ELECTROCHEMISTRY

CHEM 4700

CHAPTER 5

DR. AUGUSTINE OFORI AGYEMAN
Assistant professor of chemistry
Department of natural sciences
Clayton state university
CHAPTER 5

POTENTIOMETRY
- Based on static (zero-current) measurements

- Used to obtain information on the composition of an analyte

- Potential between two electrodes is measured


Applications
- Environmental monitoring
- Clinical diagnostics (blood testing, electrolytes in blood)
- Control of reaction processes
POTENTIOMETRY
- Also known as indicator electrodes

- Respond directly to the analyte

- Used for direct potentiometric measurements

- Selectively binds and measures the activity of one ion
(no redox chemistry)

Examples
pH electrode
Calcium (Ca
2+
) electrode
Chloride (Cl
-
) electrode
ION-SELECTIVE ELECTRODES (ISE)
Advanteages

- Exhibit wide response

- Exhibit wide linear range

- Low cost

- Color or turbidity of analyte does not affect results

- Come in different shapes and sizes
ION-SELECTIVE ELECTRODES (ISE)
- Made from a permselective ion-conducting membrane
(ion-exchange material that allows ions of one electrical
sign to pass through)

- Reference electrode is inbuilt

- Internal solution (solution inside electrode) contains ion of
interest with constant activity

- Ion of interest is also mixed with membrane

- Membrane is nonporous and water insoluble
ION-SELECTIVE ELECTRODES (ISE)
- Responds preferentially to one species in solution
Internal reference
electrode
Ion-selective membrane
Internal (filling)
solution
ION-SELECTIVE ELECTRODES (ISE)
- Selective (preferential) ion is C
+

- Membrane is made of poly(vinyl chloride) (PVC)

- Membrane is impregnated with nonpolar liquid

- Membrane contains ligand L (ion-selective ionophore)

- Membrane contains the complex LC
+

- Membrane contains hydrophobic anion R
-
(ion exchanger)
ION-SELECTIVE ELECTRODES (ISE)
- [C
+
] inside the electrode [C
+
] outside the electrode

- Results in a potential difference across the membrane
Generally (at 25
o
C)
- 10-fold change in activity implies 59/z
i
mV change in E
- z
i
is the charge on the selective ion (negative for anions)
- z
i
= +1 for K
+
, z
i
= +2 for Ca
2+
, z
i
= -2 for CO
3
2-
ION-SELECTIVE ELECTRODES (ISE)
|
|
.
|

\
|
=
+
+
inner
outer
i
] [C
] [C
ln
F z
RT
E
|
|
.
|

\
|
=
+
+
inner
outer
i
o
] [C
] [C
log
z
0.05916
E C, 25 At
- Let c
i
= molarity of C
+

- Activity (a
i
) rather than molarity is measured by ISEs

- Activity is the effective (active) concentration of analyte
(effective concentration decreases due to ionic interactions)

- z
i
= ionic charge ()

a
i
=
i
c
i

where
i
= activity coefficient (between 0 and 1)
ION-SELECTIVE ELECTRODES (ISE)
Debye-Hckel Equation

- Relates activity coefficients to ionic
strength (at 25
o
C)
= size of ion in picometers (1 pm = 10
-12
m)

= ionic strength
/305) ( 1
0.51z
log
2
i
+

=
ION-SELECTIVE ELECTRODES (ISE)
Ionic strength
- A measure of the concentration of all ions in solution
with their charges taken into account
( ) ......... z c z c z c
2
1
z c
2
1

2
i i
2
i i
2
i i
i
2
i i
+ + + = =

c
i
= the concentration of the ith species

Ionic strength of electrolytes
1:1 electrolytes (NaCl) = molarity
2:1 electrolytes (CaCl
2
) = 3 x molarity
3:1 electrolytes (AlCl
3
) = 6 x molarity
2:2 electrolytes (MgSO
4
) = 4 x molarity
ION-SELECTIVE ELECTRODES (ISE)
- For very dilute solutions a
i
c
i

- Activity coefficient decreases as ionic strength increases

For z
i
= 1
- 1 mV change in potential implies 4% change in activity

For z
i
= 2
- 1 mV change in potential implies 8% change in activity

- This is known as Nernstian behavior
ION-SELECTIVE ELECTRODES (ISE)
Selectivity Coefficient (k)

- A measure of the ability of ISE to discriminate against an
interfering ion

- It is assumed that ISEs respond only to ion of interest

- In practice, no electrode responds to only one specific ion

- The lower the value of k the more selective is the electrode

- k = 0 for an ideal electrode (implies no interference)
ION-SELECTIVE ELECTRODES (ISE)
Selectivity Coefficient (k)

For k > 1
- ISE responds better to the interfering ion than to the target ion

For k = 1
- ISE responds similarly to both ions

For k < 1
- ISE responds more selectively to ion of interest
ION-SELECTIVE ELECTRODES (ISE)
Empirical Calibration Plot
P
o
t
e
n
t
i
a
l

(
m
V
)

p[C
+
]
Slope = 59/z
i
mV

z
i
= charge of ion

Called Nernstian slope
- Used to determine the unknown concentration of analytes

- Departure from linearity is observed at low concentrations
ION-SELECTIVE ELECTRODES (ISE)
Three groups of ISEs


- Glass electrodes


- Liquid electrodes


- Solid electrodes
ION-SELECTIVE ELECTRODES (ISE)
GLASS ELECTRODES
- Responsive to univalent cations


- Employs thin ion-selective glass membrane
pH GLASS ELECTRODE
- The most widely used

- For pH measurements (selective ion is H
+
)

- Response is fast, stable, and has broad range

- pH changes by 1 when [H
+
] changes by a factor of 10

- Potential difference is 0.05196 V when
[H
+
] changes by a factor of 10

For a change in pH from 3.00 to 6.00 (3.00 units)
Potential difference = 3.00 x 0.05196 V = 0.177
pH GLASS ELECTRODE
- Thin glass membrane (bulb) consists of SiO
4

- Most common composition is SiO
2
, Na
2
O, and CaO



Glass membrane contains
- dilute HCl solution
- inbuilt reference electrode (Ag wire coated with AgCl)
pH GLASS ELECTRODE
Glass Electrode Response at 25
o
C
(potential across membrane with respect to H
+
)





pH = pH difference between inside and outside of glass bulb

1 (typically ~ 0.98)
(measured by calibrating electrode in solutions of known pH)

K = assymetry potential (system constant, varies with electrodes)
pH (0.05916) K E + =
) (a 0.05916log - K E
H
+
=
pH GLASS ELECTRODE
- Equilibrium establishes across the glass membrane with
respect to H
+
in inner and outer solutions

- This produces the potential, E

- Linearity between pH and potential

- Calibration plot yields slope = 59 mV/pH units

- Electrode is prevented from drying out by storing in aqueous
solution when not in use
pH GLASS ELECTRODE
Sources of Error

- Standards used for calibration
- Junction potential
- Equilibration time
- Alkaline (sodium error)
- Temperature
- Strong acids
- Response to H
+
(hydration effect)
OTHEER GLASS ELECTRODES
Glass Electrodes For Other Cations
K
+
-, NH
4
+
-, Na
+
-selective electrodes
- Mechanism is complex
- Employs aluminosilicate glasses (Na
2
O, Al
2
O
3
, SiO
2
)
- Minimizes interference from H
+
when solution pH > 5



pH Nonglass Electrodes
- Quinhydrone electrode (quinone hydroquinone couple)
- Antimony electrode
LIQUID MEMBRANE ELECTRODES
- Employs water-immiscible substances impregnated in a
polymeric membrane (PVC)

- For direct measurement of polyvalent cations and some anions

- The inner solution is a saturated solution of the target ion

- Hydrophilic complexing agents (e.g. EDTA) are added to inner
solutions to improve detection limits

- Inner wire is Ag/AgCl
Ion-Exchange Electrodes

- The basis is the ability of phosphate ions to form stable
complexes with calcium ions

- Selective towards calcium

- Employs cation-exchanger that has high affinity for calcium ions
(diester of phosphoric acid)

- Inner solution is a saturated solution of calcium chloride

- Cell potential is given by ) log(a
2
0.05916
K E
a
C
+ =
LIQUID MEMBRANE ELECTRODES
Other Ion-Exchange Electrodes

- Have poor selectivity and are limited to pharmaceutical
formulations

Examples
- IEE for polycationic species (polyarginine, protamine)
- IEE for polyanionic species (DNA)
- IEE for detection of commonly abused drugs
(large organic species)
LIQUID MEMBRANE ELECTRODES
Neutral Carrier Electrodes

- Employs neutral carriers such as crown ethers and
cyclic polyesters

- Carriers envelope target ions in their pockets

Used for clinical analysis
- detection of blood electrolytes
- detection alkali and alkaline earth metal cations
LIQUID MEMBRANE ELECTRODES
Neutral Carrier Electrodes

Examples of Carriers
- Monensin for sodium
- Macrocyclic thioethers for Hg and Ag
- Valinomycin for potassium ions
- Calixarene derivatives for lead
- 14-crown-4-ether for lithium
LIQUID MEMBRANE ELECTRODES
Anion-Selective Electrodes

- For sensing organic and inorganic anions

Examples of Anions
- Phosphate
- Salicylate
- Thiocyanate
- Carbonate
LIQUID MEMBRANE ELECTRODES
SOLID-STATE ELECTRODES
- Solid membranes that are selective primarily to anions


Solid-state membrane may be
- single crystals
- polycrystalline pellets
or
- mixed crystals
SOLID-STATE ELECTRODES
Examples
- Most common is fluoride-ion-selective electrode
(limited pH range of 0-8.5)
(OH
-
is the only interfering ion due to similar size and charge)

- Iodide electrode (high selectivity over Br
-
and Cl
-
)

Chloride electrode (suffers interference from Br
-
and I
-
)

Thiocynate (SCN
-
) and cyanide (CN
-
) electrodes
OTHER ELECTRODES
- Coated-wire electrodes (CWE)

- Solid-state electrodes without inner solutions

- Made up of metallic wire or disk conductor (Cu, Ag, Pt)

- Mechanism is not well understood due to lack of
internal reference

- Usually not reproducible

For detection of
amino acids, cocaine, methadone, sodium
APPLICATIONS OF ISEs
- Used as detectors for automated flow analyzers
(flow injection systems)

- High-speed determination of blood electrolytes in hospitals
(H
+
, K
+
, Cl
-
, Ca
2+
, Na
+
)

- For measuring soil samples (NO
3
-
, Cl
-
, Li
+
, Ca
2+
, Mg
2+
)

- Coupling ion chromatography with potentiometric detection

- Micro ISEs as probe tips for SECM

- Column detectors for capillary-zone electrophoresis