POTENTIOMETRY I. PRINCIPLE 1.

Potentiometry is a direct application of Nernst equation, in which we relate the measured potential of the cell to the concentration of the analyte solution. 2. We set up a complete electrochemical cell that constitutes of the following a) Indicative Electrode: An electrode whose potential depends upon the analyte concentration eg. Metal electrode, Hydrogen electrode b) Reference Electrode: An electrode which has a fixed potential irrespective of analyte concentration eg. Calomel electrode, Silver-Silver Chloride electrode c) Salt bridge: It connects the two electrodes and completes the circuit eg. Agar + NH4NO3 3. The potential of indicative electrode is given by [ The potential of the reference electrode is fixed = ]

4. When we connect the two electrodes with the Salt bridge, the electrochemical cell so generated has a cell potential given by

[ [

] ] [ ]

5. Thus in principle, making use of the above equation, we can relate the concentration of the analyte to the measurable cell potentials.

II. TYPES OF ELECTRODES a) INDICATIVE 1. Metal Electrode It consists of a metal strip dipped in an aqueous solution of the corresponding metal ion eg. Zn dipped in Zn2+ (ZnSO4) solution. The concentration of the ion is variable and hence the potential of the half cell is given by

2. Hydrogen Electrode It consists of a Platinised Platinum Electrode dipped in a solution of Hydrogen ions with Hydrogen gas bubbled through it (P = 1 bar). The concentration of the H+ ions is variable and hence the potential of the half cell is given by [ ]

Note: If the concentration of H+ is maintained fixed at 1M, then the half cell now acts as an important reference electrode ie The Standard Hydrogen Electrode (SHE)

b) REFERENCE 1. Calomel Electrode It is based on the redox reaction

It consists of a tube: at the bottom is Hg over which a paste of Hg/Hg2Cl2.Remaining is filled with a saturated solution of KCl. A platinum wire dipping into the mercury layer is used for making electrical contact. [ ] is variable and cell potential given as [ ]

For a saturated KCl solution, the IInd term is a constant and the total cell potential of this Saturated Calomel Electrode (S.C.E.) is given as (0.285 V for 1M KCl)

CALOMEL ELECTRODE 2. Silver Silver Chloride Electrode It is based on the redox reaction

Ag/ AgCl ELECTRODE

It consists of an AgCl coated Silver wire dipped in a solution of saturated KCl. The concentration of chloride ions is variable. The electrode potential of this half cell is given by [ ]

Note: Concentration Cell If two identical electrodes are placed in beakers containing solutions similar in every respect (except concentration), and connected by a salt bridge, the potential between the electrodes is related to the ratio of the two concentrations. It is extremely sensitive with minimal error

III. ION SELECTIVE ELECTRODE 1. An Ion Selective electrode responds only to a particular ion and is used for the measurement of its concentration. No Redox reaction takes place at the membrane 2. The ion selective membrane is capable of binding to only the intended ion. These membranes are called Liquid Membranes. They have a hydrophobic organic polymer ( with functional groups + to form chelates/ coordination complexes. It contains the Ligand L that only binds to cation C+ 3. On the inner side of the electrode membrane, a known conc. of the Cation with Anion present; On the outer side, the electrode is immersed in a solution of unknown conc. Ag/AgCl is the internal reference electrode which is immersed in the inner solution is .

4. The potential difference across the membrane is measured between the two reference electrodes (external / Internal). If the concentration of ions in the analyte changes, the Voltage changes 5. A calibration curve (b/w Voltage and concentration of of analyte in the solution can then help us determine the amount

In a glass electrode, the membrane is made up of PVC with Plasticisers (dioctylsebagate) that softens it and dissolves the ion selective compounds (Ionophore). is usually tetraphenyl borate WORKING 1. All the analyte inside the membrane is bound as complex which is in equilibrium with a small amount of free Ligand L. The (Hydrophobic). cant enter membrane 2. ions can diffuse across the interface. Due to the diffusion, there is slight excess charge in the aqueous phase. The diffusion results in a free energy decrease in the solution given by ( )

4. The driving force for the diffusion is the salvation of the cation. As the diffusion proceeds, there is an electrical P.D which opposes diffusion of more into aqueous phase. The corresponding free energy change (This P.D is measured by external ref.)

( ( )

5. We have

at the boundary b/w membrane and inner solution (measured by internal ref.)

6. Resultant potential across the membrane is given by

( 7. By using a saturated inner solution, we ensure that depends only on the analyte activity

) is also a constant, thus the cell potential

Types of I.S.E 1. Glass membrane (i.e. H+ electrode) 2. Solid-state electrode (e.g. F- electrode uses a Eu2+-doped LaF3 crystal) 3. Liquid-based electrode (e.g. Ca2+ electrode uses a liquid chelator) 4. Compound electrode (e.g. CO2 gas sensing electrode) Glass Electrode The most pH sensitive electrode, which consists of a thin membrane of certain varieties of glass which is responsive to changes in [H+] ions. For 2 solutions separated by thin membrane, we have a potential

The glass electrode against any suitable electrode gives a potential which is related to the pH by an expression

is the potential of the ref. electrode. (generally SCE)

Glass electrode is useful for pH measurements but not effective in highly acidic/ alkaline solutions

IV. POTENTIOMETRIC TITRATION Potentiometric titrations can be carried out for those reactions which involve the addition/ removal of some ion for which an electrode is available. The potential is measured after successive additions of small volumes of titrant or continuously with automatic recording device. The precision can be increased by use of concentration cell. Since Cell potential varies directly with log of ion concentration, the Potentiometric titration curves has a shape exactly opposite as that of pH metric titration curves

a) Neutralisation titration: Glass electrode can be used against a reference (calomel) electrode. should be less than
E = Eo + 0.0591pH

b) Precipitation/ Complexation titration: The formation of precipitate/ comples removes ions from the solution. Usually Ag/AgCl Calomel electrodes are used
E = Eo + 0.0591 log [Ag+].

c) Redox Reactions: Platinum (Inert) electrode used. Powerful oxidizing agents (KMnO4, K2Cr2O7) form metal oxide coate which is removed by catodic reduction in dilute acid solution.
E = Eo + (0.0591/n)*log([ox]/[red]).

V. ADVANTAGES OF POTENTIOMETRIC TITRATIONS 1. Equivalence point detection instead of End point detection 2. Automation. Very convenient to handle 3. Can be used in the titration of polyprotic acids and in Multiple Analyte Detection 4. Can be used if there is no suitable indicator 5. Can be used when color change is difficult to ascertain/ turbid or fluorescent analyte solution