Experiment 6A: The rmodynamics 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 (Gibb’s). The EMF of a cell is related to the Gibbs’s free energy (ΔG) by: ΔG = -nFE n- no of electrons transferred; And by Nernst equation of: Ecell =E°cell - RT/nF (log Q) R-Gas constant; (2) Q-reaction quotient (1) F-Faraday’s Constant

T-temperature (K);

Furthermore Gibb’s free energy can be broken down into entropy and enthalpy by: ΔG = ΔH-TΔS ΔH-enthalpy; ΔS-entropy (3)

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 Mass of clockglass (g) 15. EXACTLY what value is meant to be here 15.9717 15.1434 0.8283

Cu(NO3)2

Mass of clockglass and salt (g) Mass of clockglass and salt residue (g) Mass of salt used (g)

15.7471 15.1436 0.6035

Table #2: Showing Measured EMF For Copper Nitrate and Lead Nitrate Solutions Temperature (°C) 0 16 30 44 61 Temperature (K) 273 289 303 317 334 EMF (V) 0.472 0.476 0.480 0.484 0.487 EMF (mV) 472 476 480 484 487

Table #3: Showing Measured EMF for Copper Sulphate Solution Temperature (°C) 15 30 45 60 Temperature (K) 288 303 318 333 EMF (V) 0.0067 0.016 0.0025 0.0416 EMF (mV) 6.7 16.0 22.5 41.6

Graph #1: Part 6 A

Graph #2: Part 6B

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: Y°C= (Y+273)K 15°C= 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: ΔG= -nFEcell = - (2 mol x 96485 Cmol-1 x 0.478 V) = -92239.66 J Theoretical ΔG= -nFEcell = - (2 mol x 96485 Cmol-1 x 0.47 V) = -90695.9 J

ΔS = -nF(Gradient) = - (2 mol x 96485Cmol-1 x 0.2527) = -48763.519 mJK-1 = -48.763519 JK-1 ̴ -48.764 JK-1

ΔH at (298K) = ΔG + TΔS = -92239.66 J + (298 K) ( -48.764 JK-1) = -106.771 J

6B: ΔH = mCΔT = 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

ΔG = -nFEcell = - (2 mol x 96485 Cmol-1 x 0.0124325 V) = -2399.100 J

ΔS = - (-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 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.

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