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Elektro Kimia Elektro Kimia

Galvanic Cells
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GalvanicCells
Galvanic cell a spontaneous chemical Galvanic cell a spontaneous chemical
reaction generates an electric current.
Electrolytic cell an electric current drives a Electrolytic cell an electric current drives a
nonspontaneous reaction.
Galvanic Cells
UNIVERSITY INDONESIA OF
GalvanicCells
Redox reaction. edo eact o .
Oxidation a loss of electrons (an increase in oxidation
number).
Reduction a gain of electrons (a decrease in
oxidation number).
Represent oxidation and reduction aspects of the Represent oxidation and reduction aspects of the
reaction with halfreactions.
Oxidizing agent species that causes oxidation to
occur and is itself reduced.
Reducing agent species that causes reduction to
occur and is itself oxidized occur and is itself oxidized.
Galvanic Cells
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GalvanicCells
Redox reaction. Redox reaction.
If a spontaneous reaction is carried out in a
beaker:
oxidizing agent and reducing agent are in direct contact
electrons are directly transferred
th l f ti i l t t th di f enthalpy of reaction is lost to the surroundings for an
exothermic reaction
If spontaneous reaction is carried out in a galvanic p g
cell:
chemical energy released by the reaction is converted
to electrical energy to electrical energy
Galvanic Cells
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GalvanicCells
For the reaction: For the reaction:
Zn (s) + Cu
2+
(aq) Zn
2+
(aq) + Cu (s).
U D i ll ll t f l i ll t Use a Daniell cell, a type of galvanic cell, to carry
out the reaction.
consists of two half cells consists of two halfcells
beaker with a strip of Zn in a solution of ZnSO4
beaker with a strip of Cu in a solution of CuSO4
electrodes strips of zinc and copper
salt bridge a Ushaped tube that contains a gel
permeated with a solution of an inert electrolyte permeated with a solution of an inert electrolyte
Galvanic Cells
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GalvanicCells
Galvanic Cells
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GalvanicCells
The electrons can be transferred only through The electrons can be transferred only through
the wire.
oxidation and reduction half reactions occur at oxidation and reduction halfreactions occur at
separate electrodes
electric current flows through the wire electric current flows through the wire
Galvanic Cells
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GalvanicCells
Anode the electrode at which oxidation takes Anode the electrode at which oxidation takes
place.
the negative ( ) electrode the negative () electrode
produces electrons
C th d th l t d t hi h d ti Cathode the electrode at which reduction
takes place.
h ( ) l d the positive (+) electrode
consumes electrons
Galvanic Cells
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GalvanicCells
Anode and cathode halfreaction must add to ode a d cat ode a eact o ust add to
give the overall cell reaction.
Salt bridge maintains electrical neutrality by a g y y
flow of ions.
anions flow through the salt bridge from the cathode
t th d t t to the anode compartment
cations migrate through the salt bridge from the
anode to the cathode compartment p
Electrons move through the external circuit from
the anode to the cathode.
Galvanic Cells
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GalvanicCells
OxidationreductionreactionspartI
Galvanic Cells
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GalvanicCells
Galvanic Cells
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GalvanicCells
Galvanic Cells
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GalvanicCells
GalvaniccellsI:thecopperzinccell
Galvanic Cells
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GalvanicCells
Galvanic Cells
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GalvanicCells
Galvanic Cells
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GalvanicCells
Galvanic Cells
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GalvanicCells
Galvanic Cells
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GalvanicCells
GalvaniccellsII:thezinchydrogencell
Galvanic Cells
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GalvanicCells
EXAMPLE: EXAMPLE:
Describehowyouwouldconstructagalvanic
cell based on the following reaction: cellbasedonthefollowingreaction:
Pb
2+
(aq) + Zn (s) Pb (s) + Zn
2+
(aq) Pb
2+
(aq)+Zn(s) Pb (s)+Zn
2+
(aq)
Galvanic Cells
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GalvanicCells
Pb
2+
(aq) + 2 e

Pb (s) ( q) ( )
Zn (s) Zn
2+
(aq) + 2 e

Looking at the two halfreactions, we find that the Pb

2+
is being reduced, and the Zn is being oxidized.
Therefore, the anode compartment of our cell would
consist of a strip of zinc metal immersed in a solution consist of a strip of zinc metal immersed in a solution
containing Zn
2+
ions (such as zinc nitrate).
The cathode compartment would consist of a strip of p p
lead immersed in a solution containing Pb
2+
ions (such
as lead (II) nitrate).
Galvanic Cells
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GalvanicCells
Pb
2+
(aq) + 2 e

Pb (s) Pb (aq) + 2 e Pb (s)

Zn (s) Zn
2+
(aq) + 2 e

The two halfcells would be connected to each The two halfcells would be connected to each
other with a salt bridge and an external wire.
Electrons flow through the wire from the zinc Electrons flow through the wire from the zinc
anode to the lead cathode.
Anions move from the cathode compartment Anions move from the cathode compartment
towards the anode while cations migrate from
the anode compartment toward the cathode. the anode compartment toward the cathode.
Galvanic Cells
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GalvanicCells
Redox chemistryofironandcopper
ShorthandNotation
f l i ll
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forGalvanicCells
Single vertical line | represents a phase Single vertical line, |, represents a phase
boundary.
Double vertical line represents a salt bridge Double vertical line, , represents a salt bridge.
ShorthandNotation
f l i ll
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forGalvanicCells
Shorthand for the anode halfcell is always S o t a d o t e a ode a ce s a ays
written on the left of the saltbridge symbol,
followed on the right of the symbol by the
h h d f h h d h lf ll shorthand for the cathode halfcell.
Reactants in each half cell are written first, followed
by products by products.
Electrons move through the external circuit from left
to right.
For Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s):
Zn (s)|Zn2+ (aq) Cu2+ (aq)|Cu (s).
ShorthandNotation
f l i ll
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forGalvanicCells
Cell involving a gas Cell involving a gas.
Additional vertical line due to presence of
additional phase additional phase.
List the gas immediately adjacent to the
appropriate electrode. appropriate electrode.
Detailed notation includes ion concentrations
and gas pressures and gas pressures.
ShorthandNotation
f l i ll
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forGalvanicCells
EXAMPLE: EXAMPLE:
Givetheshorthandnotationforagalvaniccell
that employs the overall reaction thatemploystheoverallreaction
Pb(NO ) (aq) + Ni (s) Pb(s) + Ni(NO ) (aq) Pb(NO
3
)
2
(aq)+Ni(s) Pb(s)+Ni(NO
3
)
2
(aq)
Give a brief description of the cell Giveabriefdescriptionofthecell.
ShorthandNotation
f l i ll
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forGalvanicCells
SOLUTION: The two halfreactions for this SOLUTION:Thetwohalf reactionsforthis
overallreactionare:
Pb
2+
(aq)+2e Pb (s)
Ni(s) Ni
2+
(aq)+2e
Fromthesehalfreactions,weknowthatlead
is being reduced and nickel is being oxidized isbeingreducedandnickelisbeingoxidized.
ShorthandNotation
f l i ll
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forGalvanicCells
Therefore, Ni is the anode and Pb is the Therefore, Ni is the anode and Pb is the
cathode. The cell notation is:
Ni(s)|Ni
2+
(aq)Pb
2+
(aq)|Pb(s) Ni(s)|Ni (aq)Pb (aq)|Pb(s)
This cell would consist of a strip of nickel as
the anode dipping into an aqueous solution of the anode dipping into an aqueous solution of
Ni(NO
3
)
2
and a strip of Pb as the cathode
dipping into an aqueous solution of Pb(NO
3
)
2
.
3 2
The two halfcells would be connected by a
salt bridge and a wire.
CellPotentialsand
FreeEnergy Changes
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Free EnergyChanges
forCellReactions
Electromotive force (emf) the driving force Electromotive force (emf) the driving force
(electrical potential) that pushes the negatively
charged electrons away from the anode and pulls g y p
them toward the cathode.
Also called the cell potential (E) or the cell voltage. p ( ) g
Potential of a galvanic cell is a positive quantity.
Coulomb (C) the amount of charge transferred ( ) g
when a current of 1 ampere (A) flows for 1 s.
1 J = 1 C x 1 V
CellPotentialsand
FreeEnergy Changes
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Free EnergyChanges
forCellReactions
Cell potential measured with a voltmeter Cell potential measured with a voltmeter.
Gives a positive reading when the + and
terminals of the voltmeter are connected to terminals of the voltmeter are connected to
cathode (+) and anode (), respectively.
can use voltmetercell connections to determine which
electrode is the anode and which is the cathode
CellPotentialsand
FreeEnergy Changes
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Free EnergyChanges
forCellReactions
Two driving forces of a chemical reaction: cell Two driving forces of a chemical reaction: cell
potential, E and freeenergy change, AG.
Related by AG = nFE Related by AG = nFE.
n = number of moles of electrons transferred in the
reaction
F (faraday) the electrical charge on 1 mol of electrons
1 F = 96,500 C/mol e
AG and E have opposite signs
spontaneous reaction has a positive cell potential but negative
AG
CellPotentialsand
FreeEnergy Changes
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Free EnergyChanges
forCellReactions
Standard cell potential E
o
the cell potential Standard cell potential, E the cell potential
when both reactants and products are in their
standard states standard states.
Solutes at 1 M concentration.
Gases at a partial pressure of 1 atm Gases at a partial pressure of 1 atm.
Solids and liquids in pure form.
T 25
o
C T = 25
o
C.
AG
o
= nFE
o
.
StandardReduction
i l
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Potentials
E

= E

+ E

Can't measure potential of a single electrode.

Measure a potential difference by placing a

E
cell
= E
anode
+ E
cathode
Measure a potential difference by placing a
voltmeter between two electrodes.
Develop a set of standard halfcell potentials Develop a set of standard halfcell potentials.
choose an arbitrary standard halfcell as a reference
point and assign an arbitrary potential
express the potential of all other halfcells relative to
the reference halfcell
StandardReduction
i l
UNIVERSITY INDONESIA OF
Potentials
Standard hydrogen electrode (S H E ) Standard hydrogen electrode (S.H.E.)
reference halfcell.
Corresponding half reaction assigned an Corresponding halfreaction assigned an
arbitrary potential of exactly 0 V.
2 H
+
(aq, 1 M) + 2 e

H
2
(g, 1 atm) E
o
0 V 2 H (aq, 1 M) 2 e H
2
(g, 1 atm) E 0 V
Shorthand notation for S. H. E.
H
+
(1 M)|H
2
(1 atm)|Pt (s) ( )|
2
( )| ( )
StandardReduction
i l
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Potentials
Determine standard potentials for halfcells by constructing
a galvanic cell in which the halfcell of interest is paired up
with the standard hydrogen electrode.
Standard oxidation potential the corresponding halfcell
t ti l f id ti h lf ti potential for an oxidation halfreaction.
Standard reduction potential the corresponding halfcell
potential for a reduction halfreaction.
Whenever the direction of a half reaction is reversed the sign Whenever the direction of a halfreaction is reversed, the sign
of E
o
must be reversed.
The standard oxidation potential and the standard reduction potential
always have the same magnitude, but they have opposite signs
Construct a table of standard reduction potentials
(Appendix D in text).
StandardReduction
i l
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Potentials
Conventions used in constructing a table of Conventions used in constructing a table of
halfcell potentials:
The half reactions are written as reductions The halfreactions are written as reductions.
oxidizing agents and electrons are on the reactant side
reducing agents are on the product side reducing agents are on the product side
The halfcell potentials are standard reduction
potentials. p
also known as standard electrode potentials
StandardReduction
i l
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Potentials
Conventions used in constructing a table of Conventions used in constructing a table of
halfcell potentials:
The half reactions are listed in order of decreasing The halfreactions are listed in order of decreasing
standard reduction potential.
strongest oxidizing agents are located in the upper left strongest oxidizing agents are located in the upper left
of the table
strongest reducing agents are in the lower right of the
bl table
StandardReduction
i l
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Potentials
Conventions used in constructing a table of Conventions used in constructing a table of
halfcell potentials:
Ordering of half reactions correspond to ordering Ordering of halfreactions correspond to ordering
of the oxidation reactions in the activity series.
the more active metals at the top of the activity series the more active metals at the top of the activity series
have the more positive oxidation potential (more
negative reduction potential)
StandardReduction
i l
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Potentials
StandardReduction
i l
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Potentials
Standardreductionpotentials
UsingStandard
R d i P i l
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ReductionPotentials
Table of standard reduction potentials ab e o sta da d educt o pote t a s
summarizes an enormous amount of chemical
information.
Can arrange any two or more oxidizing or reducing
agents in order of increasing strength.
Predict the spontaneity or nonspontaneity of Predict the spontaneity or nonspontaneity of
thousands of redox reactions.
combine halfreactions of interest and use
may need to multiply halfreactions by some factor to
ensure that electrons cancel
do not multiply values of E
o
for the halfreactions by that factor
UsingStandard
R d i P i l
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ReductionPotentials
E
o
values are independent of the amount of E values are independent of the amount of
reaction.
AG
o
= nFE
o
AG
o
= nFE
o
AG
o
is an extensive property because it depends on the
amount of substance
change the amount of substance that reacts, AG
o
changes by the same amount as does n, the number of
electrons transferred electrons transferred
E
o
= AG
o
/nF remains constant
UsingStandard
R d i P i l
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ReductionPotentials
Can predict the spontaneity of a reaction by Can predict the spontaneity of a reaction by
knowing the location of the oxidizing and
reducing agent in the table reducing agent in the table.
An oxidizing agent can oxidize any reducing agent
that lies below it in the table. that lies below it in the table.
E
o
for overall reaction must be positive
UsingStandard
R d i P i l
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ReductionPotentials
EXAMPLE: EXAMPLE:
Write the balanced net ionic equation, and
calculate E
o
for the following galvanic cell: calculate E
o
for the following galvanic cell:
Al (s)|Al3+ (aq) Cu2+ (aq)|Cu (s) Al (s)|Al3+ (aq) Cu2+ (aq)|Cu (s)
StandardReduction
i l
UNIVERSITY INDONESIA OF
Potentials
UsingStandard
R d i P i l
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ReductionPotentials
Al (s)|Al3+ (aq) Cu2+ (aq)|Cu (s) Al (s)|Al3+ (aq) Cu2+ (aq)|Cu (s)
Al (s) is the anode and therefore undergoes
oxidation while Cu (s) is the cathode and Cu
2+
oxidation while Cu (s) is the cathode and Cu
2+
therefore, undergoes reduction.
Th h lf i d h i ll i l The halfreactions and their cell potentials
are:
Al (s) Al
3+
(aq) + 3 e

E
o
=+1.66V
Cu
2+
(aq) + 2 e

Cu (s) E
o
= +0.34 V ( q) ( )
UsingStandard
R d i P i l
UNIVERSITY INDONESIA OF
ReductionPotentials
Al (s)|Al3+ (aq) Cu2+ (aq)|Cu (s)
Al (s) Al
3+
(aq) + 3 e

E
o
=+1.66V
Cu
2+
(aq) + 2 e

Cu (s) E
o
= +0.34 V
V 00 . 2 V 34 . 0 V 66 . 1
o
Cu Cu Al Al
o
cell
+ 2 + 3
= + + = + =

E E E
o
Notice that although we multiplied the coefficients in both
halfreactions by the factor of 2 and 3 respectively, we did
not multiply the values of E
o
by these factors.
This is because E
o
values are independent of the amount of
reaction.
CellPotentialsand
CompositionoftheReaction
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p
Mixture:TheNernstEquation
Cell potentials depend on temperature and on Cell potentials depend on temperature and on
the composition of the reaction mixture.
AG = AG
o
+ RT ln Q AG = AG
o
+ RT ln Q.
AG = nFE;
AG
o
= nFE
o
AG nFE
nFE = nFE
o
+ RT ln Q.
CellPotentialsand
CompositionoftheReaction
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p
Mixture:TheNernstEquation
Nernst equation: Nernst equation:
(i l 2 C)

E = E

0.0592
n
logQ
(in volts at 25
o
C).
Enables us to calculate cell potentials under
d d d nonstandardstate conditions.
CellPotentialsand
CompositionoftheReaction
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p
Mixture:TheNernstEquation
Calculate Ecell for the following cell reaction: Calculate Ecell for the following cell reaction:
2 Cr(s) + 3Pb
2+
(aq) 2 Cr
3+
(aq) + 3Pb(s)
[ b
2+
] 0 [Pb
2+
] = 0.15 M;
[Cr
3+
] = 0.50 M
StandardReduction
i l
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Potentials
CellPotentialsand
CompositionoftheReaction
UNIVERSITY INDONESIA OF
p
Mixture:TheNernstEquation
2 Cr (s) 2 Cr
3+
+ 6 e

E
o
= +0 74 V 2 Cr (s) 2 Cr + 6 e E = +0.74 V
3Pb
2+
(aq)+6e

3Pb (s) E
o
=0.13V
CellPotentialsand
CompositionoftheReaction
UNIVERSITY INDONESIA OF
p
Mixture:TheNernstEquation
( )
E
cell
V

= + + = + 0 74 013 0 61 . . .
( )
cell
E = E

0.0592
n
logQ

n
E
cell
= E
cell

0.0592
6
log
Cr
3+
| |
2
Pb
2 +
| |
3

6
Pb
2 +
| |
E
cell
= +0.61
0.0592
6
log
0.5 ( )
2
0 15 ( )
3
= 0.59
6
0.15 ( )
Electrochemical
D i i f H
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DeterminationofpH
Important application of Nernst equation Important application of Nernst equation
electrochemical determination of pH using a
pH meter pH meter.
Consider a cell with a hydrogen electrode as
th d d d f l t d the anode and a second reference electrode
as the cathode.
| | Pt (s)|H
2
(1 atm)|H+ (? M)reference cathode.
E
cell
= 0.0592pH+ E
ref
Electrochemical
D i i f H
UNIVERSITY INDONESIA OF
DeterminationofpH
E
cell
= 0.0592pH+ E
ref
pH=
E
cell
E
ref
0 0592
can measure the pH of a solution by
p
0.0592
p y
measuring Ecell
Actual pH measurements use a glass electrode Actual pH measurements use a glass electrode
with a calomel electrode as the reference.
Electrochemical
D i i f H
UNIVERSITY INDONESIA OF
DeterminationofpH
EXAMPLE: EXAMPLE:
The following cell has a potential of 0.49 V.
C l l h H f h l i i h d Calculate the pH of the solution in the anode
compartment.
| | || | | Pt(s) |H
2
(g) (1 atm)|H
+
(pH = ?)||Cl

(aq) (1M)|Hg
2
Cl
2
(s) |Hg (l)
Electrochemical
D i i f H
UNIVERSITY INDONESIA OF
DeterminationofpH
The cell reaction is The cell reaction is
Hg
2
Cl
2
(s) + H
2
(g) 2 Hg (l) + 2 Cl

(aq) + 2 H
+
(aq)

StandardReduction
i l
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Potentials
Electrochemical
D i i f H
UNIVERSITY INDONESIA OF
DeterminationofpH
The cell reaction is The cell reaction is
Hg
2
Cl
2
(s) + H
2
(g) 2 Hg (l) + 2 Cl

(aq) + 2 H
+
(aq)

V 28 . 0 V 28 . 0 V 00 . 0
o
Cl Hg, Cl Hg
o
H H
o
-
2 2
+
2
= + = + =

E E E
pH=
E
cell
E
ref
0.0592
55 . 3
0592 . 0
V 28 . 0 V 49 . 0
pH =

=
StandardCell
Potentials and
UNIVERSITY INDONESIA OF
Potentialsand
EquilibriumConstants
Standard free energy change for a reaction is Standard freeenergy change for a reaction is
related to both the standard cell potential and
the equilibrium constant the equilibrium constant.
AG
o
= nFE
o
.
AG
o
RT l K AG
o
= RT ln K.
StandardCell
Potentials and
UNIVERSITY INDONESIA OF
Potentialsand
EquilibriumConstants
Can combine the two equations Can combine the two equations.
E
o
=
RT
nF
ln K =
2.303RT
nF
logK
nF nF
E

=
0.0592
n
logK
common use calculating equilibrium

n
constants from standard cell potentials.
StandardCell
Potentials and
UNIVERSITY INDONESIA OF
Potentialsand
EquilibriumConstants
Equilibrium constants for redox reactions tend Equilibrium constants for redox reactions tend
to be either very large or very small in
comparison with equilibrium constants for comparison with equilibrium constants for
acidbase reactions.
P iti l f E
o
d t K > 1 Positive value of E
o
corresponds to K > 1.
Negative value of E
o
corresponds to K < 1.
StandardCell
Potentials and
UNIVERSITY INDONESIA OF
Potentialsand
EquilibriumConstants
Three different ways to determine the value of Threedifferentwaystodeterminethevalueof
anequilibriumconstantK:
K =
C
| |
c
D
| |
d
A
| |
a
B
| |
b

ln K =
AG

RT

ln K =
nFE

RT
StandardCell
Potentials and
UNIVERSITY INDONESIA OF
Potentialsand
EquilibriumConstants
EXAMPLE: EXAMPLE:
Calculate the equilibrium constant for the
f ll i i 25
o
C following reaction at 25
o
C.
5 S
2
O
8
2
(aq) + I
2
(s) + 6 H
2
O (l) 10 SO
4
2
(aq) + 2 IO
3
(aq) + 12 H
+
(aq)
StandardReduction
i l
UNIVERSITY INDONESIA OF
Potentials
StandardCell
Potentials and
UNIVERSITY INDONESIA OF
Potentialsand
EquilibriumConstants
S
2
O
8
2
(aq) + 2 e

2 SO
4
2
(aq) E
o
= +2 01 V S
2
O
8
(aq) + 2 e 2 SO
4
(aq) E = +2.01 V
I
2
(s) + 6H
2
O (l) 2IO
3
(aq) + 12 H
+
(aq) +10e

E
o
= 1.20 V
h l f f hi i i 10

E
cell

= 2.01+ 1.20 ( )= +0.81 V

The value of n for this reaction is 10.
log K =
(10)(0.81)
=137 E

=
0.0592
logK log K =
(0.0592)
=137
K=10
137

E =
n
logK
StandardCell
Potentials and
UNIVERSITY INDONESIA OF
Potentialsand
EquilibriumConstants
Batteries
UNIVERSITY INDONESIA OF
Batteries
Most important practical application of Most important practical application of
galvanic cells is their use as batteries.
Features required in a battery depend on the Features required in a battery depend on the
application.
C. General features. C. General features.
Compact and lightweight.
Physically rugged and inexpensive. y y gg p
Provide a stable source of power for relatively
long periods of time.
Batteries
UNIVERSITY INDONESIA OF
Batteries
Lead storage battery. Lead storage battery.
Used as a reliable source of power for starting
automobiles for more than threequarters of a
century.
12 V battery six 2 V cells connected in series.
Anode a series of lead grids packed with spongy
lead.
Cathode a series of grids packed with lead Cathode a series of grids packed with lead
dioxide, dipped into an aqueous solution of H
2
SO
4
(38% w/w).
Batteries
UNIVERSITY INDONESIA OF
Batteries
Lead storage battery. Lead storage battery.
Electrode halfreactions and the overall cell
reaction.
Anode:
Pb (s) + HSO
4

(aq) PbSO
4
(s) + H
+
(aq) + 2 e E
o
= 0.296 V
Cathode: Cathode:
PbO
2
(s) + 3 H
+
(aq) + HSO
4

(aq) + 2 e 2 PbSO
4
(s) + 2 H
2
O (l) E
o
= 1.628 V
Overall:
Pb (s) + PbO (s) + 2 H
+
(aq) + 2 HSO

(aq) 2 PbSO (s) + 2 H O (l) Pb (s) + PbO
2
(s) + 2 H
+
(aq) + 2 HSO
4
(aq) 2 PbSO
4
(s) + 2 H
2
O (l)
E
0
= 1.924 V

Batteries
UNIVERSITY INDONESIA OF
Batteries
PbSO
4
adheres to the surface of the PbSO
4
adheres to the surface of the
electrodes.
recharge by using an external source of direct recharge by using an external source of direct
current to drive the cell reaction in the reverse,
nonspontaneous direction p
Batteries
UNIVERSITY INDONESIA OF
Batteries
DryCell Batteries (Leclanch cell) common Dry Cell Batteries (Leclanch cell) common
household batteries.
Anode Zn metal can Anode Zn metal can.
Cathode inert graphite rod surrounded by a
paste of solid MnO2 and carbon black paste of solid MnO2 and carbon black.
Electrolyte a moist paste of NH
4
Cl and ZnCl
2
in
starch. starch.
surrounds the MnO2 containing paste
acidic causes corrosion of the Zn anode (Zn Zn2+)
Batteries
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Batteries
DryCell Batteries (Leclanch cell) common Dry Cell Batteries (Leclanch cell) common
household batteries.
Alkaline dry cell modified version of Leclanch. Alkaline dry cell modified version of Leclanch.
replace acidic NH
4
Cl (acidic) with NaOH or KOH
electrode reactions oxidation of zinc and reduction of
d d manganese dioxide
produces ZnO due to basic conditions
zinc corrodes more slowly
battery has a longer life
produces higher power and more stable current and voltage
more efficient ion transport in the alkaline electrolyte more efficient ion transport in the alkaline electrolyte
Batteries
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Batteries
Mercury battery used in watches heart Mercury battery used in watches, heart
pacemakers, and other devices.
small size small size
anode Zn (same as dry cell)
cathode steel in contact with HgO in an alkaline cathode steel in contact with HgO in an alkaline
medium of KOH and Zn(OH)
2
Batteries
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Batteries
Lithium batteries light weight high voltage Lithium batteries light weight, high voltage,
rechargeable battery
Anode lithium metal Anode lithium metal.
highest standard oxidizing potential
Cathode metal oxide or sulfide that can Cathode metal oxide or sulfide that can
incorporate Li
+
.
Electrolyte lithium salt in an organic solvent. Electrolyte lithium salt in an organic solvent.
Used in cell phones, laptop computers and
cameras.
Batteries
UNIVERSITY INDONESIA OF
Batteries
Fuel cells a galvanic cell in which one of the Fuel cells a galvanic cell in which one of the
reactants is a traditional fuel.
Reactants are not self contained within the cell Reactants are not selfcontained within the cell.
supplied from an external reservoir
Bestknown hydrogenoxygen fuel cell Best known hydrogen oxygen fuel cell.
used in space vehicles as a source of electric power
Batteries
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Batteries
Batteries
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Batteries
Batteries
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Batteries
Batteries
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Batteries
Corrosion
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Corrosion
Corrosion the oxidative deterioration of a Corrosion the oxidative deterioration of a
metal.
Well known example of corrosion conversion Wellknown example of corrosion conversion
of iron to rust.
R i b th d t Requires both oxygen and water.
Involves pitting of the metal surface.
i d i d l i h i ll d f rust is deposited at a location physically separated from
the pits
Corrosion
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Corrosion
Proposed mechanism for formation of rust an oposed ec a s o o at o o ust a
electrochemical process in which iron is oxidized
in one region of the surface and oxygen is
d d h reduced in another region.
Anode region:
Fe (s) Fe
2+
(aq) +2 e E
o
= 0 45 V Fe (s) Fe
2+
(aq) +2 e E
o
= 0.45 V
Cathode region:
O
2
(g) + 4 H
+
(aq) + 4 e 2 H
2
O (l) E
o
= 1.23 V
2 2 o
Electrons flow from the anode to the cathode through
the metal.
Corrosion
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Corrosion
Proposed mechanism for formation of rust Proposed mechanism for formation of rust
an electrochemical process in which iron is
oxidized in one region of the surface and oxidized in one region of the surface and
oxygen is reduced in another region.
Ions migrate through the water droplets Ions migrate through the water droplets.
Fe
2+
reacts with O
2
and is oxidized to Fe
3+
Fe
3+
reacts with H
2
O to form Fe
2
O
3
.xH
2
O (s) (rust) Fe reacts with H
2
O to form Fe
2
O
3
.xH
2
O (s) (rust)
Corrosion
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Corrosion
Proposed mechanism for formation of rust an Proposed mechanism for formation of rust an
electrochemical process in which iron is oxidized
in one region of the surface and oxygen is g yg
reduced in another region.
Explains why cars rust more rapidly when road salt is p y p y
used to melt snow and ice.
dissolved salt in water greatly increases the conductivity of
the electrolyte the electrolyte
O
2
able to oxidize all metals except a few.
O
2
/H
2
O halfreaction lies above the M
n+
/M halfreaction O
2
/H
2
O half reaction lies above the M /M half reaction
Corrosion
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Corrosion
Prevention of corrosion shield the metal Prevention of corrosion shield the metal
surface from oxygen and moisture.
Durable surface coating metals such as Durable surface coating metals such as
chromium, tin, or zinc.
Galvanizing coating by dipping into a bath of Galvanizing coating by dipping into a bath of
molten zinc.
Cathodic protection protecting a metal from Cathodic protection protecting a metal from
corrosion by connecting it to a second metal that
is more easily oxidized.
Corrosion
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Corrosion
Corrosion
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Corrosion
Electrolysisand
l l ll
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ElectrolyticCells
Electrolytic cell an electric current is used to Electrolytic cell an electric current is used to
drive a nonspontaneous reaction.
Processes occurring in galvanic and electrolytic Processes occurring in galvanic and electrolytic
cells are the reverse of each other.
Electrolysis the process of using an electric Electrolysis the process of using an electric
current to bring about chemical change.
Electrolysisand
l l ll
UNIVERSITY INDONESIA OF
ElectrolyticCells
Electrolytic cell. y
Two electrodes that dip into an electrolyte and are
connected to a battery or some other source of direct
electric current. electric current.
battery an electron pump, pushing electrons into one
electrode and pulling them out of the other electrode
Anode electrode where oxidation takes place Anode electrode where oxidation takes place.
positive sign
the battery pulls electrons out of it
3 Cathode electrode where reduction takes place 3. Cathode electrode where reduction takes place.
negative sign
the battery pushes electrons into it
Electrolysisand
l l ll
UNIVERSITY INDONESIA OF
ElectrolyticCells
Electrolysis of molten NaCl Electrolysis of molten NaCl.
Cathode attracts Na
+
.
Na
+
+ e

Na (l) Na + e Na (l)
Anode attracts Cl

.
2 Cl

Cl
2
(g) + e

2 Cl Cl
2
(g) + e
Electrolysisand
l l ll
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ElectrolyticCells
Electrolysis of aqueous NaCl. y q
Electrode reactions in an aqueous solution can differ
from those for a molten salt.
Cathode reaction can involve the reduction of Na
+
or Cathode reaction can involve the reduction of Na or
the reduction of water.
reduction of water preferred.
E8
o
less negative for H O than E
o
E8
o
less negative for H
2
O than E
o
.
2 H
2
O (l) + 2 e

H
2
(g) + 2 OH

(aq)
Anode reaction can involve the oxidation of Cl

or the
oxidation of water oxidation of water.
actual reaction the oxidation of Cl

due to overvoltage
2 Cl

(aq) Cl
2
(g) + 2 e

Electrolysisand
l l ll
UNIVERSITY INDONESIA OF
ElectrolyticCells
Electrolysis of aqueous NaCl. y q
Overvoltage amount of voltage needed above the
calculated standard reduction (or oxidation) potential
for electrolysis to occur. for electrolysis to occur.
needed when the halfreaction has a substantial barrier for
electron transfer (slow rate).
surmounts barrier
reaction proceeds at satisfactory rate
small overvoltage needed for solution or deposition of
metals
large overvoltage needed for formation of O
2
or H
2
cant predict; need experimental evidence if cell potentials
are similar
Electrolysisand
l l ll
UNIVERSITY INDONESIA OF
ElectrolyticCells
Electrolysis of aqueous NaCl Electrolysis of aqueous NaCl.
Overall cell reaction:
2 Cl

(aq) + 2 H O (l) Cl (g) + 2 H (g) + 2 OH

(aq) 2 Cl (aq) + 2 H
2
O (l) Cl
2
(g) + 2 H
2
(g) + 2 OH (aq)
Na
+
is a spectator ion and reacts with the OH

to form
NaOH
Electrolysisand
l l ll
UNIVERSITY INDONESIA OF
ElectrolyticCells
F. Electrolysis of water. . ect o ys s o ate .
Electrolysis of any aqueous solution requires the
presence of an electrolyte to carry the current in
l ti solution.
If the ions of the electrolyte are less easily oxidized
and reduced than water is, then water will react at ,
both electrodes.
Anode: 2 H
2
O (l) O
2
(g) + 4 H
+
(aq) + 4 e

.
Cathode 4 H O (l) + 4 e

2 H (g) + 4 OH

(aq) Cathode: 4 H
2
O (l) + 4 e

2 H
2
(g) + 4 OH

(aq).
Overall cell reaction:
2 H
2
O (l) O
2
(g) + 2 H
2
(g)
2 2
g
2
g
Electrolysisand
l l ll
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ElectrolyticCells
Electrolysisand
l l ll
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ElectrolyticCells
Electrolysisand
l l ll
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ElectrolyticCells
Electrolysisofwater
Electrolysisand
l l ll
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ElectrolyticCells
Electrolysisand
l l ll
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ElectrolyticCells
Electrolysisand
l l ll
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ElectrolyticCells
Electrolysisand
l l ll
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ElectrolyticCells
Electroplating
Electrolysisand
l l ll
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ElectrolyticCells
Commercial
Applications of
UNIVERSITY INDONESIA OF
Applicationsof
Electrolysis
Manufacture of sodium produced commercially in a
Downs cell by electrolysis of a molten mixture of NaCl
and CaCl
2
.
Liquid Na produced at the cylindrical steel cathode is less q p y
dense than the molten salt and thus floats to the top part
of the cell, where it is drawn off into a suitable container.
Manufacture of chlorine and sodium hydroxide a u ac u e o c o e a d sod u yd o de
electrolysis of aqueous NaCl.
Basis of chloralkali industry.
Anode and cathode reactions for electrolysis of aqueous Anode and cathode reactions for electrolysis of aqueous
NaCl carried out in membrane cell.
membrane keeps Cl
2
and OH

apart but allows a current of Na to

flow
Commercial
Applications of
UNIVERSITY INDONESIA OF
Applicationsof
Electrolysis
Manufacture of aluminum HallHeroult process. p
Electrolysis of a molten mixture of Al
2
O
3
and cryolite
(Na
3
AlF
6
) at 1000
o
C in a cell with graphite electrodes.
success of process the use of cryolite as a solvent success of process the use of cryolite as a solvent
Electrode reactions involve the formation of complex
ions.
ions are reduced at the cathode to produce Al (l) ions are reduced at the cathode to produce Al (l)
ions are oxidized at the anode to produce O
2
(g)
O
2
(g) reacts with the graphite electrode to produce CO
2
(g)
Requires frequent replacement of the anodes Requires frequent replacement of the anodes
Largest single consumer of electricity in the U.S.
1 mol of electrons produces only 9 g of Al
Commercial
Applications of
UNIVERSITY INDONESIA OF
Applicationsof
Electrolysis
Electrorefining the purification of a metal by Electrorefining the purification of a metal by
means of electrolysis.
Electroplating the coating of one metal on Electroplating the coating of one metal on
the surface of another using electrolysis.
C th d bj t t b l t d ( f ll l d) Cathode object to be plated (carefully cleaned).
Electrolytic cell contains a solution of ions of the
metal to be deposited metal to be deposited.
Quantitative
Aspects of
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Aspectsof
Electrolysis
The amount of substance produced at an The amount of substance produced at an
electrode by electrolysis depends on the
quantity of charge passed through the cell.
Follows directly from the stoichiometry of the
reaction and the atomic mass of the product.
Moles of electrons passed through a cell are
determined from the electric current and the
ti th t th t fl time that the current flows.
M l f
-
h (C)
1 mol e
-
Moles of e = charge(C)
96,500 C
Quantitative
Aspects of
UNIVERSITY INDONESIA OF
Aspectsof
Electrolysis
Sequence of conversion used to calculate the mass or
volume of product produced by passing a known
current for a fixed period of time.
current moles grams or
and charge moles of e of liters of
time product product
Think of electrons as reactants in a balanced equation
and proceed as with any other stoichiometry problem. p y y p
Quantitative
Aspects of
UNIVERSITY INDONESIA OF
Aspectsof
Electrolysis
Quantitative
Aspects of
UNIVERSITY INDONESIA OF
Aspectsof
Electrolysis
EXAMPLE: EXAMPLE:
How many grams of Cl
2
would be produced in
the electrolysis of molten NaCl by a current of the electrolysis of molten NaCl by a current of
4.25 A for 35.0 min?
Quantitative
Aspects of
UNIVERSITY INDONESIA OF
Aspectsof
Electrolysis
Remember that a coulomb is an A.s or that an
ampere is C/s.
2 Cl

Cl
2
+ 2 e

moles of electrons = 2
4.25
C
s
35.0 min
60 s
1 min

1 mol e
-
96,500 C

1 mol Cl
2
2 mol e
-

70.9 g Cl
2
1 mol Cl
-
= 3.28 g Cl
2