CHAPTER 13

TITRATIONS
IN
ANALYTICAL
CHEMISTRY
(continuation)
IMPORTANT TERMS

Analyte
Titrant
Equivalence Point and End Point
Primary Standard
Standard Solution
13A-2 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 are

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

4-4
BEHAVIOR OF COMPOUNDS THAT DO NOT
EXHIBIT ATMOSPHERIC STABILITY

Deliquescent substances form an aqueous

solution by absorbing water vapor

Efflorescent substances do not absorb water

vapor but spontaneously release moisture

Hygroscopic substances can absorb water

vapor, but they do not form an aqueous
solution.
Important requirements for a
primary standard

4. Ready availability at modest cost

5. Reasonable solubility in the titration medium

6. Reasonably large molar mass so that the

relative error associated with weighing the
standard is minimized

4-6
13A-2 Primary Standards

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.

4-7
n Consider a 0.1025 M HCl was standardized
against primary standard grade Na2CO3.

n A 25-mL pipetful of 0.1025 M HCl was titrated

with 22.56 mL of NaOH.

n Based on the titration data, the molarity of NaOH

solution is 0.1136 M NaOH.

n The 0.1025 M HCl is a secondary standard.

4-8
A standard solution is a reagent of
known concentration that is used in a
titrimetric analysis

13B STANDARD SOLUTIONS

The ideal standard solution for a titrimetric
method will

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

4-10
The ideal standard solution for a titrimetric
method will

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

4-11
13C VOLUMETRIC CALCULATIONS:
ESTABLISHING THE CONCENTRATION
OF STANDARD SOLUTIONS
METHOD I: DIRECT METHOD

n The first is the direct method in which a

carefully weighed quantity of a primary
standard is dissolved in a suitable solvent
and diluted to a known volume in a
volumetric flask.

n Calculate the molar concentration of the

solution from the mass (g) of the primary
standard and volume (mL) solution
4-13
METHOD II: STANDARDIZATION

The second is by standardization in which the titrant

to be standardized is used to titrate

(1) a weighed quantity of a primary standard,

(2) a weighed quantity of a secondary standard,

(3) a measured volume of another standard solution.

4-14
Expressing the Concentration
of Standard Solutions

The concentrations of standard solutions

are generally expressed in units of either
molarity or normality.

4-15
Analyte: Acid
ACIDS – proton (H+) donor;
contain ionizable Hs or acidic Hs

REACTING UNITS

monoprotic acid contains 1

H+ per formula unit of the acid

diprotic acid contains 2 H+ per

formula unit of the acid
Analyte: Acid

Inorganic acids Organic Acids:

Carboxylic Acids
HCl HF
HBr HNO2 RCOOH common organic acid
with the functional group COOH
HI H2SO4
HNO3 H3PO4
Number of COOH = Number of acidic H
HClO4 H3PO3
CARBOXYLIC ACIDS
Examples of monoprotic
weak acids COOH

Organic weak acids C O H

O
HCOOH (formic acid)
ACIDIC
HYDROGEN
CH3CO2H (acetic acid)
Analyte: Base
BASES – proton (H+) acceptor;
negatively charged O
N atom with unshared electron pairs

REACTING UNITS

monoequivalent base reacts with

1 H+ per formula unit of the base

diequivalent base reacts with 2

H+ per formula unit of the base
Analyte: Base
Inorganic bases

Group 1A Metal Hydroxides

Ammonia, NH3

Group 2A Metal Hydroxides

Carbonates

Organic Bases: Amines

RNH2, R2NH or R3N

REQUIREMENTS FOR
TITRATION REACTIONS
In general, a titration reaction can be
represented by the chemical equation

aA + tT ¾® pP

What are the requirements so that a

chemical equation can be considered for use
in titrimetric analysis?
 aA + tT ¾® pP

Requirements for a chemical equation to be considered for

titrimetric analysis

n The reaction must be stoichiometric.

n The reaction must be rapid.

n The reaction must be quantitative.

n There should be a marked change in some property of

the solution when the reaction is complete.
Requirements for a chemical equation
to be considered for titrimetric analysis

aA + tT ¾® pP

n The reaction must be stoichiometric.

The reaction must have a well-defined

balanced chemical equation.
Requirements for a chemical equation
to be considered for titrimetric analysis

aA + tT ¾® pP

n The reaction must be rapid.

The rate of the reaction is very fast or

instantaneous.
Requirements for a chemical equation to be
considered for titrimetric analysis

aA + tT ¾® pP

n The reaction must be quantitative.

The reaction must favor the formation of the
products

The equilibrium constant of the reaction is

very large.
The equilibrium constant of the reaction is very large.

Consider the strong acid-strong base reaction between

hydrochloric acid and sodium hydroxide.

Molecular Form:
HCl(aq) + NaOH(aq) ¾® NaCl(aq) + H2O(l)

Net Ionic Form:

H+(aq) + OH-(aq) ¾® H2O(l)
The equilibrium constant of the reaction is very large.

Molecular Form:
HCl(aq) + NaOH(aq) ¾® NaCl(aq) + H2O(l)

Complete Ionic Form:

H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) ¾® Na+(aq) + Cl-(aq) + H2O(l)

H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) ¾® Na+(aq) + Cl-(aq) + H2O(l)

Net Ionic Form:

H+(aq) + OH-(aq) ¾® H2O(l)
The equilibrium constant of the reaction is very large.
Consider the strong acid-strong base reaction between
hydrochloric acid and sodium hydroxide.

H+(aq) + OH-(aq) ¾® H2O(l)

1
K RXN =
[ H + ][OH - ]
1 1
K RXN = + -
=
[ H ][OH ] KW

At 25°C and 1 atm, KW = 1.0 ´ 10 -14.

The equilibrium constant of the reaction is very large.
Consider the strong acid-strong base reaction between
hydrochloric acid and sodium hydroxide.

H+(aq) + OH-(aq) ¾® H2O(l)

1 1
K RXN = + -
=
[ H ][OH ] KW

At 25°C and 1 atm, KW = 1.0 ´ 10-14.

1 1
K RXN = = = 1.0 ´ 1014

KW 1.0 ´ 10 -14
Requirements for a chemical equation
to be considered for titrimetric analysis

aA + tT ¾® pP

n There should be a marked change (or a

remarkable change) in some property of
the solution when the reaction is
complete.
.
Titration Curve: Plot of the progress of the reaction
Titration Curve: Plot of the progress of the reaction
Titration Curve: Plot of the progress of the reaction