CHAPTER 2: ELECTROCHEMISTRY BASIC CONCEPTS AND FORMULAE KEY POINTS Oxidation is defined as a loss of electrons while reduction is defined as a gain of electrons. In a redox reaction, both oxidation and reduction reaction take place simultaneously The device which converts chemical energy into electrical energy is known as an electrochemical cell. In an electrochemical cell: a. The half-cell in which oxidation takes place is known as oxidation half-cell b. The half-cell in which reduction takes place is known as reduction half-cell. c. Oxidation takes place at anode which is negatively charged and reduction takes place at cathode which is positively charged. (In electrochemical cell) d. Transfer of electrons takes place from anode to cathode while electric current flows in the opposite direction. e. An electrode is made by dipping the metal plate into the electrolytic solution of its soluble salt. f. A salt bridge is a U-shaped tube containing an inert electrolyte in agar-agar and gelatine A salt bridge maintains electrical neutrality and allows the flow of electric current by completing the electrical circuit. When the concentration of all the species involved in a half cell is unity, then the electrode potential is known as standard electrode potential. It is denoted as E°. Oxidation potential is the tendency of an electrode to lose electrons or get oxidized. 61Reduction potential is the tendency of an electrode to gain electrons or get reduced. The electrode having a higher reduction potential has a higher tendency to gain electrons. So, it acts as a cathode. The electrode having a lower reduction potential acts as an anode and vice versa |. According to convention, the Standard Hydrogen Electrode is taken as a reference electrode and it is assigned a zero potential at all temperatures. - In the electrochemical series, various elements are arranged as per their standard reduction potential values. . The potential difference between the two electrodes of a galvanic cell is called cell potential and is measured in Volts. The cell potential is the difference between the reduction potential of cathode and anode. E con = E cathode — E anode . Cell potential is called the electromotive force of the cell (EMF) when no current is drawn through the cell. |. Nernst formulated a relationship between standard electrode potential E° and electrode potential E. ns EEO ne, , 0.059 1 Egy = E° gah? a 108 Ty |. Electrode potential increases with increase in the concentration of the electrolyte and decrease in temperature. . Nernst equation when applied to a cell: aAk+bB—cC+dD erp Busy = Ey — 2209F2 yp, [cl] “ nF (a}"[B) 6220. al. 22, 23. 24, . Relationship between equilibrium constant Kc and standard cell potential EX = 2500RT ————logkK, 159 ——log K, a logK, . Work done by an electrochemical cell is equal to the decrease in Gibbs energy AG°= - NFE% cen, ). Every conducting material offers some obstruction to the flow of electricity which is called resistance. It is denoted by R and is measured in ohm. (Q) The resistance of any object is directly proportional to its length 1 and inversely proportional to its area of cross section A. R=pxl/A p is called specific resistance or resistivity. Its SI unit is ohm metre. The inverse of resistance is known as conductance, G=1/R=A/pxl Unit of conductance is ohm’ or mho, It is also expressed in Siemens denoted by S. The inverse of resistivity is known as conductivity. It is represented by the symbol x. The SI unit of conductivity is Sm', But it is also expressed in Scm! tet So, conductivity = Conductance x Cell constant A conductivity cell consists of two Pt electrodes coated with Platinum black. They have area of cross section A and are separated by a distance 1. Resistance of such a column of solution is given by the equation: R=p VA=1/KxVA W/A is called cell constant and is denoted by the symbol G* Molar conductivity of a solution is defined as the conducting power of the ions produced by dissolving 1 mole of an electrolyte in solution. Unit of Molar conductivity is Sem? mol" Kohlrausch's Law of independent migration of ions: According to this law, molar conductivity of an electrolyte, at infinite dilution, can be expressed as the sum of individual contributions from its individual ions. If the limiting molar conductivity of 6325. 26. 27. 28. the cation is denoted by 2°, and that of the anions by 4°. _ ,then the limiting molar conductivity of electrolyte is: Am =Vho et VIE. Where v, and v- are the number of cations and anions per formula of electrolyte. Application of Kohlrausch law *To calculate 4,” of a weak electrolyte *To determine the degree of dissociation of weak electrolyte *To determine the K, of weak electrolyte Degree of dissociation: It is ratio of molar conductivity at a specific concentration 'c' to the molar conductivity at infinite dilution, it is denoted by a Ka = Ca” where K, is acid dissociation constant, ‘c’ is concentration of 1-a electrolyte, a is degree of ionization. The nature of the product obtained at cathode or anode depends upon E® value of given chemical species. The chemical species which has higher E* will form product at cathode and The chemical species which has lower E? will form product at anode. Inert electrodes do not take part in chemical reactions Faraday’s First The amount of a substance deposited or liberated at an electrode is Law of directly proportional to the quantity of electricity passed through the electrolysis electrolyte. Faraday’s When the same quantity of electricity is passed through solutions of Second Law different electrolytes, the weight of different substances deposited electrolysis or liberated at the respective electrodes are proportional to their chemical equivalent weights. Product of Electrolysis Cathode : Na(s) Anode : Cl, NaCl (molten) 6429. 30. 31. Cathode: He(g) NaCl (ai ad Anode : Cl2(g) Cathode : Hz H2SO, (dil) Anode: O2(g) Cathode : Hz (H,SO,conc) Anode: H2S,03 Peroxydisulphuric acid AgNOs(aq)-Ag Cathode : Ag(s) electrodes Anode: Ag’ (aq) AgNOs(aq)- Pt Cathode : Ag(s) electrodes Anode: O,(g) CuCle(aq)- Pt Cathode : Cu(s) electrodes Anode: O2(g) Differences between electrochemical reaction and electrolysis. Electrochemical reaction Electrolysis. Chemical reaction produce electricity Electrical energy is used to carry out chemical reaction. It is spontaneous, AG is -ve It is non-spontaneous, AG is +ve Functions of Salt Bridge 1. Salt Bridge maintains electrical neutrality in solutions. 2. It completes circuit internally * Applications of electrochemical series i) To compare the relative oxidizing and reducing powers- A chemical species with higher value of E° will be stronger oxidizing agent and a chemical species with more - ve E® will be stronger reducing agent ii) To compare the relative activities of metals-A metal with more —ve E°value will be more reactive iii) To calculate the E°,q of given cell- 65Ecc E cathode” E° anode or E%cae E*mns- E*uns NOTE: E” for SHE is taken 0 (Zero) iv) To predict whether a metal will displace hydrogen from its compound or not- All the chemical species which have —ve E® value will displace hydrogen from its compounds M —M"' + ne" (electron lost is gained by H" ion to undergo reduction and H; is formed) 32, Molar Conductivity- It the conductance due to all the ion produced from 1 mole of an electrolyte in Vem’ of the solution, It is represented by Mn at conc. *C’ and 2”, at infinite dilution. A «for strong electrolyte increases constantly on dilution. + can i be calculated on extrapolating the curve. & se ‘A wm for weak electrolyte steeply (sharply) on dilution. X”nc i. be calculated on extrapolation of the curve. It is determine: ‘imei using Kohlrausch’s law. 33, Advantages of fuel cell---long lasting, more efficient, eco friendly, give useful by products Commercial cells- These are of 4 types 1) Dry cell (primary cell) — It is a Non rechargeable cell. Used in Torch, Wall clock etc. The following reaction takes place at Anode and Cathode it the Dry cell: 66TEI Anode: Zn{s) —> Zn™ + 2e" The above reaction takes place at anode i.e. Zn plate 7 Cathode: MnO,+ NH,'+ ¢—> MnO(OH) + NH, The above reaction takes place at cathode i.e. Carbon rod 34. Mercury cell/Button Cell — It is used in hearing aids and watches etc. The cell gives constant voltage through out its life because there is no ions involved in the overall reaction. ‘Anode “Anode cap ashet Cellcan Separator Cathode The following reaction takes place at Anode and Catho¢c the Mercury cell/Button Cell : Anode: Zn(Hg + 207 —> ZnOJs) + H,0 + 26° The above reaction takes place at anode i.e. Zn containe | Cathode: HgO+H,O+2e—> Hgi)+ 20H The above reaction takes place at cathode i.e. Carbon rc 35. Lead storage battery — It is a Rechargeable battery. Used in automobiles and inverters, 36. Rechargeable batteries used Phy (ce) ‘cathode doch plates ‘Le, evra cel reaction consisting of cette and anode reactions 8: ba The asia saa ania an PbO, hat On chang te bars the react 5 reversed and PDSO 9 acid in house hold appliances etc. ‘The cell eaclons when he bllery Is tn use ae gen el Anode: PS + $0,"an) PSO) +26 Cathode: FLO,() +50;"ag) + 4a # 2° FOS0, (6) # 24,00) cit | axe and cle comet ita Pan Po, pect. Fuel cell; This cell is based on the combustion of fuels like Hydrogen by oxygen: Advantages of Fuel Cells : 1. It can be controlled by the supply Hydrogen & oxygen gas 2.It causes no pollution 673. Ils efficiency is 70% 4, Its by product (Water) is also useful. The following reaction takes place at Anode ates ° yoatese and Cathode in the fuel cell. — Cathode: 0,(@) + 2H,O(l) + 4e—> 40H (aq) 4 —+o, Anode: 2H, (@ + 40H(aq) — 4H,0f) + 4e" ‘Overall reaction being: 2H{g) + O,(g) — 2 1,01) 37.Corrosion- In this process metal surface reacts with atmospheric oxygen in presence of moisture to form a layer of oxide. It is an electrochemical reaction. The following reaction takes place during rusting : Oxidation: Fe (s)> Fe** (aq) +2c 2 Reduction: ©, (g) + 4H"(aq) +4e" + 211,0() | Anodic Reaction Cathodic Reaction Atomospherte 1: 2Fe™" 0, Ox oxidation: 2Fe™ (aq) + 21,00) + HOY) + Fe,Oy) + 41M aq) > IMPORTANT FORMULAE S| Formula What to calculateEXcen = E°catnode— Eanote Cell potential of a cell can be calculated by this equation 2 [Ec =E’ cn 222 log _ | Half Cell potential of a half-cell can be Ps . calculated by this expression Mat At T=298K 3 | Een=E%ean- © log | Cell potential of a cell can be calculated te by this expression (R] At T=298K 4 En = lop ke To calculate cell potential from K, and At roe vice versa 5 To calculate cell potential from free AG? = = nFE® ein energy change and vice versa 6. |R= pt Resistance of a metallic conductor that obeys ohm’s Law. 7. |G =RK Cell constant with respect to resistance and conductivity. 8. x1000 Molar conductivity of an electrolyte at " infinite dilution. 9. <2 (01) hq” = £4 | Conductivity as dimensions ofa conductor 10)W=ZxIxt Amount of a substance produced at any Z = E/96500 electrode 1 | Wa _ we Amount of a substance produced at an a8 electrode of different cells connected in aseries 12) Bou og Z| To calculate cell potential from pH and 69vice-versa 13 |a=A,/A" To calculate the degree of dissociation of weak electrolyte 14 | Ka=ca’/ (1-0) To calculate the dissociation constant of conductivity. a weak electrolyte from the ratio of molar conductivity and limiting molar MULTIPLE CHOICE QUESTIONS(MCQ) Qn QUESTION ANSWER 1 The limiting molar conductivity for NaCI, KBr and KCI are 126,152 and150 Scm*mol", the limiting molar Conductivity of NaBr is: a)278 Scm’mol™ b)176 Scm’mol! c) 128 Scm’mol" d) 302 Scm’mol"! Ans-c Limiting molar conductivity of NH,OH is equal to -: a)A°NH,CI +A°yNaCl + A°gNaQH b)A°,NaOH + A°, NaCl - A°,NH,CI ©)A°,NaOH -A°,.NH,Cl - A°,HCI d)A° NH,CI +A° NaOH - A°,NaCl Ans-d 70Which cell will measure standard electrode potential of copper electrode? {i) Pt (8) | H2 (g, 0.1 bar) | H’ (aq. 1M) [| Cu”*(aq..1M) | Cu (ii) Pt(s) | H2 @, 1 bar) | H* (aq. , 1 M) || Cu’* (aq., 2 M)|Cu (iii) Pt(s)| H2 (g, 1 bar) | H* (aq. , 1 M) || Cu’* (aq. M)|Cu (iv) PU(s) | H2 (g, 1 bar) | H* (aq.,0.1 M) || Cu* (aq. M)|Cu Ans-c How is electrical conductance of a conductor related with length and area of cross-section of the conductor )G=hak! ii) G=k. La] ii)G = kal iv) G=k. La Ans-c The potential of a hydrogen electrode at pH = 10 is a.0.591 V b. 0.00V c, - 0.591 V d. -0.059 V Ans-c The standard oxidation potentials (E°) for Zn and Fe are as: Zn — Zn2* + 20°; E° = +0.76 V Fe — Fe2+ + 2e-; E* = +0.44 V The standard cell potential for the cell reaction Ans-c naFe2+ + Zn > Zn2+ + Fe is -- a) 40.32 V b) +1.2V ©) 0.32 V d)-12V Resistance of a conductivity cell filled with a solution of an electrolyte of concentration 0.1 M is 100 Q. The conductivity of this solution is 1.29Sm-1, Resistance of the same cell when filled with 0.2 M of the same solution is 5202. The molar conductivity of 0.02 M solution of the electrolyte will be: a) 124 x 104 S m2 mol! b) 1.24 x 10-4 S m2 mol"! ©) 1240 x 10-4 S m2 mot! ) 12,4 x 10-4 § m2 mol! Ans-a The standard reduction potentials at 25°C of Li’ |Li, Ba’+|Ba, Nat|Na and Mg’*|Mg are -3.05, -2.73, -2.71 and - 2.37 V respectively. Which is strongest reducing agent? a)Mg b) Na ) Li d) Ba Ans-c The standard EMF of a cell involving one electron change is found to be 0.591 V al 25°C. The equilibriumconstant of the reaction is: Ans-a Ra) 10" b) 10° 10 4) 10” 10. | The factors which influence the conductance of solution: Ans-c a)solute-solvent interaction _b) solute-solute interaction c) all of these d) temperature 11.) The ionic mobility of alkali metal ions in aqueous solution is | AnS-d maximum for: a Kt b) Lit ©) Nat @) Rot 12. | Which of the following is/are the same for aZn-Cu Daniel | Ans-a cell and a dry cell? a) Oxidation half reaction _b) Both the electrodes ©) Overall cell reaction 4) Reduction half reaction 13.) During the electrolysis of molten sodium chloride, the time | 4% required to produce 0.10 mol of chlorine gas using a current of 3 ampere is: a)220 minuteb) 110 minute _c) 330 minute d) 55 minute 14, Ans-d The term infinite dilution refers when: a)a = 1, for weak electrolytes b) an electrolyte is 100% dissociated ¢) all inter-ionic effects disappears d) all of these ASSERTION AND REASONING TYPE QUESTIONS 7BNote: In the following questions a statement of assertion followed by a statementof reason is given. Choose the correct answer out of the following choices. a) Both assertion and reason are true and the reason is the correct explanation ofassertion. b) Both assertion and reason are true and the reason is not the correct explanation ofassertion. ¢) Assertion is true but the reason is false. d) Assertion is false but reason is true. QUESTION ANSWER 1, Assertion: Cu is less reactive than hydrogen. . Ans-a Reason : E cu2s/cu is positive 2. Assertion: E° cell should have a positive value for the cell to ‘Ans-c function. Reason : Ecathode < Eanode 3. Assertion: Conductivity of all electrolytes decreases on dilution. ‘Ans-a Reason : On dilution number of ions per unit volume decreases 4. Assertion: Am for weak electrolytes shows a Ans-a Sharp increase when the electrolyticsolution is diluted Reason : For weak electrolytes degree of dissociation increases with dilution of solution 745. Assertion: Mercury cell does not give a steady potential. Reason : In the cell reaction, ions are not involved Ans-d 6. Assertion: Electrolysis of NaCl aqueous solution gives chlorine at anode instead of O,. Reason : Formation of oxygen at anode requires overvoltage Ans-a 7. Assertion: For measuring resistance of an ionic solution an AC source is used. Reason : Concentration of ionic solution will change if DC source is used Ans-a 8.Assertion : Current stops flowing when Ec, = 0. Reason : Equilibrium of the cell reaction is attained. Ans-a 9.Assertior ‘Ageing, increases with increase in concentration of Ag” ions. Reason : Ejgsay has a positive value. Ans-d 10.Assertion : Copper sulphate can not be stored in zinc vessel. Reason : Zinc is less reactive than copper Ans-c 11.Assertion: Cu dissolves in HNO, Reason: In nitric acid it is oxidised by nitrate ion and not by hydrogen ion Ans-a 12. Assertion: Metals like platinum or gold are used as inert electrodes. Reason: They do not participate in the reaction but provide their surface for reactions and for the conduction of electrons. Ans-a IMPORTANT TWO MARK QUESTIONS QI. What is the effect of temperature on the electrical conduction of i) Metallic conductor. ii) Electrolytic conductor? Ans, With increase of temperature the electrical conduction of metals decreases whereas that of electrolytic conduction increases.Q2. What is the reference electrode in determining the standard electrode potential? Ans. Normal hydrogen electrode (NHE). Q3. What are the units of specific conductance? Ans: ohm" cm" or Sem". Q4What is the effect of the decreasing concentration on the molar conductivity of a weak electrolyte? Ans. Molar conductance of a weak electrolyte increase with decrease of theconcentration. QS. Arrange the following metals in order of their increasing reducing power. K*/K = - 2.93V, Ag’/Ag = 0.80V, Hg”*/Hg = 0.79 V, Mg”*/Mg = - 2.37 V Cr/Cr = -0.74V. Ans.Lower the reduction potential, easily if gets oxidized hence greater is the reducing power, therefore the increasing order of reducing power is Ag Zn?*(aq)+Cu(s) n=2 .T=298K Even = E caitode ~ E anode = 1.1V 10-4 10-2 =1.10 -[0.02955 x log 10°] =1.10 + (2 x0.02955) =1.10V+0.0591V—=1.1591V Q11What happens when a piece of copper is added to Eyen = 1.1 V- 0,0295 log (aan aqueous solution of FeSO, (b)an aqueous solution of FeCl,? Ans a. Nothing will happen when the piece of copper is added to FeSO, Because reduction potential E°c,”*cy (0.34v) is more than the reduction potential EXraure is 0.44 V b. Copper will dissolve in an aqueous solution of FeCl,because reduction ° potential E 5.*-2* 0.77 V is more than the reduction potential of E%u?*7cu ( 0.34V) Cu(s)+2FeCl, (aq) ——> Cu +2 FeCl, THREE MARK QUESTIONS 7Q1.For the standard cell Cu(s)/Cu* (aq) || Ag* (aq) /Ag(s) E° cy2"cw = 40.34 V E. aging +080 V i, Identify the cathode and the anode as the current is drawn from the cell. ii. Write the reaction taking place at the electrodes. iil. Calculate the standard cell potential. Ans:i. From the cell representation Ag/Ag* ¢lectrode is cathode and Cw/Cu* electrode is anode . ii. At anode : Cu(s) — Cu2*(aq)+2e At Cathode Ag+ ke Ag Over all reaction is Cu(s)+ Ag’ (aq) > Cu2*(aq)+2 Ag(s) BO y=E athodeE anode HED pesagE” cxescu =4.80 V - (+0.34V) =+0,80V-0.34V =0.46V Q2.Can we store copper sulphate in (i) Zinc vessel (ii) Silver vessel? Give reasons, Given E 6,2%cu= 40.34V, E9z,2% 295 -0.76V, E°agting= +0-80V Ans:(i)_A metal having lower reduction potential can displace a metal having higher reduction potential from solution of its salt. .Since standard reduction potential of Zinc (E°Zn?*/Zn=-0.76V) is less than the standard reduction potential of Copper (E°Cu2*/Cu=+0.34V), Zn can displace copper from 78copper sulphate solution. Thus, CuSQ,solution cannot be stored in zinc vessel. (if) Standard reduction potential of silver , ie. ECAg*t/Ag=+0.80 V is more than the Standard reduction potential of copper E” (cu2*/cu =+034V), silver cannot displace copper from copper sulphate solution. Hence copper sulphate can be stored in silver vessel. Q3.How many grams of chlorine can be produced by the electrolysis of molten NaC] with a current of 1.02 A for 15 min? Ans: 2NaCl q———* 2Na* @ +2Cl" 2Cl —— Ch @ +2e° 2mole Imol Q=nF Q=2 x 96500 C/mol= 1.93 x 10°C Quantity of electricity used = It =1.02 A X (15 x 60) sec =900C Molar mass of Cl, = 2 X 35.5 = 71 gmol'X10°C Mass of Chlorine produced by 1.93X 10°C of charge = 71gm Mass of Chlorine produced by 900C of charge = (71 x 900)/(1.93X104S ) =0.331 gm Q4.Determine the values of equilibrium constant (Ke) and AG° for the following reaction: Ni(s) + 2Ag+ (aq) Ni** (aq) + 2Ag (3), E°=1.05V (IF = 96500 C mol-1) Answer: According to the formula 9AG? = -nFE® = — 2 x 96500 x1.05 or AG? = -202650 J mol" = -202.65 KJ mol" Now AG? = -202650 J Molt R = 8.314 J/MoVK, T = 298 K log K = —4S2_ 2303 RT or log K = =202650 = 5202650_ _ a5, los K = S7os.e1ea1 ~ 955? K = Antilog of 35.52. +. K = 0.35 x 107 Q5.The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S cm’ mol’, Calculate the conductivity of this solution. Answer: C=1.5M, Aq = 138.9 S cm? mol! Am = Kx1000/¢ 2K = AgxC/1000=138.9x1.5/1000 = 0.20835 S em" Q6.Write the reactions taking place at cathode and anode in lead storage battery when the battery is in use. What happens on charging the battery? Answer: At Anode: Pb + SO,* — PbSO, + 2e- At Cathode : PhO, + SO,? + 4H’ + 2e + PbSO, + 2H20 On charging the battery, the reaction is reversed and PbSO, on anode and cathode is converted into Pb and PbO; respectively. Q7. The standard electrode potential for Daniel cell is 1.1 V. Calculate the standard Gibbs energy for the cell reaction. (F = 96,500 C mol-1) 80Answer: Given : E? = 1.1V, F = 96,500 C mol-5, n = 2 Zn + Cu = Cut Zn Using AG® = -nFE® = -2 x 96500 x 1.1 = 212,300 CV mol * Q8.From the given cells: Lead storage cell, Mercury cell, Fuel cell and Dry cell Answer the following: (i) Which cell is used in hearing aids? (ii) Which cell was used in Apollo Space Programme? (iii) Which cell is used in automobiles and inverters? Answer: (i) Mercury cell is used in hearing aids. (ii) Fuel cell was used in the Apollo Space Programme. (iii) Lead storage cell is used in automobiles and inverters. Q9.Calculate the degree of dissociation (a) of acetic acid if its molar conductivity (Am) is 39.05 S em2 mol. Given: 2°(H+) = 349.6 S cm2 mol-I and 2.°(CH3COO-) = 40.9 S cm’ mol" Answer: A®m(HAC) = 2°H" + 2°AC™ = )°CH3COOH = d°H+ + 4°CHyCOO- = 349.6 S cm2 mol-1 + 40.9 S cm2 mol-1 = 390.5 S cm2 mol-1 81Q10.Write the name of the cell which is generally used in transistors. Write the reactions taking place at the anode and the cathode of this cell. Answer: Leclanche cells (Dry cell) is used in transistors. Reaction at Anode: Zn(s) > Zn + 2e- At Cathode: MnO, + NH, * + e- > MnO(OH) + NH FIVE MARKS QUESTIONS, Ql.a)Explain the electrochemical theory of rusting of iron . Ans: The water layer present on the surface of iron (especially in the rainy season) dissolves acidic oxides of air like CO2 ,SO2 etc. tofrom acids which dissociate to give H+ ions: H20 + CO2—H2CO3 = 2H*+ + CO," In the presence of H* ions iron starts losing electrons at some spot to form ferrous ions, i.e. its oxidation takes place. Hence, thisspot acts as the anode: Fe(s) + Fe2+(aq) + 2e The electrons this released through the metal to reach another spot where H* ions and the dissolved oxygen takes up theseelectrons and reduction reaction takes place. Hence, this spot acts as the cathode: O2(g) + 4H*(aq) + de” + 2H20() The overall reaction is : 822Fe(s) + O2(g) + 4H* (aq) > 2Fe2*(aq) + 2H20()) Ferrous ions are further oxidized by the atmospheric oxygen to ferric ions which combine with water molecules to form hydrated ferric oxide, Fe203.xH20 which is rust b)A strip of nickel metal is placed in a 1-molar solution of Ni (NO3)2 and a strip of silver metal is placed in a 1-molar solution of AgNO3. An electrochemical cell is created when the two solutions are connected by a salt bridge and the two strips are connected by wires to a voltmeter. Write the balanced equations for the overall reaction occurring in the cell and calculate the cell potential. Ans Reactions involved for the electrochemical cells are Atanode: Ni(s) + N#* (1M) +267 At Cathode: Agt(1M) + 26~ —» 2Ag(s) Net cell reaction: Ni(s) + 2Agt (aq) > N#*+ (aq) +2Ap(9) Q2. a) The following curve is obtained when molar conductivity, Aj» is plotted against the square root of concentration, C1/2 along y and x-axis respectively for the two electrolytes X and Y. 83Y = CH;COOH X= KCI i) ‘What can you say about the nature of these two electrolytes? ii) | How do you account for the increase in A ,, for the electrolytes X and Y with dilution? iii) How can you determine A” for these electrolytes? Ans.i. Electrolyte X is a strong electrolyte and Y is a weak electrolyte. ii. Molar conductivity,A, of X (strong electrolysis) increases slowly with dilution. This is because interionic forces of attraction decreases on dilution, although the number of ions remain the same. As a result ions move freely and hence A,, increases with dilution. On the other hand, for Y (weak electrolyte) Am increases sharply with dilution. This is because degree of dissociation increases on dilution resulting in greater number of ions on dilution. Hence A,, increases iii, For X electrolyte A” can be obtained by extrapolation to zero concentration CASE -BASED QUESTIONS : Q1.Read the text carefully and answer the questions: A Lead storage battery is the most important type of secondary cell having a lead anode and a grid of lead packed with PbO2 as a cathode. A 38% solution of sulphuric acid is used as the electrolyte (Density = 1.294 gmL71), The battery holds 3.5 L of the acid. During the discharge of the battery, the density of H2SO4 falls to 1.139 g mL-1. (20% H2SOq by mass) 84a)Write the reaction taking place at the cathode when the battery is in use. ‘Ans:Reaction taking place at cathode when the battery is in use: PbO,(s) + (aq) + 4H*(aq) + 2e- — PbSO,(s) + 2H20()) b) Lead storage battery is considered a secondary cell. Why? Ansilt can be recharged after use. c)What is the Molarity of sulphuric acid before discharge? Ans:Molarity = 38 x1.294 x1000/ 98X100 = 5.02M. (or) ©)Write the products of electrolysis when dilute sulphuric acid is electrolyzed using Platinum electrodes. Ans:At anode: Oz (g) At cathode: Hz (g) Q2.Read the text carefully and answer the questions: Conductors allow the passage of electric current through them. Metallic and electrolytic are the two types of conductors. Current carriers in metallic and electrolytic conductors are free electrons and free ions respectively.Specific conductance or conductivity of the electrolyte solution is given by the relation: K= cx I/A where c = 1/R is the conductance and I/A is the cell constant. Molar conductance of strongelectrolyte depends on concentration: A n= A%q ~ Ne Am = molar conductance at infinite dilution ,c= concentration of the solution ,b = constant The degrees of dissociation of weak electrolytes are calculated as: a=Am/Am” a)Out of specific conductance and molar conductance, which one of the following decreases on dilution ofelectrolyte solution? asAns. Specific conductance decreases on dilution of electrolyte solution. b) What is the correct order of equivalent conductance at infinite dilution for LiCl, NaCl and KCI? Ans. The correct order of equivalent conductance at infinite dilution is KCI > NaCl > LiCl. c) Out of BaCl, and KCI for which electrolyte solutions A,, and A, are equal? Ans. In KCl electrolyte solution 4" and ?.° are equal (or) c) What is equal to the cell constant of the conductivity cell when the conductance of a solution of anelectrolyte is equal to that of its specific conductance? Ans. The conductance of a solution of an electrolyte is equal to that of its specific conductance. The cell constant of the conductivity cell is equal to the unity. Q3.Read the text carefully and answer the questions: The driving force AG diminishes to zero on the way to equilibrium, just as in any other spontaneous process.Both AG and the corresponding cell potential (AE = AG/nF) are zero when the redox reaction comes to equilibrium. The Nernst equation for the redox process of the cell may be given as: E= E -0,0591/nlogioQ The key to the relationship is the standard cell potential E° ..1 derived from the standard free energy change as: AE? = - AG? / nF At equilibrium, the Nernst equation is given as: E= F - 0.0591 /nlogioK a)When does the equilibrium constant Ke will be equal to Q? 86Ans. When E = O; then K.= Q b) On the basis of information available for a reaction: 4/3 Al + O,—> 2/3 AlzO3 ; AG = -827 kJ/mol of O, What is the minimum EMF required to carry out electrolysis of Al,O,? Ans G = -nFE cy -827 kJ/mol = - 4 x96500 Cx E E cell =214V coll ©) Why is the equilibrium constant k related to only B?,.4, and not Ey, ? The equilibrium constant k related to only E°.«y and not E cell because at equilibrium, Ecen = 0. (or) ©) Calculate the EMF of the cell, containing Ni and Cu electrodes. Given E* (Ni**/Ni) =-0.25 Vand EB? (Cu*/Cu) =+ 0.34 V EMF of cell =E° cathode - E° anode =E* (Cu”/Cu) - B® (Ni “/Ni) = +0.34V - (0.25 V) =0.59V HOT: JESTI QL.A current of 5 ampere is flowing through a wire for 193 seconds. Calculate number of electrons flowing through cross section of wire for 193 seconds. Ans- Q=1x t= 5x193= 965C 96500C is equivalent to flow of 6.022x10" electrons + 965C will be equivalent to flow of electrons = 6.022x 10°*x 965/96500= 6.02210" electron. 87Q2. Calculate A? m NH,OH from the following values. ‘A° m for Ba(OH)2, BaCl;, NH,Cl are 257.6, 240.6, 129.8 Scm® mol" respectively. Ans- A° m (NH,OH) = A° NH," + A°OH" = (A° NH," + A°CI) + % (A°Ba"* + 2A°OH) = -1/2 (A°Ba’* + 2A°CI) = 129.8 + % x 457.6- % 240.6 = 238.3 Scm’ mol Q3.The EMF of following reaction is 0.28V at 25°C Zn + 2H" — Zn” + H; (1 atm) E°cell = 0.76 V Calculate pH of solution at hydrogen electrode. Ans- Been = E°ccn ~ 0.0591 /n x log [Zn”*]/ [H"]? = 0.76 - 0591/2 log [0.1}/ [H*]* 0. 28 = 0.76 - 02955 (-1+ 2pH) 2pH-1 =16.244 pH =8.62