Beruflich Dokumente
Kultur Dokumente
Prof. K. A. S. Pathiratne
Department of Chemistry
University of Kelaniya
Basic Setup
A). An electrochemical cell of the type below must
be constructed
Potentiometer or
a digital
voltmeter
Reference
electrode
Indicator
electrode
Analyte solution (electrolyte)
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POTENTIOMETRY
Key Components:
Reference electrode
Indicator electrode (e.g. pH electrode, F- electrode,
etc.)
Solution containing analyte
Potentiometer to measure e.m.f. of the cell
Oxidizable / reducible species as analyte
B). Note:
1. Analyte is in the electrolytic solution
2. One of the two electrodes used must be a reference
electrode
eg. Ag(s) / AgCl(s) / KCl(aq)
Hg(l) / Hg2Cl2(s) / KCl(aq)
3. The other electrode should be an indicator electrode
C). e.m.f. of the cell, i.e. cell potential when no current flow
must be measured.
A potentiometer or a digital voltmeter with a high
internal resistance must be used.
Requirement: Cell current should be zero
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E ref
E LJ
E ind
Salt bridge
Ag
Indicator electrode
AgCl
Analyte solution
(electrolyte)
Reference electrode
The potential of the electrode does not depend on the
concentration of analyte. It is a constant.
Also,
1. Electrode must be rugged
2. Easy to assemble
3. maintain a constant potential while passing a small
current.
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Hg2Cl2 (s) + 2e
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E
SCE
= E0 + RT ln [Hg2Cl2(s)]
; Nernst equation for the
2F [Hg(l)]2 [Cl-(aq)]2 above equilibrium
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E SCE = E0 - RT ln [Cl-(aq)]
F
Depends only on [Cl- ].
Use 1 M or Saturated KCl. Therefore its potential
remains constant.
E SCE = + 0.244 V at 25 0C.
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AgCl(s) + e
E = E0 AgCl/Cl- + RT ln
F
Ag(s) + Cl-(aq)
[AgCl]
[Ag] [Cl-]
E Ag = E0 + RT ln 1
F
[Cl-]
Ag wire
AgCl, KCl
AgCl precipitate
Junction 1
Junction 2
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Indicator Electrode
Ideally it must respond to changes in concentration of an
analyte or group of analytes rapidly and reproducibly.
No indicator electrode is absolutely specific and behave as
above.
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Metallic electrodes
Indicator Electrode
Membrane electrodes
Metal Electrodes
Membrane Electrodes
Ion selective electrodes (ISE)
Molecular selective electrodes (MSE)
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Mn+(aq) + ne
M(s)
M(s)
This is an oxidation / reduction
equilibrium
Mn+ (aq)
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Nernst equation:
E = E0 Mn+/ M + RT log
nF
a Mn+
aM
a = I C
a = activity
I = activity coefficient
C = concentration
I varies with the ionic strength of the medium
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E ind = Eo - RT pM
nF
Where, pM = - log10 aMn+
E ind
Slope = - RT = - 0.059
n
nF
pM
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n
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In neutral solutions
Cu2+ / Cu
Bi3+ / Bi
Zn2+ / Zn
Tl+ / Tl
Cd2+ / Cd
Pb2+ / Pb
In deaerated solutions
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e.g.
AgCl(s) + e
Ag(s) + Cl-(aq) ;
EoAgCl = 0.222 V
pCl-
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Redox electrodes
An inert metallic conductor,
eg. Pt, Au, Pb or Carbon
E = EoCe4+/Ce3+ + RT log a Ce 4+
a Ce 3+
F
Good for redox titrations.
Its potential depends on the ratio of the concentrations
of ion at 2 oxidation states.
Useful for redox titrations of transition metals
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Membrane Electrodes
Also called p-ion electrodes
Fundamentally different from metal electrodes both in
design and in principle.
Two types of membrane electrodes:
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(III). Internal
reference
electrode
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Internal reference
electrode- Ag wire
Internal std
solution [1 M HCl]
AgCl coating
H+ sensitive glass
membrane
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Schematic representation
reference electrode 2
External soln
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E glass = L - 0.059 pH
L combination of three constants (Not standard electrode potential)
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ERRORS
1. Alkaline error
In basic solutions:
glass electrode respond to alkali metal ions (Na+) in
addition to H+
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Where:
~ 1
ax = activity of the ion to be determined
ay = activity of any interfering ion
kxy = selectivity coefficient
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Kxy =
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Ag wire
Ag/AgCl electrode
AgCl coating
Crystalline membrane
Mechanism of operation
F- actually move from one side of the membrane to the
other side by occupying vacant sites present in EuF2 sites.
1M
103
HF
~8
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Cl-, Br-, I- , SCN-, CN- , S2Crystals of AgCl, AgBr, AgI, Ag2S for Cl-, Br-, I- and
S2- respectively
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Cell
External reference
electrode
0.1 M KCl with weak
bicarbonate buffer
Spaces
0.1 M HCl
Ag
AgCl
Membrane
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Error ~ 0.1%
Digital voltmeters with 1011
available
Potentiometric Methods
Direct potentiometry
Reference electrode - ANODE
Indicator electrode - CATHODE
Eind = L - 0.0592 px
n
L = standard formal electrode potential for metal electrode
L = some of several constants for membrane electrodes
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Slope = - 0.0592
n
px
Slope = 0.0592
n
K, intercept
pA
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p (activity / concentration)
To overcome,
1. Use the potential vs. concentration calibration curve
(Called Empirical Calibration Curve ). The ionic strength of
the standards and the analyte must be the same. However,
this matching is difficult.
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or
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