XC NH ACETALDEHYDE TRONG ETHANOL NHIN LIU BNG HPLC VI U D IN HA Chu trnh hot ng in phn ca acetaldehyde v sn phm dn xut vi dinitrophenylhydrazine

2,4 (DNPHi) c nghin cu mt in cc carbon thy tinh. Nghin cu ny c s dng ti u ha cc iu kin th nghim tt nht xc nh chng bng phng php tch sc k lng hiu nng cao (HPLC) cng vi u d in ha. Acetaldehyd 2 ,4-dinitrophenylhydrazone (ADNPH) c rav tch ra bng ct pha o C18, di iu kin ng th vi pha ng cha hn hp 2 cht methanol/LiCl(aq) nng l 1.10-3 M (80:20 v/v), tc dng chy 1,0 mL min-1.iu kin ti u u d in ha ca ADNPH l 1,0 V so vi Ag / AgCl nh mt in cc tham kho. Phng php c xut n gin, nhanh chng (phn tch thi gian 7 pht) v nhy(gii hn pht hin l 3.80 L-1) ti mt t l tn hiu: nhiul 3:1. N cng rt chn

lc v c lp li .[ lch chun 8,2% 0,36 (n = 5).ng cong phn tch ca ADNPH tuyn tnh trn phm vi 3 - 300 mg L-1cho mi ln bm mu(20

), v lp li ca php phn tch l >99%.

GII THIU Ti Brazil, vic s dng ethanol nh mt nhin liu t hoc mt ph gia oxy ha xng du tng ln ng k t nm 1975 l kt qu ca Chng trnh Ru Quc gia a ra nh l mt chin lc tr nn c lp hn v du nhp khu.Hin nay, sn xut ethanol nhin liu hng nm ca Brazil l khong 14 t m3/nm, n thuc loi mt nh sn xut ln nht th gii. S c mt ca cht gy nhim v c v hu c trong nhin liu ethanol c kim sot mt cch cht ch bi mt c quan qun l lin bang (Agncia Nacional do Petroleo) theo gii hn cho thnh phn ca tp cht.Mc d, nhng cht gy nhim c coi l l mt sn phm th cp, nhung chng c nh hng

quan trng c bn khi ng c hin i c s dng, c pht trin vi cng nghcao, v do i hi nhin liu phi c tinh khit cao. Khi vic sdng nhin liu ethanol c hn ch, th phng php phn tch c sn s nhanh, chn lc v nhy nh lng cht nhim hu c tr nn kh khn. Acetaldehyd l tp cht quan trng nht c thy trong nhin liu ethanol cc mc khc nhau ca nng , m ph thuc vo qui trnh sn xut, s tch ly v cc yu t khc. Mc d tm quan trng ca n c bit n nhiu, nhng c ch l mt vi bi vit trong cc ti liu c lin quan n cc ngh thay thphng php xc nh v nh lng ca n, m chng rt quan trng i vi mc ch kim sot cht lng, chng hn nh phi bit thnh phn ha hc c th. Hu ht cc phng php HPLC lin quan n acetaldehyd u c da trn mt phn ng vi dinitrophenylhydrazine 2,4 (DNPHi) ci thin tnh nhy ca sphn tch cc hp cht cacbonyl. Mc ch ny c thit lp bi Kissinger et al, pht hin nhng hp cht ny vi u d in ha.Tuy nhin,c mt phng php HPLC xc nh acetaldehyde trong ethanol nhin liu bng cch s dng u d in ha c m t.Chng ti bo co v s pht trin ca mt phng php n gin cho nh lng acetaldehyde trong etanol nhin liu da trn phng php HPLC vi u d in ha. THC NGHIM Thuc th Tt c cc ho cht s dng ca loi thuc th ACS hoc nh ethanol, methanol v acetonitril, phi tt hn. Acetaldehyd l t Merck (Darmstadt, c). Tt c cc dung mi c s dng, c cp t Mallinckrodt HPLC (Xalostoc, Mexico). Nc kh khong c thu thp t mt H thng nc MilliQ (Millipore, CA, USA). 2,4-dinitrophenylhydrazine (DNPHi) t Merck (Darmstadt, c) c tinh ch bng ba ln recrystallizations lien tip tmethanol.H3PO4 l t Aldrich Chemical Co (Milwaukee, M). LiCl v LiOH, thu

c t Aldrich Chemical Co (Milwaukee, M), c s dng h tr in phn trong nc kh khong. Dn xut acetaldehyd-2 ,4-dinitrophenylhydrazone (ADNPH) ADNPH c s dng nh l mt cht chun c chun b t phn ngc bit n nhiu ca cc hp cht cacbonyl vi 2,4-dinitrophenylhydrazine (DNPHi), thu c nh m t. DNPHi (0,4 g; ca. 2 mmol) c ha tan trong axit photphoric m c (2 mL) vnc kh khong (3 ml). vi s ha tan ny acetaldehyde chun (1g) c ha tan trong methanol (15ml) c thm vo. Sn phm phn c tch ra thng qua lc v c lm tinh khit (hai ln) bng recrystallization t ethanol tinh khit. Dung dch chun c chun b bng cch ha tan tng trng lng (1g L-1) ca ADNPH tinh khit trong acetonitrile. Thnh phn ca dung dch ny sau c pha long vi hn hp ethanol v nc thch hp(95:5 v/v) ti thiu ha nh hng nn, cng nh lm dung dch chun cho mc ch hiu chun, chun b cho dy nng t 3 300 mg L1. Dn xut mu Mt dung dch 0.4% ca DNPHi c chun b bng cch ha tan DNPHi (0.4g) bng acetonitrile (100ml). Trong mt erlen cha 0.9ml ca dung dch DNPHi, 4.0ml mu (c pha long trc) v 50 H3PO4 1.0 mol/L c gii thiu, lin tc. Sau dung dch ny c em khuy nhit phng trong 20min. dn xut mu c lc qua b lc Millipore 0.45 c tim vo h thng HPLC. Cc iu kin sc k Mt b my HPLCProstar Varian c s dng di iu kin ng th vi mt pha ng cha hn hp methanol/LiCl(aq)(1,0.10-3M 80:20 v/v) Mt van tim mu Rheodyne 7725 vi vng lp mu 20 uL c s dng, mt ct pha o vi ct nhi Shimadzu Shim C18 (150 x 6mm i.d. 5um) c p dng hu ht cho cc php v sau

o vi mt ct bo vShimadzu Shim C18. u d in ha (Varian ProStar 370) da trn nguyn l wall-jet, bao gm mt in cc hot ng cacbon thy tinh, in cc so snh bc bc clorua v mt in cc i khng c s dng. Trc khi s dng dung mi pha ng phi c lc qua b lc 0.45um (Millipore) v c kh vi kh nit tinh khit cao. u d in ha c ci t 1.0 V v tc dng l 1.0uL/min. Cc iu kin in phn Php o in phn bng cch s dng potentiostat / galvanostat (EG & G Princeton Nghin cu ng dng Corp (PARC), Model 173) Mt pin in th cha ba ien cc c s dng mt in cc carbon thy tinh (Methrom, din tch = 0,0314 cm2) nh in cc hot ng, mt si dy bch kim nhin cc i khng v mt in cc calomel bo ha nh in cc so snh(Methrom).in cc hot ng c nh bng gia th nghim vi 0.05um bn nhm, v ra sch vi nc kh khong. Cc thng s my in th c cn bng trong 15s v qut vi tc 50mL/s, dung dch ca LiCl (1 mol/L), v LiOH(1 mol/L) cng nh methanol/LiCl(aq)(1 mol/L,50:50 v/v) v acetonitrile/ LiCl(aq) (1 mol/L, 50:50 v/v) c s dng h tr in phn. Tt c cc dung dch c lm sch vi nit tinh khit cao trong 10min trc khi tin hnh ghi in th v dng nit tip tc i qua dung dch trong sut qu trnh o. Phn tch nh lng S chuyn i hm lng acetaldehyt trong etanol nhin liu thnh dng dn xut (ADNPH) t c bng cch s dng mt lng d ln DNPHi4-6. ng cong tiu chun cho ADNPH t c bi s hi quy tuyn tnh, gin din tch peak t l vi nng . Cc h s tng quan gn nh ng nht.

Phn tch mu etanol nhin liu Cc mu etanol nhin liu thng mi c sn khc nhau c thu thp xung quanh Araraquara, So Paulo, Brazil.Nhng mu ny c lu tr trong cc bnh thy tinh Pyrex nhit kim sot 20oC trong tt c cc php o.thnh phn acetaldehyt trong nhng mu ny c dn xut v phn tch c tin hnh trn h thng HPLC. KT QU V THO LUN Phn tch HPLC cho cht chun ADNPH Khng c vn v s hp th trn b mt in cc c tm thy trong khi o acetaldehyt cho s pht sinh oxy ha v s gim thy ng lc in th c m bo. c c php o phn tch cho cc in cc hot ng trn cc h thngHPLC, n cn thit phi nh bng b mt ln u mt cch cn thn vi 0.05 um bn nhm v trc mi in th khc nhau n cn thit l mt in ha sch chng trnh c t 1,0 v -1,0 V trong 20 giy. nh hng ca in th ln thy ng lc in th c ghi li cho cht chun ADNPH 50 mg/ L cc in th lm vic khc nhau s dng mt pha ng cha methanol/LiCl(aq)(1,0.10-3M 80:20 v/v) c ch ra trong hnh 1.Tuy nhin, ng cong qu trnh oxy ha thu c cho ADNPH theo cc iu kin th nghim m t trn, c th hin trong Hnh 1a.Mc d mt tn hiu nh c quan st thy 0,8 V,nhng gi tr ti a ca peak hin ti c quan st thy mt in th cao hn 1,0 V.in th lm vic ti u choqu trnh oxy ha ca ADNPH c la chn vo khong 1,0 V.Ti in th cao hn 1,2 V thy c s gia tng ca nh hng nn do lm tng n. S gim thy ng lc in th tng ng (hnh 1) ch ra khng c tn hiu ng k di mc gi tr -0.7 V, nhng tn hiu ln nht nhn c in th cao hn -0.9Vni c hai nhm nitro c th c gim. chn u d in th ti u, l mong mun ti a ha phn ng hin thi v ng thi ti thiu ha nh hng nn.Trong trng hp ca ADNPH, chai in th-0,8 V hoc 1,0 V u c th c s dng t thy ng lc hc in

th. Ni v s xem xt ny, sc k cho cht chun ADNPH 50 mg/ L c ghi li khi s dng mt ct pha o (Shimadzu Shim-pack C18) tin hnh di iu kin ng th, s dng pha ng lmethanol/LiCl(aq)(1,0.10-3M 80:20 v/v) ti tc dng l 1mL/min. Sc ph thu c khi in th c mt gim mt s gp phn cao ca nh hng nn do c s can thip ca oxy ha tan khng c loi b trong thi gian di iu kin desaeration.Nh vy, ti u ha thng qua kh nng oxy ha c nghin cu. Hnh 2 cho thy s phn tch sc k in hnh cho cht chun ADNPH vi u d in ha. Nh vy cho thy s phn tch sc k cho ADNPH t tt iu kin th nghim ti u, v s ra gii ca hp cht nghin cu hon thnh trong thi gian t hn 7min trong mt qu trnh chy sc k. S xc nh peak sc k da vo thi gian lu tr (5.8 min) v c xc nhn bi xc thc dung dch chun ca ADNPH. ng chun phn tch ca u d in ha, da trn din tch peak t l vi nng , c u tin cho nhng peak cao caADNPH do kh nng ng c trn b mt in cc, chng lm sai lch kt qu nh lng.Cc ng cong phn tch cho ADNPH c xy dng bi biu ca din tch peak vi nng , v mi quan h tuyn tnh t c t 3300mg/L vi cc thng s nh sau: din tch=1.52 x 105+ 0.1 x 105[ADNPH] vi r2=0.9998. Gii hn pht hin (LOD) xc nh nng c tim thp nht c thc hin t l tn hiu: nhiu bng 3:1 l 3.8ug/L. Xc nh acetaldehyt trong mu etanol nhin liu S dng iu kin th nghim tt nht nh nghin cu trn, nhiu mu etanol nhin liu t nhiu ngun khc nhau c x l bng DNHPi, chng c phn tch bng HPLC vi u d in ha c iu chnh 1.0V t c php tch tt nht. Bn hnh 3 ch ra mt php tch sc k tiu biu t c t mt loi mu etanol nhin liu thng mi. S c mt DNHPi nng tng i cao khng gy ra bt nh hng r rng no ln tn hiu ca sn phm ADNPH c

to ra sau phn ng, chng c tch t mi phn ng khc. Ngoi ra nhng peak tng ng vi ADNPH,c mt thm mt vi peak khc v xc nh hu ht chng. Nhng peak xut hin thm c cho l s c mt cu cc hp cht cacbonyl. Thm vo , phng php ny c kim tra cho nhiu mu etanol nhin liu, kt qu nh lng c lin quan c lit k bng 1.thng thng thnh phn acetaldehyt trong etanol nhin liu kh cao, v im c gi tr nng cao ca acetaldehyt trong nhin liu thay i nng t 83 343mg/L . Nhng pht hin phn nh nhng kh khn lin quan vi mt hn hp nn. Hi quy c nh gi cho ADNPH bng cch s dng cc dung dch dn xut chun ca ADNPH mc khong 25% php o v thc hin nm ln phn tch sau mi ln b sung (Bng 1). Nng ca ADNPH c tnh ton da vo din tch peak. N c tnh ton da trn phng trnh hi quy tuyn tnh ca phng php thm chun. lp li ca phng php ny c xc nh bng cch tin hnh nm th nghim trn cng mt mu hn hai ngy trong 1 bn. Gi tr ca lch chun thp (8,2% 0,36) v h s bin i l 3,2%. Tuy nhin, phng php xut cho thy chn lc v nhy xc nh chng. KT LUN Mt phung php sc k lng hiu nng cao vi u d in ha c ti u ha xc nh acetaldehyt trong mu etanol nhin liu nghin cu thnh cng. c bit u d in ha th hin nhy hn v tnh chn lc cao hn, iu rt hu ch khi phn tch mu tht, bi v chng lm gim nh hng nn ,do ci thin vic nh lng acetaldehyde.V vy, pht hin ny chng ti a ra mt phng php nhanh chng, ng tin cy v n gin, cho nh lngv xc nh chng trong ethanol nhin liu.