Analisis

Elektrokimia

Oleh
Moh. Hayat

Akademi Kimia Analisis 2014

Electromotive Force (emf)
• Water only
spontaneously flows
one way in a
waterfall.
• Likewise, electrons
only spontaneously
flow one way in a
redox reaction—from
higher to lower
potential energy.
Electromotive Force (emf)
• The potential difference between the anode and
cathode in a cell is called the electromotive force
(emf).
• It is also called the cell potential, and is
designated Ecell.
Cell Potential
Cell potential is measured in volts (V).

work or electrical potential energy J

E cell   V
unit of charge moved C
 Pengukuran Potensial Sel 1/2 Reaksi
• Reaksi kimia yang terjadi terdiri dari 2 setengah reaksi yang
menggambarkan perubahan kimia yag sesungguhnya terjadi pada 2
elektroda

• Masing-masing ½ reaksi berhubungan pada beda potensial antar fasa

pada elektroda. Sehingga untuk menggambarkan ½ reaksi diperlukan
elektroda reference (RE)

• RE memiliki potensial konstan, sehingga dapat menggambarkan reaksi

yang terjadi pada working elektrode (WE)

• RE yang diterima internasional adalah Standard Hydrogen Electrode (SHE)

atau Normal Hydrogen Electrode (NHE)
 Measuring
Standard
Electrode
Potential

Potentials are measured against a hydrogen ion

reduction reaction, which is arbitrarily assigned a
potential of zero volts.
Standard Hydrogen Electrode
• Their values are referenced to a standard
hydrogen electrode (SHE).
• By definition, the reduction potential for
hydrogen is 0 V:
2 H+ (aq, 1M) + 2 e−  H2 (g, 1 atm)
• Tetapi karena SHE kurang praktis, sering
digunakan elektroda lain

• Saturated Calomel Electrode (SCE),

Hg/Hg2Cl2/KCl
DE = 0,242 V vs. NHE

• Elektroda Ag/AgCl/KCl (saturated in water)

DE = 0,197 V vs. NHE
Standard Reduction Potentials

Reduction
potentials for
many
electrodes
have been
measured and
tabulated.
Standard Cell Potentials
The cell potential at standard conditions can
be found through this equation:

Ecell  (cathode) − Ered

 = Ered  (anode)
Cell Potentials
• For the oxidation in this cell,
 = −0.76 V
Ered
• For the reduction,

 = +0.34 V
Ered
From a table of reduction potentials:
Zn2+ + 2e-  Zn E = -0.76V
Cu2+ + 2e-  Cu E = +0.34V

Zn  Zn2+ + 2e- E = +0.76V

Cu2+ + 2e-  Cu E = +0.34V

Zn + Cu2+  Zn2+ + Cu E0 = + 1.10 V

Cell Potentials
Ecell
 = Ered (cathode) − Ered
 (anode)
= +0.34 V − (−0.76 V)
= +1.10 V
Oxidizing and Reducing Agents

• The strongest
oxidizers have the
most positive
reduction potentials.
• The strongest
reducers have the
most negative
reduction potentials.
Oxidizing and Reducing Agents

The greater the

difference between the
two, the greater the
voltage of the cell.
 Calculating DG0 for a Cell
DG0 = -nFE0
n = moles of electrons in balanced redox equation
F = Faraday constant = 96,485 coulombs/mol e-
Zn + Cu2+  Zn2+ + Cu E0 = + 1.10 V
 coulombs Joules
DG   (2 mol e )(96 485
0

)(1.10 )
mol e Coulomb
DG   212267 Joules   212 kJ
0
Hubungan Potensial dan Arus
Let’s measure the current that flows as we change the voltage
of the platinum electrode
Persamaan Nernst
• Potensial sel galvani tergantung pada aktivitas
dari berbagai spesies yang bereaksi di dalam sel.
• Persamaan yang menyatakan hubungan ini
disebut Persamaan Nernst.
• Diambil dari nama Ahli Kimia Fisika Jerman
Walther Nernst yang pertama kali menggunakan
persamaan ini.
• Tinjau reaksi berikut
aA + bB cC + dD
• Perubahan energi bebas untuk persamaan
tersebut adalah :
D G = D G  RT ln
C c Dd

Aa Bb
atau

D G = D G  2,3 RT log
C c Dd

Aa Bb
• Dengan mensubstitusikan hubungan antara DG
dengan E, diperoleh

 nFE =  nFE  2,3 RT log

C c Dd

Aa Bb
E=E  2,3 RT
log
C c Dd
nF Aa Bb
• Pada 298 K persamaan menjadi

E = E 
0,059
log
C c Dd
n Aa Bb
• Pada kondisi equilibrium DG = 0, dan DE = 0,
dan

K
Cc Dd
Aa Bb
maka
D G = - RT ln K
atau
 RT
DE = ln K
nF
Contoh :
Tentukan konstanta kesetimbangan untuk
reaksi :
Zn + Cu2+  Zn2+ + Cu E0 = + 1.10 V

Jawab :

 0,059 (1,10)(2)
E=E  log K = log K
n 0,059
0 = 1,10 
0,059
log K log K  37,2
2
K  1037,2
K  1,58 x 1037
Concentration Cells

... a cell in which both

compartments have the same
components but at different
concentrations
 ???
Concentration
Cell
Both sides have
the same
components but
at different
concentrations.

Step 1: Determine which side undergoes

oxidation, and which side undergoes reduction.
 ???
Concentration
Cell
Both sides have
Anode Cathode the same
components but
at different
concentrations.

The 1.0 M Zn2+ must decrease in concentration, and

the 0.10 M Zn2+ must increase in concentration
Zn2+ (1.0M) + 2e-  Zn (reduction)
Zn  Zn2+ (0.10M) + 2e- (oxidation)
Zn2+ (1.0M)  Zn2+ (0.10M)
 ???
Concentration
Concentration Cell Cell
Both sides have
Anode Cathode the same
components but
at different
concentrations.

Step 2: Calculate cell potential using the Nernst

Equation (assuming 25 C).
Zn2+ (1.0M)  Zn2+ (0.10M)

0.0591
EE  0
log(Q)
n
Nernst Calculations
Zn2+ (1.0M)  Zn2+ (0.10M)

0.0591
EE  0
log(Q)
n
(0.10)
E  0.0 Volts n2
0
Q
(1.0)

0.0591 0.10
E  0.0  log( )  0.030Volts
2 1.0
 Terima Kasih

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