Chapter -five

Titrimetric Methods of Analysis

 Introduction
 Titrimetry is the oldest and widely used quantitative method
that is based upon measuring the amount of a reagent of
known concentration that is consumed by the analyte.
 In a chemical reaction one reactant reacts with the other based
on the stoichiometry of the reaction.
 Example, if you have one mole of HCl in a solution it requires
one mole of NaOH since the stoichiometry is 1:1 ratio.

HCl(aq) + NaOH(aq) NaCl(aq) + H2O

 Cont,d

 In titrimetry, we measure the amount of a reagent that can

react completely with analyte in volume or mass or charge and
deduce the concentration of the analyte using the
stoichiometry.
 Titrimetric methods of analysis are widely used for routine
analyses because they are rapid, convenient, accurate and
readily automated.
 Titrimetric methods are classified into three groups based on the
type of signal measured.
1. Volumetric titrimetry :is a type of titrimetry in which the
volume of the standard reagent is measured as a signal. i.e. the
volume of a reagent which is required to react completely with
the analyte is measured.
2. Gravimetric titrimetry or weight titrimetry is a type of
titrimetry in which the mass of the standard reagent is
measured. i.e. the mass of the reagent which can react with the
analyte is measured.
3. Coulometric titrimetry. The reagent is a constant direct
electrical current of known magnitude that directly or indirectly
reacts with the analyte. Here the time required to complete the
reaction is measured.
Titrimetric methods are also classified into four groups based on the type
of reaction involved.
1. Acid - Base Titration is based on acid base reaction in which an acidic
or basic titrant reacts with an analyte that is a base or an acid respectively.
2. Complexometric titration involves a metal–ligand complexation
reaction.
In this method the amount of a ligand which can complex with the metal
is measured.
3. Redox titration is where the titrant is an oxidizing or reducing agent.
4. Precipitation titration is a titrimetric method, in which the analyte and
titrant react to form a precipitate
 Titration is a process, in which a standard reagent is added to a
solution of an analyte until the reaction between the analyte
and the reagent is judged to be complete.
 It is a process where titrant slowly adds to analyte until the
reaction between the two solution is judged complete.
 Titrant is the reagent with known concentration added to a
solution containing the analyte and whose volume or mass or
electric charge is the signal. Sometimes called as reagent or
standard solution
 Equivalence Points and End Points

Equivalence point is a point in titration when the amount of

added reagent is chemically equivalent to the amount of the
analyte.
 it is the point in a titration where stoichiometrically
equivalent amounts of analyte and titrant or reagent react. It is
a theoretical point that cannot be determined experimentally.
End point is the point in a titration where we stop adding titrant
(it is experimental value).
Titration Error: The difference in volume between the
equivalence point and the end point.
E titration = V equivalence point – V end point
Under ideal conditions the equivalence point and the end point
are identical.
In most practical analyses the end point is near equal but not
identical with the equivalence point.
Indicators are substances or some physical properties that are
often added to the analyte solution or measured in order to give
an observable physical change (the end point) at or near the
equivalence point.
To determine the end point we use different types of indicators.
A. Self (internal) indicators: In these types of indicators the
analyte or titrant itself is used as indicator.
Example: in redox titration of oxalate ion by permanganate, the
titration is stopped when the oxalate solution turns pink color of
the permanganate solution permanently.
B. External chemical indicators: are added to the analyte solution
and show some color change at equivalence point.
Standard Solution: is a reagent of known concentration that is
used to carry out a titrimetric analysis. usually it is added from
the burette.
Determination of the concentration of an analyte or reagent
solution from its reaction with a standard or primary standard is
referred to as standardization.
A. Primary Standard Substance: is a highly purified compound
that serves as a reference material in all volumetric titrimetric
methods.
 Ideal requirements for standard solutions
 For a given compound to be considered as a primary standard, it should

fulfill the following criteria.

 The substance should be readily purified.
 It should not be hygroscopic.
 It should not be contain hydrate water.
 It should be readily soluble.
 It should have a relatively high equivalent weight.
 It should be available and not too expensive.
 It should be stable toward air.
 It should be stable on storage.
 It should not undergo any side-reaction.
• Compounds that meet or even approach these criteria are very few, and
only a limited number of primary standard substances are available to the
chemist.
 A solution whose concentration has been accurately
determined by titration of a primary standard and which is
used to standardize other solutions is known as a secondary
standard.
Desirable properties of the standard solution
The ideal standard solution for a titrimetric method should
 be sufficiently stable
 React rapidly with the analyte
 Undergo a selective reaction with the analyte that can be
described by a simple balanced equation
 Where ,Veq is the theoretical volume of reagent required to reach
the equivalence point and Vep is the actual volume used to arrive
at the end point.
 If the titration reaction is too slow, a suitable indicator is not
available
 there is no useful direct titration reaction, then an indirect
analysis may be possible.
 Back titration is a titration, in which a reagent is added in excess
to a solution containing the analyte, and the excess reagent
remaining after its reaction with the analyte, is determined by a
titration.
Titration Curves
 A graph showing the progress of a titration as a function of the
volume of titrant added.
 It provides us with a visual picture of how properties, such as
pH, pAg, conductance or temperature change as we add titrant.
 example
 Acid – Base Titration (Neutralization Titration
Acid–base titration: is a titration in which the reaction between
the analyte and titrant is an acid–base reaction.
That is if you have an acid analyte ,you can titrate it with a base
and vice versa.
Note: during acid base titration always we use strong acid and
strong base to titrate weak base and weak acid respectively.
Because the reaction between a strong acid and weak base or
strong base and weak acid is complete.
 To titrate strong acid and strong base we can use either strong
or weak base or strong or weak acid respectively.
 Acid Base Titration Curves
 Titration curve for neutralization titration is commonly plotted pH Vs volume

of the reagent.
 To understand the relationship between end points and equivalence points we

must know how the pH changes during a titration.

 We can plot the titration curve by measuring the pH of the analyte solution at

each addition of the reagent.

The shape of the titration curve depends on:

 Whether the titration is acid by base or base by acid

 Either we use pH or pOH

 The strength of the acid and base

 A)Titration of Strong Acids by Strong Bases
 For our first titration curve let’s consider the titration of 50.0 mL of 0.100 M
HCl with 0.200 M NaOH.
 For the reaction of a strong base with a strong acid the only equilibrium
reaction of importance is

H3O+(aq) + OH-(aq) 2H2O(1)

 The first task in constructing the titration curve is to calculate the volume of
NaOH needed to reach the equivalence point.
At the equivalence point we know from the above reaction that
Moles HCl = moles NaOH
or MaVa = MbVb
 We usually use NaVa = NbVb. We use molarities because in this
case the normality and molarity are equal)
 where the subscript ‘a’ indicates the acid, HCl, and the subscript
‘b’ indicates the base, NaOH.
 The volume of NaOH needed to reach the equivalence point,
therefore, is

 Before the equivalence point, HCl is present in excess and the pH

is determined by the concentration of excess HCl.
 Initially the solution is 0.100 M in HCl, which, since HCl is a
strong acid, means that the pH is
 pH = –log [H3O+] = –log [HCl] = –log(0.100) = 1.00
 After adding 10.0 mL of NaOH, therefore, the concentration
of excess HCl is

 Giving a pH of 1.30.
 At the equivalence point the moles of HCl and the moles of
NaOH are equal. Since neither the acid nor the base is in
excess, the pH is determined by the dissociation of water.
Kw = 1.00 x 10–14 = [H3O+][OH–] = [H3O+]2
[H3O+] = 1.00 x 10–7 M
Thus, the pH at the equivalence point is 7.00.
• Finally, for volumes of NaOH greater than the equivalence
point volume, the pH is determined by the concentration of
excess OH–.
• For example, after adding 30.0 mL of titrant the concentration
of OH– is
• To find the concentration of H3O+, we use the Kw expression
 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

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
[H+] = 1x10-14 = 3.84 x10-12 M, pH = -log 3.84x10-12 M = 11.41
2.6x10-3
Figure 5.1 Acid–base titration curve for 50.0 mL of 0.100 M HCl with 0.200 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 base un-reacted.
 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
Titration of Strong Acid Vs. Strong Base…Cont’d

A) The titration curve for 100.0 mL of B) The titration curve for 100.0 mL
0.100 M HCl with 0.100 M NaOH. Note of 0.100 M NaOH with 0.100 M HCl.
that the “vertical” section of the curve is This curve is similar to that in (a),
quite long. but inverted.
 C. Weak Acid/Strong Base Titration
As before, we can separate the calculations into four distinct
types, corresponding to four regions of the titration curves.
1. Before any base is added, the pH depends on the weak acid
alone.
2. After some base has been added, but before the equivalence
point, a series of weak acid/salt buffer solutions determines the
pH.
3. At the equivalence point, hydrolysis of the anion of the weak
acid determines the pH.
4. Beyond the equivalence point, excess strong base determines
 Titration of a Weak Acid Monoprotic with a Strong Base.
 For this example let’s consider the titration of 50.0 mL of
0.100 M acetic acid, CH3COOH, with 0.100 M NaOH.
Again, we start by calculating the volume of NaOH needed to
reach the equivalence point; thus.
Moles CH3COOH = moles NaOH

 Before adding any NaOH, the pH is that for a solution of

0.100 M acetic acid. Since acetic acid is a weak acid.
 Before adding any NaOH the pH is that for a solution of 0.100
M acetic acid. Since acetic acid is a weak acid.

 It the beginning of the titration the pH is 2.88.

 Adding NaOH converts a portion of the acetic acid to its
conjugate base
 Any solution containing comparable amounts of a weak acid,
HA, and its conjugate weak base, A–, is a buffer.
 we can calculate the pH of a buffer using the Henderson–
Hassel balch equation.
• Before the equivalence point, the concentration of unreacted
acetic acid is and the concentration of acetate is and the
concentration of acetate is
 For example, after adding 10.0 mL of NaOH the concentrations of
CH3COOH andCH3COO– is

 A similar calculation shows that the pH after adding 20.0 mL of

NaOH is 4.58.
 At the equivalence point, the moles of acetic acid initially present
and the moles of NaOH added are identical.
 Since their reaction effectively proceeds to completion, the
predominate ion in solution is CH3COO–, which is a weak base. To
calculate the pH we first determine the concentration of CH 3COO–.
The concentration of H3O+, therefore, is 1.87 x 10–9, or a pH of 8.73.
After the equivalence point NaOH is present in excess, and the pH
is determined in the same manner as in the titration of a strong acid
with a strong base. For example, after adding 60.0 mL of NaOH, the
concentration of OH– is
• Example: the titration of 50.0 mL of 0.100 M acetic acid, CH 3COOH, 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)/ 0.1 M = 50 mL

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
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.
 pH = pKa + log [salt] = pKa + log [CH3COO–]
[acid] [CH3COOH]
The concentration of acetic acid is;

[CH3COOH] = moles of un-reacted CH3COOH = MaVa -MbVb

Total volume Va + Vb

The concentration of acetate ion is;

[CH3COO-] = moles of NaOH added = MbVb
Total volume Va + Vb
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-] = 2.76 + log 0.0167 = 2.16

[CH3COOH] 0.0667
( pKa = -log Ka)
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-] = 2.76 + log 0.0286 M = 2.58

[CH3COOH] 0.043 M
At equivalent point (50 mL of NaOH)
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
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 CH3COOH = 1.75 x 10-5, then Kb for CH3COO–
Ka
Kb = 1x10-14 = 5.71x10–10
1.75 x10-5
 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
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
CH3COOH(aq) + OH–(aq) H2O(l) + CH3COO–(aq)
Initial mmol 5 6 0
Equil. mmol 0 1 5
[OH-] = MbVb - MaVa = 6 – 5 = 1 = 0.0091
Va + Vb (60 + 50) mL 110 mL
pOH = - log[OH-]= 3.04, pH = 14 - 3.04 = 11.96
Table 5.2 Titration Data for 100.0 mL of 0.100 M CH3COOH with 0.100 M
NaOH
mL 0.100 M NaOH mmol Base mmol Excess Acid or pH
Added Added Base
Figure 5.2 The titration
curve for 100.0 mL of 0.100
M CH3COOH with 0.100 M
NaOH. The “vertical”
section of this curve is much
shorter than those in Figure
5.1 because the solution is
buffered before the
equivalence point. Methyl
red indicator, which changes
over the range 4.5 to 6.4,
would obviously not be
suitable for this titration.
 D. Weak Base/Strong Acid Titration

 The calculations for the titration of a weak base with a strong

acid are handled in a similar manner except that the initial pH
It is determined by the weak base.
 The pH at the equivalence point by its conjugate weak acid,
and
 The pH after the equivalence point by the concentration of
excess strong acid
The titration curves for weak bases and strong acids are similar to
those for weak acids and strong bases except that they are
inverted (recall that strong is added to weak).
Figure 5.3 The titration curve for
100.0 mL of 0.100 M aqueous
ammonia titrated with 0.100 M
HCl. The vertical section of the
curve is relatively short because the
solution is buffered before the
equivalence point. The curve is
very similar to that in Figure 5.2,
but inverted. Phenolphthalein
indicator, which changes over the
range 8.0 to 10.0, should not be
used for this titration.
Methyl red indicator which
changes over 4.2 to 6.8 can be
used for this titration.
 E. Weak Acid/Weak Base Titration Curves
 In titration curves for weak acids and weak bases, pH changes
near the equivalence point are too gradual for color indicators to
be used. The solution is buffered both before and after the
• The titration curve for 100. mL of 0.100
equivalence point. M CH3COOH with 0.100 M aqueous
NH3. At the equivalence point for this
titration, the pH is 7.0, but this is not true
for all such combinations. Because the
solution is buffered before & after the
equivalence point, the pH changes very
gradually near the equivalence point.
• Color indicators cannot be used in such
titrations.
• Instead, physical methods such as
conductivity measurements or pH
electrode-based instruments can be used
to detect the end point.
Note that: 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.
 Acid–Base Indicators
 An acid-base indicator is a weak organic acid or a weak
organic base whose undissociated form differs in color from its
conjugate base or its conjugate acid form.
 For example, the behavior of an acid-type indicator,
HIn, is described by the equilibrium

……………. (.2)

……....(3)
 ⇰ To obtain the indicator pH range, we take the negative
logarithms of the two expressions:

pH(acid color) = -log(10Ka) = pKa - 1

pH(basic color) = -log(0.1Ka) = pKa + 1

Indicator pH range = pKa 1 …………. (5.4)

Example:
Determine the pH range over which an indicator with the Ka value
of 1 x 10-5 shows a complete color change in a given solution.
2. Precipitation titration
• The most important precipitating agent used in precipitation
reactions is the silver nitrate AgNO3 solution and titration
methods based upon utilizing silver nitrate as a precipitating
agent are termed as argentometric methods

• Silver ion is useful for the determination of halides (Cl-, Br-,

I-),halide like anions ( CN-, SCN- ,CNO-) and so on.
Titration Curves for Argentometric Titrations
• The titration curves are normally sigmoidal curves consisting
of pAg (or P analyte) versus volume of AgNO3 solution added.
The titration curve for a precipitation titration 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)

 Precipitation titration curve is influenced by the concentration of Ag+

and Cl- and by KSP value.

 The titration curve may be a plot of pAg or pCl as a function of the

titrant’s volume.
• In argentometric titration, plots of titration curves are normally
sigmoidal curves consisting of pAg (or pAnalyte) vs. volume
of AgNO3 solution added. Example: Titration of chloride with

silver.

The points on the curve can be calculated, given the analyte

concentration, AgNO3 concentration and the appropriate Ksp.
 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–]
 calculate the volume of Ag+ needed to reach the equivalence point.
From the stoichiometry:
moles Ag+ = moles Cl– at the equivalence point
Or MAg VAg = MCl VCl

Before equivalent point

Before the equivalence point Cl– is in excess.
i. addition of 10 mL of Ag+
The concentration of un-reacted 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) = 2.5x10-2
50 mL + 10 mL
pCl = -log[Cl–] = -log (2.5x10-2) = 1.60s
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) = 7.14x10-3
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
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 pCl = -log[Cl–] = -log 1.34x10-5
= 2.87
pAg =- log[Ag+] = -log 1.34x10-5 = 2.87

At the equivalent point, therefore, pCl and pAg are equal.

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
[Ag+] = (0.1 M)(35.0 mL) – (0.05 M)(50.0 mL)
35 mL + 50 mL
[Ag+] = 1.18x10-2 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 equal to pKsp (= -log Ksp).

Precipitation titration curve for 50.0 mL

of 0.0500 M Cl– with 0.100 M Ag+
(a) pCl versus volume of titrant; (b) pAg
versus volume of titrant
 End point detection methods of precipitation titration

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 adsorptions of an indicator does not
occur until an excess of titrant is added, Fajans Method
 Mohr Method
☞ Direct titration
☞ was first published in 1855 as a method for chloride analysis.
☞ Indicator: soluble chromate salt (Na2CrO4, K2CrO4)
☞ Basis of endpoint: formation of a colored secondary
precipitate
 In the precipitation of Cl- by Ag+, CrO42 is used as an indicator
in the formation of a reddish Ag2CrO4 ppt, when excess Ag+ is
present.
Ag+ + Cl AgCl(s) (Titration Reaction)
titrant analyte white ppt
Ksp= 1.8 x 10-10 (s = 1.34 x 10-5 M)
2Ag+ + CrO42 Ag2CrO4(s) (Mohr indicator rxn, end
point) titrant indicator reddish ppt
Ksp= 1.2 x 10-12 (s = 6.7 x 10-5 M)
☞ Mohr Method has to be performed only in neutral or slightly
weak basic medium (pH 7-10)
 Volhard Method

☞ First published in 1874 for determination of Cl- by back titration

of excess Ag+ with thiocyanate (SCN) using Fe3+ as an indicator

✈ First, Cl- is precipitated by excess AgNO3

Ag+ (aq) + Cl-(aq)  AgCl(s) (white ppt)
✈ Excess Ag+ is titrated with KSCN in the presence of Fe3+
Ag+(aq) + SCN-(aq)  AgSCN(s) (white ppt)
✈ When Ag+ has been consumed, a red complex forms
Fe3+(aq) + SCN-(aq)  FeSCN2+(aq) (red complex ion)
☞ The endpoint is routinely used for halide determinations where
a known excess of Ag+ is added to precipitate the halide ion,
and the excess Ag+ is back titrated with SCN- using Fe3+ as an
indicator.
☞ The AgCl precipitate is filtered, and the excess Ag+ is titrated
with SCN- producing a white precipitate of AgSCN.
☞ Once the silver is consumed, the excess SCN- reacts with the
Fe3+ producing a red FeSCN2+ complex. The appearance of the
red color indicates the endpoint.
✈ The titration is usually done in acidic pH medium to
prevent precipitation of iron hydroxides, Fe(OH)3.
☞ The AgCl precipitate must be separated from the thiocyanate to
prevent the reaction:
AgCl + SCN- AgSCN + Cl-
 To eliminate this error, AgCl must be filtered or add
nitrobenzene before titrating with SCN-; nitrobenzene will
form an oily layer on the surface of the AgCl precipitate,
thus preventing its reaction with SCN-.
 Fajan's Method (Adsorption Indicators)
• Adsorption indicators are organic compounds that tend to be
adsorbed onto the surface of the solid precipitate in the titration.
• Adsorption indicators work best when:
☞ For example, when titrating Cl– with Ag+ the anionic dye
dichlorofluoroscein is used as the indicator.
☞ Before the end point, the precipitate of AgCl has a negative
surface charge due to the adsorption of excess Cl –. The anionic
indicator is repelled by the precipitate and remains in solution
where it has a greenish yellow color.
☞ After the equivalence point, the precipitate has a positive surface
charge due to the adsorption of excess Ag+.
☞ The anionic indicator now adsorbs to the precipitate’s
surface where its color is pink. This change in color signals
the endpoint
 5.3 Complexometric Titration

 Titrations based on complex formation, sometimes called

complexometric titrations
 Titration with ethylenediamine tetra acetic acid (EDTA)

• EDTA => Ethylenediaminetetraacetic acid

• The EDTA molecule has 6 potential sites for bonding a metal

ion.
It is a type of titratimetry based on the reaction between a metal and a
ligand (complex formation reaction).
 Mostly it is used to determine level of metal ions. Example EDTA is
used to determine the concentration of ca 2+ in a given sample.
So, the standard solution used here is ligands

For complexometric titration we usually use multidentate ligands. This

is due to
Reaction between monodentate ligands and a metal involve several
steps
The reaction between multidentate ligands and metal is complete and
rapid.
 Acidic Properties of EDTA

Let H4Y represent the EDTA molecule:

 Complexes of EDTA and Metal Ions

• The reagent combines with metal ions in a 1:1 ratio

regardless of the charge on the cation.

Generally, for metal ion Mn+

𝑲 𝒇 =¿ ¿ ¿
• Need to know [Y4-], which is pH-dependent
pH dependence of Y4-:
Define: 4 =

where, CT = [Y4-] + [HY3-] + [H2Y2-] + [H3Y-] + [H4Y]

Substituting [Y4−] =4 in Kf expression:

= Kf ⟹ = 𝛼 4 Kf = Kf′

Where K is the conditional formation constant

 EDTA Titration Curve

☞ A titration curve for the reaction of Mn+ and EDTA can be

constructed by plotting of pM versus reagent volume.
Solution:
Conditional Formation Constant, K for pH = 10.0
K= (4)(Kf) = (0.35)(5.0 x 1010) = 1.75 x 1010
a) pCa value before any EDTA is added
[Ca2+] = 0.0050M and pCa = -log (0.0050) = 2.30
b) pCa values before the equivalence point (10.0mL)
• The expected titration reaction is
Ca2+ + Y4- CaY2-
Excess Limited
pCa is calculated from the excess Ca2+
☞ Excess mmol Ca2+ = mmol of Ca2+ solution – mmol of addedY4-
= (mM Ca2+ x mL Ca2+ so/n) - (mM Y4- x mL Y4- so/n)
When 10.0 mL of EDTA solution is added, [Ca2+] becomes

[Ca2+] =
= 2.50 x 10-3 M
and pCa = -log (2.50 x 10-3) = 2.60
c) pCa value at the equivalence point
At equivalence point: MCa2+ x VCa2+ so/n = MY4- x VY4- so/n
VY4- so/n = = = 25.0 mL

Ca2+ + Y4- CaY2-

at equim. 0.0 mmol 0.0 mmol 0.25 mmol
☞ [CaY2-] = (25.0 mL x 0.010 M)/(75.0 mL)) = 0.00333 M
Note: Here, the dissociation of the CaY2- should be considered
CaY2- Ca2+ + Y4- (where, Kd = 1/K)
Initial (M) 0.00333 0.0 0.0
Change (M) -x +x +x
Equil.(M) 0.00333-x x x
Kd = = 5.71 x 10-11
 EDTA Titration Curve

Kd = = 5.71 x 10-11

Assuming 0.00333 – x
= 5.71 x 10-11

x = = 4.3 x 10-7

[Ca2+] = 4.3 x 10-7 M

✈ pCa = -log (4.3 x 10-7) = 6.36

d) pCa value after the equivalence point (>25.0mL of EDTA)

Ca2+ + Y4- CaY2-

Limited Excess

☞ Excess mmol Y4- = mmol of added Y4-– mmol of Ca2+ solution

= (mM Y4- x mL Y4-so/n) - (mM Ca2+ x mL Ca2+ so/n)

At 30.0 mL of EDTA solution, [Y4-] becomes

[Y4-] =
= 6.25 x 10-4 M
Figure 5.6: EDTA
(0.010 M) titration
curves for 50.0 mL
of 0.0050 M Ca2+ at
pH 10.0.
 End Point Detection Method

Metal Ion Indicator:- formed when a compound that changes

color (indicator) binds to a metal ion
✈ For instance, titration of Mg2+ by EDTA
•Eriochrome Black T(EBT) is the common indicator for EDTA titrations
Indicator reaction:
Mg2+(Colorless)+ EBT (Blue) MgEBT (Wine red)
✈For an EDTA titration, the indicator must bind the metal ion less
strongly than EDTA
☞Needs to release metal ion to EDTA
MgEBT + EDTA MgEDTA + EBT
(Wine red) (Colorless) (Colorless) (Blue)
 5.5 Redox Titrations
 Redox Titration
☞ Based on an oxidation-reduction reaction b/n analyte & titrant
☞ Voltage change as a function of added titrant
☞ Many common analytes in chemistry, biology, environmental
and materials science can be measured by redox titrations
 Redox Titration Curve

Consider the titration of 50.00 mL of 0.0500 M Fe2+ with 0.1000 M

Ce4+ in a medium that is 1.0 M in H2SO4 at all times.
Formal potential data for both half-cell processes are available used
for these calculations. Thus,
Solution:
• The titration reaction is Fe2+ + Ce4+ ⇌ Fe3+ + Ce3+
• This reaction is rapid & reversible so that the system is at
equilibrium at all times throughout the titration.
Titration Curve has 3 regions
✈ Before the Equivalence Point
✈ At the Equivalence Point
✈ After the Equivalence Point
Region 1: Before the Equivalence Point
• Each aliquot of Ce4+ creates an equal number of moles
of Ce3+ and Fe3+
• Excess unreacted Fe2+ remains in solution
• Amounts of Fe2+ and Fe3+ are known, use to determine
cell voltage.
Before the equivalence point the titration mixture consists of
appreciable quantities of both the reduced and oxidized
forms of the analyte (i.e. Fe2+ and Fe3+), but very little
unreacted titrant. The potential, therefore, is best calculated
using the Nernst equation for the analyte’s half-reaction.
i) Initial Potential

• The solution contains no cerium species before we add titrant.

So, we don’t have enough information to calculate an initial
potential. i.e. no redox reaction.
ii) Potential after the Addition of 5.00 mL of Cerium(IV)
• The equilibrium concentration of Fe(III) becomes
[Fe3+] =
• Similarly, the Fe2+ concentration is calculated from its
excess amounts:
[Fe2+] =
✈ Substitution for [Fe2+] and [Fe3+] in the Nernst equation gives
0′
E system =E 3+ ¿ 2+ ¿ 0 . 0592
Fe / Fe − log ¿ ¿¿ ¿¿
1

= 0.64 V

☞ Note that the volumes in the numerator and denominator

cancel, indicating that the potential is independent of dilution.

Activity: Calculate when 10.0, 15.0, and

20.0 mL of cerium (IV) solutions are added.
Region 2: Equivalence-Point Potential

• At the equivalence point, the is given by both

0′
E eq =E 4 +¿ 3+ ¿ 0 .0592
Ce / Ce − log ¿¿ ¿¿ ¿
1
0′
E eq =E 3 +¿ 2+ ¿ 0 .0592
Fe / Fe − log ¿¿ ¿¿ ¿
1

☞ Adding these two expressions gives

• The definition of equivalence point requires that

[Fe3+] = [Ce3+] and [Fe2+] = [Ce4+]
Cont,d

After the equivalence point, the potential is easiest to

calculate using the Nernst equation for the titrant’s half-
reaction, since significant quantities of its oxidized and
reduced forms are present.
• The concentrations of the two cerium ion species are

[Ce3+] =

[Ce4+] =

☞ Substitution into the Nernst equation for the cerium couple gives
0
E system =E 4 +¿ 3+ ¿ 0 .0592
Ce /Ce − log¿ ¿ ¿¿ ¿
1
= 1.30 V

✈ Activity: Calculate at 26.0, 30.0, 35.0, & 40.0 mL of

cerium (IV) solution.
Figure 5.6 Titration
curve for 50.00 mL of
0.05000 M Fe2+ against
0.1000 M Ce4+ solution.
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 HClO2. The reaction is
Fe2+(aq) + Ce4+(aq)  Ce3+(aq) + Fe3+(aq)
• 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 VFe2+ = (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)
Initial mmole 5 0.5 - -
Equil. mmole 2.5 0 0.5 0.5
The concentration of species at equilibrium,
[Fe2+] = mmole = 2.5 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] = 0.71 V
1 [0.0091M]
• 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 - -
Equilibrum 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
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
Eo Ce4+/Ce3+ = 1.7 V
• Eeq = Eo Fe3+/Fe2+ + Eo Ce4+/Ce3+ = 0. 77 V + 1.7 V = 1.23 V
2 2
In general, E at the equivalence 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.
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 = 0.0091 M
total volume 60 mL + 50 mL
[Ce4+] = mmole = 1 mmole = 0.045 M
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+ = 1.66 V
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
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

E Ce4+/Ce3+ = Eo – 0. 059 log [Ce3+]

1 [Ce4+]

E Ce4+/Ce3+ = 1.7 V – 0. 059 log 0.042 M

1 0.017 M
E Ce4+/Ce3+ = 1.68 V