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Electro Analytical Chemistry
Electro Analytical Chemistry
Electro-Analytical Chemistry
Preliminaries
Terminology:
Red-ox reaction one species undergoes a loss
of electrons another gains electrons.
eFe(III) + V(II) Fe(II) + V(III)
oxidant reductant
Galvanic Cell
Analytical
Chemistry
Qualitative Analysis
property characteristic
to analyte
i rate of reaction
Ecell G of reaction
G = -nFEcell
Quantitative analysis
property related to
concentration of analyte
i, q
q = quantity of current
=it
=nF
n = #moles electrons
1 mol e- = 96485C = 1F
i
Oxidation
A
reduction
Notation: Cd|Cd+2(aq)||Ag+1(aq)|Ag
phase boundary
i, ampere; A
R resistance,
E, volts, V
i = q/t
q = charge; C
Construction of electrodes:
The electrode is made out of species involved in
the half reaction. If a metal is not involved, Pt
provides electrical connectivity.
Convention
Negative terminal
Left Black
ANODE
Convention
Positive terminal
Right Red
CATHODE
G = -nF Ecell
i = E/R
Negative terminal
COM - Black
M(s)
M+
M+ (aq)
M(s)
M+(aq) + e
if
M(s)
M+
M+ (aq)
M(s)
M+(aq) + e
Electrode Interface :
Ex: Cu/Cu+2(aq)
Electro-chemical potentials of the species Cu+2 ion is
not the same in the two phases, that has not attained
equilibrium. Natural tendency is to equalize the
electrochemical potentials of the two species.
In order to achieve such a state, ion concentration
must change in the two phases at the interface.
Cu(s)
Cu+2(aq) + 2e
IHL
OHL
Bulk
Etest or Eel
Potentiometer
Ecell = ERHS ELHS
measures the potential
difference between
Ecell = Etest ELHS
two electrodes.
Ecell = Etest ESHE
= 0, definition
Potentiometer
pH2=1atm
SHE
Electrode reaction
Li+ + e Li
K+ + e K
.
.
Cs+ + e Cs
.
.
Al3+ + 3e Al
AgI + e Ag + I
2.925
Sn2+ + 2e Sn
2.923
2H+ + 2e H2
2.92
AgBr + e Ag + Br
Electrode reaction
3.045
Ba2+ + 2e Ba
E /V
E /V
0.152 2
0.136
1.67
I3 + 2e 3I
Zn2+ + 2e Zn
0.762 6
Fe3+ + e Fe2+
Ga3+ + 3e Ga
0.529
Hg22+ + 2e 2Hg
+ 0.796 0
0.44
Ag+ + e Ag
+ 0.799 1
0.424
+ 0.911 0
0.042 5
Pd2+ + 2e Pd
+ 0.915
+ 1.358 3
V3+ + e V2+
Ni2+ + e Ni
0.255
Cl2 + 2e 2Cl
0.257
Au3+ + 3e Au
Reduction assumed
To occur at test electrode
If so Eoel = positive
+ 0.771
.
Cd2+ + 2e Cd
E+
+ 0.536
Cr3+ + e Cr2+
V>0
+ 0.071 1
Fe2+ + 2e Fe
E-
0 exactly
+ 1.52
a=1
Hg(EDTA)-2(a=1), EDTA(a=1)/Hg
RT
ln Qel
nF
@ 25o C; volts
RT
ln Qel
nF
2
8
4
4 / Mn
5 F aMnO aH
4
0
Ecell Ecell
a 4
RT aHg aEDTA4
RT
ln
Eel0
ln EDTA
2F
aHgEDTA2
2 F aHgEDTA2
Calculation of E0cell
MnO4- +8H+ +5 Fe+2 = Mn+2 + 5Fe+3 + 4H2O
Electrode
Elect Pot
Reaction Pot
Fe 2 Fe 3 e
0
Fe3 / Fe2
0
MnO4 / Mn 2
E
-
0
MnO4 / Mn 2
Tabulated
MnO4 8 H 5e Mn 2 4 H 2O
0
Fe3 / Fe2
E0+
RT
ln Qrxn
nF
0
Ecell Ecell
E0-
0
Ecell Ecell
0
Ecell Ecell
RT
ln Qrxn
nF
5
aMn2 aFe
3
RT
ln
8
5
5 F aMnO aH aFe
2
4
RT
ln Qrxn
nF
5
aMn2 aFe
3
RT
ln
8
5
5 F aMnO aH aFe
2
4
Ag/AgCl(s), HCl(aq)
Pb/PbF2(s), HF(aq)
0
Eel E AgCl
/ Ag
0.05916
log aCl
1
Ag+(aq) + e = Ag(s)
0
Eel E Ag
/ Ag
K
0.05916
1
0.05916
0
log
E Ag
log sp , AgCl
/ Ag
1
a Ag
1
aCl
0
Eel EPbF
2 / Pb
0.05916
log aF2
2
Pb+2(aq) + 2e = Pb(s)
0
Eel EPb
2 / Pb
K sp , PbF 2
0.05916
1
0.05916
0
log
EPb
log
2 / Pb
2
aPb
2
aF2
Not a viable
cell configuration.
Zn
ZnCl2 (aq)
Cu
Electrode Interface :
Silver/silver chloride:
AgCl(s) +e- = Ag(s) + Cl- (aq)
Calomel:
Hg2Cl2(s) + 2e- = 2Hg + 2Cl-(aq)
Potential @ 25
vs. SHE vs. SCE
0.288
0.210
0.047
-0.032
0.205
0.199
0.209
0.197
-0.039
-0.045
-0.035
-0.047
Hg
Hg2Cl2(s)
KCl(s)
frit
Calomel:
Hg2Cl2(s) + 2e- = 2Hg + 2Cl-(aq)
Mercury/mercurous sulfate:
Hg2SO4 (s) + 2e- = 2Hg + SO4-2 (aq)
Potential @ 25
vs. SHE
vs. SCE
Hg/Hg2Cl2, KCl (0.1M)
Hg/Hg2Cl2, KCl (1M)
NCE (Normal Calomel)
Hg/Hg2Cl2, KCl (3.5M)
Hg/Hg2Cl2, KCl (sat'd)
SCE (Sat'd Calomel)
Hg/Hg2Cl2, NaCl (sat'd)
SSCE
0.334
0.280
Potential @ 25
0.0925
0.0389
0.250
0.006
0.241
0.2360
-0.0052
vs. SHE
vs. SCE
0.682
0.441
0.674
0.430
Hg/Hg2SO4, K2SO4(sat'd)
0.64
0.40