Effect of alkyl chain length on the thermophysical properties of pyridinium carboxylates

doi:10.1016/j.cjche.2016.11.009

摘要/Abstract

摘要： In the present study, new series of pyridinium carboxylate protic ionic liquids (PILs) were synthesized by pairing pyridinium cation with carboxylate anion from C₁-C₃ forming pyridinium formate ([C₅H₆N⁺] [HCOO^-]), pyridinium acetate ([C₅H₆N⁺] [CH₃COO^-]) and pyridinium propionate ([C₅H₆N⁺] [CH₃CH₂COO^-]) respectively. The physical properties namely, density, viscosity, surface tension (298.15-343.15) K, and refractive index (293.15-323.15) K were measured. Thermal properties namely, glass transition temperature, molar heat capacity, and thermal decomposition temperatures were also determined. The thermal expansivity was calculated using the experimental density data. The effect of increasing the alkyl chain length on the thermophysical properties of the pyridinium carboxylate PILs has been evaluated. As expected the physical properties i.e. density, viscosity, surface tension and refractive index of the investigated pyridinium carboxylates decreased with increasing temperature. In general pyridinium carboxylate PILs possessed low viscosity, high thermal stability and excellent hydrogen bonding capability, and these properties lead them to outperform conventional solvents employed for lignin dissolution.

关键词: Protic ionic liquids, Pyridine, Carboxylic acids, Anion, Physicochemical properties

Abstract: In the present study, new series of pyridinium carboxylate protic ionic liquids (PILs) were synthesized by pairing pyridinium cation with carboxylate anion from C₁-C₃ forming pyridinium formate ([C₅H₆N⁺] [HCOO^-]), pyridinium acetate ([C₅H₆N⁺] [CH₃COO^-]) and pyridinium propionate ([C₅H₆N⁺] [CH₃CH₂COO^-]) respectively. The physical properties namely, density, viscosity, surface tension (298.15-343.15) K, and refractive index (293.15-323.15) K were measured. Thermal properties namely, glass transition temperature, molar heat capacity, and thermal decomposition temperatures were also determined. The thermal expansivity was calculated using the experimental density data. The effect of increasing the alkyl chain length on the thermophysical properties of the pyridinium carboxylate PILs has been evaluated. As expected the physical properties i.e. density, viscosity, surface tension and refractive index of the investigated pyridinium carboxylates decreased with increasing temperature. In general pyridinium carboxylate PILs possessed low viscosity, high thermal stability and excellent hydrogen bonding capability, and these properties lead them to outperform conventional solvents employed for lignin dissolution.

Key words: Protic ionic liquids, Pyridine, Carboxylic acids, Anion, Physicochemical properties

Tazien Rashid, Chong Fai Kait, Thanabalan Murugesan. Effect of alkyl chain length on the thermophysical properties of pyridinium carboxylates[J]. Chinese Journal of Chemical Engineering, 2017, 25(9): 1266-1272.

Tazien Rashid, Chong Fai Kait, Thanabalan Murugesan. Effect of alkyl chain length on the thermophysical properties of pyridinium carboxylates[J]. Chin.J.Chem.Eng., 2017, 25(9): 1266-1272.

参考文献

[1] Y. Zhang, H. Percival, Reviving the carbohydrate economy via multi-product lignocellulose biorefineries, J. Ind. Microbiol. Biotechnol. 35(5) (2008) 367-375.

[2] M.E. Zakrzewska, E. Bogel-?ukasik, Solubility of carbohydrates in ionic liquids, Energy Fuel 24(2) (2010) 737-745.

[3] T. Rashid, C.F. Kait, I. Regupathi, T. Murugesan, Dissolution of kraft lignin using Protic Ionic Liquids and characterization, Ind. Crop. Prod. 84(2016) 284-293.

[4] Freire, M.G. Carvalho, P.J. Fernandes, A.M. Marrucho, M. Isabel, Surface tensions of imidazolium based ionic liquids:Anion,cation, temperature andwater effect, J. Colloid Interface Sci. 314(2) (2007) 621-630.

[5] N.L. Mai, S.H. Ha, Y.M. Koo, Efficient pretreatment of lignocellulose in ionic liquids/co-solvent for enzymatic hydrolysis enhancement into fermentable sugars, Process Biochem. 49(7) (2014) 1144-1151.

[6] R. Rinaldi, Instantaneous dissolution of cellulose in organic electrolyte solutions, Chem. Commun. 47(1) (2011) 511-513.

[7] E.C. Achinivu, R.M. Howard, G. Li, H. Gracz, W.A. Henderson, Lignin extraction from biomass with protic ionic liquids, Green Chem. 16(3) (2014) 1114-1119.

[8] A. George, A. Brandt, K. Tran, S.M. Zahari, K. Marcuschamer, D.S. Ning, Design of low-cost ionic liquids for lignocellulosic biomass pretreatment, Green Chem. 17(3) (2015) 1728-1734.

[9] L. Mu, Y. Shi, L. Chen, T. Ji, R. Yuan,[N-Methyl-2-pyrrolidone] [C1-C₄ carboxylic acid]:A novel solvent system with exceptional lignin solubility, Chem. Commun. 51(70) (2015) 13554-13557.

[10] T.L. Greaves, A. Weerawardena, C. Fong, I. Krodkiewska, Protic ionic liquids:Solvents with tunable phase behavior and physicochemical properties, J. Phys. Chem. B 110(45) (2006) 22479-22487.

[11] Z. Li, J. Xu, D. Li, Extraction process of sulfur compounds from fuels with protic ionic liquids, RSC Adv. 5(21) (2015) 15892-15897.

[12] J. Reid, N. Sullivan, L. Swift, G. Hembury, Assessing the mutagenicity of protic ionic liquids using the mini Ames test, Sustain. Chem. Process. 3(1) (2015) 1-5.

[13] H. Nakamoto, M. Watanabe, Brønsted acid-base ionic liquids for fuel cell electrolytes, Chem. Commun. 2(24) (2007) 2539-2541.

[14] A.M. Cases, G. Marigliano, C. Ana, C.M. Bonatti, Density, viscosity, and refractive index of formamide, three carboxylic acids, and formamide + carboxylic acid binary mixtures, J. Chem. Eng. Data 46(3) (2001) 712-715.

[15] K.M.S.Z. Sundaram, A physicochemical study of pyridine-formic acid system, Phys. Chem. Leipzig 21(1965) 85-90.

[16] M.S. Bakshi, G.B. Kaur, Thermodynamic behavior of mixtures. 4. Mixtures of methanol with pyridine and N,N-dimethylformamide at 25℃, J. Chem. Eng. Data 42(2) (1997) 298-300.

[17] C. Yang, G. Wei, Y. Li, Densities and viscosities of N,N-dimethylformamide + formic acid, and +acetic acid in the temperature range from (303.15 to 353.15) K, J. Chem. Eng. Data 53(5) (2008) 1211-1215.

[18] J.N. Nayak, M.I. Aralaguppi, U.S. Toti, Density, viscosity, refractive index, and speed of soundin the binary mixtures of tri-n-butylamine + triethylamine, +tetrahydrofuran, +tetradecane, +tetrachloroethylene, +pyridine, or +trichloroethylene at (298.15, 303.15, and 308.15) K, J. Chem. Eng. Data 48(6) (2003) 1483-1488.

[19] J. Timmermans, Physico-chemical Constants of Pure Organic Compounds, Vol. 11, Elsevier Publishing Company, Inc., New York, 1950693-693.

[20] G.S. Gokavi, J.R. Raju, T.M. Aminabhavi, R.H. Balundgi, Viscosities and densities of binary liquid mixtures of dimethyl sulfoxide with chlorobenzene, pyridine, and methyl ethyl ketone at 25, 35, 45 and 55.degree.C, J. Chem. Eng. Data 31(1) (1986) 15-18.

[21] E.D. Dikio, S.M. Nelana, Density, dynamic viscosity and derived properties of binary mixtures of methanol, ethanol, n-propanol, and n-butanol with pyridine at T=(293.15, 303.15, 313.15 and 323.15) K, Int. J. Electrochem. Sci. 7(11) (2012) 11101-11122.

[22] A. Apelblat, E. Manzurola, Excess molar volumes of formic acid + water acetic acid + water and propionic acid + water systems at 288.15, 298.15 and 308.15 K, Fluid Phase Equilib. 32(2) (1987) 163-193.

[23] L. Moravkova, Z. Wagner, J. Linek, Volumetric properties of pyridine, 2-picoline, 3-picoline, and 4-picoline at temperatures from (298.15 to 328.15) K and at pressures up to 40 MPa, J. Chem. Thermodyn. 42(1) (2010) 65-69.

[24] C. Wohlfarth, Chapter 144 Viscosity of Formic Acid in Supplement to IV/18, Vol. 25, Springer, Berlin Heidelberg, 2009299-299.

[25] M.I. Aralaguppi, C.V. Jadar, T.M. Aminabhavi, Density, refractive index, viscosity, and speed of sound in binary mixtures of cyclohexanone with benzene, methylbenzene, 1,4-dimethylbenzene, 1,3,5-trimethylbenzene, and methoxybenzene in the temperature interval (298.15 to 308.15) K, J. Chem. Eng. Data 44(3) (1999) 446-450.

[26] D.R. Lide, H.V. Kehiaian, CRC Handbook of Thermophysical and Thermochemical Data, CRC Press, Boca Raton, FL, 199483-409.

[27] A. Xu, J. Wang, Y. Zhang, Q. Chen, Effect of alkyl chain length in anions on thermodynamic and surface properties of 1-butyl-3-methylimidazolium carboxylate ionic liquids, Ind. Eng. Chem. Res. 51(8) (2012) 3458-3465.

[28] M. Tariq, P.A.S. Forte, M.F.C. Gomes, J.N.C. Lopes, L.P.N. Rebelo, Densities and refractive indices of imidazolium-and phosphonium-based ionic liquids:effect of temperature, alkyl chain length, and anion, J. Chem. Thermodyn. 41(6) (2009) 790-798.

[29] M.G. Montalban, C.L. Bolívar, F.G. Díaz Baños, G.J. Víllora, Effect of temperature, anion, and alkyl chain length on the density and refractive index of 1-alkyl-3-methylimidazolium-based ionic liquids, Chem. Eng. Data 60(7) (2015) 1986-1996.

[30] D.W. Fang, W. Guan, J. Tong, Z.W. Wang, J.Z. Yang, Study on physicochemical properties of ionic liquids based on alanine[C_nmim] [Ala] (n=2,3,4,5,6), J. Phys. Chem. B 112(25) (2008) 7499-7505.

[31] T.J.L. Gannon, W. George, R.C.F. Philip, First observation of molecular composition and orientation at the surface of a room-temperature ionic liquid, Langmuir 15(24) (1999) 8429-8434.

[32] L. Glasser, Lattice and phase transition thermodynamics of ionic liquids, Thermochim. Acta 421(1-2) (2004) 87-93.

[33] D.W. Fang, W. Guan, J. Tong, Z.W. Wang, J.Z. Yang, Study on physicochemical properties ofionicliquidsbasedonalanine[C_nmim] [Ala](n=2,3,4,5,6), J. Phys. Chem. B112(25) (2008) 7499-7503.

[34] G.J. Janz, Chapter 3. Thermodynamic properties of long chain hydrocarbons, Thermodynamic Properties of Organic Compounds 1967, pp. 35-49.

[35] G. Janz, Physical properties and structure of molten salts, J. Chem. Educ. 39(2) (1962) 59-62.

[36] M. Rocha, F. Ribeiro, A.I.M. Ferreira, Thermophysical properties of [CN-1C1im] [PF6] ionic liquids, J. Mol. Liq. 188(2013) 196-202.

[37] M.G. Freire, A.R. Teles, M.A.A. Rocha, Thermophysical characterization of ionic liquids able to dissolve biomass, J. Chem. Eng. Data 56(2) (2011) 4813-4822.

[38] Q. Zhang, S. Liu, Z. Li, J. Li, Z. Chen, Novel cyclic sulfonium-based ionic liquids:synthesis, characterization, and physicochemical properties, Chem. Eur. J. 15(3) (2009) 765-778.

[39] R. Safdar, A.A. Omar, L.B. Ismail, Measurement and correlation of physical properties of aqueous solutions of tetrabutylammonium hydroxide, piperazine and their aqueous blends, Chin. J. Chem. Eng. 23(11) (2015) 1811-1818.

[40] A. Xu, Y. Zhang, Z. Li, J. Wang, Viscosities and conductivities of 1-butyl-3-methylimidazolium carboxylates ionic liquids at different temperatures, J. Chem. Eng. Data 57(11) (2012) 3102-3108.

[41] H. Almeida, H. Passos, Lopes-da-Silva, Thermophysical properties of five acetatebased ionic liquids, J. Chem. Eng. Data 57(11) (2012) 3005-3013.

[42] O.O. Okoturo, T.J. Vander Noot, Temperature dependence of viscosity for room temperature ionic liquids, J. Electroanal. Chem. 568(2004) 167-181.

[43] J. Huddleston, A. Visser, W. Reichert, H. Willauer, Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation, Green Chem. 3(4) (2001) 156-164.

[44] Z.B. Zhou, H. Matsumoto, K. Tatsumi, Structure and properties of new ionic liquids based on alkyl-and alkenyltrifluoroborates, Chem. Phys. Chem. 6(5) (2005) 1324-1332.

[45] S.V. Dzyuba, R.A. Bartsch, Influence of structural variations in 1-alkyl (aralkyl)-3-methylimidazolium hexafluorophosphates and bis (trifluoromethylsulfonyl) imides on physical properties of the ionic liquids, Chem. Phys. Chem. 3(2) (2002) 161-166.

[46] C. Kolbeck, J. Lehmann, K.R.J. Lovelock, T. Cremer, N. Paape, Density and surface tension of ionic liquids, J. Phys. Chem. B 114(51) (2010) 17025-17036.

[47] A. Pinkert, K.N. Marsh, S. Pang, Ionic liquids and their interaction with cellulose, Chem. Rev. 109(12) (2009) 6712-6728.

[48] S. Carda-Broch, A. Berthod, D. Armstrong, Solvent properties of the 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid, Anal. Bioanal. Chem. 375(2) (2003) 191-199.

[49] J.P. Belieres, C.A. Angell, Protic ionic liquids:Preparation, characterization, and proton free energy level representation, J. Phys. Chem. B 111(18) (2007) 4926-4937.

[50] A.S.M.C. Rodrigues, L.M.N.B.F. Santos, Nanostructuration effect on the thermal behavior of ionic liquids, ChemPhysChem 17(2) (2016) 1512-1517.