MODULE 2

VOLUMETRIC METHODS: NEUTRALIZATION METHOD –

Part 2
Prepared by : Maria Cleofe N. Badang, MS Chem

Objectives: At the end of this course, the learner is expected

to:
1. construct a titration curve for an acid-base titration
2. understand the principle behind residual acid-base titration
3. differentiate between acidimetry and alkalimetry
4. solve problems involving direct and residual titration in
acidimetry and alkalimetry.

TITRATION CURVES

The manner in which the pH of a solution changes during a

titration is best shown by preparing a graph in which the pH value
is plotted on the y axis and the volume of the titrant is plotted on
the x axis. Titration curves may be prepared from pH data
obtained experimentally, or the data for the graph may be
calculated. The equivalence point on the titration curve is that
portion where the slope of the curve is steepest and is commonly
referred to as the break in the titration curve. When an
indicator is used to detect the equivalence point, it must give a
sharp discernible color change at that point in the titration;
otherwise the color change may lead to erroneous results.

The preparation of a titration curve is not difficult if one

realizes that the calculations are based on only four types of
points, which correspond to:

1. The pH of the solution being titrated but before any titrant

is added.
2. The pH of the solution after titrant is added but before
the equivalence point is reached
3. The pH at the equivalence point
4. The pH beyond the equivalence point
Titration of a Strong Acid Using a Strong Base
In this type of titration a strong acid, such as HCl, is
titrated with NaOH, a strong base.

To illustrate, suppose that 20.00 ml of exactly 0.1 N HCl

were taken, diluted with sufficient distilled water to measure
exactly 100 ml, and titrated with exactly 0.1N NaOH solution.

1. Calculate the pH of the solution before any titrant is added.

20.00 ml x 0.1 meq/ml = 2.00 meq of HCl in 100 ml solution

[H3O+] = 2.00 meq = 2.00 x 10─2N

100 ml

pH = ─log2.00 x 10─2 = 2.00 ─ 0.30 = 1.70

2. Calculate the pH of the solution after 15.00 ml of 0.1 N NaOH

is added

20.00 ml x 0.1 meq/ml = 2.00 meq of HCl originally present

15.00ml x 0.1 meq/ml = 1.50 meq of NaOH added

This quantity of base when added to 2.00 meq of HCl produces

1.50 meq. of NaCl. Therefore 2.00 ─ 1.50 = 0.50 meq of HCl
remains, and

[H3O+] = 0.50 meq = 4.35 x 10─3N

115 ml
pH = ─log 4.35 x 10─3 = 3.00 ─ 0.64 = 2.36

3. Calculate the pH of the solution after 20.00 ml of 0.1 N NaOH

is added

20.00 ml x 0.1 meq/ml = 2.00 meq of HCl originally present

20.00ml x 0.1 meq/ml = 2.00 meq of NaOH added

This quantity of base when added to 2.00 meq of HCl produces

2.00 meq NaCl; subtracting 2.00 from 2.00 leaves no HCl
remaining. Since neither analyte nor titrant is left over, we are
at the equivalence point and the flask contains only the products
of the reaction, NaCl and H2O. Since water is the major supplier
of both H3O+ and OH─,

2 H2O D H3O+ + OH─

Kw = [H3O+] [OH─] = [H3O+]2
[H3O+] = Kw = 1.00 x 10─14 = 1.00 x 10─7 M

pH = 7.00

4. Calculate the pH of the solution after 29.00 ml of 0.1 N NaOH

is added.
20.00 ml x 0.1 meq/ml = 2.00 meq of HCl originally present
29.00ml x 0.1 meq/ml = 2.90 meq of NaOH added

This quantity of base when added to 2.00 meq of HCl produces

2.00 meq of NaCl and 2.90 ─ 2.00 = 0.90 meq of NaOH
remaining unreacted.

[OH─] = 0.90meq = 6.98 x 10─3 N

129 ml

pOH = log 6.98 x 10─3 = 3.00 ─ 0.84 = 2.16

pH = pKw – pOH = 14.00 – 2.16 = 11.84

THEORY OF RESIDUAL TITRATION

Residual titration (back titration) is carried out by adding
an accurately measured quantity of standard solution known to be
in excess and titrating the excess with another standard solution.
Residual titration is frequently used when a reaction proceeds
slowly or when the substance to be assayed does not give distinct
sharp endpoint with an indicator by direct titration. When the
sample can’t be brought into solution without changing its
chemical nature.

ACIDIMETRY
Acidimetry, the direct or residual titrimetric analysis of
bases using an accurately measured volume of acid, is supplied in
the analytical control of a considerable number of official
substances, both inorganic and organic.

Direct titration is conducted by introducing a standard acid

solution gradually from a buret into a solution of the base being
assayed until chemically equivalent amounts of each have reacted
as shown by some change in properties of the mixture. Such an
end point, which must be close to the stoichiometric point, is
made evident by a change in the color of some indicator or by
potentiometric means.

DIRECT TITRATION METHODS

Sample Problem 1: If a 0.2800-g sample of sodium bicarbonate

(96.5% NaHCO3) is titrated with 0.9165 N sulfuric acid, what
volume of the acid should be required to produce an end point?

Given: wt. sample = 0.2800 g (96.5% NaHCO3)

N H2SO4 = 0.9165 meq/ml
Req’d: V of H2SO4

Solution: meq H2SO4 = meq NaHCO3

N H2SO4 V H2SO4 = g NaHCO3
GmEW NaHCO3
V H2SO4 = g NaHCO3
GmEW NaHCO3 х N H2SO4
 GmEW NaHCO3 = 84/1000 = 0.084 g /meq

V of H2SO4 = 0.2800g (0.965) = 3.51 ml

0.084 g/meq х 0.9165 meq/ml

RESIDUAL TITRATION METHODS

Residual titration is used whenever the end point of a direct

titration deviates appreciably from the stoichiometric point for
some reason; e.g.. when the basic sample is insoluble in water and
the rate of its reaction with the standard acid is relatively slow.
In such a procedure, the basic sample is treated with an amount
of standard acid known to be in excess of a chemically equivalent
amount, and the excess acid is subsequently titrated with a
standard base. The amount of the standard acid which is
chemically equivalent to the basic sample can be calculated simply
by subtracting, from the total amount of standard acid employed,
the amount of acid neutralized by the standard base in the back
titration.

Sample Problem 2: If a 1.2500-g sample of zinc oxide, 95.0%

ZnO, were treated with 50.00 ml of 1.1230 N sulfuric acid in the
usual way, what volume of 0.9765N sodium hydroxide would be
required in the back titration?

Given: wt. sample = 1.2500 g (95.0% ZnO)

N H2SO4 = 1.1230 meq/ml
V H2SO4 = 50.00 ml
N NaOH = 0.9765 meq/ml

Required: V of NaOH req’d in the back titration

Solution: meq ZnO = meq H2SO4 ─ meq NaOH

 g ZnO = ml H2SO4 x N ─ ml NaOH x N
GmEW ZnO
g ZnO = [ml H2SO4 x N ─ml NaOH x N] GmEW ZnO

% ZnO = g ZnO x 100

g sample

% ZnO = [ml H2SO4 x N ─ml NaOH x N] GmEW ZnO x 100

g sample

Since we are looking for ml NaOH, we substitute the given data

to the equation above, and perform the necessary mathematical
calculations, you will arrive at the following answer:

V of NaOH = 27.6 ml

Other Applications: Nitrogen Determination by the Kjeldahl

Method, Assay of Milk of Magnesia

ALKALIMETRIC ANALYSIS

Acids are estimated quantitatively by methods analogous to

those employed for the quantitative estimation of bases, viz., by
directly titrating an exact quantity of the acid, acid salt, or other
acidic substance with standard alkali solutions or by adding an
excess of the latter and determining the amount in excess by
residual titration with standard acid solution. Direct titration is
employed whenever practicable, since it requires only one
standard solution, the standard base, and fewer measurements of
volume.
 In assaying acids, the quantity of acid to be taken should be
such that about 30 to 40 ml of the standard base will be
consumed. As a general principle, it is recommended that the
normality of the solution obtained by dissolving the acid sample
be approximately the same as that of the titrant. Except when
otherwise directed, the liquid to be titrated should be brought to
room temperature before titration, as many indicators give
different values at different temperatures. For most inorganic
acids, methyl red and phenolphthalein can be used as
indicators, and the alkali should be standardized with the
particular indicator used. For organic acids, phenolphthalein is
frequently used; however, thymol blue, bromothymol blue, and
thymolphthalein are also employed. In addition to the visual
methods, potentiometric methods are also used in determining
the end point.

DIRECT TITRATION METHODS

Sample Problem: A 4.0520-g sample of hydrochloric acid, sp. gr.

1.18, required 44.15 ml of 0.9035 N sodium hydroxide in a
titration. Calculate the HCl content in percent.

Given : wt sample = 4.0520 g

Sp. gr. = 1.18
V of NaOH used = 44.15 ml
N of NaOH = 0.9035 meq/ml
GmEW of HCl = 36.46/1000 = 0.03646 g /meq

Required: % HCl

Solution : % HCl = g HCl x 100

g sample
 meq HCl = meq NaOH
g HCl = ml NaOH x N
GmEW

g HCl = ml NaOH x N x GmEW of HCl

% HCl = ml NaOH x N x GmEW of HCl x 100

g sample

Substituting the given data to the equation above, the answer is:

HCl content = 35.89%

RESIDUAL TITRATION METHODS: Assay of Aspirin is done by

residual alkalimetry. For other applications, rfer to table 5.2,
p.112 of Jenkin’s.

PROBLEMS:

1. A sample of 0.100 M HCl is being titrated with 0.100 M

NaOH. Calculate the pH when the volume of titrant added
1s 95%, 100% and 105% of the equivalence-point volume.
Plot the titration curve.
2. Calculate the following titer values for 1 N sulfuric acid: (a)
KHCO3, (b) K2CO3, (c) CaCO3
3. What weight of strontium acetate containing 99%
Sr(CH3COOH)2.½H2O must be used as sample in an assay
according to the general method for alkali salts of organic
acids if, after treatment of the ash with 50.00 ml of 0.5162
N hydrochloric acid, it is desirable to consume 30.00 ml of
0.4675 N sodium hydroxide in the back titration?
 4. A 2.5000-g sample of acetanilide (98.5% C8H4NO) was
assayed by a Kjeldahl procedure. If the ammonia from the
sample were distilled into 50.00 ml of 1 N sulfuric acid,
what volume of 1.2450 N sodium hydroxide would be
required in the titration?

5. A 10.00-ml sample of sulfuric acid solution required 16.85 ml

of a sodium hydroxide solution in a titration. Each milliliter
of the sodium hydroxide solution was equivalent to 0.2472 g
of pure potassium biphthalate. Calculate the H2SO4 content
of the sulfuric acid solution in %w/v.

References:
1. A.M Knevel & F. E. Digangi, Jenkin’s Quantitative
Pharmaceutical Chemistry, 7th ed. (Reprinted), Merriam &
Webster, Inc., Philippines
2. L.G. Hargis, Analytical Chemistry, Prentice Hall, Inc. New
Jersey, 1988.