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I HC HU

TRNG I HC S PHM
KHOA HO HC

TIU LUN HO HC PHN TCH NNG CAO

MT S BI TP TNG HP
V TNH TON CN BNG
Ging vin hng dn
PGS.TS: Nguyn nh Luyn

Sinh vin thc hin


L Th Ngc Tho
Hunh Th T
Hong Th Tuyt Giang

Nin kho 2014 - 2016

MC LC
A

M U

NI DUNG

KT LUN

A. M U
Ho hc phn tch l mt nghnh khoa hc v cc
phng php xc nh thnh phn nh tnh, thnh phn
nh lng, cu trc ca cc cht trong i tng nghin
cu.
Trong , phn tch nh tnh gip tnh ton nng
cn bng cc cu t trong dung dch khi t trng thi cn
bng nhm mc ch nh gi kh nng phn ng gia cc
cht, cc yu t nh hng n phn ng . T , tm
cch iu khin phn ng xy ra theo mun.
tm hiu v phng php gii mt s bi tp tnh
ton cn bng, chng ti tm hiu ti MT S BI
TP TNG HP V TNH TON CN BNG

B. NI DUNG

CHNG
1

L THUYT LIN QUAN V


TNH TON CN BNG

CHNG MT S BI TP TNG HP
2
V TNH TON CN BNG

www.PowerPointDep.net

CHNG 1: L THUYT LIN QUAN


V TNH TON CN BNG

I. Cn bng trong dung dch axitbaz


2
Axit mnh:

Baz mnh:

h - Ca .h - W = 0
2

h + Cb .h - W = 0

(1.1)
(1.2)

Axit yu, n chc:


W Ca .K a
h=0
h h + Ka

(1.3)

Baz yu, n chc:


W Cb .K b
x=0
x x + Kb

(1.4)

Axit a chc:
K ai
W n
h- Ca i
=0
h i=1
h + K ai

(1.5)

Cch 1 Gii PT bc cao (theo phng php tip tuyn Newton)


Cch 2 Gii theo phng php gn ng lin tc
h W+K a1 .[HA1 ] K a 2 .[HA 2 ] +...+ K a n .[HA n ] (1.5.1)
h
V [HA i ] = Ca i
K ai + h

(1.5.2)

Baz a chc:

K bi
W
x- Cb i
= 0 (1.6)
x i=1
x + K bi
n

Cch 1 Gii PT bc cao (theo phng php tip tuyn Newton)


Cch 2 Gii theo phng php gn ng lin tc

x K b1 .[A1 ] K b2 .[A 2 ] +...+ K bn .[A n ]+W


V

x
[A ] = C bi
(1.6.2)
K bi + x

(1.6.1)

II. Cn bng trong phn ng oxi ho-kh


Xt bn phn ng:
Phng
Nernst:

aOx+ne

bKh

a
RT
(Ox)
0
trnh E = Eoxh/kh
+
ln
nF (Kh)b
a
0,
059
(Ox)
0
E = Eoxh/kh
+
ln
n
(Kh)b

250C, ln = 2,303lg v p dng cho dung dch rt long:


a
0,
059
[Ox]
0
E = Eoxh/kh
+
lg
n
[Kh]b

(1.7)

- Cc yu t nh hng n cn bng oxi ho-kh:


pH, cht to phc, cht t tan.

Phng trnh tng qut:


Ox1 + Kh2 Kh1 + Ox2
- Khi D E = E OX - E Kh > 0 (1.8) th phn ng oxi ha kh xy ra.
- bit mc mnh-yu ca phn ng:

K = 10

0
0
n(EOx
-EKh
)
0,059

(1.9)

III. Cn bng trong phn ng to kt ta


- Xt cn bng:

A m Bn mA n + + nBm-

KS

K S = (A n+ )m .(B m- )n

(1.10)
Khi tch s tan
- Tch s tan c vit di dng nng K C ,ta c:
S
K CS = [A n+ ]m . [B m- ]n .f Amn+ .f Bnm-

(1.11)

Trong : fi l h s hot ca ion i


- Trong dung dch long, lc tng tc gia cc ion
khng ng k fi 1, nn:
K S = K SC = [A n+ ]m . [B m- ]n

(1.12)

* Nu tan ln hn 10-4 th phi xt n nh hng ca


lc ion hay phi tnh theo hot ).

Khi c cc qu trnh ph Tch s tan iu kin


'
S

K = [A]'[B]'
.
= K
.
S. A
Vi

(1.13)

A = 1 + 1[L]+ 1 2 [L]2 + ... + 1 ... n [L]n (1.14)


2
n
h
h
h
B = 1 +
+
+ ... +
(1.15)
K n K n .K n-1
K n ....K 1

Mi quan h gia tan v tch s tan:


- Cn bng:
Khi :
Suy ra:

A m Bn

mA n+ +nBm+

KS

S
mS
nS
m
n
n+
m-
m
n

KS =
A
.
B
=
(m.S)
.(n.S)


S=

(m+n)

KS
m m .n n

(1.16)

- Nu xt n cc qu trnh ph, th tan (S) ca AmBn


'
K
c tnh theo tch s tan iu kin ( S):
'
K
(1.17)
S' = (m+n) m S n
m .n

IV. Cn bng trong dung dch phc cht


IV.1 Hng s bn ca phc cht
IV.3.1. Hng s bn tng nc (k)
S to phc
M+L

ML

ML+L
ML 2 +L

ML 2
ML3

k1
k2
k3

.....................................

Cc gi tr k cho bit bn ca tng phc v cho


php so snh kh nng to thnh phc ca tng nc.

IV. Cn bng trong dung dch phc cht


Xt qu trnh to phc chnh M + nL
ML n
Hng s bn iu kin

ba
. ML
b=
a M .a L
'

N'

Vi

a M = 1 + bi h + bj[X]
-i

i=1

aL =

j=1

h n + K a1 h n- 1 +...K a1 K a 2 ...K a n- 1 h + K a1 K a 2 ....K a n


K a1 K a2 ...K an
H

OH

a ML = 1 +b h +b

K H2O
h

LU :

C . D

K=
a
b
A . B
c

* Cn bng: aA+bB cC+dD

* Bi tp c nhiu cn bng :
Ka
- Cn bng axit baz:
- Cn bng oxi ha kh:
- Cn bng to kt ta:
- Cn bng to phc:
Cn bng chung:

K cb = 10

0
n(EOx
-E0Kh )
0,059

KS
K f =

K = Ka.Kcb.KS.Kf

CHNG 2: MT S BI TP
TNG HP V TNH TON CN BNG

I. Bi tp tng hp chng axit-baz v


oxi ha kh
Cu 1: (trch [1]) Vit na phn ng ca hai cp NO 3-/HNO2
v HNO2/NO trong mi trng axit. Chng minh rng HNO2
b phn hy trong mi trng
pH = 0 n 6. 0
0
Cho bit, 25oC: E NO3- /HNO2 =0,94V; E HNO2 /NO =0,98V

Cc na phn ng trong mi trng axit:


NO3- +3H + +2e HNO 2 +H 2O

E 0NO- /HNO =0,94V

HNO2 +H + +e NO+H 2 O

E 0HNO2 /NO =0,98V

0'
NO 3- / HNO 2

=E

0
NO3- /HNO 2

3.0, 059
.pH
2

'
0
E0HNO
=
E
HNO2 /NO - 0, 059.pH
2 / NO

+ pH = 0
E 0NO - /HNO >E 0HNO2 /NO HNO2 b phn hy:
3

3HNO 2

+ pH = 6
E

0
NO3- /HNO 2

NO3- +2NO+H + +H 2 O

(*)

3.0,059
=0,94.6=0,409V E 0
0
>E
HNO 2 /NO
2
NO3- /HNO 2

E 0HNO2 /NO =0,98-0,059.6=0,626V


HNO2 vn khng bn, b phn hy nh phng trnh (*).
Vy: - pH c nh hng n th ca cp OXH-K.
- t pH = 0 n pH = 6, HNO2 b phn hy theo
phng trnh (*)

Cu 2: (trch [NTD di]) Hy nh gi kh nng phn


ng ca K2Cr2O7 vi KBr.
a) pH =1,00
b) pH = 3,50
Gi thit hot cc cht oxi ha, kh c xt iu
kin chun.
Xy ra cc cn bng sau:
Cr2 O 72 14H 6e
2Br

2Cr 3 7H 2O

Br2 2e

Cr2 O72 14H 6Br

E 0Cr O2 / 2Cr3 1,33V(1)


2

E 0Br /2Br 1, 065V(2)


2

2Cr 3 3Br2 7H 2O(*)

Cn bng (1) ph thuc pH, ta c:


2
[Cr
O
0,
059
0, 059
0'
0
14
2 7 ]
E E
lg

lg[H
]
3 2
n
[Cr ]
n

2
3
Cc cht c xt iu kin chun: [Cr2O7 ] [Cr ] 1M

0,059
E E 14.
pH
6
a) Ti pH=1,00, thay vo biu thc trn:
0'

E 0' 1,192V E 0Br /2Br 1, 065V


2

Phn ng xy ra theo chiu thun theo cn bng (*)


b) Ti pH=3,5

E 0' 0,84V E 0Br /2Br 1, 065V


2

Vy: ti pH =3,5, Cr2 O72- khng oxi ha c ion Br- thnh Br2

Bi tp t gii
Cu 3: (trch [ NVT]) nh gi kh nng phn ng ca MnO4vi Cl- trong mi trng H+ trong hai trng hp sau:
a) pH=0
b) Dung dch NaHCO3 pH=8,33
0
0
E

1,51V;
E
1,395V
Cho bit: MnO4 /Mn 2
Cl 2 /2Cl

Hng dn:
Xy ra cn bng sau: 2MnO4 16H 10Cl 2Mn 2 5Cl 2 8H 2O
a) Da vo 2 gi tr E0 cn bng xy ra theo chiu thun
b) pH =8,33, da vo cn bng: MnO4 8H 5e Mn 2 4H 2O
8.0, 059pH
Tnh c:
E 0' E 0
0, 72V
5

E 0'MnO /Mn 2 E Cl0 /2Cl


4

MnO4- khng oxi ha c


Cl- , cn bng xy ra theo
chiu nghch

Cu 4: nh gi tnh oxi ha-kh ca cp AsO34 /AsO33 trong mi


trng natri hiro cacbonat - ngha l pH = 8; bit E 0As/O /AsO
pH = 0 l +0,57 V.
34

Hng dn:
Vi h ny xy ra phn ng:
AsO34 2H + +2e AsO33 H 2O
Th oxi ho kh ca cp ny:
E As/O3- /AsO34

3
0,059
0,059
[AsO
4 ]
E 0As/O3- /AsO3-
lg[H ]2
lg
4
3
2
2
[AsO33 ]

3
0,059
[AsO
4 ]
E 0'As/O3- /AsO3-
lg
4
3
2
[AsO33 ]

Khi [AsO34 ] [AsO33 ], [H + ]=108


E 0'As/O3- /AsO3- 0,57
4

0, 059
lg[108 ]2 0,1V
2

33

Cu 5: (trch [ ]) Xt nh hng ca pH ti tnh oxi ha


kh ca cp Fe3+ v Fe2+
- 5,92
*
- 2,17 *
0
b
=
10
Cho bit: E Fe /Fe = 0,771V, bFeOH2+ = 10 , FeOH+
K S(Fe(OH ) = 10- 3,75 , K S(Fe(OH) = 10- 15,1.
2
3+

2+

Hng dn
Xt na phn ng: Fe3+ + e Fe2+ E 0Fe /Fe = E10 = 0, 771V
* Trong mi trng axit (pH<2), th khng ph thuc
vo pH.
* Trong mi trng pH cao hn (pH >2), ion Fe2+ v
Fe3+ to phc hiroxo:
3+

2+

Fe3+ + H 2O FeOH 2+ + H + lg * bIII =- 2,17


Fe 2+ + H 2O FeOH + + H + lg * bII =- 5,92

bII khi pH tng nng ion Fe3+ gim nhiu


V lg bIII > lgnn
hn nng Fe2+, ko theo th oxi ha ca cp Fe3+ /Fe2+
gim.
* pH tng cho n khi Fe3+ v Fe2+ chuyn hon ton
thnh phc hiroxo FeOH2+ v FeOH+
FeOH 2+ + e FeOH +
[FeOH 2+ ]
E = E + 0, 0592 lg
[FeOH + ]
*
- 2,17
b
10
Vi E10 - 0,0592lg * III = 0,771- 0,0592lg - 5,92 = 0,55V
bII
10
0
2

Vy, khi pH tng th E gim, tnh kh ca Fe(II) tng,


tnh oxi ha ca Fe(III) gim.

* pH tip tc tng, kt ta xut hin, ta c cp oxi ha


kh mi:
Fe(OH)3 +e Fe(OH) 2 +OHE = E 30 - 0, 0592 lg[OH]-

Vi
E 30 = E10 + 0,0592lg

K S(Fe(OH)3 )
K S(Fe(OH)2 )

10- 37,5
= 0, 771 + 0,0592 lg - 15,1 =- 0,56V
10

0
pH
=
14,
E
=
E
*
3 =- 0,56V

E gim mnh, Fe(OH)2 c tnh kh mnh

II. Bi tp tng hp chng axit baz v


phc cht
Cu 1: Tnh cn bng trong dung dch Pb2+ 0,01M v
CH3COO- 1,0M pH=2,0.

Bit: lg PbCH3COO 2,52, lg 7,8, lg K a (CH3COOH) 4,76


C cc cn bng:
2

Pb CH 3COO PbCH 3COO

lg 2,52

Pb 2 H 2O PbOH H

lg 7,8

CH 3COO H CH 3COOH

lg K a1 4, 76

Hng s bn iu kin:
'PbCH COO
3

[PbCH3COO ]'

[Pb 2 ]' .[CH 3COO ]'

[PbCH 3COO ]' [PbCH 3COO ]


[Pb 2 ]' [Pb 2 ].(1 .h 1 ) [Pb 2 ]. Pb
[CH 3COO ] [CH 3COO ].(1 K a1.h) [CH 3COO ]. CH COO
3

2,52

10
'

0,574
7,8
2
4,76
2
Pb . CH3COO (1 10 .10 ).(1 10 .10 )

Cn bng:
Pb 2 CH 3COO
C 0, 010
1

PbCH 3COO

C' 0,010 x
1 x
Theo nh lut tc dng khi lng:

[PbCH 3COO ]'


0,574
2 '
'
[Pb ] .[CH 3COO ]
x
0, 574
(0, 01 x).(1 x)
x 1 x 3, 6.10 3 M

' 0,574

Thay gi tr x vo :
[PbCH 3COO ]' 3, 6.103 M
[Pb 2 ]' 6, 4.103 M [Pb 2 ] [Pb 2 ]' . Pb 6, 4.10 3 M
[CH 3COO ]' 1 x 1
[CH 3COO ] [CH 3COO ]' . CH3COO 1, 74.10 3

Cu 2: Thit lp biu thc v tnh hng s bn iu kin ca


phc Co(CN)64- pH =10,00 c duy tr bi h m NH3 +
NH4+, c [NH3]=1,0M. Coi trong dung dch ch hnh thnh
phc Co(CN)64- duy nht. Bit: lg CO(CN) 19, 09
i vi phc Co v NH3 c lg i 1,99; 3,5; 4, 43; 5, 07; 5,13; 4,39
lg K 11, 2
Hng s to phc hiroxo ca Co2+ :
lg K b(CN ) 4, 65
Hng s phn li baz ca ion CN- :
4
6

Cc cn bng

Co 2 6CN Co(CN)64

lg 19,09

Co 2 NH 3 Co(NH 3 ) 2

lg 1 1,99

Co 2 2NH 3 Co(NH 3 ) 2 2

lg 2 3,5

Co 2 3NH 3 Co(NH 3 )32

lg 3 4, 43

Co 2 4NH 3

Co(NH 3 ) 4 2

lg 4 5, 07

Co 2 5NH 3

Co(NH 3 )5 2

lg 5 5,13

Co 2 6NH 3

Co(NH 3 ) 6 2

lg 6 4, 39

Co 2 2H 2 O

CoOH H

lg K 11, 2

CN H 2 O

HCN OH

lg K b 4, 65

4 '
[Co(CN)
'
6 ]
Hng s bn iu kin: 2 '
[Co ] .[CN ]'6

Vi

[Co(CN) 64 ]' [Co(CN) 64 ]


[Co 2 ]' [Co 2 ] [CoOH ] i 1[Co.[NH 3 ]i2 ]
6

[Co 2 ](1+k.[H ]1 i 1[i .[NH 3 ]i ]= [Co 2 ]. Co


6

[CN ] [CN ] [HCN] [CN ].(1+K a1.[H ] ) [CN ]. CN


Co . 6CN
'

Do

Thay [H+]=10-10 , [NH3]=1M v cc gi tr hng s cn bng ta


'
13,07

10
c:

Bi tp t gii
Cu 1: Hy m t cc qu trnh xy ra khi thm HCl vo
dung dch Cd(ClO4)2 cho n d. Vit biu thc nh lut tc
dng khi lng cho cc cn bng xy ra.

Cc qu trnh:
Cd(ClO 4 ) 2 Cd 2 2ClO 4
HCl H Cl
Cd 2 Cl

CdCl

Cd 2 2Cl

CdCl 2

Cd 2 3Cl

CdCl3

Cd 2 4Cl

CdCl 24

Cd 2 H 2 O

CdOH H

- Khi cho HCl n d, qu trnh to phc hiroxo ca


ion Cd2+ khng ng k do nng ion H+ ln
- Theo nh lut tc dng khi lng, ta c cc biu thc
tnh hng s bn :

[CdCl n ]
f
[Cd].[Cl ]n

[CdOH
].[H
]


2
[Cd ]

Cu 2: Tnh % Zn2+ 0,01M cha tham gia to phc vi EDTA


0,010M trong dung dch m c pH=10,00 c thit lp bi
h m NH3 - NH4Cl c
. Bit:

C NH3 C NH 0,1174M
pK a ( NH ) 9, 24
4
4
i vi phc Zn v NH c lg i 2, 21; 4,5; 6,86; 8,89
3

Axit H4Y c cc gi tr Ka:

K ai 102 ; 102,67 ; 106,16 ; 1010,26

Hng dn:
- Vit tt c cc cn bng c th xy ra trong dung dch,
lu , ion Zn2+ to phc vi EDTA v NH3
- Da vo cn bng:
Zn 2+ +Y 4- ZnY 2'
[Zn 2+ ]pu
Kt qu: %Zn cha phn ng = 2,75.10-3%

Cu 3: Tnh pH ca h gm Ni(NO3)2 0,050M v NH4NO3


0,37M.

Hng dn:
Cc cn bng: Ni 2 H 2O NiOH H

108,94

NH 4 NH 3 H

K a 109,24

H 2 O OH H

K w 1014

p dng KP vi MK l Ni2+ ,NH4+ , H2O


h [H ] [OH ] [NH 3 ] [NiOH ]
h K w K a [NH 4 ] [Ni 2 ]

Thay cc gi tr [NH4+] v [Ni2+] gn ng vo tnh c h


Thay ngc li gi tr h vo biu thc tnh [NH4+] v
[Ni2+], nu kt qu lp, suy ra gi tr pH
Tr li: pH =4,78

III. Bi tp tng hp chng axit baz


v kt ta
Cu 1: Dung dch bo ho H2S c nng 0,1M. Hng s axit
ca H2S: K1 = 1,0.10-7 v K2 = 1,3.10-13. Mt dung dch A cha
cc cation Mn2+, Co2+ v Ag+ vi nng ban u ca mi ion
u bng 0,01M. Ho tan H2S vo A n bo ho v iu chnh
pH = 2 th ion no to kt ta?
Cho: TMnS = 2,5.10-10, TCoS = 4,0.10-21, TAg2S = 6,3.10-50

iu kin xut hin kt ta:


Ta c:

CH 2S = CS2- = S

Vi

h
h2
S2- =1+
+
K a2 K a2 .K a1

2-

M n+ . A m-

. S2-

2-

> KS

CH 2S
S2-

Khi pH = 2
10- 2
(10- 2 ) 2
15
S2- = 1 +
+
= 7.69.10
- 13
- 13
-7
1,3.10
1,3.10 .1.10

0,1
-17
S =
=1,3.10
7,69.1015
Tch cc nng :
2-

[Mn 2+ ].[S2- ]=1,3.10-19 <TMnS =2,5.10-10

Khng c kt ta MnS

[Co 2+ ].[S2- ]=1,3.10-19 >TMnS =4.10-23

To kt ta CoS

[Ag + ]2 .[S2- ]=1,3.10-21 >TAg2S =6,3.10-50

To kt ta Ag2S

Kt lun: pH c nh hng n vic to kt ta ca


cc cht

Cu 2: Bc oxalat c tch s tan trong nc l 10-10,46 ti pH =


7. Tnh tan ca bc oxalat trong dung dch axit c pH = 5.
Hai hng s phn li ca axit oxalic ln lt l: Ka1 = 5,6.10-2
v Ka2 = 6,2.10-6
Ag 2SO 4 2Ag + +C 2O 2-4

Ks

C 2O 2-4 +H + HC 2O -4

K -1a 2

HC 2O -4 +H + H 2C 2O 4

K -1a1

+
+ 2
[H
]
[H
]
4
22[C2 O 2 ]'=[C 2O 4 ]+[HC 2O 4 ]+[H 2C 2O 4 ]=[C 2O 4 ]. 1+
+
[C2O 2-4 ].C2O4

K a 2 K a 2 .K a1

[H + ] [H + ]2
C2O4 = 1+
+
(*)
K a 2 K a 2 .K a1
'
K S . C2O4
K
S
3
3
S'=

4
4

Ti pH = 7 th [H+] = 10-7

C O2- 1 S
2

10

10,46

2,05.10 4

Ti pH = 5 th [H+] = 10-5
10,46
10
.2,61
3
C2O4 2,61 S'
2,83.104
4
Kt lun: pH c nh hng n tan ca cc cht. pH
cng gim th tan cng tng.

Bi tp t gii
Cu 3: Hi phi thm bao nhiu ml dung dch H2SO4 1M vo
100ml dung dch BaCl2 0,1M bt u xut hin kt ta
BaSO4? Tnh pH ti thi im ? Cho bit tch s tan ca
BaSO4 l TBaSO4=1,26.10-10 v coi H2SO4 phn li hon ton.
Nng ion SO42- khi bt u xut hin kt ta BaSO4

TBaSO4

10
1,
26.10
9
[SO 2-4 ]= 2+

1,
26.10
M
1
[Ba ]
10
V
2
[SO 4 ] 1.
1, 26.109 V=1,26.10-7 ml
100

H 2SO 4 1M

Nng do H2SO4 cung cp:

[H + ]H 2SO4 =2.[SO 42- ] 2.1, 26.10 9 =2,52.10 9 M

[H + ]H2SO4 = [H + ]H2O [H ]dd [H + ]H2O 10 7 pH=7

Cu 4: (trch) tan ca AgCl trong nc ct mt nhit


nht nh l 1,81 mg/dm3 (dung dch). Thm HCl
chuyn pH v 2,35, gi thuyt th tch dung dch sau khi
axit ha vn gi nguyn v bng 1,00 dm3. Hy tnh xem
tan ca AgCl gim i my ln sau khi axit ha dung
dch ban u n khi c pH = 2,35.
- Ta c cn bng: AgCl Ag + +Cl+ Trong nc ct:
S = 1,81 mg/dm3 = 1,26.10-5 mol/l
KS(AgCl) = S2 = (1,26.10-5)2 = 1,59.10-10 (mol/l)2
+ Trong dung dch c pH = 2,35:

Cl - H
+ =10-pH

K S =S'.(S'+10

-pH

) S' 10 S' K S 0
2

-pH

Thay cc gi tr KS v pH ta thu c S = 3,56.10-8 mol/l


Vy tan ca AgCl gim i s ln sau khi axit ha
dung dch ban u n khi c pH = 2,35 l:
S 1,26.10-5
=
354 ln
-8
S' 3,56.10

Cu 5: nh gi kh nng ha tan CuS trong HCl 1,0 M.


Hng dn:
Trong mi trng axit, [H+ ] =1M, kh ln nn b qua qu
trnh in li ca nc, nn khng k n qu trnh to
phc hiroxo ca ion Cu2+
Vit tt c cc cn bng c th xy ra trong dung dch
CuS Cu 2 S2

K S 1035,2

(1)

S2 H HS

K a12 1012,9

(2)

HS H H 2S

1
K a1
107,02

(3)

Tng hp 3 qu trnh trn,ta c cn bng tng :

1
a2

CuS 2H Cu H 2S

1
a1

K K s .K .K 10

15,3

K kh nh nn nh gi cn bng hu nh khng xy ra
theo chiu thun
nh gi nh lng:
CuS 2H Cu 2 H 2S
C
CCB

1M
1 2x

x = 2,5.10-8 M v cng b, nn Cu2+ khng tan


trong HCl 1M.

Cu 6: Tnh nng HCl phi thit lp trong dung dch


ZnCl2 0,10M sao cho khi bo ha dung dch ny bng H2S
(CH2S =0,1M) th khng c kt ta ZnS tch ra. Bit: Ks
=10-21,6, axit H2S c Ka1 =10-12,9 ; Ka2 =10-7,02
Hng dn:
Cn bng to kt ta:

Cu 2 S2 CuS

K s1

KS
.CS2 K s CS2
(1)
Cu 2
C Zn 2
Vit tt c cc cn bng to thnh trong dung dch
H 2S H HS
K a1
kt ta khng hnh thnh:C

HS H S2

Ka2

S2 Zn 2 ZnS

K s1

K a1.K a 2 .[H 2S]


[S ]
[H ]2
2

Tnh c:

Thay vo (1) ta c gi tr H+ :

[H ]

K a1.K a 2 .[H 2S].C Zn 2


Ks

[H ] 0, 692M

Vy: khng c kt ta ZnS tch ra trong dung dch bo


ha H2S 0,10M th nng HCl phi ln hn 0,692M.

Ti pH = 7 th [H+] = 10-7

C O2- 1 S
2

10

10,46

2,05.10 4

Ti pH = 5 th [H+] = 10-5
10,46
10
.2,61
3
C2O4 2,61 S'
2,83.104
4
Kt lun: pH c nh hng n tan ca cc cht. pH
cng gim th tan cng tng.

IV. Bi tp tng hp chng kt ta v


oxi ho-kh
Cu 1: nh gi kh nng phn ng ca Cu vi Ag+ khi:
a) Khng c Clb) C Cl- d
0
0
-10
E
=0,34V,
E
=0,799V,
K
=1,78.10
Bit: Cu /Cu
S(AgCl)
Ag /Ag
2+

Ta c phn ng:
E = EOX - E Kh > 0

Cu + 2Ag Cu

2+

+ 2Ag (1)

phn ng oxi ha - kh xy ra.

a) Nu khng c ClD E 0 = E 0 Ag+ /Ag - E 0Cu 2+ /Cu = 0,799 - 0,34 = 0, 459 > 0
Phn ng (1) xy ra theo chiu thun

b) C ClAgCl Ag + + Cl+

Ag +1e Ag

K1 = K0s

K 2 =10
-

AgCl + e Ag + Cl
K = K1.K 2
Ta c:

K =10

E 0AgCl/Ag / 0,059

Ag+/Ag

/0,059

E0 AgCl/Ag /0,059

E0

Ag+ /Ag

/ 0,059

10
= K s .10
E 0 AgCl/ Ag = 0, 059 lg K s + E 0 Ag+ / Ag

= 0, 209V < E

0
Cu 2+ /Cu

D E 0 < 0 Phn ng (1) khng xy ra


Kt lun: Cu kh c Ag+ khi khng c ClKhi c mt Cl- d th phn ng gia Cu v Ag+ khng xy ra.

Cu 2:[6] Gi tr tch s tan (Ks) ca PbC2O4 250C l


8,5.10-10 v th kh chun ca cp Pb2+/Pb l E0=-0,126V. a)
Tm th in cc tiu chun ca PbC2O4/Pb.
b) Tm nng ca ion Pb2+ trong dung dch Na2C2O4
0,025M cha PbC2O4 bo ho.
c) Tnh th in cc ca PbC2O4/Pb cu b bng 2 cch.
a) PbC O Pb 2+ +C O 2KS
2 4
2 4
2+

Pb +2e

Pb

PbC 2 O 4 +2e

K1 =10
Pb+C 2O

24

K=10

n.E 0 /0,059

2.E 0' /0.059

K=K s .K1 =8,5.10-10 .10 2.(-0,126)/0,059 =10-13,34


T (1) v (2) suy ra:

-13,34.0,059
E =
=-0,394V
2
0'

(1)
(2)

b) Dung dch PbC2O4 bo ho, ta c:


K S =[Pb 2+ ].[C2 O 4 2- ]
-10
K
8,5.10
-8
S
[Pb 2+ ]=
=
=3,4.10
M
2[C2 O 4 ]
0,025

c) Cch 1: Tnh t [Pb2+]:


0,059
0,059
0
2+
E=E +
lg[Pb ] = -0,126+
lg(3, 4.10 8 )
2
2
0,346V
Cch 2: Tnh t [C2O42-]:
0,059
1
0,059
1
E=E +
lg
0,394
lg
22
[C2 O 4 ]
2
0, 025
0'

0,346V

BI TP T GiI
Cu 3: [trch 6] Cho cc th
chun
sau
y:
0
AgBr(r) +e Ag+Br

E1 =0,0713V

Ag + +e Ag

E 02 =0,7996V

Trn c s hy tnh tch s tan ca AgBr 25oC.


Hng dn:
E10 /0,059
AgBr(r) +e Ag+Br
K1 =10
Ag Ag +e
AgBr(r) Ag + +Br +

Tr li: K S 4,528.1013

-E 02 /0,059

K 2 =10
K S =K1.K 2

Cu 4: [2] nh gi kh nng oxi ho kh ca cp


Ag+/Ag khi c mt ion X- (X=Cl, Br, I, SCN).
Hng dn:

E 0AgX/Ag =E 0Ag+ /Ag +0,059lgK S(AgX)

Tr li: E 0AgX/Ag = E 0Ag /Ag .Tnh kh ca Ag tng ln, tnh


oxi ho ca Ag+ gim xung.
+

Cu 5: [2] nh gi kh nng phn ng gia Cu2+ v I-.


0
0
Cho: Ks(CuI)=10-12, E Cu /Cu =0,153V,E I /3I =0,5355V
2+

3-

Hng dn:
E 0Cu 2+ /CuI =0,86V>E 0I3- /3I- =0,5355V

Tr li: Cu2+ oxi ho d dng I- to ra I3- v CuI.

V. Bi tp tng hp chng kt ta v phc cht


Cu 1: [6] Bc oxalat c tan trong nc l 2,06.10 -4 ti pH
= 7. tan ca n b nh hng khi c tc nhn to phc. Tnh
tan ca bc oxalat trong dung dch cha 0,02M NH 3 v c
pH = 10,8. Bit vi s c mt ca amoniac th ion bc to thnh
hai dng phc Ag(NH3)+ v Ag(NH3)2+. Cc hng s to phc
3
3

1,
59.10
;

6,
76.10
tng nc tng ng l: 1
2

Trong nc pH = 7: K S Ag2C2O4 = Ag . C2O 4 2- = 2S .S


+ 2

Trong mi trng c nh hng ca tc nhn to


2
phc v pH: K'S =K S . Ag . C O = 2S' .S'
+

2-

Dung dch c c mt ca amoniac v pH=10,8


Ag + +NH 3

Ag(NH 3 ) +

Ag(NH 3 ) + +NH 3
24

C 2 O +H
4

HC 2O

HC 2 O +H

Ag(NH 3 ) 2 +

K = 5,37.10
-1
a2

K 5, 62.10
-1
a1

H 2 C2O 4

+ Ag+ =1+1. NH 3 +1 2 . NH 3 =4332,16

5 1

2 1

h
h2
+ Cr O 2- =1+
+
1
2 4
K a1 K a1.K a2

K'S =K S . Ag+ . Cr O 2- = 2S' .S'


2

4. 2, 06.10

4 3

.4332,16.1 4. S ' 3

S' 3,36.103 M

Vy: tan ca bc
oxalat b nh hng
bi pH v tc nhn
to phc.

Cu 2: [2] Trn 1,00 ml hn hp m (A) gm NH3 2,0


M v NH4NO3 2 M vi 1,00 ml dung dch B gm FeCl3
2,0.10-3 M v NaF 0,20
M. C kt ta Fe(OH)3 hay
-37
K S(Fe(OH)3 ) =10
khng? Bit:
Sau khi trn, ta c:
C NH3 =C NH + =1,00M;C Fe3+ =1,0.10-3M;C F- =0,10M
4

- Trong dung dch B:


Fe3+ +F-

Fe 2+

lg1 =5,18

(1)

Fe3+ +2F-

Fe+2

lg 2 =9,07

(2)

Fe3+ +3F-

FeF3

lg3 =12,10

(3)

CFe3+ =[Fe3+ ](1+1[F- ]+ 2 [F2- ]2 +3[F- ]3 )=1.10-3

Coi [F- ] C F- =0,10


3
1.10
13
[Fe3+ ]

7,9.10
M
5,18
1
9,07
2
12,10
3
1 10 .10 10 .10 10 .10
- Trong dung dch A:

NH 3 +H 2O NH 4+ +OH C

1,0

K b =10 -4,76

1,0

[] 1,0-x
1,0+x x
x(1,0+x)
Kb =
=10-4,76 x=[OH - ]=10-4,76
1,0-x
Ta c:
[Fe3+ ].[OH - ]3 7,9.10-13 .(10-4,76 )3 =10-26,4 >K S(Fe(OH) ) =10-37
3

Nh vy vn c kt ta Fe(OH)3.

BI TP T GiI
Cu 3: [6] Bc clorua d dng ho tan trong dung dch amoniac
v to ion phc:
AgCl +2NH 3 [Ag(NH 3 ) 2 ]+ +ClMt lt dung dch amoniac 1M ho tan c bao nhiu gam
6,77
-10

=10
AgCl. Bit: KS(AgCl)=1,8.10 , [Ag(NH3 )2 ]+

Hng dn:

[Ag(NH 3 ) 2 ]+
[Ag(NH ) ]+ =
3 2
[Ag + ].[NH 3 ]2

[Ag + ] = [Cl- ];[Ag(NH 3 ) 2 ]+ =[Cl- ];[NH 3 ]=1-2[Cl - ]


+

[Ag ]=

K S(AgCl)
[Cl- ]

[Cl- ]=0,0305M

Tr li: mAgCl = 4,38 gam

Cu 4: [6] Cadimi to thnh hyroxit hi kh tan l Cd(OH)2


a.Hy tnh tan ca Cd(OH)2 trong nc nguyn cht.
-3
b.Tnh tan ca Cd(OH)
trong
nc
c
cha
10
M
ion
CN
-15 2 3
Bit: K S(Cd(OH)2 ) =5,9.10 M
Cc hng5,48s to phc
tng nc
ln lt3,65l: -1
5,12
4,63
1 =10

; 2 =10

; 3 =10

; 4 =10

M ;

Hng dn: a. Trong nc nguyn cht K S =S.(2S)


b. Trong nc c cha ion CN-:

K 'S =K S . Cd 2+ . OH - =S'.(2S')'2
- 2
- 3
- 4

=1+
[CN
]+

[CN
]
+

[CN
]
+

[CN
]
Vi: Cd2+
1
1 2
1 2 3
1 2 3 4
OH- =1

Tr li: a. S = 1,14.10-5M.
b. S = 2,40.10-3M.

Cu 5: [2] Tnh tan ca AgBr trong dung dch NH3


0,02M. Bit KS(AgBr) = 10-12,3; cc hng s bn ca phc
[Ag(NH3)i]+ tng ng l: lg1 = 3,32 (i = 1) v lg2 = 7,23
(i = 2).
Hng dn: K'S =K S . Ag . Br
+

C NH3 >>C0Ag + = K S

2 >>1

Tr li: S = 5,65.10-5.

AgBr +2NH 3

Ag(NH 3 ) 2+ +Br -

VI. Bi tp tng hp chng oxi ha-kh v


phc cht
Cu 1: [2] Tnh nng Cu2+ v Cd2+ khi lc mt mu Cd
vi dung dch CuCl2 0,01M trong hn hp NH3 + NH4NO3
trong C NH +C NH =2M;pH=9,24. Cho:
3

Cu 2+ +4NH 3

Cu(NH 3 ) 42+

1 =1011,75

Cd 2+ +4NH 3

Cd(NH 3 ) 42+

2 =106,74

0
-9,24
E 0Cu 2+ /Cu =0,337V;E Cd
=-0,402V;K
=10
2+
/Cd
a(NH + )
4

Cd+Cu 2+ Cu+Cd 2+

Cd+Cu(NH 3 ) 4 2+ Cu+Cd(NH 3 ) 4 2+

Hn hp m NH3 + NH4NO3

pK a = pH
C +C =2 C NH4+ =C NH3 =1M
NH4+ NH3
V 1 (1011,75) >> 2 (106,74) nn Cu2+ to phc hon ton.

Cu 2+ + 4NH 3
C 0,001M 1M
[]
0,996M

Cu(NH 3 ) 42+
0,01M

1 =1011,75

T hp cc cn bng:
2+

Cu +2e
Cd

Cu

K1 =10

2+

Cd +2e

Cu(NH 3 ) 2+
4

K 2 =10

Cu 2+ +4NH 3

2.E

Cu 2+ /Cu

-2.E

Cd 2+ /Cd

/0,059
/0,059

1-1

Cd 2+ +4NH 3 Cd(NH 3 ) 2+
2
4
Cd+Cu(NH 3 ) 4 2+ Cu+Cd(NH 3 ) 4 2+
K=K1.K 2 .1-1. 2 =1020,15
C
[]

[]

0, 001
-

0, 001

Cu+Cd(NH 3 ) 4 2+

Cd+Cu(NH 3 ) 4 2+

0,001-x

K 1

Cu(NH 3 ) 4 2+
Cd(NH 3 ) 4 2+

x
x 1023,15
0, 001 x

K -1

Tnh nng Cu2+ v Cd2+ theo cc cn bng:


Cu(NH 3 ) 42+

Cu 2+ +4NH 3

1023,15

1-1

0,996

1-1.10-23,15
-35
a=
=1,28.10
(0,996) 4

Cd(NH 3 ) 42+

Cd 2+ +4NH 3

0,001-b

-12

0,996

-12 .0,001
-10
b=
=1,85.10
(0,996) 4 + -12

Vy: Cu 2+ =a=1,28.10-35 M, Cd 2+ =b=1,85.10-10M

Cu 2: [6] C th ho tan hon ton 100mg bc kim loi


trong 100ml dung dch amoniac nng 0,1M khi tip xc
vi khng kh c khng?
Cho bit nguyn t khi ca Ag = 107,88; hng s
in li baz ca amoniac l Kb = 1,74.10-5; cc hng s bn
ca phc [Ag(NH3)i]+ tng ng l: lg1 = 3,32(i = 1) v
lg2 = 6,23(i = 2).
Cc th kh (th oxy ha-kh) chun 25oC:
Eo(Ag+/Ag) = 0,799V; Eo(O2/OH-) = 0,401V. p sut ring
phn ca oxy trong khng kh l 0,2095atm. Phn ng
c thc hin 25oC.

100.10-3
n Ag =
=9,27.10-4 (mol)
107,88
S mol cc i ca NH3 cn to phc l:
9,27.10-4 . 2 = 1,854.10-3(mol) << s mol NH3 (10-2mol)
Vy NH3 rt d ho tan lng Ag nu xy ra phn ng.

Ag + e Ag
+

O2 + 4e + H2O 4OHKhi cn bng E1 = E2.

E1 =E10 +0,059.log Ag +
PO2
0,059
0
E 2 =E 2 +
.log
4
OH -

Vi OH - = K b . NH 3 = 1,74.10-5 .0,1=1,32.10 -3M


Suy ra: [Ag+] = 9,2.10-5M

Nng tng cng ca Ag+ trong dung dch:


[Ag+] = [Ag+] + [Ag(NH3)+] + [Ag(NH3)2+]
= [Ag+].(1 + 1[NH3] + 2[NH3]2) = 1,58M
Gi tr ny ln hn nhiu so vi lng Ag dng
cho phn ng.
Kt lun: C th ho tan hon ton 100mg bc kim loi
trong 100ml dung dch amoniac nng 0,1M khi tip
xc vi khng kh.

BI TP T GII
Cu 3: [1] Co2+ c tnh kh rt yu, rt kh oxi ho
thnh Co3+ trong mi trng axit, nhng khi c mt
NH3 d th Co2+ d dng b oxi ho bi H2O2. Gii
thch. 0
35,16
4,39
E
=1,84V;
=10
;
=10
Cho: Co3+ /Co
Co(NH 3 )3+
Co(NH 3 )62+
6
Hng dn: E

0
2+
Co(NH3)3+
6 /Co(NH3)6

=E

0
Co3+ /Co

+0,059.lg

Co(NH3)2+
6

Co(NH3)3+
6

Tr li: E 0Co(NH3)

3+
6

/Co(NH3)62+

=0,018V<E 0H2O2 /H2O =1,77V

Cu 4: [1] nh gi kh nng ho tan ca Ag trong NH3


1M (khi khng c khng kh).
Cho bit: Kb = 1,74.10-5; Eo(Ag+/Ag) = 0,799V; hng s
Henri = 103,12; cc hng s bn ca phc [Ag(NH3)i]+
tng ng l: lg1 = 3,32(i = 1) v lg2 = 6,23(i = 2).
Hng dn:
1
Ag+2NH 3 +H 2 O Ag(NH 3 ) 2 + H 2 +OH 2
OH - .PH2 1/2 . Ag(NH 3 ) 2 +
K
K
K'=
2

NH3
+

K=10

-E 0Ag + /Ag /0,059

. 2 .1.W

Vi [OH-] t Kb.
Tr li: [Ag(NH3)2+= 10-19,55. Ag khng tan trong NH3.

Cu 5: [3] Tnh hng s cn bng i vi phn ng sau:


2AgCl +Cu

2Ag +Cu 2+ +2Cl -

0
0
-10
E
=0,337V;E
=0,799V;K
=10
2+
+
S(AgCl)
Cho: Cu /Cu
Ag /Ag

Hng dn:
+

2 Ag +1e

Ag

Ag + +Cl-

2 AgCl
2+

2.E0

/0,059

-2.E0

/0,059

K1 =10
K S2

Cu Cu +2e
K1 =10
2AgCl+Cu 2Ag+Cu 2+ +2Cl-

Tr li: K = 10-4,34.

Ag + /Ag

Cu 2 / Cu

C. KT LUN
Trong phm vi ti, nhm em tp trung la chn v
trnh by cc ni dung lin quan n bi tp tng hp v
tnh ton cn bng. C th nh sau:
- H thng ho cng thc tng qut lin quan n cn bng
axit baz, oxi ho kh, kt ta, to phc.
- Su tm, phn loi v gii c 12 bi tp tng hp lin
quan n mi phn.
- Su tm, phn loi 18 bi tp t gii lin quan n mi
phn. Cc bi tp t gii u c phn hng dn v tr li.

D. TI LIU THAM KHO


1. Nguyn Tinh Dung (2009), Ho hc phn tch cn
bng ion trong dung dch, NXB i hc s phm.
2. Nguyn Tinh Dung
3. Ng Vn T (2010), Ho hc phn tch nh tnh,
Trng i hc s phm Hu.
- p n phn Ho hc i Cng v V C, Bng A
4. Olympic Ha hc cc Trng i hc Vit Nam ln
th ba (2005), bng A.
5. thi Olympic ho hc sinh vin ton quc ln th
V (2008), bng B.
6. Chng trnh bi dng hc sinh gii quc gia tnh
Kon Tum.

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