CHEM-352

A term paper on

INSTRUMENTAL METHODS OF ANALYSIS






i
ChEm-352

A term paper on


Instrumental methods of analysis




Submitted By

Name: Md. Hasib Al Mahbub
Student Id.: 0902045
Group No: 05 Section: A2
Level-3, Term-1
Department Of Chemical Engineering



Submitted To

Dr. Md. Rafique Ullah, Professor, Department Of Chemistry, BUET
Dr. Md. Nazrul Islam, Associate Professor, Department Of Chemistry, BUET













Date of Submission: 11
th
June, 2013 Partners Id: 0902038
0902040
0902044
Bangladesh University of Engineering and Technology

ii
PREFACE

Analytical chemistry is the art and science of chemical characterization. Instrumental method
of analysis is the part of analytical chemistry. These methods are based on the measurement of
optical, electrical, thermal and other properties. The instrumental methods of analytical
chemistry used in laboratory and research work can be mastered if chemical instrumentation is
studied in its own way. It is always desirable to get almost perfect result with high reliability
within a very short time and this is the reason behind the introduction of digital instruments in
the field of analytical chemistry that has created a revolution in this discipline. In the way of
gradual development and faster adoption of change in the field of science & technology we,
the chemical engineers, may contribute relentless effort and initiative to spread laboratory
researches and innovations to the large scale operation with the nourishment of knowledge and
skill of instrumentation in analysis. For this purpose, this course (Chem-352) has been
introduced to familiarize the students with modern analytical methods associated with
instrumentation which will lead us to future professional skills. The results obtained, by the use
of these instruments are accurate other than the classical methods: At the same time, the
consumption of time is much smaller than the classical methods. Some instruments, which have
the recorder and computer facilities, have created a new era in analytical chemistry. So,
knowledge for operation and handling of those instruments are badly needed and this course is
very much important from this point of view. To understand in depth of the instrumental
analysis, five experiments were performed in the laboratory. This term paper is just an
introduction of instrumental methods of analytical chemistry and covers the most common
instrumental methods. It is hoped that this term paper will provide the reader very basic idea
about the instrumental analysis and modern equipment used in the field of analytical chemistry.


iii
Acknowledgement

At first, I want to express utmost gratitude to the almighty Allah to let me complete this term
paper on the course Chem-352 I nstrumental Methods of Analysis. I am thankful to my
honorable teacher Dr. MD. Nazrul Islam and Dr. Md. Rafique Ullah who guided and helped
me at every stage to perform a successful substantial work. His constructive comments made
me able to complete this work successfully. I would also like to thank the lab assistants who
helped our group to establish the experimental setup. I thank my group partners for their
continuous co-operation. I am also grateful to my classmates who helped me by sharing their
knowledge and ideas about this experiment. And at last, I state my gratitude to the Department
of Chemistry, BUET.






























Md. Hasib Al Mahbub
10
th
June, 2013

iv
Table of contents



Topics Page no
Preface ii
Acknowledgement iii
Table of contents iv
List of Illustrations v
Introduction 7
Historical background 8
Analytical Chemistry 10
Approaches of analytical chemistry 12
Instrumental Methods of Analysis 14
Applications of Analytical Chemistry 17
Process of Instrumental Analysis 18
Limitations 20
Potentiometric Titration 22
Conductometric Titration 28
pH-metric Titration 38
Spectrophotometric analysis 46
Electrogravimetric Analysis 56
Conclusion 63
Bibliography 64
Appendices 65
Appendix-A: Experimental results for potentiometric titration 66
Appendix-B: Experimental results for Conductometric titration 71
Appendix-C: Experimental results for pH metric titration 75
Appendix-D: Experimental results for Spectrophotometric analysis 81
Appendix-E: Experimental results for Electrogravimetric analysis 83


v
List of ILLUSTRATIONs
Topics Page No
Figure-1: Block diagram of an analytical instrument showing the stimulus
and measurement of response
15
Figure-2: End point determination of potentiometric titration 24
Figure-3: Potentiometer in Laboratory 24
Figure-4: Conductometric titration curve for strong acid and strong base. 29
Figure-5: Conductometric titration curve for weak acid and strong base 29
Figure-6: Conductometric titration curve for acetic acid titrated using
solution of sodium
30
Figure-7: Conductometric titration curve for the hydrochloric acid acetic
acid mixture titrated using solution of sodium hydroxide.
31
Figure-8:Graph of Conductance vs. volume of NaOH 32
Figure-9: Schematic diagram of wheatstone bridge 33
Figure-10: Flask type conductance cell 34
Figure-11: Conductometer used in Laboratory; Model (CMD=750) WPA,
Linton Cambridge company
34
Figure-12: pH vs volume of HCl graph for determination of end point 40
Figure-13: Operating principle of glass electrode method 41
Figure-14: Scheme of typical pH glass electrode 41
Figure-15: Combined electrode(glass and calomel) in pH metric Titration 42
Figure-16: The electromagnetic spectrum 47
Figure-17: A typical absorbance spectrum 48
Figure-18: Components of a Spectrophotometer 49
Figure-19: Absorbance vs Wavelength graph 50
Figure-20:Absorbance vs. concentration graph 50
Figure-21: Diagram of a single-beam UV/vis spectrophotometer. 51
Figure-22:Working principle of a spectrophotometer 52
Figure-23: Samples of different concentration 53
Figure-24:Spectrophotometer in the lab

53
Figure-25:Basic construction of an electrolytic cell 56
Figure-26: Schematic Diagram of Electrogravimetric analysis 58
Figure-27: Instrument used in laboratory for electrolysis 59
Figure-28:Copper deposition on the platinum electrode 59
Graph-A.1: EMF of cell vs. Volume of K2Cr2O7 68

vi











Graph-A.2:
dV
dE
vs. Volume of K2Cr2O7
69
Graph-A.3:
2
2
dV
E d
vs. Volume of K2Cr2O7(ml)
70
Graph-B.1: Specific conductance vs. Volume of HCl graph 74
Graph-C.1: pH vs. Volume of HCl graph 77
Graph-C.2:
V
pH

vs. Volume of HCl graph

79
Graph-C.3:
2
2
V
pH

vs. Volume of HCl graph

80
Graph-D.1: Graph of absorbance(A) vs concentration of Iron 82
Table-A: Stages in Instrumental analysis 18
Table 1:Observed and calculated data for volume,cell EMF, first and
second derivative of cell EMF
66
Table 2: Table for volume of NaOH (ml) & conductance (ms) 71
Table 3: Data for Determination of the Strength of Oxalic Acid 71
Table 4: Observed and Calculated data for pH-matric titration 75
Table 5: Table for observed data of absorbance of different concentration 81

7
Introduction
Instrumental methods of chemical analysis have become the principal means of obtaining
information in diverse areas of science and technology. The speed, high sensitivity, low limits
of detection, simultaneous detection capabilities, and automated operation of modern
instruments, when compared to classical methods of analysis, have created this predominance.
Professionals in all sciences base important decisions, solve problems, and advance their fields
using instrumental measurements. As a consequence, all scientists are obligated to have a
fundamental understanding of instruments and their applications in order to confidently and
accurately address their needs. A modern, well-educated scientist is one who is capable of
solving problems with an analytical approach and who can apply modern instrumentation to
problems. With this knowledge, the scientist can develop analytical methods to solve problems
and obtain appropriately precise, accurate and valid information. The goal of a chemical
analysis is to provide information about the composition of a sample of matter. In some
instances qualitative information concerning the presence or absence of one or more
components of the sample suffices, in other instances quantitative data are sought. Regardless
of the need, however, the required information is finally obtained by measuring some physical
property that is characteristically related to the component or components of interest.
Instrumental method of chemistry is the part of analytical chemistry. It is defined as the
measurement of a physical property of a sample. Instrument have bought for mankind such
comfort as man can never dreamed of even in a fairly land. 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.
The objective of this course (Chem-352) is to introduce the students with the instruments,
which are now currently used in analytical laboratories. To understand the depth of the
instrumental analysis, five experiments are performed in the laboratory. Those are as follows:
Potentiometric titration
Conductometric titration


8
pH metric titration
Spectrophotometric analysis
Electrogravimetric analysis

It is remarkable that accuracy, precision, reproducibility are the main theme in instrumental
methods of analytical chemistry. So instrumentation has become part and parcel to modern
chemistry.

HISTORICAL BACKGROUND
Much 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 rubidium (Rb) and caesium
(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 1970s many of these techniques began to be used together to achieve a complete
characterization of samples. Starting in approximately the 1970s into the present day analytical
chemistry has progressively become more inclusive of biological questions (bioanalytical
chemistry), whereas it had previously been largely focused on inorganic or small organic
molecules. Lasers have been increasingly used in chemistry as probes and even to start and
influence a wide variety of reactions. The late 20th century also saw an expansion of the

9
application of analytical chemistry from somewhat academic chemical questions to forensic,
environmental, industrial and medical questions, such as in histology.
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 was 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
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. 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.








10
Analytical chemistry

Analytical chemistry is the study of the separation, identification, and quantification of the
chemical components of natural and artificial materials.
The goal of analytical chemistry is to provide information is finally obtained by measuring
some physical properties that is characteristically related to the component or components of
interest.
The recent rapid advantages in our knowledge of the physical world parallel a similar rapid
advance in the science of analytical methods. As a chemical engineer, the beginning student
soon becomes aware of the importance of modern analytical methods in all branches of science.
Biologists, geographycists, engineers-all practice chemistry to some extent, and nearly all
chemists practice analytical chemistry. Chemistry is the study of the composition and behavior
of the natural world. Anyone wishing to know more about the composition of substances must
employ analytical methods to determine the kinds and amounts of compounds, elements,
atoms, and sub-atomic particles present in a given sample, as well as to examine the detail
arrangements of the various species. And to study the behavior of materials, analytical methods
must be used before, during, and after certain reactions or changes. Analytical chemistry
based on the theoretical principles and instrumentation of all methods. Analytical methods are
usually classified according to the property that is observed in the final measurement process.
There are two large divisions based on the kinds of material with-
Organic
Inorganic
Both of these can be subdivided into two groups:
Qualitative analysis.
Quantitative analysis



Analytical
Chemistry
Quantitative
Analysis
Qualitative
Analysis

11
Qualitative analysis: Qualitative analysis is the study of material and the separation and
identification of the component that make up the component that make up the compound and
the mixture.
Quantitative analysis: Quantitative analysis is the determination of the amount of the
constituent of a substance. Quantitative analysis can be further subdivided in terms of the types
of method employed.
There are in general three classes of methods.
Volumetric analysis
Gravimetric analysis
Physio-chemical(instrumental) analysis



Until about 1920 nearly all the analysis were founded on two main properties - volume and
mass. As a consequence gravimetric and volumetric procedures have come to be known as
classical method of analysis.
Volumetric Method
In this method the final determination of the quantity of a substance desired is made by a direct
or indirect measurements of a volume of standard reagent reacting with the substance in a
chemical reaction.
Gravimetric Method
This method requires the separation in a weighable form of the constituent being determined
from a measured amount of the substance containing the desired constituent. The final
measurement in this case is one of the weights.
Physico-Chemical Method
This method involves the final measurements of some physical properties of the composition
of the system as a whole.


Qualitative
Analysis
Volumetric
Analysis
Gravimetric
Analysis
Physico
Chemical
Analysis

12
Approaches of Analytical Chemistry

Most modern analytical chemistry is categorized by two different approaches such as analytical
targets or analytical methods.
By Analytical Targets
Bioanalytical chemistry
Material analysis
Chemical analysis
Environmental analysis
Forensics
By Analytical Methods
Spectroscopy
Mass Spectrometry
Spectrophotometry and Colorimetry
Chromatography and Electrophoresis
Crystallography
Microscopy
Electrochemistry
Traditional analytical techniques
Although modern analytical chemistry is dominated by sophisticated instrumentation, the roots
of analytical chemistry and some of the principles used in modern instruments are from
traditional techniques many of which are still used today. These techniques also tend to form
the backbone of most undergraduate analytical chemistry educational labs. Examples include:



13
Titration
Titration involves the addition of a reactant to a solution being analyzed until some equivalence
point is reached. Often the amount of material in the solution being analyzed may be
determined. Most familiar to those who have taken college chemistry is the acid-base titration
involving a color changing indicator. There are many other types of titrations, for example
potentiometric titrations. These titrations may use different types of indicators to reach some
equivalence point.
Gravimetry
Gravimetric analysis involves determining the amount of material present by weighing the
sample before and/or after some transformation. A common example used in undergraduate
education is the determination of the amount of water in a hydrate by heating the sample to
remove the water such that the difference in weight is due to the water lost.
I norganic qualitative analysis
Inorganic qualitative analysis generally refers to a systematic scheme to confirm the presence
of certain, usually aqueous, ions or elements by performing a series of reactions that eliminate
ranges of possibilities and then confirms suspected ions with a confirming test. Sometimes
small carbon containing ions are included in such schemes. With modern instrumentation these
tests are rarely used but can be useful for educational purposes and in field work or other
situations where access to state-of-the-art instruments is not available or expedient.












14
Instrumental methods of Analysis

Instrumental methods of analysis assume the supporting role of an indispensable tool in
advancing the state of knowledge in the fields of inorganic, organic and physical chemistry.
Instrumental methods are based on the measurement of optical, thermal and other properties.
Modern instrumental methods generally involve sophisticated instrumentation and they often
possess a high degree of selectivity and hence allow more rapid analysis
Few features clearly distinguish instrumental methods from the classical ones. Some
instrumental methods are more sensitive than classical techniques, but others are not. It is
necessarily true that instrumental procedures employ more sophisticated and more costly
apparatus than classical procedures. An instrument for chemical analysis does not generate
quantitative data instead simply chemical information to a form that is more readily observable.
Thus the instrument can be viewed as a communication device. It accomplishes this purpose in
several steps that includes:
Generation of a signal.
Transmission of the signal to one of different nature (called transduction)
Amplification of the transformed signal and
Presentation of the signal as a displacement on a scale or on the chart of
recorder.
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 day 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.
Summaries of major analytical fields where instrumental methods are extensively applied are
given below-
Molecular analysis
I) Nuclear magnetic resonance ii) Infrared spectroscopy
iii) UV absorption and UV fluorescence
Spectrophotometric Analysis
I) X- ray diffraction and absorption

15
ii) Radio tracer techniques iii) Mass spectrometry
Thermal analysis
I) Gas chromatography ii) Electromicroscopy
Elemental Analysis
I) Emission spectrograph ii) Flame photometry
iii) Atomic absorption spectroscopy.
The Nature of Measurement
The steps involved in a chemical determination are the following:
Generation of signal
Detecting and transducing the signal after its interaction with (or generation by) a sample of
interest.
Amplification
Processing or modification (conversion of the signal into a form suitable to operate a read out).
Output or read out (as a line on a chart, pointer deflection on a meter, digital reading etc.). Not
all steps are required in every measurement, nor is every step necessary associated with a
separate entity; instrument modules or subassemblies that perform to or more functions are
common.
Choice Of Method Of Measurement
A measurement begins with an examination of the chemical system of interest. Kinds of
information that must be learned about available samples are:
Physical state
Expected constituents and percentage ranges.
Amounts
Whether a measurement of a property of one constituent will be affected by the presence of
other constituents.

Figure-1: Block diagram of an analytical instrument showing the stimulus and
measurement of response

16
Different instrumental methods are-
Spectroscopy
Spectroscopy measures the interaction of the molecules with electromagnetic radiation.
Spectroscopy consists of many different applications such as atomic absorption spectroscopy,
atomic emission spectroscopy, ultraviolet-visible spectroscopy, x-ray fluorescence
spectroscopy, infrared spectroscopy, Raman spectroscopy, nuclear magnetic resonance
spectroscopy, photoemission spectroscopy, Mssbauer spectroscopy and so on.
Mass Spectrometry
Mass spectrometry measures mass-to-charge ratio of molecules using electric and magnetic
fields. There are several ionization methods: electron impact, chemical ionization, electrospray,
fast atom bombardment, matrix assisted laser desorption ionization, and others. Also, mass
spectrometry is categorized by approaches of mass analyzers: magnetic-sector,quadrupole
mass analyzer, quadrupole ion trap, Time-of-flight, Fourier transform ion cyclotron resonance,
and so on.
Crystallography
Crystallography is a technique that characterizes the chemical structure of materials at the
atomic level by analyzing the diffraction patterns of usually x-rays that have been deflected by
atoms in the material. From the raw data the relative placement of atoms in space may be
determined.
Electrochemical Analysis
Electroanalytical methods measure the potential (volts) and/or current (amps) in an
electrochemical cell containing the analyte. These methods can be categorized according to
which aspects of the cell are controlled and which are measured. The three main categories are
potentiometry (the difference in electrode potentials is measured), coulometry (the cell's
current is measured over time), and voltammetry (the cell's current is measured while actively
altering the cell's potential).
Standard Curve
A standard method for analysis of concentration involves the creation of a calibration curve.
This allows for determination of the amount of a chemical in a material by comparing the
results of unknown sample to those of a series known standards. If the concentration of element
or compound in a sample is too high for the detection range of the technique, it can simply be

17
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.

Applications of Analytical Chemistry

Analytical chemistry has played critical roles in the understanding of basic science to a variety
of practical applications, such as:
Biomedical applications
Environmental monitoring
Quality control of industrial manufacturing
Forensic science and so on.
The recent developments of computer automation and information technologies have
innervated analytical chemistry to initiate a number of new biological fields. For example,
automated DNA sequencing machines were the basis to complete human genome projects
leading to the birth of genomics. Protein identification and peptide sequencing by mass
spectrometry opened a new field of proteomics.
Also, analytical chemistry has been an indispensable area in the development of
nanotechnology. Surface characterization instruments, electron microscopes and scanning
probe microscopes enables scientists to visualize atomic structures with chemical
characterizations.
Analytical chemistry is pursuing the development of practical applications and commercial
instruments rather than elucidating scientific fundamentals. This may be an arguable difference
from overlapping science areas such as physical chemistry and biophysics, although there
arent any distinct boundaries among disciplines in contemporary science and technology.
However, this aspect may attract many engineers' interest; thus, it is not difficult to see papers
from engineering departments in analytical chemistry journals.
Among active contemporary analytical chemistry research fields, micro total analysis system
is considered as a great promise of revolutionary technology. In this approach, integrated and
miniaturized analytical systems are being developed to control and analyze single cells and

18
single molecules. This cutting-edge technology has a promising potential of leading a new
revolution in science as integrated circuits did in computer developments.
Process of Instrumental Analysis

Instrumental analysis may be stated as the application of a process or series of processes to
identify and/or quantify a substance, the components of a solution or mixture, or the
determination of the structures of chemical compounds.
When a completely unknown sample is presented to an analyst, the first requirement is to
ascertain what substances are present in it. Having ascertained to the nature of the constituents
of a given sample, the analyst is then frequently called upon to determine how much of each
component, or of specified components, is present.

Stages of Analysis

The objective and purpose of the analysis has to be sensibly assessed before selecting an
appropriate procedure. A complete instrumental analysis, even for a single substance, involves
a series of steps and procedures. Each one of them has to be carefully considered and assessed
in order to minimize errors and to maintain accuracy and reproducibility. The steps are listed
in the table below:
Table-A: Stages in Instrumental analysis

Stages Examples of procedure
1. Sampling Depends on the size and physical nature of
the sample
2. Preparation of analytical sample Reduction of particle size, mixing for
homogeneity, drying, determination of
sample weight or volume.
3. Dissolution of sample Heating, ignition, fusion, use of solvent(s)
dilution
4. Removal of interferences Filtration, solvent extraction, ion exchange,
chromatographic separation

19
5. Sample measurement and control of
instrumental factors
Standardization, calibration, optimization,
measurement of response; absorbance,
emission signal, potential, current
6. Calculation Calculation of analytical result(s) and for
the sample, statistical evaluation of data
7. Presentation of data Printout, data plotting, storage(archiving)

Selecting the Method
Important factors which must be taken into account when selecting an appropriate method of
analysis include
The nature of the information which is sought
The size of sample available and the proportion of the constituent to be determined,
and
The purpose for which the analytical data is required

According to the supplied information and required data generation instrumental analyses may
be classified into four types as follows-
Proximate analysis determines the amount of each element in a sample but not the
compounds that are present.
Partial analysis determines selected constituents in the sample.
Trace constituent analysis is a type of partial analysis that determines specified
components present in very minute quantity.
Complete analysis determines the proportion of each component in the sample.

On the basis of sample size, analytical methods are often classified as follows:
Macro : > 0.1g
Meso (semimicro) : 10
-2
g to 10
-1
g
Micro : 10
-3
g to 10
-2
g
Submicro : 10
-4
g to 10
-3
g
Ultra micro : < 10
-4
g
Trace : 10
2
to 10
4
g g
-1
(100 10000 ppm)



20
Limitations


The instruments used in instrumental analysis are expensive enough that most ordinary
laboratories of third world countries cannot afford them. There are some instruments in
our laboratory which are unique of their kind in our country. So, unavailability of
instruments is a major problem for institutions and organizations of least developed
countries.
The special technique of instrumental analysis requires special treatment of samples to
be prepared for the instruments. To prepare these samples a large number of steps have
to be followed.
An instrumental method is a cost effective technique when it is used in large number of
operations. But for an occasional, non-routine analysis it is often better to use classical
method.
Some instruments are so sophisticated and sensitive that any unmindful operation can
cause a notable damage.
Most of the instruments are manufactured in developed countries and the parts, as well
as sales services, are not available everywhere so, a little damage in any parts may
results the invalidation of the instrument as a whole.

















21
Experiments performed





E
X
P
E
R
I
M
E
N
T
S
POTENTIOMETRIC
TITRATION
pH METRIC
TITRATION
CONDUCTOMETRIC
TITRATION
ELECTROGRAVIMETRIC
METHOD
SPECTROPHOTOMETRIC
METHOD

22
Potentiometric titration

SAMPLE:Fe
2+
SOLUTI ON TI TRATED WI TH K2Cr2O7

Based on the electrical properties of metals and their ionic solution, several analytical
techniques have been developed. The branch of quantitative analysis involving the estimation
of substances in solution by the measurement of potentials is known as potentiometric analysis
or potentiometric titration. The potential of an electrode relative to a reference electrode varies
in a predictable way with the activities of species, which undergo oxidation or reduction
reactions at the electrode surface. In potentiometric titration, the measurement of potential
serves to locate the equivalents points for titration. Potentiometric titration yields primarily
stoichiometric information. The essential condition to conduct this titration is that the reaction
must be involved the addition or removal of some ion for which an electrode is available.
Theory
Potentiometry deals with the measurement of potential. The cell potential depends on the
potential of the electrodes which in turn depends on the activity of the solution, temperature,
electrodes material, etc. Ordinarily the potentiometric titration involves measuring and
recording the cell potentials after each addition of reagent. This method can be applied to locate
the end point of a titration reaction provided the activity of at least one of the substances
involved can be followed by means of a suitable indicator electrode whose emf is given by
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.
RT
E =E
0
+--------- ln aM
n+
nF

Where,
E= emf of the electrode,
Eo= emf of the electrode at standard condition
n = number of electron transferred during reaction
F= Faradays number
Potentiometric titration based upon the quantitative relationship between the emf of a cell is
given by the distribution of potential
Ecel l = Eref + Ei ndi cator+Ej uncti on

23
The reference electrode potential and the junction potential is assumed to remain more or less
constant. So the change of potential of a suitable indicator electrode is observed as a function
of volume added of a titrant of precisely known concentration.

Chemistry Involved
To estimate the amount of Fe++ in a solution a platinum electrode (reference electrode) was
connected to a potentiometer. The solution was titrated against standard K2Cr2O7 solution.

Reaction

Calomel electrode (left): Hg2Cl2 + 2e- = 2Hg + 2Cl -
Platinum (right): F e
++
- e
-
= F e
+++
, E0 = 0.76v
Cr2O7
- -
+ 14H
+
+ 6e
-
= 2Cr
++
+ 7H2O
Emf of the cell is given by,
Ecel l = El eft- Eri ght (oxi dation potential )

This reaction can be divided in to two half-cell reactions. Here ferrous ion is oxidized to ferric
by leaving electrons and these are picked up by dichromate ion. The conversion to ferric ion
from ferrous causes an electromotive force, which can be recorded by the potentiometer. The
endpoint occurs when the entire ferrous ion is converted to ferric ion and this is denoted by the
abrupt change in the magnitude of potential. Here potassium dichromate was used to help the
conversion of ferrous ion to ferric ion. The electrode emf is given by

E = E0 + 0.0591 l og[ F e
+++
]/[ F e
++
]

A platinum wire dipped in to the solution picked up the potential and served as an electrical
contact between the electrodes. Plot of potential against volume of titrant added, was used to
find the endpoint of the titration. For more satisfactory deduction of the endpoint slope of the
above curve against the volume of titrant added was constructed. By such a plot it is possible
to obtain a sharp maximum value and hence within narrow limits, the volume of titrant added.
End Point Determination
The end point of a titration may be established any of several ways. The most straightforward
method involves a visual estimation of the midpoint in the steeply rising portion of the curve.

24
Various mechanical methods have been suggested for evaluation of this point; it seems
doubtful, however, these improve the accuracy of estimation greatly.
End point may be determined graphically by plotting the change in potential per unit in volume
of reagent (dE/dV) as a function of the average volume of reagent added. The end point is taken
as maximum in the curve and is obtained by extrapolation of experimental points.






Figure 2: End point determination of potentiometric titration
Instrumentation
The essential instrument used for this experiment was a potentiometer with milivolt scale
connected with saturated calomel electrode and platinum electrode. The potentiometer operated
according to the Poggendroff compensation principle. Ordinarily the titration involves
measuring and recording the cell potential after each addition of reagent. The solution is added
in large increments at the beginning, as the end point is approached the increments are made
smaller.









Figure 3: Potentiometer in Laboratory
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.

25
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 0.1 ml of
the titrant up to 13 ml of K2Cr2O7 solution.
The solution must be stirred during titration.

Reference Electrode
In this experiment a standard calomel half-cell electrode is a secondary standard electrode. In
this electrode mercury and calomel are covered with potassium chloride solution of definite
concentration which may be 0.1M, 1M or standard. These electrodes are referred to as the
deciolar, the molar and the standard calomel electrode (SCE) respectively. These electrodes
have the potentials relative to the standard hydrogen electrode (SHE) at 25
0
c of 0.3358 volt,
0.2824 volt and 0.2444 volt respectively. Calomel electrode represented as Hg|Hg2Cl2(S)/C1
-
(C). The electrode reaction is,
Hg2Cl2(S) +2e
-
=2Hg (liquid) +2Cl
-


Indicator Electrode
The indicator electrode of a cell is one whose potential is dependent upon the activity and
therefore the concentration of a particular ionic species whose concentration is to be
determined. In direct potentiometry or the potentiometric titration of a metal ion, a simple
indicator electrode will usually consist of a carefully cleaned rod or wire of the appropriate
metal (eg. pt). It is important that the surface of the metal to be dipped in to the solution is free
from oxide films or any corrosive product.

Advantages
The main advantage of the method is that it can be applied for turbid, fluorescent,
opaque, or colored solutions or when suitable visual indicators are unavailable or inapplicable.
It provides inherently more accurate data than the indicator method.
It is useful for detecting the presence of unsuspected species in a solution.

26
In acid base titration, the potentiometric method can be employed with advantage where
the solution has a natural color of their own e.g. ink, vinegar and where titration with indicators
is not possible.
Solutions containing more than one halide can be analyzed in a single titration against
silver nitrate using a silver electrode in potentiometric titration.
The end point can be located precisely, even with dilute solutions and also in the
titration of a mixture.

Disadvantages
Its main disadvantages are the more time and attention requirement and the difficulties
associated with the preparation, standardization and storage of standard titrant solution

Result
Required volume of K2Cr2O7 for titration = 4.45 ml
Strength of Fe
++
ion in the solution = 0.02225 (N)

Discussion
The aim of this experiment was to determine the end point of the titration. For this purpose
three curves have been plotted from the experimental data. The experimental plots are very
close to the theoretical plot. So the experimental performance was good.
The potentiometric titration of ferrous ferric ion system is based on the fact that the transfer of
electron takes place rapidly and reversibly when the reduced and oxidized forms have the
essentially identical structure. 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 Nernst equation. After each addition of K
2
Cr
2
O
7
this ratio changes and EMF changes
gradually. The critical problem in a titration is to recognize the point at which the quantities of
reacting species are present in equivalent amounts-the equivalence points. 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.
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

27
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.
A second approach was to calculate the change in potential per unit change in volume of reagent
[that is, E / V] as has been done in Table 1. A plot of this parameter as a function of average
volume leads to a sharp maximum at the end point. 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
2
E / V
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.
This assumption is perfectly valid, provided the participants in the chemical process react with
one another in an equimolar ratio, and also provided the electrode process is perfectly
reversible. 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.

















28
Conductometric titration

SAMPLE: HCl ACI D & CH3COOH ACI D TI TRATED WI TH NaOH SOLUTI ON

Titration in which conductivity measurements are made use of, in determining the end point of
acid base reaction, some displacement reactions or precipitation reactions are called
Conductometric titration. The conductance of a solution is a measure of how well a solution
carries a current. It is reciprocal of the electrical resistance and has the unit of ohm
-1
or mho. It
is represented by LS.
Theory

The positive ions migrate through the solution towards the cathode, where they pick up
electrons. Anions migrate towards the anode, where they deliver electrons. The net result is a
flow of electrons through the solution. Thus the electrical conductance of a solution at a
constant temperature depends upon the number of displaceable electrons in the solution and
their mobility under the influence of an applied electromotive force. The addition of an
electrolyte to a solution of another electrolyte under conditions producing no appreciable
change in volume will affect the conductance of a solution according to whether 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 NaNO3), 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 ion 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 anion D
-
of the reagent.
If the product of the reaction, AD is relatively insoluble or only slightly ionized the reaction
may be written as:
A
+
B
-
+ C
+
D
-
= A
+
D
-
+ 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
whether the conductivity of the C
+
ions is greater or less than that of the A
+
ions.




29
Chemistry of strong acids & weak acids with strong bases



End point


Conductance




Volume of base

Figure 4: Conductometric titration curve for strong acid and strong base.


Reaction: (H
+
+Cl
-
) +(Na
+
+OH
-
) =(Na
+
+Cl
-
) +H2O

Again when a weak acid like acetic acid is titrated against a strong alkali like Sodium
Hydroxide (NaOH) a curve of the following type is obtained. The initial conductivity of the
solution is low because of the poor dissociation of the weak acid. On addition of alkali, highly
ionized sodium acetate (CH3COONa) is formed. The acetate ions at first tend to suppress the
ionization of acetic acid still further due to common ion effect. But after a while the
conductivity begins to increase because the conducting power of highly ionized salt exceeds
that of the weak acid.
Reaction: CH3COOH +Na
+
+OH
-
=CH3COO
-
+Na
+
+H2O


End point

Conductance






Volume of base
Figure 5: Conductometric titration curve for weak acid and strong base.

Immediately after the end point, further addition of NaOH introduces the fast moving hydroxyl
ions and the conductivity value shows a sharp increase. The point of intersection of the two
curves therefore gives the end point.

30
Consider the titration of solution of weak acid, such as acetic acid CH3COOH, using a solution
of strong base, NOH. 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 6: 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 observed until
the equivalence point is reached, at which we have a solution of sodium acetate, CH3COONa.
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

31
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.11.

Figure 7: 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.



32
CHEMICAL REACTIONS
Sodium Hydroxide, Acetic acid and Sulfuric acid ionize in the solution in the following forms:
NaOH =Na
+
+OH
-

HCl =H
+
+Cl
-
CH3COOH =CH3COO
-
+H
+
Then the following reactions occur:
Na
+
+Cl
-
=NaCl
H
+
+OH
-
=H2O
NaOH +HCl =NaCl +H2O
NaOH +CH3COOH =CH3COONa +H2O
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 8: Graph of Conductance vs. volume of NaOH


33
Instrumentation
1. Instrument used in the lab: CMD 750 WPA conductivity meter
2. An electro chemical cell with a pair Pt electrodes

Conductometer:
The conductivity of an electrolyte solution is a function of the concentration of ions in the solution.
Because of this, each solution has a resistance that can be measured with conductivity cells.
L=1/
where, L= conductance and = resistivity of a substance. These are characteristic quality of a
material. of a material depends upon its concentration and other properties.
Conducting sensors are constructed of an insulating material imbedded with metallic pieces. The
metal pieces, serving as sensing elements, are placed at a fixed distance apart and make contact
with the solution. The cell constant, K, for a particular conductivity cell is determined by the
geometry of the cell. The value of K can be estimated by the following equation:


where d is the distance between the sensing elements and A is the surface area of one sensing
element exposed to the solution.
When measuring the resistance of a solution it is impractical to use an ohmmeter, since passing a
current through the solution will lead to errors, such as heating and polarization. Using AC
potential eliminates the latter problem, but an AC Wheatstone bridge minimizes both of the above
problems. In Figure 13, Rf1 and Rf2 are fixed resistors of known resistance; Rb is a resistance
box in which the resistance can be changed very precisely over a wide range; and Rm is the
resistance to be measured, in this case the conductivity cell with the solution of interest.



Figure 9: Schematic diagram of Wheatstone bridge

A
d
K=



34
The bridge works correctly when V2 = V4 and therefore Rm = Rb(Rf1/Rf2). If the two fixed
resistors are chosen to be identical, then Rm is equal to the reading of the variable resistance
box Rb. (2)

Conductance cell
Different types of cells are used for conductance measurement. A cell which is commonly used
is shown in figure-14. 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 10: Flask type conductance cell

Figure 11: Conductometer used in Laboratory; Model (CMD=750) WPA, Linton
Cambridge company


35
Method of Operation

20 ml mixture of HCl and acetic acid was taken in a conductivily cell.
Secondary standard NaOH was added in an amount of 0.5 ml each time from a burette.
For every addition the corresponding reading of specific conductances were taken.
A graph of specific conductance vs Volume added of NaOH was plotted
From the graph the end point strength of HCland acetic acid was determined

Advantages

Sometimes the end point in an acid-base titration reaction cannot 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 NH3) or with a strong base (e.g. NaOH) reasonably satisfactory end points are
obtained.
The apparatus required for making conductance measurements and performing titration is
generally inexpensive and basically simple in detail. For these reason the measurement of
conductance finds wide acceptance in industry as an analytical tool, both in the laboratory
and in process control.
Conductometric methods may be applied where visual or potentiometric methods fails to
give result owing to considerable solubility or hydrolysis at the equivalent point very week

36
point , such as boric acid and phenol which cannot titrated potentiometrically aqueous
solution, can be titrated conductometrically.
Another important advantage is that this method is as accurate in dilutes in more
concentrated solution.
This method can be employed with colored solution.
Disadvantages
Conductometric titration may be used only to detect the end point of a comparatively simple
system in which there is no excessive amount of reagent present. Thus many oxidation titration
which require the presence of relatively amounts of acid are not suitable to conductometric
titration.
The plot obtained in Conductometric titration cannot use for solutions of different
concentrations of the same species.
Application
Conductometric Titration is applied for determining the level of contamination of water or any
other chemical species, as the conductance of pure species of different substances are constant.
Result
Strength of `HCl= 0.19 N
Strength of CH3COOH = 0.212 N
Percentage of HCl= 35.28%
Percentage of CH3COOH = 64.72%

Discussion
In this experiment strong acid HCl and weak acid CH3COOH is titrated at the same time with
strong base NaOH solution so there should be two end points. According to Graph-C.1
(Appendix-C) two definite end points are observed. The first of these indicate neutralization of
HCl acid (strong acid) and second of these indicate neutralization of CH3COOH acid (weak
acid). So the result is satisfactory.
In this experiment, the Conductometric titration curve for a weak acid (CH3COOH) 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

37
to the second end point, which indicate the neutralization of CH3COOH acid with NaOH
solution and then the conductance rise sharply again as NaOH introduces the fast moving
hydroxyl ion. This characteristic of the curve is described in brief below
In the titration of a strong acid (HCl) with base (NaOH), the conductivity of the solution
containing acid decreases and continues to fall with every subsequent addition of alkali till the
end point is reached. After the equivalent point, the further additions of NaOH solution results
in an increase of conductance since the hydroxyl ions are no longer removed in the chemical
reaction in the form of freely ionized water. The point of minimum conductance therefore
coincides with the end point of the titration.
In the titration of a weak acid (CH3COOH) with strong base (NaOH solution), on addition of
alkali highly ionized CH3COONa is formed. The acetate ions at first tend to suppress the
ionization of an acetic acid still further. But after a while the conductivity begins to increase
because the conducting power of highly ionized salt exceeds that of the weak acid. Immediately
after the end point, further addition of sodium hydroxide introduces the fast moving hydroxyl
ions and the conductivity value shows a sharp increase.
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 size and separation of the electrodes will be governed by the change of conductance
during the titration. For low conductance solutions (e.g. when solution is extremely dilute)
the electrodes should be large and should be placed closely.
It is not necessary to know the cell constant since relative values are sufficient to permit
locating the equivalence point, &
During titration, if the cell is connected to a pen recorder in addition to the conductivity
meter a plot of change in conductance with addition of reagent can be drawn automatically.

38
P H metric titration
Sample: HCl Acid Titrated With NaOH
Introduction
The purpose of the experiment was to perform the pH metric titration of sodium carbonate by
using HCl as titrant. In 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.
Theory
Acidity and basicity of a solution may be described in terms of its hydrogen ion concentration.
Sorenson in 1909 devised a measure of hydrogen ion concentration which is convenient and at
the same time compact. He introduced the term pH and designed it as the negative value of
logarithm of hydrogen ion concentration.
pH=-log10 [H
+
]
With the introduction of the concept of activity the correct definition is
pH=-log aH
Where, aH = hydrogen ion activity
In acid base titration pH of the test solution changes with every addition of titrant. This change
is very sharp in the vicinity of end point. So, end point can be located from the change of pH.
This is the underlying principle of pH titration.
A variety of electrodes available for pH measurement the hydrogen gas electrode, the glass
electrode, the antimony electrode, the quinhydrone electrode etc. The arrangement of the cells
which are pH responsive is known as pH cell. In this course glass electrode was chosen as to
construct a pH responsive cell.
The glass electrode, actually a membrane electrode comprises a thin walled bulb of pH -
responsive glass sealed to a stem of non-pH-responsive, high resistance glass.
The potential of the glass electrode is given by,
E =Ee +.000198T (pH -pHr)
Where,
pHr= pH of the reference solution contained within the glass bulb
Ee =combination of junction potential
T =Temperature in degree Kelvin


39
From the above equation it can be seen that there exists a relation between the pH of a solution
and the electrode potential of an electrode that is dipped in the solution.
The conventional pH value may be defined in an operational manner, as follows,
pH =pHs +(E-Es).000198T.
Where,
E= emf of pH cell which cantains an unknown solution.
E s= emf of pH cell which contains standard referance of known pH.
So, change in electrode potential following a change in hydrogen ion concentration shows the
change in pH. A pH meter is added to the electrodes to convert the change in electrode-potential
in terms of pH and display it in the monitor)
CHEMISTRY INVOLVED
The combination electrode was dipped in the Na2CO3 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 Na2CO3, 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:

Na2CO3 + HCl NaHCO3 + NaCl

NaHCO3 + HCl NaCl + H2CO3


CO2 + H2O


40
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.







Figure 12:pH vs volume of HCl graph for determination of end point
To determine the more accurate end point d
2
pH/dV
2
graph is also plotted.
Instrumentation
The essential instruments used for pH measurements are.
(i) pH meter ( pH/ion meter. 150 CORNING) an electronic digital volt meter scaled to read
pH directly
(ii) A combination electrode connected to the pH meter.
The combination electrode contains an indicator electrode (a thin glass electrode) and a
reference electrode (calomel electrode) combined in a single unit. The thin glass bulb is filled
with HCl of const. pH and carry the calomel electrode.
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 hydrogen
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.

41

Figure 13: Operating principle of glass electrode method
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 14: Scheme of typical pH glass electrode
1. a sensing part of electrode, a bulb made from a specific glass
2. sometimes the electrode contains a small amount of AgCl precipitate inside the glass
electrode
3. internal solution, usually 0.1M HCl for pH electrodes or 0.1M MeCl for pMe electrodes
4. internal electrode, usually silver chloride electrode or calomel electrode

42
5. Body of electrode, made from non-conductive glass or plastics.
6. reference electrode, usually the same type as 4
7. Junction with studied solution, usually made from ceramics or capillary with asbestos or
quartz fiber.
Combined Electrode
Typical modern pH probe is a combination electrode, which combines both the glass and
reference electrodes into one body. The bottom of a pH electrode balloons out into a round thin
glass bulb. The pH electrode is best thought of as a tube within a tube. The inside most tube
(the inner tube) contains an unchanging saturated KCl and a 05M HCl solution. Also inside the
inner tube is the cathode terminus of the reference probe. The anodic terminus wraps itself
around the outside of the inner tube and ends with the same sort of reference probe as was on
the inside of the inner tube. Both the inner tube and the outer tube contain a reference solution
but only the outer tube has contact with the solution on the outside of the pH probe by way of
a porous plug that serves as a salt bridge.
The measuring part of the electrode, the glass bulb on the bottom, is coated both inside and out
with a ~10nm layer of a hydrated gel. These two layers are separated by a layer of dry glass.
The silica glass structure (that is, the conformation of its atomic structure) is shaped in such a
way that it allows Na
+
ions some mobility.






Figure 15: Combined electrode (glass and calomel) in pH metric Titration
The metal cations (Na
+
) in the hydrated gel diffuse out of the glass and into solution while H
+

from solution can diffuse into the hydrated gel. It is the hydrated gel, which makes the pH
electrode an ion selective electrode. H
+
does not cross through the glass membrane of the pH

43
electrode, it is the Na
+
which crosses and allows for a change in free energy. When an ion
diffuses from a region of activity to another region of activity, there is a free energy change
and this is what the pH meter actually measures. The hydrated gel membrane is connected by
Na
+
transport and thus the concentration of H
+
on the outside of the membrane is 'relayed' to
the inside of the membrane by Na
+
.
Procedure
Procedure mention mentioned below is followed during performing this experiment:
(1) 20 ml of NaCO3 solution is taken into a beaker
(2) 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.
(3) 0.2 (N) HCl solution is added in the beaker containing Na2CO3 solution by using a
burette and corresponding pH reading is taken from pH meter.
(4) Each time .2 to .3 ml of 0.2 N HCl acid is added until end point is reached.

Advantages
pH metric titration has some unique advantages. Some of them are given below:
In colored solutions, Indicators cannot 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 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 without 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.

44
Disadvantage
The main limitations of pH-metric titration arise 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.
Results
Strength of Na2CO3 solution = 0.05N
First dissociation constant, pK1= 7.7
Second dissociation constant, pK2= 5.25

Discussion
The purpose of this experiment was to study the nature of Na2CO3-HCl titration with the
measurement of pH and to plot the titration curve of pH vs. milliliters of titrant added. The pH
values were directly obtained from a pH meter.
The pH curve shows pH changes sharply twice during the process. This indicates that the
overall reaction takes place in two steps. pH level of Na2CO3 solution is maximum before
adding HCl. As HCl is added, pH of the resulting solution decreases gradually. At the first
vertical portion of the curve, pH decreases sharply. This point indicates the completion of 1st
step of the overall reaction:
Na
2
CO
3
+HCl =NaHCO
3
+NaCl.
Complete conversion of CO
3
-2
to HCO3
-
takes place at this point. pH value corresponding to
this point represents the 1st ionization constant of Na
2
CO
3
. As the process continues pH
decreases slowly again until the 2nd steeper portion is reached. At this 2nd end point there is
another sharp fall of pH. This indicates the completion of 2nd part of the overall reaction.
NaHCO3 +HCl =NaCl +H2O +CO2
This point indicates the conversion of HCO3
-
to H2CO3 followed by dissociation of carbonic
acid to H2O and CO2.
To locate the end points accurately, a first derivative plot of pH/V vs. volume is constructed
from the pH curve. This plot shows two sharp peaks, which indicates the locations of two
endpoints. For more accuracy a second derivative
2
pH/V
2
Vs V is plotted.

45
This point indicates the conversion of HCO3
-
to H2CO3 followed by dissociation of carbonic
acid to H2O and CO2.

From the second derivative vs volume curve the pK values for HCl can be determined,
According to the Hendersons equation:
pH=pK+log
| |
| | acid
salt

So when 50% of the acid is neutralized and forms salt then pH= pK, so from the curve the pK1
and pK2 values could be determined.

Temperature changes in the measured liquid affect both the response of the measurement
electrode to a given pH level , and the actual pH of the liquid.

Application

Titration of colored solutions can be done in this method as indicators are not suitable
for those solutions.
Electrolytes of blood and their concentration can be determined in this method
pH of amino acid and its properties in the body can be measured through it.














46
SPECTROPHOTOMETRIC ANALYSIS

Sample:Fe
3+
solution
Introduction
Spectrophotometric analysis is the most sophisticated analytical method & usually used to
analyze in ppm or ppb range both qualitatively & quantitatively. In this method the ratio of the
intensities of the incident and the transmitted beams of light is measured at a specific
wavelength by means of a detector (a photocell). The absorption spectrum also provides as a
fingerprint for qualitatively identifying the absorbing substance. The amount of visible light or
other radiant energy absorbed by a solution is measured since it depends on the concentration
of the absorbing substance; it is possible to determine quantitatively the amount 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 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. Finally, because particles in suspension will scatter
light (thus preventing it from reaching the light detector), spectrophotometers may also be used
to estimate the number of cells in suspension.
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.

47

Figure 16: 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
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.
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-20) is composed of wavelengths from
400 to 700 nm (nanometers). When visible light passes through a colored solution, some

48
wavelengths are transmitted and others are absorbed. We see the color of the transmitted
wavelengths. For instance, a 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 (Amax) for measuring absorbance is
that wavelength that is most absorbed by the compound in question. This provides maximum
sensitivity for your measurements. A hypothetical absorbance spectrum is shown in Figure -21

Figure 17: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 the slit width, the better the
ability of the instrument to resolve 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-22 for a schematic of a spectrophotometer.

49

Figure 18: Components of a Spectrophotometer
Theory
When light (monochromatic or heterogeneous) 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. If the intensity of the incident light is expressed by Io, that of the absorbed light
by Ia, that of the transmitted light by It, and that of the reflected light by Ir, than,
I o =I a +I t +I r
For air-glass interfaces, arising from the use of glass cell, it may be stated that about 4 percent
of the incident light reflected. It is usually eliminated by the use of a control, such as a
comparison cell, hence
I o =I a +I t
The two separate laws governing absorption are usually known as Lamberts Law and Beers
Law. In the combined form they are referred to as the Beer-Lambert Law, which is the
fundamental equation of spectrophotometry.
Lamberts Law states that when monochromatic light passes through a transparent medium,
the rate of decrease in intensity with the thickness of the medium is proportional to the intensity
of the light. The law may be expressed by the following equation:
dI /dt = kl
Where I is the intensity of the incident light of wavelength, t is the thickness of the medium,
and k is a proportionality factor. Integrating equation and putting I = Io,
ln (I o/I t) = kt
I t = I oe
-kt

Where Io is the intensity of the incident light falling upon an absorbing medium of thickness
l, it is the intensity of the transmitted light and k is a constant for the wavelength and the
absorbing medium used.
Beers Law states that the intensity of a beam of monochromatic light decreases exponentially
as the concentration of the absorbing substance increases arithmetically. This may be written
in the form:
I t = I o e
-k c
I t = I o.10
-k' c


Where c is the concentration and k and k' are constants. Combination of these two laws gives
Beer-Lambert Law:

50
I t = I o 10
-ccl

Since each isolated species of ion atom or molecule will exhibit an individual set of definite
energy levels, it will absorb only the frequencies that corresponds to excitation from one level
to another. In this experiment, the maximum wavelength (the wavelength at which maximum
absorbance occurs at first) was measured. Then with the help of maximum wavelength a curve
of absorbance vs. concentration was prepared by taking different concentration of the key
solution. The ion concentration at its definite absorbance at maximum wavelength is obtained
from this graph.



Chemistry Involved
When a transparent solution of Fe+3 ions is subjected to radiating light it remains inert with
respect to the system. So it is required to convert the Fe+3 ions into equivalent amount of
complexes, which are sensitive to spectrophotometry. This may be done by the addition of
ligands like SCN-. In an acidic Fe+3 ion solution, the excess amount of ligand forms ox-red
colored complex equivalent to Fe+3 ions.
F e
+3
+ SCN
-
=[F e(SCN)]
-3


Instrumentation
Spectrophotometer
UV/Vis spectroscopy is routinely used in the quantitative determination of solutions of
transition metal ions and highly conjugated organic compounds. The instrument used in
ultraviolet-visible spectroscopy is called a UV/vis spectrophotometer. It measures the intensity
of light passing through a sample (I), and compares it to the intensity of light before it passes
through the sample (Io). The ratio I / Io is called the transmittance, and is usually expressed as
a percentage (%T). The absorbance, A, is based on the transmittance:
Figure 19: Absorbance vs
Wavelength graph
Figure 20: Absorbance vs
Concentration graph

51
A = log(%T)
The basic parts of a spectrophotometer are a light source (often an incandescent bulb for the
visible wavelengths, or a deuterium arc lamp in the ultraviolet), a holder for the sample, a
diffraction grating or monochromator to separate the different wavelengths of light, and a
detector. The detector is typically a photodiode or a CCD. Photodiodes are used with
monochromators, which filter the light so that only light of a single wavelength reaches the
detector. Diffraction gratings are used with CCDs, which collects light of different wavelengths
on different pixels.


Figure 21: Diagram of a single-beam UV/vis spectrophotometer.
A spectrophotometer can be either single beam or double beam. In a single beam instrument
(such as the Spectronic 20), all of the light passes through the sample cell. Io must be measured
by removing the sample. This was the earliest design, but is still in common use in both
teaching and industrial labs.
Instrument used in the lab Bausch and Laumb spectronic-21
A spectrophotometer must consist of some essential components, such as-
Source
Prism
Screen(passing monochromatic light)
Spectrometer

52
Photo meter
Amplifier
Recorder






Figure 22: Working principle of a spectrophotometer
Each system will have proper slits, lenses, controls etc. curettes are required to hold the sample
which must be transparent to the of our interest and must be of fixed size. For a general
purpose instrument we need a way to produce broad range of with reasonable uniform
intensity. The goal of a wavelength selector is to only allow a specific to reach the detector
at any given time .

Source
Prism
Screen Spectrometer Photomete
r
Amplifier Recorder

53
Method of Operation
Procedure mentioned below is maintained during conducting this experiment-
1. Ferric solution of concentration 1 to 5 ppm are prepared and then 20ml 10% KSCN and
3ml 6(N) HNO3 acid is added in each of the prepared ferric solution.
2. Solution of concentration of 3 ppm is taken as standard solution.
3.
that each wavelength is adjusted to 100% transmittance for solvent i.e. distilled water.
4. Setting the spectrophotometer at the maximum wavelength, absorbance against each
concentration is evaluated.
5. Then absorbance VS concentration curve is constructed.
6. From the plot, which is a straight line, knowing absorbance of the unknown solution,
concentration of that solution is evaluated.
7. In order to evaluated maximum wavelength, absorbance VS wavelength spectrum is
plotted.





Advantages
Important characteristics of photometric method include
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.
Figure 23: Samples of different concentration Figure 24: Spectrophotometer in the lab



54
So as a whole it has- (a). wide applicability; (b). high sensitivity; (c). moderate to high
selectivity; (d). accuracy; & (e). convenience.

Disadvantages
For solutions that do not follow Beer-Lamberts law it cannot be used.
For very solutions (transmittance lie outside the range 0.20 to 0.65)BeerLamberts law
shows deviation. So problem arises in this range.

Results
From Calibration Curve:
If absorbance of a solution is = 0.505
Then Concentration of the solution = 3.52 ppm

Discussion
The prediction of Beer Lamberts law is verified in this experiment. By plotting absorbance Vs
concentration a straight line should be obtained which provides a linear relation between
absorbance and concentration.
The calibration curve of absorbance versus concentration (at constant wavelength) should pass
through the origin since at the zero concentration (Infinite dilution) absorbance must be zero.
But in this experiment, least square fitting of the curve 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 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
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 (Fe
3+
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. That is why KSCN is added to Fe
3+

solution. This forms a complex with Fe
3+
solution. A ligand (SCN
-
) had been added to form
color of the solution, as for colorless solutions no absorption will take place in the

55
spectrophotometer. again the Fe
3+
ion concentration is so minute that it couldnt form any color,
thats why the ligand (NH4SCN) had to be added.
The plot drown in Spectrophotometric estimation can be used for determining concentrations
of other solutions of the same species whereas in the other methods a plot can be used only for
that respective solution.

















56
ELECTROGRAVIMETRIC ANALYSIS
Sample: Brass Sample Containing Certain Amount Of Copper And Zinc

Introduction
Electrogravimetry is a special case of gravimetry where electrolysis is carried out and the
material deposited on one of the electrodes is weighed. In most applications the metal is
deposited on a weighed platinum cathode. This sort of electrolytic precipitation has been used
for over a century for the gravimetric determination of metals.
This topic will describe in brief the theory, chemistry of the process, experimental procedure,
instrumentation, advantage and limitation, result & discussion of electro gravimetric method
related to the experiment performed in the lab.
THEORY
When 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.

Figure 25: Basic construction of an electrolytic cell
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.

57
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.
Chemistry Involved
The chemistry involved in this experiment was purely the chemistry of a general electrolysis.
The positive ions of the electrolyte, in this case Cu
+
and H
+
collected

electrons from the
cathode whereas negative ions of the electrolyte, OH
-
in this experiment, delivered electrons to
anode.
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 the following reactions
occurred
Reaction at Cathode: Cu e Cu +
+
2
2


Reaction at Anode:

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


When the sample was dissolved in conc.HNO3 solution the following reactions took place-
Cu +4HNO3 =Cu
++
+2NO3
-
+2NO2 +2H2O
Zn +4HNO3 =Zn
++
+2NO3
-
+2NO2 +2H2O
The beneficial effect of nitrate ion is due to its depolarizing action at the cathode. The reaction
is

58
O H NH e H NO
2 4 3
3 8 10 + + +
+ +

The reduction potential of NO3
-
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 (SO4
2-
) is to the easy liberation of NO3
-
for depolarization
and also for liberation of nitrate ion (NO3
-
) as NO2 when it is warmed. The reaction is


+ + e O NO NO
2 2
1
2 3

Instrumentation
Instrument used in the lab- an Electrochemical cell containing platinum electrodes
An electricity source (0.4-0.5 A, 5V)
magnetic stirrer
The essential requirements for a constant current electrolytic determination a source of
(direct) current, a variable resistance, an ammeter, a voltmeter and a pair of platinum electrodes
were assembled in the laboratory. A platinum metal electrode that is covered with a rough,
large surface area platinum coating. The purpose is to produce an electrode with a large true
area that will be relatively non polarizable

Figure 26: Schematic Diagram of Electrogravimetric analysis

59
In order to carry out the electrolysis properly magnetic stirrer was used for constant stirring of
the solution. Two platinum electrodes were used for electrolysis. A constant electric supply
was maintained by changing the potential at necessary moments.

Figure 27: Instrument used in laboratory for electrolysis







Figure 28: Copper deposition on the platinum electrode

Procedure
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 HNO3 acid is added drop wise to
dissolve the brass. The color of the solution at that instant was blue;
1 ml of concentrated H2SO4 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 C2H5OH 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.

60
Advantages
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 will be 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. Thus purity of a substance can be measured.

Limitations
Some limitation of this electro gravimetric 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.


61
Result
The amount of Cu determined in the brass sample was 76.13%
Discussion
From the result it is clear that complete deposition of Cu was not achieved. This may happened
due to the following reasons:
The brass used here was 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 sulphamic 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.

62
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 off.
The voltage and current supply had been maintained constant throughout the experiment
Caution
Cathode should be removed from the solution at the time when it starts changing its
color from salmon pink to black due to oxide formation (CuO).
Cathode & anode must be removed from the solution before the switch is turned off;
otherwise there is possibility of back reaction.






















63
Conclusion

There was a time when people used to rub stones to light fire. But those days are history now.
No one will even think about lighting fire from stones now a days. With the similar manner the
classical methods of analytical chemistry will also become obsolete in near future. But the
importance of instrumental analysis is increasing day by day. It should be mentioned here that
instrumental methods of analysis is a must for an engineer who has to deal with instruments all
the times. Whereas a Chemical Engineer has to frequently deal with the problems like
separation of different components of a sample determination of the amount of an element, find
out end point of solution etc. and so on.
To deal with these types of problems, a chemical Engineer should have a good knowledge about
the instrumental methods of analysis, for example, spectrophotometer can be used for the
presence and amount of an element determination in a solution.
Since the modern world has been heading towards instrumentation, where every unit of
parameter comes out directly in digits, where control system is remote control, so a Chemical
Engineer should know the use of different types of instruments, their working methods,
principles and even their limitations.
The wide utility of analytical chemistry has sufficient reasons alone for treating it is an
individual course. The instrumental methods of analytical chemistry of this course (Chem 352)
help the students to learn careful and quantitative laboratory skills and techniques. For the
improvement of this course (Chem352) and to offer the students translucent conception about
instrumental methods of analysis the following measures should be taken under consideration

Number of apparatus and instrument in the laboratory should be increased so that every
student can perform each of the experiment individually.
A pen recorder should be provided as when it is connected to a cell during performing
conductometric titration, draws a plot of change in conductance with addition of reagent
used automatically. Drawing plots manually is time consuming and sometime gives
erroneous result.



64
Bibliography

Bahl, B. S., Tuli, G.D., Bahl, A., Essentials of Physical Chemistry, Millennium edition,
S.Chand Publications, (2000).
Besset & associates, Vogels Textbook of Quantitative Inorganic Analysis, 5th
ed.,Addison Wesely Longman Inc,(1999).
Glasstone, S., An Introduction to Electrochemistry, International edition, East-West
Press Private Ltd, (1942).
Maron, S. H., Prutton, C. F., Principles of Physical Chemistry, 4
th
edition, McMillan
Publishing Co.,(1965).
Williard, H. H., Merritt, L.L., & Dean, J.A., Instrumental method of analysis, 4
th
ed.,
Nostrand company, London.






























65
Appendices




Containing

Observed data
Calculated data
Sample calculation
graphs



















66
Appendix-a
POTENTIOMETRIC TITRATION of iron (Fe
2+
)
Concentration of K2Cr2O7 , S1= 0.1(N)
Concentration of H2SO4=6.0(N)
Volume of ferrous (Fe
++)
solution, V2=10 ml
Required volume of Kr2Cr2O7 , V1=4.45ml
Table 1: Observed and calculated data for volume, cell EMF, first and second derivative
of cell EMF
Volume of
K2Cr2O7
(ml)

E (Volt)

dV

dE

dE/dV

d
2
E/dV
2

0 0.35125 0.2 0.00625 0.03125 -0.0625
0.2 0.3575 0.2 0.00875 0.04375 0.03125
0.4 0.36625 0.2 0.0075 0.0375 -0.03125
0.6 0.37375 0.2 0.00875 0.04375 0.0625
0.8 0.3825 0.2 0.00625 0.03125 0.03125
1 0.38875 0.2 0.005 0.025 0.03125
1.2 0.39375 0.2 0.00375 0.01875 -1.3E-15
1.4 0.3975 0.2 0.00375 0.01875 -0.0625
1.6 0.40125 0.2 0.00625 0.03125 0.09375
1.8 0.4075 0.2 0.0025 0.0125 -0.03125
2 0.41 0.2 0.00375 0.01875 -0.03125
2.2 0.41375 0.2 0.005 0.025 0.03125
2.4 0.41875 0.2 0.00375 0.01875 -0.0625
2.6 0.4225 0.2 0.00625 0.03125 0.0625
2.8 0.42875 0.2 0.00375 0.01875 -0.09375
3 0.4325 0.2 0.0075 0.0375 0.0625
3.2 0.44 0.2 0.005 0.025 -0.0625
3.4 0.445 0.2 0.0075 0.0375 2.36E-15
3.6 0.4525 0.2 0.0075 0.0375 -0.125
3.8 0.46 0.1 0.005 0.05 -0.25
3.9 0.465 0.1 0.0075 0.075 -3.3E-15
4 0.4725 0.1 0.0075 0.075 0.125
4.1 0.48 0.1 0.00625 0.0625 -0.375
4.2 0.48625 0.1 0.01 0.1 8.88E-15
4.3 0.49625 0.1 0.01 0.1 -13.5
4.4 0.50625 0.1 0.145 1.45 12.125
4.5 0.65125 0.1 0.02375 0.2375 0.9375
4.6 0.675 0.2 0.01 0.05 0.0625
4.8 0.685 0.2 0.0075 0.0375 0.0625
5 0.6925 0.2 0.005 0.025 0.0625
5.2 0.6975 0.2 0.0025 0.0125 -0.03125
5.4 0.7 0.2 0.00375 0.01875 4.16E-16
5.6 0.70375 0.2 0.00375 0.01875 2.78E-15
5.8 0.7075 0.2 0.00375 0.01875 0.016632
6 0.71125 0.118542 -0.0625

67
Sample Calculation
Strength of Fe
2+
at the end point
Concentration of K2Cr2O7 ,, S1 = 0.1N
From graph required volume of K2Cr2O7 for titration,V1 = 4.45 ml
Volume of ferrous (Fe
++
) solution, V2 =20 ml
Concentration of Fe
2+
solution, S2 = ?
Now,
V1S1 = V2S2
S2 = (4.450.1) / 20
= 0.02225N

Determination of Concentration of Fe
3+
ion For 4 different points of the Graph
For V=3ml K2Cr2O7 ,Ecell=0.4325 V
Now,Ecell=EFe
2+
/Fe
3+
+Ec
=> EFe
2+
/Fe
3+
= Ecell - Ec.(Eq-1)
Here,Ec =0.244 V for saturated KCl solution
So,from Eq-1, EFe
2+
/Fe
3+
=0.1885 V
Again, EFe
2+
/Fe
3+
= E
0
Fe
2+
/Fe
3+
-

ln

3+

2+
..(Eq-2)
Here,
E
0
Fe
2+
/Fe
3+
= - 0.771 V
R=8.314 J/(mol.K)
T=32
0
C =305 K (Room temperature)
F=96500 Faraday
From Eq-2,

3+

2+
= 1.38710
-16

Strength of Fe
2+
at the point where 3ml K2Cr2O7 is used can be calculated from equivalence
relation.
4.45 ml 0.1N K2Cr2O7 = 0.02225 N 20 ml Fe
2+

1ml 0.1 N K2Cr2O7 = 0.005N 20 ml Fe
2+
3 ml 0.1 N K2Cr2O7 = 0.015 N 20 ml Fe
2
So, aFe
2+
=0.015 N
Now, aFe
3+
=1.38710
-16
aFe
2+

=2.0810
-18
N


71
APPENDIX-B
CONDUCTOMETRIC TITRATION of an acid mixture(Hcl+CH3COOH)
Observed and calculated data:
Volume of the NaOH = 10ml
Strength of Oxalic Acid = 0.1N

Table 2: Table for volume of NaOH (ml) & conductance (ms)
Volume of NaOH
(ml)
Conductance
(mS)
Volume of NaOH
(ml)
Conductance
(mS)
0.0 2.30 5.4 1.22
0.3 2.24 5.7 1.25
0.6 2.07 6.0 1.28
0.9 1.89 6.3 1.32
1.2 1.76 6.6 1.35
1.5 1.59 6.9 1.39
1.8 1.48 7.2 1.42
2.1 1.35 7.5 1.46
2.4 1.22 7.8 1.50
2.7 1.11 8.1 1.57
3.0 1.04 8.4 1.65
3.3 1.02 8.7 1.74
3.6 1.03 9.0 1.83
3.9 1.05 9.3 1.94
4.2 1.08 9.6 2.06
4.5 1.11 9.9 2.15
4.8 1.14 10.2 2.24
5.1 1.18 10.5 2.33

Table 3: Data for Determination of the Strength of Oxalic Acid

Observation
No.


Volume of
NaOH(ml)
Burette Reading
Volume of
Oxalic Acid(ml)

IBR(ml)

FBR(ml)
01 10 0 20 20
02 10 20.2 40.2 20


Sample Calculation

Standardization of NaOH by H2C2O4
Here, volume of NaOH, V1 = 10 ml
Volume of H2C2O4 , V2 = 20 ml


72
Strength of H2C2O4 , S2 = 0.1N
Strength of NaOH = S1
Now, V1 S1 = V2 S2
S1 = (20 0.1)/ 10
= 0.2N
So, the strength of NaOH = 0.2N
Calculation for HCl
Here, the volume of NaOH for neutralizing HCl, V1 = 9.5ml (from graph)
Strength of NaOH, S1 = 0.2N
Volume of HCl solution, V2 = 10ml
Strength of HCl = S2
Again, V1 S1 = V2 S2
S2 = (9.5 0.2)/ 10
= 0.19N
Now, Equivalent weight of HCl, e = 36.5
Weight of HCl = W1
Again, W1 = S2 e V2
= (0.19 36.5 10)/ 1000
= 0.06935g

Calculation of CH3COOH
Here, volume of NaOH for neutralizing CH3COOH, V1 = (20.1-9.5) = 10.6ml
Strength of NaOH, S1 = 0.2N
Volume of CH3COOH solution, V2 = 10ml
Strength of CH3COOH = S2
Again, V1 S1 = V2 S2
S2 = (10.6 0.2)/ 10
= 0.212N
Now, Equivalent weight of CH3COOH, e = 60
Weight of CH3COOH = W2
Again, W2 = S2 e V2
= (0.212 60 10)/ 1000
= 0.1272g
Percentage (%) of HCl = [W1/ (W1+ W2)] 100%


73
= [0.06935/ (0.1272 + 0.06935)] 100%
= 35.28%

Percentage (%) of CH3COOH = [W2/ (W1+ W2)] 100%
= [0.1272/ (0.1272 + 0.06935)] 100%
= 64.72%



75
APPENDIX-C
pH METRIC TITRATION
Observed and calculated data
Table 4: Observed and Calculated data for pH-matric titration


Sample Calculation
Concentration of Na2CO3, S1 = 0.05 N
From graph,
Required volume of HCl acid for complete titration, V2= 2.78 ml (from graph)
Volume of ferrous Na2CO3 solution, V1= 10 ml
Now,
V1S1 = V2S2
S2 =
.
.
= 0.1798 N
Calculations for dissociation constants
Volume of HCl for converting Na2CO3 to NaHCO3, V1 = 1.17 ml
Dissociation constant of Na2CO3, pk1 = the corresponding pH for V1/2 ml of HCl
= 7.7 (From Graph)
Volume(V) pH dV d(pH) d(pH)/dV d
2
(pH)/dV
2
0 9.93
0.8 9.13 0.8 0.8 1 6
0.9 8.97 0.1 0.16 1.6 -3
1 8.84 0.1 0.13 1.3 41
1.1 8.3 0.1 0.54 5.4 13
1.2 7.63 0.1 0.67 6.7 -20
1.3 7.16 0.1 0.47 4.7 -8
1.4 6.77 0.1 0.39 3.9 -5.08333
2 6.12 0.6 0.65 1.083333 1
2.2 6.05 0.2 0.07 0.35 3.5
2.4 5.68 0.2 0.37 1.85 -0.72222
2.7 5.21 0.3 0.47 1.566667 59.66667
2.8 4.45 0.1 0.76 7.6 -29
2.9 3.98 0.1 0.47 4.7 -16
3 3.75 0.1 0.23 2.3 -4.84
3.5 3.38 0.5 0.37 0.74 -0.92
4 3.22 0.5 0.16 0.32 0.56
4.5 3.08 0.5 0.14 0.28

76
Volume of HCl for neutralizing NaHCO3, V2 = 2.78-1.17=1.61 ml
Dissociation constant of NaHCO3, pk2 = the corresponding pH for (V1 + V2 /2) ml of HCl
= 5.25(From Graph)



81
APPENDIX-D
Spectrophotometric Determination of Iron
Observed Data
Peak Pick
Wavelength, max = 478.5nm
Absorbance = 0.4187

Table 5: Table for observed data of absorbance of different concentration

Calculated Data
From the following Graph at Absorbance = 0.505
Concentration of the known solution = 3.52ppm
And also from the graph, the equation of the line is,
y = 0.1427x
x = Concentration & y = Absorbance
At y = 0.505, From the Equation x =3.52


No. of observation Concentration (ppm) Absorbance
01 Reference cell 0.0588
02 1 0.1874
03 2 0.320
04 3 0.440
05 4 0.553
06 5 0.698
unknown - 0.503

83
APPENDIX-E
Electrogravimetric Determination Of Copper In A Brass Sample

Observed Data
Initial weight of the platinum electrode = 18.3889gm
Weight of the electrode after deposition = 18.5135gm
Weight of brass = 0.2950gm
Sample Calculation
Weight of the copper deposited = (18.3889 18.5135)gm
= 0.2246gm
Percentage recovery = (0.2246/0.2950) 100%
= 76.13%