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1 Objectives:
Measurement of electromotive forces ( EMF ) and terminal voltages of galvanic cells, determination of
the internal resistances, investigation of the dependence of EMF on the electrolyte concentration.
2 Theoretical background:
salt bridge
Cu s Zns ZnSO4 aq. saturated CuSO 4 aq. Cu s
cZnSO4 KNO3-solution cCuSO4
2.1 The electromotive force, terminal voltage, and the internal resistance of a galvanic cell
The method for the measurement of the potential difference (terminal voltage or terminal potential
difference) of a galvanic cell can be represented by a simple electric circuit (Fig. 8.1.1.). According to Ohm’s
law the current flowing through the resistances Rb (internal resistance) and Rk (load resistance) can be
given as:
EMF
I (8.1.1.)
Rb Rk
The voltage between the terminals of the cell i.e. the potential drop E k across the load resistance Rk can
be also easily calculated using Ohm’s law:
EMF
Ek I Rk Rk (8.1.2.)
Rb Rk
Fig. 8.1.1.
1
After rearranging eq. (8.1.2.) we have:
EMF Rb Rk
(8.1.3.)
Ek Rk
It can be seen from the above equation, that for a galvanic cell the terminal voltage is always smaller than
the electromotive force, however, the smaller Rb and the greater Rk is, the smaller the difference between
E MF and E k is. In the limiting case Rk , Ek EMF . It also means, that the limiting value of the
current flowing through the cell is zero.
(In other words: In case of discharging of an electrochemical cell, the terminal potential difference E k
cannot be greater than the E MF of a cell but in the absence of the internal resistance, the terminal potential
difference becomes equal to the E MF of a cell. In case of charging of an electrochemical cell having internal
resistance Rb , the terminal potential difference E k of the cell is greater than its E MF . Here, the terminal
voltage exceeds the E MF of a cell by the term I Rb . If there is no internal resistance then Rb = 0, then
EMF Ek .)
2.2 Measurement of the electromotive force with a voltmeter of high internal resistance
According to the above considerations, the E MF of a cell can be measured with a voltmeter, provided that
the internal resistance of the voltmeter is “high enough”. But what is high enough? Obviously, the current
passing the cell must be low enough to ensure the electrochemical equilibrium at both electrodes, i.e. it
should be much smaller than the exchange current of either electrode. Of course, in dubious cases this should
be checked with adequate experiments.
The determination of the E MF of a cell using a potentiometer is a classic experiment. This experiment has the
advantage that the E MF of a cell can be measured without drawing any current from the cell, in short the
measurement can be done as if it was done with a voltmeter of infinite resistance.
Figure 8.1.2. presents a compensation coupling with which the electromotive force of a voltage source
(galvanic e.g. cell) can be measured. RT (= R1 + R2 ) is the total resistance of the potentiometer in the circuit.
E x is the cell under test and E N is a standard cell. A standard cell is a galvanic cell whose voltage is
accurately known and remains sufficiently constant for instrument calibration purposes (e.g. the Weston
standard cell has a voltage of 1.018636 volts at 20°C).
2
Fig. 8.1.2.
If the S switch is open, the current in the circuit containing the voltage source (the voltage is U cvs ) equals
I Ecvs / R1 R2 . If U cvs is constant and R1 R2 is also constant, then I remains constant during the
measurement. The cell under test is connected parallel to the resistor R1 in series with the switch S and a
galvanometer G. (A galvanometer is a very sensitive ammeter.)
The value of the resistor R1 (the resistance) should be set so that the current passing the galvanometer is
zero ( I G 0 ), even if the switch is closed. (If the value of R1 is decreased, the value of R2 should be
Ex I k Rx . (8.1.4.)
Correspondingly, after replacing the cell under test with a standard cell, in case of I G 0 the
En I k Rn . (8.1.5.)
In eq. (8.1.5.) R N is the value of R1 if the current passing the galvanometer is zero ( I G 0 ), even if the
switch is closed.
From eqs. (8.1.4.) and (8.1.5.) we get:
Rx
E x En (8.1.6.)
Rn
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(The switch S should be switched on only for very short time periods, in order to avoid the polarization of
the electrodes.)
Of course, in the practice of signal processing it is impossible to deal with “zero currents”, in reality a
non-zero current is flowing through the cell. The intensity of this near-zero current depends on the sensitivity
of the galvanometer (in our case the sensitivity of the galvanometer is of the order of magnitude of 10–6 A).
There is another possibility for the determination of the electromotive force if we follow the measuring
instruction given in the definition of E MF . The method is the following: In order to measure the internal
resistance we add different load resistances in parallel with the cell, and the voltmeter of high input
impedance (see Fig. 8.1.3.).
Fig. 8.1.3.
In this case a current I passes through the electrochemical cell. Using Kirchhoff’s laws (Kirchhoff's laws:
pair of laws stating general restrictions on the current and voltage in an electric circuit. The first of these
states that at any junction of paths, or node, in a network the sum of the currents arriving at any instant is
equal to the sum of the currents flowing away. The second states that at any given instant the sum of the
voltages around any closed path, or loop, in the network is zero) the terminal voltage can be expressed as:
Ek EMF Rb I (8.1.7.)
From Ohm’s law the current I flowing in the above circuit is equal to
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Ek
I . (8.1.8.)
Rk
By substituting I from eq. (8.1.8.) into eq. (8.1.7.):
Ek
Ek EMF Rb (8.1.9.)
Rk
If Rb is constant (i.e. it is independent on I), the Ek vs. Ek Rk plot yields a straight line. The slope of the
line equals the internal resistance Rb multiplied by –1, and the intercept gives the value of EMF .
It should be noted, that the current-voltage characteristics of electrochemical cells are typically non-
linear. However, if the current is low enough, the current vs. potential curve can be well approximated by a
linear function. In such cases Rb can be treated as substantially constant.
3 Experiments
Procedure
Results sheet : In each case, label the diagram appropriately to describe the cell you have constructed.
resistance of the electrolyte solution in the glass stopcock (there is a thin layer of electrolyte solution
between the shell and the plug).
5
The potentiometer is formed from a length ( l T ) of uniform resistance wire attached to a DC source ( U CVS )
such as a lead acid accumulator (Fig. 8.1.4.). If a standard cell whose EMF is known (e.g. a Weston standard
cell) is used as one of the cells then the potentiometer can be calibrated, the standard cell is wired in series
with a galvanometer between B and a moveable probe, the galvanometer will give a zero reading at point N.
Then distance BN ( l N ) is measured. The experiment should be repeated to find point X where a zero current
Prepare serial dilutions (at least 5 solutions) of the stock mixture (0.1 mol/dm3 CuSO4-solution) in the
range of 0.001 mol/dm3 to 0.1 mol/dm3. Values of the concentrations must be selected at nearly equidistant
intervals in the logarithmic (concentration) scale.
The stock solution should be diluted with MgSO4 solution of 0.1 mol/dm3 (instead of water), in order to
maintain constant ionic strength. (At constant ionic strength the mean activity coefficients ( ) are
approximately constant.)
Using the CuSO4-solutions construct galvanic cells according to the cell diagram
6
and measure the E MF of the cell with a high-impedance digital voltmeter. Record the measured voltage in
your lab notebook (at least 5 data pairs in a table like the table below).
4.1 Measurement of the electromotive force with a voltmeter of high internal resistance
Present the experimental results with uncertainties.
Plot the Ek vs. Ek / Rk curves using the two data series measured: with the glass stopcock in closed (first
measurement series) and open position (second measurement series). According to (8.1.9.) the electromotive
force and the internal resistance of the cell can be obtained by linear regression of Ek against Ek / Rk . The
slope of the curve is Rb , and the intercept gives the value of EMF .
Plot the EMF / V vs. lg cCu2 / mol dm -3 data, and fit the data with a straight line. The two parameters
of the line, the slope and the intercept, provide the two constants in Nernst’s equation.
Perform a statistical analysis of the results.