Hng dn gii bi tp Ha phn tch - Khoa Cng Ngh Ha Hc

1

CHNG 6: CHUN OXY HA KH
6.1. Cn bng cc phn ng sau bng phng php thng bng ion- electron
Fe
2+
+ MnO
4
-
+ H
+
Fe
3+
+ Mn
2+
+ H
2
O
C
2
O
4
2-
+ MnO
4
-
+ H
+
Mn
2+
+ H
2
O + CO
2

H
2
O
2
+MnO
4
-
+ H
+
Mn
2+
+ H
2
O + 5O
2

NO
2
-
+MnO
4
-
+ H
+
Mn
2+
+ H
2
O +NO
3
-

Cr
2
O
7
2-
+ I
-
+ H
+
Cr
3+
+ I
3
-
+ H
2
O
Fe
3+
+ I
-
I
3
-
+ Fe
2+

I
3
-
+ S
2
O
3
2-
3 I
-
+ S
4
O
6
2


a. Fe
2+
+ MnO
4
-
+ H
+
Fe
3+
+ Mn
2+
+ H
2
O
Fe
2+
- 1e Fe
3+
x 5
MnO
4
-
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O x 1
5Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
b. C
2
O
4
2-
+ MnO
4
-
+ H
+
Mn
2+
+ H
2
O + CO
2

MnO
4
-
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O x 2
C
2
O
4
2-
-2e 2 CO
2
x 5
5C
2
O
4
2-
+ 2MnO
4
-
+ 16H
+
2Mn
2+
+ 8H
2
O + 10CO
2

c. H
2
O
2
+MnO
4
-
+ H
+
Mn
2+
+ H
2
O + 5O
2

MnO
4
-
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O (thiu 8H
+
) x 2
H
2
O
2
- 2e O
2
(tha 2H
+)
x 5
bn phn ng kh khi nhn 2 cn 16 H
+
bn phn ng oxy ha khi x 5 tha 10 H
+

Sau khi quy ng s e, s ion H
+
thc s thiu l 6 H
+

5H
2
O
2
+2MnO
4
-
+ 6H
+
2Mn
2+
+ 8H
2
O + 5O
2

Hng dn gii bi tp Ha phn tch - Khoa Cng Ngh Ha Hc

2

d. NO
2
-
+MnO
4
-
+ H
+
Mn
2+
+ H
2
O +NO
3
-

MnO
4
-
+ 5e Mn
2+
(tha 4 O) x 2 Tha 8 oxy
NO
2
-
-2e NO
3
-
(thiu 1 O) x 5 thiu 5 oxy
Kt hp hai bn phn ng tha 3 oxy
2MnO
4
-
+ 5NO
2
-
2Mn
2+
+ 5NO
3
(tha 3 oxy)
Gii quyt 3 oxy ny bng cch cho kt hp vi 6 H
+

2MnO
4
-
+ 5NO
2
-
+ 6H
+
2Mn
2+
+ 5NO
3
+ 3H
2
O
e. Cr
2
O
7
2-
+ I
-
+ H
+
Cr
3+
+ I
3
-
+ H
2
O
Cr
2
O
7
2-
+ 6e + 14H
+
2Cr
3+
+ 7H
2
O x 1
2I
-
-2e I
2

I
2
+ I
-
I
3
-
Cr
2
O
7
2-
+ 9I
-
+ 14H
+
2Cr
3+
+ 3I
3
-
+ 7H
2
O
f. Fe
3+
+ I
-
I
3
-
+ Fe
2+
3I
-
- 2e I
3
-
x 1
Fe
3+
+ 1e Fe
2+
x 2
2Fe
3+
+ 3I
-
I
3
-
+ 2 Fe
2+

g. I
3
-
+ S
2
O
3
2-
3 I
-
+ S
4
O
6
2-

3I
-
- 2e I
3
-
x 1
2S
2
O
3
2-
+ 2e S
4
O
6
2
x 1
I
3
-
+ 2 S
2
O
3
2-
3 I
-
+ S
4
O
6
2

6.2 Vit phng trnh trao i electron ca cc h oxy ho kh sau:
a.CrO
2
-
, H
2
O/Cr, OH-
b.SO
4
2-
,H
+
/H
2
SO
3
, H
2
O
c.AsO
4
3-
,H
+
/AsO
3
3-
,H
2
O
a. CrO
2
-
+ 3e + 2H
2
O

Cr + 4OH
-

3I
-
- 2e I
3
-
x 3
Hng dn gii bi tp Ha phn tch - Khoa Cng Ngh Ha Hc

3

b, SO
4
2-
+

2e + H
2
SO
3

(thiu 2H
+
v tha 1oxy)
SO
4
2-
+

2e + 4H
+
H
2
SO
3

+ H
2
O
c. AsO
4
3-
,H
+
/AsO
3
3-
,H
2
O
AsO
4
3-
+ 2e + 2H
+

AsO
3
3- +
H
2
O
6.4 Cho bit th oxy ha kh chun ca cc cp sau: E
0
(H
3
AsO
4
/ H
3
AsO
3
)= 0,559 V: E
0
(
I
2
/I
-
)=0,54V
a. Phn ng s xy ra theo chiu no iu kin tiu chun
AsO
3
4
+ 2I
-
+ 2H
+
AsO
3
3
+ I
2
+ H
2
O
b. Phn ng s xy ra theo chiu no pH = 8
Cc bn phn ng
AsO
3
4
+ 2e + 2H
+
AsO
3
3
+ H
2
O
2I
-
- 2e I
2

Th oxy ha kh ca cp AsO
3
4
/ AsO
3
3
xc nh bi phng trnh:
E = E
o
+
2
0,059
lg [H
+
]
2
+
2
0,059
lg
]
]
- 3
3
- 3
4
[AsO
[AsO

Th iu kin chun l th khi:
[AsO
3
4
] = [AsO
3
3
] = 1(M) v [H
+
]= 10
0
(M).
. dktc E
0
(H
3
AsO
4
/ H
3
AsO
3
)= 0,559 V > E
0
( I
2
/I
-
)=0,54V
Nn phn ng xy ra theo chiu thun
Khi pH=8. E = E
o
+
2
0,059
lg [H
+
]
2
+
2
0,059
lg
]
]
- 3
3
- 3
4
[AsO
[AsO

Th chun iu kin E
o
' pH = 8 l th khi:
[AsO
3
4
] = [AsO
3
3
] = 1(M) v [H
+
]= 10
-8
(M).
E
o'
= E
o

2
2 0,059
pH = 0,57 0,059 8 = 0,098V
NH vy pH =8 , [AsO
3
4
] = [AsO
3
3
] = 1(M) c E
o
=0.098v < E
0
( I
2
/I
-
)=0,54V. Nn I
2

s phn ng vi AsO
3
3
. Phn ng trn s xy ra theo chiu ngc.
6.5. Th oxy ho kh chun ca cp Ag
+
/Ag l 0,8V. Tnh th oxy ho kh chun iu
Hng dn gii bi tp Ha phn tch - Khoa Cng Ngh Ha Hc

4

kin ca cp Ag
+
/Ag khi c mt Cl
-

iu kin chun : Ag
+
+ 1e Ag
(1)
Khi c mt Cl
-
Ag
+
+ Cl
-
AgCl
Bn phn ng tr thnh AgCl + 1e Ag + Cl
-




(2)

Trong dung dch E ca cc cp oxy ha kh lin hp trong dung dch bng nhau v bng
E ca dung dch . Do so (1) v (2)



l th chun ca cp {AgCl / Ag, Cl
-
} v l th chun iu kin ca cp
Ag
+
/Ag khi c mt Cl
-
=>
6.7. Vit phng trnh phn ng kh MnO
4
-
trong cc mi trng axit mnh, trung tnh
v baz mnh. V tnh ng lng gam ca MnO
4
-
trong mi trng hp.
Trong mi trng axit mnh: ion MnO
4
-
b kh thnh Mn
2+
khng mu
MnO
4
-
+ 5e
-
+ 8H
+
Mn
2+
+ 4H
2
O
MnO4
=M
MnO4
/5
Trong mi trng axit yu, trung tnh hoc kim yu, ion MnO
4
-
b kh thnh MnO
2

MnO
4
-
+ 3e
-
+ 4H
+
MnO
2
+ 2H
2
O
MnO4
=M
MnO4
/3
MnO
4
-
+ 3e
-
+ 2H
2
O MnO
2
+ 4OH
-

Trong mi trng kim mnh, ion MnO
4
-
b kh thnh manganat.
MnO
4
-
+ 1e
-
MnO
4
2-

MnO4
=M
MnO4
/1
6.8. Gii thch ti sao KMnO
4
khng phi l cht gc? Ti sao ch xc nh chun ca
Hng dn gii bi tp Ha phn tch - Khoa Cng Ngh Ha Hc

5

KMnO
4
vi ngy sau khi pha ch?
KMnO
4
l cht rn c tnh oxy ha mnh, tinh th mu tm en v thng c tp cht,
ch yu l MnO
2
. Khi ha tan trong nc KMnO
4
c th b phn hy bi vt cc cht kh
c trong nc nh cc cht hu c theo bi ri vo nc to thnh MnO
2
. V vy sau khi
pha ch xong, nng dung dch gim dn, phi sau 7 10 ngy nng dung dch mi
n nh. Nu un nng dung dch KMnO
4
, qu trnh oxy ha xy ra nhanh, sau vi gi c
th lc b kt ta v c dung dch KMnO
4
c nng n nh.
dung dch KMnO
4
c bn v nng ca n khng thay i, cn phi lc b
kt ta MnO
2
c ln trong dung dch v chng c tc dng xc tc lm tng s phn hy
tip tc ca KMnO
4
:
KMnO
4
+ H
2
O = MnO
2
+ 4KOH + 3O
2
(1)
Cng nn ch pemanganat oxy ha c cao su, nt bc v giy, Do khng lc
KMnO
4
qua giy lc m phi lc bng chn lc thy tinh, hoc tch dung dch khi kt
ta MnO
2
bng ng xiphng.
Bo qun dung dch KMnO
4
trong ti, hoc trong chai mu ti v nh sng lm tng
nhanh s phn hy ca KMnO
4
theo phng trnh (1)
6.9. Tnh khi lng KMnO
4
( M= 158 ; P=95% ) cn pha 100ml KMnO
4
1N.
Tnh th tch KMnO
4
1N cn ly pha c 100ml KMnO
4
0,05N. Bit KMnO
4

c s dng l cht chun trong mi trng axit mnh.
- Cng thc m = VNM/10ZP. (Z=5)
- (VN)

= (VN)
s

S: 3,33g; 5ml
6.10. Tnh khi lng H
2
C
2
O
4
.2H
2
O ( M=126,07 ; 99,5% ) pha 100 ml H
2
C
2
O
4
chun
0,05N dng trong phng php Permanganat
S: 0,3168g
6.11. Trnh by cch pha ch 2 lt H
2
SO
4
6N t H
2
SO
4
m c 98% d=1,84.
- Tnh s ml H
2
SO
4
cn dng V (ml) = VNM/10ZPd (Z=2)=326ml
- Dung dch H
2
SO
4
6N thng c dng lm mi trng nn khi pha ch khng cn
Hng dn gii bi tp Ha phn tch - Khoa Cng Ngh Ha Hc

6

phi qu chnh xc. C th dng ng ong ong 320 325ml H
2
SO
4
6N, Chun b mt
bnh ln khong 4-5 lt , cho sn vo khong 1 lt nc ct. t ton b vo mt thau
nc ( lm ngui khi rt acid vo). Rt t t acid vo nc ct tng t mt, khuy u.
Nu nc lm ngui nng qu th thay nc khc. Rt n ht acid. Sau cho thm
nc cho 2 lt
6.12. Ly 10ml dung dch H
2
C
2
O
4
0,05N thm vo 5ml H
2
SO
4
6N v 10ml nc ct.
un nng dung dch ri chun bng dung dch KMnO
4
trn th tn ht 9,7 ml.
Tnh nng ng lng ca dung dch KMnO
4
v chun ca KMnO
4
theo Fe.
N
KmnO4
= (NV)
H2C2O4
/V
KmnO4
=0.0515N
Phn ng vi Fe
2+
5Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
T
KNMnO4
/
Fe
= N
KmnO4
x
Fe
/1000 = 2.8896 /1000 = 2.9 mg/l
S: 0,0516N; 2,8896mg/ml
6.13. Nng ng lng ca pemanganat bng 0,022N. chun ca n theo H
2
C
2
O
4

, theo st, theo H
2
O
2
bng bao nhiu?
Tnh tng t nh trn
5Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
5C
2
O
4
2-
+ 2MnO
4
-
+ 16H
+
2Mn
2+
+ 8H
2
O + 10CO
2

5H
2
O
2
+ 2MnO
4
-
+ 6H
+
2Mn
2+
+ 8H
2
O + 5O
2

S: 0,99mg/ml; 1,232mg/ml; 0,374mg/ml
6.14. Tnh lng phn trm st trong dy st, cho bit khi ha tan 0,1400g dy st trong
H
2
SO
4
m khng cho tip xc vi khng kh v chun dung dch FeSO
4
thu c cn
24,85 ml dung dch KMnO
4
0,1000N?
Fe + H
2
SO
4
= FeSO
4
+ H
2
(khng to thnh Fe
3+
)
Chun dd FeSO
4

5Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
S g st trong dy st = s gam ion Fe tham gia phn ng vi MnO
4
-

(%) Fe = [m
Fe
x (NV)
KmnO4
x 100]: m
mau

= [56 x 10
-3
x (24.85 x 0.1) x 100 ]/0.14 =99.4%
S: 99,4%
6.15. phn tch, cn ly bao nhiu qung c cha khang 70% Fe
2
O
3
sau khi ch
ha xong v chun mui st II thu c cn dng 20 30 ml KMnO
4
0,1N.
Hng dn gii bi tp Ha phn tch - Khoa Cng Ngh Ha Hc

7

Fe
2
O
3
Fe
2+
Chun ht (NV)
KMnO4
S g Fe trong qung = (NV)
KmnO4
x 10
-3
x M
fe
S g Fe
2
O
3
tng ng = (NV)
KmnO4
x 10
-3
x M
fe
x (M
Fe2O3
/2M
Fe
)
S g qung tng ng = (NV)
KmnO4
x 10
-3
x (M
Fe2O3
/2) x(100/a) (a : %Fe
2
O
3
c trong
qung)
V
KmnO4
=20ml m
quang
= 0.2286g
V
KmnO4
=30ml m
quang
= 0.3429g
6.16. Ngi ta ch ha 0,2000 g qung c cha MnO
2
vi mt lng d hn hp H
2
C
2
O
4

v H
2
SO
4
. Lng axit oxalic ly l 25,00 ml v chun lng axit oxalic cn d
khng tham gia phn ng cn 20,00ml dung dch KMnO
4
0,02N. Tnh thnh phn phn
trm mangan trong qung, bit rng mun chun 25,00ml dung dch H
2
C
2
O
4
cn
45,00ml dung dch KMnO
4
.
C
2
O
4
2-
+ MnO
2
+ 4H
+
Mn
2+
+ 2H
2
O + 2CO
2

5C
2
O
4
2-
+ 2MnO
4
-
+ 16H
+
2Mn
2+
+ 8H
2
O + 10CO
2

- Tnh nng dung dch H
2
C
2
O
4
t chun 25,00ml dung dch H
2
C
2
O
4
cn 45,00ml
dung dch KMnO
4
nng 0.02N N
H2C2O4
= 0.036N
- S g MnO
2
trong qung = m
MnO2
x [(NV)
H2C2O4
(NV)
MnO4
]
- S g Mn trong qung = (M
Mn
x10
-3
/2)

x [(NV)
H2C2O4
(NV)
MnO4
]
% Mn = (M
Mn
x10
-3
/2)

x [(NV)
H2C2O4
(NV)
MnO4
]x 100/m
mau
= 6,875%
6.17. Hi c bao nhiu gam canxi trong 250,0ml dung dch CaCl
2
, nu sau khi cho
40,00ml dung dch H
2
C
2
O
4
0,10 N vo 25,00ml dung dch CaCl
2
v sau khi tch kt ta
CaC
2
O
4
c to thnh, cn dng 15,00ml dung dch KMnO
4
0,02N chun H
2
C
2
O
4

d khng tham gia phn ng.
Phn ng :
C
2
O
4
2-
+ Ca
2+
= CaC
2
O
4

Tch kt ta chun H
2
C
2
O
4
d
5C
2
O
4
2-
+ 2MnO
4
-
+ 16H
+
2Mn
2+
+ 8H
2
O + 10CO
2

K thut chun ngc :
m
Ca+
= (M
Ca
x10
-3
/2)

x [(NV)
H2C2O4
(NV)
MnO4
] x (250/25) = 0.74g
6.18. Ti sao khi xc nh cht oxy ha bng phng php iot li phi dng d nhiu KI?
Hng dn gii bi tp Ha phn tch - Khoa Cng Ngh Ha Hc

8

V ha tan ca I
2
trong nc rt b, nn dng dung dch KI lm dung mi ha tan
I
2
, do I
2
to phc vi KI theo phng trnh : KI + I
2
KI
3.
V vy phi cho d KI.
6.19. Cn ly mt lng K
2
Cr
2
O
7
bng bao nhiu xc nh chun ca dung dch
Na
2
S
2
O
3
c nng khong 0,1 N, nu ta c bnh nh mc 200ml v pipet 10ml v ta c
gng sao cho c th tch dung dch thiosunfat dng chun iot thot ra khong
25ml?
Cch 1:
Theo gi thuyt : cn m g K
2
Cr
2
O
7
, V
m
=200ml v V
xd
=10ml v chun bng dung
dch thiosunfat V
Na 2s2o3
=25 .
S ng lng gam K
2
Cr
2
O
7
c trong m g K
2
Cr
2
O
7
l :
m
K2Cr2O7
/
K2Cr2O7

Nng ng lng dung dch K
2
Cr
2
O
7
em chun :
(m
K2Cr2O7
/
K2Cr2O7
)* (1000/200)
Theo nh lut ng lng
(m
K2Cr2O7
/
K2Cr2O7
)* (1000/200) * (10) = 25 * 0.1
m
K2Cr2O7

Cch 2: C th i t cng thc
m
K2Cr2O7
= mD
K2Cr2O7
* (NV)
Na2S2O3
* (V
dm
/Vxd)
Vi Vdm = 200ml Vxd= 10ml
S: 2,45g
6.20. C bao nhiu gam clo trong mt lt nc clo, nu mun chun lng iot thot ra
khi cho 25ml nc clo tc dng vi dung dch KI cn phi dng 20,10ml dung dch
thiosunfat 0,1100N?
Phn ng : Cl
2
+ KI = I
2
+ KCl
I
2
+ Na
2
S
2
O
3
= 2NaI

+ Na
2
S
2
O
3

m
Cl2
= mD
Cl2
* ((NV)
Na2S2O3
* (1000/25) = 3,139g