Expt.

No: POTENTIOMETRY:
Date: DETERMINATION OF MOLARITY OF HCl ACID

AIM
To determine the molarity of the given dil. HCl acid solution by potentiometric titration using
0.1 M NaOH standard solution.
PRINCIPLE
Potentiometric titration involves the measurement of potential between two electrodes, one is an
indicator electrode whose potential changes with the ionic concentration of the solution and the other a
reference electrode of constant potential. The equivalence point of thereaction will be revealed by sudden
change in the potential.
Potentiometric titration is done via the usage of two electrodes – an indicator electrode and a reference
electrode. One half-cell is formed with the indicator electrode and the ions of the analyte, which is
generally an electrolyte solution. The other half-cell is formed by the reference electrode. The
potentiometric titrations can be carried out in both aqueous and non-aqueous solvents.
The overall cell potential can be calculated using the formula given as: Ecell=Eind–Eref
The overall cell potential, Ecell is calculated in every interval where the titrant is measured and added.
Now, a graph is plotted with the Potential difference on the Y-axis and the volume on the X-axis.
It can be observed from the graph (Fig. 1) that the electrical potential of the cell is dependent on the
concentration of ions which are in contact with the indicator electrode. Therefore, the Ecell is measured
with each addition of the titrant.
APPARATUS REQUIRED
Pontentiometer, 0.1 M NaOH solution, dil. HCl sample solution, Burette,
20 mL pipette, 250 mL beaker, deionised water.
PROCEDURE
The standard sodium hydroxide (NaOH) solution is taken in a clean 25 mL burette. The given dil. HCl
solution (20 mL) is transferred into a clean 250 mL beaker and well mixed with 80 mL of deionised
water. The electrodes are placed in the beaker solution and the EMF is measured.
Now, 1 mL of NaOH solution from the burette is added to the beaker solution, well mixed and then the
EMF measured. The experiment is repeated with further additions of burette solution up to 15 mL totally
(in 1 mL addition each time).
Initially the EMF increases normally and sharply increases nearing the end point. Further addition of
NaOH after the end point increases the EMF normally.
The graph is drawn by taking volume of sodium hydroxide solution added in the x-axis and the EMF in
the y-axis. The end point is the inflexion of the curve (Fig. 1). The accurate end point is determined by
plotting E/V against the volume of NaOH added (Fig. 2). The end point volume is used to calculate
strength of HCl solution and then the amount of HCl in 1 L is calculated using the equivalent weight
value of HCl which is 36.45 g/mole.
MODEL GRAPHS
Fig-1: Potentiometric curve Fig-2: First derivative curve

Volume of NaOH added (mL) Volume of NaOH added (mL)

 VIT AP University, Amaravati (AP), INDIA

OBSERVATIONS AND CALCULATIONS

Vol. of NaOH Potential

S.No. ∆V ∆E ∆E/∆V
V, (mL) E, (mV)

1 0.00 --- --- ---

2 1.00 1.00

3 2.00 1.00
4 3.00 1.00
5 4.00 1.00
6 5.00 1.00
7 6.00 1.00
8 7.00 1.00
9 8.00 1.00
10 9.00 1.00
11 10.00 1.00
12 11.00 1.00
13 12.00 1.00
14 13.00 1.00
15 14.00 1.00

16 15.00 --- --- ---

CALCULATION
Volume of given HCl solution, V1 : 20 mL
Strength of given HCl solution, M1 : ….…. M
Volume of NaOH solution at end point : …….. mL (from graph)
Strength of NaOH solution, M2 : 0.1 M
……… × 0.1
Therefore, strength of given HCl solution, M1 : 20
= ………. M
The amount of HCl present in 1 L of : strength  equivalent weight
the given solution : ……… M  36.45 g / L
: ……… g / L

RESULT
The strength of the given HCl solution : ………. M
The amount of HCl present in 1 L of the given solution : ………. g / L

2/2 Department of Chemistry

School of Advanced Sciences (SAS)
 Expt. No: ELECTROCHEMISTRY: VERIFICATION OF
Date: NERNST EQUATION USING DANIELL CELL

Aim
To build a Daniell electrochemical cell,
To verify the Nernst equation and
To find the copper(II) ion concentration by potentiometry: (a) in Cu2+ saturated solution
and (b) in an unknown Cu2+ solution.
Principle
The Daniell Cell (built in 1836) was the starting point of modern electrochemistry because, for
the first time, a reliable source of current at a precise voltage was produced. Also, it was the first
practical cell developed that does not generate a gas under operating condition. This cell was used
as the first standard to define the unit “Volt”.

However, when the concentration of either Cu2+(aq) or Zn2+(aq) changes in the solution, the
EMF of the cell (or potential) also changes according to the Nernst equation.

with R = 8.314 J.K-1.mol-1, T = 298K, n = 2 (electrons exchanged), F = 96485 C.mol-1

The purpose of this lab experiment is to use the Daniell cell to verify the Nernst law (potential
vs. concentration).

Two 50mL beakers are used as half-cell. The salt bridge is a rolled filter paper having both ends
in contact with each solution. A few drops of 1.5M KNO3 are added to wet the paper at the center to
ensure ionic conductivity. A multimeter is used to measure the EMF of the cell. The device is set to
“mV” position. Of the two cables from multimeter each ending with its metallic contact, the black
one is connected to the electrode performing an oxidation, here the zinc. The connections are made
according to cell representation (electrons flow from the left to the right).

Since the oxidation reaction always happens at the anode, a spontaneous reaction (galvanic cell)
will give a positive EMF.
Materials Required
Multimeter, Copper rod, Zinc rod, 0.3 M Copper sulphate solution, 0.1 M Zinc sulphate
solution, 1.5M KNO3 solution, 0.1M HNO3 solution, filter paper strip, 50 mL beakers
(2 numbers).

Procedure
1. Make 100 mL of 0.1 M ZnSO4(aq) solution.
2. Make 100 mL of 0.3 M CuSO4(aq) solution.
The water used should be acidic, therefore, add 5 drops of conc. HNO3 to the distilled water to
prevent any Cu(OH)2(s) formation.
3. From the 0.3 M CuSO4(aq) solution, prepare 100 mL each of 0.1 M, 0.01 M and 0.001 M
copper (II) sulphate solutions. Hint: Use serial dilution to prepare the solutions.
4. Zinc electrode is cleaned with some diluted HNO3 acid (≈0.1M). The copper wire is refreshed
by scrubbing the surface with an emery paper. Both electrodes are rinsed with distilled water
prior to use and placed in their respective beakers.
5. Pour about 30 mL of 0.1 M ZnSO4(aq) solution in the beaker with the zinc electrode.
6. In another beaker, place the copper electrode filled with 30 mL of 0.1 M CuSO4(aq) solution.
7. Connect both electrodes with the metallic contacts of the multimeter in such a way that a
positive voltage reading (black connector for zinc electrode) is displayed. Place the salt bridge
between two beakers (strip of filter paper) to ensure the ionic conductivity between the two half
cells. The two ends of the paper should be in contact with both solutions. Use few drops
1.5 M KNO3 to wet the paper at the center. Record the EMF of this cell (in volt).
8. Repeat this process by replacing copper electrode solution with the saturated solution provided.
After the measurement, this electrode should be rinsed and stored. Repeat the process for other
copper sulphate solutions prepared (0.01 M, 0.001 M, saturated solution and an unknown
concentration solution). Plot a graph of EMF vs. ln ([Zn2+]/[Cu2+])
Note: While keeping the same zinc sulphate solution throughout the experiment, CuSO4
solution changed from experiment to experiment.
ZnSO4(aq) solution concentration: 0.1 M
CuSO4 solution [𝑍𝑛2+ ] [0.1] [𝑍𝑛2+ ] [0.1] EMF
S. No. [𝐶𝑢2+ ]
= [𝐶𝑢2+ ] 𝑙𝑛 [𝐶𝑢2+ ] = 𝑙𝑛 [𝐶𝑢2+ ]
concentration (Volt)
1 0.1 M
2 0.01 M
3 0.001 M
4 Saturated solution __ __

5 Unknown strength __ __

Using Nernst equation discussed above or from the graph, the concentrations of saturated and
unknown strength CuSO4 solutions can be calculated. For a EMF value from y-axis, the
[0.1]
corresponding x-axis value is 𝑙𝑛 [𝐶𝑢2+ ]. Then, the [Cu2+] is calculated as the copper sulphate
solution concentration.
Results:
Concentration of Cu2+ in saturated solution : _________ M
Concentration of Cu2+ in unknown strength : _________ M
 Expt. No: COLORIMETRIC STUDIES:
DETERMINATION OF CONCENTRATION OF KMnO4
Date: SOLUTION

AIM
To determine the molarity of the given KMnO4 solution using a colorimeter.

PRINCIPLE
When a chemical species absorbs visible light, electrons in the normal ground state are
raised to a higher energy excited state. The difference in energy between the two states of the
absorbing species is equal to the energy of the light quantum absorbed. As a beam of
monochromatic light, i.e., light of a single wavelength, passes through an absorbing solution,
the intensity of the light decreases as photons are removed from the beam. It is reasonable to
assume that the more light-absorbing entities there are in the light path and the more light-
quanta there are available to begin with, the greater is the amount of light that will be absorbed.
According to Beer-Lambert Law we can write, 𝐴 = 𝜖. 𝑐. 𝑙,
where A is known as the absorbance of the sample
c is the concentration of the sample, and
l is the path length that light in the cell travels.
If 𝜖 and 𝑙 are constant for a sample, then 𝑨𝒃𝒔𝒐𝒓𝒃𝒂𝒏𝒄𝒆 (𝑨) ∝ 𝒄𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏(𝒄).

MATERIALS REQUIRED
● Aqueous 0.01M KMnO4 stock solution
● Distilled water
● Colorimeter instrument

PROCEDURE
● Switch ON the colorimeter
● Set wavelength to “54” (540 nm)
● Put a cell containing distilled water and press set zero
● Preparation of solutions from Stock solution:
Prepare 0.001 M, 0.002 M, 0.003 M, 0.004 M and 0.005 M solutions.
● Place a cell containing 0.001 M solution of KMnO4 solution, measure the absorbance
and write in Table 1
● Put the next solution, e.g., 0.002 M of KMnO4 and measure its absorbance
● Complete measuring absorbance of all the known concentration solutions and also the
unknown concentration solution
● Plot Absorbance (y-axis) vs Concentration (x-axis) of all known concentration solutions
● Determine the unknown concentration of the solution from the graph.
 VIT AP University, Amaravati (AP), INDIA

OBSERVATION
Table 1
Conc. Of KMnO4
S. No. Absorbance
solution (M)
1 0.001
2 0.002
3 0.003
4 0.004
5 0.005
6 Unknown

RESULT
The strength of the given KMnO4 solution is : ………. mM

2/2 Department of Chemistry

School of Advanced Sciences
 Exp. No. 2 Estimation of Hardness of Water by EDTA Method

Part-1

Aim: (i) To estimate the amount of total hardness present in the given sample of water by
EDTA titration method.

Principle: Water quality is evaluated using a number of parameters, including total ionic
content, pH, total dissolved solids, organic compounds, and water hardness. Water hardness
is a measure of the concentration of all the polyvalent cations dissolved in the water. The
most common such cations are calcium and magnesium, although iron, strontium, and
manganese may contribute to water hardness. Water hardness is often defined as the sum of
the concentrations of Ca2+ and Mg2+ in water. Since most analyses do not distinguish between
Ca2+ and Mg2+, and hardness is caused by carbonate mineral deposits, hardness is usually
reported as parts per million (ppm) of calcium carbonate (by weight). Ca2+ and Mg2+ ions in
hard water react with the fatty acids in soap, causing them to precipitate. “Soft” water, such
as rainwater or water that has passed through a water softener, has very little Ca2+ and Mg2+.
The estimation of hardness is based on complexometric titration. Hardness of water is
determined by titrating with a standard solution of ethylene diamine tetraacetic acid (EDTA)
which is a complexing agent. Since EDTA is insoluble in water, the disodium salt of EDTA
is taken for this experiment. EDTA can form four or six coordination bonds with a metal ion.

Theory: EDTA forms colorless stable complexes with Ca2+ and Mg2+ ions present in water at
pH = 9-10. To maintain the pH of the solution at 9-10, buffer solution (NH4Cl + NH4OH) is
used. calamagite is used as an indicator. The sample of hard water must be treated with buffer
solution and calamagite indicator which forms unstable complexes with Ca2+ and Mg2+
present in water.
 EDTA-Ca2+ Complex

Determination of Sample water hardness:

(1) Pipette out 20 mL of hard water into a conical flask.
(2) Add 5 mL of buffer solution and few drops of calamagite indicator.
(3) Titrate with 0.01 M EDTA solution taken in the burette, till the wine red color changes to
blue which is the end point. Let the burette reading of EDTA be V1 mL.
(4) Titrate the solution until the last trace of red color disappears upon addition of just a
fraction of a drop of EDTA. The final color change should be from a violet color to a pale
blue. The change should be fairly sharp.

Volume of hard Burette Reading Volume of EDTA

S. No.
water sample (mL) Initial Final (V1) mL

1 20
2 20
3 20

Calculation:
1 mL of 0.01 M EDTA ≡ 1mg of CaCO3
V1 mL of EDTA ≡ V1 mg of CaCO3
Volume of EDTA solution consumed = ……. mL
Volume of hard water taken = .......... mL

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 × 1000

𝑆𝑎𝑚𝑝𝑙𝑒 𝑤𝑎𝑡𝑒𝑟 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = ppm
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 ℎ𝑎𝑟𝑑 𝑤𝑎𝑡𝑒𝑟 𝑡𝑎𝑘𝑒𝑛

𝑉1 × 1000
= ppm
20

= …………. ppm
 Part-2

Aim: To remove ca2+ and Mg2+ ions from hard water using ion exchange resin.

Principle: In this experiment, an ion-exchange resin will be used. An ion-exchange resin

consists of beads of an organic polymer. On the surface of the beads, there are functional
groups capable of removing ions from solution and replacing them with ions of like charge
from the resin. If the resin exchanges cations with the solution, it is a cation-exchange resin;
if it exchanges anions, it is an anion-exchange resin.
Some examples of the reactive groups of ion-exchange resins are:

If a cation-exchange resin is immersed in a solution containing cations (such as Na+) some of the
hydrogen ions associated with the resin will be exchanged for the sodium ions in solution. The
exchange process between a solution of sodium ions and a sulfonic acid resin is represented
below. Cations with +2 or +3 charges liberate two or three protons, displacing the protons from two
or three sulfonic acid groups, respectively.
Theory: The resin can be packed into a vertical glass tube, forming an ion-exchange column.
The solution containing cations added to the top of the resin in the column and slowly passed
through the resin. As the solution proceeds through the column, it exchanges more and more
of its cations with the hydrogen ions of the resin. The replacement of cations in the solution
by hydrogen ions from the resin will be essentially complete if the rate of flow is slow
enough to allow the exchange equilibrium to establish itself all along the column, and if all
portions of the solution have been in contact with fresh resin before leaving the column.
In this experiment, hard water solution will be passed through a cation-exchange resin. The
calcium and magnesium ions in the solution will exchange with a stoichiometric amount of
hydrogen ions on the resin. The amount of hydrogen ions in the effluent, the solution flowing off the
column, will be titrated with a solution of standard EDTA. This titration estimates the amount of
calcium ions removed from the hard water.
 + +
Ca
2 Ca
2

Determination of Purified water hardness:

1. Pass distilled water 50 mL over Amberlite IR120 ion exchange column.
2. collect the effluent and discard it.
3. Pipette out 20 mL of hard water into a beaker.
4. Pass hard water over Amberlite IR 120 ion exchange column slowly & collect drops in conical
flask.
5. Pass 100 mL of distlled water slowly over the column and collect effluent in the same conical flask.
6. Titrate with 0.01 M EDTA solution by following the procedure mentioned in part-1.

Calculations:

Volume of hard Burette Reading (mL) Volume of EDTA

S. No.
water sample (mL) Initial Final (V2) mL

1 20

1 mL of 0.01 M EDTA ≡ 1mg of CaCO3

V2 mL of EDTA ≡ V2 mg of CaCO3
Volume of EDTA solution consumed (V2) = ……. mL
Volume of hard water taken = 20 mL

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 × 1000

𝑃𝑢𝑟𝑖𝑓𝑖𝑒𝑑 𝑤𝑎𝑡𝑒𝑟 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = ppm
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 ℎ𝑎𝑟𝑑 𝑤𝑎𝑡𝑒𝑟 𝑡𝑎𝑘𝑒𝑛

𝑉2 × 1000
= ppm
20

= …………. ppm

𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑤𝑎𝑡𝑒𝑟−ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑜𝑓 𝑝𝑢𝑟𝑖𝑓𝑖𝑒𝑑 𝑤𝑎𝑡𝑒𝑟

Water purification % = × 100
ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑤𝑎𝑡𝑒𝑟

Result:
From Part I
Hardness of sample water : …….. ppm (or) mg/L
From Part II
Hardness of purified water : …….. ppm (or) mg/L
Percent purification by ion-exchange : …….. %