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• electrode - electron conductors

• electrolyte - ionic conductors
• Galvanic cell - produces electricity - spontaneous
reactions
• Electrolytic cell - nonspontaneous reactions driven
by external source

Reaction consists of 2 half cell reactions:

1. Reduction: electrons are gained
2. Oxidation: electrons are donated, given up

Electrochemical Cell
Electrochemical Cell
E
o
/V std electrode potential
anode: oxidation Zn  Zn
2+
+ 2e- -0.76 Q=a(Zn
2+
)
cathode: reduction Cu
2+
+ 2e-  Cu +0.34 Q=a
-1
(Cu
2+
)
Zn metal dissolving: Cu ions being deposited on Cu metal
Zn|Zn
2+
|Cu
2+
|Cu line indicates metal-liquid or liquid-liquid junction
Zn Cu
anode
cathode
membrane separates 2 different electrolytes
Standard cell potential – potential difference betw. ½ cell rxns.
The larger the value the more potential to do work
In order to compare different rxns to each other we need a zero point
we use: H
2
---> 2H
+
+ 2e
-
E
o
=0V Q = a
2
(H
+
)/(f
H2
/p
o
)

standard hydrogen electrode

Pt with H
2
bubbled through Pt, H
2
|H
+
f
H2
= 1 atm

noble metals have higher standard potentials
- do not corrode as easily (see slide of standard potentials)
standard calomel electrode
Hg|Hg
2
Cl
2
(mercurous chloride)|sat'd KCl

Hg
2
Cl
2
+ 2e-  2Hg(l) + 2Cl
-
(aq) E
o
= 0.245V

Reference electrode – nonpolarizable
– resist change in potential difference
work done in a cell (non P-V work) = -AG

AG
m
o
= -zFE
o
standard state is 1 molal solution
F = Faraday's constant = 96485 C/mol
z = # of electrons in one mole - unitless

E
o
/V AG
o
/J/mol
Zn  Zn
2+
+ 2e
-
0.76 -146680
Cu
2+
+ 2e
-
 Cu 0.34 - 65620
Zn + Cu
2+
 > Zn
2+
+ Cu -212300

AG
o
= -zFE
o
= -212300J/mol

E
o
= 212300J/mol/2x96485C/mol=1.1V


since AG<0  spontaneous reaction
E
o
> 0  spontaneous reaction
Example
b
B
a
A
d
D
c
C
o
m m
a a
a a
RT G G ln + A = A
Remember in solution
µ = µ
o
+ RT lna where µ
o
= standard state µ =G/n
aA + bB = cC + dD
generally we can use concentration instead of activity
0 ln = + A = A
b
B
a
A
d
D
c
C
o
m m
a a
a a
RT G G
At equilibrium:
AG
o
= -RTlnK = -zFE
o
K = eqm constant
E
o
=(RT/zF)lnK = (0.059/z)logK for T = 25
o
C
b a
d c
B A
D C
] [ ] [
] [ ] [
RTln G G
o
m m
+ A = A
b a
d c
o
B A
D C
z
E E
] [ ] [
] [ ] [
log
059 . 0
÷ =
gives variation of cell potential with concentration
divide by -zF
Nernst eqn.
| |
| |
V
x
V
Cu
Zn
V E 982 . 0
10 1
1
log
2
059 . 0
1 . 1 log
2
059 . 0
1 . 1
4 2
2
= ÷ = ÷ =
÷ +
+
Example:

Zn + Cu
2+
 Zn
2+
+ Cu

Zn(s)|Zn
2+(
1M) || Cu
+
(10
-4
M)|Cu(s) || represents salt bridge
] ][ [
] [
log
1
059 . 0
028 . 0
2
3
+ +
+
÷ =
Ag Fe
Fe
Ecell
Fe
2+
, Fe
3+
redox cell, both oxidized & reduced species present at
an inert electrode
E
o
/V
oxidation: Fe
2+
 Fe
3+
+ e
-
-0.771
reduction: Ag
+
+ e
-
 Ag 0.799
Ag
+
+ Fe
2+
 Fe
3+
+ Ag 0.028
Example:
Pt|Fe
2+
(0.1M), Fe
3+
(0.2M)||Ag
+
(1M)|Ag(s)
V Ecell 01 . 0
] 1 ][ 1 [.
2 .
log
1
059 . 0
028 . 0 = ÷ =
E
o
/V AG
o
/J/mol
Cu
+
+ e
-
 Cu 0.522
Cu
+
 Cu
2+
+ e
-
-0.158 15249
Cu
2+
+ 2e
-
 Cu 0.34 -65620
Cu
+
+ e
-
 Cu -50373

AG
o
/ -zF = E
o
= 0.522
We can add E
o
of the half cell to get E
o
only if no electrons occur in
final equation
Example:
P P
T
E
zF
T
G
S
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
÷ = A
(
¸
(

¸

|
.
|

\
|
c
c
÷ ÷ = A
P
T
E
T E zF H
We know
Thermodynamic properties & variation of electrode potential
We know AG = -zFE
AH = AG + TAS constant T
Measurement of pH and Concentration Cells
Pt, H
2
(g,1atm)|H
+
(XM)||H
+
(1M)|H
2
(g,1atm),Pt
[H+] = xM
[H+] = 1M
H
2
Pt
salt bridge
Pt
H
2
E
o
/V
oxidation: H
2
 2e
-
+ 2H
+
(XM) 0.0
reduction: 2e
-
+ 2H
+
(1M)  H
2
0.0
2H
+
(1M)  2H
+
(XM)
Pt, H
2
(g,1atm)|H
+
(XM)||H
+
(1M)|H
2
(g,1atm),Pt
concentration cell - electrochemical cell in which net reaction is
simply change in concentration of same species [H
+
]

- potential exists due to difference in concentration
For this example: E
cell
= 0.059pH
By measuring E
cell
we can find pH
- in lab use glass electrode, which contains reference electrode
of known E
o
E
o
cell
= 0
| |
| |
+
+
÷ = ÷ = H
H
E E
o
cell cell
log 059 . 0
1
log
2
059 . 0
2
2
oxidation: Pb(s)  2e
-
+ Pb
2+
(sat'd, PbCl
2
,aq)
reduction: 2e
-
+ Pb
2+
(0.1M)  Pb(s)
Pb
2+
(0.1M)  Pb
2+
(sat'd, PbCl
2
,aq) E
o
cell
= 0.0V
Measurement of Solubility
Consider: Concentration Cell
Pb(s)|Pb
2+
(sat'd, PbCl
2
,aq)||Pb
2+
(0.1M)|Pb(s) E
cell
= 0.024V
| |
024 . 0
1 . 0
log
2
059 . 0
'
2
=
÷
=
+
d sat
cell
Pb
E
| | 1 . 0 log
059 . 0
2
* 024 . 0 log
'
2
+ ÷ =
+
d sat
Pb
| | 015 . 0
'
2
=
+
d sat
Pb
K
sp
= [0.015][0.031]
2
= 1.4 x 10
-5
Can calculate solubility of PbCl
2
(K
sp
)
PbCl
2
(s)  Pb
2+
(aq) + 2Cl
-
(aq)
| | | |
2
' '
2
d sat d sat sp
Cl Pb K
÷ +
=
[Cl
-
] = 2[Pb
2+
] = 0.031
Galvanic Cells – spontaneous

Dry Cell LeClanche Cell 1.5Volts

Anode: Zn  Zn
+2
(aq) + 2e
-
oxidation
Electrolyte: paste MnO
2
, NH
4
Cl (starch as thickener)
Cathode: inert C (graphite rod)
Applications - Batteries
2NH
4
+
(aq) + 2MnO
2
(s) + 2e
-
 Mn
2
O
3
(s) + 2NH
3
(g) + H
2
O(l)
http://www.mpoweruk.com/cell_construction.htm
Zn(s) + 2 MnO
2
(s) + 2 NH
4
Cl(aq)  ZnCl
2
+ Mn
2
O
3
(s) + 2 NH
3
(g) + H
2
O
NH
3
disrupts current supply can form:
Zn
+2
+ 4NH
3
 [Zn(NH
3
)
4
]
+2
Alkaline battery – electrolyte is NaOH or KOH paste

Zn(s) + 2OH
-
(aq)  Zn(OH)
2
(s) + 2e
-

2MnO
2
(s) + H
2
O(l) + 2e
-
 Mn
2
O
3
(s) + 2OH
-
(aq)

Alkaline conditions less corrosion
http://chemwiki.ucdavis.edu/Analytical_Chemistry/Electrochemistry/Voltaic_Cells/Case_Study:_Battery_Types#Alkaline_cells
Anode: Zn + 4OH
-
→ Zn(OH)
4
2-
+ 2e
-


Fluid: Zn(OH)
4
2-
→ ZnO + H
2
O + 2OH
-

Cathode: O
2
+ 2H
2
O + 4e
-
→ 4OH
-

Overall: 2Zn + O
2
→ 2ZnO
http://www.watchbatteries-usa.com/faq.html
Primary cells – not rechargeable – electrodes cannot be reversed
Zn-air battery
Electrolyte: H
2
SO
4
solution
Rechargeable or Secondary Cells
Pb-acid storage battery - known since 1859
6 cells – 2V each connect anode to cathode
Anode: Pb(s) +SO
4
-2
(aq)  PbSO
4
(s) + 2e
-

porous Pb for max surface area
Cathode: PbO
2
(s) + 4H
+
(aq) + SO
4
-2
(aq) + 2e
-
 PbSO
4
(s) + 2H
2
O
Electrons in the positive
plates (brown) go through
an electrolytic solution of
water and sulfuric acid into
the negative plates (white).
PbSO
4
produced precipitates and deposits onto
the electrodes – cell can then be operated in
reverse to recharge battery
Eventually PbSO
4
flakes off electrode or short
circuit occurs and battery cannot be recharged
Spontaneous reaction uses up H
2
SO
4
lowering its
concentration, the cell potential and the density of
the electrolyte (water produced)
measure electrolyte density – common way of
detecting run down battery
Anode: Cd(s) + 2OH
-
(aq)  Cd(OH)
2
(s) + 2e
-

Cathode: NiO
2
(s) + 2H
2
O + 2e
-
 Ni(OH)
2
(s) + 2OH
-
(aq)

Overall: Cd(s) + NiO
2
(s) + 2H
2
O  Cd(OH)
2
(s) + Ni(OH)
2
(s)

OH
-
not used up as cell discharges – reversible

Cd does not tend to dissolve in electrolyte, so good reversibility
NiCd battery 1.3 V
Corrosion of Metals
Metal is oxidized: M(s)  M
n+
(aq) + ne
-
e
-
produced in this half cell rxn have to be taken up by reduction rxn
In acid: 2H
+
(aq) + 2e
-
 H
2
(g) acid dissolving metal
Reduction can also be caused by:
a) dissolved O
2
in water
O
2
(aq) + 2H
2
O(l) + 4e
-
 4OH
-
(aq)
b) another metal present in solution: M
n+
(aq) + ne
-
 M(s)
or
Which metals will corrode?
Those with more negative
reduction potentials
Standard Electrode Potentials in Aqueous Solution at 25°C



Standard Electrode Potentials in Aqueous Solution at 25°C
Cathode (Reduction)
Half-Reaction
Standard Potential
E
°
(volts)
Li
+
(aq) + e
-
 Li(s) -3.04
Mg
2+
(aq) + 2e
-
 Mg(s) -2.38
Al
3+
(aq) + 3e
-
 Al(s) -1.66
Zn
2+
(aq) + 2e
-
 Zn(s) -0.76
Cr
3+
(aq) + 3e
-
-> Cr(s) -0.74
Fe
2+
(aq) + 2e
-
 Fe(s) -0.41
Cd
2+
(aq) + 2e
-
 Cd(s) -0.40
Ni
2+
(aq) + 2e
-
 Ni(s) -0.23
Sn
2+
(aq) + 2e
-
 Sn(s) -0.14
Pb
2+
(aq) + 2e
-
 Pb(s) -0.13
Fe
3+
(aq) + 3e
-
 Fe(s) -0.04
2H
+
(aq) + 2e
-
 H
2
(g) 0.00
Cu
2+
(aq) + 2e
-
 Cu(s) 0.34
O
2
(g) + 2H
2
O(l) + 4e
-
 4OH
-
(aq) 0.40
Ag
+
(aq) + e
-
 Ag(s) 0.80
Au
3+
(aq) + 3e
-
 Au(s) 1.50
http://www.corrconnect.org/cp1_inspect_protect/concentration-cell
A classic example of dissimilar metal corrosion is the HMS Alarm. This
frigate was sheathed in copper in the mid-1700's to prevent attack by
barnacles. It was soon discovered however that the iron nails securing the
copper in place had become severely corroded.
By chance, some of the nails still had the brown paper from their packaging
lodged underneath their heads, separating them from the copper. These nails
were largely intact. A 1763 report to the Admiralty on the rotting of these nails
helped usher in the modern study of metal corrosion.
http://www.corrconnect.org/cp1_inspect_protect/dissimilar-metal-galvanic-corrosion-cell
Some metals such as Al readily form thin passive
(oxide) film on its surface, which protect it from
corrosion.
Other metals such as Fe – forms rust which eventually
flakes off.
O
2
+ 4e- + 2H
2
O → 4 OH
-
Fe → Fe
2+
+ 2e
-

4 Fe
2+
+ O
2
→ 4 Fe
3+
+ 2 O
2-
Fe
2+
+ 2H
2
O ⇌ Fe(OH)
2
+ 2H
+
Fe
3+
+ 3H
2
O ⇌ Fe(OH)
3
+ 3H
+

Fe(OH)
2
⇌ FeO + H
2
O
Fe(OH)
3
⇌ FeO(OH) + H
2
O
2FeO(OH) ⇌ Fe
2
O
3
+ H
2
O
http://www.chem1.com/acad/webtext/elchem/ec7.html
Corrosion often occurs where metal is under stress, such as at
a scratch or pit.
http://chemwiki.ucdavis.edu/Analytical_Chemistry/Electrochemistry/Case_Studies/Corrosion
Sacrificial Anode
Preventing Corrosion
Coat steel pipe with Zn, which is more active metal, i.e. a lower
reduction potential - Zn becomes anode & will corrode before the steel
Buried pipes, piers, hulls of ships continually exposed to
electrolytic solution
-use sacrificial anode – metal which will more easily corrode
- Mg
2+
+ 2e
-
 Mg E
o
= -2.38V
http://www.tutorvista.com/content/chemistry/chemistry-iv/electrochemistry/corrosion.php