Sri Chaitanya Narayana IIT Academy

Chemistry_Electrochemistry

Sri Chaitanya Narayana IIT Academy

Sri Sarvani Educational Society
COMMON CENTRAL OFFICE_MADHAPUR_HYD

CHEMISTRY : ELECTROCHEMISTRY

Assignment-3
Paragraph for Q estions !os" # to 3 A hydrogenoxygen fuel cell has a solid electrolyte, which is an ion exchange membrane The membranes is im!ermeable to the reactant gases, but is !ermeable to hydrogen ions, which carry the current between the electrodes To facilitate the o!eration of the cell at "# to $#%C, the electrodes are co&ered with finely di&ided !latinum that function as a catalyst 'ater is drained out of the cell during o!eration (uel cells of this general ty!e ha&e been used successfully in the s!ace !rogram and are )uite efficient Their disad&antages for large scale commercial a!!lication are that hydrogen !resents storage !roblems, and !latinum is an ex!ensi&e catalyst Chea!er catalysts ha&e been found for higher tem!erature o!eration of hydrogenoxygen fuel cells (uel cells that use hydrocarbons and air ha&e been de&elo!ed, but their !ower !er unit weight is too low to ma*e them !ractical in ordinary automobiles +etter catalysts are needed A hydrogenoxygen fuel cell may ha&e an acidic or al*aline electrolyte The halfcell reactions are . , ( g ) + ,/ + + ,e = / ,. ( l) E% 0 - ,, 11 2 , ,/3 3 ,e = / , ( g ) E% 0 # / , ( g ) + . , ( g ) = / , . ( l) E% 0 - ,,112 , or . , ( g ) + / , . ( l) + ,e = ,./ E% 0 # "##4 2 , ,/ ,. ( l) + ,e = / , ( g ) + ,./ E% 0 # 1,54 2 / , ( g ) + . , ( g ) = / ,. ( l) E% 0 - ,,11 2 , To maximi6e the !ower !er unit mass of an electrochemical cell, the electronic and electrolytic resistances of the cell must be minimi6ed Since fused salts ha&e lower electrolytic resistances that a)ueous solutions, high tem!erature electrochemical cells are of s!ecial interest for !ractical a!!lications /igh tem!erature also allow the use of li)uid metal electrode, which ma*e !ossible higher current densities than solid electrodes If 7$# m8 of /, gas at ST9 is fed into and is consumed by the fuel cell in -# minutes, then what is the current out!ut of the fuel cell: ;A< "A ;+< 1A ;C< -$A ;=< -,A
(or a /ydrogen.xygen fuel cell if / f ( / , ., l) 0 ,17 *> ? mole, then what will be its thermodynamic efficiency under standard conditions ;A< # 4;+< # ";C< # $@ ;=< # 1@

'hy are fuel cells not being used in daily life des!ite their &ery high efficiency ;A< The fuels needed for their o!eration are rarely found in nature -

C.I98_Chemistry

Sri Chaitanya Narayana IIT Academy

Chemistry_Electrochemistry

;+< Their o!eration always needs &ery high tem!erature ;C< The catalyst used in fuel cells at normal tem!erature are &ery ex!ensi&e ;=< The design of fuel cells is so com!licated that it is not feasible to construct these for daily life a!!lications $% E)ui&alence conductance of saturated solution of +aS." is conductance is A< &% At A< C< '% In acidic medium, Bn., is an oxidant as, If the !/ of the solution is decreased by one unit, the electrode !otential of the half cell 9tA will change by A< C# --1 2 +< # --1 2 C< # ,@$ 2 =< C# ,@$ 2 (% Di&en, The for the fuel cell reaction A< C"5" 1>EC+< C@,7 #>EC)% The heat of solution of anhydrous CuS." is the heat of hydration of CuS." A< +< Di&en the data at &alue of log Es! for AgI: A< +< at ,41E is, C< "5" 1>ECand that of C< =< 'hat is the C< =< =< 75- $>ECis Calculate +< /ence of C< isA =< and s!ecific

the EB( of the cell 9b?9bCl,??AgCl?Ag is # 72 and its tem!erature coefficient is If the heat of formation of is +< =< The heat of formation of AgCl is,

*%

-#<

Calculate the e)uilibrium constant for the reaction, ,(e @3 3 @I l

reduction !otentials in acidic conditions are # 55 and # 7" 2 res!ecti&ely for (e @3 ? (e,3 and I@ ? I cou!les A< 7 -#7 +< $ ,$ -#5 C< $ ,$ -#5 =< 7 -#7 Zn +, --< A gra!h is !lotted between Ecell and log The cur&e is linier with interce!t on Ecell axis e)uals to + , Cn - -#2 Calculate Ecell for the cell Zn ( s ) Zn +, ( # -M ) Cu +, ( # #-M ) cu A< - ,@2 -, +< - @,2

,(e,3 3 I@ The standard

C< - #52

=< - ,52

NO@ NO, ( acidic medium ) E # = # 1V concentra NO@ NH ,OH ( acidic medium ) E # = # 5"V ,

C.I98_Chemistry

Sri Chaitanya Narayana IIT Academy

/

Chemistry_Electrochemistry

At what 9 the abo&e two half reactions will ha&e same EB( &alues : Assume the concentration of all the s!ecies to be unity ;assume # #740# #$< A< - , +< , C< - 7 =< - $ -@ The standard !otential of O H , Ag ,O ( s ) Ag , and O H O, electrodes are, res!ecti&ely, # "" 2 and # "# 2 at ,7# CF for the formation of Ag ,O, H = ,4,4# J mol - and may be assumed to be inde!endent of tem!erature Calculate the tem!erature at which Ag ,O will begin to decom!ose in air ;,#G by &olume of ., A< ,7$ , J ? K ? mol +< ,"- , J ? K ? mol C< ,#$ " J ? K ? mol =< -"$ J ? K ? mol -" The EB( of the cellA Ag AgCl , # -MKCl # -M AgNO@ Ag is # "7 2 # - B ECl is 17G dissociated and # - B AgN.@ is 1,G dissocated Calculate the solubuluty !roduct of AgCl at ,7# C A< - 57 -#-# +< - 47 -#4 C< - 1 -#4 =< , $7 -#-# -7 Calculate the !otential corres!onding to the following cell gi&en , Pt CO +, ( , # M ) , CO +@ ( # #-M ) Cr +@ ( # 7M ) , Cr,O5 ( " #M ) , H + ( - 7M ) Pt E #CO +, ? CO +@ = - 1,V A< # ",2 -$
+, # +@ F E Cr,O5 ? Cr = - @@V +< # ,@& C< # @,&

=<C# -@&

At ,7# C , after the addition of --# m8 of # - N NaCl solution to -## m8 of # - N Ag NO@ solution, the reduction !otential of sil&er electrode !laced in it is # @$ 2 Assuming acti&ities to be identical with concentrations, calculate the solubility !roduct of AgCl A< , 1 -#-# +< , $ -#-# C< - " -#-# =< - 5@ -#-# The standard !otential of OH , Ag ,O( s ) ? Ag , and OH ? O, electrodes are res!ecti&ely # @""2 and # "#2 at ,7# C F for the formation of Ag ,O H = ,4,4# J mol and may be assumed be inde!endent of tem!erature Calculate the tem!erature at which Ag ,O will begin to decom!ose in air ;,#G by &olume of O, < A< ",5 #@K +< @4@ #@K C< "4@ #@K =< @$@ #@K

-5

-1

A staurated calomel electrode is cou!led through a salt bridge with a )uinhydrone electrode di!!ing in # -B NH "Cl The obser&ed EB( at ,7# C is # -7,2 (ind the dissociation constant of NH "OH The oxidation !otential of saturated calomel electrode 0 # $44V at ,7# C A< @ , -#7 +< " , -#7 C< , $ -#7 =< , -1 -#7 Calculate the EB( of the cell pt , H , ( - atm ) ? CH @COOH ( # -M ) ?? NH "OH ( # #-M ) ? H , , Pt ( - atm ) Ka CH @COOH = - 1 -#7 and Kb for NH "OH = - 1 -#7 A< # "757 +< +# "757 C< # $757 =< # $757

-4

,#

A cell Cu ? Cu ,+ ?? Ag + ? Ag initially contains -M Ag + and -M Cu , + ions calculate the change in cell !otential after !assage of 4 $7A of current for - hr A< Ecell decreases by # #-2 +< Ecell increases by # #-2 @

C.I98_Chemistry

Sri Chaitanya Narayana IIT Academy

C< Ecell decreases by # #72 ,Batch the following 8ist I A< Electrode re&ersible w r t cation +< Electrode re&ersible w r t anion C< Hedox Electrode =< Heference electrode

Chemistry_Electrochemistry
=< Ecell increases by # #72

8ist II !< Pt ? Fe , Fe
+, +@ + )< Pt ? H , ( -bar ) ? H ( a = -)

r< Ag ? AgCl ( s ) , HCl ( aq ) s< Ag ? AgNO@

,,

Calculate The minimum wt of Na./ re)uired to be added in H ! to consume all the H !resent in H/S of cell of emf of 3# 5#-2 at before its use ,7# C +, Zn ? Zn ( # -M ) ?? HCl ( -litre ) , H , ? Pt ( - atm ) E# = +# 5$V Zn ? Zn , + A< - ,$" gm +< , $7 gm

C< - $7 gm

=< @ , gm

,@

The e)ui&alent condutance of monobasic acid at infinite dilution is "@1 o"m-cm, If the resisti&ity of the solution containg -7g acid ( M # = "4 ) in -$ is -1 7 o"m cm what is the degree of disscussion of acid A< "7 4G +< "# ,G C< $# "G =< 7# 5G

,"

Calculate the log K eq for the reaction Zn + ,Ce+" Zn +, + ,Ce +@ E # +, = # 5$V F E # +@ = - $-V Ce ? Ce+" Zn ? Zn A< -#-# +< -#-, C< -#4

=< -#1

,7

MnO, is .xidised anodically /ow much time is re)uired to oxidise ,$ #1g of MnO, by a current of # 7A [ At #t Mn = 77] A< 7# ,-"rs +< "1 ,-"rs C< $, ,-"rs =< 7$ ,-"rs

C.I98_Chemistry

"

Sri Chaitanya Narayana IIT Academy

Chemistry_Electrochemistry

ELECTROCHEMISTRY + 3 ,EY - HI!TS

-+ 1+ -7 C ,= 4+ -$ = @C -# C -5 A " + -- C -1 = ,, A 7A -, A -4 ,@ + $+ -@ + ,# + ," A ,7 + 5+ -" A

,- A sF % r F C pF & q Cell reactionA (e;s< + ,/ + (e ,+ + / ,

E# E# E# cell 0 ,/ + ,/ , (e ,+ ,(e

0 # ;# ""< 0 3# ""2 IsaltJ = 7 ,# 3 log, 0 7 7, I/3J 0 -#7 7B !/ 0 !Ea 3 log IacidJ

# - = -#-# F n 0 , 7 7 , I/ J ;-# < # #74 # #74 E cell 0 E # log K = # "" log-#-# = # -"72 cell n , 7$# , Boles of /, 0 ,,"## 7$# 4$7## = 1 #" A Electric current 0 ,,"## $# -# @ D% 0 n(E% 0 , L 4$7## L - ,,11 >mol0 ,@5 -$# *> mol,@5 -$ = # 1@ Thermodynamic efficiency 0 ,17 $% Conce!tual K=
+ ,

I(e ,+ J9/ ,

&%

C.I98_Chemistry

Sri Chaitanya Narayana IIT Academy

'%

Chemistry_Electrochemistry

(%

)%

CCCCCCCCCC ;-< CCCCCCCCCCCC;,< Subtracting ;,< from ;-<

/eat of hydration of *% A!!lying

-# -Ecell = Ecell Zn +, # #74log +, n Cu

+, +, Ecell = - -F Zn = # -M F Cu = # #-M

-,

+alance both the half &action and a!!ly nernst e)uation Put [ NO, ] = NO@ = -M in the urt e)uation and NO@ = [ NH ,OH ] = -M in the second e)uation H Then E- = # 1 # -, P ( -)
E, = # 5" # #5 P H ( , )

E- = E, P H = - , -@ (ind ' # using ' # = nFE # $

C.I98_Chemistry

Sri Chaitanya Narayana IIT Academy

Then ' = H ( ! ! # = ,"- , J ? mol Ecell =
# Ecell

Chemistry_Electrochemistry

-"

Ag + anode 74 log + n Ag cat"ode

Ag + anode = , #77 -#4 M + 4 4 -# K !p = Ag Cl = , #77 -# ( # #17 ) = # -5"$ -# = - 57 -#

-7

$ , Co +@ Cr +@ # # #74- log Ecell = Ecell $ -" $ Co , + Cr O , H + , 5

Ecell = # @,V

-$

Cl # #74 # Ecell = Ecell log K sp

K H log , = K- , @#@ Conce!tual - - (- (,

-5 -1 -4

Ecell = E E$
Cu , + # #74 # Ecell = Ecell log , n Ag + Conce!tual (ind H Zn +, # 74 # in H / Electrode using Ecell = Ecell , log , H +

,# ,,,

,@

-### K = eq C = m ? m =
log K c = nE # # #74

,"

,7

MnO, Mn +5 + @e

C.I98_Chemistry