Volumetric behaviour of binary mixtures of (trichloromethane + amines) at temperatures between T = (288.15 and 303.15) K at p = 0.1 MPa
Introduction
This study is a continuation of our investigation on the volumetric properties of binary mixtures containing chloroalkanes as one of components [1], [2], [3]. We report in this work volumetric properties of {trichloromethane + n-butylamine (n-BA), or +s-butylamine (s-BA), or diethylamine (DEA), or +triethylamine (TEA)}, as a function of composition, at temperatures between T = (288.15 and 303.15) K and p = 0.1 MPa. These results are useful to elucidate possible interactions that occur between the compounds present in solutions.
The most important use of trichloromethane is in the production of monochlorodifluorimethane used as a refrigerant. It is still used as an extractant for pharmaceutical products [4]. Diethylamine is used principally for the production of vulcanization accelerators [5]. Triethylamine is used as an organic acid acceptor in the most diverse syntheses, or as a salt former in precipitation or purification operations. Other important fields of use include polyurethane catalysts, anticorrosion agents, textile, and photographic auxiliaries, and anodic electrocoating [5]. Butylamines are used principally for the synthesis of vulcanization accelerators of the sulfenamide type, as intermediate for the production of plasticizers, agrochemicals, and drugs [5].
Thermodynamics properties of binary liquid mixtures of chloroalkanes with amines have been studied by Oswal et al. [6] (alkylamine + haloalkanes), Resa et al. [7] (diisopropylamine + chloroform), Acevedo et al. [8] (di-n-butylamine + chloroalkanes), Acevedo et al. [9] (n-butyl-1-butanamine + chloroalkanes), Acevedo and Katz [10] (amines + chloroalkanes), Acevedo and Katz [11] (n-butylamine + chloroalkanes), Schutte et al. [12] (chloroform + triethylamine), Hepler et al. [13] (chloroform + triethylamine), Kopečni et al. [14] (tri-n-alkylamine + chloroalkanes), Handa et al. [15] (triethylamine + chlorolakanes), Chand et al. [16] (triethylamine + trichloromethane), and Hepler and Fenby [17] (triethylamine + chloroform).
Section snippets
Experimental
Trichloromethane (Merck, PA, mole fraction purity >0.990). The origins of the amines with their purity are: n-butylamine (Acros, mole fraction purity >0.995), s-butylamine (Aldrich, mole fraction purity >0.990), diethylamine (Fluka, mole fraction purity >0.990) and triethylamine (Acros, mole fraction purity >0.990). The components were purified by using the methods described in the literature [18]. The purity of each substance was evaluated from measurements of density by comparing the
Results
The excess molar volume is defined byin which Vm represents the volume of a mixture containing 1 mol of (trichloromethane + amine), x1 and x2 are the mole fractions of components 1 (trichloromethane) and 2 (amine), respectively, and and are the molar volumes of pure components.
The can be expressed by the following equationin which M1, M2, ρ1 and ρ2 represent the molar masses and densities of the pure components, respectively, and ρ
Discussion
FIGURE 1, FIGURE 2, FIGURE 3, FIGURE 4 show the values of excess molar volumes for the studied systems together with the smoothing curves using equation (3) for several temperatures.
The results presented in table 2 and FIGURE 1, FIGURE 2, FIGURE 3, FIGURE 4 indicate that is negative over the entire composition range for all systems studied and the negative deviations for different amines are: tertiary > secondary > primary. The negative deviations follow the order: TCM + TEA > TCM + DEA > TCM + s-BA > TCM + n
Acknowledgements
The authors wish to express their gratitude to Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP, No. 99/12778-7) for financial support. J.G. Magalhães thanks also to Conselho Nacional de Desenvolvimento Cientı´fico e Tecnológico (CNPq) for the scholarship.
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