Experiment

Electrochemical Determination of G, H, and S

Objectives
To determine thermodynamic properties using electrochemical techniques.

Introduction
Thermodynamics is concerned with the energy changes that occur in chemical and physical
processes. Several fundamental laws summarize these energy changes.
The first law of thermodynamics states that energy is conserved, that is, it can not be
created or destroyed. Energy can be converted from one form to another, but the total remains
constant. In chemical reactions, rearrangements of atoms and electrons occur, leading to new
species, which interact with their surroundings. This changes the chemical potential of the system,
and thus heat is evolved or absorbed. This heat energy is usually expressed as enthalpy,

H = H final H initial
The second law of thermodynamics relates to the spontaneous nature of a chemical process.
It has been established through observation that processes that are spontaneous in one direction are
not spontaneous in reverse direction. For instance, if you drop a book on the floor, it does not
spontaneously move back into your hand. This fact applies to chemical as well as physical systems.
Spontaneity is associated with an increase in randomness or disorder of a system.
Thermodynamically, this is expressed by a quantity called entropy, S. the change in entropy of a
system is expressed as

S = S final Sinitial
The free energy, G, interrelates the enthalpy and entropy of a system. For a process
occurring at constant temperature and pressure, the change in free energy of a system is expressed
by

G = H T S

(1)

The sign of G relates to the spontaneity of the reaction

1. If G is negative, the reaction is spontaneous in the forward direction.
2. If G is zero, the reaction is at equilibrium.
3. If G is positive, the reaction is spontaneous in the reverse direction.
The quantities G , H and S depend only on the initial and final states of a system
and not on the pathway of the change. Such quantities are called state functions and are said to be
path independent.
The investigation of electrochemical reactions offers a simple and direct method for
measuring thermodynamic values, because the quantity of electrical energy produced or consumed
during an electrochemical reaction can be measured very accurately. The free energy change, G ,
of an electrochemical reaction is related to the voltage, E , of the electrochemical cell:
G = nFE
(2)
Where n is the number of moles of electrons transferred in the reaction per mole of reactant,
and F is Faradays constant.

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If voltage measurements of the cell are made at different temperatures, the change in entropy,

S , of the system can be expressed at constant pressure as

d (G )
S =
dT

(3)

Substitution of Equation 2 into Equation 1 gives

S =

d (nFE )
dT

or

S = nF

dE
dT

(4)
-1

Faradays constant (F) is the electrical charge on 1 mol of electrons, 96,500 J V mol. E is
expresses in volts and the temperature in K. S can be expressed as J V-1mol-1 or cal K-1 mol-1 (1
calorie = 4.184J). Note that the quantity dE / dT in Equation 4 is a slopethe change in the
electrochemical voltage with respect to temperature. Thus, a plot of E (y axis) versus T (x axis)
will have an instantaneous slope (tangent) of dE / dT at any temperature T.
2+
2+
In this experiment, the electrochemical cell will consist of the Zn/Zn and Cu/Cu half-cells,
connected by a salt bridge. The half-cell reactions are

Zn

Zn 2+ + 2e

Cu 2+ +2e

(oxidation at the anode)

Cu

(reduction at the cathode)

__________________________________________________

Zn+Cu 2+

Zn 2+ + Cu

(overall cell reaction)

Tables of half-cell potentials can be found in Appendix. It should be noted that the potentials given
o

in these tables are of E , that is, the standard potentials. Real potentials, E, depend on
temperature, concentration of irons in solution, etc., and are obtained from the Nernst equation:

E = Eo

RT aproducts
ln
nF areac tan ts

In most cases, concentration can be used in place of activity without incurring too large of an error,
the various constants are collected, and the expression is evaluated at 25, resulting in a
simplified version of the Nernst equation:

E = Eo
2+

When the concentrations of the Zn

0.059 [products]
ln
n
[reac tan ts]
2+

and Cu

solutions are equal, the log part of the Nernst

o

equation reduces to zero. Under these conditions, the standard voltage, E , and will be 1.100V for
the cell described. (Do you experimentally obtain this value for E?). The free energy, G, may be
obtained from the voltage by the equation

G = nFE

(5)
In this experiment, the cell voltage will be measured at three or more temperatures. If several
temperatures are used, a plot of E versus T yields the value of dE/dT from the instantaneous slope
of the line, as previously discussed. Substitution of this slope into Equation 4 gives S. The value

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for H can then be calculated.

Experimental procedure
Preparation of salt bridges
The salt bridge may be prepared by dissolving agar-agar (100 mg) and KNO3 (500 mg) in 5mL of
water, and heating until the mixture thins, thickens, and then thins again. The hot solution is
transferred to the wet glass U-tube by Pasteur pipet. The solution sets to a gel in 10-15 minutes.

Preparation of Solutions and Electrodes

Obtain 7mL each of 0.500M solutions of Cu(NO3)2 and Zn(NO 3)2.
NOTE: The results of the experiments are dependent on the
accuracy of the solution concentrations.
Cut a 540 mm rectangle of copper and zinc metal from a thin sheetthese will serve as the
copper and zinc electrodes.

Construction of the Half-Cells

Prepare the copper half-cell by fitting a 10mL beaker with the copper electrode, it being held
in place by a rubber band around the upper portion of the beaker. Bend the upper end so the
electrical lead from a voltmeter can be attached with an alligator clip (See Figure 1). Add 6-7mL
of the copper nitrate solution to the beaker.

Figure 1 Copper half-cell.

Fashion the zinc electrode in a similar manner in a second beaker and add 6-7mL of the zinc
nitrate solution. Connect a salt bridge from the copper nitrate solution to the zinc nitrate solution,
as shown in Figure 2.

Measurement of Temperature and Voltage:

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Note: It is important to realize that the voltage measurements at each

temperature should not be taken until the system is at thermal equilibrium.
Usually, a period of at least 15 minutes is sufficient for these conditions to
be met. No reaction occurs until all connections are made. Connect the
wires to the meter last. If a negative deflection occurs on the meter, reverse
the wires to the meter. Disconnect one wire during the thermal
equilibration so that the concentrations dont change.

Once the cell is constructed, allow the system to reach thermal equilibrium (15 minutes).
Measure the voltage of the cell on the voltmeter and also the room temperature. Record these
values on the data sheet.

Figure 2 Electrochemical cell

Cool the cell assembly in an ice bath. After the temperature has stabilized (about 15 minutes),
measure and record the voltage and temperature. Now, place the cell in a previously warmed water
or sand bath at approximately 50. Allow the system to come to thermal equilibrium (about 15
minutes). Record the voltage and temperature.
If further readings are desired, the cell may be placed in a series of baths set at selected
temperatures. It is important to remember to allow the system to come to thermal equilibrium
before readings are obtained.

Calculation of Thermodynamic Values

Construct a plot of E(y axis) versus T(x axis). The instantaneous slope of this plot at any
temperature T gives the value of dE/dT at that temperature. Over the temperature range in this
experiment, the value of dE/dT is reasonably constant, and the plot of E versus T should give a
straight line. Substitution into Equation 4 gives S.
The value of E measured at room temperature is used to determine G of the reaction. E
may be determined by plotting E versus T and obtaining the value at 25. The literature value is
1.100V for the cell used in this experiment. G and H for the reaction can then be calculated, as
can G and H.

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Pre-laboratory Questions:
1. For the half-reaction

Sn 4 + + 2e

Sn 2 +

Calculate the cell voltage, E, at 25 if the concentration of Sn4+ is 0.1M and that of Sn4+ is
0.5M, using the Nerst equation. E for this cell is +0.15V.

2. Calculate G (in kJ) for the reaction

Cd + Pb 2+

Cd 2 + + Pb

If the potential, E, of the cell was measured as +0.29V.

2+

3. How many moles of electrons are involved in the electrochemical oxidation of 118.7g of Sn
to Sn4+? How many faradays of electricity are involved?

4. What is the function of a salt bridge in a galvanic cell?

Name:_______________________________________________________________________
Data:___________________ Section:______________________________________________

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Data sheet
Experiment Data
____________________________________________________________
Temperature ()
Voltage (mv)
____________________________________________________________
Measurement 1
______________
_____________
Measurement 2
______________
_____________
Measurement 3
______________
_____________
Measurement 4
______________
_____________
Measurement 5
______________
_____________

Calculations
1. Generate a plot of E vs. T, as discussed in the experiment, and determine the value of dE/dT and
E.

2. Determine the value of S (using E at 25):

3. Calculate the value of G (using E at 25):

4. Calculate the value of H (using E at 25):

Name:_______________________________________________________________________
Data:___________________ Section:______________________________________________

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Questions
1. The cell used in this experiment is known as a galvanic cell. What is the main feature that
distinguishes this cell from one of the electrolytic type?

2. In a galvanic cell, what happens at the anode? At the cathode? What is the direction of
election flow? Explain.

3. A typical set of data were recorded for a Cu-Pb cell like the cell described in this experiment.
________________________________
Temp ()
Voltage (E)
________________________________
26.5
0.465
2.5
0.454
80.0
0.493
Calculate S, G and H for this system at 26.5.

4. From the results of this experiment, is the reaction spontaneous? How can you tell? In which
direction is it spontaneous? Explain.

Name:_______________________________________________________________________
Data:___________________ Section:______________________________________________

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