UNIT 3 LOW-COST INSTRUMENTS

Structure
3.1 Introduction
Objectives

3.2 Colorimetry
Beer-Lambert Law
Principle of Colorimeter
Various Controls of the Low-Cost Colorimeter
Demonstration Experiment 1 : Colorimetric Estimation of Copper Sulphate

3.3 Conductometry
Theory
Various Controls of the Low-Cost Conductometer
Method of Operation
Demonstration Experiment 2 : Determination of conductance of Given Sodium
Hydroxide Solution

5.4 Potentiometry
Galvanic Cells and Cell Reaction
Measurement of E.M.F.
Nernst ~ q ' u a t i o n
Types of Electrodes
Various Controls of the Low-Cost mV/pH Meter
Method of Operation
Demonstration Experiment 3 : Construction of Daniel1 Cell and
Measurement of E.M.F.

3.5 Summary

3.6 Answers

3.1 INTRODUCTION
In this unit, we shall discuss the basic principles of colorimetry, conductometry
and potentiometry. We shall explain the procedure for using low-cost instruments
such as colorirneter, conductometer and mV/pH meter. You will be using these
instruments for some of the experiments in this course. Three demonstration
experiments will also be discussed.to illustrate the use of these instruments.

Objectives

After studying. this unit, you should be able to :

-- -
8 state the principles of colorimetry, conductometry and potentiometry,
explain the procedure for operating the contrbls in colorirneter, conductometer and
mV/pH meter, and
explain the methods of recordme absorbance or conductance or e.m.f. of the given
solution o r system.
 Laboratory Skills and
Techniques 3.2 COLORIMETRY
Chemical analysis based on measurement of intensity of light absorbed in the
visible region is termed colorilnetry. Any coloured substance may be analysed by
this method. If a substance is colourless, it can be made to form a coloured
compound by the addition of a suitable reagent and then analysed
colorimetrically. In colorimetry, generally the concentration of a substance is
obtained from the intensity of light absorbed. In order to accomplish this,
experiments are carried out to obtain the intensities of light absorbed by the
substance in solutions of known concentrations. The simple instrument used for
this measurement is termed a colorimeter. Colorimetric methods provide a simple
l
and rapid method of estimating minute quantities of substances in solution. Hence
F o r a detailed study of
the technique can be used to perform a wide variety of experiments such as
Beer-Lanlbert law,see U n i t of monitoring a reaction colorimetrically in kinetics, determining equilibrium
CHE-03 (L) and Unit 8 of concentrations for the determination of equilibrium constants, etc. Let us now
CHE-01 courses. discuss Beer-Lambert law which summarises the basic principle of colorimetric
estimation.

3.2.1 Beer-Lambert Law

When light of an appropriate wavelength is passed through a coloured solution
n e w a v e l e n g t h a t which a
substance exhibits maximum contained in a cell, a fraction of the light is absorbed. The intensity of light
absorption depends on its absorbed depends on thc nature or structure of the substance, its concentration in
structure. solution and the thickness of the absorbing medium. The part of light, which is
not absorbed, is transmitted. Though some light is reflccted back from the
solution, its amount is negligibly small and is eliminated by using a control. For
all practical purposes we may say,

where,

I0
- Intensity of incident light
Ia -- Intensity of light absorbed
It -- Intensity of transmitted light.

Beer-Lambert law relates Ia to the thickness and concentration of the medium.

Let us understand Beer-Lambert law.

Beer-Lambert law is a combination of the two laws, Beer's law and Lambert's law.
We are not going to discuss these two laws separately. Beer-Lambert law states
that t h i fraction of llght absorbed by a given absorbing medium is directly
Eq. 3.1,A = ~ c lis, of the type proportional to the thickness of thc medium and the concentration of the
'jy=mx",which is a n equation for
absorbing species. The mathematical expression of this law is given below:
a straight line passing through
the origin. T h e slope ("m") of log Io/I = A = ~ c l . . . (3.1)
the straight line plot of A against
c i s equal t o the product, el. where,
Hence, from the values of the 10
- Intensity of incident light
slope and I, e can be found out. I -- Intensity of transmitted light
= Slope A -- Absorbance
1
1 - Thickness of the medium
C - - Concentration in mol dm-3
E
-- Molar absorption coefficent
 Low-Cost Inslrumenls
E,the molar absorption coefficient, is the absorbance of a solution having unit
concentration (c = 1 M) placed in a cell of unit thickness, (I = 1 cm).
Absorbance is also called optical density (OD). E can be expressed in the unit, m2
mol-' or cm2 mol-'. If 1 is in m
According to Eq. 3.1, the absorbance or O D of a solution in a container of fured unit and c is in mol rn-) units,
path length is directly proportional to the concentration o f a solution. A plot then E is in m2 mol-' units. On
the other hand, if 1 is in cm unit
between absorbance and concentration is expected to be linear. Such a straight and c is in molarity unit
line plot (passing through the origin) shows that Beer-Lambert law is obeyed. (mo1/1000 cm3 or mol/dm3
The straight line s o obtained is known as calibration curve. A calibration curve is units), then E is in cm2 m01-'
useful in finding the concentration of a given solution. We shall discuss this units.

aspect in Demonstration Experiment 1 of this unit. Dilute solutions obey

Beer-Lambert law over a considerable concentration range, the upper limit
varying from system to system.

Deviations from Beer-Lambert h w

Beer-Lambert law does not hold good over a wide range of concentrations, if Monochromatic light has more
the nature of the absorbing species changes with concentration; for example, or less only one wavelength
when the species ionises, dissociates or associates in solution. Addition of large
amounts of noninterfering electrolytes may shift the wavelength at which
maximum asportion occurs and may also change the value of molar absorption
coefficient. Also discrepancies may occur when the light used is not
n~onochromatic.

3.2.2 Principle of Colorimeter

It is difficult t o quantify colour visually. For this we need the help of a
1
measuring device. A colorimeter is such a device. A colorimeter measures the
intensity of light before passing through the solution and after passing through
I the solution. From the intensity measurements, we can estimate the
I
concentration of a solution. You are provided with a low cost colorimeter for
measurement of light intensity.

Ii In general, the apparatus for colorimetry includes a

light source
A colorimeter operates on a
1 slits and lenses to focus a sharp beam of light, broad range of wavelengths.
i
filters to transmit a narrow range of wavelengths, A colorimeter is useful in
visible region only. But a
a cuvette which is a small vessel in which the solution is taken,
spectrophotometer is useful in
cuvette holders, and, U.V.and visible regions. A
spectrophotometer has special
a receiver which is helpful in determining the intensity of the transmitted beam. facilities for generation and
selection of specific

I1 The instruments of this type are known as filter calorimeters or filter

photometers. A schematic diagram of a colorimeter is given in Fig.3.1. The
diagram of a low-cost colorimeter is given in Fig.3.2.
wavelength.

I
t

Light Cuvcttc Detector

source
8. slit a containing I. or I. Meter
solution photocell
 Flg. 3.2 :Low-cost colorlmeter.

Three light emitting diodes (LEDs) are available in the low-cost colorimeter as
The diodes have the property of
light source. These emit light of different colours such as red, yellow o r green.
permitting current to flow with
practically no resistance in one You would be using one of them depending on the colour of absorbing
direction and offer nearly medium. The light from the source is made t o pass through a slit so that we
infinite resistance to current get a thin ray, which falls on the cell containing the solution. Some of the light
flow in the opposite direction. In is absorbed and the rest is transmitted. The light transmitted by the solution
electronic circuits, diodes have
numerous applications.
falls on the photocell where a current is generated. The magnitude of this
current is proportional to the intensity (I)of the light transmitted by the
solution. The current signal is suitably amplified and then measured with the
A photocell converts light into
electricity.
help of an ammeter. The intensity of incident light (lo) is measured by passing
the light from the same source through distilled water taken in the cuvette.
Under this condition, no light is absorbed and the whole of it falls on the
The reference sample may be
pure solvent or a solution of
photocell. In case the solution is made in a solvent other than water, the pure
lower concentration. solvent may be taken as the reference sample. The difference between the two
readings gives the amount of light absorbed. Next let us discuss the controls of
the low-cost colorimeter.

3.2.3 Various Controls of the Low-Cost Colorimeter

Power Switch This is a switch on the back of the instrument and
is used to switch the instrument o n o r off. When
the instrument is connected to the mains and
switched on, the LED on the front panel will glow.
The meter reading is called the
meter response. Instead of Colour Stleetor This control is on the front panel of the
absorbance values, meter instrument with the positions marked R, Y and
response values are used in
G signifying the three colours, red, yellow or
low-cost colorimeter
green.
experiments.

Meter Scale The scale in the colorimeter (marked A) has

markings from 1 to 10. These markings are meter
response values.
Set Zero This control is again on the front panel of the
instrument. This is adjusted to set the meter
response to zero when the solvent or reference
solution is taken in the cuvette.

Sensitivity This control is also on the left front panel o f the

instrument. This is used to give any desired scale
for the range of cencentrations under
consideration. Suppose that in an experiment, we
have solutions of concentrations varying from 0 to
8% (mass by volume). With the solvent, the set
zero knob is adjusted to set the meter response to
zero. Then with the 8 % solution, the sensitivity
knob is adjusted to set the meter response to 9.0.
Let us say, in another experiment, we have
solutions from G 6 % only. Instead of using the
same adjustment, we could have a better scale.
After setting zero with the solvent, we take the
6% solution and readjust the sensitivity knob to set
the meter response to 9.0. Remember, the earlier
setting gives a scale of 0-9 for concentrations 0--8%,
whereas-:he latter setting gives a scale of 0-9 for a
smaller concentration range 0 4 % .

Method of Operation

1) Before connecting the instrument to the mains, check whether the needle
coincides with zero in the meter. If the needle is not coinciding with zero,
make it read zero using a small screw driver into the hole under the meter.
Then connect the instrument to the mains and put on the power switch at
the back.

2) Set the colour selector knob at the desired colour. For an unknown
solution, the knob for the colour selector is set at R or Y o r G depending
on which LED gives the highest meter response, (i.e., the largest
absorbance), when the light from LED is passed through the solution in the
cuvet te.

3) Take a clean cuvette and fill it with ..i!&7HXdwater (or the reference
sample). Wipe the outside dry with tissue paper. Make an identifying mark
on one plain side ~f the curvette at the tbp and insert the curvette into the
holder in such a way that the marked plain side is towards the LED.
Maintain this position everytime you insert the curvette into the holder.
Close the lid of the holder.

4) Adjust the set zero control to make the meter read zero.

5) Next rinse and Ell the same cuvette with the solution of maximum
concentration. Wipe the outside dry. Insert into the holder and close the lid.

6) Adjust the sensitivity control to set meter response near the end of the
scale, say 9.0. Do not disturb this knob after this adjustment.

7) Rinse and fill the same cuvette again with distilled water (or the reference
sample) and insert into the holder after wiping the outside dry. Check if the
meter reads zero. If not, use the set zero control to get a meter reading
zero. After this, do not disturb this knob. The instrument is now set for a
calibration experiment or a kinetic experiment.
Laboratory S W and Precautions
Techniques

1) You should not use a plastic cuvette while using organic solvents like
chldroform, acetone, etc.

2) The reference sample, which is used to set the meter response to zero with
the set zero control, should consist of the solvent (or a solution lower
3-f

concentration) and all reagents except the specific light-absorbing substance

being studied.

3) Wash the cuvette thoroughly. Rinse it with the solvent o r the solution
depending on which is going to be taken in it for colorimetric measurement.

4) See to it that you d o no1 leave any finger marks o n the cuvette.

5) Keep the cuvette in the same position each time you insert it in lhe holder.

6) Never touch the faces of the cuvette through which light is transmitted.

7) Wipe the outside of the cuvette dry after filling and before inserling in the
holder.

3.2.4 ~ e m o n s t r a t i o n ' ~ x ~ e r i r n e1n:t Colorimetric Estimation of

Copper Sulphate
Calibration of a colorimeter is the first step in estimating the concentration of a
solution colorimetrically. In this experiment, we shall discuss the method of
obtaining the calibration curve and estimaling the concentration of given solution
of copper sulphate.

Aim : i) T o draw concentration - absorbance calibration curve for copper

sulphate solution.

ii) T o determine the concentration of a given copper sulphate solution.

Requirements
Apparatus .
Colorimeter
Volumetric flask (100 cm3)
Test tubes
Test tube stand
Measuring cylinder (10 cm3)
Beaker (250 cm3)
Burettes (50 cm3)
~ G r e t t estand
Chemicals

Stock solution of copper sulphate (10% m/V)

copper sulphate solution of unknown concentration

Procedure

Copper sulphate solutions of various concentrations are prepared in six labelled

test tubes using the stock solution. For this purpose the required volumes of
water and copper sulphate solution (stock solution) are added as shown below :-
 Low-Cost Instruments
Water and copper sulphate solutions are taken in two burettes, one containing the
stock solution and the other containing water.

Sample Volume of Volume of Mass by volume While verifying the mass by

number stock solution distilled water percentage of volume percentage values
solution entered in the table, remember
that the stock solution is 10%
rn/V in strength.

It can be seen that the concentration of the six samples vary from 0 to 10% of
copper sulphate (mlv).

Before estimating c u 2 + ions in a n unknown solution, a calibration curve will

have to be plotted between the concentration and the meter response in the
instrument. F o r this we shall follow all the instructions listed under 'Method
of Operation'. In keeping with instruction 2 stated there, set the selector knob
o n R, since copper sulphate solution has a n absorption maximum in the red
region. After adhering to the instructions 1 and 3 to 7, the following is done
without distributing the set zero and the sensitivity knobs.

The cuvette is cleaned throughly, rinsed with sample (1) mentioned above and
filled with the same. T h e cuvette is placed in the cuvette holder in the
instrument and the meter response is recorded in observation Table 3.1. Then
sample (1) is removed and the cuvette is rinsed and filled with sample (2). T h e
cuvette with sample (2) is placed in the cuvette holder and t h e meter response
is again noted. This procedure is repeated with the samples kept in tubes (3),
(4), (5) and (6), each time notins the meter response in Table 3.1.

The cuvette is again washed, rinsed with the soiution of unknown concentration
(sample 7) and filled with it. The cuvette is placed in the cuvette holder and the
meter response is noted in the table.

Table 3.1 : Meter Response as a Function of Concentration of Copper Sulphate

Sample Strength of copper sulphate Meter response

number in % m/v

4
6
8
10
Unknown solution
LPboratoIy Skills a d Calibration Cune
Techniques
The calibration curve (Fig. 3.3) is plotted in a graph sheet using the values of
strength of copper sulphate solution and meter response from Table 3.1.

g of CuS04 solution

Fig.3.3 :Calibration Cuwe.

Using the Calibration Cune

In the interpolation method, the The concentration of the test solution (solution of unknown concentration of
concentration ofthe unknown copper sulphate) is found out by interpolation method. For this, a dotted straight
solution lies between the upper line is drawn from the point corresponding to the meter response of the test
and lower 'lmlts Of concentratrons solution. The x-coordinate corresponding to the point of intersection of the
of standard solutions used for
color~metncmeasurement.
calibration curve and the dotted line gives the strength of the test solution as
shown in Fig. 3.4.

% of CuS04 solution

Fig. 3.4: Flndlng the concentration of the unknown soluliol~using the interpolation method.

Result

From the graph, % of copper sulpl~atesolution = ........ % mlV

SAQ 1 ~ m r ~ o~ndroments
st

For a substancc, E is equal to 245 m2 mol-' at a wavelength of 450 nm. Calculate

the concentration (in molarity units) of its solution which has an absorbance of
0.1250, when placed in a cell of thickness 1.00 x m.

Hints : (i) Use Eq. 3.1 (ii) Note that E is in m2 mol-' units and I is in m unit.
Hence c will be in rnol m-3 units.

T o get c in molarity unit, use the following relationship:

1 rnol m-3 = 1 rnol (10 dm)-3

= 1 x rnol dm-3

[since 1 M = 1 rnol dm-3

= I rnol per litre]

3.3 CONDUCTOMETRY
Conductometry deals with the measurement of electrical conductance of solutions
containing ions. These solutions conduct electric current due to the movement of
ions towards oppositely charged electrodes. The ability of a solution to conduct
current is given by its conductivity. The conductivity of a solution is proportional
to the number of ions, the charge o n each ion and the speed with which the ions
move. T h e speed with which an ion moves in turn depends o n the nature of the
ion, nature of t h e solvent, presence of other ions, temperature and the applied
field.

Conductometric measurements find a wide range of applications. These are used

in determining equilibrium constants, e.g. ionisation constants of weak
electrolytes, solubility products of sparingly soluble salts, hydrolysis constant, etc.
Reactions that proceed with the formation o r disappearance of ions can be
conveniently monitored conductometrically for getting their kinetic parameters.
Some substances which cannot b e volu~netricallyor potentiometrically analysed
can b e estimated conductometrically with ease.
e

3.3.1 Theory
Ionic solutions obey Ohm's law just as metallic conductors do. In accordance with
Ohm's law, the current I passing through a given solution is proportional to the
potential difference, E. T h e proportionality constant R is the resistance of the
solution.

I h r . conductance G is defined as the reciprocal of resistance.

Laboratory Skills and Resistance is measured in ohm (SZ )and conductance in siemens (S), 1 s = 1 51-'.
Techniques

The resistance of a homogeneous body of uniform cross section is' proportional to

its length, 1 and inversely proportional to its cross-section, A. The proportionality
constant is called the resistivity- (specific resistance), p. The units of p are S2 m.

The conductivity K (Kappa) is the inverse of resistivity.

The units of K are S m-l.

Conductivity of a solution can be defined as the conductance of a solution

contained between two parallel electrodes which have cross-sectional area 1 meter
square and which are kept 1 meter apart.
1 1 1
Taking the inverse of Eq. 3.4, - = - .-
R P @/A)
= K/(I/A) (using Eq. 3.5)
using Eq. 3.3., G = K/(I/A)
or K = G (//A) . . . (3.6)
The ratio //A is called the cell constant and it depends on the geometry of the
cell - the distance between the electrodes (1) and the area of the electrodes (A).
Eq. 3.6 can be written as
Conductivity = Conductance x cell constant . . . (3.7)
The cell constant values are usually obtained by an indirect method and not by
measuring 1 and A directly. The indirect method involves measuring the
conductance G of a standard solution of KC1 of know11 conductivity, K . Table 3.2
gives the K values of KC1 solutions at three different concentrations and at three
different temperatures.
Table 3.2 : Conductivity of KC1 solutions

Standard KC1 solution is taken in the cell for which CAIconstant is to be

determined. Conductance of this solution is then measured and its temperature is
noted. The conductivity at the temperature is obtained from Table 3.2.

We can get the K value of Then the cell constant can bc calculated using Eq. 3.7:
KC1 at temperatures other
than those given in Table 3.2 Conductivity of KC1 solution
from a plot of conductivity Cell constant = -
Conductance of the same solution
against temperature using
the values given inTable 3.2.
This cell of known cell constant is used for finding out the conductivity of any
other sample. For this, we have to measure the conductance of a given sample and
then use Eq.3.7.

Conductivity of a molar solution is termed molar conductivity. Molar conductivity

is represented by the symbol, A,,,,.
where K is the conductivity of a solution of concentration c mol m". Am is
Concentration in mol m-3
expressed in units of S m2 mol-'. units = Concentration in
molarity X 1000
You are provided with a low-cost conductometer (Fig. 3.5) for conductance
measurement. Tt has an operational amplifier based circuit. Operational amplifier
consists of many components mounted on a single silicon chip. Operational
amplifiers have a variety of uses and, are particularly useful in low-cost
instruments. We shall not discuss the principle behind the functioning of
operational amplifiers, since the same is not necessary to do our experiments. For
a detailed discussion o n operational amplifiers, you are advised to go through
Unit 9 of Block 3 of Electrical circuits and Electronics (PHE-10) course.

Fig. 3.5 :Low 'cost conductometer Fig. 3.6 :Low cost conductivity cell

The low cost conductometer is easv to assemble and maintain. The low cost The commercial
conductometers are based on
conductometer is more convenient to use, especially for studying reactions
wheatstone bridge principle
conductometrically in kinetics experiments; we shall be using this instrument in which is explained in Unit 16 of
Experiment 21 of this course. Block 4 o f Physical Chemistry
(CHE-04) course.
The commercial conductivity cells are expensive due to the usage of platinum
electrodes. On the other hand low-cost conductivity cell (Fig. 3.6) is made of
zero-cost carbon rods. These carbon rods are obtained from exhausted dry
batteries. Using these carbon rods, conductivity cells of various designs can be
easily made.
The conductance of solutions increases with increase in temperature. This is due
to the increase in the velocity of ions, decrease in the viscosity of the medium,
and decrease in the interactions between ions. In the case of weak electrolytes, the
increase in the degree of ionisation with increase in temperature also contributes
to the increase in conductance. Generally the conductivity of aqueous solutions
increases by about 2% per degree celsius rise in temperature. Hence it is advisable
to keep solutions in a thermostat till they acquire constancy in temperature.
Conductance, conductivity and molar conductivity values are to be given along
with the temperature values.
As ordinary distilled water contains impurities like C02, metal silicates, etc., it
cannot be used for preptiring solutions for very accurate conductance
measurements. When conductance values of high accuracy are required,
conductivity water is t o be used.
 For the conductance experiments of this course, distilled water o r deionised water
is adequate, as long as the conductivity of water is not more than S cm-' o r
s m"

33.2 Various Controls of the Low-Cost Conductometer

Power Switch
This switch is o n the back of the instrument. This is used to turn the instrument
on o r off. When the instrument is connected to the mains (220 V, A C supply) and
switched on, the indicator LED o n the front panel glows.

Range Selector

This control is on the front panel of the instrument. It has positions marked 0.2,
2, 20. These numbers stand for the full scale meter values in millisiemens (mS).
This means, for example, when the selector is at 20, the meter reads between 0
and 20 mS.

Mode Selector

A minimum volume of solution is This control is also on the front panel of the instrument. It has positions marked
required t? be taken in the cell for CAL and READ. This is used t o set the instrument in either the calibration
measuring the conductance o f the
solution. This varies from cell to cell
(CAL) or read (READ) mode. The instrument is kept on CAL mode when the
and has to be experimentally obbined. meter is being calibrated to read 0.1, 1, or 10 mS (mid point of the scale in the
This minimum volume is little more range 0.2, 2, or 20 mS, respectively) using the sensitivity control. When the
than thevolumeofsolution required instrument is on CAL mode, a standard resistor inside the instrument replaces the
to just immerse the electrodes. This
conductivity cell in the circuit. The cell is in circuit only when the control is on
volume can be determined by taking a
strong electrolyte, for example, a READ mode-
solution of KCI. Measure out a
volume, say 5 cm3, into the cell, Sensitivity '
calibrate the meter and determine the
conductance. Then add KC1 solution This control, which is also on the front panel, is used while calibrating the meter.
in 1cm3 lots and measure the
conductance after each addition. The
volume of solution beyond which 33.3 Method of Operation
conductance remains constant is the
minimum volume. This volume can The following instructions will help you in using the conductometer.
also be obtained graphically by
conductance vsvolume of 1) Check the mechanical zero of the meter before connecting the,instrument
solution (Fig. 3.7). to the mains. If the needle is not showing zero, then adjust this using a small
screw driver inserted into the hole under the meter. Then connect the instrument
to the mains and switch on the instrument using the power switch.

2) Take the minimum volume of the solution (for which conductance is to

be measured) in the conductivity cell and, connect the cell to the
instrument.

3) Keep the mode selector a t READ.

V O ~ U ~ C I C ~ ~ 4) Set the range selector at one of the positions, 0.2. o r 2 o r 20, such that
Flg. 3,7 :ConduclPnce vs. volume of
the position which gives a meter reading is around the middle of the
s~lullonplot for determining the scale.
minlmum volume.
5) Shift the mode selector at CAL. Then adiust the sensitivitv control to set
For any conductance measurement
the meter readins t~ mid+cale. After this adjustment, d o not disturb the
using this cell, the volume o f solution
t o be taken has to be equal to or more sensitivity control. The steps 1 t o 5 are collectively known as calibration of
than the minimum volume. the conductometer.
74
 6) Set the Mode selector to READ and read the meter to get the actual Low-Cost Instruments
conductance value of the solution.

Precautions

1) Measurement of conductance in the course of a titration or a kinetic

experiment may require shifting the Range Selector control. Every time you
change the range, you have to check if the meter calibration is alright.

2) Conductivity cells should never be left with any solution o r without proper
cleaning after an experiment. After cleaning and rinsing well with distilled
water or deionised water, leave the cell with electrodes well immersed in
distilledtdeionised water.

3) Rinse the conductivity cell well with the test solution a couple of times
before filling the cell for measuring conductance.

4) You must keep the mode selector at CAL (and not at READ) under the
following conditions:
0 a t the time of disconnecting the conductivity cell
changing the solution in the cell
at the time of connecting the cell but before pouring the solution into it.

5) If for any experiment you have to stir the solution in the conductivity cell,
then keep the stirring rod above the solution while reading the meter.
The method of measuring the conductance of a solution can be understood from
Demonstration Experiment 2.

3.3.4 Demonstration Experiment 2: Determination of Conductance

of Given Sodium Hydroxide Solution
We shall use the low-cost conductometer to find out the conductance of 0.01275
M NaOH solution. This experiment will help you in doing Experiment 21 of this
course which deals with the kinetics of saponification of ester.

Aim : To find the conductance of 0.01275 M NaOH solution.

Requirements

Apparatus

Conductometer - 1
Conductivity cell - 1
Wash bottle - 1
Chemicals

0.01275 M sodium hydroxide solution

Deionized water

Procedure

Before filling the conduclivity cell with 0.01275 M NaOH solution, it is washed
with water and rinsed with the given NaOH solution. The instructions 1 to 4 given
under "method of operation" are followed. We find out that it is preferable to
Laburnlury Skills and
place the range selector a t 20, since it leads to a meter reading around the middle
Techniques
of the scale. The sensitivity control is adjusted to set the meter reading to
midscale. After this adjustment, the sensitivity control is not disturbed. T h e mode
selector is shifted to "READ" position. The conductance of the given NaOH
solution is found out and the value is entered as shown below:

The conductance of 0.01275 M NaOH solution = . . . . . . . . . . . mS

SAQ 2
The conductivity of 0.1000 M potassium chloride~solutionis 1.167 S m-' at 293 K.
Calculate its molar conductance. (Hint : Use Eq. 3.9).

3.4 POTENTIOMETRY
Potentiometry deals with the measurement of difference in potential between two
electrodes which have been combined to form an electrochemical cell. The
electrochemical cells are of two types, galvanic cells and electrolytic cells. In
galvanic or voltaic cells, chemical energy is transferred into electrical energy. As a
result of this, galvanic cells act as a source of electrical energy. Daniell cell which
we are going to study in detail, is a familiar example of a galvanic cell. In
electrolytic cells, electrical energy is transformed into chemical energy. In
electrolytic cells, application of voltage higher than that of the cell results in a
chemical reaction. For example, passage of electricity through acidified water
causes electrolysis of water. It results in the production of hydrogen and oxygen at
the cathode, and anode respectively.

The difference in potential between the two electrodes of a galvanic cell is known
as cell potential. The cell potential depends on the composition of the electrodes,
concentrations of the solutions (or pressures of gases) and the temperature.
Relationship connecting the cell potential with the concentration of the species
involved in the concerned chemical reaction, known as Nernst equation, can be
derived using thermodynamic principles. A detailed discussion is given regarding
this in Sec. 17.6 of Unit 17 of Physical chemistry (CHE-04) course. Based on the
The mVlpH meter owes its dependence of cell ~ o t e n t i a ol n the concentration of the s ~ e c i e sin the cell. we
name t o the fact that it is useful
have used mV/pH meter in CHE-03(L) course as an analytical tool in acid-base
in measuring the potential
difference of (in mVunits) titration. In this course, we shall use mV1pH meter for the determination of pH
and in determining pH of the ' o f buffer solutions and the solubility product of silver chloride. In order to
solutions. understand the above two experiments, we shall study the galvanic cells in a
detaileu way.

3.4.1 Galvanic Cells and Cell Reaction

There are many types of galvanic cells. We are interested in such galvanic cells in
which the electrodes are dipped -in different electrolytes. W e shall illustrate the
functioning of galvanic cells using Daniell ,cell (Fig. 3.8).
 Low-Cost Instmmenh

Fig. 3.8 :Daniel1 cell

I) anodlc compartment, 11) eathodlc compartment, 111jsalt bridge, IV) voltmeter.

In Daniell cell, zinc gets oxidised to z n 2 + ions. Two electrons are released per
each zinc ion formed. These electrons travel towards the copper electrode and
are used in the reduction of cu2+ ions to Cu. These two reactions can be written
as follows:

Z n (s) d zn2+(cl) + 2e- Oxidation . . . (3.10)

cu2+ (c2) +2 6 CU(S) Reduction . . . (3.11)
An electrode dipping in an electrolyte constitutes a half-cell. For instance, zinc
rod dipping in zinc sulphate solution of concentration cl constitutes a half-cell
and copper rod dipping in copper sulphate solution of concentration c2 constitutes
another half-cell. Daniell cell is made by the combination of two half-cells. The
cell reaction in Daniell cell is the combination of two half-cell reactions (given by
Eqs. 3.10 and 3.11) and is represented below by Eq. 3.12.

Knowing the type of reaction taking place in a cell, we can represent the cell on
paper. For this, the following rules will be helpful.

1) The oxidation part must appear on the left side of the cell. The reduction
part must appear on the right side of the cell. The stoichiometric numbers,
the electrons and water molecules appearing in the half cell reaction (or
cell reaction) must not find a place in the cell representation.

2) The electrodes are shown at the extreme left and right positions. These are
shown distinctly separated from the corresponding electrolytes by means of
single vertical lines.

3) In case of gas'klectrodes, and many,oxidation-reduction systems like

quinone-hydroquinone, inert electrodes such as carbon rod or platinum wire
are used for electrical contact.

4) The various materials present in the same half-cell in the same phase are
written together separated by commas.
Laboratory Skills and Double vertical lines are used to join the two half-cells; this means a salt
Techniques 5)
bridge is used betwccn the two half-cells. W e shall shortly understand the
use of salt bridge in galvanic cells.

6) Concentrations o f ions, pressures of gases ctc. are indicated in brackets and

mentioned along wirh the substance.

In the light of these rules, you can understand the representation of Daniel1 cell
which is given below:

3.4.2 Measurement of E.M.F.

The potential difference across an electrode-electrolyte interface is called
electrode potential.

The cell potential of a galvanic cell (EcelI)is given by the differencc between the
two electrode potentials, El and E 2 , of the cathode and anode, respectively.

T h e junction potential developed a t the liquid junction between the two half-cells
also contributes to the cell potential. But this liquid junction potential can be
minimised by having a salt bridge between the two electrodes.

A salt bridge serves to

maintain electrical neutrality within the solutions in the two half-cells
rninimise the liquid junction potential
complete the circuit.
Let us now study the construction of salt bridge.

Preparation of Salt Bridge

Bend a glass tube in U-shape o n a burner. Prepare the agar-agar solution as

Agar-agar forms a dispersion of follows: 0.3-0.5 g of powdered agar-agar is dissolved in 10 cm3 o f saturated
liquid in solid Ge., a gel) which solution of KC1/KNO3 at 100°C on a steam bath (add agar-agar powder in small
becomes a thick mass. It
quantities s o that solution does not froth). Keep the solution at 100°C until all
prevents the free flow of
KCIKNO, into the two the agar-agar has passed into the solution. Then add 1-1.5 g of KC1/KNO3 to
half-cells. produce excess of the solid. Now connect the side arm of the bent U-tube to a
rubber tubing and suck the hot solution from the other end of the ruber tubing.
O n cooling, the agar-agar solidifies and this acts as a salt bridge.

Instead of a salt bridge, a filter paper strip soaked in'a saturated solution of KC1
o r K N 0 3 can also b e used across the two half-cells.

Let us now discuss t h e measurement of cell potential. If a current is drawn

from a cell in the course of the measurement of cell potential, t h e cell reactio
proceeds and the concentrations of the solutions change in t h e two half-cells.
Hence, it is important to measure t h e cell potential without allowing current
t o flow. T h e cell potential measured nearly under zero o r negligible current
flow is called electromotive force (e.m.f.) of the cell. W e shall b e using
low-cost mV/pH meter for measurement of e.m.f. and pH.
 Low-Cost Instruments

Fig. 3.9 :Low-cost mV/pH meter

The low-cost mV/pH meter (Fig. 3.9) has a circuit based on operational amplifier.
This instrument draws only negligible current and hence is quite useful in the
measurement of cell e.m.f. Another advantage is that it uses carbon electrodes for
pH measurement. A carbon rod extracted from used dry batteries works as the
electrode. This electrode is available almost a t zero cost. Two carbon electrodes
are provided with each low-cost mV/pH meter.
The two half-cells constituting a galvanic cell are known as the indicator half-cell
and the reference half-cell. The reference half-cell potential is maintained
constant and the indicator half-cell potential is allowed to vary in an experiment.
When we use mV/pH meter for the measurement of concentration of a species
(such as in the measurement of pH of buffers or determination of solubility
product of a salt), the concerned species must be made the electrolyte in the
indicator half-cell. Before studying the various controls of the mV/pH meter, we
should familiarise ourselves with Nernst equation.

3.4.3 Nernst Equation

The relationship between e.m.f. of a cell (or half-cell potential) and the
concentration of species involved in cell reaction (or half-cell reaction) is given by
Nernst equation. Let us consider the following cell reaction.

Nernst equation applicable to this reaction is given below:

where
A and B are reactants and C and D are products in the cell reaction
a,. b,. c and d are stoichiometric coefficients.
As per IUPAC convention,
E!&ij = &HE - E ~ H E ; &HE and &HE are the standard electrode potentials the standard electrode
of the electrodes at the right hand and left hand sides. The standard electrode potential is mentioned for
potentials of some electrodes are given in Table 3.3. The standard electrode the a Wecified
species at the electrode.
potential is the potential at the electrode when the species at the electrode are in
labombry sldlls end thelr standard states at 1 bar (= lo5 P a s 1 atm) pressure at any specified
Ttcludques
temperature and at unit concentration. The temperature usually chosen is 298 K.
n is the number of electrons involved in the cell reaction
F is equal to 96500 coulombs
T is temperature
[ A ] , [B], [C] and [Dl are the concentrations of the concerned reactants and
products.
Table 3.3: Standard Electrode Potentials

~alflcellreactions EON

For the calculation of electrode potentials when the concentration of the species
at the electrode is not equa! to unity, we have to use the following modified forms
of Eqs. 3.15 and 3.16.

Half-cell reaction: A"+(c) + n e - - 4 A(s, I or g) . . . (3.17)

Nernst equation: E = 6' + 2'303RT log c
nF
. . . (3.18)
 Low-Cost Instruments
Where E and EO are the electrode pqtential and standard electrode potential
respectively and c is the concentration of the solution in contact with the electrode.
We shall next discuss the types of electrode systems.

3.4.4 Types of Electrodes

A large number of electrodes are known. For convenience, the electrode systems
are divided into various types. We shall discuss the following three types:

i) Metal-metal ion type

A metal is in equilibrium with its ions in solution. We shall study the following
three examples under this type.
1) zinc-zinc sulphate solution
2) copper-copper sulphate solution
3) silver-silver nitrate solution

ii) Metal-insoluble salt type

A metal is in contact with a saturated solution of its sparingly soluble salt and
another soluble salt having common anion.
We shall study the following example:
Silver-silver chloride-potassium chloride solution

iii) Redox electrodes

These electrode systems have species in solution in two different oxidation states.
We shall discuss the following example:

The carbon rod is an inert electrode and is used for electrical contacl: Some other
familiar examples of redox electrodes are given below; we will not be discussing
them in detail.
Platinum-ferric ion-ferrous ion
Platinum-permanganate ion-manganous ion
These two are used in acid medium.

Let us discuss in detail some of the half-cells coming under the above types of
electrodes.

1) Zinc-zinc sulphate half-cell

The half-cell representation for zinc elctrode is,

zn(s) I znso4(c) The electrode is said to be'
Where c is the concentration of zinc sulphate solution, reversible with respect lo such
ion or ions which lake(s) part
The half-cell reaction is, in the half-cell reaction.
zn2+ (c) + 2e- - Zn(s) . . . (3.19)
This electrode is reversible with respect to z n 2 + ion.

The standard reduction potential for zinc (pznz+,Z,) is -0.76 V. The relationship
useful in calculating the electrode potential of zinc electrode dipped in
a solution of zinc sulphate of concentratioii c can be written using Elq. 3.18 as
follows:
Laboratory Skills and 2.303RT
Techniques Ezn2+/zn = Gn2+/zn+ 2~ log [Z n2+] . . . (3.20)

Construction of Zinc Electrode

Take a zinc rod and dip it in zinc sulphate solution of known concentration. If
A can is a container vessel. the zinc rod is not available, then use the can of a used dry battery. The can
should be cleaned with a sand paper and the connecting wire is to be soldered.

2) Copper-copper sulphate half-cell

The half-cell representation for copper electrode is

Where c is the concentration of copper sulphate solution.

The half-cell reaction is,

This electrode is reversible with respect to cu2+ ion. The standard reduction
0 is +0.34 V. The electrode potential of copper
potential for copper (ECU2+/Cu)
electrode is related to the concentration of cu2+ ions as per Eq. 3.22 which is
written similar to Eq. 3.18.

2.303RT
Ecu2+/cu = ELi +/cu+ log [cu2+] . . . (3.22)

= Ec; f c U + 2'3FT loge

Construction of Copper Electrode

Take a copper rod and dip it in a solution of copper sulphate of known

concentration kept in a beaker. If the rod is not available, then use a mnnecting
copper wire.

3) Silver-silver nitrate half-cell

Silver wire can be used in the construction of

i) silver-silver nitrate half-cell which is reversible with respect to Ag+ ions or

ii) silver-silver chloride half-cell which is reversible with respect to chloride

ions. We shall discuss the former type now.

For silver-silver nitrate half-cell, the representation is

Ag(s) I AgNOs(c)
where c is the concentration of silver nitrate solution.

The half-cell reaction is,

Ag+(c) + e- -+ Ag(s)

Hence this electrode is reversible with respect to A ~ ion.

+
The standard reduction potential for A ~ + - Asystem
~ is (l$Ag+lns) is +0.80 V. The I~nv-CastIns(ruwnls

electrode potential of silver-silver ion electrode is related to the concentration of

A ~ ions
+ as per the equation, a

Construction of Silver-Silver Nitrate Half-Cell

Solder a connecting wire to a small piece of silver wire and insert it from the top
of a glass tube. Use araldite at the tip of the tube and keep it overnight for
drying. Dip the silver wire in a solution of silver nitrate of known ccjncentration.

We shall be using this half-cell in the determination of the solubility product of

silver chloride in Experiment 9 of Block 3 of this course.

4) Silver-Silver Chloride HalFCell

The representation for silver-silver chloride half-cell is,

Ag(s) I AgCl(s) I KCl(c)

where c is the concentration of potassium chloride solution.
The half-cell reaction is,
AgCl(s) + e- 4 Ag(s) + CI-(c) . . . (3.25)
Hence this electrode is reversible with respect to C1- ion.
The standard reduction potential for this half-cell

Nernst equation for this half-cell is given below:

2.303RT 1
E A ~ C V C=I - EOA~CVCI- + F log -
[a-1

Construction of Silver-Silver Chloride Half-Cell

Solder a connecting wire to a small piece of silver wire and insert it from the top
of a jet type glass tube. Use araldite at the tip of the tube and keep it overnight
for drying. Keep the silver wire in contact with 0.1 M hydrochloric acid overnight.
A fine coating of AgCl is obtained over silver wire. This can be used as AgIAgC1
electrode.
5) Quinhydrone Half-Cell

Quinhydrone is a 1:1 mixture of quinone [CGH4O2]represented by the symbol Q

and, hydroquinone [C6H4(OH)2] represented by the symbol H2Q. Quinhydrone
electrode is an example ot oxidation-reduction electrode. It consists of an inert
electrode (carbon rod or platinum wire) dipped in a solution containing a mixture
of oxiclised (Q) and reduced (H2Q) forms of a substance. The half-cell
representation for quinhydrone electrode is

where c is the concen*ation of H+ ions in solution.

Laboratory sldlls and The half-cell reaction is,
Techniques

C6H402(s) + 2 ~ (c)
' + 2e- -----+ C6H4(OH)2(s) . . . (3.27)
(Q) (H2Q) -
The standard reduction potential for quinhydrone electrode is 0.699 V. The
relationship useful in calculating the electrode potential (Eo/u2Q) of quinhydrone
electrode in a solution of H+ concentration c can be written using Eq. 3.18 as
follows:

2.303RT
EQ/H,Q= E L u p + 2F log [ H + ] ~

[since - log [H+] = pH]

As per Eq. 3.27, you can understand that quinhydrone electrode is reversible with
respect to H+ ions. As per Eqs. 3.28 and 3.30, the quinhydrone electrode can be
employed for the calculation of [H'] and pH. In Experiment 8 of Block 3 of this
course, we shall see the use of quinhydrone electrode in the determination of pH
of buffer solutions. In CHE-03(L.) course, quinhydrone electrode has been used in
the potentiometric titration of vinegar under Experiment 2 of Block 1.

Construction of Quinhydrone Electrode

You are provided with two carbon rods to be used as electrodes. Use one of these
carbon rodsand dip it in a solution containing H+ ions. Add a pinch of
quinhydrone. This is quinhydrone electrode.

With this brief introduction to the elementary concepts of polentiometry, let us

now take up the functions of the various controls of a mV/pH meter and the
method of operation.

3.4.5 Various Controls of the Low-Cost mV/pH Meter

Power Switch : This is located on the back panel of the instrument.
This is used to turn the instrument OFFION. After
connectjng the instrument to the mains, if this sw:tch is
turned on, the LED on the front panel will glow.

Range selector : This switch on the front panel of the instrument may be
put on three positions marked pH, 200 mV and 2V.
This brings into the circuit the pH scale, the 200 mV
scale or 2 scale. When the switch indicates pH, the
meter reads between pH 2 and 7 o r between 7 and 12;
at 200 mV, the meter reads between 0 and 200 mV; and
at 2 V, the meter reads between 0 and 2 V.
 Meter switch : This is a sliding switch with three positiolls on the front Low-Cost Instrumcn(s
panel. The middlc posilioa serves as a standby position
(i.e., "off' position) when the meter is not in circuit.
This switch is used to reverse the polarity of
connections t o the meter for measurements in the Ijk
range 2-7 o r 7-12.

Set ten~perature: This knob on the front panel has a scale marked in
degree celsius. You must adjust it to read the
temperature of the test solution.

Set Zero : This knob o n the front panel is used for calibrating the
instrument. While calibrating for e.m.f. measurement,
this knob is used to bring the meter reading to zero.
When the meter is being calibrated for reading pH, this
knob is used lo s ~ the
t Ilieter at the pH of the indicator
cell solution.

Set slope : There are two knobs located o n the back panel; the
lower knob is used during e.m.f. calibration and the
upper o n e is used for the p H calibration.

Cell Connection There are two arrangements for connecting the cells to
the instrument. For cells using carbon electrodes, two
lead wires with black and red crocodile clips are
provided. The black goes to the reference half-cell and
the red to the indicator half-cell.

T h e other arrangement has a socket on the back panel

for plugging a commercial glass clcctrode; a terminal is
provided nearby for a reference electrode, e.g., calomel
electrode.

3.4.6 Method of Operation

Before using the p H meter, it is necessary to calibrate it. Check the mechanical
zero of the meter before turning it on. If the needle is not showing zero, then
adjust it inserting a small screw driver into the hole under the meter. The
calibration for e.m.f. measurement is given below. The calibration for pH
measurement will be done in Experiment 8 of Block 3 of this course.

Calibration of the instrument for e.m.f. measurement

1) Connect the instrument to the mains and sw~tch~t on. The LED on the
front panel should glow.

2) Short the two input leads. Shift the metergswitch to 2-7 o r 7-12 position. If
thk meter does not read zero, adjust the set zero knob until it does. D o not
disturb this knob.

3) Use a calibrated voltage source, such as the AVO source to obtain 200 mV.
Keep the meter switch a t STANDBY position. Connect the voltage source
to the mV/pH meter a t the cell connection terminals - positive lead of the
voltage source to the red terminals. Shift the meter switch to 2-7 position
and the selector switch to the 200 mV range.

4) Adjust the lower knob of the set slope until the meter reads full scale. With
this adjustment, 1he meter is c a l i b r a i ~ d10 read between U and 200 mV.
L.bOrP(Ory S W and After this, the lower set slope knob is not to be disturbed for the rest of
Tmhnlques
the experiment.
"

5) This calibrares the 2 V range also. You can check that by shifting the
selector switch to the 2 V range and, by including a 2 V calibrated input at
ihe celi connection terminals. Once the instrument is calibrated, you can
connect any cell for which e.m.f. is to be measured at the cell connection
terminals and, read the e.m.f. Each division is equal to 4 mV in the 200 mV
range and 40 mV in the 2 V range.

To explain the construction of a galvanic cell and the use of mV/pH meter in
e.m.f. measurement, the following demonstration experiment is given.

3.4.7 Demonstration Experiment 3: Construction of Daniell Cell and

Measurement of E.M.F.
We shall illustrate the way of construction of a galvanic cell and measuring the
e.m.f. For this, we shall construct Daniell cell. This experiment will help you in ,.
performing experiments 8 and 9 of Block 3 of this course.

We shall construct Daniell cell using 3.01 M Z n S 0 4 and 0.1 M CuSO? The cell
can be represented as follows:

The cell reaction for Daniell cell can be written as follows:

zn(s) + cu2+ (0.01 M) .-A zn2+(0.01 M) + CU(S) . . . . (3.31)

You can see that this equation is obtained by subtracting Eq. 3.19 from Eq. 3.21
since, Z n gets oxidised to z n 2 + and c u 2 + gets reduced to Cu. You know that Eqs.
3.19 and 3.21 are written for the reduction of the concerned species only. Again
Nernst equation appiicabie lo Eq. 3.31 is obtained as follows by subtracting Eq.
3.20 from Eq. 3.22.

2.303RT 2.303RT
E = ~ : , 2 + l c,+
2F log [cu2+]- (EZn2? zn+ ZF log [ ~ n ~ + ~ )

2.303RT [cu2+]
= (EOcu24 cu-~oZn2+l23 + 2F
log - ...
[zn2+]

Aim
i) To construct Daniell cell

ii) To find thc r.m.f. of Danicll ccll

Requicements

Apparatus
Copper rod
Zinc rod
Salt bridge o r filter paper strip
Beaker (100 cm3)
mV/pH meter
Connecting wires
 Chemicals Low-Cost Instruments

0.1 M copper sulphate solution

0.01 M zinc sulphate solution
Saturated potassium nitrate solution.
rocedure

First mV/pH meter has to b e calibrated as per the instruction given under
"calibration of the instrument for e.m.f. measurement"

Next t h e zinc rod is dipped in a solution of 0.01 M zinc sulphate. The copper rod The diagrdm of Daniel, cell ir
is dipped in 0.1 M copper sulphate solution. The zinc half-cell is connected to the given in Fig. 3.8.
indicator terminal of the mV/pH meter. The copper half-cell is connected to the
reference ~ e r m i n a l of the instrument. The two half-cells are connected by means
of a potassium nitrate salt bridge o r by means of a filter paper soaked in
saturated potassium nitrate solution.

The e m f . of the cell is measured. The measurement is made a t least two more
times and the average e.m.f. value is taken. The result is entered as follows:

Temperature - . . . .K
T h e e.m.f. of Daniell cell containing
0.1 M C u S 0 4 solution and 0.01 M
z n s - 0 4 solulion measured using
mV/pH meter:

i) first measurement
-- . . . . v
ii) second measurement - ....V
iii) third measurement - . . . .V
Average e.m.f. - . . . ./ 3 V

T h e calculated value of e.m.f. of = 1.295 V

the above Daniell cell using Eq. 3.33

SAQ 3

Calculate the e.m.f. of the following cell at 298 K:

Hints: (i) Use Eq. 3.33 (ii) Since ~ ~ ~ and

~ ~ 2 ~ + ~ / a r~e ~quantities
2 ~ + , defined
~ ~

~y standard
state, ~ ~ ~ ~ ~ 2 ~+ / ~ ~ ~~ , 2 + E/ O ~ ~, ~ + / ~~ , (which is equal tol.1
V) a r e considered t o b e exact quantities. Hence '1.1' is supported to have
2'303RT
infinite significant figures. (iii) = 0.059 V
F
Lebomtory Sldlls and
Technlqaes 3.5 SUMMARY
In this unit, we have discussed the principles of colorimetery, conductometry and
potentiometry. We have explained the use of low-cost instruments in measuring
absorbance, conductance and e.m.f. We have described three demonstration
experiments to illustrate the use of the low-cost instruments.

3.6 ANSWERS
A
1) According to Eq. 3.1, c = -
d

K
2) Using Eq. 3.,9, A, = - = 11.67 S m2 mol-'
C

[zn2+] = 5.0 x M

Using these values in Eq. 3.33,

FURTHER READING
1. Senior Practical Physical Chemistry, B.D. Khosla, A. Gulati and V.C. Garg,
R. Chand & Co., New Delhi, 4th ed., 1985.
Practical Chemistry, S. Giri, D.N. Bajpai and O.P. Pandey, S. Chand &
Company Ltd., New Delhi, 7th ed., 1993.