UNIVERSITY OF THE PHILIPPINES MANILA

TITRIMETRIC METHODS OF ANALYSIS

Titrimetric methods - quantitative procedures based upon
measurement of the amount of reagent consumed by the analyte.
Volumetric titrimetry - involves measuring the volume of a solution
of a known concentration that is needed to react completely with the
analyte.
Gravimetric titrimetry - the mass of the reagent is measured
instead of its volume.

Terminologies
Standard solution (or standard titrant) is a reagent of known
concentration that is used to carry out a titrimetric analysis.
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Equivalence point - the amount of added titrant is chemically
equivalent to the amount of analyte in the sample.
End point - observable physical change associated with the
condition of equivalence.
Indicators - added to the analyte solution in order to give an
observable physical change (the end point) at or near the
equivalence point.
Primary standard - highly purified compound that serves as a
reference material in all titrimetric methods.
Desirable Properties of Standard Solution

- stable

- reacts completely

- reacts rapidly

- selective

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Sample Calculation from Titration Data
A 0.8040-g sample of an iron ore is dissolved in acid. The iron is
then reduced to Fe2+ and titrated with 47.22 mL of 0.02242 M
KMnO4 solution. Calculate the results of this analysis in terms of a.)
% Fe (55.847 g/mol) and b.) % Fe3O4 (231.54 g/mol). The reaction
of the analyte with the reagent is described by the equation

MnO4- + 5Fe2+ + 8H+

Mn2+ + 5Fe3+ + 4H2O

5mmolFe +2
a) stoichiometric ratio
1mmolKMnO4
0.02242mmolKMnO4
amount KMnO4 47.22mLKMnO4 x
mLKMnO4

1.058 7 mmolKMnO4

2+
5mmolFe
2+
amount Fe2+ 1.0587mmolKMnO4 x
=
5.293
mmolFe
5

1mmolKMnO4
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massFe

2+

UNIVERSITY OF THE PHILIPPINES MANILA

2+

1mol
55.847gFe
= 5.2935mmolFe x
x
1000mmol
mol
2+
0.2956 3 gFe
2+

2+
0.2956
gFe
3
%Fe 2+ =
x100 = 36.77%
0.8040g

b. In order to derive a stoichiometric ratio, note that

5 Fe2+ = 1MnO4-

Therefore,

1 Fe3O4 = 3 Fe2+ = 3/5 MnO45 Fe3O4 = 15 Fe2+ = 3 MnO4and

stoichiometric ratio = 5 mmol Fe3O4

3 mmol KMnO4

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0.02242mmolKMnO4
massFe3O4 = 47.22mLKMnO4 x
mLKMnO4
5mmolFe3O4 0.2315gFe3O4
x
x
= 0.4085 4 gFe3O4
3mmolKMnO4
mmolFe 3O4

0.40854g
%Fe3O4 =
x100 = 50.81%
0.8040g

Gravimetric Titrimetry

Weight or gravimetric titrimetry differs from its volumetric

counterpart in that the mass of titrant is measured rather than
the volume.
In a weight titration, a balance and a solution dispenser are
substituted for a buret and its markings
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The most convenient unit of concentration for weight titrations is

weight molarity, Mw.

molsolute mmolsolute
Mw =
=
kgsolution
gsolution
TITRATION CURVES

sigmoidal curve

pX

equivalence point

Voltitrant
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OF THE PHILIPPINES MANILA
Titration
Data
Vol. of 0.100 M
NaOH, mL

[H3O+] mol/L

0.00

1.000 x 10-1

40.91

1.000 x 10-2

49.01

Vol. of NaOH to
cause a tenfold
decrease in [H3O+],
mL

pH

pOH

1.00

13.00

40.91

2.00

12.00

1.000 x 10-3

8.11

3.00

11.00

49.90

1.000 x 10-4

0.89

4.00

10.00

49.99

1.000 x 10-5

0.09

5.00

9.00

49.999

1.000 x 10-6

0.009

6.00

8.00

50.00

1.000 x 10-7

0.001

7.00

7.00

50.001

1.000 x 10-8

0.001

8.00

6.00

50.01

1.000 x 10-9

0.009

9.00

5.00

50.10

1.000 x 10-10

0.09

10.00

4.00

51.01

1.000 x 10-11

0.91

11.00

3.00

61.11

1.000 x 10-12

10.10

12.00

2.00

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TITRATION CURVES FOR STRONG
ACIDS AND STRONG BASES
14
12
10
8
6
4
2
0
0

10

20

30

40

50

60

70

Plot for data in table above.

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The Titration of a Strong Acid with a Strong Base
To derive a titration curve for a solution of a strong acid with a
strong base, three types of calculations are required.
(1) pre-equivalence
(2) equivalence
(3) post-equivalence

Important formulas:
Kw = [H3O+][OH-]
-log Kw = -log [H3O+][OH-]
= -log [H3O+] log[OH-]
pKw = pH + pOH
-log10-14 = 14.00 = pH + pOH
pKw = pH + pOH = 14.00
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Example

UNIVERSITY OF THE PHILIPPINES MANILA

Derive a curve for the titration of 50.00 mL of 0.0500 M HCI

with 0.1000 M NaOH.
Initial Point
At the outset, the solution is 0.0500 M in H3O+ and
pH = -log[H3O+] = -log 0.0500 = 1.30
After Addition of 10.00 mL of Reagent (Pre-equivalence)
The hydronium ion concentration decreases as a result of
both reaction with the base and dilution.
Thus, the analytical concentration of HCI is
cHCl = no. mmol HCl remaining after addition of NaOH
total volume solution
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cHCl = original no. mmol HCl no. mmol NaOH added
total volume solution
= (50.00 mL x 0.0500 M) (10.00 mL x 0.1000 M)
50.00 mL + 10.00 mL

= (2.500 mmol 1.000 mmol) = 2.500 x 10-2

M
60.00 mL
+
[H3O ] = 2.50 x 10-2
and
pH = -log [H3O+] = -log (2.500 x 10-2) = 1.602
Additional points defining the curve in the region before
the equivalence point are obtained in the same way.
Equivalence Point
At the equivalence point, neither HCI or NaOH is in excess.
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The concentrations of hydronium and hydroxide ions must be equal.

Substituting this equality into the ion product constant for water yields.

[H3O+] = sqrt(Kw) = sqrt(1.0 x 10-14) = 1.0 x 10-7

pH = - log(1.0 x 10-7) = 7.00

After Addition of 25.10 mL of Reagent (Post-equivalence)
The solution now contains an excess of NaOH, and we can write
cNaOH = 25.10 x 0.1000 50.00 x 0.0500 = 1.33 x 10-4
75.10
and the equilibrium concentration of hydroxide ion is
[OH] = cNaOH = 1.33 x 10-4 M
pOH = -log (1.33 x 10-4) = 3.88

pH = 14.00 3.88 = 10.12

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OFAcid
THE -PHILIPPINES
Titration Data
for Strong
Strong BaseMANILA
Titration
Volume of NaOH,
mL

pH

50.00 mL of 0.0500 M
HCl w/ 0.1000 M NaOH

50.00 mL of 0.000500 M
HCl w/ 0.001000 M
NaOH

1.3

3.3

10

1.6

3.6

20

2.15

4.15

24

2.87

4.87

24.9

3.87

5.87

25 (EP)

25.1

10.12

8.12

26

11.12

9.12

30

11.8

9.8

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Titration Curves for the Data in the Table above.
14
12
10
8
6

dilute

concentrated

2
0
0

10

20

24

24.9

25

25.1

26

30

Effect of Concentration on Indicator

Choice
Note that the pH break is narrower in dilute
system.
Only those indicators that change color in that
narrow range can be used.
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The Titration of Strong Base and Strong Acid
Example
Calculate the pH during the titration of 50.00 mL of 0.0500 M
NaOH with 0.1000 M HCI after the addition of the following
volumes of reagent: (a) 24.50 mL, (b) 25.00 mL and (c) 25.50 mL.

Pre-equivalence (sample > titrant)

[OH-] = cNaOH = orginal no. mmol NaOH no. mmol HCl added
total volume of solution
= (50.00 x 0.0500 24.50 x 0.1000) = 6.71 x 10-4
M
50.00 + 24.50
[H3O+] = Kw / (6.71 x 10-4) = (1.00 X 10-14)/(6.71 X 10-4)

[H3O+] =1.49 x 10-11

pH = -log(1.49 x 10-11) = 10.83

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Equivalence point (sample = titrant; [H O ] = [OH ])
3

[H3O+] = sqrt(Kw) = sqrt(1.00 x 10-14) = 1.00 x 10-7

pH = -log(1.00 x 10-7) = 7.00

Post-equivalence (titrant > sample)

[H3O+] = cHCl = (25.50 x 0.1000 50.00 x 0.050) = 6.62 x 10-14
75.50

pH = -log (6.62 x 10-4) = 3.18

Titration Curves

14

concentrated

12
10

dilute

8
6
4
2
0
0

10

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15

20

25

30

35

40

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TITRATION CURVES FOR WEAK ACIDS

Four distinctly different types of calculations are needed to derive a

titration curve for a weak acid (or a weak base):

1. At the beginning, the solution contains only the solute acid or base.
The pH is calculated from the concentration of that solute and its
dissociation constant.

2. After addition of titrant, before the equivalence point, the mixture

is a buffer solution.
The pH of the buffer can be calculated from analytical concentrations of
the conjugate base or acid and the residual concentrations of the weak
acid or base.

3. At the equivalence point, the solution contains only the

conjugate of the weak acid or base being titrated (that is, a salt).
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The pH is calculated from the concentration of this salt product.

4. Beyond the equivalence point, the excess of strong acid or

base titrant represses the acidic or basic character of the reaction
product to such an extent that the pH is governed largely by the
concentration of the excess titrant.
Example
Derive a curve for the titration of 50.00 mL of 0.1000 M acetic acid
(Ka = 1.75 x 10-5) with 0.1000 M sodium hydroxide.

Initial pH
Calculate the pH of a 0.1000 M solution of HOAc
[H3O+] = sqrt(Ka.cHOAc) = sqrt(1.75 x 10-3 x 0.1000) = 1.32 x 10-3
pH = - log (1.32 x 10-3) = 2.88
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pH after Addition of 10.00 mL of Reagent

A buffer solution consisting of NaOAc and HOAc has now been produced.

The analytical concentrations of the two constituents are

cHOAc = 50.00 mL x 0.1000 M 10.00 mL x 0.1000 M = 4.000 M
60.00 mL
60.00 mL
cNaOAc = 10.00 mL x 0.1000 M = 1.000 M
60.00 mL
60.00 mL

We substitute these concentrations into the dissociation constant

expression for acetic acid and obtain
Ka = [ H3O+](1.000/60.00) = 1.75 x
10-3
4.000/60.00
[H3O ] = 7.00 x 10-3
+

pH = 4.16
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Equivalence Point pH
At the equivalence point, all the acetic acid has been converted to
sodium acetate.
cNaOAc = (50.00 mL x 0.1000 M)/100 mL = 0.0500 M
OAc- + H2O

HOAc + OH-

but [OH-] = [HOAc]

[OAc-] = 0.0500 [OH-] 0.0500 M

Substituting in the base dissociation constant expression for OAc- gives

[OH-]2 = Kw = 1.00 x 10-14 = 5.17 x 10-10

0.0500
Ka 1.75 x 10-5

[OH-] =sqrt(0.0500 x 5.17 x 10-10) = 5.34 x 10-6

pH = 14.00 ( - log 5.34 x 10-6) = 8.73
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pH after Addition of 50.10 mL of Base

After addition of 50.10 mL of NaOH, both the excess base and the
acetate ion are sources of hydroxide ion.
The contribution of the latter is small, however, because the excess of
strong base represses the reaction.
The hydroxide ion concentration is only 5.34 x 10 -6 M at the equivalence point.
Once an excess of strong base is added, the contribution from the reaction
of the acetate is even smaller.

Thus,

[OH-] cNaOH = 50.10 mL x 0.1000 M 50.00 mL x 0.1000 M

[OH-] =1.00 x 10-4 M

100.1 mL

pH = 14.00 (-log 1.00 x 10-4) = 10.00

Note that the titration curve for a weak acid with a strong base is identical to that for a
strong acid with a strong base in the region slightly beyond the equivalence point.
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UNIVERSITY
OFAcid
THE- PHILIPPINES
Titration Data
for Weak
Strong Base MANILA
Titration
Volume of NaOH,
mL

pH

50.00 mL of 0.1000 M HAc 50.00 mL of 0.001000 M

w/ 0.1000 M NaOH
HAc w/ 0.001000 M NaOH

0.00
10.00
25.00
40.00
49.00
49.90
50.00
50.10
51.00
60.00
75.00
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2.88
4.16
4.76
5.36
6.45
7.46
8.73
10.00
11.00
11.96
12.30

3.91
4.30
4.80
5.38
6.46
7.47
7.73
8.09
9.00
9.96
10.30
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14

pH

UNIVERSITY OF THE PHILIPPINES MANILA

Basic indicator
Neutral indicator

Basic pH at EP

dilute

concentrated

50.00 mL (EP)
Vol of NaOH

14
Ka = 10-9

pH

Basic pH at EP

The smaller the Ka

(the weaker the
acid) the smaller
the rise in pH

Ka = 10-2

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50.00 mL (EP)
Vol of NaOH

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TITRATION CURVES FOR WEAK BASES
The derivation of a curve for the titration of a weak base is analogous
to that of a weak acid.

Example
A 50.00 mL aliquot of 0.0500 M NaCN is titrated with 0.1000 M HCl.
Calculate the pH after the addition of (a) 0.00, (b.) 10.00, (c) 25.00, and
(d) 26.00 mL of acid.

The reaction is

CN- + H3O+

HCN + H2O

(a). 0.00 mL of reagent (HYDROLYSIS)

CN- + H2O
HCN + OH[OH-][HCN] = Kh = Kw = 1.00 x 10-14 = 1.61 x
10-5
[CN-]
Ka
6.2 x 10-10

[CN-] = cNaCN - [OH-] cNaCN = 0.0500

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Substitution into the dissociation constant expression gives, after

rearrangement,

[OH-] = sqrt(Kh cNaCN) = sqrt(1.61 x 10-5 x 0.0500)

[OH-] = 8.97 x 10-4
pH = 14.00 (-log 8.97 x 10-4) = 10.95
(b). 10.00 mL of reagent (BUFFER)
cNaCN = 50.00 x 0.0500 10.00 x 0.1000 = 1.500
M
60.0
60.00
cHCN = 10.00 x 0.1000 = 1.000 M
60.0
60.00

These values are then substituted into the expression for the acid
dissociation constant of HCN to give [H3O+] directly:
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[H3O+] = 6.2 x 10-10 x (1.000/60.00) = 4.13 x 10-10
1.500/60.00
pH = -log (4.13 x 10-10) = 9.38
(c) 25.00 mL of reagent (WEAK ACID)

The principal solute species is the weak acid HCN.

cHCN = 25.00 x 0.1000 = 0.03333
M
75.00

Ka = [H3O+]2/cHCN
[H3O+] = sqrt(Ka cHCN) = sqrt(6.2 x 10-10 x 0.03333)
[H3O+] = 4.55 x 10-6

pH = -log (4.55 x 10-6) = 5.34

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(d) 26.00 mL of reagent (STRONG ACID)

The excess of strong acid now represses the dissociation of the

HCN to the point where its contribution to the pH is negligible.
[H3O+] = cHCl = 26.00 x 0.1000 50.00 x 0.0500 = 1.32 x
10-3
76.00
pH = -log(1.32 x 10-3) = 2.88
14

pH

Kb = 10-2

The smaller the Kb

(the weaker the
base) the narrower
the pH break.

7
Kb = 10-9

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acidic pH at EP

25.00 mL (EP)
Vol of HCl

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