Electroanalysis

Part 3

Firman Shantya Budi,S.Pd.,M.Sc

 Sel Elektrokimia
 Sel Galvani (sel Voltaic)— Reaksinya spontan;
reaksi kimia redoks menghasilkan listrik
 Sel Elektrolisis— reaksinya non-spontan;
menggunakan listrik untuk menghasilkan reaksi
kimia redoks
 Banyak sel elektrokimia dapat dioperasikan baik
secara galvani atau elektrolitik dengan
mengubah kondisi operasional eksperimen
17_360

e– e–

e– e–
Porous disk

Oxidation Reduction

e– Reducing Oxidizing e–
agent agent

(a) Anode (b) Cathode

 Zn2+(aq) + Cu(s)  Cu2+(aq) + Zn(s)

Zn gives up electrons to Cu
— “pushes harder” on e-

— greater potential energy

— greater “electrical potential”

Spontaneous reaction due to

— relative difference in metals’ abilities to give e-

— ability of e- to flow
 Cell Potential

Cell Potential / Electromotive Force (EMF):

The “pull” or driving force on electrons

Measured voltage (potential difference)

work or electrical potential energy J

E cell   V
unit of charge moved C
 Cell EMF
• Electromotive force (emf) is the force required to push
electrons through the external circuit.
• Cell potential: Ecell is the emf of a cell (in Volts).
• For 1M solutions at 25 C (standard conditions), the
standard emf (standard cell potential) is called Ecell.
Standard Reduction Potentials
• Convenient tabulation of electrochemical data.
• Standard reduction potentials, Ered are measured relative
to the standard hydrogen electrode (SHE).
1J
1V 
1C
 17_363

e– e–

e– e–
Ecell = +1.10 V

+ +
Zn 2 Cu 2
– –
SO 4 2 SO 4 2
Zn(s) Cu(s)
+ 2+
1.0 M Zn 2 1.0 M Cu
solution solution

Anode Cathode
 Cell Potential, E0cell

E0cell
cell potential under standard conditions

elements in standard states (298 K)

solutions: 1M
gases: 1 atm
 Standard Reduction Potentials
E0 values for reduction half-reactions with
solutes at 1M and gases at 1 atm

Cu2+ + 2e  Cu
E0 = 0.34 V vs. SHE

SO42 + 4H+ + 2e  H2SO3 + H2O

E0 = 0.20 V vs. SHE
 E0cell and DG0

E0cell > 0 DG0 < 0 Spontaneous

E0cell < 0 DG0 > 0 Not

E0cell = 0 DG0 = 0 Equilibrium

 Calculating E0cell
E0cell = E0cathode - E0anode

Br2(aq)+2V3+ +2H2O(l)  2VO2+(aq)+ 4H+(aq)+ 2Br-(aq)

Given: E0cell = +1.39 V

E0Br2 = +1.07 V

What is E0V3+ and is the reaction spontaneous?

 E0 values
More positive:
Stronger oxidizing agent
More readily accepts e-

More negative:
Stronger reducing agent
More readily gives e-

Stronger R.A. + O.A.  Weaker R.A. + O.A.

Free Energy and Cell Potential

wmax  DG  nFE
0 0

n: number of moles of e-
F: Faraday’s constant
96485 C
mol of e-
 DG0, E0, and K

DG  RTlnK  nFE
0 0

RT
so E 
0
lnK
nF
At equilibrium: DG0 = 0 and K = Q
At 298 K:
0.0592
E 
0
logK
n
 Nernst Equation
Under nonstandard conditions
DG  DG  RTlnQ
0

 nFE  nFE  RTlnQ

0

RT
E cell E 
0
lnQ
nF
0.0592
298K
E cell E 
0
lnQ
n
 Concentration Cells

. . . a cell in which both compartments

have the same components but at
different concentrations
17_366

e– e–

e– Porous e–
disk
Ag Ag

0.1 M Ag + 1 M Ag +
– –
0.1 M NO 3 1 M NO 3

Anode Cathode