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Thermophysical Properties of Normal Butane from 135 to 700 K at Pressures to 70 Mpa

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Thermophysical Properties of Normal Butane from 135 to 700 K at Pressures to 70 Mpa Thermophysical Properties of Normal Butane from 135 to 700 K at Pressures to 70 MPa William M. Haynes and Robert D. Goodwin Thermophysical Properties Division National Engineering Laboratory National Bureau of Standards Boulder, CO 80303 U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director Issued April 1982 Library of Congress Catalog Card Number: 82-600512 National Bureau of Standards Monograph 169 Nat. Bur. Slanii. (U.S.), Mongr. \W. 197 pages (Apr. 1982) CODEN: NBSMA6 U.S. GOVERNMENT PRINTING OFFICE WASHINGTON: 1982 Contents Page 1. Introduction 1 2. Physical Properties and Their Formulation 2 2.1 Fixed-Point Values 2 2.2 Melting Line and Vapor Pressures 3 2.3 The Orthobaric Densities 4 2.4 The Virial Equation 5 2.5 The Equation of State 6 2.6 The Ideal Gas Functions 8 2.7 Thermal Loop Computations 8 2.8 The Heats of Vaporization 9 2.9 Saturated Liquid Enthalpies and Entropies 9 2.10 Dielectric Constants 10 3. Computational Methods 11 3.1 The Homogeneous Domain 11 3.2 The Saturated Liquid 12 3.3 The Compressed Liquid 13 3.4 Fugacity Coefficients 13 3.5 Simplified Computation 13 4. Tests and Conclusions 13 5. Tables of Physical and Thermodynamic Properties 14 5.1 Calculated P-p-T Isochores and Isotherms 14 5.2 The Joule-Thomson Inversion Locus 14 5.3 Thermophysical Properties of the Saturated Liquid ..... 15 5.4 Thermophysical Properties Along Selected Isobars 15 6. Acknowledgments 15 7. References 16 APPENDIX A. Symbols and Units 23 APPENDIX B. Conversion of Units 25 APPENDIX C. Fixed-Point Values for Normal Butane 26 APPENDIX D. Normal Butane Properties Reference Index 27 APPENDIX E. Computer Program 30 i i i List of Figures Page Figure 1. Density-temperature diagram of normal butane 49 Figure 2. P-T locus of P-p-T data for normal butane 50 List of Tables Table 1. Comparisons of vapor pressure data with eq (2) 51 Table 2. Comparisons of saturated liquid density data with eq (3) . 54 Table 3. Comparisons of saturated vapor density data with eq (4) . 57 Table 4. Comparisons of second virial coefficients with eq (5). 59 Table 5. Behavior of coefficients of equation of state for normal butane (eq (6)) 62 Table 6. Calculated P(p) critical isotherm of normal butane 63 Table 7. Comparisons of experimental P-p-T data of normal butane with eq (6) 64 Table 8. Comparisons of data for ideal gas functions with eq (7). 85 Table 9. Interpolated ideal gas functions from eq (7) 86 Table 10. Comparisons of heat of vaporization data with eq (9) , . 87 Table 11. Enthalpies of saturated liquid normal butane from eq (10) . 89 Table 12. Entropies and specific heats of saturated liquid normal butane from eq ( 1 1 ) 90 Table 13. Comparisons of dielectric constant data with eq (12) .... 91 Table 14. Comparisons with saturated liquid specific heats 95 Table 15. Comparisons with C and C data 96 v p Table 16. Comparisons with velocity of sound data 97 Table 17. Calculated P(T) isochores of normal butane 98 Table 18. Calculated P(p) isotherms of normal butane 113 Table 19. The Joule-Thomson inversion locus for normal butane .... 133 Table 20. Thermophysical properties of saturated liquid normal butane 134 Table 21, Thermophysical properties of normal butane along isobars . 136 i V THERMOPHYSICAL PROPERTIES OF NORMAL BUTANE FROM 135 TO 700 K AT PRESSURES TO 70 MPa William M. Haynes and Robert D. Goodwin Thermophysical Properties Division National Engineering Laboratory National Bureau of Standards Boulder, Colorado 80303 Using a modified version of the nonanalytic equation of state, thermophysical properties of normal butane are derived from physical properties data and are tabulated at integral temperatures from 135 to 700 K along isobars at pressures to 70 MPa. These isobar tables, along with a table for the saturated liquid, give values for densities, compressibility factors, internal energies, enthalpies, entropies, heat capacities, fugacities, sound velocities, dielectric constants, and isochore and isotherm derivatives. Equations, whose coefficients are determined from a least squares fit to selected experimental data, are also presented for vapor pressures, orthobaric liquid and vapor densities, ideal gas properties, second virial coefficients, dielectric constants, heats of vaporization, melting pressures, and orthobaric liquid specific heats, enthalpies, and entropies. Comparisons between experimental and calculated values for all properties considered here are reported in detail. Key words: Densities; dielectric constants; enthalpies; entropies; equation of state; fugacities; internal energies; isobars; isochores; isotherms; Joule-Thomson inversion; latent heats of vaporization; melting line; normal butane; orthobaric densities; specific heats; vapor pressures; velocities of sound. 1 . Introduction The present work is a revision and extension of a previous provisional report [28] from this laboratory. Since that report new compressibility data [35] for normal butane at low temperatures have become available and are incorporated in the work reported here. These new data cover a range from 140 to 300 K at pressures to 35 MPa. As a result of new dielectric constant measure- ments [35,38] on normal butane, the present work also includes a correlation of dielectric constant data. The nonanalytic equation of state used here, which is modified from earlier versions [26-29], is also currently being employed in correlations for propane [30] and isobutane [31]. 1 other correlations on normal butane have been reported by Hanson [34], Prengle, et al . [57], Canjar, et al. [9], Das and Kuloor [?C], and Das, et al . [21]. Many new properties data, especially at low temperatures, have appeared since these correlations were developed. SI units are used throughout this report in tables and equations. Pressures 3 are given in MPa, densities in kg/m , and temperatures in K. For thermal properties, the mol is used for amounts of substance. However, all computations in computer programs (Appendix E) for the present work have been conducted in units of bar for pressure and mol/L for density. Symbols and units used in this report and in computations appear in Appendix A; conversion factors for units are given in Appendix B. Fixed-point values of normal butane used in this work are reported in Appendix C. A collection of references for the major physical properties of normal butane, along with ranges of data, is presented in Appendix D. Appendix E consists of computer programs used for the calculation of thermophysical properties of normal butane. In figure 1 is presented the density-temperature diagram for normal butane. 2. Physical Properties and Their Formulation In this section, first the fixed-point values selected in present work are presented and their origins are briefly discussed. As the present equation of state originates on a given liquid-vapor coexistence boundary, the P(T) melting line, the vapor pressures, and the orthobaric densities are next formulated. Then the truncated virial equation of state is given because it is used to derive some needed data. The equation of state description is followed by formulation of some thermal properties needed for the final computations of a thermodynamic network. All symbols used in the equations are defined in Appendix A. 2.1 Fixed-Point Values These values are listed in Appendix C. (a) The Triple Point. The temperature (T^ = 134.86 K) is adopted from Das, et al . [21], while the pressure is determined from the vapor pressure equation (eq (2)). The liquid density is based on consistency with data in eq (3). Equation (4) for saturated vapor densities is used for calculating the vapor density. 2 (b) The Boiling Point. The temperature {J^ = 272.638 K) is froin vapor pressure eq (2) at a pressure of 1 atm = 0.101325 MPa. Liquid and vapor densities are from eqs (3) and (4). (c) The Critical Point. The temperature (T^ = 425.16 K) is adopted from Das, et al. [21] and is in agreement within acceptable limits with the values of = Beattie, et al . [2] and Kay [44]. The density and pressure (p^ 227.85 kg/n? (3.92 mol/L) and P^ = 3.7960 MPa) are adopted on the basis of fitting orthobaric densities, vapor pressures, and P-p-T data and then examining the behavior of the calculated critical isotherm. The selected values for density and pressure are substantiated by those obtained experimentally from the data of Kay [44], Beattie, et al . [2] and by those selected in the correlation of Das, et al. [21]. 2.2 Melting Line and Vapor Pressures (a) The Melting Line. Experimental pressures from about two to ten kilobars were reported by Reeves, et al . [59] as constants for the Simon eq (1). In present work using the triple point temperature and pressure from Appendix C, the relation, = ^ [(T/T^)^ - 1] (1) % Pt Po . is obtained, where P^ = 6.7358 x lO"'' MPa, T^ = 134.86 K, P^ = 363.4 MPa, and c = 2.21. (b) The Vapor Pressures. Data used for adjusting eq (2) appear in the first part of table 1. Other data, weighted zero, appear in the continuation of the table. Values at ID = 40 have been derived via thermal loops, as described by Goodwin [27], by use of the saturated liquid specific heat data of Aston, et al . [1] from the triple- to the normal boiling-point; the heat of vaporization of Aston, et al . [1] at the normal boiling point; the ideal gas thermofunctions formulated in section 2.6; the virial equation formulated in section 2.4; and, for the minor contribution of V*dP to AH on the saturated liquid path, the preliminary vapor pressure and saturated liquid densities equations were also used. This procedure also has been described by Yarbrough and Tsai [75].
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