14-6 Cells as chemical probes

It is important to distinguish two types of equilibrium in a galvanic

cell: equilibrium between the two half-cells and equilibrium within
each half cell.

A galvanic cell that can be

used to measure the formation
constant of Hg(EDTA)2Hg2+ + 2e- Hg(l)
Eo = 0.852 V

14-7 Biochemists use E

o

Formal potential: Potential of a half-reaction (relative to

a standard hydrogen electrode) when the formal
concentrations of reactants and products are unity. Any
other conditions (such as pH, ionic strength, and
concentrations of ligands) also must be specified.

Finding the formal potential

Reduction potential of ascorbic

acid, showing its dependence
on pH.
(a) Graph of the function labeled
formal potential.
(b) Experimental polarographic
half-wave reduction potential
of ascorbic acid in a medium of
ionic strength = 0.2 M.
At high pH (>12), the half-wave
potential does not level off to a
slope of 0, as Equation 14-34
predicts. Instead, a hydrolysis
reaction of ascorbic acid
occurs and the chemistry is
more complex.

Example. Cadmium electrode immersed in a solution that is 0.015M in

Cd2+ .
Solution:
Cd2+ + 2e Cd(s) 0 = -0.403

= o -

0.0591
1
log
2
Cd 2+

0.0591
1
= -0.403 log
0.457 V
2
0.0150

Example: Calculate the potential for a platinum electrode

immersed in a solution prepared by saturating a 0.015 M
solution of KBr with Br2
Br2(l) + 2e 2Br-

E0 = 1.065 V

Solution:

Br
0.0591

E= 1.065 log
2
1.0

0.0591
2
E = 1.065 log 0.0150 1.173V
2

Important notes
1. When you multiply a reaction by a coefficient, the potential of
such a reaction does not change!
2. When you subtract or add reactions, the Gibbs energy of those reactions
can always be directly added or subtracted, not their potentials!

Chapter 15: Electrodes and

potentiometry

A few definition
Potentiometry: the use of electrodes to measure
voltages that provide chemical information.
Electroactive species: a substance that can accept or
donate electrons at an electrode.
Indicator electrode: one that develops a potential whose
magnitude depends on the activity of one or more
species in contact with the electrode.
Reference electrode: one that maintains constant
potential against which the potential of another half-cell
may be measured.

15-1 Reference electrodes

A galvanic cell that can monitor

the quotient [Fe2+]/[Fe3+] in the
right half-cell.
The electrode potential
E+ = 0.771 0.05916 log([Fe2+]/[Fe3+])
E- = 0.222 0.05916 log([Cl-])
E = E+ - E-

The Pt wire is the indicator

electrode.

Silver-silver chloride electrode:

a reference electrode.

Reference electrodes

Silver-Silver Chloride
Reference Electrode

Calomel electrode

Figure shows a double-junction

electrode that minimizes
contact between analyte
solution and KCl from the
electrode.

A problem with reference electrodes is that porous plugs become

clogged, thus causing sluggish, unstable electrical response.
Some designs incorporate a free-flowing capillary in place of the
porous plug.
Potential for the solution saturated with KCl (is not 0.222
V):
AgCl(s) + e- Ag(s) + ClEo = -0.197 V

A Hg electrode saturated with KCl is called a saturated calomel

electrode, abbreviated S.C.E. The advantage in using saturated
KCl is that [Cl] does not change if some liquid evaporates.

Ecalomel saturated with KCl 0.241 V

Voltage conversions between different

reference scales

If an electrode has a potential of 0.461 V with

respect to a calomel electrode, what is the
potential with respect to a silver-silver chloride
electrode? What would be the potential with
respect to the standard hydrogen electrode?

15-2 Indicator electrode

Metal electrodes: such as Pt, Au, Ag, etc.

Ion-selective electrodes:
Carbon electrode
Example: Use of Ag and calomel electrodes
to measure [Ag+].

1
0.799 0.0591 log
Ag

0.241

Why do we need double junction

calomel reference electrode here?

15-3 What is a junction potential

Whenever dissimilar electrolyte solutions are in contact, a voltage

difference called the junction potential develops at their interface.
This small voltage (usually a few millivolts) is found at each end of a
salt bridge connecting two half-cells. The junction potential puts a
fundamental limitation on the accuracy of direct potentiometric
measurements.
The steady-state junction potential represents a balance between
the unequal mobilities.

Development of the junction potential

caused by unequal mobilities of Na+ and
Cl.

Junction potential:
An electric potential
that exists at the
junction between two
different electrolyte
solutions or
substances. It arises in
solutions as a result of
unequal rates of
diffusion of different
ions.

A 0.1 M NaCl
solution was placed
in contact with a 0.1
M NaNO3. Which
side of the junction
is positive?

15-4 How ion-selective electrodes

work
Respond selectively to one ion.
Do not involve redox processes.
Features a thin membrane capable of
binding only the intended ion.
The electric potential difference across the
ion-selective membrane is measured with
two reference electrodes.

15-5 pH measurements with a Glass

electrode

The glass electrode used to

measure pH is the most common
ion-selective electrode.

A typical pH combination
electrode, incorporating both
glass and reference electrodes in
one body.

Glass combination electrode with

a silver-silver chloride reference
electrode. The glass electrode is
immersed in a solution of unknown
pH so that the porous plug on the
lower right is below the surface of
the liquid. The two silver
electrodes measure the voltage
across the glass membrane.

The potential difference between inner and outer silver-silver

chloride electrodes depends on the chloride concentration in each
electrode compartment and on the potential difference across the
glass membrane.

Because [Cl] is fixed in each compartment and because [H+] is

fixed on the inside of the glass membrane, the only variable is the
pH of analyte solution outside the glass membrane.

The voltage of the ideal pH electrode changes by 59.16 mV for

every pH-unit change of analyte activity at 25C.

Errors in pH measurement
1.
2.
3.
4.
5.
6.
7.
8.
9.

Standards.
Junction potential
Junction potential drift.
Sodium error.
Acid error.
Equilibration time.
Hydration of glass.
Temperature.
Cleaning.

Ion-selective electrodes-example
Most ion-selective electrodes fall into one of the following classes:
1. Glass membranes for H+ and certain monovalent cations
2. Solid-state electrodes based on inorganic salt crystals
3. Liquid-based electrodes using a hydrophobic polymer membrane
saturated with a hydrophobic liquid ion exchanger
4. Compound electrodes with a species-selective electrode enclosed
by a membrane that is able to separate that species from others or
that generates the species in a chemical reaction.

Ion-selective electrodes-example

Electrodes that respond

selectively to specific analytes
in solution or in the gas phase.

Ion exchange between heparin

and Cl associated with
tetraalkylammonium ions in the
membrane of the ion-selective
electrode.

Rotating ion-selective heparin electrode

Potentiometry with an Oscillating Reaction

The Belousov-Zhabotinskii reaction is a cerium-catalyzed oxidation

of malonic acid by bromate, in which the quotient [Ce3+]/[Ce4+]
oscillates by a factor of 10 to 100.

Oscillation between yellow and colorless is set up in a 300-mL beaker with

the following solutions:
160 mL of 1.5 M H2SO4

40 mL of 2 M malonic acid
30 mL of 0.5 M NaBrO3 (or saturated KBrO3)
4 mL of saturated ceric ammonium sulfate, (Ce(SO4)2 2(NH4)2SO4 2H2O)

Trace b shows two different cycles

superimposed in the same solution.
This unusual event occurred
in a reaction that had been oscillating
normally for about 30 min