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The Gibbs Free Energy and Cell Voltage

When an amount of charge, Q, moves through a potential difference, E w = - Q E b/c work done by the system E > 0 for galvanic (voltaic) cells Recall, G = H TS = E + PV TS For constant T and P: G = E + PV - TS (usual case in electrochemical cells) But E = q + w Total work = P-V work + electrical work (w elect) = - PV + w elect E = q + w = q + w elect - PV G = q + w elect - PV + PV - TS = = q + w elect - TS If the condition of reversibility is imposed upon the galvanic cells, q = q rev = TS Therefore, G = q rev + w elect - TS = TS + w elect - TS = w elect And w elect = - Q E If n moles of e (nF coulombs of charge) pass through the external circuit of the galvanic cell when it is operated reversibly and if E is the reversible voltage, then G rxn = - Q E = - nFE (why G rxn ? well prove it in a bit!) Electrical work is produced when G rxn < 0 Standard States and Cell Voltages G o = - n FEo, Eo (standard cell voltage): is the cell voltage in a galvanic cell in rxn which reactants and products are in their standard states. (Gases at 1 bar, solutes in 1 M, metals in their pure stable states and at a specified temperature) Example A 6.0 Volt battery delivers a steady current of 1.25 A for a period of 1.50 hours. Calculate the total charge in coulombs that passes through the circuit. Q = It = (1.25 C s-1)(1.5 hours)(3600 s hour-1) = 6750 C w elect = - Q E = - (6750 C)(6 V) = - 4.05 x 104 J (work done on the battery) - (- 4.05 x 104 J) = + 4.05 x 104 J work done by the battery.
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Half-Cell Potentials It is a very long and tedious job to tabulate all the conceivable galvanic cells We can avoid the previous job by tabulating the half-cell reduction potentials, Eo These Eo values express the intrinsic tendency of a reduction half-reaction to occur when the reactants and products are at standard states.
o o E o = Ecathode Eanode

How Eos are measured? Line notation of cell: S.H.E. || Ag+ (aq,1M) | Ag(s) Oxidation occurs in the SHE half-cell and this electrode is the anode: H2 (g 1 bar) 2H+ (aq,1M) + 2e 2H+ (aq,1M) + 2e H2 (g,1 bar) Eo (H2 / H+, oxid. = Eo (H+ / H2 , red. 0.00 V

Consider Cu2+ (aq,1 M)|Cu (s) half-cell connected to SHE. We measure E o = 0.34 V Then we assign Eo for Cu2+ (aq,1 M) + 2e Cu (s) Now consider Zn2+ (aq,1 M)|Zn (s) half-cell connected to SHE. We measure E o = - 0.76 V. Then we assign Eo = -.0.76V for Zn2+ (aq,1 M) + 2e Zn (s) Now we build the cell: Zn2+ (aq,1 M)|Zn (s) || Cu2+ (aq,1 M)|Cu (s) for which
o o E o = Ecathode Eanode = 0.34 ( 0.76) = 1.10V (>0) - Cell is galvanic

Half-cell potentials are intensive properties, namely independent of the amount of the reacting species.
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1. All values are relative to SHE ( = reference electrode) 2. Half-reactions are written as reductions (only reactants are oxidizing agents and only products are the reducing agents) 3. The more positive the Eo the more readily the reaction occurs 4. Half-reactions are shown with b/c each can occur as reduction or oxidation 5. The half-cell that is listed higher at the table acts as the cathode Writing spontaneous redox reactions a) By convention, electrode potentials are written as reductions b) When pairing two half-cells, you must reverse one reduction half-cell to produce an oxidation half-cell. Reverse the sign of the potential. c) The reduction half-cell potential and the oxidation half-cell potential are added to obtain the E o . cell d) When writing a spontaneous redox reaction, the left side (reactants) must contain the stronger oxidizing and reducing agents. Example Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)
stronger reducing agent stronger oxidizing agent weaker oxidizing agent weaker reducing agent

Example Will Ag+ oxidize Zn (s) or will Zn2+ oxidize Ag (s) Example A voltaic cell houses the reaction between aqueous bromine and zinc metal: o Br2+ (aq) + Zn (s) Zn2+ (aq) + 2Br - (aq) Ecell = 1.83 V o o Calculate Ebro min e given E zinc = - 0.76 V. o The cell is voltaic Ecell = 1.83 V > 0 (reaction spontaneous) as written. Zn is being oxidized and therefore it is the anode. o o o o o o o Ecell = Ecathode Eanode Ecathode = Ecell + Eanode = 1.83 + ( 0.76) = 1.07 V = Ebro min e Example A standard (Pt | MnO 4 , H+, Mn2+) half-cell consists of an inert electrode in contact with a solution containing MnO 4 (aq) , H+ (aq) and Mn2+ (aq) ions in standard states. Such a half-reaction is assembled and connected to a standard Zn2+ (aq,1 M)|Zn (s) half-cell/ a) Calculate E of the cell at 25oC. In Appendix D we find:
(Rxn 1): MnO 4 (aq) + 8H+ (aq) + 5e Mn2+ (aq) + 4H2O (l) Eo = 1.507V (Rxn 2): Zn2+ (aq) + 2e Zn (s) Eo = - 0.762V

Rxn 1 is the cathode because it lies above Eo (Zn2+/Zn), So o o E o = Ecathode Eanode = 1.507 ( 0.762) = +2.269 V b) Write a balanced equation for the overall reaction We multiply (Rxn 1) by 2 and (Rxn 2) by 5: 2MnO 4 (aq) + 16H+ (aq) + 5Zn (s) 2Mn2+ (aq) + 5Zn2+ (aq) + 8H2O (l) Number of e involved: 10 Now check:
G o = [2G of (Mn2+ (aq)) +5G of (Zn2+ (aq))+ 8G of (H2O (l)) ] - [2G of (MnO 4 (aq)) rxn

16G of (H+ (aq)) +5G of (Zn (s)) ] = - 2194.5 kJ


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o Grxn 2194.5 x10 3 Jmol 1 E = = = 2.27 JC 1 = 2.27V Very good match!!! 1 ne F (10)(96,485Cmol ) o

Disproportionation A single chemical species is both oxidized and reduced This species must be able to give up electrons and accept electrons and in addition the half-reaction in which it is reduced must lie higher in the table than the half-reaction in which it is oxidized If this is the case then it drives the second reaction to go in reverse and disproportionation occurs spontaneously Example (1): Cu+ (aq) + e Cu (s) Eo = 0.521 V (2): Cu2+ (aq) + e Cu+ (aq) Eo = 0.153V (1) is reduction and drives (2) as oxidation 2 Cu+ (aq) Cu2+ (aq) + Cu (s) E o = 0.521 0.153 = 0.368 V (>0) cell o o Which means E rxn > 0 and G rxn < 0 spontaneous. Yes it disproportionates. Example Decide whether Fe2+ (aq) in its standard state at 25oC is stable w/r/t disproportionation. In Appendix D we find: (1): Fe3+ (aq) + e Fe2+ (aq) Eo = 0.771V (2): Fe2+ (aq) + 2e Fe (s) Eo = - 0.447V In order for Fe2+ (aq) to disproportionate reaction (1) would have to be driven backwards (oxidation): 3Fe2+ Fe (s) + 2Fe3+ (aq) And Eo = -0.447 (+0.771) = -1.218 V (< 0) and G o > 0 (non-spontaneous) and rxn therefore stable against disproportionation. Oxygen as an oxidizing agent O2 (g) + 4H+ (aq) + 4e 2H2O (l) Eo = 1.229V good oxidizing agent! O3 (g) + 2H+ (aq) + 2e O2 (g) + H2O (l) Eo = 2.067V even better oxidizing agent!
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H2O2 (aq) + 2H+ (aq) + 2e 2H2O (l) Eo = 1.776V (bleach + germicider) O2 (g) +2H+ (aq) + 2e H2O2 (aq) Eo = 0.695V H2O2 as a reducing agent can reduce only chemical species with reduction potentials greater than 0.695 V. Relative Reactivities of Metals Metals that can displace hydrogen from acid Fe (s) + 2H+ (aq) H2 (g) + Fe2+ (aq) Why does this rxn go? Fe (s) Fe2+ (aq) + 2e Eo = - 0.44V and 2H+ (aq) + 2e H2 (g) Eo = 0.0 (SHE) E o = 0.00 ( - 0.44) = + 0.44 V (> 0) rxn will go! cell Metals that cannot displace hydrogen from acid 2Ag (s) + 2H+ (aq) 2Ag+ (aq) + H2 (g) Eo = 0.80V 2 x [Ag (s) Ag+ (aq) + e ] and 2H+ (aq) + 2e H2 (g) Eo = 0.0 (SHE) E o = 0.00 (0.80) = - 0.80 V (< 0) rxn will not go! cell Metals that can displace hydrogen from water 2H2O (l) + 2e H2 (g) + 2OH (aq) Eo = - 0.42 V However, [OH ] = 10-7 non-standard Metals active enough to reduce H2O (l) lie below ( 0.42 V) 2Na (s) + 2H2O (l) 2Na+ (aq) + H2 (g) + 2OH (aq) 2 x [Na (s) Na+ (aq) + e ] Eo = -2.71 V 2H2O (l) + 2e H2 (g) + 2OH (aq) Eo = -0.42V, E o = -0.42 (-2.71) = 2.29 V Yes, Na can! cell Metals that displace other metals in solutes Zn (s) + Fe2+ (aq) Zn2+ (aq) + Fe (s) Zn (s) Zn2+ (aq) + 2e Eo = - 0.76 V Fe2+ (aq) + 2e Fe (s) Eo = - 0.44 V E o = -0.44 (- 0.76) = 0.32 V cell Concentration Effects and the Nernst Equation G = G o + RT ln Q
G o = nFE o G = nFE

G = G o + RT ln Q nFE = nFE o + RT ln Q Divide both sides nF nFE nFE o RT ln Q = + nF nF nF RT E = Eo ln Q Nernst Equation (expresses the net driving force for a reaction) nF Eo: standard reduction potential R: 8.314 J K-1 mol-1 = 8.314 V C K-1 mol-1 F: Faradays constant = 96,485 C mol-1 T: absolute temperature (K) n: number of electrons in the half-reaction Q: reaction quotient RT at 25oC (298.15K) Let us evaluate nF
RT (8.314 JK 1mol 1 )( 29815K ) 0.0257 . = = 1 nF n(96,485Cmol ) n
o And the Nernst Equation at 298.15K becomes, E = E o Recall that ln x = 2.303 log10 x and E = E

0.0257 ln Q n

0.05916 log10 Q n

Recall, at equilibrium G = 0 G o = RT ln K nFE o = RT ln K


o And E =

RT ln K nF

Lets see in depth!


E = Eo RT ln Q nF

When Q < 1 and thus [reactant] > [product], ln Q < 0, so E > E o cell o When Q = 1 and thus [reactant] = [product], ln Q = 0, so E = E cell When Q >1 and thus [reactant] < [product], ln Q > 0, so E < E o cell

The signs of Go and E o determine the direction of the reaction at standard conditions. cell Example Suppose that the Zn |Zn2+(aq) || MnO 4 (aq) | Mn2+(aq) |Pt cell is operated at pH 2.00 with [MnO 4 ]= 0.12 M, [Mn2+|] = 0.0010 M and [Zn2+] = 0.015 M. Calculate the cell voltage, E , at 25 oC. The reaction of this cell is: 2MnO 4 (aq) + 16H+ (aq) + 5Zn (s) 2Mn2+ (aq) + 5Zn2+ (aq) + 8H2O (l) , Eo = 2.27V
E = E o 0.0257 0.0257 [ Mn 2+ ]2 [ Zn 2+ ]5 0.0257 (0.0010) 2 (0.015) 5 ln Q = 2.27 ln = 2.27 ln = 2.14V 10 10 [ MnO4 ]2 [ H + ]16 10 (0.12) 2 (0.010)16

Example An electrochemical cell is set up at 25oC. One half-cell consists of a zinc anode immersed in a 1.0 M solution of Zn(NO3)2. The second half-cell consists of a platinum cathode that has gaseous hydrogen bubbling over it at a pressure of 1.00 atm in a solution of unknown hydrogen-ion concentration. The observed cell voltage is 0.472 V. (a) Calculate the reaction quotient, Q Anode: Zn (s) Zn2+ (aq) + 2e Eo = - 0.762V Cathode: 2H+ (aq) + 2e H2 (g) Eo = 0.00 V (SHE)
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Eo = 0.00 (-0.762) = 0.762 V The cell is not at the standard state


E = E o RT nF 2 ln Q ln Q = ( E o E ) = (0.762 0.427) = 22.48 nF RT 0.0257

Q = e 22.48 5.8 x10 9

(b) Calculate the hydrogen-ion concentration in the second half-cell


Q= [ Zn 2+ ]PH 2 [ H + ]2 = (1.00)(1.00) = 5.8 x109 [ H + ] = 1.3x10 5 M + 2 [H ]

Electrolytic Cells In galvanic (voltaic) cells electrons are generated at the anode (-) and they are consumed st the cathode (+) In an electrolytic cell, electrons come from an external power source, which supplies to the cathode and removes them from the anode. Cathode (-), Anode (+) The tin-copper reaction as the basis of a voltaic and an electrolytic cell

At standard conditions the spontaneous reaction between Sn and Cu2+ generates 0.48 V (voltaic) If more than 0.48 V supplied the same apparatus and components become an electrolytic cell and the nonsponatneous reaction between Cu and Sn2+ occurs.

Concentration Cells In these cells the half-reactions are the same but the concentrations are different. A concentration cell based on the Cu/Cu2+ half-reaction

The easiest is pH. We construct a cell with cathode to be SHE and the unknown has the same apparatus dipping into an unknown [H+] solution. Oxidation: H2 (g 1 atm) 2H+ (aq, unknown) + 2e Reduction: 2H+ (aq, 1M) + 2e H2 (g 1 atm) Overall: 2H+ (aq, 1M) 2H+ (aq, unknown)
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E cell = E

o cell

By measuring the cell potential we can get [H+] and consequently pH

2 [ H + ]umknown 0.05916 0.05916 log + 2 = 0.00 log[H + ]2 = 0.05916 log[H + ] 2 [ H ]s tan dard 2

pH Meter

Example A concentration cell consists of two Ag/Ag+ half-cells. In half-cell A, electrode A dips into 0.010 M AgNO3; in half-cell B, electrode B dips into 4.0 x 10-4 M AgNO3. What is the cell potential at 298.15 K? Which electrode has a positive charge? Ag+(aq, 0.010 M) [half-cell A] Ag+(aq 4.0 x 10-4 M) [half-cell B]
Ecell = E
o cell

0.05916 [ Ag + ]B 0.05916 4.00 x10 4 log = 0.00 log = 0.0828V 1 [ Ag + ] A 1 0.010

Reduction occurs at the cathode electrode A, so electrode A has a positive charge.

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