TRNG I HC CNG NGHIP TP.

HCM
KHOA CNG NGH HA HC

N CHUYN NGNH HA PHN TCH

TM HIU CC QUY TRNH XC NH DUNG

MI D BAY HI TRONG BAO B

Ging vin hng dn: Th.S L THANH TM

Sinh vin thc hin: NGUYN TH THU HOI
MSSV: 10319781
Lp: HPT6LT
Kho: 2010-2012

TP. H Ch Minh, thng 6 nm 2012

TRNG I HC CNG NGHIP TP. HCM

KHOA CNG NGH HA HC

N CHUYN NGNH HA PHN TCH

TM HIU CC QUY TRNH XC NH DUNG

MI D BAY HI TRONG BAO B

Ging vin hng dn: Th.S L THANH TM

Sinh vin thc hin: NGUYN TH THU HOI
MSSV: 10319781
Lp: HPT6LT
Kho: 2010-2012

TP. H Ch Minh, thng 6 nm 2012

ii

LI CM N

Li u tin em xin bay to long bit n su sc n cac Thy C Trung Tm Cng

Ngh Hoa, b mn Hoa Phn Tich a truyn at cho chung em nhng kin thc quy bau
lam c s cho nhom chung em co c nhng kin thc b ich nhm phuc vu cho chuyn
nghanh phn tich sau nay.
Em cung xin chn than cam n thy L Thanh Tm a t n tinh chi bao va tao iu
ki n thu n li cho em hoan thanh tt an nay.
Trong qua trinh thc hi n bai bao cao nay chc chn khng th tranh khoi nhng
thiu sot. Kinh mong quy thy c, cac ban nhi t tinh ong gop nhng y kin quy bau
quyn bao cao cua em c tr nn hoan thi n tt hn.

ii

NHN XT CA GING VIN HNG DN

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Phn anh gia:

thc thc hin:............................................................................................................

Ni dung thc hin:........................................................................................................

Hinh thc trinh bay:........................................................................................................

Tng hp kt qua:...........................................................................................................

im bng s:....................................im bng ch:...............................................................

Tp. H Chi Minh, ngay thang nm 2012
Giang vin hng dn

Th.S. L Thanh Tm

iii

NHN XT CA GING VIN PHN BIN

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Phn anh gia:

thc thc hin:............................................................................................................

Ni dung thc hin:........................................................................................................

Hinh thc trinh bay:........................................................................................................

Tng hp kt qua:...........................................................................................................

im bng s:....................................im bng ch:...............................................................

Tp. H Chi Minh, ngay thang nm 2012
Giang vin phan bin

iv

MC LC

LI CM N..........................................................................................................ii
NHN XT CA GING VIN HNG DN.................................................iii
NHN XT CA GING VIN PHN BIN....................................................iv
MC LC................................................................................................................ v
DANH MC BNG BIU...................................................................................vii
DANH MC HNH NH......................................................................................ix
LI M U..........................................................................................................x
CHNG 1: TNG QUAN V CC DUNG MI D BAY HI.....................1
1.1. Tng quan v dung mi..................................................................................1
1.1.1. Khai nim dung mi................................................................................1
1.1.2. Tinh cht vt ly cua dung mi hu c.....................................................1
1.1.3.Tinh cht hoa hc cua dung mi..............................................................2
1.1.4. Cac chi tiu anh gia cht lng dung mi hu c.................................2
1.1.6. Ngun phat sinh nhim VOCs..............................................................3
1.1.7. c tinh cua cac dung mi hu c d bay hi........................................3
1.2. Tng quan v sc ky khi.................................................................................3
1.2.1. Gii thiu v sc ky khi...........................................................................3
1.2.2. Thit b trong sc ky khi..........................................................................4
1.2.3. K thut tim mu Headspace.................................................................5
CHNG 2: GII THIU V BAO B V MC IN.......................................10
2.1. Gii thiu v bao bi......................................................................................10
2.1.1. nh ngha.............................................................................................10
2.1.2. Chc nng cng ngh va tiu dng.......................................................10
2.1.3. Mt s loai mang bao bi thng dung.....................................................10
2.1.3.2. Polyethylen (PE)................................................................................10
2.1.4. Bao bi thc phm..................................................................................10
2.2. Gii thiu mc in..........................................................................................11

2.2.1. Khai nim..............................................................................................11

2.2.2. Cu tao, phn loai..................................................................................11
2.2.3. C ch bam dinh cua mc in ln bao bi................................................12
CHNG 3: QUY TRNH XC NH DUNG MI D BAY HI TRONG
BAO B THC PHM POLYSTYRENE...........................................................13
3.1. Pham vi nghin cu......................................................................................13
3.2. Phng phap ap dung...................................................................................13
3.3. anh gia k thut chun b mu...................................................................13
3.4. Cht phn tich va hoa cht............................................................................13
3.5. Thit b.........................................................................................................15
3.6. Phng phap kim tra vt liu......................................................................15
3.6.1. Chun b dung dch chun.....................................................................15
3.6.2. Chun b mu- k thut hoa tan.............................................................16
3.6.3. iu kin sc ky khi..............................................................................16
3.6.4. Phn tich va nh lng.........................................................................16
3.6.5. Quan ly cht lng php o..................................................................17
3.7. Phng phap HS-SPME...............................................................................17
3.7.1. Chun b dung dch chun.....................................................................17
3.7.2. Dang thc phm va iu kin ty ra....................................................18
3.7.3. Chun b mu........................................................................................18
3.7.5. Thit b..................................................................................................19
3.7.6. Phn tich va nh lng.........................................................................19
3.7.7. Ti u hoa cac tham s SPME..............................................................20
3.8. Phng phap xac nh..................................................................................20
3.8.1. c im...............................................................................................20
3.8.2. Gii han phat hin va gii han nh lng............................................21
3.8.4. chinh xac.........................................................................................22
3.9. Phn tich d liu...........................................................................................23

vi

CHNG 4: PHNG PHP PHT TRIN V PHNG PHP P DNG

XC NH HP CHT HU C D BAY HI TRONG BAO B THC
PHM POLYSTYRENE......................................................................................24
4.1. Phng phap phat trin xac nh hp cht hu c d bay hi trong bao bi
thc phm bng phng phap hoa tan.................................................................24
4.1.1. Xac nh cac vt liu bao bi..................................................................24
4.1.2. Kim tra vt liu....................................................................................25
4.1.3. Phng phap xac nhn..........................................................................27
4.2. p dung SPME trong nghin cu s chuyn dch VOCs trong bao bi thc
phm Polystyrene................................................................................................32
4.2.1. iu kin thit b...................................................................................32
4.2.2. LOD va LOQ........................................................................................33
4.2.3. Tuyn tinh.............................................................................................34
4.2.4. chinh xac.........................................................................................35
KT LUN............................................................................................................37
KIN NGH...........................................................................................................38
TI LIU THAN KHO......................................................................................39

vii

DANH MC BNG BIU

Bang 2.1. Cng thc mc in hinh........................................................................12

Bang 3.1 Danh muc cht phn tich va ni chun.....................................................14
Bang 3.2 Danh muc hoa cht...................................................................................15
Bang 3.3.Chun b dung dch hiu chun cho th nghim di chuyn......................18
Bang 3.4.anh gia cac thng s SPME...................................................................20
Bang 3.5. Bc song ring trong mu polystyrene..................................................24
Bang 4.1: So sanh hiu qua chit i vi nhng k thut chit khac nhau..............26
Bang 4.2. Nng cht phn tich trong cac mu thu c bng phng phap ni
chun (ISTD) va thm chun (SA)..........................................................................27
Bang 4.3: Nng thu hi t 10 loai mu...............................................................28
Bang 4.5. D liu cho mi hp cht th nghim da trn t l tin hiu nhiu.........29
Bang 4.7. Cac thng s cua hi quy binh phng nho nht cua 4 hp cht th
nghim 7 nng khac nhau................................................................................30
Bang 4.8. Nng cua cht phn tich trong cac mu PS khac nhau.......................32
Bang 4.9. D liu cho mi hp cht th nghim da trn tin hiu nhiu.................33
Bang 4.10. Tom tt cac kt qua th nghim tuyn tinh bng cach s dung HS-SPME
................................................................................................................................. 35
Bang 4.11. Mc nng khac nhau ap dung th nghim chinh xac..............35
Bang 4.12. anh gia chinh xac phng phap chit thu hi, p = 3......................36

viii

ix

DANH MC HNH NH

Hinh 1.1. S may sc ky khi.................................................................................4

Hinh 1.2. Ct nhi va ct mao quan..........................................................................5
Hinh 1.3. ng chit Headspace tnh..........................................................................7
Hinh 1.4. S chit mu t ng Headspace vao GC.............................................7
Hinh1.5. Cu hinh c in cua thit b P&T GC mao dn.........................................8
Hinh 3.1. Cc polystyrene vi vach anh du1 cm.................................................19
Hinh 3.2. Ph FTIR cua PS bowl (a) va PS container (b)........................................25
Hinh 4.1. So sanh phan ng bng k thut chit khac nhau, p = 6...........................25
Hinh 4.2. GC-FID tach cht phn tich 10g/mL trn mt ct DB-WAX, 30m, ID
0,25mm, day 0,25m. Peaks: 1 = Toluene, 2 = ethylbenzene, 3 = isopropylbenzene, 4 = n-Propylbenzene, 5 = 1,4-Diethylbenzene (ISTD)...................26
Hinh 4.3. Biu lng d cho (a) Toluene, (b) ethylbenzene; (c) isoPropylbenzene va (d) n-Propylbenzene vi gii han t (0.05, np-2) S res ..............31
Hinh 4.4. HS-SPME method. Peak: 1 = Toluene (45 ppb); 2 = Ethylbenzene (15
ppb); 3 = iso-Propylbenzene (5 ppb); 4 = n-Propylbenzene (5 ppb); 5 = 1,4Diethylbezene (ISTD, 5 ppb)...................................................................................33
Hinh 4.5. Biu tuyn tinh cht phn tich (a) Toluene, (b) ethylbenzene, (c) isoPropylbenzene; (d) n-Propylbenzene va vi gii han t (0.05, np-2), S res .............35

LI M U

Bao bi la mt loai san phm cng nghip c bit c dng bao goi va cha
ng, nhm bao v gia tr s dung cua hang hoa, tao iu kin thun li cho vic vn
chuyn, xp d, bao quan, tiu dng san phm. Bao bi ngay cang tr nn ph bin va c
ng dung trong mi lnh vc i sng, san xut va tiu dng
Trong san xut bao bi cng nghip, vt liu c trang mc in ma thng cha nhiu
cht co hai, cac dung mi hu c d bay hi. Do vy vic xac nh va kim soat lng
dung mi d bay hi trong bao bi gi vai tro rt quan trng, c bit trong lnh vc thc
phm.

CHNG 1: TNG QUAN V CC DUNG MI D BAY HI

1.1. Tng quan v dung mi

1.1.1. Khi nim dung mi
Dung mi la cht long co kha nng hoa tan cht rn, cht long hoc cht khi tao
thanh hn hp phn tan ng nht mc phn t hay ion gi la dung dch. Dung mi
thng dung ma chung ta gp hang ngay la nc. Dung mi thng dng co im si thp
va d dang bay hi
Phn loai dung mi.
1.1.1.1. Phn loi theo hp cht ha hc.
Da theo cu tao hoa hc, cac dung mi thng thng thuc vao loai cac hp cht
sau: hydrocacbon bo va thm, cac dn xut clo va nitro cua chung, cac ancol, axit
cacboxylic, este, amit, nitril, ete, xeton va sulfonic.
1.1.1.2. Phn loi theo cc hng s vt l
Nhng dung mi co nhit si di 100 0C 760 mmHg gi la dung mi co nhit
si thp, con vi nhit si cao hn 1500C gi la dung mi co nhit si cao.
Nhng dung mi co hng s in mi cao co tac dung nh nhng dung mi phn ly.
i khi ngi ta con gi dung mi phn cc va ngc lai la nhng dung mi co hng s
in mi thp gi la dung mi khng phn cc.
1.1.1.3. Phn loi theo tnh cht axit-baz.
Axit la nhng cht cho proton, con baz la nhng cht nhn proton. Khi axit HA hoa
tan trong dung mi baz thi cn bng acid baz c thit lp
1.1.1.4. Phn loi theo tng tc trc tip vi cht tan.
Theo Packer, co th chia dung mi thanh dung mi khng proton lng cc va
proton lng cc da vao tng tac c bit vi cac anion va cation. Trc ht phai k n
tinh lng cc va kha nng tao lin kt hydro. Co th b sung thm vao hai nhom mt
nhom th ba, nhom dung mi khng proton phn cc
1.1.1.5. Phn loi theo ngun gc dung mi.

2
Da theo cach phn loai nay, dung mi c chia thanh hai nhom: dung mi co
ngun gc du khoang va dung mi co ngun gc t thc vt, ng vt (hay con gi la
dung mi sinh hc)
1.1.2. Tnh cht vt l ca dung mi hu c.
Tinh cht vt ly cua dung mi la mt yu t quan trng khi la chn dung mi trong
cac ng dung. Trc tin, dung mi phai trang thai long di ap sut va nhit ma no
c s dung.
Cac tinh cht nhit ng cua dung mi nh: mt , ap sut bay hi, nhit tr va sc
cng b mt, nht, kha nng khch tan, kha nng dn nhit. Tinh dn in, tinh cht
quang hc, t tinh va momen lng cc, hng s in mi.
Ngoai ra, cac c im va phn t cua dung mi nh: kich thc, b mt, th tich cua
phn t dung mi cung c khao sat.
1.1.3.Tnh cht ho hc ca dung mi.
Tinh tr v mt hoa hc la iu kin tin quyt s dung mt cht long nh dung
mi. Hydrocacbon day bo va day thm la nhng cht hoa hc tr va thoa man iu kin
nay. Alcol la cht bn vng v mt hoa hc nhng lai phan ng vi kim loai kim, kim loai
kim th va nhm tao mui.
Este va xeton la nhng cht hoa hc kha bn vng trong iu kin binh thng.
1.1.4. Cc ch tiu nh gi cht lng dung mi hu c.
1.1.4.1. tan trong nc.(ASTM D1722).
Chi tiu nay xac nh tan cua dung mi trong nc. Mu o c pha loang 10
ln vi nc va hn hp nay c kim nh vn uc. Nu mu khng xut hin im vn
uc thi mu c anh gia la qua th nghim.
1.1.4.2. Ch s Kauri butanol. (ASTM D1133).
Php o gia tr Kauri butanol la php o im vn uc anh gia manh cua
dung mi hydrocacbon. Gia tr Kauri butanol cua mt dung mi th hin lng ti a
dung mi co th thm vao mt dung dch nha Kauri (mt loai nha copal) trong ru
butylic ma khng gy ra vn uc. Nha Kauri tan ngay vao ru butylic nhng khng tan
trong dung mi hydrocacbon, dung dch nha s chi tn tai trong mt gii han pha loang.
1.1.4.3. nht

3
nht la tinh cht cua mt cht long, c xem la ma sat ni tai cua cht long va
can tr s chay cua cht long.
Nguyn nhn gy ra nht la do ai lc c hc gia cac hat cu tao cac cht long.
nht ng hc la t s gia nht ng lc va t trng cua no (ca hai c xac nh
cng nhit va ap sut).
1.1.4.4. Tnh n mn
Th nghim n mon tm ng c s dung xac nh kha nng n mon tm ng
cua dung mi. Th nghim nay nhm anh gia s co mt cua axit trong dung mi sinh hc.
1.1.5. ng dng
Dung mi hu c c s dung rng rai hoa tan va phn tan cht bo, trong du,
sap, bt mau, sn du, cao su va cac cht khac.
Thng c s dung trong sn,vecni, sn mai, sap, cht anh bong san nha va giay,
keo, nhin liu, cht chng ng, ty du m, lam sach va cac lam kh mc in. Cac san
phm dc phm va thuc tr su, cht bao quan, quy trinh phong thi nghim
1.1.6. Ngun pht sinh nhim VOCs
Ngun phat sinh nhim VOCs do t khng trit xng du, cac dung mi hu c
t bay hi, bay hi cua xng du va hoa cht ri vai. Nhin chung, xng va sn la hai th
phat xa VOCs nhiu nht. Chung it gy c man tinh ma chu yu gy c cp tinh nh
chong mt, say nn, sng mt, co git, ngat vim phi. Chi mt s it cht co kha nng gy
c man tinh nh ung th mau, bnh thn kinh.
Ngoai ra, cac san phm m phm, du mo, nha, keo dan cng nghip, thuc tr su
va cng ngh in cung la nhng ngun phat sinh dung mi hu c d bay hi d9o61i vi
mi trng
1.1.7. c tnh ca cc dung mi hu c d bay hi
1.1.7.1. Con ng xm nhp dung mi vo
Hu ht cac dung mi hu c bay hi nhit thng va c hp thu qua da,
phi va mt
1.1.7.2. nh hng mt s dung mi hu c d bay hi trong bao b
Hp cht VOCs hin din trong cac bao bi nha co th anh hng sc khoe con
ngi.

4
Ethylbenzene la mt hoa cht tng hp quan trng c san xut vi s lng
ln nh la mt tin cht styrene va polystyrene. No c hp thu qua da, phi va ng
tiu hoa va gy kich thich mt, da va nim mac. Ethylbenzene la cht gy ung
th c bit n da trn cac nghin cu trn ng vt nhng bng chng khng y u
ngi. IARC phn loai ethylbenzen nh cht gy ung th nhom 2B
1.2. Tng quan v sc k kh
1.2.1. Gii thiu v sc k kh
Sc ky khi c dng phn tich cac cht tng i d bay hi (t s 3500C) va bn
nhit. Pha ng la khi mang, cac khi nay gn nh tr nhit ct sc ky nh He, N 2, Ar,
N2
Pha tnh la cac cht bn nhit khng bc hi nhit ct sc ky. Trong sc ky khi
thi pha tnh ong vai tro chinh trong vic tao nn tng tac cn thit cu t c tach ra
khoi nhau. S thay i pha tnh hoc cac thng s lam vic s anh hng n lc tng tac
gy nn s tach
1.2.2. Thit b trong sc k kh

Hinh 1.1. S may sc ky khi

1.2.2.1. Kh mang (pha ng)
Khi c chn lam khi mang phai ap ng cac yu cu: tr vi cu t khao sat, t
khi nho lam tng vn tc khi mang, tn tai dang tinh khit. Khi xt quan h gia
chiu cao a ly thuyt H va vn tc tuyn tinh cua dong khi mang, la chn khi mang cho
cc tiu cang trai rng cang tt
Cac loai khi mang thng dng la He, N2, Ar, N2
Khi hydro thng mai u tiu chun cho sc ky khi. Khi s dung hydro lam khi
mang nn cn dng N2 lam khi bao v thi qua ct trc.

5
Khi He la khi tr hoa hc rt thich hp cho sc ky khi nhit cao, khi s dung
detector ion hoa bng tia phong xa phai la khi khng co hoat tinh hoa hc c dng cho
sc ky nhit cao.
Khi N2 khng nguy him, gia r va d dang lam tinh khit nn N2 s dung rt nhiu
trong sc ky khi
1.2.2.2. Ct sc k
Ngi ta chia ct sc ky khi lam 2 loai ct tach:
Ct nhi co chiu dai L: 0.53m, ng kinh trong 24mm bng thuy tinh hay kim
loai (inox) hoc thm teflon, bn trong ct c nhi y vi hat rn tinh cu, din tich
ring > 1m2/g (dp = 100-120mesh = 150-250m). Hat c phu mt lp cht long kho bay
hi. Hiu nng ct cang ln khi ng kinh dp cang nho
Ct m (ct mao quan) thng c lam bng fused silica co tinh bn v mt vt ly
va tr v mt hoa hc, vi ng kinh trong 0.1-0.53mm, ct mao quan co chiu dai 1230/60/100m. Ct mao quan chia lam 3 loai ct: ct WCOT, ct PLOT, ct SCOT

Hinh 1.2. Ct nhi va ct mao quan

1.2.2.3. Cht rn hp ph (pha tnh)
Pha tnh s dung cho sc ky khi phai ap ng yu cu: it bay hi, bn nht, tr v
mt hoa hc, pha tnh va ct cn co phn cc tng t nhau
Gm 2 dang: pha tnh rn va pha tnh long
1.2.2.4. Phng php tim mu
Injector hay bung tim la v tri tai o mu s c hoa hi va a vao ct sc ky
theo s li cun dong khi mang. Cac loai bung tim mu c chia lam 2 nhom chinh la

6
injector cho ct nhi va in jector cho ct mao quan. trong mi nhom lai chia thanh nhiu
loai khac nhau tu thuc muc ich phn tich, loai mu va th tich mu tim
1.2.3. K thut tim mu Headspace
Headspace la khng gian khi trn mu trong mt l sc ky. Cac thanh phn mu d
bay hi khuch tan vao giai oan khi, tao thanh khi Headspace. Phn tich headspace la
phn tich cac thanh phn co mt trong khi o.
1.2.3.1. ng dng
Phn tich ham lng hp cht hu c d bay hi (VOCs) trong cht long, rn bng
cach gia nhit nhit thp. Trong cng nghip, k thut tim mu Headspace thng
c dng trong phn tich d lng dung mi trong cac san phm in, nha, keo dan
1.2.3.2. Nguyn tc
Trc khi tim mu long hoc rn c cho vao mt ng ng mu kin, mu thng
chim di 50% th tich ng va ng thng co th tich 10 hoc 20mL. ng ng mu
c t trong mt lo gia nhit co th kim soat nhit chinh xac ti hn 1 0C hoc tt
hn. Sau o, ng c gi nhit gia nhit trong mt thi gian nht nh, sau o phn
hi c hut ra va tim mu vao cng tim mu. Co th tim mu bng tay vi syring khi
hoc tim mu t ng bng h thng chuyn dung.
Nhit lo gia nhit thng khoang 35-2000C
1.2.3.3. Phng php chit Headspace
Mt tinh nng quan trng cua phn tich VOCs la trong nhiu trng hp cht phn
tich la ln u tin chuyn sang pha khi hi va sau o c phn tich bi mt thit b. Sc
ky khi (GC) la phng phap cng cu c la chn cho vic tach va phn tich cac hp
cht d bay hi.
Tuy nhin, vic phn tich tr nn kho khn khi cac cht phn tich b hoa tan hay hp
phu trong mt mu phc tap nh m phm, polyme, dc phm hay nguyn vt liu. Yu
cu trich xut cac cht phn tich va xac nh chinh xac khi lng hoc nng cua chung
Cac phng phap chit Headspce bao gm: chit Headspace tnh (SHE), chit
Headspace ng (purge & trap), chit vi pha rn (SPME), chit sut mang va chit cht
long. S la chn cua k thut phu thuc vao loai mu, thng tin yu cu (v s lng
hoc cht lng), nhay, cn t ng hoa va gia thanh.
Phng phap chit Headspace tnh (SHE)

7
Phng phap chit Headspace tnh con c gi la chit cn bng Headspace. y la
mt trong nhng k thut ph bin nht cho cac phn tich nh tinh va nh lng cua cac
hp cht hu c d bay hi t nhiu mu.
Phn tich Headspace tnh bao gm hai giai oan. u tin, mu long hay rn c
a vao mt ng kin th tich 10 hoc 20mL c iu khin nhit khng i cho n
khi at trang thai cn bng gia hai pha. Sau o, phn phn c cua pha khi trong l theo
dong khi mang vao ct va c phn tich theo cach thng thng.
Vic chuyn mu vao ct co th c thc hin bng mt s cach: bng tay nh s
dung ng tim kin khi, hoc t ng bng cach ap lc ln l mu va kim soat thi gian
hoc lng pha khi cua headspace vao ct.

Hinh 1.3. ng chit Headspace tnh

Hinh 1.4. S chit mu t ng Headspace vao GC

Phng phap chit HeadSpace ng

8
K thut headspace ng chu yu la phng phap chit khi lin tuc va phn bit
thanh phn mu d bay hi t nn bi mt dong lin tuc cua khi tr phia trn mu long hay
rn hoc bng s suc khi qua thuy tinh kt dinh mt l cao qua mu long, tt nht la qua
dung dch nc. K thut nay c gi la lam sach va by (P&T). B mt tip xuc ln cn
thit chuyn nhanh chong lng t nn mu (nc) lam sach khi va cac a thuy tinh
cho ra cac bong bong khi nho.
tng c ban cua P&T la tach hoan toan hi cn phn tich t mu sn sang
phn tich nh lng trong khi chit cui cng. Nh vy qua trinh chit trit theo cp s
nhn va do o mt mt thi gian. Cac hi c lam sach phai co mt trong khi chit loang
va tp trung trong mt cai by. iu nay co th la mt cai by lanh, hp kin vi vt liu
hp phu c s dung ma t o cac hp cht b gi lai thoat ra nh giai hp nhit va
chuyn vao ct bi dong khi mang.
Tc cao cn thit at c chit hoan toan t mu trong thi gian ngn nht.
iu nay oi hoi mt cai by u kha nng tranh chc thung trong thi gian chit. Qua la
mt cai by nh vy co chung kich thc cua mt ct ngn va chp nhn t l dong chay
so sanh, vi du 20-40mL/phut cho hp phu va giai hp. Tenax, mt polymer xp la vt
liu hp phu ph bin. No la cht hp phu yu, c bit la cn phai bao quan tranh s
pha huy cua cac hp cht bay hi. Lng b pha huy c phat hin bi Kroupaetal trong
khoang nhit t 100C n 1700C.
S bao quan cn thit nu cai by nhi vi nhiu cht giai hp khac nhau trong nhom
cng gc vi tinh hp phu tng dn, tao thanh chng trinh hp phu cac cht d bay hi
ni cac hp cht d bay hi nht b hp phu cui cng vao vt liu hp phu vao vt liu
manh nht va kt thuc qua trinh a hp thu. Cac hp cht b gi lai sau o b kh bi nhit
va quay lai ct mao dn nhng thng b gi lai tp trung trong mt cai by nhit thp

Hinh1.5. Cu hinh c in cua thit b P&T GC mao dn

9
1.2.3.4. Phng php chit vi pha rn (SPME)
Vic chuyn mu vao ct co th c thc hin bng tay hoc t ng bng cach ap
lc ln l mu va kim soat thi gian hoc lng pha khi cua headspace vao ct. Thay vi
chuyn trc tip phn khi headspace vao ct, k thut mi bao gm vic thm cac by hp
phu.
1.2.3.5. Detector
Mt s detector s dung trong sc ky khi:
Detector ion hoa ngn la (FID)
Detector cng kt in t (ECD)
Detector dn nhit (TCD)
Detector quang hoa ngn la FPD

10

CHNG 2: GII THIU V BAO B V MC IN

2.1. Gii thiu v bao b

2.1.1. nh ngha
Bao bi la mt loai san phm cng nghip c bit c dng bao goi va cha
ng, nhm bao v gia tr s dung cua hang hoa, tao iu kin thun li cho vic vn
chuyn, xp d, bao quan va tiu thu san phm.
2.1.2. Chc nng cng ngh v tiu dng
Chc nng bao quan va bao v hang hoa: Bao bi la bao v hang hoa, han ch
nhng tac ng cua cac yu t mi trng n hang hoa trong sut qua trinh t khi hang
hoa c san xut ra cho n khi hang hoa c tiu thu. Bao bi c s dung bao goi
va cha ng hang hoa, no la yu t u tin, trc tip tip xuc vi hang hoa, nhm am
bao hang hoa v cht lng va s lngva ngn cach san phm vi mi trng
2.1.3. Mt s loi mng bao b thng dng
2.1.3.1. Polystyrene (PS)
c san xut t du th bng phng phap trng hp styrene. PS thi hoan toan
trong sut nhng tinh ngn can m va khi thp. PS cng nhng khang va p thp vi
th ngi ta thng trn no vi loai cao su tng hp butadien tng thm bn va
cham.
2.1.3.2. Polyethylen (PE)
Hin nay PE tr thanh quan trng nht trong tt ca cac loai vt liu nha. PE c
phn loai thanh cac nhom chinh sau:
-

LDPE - PE mt thp, ti trng 0.91- 0.925g/cm3

MDPE (LLDPE: Linear) - PE mt trung binh, ti trng 0.926 - 0.940g/cm3
HDPE - PE mt cao, ti trng 0.941- 0.965g/cm3

2.1.3.3. Polypropylen (PP)

11
La mt loai nha olefin khac. No cng hn PE, co chu cng gian tt hn va trong
sut hn. Gia tr cua tinh thm hi m thp. Do kt tinh cao, nhit lam mm khoang
150oC nn no c s dung thanh cng khi tit trng cac san phm y khoa trong ni hp
2.1.4. Bao b thc phm
Bao bi thc phm ong mt vai tro quan trng thuc y an toan vn chuyn, phn
phi va lu tr thc phm. Bao bi lam cho thc n tin li hn cho vic bao am an toan
v sinh thc phm, thay i hoa sinh va thi gian s dung cac loai thc phm ong goi dai
hn. Trong xa hi hin ai, vt liu ong goi cung c s dung cho vic chun b thc
phm va thc phm ong goi c t trong lo nng, lo vi song, va thm chi ca trong
nc si. Kt qua la, ong goi s tr thanh mt yu t khng th thiu trong lnh vc thc
phm.
2.2. Gii thiu mc in
2.2.1. Khi nim
Mc in la mt cht mau c pha ch t nhiu thanh phn khac nhau dng tao ra
s tng phan v mau sc trn vt liu in qua khun in, no phai ph hp vi phng phap
in va tinh cht cua vt liu in.
2.2.2. Cu to, phn loi
Mc in offset la mt hn hp long quanh dang huyn ph, mn. Thanh phn cu tao
gm co: hat mau (pigment), cht lin kt, phu gia.
2.2.2.1. Pigment
Pigment la cac cht mau tao ra mau sc cho cho mc in, nu khng co pigment thi
khng tao ra mc in, mau cua pigment la mau cua mc. Pigment la nhng hp cht hu c
hoc v c co mau, co cng thc hoa hc khac nhau va chung co c im chung la khng
thm nc, khng tan trong nc, cn, kich thc siu mn (trong in offset ng kinh hat
pigment nho hn 1mm), ng thi pigment hu nh khng tan trong dung mi hu c,
khng co ai lc vi vt liu, vi cac nguyn vt liu san xut mc. Pigment quyt nh cac
tinh cht quang hc va bn mau cua mc in.
2.2.2.2. Cht lin kt
Cht lin kt la cac cht long t nhin hoc tng hp co tinh nht dinh, co kha nng
dan thanh mang mong trn b mt vt liu in va bam dinh chc vao o. Thanh phn cua

12
cht lin kt bao gm: cht tao mang (amino formandehit, phenol formandehit, du thc
vt, bitum, xenlc), dung mi hu c hoa tan cht tao mang (ru, cn, du khoang).
2.2.2.3. Cht ph gia
Cac cht phu gia: la cac cht cho thm vao mc lam tng tinh in cua mc
nh: lam tng- giam tc kh, tng hay giam bam dinh cua mc, tng hay giam kha
nng ngm cua mc trn b mt vt liu.
Thanh phn cac cht phu gia bao gm:
-

Cht du kh: cac mui kim loai nh Co, Mg, cac loai du lam thay i dinh.
Cac cht ngm: neocan... lam tng ngm cua mc.
Cac cht du m: lam tng bam dinh, bong cua mc
Cac cht phu gia c s dung phu thuc vao c trng cua tng qua trinh in.
La chn mc in ty thuc vao phng phap in, thit b in, tinh cht b mt vt liu

in, tinh cht san phm in.

Bang 2.1. Cng thc mc in hinh
Vt liu mang

Thanh phn (%V)

Pigment

12 15

Nha va amin

15 25

Cn

25

Phu gia

6 10
Nc

45 65

Cac thng s k thut cua mc: nht 25 30 st, pH: 8 9, sc cng b mt 35

38 dyn/cm
2.2.3. C ch bm dnh ca mc in ln bao b

CHNG 3: QUY TRNH XC NH DUNG MI D BAY HI

TRONG BAO B THC PHM POLYSTYRENE

13
3.1. Phm vi nghin cu
Pham vi nghin cu bao gm phng phap phat trin , phng phap xac nh va
phng phap ap dung th nghim mu. Cht phn tich c quan tm la cac dung mi
hu c d bay hi VOCs cu th la toluene, ethylbenzene, iso propylbenzene va npropylbenzene.
3.2. Phng php p dng
Phng phap rt n gian va d dang thc hin nh phng phap hoa tan va
phng phap hoa tan kt tua. Polymer c hoa tan trong dung mi hu c ph hp nh
dimethylformamide (DMF), dimethylacetamide (DMA), hoc dichloromethane (DCM).
Mt phn dung dch mu c tim trc tip vao GC-FID bng cach s dung ct mao dn
va chng trinh nhit thich hp. Trong phng phap hoa tan kt tua, methanol c thm
vao kt tua cac polymer, va mt lng nho cht b m t c tim vao GC.
3.3. nh gi k thut chun b mu
Vic chit cac hp cht d bay hi thng c thc hin bng cach s dung
Headspace (purge&trap), hoc k thut lam sach va by. Trong khi i vi mt hp cht
d bay hi va khng bay hi, chit long-long (LLE) va chit pha rn (SPE) thng c s
dung. Mt s k thut chit c in nh: chit Soxhlet va chit siu m vn con c s
dung. Tt ca nhng k thut co hiu qua, nhng co nhng han ch.
3.4. Cht phn tch v ha cht
Cac

dung

mi

bay

hi

la

chn

cho

nghin

cu

nay:

toluene, ethylbenzene (EB), iso-propylbenzene (IPB) va n-propylbenzene (NB)

Dung dch hiu chun ni b (ISTD): 1,4 diethylbenzene
Nc kh ion hoa a c chun b bng cach s dung mt h thng lc nc aqua
MAX-ultra

14
Bang 3.1 Danh muc cht phn tich va ni chun
Cht phn tich

Cng thc

Khi lng phn

t

Toluene
C6H5CH3

92

(99.9%)

Nhan hiu
Sigma-Aldrich
(Germany)

Ethylbenzene
C6H5CH2CH3
(99.8%)

Iso-Propylbenzene

106

C6H5CH(CH3)2
120

(99.9%)
n-Propylbenzene

C6H5CH2CH2CH3
120

(99.9%)
1,4diethylbenzene
(ISTD) (99.9%)

C6H4(CH2CH3)2
134

Bang 3.2 Danh muc hoa cht

Sigma-Aldrich
(Germany)

Sigma-Aldrich
(Germany)
Kanto Chemical
(Japan)
Sigma-Aldrich
(Germany)

15

Hoa cht

Cng thc

Phn loai

Tinh khit

Nhan hiu

99.8%

J.T. Baker (USA)

Utra Resi- Phn

Dichloromethane

CH2Cl2

tich lng cht

hu c con lai

Methanol

Potassium
chloride

CH3OH

HPLG

99.99%

Thuc th

99.5%

KCl

Fisher Scientific
(UK)

Scharlau Chemie
(Spain)

3.5. Thit b
Sc ky khi Shimadzu (Kyoto, Japan) GC-17A detector ion hoa ngn la (GCFID) b tim mu t ng Shimadzu AOC-20i.
Cac d liu sc ky a c phn tich va x ly bng chng trinh Shimadzu Class-VP
Nicolet 5700 (USA)

Fourier chuyn

ti

quang

ph

hng

ngoai (FT-

IR) c trang b tt dn phan xa toan phn (ATR) a c s dung xac nh

cac loai vt liu ong goi.
3.6. Phng php kim tra vt liu
3.6.1. Chun b dung dch chun
Dung dch chun gc 10g/ml trong dichloromethane (DCM).
Dung dch chun th hai a c chun b bng cach pha loang dung dch chun gc
trong DCM v nng 1g/mL.
Dung dch gc 1,4-diethylbenzene (ISTD) a c chun b bng cach hoa tan dung
dch chun trong DCM nng 10 g/mL.
Dung dch 100g/mL ISTD a c chun b bng cach pha loang dung dch
gc trong DCM va dung dch nay a c s dung cho vic hiu chun dung dch mu

16
Dung dch hiu chun nng t 0,4-80g/mL c chun b bng cach pha loang
dung dch chun th hai trong DCM va thm 1 ml dung dch ISTD nng 100g/mL
(tng ng vi 10g/mL) cho mi cp cua dung dch tiu chun.
3.6.2. Chun b mu- k thut ha tan
Mu hang hoa bao bi thc phm Polystyrene thu c t cac siu th. Cac mu
ly khng tip xuc vi thc phm.
Mu c ng nht va xac nhn la vt liu ong goi polystyrene bng FT-IR trc
khi kim nghim. Mu c t trc tip trn ca s ATR va a c qut trong khoang
bc song 4000 cm-1 n 400 cm-1. Cac ph hng ngoai thu c c mu c vi th
vin FT- IR (HR Hummel Polymer va phu gia, Th vin mu Hummel Polymer) xac
nhn cac loai polymer cac vt liu ong goi
3.6.3. iu kin sc k kh
Phn tich sc ky khi c thc hin vi h thng sc ky khi u do FID. H thng
GC-FID c trang b vi ct mao dn DB-WAX (30 m; ng kinh 0,25mm vi day
mang 0,25m ).
Nhit bung tim va detector tng ng 220 0C va 2600C. Nhit ct c gi
400C trong vong 3 phut, sau o tng 100C/phut n 120C va tip tuc tng ln n 2500C
400C /phut, nhit c gi 2500C trong 5 phut.
Khi mang heli co tinh khit 99.99%, tip tuc tinh ch bng cach i qua thit b
lam sach khi ry phn t 5A va oxy hp phu khi lc.
u vao c hoat ng trong chng chinh chia dong vi t l chia dong 10:1, tc
chia dong 10 ml/phut.
3.6.4. Phn tch v nh lng
Mu polystyrene sau khi chit c t trong ngn ly mu t ng va 1L dch
chit c tim trc tip vao GC thng qua tim mu t ng. Cac hp cht th nghim a
c xac nh bng cach so sanh thi gian lu (RT) so vi cac cht tiu chun.
nh lng xac nh lin quan n vic s dung 5 im trn ng cong ni
chun va khoang chun dao ng t 0,4-80g/mL. ng cong hiu chun c hin th
trn biu bng cach v t l din tich peak cao nht (din tich peak mu /din tich peak
1,4 diethylbenzene)

so vi t

l nng

(nng

cht

phn

tich

/nng

17
1,4 diethylbenzene) bng cach s dung chng trinh Shimadzu Class VP. Mt ng
cong hiu chun mi c tao ra cho mi l mu phn tich
Da trn ng cong hiu chun, nng cht phn tich (g/mL) a thu c. Vi
vy, nng thc cua cht phn tich trong mu (g/g) c tinh theo cng thc:
C ( g / g )

C ( g / ml )
V (ml )
m( g )

3.6.5. Qun l cht lng php o

Cac bin phap kim soat cht lng c thc hin cho hang loat mu phn tich.
Kim soat bao gm kim tra hiu sut thit b va chit thu hi. i vi mi l mu, chun
b ng thi mu blank va phn tich am bao khng nhim tap t thuc th va thuy tinh
c s dung.
Chun b dung dch chun 10g/mL tng t mu QC. Cac mu QC a c tim
vao luc bt u va kt thuc cua tt ca mu chay hang loat, va s khac bit trong thi gian
lu va din tich peak cua cht phn tich cua chun va mu c tinh toan.
S dung GC-FID nu s thay i thi gian lu it hn 5% va s khac bit din tich
peak it hn 20%. Chit thu hi c thc hin bng cach spiking mu vi 1 ml 100mg/mL
chit chun trc khi tin hanh chit mu. Mt mu a c phn tich vi tt ca cac hang
loat cac mu
3.7. Phng php HS-SPME
3.7.1. Chun b dung dch chun
Dung dch gc cua mi hp cht th nghim va dung dch chun c chun b bng
cach pha loang dung dch trong methanol.
Dung dch gc va dung dch trung gian cua 1,4 diethylbenzene (ISTD) a c
chun b tng t nh cac hp cht th nghim.

18
Bang 3.3.Chun b dung dch hiu chun cho th nghim di chuyn
Hp cht

Dung dch gc (g/mL)

Dung dch chun phu (ng/mL)

Mc 1

Mc 2

Mc 3

900

4.5

22.5

67.5

300

1.5

7.5

22.5

100

0.5

7.5

7.5

100

0.5

2.5

7.5

200

5.0

5.0

5.0

Toluene

Ethylbenzene

iso-Propylbenzene

n-Propylbenzene

1,4-diethylbenzene

Bang 3.3 cho thy nng cua mi hp cht th nghim va ISTD cho dung dch
chun gc va phu. Hiu chun bng 10 ml nc tinh khit kh ion hoa vi 10mL lng
khac nhau dung dch chun phu va ISTD, cac dung dch nay a c s dung hiu
chun
3.7.2. Dng thc phm v iu kin ty ra
Nc c chn lam dung dch ra giai ai din cho nhom thc phm co
pH =4,5 va cao hn. Dung dch ty ra c chun b bng cach nung nong nc tinh
khit kh ion hoa bng cach s dung b nhit cn thit cho vic nghin cu dch
chuyn.
Th nghim dch chuyn c thc hin 3 nhit khac nhau: 240C (nhit
phong thi nghim), 600C va 800C va thi gian u 30 phut. Lo khng khi nong c s dung
duy tri nhit 600C va 800C.
Cac iu kin lc c s dung hoc nhit phong trong 30 phut, hoc duy tri
nhit cua dung dch ra giai s dung va gi trong 30 phut.
3.7.3. Chun b mu

19
Dung tich cua mi mu (C) c xac nh bng cach lam y cac mu th bng
nc ln n 1cm vanh anh du t phia trn cng cua mi mu nh hinh. Nc sau o
c chuyn vao xi lanh o dung tich cua mi mu th nghim.
Hinh 3.1. Cc polystyrene vi vach anh du1 cm

Mu a c lam y vi dung dch ra giai, o dung tich (C) cua mi mu va lu

gi tai nhit phong hay nhit cua dung dch ra giai s dung trong 30 phut.
3.7.4. Chit HS-SPME
Cac cht phn tich c chit vi k thut HS-SPME bng cach s dung si PDMS
100m va l Headspce 22mL. Si quang c gi b tim 2500C trong 30phut. Phn
phn c cua 10mL dung dch th nghim c t trong ng headspace 22mL va 10L
ISTD 5 g/mL c thm vao ng.
Sau khi t thanh stir dai 0.8cm vao trong ng, bt kin bng np Headspace vi vach
ngn phu PTFE. Lc manh ng trong vai giy va nhit phong trong 5phut. Sau
5 phut u, si quang c a vao ng va t trn khoang 2mm so vi mu long
Thi gian chit 5 phut mu khuy lin tuc 800 rpm tng qua trinh cn bng. Sau
khi chit kt thuc, si quang ngay lp tc c rut ra va bo vao vo bc bao v, chuyn
vao voi phun cua sc ky khi giai hp nhit
3.7.5. Thit b
Cng tim mu sc ky khi ID 0,8 mm phn tich SPME.
Cac thng s thit b c thit lp ging nh cac kim tra vt liu vi cac trng
hp ngoai l la cac voi phun a c lp trinh chia dong 0,5 phut sau khi bt u chay
phn tich va thi gian gi nhit cui cng cua ct 2500C a c rut ngn n 2 phut.
3.7.6. Phn tch v nh lng

20
Si quang c giai hp nhit voi tim 2200C trong vong 3 phut va bt u phn
tich. Cac cht phn tich c tach ra bng ct mao quan va xac nh bng detector FID.
Hiu chun bng phng phap ni chun bng cach s dung 3 mc ng cong hiu
chun. Si blank a c a vao luc bt u chay va kt thuc cua tng l am
bao khng co hiu ng b nh
3.7.7. Ti u ha cc tham s SPME
Khi lng mu, cng elutropic, nhit va thi gian chit, tc khuy, anh
hng ham lng mui va thi gian giai hp a c nghin cu co c cac iu kin
ti u cho hiu qua chit tt nht.
Bang 3.4.anh gia cac thng s SPME
Thng s SPME

Bin s

Pham vi

Th tich (mL)

5, 10, 15

Methanol (%)

0.1, 0.5, 1, 5, 15

Chit xut

Nhit (0C)

24, 40, 60, 80

Chit xut

Thi gian (phut)

Lng mui ra

KCl thm vao

Khuy trn mu

Tc khuy (RPM)

Giai hp

Thi gian (phut)

Lng mu
Cng
elutropic

1, 5, 15, 30, 35, 45

vi KCl 30% hoc khng co KCl
0, 200, 400, 600, 800, 1000
1, 3, 5

3.8. Phng php xc nh

Mt s c im c trng a c anh gia chng minh s ph hp cua phng
phap cho nhim vu phn tich, va am bao rng d liu phn tich chinh xac va nht quan co
th thu c vi phng phap xac nhn.
3.8.1. c im
Th nghim nay c da trn tiu chun b sung cua cac hp cht quan tm. Nng
cua cac hp cht c thm vao trong pham vi cua phng phap nay. Mt tiu chun b

21
sung c thc hin cho mi mu va nng bao gm cac nng d kin cua mu va
khac nhau trong pham vi cua phng phap.
c im c xac minh bng cach iu chinh mt ng thng gia nng thm
vao (v) va thu hi (r) nng trong ng hi quy:
r a b

3.8.2. Gii hn pht hin v gii hn nh lng

Co mt vai cach anh gia LOD va LOQ. Ba cach cu th la t l tin hiu nhiu, xac
nh blank va phng trinh hi quy tuyn tinh da trn ICH va EURACHEM hng dn
c anh gia cho LOD, LOQ kim tra vt liu.
3.8.2.1. T l tn hiu nhiu
Bng cach s dung phng phap o tin hiu nhiu, ghi nhn peak trong thi gian lu
cua cht phn tich c o, va sau o, nng cua cht phn tich c ghi nhn bng tin
hiu nht nh va t l nhiu c c lng. Trong nghin cu nay nhiu c o
bng may tich phn t ng, 3 tin hiu nhiu c dng xac nh LOD va 10 tin hiu nhiu
c dng xac nh LOQ
3.8.2.2. Xc nh blank
LOD c th hin nh nng cht phn tich tng ng vi gia tr mu blank cng
vi ba lch chun va LOQ la nng cht phn tich tng ng vi gia tr mu blank
cng vi lch chun nh th hin trong cac phng trinh di y:
LOD xb1 3S b1

LOQ xb1 10 S b1

Trong o: xb1 nng mu blank, Sb1 lch chun mu blank

3.8.2.3. Phng trnh hi quy tuyn tnh

Trong ng cong hi quy tuyn tinh, gia tr hi quy y vi nng chun x nm
trong pham vi gii han nng . No c biu din nh sau:
y = a + bx
Phng trinh nay c s dung tinh toan nhay b va LOD, LOQ. Do o, LOD
va LOQ co th c th hin nh sau:
LOD

3S a
b

22

LOQ

10 S a
b

Trong o: Sa lch chun y, b la h s goc ng cong hiu chun

3.8.2.4. Kim tra gii hn nh lng xc nh
Kim tra am bao rng cac gia tr LOQ thu c t ba phng phap a at c.
Phn tich ring dung dch chun mc 10 ln LOQ vao nhng ngay khac nhau (p = 10),
trung binh va lch chun, S QL cua 10 ln o c tinh toan.
Cac iu kin sau y phai c ap ng theo th t cho gia tr LOQ c coi la
chp nhn. Gia tr trung binh o lng xQL khng khac nhau t cac gii han nh lng
LOQ a xac nh
-

Nu gia tr trung binh o lng xQL khng khac nhau t cac gii han nh lng
LOQ a bit
LOQ xQL
10
S QL
: LOQ c chp nhn
n

Nu 5 S QL <LOQ: LOQ phai khac 0

3.8.3. tuyn tinh

Phng phap c s dung anh gia khoang tuyn tinh c da trn hng dn
IUPAC. Mt loat cac dung dch hiu chun a c chun b cac nng khac nhau. Cac
dung dch chun a c chun b mi ngay va phn tich trong khoang thi gian cua ngay.
D liu thu c thich hp hi quy binh phng nho nht (OLS) va h s goc (b),
giao im (a), lch chun cua h s goc (Sb), xac nh h s tuyn tinh r2 c c tinh
bng cach s dung chc nng LINEST cua chng trinh Microsoft Excel. Mt khi cac
thng s c c tinh, cac m hinh phai c xac nhn bi cac phng tin th nghim
m hinh hi quy (Freg), th nghim Flof va cui cng kim tra (t-test) xac nhn y-giao
nhau qua im gc.
3.8.4. chnh xc
T matrix blank khng co sn cho th nghim nay, nghin cu thu hi c s dung
anh gia tinh chinh xac cua phng phap ap dung. Mu c cung c vi ba cp cua
dung dch tiu chun va phn tich cng vi cac mu khng cn lp thanh hai ban.
chinh xac a c anh gia da trn dung cu chinh xac va phng phap chinh
xac:

23
Cac phng trinh sau y c s dung tinh toan lp lai.
q

Sr

w
i 1

2
i

2n

Trong o: S r : lch chun lp lai

n: s lng mu th nghim
wi : lch tuyt i

lp lai r 2.8S r
3.9. Phn tch d liu
Microsoft excell (2003) a c la chn lu tr, hin th d liu va thc hin cac
tinh toan thng k vi cac tich hp chc nng thng k.

24

CHNG 4: PHNG PHP PHT TRIN V PHNG PHP P

DNG XC NH HP CHT HU C D BAY HI TRONG
BAO B THC PHM POLYSTYRENE

4.1. Phng php pht trin xc nh hp cht hu c d bay hi trong bao b thc
phm bng phng php ha tan
4.1.1. Xc nh cc vt liu bao b
Co nhiu loai khac nhau cua vt liu ong goi c s dung cho cac ng dung thc
phm. Rt kho phn bit cac loai vt liu da trn cac quan sat vt ly bao bi. Ngoai ra,
khng phai tt ca cac goi thc phm thng mai co cha ma cu th xac nh, ma nay
thng c in hoc dp ni tai c s cua cac hp polystyrene hoc cho cac muc ich tai
ch.
Bang 3.5. Bc song ring trong mu polystyrene
Nhom chc

Bc song (cm-1)

-CH2-

2919 2921

-CH-

2848 2850

C=C

1451; 1492; 1601

Peaks 1451, 1492 va 1601 cm-1 c trng cho lin kt C=C. Peak nm trong khoang
bc song 2919 - 2921 cm-1 lin kt CH2, trong khi peak 2848 - 2850 cm -1 do lin kt
CH. Cac quang ph hng ngoai cua cac mu c so sanh vi quang ph c xy dng
trong th vin FTIR xac nh polystyrene trong cac mu.

25

(a)

(b)
Hinh 3.2. Ph FTIR cua PS bowl (a) va PS container (b)
4.1.2. Kim tra vt liu
Kim tra vt liu c s dung xac nh VOCs con lai hin din trong cac san
phm thc phm ong goi thanh phm. Trong nghin cu nay, cht phn tich c la
chn cu th la toluene, ethylbenzene, iso-propylbenzene va n-propylbenzene.
4.1.2.1. Chun b mu
Cn c vao phng phap hoa tan, mt cach n gian va hiu qua phn lp va xac
nh toluene, ethylbenzene,

iso-propylbenzene va npropylbenzene trong

bao

bi thc

phm polystyrene.
Dung dch mu thu c bng cach s dung ba k thut phn tich bng GCFID trong 6 ln lp lai va kt qua c hin th trong hinh 4.1.

26

Hinh 4.1. So sanh phan ng bng k thut chit khac nhau, p = 6

Hiu qua chit T1 c gia nh 100%, va c s dung lam c s cho tinh toan hiu
qua chit T2 va T3. Kha nng chit T1 thp hn T2 va T3 cua tt ca cac cht phn tich. Do
mt

s cht

phn

tich a b

by trong polymer trong bc kt

tua. Bc ly

tm trong T3 tip tuc lam giam hiu qua chit la s giam cht phn tich xay ra trong qua
trinh chuyn dung dch mu t ng kinh vao ng ly tm.
Bang 4.1: So sanh hiu qua chit i vi nhng k thut chit khac nhau
Cht phn tich

Hiu qua chit

T1

T2

T3

Toluene

100

64

59

Ethylbenzene

100

56

54

iso-Propylbenzene

100

54

53

n-Propylbenzene

100

84

77

4.1.2.2. iu kin sc k
Cac thng s GC a c ti u hoa tach cac cht phn tich vi nhay tt hn.
ra giai 4 cht phn tich la toluene, ethylbenzene, iso-propylbenzene, n-propylbenzene
va cui cng 1,4 diethylbenzene (ISTD). Tt ca cac cht phn tich c tach ra trong
vong 13 phut va tng thi gian thc hin cho mi ln chay la 19,25 min.

27

Hinh 4.2. GC-FID tach cht phn tich 10g/mL trn mt ct DB-WAX, 30m, ID
0,25mm, day 0,25m. Peaks: 1 = Toluene, 2 = ethylbenzene, 3 = iso-propylbenzene, 4 =
n-Propylbenzene, 5 = 1,4-Diethylbenzene (ISTD)
4.1.2.3. Phng php nh lng
1,4diethylbenzene c s dung nh cht ni chun tng t nh cac cht phn
tich, hp cht nay a c th nghim cng vi cac cht phn tich trong iu kin chit va
tach nh nhau, cht ni chun c tach ra t cac cht phn tich.

28
Bang 4.2. Nng cht phn tich trong cac mu thu c bng phng phap ni chun
(ISTD) va thm chun (SA)
Nng trung binh, mg/kg (p=2)
N

Toluene

Ethylbenzene

isopropylbenzene

n-propylbenzene

ISTD

SA

ISTD

SA

ISTD

SA

ISTD

SA

26.34*

37.51*

55.11

76.41

45.26*

55.02*

31.49*

44.43*

139.54*

128.80*

82.93

77.98

27.06*

23.91*

13.46

9.43

23.72

22.40

54.55

49.50

9.18

9.81

26.40*

26.71*

27.58

24.78

21.58*

20.04*

14.36

15.77

8.49

10.58

47.46

56.07

41.32

47.79

8.06

9.15

25.54*

22.49*

32.97*

26.82*

119.73

119.93

30.47*

26.82*

28.80*

27.07*

20.37*

25.71*

14.72

23.05

21.65*

26.05*

21.50*

26.11*

19.56*

19.12*

33.68

35.36

9.37

10.00

23.83*

22.59*

17.66*

17.57*

247.14

275.04

35.50

31.34

26.03

20.80

10

20.75*

17.53*

61.11

58.82

14.23

17.55

24.11*

24.95

Bng cach s dung phng phap ni chun, anh hng cua s thay i cac li khng
kim soat ngu nhin co th c sa cha khng ging nh cac phng phap thm chun,
do o giup cai thin chinh xac cua cac phn tich nh lng.

4.1.3. Phng php xc nhn

4.1.3.1. c trng
Cac c trng cua phng phap anh gia am bao rng cac phng phap phat
trin o lng chinh xac va cht phn tich quan tm n s hin din cua cac thanh phn
khac trong

cac

mu bao

trn phng phap thm chun.

bi polystyrene.

Cac thi

nghim c

trng

da

29
Bang 4.3: Nng thu hi t 10 loai mu
Mu
n=10

Nng cht phn tich thu hi

Nng
thm, mg/k

Ethyl

iso-Propyl

n-Propyl

benzene

benzene

benzene

Toluene

Thia kem

19.98

20.50

22.54

20.83

22.17

Hp sushi

19.99

18.47

20.93

18.52

19.25

Da nho

20.00

20.75

15.41

16.41

17.50

Da

199.80

232.23

219.30

225.57

231.57

Thia o

200.00

188.01

187.47

183.49

192.87

Hp son

399.52

373.65

380.71

386.93

392.42

Thia

399.60

362.84

366.04

369.06

368.56

Na

399.76

431.96

440.25

427.62

425.60

Ly kem

400.00

362.77

357.17

358.54

377.05

Da EPS

999.50

1118.73

1125.84

1122.85

1117.49

4.1.3.2. Xc nh LOD v LOQ

Ba cach ap dung xac nh cac LOD va LOQ la xac nh blank, t l tin hiu nhiu
va phng trinh hi quy tuyn tinh. i vi muc ich so sanh, DCM c s dung nh la
mt

mu trng. Mc

nng

cho mi hp

cht va

s ln

lp

lai

cac

o c thc hin bng cach s dung cac phng phap khac nhau

4.4. Nng cht phn tich va lp lai xac nh LOD va LOQ

Phng phap

Mc g/mL, n

lp lai, p

Gia tr o, np

Tin hiu nhiu

0, 0.4

10

20

php

30

Xac nh blank
Hi quy tuyn tinh

0, 0.4
0.2, 0.4, 0.6, 0.8, 1.0,
2.0, 4.0

10

20

10

70

Tin hiu nhiu

Gia tr nhiu a c tinh toan da vao chiu cao peak blank (DCM) thi gian lu
cua cht phn tich s dung t ng tich hp. LOD a c c tinh la ba ln gia tr nhiu
va LOQ c c tinh nh la mi ln gia tr nhiu
Bang 4.5. D liu cho mi hp cht th nghim da trn t l tin hiu nhiu
Chiu cao peak, p=10
Hp cht

% RSD

S/N=3

S/N=10

Blank

Toluene

16

43

49

163

Ethylbenzene

15

44

44

146

iso-Propylbenzene

15

37

45

151

n-Propylbenzene

14

25

41

136

Cach tip cn nay c ng dung rng rai trong sc ky khi do d dang thc hin.
Trong nghin cu nay 10 s c lp cua mu trng vi dung dch chun mc 0.4g/mL
c phn tich ring bit vao nhng ngay khac nhau. lch chun tng i trong
10 php o dao ng t 25% n 44% cho 4 hp cht th nghim khac nhau.
Xac nh Blank
Xac nh blank c thc hin bng cach phn tich 10 mu c lp khoang trng,
nng trung binh va lch chun cua cac kt qua trng c tinh toan.
Bang 4.6. Nng trung binh va lch chun cua mu blank thu c bng cach s dung
phng phap xac nh blank
Blank p=10
Hp cht

Nng xbi ,
g/mL

Toluene

0.05

lch chun S bi
0.02

31

Ethylbenzene

0.05

0.02

iso-Propylbenzene

0.06

0.02

n-Propylbenzene

0.05

0.01

Hi quy tuyn tinh

Hi quy binh phng c tinh toan da trn phn tich 10 ln lp lai (p = 10) cua
cac hp cht th nghim tai 7 nng khac nhau (n-7). Cac d liu thu c c s dung
tinh toan 2 h s cua ng cong hiu chun nhm xac nhn hiu chun c la chn
la thc s tuyn tinh.
lch chun cua blank c c tinh bng cach s dung 2 lch chun cua hi
quy con lai ( S res ) va y chn ( S yo )

Bang 4.7. Cac thng s cua hi quy binh phng nho nht cua 4 hp cht th nghim 7
nng khac nhau
Hp cht
H s tng quan, r

H s goc, b

Y-chn, a

S yo

S res

Toluene

0.992

798

18

16

91

Ethylbenzene

0.990

804

17

18

102

iso-propylbenzene

0.994

804

15

13

78

n-propylbenzene

0.992

787

36

15

89

n=7, p=10

4.1.3.2. Th nghim tuyn tnh

Khoang tuyn tinh cua phng phap nay c anh gia da trn Hng dn IUPAC.
Hn hp tiu chun 7 nng (n = 7) dao ng trong LOQ t 0,4 - 80mg/mL a
c s dung chun b ng cong hiu chun.

32

Hinh 4.3. Biu lng d cho (a) Toluene, (b) ethylbenzene; (c) iso-Propylbenzene va
(d) n-Propylbenzene vi gii han t (0.05, np-2) S res

33

4.1.3.2. Nng cht phn tch trong mu

Bang 4.8. Nng cua cht phn tich trong cac mu PS khac nhau
Nng g/kg, (p=2)
Ethyl

iso-Propyl

n-Propyl

Total

benzene

benzene

benzene

VOCs

<LOQ

10 - 190

<LOQ - 25

<LOQ - 22

250 - 1156

<LOQ - 35

19 - 314

<LOQ - 56

<LOQ - 43

86 - 1905

<LOQ

11 - 209

<LOQ - 21

<LOQ - 17

400 - 2156

chai sa

<LOQ

<LOQ - 91

<LOQ - 33

<LOQ - 21

63 - 552

Hp thc

<LOQ - 88

<LOQ - 872

<LOQ - 45

<LOQ - 30

161 - 1600

Mu

Bat mi n
lin

Toluene

dng 1
ln dao
ko
dng
dao ko

34

n
%Thu hi

89- 112%

87-104%

87-106%

84-124%

4.2. p dng SPME trong nghin cu s chuyn dch VOCs trong bao b thc phm
Polystyrene
Ti u hoa chng trinh GC va thc hin chit dung dch chun trong dung dch
nc bng SPME va tim vao GC-FID
4.2.1. iu kin thit b
Tim chia dong theo t l 10:1 a c ap dung sau khi tim 0,5phut cho cac
peak nhn. Bng cach s dung cng mt chng trinh GC nh i vi vt liu kim
tra, chit SPME cho thy kha nng tach tt hn.
HS-SPME khng co peak dung mi trong sc ph. Cac peak ra sc nt va thi gian
phn tich la khoang 12 phut. rut ngn thi gian phn tich trong khi vn duy tri cac
thng s tach nh cac th nghim vt liu, ct chng trinh nhit lo a c rut ngn 3
phut va do o tng thi gian chay mt phn tich a c giam xung con 16,75 phut.

Hinh 4.4. HS-SPME method. Peak: 1 = Toluene (45 ppb); 2 = Ethylbenzene (15 ppb); 3 =
iso-Propylbenzene (5 ppb); 4 = n-Propylbenzene (5 ppb); 5 = 1,4-Diethylbezene (ISTD, 5
ppb)
4.2.2. LOD v LOQ
Gii han phat hin va nh lng c c tinh theo phng phap o tin hiu nhiu.
Cac thng s nay c tinh toan nh nng ti thiu ma tao ra mt tin hiu peak it nht
la 3ln (LOD) va hn 10ln (LOQ) so vi tin hiu nhiu lin k. Xac nh c thc hin

35
bng cach tinh trung binh t l tin hiu nhiu (S/N) t chay lp lai 10 ln mu trng vao
cac ngay khac nhau cng vi mt hn hp tiu chun nng thp.

Bang 4.9. D liu cho mi hp cht th nghim da trn tin hiu nhiu
Trung binh (chiu cao peak), p=10
Hp cht

LOD

LOQ

(ng/mL)

(ng/mL)

304

2.66

4.43

176

294

0.78

1.63

26

168

281

0.40

0.67

20

193

321

0.28

0.47

Blank

% RSD

S/N=3

S/N=5

Toluene

61

24

182

Ethylbenzene

59

23

iso-Propylbenzene

56

n-Propylbenzene

64

4.2.3. Tuyn tnh

S dung mt

loat

nng dung

dch

chun trong

nc kh

ion

hoa,

khoang tuyn tinh c xac nh cho mi cht phn tich. Mi dung dch c phn
tich HS-SPME 3ln, cac gia tr hi quy tuyn tinh cho toluene, ethylbenzene, isopropylbenzene va n-propylbenzene at c.

36

37

Hinh 4.5. Biu tuyn tinh cht phn tich (a) Toluene, (b) ethylbenzene, (c) isoPropylbenzene; (d) n-Propylbenzene va vi gii han t (0.05, np-2), S res
Khoang tuyn tinh khac nhau gia cac cht phn tich khac nhau bng cach s
dung chit SPME. Kt

qua cho

thy rng tuyn

tinh tt cho

mi cht

phn

tich trong pham vi th nghim

Bang 4.10. Tom tt cac kt qua th nghim tuyn tinh bng cach s dung HS-SPME
Khoang
Cht phn tich

tuyn tinh

Phng trinh hi quy

(ng/mL)

H s tng

y- qua

quan, r

gc

Styrene

1 - 20

y=66.590x+0.0613

0.9883

Toluene

4.5 - 90

y=26.3901x+0.0654

0.9937

Ethylbenzene

1.5 - 30

y=63.0701x+0.0681

0.9957

iso-Propylbenzene

0.5 - 10

y=110.5050x+0.0212

0.9974

38

n-Propylbenzene

0.5 - 10

y=131.6803x+0.0393

0.9971

4.2.4. chnh xc
chinh xac phng phap c anh gia bng cach kim tra nng mc thp,
trung binh va cao trong pham vi tuyn tinh trong dung dch nc
Bang 4.11. Mc nng khac nhau ap dung th nghim chinh xac
Mc

Nng (ng/mL)
Toluene

Ethylbenzene

iso-propylbenzene

n-propylbenzene

Thp

4.5

1.5

0.5

0.5

TB

45

15

Cao

90

30

10

10

Chit thu hi cac cht phn tich c tinh toan tng ng bng cach thm vao hn
hp tiu chun vi cac mu blank. Thu hi tt thu c inh trung binh va cao trong khi
inh thp, thu hi trong khoang t 60-78%
chinh xac c cai thin nh mc tng nng toluene va ethylbenzene. Cac gia
tr RSD thp hn khoang 15% va vi ngoai l cua n-propylbenzene 20,08% inh thp.
Noi chung, nhng kt qua nay cho thy hiu qua cua phng phap phat trin trong thi han
khai thac phuc hi cung nh chinh xac.

39

Bang 4.12. anh gia chinh xac phng phap chit thu hi, p = 3
Spiked level
Cht phn tich

% Thu hi

% RSD

4.5

78

12.45

22.5

116

7.69

67.5

102

1.39

1.5

61

11.63

15

101

9.56

30

89

2.42

0.5

62

6.45

105

11.20

10

84

13.59

0.5

71

20.08

2.5

107

2.16

7.5

100

7.31

(ng/mL)

Toluene

Ethylbenzene

iso-Propylbenzene

n-Propylbenzene

KT LUN

40
Toluene, ethylbenzene, iso-propylbenzene, n-propylbenzene trong bao bi thc phm
polystyrene a c xac nh bng sc ky khi u do ion hoa ngn la. Nghin cu nay
chng minh tinh kha thi cua vic s dung k thut giai th tim trc tip cho vic phn tich
cac hp cht VOCs trong bao bi thc phm polystyrene.

KIN NGH

41
M rng danh sach cac hp cht th nghim va cac mu c kim tra. Nghin cu
cac VOCs khac va cac loai bao bi nh polycarbonate, PE, PP, ... GC-MS xut cho
nghin cu hp cht VOCs va xac nh cac hp cht khac trong vt liu ong goi. HSSPME la mt cng cu manh phn tich ham lng vt, co th tng hiu sut cua phng
phap nay bng cach t ng hoa cac thit b SPME vi GC-FID

TI LIU THAN KHO

42
[1].

Kusch, P. and Knupp, G. J. Polym, Headspace-SPME-GC-MS Idenfication of

Volatile Organic Compounds Released from Expanded Polystyrene, 2004.

[2].

J Pawliszyn , Solid phase microextraction: Theory and Practice, 1997.

[3].

Marsin Sanagi, M., and Lu, Susie Ling, and Zalilah Nasir, and Wan Aini Wan
Ibrahim, and Ahmedy Abu Naim, Determination of Residual Volatile Organic
Compounds Migrated from Polystyrene Food Packaging into Food Simulant by
Headspace Solid Phase Microextraction-Gas Chromatography. Malaysian Journal
of Analytical Sciences, 12 (3). pp. 542-551. ISSN 13942506, 2008.

[4].

Lu, Susie Ling, Gas chromatographic determination of styrene and other volatile
organic compounds in polystyrene food packaging. Masters thesis, Universiti
Teknologi Malaysia, Faculty of Science, 2008.

[5].

International Life Sciences Institute. Polystyrene for Food Packaging Applications.

In: Report on Packaging Materials. International Life Sciences Institute (ILSI)
Europe Packaging Material Task Force, Belgium. May, 2002.

[6].

jm Miller. John Wiley &amp; Sons, Hoboken, Chromatography: Concepts. and

Contrasts, 2008.

[7]. Bruno Kolb and Leslie S. Ettre A, Static HeadspaceGas Chromatography: Theory
and Practic, 2006.
[8 ]

http://www.astm.org/Standards/F1884.htm

43

44