THI KIM TRA GIA K

MN HA PHN TCH
LP HA 2010
THI GIAN 60 PHT KHNG K 5 PHT C
1. Cn bng ion: 7.0 im
a. Hy vit cc phng trnh biu din phn ng trao i proton trong dung dch nc ca cc cht
sau (1.0 im)
i. Potassium hydroxide: KOH K
+
+ OH
-

ii. Acid formic: HCOOH H
+
+ HCOO
-

iii. Potassium hydrogen phthalate: KOOC-C
6
H
4
-COOH K
+
+
-
OOC-C
6
H
4
-COOH

-
OOC-C
6
H
4
-COOH H
+
+
-
OOC-C
6
H
4
-COO
-

K
a2
-
OOC-C
6
H
4
-COOH + H
2
O OH
-
+ HOOC-C
6
H
4
-COOH K
b2

iv. Potassium dihydrogen phosphate: KH
2
PO
4
K
+
+ H
2
PO
4
-

H
2
PO
4
-
H
+
+ HPO
4
2-
K
a2
HPO
4
2-
H
+
+ PO
4
3-
K
a3
H
2
PO
4
-
+ H
2
O OH
-
+ H
3
PO
4
K
b3

b. Gi s phc gia ion Cu
2+
v NH
3
c s phi tr cc i l 4. Hng s phn ly tng nc ca phc
ln lt l K
1
= 10
-2.11
; K
2
= 10
-2.87
; K
3
= 10
-3.48
v K
4
= 10
-4.11
. (1 im)
i. Hy vit cc cn bng phn ly ca cc phc Cu(NH
3
)
i
.
Cu(NH
3
)
4
2+
Cu(NH
3
)
3
2+
+ NH
3

( ) | || |
( ) | |
4
2
4 3
3
2
3 3
1
1
|
= =
+
+
NH Cu
NH NH Cu
K
Cu(NH
3
)
3
2+
Cu(NH
3
)
2
2+
+ NH
3

( ) | || |
( ) | |
3
2
3 3
3
2
2 3
2
1
|
= =
+
+
NH Cu
NH NH Cu
K
Cu(NH
3
)
2
2+
Cu(NH
3
)
2+
+ NH
3

( ) | || |
( ) | |
2
2
2 3
3
2
3
3
1
|
= =
+
+
NH Cu
NH NH Cu
K
Cu(NH
3
)
2+
Cu
2+
+ NH
3

| || |
( ) | |
1
2
3
3
2
4
1
|
= =
+
+
NH Cu
NH Cu
K


ii. Hy tnh hng s bn
1-i
ca cc phc Cu(NH
3
)
i
.
- Phc Cu(NH
3
)
2+
c
11 . 4
4
1
10
1
= =
K
|
- Phc Cu(NH
3
)
2
2+
c
59 . 7
3 4
2 1 2 1
10
1
* = = =

K K
| | |
- Phc Cu(NH
3
)
3
2+
c
46 . 10
2 3 4
3 2 1 3 1
10
1
* * = = =

K K K
| | | |
- Phc Cu(NH
3
)
3
2+
c
57 . 12
1 2 3 4
4 3 2 1 4 1
10
1
* * * = = =

K K K K
| | | | |

c. Hy tnh pH trong cc trng hp sau (2.0 im)
i. HCl 0.001 M: HCl H
+
+ Cl
-
.
C
a
>> 10
-6
M [H
+
] = C
a
pH =-lg[H
+
] = 3
ii. KCN 0.01 M, cho 4 . 9 =
HCN
a
pK : KCN K
+
+ CN
-

CN
-
+ H
2
O HCN + OH
-
pK
b
= 14 pK
a
= 4.6
H
2
O H
+
+ OH
-
pK
w
= 14
Xem CN
-
nh n baz | |
| | | |
| | | |
+
+

+
=
H OH
H OH C
K OH
b
b

- | | | |
7 . 10 3 . 3 2 6 . 4
10 10 10 * 10
+
= >> = = =
g b b g
H C K OH b qua phn ly ca nc.
[OH
-
]
g
> C
b
/100 = 10
-4
phn CN
-
phn ng vi nc l ng k so vi C
b
.
| |
| |
| |

=
OH
OH C
K OH
b
b
; gii phng trnh bc 2 pH = 10.53
iii. NaHCO
3
0.1 M, cho bit H
2
CO
3
c pK
1
= 6.35, pK
2
=10.33
NaHCO
3
Na
+
+ HCO
3
-
.
HCO
3
-
H
+
+ CO
3
2-
. pK
b2
= 14 - pK
a1
= 7.65
HCO
3
-
+ H
2
O H
2
CO
3
+ OH
-
pK
a2
H
2
O H
+
+ OH
-
pK
w
= 14
y l mui c anion lng tnh, pH = 0.5(pK
a1
+ pK
a2
) = 8.35

iv. H
2
SO
4
0.05 M bit K
2
= 10
-1.99
.
H
2
SO
4
H
+
+ HSO
4
-

HSO
4
-
H
+
+ SO
4
2-

| || |
| |

+
=
4
2
4
2
HSO
SO H
K
H
2
O H
+
+ OH
-
pK
w
= 14
y c th uc xem nh hn hp acid mnh v acid yu, nuc phn ly khng ng k
Phng trnh bo ton proton: [H
+
] = [H
+
]
nc 1
+ [H
+
]
nc 2
= C
a
+ [SO
4
2-
] =
| |
2
2
K H
C K
C
a
a
+
+
+

Gii phng trnh bc 2: [H
+
] = 0.0574 M pH = 1.24

d. Ha tan 15.6 g NaH
2
PO
4
.2H
2
O v 17.8 g Na
2
HPO
4
.2H
2
O vo nc v pha long thnh 1L (dung
dch A). Cho bit H
3
PO
4
c pK
1
= 2.12, pK
2
=7.21 v pK
3
=12.36 (1.5 im)
i. Hy tnh pH ca dung dch A.
1L dung dch A cha 0.1 mol acid yu H
2
PO
4
-
v 0.1 mol baz lin hp HPO
4
2-
tc l A l dung
dch m.
| |
| |
21 . 7 lg
4 2
2
4
2
= + =

PO H
HPO
pK pH
a

ii. Nu thm 15 mL NaOH 10 M vo 1 L dung dch A (gi s h s pha long khng ng k), hy
tnh pH ca dung dch.
S mol NaOH thm vo: mol n
OH
15 . 0
1000
10 * 15
= =

Phng trnh phn ng: H
2
PO
4
-
+ OH
-
HPO
4
2-
+ H
2
O do

>
4 2
PO H
NaOH
n n nn H
2
PO
4
-
phn
ng ht; HPO
4
2-
+ OH
-
PO
4
3-
+ H
2
O.
mol n n
du NaOH
PO
05 . 0 1 . 0 15 . 0
,
3
4
= = =

.
Lc ny dung dch c: mol n mol n
HPO PO
15 . 0 05 . 0 1 . 0 ; 05 . 0
2
4
3
4
= + = =

y l dung dch m.
| |
| |
88 . 11
15 . 0
05 . 0
lg 36 . 12 lg
2
4
3
4
3
= + = + =

HPO
PO
pK pH
a


e. Cho dung dch EDTA Na
2
H
2
Y 0.01 M. (1.5 im)
i. Hy tnh nng ca cc cu t H
+
, H
i
Y (i=04) trong dung dch. Cho bit H
4
Y c pK
1
= 2.0,
pK
2
=2.7, pK
3
=6.7 v pK
4
=10.3
Cc cn bng phn ly: Na
2
H
2
Y 2Na
+
+ H
2
Y
2-
.
H
2
Y
2-
H
+
+ HY
3-
pK
a3

HY
3-
H
+
+ Y
4-
pK
a4
H
2
Y
2-
+ H
2
O H
3
Y
-
+ OH
-
pK
b3
H
3
Y
-
+ H
2
O H
4
Y + OH
-
pK
b4
H
2
O H
+
+ OH
-
pK
w
= 14
y l mt mui cha anion lng tnh, pH = 0.5(pK
a2
+ pK
a3
) = 4.7
| |
| |
| | | | | | | |
7 . 6
4 3 2 1 3 2 1 2 1
2
1
3 4
4
4
10

+ + + +
+
=
+ + + +
= C
K K K K K K K H K K H K H H
H
Y H
| |
| |
| | | | | | | |
4
4 3 2 1 3 2 1 2 1
2
1
3 4
1
3
3
10

+ + + +
+
=
+ + + +
= C
K K K K K K K H K K H K H H
K H
Y H
| |
| |
| | | | | | | |
01 . 2
4 3 2 1 3 2 1 2 1
2
1
3 4
2 1
2
2
10

+ + + +
+
=
+ + + +
= C
K K K K K K K H K K H K H H
K K H
Y H
| |
| |
| | | | | | | |
4
4 3 2 1 3 2 1 2 1
2
1
3 4
3 2 1
10

+ + + +
+
=
+ + + +
= C
K K K K K K K H K K H K H H
K K K H
HY
| |
| | | | | | | |
6 . 9
4 3 2 1 3 2 1 2 1
2
1
3 4
4 3 2 1
10

+ + + +
=
+ + + +
= C
K K K K K K K H K K H K H H
K K K K
Y
ii. Nu trn ln 50 mL dung dch Ni
2+
0.01 M vi 50 mL dung dch Na
2
H
2
Y 0.02 M ti pH = 4.7;
hy tnh tt c cc dng H
i
Y (i=04) v NiY. Cho bit 6 . 18 =
NiY
pK .
Phn ng: Ni
2+
+ H
2
Y
2-
NiY
2-
+ 2H
+
hay Ni + Y NiY
Ti pH 4.7 c
61 . 7
7 . 21
8 . 18
7 . 19
1 . 14
17
4 . 9
3 . 10
7 . 4
) (
10
10
10
10
10
10
10
10
10
1
1
= + + + + =

H Y
o

Hng s cn bng iu kin:
| |
| || |
| |
| || |
7 9 . 10
) ( ) ( ) (
10 10
1
' '
' > = = = = =
H Y
NiY
H Y cb H Y
K
K
Y Ni
NiY
Y Ni
NiY
K o o o ,
nh vy phn ng gia Ni v EDTA l hon ton.
[NiY] = C
Ni
= 0.5*0.01 = 0.005 M
[H
2
Y]
d
= 0.5*(C
H2Y
[NiY]) = 0.005 M.
Nh vy nng cc cu t [H
i
Y] ging nh cu a vi C = 0.005 M [H
4
Y]=10
-7
M;
[H
3
Y]=10
-4.3
M; [H
2
Y]=10
-2.31
M; [HY]=10
4.3
M; [Y]=10
-9.9
M.

2. nh phn acid: 3 im
a. Chun dung dch HCl 0.1 N bng NaOH (0.1032 0.0019) N. Hy xc nh iu kin chun
vi chnh xc >99.9%? Xc nh khong bc nhy ca php chun qua cc F = 0.999; F
= 1.000 v F = 1.001? Tnh sai s im cui nu dng cc ch th methyl cam (pT = 4) v
phenolphthalein (pT=8.3)? (1.0 im)
Phng trnh chun : H
+
+ OH
-
H
2
O
iu kin chun
NQ
<0.001: pC
o
+ pD
F=1
= 1 + 0.3 = 1.3 < 4, vy php chun ny t uc
chnh xc > 99.9%.
ng cong chun :
- F = 0.999 dung dch c 99.9%C
o
D NaCl v 0.1% C
o
D HCl: dung dch n acid mnh + mui
trung tnh pH = -lg 0.1%C
o
D = 4.3
- F = 1.000 dung dch c 100%C
o
D NaCl: mui trung tnh pH = 7.
- F = 1.001 dung dch c 100%C
o
D NaCl v 0.1% C
o
D NaOH: dung dch n baz mnh +
mui trung tnh pH = 14-lg 0.1%C
o
D = 9.7
khong bc nhy: 4.3 9.7.
Sai s ch th:
- Nu dng methyl cam (pT=4): ch th i mu trc im tng ng, sai s thiu,
% 2 . 0
2 * 1 . 0
100 * 10
5 . 0 * 1 . 0
100 * 10 100 * 10
1
4 4
%
,
= = = ~ A <

+
D C
F
o
pT
H Ind
cui

Nu dng phenolphthlein (pT=8.3): ch th i mu sau im tng ng, sai s tha,
% 004 . 0
5 . 0 * 1 . 0
100 * 10 100 * 10
1
7 . 5 14
%
,
= + = + ~ A >

D C
F
o
pT
OH Ind
cui

b. Thc hin php chun lp 4 ln, mi ln vi 10.00 mL dung dch mu HCl. Th tch NaOH tiu
tn ln lt l 10.25; 10.30; 10.20 v 10.30 mL. Hy tnh nng HCl c km theo khong bt n.
Bit rng pipet 10 mL c = 0.02 mL, t
0.95;3
=3.18; u
0.95
= 1.96 (1.0 im).
mL V NaOH 2625 . 10 = ; S
4
= 0.04787 076 . 0
4
04787 . 0
18 . 3
4
3 ; 95 . 0
= = =
n
S
t
NaOH V
c
V
HCl
= 10 mL, 0266 . 0
3
02 . 0
96 . 1
95 . 0
= = =
n
u
HCl
V
o
c
) ( 105909 . 0
10
2625 . 10 * 1032 . 0
N
V
V C
C
HCl
NaOH
NaOH
HCl
= = =
02 . 0
10
02266 . 0
2625 . 10
076 . 0
1032 . 0
0019 . 0
2 2 2
2 2 2
=
|
.
|

\
|
+
|
.
|

\
|
+
|
.
|

\
|
=
|
|
.
|

\
|
+
|
|
.
|

\
|
+
|
|
.
|

\
|
=
HCl
V
NaOH
V
NaOH
C
HCl
C
V V C C
HCl NaOH NaOH HCl
c c c c


0021 . 0 105909 . 0 * 02 . 0 02 . 0 = = =
HCl
HCl
C
HCl
C
C
c
c

C
HCl
= 0.1059 0.0021 (N)
c. Trong php chun trn ngi ta c th dng cht gc Na
2
CO
3
thay cho NaOH. Hy xc nh
iu kin chun , khong bc nhy pH trong tnh hung ny chng minh rng Na
2
CO
3
ph
hp cho php chun ny vi ch th methyl cam (pT 4.0) hoc ch th Tashiro pT 5.4. Bit rng
H
2
CO
3
c pK
1
= 6.35, pK
2
=10.33, tan ca CO
2
nhit phng l 0.001 M? (1.0 im).
Phn ng: CO
3
2-
+ H
+
HCO
3
-
.
HCO
3
+ H
+
H
2
CO
3
CO
2
+ H
2
O.
Do acid carbonic c 2 nc c pK < 4 nn ch c th chun tng hai nc t chnh xc cao.
Gi s nng Na
2
CO
3
l 0.05M, iu kin chun : pK
b
+ pC
o
+ pD
F=2
= 7.65 + 1.3 + 0.3 = 9.25 <
10. khng th chun vi chnh xc >99.9% m ch min cng vi chnh xc 99% m
thi, nh vy sodium carbonate cha phi l cht gc tt???
Thc t do tnh cht c bit ca acid carbonic: phn hy thnh kh carbonic v thot ra khi h phn
ng.
F = 1.99: dung dch c 1% C
o
D NaHCO
3
= 0.0005 M v 99% C
o
D H
2
CO
3
= 0.0495 M > 0.001 M
mt phn ln H
2
CO
3
thot ra khi h dng CO
2
. Dung dch phn ng c tnh m.
| |
| |
05 . 6
001 . 0
0005 . 0
lg 35 . 6 lg
3 2
3
1
= + = + =

CO H
HCO
pK pH
a

F = 2.00: dung dch c 100% C
o
D H
2
CO
3
= 0.05 M > 0.001 M, ly | | M CO H 001 . 0
3 2
= pH = 4.675
(xem nh n acid yu).
F = 2.01: dung dch cha 100% C
o
D H
2
CO
3
v 1% C
o
D HCl = 0.01*0.05*0.5 = 0.00025 M: xem nh
ch c HCl pH = -lg 0.00025 = 3.60.
Khong bc nhy l 3.6 6.05 vi chnh xc 99%.
Trong thc t khi thc hin chun ny ngi ta thng un nng dung dch ui ht
H
2
CO
3
, gi s nng H
2
CO
3
trong dung dch lc ny cn 10
-5
M, lc ny ti
F = 1.99: dung dch c 1% C
o
D NaHCO
3
= 0.0005 M v 99% C
o
D H
2
CO
3
= 0.0495 M > 0.00001 M
mt phn ln H
2
CO
3
thot ra khi h dng CO
2
. Dung dch phn ng c tnh m.
| |
| |
05 . 8
00001 . 0
0005 . 0
lg 35 . 6 lg
3 2
3
1
= + = + =

CO H
HCO
pK pH
a

F = 2.00: dung dch c 100% C
o
D H
2
CO
3
= 0.05 M > 0.00001 M, ly | | M CO H 00001 . 0
3 2
= pH =
5.675 (xem nh n acid yu).
Khong bc nhy trong trng hp ny l 3.6 8.05 (99%) hay 4.6 7.05 (99.9%), chnh xc
ca php chun tng ln v c th dng ch th hn hp Tashiro pT 5.4 c chnh xc tt nht.

HT