(1)Journal of the Korean Chemical Society 2004, Vol

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(1)Journal of the Korean Chemical Society 2004, Vol. 48, No. 1 Printed in the Republic of Korea. --

(2) *. ). (2003. 10. 24. Shock Tube Study of Ignition of Methanol-Oxygen-Argon Mixtures Kuan Soo Shin*, Gyun Tack Bae, and Sang Jo Yoo Department of Chemistry, Soongsil University, Seoul 156-743, Korea (Received October 24, 2003). :

(3) , , , Keywords: Methanol, Ignition Delay Time, Shock tube, Combustion Reaction. !" #$%& ' ( )* +*,& -. /012 3,' 4 5& 678 9 :& ' ;< => ?@*! 9A. B C /01 :> !)! 9 DEF> GH I*J(CNG), KI*J(LNG), KL*J (LPG), , M<NOP,

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(16) #: !{&b & ' ^* , ®, ¯°ª QY ±l¢ [\] ²³´ µ ¶TU, /' y& ' ^· z] <¸´µ 9A.

(17) ¹ %> Aº < X»¼ 9A. CH OH½CH OH½CH O½HCO½CO½CO ¾ ^&b

(18) ¿Y !«l# A`' ¨© l&b

(19) #: Y À lÁTU, ] Â ÃÄ#: Å· {·& -. < ÆÇX Èl ¦§j!, V ÉY ^l!/ lÁA. cT> , & , Ê> Ë Q (R-H) %( Å·* +*lÌ < Í´ %< 9A. lx.

(20) 2 3,l >Î A} A} ¿Y j ÏT> #ÐA. 3-7. 3. 2. 2. 2. 8-10.

(21) ª Y <7 6 Ñ ¨© l&b ³ 99.

(22) . 100. lÁTU, ª& 67Ð A} ÒÓ& /] #Ô´µ 9A. Õ GÖ t % < 6.02 cm<! Í<* 478 cmh Y 67l¢ g× ØTU, ? GÖ t& %< 9.73 cm<! Í <* 112 cmh Y 67lÁA. Ù6 Ñ Ú· 5Û GÖÈ$#(PCB 113A21) timer/counter (PM6666)2 <7 ÜlÝ À8 9ØA. ÞËT>tu 1.0 cm ß´² à& áâÐ GÖÈ$#(PCB 113A21)2 <7l¢ ÀlÁ !, 0& ÞËT>tu ã 1.0 cm ß´² à& áâÐ sapphire window2 ±l¢ OH .OäF & åæ çY èZ/ +é(ARC DA-781) Y 67l¢ ÀlÁA. èZ/+é ê& áâÐ sapphire window 6<& OH filter(Andower Co., 307 nm) slitY áâlÁTU, åæ ç Z #c ëì2 ëì+í#(SRS SR445)> +íî O ï N>JSÊ(HP45601A)> ÀlÁA. #:> CH OH(99.8%, Aldrich), O (99.99%, Dongmin), Ar(Donga, 99.9993%)Y 67lÁTU, ð ² #:> He(Dongmin, 99.9995%)Y 67lÁA. Table 1&b ª& 67Ð CH OH-O -ArÃÄ#: ÂÂ Å· ª ¨©FY X»ØA.

(23) K: E2 <7 freeze-pump-thaw Y ñò 7ó 2 gñ' i 67lÁ!, V W #: ô' õ ö< V> 67lÁA. ÃÄ #: MKS GÖÝ<(122A-01000AB)2 <7l¢ xFØTU, 24 0¬ #Ae i ªY ³lÁA. ÃÄ #: ÷# GÖ(P ) 20 torr> lÝ Ll¢ ª lÁTU, ð² #:> 67' He #: GÖY È î Ñ <i ãc ¨©Y ¨ølÁA. ¾ ª 6 Ñ ¨©&b ªlÁTU, 6 Ñ ùi {·(T ) GÖ(P ) ÂÂ 1342-1735 K 0.73-1.14 bar ú<ØA. 11,12. 11. 3. 2. 3. Fig. 1&b ª&b ÀÐ Zûch #: GÖ È OH .Oä& ' è åæ ëì2 X» ü ÏT>, õº Ù6 Ñ ùi ý GÖ zþ< 9 i& 6 Ñ* ±lÌb A GÖ< zþ l! <i ' 0¬ GÖ< ´ÿ · l Ý LA* GÖ< A ] +*,Y 9 A. ' OH .Oä& ' è åæ(307 nm) ¾c h < ´XÌ X»X# ×l¢ * ¾ cT> ²³ ! (2 X»üA. ¢#b (τ) 6 Ñ* X ùitu G Ö< ] ÈlñX OH .Oä è åæ< ] +*l <A. ª&b À è åæ ëì>tu lÁA. ª Fig. 2&b <

(24) --@ Ã Ä #: #: {· ¨¿& -. . Y R 9ØA. cT> 6 Ñ ùi #: {·(T )* ÕTÌ

(25) ÃÄ#:&b Í´U, ÃÄD Å· È 5. 2. 1. 5. 5. Fig. 1. Typical experimental record showing pressure (upper) and OH emission (lower). Experimental conditions were P1=20 torr, P5=0.92 bar, and T5=1468 K in mixture 1.. Table 1. The experimental conditions of CH3OH-O2-Ar mixtures Compositions of mixtures(%). Mixture 1 Mixture 2 Mixture 3 Mixture 4 Mixture 5 Mixture 6. CH3OH. O2. Ar. 4.00 2.00 4.00 2.00 2.00 1.00. 3.00 3.00 6.00 1.50 6.00 3.00. 90.0 95.0 90.0 96.5 92.0 96.0. (µsec). T5(K). P5(bar). 40-1210 28-1213 56-928 54-1400 43-1123 80-1465. 1406-1670 1406-1735 1349-1604 1433-1711 1342-1649 1396-1641. 0.82-1.14 0.86-1.08 0.81-1.08 0.78-1.04 0.74-1.03 0.73-0.94. Journal of the Korean Chemical Society.

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(27) - - ! "#. 101. Fig. 2. Ignition delay times for the mixtures shown in Table 1. Lines indicate the ignition delays for each mixtures calculated using the equation in the text.. Fig. 3. A plot of logβ vs. 104/T5 for all mixture; β=τ/ [CH3OH]−0.12[O2]−0.70[Ar]−0.37. The solid line represents the best fit for mixtures.. & -. {·&b· < ý .. Y «8 9ØA. Fig. 2&b

(28) ª 2 logτ 10 /T > X»ØA. ¢#b h

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(30) h CH OH +M½CH OH+H+M Q Ú·* .# Ó< .! oÂ'A. cT> #:* 8 , h Å·* +*lÌ < Í´U, gh Å·* +*lÌ < @ %Y jhA. 2 FÌ [CH ] , & [C H ] , Ê>Ë [C H ] Å·ó·2 jhA. < ""h H+O ½OH+O H+R-H½ H +R < b> %#l# Ó& Å·* +*lÌ Z:cT> < Í´ %Y jhA. lx

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(37) yY & '(l¢ )*u2 <7' ªY ³l¢ 'A! oÂÐA.. 4. 5. −13. −1. 3. −0.12. 2. −0.70. [Ar]−0.37. ¢#b 5> X»ØTU Å· 5 mol/cm <A. < É »¿ Fig. 3&b <

(38) ªY log(τ/[CH OH] [O ] [Ar] ) 10 /T > VÊ* ùz& â,Y j! h8 9ØTU, ù ## {·& -} ó·2 X» T> 50 kcal/mol · Arrhenius ûÉ [¿ &q2 X»üA. & ' Â #: Å· ó·2 ¦§jÌ.

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(42) --@ ÃÄ#: Y 6 Ñ2 <7l¢ 1342-1735 K {· ú 0.731.14 bar GÖ ú&b «lÁA. #: GÖ È OH .Oä& ' è åæ> tu ^lÁTU, Â ÃÄ#: Å· {·& -. Aº ªÉT> B8 9ØA. τ = 7.810 exp(50 kcal mol /RT) [CH OH] [O ] −13. −1. 3. −0.12. 2. −0.70. [Ar]−0.37(mole/cm 3)1.19µsec. ¢#b

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(44) < r/2 3,l! 9´ A} ¿Y j<# Ó<.! oÂ'A. ¾ ^ 2002+· ^& rT > <¸´,TU, <& 62 -.yA.. 1. Borgwardt, R. H. Ind. Eng. Chem. Res. 1998, 37, 3760. 2. Gordon, A. S.; Austin, T. C. Prog. Energy Combust. Sci. 1992, 18, 493. 3. Gardiner, W. C., Jr. Ed. Gas-Phase Combustion Chemistry; Springer-Verlag: New York, 2000. 4. Held, T. J.; Dryer, F. L. Int. J. Chem. Kinet. 1998, 30, 805. 5. Egolfopoulos, F. N.; Du, D. X.; Law, C. K. Combust. Sci. and Tech. 1992, 83, 33. 6. Bowman, C. T. Combust. Flame 1975, 25, 343. 7. Grother, H. H.; Just, T. Combust. Sci. and Tech. 1993, 91, 15. 8. Jee, S. B.; Kim, W. K.; Shin, K. S. J. Korean Chem. Soc. 1999, 43, 156. 9. Shim, S. B.; Jeong, S. H.; Shin, K. S. J. Korean Chem, Soc. 1998, 42, 575. 10. Kim, K. Y.; Shin, K. S. Bull. Korean Chem. Soc. 2001, 22, 303. 11. Kim, W. K.; Shin, K. S. J. Korean Chem. Soc. 1997, 41, 600. 12. Jee, S. B.; Kim, K. Y.; Shin, K. S. Bull. Korean. Chem. Soc. 2000, 21, 1015.. Journal of the Korean Chemical Society.

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