Electrochemical thermodynamics

Electrochemical thermodynamics
welectrical V Q since nF E
The electrical work wel that can be done by this system is:

Q nF

wel QE nF E

wel GT,p

where n is the number of electrons transferred and F is Faradays constant

Combining Reduction Half-Equations

Fe3+(aq) + 3e- Fe(s) EFe3+/Fe = ? Fe2+(aq) + 2e- Fe(s) Fe3+(aq) + 1e- Fe2+(aq) Fe3+(aq) + 3e- Fe(s) EFe2+/Fe = -0.440 V EFe3+/Fe2+ = 0.771 V EFe3+/Fe = +0.331 V can add G G = +0.880 (F) J G = -0.771 (F) J G = +0.109 (F) J

but cannot simply add E G = +0.109 (F) J = -nFE

EFe3+/Fe = +0.109 (F) J /(-3F) = -0.0363 V

Hitung E0 untuk reaksi : Cr2+ + 2e Cr (s)

E01 = ? E02 = 0,5 V E03 = 0,41 V

Diketahui : Cr3+ + 3e Cr (s) Cr3+ + e Cr2+

Solution : G01 = 2FE01 G02 = 3FE02 G03 = FE03 G01 = G02 G03

G01 = 2FE01

Spontaneous Change in Oxidation-Reduction Reactions G = H T S

G < 0 for spontaneous change. Therefore Ecell > 0 because Gcell = -nFEcell Ecell > 0 Ecell = 0
Reaction is at equilibrium. Reaction proceeds in the reverse direction spontaneously.

Reaction proceeds spontaneously as written.

Ecell < 0

The Behavior or Metals Toward Acids

M(s) M2+(aq) + 2 eE = EM2+/M

2 H+(aq) + 2 e- H2(g)

EH+/H2 = 0 V

2 H+(aq) + M(s) H2(g) + M2+(aq) Ecell = EH+/H2 EM2+/M = EM2+/M

When EM2+/M < 0, Ecell > 0. Therefore G < 0.

Metals with negative reduction potentials react with acids.

Will aluminum metal displace Cu2+ from aqueous solution ? That is, will a spontaneous reaction occur in the forward direction for the following reaction ? 2 Al(s) + 3 Cu2+ (1 M) 3 Cu(s) + 2 Al3+ (1 M)

Because E0cell is positive, the direction of spontaneous change is that of the forward reaction Al(s) will displace Cu2+ from aqueous solution under standard-state conditions

Relationship Between Ecell and Keq

G = -RT ln Keq = -nFEcell RT Ecell = ln Keq nF 0.025693 ln K Ecell = eq = (0.0592/n ) log Keq z

FIGURE 20-8 A summary of important thermodynamic, equilibrium and electrochemical relationships under standard conditions.

G = G + RT ln Q nFEcell = nFEcell + RT ln Q Ecell = Ecell RT nF ln Q

Convert to log10 and calculate constants.

Ecell = Ecell

0.0592 V

log Q

The Nernst Equation

Concentration Cells

Concentration Cells
Electrolyte concentration cell
the electrodes are identical; they simply differ in the concentration of electrolyte in the half-cells.

Concentration Cells
Electrode concentration cells
the electrodes themselves have different compositions. This may be due to.
Different fugacities of gases involved in electrode reactions (e.g., The H+(aq)/H2 (g) electrode). Different compositions of metal amalgams in electrode materials.

Concentration Cells
Two half cells with identical electrodes but different ion concentrations. Pt|H2 (1 atm)|H+(x M)||H+(1.0 M)|H2(1 atm)|Pt(s)

A concentration cell

Measurement of Ksp
Ag|Ag+(satd AgI)||Ag+(0.10 M)|Ag(s)

Ag+(0.100 M) + e- Ag(s) Ag(s) Ag+(satd) + eAg+(0.100 M) Ag+(satd M)

A concentration cell for determining Ksp of AgI

Calculating Redox Equilibrium Constants Example : Calculate the equilibrium constant for the reaction

2Fe3+ + 3I- 2Fe2+ + I3Sol: 2Fe3+ + 2e- 2Fe2+ E0 = 0.771 V

I3- + 2e- 3I-

E0 = 0.536 V

E Fe 3 /Fe 2 E 0 Fe 3 /Fe 2

0.0592 [Fe 2 ]2 log 2 [Fe 3 ]2

E I /I E 0 I3 /I
3

0.0592 [I ]3 log 2 [I3 ]

E Fe 3 /Fe 2 E I /I
3

E 0 Fe 3 /Fe 2

0.0592 [Fe2 ]2 0.0592 [I ]3 log E 0 I3 /I log 3 2 2 [Fe ] 2 [I3 ]

2(E0 Fe 3 /Fe 2 - E 0 I3- /I - ) [Fe2 ]2 [I ]3 log log 3 2 0.0592 [Fe ] [I3 ]

[Fe2 ]2 [I3 ] log [Fe3 ]2 [I ]3

[Fe ] [I3 ] 2(E 0 Fe 3 /Fe 2 E 0 I3 /I ) log 3 2 3 [Fe ] [I ] 0.0592

2 2

2(E 0 Fe 3 /Fe 2 E 0 I3 /I ) 2(0.771 0.536) log K eq 7.94 0.0592 0.0592 K eq anti log 7.94 8.7 107

Calculate the equilibrium constant for the reaction 2MnO4- + 3Mn2+ + 2H2O 5MnO2(s) + 4H+ Sol: 2MnO4- + 8H+ +6e- 2MnO2(s) + 4H2O 3MnO2(s) + 12H+ + 6e- 3Mn2+ + 6H2O EMnO4-/MnO2 = EMnO2/Mn2+ E0 = +1.695 V E0 = +1.23 V

0.0592 1 0.0592 [Mn 2 ]3 1.695 log 1.23 log 2 8 6 6 [H ]12 [MnO4 ] [H ]

6(1.695 1.23) 1 [H ]12 log log 2 8 0.0592 [Mn 2 ]3 [MnO4 ] [H ]

6(1.695 1.23) [H ]12 log 2 0.0592 [MnO4 ] [Mn 2 ]3[H ]8

[H ] 47.1 log log K eq 2 2 3 [MnO4 ] [Mn ]

Keq anti log 47.1 110
47

Termodinamika sel
G = nFE
= S = nF Qp = TS = S

Example :
Cd CdCl2 25H2O AgCl(s) Ag

E.m.f sel pada 15C = 0,67531 V dan koefisien temperatur e.m.f = 0,00065 V der 1. Hitung harga H pada 15C dan aliran panas jika proses berlangsung reversibel

G = nFE = (2)(96500 C)(0,67531 V) S =(2)(96500 C)(0,00065 V der 1) H = G + TS Qp = TS