ALLEN® Electrochemistry 1

ELECTROCHEMISTRY 5 fuEufyf[kr lsy dk 298 K ij emf (V esa)

1. rRoksa dh 3d Js.kh ds fy, M2+ / M ds bysDVªksM x × 10–2 gSA

foHko dk eku ftlds fy, /kukRed gS] og gS: Zn|Zn2+ (0.1 M)||Ag+ (0.01 M)| Ag

(1) Zn (2) Fe (3) Co (4) Cu x dk eku gS ______A (fudVre iw.kk±d rd)

[fn;k gS :
2. MnO-4 / Mn2+ ;qXe dh vkWDlhdkjd {kerk esa
2.303RT
gksus okys ifjorZu dk ifjek.k x × 10–4 V gS] ;fn E0Zn2+ / Zn = -0.76V; EAg
0
+
/Ag
= +0.80V; = 0.059]
F

25°C ij H+ vk;u dh lkUærk dks 1 M ls 6. lsy fLFkjkad 1.3 cm–1 dh lsy esa 5.0 m mol dm–3
10–4 M rd ?kVk;k tkrk gSA x dk eku gS KCl ds tyh; foy;u dh pkydrk ekius ij
______A (fudVre iw.kk±d½ (H+ vk;u dh lkUærk 0.55 mS vkrh gS bl foy;u dh eksyj pkydrk

®
2+
ifjofrZr gksus ij MnO -4 rFkk Mn dh lkUærk gS _______ mSm2 mol–1
é 2.303 RT ù ¼fudVre iw.kk±d esa½
leku eku fyft,) ê fn;k gS : = 0.059ú
ë F û
7. 0.14 S m–1 pkydrk dk ,d KCl foy;u pkydrk
3. NO3– dks dkWij }kjk NO rFkk NO2 esa vip;u
lsy esa 4.19 W izfrjks/k iznf'kZr djrk gSA ;gh lsy
djuk foy;u esa HNO3 dh lkUnzrk ij fuHkZj
;fn ,d HCl foy;u ls Hkjrs gSa rks izfrjks/k fxjdj
djrk gS ([Cu2+] dks fLFkj rFkk PNO = PNO eku 2
1.03 W gks tkrk gSA HCl foy;u dh pkydrk
–
yhft,), dkWij }kjk NO dks NO rFkk NO2 esa
3 gS____× 10–2 S m–1A (fudVre iw.kk±d esa)
vipf;r djus dh Å"ekxfrd izofr leku gksus 8. vfHkfØ;k
ds fy, vko';d HNO3 dh lkanzrk 10x M gS rks 2Fe3+(aq) + 2I–(aq) ® 2Fe2+(aq) + I2(s)
2x dk eku gS _______. (fudVre iw.kkZd rd) ds fy, ekud eksyj eqDr ÅtkZ esa ifjorZu dk
[fn;k gS, 298 K ij EoCu 2+
/Cu
= 0.34 V, ifjek.k gSA DrG°m = – ______ kJ

EoNO– / NO = 0.96 V, EoNO– /NO = 0.79 V rFkk ¼fudVre iw.kk±d esa½

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3 3 2

é E oFe2+ /Fe(s) = -0.440 V; E Fe

o
3+ = -0.036 V ù
RT ê
/Fe(s)
ú
(2.303) = 0.059] ê E oI /2 I- = 0.539 V; ú
F F = 96500 C
ë 2 û
4. fuEufyf[kr vfHkfØ;k ij fopkj dhft,A 9. csfj;e DyksjkbM] lY¶;wfjd vEy rFkk
MnO -4 + 8H+ + 5e– ® Mn2+ + 4H2O, Eº = 1.51 V.
gkbMªksDyksfjd vEy dks vuUr ruqrk ij eksyj
MnO -4 ds 5 eksyksa dk vip;u djus ds fy, pkydrk,¡ Øe'k% 280, 860 rFkk 426 Scm2 mol–1
vko';d fo|qr dh ek=kk QSjkMs esa gS ____A gSA vuUr ruqrk ij BaSO4 dh eksyj pkydrk
gS________S cm2 mol–1
¼fudVre iw.kk±d esa½
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2 Electrochemistry ALLEN®
10. 6OH– + Cl– ® ClO3– + 3H2O + 6e– 15. uhps nks dFku fn;s gSA
10.0 g iksVSf'k;e DyksjV
s mRiUu djus ds fy, xA dFku I : KCl (izcy oS|qr vi?kV~;) dh lhekar
dh /kkjk dk izokg 10h rd djuk iM+rk gSA x dk eksyj pkydrk CH3COOH (nqcy
Z oS|qr vi?kV~;)
eku gSA _______A (fudVre iw.kkZad esa )
ds eku dh rqyuk esa vf/kd gSA
(KClO3 dh eksy lagfr = 122.6 g mol–1,
dFku II : fo|qr vi?kV~; dh lkUnzrk ?kVus ij
F = 96500 C)
11. fuEufyf[kr vfHkfØ;k dh ,d lsy eku yhft, & eksyj pkydrk ?kV tkrh gSA

Cu(s) + 2Ag+(1 × 10–3 M) ® Cu2+(0.250 M) + 2Ag(s)

mijksDr dFkuksa ds lnaHkZ esa uhps fn, fodYiksa esa

E 1cell = 2.97 V ls lgh mÙkj pqfu,A

(1) dFku I lR; gS ijUrq dFku II vlR; gSA
mijksDr vfHkfØ;k ds fy, Ecell ___________V
(2) dFku I vlR; gS ijUrq dFku II lR; gSA

®
gSA (fudVre iw.kkZad esa)
(3) nksuksa dFku I rFkk dFku II lR; gSA
[fn;k gS: log 2.5 = 0.3979, T = 298 K]
(4) nksuksa dFku I rFkk dFku II vlR; gSA
12. ,d lsy tks 25°C ij gS] fopkj dhft,
Zn | Zn2+(aq), (1 M) || Fe3+(aq), Fe2+(aq) | Pt(s) 16. xSYosuh lsy ds fy,
lsy foHko 1.500 V ij dqy vk;ju dk Fe3+ Zn(s) + Cu2+(0.02 M)® Zn2+ (0.04 M) + Cu(s),

vk;u ds :i esa va'k x × 10–2 gSA x dk eku Ecell =_______ × 10–2 V. (fudVre iw.kkZad esa)
________ gSA (fudVre iw.kkZad esa) 0 0
[iz;ksx djs : E Cu/Cu2+
= –0.34 V, E Zn/Zn2+
=+0.76
(fn;k gS : E 0Fe 3+
/ Fe 2 +
= 0.77 V, E 0
Zn 2 + / Zn
= - 0.76 V )
2.303 RT
V, = 0.059 V]
13. ,d nqcZy vEy HA ds 0.001 mol L foy;u dh –1 F

pkydrk 2.0 × 10–5 S cm–l gSA ;fn 17. 1.14 cm–1 lsy fLFkjkad dh pkydrk lsy ftlesa
L om (HA) = 190 S cm 2 mol -1 gks] rks HA dk 0.001 M KCl gS] dk 298 K ij izfrjks/k 1500 W gSA
vk;uu fLFkjkad (Ka) ______ × 10–6 ds cjkcj gSA 0.001 M KCl foy;u dh 298 K ij eksyj

(fudVre iw.kkZad esa) pkydrk, S cm2 mol–1 es]a gS_______A (fudVre

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14. lsy Cu(s)|Cu2+(aq) (0.1M)||Ag+(aq) iw.kk±d esa)

(0.01M)|Ag(s) 18. fuEu lsy vfHkfØ;k ij fopkj dhft, :
ds fy, lsy foHko E1 = 0.3095 V 9
2+ +
ˆˆ† CdSO4 . 9 H 2O( s ) + 2Hg( l )
Cd(s)+Hg2SO4(s)+ H2O(l ) ‡ˆˆ
lsy Cu(s)|Cu (aq) (0.01 M)||Ag (aq) (0.001M)| 5 5
Ag(s) E 0cell dk eku 25°C ij 4.315 V gSA ;fn
ds fy, lsy foHko = ______ × 10–2 V gksxk
DH° = –825.2 kJ mol–1 gS rks ekud ,UVªkWih esa
¼fudVre iw.kk±d esa½+
ifjorZu] DS°, J K–1 esa ____. (fudVre iw.kkZad esa)
2.303 RT
[mi;ksx dhft, % = 0.059 ] [fn;k gS : QSjkWMs fLFkjkad = 96487 C mol–1]
F

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 ALLEN® Electrochemistry 3
19. fyLV-I dk fyLV-II ls feyku dhft, %
fyLV-I ¼iSjkehVj½ fyLV-II ¼bdkbZ½
(a) lsy fLFkjkad (i) S cm2 mol–1

(b) eksyj pkydrk (ii) foekghu

(c) pkydrk (iii) m–1

q vi?kV~; dh fo;kstu fMxzh (iv) W–1 m–1

(d) oS|r

uhps fn;s fodYiksa esa ls lgha mÙkj pqfu,A

(1) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii)
(2) (a)-(iii), (b)-(i), (c)-(ii), (d)-(iv)
(3) (a)-(i), (b)-(iv), (c)-(iii), (d)-(ii)

®
(4) (a)-(ii), (b)-(i), (c)-(iii), (d)-(iv)

20. ;fn 0°C ij ejdjh dh pkydrk 1.07 × 106 S m–1

gS vkSj ejdjh ;qDr lsy dk izfrjks/k 0.243 W gS
rks lsy dk lsy fLFkjkad x × 104 m–1 gS]
x dk eku gS _______A (fudVre iw.kk±d esa)
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4 Electrochemistry ALLEN®
SOLUTION for same thermodynamic tendency

1. Official Ans. by NTA (4) E NO - / NO = E NO - /NO

3 3 2

Sol. Only copper shows positive value for electrode

2+
potential of M /M of 3d-series elements. 0.059 P
o
or, E NO - - log NO 4
3/NO
3 y´y
E ! / V(Cu 2+ / Cu) : + 0.34

2. Official Ans. by NTA (3776) 0.059 PNO2

= ENO
o
- - log
Sol. Eqn is-
/NO
3 2
1 y ´ y2

MnO-4 + HÅ + 5e- ® Mn+2 + 4H2O 0.059 P 0.059 PNO

or, 0.96 - log NO5
= 0.79 - log 3 2
Nernst equation: 3 y 1 y

0.059 [ Mn +2 ] é 1 ù 8
0.059 PNO 0.059 P
E cell = E Cell
0
- log
éë MnO -4 ùû êë H + úû or, 0.17 = - log 3 2 + log NO

®
5 1 y 3 y5
(I) Given [ H Å ] = 1M
0.0591 PNO 0.0591 P
[ Mn +2 ] 0.17 = - log 3 2 + log NO
0.059 1 y 3 y5
E1 = E0 - log
5 éë MnO-4 ùû
3
0.0591 PNO 0.0591 P
(II) Now : [ H Å ] = 10 -4 M 0.17 = - log 9 2 + log NO
3 y 3 y5
0.059 [ Mn +2 ] 1
E 2 = E0 - log ´
5 éë MnO4 ùû (10 -4 )8
-
0.0591 é PNO
3
PNO ù
0.17 = ê log 5
- log 9 ú
2

3 êë y y úû
0.059 Mn +2 0.059
= E0 - log + log10 -32
5 éë MnO 4 ùû
-
5
0.0591 é P y9 ù
0.059 0.17 = ê log NO ´ ú
therefore : E1 - E2 = ´ 32 3 êë y 5 PNO
3
2 ú
û
5
–4
= 0.3776 V = 3776 × 10 Assume PNO ; PNO2 = 1 bar
x = 3776

3. Official Ans. by NTA (4) 0.17 ´ 3

= log y 4 = 8.644
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0.059
Sol. If the partial pressure of NO and NO2 gas is
taken as 1 bar, then Answer is 4, else the 8.644
log y =
4
question is bonus.
NO3– + 4H+ + 3e– ¾® NO + 2H2O log y = 2.161

E oNO -
/ NO
= 0.96V y = 102.16
3

NO3– + 2H+ + e– ¾® NO2 + H2O \ 2x = 2 × 2.161 = 4.322

o
E NO3- /NO2 =0.79 Answer (4)
Let [HNO3] = y Þ [H+] = y and [NO3–] = y 4. Official Ans. by NTA (25)

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 ALLEN® Electrochemistry 5
5 Official Ans by NTA (147) 7. Official Ans. by NTA (57)
–
Sol. Zn(s) ® Zn 2+
+ 2e 1
(aq .)
Sol. k = ·G *
R
2Ag+(aq.) + 2e– ® 2Ag(s)
For same conductivity cell, G* is constant and
_________________________________________
hence k.R. = constant.
Zn ( s ) + 2Ag (+aq.) ® Zn 2(aq
+
.)
+ 2Ag(s)
\ 0.14 × 4.19 = k × 1.03
_______________________________________
0.14 ´ 4.19
E0cell = E0Ag + /Ag - E0Zn2 + /Zn or, k of HCl solution =
1.03
= 0.80 – (–0.76) –1
= 0.5695 Sm
= 1.56 V –2 –1 –2 –1
2+
= 56.95 × 10 Sm » 57 × 10 Sm
-0.059 [Zn ]
Ecell = 1.56 log 8. Official Ans. by NTA (46)
2 [Ag + ]2

®
Official Ans. by ALLEN (45)
0.059 0.1
= 1.56 - log 0
E1 E2
0

2 (0.01)2 Fe3+ Fe2+ Fe

0.059 Sol. E30

= 1.56 - ´3
2 E10 + 2E20 = 3E30
= 1.56 – 0.0885
E10 = 3E30 - 2E02
= 1.4715
= 147.15 × 10–2 = 3 (–0.036) – 2(–0.44)

6. Official Ans. by NTA (14) = + 0.772 V

n m.mol E0cell = E0Fe3+ /Fe2+ + EI0- /I = 0.233

Sol. Given conc of KCl = 2

L
D r G 0 = – 2 × 96.5 × 0.233 = –45 kJ
: Conductance (G) = 0.55 mS
9. Official Ans. by NTA (288)
ælö
: Cell constant ç ÷ = 1.3 cm -1 Sol. From Kohlrausch's law
èAø
To Calculate : Molar conductivity (lm) of sol. L ¥m (BaSO4 ) = l ¥m (Ba 2 + ) + l ¥m (SO24- )

1 k L ¥m (BaSO4 ) = L ¥m (BaCl 2 ) + L m
¥
(H 2 SO4 )
® Since l m = ´ ......(1)
1000 m –2 L ¥m (HCl)
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–3 mol
® Molarity = 5 × 10 = 280 + 860 – 2 (426)
L
= 288 Scm2mol–1
® Conductivity = G ´ æç l ö÷ = 0.55 mS ´ 1.3 m -1
èAø1 10. Official Ans. by NTA (1)
100 Sol. Given balanced equation is
–1
= 55 × 1.3 mSm 1 1
® ClO 3- + 3H 2 O + 6e -
60H + Cl ¾¾
n 1 55 ´ 1.3 mSm 2
eq (1) lm = ´ 10
1000 æ 5 ö mol ® 10g KClO3 Þ mol KCO 3 in obtained
ç ÷ 122.6
è 1000 ø
mSm 2
® from the above reaction, it is concluded that by
Þ l m = 14.3
mol 6F charge 1 mol KClO3 is obtained.

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6 Electrochemistry ALLEN®
® By the passage of 6F charge = 1 mol KClO3 13. Official Ans. by NTA (12)
x ´ 10 ´ 60 ´ 60
\ By the passage of F charge k
96500 Sol. L m = 1000 ´
M
1 x ´ 10 ´ 60 ´ 60
= ´
6 96500 2 ´ 10 –5
= 1000 ´ = 20 S cm2 mol–1
x ´ 10 ´ 60 ´ 60 10 0.001
Now =
6 ´ 96500 122.6
L m 20 æ 2 ö
Þ a= = =
Þx=
10 ´ 965
=
965
= 1.311 ; 1 L ¥m 190 çè 19 ÷ø
60 ´ 122.6 735.6
OR ˆˆ† H + + A –
HA ‡ˆˆ
E
W = ´I´t
F 0.001 (1– a) 0.001a 0.001 a
122.6 2
10 = ´ x ´ 10 ´ 3600 æ 2ö
0.001 ´ ç ÷

®
96500 ´ 6 æ a ö
2
è 19 ø
X = 1.311 Þ ka = 0.001 ç ÷=
è1- a ø æ 2ö
1- ç ÷
Ans.(1)
è 19 ø
11. Official Ans. by NTA (3)
0.059 [Cu +2 ] = 12.3 × 10–6
Sol. E = E° - log
2 [Ag+ ]2 14. Official Ans. by NTA (28)
0.059 0.25
= 2.97 - log -3 2 = 2.81V Sol. Cell reaction is :
2 (10 )
12. Official Ans. by NTA (24) Cu(s) + 2 Ag+ (aq) ® Cu2+ (aq) + 2Ag (s)
Sol. Zn ¾¾
® Zn2+ + 2e– é Cu 2 + ùû
0.059
Now, Ecell = EoCell – log ë ... (1)
2Fe3+ ¾¾
® 2e– + 2e2+ 2 éë Ag + ùû
2

_____________________________________________

Zn + 2Fe3+ ¾¾
® Zn2+ + 2Fe2+ 0.059 0.01
\ E1 = 0.3095= EoCell – . log 2 ... (2)
_____________________________________________
2 ( 0.001)
E0cell = 0.77 – (0.76) From (1) and (2) , E2 = 0.28 V = 28 × 10–2 V
= 1.53 V
2
15. Official Ans. by NTA (4 )
0.06 æ Fe 2+ ö
1.50 = 1.53 – log ç 3+ ÷ Sol. Ion H+ K+ Cl– CH3COO–
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2 è Fe ø
L ¥m S cm 2 /mole 349.8 73.5 76.3 40.9
æ Fe2+ ö 0.03 1
log ç 3+ ÷ = =
è Fe ø 0.06 2 So L¥m CH3COOH = L¥m (H+ ) + L¥m CH COO-
3
[Fe 2+ ]
= 101/2 = 10
3+
[Fe ] = 349.8 + 40.9
[Fe 3 + ] 1 = 390.7 Scm2/mole
=
[Fe 2 + ] 10
L ¥m KCl = L ¥m (K + ) + L ¥m (Cl - )
[Fe 3+ ] 1 1
2+ 3+
= =
[Fe ] + [Fe ] 1 + 10 4.16 = 73.5 + 76.3
= 0.2402
= 149.3 Scm2/mole
= 24 × 10–2
So statement-I is wrong or False.

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 ALLEN® Electrochemistry 7
As the concentration decreases, the dilution 18. Official Ans. by NTA (25)
increases which increases the degree of Sol. DG o = - nFE o = DH o - TDSo
DH o + nFE o
dissociation, thus increasing the no. of ions, =
T
which increases the molar conductance.
=
( -825.2 ´ 10 ) + ( 2 ´ 96487 ´ 4.315)
3

So statement-II is false. 298

-825.2 ´ 103 + 832.682 ´ 103
420 =
400 298
365
7.483 ´ 103
250 = = 25.11 JK -1mol -1
298
200
140 KCl \ Nearest integer answer is 25
CuSO4
CH3COOH
O 19. Official Ans. by NTA (1)

®
0 0.2 0.4
ælö
Sol. Cell constant = ç ÷ Þ Units = m–1
èAø
16. Official Ans. by NTA (109)
Molar conductivity (Lm) Þ Units = Sm2 mole–1
Sol. Galvanic cell: Conductivity (K) Þ Units = S m–1
Zn (s) + Cu (+aq2 .) ® Zn +2 + Cu(s) Degree of dissociation (a) ® Dimensionless
0.04 M
0.02 M
\ (a) – (iii)
0.059 [2n +2 ]
Nernst equation = Fcell = E o
cell - log (b) – (i)
2 [Cu +2 ]
(c) – (iv)
0.059 0.04
Þ Ecell éë E ocell - EoZn+2 / Zn ùû - log (d) – (ii)
2 0.02
20. Official Ans. by NTA (26)
0.059 2
Þ E cell [ 0.34 - ( -0.76 )] - log Sol. k = 1.07 × 106 Sm–1, R = 0.243 W
2
1 1
0.059 G= = W –1
Þ E cell 1 - 1 - ´ 0.3010 R 0.243
2
k = G × G*
–2
= 1.0911 = 109.11 × 10
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k 1.07 ´ 10 6
G* = = ; 26 × 104 m–1
= 109 G 1
0.243
17. Official Ans. by NTA (760)
ææ 1 ö ö
Sol. K <
1
≥∋l A( < çç ÷ ≥ 1.14 ÷÷ S cm - 1
R ççèççè 1500 ø÷÷ ÷ø

æ 1.14 ÷ö
çç
çè 15 00 ÷÷ø
Þ Ùm < 10 00 ≥ S cm 2 m ol –1
0.001

= 760 S cm2 mol–1

Þ 760