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The previous cell would be difficult to use for

many systems.

H2

We would like something that can be placed


in the solution we wish to measure.
The electrodes well be looking at have that
goal in mind but still represent a complete
electrochemical cell when used.

fiber
Hg2Cl2/KCl
Hg
KCl solution
asbestos fiber

Pt black
plate
1 M HCl

25oC

Several approaches have been taken.

Ag
wire
saturated AgCl/KCl

AgCl

Simple metal
Glass membrane
Liquid membrane

Well review representative examples of each.


You can assume that the proper reference
electrode is being used.

A bare metal in contact with a solution of its


cation.
Mn+

+ ne = M(s)

Solid state
Enzyme
Gas sensing

1
[Ag+]

indicating
electrode

1
Eind = Eo - 0.0592 log [ Mn+]
n

A silver wire is dipped into a silver nitrate


solution. A potential of 0.450 V was measured
vs. SCE.
What is [Ag+] for the unknown solution?

pAg = (0.800V-0.244V - Ecell) / 0.0592


Ecell

= 0.450 V

pAg

= (0.800V-0.244V - 0.450V) / 0.0592


= 1.791

[Ag+]

= 1.618 x 10-2 M

pAg = (0.800V-0.244V - Ecell) / 0.0592

[Cl-]
KSPAgCl
[Cl-]
KSPAgCl

For some metals, a good electrode cant be


made or no metal is involved - just ions.
An inert indicating electrode like Pt can be
used. This type of electrode only measures
the ratios of the ions.
No quantitation but suitable for titrations.

Ag wire
0.1N HCl
AgCl
thin
glass
wall

H3O+ partially populates


both the inner and outer
SiO2 surfaces.
The concentration
difference results in a
potential across the
glass membrane.
A special glass is used:

Si
O
Si
H3O+ O

O
Si

Si

Si

Si

Si

Si

Si

O
H3O+
O

Si

22% Na2O, 6% CaO, 72%


SiO2

Similar to a pH electrode except the


membrane is an organic polymer
saturated with a liquid ion exchanger.
Interaction of this exchanger with target
ions results is a potential across the
membrane that can be measured.
The Ca2+ electrode is one of the best
examples.

+
O H3O
+
O H3O
O H3O+

ion exchange
reservoir

Ag/AgCl
reference
electrode

The reservoir forces exchanger into the


membrane. The exchanger forms
complexes with the species of interest.

internal
reference
solution

The results in a
concentration
difference and a
resulting !V that
we can measure.

porous
membrane

sensing
area

Ion

Concentration
Range, M

Major
Interferences

Ca2+
ClNO3ClO4K+

100 - 5 x10-7
100 - 5 x10-6
100 - 7 x10-6
100 - 7 x10-6
100 - 1 x10-7

Pb2+, Fe2+, Ni2+, Hg2+, Sr2+


I-, OH-, SO42I-, ClO4-, ClO3-, Br-, CNI-, ClO3-, Br-, CNCs+, NH4+, Tl+

Ca2+

Ca2+

Ca2+ Ca2+

Membrane

Ag wire
Inert body
Ag2S/AgCl
pellet

The
primary
absorbed
ions result
in a [ ]
gradient
and !V
being
produced.

Primary
absorbed
ions

Ca2+

Ca2+ Ca2+

In this example, a normal pH electrode


is coated with a urease impregnated gel.
Urea will permeate the gel where the
enzyme will attack it, resulting in
the formation of ammonium.
The resulting change in pH can be
measured.

Here, an indicating electrode is placed


into a specific solution.
On the opposite side, there is
a permeable membrane.
Permeation of the target
analyte results in an
equilibrium change that
we can measure.

indicating
electrode

membrane

E
log(conc.)

standard concentration
unknown
concentration