1.

INTRODUCTION TO CHEMISTRY LABORATORY

Analytical chemistry is the branch of chemistry which deals with the detection of
chemical composition and estimation of the elements and compounds contained in it. It is
classified into
1. Qualitative analysis
2. Quantitative analysis
1. Qualitative analysis
Qualitative analysis deals with the detection and identification of the
constituent cations and anions present in the given substance.
2. Quantitative analysis
Quantitative analysis deals with the determination of amount of different
constituents present in a sample. The determination can be carried by three
methods.
(a) Gravimetric analysis
(b) Volumetric analysis
(c) Instrumental analysis.
a) Gravimetric analysis
In gravimetric analysis, the estimation of substance is carried out by the
process of weighing. The constituent being determined is isolated as a
compound of known and definite composition of insoluble form, which is
collected and weighed.
b) Volumetric analysis
This method of analysis deals with volumes of solution and the estimation of
substance is carried out by the process of titration. This method is rapid and
simple.
c) Instrumental analysis
It is a field of analytical chemistry that investigates analytes using scientific
instruments.
Terms used in volumetric analysis:
Titration: Titration is a process of addition of known concentration of solution to the
unknown solution up to the completion of the reaction.
Titrant: The reagent of known concentration is called titrant.
Titrate: The substance being titrated is termed as titrate.
End point: The point at which the reaction is just complete is known as the equivalence point
or end point.
Indicator: The substance which is used in the titration to locate or to identify the end point
visually on completion of titration by change of colour.
Eg. Methyl orange, Phenolphthalein, Methyl red.
Standard solution: A solution of known concentration is known as standard solution.
Primary standard: The substance whose standard solution is prepared by dissolving a
directly weighed substance in a definite volume of a solvent is called primary standard.
Commonly used primary standards are anhydrous Sodium Carbonate, Oxalic acid, Mohr’s
salt, Potassium dichromate etc.
A standard solution is prepared by dissolving an accurately weighed quantity of a highly pure
material and diluting to an accurately known volume in a volumetric flask is called primary
standard.
Secondary standard: That substance which cannot be used to prepare a solution by direct
weighing. The solutions of this type are prepared with approximate strength and then
standardised with a standard solution. The common secondary standards are Sodium
Hydroxide, Inorganic acids, Potassium Permanganate etc.
Normality (N): The number of gram equivalents of the solute per litre of the solution is
called as the normality of the solution.

No. of gram equivalents of solute

N=
Volume of solution in litres

Molarity (M): The molarity (M) of a solution is the number of moles of solute per litre of the
solution.
No . of moles of solute
M=
Volume of solution in litres

Accuracy: Accuracy of a measurement system is the degree of closeness of measurements of

a quantity to that quantity's actual (true) value. (or)
It is defined as the concordance between experimental value and true value.
Precision: Precision of a measurement system, also called reproducibility or repeatability, is
the degree to which repeated measurements under unchanged conditions show the same
results. (or) It is defined as the degree of agreement between experimental value and true
value.
Classification of Titrimetric reactions:
1. Acid-Base titrations or Neutralization titrations
Titrations based upon neutralization reactions are called acid-base titrations.
HCl + NaOH H2O+ NaCl
H+ + OH- H2O
 The determination of the concentration of acids by using standard alkali
solutions is acidimetry and the reverse process is alkalimetry.
2. Precipitation titrations
Titrations based upon the formation of insoluble precipitates when the reacting
solutions are mixed together are called precipitation titrations.
When a solution of silver nitrate is treated with sodium chloride a white
precipitate of silver chloride is obtained.
AgNO3 + NaCl NaNO3 + AgCl
3. Redox titrations
Redox titrations are based on a reduction-oxidation reaction between an
oxidising agent and a reducing agent. A potentiometer or a redox indicator is
usually used to determine the endpoint of the titration.
2KMnO4 +5H2C2O4 + 3H2SO4 K2SO4 + 2MnSO4 + 8H2O + 10CO2
4. Complexometric titrations
Complexometric titrations rely on the formation of a complex between the
analyte and the titrant. In general, they require specialised indicators that form
weak complexes with the analyte. Common examples are Eriochrome Black T
for the titration of calcium and magnesium ions, and the chelating agent EDTA
used to titrate metal ions in solution.
Ca+2 + EDTA Ca-EDTA (Complex)
Theory of indicators:

An indicator is a substance which is used to determine the end point in a titration. In acid-
Base titrations, organic substances (weak acids or weak bases) are generally used as
indicators. They change their colour within a certain pH range.

The colour change and the pH range of some common indicators are tabulated below:

Indicator pH range Colour change

Methyl orange 3.2 - 4.5 Pink to yellow
Methyl red 4.4 - 6.5 Red to yellow
Litmus 5.5 - 7.5 Red to blue
Phenol red 6.8 - 8.4 Yellow to red
Phenolphthalein 8.3 - 10.5 Colourless to pink

Two theories have been proposed to explain the change of colour of acid-base indicators with
change in pH.
1. Ostwald’s theory:

According to this theory:

(a) The colour change is due to ionisation of the acid-base indicator. The unionised form has
different colour than the ionised form.

(b) The ionisation of the indicator is largely affected in acids and bases as it is either a weak
Acid or a weak base.

In case, the indicator is a weak acid, its ionisation is very much low in acids due to common
H+ ions while it is fairly ionised in alkalis. Similarly if the indicator is a weak base, its
ionisation is large in acids and low in alkalis due to common OH– ions.

Considering two important indicators phenolphthalein (a weak acid) and methyl orange (a
Weak base), Ostwald theory can be illustrated as follows

Phenolphthalein: It can be represented as Hph. It ionizes in solution to a small extent as

HPh H+ + Ph–
Colourless pink

The unionised molecules of phenolphthalein are colourless while Ph - ions are pink in colour.
In presence of an acid the ionisation of Hph is practically negligible as the equilibrium shifts
to left hand side due to high concentration of H+ ions, the solution would remain colourless.
On addition of alkali, hydrogen ions are removed by OH– ions in the form of water molecules
and the equilibrium shifts to right hand side. The concentration of Ph– ions increases in
solution and they impart pink colour to the solution.

2. Quinonoid theory:

According to this theory:

(a) The acid-base indicators exist in two tautomeric forms having different structures; these
two forms are in equilibrium. One form is termed benzenoid form and the other is quinonoid
form.

(b) The two forms have different colors. The color change is due to the inter conversion of
one tautomeric form into other.

(c) One form mainly exists in acidic medium and the other in alkaline medium. Thus, during
titration the medium changes from acidic to alkaline or vice-versa. The change in pH
converts one tautomeric form into other and thus, the colour change occurs. Phenolphthalein
has benzenoid form in acidic medium and thus, it is colourless while it has quinonoid form in
alkaline medium which has pink colour.
 ESTIMATION OF FERROUS ION
Aim: To estimate the amount of ferrous iron in the given solution by using a
standard solution of potassium dichromate.

Apparatus: Burette, pipette, conical flask, beakers, volumetric flask.

Chemicals: Standard Ferrous iron solution (Mohr’s salt solution).
Potassium dichromate (K2Cr2O7) solution
Sulphuric acid (H2SO4)
Phosphoric acid (H3PO4)
Diphenylamine indicator
Unknown ferrous iron solution.

Principle: Ferrous Iron is oxidized to Ferric iron by Potassium Dichromate in

acid solution. The completion of oxidation reaction is marked by the
appearance of Blue violet colour of diphenylamine, which is used as an
internal indicator.
K2Cr2O7+4H2SO4 → K2SO4+Cr2(SO4)3+4H2O+3(O)
6FeSO4+3H2SO4+3 (O) → 3Fe2(SO4)3+3 H2O
K2Cr2O7+6FeSO4+ 7H2SO4 → K2SO4+ 3Fe2(SO4)3+Cr2(SO4)3+ 7H2O
Procedure:
Part-A
Standardisation of potassium dichromate:
1. Rinse and fill the burette with the given potassium dichromate solution.
2.Pipette out 20ml of standard ferrous iron solution (Mohr’s salt solution)
into a well cleaned 250ml conical flask.
3. Add10 ml of acid mixture (sulphuric acid & Phosphoric acid) and 2
drops of diphenylamine indicator to the solution.
4. Titrate the contents of the conical flask against potassium dichromate
solution. The end point is colour less to blue violet.
5. Repeat the titration till two successive concurrent values are obtained
Standardisation of potassium dichromate

Volume of standard Burette readings (ml) Volume of K2Cr2O7

S .No Mohr’s salt
solution (ml)
solution(ml) Initial Final

N 1=Normality of standard Mohr’s salt solution = N

N2 = Normality of K2Cr2O7 solution = ?
V1 = Volume of standard Mohr’s salt solution = ml
V2 = Volume of K2Cr2O7 solution = ml
N1V1 = N2V2
N1V1
N2 =
V2
Part-B
Estimation of Iron:
1. Rinse and fill the burette with the given potassium dichromate solution..
2.Make up the given unknown ferrous iron solution in 100ml volumetric
flask up to the mark with distilled water.
3. Pipette out 20ml of unknown ferrous iron solution into a well cleaned
250ml conical flask.
4. Add10 ml of acid mixture (sulphuric acid & Phosphoric acid) and 2
drops of diphenylamine indicator to the solution.
5. Titrate the contents of the conical flask against potassium dichromate
solution. The end point is colour less to blue violet.
6. Repeat the titration till two successive concurrent values are obtained.
Estimation of ferrous iron

Burette readings(ml) Volume of K2Cr2O7

Volume of Ferrous
S.No
iron solution (ml) solution (ml)
Initial Final

1
2

3
 N1= Normality of K2Cr2O7 solution = N
V2 = Volume of K2Cr2O7 solution = ml
N3 = Normality of Ferrous iron solution = ?
V3 = Volume of Ferrous iron solution = ml

N2 V2 = N3 V3
NV
N3 = 2 2
V3

Amount of ferrous iron present in the given solution

E X N3 X Volume in ml
Q= = g/100ml
1000

Where E = Gram equivalent weight of Ferrous iron = 27.9

N = Normality of Ferrous iron solution (N3) =
V = Volume of Ferrous iron solution = 100 ml

Result: The amount of ferrous iron present in the given solution = grams/100ml