The Nernst Equation

Ox + e-  Red

[Ox] exp( − Eloss / k BT )

= =exp(( E gain − Eloss ) / k BT ) =exp( µc / k BT )
[Red] exp( − E gain / kbT )

Eloss = the energy associated with the loss of an electron

Egain = the energy associated with the gain of an electron

µc = chemical potential of the solution

[Ox]
µc = k BT ln For [Ox]/[Red] = 1, µc = 0 in this equation.
[Red]

[Ox]
For µc ≠ 0 µ= µ c + k BT ln
0
c
[Red]

µc µc0
k T [Ox] RT [Ox] RT [Red]
= + B ln E=
E0 + ln E=
E0 − ln
e e e [Red] F [Red] F [Ox]
 Shorthand Notation for Cells

Anode Cathode

H+ (aq, 1M) + e- 1/2H2 (g, 1 bar)

Ag+ (aq, 1 M) + e- Ag (s)

Ecell = Ecathode – Eanode = Eright – Eleft = E+ - E-

ΔGrxn = -nFEcell = -RTln Keq
 Chapter 15 - Potentiometric Measurements
Emeas α log [x] Reference Electrode (constant E vs. t)
AgCls + e- Ags + Cl- aq Eo = 0.222 V

Reference

All potentiometric measurements are made using two electrodes: (i) an

indicator electrode that responds selectively to the analyte of interest and
(ii) a reference electrode whose potential remains constant independent of
the solution environment.
 Reference Electrode
Calomel electrode

Hg2Cl2(s) + 2e- 2Hg(l) + 2Cl-

Eo = +0.268 V vs. NHE (1 M KCl)

Eo (saturated KCl) = +0.241 V vs. NHE (4M)

E = Eo + 0.0592 V log [Hg22Cl2]-

n [Hg] [Cl ]
E = Eo + 0.0592 V log 1
Reference electrodes n 1 [Cl-]
have a constant E with
time and a potential
that is predictable from
[Hg2Cl2] = [Hg]2 = 1 M (pure substance)
Nernst Eq.
 Potentials on Difference Reference Scales

Standard hydrogen electrode is difficult to prepare and

use in the lab. Often other reference electrodes are used
to measure potentials against.
Applications of Potentiometric Measurements
Simple…….Emeas α Log [analyte]

Biomedical and environmental analysis

Anions

Cations

Some molecules

Dissolved Gases
Ion Selective Electrodes – Common Type of
Potentiometric Measurement

An ISE responds preferentially to

one analyte species in solution.

Difference in concentration of
the selected ion inside and
outside of an electrode produce
a voltage difference across a
membrane.

Membrane must be (i) an ion

conductor but electrical insulator,
(ii) selective for the chemical of
interest (molecule or ion) and (iii)
chemically stable (insoluble).
 Analytical Expression for ISE

Emeas = L + 0.059 V Log [X] Emeas = L - 0.059 V pX

z z
Y = b + mX
 Ion Selective Electrodes

One factor that limits LOD values is leakage of ions from

the high concentration internal solution to the external
side of the membrane. Change the membrane properties
and can lower LODs to 10-12 M!
Most Common ISE – pH Electrode

anode cathode
 Charge Separation Across a Thin Glass
Membrane
Errors – non-linearities
• Incorrectly prepared
standard buffer solutions.
• Sodium error – electrode
responds to Na+ when [H+]
is low.
• Acid error – low pH under
very acidic conditions.
• Poor membrane hydration

Emeas = Eext – E int E = constant + 0.0592 log [H+]

Charge separation = potential difference! E = constant – 0.0592 pH

Fluoride Ion Selective Electrode

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