Electrochemistry

Electrochemistry Definition The study of the process involved in the inter conversion of electrical energy and chemical energy. It deals with the chemical reactions produced by passing electric current or the production of electric current through chemical reactions.

Electrochemical Processes The chemical reactions involving electricity are called electrochemical reaction Electrochemical reactions are redox reactions where an oxidation and a reduction reaction go side by side and are separated in space. The reactions are two types 1. Induced electrolytic reactions- these non spontaneous reactions are forced by the passage of electricity through the reactants 2. spontaneous redox reaction that can produce electricity REDOX REACTIONS

Oxidation-reduction or redox reactions take place in electrochemical cells.

The term redox comes from the two concepts of reduction and oxidation. Oxidation describes the loss of electrons: Zn (s) Zn2+ (aq) + 2 e -

Reduction describes the gain of electrons Cu2+ (aq) + 2 e Cu (s)

Each of the reaction is known as half- reaction or half-cell and both must always go side by side The net reaction: Zn (s) + Cu 2+ (aq) Zn 2+ (aq) + Cu (s)

Electrochemical Cells
An electrochemical cell is a device capable of either deriving electrical energy from chemical reactions, or facilitating chemical reactions through the introduction of electrical energy.

There are two types of electrochemical cells. TYPES: Galvanic and Electrolytic Cells 1. Spontaneous reactions occur in galvanic (voltaic) cells; 2. Nonspontaneous reactions occur in electrolytic cells. Both types of cells contain electrodes where the oxidation and reduction reactions occur. Oxidation occurs at the electrode termed the anode and reduction occurs at the electrode called the cathode.
TYPES OF ELECTROCHEMICAL CELLS 1. Galvanic or voltaic cell: Produces energy by a spontaneous reaction which produces electricity as a result of electron transfer The cells used for the generation of electrical energy from chemical reactions are called galvanic or voltaic cells.

The redox reaction in a galvanic cell is a spontaneous reaction. For this reason, galvanic cells are commonly used as batteries. Galvanic cell reactions supply energy which is used to perform work. The energy is harnessed by situating the oxidation and reduction reactions in separate containers, joined by an apparatus that allows electrons to flow.
ex. A common galvanic cell is the Daniell cell, batteries, corrosion, etc

2. Electrolytic Cells The redox reaction in an electrolytic cell is

nonspontaneous. Electrical energy is required to induce the electrolysis reaction.

The cells used for electrolysis are called electrolytic cells ex. Charging of battery, electroplating ,etc

Electrodes & Charge The anode of a galvanic cell is negatively charged, since the spontaneous oxidation at the anode is the source of the cell's electrons or negative charge. The cathode of a galvanic cell is its positive terminal. The anode of an electrolytic cell is positive (cathode is negative), since the anode attracts anions from the solution. In both galvanic and electrolytic cells, oxidation takes place at the anode and electrons flow from the anode to the cathode.
An electrochemical cell is obtained by coupling two half cells 1. Anode: oxidation half-reaction takes place 2. Cathode: reduction half-reaction occurs 3. Salt bridge: A salt bridge is often employed to provide ionic contact between two half-cells with different electrolytesto prevent the solutions from mixing and causing unwanted side reactions. Ex.: filter paper soaked in KNO3 Functions of salt bridge: 1. The salt bridge allows ions to move on either side and maintain the electrical neutrality of the electrolyte on both sides. 2. It serves as a bridge to complete the electric circuit. 3. It prevents the liquid junction potential between the two electrodes.

Liquid junction potential occurs when two solutions of different concentrations are in contact with each other. The more concentrated
3

solution will have a tendency to diffuse into the comparatively less concentrated one. The rate of diffusion of each ion will be roughly proportional to its speed in an electric field. If anion diffuses more rapidly than the cation, it will diffuse ahead into the dilute solution leaving the later negatively charged and the concentrated solution positively charged. So an electrical double layer of positive and negative charges will be produced at the junction of the two solutions. So at the point of junction, a difference of potential will develop because of the ionic transfer. This potential is called liquid junction potential or diffusion potential. The magnitude of the potential depends on the relative speeds of the ions.

4. External circuit: These two half-cells joined together by wire through which electrons flow. 5. Electrolyte: Internal pathway that allows ions to migrate between them so as to preserve electro neutrality.

Difference in electrolytic cell and galvanic cell Electrolytic cell 1. Conversion of electrical energy into chemical energy 2. The anode carries positive charge vice versa. Galvanic cell 1. Chemical energy into electrical energy 2. The anode carries negative charge Vice versa.

3. Electrons are supplied to the cell 3. Electrons are drawn from the cell. from the external power supply. 4. Spontaneous reaction. Eocell is 4. Not a spontaneous reaction. +ve, then the process is spontaneous Eocell is -ve, then the process is nonspontaneous E.g electroplating eg. Corrosion 5. The extent of chemical reaction occurring at the electrode is governed by Fradadays law of electrolysis. 5. The e.m.f of the cell depends on the concentration of the electrolyte and chemical nature of the electrode (Nernst Equation)

6. The amount of electricity passed 6. The e.m.f produced in the cell is measured by potentiometer. during electrolysis is measured by Coulometer.

ELECTRODE POTENTIAL (E)

When a metal (M) is placed in the solution of its own ion it may act as an anode or cathode. As an anode: Positive metal ions passing into solution (oxidation) leaving behind e-s on the electode. The anode attains negative charge due to accumulation of e-s which attracts positively charged free ions (cations) from the solution. Due to the attraction the positive ions remain close to the metal. M Mn+ +ne-

As a cathode: Positive ions depositing on the metal electrode (reduction) and it attracts negatively charged ions. Mn+ +ne- ---M

HELMHOLTZ ELECTRICAL DOUBLE LAYER

Thus a sort of electrical double layer (positive or negative ions) is formed all around the metal. This layer is called Helmholtz electrical double layer. This layer prevents further passing of or deposition of metal ions on the metal. Consequently a difference in potential set up between the metal and its solution. At eqm, the potential difference is constant , which is known as Electrode potential of a metal. EMF: The diff. of potential which causes flow of current/electrons from one electrode to another is called the electromotive force

Electrode potential (E): The measure of tendency of an electrode to lose or gain electrons when it is contact with a solution of its own ion is called electrode potential. Standard electrode potential (Eo): The measure of tendency of an electrode to lose or gain electrons, when it is contact with a solution of its own salt of 1 molar concentration at 25o C is known as standard electrode potential. Oxidation electrode potential (Eooxid): The measure of tendency of an electrode to lose electrons when it is contact with a solution of its own ion is called oxidation electrode potential. Reduction electrode potential (E
o red):

The measure of tendency of an electrode

to gain electrons when it is contact with a solution of its own ion is called electrode potential. Factors affecting electrode potential 1. Nature of the electrode metal 2. Temperature 3. Concentration of metal ions in solution

Measurement of Single electrode potential

Impossible to know the absolute value of single electrode potential. To measure the ele. pot of one electrodes which is connected to reference electrode to form a complete cell The electrode whose electrode pot. is either exactly known or arbitrarily fixed is called reference electrode The pot. of one electrode is fixed arbitrarily then another electrode pot. can be measured EMF of the complete cell can be directly read from the potentiometer. Ecell= Eo cathode - Eo anode

Potential of the single electrode can be calculated by Nernst Equation:

The final and the most fundamental form the Nernst equation is written as:

where R is the universal gas constant, T is the absolute temperature in degrees Kelvin, z is the charge number of the electrode reaction (which is the number of moles of electrons involved in the reaction as written), and F is the Faraday constant (96,500 C mole-1). The notation ared represents the chemical activities of all of the species which appear on the reduced side of the electrode reaction and the notation aox represents the chemical activities of all of the species which appear on the oxidized side of the electrode reaction.

Derivation Nernst equation was derived from Vant Hoff reaction isotherm for the
redox reaction, M
2+

+ 2e- --

Vant Hoff Reaction Isotherm

G = - RT ln K +RT ln Q
Vant Hoff reaction isotherm is an equation for the change in free energy during the chemical reaction. it relates the G (free energy change) the redox reaction as Q (Reaction Quotient) = aC . aD / aA . aB aC . aD = chemical activity of products aA . aB
= chemical = [P]

and K (equilibrium constant) for

/[R]

activity of reactants

The activities of gases are usually taken as their partial pressures and the activities of solutes such as ions are usually taken as their molar concentrations.

G = - RT ln K +RT ln [P] /[R] Go = - RT ln K So equation 1 becomes

---------------(1)

At standard conditions of T and P, at equilibrium [P] = [R]

G = Go +RT ln [P] /[R] ---------------------(2)

Electrical energy (nFE) arises from the expense of free energy of the system (- G).

Let n faraday charge be taken out of a cell of emf E; then work done by the cell will be calculated as: Work = Charge x Potential = nFE

10

Work done by the cell is equal to decrease in free energy. - G = nFE

- Go = nFEo = Go + RT ln [product] / [reactant]-------------(2) becomes

-nFE = -nFEO + 2.303 RT log [product] / [reactant] E = Eo - 2.303 RT / nF log [P]/[R]

(divide by nF)

For redox cell reaction, Ecell = Eocell - 2.303 RT / nF log [P]/[R]

R = 8.314 J/K/mole At 25o C, T =298 K F= 96500 Coulombs THE STANDARD EMF OF THE CELL: Eocell = EoR - EoL

Oxidation potential
The oxidation potential of an electrode for the reaction M---Eoxid [M] = 1 = Eooxid - 0.0592/n log [Mn+] Mn+ + ne----- half cell = Eooxid - 0.0592/n log [Mn+] / [M]

Eoxid

11

Reduction potential
The reduction potential of an electrode for the reaction Mn+ + ne- ---Ered [M] = 1 Ered = Eored + 0.0592/n log [Mn+] M ----- half cell = Eored - 0.0592/n log [M] /[Mn+]

Uses of Nernst equation: 1. To calculate electrode potential of unknoun M 2. To predict the corrosion tendency of metals 3. To calculate the emf of a cell

12

ELECTROCTREMICAL SERIES: The arrangement of metals in

the increasing order of their std. reduction electrode potential Half-Reaction Li+ + eNa+ + eMg2+ + eAl3+ + 3eTi2+ + 2eMn2+ +eZn2+ + 2eFe2+ + 2eCo2+ + 2eNi2+ + 2eFe3+ + 3e2H+ + 2eSn4+ + 2eCu2+ + 2eFe3+ + eAg+ + ePt4+ + eMn4+ + 2eCr6+ + 3eAu+ + eMn7+ + 5eCr4+ + 1eAu3+ + 3eLi Na Mg Al Ti Mn Zn Fe Co Ni Fe H2 (g) Sn2+ Cu Fe2+ Ag Pt Mn2+ Cr3+ Au Mn2+ Cr3+ Au E0 -3.05 -2.70 -2.40 -1.66 -1.63 -1.18 -0.76 -0.44 -0.28 -0.25 -0.04 0.00 +.15 +0.34 +0.77 +0.80 +0.86 +1.23 +1.33 +1.50 +1.51 +1.60 +1.69

13

F2 + 2e-

2F-

+2.87

Application of electrochemical series

1. Relative ease of oxidation or reduction can be predicted The metals on the top with ve reduction pot. Can more easily undergo oxidation & act as anode. Ex. Zn = -0.76 V favours oxidation reaction While the metals at the bottom with +ve reduction. Pot. has great tendency to undergo reduction & act as cathode Ex. Cu = +0.34 V favours reduction reaction. 2. Cell representation can be predicted A galvanic cell formed by two half cells with 2 diff. metals. From EMF series, the metal which is undergoing oxidation or reduction can be predicted The electrode undergoes oxidation (anode) is written at left The electrode undergoes reduction (cathode) is written at right Salt bridge is written in between these two electrodes with in the double line Ex. For Daniel cell with Zn and Cu electrodes The cell representation Zn / Zn2+ // Cu2+ / Cu The cell reaction can also be written Anodic reaction: Zn (s) Zn2+ (aq) + 2 e Cu (s) Zn 2+ (aq) + Cu (s) Cathodic reaction: Cu2+ (aq) + 2 e The net reaction: Zn (s) + Cu 2+ (aq)

14

3. Calculation of Std emf (Eocell) of the cell Oxidn Half cell|| Redn half cell

Eocell= Eocathode Eoanode

Ex.

Standard e.m.f (Eocell) of Danial cell

Eocell = EoCu EoZn = +0.34 (-0.76) = +1.1 V OR

Eocell = Eooxid + Eored

= +0.76 + 0.34 = + 1.1 V 4. Calculation of standard free energy (Go) and equilibrium constant (Keqm) Go = - nFEo

Keqm :
Go = - RT ln Keqm - nFEo = - RT ln Keqm Eo = __RT_ 2.303 log Keqm nF log Keqm = nEo / 0.0592 at 25o C

Keqm = Antilog [nEo / 0.0592]

15

5. The spontaneity or feasibility of the cell reaction can be predicted Spontaneity of the redox reaction can be predicted from the e.m.f value of complete cell reaction. If E If E
o o

cell = + ve, Go = - ve, since Go = - nFEo the reaction is feasible. cell = - ve , Go = + ve. Then the reaction is not feasible.

6. Hydrogen liberating tendency of the metal can be predicted The metal with low reduction potential will displace H2 from an acid solution. Zn+ H2SO4 Ag + H2SO4 ZnSO4 + H2 no reactn The metal with +ve potential will not displace H2 from an acid solution

7. Replacing tendency of a metal (M) by another M: The metals with low reduction potential undergo oxidation and pass into the solution and the M ion with high red. potential undergo reduction and get deposits on electrode. Zn, Ni undergo dissolution in CuSO4 solution and will displace Cu from solution.

8. Corrosion tendency of M: The metals higher in the series are anodic or more active and they are more prone to corrosion. The metals lower in the series are noble metals and they are less prone to corrosion.

16

Potentiometric measurement of e.m.f:

EMF: The diff. of potential which causes flow of current/electrons from one electrode to another is called the electromotive force It is expressed in volts. The e.m.f cannot be determined accurately by connecting directly a voltmeter between the two electrodes, because during such a measurement, a part of the cell current is drawn, thereby causing a change in the e.m.f due to the formation of reaction products at the electrodes and change in the conc. of the electrolyte around the electrodes. In potentiometer measurement of e.m.f of a cell can be done by Poggendorffs

compensation principle.
In the potentiometric measurement of emf of a cell, an external adjustable potential is applied and its value determined, it prevents the current flow from the given cell. Weston standard cadmium cell is used as standard cell. A storage battery of high voltage is connected across the wire A, with positive terminal at A and negative terminal at B. The test cell whose emf to be measured, and the standard cell is included in another circuit with positive terminal at A and negative terminal at B through connecting keys, a galvanometer and sliding contact. The first circuit is completed by introducing the Key K1, now the test cell is included in the circuit. The sliding contact is moved along the wire AB, till the point D is reached, when there is no deflection in galvanometer. The potential difference between the points AD = EMF of the test cell. Emf of the test cell (Ex) = length AD. The second circuit is completed by introducing the Key K2, now the test cell is included in the circuit. The sliding contact is moved along the wire

17

AB, till the point D is reached, when there is no deflection in galvanometer. Emf of the standard cell (Es) = length AD Ex / Es = length AD/ length AD The unknown emf of the test cell Ex = length AD/ length AD x Es
Storage battery + B + K1 X

K2 + Standard cell

18

Reversible and irreversible cells

Daniell cell has the emf value 1.09 volt. If an opposing emf exactly equal to 1.09 volt is applied to the cell, the cell reaction, Zn + Cu2+ --> Cu + Zn2+ stops but if it is increased infinitesimally beyond 1.09 volt, the cell reaction is reversed. Cu + Zn2+ --> Zn + Cu2+ Such a cell is termed a reversible cell. Thus, the following are the two main conditions of reversibility: (i) The chemical reaction of the cell stops when an exactly equal opposing emf is applied. (ii) The chemical reaction of the cell is reversed and the current flows in opposite direction when the opposing emf is slightly greater than that of the cell. Any other cell which does not obey the above two conditions is termed as irreversible. A cell consisting of zinc and copper electrodes dipped into the solution of sulphuric acid is irreversible. Similarly, the cell Zn|H2S04(aq)|Ag is also irreversible because when the external emf is greater than the emf of the cell, the cell reaction, Zn + 2H+ --> Zn2+ + H2 is not reversed.

19

Weston Standard Cadmium Cell:

A standard cell is one which is capable of giving constant and reproducible e.m.f., and has a negligible temperature-coefficient of the e.m.f. The standard cell is a source of unvarying potential. The e.m.f of such a cell must be reproducible and the temperature coefficient (change in e.m.f with temperature) should be very low. These requirements are fulfilled by Western Standard Cadmium Cell. Description: It consists of a H-shaped. glass vessel, with the lower ends of both arms closed, having platinum wire sealed into the bottom of each arm. The positive electrode contains mercury over which a paste of mercurous sulphate (Hg2SO4) and mercury is placed. The negative electrode consists of an amalgam of Cd and Hg, containing about 12-15% of Cd by wt. Over both electrodes are sprinkled some crystals of solid CdSO4. 8/3 H2O The remaining part of the part of the cell is filled with a saturated solution of cadmium sulphate. The upper ends of the tube are closed with corks and sealing wax. When the cell operates, the following reactions occur at the electrodes: Cd (s) -Cd2+ (aq) + 2e(at negative electrode)

Hg2SO4 (s) + 2e- -

2Hg (l) + SO42- (at positive electrode)

The solid crystals of CdSO4. 8/3 H2O keep the electrolyte saturated at all temperatures. The potential of this cell is 1.01830 volts at 20o C and 1.01807 volts at 25o C and it varies slightly (about -0.09046 v per degree centigrade).The cell works for many years at a stretch, without any voltage changes.

20

Concentration cell
A concentration cell is made up of two half cells having identical electrodes, identical electrolyte, except that the concentration of the reactive ions at the two electrodes are different. The electrical energy in a concentration cell arises from the transfer of electrons from the electrode in the lower concentration side to the electrode in higher concentration side. The two half - cells may be joined by a salt bridge. When a metal (M) electrode is dipped in a solution containing its own ions [Mn+], then the potential (E) is developed at the electrode at the electrode, the value of which varies with conc. Of the ions in accordance with the Nernsts equation: E =Eo - 2.303 RT / nF log 1/ [Mn+] E =Eo + 2.303 RT / nF log C Let us consider a general conc. cell represented as: M/Mn+ (C1M) II Mn+ (C2M) I M+ Where C1 and C2 are the concentrations of active metals ions (Mn+) in contact with two electrodes respectively and C2 > C1. THE CELL REACTIONS ARE: At left electrode (anode): M -Mn+ (C1.) + neM Mn+ (C1.) At right electrode (cathode): Mn+ (C2) + ne- THE NET CELL REACTION: Mn+ (C2) --E.M.Fcell. of cell = Eright - Eleft = [Eo + 2.303RT/nF log C2 ] [Eo + 2.303RT/nF log C1] = 2.303RT/nF log C2/C1 Ecell = 0.0592/n log C2/C1

21

The e.m.f so developed is due to the mere transference of metal ions from the solution of higher conc. (C2) to lower conc. (C1.). Applications: i. ii. Determination of solubility of sparingly soluble salts: Determination of the valency of an ion.

22

REFERENCE ELECTRODS: The electrode with exactly known standard potential or fixed as constants or zero, with which we can compare the potentials of other electrodes The Characteristics of reference electrodes 1. The electrode potential should be fixed as constants or zero. 2. The temperature co-efficient should be very low. 3. It should be a reversible electrode. It can function both as an anode and a cathode 4. It should be easy to handle and use in laboratory.

1. Standard Hydrogen Electrode

Construction This is a gas electrode. It consists of a thin rectangular platinum foil which is coated with fresh platinum black to increase the adsorption capacity of the metal ot adsorb H2 gas. The inner tube is enclosed in an outer jacket having an inlet tube for sending in H2 gas and has a perforated wider base for the escape of excess of H2. This unit is dipped in 1 M HCl taken in a beaker such that the metal foil remains in the solution. In the above system, when the H2 gas at a pressure of 1atm is bubbled through 1M HCl, the electrode (constructed) or formed is called STANDARD HYDROGEN ELECTRODE (SHE) or Normal H2 electrode (NHE). Working This is represented as Pt, H2 (1 atm) / H+ (IM) When pure and dry H2 gas is passed through the inlet tube, a part of the gas gets adsorbed and the excess bubbles out through the perforations. Depends on the other half cell connected to SHE, SHE can under go either oxidation or reduction.

23

The electrode is represented as: Pt, H2 (1 atm) ; H+ (1M) The electrod potential of SHE is fixed as zero. The either of the reaction takeplace H+ (aq) + e- - H2 (g) - H2 (g) H+ (aq) + e-

Act both as anode and cathode based on another M connected, it is a reversible electrode. When M electrode with lower reduction potential than H2, is coupled with SHE, M undergoes oxidation and act as anode. Ex. Zn and SHE acts as cathode If the M electrode possesses higher reduction potential than H2, is coupled with SHE, undergoes reduction and act as cathode. Ex. Cu

24

Determination of single electrode potential of a metal

1. If the single electrode Zn in ZnSO4 is connected to SHE then the emf of the complete cell determined by means of a potentiometer. Since emf of SHE is zero, the observed e.m.f gives directly the e.m.f of half-cell containing the solution under test. Zn has the tendency to under go oxidation, act as anode. Pot. of the Zn single electrode can be obtained by E cell = Ec. -Ea Ecell = ESHE Eunknown(Zn2+, Zn) ESHE = 0 Eunknown(Zn2+, Zn) = 0 Ecell Eunknown(Zn2+, Zn) = Ecell 2. If the single electrode Cu in CuSO4 is connected to SHE then the emf of the complete cell determined by means of a potentiometer. Since emf of SHE is zero, the observed e.m.f gives directly the e.m.f of half-cell containing the solution under test. Cu has the tendency to undergo reduction & act as cathode Pot. of the Cu single electrode Ecell = Eunknown(Cu2+, Cu) - ESHE ESHE = 0 Ecell = Eunknown(Cu2+, Cu)

25

Zn possess lower red. Pot. than H2. Zn undergoes oxidation and act as anode. H2 undergoes reduction. H+ (aq) + e- - H2 (g) --act as cathode

Cu possess higher red. Pot. than H2. Cu undergoes reduction and act as cathode. H2 undergoes oxidation, H2 (g) -H+ (aq) + e- --act as anode

26

Determination of pH of the test solution

The solution of unknown pH is taken with the Pt electrode. A slow current of H2 at 1 atm is passed over the Pt electrode in the solution. This half cell is connected to the Standard hydrogen electrode The half cell reduction reaction is H+(aq) + e- -- H2 (g)

The electrode potential of the half cell is Ered(unknown) = Eored - 0.0592/n log [H2] / [H+] Eored = 0, n = 1 Ered(unknown) =0 - 0.0592 log 1/ [H+] Ered(unknown) =0 + 0.0592 log [H+] Ered(unknown) = - 0.0592 pH THE EMF OF THE CELL: Ecell = EoREF - Eounknown Ecell = 0- ( -0.0592 pH) Ecell = 0.0592 pH pH = Ecell / 0.0592 Since, pH = - log [H+]

Uses: 1) For the determination of single electrode potential of a metal electrode system 2) For the determination of pH of the solution.

27

Limitations of Hydrogen Electrode 1) It is rather difficult to regulate the pressure of the H2 gas to be at exactly 1atm throughout the experiment. 2) 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. 3) 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. 4) If the solution contains any oxidizing agent, the H2 electrode cannot be used.

Saturated Calomel electrode

A mercury mercurous chloride electrode The Saturated calomel electrode (SCE) is a reference electrode based on the reaction between elemental mercury and mercury(I) chloride. The aqueous phase in contact with the mercury and the mercury(I) chloride (Hg2Cl2, "calomel") is a saturated solution of potassium chloride in water. The electrode potential of calomel electrode depends on the conc. of KCl The electrode potential for decinormal 0.1 N KCl is +0.3335 V for normal KCl solution +0.2810 V and for saturated calomel electrode (SCE) is +0.2422 V

28

In cell notation the electrode is written as: Hg, Hg2Cl2 (s), KCl (sat.solution) / Pt

The electrode potential of SCE is arbitrarily fixed as + 0.2422 V. The electrode is based on the redox reaction Hg22+ (s) + 2e- <--- Hg2 (l) 1. If the single electrode Zn in ZnSO4 is connected to SCE SCE = cathode Zn/ Zn2+ electrode = anode The half cell reaction is HgCl2 (s) +2 e- -- Hg (l) +2 Cl- (aq) Reduction of mercurous to mercury The single electrode pot. Can be calculated Ecell = ESCE - Eunknown (Zn2+, Zn)

ESCE = +0.2422 V Eunknown (Zn2+, Zn) = +0.2422 Ecell

29

2. When Cu electrode is connected to SCE Cu undergo reduction and act as cathode and SCE act as anode At SCE oxidation takes place Hg Hg+ + eHg2Cl2 2 Hg+ + 2Cl2 Ecell

The single electrode pot. Can be calculated = Eunknown(Cu2+, Cu) - ESCE

ESCE = +0.2422 V Eounknown(Cu2+, Cu) = Ecell+ 0.2422

30

Determination of pH of the test solution

The solution of unknown pH is taken in a hydrogen electrode with the Pt electrode. A slow current of H2 at 1 atm is passed over the Pt electrode in the solution. This half cell is connected to the SCE Ecell = EoSCE - Ered(unknown) The half cell reaction is H+(aq) + e- -- H2 (g)

The electrode potential of the half cell is Ered(unknown) = Eored - 0.0592/n log [H2] / [H+] Eored = 0, n = 1 Ered(unknown) =0 - 0.0592 log 1/ [H+] Ered(unknown) =0 + 0.0592 log [H+] Ered(unknown) = - 0.0592 pH THE EMF OF THE CELL: Ecell = EoSCE - Ered(unknown) Ecell = 0.2422- ( -0.0592 pH) Ecell = 0.2422 + 0.0592 pH pH = Ecell - 0.2422 / 0.0592 Since, pH = - log [H+]

31

Quinhydrone electrode
The quinhydrone system involves the following reaction:
O OH

+ 2H

+ 2e-

<----->

OH O Q Quinone + 2H
+

+ 2e-

<----->

HQ
2

HYdroquinone

When a Pt electrode is immersed in a solution of unknown concentration of H+ containing quinhydrone, a potential is estabilished on electrode is given by, EQ = EoQ - 0.0592/2 log [H2Q] / [Q][H+]2 And, if quinine and quinhydrone are taken in equimolar concentration, [H2Q] = [Q], then the above equation reduces to: EQ=EoQ - 0.0592/2 log 1 / [H+]2 EQ=EoQ + 0.0592/2 ( 2 log [H+] ) EQ = EoQ - 0.0592 pH EQ = 0.6994 - 0.0592 pH This electrode is employed for the measuring pH of the solution as an indicator electrode. Construction: This electrode can be easily set up by preparing saturated solution of quinhydrone and an indicator electrode usually Pt electrode is inserted in it.

32

Working: pH measurement:
The half cell is combined with any other reference electrode (SCE) and the emf of the cell can be measured by a potentiometrically. The complete cell may be represented as Pt / H2Q, Q, H+ (unknown) // KCl (sat.d), Hg2Cl2(s), Hg Ecell= Esce - Equinhydrone Ecell= 0.2422 - 0.6994 + 0.0592 pH

pH = 0.6994 0.2422 + Ecell / 0.0592

Advantages: 1. It is very useful in the acid alkali titration 2. Equilibrium is rapidly attained Limitation 1. it gives good results in solutions, whose pH values are less than 8, 2. at more alkaline solution, hydroquinone ionizes appreciably as an acid (H2Q = 2H+ + Q2-), the equilibrium altered 3. it cannot be used if the solution possesses redox system ------------------------------------

33

Ion selective electrodes (ISE)

The electrodes possess selectivity towards a certain ions in the electrolyte. Classified based on the nature of the membrane used 1. Glass membrane electrodes 2. Solid state electrodes 3. Precipitate electrodes 4. liquid-liquid electrodes

The glass electrode

It is a half cell A glass electrode is a type of ion-selective electrode made of a glass membrane that is sensitive to a specific ion. Almost all commercial electrodes respond to single charged ions, like H+, Na+, Ag+. The most common glass electrode is the pHelectrode. It consists of thin walled glass membrane bulb, having low melting point and high electrical conductivity containing Pt wire in 0.1 M HCl. Pt, 0.1 M HCl / Glass When two different concentrated solutions are separated by a thin glass membrane, a potential will be induced on the membrane. The potential developed is proportional to the difference in [H+] on either side of the glass membrane.

34

 Glass membrane contains dry glass at the centre and on either side of the glass, hydrated glass gel is coated. Glass membrane act like a cation exchanger, Most of the metal cations (e.g. Na+) in the hydrated gel layer exchanged with H+ in solution. When the equilibrium is obtained between Na+ ions and H+ ions on the the glass membrane On either side of the glass membrane is set with unequal number of H+ ions on either of the glass membrane will develop some potential on the glass called glass electrode potential. The difference in H+ ions concentration on either side of glass produce a potential over glass like concentration cell

35

The potential developed on the glass is proportional to the difference of [H+] ions concentration on either side of the glass The potential of glass is given by the Nernst eqn, EG = EoG + 0.0592/n log [[H+] EG = EoG - 0.0592 pH In order to determined the pH of the solution, the glass electrode is placed in the solution and the half cell is coupled with SCE The EMF of the cell is measured from potentiometer The e.m.f of the complete cell is Ecell Ecell Ecell = E (right) - E (left) = + 0.2422 V [EoG - 0.0592 pH] = + 0.2422 V EoG + 0.0592 V pH Ecell + EoG -0.2422 V ----------------------------0.0592 V EoG can be determined by using a solution of known pH. The glass electrode produced is very low to determine by ordinary potentiometer. It needs some special electronic potentiometer. To overcome this problem the glass electrode is connected to the internal reference electrode (Ag /AgCl electrode). Pt electrode in glass electrode can be coupled with silver chloride Ag /AgCl electrode in 0.1 M HCl solution.

pH =

36

Advantages: 1. It is simple to handle. 2. Equilibrium is rapidly achieved 3. The results are accurate. 4. It is not poisoned easily. Limitations:
1. It can be used in the solution range of 0 to 10. 2. Special glasses have to be used to measure the pH upto 12. 3. above pH 12 cations of the solution affect the glass interface & render the electrode useless 4. The very thin membrane can produce extremely high resistance, which cannot be measured by ordinary potentiometer. It require special electronic potentiometer.

37

Potentiometric titration
Potentiometric titration is a technique similar to direct titration of a redox reaction. No indicator is used; instead the voltage across an electrolyte solution is measured. To do this, two electrodes are used, a neutral electrode and a standard reference electrode. The voltage is recorded at intervals as the titrant is added. A graph of voltage against volume added can be drawn and the end point of the reaction is half way between the jump in voltage. The potentiometric titration involve measurement of EMF between indicator electrode and reference electrode,with the addition of titrant. The potential of the electrode dipped in a solution of an electrolyte depends upon the conc. Of certain ions. E = Eo +RT/ nF ln C During the titration the conc. Of active metal ions vary and so the potential vary The change of the potential is measured which gives the end point of the titration. Hence, the determination of potential can be used as an indicator in Potentiometric titration These titrations are also known as Electrometric titrations It gives more accurate result. No indicators are required. No special care is necessary near the end point as the end point is ascertained graphically

38

Types of Potentiometric titration

Redox titrations Precipitation titrations Acid-base titrations

1. Redox titrations Fe2+ vs. Dichromate (K2Cr2O7) or permanganate (KMnO4)

Titrations involving oxidizing agents like K2Cr2O7 or KMnO4 and reducing agents like FeSO4 can be followed by using Pt as indicator electrode. The redox reactios are K2Cr2O7 + 6FeSO4 + 7H2SO4 --Cr3+ + 3 Fe3+ 2 MnSO4 +5 Fe2(SO4)3 + 8H2O Cr2(SO4)3 + Fe2(SO4)3 + 7H2O +

K2SO4 Or Cr6+ + 3 Fe2+ ------

2KMnO4 +10FeSO4 +8H2SO4 -Mn2+ +5 Fe3+

+K2SO4 or Mn7+ + 5 Fe2+ ------

Pt electrode connected to the reference electrode - SCE On adding K2Cr2O7 / KMnO4 from the burette, emf of the cell will Ferrous ion oxidized to ferric ion, the Cr6+ /Mn7+ ions added into the

increase solution will get reduced to Cr3+/Mn2+ ions immediately, so no Cr6+ / Mn7+ ions are in the solution. (the electrode potential of indicator electrode depends on the concentration of Fe3+ and Fe2+ ions) The emf of the cell is given by the Nernst eqn
39

Ecell = Ec Ea The standard reduction potential Eo red(Fe3+,Fe2+) = + 0.77 V EoFe3+,Fe2+ = +0.77 V ---------- Cathode ESCE = +0.2422 V ---------- anode Ered of Fe3+ + 1e- --Fe2+ EFe3+,Fe2+ = EoFe3+,Fe2+ - log [Fe2+] / [Fe3+] EFe3+,Fe2+ = 0.77 (0.0592 / 1 ) log [Fe2+] / [Fe3+] Ecell = 0 .77 + (0.0592 / 1) log [Fe3+] / [Fe2+]) 0.2422 Ecell = 0.5267 + 0.0592 / 1 log [Fe3+] / [Fe2+])

So the emf of the cell will be around (0.5267 + some increasing value) V When the titration continue, the conc. Of Fe3+ ion increases, so the

emf also increases. But at the equivalence point, there will be sudden jump in potential to This is because, after complete oxidation of Fe2+ to Fe3+ ions, there Whatever Fe3+ (oxidized) and Mn2+ ions (reduced) will be in the Now the added Mn7+ ions will not be reduced, because there are no The conc. of Mn7+ ions will increases with respect to constant Mn2+ So both Mn7+, Mn2+ ions are in solution and the indicator electrode The electrode potential for Mn7+ --------Mn2+ + 2e-

a higher value. will not be any Fe2+ ions in the solution.

solution. Fe2+ ionsto undergo Oxidation.

ions concentration. potential dependence over the [Mn7+] / [Mn2+]

40

E(Mn7+ Mn2+) = Eo(Mn7+ Mn2+) 0.0592 / 1 log [Mn2+] / [Mn7+] ESCE = 0.2422 The standard reduction potential Eo -------

Anode
red(Mn7+,Mn2+)

= + 1.51 V ----

cathode The emf of the cell is Ecell = Eo(Mn7+ Mn2+) 0.0592 / 1 log [Mn2+] / [Mn7+] - 0.2422 Ecell = 1.51 - 0.0592 / 1 log [Mn2+] / [Mn7+]- 0.2422 Ecell = 1.2678 + 0.0592 log [Mn7+] / [Mn2+] When the dependency of indicator electrode potential is shifts from

[Fe3+] / [Fe2+] to [Mn7+] / [Mn2+], the emf of the cell shifts from around 0.5267 V to around 1.2678 V. So there is jump in the emf when the equilibrium point (end

point) is obtained. On plotting E/ V vs. volume of the titrant, the point of maxima

gives the end point.

2. Precipitation titration (potentiometric titration)

41

Estimation of AgNO3
The pot. of the electrode when dipped in the solution of an electrolyte depends on the conc. Of certain active ions If these ions are precipitated by the addition some titrant, the conc. Of these ions decreases and so the ele. pot. also decreases. In the titration of silver nitrate with a standard KCl Ag electrode dipped in AgNO3 solution, The pot. on Ag electrode depends on the Ag+ ions conc. E = Eo + 0.0592 / 1 log [Ag+] Ecell = Eo + 0.0592 / 1 log [Ag+] 0.2422 as the titration proceeds the Ag ions get gradually precipitated as AgCl Ag+ + NO3- + K+ + Cl- --AgCl + K+ + NO3 The conc. goes of [Ag+] on decreasing and hence the elec. Pot. Of the indicator electrode also decreasing continuously on the progressive addition of KCl. At the equivalent point, the complete precipitation Ag+ ion as AgCl take place suddenly. The concentration of Ag+ ion in solution decrease suddenly, so the emf decreases sharply. if the addition of KCl is continued beyond the endpoint , the Ag+ ion concentration is not affected much, except a very small decrease that is due to the decrease in solubility of AgCl on account of common ion (Cl-) effect. On plotting E/ V vs. volume of the titrant, the point of maxima gives the end point.

42

3. Acid-base titrations (potentiometric titration)

Acid-base titrations, the indicator electrode depends on the concentration of H+ ions concentration. When base is added from the burette , the conc. Of H+ ions decreases So the emf of the cell decreases Ex. pH metric titration The pH meter is calibrated in such a way that the Emf of the cell is directly converted into pH The change in the emf of the cell is read as pH of the solution

43

Conductometric titration
It is a method of volumetric analysis based on the change in conductance of the solution, at the equivalence point during titration. The principle involved in these titration is that electrical conductance depends upon the number and mobility of the ions To get accurate and precise results: The temp. should be maintained as at constant. The titrant should be 10 times stronger than the solution Conductance are followed during the course of titration and the values are plotted against the volume of titrant The conductometric curves should be straight lines passing though a few points on either side of the end point The end point of the titration is the point of intersection of the straight lines

44

Conductometric titration- strong acid vs. strong base (HCl vs. NaOH)
At the beginning of the titration the conductance is high due to the presence of H+ and Cl- ions The addition of alkali decrease the H+ ions by neutralization reaction and hence conductance decreases H+ + Cl- + Na+ + OH- ------H2O + NaCl

After the complete neutralization of H+ ions the excess alkali increases the conductance due to the presence of fast moving OH- ions

45

Conductometric titration - Weak acid vs. strong base (CH3COOH vs. NaOH)
At the beginning of the titration the conductance is low, since the acetic acid is a weak acid and dissociate weakly The addition of alkali slightly increases the conductance because of the formation of highly ionized Sod. acetate (CH3COONa). CH3COOH + NaOH --CH3COO- + Na+ +H2O

After the complete neutralization of acid, the excess alkali sharply increases the conductance due to the fast moving OH- ions. The point of intersection gives the end point.

Conductometric titration-strong base vs. mixture of acids (NaOH vs. CH3COOH)

At the beginning of the titration, the strong base first neutralize the strong acid The addition of alkali decreases the H+ ions by neutralization reaction and hence conductance decreases.

46

 This is shown by the straight line AB After the complete neutralization of H+ ions the excess of alkali slightly increases the conductance because of the formation of highly ionized Sod.Acetate (CH3COONa). CH3COOH + NaOH --CH3COO- + Na+ +H2O

This slightly increase in the conductance is shown by the straight line CD After the complete neutralization of weak acid, the excess alkali sharply increases the conductance due to the fast moving OH- ions. This is shown by the straight line EF

alkali increases the conductance due to the presence of fast moving OHions These 3 lines AB, CD and EF make 2 intercepts. The first intercept is the end point (V1 ml) corresponds to the neutralization of strong acid and The second intercept is the end point (V2 V1 ml) corresponds to the neutralization of weak acid

47

Conductometric titration - Weak base vs. Weak acid (NH4Cl vs. CH3COOH)
As NH4OH is added the conductance increases as the salt CH3COONH4 is more dissociate than CH3COOH After the equilibrium point, the conductance remains almost constant as the excess base added is weakly ionized.

48

Advantages of conductometric and potentiometric titrations 1. No special care is necessary near the end point as the end point is ascertained graphically 2. Colored solution which cannot be titrated by ordinary volumetric methods with the help of indicators, can be titrated 3. The titration of weak acid vs weak base can be performed

conductometrically. These cannot be performed volumetrically as they do not produce sharp change in the color of indicators 4. Very dilute solutions can also be titrated 5. It gives more accurate result 6. No indicators are required

49