Nghiên cứu xác định các hidrocacbon thơm nhóm btex bằng phương pháp phân tích động lực học kết hợp với vi chiết pha rắn màng kim rỗng và sắc kí khí - Pdf 10


ng
lc hc kt hp vi vi chit pha r
r

 i hc Khoa hc T 
c
Lu: 60 44 27
ng dn: GS. TSKH. Nguyc Hu
o v: 2011 Abstract. Tng quan v t h
chip chng lc hnh
p chng vi chit pha r
c nghim: ch to
thit b vi ching ph trong; kh  dng c
dp chu v thit b chi
kim rng ph trong; s  dng trong thit b vi ching; kim
vi chii ht khp
cht Btex trong m th
thut cg s 
trong mc.

Keywords. ; c; ; ; ng
lc hc; Chit pha rn

Content

-               nh
c.
-   i ph  h kh thi, d         
 d
-        u trong vi     
c thi ti mt s  i.

NG QUAN
1.1. GII THIT H
1.1.1 Cu tt cp ch

Bt s t c

STT

Benzen
Toluen
Etylbenzen
m-Xilen
1
  
t
C
6
H
6
C
6
H
5

760mmHg
80,1
110,6
136,2
139,1
5
y
(
0
C)
5,5
-95
-95
-47,9
6
T trng (g/cm
3
)
0,8765
20/4
0,8669
20/4
0,8670
20/4
0,8642
20/4
7
 n cc
3,0
2,3

Ghi chú: “-”: không có số liệu
* Ứng dụng và nguồn phát thải các hợp chất hiđrocacbon thơm nhóm BTEX
c s dng
trong rt nhin xuy da, dt vi, thuc bo v
thc vt lo ng
c
ng rt ln xu dn ph
d ng s 
khi ng vp th 
 bng nhing, qua da trong thc
hoc cc b.
i s n mnh m ca khoa ht trong s d
lii mnh m 
ng s phn x 
thi ra hou qun ca m
ln chuy
dng, m  
cht rt d 
1.1.2 Gii hp chc
Bng 1.2: Quy chun Vit Nam v ch    ng v    
(QCVN 01-2009/BYT)
Cht
Benzen
Toluen
Etylbenzen
Xilen
N  t    
-
6


400
1.000

ng tuyng phc phn triu (ppm), ca m
phn nguy hi trong cht thng tuyi (H
tc
ng cht thi nguy
hng tuyi
+ N  (mg/l) ca mn nguy hi trong dung dch sau
 cht thi khi tinh chun b mu b
ching n t (C
tc
ng cht thi nguy hng
t [7, 8].
i, s m cp ch
n th nhi n
ng sng ca nhiy, cng bi
hu hi hn ch s t cng.
P CHT

Vip cht hu
sinh hc li v
- p ch 
- N p chng ng nhn
- n mng phc tp
Hin nay, ch  hp th hng ngoi ( UV- c s d
p chn chun b m  
hp vi mt s hp cht nht nh, kh ng vi nhin ch. Vic
c, tp trung m tiy mu thc t hoc tm


cht cu m u. Hiu qu cng
vic gia nhii pH cho mu hoc gin KGH mu.
* Kĩ thuật vi chiê
́
t pha rắn ma
̀
ng kim rỗng phu
̉
trong (HNF-ME)
c ct vi ching ph  ci tin ct
vi chit pha rng (s dng sc kim loi ph pha 
chit d cu t cht t ng cha ch
mc ph a mng hp kim
 (c 0,2-p ch t
c bin nhit HNF-ME, vic la ch 
 c t ng yu t  mang li hiu qu
t. So vt vi chit pha rng, s ci
tim khc phc mt s  i nh i
hn, gc tip vi m bn ca thit b i nh
d g d b hng [3, 14, 26, 36, 38].
c ph a mng vi m 
nhng cha m ng hoc KGH mu
lng, KGH mu rn Thc hi cho mt phng mc
tii my, nh ng thp ph
p th (gp thu) ct tr
bng h ng cht vi ching
 c gii hp bi
nhit khi c
mh  dng [24, 34, 48].
Kt hp vt pha rn s dng si ching lc

Mn thay th cho mn b
  ng lc hc ca vi chit pha rt
uy quan h ging cht chi u ca
ch c s d d c nghim
tu kin chi
ng lc hc ca vi chit pha r
t pha r thuc: pha l
  mt, b mt l mi b mt
   chuyn kh   khu          
c biu th bnh lut Fick th nht ca s khu
 ng chuyn kh
(1.3.1)
  l i, bng t l  
i vi s chuyn khng. D
1
 
2
 s khua ch

g
 ch
f

 chng chc
b  l chit SPME s i t l 
kh
(1.3.2)
  mt c
S khua ch
1

t SPME b . N ch
cn kit do s hp th SPME, chng s  
Ti b mt lng lc ca s bc t pha l 
lch n  ng. Gi C
0
g
 
ca chng. Lng lc ca s ch
g
0
 C
g
. T l
c gi  thun vi C
g
0
C
g
t trn
nh, t l i  b mt l b m, t l 
s bng t l 
(1.3.5)
 ng s t l  thuu yu t, din
 mu kin khuy ca pha lng. Gi C
s
 ca ch
l
1
ng s ng phn ca chia pha la


s
C
g
 hng C
0

kt qu 
(1.3.12)
 ng vi 2 bi   
c gii vu kiu sau: khi t = 0, n = 0.
(1.3.13)
Pi vng lc hc c
 hin mc tip ging chi
u C
0
 t mi quan h t l thun tuyi thi gian ly
mu t k t  
(1.3.14)
 hing tng phn. Gi
(1.3.15)
 
(1.3.16)
Mp s c s d 
s hp th c mt rc suy ra t 
ng lc hc ca s chuyn khi  hai b mt c  
m    thu s chuyn
khi, hng s t l ng s  c va h th
 t t. Mi quan h t l thun
trc tip gi
0

Th  thn tr gin c
-12
 
t hin t  c sinh ra trong ngn l-
khit. Khi ch a ra t cn la nh nhit
  b gy mch, b  oxi c  
ng h
C
6
H
6

6CH + O
2

+
+ 6e
-

1.5.1.Gii hn
Gii h thp nht (x
L
) ca ch
h th
L
u ca mu trng
n nn [22].
Hình 1.3: Sơ đồ khối thiết bị sắc kí khí
T
.

1
()
1
b
n
b bi b
i
b
S x x
n




(1.5.3)
y
.
B
B
L
kS
xx
b

(1.5.4)
Mu trc chun b vi n ch
B
i h
hi


b


(1.5.6)
1.5.2. Gii hng
Gii hc xem  thp nht (x
Q
) ca ch
c v
Q
ng v
hiu ca mu trng nn [22, 33].

.
QB
B
y y K S
(1.5.7)
i h

10.
B
Sa
LOQ
b


(1.5.8)

2: 













 ,  : 30,8mm; 





 : 0,52





 :
t s ch 
 m ta ra x            
diclometan, n-hexan. Sau khi ra sch b chun b tm kim.
2.2.2. 








 

 ng
  

  c nghi
i kt qu quan t 
2.2.3.  


 (



 ) 



 ch c
 c pha s   i mt n    
polihidromech pha
n m

 












 , ti












 .
 
 c nghim (3.1). T 
kt qu 
tr n ct qu kh 
ng n t n 0,3g/ml c

6594
7296
5
13421
13844
10940
12743
7
20635
20221
16943
19426
10
25213
24090
19368
21252
13
29268
27338
21409
24294
15
29942
28039
21740
24835
20
29938
28025

24820
2
29564
28213
21776
23719
3
29785
28024
21788
23976
4
29985
29034
21261
24965
5
30346
28209
21822
25813
6
30435
29278
22710
25898
7
29887
28217
21125

24725
14
30231
27836
21813
24036
15
30875
28095
21887
23902

 HP CH
MC
u ki
a) Điều kiện phân tích sắc kí khí của các chất nhóm BTEX
    200
0
C; t        
 
 t mao qun: Ct SPB-50: 30m x 0,25mm x 0,25   
a ct dn c c ca
 : nhi u 60
0
C, gi 15

0
C vi t 20
0
  

158
392
147
0,1
359
268
656
313
0,3
1248
741
2164
947
0,5
1989
1293
3870
1733
1
4194
2573
7504
3563
3
12320
8075
22659
11053
5
20401

8000
10000
12000
14000
Duong chuan halmiton cua toluen
Y = A + B * X
Parameter Value Error
A -2.82274 47.32021
B 2633.04112 21.05647

R SD N P
0.99984 96.97252 7 <0.0001

dien tich pic
luong chat (.10
-10
g/lit)

ng chu c
ng chu  
mc kt hp vi st qu u kin tc kho
c v n b u
kiTh ch m 
mui Na
2
SO
4
, gi  nhi 
0
C, khuu vi t t

3016
3099
2240
2487
1,00
5804
5930
4663
5093
2,00
11608
11727
8730
9623
5,00
29020
27831
22384
23502
10,00
58040
56067
42954
45439

p cht s mc tht
c ly t nguc thi cng sn xu
dt bao gm: BTEX-1: M c thi t    ng h     
khong 20m); BTEX-2: Mc t cc cc-Vic
p Vit Nam; BTEX-3: Mc thi t ng dt-t 8-ng

t pha rc s dng nhng thit b i chi
t lt thit bp phi nhng hn ch chung ct vi
chit pha r ch to thit b vi chit pha rng
ph trong mt loi kim y t ng bng hp kim
ng 
bi   ph lp
 chc chn. Na vic s dng s
trong c thy rng: st si nh 
 d n, d ki ti
n v mt kinh t u qu s dng. M ma kim ln
 hp ph cc chc nhi c
i vi nhng mu vi n thc ph l
tr m c tip vng mu. My, vi
chit pha rng ph trong (HNF-ME) l tin
t pha rng, bng ving nhiu l
ng nhiu lng cha mc tivi
 tc thi ca ch
c thit lp, nh v n tht tng ca
c n thi gian chun b m 
 ng mu c 
 sau:

          

 DNG TRONG THIT B VI CHING PH
TRONG
3.2.1. Ngc la ch ng





 





 vt liu
 dng trong ct sn). 











 , 

+  n li vi mi cht hoc mt ct
nh.
 n li v thuu t 
c c ng v c ng c 
cc chnh nhi 
n yu, lc Van der Wals.
            25
0
C
bng 1 g/cm
3
 c y p ch c
yu hoc. Qua kh ng cn hiu qu vi
chii hiu qu vi chit tt.
  
p ch
  trong trong kim vi chit
Vit mt s c
rt quan tr  u t quynh
n hiu qu ct la ch i gian vi chit, gii hn ca
c kha ch  tht
cn thi chung cho vic la chng
s  (K) cu t cng s ng
  c nhiu, t trng
[4, 36, 38, 47].
V m  ng cht chic nhi
i hn c i vu
thc t c chp. M
dng mu cc hi i
n gii h mang li mc tin to l

t loi loc ph t kim rng nh 
 thu dung dng pha  
trong ca kim rng.

I HT KH
c ci hp bi nhit   i
cc li ct
h d to thit b vi chi
rng ph   nh a kim nh, d n
 a kim b hn ch nhiu. Th 
(khong mu ti
khi vi ching m ti i gian
 i n 8cm, khi gii hp nhit ti
c 
u, dn vic gii hp ct kh
gii hp b y ra sai s.
 ch to trong vi chi 
 li hp nhi 
i hp di
 a kim ng gia nhi i hp c
chc di

P CHC
c
T kt qu khu t t vi chit trong KGH mu lng kt hp
v- 
c ch 

p chc

V c, kt
qu dng chu c ch  bng 2.5. T  liu biu din s ph
thuc ca di ca chu lng chun
  s hi quy ca tng chn mm Origin
6.0 n

Thiết bị vi chiết pha rắn màng
kim rỗng phủ trong với:
- pha tĩnh
polimetylhydrosiloxan

30000
40000
50000
60000
Duong chuan phan bo cua benzen
Y = A + B * X
Parameter Value Error

A 120.27698 42.07255
B 5787.45636 9.753

R SD N P

0.99999 87.54562 7 <0.0001

dien tich pic
nong do ban dau (.10
-6
g/lit)

ng chu ca benzen trong mc

0 2 4 6 8 10
0
10000
20000
30000
40000
50000
60000

LOD cm trong khong 0,005-
-1
, h s bing RSD trong
khong 2,02-4,61%.
ng s 
bt HF-t hp vi s
Kt qu cho thy, gii h  n LOD c      ng 0,06-

-1
, h s u trong khong 112- s bing 6,5-11,4% (n=5) 




Nu thc hin trong luc tin nh
pht chun b mu mi s d
 nhng kt qu  t s kt lun sau:
1.  ch tc dng c vi chit pha rng n, hiu qu i vi
vip cht h
2. p cht h
ng lc hc di quan h tuya n u ca ch
ng cht chit c.
3.  
c thi thc t ca mt s 
i.
Qua tht qu n thy SP
ri hn thp (c 10

7. n Vit Nam TCVN 5938: 2005 (xut bn lChất lượng không khí- nồng
độ tối đa cho phép của một số chất độc hại trong không khí xung quanh”.
8. n Vit Nam TCVN 5940: 2005 (xut bn ln 2), “Chất lượng không khí- Tiêu
chuẩn khí thải công nghiệp đối với một số chất hữu cơ”.
9. Trnh Th Thanh (2003), “Độc học môi trường và sức khoẻ con người”i hc
Qui.
10. Nguyn Anh Tun, Nguyc Hu, Trn Mu ch to kim
t pha r t s Tạp
chí phòng chống sốt rét và các bệnh ký sinh trùng (s 4), tr.59-65.
11. PhSắc kí khí cơ sở lí thuyết và khả năng ứng dụng
Qui, 264tr.
12. Trn M“ Nghiên cứu phát triển phương pháp vi chiết kết hợp với sắc kí
khí phân tích hợp chất hữu cơ bay hơi”, Lu
Ting Anh
13. Berg Fohn R. (1997), ''Method and device for solid phase microextraction'', United
States Patent 6164144.
14.        -phase microextraction/gas
chromatographic/mass spectrometric assay for the quantitative determination of
some of the main odorants causing off-flavours in wine”, Journal of
Chromatography A, 1141, pp.1-9.
15. 
of volatile chlorinated hydrocarbons in air and water with solid-phase
Analyst, 118, 1501-1505.
16. CRC Handbook of Chemistry and Physics (1985), 65th, CRC Press, Inc. Boca Raton,
Florida.
17.       
preparation for the analysis of volatile organic compounds in air and water
, Journal of Chromatography A, 1153, 130-144.
18.            
toluene, ethylbenzene and xylenes in indoor air at environmental levels using

           
samples by gas chrom     J. Petroleum &
Coal, ISSN 1337-7027, 47, (3), pp.49-53.
28.           
    Analytical Chemistry, Vol. 69,
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29. -Phase Microextraction and Related
      School of Pharmacy,
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, Anal Bioanal Chem, 396, pp.339-364.
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volatile hallogenated hydrocarbons in water by pure and trap with gas
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