2.8. 1) p dng qui tc ng lng: 125 = 41,2 0,09 103 M = 337,1.

M
125
1000
Co =

= 0,0742M
337
50
2) Khi thm 8,24 ml (cha n T)
p dng: h = K1 P K = h P vi P = CV = 009 824 = 0,1998 0,2
P
CoVo 00742 50
1P
4,3 02
5
K = 10
= 1,25 10 .
08
WK vi C' = CCo =009 00742 = 0,04067 pH = 8,75.
2) h =
C'
C + Co 009 + 00742
2.9. V = 10 ml h = K.1 P pH = 4,35.
P
WK pH = 8,14
V = 12,5 ml h2 =
C'

V = 12,45 ml h = K.1 P pH = 6,15.

P
V = 13 ml h = W V + Vo pH = 11,12
P 1 VoCo

2.10. TN1: Cho 20 ml dung dch NaOH C (M) vo 30 ml CH3-COOH Co (M) t pH = 10,5 ln hn pHT = 8,74, ngha l dung dch tng ng
vi sau im tng ng, ta c:
h = W V + Vo = 105 vi P = CV = 2C
CoVo 3Co
P 1 VoCo
Sau khi thay s 2C 3Co = 1,58 103
()
TN2: Thm tip 0,05 mmol HCl, t pH = 6 < 8,74 trc im tng ng. Ta c:
h = K.1 P = 106 P = 0,94556
P
Vi P = CV 005 = 20C 005 = 0,094556 2C 2,837Co = 5 103
()
CoVo
30Co
2
2
Gii () v () C = 3,22 10 M v Co = 2,098 10 M.
NH3 + H+
2.11. 1) NH4+
K = 109,26
0,2--------------------0,01
0,2x----------------0,01+x
p dng L tc dng khi lng vi x 0,01 x = 107,96 0,01.
Vt h = [H+] = 0,01 pH = 2.

2) Gi NaOH (C,V) v HCl (Co1,Vo) v NH 4 (Co2,Vo)

T phng trnh trung ho in: [Na+] + [H+] + [NH4] = [OH] + [Cl]
CV + h + Co2Vo h = W + Co1Vo + Co2Vo
V + Vo
V + Vo h + K h
V + Vo
CV Co1Vo = (W h) + Co2Vo Co2Vo h
V + Vo
h
V + Vo V + Vo h + K
= (W h) + Co2Vo K
h
V + Vo h + K
V
+
V
CV
o
Nhn 2 v cho
v t P =
, ta c:
CoVo
Co1Vo
P 1 = (W h)V + Vo + Co2 K
h
CoVo Co1 h + K
W
V
q = P 1 = ( h) + Vo + Co2 K vi K h, thay s vo q = 1,74 102 hay 1,74%.
h
CoVo Co1 h
3) p dng cng thc q khi tnh BNC, ch mi trng (axit)
u BNC: 150h2 0,001h 1,099.108 = 0 h = 1,25 105 pH = 4,91.
Cui BNC: 150h2 + 0,001h 1,099.108 = 0 h = 5,85 106 pH = 5,23.
2.12. V = 0 ml h =

WK = 1010,83 khng h hn nhiu so K

Co

Nu gii phng trnh bc 2 suy ra t : 1 = W 1 + K pH = 10,82.

h Co K + h
P
V = 10 ml h = K.
pH = 9,44
V = 20 ml h = K. P pH = 8,66.
1P
1P
P
V = 24,95 ml h = K.
pH = 6,56.
1P
V = 25 ml h2 = KC' vi C' = CCo = 0,0125M pH = 5,58.
C + Co
C
V
V = 25,02 ml h = (P 1) o o pH = 5
V + Vo
C
o
V = 30 ml h = (P 1) Vo pH = 2,64.
V + Vo
2.13. 1) P = 0 h =

WK = 1011,22 vi C = 0,15M
o
Co

Chun 50% , P = 0,5 h = K.

P pH = 9,26
1P

Khi P = 1 h2 = KC' vi C' = CCo = 0,09375M pH = 5,14.

C + Co
2) p dng cng thc sai s q = (h W) C + Co K vi h W v K
h CCo
K+h
h
q = 0,1% < 0,2% vy MD dng c.
2.14. 1) V = 10 ml T 1 h2 = K1K2C' vi C' = CCo = 2102M pH = 4,86.
K1 + C'
C + Co 3
V = 20 ml TD 2 h2 = K2K3 + WK2 vi C'' = CCo = 5 103M pH = 9,41.
C''
C + 2Co
2) Khi dng pH = 4,4 p dng qI sai s: 1,12%
3) Khi dng pH = 9 p dng qII sai s: 0,7%.
2
2.15. T phng trnh ng chun ca axit 2 nc: P 1 = (W h)V + Vo + 2 K1K2 h
h
CoVo
h + hK1 + K1K2

Ch rng VT1 = 25 ml v VT2 = 50 ml.

Nu V = 20 ml trc T 1 P 1 = hV + Vo + h Vi P = 0,8
CoVo h + K1
Thay s vo K1 = 5,06 103
Nu V = 50 ti T 2 P 2 = W C + 2Co h Vi P = 2
h
CCo
K2
K2 = 2 106.
2.16. 1) iu kin K1/K2 104 khng tho mn khng C ring c.
Do C lun n nc 2: h2 = WK2 C + 2Co pH = 8,34.
CCo
2) h = K2 2 P = 106 P = 1,9817 vy C c 98% k t nc 1.
P1
2.17. Chun n pH = 4,4: C n nc th 1 ca H3PO4
[H+] + [Na+] = [Ac] + [H2PO4] + [OH]
vi h v W khng ng k v [HPO4] v [PO43] khng ng k
h
Gi C1: nng mol ca ax. Axetic v C2: nng ax. H3PO4.
20 01 = K 25C1 + 25C2 thay K = 104,76 v h = 104,4
20 + 25 K + h 20 + 45 20 + 25
2 = 7,59C1 + 25C2

()

Chun n pH = 9 C n nc th 2:
[H+] + [Na+] = [Ac] + 2[HPO42] + [OH] vi h, W khng ng k
h
01 45 = 25C1 + 2 25C2 4,5 = 25C + 50C
()
1
2
25 + 45 25 + 45
70
Gii h () v () C1 = 5,091 102M v C2 = 6,454 102M
2.18. 1) Tnh c VT1= 25 ml, VT2 = 50 ml.
V = 20 ml h = K2 P vi P = CV = 0,8 h = 109,73
CoVo
1P
W
+
K
C'
2
2
V = 25 ml h =
vi C' = CCo h = 108,34.
C + Co
1 + K11C'
V = 30 ml h = K1 P 1 vi P = 1,2 h = 106,95.
2P
V = 50 ml C''= 5 103 < L = 3 102M
p dng: P 2 = h C + 2Co K1 vi P = CV = 2 v h K1
CCo
h + K1
CoVo
h = 104,325.
2
2) q = (h W)C + Co + 2 h K1K2
= 1,76 102 hay 1,76%.
h CCo
h + K1h + K1K2
2.19. Lc PP i mu: Slg NaOH + Slg Na2CO3 = Slg HCl
1,2( x 1 + y 1 ) = 30 0,5 103
()
100 40
100 106
Lc MD i mu: Slg NaOH + Slg Na2CO3 = Slg HCl
1,2( x 1 + y 1 ) = 35 0,5 103
()
100 40
100 53
Gii h x = 41,67% v y = 22,08%.

2.20. Nng dd B (NaOH): C' = 31 02 = 0,248M

25
1) Gi x: s mol NaHCO3 v y s mol Na2CO3 (trong 25 mol dung dch A)
S mol HCl tc dng vi 25 ml dd A: x + 2y = 48 0,2 103 = 0,0096 ()
Sau khi thm 50 ml dung dch B vo 25 ml dung dch A ri trung ho NaOH d bng HCl:
S mol NaOH = x + s mol HCl
50 0,248 103 = x + (25 0,2 103) x = 7,4 103 mol NaHCO3 %NaHCO3 = 82,88%
T () y = 1,1 103 mol Na2CO3 %Na2CO3 = 15,54%.
2) Ta c th xem Na2CO3 (8,5 mmol) b chun bng axit n dd A: gm Na2CO3 (1,1 mmol v NaHCO3 7,4 mmol)
s mmol NaHCO3
Lc P = CV =
= 74 = 0,87
CoVo tng s mmol Na2CO3 ban u 85
Ap dng h = K2 P = 109,5 pH = 9,5
1P
3) Nu C 25 ml dung dch A bng HCl n PP chuyn mu (n NaHCO3):
S lg Na2CO3 = Slg HCl 1,1 = V 0,2 V = 5,5 ml.
2.21. Nhn xt: pH = 7,21 h = 107,21 = K2 2 P P = 1,5
P1
(ngha l C n nc 2 ca H3PO4)
Khi pH = 9,78 pK1 + pK2 = 9,765 C n va ht nc 2 ca H3PO4.
2
Th tch NaOH C c 1 nc H3PO4: 5 2 = 10 ml.
Suy ra th tch NaOH C va ht H2SO4: 15 5 10 = 10 ml.
C (H3PO4) = 10 01 = 0,2M v C (H2SO4) = 01 10 = 0,1M.
5
52
Trung ho hon ton 5 ml dung dch hn hp H3PO4 v H2SO4 (ngha l n nc 3 H3PO4)
Ta c: V 0,1 = (0,1 2 5) + (0,2 3 5) V = 40 ml.
2.22. S mol H3PO4: 0,025 0,4 = 0,01 mol. S mol Na3PO4: 0,03 0,5 = 0,015 mol.
Xt t l f = s mol H3PO4 = 0,667 0,5 < f < 2 , ta c phn ng:
s mol Na3PO4
H3PO4 + 2Na3PO4 3Na2HPO4
2H3PO4 + Na3PO4 3NaH2PO4
a-----------2a--------------------3a
b-----------0,5b------------------1,5b
nH PO = a + b = 0,02 v nNa PO = 2a + 0,5b = 0,015 a = 002 v b = 001
3
4
3
4
3
3
nNa HPO = 3a = 0,02 mol v nNaH PO = 1,5b = 0,005 mol
2

Nu C n MD chuyn mu cn V ml HCl: 0,02 = 0,1V V = 200 ml

Nu C n PP chuyn mu cn V' ml NaOH: 0,005 = 0,1V' V' = 50 ml

EoFe + 5EoMn
= 1,37V
6
2) Dng C E = 0,83 V < 1,37 V trc T, thiu C
o
Dng E = EFe + 0,059lg P P = 0,99714 q = P 1 = 0,00286 hay 0,286%
1P
o
3.2. 1) C thiu 0,2%: E = EU + 0059lg P vi P = 0,998 E = 0,414 V
2
1P
o
o
2E + ECe
C n T: E = U
= 0,703V
3
3.1. 1) ET =

C n qu 0,2% : E = ECe + 0,059 lg(1 P) vi P = 1,002 E = 1,280 V

o
2) Dng th 0,42 V < 0,703V trc T: E = EU + 0059lg P P = 0,9988
2
1P
NV
P=
= 0,9988 V = 39,95 ml.
NoVo
o

Dng th 1,27V > 0,703 V sau T: E = ECe + 0,059 lg(1 P) P = 1,0013

P = NV = 1,0013 V = 40,052 ml
NoVo
3.3. 1) T 2 bn phn ng: Fe3+ + 1e

Fe2+

K1 = 10 EFe/0,059

Ti3+ + H2O e
TiO2+ + 2H+
K2 = 10ETi/0059
11,36
Phn ng C c K = K1K2 = 10
o
EFe + EoTi
2) Tnh VT = 50 ml v ET =
= 0,435V
2
3+
o
Theo E = EFe + 0,059lg[Fe2+] vi [Fe2+] = 005 20 = 1 thay vo biu thc E [Fe3+] = 107,52
[Fe ]
20 + 50 70
o
3) Dng E = 0,330 V < ET qu C, ta dng E = ETi + 0,059lg 1 P 1 v V 50 ml
P1
144
+
068
3.4. ET =
= 1,06V
2
* q = 0,001 P = 0,999

3+
o
o
p dng E = EFe + 0,059log[Fe2+] = EFe + 0,059log P = 0,857 V
[Fe ]
1P
* q = +0,001 P = 1,001
o

p dng E = ECe + 0,059log(P 1) = 1,263v

BNC: 0,857 1,263V: Chn Feroin chuyn mu r th 1,12V t sang xanh nht.
o

3.5. Chun c 50% (P = 0,5): E = ESn + 0059log P = 0,15V

2
1P
o
0059
Chun c 90% (P = 0,9): E = ESn +
log P = 0,178V
2
1P
o

EFe 2ESn

C c 100% (P = 1): ET =

= 0,3567V

C n 110% (P = 1,1): E = EFe + 0,059log(P 1) = 0,711V.

Au3+ + 3I
AuI + I2
a----------------------------a mol
2Cu2+ + 4I
2CuI + I2
b------------------------------0,5b mol

2
I2 + 2S2O32
2I + S4O6
S mol I2 = a + 0,5b = S mol S2O32 = 0,5(0,076132,7103) = 1,2442.103
Hay : 2a + b = 2,4884.103
()
Ngoi ra khi lng mu hp kim: 197a + 64b = 0,1676
()
a = 1,2090.104 mol v b = 2,2466.103 mol
%Au = 14,221%.
3.7. Gi x: % khi lng H2C2O4.2H2O (M = 126)
y: % khi lng KHC2O4.H2O (M = 146)
Vi php chun axit baz: Slg NaOH = Slg H2C2O4.2H2O + Slg KHC2O4.H2O
43,1 0,125.103 = ( x 12 ) + ( y 12 )
()
100 126
100 146
2
Vi php chun oxi ha kh:Slg KMnO4 = Slg H2C2O4.2H2O + Slg KHC2O4.H2O
43,1 0,125.103 = ( x 12 ) + ( y 12 )
()
100 126
100 146
2
2
Gii h () v () x = 14,37 v y = 81,57.
3.6.

3.8. Phn ng oxi ha Cr3+ thnh Cr2 O7 :

2

S2 O 8 + 2e
2 SO4

+
2Cr3+ + 7H2O 6e
Cr2 O7 +14H
2
+
3 S2 O 8 + 2Cr3+ + 7H2O
6 SO4 + Cr2 O7 + 14H
2

Slg Cr3+ = Slg Cr2 O7 = Slg Fe2+ (ly d) S lg KMnO4 (C FeSO4 tha)
( x 2 ) 20 = (35 15) 0,009 5 105.
100 52 100
3
x = 3,9%.
3.9. Gi a: s mol BaCO3 = s mol Ba2+
K Cr O

H+

2
2 7
2Ba2+
2BaCrO4 2Ba2+ + Cr2 O7
a--------------------------------------------------0,5a

3+
Cr2 O7 + 6I + 14H+
2Cr + 3I2 + 7H2O

0,5a-------------------------------------1,5a
2

I2 + 2 S2 O 3
2I + S4 O 6
1,5a-----3a 3a = 0,1013 38,68 103

3
a = 1,306 103 %Ba = 1306 10 137 100% = 34,95%
0512
3.10. Gi x: s mol PbO v y: s mol PbO2
PbO + H2C2O4 PbC2O4 + H2O
(1)
x----------x-----------------x
PbO2 + 2H2C2O4 PbC2O4 + 2CO2 + 2H2O
(2)
y----------2y--------------- ----y
5H2C2O4 + 2KMnO4 + 3H2SO4 2MnSO4 + 10CO2 + K2SO4 + 8H2O
(3)
3
3 5
S mol H2C2O4 tham gia (1) v (2): x + 2y = 20.0,25.10 10.0,04.10 .
2
Hay x + 2y = 4.103
()
Khi ha tan kt ta PbC2O4 ta thu c H2C2O4 s mol:
x + y = 5 30.0,04.103 = 3.103
()
2
Gii h () v () x = 2.103 v y = 103 mol

%PbO = 2.103.223 100% = 36,14%

1234
3
100%
%PbO2 = 10 .239
= 19,36%.
1234
3.11. Pb2O3 + 6HCl 2PbCl2 + Cl2 + 3H2O
x-----------------------------------x
Pb3O4 + 8HCl 3PbCl2 + Cl2 + 4H2O
y-----------------------------------y
2

Pb2O3 2Pb2+ 2PbCrO4 Cr2 O7

x---------------------------------------------------------x

Pb3O4 3Pb3+ 3PbCrO4 1,5 Cr2 O7

y------------------------------------------------------------1,5y
2

3+
Cr2 O7 + 6I + 14H+
2Cr + 3I2 + 7H2O

(x + 1,5y)---------------------------(3x + 4,5y)
2

I2 + 2 S2 O 3
2I + S4 O 6
2

S mol S2 O 3 = 2.S mol I2 = 2(3x + 4,5y) = 35,04.103.0,2

Hay: 6x + 9y = 7,008.103
()

Ngoi ra: Cl2 + 2I

I2 + 2Cl
(x + y)---------(x + y)
2

S mol S2 O 3 = 2(x + y) = 9,36.103.0,2

Hay: x + y = 9,36.104
()
Gii h () v () x = 4,72.104 v y = 4,64.104
%Pb2O3 = 462x100% = 36,33%
06
685y
%Pb3O4 =
100% = 52,96%.
06
3.12. Tnh c VT = 100 ml
u BNC: q = 0,001 v V = 99,9 ml
3+
o
E = EFe + 0,059log[Fe2+] Vi [Fe3+] = 001 999 + 001 100 = 1999
1999
1999
1999
[Fe ]
Fe3+ sinh ra Fe3+ c sn
V [Fe2+] = 001 01 = 0001
1999
1999
1999
E = 0,68 + 0,059log
= 0,875V
0001
Cui BNC: Vc = 100,1 ml v P = 1,001
o

E = ECe + 0,059log(P 1) = 1,263V.

3.13. Nu cho qua ct kh Ag (trong dd HCl 1M), xy ra:
2+
Fe3+ + Ag + Cl
Fe + AgCl
2+
VO2+ + Ag + 2H+ + Cl
VO + H2O
Khi chun dung dch thu c bng Ce4+ th Fe2+ Fe3+ v VO2+ VO2+
S mol Ce4+ = S mol Fe2+ + S mol VO2+
8,86.103.0,2 = x + y
Hay x + y = 1.772.103
()
Nu cho qua ct kh Zn (H2SO4 1N) :
2+
2+
2Fe3+ + Zn
2Fe + Zn
+
+
2+
2+
2VO2 + 3Zn + 8H
2V + 3Zn + 4H2O
Chun bng Ce4+ th Fe2+ Fe3+ v V2+ VO2+
S lg Ce4+ = S lgFe2+ + Slg VO2+
22.103.0,2 = x + 3y
()
Gii h () v () cho x = 4,58.104 v y = 1,314.103
4
%Fe = 200 458 10 56 100% = 20,52%
50
05
3
200
1314

10
51 100% = 53,6%.
%V =

50
05
+
3+
3+
6Fe2+ + Cr2O2
7 + 14H
6Fe + 2Cr + 7H2O
o
3+
27 ] (chp nhn [H+] = 1)
Ta c: ETD = E Fe + 6E Cr + 0059lg[Fe2+][Cr2O
7
7
[Fe ] [Cr3+]2

3.14. Phn ng:

Ti T: 6[Cr2O7 ] + 3[Cr3+] = [Fe3+] + [Fe2+] m 3[Cr3+] = [Fe3+]

2

Nn suy ra: 6[Cr2O7 ] = [Fe2+], thay vo biu thc sau log:

[Fe3+][Cr2O72-] = 3[Cr3+] [Cr2O72-] = 1
3+ 2
2
[Fe2+] [Cr3+]2
2[Cr3+]
6[Cr O ] [Cr ]
2

o
o
Vy ET = E Fe + 6E Cr + 0059lg 1 3+ = 1(EoFe + 6EoCr 0018lg[Cr3+])
7
7
2[Cr ] 7

3+
VTD = 01 100 = 100 ml [Cr3+] = [Fe ] = 1 NoVo = 01 100 = 01
3
3 V+Vo 3 200
6
01
Thay vo ETD = 1,249 volt.
Nu dng E = 1 volt: trc T E = EoFe + 0,059lg P = EoFe + 0,059lgq+1
-q
1P
q = 3,77.104%
Nu dng E = 1,3 volt sau T
227 ] = Eo + 0059lg 1
E = EoCr + 0059lg[Cr2O
+ 0059lg [Cr2O3+7 ] (1)
Cr
3+ 2
3+
6
[Cr ]
6
[Cr ]
6
[Cr ]
2
NV
3+
Ta c: 6[Cr2O7 ] + 3[Cr ] =
V+Vo
3+
3+
Sau T: 3[Cr ] = [Fe ] = NoVo [Cr3+] = NoVo 01
V+Vo
3(V+Vo) 6
2
2
NV

N
V
1
NV
NoVo
o
o
V 6[Cr2O7 ] =
[Cr2O7 ] =
V+Vo
6
V+Vo
2Vy [Cr2O3+7 ] = 1NV NoVo = P 1 = q
[Cr ]
2
NoVo
2
2
0059
Thay vo biu thc (1): E = 1,33 +
lg 6 + 0059lgq q = 2,965 105 hay 2,965 103%
6
6
2
01

3.15. Vi q = 0,2% = 0,002 P = 0,998 trc T

E = EoA + 006lg P = EoIn 006
nA 1 P
n
o
o
006
0998
006
=E A+
lg
= E In
EoA = EoIn 006 0062,698
nA 0002
n
n
nA
Vi q = + 0,2% = 0,002 P = 1,002: sau TD
E = EoB + 006lg(P 1) = EoIn + 006 EoB = EoIn + 006 + 0062,698
nB
n
n
nB
2
2698
2698
o
o
Ly hiu s (2) v (1): E B E A = 0,06( +
+
)
n
nA
nB
4.1. 1)a Ti im tng ng: [Ag+] = [Br] = T = 10123 = 106,15
[ CrO24 ] =

TAg CrO
2

[Ag ]

10

11,7

10

12,3

10

0,6

(1)

(2)

3,98M

1
7,5
b. Xt : CrO42 + H2O
HCrO4 + OH WK = 10
3
C 2.10
[ ] (2.103 x)--------------x---------x
x = 7,94.106 2.103 nn [CrO42] = 2.103M.

Khi kt thc chun : [Ag+] =

TAg CrO
2

[CrO 4 ]

10

11,7

2.10

10

4,5

so vi [Ag+]T qu C

T )C + Co = 104,5. 001 + 005 = 102,42

[Ag+] CCo
001.005
q = 3,8.103 = 0,38%.

p dng: q = ([Ag+]

2) u BNC: q = -0,001 = (m T )C + Co Vi m T
m CCo
m
123
10
001
+
005
=-0,001 =

m = 107,22 pAg = 7,22

m
001.005
Cui BNC: pAg = 12,3 7,22 = 5,08
Vy BNC: t pAg = 7,22 n pAg = 5,08
4.2. T cng thc sai s: q = ( T m) C + Co Vi m = [Pb2+]
m
CCo
T
Trc im tng ng: m m 005 + 001 = 0,001 m = 8,333.106
m
005.001
[ CrO24 ] =
[Ag+] =

TPbCrO
2

[Pb ]

10
10

12

8,92

10
10

10

14

5,079

1,54

10

8,92

= 2,88.102M

0,06
Sau im tng ng: m T T
= 0,001 T = [ CrO24 ] = 105,079
m m 0,0005
m

[Ag+] =
4.3.

10
10

12

5,079

= 3,46.104M.

Ag+ + SCN
T = 1012
AgSCN
3
Co = CAgNO = 001 55 = 5,5.10 M
; C = CSCN = 0,01M
3
100

Cng thc sai s: q = ([SCN]* [Ag+])C + Co , trong [SCN]* = [SCN] + [Fe(SCN)2+]

CCo
2+
Ta cn phi tm [Ag+]. T cn bng: Fe3+ + SCN
= 103,03
Fe(SCN )
3
6
[ ]:
5.10 ----x---------------6.10
x = 1,12.106
12
[Ag+] = T = 10 6 = 8,93.107 M
[SCN ] 112.10
V [SCN]* = [SCN] + [Fe(SCN)2+] = 1,12.106 + 6.106 = 7,12.106M
3
Vi q = ([SCN]* [Ag+])C + Co = (7,12.106 8,93.107) 001 + 55.103 = 1,754.103
CCo
001.55.10
Hay q = 0,18%.
+

4.4. Ag+ + Cl
AgCl v Ag + SCN
AgSCN
+

S mol Ag = S mol Cl + S mol SCN (p)

(500,021)103 = (1000,009).103 + a
(vi a: s mol SCN phn ng)
a = 0,15.103 mol [SCN]d =

(0,6 0,15)10

163

3
10 2,7610 M

AgCl + SCN
102
AgSCN + Cl
3
C
2,76.10
[ ]
(2,76.103 x)---------------x
x = 2,73.103 v [SCN] = 3.105M
Tnh li nng CFe3+ = 11 = 6,13.103M
163
Xt cn bng: Fe3+
+
SCN
Fe(SCN)2+ = 103,03
3
5
C
6,13.10 ------------------3.10
[ ] (6,13.103 3.105 + x)-----x-------------(3.105 x)
x = 3,98.106
[Fe(SCN)2+] = 3.105 3,98.106 = 2,602.105 > 6.106 : Vy c mu xut hin
4.5. S lg Ag+ = S lg IO3 + S lg SCN
50 0,1 = 50Co + 30.0,1 Co = 0,04M
q = ([SCN]* [Ag+])C + Co vi [SCN]* = [SCN] + [Fe(SCN)2+]
CCo
T Fe3+ + SCN
Fe(SCN)2+
= 103,03
3
6
T
[ ] 5.10
x
6.10 . LTDKL cho x = 1,12.106 v [Ag+] =
= 8,93.107
112.106
[SCN]* = [SCN] + [Fe(SCN)2+] = 1,12.106 + 6.106 = 7,12.106
3
Tnh li nng u Ag+ : Co = 300110 1000 = 0,03M (s mol Ag+ d = s mol SCN)
100
Vy: q = (7,12 106 8,93 107)003 + 01 = 2,7 104 hay 0,027%.
003 01
2
25No 8 N
2+
4.6. 1) S lg Fe = S lg Cr2O7
=
vi N = 6CM = 0,6M No = CFe2+ = 0,192M
1000
1000
Chun Cl: S lg Ag+ = S lg Cl S lg SCN
25 No = (100 0,16) (25 0,12) No = CCl = 0,52 M

2) Nu ch c (FeCl2 cha b oxi ho): CCl = 2CFe2+ = 0,52 CFe2+ = 0,29 M

0068 100
Fe2+ b oxi ho thnh Fe3+:
= 26,15%
026
2

3) T 2 biu thc Nernst ca cp Fe3+/Fe2+ v Cr2O7 /Cr3+ ta c:

3+
27 ] (chp nhn [H+] = 1)
7ET = EoFe + 6EoCr + 0,059lg [Fe2+][Cr2O
3+ 2
[Fe ] [Cr ]
2

Ti T: 6[Cr2O7 ] + 3[Cr3+] = [Fe3+] + [Fe2+] m 3[Cr3+] = [Fe3+]

2

Nn suy ra: 6[Cr2O7 ] = [Fe2+], thay vo biu thc sau log:

[Fe3+][Cr2O72-] = 3[Cr3+] [Cr2O72-] = 1
3+ 2
2
[Fe2+] [Cr3+]2
2[Cr3+]
6[Cr O ] [Cr ]
2

o
o
Vy ET = E Fe + 6E Cr + 0069lg 1 3+
7
7
2[Cr ]

4.7. S lg NaCl + S lg KCl = S lg AgNO3 S lg NH4SCN

( a 60 ) + ( a 37 ) = 25 0,1 103 5,5 0,1 103 a = 0,128 gam.
585 100
745 100
4.8. 1) Chun bng HCl: S lg NH3 = S lg HCl
C 25 103 = 0,1 15 103 CNH3 = 0,06M
Xc nh NH4Cl : xc nh Cl
S lg AgNO3 = S lg SCN + S lg Cl(NH4Cl) + s lg HCl (tc dng NH3)
60 0,1 103 = (18 0,2 103) + (C 25 103) + (15 0,1 103) C = 0,036M
2) Sau khi tnh s b mi trng mi trng baz
+

Ta c: NH3 + H2O
WK1 = 104,74
NH4 + OH
C
0,06
0,036

[ ]
0,06 x
(0,036 + x) x
p dng L tc dng khi lng: vi k x 0,036 x = 104,52 = [OH]
h = [H+] = 109,48 pH = 9,48
3) Ti T: h l NH4Cl nng C1. Th tch ti im tng ng: 25 + 15 = 40 ml
Vy C1 = (0,06 + 0,036)25 = 0,06M
40
+
+
Xt cn bng: NH4
K = 109,26
NH3 + H
[ ] (0,06 x)
x
x LTDKL x = 105,24 pH = 5,24: Dng metyl .
4.9. 1) Gi x: % NaOH v y: % NaCl
S lg NaOH = S lg HCl x 67 25 = 22.0,5.103 x = 65,67%
100 40 250
S lg AgNO3 = S lg Cl + S lg SCN
35 0,11 103 = ( y 67 25 ) + (4,7 0,095 103) y = 29,70%
100 585 250
Nng NaOH trong dung dch B: CM = 22 0,5 103 1000 = 0,44M pH = 13,64
250
W
C
+
C
W
o pH = 10 h
2) q = (h )
h CCo
h
14
W
C
+
C
10
05
+
044
o
=
= 10
= 4,27.104 q = 0,043%
h
CCo
10
05 + 044
3) Mi trng qu kim khng chun bng Mohr c.
4.10 1) Khi MD chuyn mu pT 4 (T 2)
S lg Na2CO3 = S lg HCl
25 m = 0,2 20,5 103 m = 2,173 gam % Na CO = 2173 100% = 62,08%
2
3
250 106
35
2
S lg AgNO3 = S lg NaCl + S lg HCl (mi thm)
30,5 0,2 103 = 25 m + (0,2 20,5 103) m = 1,17 g. %NaCl = 117100% = 33,43%.
250 585
35
+
CV
2) CAg+ =
= [Ag ] + mAgCl + 2mAg2CrO4 (1)
(m: s mol trong 1 lt dung dch)
V + Vo
CCl = CoVo = [Cl] + mAgCl
(2)
V + Vo
Ly (1) tr (2) : CV CoVo = ([Ag+] [Cl] + 2mAg2CrO4 )
V + Vo
Suy ra: q = ([Ag+] [Cl] + 2mAg2CrO4 )C + Co
CCo
Vi Co (Cl) : bao gm Cl trong NaCl v Cl trong HCl mi thm
3
Co = (305 0,2 10 ) 1000 = 0,1341M v C = CAg+ = 0,2M
455
575

107 1000 = 7,565 106

mAg2CrO4 =
455 + 305
[CrO42-] = (5 103) (7,565 106) = 5 103
1012 = 1,414 105 v [Cl] =
1010
[Ag+] =
= 7,07 106
5.103
1414 105
Thay vo biu thc q q = 0,027%
Bi 4.11 gii ti lp (phn l thuyt)
50.0 01
5.1. Ti im tng ng: VT =
= 25 ml
0 02
Khi V = 24,9 ml < VT : T phng trnh ng C rt ra:
Vo + V
0 02.24 9
[Sr]*
= P 1 vi P =
= 0,996 [Sr]* = 2,67.105
CoVo
0 01.50
1
1
5
pH = 10 : Sr =
=
13 18
10 1 [Sr] = [Sr]* = 2,67.10 pSr = 4,57
1 + h1 1 + 10 .10
Khi V = 25 ml : ti im tng ng [Sr] =

CCo
1
C + Co *

2 . 102 . 108 18 = 105,18

Vi * = . Sr . Y = 108,63 . 1 . K4 = 108,18 [Sr] =
h + K4
3
pSr = 5,18
CV 0 02 . 25 1
1
Khi V = 25,1 ml qu chun . p dng :
= P 1 vi P =
=
= 1,004
C
oVo
0 01.50
*[Sr]*
[Sr]* = 8 18 1
= 105,78 pSr = 5,78
10 . 0 004
K4
1
1
5.2. Tnh *CaY : Ca =
=
Y =
0,994
12 5
12 5 = 0,5 ;
1
h
+ K4
1 + h 1 + 10 .10
*CaY = CaY . Ca . Y = 1010,27

K2
1013 5
=
= 1 ;
*CaIn = CaIn . Ca . In = 103,96
h + K2 1012 5 + 1013 5 11
Ta c : *CaIn = [CaIn] = 1 [Ca]* = 103,96 = m*
[Ca]*[In]* [Ca]*
2
1 ( 1 + m*)(C + Co ) =
1
p dng cng thc sai s: q =
(103,96 2.104 )
1027
3 96
CCo
10
*m*
*
10
.10
Tnh *CaIn : In =

nh

K4
1
1
1
=
12 5
10 = 0,9968 v Y = h + K =
4
2 82
1 + h1 1 + 10 .10
*CaY = .Ca.Y = 1010,57.0,9968. 1 = 1010,12
2 82

5.3. Ca =

Ti im tng ng: [Ca]* =

*CaIn =

1 . CCo =
*CaY C + Co

1 5.103 = 106,21
1010 12

[CaIn] = 1 1 = 106,21
[Ca]*[In]* [Ca]*

q = 2,19%
1
1
5.4. Mg =
=
= 1 ; Y = K4 = 0,355 = 1
h + K4
1 + h1 1 + 10117.1010 102
282
11 6
K
10

3
In =
=
= 0,0245
h + K3 1010 + 10116
*MgY = .Mg.Y = 108,7 . 1 .0,355 = 108,24
102
1
7
*MgIn = 10 .
. 0,0245 = 105,38
102
*MgIn =

[MgIn] = 1 1 = 105,38 [Mg]* = 1 105,38 = 106,33

[Mg]*[In]* [Mg]* 9
9

Thay [Mg]* vo cng thc tnh sai s:

q = 1 ( 1 + m*)(C + Co ) = 824 1 633 106,33. 001 + 002 = 0,01223
CCo
*m*
*
10 .10
001.002
nh

nh

hay q = 1,26%

3K4
5.5.Cc gi tr : M =1 ;Y = K
= 106,45 ; In = K2 = 0,01
h2 + K3h
h + K2
*MY = MY.M.Y = 1018.1.106,45 = 1011,55
*MIn = MIn .M.Y = 6,25 1010 .1. 0,01 = 108,795
T cng thc: *MIn = 1 [MIn] = 108,795 [M]* = 108,795
[M]* [In]
C + Co
1
Cng thc sai s: q =
[M]*
=
CCo
*MY.[M]*
0 01 + 0 01
= 11 55 1 8 795 108,795
= 0,175%
10
.10
0 01.0 01
+

[NH4 ]
0 182
= 109,26.
= 109 pH = 9
[NH3]
01
1
Tnh Zn =
= 7,94.106 v Y = K4 = 0,0521
1 + K4
1 + i[NH3]i
Vy *ZnY = 1016,5.7,94.106.5,21.102 = 1010,12
Ta c VT = VoCo = 1 ml
C
Vi im quan trng trn ng cong chun :
V = 0,5 ml (P = 0,5) pZn = 8,4
V = 1 ml (P = 1) pZn = 11,66
V = 1,3 ml (P = 1,2) pZn = 14,52
Ln cn im tng ng: cn gii phng trnh bc 2:
1
[Zn]* Vo + V = P 1
CoVo
*[Zn]*
Khi P = 0,999 pZn = 10,07 v P = 1,001 pZn = 12,25.

5.6. Tnh pH dung dch m: h = KNH4+ .

5.7.1. Chun c 50% : S lg EDTA = 1 s lg MnSO4

2
V 0 02 1 100 0 01
=
V = 25 ml
1000
2
1000
Chun n im tng ng : VT = 50 ml
Chun n pMn = 5: Ta so snh vi pMn ti im tng ng xc nh im dng chun trc hoc sau im tng ng.
*(MnY) = MnY Mn Y = 1013,8.1. K4 = 1013,8.0,0521 = 1012,52
h + K4
1 CCo =
1
2 104 = 107,35
12 52
10
* C + Co
3 102
pMn = pMn* = 7,35
Nhn xt: Khi dng chun pMn = 5 trc im tng ng
Ti im tng ng: [Mn]* =

Ta p dng: [Mn]* = (1 p)

CoVo
CV
CV
CV
105 = o o
o o
V + Vo
V + Vo CoVo V + Vo
CoVo CV 100.0 01 0 02.V
105 =
=
V + Vo
V + 100

V = 49,93 ml
Chun n pMn = 9:im dng chun sau im tng ng.
CV
1
1
Ta p dng:
=P1
=
1
C
oVo
*[Mn]*
*[Mn]*
12 521
= 002.V 1 V = 50,015 ml
10 .109 0 01.100
2. Sai s khi chun n pMn = 5 :
2
5 3.10
q = 12 521
= 102,82 = 1,51.105 hay 0,15%
5 10 .
10 .10
2.104
3. pMn ti im tng ng c tnh trn.
2+
5.8. Ga3+ + MgY2-
GaY + Mg K
2+
22+
Mg + H2Y
MgY + 2H
-1
20,3
8,7
K = GaY.(MgY) = 10 .10 = 1011,6 : rt ln
S mol Ga3+ = s mol Mg2+ = s mol EDTA
m = 5,91 103 0,0701 m = 28,88 mg Ga
69 72

5.9. S lg M2+ = S lg EDTA = 31,63 103 0,01204 2 = 0,7616 103 lg

0 7616 103 1000
cng =
= 0,0152 lg/l
50
Ghi ch: Mt n v cng = 0,5mmol/l (Ca2+, Mg2+) hay 1 lg/l
Nc c cng 1,5 4 n v : nc mm; 4 8 v : nc cng trung bnh;
> 8 v: nc cng.
5.10.Gi s nng ca Mg2+ l 103M th COH - bt u kt ta =

V nng ca Ca2+ l 103M th COH - bt u kt ta =

1010 95
= 103,97
103
pH = 10,03
105 26
= 101,13
103
pH = 12,87

Suy ra pH = 9,3 c hai ion Ca2+ v Mg2+ u cha kt ta

Nu dng Ecriocrom en T ch th pH = 9,3 th chun c 2 ion Ca 2+ v Mg2+
S lg Ca2+ + S lg Mg2+ = S lg EDTA
20 [( x 0 5021) + ( y 0 5021)] = 13,5 0,015 2 103
(I)
500 100 100
100 84
2

pH = 11,5 Mg(OH)2 kt ta hon ton v Ca2+ cha kt ta

Dng Murexit pH = 11,5 ch chun Ca2+
S lg Ca2+ = S lg EDTA
20 ( x 0 5021) = 9,4 0,015 2 103
500 100 100

(II)

Gii (I) v (II) x = 70,2% CaCO3 v y = 25,72% MgCO3

5.12.Nng mol Cu2+: Co.100 = 0,1 10 Co = 0,01M
+
[NH4 ]
pH ca dung dch m: h = K.
= 109,24 0 0026 = 1011,4 pH = 11,4
0 38
[NH3]
Cu =

K4
1010 26
1
= 1010,4 ; Y = h + K =
= 100,03
11
4
4
10 4 + 1010 26
1 + 1[NH3] + + 4[NH3]

*(Cu-Y) = 1018,8. 1010,4. 100,03 = 108,37

; In = K33K4K5 2 = 103,55
h + K3h

*(Cu-In) = 1017,9. 1010,4. 103,55 = 103,95

1
Vi *(Cu-In) = [CuIn] [Cu]* = m* =
9 = 103,95 9 = 103
[Cu]*.[In]*
*(Cu-In)
1
Sai s chun : q =
m*. C + Co = - 0,11 hay 11%
CCo
*(Cu-Y). m*
(0 023 50 0 016 38)
= 2,17 102 M
25
5.11. 1) Tnh * ca AlY v FeY :
CAl3+ =

pH = 2:
K1K2K3K4
1021 09
=
= 1013,42
2
h + K1h + K1K2h + K1K2K3h + K1K2K3K4 2 14 108
rt b
1
1
1
Fe =
= 1
Al =
=
5
21
1
1 + h 1 676
1 + 'h1 1 + 10 .10
Y =

1 .1013,42 = 1011,46
1 676
*AlY = AlY.Al.Y = 1016,13.1. 1013,42 = 102,71
*FeY = FeY.Fe.Y = 1025,1.

pH = 5:
1016 42
3K4
Y = K
=
= 106,45
2
h + K3h 1010 + 1011 16
1
1
1
1
1
2,83
Fe =
=
Al =
=
2 17
5 = 10
5
5=
1 + h1 1 + 10 .10
1 + 'h1 1 + 10 .10 2
*FeY = FeY.Fe.Y = 1025,1. 102,83. 106,45 = 1015,82
*AlY = AlY.Al.Y = 1016,13.1. 1 . 106,45 = 109,38
2
2) pH = 2 ch chun c Fe3+ :
0 023 29 6
CFe3+ =
= 2,723 102 M
25
pH = 5, *AlY ln nn c th chun c bng EDTA
CAl3+ = (50.0,023 38.0,016) = 2,17 102M = 0,0217M
25