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INTRODUCTION

t the end of twentieth century, science has raised human civilization up to highest
peak. Instruments have brought for mankind such comforts as a man can never
dream of even in a fairly land. This sessional course chem-352 is entitled as
Instrumental Methods of Analysis. The main object of this course is to be introduced with
different types of instruments used in chemical analysis.
In order to optimum use of the techniques that have been developed in analytical chemistry,
scientists should know what is not available to them through analytical chemistry and, most
as important what is not available to them. Knowledge of analytical chemistry is highly
desirable in all people who use analytical data to arrive at a decision in their work.
Accurate result can be obtained by the use of these instruments other than the classical
methods. At the same time, the consumption of time is much smaller than the classical
method. Some instruments that have the recorder and computer facilities have created a new
area in analytical chemistry, so knowledge for operations and handling of those instruments a
badly needed and this course is very much important from this point of view.
Analytical chemistry is the science of obtaining, processing, and communicating information
about the composition and structure of matter. In other words, it is the art and science of
determining what matter is and how much of it exists.

Analytical chemists perform qualitative and quantitative analysis; use the science of
sampling, defining, isolating, concentrating, and preserving samples; set error limits; validate
and verify results through calibration and standardization; perform separations based on
differential chemical properties; create new ways to make measurements; interpret data in
proper context; and communicate results. They use their knowledge of chemistry,
instrumentation, computers, and statistics to solve problems in almost all areas of chemistry.
For example, their measurements are used to assure compliance with environmental and other
regulations; to assure the safety and quality of food, pharmaceuticals, and water; to support
the legal process; to help physicians diagnose disease; and to provide chemical measurements
essential to trade and commerce.


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HISTORICAL BACKGROUND OF ANALYTICAL CHEMISTRY:

uch of early chemistry (1661~1900AD) was analytical chemistry since the
questions of what elements and chemicals were present in the world around us
and what are their fundamental natures is very much in the realm of analytical
chemistry. There was also significant early progress in synthesis and theory which of course
are not analytical chemistry. During this period significant analytical contributions to
chemistry include the development of systematic elemental analysis by Justus von Liebig and
systematized organic analysis based on the specific reactions of functional groups. The first
instrumental analysis was flame emissive spectrometry developed by Robert Bunsen and
Gustav Kirchhoff who discovered Rb and Cs in 1860. Most of the major developments in
analytical chemistry take place after 1900. During this period instrumental analysis becomes
progressively dominant in the field. In particular many of the basic spectroscopic and
spectrometric techniques were discovered in the early 20th century and refined in the late
20th century. The separation sciences follow a similar time line of development and also
become increasingly transformed into high performance instruments. In the 1970's many of
these techniques began to be used together to achieve a complete characterization of samples.
Starting in approximately the 1970's into the present day analytical chemistry has
progressively become more inclusive of biological questions (bio analytical chemistry),
whereas it had previously been largely focused on inorganic or small organic molecules. The
late 20th century also saw an expansion of the application of analytical chemistry from
somewhat academic chemical questions to forensic, environmental, industrial and medical
questions.
The chronological development in the sector of Analytical Chemistry and instrumental
methods are given below for last five decades:

1950's - This was a pretty dull field. pH meters and single wavelength spectrophotometers,
and electrochemical techniques were used. Lots of titrations, gravimetric analysis. Some
important work were done to lay the theoretical groundwork. Data was primarily one
dimensional. Experiment ====> Number

1960's - Invention of Gas Chromatography and Atomic Absorption spectrophotometry make
trace analysis possible and reasonably easy. Analysis of ppm and ppb levels of metals and
organics in the environment begins. Text book triples in size. Scanning spectrophotometers
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become common. Thus data representations were now two dimensional. Experiment ===>
Graph

1970's - Invention of liquid chromatography and the common use of mass spectrometry for
analytical chemistry begins. GC and AA reach new limits of sensitivity allowing part per
trillion trace analysis. We begin to find virtually everything almost everywhere. Surface
analysis of thin layers becomes common. Analytical chemistry is brought to bear on problems
of the environment, energy, and biological and physiological analysis.

1980's - Continued strides in trace analysis and in identification of trace components through
interfaced (hyphenated) methods e.g. GC-MS, LC-MS, GC-IR, etc. Computers appear to
control instruments, manipulate data, and run experiments Robots appear to conduct
complete analytical schemes Multidimensional data representations add new dimensions to
data interpretation It becomes possible to detect single atoms of many substances. Three
dimensional data presentations become important (MS-MS and 2D NMR). Experiment ===>
3D Graphic

1990S - Detection limits continue to drop to the point that one can begin to discuss detection
of single atoms and molecules. Sample preparation is also a major focus as old, time
consuming methods of solvent extraction are replaced with fast, automated procedures.
Multi-channel analysis becomes the major thrust.













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INTRODUCTION OF ANALYTICAL CHEMISTRY

nalytical chemistry is the science of making quantitative measurements. In
practice, quantifying an analyte in a complex sample becomes an exercise in
problem solving, to be efficient and effective; an analytical chemist must know
the tools that are available to tackle a wide variety of problems. For this reason, analytical
chemistry courses are often structured along the lines of the analytical methods (the tools-of
the-trade).
Understanding the analytical toolbox requires a scientist to understand the basic principles of
the analytical techniques. With a fundamental understanding of analytical methods, a scientist
faced with a difficult analytical problem can apply the most appropriate technique(s). A
fundamental understanding also makes it easier to identify when a particular problem cannot
be solved by traditional methods, and goes an analyst the knowledge that is needed to
develop creative approaches or new analytical methods.

Analytical chemistry is divided into two parts, qualitative analysis and quantitative analysis.
Qualitative analysis shows what elements (or ions) a given substance contains. The
qualitative analysis is the detection and identification of the constituents of a compound or
mixture of compounds or elements whereas determination of percentage or molecular
composition of a sample is the province of quantitative analysis. The aim of quantitative
analysis is determination of the quantitative contents of individual elements or compounds
present in a substance.

Analytical Chemistry seeks ever improved means of measuring the chemical composition of
natural and artificial materials. The techniques of this science are used to identify the
substances which may be present in a material and to determine the exact amounts of the
identified substances.

Analytical chemists work to improve the reliability of existing techniques to meet the
demands for better chemical measurements which arise constantly in our society. They adapt
proven methodologies to new kinds of materials or to answer new questions about their
composition. They carry out research to discover completely new principles of measurement
and are at the forefront of the utilization of major discoveries such as lasers and microchip
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devices for practical purposes. They make important contributions to many other fields as
diverse as forensic chemistry, archaeology, and space science. As the emblem above points
out, analytical chemistry serves the needs of many fields.

Most of the materials that occur on Earth, such as wood, coal, minerals, or air, are mixtures of
many different and distinct chemical substances. Each pure chemical substance (e.g., oxygen,
iron, or water) has a characteristic set of properties that gives it its chemical identity. Iron, for
example, is a common silver-white metal that melts at 1,535 C, is very malleable, and readily
combines with oxygen to form the common substances hematite and magnetite. The detection
of iron in a mixture of metals, or in a compound such as magnetite, is a branch of analytical
chemistry called qualitative analysis.

Measurement of the actual amount of a certain substance in a compound or mixture is termed
quantitative analysis. Quantitative analytic measurement has determined, for instance, that
iron makes up 72.3 percent, by mass, of magnetite, the mineral commonly seen as black sand
along beaches and stream banks. Over the years, chemists have discovered chemical reactions
that indicate the presence of such elemental substances by the production of easily visible and
identifiable products. Iron can be detected by chemical means if it is present in a sample to an
amount of 1 part per million or greater. Some very simple qualitative tests reveal the presence
of specific chemical elements in even smaller amounts. Such analytic tests have allowed
chemists to identify the types and amounts of impurities in various substances and to
determine the properties of very pure materials. Substances used in common laboratory
experiments generally have impurity levels of less than 0.1 percent. For special applications,
one can purchase chemicals that have impurities totaling less than 0.001 percent. The
identification of pure substances and the analysis of chemical mixtures enable all other
chemical disciplines to flourish.


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IMPORTANCE OF ANALYTICAL CHEMISTRY

he importance of analytical chemistry has never been greater than it is today. The
demand in modern societies for a variety of safe foods, affordable consumer goods,
abundant energy, and labour-saving technologies places a great burden on the
environment. All chemical manufacturing produces waste products in addition to the desired
substances, and waste disposal has not always been carried out carefully. Disruption of the
environment has occurred since the dawn of civilization, and pollution problems have
increased with the growth of global population. The techniques of analytical chemistry are
relied on heavily to maintain a benign environment. The undesirable substances in water, air,
soil, and food must be identified, their point of origin fixed, and safe, economical methods for
their removal or neutralization developed. Once the amount of a pollutant deemed to be
hazardous has been assessed, it becomes important to detect harmful substances at
concentrations well below the danger level. Analytical chemists seek to develop increasingly
accurate and sensitive techniques and instruments.








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CLASSIFICATION OF ANALYICAL CHEMISTRY:

raditionally, analytical chemistry has been split into two main types, qualitative and
quantitative:
1. Qualitative
Qualitative inorganic analysis seeks to establish the presence of a given element or inorganic
compound in a sample.
Qualitative organic analysis seeks to establish the presence of a given functional group or
organic compound in a sample.
2. Quantitative
Quantitative analysis seeks to establish the amount of a given element or compound in a
sample.
Most modern analytical chemistry is categorized by two different approaches such as
analytical targets or analytical methods. Analytical Chemistry (journal) reviews two different
approaches alternatively in the issue 12 of each year.
By Analytical Targets
Bio analytical chemistry
Material analysis
Chemical analysis
Environmental analysis
Forensics
By Analytical Methods
Spectroscopy
Mass Spectrometry
Chromatography & Electrophoresis
Crystallography
Microscopy
Electrochemistry


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DIFFERENT METHODS AND TECHNIQUES OF ANALYSIS:

here are many techniques available for the analysis of materials; however, they are
all based on the material's interaction with energy. This interaction permits the
creation of a signal that is subsequently detected and processed for its information
content.
The types of analysis techniques conform with the various types of energy:
Spectroscopic Analysis
Spectroscopy measures the interaction of the material with electromagnetic radiation.
Electrochemical Analysis
Electrochemistry measures the interaction of the material with an electric field.
Mass Analysis
Gravimetric analysis measures the interaction of the material and a gravitational field.
Mass spectrometry measures the interaction of charged materials and electric and magnetic
fields.
Thermal Analysis
Calorimetry and thermo gravimetric analysis measure the interaction of a material and heat.
The detection and analysis of multiple simultaneous signals is the subject of cutting-edge
research in analytical chemistry. In order to utilize the techniques available currently,
complex material mixtures must be separated into simpler samples for individual analysis.
Separation Science
Separation processes are used to decrease the complexity of material mixtures. The most
utilized separation method is chromatography.
After the material is sufficiently isolated and a signal is generated, the signal must be detected
and interpreted.
Data Acquisition and Analysis
Specific data acquisition and data analysis techniques are required to obtain the information
produced by the various techniques for material analysis named above. Research and
development in this area of analytical chemistry involves interdisciplinary efforts in physics,
electronics, optics, statistics and computer science.



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INSTRUMENTAL METHOD OF ANALYSIS:

he recent rapid advances in our knowledge of the physical world parallel a similar
rapid advance in the science of analytical methods. However, neither the balance
nor burette, which provided most of our analytical measurements in the 1940's have
been relegated to the museum - both are still indispensable in any chemical laboratory and
often are the ultimate weapons in calibrating a fancier instrumental method. They were good
enough to allow Nobel laureate T.W. Richards to prove the existence of isotopes by very
precise determinations of the atomic weight of lead from various sources. But now mass
spectrometry permits atomic weights to be determined more precisely and with a fraction of
the efforts. Similarly, the American Petroleum Institute invested many thousands of man-
hours in attempting to isolate the hundreds of components in petroleum and gasoline by
tedious fractional distillations. Today one man can obtain the same results in a few hours with
a gas chromatograph.
An instrument for chemical analysis does not generate quantitative data but converts
chemical information to a more readily observable form. Sensitivity of the instrument is
increased by amplification of the original signal or its transuded form. Since amplification is
commonly accomplished electronically, instrumental analysis has developed tremendously
now a days with the advance of electronics. These methods are specially applied in industrial
laboratories where economy in time and manpower is gained by their use in routine work.

SPECIFIC TECHNOLOGIES AND INSTRUMENTATION

Atomic absorption spectroscopy (AAS)
Atomic fluorescence spectroscopy (AFS)
Alpha particle X-ray spectrometer (APXS)
Capillary electrophoresis (CE)
Chromatography
Cyclic Voltammetry (CV)
Differential scanning calorimetry (DSC)
Electron paramagnetic resonance (EPR)
Electron spin resonance (ESR)
Field flow fractionation (FFF)
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Ion Microprobe (IM)
Instrumental mass fractionation (IMF)
Ion selective electrode (ISE) eg. determination of pH
Laser Induced Breakdown Spectroscopy (LIBS)
Mass spectrometry (MS)
Mossbauer spectroscopy
Nuclear magnetic resonance (NMR)
Particle induced X-ray emission spectroscopy (PIXE)
Raman spectroscopy
Refractive index
Resonance enhanced multi-photon ionization (REMPI)
Scanning transmission X-ray microscopy (STXM)
X-ray fluorescence spectroscopy (XRF)
X-ray microscopy (XRM)

CHOICE OF METHODS

Analytical methods rely on scrupulous attention to cleanliness, sample preparation, accuracy
and precision.
Many practitioners will keep all their glassware in acid to prevent contamination, samples
will be re-run many times over, and equipment will be washed in specially pure solvents.
A standard method for analysis of concentration involves the creation of a calibration curve.
If the concentration of element or compound in a sample is too high for the detection range of
the technique, it can simply be diluted in a pure solvent. If the amount in the sample is below
an instrument's range of measurement, the method of addition can be used. In this method a
known quantity of the element or compound under study is added, and the difference between
the concentration added, and the concentration observed is the amount actually in the sample.
Analytical chemistry research is largely driven by performance (sensitivity, selectivity,
robustness, linear range, accuracy, precision, and speed), and cost (purchase, operation,
training, time, and space).

So in short, A method to be appropriate for an analysis , it should contain following qualities:
Selective: The method should have to be operated in quite a broad range of concentration
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Specific: For analysis of the definite component, the method has to be appropraite
Sensitive: The method has to be sensitive enough to measure the amount of substances.
depending on the contration level seprate methods have to be applied for chemical analysis:

The respective analysis method appropriate for the concentration levels are:
gram- Gravimetric analysis
mg- Volumetric analysis
g- Spectrophotometric analysis
ng- Atomic absorption spectrophotometry(Newton Activation)
Upto the g level of concentration Electro analytical methods of analysis are applicable.
Such as:
Electrogravimetry
Potentiometry
Conductometry
pH metry
Polarography
Coulometry
In this course we performed the 1st electrical analysis method along with spectrophotometric
analysis to measure concentration or strength of chemical species.












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ANALYTICAL CHEMISTRY AND CHEMICAL ENGINEERING

any chemical engineers like the one mentioned are faced later in life with
analytical problems of which the solution is not to be found in reference books
but which can be solved by a rational and intelligent application of the
principle of the subject. Todays dynamic world expects that an engineer will make an
industry run better today than it was yesterday. But with no practical knowledge about
instruments, what contribution can be made?
New instruments are invented; olds are replaced by modern one. So every field in science and
technology is rapidly progressing. Classical method of analysis has also been replaced by
instrumental methods due to invention of different types of instruments such as, pH-meter,
conductometer etc. In modern laboratories computers are also introduced to coordinate these
different instruments with printers and recorder to give continuous results to the chemical
change. As a chemical engineer we are to keep with the modern continuously changing world
and so we are to know about the modern instruments. In this purpose, the course chem-302
was introduced to familiarize us with the modern instrumental methods of analysis and about
modern instrumentations used with it.
Five experiments were devised in this regard:
Determination of concentration of Fe2+ ion in a solution by Potentiometric Titration
Determination of the conductance of a strong and a weak acid in a acid mixture by
Conductometric Titration
Determination of concentration of HCl acid by pH metric Titration
Determination concentration of an unknown sample of Fe3+ solution by
Spectrophotometric method
Determination of percentage of Cu present in Brass by Electro-gravimetric method

.
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Determination of concentration of Fe2+ ion in a solution by
Potentiometric Titration

Experiment No: 01
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SUMMARY

hen a potentiometric titration is being performed, interest is focused upon
charges in the emf of an electrolytic cell as a titrant of precisely known
concentration is added to a solution of the analyte. The method can be applied
to all titrimetric reactions provided that the activity of a least one of the substances involved
can be followed by means of a suitable indicator electrode. In this topic, theory of
potentiometric titration, chemistry of the process, Experimental procedure, instrumentation,
advantages and limitation Result & Discussion involved in potentiometric titration of Iron (II)
solution with potassium dichromate solution are discussed in brief.

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THEORY

t is a titrimetric procedure in which potentiometric measurements are carried out in
order to fix the end point of the reaction. In this method, changes in electrode potential
are concerned rather than an accurate value for the electrode potential with a given
solution.
This potentiometric titration can be used in any electrode system out of which a change of
potential may be derived which follows the Nernst Equation. Nernst equation can be
explained as follows:

When a metal M is emerged in a solution containing its own ion M
+
then an electrode
potential is established the value of which is given by the Nernst equation,
+
+ =
n
M
a
nF
RT
E E ln
0

where, E
0
is constant, the standard electrode potential of the metal. E can be measured by
combining the electrode with a reference electrode (commonly a standard calomel electrode)
and measuring the emf of the resultant cell.

Reproducible equilibrium cell emf is of no concern here. Requirements for reference
electrodes are greatly relaxed and it is only necessary that the response of one of the two
electrodes of a pair be substantially greater or faster than that of the other. The cell emf can
be measured at zero current (null balance) or with a constant electrolysis current flowing
through the cell.

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Chemicals:
K
2
Cr
2
O
7

H
2
SO
4

Fe
2+
solution
Distilled water

I nstrument:
Potentiometer
Beaker
Pipette
Burette
Potentiometer
FIGURE 04: Potentiometer used in the laboratory

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CHEMICAL REACTIONS

The cell reactions occurred is as follows:
Half-cell reactions:
(Left) volt 33 . 1 E ; O H 7 Cr 2 O Cr e 6 H 14
(Right) volt 77 . 0 E ; Fe e Fe
0
2
3 2
7 2
0
2 3
= + + +
= +
+ +
+ +

Overall cell reaction:
Cr
2
O
7
2-
+ 14 H
+
+ 6 Fe
2+
Cr
3+
+ 7 H
2
O + 6Fe
3+

Emf of the cell is given by,
E
cell
= E
left
- E
right
(oxidation potential)
It is to be noted that the contents of the beaker constitute one half-cell and the other half-cell
is the calomel reference electrode. During titration, both the redox complex is involved are in
the same half-cell. The dichromate reacts directly with the ferrous ion in the solution. The
reaction is so rapid that equilibrium dG = 0 and E = 0. The potential between redox couples is
zero.

E = 0 = E
Fe
2+
, Fe
3+
+ ECr
2
O
7
2-
, Cr
3+
, E = 0 = E
Fe
2+
, Fe
3+
+ Ecr
2
O
7
2-
, Cr
3+
,

The potential of the platinum electrode dipped into the solution is therefore given by the
reduction potential for the Fe couple or the reduction potential for the Cr
2
O
7
2-
couple,

E
pt
= E
Fe
3+
,
F
2+
+ Ecr
2
O
7
2-
. Cr
3+,
Ept = E
Fe
3+
, F
e
2+
+ E
cr2
O
7
2-
, Cr
3+

Since calomel electrode is used as a reference electrode, its potential has a constant value.
Electrode potential of platinum electrode is given by Nernsts equation,
] [Fe
] [Fe
ln
F
RT
E E
2
3
0
+
+
=
So Emf of the cell depends on the ratio Fe
3+
/Fe
2+
the titrant K
2
Cr
2
O
7
oxidizes
Fe
++
into
Fe
+++
.
So with every addition of the titrant the relative amount of
Fe
++
change and emf varies
gradually. At the end point emf changes abruptly.

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PROCEDURE

Procedure mentioned below is followed during performing this experiment.
A stock solution of iron (ferrous) having the strength 0.1(N) is prepared by dissolving
Mohrs salt.
From the stock solution 10ml sample is taken in a cleaned beaker and 20 ml of 6(N)
N2SO4 acid is added in this beaker.
It is then titrated with standard 0.1 N potassium dichromate solution.
The potential (emf) is recorded after addition of each 2ml of titrant, up to the addition
of 8ml of K2Cr2O7 solution. Then the potential is recorded after addition of each .1
ml of the titrant up to 13 ml of K2Cr2O7 solution.
The solution must be stirred during titration.

DETERMINATION OF END POINT

Several methods can be used to determinate end point for a potentiometer titration. The most
straightforward method involves a direct plot of potential (emf) versus volume reagent (here
K
2
Cr
2
0
7
) as in the figure in Appendix. The midpoint in the steeply rising portion of the curves
then estimated visually and taken as the midpoint.
A second approach is to calculate the change in emf per unit change in volume of reagent
(K
2
Cr
2
0
7
). A plot of this parameter as a function of average volume gives the end point at the
sharp maximum.
It is usually preferable to employ analytical or derivative methods of locating the endpoint,
these consists in plotting the first derivative curve or the second derivative curve. The first
derivative curve (AE/AV versus volume of reagent used) gives the maximum value at the
point of inflexion of the titration curve i.e. at the end point. The second derivative curve
(A
2
E/AV
2
versus volume of reagent used) is zero at the point where the slope of the first
derivative curve is maximum.


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OBSERVED AND CALCULATED DATA

Table No 01: Observed data for Potentionmetric titration.
Obs no. Volume of

(V)
(ml)
Generated
EMF
(E)
(Volt)

01 00 0.343
02 0.20 0.353 0.2 0.010 0.050
03 0.40 0.360 0.2 0.007 0.035 -0.015
04 0.60 0.365 0.2 0.005 0.025 -0.010
05 0.80 0.370 0.2 0.005 0.025 0.00
06 1.00 0.374 0.2 0.004 0.020 -0.005
07 1.20 0.378 0.2 0.004 0.020 0.00
08 1.40 0.380 0.2 0.002 0.010 -0.010
09 1.60 0.384 0.2 0.004 0.020 0.010
10 1.80 0.386 0.2 0.002 0.010 -0.010
11 2.00 0.389 0.2 0.003 0.015 0.005
12 2.20 0.392 0.2 0.003 0.015 0.00
13 2.40 0.395 0.2 0.003 0.015 0.00
14 2.60 0.397 0.2 0.002 0.010 -0.005
15 2.80 0.399 0.2 0.002 0.010 0.00
16 3.00 0.401 0.2 0.002 0.010 0.00
17 3.20 0.403 0.2 0.002 0.010 0.00
18 3.40 0.405 0.2 0.002 0.010 0.00
19 3.60 0.408 0.2 0.003 0.015 0.005
20 3.80 0.411 0.2 0.003 0.015 0.00
21 4.00 0.413 0.2 0.002 0.010 -0.005
22 4.20 0.416 0.2 0.003 0.015 0.005
23 4.40 0.418 0.2 0.002 0.010 -0.005
24 4.60 0.419 0.2 0.001 0.005 -0.005
25 4.80 0.422 0.2 0.003 0.015 0.010
26 5.00 0.425 0.2 0.003 0.015 0.00
27 5.20 0.427 0.2 0.002 0.010 -0.005
28 5.40 0.429 0.2 0.002 0.010 0.00
29 5.60 0.432 0.2 0.003 0.015 0.005
30 5.80 0.434 0.2 0.002 0.010 -0.005
31 6.00 0.437 0.2 0.003 0.015 0.005
32 6.20 0.439 0.2 0.002 0.010 -0.005
33 6.40 0.442 0.2 0.003 0.015 0.005
34 6.60 0.445 0.2 0.003 0.015 0.00
35 6.80 0.448 0.2 0.003 0.015 0.00
36 7.00 0.452 0.2 0.004 0.020 0.005
37 7.20 0.455 0.2 0.003 0.015 -0.005
38 7.40 0.461 0.2 0.006 0.030 0.015
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Table 01 Contd
Obs no. Volume of

(V)
(ml)
Generated
EMF
(E)
(Volt)

39 7.60 0.465 0.2 0.004 0.020 0.010
40 7.80 0.472 0.2 0.007 0.035 0.015
41 8.00 0.479 0.2 0.007 0.035 0.00
42 8.20 0.488 0.2 0.009 0.045 0.010
43 8.40 0.505 0.2 0.017 0.085 0.040
44 8.60 0.535 0.2 0.030 0.150 0.065
45 8.80 0.682 0.2 0.147 0.735 0.585
46 9.00 0.693 0.2 0.011 0.055 -0.680
47 9.20 0.700 0.2 0.007 0.035 -0.020
48 9.40 0.704 0.2 0.004 0.020 -0.015
49 9.60 0.705 0.2 0.001 0.005 -0.015
50 9.80 0.709 0.2 0.004 0.020 0.015
51 10.0 0.712 0.2 0.003 0.015 -0.005
52 10.2 0.714 0.2 0.002 0.010 -0.005
53 10.4 0.716 0.2 0.002 0.010 0.00
54 10.6 0.720 0.2 0.004 0.020 0.010
55 10.8 0.723 0.2 0.003 0.015 -0.005
56 11.0 0.726 0.2 0.003 0.015 0.00
57 11.2 0.728 0.2 0.002 0.010 -0.005
58 11.5 0.731 0.3 0.003 0.015 0.005
59 12.0 0.734 0.5 0.003 0.015 0.00
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Graphical Representation


Fig 06: Graphical representation of Generated Emf (volt) vs volume of K
2
Cr
2
O
7
(ml)










0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 2 4 6 8 10 12 14
G
e
n
e
r
a
t
e
d

E
M
F

(
V
o
l
t
)

Volume of K2Cr2O7 (ml)
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-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 2 4 6 8 10 12 14

(
V
o
l
t
/
m
l
)

Mean volume of K2Cr2O7 (ml)


Fig07: Graphical representation of AE/AV

versus volume of K
2
Cr
2
O
7
(ml)










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-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
0 2 4 6 8 10 12 14

)
/

(
V
o
l
t
/

m
l
)

Mean volume of K2Cr2O7 (ml)


Fig 08: Graphical representation of A
2
E/AV
2
versus volume of K
2
Cr
2
O
7
(ml)


24 | P a g e

Calculation

Concentration of K
2
Cr
2
O
7
= 0.1N
Required volume of Kr
2
Cr
2
O
7
=3.5 ml
Volume of iron solution = 20 ml

1000 ml 1N K
2
Cr
2
O
7
= 55.85 g Fe
2+
8.6 ml 0.1 N K
2
Cr
2
O
7
= (55.85 8.6 0.1)/ 1000 g Fe2+
= 0.048 g Fe
2+


Result

Required volume of K
2
Cr
2
O
7
for titration = 3.5 ml
Amount of iron = 0.048 g


Discussion

Potentiometric titration of ferrous ion (Fe
2+
) ion to ferric (Fe
3+
) is based on the charge
difference. Due to the cell reaction, a difference in charge occurs. It is then develop a cell
potential that is measured by the potentiometer. Emf of the cell constituted by calomel and
platinum electrode depends upon the potential of platinum electrode since potential of
calomel electrode is constant. Potential of platinum electrode in turn depends on the ratio
[Fe
3+
] /[Fe
2+
] as seen from Nernsts equation. After each addition of K
2
Cr
2
O
7
this ratio
changes and emf changes gradually.

A potential is developed at the beginning and end of the titration, the ratio [Fe
2+
]/[Fe
3+
] is
changing most dramatically. It begins with a number much larger than unity (say 100), and
ends much smaller (say 0.01). In the middle of the titration, the relative amounts of change
are smaller.

25 | P a g e

The main purpose of this titration is to determine the concentration of Fe
2+
ion present in the
solution that depends on determining accurately the end point of titration. From the
experimental data the following three curves are depicted for better detection of end point.
This are-
+ Potentiometric titration curve
+ First derivative plot
+ Second derivative plot

The typical titration curve can be followed point by point, plotting as ordinate successive
values of the cell emf vs. the corresponding volume of titrant added (Appendix: A; Figure
1.1). After adding K
2
Cr
2
O
7
in accurately measured increments a sigmoid curve is obtained
which is similar to the theoretical titration curve for oxidation - reduction reaction. It is seen
that emf changes slowly during the initial portion. In the vicinity of equivalence point a sharp
rise is observed as shown by the vertical portion of the graph. The midpoint in the steeply
rising portion of the curve is then estimated visually and taken as the end point. From this
curve the end point has found at 2.6 ml of K
2
Cr
2
O
7.


A plot of first derivative of potential with respect to volume vs. volume of K
2
Cr
2
O
7
leads to a
sharp maximum at the end point (Appendix: A; Figure 1.2). The end point is 2.5 ml of
K
2
Cr
2
O
7.

The third approach shows that the volume can be fixed more exactly by estimating the point
where the second derivative of the voltage with respect to volume (that is d
2
E / dV
2
) becomes
zero
All of the methods considered are based on the assumption that the titration curve is
symmetric about the equivalence point and that the inflection in the curve thus corresponds to
that point. But, from the first derivative plot one sharp and one small peak are observed.
Second derivative plot shows more than one sudden changes of the curve from the positive to
negative side. But there should be only one sharp peak in 1
st
derivative plot and only one
sudden change of the curve from the positive to negative side in second derivative plot. This
discrepancy may occur because of the following reasons
+ Presence of impurity in sample
26 | P a g e

+ After addition of 8 ml of K
2
Cr
2
07 solution, for each observation only. 1ml of titrant
should be added. But due to mishandling. 1ml of K
2
Cr
2
0
7
is not accurately added to
the Fe
2+
ion containing solution.

Ordinarily, the change in potential within the equivalence point region of these curves is large
enough so that a negligible titration error is introduced if the midpoint of the steeply rising
portion is chosen as the end point. Only when unusual accuracy is desired or where very
dilute solutions are employed must account be taken of this source of uncertainty.

Advantages of potentiometric titration

The chief advantage of the potentiometric titration method is applicability of this method to
turbid, fluorescent, opaque or colored solutions or when suitable visual indicators are
unavailable or inapplicable
In acid base titration, the potentiometric method can be employed with advantage where the
solution have a natural color of their own e.g. ink, vinegar and where titration with indicators
is not possible.
There is no problem with regard to the choice of indicator vis--vis the relative strength of the
acid and base involved. It is possible to titrate polybasic acids in steps corresponding to
different stages of neutralization.
In case of oxidation reduction titration the dependence on color changes and use of external
indicators eliminated by using potentiometric titration method.
Solutions containing more than one halide can be analyzed in a single titration against silver
nitrate using a silver electrode in potentiometric titration.

Limitation

The main disadvantage of this potentiometric titration is that it is more time consuming than a
titration performed with an indicator. When the end point is approached the standard solution
should be added in very small increments. So it is difficult to perform manually.


27 | P a g e









Determination of the conductance of a strong and a weak acid in a acid mixture by
Conductometric Titration

Experiment No: 02
28 | P a g e

Summary

lectrical conductance occurs in different materials either by the flow of electron (As
in metals) or by the movement of other charged species (As in electrolytes or
semiconductors). Conductance of electrolyte depends on the number of ions and
their speeds. In an acid-base titration, one can measure the change in conductivity of the
solution to determine the end point. This method is called a conductometric titration. The
measurement of conductance of electrolyte has been utilized for determining the end point of
titration, solubility of salts etc. In this topic, the theory and chemistry of the reaction between
acid and alkali, instrumentation, Experimental procedure and the advantages and
disadvantages result & discussion of the of the conduct metric titration are described in brief.






E
29 | P a g e

INSTRUMENTS:

Conductance cell
Different types of cells are used for conductance measurement. A cell which is commonly
used is shown in figure 3.1. The container is a glass vessel of Pyrex or other resistance glass
(A), which carries two thick platinised platinum foils (PP), securely fixed so that their
distances are not altered. Two metallic wires (BB) sealed to the platinum foils and protected
by glass tubes serve as the leads for connecting to the metallic bridge.


Figure 3.1: Flask type conductance
Figure 3.2: Conductometer in Laboratory; Model (CMD=750) WPA, Linton Cambridge company

30 | P a g e

PRINCIPLE:

n this experiment mixture of Hydrochloric acid HCl, and Acetic acid CH
3
COOH was
titrated against Sodium Hydroxide NaOH whose end point was determined in
conductometric method. The acid mixture was taken in a beaker in which a combination
electrode was dipped. Standardized NaOH from burette was being added to solution which
caused the variation in conductance with every addition of NaOH. The relative change of
conductance of the solution is measured after each addition of the small volume (0.5-ml) of
NaOH solution. The readings were taken from the conductivity meter. The data thus obtained
were plotted to get a graph. The end points were then located in the graph.

THEORY

he electrical conductance of a solution depends on many factors, such as the
solution's temperature, concentration, and the nature of the solutes. In particular, the
ability of a solution to carry electrical current is proportional to the concentrations
of dissolved ions. Conduction of an electrical current through an electrolytic solution
involves the migration of positively charged species towards the cathode and negatively
charged ions towards the anode. But if the anode is made of the attachable materials (e.g. the
alkali and alkaline earth metals) the flow of current is accompanied by the passage of the
materials from the and into the solution than to the cathode. The addition of an electrolyte to
a solution of another electrolyte under conditions producing no appreciable change in volume
will affect the conductance of the solution according to weather or not ionic reactions occur.
If no ionic reaction take place such as in the addition of one simple salt to another (e.g. KCl
to NaNO
3
), the conductance will simply rise. If ionic reaction occurs, the conductance may
either increase or decrease, thus in the addition of base to a strong acid, the conductance
decreases owing to the replacement of the hydrogen ion of high conductivity by another
action of lower conductivity. This is the under lying principle of conductometric titration.

Let us consider the conductance of a solution of a strong electrolyte A
+
B
-
will change upon
the addition of a reagent C
+
D
-
, assuming that the cation A
+
reacts with the ion D
-
of the
reagent. If the product of the reaction, AD is relatively insoluble or only slightly ionized the
reaction may be written as:
I
T
31 | P a g e

A
+
B
-
+ C
+
D
-
= AD + C
+
B
-

Thus in the reaction between A+ ions and D- ions, the A+ ions are replaced by C+ ions
during the titration, as the titration proceeds the conductance increases or decreases,
depending on weather the conductivity of the C+ ions is greater or less than that of the A+
ions. Consider a solution of a strong acid, hydrochloric acid, HCl for instance, to which a
solution of a strong base, sodium hydroxide NaOH, is added. The reaction is

For each amount of NaOH added equivalent amount of hydrogen ions is removed.
Effectively, the faster moving H
+
cation is replaced by the slower moving Na+ ion, and the
conductivity of the titrated solution as well as the measured conductance of the cell fall. This
continues until the equivalence point is reached, at which we have a solution of sodium
chloride, NaCl. If more base is added an increase in conductivity or conductance is observed,
since more ions are being added and the neutralization reaction no longer removes an
appreciable number any of them. Consequently, in the titration of a strong acid with a strong
base, the conductance has a minimum at the equivalence point. This minimum can be used
instead of an indicator dye to determine the endpoint of the titration. Conductometric titration
curve, that is a plot of the measured conductance or conductivity values against the number of
milliliters of NaOH solution, is shown in Figure 3.3.

Figure 3.3: Conductometric titration curve for hydrochloric acid titrated using solution of
sodium hydroxide.

32 | P a g e

The position of the equivalence point may be localized precisely as the point of intersection
of two straight-lines both determined using readings obtained before and after the minimum
observed, respectively. It makes the conductometric titration more objective and independent
of a nature of an indicator used in the end-point method. This is one of advantages of the
instrumental method. The same reaction of neutralization takes place when a solution of
strong base is titrated using a solution of strong acid. Thus, analogous effects and very similar
shape of conductometric titration curve are observed.

Consider the titration of solution of weak acid, such as acetic acid CH3COOH, using a
solution of strong base, NaOH. As we know, the weak acids, as well as other weak
electrolytes, are dissociated into very small extent and they exist in solution essentially in
form of the neutral acid molecules. When a solution of NaOH is added the reaction

Occurs and, as is seen, the undissociated molecules of acetic acid are transformed into
dissociated molecules of potassium acetate. The changes are accompanied by increase in
conductivity of the hydroxide solution.
Figure 3.4: Conductometric titration curve for acetic acid titrated using solution of sodium.

It should be noted, however that an initial decrease in a conductivity of the solution may be
observed after addition of the first drops of titrant. This minor important effect is related to
neutralization reaction of the protons resulting from dissociation and existing even in a
solution of the weak acid. Thus, an mild increase in conductivity of a titrated solution is
33 | P a g e

observed until the equivalence point is reached, at which we have a solution of sodium
acetate, CH
3
COONa. If an excess of titrant, that is the potassium hydroxide solution, is added
a sharp increase in conductivity is observed. This distinct difference in a rate of increase is
related to the fact that the excess OH- anions, as well as the protons, exhibit particular
mechanisms of charge migration. More detailed inspection of the Conductometric titration
curve presented in figure 3.4. Indicates that the equivalence point is less sharp than that
observed for the strong acid. Thus, it should be localized as the intersection point of two lines
determined by two section of the Conductometric curve. The slope of the first part of the
Conductometric curve is dependent on strength of the acid. It means that it is positive for
very weak acid only.
The method of Conductometric titration is thus well adapted to the estimation of mixtures of
acids of differing strengths. When a mixture of strong and weak acid is titrated a plot of
conductance against alkali added takes form of Fig.4.

Figure 3.5: Conductometric titration curve for the hydrochloric acid acetic acid mixture
titrated using solution of sodium hydroxide.

As is seen, the Conductometric titration curve is a combination of the diagrams obtained
during the titration of strong and weak acid respectively, where the first endpoint corresponds
to a neutralization of the strong acid present in the sample and the second one is associated
with a neutralization of the weak acid in the solution under investigation. The volume of the
alkali consumed by the latter is given by a difference of the respective volumes.
34 | P a g e


35 | P a g e

CHEMICAL REACTIONS:

Sodium Hydroxide, Acetic acid and Sulfuric acid ionize in the solution in the following
forms:
NaOH = Na
+
+ OH
-

HCl = H
+
+ Cl
-
CH
3
COOH = CH
3
COO
-
+ H
+

Then the following reactions occur:
Na
+
+ Cl
-
= NaCl
H
+
+ OH
-
= H
2
O
NaOH + HCl = NaCl + 2H
2
O
NaOH + CH
3
COOH = CH
3
COONa + H
2
O

Procedure

A stock solution of Hydrochloric acid and Acetic acid is taken into a beaker. The
volume of this stock solution is 20 ml.
This solution of two acids is then titrated with 0.2 (N) Sodium Hydroxide (NaOH)
solutions by adding gradually 0.5 ml of it.
The relative change of conductance of the solution is measured after each addition of
the small volume (0.5-ml) of the reagent (NaOH solution).
The reading are taken from the conductivity meter
The data thus obtained are plotted to get a graph.
The one end points are then located in the graph.

36 | P a g e

Determination of end point

Conductometric measurements provide a convenient means for the location of end points in
titrations. To establish a conductometric end point, sufficient data are needed to define the
titration curve. After correction for volume change, the conductance data are plotted as a
function of titration volume. The point of intersection of two lines is taken as the equivalence
point.









Figure 3.6: Conductance vs. volume of NaOH

37 | P a g e

Observed Data

Volume Of NaOH
V
NaOH
(ml)
Conductance
L
S
(mS)
0.0 7.28
0.3 7.18
0.6 6.91
0.9 6.66
1.2 6.52
1.5 6.34
1.8 6.13
2.1 5.92
2.4 5.78
2.7 5.58
3.0 5.40
3.3 5.27
3.6 5.05
3.9 4.90
4.2 4.73
4.5 4.58
4.8 4.38
5.1 4.23
5.4 4.10
5.7 3.93
6.0 3.78
6.3 3.61
6.6 3.44
6.9 3.28
7.2 3.13
7.5 2.95
7.8 2.82
8.1 2.68
8.4 2.53
8.7 2.40
9.0 2.31
9.3 2.17
9.6 2.09
9.9 2.10
10.2 2.10
10.5 2.12
10.8 2.15
11.1 2.18
11.4 2.20
11.7 2.24
12.0 2.27
12.3 2.32
12.6 2.34
12.9 2.37
38 | P a g e

13.2 2.40
13.5 2.44
Table-2.1 continued
Volume Of NaOH
V
NaOH
(ml)
Conductance
L
S
(mS)
13.8 2.45
14.1 2.50
14.4 2.52
14.7 2.56
15.0 2.61
15.3 2.62
15.6 2.64
15.9 2.69
16.2 2.72
16.5 2.76
16.9 2.80
17.3 2.82
17.8 2.88
18.3 2.94
18.8 3.00
19.3 3.14
19.8 3.32
20.3 3.52
20.9 3.61
21.3 3.78
21.8 3.96
22.8 4.25
23.8 4.56

39 | P a g e

Graphical Representation


Figure-16: Specific conductance(mS) vs Volume of NaOH Added(mL)


0
1
2
3
4
5
6
7
8
0 5 10 15 20 25
C
o
n
d
u
c
t
i
v
i
t
y

(
m
S
)

Volume of NaOH (ml)
40 | P a g e

CALCULATION

Standardization of NaOH
Volume of the NaOH, V
1
= 10 ml
Volume 0f oxalic acid, V
2
=20 ml
Strength of oxalic acid S
2
=0.1 N
Now,
V
1
x S
1
= V
2
x S
2

S
1
= (20X0.1)/10
= 0.2 N
So, the strength of NaOH = 0.2 N

Concentration of HCl
Volume of NaOH to neutralize HCl
,
V
1
= 9.5 ml (from graph)
Strength of NaOH, S
1
= 0.2 N
Volume of solution taken, V
2
= 20ml
Strength of HCl
,
S
2
=?
Now, V
1
x S
1
= V
2
x S
2

S
2
= (9.5X 0.2)/20
= 0.095 N
Amount of HCl, m = SeV
= (0.095 x 36.5 x 20)/1000
= 0.06935 gm
Concentration of CH
3
COOH
Volume of NaOH to neutralize CH
3
COOH
,
V
1
= 18.2 9.5 ml = 8.7 ml (from graph)
Strength of NaOH, S
1
= 0.2 N
Volume of solution taken, V
2
= 20ml
Strength of CH
3
COOH, S
2
=?
Now, V
1
x S
1
= V
2
x S
2

S
2
= (8.7 X 0.2)/20
= 0.087 N
Amount of CH
3
COOH, m = SeV
= (0.087 x 60 x 20)/1000
41 | P a g e

= 0.1044 gm
Percentage of HCl and CH
3
COOH in the mixture:
Total amount = 0.06935 + 0.1044= 0.17375 gm

% 9 . 39
% 100
17375 . 0
06935 . 0
=
= HCl of Percentage

% 1 . 60
% 100
17375 . 0
1044 . 0
3
=
= COOH CH of Percentage

Result

The percentage of HCl = 39.9%
The percentage of CH
3
COOH = 60.1 %


Discussion

In this experiment strong acid HCl and weak acid CH
3
COOH is titrated at the same time with
strong base NaOH solution so there should be two end points. According to figure (appendix)
2 definite end points are observed. The first of these indicate neutralization of HCl acid
(strong acid) and second of these indicate neutralization of CH
3
COOH acid (weak acid). So
the result is satisfactory.
In this experiment, the Conduct metric titration curve for a weak acid (CH
3
COOH) and
strong acid (HCl) with strong base (NaOH) is depicted.
This curve shows a sharp decrease in conductance till the end point of the reaction between
HCl and NaOH is reached. After this first equivalent point the conductance rise gradually up
to the second end point, which indicate the neutralization of CH
3
COOH acid with NaOH
solution and then the conductance rise sharply again as NaOH introduces the fast moving
hydronil ion. This characteristic of the curve is described in brief below

42 | P a g e

In performing the conductometric titration the following things should be taken under
consideration
The relative change of conductance of the solution during the reaction and upon the
addition of an excess of reagent largely determined the accuracy of the titration.
(Under optimum conditions this is about 0.5%).
Large amount of foreign electrolytes which do not take part in the reaction, must be
absent since those have a considerable effect upon the accuracy.
The accuracy of the method is greater when the acute angle of interception is more
and the points on the graph lie on a straight line.
It is necessary to keep the temperature constant throughout the experiment
In acid alkali titration, the titrant should be about 10 times stronger than the solution
to be titrated so that the volume change is as little as possible
Platinised platinum electrode should be used to minimize polarization effects
The electrodes should be large and should be placed closely.

43 | P a g e

ADVANTAGES

Sometimes the end point in an acid-base titration reaction can not be determined using a
chemical indicator. This may occur for the following reasons:
a) No suitable indicator
b) No stable end point
c) The solution is too dilute
d) The solution is turbid (suspension of small particles)
e) The solution is brightly or strongly colored.
The end point can still be determined by following some suitable characteristic of the solution
that is conductance. Conductometric titration is suitable for,
Very weak acid, such as boric acid and phenol, which cannot be titrated
potentiometrically in aqueous solution, can be titrated conductometrically.
Mixture of certain acids can be titrated more accurately by conductometric titration
than by Potentiometric pH methods. Thus mixtures of HCl or any other strong acid and
acetic acid or any other weak acid of comparable strength can be titrated with a weak base
(e.g. aqueous NH
3
) or with a strong base (e.g. NaOH) reasonably satisfactory end points
are obtained.
This method is as accurate in the dilute solution as in more concentrated solution.
It may be applied where visual or potentiometric methods fail to give results owing to
considerable solubility or hydrolysis at the equivalent point.

LIMITATION:

Conductometric titration may be used to detect the end points of the comparatively simple
systems in which there are no excessive amounts of reagent present. Thus many oxidation
titrations which require the presence of relatively large amount of acid are not suited to
Conductometric titration.


44 | P a g e







Determination of concentration of HCl acid by
pH Metric Titration

Experiment No: 03
45 | P a g e

Summary

n an acid base neutralization reaction the neutralization point exhibits a sharp change in
pH with small change in the volume. The process of determining the end point by
monitoring the sharp change in pH is known as pH titration.
INSTRUMENTS:
Glass electrode:
Glass electrode is potentiometric sensor made from glass of a specific composition. It is an
Ion-selective electrode (ISE) with a transducer (sensor) which converts the activity of a
hydeogen ion (H+) dissolved in a solution into an electrical potential which can be measured
by a voltmeter or pH meter. The voltage is theoretically dependent on the logarithm of the
ionic activity, according to the Nernst equation. The sensing part of the electrode is usually
made as an ion-specific membrane, along with a reference electrode. Ion-selective electrodes
are used in biochemical and biophysical research, where measurements of ionic concentration
in an aqueous solution are required, usually on a real time basis.

Figure 2.1: |Operating principle of glass electrode method
I
46 | P a g e

Construction:
A glass electrode consists of an electrode membrane that responds to pH, a highly isolating
base material to support the unit, solution inside the glass electrode, an internal electrode, a
lead wire, and a glass electrode terminal. The most critical item in this system are-


Figure 2.2: Scheme of typical pH glass electrode

a sensing part of electrode, a bulb made from a specific glass
sometimes the electrode contains a small amount of AgCl precipitate inside the
glass electrode
internal solution, usually 0.1M HCl for pH electrodes or 0.1M MeCl for pMe
electrodes
internal electrode, usually silver chloride electrode or calomel electrode
body of electrode, made from non-conductive glass or plastics.
reference electrode, usually the same type as 4
junction with studied solution, usually made from ceramics or capillary with
asbestos or quartz fiber.
47 | P a g e

PRINCIPLE:

n this experiment Na
2
CO
3
was titrated against H
2
SO
4
, whose end point was determined
in pH method. Na
2
CO
3
was taken in a beaker in which a combination electrode was
dipped. HCl from burette was being added to solution which caused the variation in pH
with every addition of HCl. The reading of pH from the pH meter was obtained.

THEORY:

n passing from acid to alkaline solutions the concentration of hydrogen ions can vary
within very wide limits to permit a convenient means of expressing the concentration of
hydrogen ions without involving negative exponents; on the pH of any solution is given
by,
pH = -log
10
a
H
+
where, a
H
+
= Hydrogen activity

Fritz, Haber and Z Klemensiewiez first showed that when a glass membrane separates two
solutions of different pH a potential established across the membrane whose magnitude
depends on the difference in the pH of the two solutions. If the pH of one of these solutions is
held constant and while that of the second is varied, the emf of the electrode follows the
equation:

F / RT 303 . 2
E E
pH
pH
F
RT 303 . 2
E
a ln
F
RT
E E
0
0
H
0

=
=
=
+


Hence it is seen that pH is the function of emf a pH meter employed which using potential
differences gives pH directly. When known solution of acid or base added to unknown base
or acid, pH changes with the addition of known solution and measuring pH against volume
added plot could be constructed this has a sharp break at the end point of each reaction.
I
I
48 | P a g e

CHEMICAL REACTIONS:

The combination electrode was dipped in the Na
2
CO
3
solution taken in a beaker. Since the
solution inside the glass tube was maintained at a constant pH potential of the calomel
electrode inserted into it was constant and so was the potential between the HCl solution and
inner surface of the glass tubes and test solution varied with the change of hydrogen ion
concentration of the solution.

With every addition of HCl from the burette into the solution of Na
2
CO
3
, pH varied and
consequently emf of the combination electrode changed. This emf was recorded by an in built
potentiometer of the pH meter. This potentiometer reading was automatically converted
electrically to a direct reading of pH of the solution.

Reactions involve in the process are-

H
+
(solution) + Na
+
(glass) = Na
+
(solution) + H+ (glass)
HA = H
+
+ A
-
| || |
| | HA
A H
K
+
=
| |
| |
| | HA
A
log H log K log

+
+ =

When 50% acid is neutralized then the concentration of acid and salt will be equal. In that
case, pK = pH
The reaction involved here is completed by two steps. They are as follows:

Na
2
CO
3
+ HCl NaHCO
3
+ NaCl

NaHCO
3
+ HCl NaCl + H
2
CO
3



CO
2
+ H
2
O
49 | P a g e

Procedure

Procedure mentioned below is followed during performing this experiment
20 ml of Na
2
CO
3
(0.05N)solution is taken into a beaker;
A combined set-up of glass electrode and calomel electrode is dipped into the above
said beaker.
This glass set-up of electrodes is connected to pH meter;
0.2 (N) HCl solution is added in the beaker containing Na
2
CO
3
solution by using a
burette and corresponding pH reading is taken from pH meter;
Each time .2 to .3 ml of 0.2 (N) HCl acid is added until end point is reached.


Observed and Calculated Data

Obs no. Volume of

(V)
(ml)
pH

01 0 10.3
02 0.2 10.14 0.2 0.16 0.8
03 0.4 9.97 0.2 0.17 0.85 0.05
04 0.6 9.76 0.2 0.21 1.05 0.2
05 0.8 9.44 0.2 0.32 1.6 0.55
06 1 8.94 0.2 0.5 2.5 0.9
07 1.2 7.51 0.2 1.43 7.15 4.65
08 1.4 7.02 0.2 0.49 2.45 -4.7
09 1.6 6.69 0.2 0.33 1.65 -0.8
10 1.8 6.44 0.2 0.25 1.25 -0.4
11 2 6.21 0.2 0.23 1.15 -0.1
12 2.2 5.94 0.3 0.27 1.35 0.2
13 2.4 5.48 0.2 0.46 2.3 0.95
14 2.6 3.86 0.2 1.62 8.1 5.8
15 2.8 3.25 0.2 0.61 3.05 -5.05
16 3 3.08 0.2 0.17 0.85 -2.2
17 3.2 2.92 0.2 0.16 0.8 -0.05



50 | P a g e

0
1
2
3
4
5
6
7
8
9
0 0.5 1 1.5 2 2.5 3 3.5

Mean volume of HCl (ml)
Graphical Representation




0
2
4
6
8
10
12
0 0.5 1 1.5 2 2.5 3 3.5
p
H

Volume of HCl (ml)
51 | P a g e



Determination of end point:

pH metric process to determine the end point of titration is an important method. By this
method, for an acid-base titration pH changes gradually as titrant is added. Around the
equivalence point, however the pH changed abruptly. The rate of change is greatest at the
equivalence point. This can be seen with the plot pH VS volume of HCl plot. A plot dpH/dV
vs. volume also shows a sharp peak at the equivalence point.

-6
-4
-2
0
2
4
6
8
0 0.5 1 1.5 2 2.5 3 3.5
(

)
/
(

2
)


Mean volume of HCl (ml)
52 | P a g e

Calculation
From the graph the 1
st
end point of the reaction was 1.1 ml HCl and the 2
nd
end point of the
reaction was 2.5 ml HCl.
VOLUME OF Na
2
CO
3
, V
1
= 20 ml
STRENGTH OF Na
2
CO
3,
S
1
=0.05 N
V
1
S
1
= V
2
S
2

S
2
= (200.05) / 2.5
= 0.4 N
From the Graph,
pK
1
=9.5
pK
2
=6.4
Result:
Strength of HCl Solution = 0.23 (N)
From graph, pK
1
= 9.8
pK
2
= 6.3

DISCISSION:

In this experiment, rather than using a base, Na
2
CO
3
salt solution has used to study the pH
behavior. Before adding any HCl acid the pH of the solution was high. pH gradually
decreases with the addition of HCl acid as Na
+
of Na
2
CO
3
is replaced by the H
+
. The pH
value changes very slowly at the beginning of the reaction but in the region of the neutral
point a very sharp change in pH value occurs on the addition of a very small quantity of base.
To determine the neutralization point accurately three curves are plotted. The plots showed
the naturalization reaction between HC1 acid and Na
2
CO
3
in the two steps by the two peaks.
In the first step, Na
2
CO
3
is converted to NaHCO
3
and in the second step NaHCO
3
is further
neutralized to H
2
CO
3
.
The experimental plots conducted in this experiment are agreed with the theoretical one. The
plots showed the naturalization reaction between HC1 acid and Na
2
CO
3
in the two steps by
the two peaks. The first peak is not as sharp as the second peak.
There may be four main reasons for the first peaks not being as sharp as the second one.
They are:
53 | P a g e


+ Impurities may present in the Na
2
Co
3
solution and distilled water used in this
experiment.
+ During each observation .2ml of the .2 (N) HC1 acids should be added in the Na
2
CO
3

solution. But this is not performed strictly.
+ To make the pH of the solution stable sometime should be given between two
successive observations, but sufficient time is not spent here.
+ The solution is not stirred properly.

From the plots, two information has found. First, the concentration of the solution can be
calculated by determining the end point. Second, the dissociation constant can be known that
gives the strength of the solution. The more the dissociation constant, the more easily the
solution will dissociate. From the plot it has found that Na
2
CO
3
has large dissociation
constant (pK1=8.9) than NaHCO
3
(pK2 = 5.9).

INDUSTRIAL APPLICATION:

The pH metric titration method has the applicability in industry, which can be classified into
four main systems:
a. Preparations where efficiency is dependent on the pH of the solutions
involved. e.g. penicillin manufacture
b. Quality control where uniformity of the products depend on pH control at
some stage e.g. the paper industry
c. Neutralization of effluents.
d. Corrosion inhibition e.g. in high-pressure boilers.

ADVANTAGES:

pH metric titration has some unique advantages. Some of them are given below:
In colored solutions, Indicators can not detect endpoints where as pH metric titration is
not subjected to this limitation.
Indicators for any acid-base titration must be chosen so that the pH at which the
indicator changes color corresponds more or less to the pH of the solution at the
54 | P a g e

equivalence point. Hence some information is required concerning the relative
strength of the acid base involved. pH metric titration always yield the equivalence
point whether this point comes exactly at the neutral point or on the acid or basic acid.
With indicators it is some-times impossible or difficult to titrate a polybasic acid or a
mixture of a strong acid and weak acid with a base. In such cases pH metric titration
gives accurate result.
Oxidation titration can be carried out by this method
In precipitation reaction, pH metric titration can be employed with out any difficulty.
Titration of weak acid-weak base, strong acid-weak base, weak acid strong base,
when indicator choosing is difficult or indicator does not show distinct color change,
then by pH metric titration end point of the titration can be detected easily.

LIMITATIONS:

The main limitation of pH metric titration arises when strong, alkaline solution is used. In this
case the glass electrode is affected by the alkaline solution. The glass electrode shows very
little response to divalent actions. Special care should be taken in handling this glass
electrode, as it is very expensive otherwise it can be damaged or broken.










55 | P a g e






Determination concentration of an unknown sample of Fe3+ solution by
Spectrophotometric method

Experiment No: 04
56 | P a g e

Summary

n the photometric method of equivalence point detection in titrations, use is made of the
difference in the molar absorptivities (at the analytical wavelength selected) of the
various species present. The appearance of an absorbing species will give a linear or
concentration dependent change in absorbance which will yield two straight lines that
intersect at the equivalence point. Spectroscopy means the separation, detection and
recording of energy changes (resonance peaks) involving nuclei, atom or molecular structure
or the value of an electric dipole moment to make an elemental analysis or to verify the
presence of a chemical bond.
Spectrophotometer
A spectrometer is used to produce a signal corresponding to the difference between the
transmitted radiation of a reference material and that off a sample at selected wavelengths It
furnishes the ratio, or a function of the ratio, of the radiant power of two beams as a function
of spectral wavelength. These two beams may be separated in time, space, or both.
Spectrophotometers are complex and versatile equipment that include a monochromator,
which provides a narrow band of continuously variable wavelength. A wide variety of
spectrophotometers are commercially available. Working principle of spectrophotometer
can be shown as follows:









Figure-2.1 Working principle of spectrophotometer.
I
SOURCE SELECTOR SAMPLE
DETECTOR
READ-OUT
57 | P a g e

PRINCIPLE:

erric solution of concentration 1 to 5 ppm is prepared and then 20ml 10% KSCN and
3ml 6 (N) HNO3 acids is added in each of the prepared ferric solution. Solution of
concentration of 3 ppm is taken as standard solution. Absorbency data are collected
against wavelengths ranging from 400 to 520 m provided that each wavelength is adjusted
to 100% transmittance for solvent i.e. distilled water. Setting the spectrophotometer at the
maximum wavelength, absorbance against each concentration is evaluated. Then absorbance
VS concentration curve is constructed. From the plot, which is a straight line, knowing
absorbance of the unknown solution, concentration of that solution is evaluated.



Figure 4.3: Solutions prepared for spectrometer
F
58 | P a g e

THEORY

hen monochromatic or heterogeneous light falls upon a homogenous medium,
a portion of incident light is reflected, a portion is absorbed with in the
medium. And the remainder is transmitted. The portion of light reflected is
usually very small for air-glass interface compared to the other terms. Intensity of the
incident light I
o
can be related with that of transmitted light I
t
by Beer Lambert law,
I =I
o
e
-


A
Where, A = absorbance
= absorption co-efficient
[c] = concentration of absorbing medium
l = thickness of the medium.
If Beer Lambert equation is obeyed, then a plat of A Vs [c] will be a straight line through the
origin provided thickness remains constant. This is the fundamental equation of
spectrophoto-metry. In many instances, sample compound does not absorb radiation
appreciably in the wave length regions provided, it is then necessary to form unabsorbing
substance by reacting the compound in question with other reagents. The reagents should be
selective in their reactions and should not form interfering absorbing species with foreign
substances likely to be present.

Basic principles of spectrophotometry

An absorbance spectrophotometer is an instrument that measures the fraction of the incident
light transmitted through a solution. In other words, it is used to measure the amount of light
that passes through a sample material and, by comparison to the initial intensity of light
reaching the sample, they indirectly measure the amount of light absorbed by that sample.
Spectrophotometers are designed to transmit light of narrow wavelength ranges (see Figure 1
the electromagnetic spectrum). A given compound will not absorb all wavelengths equally
thats why things are different colors (some compounds absorb only wavelengths outside of
the visible light spectrum, and thats why there are colorless solutions like water). Because
different compounds absorb light at different wavelengths, a spectrophotometer can be used
W
59 | P a g e

to distinguish compounds by analyzing the pattern of wavelengths absorbed by a given
sample. Additionally, the amount of light absorbed is directly proportional to the
concentration of absorbing compounds in that sample, so a spectrophotometer can also be
used to determine concentrations of compounds in solution. As particles in suspension scatter
light (thus preventing it from reaching the light detector), spectrophotometers also can be
used to estimate the number of cells in suspension.

Figure 4.4: The electromagnetic spectrum. Visible light (400-700 nm) constitutes only a
small portion of the spectrum that ranges from gamma rays (less than 1 pm long) to radio
waves that are thousands of meters long

When studying a compound in solution by spectrophotometry, it is put in a sample holder
called a cuvette and placed in the spectrophotometer. Light of a particular wavelength passes
through the solution inside the cuvette and the amount of light transmitted (passed through
the solutionTransmittance) or absorbed (Absorbance) by the solution is measured by a light
meter. While a spectrophotometer can display measurements as either transmittance or
absorbance, in chemistry researchers are usually interested in the absorbance of a given
sample. Because other compounds in a solution (or the solvent itself) may absorb the same
wavelengths as the compound being analyzed, the absorbance of test solution is compared to
a reference blank. Ideally, the reference blank should contain everything found in the sample
solution except the substance you are trying to analyze or measure. The reference blank in
this case would be water alone. The amount of light transmitted through a solution is referred
to as transmittance (T). The transmittance is defined as the ratio of the light energy
transmitted through the sample (I) to the energy transmitted through the reference blank (I0).
Since the compound being tested is not present in the reference blank, the transmittance of
the reference blank is defined as 100%T.
60 | P a g e

T = I/I
0

This number is multiplied by 100 to determine the percent transmittance (%T), the percentage
of light transmitted by the substance relative to the reference blank.
%T = I/I
0
* 100
A certain portion of the light will be absorbed by the compound in the test cuvette; therefore
its %T will be lower than that of the blank (by definition, 100%).
We measure absorbance (Al, also referred to as Optical Density or ODl, where l is the
wavelength used for the measurements), the amount of light absorbed by a solution.
Absorbance is related logarithmically to transmission thusly.
A = -log T
Again, a reference blank is used. In this case, to zero out any light absorbed by anything in
the solution other than the compound of interest. By definition, the absorbance of the
reference blank is set at zero (Al = 0). Visible light (see Figure 4.4) is composed of
wavelengths from 400 to 700 nm (nanometers). When visible light passes through a colored
solution, some wavelengths are transmitted and others are absorbed. We see the color of the
transmitted wavelengths. For instance, red color results when a solution absorbs short
wavelengths (green and blue) and transmits longer wavelengths (red). An absorbance
spectrum (a plot of absorbance as a function of wavelength) is determined to select the
optimal wavelength for analyzing a given compound. The optimal wavelength (A
max
) for
measuring absorbance is that wavelength that is most absorbed by the compound in question.
This provides maximum sensitivity for the measurements. A hypothetical absorbance
spectrum is shown in Figure 4.5.

61 | P a g e

Figure 4.5 A typical absorbance spectrum
The light from the spectrophotometers light source (in the case of measurements in the
visible range, a simple incandescent bulb) does not consist of a single wavelength, but a
continuous portion of the electromagnetic spectrum. This light is separated into specific
portions of the spectrum through the use of prisms or a diffraction grating. A small portion of
the separated spectrum then passes through a narrow slit. When you adjust the wavelength on
a spectrophotometer, we are changing the position of the prism or diffraction grating so that
different wavelengths of light are directed at the slit. The smaller is the slit width; the better is
the ability of the instrument of resolving various compounds. This small band of light then
passes through the cuvette containing the sample. Light that passes through the sample is
detected by a photocell and measured to yield the transmittance or absorbance value (optical
density) for the sample. See Figure 3 for a schematic of a spectrophotometer.

Figure 4.6: Components of a Spectrophotometer

There is a relationship between concentration and absorbance. This relationship is expressed
by the Lambert-Beer law, which is more commonly known as Beers law. This law states that
the absorbance of a light absorbing material is proportional to its concentration in solution.
A = elc
e = the extinction coefficient of the substance, has units of M-1 * cm-1
l = the sample path length measured in centimeters
c = the molar concentration of the solution
62 | P a g e


Figure 4.7: A typical absorbance vs. concentration curve

It is because of this relationship that biologists measure absorption rather than transmission.
The Lambert-Beer law can be used to calculate the concentration of a solution if its extinction
coefficient is known.
To determine the extinction coefficient, the absorbance of a known concentration of solution
is measured and then the equation is rearranged to solve for e. thus, e = A/lc
CHEMICAL REACTIONS:

Since spectrophotometric estimation involves physical property only, so no reaction takes
place. Only addition of KSCN forms a complex with Fe
+++
, which is given below:

Fe
3+
+ n (SCN)
-
= Fe (SCN)
n

3-n
Here (n = 1~6)
n

I nstrumentation
The instrument employed for this purpose is a spectrophotometer. We used two types of
spectrophotometer.
1. Single-beam spectrophotometer
Model: SPECTRONIC 21
BAUSH & LOMB
2. Double-beam Spectrophotometer:
Model: UV-1601 PC
UV- VISIBLE SPECTROPHOTOMETERSHIMADZU

63 | P a g e


Figure2.3:A spectochotometer

Cells
To investigate the absorption of radiation by a given solution, the solution must be placed in a
suitable container called cell, which can be accurately located in the beam of radiation. The
instrument is provided with a cell carrier, which serves to site the cell correctly.


Figure2.4:A cuvettes spectophotometer
Standard cells are made of glass to cover the wavelength ranging over (340~1000 qm) but for
lower wavelengths down to 720 qm, they must be made of silica. All standard cells are
supplied with a lid to prevent spillage. Standard cells are produced in three grades.




64 | P a g e

PROCEDURE

Procedure mentioned below was maintained during conducting this experiment.
Ferric solution of concentration 1 to 5 ppm is prepared and then 10ml 10% NH4SCN and
1ml 6(N) HNO
3
acid is added in each of the prepared ferric solution.
Solution of concentration of 2 ppm is taken as standard solution.
Absorbency data
that each wavelength is adjusted to 100% transmittance for solvent i.e. distilled water.
Setting the spectrophotometer at the maximum wavelength, absorbance against each
concentration is evaluated.
Then absorbance VS concentration curve is constructed.
From the plot, which is a straight line, knowing absorbance of the unknown solution,
concentration of that solution is evaluated.


Observed Data

Table-E.1 : Concentration of Ferric Solution and Absorbance of the Solution.
Sample no Concentration
(ppm)
Absorbance

1 1 0.190
2 2 0.321
3 3 0.4647
4 4 0.576
5 5 0.726
6 Unknown 0.362
65 | P a g e

y = 0.1487x
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 1 2 3 4 5 6
A
b
s
o
r
b
a
n
c
e

(
A
)

Concentration (ppm)
2.446
Graphical Representation



RESULT:

The concentration of unknown sample = 2.446 ppm

DISCUSSION:

The prediction of Beer Limbers law is verified in this experiment. By plotting absorbance Vs
concentration a straight line should be obtained which the linear relation between absorbance
and concentration is true.
The calibration curve of absorbance VS concentration (at constant wavelength) should pass
through the origin since at the zero concentration (Infinite dilution) absorbance must be zero.
66 | P a g e

But in this experiment, least square fitting of the curve (figure.. appendix) yields a straight
line while passed straightly above the origin. The following reasons may be responsible for
this:
+ In complete conversion of ferrous ion (Fe
2+
) to ferric ion (Fe
3+
) may have occurred.
+ Impurities present in the sample solution (solution of 3ppm concentration) which
may absorb light at the absorption wavelength.
+ Impurities present in the distilled water used in preparing sample solution.
In the spectrum of Fe [(SCN)
6
]
-3
(Figure Appendix) the highest peak indicates strong
(maximum) absorption while the small peak indicates weak absorption. Maximum absorption
occurs at a particular wavelength but not at any wavelength.
The sample compound (Fe3+ solution) doesnt absorb radiation appreciably in the provided
wavelength regions. It is necessary to form an absorbing substance by reacting the sample
with other reagents. Thats way KSCN is added to Fe
3+
solution. This forms a complex with
Fe
3+
solution.

ADVANTAGES:

Absorption spectroscopy is one of the most useful methods available to the chemistry for
quantitative analysis. Important characteristics of photometric method include (a) wide
applicability, (b) high sensitivity, (c) moderate to high selectivity, (d) accuracy and (e)
convenience.
Spectrophotometer can provide narrow bandwidth of radiation and also can handle absorption
spectra in ultra violet region, which turns spectrophotometric method dominating over
spectrometer or photometer. Spectrophotometric estimation can provide a simple mean of
determining minute quantities of substance. As for example, it can detect 10
-4
to 10
-6
mol/liter
in any solution.


LIMITATION:

In the analysis of very concentrated or very dilute solution, i.e. solution whose transmittance
lie outside the range 0.2 to 0.65, some problems arise with spectrophotometric estimation.
Where as in ordinary method the transmittance scale is set at zero (to represent infinite
67 | P a g e

concentration) precession is less than that attainable with volumetric or gravimetric
techniques. This is the main limitation of spectrophotometric estimation.




Determination of percentage of Cu present in Brass by
Electro-gravimetric method


Experiment No: 05
68 | P a g e

Summary:

lectrogravimetric analysis is a physico-chemical method of analysis. At the same
time it is a form of gravimetric analysis. Its characteristic feature is deposition of
the element to be determined on weighed electrode by electrolysis. This process is
used for determination of metals almost exclusively. Metals are usually present in solution as
catalyst, which migrate to the cathode during electrolysis, are discharged, and deposited as
the free metals. The amount of the metal deposited is found from the weight of the cathode.
In most applications the metal is deposited on a weighed platinum cathode and the increase in
weight is determined. In this topic theory, chemistry of the process, experimental procedure,
instrumentation, advantage and limitation, result & discussion of electrogravimetric method
are described in brief.



E
69 | P a g e

Theory

hen a direct electric current is passed through an ELECTROLYTE (such as a
molten salt or an aqueous solution of a salt, acid or base) , chemical reactions
take place at the contacts between the circuit and the solution. This process is
called ELECTROLYSIS.
Gravimetry is a quantitative analysis. In gravimetric
analysis the substance being determined is converted into
an insoluble precipitate which is collected and weighed;
in the special case of electrogravimetry, electrolysis is
carried out and material deposited on one of the
electrodes is weighed.
Electrogravimetry is a method used to separate and
quantify ions of a substance, usually a metal. In this
process, the analyte solution is electrolyzed.
Electrochemical reduction causes the analyte to be
deposited on the cathode. The cathode is weighed before
and after the experiment, and weighing by difference is
used to calculate the amount of analyte in the original solution. Controlling the potential of
the electrode is important to ensure that only the metal being analyzed will be deposited on
the electrode.
The main objective of this experiment was to know about electrogravimetric analysis and to
know its application on quantitative analysis. Here in this experiment electrogravimetric
analysis was performed to know the amount of copper present in a sample of brass. We
determined the amount as well as the purity of copper by comparing it with the literature
value of copper present in brass.
In electrogravimetric analysis, the element is to be determined is deposited electrolytically
upon a suitable electrode. Electro deposition is governed by Ohms law and by Faradays law
of electrolysis.
Ohms Law:
It expresses the relation between the three fundamental quantities: current, electromotive
force and resistance.
W
70 | P a g e

The current I is directly proportional to the resistance R,
i.e. I = E/R
Faradays Law :
1. The amounts of substances liberated or dissolved at the electrodes of a cell are directly
proportional to the quantity of electricity which passes through the solution.
2. The amounts of different substances liberated or dissolved by the same quantity of
electricity are proportional to their relative atomic (or molar) masses divided the number of
electrons involved in the respective electrode processes.


In the common method of electrogravimetric analysis, a potential slightly, in excess of the
decomposition potential of the electrolyte under investigation is applied, and the electrolysis
is allowed to proceed without further attention, except perhaps occasionally to increase the
applied potential to keep the current at approximately the same value. For this purpose an
electronic device called potentiostat is used in the circuit. This device controls the potential
difference between the cathode and the reference electrode.

71 | P a g e

CHEMICAL REACTIONS
Copper may be deposited from either sulphuric acid or nitric acid solution but here a mixture
of the two acids is employed. When this solution is electrolyzed with an emf of 3 volts the
following reaction occurred
Reaction at Cathode:
2
2
2 2
2
H e H
Cu e Cu
+
+
+
+

Reaction at Anode:

+ + e O H O OH 4 2 4
2 2

The beneficial effect of nitrate ion is due to its depolarizing action at the cathode. The
reaction is
O H NH e H NO
2 4 3
3 8 10 + + +
+ +

The reduction potential of NO
3
-
is lower than the discharge potential of hydrogen. Here the
formation of Ammonium ion occurs to the exclusion of gas evolution.
The beneficial effect of sulphate ion (SO
4
2-
) is to the easy liberation of NO
3
-
for
depolarization and also for liberation of nitrate ion (NO
3
-
) as NO
2
when it is warmed. The
reaction is

+ + e O NO NO
2 2
1
2 3



72 | P a g e

Chemicals:
Brass
HNO
3

H
2
SO
4

Distilled water
Urea
Apparatus:
Beaker
Magnetic stirrer
Bunsen burner
Platinum cathode
Fischer electrode





73 | P a g e

Working Procedure:

In this experiment determination of percentage of copper in brass was performed by
electrogravimetric process. Procedure mentioned below was followed during conducting this
experiment
By using an electronic balance weight of brass and platinum gauge cathode were
taken;
Brass was then taken into a beaker and concentrated HNO
3
acid is added drop wise to
dissolve the brass. The color of the solution at that instant was blue;
1 ml of concentrated H
2
SO
4
acid was then added into the beaker;
A small amount of distilled water was poured into the above said beaker and it is
heated until the solution becomes concentrated and white fumes are observed;
The stirrer was switched on and the electrolysis is continued until the blue color the
solution has entirely disappeared (about 1 hr);
The cathode was sunk into C
2
H
5
OH and then kept in open air for quick drying;
After drying, the weight of (cathode+Cu) was taken; &
From the increase in weight of the cathode, the copper content in brass was
calculated.





74 | P a g e

Observed Data and Calculated Data
Weight of the brass = 0.3035 gm
Weight of the uncoated cathode = 18.3897 gm
Weight of the coated cathode (cathode + Cu metal) = 18.5471 gm
So, weight of the deposited Cu= (Weight of the coated cathode- Weight of the coated
cathode)
= 0.1574 gm

% of copper recovered



=

=51.86%


Results
Weight of copper deposited, W
Cu
=0.1574gm
Weight percentage of copper in brass sample = 51.86%

75 | P a g e

Discussion:

From the result it is clear that complete deposition of Cu is not achieved. This may happened
due to the following reasons:
The brass used here is impure
In preparing Cu solution heating is required to remove excess NO3- as NO2 gas, but
in this case excess heat was given which oxidized Cu into CuO,
Cu + O2 = CuO
Since Nitrite ion resists complete deposition it should be made the HNO3 acid free
from HNO2 either
- by addition of urea to the solution,
2H+ + 2NO2- + NH2CONH2 = 2N2 + CO2 + 3H2O.
- by boiling the HNO3 before adding it; or
- by adding sulphuric acid to the solution,
H+ + NO2- + SO3-NH2 = N2 + HSO4- + H2O.
If any of the above said measures are not performed, complete deposition is quite
impossible.
In this experiment the dilute solution is prepared otherwise incomplete deposition of
Cu might take place or the deposition will not adhere satisfactorily to the cathode.
Polarization occurs due to evolution of H2 gas to cathode and it leads to deposition of
spongy and poor quality copper. Thats why the deposition of Cu is carried out in
HNO3 media because nitrate ion reduced to ammonium ion at a copper surface,
NO3- + 10H- + 8e- = NH4+ + 3H2O.
During electroplating, the concentration of Cu ion at the electrode is depleted relative
to the rest of the solution during the passage of any appreciable current. This is termed
as concentration over potential. A magnetic stirrer is used to keep this term as small as
possible.
In this experiment, low constant current density is used for better deposition.
To find out all the Cu deposited or not some water had been added, the cathode is
more dipped and it was tested that whether it becomes reddish or not, when no more
Cu deposited on the cathode then the power was turned of.
The voltage and current supply had been maintained constant throughout the
experiment
76 | P a g e

Advantages
One of the most important advantages of electrogravimetric method is the applicability of this
method in electroplating i.e. coating of metal substances by depositing on it, Ni, Cu, Au, Ag,
Pt etc. These non-corrosive metals make metallic substances long lasting and lustrous. An
interesting application of this method is the direct quantitative separation of constituents from
alloy. The constituent with low deposition potential is deposited first.
In this method, with rising and lowering the temperature of the solution, physical properties
of the deposition can be controlled.
By applying this process, constituents and also percentage composition of the constituents in
any alloy can easily be evaluated.

Limitation
Some limitation of this electrogravimetric method is also present although this process is very
much advantageous. They are listed below
For gravimetric purpose, an electrolytic deposit should be strongly adherent, dense and
smooth so that the process of washing, drying and weighing can be performed without
mechanical loss or without reaction with the atmosphere.
Fluctuating current density may result in flaky, spongy, power granular, uneven deposits,
which only loosely bound to the electrode.
At sufficiently high values of the current density evolution of hydrogen may occur owing to
the depletion of metal ions near the cathode. If appreciable evolution of hydrogen gas occurs,
the deposit will usually become broken up and irregular which may lead to spongy and
poorly adherent deposits.
If cost of electricity is high then use of this process for coating makes substances costly.
Many metals form smoother and more adherent films when deposited from solutions in
which their ions exist primarily as complexes. Deposition of these metals requires a higher
applied potential than in the absence of the legend. These effects can be large and must be
taken into account when considering the feasibility of an electrolytic determination or
separation.