Partial Molar Isentropic Compressions and Partial Molar Volumes of

Article pubs.acs.org/jced

Partial Molar Isentropic Compressions and Partial Molar Volumes of Isomeric Butanediols at Infinite Dilution in Water at Temperatures T = (278 to 318) K and Atmospheric Pressure Lubomír Hnědkovský and Ivan Cibulka* Department of Physical Chemistry, Institute of Chemical Technology, Technická 5, 166 28 Prague, Czech Republic S Supporting Information *

ABSTRACT: Speed of sound and density data for dilute aqueous solutions of all four isomeric butanediols derived from n-butane (butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, butane-2,3-diol) were obtained using an Anton Paar DSA 5000 vibrating-tube densimeter and sound analyzer in the temperature range from (278.15 to 318.15) K and at atmospheric pressure. Standard molar isentropic compressions and standard molar volumes were evaluated from the measured data. Relations between the two standard quantities and molecular structures of the solutes are discussed.

■

INTRODUCTION This work presents experimental data on the density of and speed of sound in dilute aqueous solutions of four isomeric butanediols. New density data extend the temperature range of our previous study on partial molar volumes at infinite dilution (named standard molar volumes) of three isomeric butanediols1 (butane-1,3-diol, butane-1,4-diol, and butane-2,3-diol) measured in wide ranges of temperature and pressure (T from (298 to 573) K, p up to 30 MPa). By adding butane-1,2-diol into the group of solutes investigated the present experiments provide the data for evaluation of standard molar volumes in the temperature range from (278 to 318) K of all isomeric butanediols derived from n-butane. Beside the standard molar volumes the present density data along with data on speed of sound make possible to evaluate partial molar isentropic compressions at infinite dilution (named standard molar isentropic compressions). The present study is a continuation of our recent investigation of standard molar volumes and standard molar isentropic compressions of aqueous propanediols.2 Both groups of solutes belong to the same family of organic substances, and thus the present study extends the possibility of analysis of the effects of both the molecular size and the mutual position of two hydroxyl groups on the hydrocarbon frame.

Table 1. Specifications of Chemical Samples of Solutes. All Samples Were from Sigma Aldrich and Were Used As Supplied

a

formula

CAS RN

mass fraction puritya

mass fraction of waterb

butane-1,2-diol butane-1,3-diol butane-1,4-diol butane-2,3-diol

C4H10O2 C4H10O2 C4H10O2 C4H10O2

584-03-2 107-88-0 110-63-4 513-85-9

> 0.98 0.99 0.99 0.98

0.00010 0.00029 0.00031 0.0034

Declared by the supplier. bDetermined by the Karl Fischer method.

Table 2. Values of Density ρ1 of and Speed of Sound c1 in Water (NIST)3 Used in Calculations of Standard Molar Isentropic Compression and Standard Molar Volume

■

EXPERIMENTAL SECTION The specifications of the organic solutes are summarized in Table 1. They were used as obtained from the supplier. Water was purified by distillation and demineralization (Millipore RQ). Purified water left in contact with air, that is, containing dissolved air, was used as a calibration fluid for the densimeter and for the preparation of solutions. Solutions were prepared by mass using a Precisa 40SM-200A balance (resolution = 10−2 mg, uncertainty = ± 0.1 mg, maximum load 200 g) to determine the mass of the solute and an A&D Instruments © 2013 American Chemical Society

chemical name

T/K

ρ1/kg·m−3

c1/m·s−1

278.15 283.15 288.15 293.15 298.15 303.15 308.15 318.15

999.967 999.702 999.103 998.207 997.048 995.649 994.033 990.213

1426.17 1447.27 1465.93 1482.35 1496.70 1509.15 1519.85 1536.45

GF-3000-EC balance (resolution = 10 mg, estimated uncertainty = ± 2·10−2 %, maximum load 3.1 kg) to determine the mass of water. The mass of each prepared solution was about 1 kg. Corrections with respect to content of water Received: October 4, 2012 Accepted: January 8, 2013 Published: January 18, 2013 388

dx.doi.org/10.1021/je301082y | J. Chem. Eng. Data 2013, 58, 388−397

Journal of Chemical & Engineering Data

Article

Table 3. Experimental Differences Δc = c − c1 Measured for {Butane-1,2-diol, Butane-1,3-diol, Butane-1,4-diol, or Butane-2, 3-diol (2) + Water (1)} at Atmospheric Pressurea m2/mol·kg−1

Δc/m·s−1

T/K =

278.15

283.15

288.15

0.05004 0.05004 0.05004 0.10321 0.10321 0.10321 0.15008 0.15008 0.15008 0.20002 0.20002 0.20002 0.25008 0.25008 0.25008 0.30012 0.30012 0.30012

4.23 4.21 4.21 8.66 8.63 8.66 12.54 12.51 12.55 16.64 16.64 16.64 20.70 20.71 20.73 24.75 24.74 24.77

3.89 3.87 3.89 7.97 7.97 7.98 11.55 11.54 11.55 15.33 15.33 15.34 19.09 19.09 19.11 22.82 22.83 22.85

3.59 3.60 3.59 7.38 7.38 7.39 10.67 10.71 10.70 14.18 14.18 14.19 17.66 17.67 17.66 21.10 21.12 21.11

0.100101 0.100101 0.100101 0.152009 0.152009 0.152009 0.200535 0.200535 0.200535 0.250559 0.250559 0.250559 0.302953 0.302953 0.302953 0.350636 0.350636 0.350636

7.32 7.31 7.32 11.04 11.05 11.04 14.51 14.53 14.53 18.06 18.10 18.09 21.71 21.76 21.76 25.10 25.17 25.16

6.68 6.69 6.70 10.14 10.13 10.13 13.31 13.32 13.34 16.61 16.60 16.62 19.98 19.97 19.98 23.11 23.11 23.12

6.18 6.21 6.17 9.36 9.37 9.35 12.30 12.30 12.27 15.29 15.30 15.28 18.39 18.38 18.41 21.26 21.30 21.28

0.101223 0.101223 0.101223 0.200259 0.200259 0.200259 0.301337 0.301337 0.301337 0.401591 0.401591 0.401591 0.501058 0.501058 0.501058 0.602697 0.602697 0.602697

6.88 6.87 6.86 13.54 13.49 13.49 20.21 20.18 20.18 26.73 26.69 26.69 33.12 33.08 33.09 39.56 39.53 39.53

6.30 6.29 6.29 12.36 12.36 12.36 18.47 18.48 18.48 24.46 24.46 24.46 30.30 30.30 30.29 36.18 36.18 36.19

5.81 5.80 5.81 11.40 11.39 11.40 17.00 16.99 17.00 22.49 22.48 22.48 27.85 27.84 27.85 33.25 33.24 33.26

293.15 Butane-1,2-diol (aq) 3.33 3.33 3.32 6.84 6.83 6.83 9.88 9.88 9.89 13.13 13.13 13.13 16.33 16.33 16.34 19.52 19.52 19.53 Butane-1,3-diol (aq) 5.70 5.70 5.70 8.63 8.63 8.63 11.35 11.35 11.35 14.12 14.13 14.13 16.98 16.98 17.00 19.63 19.62 19.64 Butane-1,4-diol (aq) 5.30 5.31 5.34 10.43 10.45 10.46 15.58 15.61 15.64 20.70 20.67 20.69 25.65 25.60 25.61 30.58 30.57 30.57 389

298.15

303.15

308.15

318.15

3.07 3.07 3.08 6.32 6.31 6.30 9.11 9.15 9.15 12.10 12.15 12.16 15.08 15.13 15.13 18.03 18.06 18.06

2.84 2.86 2.85 5.85 5.86 5.86 8.46 8.47 8.48 11.23 11.24 11.24 13.97 13.97 13.98 16.68 16.69 16.70

2.60 2.63 2.61 5.38 5.40 5.38 7.80 7.81 7.81 10.34 10.36 10.35 12.88 12.89 12.89 15.39 15.41 15.41

2.23 2.23 2.26 4.59 4.59 4.62 6.64 6.65 6.65 8.80 8.81 8.82 10.94 10.95 10.94 13.05 13.06 13.06

5.28 5.27

4.85 4.89 4.88 7.37 7.36 7.34 9.65 9.70 9.70 12.02 12.07 12.07 14.45 14.51 14.50 16.72 16.76 16.75

4.50 4.46 4.52 6.80 6.77 6.81 8.94 8.93 8.95 11.12 11.12 11.13 13.37 13.39 13.38 15.44 15.49 15.45

3.85 3.72 3.88 5.70 5.62 5.82 7.57 7.55 7.49 9.43 9.49 9.33 11.34 11.45 11.23 13.09 13.28 12.95

4.54

4.18 4.18 4.16 8.19 8.20 8.19 12.22 12.23 12.23 16.16 16.16 16.18 20.00 20.00 20.03 23.85 23.84 23.89

3.56 3.53 3.54 6.97 6.97 6.97 10.37 10.39 10.38 13.68 13.72 13.69 16.88 16.94 16.88 20.08 20.18 20.11

7.99 7.99 10.49 10.48 13.07 13.06 15.70 15.69 18.16 18.15

4.92 4.92 4.92 9.66 9.66 9.66 14.42 14.42 14.42 19.06 19.06 19.06 23.58 23.59 23.58 28.12 28.13 28.13

8.91

13.29

17.55

21.71

25.90



Article

Table 3. continued m2/mol·kg−1 T/K = 0.100931 0.100931 0.100931 0.150810 0.150810 0.150810 0.199859 0.199859 0.199859 0.249794 0.249794 0.249794 0.299551 0.299551 0.299551 0.349849 0.349849 0.349849

Δc/m·s−1 278.15 8.39 8.39 8.39 12.50 12.49 12.50 16.52 16.51 16.53 20.56 20.59 20.62 24.60 24.59 24.62 28.65 28.63 28.67

283.15 7.73 7.74 7.74 11.52 11.54 11.53 15.23 15.24 15.25 18.99 18.98 18.98 22.74 22.73 22.75 26.48 26.48 26.50

288.15 7.20 7.20 7.21 10.72 10.72 10.73 14.17 14.15 14.17 17.67 17.64 17.67 21.12 21.07 21.11 24.58 24.53 24.61

293.15

298.15

303.15

308.15

318.15

6.22 6.22

5.78 5.79 5.78 8.59 8.60 8.61 11.34 11.36 11.37 14.14 14.15 14.17 16.88 16.88 16.91 19.64 19.64 19.68

5.34 5.31 5.40 7.96 7.94 8.00 10.51 10.51 10.54 13.12 13.13 13.13 15.67 15.70 15.65 18.25 18.28 18.21

4.56 4.51 4.66 6.84 6.78 6.88 9.04 8.99 9.02 11.20 11.20 11.22 13.33 13.55 13.32 15.56 15.77 15.45

Butane-2,3-diol (aq) 6.67 6.67 6.67 9.94 9.94 9.94 13.15 13.14 13.14 16.36 16.36 16.35 19.59 19.58 19.58 22.80 22.80 22.80

9.26 9.25 12.24 12.23 15.25 15.24 18.21 18.20 21.18 21.18

Standard uncertainties are u(T) = 0.01 K, u(m2) = 3·10−5 mol·kg−1, and the combined expanded uncertainty is Uc(Δc) = 0.3 m·s−1 at T = 318.15 K and Uc(Δc) = 0.1 m·s−1 at lower temperatures (level of confidence = 0.95).

a

Table 4. Experimental Differences Δρ = ρ − ρ1 Measured for {Butane-1,2-diol, Butane-1,3-diol, Butane-1,4-diol, or Butane-2, 3-diol (2) + Water (1)} at Atmospheric Pressurea m2/mol·kg−1

Δρ/kg·m−3

T/K =

278.15

283.15

288.15

0.05004 0.05004 0.05004 0.10321 0.10321 0.10321 0.15008 0.15008 0.15008 0.20002 0.20002 0.20002 0.25008 0.25008 0.25008 0.30012 0.30012 0.30012

0.240 0.241 0.240 0.502 0.503 0.502 0.737 0.738 0.737 0.991 0.989 0.991 1.247 1.248 1.248 1.509 1.510 1.509

0.229 0.231 0.229 0.479 0.480 0.479 0.703 0.702 0.703 0.943 0.945 0.944 1.187 1.188 1.189 1.435 1.436 1.435

0.220 0.219 0.219 0.458 0.458 0.458 0.670 0.671 0.672 0.900 0.900 0.901 1.132 1.132 1.135 1.367 1.367 1.370

0.100101 0.100101 0.100101 0.152009 0.152009 0.152009 0.200535 0.200535 0.200535 0.250559 0.250559 0.250559

0.239 0.239 0.238 0.369 0.371 0.372 0.499 0.501 0.502 0.636 0.639 0.640

0.233 0.231 0.231 0.359 0.360 0.359 0.485 0.484 0.486 0.616 0.615 0.616

0.225 0.225 0.225 0.348 0.348 0.349 0.469 0.470 0.469 0.595 0.595 0.595

293.15 Butane-1,2-diol (aq) 0.211 0.210 0.211 0.439 0.438 0.439 0.642 0.641 0.642 0.861 0.860 0.862 1.082 1.082 1.084 1.305 1.306 1.306 Butane-1,3-diol (aq) 0.219 0.219 0.219 0.337 0.338 0.338 0.454 0.454 0.454 0.575 0.575 0.575 390

298.15

303.15

308.15

318.15

0.202 0.202 0.202 0.420 0.420 0.420 0.614 0.615 0.615 0.823 0.823 0.823 1.033 1.033 1.034 1.246 1.245 1.246

0.194 0.194 0.194 0.403 0.404 0.405 0.587 0.589 0.588 0.787 0.787 0.788 0.987 0.988 0.988 1.189 1.189 1.189

0.186 0.186 0.186 0.387 0.385 0.386 0.563 0.561 0.563 0.752 0.752 0.752 0.942 0.941 0.943 1.136 1.134 1.136

0.169 0.169 0.170 0.350 0.350 0.351 0.510 0.510 0.511 0.680 0.680 0.682 0.852 0.852 0.854 1.025 1.024 1.026

0.214 0.213

0.209 0.208 0.208 0.320 0.319 0.319 0.428 0.427 0.427 0.540 0.539 0.540

0.201 0.201 0.201 0.309 0.310 0.310 0.413 0.414 0.414 0.521 0.522 0.519

0.188 0.186 0.187 0.287 0.287 0.287 0.383 0.383 0.382 0.480 0.482 0.481

0.329 0.328 0.441 0.441 0.557 0.556



Article

Table 4. continued m2/mol·kg−1 T/K =

Δρ/kg·m−3 278.15

283.15

288.15

0.302953 0.302953 0.302953 0.350636 0.350636 0.350636

0.785 0.788 0.789 0.924 0.928 0.929

0.759 0.758 0.758 0.892 0.892 0.891

0.731 0.731 0.732 0.858 0.858 0.857

0.101223 0.101223 0.101223 0.200259 0.200259 0.200259 0.301337 0.301337 0.301337 0.401591 0.401591 0.401591 0.501058 0.501058 0.501058 0.602697 0.602697 0.602697

0.242 0.244 0.243 0.500 0.500 0.500 0.779 0.780 0.779 1.072 1.072 1.071 1.374 1.375 1.374 1.696 1.696 1.696

0.233 0.233 0.232 0.478 0.479 0.477 0.742 0.742 0.742 1.017 1.018 1.017 1.301 1.301 1.301 1.602 1.602 1.603

0.225 0.227 0.225 0.459 0.460 0.460 0.711 0.712 0.710 0.970 0.971 0.970 1.238 1.239 1.240 1.521 1.522 1.523

0.100931 0.100931 0.100931 0.150810 0.150810 0.150810 0.199859 0.199859 0.199859 0.299551 0.299551 0.299551 0.349849 0.349849 0.349849

0.437 0.438 0.437 0.661 0.662 0.662 0.885 0.886 0.887 1.356 1.357 1.358 1.599 1.600 1.601

0.424 0.425 0.424 0.642 0.641 0.642 0.859 0.858 0.858 1.312 1.311 1.312 1.544 1.543 1.545

0.413 0.414 0.413 0.623 0.623 0.622 0.832 0.833 0.833 1.268 1.269 1.268 1.492 1.493 1.492

293.15 Butane-1,3-diol (aq) 0.707 0.707 0.706 0.826 0.827 0.827 Butane-1,4-diol (aq) 0.217 0.217 0.217 0.442 0.440 0.441 0.682 0.681 0.683 0.928 0.928 0.930 1.182 1.183 1.185 1.449 1.449 1.451 Butane-2,3-diol (aq) 0.401 0.401 0.401 0.605 0.605 0.605 0.807 0.807 0.808 1.227 1.227 1.228 1.442 1.442 1.443

298.15

303.15

308.15

318.15

0.681 0.682

0.660 0.659 0.659 0.770 0.769 0.768

0.634 0.636 0.637 0.741 0.742 0.742

0.586 0.587 0.587 0.682 0.684 0.682

0.212 0.211 0.211 0.426 0.426 0.427 0.657 0.655 0.656 0.891 0.892 0.891 1.132 1.132 1.132 1.386 1.384 1.385

0.205

0.197 0.198 0.197 0.398 0.398 0.397 0.609 0.609 0.608 0.823 0.824 0.823 1.041 1.041 1.042 1.268 1.271 1.270

0.184 0.183 0.184 0.367 0.367 0.370 0.561 0.562 0.563 0.756 0.757 0.756 0.953 0.954 0.953 1.158 1.160 1.158

0.389 0.389

0.378 0.378 0.378 0.568 0.568 0.569 0.758 0.759 0.758 1.148 1.149 1.148 1.347 1.347 1.348

0.367 0.367 0.368 0.552 0.552 0.552 0.733 0.735 0.735 1.108 1.110 1.111 1.298 1.301 1.303

0.341 0.341 0.341 0.512 0.510 0.512 0.681 0.678 0.681 1.027 1.027 1.028 1.202 1.201 1.202

0.801 0.801

0.587 0.587 0.783 0.783 1.187 1.187 1.394 1.394

0.413

0.633

0.859

1.087

1.327

Standard uncertainties are u(T) = 0.01 K, u(m2) = 3·10−5 mol·kg−1, and the combined expanded uncertainty is Uc(Δρ) = 2·10−3 kg·m−3 (level of confidence = 0.95). a

Δρ = ρ − ρ1 where c and ρ are the speed of sound in and the density of the solution, respectively. It was observed that experimental values of c1 and ρ1 exhibited small systematic deviations from the values presented by NIST3 (for details see ref 2). The effect of these small deviations on the goal quantities (standard molar isentropic compressions, standard molar volumes) is negligible since in the differences Δ[(ρc)2] and Δρ (eqs 3 and 5) these systematic deviations cancel out. Therefore measured differences Δc and Δρ were regarded as direct experimental data and the values c1(NIST) and ρ1(NIST) were used for the evaluation of standard molar isentropic compressions and standard molar volumes as well as for the calculations of speeds of sound in and densities of solutions, that is, c = Δc(experimental) + c1(NIST) and

determined by the Karl Fischer method were applied for calculations of molalities. The vibrating-tube densimeter and sound analyzer manufactured by Anton Paar, model DSA 5000, with a built-in thermostat and equipped with the autosampler SP-1m (Anton Paar) was used for the measurements. The highest temperature at which the air-bubble formation had no observable effect was 318 K. The details concerning the experimental methodology can be found in our previous paper.2 To minimize the effects of both the device drifts and the systematic uncertainties in the calibration the measured speed of sound in water (c1) and density of water (ρ1) at each temperature and for each set of solutions were used to calculate the speed of sound differences Δc = c − c1 and density differences 391



Article

Table 5. Coefficients aK and bK of eq 3, Standard Molar Isentropic Compressions K0S,m,2, Coefficients aV, bV, and cV of eq 5, and Standard Molar Volumes V0m,2 for {Butane-1,2-diol, Butane-1,3-diol, Butane-1,4-diol, or Butane-2,3-diol (2) + Water (1)}. The Uncertainties σ(K0S,m,2) and σ(V0m,2) Represent the Combined Expanded Uncertainties aK·10−12

T K

−4 −2

kg ·m ·s ·mol 3

bK·10−12 −1

−4 −2

K0S,m,2 ± σ(K0S,m,2) −2

kg ·m ·s ·mol 4

278.15 283.15 288.15 293.15 298.15 303.15 308.15 318.15

0.2607 0.2444 0.2298 0.2155 0.2017 0.1888 0.1748 0.1515

−0.0073 −0.0063 −0.0077 −0.0082 −0.0086 −0.0104 −0.0067 −0.0119

278.15 283.15 288.15 293.15 298.15 303.15 308.15 318.15

0.2191 0.2039 0.1915 0.1789 0.1673 0.1559 0.1448 0.1236

−0.0055 −0.0025 −0.0060 −0.0054 −0.0057 −0.0063 −0.0054 −0.0040

278.15 283.15 288.15 293.15 298.15 303.15 308.15 318.15

0.2044 0.1904 0.1784 0.1655 0.1549 0.1444 0.1337 0.1151

−0.0043 −0.0046 −0.0063 −0.0049 −0.0067 −0.0073 −0.0063 −0.0075

278.15 283.15 288.15 293.15 298.15 303.15 308.15 318.15

0.2558 0.2402 0.2274 0.2137 0.2015 0.1895 0.1768 0.1536

−0.0011 0.0003 −0.0032 −0.0029 −0.0047 −0.0066 −0.0046 −0.0060

−1

cm ·mol ·GPa 3

−1

aV −3

bV −1

kg ·m ·mol 2

Butane-1,2-diol −17.7 ± 0.3 −11.8 ± 0.2 −7.0 ± 0.2 −2.9 ± 0.2 0.7 ± 0.2 3.8 ± 0.2 6.8 ± 0.3 11.5 ± 0.3 Butane-1,3-diol −8.7 ± 0.1 −3.5 ± 0.1 0.4 ± 0.1 3.9 ± 0.1 6.7 ± 0.1 9.3 ± 0.1 11.7 ± 0.2 15.9 ± 0.4 Butane-1,4-diol −5.1 ± 0.2 −0.4 ± 0.2 3.2 ± 0.2 6.6 ± 0.2 9.2 ± 0.2 11.6 ± 0.3 13.8 ± 0.2 17.5 ± 0.5 Butane-2,3-diol −17.5 ± 0.1 −11.8 ± 0.1 −7.4 ± 0.1 −3.4 ± 0.1 −0.2 ± 0.1 2.7 ± 0.1 5.5 ± 0.2 10.3 ± 0.4

(aq) 4.7520 4.5438 4.3463 4.1673 4.0092 3.8601 3.6941 3.3773 (aq) 2.2537 2.2000 2.1493 2.1023 2.0728 2.0225 1.9406 1.8235 (aq) 2.2951 2.2158 2.1588 2.0797 2.0365 1.9825 1.9089 1.7819 (aq) 4.2239 4.1015 4.0233 3.8952 3.7765 3.6895 3.5901 3.3468

−3

V0m,2 ± σ(V0m,2)

cV −2

kg ·m ·mol 3

−3

kg ·m ·mol 4

−3

cm3·mol−1

1.1790 1.0786 0.9650 0.8524 0.6668 0.4946 0.4091 0.1663

−0.8682 −0.9660 −0.8803 −0.8089 −0.6600 −0.5251 −0.4224 −0.1397

85.37 85.60 85.85 86.10 86.35 86.62 86.92 87.57

± ± ± ± ± ± ± ±

0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.4

1.3409 1.1966 1.0498 0.8747 0.6016 0.5921 0.7120 0.4951

−0.6404 −0.6320 −0.5825 −0.4057 −0.0145 −0.2904 −0.6260 −0.4174

87.87 87.95 88.05 88.17 88.30 88.47 88.70 89.15

± ± ± ± ± ± ± ±

0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.3

1.0681 0.8962 0.7112 0.6646 0.4918 0.4251 0.4017 0.3048

−0.3457 −0.2718 −0.1706 −0.2046 −0.0941 −0.1013 −0.1247 −0.1197

87.83 87.93 88.04 88.20 88.34 88.51 88.73 89.19

± ± ± ± ± ± ± ±

0.2 0.2 0.2 0.2 0.2 0.4 0.2 0.2

1.1430 1.0983 0.7429 0.8353 0.8661 0.6014 0.5017 0.3247

−0.4104 −0.5835 −0.1439 −0.5323 −0.7884 −0.3942 −0.3942 −0.1958

85.90 86.04 86.17 86.37 86.59 86.79 87.03 87.60

± ± ± ± ± ± ± ±

0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.3

ρ = Δρ(experimental) + ρ1(NIST) as needed for the evaluation of standard molar isentropic compressions. The values c1 and ρ1 extracted from the NIST database3 are summarized in Table 2. The vapor space in the flasks used for preparation and storage of the solutions gradually increased as the samples were withdrawn for measurements, and thus the evaporation might affect the concentrations. Measurements were started with full storage flasks at the temperature 298.15 K, and after measurements at all the other temperatures were completed, then the measurements at 298.15 K were repeated. No effects of evaporation on density and speed of sound were observed.

(probably due to formation of air bubbles) were excluded; in those cases no data are reported. Standard Molar Isentropic Compressions. Partial molar isentropic compression at infinite dilution (standard molar isentropic compression) of the solute 2 is defined as a limiting value of the derivative of standard molar volume Vom,2 with respect to pressure at constant entropy

RESULTS Direct Experimental Data. The measured values of the differences in speed of sound Δc = c − c1 and the measured values of differences in density Δρ = ρ − ρ1 along with the molalities of organic solutes m2 are recorded in Tables 3 and 4, respectively. Triplicate measurements were performed for each solution except for aqueous butane-1,4-diol at T = 303.15 K. Few measured values that deviated from the other measurements

where Vm,2app is the apparent molar volume and m2 is the molality of the solute. Based on this definition it is possible to derive2 the expression for standard molar isentropic compression

app ⎞ ⎛ ∂V 0 ⎞ ⎛ −∂V m,2 m,2 ⎟⎟ KS0,m,2 = lim ⎜ ⎟ = −⎜⎜ m2 → 0⎝ ∂p ⎠ ∂ p ⎝ ⎠S S

■

KS0,m,2 = 392

aK ⎞ 1 ⎛ ⎜M − ⎟⎟ 2⎜ 2 (ρ1c1) ⎝ (ρ1c1)2 ⎠

(1)

(2)



Article

where aK is the adjustable parameter of the fit of experimental values of the differences Δ[(ρc)2] = (ρc)2 − (ρ1c1)2 in the form (ρc)2 − (ρ1c1)2 Δ[(ρc)2 ] = = aK + bK m2 m2 m2

Table 6. Comparison of Measured Values of Standard Molar Isentropic Compression at p = 0.1 MPa with the Values Taken from the Literature this work

(3)

T

The values of the coefficients aK and bK were obtained from measured data (Tables 3 and 4) by using a least-squares method with unit weights and are recorded in Table 5 along with calculated values of K0S,m,2. Uncertainties σ(K0S,m,2) are affected mainly by the uncertainty in the speed of sound which was estimated to be about ± 0.1 m·s−1 at temperatures from (278 to 298) K and ± 0.3 m·s−1 at 318 K. Standard Molar Volumes. The partial molar volume at infinite dilution (m2 → 0) of a solute Vom,2 (standard molar volume) can be calculated from the equation4

K

literature

K0S,m,2 −1

cm ·mol ·GPa 3

298.15 308.15 318.15

0.7 ± 0.2 6.8 ± 0.3 11.5 ± 0.3

298.15

6.7 ± 0.1

308.15

11.7 ± 0.2

318.15

15.9 ± 0.4

(4)

278.15

−5.1 ± 0.2

where M2 is the molar mass of the solute and aV is an adjustable parameter of the fit of experimental values Δρ/m2 ρ − ρ1 Δρ = = aV + bV m2 + cV m2 2 m2 m2 (5)

283.15 293.15 298.15

−0.4 ± 0.2 6.6 ± 0.2 9.2 ± 0.2

308.15

13.8 ± 0.2

313.15 318.15

16.1b 17.5 ± 0.5

298.15

−0.2 ± 0.1

308.15

5.5 ± 0.2

0 app = lim (V m,2 V m,2 )= m2 → 0

a ⎞ 1⎛ ⎜⎜M 2 − V ⎟⎟ ρ1 ⎝ ρ1 ⎠

The values of the coefficients aV, bV, and cV obtained by using a least-squares method with unit weights are recorded in Table 5 along with the calculated standard molar volumes and estimated uncertainties. The presented values were combined with our previous data1 for butane-1,3-diol, butane-1,4-diol, and butane-2,3-diol and the polynomial function of temperature and pressure was fitted to the data. A polynomial fit of data obtained in this work for aqueous butane-1,2-diol at atmospheric pressure was also performed. The fitting procedure and values of adjustable parameters are presented in the Supporting Information.

■

dev.a

K0S,m,2 −1

−1

cm ·mol ·GPa 3

−1

Butane-1,2-diol (aq) −0.4 5.4 9.5 Butane-1,3-diol (aq) 6.0 6.9 ± 0.3 11.0 11.2 ± 0.3 16.7 Butane-1,4-diol (aq) −5.3 −5.3 −0.4 6.2 9.4 9.15 ± 0.29 9.0 ± 0.3 8.3 12.9 13.3 ± 0.3 15.4 16.6 17.7 Butane-2,3-diol (aq) −1.4 −0.1 ± 0.3 5.3 5.7 ± 0.3

ref

cm ·mol−1·GPa−1 3

5 5 5

1.1 1.4 2.0

5 6 5 6 5

0.8 −0.2 0.7 0.5 −0.8

7 8 7 7 8 9 6 5 5 6 7 5 8

0.2 0.2 0.0 0.4 −0.2 0.1 0.2 0.9 0.9 0.5 0.7 0.9 −0.2

5 6 5 6

1.2 −0.1 0.2 −0.2

a

Deviation between this work and the literature value. bInterpolated using the third-order polynomial.

DISCUSSION Comparison with Published Data. Experimental standard molar isentropic compressions are compared in Table 6 with values found in the literature.5−9 Satisfactory agreement is observed with data reported by Høiland6,7 and Nakajima et al.8 (butane-1,3-diol, butane-1,4-diol, butane-2,3-diol). Only one source of published data was found for butane-1,2-diol (Hawrylak et al.5). Our values are systematically greater, and deviations exceed largely the experimental uncertainties. On the other hand large deviations (all positive with one exception) are observed also for data presented by Hawrylak et al.5 for other butanediols. Experimental standard molar volumes are compared with data from the literature1,5,7,10−21 in Table 7. Deviations below 0.1 cm3·mol−1 are observed for data reported by Høiland7,15,19 (butane-1,3-diol, butane-1,4-diol, butane-2,3diol) and Nakajima et al.17 (butane-1,4-diol). Agreement within the experimental uncertainties is also observed for our previous data1 measured at slightly elevated pressure for aqueous butane1,3-diol, butane-1,4-diol, and butane-2,3-diol (for exact experimental temperatures and pressures see the footnote to Table 7; small differences in experimental temperatures from those given in the table and experimental pressures from atmospheric pressure have a negligible effect in these temperature and pressure ranges). Deviations between our data and those measured by Hawrylak et al.5 are mostly of several units of the order 0.1 cm3·mol−1 (negative for butane-1,2-diol and

butane-1,4-diol, positive other two butanediols). Rather larger deviations from published data are observed for butane-1,2-diol. Values reported by Iloukhani and Bahrami11 are significantly lower than our values and other data published in the literature. Their standard molar volumes11 were evaluated from the fits of excess volumes measured for concentrated solutions using the Redlich−Kister expansion. The lowest experimental molality of butane-1,2-diol was about 3.5 mol·kg−1 (mole fraction about 0.06), and it is likely that the deviations are caused by large uncertainty of the extrapolation to infinite dilution. Deviations between our values for aqueous butane-1,2-diol and other published data show slightly systematic character (rather large positive deviations at low temperatures, smaller and negative ones at higher temperatures). Good agreement with data reported by Romero et al.10,12 and Piekarski et al.13 is observed at temperatures T ≥ 298.15 K. Dependences of Standard Isentropic Compression on Temperature. Experimental values of standard isentropic compressibility of aqueous butanediols along with our previous data for isomeric propanediols3 are plotted against temperature in Figure 1. It can be seen that the increase in the distance between the hydroxyl groups within both series of solutes leads to the increase of the standard molar isentropic compression. This distance has a predominant effect; the values for 393



Article

Table 7. Comparison of Measured Values of Standard Molar Volume at p = 0.1 MPa with the Values Taken from the Literature this work T K

literature V 0m,2 −1

cm ·mol 3

± ± ± ±

278.15 283.15 288.15 293.15

85.37 85.60 85.85 86.10

298.15

86.35 ±

303.15

86.62 ±

308.15

86.92 ±

313.15

87.23b

318.15

87.57 ±

298.15

88.30 ±

303.15 308.15

88.47 ± 88.70 ±

318.15

89.15 ±

278.15

87.83 ±

283.15

87.93 ±

288.15

88.04 ±

T

dev. −1

cm ·mol 3

this work a

V 0m,2 Butane-1,2-diol (aq) 0.03 85.02 0.03 85.22 0.03 85.53 0.03 83.25 85.80 0.03 86.16 86.32 86.37 86.43 0.03 85.06 86.58 0.03 85.75 87.36 85.75 87.31 0.04 87.66 88.36 Butane-1,3-diol (aq) 0.02 87.56 88.19 ± 0.02 88.23 88.23 88.32 ± 0.1 88.31 ± 0.02c 0.02 88.70 0.02 88.36 88.66 ± 0.1 0.03 89.21 89.20 ± 0.02d Butane-1,4-diol (aq) 0.02 87.81 ± 0.05 87.81 87.88 0.02 87.99 88.00 ± 0.05 0.02 88.12

ref

cm ·mol

10 10 10 11 10 10 5 12 13 11 10 11 5 11 10 10 5

0.35 0.38 0.32 2.85 0.30 0.19 0.03 −0.02 −0.08 1.56 0.04 1.17 −0.44 1.48 −0.08 −0.09 −0.79

5 14 12 13 15 1 16 5 15 5 1

0.74 0.11 0.07 0.07 −0.02 −0.01 −0.23 0.34 0.04 −0.06 −0.05

7 17 10 10 7 10

0.02 0.02 −0.05 −0.06 −0.07 −0.08

3

−1

K 293.15 298.15

303.15 308.15

313.15 318.15

323.15 298.15

308.15 318.15

literature V 0m,2

cm ·mol 3

dev.a

V 0m,2 −1

cm ·mol 3

−1

Butane-1,4-diol (aq) 88.20 ± 0.02 88.19 ± 0.05 88.19 88.34 ± 0.02 88.16 88.20 ± 0.1 88.20 88.23 ± 0.02 88.27 88.30 ± 0.3 88.30 88.34 ± 0.02e 88.35 ± 0.1 88.36 88.46 88.50 ± 0.1 88.51 ± 0.04 88.38 88.73 ± 0.02 88.55 88.69 ± 0.1 89.02 88.95b 88.77 88.91 ± 0.05 89.19 ± 0.02 89.18 89.23 ± 0.02f 89.05 89.80 89.47b 89.37 Butane-2,3-diol (aq) 86.59 ± 0.02 85.46 86.40 86.47 ± 0.01 86.56 ± 0.1 86.60 ± 0.02c 86.66 87.03 ± 0.02 86.96 ± 0.1 86.05 87.60 ± 0.03 87.64 ± 0.02f 87.39

ref

cm3·mol−1

7 10 12 16 5 18 10 19 13 1 15 17 20 21 10 10 15 5 10 7 17 1 10 5 10

0.01 0.01 0.18 0.14 0.14 0.11 0.07 0.04 0.04 0.00 −0.01 −0.02 −0.12 −0.16 0.13 0.18 0.04 −0.29 0.18 0.04 0.01 −0.04 0.14 −0.61 0.10

5 12 14 15 1 13 15 5 1 5

1.13 0.19 0.12 0.03 −0.01 −0.07 0.07 0.98 −0.04 0.21

a

Deviation between this work and the literature value. bInterpolated using the third-order polynomial. cAt 298.20 K and 0.64 MPa. dAt 318.17 K and 0.50 MPa. eAt 298.21 K and 0.63 MPa. fAt 318.17 K and 0.49 MPa.

Obviously, when isomers with the identical distance of hydroxyl groups are selected (combinations -1,2-/-1,2-, -2,3-/-1,2-, and -1,3-/-1,3-) then the values of K0S,m,2(−CH2−) are close to each other; that is, the effect of the distance is greatly eliminated. On the other hand, the contributions obtained for the pair butane1,4-diol/propane-1,3-diol shown in the figure are significantly larger. The contributions calculated for the pairs butane-1,3diol/propane-1,2-diol and butane-1,4-diol/propane-1,2-diol (not shown in the figure) are even much greater being in the interval from (1.3 to 4.9) cm3·mol−1·GPa−1 and (4.9 to 6.5) cm3·mol−1·GPa−1, respectively. The next two remaining combinations (butane-1,2-diol/propane-1,3-diol and butane-2,3diol/propane-1,3-diol) give values also deviating significantly from those depicted in Figure 2 (both in the interval approximately (−18 to −5) cm3·mol−1·GPa−1). The full lines plotted for a comparison in Figure 2 represent the values calculated from data measured for linear aliphatic (C3 to C6) 1-alkanols, 2-alkanols, and α,ω-alkanediols6,7 and the values obtained as the limiting

butane-1,2-diol and butane-2,3-diol are nearly the same despite the fact that the shapes of molecules are somewhat different. Figure 1 confirms our previous observations2,22 that the slope of the dependence K0S,m,2(T) is affected by the ratio between hydrophilic and hydrophobic portions of the solute molecule (expressed as, e.g., ratio between number of carbon atoms and number of oxygen atoms); more hydrophilic solutes (in a relative scale hydrophilic/hydrophobic) exhibit smaller slopes. In our case the slopes observed for propanediols are lower than those for butanediols. There are eight pairs of butanediol/propanediol isomers which differ by one methylene group, and thus it is possible to evaluate the contribution of this group to the standard isentropic molar compression as K0S,m,2(−CH2−) = K0S,m,2(butanediol) − K0S,m,2(propanediol). The value of this contribution is strongly affected by the selection of particular isomers of both diols. The critical point is the mutual distance of the hydroxyl groups. The results for four selected pairs of isomers are shown in Figure 2. 394



Article

solutes at low temperatures in this work and for aqueous butane1,2-diol, we focus at the temperature range from (278 to 318) K. Experimental standard molar volumes obtained in this work for isomeric butanediols along with the values recently published for isomeric propanediols2 are shown in Figure 3. As it has resulted

Figure 1. Plot of experimental standard molar isentropic compressions K0S,m,2 against temperature T. The lines are to aid the eye. Dashed lines, propanediols; full lines, butanediols. ●, propane-1,2-diol;2 ○, propane1,3-diol;2 ■, butane-1,2-diol; □, butane-1,3-diol; ▲, butane-1,4-diol; △, butane-2,3-diol. Figure 3. Plot of experimental standard molar volumes V0m,2 against temperature T. The lines are to aid the eye. ●, propane-1,2-diol;2 ○, propane-1,3-diol;2 ■, butane-1,2-diol; □, butane-1,3-diol; ▲, butane1,4-diol; △, butane-2,3-diol.

Figure 2. Plot of the contribution of the methylene group K0S,m(−CH2−) to standard molar isentropic compression against temperature T. The lines are to aid the eye. ●, K0S,m,2(butane-1,2-diol) − K0S,m,2(propane-1,2-diol);2 ○, K0S,m,2(butane-2,3-diol) − K0S,m,2(propane-1,2-diol);2 ▲, K0S,m,2(butane1,3-diol) − K0S,m,2(propane-1,3-diol);2 △, K0S,m,2(butane-1,4-diol) − K0S,m,2(propane-1,3-diol)2; full lines: □, Høiland and Vinikgstad6,7 (1-alkanols, 2-alkanols, α,ω-alkanediols); ■, Nakajima et al.8 (1-alkanols, α,ω-alkanediols).

Figure 4. Plot of the contribution of the methylene group V0m,2(−CH2−) to standard molar volume against temperature T. The lines are to aid the eye. ●, V0m,2(butane-1,2-diol) − V0m,2(propane-1,20 0 (butane-2,3-diol) − Vm,2 (propane-1,2-diol);2 ▲, diol);2 ○, Vm,2 0 0 Vm,2(butane-1,3-diol) − Vm,2(propane-1,3-diol);2 △, V0m,2(butane-1,4diol) − V0m,2(propane-1,3-diol);2 full line: Cibulka and Hnědkovský.23

ones for long chain linear 1-alkanols and α,ω-alkanediols.8 Obviously, our values calculated for isomeric pairs with the identical distances of hydroxyl groups are not far from these literature data (particularly at low temperatures) despite the fact that the hydrocarbon frames of the solutes considered here are rather short (C3, C4). Dependences of Standard Molar Volumes and Derived Quantities on Temperature. Dependences of standard molar volume of aqueous butane-1,3-diol, butane-1,4-diol, and butane2,3-diol on temperature and pressure in the entire experimental temperature region from (298 up to 573) K have been analyzed in our previous paper.1 Employing new data obtained for these

from the first-order group contribution approach,23 the structural contribution related to two adjacent hydroxyl groups (the structure −C(OH)−C(OH)−) is negative at low temperatures and becomes positive as the temperature increases. In other words, this contribution behaves as a hydrophilic contribution at lower temperatures and as a hydrophobic contribution at higher temperatures. Present data confirm this observation: standard molar volumes of -1,2- and -2,3-isomers are lower than those of corresponding -1,3- and -1,4-isomers. The curves 395



Article

Table 8. Experimental Densities of Pure Liquid Solutes ρ/(kg·m−3)

a

T/K

butane-1,2-diol

butane-1,3-diol

278.15 283.15 288.15 293.15 298.15 303.15 308.15 318.15

1012.790 1009.213 1005.621 1001.969 998.268 994.526 990.743 983.067

1013.369 1010.090 1006.800 1003.582 1000.304 996.976 993.607 986.754

butane-1,4-diola

butane-2,3-diol

1012.313 1009.301 1006.280 1000.208

1012.963 1009.047 1005.062 1001.163 997.207 993.181 989.106 980.818

The temperature range is limited due to freezing.

exhibit the tendency to cross each other as the temperature increases; at high temperatures the order of magnitudes is reversed, i.e., V0m,2(butane-2,3-diol) > V0m,2(butane-1,3-diol) > 0 0 V m,2 (butane-1,4-diol) 1 and V m,2 (propane-1,2-diol) > V0m,2(propane-1,3-diol).24 From Figure 3 it is obvious, however, that the standard molar volumes are affected by the location of the structure −C(OH)−C(OH)− on the hydrocarbon chain; the standard molar volume of butane-1,2-diol is lower than that of butane-2,3-diol, probably due to the fact that the hydroxyl group bonded to the end carbon atoms is more exposed to interactions with water molecules than that located on the inner carbon atoms. The effect of the length of the hydrocarbon chain is also obvious; the differences between -1,3- and -1,2- or -2,3- isomers of butanediols are approximately two times greater than those for propanediols. On the other hand, the group contribution approach23 with a single structural contribution for −C(OH)−C(OH)− correctly predicts that V0m,2(butane-1,2-diol) < V0m,2(butane-2,3-diol) at low temperatures (the difference between standard volumes is predicted 0 within 0.06 cm 3 ·mol −1 ) with V m,2 (butane-1,2-diol) = V0m,2(butane-2,3-diol) at T = 311 K. It should be pointed out that, contrary to the data for butane-2,3-diol, data for butane-1,2-diol were not included in the evaluation of group contributions.23 Similarly as for the standard isentropic compression the contribution of the methylene group −CH2− was evaluated as V0m,2(−CH2−) = V0m,2(butanediol) −V0m,2(propanediol). The values obtained for the same four solute pairs as in Figure 2 are plotted in Figure 4. Obviously the distance between the hydroxyl groups affects the contribution. The values calculated for -1,3- and -1,4- isomers are close to each other (contrary to K0S,m,2(−CH2−), see Figure 2) and slightly higher than those resulting from our group contribution evaluation,23 while the contributions calculated using data for -1,2- and -2,3- isomers are significantly lower. The knowledge of standard molar volume V0m,2 and molar volume of pure solute Vm,2* enables us to evaluate the limiting slope of the dependence of excess (mixing) volume VE on composition, limx2→0(∂VE/∂x2)T,p = V0m,2 − Vm,2*, where x2 is the mole fraction of the solute. Molar volumes of isomeric butanediols were calculated using experimental densities measured at atmospheric pressure by DSA 5000 device (Table 8) combined with smoothed values calculated from polynomials reported by Zoreb̨ ski and Dzida.25,26 Smoothed values of standard molar volumes calculated for p = 0.1 MPa (see the Supporting Information) were then employed for evaluation of the limiting slopes that are shown in Figure 5. More hydrophilic butanediols (-1,2-, -2,3-) exhibit a larger volume contraction on mixing compared to other two butanediols (-1,3-, -1,4-). While the standard molar volumes of

Figure 5. Plot of limiting slope of excess volume limx2→0(∂VE/∂x2) = V0m,2 − Vm,2 * against temperature T.

aqueous butane-1,3-diol and butane-1,4-diol are similar (Figure 3), lower volume contraction is observed for -1,4-isomer. It is likely that this observation issues from the fact that the molar volume of pure liquid butane-1,4-diol is significantly lower than that of butane-1,3-diol (in an average by about 1.5% in the range from (293 to 353) K) and thus the “ideal” volume of the (butane-1,4diol + water) mixture is smaller than that of the (butane-1,3-diol + water) mixture.

■

CONCLUSIONS New data on speed of sound and density were reported for all aqueous butanediols in the dilute region. Experimental data were then employed for the evaluation of standard molar isentropic compressions and standard molar volumes of the solutes in the temperature range (278 to 318) K, and the effects of the structure (mutual position of the hydroxyl groups) were analyzed. The analysis confirmed the general behavior observed for other aliphatic alcohols.

■

ASSOCIATED CONTENT

S Supporting Information *

Description of the procedure of fitting the standard molar volume data of using either a polynomial function of temperature and pressure for butane-1,3-diol(aq), butane-1,4diol(aq), and butane-2,3-diol(aq) (this work and ref 1) or a polynomial function of temperature for butane-1,2-diol(aq) 396



Article

(15) Høiland, H.; Vikingstad, E. Partial Molal Volumes and Additivity of Group Partial Molal Volumes of Alcohols in Aqueous Solution at 25 and 35 °C. Acta Chem. Scand., Ser. A 1976, 30, 182− 186. (16) Nakanishi, K.; Kato, N.; Maruyama, M. Excess and Partial Volumes of Some Alcohol-Water and Glycol-Water Solutions. J. Phys. Chem. 1967, 71, 814−818. (17) Nakajima, T.; Komatsu, T.; Nakagawa, T. Apparent Molal Volumes and Adiabatic Compressibilities of n-Alkanols and α,ωAlkane Diols in Dilute Aqueous Solutions at 5, 25, and 45 °C. I. Apparent Molal Volumes. Bull. Chem. Soc. Jpn. 1975, 48, 783−787. (18) Jolicoeur, C.; Lacroix, G. Thermodynamic Properties of Aquaous Organic Solutes in Relation to their Structure 0.3. Apparent Molal Volumes and Heat Capacities of Low-Molecular Weight Alcohols and Polyols at 25 °C. Can. J. Chem. 1976, 54, 624−631. (19) Spildo, K.; Høiland, H. Complex Formation between Alkaneα,ω-Diols and Cyclodextrins Studied by Partial Molar Volumes and Compressibility Measurements. J. Solution Chem. 2002, 31, 149−164. (20) Criss, C. M.; Wood, R. H. Apparent Molar Volumes of Aqueous Solutions of Some Organic Solutes at the Pressure 28 MPa and Temperatures to 598 K. J. Chem. Thermodyn. 1996, 28, 723−741. (21) Edward, J. T.; Farrell, P. G.; Shahidi, F. Partial Molar Volumes of Organic Compounds in Water. Part. I. Ethers, Ketones, Esters, and Alcohols. J. Chem. Soc., Faraday Trans. 1 1977, 73, 705−714. (22) Šimurka, L.; Cibulka, I.; Hnědkovský, L. Partial Molar Isentropic Compressions and Partial Molar Volumes of Selected Branched Aliphatic Alcohols at Infinite Dilution in Water at Temperatures T = (278 to 318) K and Atmospheric Pressure. J. Chem. Eng. Data 2012, 57, 1570−1580. (23) Cibulka, I.; Hnědkovský, L. Group Contribution Method for Standard Molar Volumes of Aqueous Aliphatic Alcohols, Ethers and Ketones in Extended Ranges of Temperature and Pressure. J. Chem. Thermodyn. 2011, 43, 1215−1223. (24) Hynčica, P.; Hnědkovský, L.; Cibulka, I. Partial Molar Volumes of Organic Solutes in Water. XIV. Polyhydric Alcohols Derived from Ethane and Propane at Temperatures T = 298 to 573 K and at Pressures up to 30 MPa. J. Chem. Thermodyn. 2006, 38, 801−809. (25) Zorębski, E.; Dzida, M. Study of the Acoustic and Thermodynamic Properties of 1,2- and 1,3-Butanediol by Means of High-Pressure Speed of Sound Measurements at Temperatures from (293 to 318) K and Pressures up to 101 MPa. J. Chem. Eng. Data 2007, 52, 1010−1017. (26) Zorębski, E.; Dzida, M. The Effect of Temperature and Pressure on Acoustic and Thermodynamic Properties of 1,4-Butanediol. The Comparison with 1,2- and 1,3-Butanediols. J. Chem. Thermodyn. 2012, 54, 100−107.

(this work). Adjustable parameters of the smoothing polynomials. This material is available free of charge via the Internet at http://pubs.acs.org.

■

AUTHOR INFORMATION

Corresponding Author

*Phone: +420 220444063; e-mail: [email protected]. Funding

Support from the Ministry of Education, Youth and Sports of the Czech Republic (fund MSM6046137307) is acknowledged. Notes

The authors declare no competing financial interest.

■

REFERENCES

(1) Hynčica, P.; Hnědkovský, L.; Cibulka, I. Partial molar volumes of organic solutes in water. XV. Butanediols(aq) at temperatures T = 298 to 573 K and at pressures up to 30 MPa. J. Chem. Thermodyn. 2006, 38, 1085−1091. (2) Katriňaḱ , T.; Hnědkovský, L.; Cibulka, I. Partial molar volumes and partial molar isentropic compressions of three polyhydric alcohols derived from propane at infinite dilution in water at temperatures T = (278 to 318) K and atmospheric pressure. J. Chem. Eng. Data 2012, 57, 1152−1159. (3) Harvey, A. H.; Peskin, A. P.; Klein, S. A. NIST/ASME Steam Properties, Formulation for General and Scientific Use. NIST Standard Reference Database 10, Version 2.11; National Institute of Standards and Technology: Gaithersburg, MD, 1996. (4) Hynek, V.; Hnědkovský, L.; Cibulka, I. A New Design of a Vibrating-tube Densimeter and Partial Molar Volumes of Phenol(aq) at Temperatures from 298 to 573 K. J. Chem. Thermodyn. 1997, 29, 1237−1252. (5) Hawrylak, B.; Gracie, K.; Palepu, R. Thermodynamic Properties of Binary Mixtures of Butanediols with Water. J. Solution Chem. 1998, 27, 17−31. (6) Høiland, H.; Vinikgstad, E. Isentropic Apparent Molal Comppressibilities of Alcohols in Aqueous Solution. Relations to van der Walls Radii and the Scaled Particle Theory. Acta Chem. Scand. 1976, A30, 692−696. (7) Høiland, H. Partial Molal Volumes, Expansibilities, and Compressibilities for Aqueous Alcohol Solutions between 5 °C and 40 °C. J. Solution Chem. 1980, 9, 857−866. (8) Nakajima, T.; Komatsu, T.; Nakagawa, T. Apparent Molal Volumes and Adiabatic Compressibilities of n-Alkanols and α,ωAlkane Diols in Dilute Aqueous Solutions at 5, 25, and 45 °C. II. Apparent Molal Adaibatic Compressibilities. Bull. Chem. Soc. Jpn. 1975, 48, 788−790. (9) Hakin, A. W.; Høiland, H. Speed of Sound Measurements Conducted at High Pressures on Aqueous Alcohol and Aqueous Diol Systems at T = 298.15 K. Phys. Chem. Chem. Phys. 2005, 7, 2199− 2207. (10) Romero, C. M.; Lozano, J. M.; Giraldo, G. I. Effect of Temperature on Partial Molar Volumes and Viscosities of Dilute Aqueous Solutions of 1-Butanol, 1,2-Butanediol, 1,4-Butanediol, 1,2,7Butanetriol, and Butaneterol. Phys. Chem. Liq. 2008, 46, 78−85. (11) Iloukhani, H.; Bahrami, H. Excess Molar Volumes and Partial Molar Volumes for Binary Mixtures of Water with 1,2-Ethanediol, 1,2Propanediol, and 1,2-Butanediol at 298.15, 303.15, and 313.15 K. Phys. Chem. Liq. 2000, 38, 103−111. (12) Romero, C. M.; Paez, M. S. Volumetric Properties of Aqueous Binary Mixtures of 1-Butanol, Butanediols, 1,2,4-Butanetriol and Butanetetrol at 298.15 K. J. Solution Chem. 2007, 36, 237−245. (13) Piekarski, H.; Józw ́ iak, M.; Woźnicka, J.; Bald, A.; Szejgis, A. Some Physicochemical Properties of Aqueous Solutions of Isomeric Butanediols. Phys. Chem. Liq. 1995, 30, 195−207. (14) Wurzburger, S.; Sartorio, R.; Elia, V.; Cascella, C. Volumetric Properties of Aqueous Solutions of Alcohols and Diols at 25 °C. J. Chem. Soc., Faraday Trans. 1990, 86, 3891−3895. 397


Partial Molar Isentropic Compressions and Partial Molar Volumes of

Recommend Documents