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Enthalpies of Vaporization and Sublimation of the HalogenSubstituted Aromatic Hydrocarbons at 298.15 K: Application of Solution Calorimetry Approach Boris N. Solomonov,*,† Mikhail A. Varfolomeev,† Ruslan N. Nagrimanov,† Vladimir B. Novikov,† Marat A. Ziganshin,† Alexander V. Gerasimov,† and Sergey P. Verevkin*,†,‡ †

Department of Physical Chemistry, Kazan Federal University, Kremlevskaya str. 18, 420008 Kazan, Russia Department of Physical Chemistry, University of Rostock, Dr-Lorenz-Weg 1, 18059 Rostock, Germany

‡

S Supporting Information *

ABSTRACT: Recently, the solution calorimetry has been shown to be a valuable tool for the indirect determination of vaporization or sublimation enthalpies of low volatile organic compounds. In this work we studied 16 halogen-substituted derivatives of benzene, naphthalene, biphenyl, and anthracene using a new solution calorimetry based approach. Enthalpies of solution at infinite dilution in benzene as well as molar refractions for the chlorine-, bromine-, and iodine-substituted aromatics were measured at 298.15 K. Vaporization and sublimation enthalpies of these compounds at 298.15 K were indirectly derived from the solution calorimetry data. In order to verify results obtained by using solution calorimetry, vaporization/sublimation enthalpies for 1,2-, 1,3-, 1,4-dibromobenzenes, 4-bromobiphenyl, and 4,4′-dibromobiphenyl were additionally measured by using the well established transpiration method. Experimental data available in the literature were collected and evaluated in this work for the sake of comparison with our own results. Vaporization and sublimation enthalpies of halogen-substituted aromatics under study derived by using solution calorimetry approach have been in a good agreement with those measured by conventional methods. This fact approves using of solution calorimetry for determination or validation of sublimation/vaporization enthalpies for different aromatic compounds at reference temperature 298.15 K, where the conventional experimental data are absent or in disarray. Evaluated in this work a data set has been used to establish a simple group additivity scheme for prediction of vaporization enthalpies for halogen-substituted aromatic hydrocarbons.

1. INTRODUCTION Halogen-substituted aromatic compounds are well-known environmental pollutants resulting from the incomplete combustion of coal and fossil fuels, as well as of rural waste incineration. Reliable thermochemical data for these molecules are required for prediction of their environmental behavior. However, only very few experimental data are known from the literature.1,2 Experimental determination of vaporization/ sublimation enthalpies of low volatile compounds using conventional methods is a challenging task. Results available in the literature data are very often in disarray. Just recently we have developed and tested a solution calorimetry approach to derive vaporization/sublimation enthalpies for a number of aromatic and polyaromatic hydrocarbons, successfully.3 In comparison to conventional methods, where experiment is performed at elevated temperatures, the solution calorimetry based approach has some crucial advantages. First, calorimetric measurements are usually carried out directly at the reference temperature 298.15 K. Following, this method is highly suitable for studies of thermally unstable compounds. Moreover, the solution calorimetry based method is free from difficulties connected with proper temperature adjustment of experimental data to 298.15 K. Second, the calorimetric procedure is quick © 2015 American Chemical Society

and less demanding compared to the conventional methods. Third, only a small amount (about 500 mg) of the pure sample (0.98 to 0.99 mass fractions are sufficient) as a rule could be enough for the calorimetric experiment. All these facts make the solution calorimetry a useful technique for the rapid evaluation of vaporization/sublimation enthalpies of low volatile and thermally unstable organic compounds. The present work is part of a broader program, aiming evaluation of experimental data on vaporization/sublimation enthalpies of aromatic compounds using a solution calorimetry based approach in combination with well established conventional methods. We report here a systematic determination of vaporization/sublimation enthalpies of a series of 16 halogensubstituted derivatives of benzene, naphthalene, biphenyl, and anthracene by using the solution calorimetry and the transpiration method. This work has five major goals. The first is the experimental determination of solution enthalpies of 16 halogen-substituted aromatic compounds in benzene at the infinite dilution at Received: September 23, 2014 Accepted: January 20, 2015 Published: February 5, 2015 748

DOI: 10.1021/je5008795 J. Chem. Eng. Data 2015, 60, 748−761

Journal of Chemical & Engineering Data

Article

Table 1. Origin, Purity, Methods of Purification, and Analysis of Halogen-Substituted Aromatic Hydrocarbons and Solvents (Benzene and Carbon Tetrachloride)

a

chemical name

source

initial mole fraction purity

purification method

1-bromo-4-chlorobenzene 1,2-dibromobenzene 1,3-dibromobenzene 1,4-dibromobenzene hexachlorobenzene 1-bromonaphthalene 1-iodonaphthalene 1,4-dibromonaphthalene 4-bromobiphenyl 4,4′-dibromobiphenyl 9-chloroanthracene 9-bromoanthracene 9,10-dichloroanthracene 9,10-dibromoanthracene benzene I benzene II carbon tetrachloride 1-propanol potassium chloride

Aldrich Alfa Aesar Alfa Aesar Alfa Aesar Alfa Aesar Aldrich Aldrich Alfa Aesar Alfa Aesar Alfa Aesar Alfa Aesar Alfa Aesar Alfa Aesar Alfa Aesar Vecton Ekos-1 Ekos-1 Acros Aldrich

0.99 0.98 0.97 0.98 0.98 0.97 0.97 0.98 0.98 0.98 0.96 0.96 0.97 0.98 0.99 0.98 0.98 0.99 0.99

none distillation distillation sublimation sublimation none none sublimation sublimation sublimation sublimation recrystallization recrystallization recrystallization distillation distillation distillation none none

final mole fraction purity 0.999 0.999 0.999 0.999

0.998 0.998 0.998 0.995 0.995 0.995 0.995 0.999 0.999 0.999

analysis method GCa GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC GC

Gas chromatography.

from the second producer was used. For measurements of density and refractive index both of them were taken. Carbon tetrachloride was distilled over the CaH2. The final purity of benzene and carbon tetrachloride after purification was more than 0.999 according to the GC analysis (see Table 1).

298.15 K, as well as measurements of their molar refractions as auxiliary quantities. Our second goal addresses the refinement of the solution calorimetry based approach toward reliable determination of vaporization/sublimation enthalpies. The third is compilation of vaporization/sublimation enthalpies from the literature and additional measurements of these properties using the transpiration method. The fourth goal is compilation and redetermination of the molar enthalpies of fusion by means of differential-scanning calorimetry (DSC). From reconciliation of thermochemical data measured by different methods we hope to validate our results derived by using solution calorimetry, as well as to establish a consistent set of vaporization/sublimation enthalpies for aromatic compounds under study. Finally, our aim is to study the intramolecular interactions of the substituents on the aromatic ring in terms of deviations of vaporization enthalpies from the group additivity rules. These interactions could be used to predict values of vaporization enthalpies for unmeasured compounds with similar structures.

3. METHODS 3.1. Solution Calorimetry. Dissolution enthalpies, ΔsolnHAi/S, of halogen-substituted aromatic hydrocarbons in benzene at 298.15 K were measured using TAM III solution calorimeter (TA Instruments) equipped with 100 mL glass cell. The ampule breaking technique was used for dissolution of crystalline solutes. We used about (0.01 to 0.05) g of a solute for each experiment. The sample was weighed with balances resolution of 10−4 g. Liquid solutes were introduced into the measuring cell with the solvent using the 100 μL syringe equipped with a gold cannula. The solute was dropped in the solvent by the portions of 10 μL to 20 μL. The portional injection of the solute allowed controlling concentration dependence of obtained data and performing experiments close to the infinite dilution conditions. As a rule, the mole fraction of the solute (crystalline or liquid) in final solution was below 0.001. The detailed description of the calorimeter and dissolution procedure was published elsewhere.3,4 The device and experimental procedure were tested by determination of dissolution enthalpy of potassium chloride in water (17.41 ± 0.04) kJ·mol−1 (ampule breaking technique) and propan-1-ol in water (−10.16 ± 0.02) kJ·mol−1 (titration technique). For comparison, the value of dissolution enthalpy of potassium chloride in water recommended by the ICTAC working group “thermochemistry” (KCl:H2O = 1:2000) was 17.47 ± 0.07 kJ· mol−1.5 The recommended value for dissolution enthalpy of propan-1-ol in water was (−10.16 ± 0.02) kJ·mol−1.6 Thus, the deviations of our experimental tests from the recommended data do not exceed 0.4%. Experimental solution enthalpies, ΔsolnHAi/S, of halogensubstituted aromatic hydrocarbons in benzene at different

2. EXPERIMENTAL SECTION 2.1. Materials. All halogen-substituted aromatic hydrocarbons were of the commercial origin with the mass fraction purities better than 0.97. Detailed information about samples is presented in Table 1. Before experiments solid samples were purified by the repeated crystallization or by fractional sublimation in vacuum. Liquid samples were purified by fractional distillation at reduced pressure. The purity of samples was analyzed by using gas chromatograph (GC) Agilent 7890 B equipped with the flame ionization detector. Final purities of samples under study were 0.999 after purification. Some samples for solution calorimetry were used without purification (see Table 1). Benzene used in the solution calorimetry as a solvent was carefully purified by subsequent washing with H2SO4, NaOH, and water and distilled over the CaH2. It was purchased from two different producers. That is why even after distillation benzene from different producers has different density (see Table S3). For calorimetric measurements benzene 749



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Table 2. Enthalpies of Solution, ΔsolnHAi/S, and Solvation, ΔsolvHAi/S, of Halogen-Substituted Aromatic Hydrocarbons in Benzene (or Carbon Tetrachloride), Their Molar Refractions, MRAi, and Enthalpies of Sublimation or Vaporization, Δgcr,lHAmi, Calculated using eqs 12 or 13a A

A

compound

((ΔsolnHAi/S)

((MRAi)

((ΔsolvHAi/S)

((Δgcr,lHmi)

((Δgcr,lHmi)

(Δb

Ai

kJ·mol−1

cm3·mol−1

kJ·mol−1

kJ·mol−1 (eqs 12 and 13)

kJ·mol−1 (Tables 4-7)k

kJ·mol−1

1

2

1,3-dichlorobenzene (l) 1-bromo-4-chlorobenzene (cr) 1,2-dibromobenzene (l) 1,3-dibromobenzene (l) 1,4-dibromobenzene (cr) 1,2,4,5-tetrachlorobenzene (cr) hexachlorobenzene (cr) 1-bromonaphthalene (l) 1-iodonaphthalene (l) 1,4-dibromonaphthalene (cr) 4-bromobiphenyl (cr) 4,4′-dibromobiphenyl (cr) 9-chloroanthracene (cr) 9-bromoanthracene (cr) 9,10-dichloroanthracene (cr) 9,10-dibromoanthracene (cr)

1.1 ± 0.2c 17.67 ± 0.15e 1.16 ± 0.01e 2.0 ± 0.2e 19.8 ± 0.4e 25.1 ± 0.4g 24.3 ± 0.4g 1.24 ± 0.01e 1.7 ± 0.2e 20.6 ± 0.4e 20.1 ± 0.3e 23.1 ± 0.6e 21.5 ± 0.2e 21.4 ± 0.2e 27.7 ± 0.8e 24.8 ± 0.8e

3 36.2 39.3 41.4 42.4 42.9 45.4 58.0 51.4 56.6 61.5 61.3 70.1 68.9 71.4 73.7 79.5

± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±

4 0.2d 0.2f 0.2d 0.2d 0.3f 0.6h 0.3f 0.2d 0.2d 0.7f 1.0f 1.1f 0.7j 0.7j 0.8h 0.8h

5

46.2 49.6 51.9 53.0 53.5 55.8i 70.0i 62.8 68.4 73.8 73.6 83.1 81.8 84.5 87.0 93.5

47.3 67.3 53.1 55.0 73.3 80.9 94.3 64.0 70.1 94.4 93.7 106.2 103.3 105.9 114.7 118.2

± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±

6 0.4 0.4 0.2 0.4 0.7 1.0 0.7 0.2 0.4 1.1 1.3 1.7 0.9 0.9 1.6 1.6

47.7 68.7 54.3 54.9 74.5 83.5 95.7 63.7 69.9 91.3 91.0 105.5 106.6 102.2 115.9 117.5

± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ±

7 0.3 0.2 0.9 0.6 1.1 0.5 1.5 0.9 0.6 1.4 0.6 0.8 0.9 0.7 4.2 3.0

0.4 1.4 1.2 −0.1 1.2 2.6 1.4 −0.3 −0.2 −3.1 −2.7 −0.7 3.3 −3.7 1.2 −0.7

a All values at T/K = 298.15 K and 0.1 MPa. bDifference between column 6 and 5 in kJ mol−1. cCalculated from excess molar enthalpies taken from ref 19. dDetermined from the literature data of densities and refractive indices of studied compounds. eMeasured in this work by solution calorimetry. fMeasured in this work. gEnthalpies of solution in carbon tetrachloride which were taken from ref 17. hCalculated by additive scheme. i Calculated by eq 11. jDetermined from the molecular polarizability data, ref 7. kRecommended values from Tables 4 to 7. Uncertainties in this table correspond to expanded uncertainties of the mean (0.95 level of confidence).

concentrations are listed in the Supporting Information (see Table S1). The average values of solution enthalpies derived from 4 to 6 experiments are presented in Table 2. 3.2. Molar Refraction Determination. Molar refractions required for determination of vaporization/sublimation enthalpies as auxiliary properties were either taken from the literature or derived in this work. Values of (MRAi) of liquid compounds were calculated by eq 1 MRA i =

M A i n A2 i d A i n A2 i

Due to the lack of the input experimental data required for eqs 1 and 2, we assessed molar refractions for other solid halogen-substituted aromatic hydrocarbons according to eq 3 ⎡ n 2 − 1 M A x 2 + MBz(1 − x 2) i MRA i = 1/x 2⎢ 122 ⎢⎣ n12 + 2 d12 ⎤ − MRBz· (1 − x 2)⎥ ⎥⎦

−1 +2

(1)

where MRAi is the molar refraction of studied compound, x2 is the mole fraction of studied compound in benzene solutions, MBz and MAi are the molar masses of benzene and studied compound, d1,2 is the density of the benzene solution of studied compound with the mole fraction x2, and n12 is the refractive index of studied solutions in benzene. This equation was proposed and successfully tested for determination of molar refraction of solid compounds.8 Equation 3 is based on the general assumption that the molar refraction of the liquid binary mixture could be presented as an additive sum of molar refractions of every component of the mixture taking into account its mole fraction (eq 4)

where MAi is the molar mass of the liquid halogen-substituted aromatic hydrocarbon, dAi is the density of the liquid halogensubstituted aromatic hydrocarbon, and nAi is the refractive index of the liquid halogen-substituted aromatic hydrocarbon. Molar refractions for five compounds, 1,3-dichlorobenzene, 1,2dibromobenzene, 1,3-dibromobenzene, 1-bromonaphthalene, and 1-iodonaphthalene, were derived with the help of eq 1. Compilation of densities and refractive indices used for calculations is given in the Supporting Information (see Table S2). For some liquid compounds we could find data only at temperature 293.15 K. We used these values for calculations, because molar refraction of each compound is usually the same at different temperatures. This fact was confirmed by experimental data for 1,3-dichlorobenzene and 1bromonaphthalene (see Table S2). Molar refractions of 9-chloroanthracene and 9-bromoanthracene were estimated with help of eq 2 MRA i = (4/3)πNα

(3)

MR12 = x 2 MRA i + (1 − x 2)MRS

(4)

where MR12, MRAi, and MRS are molar refractions of solution, neat solute, and neat solvent, respectively; x2 is the mole fraction of solute Ai. Molar refraction of the solvent (MRS) and molar refraction of the solution (MR 12) can be determined from the experimental data of densities and refractive indices using eqs 5 and 6

(2)

where N is the Avogadro constant and α is the molecular polarizability available from experiment.7 750



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Table 3. Results from Measurements of the Vapor Pressure (p) of Dibromobenzenes, 4-Bromobiphenyl, and 4,4′Dibromobiphenyl Using the Transpiration Method T/Ka

m/mgb

V(N2)/dm3c

flow of N2/dm3·h−1

1,2-dibromobenzene;

A Δgl Hmi

p/Pad

u(p)/Pae

Δgcr,lHmi/kJ·mol−1 A

−1

(298.15 K) = (54.3 ± 0.3) kJ·mol

ln(p/Pa) = (269.57/R) − (72707.52/(R(T/K)) − (61.7/R) ln((T/K)/298.15) 290.3 292.4 292.5 295.8 298.2 301.2 304.2 307.3 310.2 313.2 316.3 319.3 320.6 322.1 325.2 325.3 328.2

4.65 2.76 2.56 2.83 2.88 2.94 2.68 2.48 3.41 2.72 2.19 2.14 2.63 2.58 2.54 2.39 2.78

3.92 2.07 2.07 2.07 1.86 2.07 1.65 2.07 1.41 2.11 1.16 2.11 0.808 2.11 0.632 2.11 0.682 1.78 0.445 1.78 0.296 1.78 0.241 1.11 0.284 1.00 0.250 1.00 0.200 1.00 0.185 1.11 0.184 1.00 A 1,3-dibromobenzene; Δgl Hmi (298.15 K) = (54.9 ±

12.51 14.08 14.51 18.02 21.58 26.61 34.82 41.15 52.36 63.99 77.36 92.84 96.86 107.48 132.42 134.97 157.86 0.2) kJ·mol−1

0.34 0.38 0.39 0.48 0.56 0.69 0.90 1.05 1.33 1.62 1.96 2.35 2.45 2.71 3.34 3.40 3.97

54.80 54.67 54.66 54.46 54.31 54.13 53.94 53.75 53.57 53.39 53.19 53.01 52.93 52.84 52.65 52.64 52.46

ln(p/Pa) = (272.96/R) − (72924.11/(R(T/K)) − (60.5/R) ln((T/K)/298.15) 276.4 278.7 281.1 282.3 284.7 286.9 288.8 289.2 292.3 292.8 295.0 296.2 298.8 301.0 301.1 304.2 304.9 307.2 308.9 310.0 312.9 313.3 315.2 317.8

2.46 2.55 2.62 2.68 2.88 2.88 3.41 2.74 2.13 2.52 2.81 3.18 1.99 3.03 5.43 4.39 4.22 4.69 4.55 4.19 7.96 4.33 6.94 9.70

5.26 4.25 3.57 3.32 2.86 2.39 2.46 1.88 1.18 1.33 1.27 1.29 0.665 0.860 1.49 0.964 0.932 0.832 0.717 0.613 1.004 0.526 0.717 0.860 1,4-dibromobenzene; ΔgcrHAmi

4.05 4.05 4.05 3.99 3.99 3.99 3.99 2.63 2.63 3.99 2.63 4.30 3.99 4.30 2.63 2.63 4.30 2.63 4.30 2.63 4.30 2.63 4.30 4.30 (298.15 K) = (73.7 ±

5.08 6.46 7.85 8.60 10.72 12.74 14.68 15.40 18.99 19.97 23.24 25.92 31.43 36.98 38.22 47.71 47.40 58.93 66.35 71.38 82.94 86.08 101.21 117.84 0.6) kJ·mol−1

0.15 0.19 0.22 0.24 0.29 0.34 0.39 0.41 0.50 0.52 0.61 0.67 0.81 0.95 0.98 1.22 1.21 1.50 1.68 1.81 2.10 2.18 2.56 2.97

56.20 56.07 55.92 55.85 55.70 55.57 55.45 55.43 55.24 55.21 55.08 55.01 54.85 54.72 54.71 54.52 54.48 54.34 54.24 54.17 54.00 53.97 53.86 53.70

0.20 0.26 0.34 0.37 0.45 0.57 0.64 0.76 0.96 1.19 1.50 1.60

73.69 73.62 73.56 73.53 73.49 73.42 73.40 73.36 73.29 73.22 73.18 73.15

ln(p/Pa) = (287.08/R) − (80361.39/(R(T/K)) − (22.5/R) ln((T/K)/298.15) 296.5 299.5 302.4 303.5 305.4 308.4 309.4 311.4 314.4 317.4 319.4 320.4

6.73 2.97 3.77 9.07 4.14 4.84 7.60 4.96 4.51 5.40 10.08 6.06

11.1 3.60 3.25 7.16 2.63 2.37 3.29 1.80 1.27 1.23 1.801 1.010

5.27 5.27 5.27 5.27 5.27 5.27 5.27 5.27 5.27 5.27 5.27 5.27 751

6.93 9.22 12.72 13.83 17.01 21.88 24.67 29.36 37.57 46.42 58.98 63.13



Article

Table 3. continued 1,4-dibromobenzene; ΔgcrHmi (298.15 K) = (73.7 ± 0.6) kJ·mol−1 A

ln(p/Pa) = (287.08/R) − (80361.39/(R(T/K)) − (22.5/R) ln((T/K)/298.15) 323.4 329.6

5.00 14.39

303.2 308.2 313.0 318.3 323.4 326.2 328.2 333.3 338.3 343.1 348.3 353.0 355.7 358.4 360.2

1.28 1.81 1.19 1.82 1.10 2.11 2.59 2.61 2.75 2.31 2.89 2.58 2.65 2.85 3.06

358.1 363.9 365.4 368.4 373.5 378.5 383.5 388.6 393.3 396.6 399.6 400.4 402.6 404.4

2.37 2.65 3.03 2.58 4.76 6.69 5.66 3.45 6.26 3.04 4.02 4.17 6.99 4.90

0.632 5.27 83.09 1.05 5.27 143.02 4-bromobiphenyl; ΔgcrHAmi (298.15 K) = (91.0 ± 0.3) kJ·mol−1

2.10 3.60

73.09 72.95

0.01 0.01 0.01 0.02 0.03 0.03 0.04 0.06 0.10 0.17 0.25 0.38 0.44 0.58 0.66

90.82 90.66 90.50 90.32 90.16 90.06 90.00 89.83 89.66 89.50 89.33 89.17 89.09 89.00 88.94

ln(p/Pa) = (313.10/R) − (100858.73/(R(T/K)) − (33.1/R) ln((T/K)/298.15) 149.6 122.5 45.90 39.51 13.83 20.20 19.75 11.85 7.902 4.320 3.333 1.890 1.677 1.350 1.267 A 4,4′-dibromobiphenyl; ΔgcrHmi

8.10 7.90 8.10 7.90 7.90 4.04 7.90 7.90 7.90 8.10 4.00 8.10 4.00 8.10 4.00 (298.15 K) = (105.5 ±

0.09 0.16 0.27 0.48 0.83 1.09 1.37 2.30 3.64 5.60 9.07 14.26 16.50 22.07 25.30 0.4) kJ·mol−1

ln(p/Pa) = (323.92/R) − (116449.67/(R(T/K)) − (36.6/R) ln((T/K)/298.15) 48.66 31.11 30.73 20.47 23.18 21.67 12.14 4.67 5.79 2.27 2.30 2.28 3.21 1.89

3.14 6.46 2.84 6.11 5.80 5.42 6.34 5.38 6.43 5.46 5.51 5.36 6.43 6.29

0.38 0.67 0.77 0.99 1.62 2.43 3.67 5.79 8.51 10.49 13.80 14.40 17.10 20.39

0.01 0.02 0.02 0.03 0.05 0.07 0.10 0.17 0.24 0.29 0.37 0.39 0.45 0.53

103.35 103.13 103.08 102.97 102.78 102.60 102.42 102.23 102.06 101.94 101.83 101.80 101.72 101.65

a Saturation temperature (u(T) = 0.1 K). bMass of transferred sample condensed at T = 243 K. cVolume of nitrogen (u(V) = 0.005 dm3) used to transfer m (u(m) = 0.0001 g) of the sample. dVapor pressure at temperature T, calculated from the m and the residual vapor pressure at T = 243 K. e The standard uncertainties (u) of the measured vapor pressures have been calculated to be u(p/Pa) = 0.025 + 0.025(p/Pa) for p > 5 to 1000 Pa and u(p/Pa) = 0.005 + 0.025(p/Pa) for p < 5 Pa (see the Supporting Information)

⎡ (n 2 − 1) M A x 2 + MS(1 − x 2) ⎤ i ⎥ MR12 = ⎢ 12 2 ⎢⎣ (n12 + 2) ⎥⎦ d12 MRS =

(nS 2 − 1) MS (nS 2 + 2) dS

measurements of molar refraction of solid compounds, we used them for the determination of MRAi of one liquid compound studied in this work. We chose 1,2-dibromobenzene for this purpose. Obtained experimental data of densities and refractive indices for solutions of 1,2-dibromobenzene in benzene are presented in Table S3. Calculated by eqs 3 to 5 molar refraction of 1,2-dibromobenzene (41.6 cm3·mol−1; see Table S3) is indistinguishable from the value determined by direct way (eq 1) using the density and refractive index of pure 1,2dibromobenzene (41.4 cm3·mol−1; see Table S2). It proves the validity of the simple additivity of molar refraction and eqs 3 to 5. Molar refractions for every solid compound under study were calculated from experimental data measured in solutions of different concentrations. Good agreement of MRAi values regardless of the composition of the binary mixture (see Electronic Supporting Information, Table S3) served as a proof of the data reliability. Molar refractions of 1,4-dibromobenzene (42.9 ± 0.3 cm3·mol−1) and 1-bromo-4-chlorobenzene (39.3 ± 0.2 cm3·mol−1) determined by eqs 3 to 5 corresponds well to

(5)

(6)

where n12 and nS are refractive indices of the solution and the neat solvent (S), d12 and dS are densities of the solution and the neat solvent (S), and MAi and MS are molar masses of the solute (Ai) and the solvent (S). Assumption for the additivity of molar refraction is only valid if the two compounds (solute and solvent) do not form complexes, hydrogen bonds, or other specific interactions. Moreover, the resulting solution is expected to form an ideal solution. In order to fulfill such assumptions, we deliberately used benzene as the solvent in this work because benzene is not capable of any specific interactions with halogen-substituted aromatic hydrocarbons. Before applying eqs 3 to 5 to the 752



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the literature values (43.3 cm3·mol−1) and (39.9 cm3·mol−1).9 It is additional confirmation of the validity of the approach used in this work for estimation of MRAi values of solid compounds. Molar refractions of 9,10-dichloroanthracene and 9,10dibromoanthracene were calculated by using additive rules starting from the molar refraction of anthracene (64.8 cm3· mol−1) and contributions due to the substitution of H atom in anthracene with Cl (4.81 cm3·mol−1) or Br (8.1 cm3·mol−1) atoms. Values of molar refractions for 16 halogen-substituted aromatic hydrocarbons used in the solution calorimetry approach are collected in Table 2. 3.3. Refractive Index Measurements. Refractive indices (ni) required for calculation of molar refractions according to eqs 1 and 3 were measured on an automatic digital refractometer RX-5000 alpha (Atago CO., Ltd.) at 298.15 ± 0.01 K and wavelength 589 nm (yellow sodium line). Details on the experimental procedure and equipment were published previously.3 The refractometer was calibrated with pure water. Experimental refractive indices measured in this work are collected in the Supporting Information (see Table S3). 3.4. Densimetry. Densities of liquid samples and solutions, di, required for calculation of the molar refraction according to eqs 1 and 3 were measured using the vibrating-tube densimeter DSA 5000 M (Anton Paar, Co). The experimental procedure was described elsewhere.3 All experiments including calibrations were carried out at 298.15 ± 0.01 K. Experimental results on di are collected in the Supporting Information (see Table S3). 3.5. Transpiration Method. 3.5.1. Vaporization/Sublimation Enthalpy Measurements. Vapor pressures over the liquid 1,2-dibromobenzene and 1,3-dibromobenzene, and over the solid 1,4-dibromobenzene, 4-bromobiphenyl, and 4,4′dibromobiphenyl were measured by the transpiration method using nitrogen as a carrier gas.10 The saturator was filled with the small glass beads covered by about 0.5 g of the sample. At constant temperature (± 0.1 K), the nitrogen stream was passed through the saturator and the transported material was collected in a cold trap. The absolute vapor pressures, pi, at different temperatures Ti were calculated from the amount of product collected within a definite period of time according to the ideal gas law. The volume of transporting gas V(N2) was determined from the flow rate and time of measurements. Vaporization or sublimation enthalpies were derived from the temperature dependences of the experimental vapor pressures (see Table 3). 3.6. Differential Scanning Calorimetry. 3.6.1. Fusion Enthalpy Measurements. The enthalpies and temperatures of fusion of 1,4-dibromonaphthalene, 4-bromobiphenyl, 9-chloroanthracene, 9,10-dichloroanthracene, 9,10-dibromoanthracene were measured using the differential scanning calorimeter DSC 204 F1 Phoenix (Netzsch, Germany) as described previously.11 Samples of about (1 to 6) mg were placed in a 40 μL aluminum crucible and closed with a lid having a hole of 0.5 mm diameter. Experiments were performed in the argon dynamic atmosphere (150 mL·min−1) with the heating/cooling rate of 10 K·min−1. For each compound three cycles of “heating-cooling” runs from room temperature up to temperature on 40 K higher than melting point and back were carried out. Uncertainties of temperature and enthalpy determination by this technique were of 0.1 K and 3%, respectively. Experimental results from DSC measurements are presented in the Supporting Information (see Table S4). It is worth mentioning that enthalpies of fusion

for 1,4-dibromonaphthalene, 4-bromobiphenyl, 9-chloroanthracene, and 9,10-dibromoanthracene measured during the first, second, and third runs were indistinguishable. However, for 9,10-dichloroanthracene only results of the first heating were taken into account due to the significant mass loss of sample at the fusion temperature. Detailed procedure of mass loss analysis and corrections made for fusion enthalpy of 9,10dichloroanthracene is described in the Supporting Information.

4. METHODOLOGY Solution calorimetry based approach for determination of vaporization and sublimation enthalpies is based on general relationships Δsolv H A i /S = Δsoln H A i /S − Δlg HmA i

(7)

Δsolv H A i /S = Δsoln H A i /S − Δcrg HmA i

(8)

between three thermochemical quantities: enthalpy of solution ΔsolnHAi/S of a solute Ai (halogen-substituted aromatic compound in this work) in a solvent S (benzene in this work), enthalpy of solvation ΔsolvHAi/S of the solute Ai in the same solvent S, and the enthalpy of vaporization Δg1HAmi of the solute Ai (for the liquid solutes) or the enthalpy of sublimation, ΔgcrHAmi, for the solid solutes. Equations 7 and 8 can be practically applied to assess vaporization/sublimation enthalpies of any solute Ai provided that the solvation and solution enthalpies are available from other sources as described below. The molar enthalpy of solution, ΔsolnHAi/S, is the heat effect of dissolution of 1 mol of a solute Ai in a sufficient amount of solvent S to give a solution of the infinite dilution. This property is directly measured at 298.15 K using the solution calorimetry or any other indirect techniques (gas chromatography,12 spectroscopy,13 and etc.). The molar enthalpy of solvation, ΔsolvHAi/S, is the heat effect of the transfer of 1 mol of a solute Ai from the ideal gas state to the solvent S to give a solution of the infinite dilution. This property is not directly available from the experiment, except for gases. However, in our previous work,3,14−18 we have found a general linear dependence between enthalpies of solvation of solutes Ai in nonpolar or polar solvents and their molar refractions (MRAi) −Δsolv H A i /S = aS + bS MRA i

(9)

where as and bs are empirical coefficients specific for different solvents S. Thus, eq 9 allows us to get indirect access to enthalpies of solvation of any solute Ai provided that molar refractions MRAi are derived according to eqs 1 to 3 from experimental data on density and refractive index. Linear relationships expressed by eq 9 were observed for different solvents S. The most extended data were available for cyclohexane as the solvent.14−17 More than 100 organic compounds of different types and structure fitted the linear equation between the solvation enthalpy and the molar refraction.16 Unfortunately, aromatic and polyaromatic compounds generally have low solubility in cyclohexane and better solubility in benzene. Due to this reason we were forced to adjust empirical coefficients as and bs for benzene as the solvent3,18 −Δsolv H A i /C6H6/kJ·mol−1 = 6.86 + 1.088MRA i (N = 11; R = 0.998; SD = 0.8kJ ·mol−1) 753

(10)



Article

Table 4. Compilation of Data on Enthalpies of Sublimation or Vaporization, Δgcr,lHAmi, of Halogen-Substituted Benzenes T

compound Ai 1,3-dichlorobenzene (l) 1-bromo-4-chlorobenzene (cr) 1-bromo-4-chlorobenzene (l) 1,2-dibromobenzene (l)

1,3-dibromobenzene (l)

1,4-dibromobenzene (cr)

1,4-dibromobenzene (l)

1,2,4,5-tetrachlorobenzene (cr)

1,2,4,5-tetrachlorobenzene (l)

hexachlorobenzene (cr)

hexachlorobenzene (l)

technique

a

K range

A

Δgcr,lHmi (Tm/K) kJ·mol

−1

Ccrp (−ΔgcrCp)b)/(Clp(−Δgl Cp))b J·mol

−1

K

−1

EB SC T SC T Ed N/A N/A T

357 to 448 298.15 280.1 to 333.1 298.15 338.8 to 365.6

44.1

170.9 (53.9)

67.9 ± 0.3

146.8c (22.7)

48.6 ± 0.4

183.2 (58.2)

403 to 476 388 to 568 290.3 to 328.2

47.8 47.0 53.7

196.8 (61.7)

SC Ed N/A T

298.15 46.9 55.1

192.0 (60.5)

SC Ed ME S N/A S S ME T ME T

298.15 262.2−278.2 308.2 to 353.2 298 to 354 274.7 to 291.3 299.0 to 353.7 228.2 to 328.2 273 to 347 248 to 303 297 to 330

75.4 71.6 73.2 74.0 72.3 73.6 73.7 59.8 73.5

145.3f(22.5)

298.15 352.5 to 491.8 361.5 to 404.3 364.5 to 385.4

50.6 49.4 50.6

187.0 (58.2)

290 to 410 298.15

82.3 83.2

183.8 (28.3)

SC N/A Eg Ed TGA TGA T T T C N/A T T S N/A

298.15 419 to 518

53.7

228.0 (69.9)

386 386 358 243 258 338 387 314 288 369 387

76 77 94.2 74.2 105.7 89.6 61.8 94.4 100.0 91.2 62.0

201.3 (30.9)

SC Eg Ed

298.15

SC N/A S S Eg Ed S+ME C N/A

417 to 500 276 to 318

to 403 to 303 to 313 to to to to to

502 373 318 397 492

276.6 (82.5)

A

Δgcr,lHmi (298.15 K)

ref

−1

kJ·mol

47.7 ± 0.3 47.3 ± 0.4 68.7 ± 0.2 67.3 ± 0.4 51.4 ± 0.4 52.2d 56.3 ± 3.0 58.1 ± 3.0 54.3 ± 0.3 54.3 ± 0.9e 53.1 ± 0.2 54.7d 56.6 ± 3.0 54.9 ± 0.2 54.9 ± 0.6e 55.0 ± 0.4 54.7d 74.8 ± 0.1 72.3 ± 0.4 73.9 ± 3.0 73.7 ± 0.3 72.8 ± 0.5 73.0 ± 0.7 74.0 ± 1.0 (60.3) 73.7 ± 0.7 74.5 ± 1.1e 73.3 ± 0.7 (57.3 ± 0.8) 54.4 ± 0.2 55.1 ± 0.1 54.1 ± 0.7g 54.9 ± 0.5e 54.7d 83.5 ± 0.3 83.2 ± 0.3 85.6 ± 0.8h 83.5 ± 0.5e 80.9 ± 1.0 65.3 ± 1.6 63.2 ± 0.6g 65.5d (80 ± 5) (81 ± 7) 96.8 ± 0.5 (73.3 ± 1.7) (105.3 ± 5.5) 90.8 ± 1.0 (66.4 ± 3.0) 95.8 ± 1.9 100.2 ± 3.1 94.4 ± 8.2 (66.3 ± 3.0) 95.7 ± 1.5e 94.3 ± 0.7 81.5 ± 1.6g 81.3d

22 this work 24 this work 24 estimated 25 26 this work average this work estimated 26 this work average this work estimated 28 28 26 29 30 31 31 32 this work average this work 33 34 28 this work average estimated 35 36 33 average this work 33 this work estimated 37 37 38 39 40 36 26 41 42 43 33 average this work this work estimated

a

Techniques: EB = ebulliometry; SC = solution calorimetry; T = transpiration method; S = static method; ME = mass effusion-Knudsen; C = calorimetry; TGA = thermogravimetry; E = estimated. bThe molar heat capacities, Ccrp and Clp, and the differences between solid and gaseous phases 754



Article

Table 4. continued (ΔgcrCp) or liquid and gaseous phases (Δgl Cp) required for adjustment to 298.15 K. The ΔgcrCp and Δgl Cp values were estimated by Chickos et al. method20 from the experimental heat capacities Ccrp and Clp, taken from http://webbook.nist.gov/chemistry/ or calculated by Chickos and Acree group-contribution method.21 cThe Ccrp value from ref 23. dEstimated as the sum of vaporization enthalpy of the benzene and the exchange increments (H to Hal). eAverage was calculated using the uncertainty of the experiment as a weighing factor. Values in brackets were disregarded by A A A the averaging. The recommended values are given in bold. fThe Ccrp value from ref 27. gCalculated as the difference Δgl Hmi = ΔgcrHmi − ΔlcrHmi. Ai h g Ai g Ai l Calculated as the sum ΔcrHm = Δl Hm + ΔcrHm. Uncertainties in this table correspond to expanded uncertainties of the mean (0.95 level of confidence).

the literature, additional studies of these compounds have been performed by using the transpiration method. Vapor pressures pi measured by the transpiration method were fitted using the equation10

For some polyhalogen aromatic compounds, it could be more preferable to use carbon tetrachloride as a solvent. It was obtained early17 that enthalpies of solvation of different solutes in carbon tetrachloride and their molar refractions are connected by the following equation: −Δsolv H

A i /CCl4

−1

/kJ·mol

Ai

= 5.44 + 1.109MR

R ln pi = a +

(11)

Combination of eqs 7, 8, and 10 has opened an independent way to get vaporization/sublimation enthalpies via direct calorimetric measurements of ΔsolnHAi/S and indirect values of ΔsolvHAi/S based on molar refractions MRAi

where a and b are adjustable parameters and is the difference of the molar heat capacities of the gaseous and the crystalline phases, respectively. T0 appearing in eq 14 is an arbitrarily chosen reference temperature (which has been chosen to be 298.15 K). Consequently, from eq 14 the expression for the sublimation enthalpy at temperature T = 298.15 K is derived

(12)

Δcrg Hm(T ) = −b + Δcrg CpT

Δcrg H A i /kJ·mol−1 = Δsoln H A i /C6H6/kJ·mol−1 + 6.86 + 1.088MRA i

(14)

ΔgcrCp

Δgl H A i /kJ·mol−1 = Δsoln H A i /C6H6/kJ·mol−1 + 6.86 + 1.088MRA i

⎛T ⎞ b + Δcrg Cp ln⎜ ⎟ T ⎝ T0 ⎠

(15)

Equations 14 and 15 are also valid for the study of the liquid samples. For this case the enthalpy of vaporization is derived from eq 15 by using the appropriate values of Δg1Cp. Values of ΔcrgCp and Δ1gCp have been calculated according to the procedure suggested by Chickos et al.20 We used available experimental isobaric molar heat capacities Ccrp and C1p of aromatic compounds to calculate ΔgcrCp and Δg1Cp or estimated heat capacities by the group-contribution method21 (see Tables 4 to 7). Results on vaporization/sublimation enthalpies available from the literature are usually referred to the average temperature of the studied experimental range or they are adjusted to the reference temperature 298.15 K in a different way. In this work we collected the original vapor pressures and treated them uniformly by using eqs 14 and 15. Compilation of available vaporization/sublimation enthalpies at 298.15 K for 16 halogen-substituted aromatic hydrocarbons is given in Tables 4 to 7. We carefully analyzed the primary references with respect to the purity of samples and experimental conditions. The analysis of purity and quality of data reported in the primary sources has allowed assessing the reliability of available data in order to calculate the averaged values. The selected values are given in Tables 4 to 7 in bold. These values were taken for comparison with the vaporization/sublimation enthalpies derived from the solution calorimetry (see Table 2).

(13)

Solution calorimetry based approach was validated with a carefully evaluated data set of vaporization/sublimation enthalpies of polycyclic aromatic hydrocarbons (PAH).3 It was shown that for the set of PAHs with Δg1HAi and ΔgcrHAi ranging from (73.3 to 213.2) kJ·mol−1 the average deviation of solution calorimetry results was less than 2 kJ·mol−1. Such a good agreement has prompted further exploration of the solution calorimetry approach (based on eqs 12 and 13) toward reliable determination of vaporization and sublimation enthalpies of organic compounds. This approach seems to be especially useful for studies of expensive, thermally unstable, or explosive compounds, because calorimetric measurements are carried out directly at 298.15 K and they are not time and material consuming.

5. RESULTS Enthalpies of solution, ΔsolnHAi/S, measured by solution calorimetry in benzene, and solvation enthalpies, ΔsolvHAi/S, derived using eq 10, for halogen-substituted aromatic hydrocarbons are given in Table 2. These data are referred directly to the reference temperature 298.15 K. So, they could be used for determination of vaporization and sublimation enthalpies at 298.15 K without any adjustments. The dissolution process for all studied systems is endothermic. Though, values of ΔsolnHAi/S of liquid halogen-substituted aromatic hydrocarbons are small in magnitude and close to zero. Hence, energies of intermolecular interactions between molecules of liquid halogen aromatics and benzene are similar. The dissolution process of solid solutes is much more endothermic (see Table 2) due to energy costs on breaking of crystal packing. Standard deviation of ΔsolnHAi/S is less than 1 kJ·mol−1. Enthalpies of solvation are significantly below zero. These values present the overall measure of solute−solvent intermolecular interactions. In order to verify vaporization/sublimation enthalpies for dibromobenzenes and bromo-substituted biphenyls available in

6. DISCUSSION This work is the second part of our project dealing with the reevaluation of the vaporization/sublimation enthalpies of aromatic compounds with the help of a solution calorimetry (SC) based approach. In the first part we have established and tested this approach with the set of reliable sublimation enthalpies for 18 aromatic compounds including phenyl substituted benzenes and naphthalenes and some polycyclic aromatics.3 For the present study we selected a series of 16 aromatic compounds (benzenes, naphthalenes, biphenyls, and anthracenes) containing chlorine, bromine, and iodine 755



Article A

Table 5. Compilation of Data on Enthalpies of Sublimation or Vaporization, Δgcr,lHmi, of Halogen-Substituted Naphthalenes T

compounds Ai 1-bromonaphthalene (l)

1-iodonaphthalene (l)

1,4-dibromonaphthalene (cr) 1,4-dibromonaphthalene (l)

technique

a

T N/A T EB SC Ed T SC Ed ME SC Ee Ed

K range 303 357 295 469

to to to to

Δgcr,lHAmi (Tm/K) −1

kJ·mol

Ccrp (−ΔgcrCp)b)/(Clp(−Δgl Cp)b

Δgcr,lHAmi (298.15 K)

−1

kJ·mol−1

ref

63.9 ± 0.3 66.2 ± 3.0 59.8 ± 1.9 58.2 ± 2.0 63.7 ± 0.9c 64.0 ± 0.2 65.8d 69.9 ± 0.6 70.1 ± 0.4 70.3d 91.3 ± 1.4 94.4 ± 1.1 72.8 ± 1.7e 76.2d

44 26 45 46 average this work estimated 44 this work estimated 1 this work this work estimated

J·mol

K

−1

336 559 359 559

63.9 54.8 58.0 42.7

233.1 (71.2)

303 to 347 298.15

69.9

237.6 (72.4)

297.4 to 322.7 298.15

90.9

203.8 (31.3)

298.15

261.2 (78.5)

a

Techniques: SC = solution calorimetry; T = transpiration method; ME = mass effusion-Knudsen; EB = ebulliometry; E = estimated. bThe molar heat capacities, Ccrp and Clp, and the differences between solid and gaseous phases (ΔgcrCp) or liquid and gaseous phases (Δgl Cp) required for adjustment to 298.15 K. The (ΔgcrCp) and (Δgl Cp) values were estimated by Chickos et al. method20 from the heat capacities Ccrp and Clp calculated by Chickos and Acree group-contribution method.21 cAverage was calculated using the uncertainty of the experiment as a weighing factor. The recommended value is given in bold. dEstimated as the sum of vaporization enthalpy of the naphthalene and the exchange increments (H to Hal). e Calculated as the difference Δgl HAmi = ΔgcrHAmi − ΔlcrHAmi. Uncertainties in this table correspond to expanded uncertainties of the mean (0.95 level of confidence).

calorimetry based approach, ΔgcrHm (298.15 K) = (73.3 ± 0.7) kJ·mol−1, was in good agreement with those obtained from the conventional methods. In contrast to 1,4-dibromobenzene, vaporization enthalpies for 1,2-dibromobenzene and 1,3-dibromobenzene were of a questionable quality.26 As a matter of fact, the comprehensive compilation by Stephenson and Malanowski26 contains vapor pressure data for some aromatic compounds over a wide range of temperature. The origin of the data, purities, and methods of measurements presented there are not clear. In spite of this fact, results from Stephenson and Malanowski26 were also treated using eqs 14 and 15 and values of Δgl Hm (298.15 K) were calculated for the sake of comparison with results from this work. However, the agreement or disagreement with other data in each case should be questionable. For this reason we have performed transpiration experiments with both 1,2- and 1,3dibromobenzenes (see Tables 3 and 4). We also used these new data for validation of the solution calorimetry based approach. As can be seen from Table 4, the solution calorimetry and transpiration results were in good agreement within their experimental uncertainties. Having proved the good ability of the SC-method to reproduce the reliable data from conventional techniques for the dihalogen-substituted benzenes, we have been encouraged to test the SC-method for polychlorobenzenes. The sublimation enthalpy of 1,2,4,5-tetrachlorobenzene was very well established by the calorimetric,36 static, and the mass-loss Knudsen effusion methods35 (see Table 4). Our result from the SC method ΔgcrHm (298.15 K) = (80.9 ± 1.0) kJ·mol−1 was in acceptable agreement with the averaged literature value of ΔcrgHm (298.15 K) = (83.5 ± 0.5) kJ·mol−1. With this coincidence we are optimistic now to resolve the contradiction within the available literature data for hexachlorobenzene. Indeed, having the enormous spread of the available sublimation enthalpies from (60 to 105) kJ·mol−1 for hexachlorobenzene (see Table 4), the SC method seems to be able to provide a reasonable estimate in order to sort out at

substituents on the aromatic rings. Enthalpies of vaporization/ sublimation of these compounds available in the literature from conventional methods were collected and evaluated (see Tables 4 to 7). Five compounds from Tables 4 to 7 have been additionally studied in Rostock using the “conventional” transpiration method in order to ascertain or validate the literature data. Collections of these results were used for attestation of solution calorimetry based approach. Using experimentally measured enthalpies of solution in benzene and molar refractions (see Table 2) values of ΔgcrHAi/Δgl HAi were calculated with the help of eqs 12 and 13 and compared with those from conventional methods. 6.1. Substituted Benzenes. Validation of the solution calorimetry approach for the halogen aromatics has been reasonable to begin with simple dihalogen-substituted benzenes having well established vaporization/sublimation enthalpies (see Table 4). Vapor pressures and vaporization enthalpies of the di-, tri-, and polychlorobenzenes were carefully evaluated in ref 22. Our result from solution calorimetry for 1,3-dichlorobenzene Δgl Hm (298.15 K) = (47.3 ± 0.4) kJ·mol−1 was in excellent agreement with the recommendation Δgl Hm (298.15 K) = (47.7 ± 0.3) kJ· mol−1. The reliable enthalpy of sublimation of 1-bromo-4chlorobenzene ΔgcrHm (298.15 K) = (68.7 ± 0.2) kJ·mol−1 has been evaluated in our previous work24 using our own transpiration experiments and the available literature data. Our result ΔgcrHm (298.15 K) = (67.3 ± 0.4) kJ·mol−1 from the solution calorimetry based approach was in good agreement within the experimental uncertainties. Experimental studies of 1,4-dibromobenzene have been a popular endeavor in the past. In Table 4 we listed eight literature results on sublimation enthalpy for this compound with the average value of ΔgcrHm (298.15 K) = (74.5 ± 1.1) kJ· mol−1. Our own additional result ΔgcrHm (298.15 K) = (73.7 ± 0.6) kJ·mol−1 from transpiration experiments (see Table 3) meets the averaged value. Also the result from the solution 756



Article A

Table 6. Compilation of Data on Enthalpies of Sublimation or Vaporization, Δgcr,lHmi, of Halogen-Substituted Biphenyls Ai 4-bromobiphenyl (cr) 4-bromobiphenyl (l)

4,4′-dibromobiphenyl (cr) 4,4′-dibromobiphenyl (l)

Δgcr,lHAmi( Tm/K)

T

compounds technique

a

T SC N/A Ed Ee T SC Ed Ee

−1


Δgcr,lHAmi (298.15 K)

−1

kJ·mol−1

ref

91.0 ± 0.6 93.7 ± 1.3 (70.0 ± 0.8)c 73.7 ± 1.2d 75.3e 105.5 ± 0.8 106.2 ± 1.7 84.7 ± 1.2d 85.7e

this work this work 33 this work estimated this work this work this work estimated

J·mol ·K

−1

K range

kJ·mol

303.2 to 360.2 298.15 371 to 583

89.9

215.4 (33.1)

56.5

276.7 (82.3)

102.5

238.8 (36.6)

358.1 to 404.4 298.15

304.8 (89.8)

a Techniques: SC = solution calorimetry; T = transpiration method; E = estimated. bThe molar heat capacities, Ccrp and Clp, and the differences between solid and gaseous phases (ΔgcrCp) or liquid and gaseous phases (Δgl Cp) required for adjustment to 298.15 K. The ΔgcrCp and Δgl Cp values were estimated by Chickos et al. method20 from the heat capacities Ccrp and Clp calculated by Chickos and Acree group-contribution method.21 A A A c Values in brackets were disregarded. dCalculated as the difference Δgl Hmi = ΔgcrHmi − ΔlcrHmi. eEstimated as the sum of vaporization enthalpy of the biphenyl and the exchange increments (H to Hal). Uncertainties in this table correspond to expanded uncertainties of the mean (0.95 level of confidence).

Table 7. Compilation of Data on Enthalpies of Sublimation or Vaporization, Δgcr,lHAmi, of Halogen-Substituted Anthracenes T

compounds Ai 9-chloroanthracene (cr) 9-chloroanthracene (l) 9-bromoanthracene (cr)

9-bromoanthracene (l) 9,10-dichloroanthracene (cr) 9,10-dichloroanthracene (l) 9,10-dibromoanthracene (cr) 9,10-dibromoanthracene (l) 2-chloroanthracene (cr) 2-chloroanthracene (l) 2-bromoanthracene (cr) 2-bromoanthracene (l) 1,5-dibromoanthracene (cr) 1,5-dibromoanthracene (l)

technique

a

C SC Ec Ed ME ME SC Ec Ed ME SC Ec Ed ME SC Ec Ed ME Ec Ed ME Ec Ed ME estimatedc estimatedd

A

Δgcr,lHmi( Tm/K)

K range 373.15 298.15

kJ·mol

−1

104.0

Δgcr,lHmi (298.15 K)

−1

kJ·mol−1

ref

106.6 ± 0.9 103.3 ± 0.9 88.8 ± 1.0c 88.5d 102.2 ± 1.0 102.1 ± 0.9 102.2 ± 0.7e 105.9 ± 0.9 87.3 ± 2.6c 91.0d 115.9 ± 4.2 114.7 ± 1.6 101.7 ± 4.2c 96.4d 117.5 ± 3.0 118.2 ± 1.6 102.3 ± 3.0c 101.4d 101.2 ± 2.6 84.8 ± 4.2c 88.5d 103.6 ± 1.2 90.2 ± 1.4c 91.0d 120.0 ± 3.0 98.7 ± 4.2c 101.4d

47 this work this work estimated 48 1 average this work this work estimated 1 this work this work estimated 1 this work this work estimated 1 this work estimated 48 this work estimated 1 this work estimated

J·mol ·K

−1

228.7 (35.0) 303.5 (89.5)

314.8 to 355.0 315.6 to 367.8

100.9 100.5

232.4 (35.6)

298.15 307.3 (90.5) 316 to 376 298.15

114.1

248.3 (38.0) 327.8 (95.8)

359.1 to 391.7 298.15

114.5

A


255.7 (39.1) 335.4(97.8)

331.4 to 371.8

99.3

228.7 (35.0) 303.5 (89.5)

334.8 to 390.4

101.3

232.4 (35.6) 307.3 (90.5)

358.0 to 407.8

116.7

255.7 (39.1) 335.4 (97.8)

a

Techniques: C = calorimetry; SC = solution calorimetry; ME = mass effusion-Knudsen; E = estimated. bThe molar heat capacities, Ccrp and Clp, and the differences between solid and gaseous phases (ΔgcrCp) or liquid and gaseous phases (Δgl Cp) required for adjustment to 298.15 K. The ΔgcrCp and ΔgcrCp values were estimated by Chickos et al. method20 from the heat capacities Ccrp and Clp calculated by Chickos and Acree group-contribution method.21 cCalculated as the difference Δgl HAmi = ΔgcrHAmi − ΔlcrHAmi. dEstimated as the sum of vaporization enthalpy of the anthracene and the exchange increments (H to Hal). eAverage was calculated using the uncertainty of the experiment as a weighing factor. The recommended value is given in bold. Uncertainties in this table correspond to expanded uncertainties of the mean (0.95 level of confidence).

least the misleading results. In this respect, the value ΔgcrHm (298.15 K) = (94.3 ± 0.7) kJ·mol−1 derived in the current study from the solution calorimetry has helped to select results from conventional methods in order to evaluate the average value of ΔgcrHm (298.15 K) = (95.7 ± 1.5) kJ·mol−1 for hexachlorobenzene. This averaged value could be safely

recommended now for the thermochemical calculations. Moreover, this result could serve as a guide value for further development of the TGA method, where hexachlorobenzene is often used for studies of sublimation enthalpies.37 6.2. Substituted Naphthalenes. The validation of the SCmethod for halogen-substituted naphthalenes was performed 757



Article A

Table 8. Compilation of Experimental Data on Enthalpies of Fusion, ΔlcrHmi, of Halogen-Substituted Aromatic Hydrocarbons compounds Ai 1-bromo-4-chlorobenzene

1,4-dibromobenzene

Tm

kJ·mol

337.8 337.9 360.0 360.1 357.7 360.5 412.6 412.2 412.9

hexachlorobenzene

501.9 502.0 505.0

1,4-dibromonaphthalene 4-bromobiphenyl

353.1 337.1 362.1 sum 440.7 379.0 376.6 375.9 485.0 486.5 497.9 497.8 495.7 493.9 482.4

9-bromoanthracene 9,10-dichloroanthracene 9,10-dibromoanthracene 2-chloroanthracene 2-bromoanthracene 1,5-dibromoanthracene

−1

K

1,2,4,5-tetrachlorobenzene

4,4′-dibromobiphenyl 9-chloroanthracene

ΔlcrHAmi (Tm/K)

Ccrp

ΔlcrHAmi (298.15 K)

Clp

−1

J·mol ·K

−1

−1

(J·mol ·k

18.8 ± 1.0 18.7 ± 0.1

146.8

b

183.2

20.0 ± 1.0 20.5 ± 1.0 18.6 ± 0.9 20.4 ± 0.1 20.4 ± 0.7 24.94 24.1 26.34

145.3d

187.0

183.8

228.0

25.0 25.2 23.9 24.7 ± 0.4 21.0 ± 0.3 4.3 ± 0.2e 16.3 ± 0.2 20.6 ± 0.5 28.4 17.3 22.0 ± 0.3 19.2 ± 0.9 27.4 ± 0.1 25.1 ± 0.4 27.0 ± 0.2 28.7 ± 0.5 27.2 ± 1.6 24.1 32.1 ± 1.4

201.3

276.6

203.8 215.4

261.2 276.7

238.8 228.7

304.8 303.5

232.4 248.3

307.3 327.8

255.7

335.4

228.7 232.4 255.7

303.5 307.3 335.4

K−1

kJ·mol−1a

ref

17.4 17.3 17.3 ± 0.7c 17.8 ± 1.0 18.3 ± 1.0 (16.4 ± 0.9) 18.2 ± 0.1 18.2 ± 0.7c 20.1 19.3 21.6 20.3 ± 0.2c 14.5 14.7 13.2 14.2 ± 0.4c 18.5 ± 0.3

52 23 average 53 52 54 27 average 36 55 56 average 57 36 55 average this work this work this work this work 58 59 this work 2 2 this work 2 this work 2 48 2

13.1 ± 0.1 17.3 ± 0.5 20.8 12.9 17.7 ± 0.3 14.9 ± 0.9 16.6 ± 0.1 14.2 ± 1.1 15.2 ± 0.1 17.0 ± 0.4 16.4 ± 1.6 13.4 21.3 ± 1.4

Values of ΔlcrHAmi(Tm/K) were adjusted to the reference temperature 298.15 K using Chickos et al. method20 from the experimental heat capacities Ccrp and Clp, taken from http://webbook.nist.gov/chemistry/ or calculated by Chickos and Acree group-contribution method.21 bThe Ccrp value from ref 23. cAverage was calculated using the uncertainty of the experiment as a weighing factor. Values in brackets were disregarded by the averaging. The recommended values are given in bold. dThe Ccrp value from ref 27. eSolid state phase transition. For 4-bromobiphenyl enthalpy of fusion was calculated as the sum of two peaks. Uncertainties in this table correspond to expanded uncertainties of the mean (0.95 level of confidence). a

(106.2 ± 1.7) kJ·mol−1 for 4,4′-dibromobiphenyl derived from SC approach with the transpiration result ΔgcrHm(298.15 K) = (105.5 ± 0.8) kJ·mol−1 was excellent. 6.4. Substituted Anthracenes. The halogen-substituted anthracenes are apparently a more challenging touch-stone for the SC based approach than the substituted naphthalenes and biphenyls. Fortunately, an extended set of the experimental sublimation enthalpies for chlorine- and bromine-substituted anthracenes (see Table 7) was measured by well established mass loss effusion method combined with the Cahn 2000 microbalance.1 We adjusted experimental sublimation enthalpies of 9-bromoanthracene, as well as of 9,10-dichloro- and 9,10-dibromoanthracene measured by mass loss effusion method to the reference temperature 298.15 K for comparison with results from the solution calorimetry based approach (see Table 7). For all substituted anthracenes the acceptable agreement (within the boundaries of experimental uncertainties) between results determined with the SC-based approach and the conventional effusion method was observed. Summing up, experimental study of 16 selected halogensubstituted aromatic hydrocarbons of different structure has demonstrated that the SC based approach was able to provide

with evaluated experimental data for 1-bromo-, 1-iodo-, and 1,4-dibromonaphthalenes (see Table 5). Consistency of vaporization enthalpies available for monosubstituted naphthalenes was discussed in our previous work.44 Sublimation enthalpy of 1,4-dibromonaphthalene was measured recently.1 As can be seen from Table 5, the values from the SC-method were in agreement within (0.2 to 0.3) kJ·mol−1 with vaporization enthalpies from conventional methods. For 1,4dibromonaphthalene the value ΔgcrHm (298.15 K) = (94.4 ± 1.1) kJ·mol−1 derived in the current study by the SC-method was in agreement within the experimental uncertainties with the value ΔgcrHm (298.15 K) = (91.3 ± 1.4) kJ·mol−1 derived from the mass effusion method.1 6.3. Substituted Biphenyls. We used in this work our own transpiration results for 4-bromobiphenyl (ΔgcrHm(298.15 K) = (91.0 ± 0.6) kJ·mol − 1 ) and 4,4′-dibromobiphenyl (ΔgcrHm(298.15 K) = (105.5 ± 0.8) kJ·mol−1) in order to test the SC method for this class of compounds. Value ΔgcrHm(298.15 K) = (93.7 ± 1.3) kJ·mol−1 for 4-bromobiphenyl derived from the SC approach was in acceptable agreement with the transpiration result ΔgcrHm(298.15 K) = (91.0 ± 0.6) kJ·mol−1. However, the agreement of ΔgcrHm(298.15 K) = 758



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accurate (within of ± 0.5 kJ·mol−1) vaporization/sublimation enthalpies for seven compounds under study. Acceptable accuracy within combined experimental uncertainties of ± (1−3) kJ·mol−1 was observed for the rest. 6.5. Effect of Halogen Heteroatoms on the Vaporization Enthalpies of Aromatic Compounds. Having established the remarkable consistency of the vaporization/ sublimation enthalpies for the set of 16 differently structured aromatic compounds, it seems to be reasonable to use these data to study the effect of halogen heteroatoms on the thermodynamics of polycyclic aromatic compounds. Admittedly,49 experimental sublimation enthalpies, ΔgcrHm, hardly lend themselves for further interpretation or comparison, because each enthalpy of sublimation consists from two contributions: the enthalpy of vaporization, Δgl Hm, and the enthalpy of fusion, Δ1crHm. In contrast, enthalpies of vaporization in most cases readily obey the additive rules,50 or they are able to demonstrate some general regularities, especially for the ortho-, meta-, and para-substituted benzenes.49−51 We collected the available enthalpies of fusion, Δ1crHm, of studied compounds from the literature and measured in this work in Table 8. We used these data to derive enthalpies of vaporization of aromatic compounds in order to reveal their structure− property relations in terms of the group-additivity. In a previous work38 we applied an incremental approach to the chlorine substituted benzenes and phenols. Indeed, the difference between vaporization enthalpies of chlorobenzene and benzene provides the increment ΔH(H → Cl) for substitution of H atom on the benzene ring by Cl group.60 Introduction of the second chlorine atom into the benzene ring produce few additional increments (ortho Cl−Cl), (para Cl− Cl), and (meta Cl−Cl), taking into account the mutual interactions of substituents on the benzene ring. For example, the double Cl-substitution of the benzene implies the following sequence of increments required for interpretation of vaporization enthalpy of polychlorosubstituted benzenes38

quantities of the corresponding increments and corrections. Similar approach is valid49−51 for any kind of poly substitution of the benzene ring (e.g., ΔH(H → Hal) for Hal = Cl, Br, and I in this work). Such a simple substitution pattern could be also applied to naphthalene, biphenyl, or anthracene derivatives provided that increments ΔH(H → Hal) derived from experimental vaporization enthalpies of chloro-, bromo-, and iodo-benzenes are transferrable to the naphthalene, biphenyl, or anthracene units. The diversity of structures presented in Tables 4−7 and the consistency of vaporization enthalpies for 16 halogen-substituted benzenes, naphthalenes, biphenyls, and anthracenes have helped to check the generalization of the ΔH(H → Hal) increments for aromatic compounds. We used the experimental enthalpies Δgl Hm(298.15 K) of benzene (33.9 ± 0.1) kJ·mol−1,61 chlorobenzene (41.8 ± 0.3) kJ·mol−1,60 bromobenzene (44.5 ± 0.1) kJ·mol−1,62 and iodobenzene (48.9 ± 0.5) kJ·mol−1 62 and calculated the following increments ΔH(H → Cl) = 7.9 kJ·mol−1, ΔH(H → Br) = 10.4 kJ·mol−1, and ΔH(H → I) = 14.9 kJ·mol−1 for calculation vaporization enthalpies of aromatic compounds (see Table S5). We adjusted eq 16 for each series of aromatic compounds. Using experimental vaporization enthalpies Δgl Hm(298.15 K)61 of the basic unities: naphthalene (55.4 ± 1.4) kJ·mol−1, biphenyl (64.9 ± 1.3) kJ·mol−1, and anthracene (80.6 ± 0.8) kJ· mol−1 together with the appropriate increment ΔH(H → Hal), vaporization enthalpies of all 16 species listed in Tables 4−7 have been estimated (see footnotes in Tables 4−7). Comparison of the experimental (from conventional method or from solution calorimetry) and estimated values has reveled that the average deviation of experimental and calculated vaporization enthalpies does not exceed 1.0 kJ·mol−1 for dihalogen-substituted benzenes, as well as for mono- and dihalogen-substituted naphthalenes and biphenyls. Following, the enthalpies of vaporization of the 1,3 and 1,4 substituted benzenes can be predicted with sufficient accuracy using the reduced eq 16 with only increments ΔH(H → Hal) and by neglecting all mutual (Hal−Hal) interactions. Apparently, the mutual interactions of the chlorine and bromine substituents in meta and para positions on the benzene ring are less than 1 kJ· mol−1 and these interactions could be neglected within the boundaries of the experimental uncertainties. The interaction of chlorine substituents in the 1,2 position is apparently also weak (about 1 kJ·mol−1) and could be neglected for the simplicity of calculations.24 This simplification still keeps true for two (ortho Cl−Cl) contributions within the 1,2,3,5-tetrachlorobenzene, where the experimental and estimated enthalpies of vaporization are in close agreement (see Table 4). However, it could be expected that with increasing of number of ortho substituents on the aromatic rings the accumulation of the neglected interactions decrease the accuracy of estimation. Surprisingly, this expectation was not fullfield, because the experimental vaporization enthalpies and those estimated by eq 16 for hexachlorobenzene were in excellent agreement (see Table 4). Comparison of the experimental and estimated enthalpies of vaporization of the chlorine and bromine substituted anthracenes exhibits an agreement within (2 to 4) kJ·mol−1 which is quite acceptable taking into account the similar range of uncertainties specific for experimental data on anthracenes. Thus, the reduced eq 16 with only ΔH(H → Hal) could be recommended for reliable assessment of anthracenes vaporization enthalpies. In order to be more confident with this recommendation, we have involved an additional experimental

The general formula for calculation of vaporization enthalpy of any polychlorobenzene (ClB) at 298.15 K was as follows: Δgl Hm(ClB) = Δgl Hm(B) + naΔH(H → Cl) + nb(ortho Cl − Cl) + nc(para Cl − Cl) + nd(meta Cl − Cl) (16)

Δgl Hm(B)

where is enthalpy of vaporization of benzene; ΔH(H → Cl) is an increment of H → Cl substitutions on the benzene ring. The mutual interactions of the Cl atoms were taken into account through the three types of corrections in ortho, para, and meta positions on the benzene ring. na, nb, nc, and nd are the 759



Article

data for 2-chloroanthracene,1 2-bromoanthracene,48 and 1,5dibromoanthracene1 reported recently (see Table 7). As can be seen from this table the agreement of the experimental and estimated enthalpies of vaporization for these additional substituted anthracenes was also within the experimental uncertainties of (2 to 4) kJ·mol−1 proving the validity of the reduced eq 16. The reduced eq 16 was also tested for iodine containing compounds. Estimated and experimental values for 1-iodonaphthalene were indistinguishable within experimental uncertainties, proving validity of the suggested additive procedure for this class of aromatic compounds.

(4) Zaitseva, K. V.; Varfolomeev, M. A.; Solomonov, B. N. Thermodynamic Functions of Hydrogen Bonding of Amines in Methanol Derived from Solution Calorimetry Data and Headspace Analysis. Thermochim. Acta 2012, 535, 8−16. (5) Sabbah, R.; An, X. W.; Chickos, J. S.; Leitao, M. L. P.; Roux, M. V.; Torres, L. A Reference Materials for Calorimetry and Differential Thermal Analysis. Thermochim. Acta 1999, 331, 93−204. (6) Wadso, I.; Goldberg, R. N. Standards in Isothermal Microcalorimetry (IUPAC Technical Report). Pure Appl. Chem. 2011, 73, 1625−1639. (7) Sanyal, N. K.; Ahmad, P.; Dixit, L. Quantum Mechanical Treatment of Bond and Molecular Polarizabilities of Some Substituted Hydrocarbons with Ring and Chain Structures. J. Phys. Chem. 1973, 77, 2552−2556. (8) Le Fèvre, R. J. W. Molecular Refractivity and Polarizability. Adv. Phys. Org. Chem. 1965, 3, 1−90. (9) Kemp, M. L.; Le Fèvre, R. J. W. 626. Molecular Polarisability. Carbon−halogen Bond Polarisabilities in Some p-Disubstituted Benzenes. J. Chem. Soc. 1965, 3463−3467. (10) Kulikov, D.; Verevkin, S. P.; Heintz, A. Enthalpies of Vaporization of a Series of Aliphatic Alcohols: Experimental Results and Values Predicted by the ERAS-Model. Fluid Phase Equilib. 2001, 192, 187−207. (11) Ziganshin, M. A.; Bikmukhametova, A. A.; Gerasimov, A. V.; Gorbatchuk, V. V.; Ziganshina, S. A.; Bukharaev, A. A. The Effect of Substrate and Air Humidity on Morphology of Films of L-leucyl-Lleucine Dipeptide. Prot. Met. Phys. Chem. 2014, 50, 49−54. (12) Heintz, A.; Kulikov, D. V.; Verevkin, S. P. Thermodynamic Properties of Mixtures Containing Ionic Liquids. 1. Activity Coefficients at Infinite Dilution of Alkanes, Alkenes, and Alkylbenzenes in 4-Methyl-n-butylpyridinium Tetrafluoroborate Using Gas− Liquid Chromatography. J. Chem. Eng. Data 2001, 46, 1526−1529. (13) Anthony, J. L.; Maginn, E. J.; Brennecke, J. F. Solution Thermodynamics of Imidazolium-Based Ionic Liquids and Water. J. Phys. Chem. B 2001, 105, 10942−10949. (14) Solomonov, B. N.; Antipin, I. S.; Gorbatchuk, V. V.; Konovalov, A. I. Solvation of Organic Compounds in Non-Polar Media. Dokl. Akad. Nauk SSSR 1979, 247, 405−408. (15) Solomonov, B. N.; Antipin, I. S.; Novikov, V. B.; Konovalov, A. I. Solvation of Organic Compounds in Cyclohexane. New Method of Estimating Heats of Evaporation of Substances. Zh. Obshch. Khim. 1982, 52, 2681−2688. (16) Solomonov, B. N.; Novikov, V. B. Solution Calorimetry of Organic Nonelectrolytes as a Tool for Investigation of Intermolecular Interactions. J. Phys. Org. Chem. 2008, 21, 2−13. (17) Solomonov, B. N.; Konovalov, A. I.; Novikov, V. B.; Gorbachuk, V. V.; Neklyudov, S. A. Solvation of Organic Compounds Determination of an Enthalpy of the Diluted Substance Specific Interaction with a Solvent. Zh. Obshch. Khim. 1985, 55, 1889−1906. (18) Solomonov, B. N.; Konovalov, A. I.; Novikov, V. B.; Vedernikov, A. N.; Borisover, M. D.; Gorbachuk, V. V.; Antipin, I. S. Solvation of Organic Compounds. Molecular Refraction, Dipole Moment and Enthalpy of Solution. Zh. Obshch. Khim. 1984, 54, 1622−1632. (19) Mato, M. M.; Balseiro, J.; Salgado, J.; Jiménez, E.; Legido, J. L.; Piñeiro, M. M.; Paz Andrade, M. I. Excess Molar Enthalpies and Excess Molar Volumes of the Ternary System 1,2-Dichlorobenzene + Benzene + Hexane at 298.15 K. J. Chem. Eng. Data 2002, 47, 4−7. (20) Chickos, J. S.; Hosseini, S.; Hesse, D. G.; Liebman, J. F. Heat Capacity Corrections to a Standard State: a Comparison of New and Some Literature Methods for Organic Liquids and Solids. Struct. Chem. 1993, 4, 271−277. (21) Acree, W. E.; Chickos, J. S. Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds. Sublimation, Vaporization and Fusion Enthalpies From 1880 to 2010. J. Phys. Chem. Ref. Data 2010, 39 (043101), 1−942. (22) Rohac, V.; Ruzicka, V.; Ruzicka, K.; Polednicek, M.; Aim, K.; Jose, J.; Zabransky, M. Recommended Vapour and Sublimation Pressures and Related Thermal Data for Chlorobenzenes. Fluid Phase Equilib. 1999, 157, 121−142.

7. CONCLUSION We have demonstrated that the solution calorimetry based approach can be used for a quick and reliable appraisal of vaporization/sublimation enthalpies of organic compounds. In this work it was shown that average deviation of Δgl Hm and ΔgcrHm values for 16 halogen-substituted aromatic hydrocarbons determined by SC method from the results of conventional methods is less than 2 kJ·mol−1. This method is based on solution enthalpies determined calorimetrically and on solvation enthalpies calculated from auxiliary molar refractions derived from experiments. It has turned out that the SC based approach becomes a valuable thermochemical option for evaluation of vaporization/sublimation data, where experimental results are absent or in disarray. The solution calorimetry based approach is highly suitable for unstable compounds and it provides results directly at the reference temperature 298.15 K without need for conventional methods temperature adjustments.

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ASSOCIATED CONTENT

* Supporting Information S

Additional tables, figures, and experimental results. This material is available free of charge via the Internet at http:// pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (solution calorimetry experiments (Kazan) and correlations). *E-mail: [email protected] (vaporization/sublimation experiments (Rostock) and data evaluation). Funding

This work has been performed according to the Russian Government Program of Competitive Growth of Kazan Federal University. Notes

The authors declare no competing financial interest.

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REFERENCES

(1) Goldfarb, J. L.; Suuberg, E. M. The Effect of Halogen HeteroAtoms on the Vapor Pressures and Thermodynamics of Polycyclic Aromatic Compounds Measured via the Knudsen Effusion Technique. J. Chem. Thermodyn. 2008, 40, 460−466. (2) Goldfarb, J. L.; Külaots, I. Melting Points and Enthalpies of Fusion of Anthracene and Its Heteroatomic Counterparts. J. Therm. Anal. Calorim. 2010, 102, 1063−1070. (3) Solomonov, B. N.; Varfolomeev, M. A.; Nagrimanov, R. N.; Novikov, V. B.; Zaitsau, D. H.; Verevkin, S. P. Solution Calorimetry as a Complementary Tool for the Determination of Enthalpies of Vaporization and Sublimation of Low Volatile Compounds at 298.15 K. Thermochim. Acta 2014, 589, 164−173. 760



Article

(23) Van Miltenburg, J. C.; Oonk, H. A. J.; van den Berg, G. J. K. Low-Temperature Heat Capacities and Derived Thermodynamic Functions of Para-Substituted Halogen Benzenes. 1. p-Chlorobromobenzene and p-Chloroiodobenzene. J. Chem. Eng. Data 2000, 45, 704− 708. (24) Verevkin, S. P.; Emel’yanenko, V. N.; Varfolomeev, M. A.; Solomonov, B. N.; Zherikova, K. V.; Melkhanova, S. V. Thermochemistry of Di-Halogen-Substituted Benzenes: Data Evaluation using Experimental and Quantum Chemical Methods. J. Phys. Chem. B 2014, 118, 14479−14492. (25) Dreisbach, R. R.; Shrader, S. A. Vapor Pressure-Temperature Data on Some Organic Compounds. Ind. Eng. Chem. 1949, 41, 2879− 2880. (26) Stephenson, R. M.; Malanowski, S. Handbook of the Thermodynamics of Organic Compounds; Elsevier: New York, 1987. (27) Van der Linde, P. R.; van Miltenburg, J. C.; van den Berg, G. J. K.; Oonk, H. A. J. Low-Temperature Heat Capacities and Derived Thermodynamic Functions of 1,4-Dichlorobenzene, 1,4-Dibromobenzene, 1,3,5-Trichlorobenzene, and 1,3,5-Tribromobenzene. J. Chem. Eng. Data 2005, 50, 164−172. (28) Oonk, H. A. J.; van Genderen, A. C. G.; Blok, J. G.; van der Linde, P. R. Vapour Pressures of crystalline and liquid 1,4-dibromoand 1,4-dichlorobenzene; lattice energies of 1,4-dihalobenzenes. Phys. Chem. Chem. Phys. 2000, 2, 5614−5618. (29) De Kruif, C. G.; van Genderen, A. C. G.; Bink, J. C. W. G.; Oonk, H. A. J. Properties of Mixed Crystalline Organic Material Prepared by Zone Levelling II. Vapour Pressures and Excess Gibbs Energies of (p-Dichlorobenzene + p-Dibromobenzene). J. Chem. Thermodyn. 1981, 13, 457−463. (30) Walsh, P. N.; Smith, N. O. Sublimation Pressure of α-pDichloro-β-p-Dichloro, and p-Dibromo-, and p-Bromochlorobenzene. J. Chem. Eng. Data 1961, 6, 33−35. (31) Stern, J. H.; Gregory, N. W. Vaporization Characteristics of pDibromobenzene. J. Phys. Chem. 1959, 63, 556−559. (32) Jones, A. H. Sublimation Pressure Data for Organic Compounds. J. Chem. Eng. Data 1960, 5, 196−200. (33) Stull, D. R. Vapor Pressure of Pure Substances. Organic and Inorganic Compounds. Ind. Eng. Chem. 1947, 39, 517−540. (34) Van der Linde, P. R. Ph.D. Thesis, Utrecht University: Utrecht, The Netherlands, 1992. (35) Blok, J. G.; van Genderen, A. C. G.; van der Linde, P. R.; Oonk, H. A. J. Vapour Pressures of Crystalline 1,2,4,5-Tetrachlorobenzene, and Crystalline and Liquid 1,3,5-Trichlorobenzene and 1,2,4,5Tetramethylbenzene. J. Chem. Thermodyn. 2001, 33, 1097−1106. (36) Sabbah, R.; An, X. W. Etude Thermodynamique des Chlorobenzenes. Thermochim. Acta 1991, 179, 81−88. (37) Vecchio, S. Vapor Pressures and Standard Molar Enthalpies, Entropies and Gibbs Energies of Sublimation of Two Hexachloro Herbicides Using a TG Unit. Thermochim. Acta 2010, 499, 27−33. (38) Verevkin, S. P.; Emel’yanenko, V. N.; Klamt, A. Thermochemistry of Chlorobenzenes and Chlorophenols: Ambient Temperature Vapor Pressures and Enthalpies of Phase Transitions. J. Chem. Eng. Data 2007, 52, 499−510. (39) Wania, F.; Shui, W. Y.; Mackay, D. Measurement of the Vapor Pressure of Several Low-Volatility Organochlorine Chemicals at Low Temperatures with a Gas Saturation Method. J. Chem. Eng. Data 1994, 39, 572−577. (40) Liu, K.; Dickhut, R. M. Saturation Vapor Pressures and Thermodynamic Properties of Benzene and Selected Chlorinated Benzenes at Environmental Temperatures. Chemosphere 1994, 29, 581−589. (41) Rordorf, B. F.; Sarna, L. P.; Webster, G. R. B. Vapor Pressure Determination for Several Polychlorodioxins by Two Gas Saturation Methods. Chemosphere 1986, 15, 2073−2076. (42) Farmer, W. J.; Yang, M. S.; Letey, J.; Spencer, W. F. Hexachlorobenzene: Its Vapor Pressure and Vapor Phase Diffusion in Soil. Soil Sci. Soc. Am. J. 1980, 44, 676−680.

(43) Sears, G. W.; Hopke, E. R. Vapor Pressures of Naphthalene, Anthracene and Hexachlorobenzene in a Low Pressure Region. J. Am. Chem. Soc. 1949, 71, 1632−1634. (44) Verevkin, S. P. Vapor Pressures and Enthalpies of Vaporization of a Series of 1- and 2-Halogenated Naphthalenes. J. Chem. Thermodyn. 2003, 35, 1237−1251. (45) Urbani, M.; Gigli, R.; Piacente, V. Vaporization Study of AlphaBromonaphthalene. J. Chem. Eng. Data 1980, 25, 97−100. (46) Hon, H. C.; Singh, R. P.; Kudchadker, A. P. Vapor PressureBoiling Point Measurements of Five Organic Substances by Twin Ebulliometry. J. Chem. Eng. Data 1976, 21, 430−431. (47) Kiselev, V. D.; Vaisman, E. A.; Solomonov, B. N.; Konovalov, A. I. Enthalpies of Sublimation and Solvation of 9,10- Substitutions of Anthracene. Zh. Obshch. Khim. 1985, 55, 1965−1969. (48) Fu, J.; Suuberg, E. M. Thermochemical and Vapor Pressure Behavior of Anthracene and Brominated Anthracene Mixtures. Fluid Phase Equilib. 2013, 342, 60−70. (49) Emel’yanenko, V. N.; Strutynska, A.; Verevkin, S. P. Enthalpies of Formation and Strain of Chlorobenzoic Acids from Thermochemical Measurements and from ab Initio Calculations. J. Phys. Chem. A 2005, 109, 4375−4380. (50) Cohen, N. Revised Group Additivity Values for Enthalpies of Formation (at 298 K) of Carbon-Hydrogen and Carbon-HydrogenOxygen Compounds. J. Phys. Chem. Ref. Data 1996, 25, 1411−1481. (51) Emel’yanenko, V. N.; Verevkin, S. P. Enthalpies of Formation and Substituent Effects of ortho-, meta-, and para-Aminotoluenes from Thermochemical Measurements and from Ab Initio Calculations. J. Phys. Chem. A 2005, 109, 3960−3966. (52) Narbutt, J. Die Spezifischen Warmen und Schmelzwarmen der Dichloro-, Chlorbrom-, Dibrom-, Bromjod-, und Dijodbenzole. I. Z. Elektrochem. 1918, 24, 339−342. (53) Ueberreiter, K.; Orthmann, H.-J. Specifische Wär me, spezifisches Volumen, Temperatur- und Wärme-leittähigkeit einiger disubstituierter Benzole und polycyclischer Systeme. Z. Natursforsch. 1950, 5a, 101−108. (54) Kuramochi, H.; Maeda, K.; Kawamoto, K. Measurements of Water Solubilities and 1-Octanol/Water Partition Coefficients and Estimations of Henry’s Law Constants for Brominated Benzenes. J. Chem. Eng. Data 2004, 49, 720−724. (55) Acree, W. E., Jr. Thermodynamic Properties of Organic Compounds: Enthalpy of Fusion and Melting Point Temperature Compilation. Thermochim. Acta 1991, 189, 37−56. (56) Mondieig, D.; Cuevas-Kiarte, M. A.; Haget, Y. Polymorphisme du Tetrachloro-1,2,4,5-Benzene et du Tetrabromo-1,2,4,5-Benzene. J. Therm. Anal. 1989, 35, 2491−2500. (57) Sabbah, R.; El Watik, L. New Reference Materials for the Calibration (Temperature and Energy) of Differential Thermal Analysers and Scanning Calorimeters. J. Therm. Anal. 1992, 38, 855−863. (58) Rai, R. N.; Reddi, R. S. B. Thermal, Solid−Liquid Equilibrium, Crystallization, and Microstructural Studies of Organic Monotectic alloy: 4,4′-Dibromobiphenyl−Succinonitrile. Thermochim. Acta 2009, 496, 13−17. (59) Goursot, P.; Girdhar, H. L.; Westrum, E. F., Jr. Thermodynamics of Polynuclear Aromatic Molecules. III. Heat Capacities and Enthalpies of Fusion of Anthracene. J. Phys. Chem. 1970, 74, 2538− 2541. (60) Verevkin, S. P.; Emel’yanenko, V. N.; Varfolomeev, M. A.; Solomonov, B. N.; Zherikova, K. V. Enthalpies of Vaporization of a Series of the Fluoro- and Chloro-Substituted Benzenes. Fluid Phase. Equilib. 2014, 380, 67−75. (61) Roux, M. V.; Temprado, M.; Chickos, J. S.; Nagano, Y. Critically Evaluated Thermochemical Properties of Polycyclic Aromatic Hydrocarbons. J. Phys. Chem. Ref. Data 2008, 37, 1885−1996. (62) Verevkin, S. P.; Sazonova, A. Yu.; Emel’yanenko, V. N.; Zaitsau, D. H.; Varfolomeev, M. A.; Solomonov, B. N.; Zherikova, K. V. Thermochemistry of Halogen-Substituted Methylbenzenes. J. Chem. Eng. Data 2015, 60, 89−103.

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