × 100%
= 1.6%
d) The variance is just the square of the absolute standard deviation.
Variance = s2 = (0.051)2
= 0.0026

126
 3.2. Accuracy and Precision of Measurements
 Accuracy:
o is a measure of how close an experimental observation lies to the
true value (X ) or the expected value, µ.
o It is usually expressed as in terms of either an absolute error or relative
error.
- Absolute error: E = X - µ
- Relative error : Er = X  µ x 100%

 Precision:
- is a measure of the degree of agreement among measured values
- it is a measure of the spread of data about a central value.
o Expressed in terms of:
- standard deviation:
- variance:
- Coefficient of variance(CV):
127
 Contn’d Accuracy and Precision of …
o Categories precision:
i. Repeatability :
- all measurements are made by: the same analyst; in a period of lab.
work; using the same solutions and the same equipment.
ii. Reproducibility :
- is the precision obtained under any other set of conditions,
including that b/n analysts, or between laboratory sessions for a
single analyst.
Note : Since reproducibility includes additional sources of variability,
the reproducibility of an analysis can be no better than its
repeatability.
128
 Contn’d Accuracy and Precision of …

129
 3.3. Errors in Analytical Results
 Types of Errors in Experimental Data:
o a) Systematic error (determinate error)
- It affects the accuracy of an analysis and are characterized by a systematic
deviation from the true value;
- Resulted from biases instrumental or human factors.
- A positive determinate error results in a central value that is larger than the
true value, a negative determinate error leads to a central value that is
smaller than the true value.
o Source:
i. Sampling errors,
ii. Measurement errors,
iii. Method errors,
iv. Personal errors.
o Example: - improperly calibrated instrument
130
 Contn’d Systematic error (determinate …
1. Sampling errors:
- is an error which occurs when our sampling strategy fails to provide a
representative sample.
- This is especially important when sampling heterogeneous materials.
- Can be minimized with a proper sampling strategy.
 2. Instrumental error (Measurement error):
- is an error due to limitations in the equipment and instruments used to
make measurements...\books\Skoog - Fundamentals of Analytical
Chemistry 8e HQ (Thomson,(3).pdf pp. 95-96
-Analytical instruments and equipments, such as glassware and balances, are
usually supplied by the manufacturer together with a statement of the
instruments and equipments maximum measurement error, or tolerance.
 Can be minimized by frequent recalibration.

131
 Contn’d Systematic error (determinate …
3. personal error
o The error arises due to personal judgments
Example:
- estimating the color of the solution at the end point in titration,
- biases, such as consistently overestimating or underestimating
the value on an instrument’s readout scale;
- misinterpreting procedural directions.
o can be minimized with proper care.

132
 Contn’d Systematic error (determinate …
4. Methodic error:
The non ideal chemical or physical behavior of the
reagent and reaction introduce systematic error.
o The non ideal include:
- the slowness of some reactions,
- incompleteness of others,
- instability of some species,
- non specificity of reagents,
- occurrence of side reaction

133
b) Random error (indeterminate error)
o Errors affecting the distribution of measurements around a
central value and are characterized by a random variation in
both magnitude and direction.
o Caused by the many uncontrollable variables part of every
that are an inevitable analysis so that never be totally
eliminated
o Exist in every measurement
o Indeterminate errors need not affect the accuracy of an
analysis.
o Examples: - electrical noise;
- differences in visual determination.
o Since indeterminate errors are randomly scattered
around a central value. The mean or median is largely
unaffected by the precision of the analysis.
134
 3.4. Confidence Limit
 Confidence Limit for Populations
o The true value of the mean (µ) cannot be determined b/c it requires huge
number of measurements. But we can establish an interval surrounding
mean(X) with in which the population mean is expected to lie with a certain
degree of probability. This interval is the confidence interval and the
boundaries are confidence limit.
o In general, an equation which used to determine the confidence limit for
a single member of a population calculated from the below equation.
X µ Where - z is the deviation of a data point from the mean
z
ó relative to one standard deviation.
- σ is the population standard deviation.
- µ is the population mean

135
 The confidence limits of a sample

The subscript (n − 1) indicates that t depends on

this quantity, which is known as the number of
degrees of freedom, d.f. (usually given the
symbol ν).

The value of t also depends on the degree of

confidence required (The probability of error α)
 Uses of confident limits

• Presentation of the results

• For evaluating the existence of a systematic
error
 Presentation of a result
The sodium ion content of a urine specimen was determined by
using an ion-selective electrode. The following values were
obtained: 102, 97, 99, 98, 101, 106 mM. What are the 95%
confidence limits for the sodium ion concentration?

The mean and standard deviation of these values are 100.5 mM

and 3.27 mM respectively.

n = 6 therefore v = n – 1 = 5.
From the table A.2, if α = 0.05 (95 % confidence limits), t = 2.57
Testing for systematic error
 Tests of significance
 Significance test: is a statistical test w/c can be employed to decide

whether the d/ce b/n the measured and standard amounts can be
accounted for by random error.
• A significance test is designed to determine whether the difference
between two values is too large to be explained by indeterminate
error.
• The first step in constructing a significance test is to state the
experimental problem as a yes or no question.
Examples:
o Does a newly developed method give results that are
significantly different from those obtained when using a standard
method?
o Is there a significant variation in the chemical composition of
samples of a similar material collected from different locations?
140
 Null hypothesis and alternative hypothesis provide answers to the

question

o The null hypothesis(Ho) in statistics states that the mean values

from two sets of measurements are not different.

- Ho: X = µ

Ho- will be retained if the significance test is conducted at 95%

confidence level (α = 0.05)

Null hypothesis (H0) is a statement that the difference between two values
can be explained by random error

141
 Alternative hypothesis(HA)
 A statement that the difference between two values is too great to be
explained by indeterminate error accepted if the significance test
shows that null hypothesis should be rejected.
o The difference between X and µ is too large to be explained by

indeterminate error and must be real

HA: X ≠ µ; Where: X- sample mean; µ- population mean

 Significance test is conducted on the null hypothesis and which is

either retained or rejected
 The alternative hypothesis is accepted if the significance test shows that
null hypothesis should be rejected 142
 After stating the null and alternative hypotheses, a significance level

for the analysis is chosen.

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 The significance level is:

 The confidence level for retaining the null hypothesis

 It is given as a percentage, e.g. 95%

 The probability that null hypothesis is incorrectly rejected

 It is given as α (or P)

Test statistic is calculated from the data and compared with the critical
value found from a table.
143
 A. Comparison of Experimental Mean with a Known Value
(𝐈𝐭 𝐢𝐬 𝐜𝐨𝐦𝐩𝐚𝐫𝐢𝐧𝐠 𝐱 𝐰𝐢𝐭𝐡 𝛍)

Example: the accuracy of an analytical method is determined by analyzing a

standard sample containing a known amount (μ) of analyte
The equation for the test (experimental) statistic (texp) is derived from the
confidence interval for μ

Rearranging the above equation:

The calculated texp is compared with a critical value of t(α,ν)

144
 The critical value is a theoretical value determined by the
 chosen significance level (α), the degrees of freedom for the

sample (ν) and whether the significance test is one-tailed or two-

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tailed
 Values for t(α,ν) are found from tables
 The value of t(α,ν) defines the confidence interval that can be
explained by random errors
 If texp is greater than t(α,ν), then the confidence interval for the data
is wider than that expected from random errors (Figure b)
 The null hypothesis is rejected
 If texp is less than or equal to t(α,ν), then the confidence interval for
the data could be attributed to random error
 The null hypothesis is retained (Figure c)

145
 1/31/2023
If tcalc > tcrit the null hypothesis is rejected. It means
that the probability of being different is smaller than
accepted error α. Usually 0.05.
So, p<0.05 denotes a significant difference.

tcal<tcrit => There is no evidence of systematic error

This doesn’t mean that there are no systematic errors, only that 146
it has not been demonstrated.
 Example: Before determining the amount of Na2CO3 in an unknown
sample, a chemist decides to check the procedure by analyzing a
sample known to contain 98.76% w/w Na2CO3. Five replicate
determinations of the %w/w Na2CO3 in the standard were made with
the following results 98.71% 98.59% 98.62% 98.44% 98.58%.Is the
mean for the five trials significantly different from the known value at
the 95% confidence level?
 Average = 98.59%, s = 0.0973%, texp = 3.91, tcrit(0.05,4) = 2.78

147
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148
 Example:

In a new method for determining selenourea in water, the following values were
obtained for tap water samples spiked with 50 ng ml−1 of selenourea:

Is there any evidence of systematic error?

Solution:

The mean of these values is 50.06 and the standard deviation is 0.956.
Adopting the null hypothesis that there is no systematic error, i.e. μ = 50, and
using equation (3.1) gives

From tTable , the critical value is t4 = 2.78 (P = 0.05). Since the observed
value of is less than the critical value the null hypothesis is retained.
tcal<tcrit => There is no evidence of systematic error
This doesn’t mean that there are no systematic errors, only that
it has not been demonstrated.
 To enhances the usefulness of the significance test:

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 Increase the number of replicate determinations (n)

 Improve the precision (s) of the analysis so as to have a good

estimate of the expected standard deviation (σ)

exercise

 It is suspected that an acid–base titrimetric method has a significant

indicator error and thus tends to give results with a positive

systematic error (i.e. positive bias). 150
 To test this an exactly 0.1 M solution of acid is used to titrate 25.00

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ml of an exactly 0.1 M solution of alkali, with the following results
(ml): 25.06, 25.18, 24.87, 25.51, 25.34, 25.41

 Test for positive bias in these results

For these data we have:

mean = 25.228 ml, standard deviation = 0.238 ml
Adopting the null hypothesis that there is no bias, H0: m = 25.00
using
t = 2.35 151

From Table the critical value is (P 0.05, one-sided test).

 Since the observed value of t is greater than this, the null hypothesis

is rejected and we can conclude that there is evidence for positive

bias from the indicator error.
B. F-test for the Comparison of s and σ
When a particular type of sample is analyzed on a regular basis,
it may be possible to determine the expected standard deviation
(σ) for the analysis
 F-test is a statistical test for comparing two variances to
see if their difference is too large to be explained by
random error.

152
  Fexp is always greater than or equal to 1
A critical value of F(α, νnum,νden), gives the largest value of F that can
be explained by random error

Example: An industrial laboratory for analyzing aspirin tablets has a

known variance of 25 mg. A sample of ten aspirin tablets is selected
and analyzed for the amount of aspirin and yields: 254, 249, 252,
252, 249, 249, 250, 247, 251, 252 mg.
Determine whether the measurement is under statistical control at
153
α = 0.05.
 Solution: s2 = 4.28, σ2 = 25, Fexp = 5.84,
Fcrit(0.05,∞,9) = 3.33

154
 1/31/2023
 Solution: s2 = 4.28, σ2 = 25, Fexp = 5.84, Fcrit(0.05,∞,9) =
3.33

155
 C. F-test For The Comparison Of Standard Deviations
 It is comparing the standard deviations (random errors) of two sets

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of data.

 One-sided test: tests whether a method is more precise than another

method.

Example: to test whether a new analytical method is more precise

than a standard method.

 Two-sided test: tests whether two methods differ in their precision

 The F-test uses the ratio of the two sample variances.

𝒔𝟐
𝟏
𝑭𝒆𝒙𝒑 = 𝟐
 (F is always ≥ 1): 𝒔𝟐
156
 example 1
A proposed method for the determination of manganese in water was
compared with a standard method.
The following results were obtained for a water sample. For each method

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eight determinations were made
 Method Mean (mg/L) s (mg/L)
 Standard method 72 3.31
 Proposed method 72 1.51
 Is the precision of the proposed method significantly greater than that of the
standard method?

Solution
Fexp = 4.805, Fcrit(0.05,7,7) = 3.787
 The variance of the standard method is significantly greater than that of the
proposed method at the 5% probability level. So, the proposed method is more
precise.
example:2

 consider the results of two analysts shown below. is there

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significant difference between their precisions

158
 We have two degrees of freedom for each of the numerator and

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denominator variances (3-1=2). Ftab.= 19.0

Since Fcalculated < Ftabulated , 16.35 < 19.0, we can say the variances
(precisions) are not significantly different
Example:3 -
Two students have a contest to see who is the more precise analyst.
John makes seven determinations of the percentage of toluene in
benzene, and Mary make five. The results are:

159
 1/31/2023
Determine the significance of the two precisions.

The table value (6 and 4 degrees of freedom) is 6.16, so the difference

is not significant at the 95% level 160
 Outliers
• Every experimentalist is familiar with the
situation in which one (or possibly more) of a
set of results appears to differ unreasonably
from the others in the set. A gross error.

• Such a measurement is called an outlier.

 Outliers (G-test)
• G is calculated:

• where Xm and s are calculated with the

suspect value included.
• The test assumes that the population is
normal.
• The suspect value is always a extreme one.
Example 1

Answer
Example 2

Answer
Table: Critical Values Of G (Α = 0.05) For A Two-sided Test
 DIXON’S TEST (Q-TEST)
It compares the difference between the suspected
outlier and its nearest numerical neighbour to the
range of the entire data set.

Remember that the largest – smaller gives the range

The tested values must be ordered
X1,X2,X3, … X(n-1), X(n)

If the calculated value of Q exceeds the critical value the suspect value is
rejected
 Example
• Example: Apply Dixon’s test to the data from the
previous Example
• 0.403, 0.410, 0.401, 0.380,
0.400, 0.413, 0.408

Q = 0.380 − 0.400/(0.413 − 0.380) =0.606

The critical value of Q (P = 0.05) for a sample size 7 is

0.570. The suspect value
0.380 is rejected (as it was using Grubbs’ test).
 Exercises
 Apply the Q test to the following data sets to determine whether the

outlying result should be retained or rejected at the 95% confidence

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level.

 a) 41.27, 41.61, 41.84, 41.70 b) 7.295, 7.284, 7.388, 7.292

2.A Chemist analyzes vitamin c from citrus fruit drink and obtained
the following data
0.219, 0.230, 0.215 & 0.220mg/ml.
a. Identify outlier (questionable result)?
b. Should the outlier retained or rejected at the 95% confidence level?
c. Calculate the mean and standard deviation

168
 Chapter Four
Solutions and Their Concentrations
 A solution is a homogeneous mixture of two or more
substances.
 A solution has two components namely, solute and solvent.


Solute
• A substance that dissolves.
• A substance existing in small proportion.
• The most active component chemically
A solvent is a substance that
 does the dissolving process,
 existing in larger proportion,
 whose physical state doesn’t change during the solution
process and the least active component chemically.
169
 Types of Solutions

 Solutions are classified;

 On the basis of state matter

Solid, liquid, gas solutions

 On the basis of concentration of solute

 Concentrated and dilute solutions

 On the basis of solvent used

 Aqueous and Non aqueous solutions

 On the basis of saturation
 Unsaturated, Saturated and Supersaturated solutions
170
Liquid solutions can be prepared by dissolving ; a solid in a liquid
(for example, ethylene glycol in water – antifreeze solution), or a
gas in a liquid (for example, carbonated beverages, which contain
dissolved carbon dioxide).
In addition to liquid solutions, it is possible to have gaseous
solutions, such as the atmosphere that surrounds the earth, as well as
solid solutions that are formed when a substance is dissolved in a
solid.

171
 Saturated, Unsaturated and Supersaturated Solutions
 A solution containing as much solute as it can stably hold at a
given temperature is said to be a Saturated solution.
If the solution contains less solute, it is said to be an Unsaturated
solution.
 More solute in the solvent at lower temperature. This type of
solution is called a Supersaturated solution.

172
 Different Ways of Expressing Concentration

 The quantity of a solute in a given quantity (weight or volume) of

the solvent or solution is known as concentration of a solution.

173
 When we want to compare in a qualitative way the concentration of
solutions, we use terms dilute and concentrated. Quantitatively the
concentration of solution can be expressed in terms of;
 Molarity (M),
 Formality (F),
 Normality (N),
 Molality (m),
 Mole fraction
ppm, etc.

174
 Molarity and Formality
 Both molarity and formality express concentration as moles of
solute per liter of solution. There is, however, a subtle difference
between molarity and formality.
Molarity is the concentration of a particular chemical species in
solution.
Formality, on the other hand, is a substance’s total concentration in
solution without regard to its specific chemical form. There is no
difference between a substance’s molarity and formality if it dissolves
without dissociating into ions.

175
 The molar concentration of a solution of glucose, for example, is the
same as its formality. For substances that ionize in solution, such as
NaCl, molarity and formality are different. For example, dissolving 0.1
mol of NaCl in 1 L of water gives a solution containing 0.1 mol of Na+
and 0.1 mol of Cl–. The molarity of NaCl, therefore, is zero since there
is essentially no undissociated NaCl in solution. The solution, instead,
is 0.1 M in Na+ and 0.1 M in Cl–. The formality of NaCl, however, is
0.1 F because it represents the total amount of NaCl in solution.

176
 For preparation of solution of any desired molarity (MD) and
volume (VD):
Grams of solute to measure = VD X MD X Msolute

 Where VD = volume desired in liter; MD = molarity desired and

Msolute = molecular weight of the solute.

177
 Normality
 Normality makes use of the chemical equivalent, which is the
amount of one chemical species reacting stoichiometrically with
another chemical species.

No. of equivalent =

N=

Equivalent weight =
178
 Note that this definition makes an equivalent, and thus normality is
a function of the chemical reaction in which the species participates.
Although a solution of H2SO4 has a fixed molarity, its normality
depends on how it reacts. The number of equivalents, n, is based on a
reaction unit, which is part of a chemical species involved in a
reaction. In a precipitation reaction, for example, the reaction unit is
the charge of the cation or anion involved in the reaction; thus for the
reaction.

Pb2+ (aq) + 2I– (aq) PbI2 (s)

179
n = 2 for Pb2+ and n = 1 for I–.
 In an acid–base reaction, the reaction unit is the number of H+ ions
donated by an acid or accepted by a base. For the reaction between
sulfuric acid and ammonia

H2SO4 (aq) + 2NH3 (aq) 2NH4+ (aq) + SO42–(aq)

We find that n = 2 for H2SO4 and n = 1 for NH3.
 For a complexation reaction, the reaction unit is the number of
electron pairs that can be accepted by the metal or donated by the
ligand. In the reaction between Ag+ and NH3

Ag+(aq) + 2NH3(aq) Ag(NH3)22+(aq )

180
The value of n for Ag+ is 2 and that for NH3 is 1.
 Finally, in an oxidation–reduction reaction the reaction unit is the
number of electrons released by the reducing agent or accepted by
the oxidizing agent; thus, for the reaction.

2Fe3+(aq) + Sn2+(aq) Sn4+(aq) + 2Fe2+(aq)

n = 1 for Fe3+ and n = 2 for Sn2+. Clearly, determining the number of
equivalents for a chemical species requires an understanding of how it
reacts. Normality is the number of equivalent weights (EW) per unit
volume and, like formality, is independent of speciation. An equivalent
weight is defined as the ratio of a chemical species’ formula weight
(FW) to the number of its equivalents.
181
 Consequently, the following simple relationship exists between
normality and molarity.
N=nxM
n is; 1) The number of ionizable hydrogen and hydroxide ions per
molecules for acids and bases respectively.
2) Total number of positive charges for salts.

3) Total number of electrons lost or gain in redox reaction.

4) Number of electrons that can share in complexation reaction.
182
 For preparation, solution of any desired normality (ND) and volume
(VD):
Grams of solute to measure = VD X ND X Equ. wtsolute
Example;
 Calculate the equivalent weight and normality for a solution of 6.0
M H3PO4 given the following reactions:

a) H3PO4 (aq) + 3OH– (aq) PO43– (aq) + 3H2O (l)

b) H3PO4 (aq) + 2NH3 (aq) HPO42– (aq) + 2NH4+ (aq)

c) H3PO4 (aq) + F– (aq) H2PO4– (aq) + HF (aq)

183
Solution; For phosphoric acid, the number of equivalents is the
=
number of H+ ions donated to the base. For the reactions in (a), (b), and
(c) the number of equivalents are 3, 2, and 1, respectively. Thus, the
calculated equivalent weights and normalities are

(a) EW = N = n X M = 3 X 6.0 = 18 N

(b) EW = =
N = n X M = 2 X 6.0 = 12 N

(C) EW = N = n X M = 1 X 6.0 = 6.0 N

184
 Molality
 Molality (m) is the mole of the solute per kilogram of the solvent.
m = mole of solute / kg of solvent
 Molality is used in thermodynamic calculations where a
temperature independent unit of concentration is needed.
Molarity, formality and normality are based on the volume of solution
in which the solute is dissolved. Since density is a temperature
dependent property a solution’s volume, and thus it’s molar, formal and
normal concentrations will change as a function of its temperature. By
using the solvent’s mass in place of its volume, the resulting
concentration becomes independent of temperature.

185
 Weight, Volume, and Weight-to-Volume Ratios
 Weight percent (% w/w), volume percent (% v/v) and weight-to-
volume percent (% w/v) express concentration as units of solute per 100
units of sample. A solution in which a solute has a concentration of 23%
w/v contains 23 g of solute per 100 mL of solution.
 Weight percent Grams of solute per 100 g of solution (% w/w).
 Volume percent Milliliters of solute per 100 mL of solution (% v/v).
 Weight-to-volume percent Grams of solute per 100 mL of solution
(% w/v).
For preparation:
 Volume to measure = (% desired/100) x solution volume desired
(% v/v)
186
 Weight to measure = (% desired/100) x solution weight desired
(% w/w)
 Weight to measure = (% desired/100) x solution volume desired
(% w/v)
Example: A concentrated solution of aqueous ammonia is 28.0 % w/w
NH3 and has a density of 0.899 g/mL. What is the molar concentration
of NH3 in this solution?

Solution:

Parts per million (ppm) and parts per billion (ppb)

 Parts per million (ppm) and parts per billion (ppb) are mass ratios of
grams of solute to one million or one billion grams of sample,
respectively.
187
  For example, steel that is 450 ppm in Mn contains 450 mg of Mn for
every kilogram of steel. If we approximate the density of an aqueous
solution as 1.00 g/mL, then solution concentrations can be expressed in
,

parts per million or parts per billion using the following relationships.

 For gases a part per million usually is a volume ratio. Thus, a

helium concentration of 6.3 ppm means that one liter of air contains
6.3 µL of He. For preparation of a desired ppm and ppb, the gram to
be measured is given by

188
Example: The maximum allowed concentration of chloride in a
municipal drinking water supply is 2.50 X 102 ppm Cl–. When the
supply of water exceeds this limit, it often has a distinctive salty taste.
What is this concentration in moles of chloride per liter?
Solution;

189
 Mole fraction
 Mole fraction (x) is the ratio of the number of mole of a given solute
to the total number of moles in a solution. For a two component system
consisting of species i and j, xi = ni /(ni + nj). Where n refer to the
moles of the components. The sum of all mole fractions is unity.
In general for multi-component system,
Xi = ni/ nT
Where nT is the total number of moles of all components.
Activity; What is the difference between mole fraction of non-
electrolytes and mole fraction of electrolytes?

190
 Preparation of Solutions
 Preparing a solution of known concentration is perhaps the most
common activity in any analytical laboratory. The method for
measuring out the solute and solvent depends on the desired
concentration unit and how exact the solution’s concentration needs to
be known.
 Two methods for preparing solutions are described in this section.

 Preparation of Stock Solutions

 Preparation of Solutions by Dilution

191
 Preparation of Stock Solutions
 A stock solution is prepared by weighing out an appropriate portion
of a pure solid or by measuring out an appropriate volume of a pure
liquid and diluting to a known volume. Exactly how this is done
depends on the required concentration unit. For example, to prepare a
solution with a desired molarity you;
 Weigh out an appropriate mass of the reagent,
 Dissolve it in a portion of solvent, and
 Bring to the desired volume.
 To prepare a solution where the solute’s concentration is a volume
percent, you measure out an appropriate volume of solute and add
sufficient solvent to obtain the desired total volume.
192
Example; Describe how to prepare the following three solutions: (a)
500 mL of approximately 0.20 M NaOH using solid NaOH; (b) 1 L of
150.0 ppm Cu2+ using Cu metal; and (c) 2 L of 4% v/v acetic acid using
concentrated glacial acetic acid (99.8% w/w acetic acid).
Solution; Since the concentration is known to two significant figures
the mass of NaOH and the volume of solution do not need to be
measured exactly. The desired mass of NaOH is;
𝐧
𝐌= n=
𝒎
𝐕(𝐋) 𝐌

where n mole, m = given mass and M = molar mass , m is calculated to

be 4 g of NaOH

193
To prepare the solution, place 4.0 grams of NaOH, weighed to the
nearest tenth of a gram, in a bottle or beaker and add approximately
500 mL of water. b) Since the concentration of Cu2+ has four
significant figures, the mass of Cu metal and the final solution volume
must be measured exactly. The desired mass of Cu metal is;

 1 .00 L = 150 mg = 0.15 g Cu

 To prepare the solution we measure out exactly 0.1500 g of Cu into

a small beaker and dissolve using small portion of concentrated HNO3.
The resulting solution is transferred into a 1-L volumetric flask.

194
Rinse the beaker several times with small portions of water, adding
each rinse to the volumetric flask. This process, which is called a
quantitative transfer, ensures that the complete transfer of Cu2+ to the
volumetric flask. Finally, additional water is added to the volumetric
flask’s calibration mark.
c) The concentration of this solution is only approximate so it is not
necessary to measure the volumes exactly, nor necessary to account for
the fact that glacial acetic acid is slightly less than 100% w/w acetic
acid (it is approximately 99.8% w/w). The necessary volume of glacial
acetic acid is;
 2000 ml = 80 ml CH3COOH

 To prepare the solution, use a graduated cylinder to transfer 80 mL of

glacial acetic acid to a container that holds approximately 2 L and add
sufficient water to bring the solution to the desired volume.

195
 Preparation of Solutions by Dilution
 Solutions are often prepared by diluting a more concentrated stock
solution. A known volume of the stock solution is transferred to a new
container and brought to a new volume. Since the total amount of
solute is the same before and after dilution, we know that;
C0V0 = CdVd
 Where Co is the stock solution’s concentration, Vo is the volume of
stock solution being diluted, Cd is the dilute solution’s concentration,
and Vd is the volume of the dilute solution.
Example 1; A laboratory procedure calls for 250 mL of an
approximately 0.10 M solution of NH3. Describe how you would prepare
this solution using a stock solution of concentrated NH3 (14.8 M).
196
Solution;
14.8 M  V0 = 0.10M  0.25 L
V0 = 1.69 × 10-3 liters, or 1.7 mL
 Since we are making a solution that is approximately 0.10 M NH3 we
can use a graduated cylinder to measure 1.7 mL of concentrated NH3,
transfer the NH3 to a beaker, and add sufficient water to give a total
volume of approximately 250 mL.

197
 Activity and Activity Coefficients
 The effective concentration of ionized ions is less than the actual
concentration. The decrease in effective concentration is due to the
interionic attraction.
Each ion is surrounded by an ionic atmosphere of net opposite
charge.
Through these electrostatic associations, each type of ion behaves as
if it were “tied up,” so its concentration seems lower than the actual
concentration.
 The factor that is used to convert actual concentration to effective
concentration (activity) is called activity coefficient.
The actual concentration is the stoichiometric concentration. 198
 If the actual concentration is C, the effective concentration is a, and
activity coefficient is f, the mathematical relationship among the three
factors is given by a = f x C.
Activity coefficient is the measure of the effect of interionic forces
on the ability of ion to take part in chemical reaction.
 If f is less than unity, this means that the ion is confined in its
movement; then a < C, that is, the given amount of ion (concentration)
acts as if there were less ions (activity). If f is equal to unity, then a =
C, i.e. the ion acts in accordance with its concentration in solution. For
strong electrolytes, this is observed only in very dilute solutions (about
0.0001 M) in which the distance between the ions is so great that the
forces operating between them have practically no effect.
199
 In the same way we may ignore forces not too concentrated solution
of weak electrolytes, where only a very small proportion of the
molecules breaks down into ions. Therefore, for such solution, we may
also assume that, f = 1 and hence a = C. The activity of an ion is its
effective, apparent concentration in chemical reactions. For example,
the activity of H+ and Cl- ions in 0.1 N HCl solutions is 0.0814; this
means that these ions behave in chemical reactions as if their
concentrations were 0.0814 g-ion/liter and not 0.1 g-ion/liter.
A further extension of the theory of strong electrolytes is the law of
ionic strength.
This law states that activity coefficient of a given electrolyte is the
same in all dilute solutions of equal ionic strength.
200
 The ionic strength of a solution (µ) is defined as half the sum of the
products of the concentration of all the ions present in solution
multiplied by the square of the charge of the given ion:

Where Ci is the molar concentration of the ion and Zi is the charge on

the ion. For a solution that contains two or more components that do
not interact each other, the ionic strength is given by
µ = ½ (C1Z12 + C2 Z22 + C3Z32 + … + Cn Zn2)

 Where C1, C2,… Cn stands for the concentrations of ion 1, 2, 3,…, n

present in the solution and Zn is their respective charges.

201
 Ionic strength of a solution and the activity coefficient are related by
the following equations developed by P. Debye and E. Huckel.

 For dilute solutions

-log fi = AZi2

 For more concentrated solution (0.1 N- 0.5 N)

-log fi =

202
 Where N is Avogadro’s number, R is universal gas constant, e is
electrical charge, T is absolute temperature and  is dielectric constant.
 The activity coefficients diminish with an increase in ionic strength
of the solution, which depends on the concentration, and charges of all
other ions present. The use of activity instead of concentration is
necessary in the accurate calculations of more advanced chemistry.
However, activity coefficient is not a constant but is dependent upon
 the concentration and the nature of the solute,
 the concentration and charge of all other electrolytes in solution,
as well as other factors.

203
 Therefore, few accurate values for activity coefficients are known and
until more exact numerical data are available for activity coefficients, it
is sufficient to use concentrations in the calculation of qualitative
analysis.
Examples:
1. Calculate the ionic strength of 0.1 M solution of NaCl.
Solution:
µ = ½ [CNa+ZNa+2 + CCl-ZCl- 2] = ½ [(0.1(+1)2 + (0.1)(-1)2] = 0.1

2. Calculate the concentration and activity of each ion in a mixture

obtained by mixing 25 mL of 0.120 M MnCl2 and 35.0 mL of 0.06 M
KCl solution.
Solution: The volume of the mixture is 60 mL. Assuming that the salts
undergo complete dissociation:
204
 Molarity of Mn2+ = (25.0 mL x 0.120 mol/L)/60.0 mL = 0.050
mol/L = 0.050 M

 Molarity of K+ = (35.0 mL x 0.60 mol/L)/ 60.0 mL = 0.035 mol/L

= 0.035 M
 Molarity of Cl- = (2 x (25.0 mL x 0.120 mol/L)/60 mL) + (35.0 mL
x 0.60 mol/L)/ 60.0 mL = 0.135 M

 The ionic strength of the solution is given by:

]

µ = + (0.035)

205
The activity of an ion is given by

-log fi =
 Substituting the values for each individual ion in the above equation,
the activity of each ion will be the same as:
 fMn+2 = 0.243, fCl- = fK+ = 0.702
And the activity of the ions

= = 0.243 x 0.050 = 0.0122 M

= = 0.702 x 0.035 = 0.0246 M

= = 0.702 x 0.035 = 0.0246 M

206
The end of this
chapter

207
 UNIT 5
TITRIMETRIC METHODS OF ANALYSIS
5.1. Fundamentals of Titrimetry
 Titrtaion
is the process by which the standard solution is
gradually added to the solution of
analyte until quantitatively (completely) react.
o Requirements for a titration:
1. The reaction must be stiochiometric.
Thus; there must be a well defined and known
reaction between the analyte and the tirtrant.
2. The reaction should be rapid.
3. There should be no side reaction and
the reaction should be specific. Fig.5.1 titration setup
4. There should be a marked change in some properties (i.e. completeness).
5. The reaction should be quantitative

208 1/31/2023
 5.1.1. Definition of terms
o Direct titration: is a known volume of analyte is
titrated with a standard solution of a reagent or a known
volume of a reagent solution can be titrated with the
analyte solution.
o Equivalent point: is a point of titration where the
reagent added is chemically equivalent to the analyte (i.e.
the reaction is at the stoichiometric ratio).
o End point: is a point at which a physical change (colour)
associated with the equivalent point appears. Ideally, the
end point should coincide with the equivalence point.
o Titration error(Et): the difference in volume or mass
b/n the equivalent point and the end point.
-
209
Et = Vend pt _ Vequ. pt . 1/31/2023
oBack titration is a process in which the excess of a standard
solution used to react with an analyte is determined by titration
with a second standard solution.
For example, the amount of phosphate in a sample can be
determined by adding a measured excess of standard silver nitrate
to a solution of the sample, which leads to the formation of
insoluble silver phosphate:
3Ag+ + PO42- Ag3PO4 (s)
The excess silver nitrate is then back titrated with a standard
solution of potassium thiocyanate:
Ag+ + SCN- AgSCN (s)
Here, the amount of silver nitrate is chemically equivalent to the
amount of phosphate ion plus the amount of thiocyanate used for
the back titration.
210 1/31/2023
 Cont;d definition of terms
• Titrant: is the reagent (standard solution) of accurately known

concentration which is made to react with the analyte or the solution

added or reagent generated in a titration.

 Titrand: The solution to which the titrant is added or it is the substance

being determined during titration. It is the analyte.

 Titrimetry- the method to determinate the concentration of a sample by
employing volumetric instruments. (Burette, pipette, volumetric flask,)
and indicators.

 Titration: It is the process of adding a measured and controlled volume of

a standard solution from a burette to a solution of known volume

(measured by pipette) containing a substance to be determined (analyte).

211 1/31/2023
 5.1.2 Ideal requirements of standard solution
o Standard solution: solutions of accurately known concentrations.
o Standardization: is the process of determination of the concentration of a
solution by measuring accurately the volume of the solution required to react
with an exactly known amount of a primary standard.
 Requirements for a primary Standard:
1 Atmospheric stability; Stable towards air.
2. should be colorless before and after titration to avoid interference with
indicators.
3. It must have high percentage purity.
4. It should have a high formula weight to minimize the effect of error in
weighing.
5. It must be soluble in the solvent of interest.
6. It should be nontoxic.
7. It should be readily available (inexpensive).
8. It should be environmentally friendly. 1/31/2023
212
 Contn’d Ideal requirements of …
o The common examples of primary standards:
a. potassium hydrogen phthalate (KHP):- used to standardize a base
using phenolphthalein as an indicator.
b. potassium hydrogen iodate (KH(IO3)): it is a strong acid used to
standardize bases.
c. sodium carbonate (Na2CO3): used to standardize strong
acids to an end point of pH 4-5 .
o Benzoic acid, sodium oxalate; borax and mercuric oxide are other
primary standards.
 Secondary standard:
 is a solution whose concentration has been accurately determined by
titration of primary standard and which is used to standardize other
solutions. Some
 examples of secondary standards are: CuSO4.5H2O, Na2B4O7.10H2O, and
NaCO3.10H2O. 1/31/2023
213
Titration curve-the curve to describe the relation ship between the
titrant volume and the solution parameter during the process of the
titration.
 In acid –base titration the parameter is pH
In complexometric titration the parameter is pM
In Redox titration the parameter is electrode potential.
Generally titration curve is a plot of function of analyte verses
volume of standard solution.

214 1/31/2023
 Stages in titration process
Any titration involves at least four stages. These are:
 Initial stage: The pure solution of analyte (in titration flask) before
any volume of reagent is added.
 before equivalence point: the volume of reagent added to the
analyte does not make the reaction complete (when there is still excess
of analyte)
 At equivalence point: the mount of reagent added is chemically
equivalent to the amount of substance being determined (analyte).
 After equivalence point: the mount of reagent added is higher
215 than the mount of substance being determined. 1/31/2023
 5.2. Acid Base Titration
5.2.1. Acid Base Titration Curves

 Acid–base titration: A titration in which the reaction between

the analyte and standard solution is an acid– base reaction.

 It is determination of acidity or basicity of a given analyte by adding a

standard solution.
 For acid-base titration, the two most common methods for
determining the end points of titrations are:
 Use of colored indicators
 Use of a pH-meter to monitor the solution pH as a function of the
volume of added titrant

216 1/31/2023
 Cont’d of Acid Base Titration

 The Main Types Of Titration Situations:

A. The sample is a solution of a strong acid and the titrant is a strong base

B. The sample of a solution is a strong base and the titrant is a strong acid

C. A solution of weak acid is titrated with strong base

D. A solution of weak base is titrated with strong acid

E. A solution of weak acid is titrated with a weak base and vice versa

F. Acid- or polyprotic acid is titrated with strong base

G. Acid- or polyprotic base is titrated with strong acid.

217 1/31/2023
 Cont’d of Acid Base Titration
 A. Titrating Strong Acids with Strong Bases
o The titrant is a strong base; the analyte is a strong acid. Both the titrant
and the analyte are completely ionized.
H3O+(aq) + OH–(aq)  2H2O(l)
 Before addition of NaOH (before titration)
o before any base is added, the total concentration of hydronium ion is the
sum of the concentration contributed from the strong acid and from water.
[H3O+]total = [H3O+]acid + [H3O+] water .
Since the acid is strong, the concentration of H3O+ = conc. strong acid
The contribution to hydronium ion from the weak electrolyte (water) is
negligible.
Therefore, [H3O+] = conc. of the strong acid
218 pH = –log [H3O+] = –log [strong acid] 1/31/2023
 Contn’d Titrating Strong Acids with Strong Bases
 Before the equivalence point,
- the acid is present in excess
- the pH is determined by the concentration of excess acid.
- The concentration of hydronium ion can be determined by the
concentration of the acid left unreacted.
[H3O+] = ini.moles of acid-moles of base
Total volume
= Ma Va –Mb Vb
Va +Vb
o Where the subscript:
‘a’ indicates the acid
‘b’ indicates the base.
219 1/31/2023
 Contn’d Titrating Strong Acids with Strong Bases
 At the equivalence point,
- the moles of acid and the moles of the base are equal.
- Since neither the acid nor the base is in excess,
- [H3O+] = [OH-], the pH is determined by the dissociation of
water.
Kw = [H3O+] x [OH-] = 1x10-14,
Since, [H3O+] = [OH-]
[H3O+]2 = 1x10-14
[H3O+] = 10-7 = [OH-]
pH = -log [H3O+]
= -log 10-7
=7
o Thus, the pH at the equivalence point is 7.00
220 1/31/2023
 Contn’d Titrating Strong Acids with Strong Bases
 After equivalent point
- The base is in excess
- the pH is determined by the concentration of excess OH–.
[OH-]excess = total no. of moles of base - no. of moles of acid
Total volume

= Mb Vb – Ma Va
Va + Vb
- The [H3O+] in this solution is not contributed from the acid because it is
completely reacted.
- the only source of hydronium ion is water .
o Hydronium ion concentration can be calculated from the ionization of
water;
[H3O+] = Kw
[OH -]
221 1/31/2023
 Contn’d Titrating Strong Acids with Strong Bases
 Example
o Titration of 50.0 mL of 0.100 M HCl with 0.20 M NaOH.
HCl + NaOH  Na+ + Cl- + 2H2O
- calculate the volume of NaOH needed to reach the equivalence
point. At the equivalence point,
Moles HCl = moles NaOH
MaVa = MbVb
 The volume of NaOH needed to reach the equivalence point,
therefore, is
MaxVa
Vb 
Mb
0.1Mx50mL
= 0.2 M

222 = 25 mL 1/31/2023
 Contn’d Titrating Strong Acids with Strong Bases
 Before equivalent point
i. after addition of 5 mL of NaOH
o Given:
mili moles of acid = Ma x Va
= 0.1 M x 50 mL = 5 mili mole
mili moles of base = Mb x Vb
= 0.2 M x 5 mL = 1 mili mole
Vtotal = Vacid + Vbase = 50 + 5
= 55 mL
o Required:
[H3O+] = ?
[H3O+] = Ma Va- MbVb = 5-1 = 4 = 0.073 M
Va +Vb 55 55
pH= - log[H3O+] = -log 0.073 M = 1.14
o 1/31/2023
223
 Contn’d Titrating Strong Acids with Strong Bases
o ii. if the volume of NaOH = 10 mL
mmole of acid= 5
mmole of base = 0.2 M x 10 mL = 2
Vtotal = (50 +10) mL
= 60 mL

[H3O+] = Ma Va- MbVb

Va + Vb
= 5-2
50 +10
= 3
60
= 0.05 M
pH = - log [H3O+]
= -log 0.05
= 1.3
224 1/31/2023
 Contn’d Titrating Strong Acids with Strong Bases
o iii. if the volume of NaOH =20 ml
mmole of acid = 5 mmole
mmole of base = 0.2 M x 20 mL = 4 mmole
Vtotal = (50 mL+20 mL) = 70 mL
[H3O+] = Ma Va - MbVb = 5 – 4 = 1 = 0.0143 M
Va + Vb 70 70
pH = - log [H3O+] = -log 0.0143 M = 1.85
 At the equivalent point
- At the equivalent point neither HCl nor NaOH is in excess and so the
concentrations of hydronium and hydroxide ions must be equal.
[H3O+] = Kw = 10-7 = [OH-]
pH = - log [H3O+] = - log 10-7 = 7
225 1/31/2023
 Contn’d Titrating Strong Acids with Strong Bases
 After equivalent point
i. addition of 26 mL of NaOH
mmoles of acid = 5
mmoles of base added = 0.2 M x 26 mL = 5.2
mmoles of base unreacted = 5.2 - 5 = 0.2
[OH-] = MbVb - MaVa = 5.2 mmol - 5 mmol = 2.6x10-3 M
Va + Vb 76 ml
o pOH = -log [OH-] = -log 2.6x10-3 M = 2.59
pH + pOH = 14
pH = 14- pOH
= 14 - 2.59
= 11.41
or, [OH-] x [H+] = 1x10-14
[H3O+] = 1x10-14,
2.6x10-3 M
-12
= 3.84 x10 M
pH = -log 3.84x10-12 M
= 11.41
226 1/31/2023
 Contn’d Titrating Strong Acids with Strong Bases
VNaOH in mL: 0 5 10 20 25 26 30
pH: 1 1.14 1.3 1.85 07 11.41 12.1

227 1/31/2023
Figure 5.1 Acid–base titration curve for 50.0 mL of 0.10 M HCl with 0.20 M NaOH.
 B. The titration of a strong base with a strong acid
 Titration curves for strong bases are derived in an analogous way to those
for strong acids.
 Before equivalent point
- the solution is basic
- the hydroxide ion concentration is the same as the concentration of the un
reacted base .
 At the equivalent point
- The solution is neutral
 Beyond the equivalent point
- The solution becomes acidic in the region
 Example.
Calculate the pH during the titration of 20 mL of 0.2 M NaOH with 0.1 M HCl after
the addition of the following volume of reagent.
A. 0 mL B. 10 mL C. 30 mL D. 40 mL E. 50 mL
- The titrant is ?
- The analyte is ?
- The volume to reach equivalent point ?
228 1/31/2023
 Contn’d the titration of a strong base with a strong …
 A. Before addition of HCl (VHCl = 0 mL)
NaOH  Na+ + OH-
0.2 M 0.2 M
- pOH = –log [OH-] = –log [NaOH] = –log (0. 200) = 0.70
- pH = 14 - 0.7 = 13.3
 B. After addition of 10 mL of HCl (i.e. before equivalent point)
- NaOH is in excess and the pOH is determined by the concentration of excess NaOH.
[OH-] = initial moles of base - moles of acid
Total volume
= MbVb - MaVa
Va + Vb
- milimoles of base = Mb x Vb = 0.2 M x 20 mL = 4
- milimoles of acid = Ma x Va = 0.1 M x 10 mL = 1
Total volume= Vacid + Vbase= 20 mL + 10 mL = 30 mL
o Required:
[OH-]= ?
[OH-] = MbVb - Ma Va = 4 - 1 = 3 = 0.1 M
Va +Vb 30 30
pOH = - log[OH-] =-log 0.1 = 1.0
229 pH = 14 - 1 = 13 1/31/2023
 Contn’d the titration of a strong base with a strong …
 C. after addition of 30 mL of HCl (it is also before equivalent point)
- milimoles of base = Mb x Vb = 0.2 M x 20 mL = 4
milimoles of acid = Ma x Va = 0.1 M x 30 mL = 3

[OH-] = MbVb - Ma Va = 4 - 3 = 1 = 0.02 M

Va +Vb 50 50
pOH = - log[OH-] = -log 0.02 = 1.70
pH = 14 - 1.70 = 12.3
 D. after addition of 40 mL of HCl (at the equivalent point)
- milimoles of base = Mb x Vb = 0.2 M x 20 mL = 4
milimoles of acid = Ma x Va = 0.1 M x 40 mL = 4
- milimoles of HCl = milimoles of NaOH
[H3O+] = [OH-].
Kw = [H3O+] x [OH-] = 1x10-14
Since, [H3O+] = [OH-]
[H3O+]2 = 1x10-14
[H3O+] = 10-7 = [OH-]
230 1/31/2023
pH = -log [H3O+] = -log 10-7 = 7
 Contn’d the titration of a strong base with a strong …
 E. addition of 50 mL HCl (after equivalent point)
After equivalent point the solution will contain excess acid.
[H3O+] = MaVa - MbVb
Va + Vb
= 5 mmol - 4 mmol = 0.0143 M
70 ml
pH = - log[H+]
= -log 0.0143 M
= 1.84

231 1/31/2023
  C. Titration of Weak Acid with a Strong Base
 Example:
- Titration of 50.0 mL of 0.100 M acetic acid, CH3COOH, with 0.100 M NaOH.
The volume of NaOH needed to reach the equivalence point;
Moles CH3COOH = moles NaOH
MaVa = MbVb
Vb = MaVa/Mb = (0.1 M) (50 mL) = 50 mL
0.1 M
 Before adding any NaOH
- The pH is that for a solution of 0.100 M acetic acid can be determined by
ionization constant method:
CH3COOH(aq) + H2O(l)  H3O+(aq) + CH3COO–(aq)
Ka = [CH3COO-] x [H3O+] ; Ka for acetic acid = 1.75 x10-5
[ CH3COOH]

- CH3COOH(aq) + H2O(l)  H3O+(aq) + CH3COO–(aq)

Initial conc. 0.1 M 0 0
At equilibrium 0.1 M- x x x
232 1/31/2023
 Contn’d Titration of Weak Acid with a Strong …
o Ka = [CH3COO-] [H3O+]
[CH3COOH]
1.75 x10-5 = (x)(x)
0.1
x2 = 1.75x10-6
x = [H3O+]
= 1.32 x10–3 M
pH = - log [1.32x10–3 M]
= 2.88.
 Before equivalent point
Adding NaOH converts a portion of the acetic acid to its conjugate base,
CH3COO–.
CH3COOH(aq) + OH–(aq)  H2O(l) + CH3COO–(aq)
The pH of a buffer solution can be calculated using the Henderson–Hasselbalch
equation.

233 1/31/2023
 Contn’d Titration of Weak Acid with a Strong …
o pH = pKa + log [salt]
[acid]
–
= pKa + log [CH3COO ]
[CH3COOH]
o The concentration of acetic acid is;
[CH3COOH] = moles of unreacted CH3COOH
Total volume
= MaVa – MbVb
Va + Vb
o The concentration of acetate ion is;
[CH3COO-] = moles of NaOH added
Total volume
= MbVb
Va + Vb

234 1/31/2023
 Contn’d Titration of Weak Acid with a Strong …
 Before the equivalent point
o i. after addition of 10 mL of NaOH
[CH3COOH] = (0.1 M)(50 mL) - (0.1 M)(10 mL) = 0.0667 M
50 mL + 10 mL
[CH3COO-] = (0.1 M)(10 mL) = 0.0167 M
10 mL + 50 mL
The pH of the solution:
pH = pKa + log [CH3COO-] ; ( pKa = -log Ka)
[CH3COOH]
= 4.76 + log 0.0167
0.0667
= 4.16
235 1/31/2023
 Contn’d Titration of Weak Acid with a Strong …

o ii. after addition of 20 mL of NaOH

[CH3COOH] = (0.1 M)(50 mL) - (0.1 M)(20 mL) = 0.043 M

50 mL + 20 mL

[CH3COO-] = (0.1 M)(20 mL) = 0.0286 M

20 mL + 50 mL
The pH of the solution:
pH = pKa + log [CH3COO-] = 4.76 + log 0.0286 M = 4.58
[CH3COOH] 0.043 M

236 1/31/2023
 Contn’d Titration of Weak Acid with a Strong …
 At equivalent point (50 mL of NaOH)
o At the equivalence point:
moles of acetic acid = moles of sodium hydroxide
The concentration of CH3COO–;
[CH3COO-] = MbVb = 0.1 M x 50 mL = 0.05 M
Va + Vb 100 mL

o The pH of the solution can be determined by the amount of the conjugate base, acetate
ion hydrolyzed shown in the reaction:
CH3COO–(aq) + H2O(l)  OH–(aq) + CH3COOH(aq)
Before calculating the pH we need to determine the concentration of OH–.
Ka x Kb = Kw
Kb = Kw ; Ka for CH3COOH = 1.75 x 10-5, then Kb for CH3COO–
Ka
Kb = 1x10-14 = 5.71x10–10
1.75 x10-5

237 1/31/2023
 Contn’d Titration of Weak Acid with a Strong …
CH3COO–(aq) + H2O(l)  OH–(aq) + CH3COOH(aq)
0.05 M – x x x

Kb = [CH3COOH] [OH-]
[CH3COO-]

5.71x10–10 = (x) (x)

0.05 – x

x2 = (5.71x10–10)(0.05)
x = [OH–] = 5.34x10–6 M
The concentration of H3O+, therefore,
[H3O+] [OH–] = 1x10-14
[H3O+] = 1x10-14 = 1x10-14 = 1.87x10–9
[OH–] 5.34x10–6

pH = 8.73
238 1/31/2023
 Contn’d Titration of Weak Acid with a Strong …
 Beyond equivalent point
After the equivalence point NaOH is present in excess
[OH-] = MbVb - MaVa
Va + Vb
pOH = -log [OH-]
i. addition of 60 mL of NaOH
mmole of acid = 5
mmole of base = 60 mL x 0.1 M = 6 mmol
[OH-] = MbVb - MaVa = 6 – 5
Va + Vb (60 + 50) mL

= 1 = 0.0091M
110 mL
pOH = - log[OH-] = 3.04,
pH = 14 - 3.04
239 1/31/2023
= 11.96
 Contn’d Titration of Weak Acid with a Strong …
ii. after addition of 70.00 ml of NaOH

CH3COOH(aq) + OH–(aq)  H2O(l) + CH3COO–(aq)

Initial mmol 5 7 -
Equil. mmol 0 2 5

The [OH-] = MbVb – MaVa

Va + Vb
= 7 mmol - 5mmol
70 + 50 ml
= 0.0167 M
pOH = - log[OH-]
= -log 0.0167 M
= 1.7
PH = 14-1.77
= 12.22 1/31/2023
240
 Contn’d Titration of Weak Acid with a Strong …

Figure. Titration curve for 50.0 mL of 0.100 M acetic acid (pKa = 4.76) with 0.100 M NaOH
241 1/31/2023
 Note that:
o The pH at the equivalent point for the titration of
i. Strong acid with strong base = 7 (neutral)
ii. Strong acid with weak base < 7 (acidic)
iii. Weak acid with strong base > 7 (basic)
iv. Weak acid with weak base = 7, < 7 or > 7 depending on the
extent of ionization of the acid or base.
i.e. if Ka = Kb, pH = 7;
if Ka > Kb, pH < 7 and
if Ka< Kb, pH > 7.

242 1/31/2023
 5.2.2 Acid base indicators
 Acid- base indicators are organic Cpds with complex structures, having colors that are
sensitive to the H3O+/ OH- concentration. They can be weak acids or weak bases
- Indicators for acid- base reaction are substances that change color over a definite pH range.
- One form may be colourless and the other coloured or both may be colored.
 Acid type indicators
- They can be represented by idealized formula, HIn, which ionizes to give its conjugate
base (anionic form) according to the following equation.
HIn(aq) + H2O H3O+(aq) + In-(aq)
Acid color base color
The unionized acid HIn, has one color, and the conjugate base, In-, has another color.
 Example:
for methyl orange the acid colour is red and the basic colour is yellow, so
that, when both forms are present, the mixture of yellow and red appear
orange.
o The pH of the indicator can be written interms of Henderson- Hasselbalch equation.
pH = pKIn + log [In-]
[HIn]

243 1/31/2023
 Contn’d Acid base indicators
o If the color of the unionized form to be observed, [In-] = 1
[HIn] 10
pH = pKIn + log [In-]
[HIn]
pH = pKIn + log 1 = pKIn - 1
10
 Base type indicator
o They can be represented by idealized formula, In,
In-(aq) + H2O OH-(aq) + HIn(aq)
Base colour acid color
 An average observer can see one indicator color rather than the other when there is about
ten times as much of one form of the indicator is compared to the other form.
o If only the colour of the ionized form is observed, [In-] = 10
[HIn] 1
pH = pKIn + log [In-]
[HIn]
pH = pKIn + log 10 = pKIn + 1
1
244 1/31/2023
 Contn’d Acid base indicators
o In going from one colour to the other the pH has changed from
pH = pKIn - 1 to pH = pKIn +1.
i.e. pH = pKIn ± 1.
This is a pH change of 2 and most indicators require a transition range of about two
pH units.
ΔpH = (pKIn + 1) - (pKIn - 1)
= 1+1
=2
o For example:
Methyl red (pKIn = 5) is effective indicator when a pH range
4.2 - 6.2 and shows red in acidic solution (pH nearly equals to 4) and
yellow in basic solution (pH near to 6).
In acidic solution, pH = pKIn – 1
=5–1
= 4, and
In a basic solution, pH = pKIn + 1
=5+1
=6

245 1/31/2023
 Contn’d Acid base indicators

246 1/31/2023
 5.3. Precipitation titration
 is type of reaction in which the analyte and titrant form an insoluble
precipitate.
 Precipitation reaction should occur rapidly and quantitatively.
 the most important precipitating agent is silver nitrate, which is used for
the determination of the halides, like anions SCN-, CN-, CNO- and
several divalent inorganic anions.
 Titrimitric methods based up on silver nitrate are is called argentometric
method
 5.3.1. Titration Curves
It follows the change in either the analyte’s or titrant’s concentration as a
function of the volume of titrant.
For example, in an analysis for Cl– using Ag+ as a titrant
Ag+(aq) + Cl–(aq)  AgCl(s)
o Precipitation titration curve is influenced by the conc. of Ag+ and Cl- and
by KSP value.
o The titration curve may be a plot of pAg or pCl as a function of the
titrant’s volume
247 1/31/2023
 Contn’d Precipitation titration
 Example: Calculate the titration curve for the titration of 50.0 mL of 0.0500 M Cl– with
0.100 M Ag+. The reaction in this case is:
Ag+(aq) + Cl–(aq)  AgCl(s)
Ksp = 1.8x10–10 = [Ag+][Cl]
o Calculate the volume of Ag+ needed to reach the equivalence point.
moles Ag+ = moles Cl– at the equivalence point
i.e. MAg VAg = MCl VCl

MClVCL 0.05M 50mL   25mL

Vag = =
MAg 0.1M

o Before equivalent point

Before the equivalence point Cl– is in excess.
i. addition of 10 mL of Ag+
The concentration of unreacted Cl– after adding 10.0 mL of Ag+ is
[Cl–] = moles of Cl- excess = MCl- VCl- - MAg+VAg+
Total volume VCl- + VAg+
[Cl–] = (0.05 M) (50 mL) - (0.1 M) (10 mL) = 2.5x10-2M
50 mL + 10 mL
248 1/31/2023
pCl = -log[Cl–] = -log (2.5x10-2) = 1.60
 Contn’d Precipitation titration
The change in concentration for Ag+
Ksp = [Ag+] [Cl–] = 1.8x10-10
[Ag+] = Ksp = 1.8x10-10 = 7.2x10-9
[Cl–] 2.5x10-2
pAg = - log[Ag+] = -log7.2x10-9 = 8.14
ii. After addition of 20 mL of [Ag+]
[Cl–] = moles of Cl- excess = MCl- VCl- - MAg+VAg+
Total volume VCl- + VAg+
[Cl–] = (0.05 M) (50 mL) - (0.1 M) (20 mL) = 7.14x10-3M
50 mL + 20 mL
pCl = -log[Cl–] = -log (7.14x10-3) = 2.15
The change in concentration for Ag+
Ksp = [Ag+] [Cl–] = 1.8x10-10
[Ag+] = Ksp = 1.8x10-10 = 2.52x10-8 M
[Cl–] 7.14x10-3
pAg = -log[Ag+] = -log(2.52x10-8 M) = 7.60

249 1/31/2023
 Contn’d Precipitation titration
o Equivalent point
At the equivalent point, the concentration of Ag+ and Cl- are equal.
The concentration of Ag+ and Cl- can be calculated using solubility
product of AgCl.
Ksp = [Ag+] [Cl–]
= 1.8x10-10
[Ag+] = [Cl–] = 1.34x10-5 M
pCl = -log[Cl–] = -log 1.34x10-5
= 4.87
pAg = -log[Ag+] = -log 1.34x10-5
= 4.87
- At the equivalent point, therefore, pCl and pAg are equal.
250 1/31/2023
 Contn’d Precipitation titration
o Beyond equivalent point
After the equivalence point, the titration mixture contains excess Ag+.
i. After adding 35.0 mL of titrant (Ag+)

[Ag+] = moles excess Ag+

total volume
= (0.1 M)(35.0 mL) – (0.05 M)(50.0 mL)
35 mL + 50 mL
-2
= 1.18x10 M
pAg = -log1.18 x10-2 M
= 1.93.
The concentration of Cl– is; [Cl–] = Ksp = 1.8x10-10 = 1.5x10-8 M
[Ag+] 1.18 x10-2 M
pCl = -log[Cl–] = -log1.5x10-8 M
= 7.82
pCl + pAg is always equals to pKsp (= -log Ksp).

251 1/31/2023
 Contn’d Precipitation titration
 VAgNO3 0 10 20 25 35
pCl 1.30 1.60 2.15 4.87 7.82
pAg - 8.14 7.60 4.87 1.93

Fig. Precipitation titration curve for 50.0 mL of 0.0500 M Cl– with 0.100
M Ag +
252 1/31/2023
(a) pCl versus volume of titrant; (b) pAg versus volume of titrant
 5.3.2 End point detection precipitation titration
o There are three distinct methods for the titration of chloride with
silver based up on the different types of indicators.
These are:
1. Reagents which can react with the excess titrant used that
yield a colored solid (precipitate), Mohr Method.
2. The indicator reacts with excess titrant to form a colored
soluble complex. The reaction product is a complex of titrant and
the indicator, Volhard Method.
3. Indicator adsorbed on the surface of the precipitate formed during
titration. The adsorbed indicator has a different colour than the
dissolved indicator. The adsorptions of an indicator does not occur
until an excess of titrant is added, Fajans Method.
253 1/31/2023
 Contn’d End point detection precipitation titration
1. The Mohr Method
o Chromate salt has been added to the solution act as the indicator.
- The excess silver ion reacts with the indicator at the equivalent point to precipitate
silver ion to form red silver chromate.
CrO42- + 2Ag+  Ag2CrO4
(yellow)pre-equi. pt (red) at equi. pt
- The concentration of Ag+ at equivalent point is 1.35x10-5 M
i.e. [Ag+] = Ksp = √(1.82x10 -10 )= 1.35 x 10-5 M
- The concentration of chromate ion required to start the formation of Ag2CrO4
(Ksp = 1.2 x 10-12)
Ag2CrO4 → 2Ag+ + CrO4-2
Ksp = [Ag+]2[CrO4-2]
[CrO4-2] = Ksp = 1.2 x 10-12
[Ag+]2 (1.35x10-5)2

[CrO4-2] = 6x10-3M
254 1/31/2023
 Cntn’d End point detection precipitation titration
o The Mohr titration must be neutral or slightly basic (pH = 7-10).
Why does the Mohr method restricted with in this pH range?
• i. If the solution is too acidic,
- to prevent removal of CrO41- as HCrO4 i.e. wastage
- the chromate reacts with H+ to form hydrogen chromate ions,
which reduces the concentration of chromate ion or it needs more Ag+ to
form Ag2CrO4 precipitate.
- It will lengthen equivalent point.
CrO4-2 + H+  HCrO4-1
• ii. If the solution is basic (at pH > 10),
- Coprecipitation of AgOH
- there are enough hydroxide ions present to cause the formation of
silver hydroxide.
2Ag+ + 2OH-  2AgOH  Ag2O + H2O
255 1/31/2023
 Cntn’d End point detection precipitation titration
 2. The Volhard method
o It is an indirect or back titration method in which an excess of a standard
solution of silver nitrate is added to a chloride solution.
The excess silver nitrate is then determined by titration with a standard
solution of ammonium or potassium thiocyanate with ferric ion as an
indicator.
Ag+ + Cl-  AgCl + Ag+ (excess)
Ag+ (excess) + SCN-  AgSCN(s) (White)
o The end point is detected by adding Fe(III) as a ferric alum (ferric
ammonium sulfate), which forms a soluble red complex with first excess
of titrant. The first excess of thiocyanate reacts with the ferric ion to form
the intensely colored FeSCN- complex,
Fe3+ + SCN-  FeSCN2+(Red)

256 1/31/2023
 Cntn’d End point detection precipitation titration
 3. The Fajans Method (adsorption indicator Method)

- Some organic compounds adsorb strongly on certain

precipitates and undergo a change in colour up on

adsorption so that they can be used as indicator for selected
titrtaions.

- For e.g. Fluorescein is a typical adsorption indicator. The

pH is adjusted b/n 7 and 10 to keep the indicator as FI- in
the soln.

- Before the equivalence point, there is excess Cl- in the

1/31/2023
solution and the Cl- adsorbed on the surface of precipitate.
257
 Cntn’d End point detection precipitation titration

o The negative fluorescein ions are repelled by the negative

charged surface and there by keeps the ions in solution.

o But after the equivalence point, silver ion exists in solution in

excess and is attracted to the silver chloride precipitate to yield a

positively charged surface.

o So the FI- can not be repelled but is adsorbed on the surface of

the precipitate with a resulting change in the color of the

precipitate from white to pink.

258 1/31/2023
 Cntn’d End point detection precipitation titration

Cl- Ag+
 Cl- Cl- Ag + AgCl(s) Ag+
AgCl(s)
Cl- AgCl(s) Cl- AgCl Ag+ Ag+
Cl- Cl- Ag+ Ag+
Before equivalent point At equivalent point After equivalent point

259 1/31/2023
 5.4 Complexometric Titration
 It is a form of Volumetric analysis which forms
colored complex that indicates the end point of
titration. It is also useful for the determination
of a mixture of different metal ion in solution.
- EDTA, is an aminocarboxylic acid,
a Lewis acid, has six binding sites (the four carboxylate groups and
the two amino groups), providing six pairs of electrons.

-
260 Figure 5.4 a structure of EDTA 1/31/2023
 Contn’d Complexometric Titration
Ethylene diamineteraacetic acid-also called (Ethylene dinitrilo
teraacetic acid) is the most widely used complexometric titrant.
 EDTA is the most commonly used chelating agents as it can form
complexes with a wide range of metals.
The ability of EDTA to complex is dependent on its form.
The most desirable state is the Y4- form.
As the pH increases, more EDTA becomes Y4-.
We will represent EDTA by the symbol H4Y .
It is a teraprotic acid and the hydrogen’s in H4Y refer to the four
ionizable hydrogen’s.
261
1/31/2023
 Contn’d Complexometric Titration
The resulting metal–ligand complex, in which EDTA forms a
cage-like structure around the metal ion is very stable. All
metal–EDTA complexes have a 1:1 stoichiometry.

 Fig. 5.4.c curve for

complexometric
titration in a metal
M with :
 A) a tetradentate
ligand to give MD
B) bidentatae ligand
to give MB2;
 Figure 5.4 b C) Unidentate ligand
EDTA forms a cage-like to give MA2
structure around the metal
ion.
262 1/31/2023
 Contn’d Complexometric Titration
 The acid EDTA is a weak acid usually written as H4Y, dissociate in four steps.
H4Y H+ + H3Y- ; Ka1 = [H+][H3Y-] = 1.02x10-2
[H4Y]

H3Y- H+ + H2Y2- ; Ka2 = [H+][H2Y-] = 2.14x10-3

[H3Y]

H2Y2- H+ + HY3- ; Ka3 = [H+][H2Y-] = 6.92x10-7

[H2Y2-]

HY3- H+ + Y4- ; Ka4 = [H+] [Y4-] = 5.5x10-11

[HY3-]

263 1/31/2023
 Contn’d Complexometric Titration
 It is the unprotonated ligand Y4- that forms complexes with metal
ions, that is the protons are displaced by the metal ions upon
Complexation.
Note: Why EDTA is a common titrant in Complexometric
titration?
 1. It combines with metal ions with 1:1

 2. The chelate formed by EDTA are stable to be used for

Titrimetric because EDTA is multidentate
 3. It can be used to determine every metal except alkali metals.

264 1/31/2023
 5.4.1. Complex of EDTA and metal Ions
o Solutions of EDTA are particularly valuable as titrants because the
reagents combine with metal ions 1:1 ratio regardless the charge on
the metal ions.
The formation constant, KMY for EDTA complexes Can be expressed as :
Mn+ + Y4- MY(n-4)+ ;
KMY (Kf ) = [MY(n-4)+] ….…….……… 1 formation constant
[Mn+][Y4-]
Example: the formation of Cd2+ and EDTA.
Cd2+(aq) + Y4–(aq) CdY2–(aq)
Al3+(aq) + Y4–(aq) AlY–(aq)
KAlY - = [AlY -]
[Al3+][Y4-]
265 1/31/2023
 Contn’d Complex of EDTA and metal Ions
o α4 = [Y4-] ; .....................................................................................2
CT
CT = total concentration of un-complexed EDTA.
α4 = the fraction of total EDTA species that exists in the form of Y4-
o CT = [EDTA] = [Y4-] +[HY3-]+[H2Y2-]+[H3Y-]+[H4Y].
Example:

o The fraction, a metal present as uncomplexed (free) Mn+ is given by:

αMn+ = [Mn+] ; .......................................................................3
CM
Where: Mn+ is uncomplexed metal
CM is total metal concentration
o Mn+ + Y4- MY(n-4)+
KMY(Kf) [MY(n-4)+] ……………. From equation 1
=
[Mn+] α4 CT
KMYα4 = KMY’(Kf ’) = [MY(n-4)+] ………...…….…...4 is conditional formation
266 1/31/2023
[Mn+]CT constant
 5.4.2. EDTA Titration Curves
 Example:
Calculate the pCd in the titration of 50.0 mL of 5.00 x10–3 M Cd2+
with 0.0100 M EDTA at a pH of 10 and in the presence of 0.0100 M
NH3.
Since the titration is carried out at a pH of 10, some of the EDTA is
present in forms other than Y4–. In addition, the presence of NH3
means that the EDTA must compete for the Cd2+. To evaluate the
titration curve, therefore, we must use the appropriate conditional
formation constant.
 From Tables 5.4.2.a , 5.4.2.b and 5.4.2.c we find that aY4– is 0.35
at a pH of 10, that a αCd2+ is 0.0881 when the [NH3] is 0.01M and
Kf = 2.9 x1016
 KMY’’(Kf ‘’ ) = αY4–x αCd2+ x Kf(KM) = (0.35)(0.0881)(2.9 x1016)
= 8.9x1014
267 1/31/2023
 Contn’d EDTA Titration Curves
 The first task in calculating the titration curve is to determine the
volume of EDTA needed to reach the equivalence point. At the
equivalence point we know that
Moles EDTA = moles Cd2+
MEDTAVEDTA = MCdVCd
VEDTA = MCdVCd = (0.005M)(50mL) = 25 mL
MEDTA 0.01M
 Before the equivalence point, Cd2+ is in excess, and pCd is
determined by the concentration of free Cd2+ remaining in solution.

268 1/31/2023
 Contn’d EDTA Titration Curves
o i. After the addition of 5.0 mL of EDTA, the total concentration of Cd2+ is
[Cd] = moles excess Cd2+ = MCdVCd - MEDTAVEDTA
VT VCd+VEDTA
= 0.005Mx50mL – 0.01Mx5mL = 0.00364M
50mL + 5 mL
o The fraction αCd2+ present as uncomplexed (free) Cd2+ we use the below equation:
αCd2+ = [Cd2+] ;
CCd
i.e. [Cd2+] = αCd2+xCCd = 0.0881x0.00364 = 0.000321M
Thus pCd = -log[Cd2+] = -log[0.000321] = 3.49
 ii. After the addition of 10 mL of EDTA
[Cd] = moles excess Cd2+ = MCdVCd - MEDTAVEDTA
VT VCd + VEDTA
= (0.005Mx50 mL) – (0.01Mx10mL) = 0.0025 M
50 mL + 10 mL
i.e. [Cd2+] = αCd2+xCCd = 0.0881x0.0025 = 0.0022
pCd = -log[Cd2+] = -log(0.0025M) = 3.66
269 1/31/2023
 Contn’d EDTA Titration Curves
 At the equivalent point
o All the Cd2+ initially present is now present as CdY2–.
o The concentration of Cd2+, therefore, is determined by the
dissociation of the CdY2– complex. To find pCd we must first
calculate the concentration of the complex.
[CdY2–] = initial moles Cd2+ = MCdVCd = 0.005Mx50 mL = 0.00333 M
VT VCd + VEDTA 50 mL+ 25 mL
CdY2- Cd2+ + Y4-
- Letting the variable x represent the concentration of Cd2+ due to the dissociation
of the CdY2– complex, we have
o Kf’’ = αCd2+xαY4-xKf = [CdY2-] = 0.00333 = 8.9x1014 X2
CCdCEDTA xx
x = CCd = 1.93x10-9 M
[Cd2+] = αCd2+xCCd = (0.0881)(1.93x10–9 M) = 1.70x10–10 M
270 pCd = 9.77. 1/31/2023
 Contn’d EDTA Titration Curves
 After the equivalence point, EDTA is in excess, and the [Cd2+] is determined
by the dissociation of the CdY2– complex. To calculate CCd we must first
calculate [CdY2–] and CEDTA.
 i. After adding 30.0 mL of EDTA
[CdY2-] = initial moles Cd2+ = MCdVCd = 0.005Mx50mL = 0.00313 M
VT VCd +VEDTA (50+30) mL
CEDTA = initial moles EDTA = MEDTAVEDTA = 0.01x30 – 0.005x50 = 0.000625M
VT VCd + VEDTA (50 + 30) mL
 From Table: 5.4.2.a , 5.4.2.b and 5.4.2.c we find that aY4– is 0.35 at a pH of 10,
that a αCd2+ is 0.0881 when the [NH3] is 0.01M and Kf = 2.9 x1016
- KMY’’(Kf˝ )= αY4–x αCd2+xKf(KM) = (0.35)(0.0881)(2.9 x1016) = 8.9x1014
Kf ’’ = αCd2+xαY4-xKf = [CdY2-]
CCdCEDTA
8.9x1014 = 0.00313 M ; CCd = 5.6x10-15M
CCd(0.000625M)
[Cd2+] = αCd2+xCCd = (0.0881)(5.6x10-15M) = 4.93x10-16
pCd = -log[Cd2+] = -log(4.93x10-16M) = 15.31
271 1/31/2023
 Contn’d EDTA Titration Curves

 Figure
Complexometric titration curve for 50.0 mL of 5x10–3 M Cd2+ with 0.0100 M
EDTA at a pH of 10.0 in the presence of 0.0100 M NH3.
272 1/31/2023
 Contn’d EDTA Titration Curves

 Tables 5.4.2.a Values of αMn+ for selected concentration of NH3

273 1/31/2023
 Contn’d EDTA Titration Curves

 Table5.4. b Values of αY-4 at selected pHs

274 1/31/2023
 Contn’d EDTA Titration Curves

 Table 5.4c Formation constant for EDTA Complexes

275 1/31/2023
 5.4.3 Complexometric Titration Indicators
 Most indicators for complexation titration are organic dyes that

form complexes with metal ions.

- The indicator, Inm-, is added to the solution of analyte forming a

colored metal-indicator complex, Minn-m .

- As EDTA is added, it react with the free analyte, and then

displaces the indicator from the metal complex, affecting a

change in the solution’s colour.

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 Contn’d Complexometric Titration Indicators
 The accuracy of the end point depends on the strength of the metal-

indicator complex relative that of the metal-EDTA complex.

 If the metal-indicator complex is too strong the color change

occurs after the equivalent point.

 If the metal-indicator complex is too weak however, the end

point is signalled before reaching the equivalent point.

 The conditional formation constant for the metal indicator

complex, therefore, depends on the solution pH.

277 1/31/2023
Contn’d Complexometric Titration Indicators
 This provides some control over the indicator’s titration error.

 The apparent strength of a metal-indicator complex can be

adjusted controlling the pH at which the titration is carried out.
 Unfortunatly, b/c they are also acid-base indicators, the color of
the uncomplexed indicator change with pH.
 A small amount of indicator is added to the sample soluton, it
forms a red complex with the part of Cd2+: the color of
uncomplexed indicator is blue.
278 1/31/2023
Contn’d Complexometric Titration Indicators
o As soon as all the free Cd2+ is titrated, the EDTA displaces the

indicator from the Cd2+, Causing in color from red to blue.

o The metal indicator complex must be less stable than the metal-

EDTA complex; otherwise EDTA will not displaced from the metal.

CdIn- + H2Y-2 CdY2- + HIn2- + H+

(Red)(colorless) (colorless)(blue)

• Dye Eriochrome Black T (EBT) is a typical metal ion indicator that

is used in the titration of several common cations.
279 1/31/2023
Contn’d Complexometric Titration Indicators

280 1/31/2023
 5.5. Redox Titration Curves
o This titration involves electron transfer reaction between two redox
species
o a titration in which the reaction between the analyte and titrant is an
oxidation/reduction reaction;
o for example, the reaction between cerium(IV) and iron(II) to form
cerium(III) and iron(III).
5.5.1. Redox Titration Curves
o Consider, for example, a titration in which the analyte in a reduced
state, Ared, is titrated with a titrant in an oxidized state, Tox.
The titration reaction is
Ared + Tox  Aox + Tred

281 1/31/2023
 Contn’d Redox Titration Curves
o The electrochemical potential for the reaction is the difference
between the reduction potentials for the reduction and oxidation half-
reactions
Erxn = Ereduced – Eoxidized
Erxn = ETox/Tred – EAox/Ared
 Before the equivalence point
It consists of a mixture of appreciable quantities of both the oxidized
and reduced forms of the analyte, but very little unreacted titrant. The
potential, therefore, is best calculated using the Nernst equation for
the analyte’s half-reaction.
E = Eo – 0.059 log [Ared] Eo = standard reduction potential
n [Aox] n = number of electrons lost or gained

282 1/31/2023
 Contn’d Redox Titration Curves
 At the equivalent point
The reaction’s electrochemical potential, Erxn, is zero, and
Ereduced = Eoxidized
ETox/Tred = EAox /Ared

Example:
Calculate the potential for the titration of 50.0 mL of 0.100 M
Fe2+ with 0.100 M Ce4+ in a matrix of 1 M HClO4.
The reaction is:
Fe2+(aq) + Ce4+(aq)  Ce3+(aq) + Fe3+(aq)

283 1/31/2023
 Contn’d Redox Titration Curves
 First we need to calculate the volume of Ce4+ needed to reach the
equivalence point. From the reaction,
Moles Fe2+ = moles Ce4+
MFe2+ x VFe2+ = MCe4+ x VCe4+
VCe4+ = MFe2+ x VFe = (0.1 M) (50 mL) = 50.0 mL
MCe4+ (0.1 M)
 Before the equivalence point
i. after adding 5 mL of Ce4+
mmole of Fe2+ = 0.1 M x 50 mL = 5
mmole of Ce4+ = 0.1 M x 5 mL = 0.5
Fe2+(aq) + Ce4+(aq)  Ce3+(aq) + Fe3+(aq)
Ini. mmole 5 0.5 - -
Equi. mmole 4.5 0 0.5 0.5

284 1/31/2023
 Contn’d Redox Titration Curves
 The concentration of species at equilibrium,
[Fe2+] = mmole = 4.5 mmole = 0.0818 M
total volume 5 mL+50 mL
[Fe3+] = mmole = 0.5 mmole = 0.0091M
total volume 5 mL+50 mL
The potential can be calculated using Nernestian equation,
Ecell = Eo – 0. 059 log[reduced] Eo Fe3+/ Fe2+ = 0.77 V
n [oxidized]
= Eo – 0. 059 log [Fe2+]
1 [Fe3+]
E Fe3+/Fe2+ = 0.77 V - 0. 059 log [0.0818 M]
1 [0.0091 M]
= 0.71 V 1/31/2023
285
 Contn’d Redox Titration Curves
o ii/ after adding 10 mL of Ce4+

mmole of Fe2+ = 0.1 M x 50 mL = 5

mmole of Ce4+ = 0.1 M x 10 mL = 1
Fe2+(aq) + Ce4+(aq)  Ce3+(aq) + Fe3+(aq)
Initial mmole 5 1 - -
Equil. mmole 4 0 1 1
The concentration of species at equilibrium,
[Fe2+] = mmole = 4 mmole = 0.067 M
total volume 10 mL+50 mL
[Fe3+] = mmole = 1 mmole = 0.0167 M
total volume 10 mL+50 mL
Ecell = Eo – 0. 059 log [reduced]
n [oxidized]
E Fe3+/Fe2+ = 0.77 V - 0. 059 log [0.067 M]
1 [0.0167 M]
= 0.73 V
286 1/31/2023
 Contn’d Redox Titration Curves
 At the equivalence point
The moles of Fe2+ and the moles of Ce4+ added are equal. As a result, the potentials for the
two half-reactions are the same.
Eeq = Eo Fe3+/Fe2+ - 0. 059 log [Fe2+] ………….(1)
1 [Fe3+]

Eeq = Eo Ce4+/Ce3+ - 0. 059 log [Ce3+]…………(2)

1 [Ce4+]
Add up these two equations:

2Eeq = Eo Fe3+/Fe2++ Eo Ce4+/Ce3+ - 0. 059 log [Ce3+][Fe2+]

1 [Ce4+][Fe3+]
At the equivalence point, [Fe2+] = [Ce4+] and [Fe3+] = [Ce3+], thus the above equation
becomes
2Eeq = Eo Fe3+/Fe2++ Eo Ce4+/Ce3+ - 0. 059 log 1 (log 1 = 0)
1 1
but : Eo Fe3+/Fe2+ = 0.7 7V and Eo Ce4+/Ce3+ = 1.7 V
287 1/31/2023
 Contn’d Redox Titration Curves
 Eeq = Eo Fe3+/Fe2+ + EoCe4+/Ce3+ = 0. 77 V + 1.7 V = 1.23 V
2 2
In general, E at the equivalnce point is given by

E = nred Eored + nox Eoox

2
Where:
Eored = standard potential for reduced substance
Eoox = standard potential for oxidized substance
nred = no. of electrons involved in reduction reaction
nox = no. of electrons involved in oxidation reaction.

288 1/31/2023
 Contn’d Redox Titration Curves
 After the equivalence point
After equivalent point, the potential determined by the concentration of the
excess Ce4+ and Ce3+ produced.
i. after adding 60.0 mL of titrant (Ce4+)
The potential can be calculated using the Nernst equation for the titrant’s half-
reaction.
mmole of Fe2+ = 0.1 M x 50 mL = 5
mmole of Ce4+ = 0.1 M x 60 mL = 6
Ecell = Eo – 0. 059 log [reduced]
n [oxidized]
Fe2+(aq) + Ce4+(aq)  Ce3+(aq) + Fe3+(aq)
Initial mmole 5 6 0 0
Equil. mmole 0 1 5 5
The concentration of species at equilibrium,
[Ce3+] = mmole = 5 mmole = 0.045 M
289
total volume 60 mL + 50 mL 1/31/2023
 Contn’d Redox Titration Curves
[Ce4+] = mmole = 1 mmole = 0.0091M
total volume 60 mL + 50 mL
E Ce4+/Ce3+ = Eo – 0. 059 log [Ce3+]
1 [Ce4+]
E Ce4+/Ce3+ = 1.7 V – 0. 059 log 0.0091 M
1 0.045 M
E Ce4+/Ce3+ = 1.66V
ii. after addition of 70 mL of Ce4+
mmole of Fe2+ = 0.1 M x 50 mL= 5
mmole of Ce4+ = 0.1 M x 70 mL= 7
Ecell = Eo – 0. 059 log [reduced]
n [oxidized]

Fe2+(aq) + Ce4+(aq)  Ce3+(aq) + Fe3+(aq)

Initial mmole 5 7 0 0
Equil. mmole 0 2 5 5
290 1/31/2023
 Contn’d Redox Titration Curves
 The concentration of species at equilibrium,
[Ce3+] = mmole = 5 mmole = 0.042 M
total volume 70 mL+50 mL

[Ce4+] = mmole = 2 mmole = 0.017 M

total volume 70 mL+50 mL

ECe4+/Ce3+ = Eo – 0. 059 log [Ce3+]

1 [Ce4+]

ECe4+/Ce3+ = 1.7 V – 0. 059 log 0.042 M

1 0.017 M
ECe4+/Ce3+ = 1.68V

291 1/31/2023
 Contn’d Redox Titration Curves
 Vlm of Ce4+ 5 10 50 60 70
E(V) 0.71 0.73 1.23 1.66 1.68

E(V)

Volume of Ce4+ (mL)

Figur. Redox titration curve for 50.0 mL of 0.100 M Fe2+ with 0.100 M Ce4+ in 1 M HClO4.
292 1/31/2023
 5.5.2. Oxidation – Reduction Indicators
 General redox indicators do not participate in the redox titration,
but whose oxidized and reduced forms differ in color.
o When added to a solution containing the analyte, the indicator
imparts color that depends on the solution’s electrochemical
potential .
o The relationship between a redox indicator’s change in color and the
solution’s electrochemical potential is easily derived by considering
the half-reaction for the indicator.

293 1/31/2023
 Contn’dmOxidation – Reduction Indicators
o Inox + ne–  Inred
Where, Inox = the indicator’s oxidized form, and
Inred = is the reduced form
The Nernst equation expresses this reaction as
E = Eo Inox/Inred – 0.0592 log [Inred]
n [Inox]
If we assume that the indicator’s color in solution changes from that of
Inox. to that of Inred. when the ratio:
[Inred] ≤ 10
[Inox] 1
E = Eo Inox/Inred – 0.059 log 10
n
E = Eo Inox/Inred – 0.059
n
If we assume that the indicator’s color in solution changes from Inred to
that of Inox when the ratio
294 1/31/2023
 Contn’dOxidation – Reduction Indicators
If we assume that the indicator’s color in solution changes from Inred to
that of Inox when the ratio: [Inred] ≥ 1
[Inox] 10
E = Eo Inox/Inred – 0.059 log 1/10
n
= Eo Inox/Inred + 0.059
n
E = Eo Inox/Inred + 0.0592
n
The potential change required to produce the full colour change of a
typical general indicator can be found by:

E = Eo Inox/Inred ± 0.0592

295
n 1/31/2023
 Contn’dOxidation – Reduction Indicators
o A typical general indicator exhibits a detectable colour change when a
titrant causes the system potential to shift from
E = Eo Inox/Inred + 0.0592 to E = Eo Inox/Inred - 0.0592
n n
- One can select the appropriate indicator for a given redox titration:
The Eo Inox/Inred must be near the equivalence point.
For example:
If the potential of a titration at the equivalent point were 0.5 V, then
the most suitable indictor would be methylene blue.

296 1/31/2023
 Contn’dOxidation – Reduction Indicators
Selected general redox indicators
Indicator Oxidized color Reduced Eo (V)
colour

indigo tetrasulfonate Blue colorless 0.36

methylene blue Blue colorless 0.53

diphenylamine Violet colorless 0.75

diphenylamine sulfonic acid red-violet colorless 0.85

tris(2,2’-bipyridine)iron pale blue red 1.120

297 1/31/2023
 UNIT SIX
GRAVIMETRIC METHODS OF ANALYSIS
6.1 Principles and Types of Gravimetric Analysis
- Gravimetric analysis is the quantitative isolation of a substance
by precipitation and the weighing of the precipitate.
- It is based on the measurement of mass.
 There are three classes of gravimetric methods of analysis.
o 1. Precipitation gravimetry
- The analyte is separated from a soln. of the sample as ppt then
washed more stable (by heating) and is converted to a cpd of
known composition that can be weighed.
o 2. Electrogravimetry
- The analyte is separated by deposition on an electrode by an
electrical current.
The mass of this product provides a measure of the analyte
concentration.
The analyte is deposited as a solid film on one electrode in an
298 electrochemical cell. 1/31/2023
 Principles and Types of Gravimetric …
o 3. Volatilization gravimetry
- The analyte is separated from other constituents of a sample by
conversion to a gas of a known composition.
The weight of this gas serves as the analyte concentration.
- For example, the gravimetric determination of water content in
barium chloride dihydrate:
BaCl2.2H2O + heat  BaCl2 + 2 H2O (g)
- These methods are highly accurate and precise because they use the
analytical balance as measurement tool.

299
 
6.2. Properties of precipitates and precipitating reagents
 Properties of good precipitates :
o Easily filterable, insoluble and washed free of contaminants(pure)
o Of sufficiently low solubility that no significant loss of the analyte occurs
during filtration and washing.
o Unreactive with constituents of the atmosphere
o Of known chemical composition after it is dried or, if necessary, ignited.
 Properties of precipitating reagents
o Specific (rare): react only with a single chemical species.
Eg. dimethylglyoxime → Ni2+
o Selective (common): react with a limited number of species.
Eg. AgNO3 → Cl-, Br-, I- & SCN-

300
 Contn’d Properties of precipitates and precipitating …
 Particle size and filterability of precipitates
o Why we prefer precipitates of large particles ?
- Large particles made by precipitates are generally desirable
in gravimetric analysis because they are easy to filter and
wash free of impurities and are usually purer than finely
divided precipitates.
The size of the precipitate’s particles determines the ease
and success of filtration.
o Factors that determine the particle size of precipitates
• Colloidal suspensions :
- Whose tiny particles are invisible to the naked eye (10-6-10-4
mm in diameter).
- Colloidal particles show no tendency to settle from solution
- Difficult to filter.
301
 Contn’d Properties of precipitates and precipitating …

• Crystalline solution :
- Particles with size greater 10-1 mm
- Will settle spontaneously
- Easily filtered.
- Higher purity than colloids
 Mechanism for Precipitation
o Precipitation formed by two distinct events:
• A. nucleation:
is the process by which minimum number of atoms, ions, or
molecules join together to form a stable solid. Some times
these nuclei form on the surface of suspended solid
contaminants such as dust particles.
302 1/31/2023
 Contn’d Properties of precipitates and precipitating …
• B. Particle growth
- The particle size of a precipitate is influenced by different
variables like:
- solubility of the precipitate,
- temperature,
- reactants concentrations
- rate at which reactants are mixed.
- The net effects of these variables are related the particle
size by relative supersaturation (RSS or Von Weimarn
ratio).
- RSS is a measure of the extent to which a solution, or a
localized region of solution, contains more dissolved solute
than that expected at equilibrium (RSS).
303
 Contn’d Properties of precipitates and precipitating …
QS
RSS = S

Where :
Q = conc. of the solute at any instant
S = equilibrium solubility.
o As the particle size of the precipitate increases, the impurities
decrease and the ease of filtration increases.
o Particle size ∝ 1
RSS
• RSS↑→ ppt size↓(colloidal)
• RSS↓→ ppt size↑(crystalline solid)

304
 Contn’d Properties of precipitates and precipitating …
o Techniques to minimize (to increase the particle size of
precipitate) RSS:
- RSS↓, Q↓, S↑ → particle size ↑
- i. Use dilute solution (Q ↓)
- ii. Slow addition of the precipitating reagent (Q ↓)
- iii. in hot solution (S↑)
- iv. pH control
example: precipitation of calcium oxalate
a. in mildly acidic,
calcium oxalate → large, easily filtered crystals
(moderately soluble)
b. adding aqueous ammonia (pH↑)
calcium oxalate → completed ppt.(insoluble)
305
 Quiz -2

 1). Write the three classes of gravimetric methods of analysis

 2). Why we prefer precipitates of large particles ?

 3). Write the two mechanism of precipitate formation.

 4). Write relative supersaturation (RSS or Von Weimarn ratio)

equation and explain their terms?

306 1/31/2023
 Contn’d Properties of precipitates and precipitating …
o Colloidal suspensions:
are often stable for indefinite periods and are not directly usable for
gravimetric analysis because their particles are too small to be readily
filtered.
- These particles can be converted in to filterable solids by the process
of coagulations or agglomeration
o Coagulation can be persuaded in two ways:
- by increasing the concentration of the ions responsible for the
secondary adsorption layer
- by heating the solution :
a. ↓ the thickness d1 of the double layer.
b. gain enough kinetic energy to overcome
the barrier to close approach posed by
307
the double layer.
 Contn’d Properties of precipitates and precipitating …

308
 6.3 Steps in Gravimetric Analysis
 The steps required in gravimetric analysis, after the sample has been
dissolved can be summarized as follows:
 1. Preparation of the solution
- it is necessary to eliminate interfering materials.
- the solution must be adjusted to maintain low solubility of the
precipitate and to obtain it in a form suitable for filtration.
- the pH of the solution must be adjusted because it influences the
solubility of the precipitate and the possibility of the interferences
from other substances.
Example CaC2O4 is insoluble in basic medium, but soluble at low
pH because oxalate ion combines with H+ to form oxalic
acid.

309
 Contn’d Steps in Gravimetric Analysis
 2. Conditions for analytical precipitation
- The precipitate should first be sufficiently insoluble that the amount lost
due to solubility will be negligible.
- It should consist of large crystals so that they can be easily filtered.
- Larger crystals have less chance of adsorbing impurities.
- When a precipitate is performed, a slightly excess of precipitating agent is
added to decrease the solubility of the substance (common ion effect) and
to assure complete precipitation.
 3. Digestion of the precipitate
- Digestion is the process in which a precipitate is heated for an hour or
more in the solution from which it was formed (the mother liquor).
- When a precipitating agent is allowed to stand in the presence of the
mother liquor, the large crystals grow at the expense of the small ones.
The small particles tend to dissolve and reprecipitate on the surfaces of
the larger crystals.
310
 Contn’d Steps in Gravimetric Analysis
o When coagulated particles are filtered, they retain the adsorbed
primary and secondary ion layers along with the solvent.
o If it is washed in water, the extent of solvent (water) molecules
between the layers is increased, causing a secondary layer to be
loosely bound and the particles revert to the colloidal state. This
process is called peptization.
o How we can remove impurities from the solution during
precipitation?
- Soluble compounds which causing contaminations of the precipitate
are removed out of the solution by the process called
coprecipitaion.
- Coprecipitation: a process in which normally soluble
compounds are carrier out of solution by a precipitate.
311
 Contn’d Steps in Gravimetric Analysis
o There are different ways of coprecipiation:
• a. Surface adsorption
Soluble compounds are carried out of the solution on the surface
of coagulated colloidal.
b. Occulation
- A type of coprecitation in which a cpd is trapped with in a
pocket formed while in a crystal growth.
-Occluded impurities are difficult to remove i.e. by washing, by
digestion, but
reprecipitation at high temperature helps the impurities to
escape in to the solution.
.
312
 Contn’d Steps in Gravimetric Analysis

Example፡ Water may be trapped in pockets when AgNO3 crystals are

formed and this can be driven off by melting.
• c. Post precipitation

It is the process of where by a precipitate is allowed to stand in

contact with the mother liquor, a second substance will slowly form
a precipitate with the precipitating agent.
Example፡ CuS will precipitate with acid solution in the presence
of Zn2+, but
eventually ZnS will precipitate
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 Contn’d Steps in Gravimetric Analysis
 4. Washing and Filtering
- The precipitate is often washed to remove impurities
adsorbed onto the surface of the particles.

-Washing may be done with a solution of the precipitating

agent, to avoid redissolving a slightly soluble salt.

- With many precipitates, peptization occurs during washing.

Here part of the precipitate reverts to the colloidal form
[e.g. AgCl(colloidal) AgCl(s)].

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 Contn’d Steps in Gravimetric Analysis

This results in the loss of part of the precipitate because the

colloidal form may pass through on filtration.
• Peptization can be reduced with careful technique and
washing with a solution of appropriate pH and ionic
strength.
• Coprecipitated impurities can be removed by washing the
precipitate after filtering.
• When a precipitate is washed, a test should be made to
determine when the washing is complete.
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 Contn’d Steps in Gravimetric Analysis
 5. Drying or igniting the precipitate
• The collected precipitate to be in a form suitable for weighng, it
must be heated to remove water and to remove the adsorbed
electrolyte from the wash liquid.
 6.Weighing
• After the precipitate is allowed to cool (preferably in a desiccators
to keep it from absorbing moisture), it is weighed (in the crucible).
The mass of the crucible is subtracted from the combined mass,
giving the mass of the precipitated analyte.
• Since the composition of the precipitate is known, it is simple to
calculate the mass of analyte in the original sample.
 7. Gravimetric calculations

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 6.4 Gravimetric Calculations
o The results of a gravimetric analysis are generally computed from
two experimental measurements:
- The mass of sample; and
- The mass of a product of known compostion
When the product is the analyte X, the concentration is given by
 g 
f .wtofanalyte 
• GF=  mol  x a
 g  b
f .wtofprecipitate 
 mol 

• g of sample(analyte)
=
g of precipitate
Where GF: - represents the weight of analyte per unit weight of ppt.
- gravimetric factor which states the relationship between
chemically equivalent amounts of two substances.
- a and b are the number of moles in the numerator and
317
denominator respectively.
 Contn’d Gravimetric Calculations
In Gravimetric analysis, the amount of a substance is generally expressed
in terms of percent composition by weights of the analyte in the sample

% substance sought = wt of substance sought (g)

wt of sample (g)
o wt of substance sought(g) = wt of ppt(g)xf.wt of substance sought (g/mol)
f.wt of precipitate(g/mol)
= wt of ppt(g) x GF (g sought/g precipitate)

 % sought = wt of precipitate (g) x GF (g sought/g precipitate) x 100

wt of sample (g)
Example: Calculate the grams of analyte per gram of precipitate for the following
conversion
Analyte precipitate
P Ag3PO4
K2HPO4 Ag3PO4
Bi2S3 BaSO4
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 Contn’d Gravimetric Calculations
o Solution
a. GF = P (g) = F. Wt of P (g/mol) x 1 (mol P)
Ag3PO4 (g) F.wt Ag3PO4(g/mol) 1 (mol Ag3PO4)

= 31 g/mol x 1 = 0.0435 g P/g Ag3PO4

711 g/mol 1
That is, every gram (1 g) of Ag3PO4 contains 0.0435 g of P.

b/ g K2HPO4 = F.wt of K2HPO4(g/mol) x 1 (mol K2HPO4) F.wt = formula weight

g Ag3PO4 F.wt of Ag3PO4(g/mol) 1 (mol Ag3PO4)
= 136 g/mol x 1 = 0.19135 g K2HPO4
711 g/mol 1 g Ag3PO4

c/ GF = g Bi2S3 = F.wt of Bi2S3 (g/mol) x 1 = 514.15 x 1 = 0.73429 g Bi2S3

g BaSO4 F.wt of BaSO4 (g/mol) 3 233.40 3 g BaSO4

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 Contn’d Gravimetric Calculations
Sought Weihed GF

SO3 BaSO4 SO3 f.wt

BaSO4 f.wt

Fe3O4 Fe2O3 Fe3O4 f.wt

Fe2O3 f.wt

Fe Fe2O3 Fe f.wt
Fe2O3 f.wt

MgO Mg2P2O7 MgO f.wt

Mg2P2O7 f.wt

P2O5 Mg2P2O7 P2O5 f.wt

Mg2P2O7 f.wt

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 Contn’d Gravimetric Calculations
o Example: A 0.4960 g sample of a CaCO3 is dissolved in an acidic solution.
The calcium is precipitated as CaC2O4.H2O and the dry precipitate
is found to weigh 0.6186 g.What is the percentage of CaO in the
sample?
Solution
Given: wt of CaCO3 sample = 0.4960 g, wt of ppt. CaC2O4.H2O = 0.6186 g
Required: % CaO in the 0.4960 g sample of CaCO3
Solution: wt of CaO = (wt of CaC2O4.H2) x 1 mole CaO x 1 mole Ca FWCaO
1 mole Ca 1 moe CaC2O4.H2O FW precipitate
= (0.6186) 1 mole CaO 56.08 (g/mol)
1 moe CaC2O4.H2O 146.12 (g/mol)
Wt of CaO = 0.2374 g
% CaO = wt of CaO x 100 = 0.2374 g x 100 = 47.87 %
wt of sample 0.4960 g
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 Contn’d Gravimetric Calculations
o Example: An ore is analysed for the manganese content by converting
the manganese to Mn3O4 and weighing it. If a 1.52g
sample yields Mn3O4 weighing 0.126 g,
a. what would be the percent Mn2O3 in the sample ?
b. The percent Mn?
Given: g of ppt(Mn3O4) = 0.126g
g of sample 1.52 g
Required: %Mn2O3
Solution: %Mn2O3 = (g of ppt x GF/g of Sample)x100

a.

= 0.126 g x[ ] x 100%

= 8.58%
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 Contn’d Gravimetric Calculations
b.

= 0.126 g x [3(54.94)/2(228.9)] x 100%

1.52 g
= 5.97%

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