VOLUMETRIC ANALYSIS

Volumetric analysis is a quantitative technique used in analytical chemistry to determine the

amount of substance in a given sample. It could be the concentration of a given sample solution,
the purity of a substance, or the composition of a sample.
In volumetric analysis also known as titrimetric analysis involves reacting samples that are in
solution .It involves measuring the volume of reagent needed to react with the substance to be
analysed (the analyte). The process of adding the reagent to the analyte using specialized
equipment and standard procedures is called titration.
 Titration is defined as a process in which solution of reagent from a burette (titrant) is
added to the analyte solution in a volumetric flask or conical flask or beaker, until the
reaction is complete.
 A reaction is said to have reached completion when one or both reactants get used up
(consumed)
Principles of volumetric analysis
Procedure
1. The volume of added reagent is taken from the burette and is called the titre.
2. The titrant should be a solution of known concentration. Such a solution is called a standard
solution.
3. The solution to be analysed is transferred to a conical flask or beaker using a graduated
pipette. The measured volume of analyte is called an aliquot.
4. The titrant is slowly added to the analyte until the end point is reached.
5. The volume of standard solution from the burette (titre) is noted.
NB. Several titrations ( 4 – 5) are carried out and the average titre is taken.
6. Calculating the amount.
Principal requirements for a titration reaction are
 Should have a large equilibrium constant.(i.e the reaction should be able to go to
completion)
 The reaction should be fast (so as to reduce the time taken to obtain results)
 The reaction must be stoichiometric
 Should have a well balanced and known reaction equation.
 There should be no side reactions. (i.e. no other reactions should take place besides the
one envisaged.
 There should be some marked change in property such as colour, PH or electrical
conductivity.
 Determining the end-point
There are several methods for determining when the analyte has been consumed:
 Observing an indicator colour change.
An indicator is a substance/compound with the colour that changes abruptly at/near
the equivalence point.
The change in colour is caused by the disappearance of the analyte or appearance of
excess titrant.
The indicator dissociates according to the following equilibrium rxn:
HInd↔ H+ + Ind-
( Colour 1) (colour 2)
 Detecting a sudden change in pH using a pH-meter.
 Electrical conductivity by measuring voltage or current using a pair of electrodes.
(conductivity meter)
Equivalence Point, is a point when the quantity of titrant added is exactly the amount necessary
for stoichiometric reaction with the analyte in the reaction flask. The equivalence point is the
ideal result we seek in a titration, but in practice what we measure, which is marked by the
sudden change in physical property of a solution , is called the end point.
The difference between the equivalence point and end- point is a titration error
Standard Solution
The validity of an analytical result depends on knowing the amount of one of the reactants used.
i.e. a standard.
 A standard solution is a solution of known concentration.
Categories of Standard solutions
a) Primary standard
 A primary standard solution is a solution of known concentration made from a primary
standard, i.e. a substance available in a sufficiently pure form that it requires no
determination of concentration
A substance becomes a primary standard if it meets the following characteristics:
(i) 99.0% pure or better
(ii) High molecular mass
(iii) Stable to drying temperatures
(iv) Hygroscopic, do not absorb water
(v) React fast and stoichiometrically
The preparation of a primary standard solution from a primary standar involves weighing the
primary standard reagent and dissolving it in suitable solvent and diluting to the required
volume.
Properties of a 1⁰ standard solution:

 Should be stable
 React rapidly with the analyte in order to minimize time.
 React more or less completely with the analyte so that the results are valid.
 Undergo a selective reaction with the analyte that can be described by a simple balanced
equation.
b) Secondary (2⁰) standard
A 2⁰ standard solution is a solution which has to be standardized, first agaist a 1⁰ standard ,but
afterwards, it will be stable enough for titrimetric work. In most cases the titrant is not available
as a 1⁰ standard . Instead, a 2⁰ is weighed and dissolved in a suitable solvent to give a solution of
approximate concentration. The solution is the standardized using a 1⁰ standard solution. This
done to get the exact concentration of the solution.
Examples of 2⁰ standard are:
 potassium manganate(VII), KMnO4 . It has to be standardized first, but afterwards can be
used for quantitative analysis
 solutions of hydrochloric acid HCl and sodium hydroxide NaOH.

TYPES OF TITRATION METHODS

Titration methods are classified into 4 types:
I. Acid-base titrations
II. Complexometric titrations
III. Redox titrations
IV. Precipitation titrations
 ACID-BASE TITRATIONS
Involve the reaction between an acid and a base, Such reactions are referred to as neutralization
reactions. An acid-base titration is the determination of the concentration of an acid or base by
exactly neutralizing the acid/base with base or acid of known concentration. This allows for
quantitative analysis of concentration of an unknown acid or base solution. It makes use of the
neutralization rxn between acids and bases and the knowledge of how acids and bases will react f
their chemical formulae are known.
Generally, neutralization is a reaction between an acid and a base to produce a salt and water
only.
The general equation is :
ACID + BASE → SALT + WATER
Some common laboratory bench acids are:
a) Hydrochloric acid HCl b) Nitric acid HNO3 c) Sulphuric acid, H2SO4
Some common bases
a) Sodium hydroxide NaOH b) Potassium hydroxide KOH, c) Ammonia solution NH3(aq)
 Acid-base titrations can also be used to find percent purity of substances/chemicals
Alkalimetry and acidimetry
 Alkalimetry a.k.a alkimetry is the specialized analytic use of acid-base titration to
determine the concentration of a (alkaline) solution.
 Acidimetry, sometimes spelled acidometry, is the same concept of specialized analytic
acid-base titration, but for an acidic substance.
After the titration has been carried out a calculation has to be carried out to determine the
concentration of the analyte or percent purity of the chemical. Calculation involve solution
stoichiometry
THEORY OF SOLUTION STOICHIOMETRY
Solution stoichiometry involves calculating amounts for reactions that take place in solution. An
important quantity when dealing with solutions is the concentration of the solutions. The basic
procedure is similar to that for calculating reacting masses
 Write the balanced equation for the titration reaction
 Find the number of moles of the substance with given concentration and volume using
expression
Number of moles (n) = concentration (c) x volume (V)

n=cxV

 Write down the stoichiometric ratio from the balanced equation

 Use the ratio to find the number of moles of the other species that have reactant with the
given molles in step 2
 Determine the concentration of the analyte using relationship
Concentration (c) = number of moles /volume (V)
c = n/v
SOLVING PROBLEMS
Example 1: In a titration a 25.0 cm3 sample of sodium hydroxide was titrated against 0.1 M
hydrochloric acid acid and it was found that 24.8 cm3 of the acid was required to reach the en-
point. Calculate the concentration of the sodium hydroxide sample
Given: volume of analyte (NaOH) V2 = 25.0 cm3 = 0.025 dm3
concentration of titrant(HCl) C1 = 0.1 M = 0.1 moldm-3
volulume of titrant (titre), V1 = 24.8 cm3 = 0.0248 dm3
concentration of analyte C2 =?
Solution: During the titration sodium hydroxide is going to react with hydrochloric acid. This
reaction between acid and base, so the products of the reaction will be a salt and water.
Step 1: Balanced equation
NaOH + HCl → NaCl + H2O
Step 2 : finding number of moles of HCl since we are given its concentration and volume
n(HCl) = c1 x V1
= 0.1 x 0.0248
= 0.00248 mol
Step 3: Stoichiometric ratio
1 mol NaOH : 1 mol HCl
Step 4: Using ratio to find n(NaOH)
Ratio is 1:1 so
⇨ n(NaOH) = n(HCl) = 0.00248 mol
Step 5: Find concentration of NaOH
c(NaOH) = n/V
= 0.00248/0.025
= 0.0992 moldm-3
= 0.1 moldm-3
ALTERNATIVE METHOD
 If from the balanced equation the stoichiometric ration is 1: !
Then number of moles of acid = number of moles of base
⇨ number of moles of acid = conc. of acid x volume of acid
n(acid) = Ca x Va
⇨ number of moles of base = conc. of base x volume of base
n(base) = Cb x Vb
Therefore, equating we get
C a x Va = Cb x V b
We then substitute given values in the formula and solve for the uknown.
NOTE: When using formula there is no need to covert volumes to dm 3.
E.g. in the above example:
Ca = 0.1 M; Va = 24.8 cm3 ; Cb = ? Vb = 25.0 cm3
Writing down formula:
C a x Va = Cb x V b
Substituting into formula:
0.1 x 24.8 = Cb x 25.0
Therefore, Cb = 0.1 x 24.8/25.0
= 0.1 M (moldm-3)
Example 2: A 50.0 cm3 sample of sulphuric acid was diluted to 1.0 dm3. A sample of the
diluted was analysed by titrating with aqueous sodium hydroxide. In the titration, 25.0 cm 3
of 1.00 mol dm-3 aqueous sodium hydroxide required 20.0 cm3 of the diluted sulphuric acid
for neutralization. Calculate the concentration of the original concentrated sulphuric acid
solution.
Given: Volume of concentrated sulphuric acid solution = 50 cm 3 = 0.050 dm
Titration data: volume of NaOH = 25.0 cm3 = 0.025 dm3; conc. of NaOH = 1.00 mol dm3
Vol of H2SO4 = 20.0 cm3 = 0.020 dm3 ; conc. of H2SO4 = ?
 Equation for the titration reaction

2 NaOH(aq) + H2SO4(aq) → Na2SO4(aq) + 2H2O(l)

  Finding number of moles of NaOH [since c and V are given]

n(NaOH) = C x V
= 1.00 x 0.025
= 0.025 mol
 Stoichiometric ratio:

2 mol NaOH : 1 mol H2SO4

 Using ratio to find number of moles of H2SO4

n(H2SO4) = ½ n(NaOH)
= ½(0.025)
= 0.0125 mol
S0 0.0125 moles are in 20.0 cm3. (used in the titration)
These 20 cm3 were taken from 1.00 dm3
So, number of moles of H2SO4 in 1.00 dm3 = 0.0125 x 1.00/20.0
= 0.0625 mol
0.0625 mol came from the original concentrated sulphuric acid solution.
Therefore, concentration of original conc. soln = n/V
= 0.0625/0.050
= 1.25 mol dm-3
Problem 1: A of sodium hydrogencarbonate was tested for purity using the following
method. 0.400g of the solid was dissolved in 250 ml of water and titrated woth 0.200 M
hydrochloric acid (HCl) using methyl orange indicator. 23.75 ml of acid was required for
complete neutralization.
a) Write the balanced equation for the reaction.
b) calculate the moles of HCl used in the titration and moles of NaHCO3 titrated.
c) calculate the mass of NaHCO3 titrated and hence percentage purity of the sample.
HINT: % purity = mass of substance ÷ mass of sample x 100
Problem 2: 0.400g of another group I hydrogencarbonate (XHCO3) in its pure state was titrated
with the same acid and 27.50 cm3 of the acid was needed to neutralize it. Calculate
a) moles of acid needed for neutralization and moles of hydrogencarbonate (XHCO3) titrated.
b) the formula mass (molar mass) of hydrogencarbonate (XHCO3).
c). By working out the atomic mass of X suggest the identity of the hydrogencarbonate.
Hints:
1. To find number of moles of HCl use the concentration of acid and volume
2. Since the metal is in grp I the stoichiometric ratio of acid to hydrogencarbonate is the same as
for NaHCO3 in problem 2.
3. Use the ratio to find number of moles of XHCO3
4. To find molar mass of XHCO3 use relationship n = m ÷ M
5. To find atomic mass of X we say:
M(XHCO3) = A(X) + A(H) + A(C) + 3A(O)
Then A(X) = M(XHCO3) - A(H) - 3A(O)
6. Use periodic table to find identity of X.
THEORY OF ACIDS AND BASES
There are several definitions of acids and bases:
An acid is defined as:
 A substance that dissolves in water and dissociates producing H+ ions.
e.g. HCl(aq) → H⁺(aq) + OH‾(aq)
HNO3(aq) → H⁺(aq) + NO3(aq)
H2SO4(aq) → 2H⁺(aq) + SO42-(aq)
 A substance that neutralizes a base
 A proton donor (H+ ) (Bronsted-Lowry theory)
NB: in our study of acids we will mainly be using the Bonsted-lowry theory definition.
According to the Bronsted-Lowry theory acids donate H+ ions (protons) in reactions
E.g. NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)
(base) (acid) (salt) (water)
In this rxn the acid HCl is donating a proton to the base (OH-) to form water.
A base is defined as :
 A substance that dissolves in water and dissociates producing hydroxyl ions (OH‾ ions)
e.g. NaOH(aq) → Na⁺(aq) + OH‾(aq)
KOH(aq) → K⁺(aq) + OH‾(aq)
 A substance that neutralizes an acid
 A proton acceptor (Bronsted-Lowry definition)
E,g. KOH(aq) + HNO3(aq) → KNO3(aq) + H2O(l)
 (base) (acid) (salt) (water)
In this rxn the base (OH‾) accepts a proton (H⁺) from the acid to form water.

DISSOCIATION OF ACIDS AND BASES

Acids and bases can categorized as strong and weak acids or bases.
 Strong acids and bases dissociate completely. The reaction proceeds in ode direction. All
the molecules of acid or base dissociate forming ions.
The dissociation can be represented by:
Acid dissociation

HA(aq) → H⁺(aq) + A‾(aq)

(acid)

e.g. HCl(aq) → H⁺(aq) + Cl‾(aq)

Base dissociation
BOH(aq) → B⁺(aq) + OH‾

e.g. NaOH(aq) → Na⁺(aq) + OH‾(aq)

 Weak acids and bases partially dissociate when in solution. The dissociation is an
equilibrium reaction. (i.e a reaction that can proceed both forward and backward) The
dissociation is represented by:

BA + H2O ⇌ BH⁺(aq) + OH‾(aq)

(base)
Also, BOH(aq) ⇌ B⁺(aq) + OH‾(aq)

e.g. NH3 + H2O ⇌ NH4⁺(aq) + OH‾(aq)

Acid dissociation constant and base dissociation constant