POTENTIOMETRY

Definition, Principle, Reference and indicator electrodes,

Membrane potentials, Potentiometric titrations
POTENTIOMETRIC ANALYSIS
* Based on potential measurement of electrochemical cells

without any appreciable current

* The use of electrodes to measure voltages from chemical

reactions
 DEFINITIONS
"Measuring the potential or emf of a solution by using the set of indicator electrode and reference
electrode".

Potentiometry is the field of electro analytical chemistry in which potential 1s measured under the

condition of no current flow.

Potentiometry is one of volumetric technique of electro-analytical chemistry.

Potentiometry is the method used in electro analytical chemistry usually to find the concentration
of solute in solution in potentiometric measurement the potential between two electrode is

measured using the high impedance volimeter

 PRINCIPLE
* When a metal strip ts placed in a solution of its own ions there are two possibilities or tendencies:

¥ Metal atoms may dissolve in the solution as posilive ions leaving electrons on the electrode.

¥ Metal tons may take up electrons from electrode and get deposited as neutral atoms

In this way a POTENTIAL DIFFERENCE is setup between electrode and solution .

The potential of an electrochemical cell is measured under static conditions.

*
Because no current, or only a negligible current flows while measuring a solution's potential, its

composition remains unchanged.

For this reason, potentiometry is a useful quantitative method.

 PRINCIPLE (Ctnd...)
E cell -

cell potential under nonstandard conditions (V)

E° = cell
cell potential under standard conditions

¢
R- gas constant, which ts 8.3 (volt-coulomb)/(mol-K)
Nernest equation
T -

temperature (K)

E cell cell
7
(RT/nF) InQ n = number of moles of electrons exchanged in the

electrochemical reaction (mol)

F -

Faraday's constant, 96500 coulombs/mol

Q = reaction quotient
POTENTIOMETRY TIMELINE
M. Cremer
observes the pH lon exchange Introduction of
Beckman Microfabricated
response of thin membranes polymeric
pH meter sensor arrays
glass developed matrices
membranes!
o
/
9011906 1913 |1930- 40's 1960's 1970's |
1990's 2000+

F. Haber
observes that First 4966 LaF, electrode for F
-

the voltage ata Introduction ionophore- 1967 liquid membrane

- Picomolar
glass electrode of the based electrode for Ca** detection
changes with hydrogen electrodes 4969 valinomycin
-
limits
the acidity of electrode electrode for K*
solution (Refs 4
 POTENTIOMETER
Ht is an instrument used to determine the potential differences between a reference electrode and an

indicator electrode. These two electrodes form electro chemical cell that are dipped in solution to

be analyzed.

Measured potential can be used to determine the quantity of analyte in terms of concentration.
 POTENTIOMETER
It is an in rode and an

indicator Reference Indicating solution to

electrode
b e analyz
electrode

The part of ration.

Measured The part
the coll that
of the cell
contains the
that is held
solution we
constant
are Interested
In measuring
 Potentiometric measurements
*
Made by using a potentiometer to determine the difference in potential between a indicator electrode and

a reference electrode,

*
Cathode is the sensing electrode. (right half-cell) potentiometer

salt bridge
¢ Anode is the reference electrode. (left half-cell) anode cathode
KCI

ecll E E,
Where :
E, is the reduction potential at the cathode. in*? porous frits
cl
E, is the reduction potential at the anode. a NO,
 Potentiometric Measurement
* Ionic composition of standards must be the same as that of

analyte to avoid discrepancies ry

Swamp sample and standard with inert electrolyte to keep

¢

ionic strength constant T

Tisaé J
¢
TISAB (Total Ionic Strength Adjustment Buffer)
-

controls
~
ionic strength and pH of samples and standards in ISE
measurements
 TYPES OF POTENTIOMETRY
1) Direct potentiometry ry

2) Potentiometric titrations
fae meted

mi

elecirude

lndicaior clectinde
 DIRECT POTENTIOMETRY
A rapid and convenient method of detecting the activity of cations and anions.
The technique used in this method is a comparison of the potential developed by the indicator
electrode when it is immersed in the solution with that when it is immersed in standard solution of
the analyte

The direct potentiometry is the method which makes use of the single measured electrode potential
to determine the activity of the ion of interest (or concentration of the ton in case of dilute
solution).

This method is widely used for the determination of pH of the solution (using Hydrogen electrode)
or determinations of other ions using different ion-selective electrodes.
 THE CALIBRATION CURVE
METHOD
* It is applied for determination of substance by direct
50
potentiometry. 450

¢ In which we plot potential of the cell Vs a series of 400-

> *°
standard solution of extra grade of the substance to be &

300
determined.
254,
©
Then measure the potential produced when using the 200.

unknown solution and from the calibration curve we 8 7 #6 5 4 a 7 1

p[Fur)
can obtain its concentrations.
EQUATIONS GOVERNING DIRECT
POTENTIOMETRY
*
For direct potentiometric measurements, the potential of a cell can then be expressed in terms of the

potentials developed by the indicator electrode, the reference electrode, and a junction potential,

°
Feet Find
-

E"ref + af

¢ For the cation X"" af 25°C, the electrode response takes the general Nemstian form

0.0592 0.0492
Ema
= pX¥
i} }?
 ~ +L)
= Eva i Eng
Substitution and rearrangement leads to pX =-loga,
4 0.0592/2

The constant terms can be combined to (Eg K) I -

pX =-loga, * =-
give anew constant K, 0.0592/ 0.0592

For an anion A- (£ call A) -

K)
Pp. {=
"0.0892 # 0.0592

When the two equations are solved for

we find that for cations 0.0592
i!

and anions
K+ 0.059? pa
Components of a Potentiometric Cell
* Reference electrode

« Salt bridge

*
Analyte
¢
Indicator electrode
REFERENCE ELECTRODE
* Half-cell with known potential (E,.;)

¢
Left hand electrode (by convention)

Easily assembled
*

hydrogen
* gas m
Rugged
¢ Insensitive to analyte concentration

1 mol
3
om
Reversible and obeys Nernst equation
a Nb
*
mol
H
«
Constant potential
platinum
black
¢
Returns to original potential
electrode
REFERENCE ELECTRODE
* Half-cell with known potential (E,,;)

©
Left hand electrode (by convention)

°
Easily assembled
hydrogen
* Sas m
Rugged
*
Insensitive to analyte concentration
-7
*
Reversible and obeys Nernst equation 1 mol dm
H*(aq)
« Constant potential
plahnum
black
¢
Returns to original potentia!
electrode
INDICATOR ELECTRODE
*
Generates a potential (E,,) that depends on analyte

concentrahen

*
Selective

Rapid and reproducible response

*
 SALT BRIDGE
*
Prevents mixing up of analyte components

*
Generales potential (Ey) = negligible
 ELECTRODES
Reference Electrode Indicator Electrode

1} Standard Hydrogen electrode 1) Metal Electrode

2) Calomel electrode 2) Hydrogen electrode

3) Silver-Silver Chlonde electrode 3) Quinhydrone electrode

4) Glass Membrane Electrode

 ELECTRODE POTENTIAL
Tendency of electrode to lose or gain electrons
¢

¢
Standard Potential

Potential of pure metal when it is dipped in l Molar solution of its own ions at 25°C (298K) is known as
standard Electrode potential.

*
Oxidation Potential

The potential of substance to pet oxidized ts called oxidation potential.

*
Reduction Potential

The potential of substance to pet reduced js called reduction potential.

REFERENCE ELECTRODES
a) Standard Hydrogen Electrode

b) Calomel Reference Electrode

c) Silver/Silver Chloride Reference Electrode

 STANDARD HYDROGEN
ELECTRODE
The standard H, electrode potential ts defined as the potential that is devcloped between the H, gas
adsorbed on the Pt metal and H of lhe solution when the H, gas at a pressure of 760 mm of Hg is in

equilibrium with H of unit concentration

It can be used as Indicator as well as Reference electrode.

It can be consist of platinum foil coated with platinum black and has a wire contacts through a mercury.

This assembly is enclesed in a glass covering.

Hydrogen gas is passed at latmospheric pressure continuously,

(Pt (H, (1 atm), H (1M)

 STANDARD HYDROGEN
ELECTRODE
The standard H, electrode potent a beiween the H, gas

adsorbed on the Pt metal and H™

H te) at
>
of 764 mm of Hg is in
} bar
equilibrium with H of unit concen
1}
it can be used as Indicator as well
a

It can be consist of platinum foil c a ets through a mercury,

2
This assembly is enclosed in a glas
Finely divided
(M) M
Hydrogen gas is passed at latmosp platinum coated
on platinum foil

(Pt (A, (1 atm), HK (1M)

STANDARD HYDROGEN ELECTRODE (Ctnd...)
*
Then electrode is dipped into the standard acid /unknown solution. 4

* All the times surface ofthe electrode and the solution should be

saturated with the gas.

*
potential , Platinum
foil covered
with e
E- E®,,+0.0592 log[H'] -

E°,, -6.0592 pH (pEI- -log [H']) platinum

black
E- -0.0592 pH
std E of H, electrode ,taken as 0 a
STANDARD HYDROGEN ELECTRODE (Ctnd...)
ADVANTAGES DISADVANTAGES
¢
It can be used over the entire pH. ° [t is effected by the presence of oxidizing agent
and reducing agent.
_
*
It can be used as a reference electrode when dipped

with standard acid solution and as a indicator [t is rather difficult to regulate the pressure of H,

electrode when dipped into a sample solution. gas to be exactly § atm throughout the experiment.

° Platinum foil the

It is the primary reference standard against which gets easily poisoned by

the potentials of other electrodes are measured. impurities present in the H, gas and HC} solution.
 SATURATED CALOMEL
ELECTRODE
It consist of inner jacket and outer sleeve

Inner tube has a wire contact with mercury (Hg) and plugged with a mixture of calomel(Hg,Cl,jand KCI.

This is surrounded by an outer sleeve. Tip is filled with Crystals of KCI and porous plug of asbestos.

The space between inner jacket and outer sleeve is filled with saturated KCI/IN KCI/0.1 N KCI.

Potential of the electrode depends on the Concentration of the KC] Solution and Temperature.

Hg.Chi(s}+ 2e- <> 2He (1)+ 2C){aq)

I = 0.2444 at 25°C
 SATURATED CAT. OMEL Wire lead

Pt wire
Hole to allow
It consist of inner jacket drainage through
porous plug
Inner tube has a wire ca gre of calomel(Hg.Cl,)jand KCI.
Hg)
This ts surrounded by a Rig, Hg. Cl.
nd porous plug of asbestos.
+ KCl
The space between inna Glass wool CVIN KCIVO.1 N KCL.
-
Opening
Potential of the electrod Saturated KCI bn and Temperature.
solution
Hp. Cl.(s)+ 2e- <> 2He KCI(s)
Glass wall
I= .2444 at 25°C
Porous plug
(salt bridge)
SATURATED CALOMEL ELECTRODE (Ctnd...)
¢
Specifications of Calomel electrodes

Nu Concentration of Potential vs SHE at 25 °C (V)

KC] H2Cla(s) + 2e Ho**
a
+
Sat Sat + 0.2412.
Normal Sat 10M +
Decinormal Sat 0 M + 0.3337
SATURATED CALOMEL ELECTRODE (Ctnd...)
ADVANTAGES DISADVANTAGES

* Concentration of chloride ions don't change Mostly saturated solution of KC] is used

* some of the solvent get evaporated. Temperature dependent.

*
Generates small junction potential so more Toxic

accurate
 SILVER-SILVER CHLORIDE
ELECTRODE
It is also widely used reference electrode

It is mainly used with Saturated KCI Electrode (KC) electrolyte) but can be used with low concentration

such as ]M KC] and even directly in sea water,

Ag-wire coated electrolytically with AgCl, and dipped into KC]

Potential depends on the concentration of the KC] and temperature.

Ag? AgCl (satd), KC] (satd)//

*
AgCl(s} + o- Apis) Cl(aq)
E 1
-0 199V
SILVER-SILVER CHLORIDE
ELECTRODE (Ctnd...)
Wire lead
Air inlet to allow
electrolyt
slowly thi Grain
Ag AgCl (satd),KCI
| (satd)| |

porous plug
re bent
into d AgCl(s) + e Ag(s)+ Cl(aq)
Aqueous solution
saturated with
KCI and AgCi
AgCl paste
E°=0.199 V
Solid KCl plus
some AgCl
Porous plug for contact
with exlernal solution
(salt bridge)
SILVER-SILVER CHLORIDE ELECTRODE
(Ctnd...)
Advantages: Limitation:
-
*
sometnnes show reactivity
¢
Easy handling

*
cost effective

*
very stable

*
non toxic
INDICATOR ELECTRODES
* Metallic IE

a) Electrodes of the First Kind

b) Electrodes ofthe Second Kind

¢) Inert Metallic Electrodes (for Redox Systems)

*
Membrane IE

a) Glass pHIE

b) Glass IE for other cations

c) Liquid Membrane IE

d} Crystallinc-Membrane IE
*
Gas Sensing Probes
METALLIC INDICATOR
ELECTRODES
 ELECTRODES OF THE FIRST
KIND
¢
Pure metal electrode in direct equilibrium with its cation

¢
Metal is in contact with a solution containing its cation.

M'" (aq) + ne- Mis)

ndicating
electrode

a
0.0592 log
41
 Disadvantages of First Kind Electrodes
™
Not very selective

Ag' interferes with

May be pH dependent

Zn and Cd dissolve in acidic solutions

*
Easily oxidized

Non-reproducible response
ELECTRODES OF THE SECOND
KIND
Respond to anions by forming precipitates or stable complex

A second-order electrode is one that responds to the presence of precipitating or complexing tons.
For example, silver wire could serve as the indicator electrode for chloride.

-ApCl+e
AgCl(s)+e <> Ag(s)+ =40.222V
= 0.0592.
Examples: ing log a _

n
= 44.222 + 0.0592pCl
Ag electrode for C]- determination
ELECTRODES OF A THIRD KIND
A metal electrode, under certain circumstances can be made to respond to a different cation.

CaY? +

Alse known as inert metallic electrodes

The most commonly used indicator electrodes are known as inert. These clectrodes are not
involved in the half-cell reactions of the electrochemical species
 INERT METALLIC (REDOX)
ELECTRODES
Inert conductors thai respond to redox systems

Electron source or sink

An inert metal in contact with a solution containing the soluble oxidized and reduced forms of the redox
half-reaction.

May not be reversible

Examples:
¢
Pt, Au, Pd, C
 MERCURY ELECTRODES
Another important second order electrode used for the measurement of EDTA and its anion Y*, is based
on the response of mercury clectrode in the presence of a small concentration of stable Hg (11) EDTA
complex.

The hali-cell reactions for this electrode process are similar to the one given above and may be written as

HeY
c + 2e ==Hg(1)+ Y-4 (Fe = 0.21 V)

0.0591 [Y*"]
E=0.21 2
log
lHgY
MERCURY ELECTRODES (Ctnd...)
For this electrode system, a small concentration of HgY? is introduced into the analyte solution.

The complex is so stable, that the dissociation to form Hg?" is minimal (K, = 6.3 x 107! for Wg Y* ) and the

concentration of the complex remains constant over a wide range of Y4 .

Hence, the above equation may be simplified as

0.059]
E=K --
Ic
log Y 4

This electrode is largely used in complexometric Utrations using EDTA.

ION SELECTIVE ELECTRODES
Other synonym: Membrane electrodes

Definition: " ISE are known as specific ion electrode, it is a membrane that converts the activity of
a specific 10n dissolved in a solution tmto an electrode potential".

The voltage is theoretically dependent on the negative logerithem of the ionic activity, according to
the Nernest equation.

Consist of a thin membrane separating two solutions ofdifferent ion concentrations

 GLASS MEMBRANE
ELECTRODE
Its most commonly used indicator electrode

it involves lon Exchange reaction

Membrane is made up of chemicaily bonded Na.O, SiO, and Al.O,

The Glass bulb is filled with solution of HCI & KCI, silver acetate coated with AgCl is inserted as

Electrode.
 GLASS MEMBRANE
ELECTRODE
« Jts most cor

¢
It involves |

« Membrane |

* The Glass 1
Electrade m with AgCl is inserted as

Electrode. Electrode 2

Af
fae' Sampie

Than glass membrane

GLASS pH ELECTRODE
Te
PH meter

Saturated
wishin) ----e
electrode Fr clectrode

oe
-
insu

ut
<
if
rH Ag Wire

Heavy-walled "
Ag wire
Oo.) MHC
saturated with
men
Thiin El
membrane stlerer
Advantages of Glass pH electrode
*
Potential not affected by the presence of oxidizing or reducing agents

Operates over a wide pH range

¢

*
Fast response

*
Functions well in physiological systems

*
Very selective

¢
Long lifespan

*
Used in pH meter
Theory of the glass membrane potential
For the electrode to become operative, it must be soaked in water.

During this process, the outer surface of the membrane becomes hydrated.

When it is so, the sodium tons are exchanged for protons in the solution:

The protons are free to move and exchange with other tons.

H
+
0
H' Charge is slowly carried
H' 0, by migration of Nat
across glass membrane
by H'
H* + 0.
HOO
Potential! is determined
internal External
by external [H*]
solution solution
 Alkaline error
In basic solutions, glass electrodes respond to the

concentration of not only hydrogen ion but alkah metal -1.0

A. Corning 015, H,S0,
ions. &, Coming 015, HC) c
C. Corning 015, 1-M Na*
BD.Beckman-GP, |-M Na*
At high pH, glass electrode indicates pH less than true £.L & N Black Dot, Na*
-0.5
F. Beckman Type E, |-M Na'

Error, ApH
value
E F
Exhibited at pH > 9

0
Electrodes respond to H and alkali cations A

C,D,E and F: measured value 1s < true value

Electrode also responds to other cations 2 0 2 4 6 i@ 12

pH
 Acid error
0
A. Corning 015, H,SO,
8. Coming 015, HC! C
C. Corning 015, 1-M Na'
D. Beckman-GP, |-M Na'
-0,§ &.L&N Black Dot, 1-M Na* * Exhibited at pH < 0.5
F. Beckman Type E, M Na*
Error, ApH

E pH readings are higher (curves A and B)

*
F
* Saturation effect with respect to H
0
A

2 0 2 4 6 10 12 14

pH
 Selectivity Coefficient
*
No electrode responds exclusively to one kind of on.

¢
The glass pH electrode is among the most selective, but it also responds to high concentration of Nat.

¢ When an electrode used to measure ion A, also responds to ion X, the selectivity coefficient gives the

relative response of the electrode to the two different species.

response to X
Kay -

to A
response

¢
The smaller the selectivity coefficient, the less interference by X.
 Selectivity Coefficient
Measure of the response of an ISE to other ions

E, = VL' + 0.0592 log (a, + kyj,b1)

kip;
= 0 means no interference

2 I means there is interference

< 1 means negligible interference

LIQUID MEMBRANE ELECTRODES
*
Potential develops across the interface between the analyte solution and a liquid ion exchanger (that
bonds with analyte)

*
Similar to a pH electrode except that the membrane is an organic polymer saturated with a liquid ion

exchanger
Ca*~ Ca
>
Used for polyvalent ions as well as some anions

*
Example:
CGa* Ca*" Ca
Calcium dialkyl phosphate insoluble in water, but binds Ca*' strongly
 Liquid membrane electrodes

Ca** electrode
Ag/AgCl
reference
electrode

internal
reference
lon exchange solution
reservoir
0.1 M CaCl,
porous
sensing memo ane
area
Responsive to Ca**
 Characteristics of Ca** ISE
*
Relatively high sensitivity
¢ Low LOD

¢
Working pH range: 5.5 -11
¢ Rejevant in studying physiological processes
 K+-selective electrode
Sensitive membrane consists H
N
valinomycin, an antibiotic
HN
o
NH

f
HN
+
-0
1

N
H
CRYSTALLINE-MEMBRANE
ELECTRODES
Solid state electrodes

Usually tonic compound

Crushed powder, melted and formed

Sometimes doped to tncrease conductivity

Operation similar to glass membrane

 CRYSTALLINE-MEMBRANE
ELECTRODES (Ctnd...)
*
AgX membrane: Determination of X

4
¢
Ag.S membrane: Determination of S

*
LaF, membrane: Determination of F-

E ind =L+0.05S92 lay

a
LaFo*
3
+ +
ho,
oLal F

Solid analyte Solid,

=L--- 0.0592 log ap
= L+0.0592 pF
 F- Selective Electrode
A LaF, is doped with EuF,.

Eu** has less charge than the La* so an anion vacancy occurs for every Eu2*

A neighboring F can jump into the vacancy, thereby moving the vacancy to another site.
Repetition of this process moves F- through the lattice.

LaF, membrane
 GAS SENSING PROBES
A galvanic cell whose potential is related to the concentration ofa gas in solution

* Consist of RE, [SE and electrolyte solution

A thin gas-permeable membrane (PTFE) serves as a barrier between internal and analyte solutions

Allows small gas molecules to pass and dissolve into internal solution O;, NH,/NH* , and

CO,/HCO,-/CO,
 To meter

Gas
electrode

Probe Nano,
Na ' internal
wil
internal
soletion
Glass
a of glass

ry

Glass
membenne

Gas-permeable Thin film

membrane of inlernal
polutron
 CELL POTENTIALS
¢
The potentials of the two reference electrodes -

depend on the electrochemical characteristics of

their respective redox couples

¢ The potential across the glass membrane: -

depends on the physicochemical characteristics of the

glass and its response to tonic concentrations on both sides of the membrane

Reference
electrode | Glass electrode

External Internal
analyte solution reference solution

+ Glass = a,. [CI-] = 0.1M, AgC! (sat'd) Ag

SCE [H,O*]=a,
- -
-

membrane |[H,O*]
|
|| | |

i kK.

Reference electrode 2

f an
= _
a T
 LIQUID JUNCTION
POTENTIAL
*
Liquid junction -
interface between two solutions containing different electrolytes or different

concentrations of the same electrolyte

¢
A junction potential occurs at every liquid junction.

« Caused by unequal mobilities of the + and -

ions.
 MEMBRANE POTENTIAL
*
Four potentials that develop in a cell when pH is being determined with a glass electrode

*
Ea gAgc] and Egcp, are reference electrode potentials that are constant. -
A 3rd potential is the junction

potential Ej across the salt bridge that separates the calomel electrode from the analyte solution.
-

The
4th and most important potential is the boundary potential, E,, which varies with the pH of the analyte

solution.
 BOUNDARY POTENTIAL
¢ The boundary potential is determined by potentials, El and E2, which appear at the two surfaces of the

plass membrane from the reactions:

H*GI"(s) - H* (aq) + Gl Os)

vhins, sonny, elass,

H*GI(s) -
H*(ag) + GI(s)
elass, soln. glass,

¢
where subscript | refers to the interface between the exterior of the glass and the analyte solution and

subscript 2 refers to the interface between the internal solution and the interior of the glass.
 BOUNDARY POTENTIAL (Ctnd...)
+ These two reactions cause the two glass surfaces to be negatively charged with respect to the

solutions with which they are in contact

¢ The resulting difference in potential between the two surfaces of the glass is the boundary

potential, which ts related to the activities of hydrogen ton tn each of the solutions by the Nernst-

like equation:
G
E, = E, -
Ey = 0.0592 log
tio
¢ where a, is the activity of the analyte solution and a, is that of the internal solution
 THE ASYMMETRY POTENTIAL
When identical solutions are placed on the two sides of a glass membrane, the boundary potential
should in principle be zero . In fact, however we frequently encounter a small asymmetry potential
that changes gradually with time due to slight imperfections in the membrane.

The sources of the asymmetry potential are obscure but undoubtedly include such causes as
differences in strain on the two surfaces of the membrane created during manufacture, mechanical
abrasion on the outer surface during use, and chemical etching of the outer surface.

To eliminate the bias caused by the asymmetry potential, all membrane electrodes must be
calibrated against one or more standard analyte solutions.

Such calibrations should be carried out at least daily, and more often when the electrode receives

heavy use.
 Potentiometric Determination of Equilibrium
Constants
¢
Numerical values for solubility-product constants, dissociation constants, and formation constants

are convenicntly evaluated through the measurement of cell potentials.

¢ One important advantage of this method is that the measurements can be made without disturbing

any equilibria that may exist in the test solution.

* EXAMPLE: Calculate the formation constant K, for Ag(CN),°:

 Determination of Equilibrium Constants (Ctnd..)
F
Combining both above equations yiclds
AG=AG°+RT Up Up
a
A
b
ila -
Fi FE = -2.3RT log K
or AG= AG +2.3RT log K and

where K is equilibrium constant.

K
i FE 1
cell
log
2.3 RT
In equilibrium condition AG = 4,
Substitution for FR and JT, leads to
AG= -.2 log K 7

"cell
AG =-nFE lo £ ~
0.0591
 Ag* + 2CN7 = AgiCN)3
SCE Ag(CN) (7.50 X 10-3 M). CN~(0.0250 M)|Ag
||
4

if the cell develops a potential of -0.625 V

Agt +e° Agis) EE" = +0.799V

-.625 = -

Eten
=
Eqgs
-
0-244
= -.625 + .244 = 0.38] V
0.0592 l
~0.381 = 0,799 low
"
- -

.1
[Ag]
[Ag*] = .2 x 10-™

LAg(CN)y] 7.50 X 0
K, +
x x a
[Ag*][(CN7] (1.2 107%\(2.5 0
.0 x 10
POTENTIOMETRIC TITRATION
Involves measurement of the potential of a suitable indicator electrode as a function of tulrant volume

It's a volumetric method in which potential between two electrodes (reference & imdicator) ts
measured as a function of added reagent volume

Potentiometric titrations are not dependent on measuring absolute values of E cell-

Potentiometric titration results depend most heavily on having a titrant of accurately known
concentration.

Provides MORE RELIABLE data than the usual ltration method

Useful with colored/turbid solutions

May be automated

More time consuming

POTENTIOMETRIC TITRATION
re

Involves measurement of tH ectrode as a function of titrant volume

pili meter
It's a volumetric method with clectrodes (reference & indicator) 1s
ema h cel
measured as a function of 1 scaly

Combination
Potentiometric titrations arg pH clecuwde
~
~ ite values of E,,)..

Potentiometric titration rq _ aving a titrant of accurately known

concentration. |

Provides MORE RELIAB bd

Useful with colored/turbid

May be automated -
_

Magaelic stirrer
More time consuming
POTENTIOMETRIC TITRATION CURVES
Equivalence
Equivalence point
point
+
t
Ala
Ay

8
+
QE
'Equivalence

Point
I

(titrant) -> J (titrant) -> (titrant) ->

(a) (b) (c)

(a) typical plot of emf vs volume; (b) typical first derivative titration curve; and (c) typical
second derivative titration curve
 DETECTING THE END POINT
0.4

V
Electrode potential vs. SCE,
« A direct plot of potential as a function of reagent
0.3
volume
End point
-
the inflection point in the steeply rising portion of
the curve, and take it as the end point.
0.2

0
20 22 24 26
Volume 0.100 M AgNQO,, mL
DETECTING THE END POINT (Ctnd...)
1.0

« Calculate the change in potential per unit volume of 0.8

titrant (i.e, AE/AV) If the titration curve is &
> 06
-

symmetrical, the point of maximum slope coincides 4°

< 0.4
with the equivalence point.

0.2

I 0
20 22 24! 26
Volume 0.100 M AgNOQ,, mL
DETECTING THE END POINT (Ctnd...)
0.6

0.4
« Calculate the second derivative for the
data changes sign at the point of inflection 0.2

This change is used as the analytical

s 0
-

signal in some automatic titrations. > -0.2

-0,4
ls

-0.6
20 22 24 26
Volume 0.100 M AsNO.. mL
WHEN POTENTIOMETRIC TITRATION IS
USED?
¢
Itis used when the endpoints are very difficult to determine either when:

1) very diluted solution.

2) coloured and turbid solution.

absence of a suitable indicator.

&
3) = f
q
k,

MT"
Potentiometric titration curve of (0.1 N) NaOH
against acetic acid
TYPES OF POTENTIOMETRIC TITRATIONS
|. Precipitation titration

2. Complex formation Titration

3. Neutralization titration

4. Oxidation -
reduction titration
 PRECIPITATION TITRATION
"
Volumetric methods based upon the formation of slightly soluble precipitate are called precipitation
titration ".
Because of the precipitating titration based upon utilizing silver nitrate (AgNO,) as a precipitating
"
agent, then it called argentimetric processes

Precipitation titration is a very important , because it ts a perfect method for determine halogens and
some metal tons

Any precipitaton titration that involves insoluble salts of metals such as mercury, silver, lead and

copper may be followed potentiometrically.

PRECIPITATION TITRATION (Ctnd...)
* For quantitative determination of several ions or elements precipitating agents are used as titrants

End point is determined by potentiometric method.

E=E,+0.0592/nlog [M™

where, [M** ]= concentration of ions

n= clectronic state.

Reference electrode: SCE, H,. Ag-AgCl, electrode

* Indicator electrode: Metal involved in the reaction or the electrode whose potential 1s poverned by
the concentration of anion being precipitated

Ex: Determination of Hg, Ag, Pb, Cu, and other ions using precipitants to form insoluble salts.
 PRECIPITATION TITRATION (Ctnd...)
The magnitude of the potential change at the end point depends on the solubility of the substance being

precipitated as well as concentration involved

The ly tration of chloride tons with a standard solution of silver nitrate using a silver metal indicator
electrode is an example of a preciptlation litration.

The potential of silver electrode will be governed by appropriate Nernst equation

E AgtiAg 0.059 log[Ag']

As soon as cnough silver nitrate solution to precipitate Cl as AgCI has been added, the following

equilibrium is established

AgCl- Ag' +Cr

PRECIPITATION TITRATION (Ctnd...)
*
The equilibrium constant of the reaction is
10+

K AgCl [Ag ][CT}- 10°

©
0.80V + 0.0591 log 10° ~ 0.2681 V ( [Agt]~ 10° N)
6
>
*
Similarly half wave through the titration will be when the chloride
2,
ions concentration has been reduced to 0.033 N >
?
= V
Fag iAg= 0.80V + 0.0591 log 10( 3*10°) 0.30
¢ At equivalent point [Ag™]=[CI}= LO" N 0 19 20 -30 -40 SO

= 0.50 V Fraction titrated

E 0.80V + 0.0591 log 10°
COMPLEX FORMATION TITRATION
Complex ions ( coordination compounds) are produce from reaction of many metal ions (electrons
*

accepter) with electron pair donors .

¢ The donor species (or called ligands) must have at least one pair of unshared electrons for bond
formation

* Metallic ions (divalent}can be titrated against disodium acetate solutions by potentiometric method

* Measurements are made in mV scale.

* Reference electrode: SCE/ any other.

Indicator electrode: Ag / Hy electrode.

Ex:- Di and Trivalent ions Qnix of Bit* ,Cd** Ce\*7+ by using EDTA).
COMPLEX FORMATION TITRATION (Ctnd...)
*
For example, a silver electrode may be used to follow the titration of cyanide ion with a standard solution of
silver,

¢
The silver ion concentration will be governed by the equilibrium constant for the complex formation
reaction, Ag' +2CN- [Ag(CN),]
* K [Ag ]LCN]*/ [Ag(CN)2)
*
At equivalent point , 2[Ag*]=
¢
In this case, solid silver cyanide begins to get precipitated soon after the equivalence point.

*
The further addition of silver neither changes the concentration of the complex nor changes the silver ion to

any extend so that the titration curve has an almost horizontal portion after the equivalence point
COMPLEX FORMATION TITRATION (Ctnd...)
¢
In case of many complexometric reactions the situation cannot be handled so easily because more

than one complex ts formed

200 -

¢
Eg. Hp" + 3CN-- Hg(CN), 14
&
He?! + 4CN-- »
He(CN),* ¢ 'BOF-
é

S too
$
&
or t
 NEUTRALIZATION TITRATION
(ACID- BASE TITRATION)
Neutralization titrations are performed with standard solutions of strong acids or bases. While a

single solution (of cither acid or base) is sufficient for the titration of a given type of analyte, it is
convenient to have standard solutions of both acid and base available in case back-titration ts

needed to locate the end point more exactly.

The concentration of one solution is established by titration against a primary standard;

The concentration of the other is then determined from the acid/ base ratio (that is, the volume of
acid needed to neutralize .004 mL of the base).

pKa values can also be directly read from the titration curves.
 +
x a
[HAI
[A
log K, = log H* + log
[HA]
[A
¢
e.g. in the titration of weak log K, = -

log -

log
acid HA, we may ordinarily [HA]
assume that at the mid-point
[A
[HA]=[A [A [H+] and pA, = pH -

log
therefore
[HA ]
At half neutralization of the acid
[A>] ¢salty = JHA] (acid)

Therefore, pK, = pH log I

or pK, = pH
A known volume of the acid to be titrated is kept in a beaker having an automatic stirrer. [t also has a standard

hydrogen electrode and connected to a calomel electrode through a salt bridge.

After the each addition of base from the burette in to the beaker, EMF is measured

The values of the EMF are then plotted against the volume of base. End point is obtained from the plot.

The potential of any hydrogen electrode is given by

E- E° -0.0591 log a, at 25°C

E= E*t 0.0591 pH

[t can be concluded that the change in electrode potential or EMF of the cell is proportional to the change in pH

during titration.

The point where the EMF increases rapidly gives the end point.

A more sensitive and satisfactory method to find the end point 1s to plot the slop of the curve. AE/AV Vs V)
(
A known volume of the acid to be titrated is kept in a beaker having an aulomatic stirrer. It also has a standard

hydrogen electrode and connected to a calomel electrode through a salt bridge.

After the each addi

Equivalence
The values of the B point atned from the plot.

The potential of an
t
E- E° -0.0591 log
<cy
'Equivalence q
E= E 0.0591 pH
'point
{t can be conclude portional to the change in pH

during Gtration. i (titrant) > (titrant) ->

The point where the EMF increases rapidly gives the end point.

A more sensitive and satisfactory method to find the end point is to plot the slop of the curve. (
AE/AV Vs V)
OXIDATION-REDUCTION TITRATION
*
A redox titration is a type of titration based on a redox reaction between the analyte and titrant.

*
Redox titration may involve the use of a redox indicator and/or a potentiometer.

° Indicator electrodes for oxidation-reduction are generally fabricated from platinum, gold mercury or silver.

¢ The metal chosen must be un-reactive with respect to the components of the reaction. It is merely a site for

electron transfer.

« Platinum electrode is most widely used for oxidation-reduction titrations. It should be recalled that the

curves for many oxidation-reduction titrations are not symmetric.

*
Thus, the equivalence point potential may be significantly different from the potential corresponding to the

point of inflection in the curve.

The determining factor in the values of potential is the ratio of the activity or concentration of the
oxidised and reduced forms of certain 10n species.

Take a general equation

Oxidised form + ne === reduced form

The potential acquired by the indicator electrode at 25°C is given by

0 OS 9] d oxidise form
E=E° log
a seduced form

In redox reactions, reducing agent is oxidised or oxidising agent is reduced and the ratio and the

potential therefore changes more rapidly at the end point of the reaction.
OXIDATION-REDUCTION TITRATION (Ctnd...)
Shape of a Redox Titration Curve

Voltage Change as a Function of Added Titrant

- Consider the Titration Reaction (essentially goes to completion):

Ce** + Fe?* - Ce** + Fett Kk 10° Butel Co

x €e* is added with a burette to a solution of Fe2* ¥

- Ptelectrode responds to relative concentration

of Fe*/Fe*? & Cet/Ce*
Indicator half-reactions at Pt electrode:
Calomel electrode used as reference

Fe + Fe2* Fe-0.767 V ont BGG,

+ & Ce?
OXIDATION-REDUCTION TITRATION (Ctnd...)
Shape of a Redox Titration Curve 1.4

Titration Curve has Three Regions 1

12
- Before the Equivalence Point
1

- At the Equivalence Point 1

Equivalence point
(inflection point)
» After the Equivalence Point 0.9

0
Region
egion : Before Equivalence Poi
Before the Equivalence Point
=E (Fe"| Fe**)

- Fach aliquot of Ce? creates an equal : 0

E SCE)

number of moles of Ce* and Fe*' 0

a
- Excess unreacted Fe- remains in solution 04 1

Amounts of Fe*' and Fe? are known, use

Q 10 20 xn 40 50

to determine cell voltage. Vegas (PL)

m a ows.
OXIDATION-REDUCTION TITRATION (Ctnd...)
Region |: Before the Equivalence Point

14
Use iron half-reaction relative to calomel reference electrode: 1 3

t + e I
+

e 1.2

E=E, (indicator electrode ) E_( reference electrode }

Potential (¥ vs. 5.0.6.)

Equivatence

point
1
-

{inflechon paint}
Potential of og
calomel
.8
electrode
a+ = E- (Fe**| Fe**}

E= 0.767 0.05916 log [Fe 1

oF -

ECE)
0.6
[Fe**1
05
Simplify t

0.4 Iv
0.3
2+
E = 0.526 -0.05916 log [Fe ]
|

10 #30
| I ]

[Rott] Vass (nL}

OXIDATION-REDUCTION TITRATION (Ctnd...)
Region : Before the Equivalence Point

- Special point when V -

1/2 V, ral
13

[Fe?* =[Fe?*] 12

1.1

ss Equivalence point
2+ o 1
{infleclon pont)
F
E = 0.526 -0.05916 be og

Fe 3+ he
-

= & iFe*| Fe**}

Log term is zero 07
0.6

E-0.526 => E,-E° -0.767V os

0.4

0.3

The point at which V= % V, is analogous to the point at a 10 20 30 a0 .50 OO 70

whirh nH = nia iin an arid hace trtratinn Vets

OXIDATION-REDUCTION TITRATION (Ctnd...)
Region : Before the Equivalence Point

> Another special point, when [Ce ]=0 rae

1 3
a
- Voltage can not be calculated 1 2

-1
gersts unknown 1

y [Fe?'] Equivalence point

1 o
{inflecton paint)

-
If[Fe*'] =0, Voltage = -20 g
-
Must be some Fe** from impurity, 2 ost &=€.-
= (Fe°" Fe*"}
or Fe 2+ oxidation 07- sce) _

0.6
- Voltage can never be lower than value 0.5
need
4 1

to reduce the solvent

0.3

-H,+
l

2H,0 + 2e 20H" = -0.828V 0 10 20 30 40 50 60 70

Vouss (mL}
OXIDATION-REDUCTION TITRATION (Ctnd...)
Region 2: At the Equivalence Point

Enough Ce*' has been added to react with all Fe*' val
-
Primarily only Ce** and Fe** present 1 3
-
Tiny amounts of Ce* and Fe** from equilibrium 1 2
x From Reaction:
1 -1

+ Fe** Ce* + Fe* ui Equivalence poinl

1.0L

{Ce3*] = [Fe**] ¥ 0.9

2+
-
[Ce 4+ -

=[Fe**] a
(Fe Fe**}
0.7
» oth Reactions are in Equilibrium at the
Pt electrode aa +

=0,767 -0,05976 in [Fe 0.5

a+
[Fe 0.4 1

0.3
3

E, =1.70-0.08016 fe
[Ce 20 a ag
4
OXIDATION-REDUCTION TITRATION (Ctnd...)
Region 2: At the Equivalence Point
Don't Know the Concentration of cither Fe?" or Ce*
Can't solve either equation independently to determine E,
Instead add both equations together

3+
= 0.767 -
0.05916 log [Fe J E, =1.70 -0.05916 fog! {Ce 1

31

[Fe [Ce |

Add

2+ 3+
[F J
2E, -0767 +470~0.05066 lop 3
0.05916 to
[ce

Rearrange
J Fe?" 3
~ 2.47
2K, -

0.05916 fog
4
(Fe? | [Ce
OXIDATION-REDUCTION TITRATION (Ctnd...)
Region 2: At the Equivalence Point
Instead add both equations togeth er 14-
1 3
Zt
2E =2.47 -0.05916 log [F 1 2
a
8 J Ice* 1

Equivalence poinl
Celt) t Fett ou
1.0
{inflechon point)
Log term is zero
(ce**)-[Fe**]
¥
E E
a 0.8-
2E, -247V > E, -1.23V
-

(Fe? | Fe**)
OF -
E(SCE)
Cell voltage
0.5

E=E, -E£(calomel ) =1.23 -0.247 0.99)

0.4

0.3
1

! i | I

Equivalence-point voltage is independent of the 0.690 «20 30 40 «50 60 70

rnnrantratinnc and of the reartante imL)
OXIDATION-REDUCTION TITRATION (Ctnd...)
Region 3: After the Equivalence Point

x Opposite Situation Compared to Before the Equivalence Point

14
-
Equal number of moles of Ce*! and Fe*' ta

> Excess unreacted Ce* remains in solution t.2

ve. $.C.E.)
- Amounts of Ce* and are known, use 1.0

to determine cell voltage. I19

(Vv
08

Potential
4
- Residuat amount of Fe-* is unknown 0.7

0.6

0.5

0.4

0 10 20 3% 40 50 60 70
OXIDATION-REDUCTION TITRATION
(Ctnd...)
Applications
« Used in procedures such as monitoring of cyanide wastes from metal plating industries or chlorine

compounds in bleach compounds manufacturing

*
Extensively used in water pollution, sewage treatment, agricultural and biochemical studies.
 ADVANTAGES OF
POTENTIOMETRIC TITRATIONS
The apparatus required is generally inexpensive, reliable and readily available

It is easy to interpret the titration curves

The method can be used for colored solutions

The method 1s applicable for analysis of dilute solutions

Several components can be titrated in the same solution without the possibility of indicators

interfering with each other. For instance bromide and todide can be titrated together