Module 4 – Principles on Volumetric Methods of Analysis

Review: • For acid solution, n is the number of H+ ions provided by a

Expressing Solution Concentrations
1. Molar Concentration, [X]
– The molar concentration of a solution of a chemical
species X is the number of moles of the solute species
that is contained in one liter of the solution (not one
liter of the solvent).
– Molar concentration, or molarity M, has the
dimensions of mol/L.
2. Analytical Molarity, CX
– The analytical molarity of a solution gives the total
number of moles of a solute in 1 L of the solution, or
alternatively, the total number of millimoles in 1 mL.
– For example, a sulfuric acid solution that has an
analytical concentration of 1.0 M can be prepared by
dissolving 1.0 mol, or 98 g, of H2SO4 in water and
diluting to exactly 1.0 L.
3. Percent Concentration
– Chemists frequently express concentrations in
terms of percent (parts per hundred).
– Three common methods are
formula unit of acid.
Ex. A 3 M H2SO4 solution is the same as a 6 N H2SO4 solution.
• For a basic solution, n is the number of OH- ions provided by
a formula unit of base.
Ex. A 1 M Ca(OH)2 solution is the same as a 2 N Ca(OH)2
solution.
• In a precipitation reaction, the reaction unit is the charge of
the cation or anion participating in the reaction; thus, for
the reaction below, n = 2 for Pb2+ (aq) and n = 1 for 2I-
Pb2+ (aq) + 2I- (aq) ⇌ PbI2 (s)
• For a complexation reaction, n is the number of electron
pairs that the metal accepts or that the ligand donates.
Ex. n = 2 for Ag+(aq) because the silver ion accepts two pairs
of electrons, and n = 1 for NH3 because each ammonia has
one pair of electrons to donate in the reaction:
Ag+(aq) + 2 NH3 (aq) ⇌ Ag(NH3)2+ (aq)
• For redox reaction, n is the number of electrons released by
the reducing agent or accepted by the oxidizing agent; thus,
n = 1 for Fe3+ (aq) and n = 2 for Sn2+ (aq) in the reaction:
2 Fe3+ (aq) + Sn2+ (aq) ⇌ Sn4+ (aq) + 2 Fe2+ (aq)
because
2 Fe3+ (aq) + 2 e- ⇌ 2 Fe2+ (aq) (Fe3+ gains 1 e-)
Sn2+ (aq) ⇌ Sn4+ (aq) + 2 e- (Sn2+ loses 2 e-)

Note: The normality of a solution is NEVER less than its molarity!

Titrimetry includes a group of analytical methods based on

determining the quantity of a reagent (called titrant) of known
concentration that is required to react completely with the
4. Parts Per Million and Parts Per Billion analyte (also known as titrand).

Volumetric titrimetry is a type of titrimetry in which the standard

reagent is measured volumetrically.
or
Reactant A + Reactant B → Products
contains analyte reacts with analyte and its
[analyte] = ? [B] is known;
5. p-Functions ↓ titration
– Scientists frequently express the concentration of a /volume volume of [B], mL
species in terms of its p-function, or p-value. The p- (mL) of ↓ *M (mmol/mL)
value is the negative base-10 logarithm (log) of the analyte mmol B
molar concentration of that species. solution ↓ mole ratio of B to
analyte in A
pX = −log[X] mmol analyte

------------------------------- END OF REVIEW------------------------------ Classification of Volumetric titrimetry:

1. Acid-Base
Analyte: both inorganic and organic that are either acids or
Normality (N)—A different Way to do Volumetric Calculations
bases
– is defined as the number of mole equivalents per liter of Titrant: a standard solution of a strong base or a strong acid
solution: Indicator: weak acid/base indicator; pH meter
N = n/L of solution, where n is the # of mole equivalents
M = N*n
2. Precipitation
– the titrant forms an insoluble product (precipitate)
with the analyte (titrand).
3. Complexometric
– the titrant (a chelating agent) forms a water-soluble
colored complex with the analyte (a metal ion).
4. Reduction-Oxidation
– involves the titration of an oxidizing agent with a
reducing agent, or vice versa. An oxidizing agent gains
electron and a reducing agent loses electrons in a
reaction between them. There must be a sufficiently
large difference between the oxidizing and reducing
capabilities of these agents for the reaction to go to
completion and give a sharp end point; that is, one
should be a fairly strong oxidizing agent (strong
tendency to gain electrons) and the other a fairly
strong reducing agent (strong tendency to lose
electrons).
Common features of all titrimetric methods:
• If a titration is to give an accurate result, we must combine
the titrand and the titrant in stoichiometrically equivalent
amounts. This stoichiometric mixture is called the
equivalence point.
• An accurate titration requires that the exact volume of
titrant at the equivalence point, Veq must be known.
• Requires calculation of moles titrant that reacted with the
titrand (MT x Veq = moles titrant)
• Moles of the titrand can be calculated using the
stoichiometry of the titration reaction.
• There is no obvious sign when to reach the equivalence
point so addition of the titrant will stop at end point.
• The end point is indicated by a slight change in the color of
a substance called an indicator that should be added to the
titrand’s solution before titration.
• The difference in volume between the equivalence point
and the end point is the titration error.
Four conditions for a reaction to serve in a titrimetric method:
1. Stoichiometry between the titrant and the titrand must be
known.
2. The titration reaction must effectively proceed to
completion.
3. The titration reaction must occur rapidly.
4. A suitable method for accurately determining the end point
must be known.
Direct titration is a process in which the titrant reacts directly
with the analyte.
Back-titration is a process in which the excess of a standard
solution used to consume an analyte is determined by titration
with a second standard solution. This process is often required
when the rate of reaction between the analyte and reagent is
slow or when the standard solution lacks stability.
A standard solution is a reagent of known concentration that is
used in a titrimetric analysis.
The ideal standard solution for a titrimetric method should
1. be sufficiently stable so that it is only necessary to
determine its concentration once;
2. react rapidly with the analyte so that the time required
between additions of reagent is minimized;
3. react completely with the analyte so that satisfactory
end points are realized;
4. undergo a selective reaction with the analyte that can
be described by a balanced equation.
Establishing the Concentration of Standard Solutions
– Two basic methods:
1. direct method - carefully weighed quantity of a primary
standard is dissolved in a suitable solvent and diluted to
a known volume in a volumetric flask
2. standardization - the titrant to be standardized is used
to titrate:
a. a weighed quantity of a primary standard,
b. a weighed quantity of a secondary standard, or
c. a measured volume of another standard solution
The concentrations of standard solutions are generally expressed
in units of either molarity (M) or normality (N).
A secondary standard is a compound whose purity has been
established by chemical analysis and that serves as the reference
material for a titrimetric method of analysis.
A primary standard is a highly purified compound that serves as
a reference material in all volumetric and mass titrimetric
methods.
Important requirements for a primary standard:
1. High purity (established methods for confirming purity
should be available)
2. Atmospheric stability
3. Absence of hydrate water so that the composition of the
solid does not change with variations in relative
humidity
4. Available at modest cost
5. Reasonable solubility in the titration medium
6. Large molar mass so that the relative error associated
with weighing the standard is minimized
The two most widely used end points involve:

1. changes in color due to the reagent, the analyte, or an

indicator, and
2. a change in potential of an electrode that responds to
the concentration of the reagent or the analyte.

To find a titration’s end point, we need to monitor some property

of the reaction that has a well-defined value at the equivalence
point. A titration curve provides a visual picture of how a
property of the titration reaction changes as we add the titrant
to the titrand.

Figure 5-1 Typical acid–base titration curve showing how the

titrand’s pH changes with the addition of titrant. The titrand is a
25.0 mL solution of 0.100 M HCl and the titrant is 0.100 M NaOH.
The titration curve is the solid blue line, and the equivalence
point volume (25.0 mL) and pH (7.00) are shown by the dashed
red lines. The green dots show two end points. The end point at
a pH of 6.8 has a small titration error, and the end point at a pH
of 11.6 has a larger titration error.

REFERENCES
Skoog, West, Holler and Crouch. (2012) Fundamentals of
Analytical Chemistry, 9th ed., Cengage Asia

Harvey, David. (2008) Modern Analytical Chemistry, McGraw-Hill

Companies. ISBN 0–07–237547–7

Prepared by:

Mary-Ann A. Landiao, RCh, MSc

Faculty, Chemistry Dept.