You are on page 1of 9

TM TT GC 06-30-2008, 07:56 PM H thng detector trong my GC (gas chromatography) pht hin kh thng qua tnh cht vt l hoc ha hc c trng

ca kh. Hin nay trong my GC s dng rt nhiu loi detector khc nhau v cu to v nguyn tc pht hin. Ty vo mc ch m ngi ta s xem xt, la chn detector thch hp nht. y chng ta ch s im qua mt s loi detector thng dng nht dng trong GC: TCD (Thermal Conductivity Detector), FID (Flame Ionization Detector), ECD (Electron-Capture Detector) v PID (PhotoIonization Detector). u tin, cn xem xt cc c im chnh ca detector. 1. Cc c trng chnh ca detector nhy tin li, detector c chia ra hai loi: detector truyn khi (mass flow detector) v detector nng (concentration-sensitive detector). Detector truyn khi pht hin kh theo lu lng kh n detector (th tch kh n detector trong mt n v thi gian ng/s), trong khi detector nng cho kt qu xut ra t l thun vi nng kh trong pha ng (v d ng/ml). nhy ca mt detector c nh ngha l s thay i ca tn hiu detector ng vi s thay i ca khi lng hoc nng kh ra. Nh vy nhy chnh l h s gc ca th biu din tn hiu xut ra ca u d theo khi lng hoc th tch kh phn tch. Dynamic range v Linear range Dynamic range l khong m trong gii hn , detector vn cn cho tn hiu thay i ng k khi thay i khi lng hoc nng ca kh. Gii hn pht hin LoD chnh l gii hn di ca dynamic range. Trong dynamic range, ngi ta lu n linear range, y l khong m trong tn hiu xut ra ca u d t l thun vi khi lng hoc nng kh phn tch. Linear range ph thuc nhiu vo nhit ct sc k, nhit detector v lu lng dng kh. http://img99.imageshack.us/img99/5452/noname1ph8.png Dynamic range v linear range

chn lc Cn c theo chn lc, c th chia detector trong GC thnh hai loi: detector ph bin (universal) v detector chn lc (selective). Detector ph bin c th nhn bit c tt c cc loi kh khc nhau thot ra t ct sc k, cn loi detector chn lc ch c th cho phn ng vi mt loi nguyn t c th no c trong mu phn tch (v d N, P). C th v d FID thng dng phn tch thnh phn du la v n c th cho tn hiu cc hydrocacbon nng rt thp, do vy FID l detector chn lc i vi cc hydrocacbon. Trong khi phn tch kh t nhin, nhiu kh (N2, CO) khng cho hoc cho tn hiu rt nh khi dng FID. Trong trng hp ny TCD thch hp hn v n c th cho tn hiu vi tt c cc kh khc nhau. Do vy TCD l mt loi detector ph bin. http://img257.imageshack.us/img257/7452/53793766kt0.png Cc detector thng gp trong GC

(to be continued ...) F91 07-01-2008, 06:23 PM 2. Thermal Conductivity Detector (TCD detector dn nhit) TCD l mt detector ph bin, khng ph hy mu c thit k ln u tin vo nhng nm 80 ca th k XIX v dng rng ri trong phn tch kh u th k XX. Hin nay vi s xut hin ca cc detector ion ha vi LoD thp hn, TCD ch cn c coi nh l mt loi detector dng trong nhng phn tch i hi yu cu khng cao. Tuy nhin detector ny rt c ch khi cc detector khc cho kt qu khng tt, nht l khi phn tch mu c cha CS2, COS, H2S, SO2, CO, CO2, NO, NO2. Cu to http://img77.imageshack.us/img77/4539/55315480ks4.png Hnh dng ca 1 TCD

Thit k cc mch in trong TCD n gin hn trong cc detector khc. Tuy nhin yu cu v ch to li kh cao, c bit l vn n nh nhit cho detector. Do tt c cc b phn ca TCD u c t trong mt hp kim loi kn v c gi nhit ln hn ct sc k. TCD thng hot ng vi kh mang l H2 hoc He do dn hai kh ny cao hn nhiu so vi nhng kh cn li. Thng thng mt dy tc xon s c dng thay cho mt dy thng tng in tr. Dy tc thng c lm bng Pt, W, Ni hoc cc hp kim ca Re v Ir. Mt mch cu Wheatstone thng c s dng cn bng in tr. R1 v R2 l hai in tr vi gi tr c nh, R3 l ni mu kh i vo v R4 l mt bin tr so snh. Tt c gi tr in tr u bng nhau nu khng c mu i vo, v do khng o c s thay i hiu in th. http://img77.imageshack.us/img77/5801/noname1jv8.png S mch cu Wheatstone s dng trong TCD

Nguyn tc lm vic TCD hot ng da trn nguyn tc o dn nhit ca cc kh khc nhau. Bnh thng ch c kh mang l H2 hoc He i vo nn gi tr R3 n nh, mch cn bng v ta khng o c s khc nhau ca hiu in th. Mu kh thot ra t ct sc k s c dn ti R3 trong detector. Do kh trong mu dn nhit km hn kh mang, do nhit ca R3 s gim v do gi tr R3 cng s gim theo cng thc R = Ro (1 + T) h s nhit in tr Ro in tr ti 0oC Do R3 gim nn mch cu khng cn cn bng, t hiu in th v dng trong mch s c o. Ty vo tn hiu in ghi nhn c detector c th tnh ton ngc tr li gi tr R3 v nhit ti R3, t c th bit c dn nhit theo phng trnh http://img65.imageshack.us/img65/4311/nonamemi8.png

3. Flame Ionization Detector (FID Detector ion ha bng ngn la) c Harley, McWilliam v Dewar ch to ln u tin vo nm 1958. K t FID tr thnh detector c s dng ph bin nht trong my GC. C nhiu nguyn nhn c th gii thch c iu ny. u tin, detector ny hot ng tt vi hu ht cc hp cht hu c vi mt nhy cao. Tn hiu khng b nh hng bi nhng bin i va phi v nhit , p sut v lu lng kh. Hn na, FID khng b gy nhiu bi nhng tp cht thng gp nh CO2 v hi nc. Cui cng, khong tuyn tnh ca detector loi ny rt rng, c th ln n 107. Cu to v nguyn tc hot ng FID bao gm mt b phn c th to ra ngn la c t bng hn hp H2 khng kh.

Khi mu cha cc hp cht hu c ti c ngn la, trong mi trng giu hydro ny chng s b chuyn thnh cc gc t do cha mt nguyn t cacbon. Vi s hin din ca oxy trong dng kh, phn ng sau s xy ra CHO+ s phn ng tip vi H2O c to thnh trong ngn la cho ion hydronium Chnh ion ny v nhng dng (H2O)nH+ khc n c in cc, cho tn hiu t l thun vi lng ion. Nh vy FID s cho kt qu t l thun vi s lng cacbon c trong hp cht thay v t l thun vi khi lng hay s mol cht n detector. Kch c ca ng dn (jet) ty thuc vo loi ct sc k v cch thc tin hnh, thng thng dao ng t 0.28 0.76mm. http://img68.imageshack.us/img68/3412/noname1lz4.png Cu to 1 FID Lu lng kh a vo nh hng nhiu n nhy ca detector, cng nh quyt nh n t l kh mang/H2. Gi tr cc i ca lu lng v t l ny ph thuc vo kh mang no s c s dng. Thng thng, vic s dng N2 s cho hiu qu tt. Cng nh i vi tt c cc detector khc c s dng trong GC, vn iu khin nhit trong FID rt quan trng. Detector cn c bo v kn v c nung nng hn mt cht so vi ct sc k trnh trng hp xy ra s ngng t ca mu kh khi lu chuyn gia cc ng dn. Tuy nhin cng khng c cho detector qu nng v khi b mt rn b t nng s bc x electron v gy tn hiu nhiu. Cc c im hot ng ca FID Tn hiu ca detector s b nh hng bi cc d nguyn t nh O, S v halogen c mt trong hydrocacbon. Mt im mnh ca FID l rt t b gy nhiu bi nhiu kh. Bng sau y cung cp mt s kh tiu biu. http://img157.imageshack.us/img157/9165/noname1kc5.png Thun li ca FID l khong tuyn tnh rt rng, n 10^7, LoD cng rt nh 10-13gC/s. iu kin hot ng bnh thng, nhng dng c 10^(-13)A u c ghi li. Mt khuyt im ca detector ny l ph hy mu, do vy trong cc h thng a cp, FID lun lun c s dng sau cng. ci tin detector loi ny c th pht hin c cc hp cht v c, thay v t trong hn hp H2 khng kh, ngi ta thay bng hn hp giu H2 trn ln vi O2 v c gi l HAFID (Hydrogen Atmosphere FID). Detector ny cng c dng pht hin cc hp cht c kim cha Fe, Sn, Pb, Mo, W http://img65.imageshack.us/img65/548/32630739gi7.png LoD ca 1 s kh khi s dng HAFID (to be continued ...)

F91 07-02-2008, 06:48 PM 4. Electron-Capture Detector (ECD Detector bt electron) ECD l u d c dng rng ri trong GC hin nay, c l ch ng sau FID. Do c th pht hin n picogam (10^(-12)g) v thm ch c th n femptogam (10^(-15g)) trong mt s trng hp nn ECD c dng nhiu trong phn tch mi trng v dc phm. Loi detector ny c ch to ln u vo nm 1951. Nm 1958, Lovelock ci tin v ngh l thuyt bt electron, theo cc nguyn t c m in ln trong cc hp cht nh halogen c th bt electron v to thnh ion m: CX + e- CX- + Nng lng Cu to Thit k ECD ch n gin gm mt bung kn cha hai in cc v mt ngun pht bc x electron ion ha. Hnh bn di trnh by hai kiu thit k detector ph bin hin nay. Cu to (a) gm c anode v cathode c thit k ng trc. Trong khi hnh (b), ngun bc x l mt tm mng, anode v cathode c thit k to thnh hai mt phng song song. iu ny to thun li hn khi dng kh i vo chuyn ng ngc chiu vi cc ht mang in tch m v do to s va chm, tip xc tt hn. Trong ECD, ngun bc x - thng gp nht l 63Ni mc d thnh thong ta vn gp T (tritium) c thng mi ha. Tm xa ca bc x t T ch khong 2mm, trong khi 63Ni l 8mm. Nhit hot ng cao nht ca T v 63Ni ln lt l 225 v 400oC. Gii hn nhit di ty thuc vo cc iu kin ca ct sc k. Nu nhit qu thp, cc cht kh thot ra t ct s ngng t trn thnh ng dn n kt qu sai lch. Detector s dng 63Ni c th thng xuyn c lau chi bng cch vn hnh nhit cao, khi cc electron ng vai tr lm v sinh cho detector. http://img92.imageshack.us/img92/7704/noname1it1.png Cu to ca ECD: (a) 2 in cc ng trc; (b) 2 in cc song song C ch hot ng Bnh thng, dng kh mang (hay s dng l N2) i qua s b cc electron bc x t 63Ni ion ha to nn cc ion dng. Cc ion v electron ny di chuyn gia hai in cc v to thnh dng in nn cn bng Io. Khi trong dng kh xut hin hp cht c mang nguyn t m in cao, n s bt electron v phn ng vi cc ion theo phng trnh MX + e- MXMX- + N2+ M + N2 Do , cng dng s gim theo hm I = Io/(1 + kC) v s c detector ghi nhn. Cc yu t nh hng Phn ng ca electron vi cc phn t hp thu l phn ng bc hai, do ph thuc rt nhiu vo nhit . Do kim sot nhit l mt yu cu rt nghim ngt. Thc t,

detector c gi c nh mt nhit ( 0.1oC) bi v s lng v nng lng ca electron pht ra t ngun bc x, c ch hp thu electron u ph thuc mnh vo nhit . C ch hp thu cn b nh hng ca chnh bn cht ca cht hp thu. gim thiu cc yu t khng n nh, iu kin vn hnh detector c kim sot cht a phn ng hp thu electron v phn ng gi bc mt. Hiu r c ch phn ng mi c th tin hnh tnh ton nng kh trong mu. http://img352.imageshack.us/img352/3010/noname1mo1.png nh hng ca nhit n tn hiu u ra ca ECD Nhiu nghin cu c gng ch to ECD m khng s dng ngun bc x -. Mt trong nhng c gng nh vy c a vo thng mi: PDECD (Pulse Discharge ECD). 5. PhotoIonization Detector (PID Detector ion ha quang hc) PID s dng ngun bc x UV ion ha mu, c Lovelock gii thiu ln u tin vo nm 1960. Detector ny cng cho mt khong tuyn tnh rng (107), ng nn n nh v thp. Hu ht PID hin nay u s dng n chiu UV ion ha, c s dng ch yu phn tch cc hp cht thm v c ni kp trong phn t. Cu to http://img230.imageshack.us/img230/9255/noname1jx2.png Cu to ca PID B phn chnh l mt n UV cng sut ty vo mu cn phn tch, thng thng nng lng UV nm trong khong 8.3 11.7 eV. Bung chiu UV v bung ion ha cn c ngn cch vi nhau bng mt ca s trong sut, thng lm bng thy tinh hoc thch anh. Tuy nhin khi s dng nng lng cao, cc tinh th florua ca kim loi kim v kim th li c s dng nhiu hn. Nguyn tc hot ng Mu kh i vo detector, nu nng lng ion ha ca chng thp hn nng lng tia UV chiu x th s xy ra qu trnh ion ha R + h R+ + eCc ion ny s di chuyn ti in cc v cho tn hiu t l thun vi s phn t b ion ha. Ty thuc vo n UV s dng, ta s c c chn lc thch hp. Vi nhng n nng lng thp s dng Kr hoc Xe, chn lc s cao hn v chng ch c kh nng ion ha mt s t cc phn t. Nhng n c nng lng cao hn nh Ar hoc H2 s cho tn hiu vi mt lng kh ln hn. Tn hiu thu c t detector tha phng trnh i = IoFNlC vi Io thng lng photon

F hng s Faraday hiu sut qu trnh ion ha N s Avogadro l qung ng di chuyn ca cc ion C nng cc phn t c th b ion ha

You might also like