REAKSI ANORGANIK DALAM MEDIUM AIR:

REAKSI REDOX DAN ELEKTROKIMIA

Oxidation and reduction in terms of oxygen transfer
Definitions
Oxidation is gain of oxygen.
Reduction is loss of oxygen.
For example, in the extraction of iron from its ore:




Because both reduction and oxidation are going on side-by-side,
this is known as a redox reaction.
Redox reaction
Oxidation and reduction in terms of electron transfer
This is easily the most important use of the terms oxidation and
reduction at A' level.
Definitions
Oxidation is loss of electrons.
Reduction is gain of electrons.


Copper(II) oxide and magnesium oxide are both ionic. The metals
obviously aren't. If you rewrite this as an ionic equation, it turns out
that the oxide ions are spectator ions and you are left with:
Oxidation and reduction always occur simultaneously
Losing electrons is oxidation, and the substance that loses the
electrons is called the reducing agent.
Gaining electrons is reduction, and the substance that gains the
electrons is called the oxidizing agent.
Mg is oxidized: loses e
-
, becomes a Mg
2+
ion
S is reduced: gains e
-
= S
2-
ion
Mg is the
reducing
agent
S is the oxidizing agent
Mg(s) + S(s) MgS(s)
Not All Reactions are Redox Reactions
- Reactions in which there has been no change in
oxidation number are NOT redox reactions.
Examples:
) ( ) ( ) ( ) (
3
2 5 1 1 1 1 1
3
2 5 1
aq O N Na s Cl Ag aq Cl Na aq O N Ag
+ + + + + +
+ +
) ( ) ( ) ( ) ( 2
2
2
1
4
2 6
2
1
4
2 6
2
1 1 2 1
l O H aq O S Na aq O S H aq H O Na
+ + + + + + +
+ + +
O- I- O
O
-
The I-O bonds are polar covalent, polarized toward
the more electronegative oxygen. If these bonds
were ionic, then the shared electron density would
reside entirely with the oxygens
This leads to an oxidation number of -2 for each oxygen (eight valence
electrons versus six in the free atom) and +5 for iodine (two valence
electrons versus seven).
As is the case for formal charge, the algebraic sum of all oxidation
numbers equals the charge on the species
Oxidation involves an increase in oxidation state
Reduction involves a decrease in oxidation state
Oxidation Numbers that occurs in compounds
Rules for Assigning Oxidation Numbers
1. The oxidation number of any uncombined
element is zero.
2. The oxidation number of a monatomic ion
equals its charge.

1 1
2
0 0
2 2
+
+ Cl Na Cl Na
3. The oxidation number of oxygen in compounds
is -2, except in peroxides, such as H
2
O
2
where it
is -1.
4. The oxidation number of hydrogen in
compounds is +1, except in metal hydrides,
like NaH, where it is -1.
2
2
1 +
O H
5. The sum of the oxidation numbers of the atoms
in the compound must equal 0.
2
2
1 +
O H
2(+1) + (-2) = 0
H O
2
1 2 2
) (
+ +
H O Ca
(+2) + 2(-2) + 2(+1) = 0
Ca O H
6. The sum of the oxidation numbers in the formula
of a polyatomic ion is equal to its ionic charge.

3
2 ?
O N
X + 3(-2) = -1
N O

2
4
2 ?
O S
thus X = +5
thus X = +6
X + 4(-2) = -2
S O
Active metals:
Lose electrons easily
Are easily oxidized
Are strong reducing agents

Active nonmetals:
Gain electrons easily
Are easily reduced
Are strong oxidizing agents
With electon configuration 1s
2
2s
2

2p
6
3s
2
,magnesium has two valence
electrons.

Consequently,the first two energies
of Mg are small relative to IE3 and
beyond.

Thus,it is reasonable to think of a
Mg
2+
ion, but no cations of higher
charge exist
Electron transfer in Aqueous Solution
Recall the basic eqiation relating enthalpy, entropy and
free energy:

For aqueous solution, it is convenient to use the
electrochemical potential in volts as a substitute for free
energy

Standard potential can be related to the equilibrium
constant by the equation:

AG = A H-TAS
AG = - nFE
log K = nE/0,05916
Pada reaksi redoks dikenal potensial standar reduksi yaitu harga
potensial sel standard dari reaksi setengah sel yang diukur dengan
pembanding potensial standard reduksi dari hydrogen. Keadaan
standar diukur pada temperatur 25
0
C, tekanan 1 atm dan
konsentrasi 1M. Reaksi reduksi H
+
menjadi H
2
dalam keadaan
standard memiliki harga E
0
=0.

2H
+
+ 2e
-
H
2
E
0
= 0,000 V

Harga potensial standard reduksi lainnya adalah harga relatif
dengan pembanding elektroda hidrogen standard.
Standard reduction potentials
Standard reduction potentials
Define a standard half-cell of
potential = 0V against which all
other half-cell reduction
potentials are measured.
Each component in these
standard cells having unit
concentration.

By convention: Standard (or
Normal) Hydrogen Electrode is
used

Pt(s) | H
2
(g) | H
+
(a) || Ag
+
(a) | Ag(s)
|_______________|
NHE
H
+
(aq) + e- H
2
(g)E
0
=0V

K
+
+ e
-
K E
0
= -2,970 V.

Reduksi K
+
menjadi K memiliki harga potensial standard reduksi
negatif, lebih rendah dibandingkan E
0
H+/H2
. Arah reaksi seperti
tertulis secara thermodinamika tidak berjalan, sehingga reduksi K
+

menjadi K bukanlah reaksi yang spontan.
Reaksi sebaliknya dengan harga potensial standard oksidasi 2,970
V lebih dapat berjalan jika ditinjau dari segi thermodinamika.
Kespontanan reaksi yang secara kuantitatif diukur dengan AG
didukung dari harga E
0
positif. Hubungan harga AG dengan harga
E
0
adalah

AG = -nF E
0

F adalah konstanta Faraday (96,487 kJ/mol V) sedangkan n adalah
jumlah elektron yang ditransfer saat proses redoks.
Basic Cell for Measurement of
Electrode Potentials
SHE Half Cell
The cell potential

E = E+ - E- (written as reductions)

Standard Reduction Potentials

Consider Zn(s) Zn
2+
(aq) + 2e
-
. We measure E
cell
relative to the
SHE (cathode):
E
cell
= E
+
(cathode) - E
-
(anode)
0.76 V = 0 V - E
red
(anode).
Therefore, E
red
(anode) = -0.76 V.
Standard reduction potentials must be written as reduction reactions:
Zn
2+
(aq) + 2e
-
Zn(s), E
red
= -0.76 V.
Since E
red
= -0.76 V we conclude that the reduction of Zn
2+
in the
presence of the SHE is not spontaneous.
Electrochemical series

half-rxns
oxidant reductant
E
0
(V)

stronger oxidant
F
2
(g) + 2e- <=> 2F
-
2.890
Ce
4+
+ e- <=> Ce
3+
1.720
Ag
+
+ e- <=> Ag(s) 0.799
Fe
3+
+ e- <=> Fe
2+
0.771
O
2
+ 2H
+
+ 2e- <=> H
2
O
2
0.695
Cu
2+
+ 2e- <=> Cu(s) 0.339
2H
+
+ 2e- <=> H
2
(g)
0.000
Cd
2+
+ 2e- <=> Cd(s) -0.402
Zn
2+
+ 2e- <=> Zn(s) -0.762
K
+
+ e- <=> K(s) -2.936
Li
+
+e- <=> Li(s) -3.040
stronger reducer
AG = -nFE


Therefore if E
cell

is positive, the
reaction is
spontaneous
J/V.mol 96,500
C/mol 500 , 96 1
=
= F
Hubungan entalpi, entropi dan energi bebas gibbs:

AG = A H-TAS


Hubungan harga AG dengan harga E
0
:

AG = -nF E
0

F adalah konstanta Faraday (96,487 kJ/mol V) sedangkan
n adalah jumlah elektron yang ditransfer saat proses
redoks.

Hubungan potensial standard reduksi dengan harga Q
adalah mengikuti persamaan Nernst

ln Q = n E
0
/RT
atau
log Q = n E
0
/0,05916

Pada keadaan non standard harga E (tidak ada tanda
0
pada E
untuk keadaan non standard) adalah sebesar:

E = E
0
- RT ln Q / n = E
0
- 0,05916 log Q/n



Diagram potensial reduksi menunjukkan harga potensial standard
reduksi pada beberapa harga tingkat oksidasi

E1
0
= +0,682 E2
0
= +1,776
O
2
H
2
O
2
H
2
O

E3
0
= +1,229

Pada diagram potensial tersebut O memiliki 3 tingkat oksidasi yaitu
0, -1, dan 2. Dengan melihat hubungan antara AG dengan E
0

maka harga AG akan sebanding dengan harga E
0
sehingga jika AG
bersifat aditif maka E
0
juga bersifat aditif. Pada contoh diagram
potensial diatas maka hubungan besaran E
1
0
, E
2
0
dan E
3
0
adalah

n
3
E
3
0
= n
1
E
1
0
+ n
2
E
2
0
(volt equivalent)
Volt equivalent
FeO
4
2-
Fe
3+
Fe
2+
Fe
+2,20 +0,771, n2 -0.440, n3
n4, E
0
4
?
E
0
4
= -0,036 V
Potensial sel (overall cell potentials) merupaka driving force reaksi
redoks.
Harga potensial sel positif menunjukkan reaksi berjalan sesuai
dengan arah reaksi tertulis.
Driving force dari reaksi dicerminkan dari harga konstanta
equilibrium, K, dan perubahan energi bebas Gibbs, AG.
Dari hubungan log K dengan E
sell
maka harga K yang tinggi
didapatkan dari harga E
sell
yang tinggi dan harga AG yang negatif
(sejumlah energi dibebaskan) didapatkan dari harga E
sell
positif.

E = E
0
- RT ln K / n = E
0
- 0,05916 log K/n


AG = -n F E
0

Driving force reasi redoks
Note, however, that if we are combining two half reactions to obtain a third half
reaction, the values are not additive, since we are not eliminating electrons. Free
energies are always additive, so we combine them.
It is obvious that the iron reaction will have to happen twice for every chlorine
molecule that reacts. Allow for that, and then add the two half-equations together.
The reaction between chlorine and iron(II) ions
The reaction between hydrogen peroxide and manganate(VII) ions
The oxidation of ethanol by acidified potassium dichromate(VI)
2 x [MnO
4
2-
+ 4H
+
+2e
-
MnO
2
+ 2H
2
O] E
0
=+2,26 V
2H
2
O O
2
+4H
+
+ 4e
-
E
0
= -1,23 V

2MnO
4
2-
+ 4H
+
MnO
2
+ 2H
2
O + O
2
E0 =1,03 V
Electrone gained in the reduction must equal the electrons lost in the oxidation
Potential is independent of stoichiometry

Potential for overall process is positive reaction is spontaneous under
standard condition
2 x [OCl
-
+ 4H
2
O + 2e
-
] Cl
-
+ 2OH
-
] E
0
=+0,89 V
OCl
-
+ 4OH
-
ClO
3
-
+2H
2
O + 4e
-
E
0
= -0,5V

3OCl
-
Cl
-
+ ClO
3
-
E0 =0,39 V
ClO
4
-
ClO
3
-
ClO
2
-
OCl
-
Cl
2
Cl
-

Standard reduction potential diagram for Cl in basic solution:
0,36
0,33
0,66 0,40
1,36
0,50
0,89
The influence of non aqueous ligand on standard
reduction potential of Fe
3+
/Fe
2+
couple
The presence of coordinating ligand can play an important
role in stabilizing or destabilizing the oxidation state of
transition metals.
Ligand E0, V Ligand E0, V
H2O
OH-
C2O42-
+0,77
-0,56
+0,02
CN-
Bipy
Phen
+1.10
+0.36
+1.12
Fe(H2O)6 2+ Fe(H2O)6 3+ E0 = -0,77
Fe(phen) 2+ Fe(phen) 3+ E0 = -1,12
Reduction of Co
III
Co
II
4 Co
3+
+ 2 H
2
O 4 Co
2+
+ 4 H
+
+ O
2
Eo = +0,579 V
[Co(NH3)6]
3+
+ 1 e- [Co(NH3)6]
2+
Eo = +0,11 V
[Co(CN)6]
3+
+ 1 e- [Co(CN)6]
2+
Eo = -0,83 V
Application of a combined oxidation-nonaqueous
ligand
2Au + 6H+ 2Au3+ + 3H2
NO3- 4H+ + 3e- NO + 2 H2O
Au + NO3- + 4 Cl- + 4 H+ AuCl4- +NO + 2 H2O
E0 =-1,52 V
E0 = 0,96 V
Au + 4 Cl- + 4H+ AuCl4- + 4H+ + 3e- E0 = -0,99 V
oksidasi
reduksi
E0 = -0,03
Non standard concentrations
Non standard temperature
Non standard pH
Non standard concentration
NiO
2
Ni
2+
Ni
+1,678 -0,250
E = -0,250 -
0,05916 log (1/[Ni
2+
])
2
= -0,250 + 0,02958 log [Ni
2+
]
Non standard Temperature
E = Eo -
(1,985 x 10
-4
) T. Log Q
n
E = -0,250 + (9,925 x 10
-5
) T. Log [Ni
2+
]
The potential changes very slowly with changing temperature
Non standard pH: pH effect
NiO
2
Ni
2+
Ni
+1,678 -0,250
NiO
2
+ 4 H
+
+ 2e- Ni
2+
+ 2 H
2
O Eo = +1,678 V
E = Eo - log
0,05916
n
[Ni
2+
]
[H+]
4
E = +1,678 - 0,1183 . pH
Jika konsentasi Ni
2+
= 1M
Ni + 2 H+ Ni
2+
+

H
2
E
0
= 0,250 V
Buktikan bahwa pada pH 5, E = -0,046
NiO
2
Ni(OH)2 Ni
+0,490 -0,720
Solubility effect
Ni(OH)2 Ni2+ + 2 OH- Ksp = 1,5 x 10
-16
Ni2+ + 2e- Ni E
0
1 = -0,250 V
Ni(OH)2 + 2e- Ni + 2 OH-
E
0
2 = ?
0,05916.log Ksp + (2 x -0,250) = 2 x E02
E
0
2 = -0,72 V
"Electron Activity" (pe)
We can imagine that electrons have a
measurable activity and use -log (e) = pe,
instead of E
H
.
For a half cell reaction.
oxidized + mH
+
+ ne = reduced




K =
(reduced)
(oxidized)(H
+
)
m
e
n
"Electron Activity" (pe) (cont.)





at 25C
Let pe = -log(e
-
)
then

logK
=
nlog(e
-
)
+
log
(reduced)
(oxidized)

mlog(H
+
)
"Electron Activity" (pe) (cont.)



log K is sometimes called pe
0

***Remember*** Electron activity is a
convenient fiction, not a physical reality.
logK = npe + log
(reduced)
(oxidized)
+ mpH
We also included protons in
the Nernst equation
E
H
= E
0

RT
2.3nF
log
(reduced)
(oxidized)
+ mpH



(

(
Comparison of the Nernst and
pe equations
log
(reduced)
(oxidized)
+ mpH= logK npe
RT
2.3nF
log
(reduced)
(oxidized)
+ mpH



(

(
= E
0
E
H
Equate the two equations
2.3nF
RT
E
0
E
H
| |
= logK- npe
At 25 C

n
0.059
E
0
E
H
| |
= logK- npe
pe can easily be calculated
from E
H

pe =
E
H
0.059
pe
0
= logK =
nE
H
0
0.059
Combining half cell reactions to
describe a complete reaction.
Question: What is the equilibrium
constant for the oxidation of Fe
2+
by O
2
?
log K
Fe
2+
= e
-
+ Fe
3+
-13.04
H
+
+ 1/4O
2
+ e
-
= 1/2H
2
O 20.78
---------------------------------------------------------------
H
+
+ 1/4O
2
+ Fe
2+
= 1/2H
2
O + Fe
3+
7.74
This equation says that O
2
can readily
oxidize Fe
2+
at acid pH values

Combining half cell reactions
(cont.)
K = 10
7.7
=
(Fe
3+
)
(H
+
)(Fe
2 +
)(P
O
2
)
1
4
log K = pH -1/4log Po
2
+ log(Fe
3+
)/(Fe
2+
)]

Combining half cell reactions
(cont.)
Find the pH at which (Fe
3+
) = (Fe
2+
) at Po
2

= 0.21 atm

Answer
7.7 = pH + .17
pH = 7.57

Combining half cell reactions
with solubility reactions

If (Fe
3+
) is controlled by the solubility of Fe(OH)
3
in a soil
then under reducing (flooded soil) conditions Fe
2+
can be
calculated as a function of pH and E
H
.

Fe(OH)
3
+ 3H
+
= Fe
3+
+ 3H
2
O log K = 2.70
(Lindsay)

Predict Fe
2+
as a function of pe in soil

Combining half cell reactions
with solubility reactions(cont.)
log K
Fe
3+
+ e
-
= Fe
2+
13.04
Fe(OH)
3
+ 3H
+
= Fe
3+
+ 3H
2
O 2.70
Soil
----------------------------------------------------------------------
Fe(OH)
3
+ e
-
+ 3H
+
= Fe
2+
+ 3H
2
O 15.74
E
H
= 0.93 V


Combining half cell reactions
with solubility reactions(cont.)
logK = pe + log
(Fe
2 +
)
(H
+
)
3
= pe + log(Fe
2+
) + 3pH
log(Fe
2+
) = logK - pe - 3pH
Combining half cell reactions
with solubility reactions(cont.)
If measured pH = 7.0 and
(Fe
2+
) = 1.0 x 10
-5
M, what is pe?
Answer
pe = 15.74 + 5 - 3(7)
pe = 15.74 - 16.0
pe = -0.26 and E
H
= -0.014
Combining half cell reactions
with solubility reactions(cont.)
Plot pe (or E
H
) vs. pH

Example: Fe(OH)
3
+ 3H
+
+ e
-
= Fe
2+
+
3H
2
O
pe = log K - 3pH - log(Fe
2+
)
at log (Fe
2+
) = -5
pe = 20.74 - 3pH

pe - pH plot for Fe
Precipitation of Siderite

log K
Fe
2+
+ CO
3
2-
= FeCO
3
10.8
H
2
O + CO
2
= H
+
+ HCO
3
-
- 7.81
HCO
3
-
= H
+
+ CO
3
2-
-10.33
-------------------------------------------------------
Fe
2+
+ H
2
O + CO
2
= 2H
+
+ FeCO
3
- 7.34
FeCO
3
(cont.)

From earlier slide

Fe(OH)
3
+ e
-
+ 3H
+
= Fe
2+
+ 3H
2
O +15.74
soil
Fe
2+
+ H
2
O + CO
2
= 2H
+
+ FeCO
3
- 7.34
--------------------------------------------------------------------
Fe(OH)
3
+ e
-
+ CO
2
+ H
+
= FeCO
3
+ 2H
2
O 8.40


K =
1
(H
+
)(P
CO
2
)(e

)
Example, FeCO
3
(cont.)
log K = pH + pe - log Pco
2

Thus at equilibrium pe is a function of pH
and Pco
2
, only.
Set the P
C02
then calc. pH
At pH = 7.0 and Pco
2
= 0.10
pe = log K - pH + log Pco
2
pe = 8.40 - 7.0 - 1.0
pe = 0.4
E
H
= (0.059)( 0.4) = - 0.024 V

pe - pH plot for Fe
Reduction Fe(III) phosphate
(strengite)

Fe
3+
+ e
-
= Fe
2+
13.04
FePO
4
2H
2
O + 2H
+
= Fe
3+
+ H
2
PO
4
-
- 6.85
---------------------------------------------------------------
FePO
4
2H
2
O + e
-
+ 2H
+
= Fe
2+
+ H
2
PO
4
3-
6.19




pe = 6. 2 log
(Fe
2+
)(H
2
PO
2

)
(H
+
)
2
Redox reaction of strengite
(cont.)

pe = 6.2 - log(Fe
2+
) - log(H
2
PO
4
) - 2pH

Let pH = 7.0, (Fe
2+
) = 10
-5
M, and
(H
2
PO
4
3-
) = 10
-5
M

pe = 6.2 + 5 + 5 -14 = 2.2
E
H
= 0.129v

Redox reaction of strengite
(cont.)
Comparison with previous computations
shows strengite is reduced at a similar pe
as Fe(OH)
3

Reduction of iron oxides releases
adsorbed P.
Drainage and restoration of oxic conditions
can tie up P.
Following draining of rice soils, phosphate can
be tied up causing P deficiency for rotation
crops.

Half-Cell Reactions of Common
Electron Acceptors in Soils

Oxidized + mH
+
+ n electrons = reduced + H
2
O

Nernst equation



At 25
0
C
E
H
=
E
o

RT
nF
ln
(reduced)
(oxidized)(H
+
)
m
E
H
= E
o

0.059
n
log
(reduced)
(oxidized)(H
+
)
m
In Volts

E
H
= E
o

0.059
n
log
(reduced)
(oxidized)
+
0.059
n
mpH
In millivolts

E
H
= E
o

59
n
log
(reduced)
(oxidized)
+
59m
n
pH
Applications of Galvanic Cells
Voltaic or Galvanic Cells
The energy released in a spontaneous redox reaction
can be used to perform electrical work.
Voltaic or galvanic cells are devices in which electron
transfer occurs via an external circuit.
Voltaic cells use spontaneous reactions.
If a strip of Zn is placed in a solution of CuSO
4
, Cu is
deposited on the Zn and the Zn dissolves by forming
Zn
2+
.
Zn is spontaneously oxidized to Zn
2+
by Cu
2+
.
The Cu
2+
is spontaneously reduced to Cu
0
by Zn.
Galvanic cells consist of
Anode: Zn(s) Zn
2+
(aq) + 2e
2

Cathode: Cu
2+
(aq) + 2e
-
Cu(s)
Salt bridge (used to complete the electrical circuit): cations move from
anode to cathode, anions move from cathode to anode.
The two solid metals
are the electrodes
(cathode and anode).
As oxidation occurs,
Zn is converted to
Zn
2+
and 2e
-
. The
electrons flow towards
the anode where they are
used in the reduction reaction.
A shorthand convention exists for describing batteries. For
the Cu/Zn battery, it would be described as follows:
Zn(s)|Zn
2+
(aq)|| Cu
2+
(aq)|Cu(s)
The ANODE... The CATHODE...
-supplies electrons to the external circuit (wire) -accepts electrons from the external circuit
(wire) -is the negative pole of the battery -is the positive pole of the battery
-is the site of OXIDATION -is the site of REDUCTION
-is written on the left hand side if the convention -is written on the right hand side if the
is followed convention is followed
-is the half-cell with the lowest electrode potential -is the half-cell with the highest electrode
potential
Applications of Galvanic Cells
Potentiometry and Ion Selective Electrodes

the measure of the cell potential to yield chemical information (conc., activity, charge ....)

A difference in the activity of an ion on either side of a selective membrane results in a
thermodynamic potential difference being created across that membrane


C a
2 +
C a
2 +
0 . 0 1 M C a
2 +
0 . 0 2 M C l
-
0 . 1 M C a
2 +
0 . 2 M C l
-
( 0 . 0 1 + o ) M C a
2 +
( 0 . 1 - o ) M C a
2 +
0 . 0 2 M C l
- 0 . 2 M C l
-
+
+
+
+
-
-
-
-
Calcium selective
molecular
recognition ligand
AG = RT ln
A
1
A
2
= nFE
E =
RT
nF
ln
A
1
A
2
=
0. 05916
n
log
A
1
A
2
( 25C)
The glass pH electrode

int ref

int
+
H

analyte

ext ref

Ag(s) | AgCl(s) | (aq)
-
Cl int), (aq, H ext) (aq, H || (aq)
-
Cl | AgCl(s) | Ag(s)
+ +
Corrosion
Fe
2+
+2e Fe E
0
=-0.44V
2H
+
+ 2e H
2
E
0
=0V
2H
2
O + O
2
=4e4OH
-

E
0
=1.23V
Iron is oxidized in water or
humid conditions to give rust.
Inhibit this by coating with
another material (Zn for example
that forms a protective oxide on
the iron), or by providing a
sacrificial anode (b).
Batteries-providing electricity from
chemistry
The Lead Acid
Storage Battery
was developed in
the late 1800's
and has remained
the most common
and durable of the
battery
technologies (in
vehicles).
Ecell ?
Lead-acid batteries
When the battery is used as a voltage supply, electrons
flow from the Pb metal to the Pb(IV)oxide. The
reactions aren't quite the reverse of the formation
reactions, because now the sulfate ions in the solution
begin to play a role. The two reactions are:
PbO
2
+ 4H
+
+ 2e + SO
4
-2
PbSO
4
+ 2H
2
O

Pb + SO
4
-2
PbSO
4
+ 2e
The overall reaction if we combine the hydrogen
ions and the sulfate:
PbO
2
+ Pb + 2H
2
SO4 2 PbSO
4
+ 2 H
2
O
Lead sulfate is fairly insoluble so that as soon as Pb(II)
ions are formed by either reaction, the ions immediately
precipitate as lead sulfate. The beauty is that this lead
sulfate stays attached to the grids so that it is there for
recharging of the battery.
Pada recharge
batery tipe ini
bagaimana
prosedurnya?
Other batteries
Primary battery-
non rechargeable

Longer shelf-life

Rechargeable


Offer higher
efficiencies
compared to
burning fuels
Images of batteries
Leclanche Alkaline Fuel Cell
Electrolysis
Use Faradays Laws to evaluate the number of moles of
a substance oxidised or reduced by passage of charge
(current over a given period of time = I.t) through an electrode
Faraday: Q (charge) = nF
N=number of moles of electrons
F=constant of 96500 Coulomb/mole
Example (try it): What current is needed to deposit
0.500g of chromium from a solution containing Cr
3+

over a one hour period (MW for Cr=52)?
(Ans=0.77A)
Electrolysis
Use Faradays Laws to evaluate the number of moles of
a substance oxidised or reduced by passage of charge
(current over a given period of time = I.t) through an electrode
Faraday: Q (charge) = nF
n=number of moles of electrons
F=constant of 96500 Coulomb/mole
1 coulomb = 1 C = 1 Ampere. s
How many grams of copper are deposoted on the cathode of an electrolytic
cell if an electric current of 2 A is run through a solution of CuSO
4
for a
period 20 min?
number of coulomb = 2 A x 2 min x 60 s/min = A C
mole e- = A x 1/(9,65 x 10
4
C) = B mol e-
Gram Cu = B x mol Cu/mol e- x 63,5 g Cu/1 mol Cu = C gram Cu
Applications of Electrolytic Cells
Aluminium refining: The major ore of aluminium is bauxite, Al
2
O
3
.
Anhydrous Al
2
O
3
melts at over 2000C. This is too high to permit its use as a molten
medium for electrolytic formation of free aluminium. The electrolytic process
commercially used to produce aluminium is known as the Hall process, named after
its inventor, Charles M. Hall. Al
2
O
3
is dissolved in molten cryolite, Na
3
AlF
6
, which
has a melting point of 1012
o
C and is an effective conductor of electric current.
Graphite rods are employed as anodes and are consumed in the electrolysis process.
The cell electrolytic reaction is:
2Al
2
O
3
+ 3C 4Al(l) + 3CO
2
(g)
Electrolysis of brine
Chlorine and sodium hydroxide are both manufactured by electrolysis of brine
(aqueous sodium chloride) using inert electrodes. Chlorine is evolved at the
anode, Cl
-
1/2Cl
2
+ e
Hydrogen is evolved at the cathode: H
+
+ e 1/2H
2
The removal of chloride ions and hydrogen ions leaves sodium ions and
hydroxide ions in solution.
Chlorine is used to disinfect municipal water supplies and water in swimming pools.
It is used to manufacture household bleaches and disinfectants. It is used to
manufacture plastics (e.g. PVC), pesticides, anaesthetics, CFCs etc.
Sodium hydroxide is used in the manufacture of synthetic fibres, soaps and
detergents.
Electroplating
In all aspects of our lives we are surrounded by products with electroplated surfaces.
Whether we are looking at a silver-plated watch through gold-plated glasses, watching
television, using the washing machine, getting into a car or boarding a plane:
electroplating plays an important part in all of these situations. The objective is to
prevent corrosion and wear,produce hardness and conductivity, and give products an
attractive appearance.

Silver electroplating was
the first large scale use of
electrolysis for coating
base metal objects with a
higher value decorative
finish.
The principle: thin
metallic layers with
specific properties are
deposited on base
materials including steel,
brass, aluminium, plastic
and die-cast parts.