MODULE 1

VOLUMETRIC METHODS: NEUTRALIZATION METHOD –

PART 1

by ; Ma. Cleofe N. Badang, PhD

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

to:

1. define relevant terms in volumetric method of analysis

2. identify ways of expressing solution concentration
3. solve problems on direct acid-base (neutralization)
titrations.

VOLUMETRIC METHOD OF ANALYSIS

Volumetric (Titrimetric) methods of analysis are analytical

methods in which the volume of a solution of known concentration
consumed during analysis is a measure of the amount of active
constituent in a sample being analyzed. The chemical substance
being analyzed is referred to as the analyte or the active
constituent in the sample. A standard solution (titrant) is one
whose concentration is accurately known. The process by which a
standard solution is brought into reaction until the desired
reaction is accomplished is known as titration. The indicator is
usually a chemical which changes color at or very near the
endpoint. Endpoint (practical) of a titration is shown by the
change of color of the indicator. The theoretical point at which
equivalent amounts of each substance have reacted is the
equivalence point or stoichiometric point or theoretical endpoint.
The theoretical and practical endpoints should coincide,
otherwise the indicator used is not suitable to accomplish the
endpoint of the titration. The following are the common
methods of expressing concentration of standard solution used in
volumetric analysis:
a) A normal solution contains one gram equivalent weight of
solute in a liter of solution or one gram milliequivalent weight in a
milliliter of solution.
* An equivalent weight of a substance is that amount equivalent in
reacting power to an atom of hydrogen. The equivalent weight
expressed in grams is the gram equivalent weight. A thousands
part of the equivalent weight is called milliequivalent weight. The
milliequivalent weight expressed in grams is the gram
milliequivalent weight (GmEW).

b) A molar solution contains a mole solute (one gram molecular

weight) in a liter of solution or one millimole per milliliter of
solution. A mole is the molecular weight expressed in grams. A
millimole is one thousandth part of a mole.

c) A molal solution contains a mole (one gram molecular weight) in

a 1000 grams of solvent.

d) Titer is the strength in grams per milliliter of solution, either

the grams of solute contained in a milliliter of solution or the
weight in grams of a substance that will react with one milliliter
of solution.

Titrimetric analysis may be direct or residual. Direct

titration is conducted by introducing a standard solution gradually
from a buret into a solution of a substance being assayed until
chemically equivalent amounts of each have reacted as shown by a
change in color of the indicator added.
The process by which the exact concentration of a solution
is determined accurately is known as standardization. It may
either be standardization using a primary or secondary standard.
A primary standard is a chemically pure solid substance which is
used in a direct standardization of a solution. Other
requirements for a primary standard are (1) it must be pure, (2)
it must be stable and non-hygroscopic, (3) it must be of
definite known composition, (4) t must react stoichiometrically
with the substance present in the solution, (5) it must be
soluble in water and (6) it must have a fairly high molecular
weight.

A secondary standard is a substance that is not necessarily

pure but whose exact purity is known. A standard solution is a
commonly used secondary standard.

Chemical Reactions Used in Titrimetry

The four types of chemical reactions which serve as the

basis of titrimetric analysis are: (1) neutralization (acid-base) in
aqueous and nonaqueous solvents, (2) oxidation-reduction, (3)
precipitation, and (4) complexation.

Regardless of the type of reaction used, however, four

requirements must be met if the reaction is to be used for
titrimetric analysis. They are: (1) the reaction must proceed to
completion, that is, the chemical equilibrium constant K must be
equal to or greater than 108; (2) the reaction must proceed in a
stoichiometric manner; (3) a suitable end-point detecting device
(chemical indicators electrodes, etc.) must be available; and (4)
for direct titrimetric methods the reaction must be rapid so a
sharp end point is discernible.

THEORY OF NEUTRALIZATION TITRATIONS

Standard solutions of strong acids and strong bases are

used extensively for determining analytes that are themselves
acids or bases or analytes that can be converted to such species
by chemical treatment.
 Neutralization reactions are chemical processes in which an
acid (proton donor) reacts with a base (proton acceptor). The
products of neutralization reaction in aqueous solution are water
and a salt, e.g., NaCl, sodium acetate, etc. depending upon the acid
and base used in the reaction. As with all chemical reactions used
in titrimetry, neutralization reactions must proceed very nearly
to completion to be of value in quantitative analysis.

Standard Solutions
The standard solutions employed in neutralization titrations
are strong acids or strong bases because these substances react
more completely with an analyte than do their weaker
counterparts and thus yield sharper end points. Standard
solutions of acids are prepared by diluting concentrated
hydrochloric or sulfuric acid. Either acid may be used in most
titrations, but hydrochloric acid is preferable to the sulfuric acid
in the titration of compounds that yield a precipitate with the
latter, such as barium hydroxide, and sulfuric acid is preferable
in hot titrations, since there would be danger of loss of
hydrochloric acid due to volatilization. Nitric acid is seldom used
because its oxidizing properties offer the potential for
undesirable side reactions.
Standard solutions of bases are ordinarily prepared from
solid sodium, potassium, and occasionally barium hydroxides.
These solutions absorb carbon dioxide from the air, thereby
changing rapidly in concentration. Sodium and potassium
hydroxides may become contaminated with carbonates that
impair their usefulness because of the liberation of carbon
dioxide during acid-alkali titration. Barium hydroxides remain
free from carbonates, since absorbed carbon dioxide is
precipitated as insoluble barium carbonate; this, however,
decreases the concentration of barium hydroxide in the solution.
Indicators
Indicators are complex organic compounds used (1) to
determine the end points in neutralization processes, (2) to
determine the hydrogen-ion concentrations [H+] or pH, or (3) to
indicate that a desired change in pH has been effected. These
organic substances may be acids or bases themselves, capable of
existing in two forms of different color that are mutually
convertible, one into the other, at given hydrogen-ion
concentrations. To explain the change in color of indicators,
three theories have been proposed which, briefly stated, are as
follows:

1. The physicochemical theory attributes the color to certain

ions an increase in which causes the appearance of a new
color, a decrease in which causes the disappearance of a
color or the appearance of a different color.
2. The organic theory attributes the color of indicators to
certain groupings of the elements in a compound, and the
change in color to a change in molecular structure.
3. The colloidal theory assumes that indicators form colloidal
solutions the change in color of which is dependent upon
change in size of the colloidal particle.

The point at which an indicator changes color in any given

titration is dependent on the hydrogen-ion concentration of the
solution and may not be indicative of the absolute neutrality or
completion of a reaction.

Rules for the Use of Indicators

1. Use 3 drops of indicator test solution for a titration unless

otherwise directed.
2. When a strong acid is titrated with a strong alkali, or a
strong alkali with a strong acid, methyl orange, methyl red,
or phenolphthalein may be used
 3. When a weak acid is titrated with a strong alkali, use
phenolphthalein as the indicator.
4. When a weak alkali is titrated with a strong acid, use methyl
red as indicator.
5. A weak alkali should never be titrated with a weak acid, or
vice versa, since no indicator will give a sharp end point.
6. The appearance of a color is more easily observable than
the disappearance. Therefore, always titrate where
possible to the appearance of a color.

CALCULATIONS IN VOLUMETRIC ANALYSIS

In any volumetric titration, we should bear in mind that the

following assumptions always apply:

milliequivalents of analyte = milliequivalents of titrant

or millimoles of analyte = millimoles of titrant

For Acid base direct titration methods: meq acid = meq base or
mmole acid = mmole base

For most calculations, meq is commonly used since the

concentration of standard solution (titrant) is usually given in
normality.

Sample Problem 1: If 25.00 ml of a sodium hydroxide solution

required 40.00 ml of a sulfuric acid solution in a titration, and
25.00 ml of the sulfuric acid solution were required in the
titration of 0.3060 g pure sodium carbonate, what was the
normality of the sodium hydroxide?

First, let us identify the given data, find out what is being asked
in the problem and find the solution.
Given : 25 ml NaOH = 40 ml H2SO4
25 ml H2SO4 required to titrate 0.3060 g Na2CO3

Required: N of NaOH

Solution : meq H2SO4 = meq Na2CO3

meq NaOH = meq H2SO4

First, let us solve for the N of H2SO4

meq H2SO4 = meq Na2CO3

N H2SO4V H2SO4 = g Na2CO3

GmEW Na2CO3

N H2SO4 = g Na2CO3
GmEW Na2CO3 х V H2SO4

GmEW Na2CO3 = 106/2000 = 0.053 g /meq

N of H2SO4 = 0.3060 g = 0.2309 meq/ml

0.053 g/meq х 25.00 ml

Finally, let’s solve for the normality of NaOH:

meq NaOH = meq H2SO4
NNaOHVNaOH = N H2SO4V H2SO4

NNaOH = 0.2309 meq/ml х 40.00 ml

25.00 ml
NNaOH = 0.3694 meq/ml

Sample Problem 2: A 50.00-ml sample of calcium hydroxide

solution required 19.50 ml of 0.1050 N hydrochloric acid solution
in a titration. Calculate (a) the amount of Ca(OH) 2 in the 50.00
ml-sample and (b) the Ca(OH) 2 concentration in %w/v.
Given: V sample = 50.00 ml
N HCl = 0.1050 meq/ml
V HCl = 19.50 ml
Required: a) g Ca(OH) 2
b) % w/v Ca(OH) 2

Solution : a) meq Ca(OH) 2 = meq HCl

g Ca(OH) 2 = N HCl V HCl
GmEW

g Ca(OH) 2 = 0.1050 meq/ml x 19.50 ml x 74.08

2000
g Ca(OH) 2 = 0.0758 g

b) % Ca(OH) 2 = g Ca(OH) 2 x 100

vol. sample
= 0.078 g x 100
50.00 ml
Ca(OH) 2 = 0.1516

PROBLEMS:

1. Define the following terms: (a) normality, (b) molarity,

(c) milliequivalent, (d) equivalent weight, (e) titer

2. What weight of 98.5% KHC8H4O4 is equivalent to (a) 35 ml of

0.01 N NaOH, (b) 35 ml of 0.1M Ba(OH) 2?

3. If 25.00 ml of hydrochloric acid solution were required in

titration of a 0.6500-g sample of pure sodium carbonate, what
weight of each of the following pure reagents would be required
to neutralize 25 ml of the hydrochloric acid solution? (a) NaHCO3,
(b) KOH, (c) Ba(OH)2, (d) CaO
4. If 25.00 ml of a sulfuric acid solution were found to be
equivalent to 20.50 ml of a sodium hydroxide solution, and 35.00
ml of the sodium hydroxide solution were found to be equivalent
to 0.7140 g of pure potassium biphthalate, what weight of barium
sulfate could be produced from 50.00 ml of the sulfuric acid
solution?

5. A 2.0284-g sample of primary standard potassium hydrogen

phthalate (KHP, MW 204.22) was dissolved and diluted to 250.0
ml. A 20.00-ml aliquot of this solution required 32.19 mlof a
sodium hydroxide solution for titration to the phenolphthalein
end point. Calculate the molar concentration of the sodium
hydroxide solution.

References:
1. A.M Knevel & F. E. Digangi, Jenkin’s Quantitative
Pharmaceutical Chemistry, 7th ed. (Reprinted). Philippines:
Merriam & Webster, Inc.

2. D.A. Skoog & D.M. West, Fundamentals of Analytical

Chemistry , 7th ed., Saunders College Publishing, New York.

CONGRATULATIONS!
You are now ready for your next module…