Vapor Pressures and Thermophysical Properties of Ethylene

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX-XXX

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Vapor Pressures and Thermophysical Properties of Ethylene Carbonate, Propylene Carbonate, γ‑Valerolactone, and γ‑Butyrolactone

Václav Pokorný, Vojtěch Štejfa, Michal Fulem, Ctirad Č ervinka, and Květoslav Růzǐ čka* Department of Physical Chemistry, University of Chemistry and Technology, Prague, Technická 5, CZ-166 28 Prague 6, Czech Republic S Supporting Information *

ABSTRACT: In this work, a thermodynamic study of four important industrial solvents, ethylene carbonate (CAS RN: 96-491), propylene carbonate (CAS RN: 108-32-7), γ-valerolactone (CAS RN: 108-29-2), and γ-butyrolactone (CAS RN: 96-48-0), is presented. The vapor pressure measurements were performed by static method using two apparatuses in a combined temperature interval (238−363) K. Heat capacities of condensed phases were measured by Tian−Calvet calorimetry in the temperature interval (262−358) K. The phase behavior of ethylene carbonate and γ-valerolactone was investigated by a heat-flux DSC from 183−303 and 328 K, respectively. Ideal-gas thermodynamic properties were calculated using the methods of statistical thermodynamics based on calculated fundamental vibrational frequencies and molecular structure data. A consistent thermodynamic description of all involved properties (calculated ideal-gas heat capacities and experimental data on vapor pressures, condensed phase heat capacities, and vaporization enthalpies) was achieved by their simultaneous correlation.

1. INTRODUCTION The four compounds selected for the present study belong to industrially important chemicals produced on a large scale. Ethylene carbonate, propylene carbonate, and γ-butyrolactone are extensively used as solvents in nonaqueous liquid electrolytes for lithium-based batteries1−6 as well as industrial solvents and/ or precursors for other products. γ-Valerolactone, besides its usage as solvent, is considered as a sustainable (biomass derived) fuel additive.7 Despite these facts, there seems to be a significant disagreement among various vapor pressure data sets for ethylene carbonate, propylene carbonate, and γ-valerolactone. Therefore, the objective of this work was to establish reliable vapor pressure data for the above-mentioned four compounds in the technologically important temperature interval covering ambient temperatures by (i) analyzing the literature vapor data and their thermodynamic consistency with calorimetrically determined vaporization enthalpies and heat capacities of condensed phases and ideal gas, (ii) performing new vapor pressure and heat capacity measurements for ethylene carbonate, propylene carbonate, and γ-valerolactone, for which inconsistencies were revealed among thermodynamically linked © XXXX American Chemical Society

properties, (iii) performing new advanced calculations of idealgas thermodynamic properties by combining quantum chemical and statistical thermodynamics calculations, and (iv) performing the simultaneous correlation of selected vapor pressure and related thermal data (SimCor method described previously;8 for reader’s convenience, the description is repeated in the Supporting Information). In the case of ethylene carbonate, the crystal heat capacities and enthalpy of fusion were measured and used for establishing the thermodynamically consistent sublimation enthalpies and pressures.

2. EXPERIMENTAL SECTION 2.1. Materials. Sample characteristics are summarized in Table 1. The compounds were studied without further purification. Propylene carbonate and γ-valerolactone were delivered in bottles with a membrane preventing contact with air humidity; ethylene carbonate was stored at 313 K (i.e., above Received: June 23, 2017 Accepted: November 6, 2017

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DOI: 10.1021/acs.jced.7b00578 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

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Table 1. Sample Descriptions compound

CAS number

supplier

ethylene carbonate propylene carbonate γ-valerolactone

96-49-1 108-32-7 108-29-2

TCI Sigma-Aldrich Sigma-Aldrich

mole fraction purity 0.999a 0.9994a >0.999a

water mass fraction

0.9999b 0.9994b 0.9991b

2.4 × 10−5d 1.2 × 10−4d 8.6 × 10−5d

nospa,c 1 × 10−5a nospa,c

a From certificate of analysis supplied by the manufacturer. bGas−liquid chromatography analysis by Hewlett-Packard 6890 gas chromatograph equipped with column HP-1, length 25 m, film thickness 0.52 μm, i.d. 0.30 mm, and FID detector. cnosp stands for not specified. dKarl Fischer analysis by Methrom 831.

Table 2. Experimental Vapor Pressures p for Ethylene Carbonate, Propylene Carbonate, and γ-Valerolactone T/K

pa/Pa

T/K

pa/Pa

T/K

pa/Pa

T/K

pa/Pa

b

272.67 272.74 272.80 272.88 278.16 278.16 278.17 283.05 283.05 283.05

0.25 0.26 0.25 0.25 0.51 0.49 0.49 0.88 0.86 0.88

292.98 292.98 293.00 297.99 297.99 297.99 298.00 302.92 302.92 302.92 307.84 307.84 307.84 307.85 312.82 312.82 312.82 312.83

3.40 3.38 3.41 5.18 5.20 5.21 5.20 7.80 7.83 7.83 11.53 11.58 11.59 11.59 16.92 16.92 16.93 16.94

278.19 278.37 278.37 278.39 283.31 283.31 283.32 283.32 288.19 288.19 288.20

1.32 1.33 1.33 1.33 2.14 2.14 2.14 2.14 3.32 3.32 3.33

ethylene carbonate (crystal) 283.05 0.87 288.10 1.54 288.10 1.52 288.10 1.51 288.10 1.52 293.01 2.58 293.01 2.56 293.02 2.54 293.02 2.56 297.98 4.31 ethylene carbonate (liquid)b 317.76 24.35 317.77 24.35 317.77 24.33 322.65 34.39 322.65 34.37 322.66 34.43 327.75 48.74 327.75 48.75 327.76 48.72 327.77 48.78 332.80 67.96 332.80 67.98 332.80 67.97 337.66 92.61 337.67 92.59 337.67 92.67 337.68 92.75 342.68 126.03 propylene carbonate (liquid)b 307.94 16.98 307.95 16.94 307.95 16.96 312.97 24.70 312.97 24.72 312.98 24.74 312.99 24.79 317.91 35.29 317.92 35.30 317.92 35.33 317.92 35.36

T/K

pa/Pa

T/K

pa/Pa

352.55 352.58 352.59 357.59 357.59 357.59 357.60 362.51 362.53 362.53 362.53

309.59 310.20 310.30 407.81 407.83 407.82 407.94 528.98 529.31 529.45 529.51

283.14 288.14 288.14 288.15 293.14 293.14 293.13 298.14 298.14 298.14 303.13 303.13 303.13 308.14 308.14 308.14

13.95 20.98 20.97 21.00 31.11 31.09 31.06 45.32 45.31 45.32 65.01 65.02 65.02 92.12 92.11 92.11

b

297.98 297.98 297.99 302.82 302.82 302.82 302.83 307.84 307.85 307.85

4.30 4.31 4.31 7.02 6.97 7.02 7.01 11.31 11.33 11.30

342.69 342.69 342.70 347.63 347.65 347.66 352.45 352.46 352.46 352.47 352.49 357.49 357.50 357.50 357.50 362.62 362.63 362.63

126.14 126.20 126.20 169.45 169.54 169.63 223.46 223.58 223.65 223.84 224.14 296.02 296.13 296.24 296.31 390.59 390.64 390.67

337.84 337.84 337.85 342.82 342.83 342.84 342.84 347.69 347.69 347.70 347.70

131.08 131.17 131.21 177.04 177.15 177.29 177.24 235.33 235.33 235.36 235.44

288.22 293.12 293.14 293.15 293.15 298.10 298.10 298.11 298.12 303.01 303.01 303.03 307.94

3.32 5.11 5.12 5.14 5.11 7.78 7.78 7.78 7.77 11.58 11.55 11.56 17.01

238.09 238.08 238.07 243.07 243.06 243.06 248.13 248.13 248.13 253.14 253.14 253.14 258.15 258.15 258.15 263.14

0.15 0.15 0.14 0.26 0.26 0.26 0.48 0.48 0.48 0.82 0.82 0.82 1.38 1.38 1.38 2.28

propylene carbonate (liquid) 322.90 49.93 322.92 49.96 322.92 50.02 322.92 50.00 327.80 69.36 327.81 69.35 327.81 69.32 327.81 69.38 332.89 96.34 332.89 96.35 332.91 96.43 332.92 96.45 337.83 131.07 γ‑valerolactone (liquid)c 263.14 2.28 263.14 2.28 268.14 3.69 268.14 3.69 268.14 3.69 273.15 5.86 273.15 5.86 273.14 5.86 273.64 6.12 273.64 6.12 273.63 6.12 278.14 9.12 278.14 9.12 278.14 9.12 283.14 13.96 283.14 13.95

a

Values are reported with one digit more than is justified by the experimental uncertainty to avoid round-off errors in calculations based on these results. bMeasured with STAT8 apparatus; the standard uncertainty in the sample temperature measurements is u(T) = 0.01 K, and combined expanded uncertainty (0.95 level of confidence, k = 2) in the vapor pressure measurements is Uc(p) = 0.01 p + 0.05 Pa. cMeasured with STAT6 apparatus; the standard uncertainty in the sample temperature measurements is u(T) = 0.02 K, and combined expanded uncertainty (0.95 level of confidence, k = 2) in the vapor pressure measurements is Uc(p) = 0.005 p + 0.05 Pa.

apparatuses were previously described in detail in this journal,9,10 we present here only their operating pressure range (0.5−1333 Pa for both apparatuses), temperature ranges (233−313 K for STAT6 and 273−368 K for STAT8), and the resulting combined expanded (0.95 level of confidence) uncertainty of vapor pressure measurements, which is adequately described by the

its normal melting temperature) over 4 Å molecular sieves for several weeks prior to measurements. All three samples were treated in a dry nitrogen atmosphere (drybox MBraun LabStar). No new measurements were needed for γ-butyrolactone. 2.2. Vapor Pressure Measurements. The vapor pressure measurements were performed using the static method with two apparatuses internally denoted as STAT6 and STAT8. As these B



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expression Uc(p/Pa) = 0.005(p/Pa) + 0.05 and Uc(p/Pa) = 0.01(p/Pa) + 0.05 for STAT6 and STAT8, respectively. 2.3. Heat Capacity Measurements. The Tian−Calvet calorimeter (SETARAM μDSC IIIa, France) was used for the heat capacity determination in the temperature range from 262 to 358 K (ethylene carbonate was measured only up to 324 K due to its higher volatility). Heat capacities were obtained using continuous method.11 A detailed description of the calorimeter and its calibration was published previously;12 the expanded uncertainty (0.95 level of confidence) of the heat capacity measurements is estimated to be Uc(Cp) = 0.01 Cp. The correction for sample vaporization according to Hoge13,14 was not applied as it would be much smaller than the experimental uncertainty of our measurements. The saturation molar heat capacities Csat,m obtained in this work are identical to 1 in the isobaric molar liquid phase heat capacities Cp,m temperature range studied as it is not necessary to make a clear distinction between C1p,m along the saturation curve and Csat,m below 0.9 Tb, where Tb is the normal boiling temperature.14 For the correlation of heat capacity data, a polynomial equation was used 1 Cp,m

R

n

=

⎛ T ⎞i ⎟ 100 ⎠

∑ Ai+ 1⎜⎝ i=0

Table 3. Overview of the Literature Vapor Pressure Data for Ethylene Carbonate, Propylene Carbonate, γ-Valerolactone, and γ-Butyrolactonea,b ref Choi and Jonich18 Verevkin et al.19 this work (STAT8) Petrov and Sandler20 Hong et al.21 Chernyak and Clements22 Chernyak and Clements22 Verevkin et al.19 Dougassa et al.23 this work (STAT8) Choi and Jonich18 Petrov and Sandler20 Hong et al.21 Wilson et al.24 Chernyak and Clements22 Nasirzadeh et al.25 Verevkin et al.19 Mathuni et al.26 Dougassa et al.23 this work (STAT8)

(1)

where R is the molar gas constant (R = 8.3144598 J·K−1· mol−115). 2.4. Phase Behavior Measurements. The phase behavior of ethylene carbonate and γ-valerolactone was investigated from 183 to 303 and 328 K, respectively, with a heat-flux differential scanning calorimeter (TA Q1000, TA Instruments, United States) using the continuous method with a heating rate of 5 K min−1. The sample load of 5−10 mg was determined by an analytical balance DENVER TB215D-A that had a readability of 0.01 mg and was periodically calibrated. Prior to the measurements, a thorough temperature and enthalpy calibration of the calorimeter was performed using water, gallium, naphthalene, indium, and tin. Standard uncertainty associated with the mean value of enthalpy of phase transition is u(Δ1s Hm) = 0.3 kJ mol−1 and u(T) = 0.3 K.

Schuette and Thomas27 (isoteniscope) Schuette and Thomas27 (ebulliometry) Horváth et al.28 Emel’yanenko et al.29 Klajmon et al.7 Zaitseva et al.30 Havasi et al.31 Havasi et al.31 this work (STAT6)

3. RESULTS AND DISCUSSION 3.1. Vapor Pressures. The vapor pressure measurements were performed in the temperature interval (238−308) K using the STAT6 apparatus and in (273−363) K using the STAT8 apparatus, respectively. The measurements were performed by varying the temperature at random to detect systematic errors caused by insufficient degassing of the sample. The experiments were carried out repeatedly at selected temperatures. When the pressure did not change with the number of measuring cycles, the sample was considered completely degassed, and the final set of data was recorded. The experimental vapor pressures obtained in this work are given in Table 2. A summary of the performed vapor pressure experiments is presented in Table 3 along with the literature data. For each compound, the data listed in Table 3 were first converted to ITS 90 according to the procedure reported by Goldberg and Weir16 and then critically assessed using the arc representation17 which allowed us to reject obvious outliers (see Figures 1−4). Because only differences among various vapor pressure data sets are highlighted by the arc method, the SimCor method was subsequently used to decide which data should be retained or

McKinley and Copes32 Yevstropov et al.33 Ismailov et al.34 Ramkumar and Kudchadker35 VonNiederhausen et al.36 Mathuni et al.26 Steele et al.37

Nc

(Tmin − Tmax)/K

ethylene carbonate (crystal) 3 273.90−296.60 9 280.60−308.40 8 272.67−307.85 ethylene carbonate (liquid) 17 382.12−436.83 21 368.36−449.01 4 451.58−466.22 4

487.10−505.50

29 310.30−369.50 5 333.15−353.15 15 292.98−362.63 propylene carbonate (liquid) 4 328.20−369.60 13 412.80−466.14 27 368.57−462.07 9 668.60−762.60 19 459.85−513.25

(pmin − pmax)/kPa 0.001−0.003 0.001−0.011 0.001−0.011 0.915−9.114 0.449−13.800 15.190−24.230 44.690−73.450 0.012−0.469 0.045−0.175 0.003−0.391 0.160−0.676 4.870−29.103 0.669−25.838 1370.0−4137.0 24.210−97.170

36 298.15−473.15 18 298.40−344.90 7 407.97−485.91 5 327.12−353.15 18 278.19−362.53 γ-valerolactone (liquid) 342.15−476.55 Sd

0.003−37.768 0.009−0.218 4.000−50.000 0.057−0.287 0.001−0.529

Sd

9.015−99.978

342.15−476.55

Ge 298.15−353.15 22 275.80−349.70 11 263.65−313.25 16 338.10−470.19 4 347.10−384.50 10 401.40−477.80 16 238.07−308.14 γ-butyrolactone (liquid) 7 392.15−474.15 Sd 338.00−360.00 Sd 357.00−435.00 10 477.00−553.00

9.086−102.488

0.007−1.033 0.003−0.134 0.580−82.180 0.670−5.070 10.130−101.190 0.001−0.092 6.679−94.392 0.945−2.526 2.094−34.163 101.000−370.000

11f

474.90−730.80

93.290−5013.000

12 22

376.99−477.54 361.09−522.60

4.000−100.000 2.000−270.020

a

The data from references written in bold were used in the SimCor method (Section 3.6). bThe references reporting single or two vapor pressure points obtained for example as part of the synthesis or VLE measurements on multicomponent mixtures are not considered. cN stands for number of experimental data points. dS stands for smoothed data. eG stands for graphical representation only. fInclusion of hightemperature vapor pressures by VonNiederhausen et al.36 would require additional parameters in the fitting equation. For application requiring high-temperature data, the reader should follow recommendation in ref 36.

rejected in the final correlation, as described below in the Section 3.6. C



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Figure 3. γ-Valerolactone: arc representation17 of vapor pressure data in the liquid phase. Green , Schuette and Thomas27 (isoteniscope); teal , Schuette and Thomas27 (ebulliometry); blue ◊, Emel’yanenko et al.;29 orange ☆, Klajmon et al.;7 magenta ▲, Havasi et al.;31 magenta △, Havasi et al.31 (excluded); cyan ●, Zaitseva et al.;30 red ■, this work (STAT6); red , data obtained by SimCor method (Section 3.6). Data sets represented by filled symbols were used in the SimCor method.

Figure 1. Ethylene carbonate: arc representation17 of vapor pressure data. Liquid phase: green ☆, Petrov and Sandler;20 forest green ▽, Hong et al.;21 blue ◊, Verevkin et al.;19 black ★, Chernyak and Clements;22 red ■, this work (STAT8); red , data obtained by SimCor method (Section 3.6). Crystalline phase: blue △, Verevkin et al.;19 cyan ○, Choi and Jonich;18 orange ◁, Dougassa et al.;23 red ▲, this work (STAT8); black , data obtained by SimCor method. Data sets represented by filled symbols were used in the SimCor method.

Figure 4. γ-Butyrolactone: arc representation17 of vapor pressure data in the liquid phase. Blue ☆, McKinley and Copes32 (partially displayed); green □, Ramkumar and Kudchadker35 (partially displayed); purple ◊, VonNiederhausen et al.36 (partially displayed); magenta ▷, Mathuni et al.;26 orange ●, Steele et al.;37 red , data obtained by SimCor method (Section 3.6). Smoothed data by Yevstropov et al.33 and Ismailov et al.34 are not displayed because they are out of scale. Data sets represented by filled symbols were used in the SimCor method.

17

Figure 2. Propylene carbonate: arc representation of vapor pressure data in the liquid phase. Green ☆, Petrov and Sandler;20 forest green ▽, Hong et al.;21 ☆, Chernyak and Clements;22 magenta ▷, Mathuni et al.;26 purple × , Nasirzadeh et al.25 (partially displayed); blue ◊, Verevkin et al.;19 cyan ☆, Choi and Jonich18 (partially displayed); orange ◁, Dougassa et al.;23 red ■, this work (STAT8); red , data obtained by SimCor method (Section 3.6). Data by Wilson et al.24 are measured at much higher temperatures and are out of scale of this figure. Data sets represented by filled symbols were used in the SimCor method.

ization Δgl Hm determined both calorimetrically and from selected vapor pressure measurements (data sets used in SimCor or commented in the Section 3.6) are shown in Figures 5−8. In the case of ethylene carbonate, the enthalpies of vaporization derived from several vapor pressure data sets20−23 as well as calorimetric values by Hong et al.21 seem to have unrealistic slope, i.e. heat capacity difference ΔgS Cp,m is unrealistic (for detailed discussion, see Section 1.1 of the Supporting Information). Similarly, unrealistic temperature dependence can

3.2. Calorimetrically Determined Vaporization Enthalpies. Calorimetrically determined enthalpies of vaporization were found for all compounds (Table 4); however, no information about the experimental setup and data uncertainty is given by Hong et al.21 for ethylene carbonate and propylene carbonate. Single vaporization enthalpy for γ-valerolactone and γ-butyrolactone was obtained by Brown et al.38 with drop microcalorimetry (stated uncertainty 5%). Enthalpies of vaporD



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Table 4. Literature Enthalpy of Vaporization Δgl Hm for Ethylene Carbonate, Propylene Carbonate, γ-Valerolactone, and γ-Butyrolactonea ref Hong et al.21

Hong et al.21

Brown et al.38 Brown et al.38

T/K ethylene carbonate 423.11 433.11 443.11 453.11 463.11 473.11 propylene carbonate 423.11 433.11 443.11 453.11 463.11 473.11 γ-valerolactone 298.14 γ-butyrolactone 298.14

Δgl Hm/kJ mol−1 56.3 55.0 54.0 53.3 52.6 52.2 55.2 54.1 53.0 52.3 51.6 50.9

Figure 6. Propylene carbonate: comparison of calorimetrically determined enthalpy of vaporization Δgl Hm and ΔH′ ≡ ΔgcdHm/Δgcdz calculated from selected vapor pressure measurements (Δgcdz is defined in eq S1). Calorimetry (Δgl Hm): forest green ▼, Hong et al.21 Vapor pressure (ΔH′): green − −, Petrov and Sandler;20 forest green − −, Hong et al.;21 blue − −, Verevkin et al.;19 − −, Chernyak and Clements;22 magenta − −, Mathuni et al.;26 purple − −, Nasirzadeh et al.;25 orange − −, Dougassa et al.;23 red − −, this work (SimCor); red  , Δgl Hm recommended in this work (SimCor, Table S6 in the Supporting Information); red ···, uncertainty of the SimCor method.

54.8 54.4

a

The data from references written in bold were used in the SimCor method (section 3.6). Values are presumably reported at saturated vapor pressure which is, however, not specified in the respective references.

Figure 7. γ-Valerolactone: comparison of calorimetrically determined enthalpy of vaporization Δgl Hm and ΔH′ ≡ ΔgcdHm/Δgcdz calculated from selected vapor pressure measurements (Δgcdz is defined in eq S1). Calorimetry (Δgl Hm): brown ⧫, Brown et al.38 Vapor pressure (ΔH′): blue − −, Verevkin et al.;19 orange − −, Klajmon et al.;7 cyan − −, Zaitseva et al.;30 magenta − −, Havasi et al.31 (after omitting apparently erroneous data below 10 kPa); red − −, this work (SimCor); red , Δgl Hm recommended in this work (SimCor, Table S7 in the Supporting Information); red ···, uncertainty of the SimCor method.

Figure 5. Ethylene carbonate: comparison of calorimetrically determined enthalpy of vaporization Δgl Hm and ΔH′ ≡ ΔgcdHm/Δgcdz calculated from selected vapor pressure measurements (Δgcdz is defined in eq S1). Calorimetry (Δgl Hm): forest green ▼, Hong et al.21 Vapor pressure (ΔH′): green − −, Petrov and Sandler;20 forest green − −, Hong et al.;21 blue − −, Verevkin et al.;19 black − −, Chernyak and Clements;22 orange − −, Dougassa et al.;23 red − −, this work (SimCor); red , Δgl Hm recommended in this work (SimCor, Table S5 in the Supporting Information); red ···, uncertainty of the SimCor method.

not considered in the SimCor method (the information from vapor pressure data set would enter the correlation twice). 3.3. Condensed Phase Heat Capacities. Liquid phase heat capacities for ethylene carbonate, propylene carbonate, and γbutyrolactone were retrieved from the literature. New data were measured for γ-valerolactone and also for two compounds, for which the agreement between different data sets was unsatisfactory (ethylene carbonate and propylene carbonate). The results are presented in Table 5.

be observed also for some vapor pressure data sets in the case of propylene carbonate,21,23 γ-valerolactone,7,31 and γ-butyrolactone.32,33,35 Final selection can be made after thermodynamic consistency test (SimCor method, Section 3.6). Note that enthalpies of vaporization Δgl Hm determined from vapor pressure measurements can serve as another criterion for judging the quality of respective vapor pressure data sets; however, they are E



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Table 5. Experimental Condensed Phase Heat Capacities Ccd p,m for Ethylene Carbonate, Propylene Carbonate, and γValerolactone at p = (100 ± 5) kPaa ethylene carbonate T/K

−1 Ccd p,m/J·K · −1

mol

crystal (cd = cr) 262.19 101.89 264.00 102.85 266.00 104.00 268.00 105.06 270.00 106.20 272.00 107.35 274.00 108.49 276.00 109.72 278.00 110.87 280.00 112.10 282.00 113.33 284.00 114.57 286.00 115.80 288.00 117.03 290.00 118.26 292.00 119.59 294.00 120.91 295.68 121.96

Figure 8. γ-Butyrolactone: comparison of calorimetrically determined enthalpy of vaporization Δgl Hm and ΔH′ ≡ ΔgcdHm/Δgcdz calculated from selected vapor pressure measurements (Δgcdz is defined in eq S1). Calorimetry (Δgl Hm): brown ⧫, Brown et al.38 Vapor pressure (ΔH′): blue − −, McKinley and Copes;32 cyan − −, Yevstropov et al.;33 green − −, Ramkumar and Kudchadker;35 purple − −, VonNiederhausen et al.36 (partially displayed); magenta − −, Mathuni et al.;26 orange − −, Steele et al.;37 red − −, this work (SimCor); orange , Δgl Hm recommended by Steele et al.;37 red , Δgl Hm recommended in this work (SimCor, Table S8 in the Supporting Information); red ···, uncertainty of the SimCor method.

liquid (cd = l) 316.43 139.49 317.00 139.58 318.00 139.75 319.00 139.84 320.00 140.02 321.00 140.10 322.00 140.28 323.00 140.37 323.60 140.46

An overview of heat capacity measurements is given in Table 6. In the case of γ-valerolactone, no literature data were found. The selected heat capacity data (written in bold in Table 6) were fitted to polynomial eq 1 and used in the SimCor method (see Section 3.6). The parameters of eq 1 are listed in Table 7. Deviations of individual data points from values calculated from eq 1 with parameters from Table 7 are graphically presented in Figures 9−12. 3.4. Phase Behavior. Precise adiabatic measurements were reported for propylene carbonate and γ-butyrolactone and therefore no new measurements were necessary (Table 8). Measurements of the phase behavior were performed for ethylene carbonate (for which literature data were inconclusive) in the temperature range from 183 to 328 K and for γvalerolactone (for which no literature values were found) in the temperature range from 183 to 303 K. Thermograms of phase behavior measurement of ethylene carbonate and γ-valerolactone are presented in Figure S19 in the Supporting Information. 3.5. Thermodynamic Properties in the Ideal-Gas State. The thermodynamic properties in the ideal-gas state were calculated by statistical mechanics using the R1SM model62 combining (i) the rigid rotor−harmonic oscillator (RRHO) approximation, (ii) corrections for methyl top rotations using the one-dimensional hindered rotor approximation (1DHR),63 and (iii) taking into account the population of conformers based on the Boltzmann distribution. The density functional theory (DFT) at the B3LYP/6-311+G(d,p) level of theory64−67 with the empirical correction for the dispersion interactions D3 developed by Grimme et al.68 as implemented in Gaussian 09 software package69 was used to optimize the molecular geometries and calculate fundamental vibrational frequencies and potential energy profiles of methyl rotations for all four molecules. All calculated vibrational frequencies used to calculate vibrational contributions to the ideal-gas thermodynamic properties were scaled by the double-linear scaling factor (SF)

propylene carbonate T/K

−1 Ccd p,m/J·K · −1

mol

liquid (cd = l) 262.22 162.94 265.00 163.34 270.00 164.16 275.00 164.98 280.00 165.79 285.00 166.61 290.00 167.53 295.00 168.45 300.00 169.37 305.00 170.29 310.00 171.20 315.00 172.23 320.00 173.14 325.00 174.17 330.00 175.19 335.00 176.11 340.00 177.13 345.00 178.15 350.00 179.17 355.00 180.09 357.99 180.70

γ-valerolactone T/K

−1 Ccd p,m/J·K · mol−1

liquid (cd = l) 265.37 167.70 270.00 168.60 275.00 169.60 280.00 170.70 285.00 171.81 290.00 172.91 295.00 174.11 300.00 175.31 305.00 176.61 310.00 177.81 315.00 179.11 320.00 180.42 325.00 181.72 330.00 183.02 335.00 184.22 340.00 185.52 345.00 186.72 350.00 187.93 355.00 189.13 358.50 189.93

a Standard uncertainty u is u(T) = 0.05 K, and the combined expanded uncertainty of the heat capacity is Uc(Cp,m) = 0.01Cp,m (0.95 level of confidence). Values are reported with one digit more than is justified by the experimental uncertainty to avoid round-off errors in calculations based on these results.

optimized on alkanes70 SF (ν > 2000 cm−1) = 0.961; SF (ν < 2000 cm−1) = 0.9980−1.55 × 10−5 νi. All vibrational modes except those corresponding to the methyl top rotations were treated in the harmonic approximation in the statistical thermodynamics calculations. All stable conformations found during the conformational analysis were found to adopt twisted geometry of the ring. For propylene carbonate and γvalerolactone, two nonisomorphic conformers with either equatorial or axial position of the methyl group were identified (in both cases the equatorial position is energetically favored over the axial position). Ethylene carbonate and γ-butyrolactone were found to adopt only one stable conformation possessing an optical isomer. Both optical isomers (isomorphic conformers) were considered in the statistical thermodynamic calculations (in this case, only the ideal-gas entropy is affected and a term Rln 2 accounting for the mixing entropy of equimolar mixture was added to the value of entropy for one isomer). Molecular structures of the optimized conformers are shown in Figure S20 and given in Table S3. Relative conformer energies, point group F



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Table 6. Overview of the Literature Liquid Phase Heat Capacities for Ethylene Carbonate, Propylene Carbonate, γ-Valerolactone, and γ-Butyrolactonea ref

(Tmin − Tmax)/K

Nb

Vasil’ev and Korkhov39 Ding40 this work

15 Se 18

Vasil’ev and Korkhov39 Chernyak and Clements22 Ding40 this work

24 4 Se 9

Vasil’ev et al.41,42 Vasil’ev et al.41,42 Wilhelm et al.43 Fujimori and Oguni44 Comelli et al.45 Brouillette et al.46 Chernyak and Clements22 Ding40 Piekarski et al.47 Comelli et al.48 Comelli et al.49 Piekarski et al.50 this work

33 64 1 38 3 1 10 Se 1 26 8 1 21

this work

20

Fuchs51 Yevstropov et al.33 Lebedev and Yevstropov52,53 Ismailov et al.34 Brouillette et al.46

1 S4e 32 S 1

ur(Cp,m)/%c

ethylene carbonate (crystal) 254.13−292.80 n/ad 280.00−309.00 5.0 262.19−295.68 1.0 ethylene carbonate (liquid) 309.48−349.98 n/ad 383.15−398.15 2.5 310.00−321.00 5.0 316.43−323.60 1.0 propylene carbonate (liquid) 227.63−307.10 n/a 253.74−414.97 n/a 298.15 n/ad 220.05−300.91 0.3 288.15−313.15 n/ad 298.15 0.5 303.15−393.15 2.5 219.00−320.00 5.0 298.15 0.3 293.15−423.15 0.1 288.15−323.15 n/ad 298.15 0.3 262.22−357.99 1.0 γ-valerolactone (liquid) 265.37−358.50 1.0 γ-butyrolactone (liquid) 298.14 0.5 229.79−329.99 0.3 218.76−328.64 0.25 290.00−409.97 n/ad 298.15 0.5

mole fraction purity

method

0.9983 0.9998 1.000

adiabatic DSC Tian−Calvet

0.9983 0.999 0.9998 1.000

adiabatic DSC DSC Tian−Calvet

0.9932 0.9932 0.99 0.9997 0.997 0.997 0.999 0.9998 n/ad 0.997 0.997 0.997 0.9994

adiabatic adiabaticf Picker flow adiabatic DSC Picker flow DSC DSC Picker flow DSC DSC Picker flow Tian−Calvet

0.9991

Tian−Calvet

0.99 0.9983 0.9983 n/ad 0.99

adiabatic adiabatic adiabatic Tian−Calvet Picker flow

The data from references written in bold were fitted to eq 1 and used in the SimCor method (Section 3.6). bN stands for number of data points. ur(Cp,m) stands for relative uncertainty in heat capacity as stated by the authors. dn/a stands for not available. eS stands for smoothed data, a number signifies how many points were tabulated. fSimplified construction apparatus.41,42 a c

Table 7. Parameters of Eq 1 for Condensed Phase Heat Capacities compound

A1

A2

A3

ethylene carbonate (crystal) ethylene carbonate (liquid) propylene carbonate (liquid) γ -valerolactone (liquid) γ -butyrolactone (liquid)

9.16145 8.52925 33.4458 41.6843 18.7996

−4.18175 3.26969 −16.8139 −24.6787 −4.66983

2.04450 −0.212330 5.94874 8.60335 1.72861

{

n

1/2

}

calc calc 2 sr = 100 ∑i = 1 [(C p,m − C p,m )/C p,m ]i /(n − m) parameters. a

A4

Tmin/K

Tmax/K

sra

−0.604224 −0.888321 −0.122409

262 309 220 265 218

296 350 415 359 329

0.151 0.081 0.549 0.093 0.141

, where n is the number of fitted data points, and m is the number of independent adjustable

different than that of the majority of previously published values. Data by Hong et al.,21 Petrov and Sandler,20 and Chernyak and Clements22 seem to agree with each other and with part of the data set by Verevkin et al.19 (see the arc representation, Figure 1). Although the temperature dependence of vaporization enthalpies was found suspicious (Section 3.2), this agreement (and disagreement with the data of this work) raised questions about the ethylene carbonate sample used in our studies. Therefore, mass spectroscopy analysis of our sample was performed, which confirmed that it was neat ethylene carbonate. A good agreement of our heat capacity (Figure 9) and temperature and enthalpy of fusion Δ1s Hm (Table 8) with the literature values also suggests that the disagreement between the vapor pressure measurements

symmetries, and products of principal moments of inertia are listed in Table S4 in the Supporting Information. 3.6. Recommended Vapor Pressure Data Developed by the SimCor Method. This section describes the procedure of developing thermodynamically consistent vaporization/ sublimation data. The procedure is based on the multiproperty simultaneous treatment of vapor/sublimation pressures and related thermal data (SimCor method, Section 1 of the Supporting Information). As described in the Section 3.1, data sets were first analyzed using the arc representation based on which obvious outliers that were distant from the rest of the data were identified and not further considered. Note that in the case of ethylene carbonate, our vapor pressure data exhibit a trend G



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exp Figure 11. γ-Valerolactone: relative deviations ΔCp,m/Ccalc p,m = (Cp,m − calc exp )/C of individual experimental heat capacities C from values Ccalc p,m p,m p,m Ccalc p,m calculated by means of eq 1 with parameters from Table 7. Red ■, this work. Data points represented by filled symbols were used to obtain the parameters of eq 1.

exp Figure 9. Ethylene carbonate: relative deviations ΔCp,m/Ccalc p,m = (Cp,m − calc calc exp Cp,m)/Cp,m of individual experimental heat capacities Cp,m from values Ccalc p,m calculated by means of eq 1 with parameters from Table 7. Brown ☆, Vasil’ev and Korkhov39 (crystal, partially displayed); brown ●, Vasil’ev and Korkhov39 (liquid); blue , Ding40 (crystal, partially displayed); forest green , Ding40 (liquid, partially displayed); purple ■, this work (crystal); red ■, this work (liquid). Data points represented by filled symbols were used to obtain the parameters of eq 1. Some data listed in Table 6 are not displayed because they are out of scale.

exp Figure 12. γ-Butyrolactone: relative deviations ΔCp,m/Ccalc p,m = (Cp,m − calc calc exp Cp,m)/Cp,m of individual experimental heat capacities Cp,m from values Ccalc p,m calculated by means of eq 1 with parameters from Table 7. Red ★, Fuchs;51 forest green ⬟, Yevstropov et al.52 and Lebedev and Yevstropov.;53 green , Yevstropov et al.;33 orange , Ismailov et al.34 Data points represented by filled symbols were used to obtain the parameters of eq 1. Some data listed in Table 6 are not displayed because they are out of scale.

exp Figure 10. Propylene carbonate: relative deviations ΔCp,m/Ccalc p,m = (Cp,m calc calc exp − Cp,m)/Cp,m of individual experimental heat capacities Cp,m from values Ccalc p,m calculated by means of eq 1 with parameters from Table 7. Brown ●, Vasil’ev et al.;41,42 orange ●, Vasil’ev et al.41,42 (simplified construction apparatus); navy blue ▼, Fujimori and Oguni;44 forest green ⬡, Comelli et al.;45 magenta ▷, Brouillette et al.;46 blue ◊, Chernyak and Clements;22 orange ⧫, Piekarski et al.;47 green ⬡, Comelli et al.;49 purple ⧫, Piekarski et al.;50 red ■, this work. Data points represented by filled symbols were used to obtain the parameters of eq 1. Some data listed in Table 6 are not displayed because they are out of scale.

contrast to ethylene carbonate, vapor pressures by Verevkin et al.19 disagree with the above-mentioned data sets. As the data by Verevkin et al.19 are significantly lower than the data of this work in the case of ethylene carbonate and significantly higher in the case of propylene carbonate, and the vapor pressures by Mathuni et al.26 for γ-valerolactone considerably differ from high-quality vapor pressures by Steele et al.;37 the mutual agreement of data from references20−22,26 does not mean the vapor pressures in these references are correct. As a next step, the data sets were tested for consistency (each data set separately) using the SimCor method, which revealed inconsistency between p and heat capacity difference ΔgS Cp,m for vapor pressure data sets by Hong et al.,21 Petrov and Sandler,20 and Chernyak and Clements22 (thermodynamic consistency tests are described in full detail for ethylene carbonate in Section 1.2 of the Supporting Information). The SimCor of single vapor pressure data set by Verevkin et al.19 with thermal data yielded reasonable derived properties (ΔgS Hm and ΔgS Cp,m); however, the vapor pressures differed from values of this work (Table 2) by 15−20% (Figure S16 in the Supporting Information), well outside the uncertainty of our measurements. The SimCor of our vapor pressures data

performed in this work and the literature values are not related to the purity of our sample. Hong et al.21 noted a decomposition when samples were exposed to temperatures higher than 473 K; however, all literature vapor pressure data for ethylene carbonate (with the exception of four values measured by Chernyak and Clements22) were measured below 473 K. The reasons for the difference remain unknown. It should be recalled, however, that the slope of enthalpies of vaporization derived from vapor pressure data was too steep for data by Hong et al.21 and Petrov and Sandler20 and too flat for data by Chernyak and Clements22 (see Figure 5). Petrov and Sandler,20 Hong et al.,21 Chernyak and Clements,22 and Verevkin et al.19 also measured vapor pressures for propylene carbonate. Mutual agreement between vapor pressures by Petrov and Sandler,20 Hong et al.,21 Chernyak and Clements,22 and Mathuni et al.26 is reasonable; however, in H



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final correlation of data for ethylene carbonate. Similar procedure was applied in the case of propylene carbonate; data of this work proved to be thermodynamically consistent with the thermal data, but in contrast to ethylene carbonate, it was not possible to combine them with any of the data sets at higher temperatures. It seems that vapor pressures by Nasirzadeh et al.25 are too high, while data by Hong et al.21 and by Chernyak and Clements22 are too low. In case of γ-valerolactone, data of this work as well as vapor pressures by Zaitseva et al.30 and selected data (above 10 kPa) of Havasi et al.31 passed thermodynamic consistency tests, however, both scatter and uncertainty of the data by Zaitseva et al.30 and Havasi et al.31 are significant. In the case of γbutyrolactone, ebulliometric data by Steele et al.37 were found to be thermodynamically consistent with the thermal data and the SimCor method was used to extend temperature range of ebulliometric data (361 to 522 K) down to 218 K. To summarize, selected vapor pressure data (data given in bold in Table 3) were treated simultaneously with selected solid or liquid heat capacities (data given in bold in Table 6), ideal-gas heat capacities (Table 9), and vaporization enthalpies (Table 4). Recommended vapor pressure data are represented by the Cox equation, which was found to be the most adequate for describing simultaneously vapor pressure and related thermal data as a function of temperature down to the triple point.71 The Cox equation has the form72

Table 8. Temperature of Fusion Tfus and Enthalpy of Fusion ΔlsHm for Ethylene Carbonate, Propylene Carbonate, γValerolactone, and γ-Butyrolactone Tfus/K

ref

ΔlsHm/kJ·mol−1

ethylene carbonate Silvestro and Lenchitz54 Le Fevre et al.55 Bonner and Kim56 Vasil’ev and Korkhov39 Thompson et al.57 Hong et al.21 Calhoun58 Ding40 Schroedle et al.59 Wachter et al.60 this worka

308.93 311.13 309.64 309.48 309.51 312.94 308.89 311.20 309.55 308.53 309.13

13.3 13.2

13.0

13.5

propylene carbonate Vasil’ev and Korkhov41 Hong et al.21 Fujimori and Oguni44 Ding40 Ding and Jow61

224.86 222.96 218.66 220.30 218.65

9.6 8.011 9.0

γ-valerolactone this worka γ-butyrolactone Yevstropov et al.,33,52 Lebedev and Yevstropov53 Wachter et al.60 Mathuni et al.26

238.34

7.1

229.78

9.57

ln

228.44 229.43

n ⎞ ⎛ T °/K ⎞ ⎛ i⎟ ⎜ A T = 1 − exp ( /K) ⎟ ⎜ ∑ i ⎟ T /K ⎠ ⎜⎝ i = 0 p0 ⎝ ⎠

p

(2)

where p is the vapor pressure, T is the temperature, T0 and p0 are the temperature and pressure of an arbitrarily chosen reference point, and Ai are correlation parameters. n = 2 for liquid phase and n = 1 for solid phase were used in this work; parameters of eq 2 are given in Table 10. This table also contains the parameters for crystalline ethylene carbonate, which were obtained by a simultaneous treatment of vapor pressure and enthalpy of sublimation at the triple point temperature and the difference cr ΔgcrC0p,m = Cg0 p,m − Cp,m. The enthalpy of sublimation at the triple point temperature was obtained from the vaporization enthalpy at the same temperature (obtained from Cox eq 2 with the

a

Mean of values obtained in at least three experiments. Standard uncertainty associated with the mean value of enthalpy of fusion is u(ΔlsHm) = 0.3 kJ mol−1 and u(T) = 0.3 K. Experiments were performed at pressure p = (100 ± 5) kPa.

(Table 2) when extrapolated to higher temperatures agreed with four vapor pressure data points by Chernyak and Clements22 measured below 473 K. This agreement can be fortuitous, as both data of this work extrapolated to higher temperatures as well as the data by Chernyak and Clements22 are associated with significant uncertainty, but both data sets were selected for the

Table 9. Standard Molar Thermodynamic Functions (in J·K−1·mol−1) of Ethylene Carbonate, Propylene Carbonate, γValerolactone, and γ-Butyrolactone in the Ideal Gaseous State at p = 105 Paa ethylene carbonate

propylene carbonate

γ-valerolactone

γ-butyrolactone

T/K

Cg0 p,m

Sg0 m

Cg0 p,m

Sg0 m

Cg0 p,m

Sg0 m

Cg0 p,m

Sg0 m

100 150 200 250 273.15 298.15 300 400 500 600 700 800 900 1000

43.3 49.5 57.4 67.6 72.8 78.7 79.1 102.3 122.5 138.9 152.3 163.2 172.3 179.8

240.9 259.6 274.9 288.7 295.0 301.6 302.1 328.0 353.1 376.9 399.4 420.5 440.2 458.8

54.6 64.9 76.7 90.4 97.1 104.6 105.1 134.1 159.2 179.8 196.7 210.6 222.3 232.1

257.8 281.9 302.2 320.8 329.1 337.9 338.6 372.9 405.6 436.5 465.6 492.8 518.3 542.2

55.8 69.1 82.8 98.3 106.0 114.4 115.1 148.3 177.5 201.7 221.6 238.3 252.4 264.3

255.4 280.6 302.3 322.4 331.5 341.1 341.8 379.5 415.8 450.4 483.0 513.8 542.7 569.9

43.9 51.5 61.5 73.9 80.2 87.2 87.7 115.5 139.9 160.1 176.7 190.5 202.0 211.8

247.8 267.0 283.1 298.1 304.9 312.2 312.8 341.9 370.3 397.7 423.7 448.2 471.3 493.1

a

Values were calculated combining B3LYP-D3/6-311+G(d,p) calculations and R1SM model.62 Calculated fundamental frequencies were scaled by a linear function SF1 = 0.9980−1.55 × 10−5 νi below 2000 cm−1 and by a constant SF2 = 0.961 above 2000 cm−1.70 I



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Table 10. Parameters of the Cox Equation (Eq 2) compound

phase

A0

A1·103

ethylene carbonate ethylene carbonate propylene carbonate γ-valerolactone γ-butyrolactone

crystal liquid liquid liquid liquid

3.445531 3.354356 3.196086 2.847077 2.718110

−0.2573954 −0.7637676 −1.134903 −1.324751 −1.271436

A2·106

T0/K

p0/Pa

(Tmin − Tmax)/K

0.5033676 0.9185314 1.060314 1.036766

309.13 309.13 373.00 478.00 523.00

12.78 12.78 898.9 99795 272400

262−308 293−466 220−373 238−478 218−523

parameters for liquid phase from Table 10) and the calorimetrically determined enthalpy of fusion (see Table 8). As a result, the parameters of the Cox equations for the crystalline and liquid phases provide consistent values of vapor pressure, enthalpy of sublimation, and vaporization at the triple point temperature. Figures 13−16 show the deviations of individual vapor pressure data points from the recommended values calculated by means of the Cox equation (eq 2) with parameters from Table 10.

Figure 14. Propylene carbonate relative deviations (p − pcalc)/pcalc of vapor pressures p from the recommended values pcalc calculated using the Cox equation, eq 2, with parameters listed in Table 10. Green ☆, Petrov and Sandler;20 forest green ▽, Hong et al.21 (partially displayed); ☆, Chernyak and Clements;22 magenta ▷, Mathuni et al.;26 purple × , Nasirzadeh et al.25 (partially displayed); blue ◊, Verevkin et al.19 (partially displayed); cyan ☆, Choi and Jonich18 (partially displayed); orange ◁, Dougassa et al.23 (partially displayed); red ■, this work (STAT8); ···, absolute deviations. Data sets represented by filled symbols were used in the SimCor method. Figure 13. Ethylene carbonate: relative deviations (p − pcalc)/pcalc of vapor pressures p from the recommended values pcalc calculated with the Cox equation, eq 2, with parameters listed in Table 10. Liquid phase: green ☆, Petrov and Sandler;20 forest green ▽, Hong et al.;21 white ☆, Chernyak and Clements22 (excluded due to possible decomposition); black ★, Chernyak and Clements;22 red ■, this work (STAT8). Crystalline phase: blue △, Verevkin et al.;19 cyan ○, Choi and Jonich18 (partially displayed); red ▲, this work (STAT8); ···, absolute deviations. Data sets represented by filled symbols were used in the SimCor method. Liquid phase data by Verevkin et al.19 and Dougassa et al.23 are not displayed because they are out of scale.

butyrolactone) were combined with selected literature data and treated simultaneously to obtain thermodynamically consistent descriptions for four industrially important compounds used frequently as, e.g., solvents or electrolytes in lithium batteries. Ideal-gas thermodynamic properties for all the studied compounds were calculated by the methods of statistical thermodynamics based on calculated fundamental frequencies and molecular parameters obtained at the DFT B3LYP-D3/6311+G(d,p) level of theory. In the case of γ-butyrolactone, available literature data were thermodynamically extrapolated toward lower temperatures, thus covering the technologically important temperature range. For the remaining compounds (ethylene carbonate, propylene carbonate, and γ-valerolactone), new measurements and calculations helped to identify inconsistent data and clarify the situation in the temperature range of technological interest. To our knowledge, the thermodynamic properties in the ideal gaseous state for all the studied compounds as well as the heat capacities and the temperature and enthalpy of fusion for γ-valerolactone are reported for the first time. At higher temperatures, it is certainly possible to improve the quality of available data by new precise (ebulliometric) measurement for ethylene carbonate, propylene carbonate, and γ-valerolactone; we believe that no new measurements are needed for the temperature range covered by experiments of this work.

As the calculation of enthalpies of vaporization via the Clapeyron equation requires an evaluation of the appropriate pVT correction and the estimation of uncertainties of vapor pressures resulting from the SimCor is not straightforward, the vapor pressures and vaporization enthalpies along with the associated uncertainties are tabulated in Tables S5−S8 in the Supporting Information for convenience.

4. CONCLUSIONS New data determined in this work (sublimation pressures and crystal heat capacities for ethylene carbonate; vapor pressures and liquid heat capacities for ethylene carbonate, propylene carbonate, and γ-valerolactone; and ideal gas heat capacities for ethylene carbonate, propylene carbonate, γ-valerolactone, and γJ



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DSC measurements); (iv) details on DFT and statistical thermodynamic calculations of ideal-gas thermodynamic properties; (v) tables containing recommended sublimation and vapor pressures and enthalpies (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Václav Pokorný: 0000-0003-4145-7982 Michal Fulem: 0000-0002-5707-0670 Ctirad Č ervinka: 0000-0003-1498-6715 Květoslav Růzǐ čka: 0000-0001-9048-1036 Funding

The authors acknowledge financial support from specific university research (MSMT No. 20-SVV/2017) and Czech Science Foundation (GACR No. 17-03875S). Access to computing and storage facilities owned by parties and projects contributing to the National Grid Infrastructure MetaCentrum, provided under the program “Projects of Large Infrastructure for Research, Development, and Innovations” (LM2010005) and the CERIT-SC under the program Centre CERIT Scientific Cloud, part of the Operational Program Research and Development for Innovations, Reg. No. CZ.1.05/3.2.00/08.0144, is highly appreciated.

Figure 15. γ-Valerolactone: relative deviations (p − pcalc)/pcalc of vapor pressures p from the recommended values pcalc calculated using the Cox equation, eq 2, with parameters listed in Table 10. Green , Schuette and Thomas27 (isoteniscope, partially displayed); teal , Schuette and Thomas27 (ebulliometry, partially displayed); blue ◊, Emel’yanenko et al.29 (partially displayed); orange ☆, Klajmon et al.;7 magenta ▲, Havasi et al.;31 magenta △, Havasi et al.31 (excluded; partially displayed); cyan ●, Zaitseva et al.;30 red ■, this work (STAT6); ···, absolute deviations. Data sets represented by filled symbols were used in the SimCor method.

Notes

The authors declare no competing financial interest.

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(1) Schäffner, B.; Schäffner, F.; Verevkin, S. P.; Börner, A. Organic Carbonates as Solvents in Synthesis and Catalysis. Chem. Rev. 2010, 110, 4554−4581. (2) Flamme, B.; Rodriguez Garcia, G.; Weil, M.; Haddad, M.; Phansavath, P.; Ratovelomanana-Vidal, V.; Chagnes, A. Guidelines to design organic electrolytes for lithium-ion batteries: environmental impact, physicochemical and electrochemical properties. Green Chem. 2017, 19, 1828−1849. (3) Xu, K. Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries. Chem. Rev. 2004, 104, 4303−4418. (4) Fulem, M.; Růzǐ čka, K.; Růzǐ čka, M. Recommended vapor pressures for thiophene, sulfolane, and dimethyl sulfoxide. Fluid Phase Equilib. 2011, 303, 205−216. (5) Růzǐ čka, K.; Fulem, M.; Mahnel, T.; Č ervinka, C. Recommended vapor pressures for aniline, nitromethane, 2-aminoethanol, and 1methyl-2-pyrrolidone. Fluid Phase Equilib. 2015, 406, 34−46. (6) Pokorný, V.; Štejfa, V.; Fulem, M.; Č ervinka, C.; Růzǐ čka, K. Vapor pressures and thermophysical properties of dimethyl carbonate, diethyl carbonate, and dipropyl carbonate. J. Chem. Eng. Data 2017, 62, 3206. (7) Klajmon, M.; Ř ehák, K.; Morávek, P.; Matoušová, M. Binary Liquid−Liquid Equilibria of γ-Valerolactone with Some Hydrocarbons. J. Chem. Eng. Data 2015, 60, 1362−1370. (8) Růzǐ čka, K.; Majer, V. Simultaneous treatment of vapor pressures and related thermal data between the triple and normal boiling temperatures for n-alkanes C5-C20. J. Phys. Chem. Ref. Data 1994, 23, 1−39. (9) Fulem, M.; Růzǐ čka, K.; Morávek, P.; Pangrác, J.; Hulicius, E.; Kozyrkin, B.; Shatunov, V. Vapor Pressure of Selected Organic Iodides. J. Chem. Eng. Data 2010, 55, 4780−4784. (10) Štejfa, V.; Fulem, M.; Růzǐ čka, K.; Morávek, P. New Static Apparatus for Vapor Pressure Measurements: Reconciled Thermophysical Data for Benzophenone. J. Chem. Eng. Data 2016, 61, 3627− 3639. (11) Höhne, G. W. H.; Hemminger, W. F.; Flammersheim, H.-J. Differential Scanning Calorimetry, 2nd ed.; Springer Verlag: Berlin, 2003.

Figure 16. γ-Butyrolactone: relative deviations (p − pcalc)/pcalc of vapor pressures p from the recommended values pcalc calculated using the Cox equation, eq 2, with parameters listed in Table 10. Blue ☆, McKinley and Copes 32 (partially displayed); green □ , Ramkumar and Kudchadker35 (partially displayed); purple ◊, VonNiederhausen et al.36 (partially displayed); magenta ▷, Mathuni et al.;26 orange ●, Steele et al.;37 ···, absolute deviations. Some data listed in Table 3 are not displayed because they are out of scale. Data sets represented by filled symbols were used in the SimCor method.

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REFERENCES

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.7b00578. (i) Description of the SimCor method; (ii) consistency tests based on SimCor method; (iii) measurement of phase behavior and enthalpies of fusion (thermograms of K



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Vapor Pressures and Thermophysical Properties of Ethylene

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