SOLVED EXAMPLES ae Example 1.4 conductivity cell contains two electrodes of area of cross-section 1.25 em?. , *y are 10.5 cm. apart. If the cell is filled with an electrolyte and offers a resistance of 1996 ohm, calculate the cell constant and specific conductivity. Sol Gell constant = + = 2°22 adem a 1.25 i Observ ivity =< ohm served conductivity 1996 ohm". Specific conductivity = Cell constant x observed conductivity. Sine = 8.4% T9096 ~ *** 1996 = 42x 10% ohmt cmt. Example Specific conductivity of an x KCl solution at 25°C is 0.0002765 mhos env}. If the resistance of cell containing this solution is 500 ohms, what is the cell constant? ; l 1 zewuae Sol. Cellconstant=— and R=p > pee oh pond vw 1B 1 pees oka k = ape P = _ 500 x 00002765 em a = 0.138 cm. aENGINEERING CHENic, 20 ante Specific cond: ofa conductivity cell containing 0.2 (N) KCl is 2.767 , 10° ohm" cm, the observed resistance of the cell is 4364 ohm. eae the cell eee. the cell is filled with another solution the observed resistance is 3050 ohm. Calculate resistance of the solution. Sol. Cell constant = 12.075 cm = 252.58 ohm. cm. conductivity cell containing 0.02 N KCI solution offers a resistance of 250 ohm at a definite temperature. The specifie conductivity of0,02.N solution at that temperature §50.002768 ohm~ cmt. Ifthe cell is now filled with 0.2 N ZnSO, the observed resistance of the cell is 72.18 ohm. Calculate the equivalent and molar conductivities of the ZnSO, solution. Sol. Cell constant = R x K = 550 x 0.002768 = 1.5224 cm Again, K-= cell constant x observed conductivity 1 z frees = 1.5224 x 7218 = 0.02109 ohm em 1000 +. {equivalent conductivity) = K, x “S~ 1000 = 0.02109 x 02 = 105.45 ohm em? Pe 100K _ 100% 2,{molar conductivity) = p= = = 210.9 ohm cm?, ; Example 5The resistance of a decinormal solution of a salt occupying a volume between two Pt electrodes 1.80 em apart and 5.4 em? in area was found to be 32 ohms. Calculate the equivalent conductance (2.,) of the solution. Peis 1 ae fel ee oe etnies 5A K = 0.010416 ohm-tem? 1000K _ 1000 x 0.010416 sgn OL = 104.166 ohm- cm. ansonductance of 1,9 onductance rf 028 x 10°? (N) acetic acid is 48.15 oh equivalent ¢ equivalent ¢, t infinite dit i Ofaces dig finite dilution is 390.6 ohm a dissociation Sevens Sol. epee 48a 2 de J Bong = 0-1233. i ‘xample 7, i ae PI The equivalent conductances at in, LHC! = 496 finite dilution of various electrolytes are +1 1 AcONa = 91.01, NaCl = 126.5. Calculate (AcOH). Sol. 4 HC] +2, AcONa —2,_Nacl = Oye +e) + Oye + Rope) — Ohyigs Hey) = hip + hog. = h AcOH 426.1 + 91,0- 126.5 =2, AcOH = 390.6 Ohm-1cm?. ae el Equivalent conductance of acetic acid at 25°C is 0.0018 ohm!m? eq. If ou nd stance of H ions and CH,COO- ions at infinite dilution are 0.0348 ohm! m? eq? .004 ohm meq, respectively. Calculate the degree of dissolution of acetic acid. Sol. _2.(CH,COOH) = 2,,H* + 4,,CH,COO- Avie CH a ound oy nw = 0.0348 + 0.004 ohm-!m? eq = 0.0388 Sua of is & Degree of dissolution = Example 9/1 f 3g of acetic acid is added to enough water to make one litre solution, what will be the concentration of acetate ion. Calculate the percentage ionisation of acetic acid. (K,, = 1.8 x 10°). 3 Sol. Strength of CH,COOH solution = oo & equiv. [1 = 0.05(N) CH,COOH == CH,COO- + H* Initially _ = 0.05 0 0 Degree of ionisation = o At equilibrium = .05(1-a) 05a 05a (CH;COO-}[H*] _ 0.05ax0.05a _ (0.05)*a? K,=TCH,COOH] ~ 0.05(1-) 0.05 [a being negligible, 1— a= 1] = 0.0502 = ez [Ba - [:8x10% _ [18x10 _ 189x108 0.05 V 0.05 0.05 = 01898.Q. 12. What do you mean by resistance? Ans. Resi i sistance (R) of any conductor is the obstruction offered to the flow of current. Re ai where J=length, a=areaof cross-section of the conductor l or ape P a where, p = proportionality constant and is known as specific resistance or resistivity. R.a i 5 P =~]; unit of R = ohms. Q. 18. What do you mean by specific resistance or resistivity? Ans. Specific resistance or resistivity is the resistance offered by the conductor of 1 cm length and 1 cm? area of cross-section. Thus it is resistance offered by a conductor of 1 cm. From, Bl are p=R; where a = 1cm?,/=1cm. unit of p = ohm-cm. Q,A4. What is conductance? s. The conductance (C) is the reciprocal of R li R Unit of conductance = ohm™ or mho It is a measure of ease with which current flows through a conductor.ENGINEERING CHEMIsTry" 226 ii ctance? What is specific conducts Me ae ‘The specific conductance (K) is the reciprocal ale) p Ria It is defined as the conductance of 1 em* a a anaes unit of K = ohm em= : ee ccnr RAC What do you mean by equivalent conductivity of an electrolytic sol i i electrolyte Ans. It is the conducting power of all the ions present in a solution of an containing 1 g equiv. pecific resistance (p). 1000K c C= normality of the solution. Unit of A, = ohm™! cm? equiv, Q. 17, What do you mean by molar conductivity of an electrolyte? Ans. It is the conductivity of all the ions produced in a solution containing one gm mole 1000K M Equivalent conductivity 2, = of the electrolyte. ie, molar conductivity 2, = where, M = molarity of the solution K = specific conductance. 7QAB. Give the relationshi, Ans. The relation is ip of molar conductivity with concentration. Nps = Age? = bE where, 6 =constant concentration ‘olar conductivity at infinite dilution 0 Ag = Ap” at is the effect of dilution on molar conductivity? Ans, Molar conductivity increases with dilution, Q@dwnat do you mean by degree of dissociation of an electrolyte? sans, The degree of dissociation (a) is the fraction of the electrolyte that dissociates into fons. For weak electrolytes itis related to 2,, and 2," as follows: dm a=, as Q. 2k What is transport number? Ans. It is the fraction of total quantity of electricity, Define Kohlrausch’s law. Ans. The molar conductance, at infinite dil ionic conductances of cations and anions. carried by cations or anions. lution of an electrolyte, is equal to the sum of Q. at are the applications of conductance measurement? Ans. (i) Measurement of degree of dissociation, (@) Determination of solubility and solubility product, (iii) Conductometric titration.ie ee WHICH 1 X25. In alll co; pe and not resistance ve vol ene tt S volume of titre—explain, t conductance vs. volume of titre Ans. Equi ivi ‘ the eBay a eer Conductivity of a weak electrolyte depends on the number of ions of nt in solution with dilution of a weak electrolyte, degree of dissociation increases, so is the number of i is i ' ions. That is wl i ivi aoe eae ‘hy equivalent conductivity of weak electrolyte ‘7. Why equivalent conductivity at infinite dilution cannot be directly determined experimentally? Ans. Kohlrausch pointed out that at high dilution the equivalent conductivity () is plotted against the square root of concentration (c) gives a straight line which meets the zero axis of concentration at”, the equivalent conductance at infinite dilution,i.e., athigh dilution 27, and c are related by the equation. nean-Kve So, 4” can be determined by extrapolation of the curve} vs. ve (Fig. 9.13) for strong electrolytes to zero concentration. However 2 are not so related in case for weak electrolytes. So 4" for weak electrolytes cannot be experimentally determined by the above equation. 3g Equivalent conductivity-A-ohm™ cm? eq A 8 e~ (C in equivalentiiter) Fig. 9.13 Extrapolation of X versus lc.ae 1a ectrochemical Cell (h! emical cell is a device which co 2 able lctrlytes. When these electro, moren de at which oxidation occurs j h Lae curs is called ieee called the cathode. Oxidation and Ret diet contact with eachother, They areca ne the help of a typical example of a g ahekers one of which contains 1.0 M sol \n teactions occur in ate called half cells, Let us disc Nanic cell, the Daniel cell (Fig lution of ZnSO, and the other Separate contai nanes which an electrochemical Fig, 148). Ie consists of z Pet cs 0, A zinc rod is dipped in the ZnSO, sol Contains 1.0 M sol cuse : Solution and copper rod is di igo satin. TRese metalic rods are known as electrodes, The metal rods (eee rodes) are connected Snanmeter By means of an insulated wire through a key. The solutions no sin th Maple bya silt bridge which is an inverted U~ «ube containing some ele {h0,or NH,NO,, These electrolytes do not undergo chemical changes dri sing ofthe U tube is plugged with some porous material such s.soonas the circuit is closed by inserting a key, current starts flowing—this is shown by deflect intheammeter. Electric current flows due to the passage of electrons from zinc to the if oad Thefllowing reactions occur. sae Aranode Zn > Zn®* + 2 € (Oxidation) Atcathode Cu + 2e° > Cu (Reduction) Je two beakers are lyte such as KCI, inges during the process, The as glass wool ot cotton, Inthe external circuit, there is a flow of electrons from the zinc rod to the copper rod. Therefore, theeurent flows from copper to zinc. It may be noted that as a convention, the flow of electric aarentis taken opposite to the flow of electrons. As the electrons move from the zinc rod to the capper rod, the zinc rod is regarded as the negative terminal, whereas the copper rod is regarded as the pit terminal, The flow of the electrons occurs from the negative terminal (anode) to the pnitve terminal (cathode). Thus in an electrochemical cell, Oridation occurs at the anode (~ ve terminal) Reduction occurs at the cathode (+ ve termina!) Bkstrons low from the anode to the cathode Te i yte and wher {Wo contai can ectrodes in contact with electrolyte and w fainers containing electro “The half cell where oxidation Mision reac i a If cells. i rs i Sion hal ail Zn in ae 7 E50) and the half ell where edueson 258 lito half el (Cu in contact with CHS? fe the oxidation and occurs is called the is called ———— 8gan ns pbeatons ion 160 © Engineering hem => Wlecrons Bow Sale bridge Cotton plugs IM ZnSO, (aq) IM CuSO, (ag) —t galvanic cell (Daniel ell gala aaa Ss Functions of sat bridge s the circuit and prevents 2 eceennins deal nearly othe t0 half cell solutions In a Daniel cl, Zn undo sniation to Zr, The elecons released by it are accepted by Cu" of CuSO, in th one Peal ad heater seduced 10 Cu: The Zions pas into the solution, hence teeing ae nlaton of Zn fons inthe solution around the anode. Tn the reduction half el sceeps electrons and changes to Ci hence there isan accumulation of $0, ions around ie Cu (reduction) J Tn such a case, a net positive charge will develop on the electrode with respect to the ay) solution resulting in charge separation. The electrode becomes positive with respect to the solution (Fig. 14.9(a)) The Cu atoms on the electrode may lose electrons to the electrode and undergo oxidation to become Cu’ ions which go into the solution. Once again, there is separation of charges and the electrode becomes negative with respect to the solution (Fig. 14.9(b)). Gu) > Cu* +2 € (Oxidation) Electrode ‘Ducto the separation of charges between the electrode and the solution, an electric potential ‘spberween the metal and its solution. The electrical potential difference set up between the metal ‘nd its solution is called the electrode potential. It can be of two types. Osidation potential It is the tendency of an electrode to lose electrons and get oxidized. ‘oxidation potential is a measure of the tendency of an electrode to lose electrons. Za = Zn’ (aq) + 20° Cu Cu (ag) + 26°, vane peeetrpscations Bal semis ee : seg 0 Engng PO ayeofthe tendency of an electrode 0 an elec, jeisa One ang tm eduction poweti reduced. Gi) ae ue Cu? ions m¢ ving fron ns metal to sol ~ op wes a ition lee Jesving ind free electrons 9 8 from CH Coe ions on Cy behind ners ne Cu? ions in solution (CuSO, solution) ) sitvewith respect to the solution (Reduction) becomes Post with respect to the solution (Oxidation) . Electrode | vidasion potential is the reverse of reduction potential For camp, £ Zn is -0.76 volts, then its oxidation potential is +0.76 volts. Ifthe arate ac rmaf he ions is 1.0 M, the emperature is 25°C and for cell reaction where ne atmosphere, then the electrode potential is called the sandud are involved, the pressure is o1 c , clectrode potential denoted by the symbol E°. The reduction potential under the above-mentioned conditions is called the standard reduction potential. ‘The electrode potential depends upon + Nature of metal and its ions Concentration of the ions in the solution and Ie may be noted that the 0? if the reduction potential o © Temperature According to the present convention, the half cell potentials are always represented as reduction potentials. EMF or cell potential of a cell A cesrothemicl cl obtained by coupling two half cells or electrodes. The eee iene Thee tection potentials. Therefor, their tendency 0 ace ete electrons, and behaves ree value of reduction potential has a greater tendency (0 8 potent thereby fag td It acquires electrons from the electrode with lower rive decode porate bene 2 eter oxidation and behave as an anode. This dies two electrodes constituting an electrochemical cell is known the electromotive forc n rce (EMF) ra es coed cell potential and is the driving force for the cell reacto® . herefore, the EMF or cell si reduced. Is expressed volts, tent: jon ential atises from the difference in the tendency of the ™°Electrochemistry © 163 3 Reduction potential of cathode — 2 E canoe Reducy UCtion potential of anode Ba" Eases ~ to note that a cell reaction will be f on b betas ct : asible only if the value of the E_.. is positive. If Je jue comes out f0 be negative, the cell reaction is not possible and the electrodes will have to ihe valu in order to bring about the cell reaction, cll porential or EMF of a cell can be measured with the help of a potentiometer. The14.10 Electrochemical Series The arrangement of elements in t he order of increasing reduction potential value electrochemical series. It is also called the activity series. The electrochemical series of some typical electrodes with their electrode potentials is tab Table 14.3. Table 14.3 Standard reduction electrode potential at 25°C Electrode Electrode reaction (reduction) ae ne Li aq)+ > Li | -3.05 K K aq) +e > K(s) = Ba Ba’ (aq) +2e° > Ba(s) ae Ca Cat (aq) #26 Calg ee Na Na‘(aq) 4° > Naw ae Mg Mg(aq)+2e Mg) Al AP*(aq) + 3e > Al(s) Zn Zn* (aq) #2e° > ZaHecrochomisry © 165 eso = Cerlag) E> Cr (6) Fe" (ag) #26 Fels) CaP*(aq)+ 2e > Cals) Colaghi2e > Cols) [2HGa9) 2 > H@) [e+ 26 2a) Fe"(aq) 36 FEC Agadie> Ag) Br) 2e > 2Br aq) 5 Gg) #26 2CF faq) ‘Au (aq)+3e > Au(s) MnO {aq)+8H,O'aq).5e5 Man FQ) #2e > 2F- (aq) Applications of the electrochemical series Relative strength of the oxidizing and reducing agents Tie electrochemical seieshelps in predicting he oxidizing and reducing ability ofa substance Bee teeticiical series, the clements are arrange inthe onder of fae increasing telition potential hence, the cements sivaed atthe bottom of the sere have greater Hendeney to get reduced —they are good oxidizing agent, On the other and, claves’ atthe Poof the table have low reduction porential and have a leser tendency of| getting reduced. Consequently, they may get oxidized and are good reducing agents Galeulation of EMF of the cell EMF of the cell isthe difference ofthe reduction Potential of the cathode and the anode E, TA a ee ® Predicting spontaneity or feasibility ofa reaction Fora call reaction to be spontaneous, the EMF of the cell as calculated above should be TEE cis negative, then the cell rection will not be feasible, i Whether a metal will react with acids to give H, gas autals whose reduction potential is es than the reduction potential of hydrogen eg 888. Such metals are placed above hydrogen in the electrochemical series, Ec ccion oven ls Apter tendicy vl cccpe ceceoce a >oda) lll, a 56. © Engineering Chem a (Monovalent) Haq) + © 7 noe in the electroch ; Metals placed below bye oly. a Earn Seties have a highes potential than hydrogen: AI do not erate eg with acids. ee toe gt, Replacementtendency THEME TOs 00 of the clectochemicl gg ‘ to eplcetheoneblow toms SS. Thisisbecusethe mea yt hn, ial and hence a greater tendency to acces tet the by ty a greater reduction potent 4 Bene erro potential FC 224 Zin teas folloyg, Pon, ~~ : % E 0.34 volts and E%,!an~ ~0-76 volts * ‘The reduction potential of copper is greater than Zn; hence Cy? ions tendency to accept electrons. have, Ived examples Calculate the standard EMF of a cell containing Sn / Sn and Br, / Br electrodes, 1.08 V] (E* (Sn*/Sn) = -0.14 V, E’ (Br/Bs Solution Ba 5 Etat) -E {aode) ~ Reduction potential of E%,,_i8 higher, itis cathodic E = 1.08 - (0.14) = 1.22 =E ‘Br Le Esq Predict whether the reaction 2Ag(s) + Zn? (aq) > 2Ag" (aq) + Zn) is feasible or not Solution From the electrochemical series, the reduction potential of Ag and Zn are as follows E seing = 0.80 V EP, 2125 = -0-763 According to the question, Zn? is getting reduced, hence itis behaving 3s acathode- Bete coiy BP (anode) = (0.763) ~ (0.8) = 1.563 y Since Ey negative, the above egg isnot feasible or spontaneousee ee Se Practice problems olution of IM CuSO, be sored in a vessel made of Lickel 2-0.25V and Elyncy =034V “Imeab Siven 1. Canas Eo oN Calculate E%,, when the following half cell reactions are combi, 2+ po ined () Ferre > Fe’ EB =40.77y Ny (ii) MnO, + 8H" +5e > Mn+ 4,0 E°= 41.49 y 3. Calculate the standard reduction potential of Ag* /Ag electrode whe, n cell Cu (9) /Cu?* (1M) // Ag’ (1M)/ Ag is 0.46 V. Given that Cu: TAns py the cel} Potentig 4 1Cus aeALTT i 14.11 Nernst Equation Seed persica lofanieleczode depends upon the concentration and the temperature. When the concentration of an electrolye scion temperature is 298 K, then the electrode potential is termed as the sundae end Nernst equation gives the relationship berween the lectrode potenti snd fn peeled eluricur Gonsidera general cell reaction: of the electrolyte Solu in and t le potenti centration M* (aq) + ne = M(s) For a reversible reaction, the free energy change (AG) and its equilibrium constant (K) ate ad by the Van't Hoff reaction isotherm as [Product] [Reactant] AG = RT InK + RT In.AG? + RT In {Product} Electrochemistry © 169 [Reactant] spe standard five energy change (;, re ois » the chan 36 tants and products are unity), Ris the gas a "Be in free energy wh tet ile) produced 3 the expen san and Tit hen the concentration of pga=-rFE and AG =p oes peer inemamber oF ls0s Heed one de wlomb) . © Fs Faraday’s constant (1 = 96500 m peeteerrode potential and Eis the standard ccd Bi sing these valves nF, (1), we hae bah os pep AF {Produc nF ~ [Reactant] O3RT Product] po 23037 |, (Product) ”F [Reactant] @ Equation (2) is called the Nernst equation and gives the dependence of electrode potential on the ‘oncentration of the electrolyte, Ac T= 298 K , F= 96500, R = 8.314 JK, Eq. (2) reduces to _ 2.303 8.314298 (Product 7x 96500 8 [Reactant] pg tout B [Reactant] For the cell reaction Me" (aq) + ne“ = Ms) The equation becomes hog nm P[M™ aq) For pure solids, (M (s)] = 1, and the equation becomes >0.0591 il E=E°- oe n PIM" (aq) 0. =E°+ 2) logiM™* (aq)] For a cell reaction, aA +bB— cC+dD The Nernst equation can be written as _2:303RT | [C} [Dy a 0 Or age carey Itis evident from the Nernst equation that the electrode potential decreases with rise in tenpem=ite the Ne! fon 3 q. ss a equation and calculate the EMF of th, sas) Me” (0-001M) 17 Cu (0.0001M) / Cut badge col Wuls) : og OVS Eegeny =-237V Solution The reactions involved are ‘Atanode Mg(s) > Mg® (aq) +2€ ‘Atcathode Cu*(aq) + 2e > Culs) Net cell reaction Mg(s) + Cu*(aq) > Mg* (aq) + Culs) 0.0591, [Mg” (aa)] Ey =E°4-— pees a Ea, B(Cun aa) Ea oe Ecsipode a E ynode 934 (2:37) = 271V Substituting the values, 0.0591, 9-001 fos ee lop— 1, Bees) n 1089 0001 Ey = 2.71-0.0295 = 2.6805 VMultiple choice questions dis 4. On dilution specific conductance of an electrolyte (a) Increases WS Decreases (c) First increases then decreases (d) Neither increases nor decreases The unit of equivalent conductance is (a) Mho (b) Ohm * cm"! (c) Ohm™ cm equiv“! & Ohm * cm? equiy ~ Cell constant is defined as (a) Ratio of distance between electrodes and their area of cross—section (b) Ratio of specific conductance to the observed conductance (Both (a) and (b) (d) None of the above Which of the following statement is incorrect about an electrochemical cell? (a) Oxidation occurs at the anode and reduction occurs at the cathode. (b) Chemical energy converts into electrical energyCall can work indefinitely (@ Sale bridge maintains the eg, The EMF e electrochemic al cel WE a= * ates @ Given qe = Zn pele = Fe ‘The cell reaction is In+Fe* = Zn**+ Fe ‘The standard potential ofthe above cell will be ie @) ~1a9y For the electrode reaction ean 20N M* (aq) + ne M6) The Nernst equation is — RT 1 E=E+— log [—_ 2 @ mie fl O) Ene EL iy fp Ru a) p° , RT ee gy [M] GRRE in [ae] The relation between E” , and AG? is @) AG? = nFE?, OAc" =-nFE", Hie specific conductance ofa solution of concentration ¢ gram equiv erlige then fis equivalent conductance is 1000 x by XXE & 2 ©) T00 1000 es .. © ro0xx EMF of an electrolyte concentration cell i given by 2.303 AT @ E (b) E= oF YS ,. n 0.0591, We 0, tog (@) B= og The cll reaction will be spontancous if its EMF is GP Positive (b) Negative (ga (d) Fixed19. 20. ois i fo The specific conductance of a solution is 0.3568 ohm'cm. When placed in 4 conductance js 0.0268 ohm". The cell constant is Lhe (@) 1331cn" 13.31 cm? (6) 0.665 cm" (d) 6.65 cm ABis According to Kohlrausch’s law, the limiting value of molar conductivity of an lech @ An +45 ()) ees 205 +22 die 0 M+sh