UNIT 3: ELECTROCHEMISTRY

UNIT 3: ELECTROCHEMISTRY
SYNOPSIS An electrochemical cell and difference between galvanic and electrolytic cells; Nernst equation for calculating the emf of cell and define standard potential of the cell; Standard Potential of the Cell, Gibbs energy of cell reaction and its Equilibrium constant; Define resistivity (), conductivity () and molar conductivity (m) of ionic solutions; Difference between ionic (electrolytic) and electronic conductivity; Measurement of conductivity of electrolytic solutions and calculation of their molar conductivity; Variation of conductivity and molar conductivity of solutions with change in their concentration and define m (molar conductivity at zero concentration or infinite dilution); Kohlrausch law and its applications; Quantitative aspects of electrolysis; Construction of some primary and secondary batteries and fuel cells; Corrosion as an electrochemical process.

INTRODUCTION:
Electrochemistry is the branch of chemistry which deals with conversion of electrical energy into chemical energy (in electrolytic cells) and chemical energy into electrical energy (in galvanic cells) and the study of behaviour of electrolytes.

Electrochemical Cells:
An electrochemical cell is a device in which inter-conversion of chemical energy and electrical energy takes place. It involves redox reactions. Electrochemical cell is of two types. (i) Electrolytic cell, (ii) Galvanic cell. ELECTROLYTIC CELL: An electrochemical cell in which electrical energy is converted into chemical energy. i.e. a device for using electrical energy to carry non-spontaneous chemical reactions. GALVANIC CELL: The device in which electrical energy generated by using a spontaneous redox reaction is called galvanic cell or voltaic cell. The free energy of the reaction is used to do the electrical work. Eg: Daniel cell, Ni-Cd cell etc. DANIEL CELL: Daniel cell consists of two beakers, one of which contains 1M ZnSO4 solution & other 1M CuSO4 solution. A zinc rod is dipped in ZnSO4 solution and a copper rod in CuSO4 solution. Externally, the zinc rod and copper rod are connected by an insulated wire. The two solutions are connected by a salt-bridge. WORKING OF DANIEL CELL: CELL REACTIONS: When the two electrodes are connected, a spontaneous chemical reaction takes place at each electrode. (a) Zn has a tendency to lose electrons. Some of the Zn atoms leave electrons on the rod and come into solution as Zn+2 ions. :2 + 2 ; (Oxidation half) Hence, Zn rod becomes negatively charged. It is called anode as oxidation takes place at this electrode. (b) Cu has a tendency to gain electrons. Some of the Cu+2 ions from the solution deposit on the metal as Cu by gaining electrons. :2 + 2 ; (Reduction half) Hence, Cu rod becomes positively charged. It is Fig. 3.1: Daniell cell having electrodes of called cathode as reduction takes place at this zinc and copper dipped in the electrode. The net cell reaction is; solutions of their respective salts. + :2 :2 + REPRESENTATION OF CELL: By convention, the anode is kept on the left and the cathode on the right while representing the galvanic cell. A galvanic cell is generally represented by putting a vertical line between metal and electrolyte solution and putting a double vertical line between the two electrolytes connected by a salt bridge. i.e Zn |Zn+2 || Cu+2 | Cu
1

UNIT 3: ELECTROCHEMISTRY EMF OF A CELL: Under this convention the emf of the cell is positive and is given by the potential of the half-cell on the right hand side minus the potential of the half-cell on the left hand side. EMF = ERHE ELHE OR EMF = Epositive electrode Enegative electrode = ECathode EAnode
1. 2. 3. 4. DISTINCTION BETWEEN ELECTROLYTIC CELL AND GALVANIC CELL ELECTROLYTIC CELL GALVANIC CELL Electrical energy is used to bring a redox 1. Electrical energy is produced using a redox reaction. reaction. Oxidation takes place at the +ve electrode. 2. Oxidation takes place at the ve electrode. Hence +ve electrode is anode. Hence ve electrode is anode. Reduction takes place at the ve electrode. 3. Reduction takes place at the + ve electrode. Hence ve electrode is cathode. Hence + ve electrode is cathode. Externally electrons enter from cathode & 4. Externally electrons move from anode to come out from anode. cathode.

ELECTRODE POTENTIAL: The potential developed when a metal is in equilibrium with a solution of its own ions is called electrode potential. In fact, it is the measure of the tendency of an electrode in a half-cell to lose or gain electrons. STANDARD ELECTRODE POTENTIAL: The potential developed when a metal is in equilibrium with a one molar solution of its ions at 298K is called standard electrode potential (or standard reduction potential). If the electrode contains a gas, its pressure should be 1 atmosphere). EMF: The potential difference between the two electrodes (cathode and anode) of a galvanic cell is called the cell potential and is measured in volts. It is called the electromotive force (emf) of the cell when no current is drawn through the cell.

Measurement of Electrode Potential:

The potential of individual half-cell cannot be measured. But the measurement of difference between the two half-cell potentials gives the emf of the cell. The potential of one electrode (half-cell) can be determined by combining with other electrode (half-cell) of known electrode potential. Standard Hydrogen Electrode is an electrode with hydrogen gas at a pressure of 1 atmosphere in equilibrium with one molar hydrochloric acid in the presence of platinum.
CONSTRUCTION OF S.H.E:

The standard hydrogen electrode consists of a platinum electrode coated with platinum black. The Inner tube electrode is dipped in an acidic solution and pure hydrogen gas is bubbled through it. The concentration of both the reduced and oxidised Pure H2 (1 atm) forms of hydrogen is maintained at unity (Fig. 3.3). Outer tube That is the pressure of hydrogen gas is one atm. and the concentration of hydrogen ion in the Pt foil solution is one molar. Hg Pure hydrogen gas is passed at 1 atm. pressure through the inlet. The platinum foil 1MHCl adsorbs some hydrogen. Thus there is a core of platinum with an adsorbed film of hydrogen in contact with hydrogen ions in the solution. Equilibrium is established between the H2 gas and H+ ions. A potential develops due to the reaction, 1 : + ; 22 The potential of S.H.E is taken as zero. The electrode is represented as, , 2 (1) | : (1) WORKING OF SHE: SHE is coupled with a given single electrode and an electrochemical cell is set up. The EMF of the resulting cell is measured using a potentiometer. Since the potential of SHE is zero, the EMF of the cell gives the potential of the given electrode. At 298 K the emf of the cell, standard hydrogen electrode || second half-cell constructed by taking standard hydrogen electrode as anode (reference half-cell) and the other half-cell
Cu wire 2

UNIT 3: ELECTROCHEMISTRY as cathode, gives the reduction potential of the other half-cell. If the concentrations of the oxidised and the reduced forms of the species in the right hand half-cell are unity, then the cell potential is equal to standard electrode potential, of the given half-cell. = As for standard hydrogen electrode is zero. = 0 = The measured emf of the cell : Pt(s), 1 H H+ (aq, 1 M) || Cu2+ (aq, 1 M) Cu is +0.34 V 2 2(g, 1 atm.) and it is also the value for the standard electrode potential of the half-cell corresponding to the reaction : Cu2+ (aq, 1M) + 2e Cu(s) Similarly, the measured emf of the cell: Zn2+ (aq, 1M) Zn || H+ (aq, 1 M) 1 H , Pt(s) is 2 2 (g, 1 atm.) 0.76 V corresponding to the standard electrode potential of the half-cell reaction: Zn2+ (aq, 1 M) + 2e Zn(s) Thus for Daniell cell, the half-cell reaction can be represented as Left electrode: Zn(s) Zn2+ (aq, 1 M) + 2 e Right electrode: Cu2+ (aq, 1 M) + 2 e Cu(s) The overall reaction of the cell is the sum of above two reactions and we obtain the equation: Zn(s) + Cu2+ (aq) Zn2+ (aq) + Cu(s) Emf of the cell = = = 0.34V ( 0.76)V = 1.10 V Sometimes metals like platinum or gold are used as inert electrodes. They do not participate in the reaction but provide their surface for oxidation or reduction reactions and for the conduction of electrons. For example, Pt is used in the following half-cells: Hydrogen electrode: Pt(s)|H2(g)| H+(aq), with half-cell reaction: H+ (aq) + e H2(g) Bromine electrode: Pt(s)|Br2(aq)| Br(aq), with half-cell reaction: Br2(aq) + e Br(aq)

ELECTROCHEMICAL SERIES:
The list of standard reduction potentials arranged in the order of their increasing value is called electrochemical series. The standard electrode potentials are very important and we get useful information from them. Table 3.1 The standard electrode potentials at 298 K
ELECTRODE Li / Li K+ / K Ba+2 / Ba Ca+2 / Ca Na+ / Na Mg+2 / Mg Al+3 / Al Zn+2 / Zn Fe+2 / Fe Ni+2 / Ni H+ / H Cu+2 / Cu Ag+ / Ag Au+3 / Au Pt, 1/2 F2 / F
+

ELECTRODE REACTION : + ; : + ; :2 + 2 ; :2 + 2 ; : + ; :2 + 2 ; :3 + 3 ; :2 + 2 ; :2 + 2 ; :2 + 2 ; 1 : + ; 22 :2 + : + :3 + 1 + 2 2 2 ; ; 3 ; ;
;

STD. RED. POTENTIAL (V) 3.05 2.93 2.90 2.87 2.71 2.37 1.66 0.76 0.44 0.25 0.00 + 0.34 + 0.80 + 1.50 + 2.55

SIGNIFICANCE OR IMPORTANCE OF ELECTROCHEMICAL SERIES: Metals in the top of the list are good reducing agents. Elements at the bottom of the list are good oxidising agents. o A metal in the electrochemical series displaces another below it from its salt solution. o Metals which are above hydrogen in the series displace hydrogen from dilute acids. o The series helps in selective discharge of different elements from a mixture of their ions.

UNIT 3: ELECTROCHEMISTRY

Nernst Equation:

: Nernst showed that for the electrode reaction: () + ; () The electrode potential at any concentration measured with respect to standard hydrogen electrode can be represented by: [] (+ / ) = ( [+ ] + / )

But the concentration of solid M is taken as unity and we have 1 (+ / ) = ( [+ ] + / )

( + / )

(3.8)

Where is standard electrode potential, R is gas constant (8.314 JK1 mol1), F is Faraday constant (96487 C mol1), T is temperature in kelvin and *Mn++ is the concentration of the species, Mn+. In Daniell cell, the electrode potential for any given concentration of Cu2+ and Zn2+ ions, we write 1 For Cathode: (2+ / ) = ( (3.9) 2+ / ) 2 [2+ ] For Anode: The cell potential,
(2+ / ) = ( 2+ / ) 2 = ( 2+ / ) (2+ / ) 1 1 = ( [2+] ( [2+] 2+ / ) 2+ / ) + 2 2 1 1 = ( [ ] 2+ / ) (2+ / ) 2+ 2 [ ] [2+ ] [2+ ] = 2 [2+ ] (3.11)

[2+ ]

(3.10)

Thus E(cell) depends on the concentration of both Cu2+ and Zn2+ ions. It increases with increase in the concentration of Cu2+ ions and decrease in the concentration of Zn2+ ions. By converting the natural logarithm in Eq. (3.11) to the base 10 and substituting the values of R, F and T = 298 K, it reduces to
= 0.0591 2

[2+ ] [2+ ]

We should use the same number of electrons (n) for both the electrodes. For eg. Ni(s) | Ni2+(aq) || Ag+(aq) | Ag The cell reaction is Ni(s) + 2Ag+(aq) Ni2+(aq) + 2Ag(s) The Nernst equation can be written as
= 2

[+ ]2

[ 2+ ]

Thus for a general electrochemical reaction of the type: aA + bB ne cC + dD Nernst equation can be written as: = 2
= 2

[][]

[] []

(3.13)

Example 3.1: Represent the cell in which the following reaction takes place Mg(s) + 2Ag+(0.0001M) Mg2+(0.130M) + 2Ag(s). Calculate its E(cell) if = 3.17 V. 2+ + Solution: The cell can be written as Mg|Mg (0.130M)||Ag (0.0001M)|Ag.
= 2

Equilibrium Constant from Nernst Equation:

0.0591 0.130 = 3.17 = 3.17 0.21 = 2.96 2 (0.0001)2

[+]2

[2+ ]

In Daniell cell, when the circuit is closed, the redox reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) (3.1) 2+ takes place and as time passes, the concentration of Zn keeps on increasing while the concentration of Cu2+ decreases. At the same time voltage of the cell as read on the voltmeter keeps on decreasing. After some time, there is no change in the concentration of Cu2+ and Zn2+ ions and voltmeter gives zero reading. This indicates that equilibrium has been attained and for which the Nernst equation may be written as:
= 0 = 2.303 [2+ ] [2+ ] 2

[2+ ] [2+ ]

OR

2.303 2

UNIT 3: ELECTROCHEMISTRY But at equilibrium, [2+ ] =

[2+ ]

for the reaction 3.1.

( = 1.10 )

and at T = 298K the above equation can be written as 0.0591 = = 1.10 2

2 1.10

= 0.0591 = 37.288 (37.288) = 2 1037 at 298 K = 2.303 In general, = Example 3.2: Calculate the equilibrium constant of the reaction: Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s) (Given = 0.46 V) Solution: Given: = 0.46 V
WKT, = 0.0591

= =

2 2 0.46

OR

0.0591

= 15.6 0.0591 (15.6) = 3.92 1015

Electrochemical Cell and Gibbs Energy of the Reaction:

Electrical work done in one second is equal to electrical potential multiplied by total charge passed. To obtain maximum work from a galvanic cell then charge has to be passed reversibly. The reversible work done by a galvanic cell is equal to decrease in its Gibbs energy and therefore, if the emf of the cell is E and nF is the amount of charge passed and rG is the Gibbs energy of the reaction, then rG = nFE(cell) (3.15) It may be remembered that E(cell) is an intensive parameter but rG is an extensive thermodynamic property and the value depends on n. Thus, for the reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) rG = -2FE(cell) 2+ 2+ And for the reaction 2Zn(s) + 2Cu (aq) 2Zn (aq) + 2Cu(s) rG = -4FE(cell) o If the concentration of all the reacting species is unity, then E(cell) = E (cell) and we have rGo = nFEo(cell) (3.16). o Also rG = RT ln K = - 2.303RT logK. Example 3.3: The standard electrode potential for Daniell cell is 1.1V. Calculate the standard Gibbs energy for the reaction: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s). Solution: rGo = nFEo(cell) For the given reaction n = 2, F = 96487 C mol1 and Eo(cell) = 1.10 V Therefore, rGo = 2 x 1.1V x 96487 C mol1 = 21227 J mol1 = 21.227 kJ mol1

Conductance of Electrolytic Solutions:

DEFINITIONS: Resistance: The electrical resistance (R) is the opposing force to the flow of current offered by the substance and it is measured in ohm () (SI unit is (kg m2)/(s3 A2). It is measured with the help of a Wheatstone bridge. The electrical resistance of any object is directly proportional to its length, l, and inversely proportional to its area of cross section, A. That is, OR = (3.17) The proportionality constant, (rho), is called resistivity (specific resistance). Its SI units are ohm metre ( m) or its submultiple, ohm centimetre ( cm) is also used. The resistivity of a substance is its resistance when it is one metre long and its area of cross section is one m2. It can be seen that: 1 m = 100 cm or 1 cm = 0.01 m The inverse of resistance, R, is called conductance, C, and we have the relation: 1 = = = (3.18) The SI unit of conductance is Siemens (S) OR ohm1 (also known as mho) or 1. The inverse of resistivity is conductivity (specific conductance), (kappa). The SI units of conductivity are S m1 but often S cm1. Conductivity of a material is its conductance when it is 1 m long and its area of cross section is 1 m2. It may be noted that 1 S cm1 = 100 S m1.

UNIT 3: ELECTROCHEMISTRY Table 3.2: The values of Conductivity of some Selected Materials at 298.15 K

Certain materials called superconductors by definition have zero resistivity or infinite conductivity. Earlier, only metals and their alloys at very low temperatures (0 to 15 K) were known to behave as superconductors, but nowadays a number of ceramic materials and mixed oxides are also known to show superconductivity at temperatures as high as 150 K. Electrical conductance through metals is called metallic or electronic conductance and is due to the movement of electrons. The electronic conductance depends on (i) The nature and structure of the metal (ii) The number of valence electrons per atom (iii) Temperature (it decreases with increase of temperature). The conductance of electricity by ions present in the solutions is called electrolytic or ionic conductance. The conductivity of electrolytic (ionic) solutions depends on: (i) The nature of the electrolyte added (ii) Size of the ions produced and their solvation (iii) The nature of the solvent and its viscosity (iv) Concentration of the electrolyte (v) Temperature (it increases with the increase of temperature). Passage of direct current through ionic solution over a prolonged period can lead to change in its composition due to electrochemical reactions.

Measurement of the Conductivity of Ionic Solutions:

Accurate measurement of an unknown resistance can be performed by Wheatstone bridge. But, this cannot be used for measuring the resistance of an ionic solution. Since, passing direct current (DC) changes the composition of the solution and a solution cannot be connected to the bridge like a metallic wire or other solid conductor. The first difficulty is resolved by using an alternating current (AC) source of power. The second problem is solved by using a specially designed vessel called conductivity cell.

It consists of two platinum electrodes coated with platinum black. Their cross sectional area is A and are kept at distance l. Therefore, solution in between these electrodes is a column of length l and area of cross section A. The resistance of such a column of solution is then given by the equation: = =

UNIT 3: ELECTROCHEMISTRY The quantity is called cell constant denoted by the symbol, C*. It depends on the distance between the electrodes and their area of cross-section and has the dimension of length1 and calculated by knowing l and A. Measurement of l and A is not only inconvenient but also unreliable. The cell constant is usually determined by measuring the resistance of the cell containing a solution whose conductivity is already known. Generally, we use KCl solutions whose conductivity is known accurately at various concentrations (Table 3.3) and at different temperatures. The cell constant, C*, is then given by the equation: = = = Table 3.3: Conductivity and Molar conductivity of KCl solutions at 298.15K

Once the cell constant is determined, we can use it for measuring the resistance or conductivity of any solution. The set up for the measurement of the resistance is shown in Fig. 3.5. It consists of two resistances R3 and R4, a variable resistance R1 and the conductivity cell having the unknown resistance R2. The Wheatstone bridge is fed by an oscillator O (a source of A.C. power in the audio frequency range 550 to 5000 cycles per second). P is a suitable detector (a headphone or other electronic device) and the bridge is balanced when no current passes through the detector. Under these conditions: Unknown resistance, R 2 =
R1 R4 R3

(3.19)

Fig.3.5: Arrangement for measurement of resistance of a solution of an electrolyte.

Conductivity meters are available which can directly read the conductance or resistance of the solution in the conductivity cell. Once the cell constant and the resistance of the solution in the cell are determined, the conductivity of the solution is given by the equation:
Cell Constant C

= = R (3.20) R MOLAR CONDUCTANCE(): Molar conductance of an electrolyte is the conductance of the solution due to all the ions produced by one mole of the electrolyte. m = c (3.21) Unit of Molar conductance: = c = mol.m3 = Sm2 mol;1 . 1 Sm2 mol;1 = 104 S cm2 mol;1 OR 1 S cm2 mol;1 = 10;4 S m2 mol;1. Example 3.4: Resistance of a conductivity cell filled with 0.1 mol L1 KCl solution is 100 . If the resistance of the same cell when filled with 0.02 mol L1 KCl solution is 520 , calculate the conductivity and molar conductivity of 0.02 mol L1 KCl solution. The conductivity of 0.1 mol L1 KCl solution is 1.29 S/m. Solution: The cell constant is given by the equation: Cell constant = C* = conductivity resistance = 1.29 S/m 100 = 129 m1 = 1.29 cm1 1 Conductivity of 0.02 mol L KCl solution = cell constant / resistance = Concentration = 0.02 mol L1 = 1000 0.02 mol m3 = 20 mol m3 Molar conductivity = = =
Sm1

129 1 520

= 0.248 S m1

248 103 1 20 3

= 124 10;4 2

;1

UNIT 3: ELECTROCHEMISTRY Alternatively, and =

1.29 1 520

= 0.248 10;2 ;1
1

= x 1000 3

= = 124 2 ;1 0.02 1 Example 3.5: The electrical resistance of a column of 0.05 mol L1 NaOH solution of diameter 1 cm and length 50 cm is 5.55 103 ohm. Calculate its resistivity, conductivity and molar conductivity. Solution: A = r2 = 3.14 0.52 cm2 = 0.785 cm2 = 0.785 104 m2 l = 50 cm = 0.5 m =

0.248 102 1 x 1000 3 1

OR

=
1

5.55 x 103 x 0.785cm2

= =

50 1

= 87.135 cm

, = =

87.135 1000 3 1

= 0.01148 ;1

0.01148 1 1000 3 1 0.05 1

= 229.6 2

;1

Variation of Conductivity and Molar Conductivity with Concentration:

Conductivity and molar conductivity change with the concentration of the electrolyte. The Conductivity of both weak and strong electrolytes decreases with decrease in concentration. This is because the number of ions per unit volume that carry the current in a solution decreases on dilution. The conductivity of a solution at any given concentration is the conductance of one unit volume of solution kept between two platinum electrodes with unit area of cross section and at a distance of unit length. This is clear from the equation: = = When A = m2 and l=m. Molar conductivity of a solution at a given concentration is the conductance of the volume V of solution containing one mole of electrolyte kept between two electrodes with area of cross section A and distance of unit length. Therefore, = = Since l=1 and A = V (volume containing 1 mole of electrolyte) = (3.22) Molar conductivity increases with decrease in concentration. This is because the total volume, V, of solution containing one mole of electrolyte also increases. When concentration approaches zero, the molar conductivity is known as limiting molar conductivity and is represented by the symbol . The variation in m with concentration is different (Fig. 3.6) for strong and weak electrolytes. Strong Electrolytes: For strong electrolytes, increases slowly with dilution and can be represented by the equation: 1/2 = (3.23) It can be seen that if we plot (Fig. 3.6) against 1/2 , we obtain a straight line with intercept equal to and slope equal to . The value of the constant for a given solvent and temperature depends on the type of electrolyte i.e., the charges on the cation and anion produced on the dissociation of the electrolyte in the solution. Thus, NaCl, CaCl2, MgSO4 are known as 1-1, 2-1 and 2-2 electrolytes respectively. All electrolytes of a particular type have the same value for A.

Fig. 3.6: Molar conductivity versus c for acetic acid (weak electrolyte) and potassium chloride (strong electrolyte) in aqueous solutions.

UNIT 3: ELECTROCHEMISTRY

Kohlrausch law of independent migration of ions:

The law states that limiting molar conductivity of an electrolyte can be represented as the sum of the individual contributions of the anion and cation of the electrolyte. Thus, if + and are limiting molar conductivity of the sodium and chloride ions respectively, then the limiting molar conductivity for sodium chloride is given by the equation: (3.24) (NaCl) = + + In general, if an electrolyte on dissociation gives v+ cations and v anions then its limiting molar conductivity is given by: (3.25) (NaCl) = : : + ; ; Table 3.4: Limiting molar conductivity for some ions in water at 298 K

Weak electrolytes:
Weak electrolytes like acetic acid have lower degree of dissociation at higher concentrations and hence for such electrolytes, the change in m with dilution is due to increase in the degree of dissociation and consequently the number of ions in total volume of solution that contains 1 mol of electrolyte. In such cases m increases steeply (Fig. 3.6) on dilution, especially near lower concentrations. Therefore cannot be obtained by extrapolation of m to zero concentration. At infinite dilution (i.e., concentration c zero) electrolyte dissociates completely ( =1), but at such low concentration the conductivity of the solution is so low that it cannot be measured accurately. Therefore, for weak electrolytes is obtained by using Kohlrausch law of independent migration of ions (Example 3.8). At any concentration c, if is the degree of dissociation then it can be approximated to the ratio of molar conductivity m at the concentration c to limiting molar conductivity, . Thus we have: Using Kohlrausch law of independent migration of ions, it is possible to calculate for any o electrolyte from the of individual ions. 2 1 Example 3.7: respectively. for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm mol Calculate o for HAc. Solution: Given: () = 126.4 2 ;1 () = 425.9 2 ;1 () = 91.0 2 ;1 From Kohlrausch Law, WKT, (HAc) = + + = + + + + + + = () + () () = (425.9 + 91.0 126.4 ) S cm2 mol1 = 390.5 S cm2 mol1. = (3.26)

Also

(1;)

(3.27)

Electrolytic Cells and Electrolysis:

Electrolytic cell is one in which an external source of voltage is used to bring about a chemical reaction. For eg: Consider an electrolytic cell consisting of two copper strips dipping in an aqueous solution of copper sulphate. If a DC voltage is applied to the two electrodes, then Cu2+ ions discharge at the cathode (negatively charged) and the following reaction takes place: Cu2+(aq) + 2e -- Cu (s) (3.28) Copper metal is deposited on the cathode. At the anode, copper is converted into Cu2+ ions by the reaction: Cu(s) Cu2+(s) + 2e (3.29)
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UNIT 3: ELECTROCHEMISTRY Thus copper is dissolved (oxidised) at anode and deposited (reduced) at cathode. This is the basis for purification of the metals. The impure copper is made an anode that dissolves on passing current and pure copper is deposited at the cathode. Many metals like Na, Mg, Al, etc. are produced on large scale by electrochemical reduction of their respective cations where no suitable chemical reducing agents are available for this purpose. Sodium and magnesium metals are produced by the electrolysis of their fused chlorides and aluminium is produced by electrolysis of aluminium oxide in presence of cryolite. ELECTROLYSIS: The decomposition of an electrolyte on passing electric current through its molten state or its solution is called electrolysis.

FARADAYS LAWS OF ELECTROLYSIS:

FIRST LAW: The mass of a substance liberated or deposited at an electrode during electrolysis is proportional to the quantity of electricity passed. i.e, W Q Where,W = Mass of substance liberated or deposited at an electrode. Q = Quantity of electricity in Coulombs. Since, Charge = Current x Time, Q=Ixt Hence, WIxt OR W = z x I x t Where, Z is called Electrochemical equivalent (e.c.e) of the substance. SECOND LAW: When the same quantity of electricity is passed through the solutions of different electrolytes connected in series, the masses of the substances deposited or liberated at respective electrodes are directly proportional to their equivalent masses. i.e, = The amount of electricity (or charge) required for oxidation or reduction depends on the stoichiometry of the electrode reaction. For example, in the reaction: Ag+(aq) + e Ag(s) (3.30) One mole of the electron is required for the reduction of one mole of silver ions. We know that charge on one electron is equal to 1.6021 x 1019C. Therefore, the charge on one mole of electrons is equal to: NA x 1.6021 x 1019C C = 6.022 x 1023 mol1 x 1.6021 x 1019 C = 96487 C mol1. This quantity of electricity is called Faraday and is represented by the symbol F. 1F 96500 C mol1. Example 3.10: A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 amperes. What is the mass of copper deposited at the cathode? Solution: Given: t = 10 mins = 600 s I = 1.5 A Charge (Q) = Current (I) time (t) = 1.5 A 600 s = 900 C According to the reaction: Cu2+(aq) + 2e = Cu(s) We require 2F or 2 96487 C to deposit 1 mol or 63 g of Cu. For 900 C, the mass of Cu deposited = (63 g mol1 900 C)/(2 96487 C mol1) = 0.2938 g.

Products of Electrolysis:
Products of electrolysis depend on the nature of material being electrolysed and the type of electrodes being used. If the electrode is inert (e.g., platinum or gold), it does not participate in the chemical reaction and acts only as source or sink for electrons. While, if the electrode is reactive, it participates in the electrode reaction. Thus, the products of electrolysis may be different for reactive and inert electrodes. The products of electrolysis depend on the different oxidising and reducing species present in the electrolytic cell and their standard electrode potentials. Moreover, some of the electrochemical processes although feasible, are so slow kinetically that at lower voltages these dont seem to take place and extra potential (called overpotential) has to be applied, which makes such process more difficult to occur. For example, When molten NaCl is electrolysed, the products are sodium metal and Cl2 gas. At cathode: : + ; 1 At anode: ; 2 2 + ; . But, during the electrolysis of aqueous sodium chloride solution, the products are NaOH, Cl2 and H2. In this case besides Na+ and Cl ions we also have H+ and OH ions along with the solvent molecules, H2O.

10

UNIT 3: ELECTROCHEMISTRY Sodium hydroxide is manufactured by the electrolysis of brine. During electrolysis, H+ and Cl ions with lower discharge potential are evolved at the cathode and anode respectively. Na + and OH ions which are not discharged combine to form sodium hydroxide. Reactions taking place during electrolysis Ionisation: NaCl Na+ + Cl ; H2O H+ + OH + At the cathode: 2H + 2e H2 At the anode : 2Cl Cl2 + 2e Na+ + OH NaOH

Batteries:
Any battery (actually it may have one or more than one cell connected in series) or cell that we use as a source of electrical energy is basically a galvanic cell where the chemical energy of the redox reaction is converted into electrical energy. However, for a battery to be of practical use it should be reasonably light, compact and its voltage should not vary appreciably during its use. There are mainly two types of batteries.

Primary Batteries:
In the primary batteries, the reaction occurs only once and after use over a period of time battery becomes dead and cannot be reused again. The most familiar example of this type is the dry cell (known as Leclanche cell) which is used commonly in our transistors and clocks. The cell consists of a zinc container that also acts as anode and the cathode is a carbon (graphite) rod surrounded by powdered manganese dioxide and carbon (Fig.3.8). The space between the electrodes is filled by a moist paste of ammonium chloride (NH4Cl) and zinc chloride (ZnCl2). The electrode reactions are complex, but they can be written approximately as follows : Anode: Zn(s) Zn2+ + 2e Cathode: MnO2 + NH4++ e MnO(OH) + NH3 In the reaction at cathode, manganese is reduced from the + 4 oxidation state to the +3 state. Ammonia produced in the reaction forms a complex with Zn2+ to give *Zn (NH3)4+2+. The cell has a potential of nearly 1.5 V. Mercury cell, (Fig. 3.9) suitable for low current devices like hearing aids, watches, etc. consists of zinc mercury amalgam as anode and a paste of HgO and carbon as the cathode. The electrolyte is a paste of KOH and ZnO. The electrode reactions for the cell are given below: Anode: Zn(Hg) + 2OH ZnO(s) + H2O + 2e Cathode: HgO + H2O + 2e Hg(l) + 2OH The overall reaction is represented by Zn(Hg) + HgO(s) ZnO(s) + Hg(l) The cell potential is approximately 1.35 V and remains constant during its life as the overall reaction does not involve any ion in solution whose concentration can change during its life time.

Secondary Batteries:
A secondary cell after use can be recharged by passing current through it in the opposite direction so that it can be used again. A good secondary cell can undergo a large number of discharging and charging cycles. The most important secondary cell is the lead storage battery (Fig. 3.10) commonly used in automobiles and invertors. It consists of a lead anode and a grid of lead packed with lead dioxide (PbO2) as cathode.
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UNIT 3: ELECTROCHEMISTRY A 38% solution of sulphuric acid is used as an electrolyte. The cell reactions when the battery is in use are given below: Anode: Pb(s) + SO42(aq) PbSO4 (s) + 2e Cathode: PbO2 (s) + SO42(aq) + 4H+(aq) + 2e PbSO4 (s) + 2H2O(l) i.e., overall cell reaction consisting of cathode and anode reactions is: Pb(s)+PbO2 (s) + 2H2SO4 (aq) 2PbSO4 (s) + 2H2O(l) On charging the battery the reaction is reversed and PbSO4 (s) on anode and cathode is converted into Pb and PbO2, respectively. Another important secondary cell is the nickelcadmium cell (Fig. 3.11) which has longer life than the lead storage cell but more expensive to manufacture. The overall reaction during discharge is: Cd(s) + 2Ni(OH)3 (s) CdO(s) + 2Ni(OH)2 (s) + H2O(l)

Fuel Cells:
Production of electricity by thermal plants is not a very efficient method and is a major source of pollution. In such plants, the chemical energy (heat of combustion) of fossil fuels (coal, gas or oil) is first used for converting water into high pressure steam. This is then used to run a turbine to produce electricity. We know that a galvanic cell directly converts chemical energy into electricity and is highly efficient. It is now possible to make such cells in which reactants are fed continuously to the electrodes and products are removed continuously from the electrolyte compartment. Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen, methane, methanol, etc. directly into electrical energy are called fuel cells. One of the most successful fuel cells uses the reaction of hydrogen with oxygen to form water (Fig. 3.12).

The cell was used for providing electrical power in the Apollo space programme. The water vapours produced during the reaction were condensed and added to the drinking water supply for the astronauts. In the cell, hydrogen and oxygen are bubbled through porous carbon electrodes into concentrated aqueous sodium hydroxide solution. Catalysts like finely divided platinum or palladium metal are incorporated into the electrodes for increasing the rate of electrode reactions. The electrode reactions are given below: Cathode: O2 (g) + 2H2O(l) + 4e- 4OH(aq) Anode: 2H2(g) + 4OH(aq) 4H2O(l) + 4e Overall reaction being: 2H2 (g) + O2 (g) 2H2O(l). The cell runs continuously as long as the reactants are supplied. Fuel cells produce electricity with an efficiency of about 70 % compared to thermal plants whose efficiency is about 40%. There has been tremendous progress in the development of new electrode materials, better catalysts and electrolytes for increasing the efficiency of fuel cells. These have been used in automobiles on an experimental basis. Fuel cells are pollution free and in view of their future importance, a variety of fuel cells have been fabricated and tried.
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UNIT 3: ELECTROCHEMISTRY

CORROSION: The chemical attack on a metal by the constituents in the environment of

the metal is called corrosion. Eg: 1. Rusting of iron on exposure to moist air. 2. Formation of a green coating of basic copper carbonate (CaCO3.Ca(OH)2) on copper. 3. Tarnishing of silver. RUSTING: When iron is exposed to moist air for a long time, a brown coating of hydrated ferric oxide Fe2O3.3H2O is formed on the surface. This is called rusting. MECHANISM OF RUSTING: The impure iron surface behaves like a small electrochemical cell in the presence of water containing dissolved O2 or CO2. In these cells, pure iron acts as anode and impure surface acts as cathode. Moisture containing dissolved O 2 or CO2 acts as the electrolyte. At anode iron gets oxidised to Fe2+ ions. 2: + 2 ; At cathode moisture and oxygen of air are reduced to OH ions. 1 2 + 2 2 + 2 ; 2 ; The Fe2+ ions formed are further oxidised to Fe3+ ions by atmospheric oxygen. It forms hydrated iron oxide Fe2O3.xH2O which is called rust. PREVENTION OF CORROSION: o PAINTING: Coating the metal surface with paints and enamels. o Coating the metal surface with a thin film of oil or grease. o GALVANISING: Coating the metal with other metals like zinc. o CHEMICAL PROTECTION: Coating the metal surface with the chemical like Ferric Phosphate.

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UNIT 3: ELECTROCHEMISTRY

Exercises:
3.1 Arrange the following metals in the order in which they displace each other from the solution of their salts. Al, Cu, Fe, Mg and Zn. 3.2 Given the standard electrode potentials, K+/K = 2.93V, Ag+/Ag = 0.80V, Hg2+/Hg = 0.79V Mg2+/Mg = 2.37 V, Cr3+/Cr = 0.74V Arrange these metals in their increasing order of reducing power. 3.3 Depict the galvanic cell in which the reaction Zn(s) + 2Ag+(aq) Zn2+(aq) + 2Ag(s) takes place. Further show: (i) Which of the electrode is negatively charged? (ii) The carriers of the current in the cell. (iii) Individual reaction at each electrode. 3.4 Calculate the standard cell potentials of galvanic cell in which the following reactions take place: (i) 2Cr(s) + 3Cd2+(aq) 2Cr3+(aq) + 3Cd (ii) Fe2+(aq) + Ag+(aq) Fe3+(aq) + Ag(s) Calculate the rG and equilibrium constant of the reactions. 3.5 Write the Nernst equation and emf of the following cells at 298 K: (i) Mg(s)|Mg2+(0.001M)||Cu2+(0.0001 M)|Cu(s) (ii) Fe(s)|Fe2+(0.001M)||H+(1M)|H2 (g) (1bar)| Pt(s) (iii) Sn(s)|Sn2+(0.050 M)||H+(0.020 M)|H2 (g) (1 bar)|Pt(s) (iv) Pt(s)|Br2 (l)|Br(0.010 M)||H+(0.030 M)| H2 (g) (1 bar)|Pt(s). 3.6 In the button cells widely used in watches and other devices the following reaction takes place: Zn(s) + Ag2O(s) + H2O(l) Zn2+(aq) + 2Ag(s) + 2OH(aq) Determine rGo and Eo for the reaction. 3.7 Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their variation with concentration. 3.8 The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm1. Calculate its molar conductivity. 3.9 The resistance of a conductivity cell containing 0.001M KCl solution at 298 K is 1500 . What is the cell constant if conductivity of 0.001M KCl solution at 298 K is 0.146 x103 S cm1. 3.10 The conductivity of sodium chloride at 298 K has been determined at different concentrations and the results are given below: Concentration/M 0.001 0.010 0.020 0.050 0.100 102 x /S m1 1.237 11.85 23.15 55.53 106.74
Calculate m for all concentrations and draw a plot between m and
5
1 2

. Find the value of om.

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3.11 Conductivity of 0.00241 M acetic acid is 7.896 x 10 S cm . Calculate its molar conductivity and if om for acetic acid is 390.5 S cm2 mol1, what is its dissociation constant? 3.12 How much charge is required for the following reductions: (i) 1 mol of Al3+ to Al. (ii) 1 mol of Cu2+ to Cu. (iii) 1 mol of MnO4 to Mn2+. 3.13 How much electricity in terms of Faraday is required to produce (i) 20.0 g of Ca from molten CaCl2. (ii) 40.0 g of Al from molten Al2O3. 3.14 How much electricity is required in coulomb for the oxidation of (i) 1 mol of H2O to O2. (ii) 1 mol of FeO to Fe2O3. 3.15 A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5 amperes for 20 minutes. What mass of Ni is deposited at the cathode? 3.16 Three electrolytic cells A, B, C containing solutions of ZnSO4, AgNO3 and CuSO4, respectively are connected in series. A steady current of 1.5 amperes was passed through them until 1.45 g of silver deposited at the cathode of cell B. How long did the current flow? What mass of copper and zinc were deposited? 3.17 Using the standard electrode potentials given in Table 3.1, predict if the reaction between the following is feasible: (i) Fe3+(aq) and I(aq) (ii) Ag+(aq) and Cu(s) (iii) Fe3+(aq) and Br(aq) (iv) Ag(s) and Fe3+(aq) (v) Br2 (aq) and Fe2+ (aq). 3.18 Predict the products of electrolysis in each of the following: (i) An aqueous solution of AgNO3 with silver electrodes. (ii) An aqueous solution of AgNO3with platinum electrodes. (iii) A dilute solution of H2SO4 with platinum electrodes. (iv) An aqueous solution of CuCl2 with platinum electrodes.
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