Electrochemistry

Electrochemical
Cells
Consists of two electrodes Anode and
Cathode immersed in a suitable
Electrolyte
Electrodes are connected via a
conductor
they permit movement of ions in
solution
electron transfer reactions can
occur
Conduction in a Cell
Galvanic Cells and Electrolytic Cells
Anodes and Cathodes

Assignment:

Chapter 22 Skoog

Cell Diagrams
Conventions
Place the anode on the left side of the
diagram
Place the cathode on the right side of
the diagram
Use a single vertical line ( | ) to
represent the boundary between
different phases, such as between
an electrode and a solution
Use a double vertical line ( || ) to
represent a salt bridge or porous
barrier separating two half-cells
4

An Example Cell Diagram

EOS
Chapter 18: Electrochemistry

Standard Hydrogen
Electrode

In the standard
hydrogen
electrode,
hydrogen gas at
exactly 1 bar
pressure is
bubbled over an
inert platinum
electrode and into
an aqueous
solution with the
EOS
concentration
Chapter 18: Electrochemistry
13
adjusted so that

Standard Electrode
Potentials
A standard electrode potential, Eo, is
based on the tendency for reduction to
occur at the electrode
The cell voltage, called the standard
cell potential (Eocell), is the difference
between the standard potential of the
cathode and that of the anode
Voltaic cells can produce electrical
work
w = n F Ecell
19

EMF and Equm Const of Cell Reactions

Consider the reaction

For a forward reaction free energy should be negative given by

G G RT ln Q
0

Where Q is the activity of the products and

the reactants.
If E is the EMF of the cell in volts and the
cell reaction involves n faradays, ie nF
coulombs, the electrical energy produced is
nFE volt coulombs or joules

nFE G 0 RT ln Q
G 0 RT ln K van ' t Hoffs reaction isotherm
(aC )c (aD ) d
nFE RT ln K RT ln
( a A ) a ( aB ) b

2.303RT
2.303RT
[C ]c [ D]d
E
log K
log
nF
nF
[ A]a [ B ]b

0.0591
0.0591
[C ]c [ D]d
E
log K
log
n
n
[ A]a [ B]b
Standard EMF of a cell is the EMF
when the activity or concentration of
the reactants and products become
unity.

2.

3.
4.

5.
6.
7.

1. a sensing part of electrode, a bulb

made from a specific glass There are
two main glass-forming systems:
silicate matrix based on molecular
network of silicon dioxide (SiO2) with
additions of other metal oxides, such as
Na, K, Li, Al, B, Ca, etc.
chalcogenide matrix based on
molecular network of AsS, AsSe, AsTe.
sometimes the electrode contains a small
amount of AgCl precipitate inside the
glass electrode
internal solution, usually 0.1M HCl for pH
electrodes or 0.1M MCl for pM electrodes
internal electrode, usually
silver chloride electrode or
calomel electrode
body of electrode, made from nonconductive glass or plastics.
reference electrode, usually the same
type as 4
junction with studied solution, usually
made from ceramics or capillary with

Working: When glass is immersed in a solution the potential developed is a

linear function to H+ ion concentration
The potential between HCl/inner glass wall and Ag/AgCl electrode remains
constant, and the variable factor is the potential out side wall and H+ ion
conc
Corning 15 : SiO2 72%, Na2O 22%, CaO 6% could reach up to PH 9, above
which it showed alkaline error
Since the glass also was sensitive towards presense of more sodium, all Na in
the glass was replaced by lithium to get better results
SiO2 63%, Li2O 28%, Cs2O 2% BaO 4% and La2O3 3% could reach up to 12.8
PH with less error.
For PH indicator glass electrode, the glass should be hygroscopic.
H+ + Na+Gl Na+ + HGl
Ag,AgCl|Hcl(0.1M)|glass|Test Solution|Calomel electrode E = K+RT/F ln(aH+) K
is a constant dependent upon the nature of construction of the glass

Ion Selective Electrodes

An Ion-selective electrode (ISE) (also known as a specific ion electrode (SIE)) is a transducer (
sensor) which converts the activity of a specific ion dissolved in a solution into an electrical potential
which can be measured by a voltmeter or pH meter. The voltage is theoretically dependent on the
logarithm of the ionic activity, according to the Nernst equation. The sensing part of the electrode is
usually made as an ion-specific membrane, along with a reference electrode. Ion-selective electrodes
are used in biochemical and biophysical research, where measurements of ionic concentration in an
aqueous solution are required, usually on a real time basis. They are also known as P ion indicators.
The main aspect is the type of membrane which is used
A. Crystalline membranes: single crystals, LaF 3 for FB. Polycrystalline membranes : Ag2S for S2- and Ag+
C. Non Crystalline membranes
1. glass: Silicate Glasses
2. Liquid: Liquid ion exchangers
3. Immobilized polymer or enzyme
4.

Minimal solubility, Stability, Electrical Conductivity, and selective reactivity with analyte

capability of selective binding to analyte ion. Ion exchange, complexation or crystallization.

For PH indicator glass electrode, the glass should be hygroscopic.
H+ + Na+Gl Na+ + HGl
To serve as an indicator for cations, the glass membrane should conduct electricity

Alkalimetal Ion selectivity can be achieved by various concentrations of Na, Al, and Si
oxides
Other Solid membranes:
Iodide selective electrode: AgI dispersed In Silicone rubber monomer and then
carrying out polymerization a glass tubes lower end is sealed with the said
polymer and KI solution is filled in it with a Ag wire.
LaF3 electrode for Flouride ion
Ion exchange membranes: Valinomycine, Dialkyl phosphates, bis thiourea derivatives
Cation Exchangers, neutral Exchangers, Anion Exchangers
Enzyme based electrodes: Urea electrode: Urease is employed to effect hydrolysis of
urea which is further analyzed by glass electrode sensitive to NH4 + ions
Enzyme Pencillinasese to destroy pencillin to produce H+ ions then estimated via
glass electrode
Gas Sensitive electrodes: Gas Dissolved in water and then estimated

Enzymes are immobilized or trapped in polymers, three dimentional

graphite or epoxy matrices or co deposition with metals like Pt or
Rh