EXPERIMENT 7

THERMODYNAMICS OF AN ELECTROCHEMICAL CELL

The standard Gibbs free energy for an electrochemical cell is given by the equation
- G nFE (1)
where n is the number of moles of electrons involved in the redox process, F is faradays
constant ( F = 96,500 C/mol) and E is the standard potential of the electrochemical cell.
Measurement of the potential of a cell can be used to determine the maximum work
obtainable but a single voltage measurement is insufficient to obtain other
thermodynamic values of entropy and enthalpy. The three standard thermodynamic
properties are expressed by the following equation:
G H T S (2)
We can combine the above relations to obtain the following equation
G nFE H T S (3)
Obtaining the partial derivative with respect to the absolute temperature at constant
pressure will give the Gibbs-Helmholtz equation


_ _


, , P P
G E
nF S
T T
(4)
Substitution for G and S in equation (2) will give an expression for H

1 _


1
, ] P
E
H nF E T
T
(5)
By substituting ( ) /
P
E E T T b + into equation (5), we shall obtain
H nFb (6)
where b is the y-intercept of the voltage-temperature plot. In this experiment a Cu/Cu
2+
-
Zn/Zn
2+
cell will be used. The cell notation is
Zn(s)|ZnSO4 (1.0 M) CuSO4 (1.0 M) |Cu(s)
The measurement of emf values at different temperatures will provide thermodynamic
values for the above electrochemical system.
APPARATUS AND MATERIALS
Water bath, Bunsen burner, tripod or iron ring, thermometer or thermocouple, small
beakers, analog or digital multitester, crucible tongs
You need to supply the following materials:
2 Beral pipets, 12 cm x 3 mm zinc strip (thickness of about 1/100 inch), copper strip
(same dimensions as the zinc strip), cutter, glue gun or mighty bond, masking tape, ice
CHEMICALS:
Prepare the following solutions from solids or concentrated acid.
1.0 M ZnSO4, 1.0 M CuSO4, 30% H2SO4, saturated HgNO3, 1.0 M NaNO3
PROCEDURE:
1. Prepare the zinc electrode by immersing the metal strip in 30% H2SO4 just long
enough to clean the metal surface. Rinse with distilled water then amalgamate it by
placing in a saturated solution of mercurous nitrate (CAUTION: avoid skin contact.
Clean spills immediately.) for 10 minutes.
2. Construct the Zn/Zn
2+
couple by making a small incision at the top of the Beral pipet
and inserting the amalgamated zinc strip through the slit. Seal the zinc strip with glue.
After the glue is dried, squeeze the bulb of the pipet to draw enough 1.0 M ZnSO4 to
cover the amalgamated part of the zinc strip.
3. Prepare the Cu/Cu
2+
half-cell in the same manner. After sealing the copper in the
pipet, the squeeze the bulb of the pipet to draw enough 1.0 M CuSO4 to cover the lower
5 cm of the copper strip.
4. Immediately after preparation, place the two couples in a small beaker filled with
1.00 M NaNO3. The pipet tips must be about 2 cm apart.
5. Place the beaker containing the half-cells in a water bath initially at 35 C, and the
potential measured at intervals of 5 C down to 15 C. Vary the temperature by adding ice
to the water bath. To check on the reproducibility of the data, raise the temperature to 35
C and finally lower again to 15 C with further periodic measurement of cell voltage.
CALCULATIONS:
1. Plot cell potential (y) versus absolute temperature (x) and perform linear regression.
Calculate H from the value of the y-intercept (eq. 6), S for the value of the
slope (eq. 4) and G from equation (1). Compare the values you obtained with
literature data.
DATA AND RESULTS:
Table 1. Temperature Dependence of Cell Voltage for the Zn/Zn
2+
-Cu/Cu
2+
Cell
Temperature (K) Measured Cell Potential,E (Volts)
Descending T Ascending T Descending T
308
303
298
293
288
Linear Regression for Voltage-Temperature Data
Slope (V/K)
E298 (V)
Corr. Coefficient (r)
y-intercept (V)
Table 2. Thermodynamic Data for the Zn/Zn
2+
-Cu/Cu
2+
Cell
Mean Experimental Value Literature Value
E298 (V)
dE/dT (V/K)
H (kJ)
S (J/K)
G (kJ)