Potentiometric Titration

Potentiometry is the part of analytical chemistry that deals with the quantitative
measurement of or estimation of potentials which gives-
- Presence of some entity
- Change in conc. of some entity
Potentiometric titration is an electrochemical analytical method where the potential change
of an electrochemical cell is measured as a function of change in conc. of the test element in
the solution by the addition of titrant whose conc. is known.
Potentiometric titration is a technique similar to direct titration of a redox reaction.

Principle of PotentiometricTitration:
- Two indicators are used:
- Reference electrode (maintains a constant potential)
- Indicator electrode (indicates a potential change)
- The solution must be stirred during titration.
- During titration-
Active ingredient being determined produces an electric potential with a suitable
indicator electrode. The titration is followed by the fall in potential as the
ingredient is used up[by titrant].
Or,
The titrant may cause production of a potential. At the end point when titrant is no
longer being used up [by active ingredient], the sudden increase in titrant conc.
result in sudden increase of potential.
- End point is determined by sudden change in potential.
- From the end point determination, the conc. of active ingredient can be measured.
- It is a regular titration but instead of the indicator we used the potentiometer.
- It measures the change in potential.
- Can be used for all kinds of titration:
1. Acid base
2. Redox
3. Complexometry
- Based on potential measurement of electrochemical cells without any appreciable current.
- The use of electrodes to measure voltages from chemical reactions.

General Principle:
A typical cell for potentiometric analysis consists of a reference electrode, an indicator
electrode and a salt bridge. This cell can be represented as:

Reference electrode | salt bridge | analyte solution| indicator electrode

Eref Ej Eind
The potential of the cell is given by the equation: Ecell = Eind – Eref + Ej
A reference electrode, Eref, is a half-cell having a known potential that remains constant at
constant temperature and independent of the composition of the analyte solution,e.g. calomel
electrodes and silver/silver chloride electrodes.
An indicator electrode has a potential that varies with variations in the concentration of an
analyte. Most indicator electrodes used in potentiometry are selective in their responses.
Metallic indicator electrode and membrane electrodes are types of indicator electrodes.
The third component of a potentiometric cell is a salt bridge that prevents the components of
the analyte solution from mixing with those reference electrodes.
 A potential develops across the liquid junctions at each end of the salt bridge.
 The junction potential across the salt bridge, Ej, is small enough to be neglected.

Potentiometer:
 An instrument, which can measure the potential developed without drawing any
current.
 In simple form, consists of two electrical circuits in combination.
Potentiometer Circuit Diagram:

Potentiometer current flow calculation:

Titration Curve:
If the ingredient being determined produces an electric potential with a suitable indicator
electrode, the titration may be followed by the fall in potential as the ingredient is used up:
- There is a relatively small fall in potential with addition of titrant
- As titration proceeds, there is a larger fall in potential with addition of the same
volume of titrant
- In the end point region, there will be a much larger fall in potential with a very small
volume of titrant
- After the end point, the fall in potential continues again with addition of titrant
If the potential of the sample being determined is plotted against the volume of titrant added
to produce a graph, such a graph is termed as “titration curve”

Preparation of Titration Curve:

Two methods:
i. Theoretical calculation (Nernst equation)
ii. Experiment in laboratory

i. Theoretical calculation:
The potential developed after addition of certain amount of titrant can be calculated
by Nernst equation:
Where,
E= measured potential
E0= standard potential
n= no. of electrons transferred in reaction
The calculated potentials after different volumes of titrant are recorded and a titration curve
can be constructed.

ii. Laboratory experiment:

A typical potentiometric cell has two electrodes:
i. Reference electrode
ii. Indicator electrode
- After adding certain amount of titrant from the burette, cell potential is measured
with electrodes.
- After each addition, a reading is noted.
- The E(potential) vs volume of titrant is plotted in the curve & titration curve can
be constructed.

Advantage over theoretical calculation:

- More reliable
- Useful with colored & turbid solution
- Automatic calculation

End Point Detection:

- It is also called “equivalence point”.
- The end point in a potentiometric titration is the sharp rise or fall in the potential
indicated by the indicator electrode.
- If the sharp rise or fall is sufficiently steep, then midpoint in the steepy portion of the
curve is selected to determine the end point.

Figure: a

However, If the rise or fall through the eq. point is more gradual it may be difficult to select
end point with certainty. In such cases, it is useful to draw a 1st derivative or even a 2nd
derivative curve to detect the end point.
1st derivative curve:

Figure: b

Calculate the change in potential per unit of volume of titrant ∆E/∆V. A plot of ∆E/∆V
against the average volume V produces a curve with a maximum point that corresponds to the
point of inflection.

2nd derivative curve:

Figure: c

Comparison of different curves

In fig (b) & (c) the end point detection are easy & accurate. Therefore, they are preferred over
fig (a) curve.
Potentiometer Cell
Composed of:
- Reference electrode
- Indicator electrode
- Salt bridge
- Analyte solution

Reference Electrodes:

- Defined as an electrodewhose potential is:

- Known
- Remain constant
- Insensitive to composition of solution under study
- It is Half-cell with known potential (Eref)
- Left hand electrode (by convention)
In potentiometric titration there is a need of one electrode to act as a reference against which
potential measurements can be made, i.e. relative comparison.

Desired Characteristics:
- Known potential
- Constant response
- Insensitive to composition of solution under study
- Obeys nernst equation
- Reversible(returns to original potential)
- Easy to assemble

Example:
- Standard Hydrogen electrode (SHE)
- Standard Calomel electrode
- Ag/AgCl electrode
 Standard Hydrogen Standard Calomel electrode Ag / AgCl electrode
Electrode

Presented by- Presented by- Presented by-

+ 2+
Pt, H2 (1 atm) | H || Cu | Cu Cl- (1M) | Hg2Cl2, Hg Ag, AgCl | Cl- (1 M)|
The electrode reaction- The electrode reaction- The electrode reaction-
H2 ↔ 2H+ + 2e- Hg2Cl2 + 2e- ↔ 2Hg + 2Cl- AgCl + e- ↔ Ag + Cl-
0
E = + 0.34 V E 0 = + 0.280 V (at 25OC) E 0 = + 0.2224 V
Advantages Advantages Advantage
- All other potentials are - Relatively cheap - One advantage over SCE
compared against this - Easily prepared is that Ag/AgCl
- Can be used in high - Most commonly used because electrode can be used at
alkaline solution of the suppressive effect of temperatures > 60oC
KCl solution on LJP
Disadvantages Disadvantages Disadvantage
- Pt black surface must be - Becomes unstable above 800C - Ag reacts with more ions
washed properly
- Pt black is sensitive to
As, Hg, H2S, CN-1,
Protein
- SHE is sensitive to
dissolved gases,
oxidizing & reducing
agents
- Pt-wire is highly
expensive
Uses
- Check the accuracy of
another reference &
indicator electrode
- Test the magnitude of LJP
Indicator Electrodes:
Defined as an electrode whose potential (Eind) -
- Depends upon the activity & conc. of any ionic species(analyte)
- is not constant but variable

Desired Characteristics:
- Rapid and reproducible response
- Selective
By knowing the potential from the indicator electrode, we can determine the conc. of the
ionic species.
Depending on the type of reaction, indicators are used:
a. For acid-base titration: Glass electrode
b. For precipitation titration: Silver electrode
c. For redox titration: Platinum electrode
d. To measure conc.: Antimony electrode

Noble Metal Electrodes

a. Platinum
- Most common metal indicator electrode
- Inert: does not participate in many chemical reactions
- Simply used to transmit electrons
b. Other electrodes include Gold and Carbon
c. Metals (Ag, Cu, Zn, Cd, Hg) can be used to monitor their aqueous ions
- Most metals are not useable
- Equilibrium not readily established at the metal surface

Example:

½ Reaction at Ag indicator electrode:

E+o = +0.799 V
½ Reaction at Calomel reference electrode:

E(satd, KCl) = +0.241 V

Cell Potential from Nernst Equation:
  1  
Ecell  E   E   0.799 
0.05916
log     0.241
   
1  [ Ag ]  

Potential of Ag indicator electrode

Cell voltage changes as a function of [Ag+]

Glass Membrane Electrode:
- Glass electrode is most common ion-selective electrode
- It is a combination electrode, which combines both the glass and reference electrodes
into one body.

- Electric potential is generated by [H+] difference across glass membrane

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 ions are exchanged for protons in the solution:
– The protons are free to move and exchange with other ions.

Properties of Glass 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
Advantages:
i. Glass electrode can be used in-
- The presence of strong oxidizing & reducing agent
- Highly viscous media
- The presence of proteins
ii. Can be applied for small volume of solutions

Disadvantages:
- Not easy to prepare

Types of Glass Membrane Electrode:

i. Solid ion-exchange membrane
Glass is a mixture of SiO2 + Trivalent metal oxide+ Mono/Divalent metal oxide
ii. Liquid ion-exchange membrane
Liquid is a mixture of long chain fatty acid and water
iii. Neutral sequestering agents
Macrocyclic molecules or Citrates

Quinhydrone Electrodes:
- Platinum wire dipped in a solution containing quinhydrone
- Quinhydrone = 1 mol quinone + 1 mol hydroquinone
- Quinhydrone electrode can be used to indicate the pH of the solution
- The solution of Quinhydrone can be oxidized or reduced as-

Advantages:
- Can be used to indicate the pH of the solution
- Can be used in combination with calomel electrode
- Very simple to use

Disadvantages:
- At pH>8, quinhydrone reacts with alkali forming anions
- May cause salt errors
Enzyme based Electrode:
- Enzymes are used in this electrode to convert the substance into an ionic product
- Due to the formation of ionic product, a potential develops which is determined by
another indicator electrode
- Example
- Urea electrode
- Penicillin electrode

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.
Junction Potential:
- Occurs whenever dissimilar electrolyte solutions are in contact
- Develops at solution interface (salt bridge)
- Small potential (few milli volts)
- Junction potential puts a fundamental limitation on the accuracy of direct
potentiometric measurements
Salt bridge:
A salt bridgeis a device used to connect the half-cells of an electrochemical cell. A saturated
KCl, KNO3 is good component for salt bridge
- Generates potential (Ej) = negligible (The net junction potential is few milli volts)
- Prevents mixing up of analyte components
- The magnitude of LJP can be minimized by placing a salt bridge

Selection of Electrode:
Advantages of Potentiometric titration:
1. It can be used when the endpoints are very difficult to determine, either when:
- Colored and turbid solution
- Very diluted solution.
- Change in potential is too small
- Absence of a suitable indicator
2. Can be used for all kinds of titration:
- Acid base
- Redox
- Complexometric
3. Can be performed automatically
4. Can be used with recorders to prepare the titration curve easily

Applications of Potentiometric titration:

- In oxidation-reduction reactions
- In complexometric titrations
- In neutralization reactions
- In non-aqueous solvents
- In precipitation titrations
- In dead-stop titrations

Potentiometry vs. Amperometry:

Parameters Potentiometry Amperometry

Constant Applied current Applied potential
Titration curve Potential vs Titrant Volume Current vs Titrant Volume
Relation of conc. Directly related to potential Directly proportional to
diffusion current
Dilute soln. Cannot be used Can be used
Reference electrode Mandatory Not mandatory
Supporting electrolytes Not required Required
Microelectrode Not required Required
Microburette Not required Required
Sensitivity Less More
Process speed Rapid Rapid
Titration method Satisfactory Unsatisfactory