CHNG 4: CN BNG OXI HA KH

I.CC KHI NIM C BN

Bi tp c hng dn
IV.1.1. Vit y v cn bng phng trnh phn ng cho di dng sau:
KMnO 4 + H 2C 2O 4 + H 2SO 4 MnSO 4 + CO 2 + ....

Vit phng trnh phn t v ion. Hy ch r cht oxi ho, cht kh, cc cp oxi
ho - kh lin quan n phn ng, qu trnh oxi ho v qu trnh kh....
Hng dn
Xc nh cp oxi ho - kh: trong phn ng trn s oxi ho ca Mn gim v s oxi
ho ca C tng. Vy c hai cp oxi ho - kh l MnO 4- /Mn 2+ v CO 2 /H 2C 2O 4
Cn bng phng trnh phn ng:
2 MnO4- +8H+ +5e Mn2++4H2O
5
H2C2O4 2CO2+2H++2e
2MnO4- +5H2C2O4 +6H+ 2Mn2+ +10CO2 +8H2O
Phng trnh phn t:
2 KMnO 4 + 5 H 2C 2O 4 + 3 H 2SO 4 2 MnSO 4 +10 CO 2 + K 2SO4 + 8 H 2O

- MnO -4 (hay KMnO 4 ) l cht oxi ho (hay cht b kh), b kh xung Mn 2+ .

- H 2 C2 O4 l cht kh (hay cht b oxi ho), b oxi ho ln CO2 .
- Qu trnh (1) l qu trnh kh, trong cht oxi ho MnO4 thu electron
chuyn thnh dng kh lin hp Mn2+
- Qu trnh (2) l qu trnh oxi ho, trong cht kh H2C2O4 nhng electron
chuyn thnh dng oxi ha lin hp CO2.
IV.1.2. Xc nh cc cp oxi ho kh v hon thnh phng trnh phn ng theo s
sau:
PbO2 + Mn2+ MnO4- + .......
Hng dn

Trong phn ng trn c s thay i s oxi ho ca Mn: tng t +2 tr ln +7;

chng t y l phn ng oxi ho - kh, trong Mn2+ ng vai tr l cht kh, hnh
thnh nn cp oxi ho - kh th nht l MnO -4 /Mn 2+
Nh vy PbO2 s ng vai tr l cht oxi ho (vi s oxi ho ca Pb l +4), s b
kh v dng c s oxi ho thp hn l Pb2+ (dng kh lin hp), hnh thnh nn cp oxi
ho - kh th hai l PbO2/Pb2+:
Mn2++4H2O MnO4- +8H+ +5e

2
5

2+

qu trnh kh

PbO2 +4H +2e Pb +2H2O

2+

qu trnh oxi ho

2+

2Mn + 5PbO2 +4H 2MnO4 +5 Pb +2H2O (phng trnh ion)

Phng trnh phn t:
2 Mn(NO3 )2 + 5 PbO 2 +6 HNO3 2 HMnO 4 + 5 Pb(NO 3 ) 2 + 2 H 2O

IV.1.3. Hy hon thnh v cn bng phng trnh phn ng theo s sau:

C r2 O72 ... ... I 2 ...

Li gii:
Trong C r2 O 72 , crom trng thi oxi ho cao nht l +6, do C r2 O 72 l cht oxi
ho v s b kh v dng kh lin hp l C r3 to thnh cp oxi ho kh th nht l
C r2 O72 /Cr 3 . V C r2 O 72 l cht oxi ho, do s phn ng vi mt cht kh to thnh

dng oxi ho lin hp l I2 (c s oxi ho l 0). Cht kh phi l I- (l cht c s oxi

ho tng t -1 n 0), to thnh cp oxi ho kh th hai l I2/2I-. Phn ng xy ra nh sau:
(qu trnh kh)
2-

3+

Cr2O7 +14H +6e

2I
Cr2O7

2-

+ 2I + H

2Cr +7H2O
I2 +2e

(qu trnh oxi ho)

3+

2Cr +7H2O+ I2

K 2Cr2O7 + 6 KI+ 7 H 2SO 4 Cr2 (SO4 )3 + 3 I2 + 4 K 2SO4 + 7 H 2O

Bi tp vn dng
IV.1.4. Cn bng cc phng trnh phn ng theo phng php ion electron. Ch r cht
oxi ho, cht kh, cc cp oxi ho - kh lin quan n phn ng, qu trnh oxi ho, qu
trnh kh:

a) Al NO3 AlO2 NH 3
b) FeCuS 2 NO3 Fe3 Cu 2 SO42 NO
c)Cu ( NH 3 )42 CN Cu (CN )34 CNO
d ) IO3 I I3
e) Sn 2 BrO3 Cl Br SnCl62

IV.1.5. Hon thnh cc phng trnh phn ng sau. Cho bit cht oxi ho, cht kh, qu
trnh oxi ho, qu trnh kh:
a) Cr 3 NO2 OH CrO42 NO
b) Fe3 P NO3 Fe3 H 2 PO4 NO
c) BiO3 Mn 2 MnO4 BiO
d) Fe2 Si NO3 H 2 SiO3 NO
IV.1.6. Hy hon thnh cc phng trnh phn ng sau di dng phng trnh ion v
phng trnh phn t cho cc cp oxi ho-kh:
a) MnO4 H 2 S H 2 SO4 S .......
b) MnO(OH )2 H 2O2 Mn 2 .......
c) Mo3 Ce 4 MoO42 .......
d) H 3 AsO4 Zn H AsH 3 .......
e) Au HNO3

HAuCl4 .......

IV.1.7. Xc nh dng oxi ho (hoc kh) cn thiu. Cn bng v vit y cc phng

trnh phn ng di dng ion v phn t:
a) SnS 2 ........

H 2 SnO3 SO42 NO2

b) Pbo2 H 2O2 ........... Pb(CH 3COO) 2 .......

c) Pt HCl ............ NO H 2O
d) AuCl4 ...........

Fe3 Cl Au

II.TH IN CC
IV.2.1. Hy vit s pin in ho biu din th in cc tiu chun ca cp:
a) Ni2+/Ni;
b) O2/H2O;
c) Fe3+/Fe2+. Cho bit catot, anot
trong mi trng pin v sc in ng (s)ca mi pin in ho.
Hng dn

a) H 2 ( Pt ), pH 1atm H 1M N i2 1M Ni

(1)

b) H 2 ( Pt ), pH 1atm H 1M H 1M , H 2O O2 ( Pt ) pO 1atm
2

(2)

c) H 2 ( Pt ), pH 1atm H 1M Fe3 1M , Fe2 1M Pt

(3)

Trong pin (1): cc Ni l anot, cc hiro l catot.

0
0
EPin (1) EPin
(1) E Ni 2 / Ni 0, 233V

Trong pin (2) v pin (3): cc Hiro l anot, cc Pt l catot.

0
0
0
0
EPin (2) EPin
(2) EO2 / H 2O 1, 229 V v EPin (3) EPin (3) EFe3 / Fe 2 0, 771V

IV.2.2. Hy cho bit phn ng no xy ra trong cc trng hp sau:

a) FeCl3+NaCl;
b) FeCl3+NaBr; c) FeCl3+NaI;
Hng dn
So snh gi tr th in cc tiu chun ca cc cp, ta c :
ECl0

2 /2 Cl

0
1, 359V EBr2 (l )/2 Br 1, 065V EFe
0, 771V E I0 0,5355V ,
3
/ Fe 2
3

3+

Do kh nng oxi ho ca Cl2v Br2 mnh hn Fe v tnh oxi ho ca Fe3+ mnh hn

I 3 , do phn ng a) v b) khng xy ra, ch c phn ng c) xy ra:

2Fe3+ +3IHay:

2FeCl3 +3NaI

0
IV.2.3. Cho ECd

/ Cd

2+
2Fe + 3I3

2FeCl2 + 3NaI3+2NaCl

0
0, 402 V ; ECu
0,337 V . Hy so snh kh nng oxi ho, kh nng
2
/ Cu

kh ca cc dng oxi ho, kh ca hai cp trn.

Hy gii thch v sao Cu khng kh c Cd2+
Nu ghp hai cp thnh pin qua cu mui KCl, hy biu din s pin v chiu
chuyn ng ca cc phn t tch in trong pin.
Hng dn
0
0
ECu
ECd
Cd 2 oxi ho km hn Cu
2
2
/ Cu
/ Cd

Cu2+ +2e
Cd

2+

Cu
Cd +2e

2+

v Cd c tnh kh mnh hn Cu:

(qu trnh kh)
(qu trnh oxi ho)

2+
Cu2+ + Cd
Cd +2e
Phn ng din ra theo chiu thun ngha l Cu khng kh c ion Cd2+.

Trn catot (cc dng) lun lun xy ra qu trnh kh trn anot (cc m) lun lun
xy ra qu trnh oxi ho, vy ta c s pin:
() Cd Cd 2 1M Cu 2 1M Cu ()

Chiu chuyn ng ca cc phn t tch in:

- Trong dy dn: electron di chuyn t tri qua phi.
- Trong dung dch: ion dng (Cd2+,Cu2+)chuyn ng t tri qua phi. ion m
( SO42 , HSO4 , nu dng cc mui sunfat) di chuyn t phi qua tri.
-

Trong cu mui: ion K+chuyn ng t tri qua phi, ion Cl- theo chiu ngc
li.

IV.2.4. Cho phn ng: Cu 2 Fe3 Cu 2 2 Fe 2

a) Hy so snh E0 ca hai cp oxi ho - kh trn. Khi ghp thnh pin th cp oxi ho
kh no ng vai tr anot, catot? V sao?
b) Biu din s pin c dng xc nh E0 ca hai cp trn. Cho bit du ca
cc cc trong pin, bit rng E0 pin trong c hai trng hp u dng.
Hng dn
a)
Theo phn ng th Fe3+ l cht oxi ho; Cu l cht kh, cc cp oxi ho kh l
Fe3+/Fe2+ v Cu2+/Cu. Phn ng xy ra gia dng oxi ho ca cp c E0 ln vi dng
0
kh ca cp c E0 b hn, v vy EFe

/ Fe 2

0
ECu
2
/ Cu

Khi ghp thnh pin th cp Fe2+/Fe3+ ng vai tr catot (cc dng) v ti xy ra

qu trnh kh : Fe3+ +e
Fe2+
Cn cp Cu2+/Cu ng vai tr anot (cc m), xy ra qu trnh oxi ho:
b) V E 0pin 0 nn in cc hiro l cc m.
H 2 ( Pt ), pH 2 1atm H 1M Fe3 1M , Fe 2 1M Pt
H 2 ( Pt ), pH 2 1atm H 1M Cu 2 1M Cu
0
IV.2.5 Cho bit E Ag

/ Ag

0
0,80 V ; EZn
0, 76 V
2
/ Zn

a) Hy biu din s pin c dng xc nh th in cc tiu chun ca cc

cp cho trn. Hy ch r catot, anot
b) Nu ghp pin gm hai in cc tiu chun Ag v Zn th s ca pin s bng bao
nhiu? Hy cho bit phn ng xy ra khi pin hot ng.

Hng dn
a)

H 2 ( Pt ), pH 2 1atm H 1M Ag 1M Ag

(1)

H 2 ( Pt ), pH 2 1atm H 1M Zn 2 1M Zn

(2)

0
Trong pin (1): cc Ag l catot, cc hiro l anot v E Ag

Trong pin (2): cc Zn l anot, cc hiro l catot v E

0
b)Theo quy c S1= E pin (1) E Ag

0
S2= E pin (2) EZn

/ Ag

/ Ag

0
Zn 2 / Zn

E20H / H

0.76 E20H / H ( 0)
2

0
E20H / H E Ag
0.80 V

/ Ag
2

0
E20H / H EZn
0.76V
2
/ Zn

/ Zn

Theo quy c: in cc tri (in cc hiro) lun xy ra qu trnh oxi ho, in

cc phi lun xy ra qu trnh kh:
H2 2H+ +2e
Ag+ +1e Ag
Zn2+ +2e Zn
Nh vy phn ng xy ra theo quy c:
H2 +2Ag+

2H+ +2Ag

(trong pin (1))

H2 +Zn2+ 2H+ +Zn(trong pin (2))

M EPin (1) 0 Phn ng thc t xy ra khi pin (1) hot ng trng vi phn ng
quy c.
Ngc li EPin (2) 0 Thc t khi pin (2) hot ng th phn ng trong pin ngc
chiu vi chiu quy c, tc l:
IV.2.6. Ghp 2 cc Pt/Fe3+, Fe2+,H+ v Pt/Sn4+, Sn2+, H+ thnh pin qua cu mui KCl, bit
hot ca cc cu t u bng 1; EFe0

/ Fe2

0
0, 771 V , ESn
0,14 V . Hy biu din s
4
/ Sn 2

pin , cho bit cc no l anot, catot? Vit phng trnh phn ng xy ra khi pin hot
0
ng v tnh E pin
.

Hng dn:
V EFe0

3+

/ Fe2

2+

4+

0
0, 771 V ESn
0,14 V nn catot l cp Fe / Fe , anot l cp Sn /Sn
4
/ Sn 2

S pin:
Pt Sn 4 ,Sn 2 , H : (i) 1M Fe3 / Fe 2 , H : (i) 1M Pt

2+

 iu kin tiu chun :

0
0
0
E pin
EFe
ESn
0, 771 0,14 0, 63 V
3
4
/ Fe 2
/ Sn2

Fe3+ +e
Fe2+
Ti anot xy ra qu trnh oxi ho :
Sn2+ Sn4+ +2e
Ti catot xy ra qu trnh kh :

V phn ng xy ra khi pin hot ng l :

2Fe3+ + Sn2+

2Fe2+ + Sn4+

Bi tp vn dng
IV.2.7. Cho bit ngha ca cc gi tr th tiu chun sau :
0
E Ag
0, 799 V ;

/ Ag

0
ECo
0, 277 V
2
/ Co

0
EPb
0,126 V ;
2
/ Pb

0
EMnO
0, 564 V

/ MnO 2

IV.2.8. Dng gi tr E

ca cc cp oxi ho- kh (tra bng th in cc). Hy xc nh

chiu phn ng xy ra trong cc trng hp sau y, vit phng trnh phn ng :

a) MnO2 MnO4 Mn 2
b) MnO4 Br MnO2 Br2
c) MnO2 S MnO4 S 2 H 2O
0

t
d ) MnO4 Ag
MnO42 Ag

e) MnO2 H 2O2 H Mn 2 O2 H 2O

Tr li : a) ; c) ; d) : chiu nghch : b) ; e) : chiu thun

IV.2.9. Da vo gi tr th in cc tiu chun, hy cho bit nhng trng hp no c
phn ng xy ra theo chiu thun ? Gii thch.
a) HClO H 2O2 HCl O2 H 2O
b)VO 2 S H 2O VO2 H 2 S H
c)Cr2O72 I H Cr 3 I 2 H 2O
d ) H 3 AsO4 I 2 H H 3 AsO3 I H 2O
e)CrO2 OH Cl Cl2 CrO42 H 2O
xt
f )Cr 3 S 2O82 H 2O
Cr2O72 SO42 H 2O

Tr li : trng hp c phn ng : a) ; c) ; f).

IV.2.10. Hy biu din s pin ,tnh sc in ng ca pin v vit cc phng trnh
phn ng xy ra trong pin(khi hot ng) c to thnh bi cc cp in cc sau iu
kin tiu chun.
a) Fe2+/Fe v Pb2+/Pb
b)Zn2+/Zn v Sn2+/Sn

c)Ni2+/Ni v Cu2+/Cu
d)Cd2+/Cd v Ag+/Ag
Tr li : a) 0,314 V ; b) 0,619 V ;c) 0,57 V ; d) 1,201 V
IV.2.qq Trong cc pin sau, pin no c phn ng thc t xy ra ngc vi phn ng quy
c? Vit cc phng trnh phn ng.
a) H 2 ( Pt ), pH2 1atm H 1M I 1M , AgI Ag
b) H 2 ( Pt ), pH 2 1atm H 1M H 1M , TiO 2 1M Ti
c) H 2 ( Pt ), pH 2 1atm H 1M V 3 1M ,V 2 1M Pt
d ) H 2 ( Pt ), pH 2 1atm H 1M H 1M , ClO41M , ClO31M Pt

IV.2.12. Hy d on cc dng bn nhit ng ca cc dng oxi ho kh ca mngn trong

dung dch pH =0. Cho bit:
0
0
0
EMnO
=0,564 V; EMnO
=2,26 V; EMnO

2
/ MnO 2
/ MnO
4

2 / Mn

=0,95 V;

0
0
EMn
=1,51 V; EMn
=-1,18 V.
3
2
/ Mn 2
/ Mn

Vit cc phng trnh phn ng minh ho.

Hng dn: So snh cc gi tr E 0 ca cc cp oxi ho kh k tip tm cc dng
c kh nng t oxi ho kh.
Tr li: Dng bn l MnO4 ; MnO2 v Mn 2 .
IV.2.27. Da vo th tiu chun ca cc cp Cl2 / 2Cl ; Br2 / 2 Br ; I 3 / 3I ; IO3 / I 2 ;
BrO3 / Br2 , hy d on kh nng phn ng trong cc trng hp sau. Vit phng

trnh phn ng (nu c).

a) Cl2 + I

b) Cl2 + I 2

c) Cl2 + Br

d) Cl2 + Br2

e) Br2 + I 2

g) Br2 + I

Tr li: Cc phn ng a); b); c); g) xy ra.

IV.2.13.Cho pin:
H 2 (Pt), pH 2 =1 atm H 1M MnO41M , Mn 2 1M , H 1M Pt

Bit rng s ca pin 250 C l +1,51 V. Hy cho bit phn ng quy c, phn
0
ng thc t xy ra trong pin v tnh EMnO

/ Mn2

IV.2.14. Thit lp s pin xc nh EFe0 (OH ) / Fe (OH ) . Xc nh catot, anot. Vit phng
3

0
trnh phn ng quy c v phn ng xy ra khi pin hot ng. Bit E pin
=-0,52 V.

Hng dn: Vit na phn ng tng ng vi cp Fe(OH )3 / Fe(OH ) 2 xc nh

thnh phn cu t c mt trong na phi ca pin v t gi tr E pin s xc nh catot,
anot
IV.2.15. Thit lp cc pin khin pin hot ng th xy ra cc phn ng theo s :
a) MnO4 + MnO2 + OH MnO42 +2 H 2O
b) H 2 + AgCl H + Ag + Cl
c) H 2C2O4 + KMnO4 CO2 + Mn 2
d) CrO2 + H 2O2 CrO42
Hng dn: Xc nh cc cp oxi ho kh. Vit phng trinh cc na phn ng v
t xc nh cc cc. V d phn ng a0 bao gm qua trnh kh MnO4 thnh
MnO42 v qu trnh oxi ho MnO2 ln MnO42 . Do cp MnO4 / MnO42 ng vai

tr catot v cp MnO42 / MnO2 ng vai tr anot.

IV.2.16. Thit lp cc s pin khi pin lm vic th xy ra c phn ng sau:
a) Hg 22 + 2 Cl Hg 2Cl2
b) Hg 2 + 2 I HgI 2
c) Zn 2 + S 2 ZnS
d) Pb 2 + CrO42 PbCrO4
Hng dn: V cc phn ng xy ra km theo s thay i nng cc kim loi, v
vy phi chn in cc lm vic thun nghch vi cc ion loi tng ng.
a) cc Hg / Hg 22 v Hg / Hg 2Cl2 , Cl
b) cc Hg / Hg 2 v Hg / HgI 2 , I
c) cc Zn / Zn 2 v Zn / ZnS , S 2
d) cc Pb / Pb 2 v Pb / PbCrO4 , CrO42 .
e)

III.S PH THUC TH THEO NNG PHNG TRNH NEC

(NERNST)
Bi tp c hng dn
IV.3.1. Vit phng trinh lin h gia th ca cc cp oxi ho kh vi nng cc cht (
250 C ) i vi cc na phn ng sau:

a) Zn + 4 CN Zn(CN )24 + 2e
b) 2 H 2O 4 H + O2 + 4e
c) Hg 2Cl2 +2e 2Hg + 2 Cl
d) Cu ( NH 3 ) 42 + e Cu ( NH 3 )2 + 2 NH 3
e) FeF63 + e Fe2 + 6 F
Hng dn
a) E = E

0
Zn ( CN )24 / Zn

b) E = EO0 H
2

/ H 2O

2
0, 0592 Zn(CN ) 4
+
lg
4
2
CN

0
c) E = E Hg
Cl / Hg +
2

4
0, 0592
lg H . pO2
4

0, 0592
1
0

lg
= E Hg
Cl2 / Hg -0,0592lg Cl
2
2
2
Cl

0
Cu ( NH 3 )42 / Cu ( NH 3 )2

d) E = E

e) E = E

0
FeF63 / Fe2

Cu ( NH 3 )42
+ 0,0592lg
2
Cu ( NH 3 )2 . NH 3

FeF63
+ 0,0592lg
.
6
Fe2 . F

IV.3.2. Cho pin

H 2 ( Pt ), pH 2 =1 atm H 1M MnO41M , Mn 2 1M , H 1M Pt

Bit rng s ca pin 25 C l 1,5 V.

a) Hy cho bit phn ng quy c, phn ng thc t xy ra trong pin v
0
EMnO
.

/ Mn2
4

b) Sc in ng ca pin thay i ra sao (xt nh hng nh tnh),

nu:
-Thm t NaHCO3 vo na tri ca pin?
-Thm t FeSO 4 vo na phi ca pin?
-Thm t CH 3COONa vo na phi ca pin?
Hng dn
a)

V S = E pin = +1,51 V > 0, cc Pt (bn phi) l catt, cc hir (bn

tri) l ant, do phn ng thc t xy ra trong pin s trng vi phn ng

quy c.

MnO4 + 8 H + 5e Mn 2 + 4 H 2O

catt xy ra qu trnh kh:

2H+ +2e

ant xy ra qu trnh oxi ho: H2

Phn ng thc t xy ra: 2MnO4 + 5H 2 + 6 H 2Mn 2 + 8H 2O

V y l pin tiu chun, nn theo quy c:
0
0
0
E pin
= E0 - E0 = EMnO
- E20H / H = EMnO

/ Mn2
/ Mn2
4

0
Vy EMnO

/ Mn2

0
= E pin
= 1,51 (V)

b) Khi thm cc cht vo na phi hoc na tri ca pin th lc pin

khng cn l pin tiu chun na.
- Nu thm t NaHCO3 vo na tri ca pin s xy ra phn ng:
HCO3 + H H 2O + CO2

lm H gim, E2 H
do E pin = EMnO

/ H2

- E2 H

/ Mn2

0, 0592 H
=
lg
gim,
2
pH 2

s tng.

/ H2

-Tng t thm t FeSO4 vo na phi ca pin th:

MnO4 + 5Fe 2 + 8H Mn 2 + 5Fe3 + 4H 2O

Ngoi ra SO42 + H HSO4 , lm cho MnO4 v H gim; Mn 2

tng, EMnO

/ Mn2

0
= EMnO

/ Mn2

0, 0592 MnO4 H
lg
5
Mn 2

gim, do s ca pin

gim.
-Nu thm t CH 3COONa vo na phi ca pin:
CH 3COO + H CH 3COOH

Do H gim, EMnO

/ Mn2

gim, nh vy s ca pin s gim.

IV.3.3. Tnh nng ban u ca HSO4 bit rng khi o s ca pin:

Pt I 0,1 M ; I 3 0, 02 M MnO4 0, 05 M , Mn2 0, 01 M , HSO4C M Pt
0
250 C c gi tr 0,824 V. Cho EMnO

/ Mn2

= 1,51 V v EI0 /3I = 0,5355 V.

Hng dn
in cc phi:

MnO4 + 8H + 5e Mn 2 + 4H 2O

in cc tri:

3I I 3 + 2e

Eph = E

Etr = E

0
MnO4 / Mn2

0
I 3 /3 I

0, 0592 MnO4 H
0, 0592 0, 05 H
+
lg
= 1,51 +
lg
5
5
0, 01
Mn 2

I3
0, 02
0, 0592
0, 0592
+
lg
= 0,5355 +
lg
= 0,574
3
2
2
(0,1)3
I

S = Eph - Etr hay 0,824 = 1,51 +

8
0, 0592
lg (5 H ) - 0,574
5

h = H = 0,054 M

Mt khc t cn bng: HSO4

[]

Ch

H + SO42

K n = 102

h2
h2
Ka
hC
Ch
Ka

Thay gi tr h=0,054 v K n =1,0. 102 , tnh c CHSO =0,346 M.

IV.3.4.
a) nh ngha th iu kin. Lp biu thc th iu kin i vi cp
Ox/Kh:
Ox + ne + m H Kh + p H 2O .
b)

Xt s ph thuc ca th iu kin vo pH ca cp H 3 AsO4 / HAsO2 .

c)

Chng minh rng pH=0 (mi trng axit mnh), I 2 khng oxi ho c HAsO2 .

Cho bit EH0 AsO / HAsO =0,56V; H 3 AsO4 c pK=2,19; 6,94 v 11,50.
3

Li gii:
a) Cng nh cc hng s iu kin khc,th iu kin o c iu
kin xc nh v cc yu t ph, v d pH, nng cht to phc ph, lc ion, v.v
E = E0 +

0, 0592 (Ox) 0, 0592

0, 0592 (Ox)
lg
lg
+
lg( H ) m = E ' +
n
( Kh)
n
n
( Kh)

Th iu kin E ' = E 0 +
b) H 3 AsO4 + 2H +2e

0, 0592 fOx 0, 0592m

lg
pH
n
n
f Kh
HAsO2 + H 2O

Cch 1: EH AsO / HAsO = E1 = E10 +

3

E10 =0,56V

0, 0592 H 3 AsO4
lg
- 0,0592pH
2
HAsO2

Mt khc: E1 = E1' +

0, 0592 H 3 AsO4
lg
2
HAsO2

E1' = E10 - 0,0592pH=0,56 - E10

Cch 2: E1' = E1 khi

H 3 AsO4 =1
HAsO2

E1' = E10 - 0,0592pH

c) pH=0, EH' AsO / HAsO = E1' = E10 - 0,0592pH=0,56V

3

'
H 3 AsO4 / HAsO2

0
I 3 / I

=0,5355V, v vy I 3 khng oxi ho c HAsO2 .

IV.3.6. Co2 c tnh kh rt yu, rt kho oxi ho thnh Co3 trong mi trng
axit (tr khi in phn) nhng khi c mt NH 3 d th Co2 d dng b oxi
ho bi H 2O2 . Hy gii thch.
Hng dn
Trong mi trng axit, ion Co3 l cht oxi ho rt mnh
0
Co3 + e Co2 c ECo
=1,84V v vy trong dung dch nc Co3
3
/ Co 2

khng bn, oxi ho nc to thnh Co2 v O2 .

Khi c mt lng d NH 3 , Co2 v Co3 u to phc amin, hinh thnh
cp oxi ho kh mi: Co( NH 3 )63 / Co( NH 3 )62 . Do phc ca Co3 bn hn,
nn th ca cp Co3 / Co2 gim xung nhiu, tnh kh ca Co2 tng ln v d
b oxi ho thnh Co (III). Th tiu chun ca cp Co( NH 3 )63 / Co( NH 3 )62 c
tnh nh sau:
Co( NH 3 )63 + e Co( NH 3 )62
E=E

Co( NH 3 )36
+ 0,0592lg
Co( NH 3 )62

0
E = ECo
( NH

+ 0,0592lg

0
Co ( NH 3 )36 / Co ( NH 3 )62

3
2
3 )6 / Co ( NH 3 )6

0
Co3 / Co 2

Mt khc: E = E
0
ECo
( NH

3
2
3 )6 / Co ( NH 3 )6

III Co3
II Co 2

Co3
+ 0,0592lg
Co 2

0
= ECo

/ Co 2

- 0,0592lg

III
II

0
ECo
( NH

3
2
3 )6 / Co ( NH 3 )6

=1.84 0,0592.(35,16 4,39) = 0,018 V

Hoc c th tnh theo s t hp cn bng nh sau:

Co( NH 3 )63 Co3 + 6 NH 3

III1 = 1035.16

Co3 + e Co2

K1 = 101,84/ 0,0592

Co2 + 6 NH 3 Co( NH 3 )63

II = 10 4,39
0

Co( NH 3 )63 + e Co( NH 3 )62

0
K 2 = K1 . III1 . II ECo
( NH
0
ECo
( NH

3
2
3 )6 / Co ( NH 3 )6

3
2
3 )6 / Co ( NH 3 )6

K 2 = 10 E2 / 0,0592

= E20 =0,018 V.

= E20 =0,018 V < E H0 O / H O =1,77 V, ngha l trong mi trng

2

NH 3 d H 2O2 d dng oxi ho c Co(II), hay ni mt cch chnh xc

Co( NH 3 )62 d dng b oxi ho bi H 2O2 chuyn thnh Co( NH 3 )63 .

Bi tp vn dng
IV.3.7. Vit phng trnh lin h gia th E vi nng p vi cc na phn
ng oxi ho kh sau:
a) Cr2O72 + 14 H + 6e 2 Cr 3 + 7 H 2O .
b) MnO42 + 2 H 2O + 2e MnO2 + 4 OH .
c) Fe(OH )3 + e Fe(OH )2 + OH .
d) CrO2 + 4 OH CrO42 + 2 H 2O +3e.
e) Co(CN )36 + e Co(CN )46 .
IV.3.8. Tnh th ca in cc platin nhng trong dung dch:
a) Cr2O72 0,010 M; Cr 3 0,10 M pH=2,00.
b) Dung dch bo ho Fe(OH )3 , Fe(OH )2 pH=10,00. Cho
0
EFe
( OH )3 / Fe ( OH )2 =-0,52V.

Tr li: a) 1,054V;
b) -0,283v.
IV.3.9. Hy xc nh in cc catot, anot v biu din s pin khi ghp:
a)

in cc platin nhng trong dung dch gm KI 0,150 M, KI3 0,030 M

vi in cc cadimi nhng trong dung dch Cd ( NO3 )2 0,10 M.

b) in cc platin ma Pt nhng trong dung dch HCl 0,0020 M c
bo ho bng kh hiro p sut 1 atm vi in cc thu ngn nhng trong

dung dch Hg ( NO3 )2 0,0010 M; HCl 1 M.

Tr li: a) in cc cadimi la anot; b) in cc thu ngn l catot.
IV.3.10. a) Vit s pin c ghp bi hai cp Fe3 / Fe 2 v Sn 4 / Sn 2
iu kin chun (pH= 0). Tnh s ca pin.
Cho bit: EFe0

/ Fe2

=0,77 V; ESn0

/ Sn2

=0,14 V.

b) Nu thm t KSCN vo dung dch pha catot ca pin thi s ca pin

s tng hay gim, ti sao?
c) Nu thm vi git I 2 vao dung dch pha anot ca pin th s ca pin
s thay i ra sao? Gii thch?
0
Tr li: a) E pin
=0,63 V; b) S gim; c) S gim.

IV.3.11. Tnh s ca pin 250 C c ghp bi hai cc:

Pt I 0,02 M; I 2 0,10 M v Pt Cr2O72 0,01 M; Cr 3 0,05 M; H 0,1 M.
Thit lp s pin v vit phng trnh phn ng xy ra khi pin
lm vic.
Tr li: E pin =0,63V.
IV.3.12. Tnh th tch ca in cc platin nhng trong cc dung dch sau:
a) V 3 0,02 M, VO 2 0,10 M, Ph=9,00.
b) VO 2 0,050 M, VO2 0,10 M, HCl0,010 M.
c) MnO4 0,10 M, Mn 2 0,050 M, H 2 SO4 0,10 M.
d) S 2O32 0,050 M, S 4O62 0,070 M.
Tr li: a) -0,724 V; b) 0,781 V; c) 1,34 V; d) 0,123 V.
IV.3.13. Tnh th ca in cc bc nhng trong cc dung dch sau:
a) Dung dch AgNO3 0,010 M v NH 3 1,0 M.
b)Dung dch AgNO3 0,020 M v Na2 S2O3 1,04 M.
c)Nu ghp ln lt cc na pin trn vi in cc calomen bo ho
( EHg Cl / 2 Hg =0,244 V) th cc no l catot, cc no l anot? Hy biu din s
2

pin, vit phng trnh phn ng t din bin v tnh s ca tng pin.
Hng dn: Xt tng tc ho hc, xc nh nng cc cu t trong
0
dung dch, tnh E Ag
( NH )

3 2 / Ag

0
, E Ag
(S O )

3
2 3 2 / Ag

, t tnh th ca in cc bc.

0
Hoc cng c th tnh th ca in cc bc theo E Ag

/ Ag

Tr li: a) E=0,253 V; b) E=-0,098 V;

c) E pin( a ) =0,009 V; E pin(b ) =0,342 V.
IV.3.14. Tnh sc in ng ca pin c to thnh bi in cc platin
nhng trong dung dch Ce3 0,053 M, Ce4 0,10 M. H 2 SO4 1,0 M v in
cc calomen bo ho.
Vit cc phng trnh phn ng thc t xy ra khi pin hot ng v
vit s pin. Cho Ecalomen =0,244 V.
Tr li: E pin =1,214 V.
IV.3.15. Thit lp s ph thuc th theo pH ca cc cp:
a) Fe(OH )3 / Fe(OH )2

( E 0 =-0,526 V)

b) MnO4 , H / Mn 2

( E 0 =1,51 V)

c) ClO3 , Cl / H

( E 0 =1,45 V)

Hot cc cht oxi kh c coi bng 1.

Tr li: a) E=0,303-0,0592pH; b)E= E 0 -0,0947pH;
c) E= E 0 -0,0592pH.
IV.3.16. Thit lp s ph thuc E-pH ca cc cp:
a) O2 , H / H 2O
b) O2 , H / H 2O2
c) H 2O2 , H / H 2O .
Tr li: a) E=1,229-0,0592pH
a)
b)

( pO =1 atm)
2

E=0,682-0,0592pH ; c) E=1,776-0,0592pH.

IV.HNG S CN BNG CA PHN NG OXI HA- KH

Bi tp c li gii
0
IV.4.1. Cho ECo

/ Co 2

0
1,84V . Tnh ECo
3
/ Co

Hng dn
T hp cn bng xut pht t trng thi u l Co3 trng thi cui l Co:

Vy 10

Co3+ +e

Co2+

K 1 1 0 1 ,8 4 / 0 , 0 5 9 2

Co2+ +2e

Co

K 2 10 2.( 0, 28 ) / 0, 0592

Co3+ +3e

Co

K K1.K 2 10

(3 E0

C o 3 / C o

) / 0 ,0592

.( 3 E 0

Co3 / Co

) / 0 ,0592

10 (1,84 0 ,56 ) / 0 ,0592 E A0 gBr / A g 0, 427 V

0
0
IV.4.2. Cho E AgB
r / Ag 0, 073 V; E Ag

/ Ag

0, 799 V . Tnh KS(AgBr)

Hng dn
T hp cn bng xut pht t trng thi u l AgBr c trng thi cui l Ag+ v Br-:
AgBr + e

Ag + Br-

Ag Ag+ + e
AgBr

Vy K S ( AgBr ) K 1.K 21 10

( E 0AgBr / Ag E 0

Ag / Ag

) / 0 , 0592

( E A0 g B r / A g ) / 0 , 0 5 9 2

K 2 1 1 0

Ag+ + Br-

K1 10

(E0

Ag / Ag

) / 0 ,0 5 9 2

S ( AgBr )

10 ( 0, 0730, 799 ) / 0,0592 10 12, 26

IV.4.3. Xt kh nng phn ng ca bc kim loi vi Hcl v HI. Cho

0
E Ag
0, , 799 V , K S ( AgCl ) 1010,0 v K S ( AgI ) 1016,0 .

/ Ag

Hng dn:
Trong dung dch : HCl H Cl
HI H+ + I2H+ + 2e H2
Ag
0
Do E Ag

/ Ag

Ag+ + e

E20H / H nu khng c mt Cl- v I- th AG kim loi khng c kh nng kh

2

ion H giI phng ra H2. Nhng trong mi trng c cha Cl- v I- s hnh thnh cc
cp oxi ho kh mi:AgCl/Ag v AgI/Ag.
0
0
E Ag
E Ag
0, 00592lg K s ( AgCl ) 0, 207 V

/ Ag
/ Ag
0
0
Tng t E AgI
/ Ag E Ag

/ Ag

0, 0592lg K s ( AgI ) 0,148 V

0
0
Ta c E AgI
/ Ag 0,148 V E2 H

/ H2

0
0 E AgCl
/ Ag 0, 207 V

Nh vy bc kim loi ch c kh nng phn ng vi dung dch HI to ra Ag v gii

phng H2.

Bi tp vn dng
IV.4.4. nh gi kh nng ho tan NiS bng HCl khi c mt H2O2.
Cho EH0 O / H O 1, 77 V ; ES0/ S 4, 48 V ; K S ( NiS ) 10 24 .
2 2

Tr li: K=1052,27 , phn ng xy ra d dng.

IV.4.5. Gii thch ti sao khi cho vi git H2O2 vo dung dch CO(NH3)62+ th dung dch
chuyn t mu vng sang mu hang m ?
0
Cho: ECo

/ Co 2

Co( NH

2
3 )6

1,84 V ; E H0 2O2 / H 2 O 1, 77 V ;

104,39 ; Co ( NH

3
3 )6

1035,16

Tr li : K=1059,18,phn ng oxi ho CO(NH3)62+ (mu vng) bi H2O2 xy ra hon ton

v dung dch c mu hng m ca CO(NH3)62+.
IV.4.6. Tnh hng s cn bng ca phn ng d li ca Br2 pH =8,00.
Cho bit EBr0 ( H O )/2 Br 1, 085V v EBr0 O

2 3 / Br2 ( H 2O )

1,52 V .

Tr li: K=1047,26
IV.4.7. hon thnh v cn bng cc phng trnh phn ng sau. Tnh hng s cn bng
ca mi phn ng:
a)Co(OH )3 HCl .......

(lg K sCo( OH )3 40,5)

b) Ag ( NH 3 ) 2 Zn Zn( NH 3 ) 42 ......
c) FeF3 Sn 2 ........

Tr li: a) 1019,25 ; b)1047,18 ; c)10-5,36.

0
0
IV.4.8.Tnh EMnO
v EMnO
/ Mn
3

3
4 / Mn

0
0
t EMnO
, EMn
/ Mn
2

/ Mn 2

0
v EMnO

Tr li: 0,95 V v 1,51 V.

IV.4.9. T ECr0 O

2
3
2 7 /2 Cr

0
a) ECr
O 2 /2 Cr 2
2 7

Tr li: a) 0,896 V

, ECr0

/ Cr 2

v ECr0

/ Cr

hy tnh

0
b) ECr
.
2
/ Cr

b) -0,912 V

IV.4.10. Hy tnh th oxi ho-kh trong cc dung dch sau y :

a) Fe3+ 0,0010 M + Fe2+ 0,050 M + H+ 1 M
b) MnO4- 0,0050 M + Mn2+ 0,020 M, pH=2
c) KI 0,0010 M + Fe3+ 0,01 M + H+ 1 M

2
4 / Mn

d) Cr2O72- 0,010 M + Cr3+ 0,10 M + H+ 1 M

Tr li : a) 0,671 V ; b)1,31V ; c)0.889 V (xt phn ng xy ra gia Fe3+ v I- cho Fe2+ v
I2, t tnh th theo cp in hot Fe3+/Fe2+).

V. NH GI NH LNG CHIU HNG V MC XY

RA CA CC PHN NG OXI HA KH
Bi tp c li gii
IV.5.1. Tnh cn bng trong dung dch Ce4+ 0.800 M v Br- 0,750 M pH = 0
Cho:
0
ECe
1, 44 V ;
4
/ Ce3

0
Br2 ( H 2O )/2 Br

0
EBr
1, 065 V ;
(1)/2 Br
2

1, 085 V ; LBr2 0, 214 M

Hng dn:
2Br- + 2Ce4+ Br2
1
2

2Ce3

10-6,33

( y CBr C Br 0, 375M LBr 0, 214 M nn cn dng EBr0 (1)/2 Br 1, 065 V

2

TPGH vi xmax = 0,375 l Ce4+: 0,05 M; Ce3+: 0,75 M

Br2 + 2Ce3+ 2Br- + 2Ce4+
0,214
0,75
0,05
0,014 (0,75-x)
x
(0,05+x)

10-6,33

( x) 2 (0, 05 x )2
10 6,33
(0, 75 x)2 (0, 214)

[Br-] = x = 4,34.10-3 M; [Ce4+] = 0,0543 M; [Br2] = 0,214 M

IV.5.2. Tnh cn bng trong dung dch PtCl62- 0, 010 M . Cho:
0
0
EPtCl
0, 73 V ; EPtCl
0, 68 V
2
2
/ Pt
/ PtCl 2
4

Hng dn
:
PtCl42- +2e

Pt+4Cl-

PtCl42- + 2Cl- PtCl62- +2e

2-

2PtCl4 2Cl +Pt+ PtCl6

0,010

C
[]

(0,010-2x)

2-

K 10

2(0,730,68)
0,0592

4,90

2x

x(2 x )2
4,90 4 x 3 4, 90(4 x 2 10 4 2.10 2 x)
2
(0, 010 2 x )
4 x3 19, 6 x 2 9,8.102 x 4,9.104 0 x 2,50.10 3 M
PtCl62 2,50.10 3 M ; Cl 5, 0.103 M ; PtCl42 5, 0.10 3 M

IV.5.3. Tnh cn bng trong h gm Fe(ClO4)2 0,050 M; Fe(ClO4)3 0,050 M HClO4 0,010
M v O2 14.10-3 M.
Cho: lgK1(Fe3+ + e Fe2+)= 12,97;
lgK2(O2 + 4H+ + 4e 2H2O) = 83,10;
lg FeOH 2 2,17; lg Fe

4
2 ( OH )2

2,85; lg FeOH 5, 92

Hng dn:
Phng trnh phn ng:
4

Fe3+ + e Fe2+
O2 + 4H+ + 4e 2H2O

lg K1 12, 97
lg K 2 83,10

4 Fe2+ + O2 + 4H+ Fe3+ + 2H2O

C

0,050

1,4.10

-3

0,010

lg K 31, 22

0,050

C
0,0444
0,0044 0,0556
3+
2+
TPGH: Fe 0,0556 M; Fe 0,0444 M; H+ 0,0044 M.
Phng trnh KP vi MK l Fe3+, Fe2+, H+:
h H CH FeOH 2 2 Fe2 (OH )24 FeOH
2

h CH 11 Fe3 h 1 2 22 Fe3 h 2 Fe 2 h 1
2

h CH h 11 Fe3 2 22 Fe3 h 1 Fe 2

(6)
(7)
(8)

- Tnh gn ng bc 1:
Chp nhn h0 C H 0, 0044M ; Fe3 0 0, 0556 M v Fe 2 0 0, 0444 M v thay

vo (8) tnh c gi tr h1 = 10-1,31 = 0,0488 M.

Thay gi tr h1 va tnh c vo biu thc (9); h1 v Fe3 vo (10) (c rt ra

0

2+

3+

t nh lut BTN ban u i vi Fe v Fe ):

CFe2
CFe3
3
Fe 2

(9);
Fe

1 h1 2 Fe3 h 2
1 h 1
11
22

(10)

tnh li Fe 2 0, 0444 Fe 2 v Fe3 0, 0462 M

1
0
1
- Tnh gn ng bc 2:
Thay gi tr h1, Fe 2 v Fe3 vo (8) tnh li h2 = 10-1,59 = 0,0255 M v t
1
1
tnh li Fe 2 v Fe3 theo (9) v (10):
2
2
Fe 2 0, 0444 (lp) v Fe3 0, 0381
2
2

Tip rc tnh lp nh vy c kt qu:

Fe3 3, 73.102 M ; Fe 2 4, 44.102 M ; FeOH 2,35.106 M ; pH 1, 64
Fe2 (OH ) 24 3,57.103 M ; FeOH 2 1,11.102 M ; O2 7, 52.1026 M

Bi tp vn dng
IV.5.4. Trn 45,00ml dung dch KMnO4 0,010 M vi 15,00ml FeSO4 0,10 M pH = 0.
Tnh TPCB ca h:
Tr li:
Fe 2 8, 7.1015 M ; Fe3 2,5.102 M ; Mn 2 5, 0.103 M
MnO4 2,5.103 M ; FeOH 2 1, 69.104 M ; Fe2 (OH ) 24 8,83.107 M

IV.5.5. Tnh cn bng trong h gm K2Cr2O7 0,010 M; KI 0,10 M pH = 0

Tr li:
Cr2 O72 1, 2.1075 M ; Cr 3 0, 020 M ; I 1,3.102 M ;
I3 2, 7.102 M ; CrOH 2 3,17.106 M

IV.5.6. Lc mt t bt Ag vi dung dch Fe3+0,010 M v H+ 1 M. Tnh nng cc ion

Ag+ v Fe2+ khi cn bng c thit lp
Tr li: Fe 2 Ag 9, 7.103 M

IV.5.7. Trn 50,00 ml dung dch Ce+ 0,100 M vi 50,00ml dung dch Fe2+ 0,050 M pH
= 0. Tnh th ca in cc platin so vi in cc calomen bo ho. Cho:
0
0
ECe
1, 44 V ; EFe
0, 68 V ; Ecal 0, 244 V
4
3
/ Ce3
/ Fe 2

Tr li: 1,196 V.
IV.5.8. Trn 25,00 ml K2Cr2O7 0,080 M vi 15,00 ml KBr 0,02 M pH = 0. Tnh th ca
in cc platin nhng trong dung dch thu c so vi in cc Ag AgCl HCl 1 M (E0
= 0,222 V).
Tr li: 1,117 V
IV.5.9. Tnh TPCB trong dung dch Fe3+ 0,10 m v I- ,0 M pH = 2,00.
Hng dn: Tnh theo th thc pH = 2,00.
Tr li:
Fe 2 0,10M ; FeOH 1, 2.105 M ; Fe3 2, 7.106 M ;
FeOH 2 1,8.106 M ; I 0,85M ; I 3 0, 050 M .

IV.5.10. Tnh cn bng trong dung dch khi nhng mt thanh bc kim loi vo dung dch
Fe(ClO4)3 0,010 M pH = 1,99.
Hng dn: Tnh theo hng s cn bng iu kin.
Tr li:
Fe 2 Ag 9,5.10 3 M ; Fe3 2, 7.10 4 M ; FeOH 2 1,3.104 M

IV.5.11. Tnh cn bng trong dung dch gm Fe3+ 0,010 M; I- 0,015 M v F- 1,0 M pH =
5,50.
Hng dn: Tnh theo hng s cn bng iu kin
Tr li:
Fe 2 3,5.109 M ; Fe3 9,5.10 15 M ; FeOH 1,3.10 9 M ; FeF3 9,95.103 M

IV.5.12. Tnh cn bng trong dung dch thu c khi lc mt mu Cd kim loi trong
10,00 ml axetic 0,010 M cho n cn bng.
Cho: LH 8.104 M ;lg CdOH 7, 62; lg Cd OH 9,1
2

Hng dn: Trong h c cc qu trnh lin quan n phn ng axit - baz nn c th tnh
theo KP.
Tr li: pH = 6,35; [Cd2+] = 4,75.10-3 M; [CdOH+] = 2,53.10-4 M;
[Cd2OH3+] = 3,98.10-8 M; [CH3COO-] = 9,75.10-3 M;
[CH3COOH] = 2,53.10-4 M

IV.5.13. Tnh nng cn bng trong dung dch thu c khi trn 75,00 ml KI 0,10 M
vi 45,0 ml FeCl3 0,20 M v EDTA 0,30 M pH = 9,00 (b qua qu trnh to phc
hiroxo a nhn ca Fe3+).
Tr li: I 3 2, 098.107 M ; I 0, 063M ; Fe 2 1, 01.1018 M
Y 4 1,95.10 3 M ; Fe3 3, 06.1024 M ; FeY 2 4, 2.10 7 M
FeY 0, 075M ; FeOH 2 2, 07.10 17 M ; FeOH 1, 21.1015 M

IV.5.14. Lc mt mu thic kim loi trong dung dch Pb2+ 0,010 M cho n cn bng.
Tnh thnh phn cn bng trong h thu c pH = 2,10.
Hng dn: Tnh theo hng s cn bng iu kin.
Tr li: [Pb2+] = 1,3.10-3 M; [Sn2+] = 4,2.10-3 M; [SnOH+] = 4,5.10-3 M.