Volumetric Study for the Binary Nitromethane with ChloroalkaneMixtures at Temperatures in the Range (298.15 to 318.15) KDaniela Gheorghe, Dana Dragoescu,* and Mariana Teodorescu
“Ilie Murgulescu” Institute of Physical Chemistry, Romanian Academy, Splaiul Independentei 202, 060021 Bucharest, Romania
ABSTRACT: The results of the density measurements for thepair systems containing nitromethane with 1,1,2,2-tetrachloro-ethane, 1,1,1-trichloroethane, chloroform, 1,2-dichloroethane,1,3-dichloropropane, 1,4-dichlorobutane, 1-chlorobutane, and1-chloropentane at T = (298.15, 308.15, and 318.15) K andatmospheric pressure on entire compositional range are reported.The derived excess molar volumes, VE, are positive for thenitromethane + 1,1,1-trichloroethane, + 1,2-dichloroethane, +1,3-dichloropropane, + 1,4-dichlorobutane, + 1-chlorobutane,and + 1-chloropentane binary mixtures, and they are negative forthe other two systems: nitromethane + 1,1,2,2-tetrachloroethane,and + chloroform, on the entire compositional range and at allthree studied temperatures. The excess molar volumes have beencorrelated with the three-parameter Redlich−Kister equation.
■ INTRODUCTION
Nitroalkanes and chloroalkanes define classes of importantindustrially compounds which are used as final products oras intermediates. Nitromethane is principally used as stabilizerfor chlorinated solvents, with high importance in degreasing,dry cleaning, and semiconductor processing.From a variety of possible combinations, a large number of
nitromethane + chloroalkane mixtures must be studied experi-mentally for obtaining the necessary data to the separationprocesses design in chemical plants. Simultaneously, theseexperimental data are very useful to the development of newthermodynamic property predictive methods and for verifyingthe existing theories of liquids.Therefore, the study of excess thermodynamic properties,
such as excess molar volume, is quite important to understandmolecular interactions in mixtures and to develop and testtheories of solutions and mathematical models.1,2
The present work is a part of our systematic study on theexcess thermodynamic properties for nitroalkanes withchloroalkanes mixtures. The paper reports excess molarvolumes data of eight binary liquid mixtures of nitromethanewith: 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, chloro-form, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobu-tane, 1-chlorobutane, and 1-chloropentane, at three temper-atures (298.15, 308.15, and 318.15) K and atmosphericpressure, over the whole range of composition.The measurements were carried out for complementing the
experimental data on vapor−liquid equilibria (VLE) of thefollowing binary mixtures: 1,2-dichloroethane + nitromethane/nitroethane,3 1,3-dichloropropane + nitromethane/nitroethane,4
1,4-dichlorobutane + nitromethane/nitroethane,5 and 1-chlor-obutane, 1-chloropentane + nitromethane/nitroethane.6
■ EXPERIMENTAL SECTIONMaterials. The commercial sources and purity levels of the
compounds used in this work are shown in Table 1. The liquids
were kept in advance on freshly reconditioned 4 Å molecularsieves and therefore dried by water traces. They were usedwithout other purification procedure. The quality of thecompounds was verified by gas chromatography, and it wasbetter than declared. In Table 2 it can be observed that ourexperimental density values for the pure substances are in fairagreement with the values from literature.
Apparatus and Procedure. The binary systems weresynthetically obtained by mixing certain weighted volumes ofpure liquids in airtight glass bottles by means of a electronicbalance GH-252 (A&D Japan) with uncertainty of ± 0.1·10−6 kg.
Received: November 26, 2012Accepted: April 1, 2013Published: April 25, 2013
Table 3. Experimental Densities, ρ, and Excess Molar Volumes, VE, for Binary Mixtures of Nitromethane with Chloroalkanes atTemperatures of (298.15, 308.15, and 318.15) Ka
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Then, for preventing the formation of absorbed gas bubbles inthe densimeter capillary at high temperatures, mixture sampleswere partially degassed for 30 min, by using an ultrasonic heatedbath (VWR TM International, model USC 300TH). Theestimated uncertainty for the experimental mole fractions wasbetter than ± 0.0002.The density measurements at the three temperatures (298.15,
308.15, AND 318.15) K for the pure components and for thebinary systems were carried out by using a density and soundvelocity meter Anton Paar DSA-5000 M with precision of± 0.05 kg·m−3. Dried air and distilled−deionized ultra purewater at atmospheric pressure were used as calibration fluids forthe cell. The probes thermostatting was maintained constant at± 0.01 K. The experimental measurement uncertainty fordensity was better than 0.4 kg·m−3.
■ RESULTS AND DISCUSSION
The experimental density values, ρ, for the eight investigatedbinary nitromethane with chloroalkane systems at temperaturesof (298.15, 308.15, and 318.15) K and for the entire composi-tion range are displayed in Table 3.The derived excess molar volumes, VE, were determined
from the equation:
ρ ρ ρ ρ= − + − −
⎛⎝⎜⎜
⎞⎠⎟⎟
⎛⎝⎜⎜
⎞⎠⎟⎟V xM x M
1 1(1 )
1 1E1
12
2 (1)
where x is the liquid mole fraction of chloroalkane, M1 and M2are molar masses of chloroalkane and nitromethane, and ρ1and ρ2 are the densities of the pure liquid compounds 1 and 2.The experimental VE values are shown also in Table 3.The obtained VE values were correlated with the three-
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The eq 2 parameters, Ak, were evaluated by using the maximumlikelihood optimization method.29
These parameters are given in Table 4, together with theobtained standard deviation, σY, expressed as follows:
∑σ = − −=
Y Y n m[ ( ) /( )]Yi
n
i i1
exp , calc,2 0.5
(3)
where Y = value of the property (the mole fraction ofchloroalkane, x, and the excess molar volumes, VE), n is thenumber of the experimental data points, and m = 3 is thenumber of the Redlich−Kister equation parameters.From the measurement results shown in Table 3 and
Figures 1 and 2 it can be seen that the VE values are negative forthe systems: nitromethane + 1,1,2,2-tetrachloroethane, +chloroform and positive for the systems: nitromethane + 1,2-dichloroethane, + 1,3-dichloropropane, + 1,4-dichlorobutane,+ 1,1,1-trichloroethane, + 1-chlorobutane, and + 1-chloropen-tane, on the entire composition domain and at all investigatedtemperatures. It is clear that the interaction factor is dominantfor the mixtures with negative VE values while the steric factorprevails for mixtures with positive VE values.
The negative values of excess volumes for nitromethane +1,1,2,2-tetrachloroethane or + chloroform mixtures decreasewith the increasing temperature. These negative values of VE
indicate that, between unlike molecules, strong intermolecularforces (probably of the H-bonded type) appear at mixing. Suchbehavior could be explained also by the packing effect whichbecame more dominant and increases with temperature, as itwas observed for other systems in literature.13,30
Generally, it seems that the strength of these intermolecularforces is higher for the systems with more chlorine atomsconnected to carbon−hydrogen pair atoms in tetra- ortrichloroalkanes (excepting 1,1,1-trichloroethane) and lesserfor systems with α,ω-dichloroalkanes where it decreases withthe increasing length of the n-alkyl chain.For the binary nitromethane + 1,2-dichloroethane, + 1,3-
dichloropropane, and + 1,4-dichlorobutane mixtures, the VE
values are positive, but small. These values of VE increase with
Figure 1. Excess molar volume, VE, for x chloroalkane + (1 − x)nitromethane binary mixtures at: ◇, 298.15 K; ▲, 308.15 K; ○,318.15 K; (a) 1,1,2,2-tetrachloroethane; (b) chloroform; solid line ,Redlich−Kister correlation.
Figure 2. Excess molar volume, VE, for x chloroalkane + (1 − x)nitromethane binary mixtures at: ◇, 298.15 K; ▲, 308.15 K; ○,318.15 K; (a) 1,1,1-trichloroethane; (b) 1,2-dichloroethane; (c) 1,3-dichloropropane; (d) 1,4-dichlorobutane; (e) 1-chlorobutane; (f)1-chloropentane; solid line , Redlich−Kister correlation.
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the increasing temperature. It appears that the positive valuesfor nitromethane + α,ω-dichloroalkanes are given by thedecreased strength of component molecules interactions andincreased unpacking of unlike molecules at mixing. Theinteractional factor of VE for this class of chloroalkanes variesin the order: 1,2-dichloroethane > 1,3-dichloropropane > 1,4-dichlorobutane. The same variation was observed in terms ofexcess Gibbs energy, GE, in our previous publications.3−5 Someother probable interpretation of the positive VE values could be“the breaking of dipole−dipole interactions between the α,ω-dichloroalkanes molecules from pure state”13 at mixing.For the systems of nitromethane with 1-chloroalkanes, the
free volume, due to the size of the chloroalkane molecules, ishigher for 1-chloropentane than for 1-chlorobutane. It seemsthat this steric effect is giving the size and the sign of the VE
values. The same effect was noticed for the values of GE in themixtures of 1-chlorobutane/1-chloropentane + nitromethane/nitroethane, in our previous paper.6
■ CONCLUSIONNew experimental density values, at T = (298.15, 308.15, and318.15) K and atmospheric pressure, for the binary mixtures ofnitromethane with 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane,chloroform, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlor-obutane, 1-chlorobutane, and 1-chloropentane were measured.They are dependent on composition, temperature, and the natureof chloroalkane.The VE values determined from densities are positive for the
nitromethane + 1,1,1-trichloroethane, + 1,2-dichloroethane, +1,3-dichloropropane, + 1,4-dichlorobutane, + 1-chlorobutane,and + 1-chloropentane binary mixtures and negative for theother two systems: nitromethane + 1,1,2,2-tetrachloroethane, +chloroform, on the entire composition range and at all studiedtemperatures from (298.15 to 318.15) K.It was shown that the interaction factor is dominant for the
mixtures with negative VE values while the steric factor prevailsfor mixtures with positive VE values.
Author ContributionsAll authors contributed equally to this paper.
FundingThe financial support of the Romanian Government and EU(ERDF), through research infrastructure acquisition under POS-CCE O 2.2.1 project INFRANANOCHEM - Nr. 19/01.03.2009,is highly appreciated.
NotesThe authors declare no competing financial interest.
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