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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 (Gibb’s).
The EMF of a cell is related to the Gibbs’s free energy (ΔG) by:
ΔG = -nFE (1)
Furthermore Gibb’s free energy can be broken down into entropy and enthalpy by:
ΔG = ΔH-TΔS (3)
ΔH-enthalpy; ΔS-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 #2: Showing Measured EMF For Copper Nitrate and Lead Nitrate Solutions
Calculations:
1000cm3 = 0.1mol
= 0.604g
= 0.8280g
Temperature:
Y°C= (Y+273)K
= 478.4946 mV
= 0.478496 V ~ 0.478 V
Theoretical
= +0.34 – (-0.13) V
=0.47 V
From Graph:
ΔG= -nFEcell
= -92239.66 J
Theoretical
ΔG= -nFEcell
= -90695.9 J
ΔS = -nF(Gradient)
= -48763.519 mJK-1
= -106.771 J
6B:
ΔH = mCΔT
= 260.359 J
=12.4325 mV
=0.0124325 V ~ 0.012 V
ΔG = -nFEcell
= -2399.100 J
= 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 Cu2+ + 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 ΔG 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 ΔG = ΔH – TΔS one can see a represent a linear function,
where ΔG can calculated over a series of temperatures while ΔH and ΔS remain constant. If the
Gibbs free energy equation is rewritten as ΔG = – T ΔS + ΔH, which is now if the form of y =
mx + c. Where ΔS represent m or the slope, x is the temperature T, ΔH 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.