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POTENTIOMETRY

Prof. K. A. S. Pathiratne
Department of Chemistry
University of Kelaniya

Basic Setup
A). An electrochemical cell of the type below must
be constructed
Potentiometer or
a digital
voltmeter

Reference
electrode

Indicator

electrode
Analyte solution (electrolyte)
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POTENTIOMETRY
Key Components:
Reference electrode
Indicator electrode (e.g. pH electrode, F- electrode,
etc.)
Solution containing analyte
Potentiometer to measure e.m.f. of the cell
Oxidizable / reducible species as analyte

B). Note:
1. Analyte is in the electrolytic solution
2. One of the two electrodes used must be a reference
electrode
eg. Ag(s) / AgCl(s) / KCl(aq)
Hg(l) / Hg2Cl2(s) / KCl(aq)
3. The other electrode should be an indicator electrode
C). e.m.f. of the cell, i.e. cell potential when no current flow
must be measured.
A potentiometer or a digital voltmeter with a high
internal resistance must be used.
Requirement: Cell current should be zero
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The cell notation


Reference electrode /salt bridge / analyte solution / indicator electrode

E ref

E LJ

E ind

Potentiometer or a digital voltmeter

Salt bridge

Ag
Indicator electrode

AgCl

Analyte solution
(electrolyte)

Sat. KCl solution

E cell = E ind E ref + E LJ

E cell value is measured


E ref value is known.
Experimental conditions are arranged in such a
way to reduce the value of ELJ .Therefore Eind value
can be obtained. It contains the information on the
concentration of the analyte.

Note: By convection reference electrode is taken to be


the anode.

Reference electrode
The potential of the electrode does not depend on the
concentration of analyte. It is a constant.

An ideal reference electrode has a potential which is,


1. Accurately known
2. Constant
3. Completely insensitive to the content in the analyte
solution

Also,
1. Electrode must be rugged
2. Easy to assemble
3. maintain a constant potential while passing a small
current.
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EXAMPLE FOR REFERENCE ELECTRODES


1). Standard hydrogen electrode in principle can be used.
But troublesome.

2). Calomel Electrode (CE) or Saturated Calomel Electrode


(SCE)
3). Silver / Silver Chloride electrode
Either lab made or commercial ones are used.

(a) Saturated Calomel electrode

2Hg (l) + 2Cl-

Hg2Cl2 (s) + 2e

1
E

SCE

= E0 + RT ln [Hg2Cl2(s)]
; Nernst equation for the
2F [Hg(l)]2 [Cl-(aq)]2 above equilibrium
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E SCE = E0 - RT ln [Cl-(aq)]
F
Depends only on [Cl- ].
Use 1 M or Saturated KCl. Therefore its potential
remains constant.
E SCE = + 0.244 V at 25 0C.
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(b) Silver / Silver Chloride electrode

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AgCl(s) + e
E = E0 AgCl/Cl- + RT ln
F

Ag(s) + Cl-(aq)
[AgCl]
[Ag] [Cl-]

E Ag = E0 + RT ln 1
F
[Cl-]

Therefore its potential too remains constant as long as


KCl (Ci-) concentration remains constant.
Note : E0AgCl /Ag = + 0.222 V
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E0 AgCl/Ag = + 0.199 V at 25 oC for saturated KCl (~4.6 M)

Note; These two electrodes can be fabricated in the


laboratory
A salt bridge to avoid mixing of the electrolyte in the
reference electrode with those in the analyte solution.
In a U tube, a salt bridge can be prepared.
5 g of agar, a heteropolysaccharide dissolved by heating in
100 ml water containing 35 g of KCl. Allow to cool to room
temperature. You will get a gel in the tube.
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Double junction reference electrode


Like in a salt bridge, if two junctions are incorporated the
value of ELJ is reduced.

It is a varying quantity which introduces an error.

Ag wire

Outer tube containing


KCl solution or if Clmust not be there, use
KNO3

AgCl, KCl

AgCl precipitate
Junction 1
Junction 2

Two junctions nearly cancels the ELJ

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With a salt bridge or double junction reference electrode,


ELJ reduces to few milli volts.
It gives a fundamental limit to the accuracy of the
potentiometric measurement.

Indicator Electrode
Ideally it must respond to changes in concentration of an
analyte or group of analytes rapidly and reproducibly.
No indicator electrode is absolutely specific and behave as
above.
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Metallic electrodes
Indicator Electrode
Membrane electrodes

Metal Electrodes

Metal electrodes of the 1st kind


Metal electrodes of the 2nd kind
Metal electrodes of the 3rd kind
Redox electrodes

Membrane Electrodes
Ion selective electrodes (ISE)
Molecular selective electrodes (MSE)
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Metal electrodes of the 1st kind


A pure metal is in direct equilibrium with its own cation in
a solution

Mn+(aq) + ne

M(s)

M(s)
This is an oxidation / reduction
equilibrium

Mn+ (aq)

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Nernst equation:

E = E0 Mn+/ M + RT log
nF

a Mn+
aM

Note: Activity must be used in the Nernst expression

a = I C
a = activity
I = activity coefficient
C = concentration
I varies with the ionic strength of the medium
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Usually potential is expressed as a p function.

E ind = Eo - RT pM
nF
Where, pM = - log10 aMn+
E ind

Intercept = EoMn+/ M (Standard electrode potential)

Slope = - RT = - 0.059
n
nF
pM
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Electrodes of the first kind are not widely used due


to several reasons.
1). They respond not only to their own cations, but also to
other ions. e.g. Cu electrode can respond to Ag(I)
2). Zn, Cd can be used only in neutral or basic solutions.
In acidic medium, the metal dissolves.
3). Other metals also oxidized. Therefore, limited only to
deaerated solutions.
4). Certain harder metals (eg. Fe, Cr, Co, Ni), do not
provide reproducible potentials
5). E vs. pM do not give theoretically expected slope of
0.059

n
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Usable first kind electrodes


Ag+ / Ag
Hg22+ / Hg

In neutral solutions

Cu2+ / Cu
Bi3+ / Bi

Zn2+ / Zn
Tl+ / Tl
Cd2+ / Cd
Pb2+ / Pb

In deaerated solutions

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Electrodes of the second kind


Metals not only respond to its own cations, but also to
anions which form stable, but sparingly soluble salts with
the metal ion:
eg. Ag+ forms sparingly soluble AgCl
Pb2+ forms sparingly soluble PbSO4
Hg forms sparingly soluble EDTA Hg
complex

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e.g.
AgCl(s) + e

Ag(s) + Cl-(aq) ;

EoAgCl = 0.222 V

Eind = EoAgCl - 0.059 log aCl-

EoAgCl + 0.059 pClEind


Slope = 0.059
1
Intercept = EoAgCl

pCl-

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Electrodes of the third kind


A metal can respond to the concentration of another metal
ion in which it is in contact
This electrodes are rarely used

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Redox electrodes
An inert metallic conductor,
eg. Pt, Au, Pb or Carbon

Respond to the potential of redox system


eg. Ce(IV) and Ce(III)

E = EoCe4+/Ce3+ + RT log a Ce 4+
a Ce 3+
F
Good for redox titrations.
Its potential depends on the ratio of the concentrations
of ion at 2 oxidation states.
Useful for redox titrations of transition metals
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Membrane Electrodes
Also called p-ion electrodes
Fundamentally different from metal electrodes both in
design and in principle.
Two types of membrane electrodes:

Ion selective electrodes (ISE)


Molecular selective electrodes (MSE)

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Several types of ISE


Glass membranes for H+ and several monovalent cations
Solid state electrodes based on inorganic salt crystals
Liquid based electrodes (A hydrophilic polymer membrane
saturated with hydrophobic ion exchanger)

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Basic components of an ion selective electrode

(III). Internal
reference
electrode

(II). Internal standard solution

(I). Ion sensitive membrane

I. A membrane sensitive only to the ion of interest


II. Standard solution kept inside of the membrane ( internal standard)
III. A reference electrode dipped in the internal standard solution
( internal reference electrode)

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e.g. for ISE : pH electrode


DVM

Internal reference
electrode- Ag wire

Internal std
solution [1 M HCl]
AgCl coating

H+ sensitive glass
membrane

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Schematic representation
reference electrode 2
External soln

SCE // [H3O+]= a1 / Glass / [H3O+]= a2 , [Cl-] = 1.0 M, AgCl (satd) / Ag


membrane
reference
Internal reference solution
electrode 1
Glass electrode

Glass membrane : specific to H+ up to pH ~9

Corning 015 glass


22% Na2O
6% CaO
Excellent specificity to H+ up to a pH limit
72% SiO2

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A potential develops across the membrane, due to an


ion exchange process.

E glass = L - 0.059 pH
L combination of three constants (Not standard electrode potential)

Note : Contribution to L is different from those obtained


for metal electrodes.
i.e.

Junction potentials, potential of external reference,


potential in internal reference and boundary potential

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ERRORS
1. Alkaline error
In basic solutions:
glass electrode respond to alkali metal ions (Na+) in
addition to H+

observed pH < actual pH


Occur above ~ pH 9
2. Acid error

observed pH > actual pH


pH < ~ 0.5
Reasons are not well understood

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Glass electrodes for other cations


Na+, Li+, K+, Cs+, Rb+, Ag+, NH4+ have been developed.
3. Dehydration may cause erratic behavior
4. Variation in junction potential
A fundamental source of uncertainty that for which a
correction can not be applied, which results due to
differences in concentration of standards and samples.
5. Errors in the pH of standard buffer.
Any error in the preparation or any change in the
composition or during storage of buffers can cause error
e.g. Action of bacteria on organic buffer
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6. Errors in low ionic strength solutions

e.g. Lake or stream water

Non reproducible junction potential due to partial


clogging of fitted plug between salt bridge and analyte
solution.
Electrodes with FFJ (Free Flow Junction) are used for
these types of application

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Response of Ion Selective Electrode


nx n
y

E = const RT log [ax + y kX,y ay


nx F

Where:

~ 1
ax = activity of the ion to be determined
ay = activity of any interfering ion
kxy = selectivity coefficient
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Kxy =

Response of electrode to any interfering ion y


Response of electrode to the interested ion x

nx, ny = charges of the ions, x and y respectively

k Na+,H+ 1/36 for pH electrode

Refer the other methods of measuring k x,y ; David Harvey

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Solid State Electrodes


Based on inorganic salt crystals (mostly for anions)
e.g. F- electrode

A crystal of LaF3 doped with EuF2 is used here.


Single crystal e.g. LaF3

Poly crystalline - e.g. Ag2S, etc.

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Ag wire

Ag/AgCl electrode

AgCl coating

0.1 M NaF + 0.1 M NaCl

Crystalline membrane

E = L (0.05916) log aF- - (out side)


1
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Mechanism of operation
F- actually move from one side of the membrane to the
other side by occupying vacant sites present in EuF2 sites.

A charge separation and a potential difference


therefore is created
Range : 10-6 M
KF-, other

1M

103

At high pH ~ 8, response to OH- is high (error)

At low pH ~ 4, H+ + F Usable pH range is pH ~4

HF
~8

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For other examples : Refer Daniel C. Harris, pg. 401

Cl-, Br-, I- , SCN-, CN- , S2Crystals of AgCl, AgBr, AgI, Ag2S for Cl-, Br-, I- and
S2- respectively

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Liquid Based ISE


For polyvalent cations (e.g. Ca2+) and certain anions
(e.g. NO3-)

e.g. For Ca2+ ion , the above electrode can be used.

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Ca 2+ ions outside the membrane form chelate with liquid


ion exchanger and moves across in to the inner tube
establishing a potential
Comparison of a liquid membrane calcium electrode with a
glass electrode

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Liquid ion exchanger, an example is (Ca2+) Ca dialkyl


phosphate is dissolved in an immiscible organic liquid.
E.g. BF4-, NO3-, K+

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Compound electrodes or gas sensing electrodes


Essential features (usual) :
1) Reference electrode (internal)

Cell

2) Specific ion electrode (internal)


Note: If an acidic or basic gas to be determined, a
pH electrode can be used as a specific electrode
3). Electrolyte solution (internal)
4). Gas permeable membrane
This represent a complete cell. Therefore it is
called A PROBE rather than an electrode
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A gas sensing probe (Schematic representation)

The thickness of the membrane ~ 1m


Pore size ~ 1m
Must permit diffusion of gases through the membrane
Selectivity is obtained with the type of membrane
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CO2 Sensing Probe


Consists of an ordinary pH electrode. i. e. Specific ion
electrode is a pH electrode

External reference
electrode
0.1 M KCl with weak
bicarbonate buffer

Spaces

0.1 M HCl

Ag

AgCl

Membrane

Membrane is made out of polyethylene, rubber or teflon

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CO2 diffuses through membrane into the weak buffered KCl

This lowers the pH of the KCl solution

Note: Ion specificity is obtained using the membrane


with different pore sizes

Other molecules (gases) determined :


SO2, NO2, H+, H2S, HCN, NH3, HN3, O2

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Instrument used for measurement of all


potentials
Resistance of a membrane ~ 108 ohm
Internal resistance of a meter should be1000 times larger
than the cell resistance.

Error ~ 0.1%
Digital voltmeters with 1011

1012 are commercially

available

Therefore in place of potentiometers, these digital voltmeters


are used.
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Potentiometric Methods
Direct potentiometry
Reference electrode - ANODE
Indicator electrode - CATHODE

E cell = E ind E ref + E LJ


For cations:

Eind = L - 0.0592 px
n
L = standard formal electrode potential for metal electrode
L = some of several constants for membrane electrodes

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For cations : Ecell = K - 0.0592 px


n
Ecell

Slope = - 0.0592
n

px

Increase in px decreases meter reading


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For anions : Ecell = K + 0.0592 pA


n
Ecell

Slope = 0.0592
n

K, intercept

pA

Increase in pA increases meter reading


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Electrode Calibration Method


Ecell = K 0.0592 pA
n
K can not be computed from theory
K can be determined by measuring Ecell with several
different known concentrations of analyte.

Assumption: K does not vary from standard to standard


and to analyte. i.e. It is the same for ANALYTE and
STANDARDS.

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An inherent error in electrode calibration


In reality, K is not the same for standards and analyte.
(because of the composition differences)
e.g. 1. Junction potential varies due to variation in ionic
strengths between solutions.
2. Activity also varies due to variation in activity coefficients
with solution composition.
Note : This error can not be avoided

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Activity and Concentration


Electrode response is related to activity and not to
concentration.

We are interested in knowing concentration.

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Variation of electrode potential with activity and


concentration
E vs. Activity
E vs. concentration

p (activity / concentration)

Concentration can be converted to activity if activity


coefficients are known. They are rarely known as ionic
strength varies from solution to solution.
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Activity coefficient decreases with increasing concentration


Therefore deviation increases with concentration
For singly charged ions, activity coefficients are less affected
with changes in concentration.

To overcome,
1. Use the potential vs. concentration calibration curve
(Called Empirical Calibration Curve ). The ionic strength of
the standards and the analyte must be the same. However,
this matching is difficult.
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2. When analyte concentration is not large, add a


measured excess of an inert electrolyte to both standards
and samples. This makes ionic strength of standards and
samples nearly the same. The effects due to sample matrix
is negligible under these conditions.
A buffer known as TISAB (Total Ionic Strength Adjusting
Buffer) to control the ionic strength of the samples and the
standards is used to achieve this purpose.
Essentials
Electrodes responds to activity
If the ionic strength is held constant,
Activity Concentration
Therefore, a plot of E vs. concentration - LINEAR
Can be used for analytical purposes.

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Note : Electrode responses to the activity of uncomplexed


ions. Therefore, ligands must be masked or absent.
When matrix is complex or its composition is not known,
use Standard Addition Method.
Standard addition is best if addition increases analyte
concentration by 1.5 to 3 times.
Results are more accurate if average of several results are
taken.

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Note : Three Approaches are used


1). When matrices of unknown and standards are the same,
Use E vs. log concentration curve
2). When composition of the matrix is not known,

a). Use TISAB

or

b). Use standard addition technique


3). For standard addition to be correct, excess of inert
electrolyte must be added to analyte to avoid changes in
ionic strength due to addition of standard.
4). Assume ELJ remain same after standard addition.

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Q: A cell consisting of a SCE and a Pb ISE gave a


potential of 0. 4706 V when immersed in 50 ml
solution. A 5.00 ml addition of 0.02 M Pb2+ solution
changed the potential to 0.449 V.
Calculate the molar concentration of Pb2+ in the sample.

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