TOPIC 2

POTENTIOMETRIC METHODS OF
ANALYSIS
1. Potentiometry
 Is a measure of the cell potential to yield chemical
information (conc., activity, charge)
 The potential is measured under static conditions (no
current/negligible current flow)
 Is useful for quantitative method (no current flow –
composition remains unchange)
 1.1 Potentiometric measurements
Power
 Potentiometric measurements are made supply

using a potentiometer.
 It is to determine the difference in potential
a c b
between a working or indicator, electrode
and a counter electrode. SW

 Since no significant current flows in

potentiometry, counter electrode functioned i
as a reference potential supplier (known as
reference electrode) Electrochemical
cell
C W

Schematic diagram of a potentiometer:

C=counter electrode; W= working
electrode; SW= slide-wire resistor; T = tap
key; i= galvanometer
 1.1 Potentiometric measurements
1.1.1 Potentiometric electrochemical cells
 Electrochemical cell is divided into two half-
cells
 Each containing an electrode immersed in a
solution containing ions whose concentrations
Cl- KCl K+
determine the electrode’s potential.
Salt bridge
 Seperation of electrods :
 Prevent the redox reaction from occurring 2e- Cl- e-
spontaneously on the surfaces of one of the Zn2+
Ag+
electrode Zn Cl-
Porous frit NO3- Ag
 Prevent short –circuiting EC 0.0167 M ZnCl2 0.100 M AgNO3
 Making the measurement of cell potential Anode Cathode
impossible
 Salt bridge containing an inert electrolyte Schematic diagram of a typical potentiometric
connect the two half cells electrochemical cell
 1.1 Potentiometric measurements
1.1.1 Potentiometric electrochemical cells

 Porous frits:
 Allowing ions to move freely between the half cells and the salt bridge
 Preventing the salt bridge contents from draining into the half cells
 The movement of ions in the salt bridge completes the electric circuit
 Electrode on the left is anode, where oxidation occurs
Zn(s) ↔ Zn2+(aq) + 2e-
 Electrode on the right is cathode, where reduction occurs
Ag+(aq) + e- ↔ Ag (s)
 The EC’s potential is obtain from the reaction;
Zn(s) + 2Ag+(aq) ↔ 2Ag(s) + Zn2+(aq)
 Potentiometric EC are defined such that the indicator electrode is cathode (right
half-cell) and the reference electrode is anode (left half cell)
1.1 Potentiometric measurements
1.1.2 Shorthand notation for electrochemical cells

Zn(s)│ZnCl2(aq, 0.0167M)║AgNO3(aq,0.100M)│Ag(s)

 Shorthand notation uses symbols to indicate the different phases present in

the EC, as well as composition of each phases
 A vertical slash (│) indicates a phase boundary where a potential develops
 A comma (,) separate species in the same phase, or two phases where no
potential develops
 The double vertical slash (║) indicates the salt bridge (the contents normally
not indicated)
 (║) also implies that there is a potential difference between the salt bridge
and each half-cell
 Shorthand cell notations begin with the anode and continue to the cathode.
 1.1 Potentiometric measurements
1.1.3 Potential and concentration – Nernst equation
 The potential of potentiometric EC is given as
Ecell = Ec - Ea
 Where Ec and Ea are reduction potentials for the reactions occurring at the cathode
and anode
 These reduction potentials are a function of the concentrations of those species
responsible for the elactrode potentials, as given by the Nernst equation
RT
E  Eo  ln Q
nF
 Where Eo is the standard-state reduction potential, R is the gas constant, T is the
temperature in Kelvin, n is the number of electrons involved in the reduction
reaction, F is Faraday’s constant, and Q is the reaction quotient.

 Under typical laboratory conditions (temp. of 25oC or 298 K) the Nernst equation
becomes
0.05916
E  Eo  log Q
n

 Where E is given in volts

1.1 Potentiometric measurements
1.1.3 Potential and concentration – Nernst equation

 Eg. Refer to the previous potentiometric EC;

0.05916 1 1
Ea  E o Zn 2 / Zn  Ec  E o Ag  / Ag  0.05916 log
2
log

Zn 2  
Ag  
 The cell potential,

 1   o 2 0.05916 1 
Ecell   E o Ag  / Ag  0.05916 log    E Zn / Zn  

 
[ Ag ]   2
log
Zn 2  

 Substituting known values for the standard-state reduction potentials (from the
standard reduction potential table provided) and the concentrations of Ag+ and
Zn2+, gives a potential for the EC.
 1   0.05916 1 
Ecell    0.7996  0.05916 log     0.7618  log 
 0.100   2 0.0167 

= +1.555 V
1.1 Potentiometric measurements
1.1.3 Potential and concentration – Nernst equation

 Despite the apparent ease of determining an analyte’s concentration using the

Nernts equation, several problems make this approach impractical
1. Standard-state potentials are temperature-dependant, most values list in the
reference tables are for a temperature of 25ºC – maintaining the EC at a
temp of 25ºC or by measuring the standard-state potential at the desired
temperature
2. Nernts eq. is a function of activities, not concentration- resulted in
significant matrix effects shown by cell potential.eg. Standard-state potential
for Fe3+/Fe2+ redox couple is +0.767 V in 1 M HClO4, +0.70 V in 1 M
HCl, and +0.53 in 10 M HCl. The shift towards more negative potentials
with an increasing concentration of HCl is due to chloride’s ability to form
stronger complexes with Fe3+ than Fe2+ - minimise by replacing the standard-
state potential with a matrix-dependent formal potential. (most tables also
include a list of selected formal potentials)
3. Presence of additional potentials in the EC (liquid junction potentials) –
develops at the interface between any two ionic solutions that differ in
composition and differs in the mobility of the ions.
 1.1 Potentiometric measurements
1.1.3 Potential and concentration – liquid junction potentials

 E.g. solutions of 0.1 M HCl and 0.01 M HCl Origin of liquid junction potential between
separated by a porous membrane. solutions of 0.1 M HCl and 0.01 M HCl
 Since the concentration on the left side of
the membrane is greater than that on the
right side of the membrane, there is a net H+
0.1 M HCl 0.01 M HCl
diffusion of H+ and Cl- in the direction of Cl-
arrows.
 The mobility of H+, however is greater than (a)
that for Cl-
 Resulted in: the solution on the right side of
the membrane develops an excess of H+ and
has a positive charge - +
 Simultaneously, the solution on the left side 0.1 M HCl
- +
+ 0.01 M HCl
of the membrane develops a negative charge - +
due to the greater concentration of Cl- - +
 The difference in potential across the (b)
membrane – liquid junction potential Elj Excess of Cl- Excess of H+
 1.1 Potentiometric measurements
1.1.3 Potential and concentration – liquid junction potentials
 The magnitude of the liquid junction potential is determined by the ionic composition
of the solutions on the two sides of the interface and may be as large as 30-40 mV.
 Eg. A liquid junction potential of 33.09 mV has been measured at the interface between
solutions of 0.1 M HCl and 0.1 M NaCl.
 A magnitude of a salt bridge’s liquid junction potential is minimise by:
 Using a salt (eg. KCl for which the mobilities of the cation and anion are
approximately equal)
 Very high concentration of salt
 Nevertheless, a small liquid junction potential, generally of unknown magnitude is
always present.
 The contribution of the liquid junction potential must be included whenever the EC
potential is measured. Ecell=Ec – Ea + Elj
 Since the junction potential is usually of unknown value, it is normally impossible to
directly calculate the analyte’s concentration using Nernts equation. Only quantitative
analytical work is possible using the standardization methods.
 1.2 Reference electrodes
 In potentiometric EC;
 one half cell’s potential provides a known reference potential – anode
 the other half cell’s potential indicates the analyte’s concentration –
cathode
 The PEC shorthand notation is → Reference ║Indicator
 And the cell potential is → Ecell = Eind – Eref + Elj
 Ideal reference electrode;
 Must provide a stable potential so that any change in Ecell is attributed to the
indicator electrode, and therefore to a change in the analyte’s concentration
 Should be easy to make and to use
 Three common types of reference electrodes are:
1. Standard hydrogen electrode
2. Calomel electrodes
3. Silver/silver chloride electrodes
 1.2 Reference electrodes
1.2.1 Standard hydrogen electrode (SHE)

 Is a reference electrode based on the

reduction of H+(aq) to H2(g) at a Pt
electrode; that is,
H+(aq) + e- ↔ ½ H2(g)
 SHE is rarely use for routine analytical
work but importantly use in establishing
the standard-state potentials for other half
reactions
 SHE consist of a Pt electrode immersed in
a solution (H+ activity = 1 and H2 gas
bubbled at 1 atm)
 Conventional salt bridge connects the
SHE to the indicator half cell
 1.2 Reference electrodes
1.2.1 Standard hydrogen electrode (SHE)

 SH notation
Pt (s), H2 (g,1 atm)│H+(aq, a = 1.00) ║
 Standard state potential for the reaction
2H+(aq) + e-↔ H2(g)
 Despites its importance as the
fundamental reference electrode against
which all other potentials are measured,
SHE is rarely used because it is difficult
to prepare and inconvenient to use.
 1.2 Reference electrodes
1.2.2 Calomel electrode (CE)
 Calomel reference electrodes are based on the redox couple
between Hg2Cl2 and Hg (calomel = common name for Hg2Cl2)
Hg2Cl2(s) + 2e- ↔ 2Hg(l) + 2Cl- (aq)
 The Nernst equation for the calomel electrode is

0.05916
E  E o Hg2Cl2 / Hg  log[ Cl  ]2
2

0.05916
 0.2682  log[ Cl  ]2
2

 The potential of a calomel electrode, therefore is determined by

the concentration of Cl-
 1.2 Reference electrodes
1.2.2 Saturated Calomel electrode (SCE)
 SCE is a reference electrode based on the reduction of to Hg
in an aqueous solution saturated with KCl; that is,
 Hg2Cl2(s) + 2e- ↔ 2Hg(l) + 2Cl- (aq)
 SCE is constucted using an aqueous solution saturated with
KCl
 It has a potential at 25ºC of +0.2444 V
 Typical SCE consists of an inner tube, packed with a paste of
Hg, Hg2Cl2, and saturated KCl
 Situated within a second tube filled with a saturated solution
of KCl
 A small hole connect the two tubes and asbestos fiber serves
as a salt bridge to the solution in which the SCE is immersed.
 The stopper in the outer tube may be removed when
additional saturated KCl is needed
 SH notation, Hg (l) │ Hg2Cl2 (sat’d),KCl (aq, sat’d) ║
 1.2 Reference electrodes
1.2.2 Saturated Calomel electrode (SCE)

 SCE advantages : the concentration of Cl- and therefore the potential of

the electrode, remain constant even if the KCl partially evaporates.
 On the other hand, a significant disadvantages of the SCE is; the
solubility of KCl is sensitive to a change in temperature.
 At higher temperature the concentration of Cl- increases, and
electrode’s potential decreases.
 E.g. the potential of SCE at 35ºC is +0.2376 V. electrodes containing
unsaturated solutions of KCl have potentials that are less
temperature-dependent, but experienced a change in potential if the
concentration of KCl increases due to evaporation
 Anoter disadvantages is the elactrodes cannot be used at temperature
above 80ºC.
1.2 Reference electrodes
1.2.3 Silver/silver chloride electrodes (SSCE)
 SSCE is based on the reduction of AgCl to Ag
AgCl(s) + e- ↔ Ag(s) + Cl-(aq)
 As with the SCE , the potential of the Ag/AgCl electrode is determined by the
concentration of Cl- used in its precipitation

E  E o AgCl/ Ag  0.05916 log[ Cl  ]

 0.2223  0.05916 log[ Cl  ]

 When prepared using a saturated solution of KCl, the Ag/AgCl electrode has a
potential of +0.197V at 25C
 Another common Ag/AgCl electrode uses a 3.5 M ssssolution of KCl has a
potential of +0.205 at 25C
 The Ag/AgCl electrode prepared with saturated KCl is more temperature-
sensitive than on prepared with an unsaturated KCl
 1.2 Reference electrodes
1.2.3 Silver/silver chloride electrodes (SSCE)
 A typical Ag/AgCl electrode consists of a silver
wire.
 The end is coated with a thin film of AgCl
 The wire is immersed in a solution that contains
the desired concentration of KCl and that is
saturated with AgCl.
 A porous plug serves as the salt bridge
 SH notation Ag(s) │ AgCl (sat’d),KCl (x M) ║
where x is the KCl concentration
 Compare to the SCE, Ag/AgCl electrode has the
advantage of being useful at higher temperature
 The disadvantage: Ag/AgCl electrode is more
prone to react with solutions to form insoluble
silver complexes that may plug the salt bridge
between the electrode and the solution.