Experiment 6A: Thermodynamics of Electrochemical Cells

Introduction:

Electrochemistry studies the relationship between electrical and chemical energy. In this sense
chemical energy is produced from electrical energy in a electrolytic cell and vice versa in a
voltaic cell. These energy transfers are in the form of electron transfers in a redox reaction where
one species looses electrons while the other gains electrons simultaneously. In the voltaic cell a
voltage is induced as the electrons move. This is called EMF (electromotive force) whose
magnitude is quantitative.

The four laws of thermodynamics (from zeroth to third) govern the relation between the
equilibrium conditions and the temperature of the reaction to the thermodynamic functions of
enthalpy, entropy and free energy (Gibbs).

The EMF of a cell is related to the Gibbss free energy (G) by:

G = -nFE (1)

n- no of electrons transferred; F-Faradays Constant

And by Nernst equation of:

Ecell =Ecell - RT/nF (log Q) (2)

R-Gas constant; T-temperature (K); Q-reaction quotient

Furthermore Gibbs free energy can be broken down into entropy and enthalpy by:

G = H-TS (3)

H-enthalpy; S-entropy

Procedure:

The experiment was done as outlined in the lab manual. In addition the solutions were kept in
each water bath steamer for approximately 25 minutes.

Results:
 Table #1: Showing Mass of Salt Used

Pb(NO3)2 Cu(NO3)2

Mass of clockglass (g) 15.

EXACTLY what
value is meant to
be here

Mass of clockglass and salt (g) 15.9717 15.7471

Mass of clockglass and salt residue (g) 15.1434 15.1436

Mass of salt used (g) 0.8283 0.6035

Table #2: Showing Measured EMF For Copper Nitrate and Lead Nitrate Solutions

Temperature (C) Temperature (K) EMF (V) EMF (mV)

0 273 0.472 472

16 289 0.476 476

30 303 0.480 480

44 317 0.484 484

61 334 0.487 487

Table #3: Showing Measured EMF for Copper Sulphate Solution

Temperature (C) Temperature (K) EMF (V) EMF (mV)

15 288 0.0067 6.7

30 303 0.016 16.0

45 318 0.0025 22.5

60 333 0.0416 41.6

Graph #1: Part 6A
Graph Showing EMF vs Temperature For Electrochemical Cell
490

f(x) = 0.25x + 403.19

485

480

475
EMF /mV

470

465

460
260 270 280 290 300 310 320 330 340

Temperature / K

Graph #2: Part 6B

Graph Showing EMF vs Temperature Difference for Electrochemical Cell
45

40

f(x) = 0.74x - 6.1

35

30

25

EMF/ mV
20

15

10

0
10 20 30 40 50 60 70

Temperature Difference/ K

Calculations:

1000cm3 = 0.1mol
25cm3 = (0.1mol x 25cm3)/ 1000cm3

= 2.5 x10 -3 mol

Mr of Copper Nitrate = 241.60gmol-1

Mass of Copper Nitrate = 241.60gmol-1 x 2.5 x10-3mol

= 0.604g

Mr of Lead Nitrate = 331.1998gmol-1

Mass of Lead Nitrate = 331.1998gmol-1 x 2.5 x10-3mol

= 0.8280g

Temperature:

YC= (Y+273)K

15C= 15 + 273 = 288K

From Graphs:

Ecell = 0.2527 (298 K) + 403.19

= 478.4946 mV

= 0.478496 V ~ 0.478 V

Theoretical

Ecell = Ecathode Eanode

= +0.34 (-0.13) V
 =0.47 V

From Graph:

G= -nFEcell

= - (2 mol x 96485 Cmol-1 x 0.478 V)

= -92239.66 J

Theoretical

G= -nFEcell

= - (2 mol x 96485 Cmol-1 x 0.47 V)

= -90695.9 J

S = -nF(Gradient)

= - (2 mol x 96485Cmol-1 x 0.2527)

= -48763.519 mJK-1

= -48.763519 JK-1 -48.764 JK-1

H at (298K) = G + TS

= -92239.66 J + (298 K) ( -48.764 JK-1)

= -106.771 J

6B:

H = mCT
 = 2.4879 g x 4.186 Jg-1K-1 x 25 K

= 260.359 J

Ecell = 0.7413 (25 K) + (-6.1)

=12.4325 mV

=0.0124325 V ~ 0.012 V

G = -nFEcell

= - (2 mol x 96485 Cmol-1 x 0.0124325 V)

= -2399.100 J

S = - (-2399.100 260.359) J/25 K

= 85.550 JK-1

Discussion and Conclusion:

The EMF of an electrochemical cell varies with temperature since the cell reaction involves a
change in entropy, S. In Part 6A of this lab the following anode and cathode half cell reactions
were noted respectively: Pb Pb2+ + 2e; Cu2+ +2e Cu, leading to an over equation of:
Cu2+ + Pb Pb2+ + Cu, while for Part 6B the Cu 2+ + 2e Cu. Through calculations and use of
the EMF vs Temp. plot the Ecell values for the reactions were found to be 0.478V for Part A and
0.012V for Part B. Both Ecell values showed no deviations from that of the theoretical values.
Following this values of H, G and S were found. The Gibbs free energy value of 92239.66J
was calculated and showed a difference in value to that of the theoretical value of -90695.9J This
negative G value indicated that the reaction was spontaneous meaning that once a reaction
began (after activation barrier is surmounted) it continues without intervention, therefore overall
the reaction is thermodynamically stable - but can be kinetically slow.
Based on the values attained the slight deviations can be attributed to a number of factors for
example fluctuations of temperature values due to the use of a waterbath in the natural
environment, change in pressure of the surroundings, accuracy and precision of the experimenter,
purity of the salts used in the reactions, effectiveness of the digital multi-meter used, to name a
few. All of which can account for any deviations for the theoretical values. Alternatively, looking
at the equation G = H TS one can see a represent a linear function, where G can
calculated over a series of temperatures while H and S remain constant. If the Gibbs free
energy equation is rewritten as G = T S + H, which is now if the form of y = mx + c.
Where S represent m or the slope, x is the temperature T, H which must correspond to c or
the y-intercept of the equation. This format can be used for determine a range of temperatures
for which a reaction may be spontaneous or not.

As a side note, to answer the question as to how efficient would a cell (whose EMF is generated
solely but temperature difference such as in Part 6B ), be in turning heat into work one needs to
look at how heat engines operate. According to Atkins, P.W., Physical Chemistry, the efficiency
of heat engines, is given by 1 - Tcold/Thot. If the temperature of the cold reservoir is negative, then
the efficiency of the engine may be greater than 1. Alternatively, an efficiency greater than 1
implies that heat can be converted completely into work provided the heat is withdrawn from a
reservoir at T < O. If both reservoirs are at negative temperatures, then the efficiency is less than
1. (ref: Atkins, P.W., Physical Chemistry, pg 585). Therefore the electrochemical cell designed in Part 6B will
work well as a heat engine.