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Elektrokimia
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Voltammetry
Polarography
Coulometry
Conductometry
Potensiometry
UAS
Electrochemistry

Electrochemistry
Electrochemical Reactions
In electrochemical reactions, electrons
are transferred from one species to
another.

Electrochemistry

Voltaic Cells
In spontaneous
oxidation-reduction
(redox) reactions,
electrons are
transferred and
energy is released.

Electrochemistry

Voltaic Cells
We can use that
energy to do work if
we make the
electrons flow
through an external
device.
We call such a setup
a voltaic cell.
Electrochemistry

Volatic / Galvanic Cells

anode
oxidation

cathode
reduction

spontaneous
redox reaction

Electrochemistry

19.2

Galvanic Cells
The difference in electrical
potential between the anode
and cathode is called:
cell voltage
electromotive force (emf)
cell potential
Cell Diagram
Zn (s) + Cu2+ (aq)

Cu (s) + Zn2+ (aq)

[Cu2+] = 1 M & [Zn2+] = 1 M

Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode
cathode

Electrochemistry

19.2

Electromotive Force (emf)

Water only
spontaneously flows
one way in a
waterfall.
Likewise, electrons
only spontaneously
flow one way in a
redox reactionfrom
higher to lower
potential energy.
Electrochemistry

Electromotive Force (emf)

The potential difference between the
anode and cathode in a cell is called
the electromotive force (emf)
/ Gaya Gerak Listrik (GGL)
It is also called the cell potential, and is
designated Ecell.
Electrochemistry

Standard Reduction Potentials

Standard reduction potential (E0) is the voltage associated
with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.

Reduction Reaction
2e- + 2H+ (1 M)

H2 (1 atm)

E0 = 0 V

Electrochemistry

Standard hydrogen electrode (SHE)

19.3

Standard Reduction Potentials

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation):

Zn (s)

Cathode (reduction): 2e- + 2H+ (1 M)

Zn (s) + 2H (1 M)
+

Zn2+ (1 M) + 2eH2 (1 atm)

Electrochemistry

Zn + H2 (1 atm)
2+

19.3

Standard Reduction Potentials

Reduction
potentials for
many
electrodes
have been
measured and
tabulated.

Electrochemistry

Oxidizing and Reducing Agents

The strongest
oxidizers have the
most positive
reduction potentials.
The strongest
reducers have the
most negative
reduction potentials.
Electrochemistry

Oxidizing and Reducing Agents

The greater the
difference between
the two, the greater
the voltage of the
cell.

Electrochemistry

E0 is for the reaction as

written

The more positive E0 the

greater the tendency for the
substance to be reduced

The half-cell reactions are

reversible

The sign of E0 changes

when the reaction is
reversed

Changing the stoichiometric

coefficients of a half-cell
reaction does not change
Electrochemistry
the value of E0
Pt2+ +2e -> Pt

E=1,2 V

19.3

Electrochemistry

Standard Reduction Potentials

0
Ecell
= 0.76 V

0
Standard emf (Ecell
)

0
0
Ecell
= E0cathode - Eanode

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

0 2+
0
Ecell
= E0H+/H2 - EZn
/Zn
0.76 V = 0 - E0Zn2+/Zn
E0Zn2+/Zn = -0.76 V
Zn2+ (1 M) + 2e-

Zn

E0 = -0.76 V

Electrochemistry

19.3

Standard Reduction Potentials

0
Ecell
= 0.34 V

0
0
Ecell
= E0cathode - Eanode

E0cell = E0Cu2+/Cu EH0 +/H

0.34 = E0Cu2+ /Cu - 0

E0Cu2+/Cu = 0.34 V

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode (oxidation):

H2 (1 atm)

Cathode (reduction): 2e- + Cu2+ (1 M)

H2 (1 atm) + Cu (1 M)
2+

2H+ (1 M) + 2eCu (s)

Cu (s) + 2H (1 M)
+

Electrochemistry

19.3

Standard Cell Potentials

The cell potential at standard conditions
can be found through this equation:
Ecell
(cathode) Ered
(anode)
= Ered
Because cell potential is based on
the potential energy per unit of
charge, it is an intensive property.

Electrochemistry

Cell Potentials
For the oxidation in this cell, Zn

Ered
= 0.76 V
For the reduction, Cu

Ered
= +0.34 V

Electrochemistry

Cell Potentials
Ecell
= Ered
(cathode) Ered
(anode)
= +0.34 V (0.76 V)
= +1.10 V

Electrochemistry

What is the standard emf of an electrochemical cell made

of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr
electrode in a 1.0 M Cr(NO3)3 solution?
Cd2+ (aq) + 2e-

Cd (s) E0 = -0.40 V Cd is the stronger oxidizer

Cr3+ (aq) + 3e-

Cr (s)

Anode (oxidation):

E0 = -0.74 V

Cr3+ (1 M) + 3e- x 2

Cr (s)

Cathode (reduction): 2e- + Cd2+ (1 M)

2Cr (s) + 3Cd2+ (1 M)

Cd will oxidize Cr

Cd (s)

x3

3Cd (s) + 2Cr3+ (1 M)

0
0
Ecell
= E0cathode - Eanode
0
Ecell
= -0.40 (-0.74)
0
Ecell
= 0.34 V

Electrochemistry

19.3

Spontaneity of Redox Reactions

Electrochemistry

19.4

Gibbs Free Energy

G for a redox reaction can be found by
using the equation
G = nFE
where n is the number of moles of
electrons transferred, and F is a
Faraday constant.
1 F = 96,485 C/mol = 96,485 J/V-mol
Electrochemistry

Free Energy
Under standard conditions,
G = nFE
Remember that
G = G + RT ln Q
This means
nFE = nFE + RT ln Q
Electrochemistry

Nernst Equation
Dividing both sides by nF, we get the
Nernst equation:
RT
ln Q
E = E
nF
or, using base-10 logarithms,
2.303 RT
log Q
E = E
nF
Electrochemistry

Nernst Equation
At room temperature (298 K),
2.303 RT
= 0.0592 V
F
Thus the equation becomes
0.0592
log Q
E = E
n
Electrochemistry

Spontaneity of Redox Reactions

G = -nFEcell
G =
0

-nFE 0

cell

n = number of moles of electrons in reaction

J
F = 96,500
= 96,500 C/mol
V mol

0
G0 = -RT ln K = -nFEcell
0
Ecell

(8.314 J/Kmol)(298 K)
RT
ln K =
ln K
=
nF
n (96,500 J/Vmol)

0
Ecell
=
0

Ecell

0.0257 V
ln K
n

0.0592 V
log K
=
n
Electrochemistry

19.4

What is the equilibrium constant for the following reaction

at 250C? Fe2+ (aq) + 2Ag (s)
Fe (s) + 2Ag+ (aq)
0

Ecell

0.0257 V
ln K
=
n

Oxidation:

2Ag

Reduction: 2e- + Fe2+

2Ag+ + 2eFe

n=2

0
E0 = E0Fe2+ /Fe EAg
+/Ag

E0 = -0.44 (0.80)
E0 = -1.24 V

0
Ecell
xn
-1.24 V x 2
= exp
K = exp
0.0257 V
0.0257 V

K = 1.23 x 10-42
Electrochemistry

19.4

The Effect of Concentration on Cell Emf

G = G0 + RT ln Q

G = -nFE

G0 = -nFE 0

-nFE = -nFE0 + RT ln Q
Q = reaction quotient = (hasil bagi reaksi)
Nernst equation
E = E0 -

RT
ln Q
nF

At 298K
E = E0 -

0.0257 V
ln Q
n

E = E0 -

0.0592 V
log Q
n
Electrochemistry

19.5

Concentration Cells

Notice that the Nernst equation implies that a cell

could be created with the same substance at both
electrodes.
For such a cell, Ecell
would be 0, but Q would not.
Therefore, as long as the concentrations
are different, E will not be 0.

Electrochemistry

Will the following reaction occur spontaneously at 250C if

[Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Fe2+ (aq) + Cd (s)
Fe (s) + Cd2+ (aq)
E0Fe2+/Fe = -0.44 V
Oxidation:

Cd

Reduction: 2e + Fe
-

ECd2+/Cd = -0.4 V
Cd2+ + 2e2Fe

2+

n=2

0
E0 = E0Fe2+ /Fe ECd
2+/Cd

E0 = -0.44 (-0.40)
E0 = -0.04 V

0.0257 V
ln Q
n
0.010
0.0257 V
ln
E = -0.04 V 2
0.60
E = 0.013
E = E0 -

Electrochemistry

E>0

Spontaneous

19.5

Applications of
Oxidation-Reduction
Reactions
Electrochemistry

Alkaline Batteries

Electrochemistry

Batteries

Mercury Battery

Anode:
Cathode:

Zn(Hg) + 2OH- (aq)

HgO (s) + H2O (l) + 2eZn(Hg) + HgO (s)

ZnO (s) + H2O (l) + 2eHg (l) + 2OH- (aq)

ZnO (s) + Hg (l)
Electrochemistry

19.6

Batteries

Dry cell
Leclanch cell

Anode:
Cathode:

Zn (s)
2NH+4 (aq) + 2MnO2 (s) + 2e-

Zn (s) + 2NH4 (aq) + 2MnO2 (s)

Zn2+ (aq) + 2eMn2O3 (s) + 2NH3 (aq) + H2O (l)

Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)

Electrochemistry

19.6

Batteries

Electrochemistry

Batteries

Lead storage
battery

Anode:
Cathode:

Pb (s) + SO2-4 (aq)

PbSO4 (s) + 2e-

PbO2 (s) + 4H+ (aq) + SO42- (aq) + 2e-

Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO42- (aq)

PbSO4 (s) + 2H2O (l)

2PbSO4 (s) + 2H2O (l)

Electrochemistry

19.6

Hydrogen Fuel Cells

Electrochemistry

A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning

Anode:
Cathode:

2H2 (g) + 4OH- (aq)

O2 (g) + 2H2O (l) + 4e2H2 (g) + O2 (g)

4H2O (l) + 4e4OH- (aq)

2H2O (l)

Electrochemistry

19.6

Corrosion

Electrochemistry

19.7

Corrosion, cont.

Electrochemistry

Corrosion Prevention

Electrochemistry

Cathodic Protection of an Iron Storage Tank

Electrochemistry

19.7

Quiz: (p.362)
1. Larutan yang mengandung 0,001 M Cr2O72- dan 0,01 M
Cr3+ mempunyai pH 2,0. Tentukan potensial sel-nya jika E0
= 1,33 V.
2. 5 mL larutan 0,1 M Ce4+ ditambahkan ke dalam 5 mL
larutan 0,3M Fe2+. Hitung potensial selnya jika E0 Fe3+/Fe2+
= 0,771 V.

Electrochemistry

Oxidation Numbers
In order to keep
track of what loses
electrons and what
gains them, we
assign oxidation
numbers.

Electrochemistry

Oxidation and Reduction

A species is oxidized when it loses electrons.

Here, zinc loses two electrons to go from neutral
zinc metal to the Zn2+ ion.
Electrochemistry

Oxidation and Reduction

A species is reduced when it gains electrons.

Here, each of the H+ gains an electron and they
combine to form H2.
Electrochemistry

Oxidation and Reduction

What is reduced is the oxidizing agent.

H+ oxidizes Zn by taking electrons from it.

What is oxidized is the reducing agent.

Zn reduces H+ by giving it electrons.
Electrochemistry

Assigning Oxidation Numbers

1. Elements in their elemental form have
an oxidation number of 0.
2. The oxidation number of a monatomic
ion is the same as its charge.

Electrochemistry

Assigning Oxidation Numbers

3. Nonmetals tend to have negative
oxidation numbers, although some are
positive in certain compounds or ions.
Oxygen has an oxidation number of 2,
except in the peroxide ion in which it has
an oxidation number of 1.
Hydrogen is 1 when bonded to a metal,
+1 when bonded to a nonmetal.

Electrochemistry

Assigning Oxidation Numbers

3. Nonmetals tend to have negative
oxidation numbers, although some are
positive in certain compounds or ions.
Fluorine always has an oxidation number
of 1.
The other halogens have an oxidation
number of 1 when they are negative;
they can have positive oxidation
numbers, however, most notably in
oxyanions.
Electrochemistry

Assigning Oxidation Numbers

4. The sum of the oxidation numbers in a
neutral compound is 0.
5. The sum of the oxidation numbers in a
polyatomic ion is the charge on the
ion.

Electrochemistry

Balancing Oxidation-Reduction
Equations
Perhaps the easiest way to balance the
equation of an oxidation-reduction
reaction is via the half-reaction method.

Electrochemistry

Balancing Oxidation-Reduction
Equations
This involves treating (on paper only) the
oxidation and reduction as two separate
processes, balancing these half reactions,
and then combining them to attain the
balanced equation for the overall reaction.

Electrochemistry

Half-Reaction Method
1. Assign oxidation numbers to
determine what is oxidized and what is
reduced.
2. Write the oxidation and reduction halfreactions.

Electrochemistry

Half-Reaction Method
3. Balance each half-reaction.
a.
b.
c.
d.

Balance elements other than H and O.

Balance O by adding H2O.
Balance H by adding H+.
Balance charge by adding electrons.

4. Multiply the half-reactions by integers

so that the electrons gained and lost
are the same.
Electrochemistry

Half-Reaction Method
5. Add the half-reactions, subtracting
things that appear on both sides.
6. Make sure the equation is balanced
according to mass.
7. Make sure the equation is balanced
according to charge.

Electrochemistry

Half-Reaction Method

Consider the reaction between MnO4 and C2O42 :

MnO4(aq) + C2O42(aq)

Mn2+(aq) + CO2(aq)
Electrochemistry

Half-Reaction Method
First, we assign oxidation numbers.
+7

+3

MnO4 + C2O42-

+2

+4

Mn2+ + CO2

Since the manganese goes from +7 to +2, it is reduced.

Since the carbon goes from +3 to +4, it is oxidized.
Electrochemistry

Oxidation Half-Reaction
C2O42

CO2

To balance the carbon, we add a

coefficient of 2:
C2O42

2 CO2
Electrochemistry

Oxidation Half-Reaction
C2O42

2 CO2

The oxygen is now balanced as well.

To balance the charge, we must add 2
electrons to the right side.
C2O42

2 CO2 + 2 e
Electrochemistry

Reduction Half-Reaction
MnO4

Mn2+

The manganese is balanced; to balance

the oxygen, we must add 4 waters to
the right side.
MnO4

Mn2+ + 4 H2O
Electrochemistry

Reduction Half-Reaction
MnO4

Mn2+ + 4 H2O

To balance the hydrogen, we add 8 H +

to the left side.
8 H+ + MnO4

Mn2+ + 4 H2O
Electrochemistry

Reduction Half-Reaction
8 H+ + MnO4

Mn2+ + 4 H2O

To balance the charge, we add 5 e to

the left side.
5 e + 8 H+ + MnO4

Mn2+ + 4 H2O
Electrochemistry

Combining the Half-Reactions

Now we evaluate the two half-reactions
together:
C2O42

2 CO2 + 2 e

5 e + 8 H+ + MnO4

Mn2+ + 4 H2O

To attain the same number of electrons

on each side, we will multiply the first
Electrochemistry
reaction by 5 and the second by 2.

Combining the Half-Reactions

5 C2O42

10 CO2 + 10 e

10 e + 16 H+ + 2 MnO4

2 Mn2+ + 8 H2O

When we add these together, we get:

10 e + 16 H+ + 2 MnO4 + 5 C2O42
2 Mn2+ + 8 H2O + 10 CO2 +10 e
Electrochemistry

Combining the Half-Reactions

10 e + 16 H+ + 2 MnO4 + 5 C2O42
2 Mn2+ + 8 H2O + 10 CO2 +10 e
The only thing that appears on both sides are the
electrons. Subtracting them, we are left with:
16 H+ + 2 MnO4 + 5 C2O42
2 Mn2+ + 8 H2O + 10 CO2
Electrochemistry

Balancing in Basic Solution

If a reaction occurs in basic solution, one
can balance it as if it occurred in acid.
Once the equation is balanced, add OH
to each side to neutralize the H + in the
equation and create water in its place.
If this produces water on both sides, you
might have to subtract water from each
side.

Electrochemistry