Saft Mie

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Expanding the Applications of the SAFT-γ Mie Group-

Contribution Equation of State: Prediction of
Thermodynamic Properties and Phase Behaviour of Mixtures
Journal: Journal of Chemical & Engineering Data
Manuscript ID je-2020-00746c
Manuscript Type: Article
Date Submitted by the

15-Aug-2020
Author:
Complete List of Authors: Haslam, Andrew; Imperial College London, CHEMICAL ENGINEERING
Gonzalez-Perez, Alfonso; CEPSA
Di Lecce, Silvia; Imperial College London Faculty of Natural Sciences,
Chemistry
Khalit, Siti Hajar; Imperial College London, CHEMICAL ENGINEERING
Perdomo, Felipe; Imperial College London, CHEMICAL ENGINEERING
Kournopoulos, Spiros; Imperial College London, CHEMICAL
ENGINEERING
Kohns, Maximilian; Technische Universitat Kaiserslautern, Laboratory of
Engineering Thermodynamics
Lindeboom, Tom; Imperial College London, CHEMICAL ENGINEERING
Febra, Sara; Equinor ASA
Jackson, George; Imperial College London, Chemical Engineering
Adjiman, Claire; Imperial College London, Centre for Process Systems
Engineering
Galindo, Amparo; Imperial College of Science, Dept. of Chem. Engng.
and Chem.Tech.; Imperial College London, Department of Chemical
Engineering
ACS Paragon Plus Environment

Page 1 of 92 Submitted to Journal of Chemical & Engineering Data
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Expanding the Applications of the SAFT-γ Mie
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11 Group-Contribution Equation of State:
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Prediction of Thermodynamic Properties and
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18 Phase Behaviour of Mixtures
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22 Andrew J. Haslam,† Alfonso González-Pérez,†,§ Silvia Di Lecce,†,k Siti H.
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24 Khalit,† Felipe A. Perdomo,† Spiros Kournopoulos,† Maximilian Kohns,‡ Tom
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27 Lindeboom,† Sara Febra,¶ George Jackson,† Claire S. Adjiman,† and Amparo
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29 Galindo∗,†
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32 †Department of Chemical Engineering, Centre for Process Systems Engineering, Imperial
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34 College London, South Kensington Campus, London SW7 2AZ, United Kingdom
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36 ‡Current address: Department of Mechanical and Process Engineering, Laboratory of
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38 Engineering Thermodynamics, University of Kaiserslautern, Erwin-Schrödinger-Straße 44
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40 Building 44/418 D-67663 Kaiserslautern
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42 ¶Current address: Equinor ASA, 1330 Fornebu,, Norway
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44 §Current address: CEPSA Oil and Energy, Madrid, Spain
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46 kCurrent address: Department of Chemistry, Imperial College London, White City
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48 Campus, London, United Kingdom
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51 E-mail: a.galindo@imperial.ac.uk
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54 Abstract
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We present the latest developments in thermodynamic modelling using the SAFT-γ
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60 ACS Paragon Plus Environment
Submitted to Journal of Chemical & Engineering Data Page 2 of 92
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Mie group-contribution equation of state. The group database is updated, featuring
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5 now 61 groups; this expanded database incorporates new parameters for interactions
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7 between both like and unlike groups. Groups now available provide the capability
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9 to treat mixtures including alcohols, ethers, ketones, carboxylic acids and acetates,
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11 amines, aromatic and cyclic compounds, electrolytes, inorganic acids and some com-
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13 mon solvents, such as water and acetone. A discussion is provided relating to the use
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15 of the groups, including some secondary groups that are introduced for multifunctional
16
molecules to capture the influence on behaviour of molecular polarisation effects. Per-
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18 formance of the SAFT-γ Mie approach is illustrated for a wide variety of systems,
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20 highlighting its use in describing solid–liquid as well as vapour–liquid and liquid–liquid
21
22 equilibria.
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25
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27 1 Introduction
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29
30 Since its appearance at the end of the 1980s, the statistical associating fluid theory (SAFT)
31 1,2
32 has assumed steadily increasing importance in the field of thermodynamic modelling of
33
34 fluids. 3–6 Its adoption and further developments by different research groups world-wide has
35
36 led to the emergence of different versions of the theory, including soft-SAFT 7 , SAFT-VR
37 8,9
38 , PC-SAFT 10,11 and, more recently, SAFT-VR Mie 12 . The original development of the
39
40 SAFT approach provided an equation of state (EoS) that could describe fluids for which the
41
42
traditional cubic EoS, such as those of Soave 13 and of Peng and Robinson 14 , fall short –
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44
in particular, fluids of highly non-spherical molecules, and associating fluids. The success of
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the approach lies in its molecular basis, with a firm foundation in the statistical mechanics
47
48
of fluids, incorporating the theory of Wertheim 15–18 for associating fluids.
49
50
In SAFT, the Helmholtz free energy of the fluid is expressed as a sum of contributions,
51
52
each arising from different features of the underlying molecular model. This makes the
53
54
approach highly adaptable; the inclusion of extra contributions have allowed for the provision
55
56
of EoS for fluids of polar molecules, 19–31 and of electrolyte solutions. 32–43 More recently, this
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1
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3
adaptability has allowed for the development of group-contribution (GC) versions of SAFT
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5 44–54
.
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7
GC approaches have featured prominently in the thermodynamic-modelling toolkit since
8
9 the 1970s. The philosophy of these approaches is that properties of a substance can be ob-
10
11 tained as a sum of contributions from appropriately defined functional groups making up the
12
13 molecules of which the substance is comprised. As early as 1955, Lydersen 55 developed a suc-
14
15 cessful GC approach to estimate critical properties; this approach was extended in the 1980s
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17 by Joback and Reid 56,57 to estimate a range of pure-component thermodynamic properties.
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19 Later Gani and co-workers 58,59 refined approaches to incorporate isomerism and proximity
20
21 effects through the concept of secondary groups. GC approaches have also been developed
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23 for mixtures, initially focussing on activity coefficients in liquid mixtures. Indeed, perhaps
24
25 the most important activity-coefficient method historically is the well-known universal func-
26
27 tional activity coefficient (UNIFAC) approach 60–62 that, together with its modifications, has
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29 been firmly established for decades.
30
31 Of more interest in the context of our current work, however, is the emergence of GC
32
33 approaches within the framework of EoS modelling of fluids. Their first appearance was
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35 in relation to mixture calculations using cubic EoS, through what have become known as
36
37 EoS/GE mixing rules. The link to GC approaches was through the incorporation, within the
38
39 mixing rules, of activity coefficients that could, for example, be obtained from a GC approach,
40
41 such as UNIFAC. The first of the EoS/GE mixing rules was developed by Huron and Vidal
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43 63
. Improved EoS/GE mixing rules were subsequently published by various researchers,
44
45 including Michelsen and coworkers 64–66 , and Wong and Sandler 67 ; the PSRK EoS 68 falls
46
47 also into this category. Later, following a slightly different strategy, a GC approach was
48
49 introduced to enable the prediction of the binary interaction parameter used in mixture
50
51 combining rules to characterise the unlike (cross) attractive EoS parameter. 69,70 Each of
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53 these two strategies renders predictive power on cubic EoS that had hitherto been largely
54
55 correlative.
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The adoption of GC approaches within the SAFT methodology was perhaps a more-
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5
natural development than their use in conjunction with cubic EoS. Whereas the molecular
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7
model underlying a cubic EoS is a single sphere (consisting of a hard core surrounded by
8
9 a region of attraction), that underlying a conventional SAFT EoS is a chain of spherical
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11 segments that interact through a particular potential (the precise nature of the potential
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13 depends on the particular implementation of SAFT under consideration). In other words,
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15 the molecule is already considered as made up of groups, albeit (in early SAFT approaches)
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17 with the fundamental difference (from GC methods) that all the segments making up the
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19 molecule are identical. In some GC adaptions of SAFT 44–46,49,51–53 , GC approaches are
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21 used to characterise this identical-segment (or homonuclear ) chain, and the fluid properties
22
23 are then evaluated using the existing SAFT theory. It has been pointed out 71 that, in
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25 general, the homonuclear-chain approach should be classified as a GC-based mixing rule for
26
27 molecular parameters rather than a GC SAFT formalism, in which the underlying theory
28
29 would explicitly capture and explain thermodynamic behaviour in terms of the different
30
31 groups making up the molecules. It can be thus argued that the homonuclear formulations
32
33 do not fully exploit the GC method, insofar as the approach presents no opportunity to
34
35 predict mixture properties from pure-component data alone.
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37 Arguably, the primary attraction of the GC method lies in its predictive power; once the
38
39 contributions from a set of functional groups are known they can, in principle, be combined to
40
41 predict the properties of any compound or mixture that comprises these groups. This concept
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43 is exploited fully in the GC-SAFT-VR 50 , hs-PC-SAFT 71 and SAFT-γ 47,48,54 approaches. In
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45 these, the formalism is based on a more-detailed molecular model in which different types of
46
47 monomeric segments are used to represent the individual chemical functional groups making
48
49 up a molecule; the model molecule is therefore heteronuclear. Contrasting the homonuclear
50
51 approaches, the GC concept is embedded within the SAFT formalism itself. The retention
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53 of the functional-group information in the molecular model provides the key advantage that
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55 thermodynamic properties of mixtures can be predicted based on pure-component data alone.
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59 4
1
2
3 48,50,54,72
The unlike EoS parameters that characterize the interactions between the different
4
5
groups present in a mixture can be determined from carefully chosen pure-component data
6
7
that implicitly contain information characterising the relevant unlike interactions, or from
8
9 appropriate combining rules (see, e.g., Ref. 73 ).
10
11 In principle, the predictive capacity of the heteronuclear SAFT approaches is consider-
12
13 able. However, it is evident that the predictive capacity of any GC SAFT formalism is, at
14
15 the same time, constrained by the availability of groups for which parameters are known.
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17 The focus of our current work is SAFT-γ Mie 54 , which can be thought of as the (more-
18
19 general) GC version of the earlier (homonuclear) SAFT-VR Mie 12 . A heteronuclear model
20
21 is implemented in SAFT-γ Mie, and a Mie (generalized Lennard-Jones) potential of variable
22
23 repulsive and attractive ranges is used to represent the segment–segment interactions. As
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25 evidenced by the growing number of published works 74–124 in which SAFT-γ Mie has been
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27 employed, the use of the approach is becoming widespread, not only in the traditional sense
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29 of GC modelling, but also as a basis for the development of coarse-grained force fields that
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31 are finding application in molecular simulations. 76–79,84,85,91,96,100,105,109–111,115,120,124
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33 In more-conventional equation-of-state modelling, the range of fluids considered and the
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35 contexts in which SAFT-γ Mie have been applied continue to broaden. Sadeqzadeh et al. 83
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37 have used SAFT-γ Mie to study the phase behaviour of aqueous mixtures comprising ace-
38
39 tone, alkanes and alkyl carboxylic acids. Silva et al. 86 have used SAFT-γ Mie to study the
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41 phase equilibria of biodiesel systems. Gopinath et al. 89,90 have pioneered the use of SAFT-γ
42
43 Mie within computer-aided molecular and process design (CAMPD) problems, focussing on
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45 the design of optimal solvents in separation processes. Kazepedis et al. 125 and Papdopoulos
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47 et al. 126 have used also used the approach in the context of computer-aided molecular de-
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49 sign (CAMD) of CO2 capture processes. Papaioannou et al. 88 have used SAFT-γ Mie in a
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51 study of fluids of relevance to the oil and gas industry. Sabattie et al. 99 have used SAFT-
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53 γ Mie, in conjuction with MD simulation, in volume-of-mixing calculations pertaining to
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55 oligomer–polymer mixtures. Hutacharoen et al. 102 have used the approach to provide accu-
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rate predictions of the phase equilibria of alkanes and alcohols in aqueous solution, including
4
5
liquid–liquid equilibria, solubility, free energies of solvation, and other infinite-dilution prop-
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7
erties, as well as predicting octanol–water partitioning and solubility for a range of organic
8
9 and pharmaceutically relevant compounds. Samsatli et al. 82 used SAFT-γ Mie to predict
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11 the thermodynamic properties of hydrogen in the context of transport in pipelines. (We note
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13 also the works of Contreras et al. 127 and Aasen et al. 128 in developing the SAFT-VR Mie
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15 and SAFT-γ Mie formalism to take account of quantum effects when modelling hydrogen or
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17 other fluids for which quantum effects are important.) Markides and co-workers have applied
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19 SAFT-γ Mie in the context of CAMD for working fluids in organic Rankine cycle engines
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21 94,103,106,121
and diffusion-absorption refrigerators 112 ; Bowskill et al. 129 have independently
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23 used SAFT-γ Mie within CAMD for ORC systems. Watson et al. 114 have used SAFT-γ
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25 Mie in the design of crystallisation solvents. Esters, in the form of pure species and binary
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27 mixtures, have been successfully modelled by Haarman et al. 119 using SAFT-γ Mie (as well
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29 as PC-SAFT 10,11 ); in related work, binary mixtures of the fatty acid methyl decanoate with
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31 linear alkanes have also been studied. 118 Bui et al. 108 have used SAFT-γ Mie to describe
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33 the thermodynamics and fluid phase equilibria for chemisorption of carbon dioxide in amine
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35 solvents, within process modelling of pilot-scale amine-based CO2 capture plants. Aqueous
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37 mixtures of CAGE (choline and geranate), classed as both an ionic liquid and deep eutectic
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39 solvent, 130–132 have been studied by di Lecce et al. 123 .
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41 To support the increasing interest in SAFT-γ Mie, there is a pressing need for the ex-
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43 pansion of the SAFT-γ Mie group database. The primary purpose of our current article
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45 is to provide an update of the status of the SAFT-γ Mie group database, as developed by
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47 our research group at Imperial College London, since it was summarised by Dufal et al. 75
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49 in 2014. Expanding upon this database, parameters for functional groups published in the
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51 interim are collected together, and newly developed parameters are presented for functional
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53 groups not previously treated. (Note that we do not include group parameters developed by
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55 other research groups.) The resulting group parameter table presented here now contains 61
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59 6
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groups, increasing the size of the previous table 75 by a factor of four; the expansion of the
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5
database includes also new tailored parameters representing the interactions between unlike
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7
groups, reducing reliance on combining rules. To complement the expanded database, a
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9 brief but wide-ranging illustration of the performance of the approach is provided, favouring
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11 systems containing groups presented here for the first time, and featuring different classes of
12
13 phase behaviour.
14
15 The remainder of this article is set out as follows. In Section 2, a brief summary is
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17 provided of the SAFT-γ Mie model and theory. In Section 3, we present the up-to-date
18
19 parameter database, together with a discussion on the usage of the different groups. Section
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21 4 comprises our illustration of the performance of the approach. Finally, in Section 5, we
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23 summarise with a short discussion and our concluding remarks.
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25
26
27
28 2 SAFT-γ Mie Model and Theory
29
30
31 The theoretical development and background to the SAFT-γ Mie EoS has been presented
32
33 in detail in Ref. 54 and summarised in Ref. 75 , with further clarification provided in Ref. 133 .
34
35 Here we provide only a brief summary of the features required to characterise the molecular
36
37 model underlying the approach.
38
39 In the framework of the SAFT-γ Mie equation of state 54 , molecules are modelled as
40
41 heteronuclear chains of fused spherical segments with associative sites. As an example, in
42
43 Figure 1, two organic compounds, phenol and cyclohexanol, are decomposed in functional
44
45 groups, as characteristic of approach. These molecules resemble each other in terms of
46
47 connectivity of the carbon backbone – both are substituted six-membered rings. However,
48
49 they differ fundamentally insofar as phenol features an aromatic ring, whereas cyclohexanol
50
51 is a substituted cyclohexane. Accordingly, the functional groups required to describe these
52
53 two molecules are significantly different; phenol is constituted by aromatic groups (aCH and
54
55 aCOH), while cyclohexanol is here represented by cyclic carbon groups (cCH2 ) and a hydroxy
56
57
58
59 7
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 (a) (b)
16
17
Figure 1: Examples of model representation within the SAFT-γ Mie approach: (a) phenol
18 is broken down into five aromatic carbon groups (aCH) and one phenol group (aCOH);
19 (b) cyclohexanol is broken down into five cyclic methylene groups (cCH2 ) and one hydroxy
20 carbon group (CHOH). Both aCOH and CHOH groups are depicted with association sites,
21 two acceptor sites representing the electron lone pairs on the oxygen atom (labelled ‘e’, and
22
23 highlighted in red) and one donor site representing the hydrogen atom (labelled ‘H’, and
24 highlighted in white).
25
26
27 carbon (CHOH) group (there is no need for a dedicated cyclic hydroxy carbon (cCHOH)
28
29 group since the regular hydroxy carbon group substitutes very satisfactorily in this role).
30
31 In general, any compound i is represented by its different constituent groups k, where
32
33 the number of occurrences of a group of type k is counted by νk,i . Each functional group is
34
35 represented as fused segments and within a functional group each segment is identical; the
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37 number of segments within a group is denoted by νk∗ .
38
39 Segments interact through Mie 134 potentials of variable attractive and repulsive ranges,
40
41 given as " λrkl λakl #
42

σkl σkl
43 ΦMie
kl (rkl ) = Ckl εkl − , (1)
rkl rkl
44
45
46 where rkl is the centre–centre separation of segments k and l, σkl is a size parameter (cor-
47
48 responding to the segment diameter in the case of like−like interactions (k = l)), εkl is the
49
50 depth of the potential well, and λrkl and λakl are, respectively, the repulsive and attractive
51
52 exponents of the interaction between the segments. The prefactor Ckl is given by
53
54 a
λr λ−λ
kl
55 λr λrkl
a
kl kl
56 Ckl = r kl a ; (2)
λkl − λkl λakl
57
58
59 8
1
2
3
this form that ensures that the minimum of the interaction is −εkl . The Helmholtz free energy
4
5
of this model is obtained as a sum of appropriate contributions of the different groups; an
6
7
additional parameter, the shape factor, Sk , is introduced to account for the proportion that
8
9 a given segment in a molecule contributes to the total free energy.
10
11 Strongly polar interactions, such as hydrogen bonding, are usually treated using addi-
12
13 tional off-center associating sites interacting through short-ranged square-well potentials,
14
15 which are placed on any given segments as required. The square-well interaction between an
16
17 association site of type a on segment k and a site of type b on segment l is given by
18
19
20

−εHB c

21 if rkl,ab ≤ rkl,ab

kl,ab
22 ΦHB
kl,ab (rkl,ab ) = , (3)
23 
0
 if rkl,ab > c
rkl,ab
24
25
26
27 where rkl,ab is the distance between the centres of the two sites, −εHB
kl,ab is the association
28 c
29 energy, and rkl,ab the cut-off range of the interaction, respectively. Site a is positioned at
30 d d c
31 a distance rkk,aa from the centre of segment k; rkk,aa and rkk,aa are both fixed to a value
32
33 of 0.4σkk in our version of the theory. 135 Parameters are defined analogously for site b on
34
35 segment l. Note that, commensurate with the thermodynamic perturbation theory (TPT1)
36
37 of Wertheim 136 used here, individual sites are independent of each other so that the relative
38
39 positions of the various sites on a segment are not taken into account. Note also that the
40 c
41
cut-off distance rkl,ab can equivalently be described in terms of a bonding volume Kkl,ab ; see
42
43
equation 69 of Ref. 54 for details. To fully describe associating groups, the number NST,k of
44
45
different site types, and the number of sites of each type, e.g., nk,a , nk,b , . . ., nk,NST,k , are also
46
47
specified.
48
49
If ions or other charged species are present, the formalism is extended following Schreken-
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51
berg et al. 41 and Eriksen et al. 43 , and di Lecce et al. 123 . Coulombic interactions pertaining
52
53
to the charged species are represented following an unrestricted primitive model; each of the
54
55
ionic species is treated as spherical with a central point charge, q. Here, the explicit repre-
56
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59 9
1
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3
sentation of solvent molecules is implicitly replaced by a dielectric medium of relative static
4
5 Born is
permittivity D. An additional parameter, representing the Born cavity diameter, σkk
6
7
required to fully describe a charged group.
8
9
10
11 To summarise, a functional group k is fully described by the number νk∗ of identical
12
13 spherical segments forming the group, the segment energy of interaction εkk , the diameter
14
15 of the segments σkk , the exponents of the Mie potential λrkk and λakk and the shape factor
16
17 of the segments Sk , as well as (where relevant) the parameters characterizing any site-site
18
19 association interactions, εHB c
kk,aa , rkk,aa (or Kkk,aa ), and nk,a , nk,b , . . ., nk,NST,k . In the event that
20
21 the group is charged, the charge ascribed to the group, qk and the Born cavity diameter,
22
23 Born , are also required to complete the description. The interactions between groups of
σkk
24
25 different types k and l are characterized analogously by the corresponding unlike parameters
26
27 εkl , σkl , λrkl , λakl , εHB c
kl,ab , and rkl,ab (or Kkl,ab ). Finally, if charged groups are present, a value
28
29 of the dielectric constant, D, is needed to complete the description of the system within the
30
31 SAFT-γ Mie methodology.
32
33 The total Helmholtz free energy A of a mixture of associating heteronuclear chains of
34
35 fused spherical segments, some of which (representing ions) may be charged, is expressed as
36
37 the sum of six separate contributions:
38
39
40
41 A = Aideal + Amono. + Achain + Aassoc. + ABorn + Aion . (4)
42
43
44
45 Here Aideal is the free energy of an ideal gas mixture of the corresponding molecules, Amono.
46
47
is the contribution accounting for the Mie segment-segment interactions (repulsion and dis-
48
49
persion) of the reference monomeric system, Achain represents the change in the free energy
50
51
due to the formation of molecules from Mie segments, and Aassoc. is the contribution to the
52
53
free energy from the association interactions. The detailed expressions for each of these four
54
55
terms are given in the original publication 54 where the association term has been replaced
56
57
58
59 10
1
2
3
by the Lennard-Jones based term in. 135 The latter two terms, ABorn and Aion , account for
4
5
electrostatic contributions. ABorn accounts for the free energy of solvation, representing the
6
7
contribution to the free energy due to the insertion of all ions in the dielectric medium,
8
9 while Aion is the contribution due to the electrostatic interactions between charged species.
10
11 Detailed discussions of the incorporation of electrostatic interactions can be found in, e.g.,
12
13 Refs. 43 and 123 .
14
15
16
17 2.1 Ideal Term
18
19
20 The free energy corresponding to an ideal mixture of molecules is given by 137
21
22 NC
!
23 Aideal X
3

24 = xi ln ρi Λi −1 , (5)
N kB T
25 i=1
26
27 where xi is the mole fraction of component i in the mixture, ρi = Ni /V is the number density
28 NC
29 X
30
with Ni the number of molecules of component i, V the total volume, N = Ni the total
31 i
32
number of molecules, kB the Boltzmann constant, and T the absolute temperature. The
NC
33 X
34 summation is over all of the components NC of the mixture (i.e., N = Ni ). The thermal
35 i
36 de Broglie volume Λ3i implicitly incorporates the effects of rotational and vibrational as well
37
38 as translational contributions to the kinetic energy.
39
40
41
42 2.2 Monomer Term
43
44 The monomer contribution to the free energy, representing dispersive (repulsive and attrac-
45
46 tive) interactions of the fluid of monomeric segments, is obtained from a Barker-Henderson 138,139
47
48 high-temperature perturbation expansion up to third order, 12 expressed as
49
50
51 Amono. AHS A1 A2 A3
52 = + + + . (6)
53
N kB T N kB T N kB T N kB T N kB T
54
55
56
In equation 6 AHS is the free energy of a hard-sphere reference system of (temperature-
57
58
59 11
1
2
3
dependent) diameter dkk . 139 This is obtained as a sum of contributions from each segment,
4
5
according to 47
6 NC NG
!
7 AHS X X
8
= xi νk,i νk∗ Sk aHS , (7)
N kB T
9 i=1 k=1
10 where xi is the mole fraction of component i, NG is the number of types of groups present,
11
12 and aHS is the (dimensionless) contribution to the hard-sphere free energy per segment. The
13
14 latter is obtained following Boublı́k 140 and Mansoori et al. 141 , as a function of the number
15
16 density ρs of the segments in the fluid:
17
18
19 6 ζ23

HS
20 a = − ζ0 ln(1 − ζ3 )
21 πρs ζ32
22 ζ23

ζ1 ζ2
23 +3 + , (8)
1 − ζ3 ζ3 (1 − ζ3 )2
24
25
26 where
27 NC NG
!
28
X X
ρs = ρ xi νk,i νk∗ Sk (9)
29
i=1 k=1
30
31 and the ζm are moment densities, given by
32
33
34 NG
πρs X
35 ζm = xs,k dm
kk , m = 0, 1, 2, 3 ; (10)
36 6 k=1
37
38
39 xs,k is the fraction of segments of a group of type k in the mixture:
40
41 NC
42
X
43
xi νk,i νk∗ Sk
i=1
44 xs,k = . (11)
N NG
45 XC X
46 xj νl,j νl∗ Sl
47 j=1 l=1
48
49
50 The remaining two terms in the expansion are evaluated using analogous summations over
51
52 the free-energy contributions per segment, each with their corresponding power of reciprocal
53
54 temperature, whence the first-order term (the mean attractive energy), the second-order
55
56
57
58
59 12
1
2
3
term (the energy fluctuation), and the third-order term are given by
4
5
6 q NC NG
!
7
Aq 1 X X
= xi νk,i νk∗ Sk aq , q = 1, 2, 3 . (12)
8 N kB T kB T i=1 k=1
9
10
11 The aq are obtained by summing the pairwise aq,kl between groups k and l over all pairs
12
13 of functional groups present in the system:
14
15 NG X
NG
16 X
17 aq = xs,k xs,l aq,kl , q = 1, 2, 3 . (13)
18 k=1 l=1
19
20 As described in Ref. 54 , in order to calculate exactly a1,kl , appearing in the first pertur-
21
22 bation term a1 , one requires prior knowledge of the radial distribution function (RDF) of the
23
24 effective hard-sphere fluid for a range of separations and, moreover, a numerical integration
25
26 is required. To obtain an analytical expression for this contribution, the mean-value theo-
27
28 rem has been employed, in the spirit of the development of the original SAFT-VR 8 , and a
29
30 mapping of the real density of the fluid to an effective density carried out. 12 This mapping
31
32 was undertaken for ranges of exponents of the Mie potentials 5 < λkl ≤ 100, leading to an
33
34 alaytical expression for a1 . The exact calculation of a2,kl , appearing in the fluctuation term,
35
36 a2 , depends on 2-, 3- and 4-body correlation functions. For this term, an analytical expres-
37
38 sion has been obtained following the improved macroscopic compressibility approximation
39
40 (MCA) proposed by Zhang et al. 142 combined with a correction in the same spirit as that
41
42 proposed by Paricaud 143 for soft potentials, 12 using a number of coefficients obtained from
43
44 the analysis of Monte Carlo molecular-simulation data of selected Mie fluids. 12 An empirical
45
46 expression is used for a3,kl , which appears in the third-order term a3 . The coefficients in
47
48 the expression were obtained from phase-equilibrium and critical data of selected Mie fluids,
49
50 whereby higher-order terms of the expansion are taken implicitly into account; in effect, one
51
52 is taking approximate account of the entire series. The nett result is that one can obtain
53
54 an excellent description of experimental thermophysical-property data of real fluids even in
55
56 regions of the thermodynamic space 12 that are near critical. The explicit expressions for the
57
58
59 13
1
2
3
aq,kl are given in Refs. 12 and 54 .
4
5
6
7 2.3 Chain Term
8
9
10 The chain term in SAFT-γ represents the change in the Helmholtz free energy of a fluid of
11
12 Mie segments when the segments are joined together into the model molecules comprising the
13
14 fluid. It is obtained, as is customary within the development of SAFT equations, using the
15
136,144
16 formal TPT1 expression of Wertheim . In order that this formalism can be adopted,
17
18 average molecular parameters (σ̄ii , d¯ii , ε̄ii and λ̄ii ) are first obtained for each molecular
19
20 species.
21
22 The average molecular segment diameter σ̄ii and the effective hard-sphere diameter d¯ii
23
24 are defined as
NG
NG X
25 X
26 σ̄ii3 = 3
zk,i zl,i σkl , (14)
27 k=1 l=1
28
29 and
NG
NG X
30 X
31 d¯3ii = zk,i zl,i d3kl , (15)
32 k=1 l=1
33
34 respectively. In these expressions zk,i represents the molecular fraction of a given group k in
35
36 a molecule i, which is given by
37
38
39 νk,i ν ∗ Sk
zk,i = PNG k ∗ . (16)
40 l=1 νl,i νl Sl
41
42
43 The average interaction energy ε̄ii and exponents which characterize the range of the poten-
44
45 tial λ̄ii are given, in similar fashion, as
46
47 NG X
NG
48 X
49 ε̄ii = zk,i zl,i εkl , (17)
50 k=1 l=1
51
52 and
53 NG X
NG
54
X
λ̄ii = zk,i zl,i λkl , (18)
55
k=1 l=1
56
57
58
59 14
1
2
3
respectively; equation 18 is used for both the repulsive λ̄rii , and the attractive λ̄aii exponents.
4
5
Using these effective molecular parameters, the TPT1 expression for the chain term is
6
7
8 N NG
!
C
Achain X X
9 =− xi νk,i νk∗ Sk − 1 lngiiMie (σ̄ii ; ζx ) , (19)
10 N kB T i=1 k=1
11
12
13 where giiMie (σ̄ii ; ζx ) is the radial distribution function evaluated at σ̄ii in a hypothetical fluid
14 NG XNG
π X
15 of packing fraction ζx = ρs xs,k xs,l d3kl , which is calculated 12 using a second-order
16 6 k=1 l=1
17 expansion :
18
19
20
21 giiMie (σ̄ii ; ζx ) = gdHS (σ̄ii ; ζx )exp[β ε̄ii g1 (σ̄ii )/gdHS (σ̄ii ; ζx )
22
23 + (β ε̄ii )2 g2 (σ̄ii )/gdHS (σ̄ii ; ζx )] . (20)
24
25
26
27 gdHS (σ̄ii ; ζx ) represents the radial distribution function of a system of hard spheres of di-
28
29 ameter d¯ii evaluated at distance σ̄ii and packing fraction ζx ; this is calculated using the
30
31 expression of Boublı́k 145 . g1 (σ̄ii ; ζx ) and g2 (σ̄ii ; ζx ), which appear in the first and second-
32
33 order terms (respectively), are each approximated by their value at the contact distance d¯ii ,
34
35 i.e., gq (σ̄ii ; ζx )) ≈ gq (d¯ii ; ζx ), for q = 1, 2 . g1 (d¯ii ; ζx ) is obtained via a self-consistent method
36
37 for the calculation of pressure from the virial and the free-energy routes 8,9,12 while an ex-
38
39 pression based on the MCA with a correction term is used for g2 (d¯ii ; ζx ). All the parameters
40
41 and free energy terms needed are evaluated using the effective molecular parameters given
42
43 in Equations 14 to 18. A more-detailed description of the development of all the expressions
44
45 can be found in the original SAFT-γ Mie paper 54 ; note, however, that there is a typograph-
46
47 ical error (misplaced bracket) in the expression for the chain term (Equation 46 in Ref. 54 ),
48
49
which is here given correctly by Equation 19.
50
51
52
53
54
55
56
57
58
59 15
1
2
3
4
2.4 Association Term
5
6 The association term represents the contribution to the free energy due to the association
7
8 of molecules via short-range bonding sites. This follows from the original TPT1 expressions
9
10 of Wertheim 15–18,144,146
by summing over the number of species NC , the number of groups
11
12 NG , and the number of site types on each group NST,k , whence
13
14
NST,k
15 Aassoc. X
NC NG
X X 1 − Xi,k,a
16 = xi νk,i nk,a lnXi,k,a + , (21)
17 N kB T i=1 k=1 a=1
2
18
19
20 where nk,a is the number of sites of type a on group k, and Xi,k,a is the fraction of molecules
21
22 of component i that are not bonded at a site of type a on group k. Xi,k,a is obtained from
23
24 the solution of the mass action equations as 18,47,146
25
26 
NST,l
−1
NC NG
27 X X X
28 Xi,k,a = 1 + ρ xj νl,j nl,b Xj,l,b ∆ij,kl,ab  . (22)
29 j=1 l=1 b=1
30
31
32 Here ∆ij,kl,ab characterizes the overall strength of the association between a site of type a on
33
34 a group of type k of component i and a site of type b on a group of type l of component j.
35
36 This is approximated as
37
38 ∆ij,kl,ab = Fkl,ab Kkl,ab Iij,kl,ab , (23)
39
40
41
where Fkl,ab = exp εHB
kl,ab /kB T − 1, Kkl,ab is a bonding-volume parameter, and Iij,kl,ab is a
42
43
polynomial temperature−density correlation of the association integral for a Lennard-Jones
44
45
monomer, expressed as
46
47 10 10−p q
48
X X p kB T
Iij,kl,ab = cpq ρs σx3 . (24)
49 ε̄ij
p=0 q=0
50
51
52
53
54
55
56
57
58
59 16
1
2
3
The coefficients cpq are given in Refs.; 133,135 σx3 and ε̄ij are given, respectively, by
4
5
6 NG X
NG
7
X
σx3 = 3
xs,k xs,l σkl , (25)
8
k=1 l=1
9
10
11 and q
12 σ̄ii3 σ̄jj
3
13
p
ε̄ij = ε̄ii ε̄jj , (26)
14 σ̄ij3
15
16 where σ̄ii and σ̄jj are given by equation 14, ε̄ii and ε̄jj by equation 17, and
17
18
19 σ̄ii + σ̄jj
20 σ̄ij = . (27)
2
21
22
23
24 2.5 Born term
25
26
Within the Born model, a spherical cavity of diameter σiiBorn is created for each ion (inde-
27
28
pendently of any others) in the dielectric medium. This leads to a change in the Helmholtz
29
30
free energy given by:
31 nion
e2 Ni Zi2
X
32 Born 1
A =− 1− . (28)
33 4π0 D σiiBorn
i=1
34
35
Here index i runs over all nion charged species, e = 1.602 × 10−19 C is the elementary
36
37
charge, 0 = 8.854 × 10−12 C2 J−1 m−1 the static permittivity in vacuum, D the relative static
38
39
permittivity and Zi the valency of ion i.
40
41
42
43 2.6 Ion term
44
45
46 Following Schreckenberg et al. 41 , the Mean Spherical Approximation (MSA) 147,148 theory
47
48 is applied in the formulation of Blum and Hoye 148,149 , whereby the contribution to the free
49
50 energy due to the electrostatic interactions between charged species is given by
51
52
53 Γ3 kB T V
54 Aion = U MSA + . (29)
3π
55
56
57
58
59 17
1
2
3
Here U MSA is the MSA contribution to the internal energy U , V is the system volume, and
4
5
Γ is the screening length of the electrostatic forces, and
6
7
8
" n #
ion
e2 V Ni Zi2

ΓX π
9 U MSA =− + ΩP 2 , (30)
10 (4π0 ) D V i=1 1 + Γσii 2∆ n
11
12
13 where Pn , ∆ and Ω are additional model functions, and σii is the diameter of each ion. ∆
14
15 details the packing fraction of the ions as a function of σii :
16
17 nion
18 π X
∆=1− Ni σii3 . (31)
19 6V i=1
20
21
22 Pn and Ω are coupling parameters; Pn couples to the charge of the ions, whereas Ω relates
23
24 to the packing fraction of the ions. Both parameters are functions of the ionic parameters,
25
26 as well as the screening length of the ions:
27
28 nion
29 1 X Ni σii Zi
30 Pn = , (32)
ΩV i=1 1 + Γσii
31
nion
32 π X Ni σii3
33 Ω=1+ . (33)
34
2∆V i=1 1 + Γσii
35
36
Finally the screening length of the ions is a function of the relative static permittivity and
37
38
the effective charge Qi (Γ) of the ions, leading to an implicit formulation through Qi :
39
40
41 nion
πe2 X
42 2
Γ = Ni Q2i , (34)
43 (4π0 ) DkB T V i=1
44
45
46 where the effective charge is related to the electric charge of the individual species and the
47
48 Pn coupling parameter:
49 Zi − σii2 Pn (π/ (2∆))
50 Qi = . (35)
1 + Γσii
51
52
53
54
55
56
57
58
59 18
1
2
3
4
2.7 Combining Rules
5
6 Unlike (or cross) group parameters are required in the expressions given in the previous
7
8 section not only in the treatment of mixtures but also, due to the heteronuclear nature
9
10 of the model in SAFT-γ Mie, in pure-component calculations. For example, the unlike
11
12 interaction between the CH3 and CH2 groups is required to represent pure n-alkanes. These
13
14 unlike parameters are generally determined using combining rules, and refined (if necessary)
15
16 by estimation using experimental data.
17
18 The unlike segment diameter σkl is obtained from the like diameters using the Lorentz
19
20 (arithmetic-mean) rule 150 , and this combining rule is used also in the calculation of the
21
22 unlike effective hard-sphere diameter, dkl :
23
24
25 σkk + σll dkk + dll
26 σkl = ; dkl = . (36)
2 2
27
28
29 It is common practice in theory and simulation of fluids to adopt a simple (Berthelot-like)
30
31 geometric-mean combining rule to obtain the unlike dispersion energy, however this approach
32
33 is not expected to be valid if there is significant size asymmetry (σkk 6= σll ). 73 Accordingly,
34
35 in SAFT-γ, the unlike dispersion energy, εkl between groups k and l, is calculated using an
36
37 augmented geometric-mean rule,
38
39
40
p
3
σkk σll3 √
41 εkl = 3
εkk εll ; (37)
42 σkl
43
44 p 3
45
the prefactor, 3
σkk σll3 /σkl , provides an accounting of any size asymmetry. 73
46
47
The exponents of the unlike segment-segment interaction λrkl and λakl are obtained as
48
49
50
p
λkl = 3 + (λkk − 3)(λll − 3) ; (38)
51
52
53
54 this expression results from an application of the Berthelot rule (i.e., enforcing the geometric
55
56 mean for the unlike integrated van der Waals energy) to a Sutherland fluid of range λkl 54 .
57
58
59 19
1
2
3
In associating mixtures, one requires also the unlike association energy, εHB
kl,ab , and the
4
5
unlike bonding volume, Kkl,ab . The former is obtained as a simple geometric mean,
6
7
8 q
9 εHB
kl,ab = εHB HB
kk,aa εll,bb , (39)
10
11
12
13 while the latter is calculated according to
14
15 p p !3
16
3
Kkk,aa + 3
Kll,bb
17
Kkl,ab = . (40)
2
18
19
20 Although these combining rules provide a good first estimate of the values of the required
21
22 unlike group parameters, in general it is better (where possible) to estimate these param-
23
24 eters using experimental data; this is particularly true in the case of the unlike attractive
25
26 interactions (dispersion and association energies). The use of a heteronuclear model, such as
27
28 is adopted in our approach, proffers the advantage that pure-component data can, in many
29
30 cases, be used in isolation to obtain an accurate estimate of the values of an unlike energetic
31
32 parameter.
33
34
35
36
37 3 SAFT-γ Mie group parameter tables
38
39
40 In table 1 we present the latest SAFT-γ Mie group matrix. Cells shaded green denote that
41
42 parameters for the indicated interaction have been optimised; these parameters are presented
43
44 in tables 4 and 5. Cells shaded grey denote that the indicated interaction is determined using
45
46 combining rules, as set out in the previous subsection.
47
48
49
50
51
52
53
54
55
56
57
58
59 20
1
2
3 Table 1: Groups developed for use within the SAFT-γ Mie approach.
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
21
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44 Green shading denotes that group–group interaction parameters have been refined by estimation using experimental data; grey shading
45 ACS Paragon
denotes that unlike interaction parameters Plus
are Environment
predicted using combining rules (eqs 36 to 38).
46
47
1
2
3
4
3.1 Use of SAFT-γ Mie groups
5
6 Selection of groups for building molecules follows the general philosophy of Marrero and Gani
7
8 59
for first-order groups. Where there is ambiguity in the possible choice of groups to build a
9
10 molecule, the heavier group incorporating the appropriate fragments should be chosen. For
11
12 example, ethanol is better represented with a CH3 group and a CH2 OH group, rather than a
13
14 CH3 , a CH2 group and an OH group. Similarly, 4-amino-1-butanol (monobutanolamine) is
15
16 better described using a CH2 OH group together with three CH2 groups and an NH2 group,
17
18 rather than an OH group, four CH2 groups and an NH2 group.
19
20 The CH2 OH group is one of a number of groups that are similar in concept to the second-
21
22 order groups of Marrero and Gani 59 insofar as they can be used for improved accuracy relative
23
24 to adopting simpler groups. As another example, two classes of ether O groups are defined
25
80
26 for modelling poly(oxyalkylene)dimethylethers, according to the proximity of the ether
27
28 group to the end of the molecule: the eO group denotes an “end ether”, i.e., connected to a
29
30 terminal CH3 group, whereas the mO group denotes a “middle ether”, bonded on both sides
31
32 to CH2 groups.
33
34 The carboxylic acid group (COOH) was characterised using carboxylic acids with chain
35
36 lengths larger than C4 . 83 In order to take into account the polarization effect in shorter-
37
38 chain carboxylic acids and carboxylate salts (acetates and propanoates), second-order groups
39
40 CH2 adj and CH3 adj are defined to represent the alkyl group adjacent to the COOH group.
41
123
42 The CH2 adj and CH3 adj groups differ from the regular CH2 and CH3 groups only insofar
43
44 as they have different interactions with COO− and COOH. All other unlike interactions
45
46 of CH2 adj and CH3 adj are taken to be the same as those of the CH2 and CH3 groups
47
48 (respectively); see tables 1, 4 and 5.
49
50 Short-chain alcohols exhibit full miscibility with water; this phase behaviour contrasts
51
52 that of binary mixtures of longer-chain alcohols with water, which features regions of liquid–
53
54 liquid immiscibility. To characterise the interaction between short-chain alcohols (i.e., those
55
56 with two or three carbons in the backbone, such as ethanol or 1-propanol) and water, the
57
58
59 22
1
2
3
group CH2 OH short is defined. 151 This group differs from the regular CH2 OH group only in
4
5
its interaction with water; in all other respects it is identical.
6
7
A second-order group, NH2 ca.OH, is also introduced to treat the NH2 (amine) group in
8
9 aqueous solutions when it is present in alkanolamine molecules containing one or more OH
10
11 groups up to and including three carbons distant along the carbon backbone. For exam-
12
13 ple, this applies to aqueous solutions of monoethanolamine (MEA) and monopropanolamine
14
15 (MPA). Similar to the CH2 OH short groups, this group differs from its regular (first-order)
16
17 counterpart only in its unlike interaction with water.
18
19 Second-order groups currently defined for use within SAFT-γ Mie, and their usage, are
20
21 summarised in table 2.
22
23 Table 2: Second-order group usage within SAFT-γ Mie
24
25
Group(s) Ref. Usage within SAFT-γ Mie
26
27 CH2 adj and CH3 adj relate to carboxylic acids and carboxylates.
28 123 The CH2 adj and CH3 adj groups have different interactions with
CH2 adj; CH3 adj
29 COO− and COOH, but all other unlike interactions are taken to be the
30 same as those of the CH2 and CH3 groups, respectively (see table 4).
31
32
CH2 OH Short relates to the interaction, with water, of short-chain
33 alcohols (ethanol and 1-propanol) or alkanolamines wherein the amine
34 151 and OH groups are situated on carbons separated by three or less
35
CH2 OH Short
carbons on the backbone chain. Apart from this interaction, all
36 other unlike interactions are taken to be the same as those of the
37
38
CH2 OH group (see table 4).
39 The NH2 ca.OH group relates to alkanolamines in aqueous solution;
40 it is used to represent an NH2 group situated on a carbon up to and
41 This including three carbons along the carbon backbone from an OH group.
42 NH2 ca.OH
work It differs from the NH2 group only in its unlike interaction with H2 O;
43
44 all other unlike interactions are taken to be those of the NH2 group
45 (see table 4).
46 The eO and mO groups relate to poly(oxyalkylene)dimethylethers;
47 eO (“end ether”) refers to an ether group situated adjacent to a
80
48 eO; mO
terminal CH3 group; mO (“middle ether”) refers to an ether group
49
50 situated between two CH2 groups.
51
52
53
54
55
56
57
58
59 23
1
2
3
4 Table 3: Like group parameters for use with the SAFT-γ Mie approach. In cases where a moiety can be modelled using different
5 combinations of groups, the group containing the most atoms should be used. νk∗ , Sk , and σkk are the number of segments
6 constituting group k, the shape factor, and the segment diameter of group k, respectively; λrkk and λakk are the repulsive and
7
attractive exponents, and εkk is the dispersion energy of the Mie potential characterizing the interaction of two k groups; NST,k
8
9 represents the number of association site types on group k, with nH , k, ne1 , k and ne2 , k denoting the number of association sites
10 of type H, e1, and e2 respectively.
11
12 ∗
k Group νkk Skk σkk /Å Born
σkk /Å λ∗r,kk λa,kk (εkk /kB )/K NST,k nH,k ne1,k ne2,k Charge Ref.
13
14 54,75
1 CH3 1 0.57255 4.0772 - 15.050 6.0000 256.77 - - - - -
15
16 54,75
2 CH2 1 0.22932 4.8801 - 19.871 6.0000 473.39 - - - - -
17
18 75
3 CH 1 0.07210 5.2950 - 8.0000 6.0000 95.621 - - - - -
19
20 75
4 C 1 0.04072 5.6571 - 8.0000 6.0000 50.020 - - - - -
21
22
24
75
5 aCH 1 0.32184 4.0578 - 14.756 6.0000 371.53 1 - 1 - -
23
24 75
6 aCCH2 1 0.20859 5.2648 - 8.5433 6.0000 591.56 1 - 1 - -
25
26 75
7 aCCH 1 0.20650 4.3128 - 8.0000 6.0000 61.325 1 - 1 - -
27
28 75
8 CH2 = 1 0.44890 4.3175 - 20.271 6.0000 300.90 - - - - -
29
30 75
9 CH= 1 0.20040 4.7488 - 15.974 6.0000 952.54 - - - - -
31
32 75
10 cCH2 1 0.24750 4.7852 - 20.386 6.0000 477.36 - - - - -
33
34 75
11 COOH 1 0.55593 4.3331 - 8.0000 6.0000 405.78 3 1 2 2 -
35
36 12 CH3 COCH3 3 0.72135 3.5981 - 17.433 6.0000 286.02 3 1 1 1 - 75
37
38 13 COO 1 0.65264 3.9939 - 31.189 6.0000 868.92 1 - 2 - - 54,75
39
40 14 H2 O 1 1.00000 3.0063 - 17.020 6.0000 266.68 2 2 2 - - 75,135
41
42
43
44
46
47
1
2
3
∗
4 k Group νkk Skk σkk /Å Born
5
75,88
6 15 CH3 OH 2 0.83517 3.2462 - 19.235 6.0000 307.69 2 1 2 - -
7
88
8 16 CH4 1 1.00000 3.7370 - 12.504 6.0000 152.58 - - - - -
9
88
10 17 CO2 2 0.84680 3.0500 - 26.408 5.0550 207.89 2 - 1 1 -
11
152
12 18 OH 1 0.96340 2.7990 - 20.702 6.0000 410.31 2 1 2 - -
13
102
14 19 CH2 OH 2 0.58538 3.4054 - 22.699 6.0000 407.22 2 1 2 - -
15
153
16 20 CHOH 2 0.18963 4.5381 - 18.185 6.0000 599.66 2 1 2 - -
17
151,154
18 21 NH2 1 0.79675 3.2477 - 10.254 6.0000 284.78 2 2 1 - -
19
151,154
20 22 NH 1 0.36589 3.2568 - 20.000 6.0000 100.00 2 1 1 - -
21
151,154
22 23 N 1 0.15069 3.0755 - 8.8971 6.0000 62.971 1 - 1 - -
25
23
154
24 24 cNH 1 0.16529 4.9810 - 19.491 6.0000 631.93 2 1 1 - -
25
154
26 25 cN(−) 1 0.07195 4.6120 - 7.0024 6.0000 174.04 1 - 1 - -
27
152
28 26 C= 1 0.15330 4.0330 - 8.0000 6.0000 1500.0 - - - - -
29
88
30 27 aCCH3 1 0.31655 5.4874 - 23.627 6.0000 651.41 1 - 1 - -
31
32 28 aCOH 1 0.74544 3.3521 - 19.205 6.0000 431.10 3 1 2 1 - *
33
154
34 29 cCH 1 0.09610 5.4116 - 8.0000 6.0000 699.92 - - - - -
35 154
36 30 cCHNH 1 0.15300 5.5000 - 9.2370 6.0000 691.557 2 1 1 - -
37 154
38 31 cCHN 1 0.10300 4.4450 - 8.0020 6.0000 709.985 1 0 1 - -
39
40 32 H3 O+ 1 1.00000 3.0063 3.0063 17.020 6.0000 68.190 1 3 - - +1 43
41
42
43
44
46
47
1
2
3
∗
5
6 32 H3 O+ 1 1.00000 3.0100 3.0100 12.000 6.0000 68.190 - - - - +1 43
7
8 33 Li+ 1 1.00000 1.8000 2.6300 12.000 6.0000 6.1039 - - - - +1 43
9
10 34 Na+ 1 1.00000 2.3200 3.3600 12.000 6.0000 31.711 - - - - +1 43
11
12 35 K+ 1 1.00000 3.0400 4.3400 12.000 6.0000 90.097 - - - - +1 43
13
14 36 Rb+ 1 1.00000 3.3200 4.6200 12.000 6.0000 130.35 - - - - +1 43
15
16 37 Mg2+ 1 1.00000 1.4400 2.9100 12.000 6.0000 259.22 - - - - +2 43
17
18 38 Ca2+ 1 1.00000 2.1200 3.7200 12.000 6.0000 404.32 - - - - +2 43
19
20 39 Sr2+ 1 1.00000 2.3600 4.1100 12.000 6.0000 599.24 - - - - +2 43
21
22 40 Ba2+ 1 1.00000 2.7000 4.4200 12.000 6.0000 725.38 - - - - +2 43
26
23
24 41 N+ 1 0.15069 3.0755 3.2908 8.8971 6.0000 62.971 1 1 - - +1 155
25
26 42 OH− 1 1.00000 2.4600 3.0100 17.020 6.0000 170.24 1 - 3 - –1 43
27
28 43 F− 1 1.00000 2.3800 2.8500 12.000 6.0000 66.06 - - - - –1 43
29
30 44 Cl− 1 1.00000 3.3400 3.8700 12.000 6.0000 113.35 - - - - –1 43
31
32 45 Br− 1 1.00000 3.6400 4.1700 12.000 6.0000 107.38 - - - - –1 43
33
34 46 I− 1 1.00000 4.1200 4.6900 12.000 6.0000 102.90 - - - - –1 43
35
36 47 COO− 1 0.55593 4.3331 4.6364 8.0000 6.0000 21.264 1 - 4 - –1 155
37
38 48 HSO−
4 1 1.00000 4.1200 4.4084 12.000 6.0000 82.086 - - - - –1 156
39
40 49 SO2−
4 1 1.00000 4.1500 4.4400 12.000 6.0000 197.05 - - - - –2 43
41
42
43
44
46
47
1
2
3
∗
5
156
6 50 HNO3 1 1.34520 3.5878 - 16.347 6.0000 496.33 2 1 3 - -
7
8 51 NO−
3 1 1.00000 3.5800 4.0000 12.000 6.0000 97.853 1 - 3 - –1 156
9
10 52 HCO−
3 1 1.00000 3.1200 4.3000 12.000 6.0000 378.24 1 - 4 - -1 156
11
151
12 53 aCCOOH 2 0.65530 3.3942 - 8.0000 6.0000 313.35 3 1 2 2 -
13
152
14 54 aCCOaC 3 0.18086 4.0670 - 9.8317 6.0000 656.71 - - - - -
15
151
16 55 aCNHaC 1 0.54263 3.3218 - 8.2761 6.0000 303.35 2 1 1 - -
17
54,123
18 56 CH3 adj 1 0.57255 4.0773 - 15.050 6.0000 256.77 - - - - -
19
54,123
20 57 CH2 adj 1 0.22932 4.8801 - 19.871 6.0000 473.39 - - - - -
21
157
22 58 CH3 CO 2 0.54685 3.9112 - 19.050 6.0000 525.22 1 - 2 - -
27
23
151,152
24 59 CH2 OH short 2 0.58538 3.4054 - 22.699 6.0000 407.22 2 1 2 - -
25
80
26 60 eO 1 0.40981 2.8566 - 10.1270 6.0000 330.18 - - - - -
27
80
28 61 mO 1 0.40981 2.8566 - 10.1270 6.0000 248.20 - - - - -
29
30 62 NH2 ca.OH 1 0.79675 3.2477 - 10.254 6.0000 284.78 2 2 1 - - This work
31
32
33
34
35
36
37
38
39
40
41
42
43
44
46
47
1
2
3
4 Table 4: Unlike group dispersion interaction energies εk,l and repulsive exponent λrk,l for use
5 within the SAFT-γ Mie group contribution approach. In all cases the unlike diameters σkl
6 and dkl as well as the unlike attractive exponent of the Mie potential λakl are obtained from
7
equations 36 and 38, respectively. CR indicates that the unlike repulsive exponent λrkl is
8
9 obtained from the combining rule given by eq 38. Only the interaction parameters that have
10 been estimated using experimental data are reported in this table.
11
12
13
14 k l group, k group, l (εkl /kB )/K λ∗r,kl Ref.
15
16
17
54
18 1 2 CH3 CH2 350.77 CR
19
75
20 1 3 CH3 CH 387.48 CR
21
75
22 1 4 CH3 C 339.91 CR
23 75
24 1 5 CH3 aCH 305.81 CR
25 75
26 1 6 CH3 aCCH2 396.91 CR
27 75
28 1 7 CH3 aCCH 455.85 CR
29 75
30 1 8 CH3 CH2 = 333.48 CR
31 75
32 1 9 CH3 CH= 252.41 CR
33 75
34 1 10 CH3 cCH2 355.95 CR
35 75
36 1 11 CH3 COOH 255.99 CR
37 75
38 1 12 CH3 CH3 COCH3 233.48 14.449
39 75
40 1 13 CH3 COO 402.75 CR
41 102
42 1 14 CH3 H2 O 358.18 100.00
43 75
44 1 15 CH3 CH3 OH 275.76 15.537
45 80
46 1 16 CH3 CH4 193.97 12.628
47 88
48 1 17 CH3 CO2 205.70 CR
49 152
50 1 18 CH3 OH 341.67 CR
51 102
52 1 19 CH3 CH2 OH 333.20 CR
53
54 1 20 CH3 CHOH 479.38 CR This work
55
56 1 21 CH3 NH2 244.15 CR This work
57
58
59 28
1
2
3
4
6
7
8
9 1 22 CH3 NH 530.87 CR This work
10
11 1 23 CH3 N 462.18 CR This work
12
13 1 24 CH3 cNH 583.72 CR This work
14
15 1 25 CH3 cN 710.00 CR This work
16
17 1 26 CH3 C= 281.40 CR 152
18
19 1 27 CH3 aCCH3 358.58 CR 102
20
21 1 28 CH3 aCOH 413.25 CR This work
22
23 1 29 CH3 cCH 690.17 CR This work
24
25 1 30 CH3 cCHNH 406.965 CR 154
26
27 1 31 CH3 cCHN 761.786 CR 154
28
29 1 41 CH3 N+ 462.18 CR 123
30
31 1 47 CH3 COO− 255.99 CR 123
32
33 1 53 CH3 aCCOOH 370.75 CR 157
34
35 1 55 CH3 aCNHaC 647.64 CR 157
36
37 1 56 CH3 CH3 adj 256.77 15.050 54,123
38
39 1 57 CH3 CH2 adj 350.77 CR 54,123
40
41 1 58 CH3 CH3 CO 344.57 CR 157
42
43 1 59 CH3 CH2 OH short 333.20 CR 151,152
44
45 2 3 CH2 CH 506.21 CR 75
46
47 2 4 CH2 C 300.07 CR 75
48
49 2 5 CH2 aCH 415.64 CR 75
50
51 2 6 CH2 aCCH2 454.16 CR 75
52
75
53 2 7 CH2 aCCH 345.80 CR
54
75
55 2 8 CH2 CH2 = 386.80 CR
56
57
58
59 29
1
2
3
4
6
7
8
9 2 9 CH2 CH= 459.40 CR 75
10
11 2 10 CH2 cCH2 469.67 CR 75
12
13 2 11 CH2 COOH 413.74 CR 75
14
15 2 12 CH2 CH3 COCH3 299.48 11.594 75
16
17 2 13 CH2 COO 498.86 CR 75
18
19 2 14 CH2 H2 O 423.63 100 102
20
21 2 15 CH2 CH3 OH 341.41 17.05 75
22
23 2 16 CH2 CH4 243.13 12.642 80
24
25 2 17 CH2 CO2 275.15 21.982 88
26
27 2 18 CH2 OH 396.27 CR 152,158
28
29 2 19 CH2 CH2 OH 423.17 CR 102
30
31 2 20 CH2 CHOH 517.64 CR This work
32
33 2 21 CH2 NH2 348.39 CR This work
34
35 2 22 CH2 NH 394.58 CR This work
36
37 2 23 CH2 N 348.30 CR This work
38
39 2 24 CH2 cNH 429.49 CR This work
40
41 2 25 CH2 cN 508.54 CR This work
42
43 2 26 CH2 C= 286.58 CR 152
44
45 2 27 CH2 aCCH3 569.18 CR 102
46
47 2 28 CH2 aCOH 484.02 CR This work
48
49 2 29 CH2 cCH 522.57 CR This work
50
51 2 30 CH2 cCHNH 309.95 CR 157
52
157
53 2 31 CH2 cCHN 893.50 CR
54
55 2 41 CH2 N+ 348.30 CR 123
56
57
58
59 30
1
2
3
4
6
7
8
9 2 47 CH2 COO− 413.74 CR 123
10
11 2 53 CH2 aCCOOH 323.72 CR 157
12
13 2 55 CH2 aCNHaC 347.75 CR 157
14
15 2 56 CH2 CH3 adj 350.77 CR 54,123
16
17 2 57 CH2 CH2 adj 473.39 19.871 54,123
18
19 2 58 CH2 CH3 CO 431.49 CR 157
20
21 2 59 CH2 CH2 OH short 423.17 CR 151,152
22
23 3 4 CH C 2.0000 CR 152
24
25 3 5 CH aCH 441.43 CR 75
26
27 3 6 CH aCCH2 65.410 CR 75
28
29 3 7 CH aCCH 67.510 CR 75
30
31 3 8 CH CH2 = 426.76 CR 75
32
33 3 9 CH CH= 502.99 CR 75
34
35 3 10 CH cCH2 570.45 CR 75
36
37 3 11 CH COOH 504.99 CR 75
38
39 3 12 CH CH3 COCH3 637.29 CR 75
40
41 3 13 CH COO 353.65 CR 152
42
43 3 14 CH H2 O 275.75 CR 152
44
45 3 18 CH OH 198.08 CR 152
46
47 3 19 CH CH2 OH 329.22 CR 152
48
49 3 20 CH CHOH 0.0000 CR This work
50
51 3 26 CH C= 378.72 CR 152
52
53 3 47 CH COO− 504.99 CR 159
54
157
55 3 53 CH aCCOOH 0.00 CR
56
57
58
59 31
1
2
3
4
6
7
8
9 3 55 CH aCNHaC 878.88 CR 157
10
11 3 58 CH CH3 CO 321.91 CR 157
12
13 4 10 C cCH2 0.0000 CR 152
14
15 4 13 C COO 0.0000 CR 152
16
17 4 14 C H2 O 420.82 CR 152
18
19 4 18 C OH 0.0000 CR 152
20
21 4 19 C CH2 OH 0.0000 CR 152
22
23 4 20 C CHOH 0.0000 CR This work
24
25 5 6 aCH aCCH2 416.69 CR 75
26
27 5 7 aCH aCCH 429.16 CR 75
28
29 5 11 aCH COOH 331.61 9.0687 75
30
31 5 12 aCH CH3 COCH3 333.11 CR 75
32
33 5 14 aCH H2 O 357.78 38.64 75
34
35 5 19 aCH CH2 OH 386.05 CR 152
36
37 5 20 aCH CHOH 512.16 CR This work
38
39 5 27 aCH aCCH3 471.23 CR 88
40
41 5 28 aCH aCOH 448.75 CR This work
42
43 5 32 aCH H 3 O+ CR CR 159
44
45 5 47 aCH COO− 331.61 9.0687 159
46
47 5 53 aCH aCCOOH 340.70 CR 157
48
49 5 55 aCH aCNHaC 549.72 CR 157
50
51 5 58 aCH CH3 CO 426.72 18.03 157
52
75
53 6 7 aCCH2 aCCH 462.04 CR
54
75
55 6 11 aCCH2 COOH 473.66 CR
56
57
58
59 32
1
2
3
4
6
7
8
9 6 12 aCCH2 CH3 COCH3 394.83 CR 75
10
11 6 14 aCCH2 H2 O 329.03 CR 152
12
13 6 19 aCCH2 CH2 OH 434.37 CR 152
14
15 6 20 aCCH2 CHOH 357.91 CR This work
16
17 6 32 aCCH2 H3 O+ CR CR 159
18
19 6 47 aCCH2 COO− 473.66 CR 159
20
21 6 53 aCCH2 aCCOOH 168.69 CR 157
22
23 6 58 aCCH2 CH3 CO 663.71 30.712 157
24
25 7 11 aCCH COOH 599.28 CR 75
26
27 7 12 aCCH CH3 COCH3 459.22 CR 75
28
29 7 14 aCCH H2 O 314.03 CR 152
30
31 7 19 aCCH CH2 OH 436.14 CR 152
32
33 7 20 aCCH CHOH 138.39 CR This work
34
35 7 47 aCCH COO− 599.28 CR 159
36
37 8 9 CH2 = CH= 275.75 CR 75
38
39 8 12 CH2 = CH3 COCH3 288.20 CR This work
40
41 8 14 CH2 = H2 O 387.25 94.463 This work
42
43 8 19 CH2 = CH2 OH 375.51 CR This work
44
45 8 20 CH2 = CHOH 449.83 CR This work
46
47 8 26 CH2 = C= 203.76 CR This work
48
49 8 56 CH2 = CH3 adj 333.48 CR 75,123
50
51 8 57 CH2 = CH2 adj 386.80 CR 75,123
52
54
53 9 10 CH= cCH2 398.35 CR
54
55 9 11 CH= COOH 453.13 CR This work
56
57
58
59 33
1
2
3
4
6
7
8
9 9 12 CH= CH3 COCH3 437.75 CR This work
10
11 9 13 CH= COO 818.79 CR 152
12
13 9 14 CH= H2 O 332.21 17.309 This work
14
15 9 18 CH= OH 625.17 CR 152
16
17 9 19 CH= CH2 OH 414.91 CR This work
18
19 9 20 CH= CHOH 540.83 CR This work
20
21 9 26 CH= C= 1195.3 CR 152
22
23 9 47 CH= COO− 453.13 CR 123
24
25 10 12 cCH2 CH3 COCH3 352.19 CR This work
26
27 10 13 cCH2 COO 498.60 CR 54
28
29 10 14 cCH2 H2 O 347.48 28.497 This work
30
31 10 17 cCH2 CO2 269.68 CR This work
32
33 10 18 cCH2 OH 376.57 CR 152
34
35 10 18 cCH2 OH 348.20 CR This work
36
37 10 20 cCH2 CHOH 554.50 CR This work
38
39 10 21 cCH2 NH2 332.15 CR This work
40
41 10 22 cCH2 NH 549.43 CR This work
42
43 10 23 cCH2 N 215.05 CR This work
44
45 10 24 cCH2 cNH 605.45 CR 154
46
47 10 25 cCH2 cN 536.66 CR 154
48
49 10 26 cCH2 C= 846.19 CR 152
50
51 10 29 cCH2 cCH 321.71 CR 154
52
157
53 10 30 cCH2 cCHNH 486.88 CR
54
157
55 10 31 cCH2 cCHN 750.06 CR
56
57
58
59 34
1
2
3
4
6
7
8
9 10 53 cCH2 aCCOOH 389.90 CR 157
10
11 10 55 cCH2 aCNHaC 564.85 CR 157
12
13 11 12 COOH CH3 COCH3 393.71 CR 54
14
15 11 14 COOH H2 O 289.76 CR 102
16
17 11 19 COOH CH2 OH 656.80 CR 102
18
19 11 26 COOH C= 609.87 CR 123
20
21 11 32 COOH H3 O+ CR CR 159
22
23 11 47 COOH COO− 405.78 8.0000 123
24
25 11 42 COOH OH- CR CR 159
26
27 11 56 COOH CH3 adj 255.99 CR 75,123
28
29 11 57 COOH CH2 adj 413.74 CR 75,123
30
31 12 13 CH3 COCH3 COO 547.44 CR This work
32
33 12 14 CH3 COCH3 H2 O 287.26 CR 54
34
35 12 18 CH3 COCH3 OH 340.81 CR This work
36
37 12 19 CH3 COCH3 CH2 OH 338.47 CR This work
38
39 12 20 CH3 COCH3 CHOH 340.81 CR This work
40
41 12 26 CH3 COCH3 C= 516.31 CR This work
42
43 12 28 CH3 COCH3 aCOH 389.74 CR This work
44
45 12 53 CH3 COCH3 aCCOOH 316.60 CR 157
46
47 12 55 CH3 COCH3 aCNHaC 261.23 8.0000 157
48
49 13 14 COO H2 O 396.81 15.140 This work
50
51 13 18 COO OH 490.95 CR 152
52
152
53 13 26 COO C= 868.11 CR
54
157
55 13 53 COO aCCOOH 331.78 CR
56
57
58
59 35
1
2
3
4
6
7
8
9 13 55 COO aCNHaC 809.96 CR 157
10
11 14 15 H2 O CH3 OH 278.45 CR 75
12
13 14 16 H2 O CH4 175.41 CR 88
14
15 14 17 H2 O CO2 226.38 CR 88
16
17 14 18 H2 O OH 375.92 CR 151,158
18
19 14 18 H2 O OH 365.33 CR This work
20
21 14 19 H2 O CH2 OH 353.37 CR 102
22
23 14 19 H2 O CH2 OH 358.02 CR This work
24
25 14 20 H2 O CHOH 479.16 CR This work
26
27 14 21 H2 O NH2 358.55 CR 151
28
29 14 22 H2 O NH 646.10 13.195 151
30
31 14 23 H2 O N 1481.3 21.217 151
32
33 14 24 H2 O cNH 523.83 8.4243 154
34
35 14 25 H2 O cN 2990.0 66.109 154
36
37 14 26 H2 O C= 310.91 8.0000 123
38
39 14 27 H2 O aCCH3 360.70 CR 152
40
41 14 28 H2 O aCOH 238.77 8.0000 This work
42
43 14 29 H2 O cCH 377.16 22.265 154
44
45 14 30 H2 O cCHNH 855.01 32.132 157
46
47 14 31 H2 O cCHN 1067.92 8.001 157
48
49 14 32 H2 O H3 O+ 391.04 CR 43
50
51 14 33 H2 O Li+ 1023.1 CR 43
52
53 14 34 H2 O Na+ 539.68 CR 43
54
55 14 35 H2 O K+ 376.25 CR 43
56
57
58
59 36
1
2
3
4
6
7
8
9 14 36 H2 O Rb+ 354.23 CR 43
10
11 14 37 H2 O Mg2+ 2235.1 CR 43
12
13 14 38 H2 O Ca2+ 1460.8 CR 43
14
15 14 39 H2 O Sr2+ 1047.0 CR 43
16
17 14 40 H2 O Ba2+ 840.44 CR 43
18
19 14 41 H2 O N+ 1481.30 21.217 123
20
21 14 42 H2 O OH- 134.41 CR 43
22
23 14 43 H2 O F− 30.571 CR 43
24
25 14 44 H2 O Cl− 95.41 CR 43
26
27 14 45 H2 O Br− 112.01 CR 43
28
29 14 46 H2 O I− 142.66 CR 43
30
31 14 47 H2 O COO− 171.61 CR 123
32
33 14 48 H2 O HSO4 - 142.57 CR 156
34
35 14 49 H2 O SO2−
4 128.03 CR 156
36
37 14 50 H2 O HNO3 288.82 CR 156
38
39 14 51 H2 O NO3 - 92.66 CR 156
40
41 14 52 H2 O HCO3 - 417.43 CR 156
42
43 14 53 H2 O aCCOOH 228.58 9.5614 157
44
45 14 56 H2 O CH3 adj 358.18 100.00 102,123
46
47 14 57 H2 O CH2 adj 423.63 100.00 102,123
48
49 14 59 H2 O CH2 OH short 358.02 CR 151
50
51 14 62 H2 O NH2 ca.OH 339.89 CR This work
52
88
53 15 16 CH3 OH CH4 233.21 CR
54
88
55 15 17 CH3 OH CO2 157.83 8.3462
56
57
58
59 37
1
2
3
4
6
7
8
9 15 53 CH3 OH aCCOOH 290.16 8.0000 157
10
11 15 55 CH3 OH aCNHaC 398.10 CR 157
12
13 16 17 CH4 CO2 144.72 11.950 88
14
15 17 21 CO2 NH2 134.58 50.060 This work
16
17 17 22 CO2 NH 94.328 49.043 151
18
19 17 23 CO2 N 100.58 49.999 151
20
21 17 24 CO2 cNH 222.72 11.863 154
22
23 17 25 CO2 cN 122.66 19.740 154
24
25 17 29 CO2 cCH 294.99 CR 154
26
27 17 30 CO2 cCHNH 100.53 31.234 157
28
29 17 32 CO2 H3 O+ 189.86 CR 156
30
31 17 52 CO2 HCO−
3 371.59 CR 156
32
33 17 59 CO2 CH2 OH short 312.30 CR 151
34
35 17 62 CO2 NH2 ca.OH 134.58 50.060 This work
36
37 18 21 OH NH2 241.94 CR 151
38
39 18 22 OH NH 188.61 CR 151
40
41 18 23 OH N 260.99 CR 151
42
43 18 26 OH C= 784.51 CR 152,158
44
45 18 26 OH C= 784.51 CR 152
46
47 18 29 OH cCH 355.95 CR This work
48
49 19 20 CH2 OH CHOH 389.23 CR This work
50
51 19 23 CH2 OH N 440.99 CR 123
52
123
53 19 26 CH2 OH C= 799.66 CR
54
152
55 19 27 CH2 OH aCCH3 486.62 CR
56
57
58
59 38
1
2
3
4
6
7
8
9 19 28 CH2 OH aCOH 307.89 41.331 This work
10
11 19 41 CH2 OH N+ 440.99 CR 123
12
13 19 47 CH2 OH COO− 656.8 CR 123
14
15 19 53 CH2 OH aCCOOH 172.57 9.2665 157
16
17 19 55 CH2 OH aCNHaC 485.03 8.0012 157
18
19 19 56 CH2 OH CH3 adj 333.20 CR 102,123
20
21 19 57 CH2 OH CH2 adj 423.17 CR 102,123
22
23 20 26 CHOH C= 245.07 CR This work
24
25 20 27 CHOH aCCH3 762.86 CR This work
26
27 20 53 CHOH aCCOOH 81.542 79.266 157
28
29 20 55 CHOH aCNHaC 451.48 8.181 157
30
31 21 24 NH2 NH2 284.78 10.254 This work
32
33 21 30 NH2 cCHNH 101.611 CR 157
34
35 21 79 NH2 CH2 OH short 528.21 52.305 This work
36
37 22 59 NH CH2 OH short 313.25 CR 151
38
39 23 59 N CH2 OH short 260.80 CR 151
40
41 24 25 cNH cN 812.26 CR 154
42
43 25 25 cN cN 174.04 7.0020 This work
44
45 26 47 C= COO− 609.87 CR 123
46
47 26 56 C= CH3 adj 281.40 CR 123,152
48
49 26 57 C= CH2 adj 286.58 CR 123,152
50
51 27 53 aCCH3 aCCOOH 455.68 CR 157
52
157
53 27 55 aCCH3 aCNHaC 941.03 CR
54
157
55 27 58 aCCH3 CH3 CO 552.62 36.429
56
57
58
59 39
1
2
3
4
6
7
8
9 29 53 cCH aCCOOH 246.61 CR 157
10
11 32 34 H3 O+ Na+ 37.480 CR 159
12
13 32 42 H3 O+ OH- 66.439 CR 43
14
15 32 43 H3 O+ F− 51.1 CR 43
16
17 32 44 H3 O+ Cl− 70.552 CR 43
18
19 32 45 H3 O+ Br− 65.806 CR 43
20
21 32 46 H3 O+ I− 59.657 CR 43
22
23 32 47 H3 O+ COO− 27.740 CR 159
24
25 32 48 H3 O+ HSO4 - 60.476 CR 156
26
27 32 49 H3 O+ SO2−
4 53.609 CR 156
28
29 32 50 H3 O+ HNO3 231.44 CR 156
30
31 32 51 H3 O+ NO−
3 61.788 CR 156
32
33 32 52 H3 O+ HCO−
3 130.28 CR 156
34
35 33 43 Li+ F− 7.6879 CR 43
36
37 33 44 Li+ Cl− 8.2904 CR 43
38
39 33 45 Li+ Br− 7.1802 CR 43
40
41 33 46 Li+ I− 5.8749 CR 43
42
43 34 42 Na+ OH- 27.898 CR 43
44
45 34 43 Na+ F− 22.891 CR 43
46
47 34 44 Na+ Cl− 27.938 CR 43
48
49 34 45 Na+ Br− 24.99 CR 43
50
51 34 46 Na+ I− 21.383 CR 43
52
53 34 47 Na+ COO− 9.9125 CR 123
54
55 35 43 K+ F− 43.681 CR 43
56
57
58
59 40
1
2
3
4
6
7
8
9 35 44 K+ Cl− 61.01 CR 43
10
11 35 45 K+ Br− 56.592 CR 43
12
13 35 46 K+ I− 50.963 CR 43
14
15 35 47 K+ COO− 23.999 CR 123
16
17 36 43 Rb+ F− 53.634 CR 43
18
19 36 44 Rb+ Cl− 78.254 CR 43
20
21 36 45 Rb+ Br− 73.489 CR 43
22
23 36 46 Rb+ I− 67.344 CR 43
24
25 37 43 Mg2+ F− 28.051 CR 43
26
27 37 44 Mg2+ Cl− 29.6 CR 43
28
29 37 45 Mg2+ Br− 25.498 CR 43
30
31 37 46 Mg2+ I− 20.708 CR 43
32
33 38 43 Ca2+ F− 63.572 CR 43
34
35 38 44 Ca2+ Cl− 76.936 CR 43
36
37 38 45 Ca2+ Br− 68.645 CR 43
38
39 38 46 Ca2+ I− 58.536 CR 43
40
41 39 43 Sr2+ F− 73.570 CR 43
42
43 39 44 Sr2+ Cl− 95.805 CR 43
44
45 39 45 Sr2+ Br− 87.132 CR 43
46
47 39 46 Sr2+ I− 76.321 CR 43
48
49 40 43 Ba2+ F− 88.214 CR 43
50
51 40 44 Ba2+ Cl− 122.051 CR 43
52
53 40 45 Ba2+ Br− 112.84 CR 43
54
55 40 46 Ba2+ I− 101.15 CR 43
56
57
58
59 41
1
2
3
4
6
7
8
9 41 44 N+ Cl− 61.989 CR 123
10
11 41 47 N+ COO− 24.28 CR 123
12
13 41 56 N+ CH3 adj 462.18 CR 123
14
15 41 57 N+ CH2 adj 348.3 CR 123
16
17 42 33 OH- Li+ 9.1482 CR 43
18
19 42 35 OH- K+ 54.733 CR 43
20
21 42 36 OH- Rb+ 67.944 CR 43
22
23 42 37 OH- Mg2+ 33.269 CR 43
24
25 42 38 OH- Ca2+ 77.245 CR 43
26
27 42 39 OH- Sr2+ 90.501 CR This work
28
29 42 40 OH- Ba2+ 109.86 CR This work
30
31 42 44 OH- Cl− 123.21 CR 159
32
33 42 47 OH- COO− 44.520 CR 159
34
35 44 47 Cl− COO− 21.265 CR 123
36
37 47 56 COO− CH3 adj 509.37 CR 123
38
39 47 57 COO− CH2 adj 780.24 CR 123
40
41 48 49 HSO−
4 SO2−
4 75.239 CR 156
42
43 50 51 HNO3 NO−
3 270.15 CR 156
44
45 53 55 aCCOOH aCNHaC 102.98 CR 157
46
47 53 58 aCCOOH CH3 CO 568.75 85.000 157
48
49 55 58 aCNHaC CH3 CO 710.53 8.0000 157
50
51
52
53
54
55
56
57
58
59 42
1
2
3
4 Table 5: Group association energies εHB
kl,ab and bonding-volume parameters Kkl,ab for use
5 within the SAFT-γ Mie group-contribution approach.
6
7
8
9 site a site b
10

k l group k group l εHB
kl,ab /kB /K Kkl,ab /Å3
11 of group k of group l
12
13
14
15 5 14 aCH e1 H2 O H 563.56 339.61
16
17 5 32 aCH e1 H 3 O+ H 563.56 339.61
18
19 5 53 aCH e1 aCCOOH H 3961.5 0.023401
20
21 6 14 aCCH2 e1 H2 O H 563.56 339.61
22
23 6 32 aCCH2 e1 H3 O + H 563.56 339.61
24
25 6 53 aCCH2 e1 aCCOOH H 3961.5 0.023401
26
27 7 14 aCCH e1 H2 O H 563.56 339.61
28
29 7 32 aCCH e1 H3 O + H 563.56 339.61
30
31 11 11 COOH H COOH H 6427.9 0.8062
32
33 11 14 COOH e1 H2 O H 1451.8 280.89
34
35 11 14 COOH e2 H2 O H 1252.6 150.98
36
37 11 14 COOH H H2 O e1 2567.7 270.09
38
39 11 19 COOH e1 CH2 OH H 1062.1 210.67
40
41 11 19 COOH e2 CH2 OH H 997.89 227.070
42
43 11 19 COOH H CH2 OH e1 3238.4 36.05
44
45 11 32 COOH e1 H3 O + H 1451.8 280.89
46
47 11 32 COOH e2 H3 O + H 1252.6 150.98
48
49 11 42 COOH H OH− e1 2036 214.16
50
51 12 12 CH3 COCH3 H CH3 COCH3 e1 980.20 2865.2
52
53 12 14 CH3 COCH3 e1 H2 O H 1588.7 772.77
54
55 12 14 CH3 COCH3 e2 H2 O H 417.24 1304.3
56
57
58
59 43
1
2
3
4
5 site a site b
6

8
9
10
11 12 14 CH3 COCH3 H H2 O e1 1386.8 188.83
12
13 12 18 CH3 COCH3 e1 OH H 1492.9 986.39
14
15 12 18 CH3 COCH3 H OH e1 1177.4 323.75
16
17 12 19 CH3 COCH3 e1 CH2 OH H 1844.8 991.95
18
19 12 19 CH3 COCH3 H CH2 OH e1 686.93 585.99
20
21 12 20 CH3 COCH3 e1 CHOH H 1323.1 635.37
22
23 12 20 CH3 COCH3 H CHOH e1 1186.9 731.08
24
25 12 28 CH3 COCH3 e1 aCOH H 2162.2 935.51
26
27 12 28 CH3 COCH3 H aCOH e1 1053.1 500.00
28
29 12 53 CH3 COCH3 e1 aCCOOH H 2732.9 478.38
30
31 12 55 CH3 COCH3 e1 aCNHaC H 2208.9 750.72
32
33 13 14 COO e1 H2 O H 1245.8 454.98
34
35 13 18 COO e1 OH H 1920.1 114.85
36
37 13 53 COO e1 aCCOOH H 1772.3 945.09
38
39 14 14 H2 O H H2 O e1 1985.4 101.69
40
41 14 15 H2 O e1 CH3 OH H 1993.5 104.11
42
43 14 15 H2 O H CH3 OH e1 1993.5 104.11
44
45 14 17 H2 O e1 CO2 e1 1398.1 91.419
46
47 14 18 H2 O e1 OH H 500.00 1383.1
48
49 14 18 H2 O H OH e1 2225.6 114.53
50
51 14 19 H2 O e1 CH2 OH H 621.68 425.00
52
53 14 19 H2 O H CH2 OH e1 2153.2 147.40
54
55 14 20 H2 O e1 CHOH H 2289.1 63.813
56
57
58
59 44
1
2
3
4
5 site a site b
6

8
9
10
11 14 20 H2 O H CHOH e1 2140.9 19.478
12
13 14 21 H2 O e1 NH2 H 1988.3 55.824
14
15 14 21 H2 O H NH2 e1 1460.0 179.60
16
17 14 22 H2 O e1 NH H 1064.5 400.82
18
19 14 22 H2 O H NH e1 3890.4 928.00
20
21 14 23 H2 O H N e1 2783.7 15.536
22
23 14 24 H2 O e1 cNH H 1701.0 1.6177
24
25 14 24 H2 O H cNH e1 2838.4 37.395
26
27 14 25 H2 O H cN e1 5203.7 0.0374
28
29 14 27 H2 O H aCCH3 e1 563.56 339.61
30
31 14 28 H2 O e1 aCOH H 2500.0 52.470
32
33 14 28 H2 O H aCOH e1 1798.2 103.92
34
35 14 28 H2 O H aCOH e2 563.56 339.61
36
37 14 30 H2 O H cCHNH e1 5903.8 0.002075
38
39 14 30 H2 O e1 cCHNH H 5477.7 0.009582
40
41 14 31 H2 O H cCHN e1 4115.359 0.2307
42
43 14 32 H2 O e1 H 3 O+ H 1985.4 101.69
44
45 14 41 H2 O e1 N+ H 2783.7 15.536
46
47 14 42 H2 O H OH− e1 1492 76.411
48
49 14 47 H2 O H COO− e1 802.21 52.555
50
51 14 50 H2 O H HNO3 e1 1606.6 38.401
52
53 14 50 H2 O e1 HNO3 H 2806.6 38.401
54
55 14 51 H2 O H NO−
3 e1 1591.1 97.014
56
57
58
59 45
1
2
3
4
5 site a site b
6

8
9
10
11 14 52 H2 O H HCO− e1 1398.1 91.419
3
12
13 14 53 H2 O H aCCOOH e1 882.05 984.34
14
15 14 53 H2 O H aCCOOH e2 882.05 984.34
16
17 14 53 H2 O e1 aCCOOH H 5192.5 0.011186
18
19 14 59 H2 O e1 CH2 OH short H 600 490.19
20
21 14 59 H2 O H CH2 OH short e1 2000.6 130.02
22
23 14 62 H2 O e1 NH2 ca.OH H 1364.4 22.450
24
25 14 62 H2 O H NH2 ca.OH e1 1877.5 459.18
26
27 15 15 CH3 OH H CH3 OH e1 2062.1 106.57
28
29 15 53 CH3 OH H aCCOOH e1 1400.7 495.32
30
31 15 53 CH3 OH e1 aCCOOH H 871.46 0.25605
32
33 15 55 CH3 OH H aCNHaC e1 2346 3.1536
34
35 15 55 CH3 OH e1 aCNHaC H 2346 3.1536
36
37 17 21 CO2 e1 NH2 e1 3313.0 328.03
38
39 17 21 CO2 e2 NH2 e1 493.60 14.264
40
41 17 22 CO2 e1 NH e1 6657.6 0.025939
42
43 17 22 CO2 e2 NH e1 2344.7 492.99
44
45 17 23 CO2 e1 N e1 4270.8 0.4634
46
47 17 23 CO2 e2 N e1 7439.8 0.00675
48
49 17 24 CO2 e1 cNH e1 2846.5 1912.9
50
51 17 24 CO2 e2 cNH e1 5136.7 1561.2
52
53 17 25 CO2 e1 cN e1 2533.5 226.63
54
55 17 30 CO2 e1 cCHNH e1 2246 0.14057
56
57
58
59 46
1
2
3
4
5 site a site b
6

8
9
10
11 17 30 CO2 e2 cCHNH e1 3870.8 6445.7
12
13 18 18 OH H OH e1 2161.0 54.398
14
15 18 21 OH H NH2 e1 1282.7 254.28
16
17 18 21 OH e1 NH2 H 1354.0 141.35
18
19 18 22 OH e1 NH H 861.12 556.32
20
21 18 22 OH H NH e1 1477.7 449.81
22
23 18 23 OH H N e1 1357.2 599.19
24
25 19 19 CH2 OH H CH2 OH e1 2097.9 62.309
26
27 19 20 CH2 OH e1 CHOH H 1464.1 591.55
28
29 19 20 CH2 OH H CHOH e1 2500.0 10.444
30
31 19 23 CH2 OH H N e1 1247.2 286.83
32
33 19 28 CH2 OH e1 aCOH H 2182.7 402.60
34
35 19 28 CH2 OH H aCOH e1 250.03 25.000
36
37 19 41 CH2 OH e1 N+ H 1247.2 286.83
38
39 19 53 CH2 OH H aCCOOH e1 1284.9 2978.8
40
41 19 53 CH2 OH H aCCOOH e2 3889.3 0.43712
42
43 19 53 CH2 OH e1 aCCOOH H 1284.9 2978.8
44
45 20 20 CHOH H CHOH e1 2480.6 8.4740
46
47 20 53 CHOH H aCCOOH e1 2278.5 73.6980
48
49 20 53 CHOH H aCCOOH e2 2278.5 73.6980
50
51 20 55 CHOH e1 aCCOOH H 2278.5 73.6980
52
53 21 21 NH2 e1 NH2 H 1070.8 95.225
54
55 21 59 NH2 H CH2 OH short e1 629.88 346.08
56
57
58
59 47
1
2
3
4
5 site a site b
6

8
9
10
11 21 59 NH2 e1 CH2 OH short H 2403.8 26.192
12
13 22 22 NH e1 NH H 1370.3 10.062
14
15 22 59 NH e1 CH2 OH short H 1390.1 947.93
16
17 22 59 NH H CH2 OH short e1 341.13 1499.8
18
19 23 59 N e1 CH2 OH short H 1210.9 950.43
20
21 24 24 cNH H cNH e1 1511.6 87.651
22
23 24 25 cNH H cN e1 901.35 1.1555
24
25 27 53 aCCH3 e1 aCCOOH H 3961.5 0.023401
26
27 28 28 aCOH H aCOH e1 1538.1 275.86
28
29 30 30 cCHNH e1 cCHNH H 1293.5 438.49
30
31 32 34 H 3 O+ H OH− e1 1492 76.411
32
33 32 47 H 3 O+ e1 COO− H 802.21 52.555
34
35 32 49 H 3 O+ H SO2−
4 e1 2266 43.7
36
37 32 52 H 3 O+ H HCO−
3 e1 1398.1 91.419
38
39 50 50 HNO3 H HNO3 e1 1300 8.9978
40
41 53 53 aCCOOH H aCCOOH H 4745.7 10.04
42
43 53 55 aCCOOH H aCNHaC e1 2424.1 990.46
44
45 53 58 aCCOOH H CH3 CO e1 2828.1 47.677
46
47 59 59 CH2 OH short e1 CH2 OH short H 2097.9 62.309
48
49
50
51
52
53
54
55
56
57
58
59 48
1
2
3
4
4 Illustration of performance
5
6 In view of the large number of groups presented in tables 1, 3, 4 and 5, it is neither practical
7
8 nor desirable to attempt a comprehensive demonstration of the performance of the SAFT-γ
9
10 Mie approach in describing the full range of thermodynamic properties of the very many
11
12 molecules that may be modelled. Nevertheless, it is important to provide some indication
13
14 of the performance that may be expected, particularly in relation to groups not previously
15
16 published. Accordingly, we provide here a brief selection of results pertaining to selected
17
18 families of chemical compounds, favouring those including groups not previously featured in
19
20 journal publications.
21
22 We begin by presenting, in tables 6 and 7, absolute average deviations from experi-
23
24 mental values of calculated equilibrium thermodynamic properties, including those pertain-
25
26 ing to vapour–liquid-equilibrium (VLE), liquid–liquid-equilibrium (LLE) and solid–liquid-
27
28 equilibrium (SLE) phase behaviour, of varying single-component and mixture systems.
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 49
1
2
3
4 Table 6: Absolute average deviations from experimental values of calculated vapour pressure, Pvap (T ), saturated-liquid density,
5 ρsat (T ), specific enthalpy of vaporisation, ∆hvap , and isobaric specific heat capacity, cp , of selected compounds; n indicates the
6 number of data points, from the reference indicated, taken for comparison.
7
8
9
10
11
12 Cyclic Alkanes
13
14 T range / K n %AAD Pvap (T ) Ref. T range / K n %AAD ρsat (T ) Ref.
15
16 ethylcyclohexane 243–403 17 0.09 160
223–548 14 1.98 160
17
18 ethylcyclopentane 301–378 20 0.11 160
249–511 15 0.7 160
19
20 methylcyclopentane 293–344 20 0.05 160
200–474 14 1.93 160
21
22 160 160
50
n-propylcyclohexane 345–431 20 0.17 264–575 147 1.9

23
24 average 0.11 1.63
25
26
27
28
29 Alkyl Amines
30
32
33 ethylamine 288–456 11 1.76 161
223–293 12 0.99 161
34
35 n-propylamine 283–343 13 0.65 162
243–293 12 0.16 162
36
37 n-butylamine 292–515 40 6.68 163
233–293 12 0.35 163
38
39 n-pentylamine 322–378 13 1.84 164
213–453 13 0.74 164
40
41 n-hexylamine 321–406 6 5.7 165
253–493 13 1.03 165
42
43
44
46
47
1
2
3
4
5 Alkyl Amines (continued )
6
8
9 n-heptylamine 327–430 7 3.57 165
288–353 14 0.13 165
10
11 n-octylamine 344–495 23 1.43 166
298–328 7 0.11 166
12
13 average 3.09 0.50
14
15
16
17 T range / K n %AAD ∆hvap Ref. T range / K n %AAD cp Ref.
18
19 ethylamine 223–403 11 7.6 167
223–423 11 4.99 167
20
21 n-propylamine 243–443 12 2.07 167
253–453 11 5.54 167
22
51
23 n-butylamine 233–458 11 2.8 167

223–473 11 6.75 167
24
25 n-pentylamine 313–353 5 2.21 168
26
27 n-hexylamine 313–373 7 2.53 168
28
29 n-octylamine 300–520 12 3.64 166
30
31 average 4.16 4.40
32
33
34
35
36
37
38
39
40
41
42
43
44
46
47
1
2
3
4
5 Dialkyl Amines
6
8
9 diethylamine 224–500 29 2.53 169
224–500 29 2.78 169
10
11 dipropylamine 291–556 28 5.72 169
291–556 28 1.92 169
12
13 dibutylamine 211–607 22 13.66 169
211–607 22 1.7 169
14
15 dipentylamine 200–650 24 18.15 169
200–650 24 1.46 169
16
17 dihexylamine 260–688 23 8.73 169
260–688 23 2.29 169
18
19 diheptylamine 274–728 25 17.08 169
274–728 25 3.7 169
20
21 dioctylamine 288–740 24 4.56 169
288–740 24 2.64 169
22
52
23 average 10.06 2.36

24
25
26
27
28 Cyclic Amines
29
31
32 pyrrolidine 293–510 50 2.12 170
275–508 10 0.55 170
33
34 piperidine 273–416 37 1.06 171
296–519 12 0.12 171
35
36 piperazine 379–625 20 0.36 172
384–620 24 0.02 172
37
38 N-methylpiperidine 273–354 11 0.03 171
288–338 6 0.76 171
39
40 N-ethylpiperidine 274–313 9 0.57 171
293.15 1 0.01 171
41
42
43
44
46
47
1
2
3
4
5 Cyclic Amines (continued )
6
8
9 N-methylpiperazine 355–410 9 0.02 171
10
11 N-ethylpiperazine 365–429 15 0.01 171
12
13 N-methylcyclohexylamine 275–314 14 0.03 173
274–552 156 0.80 173
14
15 N-ethylcyclohexylamine 274–552 16 0.00 173
350–626 17 0.82 173
16
17 N,N-dimethylcyclohexylamine 275–314 14 0.34 173
276–557 14 3.55 173
18
19 average 0.45 0.83
20
21 2-ketones
22
53

24
25 2-butanone 187–536 18 4.31 174
187–536 17 0.85 174
26
27 2-pentanone 197–561 19 4.72 174
197–561 19 1.82 174
28
29 2-hexanone 218–586 19 1.32 174
218–586 19 0.96 174
30
31 2-heptanone 237–611 18 1.23 174
237–611 18 1.07 174
32
33 2-ocatnone 253–632 19 2.77 174
253–632 19 1.45 174
34
35 2-nonanone 266–652 19 2.21 174
266–652 19 1.78 174
36
37 2-decanone 255–671 21 4.39 174
255–671 21 2.28 174
38
39 average 2.99 1.46
40
41
42
43
44
46
47
1
2
3
4
5 2-ketones (continued )
6
7 T range / K n %AAD ∆hvap Ref. T range / K n %AAD cp Ref.
8
9 2-butanone 187–536 19 9.75 174
187–536 19 11.70 174
10
11 2-pentanone 197–561 21 7.51 174
197–550 20 9.09 174
12
13 2-hexanone 218–586 20 2.59 174
218–575 20 7.03 174
14
15 2-heptanone 237–611 20 2.11 174
237–600 20 5.67 174
16
17 2-ocatnone 253–632 20 4.29 174
253–620 20 3.97 174
18
19 2-nonanone 266–652 20 2.65 174
266–640 20 4.45 174
20
21 2-decanone 255–671 22 4.82 174
255–658 22 3.55 174
22
54
23 average 4.82 6.49

24
25
26
27
28 Primary alcohols
29
31
32 ethanol 231–463 30 2.55 175
159–463 39 2.08 175
33
34 1-propanol 280–483 25 5.85 175
169–483 38 1.42 175
35
36 1-butanol 295–506 26 2.76 175
186–506 39 1.17 175
37
38 1-pentanol 278–508 29 0.71 175
278–508 29 0.95 175
39
40 1-hexanol 310–428 17 1.40 175
273–547 38 1.54 175
41
42
43
44
46
47
1
2
3
4
5 Primary alcohols (continued )
6
8
9 1-heptanol 343–445 14 1.53 175
273–563 38 1.77 175
10
11 1-octanol 296–549 31 3.59 175
263–583 39 2.00 175
12
13 1-nonanol 366–481 15 1.08 175
293-596 38 2.41 175
14
15 1-decanol 301–526 27 2.81 175
293–613 38 3.01 175
16
17 average 2.48 1.82
18
19
20
21
22
55
Secondary alcohols
23
25
26 2-butanol 260–480 23 1.1 176
260–480 23 1.3 176
27
28 3-hexanol
29 300–520 46 8.0 176
300–520 46 0.4 176
30 4-hexanol
31
32 2-octanol
33
34 3-octanol 320–560 75 8.9 176
320–560 75 1.2 176
35
36 4-octanol
37
38
39
40
41
42
43
44
46
47
1
2
3
4
5 Scondary alcohols (continued )
6
8
9 2-decanol
10
11 3-decanol
12 330–600 76 11.7 176
330–600 76 1.4 176
13 4-decanol
14
15 5-decanol
16
17
18
19 average 7.43 1.08
20
21
22
56
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
46
47
1
2
3 Table 7: Absolute average deviations from experimental values of calculated osmotic coeffi-
4
cient, Φ, and mean ionic activity coefficient, γ± , of selected electrolyte solutions over a range
5
6 of molality from 0.001 to 3.0 mol kg−1 ; nΦ and nγ± indicate the number of data points taken
7 in relation to Φ and γ± , respectively.
8
9 Aqueous electrolytes
10 nΦ %AAD Φ Ref. nγ± %AAD γ± Ref.
11 LiCl 23 1.87 177–182
23 5.79 177
12 177–181 177
13
LiBr 23 0.53 23 2.48
177 177
14 LiI 23 2.07 23 3.33
177,178,183–187 177
15 NaCl 40 0.63 12 4.05
16 NaBr 23 0.95 177,181,183
23 3.17 177
17 NaI 23 0.88 177
23 2.63 177
18 177–180 177
19 KCl 37 0.88 23 1.27
177 177
20 KBr 24 0.67 21 1.08
177 177
21 KI 23 0.35 23 0.55
22 average 0.73 2.71
23
24
25
26 In Figure 2 we illustrate the performance of SAFT-γ Mie in describing phase-equilibrium
27
28 properties of secondary alcohols, both pure and in mixtures with normal alkanes; this high-
29
30 lights the efficacy of the CHOH group. In (a) we present SAFT-γ Mie calculations of
31
32 the vapour pressures of secondary decanol and octanol, and in (b) we present pressure–
33
34 composition (P –x) isotherms for the n-hexane + 2-butanol mixture. As can be seen from
35
36 the experimental data (symbols) in (a), the vapour pressures of the different isomers (ac-
37
38 cording to the substituted position in the carbon chain of the OH moiety) are very similar,
39
40 whereby the distinction between these is not taken into account. The refinement of parame-
41
42 ters for the CHOH group is performed using experimental data for 2-butanol and secondary
43
44 hexanols, octanols and decanols substituted in all possible positions (2 and 3 for hexanols,
45
46 2, 3 and 4 for octanols and 2, 3, 4 and 5 for decanols); pure-component vapour-pressure and
47
48 saturated-liquid-density data are considered, as well as alcohol + n-alkane binary mixture
49
50 bubble-pressure data. Thereby, for secondary alcohols, in the SAFT-γ Mie approach no
51
52 distinction is made for isomers differing (only) in the substitution position of the CHOH
53
54 group within the carbon chain. As can be seen in Figure 2, SAFT-γ Mie provides an ex-
55
56 cellent description of these phase equilibrium data, including the azeotropes and dew curves
57
58
59 57
1
2
3
of the n-hexane + 2-butanol (P –x) isotherms, which were not included in the parameter
4
5
refinement.
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20 (a) (b)
21
22 Figure 2: Vapour–liquid equilibria of secondary alcohols: (a) vapour pressures of secondary
23 octanol and secondary decanol. Symbols represent pseudo-experimental data from NIST;
24 188
the continuous and dashed curves represent the SAFT-γ Mie description for n-octanol
25
26
and n-decanol, respectively. (b) Isothermal vapour-liquid equilibria of the n-hexane + 2-
27 butanol binary mixture. The symbols represent experimental data 189 , and the continuous
28 and dashed curves the description of the SAFT-γ Mie approach.
29
30
31
Further, in relation to the CHOH group, in Figure 3 we present temperature–composition
32
33
(T –x) isobars from the binary-mixture phase diagrams of 1-butanol + water and 2-butanol
34
35 + water mixtures. The unlike H2 O–CHOH interaction is refined using experimental vapour–
36
37 liquid-equilibirum (VLE) data for the 2-butanol + water and 2-hexanol + water mixtures,
38
39 and liquid–liquid-equilibrium (LLE) data for the 2-hexanol + water and 2-octanol + water
40
41 systems. One can discern from the figure that the SAFT-γ Mie approach successfully dis-
42
43 tinguishes the different phase behaviour of the primary and secondary alcohol, and provides
44
45 a qualitatively correct prediction of the LLE for the 2-butanol + water mixture, although it
46
47 over-predicts the lower critical solution temperature (LCST) below which the components
48
49 of the mixture are fully miscible.
50
51 Hitherto we have demonstrated the performance of SAFT-γ Mie in relation to both VLE
52
53 and LLE. In Figure 4 we illustrate the descriptions of the isobaric solid–liquid phase diagrams
54
55 of thymol with each of two alcohols, 1-decanol and 1-dodecaonol. Solubility is calculated
56
57
58
59 58
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17 Figure 3: Temperature–composition (T –x) isobars from the phase diagrams of 1-butanol +
18 water and 2-butanol + water binary mixtures at atmospheric pressure. Symbols represent
19 experimental data 190–192 ; curves represent calculations using SAFT-γ Mie.
20
21
22
by considering the solid–liquid equilibrium (SLE) between the pure crystalline solid and the
23
24
liquid phase containing the solvent and the solute using the expression
25
26
27 fus
∆Hm,i

1 1

28 ln xi (P, T ) = − − ln γi (P, T, xi ) (41)
29 R Tm,i T
30
31 fus
32 where xi , ∆Hm,i and Tm,i and γi are the mole fraction, molar enthalpy of fusion, the normal
33
34 melting temperature and the activity coefficient of the solute (i), respectively, and where the
35
36 difference between the heat capacities of the solid and the liquid form of the solute has been
37 fus
38 neglected. The values of ∆Hm,i and Tm,i are taken from experimental data. The SAFT-γ
39
40 Mie EoS is used in the calculation of the activity coefficient of i, γi . The descriptions of both
41
42 solid–liquid phase diagrams are seen to be excellent.
43
44 Amines represent an important class of compound in contemporary thermodynamic mod-
45
46 elling. They are present in fertilisers, and are used in pest control and in the tanning of
47
48 leather. They are present in amino acids and, thereby, peptides and many vitamins. Many
49
50 pharmaceuticals incorporate amine groups, including pain medication and analgesiscs such
51
52 as morphine and demerol. The common decongestant ephedra is an amine; amines also
53
54 feature among recreational drugs such as amphetamines and methamphetamines. Not least
55
56 in their importance is their use in the capture of CO2 from instustrial processes. The post-
57
58
59 59
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Figure 4: Isobaric (T –x) phase diagram at P = 0.1 MPa featuring solid–liquid equilibria of
20
21 thymol + 1-decanol and thymol + 1-dodecanol binary mixtures. Symbols represent exper-
22 imental data from Ref. 193 (thymol in 1-decanol) and from Ref. 194 (thymol in 1-dodecanol);
23 curves represent calculations using SAFT-γ Mie.
24
25
26 combustion capture (PCC) of carbon dioxide (and its storage) is one of the most important
27
28 methods in the reduction of CO2 emissions from coal and natural-gas-fired power plants.
29
30 In Figure 5, we present our calculations for mixtures of cyclic amines with water; the sym-
31
32 bols correspond to experimental data taken from references 195–197 while the curves represent
33
34 descriptions using SAFT-γ Mie. Isobaric vapour–liquid equilibria at atmospheric pressure
35
36 for aqueous mixtures of methyl piperazine (MPZ) and ethyl piperazine (EPZ) were used to
37
38 refine the model parameters; the isobaric (T –x) phase diagram of the liquid–liquid equilib-
39
40 ria of N-methyl piperidine (MPD) and water at a pressure of P = 0.101 MPa, depicted in
41
42 Figure 5(c), illustrates the predictive capability of the models; the SAFT-γ Mie approach
43
44 accurately predicts the LCST below which the components of the mixture are fully miscible.
45
46 We note that it is not common for GC methods to be able to simultaneously describe both
47
48 VLE and LLE accurately; its success in this regard represents a strength of the SAFT-γ Mie
49
50 approach.
51
52 In Figure 6 we consider more-complicated, ternary mixtures involving an amine, water
53
54 and carbon dioxide. In Figure 6(a), we present calculations of the solubility of CO2 in aqueous
55
56 piperazine solutions, at a range of temperatures and differing piperazine molalities; as usual,
57
58
59 60
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18 (a)
19
20
21
22
23
24
25
26
27
28
29
30
31 (b)
32
33
34
35
36
37
38
39
40
41
42
43
44
45 (c)
46
47 Figure 5: (a) (T –x) isobars at atmospheric pressure from the phase diagrams of binary
48 mixtures of water + cyclic amine: (a) vapour–liquid equilibria of aqueous methyl piperazine
49 (MPZ); (b) vapour–liquid equilibria of aqueous ethyl piperazine (EPZ); (c) liquid–liquid equi-
50
51
libria of aqueous N -methyl piperidine (MPD). Curves represent calculations using SAFT-γ
52 Mie, while symbols represent experimental data (Ref. 195 for water + MPZ, 196 for water +
53 EPZ and 197 for water + MPD).
54
55
56
57
58
59 61
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16 (a) (b)
17
18 Figure 6: Solubility of CO2 in (a) piperazine aqueous solutions and (b) 30 weight% aqueous
19
20
monoethanolamine solution, expressed as the partial vapour pressure of CO2 as a function of
21 the CO2 loading. Curves represent calculations using SAFT-γ Mie while symbols represent
22 experimental data from Refs. 198 and 199 for (a) and (b), respectively; mPZ indicates the
23 molality of piperazine.
24
25
26 the symbols represent experimental data 198 while the curves depict calculated isotherms.
27
28 One can discern that the effects of both temperature and piperazine concentration are well
29
30 captured.
31
32 As a final example of the performance of SAFT-γ Mie in modelling amines, in Figure
33
34 6(b) we present calculations of the solubility of CO2 in aqueous monoethanolamine (MEA),
35
36 a system that is highly relevant for PCC of CO2 . MEA is modelled using an NH2 group, a
37
38 CH2 group and a CH2 OH short group, as described in Section 3.1.
39
40 Ternary systems of alkanolamines, water and carbon dioxide are reacting mixtures in
41
42 which new species are formed via complex reaction schemes. 200–203 The phase behaviour of
43
44 these mixtures is modelled without explicitly treating the reactions or the new species; the
45
46 reactions are instead accounted for implicitly via the incorporation of association sites on the
47
48 CO2 molecule to mediate the interactions with the amine groups. This approach has been
49
50 successfully applied in previous work 108,204–209 using SAFT-VR ; for implementation details
51
52 see Ref. 206 .
53
54 The latest developments in the SAFT-γ approach 43,123,156,210 also incorporate charged
55
56 groups in the formalism. The free-energy contributions related to the Coulombic and solvent-
57
58
59 62
1
2
3
ion polar interactions are accounted for in the AIon and ABorn terms discussed earlier. Ex-
4
5
amples of these have been published for strong electrolytes 43,210 , weak acids 156 and deep
6
7
eutectic solvents 123 .
8
9 In Figure 7 we exemplify the performance of SAFT-γ Mie in modelling electrolyte sys-
10
11 tems, presenting osmotic coefficients of (in (a)) and mean ionic activity coefficients (in (b))
12
13 of sodium halide salts, both calculated as a function of the molality, m, of the salt, at
14
15 T = 298.15K and P = 101 kPa. The description of both properties is seen to be satisfactory.
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31 (a) (b)
32
33 Figure 7: (a) Osmotic coefficients of several aqueous salts, as indicated in the legend. (b)
34 Mean ionic activity coefficient. Curves represent calculations using SAFT-γ Mie, while
35
symbols represent experimental data 177,178,183,187 .
36
37
38
39
40
41 5 Discussion and concluding remarks
42
43
44 A significantly expanded set of functional groups for use with the SAFT-γ Mie EoS 54 has been
45
46 presented, providing an update of the current status of the SAFT-γ Mie database. The range
47
48 of chemical families for which the approach may be applied has been extended to include, for
49
50 example, secondary alcohols and amines (both linear and cyclic), as well as charged groups,
51
52 relating to the modelling of both strong and weak electrolyte solutions. Complementing this
53
54 expansion of the group database, the number of bespoke unlike interaction parameters has
55
56 also been increased, reducing reliance on combining rules.
57
58
59 63
1
2
3
Group parameters are estimated using, as far as possible, pure-component data together
4
5
with mixture data where necessary. These parameters provide for accurate descriptions of
6
7
both VLE and other thermodynamic properties of compounds of differing chemical families,
8
9 as well as VLE, LLE and SLE of binary and higher mixtures, over a wide range of condi-
10
11 tions. The approach is well suited to the calculation of solubilities, which are calculated by
12
13 considering the SLE between the pure crystalline solid and the liquid phase containing the
14
15 solvent and solute.
16
17 In some cases, second-order parameters are required to give a more-accurate description
18
19 of the thermodynamics when multicomponent systems are involved. This is most likely due
20
21 to the multi-polarisation effect. For example in an aqueous alkanolamine system, both amine
22
23 and alcohol groups appear on the same molecule, in the presence of water. The use of a
24
25 second-order CH2 OH short group to represent this moiety in MEA provides for an excellent
26
27 description of the solubilty of CO2 in aqueous MEA solutions.
28
29 In summary, the models provided here for the large variety of different chemical groups
30
31 collectively represent an excellent platform for the accurate calculation of a broad range
32
33 of properties for a diverse range of systems, at widely varying conditions, underlining the
34
35 effectiveness of SAFT-γ Mie as an ideal tool for the prediction of thermodynamic properties.
36
37
38 ACKNOWLEDGMENTS
39
40 The authors gratefully acknowledge financial support from the Engineering and Physical Sci-
41
42 ences Research Council (EPSRC) of the UK (grants GR/T17595, GR/N35991, EP/E016340,
43
44 EP/P006965, and EP/J014958) to the Molecular Systems Engineering group. We grate-
45
46 fully acknowledge support from the EPSRC and the Future Continuous Manufacturing and
47
48 Advanced Crystallisation Research Hub (Grant Ref: EP/P006965/1). Felipe A. Perdomo
49
50 thanks the European Unions Horizon 2020 research and innovation program (Grant 727503
51
52 - ROLINCAP H2020-LCE-2016-2017/H2020-LCE-2016-RES-CCS-RIA) for funding a re-
53
54 search fellowship. Siti H. Khalit thanks PETRONAS Research for funding a PhD stu-
55
56 dentship. Amparo Galindo is thankful to the Royal Academy of Engineering and Eli Lilly
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58
59 64
1
2
3
and Company for support of a Research Chair (Grant RCSRF18193). The authors gratefully
4
5
acknowledge support from Lilly through the PharmaSEL Programme and joint EPSRC/Lilly
6
7
Prosperity Partnership (EP/T005556/1). We gratefully acknowledge support from Glaxo-
8
9 SmithKline plc (GSK) via the Engineered Medicines Lab. This publication was made possi-
10
11 ble, in part, by NPRP grant number 8-1648-2-688 from the Qatar National Research Fund.
12
13 The statements made herein are solely the responsibility of the authors.
14
15
16 Data Statement
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18 Data underlying this article can be accessed on Zenodo at https://zenodo.org/record/xxxxxx,
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20 and used under the Creative Commons Attribution license.
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eling liquid–liquid and liquid–vapor equilibria of binary systems containing water with
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ACS Paragon Plus Environment

n-propylcyclohexane 345–431 20 0.17 264–575 147 1.9

23 n-butylamine 233–458 11 2.8 167

23 average 10.06 2.36

23 T range / K n %AAD Pvap (T ) Ref. T range / K n %AAD ρsat (T ) Ref.

23 average 4.82 6.49

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