Enthalpy and Heat Capacity Changes on Mixing: Fundamental

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Enthalpy and heat capacity changes on mixing: fundamental aspects and prediction by means of the PPR78 cubic equation of state Jun-Wei Qian, Romain Privat, Jean-Noeal Jaubert, and Pierre Duchet-Suchaux Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/ef401605c • Publication Date (Web): 17 Sep 2013 Downloaded from http://pubs.acs.org on September 29, 2013

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Enthalpy and heat capacity changes on mixing: fundamental aspects and prediction by means of the PPR78 cubic equation of state. Jun-Wei QIANa, Romain PRIVAT*,a, Jean-Noël JAUBERTa and Pierre DUCHET-SUCHAUXb a

Université de Lorraine, ENSIC (École Nationale Supérieure des Industries Chimiques), LRGP (Laboratoire Réactions et Génie des Procédés), 1 rue Grandville, BP 20451, Nancy cedex 9, France. b TOTAL, 2 place Jean Millier, La Défense 6, 92400 Courbevoie, France *

Corresponding author: R. Privat. Email: [email protected] Telephone number: (+33)383 175 128 – Fax number: (+33)383 175 152.

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Abstract The PPR78 model is a predictive cubic equation of state relying on the group-contribution concept. Our previous studies have highlightened its capacity to predict the phase behavior of mixtures containing a large variety of compounds: alkanes, alkenes, aromatic compounds, permanent gases, sulphur compounds, etc. In this paper, it is attempted for the first time to answer the question "can the PPR78 model be safely used in energy-rate balances?". To do so, the largest possible number of enthalpy of mixing data and isobaric heat capacity of mixing data were collected in the open literature and predicted using the PPR78 model. It is shown that although certainly perfectible, this model generally provides from acceptable to accurate estimations of these properties depending on the nature of the mixtures and the conditions of temperature and pressure as well. Furthermore, this paper proposes some general reflections both on conceptual and practical issues: - is it always possible to claim that the excess enthalpy and the enthalpy of mixing are two strictly equivalent quantities? - does an equation of state have the same capacity to reproduce enthalpy of mixing data in onephase and in two-phase regions? - which criterion to use for evaluating the accuracy of an equation of state in terms of energy-rate balances? Keywords: enthalpy of mixing; heat capacity of mixing; PPR78; cubic equation of state; excess enthalpy; prediction; ideal solution.


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1. Introduction Engineers use principles drawn from thermodynamics to analyze and design industrial processes. The first law of thermodynamics (also named energy-rate balance) applied to an open multi-component system at steady state, is given by: & = & +Q W

∑

  u2 n& out  h out + out + gzout  −   2  

∑

  u2 n& in  h in + in + gzin    2  

(1)

& are the net rates of energy transfer by work and by heat, respectively; n& is the & and Q where W molar flowrate, h denotes the molar enthalpy of a stream, u, its velocity, z, its vertical position and g, the Earth's gravity. Potential-energy terms can generally be neglected (except in e.g., an oil well) as well as kineticenergy terms (except in e.g., a gas flare). The subscripts in and out mean inlet and outlet streams, respectively. From classical thermodynamics, the molar enthalpy of a p-component homogeneous system at a given temperature

T , pressure P and composition z (mole fraction vector) is: p

h(T, P, z ) =

state (T, P) + h M (T, P, z ) pure i ∑ zi ⋅ hstable

(2)

i =1

where h pure i (T, P) is the molar enthalpy of pure component i at the same temperature T and pressure P as the mixture and in its actual stable state. The h M quantity represents the molar enthalpy change on isothermal and isobaric mixing of the p components at fixed T and P and in their actual stable states. As will be detailed in the next sections, mainly two effects contribute to the value of h M :

•

a phase change of at least one of the compounds during the mixing process,

•

the non-ideality of the mixture which is revealed when the molecules making up the mixture are different in terms of size, shape and interactions which they exert on one another.

When molecules are few polar, few associating and are sufficiently alike from the point of view of their shapes and sizes (e.g. alkane mixtures) and when phase change does not occur during the mixing process, hM terms are negligible and consequently, the energy-rate balance is essentially controlled by the pure-component terms. For the other systems, a lack of accuracy on the determination of h M may have a detrimental effect on the accuracy of the energy-rate balance. In order to manage the complexity of mixtures involved in chemical industrial processes - from petroleum to pharmaceutical applications - predictive models are more and more often considered.


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Whereas developers of predictive equations of state (EoS) generally concentrate their efforts on the prediction of phase-equilibrium properties, the prediction of enthalpy changes on mixing and of isobaric heat capacity changes on mixing, is rarely investigated. Note that isobaric heat capacities of M mixing, which are derived from mixing enthalpies according to cM p = (∂h / ∂T) P,z , are also

important properties, extensively measured and frequently used in chemical engineering (e.g., in calorimetry, heat transfer or coupled heat and mass transfer applications). In their Guidelines for

publication of equations of state [1], Deiters and De Reuck emphasize the necessity for developers to benchmark their models on derived properties such as enthalpy or heat capacity before publishing it. They indeed wrote: “The estimation of caloric data, such as residual specific heat capacities

(isochoric or isobaric) or speed of sound is also of general interest as well as industrial importance. Authors are urged to report predictions of such data.” Mainly two classes of EoS are currently developed and focus the attention of both industrialists and researchers: -

the vast family of cubic EoS acknowledged as simple and efficient for the representation of phase equilibria of petroleum mixture, which however may fail in predicting EoS derived properties (by predicting EoS derived properties, it is here meant that the EoS parameters were not fitted on derived properties data),

-

the EoS deriving from advanced statistical thermodynamics theories. Although these promising models need to be improved and in particular, exhibit difficulties to represent the critical and supercritical area with the same set of parameters as the one used in the subcritical region, their physical foundation often allows a rather pertinent prediction of derived properties.

In this paper, the PPR78 predictive cubic model, developed since the early 2000s by Jaubert and coworkers, is evaluated for the first time in terms of prediction of mixing enthalpy and mixing heatcapacity data. Such a model combines the widely used Peng-Robinson EoS [2,3] with a groupcontribution method aimed at estimating the temperature-dependent binary interaction parameters

k ij (T) . Twenty groups were previously defined [4-14]: CH 3 , CH 2 , CH, C, CH4 (methane), C2H6 (ethane), CHaromatic, Caromatic, Cfused aromatic rings, CH2,cyclic, CHcyclic ⇔ Ccyclic, CO2, N2, H2S, SH, H2, CH2=CH2 (ethylene), CH2,alkenic ⇔ CHalkenic, Calkenic and CH2,cycloalkenic ⇔ CHcycloalkenic. By considering as far as possible all the VLE, LLE, critical and azeotropic data available in the open literature (around 100,000 experimental points), 420 group-interaction parameters were determined. Note that the databank used to fit the model parameters did not include any mixing-enthalpy or mixing heat-capacity data.


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The PPR78 model has shown to be capable of representing the vapor-liquid and liquid-liquid equilibrium behaviors of various types of binary mixtures as well as their critical loci, with a good accuracy. As a major result, PPR78 can efficiently predict the phase-equilibrium behavior of synthetic petroleum blends, from natural gases to heavy oils [11]. This promising result confirms that the group-interaction parameters determined through the fitting procedure using phaseequilibrium data can be safely used to predict phase-equilibrium properties of complex mixtures. In the present paper, the PPR78 equation of state is used as a purely predictive model since the properties under consideration ( h M and cM P ) were not involved in the fitting procedure of the group-interaction parameters. It is also attempted to answer the question: can the PPR78 model be

safely used in energy-rate balances? In order to provide a fair overview of the model capacities, it was decided to consider, as far as possible, all the hM and cPM data available in the open literature and to predict them using the PPR78 model.


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2. Discussion around the significance and the representation of enthalpy change on mixing data 2.1. Enthalpy of mixing versus excess enthalpy Before getting to the heart of the matter, it is necessary to properly characterize the enthalpy change on mixing, which is pragmatically defined as the enthalpy change that would be measured if the pure components making up the mixture were mixed together in an isothermal and isobaric mixing device of a laboratory (e.g. a calorimeter). Following this definition, there is no doubt that the pure components to be mixed are considered under their actual stable state at the working temperature and pressure: M

h (T, P, z ) =

p

h(T, P, z ) 1424 3

−

molar enthalpy of the mixture

state (T, P) ∑ zi hstable pure i

(3)

i =1

where zi is the overall mole fraction of the component i in the final mixture. As pointed out by Privat and Jaubert [15], the physical state of a binary mixture is totally independent of the physical states of the pure components that were mixed together to make it up at fixed T and P (e.g., the mixing of two pure liquids can lead either to a gaseous mixture, or to a single-liquid-phase mixture, or to a mixture in liquid-liquid equilibrium or to a mixture in liquidvapor equilibrium). In classical thermodynamics, a mixing property results from the addition of an ideal mixing property (i.e., the value of the mixing property of an ideal solution having the same temperature, the same pressure, the same composition and the same aggregation state as the real mixture) and an excess property: h M = h M,id + h E

(4)

In most of textbooks of thermodynamics, it is claimed that h M,id = 0 so that: hM = hE

(5)

This identification leads experimentalists measuring enthalpy change on mixing to name the measured quantity either enthalpy of mixing [16] or excess enthalpy [17]. Some authors even speak about excess enthalpy of mixing [18] which emphasizes that the multiplicity of terms may induce confusion. More annoying, Privat and Jaubert [15] recently proved that Eq. (5) is non-general and solely applies when the mixture and the pure components that make it up, are in the same aggregation state. Indeed, by combining the definition of the molar excess enthalpy [19]: 6 - Environment ACS Paragon -Plus

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p

h E (T, P, z ) =

h(T, P, z ) 1424 3

molar enthalpy of the mixture

−

aggregation state as the mixture (T, P) ∑ zi hsame pure i

(6)

i =1

(which involves potentially-fictitious states for pure components) and the definition of the enthalpy change on mixing (see Eq. (3)), one obtains the following expression for the enthalpy change on ideal mixing:

h M,id (T, P, z ) =

p

aggregation state as the mixture state (T, P) − h stable (T, P)  ∑ zi hsame pure i pure i 

(7)

i =1

which is non necessarily equal to zero. Note in passing, that the molar excess enthalpy is not systematically measurable since its definition may involve fictitious (i.e. non-stable) states which are not accessible from experiments. On the contrary, an enthalpy change on mixing is by definition a measurable quantity. Note furthermore that if there is no phase change of the pure compounds during the mixing process ( h M,id = 0 ) and if the mixture behaves ideally ( h E = 0 ) then h M = 0 , as stated in the introduction.

To sum up, experimentalists can only measure enthalpy changes on mixing (or equivalently, heats

of mixing). They cannot access to excess enthalpies except in the case where h E = h M , occurring when a mixture is formed from pure components that are initially in the same aggregation state as the resulting mixture.

2.2. Representation of the isothermal and isobaric enthalpy change on mixing as a function of z1 in binary systems, when phase change occurs The representation of hM versus z1 at fixed T and P for a liquid solution formed from pure liquids is a well-known application of classical thermodynamics. Numerous empirical correlations of hM(T,z1) are available in the open literature (Redlich-Kister, Van Laar, Wilson etc.) to model the behavior of liquid mixtures. The representation of hM versus z1 at fixed T and P for a gaseous mixture formed from two pure gases is strictly identical to the previous case. Let us address the case of a binary system (1) + (2) characterized by an overall composition z1 and such that a VLE exists at the considered T and P. The mole fractions of component 1 in the liquid and gas phases in equilibrium are denoted x1 and y1, respectively. For the sake of simplicity, it is first assumed that the gas phase behaves as a perfect gas mixture and that the liquid phase is ideal. By convention, pure component 1 is assumed to be more volatile than pure component 2. When mixing the two pure components (1) and (2) at fixed T and P such that 7 - Environment ACS Paragon -Plus

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P2sat (T) ≤ P ≤ P1sat (T) (pure component 1 is in a gaseous state whereas pure component 2 is in a liquid state), three cases may occur, depending on the value of z1:

•

either the final mixture is made up of a single liquid phase (i.e., z1 < x1). According to Eq. (7), one has: gas liq liq M,id h liq = z1 [h liq pure 1 (T, P) − h pure 1 (T, P)] + z 2 [h pure 2 (T, P) − h pure 2 (T, P)] 14444244443 14444 4244444 3 ≠0

(8)

=0

M Consequently, h liq is a linear function of z1 .

Since the liquid phase is supposed to be incompressible and the gas phase behaves ideally: M,id h liq (T, P, z1 ) ≈ −z1 ∆ vap H pure 1 (T)

(9)

where ∆ vap H pure i (T) denotes the molar enthalpy of vaporization of pure i at T. •

either the final mixture is made up of a single gas phase (i.e., z1 > y1). According to Eq. (7), one has: gas gas liq M,id h gas = z1 [h gas pure 1 (T, P) − h pure 1 (T, P)] + z 2 [h pure 2 (T, P) − h pure 2 (T, P)] 14444244443 14444 4244444 3 =0

(10)

≠0

M Consequently, h gas is a linear function of z 2 .

As previous, it is possible to prove that: M,id h gas (T, P, z1 ) ≈ z 2 ∆ vap H pure 2 (T)

•

(11)

or the mixture is in VLE (and x1 ≤ z1 ≤ y1 ); in that case, the enthalpy of mixing of the system is given by: ,id M,id M ,id hM VLE (T, P, z1 ) = τh gas (T, P, y1 ) + (1 − τ)h liq (T, P, x1 )

(12)

τ is the molar proportion of the gas phase which according to the lever rule, is given by:

τ=

z1 − x1 y1 − x1

(13)

By combining Eqs. (12) and (13), one observes that h M VLE is a linear function of z1 Let us consider now a non-ideal binary system (1) + (2) verifying P1sat (T) > P2sat (T) exhibiting a VLE at given T and P. According to the previous study, the isothermal and isobaric hM versus z1 curve (simply called hM-curve thereafter) is made up of three branches: •

for z1 < x1 , the system is in a liquid state and according to Eqs. (4) and (9): 8 - Environment ACS Paragon -Plus

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M E h M = h liq (T, P, z1 ) ≈ −z1 ∆ vap H pure 1 (T) + h liq

•

for z1 > y1 , the system is in a gas state and according to Eqs. (4) and (11): M E h M = h gas (T, P, z1 ) ≈ z 2 ∆ vap H pure 2 (T) + h gas

•

(14)

(15)

for x1 ≤ z1 ≤ y1 , the system is in a VLE and according to Eqs. (4) and (12): M M M h M = h VLE (T, P, z1 ) = τh gas (T, P, y1 ) + (1 − τ)h liq (T, P, x1 )

(16)

As previously observed, h M VLE is a linear function of z1 (regardless of the assumption carried out on the ideality of the mixture). As an illustration, the isothermal phase diagram of the nearly-ideal binary system n-hexane(1) + noctane(2) at T = 403.2 K is given in Fig. 1 as well as the isothermal isobaric hM-composition diagram at T and three different pressures: P = 1 bar (and the system is gaseous on the whole composition range), P = 5.5 bar (and the system is liquid on the whole composition range) and P = 3 bar (and the system exhibits a VLE domain). In this last case, the three branches making up the hM curve clearly appear. Note also that the differences in the orders of magnitude of hM are well visible: when the system is made up of a single phase, absolute values of hM reach several dozens of J/mol (thus confirming the near-ideality of the binary system since in these cases h E = h M ) whereas when a phase change occurs, absolute values of hM reach several thousands of J/mol (and in this case h M ≈ h M,id ).

2.3. On the capacity of EoS to predict hM data As pointed out by Eq. (4), an enthalpy of mixing results from two different contributions that are: •

an enthalpy of ideal mixing term reflecting the phase changes of the components occurring during the isothermal and isobaric mixing process (see Eq. (7)). As shown by Eq. (9), this term essentially involves pure-component enthalpies of vaporization and consequently, an equation of state able to well reproduce pure-component phase changes should be able to well estimate h M,id .

•

an excess-enthalpy term which reflects the non-ideality of the final solution and accounts for enthalpic effects due to the differences in shape and size between unlike molecules and to the different natures of interactions between them. This term is specific to the mixture and consequently only cubic EoS combined with wellparameterized mixing rules can estimate it properly.


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Pure-component enthalpies of phase change often have at least one order of magnitude more than excess enthalpies and consequently, when a phase change occurs during the mixing process, one generally has: h M,id >> h E ⇒ h M ≈ h M,id . Therefore, an equation of state able to accurately predict an experimental phase change in the isothermal and isobaric hM versus z1 plane, essentially shows its capacity to reproduce pure-component enthalpies of vaporization. Contrary to what is sometimes asserted by model developers, it validates more the equation of state for pure components than the equation of state for mixtures.

2.4. Focus on some isothermal and isobaric (enthalpy of mixing, composition) projections of systems showing atypical phase behavior Whereas isothermal Pxy or isobaric Txy phase diagrams showing azeotropy, liquid phase split or criticality are well known and frequently exemplified through the open literature, the presence of such phenomena on isothermal and isobaric projections of the phase diagram in the (enthalpy of mixing, composition) plane is more rarely described. In order to illustrate how azeotropy can influence the shapes of hM-curves, the case of the CO2(1) + ethane(2) system is first considered. This system is known to exhibit absolute azeotropy [7] (see Fig. 2). Fig. 2.b shows a series of hM curves calculated at 273.15 K and at the pressures indicated by the horizontal lines represented in Fig. 2.a. As discussed in section 2.2, one can first note that the hM-curves plotted at pressures P1, P2 and P4 perfectly illustrate that the enthalpy of mixing of a mixture formed from two pure components in the same aggregation state as the mixture (see P1 and P4) is much smaller than the enthalpy of mixing of a mixture formed from a gaseous pure component and a liquid pure component (see P2). In addition, the hM-curve associated to pressure P2 is classically made up of three branches due to the existence of a VLE at T and P2: a liquid-like branch (on the left hand side) mathematically defined by Eq. (14), a vapor-like branch (on the right hand side) defined by Eq. (15) and a VLE branch (in the middle) verifying Eq. (16). At pressure P1, the mixture is entirely gaseous whereas at P4, the mixture is liquid on the whole composition range. It appears that the enthalpies of mixing of the gas phase are negligible by comparison with the ones of the liquid phase. This tends to show that the gas phase exhibits small departures from the ideal gas behavior whereas the liquid phase exhibits high departures from the ideal solution behavior (note by the way, that the presence of an azeotropic point on the phase diagram points out the non ideality of the liquid phase). The shape of the hM-curve at P3 is very singular and deserves some comments. One observes that for small and high values of z1 (the mole fraction of CO2), the mixture is in a liquid state and the corresponding hM-curve (at P3) is superimposed with the hM-curve plotted at P4 = 40 bar (at P4, the 10 - Environment ACS Paragon-Plus

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mixture is liquid on the whole composition range). The reason for which the liquid branches of the hM-curves at P3 and P4 are so similar can be explained by the incompressible character of liquid phases under moderate pressures. More remarkably, the hM-curve at P3 = 37 bar is made up of five branches: two liquid ones (for small and high values of z1), two branches associated to the two VLE encountered at T and P3 and one gas branch (the middle one). At the azeotropic pressure which is an intermediary pressure between P3 and P4, the hM-curve exhibits a singular shape (see Fig. 2.c). It is completely superimposed with the hM-curve at P4 except in one point: the azeotropic point, the composition of which is denoted zaz. At z1 = zaz, the hM-curve is discontinuous and is made up of a vertical line connecting the point representing the azeotropic liquid phase Laz (located on the hM-curve P4) to the point characterizing the azeotropic gas phase Vaz. The few frequent phase behavior shown in Fig. 2.d can be observed in systems exhibiting both absolute azeotropy and a temperature minimum on the critical locus in the (P, T) plane. At 293.15 K, the isothermal phase diagram has split in two parts, each of them bounded by a mixture critical point. Fig. 2.e represents the isothermal and isobaric hM-curves associated to the horizontal lines drawn in Fig. 2.d. One first observes that the curves P1 and P2 of Fig. 2.e are rather similar to the curves P1 and P2 of Fig. 2.b. The hM-curve P3 is however quite singular. Indeed, although pressure P3 belongs to the pressure range  P2sat (T), P1sat (T)  , no VLE exists at T = 293.15 K and P3 explaining why, the hM  curve calculated at pressure P3 is only made up of one branch (it is neither a liquid branch nor a gas branch but instead a fluid branch due to the existence of 2 critical points at pressures above and below P3). In addition, the proximity between the shapes of the 3-branch hM-curve P2 and the onebranch hM-curve P3 illustrates a memory effect. This memory effect can also be illustrated by the similarity between the 3-branch hM-curve P4 in Fig. 2.e and the 5-branch hM-curve P3 in Fig. 2.b: indeed, the inflection point lying on the hM-curve P4 in Fig. 2.e is issued from the presence of a second VLE at smaller pressures. Unusual and interesting shapes of hM-curves are also observed in systems in which the vapor-liquid (VL) and liquid-liquid (LL) regions superimpose each other. In isothermal phase diagrams, the phenomenon results in the presence of a vapor-liquid-liquid equilibrium line separating the VL and LL domains; this instance is exemplified with the water + 1,3,5-trimethylbenzene system in Fig. 3.a. In addition, note that the binary mixture chosen for illustration shows a heteroazeotropic phase behavior as well. Under low pressure P1, the system is gaseous regardless of the composition and 11 - Environment ACS Paragon-Plus

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exhibits weak enthalpy of mixing values (see Fig. 3.b). Under pressure P2, pure component 1 is gaseous, pure component 2 is in a liquid state and the resulting mixture can be either in liquid, vapor, or vapor-liquid state. The corresponding hM-curve is classically made up of three branches. The heteroazeotropic behavior of the considered system induces the simultaneous existence of two VLE under the same pressure P3 and at the same temperature T, as previously observed in the CO2(1) + ethane(2) system. Consequently, a five-branch hM-curve is found at P3 (see Fig. 3.b). Due to the near immiscibility of the hydrocarbon in the aqueous liquid phase, only four branches are actually visible: two VLE branch (the second and fourth ones), a liquid-like branch (located on the left hand side) and a gas-like branch (the third one). For pressures P4 and P5 above the pressure of the VLLE, two liquid phases in equilibrium (LLE) are observed. Still because of the quasi immiscibility of the hydrocarbon in the aqueous phase, only two branches are visible on the hM-curves at P4 and P5 (instead of three). Due to the large difference in pressure between P4 and P5 (100 bar), the effect of the pressure on hM-curves of liquid phases becomes visible: indeed, although similar, the hM-curves plotted at P4 and P5 are not superimposed. For a pressure equal to the pressure of the VLLE, the hM-curve is similar to the hM-curve plotted at P3 except that the gas branch (the third one) reduces to a single point denoted V* (see Fig. 3.c). The three-phase region is bounded by a triangle, the vertices of which are the points characterizing the two liquid phases (Lα* and Lβ*) and the gas phase (V*) involved in the VLLE.

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3. A short presentation of the PPR78 model As explained in the introduction, the PPR78 model relies on the Peng-Robinson EoS [2,3] with classical Van der Waals mixing rules [4-14]. Note that the PPR78 model can also be seen as an EoS/gE model combining the Peng-Robinson EoS and a Van Laar-type excess function [11,20]. In this model, the binary-interaction parameters k ij (T) are temperature-dependent and are estimated through the group-contribution concept:     k ij (T) =  E ij (T) − ∆ ij (T)  / Θij (T)  Bkl Ng Ng  −1 1   298.15  A kl (αik − α jk )(αil − α jl )  E ij (T) = −  2 k =1 l =1   T/K    2  ∆ ij (T) = δi − δ j with : δi (T) = a i (T) / bi   Θ (T) = 2δ δ i j  ij

∑∑

(

(17)

)

In Eq. (17), a i and bi are respectively the temperature-dependent attractive parameter and the temperature-independent covolume of pure i [2,3]. Eij is the so-called Van Laar interaction parameter [11,20]. N g is the number of different groups defined by the method (for the time being, twenty groups are defined and N g = 20 ). αik is the fraction of molecule i occupied by group k (occurrence of group k in molecule i divided by the total number of groups present in molecule i ). A kl = A lk and Bkl = Blk (where k and l are two different groups) are constant group-interaction parameters determined in our previous papers [4-14]. Details about the calculation of h M and cM P with the PPR78 model can be found in appendix A.


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4. Interest of a temperature dependence of the kij coefficient for predicting hM and cPM data As previously illustrated by Jaubert et al. [5], the kij coefficient may have such an important influence on the quantification of the attractive forces by the EoS that the phase behavior of a binary system may be completely upset by small kij variations. This coefficient – frequently assumed as constant (i.e., temperature independent) for a given binary system – needs to be adjusted on VLE data in order to catch the experimentally-observed phase behavior of the considered mixture. In most of the cases, this practice allows both a good restitution of the data by the EoS as well as safe predictions of fluid phase equilibrium not only in the temperature and pressure ranges considered for the regression but often beyond. The derived properties of the phases (such as heat capacity of mixing and enthalpy of mixing) are generally few considered to fit the kij coefficient. Eqs. (24) to (28) and (31) to (34) in Appendix A point out that the calculation of the enthalpy change on mixing and of the heat capacity change on mixing depends on the kij coefficient but also on the successive derivatives of the kij coefficient with respect to the temperature. When a constant kij is considered, these derivatives are naturally equal to zero. Because of these kij-derivatives, a property change on mixing (e.g., hM or cPM) of a mixture at a specified temperature T0 and pressure P0, calculated using a given cubic EoS with Van der Waals mixing rules and a fixed value of the kij coefficient at T0, may have different values depending on the nature of the temperature-dependent function used for evaluating the kij coefficients. Indeed, even if two different temperature-dependent functions k ij(1) (T) and k ij(2) (T) lead to the same kij value dk ij(1) dT

at (T0 ) ≠

T0 dk ij(2) dT

( k ij(1) (T0 ) = k ij(2) (T0 ) ),

their

derivatives

may

return

different

values:

(T0 ) thus inducing different values of hM and cPM.

As an illustration, the experimental hM-curve of the benzene(1) + isooctane(2) system at T = 298.15 K and under P = 1.0 atm is shown in Fig. 4.a. To model these data, three curves were calculated by using the Peng-Robinson EoS with Van der Waals mixing rules and three different kij(T) expressions. These three expressions of the binary interaction parameter were parameterized in order to lead to the same kij value at 298.15 K: kij = 0.0029, in accordance with the PPR78 model. They are nevertheless characterized by three different dkij/dT values: (i) dkij/dT = −1.7×10−4 K–1 14 - Environment ACS Paragon-Plus

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Energy & Fuels

(value predicted by the PPR78 model), (ii) dkij/dT = −5.7×10−5 K–1 (determined in order to obtain the best fit to experimental data) and (iii) dkij/dT = 0.0. The influence of dkij/dT on hM is very significant, in spite of its small magnitude. Similar illustrations and explanations apply to the influence of d2kij/dT2 on cPM. The curves in Fig. 4.b were calculated by considering the same kij value (kij = 0.0029, as predicted by the PPR78 model) and the same value of its first derivative (dkij/dT = −1.7×10−4 K–1, as predicted by the PPR78 model) but different values of the second derivative d2kij/dT2. It is again observed that the cPM values change a lot as d2kij/dT2 varies from −1.0×10−7 K–2(value fitted on experimental data) to 2.0×10−6 K–2 (value predicted by the PPR78 model). This example emphasizes how decisive the way used to express the kij coefficient is. Making it temperature dependent leads to more elaborated expressions for the hM and cPM properties and brings in return, more flexibility to the model. Therefore, the use of a kij(T) function instead of a constant kij can grandly improve the representation of these properties, provided kij(T) functions are well-parameterized.


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5. Predicting hM and cPM data with the PPR78 model 5.1. Database Table 1 presents the list of the 144 pure components involved in this study. The pure fluid physical properties (Tc, Pc and ω) used in this study originate from two sources [21,22]. The handbook by Poling et al. [21] was used for alkanes, aromatics, naphthenes, alkenes, mercaptans, CO2, N2, H2S and H2. As some mercaptans and alkenes were missing in this book, the DIPPR database [22] was chosen instead. In order to benchmark the PPR78 model, we endeavored to collect most of the hM and cPM data available in the open literature for binary systems containing alkanes, aromatics, naphthenes, alkenes, mercaptans, CO2, N2, H2S and H2 [18,23-425]. Tables 2 and 3 in Appendix B detail the sources of the experimental hM and cPM data considered. Tables 2 and 3 also provide the temperature, pressure, hM (or cPM) and composition ranges for each of the binary systems. Note that experimental cPM data were only found for mixtures containing alkanes, aromatic compounds and naphthenes. In summary, our database includes 24,436 hM data (18,254 data for liquid mixtures, 4,334 points for gaseous mixtures and 4,848 points for mixtures in two-phase equilibrium) over 469 binary systems, and 2,251 cPM data (for liquid mixtures only) over 107 binary systems.

5.2. Proposal of a new criterion to evaluate the capacity of an EoS to predict enthalpies of mixing Criterion used for characterizing the predictive capacity of EoS in terms of hM and cPM are classically: - the mean relative errors: n  100 h  ∆h M  M M M ∆h M % =  M  with ∆h = h exp − h cal n h i=1  h exp    i   nc  ∆c M   M 100 M M M ∆ c % =  M P  with ∆c P = c P,exp − c P,cal  P n c i =1  c P,exp    i 

∑

∑

- the mean absolute errors:


(18)

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Energy & Fuels

   M ∆h =     ∆c M =  P

nh

∑ ( ∆h M )i i =1

nh

(19)

nc

∑ ( ∆cMP )i i =1

nc

where nh and nc denote the number of hM and cPM data points, respectively. As previously discussed, when molecules are few polar and few associating (and this is often the case within petroleum blends), pure-component terms provide an excellent estimation of the molar enthalpy of the mixture. Therefore, the enthalpy-of-mixing terms can be seen as a correction, just aimed at improving the first estimation given by the pure-component ground terms. In other words, with few-polar and few-associating mixtures, hM terms are generally negligible with respect to purecomponent terms in the energy rate balance. Typically, hM terms are very small in alkane mixtures (several J/mol or several tens of J/mol) but are not negligible in petroleum mixtures containing CO2, H2O, alcohols, etc. (likely to reach up to several tens of kJ/mol). When the parameters involved in the kij correlations are not directly fitted on enthalpy-of-mixing data (and this is for instance, the case for the PPR78 model), the relative deviations between the calculated and experimental hM data ( ∆h M % ) can be very important and reach values sometimes greater than 100 %. However, since hM quantities are only used to evaluate the molar enthalpies, hin and hout, involved in the energy rate balance (see Eq. (1)), the relative hM deviations do not necessarily matter: only their impact on the accuracy of the energy balance should be actually addressed. In order to assess how errors on hM may affect the energy balance, it was decided to adopt a M M − h exp in terms of temperature effect ∆Th through: criterion converting the difference ∆h M = h calc

 For one datapoint:      For a series of data: 

∆Th =

∆h M ∆h M = cP z1cP,pure 1 + z 2c P,pure 2 + cPM nh

∆Th =

∑ ( ∆Th )i i =1

nh

where cP is the molar isobaric heat capacity of the mixture.


(20)

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Page 18 of 84

Practically speaking, the quantity ∆Th indicates the misestimating of the final temperature of a mixture obtained by mixing two pure compounds in isobaric and adiabatic conditions. Because the temperature is one of the most used and easy-to-work-with process variables, this criterion allows a better understanding of the reliability of the model. In Eq. (20), the pure-component heat capacities result from the addition of an ideal gas term and a residual term: gas res cP,pure i (T, P) = cideal P,pure i (T) + c P,pure i (T, v pure i )

(21)

with v pure i , the molar volume of pure i at given T and P. gas The ideal gas terms ( cideal P,pure i ) were estimated using the DIPPR database [21]. The residual term is

calculated as explained in Appendix A.2.

5.3. Prediction of hM data The capacity of the PPR78 model to predict hM data is provided in Table 2 for each binary system and sumed up in Table 4 which provides some synthetic statistics which are graphically illustrated in Fig. 5. The binary systems were divided up in nine different chemical families: alkanes, aromatic

compounds, naphthenic compounds, CO2, N2, H2S, mercaptans, alkenes and H2. A binary system of a given family contains at least one compound of this family, the second one belonging either to the same family or to a previous one. As an example, binary systems of the naphthenic-compound family contain at least one cycloalkane, the second component being an alkane, an aromatic compound or a cycloalkane. Table 4 and Fig. 5.a point out quite important relative mean deviations in most of the families, and more especially in the alkane and naphthene families. Absolute mean variations, shown in Fig. 5.b, are rather homogeneous along the families (< 200 J/mol), excepted in the naphthenes and mercaptans families for which much more important deviations are observed. However, these trends are completely upset when the deviations are converted in terms of temperature (see Fig. 5.c). It is then observed that the average temperature change ∆Th in the alkane family is only equal to 0.5 K which seems nearly negligible. This result can be justified by a rather weak absolute mean deviation of 88 J/mol (this weak value is certainly negligible with respect to pure component terms in an energy balance). In the naphthene family, the ∆Th value is around 2 K (and the corresponding mean relative deviation ∆h M % is equal to 1490 % which is the highest value observed in Table 4). This ∆Th


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Energy & Fuels

value is just a little above the alkane value but dramatically lower than the mercaptan value which reaches 29 K (whereas the associated relative mean deviation ∆h M % in the mercaptan family only reaches 363 %). In summary:

∆Th,naphthenes > ∆h % mercaptans Therefore, it appears that the ∆h M % and ∆Th criteria are strictly non equivalent to discuss the capacity of a model to predict hM data. As explained before, the ∆Th criterion is definitively prefered in the present study because it provides a fair overview on the model accuracy to perform an energy balance. Some predictions of hM data by the PPR78 model are shown in Figs. 6 to 10. These predictions were deemed as representative of the overall results. In addition, the results are sorted in three different classes: -

systems showing VLE,

-

liquid systems on the whole composition range,

-

gaseous systems on the whole composition range.

Figs. 6 and 7 show binary systems for which experimental hM data were found inside or in the vicinity of a two-phase equilibrium region. At a temperature and a pressure such that a two-phase equilibrium exists, a hM curve is made up of 3 branches as explained above and as illustrated in Fig. 1. We also explained in section 2.3 that when at a fixed temperature and pressure, a binary system exhibits a two-phase equilibrium, excess enthalpies (hE) are generally much lower than enthalpies of ideal mixing (this last quantity, hM,id, essentially involves pure-component vaporization enthalpies ∆vapHi). This is why we previously claimed that the capacity to predict mixing enthalpies inside two-phase regions is primarily linked to the choice of an EoS for pure components. Consequently, to predict such data, an EoS needs to: - accurately predict the VLE of binary systems (in order to properly locating the intersection points between the three branches of the hM-curves), - accurately predict enthalpies of vaporization of pure components.


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The Peng-Robinson EoS for pure components is generally acknowledged to provide accurate estimations of vaporization enthalpies for a wide variety of compounds. In addition, the groupinteraction parameters of the PPR78 model were fitted in order to reproduce VLE data with the best possible accuracy. It is thus not surprising to observe quite satisfactory prediction of hM-curves in Figs 6 and 7. It must be stressed again that these good predictions of hM data in two-phase domains are nearly independent of the ability of the PPR78 model to predict excess enthalpies. To evaluate the capacity of the PPR78 model in predicting hE data, phase change must not occur at fixed T and P (the pure components and the resulting mixture have to remain in the same aggregation state). From a quantitative point of view, hM values in these two-phase regions may reach several kJ/mol or several tens of kJ/mol (because mixing enthalpies and vaporization enthalpies have the same order of magnitude). Whereas relative mean deviations ∆h M % between experimental data and their prediction by the PPR78 model are generally quite reasonable, absolute mean deviations ∆h M (and ∆Th as well) can be rather important due to the high order of magnitude of mixing enthalpies. Enthalpies of mixing of liquid systems are shown in Figs. 8 and 9. This time, no phase change occurs during the mixing process so that enthalpies of mixing and excess enthalpies are rigorously equal (hE = hM). In agreement with our expectations in section 5.3, one classically observes that hM values are weak when considering few polar and non-associating systems (see e.g., the alkane + alkane and alkane + alkene systems shown in Figs. 8a, 8b, 9b, 9c). Weak hM values are naturally also oberved in systems forming near ideal solutions (see Figs. 8d and 8f). Although important relative deviations may exist between experimental data of such systems and their prediction by the PPR78 model (see e.g., Fig. 8.a), the predicted orders of magnitude are systematically correct. Because of the low experimental hM values and the satisfactory predictions of their orders of magnitude, absolute mean deviations are small (generally less than 100 J/mol) and deviations expressed in temperature ( ∆Th ) remain reasonable which makes the model perfectly compatible with energy balances applied to mixtures containing alkanes and/or alkenes. An increase of size difference between both molecules of a binary system makes hM values increasing as illustrated in Fig. 8.c. For instance, enthalpies of mixing of the benzene + eicosane (a linear alkane having 20 carbon atoms) system reach 1.2 kJ/mol, which is one or two orders of magnitude more than for alkane + alkane systems. Furthermore, mixtures made up of an aromatic hydrocarbon and a non-aromatic hydrocarbon (e.g. an alkane, an alkene or a naphthene) are generally characterized by more important hM values than


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Energy & Fuels

in mixtures containing two non-aromatic hydrocarbons or two aromatic hydrocarbons. As an illustration, hM values observed in the 3-methylpentane + n-heptane system (see Fig. 8.b) are much lower than those observed in the n-hexane + benzene system (see Fig. 8.c) or in the cyclohexane + benzene system (see Fig. 8.e) whereas all these systems contain components of similar sizes. Enthalpies of mixing of CO2-containing liquid systems are generally quite well predicted by the PPR78 model as illustrated in Figs. 9.a and 9.d. These systems are generally characterized by important hM values (up to several kJ/mol even outside two-phase regions) and thus non-negligible absolute deviations but reasonable relative deviations. Fig. 10 illustrates the results obtained in gaseous binary systems which essentially contain small molecules encountered in natural gases. Similarly to what was observed in liquid systems, the PPR78 model is generally able to qualitatively reproduce hM curves (shapes and signs). The series of hM curves represented in Fig. 10.e is a good illustration of this statement. Experimental data show that enthalpies of mixing of the ethylene + propane system at 373.15 K change of sign when pressure goes from P1 = 75 bar to P4 = 150 bar. This trend is properly predicted by the PPR78 model although a slight delay in pressure is observed in comparison with experimental data. Quantitatively speaking, the same conclusions as before can be drawn: relative mean deviations are rather high for some of the systems shown in Fig. 10 (see e.g., Figs. 10.a, 10.b and 10.c) whereas the corresponding absolute mean deviations remain acceptable. The results obtained with the N2 + ethylene and H2 + methane systems (see Figs. 10.d and 10.f) are remarkably accurate, especially since the group-interaction parameters of the PPR78 model were never fitted on hM data.

5.4. Prediction of cPM data The capacity of the PPR78 model to predict cPM data is provided in Table 3 for each binary system. Among the nine different classes of compounds considered in the present study (and detailed in section 5.1), cPM data were only found in binary systems containing alkanes, aromatic compounds and naphthenes. Table 5 provides the overall mean absolute deviations and overall mean relative deviations calculated over the 2,251 points present in the databank. Deviations are also given for each of the three families of compounds that were defined (alkanes, naphthenes and cycloalkanes). Histograms illustrating these statistics are represented in Fig. 11. Similarly to what was observed with hM data, the best predictions of heat capacities of mixing are observed in the alkane family with an absolute mean deviation lower than 0.4 J/mol/K, which may seem acceptable. The highest


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deviations are found in the naphthene family wherein the absolute mean deviations reach no less than 25 J/mol/K. An overview of these predictions is presented in Fig. 12. Although qualitatively correct, it must be acknowledged that the PPR78 model generally fails in quantitative representations of cPM data.


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6. Conclusion In this paper, it was decided to benchmark the PPR78 EoS regarding the prediction of two derived properties that are essential to write energy balance equations: enthalpies of mixing (hM) and heat capacities of mixing (cPM). To do so, we tried to collect the largest possible number of experimental data in binary systems containing alkanes, alkenes, aromatic compounds, cycloalkanes, permanent gases (CO2, N2, H2S and H2) and mercaptans. Results for aqueous systems are under publication [426]. The study led us to the three following conclusions: -

the PPR78 model provides nearly systematically qualitatively satisfactory results: it often predicts the right signs and shapes of hM- and cPM-curves.

-

from a quantitative point of view, predictions of hM and cPM data have generally the right order of magnitude but are not as accurate as expected.

-

although predictions of hM data could be certainly improved, we have shown that for most of families of compounds investigated in this study, the observed deviations are expected to have a small impact on the accuracy of energy balances.

Note that a similar accuracy is expected from the PR2SRK model which is a predictive version of the Soave-Redlich-Kwong EoS since we previously showed that both these models (PR2SRK and PPR78) exhibited nearly identical capacities to predict phase equilibrium data [20,427]. The kij(T) function of the PPR78 model can thus be claimed to be: -

adequate for the prediction of VLE data (as proved by our previous studies [4-14]),

-

interesting but non optimal regarding the prediction of derived properties.

Starting from this last observation, it could be possible to improve the PPR78 model by simultaneously fitting its group-contribution parameters on VLE, hM and cPM data. Therefore, this study lays the foundation stone of an ambitious future work.


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Appendix A. Calculation of hM and cPM with the PPR78 model A.1. Calculation of hM Cubic EoS can be written under the general form: P(T, v, z ) =

a m (T, z ) RT − v − b m ( z ) [v − r1 b m ( z )][v − r2 b m ( z )]

(22)

where P is the pressure of the fluid, T its temperature and v its molar volume; z denotes the mole fraction vector. R is the gas constant. Parameters r1 and r2 are two universal constants only depending on the considered EoS. For the Peng-Robinson EoS:

 r = −1 − 1   r = −1 +  2

2 2

.

Functions a m (T, z ) and b m (T, z ) are expressed following classical mixing rules (also named Van der Waals mixing rules): p p   a (T , z ) =  m  i =1 j=1   p   z i bi b m (z) = i =1 

∑ ∑ zi z j

a i (T)a j (T) [1 − k ij (T)] (23)

∑

R = 8.314472 J ⋅ mol−1 ⋅ K −1   −1 + 3 6 2 + 8 − 3 6 2 − 8 ≈ 0.253076587 X = 3   RTc,i X with Ω b = ≈ 0.0777960739  bi = Ω b Pc,i X+3  with  . 2  2 2   R Tc,i 8 ( 5X + 1) T  a = Ω ≈ 0.457235529 1 + mi 1 −  with Ωa =  i a    Pc,i  T 49 − 37X c,i     if ω ≤ 0.491 m = 0.37464 + 1.54226ω − 0.26992ω2 i i i i  if ωi > 0.491 mi = 0.379642 + 1.48503ωi − 0.164423ωi2 + 0.016666ωi3 The enthalpy change on mixing h M is defined by Eq. (3). Introducing residual molar enthalpies, this definition can then be rewritten as: M

h (T, v, z ) = h

res

p

(T, v, z ) −

res i (T, v pure i ) ∑ zi h pure i =1


(24)

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with vpure i , the molar volume of pure compound i at the same temperature T and the same pressure P as the mixture. From classical thermodynamics, residual molar enthalpies are given by the general expression:  res  ∂a res  res h (T, v, z ) = a (T, v, z ) − T  + P(T, v, z ) ⋅ v − RT ∂T    v, z  v  res [ P(T, v, z) − RT / v] dv  with a (T, v, z ) = −  +∞

(25)

∫

Combining Eqs. (22) and (25), one obtains:

h res (T, v, z ) =

RTb m (z ) a m (T, z ) − v − b m (z ) [v − r1 b m (z )][v − r2 b m (z )]  1  ∂a m    v − r1 b m (z )  +  a m (T, z ) − T    ln  b m (z ) ⋅ (r1 − r2 )   ∂T  z   v − r2 b m (z ) 

(26)

Note that the expression for pure component residual molar enthalpy is simply deduced from the previous equation: res h res pure i (T, v pure i ) = h (T, v pure i , z i = 1)

(27)

According to Eq. (23), the derivative of a m with respect to T writes:  ∂a m    =  ∂T  z

p

p

∑∑ i =1 j=1

da da  a j dTi + a i dTj dk ij    zi z j (1 − k ij ) − a ia j  dT  2 a ia j  

(28)

According to Eq. (17), the derivative of k ij with respect to T is:

dk ij dT

=

Θij (E′ij − ∆′ij ) − Θ′ij (Eij − ∆ij ) Θij2

(29)

with:  da R 2Tc a  i = −mi Ω a × i Pc T  dT  δ′ = dδ / dT =  da i  / (2b a ) i i i    i  dT   Θ′ij = dΘij / dT = 2(δ′i δ j + δi δ′j )  ∆′ij = d∆ij / dT = 2(δi − δ j )(δ′i − δ′j )  Bkl Ng N g   298.15  Akl −1  A kl  Bkl 1 (α ik − α jk )(αil − α jl ) − 1   E′ij = dEij / dT = 2 T  A kl   T / K  k =1 l =1  

∑∑


(30)

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A.2. Calculation of cPM Similarly to the enthalpy of mixing, the heat capacity of mixing at constant pressure can be expressed in terms of residual properties (that are convenient when working with EoS): res cM P (T, v, z ) = c P (T, v, z ) −

p

∑ zi cresP,pure i (T, vpure i )

(31)

i =1

According to classical thermodynamics, the residual heat capacity at constant pressure is given by: res 2 cres P (T, v, z ) = c v (T, v, z ) − R + T( κT ⋅ v)(β ⋅ P)   (β ⋅ P) := (∂P / ∂T) v,z  with: ( κT ⋅ v) := −1 / (∂P / ∂v)T,z   c res = (∂u res / ∂T) v,z and  v

(32) u res = a res − T(∂a res / ∂T) v,z

For a cubic EoS expressed from Eq. (17), these quantities write:

 (∂a m / ∂T)z R − (β ⋅ P) = v − b m (z ) [v − r1 b m (z )][v − r2 b m (z )]   −1  a m (T, z ) ⋅ [ 2v − (r1 + r2 )b m (z ) ]  −RT  +  ( κT ⋅ v) =  2 [v − r1 b m (z )][v − r2 b m (z )]    [v − b m (z )]   ∂ 2a m   v − r1 b m (z )  −T cres =   ln    v (r1 − r2 )b m (z )  ∂T 2   v − r2 b m (z )  z 

(33)

According to Eq. (23), the second derivative of a m with respect to T writes:

 ∂ 2a m  =  2   ∂ T  z

p

p

∑∑ i =1 j=1

 d 2a i da da a + 2 dTi dTj + a i j  dT 2 zi z j  (1 − k ij ) 2 aia j  

d 2a j dT 2

−2

dk ij a j

da i dT

dT

2 a ia j

+ ai

da j dT

 d 2 k ij  − a ia j  (34) dT 2  

According to Eq. (17), the second derivative of k ij with respect to T is: d 2 k ij dT 2

=

Θij2 (E′′ij − ∆′′ij ) + [2(Θ′ij )2 − ΘijΘ′′ij ](Eij − ∆ij ) − 2Θ′ijΘij (E′ij − ∆′ij ) Θ3ij

with:


(35)

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 d 2a 2 2   i = Ω mi R Tc ×  1 − a i   a  T ⋅ da i  T ⋅ Pc  dT 2 dT    2   d 2 a i  da i    δ′′i = d 2δi / dT 2 =  2a i −  /  4bi a 3i / 2  2  dT     dT       2 2 Θ′′ij = d Θij / dT = 2(δ′′i δ j + 2δ′i δ′j + δi δ′′j )  2 2 2 ∆′′ij = d ∆ij / dT = 2  (δ′i − δ′j ) + (δi − δ j )(δ′′i − δ′′j )   Bkl Ng N g   Bkl   298.15  Akl −1 1 B 2 2 k l E′′ij = d Eij / dT = − (αik − α jk )(αil − α jl ) 2  − 1    2 k =1 l=1 T  A kl   T / K   

∑∑


(36)

Energy & Fuels

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

Appendix B. Considered data - Related references and

deviations. Tables 2 and 3 provide the list of the binary systems considered for the present study. For each of them, the references of the experimental data points and the deviations observed with the PPR78 model are provided.


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(421)

Fujii, S.; Tamura, K.; Murakami, S. Thermodynamic properties of mixtures containing 1,3-diphenyl-propane at 298.15 K. Thermochim. Acta 1995, 257, 1-12.

(422)

Rajagopal, E.; Subrahmanyam, S. V. Excess Thermodynamic Functions of the Systems Cyclohexane + Isomeric Xylenes. Bull. Chem. Soc. Jpn. 1981, 54, 282-284.

(423)

Siddiqi, M. A.; Svejda, P.; Kohler, F. A Generalized van der Waals Equation of State. II. Excess Heat Capacities of Mixtures Containing Cycloalkanes (C5, C6), Methylcycloalkanes (C5, C6) and n-Decane. Ber. Bunsen-Ges. Phys. Chem. 1983, 87, 1176-1181.

(424)

Shiohama, Y.; Ogawa, H.; Murakami, S.; Fujihara, I. Excess molar isobaric heat capacities and isentropic compressibilities of (cis- or trans-decalin + benzene or toluene or iso-octane or n-heptane) at 298.15 K. J. Chem. Thermodyn. 1988, 20, 1183-1189.

(425)

Tamura, K. Excess heat capacities of the mixtures containing methylcyclohexane at 298.15 K. Fluid Phase Equilib. 2001, 182, 303-312.

(426)

Qian, J., Privat R., Jaubert, J.-N. Predicting the phase equilibria, critical phenomena and mixing enthalpies of binary aqueous systems containing alkanes, cycloalkanes, aromatics, alkenes and gases (N2, CO2, H2S, H2) with the PPR78 equation of state. Ind. Eng. Chem. Res. 2013 (submitted for publication).

(427)

Jaubert, J.-N., Qian, J., Privat R., Leibovici, C.F. Reliability of the correlation allowing the kij to switch from an alpha function to another one in hydrogen-containing systems. Fluid Phase Equilib. 2013, 338, 23-29.


Page 48 of 84

Page 49 of 84

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

Energy & Fuels

List of Tables Table 1. List of the 144 pure components used in this study. Table 2. Binary system database for hM data. Table 3. Binary system database for cPM data. Table 4. Deviations between experimental hM data and their prediction by the PPR78 model. The results are sorted out by chemical family. Table 5. Deviations between experimental cPM data and their prediction by the PPR78 model. The results are sorted out by chemical family.


Energy & Fuels

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

Page 50 of 84

Table 1. Component methane ethane propane n-butane n-pentane n-hexane n-heptane n-octane n-nonane n-decane n-undecane n-dodecane n-tridecane n-tetradecane n-pentadecane n-hexadecane n-heptadecane n-octadecane n-nonadecane n-eicosane 2-methylpropane(isobutane) 2,2-dimethylpropane 2,2,3-trimethylbutane 2-methylbutane 2,2-dimethylbutane 2,3-dimethylbutane 2-methylpentane 3-methylpentane 2,2-dimethylpentane 2,3-dimethylpentane 2,4-dimethylpentane 2,2,4-trimethylpentane(isooctane) 2-methylhexane 3-methylhexane 2,2-dimethylhexane 2,5-dimethylhexane 3,3-dimethylhexane 3,4-dimethylhexane 2,2,5-trimethylhexane 2-methylheptane 4-methylheptane 2,2-dimethylheptane 2-methyloctane 2,2,4,4,6,8,8-heptamethylnonane benzene methylbenzene(toluene) 1,2-dimethylbenzene(o-xylene) 1,3-dimethylbenzene(m-xylene) 1,4-dimethylbenzene(p-xylene) ethylbenzene

Short name 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 2m3 22m3 223m4 2m4 22m4 23m4 2m5 3m5 22m5 23m5 24m5 224m5 2m6 3m6 22m6 25m6 33m6 34m6 225m6 2m7 4m7 22m7 2m8 Hm9 B mB 12mB 13mB 14mB eB

Component 1,2,3-trimethylbenzene 1,2,4-trimethylbenzene 1,3,5-trimethylbenzene 1-metylethylbenzene(cumene ) propylbenzene butylbenzene tertiobutylbenzene p-cymene naphthalene 1-methylnaphthalene 2-methylnaphthalene 1,1’-biphenyl diphenylmethane phenanthrene cyclopropane cyclopentane methylcyclopentane trans-1,3-dimethylcyclopentane cis-1,2-dimethylcyclopentane 1,1-dimethylcyclopentane ethylcyclopentane cyclohexane methylcyclohexane ethylcyclohexane propylcyclohexane isopropylcyclohexane cycloheptane cyclooctane 1,2,3,4tetrahydronaphthalene(tetralin) trans-decalin cis-decalin 1,1’-bicyclohexyl carbon dioxide nitrogen hydrogen sulfide methyl mercaptan ethyl mercaptan propyl mercaptan butyl mercaptan isopropyl mercaptan isobutyl mercaptan tert-butyl mercaptan sec-butyl mercaptan hydrogen ethylene propene 1,2-propadiene 1-butene trans-2-butene cis-2-butene

Short name 123mB 124mB 135mB iprB prB buB tbuB tbu pcy BB 1mBB 2mBB Bph Dph phe C3 C5 mC5 t13mC5 c12mC5 11mC5 eC5 C6 mC6 eC6 prC6 iprC6 C7 C8 tet tCC6 cCC6 bcy CO2 N2 H2S 1sh 2sh 3sh 4sh iprsh ibush tbush sbush H2 a2 a3 aa3 1a4 t2a4 c2a4


Component 2-methyl-1-butene 2-methyl-2-butene 3-methyl-1-butene 2-ethyl-1-butene 1,3-butadiene 1-pentene 4-methyl-1-pentene 1-hexene trans-2-hexene cis-2-hexene trans-3-hexene trans-trans-2,4-hexadiene 1,5-hexadiene 1-heptene trans-2-heptene cis-2-heptene trans-3-heptene 1-octene trans-3-octene cis-3-octene trans-4-octene cis-4-octene myrcene 1-nonene 1-decene 1-undecene 1-dodecene 1-hexadecene 1-octadecene styrene alpha-methylstyrene 2-methylpropene 2-methyl-1,3-butadiene 2-methyl-1-pentene beta-pinene cyclopentene 1,3-cyclopentadiene 3-methylcyclopentene cyclohexene 1,3-cyclohexadiene 1,4-cyclohexadiene 1-methyl-cyclohexene 1,5-cyclooctadiene alpha-pinene

Short name 2m1a4 2m2a4 3m1a4 2e1a4 13a4 1a5 4m1a5 1a6 t2a6 c2a6 t3a6 tt24a6 15a6 1a7 t2a7 c2a7 t3a7 1a8 t3a8 c3a8 t4a8 c4a8 myr 1a9 1a10 1a11 1a12 1a16 1a18 Ba2 Bma2 2ma3 2m13a4 2m1a5 bp aC5 13aC5 3maC5 aC6 13aC6 14aC6 1maC6 15aC8 ap

Page 51 of 84

6-8

298.15413.20

6-9

298.15298.15

6-10

293.15308.15

1.013251.01325 1.00000488.0000 0 1.010001.01000 1.00000485.0000 0 1.013251.01325 1.010001.01325 1.010001.01000 1.000001.01325 1.010001.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.010001.01000 1.013251.01325 1.010001.01325 1.013251.01325

5-7 5-8 5-10

6-11 6-12 6-14 6-16 7-8 7-10 7-12 7-16 8-10 8-12 8-16 10-12 10-16 22m3-8 22m4-6 22m4-7 22m4-8 22m4-10

298.15308.15 283.15308.15 298.15298.15 293.15349.15 298.15413.20 298.15298.15 298.15298.15 293.15323.15 298.15298.15 298.15298.15 293.15323.15 298.15298.15 293.15293.15 323.15323.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15

0.50000.5000 0.50000.5000 -

References

293.15298.15

5-6

-

-

0

24

0

23

50.8

17.1

-

0

31

0

23

48.1

22.8

0.16

-

0

29

0

23

52.5

45.2

0.27

-

0

37

0

23

54.2

8.9

0.06

-

0

28

0

23

57.3

35.4

0.20

-

1

27

0

23-24

55.0

2.9

0.02

-

1

29

0

23-24

57.4

9.2

0.05

-

0

20

0

23

61.1

24.7

0.12

(T,P,hM,z)

6-7

4-8

-

Deviations ∆h M %

(T,P,hM,y)

1.013251.01325

4-6

-

0.36500.8150 0.36600.8970 0.36300.7240 0.33100.7810 0.40000.7550 0.39700.6000 0.32800.6280 0.39400.7040

Number of points (T,P,hM,x)

293.15293.15

3-8

-

z1 range (1st compound mole fraction)

5-16

3-7

16.300047.1000 23.800063.7000 70.700096.2000 9.600020.3000 44.400071.6000 2.70009.0000 10.000020.6000 34.300044.5000 20.100025.5000 149.1000 151.2000 -28.470023.4000

y1 range (1st compound gas mole fraction)

Pressure range (bar) 1.010001.01000 1.010001.01000 1.010001.01000 1.010001.01000 1.010001.01000 1.010001.01325 1.010001.01325 1.010001.01000 1.013251.01325

x1 range (1st compound liquid mole fraction)

Temperature rage (K) 344.20396.90 383.20413.20 403.20413.30 363.20393.20 403.20413.20 293.15403.20 293.15413.20 403.20413.20 293.15293.15

3-6

Enthalpy of mixing range (J/mol)

Table 2. Binary system (1st compound2nd compound)

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

Energy & Fuels

∆h M (J/mol)

∆Th / K

0.15

0.48760.6906

-

-

3

0

0

25

199.7

45.3

0.21

0.47320.5589

-

-

3

0

0

25

16.2

24.3

0.08

0.05000.9500

-

-

31

0

0

26-28

528.4

6.0

0.03

0.420022.2000

0.10040.9003

0.24800.7530

-

32

20

0

23,2931

223.2

8.9

0.04

1.90009.9000

0.10610.8931

-

-

19

0

0

32

274.2

12.3

0.05

0.410037.4000

0.04980.9620

-

-

120

0

0

25,30,3 3-35

209.4

15.9

0.07

0.590025.9800 1.060059.9000 6.700067.9000 -31.6000129.8900 0.05607.2000 1.930010.6400 5.430030.3300 33.4000111.6000 1.03904.9610 3.490020.5100 33.000087.2000 0.94005.1700 45.000049.2000 -92.52800.0000 4.20005.9000 3.970023.3700 11.360035.2000 12.780073.5500

0.04740.9818 0.04990.9829 0.04860.8986 0.03800.9860 0.05010.9510 0.05000.9500 0.05010.9500 0.26250.6651 0.05000.9500 0.05020.9499 0.46540.6417 0.05010.9499 0.50000.6279 0.29900.8550 0.18110.8142 0.05000.9500 0.10020.9000 0.05060.9498

-

-

68

0

0

36

175.4

20.1

0.08

32,3742

90.3

21.9

0.09

-

-

168

0

0

-

-

21

0

0

43

59.6

19.7

0.07

187.9

22.8

0.08

-

-

198

0

0

42,4451

0.32600.7440

-

22

20

0

23,52

226.6

2.3

0.01

-

-

19

0

0

53

65.2

4.7

0.02

-

-

19

0

0

54

32.0

6.3

0.02

19.2

12.8

0.04

-

-

19

0

0

25,42,5 5

-

-

19

0

0

56

31.6

1.1

0.00

-

-

30

0

0

54,57

11.8

1.4

0.01

-

-

7

0

0

25,42

21.3

16.4

0.05

-

-

19

0

0

54

14.0

0.5

0.00

-

-

5

0

0

25,42

41.9

19.6

0.05

-

-

17

0

0

58

267.3

196.4

0.98

-

-

5

0

0

59

1667.7

89.2

0.49

-

-

20

0

0

26

647.8

109.2

0.57

-

-

13

0

0

29,60

558.8

158.4

0.78

-

-

20

0

0

33

359.9

184.1

0.82


Energy & Fuels

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

22m4-12 22m4-16 23m4-6 23m4-7 23m4-8 23m4-10 23m4-12 23m4-16 2m5-6 2m5-7 2m5-8 2m5-10 2m5-12 2m5-16 3m5-6 3m5-7 3m5-8 3m5-10 3m5-12 3m5-16 6-24m5 24m5-7 24m5-8 24m5-12 6-224m5 7-224m5 224m5-8 224m510 224m512 224m516 22m423m4 22m42m5 22m43m5 22m4224m5 23m42m5 23m43m5 2m53m5 1-3

283.15303.15 293.15298.15 283.15313.15 298.15298.15 298.15298.15 298.15298.15 283.15303.15 293.15298.15 283.15313.15 298.15298.15 283.15313.15 298.15298.15 283.15303.15

1.010001.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

293.15298.15

1.013251.01325

283.15313.15 298.15298.15 283.15313.15 298.15298.15 283.15303.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

293.15298.15

1.013251.01325

298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15313.15 298.15323.15 298.15298.15 298.15298.15 298.15323.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 91.50302.20

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.010001.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.010001.01000 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

20.5300156.3000 58.7000254.9000 -5.58001.3500 1.67009.9300 5.970017.1800 6.440046.8800 14.9400122.1000 43.9000209.2000 0.64005.6200 2.480013.0500 6.990027.2000 7.030044.4100 14.3400104.0000 102.9000 194.8000 0.07004.7500 1.940010.9500 5.620025.0000 7.660040.6700 13.3500104.8000 114.3000 189.1000 1.30007.6600 8.140022.9900 12.890034.6100 17.8300113.3000 -11.60000.0000 1.000021.0000 5.040026.1600 12.360069.5700 20.5100117.9400 90.7000233.5000 0.41001.3500 -2.60000.0000 0.24002.2400 -10.20000.0000 -6.96000.0000 -1.11000.0000 0.43001.4000 5.1000155.3000

0.05010.9501 0.19410.9482 0.05800.9309 0.05000.9500 0.10010.9000 0.03900.9500 0.05010.9501 0.18080.9347 0.05010.9377 0.05000.9500 0.10010.9000 0.04330.9460 0.05030.9501 0.16640.8079 0.03370.9473 0.05000.9500 0.10010.9001 0.05000.9499 0.05010.9499 0.24340.7947 0.05010.9498 0.10010.9005 0.10410.8999 0.05010.9500 0.05000.9498 0.05000.9780 0.05000.9500 0.05010.9500 0.05000.9500 0.26150.9009 0.09990.8999 0.10010.9001 0.05010.8990 0.21760.7456 0.10020.9005 0.10230.8972 0.10000.9003 0.30190.8274

Page 52 of 84

-

-

83

0

0

3738,61

-

-

20

0

0

263.3

286.8

1.16

37,47

157.2

332.6

1.16

118.3

0.66

-

-

37

0

0

62

21108. 3

-

-

20

0

0

26

2130.5

152.1

0.79

-

-

9

0

0

29

1553.0

197.7

0.96

-

-

20

0

0

33

771.5

256.3

1.13

-

-

67

0

0

37-38

473.5

378.9

1.52

-

-

17

0

0

37,47

272.5

442.2

1.49

-

-

37

0

0

62

764.4

25.4

0.14

-

-

20

0

0

26

423.7

39.7

0.20

-

-

38

0

0

29,63

414.0

67.2

0.32

-

-

19

0

0

33

277.8

84.6

0.37

-

-

73

0

0

37-38

192.2

130.6

0.51

-

-

22

0

0

37,47

86.5

142.0

0.49

-

-

44

0

0

62

2647.1

27.6

0.15

-

-

20

0

0

26

542.7

42.7

0.22

505.6

71.9

0.35

-

-

41

0

0

29,6364

-

-

23

0

0

33,64

323.9

93.4

0.41

-

-

76

0

0

37-38

206.0

139.2

0.54

-

-

19

0

0

37,47

91.5

149.5

0.50

-

-

19

0

0

65

1102.1

58.9

0.30

-

-

9

0

0

65

500.7

84.5

0.40

-

-

12

0

0

65

434.3

107.6

0.48

-

-

13

0

0

65

230.6

177.5

0.65

-

-

25

0

0

66-67

2076.8

175.3

0.85

-

-

54

0

0

67-68

2112.1

182.5

0.82

-

-

34

0

0

55,67

1289.2

246.3

1.06

-

-

19

0

0

67

599.1

292.8

1.15

-

-

19

0

0

69

421.9

343.2

1.23

-

-

13

0

0

42,55

280.3

472.4

1.48

-

-

9

0

0

70

24912. 1

237.5

1.32

-

-

10

0

0

70

6233.9

104.8

0.58

-

-

10

0

0

70

7510.0

97.8

0.54

-

-

4

0

0

71

221.0

18.4

0.09

-

-

9

0

0

70

666.6

33.6

0.18

-

-

9

0

0

70

3570.3

29.1

0.16

-

-

9

0

0

70

119.6

1.2

0.01

0.13800.8920

-

11

83

0

72-73

89.8

78.5

1.87


Page 53 of 84

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

Energy & Fuels

277.00394.30 318.50403.50 343.20407.70

1.013251.01325 1.013251.01325 1.013251.01325

1-7

255.40413.30

1.01325138.0000 0

1-8

410.20418.30

1.013251.01325

2-3

200.00373.15

1.01325150.0000 0

304.50363.20 372.20403.20 403.20413.20 91.50303.20

1.010001.01000 1.010001.01000 1.010001.01000 1.013251.01325

5-B

298.15298.15

1.013251.01325

6-B

290.65323.15

0.800001.01325

B-7

288.15323.15

1.010001.01325

B-8

291.15323.15

1.010001.01325

B-10

298.15323.15

1.013251.01325

B-11

298.15298.15

1.013251.01325

B-12

298.15323.15

1.013251.01325

B-13

298.15298.15

1.013251.01325

B-14

293.15323.15

1.013251.01325

B-15

298.15298.15

1.013251.01325

B-16

293.15323.15

1.013251.01325

B-17

298.15298.15

1.013251.01325

B-18

323.15323.15

1.013251.01325

B-20

323.15323.15

1.013251.01325

22m4-B

298.15298.15

1.013251.01325

23m4-B

298.15298.15

1.013251.01325

1-4 1-5 1-6

2-4 2-6 2-8 1-2

7.500051.2000 25.800067.9000 43.600099.3000 729.0000 105.1000 84.0000140.7000 2991.000 3547.000 8.900019.0000 36.200051.7000 69.4000122.4000 1.150084.9000 175.0000 886.3450 19.7620940.0000 30.10001008.430 0 158.3100 1037.000 0 112.5000 1072.300 0 257.0000 1108.000 0 70.00001164.000 0 270.8860 1198.680 0 46.20001263.000 0 172.0000 1293.000 0 34.40001347.600 0 176.0000 1390.000 0 127.0000 1213.000 0 145.0000 1266.000 0 433.2000 909.1000 435.4000 913.8000

-

0.20900.8980 0.25500.7080 0.29400.8220

-

0

96

0

72

35.7

11.5

0.18

-

0

75

0

72

32.3

15.2

0.17

-

0

61

0

72

37.7

26.1

0.26

-

0.33000.8420

0.01960.6019

0

37

33

72,18

51.1

40.1

0.31

-

0.38000.7960

-

0

19

0

72

40.5

49.6

0.39

0.03440.9855

0.03440.9850

0.01710.9855

199

75

404

74-75

138.3

127.0

0.93

-

0

26

0

23

47.2

6.8

0.08

-

0

28

0

23

43.6

19.4

0.17

-

0

20

0

23

49.8

53.5

0.37

-

11

81

0

72-73

32.4

9.7

0.17

0.28250.7879

0.37700.6690 0.43400.7480 0.39400.7920 0.14700.8660

0.04340.8994

-

-

37

0

0

76-77

24.8

171.2

1.23

0.00430.9918

-

-

251

0

0

28,7888

19.8

124.8

0.81

0.01020.9756

-

-

320

0

0

55,89101

18.3

122.1

0.74

0.05600.9636

-

-

85

0

0

76,81,1 00,102103

17.8

136.4

0.76

0.03840.9828

-

-

155

0

0

77,81,9 2,96

16.9

127.8

0.63

0.15020.9588

-

-

24

0

0

76

17.2

152.7

0.77

0.04900.9902

-

-

83

0

0

76,81

15.0

126.7

0.60

0.12840.9649

-

-

9

0

0

77

15.3

120.4

0.51

0.03530.9952

-

-

277

0

0

76,81,9 2,104

15.7

135.4

0.56

0.16130.9808

-

-

25

0

0

76

14.2

155.3

0.71

0.03710.9965

-

-

228

0

0

55,76,8 1,104

12.4

120.8

0.50

0.16620.9827

-

-

27

0

0

76

15.1

175.1

0.76

0.12650.9868

-

-

46

0

0

81

11.1

106.1

0.38

0.14280.9860

-

-

61

0

0

81

9.3

78.5

0.29

0.18520.8522

-

-

15

0

0

88

28.6

220.4

1.54

0.15000.8536

-

-

13

0

0

88

8.8

62.7

0.43


Energy & Fuels

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

2m5-B

298.15298.15

1.013251.01325

3m5-B

298.15298.15

1.013251.01325

B-224m5

298.15323.15

1.013251.01325

1-B

363.15413.15

6-mB

293.15573.15

7-mB

255.40323.15

1.013251.01325 1.01325125.0000 0 0.79000138.0000 0

mB-8

298.15298.15

1.013251.01325

mB-10

298.15308.15

1.013251.01325

mB-12

298.15298.15

1.013251.01325

mB-14

298.15298.15

1.013251.01325

mB-16

298.15323.15

1.013251.01325

6-12mB

298.15323.15

1.013251.01325

7-12mB

298.15298.15

1.013251.01325

12mB-9

298.15318.15

1.013251.01325

6-13mB

298.15323.15

1.013251.01325

7-13mB

298.15323.15

1.013251.01325

13mB-9

298.15298.15

1.013251.01325

6-14mB

298.15323.15

1.013251.01325

7-14mB

298.15298.15

1.013251.01325

14mB-9

298.15298.15

1.013251.01325

298.15308.15 298.15298.15

1.013251.01325 1.013251.01325

298.15298.15

1.013251.01325

288.15308.15 298.15298.15

1.013251.01325 1.013251.01325

eB-9

293.60298.15

1.013251.01325

eB-10

298.15298.15

1.013251.01325

eB-12

298.15298.15

1.013251.01325

eB-14

298.15298.15

1.013251.01325

14mB-10 14mB-14 14mB-16 7-eB 8-eB

605.2000 920.5000 483.0000 921.3000 427.0500 1018.230 0 19.000062.6000

Page 54 of 84

0.18100.7010

-

-

18

0

0

88

10.6

88.1

0.58

0.14000.7252

-

-

17

0

0

88

10.5

85.1

0.57

0.15660.9047

-

-

26

0

0

55,105

32.3

261.9

1.62

-

0.28800.8710

-

0

60

0

106

42.0

19.2

0.28

22.0000592.5000

0.01640.9758

-

0.01640.9757

425

0

92

28,78,1 07-108

24.1

76.8

0.39

36.4000594.0000

0.01280.9687

-

-

198

0

0

28,55,9 2,100,1 09-114

141.3

503.4

1.04

0.13960.9438

-

-

29

0

0

115

35.3

168.8

1.11

0.03490.9883

-

-

119

0

0

92,115

35.9

163.4

0.96

0.17670.9593

-

-

31

0

0

115

71.2

373.9

2.20

0.05540.9855

-

-

58

0

0

92,115

67.8

364.7

1.94

0.15520.9713

-

-

41

0

0

55,115

67.6

420.1

2.18

0.16000.8200

-

-

35

0

0

78,116

35.3

128.3

0.76

0.24000.7700

-

-

6

0

0

117

73.0

270.3

1.87

0.15900.8950

-

-

31

0

0

118-119

93.3

308.7

1.95

0.16000.8300

-

-

30

0

0

78,120

36.5

113.9

0.73

0.15990.7918

-

-

23

0

0

55,117

66.9

225.8

1.54

0.18590.8807

-

-

11

0

0

119

162.6

506.5

3.35

0.16000.8300

-

-

23

0

0

78

44.2

124.9

0.87

0.06900.9653

-

-

35

0

0

92,117

117.5

300.9

2.09

0.18540.9025

-

-

10

0

0

119

217.6

521.2

3.38

-

-

88

0

0

92

168.8

400.5

2.28

-

-

27

0

0

92

305.1

805.8

4.29

-

-

10

0

0

117

305.7

1023.7

5.79

-

-

81

0

0

113,121 -123

28.7

125.3

1.00

-

-

39

0

0

124-125

9.6

44.4

0.25

0.18640.8810

-

-

12

0

0

119,126

15.0

75.4

0.41

0.07800.9613

-

-

29

0

0

127

21.5

105.9

0.56

0.10900.9718

-

-

32

0

0

124

31.1

167.9

0.84

0.10950.9680

-

-

25

0

0

127

37.4

210.3

1.02

144.0000 568.0000 42.4000618.4000 141.0000 630.0000 74.3000725.9000 134.0000 777.0000 236.0000 446.5000 287.5000 420.0000 185.0000 440.0000 200.0000 381.0000 229.4000 401.4000 198.0000 377.5000 163.3000 349.0000 50.1000347.0000 134.8000 319.9000 32.0000330.1000 55.1000369.1000 180.6000 412.7000 34.3000568.9000 99.0000708.9000 296.3000 744.0000 111.0000 620.0000 97.0000673.0000 129.0000 728.0000

0.03060.9779 0.07160.9783 0.20100.9180 0.01430.9792 0.04080.9277


Page 55 of 84

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

Energy & Fuels

eB-16

298.15330.00

1.013251.01325

eB-18

303.15330.00

1.013251.01325

eB-19

311.45330.00

1.013251.01325

0.14070.9971

-

-

48

0

0

124,128

41.0

181.6

0.89

0.84350.9706

-

-

12

0

0

128

29.8

98.3

0.48

0.85210.9732

-

-

12

0

0

128

28.5

89.4

0.42

313.02330.00 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

-

-

13

0

0

128

34.1

108.2

0.50

-

-

16

0

0

129

222.7

371.5

2.60

-

-

18

0

0

129

455.5

736.4

4.92

-

-

16

0

0

129

576.5

910.9

5.73

-

-

22

0

0

129

663.1

1166.4

7.84

-

-

18

0

0

129

716.1

1284.3

8.28

7-135mB

298.15298.15

1.013251.01325

0.26400.7370

-

-

6

0

0

117

188.6

533.9

4.06

135mB16

298.15298.15

1.013251.01325

0.14100.8960

-

-

7

0

0

117

472.9

1365.0

9.32

7-prB

298.15298.15

1.013251.01325

0.35800.6150

-

-

4

0

0

122

1.1

4.6

0.02

8-prB

298.15308.15

1.013251.01325

0.16500.8015

-

-

36

0

0

123

13.9

51.5

0.25

7-iprB

298.15298.15

1.013251.01325

0.27500.7920

-

-

7

0

0

117

4.9

22.9

0.13

298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

-

-

15

0

0

129

13.2

63.7

0.43

-

-

15

0

0

129

94.1

374.0

2.24

-

-

20

0

0

129-130

135.6

559.9

3.18

-

-

15

0

0

129

176.4

698.0

3.91

-

-

29

0

0

129

198.8

806.9

4.39

phe-20

391.75391.75

1.013251.01325

0.09990.9007

-

-

10

0

0

131

27.6

283.9

0.60

224m5mB

293.15363.15

1-mB

255.40310.90

1.0132516.50000 138.0000 138.0000

0.01620.9615

-

-

80

0

0

105,132 -133

24.8

95.5

0.49

-97.000019.0000

-

-

0.01280.9036

0

0

32

18

960.5

87.7

0.87

B-mB

279.45337.65

1.013251.01325

2.600079.1310

0.03580.9913

-

-

154

0

0

28,79,1 00,134142

12.6

5.5

0.04

293.15323.15 289.45323.15

1.013251.01325 1.013251.01325

23.2000214.9000 30.3000238.6480

0.03320.9753 0.04470.9701

-

-

57

0

0

143-146

32.0

34.8

0.23

27.8

29.0

0.20

287.85328.45

1.013251.01325

7.8700177.6000

0.01970.9897

46.8

54.2

0.37

B124mB

293.15298.15 298.15298.15

1.013251.01325 1.013251.01325

0.05000.9500 0.09530.9422

B135mB

298.15303.15

1.013251.01325

298.15318.15 298.15318.15 298.15318.15 298.15298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

15.8200104.5000 96.5670379.4050 119.1180 441.9140 12.7000143.7000 37.4000107.1000 57.3000195.1000 88.0000173.0000

eB-20 7-124mB 124B -10 124mB12 124mB14 124mB16

7-1mBB 101mBB 121mBB 1mBB14 1mBB16

B-12mB B-13mB B-14mB B-eB

B-prB B-iprB B-buB B-1mBB

13.7000793.0000 117.0000 531.0000 115.0000 510.0000 90.6000545.0000 18.7000274.1000 16.9000252.4000 16.5000252.3000 16.3000266.4000 18.4000275.0000 238.0000 308.6000 157.6000 389.6000 410.0000 445.0000 259.0000 430.5000 348.2000 507.0000 19.2000753.9000 40.6000697.5000 30.0000652.6000 32.5000616.5000 42.1000597.5000 354.2630 1343.150 0 39.4500662.6000

0.84910.9799 0.01950.9564 0.05670.9852 0.06550.9873 0.07430.9889 0.15920.9885

0.00700.9584 0.01780.9452 0.00880.9361 0.07240.9904 0.03610.9898

0.09650.9428 0.08200.9627 0.19720.9088 0.10140.8952 0.15870.8493

139,143 -146 135,138 ,142,14 4-149

-

-

60

0

0

-

-

302

0

0

-

-

31

0

0

150-152

40.0

29.0

0.19

-

-

13

0

0

138

17.3

46.1

0.30

-

-

22

0

0

138,153

9.0

27.4

0.18

-

-

44

0

0

154-155

37.2

35.8

0.21

-

-

39

0

0

153,156

91.8

70.6

0.45

-

-

30

0

0

154-155

40.9

55.5

0.30

-

-

13

0

0

157

91.8

132.4

0.81


Energy & Fuels

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

B-2mBB B-Bph B-Dph mB12mB mB13mB

309.15318.15 344.75344.75 308.15308.15 298.15298.15 298.15298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

54.0000143.0000 57.7780144.8630 1.38209.5880 9.400047.0000 7.300043.0000

0.15900.8833 0.13540.8747 0.16820.9094 0.06870.9476 0.06030.9574

Page 56 of 84

-

-

14

0

0

157

93.8

107.1

0.62

-

-

12

0

0

158

173.6

182.2

1.03

-

-

12

0

0

159

734.7

35.5

0.20

-

-

36

0

0

140

3.7

1.1

0.01

-

-

17

0

0

140

18.9

6.1

0.04

85.7

12.9

0.08

247.5

17.8

0.11

79,135, 138,140 ,160 151152,161 -162

mB14mB

290.65338.15

1.010001.01325

4.100050.1000

0.05000.9500

-

-

123

0

0

mB-eB

298.15303.15

1.013251.01325

-12.73000.0000

0.05000.9500

-

-

43

0

0

298.15298.15 298.15298.15 298.15318.15 298.15318.15 298.15318.15 288.65298.15 288.65298.15 298.15343.15 298.15298.15 288.65298.15 298.15343.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15318.15 298.15318.15 298.15318.15 298.15298.15 298.15298.15 318.15318.15 288.20298.20 288.20298.20 288.20298.20 288.20298.20 298.15298.15 288.20298.20 293.20308.20 298.15298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

38.6180121.5030 31.3800153.4270 0.30004.9000 -28.10000.0000 7.900022.3000 0.461011.3000 0.712010.5510 2.554039.4400 18.960092.5900 -10.88600.0000 3.224035.1500 18.330097.7900 -9.95000.0000 14.937038.8280 8.159028.6600 -20.31000.0000 -4.10008.0000 -3.70000.0000 9.100024.3000 0.70304.6020 -2.60005.9000 7.300044.4000 16.000058.4000 13.000060.8000 11.200071.1000 27.300087.2000 10.6000108.9000 33.4000166.9000 43.6000268.1000 7.940061.7100

0.14680.9063 0.11050.9509 0.10610.9210 0.17080.8930 0.07890.9006 0.03470.9822 0.03380.9649 0.03240.9650 0.09970.9241 0.03510.9666 0.03530.9652 0.09040.9179 0.03650.9663 0.12910.8929 0.09680.9224 0.08880.9610 0.05620.9230 0.18750.8489 0.11390.9306 0.06430.9144 0.07270.8893 0.05500.9500 0.06630.9316 0.06350.9336 0.06880.9642 0.09390.9276 0.20110.9728 0.08330.9474 0.10510.9524 0.00770.0623

-

-

10

0

0

138

45.5

40.2

0.23

-

-

13

0

0

138

14.7

14.8

0.09

-

-

39

0

0

154,163

1154.2

31.6

0.18

-

-

30

0

0

156,162

199.5

36.8

0.21

-

-

50

0

0

154,163

374.0

54.6

0.29

-

-

59

0

0

103.1

8.6

0.05

-

-

55

0

0

106.4

5.0

0.03

-

-

78

0

0

151,164

116.5

29.7

0.17

-

-

18

0

0

166

106.0

67.8

0.37

100.1

5.2

0.03

mB124mB mB135mB mB-prB mB-iprB mB-buB 13mB12mB 14mB12mB eB12mB 12mBiprB 14mB13mB eB13mB 13mBiprB eB14mB 14mB124mB 14mB135mB 14mBiprB eB-prB eB-iprB eB-buB 135mB124mB prB-buB 2mBB1mBB 5-C5 C5-6 C5-7 C5-8 C5-10 C5-12 C5-16 5-C6

139,164 -165 139,164 -165

-

-

63

0

0

139,164 -165

-

-

80

0

0

151,164

135.1

32.6

0.19

-

-

18

0

0

166

106.8

68.2

0.37

-

-

50

0

0

151,164

1083.4

75.4

0.45

-

-

11

0

0

138

8.3

2.6

0.01

-

-

13

0

0

138

39.6

7.5

0.04

-

-

19

0

0

166

76.7

12.0

0.07

-

-

43

0

0

154,167

63.3

2.1

0.01

-

-

24

0

0

156

465.4

11.3

0.06

-

-

49

0

0

154,167

51.7

9.6

0.05

-

-

14

0

0

138

104.9

3.2

0.02

-

-

10

0

0

154

332.5

3.1

0.01

-

-

8

0

0

95

100.1

26.5

0.12

-

-

25

0

0

168

227.8

93.7

0.69

-

-

28

0

0

168

224.0

99.8

0.68

-

-

38

0

0

168-169

182.2

96.6

0.61

-

-

26

0

0

168

159.4

108.1

0.65

-

-

11

0

0

169

169.8

107.5

0.62

-

-

26

0

0

168

84.6

89.3

0.46

-

-

37

0

0

168,170

54.6

88.1

0.42

-

-

8

0

0

171

31.1

11.3

0.07


Page 57 of 84

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

Energy & Fuels

6-C6

288.15413.21

0.79000300.0000 0

1.7000241.6000

0.00180.9909

-

-

1535

0

0

C6-7

293.15323.15

1.00000285.0000 0

4.9200293.0000

0.20300.9969

-

-

68

0

0

C6-8

298.15313.15

1.00000290.0000 0

3.6200288.2000

0.08950.9979

-

-

120

0

0

C6-9

298.15313.15

1.013251.01325

176.1500 296.2000

0.29480.8578

-

-

32

0

0

C6-10

298.15313.15

1.00000290.0000 0

2.5100365.9000

0.05000.9988

-

-

115

0

C6-11

298.15313.15

1.013251.01325

86.0000354.9000

0.16420.9535

-

-

53

0

28,58,7 879,82,8 5,87,10 8,111,1 71-217 30,55,9 0,171,1 91,218 30,171, 174,191 ,214,21 9-221

11.3

17.9

0.11

15.2

25.5

0.15

13.3

24.6

0.13

191,222

7.2

18.6

0.09

0

30,171, 174,191 ,223224

11.2

25.9

0.13

0

174,191

7.6

22.8

0.10

11.6

34.5

0.14

C6-12

293.15313.15

1.00000291.0000 0

2.1000415.0000

0.12130.9992

-

-

100

0

0

30,171, 191,214 ,222,22 5

C6-13

298.15298.15

1.013251.01325

102.0000 401.0000

0.12360.9540

-

-

27

0

0

174

8.5

28.3

0.11

C6-14

293.15308.15

1.000001.01325

2.2100483.2000

0.02920.9993

-

-

176

0

0

104,171 ,174,22 3

13.0

41.1

0.16

C6-15

298.15298.15

1.013251.01325

104.0000 478.0000

0.12750.9612

-

-

27

0

0

174

13.9

55.6

0.21

C6-16

293.15323.15

1.013251.01325

1.7300562.2000

0.00910.9995

-

-

218

0

0

55,104, 170171,174 ,191,22 6

15.7

59.6

0.22

C6-17

298.15298.15

1.013251.01325

0.15930.9641

-

-

28

0

0

174

17.5

83.8

0.31

288.20298.20 288.20298.20 288.20298.20 298.15298.15

1.013251.01325 1.010001.01325 1.013251.01325 1.013251.01325

-

-

22

0

0

227

13.1

20.1

0.12

-

-

52

0

0

227-229

11.0

16.4

0.09

-

-

23

0

0

227

9.8

17.8

0.09

-

-

10

0

0

228

10.2

15.9

0.07

C7-12

288.20298.20

1.013251.01325

0.10950.9332

-

-

21

0

0

227

4.9

14.4

0.06

C7-14

298.15298.15

1.013251.01325

0.08570.9628

-

-

10

0

0

228

18.2

52.6

0.21

C7-16

298.20308.20

1.013251.01325

0.13660.8741

-

-

21

0

0

227

11.1

39.4

0.14

288.15298.15 288.15298.15 288.15298.15 298.15298.15

1.013251.01325 1.010001.01325 1.013251.01325 1.013251.01325

-

-

22

0

0

230

13.3

21.1

0.12

-

-

49

0

0

228-230

12.4

16.6

0.09

-

-

25

0

0

230

11.2

19.4

0.09

-

-

10

0

0

228

20.7

35.7

0.16

C8-12

288.15298.15

1.013251.01325

0.11660.9299

-

-

26

0

0

230

15.4

43.9

0.17

C8-14

298.15298.15

1.013251.01325

0.07790.9589

-

-

10

0

0

228

39.5

106.4

0.40

C8-16

298.15308.15

1.013251.01325

0.10220.9360

-

-

25

0

0

230

29.7

94.4

0.32

6-tet

288.20298.20

1.013251.01325

0.09700.9339

-

-

19

0

0

231

81.5

290.1

4.38

6-C7 7-C7 C7-8 C7-9

6-C8 7-C8 8-C8 9-C8

119.0000 565.0000 62.4000226.2000 20.1000261.9000 72.9000293.7000 44.8000274.6000 109.7000 398.7000 79.2000365.8000 139.3000 480.6000 48.0000219.8000 19.3000253.5000 65.1000279.0000 40.0000254.1000 112.0000 392.8000 77.1000329.5000 102.3000 456.4000 139.1000 476.6000

0.05980.8765 0.06410.9706 0.09150.9367 0.06050.9467

0.08270.9232 0.07060.9734 0.08450.9078 0.05870.9451


Energy & Fuels

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

7-tet

288.20323.15

1.010001.01325

tet-12

288.20298.20

1.013251.01325

tet-16

298.15323.15

1.013251.01325

288.15308.15 298.15298.15 298.15298.15 288.15308.15 298.15298.15 298.15298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

22m5-C6

298.15313.15

1.013251.01325

24m5-C6

301.15301.15

1.013251.01325

C6224m5

293.15323.15

1.00000290.0000 0

C6-34m6

308.15308.15

1.013251.01325

C6-4m7

308.15308.15

1.013251.01325

288.15313.15 288.15313.15 363.15413.15

1.013251.01325 1.013251.01325 1.013251.01325

298.15308.15

1.013251.01325

C5-23m4 22m3-C6 22m4-C6 23m4-C6 2m5-C6 3m5-C6

23m4-C7 23m4-C8 1-C6 C5-B

B-C6

B-C7 B-C8 B-tet C5-mB

60.3000530.0000 138.4000 598.9000 156.4000 712.9000 -7.24004.9700 70.600098.5700 5.6000154.2000 4.4700167.0000 6.5000205.6000 5.8000185.6000 108.1000 181.4000 102.1600 172.0800 18.7000190.5000 156.4000 224.3000 164.3000 219.5000 15.7700168.3100 15.3400185.3500 20.500067.9000 145.7000 647.0000

Page 58 of 84

0.10340.9736

-

-

59

0

0

55,229, 231-232

62.6

233.0

3.17

0.15990.9515

-

-

21

0

0

231

125.7

555.1

46.90

0.07750.9497

-

-

30

0

0

55,231

41.3

219.2

0.88

-

-

94

0

0

233

58777. 1

414.8

2.90

-

-

9

0

0

234

662.2

588.0

4.05

386.8

357.8

2.28

534.5

556.1

3.42

239.3

258.3

1.57

0.03670.9805 0.23700.7360 0.04000.9900 0.00700.9900 0.00680.9900 0.02000.9900

211,235 -237 211,236 ,238 171,211 ,236

-

-

69

0

0

-

-

148

0

0

-

-

53

0

0

-

-

50

0

0

211,236

254.2

285.4

1.73

0.18800.7430

-

-

16

0

0

191

216.7

332.3

1.91

0.17580.7115

-

-

5

0

0

105

529.7

704.3

3.89

0.05710.9737

-

-

131

0

0

30,55,1 33,191, 220,239

48.9

65.8

0.37

0.34780.8218

-

-

8

0

0

220

381.2

749.3

4.04

0.39530.8221

-

-

9

0

0

220

204.3

416.3

2.16

-

-

96

0

0

240

580.2

634.5

3.68

0.02490.9713 0.02750.9741

-

-

96

0

0

241

596.6

703.0

3.92

-

0.28600.8820

-

0

60

0

106

36.9

18.7

0.23

0.10300.9423

-

-

36

0

0

169,242 -243

19.4

96.3

0.79

4.7

26.7

0.20

13.3

77.3

0.55

16.1

91.8

0.63

280.15413.21

0.8000017.54000

3.3000867.4800

0.00120.9987

298.15298.15 298.15298.15 298.15323.15

1.010001.01325 1.010001.01325 1.013251.01325

0.10160.9689 0.11130.9719 0.07500.9387

298.15298.15

1.013251.01325

98.3000820.9000 98.8000818.4000 37.7000163.0000 146.0000 365.4000

0.12930.8932

51,55,7 9,82,85, 87,90,9 7,103,1 12,138, 171,176 177,186 ,189,20 0,204205,212 213,216 218,243 -285 243,286 -287 243,286 -287

-

-

1397

0

0

-

-

32

0

0

-

-

36

0

0

-

-

25

0

0

55,288

27.6

32.7

0.20

-

-

8

0

0

243

95.7

257.8

2.02

36.3

143.3

0.98

85.3

283.7

1.77

C6-mB

290.65413.21

1.0132517.54000

18.5200627.5160

0.05300.9937

-

-

132

0

0

28,7879,137138,141 ,171,18 7,243,2 61,289

C612mB

298.15300.05

1.013251.01325

157.0000 631.7000

0.10030.8992

-

-

30

0

0

102,121 ,290


Page 59 of 84

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

Energy & Fuels

C613mB

298.15323.15

1.013251.01325

93.7080575.6000

0.18000.9664

-

-

32

0

0

C614mB

288.15313.15

1.013251.01325

20.1290587.6900

0.01610.9930

-

-

174

0

0

C6-eB

298.15298.15

1.013251.01325

0.02500.9779

-

-

57

0

0

C6124mB

298.15298.15

1.013251.01325

0.07960.9303

-

-

13

0

0

C6135mB

298.15298.15

1.013251.01325

0.08060.9312

-

-

13

0

298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15

1.013251.01325 1.013251.01325 1.010001.01325 1.010001.01000 1.010001.01325 1.010001.01000

-

-

20

-

-

-

C61mBB

298.15298.15

1.013251.01325

C62mBB

309.15318.15

1.013251.01325

288.15308.15 288.15308.15 283.15313.15 288.15318.15 283.15318.15 283.15353.15 288.20298.20 288.20323.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

288.20298.20

1.013251.01325

288.20298.20 298.15298.15 298.15298.15 298.15298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

mC5-16

298.20308.20

1.013251.01325

6-mC6

273.15298.15

1.013251.01325 1.01325138.0000 0 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.010001.01325

47.4000584.2000 146.8580 640.4870 142.0890 623.4160 78.2000694.1000 37.1000542.4000 73.7000622.3000 73.7000548.8000 70.6000619.7000 65.1000529.1000 363.0000 936.0000 395.0000 927.0000 0.860035.4700 -16.040012.8800 -56.60000.6300 -0.11009.1000 -19.400019.3000 -11.80004.7000 58.3000258.6000 95.3000503.0000 158.9000 451.9000 88.2000436.7000 52.3000107.1000 18.400096.0000 22.8000148.9000 104.0000 300.0000 4.900018.6000

C6-prB C6-iprB mB-C7 C7-eB mB-C8 eB-C8

C5-C6 C5-C7 C5-C8 C6-C7 C6-C8 C7-C8 C5-tet C6-tet C7-tet C8-tet 6-mC5 mC5-7 mC5-10

7-mC6 mC6-8 mC6-10 mC6-16 8-eC6 6-tCC6 7-tCC6

255.40323.15 298.15298.15 298.15298.15 273.15308.20 298.15298.15 298.15298.15 298.15298.15

55,290291 79,102, 138,147 ,290,29 2-294 121,291 ,295

75.6

267.2

1.69

59.6

219.1

1.40

25.2

97.6

0.61

138

54.4

237.7

1.37

0

138

58.8

253.7

1.49

0

0

295

10.1

47.5

0.27

19

0

0

295

43.4

162.0

0.97

-

23

0

0

243,287

43.1

182.0

1.20

-

-

13

0

0

287

37.6

130.9

0.77

-

-

26

0

0

243,287

53.9

224.1

1.42

-

-

13

0

0

287

56.1

182.5

1.03

0.12180.9003

-

-

14

0

0

157

6.6

50.5

0.30

0.15780.9154

-

-

13

0

0

157

5.0

34.9

0.20

-

-

98

0

0

182,242 ,296

108.4

21.1

0.16

-

-

100

0

0

182,297

1222.8

13.8

0.10

49.8

4.2

0.03

0.05000.9750 0.02500.9750 0.08640.9631 0.04230.9241 0.09490.9666 0.08340.9617

0.01060.9918 0.03350.9790 0.01230.9831 0.02990.9761 0.02120.9973 0.02960.9762 0.07620.9370 0.09440.9579

-

-

162

0

0

182,298 -299

-

-

104

0

0

182,300

529.1

11.2

0.07

-

-

174

0

0

182,297

692.1

19.6

0.11

-

-

137

0

0

182,300

75.6

1.8

0.01

-

-

19

0

0

231

23.9

45.1

0.30

-

-

31

0

0

55,231

25.7

95.6

0.55

-

-

17

0

0

231

4.3

14.0

0.08

-

-

18

0

0

231

21.5

62.9

0.33

-

-

7

0

0

173

862.1

813.9

7.78

-

-

11

0

0

169

1015.4

698.2

5.91

-

-

11

0

0

169

760.1

791.8

5.95

0.11390.9224

-

-

13

0

0

170

352.3

759.1

4.45

0.09190.9116

-

-

18

0

0

133,301

16068. 4

1743.9

18.28

6218.4

3215.9

8.56

0.11480.8712 0.09760.9508 0.27000.8400 0.13690.9576 0.17410.9677

4.700089.0000

0.09580.9378

13.300040.2000 20.390080.3300 65.0000259.1000 23.500041.1000 -34.20000.0000 -33.90000.0000

0.14080.8898 0.08100.9262 0.12130.9366 0.25000.8100 0.05000.9500 0.09900.9521

-

-

77

0

0

55,110, 173,301 -303

-

-

16

0

0

301

3194.5

969.4

7.13

-

-

11

0

0

303

1570.7

918.0

6.12

-

-

21

0

0

133,170

1038.8

1879.3

9.72

-

-

6

0

0

173

2489.6

868.3

5.52

-

-

11

0

0

304

6015.0

1281.3

14.28

-

-

36

0

0

229,256

8771.2

1630.2

17.81


Energy & Fuels

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

6-cCC6 7-cCC6 6-bcy 7-bcy 8-bcy 12-bcy bcy-16 22m3mC6 224m5mC6 22m4tCC6 23m4tCC6 2m5tCC6 3m5tCC6 224m5tCC6 22m4cCC6 23m4cCC6 2m5cCC6 3m5cCC6 2m7cCC6

298.15298.15 298.15298.15 288.20298.20 298.15298.15 288.20298.20 288.20300.05 298.20308.20 273.15273.15 273.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15

1.013251.01325 1.010001.01325 1.013251.01325 1.010001.01000 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 138.0000 138.0000

1-mC6

255.40310.90

mC5-B

298.15298.15

1.013251.01325

B-mC6

298.15308.15

1.013251.01325

B-eC6

283.15298.15

1.013251.01325

B-tCC6

298.15298.15

1.013251.01325

B-cCC6

298.15298.15

1.013251.01325

B-bcy

298.15298.15

1.013251.01325

mC6-mB

255.40310.90

0.79000138.0000 0

300.05300.05 283.15298.15

1.013251.01325 1.013251.01325

mB-eC6

283.15298.15

1.013251.01325

eC6-eB

283.15298.15

1.013251.01325

mBtCC6

298.15298.15

1.013251.01325

mBcCC6

298.15298.15 298.15298.15

1.013251.01325 1.013251.01325

mC614mB mC6-eB

C5-mC5

19.1000111.0000 21.4000139.2000 6.000033.0000 8.500024.3000 7.200046.2000 20.800084.1000 24.0000128.0000 27.300034.0000 11.010054.3900 15.400086.0000 8.200050.0000 -22.40000.0000 -0.50005.8000 15.030073.8800 29.5000158.4000 25.9000142.1000 20.9000112.9000 23.8000124.3000 33.3000178.7000 584.0000 -0.0000 192.8000 755.0000 51.9000790.0000 230.0000 876.0000 190.8900 766.4600 126.7000 776.3000 229.9000 855.5000

0.05000.9500 0.05000.9500 0.12610.9265 0.17560.9274 0.07740.9164 0.08640.9085 0.05790.9478 0.34100.7370 0.04670.9500 0.05000.9500 0.05000.9500 0.05000.9500 0.05000.9500 0.09960.9507 0.05000.9500 0.05000.9500 0.05000.9500 0.05000.9500 0.05000.9500

Page 60 of 84

-

-

11

0

0

304

1720.6

1197.9

13.85

-

-

32

0

0

229,305

1496.3

1449.9

16.43

2161.4

86.35

-

-

17

0

0

306

10516. 4

-

-

15

0

0

229

9336.9

1566.3

12.81

-

-

16

0

0

306

8572.0

2469.1

65.09

-

-

20

0

0

306-307

4941.3

2850.2

154.32

-

-

18

0

0

306

2283.1

1849.2

10.71

5540.4

36.14

-

-

4

0

0

133

17913. 3

-

-

28

0

0

133,308

5973.3

2067.1

22.41

-

-

11

0

0

304

3224.2

1767.6

24.66

-

-

11

0

0

304

3412.3

1072.0

14.75

-

-

11

0

0

304

9065.3

1164.3

14.19

1140.7

13.89

-

-

11

0

0

304

76508. 4

-

-

18

0

0

256

3892.8

2096.0

28.10

-

-

11

0

0

304

1690.9

1734.1

25.46

-

-

11

0

0

304

1123.2

1019.4

14.74

-

-

11

0

0

304

1517.7

1085.3

13.80

-

-

11

0

0

304

1353.3

1071.3

13.60

-

-

20

0

0

305

1052.3

1356.1

16.22

-

-

0.04150.9060

0

0

36

18

702.3

1793.9

24.88

0.08770.9319

-

-

11

0

0

169

60.1

326.1

1.64

0.01880.9855

-

-

66

0

0

303,309 -310

30.1

162.2

0.81

0.10300.9011

-

-

12

0

0

311

137.3

1106.5

2.40

0.09970.9500

-

-

20

0

0

256

23.8

136.5

0.56

0.05000.9500

-

-

24

0

0

55,305

24.0

131.9

0.55

0.09580.8723

-

-

13

0

0

288

5.8

35.0

0.13

57.2000557.0000

0.02620.9622

-

-

87

0

0

110111,133 ,285,31 0

2308.9

9223.0

1.89

85.0000447.0000 60.7000458.0000 183.0000 584.0000 183.0000 502.0000 166.1600 486.8300 99.5000539.1000 -12.37000.0000

0.05700.9400 0.03440.9583

-

-

10

0

0

147

152.7

406.0

2.36

-

-

31

0

0

310-311

87.4

332.4

1.17

0.10330.8932

-

-

12

0

0

311

99.1

535.7

1.40

0.14690.8868

-

-

12

0

0

311

116.9

534.1

1.41

0.09940.9011

-

-

17

0

0

256

139.0

522.0

2.50

-

-

20

0

0

305

117.6

460.3

2.22

-

-

10

0

0

303

4867.7

388.1

2.42

0.05000.9500 0.06780.9554


Page 61 of 84

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

Energy & Fuels

C5-mC6

298.15298.15

1.013251.01325

C5-tCC6

298.15298.15

1.013251.01325

C5-cCC6

298.15298.15

1.013251.01325

C5-bcy

288.20298.20

1.013251.01325

298.15298.15 293.15308.15 298.15298.15 298.15298.15 298.15298.15 288.20298.20 298.15298.15 298.15298.15 288.20298.20 298.15298.15 298.15298.15 288.20298.20

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

tet-tCC6

298.15298.15

1.013251.01325

mC5mC6 mC6eC6 mC6tCC6 mC6cCC6

298.15298.15 298.15298.15 298.15298.15 298.15298.15

CO2-5

308.15573.15

CO2-6

308.15573.15

CO2-9

373.15373.15

CO2-10

283.15573.15

CO2-12

318.15318.15

CO222m3

310.00313.15

1-CO2

283.15353.15

CO2-2

217.00323.15

CO2-B

354.50398.60

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 75.80000 124.5000 0 62.90000 125.0000 0 75.00000 125.0000 0 75.80000 125.0000 0 40.00000 140.0000 0 62.90000 104.4000 0 5.07000111.4570 0 1.01325110.0000 0 1.010001.01000

mC5-C6 C6-mC6 C6-eC6 C6-tCC6 C6-cCC6 C6-bcy C7-tCC6 C7-cCC6 C7-bcy C8-tCC6 C8-cCC6 C8-bcy

112.3000 -0.0000 270.5600 -0.0000 129.1400 -0.0000 142.6000 -0.0000 9.100046.8000 0.030023.1200 27.900072.0000 -7.430025.2200 -3.850040.6000 39.5000126.0000 -7.90000.0000 0.500014.7000 38.2000158.4000 -1.50008.4800 3.730023.1000 36.4000178.2000 124.0000 245.0000 -52.04000.0000 1.10004.2000 1.22007.2000 8.990049.2600 4022.000 4460.000 4090.000 5050.000

0.07620.9605

-

-

10

0

0

303

336.7

244.0

1.48

0.03070.9736

-

-

36

0

0

312

114.3

196.7

1.12

0.02320.9894

-

-

37

0

0

312

363.1

277.0

1.56

0.05190.9205

-

-

19

0

0

306

322.2

319.7

1.62

-

-

11

0

0

169

1462.7

479.4

2.65

8578.4

325.1

1.74

860.5

471.3

2.34

0.05260.8876 0.03420.9751 0.10300.8896 0.05000.9753 0.05000.9765 0.12370.9285 0.14500.9238 0.16320.8638 0.09970.9318 0.05000.9500 0.05000.9500 0.07420.9564

-

-

87

0

0

133,152 ,313

-

-

9

0

0

152

-

-

55

0

0

314-316

6097.0

427.2

2.10

443.0

2.19

-

-

55

0

0

314-316

14278. 9

-

-

19

0

0

306

641.1

557.7

2.42

-

-

8

0

0

315

8052.5

441.0

2.04

-

-

8

0

0

315

14707. 4

509.4

2.35

-

-

17

0

0

306

539.1

592.1

2.43

442.4

1.95

-

-

20

0

0

315-316

18759. 3

-

-

19

0

0

315-316

3058.6

473.4

2.09

-

-

18

0

0

306

494.3

607.2

2.36

-

-

9

0

0

317

8.3

17.8

0.07

-

-

10

0

0

303

62.4

22.7

0.14

-

-

10

0

0

152

386.9

9.0

0.05

-

-

11

0

0

316

1457.5

62.4

0.33

-

-

11

0

0

316

106.0

32.3

0.17

-

0.03870.9905

0.03870.9907

0

175

414

318-319

36.0

159.7

1.17

-

0.02440.9918

0.02000.9918

0

176

547

320-322

57.9

208.7

1.45

1980.000 -252.000

-

-

0.05840.9934

0

0

49

323

31.4

138.2

0.80

4750.000 3370.000

0.06310.9939

-

0.03620.9945

102

0

301

324-325

122.1

259.7

1.54

2974.800 -688.600

-

-

0.05000.9980

0

0

170

326

162.9

425.3

2.21

4300.000 -493.000

-

-

0.06000.9800

0

0

118

327

496.3

368.4

2.53

6.0003990.000

-

-

0

636

0

328-329

11.6

38.0

0.63

-373.0006514.000

0.04100.9790

0.02500.9780

0.04600.9790

118

185

105

330-333

27.3

187.3

1.35

31.900052.5000

-

0.35900.6210

-

0

40

0

334

40.6

17.4

0.24

0.20460.8634 0.05950.9491 0.11830.8783 0.05000.9500 0.05000.9500

0.09500.9000


Energy & Fuels

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

CO2-mB

298.15573.15

69.80000 175.0000 0

CO2-C6

308.15573.15

1.01000143.9000 0

N2-1

91.50298.00

N2-CO2

283.15353.15

1-H2S

293.15313.15

1.01325102.3000 0 6.310007.90000 0.470001.02000 0.440001.02000 10.13000 121.5900 0 5.0700015.20000

3SH-7

298.15298.15

1.013251.01325

283.15333.15 283.15333.15 283.15333.15

5.000005.00000 5.000005.00000 5.000005.00000

C6-4sh

283.15333.15

5.000005.00000

a2-3

273.15373.15

1-a2

115.77313.15

a2-2

273.15363.15

a2-CO2

260.95306.62

N2-a2

283.15338.15

a3-3

323.15323.15

N2-2 N2-B N2-C6

4sh-7 B-4sh 4sh-mB

1a6-6 1a6-12 t2a6-6 t2a6-7 c2a6-6 c2a6-7 t3a6-6 t3a6-7 15a6-6 6-1a7 1a7-7

92.1092.30 333.20433.20 333.20433.20

298.15298.15 293.15293.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15303.15

50.00000 150.0000 0 1.0132534.45000 50.00000 150.0000 0 35.00000 110.0000 0 10.36000 48.35000 50.00000 100.0000 0 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.010001.01325

5660.000 7060.000 4212.000 6510.000 13.00003059.000 0 17.4000178.0000 41.000071.7000 40.300075.1000 9.00004400.000 0

Page 62 of 84

0.11500.9870

-

0.03470.9946

66

0

885

335-339

59.8

149.0

1.23

-

0.03930.9902

0.03640.9902

0

137

716

334,340 -342

51.3

180.5

1.38

0.11700.7140

0.06000.7840

0.10600.8530

12

75

28

343-345

14.9

73.8

1.02

-

-

0.05000.9980

0

0

41

346-347

75.6

69.9

1.22

-

0

15

0

348

35.7

20.6

0.31

0.50000.5000

0

15

4

348-349

25.5

16.0

0.19

-

0.50000.5000 0.50000.5000

-

0.10000.9000

-

0

693

0

350-351

12.4

49.2

1.01

-

0.18400.8470

-

0

39

0

352

56.4

48.7

1.31

0.09000.8690

-

-

12

0

0

353

10.3

51.4

0.31

-

-

60

0

0

354

18.0

79.0

0.45

-

-

58

0

0

354

466.3

374.3

2.56

-

-

59

0

0

354

885.4

494.7

111.57

0.04970.9497

-

-

57

0

0

354

154.2

719.9

4.45

355

160.0

100.4

0.75

356-357

15.8

16.9

0.33

23.8000190.8000 217.2000 724.1000 72.0000698.3000 9.9000146.7000 -91.20000.0000 103.0000 682.5000 2440.000 3026.000 16.5000250.7000

0.02110.9850

0.02810.9855

0.00880.9861

146

125

567

0.23680.9313

0.20300.8160

-

18

36

0

-436.2002355.400

0.02050.9834

0.01430.9824

0.01520.9667

121

471

206

358

24.2

29.7

0.18

98.00002340.000 0

0.04100.8510

0.05000.9010

0.04200.9640

51

47

76

359

17.1

124.4

0.57

28.72001147.000 0

-

0.12300.9090

-

0

75

0

360

14.7

23.4

0.56

17.112097.9830

0.05330.9531

-

-

35

0

0

257

36.6

24.7

0.20

10.700061.1000 96.5000136.9000 22.600055.8000 24.100056.6000 21.400074.9000 32.500072.7000 21.400063.1000 28.700065.7000 82.6000246.6000 30.100047.1000 0.609059.1000

0.04750.9419 0.27370.6299 0.12510.8495 0.12940.8771 0.07590.9037 0.13040.8781 0.12700.9058 0.12920.8769 0.09680.8953 0.19820.8115 0.00210.8908

-

-

17

0

0

197,361

35.2

14.9

0.08

-

-

17

0

0

37

73.0

92.4

0.36

-

-

9

0

0

361

2.4

1.1

0.01

-

-

5

0

0

362

33.1

13.8

0.07

-

-

9

0

0

361

30.7

16.2

0.09

-

-

5

0

0

362

5.8

3.1

0.02

-

-

9

0

0

361

16.3

7.6

0.04

-

-

7

0

0

362

13.1

6.7

0.04

-

-

9

0

0

363

22.4

38.9

0.23

-

-

8

0

0

364

88.7

36.4

0.19

0

361,365 -366

21.3

9.1

0.04

0.04060.9630 0.04790.9498 0.01980.9495

-

-

26

0


Page 63 of 84

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

Energy & Fuels

298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15323.15 298.15318.15 298.15323.15 298.15318.15 298.15318.15 298.15318.15 298.15318.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

1a12-16

298.15298.15

1.013251.01325

2m4-1a5

363.13363.13

1a7-12 t2a7-7 c2a7-7 t3a7-7 6-1a8 7-1a8 1a8-8 1a8-16 t3a8-8 c3a8-8 t4a8-8 c4a8-8 1a9-9 7-1a10 1a10-10 8-1a12 9-1a12 1a12-12

37.000097.0000 13.800045.5000 11.600063.0000 21.000067.8000 13.400029.4000 22.100039.8000 17.200046.6000 60.1000163.8000 20.100055.1000 48.100057.6000 21.700064.0000 57.300066.3000 23.300040.5000 9.900026.7000 18.000045.4000 77.000077.0000 73.000073.0000 88.000088.0000 133.5000 133.5000

0.17900.9000 0.13090.8985 0.06920.8868 0.08650.9076 0.18130.8690 0.17270.8463 0.11300.8850 0.26560.9036 0.12500.8880 0.46400.5560 0.12200.8730 0.44900.6180 0.19800.8240 0.09710.8856 0.15400.8550 0.63000.6300 0.60000.6000 0.40000.4000

-

-

9

0

0

367

67.8

53.7

0.20

-

-

9

0

0

361

5.3

1.2

0.01

-

-

9

0

0

361

20.5

10.2

0.05

-

-

9

0

0

361

32.3

15.2

0.07

-

-

10

0

0

368

256.6

60.4

0.29

-

-

12

0

0

55

81.3

27.2

0.12

-

-

40

0

0

369

28.4

10.4

0.04

-

-

12

0

0

55

82.1

96.3

0.29

-

-

33

0

0

369

25.0

10.8

0.05

-

-

7

0

0

369

28.1

15.5

0.07

-

-

36

0

0

369

30.3

15.0

0.06

-

-

6

0

0

369

38.2

23.5

0.10

-

-

13

0

0

370

38.2

13.1

0.05

-

-

9

0

0

362

251.2

50.9

0.21

-

-

10

0

0

367,371

31.7

9.2

0.03

-

-

1

0

0

371

21.6

16.6

0.06

-

-

1

0

0

371

2.6

1.9

0.01

-

-

1

0

0

371

54.1

47.6

0.14

0.47000.4700

-

-

1

0

0

371

80.4

107.3

0.27

19.750057.7900

0.10510.9049

-

-

9

0

0

372

44.0

18.6

0.10

11.390062.4600 13.880079.5200 10.720058.6700 9.830054.8800 10.060055.9000 154.5000 154.5000

0.05000.9500 0.05000.9499 0.05010.9500 0.05010.9500 0.05010.9500

-

-

19

0

0

373

512.0

226.3

1.31

-

-

19

0

0

373

387.5

212.5

1.22

-

-

19

0

0

373

229.3

94.2

0.53

-

-

19

0

0

373

252.3

96.1

0.54

-

-

19

0

0

373

241.0

95.0

0.48

0.57000.5700

-

-

1

0

0

371

172.9

267.2

1.00

1a6224m5

298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15

15.00000 15.00000 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

224m51a12

298.15298.15

1.013251.01325

1a6-B

298.15363.13

1.0132524.12000

74.7540591.5000

0.03640.9499

-

-

58

0

0

197,257 ,374375

37.5

154.4

1.02

15a6-B

298.15298.15

1.010001.01000

0.11160.9004

-

-

9

0

0

376

61.6

139.6

0.99

B-1a7

298.15298.15

1.013251.01325

0.09320.9550

-

-

17

0

0

364,374

32.2

144.2

0.92

B-1a8

298.15323.15

1.013251.01325

0.10130.9587

-

-

27

0

0

55,374, 377

25.7

128.4

0.76

B-t3a8

298.20298.20

1.013251.01325

0.39600.7560

-

-

5

0

0

377

26.1

166.6

0.98

B-1a10

298.15298.15

1.010001.01000

0.11740.8646

-

-

9

0

0

376

12.5

63.9

0.33

1a6-mB

298.15298.15

1.013251.01325

0.05000.9500

-

-

19

0

0

375

18.7

35.7

0.25

mB-1a8

298.65298.65

1.013251.01325

95.0000308.0000 137.8000 614.6000 152.8000 680.0000 578.0000 674.0000 224.0000 704.0000 48.1800268.0800 124.0000 316.0000

0.17400.9040

-

-

12

0

0

377

79.9

195.1

1.19

1a622m4 1a623m4 1a6-2m5 1a6-3m5


Energy & Fuels

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

mB-t3a8

298.65298.65

1.013251.01325

mB-t4a8

298.20298.20

1.013251.01325

298.15298.15 298.15298.15 293.15293.15 298.15413.21 298.15298.15 298.15298.15 298.15298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.0132513.78000 1.013251.01325 1.013251.01325 1.013251.01325

298.15298.15

1.013251.01325

298.15323.15 298.15298.15 298.15298.15

1.013251.01325 1.013251.01325 1.000001.00000

298.15298.15

1.013251.01325

298.15298.15 298.15298.15 298.15298.15 298.15298.15

298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 49.78000 49.78000 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

2m13a45

293.15298.15

1.013251.01325

2m13a46

293.15303.15

1.013251.01325

2m13a47

293.15298.15

1.013251.01325

2m1a512

283.15303.15

2m32ma3

298.15323.15

2m13a4B

293.15303.15

1.013251.01325 50.00000 150.0000 0 1.013251.01325

2m13a4C6

293.15298.15

1.013251.01325

6-aC6

293.15298.16

1.013251.01325

1a7-eB 1a8-eB eB-Ba2 1a6-C6 t2a6-C6 c2a6-C6 t3a6-C6 C6-1a7 C6-1a8 C6-c4a8 C6-1a10 1a6-tet 1a7-tet 1a6-mC6 1a6-bcy 1a7-bcy a3-13a4 1a6-t2a6 1a6-t3a6 tt24a61a6 15a6-1a6 15a6t2a6 15a6t3a6 t3a6-t2a

273.15333.15

233.0000 294.0000 296.0000 344.0000 92.3000264.7000 60.0000302.3000 8.876012.1420 26.6540233.5800 97.0000208.6000 87.1000193.0000 61.7000165.2000 173.9000 241.4000 81.7000257.4000 89.0000174.0000 54.7000293.5000 105.0000 223.1000 90.7000235.6000 10.090056.4100 26.800067.0000 32.900064.0000

0.10480.6735 0.05000.9500 0.14630.7601 0.15530.7395

-79.990015.7100

0.02110.9810

3.40009.2000 4.100011.4000 21.600073.7000 25.000072.3000 42.4000177.9000 18.400072.0000 -2.70000.0000 150.0000 190.0000 5.3000214.1000 210.0000 210.0000 38.1000141.4000

0.10330.8711 0.10470.9102 0.11040.8911 0.10180.8941 0.10480.8966 0.12050.9101 0.10020.9129

Page 64 of 84

0.31000.8160

-

-

4

0

0

377

32.6

88.0

0.55

0.52500.6760

-

-

2

0

0

377

29.6

93.5

0.60

-

-

9

0

0

374

14.1

26.4

0.15

-

-

28

0

0

374,378

34.9

72.2

0.40

-

-

3

0

0

379

281.5

28.3

0.17

559.4

930.3

12.95

0.09010.8959 0.06150.9382 0.24900.7510 0.05000.9500 0.09880.7761 0.09930.7710 0.09860.8400

-

-

42

0

0

187,197 ,375

-

-

6

0

0

362

895.5

1375.3

18.82

-

-

6

0

0

362

992.6

1468.3

22.47

-

-

6

0

0

362

1150.7

1347.2

17.93

-

-

9

0

0

364

698.9

1526.1

18.33

-

-

21

0

0

55,362

533.7

1068.9

9.82

-

-

13

0

0

378

986.6

1431.6

14.60

-

-

18

0

0

223

506.9

1014.8

7.23

-

-

9

0

0

380

319.7

600.2

5.24

-

-

8

0

0

380

315.9

603.2

4.76

-

-

19

0

0

375

4549.5

1790.8

45.86

-

-

10

0

0

380

6351.2

3424.1

117.73

-

-

8

0

0

380

6378.7

3444.8

706.41

-

-

69

0

0

381

1992.0

46.5

0.42

-

-

9

0

0

382

723.6

48.2

0.28

-

-

9

0

0

382

564.2

46.0

0.26

-

-

9

0

0

382

145.6

71.8

0.42

-

-

9

0

0

382

5.9

2.5

0.02

-

-

10

0

0

382

42.0

49.4

0.30

-

-

9

0

0

382

264.5

128.8

0.77

-

-

10

0

0

382

101.2

2.0

0.01

0.50000.5000

-

-

2

0

0

24

124.1

205.1

1.40

0.00750.9545

-

-

25

0

0

24,383

108.8

157.4

0.99

0.50000.5000

-

-

2

0

0

24

144.9

304.3

1.78

0.21940.8933

-

-

34

0

0

37

435.7

427.4

1.73

5.4000100.5000

0.01510.9634

-

-

151

0

0

384

96.8

62.1

0.47

26.0000263.2000 305.0000 330.0000 45.0000235.3000

0.03820.9709

-

-

25

0

0

24,383

166.8

293.0

2.19

0.50000.5000

-

-

2

0

0

24

855.4

2692.9

95.40

0.04330.8898

-

-

36

0

0

24,197, 385

53.3

101.1

0.61

0.34400.8101 0.10790.8970 0.24400.8540 0.07180.9036 0.13990.7005


Page 65 of 84

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

Energy & Fuels

6-13aC6

298.15298.15

1.013251.01325

6-14aC6

298.15298.15

1.013251.01325

298.16298.16 298.16298.16 298.16298.16

1.013251.01325 1.013251.01325 1.013251.01325

aC6-14

298.16298.16

1.013251.01325

aC6-16

298.16298.16

1.013251.01325

B-aC6

293.15298.15

1.010001.01325

298.15298.15 298.15298.15

1.013251.01325 1.013251.01325

aC6-8 aC6-10 aC6-12

B-13aC6 B-14aC6

229.7000 436.9000 100.9000 443.3000 58.0000247.0000 24.0000293.0000 55.0000323.0000 107.0000 408.0000 54.0000427.0000 153.0000 389.3000 42.4000129.0000 33.300086.7000

0.13470.8024

-

-

9

0

0

386

72.0

263.9

1.61

0.18370.9328

-

-

10

0

0

386

69.6

248.6

1.54

-

-

22

0

0

385

77.3

152.0

0.83

-

-

23

0

0

385

91.9

219.1

1.07

-

-

27

0

0

385

98.5

267.3

1.19

0.09570.9489

-

-

20

0

0

385

101.9

317.9

1.40

0.09620.9623

-

-

27

0

0

385

104.3

343.9

1.35

0.12470.8724

-

-

21

0

0

24,197, 376

118.1

367.0

2.67

-

-

11

0

0

386

332.3

340.1

2.50

-

-

11

0

0

386

485.1

313.4

2.33

257.5

185.0

1.31

278.9

737.9

5.73

0.16180.9476 0.07570.9864 0.13760.9662

0.09270.8643 0.20300.8661

24,197, 363,366 ,387 363,386 ,388

C6-aC6

293.15308.15

1.013251.01325

0.9400116.7000

0.04510.9980

-

-

36

0

0

13aC6C6

298.15308.15

1.013251.01325

0.07140.9241

-

-

24

0

0

C614aC6

298.15308.15

1.013251.01325

0.07790.8970

-

-

22

0

0

363,386 ,388

238.3

711.1

5.59

298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 298.15298.15 348.15348.15 293.15298.15 298.15318.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 8.000008.00000 1.013251.01325 1.013251.01325

-

-

10

0

0

389

248.1

319.9

1.88

-

-

9

0

0

389

76.0

29.4

0.18

-

-

9

0

0

389

6.6

1.2

0.01

-

-

9

0

0

389

1189.0

378.9

2.01

-

-

12

0

0

389

689.9

1720.0

14.69

-

-

9

0

0

389

727.9

1683.0

14.45

-

-

10

0

0

197

660.8

610.4

5.89

-

-

9

0

0

372

74.5

13.5

0.08

-

-

2

0

0

24

1439.4

1025.7

136.41

-

-

21

0

0

390

1571.5

157.2

0.73

H2-1

183.00298.00

11.1000102.3000

0.08500.7480

0.08000.7280

0

85

24

343,345

7.6

48.1

1.01

H2-N2

147.00298.00

5.6700135.7800

96.9000358.3000 115.0000 415.5000 76.1000150.8000 19.800048.4000 6.700024.8000 17.900037.2000 98.1000292.6000 90.2000282.1000 52.6000116.1000 5.998026.2400 60.000080.0000 7.000013.2000 28.00003296.000 0 11.0000793.0000

0

323

0

345,391

6.8

18.1

0.47

18254

4334

4848

aC6-tet 13aC6tet 14aC6tet aC6-bcy 13aC6bcy 14aC6bcy 1a6-aC6 1a63maC5 2m13a4aC6 ap-bp

0.17550.7462 0.12510.7507 0.11350.7707 0.17170.6685 0.13290.6842 0.12090.7105 0.12080.8632 0.08790.8864 0.50000.5000 0.20000.7998 -

0.08600.7940 Total number of points


Energy & Fuels

298.15-298.15

6-8

298.15-298.15

6-12

298.15-298.15

22m4-7

298.15-298.15

23m4-7

298.15-298.15

2m5-7

298.15-298.15

3m5-7

298.15-298.15

7-224m5

298.15-298.15

22m4-8

298.15-298.15

23m4-8

298.15-298.15

2m5-8

298.15-298.15

3m5-8

298.15-298.15

6-B

298.20-298.20

B-7

293.15-303.15

B-8

298.20-298.20

B-10

298.20-298.20

B-12

298.20-298.20

B-14

298.20-298.20

B-16

298.20-298.20

23m4-B

298.15-298.15

B-224m5

298.15-323.15

6-mB

298.15-313.15

7-mB

298.15-298.20

mB-8

298.20-298.20

mB-10

298.20-298.20

mB-12

298.20-298.20

mB-14

298.20-298.20

mB-16

298.20-298.20

6-14mB

298.20-298.20

14mB-16

298.20-298.20

7-eB

298.20-298.20

eB-10

298.20-298.20

eB-12

298.20-298.20

eB-14

298.20-298.20

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

Number of points (T,P,cPM,x)

x1 range (1st compound liquid mole fraction)

Heat capacity of mixing range (J/mol/K) -0.0980-0.0000

0.1246-0.9081

19

-0.2260-0.0000

0.0480-0.9780

30

-1.3720-0.0000

0.0564-0.9500

29

-0.6830-0.0000

0.0263-0.9713

45

-0.4920-0.0000

0.0311-0.9762

40

-0.2750-0.0000

0.0302-0.9467

28

-0.3190-0.0000

0.0322-0.9503

20

-0.3512-0.0000

0.0391-0.9620

24

-1.0850-0.0000

0.0522-0.9741

20

-0.7030-0.0000

0.0532-0.9532

17

-0.4530-0.0000

0.0748-0.9524

19

-0.5760-0.0000

0.0469-0.9285

21

-2.9100-0.0000

0.0953-0.9161

7

-3.6330-0.0000

0.0487-0.9317

43

-3.3800-0.0000

0.1110-0.8959

7

-4.1500-0.0000

0.0977-0.8999

7

-5.0900-0.0000

0.0916-0.8977

7

-5.9590-0.0000

0.2457-0.9237

5

-7.2700-0.0000

0.0884-0.9006

7

-2.9190-0.0000

0.1498-0.8584

12

-2.9000-0.0000

0.1036-0.8990

27

-1.6000-0.0000

0.1078-0.9041

13

-1.3780-0.0000

0.1013-0.9097

13

-1.3200-0.0000

0.0999-0.9069

7

-1.8200-0.0000

0.0989-0.8966

7

-2.4700-0.0000

0.0870-0.9054

7

-3.7460-0.0000

0.1955-0.8608

5

-4.2400-0.0000

0.0872-0.9034

7

-0.4800-0.0000

0.1032-0.9039

7

-2.2000-0.0000

0.1002-0.9021

7

-1.6500-0.0000

0.1313-0.8699

8

-2.5220-0.0000

0.2053-0.8222

5

-3.0560-0.0000

0.1261-0.8879

5

-4.4540-0.0000

0.1836-0.8227

5


References

6-7

Pressure range (bar)

Temperature rage (K)

Table 3. Binary system (1st compound2nd compound)

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

Page 66 of 84

∆c M P %

392-393

36.8

0.0

394

28.8

0.0

395

15.3

0.2

392

489.6

2.2

392

482.6

1.5

392

241.5

0.4

392

162.9

0.4

396-397

1235.1

2.6

394

317.8

2.4

394

393.9

1.9

394

187.1

0.6

394

126.0

0.5

398

69.5

1.5

399-400

72.6

1.9

398

66.7

1.7

398

63.0

1.9

398

62.0

2.3

401

60.0

2.7

398

64.1

3.4

402-403

13.8

0.3

404-406

228.5

4.7

407

1530.9

14.6

401,404

1990.6

20.8

398

2319.9

22.9

398

1943.8

27.3

398

1709.3

30.6

401

1149.9

35.3

398

1148.3

36.1

398

9398.4

34.8

398

4636.8

75.8

401

1237.5

16.8

401

1167.1

24.3

401

1116.6

24.7

401

836.3

30.4

∆c M P (J/mol/K)

Page 67 of 84

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

Energy & Fuels

7-124mB

298.15-298.15

10-124mB

298.15-298.15

124mB-14

298.15-298.15

7-prB

298.20-298.20

prB-14

298.20-298.20

7-buB

298.20-298.20

buB-14

298.20-298.20

23m4-mB

298.15-298.15

224m5-mB

298.15-323.15

23m4-eB

298.15-298.15

23m4-buB

298.15-298.15

B-mB

298.15-298.15

B-12mB

298.15-298.15

B-13mB

298.15-298.15

B-14mB

298.15-313.15

B-eB

298.15-298.15

B-prB

298.15-298.15

B-buB

298.15-298.15

mB-12mB

298.15-298.15

mB-13mB

298.15-298.15

mB-14mB

298.15-298.15

mB-eB

298.15-298.15

13mB-12mB

298.15-321.65

14mB-12mB

298.15-321.65

eB-12mB

298.15-321.65

14mB-13mB

298.15-321.65

eB-13mB

298.15-321.65

eB-14mB

298.15-321.65

6-C6

298.15-298.20

C6-7

293.15-338.15

C6-12

298.15-323.15

C6-14

288.15-308.15

C6-224m5

298.15-323.15

C5-B

298.15-298.15

B-C6

293.15-318.15

B-C8

298.15-298.15

C6-mB

298.15-298.15

C6-12mB

298.15-323.15

C6-13mB

298.15-323.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

0.0750-0.3430

0.1174-0.9052

9

0.2220-0.6620

0.1142-0.9078

9

-0.1150-0.0000

0.0934-0.8734

9

-1.4180-0.0000

0.1408-0.8704

6

-4.0020-0.0000

0.2078-0.8525

5

-1.3870-0.0000

0.1721-0.8020

5

-4.4010-0.0000

0.1780-0.8388

5

-1.6710-0.0000

0.1369-0.8511

12

-1.2700-0.9000

0.1102-0.9015

30

-2.2840-0.0000

0.1600-0.8516

6

-1.5440-0.0000

0.2055-0.8384

5

-0.3150-0.0000

0.1127-0.8930

9

-1.4370-0.0000

0.1006-0.8931

9

-1.1090-0.0000

0.1045-0.8866

9

-0.8800-0.0000

0.1008-0.8772

15

-0.8710-0.0000

0.0962-0.8968

17

-0.9410-0.0000

0.1936-0.8677

5

-1.4510-0.0000

0.1349-0.8752

7

-0.4620-0.0000

0.1096-0.8891

9

-0.2100-0.0000

0.0949-0.8963

9

-0.0340-0.0020

0.1159-0.8829

9

0.0160-0.0560

0.0932-0.9002

9

-0.1420-0.0000

0.0504-0.9464

79

-0.2200-0.0000

0.0499-0.9607

79

-0.2820-0.0000

0.0502-0.9498

79

0.0030-0.0260

0.0490-0.9517

79

-0.0350-0.0000

0.0505-0.9499

86

0.0400-0.3510

0.0526-0.9516

79

-1.4190-0.0000

0.0394-0.9533

34

-2.7440-0.0000

0.0882-0.9604

49

-3.9300-0.0000

0.0473-0.9630

234

-6.1012-0.0000

0.0500-0.9502

52

-0.6000-0.0000

0.2496-0.7497

9

-2.6640-0.0000

0.0933-0.8778

9

-2.9810-0.0000

0.0955-0.9148

95

-3.3760-0.0000

0.1235-0.9084

9

-1.9200-0.0000

0.0250-0.9750

21

-1.1023-0.0000

0.2503-0.7498

9

-1.7294-0.0000

0.2495-0.7520

9


129

26779.7

61.0

129

17180.0

82.3

129

138259.1

111.5

401

1235.4

13.2

401

801.4

25.6

401

964.0

11.4

401

554.0

20.7

402-403

68.6

0.9

404-406

1057.3

8.9

402

140.1

2.5

402

411.7

5.4

408

49.6

0.1

408

64.5

0.7

408

58.4

0.5

408-409

32.9

0.2

408,410

506.5

3.1

410

688.9

5.2

410

601.6

6.7

408

76.0

0.3

408

57.7

0.1

408

431.5

0.1

408

1361.1

0.5

411-412

96.0

0.1

411-412

97.3

0.1

411-412

676.5

0.9

411-412

99.9

0.0

411-412

7240.9

1.0

411-412

704.3

1.3

393,399

14.6

0.1

218,393

33.6

0.5

413

55.4

1.3

414

63.8

2.3

415

2145.2

6.1

416

35.3

0.7

417-420

31.1

0.7

416

38.0

0.9

421

146.5

1.9

422

665.6

3.9

422

434.3

3.7

Energy & Fuels

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

C6-14mB

298.15-323.15

C6-eB

298.15-298.15

C6-prB

298.15-298.15

C6-iprB

298.15-298.15

mC5-10

293.15-293.15

7-tCC6

298.15-298.15

7-cCC6

298.15-298.15

22m4-tCC6

298.15-298.15

23m4-tCC6

298.15-298.15

2m5-tCC6

298.15-298.15

3m5-tCC6

298.15-298.15

224m5-tCC6

298.15-298.15

22m4-cCC6

298.15-298.15

23m4-cCC6

298.15-298.15

2m5-cCC6

298.15-298.15

3m5-cCC6 224m5cCC6

298.15-298.15

B-mC6

298.15-298.15

B-tCC6

298.15-298.15

B-cCC6

298.15-298.15

mC6-mB

298.15-298.15

mB-tCC6

298.15-298.15

mB-cCC6

298.15-298.15

C5-mC5

293.15-293.15

C5-mC6

293.15-293.15

mC5-C6

293.15-293.15

C6-mC6

298.15-298.15

C6-tCC6

298.15-298.15

C6-cCC6

298.15-298.15

C8-tCC6

298.15-298.15

C8-cCC6

298.15-298.15

mC5-mC6

293.15-293.15

mC6-tCC6

298.15-298.15

mC6-cCC6

298.15-298.15

298.15-298.15

1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325 1.013251.01325

Page 68 of 84

-1.1914-1.2102

0.2537-0.7415

9

-2.2300-0.0000

0.0250-0.9750

21

-2.1900-0.0000

0.0250-0.9750

21

-2.0300-0.0000

0.0250-0.9750

19

-1.5440-0.0000

0.0862-0.8990

10

-0.7650-0.0000

0.0500-0.9500

19

-1.4580-0.0000

0.0500-0.9500

19

-1.1720-0.0000

0.0500-0.9500

11

-0.9530-0.0000

0.0500-0.9500

11

-0.8270-0.0000

0.0500-0.9500

11

-0.7660-0.0000

0.0500-0.9500

11

-0.7430-0.0000

0.0500-0.9500

19

-1.3340-0.0000

0.0500-0.9500

11

-1.2150-0.0000

0.1000-0.9500

10

-1.3980-0.0000

0.0500-0.9500

11

-1.2350-0.0000

0.0500-0.9500

11

-1.2610-0.0000

0.0500-0.9500

19

-2.7100-0.0000

0.0500-0.9750

29

-2.7990-0.0000

0.0500-0.9500

19

-3.0960-0.0000

0.0500-0.9500

19

-1.7500-0.0000

0.0250-0.9750

20

-1.6930-0.0000

0.0500-0.9500

19

-2.0460-0.0000

0.0500-0.9500

19

-0.0270-0.0160

0.1252-0.9009

11

0.0520-0.2900

0.0402-0.9117

12

-0.2740-0.0000

0.0712-0.8951

14

-0.2800-0.2800

0.0500-0.9750

20

-0.5290-0.3720

0.0500-0.9500

11

-0.5130-0.5450

0.0500-0.9500

11

-0.2820-0.0680

0.0500-0.9500

11

-0.4650-0.0000

0.0500-0.9500

11

0.0730-0.2400

0.0608-0.9079

11

-0.5850-0.0000

0.0500-0.9500

11

-0.8170-0.0000 0.0500-0.9500 Total number of points:

11 2251


422

611.9

4.2

295

67.7

1.0

295

193.6

2.9

295

119.9

1.7

423

8138.5

85.0

424

16871.3

98.2

424

9281.8

99.0

304

12232.6

91.4

304

13784.7

90.4

304

16154.0

86.5

304

18895.5

85.6

424

22822.8

117.6

304

10105.2

92.4

304

11117.8

98.0

304

9093.0

87.2

304

10045.5

86.3

424

12680.7

118.7

416,425

2584.1

49.1

424

3471.6

69.6

424

3172.0

70.5

424

1981.1

22.9

424

2413.1

29.7

424

2085.3

30.3

423

201291.6

29.0

423

15086.9

20.2

423

17402.9

33.1

425

21471.9

18.7

316

98235.3

19.7

316

7896.1

19.7

316

14615.3

23.6

316

9047.3

24.0

423

327.3

0.6

316

626.0

2.7

316

485.5

2.6

Page 69 of 84

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

Energy & Fuels

Table 4.

Families Alkanes Aromatic compounds Naphthenes CO2 N2 H2 S Mercaptans Alkenes H2 Total

Number of experimental data

Relative mean deviation

3,405 5,544 8,368 4,940 883 39 246 3,579 432 27,436

628.7 % 88.20 % 1490. % 64.96 % 16.34 % 56.42 % 362. 9 % 227.6 % 6.978 % 595.6 %

∆h M %

Absolute mean deviation

∆h M


( J ⋅ mol ) −1

88.64 145.9 324.5 175.9 52.18 48.73 395.5 173.0 25.69 199.4

Deviation expressed in terms of temperature ∆Th K 0.51 0.77 2.3 1.3 0.99 1.3 29 3.4 0.61 1.9

Energy & Fuels

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

Page 70 of 84

Table 5.

Families

Number of experimental data

Relative mean deviation

Alkanes Aromatic compounds Naphthenes Total

312 907 1,032 2,251

327.7 % 3001 % 7038 % 4481 %

∆c M P %


Absolute mean deviation ∆c M P

( J ⋅ mol

−1

0.3746 7.125 25.03 14.50

⋅ K −1

)

Page 71 of 84

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

Energy & Fuels

List of Figures Fig. 1. Phase behavior prediction of the binary system n-hexane(1) + n-octane(2) at 403.2 K. (a) pressure-composition phase diagram at T. (b) enthalpy of mixing-composition curves (i.e., hM-curves) plotted at T and {P = 1 bar, P = 3 bar, P = 5.5 bar}. (c) Enlargement of (b). Fig. 2. Phase behavior of the binary system CO2(1) + ethane(2) at 273.15 K (showing homogeneous azeotropy) and 293.15 K (showing homogeneous azeotropy and criticality), predicted with the PPR78 model. (a) and (d): isothermal phase equilibrium diagrams in the Pxy plane. (b) and (e): isothermal and isobaric hM-curves associated to the horizontal lines in subfigures (a) and (d) respectively. (c) hM-curve plotted at 273.15 K and the corresponding azeotropic pressure; Laz and Vaz = azeotropic liquid phase and azeotropic gas phase in equilibrium; zaz = mole fraction of component 1 at the azeotropic point. Fig. 3. Phase behavior of the binary system H2O(1) + 1,3,5-trimethylbenzene(2) at 552 K (showing heteroazeotropy) predicted with the Peng-Robinson EoS using Van der Waals mixing rules and a binary interaction parameter k12 = 0.0284. (a) isothermal phase equilibrium diagram in the Pxy plane. (b) isothermal and isobaric hM-curves associated to the horizontal lines in subfigure (a). (c) hM-curve plotted at 552 K and the corresponding VLLE pressure; Lα*, Lβ*, and V* = liquid phases and gas phase involved in a 3-phase equilibrium. Fig. 4. Prediction of hM (a) and cPM (b) curves for the binary system: benzene(1) + isooctane(2) at T = 298.15 K and P = 1.0 atm. () experimental hM and cPM points (references provided in Tables 2 and 3). Solid line: calculated curves (Peng-Robinson EoS with Van der Waals mixing rules). Fig. 5

Prediction of enthalpies of mixing by the PPR78 model: overall statistical results per chemical family. (a) relative mean deviations. (b) absolute mean deviations. (c) absolute deviations expressed in terms of temperature. Dashed lines: average values.

Fig. 6

Prediction of mixing enthalpies of three binary systems (two alkane + alkane systems and one H2 + alkane system) in or near domains of two-phase equilibria, by the PPR78 EoS. Left-hand side subfigures (a,c,e): isothermal or isobaric projections of phase-equilibrium diagrams. Right-hand side subfigures (b,d,f): isothermal and isobaric (hM vs. composition) curves. Continuous curves: calculated with the PPR78 model. () experimental data.

Fig. 7

Prediction by the PPR78 EoS of mixing enthalpies of three binary systems (one CO2 + alkane system; one CO2 + naphthene system and one N2 + alkane system) in or near domains of two-phase equilibria. Left-hand side subfigures (a,c,e): isothermal or isobaric projections of phase-equilibrium diagrams. Right-hand side subfigures (b,d,f): isothermal and isobaric (hM vs. composition) curves. Continuous curves: calculated with the PPR78 model. () experimental data.

Fig. 8

Prediction by the PPR78 EoS of mixing enthalpies of liquid binary systems containing alkanes, aromatic compounds and naphthenes. Continuous curves: calculated with the PPR78 model. () experimental data.

Fig. 9

Prediction by the PPR78 EoS of mixing enthalpies of liquid binary systems containing alkanes, alkenes and CO2. Continuous curves: calculated with the PPR78 model. () experimental data. 71 - Environment ACS Paragon-Plus

Energy & Fuels

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

Fig. 10 Prediction by the PPR78 EoS of mixing enthalpies of gaseous binary systems containing alkanes, alkenes, N2 and CO2. Continuous curves: calculated with the PPR78 model. () experimental data. Fig. 11 Prediction of isobaric heat capacity of mixing by the PPR78 model: overall statistical results per chemical family. (a) relative mean deviations. (b) absolute mean deviations.. Dashed lines: average values. Fig. 12 Prediction by the PPR78 EoS of isobaric heat capacities of liquid binary systems containing alkanes, aromatic compounds and naphthenes. Continuous curves: calculated with the PPR78 model. () experimental data.


Page 72 of 84

Page 73 of 84

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

Energy & Fuels

Figure 1. 5.00

(a)

P/bar

4.00

3.00

2.00

z1

1.00

y1

x1

0.0

1.0 z 2 ⋅ ∆ vap H 2

(b)

(c)

hM/(kJ/mol)

M h gas (T, P = 3 bar, z ) ≠ h E

M E h gas (T, P = 1 bar, z ) = h gas

0.

0. M E h liq (T, P = 5.5 bar, z ) = h liq

-0.04

−z1 ⋅ ∆ vap H1

hM VLE (T, P = 3 bar, z )

-10. 0.

M h liq (T, P = 3 bar, z ) ≠ h E

0.

0.4

z1 0.8


0.4

0.8

Energy & Fuels

Figure 2. 9000. P4 = 40 bar

40.0

(b)

P/bar

(a)

hM/(J/mol)

T = 273.15 K

7000.

P3 = 37 bar

P3 = 37 bar

T = 273.15 K

5000. P2 = 30 bar

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

Page 74 of 84

P2 = 30 bar

30.0

3000.

P4 = 40 bar 1000.

P1 = 23 bar

P1 = 23 bar z1

x1,y1

-1000.

20.0 0.0

0.5

0.

1.0

0.4

0.8

10000.0

8000.0

hM/(J/mol)

Vaz

(c) T = 273.15 K

6000.0

4000.0

2000.0

P = azeotropic pressure

Laz

Liquid branch

z1 0.0 0.0

zaz

0.5

1.0

5500.

65.0 P5 = 64 bar

(e)

P/bar

P4 = 60 bar

4500.

P4 = 60 bar

(d)

P2 = 46 bar P3 = 56 bar

55.0

hM/(J/mol)

T = 293.15 K

3500. P5 = 64 bar 2500.

P2 = 46 bar

1500.

45.0

P3 = 56 bar

T = 293.15 K 500.

P1 = 36 bar P1 = 36 bar

x1, y1

35.0 0.0

0.5

1.0

z1 -500. 0.


0.4

0.8

Page 75 of 84

Figure 3. (a) 200.0

27000.

P/bar

P5 = 200 bar

(b)

hM/(J/mol) P3 = 70 bar

21000.

T = 552.00 K

150.0

T = 552.00 K

P4 = 100 bar

15000. P4 = 100 bar

100.0

9000.

P3 = 70 bar

50.0

P5 = 200 bar

P2 = 40 bar

P2 = 40 bar

3000.

P1 = 5 bar

x1,y1

P1 = 5 bar

z1

0.0

-3000.

0.0

0.5

1.0

30000.0

0.

0.4

(c)

hM/(J/mol)

V*

20000.0

T = 552.00 K P = three-phase equilibrium pressure

Lα*

3-phase region

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

Energy & Fuels

10000.0

Lβ*

0.0 0.0

0.5

1.0


z1

0.8

Energy & Fuels

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

Page 76 of 84

Figure 4. 0.0

(i) dkij/dT = -1.7× ×10−4 K–1 (PPR78)

(a)

hM/(J/mol)

1200.0 (ii) dkij/dT = -5.7× ×10−5 K–1 (best fit)

(ii) d2kij/dT2 = 0.0

-4.0

800.0

(i) d2kij/dT2 = 2.0× ×10−6 K–2 (PPR78)

(iii) dkij/dT = 0.0

400.0

T = 298.15 K P = 1.00 atm kij = 0.002869

-8.0 x1

0.0 0.0

0.5

cPM/(J/mol/K)

(iii) d2kij/dT2 = -1.0× ×10−7 K–2 (best fit)

1.0

T = 298.15 K P = 1.00 bar kij = 0.002869 dkij/dT = -1.7×10-4 K–1 0.0


0.5

(b)

x1 1.0

Page 77 of 84

Figure 5. 1600.0

(a)

400.

∆hM %

1200.0

(

(b)

∆hM J ⋅ mol−1

300.

800.0

200.

400.0

100.

∆Th K

24.0

16.0

8.0

H2

Alkenes

Mercaptans

H2S

N2

CO2

Naphthenes

Aromatic comp.

Families 0.0


H2

Alkenes

H2S

Mercaptans

N2

CO2

Naphthenes

Aromatic comp.

Alkanes

H2

Alkenes

Mercaptans

Families 0.

(c)

Alkanes

H2S

N2

CO2

Naphthenes

Aromatic comp.

Families

0.0

Alkanes

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

Energy & Fuels

)

Energy & Fuels

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

Page 78 of 84

Figure 6.

(b)

P/bar

(a)

140.0

hM/(J/mol) P3 = 150.00 bar

0.0

P2 = 100.00 bar 100.0

-1000.0

Ethane(1) + propane(2) T = 323.15 K

P1 = 50.00 bar -2000.0

60.0

x1,y1

20.0 0.0

0.5

Ethane(1) + propane(2) -3000.0 T = 323.15 K 0.0

1.0

z1

0.5

1.0

500.0

(c)

T/K

hM/(J/mol)

(d) 000.

Methane(1) + n-heptane(2) P = 138.0 bar

T2 = 310.90 K

300.0

-400.

Methane(1) + n-heptane(2) P = 138.0 bar

T1 = 255.40 K x1,y1

z1

-800.

100.0 0.0

0.5

0.

1.0

P/bar

(e)

0.4

0.8

hM/(J/mol)

(f)

P4 = 41.40 bar

3000.0

P5 = 51.60 bar

80.0

H2(1) + methane(2) T = 183.0 K

P6 = 61.70 bar P7 = 77.10 bar

2000.0

60.0

P8 = 91.30 bar

1000.0

40.0

H2(1) + methane(2) T = 183.0 K P3 = 36.40 bar P2 = 31.50 bar

x1,y1

20.0 0.0

0.5

1.0

x1,y1

P1 = 21.30 bar

0.0 0.0


0.5

1.0

Page 79 of 84

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

Energy & Fuels

Figure 7. 570.0

T1 = 293.15K T2 = 323.15K T3 = 363.15K T4 = 413.15K T5 = 470.15K T6 = 573.15K

T/K

CO2(1) + n-decane(2) P = 125.0 bar

530.0

(a) 2000.

490.0

hM/(J/mol)

(b)

450.0 410.0

0000.

370.0 330.0 x1,y1

290.0 0.0

0.5

(c) 540.0

CO2(1) + n-decane(2) P = 125.0 bar

-2000.

0.

1.0

0.4

0.8

(d)

T/K

CO2(1) + cyclohexane(2) P = 75.0 bar

z1

hM/(J/mol) T1 = 308.15 K T2 = 358.15 K T3 = 413.15 K T4 = 470.15 K T5 = 508.15 K T6 = 573.15 K

4000.0

460.0

0.0 380.0

x1,y1

300.0 0.0

0.5

CO2(1) + cyclohexane(2) P = 75.0 bar

0.0

1.0

(e)

80.0

-4000.0

P/bar

3000.0

(f)

0.5

hM/(J/mol)

P1 = 21.40 bar P2 = 31.30 bar P3 = 40.80 bar P4 = 55.50 bar P5 = 71.60 bar P6 = 82.10 bar

2000.0

40.0

1.0

N2(1) + methane(2) T = 183.0 K

N2(1) + methane(2) T = 183.0 K

60.0

z1

1000.0

x1,y1

20.0

z1 0.0

0.0

0.5

1.0

0.0


0.5

1.0

Energy & Fuels

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

Page 80 of 84

Figure 8. T1 = 283.15 K T2 = 293.15 K T3 = 298.15 K T4 = 303.15 K T5 = 308.15 K

80.0

hM/(J/mol)

(a)

240.0

hM/(J/mol)

(b)

T = 298.15 K P = 1.00 atm

3-methylpentane (1) + n-dodecane (2) n-decane (2) n-octane(2) n-heptane(2)

120.0

40.0

n-hexane(1) + n-dodecane(2) P = 1.00 atm

0.0 0.0

x1

0.5

1.0

0.0

hM/(J/mol)

(c)

1200.0

x1 0.0

T = 323.15 K P = 1.00 atm

0.5

1.0 hM/(J/mol)

(d) 40.0

800.0

20.0

Toluene(1) + p-xylene(2) P = 1.01 bar

400.0 Benzene(1)-eicosane(2) Benzene(1) + n-hexadecane (2) Benzene(1) + n-dodecane(2) Benzene(1) + n-octane (2) n-hexane + benzene(2)

0.0

T1 = 298.15 K T2 = 308.15 K T3 = 323.15 K T4 = 338.15 K

x1

x1

0.0

0.0

0.5

1.0

0.0

hM/(J/mol)

(e)

0.5

hM/(J/mol)

Cyclopentane(1) + cyclooctane(2) P = 1.00 atm T1 = 288.25 K T2 = 298.15 K T3 = 308.32 K

-10.0

800.0

1.0

-30.0

T = 298.15 K P = 1.00 atm

400.0

Benzene(1) + cyclohexane(2) Cyclohexane(1) + toluene(2) Cyclohexane(1)-ethylbenzene(2) Cyclohexane(1) + propylbenzene(2) Cyclohexane(1)+1-methylnaphthalene (2)

0.0 0.0

0.5

x1 1.0

(f)

-50.0

x1 0.0

0.5


1.0

Page 81 of 84

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Energy & Fuels

Figure 9. hM/(J/mol)

(a)

80.0

hM/(J/mol)

(b)

1600.0

40.0

800.0

T = 298.15 K P = 1.00 atm

CO2(1) + ethane (2) T = 272.10 K P1 = 45. 00 bar P2 = 110.00 bar

Hex-1-ene(1) + 2,3-dimethylbutane(2) Hex-1-ene(1) + 2,2-dimethylbutane (2) Hex-1-ene(1) + 2-methylpentane (2) Hex-1-ene(1) + 2,2,4-trimethylpentane (2)

x1

0.0

0.0

0.0

0.5

1.0

0.0

100.0 hM/(J/mol)

(c)

4000.

0.5

x1 1.0

CO2(1) + n-hexane(2) T = 470.15K

(d)

hM/(J/mol)

P1 = 75.00 bar P2 = 105.00 bar

-50.0 2000.

Ethylene(1) + propane(2) T = 273.15 K P1 = 75.00 bar P2 = 100.00 bar P3 = 125.00 bar P4 = 150.00 bar

-200.0 0.0

0.5

P3 = 125.00 bar

x1

x1 0.

1.0

0.


0.4

0.8

Energy & Fuels

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Page 82 of 84

Figure 10. hM/(J/mol)

(a)

6.0

Methane(1) + CO2(2) T = 293.15 K

(b)

hM/(J/mol)

400.0

4.0

P1 = 10.13 bar P2 = 20.27 bar P3 = 30.40 bar P4 = 40.53 bar P5 = 50.66 bar

200.0

2.0

Methane(1) + ethane(2) P = 1.00 atm T1 = 241.10 K T2 = 269.20 K T3 = 298.20 K

0.0

y1

y1 0.0

0.0

0.5

1.0

0.0

0.5

1.0

1200.0

(c)

hM/(J/mol)

N2(1) + CO2(2) T = 293.15 K

600.0

P1 = 50.66 bar P2 = 40.53 bar P3 = 30.40 bar P4 = 20.26 bar P5 = 10.13 bar

400.0

(d)

hM/(J/mol)

N2(1) + ethylene (2) T = 283.15 K

800.0 P1 = 10.36 bar P2 = 20.72 bar P3 = 34.54 bar P4 = 48.35 bar 400.0

200.0

y1

y1

0.0

0.0 0.0

2000.

0.5

Ethylene(1) + propane(2) T = 373.15 K

0.0

1.0

hM/(J/mol)

(e)

1600.0

P1 = 75.00 bar P2 = 100.00 bar P3 = 125.00 bar P4 = 150.00 bar

1000.

0.5

1.0

P1 = 11.10 bar P2 = 21.30 bar P3 = 31.80 bar P4 = 41.70 bar P5 = 51.30 bar P6 = 61.50 bar P7 = 81.50 bar

(f)

hM/(J/mol)

H2(1) + methane(2) T = 201.00 K

800.0

0.0 y1 0.0

0.5

1.0

y1

0.0 0.0


0.5

1.0

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Energy & Fuels

Figure 11. ∆cM P%

(a)

24.0

∆cPM

(b)

( J ⋅ mol

6000.0

16.0

4000.0

8.0

2000.0

Families 0.0

Alkanes

Aromatic comp.

Naphthenes

Families 0.0

Alkanes

Aromatic comp.


Naphthenes

−1

⋅ K −1

)

Energy & Fuels

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Page 84 of 84

Figure 12. 0.0

cPM /(J/mol/K)

T = 298.15 K P = 1.00 atm -2.0

n-hexane(1) + n-heptane(2) 2-methylpentane(1) + n-heptane(2) 2,3-dimethylbutane(1) + n-heptane(2) 2,2-dimethylbutane (1) + n-heptane(2)

(a)

-4.0

x1

0.0

0.5

1.0 0.0

0.0

T = 298.15 K P = 1.00 atm

-2.0

Cyclohexane(1) + n-heptane(2) P = 1.00 atm

cPM /(J/mol/K)

Cyclopentane(1) + benzene(2) Benzene(1) + cyclohexane(2) Benzene(1) + cyclooctane(2)

-1.0

T1 = 298.15 K T2 = 308.15 K T3 = 318.15 K T4 = 328.15 K T5 = 338.15 K

-2.0

-4.0

(b) 0.0

(c)

x1 0.5

cPM /(J/mol/K)

1.0

0.0


0.5

x1 1.0

Enthalpy and Heat Capacity Changes on Mixing: Fundamental

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