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CHAPTER 4
Electrochemistry
2
SCOPE
Electrochemical cells
Galvanic cells
Shorthand notation
3
SCOPE
Cell EMF
Electrochemical $ecom"osition
%
LESSON OUTCOMES
&t the end of this lecture' students should
(e a(le to)
*
Identify the oxidizing and reducing agents
in a redox reaction
*
Write equations for oxidation and reduction
half-reaction and use them to balance the
net equation.
*
Describe galvanic cells
+
LESSON OUTCOMES
&t the end of this lecture' students should
(e a(le to)
*
Draw cell diagram
*
Write shorthand notation
*
Calculate cell potential
*
Calculate ,G from cell potential
The transfer of electron durin! redox reactions can #roduce ener! in the form of
electricit.
Oxidation num$ers
+lso called oxidation state
Rules:
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
T%o t#es:
>oltaic cell 2Gal&anic cell3.
Electroltic cell.
+node, Oxidation) -
#(aq) -
2
<alance - half-reaction method.
'-
#(aq) ,-
2(s) + 'e
#
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
EJred 4 / =
The :n
21>:n electrode is the anode and 5HE is the cathode.
;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 $e the hi!her on the scale.
Cathode (reduction)
Anode (oxidation)
EJ
cell
EJ
red
EJ
red
E
J
r
e
d
2
>
3
More positive
More negative
-%e di=erence
(et>een
t%e standard
reduction
potentials pus%
e-
t%roug% an
external
circuit.
4.9 tandard Reduction
:otential 2E;
red3
Oxidation: Li(s)
Li+(aq) is easil oxidi*ed, !reat tendenc to transfer e- the
stron!est reducin! a!ent.
EJ
red 4 +&e 5tron!est oxidi*in! a!ent
EJred 4 -&e 5tron!est reducin! a!ent
The list of EJred &alues #ro&ides an orderin! of the a$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
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