12 research outputs found
Current Synthetic Methodologies For Semiconducting Polymers
No full textSince the publication of pioneering work in the 1970's, which described and evaluated conducting polymers, the preparation of precisely substituted polymers for the purpose of obtaining materials with tuned electrical and mechanical properties has seized great attention from the scientific community. The arsenal of synthetic methodologies available to access archetypal or tailored polymer structures can be either wide or limited depending upon the nature of the desired monomer. These type of materials include polyacetylene itself or its related poly(hetero)arylenevinylenes analogues and the major synthetic approaches towards polymer synthesis comprise Ullmann, Heck or Wittig type reactions, olefin metathesis, aldol condensation and, of course, electrochemical polymerizations. The regio- and chemoselectivity of these methodologies will be discussed here with special emphasis covering synthetic approaches to homopolymer preparation, although some of these reactions can be effectively used to prepare different types of copolymers. © 2013 Nova Science Publishers, Inc. All rights reserved.126Bunnett, J.F., Zahler, R.E., (1951) Chem. Rev., 49, p. 273Lindley, J., (1984) Tetrahedron, 40, p. 1433Cohen, T., Wood, J., Dietz, A.G., (1974) Tetrahedron Lett., 15, p. 3555Jones, G.O., Liu, P., Houk, K.N., Buchwald, S.L., (2010) J. Am. Chem. Soc., 132, p. 6205Kunz, K., Scholz, U., Ganzer, D., (2003) Synlett, 15, p. 2428Shirakawa, H., Louis, E.J., MacDiarmid, A.G., Chiang, C.K., Heeger, A.J., (1977) J. Chem. Soc., Chem. Commun., 578Chiang, C.K., Fincher, C.R., Park, Y.W., Heeger, A.J., Shirakawa, H., Louis, E.J., Gau, S., MacDiarmid, A.G., (1977) Phys. Rev. Lett., 39, p. 1098Goto, H., Iino, K., Akagi, K., Shirakawa, H., (1997) Synth. 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Exploitation Of A Tuned Oxidation With N -haloimides In The Synthesis Of Caulibugulones A-d
No full textMarine alkaloids caulibugulones A-D were synthesized in six steps starting from the readily available 2,5-dimethoxybenzaldehyde. Pomeranz-Fritsch reaction of N-(2,5-dimethoxybenzyl)-N-(2,2-dimethoxyethyl)-2-nitrobenzenesulfonamide proceeded smoothly to give 5,8-dimethoxyisoquinoline, which was oxidized to isoquinolinediones by a tunable oxidation reaction with N-haloimides. Therefore, NBS furnished direct conversion to the isoquinoline-5,8-dione; alternatively, N-haloimides of cyanuric acid provided both oxidation and halogenation generating 6,7-dihaloisoquinoline-5,8-diones. Aminolyses of these isoquinolinediones with methylamine or ethanolamine produced the isoquinolinedione alkaloids caulibugulones A-D in 24-57% overall yield. © 2013 American Chemical Society.781050265030Milanowski, D.J., Gustafson, K.R., Kelley, J.A., McMahon, J.B., (2004) J. Nat. Prod., 67, p. 70Wipf, P., Joo, B., Nguyen, T., Lazo, J.S., (2004) Org. Biomol. Chem., 2, p. 2173Alagille, D., Baldwin, R.M., Tamagnan, G.D., (2004) Tetrahedron Lett., 45, p. 6179Brisson, M., Foster, C., Wipf, P., Joo, B., Tomko Jr., R.J., Nguyen, T., Lazo, J.S., (2007) Mol. Pharmacol., 71, p. 184Vintonyak, V.V., Antonchick, A.P., Rauh, D., Waldmann, H., (2009) Curr. Opin. Chem. Biol., 13, p. 272Contour-Galcera, M.O., Sidhu, A., Prévost, G., Bigg, D., Ducommun, B., (2007) Pharmacol. Therapeut., 115, p. 1Konakahara, T., Kiran, Y.B., Okuno, Y., Ikeda, R., Sakai, N., (2010) Tetrahedron Lett., 51, p. 2335Birch, A.J., Jackson, A.H., Shannon, P.V.R., (1974) J. Chem. Soc., Perkin Trans. 1, p. 2185Song, Y., Shao, Z., Dexheimer, T.S., Scher, E.S., Pommier, Y., Cushman, M., (2010) J. Med. Chem., 53, p. 1979Bracca, A.B.J., Kaufman, T.S., (2007) Eur. J. Org. Chem., p. 5284Silveira, C.C., Bernardi, C.R., Braga, A.L., Kaufman, T.S., (2002) Synlett, p. 907Aizawa, K., Nakagawa, H., Matsuo, K., Kawai, K., Ieda, N., Suzuki, T., Miyata, N., (2013) Bioorg. Med. Chem. Lett., 23, p. 2340Kim, D.W., Choi, H.Y., Lee, K.J., Chi, D.Y., (2001) Org. Lett., 3, p. 445Tozetti, S.D.F., Almeida, L.S., Esteves, P.M., Mattos, M.C.S., (2007) J. Braz. Chem. Soc., 18, p. 675Almeida, L.S., Esteves, P.M., Mattos, M.C.S., (2006) Synthesis, p. 221Lisboa, C.D., Santos, V.G., Vaz, B.G., Lucas, N.C., Eberlin, M.N., Garden, S.J., (2011) J. Org. Chem., 76, p. 5264Still, W.C., Kahn, M., Mitra, A., (1978) J. Org. Chem., 43, p. 2923Almeida, L.S., Esteves, P.M., Mattos, M.C.S., (2006) Synlett, 10, p. 151
2,3,5,6-tetra(pyrazin-2-yl)pyrazine: A Novel Bis-bidentate, Bis-tridentate Chelator
No full textNovel 10-nitrogen ligand, 2,3,5,6-tetra(pyrazin-2-yl)pyrazine, has been synthesized in four steps. This compound shows different conformations and the crystal structure of one of them has been established. This structure is sustained by non-classical H-bonds and π···π interactions among heteroaromatic rings. © 2009.502840304032Bera, J.K., Campos-Fernández, C.S., Rodolphe, C., Dunbar, K.R., (2002) Chem. Commun., pp. 2536-2537Bitzer, R.S., Teles, W.M., Abras, A., Ardissom, J.D., Filgueiras, C.A.L., (2005) J. Braz. Chem. Soc., 16, pp. 963-968Pourtois, G., Beljonne, D., Moucheron, C., Schumm, S., Mesmaeker, A.K., Lazzaroni, R., Brédas, J.L., (2004) J. Am. Chem. Soc., 126, pp. 683-692Boisdenghien, A., Moucheron, C., Mesmaeker, A.K., (2005) Inorg. Chem., 44, pp. 7678-7685Constable, E.C., (2008) Coord. Chem. Rev., 252, pp. 842-855Swiegers, G.F., Malefetse, T.J., (2000) Chem. Rev., 100, pp. 3483-3538Preston, A.J., Gallucci, J.C., Parquette, J.R., (2006) Org. Lett., 8, pp. 5885-5888Lainé, P., Bedioui, F., Ochsenbein, P., Marvaud, V., Bonin, M., Amouyal, E., (2002) J. Am. Chem. Soc., 124, pp. 1364-1377Mato, A.F., Blanco, G., Quintela, J.M., Peinador, C., (2008) Tetrahedron, 64, pp. 3446-3456Zong, R., Wang, D., Hammitt, R., Thummel, R.P., (2006) J. Org. Chem., 71, pp. 167-175Angaridis, P., Berry, J.F., Albert Cotton, F., Murillo, C.A., Wang, X., (2003) J. Am. Chem. Soc., 125, pp. 10327-10334Brown, D., Muranjan, S., Jang, Y., Thummel, R., (2002) Org. Lett., 4, pp. 1253-1256Kelch, S., Rehahn, M., (1997) Macromolecules, 30, pp. 6185-6193Torres, S.F., Hutcthison, G.R., Soltzberg, L.J., Abruña, H.D., (2006) J. Am. Chem. Soc., 128, pp. 1513-1522Yuasa, J., Fukuzumi, S., (2008) J. Am. Chem. Soc., 130, pp. 566-575Leveque, J., Elias, B., Moucheron, C., Mesmaeker, A.K., (2005) Inorg. Chem., 44, pp. 393-400Bitzer, R., Gil, R.A.S.S., Filgueiras, C.A.L., (2006) J. Braz. Chem. Soc., 17, pp. 1600-1604Buelher, C.A., Addleburg, J.W., Glenn, D.M., (1955) J. Org. Chem., 20, pp. 1350-1355Ellingson, R.C., Henry, R.L., McDonald, F.G., (1945) J. Am. Chem. Soc., 67, pp. 1711-1733Rutner, H., Spoerri, P.E., (1963) J. Org. Chem., 28, pp. 1898-1899Goodwin, H.A., Lions, F., (1959) J. Am. Chem. Soc., 81, pp. 6415-6422Bock, H., Vaupel, T., Näther, C., Ruppert, K., Havlas, Z., (1992) Angew. Chem., Int. Ed. Engl., 31, pp. 299-301Padgett, C.W., Pennington, W.T., Hanks, T.W., (2005) Cryst. Growth Des., 5, pp. 737-744Steiner, T., (2002) Angew. Chem., Int. Ed., 41, pp. 48-76Ohkita, M., Kawano, M., Suzuki, T., Tsuji, T., (2002) Chem. Commun., pp. 3054-3055Jeffrey, G.A., Maluszynska, H., Mitra, J., (1985) Int. J. Biol. Macromol., 7, pp. 336-348Raymo, F.M., Bartberger, M.D., Houk, K.N., Fraser Stoddart, J., (2001) J. Am. Chem. Soc., 123, pp. 9264-9267Hunter, C.A., Lawson, K.R., Perkins, J., Urch, C.J., (2001) J. Chem. Soc., Perkin Trans. 2, pp. 651-669Jaffe, R.L., Smith, G.D., (1996) J. Chem. Phys., 105, pp. 2780-2788Hobza, P., Selzle, H.L., Schlag, E.W., (1994) J. Am. Chem. Soc., 116, pp. 3500-350
Use And Recycling Of Silica Gel Impregnated With Silver Nitrate [utilização E Recuperação De Sílica Gel Impregnada Com Nitrato De Prata]
No full textArgentation chromatography is used to increase the selectivity of the chromatographic process, chiefly in the resolution of complex mixtures of nonpolar substances. Although efficient, this technique generates residues containing heavy metal which makes its discarding through common procedures impracticable. In the present work a simple method for recycling of silica, and also silver, from argentation chromatography is described. This procedure uses initially a treatment of H2O2/HNO3, with subsequent treatment with H2O2/H2SO4, allowing an efficient recycling of both components. This methodology is simple, costless, removes impurities efficiently, and does not modify retention parameters nor specific surface in a significant way.331212215Williams, C.M., Mander, L.M., (2001) Tetrahedron, 57, p. 425Cechi, L., Malaspina, P., (1991) Anal. Biochem., 192, p. 219Siouffi, A.M., Traynard, J.C., (1977) J. Chromatogr. Sci., 15, p. 469Bhushan, R., Thiong'o, G.T., (2002) Biomed. Chromatogr., 16, p. 165Eberz, W.F., Welge, H.J., Yost, D.M., Lucas, H.J., (1937) J. Am. Chem. Soc., 59, p. 45Winstein, S., Lucas, J.H., (1938) J. Am. Chem. Soc., 60, p. 836Li, T.S., Li, J.T., Li, H.Z., (1995) J. Chromatogr., A, 715, p. 372Jarusiewicz, J., Sherma, J., Fried, B., (2005) J. Liq. Chromatogr. Relat. Technol., 28, p. 2607Damyanova, B.N., (1999) J. Liq. Chromatogr. Relat. Technol., 22, p. 1513Momchilova, S., Damyanova, B.N., (2003) J. Sep. Sci., 26, p. 261Van Beek, T.A., Subrtova, D., (1995) Phytochem. Anal., 6, p. 1Nogueira, R.T., Giacomini, R.A., Shepherd, G.J., Imamura, P.M., (2002) J. Braz. Chem. Soc., 13, p. 389Damyanova, B.N., Christie, W.W., Herslöf, B., (1996) J. Chromatogr., A, 749, p. 47Ho, Y.P., Yang, Y.C., Klippenstein, S.J., Dunbar, R.C., (1997) J. Phys. Chem. A, 101, p. 3338Kaneti, J., De Smet, L.C.P.M., Boom, R., Zuilhof, H., Sudhölter, E.J.R., (2002) J. Phys. Chem. A, 106, p. 11197Teixeira, S.C.G., Mathias, L., Canela, M.C., (2003) Quim. Nova, 26, p. 931Riehl, C.A.S., Pinto, A.C., (1988) Quim. Nova, 11, p. 329Loureiro, A.P., Souza, J.A., Aparecido, D., Fernandes, J.B., (1991) Quim. Nova, 14, p. 112A mistura dos ésteres 1, 2, 3 e 4 foi obtida do extrato hexânico do epicarpo de Hymenaea stigonocarpa por eluição em coluna cromatográfica com sílica gel 60 (Merck®) de granulometria entre 70 e 230 mesh. Este sistema foi incapaz de resolver a mistura mesmo realizando-se eluições sucessivas nas mesmas condiçõesSing, K.S.W., Everett, D.H., Haul, R.A.W., Moscou, L., Pierotti, R.A., Rouquerol, J., Siemieniewska, T., (1985) Pure Appl. Chem., 57, p. 60
Differential Oxidation Of Endocyclic Enecarbamates. Synthesis Of Cyclic β-hydroxy-α-amino Acids
No full textThe differential oxidation of five and six-membered endocyclic enecarbamates was investigated employing m-CPBA, DMD, as well as enantioselectivc protocols such as the Kochi-Jacobsen-Katsuki's epoxidation and the Sharpless dihydroxylation. By this strategy the syntheses of β- hydroxyprolines and β-hydroxypipecolic acids were accomplished, X-Ray crystallographic analysis of the trans-β-hydroxypipecolic acid was instrumental to solve structural assignment conflicts.392134133416Hanessian, S., M-Smith, G., Lombart, H.-G., Lubell, W.D., (1997) Tetrahedron, 53, p. 12789Sharma, R., Lubell, W.D., (1996) J. Org. Chem., 61, p. 202Beausoleil, E., L'Archevêque, B., Bélec, L., Atfani, M., Lubell, W.D., (1996) J. Org. Chem., 61, p. 9447Mulzer, J., Meier, A., (1996) J. Org. Chem., 61, p. 566Herdeis, C., Hubmann, H.P., (1994) Tetrahedron Asymmetry, 5, p. 119Dieterich, P., Young, D.W., (1993) Tetrahedron Lett., 34, p. 5455Pohlit, A.M., Correia, C.R.D., (1997) Heterocycles, 45, p. 2321Carpes, M.J.S., Miranda, P.C.M.L., Correia, C.R.D., (1997) Tetrahedron Lett., 38, p. 1869Correia, C.R.D., Faria, A.R., Carvalho, E.S., (1995) Tetrahedron Lett., 36, p. 5109Faria, A.R., Matos, C.R., Correia, C.R.D., (1993) Tetrahedron Lett., 34, p. 27Williams, R.M., Cao, J., (1996) Tetrahedron Lett., 37, p. 5441Cooper, J., Gallagher, P.T., Knight, D.W., (1988) J. Chem. Soc., Chem. Commun., p. 509Knight, D.W., Lewis, N., Share, A.C., Haigh, D., (1993) Tetrahedron Asymm., 4, p. 625Kusano, G., Ogawa, H., Takahashi, A., Nozoe, S., Yokoyama, K., (1987) Chem. Pharm. Bull, 35, p. 3482Burgess, L.E., Gross, E.K.M., Jurka, J., (1996) Tetrahedron Lett., 37, p. 3255Larrow, J.F., Jacobsen, E.N., Gao, Y., Hong, Y., Nie, X., Zepp, C.M., (1994) J. Org. Chem., 59, p. 1939notenoteKolb, H.C., Vannieuwenhze, M.S., Sharpless, K.B., (1994) Chem. Rev., 94, p. 2483Thaning, M., Wistrand, L.-G., (1989) Acta Chemica Scandinavica, 43, p. 290Mulzer, J., Meier, A., (1996) J. Org. Chem., 61, p. 566Roemmele, R.C., Rapoport, H., (1989) J. Org. Chem., 54, p. 1866Greck, C., Ferreira, F., Genêt, J.P., (1996) Tetrahedron Lett., 37, p. 2031Agami, C., Couty, F., Mathieu, H., (1996) Tetrahedron Lett., 37, p. 4001notenot
Thermal Properties Of Biodiesel And Their Corresponding Precursor Vegetable Oils Obtained By Photopyroelectric Methodology
No full textThe photopyroelectric technique (PPE) was used for thermal characterization of biodiesel and their corresponding precursor vegetable oils. Different configurations of PPE were applied in these studies. The standard and inverse configurations allowed the determination of the thermal diffusivity (α) and thermal effusivity (e), respectively. From these two parameters the thermal conductivity was calculated. Measurements were performed for reference samples (water and ethylene glycol), biodiesel, and some corresponding precursor vegetable oils. The experiments showed good reproducibility, with uncertainties around 1 % to 2 % for all the samples. Lower values for both α and e of the biodiesel when compared to their corresponding precursor vegetable oils were observed, indicating that these thermophysical properties were sensitive to structural changes during the transesterification process. © 2012 Springer Science+Business Media, LLC.3310-1118481855Knothe, G., Gerpen, J.V., Krahl, J., Ramos, L.P., (2005) The Biodiesel Handbook, , AOCS Press Champaign, IL 10.1201/9781439822357Vargas, H., Miranda, L.C.M., (2003) Rev. Sci. Instrum., 74, p. 794. , 2003RScI.74.794V 10.1063/1.1519682Coufal, H., (1984) Appl. Phys. Lett., 44, p. 159. , 10.1063/1.94551Delgadillo-Holfort, I., Pereira, J.R., Guimarães, A.O., Da Silva, E.C., (2004) Int. J. Thermophys., 25, p. 587. , 2004IJT.25.587D 10.1023/B:IJOT.0000028492.71162.e4Chirtoc, M., Miháilescu, G., (1989) Phys. Rev. B, 40, p. 9606. , 1989PhRvB.40.9606C 10.1103/PhysRevB.40.9606Matvienko, A., Mandelis, A., (2005) Int. J. Thermophys., 26, p. 837. , 2005IJT.26.837M 10.1007/s10765-005-5581-7Dadarlat, D., Neamtu, C., (2009) Acta Chim. Slov., 56, p. 225Dadarlat, D., Nematu, C., Streza, M., Socaciu, C., Bele, C., Dulf, F., (2009) Eur. J. Lipid Sci. Technol., 111, p. 148. , 10.1002/ejlt.200800076Hadj Sahraoui, A., Longuemart, S., Dadarlat, D., Delencos, S., Kolinsky, C., Buisine, M., (2002) Rev. Sci. Instrum., 73, p. 2766. , 2002RScI.73.2766S 10.1063/1.1482151Castro, M.P., (2011) Biodiesel - Quality, Emissions and By-Products, pp. 29-46. , chap. 2 (InTech, Rijeka-CroatiaDardalat, D., Neamtu, C., (2006) Meas. Sci. Technol., 17, p. 3250. , 2006MeScT.17.3250D 10.1088/0957-0233/17/12/008Bindhu, C.V., Harilal, S.S., Nampoori, V.P.N., Vallabhan, C.P.G., (1998) Opt. Eng., 37, p. 2791. , 1998OptEn.37.2791B 10.1117/1.601825Castro, M.P.P., Andrade, A.A., Franco, R.W.A., Miranda, P.C.M.L., Sthel, M., Vargas, H., Constantino, R., Baesso, M.L., (2005) Chem. Phys. Lett., 411, p. 18. , 2005CPL.411.18C 10.1016/j.cplett.2005.06.003Menon, P.M., Rajesh, R.N., Glorieux, C., (2009) Rev. Sci. Instrum., 74, p. 054904. , 2009RScI.80e4904M 10.1063/1.3131625Hadj Sahraoui, A., Longuemart, S., Dadarlat, D., Delencos, S., Kolinsky, C., Buisine, M., (2002) Rev. Sci. Instrum., 73, p. 2766. , 2002RScI.73.2766S 10.1063/1.1482151Delencos, S., Chirtoc, M., Hadj Sahraoui, A., Kolinsky, C., Buisine, M., (2002) Rev. Sci. Instrum., 73, p. 2773. , 2002RScI.73.2773D 10.1063/1.148814
Synthesis Of Aryl Pyrrolizidines From Endocyclic Enecarbamates. Novelapplications Of The Heck Arylation Of 3-pyrrolines Using Diazonium Salts
No full textThe novel aryl platynecines 3a/3b were synthesized from endocyclic 4-aryl enecarbamates 8a/8b by a concise and practical route. The synthesis was based on an efficient preparation of 4-aryl enecarbamates 8a/8b from 3-pyrrolines by means of a Heck arylation using aryldiazonium tetrafluoroborates, followed by a highly stereoselective cycloaddition of the 4-aryl enecarbamates 8a/8b to 2-chloroethyl ketene to afford exclusively the 7-endo-(2-chloroethyl) cyclobutanones 12a/12b in good yields (67% and 65%). Baeyer-Villiger oxidation of the cyclobutanones 12a/12b occurred with high regioselectivity to furnish the aza-lactones 13a/13b in 96% and 90% yields. Reduction of lactones 13a and 13b with LiAlH4 gave the desired aryl platynecines 3a/3b. The total synthetic sequence involved 6 steps and provided the aryl platynecines 3a/3b in an overall yield of 41% and 38%, respectively. These compounds are the first examples of necine bases bearing an aromatic substituent on the azabicyclo[3.3.0]octane framework and incorporate some of the key structural element of the pharmacologically active 1,3,4-trisubstituted pyrrolines which act as antagonists of the chemokine receptor CC5.200310390403Liddel, J.R., (2000) Nat. Prod. Rep., 17, p. 455Robins, D., (1989) Chem. Soc. Rev., 18, p. 375Mattoc, A.R., (1986) Chemistry and Toxicology of Pyrrolizidine Alkaloids, , Academic Press: LondonCooper, R.A., Huxtable, R., (1996) Toxicon, 34, p. 604Couet, C.E., Hopley, J., Hanley, A.B., (1996) Toxicon, 34, p. 1058Ober, D., Hartmann, T., (1999) J. Bio. Chem., 274, p. 32040Gordon, G.J., Coleman, W.B., Grisham, J.W., (2000) Experimental and Molecular Pathology, 69, p. 17Hanselmann, R., Benn, M., (1993) Tetrahedron Lett., 34, p. 3511Faria, A.R., Salvador, E.L., Correia, C.R.D., (2002) J. Org. Chem., 67, p. 3651Faria, A.R., Matos, C.R., Correia, C.R.D., (1993) Tetrahedron Lett., 34, p. 27Faria, A.R., Carvalho, E.S., Correia, C.R.D., (1995) Tetrahedron Lett., 36, p. 5109Willoughby, C.A., Rosauer, K.G., Hale, J.J., Budhu, R.J., Mills, S.G., Chapman, K.T., MacCoss, M., Emini, E.A., (2003) Bioorg. Med. Chem. Lett., 13, p. 427Lynch, C.L., Hale, J.J., Budhu, R.J., Gentry, A.L., Mills, S.G., Chapman, K.T., MacCoss, M., Emini, E.A., (2002) Bioorg. Med. Chem. Lett., 12, p. 3001Hale, J.J., Budhu, R.J., Mills, S.G., MacCoss, M., Gould, S.L., DeMartino, J.A., Springer, M.S., Emini, E.A., (2002) Bioorg. Med. Chem. Lett., 12, p. 2997Lynch, C.L., Hale, J.J., Budhu, R.J., Gentry, A.L., Finke, P.E., Caldwell, C.G., Mills, S.G., Emini, E., (2003) Org. Lett., 5, p. 2473Garcia, A.L.L., Correia, C.R.D., (2003) Tetrahedron Lett., 44, p. 1553Carpes, M.J.S., Correia, C.R.D., (2000) Synlett, 7, p. 1037Oliveira, D.F., Miranda, P.C.M.L., Correia, C.R.D., (1999) J. Org. Chem., 64, p. 6646Roe, A., (1949) Org. React., 5, p. 193Cabri, W., Candiani, I., (1995) Acc. Chem. Res., 28, p. 2Hallberg, A., Clas, S., Larbed, M., Nyqvist, C., (1996) J. Org. Chem., 61, p. 4756Krow, G.R., (1991) Comprehensive Organic Synthesis, 7, p. 671. , Ley, S. V. Ed.Pergamom Press: Oxfor
Thermal Effusivity And Thermal Conductivity Of Biodiesel/diesel And Alcohol/water Mixtures
No full textThe photopyroelectric (PPE) technique was used for the determination of the thermal effusivity and thermal conductivity of biodiesel in diesel and other binary liquid mixtures, precisely, ethanol, and ethylene glycol in water. The front configuration (FPPE) has been explored in the frequency scan approach for obtaining thermal-effusivity values. Measurements show good reproducibility, with uncertainties around 1 % to 2 %, and the results for reference samples, such as ethanol and water, are in good agreement with literature values. The thermal-conductivity values of all samples were determined using the thermal-effusivity data presented here and the thermal-diffusivity data of exactly the same set of samples, reported elsewhere. Based on these results, the different strengths in the molecular interactions related to the several mixtures were evidenced, as proposed by Dadarlat et al. It was shown that, indeed, the thermal effusivity is the property presenting the smallest sensitivity for the molecular association phenomenon, while the thermal conductivity presents an intermediate sensitivity. Nevertheless, the analysis of both properties revealed the existence of weak cohesive interactions among the hydrocarbons of diesel and the esters of biodiesel. © 2012 Springer Science+Business Media, LLC.3310-1118421847Knothe, G., Van Gerpen, J., Krahl, J., (2005) The Biodiesel Handbook, , (eds) AOCS Press Champaign, ILBasha, S.A., Gopal, K.R., Jebaraj, S., (2009) Renew. Sustain. Energy Rev., 13, p. 1628. , 10.1016/j.rser.2008.09.031Sazhin, S.S., Abdelghaffar, W.A., Krutitskii, P.A., Sazhina, E.M., Heikal, M.R., (2005) Int. J. Heat Mass Transf., 48, p. 4215. , 1188.76263 10.1016/j.ijheatmasstransfer.2005.04.007Aliske, M.A., Zagonel, G.F., Costa, B.J., Veiga, W., Saul, C.K., (2007) Fuel, 86, p. 1461. , 10.1016/j.fuel.2006.11.008Morón-Villarreyes, J.A., Soldi, C., De Amorim, A.M., Pizzolatti, M.G., De Mendonça, Jr.A.P., D'Oca, M.G.M., (1977) Fuel, 86, p. 1977. , 10.1016/j.fuel.2007.01.003Almond, D.P., Patel, P.M., (1996) Photothermal Science and Techniques, , Chapman & Hall LondonGuimaraes, A.O., Machado, F.A.L., Zanelato, E.B., Sthell, M.S., Da Silva, E.C., Aranda, D.A.G., (2009) Int. Rev. Chem. Eng., 623, p. 623Castro, M.P.P., Andrade, A.A., Franco, R.W.A., Miranda, P.C.M.L., Sthel, M., Vargas, H., Constantino, R., Baesso, M.L., (2005) Chem. Phys. Lett., 411, p. 18. , 2005CPL.411.18C 10.1016/j.cplett.2005.06.003Delgadillo-Holtfort, I., (2004) Int. J. Thermophys., 2, p. 587Guimarães, A.O., Machado, F.A.L., Da Silva, E.C., Mansanares, A.M., (2012) Thermochim. Acta, 527, p. 125Chirtoc, M., Bentefour, E.H., Antoniow, J.S., Glorieux, C., Delenclos, S., Sahraoui, A.H., Longuemart, S., Buisine, J.M., (2003) Rev. Sci. Instrum., 74, p. 648. , 2003RScI.74.648C 10.1063/1.1520314Chirtoc, M., Miháilescu, G., (1989) Phys. Rev. B, 40, p. 9606. , 1989PhRvB.40.9606C 10.1103/PhysRevB.40.9606Hadj Sahraoui, A., Longuemart, S., Dadarlat, D., Delenclos, S., Kolinsky, C., Buisine, M., (2003) Rev. Sci. Instrum., 74, p. 618. , 2003RScI.74.618S 10.1063/1.1512976Dadarlat, D., Neamtu, C., (2006) Meas. Sci. Technol., 17, p. 3250. , 2006MeScT.17.3250D 10.1088/0957-0233/17/12/008Delenclos, S., Chirtoc, M., Hadj Sahraoui, A., Kolinsky, C., Buisine, M., (2002) Rev. Sci. Instrum., 73, p. 2773. , 2002RScI.73.2773D 10.1063/1.1488147Neamtu, C., Dadarlat, D., Chirtoc, M., Hadj Sahraoui, A., Longuemart, S., Bicanic, D., (2006) Instrum. Sci. Technol., 34, p. 225. , 10.1080/10739140500374088Dadarlat, D., Neamtu, C., (2009) Acta Chim. Slov., 56, p. 22
Modelagem e simulação de um reator tubular contínuo para a produção de biodiesel
No full textTese (doutorado) - Universidade Federal de Santa Catarina, Centro Tecnológico. Programa de Pós-Graduação em Engenharia QuímicaO impacto ambiental devido ao uso de combustíveis fósseis e as questões políticas envolvendo seu uso tem impulsionado a busca por combustíveis derivados da biomassa. Desta forma, o biodiesel tem aparecido nesse contexto com o objetivo de substituir, parcialmente ou totalmente, a utilização de combustíveis derivados de petróleo. O biodiesel é definido como uma mistura de ésteres obtidos principalmente a partir da reação de triglicerídeos e álcool. A reação mais comumente utilizada para sua síntese é a transesterificação. Este trabalho tem como objetivo desenvolver um modelo multifísico, empregando o método de elementos finitos, para a produção de biodiesel em reator tubular, considerando escala laboratorial e industrial. A reação de transesterificação foi idealizada segundo uma proporção molar de 1:5 (óleo de colza:metanol), considerando catalisador básico, juntamente com um modelo cinético completo, incluindo as reações diretas e reversas. Foram estudados aspectos da transferência de massa, calor e quantidade de movimento ao longo do reator. Foi analisado o efeito da presença do meio poroso e da prática de mistura prévia dos reagentes à injeção no reator, juntamente com o efeito da perda de calor por fluxo convectivo nas paredes do reator. Verificou-se que a reação do óleo de colza e metanol é muito rápida, atingindo altas conversões (99,44%) em poucos minutos de reação. Com relação à cinética reacional da produção de biodiesel, os dados obtidos por meio do modelo desenvolvido foram validados com dados experimentais da literatura, obtendo-se boa concordância entre estes e o modelo. Verificou-se que o reator tubular estudado possui comportamento teórico de um Reator Perfeitamente Misturado, apresentando um grande desvio do ideal Plug Flow. Constatou-se a partir do Planejamento Fatorial 23 que as variáveis temperatura e razão molar (metanol:triglicerídeo) são significativas com relação à conversão em biodiesel, juntamente com a interação entre elas, sendo seus efeitos positivos, ou seja, quanto maiores os valores para tais variáveis, maior será a conversão em biodiesel obtida. O modelo de regressão ajustado apresentou um excelente coeficiente de determinação, podendo ser empregado para fins preditivos. A utilização da plataforma multifísica para a simulação por meio do método de elementos finitos se mostrou uma ferramenta valiosa para o estudo da produção de biodiesel em sistemas contínuos, nos quais se pode colocar em evidência aspectos fenomenológicos do escoamento reativo. Tal estudo é importante por fornecer parâmetros que podem ser empregados para descrever o sistema reacional e auxiliar no projeto e otimização de reatores tubulares, visando condições ótimas de operação.The environmental impacts due to the use of fossil fuels and the political issues surrounding its use have driven the search for fuels derived from biomass. Thus, biodiesel has appeared in this context in order to replace partially or totally the use of petroleum fuels. Biodiesel is defined as a mixture of esters derived mainly from the reaction of triglycerides and alcohol. The reaction most commonly used for their synthesis is the transesterification. This work aims to develop a multiphysics model using the finite element method for biodiesel production in tubular reactor considering laboratorial and industrial scale. The transesterification reaction was idealized according a molar ratio of 1:5 (rapeseed oil: methanol), considered basic catalyst, together with a complete kinetic model, including direct and reverse reactions. Aspects of mass transfer, heat and momentum along the reactor was studied. The effect of the presence of the porous medium and the mixing process of reactants prior to the injection into the reactor, together with the effect of heat loss by convective flows in the walls of the reactor were analyzed. It was found that the reaction of rapeseed oil and methanol was very fast, reaching high conversions ratio (99.44%) in a few minutes of reaction. About the reactional kinetics for the biodiesel production, the data obtained through the developed model was validated with experimental data from the literature, obtaining good agreement between these and the model. It was found that the studied tubular reactor has the same theoretical behavior of a Perfectly Mixed Reactor with a large deviation from the ideal Plug Flow. It was found from the Factorial Design 23 that the variable of temperature and molar ratio (methanol:triglyceride) are significant in relation to the biodiesel conversion, along with the interaction between them and its positive effects, that is, the higher the values for these variables, the greater the conversion of the biodiesel obtained. The adjusted regression model showed an excellent coefficient determination. It can be used for predictive purposes. The use of the multiphysics platform for the simulation using the finite element method has proved a valuable tool for studying the production of biodiesel in continuous systems, in which bringing to light phenomenological aspects of the reactive flow. This study is important to provide parameters that can be used to describe the reaction system and assist in the design and optimization of tubular reactors, aiming at optimal operating conditions
Investigating Thermal Properties Of Biodiesel/diesel Mixtures Using Photopyroelectric Technique
No full textIn this work we explored the photopyroelectric technique (PPE) for the thermal characterization of biodiesel/diesel and other binary liquid mixtures, such as ethanol and ethylene glycol in water. We have used the back configuration (BPPE), in the thickness scan approach, and the front one (FPPE), in the frequency scan approach, for getting the thermal diffusivity and effusivity values, respectively. For all the measured systems, we got good data fittings when using the model proposed by Matvienko and Mandelis for thermal diffusivity of liquid mixtures. In addition, we could evidence the different strength in the molecular interaction related to the several mixtures, based on the normalized excess values for thermal diffusivity, as proposed by Dadarlat et al. For biodiesel/diesel mixtures, which present weak cohesive interactions among the saturated/aromatic hydrocarbons of diesel and the alkyl esters of biodiesel, we proposed a semi empirical model for the thermal diffusivity, based on the logarithm mixing model for the thermal conductivity and a simple addictive law for the heat capacity per unit volume. © 2011 Elsevier B.V. All rights reserved.527125130Schramm, D.U., Sthel, M.S., Da Silva, M.G., Carneiro, L.O., Junior, A.J.S., Souza, A.P., Vargas, H., Application of laser photoacoustic spectroscopy for the analysis of gas samples emitted by diesel engines (2003) Infrared Phys. Technol., 44 (4), pp. 263-269Knothe, G., Gerpen, J.V., Krahl, J., Ramos, L.P., (2005) The Biodiesel Handbook, , AOCS PressBasha, S.A., Gopal, K.R., Jebaraj, S., A review on biodiesel production, combustion, emissions and performance (2009) Renew. Sust. Energy Rev., 13 (67), pp. 1628-1634Marchetti, J.M., Miguel, V.U., Errazu, A.F., Possible methods for biodiesel production (2007) Renew. Sustain. Energy Rev., 11 (6), pp. 1300-1311Bertoli, C., Na Migliaccio, M., A finite conductivity model for diesel spray evaporation computations (1999) Int. J. Heat Fluid Flow, 20, pp. 552-561Sazhin, S.S., Abdelghaffar, W.A., Krutitskii, P.A., Sazhina, E.M., Heikal, M.R., New approaches to numerical modelling of droplet transient heating and evaporation (2005) Int. J. Heat Mass Transfer, 48 (1920), pp. 4215-4228Aliske, M.A., Zagonel, G.F., Costa, B.J., Veiga, W., Saul, C.K., Measurement of biodiesel concentration in a diesel oil mixture (2007) Fuel, 86 (1011), pp. 1461-1464Morón-Villarreyes, J.A., Soldi, C., De Amorim, A.M., Pizzolatti, M.G., De Mendona, A.P., D'Oca, Jr.M.G.M., Diesel/biodiesel proportion for by-compression ignition engines (2007) Fuel, 86 (1213), pp. 1977-1982Vargas, H., Miranda, L.C., Photoacoustic and related photothermal techniques (1988) Phys. Rep., 161 (2), pp. 43-101Almond, D.P., Patel, P.M., (1996) Photothermal Science and Techniques, , Chapman & HallChirtoc, M., Miháilescu, G., Theory of the photopyroelectric method for investigation of optical and thermal materials properties (1989) Phys. Rev. B, 40 (14), pp. 9606-9617Delenclos, S., Dadarlat, D., Houriez, N., Longuemart, S., Kolinsky, C., Hadj Sahraoui, A., On the accurate determination of thermal diffusivity of liquids by using the photopyroelectric thickness scanning method (2007) Rev. Sci. Instrum., 78 (2). , 024902-1-024902-5Menon, P.M., Rajesh, R.N., Glorieux, C., High accuracy, self calibrating photopyroelectric device for the absolute determination of thermal conductivity and thermal effusivity of liquids (2009) Rev. Sci. Instrum., 80 (5). , 054904-1-054904-5Dadarlat, D., Neamtu, C., Detection of molecular associations in liquids by photopyroelectric measurement of thermal effusivity (2006) Meas. Sci. Technol., 17 (12), pp. 3250-3254Longuemart, S., Garcia Quiroz, A., Dadarlat, D., Hadj Sahraoui, A., Kolinsky, C., Marc Buisine, J., Da Silva, E.C., Neamtu, C., An application of the front photopyroelectric technique for measuring the thermal effusivity of some foods (2002) Instrum. Sci. Technol., 30 (2), pp. 157-165Delgadillo-Holtfort, I., De, J., Pereira, R., Guimarães, A.O., Da Silva, E.C., Photothermal investigations of de-emulsification of fat/water-based pasty materials: Margarine (2004) Int. J. Thermophys., 2 (2), pp. 587-602Chirtoc, M., Bentefour, E.H., Antoniow, J.S., Glorieux, C., Delenclos, S., Sahraoui, A.H., Longuemart, S., Buisine, J.M., Current mode versus voltage mode measurement of signals from pyroelectric sensors (2003) Rev. Sci. Instrum., 74 (1), pp. 648-650Dadarlat, D., Neamtu, C., High performance photopyroelectric calorimetry of liquids (2009) Acta Chim. Slov., 56, pp. 225-236Balderaz-López, J.A., Mandelis, A., Garcia, J.A., Thermal-wave resonator cavity design and measurements of the thermal diffusivity of liquids (2000) Rev. Sci. Instrum., 71 (7), pp. 2933-2937Dadarlat, D., Neamtu, C., Streza, M., Socaciu, C., Bele, C., Dulf, F., Highly accurate photopyroelectric measurement of thermal diffusivity of vegetable oils (2009) Eur. J. Lipid Sci. 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