Twenty Years of Experimental Determinations of Thermophysical

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Twenty Years of Experimental Determinations of Thermophysical Properties with High Accuracy: Thermodynamics Laboratory, ESIQIE-IPN, México Luis A. Galicia-Luna,* Alfredo Pimentel-Rodas, José J. Castro-Arellano, Angel M. Notario-López, Carmen Sánchez-García, and Pedro Esquivel-Mora

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Laboratorio de Termodinámica, S.E.P.I.-E.S.I.Q.I.E., Instituto Politécnico Nacional, UPALM, Edif. Z, Secc. 6, 1ER piso, Lindavista C.P. 07738, México, Cd. México, México

ABSTRACT: In 1997, a new thermodynamic laboratory was create from scratch. Throughout 20 years of work, this laboratory has performed and reported experimental determinations of thermophysical properties, such as phase equilibria (VLE, SLE, SLVE), critical points of pure fluids and mixtures, volumetric properties (PvT), dynamic viscosities, supercritical fluid extraction (SFE), and studies on the formation of gas hydrates. Over time, experimental systems have been designed, developed, and/or modified according to the experiments. Besides, molecular simulations have been carried out, resulting in the proposal of equations of state based on perturbation theory. All of the measurements that have been carried out have reported the experimental uncertainty according to the NIST technical note 1297. In this work, experimental determinations of each thermophysical property, VLE, solid solubility in supercritical fluids, PvT, dynamic viscosities, and gas hydrate dissociation data, are reported in the 293.15−353.15 K temperature range and at pressures up to 30 MPa. The experimental uncertainty of reported data was determined and is mentioned for each property.

1. INTRODUCTION Experimental determination and representation of multiphase equilibria, critical points, solubility, volumetric properties (PvT), viscosity, and hydrate formation of multicomponent mixtures are of great interest in the design, development, simulation, synthesis, and optimization of processes as well as in the chemical, petrochemical, and refining industries and in the enhanced recovery of petroleum. However, in México, there was no laboratory capable of experimentally determining the mentioned properties. In response to this situation, in 1994, a project was presented to the authorities of the Instituto Politécnico Nacional (IPN) to create and develop a laboratory of experimental thermodynamics at high pressures focused on the development of processes without environmental impact. Since 1997, it has been possible to measure with high accuracy these thermophysical properties of binary and multicomponent mixtures at pressures up to 100 MPa and temperatures up to 673 K; here, the measurement range was limited at temperatures up to 353.15 K and up to 30 MPa of pressure. This experimental information is necessary for basic research © XXXX American Chemical Society

and for application in the chemical processes, particularly for those using supercritical fluids. The experimental determination of the thermophysical properties aforementioned has been carried out via apparatuses, some of them developed in the laboratory. Table 1 shows the experimental facilities available in the laboratory for the determination of thermophysical properties. Briefly, the main equipment used by the Thermodynamics Laboratory is described below. Equipment for Pressure and Temperature Calibration. Given that the thermophysical properties measured depend on the pressure and temperature of the system, it is necessary to know the level of confidence of these variables. For this, prior to the measurements, the pressure and Special Issue: Latin America Received: November 2, 2018 Accepted: January 18, 2019

A

DOI: 10.1021/acs.jced.8b01027 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

the development of extraction processes, mainly in supercritical fluid extraction (SCFE) processes.10−12 Given that the most used solvents in the industry are alcohols, initially the Thermodynamics Laboratory conducted a systematic study to experimentally obtain VLE and PvT data of CO2 + alcohol mixtures.10−13 Subsequently, systems containing alkanes were considered.14−16 The first equipment used for the determination of PvT properties (simultaneous with VLE) is based on the static-synthetic method and consisted mainly of a highpressure visual cell (sapphire tube), a vibrating tube densimeter (VTD), and a cathetometer with a video camera.17,18 Subsequently, another VTD was obtained; therefore, another experimental system was developed with the difference that the visual cell was replaced by a blind cell, with the aim of increasing the pressure of the system; in addition, a real time data acquisition via RS-232 ports was added.19,20 Today, both apparatuses are available in the laboratory. The development of SCFE processes requires the knowledge of accurate thermodynamic data as PvT properties and phase equilibria of pure compounds and mixtures. Measurements of volumetric properties of binary systems containing alkanes and CO2 constitute a set of experimental data, which are part of a project that is undergoing at the Thermodynamics Laboratory of the ESIQIE-IPN, and since octane is a component present in fuels, it can be used as a model fuel.18 In this work, PvT properties of the CO2 + octane system have been measured using the last apparatus described above. Solubility Measurements. Solubility data of solids or liquids in supercritical fluids are of great importance in the petroleum, food, and pharmaceutical industries, separation processes, particularly in SCFE because supercritical fluids have several advantages over organic solvents related to physical properties such as nontoxicity, nonflammability, and low price. 21,22 Initially, the equipment used for the determination of solubility data was based on the staticanalytical method (using a high-pressure equilibrium cell with sapphire windows).7,23 In order to determine the solubility and saturation density, a method that showed the versatility of the VTD and demonstrated that this apparatus can determine the solubility of solids in supercritical fluids and their corresponding saturation density quasi-simultaneously was developed.22,24,25 Due to the sensitivity limitations of this apparatus, a high-performance liquid chromatograph (HPLC) was acquired which was coupled to a high-pressure cell (equilibrium cell with sapphire windows), developing a third experimental apparatus for the determination of solubilities of solids in sub- and supercritical carbon dioxide, on the basis of the static-analytic method.26−28 Currently, all three systems are available and operational. Coconut oil is one of the most common natural vegetable oils; it consists of free fatty acids as well as triglycerides. Lauric acid is the main component in coconut oil and is one of the most commonly used oils in the food and pharmaceutical industries. Thus, in this work, experimental determination of the solubility of solid lauric acid in supercritical carbon dioxide (scCO2) was performed using the first apparatus described above. Viscosity Measurements at High Pressures. Viscosity data of polar and nonpolar fluids are of great importance for several technological applications and in chemical engineering mainly where the movement of the fluids controls the process.29,30 In the literature, several experimental methods

Table 1. Overview on the Different Experimental Facilities of the Thermodynamics Laboratory experimental method VLE (P, T, x, y) VLE (P, T, x, y, ρLiq, ρVap) PvT VTD - PvT (solubility) VTD solubility solubility - PvT hydrates viscosities SFE

method analytical analytical - VTD synthetic - visual synthetic - visual synthetic analytical synthetic synthetic - static (visual, nonvisual) capillary flow (straight, coil) analytical - dynamic

P/MPa

T/K

60 30 25 25 140 40 60 40

313−673 313−473 313−473 313−473 260−473 278−473 263−423 260−373

40

283−473

60

308−423

temperature indicators are calibrated using the following equipment: The pressure transducers used in all pressure measurements are calibrated against a dead-weight balance (Desgranges & Huot, model 5304) with a certified precision of the order of ±0.005% (full scale). The temperature of the system is usually measured with platinum probes (Pt 100 Ω, Specitec). The temperature calibrations are performed using (a) a resistance bridge system (Automatic Systems Laboratories F300) using a 25 Ω reference probe (model, Rosemount, 162CE ± 0.005 K) or (b) a triple-point water cell (Fluke Hart Scientific). Also, when mass measurements are required, the laboratory has a comparator balance by Sartorius LC1201S brand with a standard uncertainty of 1 × 10−7 kg. Some experiments require the determination of height or length, so a displacement transducer (model LS303C + ND 221, Microma-Heidenhain) with a standard uncertainty of 10 μm is part of the laboratory instruments. High-Pressure Equilibria Data. Phase equilibria data are of great importance for the chemical industry and for the development and/or validation of thermodynamic models; particularly the supercritical fluid extraction depends on accurate vapor−liquid and liquid−liquid equilibrium data.1−5 This thermophysical property and critical points were the first measured in the laboratory (CO2 + ethanol and CO2 + propanol systems).6 Initially, the apparatus used was based on the static-analytic method and has been designed to perform fast determinations of vapor−liquid equilibria and critical pressures up to 60 MPa and 523 K.7 However, in order to determine other thermophysical properties within the phase equilibrium, a second experimental apparatus was developed to simultaneously determine at high pressures liquid−vapor equilibrium or vapor−liquid−liquid equilibrium and saturation densities.8,9 Actually, both apparatuses are part of the experimental facilities of the Thermodynamics Laboratory. Limonene is a compound of interest due to its applications as a base aroma and heat transfer agent. As mentioned above, the knowledge of vapor−liquid equilibrium (VLE) allows one to develop, evaluate, and optimize an extraction process, considering a wide range of pressure and temperature. Therefore, in this work, the VLE of the CO2 + limonene and propane + limonene systems was determined using the first apparatus described above. PvT Properties. Experimental PvT and phase equilibrium data of pure fluids and mixtures at high pressures are required for diverse applications in science and chemical industry and in B



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6.08 × 10−4; TBAB, 4.62 × 10−4. The standard uncertainty of the content of water is 0.48 × 10−4 mass fraction. Table 2 shows the name of the substance used, the source, and the purity in mass fraction.

for measuring the viscosity of liquids at high pressures are presented, in which the capillary flow technique stands out. Recently,29 a new experimental system has been developed to determine simultaneously the viscosity and density of pure liquids and liquid mixtures up to 70 MPa and 423 K, according to the modified Hagen−Poiseuille equation. Due to the lack of high-pressure viscosity data of alkanes and alcohols, an extensive experimental study has been initiated in the Thermodynamics Laboratory. Dynamic viscosity data of alcohols are of great importance in many industrial applications, such as additives to gasoline and solvents in paints or pharmaceuticals. In this work, viscosity data of 1-decanol at 298.15, 303.15, 313.15, and 323.15 K and up to 30 MPa are presented using the aforementioned equipment. Gas Hydrate Dissociation Conditions. In the oil industry, the formation of gas hydrates is considered as a potential to cause operational problems.31,32 The hydrates have properties that involve a large capacity of gas storage, fractionation of gas mixtures, and a high heat of formation and decomposition. These properties allow gas hydrates to be applied for several applications such as water desalination, transportation, and storage of natural gases, air-conditioning use, etc.33,34 Attending the possibility of developing a process using this technique, two experimental systems capable of determining the dissociation points of gas hydrates at temperatures from 263 to 293 K and pressures of up to 30 MPa were developed. These apparatuses are based on the isochoric method (synthetic nonvisual method) and were developed recently. Nowadays, information on the equipment developed, as well as measurements of dissociation conditions of gas hydrates of systems containing N2 and CO2, are about to be published. In this work, dissociation points of gas hydrates for the hexane + CO 2 + H 2 O, hexane + CO 2 + tetrabutylammonium bromide (TBAB) + H2O, and hexane + decane + CO2 + H2O systems are reported in the 274.76− 278.75 K temperature range and the 19.43−28.43 MPa pressure range. The infrastructure and equipment of the Thermodynamics Laboratory have allowed a total of 68 publications in international journals. This paper aims to expose the contribution of the laboratory to the scientific, research, and/or technological community focused on the possible development of industrial processes.

Table 2. Chemical Information compound N2 CO2 propane limonene water TBAB octane lauric acid 1-decanol hexane decane a

source Infra Air Products Infra Air Products Infra Air Products Fluka Sigma-Aldrich Sigma-Aldrich Sigma-Aldrich Sigma-Aldrich Sigma-Aldrich Sigma-Aldrich Sigma-Aldrich

CAS No.

mass fraction puritya

purification method

7727-37-9

0.99995

none

124-38-9

0.99995

none

74-98-6

0.99995

none

5989-27-5 7732-18-5 1643-19-2 111-65-9 143-07-7 112-30-1 110-54-3 124-18-5

0.9950 0.9995 0.9980 0.9950 0.9870 0.9940 0.9670 0.9950

none none none none none none none none

Analysis method: gas chromatography.

Apparatus and Procedure. All experimental apparatuses and experimental procedures used have been described previously.7,19,23,29 The apparatuses used in this work are five of the experimental facilities that the laboratory has. Briefly, the equipment used are described as follows: The experimental determinations of vapor−liquid equilibrium were performed in an apparatus on the basis of the static-analytic method; the equipment uses a compressed airmonitored sampler injector for extracting and injecting phase samples into the carrier gas circuit of a gas chromatograph. The high-pressure cell (with sapphire windows) allows observing and following the position of the capillary (the capillary extends a short distance outside of the high-pressure cell, thus ensuring a small internal volume compared to that of the withdrawn samples). The temperature of the system is controlled by an air bath (spame) and is monitored by two platinum probes (PT100), previously calibrated (standard uncertainty of 0.015 K), collocated in the top and bottom of the high-pressure cell. The pressure measurements were performed using a pressure transducer previously calibrated (standard uncertainty of 0.01 MPa). For details about the method and procedure used, the reader is referred to the previous works.5−7 The density measurements (PvT) were carried out using a static-synthetic method (VTD) coupled with a visual cell (high-pressure cell with two sapphire windows). The temperature in the cell is controlled using an air bath (spame), while the temperature in the VTD is controlled by a liquid bath (polyscience PP15R). The temperature is measured with a platinum probe (PT100) previously calibrated (combined uncertainty of 0.012 K) and collocated in the VTD. The pressure is monitored with a pressure transducer previously calibrated (combined uncertainty of 0.010 MPa). For details about the method and procedure used, the reader is referred to the previous works.19,20 Solubility determinations were performed in an apparatus on the basis of the static-analytic method and containing an equilibrium cell, a gas chromatograph (HP 5890 II) with a thermal conductivity detector (TCD), and helium like carrier

2. EXPERIMENTAL SECTION Materials. Carbon dioxide (0.99995 in mass fraction), propane (0.99995 in mass fraction), and nitrogen (0.99995 in mass fraction) are from Infra México. Limonene (0.995 in mass fraction) is provided by Fluka. Octane (0.995 in mass fraction), lauric acid (0.987 in mass fraction), 1-decanol (0.994 in mass fraction), water (0.9995 in mass fraction), hexane (0.967 in mass fraction), decane (0.995 in mass fraction), and TBAB (0.998 in mass fraction) are from Sigma-Aldrich. The purity of each sample was obtained from the certificate of analysis acquired by the provider (checked by GC). All liquid substances were used as received from the manufacturer and were carefully degassed by agitation under a vacuum prior to injection into the system. The water content for solid and liquid samples was determined using a Karl Fischer coulometer (Metrohm, 831) where the mass fractions were as follows: limonene, 5.66 × 10−4; octane, 5.73 × 10−4; lauric acid, 6.01 × 10−4; 1-decanol, 5.79 × 10−4; hexane, 7.30 × 10−4; decane, C



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gas. Pressure was measured with a pressure transducer, while temperature was measured with two platinum probes. Pressure transducer and platinum probes were calibrated, and the standard uncertainties were estimated to be u(P) = 0.01 MPa and u(T) = 0.015 K. For details about the method and procedure used, the reader is referred to the previous works.23−25 Viscosity data were obtained using the capillary flow method with the modified Hagen−Poiseuille equation. This equipment was developed for simultaneous determination of viscosity and density data. The main parts of this apparatus are the syringe pump (standard uncertainty of 1 × 10−4 cm3·min−1), a VTD, two pressure transducers placed at the ends of the capillary tube, two platinum probes located in the VTD and in the capillary tube, and three temperature regulators (liquid bath). Pressure transducers and platinum probes were calibrated, and the combined uncertainties were estimated to be uc(P) = 0.002 MPa and uc(T) = 0.009 K. For details about the method and procedure used, the reader is referred to the previous works.29,30 Measurements of dissociation conditions of gas hydrates were performed in an experimental apparatus designed and built in house, consisting of a synthetic nonvisual apparatus. The equilibrium cell is “blind” and made of stainless steel. The cell has two ports, one of them for temperature measurement with a platinum probe previously calibrated (u(T) = 0.025 K). The pressure of the system is provided by the gas under study and is monitored by a previously calibrated pressure transducer (u(P) = 0.02 MPa). So far, there are no publications on this topic; however, information on experimental determinations as well the equipment developed is about to be published. All apparatuses are connected to a PC through RS232 ports, which allows an acquisition of data in real time.

Table 4. Vapor−Liquid Equilibria for the C3H8 + Limonene Systema

yCO2

P/MPa

xCO2

yCO2

2.19 3.18 4.25 5.10 6.29 7.17 8.09 8.85 9.44

T = 323.36 K 0.1643 0.2835 0.3470 0.4286 0.5339 0.6046 0.6878 0.7546 0.8975

0.9987 0.9989 0.999 0.9989 0.9986 0.9975 0.9948 0.9927 0.9831

2.25 3.14 4.12 5.16 6.17 7.15 8.15 9.09 10.06 11.15 12.19 12.97

T = 348.29 K 0.1401 0.1877 0.2550 0.3212 0.3670 0.4278 0.4955 0.5522 0.6070 0.6645 0.7217 0.7709

0.9961 0.9967 0.9970 0.9968 0.9965 0.9961 0.9957 0.9951 0.9932 0.9848 0.9690 0.9598

yC3H8

3.95 4.41 4.97 5.42 5.73

0.9868 0.9853 0.9824 0.9785 0.9728

Figure 1. Vapor−liquid equilibria for the CO2 + limonene at T = 323.36 K: (○) Chieh-Ming and Chia-Cheng;35 (■) Gironi and Maschietti;36 (▲) this work; (−) the PR-WS EoS; (- -) the PR-vW EoS.

experimental data is in agreement between the different works. Experimental VLE data for the binary system are correlated using the Peng−Robinson equation of state (eq 1) with two different mixing rules: one parameter van der Waals (eqs 2 and 3) and Wong−Sandler (eqs 6−8).

Table 3. Vapor−Liquid Equilibria for the CO2 + Limonene Systema xCO2

xC3H8 T = 413.53 K 0.6995 0.7551 0.8065 0.8530 0.8908

a Standard uncertainties u are u(P) = 0.01 MPa and u(T) = 0.015 K. The relative expanded uncertainty (k = 2) is estimated to be Ur(x) = Ur(y) = 0.0193.

3. RESULTS AND DISCUSSION Phase Equilibria Data. Vapor−liquid equilibrium data for the carbon dioxide + limonene and propane (C3H8) + limonene systems are reported in Tables 3 and 4, respectively, at 323.36, 348.29, and 413.53 K. Figure 1 shows the VLE data for carbon dioxide + limonene at 323.36 K reported in the literature and obtained in this work, where the trend of the

P/MPa

P/MPa

p=

a(T ) RT − v−b v(v + b) + b(v − b)

am =

∑ ∑ xixj(aiaj)1/2 (1 − kij) i

bm =

(1)

(2)

j

∑ xibi

(3)

i

The parameters ai and bi for pure components are related to a(T ) = 0.45724

R2Tc 2 [1 + (0.37464 + 1.54226ω Pc

− 0.26992ω 2)(1 − Tr1/2)]2 b = 0.07780

a

Standard uncertainties u are u(P) = 0.01 MPa and u(T) = 0.015 K. The relative expanded uncertainty (k = 2) is estimated to be Ur(x) = Ur(y) = 0.0193.

RTc Pc

(4)

(5)

The Wong−Sandler mixing rules are expressed as D



(

∑i ∑j xixj b − bm =

Article

a RT ij

a

1 − ∑i xi b RTi − i

Table 5. VLE Correlation for Binary Systems Using the PREoS

)

Gγexc

system T/K

(6)

CRT

with

a yz ij jjb − zz RT k {ij

k12 %Δp %Δy1

aj

(bi − RTa ) + (bj − RT ) (1 − k ) = i

ij Gγexc yzz a zz am = bmjjjj∑ xi i + j i bi C zz k {

2

ij

(7)

k12 τ12/kJ·mol−1 τ21/kJ·mol−1 %Δp %Δy1

(8)

where C = ln( 2 − 1)/ 2 . The NRTL model was selected to obtain the excess Gibbs energy Gexc γ : Gγexc RT τij =

=

∑ xi i

carbon dioxide + limonene 323.36 and 348.29 Classical Mixing Rules 0.0939 6.4 0.2 Wong−Sandler Mixing Rules 0.6669 6.5482 −1.2529 2.6 0.3

propane + limonene 413.52 −0.1243 2.9 0.3

∑j τjigjixj ∑k gkixk

(9)

δij RT

gij = exp( −αijτij)

(10) (11)

The nonrandomness parameter αji for the NRTL model was fixed to 0.3. Binary interaction parameters were computed by minimizing the following objective function: É ÅÄÅ 2Ñ Ñ 2 ij pcalcd − pexptl yz ÑÑÑ ÅÅ Nc ij y calcd − y exptl yz NP Å ÅÅ jj ij zz jj j zz ÑÑ ij j zz + jj zz ÑÑ OF = ∑ ÅÅÅ∑ jjj exptl exptl z j ÅÅ jj z j zzz ÑÑÑ y p z j j=1 Å ij j ÅÅÅ i = 1 k { k { ÑÑÑÑÖ Ç

Figure 2. Experimental density data for the CO2 + C8H18 system at xC8H18 = 0.1965 at high pressures: (●) T = 313.05 K, (○) T = 322.96 K, (▼) T = 332.84 K, (△) T = 342.78 K, (■) T = 352.64 K.

(12)

NP is the number of data points, Nc is the number of components, y is the vapor mole fraction, and the superscripts calcd and exptl denote the calculated and experimental values, respectively. Deviations in pressure and composition were computed using NP |pexptl − pi calcd | i 100 yz zz∑ i %Δp = jjj pi exptl k NP { i = 1

NP yi exptl − yi calcd ij 100 yz zz∑ %Δy = jj yi exptl k NP { i = 1

The trend of the data obtained is consistent with the low concentration of octane in the mixture. Solubility Data. The solubility for the solid lauric acid in supercritical carbon dioxide (scCO2) was obtained in this work at T = 307.75 K and pressures up to 20 MPa. The results obtained were compared with literature data in Figure 3. As can be observed, data reported in this work are in good agreement with literature data. It is worth mentioning that the reproducibility of the data was checked by performing several measurements at the same composition. As expected, at constant temperature, the solubility increases as the pressure increases. The experimental data for the solid lauric acid + scCO2 mixture are reported in Table 7. Viscosity Data. Figure 4 shows the viscosity data of 1decanol obtained in this work as a function of temperature and pressure. As expected, the viscosity increases when the pressure of the system increases (at fixed temperature). On the contrary, at constant pressure, while the temperature increases, the viscosity decreases. It should be mentioned that the viscosity of 1-decanol is considerably large but it is within the limits of the equipment used. The experimental data of 1decanol are presented in Table 8. Dissociation Data of Gas Hydrates. Experimental dissociation conditions for the CO2 + C6H14 + water system, the CO2 + C6H14 + TBAB + water system, the CO2 + C6H14 + C10H22 + water system, and the CO2 + C6H14 + C10H22 +

(13)

(14)

Optimized parameters and deviations for the VLE of binary systems are listed in Table 5 for the studied systems. According to these results, deviations in pressure and composition are lower for the Wong−Sandler mixing rules than for the classical mixing rules. PvT Properties. The VTD was calibrated using water and nitrogen as reference fluids. A maximum deviation of 0.04% was obtained with respect to the literature. The known composition of CO2 + octane (C8H18) mixture was carefully prepared by successive weightings using a comparator balance. The density data obtained in this work at xC8H18 = 0.1965 are shown in Figure 2 and presented in Table 6. The results show that, at constant pressure, increases of temperature mean a decrease of density; also, the increases of pressure, at constant temperature, generate an increase in the density of the mixture. E



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Table 6. Experimental Data of Density (ρexp) at Temperature (T) and Pressure (P) for the CO2 + Octane System at xC8H18 = 0.1965a T/K

P/MPa

ρexp/kg·m−3

313.05

8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.17 20.00 21.00 22.00 22.99 24.00 24.55 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00 21.00 22.00 22.96 23.96 16.00 17.00 18.00 19.00 20.00 21.02 22.02 22.98 23.99 24.79

740.9 750.1 758.3 765.4 771.9 777.9 783.5 788.7 793.6 798.2 802.7 807.0 811.1 815.0 818.7 822.2 825.6 827.5 716.1 724.1 731.9 739.1 745.8 752.0 757.7 763.10 768.2 772.9 777.5 781.8 786.0 789.9 793.6 797.3 732.9 739.2 745.1 750.6 755.8 760.8 765.4 769.7 773.9 777.1

322.96

332.84

Figure 3. Solubility data of solid lauric acid in scCO2 in a wide range of pressures: (○) Garlapati and Madras at T = 308.00 K;37 (●) this work at T = 307.75 K.

Table 7. Experimental Solubility Data (y) at Different Temperatures (T) and Pressures (P) of Solid Lauric Acid in scCO2a T/K

P/MPa

y/mol·mol−1 × 103

307.75

8.79 9.93 11.34 13.23 13.64 14.08 15.32 19.82

4.50 4.96 6.11 7.05 7.88 8.56 10.90 14.90

a

Standard uncertainties u are u(P) = 0.01 MPa and u(T) = 0.015 K. The relative expanded uncertainty (k = 2) is estimated to be Ur(y) = 0.0223.

a

The relative standard uncertainty is estimated to be ur(xi) = 0.0008; the combined uncertainties uc are uc(P) = 0.010 MPa and uc(T) = 0.012 K; the relative combined expanded uncertainty with a 0.95 level of confidence (k = 2) for the density is Urc(ρexp) = 0.001. Figure 4. Experimental viscosity data of 1-decanol as a function of pressure and temperature: (●) T = 298.15 K, (○) T = 303.15 K, (▼) T = 313.15 K, (△) T = 323.15 K.

TBAB + water system are shown in Tables 9−12, respectively. The effect of alkanes and TBAB on the dissociation of the gas hydrate is shown in Figure 5. As can be seen, for the compounds considered here, the alkanes seem to have no effect on the formation of the gas hydrate; dissociation data from systems containing hexane or decane are on the same equilibrium curve within the experimental uncertainty. However, when TBAB is added to the system, the dissociation

temperature increases, consistent with the effect of a thermodynamic promoter.

■

CONCLUSIONS A brief description of the experimental facilities of the Thermodynamics Laboratory is mentioned. Also, a summary F



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Table 8. Viscosity Experimental Data (ηexp) at Different Temperatures (T) and Pressures (P) of 1-Decanola T/K

P/MPa

ηexp/μPa·s

298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 298.15 303.15 303.15 303.15 303.15 303.15 303.15 303.15 303.15 303.15 303.15 303.15 303.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 313.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15 323.15

2.00 3.99 6.01 8.01 10.01 13.01 16.01 19.01 22.01 25.00 28.00 29.99 1.99 4.00 5.98 8.01 10.02 12.98 15.97 19.02 22.00 24.98 27.98 30.01 2.03 4.02 6.00 7.98 9.98 12.99 15.99 18.99 22.01 25.02 28.02 29.98 2.00 4.01 6.01 8.01 9.99 13.01 16.01 19.02 22.02 25.01 28.00 30.01

11254 11536 11791 12052 12347 12743 13160 13568 14007 14458 14890 15185 8894.6 9116.8 9337.3 9562.5 9784.3 10112 10442 10781 11111 11442 11774 11999 6219.3 6373.9 6526.3 6680 6835 7067.7 7299.4 7532.5 7765.6 7998.8 8230.7 8382.1 4735.1 4856.8 4970.3 5090.5 5202.4 5369.2 5540.1 5726 5892.2 6072.5 6247.2 6372.7

Table 9. Experimental Hydrate Dissociation Conditions, Temperature (T) and Pressure (P), for CO2 + C6H14 (1) + Water (2) Aqueous Solution Systems (w = Mass Fraction of Hexane)a w1

T/K

P/MPa

0.10

273.65 275.54 278.25 279.51 280.59

1.28 1.61 2.22 2.65 3.06

a

Standard uncertainties u are u(P) = 0.02 MPa and u(T) = 0.025 K. The relative standard uncertainty is estimated to be ur(wi) = 0.0009.

Table 10. Experimental Hydrate Dissociation Conditions, Temperature (T) and Pressure (P), for CO2 + C6H14 (1) + TBAB (2) + Water (3) Aqueous Solution Systems (w = Mass Fraction of Hexane or TBAB)a w1

w2

T/K

P/MPa

0.10

0.10

286.26 287.24 287.76 288.44 288.74

1.338 1.865 2.262 2.770 3.297

a


Table 11. Experimental Hydrate Dissociation Conditions, Temperature (T) and Pressure (P), for CO2 + C6H14 (1) + C10H22 (2) + Water (3) Aqueous Solution Systems (w = Mass Fraction of Alkanes)a w1

w2

T/K

P/MPa

0.04

0.06

274.99 277.24 278.84 279.93 280.91

1.53 1.96 2.43 2.86 3.21

a


Table 12. Experimental Hydrate Dissociation Conditions, Temperature (T) and Pressure (P), for CO2 + C6H14 (1) + C10H22 (2) + TBAB (3) + Water (4) Aqueous Solution Systems (w = Mass Fraction of Alkanes or TBAB)a

a

w1

w2

w3

T/K

P/MPa

0.04

0.06

0.10

286.91 287.46 288.18 289.20 289.88

1.83 2.20 2.71 3.28 3.79

Combined uncertainties uc are uc(P) = 0.002 MPa and uc(T) = 0.009 K; the relative combined expanded uncertainty with a 0.95 level of confidence (k = 2) for viscosity is Urc(ηexp) = 0.009.


of the thermophysical properties that have been experimentally determined over 20 years up to 673 K and 100 MPa is presented. Besides, experimental determinations of several thermophysical properties are reported as follows:

• VLE of the CO2 + limonene and C3H8 + limonene systems, from 323.36 to 348.29 K and pressures up to 23 MPa. • Solubility data of lauric acid in supercritical carbon dioxide at 307.75 K and pressures up to 20 MPa. • PvT properties of the CO2 + octane system at 313.05, 322.96, and 322.84 K and pressures up to 25 MPa.

a

G



Article

namics to H. Renon, S. I. Sandler, J. Gmehling, T. W. de Loos and my bachelor advisors in physics and PhD, A. MondragonBallesteros (Physics Institute of UNAM) and D. Richon (Ecole Nationale Superieure des Mines de Paris), respectively. Finally, thanks to all of my former students, especially I. Rojas-Hidalgo, F. F. Betancourt-Cardenas, and A. Pimentel-Rodas.

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(1) Silva-Oliver, G.; Galicia-Luna, L. A. Vapor−liquid equilibria near critical point and critical points for the CO2 + 1-butanol and CO2 + 2butanol systems at temperatures from 324 to 432 K. Fluid Phase Equilib. 2001, 182, 145−156. (2) Duran-Valencia, C.; Valtz, A.; Galicia-Luna, L. A.; Richon, D. Isothermal Vapor-Liquid Equilibria of the Carbon Dioxide (CO2)N,N-Dimethylformamide (DMF) System at Temperatures from 293.95 to 338.05 K and Pressures up to 12 MPa. J. Chem. Eng. Data 2001, 46, 1589−1592. (3) Silva-Oliver, G.; Galicia-Luna, L. A.; Sandler, S. I. Vapor−liquid equilibria and critical points for the carbon dioxide + 1-pentanol and carbon dioxide + 2-pentanol systems at temperatures from 332 to 432 K. Fluid Phase Equilib. 2002, 200, 161−172. (4) Durán-Valencia, C.; Galicia-Luna, L. A.; Richon, D. Phase equilibrium data for the binary system N,N-dimethylformamide + ethylene and + ethane at several temperatures up to 18 MPa. Fluid Phase Equilib. 2002, 203, 295−307. (5) Elizalde-Solis, O.; Galicia-Luna, L. A.; Sandler, S. I.; SampayoHernández, J. G. Vapor−liquid equilibria and critical points of the CO2 + 1-hexanol and CO2 + 1-heptanol systems. Fluid Phase Equilib. 2003, 210, 215−227. (6) Mendoza-de la Cruz, J. L.; Galicia-Luna, L. A. High-pressure vapor-liquid equilibria for the carbon dioxide + ethanol and carbon dioxide + propan-1-ol systems at temperatures from 322.36 to 391.96 K. ELDATA: Int. Electron. J. Phys.-Chem. Data 1999, 5, 157−164. (7) Galicia-Luna, L. A.; Ortega-Rodriguez, A. New Apparatus for the Fast Determination of High-Pressure Vapor-Liquid Equilibria of Mixtures and of Accurate Critical Pressures. J. Chem. Eng. Data 2000, 45, 265−271. (8) Galicia-Luna, L. A.; Elizalde-Solis, O. New analytic apparatus for experimental determination of vapor−liquid equilibria and saturation densities. Fluid Phase Equilib. 2010, 296, 46−52. (9) Elizalde-Solis, O.; Galicia-Luna, L. A. Vapor−liquid equilibria and phase densities at saturation of carbon dioxide + 1-butanol and carbon dioxide + 2-butanol from 313 to 363K. Fluid Phase Equilib. 2010, 296, 66−71. (10) Zúñiga-Moreno, A.; Galicia-Luna, L. A. Compressed Liquid Densities of Carbon Dioxide + Ethanol Mixtures at Four Compositions via a Vibrating Tube Densimeter up to 363 K and 25 MPa. J. Chem. Eng. Data 2002, 47, 149−154. (11) Zúñiga-Moreno, A.; Galicia-Luna, L. A.; Horstmann, S.; Ihmels, C.; Fischer, K. Compressed Liquid Densities and Excess Volumes for the Binary Systems Carbon Dioxide + 1-Propanol and Carbon Dioxide + 2-Propanol Using a Vibrating Tube Densimeter up to 25 MPa. J. Chem. Eng. Data 2002, 47, 1418−1424. (12) Zúñiga-Moreno, A.; Galicia-Luna, L. A.; Betancourt-Cárdenas, F. F.; Bernal-García, J. M. Compressed Liquid Densities and Excess Molar Volumes of CO2 + Hexan-1-ol Mixtures from (313 to 363) K and Pressures up to 25 MPa. J. Chem. Eng. Data 2006, 51, 1723− 1730. (13) Zúñ iga-Moreno, A.; Galicia-Luna, L. A.; Sandler, S. I. Measurements of Compressed Liquid Densities for CO2 (1) + Butan-1-ol (2) via a Vibrating Tube Densimeter at Temperatures from (313 to 363) K and Pressures up to 25 MPa. J. Chem. Eng. Data 2007, 52, 1960−1969. (14) Camacho-Camacho, L. E.; Galicia-Luna, L. A. Experimental Densities of Hexane + Benzothiophene Mixtures from (313 to 363) K and up to 20 MPa. J. Chem. Eng. Data 2007, 52, 2455−2461. (15) Zamora-López, H. S.; Galicia-Luna, L. A.; Elizalde-Solis, O.; Hernández-Rosales, I. P.; Méndez-Lango, E. Derived thermodynamic

Figure 5. Experimental hydrate dissociation conditions for CO2 + C6H14 + C10H22 + TBAB + H2O systems: (●) CO2 + C6H14 + H2O system; (○) CO2 + C6H14 + TBAB + H2O system at xTBAB = 0.10; (▼) CO2 + C6H14 + C10H22 + H2O system at xC6H14 = 0.10; (△) CO2 + C6H14 + C10H22 + TBAB + H2O system at xC6H14 = 0.10 and xTBAB = 0.10.

• Viscosity data of 1-decanol at 298.15, 303.15, 313.15, and 323.15 K and up to 30 MPa. • Dissociation conditions of gas hydrates of hexane + CO2 + H2O, hexane + CO2 + TBAB + H2O, and hexane + decane + CO2 + H2O systems are reported in the 274.75−278.75 K temperature range and the 19.43− 28.43 MPa pressure range. In some cases, comparisons were performed, showing that the data reported here are in good agreement with those data reported in the literature. Finally, on the basis of 20 years of thermophysical measurements, we can say that the Thermodynamics Laboratory has contributed to the scientific, research, and/or technological community with the determination of thermophysical properties with high precision for the development of processes.

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REFERENCES

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Luis A. Galicia-Luna: 0000-0003-1862-8499 Alfredo Pimentel-Rodas: 0000-0002-5379-003X Funding

The authors would like to thank the Instituto Politécnico Nacional and CONACyT for the financial support of this research. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS L.A.G.-L. gives special thanks to the former directors of the ESIQIE (Eng. Timoteo Pastrana Aponte) and the Department of Postgraduate Studies and Research (Prof. Jose Enrique Villa Rivera) for their interest, vision, and support that were fundamental for the creation of the Experimental Thermodynamics Laboratory. Besides, special thanks for all of your fruitful discussions in experimental and theoretical thermodyH



Article

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properties for the (ethanol + decane) and (carbon dioxide + ethanol + decane) systems at high pressures. J. Chem. Thermodyn. 2012, 55, 130−137. (16) Elizalde-Solis, O.; García-Fuentes, D.; Á lvarez-Badillo, S.; Zúñiga-Moreno, A.; Camacho-Camacho, L. E.; Galicia-Luna, L. A. Densities of Cresols and Linear Alkane Mixtures at High Pressure. J. Chem. Eng. Data 2013, 58, 2163−2175. (17) Zúñiga-Moreno, A.; Galicia-Luna, L. A. Densities of 1-Propanol and 2-Propanol via a Vibrating Tube Densimeter from 313 to 363 K and up to 25 MPa. J. Chem. Eng. Data 2002, 47, 155−160. (18) Zúñiga-Moreno, A.; Galicia-Luna, L. A.; Camacho-Camacho, L. E. Compressed Liquid Densities and Excess Volumes of CO2 + Decane Mixtures from (313 to 363) K and Pressures up to 25 MPa. J. Chem. Eng. Data 2005, 50, 1030−1037. (19) Quevedo-Nolasco, R.; de la Cruz-Hernández, L. A.; GaliciaLuna, L. A.; Elizalde- Solis, O. Volumetric Properties for the Binary Systems Hexane + Octane and Hexane + Decane at High Temperatures and Pressures. J. Chem. Eng. Data 2011, 56, 4226− 4234. (20) Quevedo-Nolasco, R.; Galicia-Luna, L. A.; Elizalde- Solis, O. Compressed liquid densities for the (n-heptane + n-decane) and (noctane + n-decane) systems from T = (313 to 363) K. J. Chem. Thermodyn. 2012, 44, 133−147. (21) Elizalde-Solis, O.; Galicia-Luna, L. A. Solubility of thiophene in carbon dioxide and carbon dioxide + 1-propanol mixtures at temperatures from 313 to 363K. Fluid Phase Equilib. 2005, 230, 51−57. (22) Zúñiga-Moreno, A.; Galicia-Luna, L. A.; Camacho-Camacho, L. E. Measurements of solid solubilities and volumetric properties of naphthalene + carbon dioxide mixtures with a new assembly taking advantage of a vibrating tube densitometer. Fluid Phase Equilib. 2005, 234, 151−163. (23) Serrano-Cocoletzi, V.; Galicia-Luna, L. A.; Elizalde-Solis, O. Experimental Determination of the Solubility of Thiophene in Carbon Dioxide and in Carbon Dioxide + Ethanol. J. Chem. Eng. Data 2005, 50, 1631−1634. (24) Elizalde-Solis, O.; Galicia-Luna, L. A. Solubilities and Densities of Capsaicin in Supercritical Carbon Dioxide at Temperatures from 313 to 333 K. Ind. Eng. Chem. Res. 2006, 45, 5404−5410. (25) Brandt, L.; Elizalde-Solis, O.; Galicia-Luna, L. A.; Gmehling, J. Solubility and density measurements of palmitic acid in supercritical carbon dioxide + alcohol mixtures. Fluid Phase Equilib. 2010, 289, 72−79. (26) Elizalde-Solis, O.; Galicia-Luna, L. A. New Apparatus for Solubility Measurements of Solids in Carbon Dioxide. Ind. Eng. Chem. Res. 2011, 50, 207−212. (27) Rojas-Á vila, A.; Pimentel-Rodas, A.; Rosales-García, T.; DávilaOrtiz, G.; Galicia-Luna, L. A. Solubility of Binary and Ternary Systems Containing Vanillin and Vanillic Acid in Supercritical Carbon Dioxide. J. Chem. Eng. Data 2016, 61, 3225−3232. (28) Rosales-García, T.; Rosete-Barreto, J. M.; Pimentel-Rodas, A.; Dávila-Ortiz, G.; Galicia-Luna, L. A. Solubility of Squalene and Fatty Acids in Carbon Dioxide at Supercritical Conditions: Binary and Ternary Systems. J. Chem. Eng. Data 2018, 63, 69−76. (29) Pimentel-Rodas, A.; Galicia-Luna, L. A.; Castro-Arellano, J. J. Capillary Viscometer and Vibrating Tube Densimeter for Simultaneous Measurements up to 70 MPa and 423 K. J. Chem. Eng. Data 2016, 61, 45−55. (30) Pimentel-Rodas, A.; Galicia-Luna, L. A.; Castro-Arellano, J. J. Simultaneous Measurement of Dynamic Viscosity and Density of nAlkanes at High Pressures. J. Chem. Eng. Data 2017, 62, 3946−3957. (31) Hammerschmidt, E. G. Formation of Gas Hydrates in Natural Gas Transmission Lines. Ind. Eng. Chem. 1934, 26, 851−855. (32) Mohammadi, A. H.; Richon, D. Clathrate Hydrates of Isopentane + Carbon Dioxide and Isopentane + Methane: Experimental Measurements of Dissociation Conditions. Oil Gas Sci. Technol. 2010, 65, 879−882. (33) Akiba, H.; Ueno, H.; Ohmura, R. Crystal Growth of Ionic Semiclathrate Hydrate Formed at the Interface between CO2 Gas and I


Twenty Years of Experimental Determinations of Thermophysical

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