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 tn tinh chi bao va tao iu
kin thun li cho em hoan thanh tt an nay.
Trong qua trinh thc hin bai bao cao nay chc chn khng th tranh khoi nhng
thiu sot. Kinh mong quy thy c, cac ban nhit tinh ong gop nhng y kin quy bau
quyn bao cao cua em c tr nn hoan thin tt hn.

ii

NHN XT CA GING VIN HNG DN

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Phn nh gi:

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

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

Hnh thc trnh by:.....................................................................................................

Tng hp kt qu:.........................................................................................................

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

Tp. H Ch Minh, ngy thng nm 2012
Ging vin hng dn

Th.S. L Thanh Tm

iii

NHN XT CA GING VIN PHN BIN

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Phn nh gi:

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

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

Hnh thc trnh by:.....................................................................................................

Tng hp kt qu:.........................................................................................................

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

Tp. H Ch Minh, ngy thng nm 2012
Ging vin phn bin

iv

MC LC

LI CM N.........................................................................................................................i
NHN XT CA GING VIN HNG DN................................................................ii
NHN XT CA GING VIN PHN BIN..................................................................iii
MC LC.............................................................................................................................iv
DANH MC BNG BIU.................................................................................................vii
DANH MC HNH NH..................................................................................................viii
LI M U.........................................................................................................................i
CHNG 1: TNG QUAN V CC DUNG MI D BAY HI.....................................1
1.1. Tng quan v dung mi..............................................................................................1
1.1.1. Khi nim dung mi............................................................................................1
1.1.2. Tnh cht vt l ca dung mi hu c.................................................................2
1.1.3.Tnh cht ho hc ca dung mi..........................................................................2
1.1.4. Cc ch tiu nh gi cht lng dung mi hu c.............................................2
1.1.6. Ngun pht sinh nhim VOCs.........................................................................3
1.1.7. c tnh ca cc dung mi hu c d bay hi ...................................................3
1.2. Tng quan v sc k kh.............................................................................................4
1.2.1. Gii thiu v sc k kh......................................................................................4
1.2.2. Thit b trong sc k kh ....................................................................................4
1.2.3. K thut tim mu Headspace............................................................................6
CHNG 2: GII THIU V BAO B V MC IN.......................................................10
2.1. Gii thiu v bao b..................................................................................................10
2.1.1. nh ngha.........................................................................................................10
2.1.2. Chc nng cng ngh v tiu dng...................................................................10
2.1.3. Mt s loi mng bao b thng dng.................................................................10
2.1.3.2. Polyethylen (PE)............................................................................................10
2.1.4. Bao b thc phm..............................................................................................11
2.2. Gii thiu mc in......................................................................................................11
2.2.1. Khi nim..........................................................................................................11
2.2.2. Cu to, phn loi..............................................................................................11

v
2.2.3. C ch bm dnh ca mc in ln bao b............................................................12
CHNG 3: QUY TRNH XC NH DUNG MI D BAY HI TRONG BAO B
THC PHM POLYSTYRENE.........................................................................................12
3.1. Phm vi nghin cu..................................................................................................13
3.2. Phng php p dng...............................................................................................13
3.3. nh gi k thut chun b mu...............................................................................13
3.4. Cht phn tch v ha cht........................................................................................13
3.5. Thit b......................................................................................................................15
3.6. Phng php kim tra vt liu..................................................................................15
3.6.1. Chun b dung dch chun.................................................................................15
3.6.2. Chun b mu- k thut ha tan........................................................................16
3.6.3. iu kin sc k kh..........................................................................................16
3.6.4. Phn tch v nh lng....................................................................................16
3.6.5. Qun l cht lng php o..............................................................................17
3.7. Phng php HS-SPME...........................................................................................17
3.7.1. Chun b dung dch chun.................................................................................17
3.7.2. Dng thc phm v iu kin ty ra...............................................................18
3.7.3. Chun b mu....................................................................................................18
3.7.5. Thit b..............................................................................................................19
3.7.6. Phn tch v nh lng....................................................................................19
3.7.7. Ti u ha cc tham s SPME..........................................................................20
3.8. Phng php xc nh..............................................................................................20
3.8.1. c im...........................................................................................................20
3.8.2. Gii hn pht hin v gii hn nh lng.......................................................21
3.8.4. chnh xc.....................................................................................................22
3.9. Phn tch d liu.......................................................................................................23
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 php pht trin xc nh hp cht hu c d bay hi trong bao b thc
phm bng phng php ha tan.....................................................................................24
4.1.1. Xc nh cc vt liu bao b..............................................................................24

vi
4.1.2. Kim tra vt liu................................................................................................25
4.1.3. Phng php xc nhn......................................................................................28
4.2. p dng SPME trong nghin cu s chuyn dch VOCs trong bao b thc phm
Polystyrene .....................................................................................................................34
4.2.1. iu kin thit b...............................................................................................34
4.2.2. LOD v LOQ....................................................................................................34
4.2.3. Tuyn tnh.........................................................................................................35
4.2.4. chnh xc.....................................................................................................38
KT LUN..........................................................................................................................39
KIN NGH.........................................................................................................................40
TI LIU THAN KHO....................................................................................................41

vii

DANH MC BNG BIU

Bng 2.1. Cng thc mc in hnh.....................................................................................12

Bng 3.1 Danh mc cht phn tch v ni chun.................................................................14
Bng 3.2 Danh mc ha cht...............................................................................................14
Bng 3.3.Chun b dung dch hiu chun cho th nghim di chuyn..................................18
Bng 3.4.nh gi cc thng s SPME...............................................................................20
Bng 3.5. Bc sng ring trong mu polystyrene..............................................................24
Bng 4.1: So snh hiu qu chit i vi nhng k thut chit khc nhau..........................26
Bng 4.2. Nng cht phn tch trong cc mu thu c bng phng php ni chun
(ISTD) v thm chun (SA).................................................................................................28
Bng 4.3: Nng thu hi t 10 loi mu...........................................................................29
Bng 4.5. D liu cho mi hp cht th nghim da trn t l tn hiu nhiu....................30
Bng 4.7. Cc thng s ca hi quy bnh phng nh nht ca 4 hp cht th nghim 7
nng khc nhau...............................................................................................................31
Bng 4.8. Nng ca cht phn tch trong cc mu PS khc nhau...................................33
Bng 4.9. D liu cho mi hp cht th nghim da trn tn hiu nhiu............................35
Bng 4.10. Tm tt cc kt qu th nghim tuyn tnh bng cch s dng HS-SPME.......37
Bng 4.11. Mc nng khc nhau p dng th nghim chnh xc.........................38
Bng 4.12. nh gi chnh xc phng php chit thu hi, p = 3..................................39

viii

DANH MC HNH NH

Hnh 1.1. S my sc k kh.............................................................................................4

Hnh 1.2. Ct nhi v ct mao qun.......................................................................................5
Hnh 1.3. ng chit Headspace tnh.......................................................................................7
Hnh 1.4. S chit mu t ng Headspace vo GC.........................................................7
Hnh1.5. Cu hnh c in ca thit b P&T GC mao dn.....................................................8
Hnh 3.1. Cc polystyrene vi vch nh du1 cm.............................................................19
Hnh 3.2. Ph FTIR ca PS bowl (a) v PS container (b)....................................................25
Hnh 4.1. So snh phn ng bng k thut chit khc nhau, p = 6......................................26
Hnh 4.2. GC-FID tch cht phn tch 10g/mL trn mt ct DB-WAX, 30m, ID
0,25mm, dy 0,25m. Peaks: 1 = Toluene, 2 = ethylbenzene, 3 = iso-propylbenzene, 4
= n-Propylbenzene, 5 = 1,4-Diethylbenzene (ISTD)...........................................................27
Hnh 4.3. Biu lng d cho (a) Toluene, (b) ethylbenzene; (c) iso-Propylbenzene v
(d) n-Propylbenzene vi gii hn t (0.05, np-2) ..............................................................32
Hnh 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)......................................................................................................................................34
Hnh 4.5. Biu tuyn tnh cht phn tch (a) Toluene, (b) ethylbenzene, (c) isoPropylbenzene; (d) n-Propylbenzene v vi gii hn t (0.05, np-2), ...............................37

LI M U

Bao b l mt loi sn phm cng nghip c bit c dng bao gi v cha

ng, nhm bo v gi tr s dng ca hng ha, to iu kin thun li cho vic vn
chuyn, xp d, bo qun, tiu dng sn phm. Bao b ngy cng tr nn ph bin v c
ng dng trong mi lnh vc i sng, sn xut v tiu dng
Trong sn xut bao b cng nghip, vt liu c trng mc in m thng cha nhiu
cht c hi, cc dung mi hu c d bay hi. Do vy vic xc nh v kim sot lng
dung mi d bay hi trong bao b gi vai tr 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 l cht lng c kh nng ha tan cht rn, cht lng hoc cht kh to
thnh hn hp phn tn ng nht mc phn t hay ion gi l dung dch. Dung mi
thng dng m chng ta gp hng ngy l nc. Dung mi thng dng c im si thp
v d dng bay hi
Phn loi dung mi.
1.1.1.1. Phn loi theo hp cht ha hc.
Da theo cu to ha hc, cc dung mi thng thng thuc vo loi cc hp cht
sau: hydrocacbon bo v thm, cc dn xut clo v nitro ca chng, cc ancol, axit
cacboxylic, este, amit, nitril, ete, xeton v sulfonic.
1.1.1.2. Phn loi theo cc hng s vt l
Nhng dung mi c nhit si di 100 0C 760 mmHg gi l dung mi c nhit
si thp, cn vi nhit si cao hn 1500C gi l dung mi c nhit si cao.
Nhng dung mi c hng s in mi cao c tc dng nh nhng dung mi phn ly.
i khi ngi ta cn gi dung mi phn cc v ngc li l nhng dung mi c hng s
in mi thp gi l dung mi khng phn cc.
1.1.1.3. Phn loi theo tnh cht axit-baz.
Axit l nhng cht cho proton, cn baz l nhng cht nhn proton. Khi axit HA ho
tan trong dung mi baz th cn bng acid baz c thit lp
1.1.1.4. Phn loi theo tng tc trc tip vi cht tan.
Theo Packer, c th chia dung mi thnh dung mi khng proton lng cc v
proton lng cc da vo tng tc c bit vi cc anion v cation. Trc ht phi k n
tnh lng cc v kh nng to lin kt hydro. C th b sung thm vo hai nhm mt
nhm th ba, nhm dung mi khng proton phn cc
1.1.1.5. Phn loi theo ngun gc dung mi.

2
Da theo cch phn loi ny, dung mi c chia thnh hai nhm: dung mi c
ngun gc du khong v dung mi c ngun gc t thc vt, ng vt (hay cn gi l
dung mi sinh hc)
1.1.2. Tnh cht vt l ca dung mi hu c.
Tnh cht vt l ca dung mi l mt yu t quan trng khi la chn dung mi trong
cc ng dng. Trc tin, dung mi phi trng thi lng di p sut v nhit m n
c s dng.
Cc tnh cht nhit ng ca dung mi nh: mt , p sut bay hi, nhit tr v sc
cng b mt, nht, kh nng khch tn, kh nng dn nhit. Tnh dn in, tnh cht
quang hc, t tnh v momen lng cc, hng s in mi.
Ngoi ra, cc c im v phn t ca dung mi nh: kch thc, b mt, th tch ca
phn t dung mi cng c kho st.
1.1.3.Tnh cht ho hc ca dung mi.
Tnh tr v mt ho hc l iu kin tin quyt s dng mt cht lng nh dung
mi. Hydrocacbon dy bo v dy thm l nhng cht ho hc tr v tho mn iu kin
ny. Alcol l cht bn vng v mt ho hc nhng li phn ng vi kim loi kim, kim loi
kim th v nhm to mui.
Este v xeton l nhng cht ho hc kh bn vng trong iu kin bnh thng.
1.1.4. Cc ch tiu nh gi cht lng dung mi hu c.
1.1.4.1. tan trong nc.(ASTM D1722).
Ch tiu ny xc nh tan ca dung mi trong nc. Mu o c pha long 10
ln vi nc v hn hp ny c kim nh vn c. Nu mu khng xut hin im vn
c th mu c nh gi l qua th nghim.
1.1.4.2. Ch s Kauri butanol. (ASTM D1133).
Php o gi tr Kauri butanol l php o im vn c nh gi mnh ca
dung mi hydrocacbon. Gi tr Kauri butanol ca mt dung mi th hin lng ti a
dung mi c th thm vo mt dung dch nha Kauri (mt loi nha copal) trong ru
butylic m khng gy ra vn c. Nha Kauri tan ngay vo ru butylic nhng khng tan
trong dung mi hydrocacbon, dung dch nha s ch tn ti trong mt gii hn pha long.
1.1.4.3. nht

3
nht l tnh cht ca mt cht lng, c xem l m st ni ti ca cht lng v
cn tr s chy ca cht lng.
Nguyn nhn gy ra nht l do i lc c hc gia cc ht cu to cc cht lng.
nht ng hc l t s gia nht ng lc v t trng ca n (c hai c xc nh
cng nhit v p sut).
1.1.4.4. Tnh n mn
Th nghim n mn tm ng c s dng xc nh kh nng n mn tm ng
ca dung mi. Th nghim ny nhm nh gi s c mt ca axit trong dung mi sinh hc.
1.1.5. ng dng
Dung mi hu c c s dng rng ri ha tan v phn tn cht bo, trong du,
sp, bt mu, sn du, cao su v cc cht khc.
Thng c s dng trong sn,vecni, sn mi, sp, cht nh bng sn nh v giy,
keo, nhin liu, cht chng ng, ty du m, lm sch v cc lm kh mc in. Cc sn
phm dc phm v thuc tr su, cht bo qun, quy trnh phng th nghim
1.1.6. Ngun pht sinh nhim VOCs
Ngun pht sinh nhim VOCs do t khng trit xng du, cc dung mi hu c
t bay hi, bay hi ca xng du v ho cht ri vi. Nhn chung, xng v sn l hai th
pht x VOCs nhiu nht. Chng t gy c mn tnh m ch yu gy c cp tnh nh
chng mt, say nn, sng mt, co git, ngt vim phi. Ch mt s t cht c kh nng gy
c mn tnh nh ung th mu, bnh thn kinh.
Ngoi ra, cc sn phm m phm, du m, nha, keo dn cng nghip, thuc tr su
v cng ngh in cng l nhng ngun pht 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 cc dung mi hu c bay hi nhit thng v c hp th qua da,
phi v 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 cc bao b nha c th nh hng sc khe con
ngi.

4
Ethylbenzene l mt ha cht tng hp quan trng c sn xut vi s lng
ln nh l mt tin cht styrene v polystyrene. N c hp thu qua da, phi v ng
tiu ha v gy kch thch mt, da v nim mc. Ethylbenzene l cht gy ung
th c bit n da trn cc nghin cu trn ng vt nhng bng chng khng y
ngi. IARC phn loi ethylbenzen nh cht gy ung th nhm 2B
1.2. Tng quan v sc k kh
1.2.1. Gii thiu v sc k kh
Sc k kh c dng phn tch cc cht tng i d bay hi (t s 3500C) v bn
nhit. Pha ng l kh mang, cc kh ny gn nh tr nhit ct sc k nh He, N 2, Ar,
N2
Pha tnh l cc cht bn nhit khng bc hi nhit ct sc k. Trong sc k kh
th pha tnh ng vai tr chnh trong vic to nn tng tc cn thit cu t c tch ra
khi nhau. S thay i pha tnh hoc cc thng s lm vic s nh hng n lc tng tc
gy nn s tch
1.2.2. Thit b trong sc k kh

Hnh 1.1. S my sc k kh
1.2.2.1. Kh mang (pha ng)
Kh c chn lm kh mang phi p ng cc yu cu: tr vi cu t kho st, t
khi nh lm tng vn tc khi mang, tn ti dng tinh khit. Khi xt quan h gia
chiu cao a l thuyt H v vn tc tuyn tnh ca dng kh mang, la chn kh mang cho
cc tiu cng tri rng cng tt
Cc loi kh mang thng dng l He, N2, Ar, N2
Kh hydro thng mi tiu chun cho sc k kh. Khi s dng hydro lm kh
mang nn cn dng N2 lm kh bo v thi qua ct trc.

5
Kh He l kh tr ha hc rt thch hp cho sc k kh nhit cao, khi s dng
detector ion ha bng tia phng x phi l kh khng c hot tnh ha hc c dng cho
sc k nhit cao.
Kh N2 khng nguy him, gi r v d dng lm tinh khit nn N2 s dng rt nhiu
trong sc k kh
1.2.2.2. Ct sc k
Ngi ta chia ct sc k kh lm 2 loi ct tch:
Ct nhi c chiu di L: 0.53m, ng knh trong 24mm bng thy tinh hay kim
loi (inox) hoc thm teflon, bn trong ct c nhi y vi ht rn tinh cu, din tch
ring > 1m2/g (dp = 100-120mesh = 150-250m). Ht c ph mt lp cht lng kh bay
hi. Hiu nng ct cng ln khi ng knh dp cng nh
Ct m (ct mao qun) thng c lm bng fused silica c tnh bn v mt vt l
v tr v mt ha hc, vi ng knh trong 0.1-0.53mm, ct mao qun c chiu di 1230/60/100m. Ct mao qun chia lm 3 loi ct: ct WCOT, ct PLOT, ct SCOT

Hnh 1.2. Ct nhi v ct mao qun

1.2.2.3. Cht rn hp ph (pha tnh)
Pha tnh s dng cho sc k kh phi p ng yu cu: t bay hi, bn nht, tr v
mt ho hc, pha tnh v ct cn c phn cc tng t nhau
Gm 2 dng: pha tnh rn v pha tnh lng
1.2.2.4. Phng php tim mu
Injector hay bung tim l v tr ti mu s c ha hi v a vo ct sc k
theo s li cun dng kh mang. Cc loi bung tim mu c chia lm 2 nhm chnh l

6
injector cho ct nhi v in jector cho ct mao qun. trong mi nhm li chia thnh nhiu
loi khc nhau tu thuc mc ch phn tch, loi mu v th tch mu tim
1.2.3. K thut tim mu Headspace
Headspace l khng gian kh trn mu trong mt l sc k. Cc thnh phn mu d
bay hi khuch tn vo giai on kh, to thnh kh Headspace. Phn tch headspace l
phn tch cc thnh phn c mt trong kh .
1.2.3.1. ng dng
Phn tch hm lng hp cht hu c d bay hi (VOCs) trong cht lng, rn bng
cch gia nhit nhit thp. Trong cng nghip, k thut tim mu Headspace thng
c dng trong phn tch d lng dung mi trong cc sn phm in, nha, keo dn
1.2.3.2. Nguyn tc
Trc khi tim mu lng hoc rn c cho vo mt ng ng mu kn, mu thng
chim di 50% th tch ng v ng thng c th tch 10 hoc 20mL. ng ng mu
c t trong mt l gia nhit c th kim sot nhit chnh xc ti hn 1 0C hoc tt
hn. Sau , ng c gi nhit gia nhit trong mt thi gian nht nh, sau phn
hi c ht ra v tim mu vo cng tim mu. C th tim mu bng tay vi syring kh
hoc tim mu t ng bng h thng chuyn dng.
Nhit l gia nhit thng khong 35-2000C
1.2.3.3. Phng php chit Headspace
Mt tnh nng quan trng ca phn tch VOCs l trong nhiu trng hp cht phn
tch l ln u tin chuyn sang pha kh hi v sau c phn tch bi mt thit b. Sc
k kh (GC) l phng php cng c c la chn cho vic tch v phn tch cc hp
cht d bay hi.
Tuy nhin, vic phn tch tr nn kh khn khi cc cht phn tch b ha tan hay hp
ph trong mt mu phc tp nh m phm, polyme, dc phm hay nguyn vt liu. Yu
cu trch xut cc cht phn tch v xc nh chnh xc khi lng hoc nng ca chng
Cc phng php chit Headspce bao gm: chit Headspace tnh (SHE), chit
Headspace ng (purge & trap), chit vi pha rn (SPME), chit sut mng v chit cht
lng. S la chn ca k thut ph thuc vo loi mu, thng tin yu cu (v s lng
hoc cht lng), nhy, cn t ng ha v gi thnh.
Phng php chit Headspace tnh (SHE)

7
Phng php chit Headspace tnh cn c gi l chit cn bng Headspace. y l
mt trong nhng k thut ph bin nht cho cc phn tch nh tnh v nh lng ca cc
hp cht hu c d bay hi t nhiu mu.
Phn tch Headspace tnh bao gm hai giai on. u tin, mu lng hay rn c
a vo mt ng kn th tch 10 hoc 20mL c iu khin nhit khng i cho n
khi t trng thi cn bng gia hai pha. Sau , phn phn c ca pha kh trong l theo
dng kh mang vo ct v c phn tch theo cch thng thng.
Vic chuyn mu vo ct c th c thc hin bng mt s cch: bng tay nh s
dng ng tim kn kh, hoc t ng bng cch p lc ln l mu v kim sot thi gian
hoc lng pha kh ca headspace vo ct.

Hnh 1.3. ng chit Headspace tnh

Hnh 1.4. S chit mu t ng Headspace vo GC

Phng php chit HeadSpace ng

8
K thut headspace ng ch yu l phng php chit kh lin tc v phn bit
thnh phn mu d bay hi t nn bi mt dng lin tc ca kh tr pha trn mu lng hay
rn hoc bng s sc kh qua thy tinh kt dnh mt l cao qua mu lng, tt nht l qua
dung dch nc. K thut ny c gi l lm sch v by (P&T). B mt tip xc ln cn
thit chuyn nhanh chng lng t nn mu (nc) lm sch kh v cc a thy tinh
cho ra cc bong bng kh nh.
tng c bn ca P&T l tch hon ton hi cn phn tch t mu sn sng
phn tch nh lng trong kh chit cui cng. Nh vy qu trnh chit trit theo cp s
nhn v do mt mt thi gian. Cc hi c lm sch phi c mt trong kh chit long
v tp trung trong mt ci by. iu ny c th l mt ci by lnh, hp kn vi vt liu
hp ph c s dng m t cc hp cht b gi li thot ra nh gii hp nhit v
chuyn vo ct bi dng kh mang.
Tc cao cn thit t c chit hon ton t mu trong thi gian ngn nht.
iu ny i hi mt ci by kh nng trnh chc thng trong thi gian chit. Qu l
mt ci by nh vy c chung kch thc ca mt ct ngn v chp nhn t l dng chy
so snh, v d 20-40mL/pht cho hp ph v gii hp. Tenax, mt polymer xp l vt
liu hp ph ph bin. N l cht hp ph yu, c bit l cn phi bo qun trnh s
ph hy ca cc hp cht bay hi. Lng b ph hy c pht hin bi Kroupaetal trong
khong nhit t 100C n 1700C.
S bo qun cn thit nu ci by nhi vi nhiu cht gii hp khc nhau trong nhm
cng gc vi tnh hp ph tng dn, to thnh chng trnh hp ph cc cht d bay hi
ni cc hp cht d bay hi nht b hp ph cui cng vo vt liu hp ph vo vt liu
mnh nht v kt thc qu trnh a hp th. Cc hp cht b gi li sau b kh bi nhit
v quay li ct mao dn nhng thng b gi li tp trung trong mt ci by nhit thp

Hnh1.5. Cu hnh c in ca thit b P&T GC mao dn

9
1.2.3.4. Phng php chit vi pha rn (SPME)
Vic chuyn mu vo ct c th c thc hin bng tay hoc t ng bng cch p
lc ln l mu v kim sot thi gian hoc lng pha kh ca headspace vo ct. Thay v
chuyn trc tip phn kh headspace vo ct, k thut mi bao gm vic thm cc by hp
ph.
1.2.3.5. Detector
Mt s detector s dung trong sc k kh:
Detector ion ha ngn la (FID)
Detector cng kt in t (ECD)
Detector dn nhit (TCD)
Detector quang ha 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 b l mt loi sn phm cng nghip c bit c dng bao gi v cha
ng, nhm bo v gi tr s dng ca hng ha, to iu kin thun li cho vic vn
chuyn, xp d, bo qun v tiu th sn phm.
2.1.2. Chc nng cng ngh v tiu dng
Chc nng bo qun v bo v hng ha: Bao b l bo v hng ha, hn ch
nhng tc ng ca cc yu t mi trng n hng ha trong sut qu trnh t khi hng
ha c sn xut ra cho n khi hng ha c tiu th. Bao b c s dng bao gi
v cha ng hng ha, n l yu t u tin, trc tip tip xc vi hng ha, nhm m
bo hng ha v cht lng v s lngv ngn cch sn phm vi mi trng
2.1.3. Mt s loi mng bao b thng dng
2.1.3.1. Polystyrene (PS)
c sn xut t du th bng phng php trng hp styrene. PS th hon ton
trong sut nhng tnh ngn cn m v kh thp. PS cng nhng khng va p thp v
th ngi ta thng trn n vi loi cao su tng hp butadien tng thm bn va
chm.
2.1.3.2. Polyethylen (PE)
Hin nay PE tr thnh quan trng nht trong tt c cc loi vt liu nha. PE c
phn loi thnh cc nhm chnh sau:
- LDPE - PE mt thp, t trng 0.91- 0.925g/cm3
- MDPE (LLDPE: Linear) - PE mt trung bnh, t trng 0.926 - 0.940g/cm3
- HDPE - PE mt cao, t trng 0.941- 0.965g/cm3
2.1.3.3. Polypropylen (PP)

11
L mt loi nha olefin khc. N cng hn PE, c chu cng gin tt hn v trong
sut hn. Gi tr ca tnh thm hi m thp. Do kt tinh cao, nhit lm mm khong
150oC nn n c s dng thnh cng khi tit trng cc sn phm y khoa trong ni hp
2.1.4. Bao b thc phm
Bao b thc phm ng mt vai tr quan trng thc y an ton vn chuyn, phn
phi v lu tr thc phm. Bao b lm cho thc n tin li hn cho vic bo m an ton
v sinh thc phm, thay i ha sinh v thi gian s dng cc loi thc phm ng gi di
hn. Trong x hi hin i, vt liu ng gi cng c s dng cho vic chun b thc
phm v thc phm ng gi c t trong l nng, l vi sng, v thm ch c trong
nc si. Kt qu l, ng gi s tr thnh mt yu t khng th thiu trong lnh vc thc
phm.
2.2. Gii thiu mc in
2.2.1. Khi nim
Mc in l mt cht mu c pha ch t nhiu thnh phn khc nhau dng to ra
s tng phn v mu sc trn vt liu in qua khun in, n phi ph hp vi phng php
in v tnh cht ca vt liu in.
2.2.2. Cu to, phn loi
Mc in offset l mt hn hp lng qunh dng huyn ph, mn. Thnh phn cu
to gm c: ht mu (pigment), cht lin kt, ph gia.
2.2.2.1. Pigment
Pigment l cc cht mu to ra mu sc cho cho mc in, nu khng c pigment th
khng to ra mc in, mu ca pigment l mu ca mc. Pigment l nhng hp cht hu c
hoc v c c mu, c cng thc ho hc khc nhau v chng c c im chung l khng
thm nc, khng tan trong nc, cn, kch thc siu mn (trong in offset ng knh ht
pigment nh hn 1mm), ng thi pigment hu nh khng tan trong dung mi hu c,
khng c i lc vi vt liu, vi cc nguyn vt liu sn xut mc. Pigment quyt nh cc
tnh cht quang hc v bn mu ca mc in.
2.2.2.2. Cht lin kt
Cht lin kt l cc cht lng t nhin hoc tng hp c tnh nht dnh, c kh nng
dn thnh mng mng trn b mt vt liu in v bm dnh chc vo . Thnh phn ca

12
cht lin kt bao gm: cht to mng (amino formandehit, phenol formandehit, du thc
vt, bitum, xenlc), dung mi hu c ho tan cht to mng (ru, cn, du khong).
2.2.2.3. Cht ph gia
Cc cht ph gia: l cc cht cho thm vo mc lm tng tnh in ca mc
nh: lm tng- gim tc kh, tng hay gim bm dnh ca mc, tng hay gim kh
nng ngm ca mc trn b mt vt liu.
Thnh phn cc cht ph gia bao gm:
-

Cht du kh: cc mui kim loi nh Co, Mg, cc loi du lm thay i dnh.

Cc cht ngm: neocan... lm tng ngm ca mc.

Cc cht du m: lm tng bm dnh, bng ca mc

Cc cht ph gia c s dng ph thuc vo c trng ca tng qu trnh in.
La chn mc in ty thuc vo phng php in, thit b in, tnh cht b mt vt liu

in, tnh cht sn phm in.

Bng 2.1. Cng thc mc in hnh
Vt liu mng

Thnh phn (%V)

Pigment

12 15

Nha v amin

15 25

Cn

25

Ph gia

6 10
Nc

45 65

Cc thng s k thut ca 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
Phm vi nghin cu bao gm phng php pht trin , phng php xc nh v
phng php p dng th nghim mu. Cht phn tch c quan tm l cc dung mi
hu c d bay hi VOCs c th l toluene, ethylbenzene, iso propylbenzene v npropylbenzene.
3.2. Phng php p dng
Phng php rt n gin v d dng thc hin nh phng php ha tan v
phng php ha tan kt ta. Polymer c ha 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 vo GC-FID bng cch s dng ct mao dn
v chng trnh nhit thch hp. Trong phng php ha tan kt ta, methanol c thm
vo kt ta cc polymer, v mt lng nh cht b mt c tim vo GC.
3.3. nh gi k thut chun b mu
Vic chit cc hp cht d bay hi thng c thc hin bng cch s dng
Headspace (purge&trap), hoc k thut lm sch v by. Trong khi i vi mt hp cht
d bay hi v khng bay hi, chit lng-lng (LLE) v chit pha rn (SPE) thng c s
dng. Mt s k thut chit c in nh: chit Soxhlet v chit siu m vn cn c s
dng. Tt c nhng k thut c hiu qu, nhng c nhng hn ch.
3.4. Cht phn tch v ha cht
Cc

dung

mi

bay

hi

la

chn

cho

nghin

cu

ny:

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

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

14
Bng 3.1 Danh mc cht phn tch v ni chun
Cht phn tch

Cng thc

Khi lng phn

t

Toluene
C6H5CH3

92

(99.9%)

Nhn hiu
Sigma-Aldrich
(Germany)

Ethylbenzene
C6H5CH2CH3
(99.8%)

Iso-Propylbenzene

106

C6H5CH(CH3)2

120

(99.9%)
n-Propylbenzene

C6H5CH2CH2CH3

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

C6H4(CH2CH3)2

120

134

Bng 3.2 Danh mc ha cht

Sigma-Aldrich
(Germany)

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

15

Ha cht

Cng thc

Phn loi

Tinh khit

Nhn hiu

99.8%

J.T. Baker (USA)

Utra Resi- Phn

Dichloromethane

CH2Cl2

tch lng cht

hu c cn li

Methanol

Potassium
chloride

CH3OH

HPLG

99.99%

Thuc th

99.5%

KCl

Fisher Scientific
(UK)

Scharlau Chemie
(Spain)

3.5. Thit b
Sc k kh Shimadzu (Kyoto, Japan) GC-17A detector ion ha ngn la (GCFID) b tim mu t ng Shimadzu AOC-20i.
Cc d liu sc k c phn tch v x l bng chng trnh Shimadzu Class-VP
Nicolet 5700 (USA)

Fourier chuyn

ti

quang

ph

hng

ngoi (FT-

IR) c trang b tt dn phn x ton phn (ATR) c s dng xc nh

cc loi vt liu ng gi.
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 c chun b bng cch pha long dung dch chun gc
trong DCM v nng 1g/mL.
Dung dch gc 1,4-diethylbenzene (ISTD) c chun b bng cch ha tan dung
dch chun trong DCM nng 10 g/mL.
Dung dch 100g/mL ISTD c chun b bng cch pha long dung dch
gc trong DCM v dung dch ny c s dng cho vic hiu chun dung dch mu

16
Dung dch hiu chun nng t 0,4-80g/mL c chun b bng cch pha long
dung dch chun th hai trong DCM v thm 1 ml dung dch ISTD nng 100g/mL
(tng ng vi 10g/mL) cho mi cp ca dung dch tiu chun.
3.6.2. Chun b mu- k thut ha tan
Mu hng ha bao b thc phm Polystyrene thu c t cc siu th. Cc mu
ly khng tip xc vi thc phm.
Mu c ng nht v xc nhn l vt liu ng gi polystyrene bng FT-IR trc
khi kim nghim. Mu c t trc tip trn ca s ATR v c qut trong khong
bc sng 4000 cm-1 n 400 cm-1. Cc ph hng ngoi thu c c mu c vi th
vin FT- IR (HR Hummel Polymer v ph gia, Th vin mu Hummel Polymer) xc
nhn cc loi polymer cc vt liu ng gi
3.6.3. iu kin sc k kh
Phn tch sc k kh c thc hin vi h thng sc k kh u d FID. H thng
GC-FID c trang b vi ct mao dn DB-WAX (30 m; ng knh 0,25mm vi dy
mng 0,25m ).
Nhit bung tim v detector tng ng 220 0C v 2600C. Nhit ct c gi
400C trong vng 3 pht, sau tng 100C/pht n 120C v tip tc tng ln n 2500C
400C /pht, nhit c gi 2500C trong 5 pht.
Kh mang heli c tinh khit 99.99%, tip tc tinh ch bng cch i qua thit b
lm sch kh ry phn t 5A v oxy hp ph kh lc.
u vo c hot ng trong chng chnh chia dng vi t l chia dng 10:1, tc
chia dng 10 ml/pht.
3.6.4. Phn tch v nh lng
Mu polystyrene sau khi chit c t trong ngn ly mu t ng v 1L dch
chit c tim trc tip vo GC thng qua tim mu t ng. Cc hp cht th nghim
c xc nh bng cch so snh thi gian lu (RT) so vi cc cht tiu chun.
nh lng xc nh lin quan n vic s dng 5 im trn ng cong ni
chun v khong chun dao ng t 0,4-80g/mL. ng cong hiu chun c hin th
trn biu bng cch v t l din tch peak cao nht (din tch peak mu /din tch peak
1,4 diethylbenzene)

so vi t

l nng

(nng

cht

phn

tch

/nng

17
1,4 diethylbenzene) bng cch s dng chng trnh Shimadzu Class VP. Mt ng
cong hiu chun mi c to ra cho mi l mu phn tch
Da trn ng cong hiu chun, nng cht phn tch (g/mL) thu c. V
vy, nng thc ca cht phn tch trong mu (g/g) c tnh theo cng thc:
C ( g / g ) =

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

3.6.5. Qun l cht lng php o

Cc bin php kim sot cht lng c thc hin cho hng lot mu phn tch.
Kim sot bao gm kim tra hiu sut thit b v chit thu hi. i vi mi l mu, chun
b ng thi mu blank v phn tch m bo khng nhim tp t thuc th v thy tinh
c s dng.
Chun b dung dch chun 10g/mL tng t mu QC. Cc mu QC c tim
vo lc bt u v kt thc ca tt c mu chy hng lot, v s khc bit trong thi gian
lu v din tch peak ca cht phn tch ca chun v mu c tnh ton.
S dng GC-FID nu s thay i thi gian lu t hn 5% v s khc bit din tch
peak t hn 20%. Chit thu hi c thc hin bng cch spiking mu vi 1 ml 100mg/mL
chit chun trc khi tin hnh chit mu. Mt mu c phn tch vi tt c cc hng
lot cc mu
3.7. Phng php HS-SPME
3.7.1. Chun b dung dch chun
Dung dch gc ca mi hp cht th nghim v dung dch chun c chun b bng
cch pha long dung dch trong methanol.
Dung dch gc v dung dch trung gian ca 1,4 diethylbenzene (ISTD) c
chun b tng t nh cc hp cht th nghim.

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

Dung dch gc (g/mL)

Dung dch chun ph (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

Bng 3.3 cho thy nng ca mi hp cht th nghim v ISTD cho dung dch
chun gc v ph. Hiu chun bng 10 ml nc tinh khit kh ion ha vi 10mL lng
khc nhau dung dch chun ph v ISTD, cc dung dch ny c s dng hiu
chun
3.7.2. Dng thc phm v iu kin ty ra
Nc c chn lm dung dch ra gii i din cho nhm thc phm c
pH =4,5 v cao hn. Dung dch ty ra c chun b bng cch nung nng nc tinh
khit kh ion ha bng cch s dng b nhit cn thit cho vic nghin cu dch
chuyn.
Th nghim dch chuyn c thc hin 3 nhit khc nhau: 240C (nhit
phng th nghim), 600C v 800C v thi gian 30 pht. L khng kh nng c s dng
duy tr nhit 600C v 800C.
Cc iu kin lc c s dng hoc nhit phng trong 30 pht, hoc duy tr
nhit ca dung dch ra gii s dng v gi trong 30 pht.
3.7.3. Chun b mu

19
Dung tch ca mi mu (C) c xc nh bng cch lm y cc mu th bng
nc ln n 1cm vnh nh du t pha trn cng ca mi mu nh hnh. Nc sau
c chuyn vo xi lanh o dung tch ca mi mu th nghim.
Hnh 3.1. Cc polystyrene vi vch nh du1 cm

Mu c lm y vi dung dch ra gii, o dung tch (C) ca mi mu v lu

gi ti nhit phng hay nhit ca dung dch ra gii s dng trong 30 pht.
3.7.4. Chit HS-SPME
Cc cht phn tch c chit vi k thut HS-SPME bng cch s dng si PDMS
100m v l Headspce 22mL. Si quang c gi b tim 2500C trong 30pht. Phn
phn c ca 10mL dung dch th nghim c t trong ng headspace 22mL v 10L
ISTD 5 g/mL c thm vo ng.
Sau khi t thanh stir di 0.8cm vo trong ng, bt kn bng np Headspace vi vch
ngn ph PTFE. Lc mnh ng trong vi giy v nhit phng trong 5pht. Sau
5 pht , si quang c a vo ng v t trn khong 2mm so vi mu lng
Thi gian chit 5 pht mu khuy lin tc 800 rpm tng qu trnh cn bng. Sau
khi chit kt thc, si quang ngay lp tc c rt ra v b vo v bc bo v, chuyn
vo vi phun ca sc k kh gii hp nhit
3.7.5. Thit b
Cng tim mu sc k kh ID 0,8 mm phn tch SPME.
Cc thng s thit b c thit lp ging nh cc kim tra vt liu vi cc trng
hp ngoi l l cc vi phun c lp trnh chia dng 0,5 pht sau khi bt u chy
phn tch v thi gian gi nhit cui cng ca ct 2500C c rt ngn n 2 pht.
3.7.6. Phn tch v nh lng

20
Si quang c gii hp nhit vi tim 2200C trong vng 3 pht v bt u phn
tch. Cc cht phn tch c tch ra bng ct mao qun v xc nh bng detector FID.
Hiu chun bng phng php ni chun bng cch s dng 3 mc ng cong hiu
chun. Si blank c a vo lc bt u chy v kt thc ca tng l m
bo khng c hiu ng b nh
3.7.7. Ti u ha cc tham s SPME
Khi lng mu, cng elutropic, nhit v thi gian chit, tc khuy, nh
hng hm lng mui v thi gian gii hp c nghin cu c c cc iu kin
ti u cho hiu qu chit tt nht.
Bng 3.4.nh gi cc thng s SPME
Thng s SPME

Bin s

Phm vi

Th tch (mL)

5, 10, 15

Methanol (%)

0.1, 0.5, 1, 5, 15

Chit xut

Nhit (0C)

24, 40, 60, 80

Chit xut

Thi gian (pht)

Lng mui ra

KCl thm vo

Khuy trn mu

Tc khuy (RPM)

Gii hp

Thi gian (pht)

Lng mu
Cng
elutropic

1, 5, 15, 30, 35, 45

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

3.8. Phng php xc nh

Mt s c im c trng c nh gi chng minh s ph hp ca phng
php cho nhim v phn tch, v m bo rng d liu phn tch chnh xc v nht qun c
th thu c vi phng php xc nhn.
3.8.1. c im
Th nghim ny c da trn tiu chun b sung ca cc hp cht quan tm. Nng
ca cc hp cht c thm vo trong phm vi ca phng php ny. Mt tiu chun

21
b sung c thc hin cho mi mu v nng bao gm cc nng d kin ca mu v
khc nhau trong phm vi ca phng php.
c im c xc minh bng cch iu chnh mt ng thng gia nng thm
vo (v) v thu hi (r) nng trong ng hi quy:
r = a + b

3.8.2. Gii hn pht hin v gii hn nh lng

C mt vi cch nh gi LOD v LOQ. Ba cch c th l t l tn hiu nhiu, xc
nh blank v phng trnh hi quy tuyn tnh da trn ICH v EURACHEM hng dn
c nh gi cho LOD, LOQ kim tra vt liu.
3.8.2.1. T l tn hiu nhiu
Bng cch s dng phng php o tn hiu nhiu, ghi nhn peak trong thi gian lu
ca cht phn tch c o, v sau , nng ca cht phn tch c ghi nhn bng tn
hiu nht nh v t l nhiu c c lng. Trong nghin cu ny nhiu c o
bng my tch phn t ng, 3 tn hiu nhiu c dng xc nh LOD v 10 tn hiu nhiu
c dng xc nh LOQ
3.8.2.2. Xc nh blank
LOD c th hin nh nng cht phn tch tng ng vi gi tr mu blank cng
vi ba lch chun v LOQ l nng cht phn tch tng ng vi gi tr mu blank
cng vi lch chun nh th hin trong cc phng trnh di y:
LOD xb1 + 3S b1
LOQ xb1 +10S b1

Trong : 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 tnh, gi tr hi quy y vi nng chun x nm
trong phm vi gii hn nng . N c biu din nh sau:
y = a + bx
Phng trnh ny c s dng tnh ton nhy b v LOD, LOQ. Do , LOD
v LOQ c th c th hin nh sau:
LOD =

3S a
b

22

LOQ =

10 S a
b

Trong : Sa lch chun y, b l h s gc ng cong hiu chun

3.8.2.4. Kim tra gii hn nh lng xc nh
Kim tra m bo rng cc gi tr LOQ thu c t ba phng php t c.
Phn tch ring dung dch chun mc 10 ln LOQ vo nhng ngy khc nhau (p = 10),
trung bnh v lch chun, S QL ca 10 ln o c tnh ton.
Cc iu kin sau y phi c p ng theo th t cho gi tr LOQ c coi l
chp nhn. Gi tr trung bnh o lng x QL khng khc nhau t cc gii hn nh lng
LOQ xc nh
-

Nu gi tr trung bnh o lng xQL khng khc nhau t cc gii hn nh lng

LOQ bit
LOQ xQL
< 10
S QL
: LOQ c chp nhn
n

Nu 5 S QL <LOQ: LOQ phi khc 0

3.8.3. tuyn tnh
Phng php c s dng nh gi khong tuyn tnh c da trn hng dn

IUPAC. Mt lot cc dung dch hiu chun c chun b cc nng khc nhau.
Cc dung dch chun c chun b mi ngy v phn tch trong khong thi gian ca
ngy.
D liu thu c thch hp hi quy bnh phng nh nht (OLS) v h s gc (b),
giao im (a), lch chun ca h s gc (Sb), xc nh h s tuyn tnh r2 c c tnh
bng cch s dng chc nng LINEST ca chng trnh Microsoft Excel. Mt khi cc
thng s c c tnh, cc m hnh phi c xc nhn bi cc phng tin th nghim
m hnh hi quy (Freg), th nghim Flof v cui cng kim tra (t-test) xc nhn y-giao
nhau qua im gc.
3.8.4. chnh xc
T matrix blank khng c sn cho th nghim ny, nghin cu thu hi c s dng
nh gi tnh chnh xc ca phng php p dng. Mu c cng c vi ba cp ca
dung dch tiu chun v phn tch cng vi cc mu khng cn lp thnh hai bn.

23
chnh xc c nh gi da trn dng c chnh xc v phng php chnh
xc:
Cc phng trnh sau y c s dng tnh ton lp li.
q

Sr =

w
i =1

2
i

2n

Trong : S r : lch chun lp li

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

lp li r = 2.8S r
3.9. Phn tch d liu
Microsoft excell (2003) c la chn lu tr, hin th d liu v thc hin cc
tnh ton thng k vi cc tch 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
C nhiu loi khc nhau ca vt liu ng gi c s dng cho cc ng dng thc
phm. Rt kh phn bit cc loi vt liu da trn cc quan st vt l bao b. Ngoi ra,
khng phi tt c cc gi thc phm thng mi c cha m c th xc nh, m ny
thng c in hoc dp ni ti c s ca cc hp polystyrene hoc cho cc mc ch ti
ch.
Bng 3.5. Bc sng ring trong mu polystyrene
Nhm chc

Bc sng (cm-1)

-CH2-

2919 2921

-CH-

2848 2850

C=C

1451; 1492; 1601

Peaks 1451, 1492 v 1601 cm-1 c trng cho lin kt C=C. Peak nm trong khong
bc sng 2919 - 2921 cm-1 lin kt CH2, trong khi peak 2848 - 2850 cm -1 do lin kt
CH. Cc quang ph hng ngoi ca cc mu c so snh vi quang ph c xy dng
trong th vin FTIR xc nh polystyrene trong cc mu.

25

(a)

(b)
Hnh 3.2. Ph FTIR ca PS bowl (a) v PS container (b)
4.1.2. Kim tra vt liu
Kim tra vt liu c s dng xc nh VOCs cn li hin din trong cc sn
phm thc phm ng gi thnh phm. Trong nghin cu ny, cht phn tch c la
chn c th l toluene, ethylbenzene, iso-propylbenzene v n-propylbenzene.
4.1.2.1. Chun b mu
Cn c vo phng php ha tan, mt cch n gin v hiu qu phn lp v xc
nh toluene, ethylbenzene,

iso-propylbenzene v npropylbenzene trong

bao

b thc

phm polystyrene.
Dung dch mu thu c bng cch s dng ba k thut phn tch bng GCFID trong 6 ln lp li v kt qu c hin th trong hnh 4.1.

26

Hnh 4.1. So snh phn ng bng k thut chit khc nhau, p = 6

Hiu qu chit T1 c gi nh 100%, v c s dng lm c s cho tnh
ton hiu qu chit T2 v T3. Kh nng chit T1 thp hn T2 v T3 ca tt c cc cht
phn tch. Do mt s cht phn tch b by trong polymer trong bc kt ta. Bc ly
tm trong T3 tip tc lm gim hiu qu chit l s gim cht phn tch xy ra trong qu
trnh chuyn dung dch mu t ng knh vo ng ly tm.
Bng 4.1: So snh hiu qu chit i vi nhng k thut chit khc nhau
Cht phn tch

Hiu qu 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
Cc thng s GC c ti u ha tch cc cht phn tch vi nhy tt hn.
ra gii 4 cht phn tch l toluene, ethylbenzene, iso-propylbenzene, n-propylbenzene
v cui cng 1,4 diethylbenzene (ISTD). Tt c cc cht phn tch c tch ra trong
vng 13 pht v tng thi gian thc hin cho mi ln chy l 19,25 min.

27

Hnh 4.2. GC-FID tch cht phn tch 10g/mL trn mt ct DB-WAX, 30m, ID
0,25mm, dy 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 dng nh cht ni chun tng t nh cc cht phn
tch, hp cht ny c th nghim cng vi cc cht phn tch trong iu kin chit v
tch nh nhau, cht ni chun c tch ra t cc cht phn tch.

28
Bng 4.2. Nng cht phn tch trong cc mu thu c bng phng php ni chun
(ISTD) v thm chun (SA)
Nng trung bnh, 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 cch s dng phng php ni chun, nh hng ca s thay i cc li khng

kim sot ngu nhin c th c sa cha khng ging nh cc phng php thm chun,
do gip ci thin chnh xc ca cc phn tch nh lng.

4.1.3. Phng php xc nhn

4.1.3.1. c trng
Cc c trng ca phng php nh gi m bo rng cc phng php pht
trin o lng chnh xc v cht phn tch quan tm n s hin din ca cc thnh phn
khc trong

cc

mu bao

trn phng php thm chun.

b polystyrene.

Cc th

nghim c

trng

da

29
Bng 4.3: Nng thu hi t 10 loi mu
Mu
n=10

Nng cht phn tch thu hi

Nng
thm, mg/k

Ethyl

iso-Propyl

n-Propyl

benzene

benzene

benzene

Toluene

Tha kem

19.98

20.50

22.54

20.83

22.17

Hp sushi

19.99

18.47

20.93

18.52

19.25

Da nh

20.00

20.75

15.41

16.41

17.50

Da

199.80

232.23

219.30

225.57

231.57

Tha o

200.00

188.01

187.47

183.49

192.87

Hp son

399.52

373.65

380.71

386.93

392.42

Tha

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 cch p dng xc nh cc LOD v LOQ l xc nh blank, t l tn hiu nhiu
v phng trnh hi quy tuyn tnh. i vi mc ch so snh, DCM c s dng nh l
mt

mu trng. Mc

nng

cho mi hp

cht v

s ln

lp

li

cc

o c thc hin bng cch s dng cc phng php khc nhau

4.4. Nng cht phn tch v lp li xc nh LOD v LOQ

Phng php

Mc g/mL, n

lp li, p

Gi tr o, np

Tn hiu nhiu

0, 0.4

10

20

php

30

Xc nh blank
Hi quy tuyn tnh

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

10

20

10

70

Tn hiu nhiu
Gi tr nhiu c tnh ton da vo chiu cao peak blank (DCM) thi gian lu
ca cht phn tch s dng t ng tch hp. LOD c c tnh l ba ln gi tr nhiu
v LOQ c c tnh nh l mi ln gi tr nhiu
Bng 4.5. D liu cho mi hp cht th nghim da trn t l tn 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

Cch tip cn ny c ng dng rng ri trong sc k kh do d dng thc hin.

Trong nghin cu ny 10 s c lp ca mu trng vi dung dch chun mc 0.4g/mL
c phn tch ring bit vo nhng ngy khc nhau. lch chun tng i trong
10 php o dao ng t 25% n 44% cho 4 hp cht th nghim khc nhau.
Xc nh Blank
Xc nh blank c thc hin bng cch phn tch 10 mu c lp khong trng,
nng trung bnh v lch chun ca cc kt qu trng c tnh ton.
Bng 4.6. Nng trung bnh v lch chun ca mu blank thu c bng cch s dng
phng php xc 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 tnh

Hi quy bnh phng c tnh ton da trn phn tch 10 ln lp li (p = 10) ca
cc hp cht th nghim ti 7 nng khc nhau (n-7). Cc d liu thu c c s dng
tnh ton 2 h s ca ng cong hiu chun nhm xc nhn hiu chun c la chn
l thc s tuyn tnh.
lch chun ca blank c c tnh bng cch s dng 2 lch chun ca hi
quy cn li ( S res ) v y chn ( S yo )

Bng 4.7. Cc thng s ca hi quy bnh phng nh nht ca 4 hp cht th nghim 7

nng khc nhau
Hp cht
H s tng quan, r

H s gc, 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

Khong tuyn tnh ca phng php ny c nh gi da trn Hng dn IUPAC.
Hn hp tiu chun 7 nng (n = 7) dao ng trong LOQ t 0,4 - 80mg/mL
c s dng chun b ng cong hiu chun.

32

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

33

4.1.3.2. Nng cht phn tch trong mu

Bng 4.8. Nng ca cht phn tch trong cc mu PS khc 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

Bt m 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 ha chng trnh GC v thc hin chit dung dch chun trong dung dch
nc bng SPME v tim vo GC-FID
4.2.1. iu kin thit b
Tim chia dng theo t l 10:1 c p dng sau khi tim 0,5pht cho cc
peak nhn. Bng cch s dng cng mt chng trnh GC nh i vi vt liu kim
tra, chit SPME cho thy kh nng tch tt hn.
HS-SPME khng c peak dung mi trong sc ph. Cc peak ra sc nt v thi gian
phn tch l khong 12 pht. rt ngn thi gian phn tch trong khi vn duy tr cc
thng s tch nh cc th nghim vt liu, ct chng trnh nhit l c rt ngn 3
pht v do tng thi gian chy mt phn tch c gim xung cn 16,75 pht.

Hnh 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 hn pht hin v nh lng c c tnh theo phng php o tn hiu nhiu.
Cc thng s ny c tnh ton nh nng ti thiu m to ra mt tn hiu peak t nht
l 3ln (LOD) v hn 10ln (LOQ) so vi tn hiu nhiu lin k. Xc nh c thc hin

35
bng cch tnh trung bnh t l tn hiu nhiu (S/N) t chy lp li 10 ln mu trng vo
cc ngy khc nhau cng vi mt hn hp tiu chun nng thp.

Bng 4.9. D liu cho mi hp cht th nghim da trn tn hiu nhiu

Trung bnh (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 dng mt

lot

nng dung

dch

chun trong

nc kh

ion

ha,

khong tuyn tnh c xc nh cho mi cht phn tch. Mi dung dch c phn
tch HS-SPME 3ln, cc gi tr hi quy tuyn tnh cho toluene, ethylbenzene, isopropylbenzene v n-propylbenzene t c.

36

37

Hnh 4.5. Biu tuyn tnh cht phn tch (a) Toluene, (b) ethylbenzene, (c) isoPropylbenzene; (d) n-Propylbenzene v vi gii hn t (0.05, np-2), S res
Khong tuyn tnh khc nhau gia cc cht phn tch khc nhau bng cch s
dng chit SPME. Kt

qu cho

thy rng tuyn

tnh tt cho

mi cht

phn

tch trong phm vi th nghim

Bng 4.10. Tm tt cc kt qu th nghim tuyn tnh bng cch s dng HS-SPME
Khong
Cht phn tch

tuyn tnh

Phng trnh 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
chnh xc phng php c nh gi bng cch kim tra nng mc thp,
trung bnh v cao trong phm vi tuyn tnh trong dung dch nc
Bng 4.11. Mc nng khc nhau p dng th nghim chnh xc
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 cc cht phn tch c tnh ton tng ng bng cch thm vo hn
hp tiu chun vi cc mu blank. Thu hi tt thu c nh trung bnh v cao trong khi
nh thp, thu hi trong khong t 60-78%
chnh xc c ci thin nh mc tng nng toluene v ethylbenzene. Cc gi
tr RSD thp hn khong 15% v vi ngoi l ca n-propylbenzene 20,08% nh thp.
Ni chung, nhng kt qu ny cho thy hiu qu ca phng php pht trin trong thi hn
khai thc phc hi cng nh chnh xc.

39

Bng 4.12. nh gi chnh xc phng php chit thu hi, p = 3

Spiked level
Cht phn tch

% 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 b thc phm
polystyrene c xc nh bng sc k kh u d ion ha ngn la. Nghin cu ny
chng minh tnh kh thi ca vic s dng k thut gii th tim trc tip cho vic phn tch
cc hp cht VOCs trong bao b thc phm polystyrene.

KIN NGH

41
M rng danh sch cc hp cht th nghim v cc mu c kim tra. Nghin cu
cc VOCs khc v cc loi bao b nh polycarbonate, PE, PP, ... GC-MS xut cho
nghin cu hp cht VOCs v xc nh cc hp cht khc trong vt liu ng gi. HSSPME l mt cng c mnh phn tch hm lng vt, c th tng hiu sut ca phng
php ny bng cch t ng ha cc 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