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Bi 4: S DNG MY SC K GC14B-SHIMADZU Phn 1: Gii thiu v phng php sc k. Phn 2: Gii thiu v sc k kh. Phn 3: Gii thiu v sc k lng. Phn 4: Gii thiu v ni dung th nghim.

Phn 1: Gii thiu v phng php sc k. 1. Gii thiu v phng php sc k: nh ngha: Sc k l mt phng php tch trong cc cu t ca mt hn hp c phn b gia hai pha, mt trong hai pha tnh ng yn cn pha kia chuyn ng theo mt hng xc nh. 2. Phn loi: Ngi ta c th phn loi cc phng php sc k da vo c ch hot ng sc k, tnh cht pha tnh hay da vo ct sc k. Da vo c ch hot ng ca sc k ngi ta c th phn thnh sc k hp ph, phn b, trao i ion. Da theo tnh cht pha c sc k lng rn, sc k kh lng, sc k lng lng. Da trn dng ct c ct v bng phng. Thng thng ngi ta thng gi tt cc phng php sc k nh sc k kh, sc k lng, sc k lng cao p, sc k lp mng, sc k gel Bng cc phng php sc k:
Phn loi sc chung Sc k lng LC lng. + Lin kt lng. + Hp th v trao i ion lng- rn. Sc k kh GC kt. + Kh rn. Sc k lng siu Pha lng: cht lng + Kh lng. + Kh pha lin + Phn b lng + lng ph ln trn mt lp rn. + Cht hu c c gn trn mt b mt rn. + Nha trao i ion dng rn. + Lng c ph trn mt cht rn. + Cht hu c c gn trn mt b mt rn. + Nha trao i ion dng rn. Cht hu c c + Phn b. + Phn b gia cht lng v b mt lin kt. + Hp th ion. + Phn b gia kh v lng. + Hp th ion. Phn php Pha tnh Kiu cn bng

Phn

gia

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ti hn siu ti hn. lin kt trn mt b mt rn. cht lng siu ti hn v b mt lin kt.

3. C s chung ca phng php sc k: Xt vi mt qu trnh sc k kh: pha tnh l mt lp phin lng ph ln trn b mt rn, pha ng l dng kh nn p sut mang cht phn tch qua ct. Trong sut qu trnh cht phn tch chuyn ng qua ct sy ra hin tng phn b ca cht phn tch gia pha tnh v pha ng, iu ny lm cho cht phn tch b gi li trong ct sc k mt thi gian lu hn so vi thi gian ra ca pha ng. Lng pha tnh ra khi ct c phn b di dng mt pic m thi gian xc nh nh pic ph thuc vo tng tc gia cht phn tch vi pha ng, pha tnh, v iu kin tin hnh th nghim, thi gian ny l c trng cho mi cht phn tch. Thng thng th nhng cu t tng tc mnh vi pha tnh th s c thi gian lu lu hn. Nh vy nh ct sc k ta c th tch c cc cht khc nhau trong mt mu phn tch. Din tch ca pic c trng cho lng cht phn tch trong mu v nh vy ta s xc nh c hm lng cht phn tch trong mu. 4. Cc phng pho tin hnh tch sc k: a. Phng php ra gii: L phng php c s dng thng dng nht hin nay. Cht ra gii hay chnh l pha ng trong qu trnh phn tch. Dng a cht phn tch qua ct, thng th cht ra gii c i lc vi pha tnh b nht (b hn mi cht c trong pha tnh). Dung dch ra gii c th dng l mt cht, hay mt dung dch c nng c nh hay thay i hoc hn hp ca cc dung dch ra gii. b. Phng php tin lu: Hn hp cn tch A, B, C c a vo pha trn ca ct mt cch lin tc v c chy qua ct. Gi s th t tng tc vi pha tnh l C>B>A th th t cc cht ra khi ct l A sau l A+B v cui cng l A+B+C. S d nh vy l v theo th t u tin i lc th A ra trc ri n B v cui cng l C. Cc cht u b thot ra v sau khi ct hp th bo ha vi cc cht th khng cn kh nng gi cc cht na, v phi cc cht thot ra ngoi. Phng php ny khng c kh nng tch hon ton cc cu t nn t c s dng. c. Phng php th y: Mu c cho vo ct, sau s dng dung mi c i lc mnh nht i vi pha tnh a vo ct. Khi cht c i lc yu nht so vi pha tnh th b y ra
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u tin, sau l n cc cht c i lc yu tip theo, v cui cng l ch c pha ng i ra. i vi phng php ny th c nhiu khi pha i ra l khng c tch hon ton m c ln vi cc cu t khc. c bit vi nhng mu phn tch phc tp, th ngi ta phi dng phng php ra gii. 5. Mt s khi nim: Th tch lu Vr l th tch pha ng cn thit vn chuyn cht tan I ra khi ct v n detector. Thi gian lu tRi l thi gian t lc cht tan I c np vo ct tch ct tim mu n lc ra khi ct thi im to pic cc i. Mi lin h: Vr = Fc*tR vi Fc l lu lng pha ng i trong ct. Tm l gi tr thi gian lu ca pha ng trong ct, TR l gi tr thi gian lu ca cht phn tch I i trong ct. hiu TR Tm = TR gi l thi gian hiu chnh ca cht I. H s K phn b ca cht I c nh ngha l t s nng ca cht I gia pha tnh v pha ng. K= CS/CM. cn K li l h s dung lng c o bng t s lng cht phn tch trong pha tnh v pha ng. K = Ns/NM= tR/tM l i lng c chng cho tc chuyn ng ca cht phn tch trong ct. khi K nh hn mt th s ra ri l qu nhanh nn kh c th xc nh c thi gian lu, khi K c gi tr t 20 n 30 th s ra gii l qu chm. Thng thng gi tr ca K ph hp cho php phn tch sc k l 1 n 5. Vic iu khin gi tr ca K l c th thc hin c nh s dng cc bin php thay i nhit , cch nhi ct, thay i thnh phn pha tnh v pha ng. H s tch ca 2 cht c pic gn nhau l i lng c trng cho s phn ring, s tch gia 2 cht , nu cng ln th cc pic cng nm xa nhau, s tch ring 2 cu t cng tt. = TRA/ TRB = tA/ tB= KA/ KB. cho s tch c tt th nm trong khong 1,05 n 2 gi tr ny khng c ln qu v n s lm tng thi gian th nghim. dong rng ca pic W, W1/2. Nh hnh v. don rng ca pic th s lin quan n s tch ca cht, nguyn nhn gy ra dn di ca pic l do s khuch tn.

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khuch tn: J (mol/m2.s) = D x l di di chuyn.

vi D l h s khuch tn, C l nng ,

rng ca di sc k c biu din theo phng trnh: C l nng (mole/cm3), t l thi gian, x l khong cch di chuyn c dc theo ct, D l h s khuch tn, m l s mole cht tan dch chuyn qua mt n v tit din ngang ca ct. phng trnh trn cho bit lch chun . Chiu cao a l thuyt H l hng s t l gia phng sai 2 ca di cht tan v khong cch x m n di chuyn. Tn chiu cao a l thuyt H c ly t l thuyt chng ct trong s tch c thc hin trong nhng giai on ri rc c gi l a tch.

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Vi L l chiu di ca ct. C th gi nh ct sc k c chia thnh N phn mng hay N lp hay N a tch. mi s phn b cht tan vo hai pha li t n mt trng thi cn bng mi (sc k l mt qu trnh ng, thc ra pha ng chuyn ng chy lin tc v thi gian khng thit lp trng thi cn bng). Nu chiu cao l thuyt cng nh th rng hay s dong rng pic cng nh. Kh nng tch ca cu t mt hn hp ca mt ct c ci thin nu gim chiu cao mt a l thuyt. Cc cht tan khi chuyn qua mt ct tch c chiu cao a l thuyt khc nhau bi v chng c h s tch khc nhau. Chiu cao ct a l thuyt khong t 0.1 n 1 mm trong sc k kh v khong 10 trong ct sc k lng hiu nng cao v nh hn 1 trong sc k in di mao qun. S a l thuyt Vi tR l thi gian lu ca pic, W l don rng ca pic, W1/2 l chiu rng ca pic o na chiu cao t nh n y pic. phn gii ca ct Rs ca hai ct c nh ngha:

phn gii ca hai ct cho bit kh nng tch ca hai cht phn tch bi ct. Nu phn gii khong 1,5 th cho php tch A v B gn nh hon ton( s xen ph ch khong 0,3%, nu phn gii khong 0,75 th khng tch c cn phn gii bng 1 th xen ph c 2 pic l 4%. 6. Cc yu t nh hng ti qu trnh phn tch Chng ta c th thay i cc iu kin phn tch ny tc ng n hiu ng tch ct v phn gii ca php phn tch. Tc pha ng: tc ng n chiu cao H, hiu lc tch ca ct tng nu tng thi gian lu ca tip xc pha tnh ng, tc l gii tc chy ca pha ng, song vic ny s ko gii thi gian phn tch. Ngoi tc pha ng cc yu t khc nh hng cn c h s khuch tn pha ng v pha tnh, t s phn b, ng knh ht nhi, b dy lp cht lng ph ln ht
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S khuch tn xoy: l hin tng cc cht phn tch c ng i khc nhau khi i qua pha tnh, v vy s gy ra thi gian ra khi ct l khc nhau. Thng thng tnh trng ny sy ra do ht ln, kch thc ht khng u, v vy cch khc phc l s dng pha tnh l cc ht c kch thc b, kch thc ng u. Nhng nu kch thc ht cng b, th tr lc ln pha ng cng ln s cn p sut pha ng cao. A = c trng cho khuch tn xoy, ph thuc ng th ca cht nhi, hnh dng hnh hc, v kch thc ca ct nhi, l ng knh trung bnh ca ht. S khuch tn dc: l qu trnh cht di chun t ni c nng cao xung ni c nng thp. S khuch tn dc gy ra s gin rng ca pic. i lng c chng cho s khuch tn dc l B= 2 vi l h s khuch tn ca cht tan trong pha ng, l h s tr khng ca cht nhi ct n s khuch tn. S chuyn khi trong pha tnh: khi pha tnh l cht lng, h s chuyn khi Cs t l thun vi bnh phng chiu dy lp phin, t l nghich vi Ds ca cht tan trong phin. Vi lp phin dy cht phn tch phi di chuyn trung bnh lu hn n b mt, vi khuch tn nh, cht tan di chuyn chm hn. Khi pha tnh l mt b mt rn, s chuyn khi Cs t l thun i hi cho cc cu t c hp ph v gii hp ph. S chun ng trong pha tnh i hi mt thi gian lu hn trong khi cc cht trong pha ng lin tc c y v pha trc, chnh v vy gy ra s dn di ca pic. Khc phc i vi pha tnh l phin lng th cn la chn nhng cht lng c nht nh s lm tng h s khuch tn, lp phin mng nhng nu lp phin qu mng s lm gim dung tch hp ph, v c th gy hin tng lng khng bao kn cht nn. S chuyn khi trong pha ng: h s chuyn khi trong pha ng Cm t l nghich vi h s khuch tn ca cht tan trong pha ng Dm, bnh phng ng knh ca ht, bnh phng ng knh ca ct v tc chy ca pha ng. Ci thin Rs bng nh gim chiu cao ca mt a l thuyt v phn gii t l thun vi ( khi tng s a ln 2 ln ng ngha tng phn gii ca ct ln ln. Tng s a l thuyt bng cch tng chiu di ct th phi tiu tn nhiu thi gian phn tch hn. Gim chiu cao mt a l thuyt c th thc hin vi sc k kh l tng nhit ct, vi sc k lng l gim chiu di lp phin.

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Ci thin Rs nh h s chn lc : khi tng th s tch ca ct cng tng, s thay i l thay i pha tnh hay c pha tnh ln pha ng. i vi sc k kh l thay i theo trng trnh nhit cn pha lng l thay i theo nng pha ng. Ci thin Rs nh h s dung lng K, ni chung khi K tng th phn gii tng. Rs = nh vy khi K>10 th s tng K ch tng mt cht t Rs, thng thng K ti u trong khong 1 n 5.

PHN 2: SC K KH. 1. H thng sc k kh: H thng sc k gm c c 4 phn chnh l b phn to kh mang, b phn tim mu, b phn ct tch, b phn detector v cui cng l mn hnh hin th. 2. H thng kh mang: Kh mang phi tr v mt ha hc nh He, Ar, N2, CO2, H2. Vic la chn kh mang ph thuc vo detector. La chn kh mang nh sau: detector o dn cn s dng kh mang c dn cao nh H2, He. Detector ion ha ngn la cn chn kh mang N2 khi khng cn ghp ni vi cc thit b khc, nu c ghp ni th chn He. Detector cng kt ngn la th dng N2. Cc c im khi s dng cc kh mang thng thng: H2 s dng cn dng kh N2 ui ht O2 trong ct trc v cn c my r nu c s c h H2, he, Ar l kh tr thch hp nhit d cao. Kh N2 kh tr, r tin nn dng nhiu trong cc my phn tch, nhng cn ch N2 c dn kh gn vi mt s kh, hi hu c nn c th nhn sc k pic nghch. H thng cung cp kh mang bao gm b iu chnh p sut, thit b o p suaatsm thit b o tc dng, thit b lc kh trc khi a vo ct. thng thng p sut kh t 10 n 50 psi s c tc dng t 30 n 150 ml/ph i vi ct nhi v 1 n 25 ml/ph i vi ct mao qun. ni chung, khi p sut c khng ch khng i th tc kh i vo ct cng khng i.

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3. H thng tim mu: Dng bm tim vi lng a mu lng hoc kh vo ct qua mt van cao su silicon. Lng mu a vo t mt n 20 . i vi ct mao qun lng mu s dng rt t, chnh v vy h thng chia dng c s dng ch mt phn rt nh mu c a vo ct cn hu ht c thi ra ngoi.

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S dng bm tim: ht dung dch n vch ri ko ngc bm kim tt c mu i vo xilanh, sau khi xuyn kim qua lp m silicon th yn 3 n 5 s sau mi y piston.

a. Tim mu c chia dng: S dng cho tim mu c nng phn tch cao hoc phn tch kh, tuy nhin phng php ny c th gy mt mt mu kh bay hi trong qu trnh tim mu. tim mu chia dng c phn gii cao v c th x l cc mu bn nu nhi vo trong ng tim cht hp ph thch hp. Cc cht c nhit phn hy thp c th phn hy trong xut qu trnh tim mu nhit cao. b. Tim mu khng chia dng S dng cho cc dung dch rt long. N cung cp phn gii tt cho nhng dung dch phn tch nh lng c th c cc thnh phn phn tch km bay hi b mt trong qu trnh tim. c. Tim mu trn ct( on- column injector): S dng tt nht cho phn tch cc cht km bn nhit. l k thut c phn gii thp v khng th s dng cho nhng ct c ng knh b hn 0.25 mm. N c th x l cc dung dch lng hay c.
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4. Ct sc k: a. Ct nhi: Lm bng thp khng r vi ng knh t 3 n 6 mm v chiu di t 1 n 5 m. Ct cha cc ht cht mang rn thng l cht mang c ph lp pha tnh lng. kch thc ht ng nht s lm ci thin chiu cao ct v phn gii. c ht nh s lm gim thi gian cn bng ha tan v nh gim c chiu cao ct. tuy nhin nu kch thc ht qu nh s lm gim khng gian gia cc ht v tng p sut ct. Kch thc ht c biu din bi 80/100 mesh. Mt s loi cht rn: hu ht cc cht mang trong sc k ct u c to t diatomite nh chromosorb A,B,G,W,P. C 2 yu t cn lu khi chn cht mang l cu trc v c tnh b mt. Tng tc gia b mt cht mang l nguyn nhn gy ra s ko di ui pic. Kch thc ht nh s lm tng phn gii ca ct nhng ng thi lm tng p sut ct, chnh v vy ti u ct ngi ta thng ch to ht mang c kch thc ng u. T l phn trm pha lng: bao bc ht ton b b mt ca cht mang, ngn cn s tip xc gia cht mang v pha ng. T l pha lng/ cht mang khng c qu nhiu, trn 30% th hiu qu tch ca ct gim i rt nhiu, trc y ngi ta khng ch t 15 n 30% cn by gi l 2 n 10%. T l pha lng cn ph thuc vo cht phn tch, nu cht phn tch kh bay hi th chn t l pha lng thp (<3%) cn nu cht d bay hi th chn t l pha lng cao. Mt nhi ct: nh hng r rt n kh nng lu gi pha tnh. Khi mt nhi ct tng th khi lng pha tnh tng. Luyn ct: t t nht ct trong 2 gi nhit >25 oC so vi nhit ti a m ct s s dng. Cp dng kh mang tc 5 n 10 pht qua ct. u ra ca ct h, khng ni vi detector trnh lm bn. b. Ct mao qun: Ct mao qun c chiu di 15 n 100 m v ng knh t 0.1 n 53 mm. ct c ch to t thy tinh oxit tinh khit nu chy c mc lin kt ngang cao hn nhiu so vi thy tinh thng v chu c nhit 350 oC. lc cng cao ca ng thy tinh cho php ch to ct c thnh mng v d un.

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Cc ct mao qun c trng lp lng ln thnh cung cp phn gii cao hn v thi gian phn tch ngn hn so vi ct nhi. Ct mao qun hp c phn gii cao hn so vi ct mao qun rng nhng chng i hi p sut cao hn v c dung lng lm vic nh hn. Lp phin mng trn b mt trong mao qun t 0.1 n 5 nu gim lp phin ny s lm tng phn gii, gim thi gian phn tch nhng s lm gim dung lng hp ph. Ct mao qun

Cu trc bn trong ca ct mao qun:

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5. Yu cu pha tnh: Mt pha tnh l tng trong sc k cn th hin chn lc v kh nng ha tan ca cc cu t c tch v khong nhit lm vic rng. N cng phi bn ha hc, c p sut hi bo ha thp theo nhit , nhit lm vic nh nht theo nhit phng pha lng phi tn ti trng thi lng ( khng c tn ti trng thi rn). Cc php phn tch trong sc k l kt qu qu ca nhng phn tng tc gia pha tnh ha tan chn lc v s khc nhau p sut hi bo ha ca cc cht tan. Lc tng tc chu trch nhim chnh l lc phn b, cm ng, nh hng v tng tc cho nhn, tng cc lc tng tc c c trng bi phn cc phn t. Kh nng chn lc s chi phi phn tch gia cc pic v cao, hp ca pic thu c. khc nhau ca s chn lc cho php tch cc cc cht tan c cu trc gn ging nhau ca mt pha tnh. Cc yu t nh hng n chn lc gm bn cht pha tnh, nng pha tnh, nhit ct v vic chn la v s l s b cht mang rn hoc cht hp ph.

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Mt s pha tnh thng dng nh squalance, polysioxanes polyethylene, glycol. Vic la chn pha tnh ph thuc vo bn cht ca cht phn tch, ct phn cc tch mu phn cc v ngc li. 6. Cc loi detector: a. Detector o dn nhit Cu to n gin, p ng hu ht cc cht phn tch. Tuy nhin n c hn ch l dn nhit khng nhy d tm cc lng cht phn tch t cc ct mao qun m c ng knh <0.53 mm. dn nhit ca mt s kh 273 oK v 1 atm

dn nhit l kh nng vn chuyn nhit t vng nng sang vng lnh. Trong th nghim o dn nhit, cc phn t kh p vo si t s ly nhit ca si t ri bt ra vi ng nng ln hn. S va chm s tier l vi tc mt nhit. s khc nhau v khi lng phn t cht dn n s khc nhau tc chuyn ng ca cc phn t kh s dn n dn nhit khc nhau. Nh vy dn nhit H2 cao nht ri He ngi ta hay s dng He lm kh mang v He c dn nhit ln (th 2 sau H2) v tr.

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Nguyn tc: Mt dng kh mang lm kh so snh i qua cc cu R1, R2. Kh mang v mu sau khi qua ct c dn qua S1 v S2. C 4 si t S1,S2,R1,R2 c duy tr cng nhit , in tr chng c cng gi tr, cu cn bng, tn hiu ra bng 0. Nu in tr S1 v S2 thay i do kh mang cun theo cht phn tch th cu mt cn bng, xut hin tn hiu. nhy ca detector t l nghch vi tc dng kh, tng theo s khc nhit gia dy t v mi trng xung quanh, tng theo bnh phng cng dng dy. b. Detector ion ha ngn la: Nguyn tc hot ng: da trn s bin i dn in ca ngn la c cu to bi hn hp kh H2 v O2 trong khng kh v c t trong mt in trng. Kh mang sau khi ri khi ct i qua ngun ion ha vo bung in cc. chng b bn ph bi cc chum ht e to thnh cc ht tch in (ion dng, ion m, election). Kt qu to thnh dng in i qua in tr o R. S ri th Eo qua in tr R ny s c khuch i ri a ra my ghi. Nu ch c kh mang i qua 2 bn ca in cc, dng in sinh ra gi l dng nn, lm gim thiu dng ny ngi ta dng mt dng in b chnh. Kh mang em theo cc phn t mu, cc phn t ny b ion ha v dng in qua in cc tng ln. Cc tn hiu c ghi li di dng cc pic. ng dng: nhy ca detector FID cao hn rt nhiu so vi nhy ca detector TCD khong 100 n 1000 ln. Tuy nhin n khng s dng thc hp vi
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cc hp cht hu c: CO, CO2, axit formic, formaldehit, NOx, NH3, h p cht cha halogen, CS2, H2S, H2O v bn thn cc kh cn thit dng hot ng detector ny nh H2, N2, He. c. Detector cng kt in t (ECD) Nguyn tc: b phn chnh trong detector l bung ion ha, ni din ra cc qu trnh ion ha, bt gi electron v ti lin hp. qu trnh ion ha: t mt ngun phng x 63Ni c lp rp sn trong detector pht ra chum tia vi tc khong 108, 109 ht/ giy. Cc ht ny s ion ha phn t kh mang N2 hoc 5% metan trong Ar to cc ion dng ca phn t kh mang v in t t do s cp. So vi cc in t ca chum tia , cc in t ny chm hn. Chng c gia tc nh mt in trng v chuyn dch v pha anot. Ti y chng b ly mt in tch v qua to ra dng nn ca detector. Qu trnh cng kt in t din ra khi cc phn t cc cht phn tch vi cc i lc electron cao i vo detector. Chng bt mt electron dn n detector thay i hiu in th gia anot v catot duy tr dng nn khng i. s thay di ny c ghi nhn di dng pic sc k trn giy ghi hoc bng computer. ng dng: Detector loi ny c bit nhy vi nhng phn t hp cht c kh nng cng kt vi cc in t t do trong pha kh nh cc phn t cha halogen, cacbonyl lin hp, nitril, hp cht nitro, v hp cht hydrocacbon, cc ru v xeton. d. Detector ph khi My ph khi l mt detector vn nng cho phn tch nh tnh v nh lng cc cht hu c sc k ln sc k lng. Trong phng php ph khi, cc phn t kh ion ha (thng to catrion) c tng tc trong mt mi trng in t v sau c tch theo khi lng ca n. Qu trnh ion ha thng cung cp nng lng n phn t ph v n thnh nhng mng khc nhau. Mt ph khi l mt biu cho thy lng tng ng i ca mi mnh v to ra t detector ph khi. Trong sc k kh mi pic ca sc k tng ng vi mt cht phn tch c tch ra c nhn din vi mt ph khi. e. My ph khi nam chm hnh qut

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Nguyn tc hot ng vi ngun ion ha bng chum electron, cc phn t kh i vo ngun ion ha bng va chm electron v b bn ph bi cc electron c nng lng ng hc khong 70 eV. Nng lng ny ln ion ha cc phn t (M + e M+ + 2e) v ph v thnh nhng mnh nh hn. Mt hiu in th dng nh a y (repeller plate) y nhng ion hng v ng phn tch v mt th nh cc a hi t ion (ion focus plate) gia tc gip ion c vn tc cao b tng khi phn y ca b phn ny vo i vo ng phn tch. ng phn tch (analyser tube) c duy tr p sut chn khng cao ( khong 10-5 Pa) cc ion chuyn ng qua ng khng b lch hng bi nhng va chm vi cc phn t kh pha ng. Cc cation di chuyn qua ng phn tch chu tc ng ca t trng t vung gc vi hng di chuyn ca chng. Trng ny s hng cc cation v detector t cui ng phn tch. Mt khe detector ch cho nhng ion trong mt khong gi tr khi lng nh xc nh tip cn detector. Cc phn t c khi lng khng ph hp va phi cc thnh ng hoc b loi b bi khe thot ion nn khng vn ti c detector. Ti b phn thu ion (ion collector), mi catrion n b trung ha bi mt electron. Dng in i hi trung ha chm ion t l vi s lng cc ion n b phn thu ion ny. Ph khi l mt th cho thy dng in nh l mt hm s ca s khi c chn bi t trng. Phng php ion ha bi tng tc electron (electron impact ionization) cho ph khi c nhiu mnh v. Ion phn t c th c hm lng thp thm ch l bin mt. Nu phn t ln, th vic c qu nhiu mnh v s lm kh khn cho qu trnh c ph. Nguyn tc hot ng vi ngun ion ha ha hc: l mt k thut phn tch tinh t sn sinh ra t mnh v hn. Trong trng hp ny ngun ion ha c y metan vi p sut 10 pa. Cc electron c cung cp nng lng chun CH4 thnh sn phm hot ng CH4 + e CH4+ + 2e CH4+ + CH4 CH5+ + CH3 CH5+ l cht nhng proton khi tng tc vi cht phn tch cho MH+, thng l ion c hm lng ln nht trong ph khi ion ha hc metan. CH5+ + M CH4 + MH f. My Ph khi t cc Dng thay th cho my ph khi s dng nam chm hnh qut thng c t la chn ghp ni sc k bi t trng khng nhanh ghi ph ca nhng di hp. 7. L thuyt v phn tch nh tnh v nh lng ca phng php phn tnh sc k kh: a. Phn tch nh tnh: Trong phn tch nh tnh, hai detector c th nhn din cc hp cht l sc k ph khi v sc k hng ngoi chuyn ha fourier. Mt pic c th nhn din bng cch so snh ph ca chng vi mt th vin ph khi clu gi trong my tnh. Mt phng php km tinh t hn l nhn din thi gian lu ca mt cht vi
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thi gian lu ca cht trong mt mu bit trc ( mu chun) trn cc ct c phn cc khc nhau. Cch nh tin cy nht l so snh cc thi gian lu trong cng mt sc k thu c bi cc mu bit trc (mu chun) c thm mu cn d tm vo trong cng iu kin phn tch. Nu nh cht cn d tm trng vi cht c trong mu chun th pic ca mu chun s c din tch ln hn, chiu cao pic cao hn. S nhn din ch mc thm d khi thc hin trn mt ct, nhng ch khng nh khi thc hin trn mt vi ct trn nhng loi pha tnh khc nhau.

b. phn tch nh lng Mt s nguyn nhn gy sai s: chun b mu, tim mu khi tim cht lng tim mu iu kin nhit nu cao qu s gy phn hy cht phn tch. K thut tim mu cng gy sai s. Mu b phn hy hay hp ph: c nhiu trng hp c s phn hy hoc hp ph mu trong bung tim, trong ct, trong detector c th lm cho cc pic khng i din cho lng ca cc cht phn tch trong mu. khc phc hin tng nu ngi ta lp ng chun bit din tch pic hay chiu cao ca pic c t l tuyn tnh vi lng mu a vo hay khng. p ng ca detector cng c th gy sai s v cc detector p ng khc nhau vi cc hp cht khc nhau. V vy cn phi bit r cc h s p ng ny. Hn na khi thay i iu kin lm vic ca thit b p ng ca detector cng thay i. Trong GC c
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th dng phng php ni chun khc phc sai s ny. K thut phn tch: trong GC c nhiu phng php thit lp lin quan gia thng tin ghi nhn v hm lng cu t: o chiu cao pic, dng my ghi v tch phn, ct v cn giy. Cc cch ny c th gy sai s ring trong qu trnh x l. b. Cc phng php phn tch nh lng Phng php chun ha din tch: y l phng php tnh thnh phn phn trm ca mu bng cch o din tch tng mu trn sc k . Theo cch ny, em mu phn tch ca cht cn quan tm A cho tng din tch cc pic %A = (din tch pic A/ tng din tch cc pic) *100%. Khi phn tch thnh phn c im si khc nhau ca mt dy ng ng, phng php ny c th s dng tnh t l phn trm khi lng. phng php ny ch ng nu tt c cc cht phn tch u c ra gii v p ng detector vi mi cu t l ging nhau. Nu nhng iu kin ny m tha mn th y l mt phng php nhanh v hiu qu. Phn php tnh theo h s hiu chnh: nh bit detector p ng khc nhau i vi cc cht khc nhau. V vy cn phi tnh h s hiu chnh. Nh h s ny c th tnh c phn trm ca cc cu t trong mu. ( ) %A=
( )

Cch xc nh h s hiu chnh: tim dung dch chu bit nng cc cu t A,B,C, vo GC. Sc k thu c c cc pic phn gii hon ton v din tch thu c tng ng l SA, SB, SC, tng ng vi cc mu c khi lng mA, mB, mC. Chn mt pic lm chun v d A c t l SA/ mA c gn gi tr FA=1. T t l SB/mB, SC/mC suy ra FB, FC c. Phng php lp ng chun: Lp cc ng chun ring r i vi tng cu t trong hn hp cch tim nhng th tch bng nhau ca mt lot dung dch hn hp cht chun c nng khc nhau. Nh vy, mi mt lot cc nng ca cc cht chun c phn tch v c din tch c xc nh. Mt ng chun c xuy dng cho mi cu t vi mt trc l nng cn trc kia l din tch ca chng. Kim tra s p ng tuyn tnh ca detector. Tim cng th tch mu ca cu t cn phn tch v chy sc k trong iu kin nh chy chun. T th v din tch o ca mu phn tch ta xc nh c nng ca mu. d. Phng php ni chun Phng php ny cn gi l phng php chun ha tng i hay gin tip. xc nh lng mt cu t X ta cn phi chn mt cht chun S sao cho: Nu trn ln X v S ta phi thu c 2 nh ring bit trn sc k . Pic X v S phi kh gn nhau. Sau ta phi pha cc hn hp c t l trng lng ca X v S bit trc, chy sc k, o din tch cc pic, lp t s din tch cc pic tng ng, cui cng lp ng chun tng i.

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y : Sc/Ss l t l th tch ca cc cp cu t cn xc nh X v cht ni chun, Wc/Ws l t l trng lng ca cc cp cu t cn xc nh X v cht ni chun. Khi phn tch mu tht, ta cho mt lng bit trc cht ni chun S vo mu ri tin hnh sc k hn hp, t t l din tch o c, bng ng chun tng i va xuy dng ta c th xc nh trng lng cht X. Phng php ny c u im l: Khng cn bit n p ng ca detector, khng cn duy tr nghim ngt cc iu kin phn tch sc k v cc sai s c loi tr nh cch tnh t s.

PHN 3: SC K LNG 1. Cc b phn ca b sc k lng:

Nguyn l hot ng: hn hp cn phn tch c ha tan trong mt dung mi thch hp, tim mt th tch chnh xc vo b phn tim mu v c mang
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vo ct bi mt dng chy lin tc ca dung mi (pha ng) trong mu c ha tan. S tch din ra trong ct c cha nhng ht xp c din tch b mt ln (pha tnh). Cc cu t trong mu lin tc tng tc vi pha tnh. Pha ng ( cn gi l cht ra gii) c bm qua ct nhi cht cc ht sc k. Vi vic chn pha ng v chn vt liu nhi ct thch hp, cc cu t trong mu s di chuyn dc trn ct vi nhng tc khc nhau, khi nhng cu t ln lt thot ra khi ct v i vo detector thich hp, ay tn hiu c s l v chuyn ra ngoi ct sc k cho bit s hin din ca cc cu t di dng mt pic. Khi lng cc cu t c trong mu c tnh ton da vo chiu cao hoc din tch pic ca n. a. Bnh cha dung mi Bnh thy tinh 1 dm3. Dung mi bm vo phi khng cha bi bn v cc vt th l khc v iu ny c th lm nh hng ti tui th ca bm hoc lm kt cc ct tch. Cn lc dung mi qua giy lc 0.45 trc khi s dng v an ton hn, u ng nha trong bnh cha dung mi phi c u lc. cn loi b hoc ui cc bt kh ha tan trong dung mi bng cch chy siu m, sc kh tr nh He. Trong phng php ra gii c th s dng mt dung mi hay hn hp cc dung mi. T l trn cc dung mi phi c lp trnh theo lich trnh v t l cho trc. b. p sut ct tch p sut trong ct tch c th ln hn 200 ln p sut kh quyn. n v s dng l bar, psi,p sut ct c th chu l 200 bar, ct lm vic trong iu kin 20 n 100 bar. c. H thng bm Chc nng chnh ca h thng bm l vn chun pha ng i qua ct tch vi mt tc xc nh. C 2 loi bm c s dng l bm dng c nh kiu syringe y lin tc, loi th 2 l bm piston ht y lun phin. d. H thng tim mu Phng php tim mu s dng trong sc k GC. Phng php tim mu stopped flow. Phng php tim mu vng mu l phng php ph bin nht hin nay, dng van tim mu c mt vng mu dung tch 5 n 500 . Phng php ny rt d s dng, t ng, v chnh xc kh cao. Mu u tin c tim bng xylanh vo vng mu, sau chuyn van t v tr np mu n v tr tim mu ni vng mu vo v tr ca dng chy pha ng. e. Ct sc k lng hiu nng cao Cc ct s dng trong HPLC c lm t vt liu thp khng r, vi mt trong c lm nhn, kch thc ph bin l 6,35 ng knh ngoi, 4,6 mm ng knh trong, chiu di 25 cm. ct c nhi cc ht c ng knh 3,4,5,10 . Cht nhi l silicagen c bc mt lp mng hu c. 2. Cc loi detector trong sc k LC
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C kh nhiu thit b c ng dng lm detector trong HPLC. Nhng c trng quan trng ca detector trong HPLC l: Nhy, tuyn tnh, p ng (respond) chn lc hoc thng dng, p ng khng b tc ng bi nhng thay i ca cc iu kin th tch cht thp, khng d b ph hy, r tin, ng tin cy v d s dng. Khng c detector no c th s hu tt c nhng c trng trn v chng khng hon ton c lp vi nhau nn ci thin mt c tnh ca n c th lm ti thm ci kia. Bt k mt detector no cng chu ting n ca thit b, ch yu l phn in, ln ca n xc nh lng cht ha tan nh nht c th c d tm. Bi v khi ta gim lng cht phn tch n mt gi tr no th tn hiu t detector s qu nh c th phn bit n vi ting n ca detector. nhy ca detector thng c xem nh nng to ra tn hiu c nh tn hiu to ra bi ting n. Mt detector tuyn tnh c tn hiu t l thun vi lng hoc nng ca cht tan. Khong tuyn tnh ca detector chnh l khong nng m s tuyn tnh ny tun theo. Gii hn pht hin cho bit lng ti thiu ca cu t c th c thy mt cch ng tin cy trn sc k . V mt thc nghim gii hn d tm ca mt cht l lng cht cho mt pic gp vi ln ting n ca nn (thng 3 ln). Mt detector vn nng th nhy vi mi th c trong mu v d detector khi ph, cn mt detector chn lc th ch nhy vi mt vi cu t no nh detector ECD nhy vi hp cht cha halogen.

a. Detector UV-VIS y l loi ph bin nht trong HPLC. Nguyn tc ca n l cho pha ng t ct c chy qua mt ng o (flowcell) nh c mt chm bc x n sc UV/VIS chiu qua.
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S hp thu bc x ca cht tan l mt hm ph thuc tuyn tnh vo nng C ca n theo nh lut Lambert-Beer: D = lC y: - D l i lng mt quang; - l l chiu di ca cell; - l h s hp thu phn t v l hng s cho mt cht tan v bc sng. n v ca ph thuc vo th nguyn ca l v C. Trong h SI th nguyn ca C l mol m-3, l l mt nhng trong thc t C c o vi mol dm-3 cn l l cm nn l dm3 mol-1 cm-1. nh lut Lambert Beer ch ng khi chm sng b hp thu l n sc, nhng h thng detector thng khng cung cp chm tia n sc m ch mt di hp cc chm tia quanh gi tr bc sng c chn. Mt ng o (flow cell) trong UV detector c ng knh trong khong 1 mm v chiu di nh sng i qua khong 10 mm, nh vy th tch cha khong di 8 l b. Detector chui photodiot Trong detector UV-VIS chm sng a sc c cho i qua mu sau hi t vo khe vo ca b n sc ha (monochromator) tch chm tia n sc cn o hng vo b d tm. Mt quang ca mt mu c tm thy nh so snh gia cng ca chm tia ti b d tm khi khng c mu (cn gi l mu trng) vi chm tia i qua mu. o mt quang ti nhng bc sng khc nhau, bc sng c thay i nh quay chm lng knh hoc b cch t (grating) trong b n sc ha. S hin din ca b phn quay trong thit b gii thiu thm sai s (v d do s git li c hc) v vic quay chm c th gy tn thi gian. Trong detector chui photodiot, chm tia a sc sau khi i qua mu c tn x bi b cch t c c nh ri ri vo mt chui cc photodiot. Mi photodiot o mt di hp cc bc sng trong quang ph, nh vy n l b thu nhn s liu song song, ngha l tt c cc im c o ng thi. H thng ny c mt s thun li nh sau: + Bi v l b thu nhn s liu song song nn vic x l v lu tr quang ph c th c thc hin trong khong 0.5 s so vi vi pht trong detector UV. + V khng c b phn di chuyn c th b lm mi mn nn nhng sai s khi thit lp li mt bc sng cn chn c gim xung v thit b cng t i hi bo dng mnh thit b khc. + Nh kh nng thc hin nhng php o nhiu bc sng cng mt lc v tc thu nhn s liu nn nhng k thut ly trung bnh s liu khc nhau c th c s dng lm gim ting n v tng nhy.
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+ Khi c s dng nh mt detector trong HPLC, mc d t tin hn so vi loi UV truyn thng nhng n cng c nhng u im ng k: + Quang ph ca mi pic trong sc k c th c lu gi v ln lt so snh vi ph chun gip tin li trong vic nhn din cc pic. + Bc sng ti u cho vic d tm cng d dng c tm thy v nhng thay i ca bc sng trong qu trnh d tm cng c th c chng trnh ha xy ra ti nhng im khc nhau trong sc k . + N cng cung cp nhy cc i cho cc pic. c. Detector hunh quang Nhiu hp cht c kh nng hp th chm tia UV ri sau ngay lp tc pht ra bc x c bc sng di hn (hunh quang) hoc sau mt s tr thi gian (ln quang -phosphorescence). Thng phn nng lng b hp th sau pht x tr li l tng i thp nhng c mt vi hp cht, phn pht x tr li c th t 0.1-1 nn thch hp cho vic d tm hunh quang. Nhng hp cht nh vy thng c vng lin hp nh cc hp cht vng thm c nhiu nhn. Nhiu hp cht khng c ph hunh quang c th chuyn sang cc dn xut c ph ny nh x l vi nhng thuc th thch hp. d. Detector o ch s khc x Detector (RI) ny nhy vi s khc nhau gia ch s khc x ca cc cht ra gii t ct vi dng chy ca pha ng nguyn cht. y l loi detector thng dng nht v bt k cht ha tan no cng c th c d tm min l n c ch s khc x khc vi dng chy ca pha ng nguyn cht.Tuy nhin, loi detector ny km nhy khong 1000 ln so vi detector UV. Mc ting n tt nht c th thu c vo khong 10-7 n v ch s khc x, iu ny tng ng vi nng tng ng ting n khong 10-6 g.cm3 cho hu ht cc cht tan. C nhiu mu thit k cho detector o ch s khc x, nguyn tc c bn hot ng: + Cuvet c hai bnh tam gic c th tch 5 n 10 microlit trong mi bnh c dung mi nguyn cht v dung dch cht tan chy vo. + Chm sng kh kin lc cc bc x hng ngoi (c th lm nng mu) c chiu qua cuvet c dung mi nguyn cht chy qua 2 bnh tam gic v c hng vo ng nhn quang in nh mt a deflection. + Khi cht tan vi ch s khc x khc i vo cuvet, chm sng b lch lm tn hiu ca ng nhn quang in thay i. Detector RI khng dng trong sc k ra gii bin i nng u (gradient) v n khng th d tm chnh xc khi thnh phn pha ng b thay i. RI nhy vi s thay i nh ca nhit v p sut (0.01oC). V c nhy thp nn n khng c dng trong phn tch lng vt. RI cng c khong nng tuyn tnh hp.
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PHN 4: QUY TRNH THAO TC MY GC 14B SHIMADZU -Bt my sinh kh N2 -Bt my GC,CR-6A -t chng trnh nhit +Nhit bung bm mu 1200 C +Nhit detector 2000 C

+t nhit u v cui ca ct l 800 C( ng nhit) +Bt cng tc heater ca my +Bt my nn kh ,bt my sinh kh H2 +nh la ca FID, kim tra xem c ngn la khng +Bm mu phn tch, bm Start CR-6A v ch kt qu. Khi kt thc mu phn tch bm Stop -Khi khng s dng my th tt: +Tt CR-6A +t nng bung bm mu, detector,ct v 250 C Tt cng tc heater ca GC-14B +Tt my sinh H2 ,tt my nn kh +Ch khi t bung bm mu xung di 1000 C th tt my sinh N2 +Tt my GC-14B Ch : -Khng t t ct >3000 C , t0detector,injector >3200 C -t0detector,injector t0 ct+300 C
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-Mu khng c cha nc v phi bay hi c -Lng mu nn dng: 0.1-0.2l (lng); 0.5-1 ml -Ra kim bm 15-20 ln(bng n-hexan) trc v sau khi bm mu

xc nh c din tch pic c th dng cc phng php sau: -Dng thit b o din tch -Tnh din tch tam gic bng phng php th cng -Phng php ct sc v cn trng lng -Dng tch phn k in t v chng trnh my tnh tnh Spic

PHN 5: BO CO KT QU TH NGHIM 5.1. Ch phn tch Nhit detector : t =2000 C Nhit injector : t=1200 C Phn tch ng nhit: tct =800C 5.2. S liu o c :
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Mu 100% n-hexan 100% toluen Mu 0.1%toluen 1% toluen 10% toluen

Tgian lu 2.508 5.902 2.588 5.462 2.74 5.782 2.793 5.897 2.9 6.173

spic 22067812 23679610 1080329 4401558 21803222 87646 16460220 845138 14537756 6395758

5.3.

X l s liu. Xy dng th S-C (%toluen)

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TH NG CHUN CA TOLUEN
30000000

25000000

y = 224016x + 2E+06 R = 0.9726

20000000 DIN TCH PIC

15000000

Series1 Linear (Series1)

10000000

5000000

0 0 20 40 60 80 100 120 NNG TOLUEN

Hnh 1 :

th S-C y

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DIN TCH PIC

TH NG CHUN CA TOLUEN
7000000 y = 628894x + 115941 R = 0.9992 6000000

5000000

4000000 Series1 3000000 Linear (Series1)

2000000

1000000

0 0 2 4 6 8 10 12

% toluen

Hnh 2 : th S-C loi b im A

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25000000 y = 233453x + 336754 R = 0.9996

20000000

15000000 DIN TCH PIC

Series1 Linear (Series1) 10000000

5000000

0 0 20 40 60 80 100 120 % C TOLUEN

Hnh 3 : th SC loi b im B Nhn xt : ta thy tin cy R2 hnh 2 < 0,99 . theo phng php bnh phng nh nht th kt qu ng thng bnh phng nh nht l khng chnh xc . V vy ta loi b cc gi tr gy sai s cho vic xc dnh ng chun trung bnh. Da trn th ta thy 2 gi tr c th l sai s l
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A ( 100 ; 23679610) v B (10; 6395758) Trng hp 1 : loi b gi tr A suy ra R2 = 0.9992 Trng hp 2 : loi b gi tr A suy ra R2 = 0.9996 Ta thy 2 trng hp trn c gi tr tin cy u ln hon 0,99 nhng trng hp 2 chnh xc hn . vy : Y= 233453X + 336754 . Mu X c din tch pic i vi toluen l Y= 4401558 => mu c nng toluen l : X = 17.4% . 5.4. Sai s mc phi - Do qu trnh ly mu bng tay nn khng th ly chnh xc dc 2 micromet mu nn s n n sai s xc nh S pic so vi Spic thc t ng vi nng cc ln ly. V Spic ph thuc vo lng cht phn tch i ra tc l ph thuc vo nng mu phn tch v th tch mu phn tch. Mun xc nh chnh xc S pic ng vi thay i nng iu kin tin quyt l Vmu =const. - Sai s mc phi do qu trnh luyn ct khng tt, cha y ht cc cht hp ph trong ct t cc ln trc.

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