Sri Chaitanya Narayana IIT Academy Chemistry_Electrochemistry

Sri Chaitanya Narayana IIT Academy

Sri Sarvani Educational Society
COMMON CENTRAL OFFICE_MADHAPUR_HYD
CHEMISTRY : ELECTROCHEMISTRY
Assignment-2
1)
Match the following :-
Column-I Column-II
(A) or a gal!anic cell" the E
cell
# $ (%) &'($$ co)lom*s
(+) The charge carried *y
electrons
(,) The cell reactions are at
e,)ili*ri)m
(C) -)ring discharge of lead
storage *attery
(r) .
(-) (s) . moles of /
.
S0
1
are cons)med
(t) Cell reactions are re!ersed
2)
The chlorate ion can dis%ro%ortionate in *asic sol)tion according to the reaction
2 The e,)ili*ri)m concentration of the ions res)lting from
a sol)tion initially at $2& M in chlorate ion is then a is _______
( and )2
PARAGRAPH FOR !ESTIO" "O 2# - $%

2 ollowing techni,)e is ado%ted to chec3 s)s%ected dr)n3 dri!ers2 4ead the %assage and answer the
,)estions at the end of it2
5hen s)s%ected dr)n3 dri!ers are tested with a +reathaly6er" the alcohol (ethanol) in the e7haled *reath is
o7idi6ed to ethanoic acid with an acidic sol)tion of %otassi)m dichromate:
The +reathaly6er meas)res the colo)r change and %rod)ces a meter reading cali*rated in terms of *lood
alcohol content2
$)
Colo)r of the testing sol)tion changes from:
&)
If the standard half-cell %otential for red)ction of ethanoic acid to ethanol is $2$8 9 and that of red)ction
of to is &2(( 9" then of the reaction ta3ing %lace in alcohol meter is:
&) &2(' 9 .) &2.: 9 () -&2(' 9 1) -&2;& 9
')
5hat is the !al)e of E for the reaction when the concentrations of ethanol" ethanoic acid" "and
are &2$ M and the %/ is 12$$ <
&) $2(& 9 .) -&2$& 9 () &281 9 1) $2'; 9
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Sri Chaitanya Narayana IIT Academy Chemistry_Electrochemistry
PARAGRAPH FOR !ESTIO" "O ( ) #
0ne of the nicest a%%lication of red)ction %otential is the %rediction of the %rod)cts of reaction
in!ol!ing elements ha!ing se!eral o7idation states2 Consider the reaction of iodine with %ermanganate
in acid sol)tion2 The %ertinent diagram is shown *elow
()
5hat are s%ecies which are )nsta*le towards dis%ro%ortion
*)
5hen the reaction *etween and carried o)t with iodide in e7cess" then the %rod)cts of the
reaction are
#)
To the acidic %ermanganate sol)tion" iodide sol)tion is added dro%
wise the %rod)cts of reaction are
&) .) () 1)
PARAGRAPH FOR !ESTIO" "O + ) 11
?;2;ml of $28:. Normal sol)tion of Sodi)m *romate was %re%ared2 /alf cell reaction is
The dri!ing force diminishes to 6ero on the way to e,)ili*ri)m" @)st as in any other s%ontaneo)s
%rocess2 +oth and the corres%onding cell %otential are 6ero when the redo7 reaction comes
to e,)ili*ri)m2
The Nernst e,)ation for the redo7 %rocess of the cell may *e gi!en as
The 3ey to the relationshi% is the standard cell %otential E
$
" deri!ed from the standard
free energy change as :
+)
The e,)ili*ri)m constant Ac for the reaction :
5ill *e :
1%)
The !al)e of the reaction ,)otient B" for the cell is
11)
The standard emf of the cell" in which the cell reaction is $28&'; 9
at $
$
C and $28:;( 9 at .;
$
C2 The !al)e of of the reaction at .;
$
C is2
&.2 A hydrogen electrode %laced in a *)ffer sol)tion of NaCN and /CN in the mole ratio of C : D and D :
C has an o7idation electrode %otential !al)es E
&
and E
.
!olts res%ecti!ely at .;EC2 The %Aa !al)e of
/CN is
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Sri Chaitanya Narayana IIT Academy Chemistry_Electrochemistry
(A)
( )
& .
E E
$2&&?
+
(+)
( )
& .
E E
$2&&?
+

(C)
( )
& .
E E
$2&&?

(-)
( )
. &
E E
$2&&?

&(2 The e2m2f2 of the cell

Cd (s) F /g
.F
(a,) Cd
F.
(a,) F /g
is gi!en *y E # $28:$? G &2$. H &$
G1
(T G .; 9) where T is the tem%erat)re in EC and E in !olts2 The
entro%y change for the reaction is
(A) G &'28' I deg
G&
(+) G &.'2( 3I
(C) &'28' 3I deg
G&
(-) G '2?; I deg
G&

&12 If .
1
Mn0 J Mn
E &2;&9
+

and .
.
Mn0 J Mn
E &2.(9
+

" then
1 .
Mn0 J Mn0
E

is
(A) F$2.? 9 (+) G $2.? 9
(C) F $2:1 9 (-) F &28' 9
&;2 A gra%h is %lotted *etween E
cell
of ,)inhydrone half cell and %/ of sol)tion2 Interce%t is $28'' 92 At
what %/" E
cell
will *ecome $21'. 9<
(A) (2; (+) 12.
(C) : (-) &$
&82 Calc)late the cell EM in m9 for
( ) ( )
.
=t K / &atm K /Cl $2$&M K AgCl(s) K Ag(s)
at .'? A
Li!en :
f
L

(AgCl) # G &$'2;8 3Imol

G&
and
f
L

(/
F
F Cl
G
)
(a,)
# &($2:' 3I mol
G&


(A) 1;8 m9 (+) 8;1 m9
(C) ;18 m9 (-) none of these
&:2 At what
.
(
+r
C0

1
]
1
]
does the following cell ha!e its reaction at e,)ili*ri)m<
( ) ( )
. ( . (
Ag(s) K Ag C0 s K Na C0 a, KK A+r(a,) K Ag+r(s) K Ag(s)
Li!en : A
s%
# ? H &$
G&.
for Ag
.
C0
(
and A
s%
# 1 H &$
G&(
for Ag+r
(A)
:
& &$

(+)
:
. &$

(C)
:
( &$

(-)
:
1 &$

&?2 Calc)late the EM of the cell at .'? A

=t K /
.
(& atm) K Na0/ (7M)" NaCl (7M) K AgCl (s) K Ag (Li!en
Cl J AgClJ Ag
E $2...9

+
)
(A) &2$1? 9
(+) G $2$1 9
(C) G $28$1 9
(-) emf de%ends on 7 and cannot *e determined )nless !al)e of 7 is gi!en
&'2 Consider the cell Ag ( ) ( )
& .
Ag 7" C Ag y" C
+ +
Ag2 Li!en that C
.
# &$C
&
and that 7 and y are degrees
of dissociation in AgN0
(
sol)tion of concentrations C
&
and C
.
in the two half cells" then log
y
7
_

,
in
terms of the emf E of the cell at .'? Ael!in will *e
(A)
E
$2$;'
(+)
E
&
$2$;'
+
(C)
E
&
$2$;'
(-)
E
$2&&?
2
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Sri Chaitanya Narayana IIT Academy Chemistry_Electrochemistry
.$2 The standard red)ction %otentials of some half cell reactions are gi!en *elow :
.
. .
=*0 1/ .e =* ./ 0
+ +
+ + +


E &21;;9
.
1 .
Mn0 ?/ ;e Mn 1/ 0
+ +
+ + +


EE # &2;& 9
1 (
Ce e Ce
+ +
+


EE # &28&9
. . .
/ 0 ./ .e ./ 0
+
+ +


EE # &2:& 9
=ic3 o)t the correct statement :
(A) Ce
F1

will o7idi6e Mn
F.
to
1
Mn0

(+)
1
Mn0

will o7idi6e =* to =*0

.
(C) /
.
0
.
will o7idi6e Mn
F.
to
1
Mn0

(-) =*0
.
will o7idi6e Mn
F.
to
1
Mn0

.&2 Identify the incorrect statement (s)

(A) In the s%ontaneo)s chemical reaction of a gal!anic cell" electrons flow from the cathode to the
anode2
(+) In the e,)ation
cell 4/S >/S
E E E "

the
4/S
E

and
>/S
E

are the standard red)ction %otentials2

(C) -o)*ling the coefficients in a chemical reaction will s,)are the !al)e of A
e,
will do)*le LE and
will do)*le
cell
E

2
(-) Salt +ridge is essential for all ty%es of cells2
..2 Consider the cell Ag K Ag+r K A+r ($2$& M) K K ACl (&M) K AgCl K Ag with EM $2$;' 92 Concl)sion
inferred may *e
(A) The ratio of the sim)ltaneo)s sol)*ilities of AgCl and Ag+r in %)re water is &$$$
(+) It is concentration cell
(C) Change in concentration of ACl will not affect EM2
(-) A
S=
(AgCl) M A
S=
(Ag+r)
PARAGRAPH FOR !ESTIO" "O 2$ - 2'
Com,-e.ension:
The %otential of an electrode when each s%ecies in!ol!ed in it e7ists in the standard state is called its standard
%otential2 The standard red)ction %otential of a co)%le is the meas)re of its tendency to get red)ced2 A series
o*tained *y arranging the !ario)s co)%les in order of their decreasing standard %otential is called
electrochemical series2 Any of the two co)%les of this series @oined together gi!es an electrochemical cell in
which red)ction occ)rs at the electrode which occ)%ies the higher %osition2 The standard %otential of
hydrogen electrode is ta3en to *e 6ero *y con!ention2
Li!en *elow are the se,)ence of halfGreactions (acidic media) with rele!ant E
$
!al)es in !olt at .'?A2
$2;8$ .2.8 $2'; &2;$ &2&? . ( .
1 1 .
Mn0 Mn0 Mn0 Mn Mn Mn
+ +

Also gi!en some more
$
.'?
E data are:
$211 $2$(8 . (
(s)
e e e
+ + +

.(2 The E
$
for
.
1
Mn0 Mn
+
is e,)al to
(A) &2$;19 (+) &2;$89
(C) ;2.:9 (-) :2;(9
.12 The !al)e of E
$
of reaction:
. . (
1 .
Mn0 ;e ?/ Mn ;e 1/ 0
+ + + +
+ + + +
(A) $2:(19
(+) $2.?.9
(C) 121'?9
(-) CanNt *e calc)lated as concentrations of s%ecies are not gi!en2
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Sri Chaitanya Narayana IIT Academy Chemistry_Electrochemistry
.;2 or the all
e
(s)
K e
.F
($2&M) KK &$$ m> $2(M /A (%Aa #;2.)
mi7ed with ;$ m> $21M Na0/ K /
.
(& atm)" =t
the E
cell
at .'? (
4T
.2($( $2$;'9

and log
&$
.$ # &2() is e,)al to
(A) G$2&;9 (+) F$2&?;9
(C) G$2119 (-) F$2&1;9
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Sri Chaitanya Narayana IIT Academy Chemistry_Electrochemistry
ELECTROCHEMISTRY ) 2 /EY 0 HI"TS
&2 A- B O +-="4O C- ="4"S O -- T .2. (2( 12. ;21 82(
:2. ?2& '2& &$21 &&2& &.2A &(2A &12- &;2A &82A &:2+
&?2A &'2C .$2A"+"C .&2A"+"C"- ..2A"+"- .(2+ .12A .;2-
1)
/int) Conce%t)al2
2)
/int) .
$)
/int)
is orange changing to
&)
/int)
')
/int)
()
/int)or dis%ro%ortion of a s%ecies its s)ccessi!e red)ction %otential sho)ld *e greater than
%re!io)s ed)cation %otential2
*)
/int)
As" o7idi6es to " it will *e a*sor*ed *y %resent in the mi7t)re forms
#)
/int)
The %rod)cts of the reaction m)st *e sta*le in %resence at is not formed as
o7idi6e it to and is also not formed only is formed2
+)
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Sri Chaitanya Narayana IIT Academy Chemistry_Electrochemistry
/int)
1%)
/int)
11)
/int)
&.2 E
&
#
I
I
$2$;' &
log $2$;'%/
& /
+
+ +
1
]
# $2$;'
&
7
%Aa log
y
_
+

,
E
.
# F $2$;' %/
II
# $2$;'
y
%3a log
7
_
+

,
%Aa #
& .
E E
$2&&?
+
2
&(2
=
E
S n
T
_

,
here
1
=
E
&2$. &$
T

_

,
9 degree
G&

# . H '8;$$ (G &2$. H &$
G1
)
# G &'28' Ideg
G&
2
&82 Cell 4eaction : /
.
F .AgCl .Ag F ./
F
F .Cl

( ) ( )
cell reaction
L . &($2:' . &$'2;8 1.218

3I mol
G&

cell
1.18$
E $2..$9
. '8;$$

+

E
cell
# F$2..$ F
( )
1
$2$;' &
log
.
$2$&
# 1;8 m92
&:2 Ag
F

(cathod)

( )
&e
anode
Ag

E
cell
# E
cell
F
( )
( )
s%
s% . ( (
A Ag+r J +r
$2$;'
log
&
A Ag C0 J C0

1
]
1
]
:
(
+r
. &$
C0

1
]

1
]
2
&?2
&e
.
&
/ AgCl / Ag Cl
.

+
+ + +
E
cell
# $2.. F
$2$;' &
log
& / Cl
+
1 1
] ]
2
&'2 Cell reaction : Ag
F
(y" C
.
) Ag
F
(7" C
&
)
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E #
.
&
yC $2$;' &$ y
log $2$;'log
& 7 C 7

2
y E
log &
7 $2$;'

2
.$2 or .Mn
.F
F ;=*0
.
F 1/
F
;=* F
1
.Mn0

F ./
.
0 EE # &21;; G &2;& # negati!e2
4eaction is not fissi*le2
..2 The cell can *e re%resented as
Ag K Ag
F

( ) ( )
s% s%
A Ag+r A AgCl
KK Ag K Ag
+r Cl
+

_ _


1 1
] ]
, ,
Net reaction :
C A
Ag Ag
+ +

E
cell
# $2$;' log
( )
( )
s%
s%
A AgCl $2$&
& A Ag+r

( )
( )
s% (
s%
A AgCl
&$
&$
A Ag+r $2$&

>et the sim)ltaneo)s sol)*ilities of AgCl and Ag+r and 7 and y moles J litre res%ecti!ely2
AgCl (s)
( )
7
7 y
Ag Cl
+

+
+


Ag+r (s)
( )
y
7 y
Ag +r
+

+
+


A
s%
(AgCl) # ( ) 7 y 7 +
A
s%
(Ag+r) # ( ) 7 y y +

( )
( )
s% (
s%
A AgCl
7
&$
A Ag+r y

Th)s" the sim)ltaneo)s sol)tion of AgCl is &$

(
times the sim)ltaneo)s sol)tion of Ag+r2
.12
( . $
1 1
Mn0 Mn0 O E $2;89
+

.e . $
1 .
Mn0 Mn0 O E .2.89
+

e ( $
.
Mn0 Mn O E $2';9
+ +

e ( . $
Mn Mn O E &2;$9
+ + +

GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG
;e . $
1
$2;8 . .2.8 $2'; &2;$
Mn0 Mn O E
;
+ +
+ + +
# &2;$89
.;2
. $
e .e eO E $2119
+
+
( $
e e (eO E $2$(89
+
+
GGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGGG
. ( $
( $211) (($2$(8)
e e eO E
&
+ +
+
+ # G$2::.9
$
cell
E # . ( .
1
$ $
Mn0 "?/ "Mn e "e
E E
+ + + +

# &2;$8 G (F$2::.)
# F$2:(19
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