Ch13 Fundamentals of Electrochemistry (By Prof. Myeong Hee Moon)

13.
1
Anal. Chem. by Prof. Myeong Hee Moon 13:20
Ch. 13 Fundamentals of Electrochemistry
13-1. Basic Concepts of electrochemistry
redox reaction : reactions with electron transfer
oxidized : loses electrons
reduced : gains electrons
oxidizing agent (oxidant) : takes electrons from others and reduces
reducing agent (reductant) : oxidizes itself
Fe
3+
+ V
2+
Fe
2+
+ V
3+
1. Electric charge (q)
q : [coulomb] or [C] = 1.602 x 10
-19
C for a single electron
for 1 mole of e
1.602 x 10
-19
C x 6.02x10
23
/mol
9.649x10
4
C/mol Faraday constant [F]
q = n F
13.2
ex) If 5.585 g of Fe
2+
was reduced in the reaction above, how many
coulombs of charge must have been transferred from V
2+
to Fe
3+
?
9.649x10
3
C
13.3
: quantity of charge per second [A], ampere
<a charge of one coulomb per second>
ex) Suppose that electrons are forced into a platinum wire immersed
in a solution containing Sn
4+
, which is reduced to Sn
2+
at a constant
rate of 4.24 mmol/h. How much current flows into the solution ?
2. Electric Current
0.227 C/s = 0.227A
13.4
3. voltage, work, free energy
difference in electrical potential (E) between two points
= potential difference [V], volts
work : energy in joules [J]
J = E q
one joule of energy = one coulomb of charge is moved
between points whose potential differ by one volt.
Ex) How much work is required to move 2.36 mmol of electrons
through a potential difference of 1.05 V ?
2.39x10
2
J
13.5
The free energy change : AG
work done on surrounding : - AG
AG = -E q = - n F E
4) Ohm's law
current, I, flowing through a circuit
R
E
I =
[O]
13.6
work done per unit time, J/s or watt
5) power : p
E I
s
q
E
s
Eq
s
work
p
=
= = =
13.7
Galvanic Cells
: A cell generates electric energy
from where ? chemical reaction. = spontaneous reaction
Electrolytic Cells
: requires an external source of E.E.
one reagent must be oxidized, the other reduced.
Type of Electrochemical cells
13.8
13-2. A galvanic cell in Action
reduction : 2AgCl (s) + 2 e
-
2 Ag(s) + 2 Cl
-
(aq)
oxidation : Cd(s) Cd
2+
(aq) + 2 e
-
Net Cd(s) +2AgCl (s) Cd
2+
(aq) + 2 Cl
-
(aq)
+ Ag(s)
AG = -150 KJ/mol of Cd
13.9
cathode: 2 Ag
+
(aq) + 2 e
-
2 Ag(s)
anode : Cd (s) Cd
2+
(aq) + 2 e
-
net : Cd(s) + 2 Ag
+
(aq) Cd
2+
+ 2 Ag(s)
KCl contained gel agar with KCl
3) Line notation
| phase boundary
|| salt bridge
Cd(s) | Cd(NO
3
)
2
(aq) || AgNO
3
(aq) | Ag (s)
2. Salt Bridge
13-2. A galvanic cell in Action
13.10
13-3. Standard Potentials
measured voltage potential difference between Ag and Cd electrodes
- Positive voltage when e- flows
from anode into neg terminal.
- Opposite connection : negative
- standard reduction potential (E
o
)
: activities of all species are unity
- left half cell
:standard hydrogen electrode(SHE)
if P
H2(g)
is 1 atm,
definition , 0
,
2
=
+
H H
E
By convention, it is written as
SHE || Ag
+
| Ag(s)
13.11
Standard Reduction Potentials
std. Reduction potential
= potential difference between
the std potential of the reduction
of interest
and the potential of SHE
positive: electrons move
from SHE to Ag
+
negative: electrons moves
reverse direction
13-3. Standard Potentials
13.12
13-4. Nernst eq : net driving force
1) Nernst eq. for a half reaction,
a A + n e
-
b B
E
0
: std.reduction potential
R: gas constant 8.314 J/mol-K
n: number of moles
a
A
b
B
A
A
nF
RT
E E log
0
=
It shows two terms.
1. driving force under std. condition = E
0
2. concentration dependence (activity term)
concentration term in Nernst Eq.
reaction quotient
pure solids, pure liquids, solvent not included
At 25
0
C Nernst equation simplifies to
59.16mV change per 10 fold change
Q
A
A
a
A
a
B
=
a
A
b
B
A
A
n
E E log
05916 . 0
0
=
13.13
2) Nernst equation for a complete reaction
voltage difference (E) for the two electrodes.
E = E
+
- E
-
E
+
: potential of electrode at positive input terminal of potentiometer
= E
cathode
Procedure:
1. write half reactions with S.R.P.
2. write Nernst equation for half reaction
3. The more positive E
0
reduction predominantly happen
4. calculate net cell voltage
E = E
+
- E
-
5. write balanced reaction by subtracting the half reaction
13.14
ex) Find the voltage of the cell in Figure 14-5 if the right half cell contains 0.50 M
AgNO
3
(aq) and the left half cell contains 0.010 M CdCl
2
(aq). Write the net cell
reaction and state whether it is spontaneous in the forward or reverse direction.
right: 2 Ag
+
(aq) + 2 e
-
2 Ag(s) 0.799V
left: Cd
2+
(aq) + 2 e
-
Cd (s) -0.402V
net : Cd(s) + 2 Ag
+
(aq) Cd
2+
+ 2 Ag(s)
E
+
= 0.781V, E
-
=-0.461V, E = E
+
-E
-
= 1.242V
13.15
* Advice for finding relevant half-cell reactions
Pb(s) | PbF
2
(s) | F
-
(aq) || Cu
+2
(aq) | Cu(s)
anode cathode
oxidation reduction
right : Cu
2+
+ 2 e Cu (s)
left: PbF
2
(s) + 2 e 2 F
-
+ Pb (s)
in fact, 2 F
-
+ Pb (s) PbF
2
(s) + 2 e
13.16
13-5. E
0
and the equilibrium constant
E
0
and the equilibrium constant
: galvanic cell produces electricity until the cell reaches eq.
At eq. E=0
right electrode : a A + n e
-
c C E
+
0
left electrode : d D + n e
-
b B E
-
0
|
|
.
|
\
|
= =
+ + d
D
b
B
a
A
c
C
A
A
A
A
n
E E E E E log log
05916 . 0
) (
0 0
|
|
.
|
\
|
= } log{
05916 . 0
0
b
B
d
D
a
A
c
C
A
A
A
A
n
E Q : reaction quotient
at eq. E=0 as Q=K
E
0
= (at 25
0
C)
K =
k
n
log
05916 . 0
05916 . 0
0
10
nE
13.17
13-6. Cells as chemical probes
right half cell : AgCl(s) Ag
+
(aq) + Cl
-
(aq)
left half cell : CH
3
COOH CH
3
COO
-
(aq) + H
+
(aq)
they come to equilibrium without other half-cell
--- chemical reaction
13.18
with cell assembled,
AgCl(s) + e
-
Ag (s) + Cl
-
(aq, 0.10M) E
+
0
= 0.222V
in left : the only element -- hydrogen gas bubbles out
2 H
+
(aq, ?M) + 2 e
-
H
2
(g, 1.0atm) E
-
0
= 0
E = E
+
- E
-
= (0.222- log[Cl
-
]
2
) - (0- log )
in order to have same electrons
2
05916 . 0
2
05916 . 0
2
] [
2
+
H
P
H
= 0.222 - log = 0.503 V
2
2 2
] [ ] [
H
P
Cl H
+
we know [Cl
-
], adjusted = 1.
Thus, [H
+
] = 1.8 x 10
-4
M
2
H
P
we can calculate K for this case (K
a
)
K
a
= =
cell probe to measure the unknown H
+
conc.
13.19
ex) The cell in the following figure measures the formation constant (K
f
) of
Hg(EDTA)
2-
. The solution in the right hand compartment contains 0.500 mmol of
Hg
2+
and 2.00 mmol of EDTA in a volume of 0.100 L buffered to pH 6.00. If the
voltage is 0.331V, find the value of K
f
for Hg(EDTA)
2-
.
13.20
Selected Problem No.
14-4, -5, -10, -17, -35, -38,

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