2.1 INTRODUCTION
are the resistances of the connecting wires which are usually negligible, Cdi *
and Cd! 2 are the double layer capacitances of the two electrodes, Cp represents
the interelectrode capacitance in parallel with the cell and RS0| is the resistance
of the solution between the electrodes. Rfl and Rn represent the Faradic
22
resistances at two electrodes (i.e. the electrical equivalent of any possible
<2sy
C
v"p - Interelectrode capacitance
current will flow through the resistive components and R^i On the other hand,
if an ac voltage in applied, alternating current will flow through the Cat’s, Rs0t
and Cp This prevents building of voltages across Rn and Rq which would lead to
Faradic current flow. This situation demands for a small value of Cp and large
CarSj so that the effect of solution resistance (R^oi) can be studied by itself.
23
Practically, the double layer capacitance is increased by coating the platinum
electrodes with spongy platinum black, which also greatly enhances the
and the resulting voltage is measured. The aim is to measure the solution
the electrodes and the field effect interferes with the measurement, and both
The 3-pole cell is not as popular now as it has been replaced by the 4-pole one.
The advantage of this design was that the third pole which was linked to pole 1
allowed the field lines to be guided and confined in an optimal manner, limiting
such as beaker volume and position of the cell in the beaker (field effect). It
In a 4-pole cell, a current is applied to the outer rings (1 and 4) in such a way
that a constant potential difference is maintained between the inner rings (2 and
24
3). As this voltage measurement takes place with a negligible current, these two
electrodes are not polarized (R2 = R3 = 0), The conductivity will be directly
operational to the applied current. The geometry of 4-pole cells with an outer
tube minimizes the beaker field effect, due to the measurement volume being
well defined within the tube. The position of the conductivity cell in the
measurement.
immersed in the solution, an electric current flows due to the migration of ions
solutions of electrolytes also obey the Ohm’s Law, with deviations arising only
in cases of high voltages & high frequency currents being passed through the
solution.
• DC contact measurement.
25
2.3.1 DC Contact measurement
contact between the test substance and measuring device should have perfect
conductance and introduces no additional voltages into the circuit such as the
substances and measurements are sufficiently idle and the simple relationship
device that provides the resistance of conductor in Ohms (Q, when connected
across the ends of the conductor. A simple circuit of this kind is shown in
figure 2.2
After initial adjustment, i.e. short-circuiting the probe and adjusting the
potentiometer to lead full scale (Ii), then the total resistance of the circuit is
given by
R = Rm + Rf + Ra ----------------------------------------------- (2.1)
the current value decreases to I2, which is depends on the value of ‘Ru’.
Therefore,
1.5KQ. Then the relationship between the unknown resistance and current
converters. From Ohm’s law, V=IR, it is observed that the voltage across a
flowing through the resistor for a constant voltage. Therefore, the first case
an operational amplifier.
27
point is maintaining zero potential, the input current I, produces an output
voltage.
V0= I Rf
V0 = - V/R, Rf = - VGRf ------------------------ (2.4)
operational Amplifier.
Rf
G to I Converter I to V Converter
Rf
28
2.3.2 Null comparison measurement
In this technique, the effect of an unknown resistance must be compared
standard resistances can be kept in two arms of a wheat stone bridge, and
varying the standard resistance until the difference between the voltages or
il+i2
1 V ll
i2
->
BATTERY
- - - - - - Wv- - - - - - —wv- - - - - - - -
RA RB
NULL DETECTOR
RC RV
——m- - - - - - I—m- - - - - - - -
Rc//Rr = R/Rb
the values of standard resistance values Raand RBi and the variable resistance Rv
29
An assumption made in the DC contact and null comparison
measurement discussed above is that the probe leads and contact to the
measured conductor are assumed to be ideal. An ideal and contact has zero
other effect. Generally, the above discussion applies for high resistance
shown in fig 2.5 (a) are suitable. But the demerit with this technique is that it
ohmmeter. The reason for this is that the contact between the metallic electrode
and electrolytic solution is far from ideal. This problem is, overcome by using
Fig 2.5 (b) depicts the type of cell arrangement used for the
the part of solution that is in the capillary tubing between the two vials of the H
cell, the reference type of electrodes are commonly used for the voltmeter
probes.
30
VOLT METER
\ \
A "TiV
\ ________ \
CURRENT SOURCE
VOLTMETER
□
CURRENT SOURCE
□
Fig. 2.5(b) Four Contact Measurement of Electrolytic Conductivity
31
2.3.3 Capacitive contact measurement of conductance
may be represented as the double layer capacitance Cd> in series with the
given by,
t = time (s)
written as
32
Rs
(a)
O M 2)C
33
The relation between Xc and frequency is inverse in nature i.e. Xc
decreases as frequency increases and vice-versa. Typical values for the double
layer capacitive reactance for aqueous solutions are 10-100 pf/cm2. Thus, the
the total opposition to the current in an AC circuit, for the network under
consideration.
From expressions 2.8 and 2.9, it is clear that as the signal frequency is
The potential across Cd also decreases gradually and the phase angle <}» between
method of realizing this is to increase the surface area and hence the
When the frequency of the applied signal is above several KHz, even
then the impedance of the conductance cell tries to deviate from Rs. Since the
34
solution medium is itself a dielectric situated between two parallel charged
surfaces, the equivalent circuit of such a situation in shown in fig 2.7(a). Here
velocity of light and the cell constant respectively. The dielectric constant of a
dilute aqueous solution is approximately 80, and if the cell constant is assumed
to be 1 cm"™ then the Cp value will be about lOpf. if the applied signal
frequency is 1.6 KHz, this results in a reactance Xc-10Mn. The same analysis
holds good for a series circuit with the exception being that the voltages across
35
71
o
(b)
The current flowing through the resistor in phase with the applied
voltage, while the current in the capacitor leads the applied voltage by 90° as
36
vs/xc
Therefore, the cell impedance in expressed as
electrolyte in the solution of interest. Other factors also try to add up to the
parallel capacitance like, contact capacitance at the junction of the cell leads
and the measurement system, lead capacitance and the capacitance due to the
by using an oil bath rather than water bath for thermo stating and choosing a
high and low frequency models of the conductance. The response of the system
-2 O .2 4- <f ~ ~ i-
lOfi !
From above the graph it is evident that the solution resistance can be
measured effectively in the plateau or the narrow mid frequency range. For
most of the solutions if the plateau is located, the solution resistance is directly
proportional to the resistive component of the cell impedance. Fig 2.9 (b)
depicts the circuit for measuring impedance of the cell based on the above
2.9(c). the switches S[ and S2 are used to calibrate the output and selection of
DC SIGNAL
IC08
w, -
-w-
pace
■r>
(b) Circuit Diagram
39
(C) Wave forms
40
100R
chromatography.
accomplish this task and the waveforms are shown in Fig. 2.10. Waveforms (a)
and (c) shows that the magnitude of the correlation integral is proportional to
alti.
ACC.
UBBftKf ) 4]
1
CpOllo |j
waveform (iii). That will cancel upon integration and unshaded region
represents Jr Vs dt. The cell in the circuit becomes impedance to the current
follower. When a sinusoidal signal (Vs) is applied across. The cell, the output
shown in waveform (i). Since I is in phase with VR, the bipolar square
Rn
42
Fig. 2.10 Conductance measurement by phase selective
Demodulation Circuit schematic and waveforms.
which performs the multiplication of the bipolar square wave with the input
signal (sinusoidal) Vs. The output of the multiplier is then passed through an
active low pass filter designed using op-Amp and the output dc voltage is
43
proportional to R. By using the phase selective demodulation technique an
accuracy and resolution better than 1 part of 104 over a frequency range of
which has been the traditional instrument of choice for accurate conductance
condition for the AC Bridge is same as that for the DC Bridge except, when
reactive elements are present, then the impedance vectors must be substituted
oscilloscope.
the bridge balances when Rj = ICeii and Cs = Ccea By balancing the bridge
capacitance and double layer capacitance, which poses problems with regard to
Large current flow through the solution leads to the Faraday process,
which charges the double layer capacitance. Also these capacitances are
44
A
determine the area of the voltage time curve. They have further shown that this
of parallel capacitance CP over a wide range of values. The paper also details
utility was demonstrated by the studies on KCl solution and acetyl chloride
ethanolysis reaction.
45
A wide band, precision, dc coupled lock-in detector and gated integrator
design was simple and was capable of measuring ac cell admittance from 0.005
dynamic range (10'! to 10~8Q) and the signal-to-noise ratios of up to 6X103 for
single data acquisition and 6xl05 for ensemble averages of 2000 acquisition
were obtained. The accuracy of the system was reported to be in the range of
data rate. Numerical correction factor for temperature changes, which occur in
developed by Diard et al [9]. An new method was devised for synthesizing the
signal analyzer was used to measure the electrolyte solution resistance. With
conductivity measurement.
46
Boiko and Boiko [10] have developed a new cell to measure the
electrical conductivity of the solutions. The cell design made the unlimited
solution level.
and Enke [11] have developed a new method. An added advantage of this
analysed. The analysis is done with respect to polarization, the series (C<n) and
voltmeter as a null detector in the conductance bridge the ideal frequency was
47
taking a detailed review an attempt is made here to mention some of the
missing links.
appropriate for conductance measurements if the loss tangent is low and phase
of frequency.
analyzer.
response does not correspond to that predicted by simple ideal circuits; for
Cole Cole-Davison [17] expressions have been used to fit the experimental
48
results. They conducted two terminal ac measurements over the frequency
3 7
range 10' - 10 using a combination of bridge and automated phase sensitive
developed Aswani Sharma and Bhatia [18) with a GRU (USA) capacitance
found that at higher temperature cr{co) exhibits a much faster increase with
measurements over the frequency range 5Hz to 13MHz. This measuring cell
49
measurements using network analyzers, HP instruments number (1-1300MHz)
and 4192A(5Hz-10MHz) was performed by Behrooz and Zettle [20] for high
dependent voltage S sin (<y t) across a ceramic sample and the response form
co. The real and imaginary parts Z i.e., Z1 and Z11 is determined by using a
quadrate oscillator, current to voltage converter and phase sensitive detector for
and also developed PC-based automated impedance analyser system which can
be used in the frequency range 1Hz to 30MHz and temperature range 299K -
573K. This technique is found to be useful for the study of bulk conductivity,
50
bulk capacitance, grain boundary resistance and grain boundary capacitance at
plots for certain range of temperature are found to have low frequency loops.
Subba Rao [25] and his co-workers carried out electrical conductivity
frequency range 70-100KHz and temperature ranging 300 to 950K. From the
at high frequencies.
complex. It is evident from the review of literature that very little work has
51
allows a researcher to borrow the knowledge of already established ac and dc
circuit theory and characterize the sample as electronic equivalent circuit. This
direct connection between the behavior of sample under test and that of an
presented in Chapter 1.
complex and involve several IC’s. In this work a modest attempt is made to
develop a low cost simple circuit for measurement of complex impedance and
conductivity.
controller.
52
2.5 AIM AND SCOPE OF THE PRESENT STUDY
increased manifold in the present days. This has led to their introduction in the
attempt is being made to interface the personal computer with the experiment.
53