ENGINEERING/APPLIED CHEMISTRY

LAB MANUAL
FOR I/II SEMESTER B.TECH STUDENTS OF
REVA UNIVERSITY

NAME

SRN

CLASS

BRANCH

COURSE

1
 Contents
Part A

Sl. No. EXPERIMENT Date Page No.

1 Estimation of Iron by Potentiometric sensor. 8
Verification of Beer-Lambert’s Law by detection of
2 Copper by spectroscopy. 13
Estimation of concentration of acid mixture by
3 Conductometric sensor. 17
Determination of pH/pKa of solutions using glass
4 membrane electrode sensor. 21
Preparation of semiconducting nanomaterials and their
5 characterization. 26
Preparation of Conducting polyaniline thin film by electro
6 polymerization. 33

Part B
Estimation of Total Hardness of Water by
1 Complexometric Method Using EDTA 37
Evaluation of Dissolved Oxygen by Winkler’s method
2 and hence assessment of quality of water. 42
3 Determination of percentage of Iron in corrosion products. 46
Estimation of percentage of Copper in brass alloy by
4 iodometric method 53
5 Faraday’s law verification by using Electrodeposition of
Cu/Ni/Zn on stainless steel. 56
6 Construction of Daniel cell 59

Part C – Demo
1 Flame Photometric metal ions detection 63
2 Determination of optical band gap of materials 67
3 Dye sensitized solar cell 70

2
 General Instructions and Laboratory Rules

 DO NOT work alone in a laboratory.

 Know the location and proper use of fire extinguishers, fire blankets, safety showers, eye
wash devices, and first aid kits.
 DO NOT perform unauthorized experiments.
 YOU ARE ULTIMATELY RESPONSIBLE FOR YOUR OWN SAFETY AND THAT OF
YOUR FELLOW STUDENTS, WORKERS AND VISITORS.
 The following PPE (Personal Protective Equipment) must always be worn in the laboratory:
1. Lab coat
2. Eye protection: Splash proof chemical goggles. If you do get a chemical in your eye,
rinse your eye immediately using large quantities of water or an eye wash bottle
3. Closed shoes with socks must always be worn – open-toed shoes, backless shoes,
sling backs, clogs, and sandals are not permitted.
4. Always wear gloves when working with unknown substances.
5. Always wear the appropriate breathing masks when working with toxic or irritating
vapors.
6. Use the fume hoods when toxic or irritating vapors are involved.
7. Always work in a well-ventilated area
8. Eating, smoking, and drinking are not allowed in a chemistry laboratory.
9. Labels and equipment instructions must be read carefully before use
10. Observe good housekeeping practices. Work areas should always be kept clean and
tidy.
11. Dispose of all chemical waste properly. Use the waste containers marked for this
purpose and update the waste register every time. Liquid and solid waste containers
must be properly used at all times.
12. Thoroughly wash your hands before leaving the laboratory.
13. Long hair and loose clothing must be confined while in a laboratory.
14. Unused chemicals should not be returned to their original container unless directed
to do so by the lab instructor.
15. Securely replace lids, caps, and stoppers after removing reagents from containers.
16. All flammable reagents must be removed before lighting a burner.
17. Never pour water into concentrated acid.
18. Mouth suction is never used to fill a pipette.
19. Always wipe spatulas clean before and after inserting into reagent bottles.
20. Report any accident and/or injury, however minor, to your instructor immediately.
21. Clean up any spill immediately.

3
 22. Before leaving the laboratory, make sure your work area is clean and dry and ensure
that all gas, water, vacuum, and air valves are completely turned off.
23. Never hesitate to ask questions especially if there is any question concerning proper
operating procedure. Be sure that you understand every instruction before
proceeding.

TOXICITY OF CHEMICALS:

Laboratory work involves the use of several chemicals that are potentially hazardous.
Toxic chemicals can enter the body by ingestion, skin absorption, and inhalation.

Procedures that are performed correctly have minimum risk.

You are required to do the following before working with any chemical substance:

1. Read the MSDS of each chemical to be used carefully. There must be a file in the
lab containing the MSDS’s of the all the chemicals used in the laboratory. Please
obtain the relevant MSDS if not in the file before working with the particular
chemical.
2. Fill in the form, supplied, stating that you have read the relevant MSDS’s of the
chemicals to be used.
3. This form must be signed by yourself and the lab supervisor.
4. Read the label and instructions on the chemical container carefully
5. Make sure all the correct PPE are used when working with any chemical substance.
6. Return materials used in the storage facility.
7. Label sample material and store safely.

Laboratory Records:

Laboratory work records are to be maintained in a laboratory record book; to include

the work done, the material used-quantities, methods and processes.

General Laboratory Rules for equipment and instrumentation

1. Computers dedicated to the operation of an instrument should not be used for any
private work or the storing of private information for example music.
2. Follow the correct operating procedure for each instrument.
3. It is your responsibility to report malfunctioning equipment.
4. Do not use equipment that malfunctions or in your opinion may endanger yourself or
your colleagues.

4
 Laboratory Safety Rules
 Personal Protective Equipment
 Always wear safety goggles when working in the Lab.
 Always wear gloves when working in the Lab.
 Always handle hot objects with thermal gloves.
 Always wear shoes that completely cover and protect your feet.
 Always wear Lab coat and long pants when working in the Lab.
 Always use a Face shield, safety goggles and cryogenic gloves when working with
cryogenic liquids.

 Standard Precautions for Laboratory

 Keep calm and follow lab safety rules.
 Remove gloves before leaving the laboratory and entering common use spaces such as
Elevators, corridors outside your laboratory and using the telephone.
 Use an appropriate secondary container when transporting materials through common
use area.
 No food or drinks in the lab.
 Always discard any types of broken glass in separate glass container.
 Always wear personal protective equipment.
 Never leave any garbage or chemical waste around the lab. Always clean it up.
 Toxic chemicals must be used inside fume hoods with active exhaust.
 Waste sharps include needles, syringes with fixed needles, blades and other
contaminated sharps object that may cause puncture and cuts should be discarded into
tamper proof container.
 In the case of chemical spill/splash, use emergency shower and eyewash for at least 15
minutes. Report the incident and seek medical attention soon after the shower.

 Gas Cylinder Safety

 Secure cylinders properly always.
 Cylinders must be secured with two chains at 1/3 and 2/3 height.
 Store cylinders in cool, well ventilated, fire-resistant areas.
 Place cylinders where they will not be damaged by forklifts knocked over or hit by
falling objects.
 Close valves and tighten caps when not in use.

5
 Inspect cylinders for leaks and check support brackets regularly for strength and
integrity.
 Move cylinders using hand trucks/trolley designed for the purpose
 Report leaks or any damage to supervisor/safety officer immediately.

6
Part - A

7
 Estimation of Iron by Potentiometric Sensor

Expt. No. 1 Date:.........................

Aim
Potentiometric estimation of Mohr’s salt (Ferrous ammonium sulphate, FAS) in a given sample
solution using 0.5 N K2Cr2O7 solution

Principle
Titration of Mohr’s salt solution with K2Cr2O7 solution is a redox titration, in which, FeSO4 of
Mohr’s salt is a reducing agent and K2Cr2O7 an oxidizing agent. Inert electrode in redox system acts
as indicator electrode and its potential is a function of ratio of concentration of reduced species to
the concentration of oxidized species.
Mohr’s salt solution acidified with dil H2SO4 is taken in a beaker and a platinum electrode is
inserted. The potential of this indicator electrode (redox electrode) is measured wrt a reference
electrode (calomel electrode) using potentiometer.

Pt (s) |Fe3+, Fe2+

Potential developed at this electrode is given by the Nernst equation

E = E0 – 0.0592 log [Fe2+]

[Fe3+]
Fe+2/ Fe+3 Fe+2/ Fe+3

[Fe2+]
Thus the potential of this electrode is determined by the ratio [Fe3+] . The formal potential
(standard potential under the specified experimental conditions) of this system is +0.68V in
1 M H2SO4 w.r. to SHE.
Fe2+ ions are oxidized to Fe3+ ions by the addition of dichromate solution.
Cr2O72– + 14 H+ + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O

Dichromate ions are reduced to Cr 3+ ions by Fe2+ ions. Thus the ratio [Fe2+]/[Fe3+] gradually
decreases and hence EFe+2/ Fe+3 gradually increases in accordance with the Nernst equation till the end
point. After the end-point, dichromate remains in the solution, due the conversion of all Fe2+ ions into
Fe3+ ions. Hence the potential of the redox electrode is determined by Cr2O72- / Cr3+ couple instead of
Fe2+ / Fe3+ couple after the end-point. The formal potential of Cr 2O72– / Cr3+ system is about +1.3 V
in 1 M H2SO4 w.r. to SHE. Hence a steep change in the electrode potential results at the end-point.
Reduction reaction of Cr2O72- / Cr3+ system is
Cr2O72– + 14 H+ + 6e– → 2Cr3+ + 7H2O
Potential of the electrode is given by the Nernst equation

E = E0 –
Cr+6/ Cr+3 Cr+6/ Cr+3

8
 Potential increases gradually after the end-point with the addition of dichromate in accordance
with this equation.

It is not possible to measure single electrode potential experimentally. A galvanic cell must be
formed by coupling a indicator electrode with a reference electrode (like saturated calomel
electrode). The resulting cells can be represented as:

(i) Pt(s)| Fe2+, Fe3+ | | SCE, before the end-point &

(ii) Pt(s)| Cr2O72–, Cr3+ | | SCE, after the end-point

Potential of the reference electrode remains constant during the titration. Hence emf of the cell
changes with the potential of the indicator electrode, gradually before and after the end-point and
steeply in the neighborhood of the end point. End-point of the titration is determined by plotting a
differential graph of E / V versus volume of potassium dichromate.

Procedure

Add 1 TT of dil. H2SO4 into a 100 mL beaker containing the given Mohr’s salt solution. Immerse
calomel electrode and platinum electrode assembly and record potential. Add 0.5 mL of 0.5N
K2Cr2O7 each time from the burette and record the corresponding potential. After sharp increase in
the potential (corresponds to equivalence point), take 4 more readings.
Plot a differential graph of (E / V) versus volume of K2Cr2O7 and determine the equivalence
point that corresponds to the volume of K 2Cr2O7 at which, (E / V) is maximum. From the normality
and equivalence point of K2Cr2O7, the normality & amount of Mohr’s salt is calculated.

Result

Amount of Mohr’s salt in the given solution = ……….........… g / dm3

9
OBSERVATIONS AND CALCULATIONS
Volume of given Mohr’s salt solution = ------ mL
Normality of K2Cr2O7 = 0.5 N

Vol. of EMF ∆V ∆E ∆E / ∆V
K2Cr2O7 (mL.) E (mV) (V2–V1) (E2–E1)
0

0.5 0.5

1.0 0.5

1.5 0.5

2.0 0.5

2.5 0.5

3.0 0.5

3.5 0.5

4.0 0.5

4.5 0.5

5.0 0.5

5.5 0.5

6.0 0.5

6.5 0.5

7.0 0.5

7.5 0.5

8.0 0.5

8.5 0.5

9.0 0.5

9.5 0.5
10.0 0.5

10
 N  V
Normality of Mohr’s salt solution, NM =
K2 Cr2 O7 K2 Cr2 O7 7
22 7 2 2 7

V
Mohr 's salt

= .......................... N

Amount of Mohr’s salt solution in the given solution(A) = N Mohr’s salt X Eq.wt. of FAS(392)

= ............................. g / dm3

11
12
 Verification of Beer-Lambert’s Law by
detection of Copper by spectroscopy.
Expt. No. 2 Date:.........................

Aim
Estimation of copper present in the given copper sulphate solution using a photoelectric
colorimeter.

Principle
When a monochromatic light of intensity I0 is incident on a transparent medium, a part of light
is absorbed by the media (Ia), a part of light is reflected (Ir) and the remaining part of light is
transmitted (It) i.e.,
I0 = Ia + Ir + It
For a glass-air interface, Ir is negligible
I0 = Ia + It

Colorimetry is based upon Beer-Lambert Law.

Beer’s Law
The intensity of transmitted beam of a monochromatic light decreases exponentially as the
concentration of the absorbing medium increase arithmetically.

Lambert’s law
The intensity of transmitted light decreases exponentially as the thickness of the absorbing
medium increase arithmetically
Beer-Lambert Law is the combination of the two laws stated above.
Beer-Lambert Law

The intensity of transmitted beam of a monochromatic light decreases exponentially as the

concentration and thickness of the absorbing medium increase arithmetically.

I
It –abc
t
––∈bc

I0 = 10
OR I0 = 10 =T
T is called transmittance of the light absorbing transparent solution sample t x 100 = %. T is
called percent transmittance.
Inversing the above ratio and taking log we get
I
log 0 = abc = ∈bc = A
I
t

13
 Where ‘a’ is extinction coefficient, when concentration ‘c’ is expressed in g/L and ∈is the molar
extinction coefficient when concentration c is expressed in mol/L and b is the path length.

A is called absorbance (or optical density) of the light absorbing transparent solution sample.

This law can also be stated as absorbance of a monochromatic light is directly proportional to
path length and concentration of homogeneous absorbing medium.

For a given substance Î is constant at a given wavelength, and also the path length ‘b’ is constant for
a given cuvette. Therefore A a C. Hence, a plot of absorbance against concentration of the solution gives
a linear graph passing though the origin, there by verifying the Beer-Lambert’s Law.

A series of standard solution of copper Sulphate and test solution is added with ammonia to get
blue cuprammonium sulphate complex [Cu(NH3)4]SO4.H2O and is diluted to a definite volume. The
absorbance of each of these solution and test solution is measured at 620 nm, since the complex
shows maximum absorbance at this wavelength. The absorbance values are plotted against the
volume of copper sulphate solution to get a calibration curve and the volume of test sample is
determined from the graph.

Procedure
Add accurately 5, 10, 15, 20 and 25 mL of given copper sulphate solution from a 50 mL burette
into five separate 50 mL standard flasks. Further, add 5 mL ammonia to each flask and also into the
50 mL standard flask containing the test solution, make upto the mark with distilled water and shake
well. Prepare blank solution by adding 5 mL ammonia to an empty 50 mL standard flask and make
upto the mark with distilled water.

Blank solution is taken in a cuvette and placed in the photoelectric colorimeter. The variable
diaphragm is adjusted to get zero absorbance at 620 nm. Measure the absorbance of all standard
solutions and test solution using the same cuvette at 620 nm. A graph of absorbance (OD) versus
volume of CuSO4 is plotted and the volume of test solution is determined.

Results

Volume of copper sulphate in the given test solution (V) = …….……….. mL

Amount of Cu2+ ions present in the given test solution =….. ………….. mg

14
OBSERVATIONS AND CALCULATIONS
Amount of Cu2+ present per mL of the solution = 1.018 mg

Sl Vol. of standard Cu2+ solution in 50 mL std. Concentration of copper in

Absorbance
No. flask (mL) std. flask (mL) mg / mL
1
2
3
4
5
6
7 Test solution

Amount of penta hydrate copper sulphate present in 1000 mL =4g

Amount of penta hydrate copper sulphate present in 1mL = (4 x 63.54) / (1000 x 249.54) mg
= 1.018 mg

Unknown volume (from the graph) = ................. mL (V)

Amount of Cu2+ present in the given test solution = V × 1.018

= ................. mg

Graph :

15
16
 Estimation of concentration of Acid mixture by
Conductometric sensor
Expt. No. 3 Date:.........................

Aim
Conductometric estimation of strong & weak acids from their mixture using standard sodium
hydroxide solution.

Principle
Reciprocal of resistance (R) is conductance (L) and is measured in Siemens (Mho’s) i.e.
L =1/R
A conductivity cell consists a pair of platinized foils of definite average area “a” fixed at a
definite distance “l” apart. Thus l/a of a given conductivity cell has a definite value and it is known
as CELL CONSTANT.

Specific Conductance is the conductance of an electrolyte solution, placed between two parallel
electrodes 1 cm. apart and area of cross section 1 cm2.

Equivalent Conductance is the conductance of the solution due to all the ions produced by
dissolving one-gram equivalent weight of a solute in one litre of a solution.

Molar Conductance is the conductance of the solution due to all the ions produced by dissolving
one-gram Molecular weight of a solute in one litre of a solution.

Conductance of an electrolyte is directly proportional to the mobility of ions and number of

ions present in unit volume. Conductance measurements can be employed to find the end points of
acid-base and other titration.

Consider for instance, the titration of a mixture of a strong acid (HCl) and a weak acid
(CH3COOH) against a strong base (NaOH) which takes place in two steps.

In the beginning, highly mobile H+ ions are replaced by less mobile Na + ions and hence the
specific conductance of the solution decreases sharply till the complete neutralization of HCl (V1).

Afterwards, CH3COOH undergo neutralization and completes at V2. The marginal increase in
specific conductance from V1 to V2 is due to the formation of CH3COONa, which is a stronger
electrolyte than acetic acid.

Further, addition of excess NaOH beyond V2 leads to significant increase in specific

conductance due to excess OH- ions.
Volume of NaOH required to neutralize HCl = V1 mL
Volume of NaOH required to neutralize CH3COOH = (V2 - V1) mL Volume
of NaOH required to neutralize both HCl and CH3COOH = V2 mL

17
 Specific conductance of the solution is plotted versus volume of NaOH added. The intersection
of first two straight lines corresponds the neutralization of HCl and the intersection of second and
third straight lines corresponds to neutralization of CH3COOH.

Procedure
The conductivity cell is dipped in a beaker containing given acid mixture. Burette is filled with
standard NaOH solution. Connect the conductivity cell to the conductivity meter and initial specific
conductance is recorded. Add 0.5 mL of NaOH from the burette each time and corresponding specific
conductance is recorded. Initially, specific conductance decreases sharply, then increases marginally
and further increases significantly. Take 6 readings from the point where a significant increase in the
specific conductance is observed.

Plot a graph of specific conductance versus volume of NaOH. From the graph, find
neutralization points of HCl (V1) and acetic acid (V2 - V1) and calculate the amount of strong and
weak acids present in the mixture.

Result
Amount of HCl in a dm3 of the solution Amount = ….. ………….. g
of CH3COOH in a dm3 of the solution = ….. ………….. g

Graph :

Scale:
X-axis, 1 cm = 1 mL
Y-axis, 1 cm = 1 S/cm
→conduct
ance

V1=.......mL V2=.......mL
eci
fic
Sp

Volume of NaOH

18
OBSERVATIONS AND CALCULATIONS

Volume of acid mixture given (Vmixture) = ------ cm3

Strength of standard NaOH solution = 0.5 N

Volume of NaOH Specific conductance Volume of NaOH Specific conductance

(ml) (Siemens/cm) (ml) (Siemens/cm)
0 7.5
0.5 8.0
1.0 8.5
1.5 9.0
2.0 9.5
2.5 10.0
3.0 10.5
3.5 11.0
4.0 11.5
4.5 12.0
5.0 12.5
5.5 13.0
6.0 13.5
6.5 14.0
7.0

Volume of NaOH required to neutralize HCl ( V1) = ....................... mL (from the graph)

Normality of HCl ( NHCl ) = ( V1 x NNaOH ) / Vmixture =

=................. N.
Amount of HCl in a dm3 of the solution = NHCl × Equivalent weight of HCl (36.5)

= .................. g

Volume of NaOH required to neutralize CH 3COOH ( V2 - V1) = ..................... mL (from the graph)

= [(V - V ) x N ]/V
Normality of CH3COOH ( NCH3COOH ) 2 1 NaOH mixture =
=................. N.
Amount of CH COOH in a dm3 of the solution = N × Equivalent weight of CHCOOH(60)
3 CH3COOH 3

= .................. g

19
20
 Determination of pH/pKa of solutions using
glass membrane electrode

Expt. No. 4 Date:.........................

Aim
Determination of pKa of a given weak acid using pH meter
Principle
A weak acid, like acetic acid dissociates in its aqueous solution partially as follows
CH3COOH + H2O H3O+ + CH3COO–
The equilibrium constant for the above reaction is

Ka =
The solution is considered to be very dilute and the activity of water in very dilute solution is
assumed to be constant.
Ka [CH3COOH]
[CH3COO-]
Taking ‘–log’ on both sides

– log [H3O+] = –log Ka – log

i.e., pH = pKa + log Henderson - Hasselbalch equation

When acetic acid (titrand) is titrated with NaOH solution (titrant), pH of the titrated solution increases
in accordance with the above equation; since concentration of sodium acetate, (CH 3COO -) increases and
concentration of unreacted acetic acid, [CH3COOH] decreases as the titration progresses.
When the acid is titrated to reach half of the equivalence point,
[CH3COO–] = [CH3COOH]
and hence pH = pKa

That is, pKa of the acid is pH at the half equivalence point.

21
 Weak acid can be titrated potentiometrically, using a pH sensitive Glass Electrode as an indicator
electrode and reference electrode (either Ag/AgCl electrode or saturated calomel electrode), both being
connected to a pH meter to measure the pH of the titrand after each addition of NaOH solution from a
burette. Plot a differential graph of ∆pH / ∆V versus volume of NaOH and find the volume of NaOH that
corresponds to maximum ∆pH / ∆V value as equivalence point. Plot another graph of pH versus volume
of NaOH, and find out pH correspond to half equivalence point is pK a of weak acid.

The pH meter should be standardized using a buffer solution of known pH in order to set the pH
meter to read the pH of the titrating solution directly from the meter as accurately as possible.

Procedure
Immerse glass electrode and reference electrode assembly into a 100 mL beaker containing the
given weak acid, connect to pH meter and record pH of the sample. Add 0.5 mL of NaOH each time
from the burette and record the corresponding pH. After sharp increase in the pH (corresponds to
equivalence point), take 4 more readings.

Plot a differential graph of pH / ∆V) versus volume of NaOH and find out equivalence point.
Plot another graph of pH versus volume of NaOH and determine pK a, which corresponds to the pH
value at half equivalence point.

Results
pKa of the given weak acid = ……….…………..

22
 Vol. of ∆V ∆pH
pH ∆pH / ∆V
NaOH (mLs.) (V2–V1) (pH2–pH1)

0
0.5 0.5
1.0 0.5
1.5 0.5
2.0 0.5
2.5 0.5
3.0 0.5
3.5 0.5
4.0 0.5
4.5 0.5
5.0 0.5
5.5 0.5
6.0 0.5
6.5 0.5
7.0 0.5
7.5 0.5
8.0 0.5
8.5 0.5
9.0 0.5
9.5 0.5
10.0 0.5

23
 Graphs :

Scale:
X-axis, 1 cm = 1 mL
Y-axis, 1 cm = 1 pH
pH

pH=pKa =.........

Half equivalence point = ..........mL

Equivalence point = ..........mL

Volume of NaOH

24
25
 Preparation of semiconducting (CuFe2O4)
nanoparticles and characterization
Expt. No. 5 Date:.........................

Aim : Preparation of semiconducting CuFe2O4 nanoparticles and characterization

1. Introduction

Copper ferrite (CuFe2O4) nanoparticles are one of the most considerable or promising metal-
oxide nanomaterials due to their novel magnetic properties. Hence, they were used successfully in
various applications like photo catalyst, Ferro fluids technology, high-energy density magnetic
recording, magnetic imaging, biomedical drug delivery systems, biosensors, data storage, magneto-
optical devices, gas sensors, and other magnetic applications.

In general ferrites have the chemical formula of MFe2O4 (M= Mn, Fe, Co, Ni, Cu etc.) and have
outstanding electrical, optical, catalytic, and magnetic properties. Typically, copper ferrite (CuFe 2O4)
is an important effective material like other spinel ferrites.

2. Synthesis of Copper ferrites (CuFe2O4) nanoparticles

Copper ferrite nanoparticle was synthesized by co-precipitation method. In a typical
experiment, 25ml of 0.4M FeCl3, 25ml of 0.2M CuSO4, and 50 mg of SDS (sodium dodecyl sulfate)
are taken in a beaker, and then they were dissolved by continuous magnetic stirring. In continuous
magnetic stirring two solutions were mixed until a homogenous solution is formed. Then 25ml of
1.5 M NaOH was added drop by drop to the above mixture. The color of the solution changes and
precipitate formation takes place. The obtained precipitate is filtered, dried, and calcined at 600oC
for 3 hours to get well-crystallized copper ferrite. Then the obtained precipitate was washed with
acetone to make it free of impurities and dried in a hot air oven at 50 o C. finally grained to get a fine
powder CuFe2O4 using an agate motor.

26
Schematic representation of the experimental procedure.

27
3 UV-Visible spectra of copper ferrite(CuFe2O4) NPs:

28
Fig.1(A) UV-Visible spectra for CuFe 2O4 and (B) Energy band gap
calculated graph for CuFe2O4.
The copper ferrite nanoparticle was characterized by UV–visible absorption
spectroscopy. The UV–visible absorption spectra of the prepared CuFe2O4 NPs dispersed in
ethanol solution and scanned in the wavelength between 200–800nm range, show the
maximum absorbance at 402nm (fig1(A)) and we found the energy band gap of CuFe 2O4 at
3.06eV (fig1(B)).

Band gap calculation:

Using the formula Ebg = hc/λ where,

h = Planck’s constant
c = velocity of light
λ = wavelength the obtained value i.e., E bg=3.09ev
was evident when compared to the previously
reported work] using same formula.

SEM images of CuFe2O4 NPs

29
 XRD pattern of copper ferrite CuFe2O4 NPs

The average crystallite size is estimated to be 70.7nm calculated using

Debye-Scherrer's formula. The sharp peaks suggest that copper ferrite
nanoparticles are well crystallized.

30
Table showing size of the nanomaterial:

31
6

In this study the copper ferrite (CuFe2O4) nanoparticles were synthesized.

Report:
o Synthesized CuFe2O4 nanoparticles and characterized by UV-Visible spectra,
and XRD.
o Prepared CuFe2O4 nanoparticles show blue shift (402 nm) and energy band
gap (3.06 eV).
o XRD results show that particle is crystalline in nature, the average crystalline
size is found to be 70 nm with a face-centered cubic structure.

32
 Preparation of Conducting Polyaniline Thin film
by Electropolymerization

Expt. No. 6 Date :.........................

Aim: Synthesis of PANI (Polyaniline) by electrochemical polymerization method

Electrochemical polymerization of aniline into PANI (Polyaniline).

Principle: Electrochemical polymerization or electro-polymerization is based on the

deposition of the polymer onto the surface of a solid electrode material. This occurs
through a generally accepted mechanism that involves the formation of cationic radical by
the oxidation of the monomer on the solid electrode material, followed by the growth of the
polymer film on the surface of the working electrode, which may be a carbonaceous, a
metallic, or a conducting glass material. As the oxidation of the monomer is voltage- or
current-induced, electrochemical polymerization is, therefore, a green chemistry
methodology.

Chemicals required: Aniline and H2SO4 were purchased from Sigma-Aldrich. All
chemicals used were analytical grade. The monomer aniline was distilled under reduced
pressure and stored in the refrigerator (about 4 C) before use. All aqueous solutions were
prepared using double distilled water.

Procedure:

Electro polymerization of aniline: At first, before each scan the Pt electrode was prepared to
ensure a reproducible surface by polishing, rinsing with distilled water and then
electrochemically cleaned by cyclic voltammetry in 1 M of H 2SO4 solution until a
reproducible voltammogram was obtained. The electro polymerization of the aniline was
performed on a PGZ 301 Potentiostat/ Galvanostat with a three-electrode system, containing
a Pt wire (0.2 cm2) as the working electrode, a saturated calomel electrode (SCE) as a
reference electrode and glassy carbon as a counter electrode. All potentials recorded are
referred to this reference electrode. PANI films were prepared on the platinum working
electrode by the cyclic voltammetry in 1 M H2SO4 solution containing aniline at room
temperature (20°C). After the electro-polymerization of the aniline, the PANI electrode was
repeatedly washed with doubly distilled water.

33
The potential range applied for the
electrodeposition is +0.75V to +1.5V,
maximum deposition takes place at +1.5V.

[The electrodeposition of Polyaniline (PANi) at +1.50 V was 2.5 times faster than at +1.0V
and 23 times faster than at +0.75V. The thin compact PANi film is a promising material to
be used in electrochromic windows due to its good adhesion, transparency and
electrochromism.

Observation and calculation:

a. Colour of the working electrode after deposition………………

b. Weight of the WE, before the deposition (w1)= ……………..mg
c. Weight of the WE, after the the deposition (w2)= ………….mg
d. Weight of the PANI deposited, W = w2-w1 = ……….mg.

The synthesized PANI is characterized by FTIR, the model FTIR of PANI is given below.

Result:

34
35
Part - B

36
 Estimation of total hardness of water

Expt. No. 1 Date:.........................

Aim
Estimation of total hardness of give water sample using standard EDTA solution

Principle
Water which does not produce lather with soap solution readily, but forms a white curd, is called
hard water. On the other hand, water which lathers easily on shaking with soap solution is called soft
water. Hardness of water may be divided into two classes.
1. Temporary or carbonate hardness is caused by the presence of dissolved bicarbonates of
calcium, magnesium and other heavy metals and the carbonate of temporary hardness is
removed by boiling.
2. Permanent or non-carbonate hardness is due to the presence of chlorides and sulphates of calcium,
magnesium, iron and other heavy metals. Permanent hardness is not removed by boiling.
Temporary and permanent hardness together are called total hardness. Hardness is expressed in
parts of CaCO3 equivalents per million parts of water, i.e. ppm or mg of CaCO 3 equivalents per litre
or dm3 of water, i.e. mg/L.
EDTA is ethylene diamine tetra acetic acid

EDTA, H4Y (H4C10H12O8N2) is insoluble in water whereas, its disodium salt, Na 2H2Y is readily
soluble. For hardness estimation, 0.025 M solution is used.
Molarity = g of EDTA / Litre
Mol.wt.

(g of EDTA / 250 mL) 

4
=
Mol.wt.

Molarity x Mol.wt.
g of EDTA / 250 mL =
4

= 0.025x372.24
4

= 2.3265 g.

37
 EDTA combines with all bivalent metal ions in 1:1 ratio and forms highly soluble complex
ions. Thus when EDTA solution is added to hard water, Ca 2+ and Mg2+ ions combine with EDTA and
form highly soluble complex ions.
Na2H2Y + Ca2+ → Na2CaY + 2H+

Removal of H+ ions produced, increases the stability of the complex ions formed. This is
achieved by maintaining pH of the solution in basic range using an appropriate buffer solution.

Eriochrome Black – T (EBT) is a suitable indicator for this titration. It is a triprotic acid (H3D).
It dissociates remarkably easily giving the first H+ ion and hence exists as H2D- in its solutions.
Further dissociation of H2D- is pH dependent as shown below
H D–2
H+ + HD2– H+ + D3–
Red 5.3 – 7.3 Blue 10.5 – 12.5 Yellow – Orange

It exists as HD2- in the pH range 7-11, exhibiting blue colour. Many metal ions like, Mg2+, Ca2+
etc form red coloured soluble complex ions with HD2-.

HD2– + Ca2+ Ca HD
Blue Red
Hence EBT is known as a metal ion indicator. These complexes are less stable than the EDTA
complexes of the corresponding metal ions.

When EBT indicator is added to hard water at pH 10, HD2- of the indicator forms red complex
ion with a small fraction of Ca 2+ and Mg2+ depending upon the quantity of indicator used. When
EDTA is added to this solution, it complexes all the free Ca 2+ and Mg2+ ions present. Ca2+ and Mg2+
ions combined with the indicator start reacting with EDTA, when the solution does not contain free
Ca2+ and Mg2+ ions. When enough EDTA is added to react with all the Ca2+ and Mg2+ combined with
the indicator, free indicator, (HD2-) is set free. This happens at the end-point and hence colour changes
from red to blue.

CaHD + Na2H2 Y → Na2Ca Y + HD2– + 2H+

Red Blue
NH4OH – NH4Cl buffer is used to maintain the pH at 10 during the titration.

Procedure
Preparation of standard solution of disodium salt of EDTA
Weigh accurately the given amount of disodium salt of EDTA crystals and transfer into a 100 mL
standard flask. Dissolve the crystals by adding 5 mL ammonia solution and then add distilled water upto
the mark and shake well for uniform concentration. This solution is taken in a 25 ml burette.

Estimation of hardness of water

25 mL of given hard water is pipetted out into a clean conical flask. 5 mL of NH4OH – NH4Cl buffer and
2 drops of Eriochrome Black – T indicator are added. The resulting wine red coloured solution is titrated with
EDTA until clear blue solution is obtained. No tinge of reddish blue should remain at the end point. Titration
is conducted slowly near the end-point. Titration is repeated until agreeing value is obtained.
Result
Total Hardness of water = ……………… ppm CaCO3 equivalents or mg/L

38
OBSERVATIONS AND CALCULATIONS
Preparation of standard solution of EDTA

Wt. of weighing bottle with solid EDTA salt, (W1) = …………………….. g

Wt. of empty weighing bottle, (W2) = .…………………… g

Wt. of EDTA salt dissolved / 250 mL, (W1-W2) =…………………….. g

Weight of EDTA x

Molarity of EDTA salt solution, MEDTA =
Mol. wt.of EDTA (372.24)

= .......................... M (X)

Estimation
Burette : Standard EDTA salt solution.

Conical flask : 25 mL of Hard water + 5 mL NH 4 OH – NH4 Cl buffer

Indicator : 2 drops of Eriochrome black T
End Point : Change of colour from wine red to blue

Trial No. 1 2 3

Final Burette Reading

Initial Burette Reading 0.0 0.0 0.0

Vol. of EDTA salt solution (mL)

Agreeing value, V EDTA = ........................ mL

39
1000 cm3 of 1 M EDTA = 100 g of CaCO3 (Mol. wt of CaCO3 is 100)

100  VEDTA  X
∴ ‘VEDTA ’ cm3 of ‘X’ MEDTA = 1000 g of CaCO3.

= ......................... g (Y)

25 cm3 of Hardwater contains ‘Y’ g of CaCO3.

Y x106
106 cm3 of Hardwater contains = 25 ppm of CaCO3.

Thus total Hardness of Water =

= ......................... ppm of CaCO3

40
41
 Evaluation of Dissolved Oxygen by Winkler’s
method and hence assessment of quality of water.
Expt. No. 2 Date:.........................

AIM: To estimate the amount of dissolved oxygen in the given sample of water by
Winkler’s iodometric method & waste water by Chemical Oxygen demand method.
Principle: Dissolved oxygen (DO) determination measures the amount of dissolved (or
free) oxygen present in water or wastewater. Aerobic bacteria and aquatic life such as fish
need dissolved oxygen to survive. If the amount of free or DO present in the wastewater
process is too low, the aerobic bacteria that normally treat the sewage will die. DO is
determined by the titrimetric method developed by Winkler.
1. Dissolved molecular oxygen in water is not capable of reacting with KI, therefore an
oxygen carrier such as manganese hydroxide is used. Mn(OH) 2 is produced by the action
of KOH on MnSO4.
2. Mn(OH)2 so obtained reacts with dissolved molecular oxygen to form a brown
precipitate of basic manganic oxide, MnO(OH) 2.
3. MnO(OH)2 then reacts with concentrated sulphuric acid to liberate nascent oxygen.
4. Nascent oxygen results in oxidation of KI to I 2.
5. This liberated iodine is then titrated against standard sodium thiosulphate solution using
starch as an indicator.
6. Thiosulphate reduces iodine to iodide ions and itself gets oxidized to tetrathionate ion.
(Refer the reactions below.)

Reaction:
2NaOH + MnSO4 Mn(OH)2 + K2SO4 ...(1)
2Mn(OH)2 + O2 2MnO(OH)2 ...(2)
MnO(OH)2 + H2SO4 MnSO4 + 2H2O + [O] ...(3)
2KI + H2SO4 + [O] K2SO4 + H2O + I2 ...(4)
I2 + I- I3- ...(5)
2S2O32 — + I3— 3I— + S4O62 — ...(6)

Procedure:
PART A: Preparation of Sodium thiosulphate solution
A known weight of sodium thiosulphate crystals given in a weighing bottle is weighed and
transferred into a 100 ml standard flask. It is dissolved with water and then made upto the
mark. The solution is shaken thoroughly to obtain uniform concentration. The normality of
sodium thiosulphate solution is calculated.

42
PART B: Estimation of dissolved oxygen (DO):

Transfer about 300 ml of water sample into a clean glass stoppered bottle. Add 3 ml of
manganous sulphate (MnSO4) solution carefully by dipping the tip of the pipette below the
surface of water. Add 3 ml of alkaline potassium iodide solution. Stopper the bottle and
shake well and allow the precipitate to settle down. Now add 1 ml of concentrated Sulphuric
acid and mix well until the precipitate dissolve completely. Pipette out 100 ml of this
solution into a clean conical flask and slowly titrate against standard sodium thiosulphate
solution using starch indicator near the end point. Let the volume of Sodium thiosulphate
be V ml.

Precautions
1. Do not allow air to trap while sampling water during BOD analysis.
2. Dip the tip of the pipette just at the bottom of the BOD bottle and gently release the reagents.
3. Take care that the chemicals do not flow out from the bottle while shaking/swirling.
4. Observe the colour changes during the BOD reaction, if any.

Result:

DO of the given water sample =………………….. ppm/mg per litre

Observations & Calculations:

PART A:
Wt. of weighing bottle + Sodium thiosulphate crystals = w1 =____________ g
Wt. of empty weighing bottle = w2 = ____________ g
Wt. of Sodium thiosulphate crystals W = (w1 – w 2) =
______________ g.

Normality of Na2S2O3 salt solution, N Weight of Na2S2O3 x

Na2S2O3 = Mol. wt.of Na2S2O3
(248.18)

= .......................... N (X)

43
PART B:
Burette : Sodium thiosulphate solution
Conical Flask : 100cm3 of the solution after dissolution of precipitate.
Indicator : Starch solution – added towards the end point
End point : Blue to colourless.

Burette Reading Trial I Trial II Trial III

Final Burette Reading

Initial Burette Reading

Volume of Na2S2O3
solution added in cm3

Calculations
1000 mL of 1N Na2S2O3 = 8 g oxygen.
‘V’ mL of ‘X’N Na2S2O3 = (V×X×8) / 1000 g oxygen per 100 mL water sample
= V × X × 8 mg oxygen per 100 mL water sample
= V × X × 8 × 10 mg oxygen per 1000 mL water sample
= V × X × 8 × 10 mg oxygen per 1000 mL water sample.

44
45
 Determination of percentage of iron in corrosion
products
Expt. No. 3 Date:.........................

Aim
Estimation of percentage of iron in a given sample of haematite solution using potassium
dichromate solution.
Principle
Haematite is an important ore of iron containing mainly ferric oxide (Fe2O3) and a small amount
of silica (SiO2). A known weight of the ore is digested with hydrochloric acid and the insoluble
residue mainly containing silica is removed by filtration. The filtrate is diluted to 250 mL and is
supplied for the estimation. Ferric salts are oxidizing agents and they do not react with another
oxidizing agent like K2Cr2O7. FeCl3 must be reduced to ferrous chloride (FeCl2) which is a reducing
agent and hence reacts with K2Cr2O7 as

(i) K2Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 + 4H2O + 3 (O)

(ii) 6FeCl2 + 6HCl + 3(O) → 6 FeCl3 + 3 H2O

According to Equation (i):

1 molecule of K2Cr2O7 ≡ 3 atoms or 6 equivalents of oxygen

Equivalent wt. of K2 Cr2O7 =Mol.wt.of K2Cr2O7 = 294.18 = 49.03

6 6

According to Equation (ii)

6 molecules of FeCl2 = 6 molecules of FeCl3
= 6 atoms of iron
= 3 atoms or 6 equivalents of oxygen.
∴ Equivalent wt. of FeCl2 = Mol. wt. of FeCl 2 = 126.8
= Mol. wt. of
Equivalent wt. of FeCl3 FeCl3 = 162.2
Equivalent wt. of iron = At. wt. of iron = 55.85

FeCl3 is quantitatively reduced to FeCl2 by adding a slight excess of stannous chloride (SnCl2)
solution in hot condition in the presence of concentrated HCl. Unreacted SnCl 2 is destroyed by
adding saturated mercuric chloride (HgCl2) solution. Resulting solution containing FeCl2 is titrated
with a standard solution of K2Cr2O7 prepared, using potassium ferricyanide, K3[Fe(CN)6] as external
indicator. When a tiny drop of solution from the flask containing ferrous, Fe2+ ions is mixed with a
tiny drop of K3[Fe(CN)6] solution on a wax paper, a blue ppt forms. The blue ppt is considered to
be ferrous ferric cyanide, Fe3 [Fe(CN)6]2 complex.
3FeCl2 + 2K3[Fe(CN)6] → Fe3 [Fe(CN)6]2 + 6KCl
When the indicator drop fails to produce blue colur with a drop of reaction mixture mark the end
point due to non-availability of Fe(II) ions.

The precautions given below should be adopted in the experiment :

46
 (i) Only slight excess of SnCl2 should be used to reduce FeCl3 to
FeCl2. 2FeCl3 + SnCl2 → SnCl4 + 2 FeCl2
Stannic chloride
SnCl2 solution should be added drop wise to the hot yellow coloured solution containing
FeCl3 and conc. HCl, until the solution becomes colourless and then one or two drops of
SnCl2 solution in excess should be added to ensure complete reduction of FeCl3.
(ii) SnCl2 is a strong reducing agent. If the ore solution is titrated with K2Cr2O7 solution, before
the destruction of unreacted SnCl2, both FeCl2 and SnCl2 present in the solution react with
K2Cr2O7 giving rise to higher titre value. Therefore unreacted SnCl2 must be destroyed
before titration. It is achieved by adding saturated HgCl 2 solution.
SnCl2 + 2HgCl2 → Hg2Cl2 ↓ + SnCl4 mercurous
chloride (silky white)
Hg2Cl2 does not react with K2Cr2O7 even though it is also a reducing agent, since it present
as ppt and not in solution.

(iii) A silky white ppt must be produced on adding HgCl2. If the ppt does not appear, the solution
does not contain unreacted SnCl2 and hence reduction of FeCl3 is incomplete. On the other
hand, if a black ppt of finely divided mercury is produced, the solution contains too much
unreacted SnCl2.
SnCl2 + Hg2Cl2 → 2 Hg + SnCl4
(black)
Finely divided mercury, being a good reducing agent, reduces K2Cr2O7. In either case, the
solution must be rejected and the reduction must be repeated with fresh ore solution and a
solution containing slight silky white ppt. should only be used for titration.

(iv) The solution must be diluted to a large volume before titration in order to minimise the loss
of iron in the drops removed from the solution for testing with the drops of indicator to detect
the end-point.

47
Procedure

Preparation of standard K2Cr2O7 solution

Weigh accurately the given amount of K2Cr2O7 crystals and transfer into a 100 ml standard
flask. Dissolve the crystals by adding distilled water and make upto the mark and shake well for
uniform concentration. This solution is taken in a 25 mL burette.
Estimation
Pipette out 25 mL of haematite solution into a conical flask. Add 5 mL of conc. HCl and heat
to boiling. To this hot solution, add SnCl2 solution drop wise till yellow colour just disappears. Add
one or two drops of SnCl2 in excess and cool the contents of conical flask to room temperature. Now,
add 5 mL HgCl2 solution in one lot and mix thoroughly to get a thin silky white precipitate of Hg2Cl2.
Reject the sample in case of thick silky white ppt. or no ppt. or black ppt. and repeat the above process
with a fresh ore sample. Further, add 2 TT of distilled water to the flask and titrate with standard
K2Cr2O7 solution, until a drop of the titrated solution fails to give blue ppt or green colour with a
drop of indicator taken on a wax paper and record the burette reading. The titration is repeated until
agreeing value is obtained.

Result

Percentage of iron in the given haematite ore sample = …………………….

48
OBSERVATIONS AND CALCULATIONS

Preparation of standard K2Cr2O7 solution

Wt. of weighing bottle with K2Cr2O7, (W1) = ……………………….g

Wt. of empty weighing bottle, (W2) =………………………. g

Wt. of K2Cr2O7 dissolved, (W1- W2) =… …………………… g

Normality of K2Cr2O7 solution, NK2Cr2O7

= Wt. of K2Cr2O7 X 10
Eq. wt. of K2Cr2O7 (49.03)
=

= ........................ N.

Estimation

Burette : Standard K2Cr2O7 solution

Conical flask : 25 mL haematite ore solution + 5 mL Conc. HCl (heated to boiling)

+ SnCl2 (cooled) + 5 mL saturated HgCl2 solution (added rapidly) + 2

test tube distilled water
Indicator : Drops of potassium ferricyanide solution on wax paper

(External indicator)
End point : No blue ppt or green colour on mixing a drop of titrated solution with a

drop of indicator.

Trial No. 1 2 3

Final Burette Reading

Initial Burette Reading 0.0 0.0 0.0

Vol. of K2Cr2O7 (mL)

Agreeing value, V K2Cr2O7 = ...................... mL

49
Weight of haematite ore in 250 ml. of the given solution, a = …………….g

N  V
Normality of iron in haematite ore solution, NFe
= K2Cr2O7 K2Cr2O7

V
Fe

= ……………. N.

= NFe X Eq. wt of Fe (55.85)

Wt. of iron present in 250 ml. of ore solution,
4

X = ……………. g.

= X 100
Percentage of iron in the given haematite ore sample
a

= …………….

50
51
 Estimation of percentage of Copper in brass
alloy by iodometric method
Expt. No. 4 Date:.........................

Determination of percentage of copper in brass using a standard sodium thiosulphate

solution.

Aim: To determine the percentage of copper in the given brass sample using standard
sodium thiosulphate solution.
Principle: Brass is an alloy of copper and zinc. When brass dissolves in conc. nitric acid
copper forms copper nitrate when the reacting brass solution is treated with KI with slight
acidic conditions. Copper reduces KI to iodine and copper is precipitated as cuprous
iodide. The liberated iodide is treated with sodium thiosulphate using starch indicator. The
volume of sodium thiosulphate consumed corresponds to the iodine liberated which is in
turn is equivalent to copper nitrate.
Cu(NO3)2+2NH4OH Cu(OH)2 +2NH4NO3
Cu(OH)2+KI → Cu2I2 +I2
I2+Na2S2O3 Na2S4O6+NaI

Chemicals Required: Brass sample, Conc. HNO3, urea, NH4OH, acetic acid, 10% KI,
Sodium thiosulphate, Starch indicator.

Procedure:

Preparation of brass solution:

Weigh accurately brass sample into a clean conical flask/beaker. Add 1ml of conc HNO 3,
when brass completely dissolves add 1g of urea and 1 test tubes of distilled water and boil
the solution till all the oxides of nitrogen are completely expelled and cool the solution.
Transfer the entire solution into 100ml standard flask and dilute upto the mark with
distilled water.

Estimation of Copper in brass:

Pipette out 25ml of the prepared brass solution into the conical flask. Add dropwise
ammonium hydroxide until a permanent bluish colour (precipitate of cupric hydroxide)
appear. Add acetic acid till the precipitate dissolves. Add 10ml of 10% KI and titrate the
liberated iodine against standard sodium thiosulphate solution taken in burette till the
colour of the solution is pale yellow. Add 5 drops of starch indicator and titrate further till
the milky white precipitate persists. Repeat the procedure with another sample of brass. Let
the volume of sodium thiosulphate consumed be ‘x’ ml.

Result: Percentage of copper in the given sample of Brass = ______________.

52
Observations and Calculations:

a) Weight of brass sample = ___________ g.

b) Estimation of brass:

Burette reading 1 2 3
Initial reading
Final reading
Volume of Na2S2O3
Agreeing value = ________ml (Y)

Calculations:

Normality of Na2S2O3 (X) = 0.05 N

Normality of Brass sample = Volume of Na2S2O3(Y) x Normality of Na2S2O3(X)

Volume of Brass sample (25ml)

= ……………………..

Weight of copper present in 100ml of Brass solution

= Normality of Brass sample x equivalent weight of copper (63.55) x100
1000

=……………………..

Percentage of copper = Weight of copper x 100

Weight of Brass

= ……………………

53
 Construction of Daniel Cell

Expt. No. 5 Date:

Aim: Construction of Daniel cell:

Principle: In a Daniel cell electrons flow from zinc electrode to copper electrode through an
external circuit, while metal ions form one half cell to the other through the salt bridge. Here
current flows from copper electrode to zinc electrode that is cathode to anode via an external
circuit.

Reagents required:

1M Copper (II) sulfate

Copper wire

0.5M Sodium hydrogen sulfate

1M Zinc sulfate

Zinc wire

Procedure: Prepare 1M of copper sulfate CuSO4 solution and 1M of zinc sulfate ZnSO4
solution. Connect the solutions with a piece of fabric treated with 1M KCl solution. Connect
a zinc Zn wire to the black crocodile clip, and a copper Cu wire to the red crocodile clip.
Immerse the metal wires in the vials: put the Zn wire in the vial of ZnSO 4 solution and the
Cu wire in the vial of CuSO4 solution. Connect the two ends to the ammeter for detection of
current or connect the two ends to a led.

Theory: In the Daniel cell, copper and zinc electrodes are immersed in a solution of
copper(II) sulfate and zinc sulfate, respectively. At the anode (negative electrode), zinc is
oxidized as per the following half reaction:

Zn(s) → Zn2+ (aq) + 2e− (Standard electrode reduction potential −0.7618 V)

At the cathode (positive electrode), copper is reduced as per the following reaction:

Cu 2+ (aq) + 2e− → Cu(s). (Standard electrode reduction potential +0.340 V)

The total reaction is:

Zn(s) + Cu 2+ (aq) → Zn2+ (aq) + Cu(s). (Open-circuit voltage 1.1018V)

These processes result in the accumulation of solid copper at the cathode and the corrosion
of the zinc electrode into the solution as zinc cations.
54
Use of Salt bridge:

It maintains electrical neutrality in two compartments by allowing movement of anions

towards anodic compartment and cations towards cathodic compartment.

 It is a glass tube having potassium chloride or ammonium nitrate in a gelatin form.

 The gelatin allows ionic movement but prevents any kind of mixing.
 In the case of potassium chloride or ammonium nitrate the ionic mobilities of cations
and anions are the same.
Functions of Salt bridge:

 A salt bridge acts as an electrical contact between the two half cells.
 It prevents mechanical flow of solution, but it provides a free path for the migration
of ions, to maintain an electric current through the electrolyte solution. It prevents
the accumulation of charges.
 A salt bridge helps in maintaining the charge balance in the two half cells.
 A salt bridge minimizes or eliminates the liquid junction potential.

55
56
 Faraday’s law verification by using
Electrodeposition of Cu/Ni/Zn on stainless steel.

Expt. No. 6 Date:.........................

Aim

To verify the Faraday’s law by using electrodeposition of Cu/Ni on Stainless steel substrate

Principle
Electrodeposition is a simple and a soft method for direct deposition of materials on the
conductive substrate. This is widely used for modification surfaces, protection of reactive surfaces,
metal finishing and in device fabrications. This method use the electrochemical cell which should
have minimum two electrodes and electrolyte.

Faraday’s Law
First Law: The mass of a substance liberated at an electrode is directly proportional to the charge
passing through the electrolyte. The mass of a substance altered at an electrode during electrolysis
is directly proportional to the quantity of electricity transferred at that electrode. Quantity of
electricity refers to the quantity of electrical charge, typically measured in coulomb.
m∝Q

m=ZQ

where

Q – Charge = i.t

Z – Electrochemical equivalent

Faraday’s Second Law of Electrolysis states that “the mass of a substance deposited at any
electrode on passing a certain amount of charge is directly proportional to its chemical equivalent
weight.” Or “when the same quantity of electricity is passed through several electrolytes, the mass
of the substances deposited are proportional to their respective chemical equivalent or equivalent
weight”. Mathematically it can be represented as follows

w∝ E

Where w = mass of the substance

E = equivalent weight of the substance

57
It can also be expressed as – w1/w2=E1/E2

The equivalent weight or chemical equivalent of a substance can be defined as the ratio of
its atomic weight and valency.

Equivalent weight=Atomic weight/Valency

The cathode is reinserted in the cell and a different current I2 is passed for the same time t. The
mass m2 of the deposit is obtained. It is found that –

m1/m2 = I1/I2

so, m α I … … … (1)

The electrochemical equivalent of a substance is defined as the mass of substance liberated in

electrolysis when the one-coulomb charge is passed through the electrolyte. The experiment is
repeated for the same current I but for different times t 1 and t2. If the masses of the deposits are
m3 and m4 respectively, it is found that

m3/ m4 = t1/ t2

so, m α t … … … (2)

From relations (1) and (2)

m α It or m α q Thus, the first law is verified.

Verify Faraday’s First law by passing different quantities of electricity in the same solution and
calculating the ratio of masses of the formed materials at the cathode or dissolved from the anode
and comparing these ratios of the passed quantities of electricity.
Increasing the mass of substance at the cathode by increasing of quantity of electricity passed in
solution, we find that m ∝ Q.

Electrodeposition of metals

Cu2+ + Supporting electrolyte Cu

Here the metal ions are reduced by applying negative potential or cathodic current. The reduction
potential depends on various factors like, concentration of metal ions, conductivity of the medium,
temperature. Supporting electrolytes are used to reduce the resistance of the solution. They should
not interfere in the electrochemical reduction in the given potential window. Usually the ionic salts
like NaCl, Na2SO4 dissolved in water is used as supporting electrolyte.

The current values observed also depends on the extent of reduction reaction. The faster the rate of
the reaction the current increases substantially.
One mole of electrons is required for the reduction of one mole of ions. As we know, the Charge on
one electron is equal to

1.6021×10-19

58
C and one mole of electrons is equal to

6.023×1023 electrons.

So, charge on one mole of electrons is equal to –

(6.023×1023)×(1.6021×10-19C)=96500 C

This charge (96500 C) is called 1 Faraday.

If we pass 1 Faraday of charge in an electrolytic cell, then 1gm of the equivalent weight of the
substance will get deposited

Procedure

Prepare a 15 ml of 0.2 M Na 2SO4 solution in a clean cell/beaker. To this add the weight
corresponding to 0.2 M CuSO4 dissolve it completely. The stainless-steel plates thoroughly
cleaned and washed is used for the electrodeposition. Both anode and cathodes are SS substrate.
The cathode is cleaned, dried, weighed, and then inserted in the cell. A current I 1 is passed for a
time t. The current is measured by the ammeter. The cathode is taken out, washed, dried, and
weighed again. Hence the mass m1 of the substance deposited is obtained.

Plot the graph of current vs potential

Result

Amount of copper deposited for the time at constant current = ……….........… g

59
60
 Estimation of Sodium Using
Flame Photometer
Expt. No. 1
Demo Date:.........................

Aim
Estimation of sodium present in the given solution using Flame Photometer.
Principle
Flame photometry is an atomic emission technique used for the detection of metals. If a solution
containing metallic salts is aspirated into a flame, a vapour, which contains metallic atoms is formed.
The electrons from the metallic atoms are then excited from ground state (E 1) to higher energy state
(En) where n = 2,3,4 ….7, by making use of thermal energy
of flame. From higher energy states these electrons will return
to the ground state by emitting radiations (En-E1 = h ν by
where n = 2,3,4…..7), which are the characteristic of
each element.
Flame photometer correlates the emitted radiations
with the concentration of these elements. It is a simple and
rapid method for the elements that can be easily excited
(Sodium and other alkali metals).
A flame photometer consists of a pressure regulator and
flow meter for fuel gases an automiser, a burner, an optical
system, a photosensitive detector and an output recorder. A
filter of the element whose concentration is to be determined, is inserted between the flame and the
detector. Propane gas is used as fuel and air or oxygen is used as oxidant. A Combination of these
two will give a temperature of 1900 OC. The whole analysis depends on the flow rate of the fuel,
oxidant, the rate of introduction of the sample and the droplet size.
The sample containing the analyte is aspirated into the flame through an automiser. Radiation
from the resulting flame is collected by the lens and allowed to pass through an optical filter, which
permits only the radiation characteristic of the element under investigation into the photocell. The
output from the photocell represents the concentration and nature of the element.

Procedure
Transfer 2, 4, 6, 8 and 10 cm3 of standard sodium solution into different 50 cm3 volumetric flasks
from a burette. Make up all the solutions using distilled water. Stopper the flaks and shake well to get
uniform concentration. To the test solution also add distilled water upto the mark and shake well. Switch
on the instrument, turn the gas supply on and light the gas at the burner. Adjust the air supply from the
compressor to 10 psi, using the pressure regulator knob. Place the sodium filter (589 nm) in position. Now
dip the capillary tube in a cell containing distilled water. The stream of air automised as a fine mist draws
up the liquid. Regulate the gas supply so that the colour of the flame completely turns to blue. Adjust the
flame photometer to zero by means of the zero control knob. Now feed the 100ppm sodium ion solution
and adjust the reading to hundred. Repeat the process to confirm the
accuracy of the calibration.

61
 Feed the various sodium solutions prepared through the flame by spraying with automiser one
by one including the test solution. Note down the flame photometer readings. Plot a graph of flame
photometer reading against volume of the solution to form the calibration curve. Using the curve
obtained find out the volume of the test solution containing sodium ions and calculate the amount of
sodium ions in it.

Result:
Volume of the test solution = ......................... ml

Amount of Sodium ion in the given test solution = ......................... mg.

62
OBSERVATIONS AND CALCULATIONS

Concentration of the standard solution = 100 ppm

Amount of sodium in 1cm3 of the solution (w) = ....................... mg.

Vol. of sodium solution taken in 50 mL std. flask

Sl No. Flame Photometer reading
(mL)
1
2
3
4
5
6
7 Test Solution

Volume of the test solution, V ( from the graph) = .................. ml.

Amount of Sodium ion in the given test solution = V×w

= .................. mg.

Volume. of Na+ ion solution

63
64
 Determination of band gap energy
from Absorbance/Diffused
Reflectance Spectroscopy

Expt.No. Demo Date:.........................

Aim: To determine the band gap energy from Absorbance/Diffused Reflectance

Spectroscopy

Theory: The bandgap is related to the electric conductivity of the material. Generally, there
is no bandgap for metals, larger band gap in Insulators and in case of semiconductors the band
is intermediate between metal and insulator. The band gap energy of a semiconductor
nanomaterial shows the energy required to excite an electron from the valence band to the
conduction band. A correct determination of the band gap energy is important in predicting
photophysical and photochemical properties of semiconductors. There are two different types
of band gap i.e., direct and indirect bandgap. When the momentum of electron is same for
both bands (valence band and conduction band) then it is direct band gap and when the
momentum of electron changes for VB and CB it is called Indirect bandgap.
Principle: When light shines onto a sample, it is reflected in all directions, some of the light
undergoes specular reflection at the sample surface. Different sample will reflect light in
different directions. The rest of the light is refracted as it enters the sample, where it is
scattered due to internal reflection, reflection from the surfaces of other powder grains, or
repeated refraction entry into the powder. Some of this scattered light is emitted back into the
air. As the diffuse reflected light is reflected or passes through the powder, it becomes weaker
if absorption by the powder occurs. This results in a diffuse reflected spectrum. However, in
regions where the powder exhibits strong absorption, most of the diffuse reflected light in
long light paths is absorbed, such that only the diffuse reflected light from short light paths is
emitted back into the air. Conversely, in bands of weak absorption, some light is not absorbed
even in long light paths and this diffuse reflected light is emitted to the air, resulting in stronger
peaks than the transmission spectrum. In such a diffuse reflectance spectrum, the absorbed
wavenumber positions are the same as the transmission spectrum. However, the relative
intensity between peaks differs from the transmission spectrum because the weak peaks in the
transmission spectrum become comparatively stronger in the diffuse reflectance spectrum.
The so-called K-M function (f(R∞)) derived by Kubelka-Munk is used for comparison to
transmission spectra or quantitative analysis.

65
 Procedure:
a. The standard of the sample is placed in the sample holder in the primary slot which is used
as a reference.
b. The powdered sample is placed in the sample holder in secondary slot to measure the
absorbance / reflectance of a sample.
c. Set the range of UV-visible (200-800nm).
d. Select the absorbance or reflectance to be measured followed by baseline correction.
e. Click on measure to obtain a data.
f. Acquired data is calculated using Kumbelka-munk equation.
g. Plot wavelength vs calculated reflectance / absorbance to obtain a graph.

Observation and calculation:

Steps to calculate Band gap (Eg) from Absorbance/Diffused Reflectance Spectroscopy:
1) The Reflectance values are obtained at different wavelength from (200nm-1400nm).
2) The band gap is calculated by plotting the square product of the Kubelka-Munk function and
the energy F (R) hν versus the energy hν
The relative simple form is solved from k/s yielding by KM transform:
k = (1-R)2 ---i
s 2R
Where, k is absorption coefficient of sample, s is scattering coefficient

3) Energy E=1240/λ ---ii

4) Calculation of Kumbelka-Munk function (F(R)× hν) 2

F(R) hν is calculated by k/s × E ---iii

Example: Finding the band gap of Se-PVDF.

Wavelength (λ) 200nm
Reflectance (R)  71.3
%R= R x 100 0.713
k/s = (1-%R)2/(2x%R)  0.0577
Energy E= 1240/200 6.2
F(R) hν = k/s × E  0.0577 x 6.2  0.35812
(F(R)× hν)2(0.8489)2 0.12825

Similarly, for different wavelength the Kubelka-Munk function is calculated and F(R)hν
versus the Energy (hν) is plotted as given below. The band gap Eg is found to be 1.72eV.

66
Graph:

Plot of Diffused reflectance spectroscopy v/s wavelength

Result: Bandgap energy value/s for nanomaterial is __________.

67
 Dye Sensitized Solar Cell

Expt. No. Demo Date:.........................

Aim: To assemble the dye sensitized solar cell (DSSC)

Materials required-
Fluoride-doped tin dioxide conductive glass (≥2 plates)
A source of organic dye (ex: raspberries)
- Titanium Dioxide Paste
- Acetic Acid
- Water
- Glass Stirring Rod
- Scotch Tape
- Graphite Pencil
- Liquid Electrolyte Solution
- Binder Clips
- Wires
- A Solar-powered Calculator (You will be removing the stock PV solar cell and replace it
with your assembled DSSC)
- Soldering Equipment
- A Multimeter or Vernier Lab Quest (with Voltage & Current Probe(s))
- Tungsten Halogen Lamp
- Testing Apparatus

For every solar cell you assemble, you will need an anode and a cathode. The anode will
contain the dye and titanium dioxide molecules. Photons will excite the dye molecules'
electrons, and the electrons will jump from the dye molecule to the titanium dioxide to the
glass anode through diffusion. The electrons will subsequently travel through a circuit that
connects the two electrodes and return to the cell through the glass cathode. To complete
the circuit, an interstitial electrolyte solution facilitates the flow of electrons back to the
anode's organic dye molecules.

So, to assemble your anode, you must:

1) Prepare a titanium dioxide solution

Slowly add 20mL of an acetic acid solution (0.1675 mL CH3COOH per 99.8225 mL
water) to 12g of titanium dioxide powder. Slowly adding the acid, in addition to vigorously
mixing the solution, will ensure a uniform paste. It is recommended that you use a mortar

68
and pestle for this step.

2) Anneal titanium dioxide to your first glass plate

Cover each of the FTO glass plate's four edges with a 2mm-thick piece of scotch tape (on
the conductive side, as determined by a multimeter). This will create an ultra-thin "bowl"
that will be filled with the titanium dioxide solution. Apply three drops of the TiO2
solution to your electrode, and spread evenly and gently with a glass stirring rod.

Anneal the glass plate with an oven (or other heat source) at 450C for 30 minutes.

3) Soak the annealed electrode in your dye solution

Create a solution that contains dye molecules. This is done most easily with the juice from
frozen raspberries (which can easily be purchased in the frozen foods section of a
supermarket). The organic dye solution can be purified through filtration methods (Note,
however, my research team used very basic methods. We pulverized frozen raspberries
into a juice with a mortar and pestle. Afterwards, we squeezed this solution through a
cheesecloth, and this process removed the largest pieces of pulp.) Regardless, soak the
annealed electrode in your dye solution for ten minutes. (You should notice by then end of
this period that the color of your glass plate has changed as dye molecules covalently
bonded to the TiO2. This is the process known as sensitization. You should also be aware
that other dye solutions might require soaking for different lengths of time) Gently rinse
off the glass plate with water once and ethanol twice so that remaining pulp and sugars are
removed.

As for your cathode:

1) Cover one side of the glass surface with a carbon film (using the graphite pencil).

This process is rather self-explanatory. Just make sure that you are applying a complete
coating of graphite to the plate. This may take time depending on your pencil. (Figure 11)

2) Optional: Anneal the cathode in an oven at 450C for a few minutes.

3) Gently rinse the cathode with ethanol.

Step 3: Assemble Your Solar Cell

To assemble this DSSC, place the carbon-coated side of your cathode on top of the dye-
coated side of your anode. Do not allow your glass plates to overlap completely, offset the
electrodes so that they fully line up horizontally but extend beyond each other's vertical
ends. The offset will allow alligator wires to clip into each of the electrodes, thus allowing
you to assemble a circuit. Secure your offset glass plates with binder clips on the two
horizontal sides that line up completely.

To insert the electrolyte solution between the two electrodes, apply the electrolyte liquid
along an offset edge in between the two glass plates. Then, open and close the binder clips
in an alternating fashion (one binder clip at a time, not both). This will cause the
69
electrolyte solution to be sucked up into the cell and be distributed evenly among the
graphite coating and TiO2/anthocyanin complex.

Step 4: Test Your Solar Cell

Connect your assembled DSSC to a multimeter via alligator clips and wires. After the
assembled circuit is complete, place your cell under an indoor light source---or along a
windowsill. (Warning: Placing your solar cell directly under the sun without the proper
protection will cause severe degradation. Do initial testing under light sources that do not
emit UV radiation). Record the maximum voltage and current produced by your solar cell.
Multiply these two figures to obtain the power output.

Power is simply the voltage potential multiplied by the current. So, for example, if my DSSC
produced 0.400 Volts and 250 microamps (0.000250A), the power output would be 0.1
milliwatt (0.0001 watt).

70
 MODEL PROCEDURE
PART - A
Experiment 1

Estimation of Iron by Potentiometric Sensor

POTENTIOMETRIC ESTIMATION OF MOHR’S SALT

Add 1 TT of dil. H2SO4 into a 100 mL beaker containing the given Mohr’s salt solution. Immerse
calomel electrode and platinum electrode assembly and record the potential. Add 0.5 mL of 0.5N
K2Cr2O7 each time from the burette and record the corresponding potential. After the sharp increase
in the potential (corresponds to equivalence point), take 4 more readings.
Plot a differential graph of (E / V) versus volume of K2Cr2O7 and determine the equivalence point
that corresponds to the volume of K2Cr2O7 at which, (E / V) is maximum. From the normality
and equivalence point of K2Cr2O7, the normality & amount of Mohr’s salt is calculated.

71
 Experiment 2

Verification of Beer-Lambert’s Law by

detection of Copper
COLORIMETRIC by spectroscopy
ESTIMATION OF COPPER .

Add accurately 5, 10, 15, 20 and 25 mL of given copper sulphate solution from a 50 mL burette into
five separate 50 mL standard flasks. Further, add 5 mL ammonia to each flask and also into the 50
mL standard flask containing the test solution, make upto the mark with distilled water and shake
well. Prepare blank solution by adding 5 mL ammonia to an empty 50 mL standard flask and make
up the mark with distilled water.

Blank solution is taken in a cuvette and placed in the photoelectric colorimeter. The variable
diaphragm is adjusted to get zero absorbance at 620 nm. Measure the absorbance of all standard
solutions and test solution at 620 nm. A graph of absorbance (OD) versus volume of CuSO 4 is plotted
and the volume of test solution is determined.

72
 Experiment 3

Estimation of concentration of Acid mixture by

Conductometric sensor
The conductivity cell is dipped in a beaker containing given acid mixture. Burette is filled
with standard NaOH solution. Connect the conductivity cell to the conductivity meter and initial
specific conductance is recorded. Add 0.5 mL of NaOH from the burette each time and
corresponding specific conductance is recorded. Initially, specific conductance decreases sharply,
then increases marginally and further increses significantly. Take 6 readings from the point where a
significant increse in the specific conductance is observed.

Plot a graph of specific conductance versus volume of NaOH. From the graph, find
neutralization points of HCl (V1) and acetic acid (V2 - V1) and calculate the amount of strong and
weak acids present in the mixture.

Scale:
X-axis, 1 cm = 1 mL
Y-axis, 1 cm = 1 S/cm
→conduct
ance

V1=.......mL V2=.......mL
eci
Sp

fic

Volume of NaOH

73
 Experiment No. 4

Determination of pH/pKa of solutions using glass

membrane electrode

Immerse glass electrode and reference electrode assembly into a 100 mL beaker containing the
given weak acid, connect to pH meter and record pH of the sample. Add 0.5 mL of NaOH each time
from the burette and record the corresponding pH. After sharp increase in the pH (corresponds to
equivalence point), take 4 more readings.

Plot a differential graph of pH / ∆V) versus volume of NaOH and find out equivalence point.
Plot another graph of pH versus volume of NaOH and determine pK a, which corresponds to the pH
value at half equivalence point.

Scale:
X-axis, 1 cm = 1 mL
pH Y-axis, 1 cm = 1 pH

pH=pKa =.........

Half equivalence point = ..........mL

Equivalence point = ..........mL

Volume of NaOH

74
 Experiment No. 5

Preparation of semiconducting (CuFe2O4)

nanoparticles and characterization

Copper ferrite nanoparticle was synthesized by co-precipitation method. In a typical

experiment, 25ml of 0.4M FeCl3, 25ml of 0.2M CuSO4, and 50 mg of SDS (sodium dodecyl sulfate)
are taken in a beaker, and then they were dissolved by continuous magnetic stirring. In continuous
magnetic stirring two solutions were mixed until a homogenous solution is formed. Then 25ml of
1.5 M NaOH was added drop by drop to the above mixture. The color of the solution changes and
precipitate formation takes place. The obtained precipitate is filtered, dried, and calcined at 600 oC
for 3 hours to get well-crystallized copper ferrite. Then the obtained precipitate was washed with
acetone to make it free of impurities and dried in a hot air oven at 50 o C. finally grained to get a fine
powder CuFe2O4 using an agate motor.

75
 Experiment No. 6

Preparation of Conducting Polyaniline Thin film

by Electropolymerization

Electro polymerization of aniline: At first, before each scan the Pt electrode was prepared to
ensure a reproducible surface by polishing, rinsing with distilled water and then
electrochemically cleaned by cyclic voltammetry in 1 M of H 2SO4 solution until a
reproducible voltammogram was obtained. The electro polymerization of the aniline was
performed on a PGZ 301 Potentiostat/ Galvanostat with a three-electrode system, containing
a Pt wire (0.2 cm2) as the working electrode, a saturated calomel electrode (SCE) as a
reference electrode and glassy carbon as a counter electrode. All potentials recorded are
referred to this reference electrode. PANI films were prepared on the platinum working
electrode by the cyclic voltammetry in 1 M H2SO4 solution containing aniline at room
temperature (20°C). After the electro-polymerization of the aniline, the PANI electrode was
repeatedly washed with doubly distilled water.

76
 PART - B
Experiment - 1

Estimation of total hardness of water

Preparation of standard EDTA Solution -

Weigh accurately the given amount of disodium salt of EDTA crystals and transfer into a 100 ml
standard flask. Dissolve the crystals by adding 5 mL ammonia solution and then add distilled water
upto the mark and shake well for uniform concentration. This solution is taken in a 25 ml burette.

Weight of EDTA taken X 10

Molarity of EDTA = molecular weight of EDTA ( 372.24)

Estimation of total Hardness -

Burette : Standard EDTA Solution
Conical flask : 25mL hard water sample + 5 ml NH 4 OH–NH 4 Cl buffer soln (pH = 10)
Indicator : 2 drops of Eriochrome black – T
Colour Change : Wine red to clear blue

From the volume of EDTA consumed, calculate the total hardness of the given water
sample.

77
 Experiment - 2

Evaluation of Dissolved Oxygen by Winkler’s

method and hence assessment of quality of water.

Procedure:
Preparation of Sodium thiosulphate solution
A known weight of sodium thiosulphate crystals given in a weighing bottle is weighed and
transferred into a 100 ml standard flask. It is dissolved with water and then made upto the
mark. The solution is shaken thoroughly to obtain uniform concentration. The normality of
sodium thiosulphate solution is calculated.

Weight of Na2S2O3 x

Normality of Na2S2O3 salt solution, N Eq. wt.of Na2S2O3
Na2S2O3 = (248.18)

Estimation of DO:
Burette : Standard Na2S2O3 Solution
Conical flask : 100mL water sample + 3 ml MnSO4 + 3ml Alkaline KI solution
Indicator : 2 drops of Starch towards the endpoint
Colour Change : Blue to colourless

From the volume of Na2S2O3 consumed, calculate DO of the water sample.

78
 Experiment - 3

Determination of percentage of iron in corrosion

products

Preparation of Standard K2Cr2O7 solution –

Weigh accurately the given amount of K2Cr2O7 crystals and transfer into a 100 mL standard flask.
Dissolve the crystals by adding distilled water and make upto the mark and shake well for uniform
concentration.This solution is taken in a 25 mL burette.

Weight of K2Cr2 O7 X 10
Normality of K2Cr2O7 =
equivalent weight of dichromate (49.03)

Estimation of Iron in Haematite -

Burette : Standard K2Cr2O7 Solution
Conical Flask : 25 mL haematite ore solution + 1 TT of conc. HCl, boil +
SnCl2 (to the hot solution) drop wise till colourless.
Cool and add 5 mL HgCl2 in one lot+ 2 TT of distilled water
Indicator : K3 [Fe(CN)6] - [External Indicator]
End point : Indicator drop fails to develop blue ppt or green colour with the test solution
drop
From the volume of K2 Cr2O7 consumed, calculate the percentage of iron in the given haematite solution.

79
 Experiment 4

Estimation of percentage of Copper in brass

alloy by iodometric method
Preparation of brass solution:
Weigh accurately brass sample into a clean conical flask/beaker. Add 1ml of conc HNO 3,
when brass completely dissolves add 1g of urea and 1 test tubes of distilled water and boil
the solution till all the oxides of nitrogen are completely expelled and cool the solution.
Transfer the entire solution into 100ml standard flask and dilute upto the mark with
distilled water.

Estimation of Copper in brass:

Estimation of Copper in Brass:

Burette : Standard Na2S2O3 Solution
25mL brass solution + NH4 OH till blue colour + dil. Acetic acid +
Conical flask : 5 ml 10% KI
Indicator : 2 drops of Starch towards end piont
Colour Change : Blue to milky white ppt

From the volume of Na2S2O3 consumed, calculate the amount Copper present in brass
sample.

80
 Experiment 5

Construction of Daniel Cell

Procedure: Prepare 1M of copper sulfate CuSO4 solution and 1M of zinc sulfate ZnSO4
solution. Connect the solutions with a piece of fabric treated with 1M KCl solution. Connect
a zinc Zn wire to the black crocodile clip, and a copper Cu wire to the red crocodile clip.
Immerse the metal wires in the vials: put the Zn wire in the vial of ZnSO 4 solution and the
Cu wire in the vial of CuSO4 solution. Connect the two ends to the ammeter for detection of
current or connect the two ends to a led.

 A salt bridge minimizes or eliminates the liquid junction potential.

81
 Experiment 6

Faraday’s law verification by using

Electrodeposition of Cu/Ni/Zn on stainless steel.

Prepare a 15 ml of 0.2 M Na2SO4 solution in a clean cell/beaker. To this add the weight
corresponding to 0.2 M CuSO4 dissolve it completely. The stainless-steel plates thoroughly
cleaned and washed is used for the electrodeposition. Both anode and cathodes are SS substrate.
The cathode is cleaned, dried, weighed, and then inserted in the cell. A current I 1 is passed for a
time t. The current is measured by the ammeter. The cathode is taken out, washed, dried, and
weighed again. Hence the mass m1 of the substance deposited is obtained.

Plot the graph of current vs potential

82
 ENGINEERING CHEMISTRY LABORATORY
Model - Viva-Voce
Volumetric Analysis

1. What is Volumetric Analysis or titrations?

The amount of substance present in solution can be determined by a procedure using the
measurement of volumes of solutions. This experiment is referred to as titration.

2. Define Normality (N)

It is the number of gram equivalent weight of the solute dissolved in one litre of the
solution.

3. Define Molarity (M)

It is the number of gram molecular weight of the solute dissolved in one litre of the
solution.

4. Define Molality (m)

It is the number of gram molecular weight of the solute dissolved in one Kg of the
solvent.

5. Define Basicity of an acid

The number of replaceable hydrogen present in one molecule of an acid is called basicity
of the acid.
Basicity of HCl, HNO3, CH3COOH is one
Basicity of H2SO4, H2C2O4 (oxalic acid) is two
Basicity of H3PO4 is three

6. Define equivalent weight of an acid

Molecular weight
Equivalent weight of an acid =
Basicity of the acid
7. Define Acidity of a base
The number of replaceable hydroxyl groups present in one molecule of the base
NaOH, KOH, NH4OH acidity = 1
Ca(OH)2, Ba(OH)2, Mg (OH)2 acidity = 2
Al(OH)3, acidity = 3

8. Define Equivalent Weight of a base

Molecular weight
Equivalent weight of a base = Acidity of the base

9. How mass of substance in dm3 of solution related with Normality and Gram
equivalent weight?
Mass of substance in dm3 of solution = Normality × gram equivalent weight in dm3 of the
solution.

10. What are indicators?

Indicators are the substances which indicate the completion (or end point) of a chemical
reaction by change of colour.
83
11. Define equivalent weight of an oxidizing agent
The equivalent weight of an oxidizing agent is that mass of the oxidizing agent which contain
8 parts by weight of available oxygen for oxidation.

12. Define equivalent weight of reducing agent

The number of parts by mass of the reducing agent, which reacts with one equivalent
weight of an oxidizing agent.

13. What is a standard solution?

A standard solution of a substance is a solution, which contains a known mass of the
substance dissolved in a known volume of the solution.

14. Which types of indicators are used in volumetric analysis?

Internal indicators - Phenolphthalein, starch
External indicators - Potassium ferricyanide
Self indicator - Potassium Permanganate

Part A
Potentiometric Sensor
1. What is potentiometric titration?
The estimation of substances in solution by measurement of emf is known as
potentiometric titration.

2. What are the electrodes used in the determination of FAS potentiometrically?

Calomel electrode – reference electrode (acts as a cathode)
Platinum electrode in redox system – indicator electrode (acts as an anode)

3. Give the principle of potentiometric titration?

In a potentiometric titration the end-point of the titration is determined by following the
variation of the potential difference between indicator electrode and reference electrode
immersed in to the solution to be examined (analyte) as a function of the quantity of titrant
added. At the end point, sharp increase in potential is observed.

4. What is an indicator electrode?

The electrode whose potential is dependent upon the concentration of the ion to
be determined is termed as indicator electrode.

5. What is the reaction that occurs between FAS and K2Cr2O7 in

potentiometric titration?
Acidified K2Cr2O7 oxidises ferrous sulphate to ferric sulphate and itself gets reduced
to chromic sulphate.
6FeSO + 7H SO + K Cr O → 3Fe (SO ) + KSO + Cr (SO ) + 7H O
4 2 4 2 2 7 2 4 3 2 4 2 4 3 2

6. What are the advantages of potentiometric titrations?

1) Turbid, coloured solutions can be titrated.
2) Mixture of solutions or very dilute solutions can be titrated.
3) The results are more accurate and reproducible.
84
 4) Titrations can be carried out without indicators.

Colorimetric determination of copper

1. What is colorimetry?
Chemical analysis through measurements of absorption of light radiation in the visible region
of the spectrum (400-760 nm) with respect to a known concentration of the substance is
known as colorimetry.

2. Why filters are used in colorimetric experiments?

The filters are used in colorimetric experiments for selecting desired spectral region.

3. What is wave length?

The distance between any two successive peaks or troughs of waves is called wave length.
It is represented by ë.

4. What is frequency?
It is the number of waves passing through a point per second. It is represented by í.

5. State Beer’s Law?

The intensity of transmitted beam of a monochromatic light decreases exponentially as the
concentration of the absorbing medium increase arithmetically.

6. State Lambert’s Law?

The intensity of transmitted light decreases exponentially as the thickness of the absorbing
medium increase arithmetically

7. State Beer-Lambert’s law?

The intensity of transmitted beam of a monochromatic light decreases exponentially as the
concentration and thickness of the absorbing medium increase arithmetically.
OR
It states that the absorbance of a monochromatic light is directly proportional to the
path length, t and concentration, c of the light absorbing analyte.

8. What is calibration curve?

It is the graph of optical density (absorbance) versus concentration of standard solutions
using which, the concentration of analyte can be estimated.

9. What is meant by transmittance?

It is the ratio of amount of light transmitted (It) to the total amount of light absorbed (I0)

10. What is absorbance or optical density?

Reciprocal of transmittance, is called absorbance or optical density.
A = log I0 = log 1 = –log T
It T
11. Can we use cuvettes of different path lengths for absorbance measurements?
No, since absorbance varies with path length, it is recommended to use fixed path length
for the entire experiment.

85
 12. Why is ammonia added?
Ammonia is added to get cuprammonium sulphate [Cu(NH3)4SO4] (intense blue complex).

13. What is blank solution? Why it is used?

A blank solution is the one comprises all the reagents except the analyte. It used in order to
nullify the adsorbance due to the impurities present.

14. Why copper estimation is carried out at 620 nm?

The estimation of copper is carried out at 620 nm because the complex shows maximum
absorbance at 620 nm.

15. What are the criteria for a satisfactory colorimetric analysis?

1. Solute must not undergo solvation, association, dissociation, precipitation or hydrolysis.
2. The colour produced should be sufficiently stable during analysis.
3. Beer-Lambert’s law holds good for dilute solutions and deviates at higher concentrations.

Conductometric estimation of Acid Mixture

1. State Ohm’s law
Ohm’s law states that the current, I (ampere) flowing in a conductor is directly
proportional to the applied electromotive force, E (volt) and inversely proportional to the
resistance, R (ohm) of the conductor.

2. What is specific conductivity?

It is the conductance of an electrolyte solution, placed between two parallel electrodes 1
cm. apart and area of cross section 1cm2.

3. What is conductometric titration?

Determination of end point of a titration by means of conductance measurements is known
as conductometric titration.

4. What is the principle involved in conductometric titration?

In conductometric titration, end-point of the titration is determined by following the
variation of the conductance of an analyte as a function of the quantity of titrant added. The
end point is determined graphically by plotting conductance versus quantity of titrant.

5. Conductance decreases initially on adding NaOH to the acid mixture, why?

The strong acid, HCl undergo neutralization first and conductance decreases because of
replacement of highly mobile H+ ions by the less mobile Na+ ions.

6. Conductance increases marginally after the neutralization of HCl, why?

Acetic acid undergo neutralization and forms its salt, sodium acetate, which is relatively
stronger electrolyte and shows marginal increase in conductance.

7. After neutralization of acetic acid, conductance increases significantly, why?

Since, neither of the acids is left over at this stage, the added NaOH contributes
significantly towards conductance due to highly mobile OH- ions.

86
 8. What are the advantages of conductometric titrations?
1. Accurate results with dilute solutions
2. Colored or turbid solutions can be titrated
3. Acid / base mixtures can be titrated
4. Useful for titrations in which there is no suitable indicator is available

Determination of pka value of a weak acid

1. What is Ka?
Ka is dissociation constant of a weak acid. e.g. dissociation of acetic acid,
CH3COOH + H2O H3O+ + CH3COO–

K =
a(CH3COOH)

2. What is pKa of weak acid?

PKa of a weak acid is the negative logarithm to base 10 of its dissociation
constant. pKa = – log10 Ka

3. How are pH and pKa related?

pH and pKa are related by Henderson – Hasselbalch equation and is given

by pH = pKa + log

4. Which electrodes are used in the measurement of pH?

Glass electrode (indicator electrode) - Calomel electrode (reference electrode) assembly is
used in the measurement of pH.

5. Under which condition/s, pH is equal to

pKa? At half equivalence, [salt] = [acid]
According to Henderson – Hasselbalch equation, pH = pKa + log

Here log =0

Hence, pH = pK a

6. Why pH increases suddenly after the equivalence point?

At the equivalence point, weak acid gets neutralized completely; further, addition of strong
base, NaOH results in sharp increase in pH due to introduction of OH - ions.

11. Comment on the relation between pKa and acid

strength.
Higher the pKa, weaker the acid and vice-versa.

12. Define pH ?
87
 It is the negative logarithm to base 10 of hydrogen ion concentration.
pH = –log10 [H+]

Preparation of semiconducting nanomaterials and their

characterisation
1.What is band gap?
Energy gap between HOMO and LUMO

2.Give some examples for semiconductors

Si, Cu2O, ZnO

3.What are nanomaterials?

The materials which in the size range of 1 to 100 nm

4.What is the range of UV-Vis wavelength?

EMR in the range of 200 to 800 nm

5.Why absorbance occur in coloured materials?

Due to the electronic excitation in the UV and Visible range

Preparation of Conducting polyaniline thin film by

electro polymerization.

1.What is conducting polymers

Materials which can allow electrons to flow

2.What type of conductivity occur in polyaniline

Electronic conductivity

3.What surface is required to do electropolymerisation

Any conductive metal or semiconductive substrates

4.What is the electrochemical process occur at anode

Oxidation of aniline to polyaniline

5.What is the reaction occur at cathode

Reduction of proton to hydroge
88
 Part B
Determination of Total Hardness of water

1. What is hard water?

Hardness in water is that characteristic, which prevents the lathering of soap and also
produces scale in boilers.

2. How is hardness of water caused?

Hardness of water is caused by the presence of certain salts of calcium, magnesium and
other heavy metals dissolved in water.

3. Mention the compounds responsible for temporary hardness.

Temporary hardness is caused by the presence of dissolved bicarbonates of calcium,
magnesium and other heavy metals.

4. How is temporary hardness removed?

Temporary hardness of water can be removed by boiling water. While boiling bicarbonates
decompose to give carbonates.
Ca(HCO3 )2 → CaCO3 + H2O + CO2

5. Which compounds impart permanent hardness to water?

Permanent hardness is caused by the presence of chlorides and sulphates of calcium and
magnesium in water.

6. How do you express the total hardness of water?

The concentrations of hardness causing ions are usually expressed in terms of equivalent
amount of CaCO3.

7. How do you express the total hardness of water?

Parts per million (PPM) is the parts of CaCO3 equivalent hardness per 106 parts of
water. i.e., 1 PPM = 1 part of CaCO3 equivalent hardness in 106 parts of water.

8. What is EDTA ? Write the structural formula of EDTA.

EDTA (Ethylene Diamine Tetra Acetic acid) is a complexing agent (Ligand) used in
complexometric titrations.

9. What is buffer solution? What is the role of buffer solution?

Buffer solution is generally made up of weak acid and its salt or weak base & its salt and
possess definite pH value. It resist the alteration in pH of a solution due to addition of small
quantity of an acid or a base.

89
10. Why ammonium chloride – ammonium hydroxide buffer is used in the determination
of total hardness of water?
NH4Cl –NH4OH buffer is used to maintain pH value of about 10 and helps EDTA to form
stable complex with Ca2+ and Mg 2+ ions.

11. Which is the indicator used in the determination of total hardness of water? Why
indicator show wine red colour along with hard water?
Erichrome black–T indicator is used in this experiment. Indicator combines with Ca 2+ and
Mg2+ ions present in hard water and forms wine red coloured complex.

12. What is the end point in the determination of total hardness of water?
Change of colour from wine red to clear blue mark the end of titration.

13. Why is disodium salt of EDTA preferred to EDTA?

EDTA is a weak acid and sparingly soluble in water due to partial dissociation. Therefore
disodium salt of EDTA is preferred.

14. Ammonia solution is added during the preparation of EDTA solution, why?
Ammonia solution is added to increase the rate of dissolution of EDTA salt.

15. In EDTA titrations, near the end point, titration has to be carried out slowly, why?
The titrations involving EDTA are carried out slowly towards the end point, because the
rate of formation of the metal complex of EDTA is very slow.

16. What is the significance of hardness determination?

1. In determining the suitability of water for domestic and industrial applications.
2. In water softening process.

Determination percentage corrosion products.

1. What is the main constituent of haematite?

The main constituent of haematite ore are ferric oxide (Fe2O3) and silica (SiO2)

2. What is the oxidation state of iron in haematite?

The oxidation state of iron in haematite ore is Fe3+ (Ferric)

3. What is the role of stannous chloride in the determination of iron in haematite?

Stannous chloride acts as a reducing agent, it reduces Fe3+ (ferric) to Fe2+(ferrous).
2FeCl3 + SnCl2 → 2 FeCl2 + SnCl4

4. What is the role of mercuric chloride in this determination?

Addition of mercuric chloride removes excess of stannous chloride. It reacts with
stannous chloride to form a silky white precipitate of mercurous chloride.
SnCl2 + 2HgCl2 → Hg2Cl2 + SnCl4

5. Name the indicator used in this experiment.

Potassium ferricyanide [K3 Fe(CN)6] is used as an external indicator.
90
 6. What is the colour of [K3Fe(CN)6] with ferrous ion?
Potassium Ferricyanide produces an intense deep blue colour with ferrous iron due to the
formation of ferrous ferric cyanide complex.

7. Why is potassium ferrocyanide not used as an indicator in the estimation of iron?

Potassium ferrocyanide cannot be used as a indicator in the estimation because,
ferrocyanide does not react with ferrous ions.

8. Why does the colour of the indicator drop remain the same at the end point?
Only ferrous ions form intense deep blue colour complex with potassium ferricyanide. At the
end point, ferrous ions are not available because they get oxidized to ferric ions by K 2Cr2O7
and fails to produce change in colour for indicator.

9. Why is potassium ferricyanide not used as an internal indicator in the analysis

of haematite?
Potassium ferricyanide combines irreversibly with ferrous ion to form a deep blue ferrous
ferricyanide complex (Turnbiull’s blue). These ferrous ions involved in complex formation
are not available for reaction with potassium dichromate.
3Fe2+ + 2K3 [Fe (CN)6] → Fe3 [Fe(CN)6]2 + 6K+

10. What is the reaction that occurs during the titration?

Acidified potassium dichromate oxdises ferrous ions present in the haematite solution to
ferric ions and itself gets reduced to chromic ions.
6Fe2+ + Cr2O72- + 14 H+ → 6 Fe3++ 2Cr3+ + 7H2O

Evaluation of Dissolved Oxygen by Winkler’s method and hence

assessment of quality of water.

1.Name few oxidation reagent

K2Cr2O7, KMnO4

2. What is role of starch

It act as indicator

3. How Mn(OH)2is converted to MnO(OH)2

By oxidation with dissolved oxygen
4.Why KI is used in this experiment
To generate I2 through oxidation
5. How dissolved oxygen is important affect corrosion and living organisms
Highly concentration – more corrosion, less concentration – living organisms will be
affected

91
 Estimation of copper in brass alloy by iodometric method
1. What are the constituents of brass?
Brass is an alloy of copper. The chief constituents of brass are copper and Zinc
(Cu: 50-90%, Zn: 20-40%, tin, lead and Iron )
2. How is brass solution prepared?
Brass solution is prepared by dissolving the brass sample(brass foil) in
minimum amount of concentrated nitric acid
3. What is the purpose of adding urea to the brass solution?
Urea is added to expel to oxides of nitrogen from solution
4. Excess of nitric has to be removed before titration, why?
Presence of excess nitric acid, oxidizes iodine to iodic acid and also
decomposes sodium thiosulphate during titration and thereby introduces
error in burette reading.
5. Ammonium hydroxide is added to the brass solution, why?
Ammonium hydroxide is added to neutralize excess of nitric acid present in
the brass solution.
6. Why excess acetic acid is added to the brass solution?
Acetic acid is added to neutralize the excess of ammonium hydroxide and
slight excess of this acid makes the solution acedic and ensures 100%
availability of copper(II) ions.
Note: If, the added acetic acid is insufficient, the solution will be basic, then few
copper(II) ions will exists as [ Cu(NH3)4SO4] complex and are not available to react with
potassium iodide and introduce error in burette reading.
7. Why potassium iodide is added to the brass solution?
Addition of KI reduces cupric ions to cuprous ions, which precipitate out as
cuprous iodide and liberates Iodine equivalent to the amount of copper
present.
8. On addition of KI, brass solution colour turns from blue to reddish
yellow, why?
Liberated I3+2 combines with Iodide ions and forms soluble reddish yellow
coloured I ions.
9. Why starch is preferred for iodometric titrations? Why it is added near
the end point?
Starch combines with iodine to form intense blue coloured complex and
helps in identifiying the availability of iodine during titration, starch is
added near the end point when the concentration of iodine is low, if we add
starch in earlier stage of the titration i.e (high iodine concentration), water
insoluble starch-iodine complex is formed and which makes the detection
of end point difficult.
10. How is liberated Iodine is estimated?
The amount of iodine liberated is estimated by titrating against standard
sodium thiosulphate solution using starch as an indicator.

92
 Construction of Daniel cell
1.What is the anode in Daniel cell
Zinc

2.What is the cathode in Daniel cell

Copper

3.What is the anodic reaction in Daniel cell

Oxidation of Zinc

4.What is the cathodic reaction in Daniel cell

Reduction of copper

5. What is the role of salt bridge

To prevent the cross over of Copper ion and the reduction at anode

Faraday’s law verification by using Electrodeposition of Cu/Ni/Zn on

stainless steel

1.What is the relation between the weight of deposit and current passed
Amount of current passed is directly proportional to the weight of the maerials

2.What is the reaction occur at cathode

Electrochemical reduction of copper ions to copper metal

3.Why supporting electrolyte is used in the electroyte preparation

To improve the conductivity of electrolyte

4.What surface is required to do electrodeposition

Any conductive metal or semiconductive substrates

5. What is the simultaneous reaction occurs at anode

Oxidation of water to relearse oxygen and proton

93
 Flame Photometric Estimation of Sodium.

1. What is meant by atomic emission?

When a neutral atom is excited to higher energy state, it comes back to the lower energy state
by emitting the excess energy in the form of radiation (photons). This emission of radiation
by an atom is called an atomic emission.

2. What is flame photometry?

It is an analytical technique of measuring the intensity of emitted radiation by an excited
atom under test.

3. What are alkali and alkaline earth metals?

Li, Na, K,Rb,Cs etc, are alkali metals.
Be, Mg, Ca, Sr etc, are alkaline earth metals.
Alkali and alkaline earth metals together called S-block elements and they belong to
group-I and group-II respectively of periodic table.

4. What are various events that occur when a solution containing metal ions
automised through a flame?
Following steps explain the sequence of events that occur during the experiment.
a) Liquid sample containing element is subjected to flame
b) Formation of liquid droplets
c) Evaporation of droplets resulting in the formation of residue
d) Decomposition of residue into neutral atoms
e) Formation of excited atoms and emission of radiation during deexcitation
f) Measurement of wavelength and intensity of emitted radiation by flame photometry

5. What are different components of Flame photometer?

Pressure regulator, flow meter, automiser, burner, optical system, photosensitive
detector, and output recorder.

6. Why the analysis of Sodium is advantageous in Flame photometry?

Sodium being an alkali metal and also electropositive in nature can be easily excited and
hence ease of analysis.

7. What is the role of filter in Flame photometry?

A suitable filter is used to choose desired wavelength from the flame and allowed into
detector, thereby detection of the element becomes easy. For this purpose filter is placed
between the flame and detector.

8. What are the errors that can occur in Flame photometry?

The following errors are encountered during the experiment.
a) Spectral interference b) Ionisation interference
c) Cation-anion interference d) Oxide formation interference

9. What are the factors that influence this experiment?

a) Viscosity b) Presence of acids c) Presence of other metals.
10. Name the fuel and oxidant used in this experiment.
Hydrogen / propane is the fuel and oxygen is the oxidant
94