Professional Documents
Culture Documents
Electrochemistry
9. Fundamentals of Electrochemistry
Data treatment and analysis
10. Potentiometry
1. Errors in Chemical Analysis
11. Ion Selective Electrodes
2. Significance Tests
12. Voltammetry
3. Sampling and Calibration Methods
Separation science
4. Extraction Techniques
5. Introduction to Chromatography
6. Gas Chromatography
7. High Pressure Liquid
Chromatography
8. Electrophoresis
Nanoanalysis
13. Nanoanalysis
Equilibria
14. Chemical Equilibrium
15. Acid, Bases and Acid-Base
Equilibrium
16. Chemical Equilibrium for Complex
Systems
17. Chemical Equilibrium for Titrations
CM2142
Fundamentals of Electrochemistry
1.
2.
3.
4.
5.
6.
7.
8.
9.
Introduction
Oxidation Numbers
Balancing Redox Equations
Voltaic/Galvanic Cells
Cell Diagrams
Cell Potentials
Free Energy and Nernst Equations
Electrolytic Cells
2-Electrode and 3-Electrode Systems
CM2142
eLecture prepared by
Dr Emelyn Tan
What is Electrochemistry?
Electrochemistry involves chemical phenomena
associated with charge separation and charge transfer,
with applications ranging from fundamental studies and
research to industrial, environmental and clinical
applications.
CM2142
Terminology
Term
Units
Equation
Definition
Current (i)
Amperes (A)
A=C/s
Quantity of charge
flowing in a circuit per
second.
Potential (E)
Volts (V)
V=J/C
Resistance (R)
ohm ()
V=iR
Ohms Law
Q=nF=it
A charge of single
electron is 1.602 x 10-19
C.
1 mol of electron has
96485 C (Faradays
constant).
Work (w)
Joules (J)
w=nFE=QE
Power (P)
Watt (W) = 1 J / s P = w / t = i E
CM2142
A=C/s
V=J/C
Current
Potential
CM2142
Reduction:
- Gain of electrons
- Decrease in oxidation number
- Loss of oxygen
- Gain of hydrogen
Oxidising Agent:
- Species is reduced
Reducing Agent:
- Species is oxidised
2.
CM2142
5.
O.N of H in H2O2
O.N of l in lO65-
1 + x + 4(-2) = 0
x = +7
2x + 2(-1) = 0
x = +1
x + 6(-2) = -5
x = +7
O.N. of Mn is +7
O.N. of H is +1
O.N. of I is +7
O.N of Mn in CsMnO4
CM2142
10
Balancing Oxidation-Reduction
Equations
Perhaps the easiest way to balance the equation of an
oxidation-reduction reaction is via the half-reaction method.
This involves treating (on paper only) the oxidation and
reduction as two separate processes, balancing these half
reactions, and then combining them to attain the balanced
equation for the overall reaction.
1 oxidation half reaction
+ 1 reduction half reaction
Overall reaction
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11
Half-Reaction Method
This must be done in sequential order.
1.
2.
3.
CM2142
12
Half-Reaction Method
4.
5.
6.
7.
13
+3
+2
+4
10
+ 2e-
Mn2+ + 4H2O
2
8
X5
X2
Balancing
+ 16OH-(aq)
+ 16OH-(aq)
in Basic
Solution: 2MnO + 5C O 2 + 16H O 2Mn2+ + 10CO + 8H O + 16OH4
2 4
2
2
2
2MnO4 + 5C2O42 + 8H2O 2Mn2+ + 10CO2 + 16OHCM2142
14
Figure 21.3
Silberberg
ELECTROLYTIC CELL
Oxidation half-reaction
X
X+ + e- from electrode
Oxidation half-reaction
AA + e- in solution
Reduction half-reaction
at electrode Y++ eY
Reduction half-reaction
in solution B++ eB
Inert
electrodes
Cells
Ecell
Electrode
name
Process at Sign of
electrode electrode
Voltaic/
Galvanic
>0
Spontaneous
Anode
Cathode
Ox.
Red.
Electrolytic
Tunable,
Nonspontaneous
Anode
Cathode
Ox.
Red.
+ (anions)
- (cations)
CM2142
Electrodes
Electrodes
are (usually)
inert
16
Voltaic Cells
In spontaneous oxidationreduction (redox) reactions,
electrons are transferred and
energy is released.
The energy can be used to do
electrical work when the
electrons are channeled
through an external device =>
voltaic cell.
CM2142
17
Voltaic Cells
Connect electrodes by a
wire/voltmeter.
Connect solutions by a
salt bridge.
-ve
+ve
Ox.
Red.
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18
Salt Bridge
Once even just one electron flows from the anode to the cathode, the
charges in each beaker would not be balanced and the flow of electrons
would stop. (right half cell will be -ve, preventing further electron flow)
Therefore, a salt bridge is used, usually a U-shaped tube that contains a salt
solution, to keep the charges balanced.
Left half cell: net + ve charge in solution so anions move toward the anode.
Right half cell: net - ve charge in solution so cations move toward the
cathode.
Migration of ions out of the salt bridge is higher than into the salt bridge.
Diffusion from high to low ion concentration.
Besides NaNO3, other usual choices for the electrolyte in the salt bridge are
KCl or KNO3.
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19
Cell Diagrams
Salt bridge
If both ox. and red. species are ions, then use Pt (or graphite) as
the electrode. e.g Zn(s) I Zn2+(aq) II Fe3+(aq), Fe2+ (aq) I Pt(s)
Cannot dip wire into solution, need an electrode.
CM2142
20
CM2142
21
Appendix 5 Skoog
Standard:
g = 1 atm
aq = 1 molL-1
a=1
Lower red.
potential, more
easily oxidised,
half-cell will be the
anode.
Strong reducing
agents.
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22
aq = 1 molL-1
i.e. pH = 0
CM2142
23
Potential
readings can
be negative.
o
Ered
0V
CM2142
H+ is more readily
reduced cf. Zn2+
Ered (Zn2+) < 0 24
= Ered
(cathode) Ered
(anode)
Ecell
Larger Ered,
Reduction process
CM2142
Smaller Ered,
Oxidation process
25
Cell Potentials
For the oxidation (anode) in this cell,
= 0.76 V
Ered
Ecell
(cathode) Ered
(anode)
= Ered
= +0.34 V (0.76 V)
= +1.10 V
CM2142
26
E0 = -1.66 V
E0 = -0.40 V
Write the cell reaction for a voltaic cell based on these two
electrodes, and calculate the standard cell potential, Eocell.
Indicate which is the positive and negative electrode.
Al is oxidised at the anode. In voltaic cells, anode is negative.
Cd2+ is reduced at the cathode. In voltaic cells, cathode is positive.
2Al(s) + 3Cd2+(aq) 2Al3+(aq) + 3Cd(s)
V=J/C
27
Free Energy
Go for a redox reaction under standard conditions, can be
written as the equation:
Go = total charge x Eocell = -RT ln K
Go = nF x Eo
Go = nFEo = wmax For redox reaction to be
where:
n is the number of moles of electrons transferred per mole of
reaction
F is the Faraday constant (1 F = 96,485 Cmol-1)
Eo is in V = J/C
CM2142
28
Nernst Equation
Recall that G = G + RT ln Q
then nFE = nFE + RT ln Q
By dividing both sides of nFE = nFE + RT ln Q by nF,
we obtain the Nernst equation:
At 298 K,
RT
Ecell = Ecell
nF
In
x 2.303
ln Q
log
x ln 10
CM2142
29
RT ln products
reactants
nF
30
Ecell = Ecell
RT
nF
ln Q
[Cu2 ] 1
Q
2 1
2
[Ag ] 1
Figure 18-5
Skoog
CM2142
31
Concentration Cells
Ni
Ecell = Ecell
RT
nF
ln Q
Ni
Notice that the Nernst equation implies that a cell could be created
that has the same substance at both electrodes.
For such a cell, Ecell would be zero, but Q would not.
Therefore, as long as the concentrations are different, Ecell
will not be 0.
CM2142
32
CM2142
33
RT [Cu2 ]
E E
ln
2F [Ag ]2
V=J/C
CM2142
RT [Cu2 ]5
E E
ln
10F [Ag ]10
RT
E E
(ln[Cu 2 ]5 - ln[Ag ]10 )
10F
RT
E E
(5ln[Cu 2 ] - 10ln[Ag ])
10F
RT
E E
5(ln[Cu 2 ] - 2ln[Ag ])
10F
RT
E E
(ln[Cu 2 ] - ln[Ag ]2 )
2F
RT [Cu2 ]
E E
ln
2F [Ag ]2
34
o
Ag /Ag
0.059
1
log
1
[Ag ]
K sp
1
[Cl ]
[Ag ][Cl ]
[Ag ] K sp
E AgCl/Ag E
KCl + AgNO3 AgCl + KNO3
Figure 18-9
Skoog
o
Ag /Ag
EoAgCl/Ag 0.80
0.059
[Cl ]
log
1
K sp
0.059
1
log
1
1.8 x 10 -10
EoAgCl/Ag 0.22 V
36
Ag+(aq) + e- Ag(s)
E Ag /Ag EoAg /Ag
E AgCl/Ag E
o
Ag /Ag
0.059
1
log
1
[Ag ]
0.059
[Cl ]
log
1
K sp
E AgCl/Ag 0.80
0.059
0.05
log
1
1.8 x 10-10
E AgCl/Ag 0.30 V
CM2142
37
log
2
[Ag ]2 [H2 ]
Ecell E
o
cell
Ecell E
o
Ag /Ag
Ecell E
o
Ag /Ag
0.059
1
0.059
[H ]2
o
log
EH /H
log
2
2
2
[Ag ]
2
[H2 ]
o
H /H2
0.059
1
[H ]2
(log
log
)
2
2
[Ag ]
[H2 ]
SHE, 0 V
Ecell E
o
Ag /Ag
0.059
1
log
1
[Ag ]
WE
CM2142
RE
38
mass of Cr needed
Cr(s)
divide by M
mol of Cr needed
3 mol e-/mol Cr
mol of e- transferred
0.86g
x 3 mol e-
= 0.050 mol e-
52.00 gmol-1
0.050 mol e- (96485 Cmol-1 e-) = 4787 C
charge (C)
12.5 min x 60 s
divide by time
current (A)
CM2142
= 6.4 A
39
Components involved in
Electrolytic Cells
Component
Electrolyte
Electrochemical Solution
Electrodes:
- Working electrode (WE)
- Counter/Secondary/Auxiliary
electrode (CE)
CM2142
40
Potentiostat
i
Working
Electrode
(WE)
Counter
Electrode
(CE)
Pt wire
Satd AgCl
Ag wire
Au wire
Reference
Electrode
(RE)
Salt
bridge
Electrochemical Solution
Analyte, Electrolyte, Solvent
CM2142
41
V = J/C
A = C/s
No analyte
CM2142
42
Measures V or i
2 electrodes system
- Voltaic cells
- Small currents, no CE
- Small V = iRsolution
Applies V or i and
measures the other.
3 Electrode system
- Electrolytic cells
- Large currents
- Large V = iRsolution (e.g. in
non-aqueous solvents)
CM2142
43