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NAME: Ananda Lawkaran Friday NAME: Lauren Khandan DATE: Monday 31st October, 2011.

Experiment 6

LAB DAY: WEEK: 3

TITLE: Experiment 6: The Thermodynamics of Electrochemical Cells.

INTRODUCTION/ THEORY: The Gibbs free energy equation is as follows: G = H - TS The TS term in the Gibbs free energy equation is highly dependent on temperature due to the presence of T in the equation. The H term however, is very weakly dependent on temperature. The Gibbs free energy is a measure of how spontaneous a reaction is and can be defined as the maximum amount of obtainable work from a reaction. This experiment involves the use of different cells with different solutions at varying temperatures to investigate the effect of temperature on the Gibbs free energy. H0 < 0 and S< 0 when a reaction is favourable for enthalpy and but unfavourable for entrophy. Furthermore, the reaction becomes less spontaneous as temperature increases. This is because as the temperature increases the TS0 term which is added to the enthalpy if the entrophy is unfavourable also increases. Over time the TS0 term becomes larger than the H0 term and G is positive. Eventually the reaction is no longer spontaneous. The driving force in the reaction is entrophy which is defined as the level of disorder. The system and closed surroundings is a closed isolated system so that the only spontaneous reactions allowed are those which increase the entrophy. G/T is more applicable than G in determining how spontaneous a reaction is. G is not directly related to the entrophy change of the universe but 1/G is. Some reactions are spontaneous because they give off energy in the form of heat and some are spontaneous because they lead an increase in the

disorder of the system. This experiment seeks to investigate the level of disorder in systems and the Gibbs free energy at varying temperatures.

PROCEDURE: As outlined on pages 27-30 of the CHEM 2360 Laboratory Manual. The half cells were monitored and EMFs were recorded at 15 minute intervals. RESULTS: Part 6A: Mass of Pb(NO3)2 used = 8.2833g Mass of Cu(NO3)2 = 6.0502g Table 1: Table Showing the Electromotive Force Readings recorded at different temperatures for the cell made up with solutions of Pb(NO3)2 and Cu(NO3)2 Temperature (0C) 0 15 30 45 60 Temperature (K) 273 288 303 318 333 EMF (mV) 505 507 511 515 520

Part 6B: Table 2: Table Showing the Mass of Cupric Sulphate used Mass of dry clock glass (g) Mass of clock glass and cupric sulphate (g) Mass of cupric sulphate used (g) 57.6548 60.1519 2.4971

Table 3: Table Showing the Electromotive Force Readings obtained for the half cells each filled with Cupric Sulphate solution and subjected to different temperatures. Temperatur e of first half cell (0C) 0 0 0 0 Temperatur e of first half cell (K) 273 273 273 273 Temperatur e of second half cell (0C) 15 30 45 60 Temperatur e of second half cell (K) 288 303 318 333 EMF (mV) EMF (V)

04.1 13.6 22.2 37.7

0.0041 0.0136 0.0222 0.0377

CALCULATIONS AND GRAPHS: CALCULATIONS USED IN PROCEDURE: Required to calculate: the mass of cupric sulphate needed to make up 100ml of 0.1M cupric sulphate solution Soln: 1000ml of solution will contain 0.1 moles 100ml of solution will contain (0.1 1000) x 100 = 0.01 moles Mass required = number of moles x R.M.M =0.01mol X 249.68gmol-1 =2.4968g

Required to calculate: the mass of copper nitrate needed to make up 25ml of 0.1M copper nitrate solution

Soln: 1000ml of solution will contain 0.1 moles 25ml of solution will contain (0.1 1000) x 25 = 0.0025 Mass required = 6.0502g

Required to calculate: the mass of lead nitrate needed to make up 25ml of 0.1M lead nitrate solution Soln: 1000ml of solution will contain 0.1 moles 25ml of solution will contain (0.1 1000) x 25 = 0.0025 Mass required = 8.2833g

GRAPHS: Table 4: Table Showing The Values Of Temperature And Emf Used To Plot Graph 1. Temperatu EMF (mV) re (K) 273 288 303 318 333 505 507 511 515 520

PART 6A Equations used in calculations: Go= -nFEo ...(1)

Go = Ho - TSo ...(2)

Pb(s)/ Pb(NO3)2 (aq,0.1M): Cu(NO3)2 (aq.0.1M)/Cu(s) Half Equations of Cell: Anode: Pb(s) Pb2+(aq) + 2e- Eo= -0.13V Cathode: Cu2+(aq) + 2e- Cu(s) Eo = +0.34V Overall Equation: Pb(s) + Cu2+(aq) Pb2+(aq) + Cu(s) where n= 2

Theoretical Eoof reaction is found by: Ecathode- Eanode Eocell= +0.34V-(-0.13V) = +0.47V

Equation obtained from graph is y = 0.2533x + 434.84 Ecell from graph is found by: = 0.2533 (298) + 434.84 = 510.3234 mV = 0.51V Theoretical Go of reaction is found by: Go = -nFEo

= - (2 moles) (96485Cmol-1) (0.47V) = -90695.9 Jmol-1 E298K = 0.51V (Obtained from graph) Go can be obtained from graph by Go= -nFEo = -(2 moles x 96485 Cmol-1 x 0.51V) = -98414.7 Jmol-1

Combining equations (1) and (2): -nFEo= Ho - TSo An E equation of the form y= mx + c is required. Divide LHS and RHS by -nF -nFEo -nF = (Ho -nF)- (TSo -nF) Eo= (Ho-nF) (TSo-nF) = (TSo nF) (Ho nF)... (a) Equation (a) is in the form y= mx + c Where: y= Eo, m= So nF, x= T and c= - Ho nF From Graph 1: y = 0.2533x + 434.84 As such, m= 0.2533 which from Equation (a) is equivalent to So nF So = 2 moles x 96485Cmol-1 x 0.2533 = 48879.30 mJK-1 = 48.879 JK-1 Theoretical Value of So = 78.5 JK-1

Using equation (2): Go = Ho - TSo

Ho= Go + TSo = -98414.7J + (298K x 48.879JK-1) = -83848.758J = -83.848 KJ (per mole) Theoretical Value of Ho = -66.5 KJ (per mole)

Table 5: Table Showing The Values Of Temperature (K) And EMF (Mv) Used To Plot Graph 2: Temperatu re (K) 288 303 318 333 EMF (mV) 4.1 13.6 22.2 37.7

Part 6B Equations used in calculations: Go= -nFEo ...(1)

Go = Ho - TSo ...(2)

Cu(s)/CuSO4(aq.0.1M,0oC):CuSO4(aq.0.1M,ToC)/Cu(s) Half Equations of Cell: Anode: Cu2+(aq) + 2e- Cu(s)Eo = +0.34V (0.1M,0oC) Cathode: Cu2+(aq) + 2e- Cu(s)Eo = +0.34V (0.1M,ToC) Overall Equation: Cu2+(aq) + 2e- Cu(s)Eo = +0.34V where n= 2

Theoretical Eoof reaction was found by Ecathode- Eanode Eocell= +0.34V From Graph, y = 0.7293x - 207.06 Ecell from graph = 0.7293 (25K) 207.06 = 10.27 mV = 0.0103 V Theoretical Go was found by= -nFEo = - (2moles) (96485Cmol-1) (0.34V) = -65609.8 J = -65.61 KJ Go= -nFEo = -(2 moles x 96485 Cmol-1 x 0.0103V) = -1987.59 J = -1.988 KJ Combining equations (1) and (2): -nFEo= Ho - TSo An E equation of the form y= mx + c is required. Divide LHS and RHS by -nF -nFEo -nF = (Ho -nF)- (TSo -nF) Eo= (Ho-nF) (TSo-nF) = (TSo nF) (Ho nF)... (a) Equation (a) is in the form y= mx + c Where: y= Eo, m= So nF, x= T and c= - Ho nF As such, m= 0.2533 which from Equation (a) is equivalent to So nF

So = (2moles x 96485Cmol-1 x 0.7293) = 140733.02 mJK-1 = 140.73 JK-1

Using equation (2): Go = Ho - TSo Ho= Go + TSo = -1987.59 Jmol-1+ (298K x 140.73 JK-1mol-1) = 43925.13 J = 43.925 kJ So of lead half cell = So of Copper-Lead cell (6B)- So of Copper cell (6A) = 140.73 - 48.879 = 91.851 JK-1

From Atkins, P.W. Physical Chemistry p. 585: The efficiency of heat engines, which is a direct consequence of the Second Law, is still given by 1 - Tcold/Thot. However, if the temperature of the cold reservoir is negative, then the efficiency of the engine may be greater than 1. This condition corresponds to the amplification of signals achieved in lasers. 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<0. If both reservoirs are at negative temperatures, then the efficiency is less than 1 Therefore the typical electrochemical cell used in Part 6B will indeed work as a heat engine.

DISCUSSION:

The Electromotive force (EMF) across an electrochemical cell varies with temperature due to the fact that the cell undergoes a change in entropy. In part 6A of the laboratory experiment, the following half cell reactions were observed: At the anode: Pb Pb2+ + 2eAt the cathode: Cu2+ +2e- Cu Therefore overall: Cu2+ + Pb Pb2+ + Cu In part 6B, it was noted that: Cu2+ + 2e Cu Inspecting the equation: G = H TS or: G = T S + H

It may be seen that a linear relationship exists between G and T. Such a relationship is of the form y = mx + c where the gradient, m is represented by S.
By plotting EMF values against temperature readings and carrying out calculations, the EMF of each cell could was found: Ecell of Part A = 0.51V Ecell of Part B = 0.01V The values of H, G and S were subsequently calculated. The Gibbs free energy for Part A was determined to be -98.41kJ while that of Part B was found as -1.98759kJ. The fact that the G values were negative indicates that the reactions can occur spontaneously, after the activation barrier has been exceeded, and will continue once left uninterrupted pointing to thermodynamic stability. It should be noted that the theoretical values for the two reactions were -90.69kJ for Part A and -65.61 for Part B. Most values calculated from data obtained are comparable to their theoretical values. In cases where they differ greatly, the difference can be accounted for by sources of error.

Additionally, G = H TS represents a linear function, whereas G was calculated over a series of increasing temperatures while H and S stayed

constant. Gibbs free energy equation can be rewritten as G = T S + H, which is now if the form of y = mx + c to allow the graph to show linearity at different temperatures
From Atkins, P.W. Physical Chemistry p. 585: The efficiency of heat engines, which is a direct consequence of the Second Law, is still given by 1 - Tcold/Thot. However, if the temperature of the cold reservoir is negative, then the efficiency of the engine may be greater than 1. This condition corresponds to the amplification of signals achieved in lasers. 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<0. If both reservoirs are at negative temperatures, then the efficiency is less than 1 Therefore the typical electrochemical cell used in Part 6B will indeed work as a heat engine.

CONCLUSION:

REFERENCES: Atkins, P., de Paula, J. 2006. Atkins Physical Chemistry, 8th Edition. Cambridge University Press. http://www.chem.arizona.edu/~salzmanr/480a/480ants/gibshelm/gibshelm.ht ml http://library.thinkquest.org/C006669/data/Chem/thermodynamics/gibbs.html http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/helmholtz.html http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch21/gibbs.php#d epend