Thermodynamic Properties of 1, 2-Dichloroethane and 1, 2

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Thermodynamic Properties of 1,2-Dichloroethane and 1,2-Dibromoethane Under Elevated Pressures: Experimental Results and Predictions of a Novel DIPPR-Based Version of FT-EoS, PC-SAFT and CP-PC-SAFT. Miros#aw Chor##ewski, Eugene B Postnikov, Kamil Oster, and Ilya Polishuk Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.5b02626 • Publication Date (Web): 11 Sep 2015 Downloaded from http://pubs.acs.org on September 11, 2015

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Industrial & Engineering Chemistry Research

Thermodynamic Properties of 1,2-Dichloroethane and 1,2-Dibromoethane Under Elevated Pressures: Experimental Results and Predictions of a Novel DIPPR-Based Version of FT-EoS, PC-SAFT and CP-PC-SAFT. Miroslaw Chorążewski*1, Eugene B. Postnikov2, Kamil Oster1 and Ilya Polishuk*3 1

Institute of Chemistry, University of Silesia, Szkolna Street 9, 40-006 Katowice, Poland

2

Department of Theoretical Physics, Kursk State University, Radishcheva st., 33, 305000 Kursk, Russia.

3

Department of Chemical Engineering & Biotechnology, Ariel University, 40700, Ariel, Israel.

Abstract This study reports the experimental measurements of speeds of sound from 293.15 to 313.15 K and pressures up to 100 MPa in 1,2-dichloroethane, and up to 45 MPa in 1,2-dibromoethane, approaching solidification of this compound. In addition, new atmospheric pressure data on densities of 1,2dichloroethane from 278.15 K to 348.15 K are presented. These experimental data have been implemented for calculating densities, isobaric heat capacities and coefficients of thermal expansion, isentropic and isothermal compressibilities, and internal pressures as functions of pressure and temperature by using an acoustic method of Davis-Gordon-Sun. Development of a new DIPPR-based version of the FT-EoS is presented. This model could become a simple and reliable tool implementing the DIPPR’s saturated state expressions for predicting the high pressure densities and speeds of sound. It has also been demonstrated that both compounds under consideration can be included in the applicability range of the predictive CP-PC-SAFT approach employing the DIPPR’s critical constants. In spite of its poor modeling of vapor pressures of these substances away from their critical points, CP-PC-SAFT appears as a robust estimator of various thermodynamic properties of both pure compounds and mixtures in the entire pressure range, and as well of the high pressure phase equilibria. Unlike CP-PC-SAFT, parametrization of PC-SAFT comprises fitting large experimental databases and it cannot be implemented for simultaneous modeling of the critical and the sub-critical states. Although this model is the less successful estimator of sound velocities and compressibilities, it has a doubtless advantage in modeling the low-pressure phase equilibria.

______________________________________________________________________ Keywords: 1,2-dichloroethane, 1,2-dibromoethane, fluctuation theory, statistical association fluid theory, density, speed of sound. *

Corresponding authors.

E-mails: [email protected]; phone: +48323591545; fax: +48322599978. [email protected]. Phone +972-3-9066346. Fax +972-3-9066323.

ACS Paragon Plus Environment

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I. Introduction. This study continues a series of investigations implementing an acoustic method for determining various thermodynamic properties of α,ω-dihaloalkanes in the temperature range from 293.15 to 313.15 K and at pressures up to 100 MPa. Previously, the data on 1,3dibromopropane and 1,5-dibromopentane1, 1,4-dibromobutane and 1,6-dibromohexane,2 dichloromethane, bromochloromethane, and dibromomethane3 have been reported. Yet 1,2dichloroethane and 1,2-dibromoethane are considered. 1,2-dichloroethane is a precursor for production of polyvinyl chloride and several chemicals such as 1,1,1-trichloroethane. The global market of 1,2-dichloroethane reaches several dozens of millions of tons and it is expected to grow in the coming years.4 Consequently, this compound is one of the most intensively investigated α,ω-dihaloalkanes. The high pressure measurements of its densities cover the range of 278.15 - 398.15 K and 2 - 394.4 MPa.5 In addition, the density-originated elevated pressure isobaric heat capacity and thermal expansion coefficient along with the isothermal compressibility data are available.6,7 Nevertheless, to the best of our knowledge, thus far no high pressure speed of sound data for this compound have been reported in the open literature. 1,2-dibromoethane is mainly used as a pesticide in several developing countries and as a chemical intermediate in the production of vinyl bromide, some plastics and resins. Its global market its substantially smaller in comparison to 1,2-dichloroethane.8 So far its thermodynamic properties have been investigated less intensively as well. In particular, the high pressure liquid densities of this compound have been measured through the 293.15 K isotherm and up 42.6 MPa.9 Other studies10,11 provide just two additional high pressure liquid density points. To the best of our knowledge, no high pressure auxiliary thermodynamic property data of 1,2-dibromoethane are available in the open literature. In this investigation speeds of sound have been measured from 293.15 to 313.15 K and pressures up to 100 MPa in 1,2-dichloroethane, and up to 45 MPa in 1,2-dibromoethane, approaching solidification of this compound. The atmospheric pressure densities of 1,2dichloroethane have been measured from 278.15 to 348.15 K. Then, the densities and the auxiliary thermodynamic properties under elevated pressure have been determined while implementing a computational acoustic method of Davis and Gordon12 modified by Sun et al.13. These data have been used for validating the accuracy of two predictive models originated from different theoretical considerations and having dissimilar degrees of complexity, namely


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a new version of the Fluctuation Theory-based Tait-like Equation of State (FT-EoS)2,14-17 and the Critical Point-based Perturbed-Chain Statistical Association Fluid Theory (CP-PCSAFT).17-20 Initially, derivation of FT-EoS has aimed at development of a Tait-like equation having just two adjustable parameters. This decrease of the number of adjustable parameters has become possible thanks to the detection of some fundamental regularities characteristic for liquids. At the same time, the model’s parameters have still been adjusted to the available high pressure experimental data. In this study we present a novel DIPPR21-based version of FT-EoS. In this version the number of adjustable parameters is reduced from two to one. Moreover, evaluation of the remaining adjustable parameter requires just a single low pressure isothermal compressibility datum. In other words, a current version of the model is entirely predictive in the high pressure range. A rational of the second predictive approach considered in this study, CP-PC-SAFT, was replacing the non-transparent fitting procedures of the SAFT’s substance-dependent parameters by their standardized numerical solution at the characteristic states, namely the pure compound critical and triple points. Previously, CP-PC-SAFT has been implemented for predicting various thermodynamic properties of light compounds, n-alkanes, 1-alkenes, 1alkanols, aromatic, haloaromatic compounds and their mixtures. However so far properties of only one haloalkane, namely 1-chloropropane,20 has been considered for evaluating the predictive potential of this model. Although the expression of CP-PC-SAFT is substantially more sophisticated in comparison with FT-EoS, its applicability range is much wider, and it covers the critical states, the properties of gases and mixtures. Consequently, in this study the performance of CP-PC-SAFT in estimating the available binary single phase, critical and high pressure VLE data of the systems comprising the considered α,ω-dihaloalkanes is evaluated. In order to enhance this analysis, a comparison with the original version of PC-SAFT22 is performed as well.

2. Experimental section and PVT calculations. 2.1. Chemicals. 1,2-dibromoethane (Lancaster, 99 %) and 1,2-dichloroethane (Avocado, 99%) have been purified before each measurement by the fractional distillation, while collecting the middle fraction (approximately 5 %). Both liquids have been dried with the molecular sieve (Lancaster, type 3Å, beads). After the purification, a determined by the Karl Fischer’s


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titration method mass fraction of water in both compounds was less than 3 × 10−5. Finally, before each measurement the samples have been degassed in the ultrasonic stream. 2.2. Speed of sound and density measurements. The liquid phase speeds of sound have been measured by the pulse-echo overlap method at the frequency of 2 MHz. An uncertainty of this method is about ± 0.5 m·s-1 at the atmospheric pressure, and ± 1 m·s-1 under elevated pressures. Details of the apparatus, the experimental procedure, and the calibration method can be found elsewhere.23,24 The atmospheric pressure densities of 1,2-dichloroethane have been measured from 278.15 K to 348.15 K by the vibrating-tube densimeter Anton Paar DMA 5000. An uncertainty of this device is ± 5·10-2 kg·m-3. Details on this experimental procedure and calibration, along with the atmospheric pressure data of 1,2-dibromoethane can be found in the previous papers.25 Comparison between the literature data and the data presented in this and the previous25,26 studies for the ambient conditions are listed in Table S1 of the Supporting Information. The speeds of sound in both liquids under elevated pressures have been measured in the temperature range from ~293 to ~313 K and pressures up to 101.32 MPa for 1,2-dichloroethane, and up to 45.59 MPa for 1,2-dibromoethane, approaching solidification of this compound. The experimental values of speeds of sound and densities at the atmospheric pressure for 1,2-dichloroethane are listed in Table 1. The results for speeds of sound at pressures higher than the atmospheric one are listed in Table 2. 2.3. PVT calculations. These experimental results have been implemented for calculating densities, isobaric heat capacities,

isobaric coefficients of thermal expansion,

isentropic

and

isothermal

compressibilities, and internal pressures as functions of pressure and temperature. An acoustic method proposed by Davis and Gordon12 followed by the numerical procedure of Sun et al.13 has been applied for the PVT calculations. Details of this method along with the required atmospheric pressure CP data obtained from the previous studies25,26, the values of coefficients and the calculated results are listed in the Supporting Information. The overall uncertainties have been estimated by means of the perturbation method

1,13,27

,

while the speed of sound has been considered as a main source of error. However, as reported previously,1-3,28 the total uncertainties, including the comparison of our results with other data obtained by different methods, can be roughly be estimated as smaller than ±1 %, ±0.05 %, ±1 %, ±0.15 %, ±0.3 %, ±1 %, for heat capacity, density, thermal expansion coefficient, isentropic compressibility, isothermal compressibility, and internal pressure, respectively.


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3. Models considered in this study and their predictions. 3.1. A novel DIPPR-based version of FT-EoS. The fluctuation theory-based isothermal equation of state (FT-EoS)2,15,17 relates the microscopic density fluctuations with a macroscopic thermodynamic property, namely the isothermal compressibility κT.

1

 kM



w ρ = ρ 0 + ln  ( P − P0 ) + 1 k ν (ρ0 )RT 

(1)

where ν is the parameter of the inverse reduced fluctuation14,16 defined as:

ν=

Mw 1 RT ρκT

(2)

ρ, Mw, k, and R are the density, molecular weight, the slope coefficient and the gas constant correspondingly. In Eq. (1), the subscript 0 denotes the reference value corresponding to the saturated pressure. In its previous version, the model has required the experimental low pressure ρ and κT data in order to estimate a large variety of thermodynamic properties at the high pressures. Following the fundamental regularity exhibited by ν for various liquids, namely the nearly exponential dependence of this parameter on density, the following expression has been obtained:

ν = exp(kρ + b )

(3)

Eq. (3) has allowed achieving a remarkable accuracy with just 2 adjustable parameters, k and b. This simplification can be considered as an advantage in the comparison with the Tait-like models, which typically require the substantially larger amount of adjustable parameters. Moreover, the predictive character of FT-EoS can be enhanced by taking a constant value of k and generalizing b for homologues series of compounds.17 In the current study further progress in enhancing the predictive value of FT EoS is reported. As known, the databases such as DIPPR21 provide saturation properties for many thousands of compounds. However the current collection of the high pressure properties is substantially smaller. Consequently, a particularly high practical value should be attributed to the model


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implementing the available in the databases low pressure information for the reliable estimation of the unavailable high pressure data. Following this concept, the current modification of FT-EoS implements the empirical saturated state expressions of DIPPR21. In particular, according to this database, the saturated densities are given as follows:

ρs =

Mw A  T 1+  1−   C

(4)

D

B

where A, B, C, D are the constants tabulated for each individual substance. Unfortunately, DIPPR does not provide data on the isothermal compressibilities. As a preliminary approach, the universal approximation of Brelvi and O’Connell29 for the dimensionless compressibility (ν BO ) has been implemented:

ν BO = exp[− 0.42704( ρ * − 1) + 2.089( ρ * − 1) 2 − 0.42367( ρ * − 1) 3 ] − 1

(5)

The latter correlation is considered as one of the standard reference lines in the applied calculations of the isothermal compressibility.30 In Eq. (5) ρ* is given as follows:

ρ * = ξ ρ s ρc

(6)

ξ = 1 results in ν BO = 0 at the critical point. However for the dense liquids away from the critical temperatures vBO >> 1 , which allows postulation of close proximity between Eqs. (3) and (5). The derivative of the logarithm of Eq. (5) can be easily found in the explicit form, which yields the slope coefficient k required by FT-EoS (Eq. 1) as follows:

k =ξ

−1 1 + ν BO

ρc

(− 0.42704 + 4.178( ρ

*

− 1) − 1.27101( ρ * − 1) 2

)

(7)

Finally, the reference pressure substituted to Eq. (1) can be taken from another DIPPR expression:


6

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B'   P0 = Ps = exp  A'+ + C ' log T + D'T E '  T  

(8)

In summary, in the current approach Eq. (5) replaces Eq. (3) in the entire pressure range, which eliminates the adjustable parameter b. In addition, Eq. (7) provides an expression for the slope coefficient k in Eq. (1) and Eq. (8) – for P0. At the same time, another coefficient, ξ is introduced. Yet ξ becomes a single adjustable parameter of FT-EoS. Moreover, ξ can be adjusted just to one low pressure κT datum. In other words, the current model is entirely predictive in the high pressure range. In order to obtain ξ, a 303.15 K and 1 bar value of κT reported in this study has been implemented. For 1,2-dichloroethane and 1,2-dibromoethane

ξ = 1.031 and ξ = 0.982, respectively, have been obtained. The saturated speeds of sound can be calculated implementing the DIPPR’s expression for the saturated liquid isobaric heat capacities CPs :

1

us =

κ T0 ρ s −

(α )

(9)

2

0 P

T

CPs

Following the previous study17, speeds of sound at the high pressures are:

u = us +

ν BO ( ρs ) RT MW

k k2 2  ( ρ − ρs ) + ( ρ − ρs )  8 2 

(10)

Once obtaining the densities (Eq. 1) and speeds of sound (Eq. 10), other thermodynamic properties in the high pressure range can be predicted. Further efforts will be invested in generalization this last model’s adjustable parameter in order to attach the model by an entirely predictive character. For example, an expression for the isothermal compressibility can be derived from the thermodynamic equalities discussed by Otpushchennikov et al.31 In particular, the following full derivative along the coexistence curve

dρ s  ∂ρ s   ∂ρ s  dP =  +  dT  ∂T  P  ∂P T dT

(11)


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provides an expression connecting the isothermal compressibility and the isobaric expansion coefficient:

α p + κT

dPs d = log(ρ s ) , dT dT

(12)

where ρ = ρ s is given by Eq. (4), while Ps is given by Eq. (8). The latter dependences allow the explicit analytical formulation of their temperature derivatives. However, Eq. (12) contains both κ T and α P , which require provision of some additional expression for creating a system of two equations with respect to the considered variables. This problem can be solved by considering an additional property, namely the internal pressure (Pi)

 ∂E  Pi =    ∂V  T

(13)

where E is the internal energy that can be expressed as:

 ∂E   ∂P    = T  −P  ∂V  T  ∂T V

(14)

Since

α  ∂P    = P  ∂T V κ T

(15)

The following relation is obtained:

α P − κT

P P = Pi . T T

(16)


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Then αp can be excluded from Eqs. (12) and (16) yielding the following expression for the isothermal compressibility along the coexistence curve:

d log(ρ s )  dPs Pi + Ps   dT − T  . dT   −1

κT =

(17)

Being substituted into Eq. (2), Eq. (17) provides the exact expression for the reduced density fluctuations at the saturation conditions:

ν=

Pi T

−1

 RT dρ s   T  dPs Ps  −  . −  1 −   M w dT   Pi  dT T 

(18)

As seen, the internal pressure Pi plays a central role in the proposed parameterization procedure. In this respect it should be pointed out that several attempts of deriving models for the internal pressures of liquids along the entire coexistence curves have been made during the last century.32-34 Unfortunately, this problem has generally remained unsolved.35 At the same time, ξ can be determined around the boiling points implementing the correlation of Srivastava36 accurate for a large amount of liquids34,35: Pi b ( MPa ) = 4.5(24.5Tb -1400)ρ b M w

(19)

where ρb (the saturated density at the boiling temperature Tb) can be obtained from DIPPR. Then the value of ξ is obtained by substituting Eq. (19) into Eq. (18) and equalizing with Eq. (5). Two assumptions allow derivation of an analytical expression for ξ: (i) Since the internal pressures are larger by several orders of magnitude than the vapor pressures, the second part of Eq. (18) can be eliminated. (ii) ξ is close to unity, which allows linearization of lnν BO with respect to 1-ξ. The resulting analytical expression is:

ξ = 1+

[

log(ν Sb + 1) - - 0.42704( ρ rb - 1) + 2.089( ρ rb - 1) 2 - 0.42367( ρ rb - 1) 3

ρ b (- 5.87605 + 6.72002 ρ - 1.27101ρ b r

2 r

)


]

(20)

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where:

4.5(24.5Tb - 1400) ρ b ν = M w Tb b S

 RTb dρ s −  M w dT

  ρ s = ρb  

−1

(21)

and ρ rb = ρ b ρ c are the reduced saturated densities at the normal boiling points. The proposed technique allows final eliminating of adjustable parameters in FT-EoS and referring to the DIPPR’s data only. In the particular cases of 1,2-dichloroethane and 1,2-dibromoethane Eqs. (20) and (21) yield ξ = 1.039 and ξ = 0.971, correspondingly. As seen, these values are in relatively good agreement with the values obtained by fitting the 303.15 K κT datum (ξ = 1.031 and ξ = 0.982). Nevertheless, the quantitative accuracy of this entirely predictive method still requires further considerations and, therefore, it has not been implemented yet.

3.2. CP-PC-SAFT. In this study the predictions of the DIPPR-based version of FT EoS are compared with the critical point-based version (CP)17-19 modifying the popular PC-SAFT EoS.22 In addition to the entirely transparent numerical procedure for solving the model parameters, this revision has targeted addressing two other issues, namely removal of the numerical problems affecting the original version of PC-SAFT37-43, and allowing simultaneous prediction of critical and sub-critical data. For the non-associating and non-polar compounds PC-SAFT expresses the residual Helmholtz energy as a sum of hard-sphere, chain and dispersion contributions:

Ares = AHS + Achain + Adisp

(22)

The pressure-explicit EoS expression is then obtained as:

RT  ∂Ares  P= −  v  ∂v T

(23)

Unlike many SAFT approaches whose substance-dependent parameters are typically evaluated by fitting relatively large and sometimes vague experimental databases, CP-PCSAFT applies their standardized numerical solution at the characteristic states, namely the


10

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critical points. In addition, it requires one liquid density point datum, normally at the triple point. In other words, this approach can be characterized by an advanced predictive capacity thanks to the substantial reduce of the required experimental data. According to CP-PCSAFT, the values of m (the effective number of segments), σ (the segment diameter, Å), ε/k (segment energy parameter divided by Boltzmann's constant, K) and δ (the critical volume displacement, a ratio between the EoS’s and the experimental values) are solved numerically. The pertinent system of four equations is:

 ∂P 2   ∂P  =  2  =0    ∂v Tc  ∂ v Tc vc , EoS = δ vc

(24,25)

Pc , EOS = Pc

(26)

ρ L, EoS = ρL,experimental at the triple point

(27)

Detailed description of this model along with the procedure for solving a system of Eqs. (24)(27) can be found in Reference 18. Obviously, the performance of the model is reliant on the reliability of the critical data. As indicted previously18, the CP-PC-SAFT approach can hardly been implemented for the heavy compounds decomposing in the sub-critical temperature range, and whose reported critical constants are therefore imaginary. Similar problem may arise in the cases of compounds whose available critical data are characterized by significant uncertainty. For example, in the case of 1,2-dichloroethane the NIST’s44 recommended values for the critical pressure fall in the relatively narrow range of 561 K < Tc < 561.8 K. However in the case of the critical pressures this range is particularly wide: 53 bar < Pc < 56.78 bar. Figure 1 indicates that implementing the lowest lateral of the critical constants range (561 K & 53 bar) and the highest one (561.8 K & 56.78 bar) have significant consequences of the performance of CP-PC-SAFT. While with the lowest values the model slightly overestimates the speed of sound data and yields accurate predictions of the densities, the highest values result in substantial underestimation of u and inaccurate results for ρ. Consequently, sets of Tc and Pc yielding the precise modeling of the data can be found within the range recommended by NIST. Obviously, detecting these sets cannot be considered as a predictive practice and it has not been implemented.


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The critical constants and the triple point liquid densities used for solving these equations have been obtained from the DIPPR databank.21 The critical pressure of 1,2-dichloroethane reported by this databank (53.7 bar) is on the low side of the NIST’s scale and the critical temperature (561.6 K) falls inside the recommended range. The CP-PC-SAFT parameters of compounds considered in this study are listed in Table S6 of the Supporting Information. Unlike CP-PC-SAFT, the original version of PC-SAFT22 cannot be implemented for simultaneous modeling of the critical and the sub-critical data. Consequently, its parametrization requires fitting to large experimental databases and tabulating the values for the particular compounds. Although furtherly these values can be generalized for particular groups of compounds by various methods45-47, currently these strategies can hardly be implemented for the α,ω-dihaloalkanes considered in this study. The most comprehensive list of the PC-SAFT pure compound parameters (including 1,2-dichloroethane) thus far has been reported by Reference 46. Nevertheless, some compounds considered in this study (vinyl chloride, 1-methyl-2-pyrrolidone, N,N-dimethylformamide and N,N –dimethylacetamide) have not been covered by this or other available to us references. Consequently, PC-SAFT has not been implemented for modeling the pertinent data. Since the PC-SAFT parameters for 1,2-dibromoethane cannot be found in the open literature as well, they have been evaluated in this study. Following the strategy of the previous works22,45,46, a major attention during the fitting procedure has been paid to the precise representation of the vapor pressure curve, while neglecting the near-critical range and attempting to achieve the maximal possible accuracy for the densities. The resulting values are: m = 2.30400, σ = 3.73723 Å and ε/k = 344.857 K.

3.3. Results. Figure 2 and Figs. S1-S4 of the Supporting Information depict the predictions yielded by the considered models for the high pressure properties of 1,2-dichloroethane. A remarkable good agreement between the current data and the data of Malhotra and Woolf7 should be noticed. As seen, both CP-PC-SAFT and FT-EoS yield particularly accurate description of densities with certain advantage of CP-PC-SAFT at the elevated pressure range above 2000 bar. At the same time FT-EoS is superior in predicting speeds of sound. While the results of this model are nearly precise below 400 bar and slight underestimation of data can be observed at the higher pressures, CP-PC-SAFT implementing the DIPPR critical constants tends to overestimate speeds of sound in the entire pressure range. The AAD% from the speed of sound data are 0.796 and 1.35 for FT-EoS and CP-PC-SAFT, respectively. As seen, PC-


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SAFT overestimates the pressure dependence of the densities and, as a result substantially underestimates the speeds of sound. Consequently, CP-PC-SAFT seems to be a more reliable estimator of the κT data at the elevated pressure range, while FT-EoS has an advantage in predicting κS. PC-SAFT appears as the less accurate estimator of these data. Reliable predictions of the isobaric coefficient of thermal expansion in general and the intersection of its isotherms in particular present a severe test for thermodynamic models. As seen, CP-PCSAFT fails to estimate these data accurately. In particular, it underestimates the 278.15 K isotherm and substantially over-predicts the pressure of the isotherms intersection. In addition, CP-PC-SAFT underestimates the low temperature CP data as well, and generates an inaccurate pressure dependence of this property. Unlike that, it can be seen that FT-EoS yields a much more realistic description of αP and intersection of its isotherms. Unfortunately, the latter prediction still seems to be qualitatively inaccurate. In particular, while the actual datum is most probably located around 1200-1400 bar, the model estimates it at the lower pressure around 700 bar. As a result, FT-EoS as well generates a wrong pressure dependence of CP, with the deviation is opposite to CP-PC-SAFT. Although PC-SAFT is also capable of predicting the intersection of αP isotherms, the results are imprecise. Its estimations of CP are slightly more accurate in comparison with CP-PC-SAFT. And, finally, the doubtless advantage of CP-PC-SAFT over PC-SAFT and FT-EoS in predicting the internal pressures should be pointed out. Figure 3 presents the high pressure densities and speeds of sound in 1,2-dibromoethane. Yet the previous results for density9,10 do not agree with our data, outlining the intricacy of the compound under consideration. As seen, both CP-PC-SAFT EoS and FT-EoS match the currently reported densities, a result which supports our data. At the same time, CP-PC-SAFT tends to overestimate the speeds of sound, while FT-EoS establishes an opposite trend. The AAD% from the speed of sound data are yet 1.88 and 1.70 for FT-EoS and CP-PC-SAFT, respectively. Once again, PC-SAFT is the less successful estimator of these data. In the following discussion let us examine the accuracies of PC-SAFT and CP-PC-SAFT in modeling phase equilibria in pure α,ω-dihaloalkanes under consideration and their mixtures. As seen (Fig. 4), unlike PC-SAFT, CP-PC-SAFT underestimates the vapor pressures away from the critical states. This result should be considered as a major drawback of the CP-PCSAFT, which doubtlessly requires further considerations and improvements of the model. Indeed, in its current form, this approach can hardly be implemented for predicting the low


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pressure VLE data in mixtures, since they are demarcated by the pure compound vapor pressures. At the same time, CP-PC-SAFT still can be implemented for modeling the high pressure phase equilibria. Unfortunately, these data for the systems containing 1,2-dibromoethane are currently unavailable in the open literature and only four binary systems of 1,2-dichloroethane have been reported so far. The results for these systems are presented on Fig. 5(A-D). As seen, CP-PC-SAFT yields accurate predictions with k12 = 0 for the asymmetric systems of carbon dioxide and ethane with 1,2-dichloroethane (Figs. 5A and 5B). Remarkable, PC-SAFT fails in accurate description of these data in predictive manner. At the same time, k12 = 0.02 produces reasonable modeling of the more symmetric systems with vinyl chloride and propene (Figs. 5C and 5D). In order to improve the predictive character of the approaches under consideration, this value of the binary adjustable parameter has been furtherly implemented for all other relatively symmetric mixtures of 1,2-dichloroethane treated in this study. Figure 5E demonstrates that PC-SAFT is unsurprisingly much more accurate in modeling the low pressure VLE. At the same time, in the middle pressure range both models can exhibit a comparable accuracy in estimating phase equilibria (Fig. 5F). A disadvantage of CP-PC-SAFT in predicting the vapor pressures at the low temperatures is compensated by its precise results for the pure compound critical pressures and temperatures. Consequently, this model has a doubtless advantage over PC-SAFT in predicting the critical lines in symmetric systems. Figure 6 depicts its results for the critical states of the 1,2dichloroethane – n-alkanes systems investigated with great details by Garcia-Sanchez and Trejo54 and Christou et al.55 As seen, the predictions of CP-PC-SAFT for the critical temperatures, pressures and compositions in the series of systems from n-butane and till ntetradecane are particularly accurate. At the same time, less impressive results are obtained for the critical data of a propane system, which requires re-fitting of k12 in this particular case. Figure 7 and Table 3 depict the results of both approaches under consideration in predicting the single phase high pressures densities of the available mixtures containing 1,2dichloroethane. Although in the case of CP-PC-SAFT k12 = 0.02 results in systematic underestimation of the negative values of the excess densities, in most of the cases the AAD% is still less than 1%. These results should be recognized as particularly accurate while taking into account the predictive character of the model and the complexity of the considered systems. Only in the cases of mixtures containing isooctane and N,N-dimethylformamide the AAD% exceed 1%, which should be attributed to the less precise predictions of these pure compounds. As seen, PC-SAFT yields the comparable accuracy for the mixtures of 1,2-


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dichloroethane with alkanes. However in spite of the fact that this model considers the association of 1-propanol, the results in this particular case are less accurate. And, finally, let us consider modeling the atmospheric pressure properties of the binary system 1,2-dibromoethane – n-heptane (Fig. 8). As seen, CP-PC-SAFT yields reasonable predictions for the pure compound properties. PC-SAFT predicts slightly better the isobaric heat capacity of 1,2-dibromoeathane, however its results for the speeds of sounds are significantly less accurate. The results for changes on mixing61 are improved by taking k12 = 0.05 for both PC-SAFT and CP-PC-SAFT. However reproduction of the W-type shape of CPE obviously goes beyond the capabilities of the models under consideration.

4. Conclusions In this study we have reported the experimental measurements of speeds of sound from 293.15 to 313.15 K and pressures up to 100 MPa in 1,2-dichloroethane, and up to 45 MPa in 1,2-dibromoethane, approaching solidification of this compound. In addition, the new atmospheric pressure data on densities of 1,2-dichloroethane from 278.15 K to 348.15 K have been measured as well. These experimental results have been implemented for calculating densities, isobaric heat capacities and coefficients of thermal expansion, isentropic and isothermal compressibilities, and internal pressures as functions of pressure and temperature implementing an acoustic method of Davis-Gordon-Sun. Our results for densities, isothermal compressibilities, isobaric heat capacities and coefficients of thermal expansion and are in good agreement with the previously reported data of Malhotra and Woolf.7 At the same time, disagreement with the earlier measurements of Hilczer and Goc9 and Skinner et al10 for the high pressure densities of 1,2-dibromoethane takes place. Apparently, the accuracy of the two latter data sources should be considered as questionable. Comprehensive literature comparison of the ambient condition densities, isobaric heat capacities and speeds of sound for both compounds under consideration has been performed as well. A reasonable agreement between most of the data sources can be identified. In this study we have presented a development of a new DIPPR-based version of the FTEoS. A number of adjustable parameters in this version is reduced from two to one, requiring no high pressure data. A preliminary method for eliminating the remaining adjustable parameter considering the internal pressures has been presented. Unfortunately, currently this method is not entirely accurate, which requires its further development. One of its alternatives could be implementation of the DIPPR-based version of the FT-EoS to large variety of


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compounds followed by generalization of its adjustable parameter. As a result, this model could become a simple and reliable tool that implements the DIPPR’s saturated state expressions for predicting the high pressure densities and speeds of sound. This study has also demonstrated that both compounds under consideration can be included in the applicability range of the predictive CP-PC-SAFT approach employing the DIPPR’s critical constants. A major drawback of this model is its poor results for the vapor pressures of these compounds away from their critical points. In addition, CP-PC-SAFT may inaccurately predict the isobaric coefficients of thermal expansion. As seems, there is some unavoidable price to pay for the attempts to make thermodynamic models entirely predictive. Nevertheless, once again, it has been confirmed that CP-PC-SAFT is a reliable estimator of densities, speeds of sound and compressibilities of pure compounds and mixtures in the entire pressure range, and as well of the high pressure phase equilibria. Unlike CP-PC-SAFT, PCSAFT cannot be implemented for simultaneous modeling of the critical and the sub-critical states. Consequently, a parametrization of comprises fitting large experimental databases. Although this model is the less successful estimator of sound velocities, compressibilities and the critical states, it has a doubtless advantage in modeling the low-pressure phase equilibria.

Associated content. Supporting Information Table S1 compares the ambient condition densities, isobaric heat capacities and speeds of sound with the literature data. Tables S2 and S3 list the coefficients obtained by the acoustic method of Davis-Gordon-Sun. A description of this method is provided as well. Tables S4 and S5 list the thermodynamic properties of 1,2-dichloroethane and 1,2-dibromoethane. Table S6 lists the solutions of a system of Eqs. (24)-(27) for the compounds considered in this study. Figures S1 – S4 depict the results for the auxiliary thermodynamic properties of 1,2dichloroethane predicted by the considered models. This material is available free of charge via the Internet at http://pubs.acs.org.


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References (1) Chorążewski, M.; Skrzypek, M. Thermodynamic and Acoustic Properties of 1,3dibromopropane and 1,5-dibromopentane Within the Temperature Range from 293 K to 313 K at pressures up to 100 MPa. Int. J. Thermophys. 2010, 31, 26. (2) Chorążewski, M.; Postnikov, E. B. Thermal Properties of Compressed Liquids: Experimental Determination via an Indirect Acoustic Technique and Modeling Using the Volume Fluctuations Approach. Int. J. Therm. Sci. 2014, 90, 62. (3) Chorążewski, M.; Troncoso, J.; Jacquemin, J. Thermodynamic Properties of Dichloromethane, Bromochloromethane, and Dibromomethane Under Elevated Pressure: Experimental Results and SAFT-VR Mie Predictions. Ind. Eng. Chem. Res. 2015, 54, 720. (4) Global Ethylene Dichloride (EDC) Market 2015-2019, Business Report, ReportsnReports,

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(25) Chorążewski, M. Thermophysical and Acoustical Properties of the Binary Mixtures 1,2Dibromoethane + Heptane within the Temperature Range from 293.15 K to 313.15 K. J. Chem. Eng. Data 2007, 52, 154. (26) Góralski, P.; Tkaczyk, M.; Chorążewski, M. Heat Capacities of α,ω-Dichloroalkanes at Temperatures from 284.15 K to 353.15 K. J. Chem. Eng. Data 2003, 48, 492. (27) Peleties, F.; Segovia, J. J.; Trusler, J. P. M.; Vega-Maza, D. Thermodynamic properties and equation of state of liquid di-isodecyl phthalate at temperature between (273 and 423) K and at pressures up to 140 MPa. J. Chem. Thermodyn. 2010, 42, 631. (28) Chorążewski, M.; Dzida, M.; Zorębski, E., Zorębski, M. Density, speed of sound, heat capacity, and related properties of 1-hexanol and 2-ethyl-1-butanol as function of temperaturę and pressure. J. Chem. Thermodyn. 2013, 58, 389. (29) Brelvi, S.W.; O’Connell, J.P. Corresponding States Correlations for Liquid Compressibility and Partial Molal Volumes of Gases at Infinite Dilution in Liquids. AIChE J.

1972, 18, 1239. (30) Olson, J. D.; Wilson, L. C. Benchmarks for the Fourth Industrial Fluid Properties Simulation Challenge. Fluid Phase Equilib. 2008, 274, 10. (31) Otpushchennikov, N.F.; Zotov, V.V.; Neruchev, Yu. A. Compressibility of a liquid. Russ. Phys. J., 1970, 13, 648. (32) Lewis, W.C.M. Internal, molecular, or intrinsic pressure — a survey of the various expressions proposed for its determination. Trans. Faraday Soc., 1911, 7, 94. (33) Hildebrand, J.H. Solubility III. Relative values of internal pressures and their practical application. J. Am. Chem. Soc., 1919, 41, 1067. (34) Dack, M.R.J. The importance of solvent internal pressure and cohesion to solution phenomena. Chem. Soc. Rev., 1975, 4, 211. (35) Marcus, Y. Internal Pressure of Liquids and Solutions. Chem. Rev. 2013, 113, 6536. (36) Srivastava, S.C. Relationship between ultrasound velocity and other physical properties of pure organic liquids. Indian J. Phys. 1959, 33, 503. (37) Polishuk, I.; Privat, P.; Jaubert, J.-N. Novel Methodology for Analysis and Evaluation of SAFT-Type Equations of State. Ind. Eng. Chem. Res. 2013, 52, 13875. (38) Yelash, L.; Müller, M.; Paul, W.; Binder, K. A Global Investigation of Phase Equilibria Using the Perturbed-Chain Statistical-Associating-Fluid-Theory Approach J. Chem. Phys.

2005, 123, 14908. (39) Privat, R.; Gani, R.; Jaubert, J.-N. Are Safe Results Obtained When the PC-SAFT Equation of State is Applied to Ordinary Pure Chemicals? Fluid Phase Equilib. 2010, 295, 76.


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(40) Privat, R.; Conte, E.; Jaubert, J.-N.; Gani, R. Are Safe Results Obtained When SAFT Equations are Applied to Ordinary Chemicals? Part 2: Study of Solid-Liquid Equilibria in Binary Systems. Fluid Phase Equilib. 2012, 318, 61. (41) Polishuk, I. About the Numerical Pitfalls Characteristic for SAFT EOS Models. Fluid Phase Equilib. 2010, 298, 67. (42) Polishuk, I.; Addressing the Issue of Numerical Pitfalls Characteristic for SAFT EOS Models. Fluid Phase Equilib. 2011, 301, 123. (43) Polishuk, I.; Mulero, A. The Numerical Challenges of SAFT EoS Models. Rev. Chem. Eng. 2011, 27, 241. (44) NIST Standard Reference Database 203 Web Thermo Tables (WTT) - Professional Edition, http://www.nist.gov/srd/nistwebsub3.cfm. (45) Tihic, A.; Kontogeorgis, G. M.; von Solms, N.; Michelsen, M. L. Applications of the Simplified Perturbed-Chain SAFT Equation of State Using an Extended Parameter Table. Fluid Phase Equilib. 2006, 248, 29. (46) Tihic, A. Group Contribution sPC-SAFT Equation of State. Ph D Thesis, Technical University of Denmark, 2008. (47) Burgess, W. A.; Tapriyal, D.; Gamwo, I. K.; Wu, Y.; McHugh, M. A.; Enick, R. M. New Group-Contribution Parameters for the Calculation of PC-SAFT Parameters for Use at Pressures to 276 MPa and Temperatures to 533 K. Ind. Eng. Chem. Res. 2014, 53, 2520. (48) Kumagi, A; Takahashi, S. (Pressure, Volume, Temperature) Behaviour of Liquid 1,1Dichloroethane and 1,2-Dichloroethane. J. Chem. Thermodyn. 1985, 17, 977. (49) Sengupta, S.; Gupta, S.; Dooley, K. M.; Knopf, F. C. Measurement and Modeling of Extraction of Chlorinated Hydrocarbons from Water with Supercritical Carbon Dioxide. J. Supercrit. Fl. 1994, 7, 201. (50) Owens, J. L.; Brady, C. J.; Freeman, J. R. Vapor-Liquid Equilibrium Measurements. AIChE Symp. Ser. 1987, 83 (256), 18. (51) Konobeev, B. I.; Lyapin, V. V.

Solubility of Ethylene and Propylene in Organic

Solvents. Khim. Prom. 1967, 43, 114. (In Russian). (52) Chaudhari, S.K.; Katti, S.S. Vapour-Liquid Equilibria of Binary Mixtures of n-Hexane, n-Heptane and n-Octane with 1,2-dichloroethane at 323.15 K. Fluid Phase Equilib. 1990, 57, 297. (53) Amireche-Ziar, F.; Boukais-Belaribi, G.; Jakob, A.; Mokbel, I.; Belaribi, F. B. Isothermal Vapour–Liquid Equilibria of Binary Systems of 1,2-Dichloroethane With Ethers. Fluid Phase Equilib. 2008, 268, 39.


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(54) Garcia-Sanchez, F.; Trejo, A. Critical loci for binary chloroalkane-n-alkane mixtures. I. 1,2-Dichloroethane with C3-C9 n-alkanes. Fluid Phase Equilib. 1985, 24, 269. (55) Christou, G.; Sadus, R. J.; Young, C. L.; Svejda, P. Gas-Liquid Critical Properties of Binary Mixtures of n-Alkanes and 2,2,4-Trimethylpentane with the Weakly Polar Halocarbons 1,2-Dichloroethane, cis-1,2-Dichloroethene, trans-1,2-Dichloroethene, and Tetrachloromethane. Ind. Eng. Chem. Res. 1989, 28, 481. (56) Gil-Hernandez, V.; Garcia-Gimenez, P.; Embid, J. M.; Artal, M.; Velasco, I. Temperature and Pressure Dependence of the Volumetric Properties of Binary Liquid Mixtures Containing 1-Propanol and Dihaloalkanes. Phys. Chem. Liq. 2005, 43, 523. (57) Garcia-Gimenez, P.; Gil-Hernandez, V.; Velasco, I.; Embid, J. M.; Otin, S. Temperature and Pressure Dependence of the Volumetric Properties of Binary Liquid Mixtures Containing Dihaloalkanes. Int. J. Thermophys. 2005, 26, 665. (58) Garcia-Gimenez, P.; Gil, L.; Blanco, S. T.; Velasco, I.; Otin, S. Densities and Isothermal Compressibilities at Pressures up to 20 MPa of the Systems 1-Methyl-2-pyrrolidone + 1Chloroalkane or + α,ω-Dichloroalkane. J. Chem. Eng. Data 2008, 53, 66. (59) Garcia-Gimenez, P.; Martinez-Lopez, J. F.; Blanco, S. T.; Velasco, I.; Otin, S. GarciaGimenez, P.; Gil, L.; Blanco, S. T.; Velasco, I.; Otin, S.

Densities and Isothermal

Compressibilities at Pressures up to 20 MPa of the Systems N,N-Dimethylformamide or N,NDimethylacetamide + α,ω-Dichloroalkane. J. Chem. Eng. Data 2007, 52, 2368. (60) Hahn, G.; Ulcay, K.; Svejda, P.; Siddiqi, M. A. Isothermal Compressibilities of Binary Liquid Mixtures of 1,2-Dichloroethane and of trans- and cis-1,2-Dichloroethene + n-Alkanes or + 2,2,4-Trimethylpentane in the Pressure Range (0.1 to 10) MPa and at 293.15 K. J. Chem. Eng. Data 1996, 41, 319. (61) Privat, R.; Jaubert, J.-N. Discussion Around the Paradigm of Ideal Mixtures with Emphasis on the Definition of the Property Changes on Mixing. Chem. Eng. Sci. 2012, 82, 319. (62) Douhéret, G.; Davis, M. I.; Reis, J. C. R.; Blandamer, M. J. Isentropic Compressibilities Experimental Origin and the Quest for Their Rigorous Estimation in Thermodynamically Ideal Liquid Mixtures. CHEMPHYSCHEM 2001, 2, 148.


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Table 1. Experimental speeds of sound and densities of 1,2-dichloroethane at the atmospheric pressure (p0).* T/K

u0 / m·s-1

T/K

ρ0/ kg·m3

1.2-dichloroethane 292.24 298.64 303.76 308.62 314.67

1216.78 1192.11 1172.58 1153.94 1130.97

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 338.15 343.15 348.15

1275.06 1267.83 1260.57 1253.29 1245.98 1238.65 1231.30 1223.91 1216.48 1209.02 1201.52 1193.98 1186.40 1178.76 1171.07

* - The standard uncertainties are: u(p0) = 10 kPa, u(T) = 0.01 K. The combined expanded uncertainties Uc(ρ) = 0.05 kg·m-3 and Uc(u0) = 0.5 m·s-1


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Table 2. Experimental speeds of sound in 1,2-Dibromoethane and 1,2-Dichloroethane at high pressures.* 1,2-Dichloroethane T / K p / MPa u/m s−1 293.19 15.20 1267.35 293.18 30.40 1316.20 293.19 45.60 1360.77 293.15 60.79 1402.48 293.19 75.99 1441.20 293.19 91.19 1477.97 293.18 101.32 1501.35 298.17 15.20 1249.19 298.17 30.40 1298.92 298.17 45.60 1344.58 298.17 60.79 1386.79 298.16 75.99 1426.33 298.16 91.18 1463.59 298.17 101.32 1487.05 303.16 15.20 1231.20 303.15 30.40 1281.87 303.15 45.60 1328.34 303.15 60.79 1371.14 303.15 75.99 1411.44 303.15 91.19 1449.00 303.15 101.32 1472.88 308.13 15.20 1213.36 308.13 30.40 1265.15 308.13 45.60 1312.48 308.13 60.79 1356.10 308.13 75.99 1396.67 308.13 91.18 1434.84 308.13 101.32 1459.18 313.31 15.20 1195.05 313.30 30.39 1247.91 313.30 45.59 1296.02 313.30 60.79 1340.39 313.30 75.99 1381.71 313.30 91.19 1420.41 313.30 101.32 1445.02

1,2-Dibromoethane T / K p / MPa u/m s−1 293.07 15.20 1041.70 293.07 30.39 1074.34 293.07 45.60 1104.74 298.17 15.20 1029.17 298.17 30.39 1062.37 298.17 45.59 1093.37 303.14 15.20 1017.11 303.13 30.39 1050.87 303.12 45.59 1082.36 308.12 15.20 1005.10 308.12 30.39 1039.50 308.12 45.59 1071.46 313.28 15.20 992.76 313.28 30.39 1027.84 313.28 45.59 1060.29

* - The standard uncertainties u at elevated pressures are u(p) = 0.0015·p, u(T) = 0.05 K, and the combined expanded uncertainties Uc(u) < 1 m·s-1.


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Table 3. Accuracy of predicting densities of mixtures of 1,2-chloroethane by CP-PC-SAFT and PC-SAFT at high pressures with k12 = 0.02.

2nd compound

T range (K)

P range (bar)

Nr of points

AAD%

AAD%

CP-PC-SAFT

PC-SAFT

Reference

isooctane

278.15-338.15

1-2838

583

2.299

1.867

7

1-propanol

298.15

2-197

51

0.6683

1.858

56

ethyl acetate

298.15

2-199

51

0.5928

0.6190

57

1-methyl-2-pyrrolidone

298.15

1-200

99

0.5484

-

58

N,N-dimethylformamide

298.15

1-200

99

1.484

-

59

N,N -dimethylacetamide

298.15

1-200

99

0.8094

-

59

n-decane

293.15

1-100

54

0.8945

0.4323

60

n-dodecane

293.15

1-100

54

0.6529

0.7432

60

n-tetradecane

293.15

1-100

54

0.4483

0.4087

60

n-hexadecane

293.15

1-100

54

0.4095

0.7221

60

24 ACS Paragon Plus Environment

Page 25 of 34

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure captions Figure 1. Speeds of sound and densities of 1,2-dichloroethane at high pressures. Experimental data: empty circles – Malhotra and Woolf7, filled circles – Kumagi and Takahashi48, half-filled circles – current work. Predictions: solid lines – CP-PC-SAFT implemented with the critical constants 561.8 K & 56.78 bar, dashed lines – 561 K & 53 bar.

Figure 2. Speeds of sound and densities of 1,2-dichloroethane at high pressures. Experimental data: see legend of Fig. 1. Predictions: solid lines – FT-EoS, dashed lines – CPPC-SAFT, dashed-dotted-dotted lines – PC-SAFT.

Figure 3. Speeds of sound and densities of 1,2-dibromoethane at high pressures. Experimental data: empty circles – Hilczer and Goc9, filled circles – Skinner et al.10, halffilled circles – current work. Predictions: solid lines – FT-EoS, dashed lines – CP-PC-SAFT, dashed-dotted-dotted lines – PC-SAFT.

Figure 4. Vapor pressures of 1,2-dichloroethane and 1,2-dibromoethane. Data obtained from DIPPR21 – points. Solid lines – CP-PC-SAFT, dashed lines – PC-SAFT.

Figure 5. High pressure VLE in binary systems containing 1,2-dichloroethane. Experimental data49-53 – points. Solid lines – CP-PC-SAFT, dashed lines – PC-SAFT.

Figure 6. Critical lines in binary systems containing 1,2-dichloroethane and n-alkanes. Points - experimental data.54,55 Solid lines – CP-PC-SAFT, dashed lines – PC-SAFT (k12 = 0.02 for both models).

Figure 7. High pressure densities of binary systems containing 1,2-dichloroethane. Experimental data.7,56-60 Solid lines – CP-PC-SAFT, dashed lines – PC-SAFT (k12 = 0.02 for both models).

Figure 8. Thermodynamic properties of 1,2-dibromoethane – n-heptane at atmospheric pressure. Data25 – points. Solid lines – CP-PC-SAFT, dashed lines – PC-SAFT. (k12 = 0.05 for both models). Here uM* indicates the deviation from linearity and not the rigorous changing on mixing property.62


25


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 34

Figures


26

Page 27 of 34

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1450

ρ (g/dm3)

K 15 . 8 27 K 15 . 3 31

1350

K .15 8 3 3 5K 1 . 398

1250

1150

A 1050 0

1500

P(bar)

3000

4500

1510

u (m/s) 1340

K .15 3 30 K .15 3 29 .1 5 3 1 3

1170

K

B 1000 0

400

P(bar)

800

1200

Figure 1 ACS Paragon Plus Environment

27


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 34

1450

ρ (g/dm3)

.1 278

1350

5K

.1 313

5K

.1 338

5K

K 15 . 8 39

1250

1150

A 1050 0

1500

P(bar)

3000

4500

1510

u (m/s) 30

1340 2

5 3 .1

K 15 . 3 9 .1 313

1170

K

5K

B 1000 0

400

P(bar)

800

1200


28

Page 29 of 34

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2250

ρ (g/dm3) K .15 3 9 2

2210

.1 303

5K

2170 . 313

K 15

A 2130 0

200

P(bar)

400

600

1120

u (m/s) 1060

5 293.1

K

5K 303.1

1000

313.1

5K

940

880

B 820 0

200

P(bar)

400

600

Figure 3


29


66

100

1, 2-

P (bar)

Di ch lo ro

e an th oe

1

om br Di 2-

10

1,

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 34

44

et ha ne

22

0 350

430

510

590

T (K)

.1

.01

.001

.0014

.0026

1/T (1/K) .0038

.0050

Figure 4


30

670

Page 31 of 34

40

100

A CO2(1) - 1,2-Dichloroethane(2) k12 = 0

5K

P(bar) K

3 .1

30

3 32

31

60

K

3.

.2

31

80

2

20

40 .6

K .15 3 9

K 3.2 10

.4

15

33

P(bar)

.8

x1,y1

1.0

B Ethene(1) - 1,2-Dichloroethane(2) k12 = 0

0 0.00

.15

.30

x1

.45

9

30

C Vinyl Chloride(1) - 1,2-Dichloroethane(2) k12 = 0.02

5K

P(bar)

3.1

P(bar)

33

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


6

20

3 31 K .15 3 7 3

10

.2

.4

x1,y1

.6

K

15 K 293.

3

15 K 346. 320.15 K

D Propene(1) - 1,2-Dichloroethane(2) k12 = 0.02

0 0.0

.15

.8

1.0

0 0.00

.15

.30

x1

.45

2.4

.4

F Diethyl Ether(1) - 1,2-Dichloroethane(2) P(bar) k12 = 0.02

E P(bar) 1,2-Dichloropropane(1) - n-Octane(2) k12 = 0.02 .3

1.6 .2

3

K .15 3 2

3 33. .8

15 K

313.15 K

.1

298.15 K 0.0

273.15 K

0.0 0.0

.2

.4

x1,y1

.6

.8

1.0

0.0

.2

.4

x1

.6

.8


31

1.0


Page 32 of 34

80 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

P(bar)

A

60

40

C3 n-C4 n-C5

n-C6

20 350

450

n-C7 n-C 8

n-C9

550

T(K)

650

80

B

P(bar) C3 60 n-C4

n-C

6

40

n -C

n-C

7

9

20 0.0

.2

.4

x1

.6

.8

1.0

800

T(K)

C n-C 14

650

n-C10

n-C7

500

n-C 4

350 0.0

.2

.4

x1

.6


.8

1.0

Figure 6 32

Page 33 of 34


1 1220 1500 2 1,2-Dichloroethane(1)+1-Propanol(2) ρ 1,2-Dichloroethane(1)+Isooctane(2) ρ 3 3 298.15 K; k12 = 0.02 3 278.15 K; k12 = 0.02 (g/dm ) 4 (g/dm ) 1140 x1 = 0.6856 5 994 4 .8 0 = 1200 6 x1 7 8 x1 = 0.5042 1060 7 8 9 9 .4 x1 = 0 10 900 11 6 x1 = 0.0998 980 12 x1 = 0.3030 13 14 A B 15 900 600 16 0 80 240 0 1000 3000 P (bar) 2000 P (bar) 160 17 18 1400 1250 19 1,2-Dichloroethane(1)+1-Methyl-2-pyrrolidone(2) 1,2-Dichloroethane(1)+Ethyl Acetate(2) ρ 20 ρ 298.15 K; k12 = 0.02 3 298.15 K; k12 = 0.02 21 (g/dm ) (g/dm3) 22 1170 23 x1 = 0.9007 1250 x1 = 0.6994 24 25 1090 26 x1 = 0.5025 x1 = 0.5013 27 28 1100 x1 = 0.0971 29 95 0.29 = x 1010 1 30 31 D C 32 950 930 33 0 80 240 0 80 240 34 P (bar) 160 P (bar) 160 35 36 1440 1440 37 1,2-Dichloroethane(1)+N-N-Dimethylacetamide(2) ρ 1,2-Dichloroethane(1)+N,N-Dimethylformamide(2) 38 ρ 3 298.15 K; k12 = 0.02 298.15 K; k12 = 0.02 (g/dm ) 39 (g/dm3) 40 x1 = 0.9195 41 1260 x1 = 0.9023 1260 42 43 44 x1 = 0.5012 x1 = 0.5001 45 1080 1080 46 47 x1 = 0.0929 x1 = 0.1003 48 49 F E 50 900 900 51 0 80 240 0 80 240 P (bar) 160 P (bar) 160 52 53 54 55 56 Figure 7 57 58 59 60 ACS Paragon Plus Environment

33

Industrial & Engineering Chemistry Research 0

1200

1 A u(m/s) 2 3 1100 4 5 6 1000 7 8 9 10 900 11 12 13 800 14 0.0 .2 15 16 17 2400 18 19 ρ 20 3 ) (g/dm 21 22 1800 23 24 25 26 27 1200 28 29 30 T = 293.15 K 31 32 600 0.0 .2 33 34 35 240 36 CP 37 E 38 (J/mol) 39 210 40 41 42 180 43 44 45 46 150 47 48 49 120 50 0.0 .2 51 52 53 54 55 56 Figure 8 57 58 59 60

Page 34 of 34

B

M*

u (m/s) -25

-50

-75

T = 292.7 K

T = 292.7 K -100

.4

x1

.6

.8

1.0

0.0

.2

.4

x1

.6

.8

1.0

0

D

ρΜ

C

3

(g/dm ) -100

-200

T = 293.15 K -300 .4

x1

.6

.8

1.0

0.0

.2

.4

x1

.6

.8

1.0

1.5

F

CP M (J/mol) .5

-.5

T = 293.15 K

T = 293.15 K -1.5

.4

x1

.6

.8

1.0

0.0


.2

.4

x1

.6

.8

34

1.0

Thermodynamic Properties of 1, 2-Dichloroethane and 1, 2

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