Korean Chemical Engineering Research

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(1)Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005, pp. 181-185. ! +. Tag gt ð£Ç ¿ô§ K;| ¿|Ï ´W£ Ã[ l` Z Sl. £Ð ¿|* ìLS** †. §¬H/ 8MàHê, */Hz 309-711 £{ fMQ Uö 21 **£{¬H/ 8MàHê 361-763 £{ Y?Q ^ C íU 48 (2004¸ 9ö 22³ [¤, 2004¸ 11ö 26³ >) Measurement and Prediction of the Flash Point for the Flammable Binary Mixtures using Tag Open-Cup Apparatus Dong-Myeong Ha†, Sungjin Lee* and Young-Ho Song** Department of Safety Engineering, *Department of Liberal Arts and Science, Semyung University, 21, Sinwoul-dong, Jecheon 390-711, Korea **Department of Safety Engineering, Chungbuk National University, San 48, Gaesin-dong, Henngduk-gu, Cheongju 361-763, Korea (Received 22 September 2004; accepted 26 November 2004). ß È. ¯@Yo Íõ í0 @é Ú °è Ùé.× s _G2) Íß O®K õ 7 j ÍÒ) G÷«. ¯@ Y _AK (Ro Æ @é ö, Í Ú JQK öÑ O®G. á õCÑ n-butanol+n-propionic acidªQ, n-propanol+n-propionic acidª íöª ¯@Ys TagR íöª ßj(ASTM D 1310-86)õ «ÄGñ +_G. Y ×ào ¶Ö rkê van LaarRÑ g ªê àê 9/G. ê, van LaarRÑ K +à« ¶Ö rk Ñ K +à Ý Y×àÑ

(2) Ï Ws A¯G. Abstract − The flash point is one of the most important combustible properties used to determine the potential for fire and explosion hazards of industrial material. An accurate knowledge of the flash point is important in developing appropriate preventive and control measures in industrial fire protection. The flash points for the n-butanol+n-propionic acid and n-propanol+n-propionic acid systems were measured by using Tag open-cup apparatus(ASTM D 1310-86). The experimental data were compared with the values calculated by the laws of Raoult and van Laar equation. The calculated values based on the van Laar equation were found to be better than those based on the Raoult’s law. Key words: Flash Point, Tag Open-Cup Apparatus, n-Propanol+n-Propionic Acid System, n-Butanol+n-Propionic Acid System, van Laar Equation. 1.. g «. U U

(3) Í>« ¯dO ) 1®K ,õ èG2 U MI5³ _K. ¯dYÑ2 Gz¯dYê z¯dYk³ ÷Ê Àk, ³äJk³ Gz¯dYs ¯dY«¶ K[1, 2]. ¯ dY +_ ßj³2 ASTM D 56 Tag ÊR, ASTM D 1310 Tag íöª, ASTM D 92 Cleveland íöª, ASTM D 93 Pensky-Martens Êª, ASTM D 3278 Setaflash Êª, ASTM D 3828 Small Scale Êª ßj Ù« À[3]. K Yagyu[4]Í Ê8K Êª ¯ dY +_ ßjÍ À. « ÍÒ) ASTM D 1310 TagR íöª ß j2 á Y×Ñ íöª ¯dY +_Ñ ÄK ßj³ K ¨¤í0 Ú HYí íöª ¯dY +_s ÁêJk³ O ¤ À 2 U8s Í(Ê À. dHí0o ¨¤í0³ Äæ2 ÎÝ2 Í( ¨¤í0«. dHà_ªÑ À´ 5, Ft, ÙÑ ¬K ÒM p.Q ä í, OÑ@ í, @ í Ú zí í-J Ú dHJ U , 8 M , Ùs ²5G2 a« åÈÝ O®G. à_ Ñ Í õ í0 @, s-, ¤, IßO ) í z?³ dé Ú ° è« t,î ¤ À. ¶ Íõ í0 8MK ís .g 2 «Ë í0 O®K ,ðJ¯ 8MU É0¯ ¯dYÑ ¬K (Rs 1®³ K. ¯dYo Íõ U dé .× s ÷2 (,³, Íõ † To. whom correspondence should be addressed. E-mail: [email protected] 181.

(4) Gö« ,ö,. 182. ¯ HYí0³ Äæ2 ÎÍ ¬z~«. í0ÝQ8MÉ0 (MSDS, material safety data sheets) fÍ G2 ao dHí 0s 8MGj íWk³ Êõ öG2 a«. «6K IJ s G, .g í08MÝQÉ02 HYí É .× Q ×s M° ÍæÊ «õ à3k³ Ê G2 a« òk«. 6 ÷ YJk³ Kg .× , 8M Ù fu )éÑ ß,J«Ê ÜYJ Q×s M° _eGj Íê Î2 M §ªJk³ Q( :k, U¾ Î-÷¶Ñ2 «Ñ ¬K õgÍ M Ç2 =« . ¶ ¬z~ dHÆÑ ÄGÊ À2 ¤Qo Íõ H YÄf .× s ¶_G2 ao OÏ ´ . é>( è,ê HYí0Ñ ¬K ¬,J¯ ¯dY õgõ o Ý

(5) , Affensê Mclaren[5]o ¨¤ !d¤Q ~ª HYí ¯dY +Ñ îK õgõ GÊ, WuQ Finkelmen[6]o setaflash Êª ßjõ «ÄK ¯dY +_ê + H1s MíGk, Gmehlingê Rassmussen[7]o Íõ 3 ~ªÑ ¬g b,ñr (group contribution method)¯ UNIFACrs «ÄGñ lª¤ õ ªGÊ, «õ ÄGñ ¯dYs +Gñ éËàê 9GG . K, Walsham[8]o TagR íöª ßjõ «ÄK ¯dY + örs fQG. MÑ HaQ Kim[9]o RSM(response surface methodology)s « ÄGñ Íõ 3 ~ªÑ ¬K ¯dY H1s MíGk, Hanley[10]2 ~ª Êª ¯dY ªÑ ¬K H1s fQG . Mitchell Ù[11]o ÆßÑ Q« ÄG2 4Æª ¯ dYs +_GÊ, JonesQ Godefroy [12, 13]o formic acidÑ ¬g ,Ê ¯dY +_j Uõ ÍGk, Ha Ù[14, 15]o 2 ~ª Íõ U HYí Gz Ú z ¯dYs +_ Ú G. á õgÑ2 Íõ í0¯ n-butanol+n-propionic acidªQ, n-butanol+n-propionic acidª HYíÑ ¬g TagR íöª ßjõ «ÄGñ íöª ¯dYs +_GÊ, «õ ¶Ö rkê van Laar H1Rs «ÄK ªàê 9G ]G. ñ,, »o É0õ dé Ú °ès ö(G2 ,ð É0³ fàGÊÉ G, Íõ H Yí ¯dYs +G2 örk³ lÄæ,õ ,¬K. 2.. K;| ´ôg£ Tag( gt Ã[ Sl. ,F, γ 2 i ~ lª¤, M 2 è~É

(6) «. ¶, R (1)s R (2)Ñ ¬½Gñ _-G

(7) , {ê ç. i. r. N. xi Pi γ i M r. i=1. PF iM i. 1.25. -=1 ∑ -----------------------1.25. (3). ¶, íöª ¯dYs gG, .g2 R (3)s OÇQÿ2 5õ Q}1órk³ ªG

(8) ê. Ks, R (3) P õ ªG , .g á õgÑ2 AntoineRs «ÄG[16]. 9« ÄUk³ Í_K Î, van LaarR[17]s «ÄGñ l ª¤õ ªGk, « ~ª HYíÑ JÄQÿ

(9) {ê ç. i. 2 A21x2  ln γ1 = A 12 ------------------------------- A12 x1 + A21 x2. (4). 2 A12x1  ln γ2 = A 21 ------------------------------- A12 x1 + A21 x2. (5). ñ, A Q A 2 DÊÄ ²¶Â³, «Ëo îw éËÑ s ¤ À[18]. Ks, « ÄUk³ Í_K ÎÑ2 ¶Ö rks JÄG. 12. 21. 3.. / #. /ð£ á ßj2 Íõ HYí íöª ¯dY +_« ÍDK ßj³ Q« ÄæÊ Àk, Y×Qó2 ASTM D 1310-86(standard test method for flash point and fire point of liquids by tag open-cup apparatus)Ñ ä_æ´ À[3]. Y×Ñ ÄK TagR íöª +_ ßjõ Fig. 1Ñ ÷É. ßj2 ¿j Q0, 95 «¼, ¤Æ, Q× è@ ßj Ùk³ g æ´ Àk, zÍ ßj³2 Q0 Q0 ¤.õ ÆQO ¤ À2 S ¤C K(ßj(level device)Í À. 3-2. /'È á Y×Ñ2 ÆßÑ - ÄæÊ À2 n-propanol, n-butanol ê n-propionic acidõ ¬ k³ G. n-propanolo Carlo Erba. (99.5%), n-butanolo Junsei (99%) Qus ÄGÊ, n-propionic 3-1.. Íõ HYÄf TagR íöª ¯dYo « ÄU(ideal solution) ¯ Î Raoult rks «ÄGñ +GÊ, 9« ÄU(non-ideal solution)Ñ ¬g2 lª¤(activity coefficient) H1s «ÄG ñ +O ¤ À. Î, Íõ í0 ¯d(,õ {ê ç« _ê[8]. 1 Ii = -------------------1.25 PFi Mi. (1). ñ,, I 2 i ~ ¯d(,, M 2 i ~ ~É

(10) , PF2 íöª ¯dYÑ ~ ,F«. K, Íõ HYÄf íöª ¯dYo {ê ço ¤Rs O ÇQÿ2 5³ _ê. i. i. i. N. 1.25 ∑ I i xi P i γ i Mr = 1. (2). i=1. ñ,, No ~¤, x 2 i ~ P~S, P 2 Î 5Ñ i ~ i. ¤@¤ C43× C1 2005 2. i. Fig. 1. Photograph of the experimental apparatus..

(11) R íöª ßjõ «ÄK Íõ « ~ª 0Yí ¯@Y +_ Ú +. Tag. 2 Acros (99%) Qus ÄGk, Î Quo ¥ _ fê_s Mj( :I. 3-3. /tà Y×öro ASTM D 1310-86 äÑ ¶ Y×Gk, Qó2 {ê ç. 1) Qus ÎÎ Y×GÊÉ G2 P9(mole fraction)³ HYG. 2) Q0 70 mlõ Q0Ñ Ê, + ¯dYÝ u 20 C o 5z ÍùG. 3) 95õ 1 0.25 C/minÍ æ´ ÆQG. 4) 5Í 0.5 C ÍO )K Q×s Íõ U ,

(12) Ñ 1ð 8 [QZ. 5) M« è@G2 5õ ¯dYk³ Gk, ³K Y×s äÞGs ) ¯dY ¶_Ñ À´ é o âo êõ ÷ É. acid. o. o. o. 4.. ûG Z +{. á õgÑ2 Y×Ñ »´, +_àê «·RÑ »´, às 9G ]G. n-Propanol+n-propionic acidªQ, n-butanol+n-propionic acidª íöª ¯dY Y×É0Í « ÄUê 9« ÄU 0 ÍÒ) ´. ÄU 0s (nÊ À2( oÝ, .g « ÄUk³ Í_K Î Raoult rks JÄGÊ, 9« ÄU¯ ÎÑ2 lª¤õ «ÄK +Rs ÄG. Y×É0 U Êûs .g 9« ÄU¯ Î lª¤ ª« 1®G, « ªs .g ,U É0Í À´t K. n-Propanol+n-propionic acidªQ, n-butanol+n-propionic acidª , U É02 DECHEMA éË[18]Ñ »Ék, van LaarRs «ÄGñ lª¤õ ªK á ¯dYs +G. Table 1Ñ 2 ¯dY ªÑ 1®K Î ¨¤í0 Antoine ¤õ ÷É [18, 19]. K, ¯dY +_ ßj QM s e¯G, .g á õgÑ +_ê ¨¤ ~(n-propanol, n-butanol, n-propionic acid) íöª ¯dYê ,Ê éËj[20]õ 9Gg ÝI. n-propanol, n-butanol, n-propionic acid éËj2 ÎÎ 29 C, 42 C, 57 C³ fQæ´ Àk, «2 á õg Y×àê M ³jG, u 0.5-2 C ó« Í è@K ao íöª ßj U Ñ ,¯K. ¶ +_ ßj2 QMK ak³ ¶ê. Table 2ê 3Ñ2 Y×àê «·R(RaoultR Ú van LaarR)Ñ K +às 9GGñ ÷ÉÊ, Y×àê +à ó« _ õ <, .g A.A.P.E.(average absolute percent error)Q A.A.D. (average absolute deviation)õ ÄGÊ, K 0ª ~s .g ,CsóQ ,á_ª¤õ ÄG[21, 22]. o. o. o. o. Table 1. Antoine constants for n-propanol, n-butanol and n-propionic acid Properties Components n-Propanol n-Butanol n-Propionic acid. A. B. C. 183. Table 2. Comparison of the experimental and calculated flash points for n-propanol(X1)+n-propionic acid(X2) system Mole fraction X1 X2 1.000 0.000 0.916 0.084 0.813 0.187 0.710 0.290 0.509 0.491 0.306 0.694 0.081 0.919 0.000 1.000 A.A.P.E. A.A.D.. Flash point (oC) Raoult van Laar 25.99 25.99 27.17 27.25 28.76 29.02 30.56 31.06 34.90 36.00 41.17 42.83 53.55 54.87 61.86 61.86 6.12 5.41 2.18 1.96. Exp. 28.5 30.0 30.5 34.5 36.5 42.5 53.0 59.0 -. Table 3. Comparison of the experimental and calculated flash points for n-butanol(X1)+n-propionic acid(X2) system Mole fraction X1 X2 1.000 0.000 0.916 0.084 0.824 0.176 0.714 0.286 0.507 0.493 0.306 0.694 0.098 0.902 0.000 1.000 A.A.P.E. A.A.D.. Flash point (oC) Raoult van Laar 42.24 42.24 43.07 45.05 44.05 46.25 45.33 47.53 48.13 50.09 51.57 53.07 56.36 57.02 59.35 59.35 1.91 1.65 0.93 0.76. Exp. 42.5 42.5 45.0 47.0 50.0 53.0 56.0 59.0 -. ∑ ( yi – y˜i) S = ------------------------n–1. (6). 2 SSR r = ----------SST. (7). 2. ñ, S2 ,Csó, y 2 ,á, y˜ 2 ,á è, no ,áí¤, r 2 ,á _ª¤, SSRo ¡ÇÑ K fÜY(sum of squares due to regression), SST2 SSRê ÍóÑ K fÜY(sum of squares due to residual errors) Y«. Y×àê RaoultR Ú van LaarRÑ K +às 9GK ê õ

(13) Ï j å ¤ À´ Fig. 2Q 3Ñ ÷É. n-Propanol+n-propionic acidªÑ íöª ¯dY Î, Raoult rkÑ g ªê àê Y×à A.A.P.E.2 6.12%«Ê, è 5 ó«Í 2.18 C«, ,CsóÍ 2.56 C -Ê _ª¤(r ) 2 0.95³ ÷

(14) . van LaarRÑ g ªê àê Y×à A.A.P.E.2 5.41%«Ê, è5 ó«Í 1.96 C«, ,CsóÍ 2.38 C -Ê _ª¤(r )2 0.96k³ ÷

(15) . ¶ « ª ÎÑ2, van LaarRÑ g ªê à« Raoult rkÑ g ª ê àÝ Y×àÑ

(16) Ï G. n-Butanol+n-propionic acidªÑ íöª ¯dY ÎÑ2, Raoult rkÑ g ªê àê Y×à A.A.P.E.2 1.91%«Ê, è5 ó«Í 0.93 C«, ,CsóÍ 1.19 C -Ê r o 0.96 k³ ÷

(17) . van LaarRÑ g ªê àê Y×à A.A.P.E. 2 1.65%«Ê, è5 ó«2 0.76 C«, ,CsóÍ 1.17 C -Ê r 2 0.97³ ÷

(18) . ¶ n-butanol+n-propionic acidª ÎÑ, van LaarRk³ ªê à« Raoult rkÑ g ª ê àÝ Y×àÑ

(19) Ï G. Ks, & Q)Ê íöª ¯ 2. i. i. o. o. 2. o. o. 2. o. o. o. 2. o. 2. 7.84767 7.838 7.99064. 1499.21 1558.19 1929.300. 204.64 196.881 236.430. Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005.

(20) 184. Gö« ,ö,. Ok³ á õgÑ fQK ör·« ÆßÑ íG2 ¤ Qo ¯d HYÄf íöª ¯dYËs +O ¤ À2 örk ³ lÄæ,õ ,¬K. 5.. û «. n-Propanol+n-propionic acidªQ, n-butanol+n-propionic acidªÑ ¬g TagR íöª ßjõ «ÄK íöª ¯dY +_àê U H Y ùòH íÄÑ K ªàs 9G ]Gñ {ê ço · s »É. (1) n-Propanol+n-propionic acidª ÎÑ2 Raoult rkÑ g ªê àê Y×à A.A.P.E.2 6.12%«Ê, è5 ó« Í 2.18 Cõ ÝÊ, van LaarRÑ g ªê àê Y×à A.A.P.E. 2 5.41%«Ê, è5 ó«Í 1.96 Cõ Ý. (2) n-Butanol+n-propionic acidª Î2 Raoult rkÑ g ªê àê Y×à A.A.P.E.2 1.89%«Ê, è5 ó«Í 0.93 C õ ÝÊ, van LaarRÑ g ªê àê Y×à A.A.P.E.2 1.65%«Ê, è5 ó«2 0.76 Cõ Ý. (3) Íõ 2 ~ª HYíÑ ¬K íöª ¯dY + H1s MíGk, A.A.D. àÑ < ¤ À×« van LaarRÑ g ª ê à« Raoult rkÑ g ªê àÝ Y×àÑ

(21) Ï . G. o. o. o. o. Fig. 2. Comparison of the experimental and predicted flash points for n-propanol(X1)+n-propionic acid(X2) system.. ÷ô{ A, B, C : antoine constant A12, A21 : parameter in the equation of van Laar Ii Mi. : flashing index : molecular weight. PFi Mr. : vapor pressure of component i at its flash point : calculated mean vapor molecular weight. Pi. : actual partial pressure of component i in vapor-air mixture [mmHg]. Pis xi. : vapor pressure of component i [mmHg] : mole fraction of component i. S yi y˜i. : sample standard deviation : sample. n. : sample mean : sample number. SSR SST. : sum of squares due to regression : sum of squares total. +÷¿ïSÛ. Fig. 3. Comparison of the experimental and predicted flash points for n-butanol(X1)+n-propionic acid(X2) system.. dY +Ñ n-propionic acid ¯dY +à« ³ uÑ ó «õ Ý«2 ao, Walsham« fQK R (3)s JÄO ), & Q) Ê è ~É

(22) ó«Ñ ,¯K ê«. ¤@¤ C43× C1 2005 2. γi r2. : activity coefficient of component i : sample coefficient of determination. +S 1. Meyer, E., “Chemistry of Hazardous Materials,” 2nd ed., Prentice-Hall Inc., New Jersey, NJ(1990)..

(23) R íöª ßjõ «ÄK Íõ « ~ª 0Yí ¯@Y +_ Ú +. Tag. 2. Lee, S. K. and Ha, D. M., “Newest Chemical Engineering Safety Engineering,” Donghwagisul Publisher, Seoul(1997). 3. Lance, R. C., Barnard, A. J. and Hooyman, J. E., “Measurement of Flash Points: Apparatus, Methodology, Applications,” J. of Hazardous Materials, 3, 107-119(1979). 4. Yagyu, S., “Diagram Relationship Between the Flash Point and Flammability Limit,” J. of Japan Society for Safety Engineering, 24(3), 152-158(1985). 5. Affens, W. A. and Mclaren, G. W., “Flammability Properties of Hydrocarbon Solutions in Air,” J. of Chem. Eng. Data, 17(4), 482-488 (1972). 6. Wu, D. T. and Finkelmen, R., “A Mathematical Model for the Prediction Closed Cup Flash Points,” American Chemical Society. Division of Organic Coatings and Plastics Chemistry, 61-67 (1978). 7. Gmehling, J. and Rassmussen, P., “Flash Points of Flammable Liquid Mixtures using UNIFAC,” Ind. Eng. Chem. Fundam., 21(2), 186-188(1982). 8. Walsham, J. G., “Prediction of Flash Points for Solvent Mixtures,” Advan. Chem. Ser. Publ. 73 Ser. 124, American Chemical Society, Washington, DC, 56-59(1973). 9. Ha, D. M. and Kim, M. G., “Prediction of Flash Point for the Flammable Ternary System,” J. of the Korean Institute for Industrial Safety, 12(1), 76-82(1997). 10. Hanley, B. F., “A Model for the Calculation and the Verification of Closed Flash Points Multicomponent Mixtures,” Process Safety Progress, 17(2), 86-97(1998). 11. Mitchell, J. W., Vratsanos, M. S., Hanley, B. F. and Parekh, V. S., “Experimental Flash Points of Industrial Amines,” J. of Chem. Eng. Data, 44(2), 209-211(1999).. 185. 12. Jones, J. C. and Godefroy, J., “A Reappraisal of the Flash Point of Formic Acid,” J. of Loss Prevention in the Process Industries, 15(3), 245-247(2002). 13. Godefroy, J. and Jones, J. C., “A Reappraisal of the Flash Point of Formic Acid,” J. of Loss Prevention in the Process Industries, 15(3), 241-243(2002). 14. Ha, D. M., Mok, Y. S. and Choi, J. W., “Flash Points of a Flammable Liquid Mixture of Binary System,” HWAHAK KONGHAK, 37(2), 146-150(1999). 15. Ha, D. M., Lee, S. J., Choi, Y. C. and Oh, H. J., “Measurement of Flash Points of Binary Systems by using Closed Cup Tester,” HWAHAK KONGHAK, 41(2), 186-191(2003). 16. Smith, J. M. and Van Ness, H. C., “Introduction to Chemical Engineering Thermodynamics,” 4th ed., McGraw-Hill, New York, NY(1987). 17. Reid, C. R., Prausnitz, J. M. and Poling, B. E., “The Properties of Gases and Liquids,” 4th ed., McGraw-Hill, New York, NY(1988). 18. Gmehling, J., Onken, U. and Arlt, W., “Vapor-Liquid Equilibrium Data Collection, Vol. 1, Part 1 Part 7,” Deutsche Gesellschaft für Chemisches Apparatewessen(DECHEMA)(1980). 19. Dean, J. A., Lange’s Handbook of Chemistry, 15th ed., McGrawHill(1999). 20. Stephenson, R. M., “Flash Points of Organic and Organometallic Compounds,” Elsevier, NY(1987). 21. Kim, M. G., Ha, D. M. and Park, J. C. “Modified Response Surface Methodology(MRSM) for Phase Equilibrium - Application,” Korean J. Chem. Eng., 12(1), 39-47(1995). 22. Kleinbaum, D. G., Kupper, L. L. and Muller, K. E., “Applied Regression Analysis and Other Multivariable Methods,” 2nd ed., PWS-KENT Publishing Company, Boston(1988).. Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005.

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