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Semi-empirical algorithm for estimation of calorimetric properties in binary liquid mixtures from acoustic and volumetric data
⁎Corresponding authors at: Center of Applied Nanoscience (CANS), Facultad de Ciencias Exactas, Universidad Andres Bello, Av. República 330, Santiago, Chile. mspaezm@correo.unicordoba.edu.co (Manuel S. Páez Meza), pliniocantero@gmail.com (Plinio Cantero-López) p.canterolpez@uandresbello.edu (Plinio Cantero-López)
-
Received: ,
Accepted: ,
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.
Peer review under responsibility of King Saud University.
Abstract
Abstract
In the present work, a semi-empirical algorithm is proposed for estimating the adiabatic coefficient ( ), the isothermal compressibility ( ), the heat capacity at constant pressure ( ), and constant volume ( ), for liquid mixtures of organic compounds as a function of temperature and concentration. The algorithm was applied to the binary systems: 1,6-Dichlorohexene (x) + Dodecane (1-x) and 1,5-Dichloropentane (x) + Dodecane (1-x) reported in literature. The obtaining values for , and are reported at all concentrations and temperatures. The implementation of the algorithm required experimental data of the adiabatic coefficients of the pure components ( ) to 298.15 K, acoustic and volumetric data of the binary mixture in the entire concentration and temperature range between (278.15–328.15) K every 5 K. The results obtained are in excellent agreement with the experimental results.
Keywords
Semi-empirical algorithm
Isothermal compressibility
Heat capacity
Adiabatic coefficient
Speed of sound
Isobaric expansibility
1 Introduction
The study of thermophysical properties of mixtures containing organic compounds is a fundamental topic at the industrial and scientific level (Chiu et al., 1999; Tkachenko et al., 2011). The analysis of their magnitudes and trends allows obtaining microscopic and macroscopic information on the behavior of different molecules in the liquid mixtures(González-Salgado et al., 2004). In this context, the adiabatic coefficient, heat capacities, and isothermal compressibilities are important quantities to achieve this goal(Chen et al., 2001; Paulechka et al., 2010). However, its obtaining and calculation in many cases is not easy or requires the use of specialized equipment that has a high monetary cost(Pandey et al., 2003; Srinivasa Reddy et al., 2016). One of the problems consists in obtaining the adiabatic coefficient, or also the heat capacity at constant volume ( ), perhaps due to the high sensitivity to changes in pressure and temperature compared to the heat capacity at constant pressure ( ). The reported values of the isobaric heat capacities of liquids are normally obtained by direct calorimetric determination, the relatively scarce values of isochoric heat capacities are for the most part obtained indirectly by the use of the acoustic method (Perkins and Magee, 2009; Wilhelm, 2010, 1955; Zorębski, 2014; Zorȩbski et al., 2017).
In the literature have been proposed different theoretical approach for estimating the heat capacities based primordially on the use of group contribution methods (Ceriani et al., 2009; Kolská et al., 2005; Marrero and Gani, 2001) or molecular volumes(Naef, 2019). Where some of them involve multiple steps and are quite tedious to follow. However, based on the importance of this topic in order to contribute to the solution of the previously mentioned difficulties regarding the accessibility of experimental data, in this work a semiempirical algorithm was developed to evaluate the adiabatic coefficient, supported by the abundance of densitometric and acoustic data. So , the access to the acoustic and densitometric data guarantee the evaluation of the adiabatic compressibility using Laplace’s equation(González-Salgado et al., 2004), isothermal compressibility and heat capacities using Mayer’s Relationship(Güémez et al., 1995). This indirect method is attractive because calorimetric determination of isochoric heat capacities of liquids is still difficult. In this context, Pandey and coworkers (Md Nayeem et al., 2014; Pandey et al., 2003) used the equation of the state for hard sphere to calculated the isothermal compressibility for six binary liquid mixtures: n-heptane + toluene (I); n-heptane + n-hexane (II); toluene + n-hexane (III); cyclohexane + n-heptane (IV); cyclohexane + n-hexane (V), and n-decane + n-hexane (VI) at 298.15 K, using density and speed of sound data. However, a deeply examination of the obtained results, showed that only one equation of the eight illustrated is close to the experimental results, showing anomalies if the system changes. So, the developed algorithm does not have this problem. Additionally, the proposed model provides an easy and low-cost protocol to complement the results obtained from volumetric and acoustic data of different organic liquid mixtures.
2 Methodology
2.1 Variable evaluation
To validate the proposed model, density and sound velocity data of 1,6-Dichlorohexene (x) + Dodecane (1-x) and 1,5-Dichloropentane (x) + Dodecane (1-x) obtained from Gómez-Díaz (González-Salgado et al., 2004) and coworkers were used (see Table 1).These data allow us to evaluate the adiabatic compressibility (
), the molar volumes (V), the coefficient of thermal expansion
and the derivative of the density with respect to the temperature
. The adiabatic compressibility (
), was evaluated using the Newton-Laplace equation:
*The related information about chemical reagents were taken from the literature (González-Salgado et al., 2004).
Component
CAS
Suppliers
Mol fraction
1,6-Dichlorohexene
2163-00-0
Sigma Aldrich
Dodecane
112-40-3
Sigma Aldrich
0.990
1,5-Dichloropentane
628-76-2
Sigma Aldrich
Molar volumes V was evaluated using the following equation:
The coefficient of thermal expansion
, at the temperature T can be calculated using the expression
3 Method implementation
was evaluated for , and for , using the Eq. (16), as input data of the 1,6-Dichlorohexene (x) + Dodecane (1-x) system: = 1.2089 and = 1.2649 and for the 1,5-Dichloropentane (x) + Dodecane (1-x) system: = 1.2089 and = 1.2855 for the pure components at the temperature of 298.15 K. The rest of the experimental measures ( ) were reported by González-Salgado and coworkers(González-Salgado et al., 2004). In the Eqs. (13) to (15), , , and were evaluated for each solution of Eq 17 was solved to obtain values for all temperatures and concentrations. Finally, we evaluated and using the values previously obtained.
4 Results and discussion
The semiempirical algorithm is based on the solid and well-grounded thermodynamic arguments. Based on this, it is possible to show that the heat capacity at constant pressure can be obtained by:
Based on Eq. (1) and by analogy with Laplace’s equation for adiabatic compressibility (
), it is possible to express the isothermal compressibility (
), the heat capacity at constant pressure (
) and constant volume (
), using the following equations:
The Eq. (11) is in full agreement with the generalized Mayer equation(Güémez et al., 1995) for the isothermic compressibility.
On the other hand, empirical observations allowed us to infer that the J parameter, for a fixed concentration is approximately constant, this fact validates the use of the average (
) instead of a specific J values. So, the determination of this parameter constitutes a key factor on which the development of this article is based. Therefore, we proposed to empirically evaluate this parameter from the following equation:
Which results from equating Eqs. (12) and (13). Eq. (17) can be applied to both components, pure and mixed components. In this context, the problem is reduced to finding the value of
that is a solution of Eq. (17) at all temperatures and concentrations of the different binary liquid mixtures. The resolution of Eq. (17) was solved by numerical manipulation. The results obtained are reported in Tables 2 and 3, for the pure liquids and their mixtures *The measurement used in this work were determined under pressure of 0.1 MPa. The standard uncertainties u are u(p) = 0.04 MPa for pressure, u(T) = 4.07 K for temperature , u(x) = 0.5946 for molar fraction (0.68 level of confidence). *The measurement used in this work were determined under pressure of 0.1 MPa. The standard uncertainties u are u(p) = 0.04 MPa for pressure, u(T) = 4.07 K for temperature, u(x) = 0.5946 for molar fraction (0.68 level of confidence).
%error
x2 = 0.00000
278.15
1.2129
1.2138
0.07
365.07
0.42
300.77
0.49
8.676E-10
0.07
283.15
1.2122
1.2127
0.05
367.52
0.26
303.06
0.30
8.970E-10
0.05
288.15
1.2113
1.2116
0.02
370.00
0.13
305.39
0.15
9.276E-10
0.02
293.15
1.2102
1.2103
0.01
372.51
0.06
307.79
0.07
9.594E-10
0.01
298.15
1.2089
1.2089
0.00
375.04
0.00
310.23
0.00
9.925E-10
0.00
303.15
1.2076
1.2075
0.01
377.60
0.05
312.72
0.05
1.027E-09
0.01
308.15
1.2060
1.2059
0.01
380.20
0.05
315.28
0.05
1.063E-09
0.01
313.15
1.2043
1.2043
0.00
382.82
0.02
317.88
0.03
1.100E-09
0.00
318.15
1.2026
1.2026
0.00
385.47
0.00
320.53
0.00
1.139E-09
0.00
323.15
1.2008
1.2008
0.01
388.15
0.04
323.23
0.04
1.179E-09
0.01
328.15
1.1987
1.1990
0.03
390.86
0.16
325.98
0.19
1.221E-09
0.03
x2 = 0.04980
278.15
1.2154
1.2156
0.02
358.89
0.09
295.25
0.10
8.601E-10
0.02
283.15
1.2145
1.2145
0.00
361.22
0.01
297.42
0.01
8.889E-10
0.00
288.15
1.2135
1.2133
0.02
363.57
0.09
299.65
0.10
9.192E-10
0.02
293.15
1.2122
1.2120
0.02
365.93
0.12
301.93
0.14
9.506E-10
0.02
298.15
1.2109
1.2106
0.03
368.33
0.16
304.26
0.19
9.833E-10
0.03
303.15
1.2094
1.2091
0.03
370.75
0.16
306.64
0.18
1.017E-09
0.03
308.15
1.2077
1.2075
0.02
373.21
0.13
309.09
0.15
1.053E-09
0.02
313.15
1.2060
1.2058
0.02
375.69
0.09
311.57
0.10
1.089E-09
0.02
318.15
1.2042
1.2041
0.01
378.19
0.03
314.09
0.04
1.128E-09
0.01
323.15
1.2022
1.2023
0.01
380.73
0.03
316.67
0.04
1.167E-09
0.01
328.15
1.2003
1.2004
0.01
383.29
0.08
319.30
0.09
1.209E-09
0.01
x2 = 0.10030
278.15
1.2164
1.2168
0.03
351.56
0.18
288.91
0.21
8.513E-10
0.03
283.15
1.2156
1.2158
0.02
353.81
0.11
291.00
0.13
8.798E-10
0.02
288.15
1.2145
1.2146
0.01
356.07
0.04
293.16
0.04
9.096E-10
0.01
293.15
1.2133
1.2133
0.00
358.37
0.00
295.37
0.00
9.406E-10
0.00
298.15
1.2119
1.2119
0.00
360.68
0.01
297.63
0.01
9.728E-10
0.00
303.15
1.2103
1.2103
0.00
363.02
0.01
299.93
0.02
1.006E-09
0.00
308.15
1.2087
1.2088
0.01
365.39
0.04
302.28
0.05
1.041E-09
0.01
313.15
1.2069
1.2071
0.02
367.79
0.09
304.69
0.11
1.077E-09
0.02
318.15
1.2051
1.2054
0.02
370.20
0.13
307.13
0.15
1.115E-09
0.02
323.15
1.2031
1.2035
0.03
372.66
0.19
309.63
0.22
1.154E-09
0.03
328.15
1.2011
1.2017
0.04
375.13
0.26
312.18
0.30
1.195E-09
0.04
x2 = 0.14973
278.15
1.2198
1.2193
0.04
346.17
0.22
283.91
0.26
8.428E-10
0.04
283.15
1.2189
1.2183
0.05
348.36
0.28
285.95
0.33
8.708E-10
0.05
288.15
1.2178
1.2170
0.06
350.57
0.35
288.05
0.41
9.003E-10
0.06
293.15
1.2165
1.2157
0.06
352.80
0.35
290.20
0.41
9.308E-10
0.06
298.15
1.2151
1.2143
0.07
355.06
0.37
292.40
0.44
9.627E-10
0.07
303.15
1.2135
1.2128
0.06
357.34
0.36
294.64
0.42
9.958E-10
0.06
308.15
1.2119
1.2112
0.05
359.65
0.32
296.94
0.37
1.030E-09
0.05
313.15
1.2101
1.2095
0.05
361.99
0.27
299.28
0.32
1.066E-09
0.05
318.15
1.2082
1.2078
0.03
364.35
0.20
301.66
0.24
1.103E-09
0.03
323.15
1.2062
1.2060
0.02
366.73
0.12
304.10
0.14
1.142E-09
0.02
328.15
1.2042
1.2041
0.01
369.14
0.04
306.57
0.04
1.182E-09
0.01
x2 = 0.25271
278.15
1.2243
1.2234
0.07
332.92
0.40
272.12
0.47
8.224E-10
0.07
283.15
1.2234
1.2224
0.08
334.97
0.42
274.02
0.50
8.495E-10
0.08
288.15
1.2222
1.2212
0.08
337.03
0.45
275.99
0.53
8.780E-10
0.08
293.15
1.2208
1.2199
0.08
339.12
0.44
277.99
0.52
9.075E-10
0.08
298.15
1.2194
1.2184
0.08
341.23
0.44
280.05
0.52
9.383E-10
0.08
303.15
1.2178
1.2169
0.07
343.36
0.42
282.15
0.49
9.703E-10
0.07
308.15
1.2161
1.2153
0.06
345.52
0.36
284.31
0.43
1.004E-09
0.06
313.15
1.2143
1.2137
0.05
347.70
0.31
286.49
0.36
1.038E-09
0.05
318.15
1.2124
1.2119
0.04
349.90
0.22
288.72
0.26
1.074E-09
0.04
323.15
1.2104
1.2101
0.03
352.13
0.15
291.00
0.17
1.111E-09
0.03
328.15
1.2082
1.2081
0.00
354.38
0.02
293.33
0.03
1.150E-09
0.00
x2 = 0.40173
278.15
1.2314
1.2303
0.10
313.91
0.51
255.2
0.61
7.889E-10
0.10
283.15
1.2303
1.2292
0.09
315.70
0.49
256.8
0.58
8.147E-10
0.09
288.15
1.2291
1.2279
0.09
317.51
0.50
258.6
0.60
8.416E-10
0.09
293.15
1.2276
1.2266
0.08
319.35
0.46
260.4
0.54
8.694E-10
0.08
298.15
1.2261
1.2251
0.08
321.20
0.44
262.2
0.52
8.985E-10
0.08
303.15
1.2244
1.2236
0.07
323.08
0.38
264.0
0.45
9.286E-10
0.07
308.15
1.2226
1.2219
0.06
324.97
0.32
266.0
0.37
9.599E-10
0.06
313.15
1.2207
1.2202
0.04
326.89
0.22
267.9
0.26
9.923E-10
0.04
318.15
1.2187
1.2184
0.02
328.82
0.13
269.9
0.15
1.026E-09
0.02
323.15
1.2166
1.2165
0.00
330.78
0.02
271.9
0.02
1.061E-09
0.00
328.15
1.2143
1.2146
0.02
332.74
0.11
274.0
0.13
1.097E-09
0.02
x2 = 0.50199
278.15
1.2361
1.2350
0.09
300.73
0.48
243.5
0.57
7.639E-10
0.09
283.15
1.2350
1.2340
0.08
302.42
0.43
245.1
0.51
7.884E-10
0.08
288.15
1.2338
1.2328
0.08
304.12
0.43
246.7
0.51
8.141E-10
0.08
293.15
1.2324
1.2315
0.08
305.85
0.41
248.4
0.48
8.407E-10
0.08
298.15
1.2309
1.2301
0.07
307.59
0.37
250.1
0.44
8.684E-10
0.07
303.15
1.2292
1.2285
0.06
309.35
0.31
251.8
0.37
8.972E-10
0.06
308.15
1.2275
1.2269
0.04
311.13
0.24
253.6
0.29
9.271E-10
0.04
313.15
1.2256
1.2252
0.03
312.93
0.16
255.4
0.19
9.581E-10
0.03
318.15
1.2236
1.2235
0.01
314.74
0.06
257.3
0.07
9.902E-10
0.01
323.15
1.2215
1.2216
0.01
316.58
0.04
259.2
0.05
1.024E-09
0.01
328.15
1.2194
1.2196
0.02
318.42
0.12
261.1
0.14
1.058E-09
0.02
x2 = 0.59998
278.15
1.2421
1.2407
0.11
288.48
0.58
232.5
0.70
7.374E-10
0.11
283.15
1.2410
1.2397
0.11
289.98
0.57
233.9
0.68
7.607E-10
0.11
288.15
1.2397
1.2384
0.10
291.50
0.54
235.4
0.65
7.852E-10
0.10
293.15
1.2382
1.2371
0.09
293.03
0.48
236.9
0.58
8.104E-10
0.09
298.15
1.2366
1.2356
0.08
294.58
0.41
238.4
0.49
8.368E-10
0.08
303.15
1.2348
1.2341
0.06
296.15
0.32
240.0
0.39
8.641E-10
0.06
308.15
1.2329
1.2324
0.04
297.73
0.22
241.6
0.26
8.924E-10
0.04
313.15
1.2309
1.2307
0.02
299.33
0.11
243.2
0.13
9.218E-10
0.02
318.15
1.2288
1.2289
0.00
300.94
0.01
244.9
0.01
9.522E-10
0.00
323.15
1.2266
1.2270
0.03
302.57
0.14
246.6
0.17
9.839E-10
0.03
328.15
1.2242
1.2250
0.06
304.21
0.32
248.3
0.38
1.017E-09
0.06
x2 = 0.70111
278.15
1.2482
1.2467
0.11
275.29
0.58
220.8
0.70
7.078E-10
0.11
283.15
1.2472
1.2458
0.11
276.67
0.58
222.1
0.70
7.298E-10
0.11
288.15
1.2459
1.2446
0.10
278.06
0.53
223.4
0.63
7.529E-10
0.10
293.15
1.2443
1.2432
0.09
279.47
0.45
224.8
0.54
7.768E-10
0.09
298.15
1.2427
1.2418
0.07
280.89
0.37
226.2
0.44
8.016E-10
0.07
303.15
1.2409
1.2402
0.05
282.33
0.28
227.6
0.33
8.274E-10
0.05
308.15
1.2390
1.2386
0.03
283.78
0.15
229.1
0.18
8.542E-10
0.03
313.15
1.2370
1.2369
0.01
285.24
0.03
230.6
0.04
8.818E-10
0.01
318.15
1.2349
1.2351
0.02
286.72
0.10
232.1
0.12
9.104E-10
0.02
323.15
1.2326
1.2332
0.04
288.22
0.23
233.7
0.28
9.403E-10
0.04
328.15
1.2303
1.2312
0.07
289.71
0.37
235.3
0.44
9.711E-10
0.07
x2 = 0.79862
278.15
1.2561
1.2539
0.18
263.25
0.87
209.9
1.05
6.777E-10
0.18
283.15
1.2549
1.2529
0.16
264.43
0.79
211.1
0.95
6.984E-10
0.16
288.15
1.2533
1.2516
0.14
265.64
0.68
212.2
0.82
7.202E-10
0.14
293.15
1.2516
1.2503
0.11
266.85
0.55
213.4
0.66
7.426E-10
0.11
298.15
1.2499
1.2488
0.09
268.07
0.44
214.7
0.53
7.659E-10
0.09
303.15
1.2479
1.2472
0.06
269.31
0.30
215.9
0.36
7.901E-10
0.06
308.15
1.2458
1.2455
0.03
270.56
0.15
217.2
0.18
8.151E-10
0.03
313.15
1.2437
1.2437
0.00
271.82
0.02
218.6
0.02
8.410E-10
0.00
318.15
1.2414
1.2418
0.04
273.09
0.19
219.9
0.22
8.678E-10
0.04
323.15
1.2390
1.2399
0.07
274.38
0.36
221.3
0.43
8.957E-10
0.07
328.15
1.2365
1.2378
0.11
275.66
0.55
222.7
0.66
9.244E-10
0.11
x2 = 0.89982
278.15
1.2637
1.2615
0.17
250.00
0.84
198.2
1.02
6.441E-10
0.17
283.15
1.2621
1.2604
0.13
250.97
0.64
199.1
0.78
6.634E-10
0.13
288.15
1.2603
1.2591
0.10
251.95
0.48
200.1
0.57
6.837E-10
0.10
293.15
1.2584
1.2576
0.06
252.94
0.28
201.1
0.34
7.045E-10
0.06
298.15
1.2563
1.2561
0.02
253.93
0.10
202.2
0.12
7.262E-10
0.02
303.15
1.2542
1.2544
0.01
254.94
0.07
203.2
0.08
7.485E-10
0.01
308.15
1.2519
1.2526
0.05
255.95
0.26
204.3
0.32
7.718E-10
0.05
313.15
1.2496
1.2507
0.09
256.98
0.46
205.5
0.56
7.958E-10
0.09
318.15
1.2471
1.2488
0.14
258.00
0.68
206.6
0.81
8.205E-10
0.14
323.15
1.2445
1.2468
0.18
259.05
0.91
207.8
1.08
8.462E-10
0.18
328.15
1.2419
1.2446
0.22
260.09
1.12
209.0
1.34
8.728E-10
0.22
x2 = 0.94934
278.15
1.2683
1.2659
0.19
243.83
0.90
192.6
1.09
6.272E-10
0.19
283.15
1.2669
1.2649
0.16
244.73
0.77
193.5
0.93
6.458E-10
0.16
288.15
1.2650
1.2635
0.12
245.65
0.58
194.4
0.70
6.652E-10
0.12
293.15
1.2630
1.2621
0.08
246.57
0.37
195.4
0.44
6.854E-10
0.08
298.15
1.2609
1.2605
0.03
247.51
0.17
196.4
0.20
7.062E-10
0.03
303.15
1.2588
1.2589
0.01
248.45
0.03
197.4
0.03
7.277E-10
0.01
308.15
1.2565
1.2571
0.05
249.39
0.24
198.4
0.29
7.500E-10
0.05
313.15
1.2541
1.2552
0.09
250.35
0.46
199.4
0.55
7.730E-10
0.09
318.15
1.2516
1.2533
0.14
251.31
0.68
200.5
0.81
7.968E-10
0.14
323.15
1.2490
1.2513
0.18
252.29
0.90
201.6
1.07
8.215E-10
0.18
328.15
1.2463
1.2491
0.23
253.26
1.14
202.7
1.36
8.470E-10
0.23
x2 = 0.96911
278.15
1.2702
1.2677
0.20
241.36
0.93
190.4
1.13
6.204E-10
0.20
283.15
1.2688
1.2667
0.17
242.28
0.79
191.3
0.95
6.387E-10
0.17
288.15
1.2670
1.2654
0.13
243.22
0.61
192.2
0.74
6.579E-10
0.13
293.15
1.2652
1.2641
0.09
244.16
0.42
193.2
0.51
6.777E-10
0.09
298.15
1.2632
1.2625
0.05
245.11
0.24
194.1
0.29
6.982E-10
0.05
303.15
1.2611
1.2609
0.01
246.08
0.07
195.2
0.09
7.195E-10
0.01
308.15
1.2589
1.2592
0.03
247.05
0.13
196.2
0.16
7.414E-10
0.03
313.15
1.2565
1.2574
0.07
248.03
0.33
197.3
0.40
7.641E-10
0.07
318.15
1.2541
1.2555
0.11
249.01
0.54
198.3
0.65
7.876E-10
0.11
323.15
1.2516
1.2535
0.15
250.01
0.75
199.4
0.90
8.119E-10
0.15
328.15
1.2490
1.2514
0.20
251.00
0.98
200.6
1.17
8.370E-10
0.20
x2 = 1.00000
278.15
1.2723
1.2701
0.17
237.00
0.82
186.6
0.99
6.094E-10
0.17
283.15
1.2705
1.2691
0.12
237.89
0.55
187.5
0.66
6.272E-10
0.12
288.15
1.2688
1.2678
0.08
238.78
0.37
188.3
0.45
6.460E-10
0.08
293.15
1.2669
1.2664
0.04
239.69
0.18
189.3
0.22
6.653E-10
0.04
298.15
1.2649
1.2649
0.00
240.60
0.00
190.2
0.00
6.853E-10
0.00
303.15
1.2629
1.2633
0.04
241.52
0.17
191.2
0.21
7.059E-10
0.04
308.15
1.2606
1.2616
0.08
242.45
0.38
192.2
0.46
7.273E-10
0.08
313.15
1.2583
1.2598
0.12
243.39
0.58
193.2
0.70
7.494E-10
0.12
318.15
1.2559
1.2579
0.16
244.33
0.79
194.2
0.95
7.722E-10
0.16
323.15
1.2534
1.2560
0.20
245.29
1.00
195.3
1.20
7.959E-10
0.20
328.15
1.2510
1.2539
0.23
246.23
1.12
196.4
1.35
8.202E-10
0.23
x2 = 0.00000
278.15
1.2129
1.2138
0.07
365.07
0.42
300.77
0.49
8.676E-10
0.07
283.15
1.2122
1.2127
0.05
367.52
0.26
303.05
0.30
8.970E-10
0.05
288.15
1.2113
1.2116
0.02
370.00
0.13
305.39
0.15
9.276E-10
0.02
293.15
1.2102
1.2103
0.01
372.51
0.06
307.78
0.07
9.594E-10
0.01
298.15
1.2089
1.2089
0.00
375.04
0.00
310.22
0.00
9.925E-10
0.00
303.15
1.2076
1.2075
0.01
377.60
0.05
312.72
0.05
1.027E-09
0.01
308.15
1.2060
1.2059
0.01
380.20
0.05
315.27
0.05
1.063E-09
0.01
313.15
1.2044
1.2043
0.00
382.82
0.02
317.88
0.03
1.100E-09
0.00
318.15
1.2026
1.2026
0.00
385.47
0.00
320.53
0.00
1.139E-09
0.00
323.15
1.2008
1.2009
0.01
388.15
0.04
323.23
0.04
1.179E-09
0.01
328.15
1.1987
1.1990
0.03
390.86
0.16
325.98
0.19
1.221E-09
0.03
x2 = 0.05237
278.15
1.2147
1.2159
0.10
355.55
0.57
291.89
0.85
8.616E-10
0.10
283.15
1.2138
1.2148
0.08
357.81
0.47
294.02
0.73
8.907E-10
0.08
288.15
1.2128
1.2136
0.07
360.10
0.38
296.20
0.62
9.209E-10
0.07
293.15
1.2115
1.2122
0.06
362.41
0.33
298.44
0.56
9.524E-10
0.06
298.15
1.2101
1.2108
0.05
364.75
0.31
300.72
0.54
9.852E-10
0.05
303.15
1.2086
1.2093
0.06
367.10
0.32
303.05
0.55
1.019E-09
0.06
308.15
1.2069
1.2076
0.06
369.49
0.35
305.44
0.58
1.055E-09
0.06
313.15
1.2051
1.2059
0.07
371.90
0.40
307.87
0.64
1.092E-09
0.07
318.15
1.2032
1.2042
0.08
374.34
0.46
310.35
0.70
1.130E-09
0.08
323.15
1.2013
1.2023
0.09
376.81
0.53
312.87
0.79
1.170E-09
0.09
328.15
1.1991
1.2005
0.11
379.32
0.65
315.45
0.92
1.211E-09
0.11
x2 = 0.10136
278.15
1.2172
1.2183
0.09
347.21
0.51
284.04
0.94
8.553E-10
0.09
283.15
1.2162
1.2172
0.09
349.43
0.48
286.12
0.90
8.840E-10
0.09
288.15
1.2151
1.2160
0.07
351.68
0.42
288.25
0.82
9.140E-10
0.07
293.15
1.2139
1.2147
0.07
353.96
0.38
290.44
0.78
9.452E-10
0.07
298.15
1.2125
1.2132
0.06
356.24
0.36
292.67
0.75
9.777E-10
0.06
303.15
1.2110
1.2117
0.06
358.56
0.35
294.95
0.73
1.011E-09
0.06
308.15
1.2093
1.2101
0.07
360.91
0.38
297.28
0.77
1.047E-09
0.07
313.15
1.2075
1.2084
0.07
363.28
0.43
299.67
0.82
1.083E-09
0.07
318.15
1.2056
1.2066
0.08
365.68
0.49
302.09
0.89
1.121E-09
0.08
323.15
1.2037
1.2048
0.09
368.10
0.56
304.56
0.96
1.161E-09
0.09
328.15
1.2015
1.2029
0.11
370.56
0.68
307.08
1.11
1.202E-09
0.11
x2 = 0.20075
278.15
1.2220
1.2238
0.14
331.04
0.77
268.84
1.52
8.405E-10
0.14
283.15
1.2215
1.2227
0.09
333.14
0.51
270.80
1.21
8.686E-10
0.09
288.15
1.2205
1.2215
0.08
335.27
0.45
272.81
1.14
8.980E-10
0.08
293.15
1.2192
1.2201
0.07
337.42
0.41
274.86
1.09
9.285E-10
0.07
298.15
1.2178
1.2187
0.07
339.58
0.40
276.96
1.07
9.602E-10
0.07
303.15
1.2163
1.2171
0.07
341.78
0.38
279.12
1.04
9.932E-10
0.07
308.15
1.2146
1.2155
0.08
344.00
0.43
281.32
1.09
1.028E-09
0.08
313.15
1.2128
1.2138
0.08
346.24
0.47
283.57
1.14
1.063E-09
0.08
318.15
1.2109
1.2120
0.09
348.51
0.52
285.86
1.20
1.100E-09
0.09
323.15
1.2083
1.2101
0.15
350.80
0.87
288.19
1.60
1.139E-09
0.15
328.15
1.2063
1.2082
0.16
353.12
0.92
290.57
1.65
1.179E-09
0.16
x2 = 0.30395
278.15
1.2277
1.2296
0.15
314.17
0.80
253.31
1.80
8.219E-10
0.15
283.15
1.2267
1.2284
0.14
316.08
0.75
255.10
1.74
8.493E-10
0.14
288.15
1.2256
1.2272
0.13
318.01
0.72
256.93
1.70
8.777E-10
0.13
293.15
1.2243
1.2258
0.13
319.96
0.69
258.81
1.65
9.073E-10
0.13
298.15
1.2228
1.2243
0.13
321.93
0.69
260.74
1.65
9.381E-10
0.13
303.15
1.2212
1.2227
0.13
323.92
0.69
262.70
1.64
9.701E-10
0.13
308.15
1.2194
1.2211
0.13
325.94
0.74
264.72
1.70
1.003E-09
0.13
313.15
1.2175
1.2193
0.14
327.97
0.80
266.77
1.76
1.038E-09
0.14
318.15
1.2155
1.2174
0.16
330.03
0.87
268.87
1.84
1.074E-09
0.16
323.15
1.2135
1.2155
0.17
332.12
0.94
271.01
1.91
1.111E-09
0.17
328.15
1.2114
1.2135
0.18
334.22
1.00
273.18
1.97
1.150E-09
0.18
x2 = 0.3945
278.15
1.2337
1.2356
0.15
300.38
0.80
240.64
1.96
8.037E-10
0.15
283.15
1.2328
1.2345
0.13
302.18
0.70
242.31
1.84
8.302E-10
0.13
288.15
1.2317
1.2332
0.12
304.01
0.65
244.04
1.76
8.578E-10
0.12
293.15
1.2303
1.2319
0.12
305.84
0.65
245.80
1.76
8.866E-10
0.12
298.15
1.2290
1.2304
0.11
307.71
0.61
247.61
1.71
9.164E-10
0.11
303.15
1.2274
1.2288
0.12
309.58
0.62
249.46
1.72
9.475E-10
0.12
308.15
1.2256
1.2271
0.12
311.49
0.66
251.36
1.75
9.798E-10
0.12
313.15
1.2237
1.2253
0.13
313.41
0.72
253.29
1.82
1.013E-09
0.13
318.15
1.2217
1.2234
0.14
315.35
0.79
255.27
1.89
1.048E-09
0.14
323.15
1.2196
1.2215
0.16
317.32
0.86
257.28
1.97
1.085E-09
0.16
328.15
1.2173
1.2195
0.18
319.30
0.99
259.33
2.12
1.122E-09
0.18
x2 = 0.49832
278.15
1.2406
1.2426
0.16
284.24
0.80
226.18
2.06
7.795E-10
0.16
283.15
1.2395
1.2414
0.15
285.86
0.79
227.69
2.05
8.049E-10
0.15
288.15
1.2384
1.2401
0.14
287.50
0.74
229.25
1.98
8.314E-10
0.14
293.15
1.2369
1.2387
0.15
289.15
0.75
230.85
1.99
8.590E-10
0.15
298.15
1.2354
1.2372
0.14
290.82
0.75
232.48
1.98
8.876E-10
0.14
303.15
1.2337
1.2355
0.15
292.50
0.77
234.16
2.00
9.174E-10
0.15
308.15
1.2318
1.2338
0.16
294.21
0.83
235.87
2.07
9.484E-10
0.16
313.15
1.2299
1.2319
0.17
295.93
0.89
237.63
2.12
9.806E-10
0.17
318.15
1.2279
1.2300
0.17
297.68
0.90
239.41
2.13
1.014E-09
0.17
323.15
1.2256
1.2280
0.19
299.45
1.04
241.24
2.28
1.049E-09
0.19
328.15
1.2236
1.2259
0.19
301.21
1.05
243.09
2.28
1.085E-09
0.19
x2 = 0.60144
278.15
1.2485
1.2502
0.14
268.52
0.68
212.33
1.94
7.519E-10
0.14
283.15
1.2476
1.2491
0.13
270.02
0.63
213.72
1.88
7.762E-10
0.13
288.15
1.2464
1.2479
0.12
271.55
0.60
215.16
1.84
8.014E-10
0.12
293.15
1.2450
1.2465
0.12
273.09
0.62
216.63
1.85
8.277E-10
0.12
298.15
1.2435
1.2450
0.12
274.66
0.61
218.15
1.84
8.550E-10
0.12
303.15
1.2418
1.2433
0.12
276.23
0.63
219.70
1.85
8.834E-10
0.12
308.15
1.2400
1.2416
0.13
277.82
0.68
221.29
1.90
9.129E-10
0.13
313.15
1.2380
1.2398
0.14
279.43
0.73
222.92
1.96
9.435E-10
0.14
318.15
1.2359
1.2378
0.15
281.06
0.80
224.58
2.03
9.753E-10
0.15
323.15
1.2338
1.2358
0.17
282.70
0.87
226.27
2.10
1.008E-09
0.17
328.15
1.2315
1.2338
0.18
284.35
0.97
227.99
2.21
1.043E-09
0.18
x2 = 0.69872
278.15
1.2572
1.2584
0.09
253.92
0.45
199.65
1.60
7.228E-10
0.09
283.15
1.2561
1.2572
0.09
255.27
0.44
200.90
1.58
7.458E-10
0.09
288.15
1.2548
1.2559
0.09
256.63
0.45
202.19
1.58
7.698E-10
0.09
293.15
1.2533
1.2545
0.10
258.00
0.47
203.51
1.61
7.947E-10
0.10
298.15
1.2517
1.2530
0.11
259.39
0.52
204.87
1.66
8.205E-10
0.11
303.15
1.2500
1.2513
0.11
260.80
0.54
206.27
1.67
8.474E-10
0.11
308.15
1.2480
1.2495
0.12
262.22
0.61
207.70
1.75
8.752E-10
0.12
313.15
1.2460
1.2477
0.14
263.66
0.68
209.17
1.83
9.042E-10
0.14
318.15
1.2438
1.2457
0.15
265.10
0.76
210.66
1.91
9.342E-10
0.15
323.15
1.2416
1.2436
0.17
266.57
0.85
212.19
2.01
9.654E-10
0.17
328.15
1.2393
1.2415
0.18
268.04
0.92
213.73
2.09
9.977E-10
0.18
x2 = 0.79749
278.15
1.2664
1.2672
0.06
238.81
0.28
186.83
1.20
6.895E-10
0.06
283.15
1.2653
1.2661
0.07
240.08
0.31
187.99
1.23
7.112E-10
0.07
288.15
1.2641
1.2649
0.06
241.37
0.29
189.19
1.21
7.337E-10
0.06
293.15
1.2627
1.2636
0.07
242.67
0.32
190.42
1.23
7.571E-10
0.07
298.15
1.2612
1.2621
0.07
243.99
0.32
191.68
1.23
7.814E-10
0.07
303.15
1.2596
1.2605
0.07
245.32
0.35
192.99
1.26
8.066E-10
0.07
308.15
1.2577
1.2588
0.09
246.66
0.41
194.32
1.33
8.328E-10
0.09
313.15
1.2558
1.2569
0.09
248.03
0.46
195.68
1.38
8.600E-10
0.09
318.15
1.2536
1.2550
0.11
249.39
0.53
197.07
1.46
8.882E-10
0.11
323.15
1.2515
1.2530
0.12
250.78
0.59
198.50
1.52
9.174E-10
0.12
328.15
1.2493
1.2509
0.13
252.17
0.65
199.94
1.60
9.477E-10
0.13
x2 = 0.9021
278.15
1.2802
1.2794
0.06
224.06
0.29
174.25
0.16
6.510E-10
0.06
283.15
1.2789
1.2782
0.06
225.06
0.26
175.20
0.18
6.710E-10
0.06
288.15
1.2773
1.2768
0.04
226.08
0.17
176.18
0.29
6.918E-10
0.04
293.15
1.2755
1.2753
0.02
227.11
0.08
177.20
0.40
7.134E-10
0.02
298.15
1.2736
1.2736
0.00
228.15
0.01
178.24
0.50
7.357E-10
0.00
303.15
1.2716
1.2719
0.02
229.20
0.08
179.32
0.59
7.590E-10
0.02
308.15
1.2694
1.2700
0.04
230.25
0.21
180.42
0.74
7.830E-10
0.04
313.15
1.2671
1.2680
0.07
231.33
0.33
181.55
0.88
8.080E-10
0.07
318.15
1.2647
1.2659
0.10
232.40
0.46
182.70
1.04
8.338E-10
0.10
323.15
1.2622
1.2637
0.12
233.49
0.58
183.88
1.18
8.606E-10
0.12
328.15
1.2595
1.2614
0.15
234.58
0.73
185.07
1.36
8.882E-10
0.15
x2 = 0.94974
278.15
1.2863
1.2852
0.09
217.05
0.41
168.42
0.22
6.319E-10
0.09
283.15
1.2849
1.2840
0.08
217.99
0.34
169.31
0.14
6.512E-10
0.08
288.15
1.2833
1.2826
0.05
218.95
0.25
170.23
0.02
6.712E-10
0.05
293.15
1.2816
1.2811
0.04
219.91
0.17
171.19
0.07
6.919E-10
0.04
298.15
1.2796
1.2794
0.02
220.89
0.07
172.17
0.19
7.134E-10
0.02
303.15
1.2776
1.2777
0.00
221.87
0.01
173.18
0.29
7.357E-10
0.00
308.15
1.2754
1.2758
0.03
222.87
0.12
174.21
0.42
7.587E-10
0.03
313.15
1.2731
1.2738
0.05
223.87
0.24
175.27
0.56
7.827E-10
0.05
318.15
1.2707
1.2717
0.08
224.88
0.37
176.36
0.71
8.074E-10
0.08
323.15
1.2681
1.2695
0.10
225.90
0.49
177.47
0.87
8.331E-10
0.10
328.15
1.2656
1.2672
0.13
226.92
0.61
178.59
1.00
8.595E-10
0.13
x2 = 1.00000
278.15
1.2928
1.2915
0.10
209.57
0.45
162.27
0.55
6.110E-10
0.10
283.15
1.2913
1.2903
0.08
210.40
0.36
163.07
0.44
6.294E-10
0.08
288.15
1.2895
1.2888
0.05
211.24
0.24
163.90
0.30
6.485E-10
0.05
293.15
1.2875
1.2872
0.02
212.09
0.09
164.76
0.11
6.683E-10
0.02
298.15
1.2855
1.2855
0.00
212.94
0.00
165.64
0.00
6.888E-10
0.00
303.15
1.2833
1.2837
0.03
213.80
0.12
166.55
0.15
7.100E-10
0.03
308.15
1.2810
1.2817
0.05
214.67
0.25
167.49
0.30
7.320E-10
0.05
313.15
1.2786
1.2796
0.08
215.55
0.38
168.45
0.47
7.547E-10
0.08
318.15
1.2760
1.2775
0.11
216.43
0.52
169.42
0.63
7.783E-10
0.11
323.15
1.2734
1.2752
0.14
217.33
0.65
170.43
0.79
8.026E-10
0.14
328.15
1.2706
1.2729
0.17
218.22
0.81
171.44
0.98
8.277E-10
0.17
The results obtained are in excellent agreement with the experimental results, obtaining for: , , and a percentage of absolute error with respect to the 1,6-Dichlorohexene (x) + Dodecane (1-x) system is practically below 1 at all concentrations. While with respect to the 1,5-Dichloropentane (x) + Dodecane (1-x) system, this was also practically below unity at all concentrations except for , where the percentage of error in some concentrations was around two units.
5 Conclusion
A semiempirical algorithm was developed to evaluate the adiabatic coefficient, heat capacities and isothermal compressibility of binary liquid mixtures from acoustic and volumetric data. Mathematical developments were obtained using Laplace's equation and Mayer's Relationship. The new method was implemented with the systems (1,5-Dichloropentane or 1,6-Dichlorohexane) + Dodecane in the entire concentration range and temperatures between (278.15–328.15) K. This algorithm is an easy protocol to implement, and represents an alternative to complement the results obtained from volumetric and acoustic data. The proposed model is not universal. However, it works well for mixtures and pure compounds whose product of density and the nth root of adiabatic compressibility is highly independent of temperature; In addition, it can be applied throughout a wide concentration and temperature range, and give information about 4 parameters ( , , , ). Information that other models do not provide
Acknowledgements
We gratefully acknowledge to Universidad Andres Bello and Universidad de Córdoba for the support provided during this investigation. P.C.L. also thanks: a) The National Agency for Research and Development (ANID) for his postdoctoral Project FONDECYT/Postdoctorado-2018 No. 318044, and b) Universidad de Santiago de Chile, for the funding through the postdoctoral project [POSTDOC_DICYT, Code 0921SP_POSTDOC].
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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