Article pubs.acs.org/jced
Solubility, Thermodynamic Properties, and Derived Excess Properties of Benzoic Acid in (Acetic Acid + Water) and (Acetic Acid + Toluene) Binary Mixtures Alka Kumari,†,‡ Kadakanchi Sandeepa,† Thella Prathap Kumar,† and Bankupalli Satyavathi*,† †
Chemical Engineering Division, Indian Institute of Chemical Technology, Hyderabad 500007, India Academy of Scientific and Innovative Research (AcSIR), New Delhi 110001, India
‡
S Supporting Information *
ABSTRACT: The solubility of benzoic acid in (acetic acid + water) and (acetic acid + toluene) binary mixtures has been investigated by the gravimetric method. The study was carried out at different mass fractions of acetic acid ranging from 0.1 to 0.8 at 299.15 K. The results indicated that the solubility of benzoic acid in both binary mixtures exhibited an increasing trend with an increase in the mass fraction of acetic acid. The solubility of benzoic acid with respect to acetic acid in the (acetic acid + water) mixture was less than that in the (acetic acid + toluene) mixture. Furthermore, the refractive indices, nD, and densities, ρ, have been measured for (acetic acid + water) and (acetic acid + toluene) binary mixtures as well as mixtures saturated with benzoic acid salt at different temperatures over the entire composition range, and the same have been reported. The molar refractivity, Rm, was estimated using refractive index, nD, and molar volume, Vm, employing the Lorentz−Lorenz equation. The excess properties, namely deviations in molar refractivity, ΔR, and excess molar volumes, VEm, were calculated for both binary mixtures. The deviations in molar refractivity resulted in negative values for both binary mixtures, whereas the excess molar volumes VEm gave negative values for the (acetic acid + water) mixture and positive values for the (acetic acid + toluene) mixtures. The results obtained in the present study are discussed in terms of structural packing and interactions present among the mixing components and are fitted to the Redlich−Kister third order polynomial equation. Different mixing rules were also employed to predict the refractive index and compared with experimental values.
1. INTRODUCTION The solubility data of solids in pure solvents as well as in mixtures is an essential process parameter for industrial applications. For many separation and purification processes, such as recycling of catalysts and unreacted reactants, isolation of products, and separation of byproducts, the property that is of utmost importance is the crystallization of solutes from a mixture of solvents. The solubility of the substance will dictate the product purity, yield, and crystal size distribution; therefore, knowledge of this data is extremely useful in the design of separation processes and for the development of thermodynamic models.1−5 Benzoic acid is used as an intermediate in the biosynthesis of various secondary metabolites as well in the preparation of cosmetics, resins, dyes, and pharmaceutical industries. Its salts are mainly used as food preservatives, fats, and fruit juices.6 Industrially, it is obtained as a byproduct during the liquid phase oxidation of toluene with air as an oxidant and acetic acid as solvent. Therefore, knowledge of the solubility of benzoic acid in solvents as well as in reactants is important for making the reaction mixture homogeneous and also for separations. The generated data will help in understanding solute−solvent interactions and in process optimization.2 © XXXX American Chemical Society
Accurate measurements of excess thermodynamic properties, such as deviations in molar refractivity and excess molar volumes of liquid mixtures, are necessary for the design of chemical process equipment, such as distillation, extraction, or absorption towers. Furthermore, for the structural properties of liquid mixtures and characterization of thermodynamic properties, awareness of refractive index properties at different temperatures is noteworthy.7,8 Generally, the refractive index is measured for sodium light (586.9 nm), which is the most significant. Nevertheless, the refractive index at other wavelengths is handy in the field of optics and for processes that are phase matched.9 Understanding of the volumetric and transport properties of a binary system gives insight into the nature of the interactions between mixing components. These properties are complex because they depend on not only interactions but also structural effects arising from interstitial accommodations due to the difference in volume and free volume between mixing ponents.9,10 Received: March 3, 2015 Accepted: November 4, 2015
A
DOI: 10.1021/acs.jced.5b00197 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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GC-2010) using FID fitted with a ZB-5 column having 30 m length and 0.53 mm ID. The purity of acetic acid is confirmed by acid−base titration. Benzoic acid is dried in an oven for several hours until a constant weight is recorded for the removal of moisture content. Double distilled water used in the experiments was prepared in the laboratory and checked for any impurities by a Shimadzu GC using a TCD detector. The specific conductance of the double distilled water is 1.3 μS/cm at 25 °C. The densities and refractive indices of the pure components were measured and are compared with literature values1,12,26−29 in Table 2.
In the present study, thermodynamic properties of solvents used to solubilize benzoic acid, namely, the (acetic acid + water) and (acetic acid + toluene) systems, are considered due to extremely complex interactions of acetic acid with water and untypical mixing behavior of acetic acid with tolune.11,12 The study of excess properties is performed to understand the physical and chemical changes in the process. The main objective of the present work is to study the solubility of benzoic acid in (acetic acid + water) and (acetic acid + toluene) mixtures for various mass fractions of acetic acid at a temperature of 299.15 K by the gravimetric method. The present study is restricted to a lower mass fraction of acetic acid as the literature is scarce for these compositions. A few researchers have reported solubility data of benzoic acid in pure solvents and binary mixtures.1,5,6,13−17 Others have investigated the solubility of benzoic acid in pure acetic acid and water.1,13,18−20 Xi et al.21 have studied the solubility of benzoic acid in an (acetic acid + water) binary mixture for the higher mass fraction of acetic acid. The authors have not come across any literature on the solubility of benzoic acid in (acetic acid + toluene) mixtures or at the lower mass fraction of acetic acid in (acetic acid + water) mixtures. The present study is directly applicable in the industrial production of benzaldehyde and benzoic acid by air oxidation of toluene in the presence of acetic acid. Additionally, densities, ρ, refractive indices, nD, and derived excess properties, such as deviations in molar refractivity, ΔR, and excess molar volumes, VEm, for the binary mixtures of (acetic acid + water) and (acetic + toluene), have been reported at different temperatures from (293.15 to 303.15) K. Furthermore, ρ and nD data for the saturated ternary mixtures of benzoic acid in (acetic acid + water) and (acetic acid + toluene) at different temperatures from 299.15 to 303.15 K and local atmospheric pressure of 94.86 kPa are measured. Although researchers have reported the ρ, nD, viscosity, and measured V mE data of an (acetic acid + water)12,22−24 binary mixture; no reported data is available on the Rm and ΔR values for the considered system. Rattan et al.11 reported only the density and viscosity data for (acetic acid + toluene). Therefore, in the present study, the excess properties, excess molar volumes, VEm, and deviations in molar refractivity are derived, which will draw an accurate picture of molecular interactions among the mixing components. The refractive indices of binary mixtures were correlated by various mixing equations, including Lorentz−Lorenz, Gladstone−Dale, Eyring−John, Arago−Biot, Weiner, Heller, and Newton. Deviations between experimental and predicted values have been reported in terms of average percentage deviation (APD).25
Table 2. Comparison of Measured Density, ρ, and Refractive Index, nD, of Pure Toluene and Acetic Acid with Literature Dataa ρ/g cm−3 substance toluene
acetic acid
water
toluene acetic acid benzoic acid, extra pure
SD Fine-Chem Limited, Mumbai, India Molychem, Mumbai, India Molychem, Mumbai, India
exp.
lit.
exp.
lit.
0.86675 0.86174 0.85681 1.04963
1.49687 1.49406 1.49124 1.37224
1.49701b 1.49413c 1.49390d 1.37260e
298.15
1.04357
0.86687b 0.86219c 0.86234d 1.04900e 1.04930i 1.04395f
1.37012
1.36969f 1.36980g 1.37046h
303.15
1.03764
293.15 298.15 303.15
0.99816 0.99661 0.99487
1.04392g 1.04322h 1.04365i 1.04400j 1.04392j 1.03830j 1.03800i 0.99800k 0.99708l
1.36809 1.33308 1.33256 1.33199
1.37046j 1.36980j 1.36858j
1.33250l
Standard uncertainties, u. are u(T) = ± 0.01 K, u(ρ) = ± 5·10−5 g cm−3, u(nD) = ± 1·10−4. bFrom ref 26. cFrom ref 27. dFrom ref 28. e From ref 1. fFrom ref 12. gFrom ref 29. hFrom ref 30. iFrom ref 22. j From ref 31. kFrom ref 32. lFrom ref 33.
2.2. Apparatus and Procedure. Solubility Measurement. The solubility of benzoic acid in (acetic acid + water) and (acetic acid + toluene) mixtures was measured at a temperature of 299.15 K using the gravimetric method.29 Experiments were carried out in a shaking incubator (Model No. LSI-4018R) provided by Daihan Labtech India Pvt. Ltd. capable of maintaining the temperature within ± 0.1 K. An excess amount of benzoic acid was added to 100 g of binary mixture with varying mass fractions of acetic acid in water or toluene in Teflon-coated glass-stoppered flasks. The solutions in the flasks were continuously stirred for 9 h at constant temperature and atmospheric pressure. The temperature of the samples was confirmed using a glass thermometer with ± 0.05 K accuracy. Undissolved benzoic acid was then allowed to settle for 24 h, maintaining the same conditions of the samples. A glass syringe, maintained at elevated temperature and then solution fitted with a micron filter at the tip, was used to take out the clear layer of the solution into a previously weighed measuring vial (m0), closed tightly, and weighed (m1) to verify the mass of the sample (m1 − m0). The vial was then uncorked and placed in an oven at ∼383 K for complete evaporation of solvent for 6 h. After complete evaporation of the solvent, the vial was weighed again (m2) to record the mass of the residual solid (m2 − m0).
Table 1. List of Chemicals Used source
T/K 293.15 298.15 303.15 293.15
a
2. EXPERIMENTAL SECTION 2.1. Materials. For preparation of binary mixtures, chemicals used in the experiments are described in Table 1.
chemical name
nD
mass fraction purity ≥ 0.990 ≥ 0.995 ≥ 0.995
Toluene and acetic acid are stored in desiccators to prevent absorption of moisture and evaporation losses. The purity of toluene is verified by gas chromatography (Model Shimadzu B
DOI: 10.1021/acs.jced.5b00197 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Figure 1. Solubility of benzoic acid (in terms of mole fraction) in the binary systems of (a) (acetic acid + water) and (b) (acetic acid + toluene) as a function of acetic acid mole fraction (x1) in mixtures on a solute-free basis at a constant temperature of 299.15 K; (−) lines are calculated using eq 2.
measurement of the refractive index. The properties of solutions saturated with salts were measured at temperatures of 299.15 and 303.15 K. The measured properties of the systems were used for the estimation of excess properties, such as deviations in molar refractivity and excess molar volumes. The uncertainty in the measurement of the mole fraction was determined to be ± 0.0002. The average uncertainty in the estimation of excess molar volumes, VEm, and deviations in molar refractivity, ΔR, for acetic acid + water is ± 0.0516 and ± 0.0097 cm3 mol−1 and for acetic acid + toluene is 0.0573 and 0.0132 cm3 mol−1, respectively.
The solubility of benzoic acid in the sample solution (in mole fraction) is then calculated according to eq 1.34,35 x=
(m2 − m0)/M1 (m2 − m0)/M1 + (m1 − m2)w/M 2 + (m1 − m2)(1 − w)/M3
(1)
where x is the mole fraction solubility of benzoic acid in the solvents, M1, M2, and M3 are the molar masses of the benzoic acid, acetic acid, and water/toluene, which are 122.1, 60.05, and 18.05/92.14, respectively, and w is the mass fraction of acetic acid in the solvents. Samples were taken at different dissolution times to ensure the saturation point. It was found that 7 h was sufficient to attain the solid−liquid equilibrium in both binary mixtures. For each composition, the measurement was repeated three times and the average value was reported. The uncertainty in the solubility measurement in the two binary systems of repeated observations was within ± 2 % accuracy. Refractive Index and Density Measurement. Unsaturated mixtures of the samples were prepared gravimetrically by weighing the required amount of the pure liquids and stirring them well before charging. For recording the weight of the samples, a high precision Citizon balance, capable of recording weights to an accuracy of ± 0.0001 g was used. The samples were prepared just before the property measurements and stored in glass bottles with airtight Teflon-coated lids. The density and refractive index of mixed solvents with and without saturated salts were measured using a Rudolph Research Analytical automatic densitometer (Model DDM 2911, Hackettstown, USA) and Schmidt + Haensch refractometer (Model DSR λ, WaldstraBe, Berlin), respectively. The accuracy of these instruments has been determined to be 0.00005 g cm−3 and 0.0001, respectively. For a typical measurement of density, the sample is drawn by a syringe and loaded into the instrument through an inlet nozzle connected to the U-tube. The outlet nozzle is attached to a drain line for the collection of measured sample and waste solvents used during drying and cleaning. The density measurements are recorded at the required temperatures. For the measurement of refractive index, the sample well is rinsed a few times with the sample to be loaded. The sample is then loaded, and the nD values are measured at different wavelengths and specified temperatures. The instrument displays nD of the sample at seven wavelengths consecutively based on the dispersion of light. A sample size of 0.3 mL is sufficient for the
3. RESULTS AND DISCUSSION The mole fraction of soluble benzoic acid in each binary mixture is plotted as ln x versus acetic acid mole fraction x1 on a solute-free basis. A second order polynomial equation was fitted for the mixed solvents to check the variation in solvent composition with solubility at a constant temperature. The equation is expressed as6 ln x = ax12 + bx1 + c
(2)
where x is the solubility of benzoic acid (mole fraction), and x1 is the mole fraction of acetic acid in water or toluene on a solutefree basis. a, b, and c are the correlation parameters at constant temperature and were calculated using the nonlinear regression least-squares method. The regressed parameters were used to predict the solubility of benzoic acid in both the binary systems, and this along with the experimental values is illustrated graphically in Figure 1a and b. The relative deviations of the measured solubility compared to the predicted values using eq 2 are presented in Table 3 along with the experimental data at 299.15K. As is evident from the table, the solubility of benzoic acid in (acetic acid + water) and (acetic acid + toluene) increases with an increase in the mass fraction of acetic acid from 0.1 to 0.8. The solubilities of benzoic acid in pure water and toluene are 0.00035 and 0.078, respectively, as reported in the literature.6,36 A significant increase in the solubility is observed with an increase in the mass fraction of acetic acid. This is attributed to the association of a hydrogen bond between acid−acid and acid− water molecules. The mixed solvents exhibit greater influence on the dissolution of benzoic acid than pure solvents. It is also observed that the benzoic acid solubility in (acetic acid + toluene) mixtures is more than in (acetic acid + water) mixtures for the same mass fraction of acetic acid in both mixtures and results in an increase in solubility as the mass fraction of acetic acid increases. Wang et al.21 have reported the solubility of C
DOI: 10.1021/acs.jced.5b00197 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 3. Solubility of Benzoic Acid, x, in (Acetic Acid + Water) and (Acetic Acid + Toluene) Mixtures at a Temperature of 299.15 Ka (acetic acid + water)
(acetic acid + toluene)
w(x1)b
xexp
xcal
RDc
xexp
xcal
RDb
10 (0.0322) 20 (0.0697) 30 (0.1140) 40 (0.1670) 50 (0.2310) 60 (0.3100) 70 (0.4120) 80 (0.5450)
0.0004 (0.0001) 0.0006 (0.0001) 0.0017 (0.0011) 0.0044 (0.0002) 0.0153 (0.0003) 0.0224 (0.0012) 0.0420 (0.0001) 0.0743 (0.0005)
0.0004 0.0006 0.0015 0.0032 0.0142 0.0235 0.0420 0.0702
0.0000 0.0000 0.0941 0.2852 0.0708 −0.0494 0.0000 0.0543
0.1397 (0.0002) 0.1676 (0.0001) 0.1919 (0.0012) 0.2156 (0.0001) 0.2218 (0.0011) 0.2381 (0.0005) 0.2427 (0.0002) 0.2561 (0.0003)
0.1597 0.1683 0.1894 0.1939 0.2134 0.2391 0.2674 0.2494
−0.1434 −0.0043 0.0649 0.1004 0.0380 −0.0044 −0.1021 0.0262
a
Standard uncertainty in T is u(T) = 0.05 K; relative standard uncertainty of the solubility measurement is ur(x) = 2%. The numbers are average values of three samples; parentheses contain the reported standard deviations. bMass percent (mole fraction) of acetic acid in water or toluene on a solute-free basis; xexp and xcal represent the experimental and calculated (by eq 2) values. cRelative deviation (RD) = (xexp − xcal)/xexp.
benzoic acid in (acetic acid + water) for the higher mass fraction of acetic acid ranges from 0.8 to 1.0. The present data is in good agreement with reported literature with a relative deviation of less than 0.03 (RD = (xexp − xlit)/xexp) at 299.15 K for the acetic acid mass fraction of 0.8. In the (acetic acid + toluene) system, the solubility of benzoic acid increases nonlinearly with a decreasing mass fraction of the nonpolar solvent toluene, and the same trend has been reported by Thati et al.6 The authors have not come across any reports on the solubility of benzoic acid in (acetic acid + toluene) mixtures to compare with the present data. The root-mean-square deviations, δ, calculated using eq 3 are reported in Table 4.
Table 4. Regressed Coefficients of eq 2 of Benzoic Acid in (Acetic Acid + Water) and (Acetic Acid + Toluene) Binary Mixtures at a Temperature of 299.15 K
∑i (xexp − xcal)2 N−1
a
b
c
δ
−6.6988 −0.0299
12.3785 0.2633
−7.9641 −1.8783
0.0017 0.0158
(acetic acid + water) mixtures was observed, and assemblage of water ultimately prevailed in the mixtures at x1 ≤ 0.18.37 As the mole fraction of acetic acid increases, the hydrogen bonds of acid−acid and acid−water gradually increase, and the chain structure of acetic acid molecules forms at x1 ≥ 0.6, which consequently decreases the thermodynamic properties (density and refractive index) at both the dilute regions, i.e., water-rich and acetic acid-rich regions. The ionic dipole bond (the bond between CH3COO− and H2O) are stronger between 0.4 ≤ x1 ≤ 0.6 than a hydrogen bond,23 resulting in more contraction of volume in this range, which eventually increases the density. The tabulated data also reveals that the density decreases with increasing temperature, which is manifested by the increase in the translational energy of the molecules, leading to a decrease in intermolecular interactions of the molecules.38 The refractive index of a substance is interrelated to its density and generally decreases with decreasing density (or increasing temperature); therefore, the nD of the binary mixtures studied decreased with increasing temperature and decreased with increasing wavelength. In Table 7, the Abbe number has also been reported along with the data. The Abbe number, V, is a measure of the material’s dispersion in relation to the refractive index with high values of V indicating low dispersion. It is defined as n −1 V= D nF − nC (4)
N
δ=
solvent system acetic acid + water acetic acid + toluene
(3)
where xexp and xcal are the experimental and calculated solubilities of benzoic acid in the binary solvents, and N is the number of experimental data points. The reported values in the table show that the solubility data at a constant temperature is well represented by eq 2 with R2 > 0.992 for the (acetic acid + water) system, and the rmsd values for the binary mixtures of (acetic acid + water) and (acetic acid + toluene) are 0.0017 and 0.0158, respectively, which is much lower. The densities, refractive indices, deviations in molar refractivity, and excess molar volumes of the two binary systems (acetic acid + water) and (acetic acid + toluene) at different temperatures from (293.15 to 303.15) K and local atmospheric pressure of 94.64 kPa are reported in Tables 5 and 6, respectively, and the ρ and nD data at different wavelengths for the saturated benzoic acid solutions at temperatures of 299.15 and 303.15 K are listed in Table 7. Refractive indices of both mixtures with and without salt were also reported at 404.7, 435.8, 486.1, 546.1, 589.3, 632.8, 644, and 706.5 nm frequencies. It is observed from Table 5 that the density of (acetic acid + water) increases from x1 = 0 to 0.5450 and then decreases from 0.6290 to 1 at all temperatures. Furthermore, the refractive index increases from x1 = 0 to 0.6290 and then decreases from 0.7290 to 1. A similar trend has been noticed by multiple researchers.12,22,23 The reason for this is attributed to the increase in hydrogen bonds of acetic acid−water and water−water in (acetic acid + water) mixtures with decreasing mole fraction of acetic acid, x1, due to breakage of the chain structure of acetic acid. For the lower mass fraction of acetic acid, x1 ≤ 0.4, association of hydrogen bonds among water molecules in
where nD, nF, and nC are the refractive indices of the material at wavelengths of 589.3, 486.1, and 656.3 nm, respectively. The usage of the Abbe number has declined over the years because of high resolution and accuracy of the instruments that resolve RI differences up to 0.00001. The Abbe numbers are also reported in Tables S1 and Table 7. The deviation in molar refractivity, ΔR, was calculated from the measured refractive indices, densities, and molar refractivity data using the correlations ΔR (cm 3 mol−1) = R m −
∑ ϕiR i i
D
(5)
DOI: 10.1021/acs.jced.5b00197 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 5. Refractive Index, nD, Molar Refractivity, Rm, Density, ρ, and Derived Excess Properties, such as Deviations in Molar Refractivity, ΔR, and Excess Molar Volumes, VEm, of the Binary System (Acetic Acid + Water) at Temperatures from (293.15 to 303.15) K, Wavelength of 589.3 nm, and P = 94.64 kPaa (acetic acid + water) ϕ1c
nD
0.0000 0.0322 0.0697 0.1140 0.1670 0.2310 0.3100 0.4120 0.5450 0.6290 0.7290 0.8500 1.0000
0.0000 0.0954 0.1920 0.2898 0.3886 0.4878 0.5876 0.6896 0.7916 0.8432 0.8951 0.9473 1.0000
1.33308 1.34079 1.34792 1.35489 1.36090 1.36583 1.37062 1.37406 1.37703 1.37724 1.37721 1.37559 1.37224
0.0000 0.0322 0.0697 0.1140 0.1670 0.2310 0.3100 0.4120 0.5450 0.6290 0.7290 0.8500 1.0000
0.0000 0.0958 0.1926 0.2906 0.3896 0.4889 0.5886 0.6905 0.7923 0.8437 0.8955 0.9475 1.0000
1.33257 1.34007 1.34695 1.35372 1.35957 1.36436 1.36900 1.37233 1.37519 1.37545 1.37530 1.37359 1.37012
0.0000 0.0322 0.0697 0.1140 0.1670 0.2310 0.3100 0.4120 0.5450 0.6290 0.7290 0.8500 1.0000
0.0000 0.0961 0.1932 0.2914 0.3906 0.4899 0.5895 0.6914 0.7929 0.8442 0.8958 0.9477 1.0000
1.33198 1.33927 1.34593 1.35250 1.35822 1.36288 1.36736 1.37058 1.37331 1.37349 1.37335 1.37160 1.36809
x1
b
d
Rm /cm3 mol−1 e
ρf/g cm−3
VEmg/cm3 mol−1
ΔRh/cm3 mol−1
0.99816 1.01310 1.02911 1.04003 1.04979 1.05769 1.06429 1.06857 1.06893 1.06742 1.06282 1.05962 1.04963
0.0000 −0.1911 −0.4253 −0.5834 −0.7406 −0.8816 −1.0179 −1.1169 −1.1065 −1.0341 −0.9011 −0.6155 0.0000
0.0000 −0.5847 −1.1422 −1.6294 −2.0517 −2.3798 −2.5682 −2.2787 −2.2664 −1.8161 −1.4994 −0.8931 0.0000
0.99661 1.01007 1.02431 1.03643 1.04544 1.05312 1.05945 1.06331 1.06347 1.06115 1.05808 1.05373 1.04357
0.0000 −0.1716 −0.3792 −0.5700 −0.7203 −0.8662 −1.0070 −1.1067 −1.1038 −1.0074 −0.8598 −0.6185 0.0000
0.0000 −0.5852 −1.1411 −1.6382 −2.0605 −2.3900 −2.5790 −2.5812 −2.2735 −1.8161 −1.5018 −0.8942 0.0000
0.99487 1.00737 1.02116 1.03293 1.03959 1.04856 1.05448 1.05816 1.05801 1.05717 1.05326 1.04795 1.03764
0.0000 −0.1614 −0.3685 −0.5609 −0.6668 −0.8520 −0.9926 −1.0990 −1.0988 −1.0683 −0.8976 −0.6215 0.0000
0.0000 −0.5876 −1.1474 −1.6478 −2.0413 −2.4004 −2.5893 −2.5913 −2.2818 −1.8178 −1.5052 −0.8971 0.0000
293.15 K 3.7122 4.0148 4.3548 4.7770 5.2740 5.8683 6.6071 7.8454 8.8059 9.7358 10.5351 11.6269 13.0103 298.15 K 3.7128 4.0191 4.3642 4.7794 5.2784 5.8725 6.6113 7.5578 8.8125 9.7486 10.5445 11.6363 13.0192 303.15 K 3.7133 4.0213 4.3661 4.7807 5.3107 5.8766 6.6161 7.5626 8.8184 9.7604 10.5536 11.6448 13.0293
Standard average uncertainties, u, are u(x) = ± 0.0002, u(T) = ± 0.01 K, u(ρ) = ± 5·10−5 g cm−3, and u(nD) = ± 1·10−4. bMole fraction of acetic acid. cVolume fraction of acetic acid. dRefractive index of pure components and binary mixtures. eMolar refraction of pure components and binary mixtures. fDensity of pure components and binary mixtures. gExcess molar volumes. hDeviations in molar refractivity. a
The Lorentz−Lorenz equation18 was used to determine Rm values for the binary mixture as shown in eq 6. ⎛ n2 − R m = ⎜ D2 ⎝ nD +
1⎞ ⎟Vm 2⎠
ϕi =
(8)
Excess molar volumes, VEm, were calculated using eq 9 as (6)
VmE (cm 3 mol−1) =
where Vm = (∑ixiMi/ρm)
⎛ n 2 − 1 ⎞⎛ M ⎞ D, i ⎟⎟⎜⎜ i ⎟⎟ R i = ⎜⎜ 2 + n 2 ⎝ D, i ⎠⎝ ρi ⎠
xiVi ∑k xkVk
⎛x M x1M1 + x 2M 2 xM ⎞ − ⎜⎜ 1 1 + 2 2 ⎟⎟ ρm ρ2 ⎠ ⎝ ρ1 (9)
where ϕi and xi are the volume and mole fraction of pure component i in the mixture, nD and nD,i are the refractive index of
(7) E
DOI: 10.1021/acs.jced.5b00197 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 6. Refractive Index, nD, Molar Refractivity, Rm, Density, ρ, and Derived Excess Properties, Such As Deviations in Molar Refractivity, ΔR, and Excess Molar Volumes, VEm, of Binary System (Acetic Acid + Toluene) at Temperatures from (293.15 to 303.15) K, Wavelength of 589.3 nm, and P = 94.64 kPaa (acetic acid + toluene) ϕ1c
nD
0.0000 0.1460 0.2770 0.3970 0.5060 0.6050 0.6970 0.7820 0.8590 0.8970 0.9320 0.9670 1.0000
0.0000 0.0843 0.1709 0.2616 0.3554 0.4518 0.5532 0.6588 0.7663 0.8242 0.8806 0.9404 1.0000
1.49687 1.48448 1.47082 1.45878 1.44593 1.43372 1.4212 1.40891 1.39681 1.38731 1.38235 1.37721 1.37224
0.0000 0.1460 0.2770 0.3970 0.5060 0.6050 0.6970 0.7820 0.8590 0.8970 0.9320 0.9670 1.0000
0.0000 0.0843 0.1709 0.2616 0.3554 0.4518 0.5532 0.6588 0.7663 0.8242 0.8806 0.9404 1.0000
1.49406 1.48174 1.46810 1.45618 1.44332 1.43116 1.41872 1.40650 1.39453 1.38466 1.38029 1.37520 1.37012
0.0000 0.1460 0.2770 0.3970 0.5060 0.6050 0.6970 0.7820 0.8590 0.8970 0.9320 0.9670 1.0000
0.0000 0.0843 0.1709 0.2616 0.3553 0.4518 0.5532 0.6588 0.7663 0.8241 0.8806 0.9404 1.0000
1.49124 1.47906 1.46535 1.45352 1.44065 1.42842 1.41617 1.40452 1.39228 1.38303 1.37820 1.37315 1.36809
x1
b
d
Rm /cm3 mol−1 e
293.15 K 31.1002 28.4909 26.0169 23.8982 21.9007 20.1275 18.4387 16.9383 15.5409 14.6661 14.1020 13.5461 13.0103 298.15 K 31.1308 28.5250 26.0422 23.9214 21.9221 20.1456 18.4566 16.9529 15.5529 14.6632 14.1170 13.5593 13.0192 303.15 K 31.1580 28.5587 26.0700 23.9463 21.9394 20.1545 18.4704 16.9828 15.5682 14.6942 14.1297 13.5705 13.0293
ρf/g cm−3
VEmg/cm3 mol−1
ΔRh/cm3 mol−1
0.86675 0.87894 0.89411 0.90790 0.92408 0.94043 0.96000 0.97840 1.00020 1.01774 1.02784 1.03811 1.04963
0.0000 0.3630 0.4046 0.6402 0.6751 0.7293 0.5942 0.5525 0.2788 0.10164 0.0726 0.0348 0.0000
0.0000 −1.0852 −1.9910 −2.4694 −2.7711 −2.7989 −2.6547 −2.2449 −1.6973 −1.5252 −1.0680 −0.5429 0.0000
0.86174 0.87365 0.88881 0.90258 0.91849 0.93475 0.95412 0.97248 0.99434 1.01175 1.02182 1.03217 1.04357
0.0000 0.3892 0.4209 0.6511 0.7016 0.7540 0.6233 0.6352 0.4368 0.1595 0.0924 0.0399 0.0000
0.0000 −1.0798 −1.9926 −2.4710 −2.7727 −2.8017 −2.6555 −2.2466 −1.6993 −1.5409 −1.0645 −0.5399 0.0000
0.85681 0.86847 0.88338 0.89710 0.91296 0.92915 0.94831 0.96660 0.98834 1.00581 1.01590 1.02628 1.03764
0.0000 0.4128 0.4608 0.6870 0.7318 0.7810 0.6557 0.6633 0.4618 0.1719 0.1009 0.0334 0.0000
0.0000 −1.0719 −1.9892 −2.4690 −2.7766 −2.8124 −2.6596 −2.2329 −1.6982 −1.5231 −1.0640 −0.5398 0.0000
Standard average uncertainties, u, are u(x) = ± 0.0002, u(T) = ± 0.01 K, u(ρ) = ± 5·10−5 g cm−3, and u(nD) = ± 1·10−4. bMole fraction of acetic acid. cVolume fraction of acetic acid. dRefractive index of pure components and binary mixtures. eMolar refraction of pure components and binary mixtures. fDensity of pure components and binary mixtures. gExcess molar volumes. hDeviations in molar refractivity. a
mixture. The F-test was used to optimize the order of the equation.41 The nonlinear regression least-squares fit method was used to obtain the correlation parameters ai in eq 10. The difference between the observed and calculated values of VEm or ΔR are reported in terms of standard deviation, σ, which is defined as
the mixture and pure component, Vm and Vi are the molar volume of mixture and pure component, ρm and ρi are the density of the mixture and pure component, respectively, and Mi is the molar mass of the component. The excess values at different temperatures are fitted to the Redlich−Kister third order polynomial39,40 and are given by eq 10. p
Y E = x1x 2 ∑ ai(x1 − x 2)i where p = 3 i=0
0.5 E E 2 σ = ⎡⎣∑ (Yexp − Ycal ) /(D − N )⎤⎦
(10)
where YE represents VEm or ΔR, p is the degree of the polynomial, and x1 and x2 are the mole fraction of pure components in the
(11)
where D and N are the number of experimental data points and adjustable parameters, respectively. F
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Table 7. Refractive Indices, nD, Densities, ρ, of Saturated Ternary Mixtures of Benzoic Acid in (Acetic Acid + Water) and (Acetic Acid + Toluene) at Temperatures of 299.15 K and 303.15 K and at Wavelengths from 404.7 to 706.5 nma nD x1b
x2c
ρ/g cm−3
404.7
0.0322 0.0697 0.1140 0.1670 0.2310 0.3100 0.4120 0.5450
0.0004 0.0006 0.0018 0.0045 0.0155 0.0299 0.0439 0.0802
1.00622 1.02800 1.03806 1.05049 1.06026 1.06717 1.06915 1.07515
1.35158 1.35928 1.36803 1.37711 1.38671 1.39518 1.40378 1.40527
0.0322 0.0697 0.1140 0.1670 0.2310 0.3100 0.4120 0.5450
0.0004 0.0006 0.0018 0.0045 0.0155 0.0299 0.0439 0.0802
1.00295 1.02275 1.03399 1.04624 1.05522 1.06186 1.06324 1.06890
1.35071 1.35843 1.36677 1.37738 1.38513 1.39537 1.40527 1.41234
x1b
x2c
ρ/g cm−3
404.7
0.1460 0.2770 0.3970 0.5060 0.6050 0.6970 0.7820 0.8590
0.1624 0.2014 0.2376 0.2748 0.2850 0.3125 0.3208 0.3443
0.92195 0.94590 0.95347 0.98671 0.99853 1.01975 1.02489 1.04546
1.51993 1.51017 1.50032 1.49358 1.48473 1.47081 1.46697 1.45560
0.1460 0.2770 0.3970 0.5060 0.6050 0.6970 0.7820 0.8590
0.1624 0.2014 0.2376 0.2748 0.2850 0.3125 0.3208 0.3443
0.90874 0.93947 0.94742 0.98048 0.99179 1.01436 1.02125 1.03817
1.51740 1.50809 1.49998 1.49109 1.48533 1.46839 1.46454 1.45352
435.8
486.1
546.1
587.6
589.3
Saturated Solution of (Benzoic Acid + Acetic Acid + Water) 299.15 K 1.34889 1.34575 1.34304 1.34157 1.34152 1.35647 1.35325 1.35043 1.34893 1.34887 1.36507 1.36168 1.35878 1.35726 1.35721 1.37392 1.37034 1.36730 1.36570 1.36564 1.38329 1.37944 1.37620 1.37451 1.37444 1.39154 1.38736 1.38386 1.38205 1.38198 1.39987 1.39550 1.39186 1.39000 1.38993 1.40125 1.39675 1.39302 1.39114 1.39033 303.15 K 1.34802 1.34493 1.34220 1.34076 1.34071 1.35561 1.35240 1.34958 1.34810 1.34804 1.36383 1.36045 1.35756 1.35604 1.35598 1.37417 1.37050 1.36743 1.36579 1.36513 1.38172 1.37787 1.37466 1.37295 1.37289 1.39165 1.38745 1.38399 1.38218 1.38212 1.40125 1.39675 1.39302 1.39114 1.39107 1.40807 1.40334 1.39941 1.39743 1.39736 nD 435.8
486.1
546.1
587.6
589.3
Saturated Solution of (Benzoic Acid + Acetic Acid + Toluene) 299.15 K 1.51169 1.50236 1.49490 1.49125 1.49112 1.50225 1.49328 1.48614 1.48261 1.48248 1.49272 1.48415 1.47729 1.47396 1.47384 1.48623 1.47797 1.47132 1.46809 1.46797 1.47776 1.47003 1.46367 1.46054 1.46043 1.46427 1.45698 1.45110 1.44823 1.44813 1.46055 1.45335 1.44759 1.44475 1.44465 1.44959 1.44286 1.43744 1.43479 1.43469 303.15 K 1.50920 1.49990 1.49247 1.48895 1.48872 1.50017 1.49123 1.48407 1.48058 1.48045 1.49233 1.48370 1.47680 1.47346 1.47334 1.48376 1.47555 1.46894 1.46574 1.46563 1.47819 1.47018 1.46377 1.46069 1.46058 1.46188 1.45461 1.44875 1.44590 1.44580 1.45816 1.45097 1.44524 1.44242 1.44232 1.44756 1.44087 1.43550 1.43286 1.43277
632.8
644.0
706.5
Abbe No.
1.34023 1.34754 1.35583 1.36429 1.37294 1.38039 1.38831 1.38943
1.33992 1.34722 1.35549 1.36397 1.37258 1.38000 1.38792 1.38902
1.33337 1.34560 1.35383 1.36239 1.37082 1.37813 1.38600 1.38706
55.40 54.67 54.48 54.53 51.65 49.12 48.71 47.82
1.33943 1.34673 1.35462 1.36428 1.37139 1.38052 1.38943 1.39564
1.33911 1.34640 1.35428 1.36393 1.37103 1.38014 1.38902 1.39522
1.33757 1.34480 1.35263 1.36223 1.36928 1.37830 1.38706 1.39321
55.29 54.67 54.48 52.69 51.67 49.51 47.82 46.32
632.8
644.0
706.5
Abbe No.
1.48807 1.47955 1.47103 1.46524 1.45779 1.44569 1.44224 1.43242
1.48735 1.47886 1.47034 1.46458 1.45714 1.44509 1.44166 1.43187
1.48405 1.47569 1.46727 1.46158 1.45424 1.44236 1.43899 1.42935
31.13 31.86 32.59 33.20 33.90 35.72 36.09 37.53
1.48569 1.47753 1.47050 1.46292 1.45794 1.44337 1.43993 1.43052
1.48497 1.47683 1.46982 1.46226 1.45729 1.44277 1.43935 1.42997
1.48169 1.47365 1.46671 1.45929 1.45438 1.44007 1.43671 1.42747
31.12 31.72 32.40 33.25 33.87 35.72 36.16 37.67
Standard average uncertainties, u, are u(x) = ± 0.0002, u(T) = ± 0.01 K, u(ρ) = ± 5·10−5 g cm−3, and u(nD) = ± 1·10−4. bMole fraction of acetic acid on solute-free basis. cMole fraction of benzoic acid on solute-free basis. a
Experimental ΔR and VEm values were correlated with the Redlich−Kister polynomial equation. The adjustable Redlich− Kister parameters and standard deviations are summarized in Table 8. The deviations in molar refractivity, ΔR, as a function of composition over the entire range for the binary systems of (acetic acid + water) and (acetic acid + toluene) are drawn in Figures 2a and 3a. It can be seen that ΔR exhibits negative values at all temperatures, which represents the dominance of dispersive forces in mixtures rather than pure components.42 It also depicts that there is no effect of temperature on ΔR values. This fact can be attributed to the change in density compensated by the variation in nD with temperature. ΔR has been reported instead of deviation in the refractive index as it illustrates more
information about the mixture phenomenon by taking into consideration the electronic perturbation of the molecular orbital.43 The dependence of VEm at different temperatures for the binary systems of (acetic acid + water) and (acetic acid + toluene) over the entire composition range are plotted in Figures 2b and 3b. Generally, VmE is affected by three factors: (a) physical contribution, which arises due to disruption of liquid order, i.e., weak dipole−dipole interactions resulting in positive VEm (b) chemical contribution, which is attributed to the predominace of interactions between unalike molecules (dipole−ionic bond) rather than like molecules (hydrogen bond formation), and leads to a negative VEm, and (c) structural contribution, which arises due to a packing effect of components into each other’s structure G
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Table 8. Adjustable Parameters, ai, of the Redlich−Kister, eq 10, and Standard Deviations, σ, eq 11, of Excess Properties of Binary Systems (Acetic Acid + Water) and (Acetic Acid + Toluene) at Temperatures of T = (293.15 to 303.15) K excess property
T/K
a0
VEm/cm3 mol−1 ΔR/cm3 mol−1 VEm/cm3 mol−1 ΔR/cm3 mol−1 VEm/cm3 mol−1 ΔR/cm3 mol−1
293.15 293.15 298.15 298.15 303.15 303.15
−4.4504 −9.0410 −4.3979 −9.4190 −4.4383 −9.4506
VEm/cm3 mol−1 ΔR/cm3 mol−1 VEm/cm3 mol−1 ΔR/cm3 mol−1 VEm/cm3 mol−1 ΔR/ cm3 mol−1
293.15 293.15 298.15 298.15 303.15 303.15
2.8089 −10.9979 2.8461 −11.0072 2.9833 −11.0279
a1 (acetic acid + water) 0.1917 4.8683 0.4524 5.7403 0.2188 5.7691 (acetic acid+ toluene) 1.8557 −2.5388 2.3086 −2.5266 2.2738 −2.5687
a2
a3
σ
−1.3955 −4.3321 −1.2416 −3.4848 −0.5952 −3.4489
0.6943 2.0430 −0.0860 0.4483 0.0313 0.3934
0.0152 0.0754 0.0170 0.0405 0.0305 0.0437
−0.2563 −1.3574 −0.1715 −1.3342 −0.1044 −1.1669
−4.7803 −3.3189 −5.6071 −3.4360 −5.6735 −3.3568
0.0319 0.0515 0.0163 0.0541 0.0156 0.0532
Figure 2. Plot of deviations in molar refraction (ΔR) (a), excess molar volumes (VEm) (b) against the mole fraction of acetic acid (x1) for the binary mixture of (acetic acid + water) at ■, 293.15 K; ●, 298.15 K; ▲, 303.15 K; (−) correlates values as per the Redlich−Kister equation for this work; ☆, 293.15 K ; ×, 298.15 K; ◊, 303.15 K (ref 22); and ○, 298.15 K (ref 12).
Figure 3. Plot of deviations in molar refraction (ΔR) (a), excess molar volumes (VEm) (b) against the mole fraction of acetic acid (x1) for the binary mixture of (acetic acid + toluene) at ■, 293.15 K; ●, 298.15 K; and ▲, 303.15 K; (−) correlated values as per the Redlich−Kister equation.
caused by differences in the molar volumes and free volumes of components contributing a negative value to VEm.44−46 It can be observed from Table 5 that the binary mixtures of (acetic acid + water) show negative values of VEm over the entire composition. In these mixtures, a hydrogen bond forms between the molecules of pure components water−water and acid−acid, and the nature of the bond between solute (acetic acid) and solvent (water)
molecules are dipole−ionic. In the binary mixtures of (acetic acid + water), the ionic−dipole bond (CH3COO− and H2O) is stronger than hydrogen bonds between the pure components.23 Moreover, the negative VEm values also arise due to the different sizes of the components for acetic acid (57.2106 cm3 mol−1) and water (18.0432 cm3 mol−1) at 293.18 K. More interstitial accommodation of molecules into each others structure is due to H
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Table 9. Average Percentage Deviations (APD) for the Binary Systems of (Acetic Acid + Water) and (Acetic Acid + Toluene) over the Entire Composition Range at Temperatures of T = (293.15 to 303.15) Ka (acetic acid + water)
a
(acetic acid + toluene)
mixing rules
293.15 K
298.15 K
303.15 K
293.15 K
298.15 K
303.15 K
L-L G-D A-B N-W E-J W H
0.8927 0.8854 0.8854 0.8774 0.8894 0.8879 0.8934
0.8826 0.8759 0.8759 0.8685 0.8796 0.8782 0.8832
0.8677 0.8616 0.8616 0.8548 0.8650 0.8637 0.8684
−0.3583 −0.4372 −0.4372 −0.5142 −0.3987 −0.4055 −0.3395
−0.3617 −0.4396 −0.4396 −0.5159 −0.4015 −0.4083 −0.3429
−0.3608 −0.4376 −0.4376 −0.5130 −0.3999 −0.4066 −0.3420
(APD100/n)∑(nD,exp − nD,cal/nD,exp), where n is the number of observations.
the smaller size of the solvent than solute,9,23 leading to negative VEm. Therefore, the second and third factors contribute negative VEm of (acetic acid + water). For the binary system of (acetic acid + toluene), VEm shows positive values and is increasing as the temperature increases from (293.15 to 303.15) K. This variation is caused by the expansion of the binary mixtures due to the dominace of dispersive forces in mixtures relative to those in pure components and the function of dipolar forces in the absence of specific interactions.45 In the present study, acetic acid with water exhibits a minimum value at a molar composition of around x1 = 0.412 in tune with the results reported by Tojo et al.22 and Koohyar et al.23 and shows a maximum value with toluene at around x1 = 0.605 at all of the temperatures studied. The reported VEm data for the aqueous acetic acid system compare well with the reported values in the literature.24,30,47,48 The excess properties ΔR and VEm computed from the Redlich−Kister equation fit well with the experimental results. To correlate the measured refractive index, nD, different mixing rules, such as Lorentz−Lorenz (L-L), Wiener’s (W), Gladstone− Dale (G-D), Arago-biot (A-B), Eyring and John (E-J), Newton (N-W), Heller (H), Oster (Os), and Eykman (Eyk) can be employed.25 In the present study, following relations were used for the quantitative prediction of refractive index for the binary mixtures: Lorentz−Lorenz (L-L) relation ⎛ n 2 − 1⎞ ⎛ n 2 − 1⎞ D,1 D,2 ⎜ ⎟ ⎟⎟Φ2 =⎜ ⎟Φ1 + ⎜⎜ 2 2 2 nD + 2 ⎝ nD,1 + 2 ⎠ ⎝ nD,2 + 2 ⎠
Heller (H) relation nD − nD,1 nD,1
nD2 + nD,12
(12)
(13)
Gladstone−Dale (G-D) relation nD − 1 = (nD,1 − 1)Φ1 + (nD,2 − 1)Φ2
(14)
Arago-biot (A-B) relation nD = nD,1Φ1 + nD,2 Φ2
(15)
Eyring and John (E-J) relation nD = nD,1Φ12 + 2(nD,1nD,2)1/2 Φ1Φ2 + nD,2 Φ2 2
(16)
Newton (N-W) relation nD2 − 1 = (nD,12 − 1)Φ1 + (nD,2 2 − 1)Φ2
(18)
4. CONCLUSIONS In the present work, the solubility of benzoic acid in (acetic acid + water) and (acetic acid + toluene) binary mixtures was measured at lower mass fractions of acetic acid from 0.1 to 0.8 at a constant temperature of 299.15 K. Significant changes in the solubility of benzoic acid were observed, as the amount of acetic acid was increased to the binary solvent of (acetic acid + water). The addition of acetic acid favored the solubilization of benzoic acid. Conversely, higher solubility of benzoic acid was observed for the (acetic acid + toluene) system with increased acetic acid amount. It is therefore concluded that mixed solvents exhibit greater influence on the dissolution of benzoic acid compared to pure solvents. Furthermore, experimental findings of densities, refractive index and derived excess properties like deviations in molar refractivity, ΔR, and excess molar volume, VEm, of the binary systems of (acetic acid + water) and (acetic acid + toluene) were determined at different temperatures from (293.15 to 303.15) K. For both binary systems, ΔR exhibits negative values. VEm showed a negative value for the (acetic acid + water) system and a positive value for the (acetic acid + toluene) system that increased with
Wiener’s (W) relation ⎛n 2−n 2 ⎞ D,2 D,1 ⎟ = Φ2⎜⎜ 2 2⎟ ⎝ nD,2 + 2nD,1 ⎠
2 3 ⎡⎢ (nD,2 /nD,1) − 1 ⎤⎥ Φ2 2 ⎢⎣ (nD,2 /nD,1)2 + 2 ⎥⎦
where nD, nD,1, and nD,2 are the refractive index of the mixture, component 1, and component 2, respectively, and Φ1 and Φ2 are the volume fractions of components 1 and 2, respectively. Various mixing rules were tested to predict the refractive index and compared with experimental values in terms of average percentage deviations (APD), which are shown in Table 9. Generally, dispersion and dipolar interactions are predominant for the binary systems where deviations are found to be negative.49 In the present study, deviations are negative for the (acetic acid + toluene) mixtures, which results in dispersion and dipolar interactions. However, positive deviations in (acetic acid + water) mixtures exhibit contraction in the volume of the mixtures. The results coordinate with VEm and ΔR observations with both representing the interaction between components. All of the studied mixing rules predict the experimental refractive index data adequately. G-D and A-B relations exhibit exactly the same deviations at all of the temperatures. This similarity is probable due to a similar functional group present in these equations.24 In the (acetic acid + water) mixture, the least deviation was observed in the case of Newton’s relation compared to other mixing rules, and the Heller relation shows minimum deviation for (acetic acid + toluene) mixtures.
nD2 − 1
nD2 − nD,12
=
(17) I
DOI: 10.1021/acs.jced.5b00197 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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(14) Pires, R.; Franco, M. R. Solubility of benzoic acid in aqueous solutions containing ethanol or N-propanol. J. Chem. Eng. Data 2008, 53, 2704−2706. (15) Chipman, J. The solubility of benzoic acid in benzene and in toluene; Contribution from the Department of Chemistry, Illinois Wesleyan University: Bloomington, IL, 1924; Vol. 46. (16) Krik, E.; Othmer, F. Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.; Wiley: New York, 1993; Vol. 4, p 105. (17) Dian-Qing, L.; Jiang-Chu, L.; Da-Zhuang, L.; Fu-An, W. Solubilities of terephthalaldehydic, p-toluic, benzoic, terephthalic and isophthalic acids in N,N-dimethylformamide from 294.75 to 370.35 K. Fluid Phase Equilib. 2002, 200, 69−74. (18) Ma, P. S.; Xia, Q. Determination and correlation for solubility of aromatic acids in solvents. Chin. J. Chem. Eng. 2001, 9, 39−44. (19) Liu, J. C.; Chen, Z. M.; Tian, H. H.; Li, D. Q.; Liu, D. Z. Measurement and correlation of solubilities of benzoic acid in different solvents. J. Zhengzhou Univ. Technol. 2001, 22, 97−99. (20) Zhu, L.; Wang, L. S. Aqueous solubility of m-phthalic acid, ophthalic acid, and p-phthalic acid. Ind. Eng. Chem. 1999, 16, 236−238. (21) Wang, Q.; Hou, L.; Cheng, Y.; Li, X. Solubilities of Benzoic acid and Phthalic acid in acetic acid + water solvent mixtures. J. Chem. Eng. Data 2007, 52, 936−940. (22) Gonzalez, B.; Dominguez, A.; Tojo, J. Dynamic Viscosities, Densities, and Speed of Sound and Derived Properties of the Binary Systems Acetic Acid with Water, Methanol, Ethanol, Ethyl Acetate and Methyl Acetate at T= (293.15, 298.15, and303.15) K at Atmospheric Pressure. J. Chem. Eng. Data 2004, 49, 1590−1596. (23) Koohyar, F.; Ghasemnejad-Bosra, H.; Sharifirad, M. Investigation on thermodynamic properties for binary systems of water + formic, acetic, trichloroacetic, lactic, and citric acid at T= 292.15 K and atmospheric pressure. Stud. Univ. Babes-Bolyai, Chem. 2012, 4, 217−230. (24) Campbell, A. N.; Kartzmark, E. M.; Gieskes, J. M. T. M. Vaporliquid equilibriums, densities, and refractivities in the system acetic acid-chloroform-water at 25 °C. Can. J. Chem. 1963, 41, 407−429. (25) Vuksanovic, J. M.; Zivkovic, E. M.; Radovic, I. R.; Djordjevic, B. D.; Serbanovic, S. P.; Kijevcanin, M. L. Experimental study and midelling of volumetric properties, viscosities and refractive indices of binary liquid mixtures benzene + PEG 200/ PEG 400 and toluene + PEG 200/PEG 400. Fluid Phase Equilib. 2013, 345, 28−44. (26) Al-Kandary, J. A.; Al-Jimaz, A. S.; Abdul-Latif, A. M. Excess molar volumes and refractive indices of (methoxybenzene + benzene, or toluene, or o-xylene, or m-xylene, or p-xylene, or mesitylene) binary mixtures between T = (288.15 to 303.15) K. J. Chem. Thermodyn. 2006, 38, 1351−1361. (27) Riddick, J. A.; Bunger, W. B. Organic Solvents, Vol. II in Techniques of Chemistry; Wiley-Interscience: New York, 1970. (28) Mariano, A.; Postigo, M.; González-Salgado, D.; Romaní, L. Densities, speeds of sound, and refractive indices of the ternary mixtures (toluene + methyl acetate + butyl acetate) and (toluene + methyl acetate + methyl heptanoate) at 298.15 K. J. Chem. Thermodyn. 2007, 39, 218− 224. (29) Riddick, J. A., Bunger, W. B., Sakano, T. K., Eds. Organic Solvents (in Techniques of Chemistry); Weissberger, A., Ed.; Wiley-Interscience: New York, 1986; Vol. II. (30) Apelblat, A.; Manzurola, E. Excess molar volume of formic acid + water, acetic acid + water and propionic acid + water systems at 288.15, 298.15, and 308.15 K. Fluid Phase Equilib. 1987, 32, 163−193. (31) Cases, A. M.; Gomez Marigliano, A. C.; Bonatti, C. M.; Solimo, H. N. Density, viscosity and Refractive index of Formamide, three Carboxylic acids, and formamide + carboxylic acid binary mixtures. J. Chem. Eng. Data 2001, 46, 712−715. (32) Thella, P. K.; Das, P. K. Solubility and Tie-line data for water + formic acid + methyl isobutyl ketone ternary system at different temperatures. Chem. Eng. Commun. 2010, 197, 1163−1171. (33) Ince, E. Liquid-Lquid Equilibria of Water + Aceti acid + Dimethyl Glutarate Ternary System. J. Chem. Eng. Data 2005, 50, 1539−1542. (34) Zhu, M. Solubility and Density of the Disodium Salt Hemiheptahydrate of Ceftriaxone in Water + Ethanol Mixtures. J. Chem. Eng. Data 2001, 46, 175−176.
increasing temperature. To predict the refractive index values, various mixing rules, including Lorentz− Lorenz (L-L), Wiener’s (W), Gladstone−Dale (G-D), Arago-biot (A-B), Eyring and John (E-J), Newton (N-W), and Heller (H) have been employed. In the (acetic acid + water) mixture, the least deviation was observed in the case of Newton’s relation, and the Heller relation shows minimum deviation for (acetic acid + toluene) mixtures.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.5b00197. Refractive indices, nD, of binary systems (acetic acid + water) and (acetic acid + toluene) at temperatures from (293.15 to 303.15) K and at wavelengths from (404.7 to 706.5) nm (PDF)
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AUTHOR INFORMATION
Corresponding Author
*Tel.: +91 040 27191399/040 27193141; fax: +91 04027193626; e-mail:
[email protected]. Notes
The authors declare no competing financial interest.
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REFERENCES
(1) Long, B.; Li, J.; Zhang, R.; Wan, L. Solubility of benzoic acid in acetone, 2-propanol, acetic acid and cyclohexane; Experimental measurement and thermodynamic modeling. Fluid Phase Equilib. 2010, 297, 113−120. (2) Ding, Z.; Zhang, R.; Long, B.; Liu, L.; Tu, H. Solubilities of mPhthalic acid in petroleum ether and its binary solvent mixture of alcohol + petroleum ether. Fluid Phase Equilib. 2010, 292, 96−103. (3) Nordstrom, F. L.; Rasmuson, A. C. Solubility and melting properties of salicylamide. J. Chem. Eng. Data 2006, 51, 1775−1771. (4) Long, B.; Wang, Y.; Zhang, R.; Xu, J. Measurement and correlation of solubilities of m-Phthalic acid in monobasic alcohols. J. Chem. Eng. Data 2009, 54, 1764−1766. (5) Oliviera, A. C.; Coelho, M. G.; Pires, R. F.; Franco, M. R. Solubility of benzoic acid in mixed solvents. J. Chem. Eng. Data 2007, 52, 298−300. (6) Thati, J.; Nordstrom, F. L.; Rasmuson, A. C. Solubility of Benzoic Acid in Pure Solvents and Binary Mixtures. J. Chem. Eng. Data 2010, 55, 5124−5127. (7) Shukla, R. K.; Kumar, A.; Srivastava, U.; Srivastava, K.; Gangwar, V. S. Arabian J. Chem. 2012, in press DOI: 10.1016/j.arabjc.2012.02.013. (8) Isehunwa, S. O.; Olanisebe, E. B.; Ajiboye, O. O.; Akintola, S. A. Estimation of the refractive indices of some binary mixtures. Afr. J. Pure Appl. Chem. 2015, 9, 58−64. (9) Ciocirlan, O.; Iulian, O. Density, viscosity and refractive index of the dimethyl sulfoxide + o- xylene system. J. Serb. Chem. Soc. 2009, 74, 317−329. (10) Huang, J. F.; Lee, L. S. Simultaneous estimation of excess enthalpy, excess Gibbs energy and Vapor-Liquid equilibrium using modified Wilson model. Fluid Phase Equilib. 1996, 121, 27−43. (11) Rattan, V. K.; Kapoor, S.; Tochigi, K. Viscosities and Densities of Binary Mixtures of Toluene with Acetic Acid and Propionic Acid at (293.15, 313.15, and 323.15) K. J. Chem. Eng. Data 2002, 47, 1182− 1184. (12) Granados, K.; Gracia-Fadrique, J.; Amigo, A.; Bravo, R. Refractive Index, Surface Tension, and Density of Aqueous Mixtures of Carboxylic Acids at 298.15 K. J. Chem. Eng. Data 2006, 51, 1356−1360. (13) Apelblat, A.; Manzurola, E.; Balal, N. A. The solubilities of benzene polycarboxylic acids in water. J. Chem. Thermodyn. 2006, 38, 565−571. J
DOI: 10.1021/acs.jced.5b00197 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
(35) Long, B. W.; Wang, L. S.; Wu, J. S. Solubilities of 1,3Benzenedicarboxylic acid in water + acetic acid solutions. J. Chem. Eng. Data 2005, 50, 136−137. (36) Wang, H.; Wang, Q.; Xiong, Z.; Chen, C.; Shen, B. Solubilities of benzoic acid in binary (benzyl alcohol + benzaldehyde) solvent mixtures. J. Chem. Thermodyn. 2015, 83, 61−66. (37) Takamuku, T.; Kyoshoin, Y.; Noguchi, H.; Kusano, S.; Yamaguchi, T. Liquid Structure of Acetic Acid- Water and Trifluoroacetic Acid- Water Mixtures Studied by Large-Angle X-ray Scattering and NMR. J. Phys. Chem. B 2007, 111 (31), 9270−9280. (38) Sun, Y.; Su, L.; Wang, H. Volumetric properties of binary liquid mixtures: Application of the Prigogine-flory-patterson theory to excess molar volumes of dichloromethane with benzene or toluene. J. Chem. Thermodyn. 2009, 41, 1154−1161. (39) Redlich, O.; Kister, A. T. Algebraic Representation of Thermodynamic Properties and the Classification of Solutions. Ind. Eng. Chem. 1948, 40, 345−348. (40) Fermeglia, M.; Torriano, G. Density, viscosity, and refractive index for binary systems of n-C16 and four Nonlinear Alkenes at 298.15 K. J. Chem. Eng. Data 1999, 44, 965−969. (41) Bevington, P. Data Reduction and Error Analysis for the Physical Sciences; McGraw-Hill: New York, 1969. (42) Pineiro, A.; Brocos, P.; Amigo, A.; Pintos, M.; Bravo, R. Surface tensions and refractive indices of (tetrahydrofuran+n-alkanes) at T ≥ 298.15 K. J. Chem. Thermodyn. 1999, 31, 931−942. (43) Aminabhavi, T.; Phayde, H. T. S.; Khinnavar, R. S.; Gopalakrishna, B.; Hansen, K. C. Densities, refractive indices, speeds of sound, and shear viscosities of diethylene glycol dimethyl ether with ethyl acetate, methyl benzoate, ethyl benzoate, and diethyl succinate in the temperature range from 298.15 to 318.15 K. J. Chem. Eng. Data 1994, 39, 251−260. (44) Moosavi, M.; Motahari, A.; Omrani, A.; Rostami, A. O. Thermodynamic study on some alkanediol solutions: Measurement and modeling. Thermochim. Acta 2013, 561, 1−13. (45) Mesquita, F. M. R.; Feitosa, F. X.; Aznar, M.; Sant’Ana, H. B. D. Density, viscosities, and excess properties for binary mixtures of sulfolane + alcohols at different temperatures. J. Chem. Eng. Data 2014, 59, 2196−2206. (46) Thakur, P. K.; Patre, S.; Pande, R. Thermophysical and excess properties of hydroxamic acids in DMSO. J. Chem. Thermodyn. 2013, 58, 226−236. (47) Casanova, C.; Wilhelm, E.; Grolier, J.-P. E.; Kehiaian, H. V. Excess volumes and excess heat capacities of (water + alkanoic acid). J. Chem. Thermodyn. 1981, 13, 241−148. (48) Korpela, J. Densities and compression isotherms of formic acidwater, acetic acid-water, propionic acid-water, and isobutyric acid-water mixtures. Acta Chem. Scand. 1971, 25, 2852−2864. (49) Sharma, S.; Patel, P. B.; Patel, R. S.; Vora, J. J. Density and Comparative Refractive Index Study on Mixing Properties of Binary Liquid Mixtures of Eucalyptol with Hydrocarbons at 303.15, 308.15 and 313.15K. E-J. Chem. 2007, 4, 343−349.
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DOI: 10.1021/acs.jced.5b00197 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
