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BI TP IN PHN V QU TH

1. 298K, dng in cc Pt in phn dung dch c nng Zn2+ v Cd2+ u l 0,1


mol.kg-1 tch 2 kim loi . Cho bit qu th ca H2 in cc Pt l 0,6V; h s hot
ca cc cht u bng 1.
(1) Kim loi no xut hin trc catot?
(2) Khi kim loi th 2 bt u xut hin th nng ca kim loi th nht cn li trong
dung dch l bao nhiu?
(1) Cd b kh trc; (2) [Cd2+] 6,0 10-14m
(1) Th phn hy cc cation c th b kh catot
RT
RT
ln a Zn 2+ = -0,763 +
ln 0,1 = -0,793V
2F
2F
RT
RT
o
ln a Cd 2+ = -0,403 +
ln 0,1 = -0,433V
Cd2+ /Cd = Cd2+ /Cd +
2F
2F
RT
RT
ln a H+ - H2 =
ln10 7 - 0,6 = -1,014V
H+ / H2 =
F
F

Zn 2+ / Zn

o
Zn 2+ / Zn

Th phn hy dng hn s b kh trc, nh vy Cd s xut hin trc.


(2) Zn2+ bt u b kh, tc s kh Zn2+ v Cd2+ xy ra ng thi, lc ny:
Zn / Zn = Cd /Cd
2+

Zn 2+ / Zn

2+

= - 0,793 =

Cd 2+ /Cd

o
Cd2+ /Cd

RT
RT
ln a Cd 2+ = -0,403 +
ln a Cd 2+
2F
2F

a Cd = 6,0 10-4 [Cd2+] = 6,0 10-4 mol.kg-1


2+

2. Dng in cc Pt in phn dung dch SnCl2. Do c qu th ca H2 catot nn Sn2+ b


o
kh trc. anot c kh O2 xut hin. Bit a Sn = 0,10, a H = 0,01. Sn /Sn = -0,140V,
2+

o
O2 ,H + /H 2O

2+

= 1,23V. Qu th O2 anot l 0,3V.


(1) Sc in ng phn cc l bao nhiu
(2) Bit qu th H2 catot l 0,5V. Hi bt u c kh H2 thot ra th nng Sn2+ l
bao nhiu?
(1) Epc 1,782V; (2) [Sn2+] 2,9 10-14m
(1) Cc phn ng xy ra: catot Sn2+ + 2e Sn
1
2

Anot H2O 2e O2 + 2H+

catot

anot

RT
RT
ln a Sn 2+ = -0,140 +
ln 0,10 = -0,170V
2F
2F
RT
RT
o
ln a H+ + O2 = 1,23 +
ln 0, 01 + 0,5 = 1,612 V
= O2 ,H+ /H 2O +
F
F

Epc =

o
Sn 2+ /Sn

anot

catot

= 1,612 0,170 = 1,782V

(2) anot, ng thi c s thot kh O2 v s hnh thnh H+. Khi Sn2+ b kh gn ht th


H+ 0,1 2 + 0,01 = 0,21
c H2 thot ra th

H + / H2

a Sn

2+

RT
ln a H+ -
F

H2

RT
ln 0, 21 - 0,5 =
F

Sn 2+ /Sn

o
Sn 2+ /Sn

RT
ln a Sn 2+
2F

= 2.9 10-4 [Sn2+] = 2.9 10-4 mol.kg-1

/Sn

3. Dng in cc Ni in phn dung dch ZnSO4 1,10m. Bit Ni / Ni = -0,25V. Qu th


H2 trn Ni l 0,42V, qu th O2 trn Ni l 0,1V. Hi cht no xut hin trc catot v
anot? Gi thit dung dch l trung tnh v h s hot ca cc cht u l 1.
Ni2+ b kh trc, Ni2+ b oxi ha trc
catot c th xy ra s kh Ni2+ v H+. th phn hy l:
2+

Ni 2+ / Ni

H+ / H2

=
=

o
Ni2+ / Ni

RT
RT
ln a Ni2+ = -0,25 +
ln1,10 = -0,249V
2F
2F

RT
ln a H+ -
F

H2

RT
ln107 - 0,42 = -0,833V <
F

Ni 2+ / Ni

Ni2+ b kh trc
anot c th xy ra s oxi ha H2O v Ni (dng lm in cc) cn SO 24 rt kh b
oxi ha (2SO 24 - 2e S2O82- 2,05V)
1
2

H2O -2e O2 + 2H+


Ni 2e Ni2+
( vn tnh theo th kh)
O

2 ,H

Ni 2+ / Ni

/H 2O

= Oo

2 ,H

RT
RT
ln a H2 + a1/2
ln10 7 + 0,1 = 0,917V
O 2 + O 2 = 1, 23 +
2F
2F
RT
RT
ln a Ni 2+ = -0,25 +
ln1,10 = -0,249V< O2 ,H + / H2O
+
2F
2F

/H 2 O

o
Ni2+ / Ni

Ni b oxi ha trc
4. Mun dng in cc Pt in phn dung dch cha CdCl2 1,0m, NiSO4 1,0m th cn
phi t vo hai in cc ca bnh in phn mt hiu in th bng bao nhiu? V lc
hai cc bnh in phn xut hin cht g? (khng tnh n qu th, u bng 1)
E = 1,065, xut hin Ni v O2
2+
2+
+
catot c th xy ra cc phn ng kh Cd , Ni v H :
o
Ni / Ni = Ni / Ni = -0,25V
2+

Cd 2+ /Cd

H+ / H2

2+

=
=

o
Cd2+ /Cd

= -0,402V

RT
RT
ln a H+ =
ln107 = -0,414V
F
F

Th dng hn s b kh trc Ni2+ b kh thnh Ni xy ra trc

1
2

anot c s oxi ha Cl- v OH- (2OH- -2e O2 + H2O)


Cl
O

2 /Cl

RT
RT
ln aCl = 1,358
ln 2, 0= 1,340V
F
F
RT
RT
= oO ,H O/OH
ln a OH = 0, 401
ln10 7= 0,815V
2
2
F
F

o
= Cl

2 ,H 2 O/OH

2 /Cl

Nh vy anot xy ra s oxi ha to O2 trc


5. 298K, 1 atm, dng Pt lm catot, C (than ch) lm anot in phn dung dch c cha
CdCl2 0,01m v CuCl2 0,02m. Khng tnh n qu th v h s hot cc cht l 1.
Hi:
(1) Kim loi no b kh trc
(2) Kim loi th 2 bt u b kh th hiu in th lc ny l bao nhiu?
(3) Khi kim loi th 2 bt u b kh th nng ion cht u cn trong dung dch l bao
nhiu?
(4) Thc t c s tn ti ca qu th O2 trn than ch, nu (O2) = 0,6V anot xy ra
phn ng no trc?
Cu2+, H+, Cd2+; (2) E=1,608V; (3) [Cu2+] 9,346.10-28m; (4) O2 b oxi ha trc
(1) Cc ion c th b kh l Cd2+, Cu2+ v H+
RT
RT
ln a Cd 2+ = -0,403 +
ln 0, 01 = -0,462V
2F
2F
RT
RT
o
ln a Cu 2+ = 0,337 +
ln 0, 02 = 0,287V
Cu 2+ /Cu = Cu2+ /Cu +
2F
2F
RT
RT
ln a H+ =
ln107 = -0,414V
H+ / H2 =
F
F

Cd 2+ /Cd

o
Cd 2+ /Cd

Cu2+ b kh trc, tip theo l H+, cui cng l Cd2+


(2) anot:
Cl
O

2 /Cl

2 ,H

RT
RT
ln
a
ln 0, 06= 1, 430V
= 1,358
Cl
2 /Cl
F
F
RT
RT
= Oo ,H+ /H O +
ln aH + = 1, 229+
ln10 7 = 0,815V < Cl2 /Cl
2
2
F
F

o
= Cl

/H 2O

H2O b oxi ha thnh O2 trc.


Khi Cd2+ bt u b kh th Cu2+ b in phn gn ht, ng thi c s oxi ha
to thnh H+ anot.
a H+ = 2 0, 04 = 0, 04

2 ,H

/H 2O

E = O ,H
2

= Oo
+

/ H 2O

2 ,H

/H 2O

RT
RT
ln aH + = 1, 229+
ln 0, 04= 1,146V
F
F

Cd 2+ /Cd

= 1,146 (-0,462) = 1,608V

(3) Khi kim loi th 2 bt u b kh th Cu

2+

/Cu

= Cd 2+ /Cd

0,337 +

RT
ln a Cu 2+ = 0, 642
2F

a(Cu2+) = 9,346 10-28 [Cu2+] = 9,346 10-28m


(4) Khi tnh n qu th ca O2 th:
O

2 ,H

/H 2 O

= Oo

2 ,H

/H 2 O

RT
RT
ln aH+ + O2 = 1, 229+
ln10 7 + 0, 6= 1, 415V < Cl2 /Cl
F
F

vn l s oxi ha to ra O2 xy ra trc
6. 298K, 1atm, in phn dung dch c cha Ag+ (a=0,05), Fe2+ (a=0,01), Cd2+
(a=0,001), Ni2+ (a=0,1) v H+ (a=0,001) v gi thit rng nng H+ khng thay i
trong qu trnh in phn. Bit qu th ca H2 trn Ag, Ni, Fe v Cd ln lt l 0,20,
0,24, 0,18 v 0,30V. t vo hai in cc mt hiu in th tng dn t 0, hi th t cc
cht b kh catot.
Ag, Ni, H2, Cd, Fe
in cc Pt:

RT
RT
ln a Ag+ = -0,7794 +
ln 0, 05 = 0,722V
F
2F
RT
RT
o
ln a Fe2+ = -0,4402+
ln 0, 01 = -0,4994V
Fe2+ /Fe = Fe2+ / Fe +
2F
2F
RT
RT
o
ln a Cd 2+ = -0,403 +
ln 0, 001 = -0,4917V
Cd 2+ /Cd = Cd 2+ /Cd +
2F
2F
RT
RT
o
ln a Ni 2+ = -0,25 +
ln 0,1 = -0,2796V
Ni 2+ / Ni = Ni2+ / Ni +
2F
2F
RT
RT
ln a H+ =
ln 0, 001 = -0,1775V
H+ / H2 =
F
F
Ag + /Ag

o
Ag+ / Ag

cc in cc khc:
RT
ln a H+ -
F
RT
ln a H+ -
Ni: H+ / H2 =
F
RT
ln a H+ -
Fe: H+ /H2 =
F
RT
ln a H+ -
Cd: H+ /H2 =
F

Ag:

H + /H2

H2

/Ag= -0,1775 - 0,2 = -0,3775V

H2

/Ni= -0,1775 - 0,24 = -0,4175V

H2

/Fe= -0,1775 - 0,18 = -0,3575V

H2

/Cd= -0,1775 - 0,3 = -0,4775V

> Ni / Ni > H /H /Ag, Ni, Fe, Cd > Cd /Cd >


th t cc cht sinh ra catot l: Ag, Ni, H2, Cd, Fe
Ag + / Ag

2+

2+

Fe2+ /Fe

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