SECTION-A (ELECTRO CHEMISTRY)

A brief review of the basic concepts

1. Electrochemistry: The branch of chemistry which deals with the study of the conversion of chemical energy into electrical energy or vice versa and their mutual relationship is called electrochemistry. 2. Oxid tio! !d red"ctio!: oxidation is the process in which an atom, molecule or ion loses one or more electrons. For example, H H+ + el l + e!+ "+ !Fe Fe + e #n$ % #n$% + e $xidation is always followed by an increase in the oxidation number of the substance undergoing oxidation. &eduction is the process in which an atom, molecule or ion gains one or more electrons. For example, H+ + e- H ' + !e '!!+ + u + e u $! + %e !$!&eduction is always followed by a decrease in the oxidation number of the substance undergoing reduction.

3. Oxid tio! !d red"ci!# #e!ts: an oxidi(ing agent is the substance which gains electrons while a reducing agent is the substance which loses electrons. For example, )n*s+ + !H+ *a,+ )n!+*a,+ + H!*g+ 4. Redox re ctio!$ oxid tio! !d red"ctio! h l% re ctio!s: the reaction which involves the simultaneous occurrence of both oxidation and reduction processes is called a redox reaction. The redox reaction can be spilt into two half e,uations, one corresponding to the oxidation process *called oxidation half reaction+ and the other corresponding to the reduction process *called reduction half reaction+. For example, the oxidation and reduction half reactions of the redox reaction are as follows.. )n*s+ + u!+*a,+ )n!+ *a,+ + u*s+ )n*s+ )n!+*a,+ + !e*oxidation half reaction+ !+ u *a,++ !e u * reduction half reaction+ 5. Si!#le electrode (h l% cell) !d si!#le electrode &ote!ti l: when a metal rod is dipped in its salt solution. -t develops a positive or negative potential. This assembly is .nown as a single electrode or half cell and the potential developed on it is called single electrode potential. $xidation electrode *oxidation half cell+ and oxidation potential/ when the electrolytic solution pressure of the metal is greater than the osmotic pressure of the solution the metal rod develops a negative potential due to the following oxidation process. # #n+ + e'uch an electrode is called an oxidation electrode or oxidation half cell and the potential developed on it is called oxidation potential. -t is represented as 0oxi or 0#1#n+ &eduction electrode *reduction half cell+ and reduction potential/ when the electrolytic solution pressure of the metal is less than the osmotic pressure of the solution, the metal rod develops a positive potential due to the following reduction process. #n+*a,+ + ne #*s+ 'uch an electrode is called a reduction electrode or reduction cell and the potential developed on it is called reduction potential. -t is represented as 0red or 0#n+1# 2ull electrode/ when the electrolytic solution pressure of the metal is e,ual to the osmotic pressure of the solution, neither oxidation nor reduction process ta.es place and no potential is developed on the metal rod . 'uch an electrode assemble is called a null electrode.

6. St !d rd electrode &ote!ti l(E'): the potential of an electrode assembly is said toe be the standard electrode potential when i+ The temperature of the electrode assembly is !45 ii+ The ion solution used in the assembly has a concentration of 3 mol 6-3 , and iii+ The pressure of the gas, if used in the assemble , is 3 atm, For a particular type of assembly, the standard oxidation potential * 0oxi or 0#1#n++ and the standard reduction potential *0red or 0#n+1#.+ are numerically e,ual but their signs are opposite. Thus, 0#1#n+7 - 0#n+1# For example, 05)n 1 )n+! 7 -05)n+! 1 )n and 05 u1 u+! 7 -05 u+! 1 u 8ccording to the -9:8 convention, the term standard potential refers to standard reduction potential. Thus, if no subscript is mentioned, 05 represents the standard reduction potential. 7. St !d rd hydro#e! electrode (SHE or NHE): standard hydrogen electrode is set up by passing pure hydrogen gas at 3 atm. :ressure in a solution of H+ *#ore correctly H"$++ ions of concentration 3 mol 6-3 in contact with a :latoni(ed platinum foil and can be represented as :t, H! *g+ *3 atm +1H+ *3 mol 6-3+ The half cell reactions are as follows 5 ; H *g+ H+*a,+ + e-< E 3
!
! 5 H+ *a,+ + e- ; H!*g+< E H + 1 3 H ! ! 5 5 =y convention, E 3 H ! 1 H + 7 E H + 1 3 H ! 7 5 ! !

H! 1 H +

*when the electrode wor.s as anode+ *when the electrode wor.s as cathode+

8. Me s"reme!t o% st !d rd electrode &ote!ti l: the standard electrode potential of an electrode assembly is measured by connecting it to a standard hydrogen electrode and measuring the potential difference. The measured value of potential difference is numerically e,ual to the standard electrode potential of the given electrode assembly because the potential of standard hydrogen electrode is (ero by convention. The sign of the electrode potential thus measured is ascertained by ascertaining the direction of the flow of current. The direction of flow of current is regarded opposite to the direction of flow of electrons. -n a galvanic cell, electrons flow from anode to the cathode. The potential difference between the anode and the cathode in a galvanic cell in the standard state is represented by 0 cell. This is given by 05 cell 7 05 cathode- 05 anode Thus identifying the anode and the cathode, in the galvanic cell constructed for the measurement of electrode potential, the sign of the electrode potential can be ascertained with the help of the above e,uations. For example let us consider the following two cases.

>hen a (inc electrode in the standard state is connected to a standard hydrogen electrode, the current flows from hydrogen electrode towards the (inc electrode and a potential difference of 5.?@ volts is obtained. $bviously, the electrons flow from (inc electrode to hydrogen electrode. Thus , in this case, (inc electrode acts as anode whereas the hydrogen electrode as the cathode, hence, E 5 + 3 E 5 Zn+! 1 Zn 05 7 05 - 05
cell cathode anode
H 1 H! !

5.?@

E 5 Zn+! 1 Zn 7 5 E 5 Zn+! 1 Zn 7 -5.?@ volts.

>hen a copper electrode in the standard state is connected to standard hydrogen, electrode, the current flows from the copper electrode towards the hydrogen electrode. $bviously electrons flow from hydrogen electrode to copper electrode. Therefore, in this case, hydrogen electrode acts as anode and the copper electrode as cathode. The measured potential difference is 5."% volts. Hence. 5."%volts = E 5Cu +! 1 Cu E 5 + 3 = E 5Cu +! 1Cu 5
H 1 H! !

E 5Cu +! 1 Cu = +5."%volts

"

9. Electrochemic l series: the electrochemical series is the arrangement of various electrode systems in the increasing order of their standard reduction potentials.. the electrochemical series consisting of some electrode systems along with their half cell reactions is give below. Electro chemic l series

Im&ort !t %e t"res o% electrochemic l series: the electrode systems having negative values of standard reduction potetentials act as anode when connected to a standard hydrogen electrode whiles those having positive values as cathode. The metal placed at the top *6i+ of the series has the minimum value of standard reduction potential i.e. it has the minimum tendency to get reduced or maximum tendency to get oxidi(ed. Therefore it is the strongest oxidi(ing agent and can reduce any other substance placed below it. -n fact, any substance can reduce any other substance placed below it in the series. The reducing power of the substances decreases in going down the series. The substance placed at the bottom of the series *F+ possesses the highest value of standard reduction potential i.e. it has the strongest tendency to get reduced. onse,uently, it acts as the strongest oxidi(ing agent. The oxidi(ing power of the substances decreases in going from bottom to the top of the series. Some im&ort !t co!cl"sio!s %rom the electrochemic l series: The reactivity of metals decreases on moving down the series. 8ny metal placed above hydrogen in the series can displace hydrogen from a dilute acid The electropositive character of metals decreases on moving down the series. 8 metal can displace any other metal placed below it in the series from its salt solution. The stability of the oxides of metals decreases on moving down the series. 8 redox reaction is feasible when the substance having higher reduction potential gets reduced and the one having lower reduction potential gets oxidi(ed.

i+ ii+ iii+ iv+ v+ vi+

10. ( l) !ic cells: a galvanic cell is a device in which chemical energy is concerted into electrical energy. 8 galvanic cell generates electric current on account of a redox reaction occurring in it. Aaniel cell, dry cell, 6eclanche cell etc, are the cell of this type. Co!str"ctio! o% # l) !ic cell: a galvanic cell can be constructed by uniting an oxidation electrode with a suitable reduction electrode. The solutions involved in the two electrodes can be made in communication with each other either by a direct contact through a porous diaphragm. $r through a salt bridge. -n outer circuit, the two electrodes are connected to a device which is capable of utili(ing the electrical energy produced. 8 salt bridge is a 9-shaped glass tube filled with the concentrated solution of an inert electrolyte such as B l, B2$", B!'$% etc. it completes the electrical circuit by allowing the ions to flow from one half cell to another half cell and maintains the electrical neutrality of the solutions present in the two half cells. -n a galvanic cell, the electrode at which oxidation process occurs is called the anode while the one at which the reduction process ta.es place is called the cathode. -t is to be moved that the anode is of negative polarity while the cathode is of positive polarity in a galvanic cell.

Re&rese!t tio! o% # l) !ic cell: a galvanic cell is always represented by waiting oxidation electrode *anode+ at the left and the reduction electrode *cathode+ at the right. Airect contact of the two solutions is represented by a vertical line *C+ while the contact of the two solutions through a salt bridge is shown by two parallel vertical lines *CC+. For example a Aaniel cell involving a salt bridge is represented as given below )nC)n!+* 3+CC u!+* !+C u 8node athode

The cell re ctio!: The 0#F of a galvanic cell is due to a redox reaction. -t can be obtained by adding oxidation and reduction reactions in such a way that electrons get cancelled. For example, the cell reaction of a Aaniel cell can be obtained as follows )n u!+ + )n!+ + !e!e u
-

*at anode+ * at cathode+ *over all reaction+

)n + u!+ )n!+ +

0.#.F.of a galvanic cell/ the electromotive force *0.#.F+ of a galvanic cell is defined as the difference of electrical potential which causes the flow of current from one electrode to another when virtually no current is drawn from the cell. 8ccording to the -.9.:.8. convention, the 0#F of a cell is given by 05 cell 7 05&ight 056eft >here 05& 7 standard reduction potential at the right had electrode *cathode+ and 0567 standard reduction potential at the left hand electrode *anode+. 11. *e&e!de!ce o% E+M+, o! co!ce!tr tio! !d tem&er t"re: the electrode potential of an electrode assembly depends upon i+ the nature of metal and its ions, ii+ the concentration of ions in the solution and iii+ temperature. Ner!st e-" tio! %or si!#le electrode: for an electrode involving the processes of reduction, 2ernst e,uation can be written as follows. RT DoxidisedstateE Ecell = 0 5 + log nF D reducedstaeE

>here 0cell7 reduction potential of the electrode assembly, 05 7 standard reduction potential of the same electrode assembly, &7 gas constant, n7 number of electrons involved in the electrode reduction, F7 3 Faraday *F@455 coulombs+ D$xidi(ed stateE7conc. $f the substance undergoing reduction, D&educed stateE7conc. $f the substance obtained on reduction. For the electrode reaction #n+*a,+ + ne- #*s+ The above e,uation can be written as RT D M n + * aq+E log 0#n+1# 7 05#n+1# + nF D M * s +E RT log logD M n + E 0#n+1# 7 05#n+1# + nF -f T7!FG B*!45 + the above e,uation can be written as 5.54F EMn + 1 M = E 5 Mn + 1 M + logD M n + E n For an oxidation electrode involving the process #*s+ #n+*a,+ + ne- , the 2ernst e,uation can be written as follows. @

EMn + 1 M = E 5 Mn + 1 M

5.54F logD M n + E n

2ernst e,uation for the 0.#.F of a cell/ for a galvanic cell involving the cell reaction a8 + b= c + dA, 2ernst e,uation can be written as follows. RT DC Ec D DEd log 0cell 7 05cell nF D AEa D BEb 8t T7 !FG B *!45 + , we have 5.54F DC Ec D DEd 0cell 7 05cell 7 log n D AEa D BEb DC Ec D DEd E-"ili.ri"m co!st !t %rom Ner!st e-" tio!: The term is e,ual to the D AEa D BEb concentration ,uotient *H+ of the cell reaction. Therefore, the above e,uation can be used to calculate the e,uilibrium constant of a redox reaction if the reaction is in e,uilibrium. >hen the cell reaction is in e,uilibrium, 0 cell7 5 hence, From the above e,uation we have !."5"RT log Bc 5 7 0o cell nF !."5"RT log Bc 05cell7 nF (i..s %ree e!er#y !d E+M+,+ o% cell: the 0.#.F. of a cell in the standard state is related to the standard free energy change as IJ5 7 - n F05 cell ,rom this e-" tio! %ollo/i!# co!cl"sio!s c ! .e o.t i!ed/ i+ >hen 0cell is positive , the cell reaction is feasible ii+ >hen 0cell is negative< the cell reaction is not feasible. iii+ >hen 0cell is (ero, the cell reaction is in e,uilibrium. 12. Co!d"ctors !d i!s"l tors: The substances which allow the passage of current through the n are called co!d"ctors+ 8ll metals, fused ionic compounds and the a,ueous solutions of ionic compounds are the substances of this type. The substances which do not allow the passage of the electric current through them are called i!s"l tors+ &ubber, glass, plastic, sulphur, dry wood etc. are the substances of this type. The conduction of current by a conductor is either due to the flow of electrons or due to the movement of ions. The metallic conduction decreases with increase in temperature whereas the electrolytic conduction increases with a rise in temperature. 13. Electrolytic co!d"ct !ce: the ease of flow of current through a conductor is called its electrical conductance or electrical conductivity. The ease of flow of current through an electrolytic solution is termed as electrolytic conductance. The conductance * + is defined as the reciprocal of the resistance * & + i.e. 3 C= R The unit of conductance is ohm-3, 3 ' 7ohm-3 S&eci%ic resist !ce: the resistance of a conductor is directly proportional to its length l and inversely proportional to its area of cross section 8 i.e. l R A l &7 A The constant is called the specific resistance or resistivitty of the conductor. -t may be defined as the resistance of the conductor having a length of 3 cm and area of cross section e,ual to 3 cm!. The units of specific resistance are ohm cm. S&eci%ic co!d"cti)ity (0): it is defined as the conductance of a conductor whose length is 3 cm and area of cross section e,ual to 3 cm!. -t is e,ual to the reciprocal of specific resistance *p+ of the solution. ?

3 For an electrolytic solution, specific conductivity is defined as the conductance of 3 cm" of the solution. The units of specific conductivity are ohm -3 cm-3

Mol r co!d"cti)ity m : molar conductivity of an electrolytic solution at dilution Km is the conductance of the solution containing 3 mole of the electrolyte dissolved in Km cm" of the solution. m is related to the specific conductivity . as m 7 . L Km >here Km is the volume of the solution containing one mole of the electrolyte The units of m are ohm -3cm! mol-3 For an electrolytic solution, m is related to eq as molarmass + X eq m 7 * equivalentmass 1 ri tio! o% eq !d m /ith dil"tio!: =oth eq and m of an electrolytic solution increase of a dilution and approach limiting values when dilution approaches to infinity. The limiting values are expressed as eq and m respectively, thus, eq m 7 7 e,uivalent conductivity at infinite dilution molar conductivity at infinite dilution.

14. 2ohlr "sch l /: The molar conductivity at infinite dilution of an electrolyte is e,ual to the sum of molar conductance sod its cations and anions, with each conductance term multiplied by the number of respective ion present in the formula unit of the electrolyte. m = H + + Cl Thus, for H l, For H" $$H, For =a l! m = H + + CH " COO m = Ba !+ + ! Cl

2ohlr "sch l / c ! lso .e st ted s %ollo/s+ The e,uivalent conductance of an electrolyte at infinite dilution is e,ual to the sum of the e,uivalent conductances of its cations and anions. Thus. m = cation + anion
e.g. for 2acl, m = Na + Cl

34.

Electrolytic cell: The cell which converts electrical energy into chemical energy is called an electrolytic cell. The process involved in the conversion of electrical energy into chemical energy is called electrolysis. 8n electrolytic cell consists of two metallic or graphite rods dipping in the solution of an electrolyte and connected to a battery. The rod connected to the positive terminal of the battery acts as anode while that connected to the negative terminal of the battery acts as cathode. -t is to be noted that the anode in an electrolytic cell is of positive polarity while the cathode is of negative polarity. Electrolysis: 0lectrolysis is the process which involves the conversion of electrical energy into chemical energy. 0lectrolysis may be defined as the process which leads to a chemical change on the passage of electricity through an electrolyte present either in the dissolved state or in the molten state. -n the process electric current is passed through an electrolyte ta.en in an electrolytic cell either in the form of an a,ueous solution or in the fused state. 9nder the influence of electric current, ions migrate towards the oppositely charged electrodes and get discharged at them. Thus, the electrolyte gets chemically decomposed into the species obtained at the two electrodes. For example, electrolysis of fused sodium chloride ta.es place as follows< 8t cathode/ 8t anode 2a l 2a+ + l+ 2a + e 2a l- - e- l l + l l! G * in the molten state+ *reduction+ *oxidation, primary change+ *secondary change+

35+

Thus, on account of electrolysis of fused sodium chloride, sodium is obtained at the cathode and chlorine gas at the anode. 36+ , r d y7s l /s o% electrolysis: #ichael Faraday *3G"!+ formulated following two laws which govern the process of electrolysis. ,irst l /: the amount a substance liberated at an electrode during electrolysis is directly proportional to the ,uantity of electricity which passes through the electrolytic solution. -f w grams of a substance get liberated on a particular electrode on passing a current of amperes for t seconds, we have > M -. t > 7 ). -.t >here, ) is a constant .nown as electrochemical e,uivalent of the substance. -t is given by Equivalentmass Equivalentmass = ) 7 F F@455 -t has been found that the ,uantity of electricity re,uired to liberate. 3 gram e,uivalent of a substance is F@455 coulombs. This ,uantity of electricity is called Faraday and is denoted by F. it is actually the charge carried by one mole of electrons. The ,uantity of electricity needed to deposit 3 mole of an ion 7 nF, where n is the charge on the ion. Seco!d l /: when the same ,uantity of electricity is passed thorough the solutions of different electrolytes connected in series the masses of the substances liberated at the electrodes are in the ration of their e,uivalent masses. -f w 3 and w! are respectively their e,uivalent masses, then according to this law, E 3 = 3 E! !

Criteri %or &rod"ct %orm tio! d"ri!# electrolysis: when electrolytic solution contains several types of ions, the nature of products formed on account of electrolysis of the solution can be predicted on the basis of the following criteria. The substance which possesses higher standard reduction potential is preferentially reduced at the cathode. -f the cation produced from the electrolyte in a,ueous solution has higher standard reduction potential than that of water, the cation gets reduced at the cathode and the corresponding product is obtained. >hen the standard reduction potential of the cation is less than that of water, water gets preferentially reduced at the cathode and H ! gas is liberated. This is why ions li.e 2a+, #g!+, a!+ etc. can not be reduced in a,ueous solutions as their reduction potential are much lower than that of water. The substance which possesses lower standard reduction potential is preferentially oxidi(ed at the anode.

-f the anion produced from the electrolyte in a,ueous solution has lower standard reduction potential then that of water, the anion will get oxidi(ed at the cathode and the corresponding product will be obtained at the anode. >hen the reduction potential of the anion - higher than that of water, water gets preferentially oxidi(ed and $! gas - liberated at the cathode. 38+ Some ex m&les o% electrolysis: some examples of the electrolysis of a,ueous solutions of some substances are given below Electrolysis o% co!c+ A-"eo"s sol"tio! o% N Cl: 'ince the standard reduction potential of 2a+ *2a+ + e- 2a< 05 7 -!.?3 K+ is less than that of water *!H !$*l+ + !e- H!*g+ + !$H-*a,+< 057 -5.G" K+, water gets preferentially reduced at the cathode in this case. 8t anode, l- ions get oxidi(ed in preference to water, although the former has a higher value of standard reduction potential. This is due to over voltage. Thus the electrolysis ta.es place as follows/ 8t anode/ ! l- l! + !e*$xidation+ N 8t cathode/ !H!$ + !e H! + !$H *&eduction+ F

Thus, during the electrolysis of a,ueous 2a l solution, chlorine gas is evolved at the anode and hydrogen gas at the cathode. 0lectrolysis of a,ueous copper sulphate solution using platinum electrodes/ in this case the electrolysis ta.es place as follows/ 8t anode< H!$ ; $! + !H+ +!e!+ 8t cathode< u + !e- u Thus, copper is obtained at the cathode and oxygen gas at the anode. Electrolysis o% -"eo"s co&&er s"l&h te sol"tio! "si!# co&&er electrodes: in this case copper gets deposited at the cathode and an e,uivalent amount of copper from the anode dissolves into the solution u!+ ions. This is because the reduction potential of copper is less than that fo 'o!-% ions and water. The electrolysis ta.es place as follows/ 8t anode/ u u!+ + !e8t cathode/ u!+ + !e- u Electrolysis o% dil"te -"eo"s H9SO:: in this case hydrogen gas is evolved at the cathode and oxygen gas at the anode as shown below. 8t anode H!$ ; $! + !H+ + !e8t cathode !H+ + !e- H! Electrolysis o% / ter: pure water is a very wea. electrolyte and does not conduct much current. However, electrolysis of water can easily be carried out if a few drops of sulfuric acid are added to it. 8ddition of sulphuric acid ma.es water conducting and the electrolysis ta.es place as follows/ 8t anode %$H- !H!$ + $! + %e+ 8t cathode !H + !e- H! Thus, oxygen gas is liberated at the anode and hydrogen gas at the cathode.

SECTION-;(ELECTRO CHEMISTRY)
3+ <rite the ! me o% Sol"tio!: =isphenol. chemic l s".st !ce /hich is "sed to &re)e!t the corrosio!+

9+

<h t is the "!it o% s&eci%ic co!d"ct !ce= Sol"tio!: $hm-3 cm-3 or ' cm-3 <h t is mol r co!d"cti)ity= <rite t/o "!it lso+ Sol"tio!: -t is conduction power of all the ions produced by one mole of an electrolyte in given solution. -ts unit is ohm-3 or ' cm! mol-3. <h t is cell co!st !t= Sol"tio!: l ell constant 7 a >here l is distance in cm between electrodes and a is cross-section area of electrodes. <hy lter! ti!# c"rre!t is "sed %or me s"ri!# electrolytic co!d"cti)ity= Sol"tio!: -n order to avoid electrolysis, alternating current is used At /h t co!ce!tr tio!$ the mol r co!d"ct !ce o% ! electrolyte &&ro ches t m xim"m limiti!# ) l"e= Sol"tio!: 8t infinite dilution * oncentration approaches to (ero+ *e%i!e de#ree o% dissoci tio! i! terms o% mol r co!d"ct !ce+ Sol"tio!: The fraction of total number of molecules dissociated is called degree of dissociation c 7 5m m <rite the % ctors %%ecti!# co!d"ct !ce o% electro!ic or met llic co!d"ctor+ Sol"tio!: i+ 2ature and structure of the metal ii+ The number of valence electrons per atom iii+ Aestiny of metal iv+ Temperature *conductance decreases with increase of temperature+. <hich & rticles c rry the ch r#e i! electrolytic co!d"ctio!= Sol"tio!: -n electrolytic conduction the charge is carried by the ions. <h t is the e%%ect o% tem&er t"re o! resist !ce o% electrolytic co!d"ctors= Sol"tio!: The resistance of electrolytic conductors generally decreases as temperature increases. *e%i!e s&eci%ic co!d"cti)ity+ Sol"tio!: 'pecific conductivity/ -t is the reciprocal of specific resistance. -t may be defined as the conductance of one centimeter cube of the conductor. 3 3 3 ! = X or! = l = 3cm, a = 3cm ! R a " 3 != R <hich met l h s Sol"tio!: )inc *)n+ #re ter te!de!cy %or oxid tio!$ @i!c or co&&er=

>+

:+

4+

5+

6+

8.

?+ 3'+

33+

39+

3>+

<hich electrode c ! .e "sed s re%ere!ce electrode= Sol"tio!: 'tandard hydrogen electrode or normal hydrogen electrode or calomel electrode. <h t is the %"!ctio! o% s lt .rid#e i! electrochemic l cell= Sol"tio!: i+ To complete the electric circuit. ii+ To maintain the electrical neutrality around the electrodes. *i%%ere!ti te .et/ee! met llic !d electrolytic co!d"ctor+ Sol"tio!: '.2o #etallic conductor 3 Flow of electric current ta.es place without the decomposition of material ! Flow of electricity is due to flow of electron 0lectrolytic onductor Flow of electric current cause decomposition of substance. Flow of electricity is due to flow of ions. l di%%ere!ce+ :otential difference -t is a difference in electrode potential of the two electrodes when the cell is sending current through the circuit. -t is less than the maximum voltage obtained from the cell.

3:+

34+

35+

*i%%ere!ti te .et/ee! e+m+% !d Aote!ti Sol"tio!: '.2o e.m.f 3 -t is the difference in potential of two electrodes when no current is flowing in an open circuit. ! -T is maximum voltage obtained from the cell.

36+

*i%%ere!ti te .et/ee! electrochemic l !d electrolytic cell+ Sol"tio!: '.2o 0lectrochemical cell 0lectrolytic cell 3 -t is device to concert chemical -t is a device to concert electrical energy energy into electrical energy. to chemical energy. ! onsists of two electrodes in =oth the electrodes are immersed in same different compartments Ooined by a solution. salt bridge. <h t ty&e o% re ctio! is res&o!si.le %or #e!er tio! o% electricity i! )olt ic or electrochemic l cell= Sol"tio!: &ed ox reaction. St te !d ex&l i! , r d y7s %irst l / o% electrolysis+ Sol"tio!: -t states that during electrolysis the amount of substance deposited at any electrode is proportional to amount of electric current passed H7- L t *e%i!e st !d rd electrode &ote!ti l+ Sol"tio!: >hen a metal rod is immersed in the molar solution of its own salt at 3 atm. :ressure !4 5 , the potential developed in .nown as its standard electrode potential. St te !d ex&l i! 2ohlr "sch l / o% i!de&e!de!t mi#r tio! o% io!s+ Sol"tio!: -t states that the molar conductivity of solution at infinite dilution id e,ual to sum of molar conductance as anions and the cations respectively. 5 + 5 5 #athematically, m = v + + v >here v+ and v- number of cations and anions per formula. 5 + 8nd 5 are molar conductivity of cation and anion at infinite dilution. <rite *e.ye-H"c0el-O!s #er e-" tio!+ <h t do di%%ere!t sym.ols si#!i%y= Sol"tio!: 5 m = 5 m A c , where m is the molar conductivity at concentration c, 5 m is the molar conductivity at infinite dilution and 8 is a constant. 3

38+

3?+

9'+

93+

99+

9>+

<hich &rod"cts /ill .e o.t i!ed .y electrolysis o% -"eo"s sol"tio! o% sodi"m chloride= S"&&ort yo"r !s/er i! terms o% electrode &ote!ti l+ Sol"tio!: -n a,ueous solution of sodium chloride electrolysed, l! and H! are produced at anode and cathode. 2a l *a,+ 2a + *a,+ + l-*a,+ At C thode: 2a+*a,++ e- 2a*s+, 05 7 -!.?3 K 3 H+*a,+ + e- H!*g+, 0575.55 K ! 8s the reaction with higher value of 05 is preferred, therefore the reaction at the cathode. 3 H+*a,+ + e- H!*g+ ! =ut H+*a,+ obtained due to dissociation of H!$ 3 H!$*l+ + e- H!*g+ + $H-*a,+ ! At !ode: $xidation occurs at anode, at anode the substance with lower oxidation potential will get oxidi(ed preferably. 3 O! + ! H + !e H !O *e+ E 5 = 3.!"# ! ! l+!e ! l-*a,+ 05 7 3."@ K 'ince the standard reduction potential of water is slightly less than of chlorine. Therefore it has a more chance of getting oxidi(ed. The net reaction may be represented as under 3 3 NaCl *aq + + H !O *l + Na + *aq + + OH *aq + + H ! * $ + + Cl! * $ + ! ! <rite i! det il .o"t the electrochemic l series+ Sol"tio!: i+ &elative case of oxidation or reduction is predicted/ 8 system with higher reduction potential has greater tendency to undergo reduction. 0xample/ the reduction potential of F!1F- system is highest, so F ions are easily oxidi(ed to F!. ii+ :lacement tendency/ Higher value of reduction potential shows the greater tendency to ac,uire the reduced form. Thus )n will displace u from the solution of the latter. iii+ :redicting spontaneity of red ox reaction/ the value of 0cell indicates that the reaction -s spontaneous. >hen 0cell is Pve, the reaction is not feasible. <h t re the %"el cells= Ex&l i! the /or0i!# o% H9-O9 %"el cell+ Sol"tio!:

9:+

94+

Fuel cells are galvanic cells which directly concerts the heat energy of fuel into electrical energy. -n the cell hydrogen and oxygen are bubbled through porous carbon electrodes into concentrated a,ueous 2a$H or B$H solution. The electrode reactions are/ 8t anode H!*g+ + !$H-*a,+ !H!$ + ! e8t athode $!*g+ + !H!$*l+ + %e- %$H-*a,+ NNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNN !H!*g+ + $!*g+ !H!$*l+ 3

95+

<h t is electrochemic l series= List its ) rio"s ch r c teristics+ Sol"tio!: The standard reduction, the arrangement of elements in order of increasing reduction potential values is called electrochemical series. haracteristics/ i+ -n electrochemical series 6i16i+ is at the top F!1F- is at bottom. -t shows that lithium has greater tendency to form 6i+ ii+ The tendency of an element to undergo reduction increase from top to bottom. iii+ Fluorine occupying the total position shows greater tendency to undergo reduction and is powerful oxidi(ing agent. iv+ 0lectrochemical series helps to predict the activity as metals. v+ Tendency to get reduced increases on moving downwards or the power of oxidi(ing agent increases on moving downwards in electrochemical series. <rite Ner!st e-" tio!+ Sol"tio!: The 2ernst e,uation for electrode reaction #n+ + ne- #*s+ !."5"RT DM E log 0 #n+1# 7 05 #n+1# nF DM n+ E Here 0 #n+1# is standard electrode potential for molar solution of a metal ion #n+ at !FG B which is determined by using standard hydrogen electrode, & is gas constant. T is absolute temperature, n is number of moles of electrons, F is the FaradayQs number for chemical cell 5.54F DoxidationE Ecell = E 5 cell log n reduction (i)e .rie% cco"!t o% corrosio! !d its mech !ism+ Sol"tio!:

96+

98+

orrosion is an electrochemical phenomenon. -nitially the metal is oxidi(ed by way of loss of electrons. Further it is oxidi(ed to its oxide in the presence of water and air. #echanism/ $xidation occurs at, 8node/ Fe*s+ Fe!+ *a,+ + !e0lectrons released at anode move through the metal and go to another spot on the metal and reduce the oxygen in presence of H+ ions. athode/ $!*g+ %H+*a,+ + %e- !H!$*l+ Here Fe!+ ions move through water on surface of iron obOect. The overall reaction of the cell can be summari(ed as !Fe *s+ + $!*g+ %H+*a,+ +%e- !H!$*l+ %Fe!+*a,+ + $!*g+ + %H!$*l+ Fe!$"*s+ + G H+ H+ ions produced in above reaction help further in rusting. The Fe!+ ions are now oxidi(ed to Fe"+ ions, which form -ron *---+ oxide, *Fe!$".xH!$+. -f the water on the surface is saline or if impurities are present, the process of corrosion is ,uic.ened.

9?+

Ex&l i! the electrolysis o% s"l&h"ric cid+ Sol"tio!: Auring the electrolysis of H!'$% hydrogen gas in liberated at cathode 8t cathode H+*a,+ + e- ; H! *g+ =ut following two processes can ta.e place at the anode 8t anode !H!$*l+ $!*g+ + %H+*a,+ +%e- 0573.!" K !'$% !-*a,+ '!$s!-*a,+ + !e0573.F@ K For dilute sulphuric acid, reaction *i+ is preferred but at higher concentration of H!'$% process ii+ is preferred resulting in formation of solution of peroxodisulphuric acid *H!'!$G+ <h t re seco!d ry cells= (i)e the !ode or c thode re ctio! o% Nic0el C dmi"m stor #e cell= Sol"tio!:

>'+

'econdary cells are those cells which can be recharged by passing a direct current through them and can be used again as a source of electric current. 2ic.el- admium storage cell 8t anode d*s+ + !$H-*a,+ d*$H+!*s+ + !e-*$xidation+ 8t cathode 2i$!*s+ + !H!$*l+ + !eN 2i*$H+!*s+ + !$H- *&eduction+ $ver all d*s+ + 2i$!*s+ + !H!$*l+ d*$H+!*s+ + 2i*$H+! *s+ >3+ <hy mol r co!d"cti)ity %or CH>COOH c ! !ot .e determi!ed ex&erime!t lly= Sol"tio!: #olar conductivity of wea. electrolyte .eeps on increasing with dilution and does not become constant even at very large dilutions. <h t is the "se o% Al ti!"m %oil i! the hydro#e! electrode= Sol"tio!: -t is used for the inflow and out low of electrons. C" is co!d"cti!# s s"ch /hile C"SO: is co!d"cti!# o!ly i! molte! st te or is -"eo"s Sol"tio!+ <hy= Sol"tio!: u is conduction as such because it contains free electrons. u'$ % is conduction in molten state or in a,ueous solution because it gives ions in the molten state or a,ueous solution. O"t o% B! !d S! /hich o!e &rotects iro! .etter e)e! %ter cr c0s !d /hy= Sol"tio!: )n protects better because oxidation potential of )n is greater but that of tin is less than that of iron. <hich cell / s "sed i! &&ollo s& ce &ro#r mme= Sol"tio!: Hydrogen-oxygen fuel cell. 3

>9+

>>+

>:+

>4+

>5+

Ho/ is c thodic &rotectio! o% iro! di%%ere!t %rom its # l) !i@ tio!= Sol"tio!/ -n athodic protection, the iron is connected by a wire with amore active metal such as )n or 8l. onse,uently, the more active metal acts as anode and loss electrons in preference -ron. CO9 is l/ ys &rese!t i! ! t"r l / ter+ Ex&l i! its e%%ect o! r"sti!# o% iro!+ Sol"tio!: -n the presence of dissolved $! in H!$ the acidity of water adOacent to the iron obOect increase and its electrical conductivity also increases. The ions present, will favour the formation of more electrochemical cell and will thus promote rusting or corrosion. I% c"rre!t o% 4 A %lo/s %or >+''mi!"te$ the! /h t -" !tity o% ch r#e h s %lo/ed= Sol"tio!: harge 7 urrent L Time @5sec 4 AX *".55 min X + 7 3min = F55c harge on 3 mol of electrons is F@455 coulomb c% arg eincoulomb F@455Cmol 3 #ole electrons 7 F55C = F@455Cmol 3 7F."" L 35-" mole electrons. The resisti)ity o% '+'3 MAC ;- sol"tio!s is >''D cm !d co!d"cti)ity cell co!t i!i!# s"ch s sol"tio! / s %o"!d to h )e resist !ce o% :4' D+ <h t is the cell co!st !t= Sol"tio!: 3 &"eci'icconductvit( = &e sistivit( cell cons tan t = s"eci'icconductivit(Xresis tan ce 3&cm 3 X %45 "55 = 3.4cm 3 =

>6+

>8+

>?+

:'+

The mol r co!d"cti)ity o% '+34M or# !ic cid sol"tio! is 4+4 S cm9 mol-3+ /h t is the s&eci%ic co!d"cti)ity !d resisti)ity o% the sol"tio!= Sol"tio!: !X 3555 m = &cm ! mol 3 M XM != m 3555 4.4&cm ! mol 3 X 5.34M = = 5.555G!4&cm 3 3555 3 3 resistivit( * " + = = = 3!3.!o%mcm ! 5.555G!4&cn 3 C lc"l te mol r co!d"ct !ce t i!%i!ite dil"tio! %or cetic cid+ (i)e!: 5 m * HCl + = %!4 3cm ! mol 3 5 * NaCl + = 3GG 3cm ! mol 3 5 *CH"COONa + = F@ 3cm ! mol 3 Sol"tio!: 8ccording to BohlraushQs law 5 5 5 3 ! 3 a+ m * HCl + = H + + cl %!4 cm mol
5 5 5 3 ! 3 b+ * NaCl + = Na + + cl = 3GG cm mol 5 5 5 3 ! 3 c+ * HCl + + * CH "COONa + * NaCl + = F@ cm mol 0,*a+ +0, *c+ P0,*b+

:3+

7 :9+

m *CH "COOH + = * H + + + *CH "COO +

= %!4 + F@ 3GG = """cm ! mol 3

The co!d"cti)ity o% '+'3M eth !oic cid is '+3:4E33'-> S cm-3 !d the mol r co!d"cti)ity o% HC !d CH>COO- re >4' !d :3 S cm9 mol-3 res&ecti)ely+ C lc"l te he dissoci tio! co!st !t o% the cid+ Sol"tio!: 5 *CH "COOH + = H + CH "COO 7"45 ' cm! mol-3 + %3 ' cm! mol-3 7"F3 cm! mol-3 !X 3555 5.3%4 X 35" &cm 3 X 3555 m *CH "COOH + = = = 3%.4cm ! mol 3 M 5.53M Molarconductivit(o' 5.53MCH "COOH Aegree of dissociation 7 Molarconductivit(o'CH "COOHat inf initedilution 3%.4cm ! mol 3 = 5.5"? "F3cm ! mol 3 CH " COOH CH "COO + H + = C *3 + C C C XC = C ! Ba 7 C *3 + 75.53 # L *5.5"?+!73.%L35-4

:>+

A! electrochemic l cell is set-"& .et/ee! c dmi"m !d !ic0el Cd(s) F Cd9C (3M) FF Ni9C) (3M) F Ni(s) I% t/o h l%-cells /or0 "!der st !d rd co!ditio!s$ c lc"l te the cell &ote!ti l (em%)+ E' cd9CGCd H -'+:' 1$ E'Ni9CGNiH-'+941 Sol"tio!: d *s+ C d!+ *3#+ CC 2i!+ *3#+ C 2i*s+ 8ccording to the convention, the right had side electrode is cathode and the left hand side electrode is anode.

8node Half-reaction/ d*s+ d!+ *a,+ +!eathode Half reaction/ 2i!+*a,++!e- 2i*s+ The cell reaction is / d*s++2i!+*a,+ 2i*s+ + d!+*a,+ 05 cell705red*right+-05red*left+ 7 05*redcathode+-05red*8node+ 7052i!+12i-05 A!+1 d 05 cell7-5.!4 K-*-5.5%K+ 7 + 5.34 K ::+ C lc"l te the st !d rd cell &ote!ti l o% the electrochemic l cell i! /hich %ollo/i!# re ctio! occ"rs+A. C 9A#C I A.9C C 9A#(s) E'&.9CGA.H-'+3> 1 E'A#CGA#HC'+8'1 Sol"tio!: 8node half reaction/ :b :b!+ + !e+ athode half reaction/ !8g + !e !8g 8ccording to the convention, cathode is written on the right hand side. 05cell705*redcathode+-05red*8node+ 7 05 8g+18g-05 pb!+1:b 05cell7 +5.G5 K-*-5.3" K+ 7 5.F" K The E' ) l"es %or the t/o met l electrodes re #i)e! .elo/: i) Cr>CGCr9C H - '+: 1 ii) ,e>CG,e9C H C '+81 Comme!t o! the res"lt o% tre ti!# sol"tio! o% Cr (II) /ith sol"tio! co!t i!i!# ,e (III) io!s+ Sol"tio!: $n the basis of above value we can say the value of reduction electrode potential of r"+1 r!+ is -5.% K. it is less than reduction electrode potential of Fe"+1Fe!+ is +5.G K. in both cases r!+ will be oxidi(ed to r"+ and Fe"+ will be reduced to Fe!+ r!+ + Fe"+ r"+ + Fe!+ 3

:4+

Thus when Fe"+ ion is added to r!+ solution, Fe"+ will be reduced to Fe"+ and r!+ will be oxidi(ed to r"+ :5+ <h t is the h l% Jcell &ote!ti l %or A#CGA# electrode t 94'C i! /hich co!ce!tr tio! o% sil)er io!s is '+4M= Eo A#CGA#H C'+8' 1 Sol"tio!: 8g+*a,+ + e- 8g*s+ n73 D8g*s+E 7 3 !."5"RT D A$ * s+E log 08g+18g7058g+18gnF D A$ + E !."5" X G."3%")* 3 X !FG* 3 5 log 7 E A$ + 1 A$ 3 + 3molX F@455cmol D A$ *aq+E 3 7+5.G5 K- 5.54F3@ L log 5.4 7+5.G5 K- 5.54F3@ L log ! 7+5.G5K-5.54F3@L5."535 7+5.G5-5.53?G7+5.?G!!K C lc"l te the electrode &ote!ti l o% M#9CGM# electrode i! /hich KM#9CL is '+3 M+ E'M#9CGm#H-9+>5 1 Sol"tio!: #g!+*a,+ + !e- #g*s+ n7! 3 6og H7log 7log 3573 5.3 !."5"RT D M$ * s +E log 0#g!+1#g7 05#g!+1#gnF D M$ !+ *aq +E 5.54F 3 log 8t !45 0#g!+1#g7 05#g!+1#gn 53 5.54F log35 0#g!+1#g7 05#g!+1#g! 5.54F3@ X3 7-!."@ K ! 7-!."@ K-5.5!F4G K 7-!."@ K-5.5"7-!."F K C lc"l te the electrode &ote!ti l o% the %ollo/i!# h l% cell: Cr9O69-( -) C 3:HC( -) C5e- I 9Cr>C ( -) C 6H9O(l) E'redH C 3+>> 1 <he! KCr9O69-LH'+9MMKHCLH3MMKCr>CLH'+3M Sol"tio!: n7@ DCr "+ E! D H !OE? += DCr!O ! ? ED H + E3% *5.3M + ! X 3 = = 5.54 *5.!M + X *3+3% log + = 3o$ 5.54 = log 4 X 35! = 5.@FF5 ! = 3."535 !."5"RT Ered = E 5 red log + nF 5.54F3@ Ered = E 5 red log + n 5.54F3@ = +3.""# X *3."535+ @ = 3."" + 5.53"# = +3."%"#

:6+

:8+

:?+

The me s"red cell &ote!ti l o% the %ollo/i!# cell is 3+99 C lc"l te KCdC9L i! the !odic com& rtme!t+ E'Cd9CGCd H -'+:'1 E'A#CGA# H '+8'1: Cd G CdC9('+3M) P A#C ('+4M) G A# Sol"tio!: 05 cell 7 05 cathode - 05 anode 7 +5.G5 - *-5.%5+ 7 +3.!5K !."5"RT log + nF ! ,o$+ = * E 5 cell E cell + X 5.54F ! = *3.!5# 3.!!# + X 5.54F + = Anti log*5.!F53 5+ Ecell = E 5 cell 3.F45 x353 += DCd +! E D A$ + E!

DCd +! E = +X D A$ + E! = 5.3F4 X *5.4M + ! = 5.%G?4M

4'+

G NiC9 P A#C G A#$ C lc"l te the e-"ili.ri"m co!st !t t 94'C+Ho/ m"ch /or0 /o"ld .e o.t i!ed .y o&er tio! o% this cell= E'Ni9CGNi H --'+941 E'A#CGA# H '+8'1: Sol"tio!: 2i 2i+! + !e+ !8g !e !8g NNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNN 2i +!8g+! d+! +!8g
,or the cell re ctio! Ni

cell

70

cathode

2umber of electrons lost or gained *n+ 7 5 0 anode 7 +5.G5 - *-5.!4+ 7 +3.54K

+ = *c =

D Ni +! E D A$ + E! 5.54F E 5 cell = log * c n nXE 5 nX 3.54# ,o$* c = = = "4.@ 5.54F 5.54F

Bc 7 8nti log "4.@ 7 ".FG3 L35"4 7 % L L35"4 - 5 = nFE 5 = ! X F@455C 1 mol = !5!@45 ) = !5!.@4!.. 43+ Ho/ m !y co"lom.s o% electricity re re-"ired %or the %ollo/i!# red"ctio! &rocesses: i) 3mole o% A#C ii)3 mol o% C"9C iii) 3 mol o% Al>C+ i)) 3 mole o% / ter to dioxy#e!+ Sol"tio!: i+ 8g+3 + e 8g 3mol 3mol 3mol 3mol 3F 3mol 3 mol 8g is deposited by 3 Faraday73 FLF@455 mol -37F@455 ii+ u!+ + !e u 3mol !mol 3mol 3mol !F 3mol 3 mol u is deposited by ! Faraday 7 !FLF@455 mol-373F"555 iii+ 8l"+ + "e 8l 3mol "mol 3mol 3mol "F 3mol 3 mol 8l is deposited by " Faraday7" FLF@455 7 !GF455 iv+ !H!$*l+ %H+*a,+ $!*g+ + %e!mol %mol !mol %F 3

!mol water is reduced by 7!FLF@455 49+

%F X 3mol !mol mol-373F"555

Ho/ m !y co"lom.s re re-"ired to &rod"ce 9'' # c lci"m %rom C Cl9+ Sol"tio!: a+! + !e a*s+ 3mol !mol 3mol :roduction of %5 g re,uires ! F electricity. :roduction of !5 g a re,uires 3 F electricity. 3 F 7 F@455 Ho/ m !y #r ms o% .romi!e c ! .e &rod"ced .y the electrolysis o% molte! m #!esi"m .romide /ith c"rre!t o% >+9 m&ere %or 4' mi!"tes= (M#H39M;rH8' m") Sol"tio!: H7 - L t @5sec ".!am"X *G5 min X + = F@55C 3min F@55 = F F@455 !=r- =r! + !e!mol 3 mol !mol !mol 3mol !F ! F charge produce 3mol =r! 7 ! LG5gLmol-373@5 g F@55 3@5 $ F@55 = Felectricit("roduce3molbr ! = X F@455 !F F@455 = ?.F@ $ Ho/ lo!# c"rre!t o% > m&s h s to .e & ssed thro"#h sol"tio! o% sil)er !itr te to co t met l s"r% ce o% 8'cm9 /ith '+''4 mm thic0 l yer= *e!sity+ Sol"tio!: Kolume of silver to be deposited7 8rea L Thic.ness 5.54 = G5cm ! X cm 35 #ass of silver to be deposited 7Kolume L Aensity 5.54 cmX 35.4 $cm " 7G5 cm!L 35 75.%!g The cathode reaction is 8g+ + e 8g 3mol 3mol 3mol 3mol 3F 3mol 35G g 8g is deposited by F@455 coulomb of electricity F@455C X 5.%! $ 7"?4." coulombs 5.%! g 8g us deposited by 35G $ H7 L t + "?4."C t= = = 3!.43 / "C 1 &ec Aredict i% the %ollo/i!# re ctio! is %e si.le or !ot $ !d Sol"tio!: #ust be positive for cell reaction to be feasible. -n the given reaction, 8g is oxidi(ed. 'o, it is acting as anode and u is reduced so, it is acting as cathode. 7 7 +5."% P *+5.G5+ 7 5."% P 5.G5 7 P 5.%@ K 'ince is having negative value, so the reaction is not feasible. !

4>+

4:+

44+

45+

Chromi"m met l c ! .e &l ted o"t %rom cidic sol"tio! co!t i!i!# CrO> ccordi!# to %ollo/i!# re ctio!C lc"l te the m ss o% chromi"m th t /ill .e &l ted o"t .y 39''' C o% ch r#e+ Sol"tio!:

@ mole of eP deposit 7 3 mole of r 7 4!g of r Huantity of electricity on @ moles of eP 7 4?F555 of charge deposits on 7 4!g of r 7 4?F555

3!,555 7 46+

of charge deposits on 7

A! "!0!o/! met l M dis&l ces Ni %rom NiCl9 sol"tio! ."t it does !ot dis&l ce M! %rom M!Cl9 sol"tio!+ Arr !#e met l M$ Ni !d M! i! correct order o% red"ci!# &o/er+ Sol"tio!: i+ $xidation potential of # is more than 2i because # displaces 2i!+ from 2i l!. *ii+ $xidation potential of # is less than #n!+ because # cannot displace #n!+ from #n l!.$rder of oxidation potential is 2i R # R #n . #ore the oxidation potential means stronger reducing power. orrect order of reducing powers is #n S # S 2i

48+

The resist !ce o% '+4 M CH>COOH sol"tio! is 3'' ohm+ The cell co!st !t is '+'>4Gcm+ C lc"l te mol r co!d"cti)ity o% sol"tio!+ Sol"tio!: 0lectrolyte onductivity 7

H H

#olar onductivity 7

7 4?.

5 Zn + !1 Zn = 5.?@# ,i!d the emf o% %ollo/i!# cell 5 0b + !1 0b = 5.3!# Sol"tio!: From the cell representation, it is clear the )n is anode and :b is cathode. 05cell 7 7 P5.3! P *P5.?@+ 7 P5.3! + 5.?@ 7 + 5.@% K Jiven

5'+

The resist !ce o% 3N sol"tio! o% CH>COOH is 94' ohm+ The cell co!st !t is 3+34 cmJ3+ C lc"l te the e-"i) le!t co!d"ct !ce o% sol"tio! Sol"tio!: onductivity 7

Te,. 7

7 7 53+ C lc"l te the !"m.er o% co"lom.s re-"ired to de&osited 6+94# o% Al+ Sol"tio!:

!?g *7 3 mole+ of 8l is deposited by 7 " moles of eP harge re,uired to deposit !?g of 8l 7

harge re,uired to deposit ?.!4g of 8l 7 7 ???"@.33 . 59+ C lc"l te m ss o% co&&er de&osited /he! co&&er s"l&h te %or t/o ho"r+ Sol"tio!: 0,uivalent wt. of u 7 c"rre!t '+> m&ere is & ssed i! - sol"tio! o%

) for u 7 >7)it 7 7 5.?35@ g. 5>+ The em% o% B! J C" cell is 3+3 1 t 9?8 2+ C lc"l te e-"ili.ri"m co!st !t o% the re ctio!+ Sol"tio!:

3.3 7

log B 7 B 7 8ntilog "?.!! 7 !

5:+

C lc"l te st !d rd %ree e!er#y ch !#e %or the %ollo/i!# chemic l re ctio! J $ Sol"tio!: -t is clear from 7 7 5.G5 P *P 5.%5+ 7 3.!5 K n7! 7 7 7 !"3@55 U 7 !"3.@ .U data that 8g is anode and d is athode.

54+

,i!d em% o% H9JO9 %"el cell %rom the %ollo/i!# d t Sol"tio!: 7 P !"4 .U molP3 7 7 7 7 3.!3G K

55.

C lc"l te mol r co!d"cti)ity o% sol"tio! o% M#Cl9 t i!%i!ite dil"tio! %rom the #i)e! d t + Sol"tio!:

7 7 7 35?.3! + 34!.@G 7 !4F.G ohmP3 cm! molP3 56+ ,i!d the ) l"e o% e-"ili.ri"m co!st !t %rom the %ollo/i!# d t Sol"tio!: 7

5.!F4 7

6og B 7 B7

SECTION NCO (ELECTRO CHEMISTRY)

P3+ <rite the cell re ctio!s /hich occ"r i! le d stor #e . ttery /he! the . ttery is "se !d /he! the . ttery is o! ch r#i!#+ Sol"tio!: The cell re ctio! occ"rri!# i! le d stor #e . ttery+ i+ >hen battery is in use/ 8node/ :b'$% + !e :b + '$%-! athode :b$! + '$%-! + %H+ + !e :b'$% +!H!$! ii+ >hen battery is charging $n charging the reaction is reversed and :b'$%*s+ and on anode and cathode is converted in to :b and :b$! respectively. Co!d"cti)ity o% '+''9:3M cetic cid is 6+8?5 x 3'-4SGcm+C lc"l te its mol r co!d"cti)ity+ I% cetic cid is >?'+4Scm mol-3$ /h t is the dissoci tio! co!st !t= Sol"tio!: ?.GF@ X 354 &cm3 m = = C 5.55!%3molX *3555cm" + 3 ?.GF@ X 354 &cm 3 X 3555cm" " !.%3X 35 mol ?.GF@ X 35 &cm ! mol 3 = !.%3 ?G.F@ = &cm ! mol 3 !.%3 = "!.?@ &cm ! mol 3 %ence =

P9+

=
*= P>

m "!.?@&cm ! mol 3 = = 5.5G"F5 5 "F5.4&cm ! mol 3

C ! 5.55!%3X *5.5G%+ ! = = 3.G4 X 354 3 *3 5.5G%+

i) *e%i!e electric l co!d"cti)ity !d mol r co!d"cti)ity o% sol"tio! !d /rite "!its o% mol r co!d"cti)ity+ ii) The ) l"es corres&o!di!# to the %ollo/i!# t/o red"ctio! electrode &rocesses re: )C"CGC" H C'+49 1 .) C"C9GC"C H '+35 1+ ,orm"l te the # l) !ic cell %or their com.i! tio!+ <h t /ill .e the st !d rd cell &ote!ti l %or it= C lc"l te+ - 5 %or the cell re ctio!+ Sol"tio!: i+ 0lectrical conductivity may be defined as the conductance produced by the ions when electric current is passed through an electrolyte. #olar conductivity m may be defined as the conductance of all the ions in one mole of electrolyte in the solution at given dilution. This is mathematically represented as * m = m = *X#m < Km 7 Kolume of the solution. Cm 7 oncentration the solution. m The units of molar conductivity is ohm-3cm! or 'cm!mol-3 ii+ The galvanic cell is represented as u+ 1 u+! P u+ 1 u 8node athode The cell reaction is u+ + u+ u+! + u Jiven u+1 u 7 +5.4! u+!1 u+ 7 5.3@ K. 5 cell 7 5.4!K - 5.3@K 7 5."@K alculation of free energy. - 5 = nFE 5

- 5 = 3X F@455Cmol 3 X 5."@# = "%?%5C#mol 3 = "%?%5 )mol 3 "%.?%!.mol 3 P: i) I! the ."tto! cell /idely "sed i! / tches !d de)ices$ the %ollo/i!# re ctio!s t 0es &l ce: B! C A#9O CH9O I B!C9 C 9A# C9OH5 5 *etermi!e E' !d - 5 %or the re ctio!+ (i)e! th t A$ + 1 A$ = +5.G5# , E Zn+! 1 Zn = 5.?@# ii) Ex&l i! /ith ex m&les the terms /e 0 !d stro!# electrolytes+ Ho/ c ! these .e disti!#"ished= Sol"tio!: -n galvanic cell, the anode has grater tendency to lose electron than cathode. >hen two electrodes are connected, the electrode having grater Pve *lesser +Ke+ value of reduction electrode potential acts as anode, while the other electrode as cathode. The reduction potential of )inc )n+! + !e )n 5 = 5.?@# 8nd silver oxide is 8g!$ + H!$ + !e !8g + !$H- 5 = 5.G5# &eduction potential of silver electrode is higher than that of )inc electrode. )n 1 )n+! P 8g!$ 1 8g 8node athode
8t 8g electrode &eduction ta.es place 8t )n electrode &eduction ta.es place

8g!$ + H!$ + !e)n

NNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNN

!8g + !$H- 5 = 5.G5# )n+! + !e- 5 = 5.?@# !8g +!$H05cell7 3.4@K

8g!$ + H!$ + )n
5 5

- = nFE - 5 = ! X F@455Cmol 3 X 3.4@# = "%?%5C#mol 3 = ".53X 354 )mol 3 ii+ 8 strong electrolyte is completely ioni(ed at all dilutions and hence its e,uivalent or molar conductivity does not change much by increasing dilution *lowering the concentration+ small in increase is due to increase in mobility if ions. 8 wea. electrolyte is not completely ioni(ed at all dilutions and hence its e,uivalent or molar conductivity changes much by increasing dilution *lowering the concentration+. The increase is due to a+ -ncrease in ioni(ation, which causes increase in number of ions. 8nd b+ #obility if ions. P4 i) Ex&l i! /hy electrolysis o% -"eo"s sol"tio! o% N Cl #i)es H9 t c thode !d Cl9 t !ode+ <rite o)er ll re ctio!+ 5 5 5 5 ii) Na + 1 Na = !.?3# , E H !O +! 1 H ! = 5.G"# Cl !1! Cl = +3."@# , E H = +O !1 H !O = 3.!"# iii) C lc"l te the e$m+% o% the cell B! G B!C9('+3M) P CdC9('+'3M) G Cd t 9?82 5Cd +! 1 Cd = 5.%5# , E 5 Zn+! 1 Zn = 5.?@# Sol"tio!: 'tandard reduction potential for reduction of water *-5.G"K+ is more than the standard reduction potential of 2a+*-!.?3K+.Hence ,reduction of water ta.es place in the preference to 2a+ -ons and H! gas will liberate at cathode. &eactions at cathode/ 2a+ + e 2a !H!$ + !e H! +!$H&eactions at anode ! l- l! +!e3 !H!$ + !e $! + !H+ + !e! $xidation of water needs large activation due to slow transfer of electrons. -t creates electrical resistance at anode surface< extra voltage is re,uired to over come this resistance. Aue to re,uirement of extra voltage for oxidation of l- ions tales place in preference to water. Hence, 3 3 chlorine is given out at anode.2a l + H!$ 2a+ + $H- + H! + l! ! ! ii+ The cell/ )n 1 )n+!*5.3#+ P d+!*5.53#+ 1 d at !FGB 8node athode !

The cell reaction is )n+ d+! 05 cell 7 05 cathode - 05 anode 2erest e,uation

)n+! 7

+ d -.%5 - *-5.?5+ 7 5."@K

5.54F3 Doxdn.E log n D ReductionE 5.54F3 D Zn +! E Ecell = 5."@ log ! DCd +! E 5.54F3 D5.3E = ."@ log ! D5.53E = ."@ 5.5!F4log35 = ."@ 5.5!F4*3+ = 5.""54# Ecell = E5 P5 Acco"!t %or the %ollo/i!# i) Al0 li!e medi"m i!hi.its the r"sti!# o% iro!+ ii) Iro! does !ot r"st e)e! i% the @i!c co ti!# is .ro0e! i! # l) !i@ed iro! &i&e+ iii) C"9C C 9e- I C" M E' H C '+>: 1 !d A#C C 3e- I A# M E' H C '+8' 1 Co!str ct # l) !ic cell "si!# The .o)e e-" tio!s+ iii) ,or /h t co!ce!tr tio! o% A#C io!s /ill the em% o% the cell .e @ero t 94'C$i% the co!ce!tr tio! o% C"9C is '+'3M+ Sol"tio!: i+ &usting ta.es p5lace in the presence of H+ ions more rapidly. 8n al.aline medium inhibits the rusting by neutrali(ing H+ ions. Thus the presence of $HN furnished al.aline solution removes H+ ions from the reaction and hinders the rusting of Fe to Fe+! and Fe+". ii+ )inc is more reactive than iron. )inc has lower reduction potential than iron. #ore electropositive (inc metal coated on iron acts as anode and loses electrons to iron which act as cathode. Thus, iron does not get rusted because any Fe!+ formed will gain electron from (inc to from -ron. iii+ u 1 u+! P 8g+ 1 8g at !FGB 8node athode 05
u1 u+!

7 + 5."% K and 058g18g+ 7 + 5.G5 K

iv+ u 1 u+!*5.53+ P 8g+*#3+ 1 8g at !FGB 8t 8node. u 8t athode !8g u n7!

5

!e

u+! !8g !8g + u+!

+ !e-

NNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNN

+ !8g 05 anode

NNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNNN

and 0 cell 7 05 cathode +! 5.54F3 DCu E cell = 5 cell log n D A$ + E! 5.54F3 D5.53E = 5cell log ! D M 3 E! = 5.%@ 5.5!F4log log D5.53E D M 3 E!

7 5.G5 P * 5."%+ 7 5.%@K

D5.53E 5.%@ = = 34.4F" ! 5.5!F4 DM3 E

D5.53E = Anti log34.4F" = ".F3F X 3534 D M 3 E! D M 3 E! = 5.53 3 = 34 ".F3F X 35 ".F3F X 353? = 5.!44 x35? = !.44 X 353G M 3 = !.44 X 353G = 3.4F X 35F M

P6

i) C lc"l te the em% o% cell M# G M#C9('+3') P C"C9(3E3'->) G C" t 9?82E'C"GC"C9 H C '+>: 1 !d E'M#C9GM# H - 9+>6 1 ii) Ex&l i! /ith ex m&les the terms /e 0 !d stro!# electrolytes+ Sol"tio!: The cell reaction is #g + u #g+! + u n7! +! 5.54F D M$ EDCu E E 5 cell = E 5 + log ! D M$ +! EDCu E 5.54F DCu +! E = VE u 1 u E u 1 u W + log ! D M$ +! E 5.54F 5.5553 = 5."% *!."@+ + log ! 5.553 = !.?5 + 5.5!F4*3+ = !.@?54# ii+ >ea. electrolytes are those which ioni(e partially and reversibly in a,ueous solutions. 0xamples/2H%$H, H" $$H,H 2. 'trong electrolytes are those which ioni(e completely at all dilutions. 0xamples/ /2a$H,B$H,2a l,H l,H2$",H!'$%
5 +! 5 +!

>ea. electrolytes 3. These are not fully dissociated at high concentrations. !. There are no strong interring ionic attractions between the ions even at high concentrations. ". Their conductance increases with increase of dilution due to increase in ioni(ation as well as mobility of ions, so this increase is very sharp and more.

'trong electrolytes 3. 3. These are ompletely dissociated at all concentrations. !. There are strong interring ionic attractions between the ions even at high concentrations. ". Their conductance increases with increase of dilution due to increase in mobility of ions, so this increase is liner and less.

P8

i)The resist !ce o% co!d"cti)ity cell co!t i! )+''3M 2Cl sol"tio! t 9?82 is 34'' +<h t is the cell co!st !t $i% the co!d"cti)ity o% '+''3M 2Cl sol"tio! t 9?82 is '+3:5 E 3'-> S cm3 = ii) Aredict the &rod"cts o% electrolysis i! the electrolysis o% dil"te H9SO: /ith &l ti!"m electrodes+ Sol"tio!: i+ ell constant 7 onductivity L &esistance75.3%@L35-" ' cm-3 L3455 75.!3Fcm-3 ii+ -n electrolysis of H!$, the two possible anode reactions are a+ !H!$ b+ !'$%-! $! + %H+ -! '!$G + +!e+ %e-

For dilute solution of H!'$% reaction a+ is preferred and the product obtained at anode is $! gas. =ut at higher concentration of H!'$% the reaction b+ is preferred. athode/ !H!$ + !e H! + !$H+ 8node / !H!$ $! +%H + %e!

P?

<rite the Ner!est e-" tio! !d c lc"l te the em% o% the %ollo/i!# cell t 9?82 C" G C"C9('+3>') P A#C (3E3'-:M) G A# t 9?82 #i)e! th t E'A#CGA# H C'+8'1 E'C"C9GC" H C '+>: 1+ Sol"tio!: The cell reaction can be written as u + !8g u+! + !8g +! 5.54F DCu E Ecell = E 5 cell log n D A$ + E! = E 5 cell + 5.54F D A$ + E! log ! DCu +! E

5.54F D5.3"5E! log ! D35% E 5.3"5 = 5.%@# D5.5!F4log G 35 = 5.%@# D5.5!F4log3." X 35? E# = *5.G5 ."%+ = 5.%@# 5.5!F4Dlog3." + ? log35 E# = 5.%@# 5.5!F4D5.33"F + ?E# = 5.%@# D5.5!F4 X ?.33"FE# = .%@# 5.!3# = 5.!4#

P3'

Aredict the &rod"cts o% electrolysis o.t i!ed t the electrodes i! e ch c se /he! the electrodes "sed re &l ti!"m+ i)A! -"eo"s sol"tio! o% A# NO> ii) A! -"eo"s sol"tio! o% H9SO: Sol"tio!: i+ >hen a,ueous solution of 8g2$" is electroly(ed using platinum electrodes, deposition of silver would ta.e place on inert cathode and the evaluation of oxygen would ta.es place at the anode. 8t cathode/ 8g+ + e 8g 8t anode/ !H!$ $! +%H+ %eii+ >hen an a,ueous solution of sulphuric acid *H!'$%+ is electroly(ed using platinum electrodes the evolution of hydrogen gas at the cathode and evolution of oxygen gas at anode would occur. 3 8t cathode/ H!$ + e H! + $H! 8t 8node/ ! H!$ $! + %H+ + %e) St te t/o d) !t #es o% H9-O9 %"el cell o)er ordi! ry cell+ .) Sil)er is electrode&osited o! met llic )essel o% tot l s"r% ce re ?'' cm9 .y & ssi!# c"rre!t o% '+4 m&s %or t/o ho"rs+ C lc"l te the thic0!ess o% sil)er de&osited+ K(i)e!: de!sity o% sil)erH3'+4 # cm->$ tomic m ss o% sil)er H3'8 m"$ ,H?54''C mol-3L Sol"tio!: a+ advantages of H!-$! fuel cell over ordinary cell are/ i+ The fuel cell converts energy of fuel directly into electricity. ii+ The products formed by them do not cause pollution. b+ Jiven/-75.4 amp, t 7 !h, H 7 - L t 7 5.4 8 L ! L @5 L @5 s7 "@55 8g+ + e 8g*deposited+ F@455 deposit silver 735G g 35G X "@55 = %.5!F $ "@55 deposit silver 7 F@455 Mass %.5!F $ = = 5."G"cm" Kolume of silver deposited 7 " Densit( 35.4 $cm #olume 5."G"cm" = = 5.555%!44cm 35.4 $cm ! Thic.ness 7 Area = %.!44 X 35% cm

P33+

P39+

(i)e re so!s %or the %ollo/i!#M i) R"sti!# o% iro! is -"ic0er i! s li!e / ter th ! i! ordi! ry / ter+ ii) Al"mi!"m met l c !!ot .e &rod"ced .y the electrolysis o% -"eo"s sol"tio! o% l"mi!"m s lt+ Sol"tio!: i+ &usting of iron is ,uic.er in saline water than in ordinary water because conductivity of saline water is more than that of ordinary water. ii+ 8luminum metal is highly reactive and can not be reduced easily. 8s compared to water is reduced more easily.

P3>+ Resist !ce o% co!d"cti)ity cell %illed /ith '+3M 2Cl sol"tio! is 3'' ohms+ I% the resist !ce o% the s me cell /he! %illed /ith '+'9M 2Cl sol"tio! is 49' ohms$ c lc"l te the co!d"cti)ity !d mol r co!d"cti)ity o% '+'9 M 2Cl sol"tio!+ Co!d"cti)ity o% '+3 M 2Cl sol"tio! is 3+9? S m-3+ Sol"tio!: ell constant *JX+ 7 onductivity L resistance 7 3.!F'm-3L355 ohms73!F m-3 onductivity of 5.5! # B l solution 7 cellcons tan t 3!Fm 3 = = 5.!%G&cm 3 resis tan ce 4!5 oncentration 7 5.5! mol 6-3 7 3555 L 5.5!" mol m-" 7!5 mol m-" #olar conductivity ! *conductivit( + m = C 3 !.%G X 35 &m 3 = = 3!% X 35% &m ! mol 3 !5molm " Alternativel( 3.!Fcm 3 = 5.!%G X 35! &cm 3 4!5 !X 3555cm" ,3 m = molarit( != = 5.!%G X 35! &cm 3 X 3555cm" ,3 = 3!%cm ! mol 3 3 5.5!mol,

P3:+ C lc"l te the st !d rd cell &ote!ti l o% ( l) !ic cell i! /hich the %ollo/i!# re ctio! t 0es &l ce+ 9Cr C >CdC9 I 9Cr>C C >Cd ' Also c lc"l te Q( ) l"e %or the re ctio!+ ((i)e!: E'CrC>GCr H - '+6: 1+ E'CdC9GCd H - '+:' 1+) Sol"tio!: 05 cell 7 05 cathode - 05 anode 7 -5.%5 - *-5.?%+ 7 5."%K 2umber of electrons lost or gained n7 @ - 5 = nFE 5 - 5 = @ X F@455Cmol 3 X 5."%# = 3F@.G@C#mol 3 = 3F@.G@ *)mol 3 P34+ *e%i!e co!d"cti)ity !d mol r co!d"cti)ity o% the sol"tio! o% ! electrolyte+ Sol"tio!: The conductivity is defined as the conductance of any solution placed between the two electrodes of one unit area each, and separated by distance of one unit. The conductivity measures the ease with which the current can be passed through an electrolytic solution. -t is given by . *Bappa+ Cellcons tan t 7 resis tan ce #olar conductivity * m + is the conducting power of cell the ions produced by one mol of an electrolyte. -t is given by

X 3555 &cm ! mol 3 M Kariation of and m with concentration

m 7 !

onductivity decreases with dilution. =ecause the number of ions per unit volume that carry the current in a solution decreases. #olar conductivity increases with decrease in concentration. This is because the total volume, K of a solution containing one mole of electrolyte also increases. #olar conductivity is the conductance of solution with unit length but the electrodes having area of cross section. A = = # l The decrease in . on dilution is more than compensated by increase in its volume. Hence m -ncrease with decrease in concentration.

SECTION- * (ELECTRO CHEMISTRY)

"

3+

i+ >hich electrolyte is used in dry cellY ii+ >hat is fuel cellY Jive the electrode reactions of H!$! fuel cell. iii+ >hy type of metals can be used for cathodic protection of iron against rusting. iv+ Jive the mathematical expression which relates molar conductivity *8m+ of wea. electrolyte to its degree of dissociation *Z+. 0xplain the meaning o f the terms a+ ionic mobility b+ over voltage c+ ell constant d+ orrosion. How would you test whether the given electrolyte is strong electrolyte or wea. electrolyteY by the measurement of conductivity. 0xplain the following in brief. i+ >hat is the use of platinum foil in hydrogen electrodeY ii+ $n the basis of 05 values given bellow comment whether it is safe or not to stir 3 # 8g2$" solution with copper spoon. 05 8g+ 1 8g 7 5.G5 K< 05 u!+ 1 u 7 5."% iii+ 0lectrolysis of fused BHF! gives fluorine at anode but hydrogen at cathode. i+ How does electrical conduction of metals differ from that of electrolytic conduction. How do the two change with the rise in temperature. ii+ >hat is a calomel electrode write its electrode reaction when it acts as anode. iii+ How would you arrive at the dimensions of ohm . >hat is disproportionationY alculate the e,uilibrium constant for the disproportionation of copper *-+ ion in a,ueous solution. Jiven that 0 5 u!+ 1 u 7 + 5."% K and 0 5 u3+ 1 u 7 + 5.4! K. 4 6 of 5.3 # u'$% was to be electrolysed using a current strength of !.5 amperes. =ut before electrolysis 35 g of (inc dust was added to the electrolytic cell. For how long the electrolysis has to be carried out in order to completely deposit the copper ions from the 'olutionY *8tomic masses of copper and (inc are @".4 and @4 respectively+. alculate the 0#F of the cell #g*s+ 1 #g!+*5.! #+ CC 8g+ * 3 x 35-" #+ 1 8g< 0 5 #g!+ 1 #g 7 -!."? K, 0 5 8g+ 1 8g 7 + 5.G5 K. >hat will be the effect on 0#F if concentration of #g!+ ion is decreased to 5.3 #Y 0xplain the following. i+ &usting of iron becomes rapid in saline water than ordinary water. ii+ #obility of H + ions is high through the ice than the li,uid water. iii+ >hy does a cell stops wor.ing after some time. )inc electrode is constituted at !FG B by placing (inc rod in 5.3 # a,ueous solution of (inc sulphate which is F4[ dissociated at this concentration. >hat will be the electrode potential *0)n!+ 1 )n+ of the electrode given that 05 )n!+ 1 )n 7 - 5.?@ K. rude copper containing iron and silver as contaminations was subOected to electro refining using a current of 3?4 8 for @.%"% min. The mass of anode was found to decrease by !!.!@5g while that of cathode was increased by !!.533 g. 0stimate the [ age of u, -ron and silver in crude copper. )n rod weighing !4 g was .ept in 355 m6 of 3 # u'$% solution. 8fter a certain time interval, the molarity of u!+ was found to be 5.G #. >hat is molarity of '$%!- ions in the resulting solution and what should be the mass of )n rod after cleaning and drying. The emf of the cell, 8g 1 8g l *'aturated 'ol.+ CC 5.53 # 8g2$" 1 8g at !FG B is 5.3@F K. alculate solubility and solubility product of 8g l at !FG B. onsider the reaction given below Hg!+ + 8g 8g+ + Hg. omment on the feasibility of reaction under different concentration of ions given below. i+ DHg!+E 7 35-% # < D8g+E 7 35-3 # ii+ D8g+E 7 35-% # < DHg!+E 7 35-3 #. Jiven 05 8g+ 1 8g 7 5.G5 K< 05 Hg!+1 Hg 7 5.?F K Jiven that 05 #n"+ 1 #n!+ 7 + 3.43 K< 05 #n!+ 1 #n 7 - 3.3G K "

9+ >+ :+

4.

5.

6.

8+

?+

3'+

33.

39+

3>+ 3:+

34+

05 r"+ 1 r!+ 7 - 5.%3 K< 05 r!+ 1 r7 - 5.F3 K >hich oxidation state *+! or +"+ will be more stable for manganese and chromium as per the data. 35+ For the galvanic cell/ 8g 1 8g l*s+, B l*5.! #+ CC B=r *5.553 #+. 8g=r*s+ 1 8g assign correct polarity to each electrode for a spontaneous process ta.ing into account the cell reaction at !45 Bsp*8g l+ 7 !.G x 35-35< Bsp*8g=r+ 7 "." x 35-3"< -f a current of 5.!55 8 is passed through 45 ml of # 1 35 2a l solution for 35 min. calculate the concentration of $H- ions in the solution after the electrolysis. The 0dison storage cell is represented as Fe*s+ 1 Fe$*s+ 3 2i!$"*s+ 1 2i*s+ The half-cell reactions are 2i!$"*s+ + H!$*l+ + !e- \ !2i$*s+ + !$H- < 05 7 + 5.%5 K Fe$*s+ + H!$*l+ + !e- \ Fe*s+ + !$H-< 05 7 - 5.G? K i+ >hat is the cell reactionY ii+ >hat is the cell emf Y How does it depend on the concentration of B$H Y iii+ >hat is the maximum amount of electrical energy that can be obtained from one mole of 2i!$" Y 3?+ The standard reduction potential of the 8g+ 1 8g electrode at !FG B is 5.?FF K. Jiven that for 8g-, Bsp 7 G.? x 35-3?, evaluate the potential of the 8g+ 1 8g electrode in a saturated solution of 8g-. 8lso calculate the standard reduction potential of the -- 1 8g- 1 8g electrode. The standard reduction potential for u!+ 1 u is 5."% K. alculate the reduction potential at pH7 3% for the above couple . Bsp of u*$H+! is 3.5 x 35-3F. How many gram of silver could be plated out on a serving tray by electrolysis of a solution containing silver in + 3 oxidation state for a period of G.5 hrs at a current of G.%@ ampereY >hat is the area of the tray if the thic.ness of silver plating is 5.55!4% cmY Aensity of silver is 35.4 g cm-". 0lectrolysis of a solution of #n'$% in a,ueous sulphuric acid is a method for the preparation of #n$! as per the chemical reaction #n!+*a,+ + !H!$ #n$!*s+ + !H+ + H!*g+. :assing a current of !? 8 for !% hrs gives one .g of #n$!. >hat ids the current 0fficiency and what are the reaction occurring at cathode and anodeY alculate the e,uilibrium constant for the reaction, !Fe"+ +"F \ !Fe!+ + -"-. The standard reduction potentials in acidic conditions are 5.?? and 5.4% K respectively for Fe"+ 1 Fe!+ and -"- 1 --couples. Find the solubility product of a saturated solution of 8g! r$% in water at !FG B if the emf of the cell 8g 1 8g+ *saturated 8g! r$%+ CC 8g+ *5.3 #+ 8g is 5.3@% K at !FG.

36+ 38+

9'+ 93+

99+

9>+

9:+

94. 8 cell 8g 1 8g+ CC u!+ 1 u initially contains 3 # 8g+ and 3 # u!+ ions. alculate the change in cell potential after the passage of F.@4 8 of current for 3 hour. 95+ 'ilver electrode is immersed in saturated solution of 8g!'$%. The potential difference between the silver and standard hydrogen electrode is found to be 5.?33 K. Aetermine the Bsp of 8g!'$%. 96. !45 ml of copper sulphate solution was electroly(ed using platinum anode and copper athode. 8 constant current of ! m8 was passed for 3@ minutes. -t was found that after electrolysis the absorbance of solution was reduced to 45[ of its original value calculate oncentration of copper sulphate solution to begin with. 98+ 8 solution containing %.4 m# of r!$?!- ions and 34 m# of r"+ ions shows a :H !.5. >hat is the potential of half reactionY r!$?!- r"+ Two students use same stoc. solution of )n'$% and a solution of u'$%. The emf of one of the cell is 5.5" K higher than the other. The conc. of u'$% in the cell with higher emf is 5.4 "

9?+

#. calculate the conc. of u'$% in the other cell. *!."5" &T 1 F 7 5.5@+ >'+ Find e,uilibrium constant at !FG B for the reaction -n"*a,+ Jiven that/ 05 u!+ 1 r+ 7 5.34 K < 05 -n"+ 1 -n+ 7 - 5.%! K < 05 -n"+ 1 -n+ 7 - 5.%5 K u!+*a,+ + -n!+*a,+ \ u+*a,+ +

"