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TRNG I HC S PHM THI LP HA 3 HC K 2 (2013-2014)

TP. H CH MINH MN THI: MT S PP PHN TCH HA L
KHOA HA THI GIAN THI: 120 PHT
( thi c 2 trang)

Cu I: (2,5 im)
Thy ngn (II) to phc 1:1 vi triphenyl-tetrazoly clorua (TTC) c cc i hp th ti 255 nm. Thy ngn
(II) trong 100 gam mu t c chit trong mt dung mi hu c cha lng d TTC, sau nh mc
thnh 100 mL (dung dch A). Ngi ta chun b mt dung dch chun cha Hg (II) 5,00.10
-6
M (dung dch
B). tin hnh nh lng, nh phn tch pha ch 6 dung dch trong cc iu kin nh nhau. Tin hnh o
quang cc dung dch ti 255 nm trong cuvet 1 cm. Kt qu c cho bng sau:

Dung dch 1 2 3 4 5 6
Dung dch A 5 mL 5 mL 5 mL 5 mL 5 mL 5 mL
Dung dch B 0 mL 2 mL 4 mL 6 mL 8 mL 10 mL
nh mc n 25 mL
hp th 0,582 0,689 0,767 0,869 1,009 1,127

1. Nh phn tch s dng phng php trc quang no m anh / ch hc? Gii thch v nu u
im ca phng php trn.
2. Tnh hm lng thy ngn c trong mu t trn theo n v ppm (m/m). Cho Hg = 200,59.

Cu II: (2 im)
Hin nay, trong cc phng th nghim hin i th pH thng c o bng in cc thy tinh, cc
trng hp cn li th c o bng phng php quang hc kt hp vi dng cht ch th. V d nh khi
xc nh pH trong mu nc bin. V hm lng mui tan trong nc bin l rt cao dn n sai s h thng
rt ln khi o pH bng in cc thy tinh nn ngi ta hay s dng phng php o quang.
Thymol xanh (M = 466,59 gmol
1
) l ch th c mu thuc dng axit hai ln axit. Nng ca dng
khng phn li, H
2
In c th b qua pH ca nc bin. 298 K, hng s phn li nc th 2 ca thymol xanh,
c hiu chnh, l K
a2
= 10
8.09
. H s hp th phn t gam (

) ca HIn

v In
2
ti hai bc sng ()
nh trong bng sau:
Ion c
436
(L.mol
1
.cm
1
) c
596
(L.mol
1
.cm
1
)
HIn

13900 44,2
In
2
1930 33800

Tin hnh o mu nc bin trong cuvet loi 10,00 cm, kt qu nh sau:

A (436 nm) A (596 nm)
Mu nc bin 0,052 0,023
Mu c thm ch th thymol xanh 0,651 0,882
1. Tnh nng mol ca thymol xanh trong mu.
2. Tnh pH ca mu nc bin.

Cu III: (2 im)
1. Nu cc nguyn nhn sai s khi s dng in cc thy tinh.
2. Trong phng php cc ph c in, cc yu t no dng nh tnh, nh lng.
3. u im ca phng php cc ph xung vi phn so vi phng php cc ph thng thng l g?
4. To sao phng php phn tch volt ampe ha tan l phng php in ha hin i nht hin nay?
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Cu IV: (1,5 im)
in cc chn lc ion (ISE) l mt trong nhng phng php xc nh nhanh v r tin m khng qua
nhiu giai on ch ha cn thit. Th ca mng s t l vi nng ion cn xc nh theo cng thc sau:
( ) m m
Cell
M M
0, 059
E K lgC
m
+ +
= +

Nng ca ion Ca
2+
trong mu nc bin c xc nh bng in cc mng chn lc ion.
10 mL dung dch mu c chuyn vo bnh nh mc 100,0 mL v pha long ti vch, gi l dung dch
(C). Ly 50,0 mL dung dch (C) cho vo cc c nhng in cc chn lc ion Ca
2+
v in cc so snh, th
o c l 0,05290 V. Thm 1,00 mL dung dch Ca
2+
nng 5,00.10
2
M vo cc. Th o c lc ny
l 0,04417 V.
1. Nh phn tch s dng phng php nh lng g m cc anh/ch c hc ?
2. Tnh nng mol ca ion Ca
2+
trong mu nc bin (ch n s pha long th tch).

Cu V: (1 im)
Mt php sc k kh s dng ct di 36m, chy cht chun 3 th nghim vi tc pha ng khc nhau
cho cc pic c thi gian lu v rng pic nh sau:
TN u(cm/s) t
R
(s) w(s)
1
2
3
10
20
30
300
250
150
20
16
10

Xc nh vn tc ti u, s a l thuyt cho ct khi vn hnh vn tc ti u .

Cu VI: (1 im)
Transferrin is the iron-transport protein found in blood. It has a molecular mass of 81000 and carries two
Fe
3+
ions. Desferrioxamine B is a chelator used to treat patients with iron overload. It has a molecular mass
of about 650 and can bind one Fe
3+
. Desferrioxamine can take iron from many sites within the body and is
excreted (with its iron) through the kidneys. Molar absorptivities of these compounds (saturated with iron) at
two wavelengths are given in the table. Both compounds are colorless (no visible absorption) in the absence
of iron.


(a) A solution of transferrin exhibits an absorbance of 0.463 at 470 nm in a 1.000-cm cell. Calculate the
concentration of transferrin in milligrams per milliliter and the concentration of bound iron in
micrograms per milliliter.
(b) After adding desferrioxamine (which dilutes the sample), the absorbance at 470 nm was 0.424 and the
absorbance at 428 nm was 0.401. Calculate the fraction of iron in transferrin and the fraction in
desferrioxamine. Remember that transferrin binds two iron atoms and desferrioxamine binds only one.

HT.
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P N
Cu I:
Dung dch 1 2 3 4 5 6
Dung dch A 5 mL 5 mL 5 mL 5 mL 5 mL 5 mL
Dung dch B 0 mL 2 mL 4 mL 6 mL 8 mL 10 mL
nh mc n 25 mL
hp th 0,582 0,689 0,767 0,869 1,009 1,127
C
thm
x 10
7
(M) 0 4,00 8,00 12,0 16,0 20,0

1. Phng php thm chun. Lp dy chun vi dd u l dd nghin cu, cc dd sau l dd nghin cu
c thm cc cht chun bit trc nng chnh xc. u im: loi tr nh hng ca nn mu.
2. Phng trnh hi quy: Y = 0,57 + 0,02705.X. C
Hg(II)
(dd o) = 21,1.10
-7
M.
C
Hg(II)
(dd A) = 10,55.10
-6
M
m
Hg
= (10,55.10
-6
mol.L
-1
)x(100 mL)x(1L/1000 mL)x(200,59 gam.mol
-1
) = 2,12.10
-4
gam.
C
Hg
(m/m) = (2,12.10
-4
gam) / (100 gam) x 10
6
= 2,12 (ppm).

Cu II:
1. Ta c h phng trnh ti 2 bc sng nh sau:
2
2
0, 651 0, 052 0, 599 13900.10.[HIn ] 1930.10.[In ]
0, 882 0, 023 0, 859 44, 2.10.[HIn ] 33800.10.[In ]


= = +

= = +

[HIn
-
] = 3,96.10
-6
M; [In
2-
] = 2,54.10
-6
M. -> C
thymol xanh
= 6,5.10
-6
M.
2.
2 6
a2 6
[In ] [2, 54.10 ]
pH pK lg 8, 09 lg 7, 90.
[HIn ] [3, 96.10 ]


= + = + =
Cu III:
1. Cc nguyn nhn sai s khi s dng in cc thy tinh:
- Cht chun, th tip xc, sai s axit, sai s kim, thi gian cn bng, lp hydrat ha, nhit , lm
sch b mt in cc.
2. Cc ph c in: - nh tnh: E
1/2
; nh lng: I
gii hn
hay

I
khuch tn
.
3. u im cc ph xung vi phn: - loi tr dng t in, tng nhy v chn lc ( phn gii).
4. Votl ampe ha tan: Lm giu trn b mt in cc -> gim LOD v LOQ, tng nhy rt nhiu.

Cu IV:
1. Phng php thm.
2. Ta c cc phng trnh sau:
2
2 2
0, 059
0, 05290 K lg[Ca ]
2
0, 059 50.[Ca ] 5.10 x1
0, 04417 K lg
2 50 1
+
+

= +

| | +

= +
|
+
\ .


2 2
0,296
2
50.[Ca ] 5.10
10 1, 977
51.[Ca ]
+
+
+
= = [Ca
2+
] = 9,84.10
-4
M C
Ca
2+
(nc bin) = 9,84.10
-3
M.
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Cu V:
Theo phng trnh Van Deemter, mun xc nh c vn tc ti u, H
min
v s a l thuyt, cn xc nh
cc h s A, B, C, mun vy ta xc nh s a l thuyt v chiu cao a l thuyt cho tng th nghim:
TN1:
2
1
300
N = 16 = 3600
20
| |
|
\ .
;
1
3600
H = =1cm
3600
, TN2:
2
2
250
N =16 =3906
16
| |
|
\ .
;
2
3600
H = = 0,92 cm
3906
;
TN3:
2
3
150
N =16 =3600
10
| |
|
\ .
;
3
3600
H = =1cm
3600
; Ta c h phng trnh:
B
1=A+ +10.C
10
B
0,92=A+ +20.C
20
B
1=A+ +30.C
30

Gii h phng trnh ta c: A = 0,36 cm; B = 4,8 cm
2
/s ; C = 0,016 s;

t.u
-2 -1
min
B
u = = 17,32 cm/s
C
H = A + 2 B.C= 0,36 + 2 7,68.10 = 9,14.10 cm = 0,914 cm
3600 cm
N= 3939.
0,914 cm
~

Cu VI:
(a) C
Tr
= 1,110.10
-4
M = 8,99 mg.mL
-1
. C
Fe
= 12,4 g.mL
-1
.
(b) [Tr] = 7,30.10
-5
M; [De] = 5,22.10
-5
M. %Fe (Tr) = 73,7 %; %Fe (De) = 26,3%.