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POTENTIOMETRY by Mr. Shaise Jacob Faculty – Pharmaceutical Analysis Nirmala College of Pharmacy Muvattupuzha, Kerala, India :

POTENTIOMETRY by Mr. Shaise Jacob Faculty – Pharmaceutical Analysis Nirmala College of Pharmacy Muvattupuzha, Kerala, India

Slide 2:

Measuring the potential or emf of a solution Using a set of indicator & reference electrode. INDICATOR ELECTRODE Responds to changes in emf or Ph of the solution To indicate emf or ph Example – Glass electrode, antimony electrode


REFERENCE ELECTRODE Which has a standard potential on its own And its potential does not change to whichever solution it is dipped. E.g. hydrogen electrode, saturated calomel electrode & silver-silver chloride electrode Most commonly used is saturated calomel electrode

Nernst equation:

Nernst equation The Nernst Equation allows us to calculate the voltage produced by any electrochemical cell given Eo values for its electrodes and the concentrations of reactants and products.

Slide 5:

The potential (E) of a metal electrode at 25 o C immersed into a solution of its own ions is given by E o – Standard potential of the metal N – valency of ions C – concentration of ions



Slide 8:

It can be used as indicator as well as reference electrode Platinum coil coated with platinum black and has wire contacts through mercury The assembly enclosed in a glass covering through which Hydrogen 99.8% is passed at 1 atm pressure

Slide 9:

The standard H2 electrode potential is defined as the potential that is developed between the H2 gas adsorbed on the pt metal and H+ of the solution when the H2 gas at a pressure of 760 mm of Hg is in equilibrium with H+ of unit concentration The magnitude of SHE potential is considered to be zero. It is used- 1) For the determination of electrode potential of metal electrode system. 2) For the determination of pH of the solution.

Limitations :

Limitations 1) It is rather difficult to regulate the pressure of the H2 gas to be at exactly 1atm throughout the experiment. 2) If the solution contains any oxidizing agent, the H2 electrode cannot be used. 3) Excess of H2 bubbling out carries little HCl with it and hence the H+ concentration decreases. In such a system, it is difficult to maintain the concentration of HCl at 1M. 4) Platinum foil gets easily poisoned by the impurities present in the gas and HCl. In fact, the attainment of equilibrium is ensured by trial and error.



Slide 15:

It contains of an inner jacket and outer sleeve Inner jacket has wire contact with Hg and plugged with a mixture of calomel Hg 2 Cl 2 & KCl Outer sleeve – crystals of KCl & porous plug of asbestos Space b/w inner jacket & outer sleeve is filled with either saturated KCl or 1N KCl or 0.1N KCl

Slide 16:

Application The SCE is used in pH measurement, cyclic voltammetry and general aqueous electrochemistry. This electrode and the silver/silver chloride reference electrode work in the same way. In both electrodes, the activity of the metal ion is fixed by the solubility of the metal salt. The calomel electrode contains mercury, which poses much greater health hazards than the silver metal used in the Ag/AgCl electrode


MERITS OF SCE Ease of construction Stability of potential

Silver- Silver chloride electrode:

Silver- Silver chloride electrode The silver/silver chloride reference electrode is a widely used reference electrode because it is simple, inexpensive, very stable and non-toxic. it is mainly used with saturated potassium chloride (KCl) electrolyte, but can be used with lower concentrations such as 1 M KCl and even directly in seawater.

Slide 20:

Silver wire coated electrolytically with silver chloride and dipped into KCl It has the advantage that it is easy to use Demer it is that it is difficult to prepare

Mercurous Sulphate Electrode:

Mercurous Sulphate Electrode Type – Reference electrode ♠ Similar in construction to the calomel electrode but utilizes dilute sulphuric acid saturated with mercurous sulphate. Use - I t is used in solution, where silver or lead ions are present




INDICATOR ELECTRODES ♠ Indicator electrode indicates the potential or Ph of a solution in comparison to a reference electrode of a known potential. Hydrogen Electrode Glass Electrode Most widely used indicator electrode

Slide 26:

It is selective to change in conc. of hydrogen ions . It consists of a glass tube with a thin Ph sensitive glass bulb at its tip. Ag- AgCl wire at the centre of the tube Lower tip immerses into the 0.1N HCl Filled in the glass bulb. Glass Membrane of the bulb is extremely thin & chemically made up of alumino silicate.

Slide 27:

Potential of the glass electrode given by the following equation – E = K + 0.0592 (Ph 1 – pH 2 ) at 25 o C K = Constant for the electrode, depends on - Thickness of glass bulb Composition of solution Ph 1 = pH of solution in bulb pH 2 = pH of test solution Now, pH 1 is constant for given electrode so, E = K – 0.0592 pH 2


ADVANTAGES Response is very rapid Chemically resistant to oxidizing & reducing agents, dissolved gases, salts etc. When Lithia -silica glasses are used, it can be used over the entire Ph range.

Use – for pH measurement:

Use – for pH measurement DISADVANTAGES It is extremely fragile Minute abrasions on the surface of the tip, damages the electrode It cannot be used with simple potentiometers, because of the high resistance.

Antimony – Antimony Oxide Electrode :

Antimony – Antimony Oxide Electrode it consists of a antimony rod dipped into a solution, whose potential or Ph to be determined. Antimony oxide is formed on exposure to air ADVANTAGES It can be used from Ph 3 to Ph 8. it can be used even up to Ph 12 It is not easily poisoned or damaged Can be used even with viscous fluids


DISADVANTAGES 1. This electrode cannot be used in presence of dissolved oxygen, oxidizing agents, complexing agents etc..


ION SELECTIVE ELECTRODE a ) General i. electrodes based on determination of cations or anions by the selective adsorption of these ions to a membrane surface. ii. Often called I on S elective E lectrodes (ISE) iii. Desired properties of ISE’s ‚ minimal solubility – membrane will not dissolve in solution during measurement – silica, polymers, low solubility inorganic compounds ‚ Need some electrical conductivity ‚ Selectively binds ion of interest




ION SELECTIVE ELECTRODE This is a extension of concept of glass electrode Electrodes which is specifically permeable to specific types of ions only & other ions are resisted. Now-a-days verities of ion selective electrodes are available SOLID MEMBRANE ISE solid substance of crystal structure is used to select any ion

Slide 36:

Specifically designed liquid is filled in specific plastic material or resin material, - semi permeable membrane, highly selective for particular ions.


LIQUID MEMBRANE ISE LIQUID IS FILLED IN PLASTIC OR RESIN MATERIAL , WHICH HAS SEMI PERMIABLE MEMBRANE - SELECTIVE FOR PARTICULAR ION . Membrane” usually consists of organic liquid (not soluble in sample) held by porous disk between aqueous reference solution and aqueous sample solution. ‚ Membrane has ability to selectively bind ions of interest

Example: Calcium dialkyl phosphate Liquid membrane electrodes :

Example : Calcium dialkyl phosphate Liquid membrane electrodes


ENZYME ELECTRODE Enzyme is chemically bonded to some inner surface They are very selective for reaction with substrate Thus, this electrode is useful for measurement of insulin or adrenaline etc.


QUINHYDRONE ELECTRODE This electrode is used as a substitute of hydrogen electrode to overcome its disadvantages. Bright platinum wire dipped into the test solution which has been saturated with quinhydrone .


PLATINUM ELECTRODE MOST SIMPLE ELECTRODE It has a platinum plate or wire or ring Platinum is the most inert & non reactive metal – which is a good character for stable electrode USE – It is used in all redox titrations


pH METERS Same as potentiometers pH meters consists of two electrodes 1. Saturated Calomel electrode 2. Glass electrode ☼ USE – they are used to measure pH. * here instead of platinum electrode, glass electrode is used

Slide 47:

Bze for measurement of Ph, we want to measure selectively only H + Ion conc. & glass electrode is H ion electrode. FEATURES / ADVANTAGES OF pH METERS Due to the following features temperature control knob Calibration knob Temperature display Internal calibration, without external calibration using buffers


POTENTIOMETRIC TITRATIONS End point of titrations can be determined by measuring changes in potential of a solution caused by addition of titrant. ADVANTAGES Colored solutions, dil. Solutions or turbid suspensions can be titrated. Titration can be automated Mixture of components can be titrated Inexpensive & more accuracy Reference electrode potential need not be known - constant



Method of detecting end point:

Method of detecting end point Indicator method not suitable Potentiometer – determining end point graphically by using – Normal titration curve Emf vs vol. of titrant

2. First derivative curve:

2. First derivative curve A plot of ▲E/▲V VS Vol. of titrant

Second derivative curve:

Second derivative curve A plot of ▲ 2 E/▲ 2 V VS Vol. of titrant

Slide 56:

At the end point , the rate change of potential is maximum. APPLICATIONS Following types of titrations can be done by potentiometry. Acid base titrations Redox titrations Diazotisation titrations Precipitation titrations Complexometric titrations

Dead stop end point technique ( Biamperometry):

Dead stop end point technique ( Biamperometry) E.g. – determination of water ( moisture content) by KARL FISCHER REAGENT It contains two platinum electrodes b/w which Small emf is applied No current flows till the solution is free from polarizing substances Current flows only when both electrodes are depolarized

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