Measurement of Flash Points of Binary Systems by Using Closed Cup Tester

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1 HWAHAK KONGHAK Vol. 41, No. 2, April, 2003, pp * **, * ** ( !, "#) Meaurement of Flah Point of Binary Sytem by Uing Cloed Cup Teter Dong-Myeong Ha, Sungjin Lee*, Yong-Chang Choi and Haejin Oh** Department of Safety Engineering, *Department of Liberal Art and Science, Semyung Univerity, San 21-1, Sinwol-dong, Jecheon , Korea **Department of Civil & Environmental Engineering, Dongguk Univerity, 26, Pil-dong 3 ga, Jung-gu, Seoul , Korea (Received 14 October 2002; accepted 10 February 2003)! "#$. % &' () *+, -.*/ $. n-propanol+n-propionic Acid01, n-butanol+n-propionic Acid0 2 Penky-Marten 34' 5 #67 89$. : ;< =>?@A van Laar'/ B 0(C DA EF 9$. n-propanol+n-propionic Acid0/ G 2 HI/ van Laar'/ B.8C D J$ =>?@ B.8C D# K L 9$. n-butanol+n-propionic Acid0/ G 2 HI/ B.8C DJ$ van Laar'/ B.8C D# K L 9$. Abtract The flah point i one of the mot important combutible propertie ued to determine the potential for fire and exploion hazard of indutrial material. An accurate knowledge of the flah point i important in developing appropriate preventive and control meaure in indutrial fire protection. The lower flah point of the n-propanol+n-propionic Acid and n- Butanol+n-Propionic Acid ytem were meaured by uing Penky-Marten cloed cup teter. The experimental data were compared with the value calculated by the law of Raoult and van Laar equation. In cae of the lower flah point of the n-propanol+n-propionic Acid ytem, the calculated value baed on the Raoult law were found to be better than thoe baed on the van Laar equation. In cae of the lower flah point of the n-butanol+n-propionic Acid ytem, the calculated value baed on the van Laar equation were found to be better than thoe baed on the Raoult law. Key word: Flah Point, Penky-Marten Cloed Cup Teter, n-propanol+n-propionic Acid Sytem, n-butanol+n-propionic Acid Sytem, van Laar Equation 1.!" #$ %&'(. )*+,-. /01 2 3# ) *, 9: ;< =>?@ ABC D E(. FG 3# H, IJ,,-, KL M NO 7PC ' QRS, E(. TU 3# )*" NO 2!" )*% VW (flah point) 6" XY Z!C "(. To whom correpondence hould be addreed. hadm@emyung.ac.kr 3# [\ ]^_ X`Ca, 3#[ \ [b 3c' L M Z!" dr1 [\ ekf gc "(. 7+ G7BC ]hd EB i, jkbc 7 'U "([1, 2]. l mn BC ASTM D56 Tag opy[3], ASTM D1310 Tag qmy[3], ASTM D92 Cleveland qmy[4], ASTM D93 Penky-Marten op Y[5], ASTM D3278 Setaflah opy[6], ASTM D 3828 Small Scale opy[7].' E(. r" Yagyu[8]3 D)" opy l &3 E(. ' 3 ASTM D93 Penky-Marten opy ' 396 o C ' t0, uv, w[, xyz, #W. l PC {(. } ~kr8 0FD, ( " [\ l L, E % 3XD E([9]. 186

2 ƒ,c : ;( 3X,' ˆ C : 3 675'(. ;<)*VW(MSDS, material afety data heet) 0g3 g } ƒ )*Š NOBCa D1 m }'(. 'Œ" ŽR 2 )*;<VW ˆ V\ 3D '1 BC }' '(. Œ] ABC t2, ) *. 0 M R'D š Š 3 { : *œ BCg J žx ŸBi, % J]U ' 6" #43 G '(. TU 675 ƒ D E,ž 3# ˆ 0 R ' E(. #4 3# n-propanol+n-propionic Acid 8, n-butanol +n-propionic Acid ˆ 62 Penky-Marten opy &1 'ª 7 l«d, '1 'G[+ 'G[ q " ' + ~ ±«(. ªR, ² VW1 mx R³ VWC 0FDV i, 3# ˆ l mnbc yr1 R6"( ' ]^_ RµBC FR [\1 3 L M [\ `b dr3 Hª dr3 ¹L : [\ ekfg1 º"(.», 3# dr ¼' " (LEL, lower exploive limit) ½g8 ¾ M fg 1 7'U D, G" (UEL, upper exploive limit)8 d R¼' ] G7'U "(. dr¼+ " 6",3# [\ Fig. 1 ]^_ ( #ˆ 0 'G[(ideal olution) : Raoult n 'ª ld, 'G[(non-ideal olution) 62 yàg,(activity coefficient) =Á 'ª ll, E(. cx `{ ˆ 6" 6` #41 ÂÃ;b, Affen+ Mclaren[10], Ä,$8 (5 ˆ l Å" #41 «D, Wu8 Finkelmen[11] Setaflah opy &1 '" l+ l =Á *q «Bi, Gmehling+ Ramuen[12] 3# ÆRªn(group contribution method) UNIFACn 'ª yàg,1 D, '1 ª lª Ç + ~«(. e¹ Ha8 Kim[13] RSM(repone urface methodology) 'ª 3# " È =Á *q «Bi, Hanley[14] (5 op 6" =Á 0 «(. Ha.[15] 25 3# [\ ˆ 7 G7 l È«Bi, Mitchell.[16] ž' ÉÊ l«d, Jone.[17]+ Godefroy.[18] Formic Acid 62 RË l & ÌÍg1 3«(. #4 A ² Î 3# 25 VW ÌÍ ÂÃ;R 2 ÏK,3# 6" 7 Fig. 1 ]^Ð 8 ¾' " 8 dr¼' ] ll, EBi, (Ñ+ ¾ Y (1)C `{( = 1 L i () t ªR ÒdR¼, L i (t) fg Ó TÔ " '(.,5 l ' ¹ C ª 25 'G (5 l 2 Le Chatelier n '«(. ' n Õ 5¼+ " C ]^_b (Ñ+ ¾(. n = 1 L i () t i = 1 ªR 75¼'(. Y (1)+ (2)1 'ª 3#ˆ ldv " : 75¼( ) ÖÉQ "(. 75¼ R _ W R-[ G UD 3«BØC 'G[ : Raoult n 2 (Ñ + ¾' ]^Ù, E(. = x i 'G[ : ;, yàg,(γ i )1 '" YBC (Ñ+ ¾' `{(. = γ i x i (4) r" ˆ 0 7 lr 2 dr¼ ÚJ AntoineY[19] '«(. lr 2 dr¼ 6" VWÛ ÉÜU " (#$" ) 6" XYg Z!(. " ' ËL M 3#3v8 FR3 ˆ ª j ½gÝ _ #$3 'Þ X Ý1 º"(. " " 8 G" C ]h Xi ' ß fg, ¼à, $ ½g, áy3v. âã ä(. jk BC " VW 1R¼, 25 o C 3# 7åæ5ç (volume percent)8 7å5ç(volume fraction)c 0 D E(. " ¼à' jl : fg3 d3b Ý3 ÓØ C ' Å" AY «(. Alcohol 6" " fg Ë : Ha[20]3 0 " Y «(. Y (Ñ+ ¾(. L i () t = L i ( 25) [ ( t 25) ] Acid 6" : Zabetaki[21]3 0 " Y «(. Y (Ñ+ ¾(. L i () t = L i ( 25) [ ( t 25) ] (1) (2) (3) (5) (6) Fig. 1. Flah temperature(t Lf and T Uf ) for a pure ubtance by mean of vapor preure and exploive limit. ªR L i (25) 1R¼, 25 o C " '(. 'G[ : van LaarY[22] 'ª yàg,1 «Bi, '5 ˆ èb (Ñ+ ¾(. A lnγ 1 A 21 x 2 = A 12 x 1 + A 21 x 2 (9) HWAHAK KONGHAK Vol. 41, No. 2, April, 2003

3 188 A lnγ 2 A 12 x 2 = A 12 x 1 + A 21 x (10) ªR A 12 8 A 21 van Laar G,C, 'ß R[ VW3 E : Ç[23] 0 E(. '8 ¾' Modified Raoult n, Dalton n, Le Chatelier n JD yàg, ÈY. ª 3# ß ll, E( A { A& Penky-Marten Cloed Cup(ASTM- D93)&1 «D, Vœ" é Fig. 2 ]^_ (. & ê\7, Tet cup &7, ~k7, ë FO7C ìš ]í, E(. ê\7 3 FR?, * qpr, *?îr, ï4.bc 4 EBi, Tet cup &7 Tet cup ð' 100 ml g'i, *gg3 ñ 4JC ED, Tet cup handle, fg òó 4, Tet cup G7 qpr ôõ'c 4 E(. ~k7 ~kr, ö Fig. 2. Schematic diagram of experimental apparatu. 1. Tet cup 9. M4 NO# 2. FP 10. Tet cup handle 3. QRS 11. T UV WX 4. YZ[ 12. T\ 5. ]^_ 13. V` M4 6. ab0 14. VY [- 7. Flame expoure device 15. Vc 8. d[- ø, ù/min ~k *ÀRC 4 E(. ë FO7 ë ¹&(flame expoure device), #Wú, ë?îr, 3vÅ, 3v )* ûü.bc 4 E( A ÚJ D E n-propanol, n-butanol + n-propionic Acid1 6GBC «(. n-propanol+ n-butanol ƒ(ýþÿ)pyù(99%) «D, n-propionic Acid Acro(99%) «(. 'ß ÕÕ (Ô (mole fraction)c ˆ ª A«( #4 A mn ASTM-D93(Penky-Marten Cloed Cup) / È A«(. (1) ÕÕ ADV (mole fraction)c ˆ «(. (2) Tet Cup W(ˆ 0)1 65 ml D, Tet Cup G71 fg 8 ~kr1 òó" 1 'ª W fg1 _ (. (3) Tet Cup 3 F?R ) D D ~kr1 ö ø + #«(. (4) W ù/minC ~k«d, 5-6 o C/minC 3 «(. (5) W fg3 1 o C GL M ( qpr ôõ'1 'ª Tet Cup) ¹ (. á' H fg1 BC «Bi, Àj" A k«m E +1 ]^_ (. 4. À) J #4 3#ˆ 0 62 lª VW1 0 "«B], #4 A ² Î VW 8 ' Y ² Î È ~ ±ª 0 { AVW Ì Í D«(. #4 n-propanol+n-propionic Acid 8, n-butanol+n-propionic Acid AVW3 'G[+ 'G[ 3 [ XÜD EX ÂÃ;R 2 'G[BC 3 " : Raoult n «D, 'G[ : yàg,1 '" ly «(. AVW ÌÍ D 2 'G[ : yàg, ' Z!i, ' 2 R[ VW3 E Q (. n-propanol+ n-propionic Acid 8, n-butanol+n-propionic Acid R[ VW DECHEMA Ç[23] ² Bi, van LaarY 'ª yàg,1 " l«(. Table 1 Z! " Õ, Antoine G,, " 1 ]^_ ([24-26]. Table 28 3 A + ' Y(RaoultY van LaarY) " l ~ª ]^_ D, A + l ' g1 ÖR 2 A.A.P.E.(average abolute percent error)8 A.A.D.(average abolute deviation)1 «D, r" ú 5 2 `µ8 `,1 «([27-29]. Table 1. Antoine contant and lower exploive limit for n-propanol, n-butanol and n-propionic acid Propertie Component A B C LEL(vol%) n-propanol n-butanol n-propionic acid

4 Table 2. Comparion of experimental and calculated lower flah point by Raoult law and van Laar equation for n-propanol(x 1 )+npropionic acid(x 2 ) ytem Mole fraction Flah point( o C) X 1 X 2 Exp. Raoult van Laar A.A.P.E A.A.D Table 3. Comparion of experimental and calculated lower flah point by Raoult law and van Laar equation for n-butanol(x 1 )+npropionic acid(x 2 ) ytem Mole fraction Flah point( o C) X 1 X 2 Exp. Raoult van Laar A.A.P.E A.A.D Fig. 3. Comparion of lower flah point of experimental and predicted for n-propanol(x 1 )+n-propionic acid(x 2 ) ytem. S = r 2 ( y i ỹ i ) n 1 = SSR SST (11) (12) ªR S `µ, y i `, ỹ `, n ` q,, r 2 i `,, SSR ù " 0 (um of quare due to regreion), SST SSR+ " 0 (um of quare due to reidual error) '(. A + RaoultY van LaarY " l ~" +1 ; ( Š, Eg Fig ]^_ (. n-propanol+n-propionic Acid 7 :, Raoult n 2 { + A A.A.P.E. 4.96%'D, fg ' o C'i, `µ o C JD,(r 2 ) 0.94C ] ^(. van LaarY 2 { + A A.A.P.E. 6.38%' D, fg ' o C'i, `µ o C JD, (r 2 ) 0.91C ]^(. TU ' :, Raoult n 2 { ' van LaarY 2 { ;( j&«(. n-butanol+n-propionic Acid 7 :, Raoult n 2 { + A A.A.P.E. 4.90%'D, f g ' o C'i, `µ o C JD r BC ] ^(. van LaarY 2 { + A A.A.P.E. 3.38% 'D, fg ' 1.34 o C'i, `µ o C JD r C ]^(. TU n-butanol+n-propionic Acid :, Fig. 4. Comparion of lower flah point of experimental and predicted for n-butanol(x 1 )+n-propionic acid(x 2 ) ytem. van LaarYBC { ' Raoult n 2 { ;( j &«(. A + #4 0 " l j&d EB], n-propanol +n-propionic Acid 8, n-butanol+n-propionic Acid n-propionic Acid 5ç' 1 3c!, + A ' '1 ;«(. ' n-propionic Acid L i (25) âã' E }BC W{(. "BC #4 0 " mn ' NO,ž HWAHAK KONGHAK Vol. 41, No. 2, April, 2003

5 190 ˆ 0 Rµ ß ll, E m nbc 'R1 R6"(. 5. n-propanol+n-propionic Acid 8, n-butanol+n-propionic Acid 6 2 opy &1 '" l&8 [\ ˆ #ƒ q " ~ ±ª (Ñ+ ¾ ² (. (1) n-propanol+n-propionic Acid 7 : Raoult n 2 { + A A.A.P.E. 4.96%'D, fg ' o C1 ;«D, 'G[ q " van LaarY " A.A.P.E. 6.38%'D, fg ' o C1 ;«(. (2) n-butanol+n-propionic Acid : Raoult n 2 { + A A.A.P.E. 4.90%'D, fg ' o C1 ;«D, 'G[ q " van LaarY " A.A.P.E. 3.38%'D, fg ' 1.34 o C1 ;«(. (3) 3# 25 ˆ 6" l =Á *q«(. (4) n-propanol+n-propionic Acid 8, n-butanol+n-propionic Acid VW ƒf$,- )* ; R VWC 0F (. A, B, C : antoine contant A 12, A 21 : parameter in the equation of van Laar L i : lower exploive limit : upper exploive limit U i T Lf T Uf L i (25) L i (t) x i : lower flah point : upper flah point : lower exploive limit at 1atm, 25 o C [vol%] : lower exploive limit at t o C [vol%] : actual partial preure of component i in vapor-air mixture [kpa] : vapor preure of component i [kpa] : mole fraction of component i t : temperature [ o C] S : ample tandard deviation y i : ample ỹ i : ample mean n : ample number SSR : um of quare due to regreion SST : um of quare total r i r 2 : activity coefficient of component i : ample coefficient of determination 1. Meyer, E., Chemitry of Hazardou Material, 2nd ed., Prentice-Hall Inc., New Jerey, NJ(1990). 2. Lee, S. K. and Ha, D. M., Newet Chemical Engineering Safety Engineering, Donghwagiul Publiher, Seoul(1997). 3. American Society for Teting Material, Annual Book of ASTM Standard, 05(01) (1999). 4. American Society for Teting Material, Annual Book of ASTM Standard, 05(01) (1999). 5. American Society for Teting Material, Annual Book of ASTM Standard, 05(01) (1999). 6. American Society for Teting Material, Annual Book of ASTM Standard, 06(01) (1999). 7. American Society for Teting Material, Annual Book of ASTM Standard, 05(02) (1999). 8. Yagyu, S., Diagram Relationhip Between the Flah Point and Flammability Limit, J. of Japan Society for Safety Engineering, 24(3), (1985). 9. Lance, R. C., Barnard, A. J. and Hooyman, J. E., Meaurement of Flah Point: Apparatu, Methodology, Application, J. of Hazardou Material, 3, (1979). 10. Affen, W. A. and Mclaren, G. W., Flammability Propertie of Hydrocarbon Solution in Air, J. of Chem. Eng. Data, 17(4), (1972). 11. Wu, D. T. and Finkelmen, R., A Mathematical Model for the Prediction Cloed Cup Flah Point, American Chemical Society. Diviion of Organic Coating and Platic Chemitry, 61-67(1978). 12. Gmehling, J. and Ramuen, P., Flah Point of Flammable Liquid Mixture Uing UNIFAC, Ind. Eng. Chem. Fundam., 21(2), (1982). 13. Ha, D. M. and Kim, M. G., Prediction of Flah Point for the Flammable Ternary Sytem, J. of the Korean Intitute for Indutrial Safety, 12(1), 76-82(1997). 14. Hanley, B. F., A Model for the Calculation and the Verification of Cloed Flah Point Multicomponent Mixture, Proce Safety Progre, 17(2), 86-97(1998). 15. Ha, D. M., Mok, Y. S. and Choi, J. W., Flah Point of a Flammable Liquid Mixture of Binary Sytem, HWAHAK KONGHAK, 37(2), (1999). 16. Mitchell, J. W., Vratano, M. S., Hanley, B. F. and Parekh, V. S., Experimental Flah Point of Indutrial Amine, J. of Chem. Eng. Data, 44(2), (1999). 17. Jone, J. C. and Godefroy, J., A Reappraial of the Flah Point of Formic Acid, J. of Lo Prevention in the Proce Indutrie, 15(3), (2002). 18. Godefroy, J. and Jone, J. C., A Reappraial of the Flah Point of Formic Acid, J. of Lo Prevention in the Proce Indutrie, 15(3), (2002). 19. Smith, J. M. and Van Ne, H. C., Introduction to Chemical Engineering Thermodynamic, 4th ed., McGraw-Hill, New York, NY(1987). 20. Ha, D. M., A Study on Exploive Limit of Flammable Material, J. of the Korean Intitute for Indutrial Safety, 14(1), (1999). 21. Zabetaki, M. G., Flammability Characteritic of Combutible Gae and Liquid, U.S. Bureau of Mine, Bulletin 627(1965). 22. Reid, C. R., Praunitz, J. M. and Poling, B. E., The Propertie of Gae and Liquid, 4th ed., McGraw-Hill, New York, NY(1988). 23. Gmehling, J., Onken, U. and Arlt, W., Vapor-Liquid Equilibrium Data Collection, Vol. 1, Part 1~Part 7, Deutche Geellchaft fur Chemiche Apparateween(DECHEMA)(1980). 24. Lenga, R. E. and Votoupal, K. L., The Sigma-Aldrich Library of Regulatory and Safety Data, Vol. I~Vol. III, Sigma Chemical Company and Aldrich Chemical Company Inc.(1993). 25. Lide, D. R., CRC Handbook of Chemitry and Phyic, 75th ed.,

6 2 191 CRC Pre(1994). 26. NFPA, Fire Hazard Propertie of Flammable Liquid, Gae, and Volatile Solid, NFPA 325M, Quincy, MA(1991). 27. Ha, D. M. and Park, J. C., The Repreentation of the Ternary Sytem by the Etimation of the Group-Group and Interaction Parameter for MRSM-1 Model, HWAHAK KONGHAK, 29(3), (1991). 28. Kim, M. G., Ha, D. M. and Park, J. C. Modified Repone Surface Methodology(MRSM) for Phae Equilibrium-Application, Korean J. Chem. Eng., 12(1), 39-47(1995). 29. Kleinbaum, D. G., Kupper, L. L. and Muller, K. E., Applied Regreion Analyi and Other Multivariable Method, 2nd ed., PWS- KENT Publihing Company, Boton(1988). HWAHAK KONGHAK Vol. 41, No. 2, April, 2003

Prediction and measurement of the lower flash points for flammable binary solutions by using a setaflash closed cup tester

Korean J. Chem. Eng., 8(5), 1161-1165 (011) DOI: 10.1007/s11814-010-0478-y INVITED REVIEW PAPER Prediction and measurement of the lower flash points for flammable binary solutions by using a setaflash