Effect of high pressure and temperature on volumetric properties of {water (1) + ethylenediamine (2)} mixtures

Accepted Manuscript Effect of high pressure and temperature on volumetric properties of {water (1)+ethylenediamine (2)} mixtures

Gennadiy I. Egorov, Dmitriy M. Makarov PII: DOI: Reference:

S0167-7322(16)31017-0 doi: 10.1016/j.molliq.2017.03.095 MOLLIQ 7130

To appear in:

Journal of Molecular Liquids

Received date: Accepted date:

26 April 2016 25 March 2017

Please cite this article as: Gennadiy I. Egorov, Dmitriy M. Makarov , Effect of high pressure and temperature on volumetric properties of {water (1)+ethylenediamine (2)} mixtures. The address for the corresponding author was captured as affiliation for all authors. Please check if appropriate. Molliq(2017), doi: 10.1016/j.molliq.2017.03.095

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ACCEPTED MANUSCRIPT Effect of high pressure and temperature on volumetric properties of {water (1) + ethylenediamine (2)} mixtures Gennadiy I. Egorov*, Dmitriy M. Makarov * To whom correspondence may be addressed. E-mail: [email protected] G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo, Russia

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Abstract For {water (1) + ethylenediamine (2)} binary mixture the densities at atmospheric pressure and compressions, k  V Vo , at pressures from 10 to 100 MPa of have been measured over the whole concentration range and temperatures from 278.15 to 323.15 K. The molar isothermal compressions and molar isobaric expansions, the thermal pressure coefficients and the internal pressure of water + ethylenediamine mixture have been calculated at all state parameters examined. It was shown that the values of molar isothermal compression and molar isobaric expansion of the mixtures rich in water varied insignificantly whereas the thermal pressure coefficients changed strongly within that concentration range. The magnitude of the extreme on the concentration dependence of the thermal pressure coefficient was unusually large that was probably connected with the influence of 2H2O-EDA hydrate complex.

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Key words: Ethylenediamine Aqueous mixture · Molar isothermal compressions Molar isobaric expansions Internal pressure

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1. Introduction The solvents with spatial H-bond network have some characteristic features such as small compressibility and expansibility, moreover the hydrogen bonds cooperativity is their distinctive property. Ethylenediamine (EDA) is normally reckoned among the above solvents, though, according to the opinion of many researchers [1-6], the H-bond network in EDA is less developed than the network in water. In the mixtures of ethylenediamine with water different EDA–water and EDA–EDA hydrogen bonds can form, e.g. Н-О•••Н-O, H-O•••H-N, and H-N•••H-N (hydrogen atoms of ethylene groups are out of our consideration), and the ratio of these bonds determines the physico-chemical properties and packing of the mixture. The interest to investigation of intermolecular interactions and structural properties of aqueous EDA solutions is caused by their numerous applications. EDA is widely used in petrochemical industry, as well as for production of dyes, emulsifiers, latexes stabilizers, antioxidant motor oil additives, plasticizers, fungicides, and drugs. Moreover some EDA-based technologies are developed for greenhouse gases control [7-8]. The volumetric properties of water + ethylenediamine mixture at atmospheric pressure were studied by us earlier [9]. For better understanding of intermolecular processes in water + ethylenediamine mixture, the compression of the system has been measured over the wide range of concentrations, pressures, and temperatures. So far there is the lack of the experimental data on the compressibility of water + ethylenediamine mixture over the wide pressure range. For example only one work [10] presents the results of the system compression measurements at pressures close to the atmospheric one (direct method of isothermal compression measurement at very small pressure differential) over the temperature range of (278.15 to 333.15) K and the data on pure EDA compression at temperatures from (293.15 to 333.15) K are performed in [2].

2. Experimental Section For the solutions preparation the solvents of the highest available purity were used and their properties are shown in Table 1. EDA was purified by means of its boiling with sodium metal, according to Refs. [11, 12], and further double distillation. EDA purified was kept under vacuum. The water content was determined by K. Fisher’s method and did not exceed 0.05 wt.% (or ≈17·10-4 mole

ACCEPTED MANUSCRIPT 2 fraction). The mixtures were prepared gravimetrically from the solvents degasified. The calculated amounts of EDA and water were loaded under vacuum into individual vessels. Then the solvents were mixed using the capillary system. The mixtures preparation, loading, and measurements of the compression were carried out without the contact of the solutions with atmospheric air, which was very important because of active reaction of EDA with CO2. About 250 ml of every solution was prepared for every measurement. Only freshly prepared solutions were investigated. The highest uncertainty of the mixture compositions did not exceed 1·10-4 molar fraction (the water determined in EDA was considered as an impurity).

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Purification method Double vacuum distillation with sodium metal Double distillation (≈ 2·10-4 S·m-1)

Analysis method K. Fisher method

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Table 1. Supplier and purity of the chemicals used. Chemical name Supplier Purity (% mass) Ethylenediamine Chemical ≥0.995 (mass Line fraction)

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The densities,  o , at atmospheric pressure were measured using an Anton Paar DMA-4500 vibration densimeter with U-shaped vibrating tube. The temperature reproducibility was equal to 0.01 K. The reproducibility of the density values was equal to 1·10-5 g·cm-3. The density measurements were carried out at five temperatures: 278.15, 288.15, 298.15, 308.15, and 323.15 K. The standard uncertainty of the temperature measurement during the density determining did not exceed 0.03 K. The combined expanded uncertainty of the density measurements (0.95 level of confidence) did not exceed 5·10-5 g·cm-3. The procedure was described in details earlier [13, 14]. The compression measurements were conducted with installation described in Refs. [14-16] and using the constant volume piezometers (40 ml). The reproducibility of the compression k, was about 5·10-5 as an averaged of four measurements for water at 100 MPa and 298.15 K. The uncertainty of the pressure measurement was about 0.02%; the uncertainty of the temperature keeping during the compression measurements was 0.02 K. The standard uncertainty of k measurements was lower than 1·10-4. The compressibility of the mixtures with small EDA concentrations was measured with a piezometer of 230 ml volume. The detailed description of the experimental technique was performed in [13-14]. The compression (the relative volume change), k , was determined by the following equation: (1) k = vo  v  / vo =   o  / 

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where vo ,  o and v ,  were the specific volumes and densities of {water (1) + ethylenediamine (2)} mixture at atmospheric pressure ( po =0.101±0.003 MPa) and at pressure p , respectively. The densities of the mixture obtained with equation (1) are listed in Table S1 (Supporting Information section). 3. Results The molar isothermal compression, KT , m , was determined as following:

KT , m  Vm pT , x   T Vm  M  2   p T , x

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where  T was the coefficient of isothermal compressibility, Vm was the molar volume,  was the mixture density, M was the molar weight of the mixture with a certain composition. To calculate KT , m values the pressure dependences of the mixture density at every composition and temperature studied were fitted with 2nd order polynomials ; those polynomials were then differentiated. The calculation results are listed in Supporting Information section (Table S2). The molar isobaric expansion, EP , m , was calculated with equation (3):

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where  p was the coefficient of the isobaric thermal expansion. The procedure of EP , m calculation was similar to the one for the molar isothermal compression determination, i.e.   f (T ) p , x functions were fitted with 2nd order polynomials for every mixture composition, and the resulting polynomials were differentiated. The results are shown in Supporting Information section (Table S3). In Tables S1 and S2 the literature data on the molar isothermal compression, KT , m , and the molar isobaric expansion, EP , m , of ethylenediamine are shown for comparison. As one can see from the tables our results are in a good agreement with the literature data. The thermal pressure coefficient,  , was calculated by the following equation:   p T V  E P , m KT , m T , p, x

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The internal pressure, pint , characterizing the change of the internal energy U of the mixture under small isothermal expansion, V , was determined as following: (5) pint  U V T , x   T p T V , x  p

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In equation (5) the internal pressure is assumed to be the negative value, pint <0, as the wellknown Maxwell equation ( p  T (p T )V  (U V )T ) is regarded as the sum but not the difference of kinetic (external) pressure pext  T (p T )V and static (internal) pressure pint  (U V )T [1721]. The relative average uncertainty of determination of the molar isothermal compressions, molar isobaric expansions, coefficients of thermal pressure, and the internal pressures did not exceed ±3·10-5 cm3·mol-1·MPa-1, ±3·10-5·cm3·mol-1·K-1, ±0.15·MPa·K-1, and ±30·MPa, respectively.

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4. Discussion

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The intrinsic spatial H-bond networks in pure water and EDA predetermine the properties of these solvents mixture. Because of their different structures each of those networks dominates when the appropriate solvent is in excess, but within some limited concentration range. The formation of any water-EDA complexes also varies significantly the number of hydrogen bonds in the mixture. The temperature and pressure also affect the H-bonds number. Liquid water has, due to its structure, some unique properties which distinguish it from other solvents. It is known that the temperature dependence of the molar isothermal compression of water is extremal and passes through the minimum at ≈318 K whereas the pressure dependence of the molar isobaric expansion of water has the temperature inversion region. Moreover EP , m and  are negative within the temperature interval from 273.15 to 277.13 K, i.e. the heating within these limits under isochoric conditions causes some “vacuum” formation inside the intrinsic water structure. In contrast to other solvents the isochoric elasticity of water increases with temperature growth and the temperature dependences of its internal pressure at ≈315 K are also characterized by the region of baric inversion [22-26]. Ethylenediamine, unlike water, is a “normal” liquid and its volume characteristics do not stand out from the properties of the most solvents; however there are some peculiarities.

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Fig. 1. Densities of {water (1) + ethylenediamine (2)} mixture,  , depending on EDA molar fraction, x2 : (a) at 100 MPa and various temperatures: (- 278.15 K, - 288.15 K, - 298.15 K, - 308.15 K, and - 323.15 K); (b) at 278.15K and various pressures: (- 0.10 MPa, - 10 MPa, - 25 MPa, 50 MPa, - 75 MPa, and - 100 MPa).

  f ( x2 ) functions of water + EDA mixtures at low temperatures have distinct extremes at

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x2` ≈ 0.3 (Fig. 1). These extremes are leveled by both temperature and pressure increase and transform into the curve inflection. The extreme appears due to intense breaking of water under the influence of small EDA concentrations, on the one hand, and , on the other hand, to formation of water-EDA associates. Earlier [11, 27] it was shown that the phase melting diagram of water + ethylenediamine mixture was indicative of the presence of two hydrate complexes in the solid phase: the first one (1:1) melted congruentially at 283 K and the second one (2:1) melted incongruently at 263 K. In the liquid phase these complexes reveal themselves also and, especially, under the temperature lowering [28]. All these processes result in different concentration dependences of the mixture compression and expansion at low and high EDA concentrations. As one can see in Figure 2 the molar isothermal compressions of water + ethylenediamine mixtures rich in water are small. Moreover KT , m  f ( x2 ) functions pass through weak minima within

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Fig. 2. Molar isothermal compressions of {water (1) + ethylenediamine (2)} mixture, KT ,m , depending on EDA molar fraction, x2 : (a) at 0.101 MPa and various temperatures: (- 278.15 K, - 288.15 K, - 298.15 K, - 308.15 K, - 323.15 K); (b) at 278.15 K and at various pressures: (- 0.10 MPa, - 10 MPa, - 25 MPa, - 50 MPa, - 75 MPa, and - 100 MPa).

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ACCEPTED MANUSCRIPT 5 The temperature inversion region appears on KT , m  f ( x2 ) dependences at low EDA concentrations. Such behavior is the result of the opposite temperature dependences of the molar isothermal compressions of water and EDA. The similar KT , m  f ( x2 ) dependences are observed for the most of aqueous nonelectrolytes solutions which is connected with the peculiarities of water structure.

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Fig. 3. Comparison of our experimental and literature data on the coefficients of isothermal compressibility of {water (1) + ethylenediamine (2)} mixture,  T , depending on EDA molar fraction, x2 , at 0.10 MPaed: (- this work, 278.15K; - Dhondge et al. at 279.15K [29]; - this work, 298.15K; - Kartsev et al., 298.15 K [30, 10].

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In Figure 3 the concentration dependences of the coefficients of isothermal compressibility of water + ethylenediamine mixture obtained in this work and taken from Refs. [30, 10, 29] are shown. Unfortunately it was possible to convert  T literature values into KT ,m ones not at every temperature.

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The values of  T were obtained by Dhondge et al. [29] from acoustical measurements; Kartsev et al. [30, 10] measured the coefficients by direct method at small pressure differential. As one can see in Fig. 3 satisfactory agreement is observed between the values obtained by us and the literature data. The molar isobaric expansion of the mixture, EP , m , (Fig. 4) increases with EDA concentration rising at all temperatures and pressures studied. Unlike the dependences at atmospheric pressure, the temperature inversion appears on EP , m  f ( x2 ) functions at pressures above 50 MPa and high EDA values increase for the mixtures rich in water but decrease when the

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Fig. 4. Molar isobaric expansions of {water (1) + ethylenediamine (2)} mixture, EP , m , on EDA molar fraction, x2 : (a) at 100 MPa and various temperatures: (- 278.15 K, - 288.15 K, - 298.15 K, -

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Fig. 5. Comparison of our experimental and literature data on the coefficients of isobaric thermal expansion of {water (1) + ethylenediamine (2)} mixture,  P , depending on EDA molar fraction, x2 , at 0.10 MPa: - at 298.15 K (this work) - at 308.15 K (this work),  - at 298.15K (by Kartsev et al. [10]), - at 308.15 K (by Saleh et al. [31]).

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The coefficient of thermal expansion was measured earlier with dilatometric method [10] and calculated using the density values [31]. As one can see in Fig. 5 our data agree satisfactorily with both these results. The thermal pressure coefficient,  , is sensitive to variation of intermolecular associative equilibria in liquids. The thermal pressure under isochoric conditions is determined both by the intensity of the molecules thermal vibrations and by the system structural variability under external parameters variation. The value of the coefficient in a liquid mixture depends on the force of intermolecular interactions and on the system packing density;  is able to vary significantly with the external parameters variation. In the case of strong structural transformations in a liquid, as, for example, it occurs in water at temperatures from 273.15 K to 277.13 K at atmospheric pressure, the thermal pressure coefficient is able to possess even the negative values.

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Fig. 6. Thermal pressure coefficient,  , of {water (1) + ethylenediamine (2)} mixture depending on EDA molar fraction, x2 : (a) at 0.101 MPa and various temperatures: (- 278.15 K, - 288.15 K, -

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The thermal pressure coefficient of water + ethylenediamine mixture is positive at all state parameters and over the whole concentration range (Fig. 6). With the first batches of EDA the thermal pressure coefficient of the mixture goes up sharply and reaches the maximum at x2 ≈0.3. Small  values for pure water and mixtures with low EDA content are connected with the skeleton structure of their H-bond networks and with the presence of empty cavities [24, 35-37, 32, 38]; within this concentration range the increase of temperature, pressure or EDA concentration results in the rising of the thermal pressure coefficient. In aqueous mixtures of non-electrolytes bearing hydrophobic groups as, for example, acetone, isopropanol or tert-butanol, such process results in formation of sharp extreme on   f ( x2 ) function [13, 32, 39]. The participation of non-electrolyte molecules in H-bond network formation, e.g. in water+ ethylene glycol or water + glycerol mixtures, results in appearance of diffused extreme on   f ( x2 ) dependence, and the extreme shifts to the region of higher concentrations at that. On the one hand, the extreme is clearly defined (Fig. 6) for the system under investigation as against the dependence for water + ethylene glycol mixture. On the other hand, the extreme is observed at higher concentrations of nonelectrolyte as compared with the extreme on   f ( x2 ) function for water+ tert-butanol mixture. The extreme position corresponds to the mixture composition, where 2H2O-EDA hydrates form. As one can see in Fig. 6 the extreme for water + ethylenediamine mixture is much higher then the corresponding values for water+ tert-butanol, water + ethylene glycol and water + glycerol mixtures. It is the evidence of strong intermolecular interactions in water + EDA mixture. Probably the mechanism of interaction between H-bond network of water and non-electrolyte molecules, described in Refs. [13, 32-34, 39], is effected by some peculiarities of water + ethylenediamine mixture, namely by the formation of the complexes (2:1) mentioned above. As it was shown earlier [40-42], the thermal coefficient of internal pressure, pint T , is sensitive to the structure of liquids and can be used for analysis of the structure of solvents in which the spatial H-bond network forms. The solvents with relatively weak intermolecular interactions are characterized by the positive pint T values whereas the negative values of the coefficient point out the formation of developed H-bond network.

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5. Conclusions The changes of isothermal compression, isobaric expansion, and thermal pressure coefficient of {water (1) + ethylenediamine (2)} mixture point out the fact that the mixture properties are mainly determined by the prevalence of water H-bond network. The liquid mixture of water and ethylenediamine is characterized by the developed H-bond network. The hydrate complexes (2Н2О-EDA), formed in the system under investigation, influence the dependences of the volumetric properties of water + ethylenediamine mixture. The analysis of the above characteristics of water + ethylenediamine mixture reveals that the temperature and pressure changes cause rearrangement of the hydrogen bonds between the mixture components.

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Acknowledgments This work was supported by the Russian Foundation for Basic Research (projects 15-43-03092r_centre_а and 15-43-03093-r_centre_а). The density measurements were made with a densimeter Anton Paar 5000 at the center for joint use of scientific equipment (the Upper Volga Regional Center for Physioc-Chemical Research).

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Appendix A. Supplementary data Supplementary data to this article can be found online at ______________

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References: [1] A.L. Wilson, New Aliphatic Amines, Ind. Eng. Chem. 27 (1935) 867–871. [2] M.N. Buslaeva, V.N. Kartsev, K.T.Dudnikova, Structure and isothermal compression of liquid ethylenediamine, Zh. Fiz. Khim. 56 (1982) 1254–255. [3] M.N. Rodnikova, A.N. Isaev, S.A. Zasypkin, Conformation of ethylenediamine in gaseous phase and in aqueous solution, Koord. Khim. 17 (1991) 1467–1472. [4] Y. Cheng, M. Pagé, C. Jolicoeur, Comparative Study of Hydrofobic Effects in Water/Alcohol and Water/Ethylene Glycol, Water/Ethanolamine, Water/Ethylenediamine and Water/2Methoxyethanol Systems, J. Phys. Chem. 97 (1993) 7359-7363. [5] Y.-P. Chang, T.-M. Su, T.-W. Li, I. Chao, Intramolecular Hydrogen Bonding, Gauche Interactions, and Thermodynamic Functions of 1,2-Ethanediamine, 1,2-Ethanediol, and 2-Aminoethanol: A Global Conformational Analysis, J. Phys. Chem. A 101 (1997) 6107-6117. [6] A.V. Gubskaya, P.G. Kusalik, Molecular Dynamics Simulation Study of Ethylene Glycol, Ethylenediamine, and 2-Aminoethanol. 2. Structure in Aqueous Solutions, J. Phys. Chem. A 108 (2004) 7165-7178. [7] H. Lepaumier, D. Picq, P.L. Carrette, New amines for CO2 capture. I. Mechanisms of amine degradation in the presence of CO2, Ind. Eng. Chem. Res. 48 (2009) 9061–9067. [8] E. Sada, H. Kumazawa, M.A. Butt, Absorption of carbon dioxide into aqueous solutions of ethylenediamine: effect of interfacial turbulence, Chem. Eng. J. 13 (1977) 213–217. [9] G.I. Egorov, D.M. Makarov, A.M. Kolker, Thermochimica Acta. 2016, (in press) [10] V.N. Kartsev, V.N. Tsypulin, M.N. Rodnikova, K.T. Dudnikova, Piezometry and densimetry of diluted aqueous solutions of diamines, amino alcohols and diols. I. Diamines’ solutions. Zh. Fiz. Khim. 62 (1988) 2233-2236. [11] M. S. El'gort, Internal friction and meltability of ethylenediamine – water mixture, J. Rus. Phys. Chem. Soc., 61 (1929) 947-959. [12] V.F. Ust’-Kachkintsev, Surface tension and refraction of ethylenediamine – water system and their relation with other properties, Zh. Fiz. Khim. 6 (1935) 67–72.

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[13] G.I. Egorov, D.M. Makarov, Compressibility Coefficients of Water–2-Propanol Mixtures over the Temperature and Pressure Ranges 278–323.15 K and 1–1000 bar Russ. J. Phys. Chem. A, 82 (2008) 1037–1041. [14] G.I. Egorov, D.M. Makarov, A.M. Kolker, Densities and Volumetric Properties of Ethylene Glycol + Dimethylsulfoxide Mixtures at Temperatures of (278.15 to 323.15) K and Pressures of (0.1 to 100) MPa, J. Chem. Eng. Data 55 (2010) 3481–3488. [15] G.I. Egorov, A.A. Sirbu, A.M. Kolker The installation for measurement of compression of nonelectrolyte solution at temperatures from 240 to 500K and pressures from 0.1 to 150 MPa Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. (in Russian) 42 (1998). 59-62. [16] G.I. Egorov, D.M. Makarov, A.M. Kolker Liquid phase PVTx properties of (water + tert-butanol) binary mixtures at temperatures from 278.15 to 323.15 K and pressures from 0.1 to 100 MPa I. Experimental results, excess and partial molar volumes. J. Chem. Thermodyn. 61 (2013) 161–168 [17] E.A. Moelwin-Hughes, Physical Chemistry; Pergamon Press: London, 1961. [18] J.H Hildebrand, The Solubility of Non-Electrolytes, New York, Reinhold, 1936 (Moscow: GONTI NKTP, 1938 166p.) [19] V.N. Kartsev, M.N. Rodnikova, S.N. Shtykov, On Internal Pressure, Its Temperature Dependence, and the Structure of Liquid-Phase Systems. J. Struct. Chem. 45 (2004) 96−99. [20] E.V. Ivanov, V.K. Abrosimov, Relationship Between the Internal Pressure and Cohesive Energy Density of a Liquid Nonelectrolyte. Consequences of Application of Dack’s Concept. J. Struct. Chem. 46 (2005) 856−861. [21] V.N. Kartsev, S.N. Shtykov, K.E. Pankin, D.V. Batov, Intermolecular Forces and the Internal Pressure of Liquids. J. Struct. Chem. 53 (2012) 1087−1093. [22] G.S. Kell, E. Whalley, Reanalysis of the density of liquid water in the range 0°–150ºC and 0–1 kbar, J. Chem. Phys. 62 (1975) 3496–3503. [23] B. Guignon, C. Aparicio, P.D. Sanz, Specific Volume of Liquid Water from (253 to 323) K and Pressures up to 350 MPa by Volumetric Measurements, J. Chem. Eng. Data 55 (2010) 3338– 3345. [24] F. Mallamace, C. Corsaro, H.E. Stanley, A singular thermodynamically consistent temperature at the origin of the anomalous behavior of liquid water. Sci. Rep. 2 (2012) 993-5. [25] Ch-T. Chen, R.A. Fine, F.J. Millero, The equation of state of pure water determined from sound speeds, J. Chem. Phys. 66 (1977) 2142–2144. [26] S. Asada, T. Sotani, J. Arabas, H. Kubota, S. Matsuo, Y. Tanaka, Density of water at subzero temperature under high pressure: measurements and correlation, J. Phys.: Condens. Matter 14 (2002) 11447–11452. [27] de R. Guieu, J.-C. Rosso, Luce Carbonnel, Les systemes binaires eau-ethylene diamine et eau propylene 1.3-diamine. C. R. Acad. Sc. Paris, 287C (1978) 495–498. [28] T. M. Val’kovskaya, M. N. Rodnikova, F. M. Samigullin, and G. V. Spivak Mobility of Water Molecules in Diamine Solutions J. Phys. Chem. A 72 (1998) 527–532 [29] S.S. Dhondge, C. Pandhurnekar, L. Ramesh, Thermodynamic studies of some non-electrolytes in aqueous solutions at low temperatures, J. Chem. Thermodyn. 40 (2008) 1–15. [30] V.N. Kartsev, M.N. Buslaeva, V.N. Tsypulin, , K.T. Dudnikova, Isothermal compressibility within the homologous series of alkanes, alcohols and diamines, Zh. Fiz. Khim. 58 (1984) 2687– 2691. [31] M.A. Saleh, S. Akhtar, M.S. Ahmed, Excess molar volumes of aqueous systems of some diamines, J. Mol. Liq. 116 (2005) 147–156. [32] G.I. Egorov, D.M. Makarov, A.M. Kolker, Liquid phase PVTx properties of (water + tertbutanol) binary mixtures at temperatures from 278.15 to 323.15 K and pressures from 0.1 to 100 MPa. II. Molar isothermal compressions, molar isobaric expansions, molar thermal pressure coefficients, and internal pressure, J. Chem. Thermodyn. 61 (2013) 169–179. [33] G.I. Egorov, D.M. Makarov, A.M. Kolker, Liquid phase PVTx properties of binary mixtures of (water + ethylene glycol) in the range from 278.15 to 323.15 K and from 0.1 to 100 MPa. II.Molar isothermal compressions, molar isobaric expansions, thermal pressure coefficients and internal pressure, Fluid Phase Equilib. 354 (2013) 133–146.

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[34] G.I. Egorov, D.M. Makarov, Volumetric properties of binary liquid-phase mixture of (water + glycerol) at temperatures of (278.15 to 323.15) K and pressures of (0.1 to 100) MPa, J. Chem. Thermodyn. 79 (2014) 135–158 [35] B. Santra, R.A. DiStasio Jr, F. Martelli, R. Car, Local structure analysis in ab initio liquid water. Mol. Phys. 113 (2015) 2829–2841 [36] G. Malenkov, Liquid water and ices: understanding the structure and physical properties. J. Phys.: Condens. Matter 21 (2009) 283101 (35pp). [37] G.N.I. Clark, C.D. Cappa, J.D. Smith, R.J. Saykally, T. Head-Gordon, The structure of ambient water. Mol. Phys. 108 (2010) 1415–1433. [38] G.I. Egorov, D.M. Makarov, Densities and volume properties of (water + tert-butanol) over the temperature range of (274.15 to 348.15) K at pressure of0.1 MPa, J. Chem. Thermodyn. 43 (2011) 430–441. [39] G.I. Egorov, E.L. Gruznov, A.M. Kolker, The p-Vm-T-x properties of water-acetone mixtures over the temperature range 298-323 K and pressures from 1 to 1000 bar. II. Isothermal compressions, isobaric expansions and internal, Russ. J. Phys. Chem. A 70 (1996) 197–203 [40] V.N. Kartsev, M.N. Rodnikova, I. Bartel, S.N. Shtykov, The Temperature Dependence of Internal Pressure in Liquids, Russ. J. Phys. Chem. A 76 (2002) 903–905. [41] V.N. Kartsev, M.N. Rodnikova, S.N. Shtykov, J. Bartel, Internal Pressure in Binary Aqueous Solutions of Monoethanolamine, Diamines, and Diols, Russ. J. Phys. Chem. A 77 (2003) 1303– 1309. [42] V.N. Kartsev, S.N. Shtykov, M.N. Rodnikova, Inversion of the Temperature Coefficient of Internal Pressure and Structural Organization of Liquid Phase Systems, J. Struct. Chem. 45 (2004) 91–95.

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Supporting Information Effect of high pressure and temperature on volumetric properties of {water (1) + ethylenediamine (2)} mixtures

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Gennadiy I. Egorov*, Dmitriy M. Makarov G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo, Russia

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* To whom correspondence may be addressed. E-mail addresses: [email protected]

11

ACCEPTED MANUSCRIPT 12

1.00430 1.00312 1.00083 0.99767 0.99160

1.01119 1.00973 1.00720 1.00392 0.99782

0.00721

278.15 288.15 298.15 308.15 323.15

0.99943 0.99838 0.99620 0.99309 0.98700

1.00405 1.00283 1.00050 0.99730 0.99117

1.01084 1.00937 1.00681 1.00352 0.99733

0.00898

278.15 288.15 298.15 308.15 323.15

0.99932 0.99823 0.99601 0.99287 0.98675

1.00390 1.00265 1.00028 0.99705 0.99089

0.01234

278.15 288.15 298.15 308.15 323.15

0.99907 0.99787 0.99554 0.99239 0.98624

0.02220

278.15 288.15 298.15 308.15 323.15

1.03284 1.03046 1.02726 1.02361 1.01716

1.04293 1.04002 1.03656 1.03264 1.02624

1.02183 1.01990 1.01699 1.01349 1.00711

1.03237 1.02992 1.02672 1.02306 1.01654

1.04229 1.03938 1.03597 1.03202 1.02548

1.01063 1.00916 1.00657 1.00321 0.99702

1.02153 1.01961 1.01669 1.01316 1.00677

1.03198 1.02957 1.02636 1.02263 1.01611

1.04187 1.03898 1.03554 1.03161 1.02507

1.00357 1.00224 0.99976 0.99652 0.99034

1.01021 1.00865 1.00597 1.00263 0.99638

1.02095 1.01897 1.01599 1.01247 1.00607

1.03123 1.02882 1.02557 1.02186 1.01537

1.04115 1.03815 1.03466 1.03078 1.02425

0.99862 0.99712 0.99461 0.99125 0.98489

1.00294 1.00134 0.99870 0.99527 0.98889

1.00928 1.00750 1.00474 1.00118 0.99477

1.01957 1.01746 1.01447 1.01080 1.00429

1.02952 1.02704 1.02379 1.01996 1.01334

1.03909 1.03621 1.03265 1.02865 1.02204

0.04365

278.15 288.15 298.15 308.15 323.15

0.99859 0.99636 0.99331 0.98953 0.98266

1.00256 1.00029 0.99716 0.99333 0.98649

1.00838 1.00603 1.00283 0.99896 0.99216

1.01785 1.01532 1.01198 1.00804 1.00124

1.02701 1.02423 1.02075 1.01674 1.00997

1.03583 1.03276 1.02911 1.02504 1.01817

0.06094

278.15 288.15 298.15 308.15 323.15

0.99931 0.99647 0.99296 0.98877 0.98144

1.00303 1.00020 0.99663 0.99244 0.98515

1.00852 1.00566 1.00208 0.99786 0.99069

1.01744 1.01451 1.01087 1.00661 0.99949

1.02607 1.02301 1.01930 1.01498 1.00793

1.03436 1.03114 1.02733 1.02295 1.01584

0.08265

278.15

1.00079

1.00423

1.00941

1.01780

1.02584

1.03354

NU

MA

D

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CE

AC

1.02228 1.02035 1.01746 1.01397 1.00771

RI

0.99962 0.99864 0.99650 0.99342 0.98740

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0.00465

278.15 288.15 298.15 308.15 323.15

PT

Table S1 Densities of {water (1) + ethylenediamine (2)} mixture,  , within the pressure range from 0.10 to 100 MPa and at temperatures from 278.15 to 323.15 K a.  /(g·cm-3) x2 Т/K 0.101 10.0 25.0 50.0 75.0 100.0 278.15 0.99996 1.00478 1.01188 1.02320 1.03392 1.04408 288.15 0.99909 1.00366 1.01042 1.02121 1.03147 1.04123 298.15 0.99704 1.00146 1.00799 1.01844 1.02838 1.03786 0.00000 308.15 0.99403 0.99836 1.00474 1.01497 1.02471 1.03401 0.98803 0.99230 0.99861 1.00868 1.01827 1.02742 323.15

12

ACCEPTED MANUSCRIPT 1.00071 0.99655 0.99190 0.98400

1.00589 1.00175 0.99711 0.98935

1.01426 1.01013 1.00554 0.99787

1.02229 1.01818 1.01362 1.00601

1.02995 1.02585 1.02132 1.01364

0.10597

278.15 288.15 298.15 308.15 323.15

1.00272 0.99837 0.99356 0.98834 0.97964

1.00596 1.00168 0.99686 0.99170 0.98313

1.01084 1.00658 1.00181 0.99669 0.98832

1.01873 1.01454 1.00983 1.00477 0.99663

1.02633 1.02219 1.01753 1.01253 1.00450

1.03358 1.02950 1.02492 1.01997 1.01191

0.14808

278.15 288.15 298.15 308.15 323.15

1.00644 1.00083 0.99490 0.98868 0.97870

1.00942 1.00388 0.99801 0.99188 0.98201

1.01390 1.00848 1.00269 0.99663 0.98702

1.02118 1.01593 1.01025 1.00433 0.99504

1.02820 1.02306 1.01752 1.01175 1.00263

1.03495 1.02989 1.02449 1.01886 1.00979

0.20630

278.15 288.15 298.15 308.15 323.15

1.00932 1.00248 0.99533 0.98795 0.97641

1.01213 1.00539 0.99832 0.99104 0.97964

1.01642 1.00981 1.00286 0.99570 0.98457

1.02336 1.01692 1.01015 1.00316 0.99244

1.03000 1.02368 1.01709 1.01027 0.99985

1.03636 1.03008 1.02364 1.01700 1.00677

0.25129

278.15 288.15 298.15 308.15 323.15

1.00893 1.00108 0.99349 0.98555 0.97314

1.01172 1.00396 0.99647 0.98863 0.97637

1.01601 1.00837 1.00100 0.99330 0.98133

1.02293 1.01545 1.00827 1.00076 0.98922

1.02954 1.02218 1.01517 1.00783 0.99663

1.03582 1.02853 1.02171 1.01449 1.00353

0.31480

278.15 288.15 298.15 308.15 323.15

1.00273 0.99500 0.98582 0.97870 0.96484

1.00556 0.99794 0.98887 0.98187 0.96816

1.00994 1.00245 0.99348 0.98666 0.97327

1.01700 1.00965 1.00085 0.99430 0.98135

1.02374 1.01648 1.00781 1.00149 0.98886

1.03014 1.02289 1.01435 1.00820 0.99578

0.34097

278.15 288.15 298.15 308.15 323.15

1.00140 0.99278 0.98426 0.97515 0.96196

1.00427 0.99577 0.98736 0.97838 0.96535

1.00872 1.00033 0.99204 0.98325 0.97054

1.01591 1.00764 0.99952 0.99102 0.97874

1.02281 1.01459 1.00662 0.99829 0.98633

1.02927 1.02115 1.01331 1.00507 0.99331

0.40378

278.15 288.15 298.15 308.15 323.15

0.99234 0.98369 0.97496 0.96590 0.95212

0.99531 0.98678 0.97819 0.96926 0.95566

0.99989 0.99149 0.98308 0.97437 0.96108

1.00736 0.99911 0.99089 0.98247 0.96960

1.01460 1.00637 0.99824 0.99004 0.97746

1.02159 1.01329 1.00511 0.99704 0.98461

0.49282

278.15 288.15 298.15 308.15 323.15

0.97780 0.96871 0.95994 0.95076 0.93696

0.98096 0.97201 0.96340 0.95436 0.94073

0.98579 0.97704 0.96865 0.95986 0.94650

0.99370 0.98514 0.97698 0.96847 0.95556

1.00135 0.99287 0.98476 0.97636 0.96383

1.00877 1.00020 0.99194 0.98349 0.97132

0.59066

278.15 288.15 298.15 308.15

0.96176 0.95242 0.94388 0.93472

0.96512 0.95591 0.94755 0.93856

0.97028 0.96124 0.95310 0.94443

0.97869 0.96985 0.96194 0.95356

0.98686 0.97806 0.97022 0.96185

0.99475 0.98587 0.97792 0.96924

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0.99720 0.99306 0.98838 0.98039

AC

13 288.15 298.15 308.15 323.15

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ACCEPTED MANUSCRIPT 14 0.92079

0.92482

0.93095

0.94051

0.94925

0.95710

0.68432

278.15 288.15 298.15 308.15 323.15

0.94787 0.93888 0.92980 0.92072 0.90680

0.95140 0.94254 0.93365 0.92474 0.91105

0.95687 0.94816 0.93950 0.93088 0.91745

0.96571 0.95719 0.94875 0.94041 0.92746

0.97417 0.96575 0.95732 0.94907 0.93658

0.98225 0.97381 0.96519 0.95678 0.94476

0.79536

278.15 288.15 298.15 308.15 323.15

0.93317 0.92408 0.91493 0.90570 0.89179

0.93690 0.92796 0.91900 0.90997 0.89629

0.94257 0.93382 0.92512 0.91637 0.90300

0.95177 0.94320 0.93478 0.92633 0.91345

0.96065 0.95203 0.94370 0.93538 0.92291

0.96896 0.96030 0.95187 0.94345 0.93132

0.85052

278.15 288.15 298.15 308.15 323.15

0.92649 0.91735 0.90814 0.89888 0.88484

0.92134 0.91233 0.90327 0.88946

0.92739 0.91862 0.90982 0.89630

0.93699 0.92848 0.91998 0.90696

0.94590 0.93752 0.92915 0.91659

0.95408 0.94566 0.93726 0.92513

0.89800

278.15 288.15 298.15 308.15 323.15

0.92128 0.91203 0.90285 0.89440 0.87953

0.91612 0.90715 0.89892 0.88428

0.92232 0.91359 0.90562 0.89125

0.93211 0.92363 0.91598 0.90209

0.94111 0.93273 0.92524 0.91186

0.94930 0.94085 0.93334 0.92049

0.92815

278.15 288.15 298.15 308.15 323.15

0.91789 0.90876 0.89958 0.89023 0.87610

0.91291 0.90396 0.89482 0.88092

0.91923 0.91052 0.90162 0.88800

0.92915 0.92068 0.91203 0.89899

0.93824 0.92991 0.92146 0.90887

0.94646 0.93803 0.92959 0.91756

0.95840

278.15 288.15 298.15 308.15 323.15

0.91489 0.90541 0.89608 0.88670 0.87278

0.90962 0.90052 0.89135 0.87768

0.91605 0.90718 0.89819 0.88485

0.92610 0.91748 0.90881 0.89599

0.93530 0.92677 0.91829 0.90600

0.94359 0.93495 0.92666 0.91483

0.97933

288.15 298.15 308.15 323.15

0.90345 0.89401 0.88480 0.87049

0.90773 0.89852 0.88951 0.87545

0.91425 0.90527 0.89644 0.88271

0.92444 0.91571 0.90714 0.89397

0.93373 0.92506 0.91674 0.90409

0.94203 0.93327 0.92514 0.91298

1.00000

288.15 298.15 308.15 323.15

0.90126 0.89190 0.88249 0.86823

0.90560 0.89648 0.88725 0.87323

0.91222 0.90331 0.89426 0.88054

0.92253 0.91386 0.90510 0.89189

0.93184 0.92330 0.91483 0.90214

0.94011 0.93155 0.92336 0.91119

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323.15

a

Standard uncertainties, u, are u(T) = 0.03 K, u(p) = 0.02%p, u(x) = 0.0001, and the combined expanded uncertainties Uc are Uc(ρ) = 5·10-5 (0.95 level of confidence) and Uc(ρ) = 1·10-4 (0.95 level of confidence) at p=0.101 MPa and p>0.1 MPa, respectively.

Table S2 Molar isothermal compressions, K T , m , of {water (1) + ethylenediamine (2)} mixture at temperatures from 278.15 to 323.15 K and pressures from 0.10 to 100 MPa a.

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ACCEPTED MANUSCRIPT 15 x2

Т (K)

K T , m ·103/(cm3·mol-1·MPa-1) at p (MPa) 0.10 0.88 0.83 0.81 0.80 0.80

10.0 0.85 0.81 0.79 0.78 0.78

25.0 0.82 0.78 0.76 0.75 0.75

50.0 0.76 0.73 0.71 0.70 0.70

0.00465

278.15 288.15 298.15 308.15 323.15

0.86 0.83 0.80 0.79 0.79

0.84 0.81 0.78 0.77 0.77

0.81 0.78 0.75 0.75 0.74

0.00721

278.15 288.15 298.15 308.15 323.15

0.86 0.83 0.80 0.79 0.79

0.84 0.81 0.78 0.77 0.77

0.81 0.78 0.75 0.74 0.74

0.00898

278.15 288.15 298.15 308.15 323.15

0.85 0.83 0.80 0.79 0.79

0.83 0.80 0.78 0.77 0.77

0.80 0.77 0.75 0.74 0.74

0.01234

278.15 288.15 298.15 308.15 323.15

0.84 0.82 0.80 0.79 0.79

0.82 0.80 0.78 0.77 0.77

0.02220

278.15 288.15 298.15 308.15 323.15

0.82 0.80 0.79 0.79 0.79

0.04365

278.15 288.15 298.15 308.15 323.15

0.70 0.68 0.66 0.65 0.65

100.0 0.65 0.63 0.61 0.61 0.60

0.76 0.73 0.71 0.70 0.70

0.70 0.67 0.66 0.65 0.65

0.65 0.62 0.61 0.60 0.61

0.75 0.72 0.71 0.70 0.70

0.70 0.67 0.66 0.65 0.65

0.65 0.62 0.61 0.60 0.60

0.75 0.72 0.71 0.70 0.70

0.70 0.67 0.66 0.65 0.65

0.65 0.62 0.61 0.60 0.61

0.80 0.77 0.75 0.74 0.74

0.75 0.72 0.70 0.70 0.70

0.70 0.67 0.66 0.65 0.65

0.66 0.62 0.61 0.60 0.61

0.81 0.79 0.77 0.77 0.77

0.78 0.76 0.75 0.74 0.74

0.74 0.72 0.70 0.70 0.70

0.70 0.67 0.66 0.65 0.66

0.66 0.63 0.61 0.61 0.61

0.79 0.79 0.78 0.78 0.80

0.78 0.77 0.76 0.76 0.78

0.75 0.74 0.74 0.74 0.75

0.72 0.70 0.70 0.70 0.71

0.68 0.66 0.65 0.65 0.66

0.64 0.62 0.61 0.61 0.61

0.06094

278.15 288.15 298.15 308.15 323.15

0.77 0.78 0.78 0.78 0.81

0.76 0.76 0.76 0.77 0.79

0.73 0.74 0.74 0.74 0.76

0.70 0.69 0.69 0.70 0.71

0.66 0.65 0.65 0.65 0.66

0.62 0.61 0.61 0.61 0.61

0.08265

278.15 288.15 298.15 308.15

0.76 0.77 0.77 0.79

0.74 0.75 0.76 0.77

0.72 0.73 0.73 0.74

0.68 0.69 0.69 0.70

0.64 0.65 0.65 0.66

0.61 0.60 0.61 0.62

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NU

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AC

75.0

PT

0.00000

278.15 288.15 298.15 308.15 323.15

15

ACCEPTED MANUSCRIPT 16 0.82

0.80

0.77

0.72

0.67

0.62

0.10597

278.15 288.15 298.15 308.15 323.15

0.74 0.76 0.77 0.78 0.83

0.73 0.74 0.75 0.77 0.82

0.71 0.72 0.73 0.74 0.78

0.67 0.68 0.69 0.71 0.73

0.63 0.64 0.66 0.67 0.68

0.60 0.61 0.62 0.63 0.63

0.14808

278.15 288.15 298.15 308.15 323.15

0.73 0.76 0.78 0.80 0.87

0.72 0.74 0.76 0.79 0.85

0.70 0.72 0.74 0.77 0.82

0.67 0.68 0.70 0.73 0.76

0.63 0.65 0.67 0.69 0.71

0.60 0.61 0.63 0.65 0.66

0.20630

278.15 288.15 298.15 308.15 323.15

0.76 0.80 0.84 0.87 0.95

0.75 0.79 0.82 0.85 0.92

0.73 0.76 0.79 0.82 0.89

0.69 0.72 0.74 0.77 0.83

0.65 0.67 0.70 0.72 0.77

0.62 0.63 0.65 0.68 0.71

0.25129

278.15 288.15 298.15 308.15 323.15

0.82 0.86 0.90 0.94 1.03

0.80 0.84 0.88 0.92 1.00

0.78 0.81 0.85 0.88 0.96

0.74 0.76 0.80 0.83 0.89

0.70 0.72 0.75 0.77 0.83

0.66 0.67 0.70 0.72 0.76

0.31480

278.15 288.15 298.15 308.15 323.15

0.92 0.97 1.02 1.07 1.18

0.91 0.95 0.99 1.05 1.15

0.88 0.92 0.96 1.01 1.09

0.83 0.86 0.89 0.94 1.01

0.79 0.80 0.83 0.87 0.93

0.74 0.75 0.77 0.80 0.84

0.34097

278.15 288.15 298.15 308.15 323.15

0.98 1.02 1.07 1.14 1.25

0.96 1.00 1.04 1.11 1.21

0.93 0.97 1.01 1.07 1.16

0.88 0.91 0.95 0.99 1.07

0.83 0.85 0.88 0.91 0.97

0.78 0.79 0.82 0.84 0.88

0.40378

278.15 288.15 298.15 308.15 323.15

1.10 1.16 1.24 1.32 1.44

1.08 1.14 1.21 1.28 1.40

1.05 1.10 1.16 1.23 1.33

1.01 1.04 1.08 1.13 1.22

0.97 0.98 1.00 1.04 1.11

0.93 0.92 0.92 0.95 0.99

0.49282

278.15 288.15 298.15 308.15 323.15

1.32 1.41 1.52 1.63 1.76

1.30 1.38 1.48 1.58 1.70

1.27 1.34 1.41 1.50 1.62

1.22 1.26 1.31 1.36 1.47

1.17 1.19 1.20 1.23 1.32

1.11 1.11 1.09 1.09 1.17

0.59066

278.15 288.15 298.15 308.15 323.15

1.61 1.72 1.84 2.00 2.15

1.59 1.68 1.79 1.93 2.07

1.55 1.62 1.71 1.82 1.96

1.48 1.53 1.58 1.64 1.77

1.42 1.44 1.46 1.46 1.58

1.35 1.35 1.33 1.28 1.40

0.68432

278.15

1.93

1.89

1.83

1.73

1.64

1.54

RI SC

NU

MA

D

PT E

CE

AC

PT

323.15

16

ACCEPTED MANUSCRIPT

0.95840

0.97933

1.00000

1.55 1.52 1.49 1.62

278.15 288.15 298.15 308.15 323.15

2.29 2.42 2.60 2.80 3.03

2.24 2.36 2.52 2.70 2.92

2.17 2.27 2.40 2.54 2.75

2.04 2.11 2.19 2.28 2.46

1.92 1.95 1.98 2.02 2.17

1.80 1.79 1.77 1.76 1.88

288.15 298.15 308.15 323.15

2.67 2.85 3.05 3.30

2.59 2.76 2.93 3.17

2.47 2.61 2.76 2.98

2.26 2.36 2.46 2.65

2.06 2.11 2.16 2.33

1.86 1.86 1.86 2.01

288.15 298.15 308.15 323.15

2.88 3.08 3.29 3.53

2.79 2.96 3.15 3.39

2.65 2.79 2.95 3.18

2.41 2.50 2.61 2.83

2.17 2.21 2.27 2.47

1.94 1.93 1.93 2.12

288.15 298.15 308.15 323.15

3.02 3.23 3.44 3.70

2.92 3.11 3.29 3.55

2.77 2.92 3.08 3.33

2.51 2.61 2.72 2.95

2.25 2.30 2.36 2.57

1.99 1.98 2.01 2.19

288.15 298.15 308.15 323.15

3.17 3.38 3.57 3.87

3.06 3.25 3.43 3.71

2.89 3.05 3.21 3.47

2.62 2.71 2.84 3.08

2.34 2.38 2.48 2.68

2.06 2.05 2.11 2.29

288.15 298.15 308.15 323.15

3.29 3.51 3.69 3.99

3.17 3.37 3.54 3.83

2.99 3.15 3.31 3.58

2.69 2.79 2.92 3.17

2.40 2.44 2.54 2.76

2.10 2.08 2.16 2.35

288.15 298.15

3.41 3.62 3.40b 3.80 4.09

3.28 3.48

3.09 3.25

2.76 2.88

2.44 2.50

2.12 2.13

3.65 3.93

3.41 3.68

3.02 3.27

2.63 2.85

2.23 2.44

RI SC

AC

308.15 323.15

PT

1.67 1.69 1.71 1.85

NU

0.92815

1.79 1.85 1.92 2.08

MA

0.89800

1.91 2.02 2.14 2.31

PT E

0.85052

1.99 2.12 2.27 2.45

CE

0.79536

2.04 2.18 2.35 2.54

D

17 288.15 298.15 308.15 323.15

a

standard uncertainties, u, of the values measured: u(T)=0.03 K, u(p)=0.02 %, u(x) = 1·10-4, u( K T , m ) = 6·10-5 cm3·mol-1·MPa-1. b calculated from Ref.[30]

Table S3 Molar isobaric expansions, E P , m , of {water (1) + ethylenediamine (2)} mixture at temperatures from 278.15 to 323.15 K and pressures from 0.1 to 100 MPa a.

x2 0.00000

Т (K) 278.15 288.15 298.15

E P , m ·102/(cm3·mol-1·K-1) at p (MPa) 0.10 0.096 0.269 0.443

10.0 0.141 0.302 0.464

25.0 0.203 0.347 0.492

50.0 0.294 0.415 0.535

75.0 0.373 0.472 0.571

100.0 0.435 0.518 0.601

17

ACCEPTED MANUSCRIPT 0.625 0.867

0.637 0.854

0.655 0.836

0.671 0.820

0.685 0.810

0.00465

278.15 288.15 298.15 308.15 323.15

0.120 0.291 0.462 0.633 0.889

0.160 0.319 0.479 0.639 0.879

0.218 0.361 0.504 0.647 0.861

0.306 0.426 0.546 0.666 0.846

0.379 0.480 0.581 0.682 0.833

0.468 0.542 0.615 0.688 0.798

0.00721

278.15 288.15 298.15 308.15 323.15

0.132 0.302 0.473 0.644 0.901

0.167 0.328 0.490 0.651 0.893

0.222 0.367 0.513 0.658 0.876

0.304 0.429 0.554 0.679 0.866

0.386 0.488 0.590 0.692 0.845

0.459 0.540 0.622 0.703 0.824

0.00898

278.15 288.15 298.15 308.15 323.15

0.141 0.311 0.482 0.652 0.907

0.176 0.337 0.498 0.659 0.901

0.227 0.373 0.520 0.666 0.886

0.305 0.431 0.558 0.684 0.874

0.386 0.490 0.595 0.699 0.856

0.462 0.543 0.625 0.706 0.828

0.01234

278.15 288.15 298.15 308.15 323.15

0.167 0.333 0.498 0.664 0.911

0.200 0.357 0.513 0.670 0.904

0.246 0.390 0.534 0.678 0.893

0.321 0.445 0.569 0.693 0.879

0.396 0.498 0.601 0.703 0.857

0.484 0.560 0.635 0.710 0.823

0.02220

278.15 288.15 298.15 308.15 323.15

0.225 0.388 0.550 0.712 0.956

0.251 0.406 0.561 0.716 0.948

0.285 0.430 0.576 0.721 0.939

0.345 0.472 0.600 0.727 0.918

0.409 0.519 0.628 0.737 0.901

0.489 0.573 0.658 0.742 0.869

0.04365

278.15 288.15 298.15 308.15 323.15

0.382 0.531 0.681 0.830 1.054

0.396 0.540 0.683 0.827 1.042

0.415 0.550 0.684 0.819 1.021

0.449 0.570 0.691 0.813 0.994

0.493 0.597 0.701 0.806 0.962

0.536 0.627 0.717 0.808 0.944

0.06094

278.15 288.15 298.15 308.15 323.15

0.523 0.661 0.800 0.938 1.145

0.527 0.662 0.796 0.930 1.132

0.536 0.662 0.787 0.912 1.100

0.547 0.664 0.781 0.898 1.074

0.570 0.675 0.779 0.884 1.040

0.591 0.688 0.785 0.882 1.027

0.08265

278.15 288.15 298.15 308.15 323.15

0.711 0.836 0.962 1.087 1.275

0.704 0.826 0.949 1.071 1.255

0.701 0.817 0.932 1.047 1.220

0.696 0.804 0.912 1.020 1.181

0.687 0.790 0.893 0.996 1.150

0.676 0.779 0.882 0.985 1.139

0.10597

278.15 288.15 298.15 308.15 323.15

0.918 1.031 1.145 1.258 1.428

0.909 1.017 1.126 1.235 1.397

0.902 1.002 1.102 1.202 1.352

0.885 0.976 1.067 1.158 1.294

0.862 0.950 1.038 1.126 1.258

0.827 0.920 1.013 1.106 1.246

0.14808

278.15

1.298

1.273

1.249

1.206

1.158

1.111

SC

NU

MA

D

PT E

CE

AC

PT

0.617 0.878

RI

18 308.15 323.15

18

ACCEPTED MANUSCRIPT 1.369 1.465 1.561 1.705

1.337 1.426 1.514 1.647

1.287 1.368 1.449 1.571

1.238 1.317 1.397 1.516

1.194 1.276 1.359 1.482

0.20630

278.15 288.15 298.15 308.15 323.15

1.759 1.858 1.957 2.055 2.203

1.727 1.824 1.920 2.017 2.162

1.688 1.778 1.867 1.957 2.092

1.631 1.710 1.789 1.868 1.986

1.580 1.651 1.721 1.792 1.898

1.537 1.601 1.666 1.731 1.828

0.25129

278.15 288.15 298.15 308.15 323.15

2.106 2.196 2.286 2.376 2.511

2.070 2.158 2.245 2.332 2.463

2.029 2.107 2.184 2.261 2.377

1.968 2.032 2.094 2.158 2.253

1.910 1.965 2.018 2.072 2.153

1.858 1.907 1.955 2.004 2.077

0.31480

278.15 288.15 298.15 308.15 323.15

2.507 2.639 2.680 2.800 2.988

2.419 2.531 2.628 2.748 2.934

2.368 2.482 2.556 2.661 2.827

2.293 2.359 2.451 2.536 2.671

2.220 2.292 2.366 2.435 2.546

2.221 2.298 2.301 2.358 2.450

0.34097

278.15 288.15 298.15 308.15 323.15

2.705 2.826 2.927 3.012 3.139

2.633 2.759 2.870 2.954 3.080

2.580 2.705 2.791 2.860 2.961

2.520 2.605 2.680 2.727 2.798

2.471 2.539 2.594 2.625 2.670

2.405 2.498 2.525 2.553 2.593

0.40378

278.15 288.15 298.15 308.15 323.15

3.021 3.150 3.279 3.408 3.601

2.955 3.083 3.210 3.337 3.528

2.882 2.997 3.112 3.226 3.398

2.793 2.887 2.981 3.075 3.216

2.749 2.820 2.891 2.962 3.069

2.746 2.794 2.842 2.890 2.962

0.49282

278.15 288.15 298.15 308.15 323.15

3.586 3.696 3.805 3.916 4.080

3.495 3.608 3.719 3.831 3.999

3.373 3.483 3.591 3.699 3.862

3.246 3.338 3.428 3.519 3.655

3.205 3.267 3.327 3.388 3.480

3.262 3.276 3.289 3.302 3.322

0.59066

278.15 288.15 298.15 308.15 323.15

4.095 4.226 4.355 4.485 4.680

3.989 4.120 4.247 4.377 4.572

3.844 3.970 4.092 4.216 4.403

3.695 3.800 3.900 4.002 4.156

3.660 3.726 3.788 3.852 3.949

3.740 3.750 3.757 3.768 3.781

0.68432

278.15 288.15 298.15 308.15 323.15

4.644 4.788 4.932 5.075 5.292

4.526 4.665 4.804 4.942 5.150

4.371 4.501 4.631 4.760 4.955

4.206 4.308 4.408 4.508 4.660

4.163 4.217 4.270 4.324 4.404

4.239 4.228 4.218 4.208 4.191

0.79536

278.15 288.15 298.15 308.15

5.351 5.501 5.651 5.802

5.204 5.350 5.495 5.640

5.007 5.143 5.279 5.415

4.799 4.904 5.008 5.113

4.757 4.804 4.851 4.897

4.795 4.786 4.777 4.768

RI

SC

NU

MA

PT E

CE

AC

PT

1.395 1.492 1.589 1.735

D

19 288.15 298.15 308.15 323.15

19

ACCEPTED MANUSCRIPT 20 6.027

5.858

5.620

5.270

4.968

4.753

0.85052

278.15 288.15 298.15 308.15 323.15

5.697 5.865 6.032 6.200 6.451

5.663 5.844 6.024 6.294

5.424 5.609 5.793 6.069

5.154 5.311 5.467 5.702

5.031 5.125 5.220 5.361

5.063 5.054 5.045 5.031

0.89800

278.15 288.15 298.15 308.15 323.15

5.942 6.119 6.278 6.531 6.821

5.909 6.139 6.337 6.608

5.682 5.888 6.096 6.324

5.305 5.559 5.753 5.939

5.307 5.397 5.474 5.606

5.320 5.297 5.269 5.293

0.92815

278.15 288.15 298.15 308.15 323.15

6.199 6.334 6.538 6.744 6.945

6.093 6.320 6.546 6.725

5.886 6.063 6.299 6.549

5.586 5.759 5.934 6.194

0.95840

278.15 288.15 298.15 308.15 323.15

6.378 6.528 6.808 6.917 7.233

6.318 6.569 6.706 6.980

6.102 6.327 6.455 6.700

0.97933

288.15 298.15 308.15 323.15

6.721 6.927 7.131 7.403

6.482 6.701 6.919 7.171

6.240 6.449 6.656 6.969

RI

5.497 5.459 5.424 5.369

5.796 5.988 6.074 6.291

5.702 5.774 5.767 5.899

5.775 5.648 5.521 5.504

5.971 6.121 6.270 6.496

5.817 5.893 5.947 6.030

5.866 5.758 5.684 5.574

MA

NU

SC

5.421 5.533 5.647 5.733

6.862 6.637 6.403 6.110 5.913 5.984 7.164 6.860 6.616 6.273 6.000 5.806 c 7.177 7.248b 1.00000 308.15 7.300 7.084 6.828 6.436 6.087 5.783 7.196d 323.15 7.506 7.316 7.146 6.681 6.217 5.749 7.775d a standard uncertainties, u, of the values measured: u(T)=0.03 K, u(p)=0.02 %, u(x) = 1·10-4, u( E P , m )

CE

PT E

D

288.15 298.15

PT

323.15

AC

= 6·10-5 cm3·mol-1·K-1. b calculated from Ref. [30], c calculated from Ref. [10], d calculated from Ref. [31]

20

ACCEPTED MANUSCRIPT 21 Highlights Compression of water + ethylenediamine mixture were measured.



Molar isothermal compression and isobaric expansion of the mixture were evaluated.



Influence of hydrate complex on the thermal pressure coefficient was analyzed.

AC

CE

PT E

D

MA

NU

SC

RI

PT



21