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# 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

## 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

## 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.

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

## 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.

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)

## A concentration cell for determining Ksp of AgI

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

## I3- + 2e- 3I-

E0 = 0.536 V

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

## [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

## [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