1

Basics
Electrode potential and Galvanic cells Potential The potential is the basic expression of electrical energy. By potential, what we mean is potential difference and it is commonly known as electromotive force. Whether the potential is applied to a voltaic cell to carry out electrolysis or the potential is derived from a Daniel cell or a battery, it is the expression of electrical energy. The driving force in electrolysis is the electrical energy, which is converted to chemical energy. Similarly in an electrochemical cell or Daniel cell the driving force is the chemical reaction and the chemical energy is converted to electrical energy. But the point to remember is whether it is application of electrical energy into a voltaic cell or derivation of electrical energy from an electrochemical cell, two terminals are required. Even in the measurement of potential, two probes are required. By potential, we mean potential difference. In AC the potential difference is measured between phase and neutral terminals. In DC, the potential difference is across electron deficient (+) and the electron rich (-) terminals. The flow of electron is the flow of electricity. The unit for potential or potential difference or EMF is volt, which is the basic unit. Basic expression The current is measured in Ampere and it can be regarded as the electrical equivalent of quantity of chemical undergoing change in an electrochemical system. When it is combined with time or duration of the reaction, the quantity of electricity coulomb is obtained. Coulomb is the quantity of electricity when 1 ampere is passed through a load for one second q = As. Electrical power is expressed in watt, which is the product of potential difference in volts and current strength in ampere, Watt = VA The consumption of electricity is measured as units of electricity. One unit of electricity = one Kwh. (when one kilowatt power is consumed for one hour) Energy term Joule is related to electrical potential by Joule = Volt coulomb = Volt Ampere second VAs = Watt second 1HP = 750 watts

2 Electrochemical cell or Daniel cell A cell in which chemical energy is spontaneously converted to electrical energy is called electrochemical cell. What is the origin of potential? Why should the reaction occur in the cell? What is the driving force? The following section brings answer to all these questions. Origin of potential: When a metal rod is kept immersed in its salt solution, some metal atoms go into solution as ions, leaving behind the electrons in the metal lattice. For example when a zinc rod is kept immersed in zinc sulphate solution, zinc goes into solution as zinc ions. The electrons in the metal lattice and the positive ions in the solution orient themselves in an array called electrical double layer, as shown in figure.

Figure 1.1 Formation of Electrical Double Layer At this stage some of the metal ions return to metal lattice, by combining with electrons. Soon, an equilibrium is established between the metal atoms and the ions, which is dynamic. At this stage a potential is generated at the Zn rod.

Z n n Z
The zinc rod is now called zinc electrode.

+ +

+2e

(1.1)

The formation of electrical double layer and the onset of equilibrium are responsible for the generation of potential. This equilibrium potential is called single electrode potential. A direct way to establish this fact, is to measure the potential. But as described earlier, the potential is the potential difference. For this another such system is needed. A copper metal in contact with its ions may be taken as the other electrode. Formation of double layer and establishment of equilibrium between copper and its ions occur in the system.

C u u C

+ +

+2e

(1.2)

3 These dynamic equilibria will exist for a long time if undisturbed. The two metal rods are externally connected by a conducting wire, which provided a path for the flow of electrons. The two electrolytes are connected by a salt bridge, which facilitates ionic charge transfer.

Figure 1.2 Electrochemical cell-Daniel cell A voltmeter if connected across the two electrodes (zinc and copper) a potential difference is recorded. This is a direct proof for the generation of potential at the two electrodes. This system is an electrochemical cell and each electrode is a single electrode or a half cell. The potential difference arises from chemical reactions that occur at the electrodes. In an electrochemical system the basic reactions are simultaneous oxidation and reduction. The next aspect is to find out the sites of oxidation and reduction in the cell. It is well known that of the two electrodes, zinc is more electropositive or baser than copper and hence has a higher tendency to undergo oxidation. Copper is nobler or more electronegative than zinc and hence has a higher tendency to undergo reduction. When the two are combined in the cell, zinc undergoes oxidation spontaneously. The equilibrium is disturbed and shifted to right.

Z n n Z

+ +

+2e

The electrons travel through zinc lattice, pass through the metallic wire and reach copper electrode. There they combine with copper ions from the solution to form metallic copper, which deposits on the copper rod. The equilibrium (4.2) is shifted to the left i.e., copper ions are reduced.

C u

+ +

+2e u C

The overall cell reaction is oxidation of zinc and reduction of copper ions. Physically the overall reaction is dissolution of zinc and deposition of copper. This electrochemical system is called a Redox system, since reduction and oxidation occur simultaneously. Likewise any two metals can be combined and a cell can be constructed. One of them will undergo oxidation and the other reduction. Hence the driving force for the occurrence of chemical reaction in an electrochemical cell is the difference in the oxidizing or reducing tendency of the two electrodes. The oxidizing tendency of a metal electrode is called its oxidation potential and the reducing tendency, the reduction potential. For assigning numerical values to the oxidation or reduction potentials, hydrogen electrode is chosen as the base. The hydrogen electrode is set up as follows:

Figure 1.3 Standard hydrogen electrode A platinum foil is kept immersed in hydrochloric acid and pure dry hydrogen gas is bubbled through a fine nozzle kept close to the foil. The gas molecules get adsorbed on the foil surface. When considerable concentration of absorbed hydrogen molecules is reached, some of the molecules ionize into the solution as hydrogen ions. Soon, an equilibrium is established between hydrogen molecules and hydrogen ions in solution.

H 2 H + +2e 2
This equilibrium is similar to any metal/metal ion equilibrium. Hence a potential is generated and the electrode is called hydrogen electrode (HE). At this point it may be appropriate to point out that if any substance in its normal state of existence is capable of establishing an

5 equilibrium with its ion in solution, it forms an electrode and generates a potential. For assigning a value to HE, the conditions which affect the potential are standardized. i. ii. iii. iv. Activity of molar concentration of the hydrogen ions is fixed as unity. Temperature unless otherwise specified is taken to be 25 oC or 298 K. Pressure of hydrogen gas is fixed as one atmosphere. The surface of platinum should be pure and fresh and to ensure this platinized platinum foil is taken. Under these standard conditions, the hydrogen electrode, HE becomes standard hydrogen electrode (SHE) and its potential is arbitrarily fixed to be zero. The potential of any other electrode can be determined by coupling it with SHE and forming an electrochemical cell. The cell is connected to a very sensitive potentiometer, which draws negligible current from the cell. At this zero current condition, the potential difference of the cell or EMF is determined. The potential of the test electrode is the potential difference measured, since the potential of SHE is zero. Likewise, the potentials are determined under zero current condition and arranged in an order. According to IUPAC convention, the potentials of electrodes under standard condition are expressed as reduction potential and arranged in the increasing order. This list is called electrochemical series or EMF series or standard electrode potentials or equilibrium electrode potentials. It is to be noted that the oxidation potentials of these electrodes will be the same, with sign reversed.

Table 1.1 Standard reversible potentials (reduction) E0 values Species in equilibrium Li+/Li E0 Volts 3.01 Species in equilibrium H+/H E0 Volts 0.0

6 K+/K Ba++/Ba Ca++/Ca Na+/Na Mg++/Mg Al+++/Al Mn++/Mn Zn++/Zn Fe++/Fe Cd++/Cd Co++/Co Ni++/Ni Sn++/Sn Pb++/Pb Significance of the EMF series: i. The sign of the potential indicates the spontaneity of the reaction. If it is positive the reaction occurs from left to right spontaneously i.e., reduction is favoured. If it is negative, oxidation is spontaneous. ii. When the potential of Mg electrode is compared with that of SHE, it is less reducing or more oxidizing to the extent of 2.38 volts. If the two are coupled in a cell, Mg will undergo oxidation and hydrogen ion reduction. 2.92 2.90 2.87 2.713 2.38 1.66 1.18 0.763 0.44 0.402 0.28 0.25 0.14 0.126 Cu++/Cu O2/OHCu+/Cu I2/IHg22+/Hg Ag+/Ag Hg++/Hg Br2 (l) /Br Pt++/Pt Cl2(g)/Cl Au+/Au H2/H F2(g)/F 0.34 0.401 0.52 0.536 0.798 0.799 0.858 1.065 1.2 1.358 1.70 2.2 2.87

M g g M

+ +

+2e

2 H + +2e 2 H
iii. If SHE is combined with copper electrode which is more reducing, the spontaneous cell reaction is oxidation in SHE and reduction in copper electrode.

H 2 H + +2e 2 C u
+ +

+2e u C

7 iv. When any two electrodes are combined in this series, one with a lower reduction potential (higher oxidation potential) undergoes oxidation and the other with a higher reduction potential, undergoes reduction. v. One with a higher oxidation potential displaces the one lower in the series, with less oxidation potential. Iron dipped in copper sulphate solution, displaces copper from the solution. vi. vii. When the potential difference between two electrodes is large, the oxidation and reduction occur readily. For metals whose oxidation potentials are very high compared to SHE, such as K, Li, Ba, Ca and Na an equilibrium in aqueous solution is not attainable. G is highly negative and the oxidation occurs extremely fast and irreversibly. For these electrodes Eo values are obtained indirectly from thermodynamic data. (Calculation beyond the scope of this book) viii. Due to the above said fact, sodium reacts with water very fast, displacing hydrogen.

N +H 2O a H a NO
As a redox couple,

+ / 2H 2 1

N a a N

+e

H + +e / 2 H 2 o 1 r
H 2 O +e / 2 H 2 +O 1 H

The amount of hydrogen ion present in water is very low, 10 -7 gm.eqts / L. The oxidizing power of Na, Li or K is so high to initiate the reduction of this H+ or reduction of water. ix. Down the series, Mg, Al, Zn, Fe, do not undergo oxidation so fast in water. But in dilute acid where H+ concentration is more, redox couples are set up and the metals dissolve displacing hydrogen. x. But nickel and lead which are above SHE, do not displace hydrogen even from dilute acids. The threshold energy requirement is high and the difference in potential with SHE, is not high enough to initiate the reaction. Metals below SHE, as expected do not displace hydrogen from acids.

8 Spontaneity of the cell reaction: For any spontaneous reaction, it has already been seen, that the free energy change must be negative. i.e., G = -nEF G - free energy change. N - number of electrons involved in the change. F - Faraday. E - Potential For any electrochemical reaction, when E is positive, G becomes negative and the reaction is favoured from left to right. When E is negative, G is positive and the reaction is favoured in the other direction. Cell Notation According to IUPAC convention, an electrochemical should be represented such that the spontaneous reaction occurs from left to right and the cell potential should be positive. For example when zinc and silver electrodes are combined, the cell notation, Interface

Zn(s)

Zn++

1.0M

Ag+
1.0M

Ag

Salt Bridge Spontaneous reactiion The metals are in the solid state. The concentration of each solution is one molar. Two single vertical lines represent solid-solution interfaces. One double vertical line denotes salt bridge or porous diaphragm. As per the convention, the spontaneous reaction occurs from left to right. That is zinc gets oxidized and silver ions are reduced. If the total cell EMF is positive the above assumption and notation are correct. The total cell reaction:

Z +2 A n g

n Z

+ +

+2 A g

9 The total cell potential can be determined as i. Algebraic difference of the oxidation potentials of the two electrodes so that E is positive. Standard oxidation potential for zinc is EoOP = +0.763 V (R.P is 0.763) Standard oxidation potential for silver is EoOP = -0.799 V (R.P is +0.799) Total cell potential is Eocell = EoOP of Zn EoOP of Ag = 0.763 (-0.799) = 1.562 V ii. The algebraic difference of the reduction potential of the two electrodes, such that the result is positive. Standard reduction potential of zinc is EoRP = -0.763 V Standard reduction potential of silver is EoRP = +0.799 V Total cell potential Eocell = Higher RP Lower RP = EoAg+/Ag - EoZn++/Zn = 0.799-(-0.763) = 1.562 V iii. The total cell potential may also be determined as the algebraic sum of oxidation potential of one electrode and the reduction potential of the other so that a positive EMF value is obtained. Eocell = Eoop of Zn + Eoop of Ag = 0.762 + 0.799 = 1.562 V HE and SHE are represented as Pt;H2(g) (any pressure) Pt;H2(g) (1 atm pr.) H+ [M] H+ [M] HE at 25 oC at 25 oC

The cell reaction in this notation is oxidation

10

H 2 H + +2e 2
If reduction reaction of SHE is to be expressed the notation is H+ [1M] H2(g), Pt (1atm. Pr.) SHE at 25 oC

Whether oxidation or reduction occurs in hydrogen electrode depends on the other electrode with which it is combined. When coupled with electrodes placed above SHE, reduction occurs and with electrodes below, oxidation occurs in SHE spontaneously. Reversible and Irreversible cells: Daniel cell discussed earlier is an example of reversible cell. A reversible cell is one in which the spontaneous cell reaction can exactly be reversed when a higher potential than the cell potential is applied externally to the cell, opposing the cell EMF. With 1molar concentration each of zinc and copper ions, the cell voltage at 25 oC is 1.103 volts. During this zinc dissolves and copper gets deposited. Cell reaction:

Z +C n u

+ +

n Z

+ +

+C u

When an external potential is applied to the cell opposing the cell voltage, the rates of zinc dissolution and copper deposition decrease. When the external potential is increased to exactly 1.103 volts, the cell reaction completely stops. When the applied potential is still increased, copper gets oxidized i.e., goes into solution as Cu++ and zinc ions are reduced i.e., zinc gets deposited as zinc metal.

C +z ++ u u n C

+ +

+Z n

The reactions are exactly reversed and this is a reversible cell. Irreversible cell: This is one in which the spontaneous reactions are not exactly reversed, when an external voltage is applied to the cell. For example, a pair of zinc and copper electrodes are kept immersed in dilute sulphuric acid and are connected. Immediately hydrogen bubbles appear on copper. The spontaneous cell reaction is dissolution of zinc and zinc ions (oxidation) and reduction of hydrogen ions to hydrogen gas which bubbles on copper. Cell reaction

Z n n Z

+ +

+2e ;2 H + +2e 2 (o C ) H n u

11 When an external potential higher than the cell potential is applied in an opposing way, the reactions are dissolution of copper and reduction of hydrogen ion to hydrogen, which appears now on zinc. If the reactions are exactly reversed, then hydrogen should have been oxidized and zinc ions reduced. This kid of cell is called an irreversible cell. Cell reaction:

C u u C

+ +

+2e ;2 H + +2e 2 (o zin H n c

Variation of potential with concentration: How does the change in concentration of the electrolyte reflect on the potential? The relationship between electrode potential and the concentration of the solution is given by Nernst equation. For a general reversible reaction, the free energy change at constant pressure and temperature and its equilibrium constant are related as shown below.

a +b C +d A B c D
The free energy change for this reaction is [C]c[D]d G = -RTlnK + RTln [A]a[B]b K = equilibrium constant The terms in square brackets are the activities of the species, which may be assumed to be their molar concentrations. It is already noted that G = -nEF Substitution for G, E = RT lnK + RT ln [A]a[B]b nF nF [C]c[D]d

If the concentration ratio term is unity, E = RT lnK nF = E0

Eo is the standard equilibrium potential. Substituting this value in the earlier equation. E = E0 + RT ln [A]a[B]b nF [C]c[D]d

12 In general terms, E = E0 + RT ln [Product of molar concentration of reactants] nF [Product of molar concentration of products]

This is called Nernst equation. Substituting the values of R, T, F R = 8.314 joule, T = 298 K, F = 96 500 coulombs and converting natural logarithm to log to base 10, E = E0 + 0.059 log [Reactants] n [Products] n is the number of electrons taking part in the electrochemical reaction. For a given electrode/electrolyte system Eo is constant. When the ratio [Reactants] [Products] becomes one, E = Eo i.e the standard equilibrium potential. E is made up of two terms, of which one is constant and other varies with concentration. The following examples illustrate the application of the Nernst equation. 1. Hydrogen electrode (HE) The electrode reaction (as reduction)

2 H + +2e 2 H
Applying Nernst equation, E = E0 + 0.059 log [H+]2 2 [H2] The activity or molar concentration of any substance in its normal state of existence is unity. On simplification, E = E0 + 0.059 log [H+], When [H+] = 1, E = E0 = 0 [SHE =0] E = 0.059 log [H+] The potential of hydrogen electrode depends on the concentration of hydrogen ion. The potential is related to pH as, E = 0.059pH

13 2. A cell can be constructed by combing hydrogen electrode (HE) and standard hydrogen electrode (SHE). Let us see how the potential of hydrogen electrode (as reduction) varies when the concentration is more than unity and b) less than unity (at unity it is zero). a) [H+] = 1.5 M E = 0.059 log (1.5) = 0.0104 V At concentration > 1, reduction of [H+] is favoured [H+] = 0.1 M E = 0.059 log (0.1) = 0.059 V Since a negative value is obtained, reduction is not favoured when [H+] is < unity. Oxidation is favoured. Hence the cell notation will be (SHE and HE) a) Pt;H2(g) (1 atm) [1 M] SHE H+ 1.5 M HE H+ H2 (g); Pt 1 atm.

Spontaneous reaction. b) Pt;H2(g) H+ H+ (1 atm) [0.1 M] 1 M HE SHE H2 (g); Pt 1 atm.

Spontaneous reaction. 3. For Daniel cell type. [Zn2+] = 0.1 M; [Cu2+] = 1.8 M The cell is, Zn (s) Zn++ [0.1 M] Cu++ Cu (S) 1.8 M

Spontaneous reaction. Zn undergoes oxidation and copper ion reduction. Ecell = EOP + ERP

Z n n Z

+ +

+2e

Applying Nernst equation.

14 Eop = E0op + 0.059 log [Zn] 2 [Zn2+] = 0.763 + 0.059 log 1.0 2 0.1 = 0.7925 V When the solution becomes more dilute, the oxidation potential is more which indicates that the dissolution or corrosion is more in dilute solution. At copper electrode reduction occurs
2+

C u

+2e u C

Applying Nernst equation, ERP = E0RP + 0.059 log [Cu2+] 2 [Cu] = 0.34 + 0.059 log 1.8 2 1.0 = 0.3475 V It is seen here that the reduction potential of the electrode increases, when the concentration of the solution increases. In concentrated solution, the population of ions per unit volume is more and hence the tendency of the ions to come out of the solution is more. Ecell = EOP + ERP = 0.7925 + 0.3475 = 1.14 V For any electrode, its OP increases with dilution and RP increases with increase in concentration. 4. The total potential can be found out by the difference between their oxidation potentials. For this method, the electrode reaction should be written as oxidation, whether it is spontaneous or not. For zinc electrode: (as oxidation)

Z n n Z

+ +

+2e

Applying Nernst equation Eop = E0op + 0.059 log [Zn] 2 [Zn2+]

15

= 0.763 + 0.059 log 1.0 2 0.1 = 0.7925 V For copper electrode (as oxidation)

C u u C

+ +

+2e

Applying Nernst equation. Eop = E0op + 0.059 log [Reactants] 2 [Products] = 0.34 + 0.059 log Cu 2 Cu2+ [Cu] = unity [Cu2+] = 1.8 M Eop = -0.34 + 0.059 log [1] 2 [1.8] = 0.3475 V Ecell = EOP of Zn EOP of Cu = 0.7925 (0.3475) = 1.14 V The total cell potential can be determined by the algebraic difference of reduction potentials. The half cell reactions are written as reduction. For zinc electrode
2+

Z n

+2e n Z

Applying Nernst equation, ERP = E0RP + 0.059 log [Reactants] 2 [Products] = 0.763 + 0.059 log 0.1 2 1.0 = 0.7925 V For copper electrode, the reduction is
2+

C u

+2e u C
ERP = E0RP + 0.059 log [Cu2+] 2 [Cu] = 0.34 + 0.059 log 1.8 2 1.0

16 = 0.3475 V Ecell = ERP of Cu ERP of Zn = 0.3475 (0.7925) = 1.14 V Example: Construct as many cells as possible by combining the following electrodes, [Zn2+]/[Zn]; [Cu2+]/[Cu]; [Cu+]/[Cu]; and [Ag+]/[Ag]; Each electrolyte is 0.1M concentrated. Write the cell notation and calculate the EMF of the cell at 25 oC. Eo values can be taken from the table 1.1. a) Zn (s) Zn++ Cu++ [0.1 M] 0.1 M Cu (S)

Z n n Z

+ +

+2e

Eop = E0op + 0.059 log [Zn] 2 [Zn2+] = 0.763 + 0.059 log 1.0 2 0.1 = 0.7925 V

C u

2+

+2e u C

ERP = E0RP + 0.059 log [Cu2+] 2 [Cu] = 0.34 + 0.059 log 0.1 2

Foot Note: In calculating the potential for half cells and total cells, the students are advised, i. To follow Nernst equation, in the form given here E = E0 + 0.059 log [Reactants] n [Products] ii. iii. To write the cell reaction, split it into 2 half cell reactions. To find the total cell potential follow one of the three methods given above.

17

= 0.3105 V Ecell = 0.7925+0.3105 = 1.103 V b) Zn (s) Zn++ Cu+ [0.1 M] 0.1 M = 0.7925 V
+

Cu (S)

Zn electrode potential

C u

+e u C
ERP = E0RP + 0.059 log [Cu+] 1 [Cu] = 0.52 + 0.059 log 0.1 1 = 0.461 V

Ecell = 0.7925+0.461 = 1.254 V c) Zn (s) Zn++ Ag+ [0.1 M] 0.1 M EZn/Zn++ = 0.7925 V
+

Ag (S)

A g

+e g A

ERP = E0RP + 0.059 log [Ag+] 1 [Ag] = 0.8 + 0.059 log 0.1 1 = 0.741 V Ecell = 0.7925+0.7410 = 1.5335 V d) Cu (s) Cu++ Cu+ [0.1 M] 0.1 M Cu (S)

C u u C

+ +

+2e

Eop = E0op + 0.059 log [Cu] 2 [Cu2+] = 0.34 + 0.059 log 1.0 2 0.1 = 0.3105 V

18 The reduction potential of cuprous electrode is 0.461 Ecell = 0.3105 + 0.461 = 0.1505 V e) Cu (s) Cu++ [0.1 M] Ag+ Ag (S) 0.1 M

The oxidation potential of copper is 0.3105 V The reduction potential of Ag is +0.741 V Ecell = 0.3105 + 0.741 = 0.4305 V f) Cu (s) Cu+ Ag+ [0.1 M] 0.1 M Ag (S)

C u u C

+e

Eop = 0.52 + 0.059 log 1.0 2 0.1 = 0.461 V Silver reduction potential is found as 0.741 V Ecell = 0.461 + 0.741 = 0.2800 V Reference Electrode There are some basic defects with standard hydrogen electrode. 1) Setting up of SHE is very cumbersome and tedious. 2) Platinum electrode is highly prone to get poisoned by traces of impurities in hydrogen gas. Hence hydrogen gas passed must be in a high state of purity. 3) Reproducibility is of low order. Hence other electrodes, whose potential will not vary with use, are developed, which are called reference electrodes. Very widely used reference electrodes are calomel and silver/silver chloride electrodes. Calomel Electrode Calomel is Hg2Cl2 mercurous chloride. A small quantity of a paste consisting of a few drops of mercury, a pinch of calomel (mercurous chloride) and a few drops of saturated potassium chloride solution is prepared and taken in a small hard glass tube. The tube is fitted with a porous, sintered glass frit. A platinum wire kept immersed in the paste, facilitates external connection. This glass tube is kept in an outer glass tube, also fitted with a porous frit at the bottom as shown in the

19 figure. This frit serves as a salt bridge, when the electrode is immersed in the test solution, during measurement. Potassium chloride solution of a fixed concentration (0.1 N, 1.0 N or saturated) is filled in the outer tube. The electrode can be immersed in the test solution and the measurement can be made conveniently.

Figure1.4: Calomel Electrode Reactions and functioning of calomel electrode: Mercurous chloride, being a sparingly soluble salt, forms a very dilute but saturated solution in water. Hence the following equilibria are exhibited. Hg 2Cl2 ( s ) ( Hg 2Cl2 aq ) Hg 2
++

+ 2Cl

Hg2Cl2 aq is transitory because it is fully dissociated, being very dilute and the real equilibrium is ++ Hg 2Cl2 ( s) Hg 2 + 2Cl Hg 2 + 2Cl 2 Hg Hg 2Cl2 ( s ) + 2Cl 2 Hg + 2Cl Applying Nernst equation, Ecalomel = E0calomel + 0.059 log [Hg2Cl2(s)] 2 [Hg]2[Cl]2 [Hg2Cl2(s)] = 1; [Hg] = 1 Rearranging Ecalomel = E0calomel 0.059 log [Cl-] EoCalomel is constant and the potential of calomel electrode depends on the concentration of Cl-. But the amount of chloride ions obtained by dissociation of mercurous chloride is very low; but chloride ions from KCl is very large and also is constant. Thereby the potential of calomel electrode is constant. When it is coupled with another electrode of higher oxidation potential,
++

20 reduction occurs in calomel electrode. Hg2Cl2 will be converted to mercury and chloride ion. If calomel electrode is connected to another electrode of higher reduction potential, oxidation will occur at calomel electrode. Some Cl- will be converted to Hg2Cl2. This addition or removal of Cl from the already present very large quantity of chloride ions from potassium chloride, does not make any significant change in potential. Hence the potential of calomel electrode is constant. Silver-Silver chloride electrode: This is very similar in construction and functioning to calomel electrode. A silver rod, having a thin surface film of silver chloride is used instead of Hg2Cl2/Hg paste. Other aspects of construction are the same. The reaction is, AgCl ( s) + e Ag + Cl E = E0 + 0.059 log [AgCl(s)] 1 [Ag][Cl] = [AgCl(s)] = 1; [Ag] = 1 E = E0 0.059 log [Cl-] Indicator Electrodes: The electrode whose potential changes according to the concentration of some species present in the solutions is called an indicator electrode. Concentration dependence of the electrode is selective. For example the electrode which follows change in hydrogen ion concentration will not respond to change in concentration of metal ions. Two electrodes, i) quinhydrone electrode and ii) glass electrode are typical examples for indicator electrodes for hydrogen ion (H+) concentration changes. Quinhydrone Electrode: This is constructed by keeping a platinum wire in a solution of H + (acid), containing a small quantity of quinhydrone. The potential of this is a function of [H+]. Quinhydrone is an equimolar mixture of quinone and hydroquinone. The equilibrium between them can be represented as Q + 2 H + + 2e H 2Q EQH = E0QH + 0.059 log [Q][H+]2 2 [H2Q] [Q] = 1; [H2Q] = 1 E = E0 + 0.059 log [H+]

21 E = E0 0.059 pH This is used as an indicator electrode in pHmetric titration. Glass electrode: When two solutions of different hydrogen ion concentrations are separated by a thin glass membrane, a potential difference, depending on (H+) concentration difference is developed. The electrode consists of a glass bulb containing a solution of constant (H+) and a Ag/AgCl reference electrode. When it is dipped in a test solution of [H+], the potential of the electrode responds to the change in concentration of H+. Its potential is Eglass = E0glass + 0.059 log [H+] E = E0 0.059 pH E depends on [H+] change. It is used as an indicator electrode in acid-base titration. Ion selective electrodes: a) Solid state electrodes consist of compact disc of active material like silver halides or silver sulphide and are selective to the respective anions. b) Fluoride ion selective electrode consists of a single crystal membrane of LaF3 in contact with a mixture of 0.1M solution of NaCl and NaF. This is used to estimate F in water and fluoride-tooth pastes. c) Heterogeneous membranes or pungor electrodes are prepared from varied active materials like insoluble salts, metal complexes and ion exchange resins. The active material is impregnated in silicone rubber and used as a membrane. They respond to changes in SO42, NO3, PO43. A graphite matrix is also used instead of silicone rubber. These ion selective electrodes are called selectrodes. The electrodes discussed in detail in the above sections can be grouped or classified as: I. II. III. IV. V. VI. Metal-metal ion electrode (Zn++/Zn, Cu++/Cu) Metal-insoluble salt electrode (Reference electrodes)-(Calomel, AgCl/Ag) Gas electrode-(HE and SHE) SHE is a standard electrode. Indicator electrodes-(Glass and Quinhydrone) Ion selective electrodes-(Pungor electrodes) Inert or redox electrodes used in potentiometric titration to follow change in the ratio of oxidized species to reduced species-Pt and Au electrodes.

22 VII. Amalgamated electrodes. The potential depends on the concentration of the metal in the amalgam. Concentration cells: Any two electrodes, in the EMF series when combined, give rise to a potential difference due to their inherent property of oxidizing or reducing power. But a concentration cell is one in which the same electrodes and same electrolyte of different concentrations are used. The driving force for the reaction is the difference in concentration of the solution.

Figure 1.5: Concentration cell In the previous section it was seen that in concentrated solution reduction is favoured. This was evident from the increase in reduction potential as the concentration was more than one molar. From a physical sense, as more number of ions are crowded in unit volume of solution of higher concentration, the tendency of the ions to come out of the solution is more. Similarly, it was also seen that the oxidation potential of an electrode increases when the concentration is less than one molar. Metal dissolution is more in dilute solution. The following example may be considered. Two silver rods are dipped separately in two silver nitrate solutions of concentration C1 and C2 molar. The two rods are connected by a metal wire externally and the two solutions by a salt bridge. Since C2>C1 oxidation occurs in lower concentration C1 and reduction in solution of higher concentration C2. The cell is represented as, Ag (s) Ag+ [C1] Spontaneous Ag+ [C2] Ag (S)

23 According to convention, oxidation half cell is placed on the left and reduction half cell on the right. Cell potential is calculated as the sum of oxidation potential of left half cell and the reduction potential of right half cell. Left hand side Ag Ag + + e Eop = E0op + 0.059 log [Ag] 1 [Ag+] 0 E op + 0.059 log 1 1 [C1] Right hand side, Ag + + e Ag ERP = E0RP + 0.059 log [Ag+] 1 [Ag] 0 = E RP + 0.059 log [C2] 1 Ecell = EOP +ERP = [E0OP +E0RP] + 0.059 log [C2] n [C1] = E0RP = E0op = E0op + E0RP = 0 Ecell = 0.059 log [C2] 1 [C1] Generally, the potential of a concentration cell, E = 0.059 log [C2] n [C1] Where n is the number of electrons taking part in the reaction. C2 should be higher C1: only then E will be positive. During working of the cell, the concentration increases in the anode half cell and decreases in the cathode half cell. Finally the cell stops functioning when both concentrations become equal. Measurement of EMF of a Cell The electrochemical cell is formed by coupling two electrodes as discussed above. The electrodes can be connected to a voltmeter across (in parallel) and the emf can be directly measured. But the voltage will be maximum only under zero current withdrawal condition. If the measuring device draws current, erroneous result is produced.

24 But with the advancement of technology, very sensitive vacuum tube voltmeters (VTVM), which draw negligible current (<microampere) are available. These can be used to measure the potential. The traditional age-old method is the Poggendorf compensation method. A DC source is connected to a long, uniform potentiometer wire AB. A is connected to a standard Weston cadmium cell, a galvanometer and a sliding contact in series. The connection should be made in such a way that the potential of standard cell opposes the applied potential from DC source. The point of no current (D) flow (Galvanometer is Zero) is determined by sliding the contact over the wire. Weston cell is replaced by the test cell and the null point (E) is determined as above.

Figure 1.6: Measurement of emf of a cell AD = EMF of Weston cell AE EMF of test cell Values of AD, AE and EMF of Weston cell being known, EMF of test cell is determined E of western cell = 1.0183 V at 25oC. Besides the determination of EMF by this method, the polarity of the cell electrodes can be fixed. As mentioned above the standard cell must be connected so that its potential opposes the applied potential. If the connection is made otherwise the null point can not be determined. The electrode of the test cell which is connected to the positive (electron deficient) terminal of the DC source becomes positive. (null point is determined) and other electrode of the test cell in negative. In Daniel cell electron flows from Zn to Cu and positive electricity from Cu to Zn. Weston cadmium cell

25 One of the widely used standard cells is Weston cadmium cell. It has a constant emf of 1.0183 V at 25 oC and has a low temperature coefficient of 4 10-5 v/deg. Weston cadmium cell is represented as, 12.5% Cd in Hg 3 CdSO4.8H2O (s) CdSO4 (aq. satd.) Hg2SO4 Hg (l) It consists of cadmium amalgam (12.5%) in a glass limb. On top of this a layer of solid crystals of 3CdSO4.8H2O and a saturated solution of the same salt are present. The other limb contains saturated mercurous sulphate over Hg at the bottom and saturated cadmium sulphate solution.

Figure 1.7: Weston Cadmium cell Applications of EMF measurements 1) Equilibrium constant for a reversible reaction under standard conditions of temperature and pressure can be determined from EMF values. The relation is, E0 = RT lnK nF Eo is the standard potential of the cell or electrode. R = 8.317 J, T = 298 K, F = 96 500 The equation is simplified as, E0 = 0.059 log K n For the equilibrium

Z n n Z

+ +

+2e

26 E = 0.763; K = 7.318 10
o 0 25 0

n = 2,

G = -nE F = -2 0.763 96 500 = 1,47,259 Joules or 147.3 KJ. For the reaction, Zn + FeSO4 ZnSO4 + Fe

Z n n Z
E0cell = E0op + E0RP

+ +

+2e ; F e

2+

+2e e F

= 0.763 + (0.44) = 0.323 V G = -nE F = -2 0.323 96 500 = -62.3 KJ/mol 2) Thermodynamic parameters like enthalpy change, entropy change and free energy change can be calculated from EMF values. Example: i. The EMF of the cell Pt;H2 HCl (aq) AgCl Ag at 25 oC is 0.35 V
o 0

The temperature coefficient of the EMF is 0.45 mv/deg. The spontaneous cell reaction is from left to right. Write the cell reaction and calculate G, H and S for the reaction. Oxidation reaction at anode is

1/ 2H 2 ( g ) H + + e
Reduction or cathodic reaction is,

AgCl ( s) + e Ag + Cl
Cell reaction 1 / 2 H 2 ( g ) + AgCl ( s ) Ag ( s ) + H + + Cl Free energy change

27 G = -nEF = 1 0.35 96 500 = 33.78 KJ/mol = 8.07 Kcal/mol H = nEF + nFT E T

P

= 33.78+96500 298 (-0.45 103) 1000 = 46.72 KJ/mol or 11.17 Kcal/mol G = H TS or S = nF E T S = 1 96500 0.45 10 = 43.43 J/per degree = 10.38 Cal deg
1 3 P

3) pH measurements and pH metric estimations can be made using HE, quinhydrone and glass electrodes. 4) Solubility product of a substance can be determined, eg., AgCl from coupling AgCl/Ag electrode with SHE or Hg2Cl2 by coupling calomel with SHE. 5) Very important analytical application of EMF measurements is potentiometric titration a) K2Cr2O7 Vs FeSO4 It is called redox titration because the potential depends on the ratio of the activities of oxidized and reduced species. When dichromate is added to ferrous solution in acidic medium, the reactions are, Fe 2 + Fe3+ + e Applying Nernst equation EOP = EoOP + 0.059 log [Fe2+] 1 [Fe3+] Cr 6 + + 3e Cr 3+ Applying Nernst equation

28 ERP = EoRP + 0.059 log [Cr6+] 3 [Cr3+] Polarization and overvoltage The flow of electrons or charge in an electro chemical system at dynamic equilibrium is known as exchange current. For unit area of the electrode surface it is called exchange current density and its value is very low, of the order of 10-8 . In any industrial electrolysis this value is very low has no practical significance. In any electrochemical cell the electrodes are polarized i.e. charged and the potential is called rest potential. For the reaction to occur at a desired rate of practical importance much higher potential is required to overcome the polarization, that is, higher than the rest potential. This excess potential over the equilibrium potential for any electrochemical reaction to occur at a definite rate is called over potential. Hence Applied potential = Equilibrium potential + over potential Over potential is classified as 1. Activation over potential 2. Concentration over potential 3. IR over potential. Activation over potential This activation energy or over potential depends on the system i.e., the following factors. a) Nature of the reactions: It varies from one reaction to another. But an approximate generalization is possible. The activation over potential for a gaseous discharge reaction is considerably higher than a metal ion discharge reaction. Activation over potential for hydrogen ion discharge reaction 2H+ Cl 4OH salt solution. Cu++ + 2e Cu + 2e + H2 or e or Chlorine gas evolution 1/2Cl2 Hydroxyl ion discharge leading to oxygen evolution 2H2O + O2 + 4e is much higher than copper or nickel or silver ion discharge from the corresponding metal

29 Ag+ Ni++ + e Ag + 2e Ni

In fact the activation energy values among the gaseous discharge reactions or among the metal ion discharge reactions, differ under other conditions being identical but the difference is not much. b) Nature of the substrate: The AOP values for the same reaction differ from one substrate to another. For example hydrogen ion discharge reaction needs different energy values for different metals. The AOP for H+ discharge is the lowest on platinum and the highest on mercury. Other metals like lead, silver, nickel and copper show intermittent values. For this reason, Platinum electrodes are used in industrial electrolysis of water, so as to minimize the voltage to be applied. In lechelanche cell mercuric compounds are used as additives in order that hydrogen should not be evolved. For the same reason mercury is used as polarographic liquid (dropping mercury electrode), which facilitates the study of the reduction of most of the metal ions before H+ is reduced. Similarly oxygen over voltage on platinum is high and low on lead. Lead-antimony alloy electrodes are used as anodes in chromium plating, which effects oxygen evolution at lower applied potential than with other electrodes. Graphite electrodes are used in electrolytic manufacture of chlorine gas, where the over voltage is moderate. c) Texture of the substrate: The surface texture or finish plays a role in deciding the AOP value. Micro-etched or matt metal surface has lower AOP than polished surface of the same electrode, for the same reaction. Similarly a porous surface facilitates more easily gaseous discharge reaction and eventually gaseous evolution than an ordinary surface of the same metal. d) Surface area: As the area increases AOP decreases, all other conditions being the same. Platinizing platinum is deposition of micro fined platinum on platinum surface. This increases the surface area many fold and brings down the AOP. e) Current density: Activation over potential is directly proportional to the current density. If the reaction rate is increased, activation energy increases; the limit will be the reach of applied potential for the

30 reduction of metal species present in the solution. For examples nickel deposition from nickel sulphate solution can be considered. The rate of deposition can be increased by increasing over potential or by increasing applied potential (equilibrium potential, for a reaction, at a particular concentration is constant) till reduction of H+ or H2O occurs, leading to hydrogen evolution. f) Temperature: AOP is inversely proportional to temperature. As temperature is increased ionic mobility increases and thereby ion transport is facilitated. Hence AOP decreases. But in industrial practice where a rise in temperature is needed to sustain the desired current heating is accomplished. Other wise the process is conducted at room temperature. For example bright nickel and bright chromium deposition are carried out at elevated temperature. But copper deposition from acid copper sulphate is carried out at room temperature at lower current densities and 50-60 oC for higher current densities beyond 5 A/dm2. Concentration over potential: This phenomenon is explained by taking the example of nickel deposition from NiSO4 solution, using nickel soluble anode. The positive terminal of DC supply is connected to nickel anode through an ammeter in series. The negative terminal of the supply is connected to a copper cathode (or any substrate) through a variac. A voltmeter is connected across the DC supply. Let us assume that 4 volt is applied to effect a current of 100 A (at 4 A/dm2). As the deposition occurs, nickel ions present near the cathode will be discharged. Ni++ + 2e Ni This leads to a decrease in concentration of nickel ions at the vicinity of the cathode than in the bulk. Nickel ions from the bulk will migrate to the cathode.

Figure On the other hand, as the nickel anode dissolves forming nickel ions, which crowd near the anode. Thereby the concentration of nickel ions is more near the anode than in the bulk. Ni Ni 2 + + 2e They migrate slowly towards the bulk.

31 Hence at any instant of time the concentration of Nickel ions is high near the anode and gradually decreases to the bulk and finally to the cathode, where it is the least. That is, a concentration gradient in decreasing order from anode to cathode gets established. This concentration gradient is equivalent to a potential gradient (evident from Nernst equation). This potential opposes the external applied voltage. This opposition manifests itself as a reduction in the rate of deposition; reading in the ammeter falls (probably from 100 to 80). Voltmeter reading does not change. To bring back the rate of deposition to the original level (80 to 100), an extra potential (from 4 to 4.5 perhaps) will be required. This extra potential is required to overcome the resistance offered by concentration gradient or concentration polarization and is known as concentration overpotential. Application of a higher voltage is not a permanent solution. Again the current will decrease and potential is to be increased further and this is repetitive. Permanent remedy to overcome this is to stir or agitate the solution effectively to maintain a uniform concentration throughout the entire bath. The energy spent in providing air or mechanical agitation is equivalent to concentration overpotential. 4. IR overpotential: This extra energy is required to overcome the resistance offered by the system. The electrical connection from the DC power supply to the bus bar of the reaction tank, the jig carrying the job, the electrolyte and the electrodes. Proper care must be exercised to minimize internal resistance. i. Electrical Connections: The materials used for connecting the DC supply to the tank, the bus bar and the jigs must be of high conducting ones electrically and thus copper is extensively used for this purpose. The dimension (size and shape) of the connecting materials, the bus bar and the jigs must be adequate to carry the desired current. If sufficient cross section is not available, energy will be dissipated as heat. For example 4 copper flats can carry current upto 1200 A. Where higher current is required, copper flats of appropriate size are used for electrical connection (Remember R 1/a) R-resistance and a is area of cross section). ii. Electrolyte To reduce the resistance offered by the electrolyte, its concentration must be increased to the maximum. The limit will be its solubility in water, for aqueous electrolyte. Generally sulphates, nitrates and chlorides are soluble in water. In plating, sulphate is preferred. The use

32 of nitrate and chloride salts increases the anodic polarization i.e., anodic dissolution. The maximum amount than can dissolve at room temperature is generally taken. Wherever permitted strong acids such as H2SO4 can be added to increase the conductance or reduce the IR component. iii. Electrodes: The electrode at which the desired reaction is carried out is called job and no choice is available here. For example if plating is to be done on an MS article, a lead or graphite article cannot be taken even though the AOP may be lesser on Pb or C, than on MS, for that deposition. Similarly in plating, soluble anode is employed whenever possible. At other proceses SS, graphite and lead anodes are used for economic considerations. But the positioning of electrodes is done to minimize internal resistance. If they are far apart, the resistance is more and increases the AP; if they are too close the volume of entrapped electrolyte will be less and this hastens the onset of concentration polarization. Agitation must be more efficient to overcome this. Hence the electrodes are positioned at optimum distance. Thus the applied potential for an electrochemical process is AP = EP + [AOP + COP + IROP] EP- is equilibrium potential at the employed concentration and is constant for a particular reaction. AOP-Activation over potential this increases the AP. COP controlled by agitation. IROP- minimized Tafel equation and Tafel plots Tafel equation governs the irreversible behaviour of an electrode. To understand this we can consider the general mechanism of electron transfer to an electrode. Consider an electrolyte in which an inert or noble electrode is kept immersed. It is called working electrode, (WE). Also assume that an oxidized and a reduced species are present near the electrode and exhibit the following electron transfer reaction. O + ne R (1)

O is oxidized and R is reduced species present at equilibrium and is stable in the solution. Let us assume that no other electron transfer reaction other than the above occurs. Let the concentration of O and R be CO and CR respectively and they are very low. An inert electrolyte is also present to minimize IR drop. Along with WE, a reference electrode (RE) is also kept immersed, to form the

33 cell. Since the potential of RE is constant, variation in cell emf is the variation in WE, and vice versa. At the thermodynamic equilibrium of the system no net current flows across RE and WE, no chemical reaction takes place and hence the composition of the solution remains unchanged. The potential of the working electrode will be its equilibrium potential Ee, which according to Nernst equation is Ee = Ee + RT ln[CO / CR ] (2) nF o Where Ee is the standard or formal reversible potential and is constant. Ee depends on the ratio of [CO/CR]. The square bracketed term should be in terms of activity rather than molar concentration; but at low concentration the replacement is error free. The equilibrium mentioned above is dynamic. Though no net current flows across the electrodes, both reduction and oxidation takes place at equal rate, so that the composition of the electrolyte does not change. The dynamic flow of electrons or charge in both directions can be written in terms of current densities as follows. IA = IC = I0 ---- (3)
o

Where IA is anodic and Ic is cathodic current densities. By convention anodic current density is given +ve sign and cathodic ve sign. Io is known as exchange current density. It may be defined, as the flow of charge or electrons across an electrochemical system in equilibrium is known as exchange current density. Its value normally is very low, of the order 10 -8 A. It refers to the extent of both oxidation and reduction that occurs. The equilibrium situation at an electrode is characterized by equilibrium potential and exchange current density. For the reaction to have practical significance, a net current should flow and a net reaction either oxidation or reduction should occur. For this the kinetic aspect of the system must be considered. It is to be recalled that thermodynamics fixes the direction and kinetics determines the rate. For this let as apply an external potential to WE, more negative than Ee. This cause, an increase in cathodic current and a net quantity of O will be reduced to R. The value of the ratio [CO/CR] at the electrode surface will diminish. The magnitude of net cathodic current and the time for the new value of [CO/CR] takes to achieve depend on the rate or the kinetics of the electron

34 transfer reaction. The net cathodic current will be due to the increase in partial cathodic current (Ic) and a decrease in partial anodic current (IA) at this new potential. Hence reversible condition changes to irreversible condition. This is achieved by applying a more ve potential or excess potential than Ee, which is known as overpotential. Conversely it can be argued that if WE is made more positive than Ee (by applying external potential more positive than Ee) a net anodic current will flow through the cell. To summarize the situation. At the equilibrium potential Ee -IC IA -IC Negative to Ee IA -IC Positive to Ee IA I = -IC + IA > 0 net anodic current I = -IC + IA < 0 net cathodic current I = -IC +IA = 0 No net current

The kinetic equation for this electron transfer reaction can be derived. Generally electron transfer processes are first order reactions. Hence rate of reduction of [O] is proportional to its concentration at the electrode surface (Remember that it is assumed that surface concentration is equal to bulk concentration). Rate of reduction of [O] = kRCo The partial cathodic current density will be -Ie = nFKc[CO] dependence is of the form Kc = K0 exp [cnF E] RT and E is the applied potential. Substituting for the kc value in 5, we get -Ie = nFKoCoexp [cnF E] RT Rate of oxidation = kACR ... (7) ... (6) .. (5) The rate of the electron transfer process depends on the applied potential and the potential (4)

Where c is the cathodic transfer coefficient and ko is the rate constant for electron transfer at E = 0

The corresponding equation for oxidation of R, occurring simultaneously will be .. (8)

35 IA = nFKACR KA = K0 exp [AnF E] RT IA = nFKoCR exp [AnF E] RT .. (9) ... (10) ... (11)

The current density at any potential will be the sum of cathodic and anodic current densities. I = IA + (-IC) = nF KoCRexp(AnF E) KoCoexp(CnF E) RT RT But overpotential = E -Ee Hence Io = nFKoCRexp(AnF Ee) = nFKoCoexp(CnF Ee) .. (15) RT RT Substitution of (14) in (13) and using equation (15), the famous Butler-Volmer equation is obtained. I = I0 exp(AnF ) exp(CnF ) RT RT .. (16) (14) is a deviation of experimental potential from equilibrium potential. At E = Ee, I A = -IC = Io. ... (12) .. (13)

From this equation, it can be understand that the measured current density is a function of i) over potential () ii) exchange current density (Io) and iii) anodic and cathodic transfer coefficients (A + C) Transfer coefficients are not independent variables. In general A + C = 1 For many reaction A + C = 0.5 Equation 16 indicates that the current density at any overpotential is the sum of cathodic and anodic current densities. At the extreme condition of overpotential being highly negative. Cathodic current density increases while anodic current density becomes negligible. At this stage, the first term in Butler-volmer equation (16) becomes negligible. The equation can be written as -I = -IC = Io exp(-cnF ) RT .. (18) (17)

36

When the overpotential is higher than above 52mV, this equation shows that the increase in current is exponential with overpotential. The current also depends on Io. Equation 18, may also be written as log-IC = log Io cnF 2.303RT .. (19)

Equation 19 is called cathodic tafel equation. Similarly at positive overpotentials higher than 52 mV anodic current density is much higher than cathodic and the second term in equation 16 can be neglected. Hence I = IA = Io exp(AnF ) RT Log IA = log Io + (AnF ) 2.303RT Equation 21 is called anodic Tafel equation. When log I values are plotted against overpotential we get Tafel plots. These offer simple method for experimentally determining Io, transfer coefficients. The intercept is log Io from which Io can be calculated. .. (20) .. (21)

From the anodic slope, A and from cathodic slope C can be determined.

37 At very low values say < 10 mV, Butler-Volmer equation has another form when A = c = 0.5, I = Io (nF/RT) by standard rate constant. Then Io = nFKoCoA CRC Or Io = nFKoCo CR1- .. (23) (24) .. (22) Since exchange current density depends on both the concentration of O and R, it can be replaced

The effect of C on current density is shown in the following plot.

a) C = 0.25 oxidation is favoured b) C = 0.50 symmetrical c) C = 0.75 reduction is favoured As cathodic transfer coefficient value increases reduction is favoured and oxidation is not favoured and vice versa for anodic transfer coefficient. Note: The above simple treatment assumes that the concentration of (O) + ( R ) are uniform in the electrolyte as well as near the electrodes. Modes of mass transport like migration, convection and diffusion are not treated.

38