CHAPTER

9
Theory of Potentiometry and its
applications
 Syllabus
Topics to be Covered
1. Electrochemical cell, Cell representation, Nernst equation, Formal
potential, Liquid junction potential
2. Reference electrode
3. Indicator electrodes: Metallic indicator electrode
4. Glass membrane electrodes for pH measurement
5 Liquid membrane and Crystalline membrane electrodes
6. Direct potentiometric measurements, Potentiometric titrations.
 General principle about the Electrochemical Cell
• Device : either converts chemical energy into electrical energy or vice
versa.
• Consists of two electrodes (cathode and anode) which are dipped in
separate/ common electrolyte.
• The redox process occurs on the surface of the electrodes.
• Oxidation reaction occurs at the anode and Reduction reaction occurs at
the cathode
Some of the common oxidation and reduction reactions
• Oxidation – reactions Reduction –reactions
• Cu(s) Cu2+ + 2e- Ag+ + e- Ag(s)
• 2Cl - Cl2(g) + 2e- Fe3+ + e- Fe2+
• Fe2+ Fe3+ + e- AgCl(S) + e- Ag(s) + Cl-
• H2 2H+ + 2e- NO3- +10H+ + 8e- NH4++
3H2O(l)3

Terms in potentiometry:
• Galvanic cell: An electrochemical cell• Salt bridge: It is U shaped tube
where redox reaction occurs
spontaneously on the surface of
electrodes producing the external
voltage. Some examples are
– (a) Cu/Ag cell. E0 = 0.46V.
– (b) Zn/ Cu cell. E0 = 1.10V.
Where E0 = standard cell potential.
• Electrolytic cell: An electrochemical
cell where externally supplied voltage
(electricity) brings to cause the redox
reaction.
• Differences:
o About spontaneity of the reaction.
o Direction of energy conversion
o Sign of Cell potential (positive and
negative).
o Necessity of salt bridge.
o Charge on the electrodes. etc..
(generally) which is filled with inert
electrolytes trapped in the gelatinous
substance (agar-agar) with two of its
ends dipping in the electrolytes of two
half cells constituting the galvanic cell.
Its major functions are,
– Provides internal connections
between two half cells (path for
migration of ions).
– To make electrolytes of two half
cells electrically neutral.
– Prevent the sudden mixing of two
electrolyte solutions.
– Minimizes the magnitude of
junction potential. e.t.c.
• Half cell potential (single electrode potential)
 The half cell potential is the reduction potential as compared
to the reduction potential of the standard hydrogen
electrode.
 STP: Standard half cell potential is the potential at the
standard condition (electrolyte of 1M concentration, 25oc
temperature, most stable electrode and gases at 1 atm.
pressure).
• Cell potential:
– The thermodynamical cell potential is the difference of the
reduction potential of the two half cells.
• Ecell = Ecathode – Eanode. (Reduction potential: cathode –anode)
 It is the driving force, causes the spontaneous redox reaction
to occur.
 Some conventions:
 Anode lies at the left (oxidation occurs) and cathode at the right (reduction occurs).
 Vertical line represents interfaces between electrode, electrolyte and salt bridge.
 Concentrations of electrolytes are mentioned in the bracket.
 The inert electrodes are separated by comma. For example,
Cu/Ag cell: Cu | Cu2+(0.02M) | | Ag+(0.02M) | Ag
 Cell potential is : Ecell = ER – EL.
 Can also be calculated either applying Nernst equation directly

 Nernst Equation:
𝐜 𝐝
•For the redox reacxtion: 𝟎 𝟐.𝟑 𝐑𝐓 [𝐂 ] [ 𝐃 ]
∆ 𝐄=∆ 𝐄 − 𝐥𝐨𝐠 𝐚 𝐛
aA + bB cC + dD 𝐧𝐅 [𝐀 ] [𝐁]
 Cell reaction is a charge balanced equation (it is sum of two half cell reactions. For
Net reaction:
Oxidation Half: Cu(s)  Cu 2+ + 2e - E0 = 0.337 V Cu(s) + 2Ag+  Cu 2+ + 2Ag(s)
Reduction Half: Ag+ + e -  Ag(s)}  2 E0 = 0.799 V
Net Cell reaction: Cu(s) + 2Ag+  Cu 2+ + 2Ag(s), E0 = 0.799 – 0.337 = 0.462 V
 Liquid Junction Potential (EJ)

• It is a small potential (mV) developed across the interface (may be

porous partition) between the two solution possessing different
electrolyte composition.
• Junction potential is developed due to different diffusion rate of ions
through the separating medium, like salt bridge.
Fig. Representation of liquid-junction potential.

More examples: Ej(mV)

0.1M KCl||0.1M NaCl +6.4
3.5M KCl||0.1M NaCl +0.2
0.1M KCl||0.1M HCl -27.0
The flux of the migration of
3.5M KCl||0.1M NaOH +2.1
this H+ is much greater than
3.5M KCl||1M NaCl +10.5
Cl-, and determines Ej.

Ej =

• Junction potential puts a fundamental limitation on the accuracy of

direct potentiometric measurements.
• It could be minimized using high concentration of a salt with equal
mobilities of cation and anion in the salt bridge, e.g., saturated KCl.
 Formal potential (Eo|)/conditional electrode potential
• The formal potential Eo| of the (redox couple) is the electrode potential of the
half cell with respect to SHE measured under condition such that the ratio of
analytical concentration of reactants and products as they appear in the Nernst
equation is exactly unity and the molar concentrations of other species in the
system (buffers, acids or whatever) are all carefully specified.
 Eo = 0.771V is standard electrode potential.
• Fe + e
3+ -
Fe 2+
 Eo’ = 0.770V in dilute perchloric acid.
 Eo’ = 0.732V in 1 M perchloric acid.
 Eo’ = 0.700V in 1 M hydrochloric acid.
 Eo’ = 0.68V in 1 M sulphuric acid.

• Ag + e Ag E0 = 0.799; E0|= 0.792 in 1M HClO4, Concentration of Ag

decreases??? in presence of acid.
• Fe(CN)63 + e Fe(CN)64 E0 = 0.36; E0|= 0.72 in 1M HClO4, in presence of
proton, both ions will form hydroferrocyanic acid species H4Fe(CN)6, H3Fe(CN)6.
H4Fe(CN)6 is a weak acid so the ratio Fe(CN)64/ Fe(CN)63 in Nernst equation is
less than one.
• Substitution of formal potential for standard electrode potential in the Nerst
equation yields better agreement between calculated and experimental results.
General principle of Potentiometry
Analytical methods that are based upon potential measurement uses two
electrodes, a reference electrode couples with indicator electrode. The cell
potential is measured using the relation:.

Ecell = Eind – Eref + Ej

We will discuss some of the reference and

some of the indicator electrodes which are
commonly employed in chemical analysis.
Reference electrodes
• The ideal reference electrode is that, whose potential is
accurately known, constant and completely insensitive to
the composition of the analyte solution (solution in which it
is dipped). In addition they should be rugged, easy to
assemble and should maintain constant potential while
passing small currents.
a) known or fixed potential
b) constant response
c) insensitive to composition of solution under study
d) obeys Nernest Equation
e) Reversible reaction
• Reference electrodes are used to calculate the potential of the
indicator electrode with which it is coupled. In that condition
reference electrode is assembled as the anode.
SHE SCE Sat, Ag-AgCl
Standard hydrogen Saturated calomel Saturated Ag-AgCl
Electrode (0V) Electrode (0.244 V) Electrode (0.199V)
 Calomel Reference Electrode (SCE)

 Symbolic representation:
Hg / Hg2Cl2(satd), KCl(xM)//
Electrical lead

 The electrode reaction is:

Hg2Cl2(s) + 2e– 2Hg(l) + 2Cl– (aq) Inner tube connecting
paste of Hg, Hg 2Cl 2,
& saturated KCl
 KCl concentration: 0.1 M, 1 M (S/NCE) and Saturated KCl

4.6 M (SCE). Small hole

 Potential: 0.244V at 25oC. (for SCE) Fritted disk

Commertial saturated calomel electrode Ag electrode
 Limitation: has high temperature coefficient Ag wire
Glass or plastic tubing

Liquid ion
exchanger

5-15 cm long tube

Saturated KCl + (organic)
1 to 2 drops 1M AgNO 3 Aqueous solution
sat'd AgCl + CaCl
0.5-1 cm diameter
2
2+
[Ca ] = a 2
Solid KCl
Porous plug Agar plug saturated Porous plastic membrane
with KCl holding liquid ion exchanger
2+
Liquid membrane electrode for Ca
Half reaction
- -
AgCl(s) + e Ag(s) + Cl (aq)
 Ag /AgCl Reference Electrode
• Arrangement : analogous to SCE
• The electrode representation:
Electrical lead

Ag / AgCl(satd), KCl(x M) //
• The half cell reaction is: Inner tube connecting
paste of Hg, Hg 2Cl 2,
& saturated KCl

AgCl(s) + e– Ag(s) + Cl– (aq) Saturated KCl

Small hole

• Commonly used concn of the KCl Fritted disk

Commertial saturated calomel electrode Ag electrode
Glass or plastic tubing

are 3.5 M and 4.6 M (saturated).

Ag wire

Liquid ion
exchanger

• The potential of saturated Ag/AgCl Saturated KCl +

1 to 2 drops 1M AgNO 3
(organic)
Aqueous solution
sat'd AgCl + CaCl
2+
2

electrode is 0.199V at 25oC.

[Ca ] = a 2
Solid KCl
Porous plug Agar plug saturated Porous plastic membrane
with KCl holding liquid ion exchanger
2+

• Less temperature coefficient and

Liquid membrane electrode for Ca
Half reaction
- -
AgCl(s) + e Ag(s) + Cl (aq)

can be used at temperature

greater then 60oC.
 Indicator electrodes
• Ideally, indicator electrodes are those,
• Whose half cell potential rapidly and reproducibly responds
to the the concentration of analyte ions in the sample.
• In ideal sense,
– Should be: specific/selective/universal, High sensitivity, Larger
dynamic range, Linear response, Reproducible result, Fast response,
Universal, Affordable cost, Easy to handle in the laboratory.
– No such indicators electrodes are available.
– Most of the common electrodes used in potentiometry
are :
 metallic electrodes,
 membrane electrodes and
 ion selective field effect transistors.
Metallic indicators electrodes
• Metal that is dipped into the analyte solution, which directly or
indirectly take part in the redox reaction are metallic indicator
electrodes.
• The potential of the electrode depends on analyte ion
concentration.
These electrodes are basically divided into four types:
Categories Response
(1) I kind metallic • Responds its own cation/s
indicators electrodes:
(2) II kind metallic • Responds to anions (that forms
indicators electrodes: sparingly soluble ppt or complex ).
(3) III kind metallic • Rresponds other cations (there is
indicators electrodes: certain condition)
(4) Inert metallic • Metal in the electrode has no any
indicators electrodes direct/indirect relation to anion or cation, but
responds potential accordingly to analyte
concentration.
 Electrodes of First Kind
• A pure metal which reacts reversibly with its own cation in the solution so the
electrode potential is governed by the activity of its ion in the solution is first kind
metallic indicator electrode:
• Look, general expression and example for it here:

Fig: First Kind metallic indicator

electrode potential as a function of
p-ion concentration of analyte.
Few Limitations
• Do not respond the single cation, For example Cu2+ determination is interfered by Ag+.
• Many electrodes Zn, Cd are easily attacked by acid (used in neutral or basic solution).
• Some metals Hg, Ag are easily oxidized so only de-aerated solution is to be used.
• Hard metals like Fe, Cr, Ni, Co do not give reproducible potential
Some commonly used metallic electrodes are: Ag/Ag +, Hg/Hg22+ in neutral solution and
Cu/Cu2+, Zn/Zn2+, Cd/Cd2+, Bi/Bi2+, Tl/Tl+, Pb/Pb2+ in deaerated solution.
 Electrodes of second kind
• The metal which respond anion concentration
• Anion must form sparingly soluble ppt. or complex with the cation of the metal
• There is existence of two equilibria: (a) Redox, and (b) Dissociation.

This example include the precipitation equilibria. If Ag- electrode is considered:

1. Ag wire coated with thin layer of AgCl
Also,
Can respond Cl- ion concentration

= 0.222 -

Fig: Second Kind metallic indicator electrode potential

as a function of p-ion concentration of analyte anion.
 This example include the complex equilibria.
2. Hg – electrode to respond EDTA anion of the (Y2-).
• If small amount of HgY2- is added in the solution containing Y4- . Some of
stable Hg – EDTA complex under go reduction,
Consider Hg – electrode Hg2+ + 2e- = Hg

Y4-,HgY2- Also,
Hg
+
= 0.21 - = K +
 Electrodes of the third kind
• Metallic electrodes, can respond concentration of other cations. Ca2+, Y4-
• Potential vs concentration Relation is similar to electrode of first kind. ,HgY2-
• There is: a redox equilibria and two more dissociation equilibria. Hg
Mercury electrode to respond Ca2+ concentration +
Mercury electrode is dipped in a solution saturated with Hg-chelate of EDTA.
Analyte, Ca2+ ions in solution also forms the complex with the same chelate Y 4-.
But this must be less stable than Hg-complex. [Kf (CaY2-) = 5 X 1010].
If Hg electrode is considered , Hg 2   2e -  Hg
0.0591  1 
E ind  E 0Hg - log 
2 
2  [Hg ] 
[HgY 2 - ] 1 K 'f [Y 4 - ]
also, K 'f   
[Hg 2  ][Y 4 - ] [Hg 2  ] [HgY 2 - ]
[CaY 2 - ] [CaY 2 - ] 1
also, K 'f'  2
 [Y 4 - ]  
[Ca ][Y ] 4-
K 'f' [Ca 2  ]

0.0591  K f 
'
4- 
So, E ind  E 0
- log  [Y ]
Hg
2  [HgY 2 - ] 
 
0.0591  K f 1 
'
[CaY 2 - ]
E 0
- log  
Hg
2  [HgY ]
2- ''
Kf [Ca 2  ] 

0.0591  K f  0.0591  1
'
[CaY 2 - ] 
 E 0Hg - log - log 
 [Ca 2  ] [HgY 2 - ] 

2  K ''  2  
 f 
0.0591  6.3  10 21  0.0591  1 [CaY 2 - ] 
 0.854 - log -
10 
log 2
 2- 

2  5  10  2  [Ca ] [HgY ] 
0.0591  1 [CaY 2 - ]  0.0591
 0.53 - log 2
 2- 
  K'  pC a
2  [Ca ] [HgY ]  2
 Inert Metallic Redox Indicator Electrodes:-
• Electrodes made from inert metals (Pt, Au, Pd)
• Used to detect oxidation/reduction potential
• Electrode acts as source and sink for electrons
• Analyte solution contains the soluble oxidized and reduced forms.
• Example: Detection of Ce3+ with Pt electrode

Ce4+ + e- Ce3+

Eind responds to [Ce3+] /[Ce4+]:

Eind = Eo – (0.0592/1) log aCe3+/aCe4+

Problems:
- electron-transfer processes at inert electrodes are frequently not reversible
- do not respond predictably to ½ reactions in tables
Membrane Indicator Electrodes
General
• Typical electrode based on determination of cations or anions by the selective
adsorption of these ions to a membrane surface.
• Often called Ion Selective Electrodes (ISE) or p-ion Electrodes
Desired properties
• Selective reactivity with the analyte (ion of interest)
• Minimal solubility – membrane will not dissolve in solution during
measurement – silica, polymers, low solubility inorganic compounds (AgX) can
be used
• Electrical conductivity membrane must exhibit some electrical conductivity,
albeit small.
Common membrane electrodes: Analyte ions
• Glass membrane

Charge separation
• Liquid membrane
• ++
Crystalline membrane
--
+++++++++++++++++++++
---------------- -
Fig: Selective respond to certain ion will develops a
potential, proportional to analyte concentration.
• Glass Membrane Electrode (pH Measurement)
 glass membrane is used, that preferentially binds H+
 Consist of two reference electrodes
 one SCE outside of membrane/May be Ag/AgCl
 one Ag/AgCl inside membrane
 pH sensing element is glass tip of Ag/AgCl electrode

Fig: Structure of glass membrane electrode

Glass membrane: Structure and Properties
• Glass membrane is composed of 3-dimensional silica
(SiO44–), doped with metal ions.
• The common one is corning 015 glass whose
composition is
Na2O = 22%, CaO = 6% and SiO44- = 72%.
• Glass membrane is hygroscopic: Should go H + ion
exchange reaction with solution on its surface. (look rxn)
• This membrane is conductive.
– Movement (or exchange) of hydrogen and SiO─ Na+ (solid) + H+ (solution) Selective binding
sodium ions conducts electricity in the  of cation (H+) to
hydrated layer (gel layer) and also in the SiO─H+ (solid) + Na+ (solution) glass membrane
interface with the solution.
– Movement of mobile Na +ions conducts
electricity in the dry interior of the glass.
• Ca2+ carries no current (immobile)
– Singly charged cations like Na+, Li+ etc are
mobile
– highly charged cations like Fe3+, Al3+ forms a
stronger ionic bond and are immovable.
• The cations in the interstices balance the
negative charge.
Boundary potential (glass electrode)
• When H+ ion get exchanged with Na+ of the glass it forms silicic acid.
(This exists only in the hydrated layer). E1 E2
Na+Gl– glass + H+soln H+Gl– glass + Na+soln.
Silica Hydrogen ion Silicic acid Sodium IOn

• When the electrode is dipped in solution, the silicic acid of the gel
layer undergo dissociation leaving H + ions in the solution as, (In fact the
dissociation occurs in both sides)
– H+Gl– glass H+ soln1 + Gl– glass1 } 1 for the side towards the analyte solution.
– H+Gl– glass H+soln2 + Gl– glass2 } 2 for side towards the internal reference solution

• As a result the glass layer will be negatively charged and the solution
side possess positive charge.
– The position of the dissociation equilibria is determined by the
hydrogen ion concentration in the solution.
• This charge separation generates potentials E1 and E2.
• The surface where greater dissociation occurs (side with low Eb = E1 – E2
concentration of H+) will be more negative as compared to the other.
• This difference of potential on the two side of the membrane creates
a potential called as the boundary potential. The magnitude of the
potential depends on the ratio of H+ ion in the two solutions.
Eb = E 1 – E 2
 Continued Boundary Potential
• The potential developed on outer and inner
surface of the glass membrane due to the
dissociation can be written in the form of Nerst
equation.
0.0591 a1| 0.0591 a 2|
E1  j1  log E2  j2  log
1 a1 1 a2

• Now, boundary potential is calculated as:

a1
Eb = E1 – E2 = 0.0592 log
a2
• are a1| , and a 2| and j1 and j2 be equal?*
* We consider that the composition
• a2 (activity of H +
in reference solution is constant), of the glass as well as the hydrated
Eb  L'  0.0592 log a1  L'0.0592 pH layers in outer and inner layers are
• Where L’ = - 0.0592 log a2 . identical.

• Thus boundary potential is the measure of hydrogen ion activity of the analyte solution.
Asymmetry potential
• If the activity/concentration of hydrogen in the external analyte solution
is identical to, the internal reference solution boundary potential will be
zero. a1
Eb = E1 – E2 = 0.0592 log a=2 0, where a1 = a2

• On the contrary to this, in practical there there exists a small boundary

potential, which is defined as asymmetry potential.
• The causes of asymmetry potential are unclear, but may be,
– Different strain on the two surfaces of the membrane at the time of
manufacture.
– Mechanical abaration on the outer surface during use.
– Chemical etching on the outer surface due to long use.
– Contamination of outer surface during use.
• The error due to variable asymmetric potential in all membrane
electrodes is eliminated by frequent calibration .
The potential of glass electrode and
Expression for pH (using glass membrane electrode)

Substituting
Beside SCE, the remaining Eb = L| - 0.0592 pH
part of this cell represents
the indicator electrode.
Indicator potential is the
sum of three potentials as

This again shows that glass electrode potential depends on the pH (or
hydrogen ion concentration) of analyte solution.

Ag(s)|AgCl(s)|Cl-(aq)||H+(aq,outside) H+(aq,inside),Cl-(aq)|AgCl(s)|Ag(s)

Outer reference [H+] outside [H+] inside Inner reference

electrode (analyte solution) electrode
 The overall cell potental, when the glass electrode is
assembled to the reference electrode

Using general
principle of Ecell = Eind – Eref + Ej
Potentiometry = L - 0.0592pH – Eref + Ej

E Cell - (L - E SCE  E j ) E Cell - K

pH   
0.0592 0.0592
Alkaliine Error
• When glass electrode measure pH of basic solution (above pH 9); the measured pH will be less than
the true pH. This error is called alkaline error. This negative error is obtained because in basic medium
glass membrane not only monitor the hydrogen ion concentration, but also responds the
concentration of alkali metal ion like Na+, K+, and more.
Among different cations, like H+, Na+, K+, H+ possess the
strongest binding in the hydrated layer of the glass. If the
concentration of other alkali metal ions in the solution is
much higher than hydrogen ion, the situation will be
different. Alkali metal ion replaces the hydrogen ion
as, H+Gl– glass + B+soln B+Gl– glass + H+soln

The exchange equilibrium

|
constant for the
|
process
a1 b1 b1 b1
K ex  On arranging,  K ex 
a1| b1 a1| a1

b1|
Let us assume pH of 11 and [Na ] = 1M ,
+
|
 1011  K ex
a1

• The magnitude of the alkaline error at particular pH

depends upon the composition of glass membrane. Even if K is too small, the ratio
• Using Li+ and Ba++ in place of Na+ and Ca++ enhances
will be large. Which shows that
glass electrode also respond the
both selectivity and the life time of the electrode.
alkali metal ion.
• Graphically the alkaline error can be shown as in fig.
Most of glass exhibit alkali error above pH 9.
Acid Error :
• In the solution below pH of 0.5: positive errors opposite to that of alkaline
error is obtained. This error is called acid error.
• There are many factors contributing this error. Non of them is of prime
important so less importance is given for these factors. This error is not
reproducible and it is shown in curves A and B in figure.
Errors at low pH (Acid
error) can give
readings that are too
high
Exact cause not known
- usually
occurs at pH < 0.5
 Glass electrode for measurement of pH of a solution
• Glass electrode coupled with reference SCE is used for the analysis.

Ag(s)|AgCl(s)|Cl-(aq)||H+(aq,outside) H+(aq,inside),Cl-(aq)|AgCl(s)|Ag(s)

Outer reference [H+] outside [H+] inside Inner reference

electrode (analyte solution) electrode

• Glass electrode is not interfered by strong reductants/oxidants, protein and gases.

• pH of viscous solution, semi-solid fluid can be monitored, (manually or automatically).
• The pH meter of different size and cost are available in the market.
• Electrodes for special application are available:
• Small electrodes: to measure pH of: drop of liquid, tooth cavity, sweat, acidity of the
stomach. Micro electrode can even measure pH of living cell.
 DIRECT POTENTIOMETRY (General Equations)
• The activity of cations/anions can be determined in a single step.

First the indicator electrode is coupled to reference electrode.

For the cell: Ref. | Salt. | Analyte soln | Ind.
Electrode Bridge Electrode
• The cell potential is : Ecell = Eind – Eref+ Ej Intercept = K For cations

- 0.0592
Slope =
• If the indicator electrode response the cation Ecell n

concentration, The indicator electrode

potential can0.0592
be written as 0.0952
Eind  L  log a X  L  pX pX
n n

E cell - (E j  E ref  L)
pX  - loga X  
• Combining above equations 0.0592 / n
E -K
  cell
0.0592 / n
0.0592
Ecell K pX
n
• If the indicator electrode response the anion
concentration, The indicator electrode 0.0592
potential can be written as Eind  L pA
• Then the cell potential
n
Ecell = Eind – Eref 0+.0592
Ej
 L pA  Eref  E j For anions
n
ECell  ( L  Eref  E j ) Ecell 0.0592
pA  Slope =
n
0.0592 / n Intercept = K

• For the response of anion pA

E -K
pA  cell 0.0592
0.0592 / n Ecell K pA
n
1. Prepare a number of standard solutions for calibration curve.
i. Simple calibration curve / Standard addition method is used.
ii. Eliminate constant in mathematical expression & determine analyte ion concn.
2. Ionic composition of standards is matched to that of analyte by
1. Swamp sample and standard with inert electrolyte to keep ionic strength constant
2. TISAB (Total Ionic Strength Adjustment Buffer) = controls ionic strength and
pH of samples and standards in ISE measurements
Potentiometric Measurement

(a) Calibration Curve Method

(b) Standard – Addition Method

The electrode Calibration method K includes [Ej, Easy etc].
• The general equation for the direct potentiometry is
E cell - K
pX  
0.0592 / n
• But, electrode calibration method assumes that magnitude of K remains
unchanged when standard solution is replaced by the analyte solution.
• The method of experimental determination of K before calculating pX or pA, is
defined as electrode calibration.
• Is done using standard solutions. two standard solutions whose ionic strength lie on
the two side of the ionic strength of the analyte solution are used to determine K.
• In case of membrane electrode calibration should be done frequently due to the presence of the time
dependent asymmetric potential.

Magnitude Ej depends on the composition of

the electrolyte /whose exact magnitude
cannot be calculated theoretically or from the
experiment.
 Inherent error in electrode calibration
• Assumption that, K remains constant after the calibration may not be true due to
uncertain junction potential. The variation in Ej may be about 1mV.
• This finally introduces error in the final result which cannot be eliminated at all.
E cell -K
• The equation for direct potentiometry for cation is pX  
0.0592 / n
• The change in cation concentration due to change in K can be obtained
by differentiating cation activity w.r.t. K. If we assuming E cell­is constant.
=
1
logA   ln A
ln 10

• The uncertainty in the value of K is

amplified and appears in the activity
measurement due to activity potential
relationship.

That is the relative error of a1(∆a1/a1) is about 4000n times greater than the absolute
error in K. Thus even the small error in K cannot be eliminated or removed.
 Activity versus Concentration
Activity of an ion in the solution refers to the effective
concentration that is directly related to its contribution to
certain physical properties or the chemical properties like
reactivity.

The ion in the solution may under go recombination,

solvolysis, complexation etc. so molar concentration cannot
be considered to be the activity.
For solution with unknown ionic strength or high ionic
strength (Debye Huckel equation is not applicable) activity
cannot be determined from molar concentration.
Fig : Response of a liquid-
The effect of Ca2+ activity and the molarity on the electrode membrane electrode to variations
potential can be observed from the plot of electrode in the concentration and activity of
potential vs activity/molar concentration plot shown in the
calcium ion.
figure.
At high concentration potential vs molar conc n deviates from
linearity. Using the activity straight line with Nernstian slope
(0.0592/2 =0.02958) is observed.

Matching the ionic strength of sample with that of the standard is very difficult or is
impossible. But if ionic strength is not too high, measured excess of inert electrolyte
could be added to both of the solutions.
 • Standard addition method: This is alternative process to least square (Calibration Curve)
fitting. This is more appropriate for the matrix matching between sample and standard solutions.
Measurement is done after adding an different amount of standard to the same replicate volume
of samples. Finally the calibration curve is plotted, to determine sample concentration.
• Assumptions:
o Addition of the standard does not affect the ionic strength and thus the activity coefficient
“f” of the analyte solution.
o Added standard does not significantly change the junction potential.
• Consider the following example::

Q: A cell consisting of a SCE and a Pb-ion electrode develop a potential of 0.4706V

when immersed in 50ml of a sample. Addition of 5ml of 0.02M Pb-solution shifts
the potential to 0.4490V. Calculate the molar concentration of lead in the sample .
E cell - K
We use the formula: pX   log[ X ]  
0.0592 / n Standard – Addition Method

0.4706 - K
 log[ Pb 2 ]   ...............(i)
0.0592 / 2
 50  [ Pb 2 ]  5  0.02  0.449 - K
 log    ...............(ii)
 55  0.0592 / 2
Subtracting (ii) from (i) to eliminate K, and solving for [Pb 2+]

[Pb2+] = 4.08 ×10-4M

 Operational definition of pH

• pH is defined theoretically as: pH = - log[H3O+]

• In lab is calculated using glass membrane electrode. To make
unique way of measurement, recommended method by NIST,
IUPAC and other standard laboratories is:
– Calibration with known buffer. Where pH of standard buffer solution is
measured first. ES - K
pH S  
0.0592
– Second steps is the determination of pH of unknown solution.
EU - K
pH U  
0.0592
– Solving these equation , pH of unknown solution will be
E - ES
pH U  pH S  U
0.0592
This relation is adopted throughout the world as the OPERATIONAL DEFINITION
of pH
 Possible Errors in pH Measurement
 Standards (error in pH at standardization)
- pH measurements cannot be more accurate than standards (±0.01). Again if the glass
electrode is calibrated with the buffer whose estimated pH is not accurate will
introduce more error in the result.
 Junction potential
- If ionic strengths differ between analyte and standard buffer, junction potential will
differ resulting in an error of ±0.01.
 Dehydration of glass
- A dry electrode will not respond to H+ correctly (unstable performance)
 Temperature
- Calibration needs to be done at same temperature of measurement
 Junction Potential Drift (due to low ionic strength of the analyte solution)
- Caused by slow changes in [KCl] and [AgCl] concentration of the SCE
- In place of fritted disk, free diffusion junctions (FDJ) of various kinds can be used.
 Sodium Error (Alkaline error)
- At low [H+], electrode responds to Na+ and the apparent pH is lower than the true pH
 Acid Error
- At high [H+], the measured pH is higher than actual pH, glass is saturated
 Equilibration Time: Takes ~30s to minutes for electrode to equilibrate with solution
 Cleaning: Contaminates on probe will cause reading to drift until properly
cleaned or equilibrated with analyte solution
 Crystalline membrane electrode

• Crystalline membrane is usually made from ionic compound (inorganic),

which is insoluble in analyte solytion.
• Thin film/membrane is prepared by a single crystal or pressing crushed
powder into thin disk membrane or by casting melted crystal to a
desired shape.
• Sometimes membrane is doped (Li+) to increase conductivity
• Membrane is often sensitive to one of the lattice ion
• Operation similar to glass membrane Typical size:
Diameter = 10 mm
– Development of boundary potential
Thickness = 1-2 mm
– Conductance in the membrane Sealed using Teflon of P
– Selective response
– interference
Some of crystalline-membrane electrodes are:
1. AgX membrane: Determination of X-
2. Ag2S membrane: Determination of S-2
3. Cu2S membrane: Determination of Cu2+
4. LaF3 membrane: Determination of F-
 1. F- Selective Electrode
• LaF3 is an ideal membrane material.
• LaF3 is doped with EuF2 to increase conductivity.
• Eu2+ has less charge than the La3+, so an
anion vacancy occurs for every Eu2+.
• Potential is developed at two interfaces of the
membrane from the dissociation/ recombination
reaction: Side of the membrane with
• LaF3  LaF2+ + F- lower aF- becomes positive
relative to the other surface:
Eind = L + 0.0592 pF Recombination
Solid Solution
(membrane surface)

This electrode works between 0–80oc. the

electrode shows good response up to
F- concentration up to 10-6M (0.02ppm).
Interference by OH-, and H+ ions is happening
above pH 8 and below pH 5 respectively.
 Silver - Electrode
Silver
Silverhalide
halideacts
actsas
asthe
themembrane/
membrane/Doped
Dopedwith
withAg
Ag2X.
2X.

Membrane
Membraneisisconstructed
constructedeither
eitherpressing
pressingfine
finepowder
powderor orcutting
cuttingthe
thecrystal.
crystal.
Membrane
Membranehas
haslow
lowmechanical
mechanicalstrength
strengthand
andhigh
highphotoelectric
photoelectriceffect.
effect.

• The method of preparation of the disk

is similar to fluoride electrode.
• The electrode is selective to the Ag+
and X- ions.
• The electrode has low mechanical
strength and high photoelectric effect
that’s why it does not behave ideally.
• The disadvantages are minimized by
mixing Ag2S in the 1:1 molar ratio.
• The conductivity increases due to the
movement of Ag+ ions in the sulphide
matrix. But at this time the electrode
also response to S2- ion.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Liquid Membrane Electrodes
• Thin liquid membrane, composed of water-immiscible liquid ion
exchanger (organic)
• Is filled and supported inside the porous membrane.
• The dissociation of ion exchanger depends on the concentration of
the analyte ion in the solution
• As in GE, partial dissociation of IE develops potential across the
interface between the analyte solution and a liquid ion exchanger
• Membrane has ability to selectively bind ions of interest
• Similar to a pH electrode except that the membrane is an organic
polymer saturated with a liquid ion exchanger
• Used for polyvalent ions as well as some anions
Example:
• Calcium dialkyl phosphate membrane: insoluble in water, but
binds Ca2+ strongly
 Liquid-membrane electrode for Ca2+.

Electrical lead

Outer reservoir
Inner tube connecting
paste of Hg, Hg 2Cl 2,
& saturated KCl

Saturated KCl

Small hole

Fritted disk
Commertial saturated calomel electrode Ag electrode
Glass or plastic tubing
Ag wire

Inner reservoir Liquid ion

exchanger
(organic)
Saturated KCl +
1 to 2 drops 1M AgNO 3 Aqueous solution
sat'd AgCl + CaCl 2
2+
[Ca ] = a 2
Solid KCl ©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
Porous plug Agar plug saturated Porous plastic membrane
with KCl holding liquid ion exchanger
2+
Liquid membrane electrode for Ca
Half reaction
- -
AgCl(s) + e Ag(s) + Cl (aq)

• Ion exchanger is calcium dialkyl phosphate. Dissolved in organic solvent.

di-n-decylphosphate di-n-octylphenylphosphate
• Ion exchangers is fixed into the pores of polyvinyl chloride, membranes due to
the gravity. This disk then serves as the membrane , that separates internal
solution from the reference solution.
 Charge separation and development of Calcium dialkyl phosphate
boundary potential
R-O O O
O-R
[(RO)2POO]2Ca  2(RO2)POO- + Ca2+ P P

R-O O-Ca-O O-R

Organic Organic Solution

(membrane) (membrane surface) (aqueous sample)

• The dissociation equilibrium develops at each

interface of the membrane, produces boundary
potential.
• The side of the membrane with the lower aCa2+
becomes negative relative to the other surface:
0.0592 Ca
Eind L– p
2

 It is sensitive to Ca2+ below up to 5 x 10-7 M

 Sensitivity to Ca2+ is
– 50 times greater than Mg2+
– 1000 times more than K+ and Na+
 Proper working range, pH 5.5 to 11.
 Measures : Ca2+ ion in different samples (organic
and inorganic)
 Liquid Membrane Electrodes for K+

• Sensitive membrane consists of

valinomycin, an antibiotic, a cyclic ether
• This membrane has high affinity to
potassium (104 times more than sodium).
• Useful for : Studying various physiologies
in living body, like transport of natural
signals in the nerves. For this micro
electrodes should be used.

valinomycin (antibiotic i.e.

cyclic ether) in diphenyl ether
as the solvent. It has strong
affinity for potassium.
 Potentiometric Titration
Volumetric analysis, where concentration of an analyte in a sample solution is determined
reacting it with equivalent amount of standard solution, in this method the equivalence point
is observed by sudden change in potential, which is often observed as a sharp peak or
inflection point on a titration curve.
Common examples of potentiometric titrations include acid-base titrations and redox
titrations. pH electrodes are commonly used in acid-base titrations, while redox electrodes
are employed in redox titrations.
Potentiometric titrations offer several advantages
1. Provides more accurate and reliable data than the usual
titration method, using chemical indicators.
2. Useful with colored/turbid/viscous/very dilute solutions
3. To perform titrations in non-aqueous solvents
4. May be automated.
• Involves measurement of the potential of a suitable indicator electrode as a
function of titrant volume
• Suitable indicator electrode is chosen depending upon the nature of analyte.
• Potential is recorded with volume of titrant once the equilibria is established.
• Titrant is introduced in large increment initially but less near to the end point.
• The sharp change in potential at the equivalent point for the small volume of titrant can
detect the end point. (End point is detected from the graph in next slide ……)
 Detecting end point The three common methods:
Potentiometric titration data 0.1 ML Cl-
• First: Normal (sigmoid) curve
with 0.1M AgNO3 method. (plotting potential as the
function of reagent volume)
N V. E E/V 2E/V2  Position of maximum slope predicts
1 5 0.062 the end point.
2 15 0.085 0.002 • Second: differential curve
3 20 0.107 0.004 0.002 method.
4 22 0.123  sharp maxima predicts the end
point.
POTENTIOMETRY • Third: double derivative or
Titration curves analytical curve method.
 zero y value; in the plot can predict
the end point.
1st derivative

2 derivative
nd
 APPLICATIONS OF POTENTIOMETRIC TITRATION:

For different kind of reactions

• AgI get first, it has less
1. PRECIPITATION TITRATION solubility.
• 0.02% of I- remains, at the
start of precipitation of Br-
Titrant: AgNO3 (very • 0.3% Br- remains at the start
common). of precipitation in of Cl-
Electrode system:
(a) Ago/Ag+)
(b) Ag0/AgX/X-) E
(c) Ag2S membrane
Analytes: Halides, sulfides,
mercaptans, phosphates, I- Br- Cl-
oxalates.
mL of AgNO3
Mixture of analyte can also be
determined if the value of Ksp
is significantly different. Fig: Determination of mixture of halides (Cl -, Br-, and I-)
by potentiometric titration
 Complex formation titration
Determination of a mixture of metals
(Ca2+,Cd2+, Bi3+ by EDTA)
• Both metal and membrane can be
used as the indicator electrode pH = 1.2 pH = 4
– first type electrode (Cuo/Cu2+) as indicator pH = 8
electrode.[Determination of Single metal E
e.g. Cu2+ with EDTA]
– second type electrode (Hgo / Bi3+ Cd2+
Hg2y2- / y4-) as indicator electrode Ca2+
[Determination of a mixture of
metals (Ca2+,Cd2+, Bi3+) by EDTA
• The commonly used complexion
agent is EDTA, the reaction is
• Mn+ + H4Y = MY(n-4) + 4H+ . mls of titrant
• This technique is used to calculate At PH 1.5 Bi3+ reacts and the end point is
Ca2+ and Mg2+ in the water¨ detected by sharp change in potential, then
• Bismuth is complexed at pH =2, adjust the pH to 4, only Cd2+ reacts, similarly at
the end point distinct decrease in potential is
cadmium at pH 4(OAc-/HOAc) and
observed. Now raise the pH to 10 with
calcium in basic condition (NH 4+/NH3). ammonia buffer where EDTA forms a stable
complex with Ca2+.
 Neutralization reaction
• Indicator electrode is glass
electrode coupled to SCE. pH
• The titration is feasible if Ka ≥
10-5 CH3COOH
• The analysis of mixture of acid
HCl
or base can also be done if the
value of Ka and Kb are highly mls of titrant
different (about 104 folds or
more)
• The titration curve can also be
used to determine dissociation
constant of weak acids or bases
 Ka from pH at half neutralization
• According to the Henderson’s equation, we have
[Salt]
pH = pKa + log
[Acid]
• Where Ka is the dissociation constant of the acid (pKa =
-logKa).
• At a point acid is half neutralized, we have
[Salt] = [Acid]
• Therefore, pH1/2 = pKa
• Hence the dissociation constant of the acid can be
calculated from the pH at the half neutralization point
i.e. pH1/2
 Oxidation Reduction titration

• In this case platinum or gold electrode used as an

indicator electrode in most of the cases.
• The potential developed depends the activity of the
redox couple.
• In the titration of Fe2+ with Ce4+ the end point can be
calculated. The reduction reactions ere,
Ce4+ + e- = Ce3+ Eo = 1.44V
Fe3+ + e- = Fe2+ Eo = 0.771V
• at the equivalent point the potential obtained from
both should be equal.
Oxidation Reduction titration
E = 1.44 – 0.0592 log [Ce 3+
] Ce4+/Ce3+

[Ce4+]
E
E = 0.771 – 0.0592 log [Fe ]
2+
Fe3+/Fe2+ E =1.44+0.77
[Fe3+] 2
E.p.
mls of titrant
When eq. pt. is reached:
[Ce3+] = [Fe3+] and [Ce4+] = [Fe2+]

The titration of mixture of two or more analyte ion is also possible if Eo differs at least by two volts.
 Some problems

• Q. Calculate the formation constant Kf for Ag(CN)2- [Ag+

+ 2CN- Ag(CN)2-], if the cell
SCE|| Ag(CN)2-(7.5X10-3M), CN-(0.025M)|Ag
develops a potential of -0.625V.{Eo Ag+/Ag = 0.799V}.
• Q: Calculate the dissociation constant of the weak acid
HP if the cell,
SCE|| HP(0.01M), NaP(0.04M)|Pt,H2(1atm)
develops a potential of – 0.591
• Q. The following cell was used for the determination of
pCrO4: SCE||CrO42- (xM), Ag2CrO4 (sat’d)|Ag .
Calculate pCrO4 if the cell potential is -0.386
Some previous end semester questions

•A solution contains the following ions, each at concentration of 1.0M: Zn 2+, H+, Cu2+ and Ag+. Platinum electrodes are inserted and the applied
voltage is increased until electrolysis begins,
1.What product is formed at first and why?
2.If the concentration of Ag+ is reduced to 0.1M then what is the potential of the cell. [3]
3.Which one is strong oxidizing agent? E o Ag+ = 0.8V Eo Cu2+ = 0.34V Eo Zn2+ = -0.76V
•Calculate equilibrium decomposition potential of the cell. Pt,O 2|H+ + H2O + Cu2+|Cu [2] ½ O2 + 2H+ +2e- = H2O Eo = 1.23V
•What is junction potential? Discuss any two application of potentiometric titration. [5]
•For the reaction Fe3+ + e- a Fe2+/ Eo = 0.7V, what should be the molar ratio of Fe 3+ to Fe2+ to prevent the cathode potential becoming more
negative than 0.8V? [2]
•Discuss in brief on glass membrane electrode selective to hydrogen ions. Write its advantages and disadvantages. [3+2]
•Galvanic potential is not enough for an electrolytic reaction to start. Potentiometric titration technique is mostly used than direct
potentiometry during analysis. For an electrolytic reaction to occur, the applied potential should be greater than decomposition potential.
•Differentiate: Indicator electrode and ion selective electrode
First and second derivative curve in potentiometry.
Reference electrode and indicator electrode.
Galvanic and electrolytic cell.
Concentration and activity..
•Define the terms : junction potential, liquid membrane electrode, reference electrode,
indicator potential, alkaline error, boundary potential,
•Write short notes on a. Potentiometric titration. b. Crystalline membrane electrode.
c. glass electrode, d. indicator electrode of the first kind.
e. operational definition of pH. f. liquid membrane electrode for calcium
g. metallic indicator electrode of third kind. h. Advantages of potentiometric titration.
•Give reason: For an electrolytic reaction to occur, the applied potential should be greater than decomposition potential. Glass electrode must
be kept wet.
•A cell is set up as, Zn|Zn 2+(0.1M)||I2, I-(0.01M)|Pt, i. Calculate the emf of the cell E o Zn2+ = -0.76V Eo I2 =0.54V. ii. If 0.01M H+ is added with the
0.01M I- solution, which one will get reduced first in cathode? [2+1]
•Calculate the potential that must be applied to prevent a current from developing in the cell Ag/AgCl, Cl -(0.5M),Cd2+(0.5M)/CdEo AgCl = 0.222V,
Eo Cd = -0.403V.
•In a given reaction, for a electrode of second kind, if activity of Cl - ion is 0.01M, calculate Eind.AgCl (s) = Ag(s) + Cl-(aq) Eo = 0.222V
•What is indicator electrode? Elaborate about first and second kind metallic indicator electrode. [5]
•Explain the errors that affect pH measurement with the glass electrode.
http://ull.chemistry.uakron.edu/analytical/
Potentiometry/
http://chem.ch.huji.ac.il/~eugeniik/instruments/
electrochemical/potentiometric_titrators.htm
http://www.fz-juelich.de/isg/sensorik/bcs-isfet-
e.html
http://www.chemistry.msu.edu/courses/cem333/
Chapter23,potentiometry.PDF