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Electrochemical Cells Chp3 Sept2014
Electrochemical Cells Chp3 Sept2014
Electrochemical Cells Chp3 Sept2014
ELECTROCHEMICAL CELLS
BY
MDM HAIRUL AMANI BINTI ABDUL HAMID
OUTLINE
Components of a cell
Conventional representation of a cell
Potential of cells and electrodes
Thermodynamic of cells
Work and free energy
Standard electrode potentials
Equilibrium constant
Nernst equation
OUTLINE
Types of electrodes and general form of
Nernst equation for an electrode
QUIZ 4
Types of galvanic cells and general form of
Nernst equation for a galvanic cell
Applications of galvanic cell potentials
Activity coefficients
Equilibrium constants
Solubility constants
pH
3
TEST 2
ELECTROCHEMICAL CELLS
Redox Reaction
- Is a reaction in which there is a transfer of electron
Redox Reaction
Half reactions
Cu2+(aq) + 2e- Cu(s) (Reduction of Cu2+)
Zn(s) Zn2+(aq) + 2e- (Oxidation of Zn)
Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) (Overall)
The reduced and oxidised substances in half
reactions form redox couple:
Cu2+/Cu and Zn/Zn2+
Half reactions
In general the redox couple is written as Ox/Red with
the half reaction as:
Ox + ne- Red
Example:
Cu2+(aq) + 2e- Cu(s)
Zn2+(aq) + 2e- Zn(s)
Redox couple
Cu2+/Cu
Zn2+/Zn
Reaction Quotient, Q
For half reaction:
Cu2+(aq) + 2e- Cu(s)
Q=
1
(Cu2+)
Zn2+(aq) + 2e- Zn(s)
Q= 1
(Zn2+)
For the standard state of pure material
(element) it has unity activity eq Cu = 1
10
Reaction Quotient, Q
Reaction quotient for the reudction of O2 to H2O in
acid solution,
O2(g) + 4H+(aq) + 4e- 2H2O(l)
Q = 2H2O since O2 behaves as perfect gas
4H+ O2
O2 = PO2
= P
P
4H+ PO2
and 2H2O = 1
11
Reactions at electrode
When spontaneous
reaction takes
place in a galvanic
cell, electron are
deposited in
anode(oxidation)
and collected from
cathode (reduction)
Galvanic cell
Electrolytic cell
14
Varieties of electrode
1. Metal/metal ion electrode
Cu2+ + 2e- Cu
15
Varieties of electrode
2. Redox electrode
Species exist in solution in 2
oxidation state.
Fe3+ to Fe2+
16
Varieties of electrode
3. Gas electrode
Varieties of electrode
3. Gas electrode (Cont)
eg. Hydrogen electrode
inert metal as electrode.
gas in equilibrium with its ion
2H+(aq) + 2e- H2 (g) (Reduction)
Redox couple: H+/H2
It may either be a cathode or an anode
The standard hydrogen electrode is attached to the electrode
system under investigation.
18
AgCl(s) + e
Ag(s) + Cl-(sat)
19
Cell Notation
ZnZn2+(1 M) Cu2+(1 M)Cu
Phase
boundary
Single cell
compartment
interphase
Anode
(oxidation)
Salt bridge
Cathode
(reduction)
Half Equations:
Zn(s) Zn2+(aq) + 2e
20
Cu2+(aq) + 2e Cu(s)
Cell reaction
The reaction in the cell written on the assumption that righthand electrode is cathode and with spontaneous reaction,
reduction is taking place in the right-hand compartment
Cu2+(aq) + 2e Cu(s)
(Reduction)
Zn(s) Zn2+(aq) + 2e
(Oxidation)
21
Example 1
Write the half-equations and cell reactions for each
of the following cells:
a) AgAg+H+H2, Pt
b) PtCr2O72, Cr3+, H+BrBr2(l), Pt
22
Answer:
a) AgAg+H+H2, Pt
Ag Ag+ + e (Oxidation) (2x)
2H+ + 2e H2 (Reduction)
2Ag + 2H+ 2Ag+ + H2(g) (overall = cell reaction)
b) PtCr2O72, Cr3+, H+BrBr2(l), Pt
2Cr3+ + 7H2O Cr2O72 + 14H+ + 6e (Oxidation)
(Br2(l) + 2e 2Br) 3
(Reduction)
2Cr3+ + 7H2O + 3Br2(l) Cr2O72 + 14H+ + 6Br
23
Example2
Describe in shorthand notation a galvanic cell for
which the cell reaction is
Cu(s) + 2Fe3+(aq) Cu2+(aq) + 2Fe2+(aq)
Answer:
Oxidation:
Cu(s) Cu2+(aq) + 2e
Reduction:
Fe3+ + e Fe2+
Cell Notation: CuCu2+ Fe2+, Fe3+Pt
(Since both Fe2+ and Fe3+ are in solution, a Pt electrode
is used.)
24
Varieties of cells
1. Daniell cell
25
Varieties of cells
2.
Varieties of cells
3. Electrode concentration cell
The potential difference is developed between two like
electrodes at different concentrations dipped in the same
solution of the electrolyte.
For example, two hydrogen electrodes at different pressure
in the same solution of hydrogen ions constitute a cell of
this type.
Pt,H2 (Pressure p1)) |H+ ||H+, H2 (Pressure p2)Pt
Cell Potential, V
- The potential difference between two electrodes.
29
30
Voltmeter
A voltmeter is an instrument used for
32
Multimeter
Voltmeter
Go = - RT lnQ )
34
Standard Potentials
Define a potential of one electrodes as having zero
potentials, then assign values to others on that
basis.
SHE (LH) Standard Hydrogen Electrode.
Pt | H2(g)|H+(aq) E0= 0 at all temperatures
Example:
The standard potential of Cu2+/Cu couple (RH
electrode)
Pt | H2(g)|H+(aq) || Cu2+|Cu
E0 (Cu2+/Cu)=0.337V
35
1 atm
Eo = - 0.76
37
Eocell = 0.76 V
38
39
reversible
The sign Eo changes
metric coefficients of
half cell reaction does
not change value of Eo
40
Example
Consider the following reaction:
Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq)
Determine the emf of the cell given the
concentration of Cu2+ and Zn2+ are 5.0M and
0.050M respectively at 298K.
41
Answer
Cu2+(aq) + 2e- Cu(s) EoCu2+/Cu = +0.34 V
Zn2+(aq) + 2e- Zn(s)
EoZn2+/Zn = - 0.76 V
Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) Eocell = ?
42
Answer(cont)
Using Nernst equation:
Example
Consider the following reaction:
Cr2O72- (aq) + 14H+ (aq) + 6I- (aq) 2Cr3+(aq)
3I2(s) + 7H2O(l)
Determine the emf of the cell given the
concentration:
[Cr2O72-]= 2M, [H+] =1M, [I-] = 1M and
[Cr3+] = 1.0 x 10-5M
44
Answer
Cr2O72- (aq) + 14H+ (aq) + 6I- (aq) 2Cr3+(aq) 3I2(s) +
7H2O(l)
Eocell = Eocathode - Eoanode
= EoCr2O72-/Cr3+ - EoI2/I= 1.33 0.53
= 0.8 V
45
Answer
Cr2O72- (aq) + 14H+ (aq) + 6e 2Cr3+(aq) +7H2O(l)
6I- (aq) 3I2(s) + 6e
n=6
Using Nernst equation:
E cell= Eocell 0.0592 logQ = Eocell 0.0592 log[Cr3+]2
n
n
[Cr2O72-][H+]14[I-]6
= 0.8 - 0.0592 log (1.0 x 10-5) 2
6
[2] [1]14[1]6
= 0.8 - 0.0592 log 5 x 10-11
6
= 0.8 (- 0.10) = 0.90 V
Since [reactant]>[product] -- E cell > Eocell
46 If value of Q increases -- value of E cell decreases.
Concentration Cell
Cell Notation:
M(s)|M+(aq, L) M+(aq, R)| M(s)
[R] > [L], E 0
Positive potential arises because positive ions tend to
be reduced , withdrawing electrons from the electrode.
This occur in the right hand electrode compartment
which is more concentrated
M+ (m2) + e M
The reaction at the left hand electrode is:
M M+(m1) + e
Overall reaction:
M+ (m2) M+ (m1)
47
Overall reaction:
M+ (m2) M+ (m1)
If m2 > m1 the reaction is a forward direction, positive
emf is produced.
If m2 < m1 electrons flow from right to left electrode,
negative emf is produced.
G associated with transfer of M+ ions from M+ (m1)
M+ (m1) is given by:
G = RT ln m1
m2
Since no. of mol of e- = 1,
E = RT ln m2
E is positive if m2 > m1
F
m1
Go = 0 and Eo = 0 since a cell cannot drive a current
through a circuit with 2 identical electrode
compartment.
48
Example:
Calculate the emf at 25oC of a concentration cell of
this type in which the molalities are 0.2m and
3.0m.
E = RT ln m2
F
m1
49
at 25oC
E = 0.0257 ln m2
m1
= 0.0257 ln 3.0
0.2
= 0.0696 V
Concentration Cell
Calculate the emf of the
cell in the diagram at
25oC
50
1.00 x 10-3
Cell Equlibrium
When a cell has reached equilibrium, then Q = K,
while E = 0 since chemical reaction at equilibrium do no work
and generates 0 potential difference between the electrodes
of the cell.
E= Eo - RT lnQ
nF
0 = Eo - RT lnK
(x nF
nF
0 = nFEo RTlnK
nFEo = RT lnK
ln K = nFEo
RT
51
E= 0
and Q = K)
Example:
Calculate the equilibrium constant at 25oC for the
reaction occurring in the Daniell cell, if the
standard emf is 1.10V.
Answer:
ln K = nFEo
RT = 0.0257
RT
F
ln K = 2 x 1.10 = 85.6
0.0257
K = e85.6 = 1.50 x 1037
For spontaneous process, Go <0, Eo > 0 and K > 1
52
Example
A reaction important in an acidic environment:
Fe(s) + 2H+(aq) + O2 (g) Fe2+ (aq) + H2O(l)
Does the equilibrium constant favour the formation of
Fe2+ (aq)?
Reduction half reaction:
Fe2+ + 2e Fe(s)
Eo = - 0.44 V
(anode)
2H+(aq) + O2 (g) + 2e H2O(l) Eo = +1.23 V
(cathode)
Eo cell = Eocathode Eoanode = 1.23 (-0.44)= 1.67 V
Since Eo cell > 1, the reaction has K>1
Favour the formation of Fe2+
53
54
Metal electrode
-potential of an Ag+/Ag electrode is given by:
Electrode half reaction:
Ag+(aq) + e Ag(s) n = 1
E Ag+/Ag = EoAg+/Ag RT ln 1
F
(Ag+)
2.
55
n=2
Electrolysis
- is a chemical process that uses
56
Electrolytic cell
Battery function as a
source of direct current
- Forces electrons out
of anode
- Pushes electrons
towards the
cathode.
Yn- Y + ne
(oxidation)
Cathode: Xn+ + ne X
(reduction)
Anode:
57
58
59
60
Eo = - 2.71V
Eo = - 0.83V
Eo = -1.36V
Eo = -1.23V
61
Corrosion
62
Corrosion
Corrosion is the gradual (spontaneous)
63
Figure 21.20
(1)
(2)
(3)
64
1
2 Fe 2 (aq) O2 ( g ) (2 n) H 2O(l ) Fe2O3 .nH 2O( s) 4 H (aq)
2
3
Overall 2 Fe( s) O2 ( g ) nH 2O(l ) Fe2O3 nH 2O( s)
2
Figure 21.22
faster corrosion
65
cathodic protection
Figure 21.23
67
68