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CHAPTER 4
Electrochemistry
2
SCOPE

Oxidation and reduction

Balancing net ionic equations for


redox reaction in acidic solution

Electrochemical cells

Galvanic cells

Shorthand notation
3
SCOPE

Cell EMF

Standard eduction !otential

S"ontaneit# of edox eactions

EMF and Free Energ# Change

Electrochemical $ecom"osition
%
LESSON OUTCOMES
&t the end of this lecture' students should
(e a(le to)
*
Identify the oxidizing and reducing agents
in a redox reaction
*
Write equations for oxidation and reduction
half-reaction and use them to balance the
net equation.
*
Describe galvanic cells
+
LESSON OUTCOMES
&t the end of this lecture' students should
(e a(le to)
*
Draw cell diagram
*
Write shorthand notation
*
Calculate cell potential
*
Calculate ,G from cell potential

LEO - Loss Electron Oxidation

GER - Gain Electron Reduction


Zn(s) + 2H
+(aq) Zn2+(aq) + H
2(g)

This reaction: Zinc increases from 0 in Zn(s) to +2 in Zn


2+(aq).
Hdro!en reduces from +" to 0.

This reaction is called oxidation-reduction reactions or redox reactions.

The transfer of electron durin! redox reactions can #roduce ener! in the form of
electricit.

Electrochemistr : Relationshi# $et%een electricit and chemical reactions.


4.1 Oxidation and reduction

To determine a !i&en chemical reaction is


an oxidation-reduction reaction.

'ee# trac( of the oxidation num$ers.


Zn(s) + 2H
+(aq) Zn2+(aq) + H
2(g)
0 +" +2 0

)n redox reaction: one su$stance is oxidi*ed and another must $e


reduced.
4.1 Oxidation and reduction

Oxidation num$ers
+lso called oxidation state

)s the char!e that an atom in a molecule


%ould #ossess if the shared electron
#airs in each co&alent $ond %ere
assi!ned to the more electrone!ati&e
element in the $ond

The oxidation num$er is assi!ned


accordin! to a set of rules
-
4.1 Oxidation and reduction

Rules:

The oxidation num$er of an free element is


0

The oxidation num$er for an sim#le,


monoatomic ion is e-ual to the char!e

The sum of all oxidation num$ers of the


atoms in a neutral molecule must e-ual
*ero. The sum of all the oxidation num$ers in
a #olatomic ion must e-ual the char!e on
the ion

)n its com#ounds, .uorine is /"

)n most of its com#ounds, hdro!en is +"

)n most of its com#ounds, ox!en is /2


.
4.1 Oxidation and reduction

0ote that the oxidation num$er does


not actuall e-ual a char!e on an
atom

1ractional &alues of oxidation


num$ers are allo%ed

Oxidation is an increase in oxidation


num$er

Reduction is a decrease in oxidation


num$er
1/
4.1 Oxidation and reduction

The su$stance ma(es another


su$stance to $e oxidi*ed is called the
oxidi*in! a!ent or oxidant.

The su$stance causin! another


su$stance to $e reduced is called a
reducin! a!ent or reductant.
4.1 Oxidation and reduction
Zn(s) + 2H
+(aq) Zn2+(aq) + H
2()
0 +" +2 0

Zn2s3 are oxidised 2LEO3 4 cause another su$stance to $e reduced: H


+ is
reduced 2GER3.

Therefore, Zn2s3 is a reducin! a!ent and H+2a-3 is an oxidi*in! a!ent.


[Oxidising agent is itself reduced]
[Reducing agent is itself oxidized]
4.1 Oxidation and reduction
Example
The nic(el-cadmium $atter- the redox
reaction is as follo%s:
C!(s) + NiO
2(s) + 2H2O(l) C!(OH)2(s) + Ni(OH)2(s)
)dentif: 5u$stances that are oxidi*ed and reduced.
6hich are oxidi*in! and reducin! a!ents7
olution
". +ssi!n oxidation num$ers.
C!(s) + NiO
2(s) + 2H2O(l) C!(OH)2(s) + Ni(OH)2(s)
2. Elements that are chan!in! oxidi*in! num$er.
8d: from 0 +2 2LEO3
0i: from +9 +2 2GER3
:. 8d is oxidi*ed - a reducin! a!ent.
0i is reduced - an oxidi*in! a!ent.
0 +9 -2 +" -2 +2 -2 +" +2 -2 +"
4.! "alancing net ionic e#uations
for redox reactions in acidic solution

;an redox reactions ta(e #lace in a-ueous


solution

The oxidation and reduction #rocesses are


di&ided into e-uations called half-reactions

<oth the char!e and the num$er of each


t#e of atom must $e $alanced

8har!e is $alanced $ addin! electrons to


the side of the e-uation that is more #ositi&e
or less ne!ati&e

The half-reactions are $alanced se#aratel,


then com$ined into the full $alanced net
ionic e-uation
1+
$onsider:
Reaction $et%een #erman!anate ion, ;nO
9
- and
oxalate ion 8
2O9
2-.
MnO
"
#(aq) + C
2O"
2#(aq) Mn2+(aq) + CO
2(g)
1. ! %alf e#&reactions: one %alf e# to represent oxidation' one %alf
e# to represent reduction
MnO"
#(aq) Mn2+(aq) E#. 1
C
2O"
2#(aq) CO
2(g) E#. !
4.! "alancing net ionic e#uations
for redox reactions in acidic solution
!. "alance eac% %alf-reaction:
a3 $alance the elements other than H and
O
$3 $alance the O atoms $ addin! H
2O
c3 $alance the H atoms $ addin! the H
+
d3 $alance the char!e $ addin! e-
4.! "alancing net ionic e#uations
for redox reactions in acidic solution
E#. 1: Reduction' MnO
%
0(aq) Mn21(aq)
Ox!en: MnO
%
0(aq) Mn21(aq) 1 %2
2O(l)
Hdro!en: -2
1(aq) 1 MnO
%
0(aq) Mn21(aq) 1 %2
2O(l)
8har!e: Total char!e of reactants:
-3114 1 3014 5 16
Total char!e of #roducts:
3214 1 %3/4 5 12
Therefore=
$e
# + %H+(aq) + MnO
"
# (aq) Mn2+ (aq) + "H
2O(l)
4.! "alancing net ionic e#uations
for redox reactions in acidic solution
E#. !: Oxidation
C
2O%
20(aq) 2CO
2(g)
8har!e: Total char!e of reactants 4 -2
Total char!e of #roducts 4 0
Therefore=
C2O%
20 (aq) 2CO
2 (g) 1 2e
0

O (alance
4.! "alancing net ionic e#uations
for redox reactions in acidic solution
). O*erall Rxn: +ultipl, eac% %alf-reaction
and add.

0o. of e
- lost 4 0o. of e- !ained
1/e0 1 1721(aq) + 2MnO
%
0 2Mn21(aq) 1 -2
2O(l)
+C2O%
20(aq) 1/CO
2(g) 1 1/e
0

-%us' (alance net ionic&redox e#uation:
&'H+(aq) + 2MnO
"
#(aq) + $C
2O"
2#(aq) 2Mn2+(aq) + %H
2O(l) + &(CO2(g)
4.! "alancing net ionic e#uations
for redox reactions in acidic solution
Example
8om#lete and $alance:
Cr
2O6
20(aq) 1 Cl0(aq) Cr31(aq) 1 Cl
2(g)
Sol)tion
1st: 2 half eq/reactions
Cr2O6
20(aq) Cr31(aq)
Cl0(aq) Cl
2(g)
4.! "alancing net ionic e#uations for
redox reactions in acidic solution
!nd: balance each half reaction
Cr
2O6
20(aq) 2Cr31(aq)
Ox!en: Cr
2O6
20(aq) 2Cr31(aq) 1 62
2O(l)
Hdro!en: 1%2
1(aq) 1 Cr
2O6
20(aq) 2Cr 31 1 2
2O(l)
8har!e: 311%4 1 3024 5 112 2reactant3
3174 1 3/4 5 17 2#roduct3
7e
0 1 1%21(aq) 1 Cr
2O6
20(aq) 2Cr 31(aq) 1 62
2O(l)
Sol)tion (cont*)
4.! "alancing net ionic e#uations for
redox reactions in acidic solution
!nd: balance each half reaction
Cl
0(aq) Cl
2(g)
2Cl
0 aq) Cl
2 (g)
8har!e: 2 2reactant3
/ 2#roduct3
2Cl
0 (aq) Cl
2 (g) 1 2e
0
multi#l : 7Cl0(aq) 3Cl
2 (g) 1 7e
0
Sol)tion (cont*)
4.! "alancing net ionic e#uations for
redox reactions in acidic solution

)rd: Add two half eq/reactions
&"H
+(aq) + Cr
2O+
2#(aq) + 'Cl#(aq) 2Cr ,+(aq) + +H
2O(l) + ,Cl2 (g)
4.! "alancing net ionic e#uations for
redox reactions in acidic solution
Sol)tion (cont*)
4.) Electroc%emical $ell

8onsists of t%o electrodes, in contact %ith an


electrolte

T%o t#es:
>oltaic cell 2Gal&anic cell3.
Electroltic cell.

+ &oltaic2!al&anic cell3 - an electrochemical cell


that #roduces electricit as a result of the
s#ontaneous reaction occurrin! inside it.
e.!. $atter sstem

+n electroltic cell - an electrochemical cell in


%hich a non-s#ontaneous reaction is dri&en $
an external source of current.
e.!. 8hloro - al(ali #rocess
4.4 .oltaic $ell&Gal*anic
$ell

The ener! released in a s#ontaneous redox.


electrical %or(.
throu!h a &oltaic 2or !al&anic3 cell.

+ stri# of *inc is #laced in a solution of co##er 2))3


sulfate.
Electrons are transferred form Zn to the 8u
2+
ion.
/n(s) 0 $u!0(aq) /n!0(aq) 0 $u(s)
The *inc metal and 8u
2+
(aq)
not in direct contact.
The t%o solid metals -
connected $ the
external circuit ie.
electrode.
Electrode at 8hich
oxidation occurs
anode9
Electrode at 8hich
reduction occurs
cathode9

+s the &oltaic cell o#erates:


Oxidation of Zn: :n(s) :n
21(aq) 1 2e0
8oncentration of :n21 increases, increase in +&e char!e.
Zinc metal is oxidi*ed at the anode - e-s .o% throu!h the external circuit to the cathode.
Reduction of 8u2+: Cu21(aq) 1 2e0 Cu(s)
?ecrease in 8u2+ as it is reduced to 8u, 8u electrode !ain mass, increase in -&e char!e
2more SO
%
203

5alt $rid!e is re-uired to neutrali*e this.

)f not, no further redox can ta(e #lace


.
4.4 .oltaic $ell&Gal*anic
$ell

8an use #orous $arrier instead of salt $rid!e

Oxidation and reduction #roceed:


- ions from the salt $rid!e mi!rate to neutrali*e
char!e.

+nions mi!rate to%ard the anode.

8ations mi!rate to%ard the cathode.


4.4 .oltaic $ell&Gal*anic
$ell
+s the &oltaic cell o#erates:
1 summar, of *oltaic
cell

Electrons .o% s#ontaneousl from anode to


cathode.

+nions mo&e to%ard the anode and cations


to%ard the cathode
-
+
+nions
8ations
@orous $arrier
or salt $rid!e
Electron .o%
+node 8athode
Example
The follo%in! oxidation-reduction is s#ontaneous:
Cr
2O+
2#(aq) + &"H+(aq) + '-#(aq) 2Cr,+(aq) + ,-
2 + +H2O(l)
+ solution containin! '28r2OA and H25O9 is #oured into one $ea(er and a solution of ') is
#oured into another. + salt $rid!e is used to Boin the $ea(ers. + metallic conductor that %ill
not react %ith either solution is sus#ended in each solution, and the t%o conductors are
connected %ith %ire throu!h a &oltmeter. )ndicate the reaction occurrin! at the anode, the
reaction at the cathode, the direction of electron mi!ration, the direction ion mi!rations, and
the si!ns of the electrodes.
olution
?i&ide into half-reactions:
8athode, Reduction: Cr
2O+
2# (aq) 2Cr,+
<alance - half-reaction method.
Cr
2O+
2#(aq) + &"H+(aq) + 'e# 2Cr,+(aq) + +H
2O(l)

+node, Oxidation) -
#(aq) -
2
<alance - half-reaction method.
'-
#(aq) ,-
2(s) + 'e
#

+nion to%ard anode

8ation to%ard cathode


-
0
alt (ridge
cat%od
e
e-
olution 2cont.3
anion cation

anode
'-
# (aq) ,-
2 (s) + 'e
#
Cr
2O+
2#(aq) + &"H+(aq) + 'e# 2Cr ,+(aq) + +H
2O

4.4 %ort%and
5otation

5horthand notation for descri$in! the


com#onents of an electrochemical cell
/n2s3 6 /n
!02a#3 66 $u!02a#3 6 $u2s3
oxidation reduction
5alt $rid!e
e
-
Zn
anode
8u
cathod
e
Zn5O
92a-3
8u5O
92a-3

Other exam#le of a shorthand notationCcell


dia!ram:
8r2s3 D 8r
:+2a-3 DD +!+2a-3 D +!2s3

To deduce cell reaction from a !i&en shorthand notationCcell dia!ram:


Left hand side 2LH53 - oxidation 2anode3
Ri!ht hand side 2RH53 - reduction 2cathode3
e.!. LH5 Zn2s3 D Zn2+2a-3 DD 8u2+2a-3 D 8u2s3 RH5
oxidation reduction
Zn Zn2+ + 2e- 8u2+ + 2e- 8u
e.!. @t2s3 D H
22!3 D H
+2a-3 DD 8u2+2a-3 D 8u2s3
2inert or inacti&e electrode, e.! car$on !ra#hite3
4.4 %ort%and
5otation
4.7 $ell E+8
6h e- .o% s#ontaneousl throu!h the
external circuit7

?ue to a diEerence in #otential ener!.

The #otential ener! of e


- is hi!her in the anode.

@otential ener! at anode than cathode.

e- .o% s#ontaneousl from anode to cathode.

The #otential diEerence $et%een t%o


electrodes is measured in units of volt.

1 volt: the #otential diEerence re-uired to


im#art 1; of ener! to a char!e of 1 Coulom(
3C49

The #otential diEerence is called


electromoti&e 2causin! e- motion3 force or
emf.
The emf of a cell , E
cell : cell #otential.

Ecell is measured in &olts - refer as the cell &olta!e.


8
F
" > " =
4.7 $ell
E+8
+n cell reaction, #roceed s#ontaneousl: the E
cell
%ill $e #ositi&e.

The emf 2Ecell3 de#ends on:

s#eciGc reactions occur at cathode-anode.

the concentrations of reactants and #roducts.

Tem#erature.

Hnder standard conditon: " ; concentration for reactants and #roducts I 2+<C9

The emf is called the standard emf or the standard cell #otential.

?enoted as EJcell.
4.7 $ell
E+8
4.9 tandard Reduction
:otential

?etermine EJ
cell


The cell #otential

E;cell < E;red 2cat%ode3 - E;red 2anode3

EJred : standard reduction #otentials.

E&er &oltaic cell in&ol&es t%o half-cells.

not #ossi$le to directl measure the EJred of a half-reaction.


Reduction at cathode
Reduction at anode
4.9 tandard Reduction
:otential

The reference half-reaction is the


reduction of 2
1 (aq) to 2
2(g) under standard conditions.

EJred 4 / =

This is called a standard hdro!en electrode 25HE3.



Hydrogen electrode (gas electrode)

H
+(aq)
H
2(g)
Pt wire
Pt gauze coated
with Pt black
(To catalyse the reaction)
!t2
23g42
13aq4
Oxidation of Zn and reduction of
H
+
Zn (s) + 2H+ (aq) Zn2+ (aq) + H
2 (g)

The :n
21>:n electrode is the anode and 5HE is the cathode.

The cell &olta!e is /967 =9


- usin! the EJ
red of 2
1 5 /, the standard reduction #otential EJ
red for
Zn
2+CZn half-reaction.
E<
cell 5 E<red 3cathode4 0 E<red 3anode4
/967 = 5 / = 0 E<red 3anode4
E<red 3anode4 5 0/967 =
4.9 tandard Reduction
:otential

+ standard reduction #otential of 0/967 =


can $e assi!ned:
Zn
2+(aq, 1 M) + 2e# Zn(s) . #(*+' /
0ote:
8han!in! the stoichiometric coeKcient in a half-reaction does not eEect the
&alue of the standard reduction #otential.
e.!: 2Zn 2+ (aq, 1 M) + "e# 2Zn (s)
E<
red 5 0/967 =
4.9 tandard Reduction
:otential
$ell :otentials
0or a s1ontaneo)s 1rocess2
E
o
cell . E
o
catho!e 3 E
o
ano!e 4 (
Example
For the :n0Cu
21 voltaic cell' E<
cell 5 191/ = and the :n electrode is the
anode9
E<red of :n
21 5 0/967 =
Calculate the E<
red for the reduction of Cu
21 to Cu9
olution
E<
cell 5 E<red 3cathode4 0 E<red 3anode4
191/ = 5 E<red 3cathode4 0 30/967 =4
E<red 3cathode4 5 191/ = 0 /967 = 5 /93% =
Example
8alculate the EJ
cell for this reaction.
Cr2O+
2#(aq) + &"H+(aq) + '-#(aq) 2Cr,+ + ,-
2 + +H2O
olution
half-reaction:
8athode:
Cr2O+
2#(aq) + &"H+(aq) + 'e# 2Cr,+ + +H
2O
+node:
'-
#(aq) ,-
2(s) + 'e
#
olution
E<
red 5 Cr2O6
20 Cr31 5 1933 =
E<
red 5 ?2 ?
0 5 /9+% =
E<
cell 5 E<red 3cathode4 0 E<red 3anode4
5 1933 = 0 /9+% =
5 /96. =
@ote)
Ahe value of ?2 ?
0 is not multi"lied (# 39
?ntensive "ro"ert#) does not de"end on the s"ecific stoichiometric coefficients9
4.9 tandard Reduction
:otential 2E;
red3
E;
cell < E;red2cat%ode3 - E;red2anode3

The standard reduction #otentials 2EJred3 #ro&ide a measure of the dri&in!


force for a reduction to occur.

;ore +&e of EJred - the !reater the dri&in! force for reduction.

5#ontaneous o#eration - cathode must ha&e more +&e EJred than at the
anode
4.9 tandard Reduction
:otential 2E;
red3
The cell #otential, EJ
cell is the diEerence $et%een the
standard reduction #otential of the cathode reaction, EJred 2cathode3 and
anode reaction, EJred 2anode3.

>oltaic cell - the cathode reaction %ill $e the hi!her on the scale.
Cathode (reduction)
Anode (oxidation)
EJ
cell
EJ
red
EJ
red
E
J
r
e
d

2
>
3
More positive
More negative
-%e di=erence
(et>een
t%e standard
reduction
potentials pus%
e-
t%roug% an
external
circuit.
4.9 tandard Reduction
:otential 2E;
red3

The more #ositi&e the E &alue for a half


reaction, the !reater the tendenc for the
reactant of the half-reaction to $e reduced
and therefore to oxidi*e another s#ecies.
F
23g4 1 2e
0 2F03aq4 E<
red 5 29-6 =
12 is more easil reduced s#ecies and is the stron!est oxidi*in! a!ent.
Leasil reduced stron!est oxidi*in! a!entM
4.9 tandard Reduction
:otential 2E;
red3

Lithium ion, Li+ is the most diKcult s#ecies to


reduce: the #oorest oxidi*in! a!ent.
Bi
1(aq) 1 e0 Bi(s) E<
red 5 039/+ =

Oxidation: Li(s)
Li+(aq) is easil oxidi*ed, !reat tendenc to transfer e- the
stron!est reducin! a!ent.
EJ
red 4 +&e 5tron!est oxidi*in! a!ent
EJred 4 -&e 5tron!est reducin! a!ent

The list of EJred &alues #ro&ides an orderin! of the a$ilit of su$stances to act as
oxidi*in! or reducin! a!ent.
4.9 tandard Reduction
:otential 2E;
red3
-%e standard reduction potentials
E;
red is related to oxidizing or reducing agent
F
2(g) 1 2e
0 2F0(aq)
221(aq) 1 2e0 2
2(g)
Bi
1(aq) 1 e0 Bi(s)
?
n
c
r
e
a
s
i
n
g

s
t
r
e
n
g
t
%

o
f

o
x
i
d
i
z
i
n
g

a
g
e
n
t
?
n
c
r
e
a
s
i
n
g

s
t
r
e
n
g
t
%

o
f

r
e
d
u
c
i
n
g

a
g
e
n
t
+ost 0*e
+ost -*e
trongest oxidizing
agent
trongest reducing
agent
Example
$etermine 8hich one of the three metals :n' Fe' and @a
is the most active metal' given the follo8ing data)
@a
1(aq) 1 e0 @a(s) E
red 5 02961 =
:n
21(aq) 1 2e0 :n(s) E
red 5 0/967 =
Fe
21(aq) 1 2e0 Fe(s) E
red 5 0/9%% =
+n acti&e metal is one that is easil oxidi*ed
2that is, a !ood reducin! a!ent3. ;etals %ith
lar!e ne!ati&e standard reduction electrode
#otentials 2lar!e #ositi&e standard oxidation
#otentials3 are !ood reducin! a!ents. 5odium
metal is the most acti&e metal $ecause its
reduction reaction has the lar!est ne!ati&e
standard reduction #otential 2lar!est #ositi&e
oxidation #otential3. 0a(s) is, therefore, the
most acti&e metal 2$est reducin! a!ent3 of
those listed.
olution

>oltaic cell - reaction occurs and #roduces a


#ositi&e emf must $e s#ontaneous.
EJ
cell 4 EJred 2cathode3 - EJred 2anode3
if %e ma(e a !eneral e-uation:
*
General statement a$out the s#ontaneit of a reaction and its associated emf:

+ #ositi&e &alue of E indicates a s#ontaneous #rocess, and

+ ne!ati&e &alue of E indicates a non s#ontaneous #rocess.


4.@ pontaneit, of Redox
Reactions
EJ 4 EJ
red 2red. #rocess3 - EJred 2ox. #rocess3
EJ 4 EJ
red 2red. #rocess3 - EJred 2ox. #rocess3
Example
Hsin! the standard reduction #otential,
determine %hether the reactions are
s#ontaneous under standard conditions:
Cl
2(g) 1 2?
0(aq) 2Cl0(aq) 1 ?
2(s)
Reduction: Cl2(g) 1 2e
0 2Cl03aq4 E<
red 5 1937 =
Oxidation: 2?0(aq) ?2 (s) 1 2e
0 E<
red 5 /9+% =
olution
E< 5 31937 =4 0 3/9+% =4 5 /9-2 =
EJ is #ositi&e - this reaction is s#ontaneous and could $e used to $uild a &oltaic cell.
4.A E+8 and 8ree-Energ,
$%ange

Gi$$s free ener! G is a measure of the


s#ontaneit of a #rocess that occurs at constant
tem#erature and #ressure.

E;1 of a redox reaction indicates %hether the


reaction is s#ontaneous.

Relationshi# exists $et%een emf and the free-


ener! chan!e.
n 5 the no9 of moles of electrons transferred in the reaction9
F 5 Farada# constant 0 quantit# of electrical charge of 1 mol electron9
1 F 5 .7'+// C>mole 5 .7'+// ;>=0mole
Cn and F are "ositive quantities
G < -n8E
G < -n8E

E #ositi&e leads to a ne!ati&e G

E #ositi&e and G ne!ati&e indicate that a


reaction is s#ontaneous.

6hen $oth the reactants and #roducts are in


their standard states:

0ote: the n is not the sum of the num$er of
electron used in oxidation and reduction.
G 4 -n1E
G 4 -n1E
G
o 4 -n1Eo
G
o 4 -n1Eo
4.A E+8 and 8ree-Energ,
$%ange
Example
8alculate GJ
25r
#(aq) + 0
2(g) 5r2(l) + 20
#(aq)
olution
Reduction: F
2(g) 1 2e
0 1 2F0(aq) E<
red 5 29-6 =
Oxidation: 2Br
0(aq) Br
2(l) 12e
0 E<
red 5 19/7 =
E 5 29-6 0 19/7 5 19-1 =
5toichiometr of the half-reactions tells us that 2 mol of electrons are transferred durin!
the reaction. Ln 4 2M
G< 5 0nFE<
5 032 mol e043.7'+// ;>=0mole4319-1 =4
5 03%. D;
71
4.1B lectroc%emical
decomposition

C%at is electrol,sisD
6hen electricit is #assed
throu!h a molten ionic
8om#ound or throu!h
a solution of an
Electrolte, a chemical
reaction called
electrolsis can occur
4.1B Electroc%emical
decomposition

The ?8 source ser&es as an Nelectron


#um#O, #ullin! electrons a%a from one
electrode and #ushin! them throu!h the
external %irin! onto the other electrode

<ecause of the nature of the chemical


chan!e in an electrolsis cell, the
#ositi&e electrode $ecomes the anode, to
%hich the anions mo&e

The ne!ati&e electrode is the cathode,to


%hich the cations mo&e
72
4.1B Electroc%emical
decomposition
$omparison of electrol,tic and
gal*anic cells
*
The names anode and cathode are
assi!ned accordin! to the nature of the
reaction ta(in! #lace at the electrode
*
)n an electroltic cell, the cathode is
ne!ati&e and the anode is #ositi&e
*
)n a !al&anic cell, the cathode is #ositi&e
and the anode is ne!ati&e
73
4.1B Electroc%emical
decomposition
7%
Electrolysis in aq)eo)s sol)tions
@eed to consider oxidation and reduction of the solute as
8ell as oxidation and reduction of 8ater
E
13aq4 1 e0 E3s4 Eo 5 0 29.2=
22
2O3l4 1 2e
0 2
23g4 1 2O2
0 Eo5 0 /9-3 =
2
2O is reduced at the cathode' not E
1
S
2O-
203aq4 1 2e0 2SO
%
203aq4 Eo5 29/1 =
O
23g4 1 %21 3aq4 1 %e0 222O3l4 E
o 5 1923=
&t the anode' O
2 is formed9
Ahe half reaction 8ith smaller reduction
"otential occurs more easil# as an
oxidation9
4.1BElectroc%emical
decomposition
toic%iometr, of electroc%emical
reactions
*
The amount of chemical chan!e that occurs durin!
electrolsis is directl #ro#ortional to the amount of
electric char!e that is #assed throu!h an electrolsis
cell
*
The 5) unit of electric current is am#ere
*
The amount of #roduct can $e calculated usin!
1aradaOs la%
*
+mount of #roduct 4 ) t C n1
6here ) 4 current 2+3, t 4 time 2s3
n 4 mol electrons transferred
14 1aradaOs constant 2PQR00 8 mol
-"3
7+
-EE E5F
77