You are on page 1of 58

1

I. OLYMPIC HA HC VIT NAM


OLYMPIC HA HC SINH VIN VIT NAM 2005 (Bng A):
Ion Fe(SCN)
2+
c mu nng bng hoc ln hn 10
-5
M. Hng s in li ca n l 10
-2
.
1. Mt dung dch cha vt Fe
3+
. Thm vo dung dch ny mt dung dch KSCN 10
-2
M (coi th tch
khng i). Xc nh nng ti thiu ca Fe
3+
dung dch xut hin mu .
2. Mt dung dch cha Ag
+
10
-2
M v Fe
3+
10
-4
M. Thm dung dch SCN
-
vo to kt ta AgCN (coi
th tch khng i). Xc nh nng Ag
+
cn li trong dung dch khi xut hin mu . Bit
T
AgSCN
= 10
-12

3. Thm 20cm
3
dung dch AgNO
3
5.10
-2
M vo 10cm
3
dung dch NaCl khng bit nng . Lng
d Ag
+
c chun bng dung dch KSCN vi s c mt ca Fe
3+
. im tng ng (khi
bt u xut hin mu ) c quan st thy khi thm 6cm
3
dung dch KSCN 10
-1
M. Tnh nng
ca dung dch NaCl.
BI GII:
1. Fe
3+
+ SCN
-
Fe(SCN)
2+

Nng cn bng: C
o
x 10
-2
x x = 10
-5

Ta c:
| |
2
5 2 3
5
10
) 10 10 (
10

+

=
Fe

[Fe
3+
] = 10
-5
M C
o
= 2.10
-5
M
2. Khi xut hin mu th: [Fe(SCN)
2+
] = 10
-5
M. Vy nng Fe
3+
cn li l: 9.10
-5
M
Ta c:
| |
| | | | M Ag M SCN
SCN
10 3
2
5
5
10 . 1 , 9 10 . 1 , 1
10
10 . 9
10
+

= =
=

3 n(Ag
+
) = n(AgCl) + n(AgSCN)
20.10
-3
.5.10
-2
= 10.10
-3
C + 6.10
-3
.10
-1
C = 4.10
-2
M
K THI CHN HC SINH GII QUC GIA NM 2002 (BNG A)
Dung dch X gm Na
2
S 0,010M, KI 0,060M, Na
2
SO
4
0,050M.
(a) Tnh pH ca dung dch X.
(b) Thm dn Pb(NO
3
)
2
vo dung dch X cho n nng 0,090M th thu c kt ta A v dung
dch B.
i Cho bit thnh phn ho hc ca kt ta A v dung dch B.
ii Tnh nng cc ion trong dung dch B (khng k s thu phn ca cc ion, coi th tch
dung dch khng thay i khi thm Pb(NO
3
)
2
).
iii Nhn bit cc cht c trong kt ta A bng phng php ho hc, vit cc phng trnh
phn ng (nu c).
BI GII:
a) Tnh pH ca dung dch Na
2
S 2 Na
+
+ S
2-
0,01 0,01
KI K
+
+ I
-
0,06 0,06
Na
2
SO
4
2Na
+
+ SO
4
2-
0,05 0,05
S
2-
+ H
2
O HS
-
+ OH
-
K
b(1)
= 10
-1,1
(1)
SO
4
2-
+ H
2
O H SO
4
-
+ OH
-
K
b(2)
= 10
-12
(2)
2
K
b(1)
>> K
b(2)
nn cn bng (1) quyt nh pH ca dung dch:
S
2-
+ H
2
O HS
-
+ OH
-
K = 10
-1,1

[ ] (0,01 -x) x x
x = 8,94. 10
-3


[OH
-
] = 8,94.10
-3
pH = 11,95
b) Pb
2+
+ S
2-
PbS | (Ks
-1
) = 10
26
.
0,09 0,01
0,08
Pb
2+
+ SO
4
2-
PbSO
4
| (Ks
-1
) = 10
7,8
.
0,08 0,05
0,03
Pb
2+
+ 2 I
-
PbI
2
(Ks
-1
) = 10
7,6
.
0,03 0,06
Thnh phn hn hp: |A : PbS , PbSO
4
, PbI
2

Dung dch B : K
+
0,06M Na
+
0,12M
Ngoi ra cn c cc ion Pb
2+
; SO
4
2-
; S
2-
do kt ta tan ra.
tan ca
Bi v tan ca PbI
2
l ln nht nn cn bng ch yu trong dung dch l cn bng tan ca PbI
2
.
PbI
2
| = Pb
2+
+ 2I
-
Ks
Do [Pb
2+
] = 10
-47
= 2 x 10
-3
M v [I
-
] = 4.10
-3
M.
10
7,8

[SO
4
2-
] = = 5. 10
5,8
= 7,9.10
6
M << [Pb
2+
]
2 10
3


10
26

[S
2-
] = = 5. 10
24
<< [Pb
2+
]
2 10
3

Cc nng SO
4
2-
, S
2-
u rt b so vi nng Pb
2+
, nh vy nng Pb
2+
do PbS v PbSO
4
tan ra l
khng ng k nn cch gii gn ng trn l hon ton chnh xc.
Nhn bit cc cht c trong kt ta A: PbS; PbSO
4
; PbI
2
.
Cho kt ta ho tan trong NaOH d : | PbS khng tan, c mu en.
Dung dch c PbO
2
2-
, SO
4
2-
, I
-
, OH
-

PbSO
4
+ 4 OH
-
PbO
2
2-
+ SO
4
2-
+ 2 H
2
O
PbI
2
+ 4 OH
-
PbO
2
2-
+ 2 I
-
+ 2 H
2
O
Nhn ra ion SO
4
2-
: cho BaCl
2
d: c kt ta trng BaSO
4
, trong dung dch c PbO
2
2-
, OH
-
, Ba
2+
,
I
-
.
Nhn ra I
-
, Pb
2+
: axit ho dung dch bng HNO
3
d s c kt ta vng PbI
2
xut hin:
OH
-
+ H
+
H
2
O
PbO
2
2-
+ 4 H
+
Pb
2+
+ 2H
2
O
Pb
2+
+ 2 I
-
PbI
2
|




9 , 3
-7,8
4
10 10 S : PbSO

= =
13 -26
10 10 S : PbS

= =
0 10 x 0794 , 0 x 10
x 01 , 0
x
1 , 3 2 1 , 1
2
= + =


7 , 2 3 6 , 7
2
10 4 / 10 : PbI

=
3
K THI CHN HC SINH GII QUC GIA NM 2003 (BNG A)
1. Trong phng th nghim c cc dung dch b mt nhn: AlCl
3
, NaCl, KOH, Mg(NO
3
)
2
, Pb(NO
3
)
2
,
Zn(NO
3
)
2
, AgNO
3
. Dng thm mt thuc th, hy nhn bit mi dung dch. Vit cc phng trnh phn
ng (nu c).
2. Dung dch bo ha H
2
S c nng 0,100 M. Hng s axit ca H
2
S: K
1
= 1,0 x 10
-7
v
K
2
= 1,3 x 10
-13
.
a) Tnh nng ion sunfua trong dung dch H
2
S 0,100 M khi iu chnh pH = 2,0.
b) Mt dung dch A cha cc cation Mn
2+
, Co
2+
, v Ag
+
vi nng ban u ca mi ion
u bng 0,010 M. Ho tan H
2
S vo A n bo ho v iu chnh pH = 2,0 th ion no to
kt ta.
Cho: T
MnS
= 2,5 x 10
-10
; T
CoS
= 4,0 x 10
21
; TAg
2
S = 6,3 x 10
-50

BI GII:
1. C th dng thm phenolphtalein nhn bit cc dung dch AlCl
3
, NaCl, KOH, Mg(NO
3
)
2
, Pb(NO
3
)
2
,
Zn(NO
3
)
2
, AgNO
3
.
* Ln lt nh vi git phenolphtalein vo trong dung dch.
- Nhn ra dung dch KOH do xut hin mu ta.
* Ln lt cho dung dch KOH vo mi dung dch cn li:
- Dung dch AgNO
3
c kt ta mu nu
Ag
+
+ OH

AgOH | ; (hoc 2Ag


+
+ 2OH

Ag
2
O + H
2
O)
- Dung dch Mg(NO
3
)
2
c kt ta trng, keo
Mg
2+
+ 2OH

Mg(OH)
2
|
- Cc dung dch AlCl
3
, Pb(NO
3
)
2
, Zn(NO
3
)
2
u c chung hin tng to ra kt ta trng,
tan trong dung dch KOH (d).
Al
3+
+ 3OH

Al(OH)
3
| ; Al(OH)
3
| + OH

AlO
2

+ 2H
2
O
Pb
2+
+ 2OH

Pb(OH)
2
| ; Pb(OH)
2
| + OH

PbO
2

+ 2H
2
O
Zn
2+
+ 2OH

Zn(OH)
2
| ; Zn(OH)
2
| + OH

ZnO
2

+ 2H
2
O
- Dung dch NaCl khng c hin tng g.
- Dng dung dch AgNO
3
nhn ra dung dch AlCl
3
do to ra kt ta trng
Ag
+
+ Cl

AgCl |
- Dng dung dch NaCl nhn ra dung dch Pb(NO
3
)
2
do to ra kt ta trng
Pb
2+
+ 2 Cl

PbCl
2
|
- cn li l dung dch Zn(NO
3
)
2
.
2.
a) Tnh nng ion S
2
trong dung dch H
2
S 0,100 M; pH = 2,0.
CH
2
S = [H
2
S] = 0,1 M H
2
S (k) H
2
S (aq)
[H
2
S] = 10
-1
H
2
S (aq) H
+
+ HS

K
1
= 1,0 x 10
-7

[H+] = 10
-2
HS H
+
+ S
2-
K
2
= 1,3 x 10
-13

H
2
S (aq) 2H
+
+ S
2-
K =
| |
2
2
2
H S
H S
+


= K
l
. K
2

[S
2-
] = 1,3 x 10
-20
x
| |
2
2
H S
H
+


= 1,3 x 10
-20
x
( )
1
2
2
10
10

= 1,3 x 10
-17
(M)
b)
[Mn
2+
] [S
2-
] = 10
-2
x 1,3 x 10
-17
= 1,3 x 10
-19
< T
MnS
= 2,5 x 10
-10
khng c kt ta
4
[Co
2+
] [ S
2-
] = 10
-2
x 1,3 x 10
-17
= 1,3 x 10
-19
> T
CoS
= 4,0 x 10
-21
to kt ta CoS
[Ag
+
]
2
[S
2-
] = (10
-2
)
2
x 1,3 x 10
-17
= 1,3 x 10
21
> TAg
2
S = 6,3 x 10
-50
to kt ta Ag
2
S
K THI CHN HC SINH GII QUC GIA NM 2004 (BNG B)
1. Dung dch A gm Ba(NO
3
)
2
0,060 M v AgNO
3
0,012 M.
a) Thm tng git K
2
CrO
4
vo dung dch A cho n d. C hin tng g xy ra?
b) Thm 50,0 ml K
2
CrO
4
0,270 M vo 100,0 ml dung dch A.
Tnh nng cc ion trong hn hp thu c.
2. Trnh by s nhn bit v phng trnh ion ca cc phn ng xy ra khi nhn bit cc cation
trong dung dch X gm Ba
2+
, Fe
2+
, Pb
2+
, Cr
3+
, NO
3
-
.
Cho: BaCrO
4|
+ H
2
O Ba
2+
+ HCrO
4
-
+ OH
-
; K = 10
-17,43

Ag
2
CrO
4
+ H
2
O 2Ag
+
+ HCrO
4
-
+ OH
-
; K = 10
-19,50

pK
a
ca HCrO
4
-
bng 6,50.
BI GII:
1.
a) Hin tng: C kt ta BaCrO
4
v Ag
2
CrO
4
.
Xt th t xut hin cc kt ta:
bt u c BaCrO
4
| :
+

>
2
4
2
4
Ba
) BaCrO ( s
CrO
C
K
C
(1)
bt u c Ag
2
CrO
4
| :
+

>
Ag
2
) CrO Ag ( s
CrO
C
K
C
4 2
2
4
(2)
tnh tch s tan K
s
cn t hp cn bng :
BaCrO
4
| Ba
2+
+ CrO
4
2-
K
s1

H
2
O H
+
+ OH
-
K
w

CrO
4
2-
+ H
+
HCrO
4
-
K
a
-1

BaCrO
4
| + H
2
O Ba
2+
+ HCrO
4
-
+ OH
-

C K= K
s1
. K
w
. K
a
-1

Suy ra
93 , 9
14
50 , 6 43 , 17
w
a
1 s
10
10
10 . 10
K
K . K
K


= = =
Ag
2
CrO
4
| 2 Ag
+
+ CrO
4
2-
K
s2

H
2
O H
+
+ OH
-
K
w
CrO
4
2-
+ H
+
HCrO
4
-
K
a
-1

Ag
2
CrO
4
| + H
2
O 2 Ag
+
+ HCrO
4
-
+ OH


C K = 10
-19,50

5
12
14
50 , 6 50 , 19
2 s
10
10
10 . 10
K


= =
T (1)
M 10 . 96 , 1
060 , 0
10
C
9
93 , 9
CrO
2
4

= >


T (2)
M 10 . 94 , 6
) 012 , 0 (
10
C
9
2
12
CrO
2
4

= >



< nhng khng nhiu, v vy s c hin tng kt ta vng ca BaCrO
4

xut hin trc mt t, sau n kt ta vng nu ca Ag
2
CrO
4
( gch ) v BaCrO
4
vng cng xut
hin.
b) Sau khi thm K
2
CrO
4
:
M 090 , 0
000 , 150
00 , 50 x 270 , 0
C
2
4
CrO
= =

;
M 040 , 0
000 , 150
00 , 100 x 060 , 0
C
2
Ba
= =
+

M 0080 , 0
000 , 150
00 , 100 x 0120 , 0
C
2
Ag
= =

Cc phn ng:
Ba
2+
+ CrO
4
2-
BaCrO
4
|
0,046 0,090
- 0,050
2 Ag
+
+ CrO
4
2-
Ag
2
CrO
4
|
0,0080 0,050
- 0,046
Thnh phn sau phn ng :
BaCrO
4
| ; Ag
2
CrO
4
| ; CrO
4
2-
(0,046 M ).
Ag
2
CrO
4
| 2 Ag
+
+ CrO
4
2-
10
-12

BaCrO
4
| Ba
2+
+ CrO
4
2-
10
-9,93

Nng CrO
4
2-
d kh ln, c th coi nng CrO
4
2-
do 2 kt ta tan ra l khng ng k.
CrO
4
2-
+ H
2
O HCrO
4
-
+ OH
-
K
b
= 10
-7,5

C 0,046
| | (0,046 x ) x x
C
CrO
4
2-
(BaCrO
4
)
C
CrO
4
2-
(Ag
2
CrO
4
)
6
5 , 7
2
10
x 046 , 0
x

=

x = 3,8.10
-5
<< 0,046; | | M 046 , 0 CrO
- 2
4
=
| |
| | M 10 . 55 , 2
046 , 0
10
Ba
; M 10 . 66 , 4
046 , 0
10
Ag
9
93 , 9
2
6
0 , 12

+
= =
= =

[Ba
2+
] v [Ag
+
] u << [CrO
4
2-
], chng t nng CrO
4
2-
do 2 kt ta tan ra l khng ng k.
Vy trong dung dch c:
[Ba
2+
] = 2,55.10
-9
M ; [Ag
+
] = 4,66.10
-6
M ;
[CrO
4
2-
] = 0,046M ; [OH
-
] = 3,8.10
-5
M ; [H
+
] = 2,63.10
-10
M;
[K
+
] = C
K+
= 0,18M ;
0,088M. C
-
3
NO
=

2.
+ H
2
SO
4
BaSO
4

+
PbSO
4
Cr
3+
, Fe
2+
+ NaOH + NaOH d- + H
2
O
2
BaSO
4
PbO
2
Fe(OH)
3
CrO
4
2-
2-
2-
Kt ta trng SO
4
, OH
-
Kt ta nu Dung dch mu vng


+ HNO
3
PbSO
4
Kt ta trng (hoc + H
2
S cho kt ta PbS mu en)
Dung dch X (Ba
2+
, Fe
2+
, Pb
2+
, Cr
3+
, NO
3
-
)

Ba
2+
+ HSO
4
-
BaSO
4
|

+ H
+

Pb
2+
+ HSO
4
-
PbSO
4
|

+ H
+

H
+
+ OH
-
H
2
O
PbSO
4
| + 4 OH
-
PbO
2
2-


+ SO
4
2-
+ H
2
0
PbO
2
2-


+ SO
4
2-
+ 4 H
+
PbSO
4
|

+ 2 H
2
O
( PbO
2
2-


+ 2 H
2
S PbS|

en + 2 H
2
O )
Cr
3+


+ 3 OH
-
Cr(OH)
3
|


7
Cr(OH)
3
| + OH
-


CrO
2
-
+ 2 H
2
O
2 CrO
2
-
+ 3 H
2
O
2
+ 2 OH
-

2 CrO
4
2-
+ 4 H
2
O
Fe
2+
+ 2 OH
-
Fe(OH)
2
|


2 Fe(OH)
2
+ H
2
O
2
Fe(OH)
3
|
K THI CHN HC SINH GII QUC GIA NM 2005 (BNG A)
Bng dung dch NH
3
, ngi ta c th lm kt ta hon ton ion Al
3+
trong dung dch nc
dng hydroxit, nhng ch lm kt ta c mt phn ion Mg
2+
trong dung dch nc dng hydroxit.
Hy lm sng t iu ni trn bng cc php tnh c th.
Cho bit: Tch s tan ca Al(OH)
3
l 5.10
33
; tch s tan ca Mg(OH)
2
l 4.10
12
; hng s phn
ly baz ca NH
3
l 1,8.10
5
.
BI GII:
Tnh hng s cn bng K ca phn ng kt ta hidroxit:
3 NH
3
+ H
2
O NH
4
+
+ OH

; K = 1,8.10
5

Al(OH)
3
Al
3+
+ 3 OH

; K
S,
= 5. 10
33


Al
3+
+ 3 NH
3
+ 3 H
2
O Al(OH)
3
+ 3 NH
4
+
; K = = 1,17.10
18


Tng t nh vy, i vi phn ng:
Mg
2+
+ 2 NH
3
+ 2 H
2
O Mg(OH)
2
+ 2 NH
4
+
; K = = 81

Phn ng thun nghch, Mg
2+
khng kt ta hon ton di dng magie hidroxit nh Al
3+
.
K THI CHN HC SINH GII QUC GIA NM 2005 (BNG B)
1. Tnh in li ca ion CO
3
2
trong dung dch Na
2
CO
3
c pH =11,60 (dung dch A).
2. Thm 10,00 ml HCl 0,160 M vo 10,00 ml dung dch A. Tnh pH ca hn hp thu c.
3. C hin tng g xy ra khi thm 1 ml dung dch bo ho CaSO
4
vo 1 ml dung dch A.
Cho: CO
2
+ H
2
O HCO
3

+ H
+
; K = 10
6,35

HCO
3

H
+
+ CO
3
2
; K = 10
10,33

tan ca CO
2
trong nc bng 3,0.10
2
M.
Tch s tan ca CaSO
4
bng 10
5,04
; ca CaCO
3
bng 10
8,35

BI GII:
1. CO
3
2
+ H
2
O HCO
3

+ OH

; K
b1
= 10
-14
/10
-10,33
= 10
3,67
(1)
HCO
3

+ H
2
O ( H
2
O.CO
2
) + OH

; K
b2
= 10
-14
/10
-6.35
= 10
7,65
(2)
K
b1
>> K
b2
, cn bng (1) l ch yu.
CO
3
2
+ H
2
O HCO
3

+ OH

; 10
3,67

C C

NH
3


Al(OH)
3



K
3

K
S;

NH
3

Al(OH)
3


NH
3

Mg(OH)
2

K
2

K
S;

a
1

a
2

8
[ ] C 10
2,4
10
2,4
10
2,4


( )
4 , 2
2
4 , 2
10
10

C
= 10
3,67
C = 10
2,4
+ (10
-4,8
/10-3,67) = 0,0781 M

o = = 5,1 %
2.
C
HCl
= 0,16/2 = 0,08 M ; C = = 0,03905 M
CO
3
2
+ 2 H
+
CO
2
+ H
2
O
[ ] 0,03905 0,08
1,9. 10
3
0,03905
C > L
CO
2
+ H
2
O H
+
+ HCO
3

; 10
6,35
(do K
a1
>> K
a2
)
C 3,0 10
2
1,9. 10
3

3,0 10
2
x 1,9. 10
3
+ x x
= 10
6,35
x = 7,05.10
6
<< 1,9. 10
3
[H
+
] = 1,9.10
3

Vy pH = lg 1,9. 10
3
= 2,72
3.
C = 0,0781/2 = 0,03905 ~ 0,0391
CaSO
4
Ca
2+
+ SO
4
2
; K
S1
= 10
5,04

x x
x = (K
S1
)
0,5

= 10
2,52
C
Ca
2+
= (10
-2,52
/2) = 10
2,82

CO
3
2
+ H
2
O HCO
3

+ OH

; 10
3,67
(do K
b1
>> K
b2
)
C 0,0391
[ ] 0,0391 x x x


3 67 , 3
2
10 . 89 , 2 10
0391 , 0

= =

x
x
x

C = 0,0391 2,89.10
3
= 0,0362 M
C . C
Ca
2+
= 0,0362 10
2,82
= 5,47.10
5
> 10
8,35


Kt lun: c kt ta CaCO
3

10
2,4
10
2

0,0781

CO
3
2


Na
2
CO
3


0,0781
2

CO
2


CO
2


x(1,9. 10
3
+x) +
3,0 10
2
x

CO
3
2


CO
3
2


CO
3
2


9
II. OLYMPIC HA HC QUC T:
OLYMPIC HA HC QUC T LN TH 28:
Kali dicromat l mt trong nhng tc nhn to kt ta c s dng rng ri nht. Nhng cn
bng sau c thit lp trong dung dch nc ca Cr(VI)
HCrO
4
-
+ H
2
O CrO
4
2-
+ H
3
O
+
. pK
1
= 6,50
2HCrO
4
-
Cr
2
O
7
2-
+ H
2
O pK
2
= -1,36
1. Tch s ion ca nc K
W
= 1,0.10
-14

Tnh hng s cn bng ca cc phn ng sau:
a) CrO
4
2-
+ H
2
O HCrO
4
-
+ OH
-

b) Cr
2
O
7
2-
+ 2OH
-
2CrO
4
2-
+ H
2
O
2. Tch s tan ca BaCrO
4
l T = 1,2.10
-10
. Ba
2
Cr
2
O
7
tan dn dng trong nc. Cn bng ca phn ng
(1b) s di chuyn theo chiu no khi thm cc tc nhn sau vo dung dch tng i m c ca
kali dicromat?
a) KOH
b) HCl
c) BaCl
2

d) H
2
O (xt tt c cc cn bng trn).

3. Hng s phn ly ca axit axetic l K
a
= 1,8.10
-5
. Hy tnh tr s pH ca cc dung dch sau:
a) K
2
CrO
4
0,010M
b) K
2
Cr
2
O
7
0,010M
c) K
2
Cr
2
O
7
0,010M + CH
3
COOH 0,100M
4. Hy tnh nng ti cn bng ca cc ion sau trong dung dch K
2
Cr
2
O
7
0,010M + CH
3
COOH
0,100M.
a) CrO
4
2-
.
b) Cr
2
O
7
2-
.
BI GII:
1) a) Hng s cn bng:
K = [HCrO
4
-
][OH
-
]/[CrO
4
2-
] = [H
+
][OH
-
]/([H
+
][CrO
4
2-
]/[HCrO
4
-
]) = K
w
/K
1
= 3,2.10
-8

b) Hng s cn bng:
K = ([CrO
4
2-
][H
+
]/[HCrO
4
-
])
2
/([HCrO
4
-
]
2
/[Cr
2
O
7
2-
])/([H
+
][OH
-
])
2
= 4,4.10
13
.
2) a) phi
b) Tri
c) BaCl
2
di cn bng qua phi do ion cromat lin kt to thnh hp cht kh tan:
Ba
2+
+ CrO
4
2-
= BaCrO
4

d) H
2
O di cn bng qua phi do khi thm nc vo dung dch dicromat dn n vic lm long
dung dch v lm cho cn bng phn ly ca ion dicromat qua bn phi. Theo bi th pH ca
dung dch phi b hn 7. Vi s pha long ny th pH ca dung dch s tng ln nn cn bng
phi chuyn dch v bn phi.
3) a) CrO
4
2-
+ H
2
O = HCrO
4
-
+ OH
-
K = 3,16.10
-8
.
C
Cr
= [CrO
4
2-
] + [HCrO
4
-
] + 2[Cr
2
O
7
2-
] ~ [CrO
4
2-
]
[HCrO
4
-
] ~ [OH
-
]
Nh vy [OH
-
]
2
/C
Cr
= K [OH
-
] = 1,78.10
-5
M nn [H
+
] = 5,65.10
-10
.
Vy pH = 9,25
b) Cr
2
O
7
2-
+ H
2
O = 2HCrO
4
-
K = 1/K
2
= 4,37.10
-2

10
HCrO
4
-
= H
+
+ CrO
4
2-
K = K
1
= 3,16.10
-7
.
C
Cr
= 2,0.10
-2
M = [CrO
4
2-
] + [HCrO
4
-
] + 2[Cr
2
O
7
2-
] ~ [HCrO
4
-
] + 2[Cr
2
O
7
2-
]
[H
+
] ~ [CrO
4
2-
] = x = (K
1
[HCrO
4
-
])
1/2
K
2
= [Cr
2
O
7
2-
]/[HCrO
4
-
] = (C
Cr
x)/2x
2

iu ny dn n phng trnh: 2K
2
x
2
+ x C
Cr
= 0
Gii phng trnh trn ta thu c: x = 1,27.10
-2
M [H
+
] = 6,33.10
-5
M
Vy pH = 4,20
c) Trong CH
3
COOH 0,10M th [H
+
] = (K
a
C)
1/2
= 1,34.10
-3
pH = 2,87
y l tr s cn thit. So snh tr s ny vi pH ca dung dch dicromat 0,1M cho trn (b) cho
thy nh hng ca K
2
Cr
2
O
7
trn pH c th an tm b qua c.
4) C th tnh bng hai cch:
Cch 1:
a) [HCrO
4
-
] = 1,3.10
-2
M (3b) [CrO
4
2-
] = K
1
[HCrO
4
-
]/[H
+
] = 3,0.10
-6
M
b) C
Cr
= [CrO
4
2-
] + [HCrO
4
-
] + 2[Cr
2
O
7
2-
] [Cr
2
O
7
2-
] = 3,7.10
-3
M
hoc [Cr
2
O
7
2-
] = K
2
[HCrO
4
-
] = 3,9.10
-3
M
Cch 2:
a) [CrO
4
2-
] = x; [HCrO
4
-
] = x[H
+
]/K
1

[Cr
2
O
7
2-
] = K
2
[HCrO
4
-
] = x
2
K
2
[H
+
]
2
/K
1
2
.
C
Cr
= [CrO
4
2-
] + [HCrO
4
-
] + 2[Cr
2
O
7
2-
] = 2K
2
[H
+
]
2
/K
1
2
x
2
+ (1 + [H
+
]/K
1
)x
K
1
= 3,16.10
-7
; K
2
= 22,9; [H
+
] = 1,34.10
-3
.
8,24.10
8
x
2
+ 4,24.10
3
x 2,0.10
-2
= 0
x = 3,0.10
-6
M
b) [Cr
2
O
7
2-
] = K
2
[HCrO
4
-
] = K
2
[H
+
]
2
/K
1
2
[CrO
4
2-
] = 3,7.10
-3
M
OLYMPIC HA HC QUC T LN TH 28:
Cc phng php o hiu th v quang ph c s dng rng ri xc nh cc nng cn
bng v hng s cn bng trong dung dch. C hai phng php thng xuyn c dng kt hp xc
nh ng thi nhiu tiu phn.
Dung dch nc axit ha I cha mt hn hp FeSO
4
v Fe
2
(SO
4
)
3
, v dung dch nc II cha
mt hn hp K
4
[Fe(CN)
6
] v K
3
[Fe(CN)
6
]. Nng ca cc tiu phn c cha st tho mn cc quan h
[Fe
2+
]
I
= [Fe(CN)
6
4-
]
II
v [Fe
3+
]
I
= [Fe(CN)
6
3-
]
II
. Th ca in cc platin nhng trong dung dch I l
0,652V (so vi in cc hydro tiu chun), trong khi th ca in cc platin nhng trong dung dch II l
0,242V (so vi in cc hydro tiu chun). Phn trm truyn x ca dung dch II o c so vi dung
dch I ti 420nm bng 10,7% (chiu di ng truyn quang l = 5,02mm). Gi thit rng phc
[Fe(CN)
6
4-
] Fe
3+
(aq); Fe
2+
(aq) khng hp th nh sng ti 420nm. hp th mol c(Fe(CN)
6
3-
) =
1100L/mol.cm ti bc sng ny. Th kh chun ca Fe
3+
/Fe
2+
l 0,771V. Yu t ghi trc logarit thp
phn ca phng trnh Nernst bng 0,0590 (v ghi trc logarit t nhin l 0,0256). Gi thit rng tt c
cc h s hot u bng 1.
1) Vit phng trnh Nernst ca h thng oxy ha - kh ca:
a) Dung dch 1.
b) Dung dch 2 (ngoi tr phc xiano, b qua mi dng khc c trong dung dch)
2) n v ca yu t ghi trc logarit trong phng trnh Nernst c n v l g?
3) Tnh t s cc hng s bn vng |(Fe(CN)
6
3-
)/|(Fe(CN)
6
4-
)
4) Khong bin thin tuyt i trong ln (bin ) ca cc tham s vt l sau l bao nhiu.
a) truyn x (T)%
b) Mt quang (A) %.
5) Tnh nng ca
11
a) Fe
3+
trong dung dch I
b) Fe
2+
trong dung dch I
BI GII:
1) Phng trnh Nernst:
a) E
I
= E
o
(Fe
3+
/Fe
2+
) + 0,0590lg([Fe
3+
]/[Fe
2+
]
b) E
II
= E
o
(Fe(CN)
6
3-
/Fe(CN)
6
4-
) + 0,0590lg([Fe(CN)
6
3-
]/[Fe(CN)
6
4-
])
2) Volt (V)
3) E
II
= E
o
(Fe(CN)
6
3-
/Fe(CN)
6
4-
) + 0,0590lg([Fe(CN)
6
3-
]/[Fe(CN)
6
4-
]
= E
o
(Fe
3+
/Fe
2+
) + 0,0590lg(|
1
/|
2
) + 0,0590lg([CN
-
]
6
/[CN
-
]
6
) + 0,0590lg([Fe(CN)
6
3-
]/[Fe(CN)
6
4-
])
= 0,242
Trong |
1
v |
2
ln lt l cc hng s bn vng ca [Fe(CN)
6
4-
] v [Fe(CN)
6
3-
].
[Fe(CN)
6
3-
]/[Fe(CN)
6
4-
] = Fe
3+
/Fe
2+
nn E = E
II
E
I
= 0,059lg(|
1
/|
2
) = 8,90.10
6
.
4) a) T 0 n 100%
b) T 0 n
5) a) Dng nh lut Bouger Lambert Beer
A = c.l.C = c.l.[Fe(CN)
6
3-
] = 0,971
[Fe(CN)
6
3-
] = [Fe
3+
] = 1,76.10
-3
M
b) Dng phng trnh Nernst:
E
I
= E
o
(Fe
3+
/Fe
2+
) + 0,0590lg([Fe
3+
]/[Fe
2+
]) = 0,652V
T : [Fe
3+
]/[Fe
2+
] = 9,62.10
-3
M [Fe
2+
] = 0,183M

OLYMPIC HA HC QUC T LN TH 29:
HIn l mt cht ch th c tnh axit yu:
Hin + Na
+
OH
-
Na
+
In
-
+ H
2
O
nhit thng, hng s phn li axit ca cht ch th ny l 2,93.10
-5
.
Tr s bc sng di hp th (cuvet 1,00cm) cho cc dung dch 5,00.10
-4
M (mol.dm
-3
) ca cht
ch th ny tng cc dung dch axit mnh v kim mnh c cho trong bng sau:
Tr s bc sng di hp th
(nm) pH = 1,00 pH = 13,00
400 0,401 0,067
470 0,447 0,050
485 0,453 0,052
490 0,452 0,054
505 0,443 0,073
535 0,390 0,170
555 0,342 0,342
570 0,303 0,515
585 0,263 0,648
615 0,195 0,816
625 0,176 0,823
635 0,170 0,816
650 0,137 0,763
680 0,097 0,588
1) D on mu ca:
a) Dng axit.
12
b) Dng baz ca cht ch th.
2) Knh lc c mu no l thch hp nht phn tch bng quang k cht ch th ny trong mi trng
axit mnh?. Bit knh lc c t gia ngun sng v mu cht ch th.
3) Khong no ca bc sng l thch hp nht phn tch bng quang k cht ch th ny trong mi
trng baz mnh?
4) Cc dung dch ca cht ch th ny c pha ch trong dung dch HCl 0,1M v trong dung dch
NaOH 0,1M. xc nh c cc biu thc hon ton tuyn tnh gia bc sng di hp th v
nng ti 490nm v 625nm cho tng mi trng tng ng trn. ln ca hng s phn li axit
cho thy rng cht ch th ny hon ton khng phn li trong HCl 0,1M m li phn li hon ton
trong NaOH 0,1M

490nm

625nm

HIn (M
-1
.cm
-1
) 9,04.10
2
3,52.10
2
In
-
(NaOH) 1,08.10
2
1,65.10
3
Hy tnh bc sng di hp th (cuvet 1,00cm) hai bc sng trn ca mt dung dch khng
cha cht m ca cht ch th ny c nng 1,80.10
-3
M
BI GII:
1) Mu quan st c l mu kt hp vi mu ca s hp th ti a
a) iu kin axit (pH = 1): Mu hp th 490 25 (xanh lam - lc) v nh vy s truyn mu kt
hp v c mu vng cam (625 25 nm)
b) iu kin baz (pH = 13): Mu hp th 625 25 (vng cam) v nh vy s truyn mu kt hp
v c mu xanh lam - lc (490 25nm).
2) Knh lc cn truyn mu m mu s hp th hiu qa nht. Mu axit hp th mnh nht trong
khong xanh (490 25nm) v nh vy mt knh lc mu tng t s thch hp nht cho s phn tch
bng quang k ca mu th.
3) Khong bc sng c dng vi nhy cao nht s tng ng vi bc sng m mu th hp th
mnh nht. hp th ti a trong dng baz ca cht ch th trong dung dch xy ra 625 25 nm
v y l bc sng thch hp nht cho s phn tch.
4) Hng s in li ca cht ch th l:
| || |
| | HIn
In H
K
a
+
= (1)
Ta li c:
[H
+
] = [In
-
] (2)
[HIn] + [In
-
] = 1,80.10
-3
M (3)
Thay (3) v (2) vo (1) ta c [In
-
] = 2,15.10
-4
M [HIn] = 1,58.10
-3
M
Khi y ta c th tnh c mt quang hai bc sng l:
A
490
= 1,45
A
625
= 0,911
OLYMPIC HA HC QUC T LN TH 31:
PHN A:
Mt axit hai cha H
2
A tham gia vo cc phn ng phn li sau:
H
2
A HA
-
+ H
+
K
1
= 4,50.10
-7

HA
-
A
2-
+ H
+
K
2
= 4,70.10
-11
.
Mt mu 20,00mL dung dch cha hn hp Na
2
A v NaHA c chun vi axit clohydric
0,300M. Qa trnh chun c thc hin vi mt pH - k in cc thy tinh. Hai im tng ng
trn ng cong chun nh sau:
13
S mL HCl thm vo pH
1,00 10,33
10,00 8,34
1) Khi thm 1,00mL HCl, tiu phn no phn ng trc ht v to sn phm g?
2) Lng sn phm to thnh (mmol) cu 1 l bao nhiu?
3) Vit cn bng chnh ca sn phm cu 1 tc dng vi dung mi
4) Lng (mmol) Na
2
A v NaHA c mt lc u?
5) Tnh tng th tch ca HCl cn thit t n im tng ung th hai.
PHN B:
Cc dung dch I, II v III c cha cht ch th pH HIn (K
In
= 4,19.10
-4
) v cc tc nhn khc ghi
trong bng. Cc ga tr hp th ti 400nm ca cc dung dch c o trong cng mt cuvet cng c
cho trong bng. K
a
ca CH
3
COOH l 1,75.10
-5
.
Dung dch I Dung dch II Dung dch III
Nng ton phn ca
HIn
1,00.10
-5
M 1,00.10
-5
M 1,00.10
-5
M
Cc tc nhn khc 1,00M HCl 0,100M NaOH 1,00M CH
3
COOH
hp th ti 400nm 0,000 0,300 ?
6) Hy tnh hp th ti 400nm ca dung dch III.
7) Ngoi H
2
O, H
+
v OH
-
cn c tt c nhng tiu phn no c mt trong dung dch thu c t s trn
ln dung dch II v dung dch III theo t l th tch 1:1
8) hp th ti 400nm ca dung dch cu 7 l bao nhiu?
9) truyn x ti 400nm ca dung dch cu 7 l bao nhiu?
BI GII:
PHN A:
1) Tiu phn phn ng trc ht l: A
2-

Sn phm l HA
-

2) S mmol sn phm = 1,00.0,300 = 0,300mmol.
3) HA
-
+ H
2
O H
2
A + OH
-

4) Ti pH = 8,34 = (pK
a1
+ pK
a2
)/2 tt c A
2-
u b proton ha thnh HA
-
.
Do s mmol A
2-
c mt trong dung dch lc u = 3,00mmol
Ti pH = 10,33 h l mt dung dch m vi t l [A
2-
]/[HA
-
] = 1. Nh vy:
[HA
-
]
lc u
+ [HA
-
]
to thnh
= [A
2-
]
lc u
- [HA
-
]
to thnh

Nh vy s mmol HA lc u = 3,00 0,300 0,300 = 2,40mmol.
5) V
HCl
= [(2.3,00) + 2,40]/0,300 = 28,00mL
PHN B:
6) Dung dch III l dung dch ch th ti 10
-5
M trong dung dch c cha CH
3
COOH 1,0M.
c c hp th hay mt quang ca dung dch, cn thit phi tnh nng dng cn
bng ca cht ch th tu thuc vo [H
+
] ca dung dch
[H
+
]
III
= (K
a
.C)
1/2
= 4,18.10
-3
M
T HIn H
+
+ In
-
ta c:
| || |
| | HIn
In H
K
a
+
=
| |
| | | |
100 , 0 = =
+

H
K
HIn
In
In
(1)
Ta li c: [HIn] + [In
-
] = 10
-5
(2)
T (1) v (2) ta tnh c [In
-
] = 0,091.10
-5
M
14
hp th ca dung dch III = 027 , 0 300 , 0 .
10 . 00 , 1
10 . 091 , 0
5
5
=


7) CH
3
COOH, CH
3
COO
-
; Na
+
; HIn; In
-
.
8) Khi cc dung dch II v III c trn ln theo t l th tch 1:1 thu c mt dung dch m gm
CH
3
COO
-
0,05M/CH
3
COOH 0,45M
| |
| |
| |
5
3
3
10 . 75 , 15

+
= =
COO CH
COOH CH
K H
a

V vy:
| |
| | | |
65 , 2
10 . 75 , 15
10
5
38 , 3
= = =

H
K
HIn
In
In
(3)
Ta li c: [HIn] + [In
-
] = 10
-5
(2)
T (2) v (3) ta tnh c [In
-
] = 0,726.10
-5
M
hp th ca dung dch = 218 , 0 300 , 0 .
10 . 0 , 1
10 . 726 , 0
5
5
=


9) truyn x ca dung dch = 10
-( hp th)
= 0,605
OLYMPIC HA HC QUC T LN TH 32:
Transferin (Tf) - mt loi huyt thanh - l mt n protein c chc nng chnh l tham gia qa
trnh vn chuyn st (III) trong c th ngi. Mi phn t transferin c th vn chuyn hai ion Fe
3+
theo
phn ng:
Fe
III
+ Tf (Fe
III
)Tf K
1
= 4,7.10
20
M
-1
.
Fe
III
+ (Fe
III
)Tf (Fe
III
)
2
Tf K
2
= 2,4.10
19
M
-1
.
phn t (Fe
III
)
2
Tf 2 ion Fe
3+
lien kt tng t nhau nhng khng cng mt pha v 2 phn t
st monotransferin (Fe
III
)Tf c th c biu th bng {Fe
III
.Tf} v {Tf.Fe
III
}. Bit K =
[{Tf.Fe
III
}].[{Fe
III
.Tf}] = 5,9.
1. Tnh ga tr ca K

1
= [{Fe
III
.Tf}].[Fe
III
]
-1
. [Tf]
-1
v K

1
=[{Tf.Fe
III
}].[Fe
III
]
-1
. [Tf]
-1
.
2. Tnh gi tr ca K

2
= [(Fe
III
)
2
Tf].[Fe
III
]
-1
.[{Fe
III
.Tf}]
-1
v K

2
=[(Fe
III
)
2
Tf].[Fe
III
]
-1
.[{Tf.Fe
III
}]
-1
.
Lin kt gia st (III) mi pha ca lin kt c bao quanh bi 6 nguyn t nhn t cc ligand
khc nhau. Theo cch ny, 2 nguyn t oxy ca anion CO
3
2-
phi tr vi kim loi v mi aminoaxit cu
trc bc 1 ca protein l: 1 Aspartic, 1 Histidin, 2 Tyrosin cng phi tr vi st (III).
3. C bao nhiu nguyn t oxy xung quanh mt ion st (III) trong transferin.
BI GII:
1. Nng ca phc monoferric transferin:
[(Fe
III
)Tf] = [{Fe
III
.Tf}] + [{Tf.Fe
III
}]
K
1

+ K
1

= K
1
; K
1

.K = K
1


1 20 20 '
1 1
"
1
1 19
20
1 '
1
10 . 0 , 4 10 ). 68 , 0 7 , 4 (
10 . 8 , 6
9 , 5 1
10 . 7 , 4
1

= = =
=
+
=
+
=
M K K K
M
K
K
K

2. Ta c:
1 19
"
1
2 1 "
2 2 1
"
2
'
1
1 20
'
1
2 1 '
2 2 1
"
2
"
1
'
2
'
1
10 . 8 , 2
10 . 7 , 1

= = =
= = = =
M
K
K K
K K K K K
M
K
K K
K K K K K K K

3. S nguyn t oxy = 2(CO
3
2-
) + 1(Asp(O
-
)) + 2(2xTyr(O
-
)) = 5
15
OLYMPIC HA HC QUC T LN TH 33:
Axit Photphoric l mt loi phn bn quan trng. Bn cnh axit photphoric v mui ca n c
nhiu ng dng trong x l kim loi, thc phm, cht ty ra v cng nghip ch to thuc nh rng.
1. Ga tr pK ca ba nc phn ly ca H
3
PO
4
25
o
C l: pK
a1
= 2,12; pK
a2
= 7,21; pK
a3
=12,32. Vit cng
thc baz lin hp ca H
2
PO
4
-
v tnh ga tr K
b
ca n.
Mt lng nh H
3
PO
4
c s dng rng ri to v chua hay v cht cho nhiu thc ung nh
cola v bia. Cola c t khi 1,00gmL
-1
cha 0,05% H
3
PO
4
v khi lng.
2. Tnh pH ca cola (b qua nc phn li th 2 v 3). Gi s rng nguyn nhn gy ra tnh axit ca cola
l do H
3
PO
4
.
3. H
3
PO
4
c s dng lm phn bn trong nng nghip ; 1,00.10
-3
M H
3
PO
4
c thm vo dung
dch huyn ph ct v pH ca dung dch thu c l 7,00. Tnh nng phn mol ca cc loi
photphat khc nhau trong t bit rng trong t khng c cht no phn ng vi photphat.
4. Km l nguyn t vi lng quan trng cn cho s pht trin cy trng. Cy trng c th hp th
c km dng dung dch nc. trong dung dch ncc ngm c pH = 7,0 ngi ta tm thy
c Zn
3
(PO
4
)
2
. Tnh [Zn
2+
] v [PO
4
3-
] trong dung dch bo ha. Bit T ca km photphat l
9,1.10
-35
.
BI GII:
1. Baz lin hp ca dihidro photphat (H
2
PO
4
-
) l monohydrophotphat (HPO
4
2-
)
H
2
PO
4
-
+ H
2
O HPO
4
2-
+ H
3
O
+
K
2a

HPO
4
2-
+ H
2
O H
2
PO
4
-
+ OH
-
K
2b

2H
2
O H
3
O
+
+ OH
-
K
w
.
pK
2a
+ pK
2b
= pK
w
= 14
pK
2b
= 6,79
2. C(H
3
PO
4
) = 0,0051M
H
3
PO
4
+ H
2
O H
2
PO
4
-
+ H
3
O
+

0,0051 x x x
pK
a1
= 2,12. Vy K
a
= 7,59.10
-3
.
Ta c:
| || |
| |
| |
46 , 2
10 . 49 , 3
10 . 59 , 7
0051 , 0
3
3
3
2
4 3
3 4 2
=
= =
=

=
+

+
pH
O H x
x
x
PO H
O H PO H

3. t:
| |
| |
| |
| |
C
X
f
C
HX
f
C
X H
f
C
X H
f
o

=
=
=
=
3
3
2
2
2
1
3

16
k hu cc phn s nng ca cc loi photphat khc nhau; C l tng nng ban u ca
H
3
X (X = PO
4
):
| || |
| |
| |
| || |
| |
| |
| || |
| |
| |
+

+
+

+
+
+
= =
= =
= =
= + + +
O H
f
f
HX
O H X
K
O H
f
f
X H
O H HX
K
O H
f
f
X H
O H X H
K
f f f f
a
a
o
a
o
3
2
3
2
3
3
3
3
1
2
2
3
2
2
3
1
3
3 2
1
3 2 1
1

Cc phng trnh trn y dn n:









| |
| |
| |
D
K K K
f
D
O H K K
f
D
O H K
f
D
O H
f
a a a
a a
a
p
3 2 1
3
3 1 2
2
2
3 1
1
3
3
.
=
=
=
=
+
+
+

Vi D = K
a1
.K
a2
.K
a3
+ K
a1
.K
a2
.[H
3
O
+
] + K
a1
[H
3
O
+
] + [H
3
O
+
]
3
.
T cc ga tr K
a1
; K
a2
; K
a3
v pH ta c c cc kt qa sau:
K
a1
= 7,59.10
-3
; K
a2
= 6,17.10
-8
; K
a3
= 4,79.10
-13
v [H
3
O
+
] = 10
-7
.
V cc phn s nng ca cc loi photphat khc nhau s l:
H
3
PO
4
(f
o
) = 8,10.10
-6
.
H
2
PO
4
-
(f
1
) = 0,618
HPO
4
2-
(f
2
) = 0,382
PO
4
3-
(f
3
) = 1,83.10
-6
.
4. t S(M) l tan ca km photphat trong nc ngm:
[Zn
2+
] = 3S
Tng nng ca cc dng khc nhau ca photphat = 2S
[PO
4
3-
] = f
3
.2S
f
3
c th c xc nh t cc quan h cu 3
i vi pH = 7 th f
3
= 1,83.10
-6
.
T = [Zn
2+
]
3
[PO
4
3-
]
2
= (3S)
3
.(f
3
.2S)
2
= 9,1.10
-33

17
S = 3,0.10
-5
M
[Zn
2+
] = 9.10
-5
M
[PO
4
3-
] = 1,1.10
-10
M
OLYMPIC HA HC QUC T LN TH 37:
Kh nng nhn ion H
+
ca nc c gi l tnh kim. Tnh kim rt quan trng i vi vic x
l nc, tnh cht ho hc v sinh hc ca nc. Ni chung, cc thnh phn ch yu nh hng n tnh
kim ca nc l HCO
3
-
, CO
3
2-
v OH
-
. ga tr pH di 7 th H
+
trong nc lm gim tnh kim ca
nc. Chnh v vy, phng trnh nu kim ca nc khi c mt cc ion HCO
3
-
, CO
3
2-
v OH
-
c th
c biu din bi:
kim = [HCO
3
-
] + 2[CO
3
2-
] + [OH
-
] - [H
+
].
Cc cn bng v hng s cn bng ( 298K) c cho sau y:
CO
2(k)
CO
2(aq)
K(CO
2
) = 3,44.10
-2
.
CO
2
+ H
2
O H
2
CO
3
K(H
2
CO
3
) = 2,00.10
-3
.
H
2
CO
3
HCO
3
-
+ H
+
K
a1
= 2,23.10
-4
.
HCO
3
-
CO
3
2-
+ H
+
K
a2
= 4,69.10
-11

CaCO
3
Ca
2+
+ CO
3
2-
K
sp
= 4,50.10
-9
.
H
2
O H
+
+ OH
-
K
w
= 1,00.10
-14

1. Nc t nhin (nc sng hay h) lun cha CO
2
ho tan. T l [H
2
CO
3
] : [HCO
3
-
] : [CO
3
2-
] = a
: 1,00 : b. Xc nh a, b trong nc c nng [H
+
] = 1,00.10
-7
M.
2. Kh CO
2
trong kh quyn c th lin quan ti tnh kim ca nc do n nm cn bng vi hm
lng CO
2
tan trong nc. Tnh nng ca CO
2
(mol/L) trn nc tinh khit nm cn bng vi
khng kh khng b nhim p sut 1,01.10
5
Pa v 298K cha 0,0360% (v s mol) CO
2
. Gi
s p sut tiu chun l 1,01.10
5
Pa.
Nu bn khng lm c cu ny th c th gi s rng nng CO
2(aq)
= 1,11.10
-5
M.
tan ca CO
2
trong nc c th c nh ngha bng biu thc S=[CO
2(aq)
] + [H
2
CO
3
] +
[HCO
3
-
] + [CO
3
2-
]. tan ca kh CO
2
trong nc nm cn bng vi khng kh khng b nhim
298K v 1,01.10
5
Pa lun khc vi kim
3. Tnh tan ca CO
2(k)
tring nc tinh khit (mol/L). B qua s phn li ca nc.
4. Khi trong nc c 1,00.10
-3
M NaOH th tan ca CO
2(k)
lc ny s l bao nhiu?
298K, 1,01.10
5
Pa th kh khng nhim s nm cn bng vi nc thin nhin cha CaCO
3

ho tan. Cn bng sau y c th tn ti:
CaCO
3(r)
+ CO
2(aq)
+ H
2
O Ca
2+
+ 2HCO
3
-
.
5. Tnh hng s cn bng ca phn ng trn.
Nu khng tnh c th ta c th gi s K = 5,00.10
-5
tnh ton cho cu tip theo.
6. Tnh nng Ca
2+
(mg/L) trong CaCO
3
ho tan trong nc nm cn bng vi CO
2
trong kh
quyn.
Nu khng tnh c th ta c th gi s rng nng ca Ca
2+
(aq)
l 40,1mg/L tnh ton.
7. Tnh kim ca dung dch trn.
8. mt h nc ngm cha CaCO
3
ho tan th nc c lng CO
2
rt cao. Nng ca Ca
2+
-
trong h cao n 100mg/L. Gi thit rng h nc v khng kh bn trn l mt h kn, tnh hot
p ca CO
2
(Pa) trong khng kh nm cn bng vi Ca
2+
trn.
BI GII:
1
[H
+
] = 1,00.10
-7
M
18
K
a1
= [HCO
3
-
][H
+
]/[H
2
CO
3
] = 2,23.10
-4
[HCO
3
-
]/[H
2
CO
3
] = 2,23.10
3

K
a2
= [CO
3
2-
][H
+
]/[HCO
3
-
] = 4,69.10
-11
[CO
3
2-
]/[HCO
3
-
] = 4,69.10
-4

[H
2
CO
3
] : [HCO
3
-
] : [CO
3
2-
] = 4,48.10
-4
: 1,00 : 4,69.10
-4

(a) (b)
2.
P(CO
2
) = 1,01.10
5
.3,60.10
-4
= 36,36Pa
[CO
2(aq)
] = K(CO
2
).P(CO
2
) = 1,24.10
-5
mol/L
Nu khng lm c cu 6 2 th c th gi s [CO
2(aq)
]=1,11.10
-5
M tnh cc cu tip theo.
3.
a) tan = [CO
2(aq)
] + [H
2
CO
3
] + [HCO
3
-
] + [CO
3
2-
]
= [CO
2(aq)
] + [HCO
3
-
]
([H
2
CO
3
] = [CO
2(aq)
] . K(H
2
CO
3
) = 2,48.10
-8
M v
[CO
3
2-
] = K
a2
/([H
+
].[HCO
3
-
] = K
a2
= 4,69.10
-11
M u qa nh nn ta b qua).
[H
+
].[HCO
3
-
]/[CO
2(aq)
] = K
a1
.K(H
2
CO
3
) = 4,46.10
-7

T cu 6 2 [CO
2(aq)
]=1,24.10
-5
M ta tnh c [H
+
]=[HCO
3
-
]=2,35.10
-6
M
Vy tan ca CO
2
s bng 1,48.10
-5
M.
b) S dng [CO
2(aq)
]=1,11.10
-5
M tnh ton:
tan = [CO
2(aq)
] + [H
2
CO
3
] + [HCO
3
-
] + [CO
3
2-
]
= [CO
2(aq)
] + [HCO
3
-
]
([H
2
CO
3
] = [CO
2(aq)
] . K(H
2
CO
3
) = 2,48.10
-8
M v
[CO
3
2-
] = K
a2
/([H
+
].[HCO
3
-
] = K
a2
= 4,69.10
-11
M u qa nh nn ta b qua).
[H
+
].[HCO
3
-
]/[CO
2(aq)
] = K
a1
.K(H
2
CO
3
) = 4,46.10
-7

T cu 6 2 [CO
2(aq)
]=1,11.10
-5
M ta tnh c [H
+
]=[HCO
3
-
]=2,225.10
-6
M
Vy tan ca CO
2
s bng 1,34.10
-5
M.
4.
a) S dng [CO
2(aq)
] = 1,24.10
-5
M tnh ton:
Trong dung dch NaOH 1,00.10
-3
M, tan ca CO
2
phi tng ln do phn ng sau:
(1) CO
2(aq)
+ 2OH
-
CO
3
2-
+ H
2
O K = K(H
2
CO
3
).K
a1
.K
a2
/(1,00.10
-14
)
2
= 2,09.10
11

(2) CO
2(aq)
+ CO
3
2-
+ H
2
O 2HCO
3
-
K = K(H
2
CO
3
).K
a1
/K
a2
= 9,37.10
3

Kt hp (1) v (2): CO
2(aq)
+ OH
-
HCO
3
-
K = 4,43.10
7
.
Do K rt ln nn ton b lng OH
-
u chuyn ht v HCO
3
-
.
[HCO
3
-
] = 1,00.10
-3
M
[OH
-
] = 1,82.10
-6
M
[H
+
] = 5,49.10
-9
M
[CO
3
2-
] = 8,54.10
-6
M
tan = [CO
2(aq)
] + [H
2
CO
3
] + [HCO
3
-
] + [CO
3
2-
]
~ [CO
2(aq)
] + [HCO
3
-
] + [CO
3
2-
] = 1,02.10
-3
M
b) S dng [CO
2(aq)
] = 1,11.10
-5
M tnh ton:
Trong dung dch NaOH 1,00.10
-3
M, tan ca CO
2
phi tng ln do phn ng sau:
(3) CO
2(aq)
+ 2OH
-
CO
3
2-
+ H
2
O K = K(H
2
CO
3
).K
a1
.K
a2
/(1,00.10
-14
)
2
= 2,09.10
11

(4) CO
2(aq)
+ CO
3
2-
+ H
2
O 2HCO
3
-
K = K(H
2
CO
3
).K
a1
/K
a2
= 9,37.10
3

Kt hp (1) v (2): CO
2(aq)
+ OH
-
HCO
3
-
K = 4,43.10
7
.
Do K rt ln nn ton b lng OH
-
u chuyn ht v HCO
3
-
.
[HCO
3
-
] = 1,00.10
-3
M
19
[OH
-
] = 1,82.10
-6
M
[H
+
] = 5,49.10
-9
M
[CO
3
2-
] = 8,54.10
-6
M
tan = [CO
2(aq)
] + [H
2
CO
3
] + [HCO
3
-
] + [CO
3
2-
]
~ [CO
2(aq)
] + [HCO
3
-
] + [CO
3
2-
] = 1,02.10
-3
M
5.
K
eq
= K
sp
.K(H
2
CO
3
).K
a1
/K
a2
= 4,28.10
-5

Nu khng tnh c cu 6 5 th ta c th gi s rng K
eq
= 5,00.10
-5
tnh ton.
6.
a) S dng K
eq
= 4,28.10
-5
v [CO
2(aq)
] = 1,24.10
-5
M tnh ton:
Cn bng khi lng: [HCO
3
-
] = 2[Ca
2+
]
T cu 6 5: K = 4,28.10
-5
= [Ca
2+
][HCO
3
-
]
2
/[CO
2(aq)
]
= [Ca
2+
](2[Ca
2+
])
2
/[CO
2(aq)
]
T cu 6 2: [CO
2(aq)
] = 1,24.10
-5
M
[Ca
2+
] = 0,510.10
-3
M = 20,5mg/L
b) S dng K
eq
= 5,00.10
-5
v [CO
2(aq)
] = 1,11.10
-5
M tnh ton:
Cn bng khi lng: [HCO
3
-
] = 2[Ca
2+
]
T cu 6 5: K = 5,00.10
-5
= [Ca
2+
][HCO
3
-
]
2
/[CO
2(aq)
]
= [Ca
2+
](2[Ca
2+
])
2
/[CO
2(aq)
]
T cu 6 2: [CO
2(aq)
] = 1,11.10
-5
M
[Ca
2+
] = 0,5177.10
-3
M = 20,75mg/L
c) S dng K
eq
= 5,00.10
-5
v [CO
2(aq)
] = 1,24.10
-5
M tnh ton:
Cn bng khi lng: [HCO
3
-
] = 2[Ca
2+
]
T cu 6 5: K = 5,00.10
-5
= [Ca
2+
][HCO
3
-
]
2
/[CO
2(aq)
]
= [Ca
2+
](2[Ca
2+
])
2
/[CO
2(aq)
]
T cu 6 2: [CO
2(aq)
] = 1,24.10
-5
M
[Ca
2+
] = 0,5372.10
-3
M = 21,53mg/L
d) S dng K
eq
= 4,28.10
-5
v [CO
2(aq)
] = 1,11.10
-5
M tnh ton:
Cn bng khi lng: [HCO
3
-
] = 2[Ca
2+
]
T cu 6 5: K = 4,28.10
-5
= [Ca
2+
][HCO
3
-
]
2
/[CO
2(aq)
]
= [Ca
2+
](2[Ca
2+
])
2
/[CO
2(aq)
]
T cu 6 2: [CO
2(aq)
] = 1,11.10
-5
M
[Ca
2+
] = 0,4916.10
-3
M = 19,70mg/L
7.
HCO
3
-
l thnh phn ch yu trong dung dch:
pH ca dung dch ny c th c tnh bng cng thc:
pH = (pK
a1
+ pK
a2
)/2 = 6,99 ~ 7,00
Vi K
a1
v K
a2
l hng s axit ca H
2
CO
3
.
Ti pH = 7,00 th [OH
-
] v [H
+
] ta c th b qua.
Bn cnh theo cu 6 1 th:[CO
3
2-
] << [HCO
3
-
]
kim = [HCO
3
-
] + 2[CO
3
-
] + [OH
-
] - [H
+
] ~ [HCO
3
-
]
T cu 6 6: ta c th c 5 kt qa sau:
a) 1,02.10
-3
M
b) 1,035.10
-3
M
c) 1,0744.10
-3
M
d) 0,9831.10
-3
M
20
e) 2,00.10
-3
M (gi s [Ca
2+
(aq)
] = 40,1mg/L)
8.
a) S dng K
eq
= 4,28.10
-5
tnh ton
Cn bng khi lng: [HCO
3
-
] = 2[Ca
2+
]
[Ca
2+
] = 100mg/L = 2,50.10
-3
M
Thay vo biu thc K
eq
= 4,28.10
-5
= [Ca
2+
][HCO
3
-
]
2
/[CO
2(aq)
]
= 4[Ca
2+
]
3
/[CO
2(aq)
]
[CO
2(aq)
] = 1,46.10
-3
M
P(CO
2
) = {[CO
2(aq)
]/K(CO
2
).1,01.10
5
= 4,28.10
3
Pa
b) S dng K
eq
= 5,00.10
-5
tnh ton:
Cn bng khi lng: [HCO
3
-
] = 2[Ca
2+
]
[Ca
2+
] = 100mg/L = 2,50.10
-3
M
Thay vo biu thc K
eq
= 5,00.10
-5
= [Ca
2+
][HCO
3
-
]
2
/[CO
2(aq)
]
= 4[Ca
2+
]
3
/[CO
2(aq)
]
[CO
2(aq)
] = 1,25.10
-3
M
P(CO
2
) = {[CO
2(aq)
]/K(CO
2
).1,01.10
5
= 3,67.10
3
Pa
III. BI TP CHUN B CHO OLYMPIC HA HC QUC T:
OLYMPIC HA HC QUC T LN TH 30:
Tnh axit ca mt mu nc ty thuc s hp th kh. Ni chung, kh quan trng nht gy nn
tnh axit l cacbon dioxit.
a) Vit ba phng trnh phn ng minh ha nh hng ca CO
2
trong khng kh ln tnh axit ca
nc.
b) Xp cc hn hp kh sau theo th t tng dn kh nng ha tan ca CO
2(k)
trong dung dch nc
(tnh theo % s mol)
i) 90% Ar; 10% CO
2
.
ii) 80% Ar; 10% CO
2
; 10% NH
3
.
iii) 80% Ar; 10% CO
2
; 10%Cl
2
.
Vit cc phng trnh ca bt k phn ng ho hc no xy ra trong dung dch nc khi phi
kh cc hn hp kh trn.
c) Xp cc h sau (trong nc) theo th t kh nng ho tan ca CO
2
. Gi thit rng trc khi phi
di hn hp 10% CO
2
trong Ar, chng t cn bng vi khng kh.
i) Nc ct.
ii) Dung dch HCl 1M
iii) Dung dch CH
3
COONa 1M
d) Gi thit rng khng kh c cha 350ppm CO
2
(theo th tch), v t cn bng gia CO
2
kh v
tan (trong nc), hy tnh pH ca mt git nc ma p sut khng kh. Cc hng s thch hp
ti 25
o
C l: k
H
(CO
2
) = 3,39.10
-2
mol.L
-1
.atm
-1
; K
b
(HCO
3
-
) = 2,24.10
-8
; K
b
(CO
3
2-
) = 2,14.10
-4
.
e) Tnh pH ca mt chai nc c ga (P(CO
2(k)
) = 1atm)
BI GII:
a) Cc phn ng:
CO
2(k)
CO
2(aq)
(1)
CO
2(aq)
+ H
2
O HCO
3
-
(aq)
+ H
+
(aq)
(2)
HCO
3
-
(aq)
CO
3
2-
(aq)
+ H
+
(aq)
(3)
l ta c thm cn bng:
CO
2(aq)
+ H
2
O H
2
CO
3(aq)

21
C th c gii thiu gii thch s tn ti ring bit ca CO
2
dng ho tan v ca axit
cacbonic phn t trong dung dch nc nhng khng bt buc phi dng cn bng ny gii thch phn
ng ho hc phn ng ca cacbonat trong nc.
Do cn bng c thit lp vi s c mt ng thi ca cc cht hai v ca mi phn ng v
do ta bt u t CO
2(k)
v H
2
O nn dung dch thu c r rng phi c tnh axit.
b) NH
3
l mt kh c tnh baz:
NH
3(k)
NH
3(aq)

NH
3(aq)
+ H
2
O NH
4
+
(aq)
+ OH
-
(aq)

Nn s xy ra phn ng axit baz, ko cn bng (2) v (3) theo chiu thun. iu ny lm tng
kh nng ho tan ca CO
2
c trong kh quyn.
Cl
2
l mt kh c tnh axit:
Cl
2(k)
Cl
2(aq)

Cl
2(aq)
+ H
2
O Cl
-
(aq)
+ H
+
(aq)
+ HOCl
(aq)

HOCl
(aq)
H
+
(aq)
+ OCl
-
(aq)

S gia tng [H
+
] sinh ra t cc phn ng ny s di cc cn bng (2) v (3) theo chiu nghch.
iu ny lm gim kh nng ho tan ca CO
2
trong kh quyn.
Nh vy chiu hng CO
2
ho tan l: ii>i>iii.
c) Axetat CH
3
COO
-
l baz lin hp ca mt axit yu:
CH
3
COO
-
(aq)
+ H
2
O CH
3
COOH
(aq)
+ OH
-
(aq)

Dung dch natri axetat c tnh kim v s di mi cn bng ca CO
2
theo chiu thun.
Dung dch HCl s di cn bng ca CO
2
theo chiu nghch.
Nh vy chiu hng CO
2
hoa tan l: iii>i>ii
d) Nng ca CO
2
trong dung dch nc c tnh bi nh lut Henry:
[CO
2(aq)
] = k
H
.P(CO
2
) = 1,187.10
-5
M
K
a
= K
w
/K
b

K
a
(CO
2(aq)
) = 4,46.10
-7

K
a
(HCO
3
-
(aq)
) = 4,67.10
-11

Do K
a
(CO
2(aq)
) >> K
a
(HCO
3
-
(aq)
) ta gi s rng trong dung dch axit ch c cn bng ca qa trnh
tch loi proton H
+
th nht l ng k (c th kim tra li iu ny mt khi tm c [H
+
]). Do :
[H
+
] = [HCO
3
-
] = 2,30.10
-6
M
Vy pH = 5,64
Nay, vi [H
+
] = [HCO
3
-
] = 2,30.10
-6
M ta c th thy [CO
3
2-
] = 4,67.10
-11
M. Do mc phn
ly ca HCO
3
-
thnh H
+
v CO
3
2-
rt nh v gi thit nu trn l ng.
e) Thy ngay l 1atm CO
2(k)
s to dung dch axit hn l 350ppm CO
2(k)
: Vy vi cc l do nh
trnh by cu d ta ch cn xt cn bng:
CO
2(k)
CO
2(aq)
CO
2(aq)
+ H
2
O HCO
3
-
(aq)
+ H
+
(aq)

gii quyt cu hi
[CO
2(aq)
] = k
H
.P(CO
2
) = 3,39.10
-2
M
v [H
+
] = [HCO
3
-
] = (K
a
[CO
2(aq)
])
0,5
= 1,23.10
-4
M
Vy pH = 3,91
OLYMPIC HA HC QUC T LN TH 31:
a) Axit photphoric, H
3
PO
4
l mt axit ba chc. Nu chun mt dung dch H
3
PO
4
0,1000M vi
NaOH 0,1000M. Hy c lng pH ti cc thi im sau:
22
i) Gia im bt u v im tng ng th nht.
ii) Ti im tng ng th hai.
iii) Ti sao rt kh xc nh ng cong chun sau im tng ng th hai?
K
1
= 7,1.10
-3
K
2
= 6,2.10
-8
K
3
= 4,4.10
-13
.
b) Mt dung dch cha 530mmol Na
2
S
2
O
3
v mt lng cha xc nh KI. Khi dung dch ny c
chun vi AgNO
3
th dng c 20,0mmol AgNO
3
trc khi bt u vn c v AgI kt
ta. C bao nhiu mmol KI?. Bit th tch sau cng l 200mL.
Ag(S
2
O
3
)
2
3-
Ag
+
+ 2S
2
O
3
2-
(aq)
K
d
= 6,0.10
-14
.
AgI
(r)
Ag
+
(aq)
+ I
-
(aq)

T = 8,5.10
-17
.
BI GII:
a) (i) C dung dch m H
3
PO
4
v H
2
PO
4
-

| |
| |
| |
| |
15 , 2
10 . 1 , 7
3
4 3
4 2
4 3
1
=
=
=

+
pH
M PO H
PO H
PO H
K H

(ii) Ti im tng ng th hai, c HPO
4
2-
nn:
[H
+
] = (K
2
K
3
)
0,5
= 1,7.10
-10
M
pH = 9,77
(iii) HPO
4
2-
(K
3
= 4,4.10
-13
) c tnh axit khng mnh hn H
2
O bao nhiu (K
w
= 1,00.10
-14
). Thm
baz mnh vo dung dch HPO
4
2-
tng t nh thm baz mnh vo nc.
b) Do hng s to phc ca Ag(S
2
O
3
)
2
3-
, K
f
= (K
d
)
-1
= 1,667.10
13
l rt ln nn hu ht Ag
+
thm
vo s to phc vi S
2
O
3
2-
v:
[Ag(S
2
O
3
)
2
3-
] = 0,100M
s mmol S
2
O
3
2-

t do = 530 (2.20) = 490mmol.
[S
2
O
3
2-
] = 2,450M
Nng ion Ag
+
t do c tnh t K
d

| || |
| |
| |
15
14
3
2 3 2
2
2
3 2
10 . 0 , 1
10 . 0 , 6
) (
+

+
=
= =
Ag
O S Ag
O S Ag
K
d

Ag
+
+ I
-
AgI
T = [Ag
+
][I
-
] = 8,5.10
-17

[I
-
] = 8,5.10
-2
M
mmol KI = 17,0mmol.










23
OLYMPIC HA HC QUC T LN TH 31:
Cc dung dch X, Y tun theo nh lut Beer trn mt khong nng kh rng. S liu ph ca
cc tiu phn ny trong cuvet 1,00cm nh sau:
(nm) Mt quang A
X (8,00.10
-5
M) Y (2,00.10
-4
M)
400 0,077 0,555
440 0,096 0,600
480 0,106 0,564
520 0,113 0,433
560 0,126 0,254
600 0,264 0,100
660 0,373 0,030
700 0,346 0,063
a) Hy tnh hp th mol ca X v Y ti 440 v 660nm
b) Hy tnh mt quang ca mt dung dch 3,00.10
-5
M theo X v 5,00.10
-4
M theo Y ti 520 v
600nm.
c) Mt dung dch cha X v Y c mt quang 0,400 v 0,500 theo th t ti 440 v 660nm. Hy
tnh nng ca X v Y trong dung dch. Gi s khng xy ra phn ng gia X v Y.
BI GII:
a) T nh lut Beer A = c.l.C
Thay s t bng s liu ta c bng sau:
c
X
(cm
-1
.mol
-1
.L) c
Y
(cm
-1
.mol
-1
.L)
440nm 1,2.10
3
3,00.10
3
660nm 4,67.10
3
1,50.10
2
b) Ti 520nm
A = A
X
+ A
Y
= 1,125
Ti 600nm
A = A
X
+ A
Y
= 0,349
c) Ti 440nm ta c: 0,400 = 1,2.10
3
C
X
+ 3,0.10
3
C
Y

Ti 660nm ta c: 0,500 = 4,67.10
3
C
X
+ 1,5.10
2
C
Y

Gii h phng trnh trn ta c:
C
X
= 1,04.10
-4
M v C
Y
= 9,17.10
-5
M
OLYMPIC HA HC QUC T LN TH 32:
Tr s pH ca nc nguyn cht l 7,0; trong khi nc ma t nhin c tnh axit yu do s
ho tan ca cacbon dioxit trong kh quyn. Tuy nhin trong nhiu khu vc nc ma c tnh axit mnh
hn. iu ny do mt s nguyn nhn trong c nhng nguyn nhn t nhin v nhng nguyn nhn
xut pht t cc hot ng ca con ngi. Trong kh quyn SO
2
v NO b oxy ha theo th t thnh SO
3

v NO
2
, chng phn ng vi nc chuyn thnh axit sunfuric v axit nitric. Hu qa l to thnh
ma axit vi pH trung bnh khong 4,5. Tuy nhin cng o c cc tr s thp n mc 1,7.
Lu hunh dioxit SO
2
l mt axit hai chc trong dung dch nc. Ti 25
o
C cc hng s axit
bng:
SO
2(aq)
+ H
2
O
(l)
HSO
3
-
(aq)
+ H
+
(aq)
K
a1
= 10
-1,92
M
HSO
3
-
(aq)
SO
3
2-
(aq)
+ H
+
(aq)
K
a2
= 10
-7,18
M
Tt c cc cu hi sau u xt 25
o
C:
a) Tnh tan ca SO
2
l 33,9L tng 1L H
2
O ti p sut ring phn ca lu hunh dioxit bng 1 bar.
24
i) Hy tnh nng ton phn ca SO
2
trong nc bo ho kh SO
2
(b qua s thay i
th tnh xy ra do s ho tan SO
2
)
ii) Hy tnh thnh phn phn trm ca ion hydrosunfit.
iii) Tnh pH ca dung dch.
b) Hy tnh [H
+
] trong dung dch nc ca Na
2
SO
3
0,0100M
c) Cn bng chnh trong dung dch nc ca NaHSO
3
.
2HSO
3
-
(aq)
SO
2(aq)
+ SO
3
2-
(aq)
+ H
2
O
(l)
.
i) Hy tnh hng s cn bng ca cn bng trn.
ii) Hy tnh nng ca lu hunh dioxit trong dung dch nc ca natri hydrosunfit
0,0100M nu ch xt cn bng ghi trn.
d) Tnh tan ca bari sunfit trong nc bng 0,016g/100mL
i) Hy tnh nng ion Ba
2+
trong nc bo ho.
ii) Hy tnh nng ca ion sunfit trong nc bo ho.
iii) Tnh T ca bari hydrosunfit.
e) Tch s tan ca bc sunfit bng 10
-13,82
M
3
. Hy tnh nng ion bc trong dung dch nc ca
bc sunfit bo ho (b qua tnh baz ca ion sunfit).
f) Tch s tan ca canxi sunfit bng 10
-7,17
M
2
. Hy tnh hng s cn bng ca phn ng:
Ca
2+
(aq)
+ Ag
2
SO
3(r)
CaSO
3(r)
+ 2Ag
+
(aq)

g) Nh tng git brom n d vo dung dch lu hunh dioxit 0,0100M. Ton b lu hunh dioxit
b oxy ha thnh sunfat (VI). Brom d c tch ra bng cch sc vi kh nit
Vit mt phng trnh phn ng ca qa trnh v tnh nng ion hydro tng dung dch thu
c. Gi s cc qa trnh ho hc cng nh cc thao tc th nghim u khng lm thay i th tch
dung dch. Tr s pK
a
ca ion hydrosunfat bng 1,99.
h) Sau mi t phun tro ni la, tr s pH ca nc ma o c bng 3,2. Hy tnh nng ton
phn ca axit sunfuric trong nc ma, gi thit rng s axit ho ch so axit sunfuric. Proton th
nhn trong axit sunfuric c th c xem nh phn li hon ton.
BI GII:
a) i) pV = nRT n = 1,368 mol C(SO
2
) = 1,368M
ii) SO
2(aq)
+ H
2
O HSO
3
-
(aq)
+ H
+
(aq)

vi [H
+
] = [HSO
3
-
] = x th M x
x
x
1224 , 0 10
368 , 1
99 , 1
2
= =



Vy %HSO
3
-
= 8,95%
iii) pH = 0,91
b) SO
3
2-
(aq)
+ H
2
O
(l)
OH
-
(aq)
+ HSO
3
-
(aq)

Vi [OH
-
] = [HSO
3
-
] = x th:
| | M H M x
x
x
10 5 82 , 6
18 , 7
14 2
10 . 57 , 2 10 . 89 , 3 10
10
10
01 , 0
+

= = = =


c) Ta c:
i)
| || |
| |
| || |
| |
| |
| |
26 , 5
1
2
3
2
3 2
3
2
3 2
10 .

+
+

= = = =
a
a
K
K
H
H
HSO
SO SO
HSO
SO SO
K
ii) [SO
2
] + [HSO
3
-
] + [SO
3
2-
] = 0,01M v [SO
2
] = [SO
3
2-
]
Vy ta c:
| |
| |
| | M SO
SO
SO
5
2
26 , 5
2
2
2
10 . 33 , 2 10
) 2 01 , 0 (

= =


25
d) M(BaSO
3
) = 217,39g.mol
-1
.
i) [Ba
2+
] = 7,36.10
-4
M
ii) SO
3
2-
(aq)
+ H
2
O
(l)
OH
-
(aq)
+ HSO
3
-
(aq)

[OH
-
] = [HSO
3
-
] = x
[HSO
3
-
] + [SO
3
2-
] = [Ba
2+
]
| | M SO M x
x
x
4 2
3
5
82 , 6
4
2
10 . 26 , 7 10 . 0479 , 1
10
) 10 . 36 , 7 (

= =
=

e) [Ag
+
] = 3,927.10
-5
M
f) K =
| |
| |
| |
| |
| |
| |
65 , 6
O
2
3
2
3
2
2
2
2
10 .
3
3 2

+
+
+
+
= = =
CaS
SO Ag
T
T
SO
SO
Ca
Ag
Ca
Ag

g) Phn ng: 2H
2
O
(l)
+ SO
2(aq)
+ Br
2(aq)
SO
4
2-
(aq)
+ Br
-
(aq)
+ 4H
+
(aq)

Cn bng: HSO
4
-
(aq)
SO
4
2-
(aq)
+ H
+
(aq)
K
a
= 10
-1,99
M
[SO
4
2-
] = [HSO
4
-
] = 0,01M v [H
+
] + [HSO
4
-
] = 0,04M
[HSO
4
-
] = 0,04 - [H
+
] v [SO
4
2-
] = [H
+
] 0,03M [H
+
] = 0,0324M
h) [H
+
] = 10
-3,2
M; K
a
= 10
-1,99
M; [HSO
4
-
] = 10
-1,28
[SO
4
2-
]
[H
+
] = 10
-3,2
= 10
-1,28
[SO
4
2-
] + 2[SO
4
2-
] + 10
-10,8
.
[SO
4
2-
] = 3,074.10
-4
M v [HSO
4
-
] = 1,613.10
-5
M
C(H
2
SO
4
) = [HSO
4
-
] + [SO
4
2-
] = 3,24.10
-4
M.
OLYMPIC HA HC QUC T LN TH 32:
Ho tan 1,00NH
4
Cl v 1,00g Ba(OH)
2
.8H
2
O vo 80mL nc. Pha long dung dch thu c
bng nc n 100mL ti 25
o
C.
a) Tnh pH ca dung dch (pK
a
(NH
4
+
) = 9,24
b) Hy tnh nng ca tt c cc ion trong dung dch.
c) Hy tnh pH sau khi thm 10,0mL dung dch HCl 1,00M vo dung dch trn.
d) Hy tnh [NH
3
] ca dung dch mi.
BI GII:
a) NH
4
+
(aq)
+ OH
-
(aq)
NH
3(aq)
+ H
2
O
(aq)

18,7mmol NH
4
Cl v 3,17 mmol Ba(OH)
2
.8H
2
O (6,34mmol OH
-
) to ra 6,34mmol NH
3
v
12,4mmol NH
4
+
cn li khng i.
| |
| |
| |
95 , 8 10 . 13 , 1
9
3
4
= = =

+
+
pH M
NH
NH
K H
a

b) [NH
4
+
] = 0,124M; [Ba
2+
] = 0,0317M; [H
+
] = 1,13.10
-9
M; [Cl
-
] = 0,187M; [OH
-
] = 8,85.10
-6
M
c) Thm 10,0mmol HCl, trong c 6,34mmol c NH
3
trung ho. Gi thit rng th tch bng
110mL, v b qua axit yu NH
4
+
ta c: [H
+
] = 0,0333M pH = 1,48
d) Trong dung dch axit mnh [NH
3
] s rt nh: [NH
4
+
] = 0,170M
| |
| |
| |
M
H
NH
K NH
a
9 4
3
10 . 9 , 2

+
+
= =




26
OLYMPIC HA HC QUC T LN TH 32:
Mt hc sinh iu ch dung dch bo ho magie hydroxit trong nc tinh khit ti 25
o
C. Tr s
pH ca dung dch bo ho c tnh bng 10,5.
a) Dng kt qa ny tnh tan ca magie hydroxit trong nc. Phi tnh tan theo mol.L
-1

cng nh g/100mL.
b) Hy tnh tch s tan ca magie hydroxit.
c) Hy tnh tan ca magie hydroxit trong dung dch NaOH 0,010M ti 25
o
C.
Khuy trn mt hn hp gm 10g Mg(OH)
2
v 100mL dung dch HCl 0,100M bng my khuy
t tnh trong mt thi gian ti 25
o
C.
d) Hy tnh pH ca pha lng khi h thng t cn bng.
BI GII:
a) Mg(OH)
2
Mg
2+
+ 2OH
-

pOH = 14,0 10,5 = 3,5 [OH
-
] = 10
-3,5
= 3,2.10
-4
M
Tng ng vi [Mg
2+
] = [Mg(OH)
2
in ly] = tan ca Mg(OH)
2
= 1,6.10
-4
M hay 9,2.10
-4
g/100mL.
b) K
sp
= [Mg
2+
][OH
-
]
2
= 1,6.10
-11
M
3

c) Mg(OH)
2
(r) Mg
2+
(aq) + 2OH
-
(aq)
[Mg
2+
] = x; [OH
-
] = 0,010 + 2x ~ 0,010M
K
sp
= [Mg
2+
][OH
-
]
2
= x[OH
-
]
2
= 1,6.10
-11
M x
7
2
11
10 . 6 , 1
) 010 , 0 (
10 . 6 , 1

= =
tan bng 1,6.10
-7
M hay 9.10
-7
g/100mL
d) Mg(OH)
2
c rt d v axit clohydric b trung ho hon ton theo phn ng:
Mg(OH)
2
(r) + 2H
+
(aq) Mg
2+
(aq) + 2H
2
O (l)
Gi s th tch khng i v bng 100mL, phn ng ny to ra Mg
2+
c nng 0,050M.
Ri Mg(OH)
2
ho tan trong dung dch [Mg
2+
] = 0,010 + x ~ 0,050M
| |
| |
3 , 9 ) 10 . 8 , 1 lg( 14 14 10 . 8 , 1
5 5
2
= + = = = =

+

pOH pH M
Mg
K
OH
sp

OLYMPIC HA HC QUC T LN TH 32:
Cadimi l mt trong nhng kim loi rt c c tm thy vi nng cao trong cht thi t s
luyn km, m in v x l nc thi. Ht phi cadimi dng ht nh s nhanh chng nh hng n h
h hp ri sau l thn. Cadimi cho thy s cnh tranh vi km ti cc vng hot ng ca enzym.
Cadimi to thnh hydroxit hi kh tan l Cd(OH)
2
.
a) Hy tnh tan ca Cd(OH)
2
trong nc nguyn cht (b qua cn bng t proton phn)
b) Hy tnh tan ca Cd(OH)
2
trong dung dch NaOH
(aq)
0,010M
Ion Cd
2+
c i lc mnh vi ion CN
-
:
Cd
2+
(aq)
+ CN
-
(aq)
Cd(CN)
+
(aq)
K
1
= 10
5,48
M
-1
.
Cd(CN)
+
(aq)
+ CN
-
(aq)
Cd(CN)
2(aq)
K
2
= 10
5,12
M
-1
.
Cd(CN)
2(aq)
+ CN
-
(aq)
Cd(CN)
3
-
(aq)
K
3
= 10
4,63
M
-1
.
Cd(CN)
3
-
(aq)
+ CN
-
(aq)
Cd(CN)
4
2-
(aq)
K
4
= 10
3,65
M
-1
.
c) Hy tnh tan ca Cd(OH)
2
trong nc c cha ion CN
-
. Nng cn bng l [CN
-
]=1,00.10
-
3
M
d) Gi thit rng ch to thnh phc Cd(CN)
4
2-
, hy tnh phn trm sai lch tan so vi tan tm
c cu c.
Bit T(Cd(OH)
2
) = 5,9.10
-15
M
3
.
27
BI GII:
a) S = 1,14.10
-5
M
b) S = 5,9.10
-11
M
c) S = 0,5[OH
-
] = C(Cd)
C(Cd) = [Cd
2+
] + [Cd(CN)
+
] + [Cd(CN)
2
] + [Cd(CN)
3
-
] + [Cd(CN)
4
2-
]
0,5[OH
-
] = [Cd
2+
](1 + K
1
[CN
-
] + K
1
K
2
[CN
-
]
2
+ K
1
K
2
K
3
[CN
-
]
3
+ K
1
K
2
K
3
K
4
[CN
-
]
4
)
[OH
-
] = [2.T(1 + K
1
[CN
-
] + K
1
K
2
[CN
-
]
2
+ K
1
K
2
K
3
[CN
-
]
3
+ K
1
K
2
K
3
K
4
[CN
-
]
4
)]
3/2

= 4,79.10
-3
M
S = 2,4.10
-3
M
d) [OH
-
] = [2.T.(1 + K
1
K
2
K
3
K
4
[CN
-
]
4
)]
3/2
= 4,47.10
-3
M
S = 2,24.10
-3
M
Phn trm sai lch = 6,7%
OLYMPIC HA HC QUC T LN TH 33:
Hai yu t quan trng nht nh hng ln tan ca cc mui kh tan l pH v s c mt ca tc
nhn to phc. Bc oxalat l mt v d in hnh: Tch s tan ca n trong nc l T = 2,06.10
-4
ti
pH=7. tan ca n b nh hng bi pH khi anion oxalat phn ng vi ion hydroni v bng tc nhn
to phc chng hn nh amoniac to phc vi cation bc.
a) Tnh tan ca bc oxalat trong dung dch axit c pH = 5,0. Hai hng s phn li ca axit oxalic
ln lt l: K
1
= 5,6.10
-2
v K
2
= 6,2.10
-6
.
b) Vi s c mt ca amoniac th ion bc to thnh hai dng phc Ag(NH
3
)
+
v Ag(NH
3
)
2
+
. Cc
hng s to phc tng nc tng ng s l |
1
= 1,59.10
3
v |
2
= 6,76.10
3
. Tnh tan ca bc
oxalat trong dung dch cha 0,02M NH
3
v c pH = 10,8.
BI GII:
a) T = [Ag
+
]
2
[C
2
O
4
2-
]
Ta c: [Ag
+
] = 2S
C(C
2
O
4
2-
) = S = [C
2
O
4
2-
] + [HC
2
O
4
-
] + [H
2
C
2
O
4
]
H
2
C
2
O
4
= H
+
+ HC
2
O
4
-
K
1
= 5,6.10
-2
.
HC
2
O
4
-
= H
+
+ C
2
O
4
2-
K
2
= 6,2.10
-6
.
Ta c kt qa sau: S = | |
| | | |
|
|
.
|

\
|
+ +
+ +

2 1
2
2
2
4 2
1
K K
H
K
H
O C
| |
| | | |
S S
K K H K H
K K
O C . .
2 1 1
2
2 1 2
4 2
o =
+ +
=
+ +


Ti pH = 7 th [H
+
] = 10
-7
o ~ 1
T = 3,5.10
-11
.
Ti pH = 5 th [H
+
] = 10
-5
o ~ 0,861
S = 2,17.10
-4
.
b) [NH
3
] = 0,02M
Ti pH = 10,8 th [H
+
] = 1,585.10
-11
o ~ 1
Tng nng [Ag
+
] trong dung dch c xc nh bi phng trnh
C
Ag
= 2S = [Ag
+
] + [Ag(NH
3
)
+
] + [Ag(NH
3
)
2
+
]
Cc phn ng to phc:
Ag
+
+ NH
3
= Ag(NH
3
)
+

|
1
= 1,59.10
3

Ag(NH
3
)
+
+ NH
3
= Ag(NH
3
)
2
+

|
2
= 6,76.10
3

T cc phng trnh trn ta d dng suy ra c biu thc sau:
28
C
Ag
= 2S = [Ag
+
](1 + |
1
[NH
3
] + |
1
|
2
[NH
3
]
2
)
| |
| | | |
S S
NH NH
Ag
| | |
=
+ +
=
+
.
1
1
2
3 2 1 3 1

Thay vo biu thc ca T ta tnh c S = 5,47.10
-2
.
OLYMPIC HA HC QUC T LN TH 33:
Mt hp cht nitro hu c (RNO
2
) c kh bng phng php in ha trong dung dch m
axetat c tng nng axetat (HOAc+ OAc
-
) l 0,500M v c pH = 5. 300mL dung dch m cha
0,01M RNO
2
em kh in ha hon ton. Axit axetic c K
a
= 1,75.10
-5
25
o
C. Phn ng kh in ha
hp cht nitro xy ra nh sau:
RNO
2
+ 4H
+
+ 4e RNHOH + H
2
O
Tnh pH ca dung dch sau khi kt thc phn ng.

BI GII:
RNO
2
+ 4H
+
+ 4e RNHOH + H
2
O
Ta c:
| |
| |
| |
| |
5715 , 0 =
=

OAc
HOAc
OAc
HOAc
pH pK
a

Mt khc ta c: [HOAc] + [OAc
-
] = 0,500
[HOAc] = 0,1818
[OAc
-
] = 0,3182
Nh vy s mmol cc cht lc ban u l:
n(OAc
-
) = 95,45
n(HOAc) = 54,55
S mmol RNO
2
b kh s l: 300.0,0100 = 3mmol
T phng trnh bn phn ng ta thy rng kh ha hon ton 3mmol hp cht nitro cn
12mmol H
+
. S mmol H
+
ny nhn c t s phn ly ca HOAc.
Khi phn ng xy ra hon ton th:
n(HOAc) = 54,55 12,00 = 42,55mmol
n(OAc
-
) = 95,45 12,00 = 83,45mmol
Vy
| |
| |
16 , 5 = + =

OAc
HOAc
pK pH
a

OLYMPIC HA HC QUC T LN TH 34:
tan l mt thng s quan trng xc nh c s nhim mi trng do cc mui gy ra.
tan ca mt cht c nh ngha l lng cht cn thit c th tan vo mt lng dung mi to ra
c dung dch bo ho. tan ca cc cht khc nhau tu thuc vo bn cht ca dung mi v cht tan
cng nh ca cc iu kin th nghim, v d nh nhit v p sut. pH v kh nng to phc cng
nh hng n tan.
Mt dung dch cha BaCl
2
v SrCl
2
u nng 0,01M. Khi ta thm mt dung dch bo ho
natri sunfat vo dung dch th 99,9% BaCl
2
s kt ta di dng BaSO
4
v SrSO
4
ch c th kt ta nu
trong dung dch cn di 0,1% BaSO
4
. Tch s tan ca cc cht c cho sau y: T(BaSO
4
) = 10
-10
v
T(SrSO
4
) = 3.10
-7
.
1) Vit cc phng trnh phn ng to kt ta.
29
Tnh nng Ba
2+
cn li trong dung dch khi SrSO
4
bt u kt ta.
Tnh %Ba
2+
v Sr
2+
sau khi tch ra.
S to phc gy nn mt nh hng ng k n tan. Phc l mt tiu phn tch in cha
mt ion kim loi trung tm lin kt vi mt hay nhiu phi t. V d Ag(NH
3
)
2
+
l mt phc cha ion
Ag
+
l ion trung tm v hai phn t NH
3
l phi t.
tan ca AgCl trong nc ct l 1,3.10
-5
M
Tch s tan ca AgCl l 1,7.10
-10
M
Hng s cn bng ca phn ng to phc c ga tr bng 1,5.10
7
.
2) S dng tnh ton cho thy rng tan ca AgCl trong dung dch NH
3
1,0M th cao hn trong
nc ct.
BI GII:
1) Cc phn ng to kt ta:
Ba
2+
+ SO
4
2-
= BaSO
4

Sr
2+
+ SO
4
2-
= SrSO
4

Kt ta BaSO
4
s xy ra khi [SO
4
2-
] = T(BaSO
4
)/[Ba
2+
] = 10
-8
M
Kt ta SrSO
4
s xy ra khi [SO
4
2-
] = 3.10
-5
M
Nu khng xy ra cc iu kin v ng hc (chng hn nh s hnh thnh kt ta BaSO
4
l v
cng chm) th BaSO
4
s c to thnh trc, kt qa l s c s gim nng Ba
2+
. Khi nng
SO
4
2-
tho mn yu cu kt ta SrSO
4
th lc ny nng cn li ca ion Ba
2+
trong dung dch c th
c tnh t cng thc:
T(BaSO
4
) = [Ba
2+
][SO
4
2-
] = [Ba
2+
].3.10
-5
[Ba
2+
] = 0,333.10
-5
M
%Ba
2+
cn li tng dung dch = % 033 , 0
10
10 . 333 , 0
2
5
=


2) Cn bng to phc gia AgCl v NH
3
c th c xem nh l t hp ca hai cn bng:
AgCl
(r)
Ag
+
(aq)
+ Cl
-
(aq)
T = 1,7.10
-10
.
Ag
+
(aq)
+ 2NH
3(aq)
Ag(NH
3
)
2
+
K
f
= 1,5.10
7

AgCl
(r)
+ 2NH
3(aq)
Ag(NH
3
)
2
+
+ Cl
-
(aq)
K = T.K
f
= 2,6.10
-3

Cn bng: (1,0 2x) x x
Do K rt b nn hu ht Ag
+
u tn ti dng phc:
Nu vng mt NH
3
th cn bng: [Ag
+
] = [Cl
-
]
S hnh thnh phc dn n: [Ag(NH
3
)
2
+
] = [Cl
-
]
Nh vy:
| || |
| |
M x
x
x
NH
Cl NH Ag
K 046 , 0 10 . 6 , 2
2 0 , 1
) (
3
2
2
3
2 3
= =

= =

+

Kt qa ny c ngha l 4,6.10
-2
M AgCl tan trong dung dch NH
3
1,0M, nhiu hn trong nc
ct l 1,3.10
-5
M. Nh vy s to thnh phc Ag(NH
3
)
2
+
dn n vic lm tng tan ca AgCl.
OLYMPIC HA HC QUC T LN TH 35:
Cc axit yu c chun vi dung dch baz mnh bit trc nng (dung dch chun).
Dung dch axit yu (cht phn tch) c chuyn vo bnh nn 250cm
3
v dung dch baz mnh (cht
chun) c cho vo buret. im tng ng ca php chun t c khi lng cht chun cn
bng vi lng cht phn tch. Gin biu th s thay i ca pH nh l mt hm ca th tch cht
chun c thm vo c gi l ng cong chun .
im tng ng ca php chun ch c th c xc nh bng l thuyt, n khng th
c xc nh bng thc nghim. N ch c th c lng c bng cch xc nh s thay i ca mt
30
vi tnh cht vt l trong qa trnh chun . Trong phng php chun axit baz, im cui ca
php chun c xc nh bng cch s dng cht ch th axit baz.
1) Xy dng ng cong chun bng cch tnh mt vi im c trng v chn cht ch th thch
hp trong vic chun 50,00cm
3
CH
3
COOH 0,1000M (K
a
= 1,8.10
-5
) bng dung dch NaOH
0,1000M. V cht ch th c th tham kho bng 1:
Tn ch th Khong chuyn mu Mu dng axit baz
Metyl da cam 3,2 4,4 - da cam
Matyl 4,2 6,2 - vng
Bromthymol xanh 6,0 7,6 Vng - xanh
Phenol 6,8 8,2 Vng -
Phenolphtalein 8,0 -9,8 Khng mu -
Thymophtalein 9,3 10,5 Khng mu xanh
2) Axit ascorbic (Vitamin C) l mt axit yu v chu s phn ly theo phng trnh:

Chnh v vy axit ascorbic c th chun c nc 1 bng NaOH
50,00cm
3
dung dch C
6
H
8
O
6
0,1000M c chun bng 0,2000M:
(i) pH ca dung dch lc u l:
a) 7,00; b) 2,58 c) 4,17 d) 1,00
(ii) Th tch ca cht chun cn t n im tng ng l:
a) 50,00cm
3
b) 35,00cm
3
c) 25,00cm
3
d) 20,00cm
3

(iii) Sau khi thm 12,5cm
3
dung dch chun th pH ca dung dch s l:
a) 4,17 b) 2,58 c) 7,00 d) 4,58
(iv) pH im tng ng s l:
a) 7,00 b) 8,50 c) 8,43 d) 8,58
(v) Cht ch th c s dng trong phn ng ny s l (xem bng 1)
a) bromthymol xanh b) phenol c) phenolphthalein d) thymolphtalein
(vi) pH ca dung dch sau khi thm 26,00cm
3
cht chun l:
a) 13,30 b) 11,30 c) 11,00 d) 11,42
BI GII:
Phn ng chun : CH
3
COOH + OH
-
= CH
3
COO
-
+ H
2
O
a) pH trc khi tin hnh chun
Do trc khi chun th trong bnh nn ch c CH
3
COOH nn pH ca dung dch s c tnh
t phng trnh phn ly CH
3
COOH
CH
3
COOH CH
3
COO
-
+ H
+

T phng trnh phn ly:

th nng H
+
c th c tnh theo biu thc:

pH = 2,87
b) pH sau khi thm 10,00cm
3
cht chun:
Trong dung dch lc ny cha mui natri axetat v axit axetic cn d nn n l dung dch m:
Nng ca mi cht trong dung dch c tnh nh sau:
31

Nng H
+
lc ny c th tnh c bng cch p dng phng trnh Henderson
Hasselbatch:

pH = 4,14
c) pH im tng ng
Lc ny th ton b lng axit axetic phn ng ht vi lng NaOH thm vo nn trong dung
dch lc ny ch cn li anion axetat. Lc ny pH c quyt nh bi s phn ly ca anion ny:
CH
3
COOH + H
2
O CH
3
COOH + OH
-

Th tch cht chun cn t n im tng ng (V
ep
) c tnh nh sau:

Vo lc ny th tng th tch dung dch l 100cm
3
. Vo thi im ny ca vic chun th
[CH
3
COOH] = [OH
-
] v:

pOH = 5,28 pH = 8,72
d) pH sau khi thm 50,10cm
3
cht chun
Vo thi im ny th ton b axit axetic chuyn ht thnh natri axetat nn pH ca dung dch
lc ny s c quyt nh bi lng d dung dch natri hydroxit thm vo. Nh vy:

pOH = 4,00 pH = 10,00
Lc ny ng nh phn s c dng

Do pH im tng ng l 8,72 nn ch th ph hp lc ny l phenolphthalein
2) (i) b, (ii) c, (iii) a, (iv) b, (v) c, (vi) d
32
OLYMPIC HA HC QUC T LN TH 35:
Dung dch m l dung dch c kh nng chng li s thay i pH. Thng thng dung dch m
gm mt axit yu v baz lin hp ca n (v d: CH
3
COOH/CH
3
COO
-
) hay mt baz yu v axit lin
hp ca n (V d NH
3
/NH
4
+
). Dung dch m c to thnh khi trung ho mt phn axit yu bi baz
mnh hay baz yu v axit mnh. Chnh v vy ta c th chun b dung dch m bng cch trn mt
lng axit (hay baz) yu tnh trc vi phn lin hp ca n.
pH ca dung dch m c to thnh bi axit yu HA v baz lin hp A
-
c tnh theo
phng trnh Henderson Hasselbalch:

| |
| |

+ =
OAc
HOAc
pK pH
a

3) Tnh pH ca dung dch m cha 0,200M axit fomic (K
a
= 2,1.10
-4
) v 0,150M natri fomiat.
4) Tnh pH ca dung dch khi thm 0,01000M dung dch NaOH vo dung dch m cu 1
5) Tnh th tch ca dung dch NaOH 0,200M cn thm vo 100,0cm
3
dung dch CH
3
COOH 0,150M
(K
a
= 1,8.10
-5
) thu c dung dch m c pH = 5,00
6) pH ca dung dch m cha 0,0100M axit benzoic (K
a
= 6,6.10
-5
) v C
6
H
5
COONa

0,0100M s l:
a) 5,00
b) 4,18
c) 9,82
d) 9,0
7) Khi trn cng mt th tch 0,100 CH
3
COOH (K
a
= 1,8.10
-5
) v 0,0500M NaOH th:
i) Dung dch sau cng s l:
a) D axit yu.
b) D baz mnh
c) Dung dch m
d) C ba u sai.
ii) pH ca dung dch cui s l:
a) 3,02
b) 4,44
c) 3,17
d) 7,00
6) Khi trn cng mt th tch dung dch CH
3
COOH 0,100M v NaOH 0,150M th:
i) Dung dch cui cng s l:
a) D axit yu.
b) D baz mnh
c) Dung dch m
d) C ba u sai.
ii) pH ca dung dch cui s l:
a) 12,00
b) 12,70
c) 13,18
d) 12,40
7) Khi trn cng mt th tch dung dch CH
3
COOH 0,150M v NaOH 0,100M th:
i) Dung dch cui cng s l:
a) D axit yu.
b) D baz mnh
c) Dung dch m
33
d) C ba u sai.
ii) pH ca dung dch cui s l:
a) 3,17
b) 3,02
c) 2,78
d) 3,22
8) Khi trn cng mt th tch dung dch CH
3
COOH 0,100M v NaOH 0,100M th:
i) Dung dch cui cng s l:
a) D axit yu.
b) D baz mnh
c) Dung dch m
d) C ba u sai.
1. pH ca dung dch cui s l:
a) 7,00
b) 13,00
c) 2,87
d) 3,02
BI GII:
1) pH = 3,55
2) Natri hydroxit s phn ng vi HCOOH:
HCOOH + OH
-
HCOO
-
+ H
2
O
Phn ng ny xy ra hon ton nn:
[HCOOH] = 0,140M
[HCOO
-
] = 0,160M
Vy pH = 3,60
Lu rng ta thm mt baz mnh nh NaOH m pH ch thay i 0,05 n v
3) Gi V l th tch ca dung dch NaOH. Nh vy th tch cui ca dung dch s l (100,0 + V) v s
mmol CH
3
COOH v OH
-
l 100,0.0,150 = 15,00mmol v V.0,200 = 0,200V mmol tng ng. T
phn ng:
CH
3
COOH + OH
-
CH
3
COO
-
+ H
2
O
Nh vy lng CH
3
COO
-
sinh ra s l 0,200V mmol v lng CH
3
COOH cha phn ng s l
(15,00-0,200V)mmol. Nh vy nng ca cc tiu phn trong dung dch m s l:
| |
| | M
V
V
COO CH
M
V
COOH CH
+
=
+

0 , 100
200 , 0
0 , 100
200 , 0 00 , 15
3
3

T biu thc hng s phn li ca axit axetic ta c th nhn c:
| |
| | | |
3
5
5
3
3
21 , 48
10 . 0 , 1
10 . 8 , 1
100
200 , 0 00 , 15
0 , 100
200 , 0
cm V
V
V
V
H
K
COOH CH
COO CH
a
= =
+

+
=


OLYMPIC HA HC QUC T LN TH 37:
34
Nha trao i ion c th c s dng hp th v phn lp cation v anion. Chng c th
c iu ch t cc vt liu v c v hu c. Mt loi nha trao i cation hu c c th c tng
hp bng s ng trng hp styren /divinyl benzen tip theo bi s sunfo ho bng H
2
SO
4
nh s
1:










S 1
Nha trao i cation (k hiu l R
-
H
+
) c th c s dng hp th cc cation. Phn ng c
th c biu din nh sau:
R
-
H
+
+ M
+
= RM + H
+
K
C
= [RM][H
+
]/[R
-
H
+
][M
+
] (1)
K
D
= [RM]/[M
+
] (2)
Nha trao i cation R
-
H
+
c th c chuyn ha thnh cht trao i ion R
-
M
+
hay R
-
M
2+
bng
phn ng gia R
-
H
+
vi mt hydroxit kim lai M(OH)
z
. Phng trnh phn ng s l:
R
-
H
+
+ MOH = R
-
M
+
+ H
2
O (3)
V zR
-
H
+
+ M(OH)
z
= (R
-
)
z
M
+
+ zH
2
O (4)
1) Mt loi nha trao i cation R
-
Na
+
c s dng loi CaCl
2
trong nc my.
a) Vit phng trnh phn ng.
b) Nu mt loi nha trao i khc R
-
H
+
c s dng thay th cho R
-
Na
+
.
i) Vit phn ng xy ra.
ii) Cho bit loi nha trao i ion no R
-
H
+
hay R
-
Na
+
th ph hp hn trong vic loi Ca
2+
ra khi
nc thi v cho bit l do.
2) Mt loi nha trao i anion hu c (R
+
Cl
-
) c th c tng hp bng s ng trng hp styren
/divinyl benzen vi xc tc l mt axit Lewis nh AlCl
3
v mt amin bc 3 NR
3
, nh s sau:

Loi nha trao i ion R
+
OH
-
c th nhn c t phn ng:
R
+
Cl
-
+ NaOH = R
+
OH
-
+ NaCl (5)
a) Bng cch no m H
+
sinh ra t dung dch HCl c th b loi b vi mt loi nha trao i ion
R
+
OH
-
. Vit cc phng trnh phn ng xy ra.

H
2
SO
4
C C C C
C C C C
SO
3
-
H
+
[ cationic exchanger ]
R
-
H
+
C C
+
C C
C C
Na
2
S
2
O
8
C C C C
C C C C
[ polymer ]
35
b) Bng cch no ta c th loi c ion SO
4
2-
trong nc my bng loi nha trao i ion R
+
OH
-

trn. Vit cc phng trnh phn ng xy ra.
Dung lng (S) ca nha trao i cation R
-
H
+
i vi mt ion b hp th c th c xc nh
bng s mol ca ion hp th/gam ca mt nha trao i ion tng 1,0mL dung dch nc v c th c
tnh bng cch s dng phng trnh sau:
S = ([RM] + [RH]).10
-3
(6)
Dung lng (S) ca mt nha trao i cation R
-
H
+
i vi ion M
+
trong mt dung dch nc c
th c xc nh t hng s cn bng K
C
, hng s phn b K
D
v nng ca cc ion M
+
v H
+
trong
dung dch.
3) Hy chng minh phng trnh sau:
1/K
d
= [M
+
]/1000S + [H
+
]/K
C
.S.1000 (7)
4) Nha trao i ion c th c s dng lm pha tnh trong php sc k lng hp th v phn lp
cc loi ion khc nhau. V d: nha trao i anion R
+
OH
-
c th c s dng phn lp cc ion X
-

v Y
-
c th c ra gii bng NaOH. Php sc k lng trong vic phn tch cc anion X
-
v Y
-

s dng 30cm ct nha trao i ion nh hnh 1.
Vi t
1
, t
2
v t
o
l thi gian duy tr (Retention time)(t
R
) i vi X
-
v Y
-
v dung mi ra gii tinh
khit NaOH c th i qua ct, e1 v e2 l chiu rng pic ca X
-
v Y
-
. S a l thuyt N v chiu
cao a H (chiu cao ca tng s a l thuyt) ca ct c th c tnh bi cc biu thc sau:
N = 16(t
R
/e)
2
. (8)
v H = L/N (9)














Hnh 1: Sc k ph ca ion X
-
v Y
-

vi L l chiu di ct. phn gii (R) ca ct v h s phn ly o i vi X
-
v Y
-
c th c xc nh
bi cc h thc:
R = 2 (t
2
- t
1
) / (e
1
+ e
2
) (10)
v o = (t
2
t
o
) / (t
1
t
o
) (11)
a) Tnh s a l thuyt ca ct
b) Tnh chiu cao a.
c) Tnh phn gii (R) ca ct i vi hai anion X
-
v Y
-
.
d) Tnh h s phn ly o i vi X
-
v Y
-

1.0 10.0 14.0
t
0

t
1
t
2

1.0 1.5
t
R

Retention Time / min

X
-

Y
-

36
5) Mt s loi nha trao i ion c th nhn c t nhng vt liu v c. Zeolit
[(M
2+
)(Al
2
O
3
)
m
/(SiO
2
)
n
] (M
2+
= Na
+
; K
+
hay Ca
2+
; Mg
2+
) l nhng v d in hnh v nhng nha
trao i ion v c. Mt s v d v zeolit c cho trong hnh 2.

Hnh 2: Mt s loi zeolit
Mt loi Na* - zeolit (k hiu l Z-Na*) vi kch thc l hng l 13 l mt loi nha trao i
ion quan trng loi cc ion Ca
2+
v Mg
2+
ra khi nc my. Cc loi zeolit vi kch thc l hng
xc nh th c chn lc hp th rt cao i vi cc phn t khc nhau. V d H
2
O v iso-butan. Nh
vy, zeolit ng vai tr nh l mt ci ry phn t. Zeolit cng c th c s dng nh l mt cht xc
tc trong cng ngh ha du. V d: trong ha du iso-butan l kt qa ca s tng tc crackinh cc
tc nhn hp ph chn lc.
a) Vit phng trnh phn ng loi Ca
2+
ra khi nc my vi zeolit Z-Na*.
b) Vit phng trnh phn ng ca vic hp th K
+
vi zeolit Z-Na*.
BI GII:
1) a) 2RNa + Ca
2+
= (R)
2
Ca + 2Na
+

hay 2RNa + CaCl
2
= (R)
2
Ca + 2NaCl
b) i) 2RH + Ca
2+
= (R)
2
Ca + 2H
+

hay 2RH + CaCl
2
= (R)
2
Ca + 2HCl
ii) S dng RNa th kh thi hn so vi vic s dng RH bi v sn phm ca s hp th Ca
2+
bng
RNa l NaCl l sn phm t c hi hn l HCl (lm gim pH)
2) a) R
+
OH
-
+ HCl = R
+
Cl
-
+ H
2
O
b) Bc u tin s xy ra phn ng:
2R
+
OH
-
+ SO
4
2-
= (R
+
)
2
SO
4
2-
+ 2OH
-

Sau th thm HCl vo trung ho lng OH
-
sinh ra bc 1:
H
+
+ OH
-
= H
2
O
3 Thay phng trnh (1), (2) vo (6) v s dng mt s bin i ton hc n gin ta nhn c:
1/K
d
= [M
+
]/1000S + [H
+
]/K
C
.S.1000
4 a) N
1
= 16(t
1
/e
1
)
2
= 1600
N
2
= 16(t
2
/e
2
)
2
= 1394
N = (N
1
+ N
2
)/2 = 1497
b) H = L/N = 0,021cm
c) R = R = 2 (t
2
- t
1
) / (e
1
+ e
2
) = 3,2
d) o = (t
2
t
o
) / (t
1
t
o
) = 1,44
5. a) Z-Na
+
+ Ca
2+
= Z-Ca + Na
+

b) Z-Na
+
+ K
+
= Z-K
+
+ Na
+
OLYMPIC HA HC QUC T LN TH 37:
Lng canxi trong mu c th c xc nh bi cch sau:
37
Bc 1: Thm mt vi git ch th metyl vo dung dch mu c axit ha v sau l
trn vi dung dch Na
2
C
2
O
4
.
Bc 2: Thm ure (NH
2
)
2
CO v un si dung dch n khi ch th chuyn sang mu vng (vic
ny mt 15 pht). Kt ta CaC
2
O
4
xut hin.
Bc 3: Dung dch nng c lc v kt ta CaC
2
O
4
c ra bng nc lnh loi b lng
d ion C
2
O
4
2-
.
Bc 4: Cht rn khng tan CaC
2
O
4
c ho tan vo dung dch H
2
SO
4
0,1M sinh ra ion Ca
2+

v H
2
C
2
O
4
. Dung dch H
2
C
2
O
4
c chun vi dung dch chun KMnO
4
n khi dung dch c mu
hng th ngng.
Cc phn ng xy ra v cc hng s cn bng:
CaC
2
O
4(s)
Ca
2+
(aq)
+ C
2
O
4
2-
(aq)
T = 1.30x10
-8

Ca(OH)
2(s)
Ca
2+
(aq)
+ 2OH
-
(aq)
T = 6.50x10
-6

H
2
C
2
O
4(aq)
HC
2
O
4
-
(aq)
+ H
+
(aq)
K
a1
= 5.60x10
-2

HC
2
O
4
-
(aq)
C
2
O
4
2-
(aq)
+ H
+
(aq)
K
a2
= 5.42x10
-5

H
2
O H
+
(aq)
+ OH
-
(aq)
K
w
= 1.00x10
-14

1. Vit v cn bng cc phng trnh phn ng xy ra bc 2.
2. 25,00mL dung dch mu canxi c xc nh bng phng php trn v s dng ht 27,41mL
dung dch KMnO
4
2,50.10
-3
M bc cui cng. Xc nh nng Ca
2+
trong mu.
3. Tnh T ca CaC
2
O
4
trong mt dung dch m c pH = 4. (B qua h s hot )
Trong php phn tch trn th ta b qua mt nguyn nhn quan trng gy nn sai s. S kt ta
CaC
2
O
4
bc 1 s khng hon ton nu ta thm mt lng d C
2
O
4
2-
do cc phn ng sau:
Ca
2+
(aq)
+ C
2
O
4
2-
(aq)
CaC
2
O
4(aq)
K
f1
= 1.0 x 10
3

CaC
2
O
4(aq)
+ C
2
O
4
2-
(aq)
Ca(C
2
O
4
)
2
2-
(aq)
K
f2
= 10
4. Tnh nng cn bng ca Ca
2+
v C
2
O
4
2-
trong dung dch sau khi to thnh lng kt ta ti a ca
CaC
2
O
4
.
5. Tnh nng ion H
+
v Ca
2+
trong dung dch bo ho CaC
2
O
4
(B qua h s hot ).



BI GII:
1. (NH
2
)
2
CO + H
2
O
2 3
2 CO NH +
A

2. [Ca
2+
] = 6,85.10
-3
M
3. [Ca
2+
] = [C
2
O
4
2-
] + [HC
2
O
4
-
] + [H
2
C
2
O
4
]
= [C
2
O
4
2-
](1 + [H
+
]/K
1
+ [H
+
]
2
/K
1
K
2
)
Vy [C
2
O
4
2-
] = [Ca
2+
]/(1 + [H
+
]/K
1
+ [H
+
]
2
/K
1
K
2
) (1)
Thay (1) vo biu thc tch s tan: T = [Ca
2+
][C
2
O
4
2-
] ta tnh c [C
2
O
4
2-
] = 1,92.10
-4
M
4. Ta c:
38
| | | | ( ) | |
| |
| |
| |
| |
| | M Ca M O C
K TK
O C
T
O C d
dC
O C K K K
O C
T
O C Ca O CaC Ca C
f f
Ca
f f f
aq Ca
6 2 2 2
4 2
2 1
2
2
4 2
2
4 2
2
4 2 2 1 1
2
4 2
2
2 4 2 ) ( 4 2
2
10 . 3 , 1 10 . 0 , 1
0
1
1
+

+
= =
= + =
|
|
.
|

\
|
+ + =
+ + =

5. Cn bng in tch: 2[Ca
2+
] + [H
+
] = 2[C
2
O
4
2-
] + [HC
2
O
4
-
] + [OH
-
] (1)
Cn bng khi lng: [Ca
2+
] = [C
2
O
4
2-
] + [HC
2
O
4
-
] + [H
2
C
2
O
4
] (2)
V K
b2
rt nh nn nng ca H
2
C
2
O
4
c th b qua.
Kt hp (1) v (2) ta c: [HC
2
O
4
-
] = K
w
/[H
+
] - [H
+
] (3)
[C
2
O
4
2-
] = (K
2
K
w
)/[H
+
]
2
K
2
(4)
[Ca
2+
] = T/[C
2
O
4
2-
] = T[H
+
]
2
/(K
2
K
w
K
2
[H
+
]
2
) (5)
Thay (3), (4), (5) vo (2) v gii phng trnh sinh ra ta c: [H
+
] = 5,5.10
-8
M
[Ca
2+
] = 1,04.10
-4
M
OLYMPIC HA HC QUC T LN TH 37:
Mt hc sinh nghin cu phn ng ha hc gia cc cation A
2+
, B
2+
, C
2+
, D
2+
, E
2+
trong
dung dch nitrat v cc anion X
-
, Y
-
, Z
-
, Cl
-
, OH
-
trong dung dch cha cation natri ng thi c mt
phi t hu c L. Hc sinh ny xc nh c mt s hp cht kt ta v mt s phc cht mu nh
trong Bng 1 di y:
Bng 1

X
-
Y
-
Z
-
Cl
-
OH
-

L
A
2+

***

*** *** *** kt ta
trng
***
B
2+

kt ta
vng
kt ta
trng
*** *** ***
Phc BL
n
2+


C
2+

kt ta
trng
kt ta
nu
kt ta
nu
kt ta
trng
kt ta
en
Cc phc
CL
2+
, CL
2
2+


D
2+

***

kt ta *** *** *** ***
E
2+

***

kt ta kt ta
trng
*** *** ***
*** = khng phn ng,
1 Lp s tch cc cation A
2+
, B
2+
, C
2+
, D
2+
, E
2+
trong dung dch nitrat bng cch s dng cc
dung dch thuc th khc nhau cha cc anion X
-
, Y
-
, Z
-
, Cl
-
, OH
-
. Ghi r sn phm cc sn phm
hnh thnh trong mi bc.
2 Lp s tch cc anion X
-
, Y
-
, Z
-
, Cl
-
, OH
-
trong dung dch cha cation natri bng cch s dng
cc dung dch thuc th khc nhau cha cc cation A
2+
, B
2+
, C
2+
, D
2+
, E
2+
. Ghi r sn phm cc
sn phm hnh thnh trong mi bc.
39
3 Kt ta trng BY
2
v kt ta nu CY
2
tan t trong nc vi tch s tan tng ng ti 25
o
C ln lt
l 3.20 10
-8
v 2.56 10
-13
.
a) Tnh tan ca BY
2
.
b) Tnh tan ca CY
2
.
4 Chun b trong cc bnh nh mc 50 mL mt nhm cc dung dch cha B
2+
v L bng cch thm
vo mi bnh 2 mL dung dch B
2+
8,2 10
-3
M. Thm vo mi bnh cc lng khc nhau ca dung
dch cha phi t L nng 1,0 10
-2
M. Pha long dung dch trong mi bnh bng nc n
vch mc (50 mL). o h s hp th ca phc BL
n
ti 540 nm cho mi dung dch trong mt ng
di 1,0 cm. Cc d liu thu c trong Bng 2. (C B
2+
v phi t L khng hp th (A = 0) ti
540 nm.) [Phng php t l mol]
a) Tnh gi tr n (s phi tr) trong phc BL
n
2+
.
b) Tnh hng s to thnh (K
f
) ca phc BL
n
2+
.
Bng 2
L thm vo
V
L
(mL)
H s hp th
(A)
L thm vo
V
L
(mL)
H s hp th
(A)
1.00 0.14 2.00 0.26
3.00 0.40 4.00 0.48
5.00 0.55 6.00 0.60
7.00 0.64 8.00 0.66
9.00 0.66 10.00 0.66
5 Thm rt chm cht rn NaY (tan) vo mt dung dch cha B
2+
0,10M v C
2+
0,05 M c pha t
cc dung dch mui nitrat tng ng ca chng.
a) Cation no kt ta trc (B
2+
hay C
2+
)? Nng [Y
-
] bng bao nhiu khi ion ny kt ta? (Cho
K
sp
(BY
2
) = 3.20 10
-8
v K
sp
(CY
2
) = 2.56 10
-13
ti 25
o
C.) [Tch bng kt ta]
b) Nng ca ion Y
-
v cation cn li bng bao nhiu khi cation u tin kt ta hon ton (gi
thit rng sau khi kt ta hon ton nng cation u tin trong dung dch s 10
-6
M)? S dng tc
nhn Y
-
c th tch B
2+
v C
2+
bng phng php kt ta hay khng?



BI GII:
1. cch tch:
40

2. Cch tch:

3.a)

4S
1
3
= 3,2.10
-8
S
1
= 2,0.10
-3

b)
41

4S
2
3
= 2,56.10
-13
S
2
= 4,0.10
-5

4) a) th ph thuc gia h s hp th A v th tch V
L
ca cht L c dng nh sau:


T th tch L im gy B (tt c cc ion B
2+
u to phc vi L) trn th th ta c th tnh
n nh sau:
n = s mol L / s mol B
2+
= 5,1.10
-3
.10
-2
/ 2.10
-3
. 8,2.10
-3
= 3
iu c ngha l phc gia B
2+
vi L c dng BL
3
2+

b) * Tnh h s tt mol c:
im gy A = 0,66 = c.1. [BL
3
2+
] c = 2,01.10
3

* Chn mt im bt k trn th, v d:
Ti im P: l im m 2,0mL L c thm vo; A = 0,26


Nh vy:

5 a) Khi bt u hnh thnh kt ta CY
2
th:
42
K
sp
= [C
2+
][Y
-
]
2
= 2,56.10
-13


Tnh tng t cho khi hnh thnh kt ta BY
2
ta c: [Y
-
] = 5,06.10
-4
M
Vy cht CY
2
kt ta trc
b. Cht C
2+
s kt ta hon ton di dng CY
2
khi [C
2+
] = 10
-6
M
Nh vy [C
2+
][Y
-
]
2
= 2,56.10
-3
[Y
-
] lc ny s bng 5,06.10
-4
M
iu ny c ngha l C
2+
s b kt ta hon ton di dng CY
2
khi [Y
-
] = 5,06.10
-4
M
Lc ny th i vi kt ta BY
2
th
[B
2+
][Y
-
]
2
= 2,56.10
-8
< K
sp
(BY
2
) = 3,2.10
-8

Nh vy lc [Y
-
] = 5,06.10
-4
M v [B
2+
] = 0,1M th cht BY
2
vn cha c kt ta
iu ny c ngha l ta hon ton c th tch cc ion B
2+
v C
2+
ra khi dung dch bng phng
php kt ta phn on vi Y
-
l tc nhn.
IV. OLYMPIC HA HC CC NC TRN TH GII:
OLYMPIC HA HC O 1999:
Lng oxi trong mu c xc nh bng php phn tch iot nh sau (phng php Winkler):
Bc 1: Oxi trong dung dch oxi ho Mn
2+
thnh Mn(IV) trong mi trng kim to thnh
MnO(OH)
2
.
Bc 2: Thm axit vo hp cht ca mangan ni trn phn ng vi lng d Mn
2+
to thnh ion
Mn
3+
.
Bc 3: Ion Mn
3+
ny oxi ha thuc th iodua to thnh iot v Mn
3+
b kh thnh Mn
2+
.
Bc 4: Lng iot sinh ra trong bc 3 c chun bng dung dch thiosunfat.
2) Vit phng trnh ion ca 4 phn ng trn.
2) Phn tch nhng mu nc sng Schwechat cho kt qa sau:
Chun ho dung dch natri thiosunfat Na
2
S
2
O
3
: dng KIO
3
trong mi trng axit, khi ion
iodat b kh thnh ion iodua. Vi 25,00mL dung dch KIO
3
(|(KIO
3
) = 174,8mg/L) phi dng ht
12,45mL dung dch Na
2
S
2
O
3
.
Ngay sau khi ly mu nc, lng oxy ca n c xc nh theo phng php Winkler.
phi dng 11,80mL dung dch Na
2
S
2
O
3
trn cho 103,50mL mu nc 20,0
o
C. Nng oxy bo ho
trong nc 20,0
o
C l 9,08mg/L.
Mu th hai (V = 202,20mL, T = 20,0
o
C) c trong 5 ngy nhit 20,0
o
C, ng vi
6,75mL dung dch Na
2
S
2
O
3
.
iii) Vit phng trnh ion ca phn ng chun ho dung dch thiosunfat.
iv) Tnh nng mol/L ca dung dch thiosunfat
v) Tnh hm lng oxy (mg/L) ca mu nc ngay sau khi ly mu.
vi) Tnh ch s bo ho oxy ca mu nc ny.
vii) Tnh hm lng oxy ca mu nc ny sau khi 5 ngy.
viii) T cc kt qa trn c th xc nh c cc thng s c trng no? Gi tr ca n l
bao nhiu?
BI GII:
i. Bc 1: 2Mn
2+
+ O
2
+ 4OH
-
= 2MnO(OH)
2
.
Bc 2: 2MnO(OH)
2
+ 2Mn
2+
+ 8H
+

= 4Mn
3+
+ 6H
2
O
Bc 3: 4Mn
3+
+ 4I
-
= 2I
2
+ 4Mn
2+
.
Bc 4: 2I
2
+ 4S
2
O
3
2-
= 2S
4
O
6
2-
+ 4I
-
.
ii. a) IO
3
-
+ 6S
2
O
3
2-
+ 6H
+
= I
-
+ 3H
2
O + 9S + 3SO
4
2-

b) C(S
2
O
3
2-
) = 9,841.10
-3
M
c) n(O
2
) = 2,903.10
-2
mmol |(O
2
) = 8,976mg/L.
43
d) SSI = 98,9%
e) n(O
2
) = 0,0166mmol |(O
2
) = 5,20mg/L
f) BSB
5
= 3.78mg/L
OLYMPIC HA HC O 2005:
25.0C v p sut ring phn ca CO
2
l: p(CO
2
) = 1.00 bar. 0.8304 lt kh CO
2
ho tan trong
1.00 lt nc.
1. Tnh nng mol ca CO
2
ho tan
2. Tnh hng s Henry ca CO
2
25.0C.
3. Tnh nng mol ca CO
2
ho tan trong nc ma, nu phn th tch ca CO
2
trong kh quyn
c hm lng 380 ppm mi ngy v p sut ca CO
2
c ga tr l 1.00 bar.
Mt phn CO
2
ho

tan s phn ng vi nc to thnh axit cacbonic. Hng s cn bng ca
phn ng ny l K=1.6710
-3
vi nng ca nc c a vo K
a

4. Tnh nng ca axit cacbonic ho tan trong nc ma? Bit nng ca CO
2
l khng i.
i vi hng s phn li th nht th [H
2
CO
3
]* c s dng thay th cho nng ca axit
cacbonic. [H
2
CO
3
]* l tng nng ca axit cacbonic v lng kh CO
2
ho tan trong nc.
Cc ga tr l: K
A1
= 4.45 10
-7
and K
A2
= 4.84 10
-11
.
5. Tnh pH ca nc ma. B qua cn bng t proton phn ca nc v hng s phn li K
A2
ca
axit cacbonic. Bit rng nng ca [H
2
CO
3
]* l khng i trong sut qa trnh.
Vo nm 1960 th phn th tch ca CO
2
trong kh quyn l 320ppm
6. Tnh pH ca nc ma vo thi im ny (tt c cc iu kin khc u nh cu 3.5.).
vi (CaCO
3
) c tch s tan T = 4.7010
-9
.
7. Tnh tan ca vi trong nc tinh khit. Gi thit rng c mui hydrocacbonat v mui
cacbonat u khng phn ng sinh ra axit cacbonic.
Tnh tan ca CaCO
3
trong nc ma vo thi im ny. Nh ni trn [H
2
CO
3
]* lun l
hng s. tr li cu hi ny phi lm nhng vic sau:
8. Hy xc nh nhng ion cha bit nng .
9. Vit cc phng trnh cn thit tnh nng cc ion ny.
10. Xc nh phng trnh cui cng vi [H
3
O
+
] l n s.
Vi nhng phng trnh bc cao th ta kh lng gii c chnh xc. Ta c th gi thit gn ng
rng pH = 8.26 tin tnh ton
11. S dng tt c nhng thng tin trn tnh tan ca vi.
BI GII:
1. Nng ca CO
2
ho tan:
p V = n R.T
mol 0335 . 0
K 15 . 298 08314 . 0
8304 . 0 00 . 1
T R
V p
n =

=
L / mol 0335 . 0
1
0335 . 0
c = =
2. Hng s Henry: c
i
= p
i
K
H

L bar / mol 0335 . 0
1
0335 . 0
K
H
= =
3. C(CO
2
) trong nc ma:
2
CO
c =3.8 10
-4
0.0335 = 1.27 10
-5
mol/L
4. Nng ca axit cacbonic ho tan trong nc ma:
44
CO2 + H2O H2CO3

3
2
3 2
10 67 . 1
] CO [
] CO H [

=
[H2CO3] = 1.6710
-3
[CO2] = 2.1310
-8
mol/L
5. pH ca nc ma vo thi im ny:
[H
2
CO
3
]* = [CO
2
] + [H
2
CO
3
] = 1.28 10
-5
mol/L
H
2
CO
3
+ H
2
O HCO
3
-
+ H
3
O
+

7
3 2
3 3
1 S
10 45 . 4
] CO H [
] O H [ ] HCO [
K

+
=

=
[H
3
O
+
] = [HCO
3
-
] = x
1 S
5
2
K
10 275 . 1
x
=



x = 2.382 10
-6
mol/L
pH = -log x = 5,62
6. Ga tr pH ca nc ma vo nm 1960:
[CO
2
] = 3.2 10
-4
bar 0.0335 mol/bar L = 1.07 10
-5
mol/L
[H
2
CO
3
] = 1.67 10
-3
[CO
2
] = 1.79 10
-8
mol/L
[H
2
CO
3
]* = [CO
2
] + [H
2
CO
3
] = 1.07 10
-5
mol/L
L / mol 10 19 . 2 K * ] CO H [ ] O H [
6
1 S 3 2 3
+
= =
pH = -log [H
3
O
+
] = 5,66

7. tan ca vi trong nc ct:
[Ca
2+
][CO
3
2-
] = K
L
= 4.7 10
-9
[Ca
2+
] =
9
10 7 . 4

= 6.856 10
-5
mol/L
S (CaCO
3
) = 6.86 10
-5
mol/L
8. Cc ion cha xc nh c nng :
[Ca
2+
], [H
3
O
+
], [OH
-
], [CO
3
2-
], [HCO
3
-
]
9. Cc phng trnh cn thit:
(I) [Ca
2+
][CO
3
2-
] = K
L

(II) [H
3
O
+
] [OH
-
] = K
W

(III)
1 S
3 2
3 3
K
* ] CO H [
] O H [ ] HCO [
=

+

(IV)
2 S
3
3
2
3
K
] HCO [
] O H [ ] CO [
=

+

a. 2 [Ca
2+
] + [H
3
O
+
] = [OH
-
] + [HCO
3
-
] + 2 [CO
3
2-
]
10. Nhn c t phng trnh ca H
3
O
+
:
] O H [
* ] CO H [ K
] HCO [
3
3 2 1 S
3
+


=

2
3
3 2 1 S 2 S
3
3 2 S 2
3
] O H [
* ] CO H [ K K
] O H [
] HCO [ K
] CO [
+ +

=
45
* ] CO H [ K K
] O H [ K
] CO [
K
] Ca [
3 2 1 S 2 S
2
3 L
2
3
L 2


= =
+

+

] O H [
K
] OH [
3
W
+

=
Thay vo (V):
2
* ] CO H [ K K
] O H [ K
3 2 1 S 2 S
2
3 L


+
+ [H
3
O
+
] =
] O H [
K
3
W
+
+
] O H [
* ] CO H [ K
3
3 2 1 S
+

+ 2
2
3
3 2 1 S 2 S
] O H [
* ] CO H [ K K
+


Chuyn v:
* ] CO H [ K K
] O H [ K 2
3 2 1 S 2 S
4
3 L


+
+[H
3
O
+
]
3
(K
W
+K
S1
[H
2
CO
3
]*)[H
3
O
+
]2 K
S1
K
S2
[ H
2
CO
3
]* = 0
11. tan ca vi:
S (CaCO
3
) =
4
3 2 1 S 2 S
2
3 L 2
10 17 . 5
* ] CO H [ K K
] O H [ K
] Ca [

+
+
=


= mol/L
OLYMPIC HA HC BUNGARI 1998:
Bc clorua d dng ho tan trong dung dch amoniac trong nc v to ion phc:
AgCl
(r)
+ 2NH
3
[Ag(NH
3
)
2
]
+
+ Cl
-
.
a) Mt lt dung dch amoniac 1M ho tan c bao nhiu gam AgCl? Bit:
AgCl
(r)
Ag
+
+ Cl
-
T = 1,8.10
-10
.
[Ag(NH
3
)
2
]
+
Ag
+
+ 2NH
3
K = 1,7.10
-7
.
b) Xc nh tch s tan T ca AgBr. Bit rng 0,54g AgBr c th tan c trong dung dch amoniac
1M.
BI GII:
a) Ta c:
| || |
| |
| || |
10
7
2 3
2
3
10 . 8 , 1
10 . 7 , 1
) (
+

+
+
= =
= =
Cl Ag T
NH Ag
NH Ag
K

V [Ag
+
] << [Cl
-
]; [Ag(NH
3
)
2
]
+
= [Cl
-
]; [NH
3
] = 1 - 2[Cl
-
]
[Ag
+
] = T/[Cl
-
] nn thay tt c cc ng thc trn vo phng trnh ca K ta tnh c
[Cl
-
] = 0,0305M. m
AgCl
= 4,38g
b) [Br
-
] = 0,33/188 = 1,75.10
-3
M
| |
| |
| |
13
7
2
10 . 3 , 5
10 . 7 , 1
) 2 1 .(

=
=

AgBr
AgBr
T
Br
Br
Br
T

OLYMPIC HA HC BUNGARI 1998:
a) Xc nh nng ion hydro v ga tr pH ca dung dch to thnh khi cho 0,82g CH
3
COONa

vo 1L dung dch CH
3
COOH 0,1M
b) Phi thm vo bao nhiu gam NaOH rn vo dung dch ny lm pH tng mt n v.
c) So vi nng ca phn t CH
3
COOH trong dung dch CH
3
COOH 0,1M th nng phn t
CH
3
COOH trong cc dung dch th nht v th hai thay i theo nhng t s no? (C th
tnh gn ng). Bit K
a
(CH
3
COOH) = 1,8.10
-5

46
BI GII:
CH
3
COOH CH
3
COO
-
+ H
+


| || |
| |
5
3
3
10 . 8 , 1 = =
+
COOH CH
H COO CH
K
a

CH
3
COONa = CH
3
COO
-
+ Na
+

CH
3
COOH + NaOH = CH
3
COONa + H
2
O
i vi dung dch axit axetic (tinh khit) ban u:
[CH
3
COO
-
] = [H
+
]; [CH
3
COOH]
1
= C
axit
~ 0,1M
[H
+
] = (0,1K
a
)
1/2
= 1,34.10
-3
M
a) Hn hp axit yu v mui ca n l dung dch m nn:
| |
| |
74 , 3 = + =

OAc
HOAc
pK pH
a

b) Khi thm baz mnh nng C
b
th C
mui
= C
mui
+ C
b
; C
axit
= C
axit
- C
b

pH tng mt n v tng ng vi [H
+
] gim 10 ln:
[H
+
]
2
/[H
+
]
3
= [C
axit
.(C
mui
+ C
b
)]/[C
mui
.(C
axit
C
b
)]
[H
+
]
3
= 1,8.10
-5
M; C
b
= 0,045M
m
NaOH
= 1,8g
c) [CH
3
COOH]
1
= ([H
+
]
1
)
2
/K
a
~ 0,1M
[CH
3
COOH]
2
= [H
+
].C
mui
/K
a
~ 0,1M hoc chnh xc hn
[CH
3
COOH]
2
= C
axit
- [H
+
]
2
= 0,0986M
[CH
3
COOH]
3
= [H
+
].(C
mui
+ C
b
)/K
a
= 0,055M
[CH
3
COOH]
2
/[CH
3
COOH]
1
~ 1
[CH
3
COOH]
3
/[CH
3
COOH]
1
~ 0,55
OLYMPIC HA HC ITALY 1999:
Phi iu ch mt dung dch m (pH = pK
a
) t mt dung dch axit n chc. Phi thm vo dung
dch ny mt lng cht theo s mol l:
a) Bng (s mol ca baz lin hp)
b) Gp i (s mol ca baz lin hp)
c) Khng (s mol ca baz lin hp).
d) Bng (s mol ca baz mnh)
BI GII: Cu a.
OLYMPIC HA HC ITALY 1999:
Trong phn ng cn bng:
HCN + H
2
O = H
3
O
+
+ CN
-

Nhng phn t no l axit theo nh ngha ca Bronsted v Lowry:
a) HCN; CN
-

b) H
2
O; H
3
O
+

c) HCN; H
2
O
d) HCN; H
3
O
+

BI GII: Cu d
OLYMPIC HA HC ITALY 1999:
iu ch dung dch H
2
SO
4
0,12M bng cch pha long H
2
SO
4
c (95%. d = 1,84g/mL), c
th pha long vi nc.
a) 5,00mL axit thnh 500mL.
b) 11,00mL axit thnh 1000mL.
47
c) 15,00mL axit thnh 2000mL.
d) 7,00mL axit thnh 1000mL.
BI GII: Cu d
OLYMPIC HA HC ITALY 1999:
Trong phn ng:
NH
3
+ HCl = NH
4
+
+ Cl
-

th NH
3
l:
a) Axit Arrhenius.
b) Baz Bronsted.
c) Baz Arrhenius.
d) Cht trung tnh.
BI GII: Cu d
OLYMPIC HA HC ITALY 1999:
Nng ion Na
+
trong dung dch do 19,0g Na
2
CO
3
tan trong nc to thnh 870mL dung dch
l:
a) 0,206M
b) 0,312M
c) 0,412M
d) 0,103M
BI GII: Cu c
OLYMPIC HA HC ITALY 1999:
Baz lin hp ca NH
3
khi phn ng vi axit l:
a) NH
3
-
.
b) NH
2
-
.
c) NH
4
+
.
d) NH
3
+
.
BI GII: Cu b
OLYMPIC HA HC ITALY 1999:
Trong s cc axit sau y, cht no to c baz lin hp mjanh nht khi n phn ng nh mt
axit?
a) H
2
SO
4

b) H
3
PO
4.

c) H
2
O
d) CH
3
COOH
BI GII: Cu c
OLYMPIC HA HC ITALY 1999:
Nu trn hai dung dch (trong nc) m mt cha NH
3
(20mL; 0,5M) cn dung dch kia cha
HCl (20mL; 0,5M) th pH ca dung dch to thnh s l:
a) 7
b) 1
c) 10
d) 5
BI GII: Cu d
OLYMPIC HA HC ITALY 1999:
Cht in ly lng tnh l nhng cht m trong dung dch:
a) C th phn ng nh cht oxy ho hoc cht kh.
48
b) C th phn ng nh axit hoc baz.
c) C th phn ng theo kiu ng ly v d ly.
d) Th hin l mt phn t c mt phn a nc v mt phn k nc.
BI GII: Cu b
OLYMPIC HA HC ITALY 1999:
Trong chc dung dch HCl sau y dung dch no c hn?
a) HCl 10
-2
M.
b) HCl 3,6%
c) HCl 10
-2
m
d) HCl 3,7% m/V
BI GII: Cu b
OLYMPIC HA HC ITALY 1999:
Lng H
2
SO
4
trong mt dung dch nc (2000mL; 27,27%; d = 1,20g.cm
-3
) l:
a) 6,00 mol
b) 4,82 mol
c) 6,79 mol
d) 5,20 mol
BI GII: Cu c
OLYMPIC HA HC ITALY 1999:
chun CH
3
COOH bng NaOH th trong cc cht ch th sau y th cht no tt nht?
a) Metyl da cam pKa = 3,7
b) Metyl pKa = 5,1
c) Bromthymol xanh pKa = 7,0
d) Phenolphtalein pKa = 9,4
BI GII: Cu d
OLYMPIC HA HC ITALY 1999:
Trong s cc mui sau y th mui no l axit Bronsted?
a) NaHSO
4
.
b) Na
3
PO
4
.
c) NaCN.
d) Na
2
S.
BI GII: Cu a
OLYMPIC HA HC ITALY 1999:
Cht phi thm vo dung dch nc lm thay i pH t 12 thnh 10 l:
a) Nc ct.
b) Natri hydroxit.
c) Hidro clorua.
d) Natri axetat.
BI GII: Cu c
OLYMPIC HA HC C 1999 (Vng 3):
Ngi ta c th xc nh amoniac bng phng php quang k t phn ng vi phenol vi s c
mt ca hipoclorit.
49
OH
+ NH
3
N O O

Xanh lam:
max
= 625nm
Trong 7,56mg mt mu th mioglobin ca b c, ngi ta chuyn ha nit c trong thnh
amoniac, sau mu th c pha long thnh 10,0mL. Sau ngi ta cho 10,0mL dung dch vo mt
bnh nh mc 500mL, cho thm vo 5mL dung dch phenol v 2mL dung dch hipoclorit , ri pha thnh
50,0mL dung dch c ng yn 30 pht. Sau ngi ta o tt ti 625nm trong cuvet 1,00cm.
Bn cnh , ngi ta pha ch mt dung dch chun gm 0,0154g NH
4
Cl trong 1L nc. Ngi
ta cho 5,00mL dung dch vo mt bnh nh mc 50,0mL v sau vic phn tch c tin hnh
nh m t trn.
Ngoi ra ngi ta cn o mt mu khng (mu m) vi nc nguyn cht trong ng cuvet:
Mu tt ti 625nm
Khng 0,132
i chng 0,278
Cha bit 0,711
a) Hy tnh h s tt mol (mt quang mol ca sn phm mu xanh).
b) Hy tnh phn khi lng (bng phn trm) ca nit trong mioglobin.
BI GII:
a) i vi mu th i chng th trong tng s tt c 0,132 c quy nh cho nc nguyn
cht, phn cn li 0,278 0,132 = 0,146 l do hp cht ca nit gy ra.
Ta bit A = c.l.C vi l = 1,00cm
Tnh C trong mu i chng:
n(NH
4
Cl) trong 5,0mL = (0,0154/53,50).0,005 = 1,439.10
-6
M.
Khi pha ln 50mL ta c dung dch c nng C = 2,88.10
-5
M.
0,146 = c.1,00.2,88.10
-5
c = 5072L/cm.
b) Vi c ngi ta c th tnh c nng trong dung dch cha bit. C y cng phi ch
n mu khng.
OLYMPIC HA HC C 1999 (Vng 3):
C mt s thuyt v nh ngha khc nhau v axit v baz. Mt trong s cc nh ngha c
lin quan n s t phn li ca dung mi:
2HB H
2
B
+
+ B
-
.
Theo l thuyt ny th cht no lm tng phn cation ca dung mi (H
2
B) l mt axit v cht no
lm gim phn (hoc tng phn anion) l mt baz.
Chng hn nc t phn ly: 2H
2
O H
3
O
+
+ OH
-

Axit l nhng cht no lm tng [H
3
O
+
] v baz l nhng cht no lm tng [OH
-
]
Trong etanol th: 2C
2
H
5
OH C
2
H
5
OH
2
+
+ C
2
H
5
O
-

Axit l nhng cht no lm tng nng [C
2
H
5
OH
2
+
] v baz l nhng cht no lm
tng[C
2
H
5
O
-
]
50
Khi phn ng trung ho l phn ng trong mt axit phn ng vi mt baz to thnh mt
mui v mt dung mi.
Theo l thuyt ny th pH = -lg[H
2
B
+
] (L thuyt ny cng c th p dng c cho cc dung
mi phi proton).
a) Hy n c mt v d v mt axit v mt baz trong dung mi amoniac lng.
b) Tch s ion ca amoniac l 1,0.10
-29
(mol/L)
2
. Hi amoniac lng nguyn cht c pH no?
c) Nc l mt axit hay l baz trong amoniac lng?. Gii thch.
d) Hy l gii ti sao CH
3
COOH l mt axit tng amoniac lng. N mnh hn hay yu hn tng
dung dch nc.
e) Mt hp cht l mt axit mnh trong nc c th l mt baz yu trong amoniac lng hay
khng? Nu c th hy cho v d cn nu khng th hy gii thch.
f) Hy ch ra rng NaOH l mt mui trong NH
3
lng. Hy ch v d v mt phn ng m n
c to ra trong mi trng amoniac lng.
g) C hp cht no l mt baz trong nc m li l mt axit trong NH
3
lng khng? Nu c th
hy cho v d cn nu khng th hy gii thch.
h) Hy t b NH
3
. Liu c mt dung mi no m n l mt baz khng?. Nu c th hy cho v
d cn nu khng th hy gii thch.
i) Trong CCl
4
c axit hay baz khng? Nu c th hy cho v d cn nu khng th hy gii thch.
Lu : Tt c cc khi nim dng trong bi tp u lin h vi l thuyt v cc h dung mi
c gii thch trn.
BI GII:
a) Trong amoniac lng din ra qa trnh t phn ly nh sau:
2NH
3
NH
4
+
+ NH
2
-
.
Nh vy axit l cc cht lm tng nng NH
4
+
cn baz l cc cht lm tng nng NH
2
-
.
V d v mt axit: NH
4
Cl
V d v mt baz: KNH
2
.
b) Theo nh ngha u bi th pH = -lg[NH
4
+
]
Ta bit: K
amoniac
= [NH
4
+
][NH
2
-
] = 1,0.10
-29
[NH
4
+
] = 1,0.10
-14,5
pH = 14,5
c) Nc phn ng nh l mt axit v n lm tng nng NH
4
+
:
H
2
O + NH
3
NH
4
+
+ OH
-
.
d) CH
3
COOH + NH
3
NH
4
+
+ CH
3
COO
-

Axit axetic lm tng nng NH
4
+
nn n l mt axit
V rng NH
3
l cht cho cp in t mnh hn nc cho nn s ho tan axit axetic tng amoniac
th ln hn trong nc v nh vy th tnh axit mnh hn.
e) NH
3
l phn t cho cp in t mjanh hn H
2
O (NH
4
+
hnh thnh d hn H
3
O
+
). Nh vy th s
ho tan mi axit trong amoniac u mnh hn nc. V vy mt axit trong h nc khng th l
mt baz trong h amoniac.
f) Ch cn chng minh rng NaOH c hnh thnh trong mt phn ng trung ho l :
NaNH
2
+ H
2
O NH
3
+ NaOH
(axit + baz = dung mi + mui)
g) Mt hp cht nh vy cn phi to thnh OH
-
trong nc v NH
4
+
trong amoniac. C th
l mt hp cht c hai chc nng, vi mt chc nng baz yu hn amoniac trong nc v mt
nhm axit lin hp vi chc nng baz trong dung dch nc. Mt v d y l hydroxilamin
NH
2
OH trong nc s hnh thnh cn bng:
51
H
2
O + H
2
NOH H
3
NOH
+
+ OH
-
.
trong amoniac th cn bng chim u th l:
H
2
NOH + NH
3
NH
4
+
+ H
2
NO
-
.
(Gii thch b sung nhng trong phn bi tp khng yu cu: Cht cha bit cn cha t nht l
mt H c kh nng tch ra thnh proton, tc l nn vit tt H
n
X)
trong nc th H
n
X tc dng nh l mt baz:
H
n
X + H
2
O H
n+1
X
+
+ OH
-
(a)
V trong amoniac nh l mt axit:
H
n
X + NH
3
NH
4
+
+ H
n-1
X
-
. (b)
cho (b) xy ra th nhm tc ng nh l baz trong nc phi l tc nhn nhn proton km
hn NH
3
. iu c ngha l nhm phi l mt baz yu hn NH
3
. Qa thc pK
b
(NH
3
) = 4,75 v
pK
b
(H
2
NOH) = 8,2.
cho (a) xy ra th nhm tc ng nh l axit trong NH
3
phi c tc dng cho proton yu hn
axit H
n+1
X
+
, H
n+1
X
+
l axit lin hp ca nhm H
n
X, nhm ny tc dng nh l mt baz. Qa thc
pK
a
(NH
3
+
OH) = 5,4 v pK
a
(NH
2
OH) = 13,2.
h) C. V d nh axit sunfuric:
2H
2
SO
4
H
3
SO
4
+
+ HSO
4
-

H
2
O + H
2
SO
4
H
3
O
+
+ HSO
4
-
.
i) Khng, do CCl
4
khng phn li.
OLYMPIC HA HC C 1999 (Vng 4):
Mt dung dch ceri (IV) sunfat cn c chun ha, Cho cc dung dch v cc cht sau y:
Natri oxalat rn, dung dch kali pemanganat v dung dch st (II) sunfat, c hai u khng bit
nng .
Ngi ta tin hnh ba ln chun trong dung dch axit (mi ln u i vi mt lng d axit
sunfuric) v thu c nhng kt qa sau y:
+ 0,2228g natri oxalat dng ht 28,74cm
3
dung dch kali pemanganat.
+ 25,00cm
3
dung dch st (II) sunfat dng ht 24,03cm
3
dung dch kali pemanganat.
+ 25,00cm
3
dung dch st (II) sunfat dng ht 22,17cm
3
dung dch ceri (IV) sunfat.
1. Vit cc phng trnh phn ng ca ba ln chun .
2. Hy tnh nng ca dung dch ceri (IV) sunfat.
Ngi ta p dng cc th in cc tiu chun sau y:
Fe
3+
+ e = Fe
2+
E
o
= 0,77V
Ce
4+
+ e = Ce
3+
E
o
= 1,61V
3. Hy tnh K
C
ca phn ng: Fe
2+
+ Ce
4+
= Fe
3+
+ Ce
3+
.
(i vi phn cn li ca bi tp cn gi thit cc iu kin l tiu chun)
4. Hy tnh t s:
| |
| |
+
+
2
3
Fe
Fe
ti im tng ng.
5. Hy tnh th ca dung dch ti im tng ng.
Nu nh ngi ta s dng mt cht ch th oxi ha - kh (In) vi E
o
= th ca dung dch ti im
tng ng nhn bit im kt thc ca vic chun th s khng c vn g v chnh xc
ca vic nhn bit im kt thc.
Nhng i vi cht ch th sau y th:
In
Ox
+ 2e = In
2-
kh
E
o
= 0,80V
52
S chuyn mu s th hin r khi:
| |
| | 1
10
2
=

kh
Ox
In
In

6. Hy tnh
| |
| |
+
+
2
3
Fe
Fe
ti im chuyn mu ca cht ch th ny v cho bit sai s phn trm trong
ln chun tin hnh.
BI GII:
1. 2MnO
4
-
+ 5C
2
O
4
2-
+ 16H
3
O
+
= 2Mn
2+
+ 10CO
2
+ 24H
2
O
5Fe
2+
+ MnO
4
-
+ 8H
3
O
+
= 5Fe
3+
+ Mn
2+
+ 12H
2
O
Fe
2+
+ Ce
4+
= Fe
3+
+ Ce
3+
.
2. Chun 1: 0,2228g Na
2
C
2
O
4
tng ng 1,66.10
-3
mol C
2
O
4
2-
.
(2/5).1,66.10
-3
= [MnO
4
-
].V(MnO
4
-
)
[MnO
4
-
] = 0,0023M
Chun 2: [MnO
4
-
].V(MnO
4
-
) = (1/5)[Fe
2+
]V(Fe
2+
)
[Fe
2+
] = 0,111M
Chun 3: [Ce
4+
] = [Fe
2+
].V(Fe
2+
)/V(Ce
4+
) = 0,125M
3. Ta c:

14
o
/ Fe /
10 . 61 , 1
). (
lg
2 3 3 4

=
+ + + +
K
RT
F E E
K
Fe
o
Ce Ce

4. Ti im tng ng th lng cht cho vo n(Ce
4+
) = n
o
(Fe
2+
). Vi mi ion Ce
3+
mi hnh
thnh th cng hnh thnh mt ion Fe
3+
, tc l [Ce
3+
] = [Fe
3+
] v c [Ce
4+
] = [Fe
3+
]
Ta c:
| || |
| || |
| |
| |
| |
| |
7
2
3
2
2
2
3
2 4
3 3
10 . 27 , 1 ; = = =
+
+
+
+
+ +
+ +
Fe
Fe
Fe
Fe
K
Fe Ce
Fe Ce
K
C C

5. a ga tr mi tm c vo phng trnh Nernst i vi th ca st ngi ta thu c: E =
1,19V
(Cng tng t nh vy ngi ta c th a ga tr [Ce
4+
]/[Ce
3+
] = (1,27.10
-7
)
-1
vo phng trnh
Nernst i vi th ca ceri).
6. Th ca dung dch ti im chuyn mu l:
E = 0,80 + RT/2F(ln10) = 0,83V
a ga tr ny vo phng trnh Nernst i vi st:
| |
| |
| |
| | 1
2 , 10
ln 77 , 0 83 , 0
2
3
2
3
= + =
+
+
+
+
Fe
Fe
Fe
Fe
F
RT

Nh vy sai s s l: (11,2)
-1
.100% = 8,95%
OLYMPIC HA HC C 2000:
HCN l mt axit yu (K
a
= 6,2.10
-10
). NH
3
l mt baz yu (K
b
= 1,8.10
-5
). Mt dung dch
NH
4
CN 1,0M s c tnh cht:
a) Axit mnh.
b) Axit yu.
c) Trung tnh.
d) Baz yu.
e) Baz mnh.
BI GII: Cu d
OLYMPIC HA HC C 2000:
53
20,00mL mu dung dch Ba(OH)
2
c

chun bng 0,245M. Nu s dng 27,15mL HCl th
nng mol ca Ba(OH)
2
lc ny s l bao nhiu?
a) 0,166M
b) 0,180M
c) 0,333M
d) 0,666M
e) 1,136M
BI GII: Cu a
OLYMPIC HA HC C 2000:
Tch s ion ca nc 45
o
C l 4,0.10
-14
. Vy pH ca nc tinh khit thi im ny l bao
nhiu?
a) 6,7
b) 7,0
c) 7,3
d) 8,5
e) 13,4
BI GII: Cu a
OLYMPIC HA HC C 2000:
Tch s tan ca mt s mui sunfat c cho bng sau:
Mui T
1 CaSO
4
9.10
-6

2 SrSO
4
3.10
-7

3 PbSO
4
2.10
-8

4 BaSO
4
1.10
-10

Khi cho dung dch Na
2
SO
4
0,0001M vo dung dch cc mui tan ca cc cation trn th mui no
s kt ta.
a) 1, 2 v 3.
b) 1 v 2
c) 1 v 3
d) 2 v 4
e) ch 4
BI GII: Cu e
OLYMPIC HA HC C 2000:
Khi trn dung dch NaOH 0,5M vi mt lng bng nhau ca dung dch no sau y th s xy
ra s gim pH.
1) H
2
O.
2) 0,25M Na
2
CO
3
.
3) 0,5M HCl.
4) 0,6M KOH
a) 1, 2 v 3.
b) 1 v 2
c) 1 v 3
d) 2 v 4
e) ch 4
BI GII: Cu e
OLYMPIC HA HC C 2001:
54
Dung dch KOH 0,025M c pH bng bao nhiu?
a) 1,60
b) 3,69
c) 7,00
d) 10,31
e) 12,40
BI GII: Cu e
OLYMPIC HA HC C 2001:
Cht no l axit lin hp ca HPO
4
2-
?
a) H
3
PO
4(aq)
.
b) H
2
PO
4
-
(aq)
.
c) H
3
O
+
(aq)

d) H
+
(aq)
.
e) PO
4
3-
(aq)

BI GII: Cu b
OLYMPIC HA HC C 2001:
Dung dch axit yu HA 0,075M c [H
+
] bng bao nhiu nu K
a
(HA) = 4,8.10
-8

a) 6,1.10
-4
M
b) 2,2.10
-4
M
c) 6,0.10
-5
M
d) 4,8.10
-8
M
e) 3,1.10
-9
M
BI GII: Cu c
OLYMPIC HA HC C 2001:
Nu trn cng mt lng th tch ca BaCl
2
v NaF th nng no ca mi cht th kt ta
c hnh thnh?. Bit T(BaF
2
) = 1,7.10
-7
.
a) 0,020M BaCl
2
v 0,0020M NaF.
b) 0,015M BaCl
2
v 0,010M NaF.
c) 0,010M BaCl
2
v 0,015M NaF.
d) 0,0040M BaCl
2
v 0,020M NaF.
e) Tt c u khng th to kt ta.
BI GII: Cu a
OLYMPIC HA HC C 2002:
Nu trn cng mt lng th tch ca cc cht sau th hn hp no s hnh thnh dung dch m?
1) 0,1M HCl v 0,1M NH
3
.
2) 0,1M HNO
2
v 0,05M NaOH.
3) 0,05M HNO
2
v 0,05M NH
3
.
a) 1
b) 2
c) 3
d) 1 v 3
e) 2 v 3
BI GII: Cu e
OLYMPIC HA HC C 2002:
55
S mol KOH trong 500mL dung dch c xc nh bng cch chun 10,00mL dung dch
KOH ny vi dung dch HCl 0,115M . Nu s chun trn cn 18,72mL HCl th s mol KOH trong
500mL dung dch u s l bao nhiu?
a) 0,00215 mol.
b) 0,00430 mol.
c) 0,108 mol
d) 0,215 mol
e) 0,115 mol
BI GII: Cu c
OLYMPIC HA HC C 2002:
tan ca bc sunfat l 1,5.10
-5
mol
-3
.L
-3
. Trong mt dung dch m nng ion SO
4
2-
l 2,4.10
-
2
M th nng Ag
+
cc i s l:
a) 0,025M
b) 6,25.10
-4
M
c) 3,125.10
-4
M
d) 2,5.10
-4
M
e) 6,25.10
-2
M
BI GII: Cu a
OLYMPIC HA HC C 2003:
Tch s tan ca Ag
2
CrO
4(r)
25
o
C l 2,6.10
-12
. Vy tan ca Ag
2
CrO
4
trong 1L nc l bao
nhiu?
a) 1,6.10
-6
M
b) 2,6.10
-12
M
c) 2,1.10
-8
M
d) 1,4.10
-4
M
e) 8,7.10
-5
M
BI GII: Cu e
OLYMPIC HA HC C 2003:
Mt axit mnh hai nc H
2
A ho tan trong nc 25
o
C cho mt dung dch c pH = 1,85. Nng
ca axit trong dung dch (gi s n phn li hon ton thnh A
2-
) lc ban u s nm trong khong:
a) 0,05 v 0,1
b) 0,01 v 0,05
c) 0,1 v 0,5
d) 0,001 v 0,005
e) 0,005 v 0,01
BI GII: Cu e
OLYMPIC HA HC C 2003:
Mt dung dch axit axetic 0,100M c chun bng dung dch NaOH 0,05M. Khi 60% axit
c trung ho th pH ca dung dch lc ny l bao nhiu?
a) 2,38
b) 4,56
c) 4,74
d) 4,92
e) 7,00
BI GII: Cu d
OLYMPIC HA HC C 2003:
56
a) Tnh pH cui c cc h sau y khi ho tan:
i) 2,00M HCl
ii) 0,500M NaOH
vo 500,0mL nc 25
o
C (pH ca nc iu kin ny l 7,00)
b) Mt lnh vc quan trng trong ho hc phn tch l dung dch m. N bao gm mt hn hp
ca mt axit yu (HA) v baz lin hp ca n (A
-
). N c gi l dung dch m v n chng
li s thay i pH khi thm vo h mt axit mnh hay baz mnh.
S dng cc phng trnh ha hc (v ch ra trng thi ca mi hp phn), hy cho bit chuyn
g s xy ra khi thm vo dung dch m
i) Kh HCl.
ii) NaOH vin
pH ca dung dch m c xc nh bi t l mol ca axit yu v baz lin hp ca n. Nu
hng s phn ly axit K
a
c bit th pH ca dung dch m s c tnh theo phng trnh Henderson
HasselBatch:
pH = pK
a
+ lg([A
-
]/[HA])
c) Hy chng minh phng trnh Henderson HasselBatch t biu thc ca K
a
.
d) 1,00L ca mt dung dch m cha 0,500mol ca axit yu v baz lin hp ca n. pH ca dung
dch o c l 7,00. Xc nh pK
a
ca cp axit baz lin hp.
e) Tnh pH ca dung dch sinh ra khi thm vo 500,0mL dung dch m cu d:
i) 2,00M HCl
ii) 0,500M NaOH
f) K
a
ca axit axetic l 1,75.10
-5
M
1,00L dung dch m cha axit axetic v ion axetat c pH c xc nh l 5,30. Tng nng
ca axit axetic v ion axetat l 1,00M.
i) Tnh t l [A
-
]/[HA]
ii) Tnh nng ca tmh tiu phn trong dung dch m.
Ngoi vic trn mt axit yu v baz lin hp ca n to thnh dung dch m th ta cn c
th s dng mt phng php khc l: chun b sn mt trong hai cht trn ri thm vo dung dch
chun b sn mt lng axit hoc baz mnh.
g) Gii thch?
h) Nh ha hc tp s Bob nh chun b mt dung dch m c pH bng 4,00 bng cch s dng
dung dch CH
3
COONa 0,500M v dung dch HCl 2,00M. Gi s th tch ca HCl thm vo l V
lt. Tr li cc cu hi sau:
i) Th tch dung dch CH
3
COONa 0,500M cn thm vo l bao nhiu hnh thnh dung dch
m?
ii) C bao nhiu mol axit axetic sinh ra?
iii) C bao nhiu mol ion axetat phn ng vi HCl?
iv) Vi pH xc nh th t l [A
-
]/[HA] s l bao nhiu?
v) Tnh V
i) pH m l tng l pH m ti dung dch m c kh nng chng li s thay i pH tt nht
khi thm vo mt lng dung dch axit mnh hay baz mnh. i vi dung dch m axetat
th pH m l tng l bao nhiu?
j) Khng thnh cng vi th nghim trn ca mnh. Bob tip tc tin hnh mt th nghim khc. Bt
u vi 250mL ca dung dch m axetat pH m l tng. Nhng do s bt cn khi lm th
nghim th anh ta cho vo dung dch m mt vi git dung dch NaOH 0,340M. Anh y
57
nhanh chng khc phc s c v o li pH ca dung dch th thy pH tng ln 1 n v so vi lc
u. Bit tng nng cc tiu phn trong dung dch m ban u l 0,500M
i) Tnh t l [A
-
]/[HA] trong dung dch mi
ii) Tnh s mol axit axetic v ion axetat trong dung dch ban u
iii) Sau khi thm NaOH vo th s mol ca axit axetic v anion axetat s l bao nhiu?
iv) Sau khi xy ra s c th s mol ion axetat s tng ln bao nhiu?
v) Th tch NaOH m Bob thm vo dung dch m s l bao nhiu?
BI GII:
a) (i) pH = 1,70
(ii) pH = 11,69
b) HCl
(k)
+ A
-
(aq)
HA
(aq)
+ Cl
-
(aq)

NaOH
(r)
+ HA
(aq)
Na
+
(aq)
+ A
-
(aq)
+ H
2
O
(l)

c) Ta c:
| || |
| |
| |
| |
| |
| |
| |
| |
| |
| |
|
|
.
|

\
|
+ =
=
)
`

|
|
.
|

\
|

=
|
|
.
|

\
|
=

+
HA
A
pK pH
H
A
HA
K
H
A
HA
K
HA
A H
K
a
a
a
a
lg
lg lg

d) pH = 7,00
e) (i) n(H
+
thm vo) = 0,01mol
[A
-
] = 0,499M
[HA] = 0,501M
pH = 6,98
(ii) Tng t nh (i) ta tnh c pH = 7,0043
f) (i)
| |
| |
492 , 3 =

HA
A
(1)
(ii) [A
+
] + [HA] = 1 (2)
Gii h phng trnh (1) v (2) ta thu c kt qa: [HA] = 0,223M v [A
-
] = 0,777M
g) Axit mnh/ baz mnh s phn ng vi baz yu hay axit yu to ra hp phn cn li ca
dung dch m. Nh vy th dung dch thu c s cha axit yu v baz lin hp ca n.
h) (i). Gi th tch HCl l V mL
Vy th tch ca dung dch natri axetat s l 1 V(mL)
(ii) S mol axit axetic l 2,00.V (mol)
(iii) S mol baz sinh ra = 0,500 2.500V (mol)
(iv)
| |
| |
175 , 0 =

HA
A

(v) V = 175mL
Nh vy cn phi trn 825mL dung dch natri axetat 0,500M vi 175mL dung dch HCl 2,00M
i) pH = pK
a
= 4,76
58
j) (i) Ta c: pH = 4,76 + 1 = 5,76
| |
| |
| |
| |
10
lg 76 , 4 76 , 5
=
+ =

HA
A
HA
A

(ii) Trong dung dch m l tng [HA] = [A
-
] = 0,0625mol
(iii) Tng s mol axit axetic v axetat c bo ton = 0,0625.2 = 0,125mol
Ta c: [A
-
] = 10[HA]
[A
-
] = 0,114mol
[HA] = 0,0114mol
(iv) n(NaOH) thm vo = 0,0515 mol
(v) V(NaOH) thm vo = 0,152L = 152mL
OLYMPIC HA HC C 2004:
Ch th quinain l mt cht ch th axit baz rt hu ch. N c mu trong dung dch c
pH ln hn 3,5 nhng khng c mu pH nh hn 1,5. Dung dch no sau y s lm cht ch th ha
nu ta nh mt vi git quinain vo cc dung dch:
1) HCl 0,1M
2) NH
3
0,05M
3) CH
3
COOH 0,0005M
a) 1 v 2
b) 1 v 3
c) 2 v 3
d) ch 2
e) ch 3
BI GII: Cu c
OLYMPIC HA HC C 2004:
Bob ho tan 4,021g NaOH trong nc v pha long bng nc n th tch 1L. Sau anh ta s
dng pipet ly 10,00mL dung dch thu c cho vo bnh nn v cho dung dch HCl 0,050M vo
buret, im cui ngi ta xc nh c th tch HCl cn dng l 20,32mL. Thy gio ca Bob
nhn xt:
a) Php phn tch trn khng chnh xc.
b) NaOH hp th hi nc ngoi khng kh cho nn khi lng ca n c o khng chnh
xc.
c) Buret c trng bng nc thay cho HCl.
d) Bnh nn c trng bng HCl thay cho nc.
e) Pipet c trng bng nc thay cho NaOH
BI GII: Cu c

You might also like