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BI 1: 0,1 g mu phn tch cha V, Cr, Mn c phn hy thnh dung dch . Sau khi ch
ha dung dch cc nguyn t tn ti di dng VO 2+ , Cr2O72- , MnO4- .Chun dung dch
bng dung dch chun Fe2+ 0,1 M ch ht 50 ml . Ion VO 2+to thnh c chun
bng dung dch chun KMnO4 0,01M th ht 5ml . Sau thm vo lng mui
pitphtphat to phc vi Mn(III) khi chun Mn 2+ bng dung dch KMnO4 trn ,
th tch tiu tn ln chun ny l 10ml . Tnh hm lng % mi kim loi trong mu
( V=50,49 ; Cr =52 ; Mn=54,94 ). Bit E 0Fe3+/Fe2+ = 0,77V ; E0VO2+/VO2+=1 V ;
E0Cr2O72-/ 2Cr3+= 1,36V ;E0MnO4-/Mn2+= 1,51V
V, Cr, Mn
Ch ha
VO2+,,
Fe2+
Bi tp ln
Ta c:
E o Fe3+ / Fe2+
= 0,771(V)
E o Cr2O72 / 2Cr3+
= 1,33 (V)
E oVO2+ /VO2+
= 1 (V)
E o MnO4 / Mn2+
= 1,51 (V)
Vy th t phn ng chun xy ra l:
+ u tin Fe2+ kh MnO4 thnh Mn2+:
5
Fe2+
Fe3+ + e
MnO4 + 8H+ + 5e
Mn2+ + 4H2O
Fe2+
(1)
thnh Cr3+:
Fe3+ + e
2
Cr2 O7 + 14H+ + 6e
2Cr 3+ + 7H2O
Fe3+ + e
+
VO2 + 2H+ + e
VO2+ + H2O
Fe3+ + VO2+ + H2O
Vy ta c:
S lg VO2 + + S lg Cr2 O7
SVO + + S Cr O 2 + S MnO = S 2 +
2
2 7
4
Fe
Bi tp ln
SVO +
Ta c :
= SV = x
S Cr O 2 = 3 SCr = 3y
2 7
S MnO = 5 SMn = 5z
4
S Fe2 + =
5.10-3
= 5.10-3 (**)
Thay vo (*) ta c : x + 3y + 5z =
*Sau chun ion VO2+ to thnh bng dung dch chun KMnO4 0,01M ht 5ml.
5
VO2+ + H2O
+
VO2 + 2H+ + e
MnO4 + 8H+ + 5e
Mn2+ + 4H2O
Ta c:
SVO 2 + = S MnO =
4
= 2,5.10-4 = x
(***)
* Mt khc qu trnh chun VO2+ bng dung dch chun KMnO4 to ra Mn2+ , vy
Mn2+ trong dung dch lc ny c tao ra t phng trnh (1) v (2).
+ (1) : SMn2+ to ra = SMn ban u = z
+ (2) : SMn2+ to ra =
1S
1
MnO4 chun =
5
5
= 5. 10-5
Bi tp ln
Mn2+
Mn3+ + e
MnO4 + 8H+ + 4e
Mn3+ + 4H2O
4Mn3+ + 4H2O
Ta c:
SMn2+ = S MnO4
Hay :
z + 5. 10-5 =
= 4.10-4
y = 10-3
z = 3,5 .10-4
Vy:
+ SV = x = 2,5.10-4
v = 2,5.10-4 50,94 = 0,0127 (g )
Khi lng ca V l : mV = SV
Phn trm ca V l :
12,7 %
+ SCr = y = 10-3
Khi lng ca Cr l : mCr = SCr
Phn trm ca Cr l :
Cr
= 10-3
= 0,052 (g)
= 52 %
+ SMn = z = 3,5.10-4
Khi lng ca Mn l : mMn =SMn
Phn trm ca Mn l :
Mn
= 19,2%
( : ng lng gam )
4
Trn Th M L Lp Ha 3B
Bi tp ln
BI GII:
Tm tt s chun nh sau:
Fe, Cr, Ti
Fe3+
, Cr3+
, TiO2+
3+
3+
Fe , Cr , TiO2+
Fe3+Cr2O72- TiO2+
5
Trn Th M L Lp Ha 3B
3+
3+
2+
Fe , Cr , TiO
Bi tp ln
3+
3+
2+
Fe , Cr , TiO
3+
Fe , Cr3+, TiO2+
Ch ho
Ct kh km
ct kh bc NH3,H2O2
KMnO4 K2Cr2O7Fe2+
Ta c:
E o Fe3+ / Fe2+
6
Trn Th M L Lp Ha 3B
Bi tp ln
E oTiO2+ /Ti3+
*Cho 20 ml dung dch A qua ct kh km, khi Cr3+, Fe3+, TiO2+ u b kh:
Vy th t phn ng xy ra:
+ u tin Zn kh Fe3+ v Fe2+ :
Zn + Fe3+
Fe2+
Fe3+ + e
Zn
Zn2+ + 2e
Fe2+ + Zn2+
Zn
TiO2+ + 2H+ + e
Ti3+ + H2O
Zn + 2TiO2+ + 4H+
Zn
2
Cr3+ +1e
Cr2+
Zn + 2Cr3+
2Cr2+ + Zn2+
S Fe2+ = S Fe3+ = x
S Cr 2+ = S Cr3+ = y
STi 3+ = STiO2 + = z
7
Trn Th M L Lp Ha 3B
Bi tp ln
E o MnO4 / Mn2+
Cr3+ + e
MnO4 + 8H+ + 5e
Mn2+ + 4H2O
MnO4 + 8H+ + 5e
TiO2+ + 2H+ + e
Mn2+ + 4H2O
Mn2+ + 5TiO2+ + 2H+
Fe3+ + e
MnO4 + 8H+ + 5e
Mn2+ + 4H2O
= 4,3.10-3 ( *)
Ta c : E0Ag+ / Ag = 0,799 V
*Ly 20ml dung dch A cho qua ct kh bc th:
Khi ch c Fe3+ b kh to thnh Fe2+:
Fe3+ + Ag
Fe2+ + Ag+
8
Trn Th M L Lp Ha 3B
Bi tp ln
Fe2+
Cr2O7
6Fe2+ + Cr2 O7
Fe3+ + e
2
+ 14H+ + 6e
+ 14H+
2Cr3+ + 7H2O
Ta c:
S Fe2+ = S Cr2O7 2
Hay
= 1,512.10-3 (**)
x =
*Ly 20ml dung dch A, thm vo NH3 v H2O2. Khi ch c Cr3+ b oxi ho thnh
2
Cr2O7 .
3
2OH- + 2e
H2O2
2Cr3+ + 14OH- + 6e
Cr2 O7 + 7H2O
Cr2 O7 + 7H2O
(1)
Vy dung dch sau khi cho thm NH3 v H2O2 gm: Fe3+ , Cr2 O7
, TiO2+
Fe2+
Fe3+ + e
9
Trn Th M L Lp Ha 3B
Bi tp ln
Cr2O7
+ 14H+ + 6e
6Fe2+ + Cr2 O7
+ 14H+
S Cr O 2 = S Fe2+ =
2 7
Ta c:
V: Cr2 O7
Nn :
2Cr3+ + 7H2O
+ 14H+ + 6e
S Cr3+ =
= 6,2 . 10-4
2Cr3+ + 7H2O
1 S
Cr2O7 2
6
S Cr3+ = 2.
Hay
y = 2.
1 S
Cr2O7 2
6
1
.6,2 . 10-4 = 2,0667 .10-4 (***)
6
x + y + z = 4,3.10-3
x = 1,512.10-3
z = 2,5813.10-3
y = 2,0667 .10-4
Gi mFe , mCr , mTi ln lt l khi lng ca Fe, Cr, Ti trong hn hp phn tch
10
Trn Th M L Lp Ha 3B
Bi tp ln
Trong 20ml ta c:
S Fe3+ = x = SFe= 1,512.10-3
=1,512 .10-3 56 = 84,672.10-3 g = 84,672 mg
mFe= SFe
-4
S Cr 3+ = y = SCr = 2,0667.10
mcr= SCr
mTi= STi
= 423,4 mg
macr= 10,746
= 53,73 mg
mTi= 132,902
= 619,51mg
BI 3 : Cho 1g mu lom ( thnh phn H2SO4 , SO3 v SO2 ) vo nc pha thnh 250 ml .
Chn 25 ml dung dch ht 21,2 ml NaOH 0,1 M ( chun n pH = 4) . Mc khc ,
cng chun 100 ml dung dch phn tch trn bng dung dch It ht 37 ml dung dch I2
0,025 N . Tnh thnh phn % cc cu t c trong mu
( Bit H2SO3 c pK1 =1,76 ; pK2 = 7,21 ).
BI GII :
lum ( H2SO4 ; SO3 ; SO2 ) vo nc pha thnh 250 ml ta c dung dch c cha H2SO4;
H2SO3 do:
SO3 +H2O
SO2 +H2O
Ta c :
H2SO4
H2SO3
H2SO3
H+ + HSO3-
K1 = 10-1,76
HSO3-
H+ +SO32-
K2 = 10-7,21
Nhn xt :
11
Trn Th M L Lp Ha 3B
Bi tp ln
pH =
= 4,49
pH =4
Chun n pH = 4
H2SO4 + 2NaOH Na2SO4 + 2H2O
H2SO3 + NaOH NaHSO3 + H2O
=
SO3 =
SO2 =
Gi x l s gam H2SO4 , y l s gam SO3 , z l s gam SO2
Ta c:
S lg H2SO4 + S lg SO3 + S lg SO2 = S lg NaOH
Chun vi I2:
SO2 + 2 H2 + I2
H2SO4 + 2HI
SO2 =
S lg SO2 = S lg I2
z = 0,148
(2)
x +y +z = 1
(3)
Gii phng trnh (1) ,(2) ,(3) ta c
x= 0,5254 ; y= 0,3266 ; z = 0,1480
12
Trn Th M L Lp Ha 3B
Bi tp ln
BI 4: 1,234 g cht phn tch cha PbO v PbO2 c ch ha vi 20ml H2C2O4 0,25 M
kh PbO2 thnh Pb2+ . Sau dung dch c trung ha bng NH3 kt ta ton b
ch di dng xalat ch . Chun nc lc thu c bng dung dch KMnO4 0,04M th
ht 10ml. Ho tan kt ta trong axit v chun dung dch bng dungdch KMnO4
0,04M ht30 ml.Hy tnh thnh phn % ca PbO v PbO2 trong mu phn tch bit
PbO = 223 ; PbO2 = 239 .
PbO, PbO2
H2C2O4
Pb2+,PbC2O4
H2C2O4
H2C2O4d
PbC2O4
KMnO4Axit ho
CO2, H2O
H2C2O4
KMnO4
CO2, H2O
13
Trn Th M L Lp Ha 3B
Bi tp ln
2H+ + C2O42-
Pb2+ +2 H2O
2CO2+2e
PbO2 + 2H2C2O4
PbC2O4
(3)
= y
14
Trn Th M L Lp Ha 3B
Bi tp ln
Ta c:
y = S3
hay
S2 = S 3
2H+ + C2O42-
2 MnO4 + 8H + 5e
5 C2O42-
Mn2+ + 4H2O
2CO2+2e
= 2.10-3
Pb2+ + H2C2O4
(5)
V vy :
S H 2C2O4 (5) = S1 + S3
*Chun dung dch thu c bng dung dch KMnO4 0,04M ht 30 ml. Tc l chun
lng H2C2O4 to thnh:
5H2C2O4 + 2MnO4- + 6H+
Ta c:
Hay :
S H 2C2O4 = S KMnO4
S1 + S3 =
= 6.10-3
= 0,01
15
Trn Th M L Lp Ha 3B
Bi tp ln
Vy ta c:
S1 = 4.10-3 =x
S1 + S2 + S3 + S4 = 0,01
S2 = S3
S2 = 2.10-3 = y
S4 = 2.10-3
S3 = 2.10-3
S1 + S3 = 6.10-3
S4 = 2.10-3
Vy :
SPbO = S1 = 4.10-3 =x
Khi lng ca PbO l : mPbO
= SPbO
4.10-3
223
= 0,446 (g)
2
S PbO2 = S2 = 2.10-3 = y
Khi lng ca PbO2 l : mPbO2 = S PbO2
= 2.10-3
239
= 0,239 (g)
2
Bi tp ln
BI GII :
*Xt trng hp chun ca KOH :
3 KOH + KHC2O4.H2C2O4.2H2O K2C2O4.K2C2O4.2H2O + 3 H2O
ng lng ca KHC2O4.H2C2O4.2H2O l :
(1)
= 84,667
Ta c :
S lg KHC2O4.H2C2O4.2H2O (1) = S lg KOH =
=4,9815.10-3
2H+ + C2O42-
H2C2O4
2 MnO4 + 8H + 5e
Mn2+ + 4H2O
5 C2O42-
2CO2+2e
Ta c :
S lg MnO4 = S lg H2C2O4 =
= 6,64.10-3
ng lng ca KHC2O4.H2C2O4.2H2O l :
= 63,5
Trn Th M L Lp Ha 3B
Bi tp ln
Vy :
Khi lng ca KHC2O4.H2C2O4.2H2O tiu th trong cc qu trnh chun trn l :
0,4218 + 0,4316 = 0,8434 (g)
BI GII :
a) Cc phn ng ln lt l:
MnO2 + 2e +4H+
H2C2O4
2H+ + C2O42-
C2O42-
2CO2+2e
Mn2+ + 2H2O
18
Trn Th M L Lp Ha 3B
Bi tp ln
(1)
2H+ + C2O42-
3 H2C2O4
3 C2O42-
2CO2+2e
HNO3 + 3H+ + 3e
(2)
NO + 2H2O
6 Mn2+ + 4H2O
(3)
MnO4- + 8H+ + 5e
5 Cr2 O7 + 14H+ + 6e
2Cr3+ + 7H2O
Cr2O7 + 14H+ + 6e
3
(4)
2Cr3+ + 7H2O
2I-
I2 + 2e
(5)
T phng trnh ta c: mu xanh nht l mu ca ion Cr3+ , cn xanh m l do iot sinh ra (5)
kt hp vi h tinh bt nn c mu xanh m . Nn ta thy hin tng dung dch chuyn t
mu xanh nht sang mu xanh m
19
Trn Th M L Lp Ha 3B
Bi tp ln
b) Ta c :
=
=
= 6,25 10-3
= 1,29
10-3
= 2,48 10-3
Khi lng MnO2 trong mu phn tch l : 2,48 10-3 87 = 0,215 (g)
Vy phn trm MnO2 trong mu phn tch l :
%
= 86 %
20
Trn Th M L Lp Ha 3B
Bi tp ln
TRNG I HC S PHM HU
KHOA HA HC
Cn b hng dn
Thy Nguyn Hu Hin
HU, 11 /2011
21
Trn Th M L Lp Ha 3B
Bi tp ln
TRNG I HC S PHM HU
KHOA HA HC
Cn b hng dn
Thy Nguyn Hu Hin
HU, 11 /2011
22
Trn Th M L Lp Ha 3B
Bi tp ln
TRNG I HC S PHM HU
KHOA HA HC
HU, 11 /2011
23
Trn Th M L Lp Ha 3B
Bi tp ln
24
Trn Th M L Lp Ha 3B
Bi tp ln