THE DIRECT DETERMINATION OF THE ENTHALPY OF FLUIDS UNDER PRESSURE by Alan Edward Mather A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the University of Michigan 1967 Doctoral Committee: Professor Donald L. Katz, Chairman Professor Joseph J. Martin Professor John E. Powers Professor Edgar F. Westrum, Jr. Professor G. Brymer Williams

A CK Otw 0LE D G EMEN T S The author wishes to express his appreciation for the assistance of many people during the course of this research: To Professor D. L. Katz for his advice and encouragement during the supervision of the work. To Professor J. E. Powers who was closely involved with this research, for his help, understanding, and encouragement. To Professors J. J. Martin, E. F. Westrum, Jr., and G. B. Williams, for serving on the doctoral committee. To J. C. Golba and V. F. Yesavage who contributed greatly to this work by assisting in all phases of the enthalpy project. To N. W. Prodany for many helpful discussions, some of which involved the present research. To E. A. Manker and D. T. lMage, who introduced me to the enthalpy project. To E. R. Freedman, J. C. Golba, Jr., and P. Bandyopadhyay for assistance in reduction of data, I.J.S. Sehgal for preparation of figures and comparison of methods of prediction, and J. R. Gwozdz for calculations in the design of the calorimeter. To members of the ORA Instrument Shop, particularly E. Rupke, Supervisor, who made the shop services available whenever they were needed, and H. Senecal, who fabricated the isothermal throttling calorimeter and made suggestions which contributed much to its success, To members of the staff of the Chemical and Metallurgical Engineering Department in particular C. Bolen, D. Connell, and F. Drogosz ii

for their help in the mechanical and analytical problems which arose. The author is also indebted to the following organizations: To the Natural Gas Processors Association for continued support of the research and for provision of fellowships. To the Continental Oil Company for a fellowship. To the American Petroleum Institute for support of Mr. Golba. To the Southern California Gas Company for the supply of the methane used in this work. To the Dow Chemical Company for the gift of a large quantity of Styrofoam. To the National Bureau of Standards for the calibration of thermocouples and standard cells. iii

TABLE OF CONTENTS Page ACKNOWLEDGEIIENTS LIST OF TABLES vi LIST OF FIGURES NOMENCLATURE xiv ABSTRACT xvi INTRODUCTION 1 SECTION I - PRELIMINARY CONSIDERATIONS 3 Thermodynamic Relations 3 Review of Experimental Data 7 Methods of Prediction of Enthalpies of Mixtures 12 The Methane - Propane System 20 The Methane - Nitrogen System 25 SECTION II - THE ISOBARIC EFFECT OF TEMIPERATURE ON 28 ENTHALPY Experimental Equipment 28 Measuring Instruments 30 Procedure for Isobaric Measurements 34 Materials Used 34 Experimental Data on the Methane - Propane System 35 Nomninal 5 Perc ent Propane in Methane Mixture 35 Nominal 12 Percent Propane in Methane Mixture 39 Nominal 28 Percent Propane in Methane Mixture 49 Experimental Data on the Nominal 43 Percent Nitrogen in 59 Methane Mixture Experimental Data on Niitrogen to Evaluate Heat Leak 68 iv

Pare SECTION III - THE ISOTHIERMiAL EFFECT OF PRESSURE ON ENTIIALPY 75 Background in Isothermal Throttling Calorimetry 75 Design of Isothermal Throttling Calorimeter 78 Description of Calorimeter 80 Measuring Instruments 83 Procedure for Isothermal Measurements 85 Experimental Results with Nitrogen 85 Analysis of Results with Nitrogen 87 Experimental Results for a Nominal 5 Percent Propane in 103 Methane Mixture Analysis of Results (Nominal 5 Percent Mixture) 103 SECTION IV - ENTHALPY TABLES AND DIAGRAMIS 110 Nominal 5 Percent Propane in Methane Mixture 110 Nominal 12 Percent Propane in Methane Mixture 114 Nominal 28 Percent Propane in Methane Mixture 118 Nominal 43 Percent Nitrogen in Methane Mixture 126 Comparison of Methane - Nitrogen Enthalpy Data 132 Vapor - Liquid Equilibria 138 Isobaric Heats of Vaporization 139 SUMIMARY AND CONCLUSIONS 142 RECOIMENIJDATIONS FOR FUTURE WORK 143 APPENDICES A. Calorimeter Construction Drawings 14]h B. Calibrations 154 C. Enthalpy Formulae and Loop Checks 166 D, Experimental Data 173 REIFEREINCES 188

LIST OF TABLES Table Page I Recent References to Experimental Thermal Data on Fluids Under Pressure 8 II Methods of Prediction of Enthalpies of Mixtures 18 III Experimental Investigations on the Methane - Propane System 23 IV Experimental Investigations on the Methane - Nitrogen System 26 V Comparison of Mass Flow Rates Determined by Direct Weighing with Values Calculated from Earlier Calibration Curve 33 VI Materials 35 VII Composition of Nominal 5 Percent Mixture 37 VIII Tabulated Values of Isobaric Heat Capacities of Nominal 5 Percent Mixture 40 IX Comparison of Analyses of Nominal 12 Percent Mixture 43 X Composition of Nominal 12 Percent Mixture 45 XI Tabulated Values of Isobaric HIeat Capacities of Nominal 12 Percent Mixture 46 vi

Table Page XII Heats of Vaporization of INominal 12 Percent Mixture 49 XIII Composition of Nominal 28 Percent Mixture 53 XIV Tabulated Values of Isobaric Heat Capacities of Nominal 28 Percent Mixture 56 XV Heats of Vaporization of Nominal 28 Percent Mixture 55 XVI Comparison of Analyses of the Methane - Nitrogen Mixture (1965) 59 XVII Comparison of Analyses of the Methane - Nitrogen Mixture (1967) 61 XVIII Composition of Nominal 43 Percent Mixture 63 XIX Tabulated Values of Isobaric Heat Capacities of Nominal 43 Percent Mixture 64 XX Heats of Vaporization of Nominal 43 Percent Mixture 68 XXI Accuracy of Isothermal Measurements 85 XXII Comparison of Difference Thermocouple Readings 89 XXIII Comparison of Experimental Enthalpy Departures for Nitrogen with Values from Other Sources 101 XXIV Isothermal Throttling Coefficients for the Nominal 5 Percent Mixture 105 vii

Table Page XXV Comparison of Experimental Enthalpy Departures for the Nominal 5 Percent Mixture with Values from Other Sources 108 XXVI Calculation of Zero - Pressure Isothermal Throttling Coefficients from Virial Coefficient Data 109 XXVII Tabulated Values of Enthalpy for the Nominal 5 Percent Mixture 117 XXVIII Tabulated Values of Enthalpy for the Nominal 12 Percent Mixture 122 XXIX Tabulated Values of Enthalpy for the Nominal 28 Percent Mixture 125 XXX Tabulated Values of Enthalpy for the Nominal 43 Percent Mixture 130 XXXI Comparison of Enthalpies Predicted by BWR Equation of State with Experimental Results 131 XXXII Comparison of Phase Equilibria Obtained from Enthalpy Traverses with Vapor - Liquid Equilibrium Data. 138 XXXIII Calculated and Experimental Isobaric Heats of Vaporization 141 XXXIV Main Thermopile Calibrations 155 XXX Calibration of High Pressure Gauge 156 XXXVI Calibration of Dead Weight Gauge 157 viii

Table Page XXXVII Flow Meter Calibration Data for INominal 5 Percent Mixture 158 XXXVIII Flow Ileter Calibration Data for Nominal 12 Percent Mixture 160 XXXIX Flow Meter Calibration Data for Nominal 43 Percent Mixture 162 XL Flow tMeter Calibration Data for Nitrogen 164 XLI Consistency Checks on Nitrogen 169 XLII Consistency Checks on the Nominal 5 Percent Mixture 172 XLIII Tabulated Experimental Isobaric Data for the Nominal 5 Percent MIixture 174 XLIV Tabulated Experimental Isobaric Data for the Nominal 12 Percent Mixture 175 XLV Tabulated Experimental Isobaric Data for the Nominal 28 Percent Mixture 177 XLVI Tabulated Experimental Isobaric Data for the Nominal 43 Percent Mixture 180 XLVII Tabulated Experimental Isobaric Data for Nitrogen 182 XLVIII Tabulated Experimental Isenthalpic Data for Nitrogen 182 ix

Tab le Page XLIX Tabulated Experimental Isothermal Data for Nitrogen 182 L Tabulated Experimental Isothermal Data for the Nominal 5 Percent Mixture 183 LI Constants for Benedict-Webb-Rubin Equation of State 185 LII Combining Rules for Constants in the Benedict-Webb-Rubin Equation of State 186

LIST OF FIGURES Fire Page 1. Flow Diagram of the Apparatus 29 2. Corblin Diaphragm Compressor 31 3. Range of Experimental Measurements on the Nominal 5 Percent Mixture 36 4. Blending of Experimental Heat Capacities with Values Calculated from B-W.-R Equation of State 38 5. The Heat Capacity of the Nominal 5 Percent Mixture as a Function of Pressure 41 6. Range of Experimental Measurements on the Nominal 12 Percent Mixture 42 7. Composition of the Nominal 12 Percent Mixture as a Function of Time 44 8. Enthalpy Traverse of the Two-Phase Region 50 9. Range of Experimental Measurements on the Nominal 28 Percent Mixture 51 10. Composition of the Nominal 28 Percent Mixture as a Function of Time. 52 11. Flow Meter Calibrations with Nominal 28 Percent Mixture 54 12. Range of Experimental Measurements on the Nominal 43 Percent Mixture 60 13. Composition of the Nominal 43 Percent Mixture as a Function of Time 62 14, Heat Capacity of the Nominal 43 Percent Mixture at 1500 psia 67 15. Heat Capacity as a Function of Reciprocal Flow Rate for Nominal 5 and 12 Percent Mixtures 70 16. Heat Capacity as a Function of Reciprocal Flow Rate for Nominal 28 and 43 Percent Mixtures 71 17. Heat Capacity as a Function of Reciprocal Flow Rate for Nitrogen 72 xi

LIST OF FIGURES - (Cont,) Figure Page 18. Apparent Heat Leak as a Function of Temperature Rise Across the Calorimeter 74 19. Isothermal Throttling Calorimeter 81 20. Range of Experimental Measurements of Nitrogen 86 21. Isenthalpic (Joule-Thomson) Data on Nitrogen 88 22. Comparison of the Types of Joule-Thomson Experiments 90 23. Isothermal Data on Nitrogen at -147.10 F 91 24. Isothermal Data on Nitrogen at 32.60 F 92 25. Isothermal Data on Nitrogen at 201.3 F 93 26. Comparison of Isothermal Data With Other Experimental Data 95 27. Comparison of Isothermal Data With Equations of State 96 28. Comparison of Isothermal Data at -147.1~ F with Values from Compilations 98 29. Comparison of Isothermal Data at 32.60 F with Values from Compilations 99 30. Comparison of Isothermal Data at 201.30 F with Values from Compilations 100 31. Comparison of Zero-Pressure Isothermal Throttling Coefficients for Nitrogen 102 32, Comparison of Isothermal Data Obtained with Different Capillaries 104 33, Comparison of Isothermal Data at 2000 F With Other Experimental Data 107 34. Enthalpy Departures for the Nominal 5 Percent Mixture 113 35. Pressure-Temperature-Enthalpy Diagramn for the Nominal 5 Percent 'M1ixture (High Temperature) 115 35. Pressure-Temperature-Enthalpy Diagram for the Nominal 5 Percent Mixture (Low Temperature) 116 36. Enthalpy Departures for the Nominal 12 Percent Mixture 119 37. Pressure-Temperature-Enthalpy Diagram for the Nominal 12 Percent Mixture (High Temperature) 120 xii

LIST OF FIGURES - (Cont.) Figure Pa 37. Pressure-Temperature-Enthalpy Diagram for the Nominal 12 Percent Mixture (Low Temperature) 121 38. Pressure-Temperature-Enthalpy Diagram for the Nominal 28 Percent Mixture (High Temperature) 123 38. Pressure-Temperature-Enthalpy Diagram for the NIominal 28 Percent Mixture (Low Temperature) 124 39. Pressure-Temperature-Enthalpy Diagram for the Nominal 43 Percent Mixture (IIigh Temperature) 128 39. Pressure-Temperature-Enthalpy Diagram for the Nominal 43 Percent Mixture (Low Temperature) 129 40, Heats of Mixing at High Pressure 133 41. Isothermal Enthalpy Comparison at Low Temperature 134 42. Isothermal Enthalpy Comparison at High Temperature 135 43. Isobaric Enthalpy Comparisons at 500 psia 136 44. Isobaric Enthalpy Comparisons at 1500 psia 137 45, Assembly Drawing for Isothermal Throttling Calorimeter 145 46. Detail Drawings for Isothermal Throttling Calorimeter 146 47. Flow Meter Calibration for Nominal 5 Percent Mixture 159 48. Flow Meter Calibration for Nominal 12 Percent MIixture 161 49, Flow Meter Calibration for Nominal 43 Percent Mixture 163 50. Flow Meter Calibration for Nitrogen 165 51. Location of Experimental Loops for Nitrogen 170 52. Location of Experimental Loops for Nominal 5 Percent Mixture 171 xiii

IO:AI4EJCLATURE a,b,c Constants in B-W-R equation of state A,B,C Constants in B-W-T-R equation of state A,B,C,D Flow meter calibration constants B Second virial coefficient in volume expansion B' Second virial coefficient in pressure expansion C Third virial coefficient in volume expansion C' Third virial coefficient in pressure expansion f Fugacity f Fugacity in a solution F Mlass flow rate H Specific enthalpy H Partial molal enthalpy AHvap Enthalpy change on vaporization P Pressure P Critical pressure C P Reduced pressure, P/P AP Pressure drop Q Rate of transfer of heat R Gas constant T Temperature T Critical temperature c Tr Reduced temperature, T/TV Specific volume xiv

W Rate of transfer of work x Composition Z Compressibility factor, PV/RT a Constant in B-.W-R equation of state y Constant in B-W-R equation of state 6 Constant in modified B-W-R equation of state Percentage error Joule-Thomson coefficient Viscosity p Density Isothermal throttling coefficient W Acentric factor Subscripts c Critical property H Constant enthalpy i Component in mixture mix Mixture property P Constant pressure T Constant temperature 1 Initial state 2 Final state 11,22 Pure component interaction 12 Mixture interactions between 1 and 2 Superscripts E Excess property o Zero-pressure property xv

ABSTRACT Accurate values of enthalpy are directly useful in design but they are also needed to test theories of fluids, to improve methods of prediction, and to derive other thermodynamic properties. The purposes of this work were: 1) To modify the existing recycle system and isobaric flow calorimeter to allow measurements under conditions different from those for which the equipment was originally designed. 2) To obtain accurate data on the effect of temperature on enthalpy for mixtures of methane with propane and with nitrogen. 3) To design, construct, and test a device for the direct measurement of the effect of pressure on enthalpy. The flow calorimeter recycle system was modified by the installation of a Corblin diaphragm compressor to prevent contact of the gas mixture with the compressor oil. A second six-Junction calibrated thermopile was installed in the isobaric calorimeter as a check on the original thermopile. The new thermopile is calibrated up to +150 C thus allowing accurate measurements to higher temperatures. Other modifications were made to the recycle system to increase the ease of operation. The facility was used to obtain isobaric data on the effect of temperature on enthalpy for mixtures of 11.7 mole percent propane in methane, 28 mole percent propane in methane, and 43.4 mole xvi

percent nitrogen in methane. These experimental data covered the liquid, twc-phase, and gaseous regions at temperatures from -2400F to +1300F at pressures from 250 to 2000 psia. With supplemental data on the effect of pressure on enthalpy from the literature, pressure - enthalpy - temperature diagrams and skeleton enthalpy tables for these mixtures were prepared. Detailed consideration of the various means of measuring the effect of pressure on enthalpy led to the choice of an isothermal throttling calorimeter. In common with several other throttling calorimeters, a capillary tube is used to cause the pressure drop and electrical energy is added to make the expansion essentially isothermal. However, an innovation in this design is the heater, an insulated resistance wire which passes axially through the capillary. The pressure drop across the calorimeter is measured by a differential pressure balance and any temperature difference between the inlet and outlet is sensed by calibrated duplicate sixjunction thermopiles. Measurements of the effect of pressure on enthalpy were made 0 0 0 with nitrogen as a test gas at -147 F, 33 F, and 201 Fr at pressures from 2000 psia to 100 psia. The data are in agreement with values from the literature; however, the literature values disagree among themselves by up to 4 percent. Measurements were made on a mixture of 5,2 mole percent propane in methane at temperatures of -147~F, -27~F, 92~Fr', and 200~F. At the highest isotherm, measurements were made in two different capillary coils to test the effect of flow xvii

rate. The data from the two coils agreed with a maximum deviation of +1 percent. Isobaric measurements were also made on the 5.2 mole percent propane in methane mixture to extend the data of dianker from 80 F to 250'F. A skeleton enthalpy table and an enthalpy diagram for this mixture covering the range -280 F to + 300 0F at pressures up to 2000 psia was constructed which is based almost entirely on direct experimental determinations. xviii

THE DIRECT DETERMIITATION OF TIE ENiTIHALPY OF FLUIDS UNIDER PRESSURE INTRODUCTION A knowledge of the enthalpy behavior of a fluid is necessary for the rational design of processes involving the transfer of heat and work. In the past, the data used in design were obtained principally from P-V-T data, either directly using thermodynamic relations or indirectly using an equation of state. The process of generating enthalpies from compressibility data involves differentation with attendent loss in accuracy of at least one order of magnitude. In a region V;here the derivatives are changing rapidly, such as the critical region, the error may be very large. For this reason, it is desirable to have enthalpies which were measured directly; because of the time involved and the expense of obtaining such data, few have been published. It is, of course, impossible to obtain data for all the materials of interest over wide ranges of pressures and temperature; however, experimental data on selected materials and mixtures are useful not only in themselves, but also for derivation of other thermodynamic properties. The goal of this work i;as to obtain data on the isobaric effect of temperature on enthalpy for mixtures of methane with propane and with nitrogen, and to develop, fabricate, and test a device for the measurement of the effect of pressure upon enthalpyr. Section I pre

-2 -sents the pertinent thermodynamic relations, reviews the recent literature on enthalpy data and methods of prediction, and presents a listing of previous work on the two, binary systems studie d in.this work. Section II considers the isobaric effect of temperature on enthalpy, describes modifications to the equipme:nt used and presents data for nitrogen, a mixture of methane and nitrogen and three mixtures of propane and methane. Section III considers the isothermal effect of pressure on enthalpy, reviews previous work of this type and describes the calorimeter developed in the course of this work. The experimental results obtained are compared with other direct measurements, with Joule-Thomson data, and with values derived from compressibility data. The construction of skeleton enthalpy tables and pressure - enthalpy - temperature diagrams for the mixtures is discussed in Section IV along with comparisons of some of the results of this work with data from the literature.

SECTION I - PRELIMINIARY CONISIDERATIONS In this section, the thermodynamic relations which will be required are presented, a review of recent experimental enthalpy data is given and the methods of prediction of the enthalpy of mixtures are considered briefly with emphasis on those methods which will be used later in comparison with the experimental data. A review of all experimental data on the two binary systems studied in this work, methane - propane and methane - nitrogen, is also presented. Thermodynamic Relations The first law of thermodynamics, applied to a flow calorimeter with negligible potential and kinetic energy effects is: H e L2'-2 =)l F (1) 0 P where Q is the rate of heat leak, W is the rate of electrical energy transfer, and F is the mass flow rate. Flow calorimeters may be designed for various modes of operation. In the isobaric mode, the pressure difference P2-P1 is made small and the fluid is heated to change its temperature. Equation (1) becomes: H-~, _ H. p = F - i 4) d3P (2) r2 - ~ P1'X F - ap T where the integral term is the correction for the small pressure drop and Q is assumed to be negligible. In the isenthalpic mode, no energy - 3 -

is added to the system and the heat leak is made negligible. For this case Equation (1) reduces to >2,P2 ' 1,P x= (3) In a flow calorimeter operated in the isothermal mode, a pressur'e drop is imposed on the fluid, and electrical energy is added to retuirn the outlet temperature to that of the inlet. It is possible to utilize this scheme only when the Joule-Thomson coefficient is positive, i.e. when the fluid cools upon expansion. For an isothermal expansion, Equation (1) reduces to: H —P2 P p [;;2 f~1] TlX F, C T1 2 where Q is assumed negligible and the integral corrects for any mismatch between the inlet and outlet temperatures. In the two-phase region, Equation (1) can be used to determine the enthalpy change on vaporization. For a binary mixture, it is possible to define an infinite number of paths across the two-phase region, but only the isobaric and isothermal paths are of general interest and the -enthalpy changes are obtained from Equations (2) and (4), The relations presented above involve integral changes in enthalpy. These integral data in a single-phase region may be interpreted to yield the derivative enthalpy properties: the heat capacity, the Joule-Thomson coefficient, i, and the isothermal throttling coefficient,. Thus,-h

P \ ~ T/ - lia O 2 _ 1. (5 C E lim [ T P -AT 0 T2 - T11 and '-T -T I =H urn 125, 1 1 ~(6) V v* T = r lim, (7) apT AP + O I P2- P ) These three derivatives are related by the mathematical identity: = -~ C (8) of volume, temperature, and pressure as: =- v - T T p (9) thus allowing this coefficient to be obtained from compressibility data or an equation of state. It is instructive to consider the zero-pressure limit of $. The virial expansion, which is an open form of an equation of state, is a power series in density: PV B C 1 + + + --- (10) RT _ V V The terms B, C, --- are known as the second, third, --- virial coefficients and they are related by the statistical theory of imperfect gases to the interactions of molecules in pairs, triplets, etc.

A similar power series is an expansion in pressure: PV - = I + B'P + C'P + --- (11) RT The coefficients of the two series are related by: B' = B/RT (12) C' = (C-B2) / (RT)2 (13) Using equations (9), (11), (12) and (13), ~ can be expressed as: -T= 2T i dT T) +P — ' (14) The zero-pressure value of ' is finite and depends only on B: o dB B - T () (15) dT Experimental values of can be used to derive changes in B upon integration of Equation (15) or they can be compared with values of 0 calculated from virial coefficients obtained from other types of experiments. For binary mixtures, B is of the form: 2 2 mix 1 11 + 2X1X2 12 2 22 (16) where Bll and B22 are the pure component second virial coefficients and B12 is the interaction virial coefficient. It follows that the derivative of B. is: mix dB dB d2dB mix 2 11 +d 2 22 dT 1 dT dT (17) -6 -

The enthalpy change on mixing can be determined in a flow calorimeter by mixing two pure gases in a chamber and adding electrical energy to equalize the inlet and outlet temperatures. The first law of thermodynamics for this calorimeter reduces to: mix T' 2 P2 2 X1-1 2- T1'P = F (18) Corrections can be made for the differences in pressure and temperature between the inlet and outlet and the excess enthalpy or heat of mixing can be determined by: HE -i x xl Hl x2 3 X P,T (19) Review of Experimental Data All of the thermal properties mentioned above have been measured experimentally with most data being obtained on pure components. Reviews of data have been presented by Masi128 and Barieau5. A review of JouleThomson data was made by Johnston and White93, while Potter has considered both Joule-Thomson and isothermal throttling coefficient data. Table I presents a listing of the experimental determinations of thermal 120 properties under pressure, supplementing that of Mage. Emphasis has been placed on mixture data and, in general, references to pure component data are included only if they did not appear in earlier reviews. Although an increased amount of enthalpy data has become available, the need for more data to test methods of prediction and improve correlations remains.

TABLE I RECENT REFEREINCES TO EXPERIMENTAL THERIIAL DATA ON FLUIDS UNDER PRESSURE Constant Pressure Heat Capacity_p ata Year System Authors Reference 1956 Methanol, benzene McCracken and Smith 115 Methanol-benzene Methanol-hexane Mlethanol-benzene-hexane 1960 Carbon dioxide Koppel and Smith 105 1960 Ethanol, benzene, Storvick and Smith 178 n-Pentane, Ethanolbenzene, Ethanol-n-pentane 1962 1-Propanol, ethyl ether, Eubank and Smith 54 isopropyl ether, acetone, methyl ethyl ketone 1963 Methane Jones et al. 95 1963 Nitrogen Mage et al. 119 1963 Natural gas, methane HuJsak, Froning, 88 and Goddin 1963 Air, nitrogen, methane- Jenkins and Berwaldt 92 nitrogen 1963 l-Propanol-benzene Costa and Smith 34 1964 Mlethane-propane Manker et al., 122

Year System Authors References 1965 Carbon dioxide Vtikalovich, Altunin, 191 and Gureev 1965 IMethane-ethane-propane- Nathan 136 nitrogen 1965 Heavy water Stepanov and Mfursalov. 175 1965 Methane, nitrogen Sahgal et al. 166 1966 Methane-propane, Mather et al. 130 methane-nitrogen 1966 Water Sirbta and Grishkov 171 1966 Heliurm-nitrogen Mage and Katz 121 1966 Methane, nitrogen, Wiener 193 methane-hydrogen 1967 Natural gas Wilson and Barton 196 1967 Methane-propane 1Mather et al. 131 1967 Propane-isopentane Lenoir 112 1967 Natural gas Laverman and 111 Selcukoglu 1967 Hydrogen Medvedev, Dedikov, 134 and Astrov Latent Heat Data 1951 Carbon dioxide-ethylene Barnard et al. 6 1960 n-Pentane Kozicki and Sage 106 1960 n-Octane McKay and Sage 116 1961 Methane Iestermans and White 78 1961 Cyclohexane Kozicki and Sage 107 1962 l-Butene Kozicki, Cuffel, and 108 Sage -9 -

Year System Authors References 1963 Methane Jones et al. 95 1963 Nitrogen Mtage et al. 119 1963 1-Pentene Cuffel, Kozicki, 37 and Sage 1963 n-Decane Couch, Kozicki, 35 and Sage 1963 n-Butanol-benzene Shannon, Gustafson 169 and O'Neill 1963 t-Butanol-benzene, Shannon and O'Neill 170 t-Butanol-wat er 1964 Methane-propane Hanker 123 1964 n-Hexane Huisman and Sage 86 1964 trans-2-Butene Huisman and Sage 87 1965 n-Butane-n-Decane HIouseman and Sage 83 1967 Methane-ethylene Tully and Edmister 187 1967 Propane Helgeson and Sage 76 Joule-Thomson Data 1933 Helium-air Roebuck and Osterberg 156 1934 Petroleum naphtha, Pattee and Brown 143 n-pentane 1938 Helium-nitrogen Roebuck and Osterberg 158 1939 Methane-ethane Budenholzer, Sage 21 and Lacey 1940 Methane-n-Butane Budenholzer, Sage 22 and Lacey 1940 Helium-argon Roebuck and Osterberg 159 1942 Mlethane-propane Budenholzer et al. 23 1943 Natural gas Sage, Botkin, and 164 Lac ey - 10 -

Year System Authors References 1959 Carbon dioxide-propylene Sahgal 165 1959 Nitrogen-argon, Koeppe 103 nitrogen-hydrogen, argon-oxygen 1960 Nitrogen, methane, ethane, Head 75 methane-ethane, methanepropane, ethane-nitrogen 1962 Nitrogen Potter and Levy 149 1964 Nitrogen-ethane Stockett and Wenzel 177 1964 Nitrogen, methane, Ahlert 1 nitrogen-methane-ethane 1965 Methane-hydrogen, Ayber 4 ethylene-hydrogen 1966 Neon Gladun 71 Isothermal Throttling Data 1940 Benzene-n-heptane Parekh 142 1955 Carbon dioxide-ethylene Charnley et al. 27 Carbon dioxide-nitrous oxide Nitrous oxide-ethylene Nitrous oxide-nitrogen 1957 Argon-nitrogen Ishkin and Rogovaya 90 1965 Propane-benzene Yarborough and 199 Edmister 1966 Methane-propane Dillard 41 1966 Nitrogen-hydrogen Bolshakov et al. 17 1967 Steam Stribolt and Lydersen 180 1967 Methane-hydrogen Gelperin et al. 67 1967 Methane-nitrogen Bolshakov et al. 18 - 11 -

Year Syst.em Authors References IHeat of Mixing Data 1962 Hydrogen-nitrogen Beenakker and 8 Coremans 1965 Hydrogen-nitrogen, Beenakker et al. 9 hydrogen-argon, nitrogenargon-methane-hydrogen, argon-methane 1967 Hydrogen-nitrogen, Knoester, Taconis, 102 hydrogen-argon, nitrogen- and Beenakker argon, hydrogen-nitrogenargon 1967 Hydrogen-methane, helium- Van Eijnsbergen and 189 methane, methane-nitrogen, Beenakker methane-argon, helium-argon Methods of Prediction of Enthalpies of Mixtures In most engineering problems, enthalpies must be generated from correlations and prediction methods. The number of systems of interest is so large and the rate of production of experimental enthalpy data so small because of the time and effort involved that it is unlikely that experimental data are available for the problem under consideration. The ideal solution would be the calculation of thermodynamic properties, including enthalpy, from a knowledge of the interactions between molecules. At present this can only be done for relatively simple molecular models, but increasing efforts are being made in this area. For example, Hermsen and Prausnitz and Eckert, Renon, and Prausnitz have calculated excess functions for binary liquid mixtures of hydrocarbons at low pressure which are in agreement with experimental values. Osborne o has also presented a method for the prediction of liquid mixture - 12 -

enthalpies from a molecular model for liquid mixing. Limited comparisons were in agreement with experimental data. A combination of the hard-sphere and Lennard-Jones potentials was used by Orentlicher and Prausnitz 39 to obtain a three parameter equation for the density and energy of dense fluids. The parameters evaluated from pure component density and enthalpy were found to predict enthalpies for simple fluid mixtures within about 4 percent. Despite this recent trend toward more fundamental methods of prediction, empirical or semi-empirical methods will continue to be used, especially since they may be applicable over a wider range of conditions than the theoretical methods. A detailed investigation of various prediction methods will not be given here, but the main classes of methods will be considered and methods will be compared with experimental data later. Hobson and Weber ' have reviewed prediction methods, and Reid and Sherwood 15 have recommended various correlations. A recent review of the types of mixture prediction methods was made by Nathan137 The main groups into which the methods can be divided are: 1. Pure Component 2. Equivalent component 3. Corresponding states 4, Fugacity relationships 5. Equations of state 1. Pure Comnonents The assumption of zero heat of mixing allows the enthalpy of a mixture to be calculated from the sum of the enthalpies of the pure

components present, This method may give good results at moderate pressures and relatively high temperatures, for chemically similar compounds such as hydrocarbons in a homologous series. Charts for 133 145 the pure component enthalpies are given by Maxwell, Peters 167 and Scheibel and Jenny. Difficulty arises in using these charts when the pure component does not exist in the phase that it is in the mixture (i.e. a liquid above, or a vapor below the critical temperature of the component). Peters has derived auxiliary curves for estimation of partial enthalpies under those conditions and Maxwell used an extension of the vapor pressure curve for the partial enthalpy of a low-boiling component in a liquid mixture. 2. Equivalent Comn6nent Conceot for Mixtures Several methods have been proposed which consider the mixture to be a hypothetical pure component and correlate enthalpies on the basis of a parameter such as molal average boiling point, mixture molecular weight, or mixture specific gravity. The assumption is made that a mixture and a pure component with the same correlative parameter exhibit the same enthalpy behavior. Scheibel and Jenny167 and CanJar and Peterka24 have presented correlations of this type for hydrocarbons. 3. Corresppnding States The principle of corresponding states was first applied to the correlation of P-V-T data, but the extension to enthalpies using the integrated form of Equation (9) follows directly. Among the earliest correlations of this type are those of Cope,Lewis and 33 47

Later work on generalized correlations has employed a third parameter to improve the agreement with experimental data. Lydersen, li4 Greenkorn, and Hougen used the compressibility factor at the 38 critical point, zc, while Curl and Pitzer employed the acentric factor w, which is related to the shape of the reduced vapor pres& sure curve. In applying these correlations to mixtures it is necessary to obtain values for the critical temperature, T, the critical pressure, Pc, and the third parameter of the mixture. In most cases, recourse is made to rules which allow the mixture critical properties to be calculated from those of the pure components. For example, the values for a number of correlations are obtained 96 by the linear mixing rules suggested by Kay, but non-linear mixing rules have been proposed by Pitzer and Hultgren and Prausnitz and Gunn150 4. Enthalpies from Fugacities The effect of temperature on the fugacity of a component in a mixture is given by: ain f. H. - H. t aT) Px -rT (20) and if a relation for the fugacities is known, the partial molal enthalpy Hi can be calculated. The disadvantage of this method is that any error in the expression for fugacity (which is derived from P-V-T and vapor-liquid equilibrium data) is magnified in the differentiation. The advantage claimed for this method is -15 -

that the enthalpies obtained are consistent with the vapor-liquid equilibrium data, a point of importance in multicomponent mixtures. The chief proponents of this method have been Edmister and co50,53 workers. 5 5, quations of State The enthalpy of many substances is known in the ideal gas state from spectroscopic calculations and direct experimental 161 determinations at low pressures. Rossini has tabulated values for many hydrocarbons and simple gases. With the effect of temperature on enthalpy known at zero pressure, the effect of pressure on enthalpy can be obtained from Equation (9) if an equation of state is used to represent the P-V-T behavior of the substance. A large number of equations of state have been proposed, but only a few have been used for extensive calculations of enthalpies. Martin 7 has recently reviewed equations of state primarily from the standpoint of representation of the P-V-T surface of a substance. Relatively simple equations like the Redlich-Kwong equation have been used for enthalpy prediction and the recent modification by Wilson 95 is claimed to improve the accuracy of such predictions, 10 More complex equations such as the Benedict-Wlebb-Rubin and Martin125 Hou equations have also been used to predict thermodynamic properties, including enthalpy. Values of the enthalpy of CO2 in the critical region have been calculated from the Martin-Hou equationl26 which agree within a few percent with the experimental enthalpy data of Koppel and Smith105 A problem arises in the extension of equation of state

calculations to mixtures since the constants for particular mixtures are not available and usually must be calculated from empirical mixing rules utilizing the constants of the pure components. The virial equation is one of the few equations for which the composition dependence of the constants is known exactly. This equation is restricted to vapors since the power series relation tends to diverge at densities approaching those of liquids. 6. Special Considerations for Latent Heats IMlany of the methods described above can be used for latent heat prediction, but some have been specifically developed for this purpose. 181 Strickland-Constable has presented the rigorous equations for calculation of the enthalpy change of vaporization of a binary mixture at constant pressure and at constant temperature from the properties of the phases. Only the isothermal change can be calculated from P-V-T data; the isobaric change requires a knowledge of the heat capacities of the two phases. For most mixtures the data are not extensive enough for accurate calculations and few have been attempted, 49 Edmister has derived a simple approximate expression for the isobaric latent heat which requires only a knowledge of the phase be176 havior and ideal gas enthalpies. Stevens and Thodos have fit the 114 tables of Lydersen-Greenkorn-Hougen for the saturated liquid and vapor envelopes and applied the resulting equations to mixtures using pseudocritical properties calculated by Kay's rule. A listing of commonly-used methods of prediction is given in Table II, along with the region of applicability and the type of the correlation. Most of these methods are applicable only to non-polar

materials and many are specifically for hydrocarbons. Comparisons of various prediction methods with experimental data have appeared in a number of recent articles. Wiener94 and Findlay, Mora, and Jacoby compared some of the data of this work with various correlations. More extensive comparisons with other published data as well as the data of this work are made by Sehgal. 168 et al. General conclusions that can be dramwn from these comparisons is that no method of prediction is suitable in the region of the critical point or in the two-phase region, but that a number of methods are satisfactory in the liquid and gaseous regions. TABLE II METHODS OF PREDICTION OF EINTHALPIES OF MIXTURES Method Application of Correlation Author Reference 3 Tr 0.8 to 2.5 Pr < 5.5 Edmister 47 2,3 0 to 600 F. < 10,000 psia IIolcomb and 82 Brown 1,2 -100 to 8000 F. < 1000 psia Scheibel and 167 Jenny 1 -260 to 4000 F. < 600 psia Peters 145 1 -200 to 7000 F. < 2200 psia Maxwell 133 4 -100 to 4000 F. < 600 psia CanJar and 25 Edmister 2,4 -100 to 3000 F. < 3500 psia Papadopoulos et al. 141 3,4 Tr 0o.6 to 2 Pr 0.2 to 1 Edmister and 48 Canjar 4 Isobaric integral heat of vaporization 49 Edmister 3 Tr 0.5 to 15 Pr < 30 Lydersen et al. 114 2 -200 to 5000 F. < 1500 psia CanJar and 24 Peterka

TABLE II (Cont.) Method Application of Correlation Author Reference 3 Tr 0.8 to 4 Pr < 9 Curl and 38 Pitzer 5 Virial equation of state Brewer and 19 Geist 3 Saturated liquid and vapor Stevens and 176 enthalpies Thodos 5 Virial equation of state Tooke and Hays 184 5 Redlich-Kwong equation of Edmister, Thompson 51 State and Yarborough 3 100 to 4600 F. 200 to 2000 psia Edmister and 52 Yarborough 4 Saturated liquid and vapor Edmister, Persyn 50 enthalpies and Erbar 4 Saturated liquid and vapor Erbar, Persyn 53 enthalpies and Edmister 3 Tr 0.5 to 30 Pr < 30 Yen and Alexander 200 5 Modified Redlich-Kwong equation Wilson 195 of state 5 Modified B-W-R equation of state Barner and 7 Schreiner 3 Tr 0.5 to 4 Pr < 10 NGPSA 138 3 Tr 0.4 to 60 Pr < 100 Yen 201 1 Pure Component 2 Equivalent Component 3 Corresponding states 4 Partial enthalpies from fugacity 5 Equation of state - 19 -

The Methane Propane System Both of the pure components of this system have been extensively studied and compilations of the thermodynamic properties of methane and propane are presented by Tester183 and Kuloor et.al.10 Some enthalpy determinations made since these compilations were 94 166 published include the work of Jones, Sahgal et al, and Colwell, Gill, and Morrison3 for methane and Yarborough98 and Helgeson and Sage76 for propane. Fewer data exist on the properties of methane-propane mixtures, but they include volumetric, phase equilibrium, Joule-Thomson and heat capacity measurements. Comrressibility Data Sage, Lacey, and Schaafsma 63 measured the density of mixtures of methane and propane at temperatures between 200 and 90 C at pressures from 10 to 200 atmospheres. The compositions of the coexisting phases were also determined in this temperature range. A 152 later investigation by Reamer, Sage, and Lacey extended the earlier work to pressures up to 10,000 psia for temperatures between 400 and 4600F and increased the accuracy of values in the range covered by the older work. Again both volumetric and phase behavior were studied. Phase eaulibr ia Other studies of the phase behavior of the methane-propane system besides the work of Sage and co-workers have been published, 65 Frolich et al. determined the solubility of methane in propane -20 -

at 25 C at pressures up to 90 atmospheres. Data in the low temperature region from -1760 to 320F were obtained by Akers, Burns, and Fairchild2 These data have appreciable scatter and the later work of Price and Kobayashil51 from 50~ domwn to -200 F is to be preferred. A few data points of the solubility of methane in propane from 920 to 128 K are 28 given by Cheung and Wang in a study of hydrocarbon solvents at low temperatures. Above 90~F Roof and Baron report serious disagreement (as much as 50 psi) between the critical locus determined by Reamer, Sage and Lacey152 and their visual observations. However, their values differ by 18 psi at 110 F from the value determined by Rutherfordl in the same laboratory. Thermal Data Joule-Thomson coefficients for three mixtures of methane and 23 propane have been determined by Budenholzer et al. at pressures up to 1500 psia in the temperature interval between 700 and 3100F, Head75 measured Joule-Thomson coefficients for a mixture of 51.1 mole percent propane in methane at pressures up to 40 atmospheres between 2600 and 3600K. Attempts were made to obtain data in the twophase region but surging flow through the throttle valve led Head to estimate the accuracy of the two-phase results as + 10 percent, 39 Cutler and Morrison have measured the vapor pressures and heat capacities of liquid mixtures of methane and propane and heat of vaporization of methane from the mixtures in the temperature range 90 to 110 0K. This work is quite valuable since it gives the heat of mixing of methane-propane mixtures directly over the entire range of compositions. h 2 Dillard et al. present data of the isothermal effect of pressure - 21 -

on enthalpy for methane and two mixtures of methane and propane in the range 900 to 200~F at pressures up to 2000 psia. The data for methane and a nominal 5 percent propane in methane mixture appeared in the thesis 41 of Dillard 123 Manker obtained isobaric data on a nominal 5 percent propane in methane mixture at temperatures from -2450 to 87 F at pressures from 250 to 2000 psia. Approximate Joule-Thomson coefficients were obtained at 60 F at pressures up to 2000 psia. A preliminary report of this work has been published122 Some of the results of this thesis have been presented in publications prior to this report. Some data and preliminary enthalpy diagrams for the nominal 12 percent propane in methane 29'130 and 28 percent 131 propane in methane mixtures have been published. Other experimental data of the methane-propane system are presented in Table III. - 22 -

T]~ABLE II I EXPERIMENTTAL' INVESTIGATIONS' ON TH,.E MIiETHIANTE PROPANE SYSTEM Property, Teperature Prtessure Year Author Reference (OF) (psia) P-V-T-x, V-L 68 to 1914 1147 to. 2840 1934 Sage, Lacey, and Schaafsma 163 P-V-T-x, V-L ho to 450 200 to 10,000 1950 Reamer, Sage, Lacey 152 V-L 77 1320 1931 Frolich et al. 65 V-L -176 to 32 50 to 1450 1954 Akers, Burns and Fairchild 2 V-L -200 to 50 100 to 1300 1959 Price and Kobayashi 151 ~ V-L 110 950 to 1268 1962 Rutherford 162 V-L -295 to -220 0.2 to 24 1964 Cheung and Wang 28 V-L 89 tc 181 823 to 1323 1967 Roof and Baron 160 Joule-Thomson 70 to 310 0 to 1500 1942 Budenholzer et al, 23 Joule-Thomson 10 to 190 25 to 590 1960 Head 75 C SAH -2142 tc 80 250 to 2000 19614 Manker 123 C LH vap -298 to 262 < 14.7 1965 Cutler and Morrison 39 LHT 90 to 200 0 to 2000 1966 Dillard 141 1966 Dillard et al1.42 Viscosity 68 to 482 114.7 1931 Trautz and Sorg 186

TABLE IIL (Cont.) Property Te6peYr-ture Pressure Year Author Reference Viscosity 77 to 437 400 to 5000 1943 Bicher and Katz 12 Viscosity 40 to 280 100 to 8000 1966 Giddings, Kao and Kobayashi 68 Viscosity, density -.239 to 70 100 to 5000 1967 Huang, Swift and Kurata 84 Thermal Conductivity 122 to 302 14,7 1960 Smith, Durbin, and Kobayashi 172 Surface Tension 5 to 194 40 to 1500 1943 Weinaug and Katz 192

The i4ethane-NIitrogen_ System A number of compilations of the thermodynamic properties of the pure components of this system are available. References for methane are given in the section on the methane-propane system and recent tab43 182 ulations for nitrogen include those of Din and Strobridge. Enthalpy measurements on nitrogen since these works were compiled 119 166 include the work of sMage et al.9 and those of Sahgal et al. Other references to recent enthalpy data on nitrogen are given in Table I. The thermodynamic properties of mixtures containing 10 to 30 mole percent nitrogen in methane have been calculated by Bloomer et al.16 from volumetric data and ideal gas heat capacities. Joule-Thomson coefficients for mixtures of methane and nitrogen were calculated from 144 P-V-T data by Perry and Herrmann and heats of mixing for liquid mixtures have been calculated from volumetric and phase behavior data 101 by Knapp. Few direct enthalpy measurements have been made on methane-nitrogen mixtures, but extensive phase equilibria and volumetric data are available. Table IV lists the experimental investigations which have been made on this system. - 25 -

TABLE IV EXPERIMETAL 'INVESTIGATIONS 'ON 'THE METHLANE-M'NITROGEN 'SYSTEM Property TetP56rettitre Pressure Year Author Reference (OF) (psia) P-V-T-x 32 wo 392 425 to 48oo 1928 Keyes and Burks 99 P-V-T-x 32 to $92 1470 to 10,300 1942. Kritschewsky and Levchenko 109 P-V-T-x -280 tc 200 0 to 1500 1955 Bloomer'etal. 16 V-L -303 to -268 14.7 1919 McTaggart and Edwards 117 V-L -298 tc -220 12 to 337 1939 Torocheshnikov and Levius 185 V-L a266 147 1939 Steckel and Zinn V-L -293 7 1943 Vellinger and Pons 190 V-L -202 tc -148 225 to 688 1951 Kelley and Lipscomb 97 V-L -295 tc -119 9 to 685 1952 Bloomer and Parent 14 V-L -"28) tc -150 20 to 650 1953 Cines et al. 29 V-t -313 tc -175 29 to 230 1957 Fastovsky and Petrovsky 59 V-L -295 tc -236 < 82 1964 Cheung and Wang 28 V-eL -95 < 4 1966 Sprow and Prausnitz 173 V-L -309 tc -296 < 4 1967 Fuks and Bellemans 66 VE -329 tc -298 < 14.7 1959 Blagoi 13 S-L -$45 tc -298 < 14.7 1939 Fedorova

TABLE IV (Cont.) Property Te,perature e Pressure Year Reference (OF) (psia) S-L -332 to -317 < 14.7 1941 Fastovsky and Krestinsky 58 Cp -207 to 69 300 1963 Jenkins and Berwaldt 92 Cp -224 to -186 125 to 350 1966 Kohne, Anderson, Miller 104 -148 to 32 0 to 735 1967 Bolshakov et al. 18 HE -T7 to 68 190 to 1610 1966 Van EiJnsbergen 188

SECTION II - THE ISOBARIC EFFECT OF TFJIPERATURE ON ENITHALPY Enthalpy data were obtained on binary mixtures of methane with propane and with nitrogen using the isobaric flow calorimeter designed by Faulkner. This calorimeter is part of a recycle system, the evolution of which can be traced in the theses of Faulkner, Jones9, 120 123 Mage and Manker. The recycle system serves to bring the fluid under investigation to desired conditions of temperature and pressure for measurements. Experimental Equipment A schematic diagram of the flow system is shown in Figure 1. The fluid is compressed to a pressure higher than that at which measurements are to be made and is passed through two large filters (4,5) to remove any oil or water in the gas. The fluid is throttled to the approximate measuring pressure and a portion throttled again (7) back to the compressor intake. The compressor is a constant volume machine and therefore the flow rate through the calorimeter section is varied by regulation of the amount of this bypass stream. The fluid passing through the calorimeter section is cooled in the dry ice bath (9) if the desired measurement temperature is below about -100l F. Further cooling is accomplished in the heat exchange bath (11) which contains coils through which liquid nitrogen is passed. The fluid is brought to within a few degrees of the desired temperature in this bath and passes to the calorimeter bath (14). In the calorimeter bath the fluid is brought to bath temperature by passing through 100 feet of 3/16" O.D. copper coil before entering the isobaric flow calorimeter (18). Here electrical energy is added - 28 -

- 29 - 1000-2500 PSIA 250-2000 PSIA 4 5 _-95 PSIA 20 20 19 32 13 LEGEND 1. Compressor intake buffer tank 17. Platinum thermometer 2. Micron filter 18. Calorimeter 3. Corblin Diaphragm Compressor, 4 SCFM 19. Finned tubing 4. Oil removal unit (fiberglass) 20. Calorimeter metering valves 5. Water removal unit (anhydrous calcium sulfate) 21. Line heater 6. Metering valves 22. Metering bath 7. Calorimeter by-pass metering valves 23. Water cooling 8. Gas storage tanks 24. Thermometer 9. Dry ice cooler 25. Flowmeter (Meriam) 11. Low temperature cooling bath 27. U-tube and wa meter manometer 12. Liquid nitrogen cooling 28. Lead to 180" mercury manometer 13. Stirrer 29. Buffer tank 14. Low temperature measuring bath 30. Pressure balance 15. Controlled heat input 31. High pressure mercury manometer 16. Nickel resistance-sensor for heat input 32. Resistance thermometer for bath controller controller Figure 1. Flow Diagram of the Apparatus

and the resulting temperature rise measured. Measurements are made of the inlet pressure to the calorimeter, the pressure drop across the calorimeter and the temperature of the calorimeter bath. After leaving the calorimeter the fluid is brought back to room temperature before throttling to 80 psig (Valve 20). The gas is then passed to the flow meter bath (22) where the flow rate is measured by a calibrated IMeriam flow meter (25). After leaving the flow meter bath the gas passes through several buffer tanks before returning to the intake of the compressor. The pressure level of the measurements is changed by adjustment of the amount of gas in the storage tanks (8) relative to the amount in the recycle system. A major revision to the system made before the start of this work was the replacement of the oil-lubricated compressor previously employed, with an A2CCV50/250 Corblin diaphragm compressor with remote heads (3). This compressor removes the source of oil which had caused composition variations because of the different solubilities of the components of the mixture in the compressor oil. The remote heads allow operation at fluid temperatures up to 3000 F without expensive hydraulic oils. A photograph of this compressor is shown in Figure 2. Measuring Instruments A detailed description of the measuring instruments has been 94 given by Jones and only changes from that work are given here. The important measurements are: 1. The temperature rise in the calorimeter. This is measured by duplicate six-junction copper-constantan thermopiles which were calibrated at the oxygen and nitrogen points and compared with a - 30 -

Figure 2. Corblin Diaphragm Compressor

platinum thermometer at 200 C intervals by the National Bureau of Standards. In previous work only one thermopile was used (G25691T) which was calibrated from -196~ to 00 C. The second thermopile added before this work was begun (G-32321) is calibrated from -196 to +150 C and the calibration data are given in Table XXXIV of Appendix B. The accuracy of the temperature rise measurement is about + 0.2%, 2. The temperature of the calorimeter bath, which is assumed to be the inlet temperature to the calorimeter, is measured using a platinum resistance thermometer, The calibration constants are given by 94 Jones 3. The electrical energy input to the calorimeter supplied by a DC power supply is measured by a K-3 potentiometer using standard resistors to scale the voltages to the range of the potentiometer. The circuitry and the calibration data for the potentiometer and standard 94 resistors are given by Jones. The accuracy of the electrical energy determination is + 0.05%. 4, The mass flow rate of gas is determined from the measurement of the pressure drop across the laminar flow element together with the temperature and pressure at the element. These data are used to solve the calibration equation: A? i= B+ )A + C+( + D (21) for the mass flow rate, F. The calibration constants A,B,C,D are obtained from a least squares fit of calibration data obtained by direct weighing. The calibration equipment and procedure are described by Jones A comparison between values determined by direct - 32 -

weighing (recalibration) in the third set of calibration data with values calculated from Equation (21) using constants determined from the previous two calibration sets is given in Table V, These data were obtained on the nominal 5 mole percent propane in methane mixture. TABLE V COMPARISON OF MASS FLOW RATES DETERMINED BY DIRECT WEIGHING (RECALIBRATION) WITH VALUES CALCULATED FROM EARLIER CALIBRATION CURVE Run Recalibration Calculated Percent lb/min lb/min Deviation 31.06930.06937 -0.10 32,06921,06923 -0.03 33,10518.10522 -0,04 34.10511.10516 -0.05 35.15961.15943 +0.11 36.15960.15938 +0,14 37.20027.19981 +0.23 38.19999.19957 +0.21 39.22448,22379 +0.31 310.22359.22303 +0,25 It can be seen that the maximum deviation is 0.31 percent while the absolute average deviation is 0.15 percent. The accuracy of the mass flow rate determination is believed to be about + 0.2%, 5. The pressure at the inlet to the calorimeter was measured - 33 -

with a calibrated IHecise gauge during measurements on the nominal 12 and 28 percent propane in methane and nominal 43 percent nitrogen in methane mixtures. The calibration of this gauge is given in Table XXXV of Appendix B. The accuracy of the gauge is 0.1 percent of full scale. In the work on the nominal 5 mole percent propane in methane mixture a calibrated dead weight gauge was used to measure the inlet pressure to the calorimeter. The calibration data for this gauge are given in Table XXXVI of Appendix B and can be seen to be accurate to 0.03 percent. 6. The pressure drop across the isobaric calorimeter is measured with a 40-inch high pressure mercury manometer. The accuracy of this measurement is - 0.1 inches of mercury which does not introduce appreciable error since the correction term for the pressure drop, which is calculated from the B-W-R equation of state, is rarely one percent of the total energy input. Procedure for Isobaric Measurements The fluid being studied is brought to the desired state of pressure and temperature with the recycle system shown in Figure 1 and passed into the isobaric calorimeter at a desired flow rate. Electrical energy is added at a rate which results in the desired fluid temperature at the calorimeter outlet. The temperature rise is monitored until it reaches a constant value indicating attainment of steady state. This period is usually 3/4 to 1 hour, and at this point the values of the variables are recorded. Materials Used The source and purity of the gases used in this work are given in Table VI, The gases were used without further purification. - 34 -

TABLE VI MATERIALS Component Supplier Pur UMethane Southern California Gas Co. 99.7% Propane Phillips Petroleum Co. 99.9% Nitrogen Liquid Carbonic Corp. 99.95% Experimental Data On The Methane Propane System Isobaric enthalpy determinations were made on three mixtures of methane and propane, of nominal composition 5, 12, and 28 mole percent propane. Nominal 5 Percent Prppane in Methane Mixture Isobaric data for this mixture were obtained at temperatures from 80o F. to 257eF. at pressures from 500 to 2000 psia. This mixture was previously studied by Manker123 at temperatures from -2450F. to 87 F. at pressures from 250 to 2000 psia. The range of the present experiments is shown in Figure 3, where dashed lines indicate the experimental determinations of Manker. Initial experiments were made using the mixture of Manker, which had been stored in cylinders since his work. This gas was analyzed chromatographically to be 5.2 mole percent propane. After about half the data runs-on this mixture had been made, additional gas was required to replace losses. The final mixture did not match the initial mixture exactly and was analyzed to be 5.1 mole percent propane in methane. Impurities were determined by mass spectrometer analyses and the composition of the nominal 5 percent mixture is given in Table VII. - 35

~~~~2000r~~ -'__+_ - I~~~~ I l lNOMINAL MOLE 1800 -I FRACTIONS 0 ---F~ |. __ __ b I | ||C3H80-.05 IlCH4 0.95 ~~~~~~~~~~~~1600jj~~~~~~~ l ||MANKER (1964) — ~- - -t- --— *a- — *t t~- *. -~ *THIS WORK 1400 - 1200 - --— _ I O ----.... Co I cr: z~........... l- I I1 w 800 a — a- ~ ~ ~ ~ ~ 0 600 -----. 400 ------- - 200 a 0 I I I I I I I I I -250 -200 150 -100 -50 0 50 100 150 200 250 TEMPERATURE - ~F Figure 3. Range of Experimental Measurements on the Nominal 5 Percent Mixture

TABLE VII COMPOSITION OF NOMINIAL 5 PERCENT MIXTURE Mole Fraction Methane 0.9463 * Propane 0.051 +.001 Carbon Dioxide 0.0003 Ethane } 0.0013 Nitrogen Oxygen/Argon 0.00001 1.0000 * by difference The flow meter was calibrated three times in the course of the experimental work on this mixture. All three calibration sets are in good agreement and a cubic equation fits the 34 calibration points within 0.17 percent. The calibration data are given in Table XXXVII of Appendix B and the data are plotted on Figure 47. The experimental data converted to units used in this work, psia, 0F, pounds mass and Btu, are presented in Table XLIII of Appendix D. The experimental enthalpy data were plotted as mean heat capacity versus temperature to obtain point values of heat capacity as showm in Figure 4. The data are seen to blend smoothly into the results of Hanker at lower temperatures and into the results of calculations using the B-W-R equation of state at higher temperatures. Although Manker tabulated C up to 1000F, most of his data end about 600F and the P values up to 100 F are extrapolations. Figure shows that the extrapolated values of Manker are low. The same behavior was found at other pressures, the extrapolated values being too low in all cases. The table - 37 -

1.00 Methane - Propane Mole Fraction C3H8 0.052 Mole Fraction CH2 0.948 Pressure 2000 PSIA Data Points T Difference Pointsrisork.900 k,Experimental Data of o Tabulated Values of Manker End Manker (1964) o | * Benedict, Webb, Rubin(1940,1942) D.80 ~o I~~ cDr t1%.70.60 I 20 60 100 140 180 220 260 300 TEMPERATURE (~F) Figure 4. Blending of Experimental Heat Capacities with Values Calculated from B-W-R Equation of State

of heat capacities for this mixture presented by Manker has been revised and extended to 300 F. The values are listed.in Table VIII with entries in italics indicating interpolation or extrapolation of experimental data. Experimental values of the heat capacity at 200 F are plotted as a function of pressure in Figure 5. Below 1500 psia the results are linear in pressure and the value at zero pressure obtained by linear extrapolation agrees within 0.1 percent with the point calculated for the mixture from the ideal gas values for methane and propane of Rossini. Nominal 12 Percent Pronane in ]Methane Mixture _._._. _..___ ___. _._ __ _ __. _ _ _ Isobaric determinations in this mixture cover the liquid, twophase, and gaseous regions at temperatures from -2400F to 1400F at pressures from 250 to 2000 psia. The location of the experimental data is shown in Figure 6. Chronologically, this mixture was the first to be studied and many problems arose in the experimental work. The Corblin diaphragm compressor high pressure diaphragms failed at irregular intervals much shorter than the 500 to 1000 hours service life claimed by the manufacturer. In one case, the high pressure diaphragms failed 8 hours after replacement. The continual dismantling of the compressor heads led to the loss of mixture and it appears that the system gas was never thoroughly mixed for the early experiments. Another problem was encountered in the calibration of the flow meter. The pipe dope used to Join the threaded connections on the flowmeter was found to have entered the element causing shifts in the flow meter calibration. As a result of these problems, the preliminary data presented on this mixture9 are believed - 39 -

-40 -TABLE VIII TABULATED VALUES OF ISOBARIC HEAT CAPACITIES FOR THE NOMINAL 5 PERCENT MIXTURE C (Btu/lb - ~F) p Temperature Pressure, psia OF 0 250 500 750 1000 1200 1500 1700 2000 -280 o.460 0.740 0.742 0.747 0.749 0.751 0.753 0.753 0.752 -270 0.460 0.746 0.749 0.752 0.754 0.755 0.756 0.755 0.752 -260 0.461 0.753 0.757 0.758 0.759 0.760 0.759 0.757 0.753 -250 0. 462 0.763 0.764 0.765 0.764 0.764 0.763 0.760 q 755 -240 0.462 0.773 0.772 0.772 0.770 0.769 0.767 0.764 0.758 -230 0.463 0.787 0.782 0.780 0.776 0.774 0.771 0.767 0.761 -220 0.463 0.801 0.795 0.789 0.784 0.781 0.775 0.772 0. 766 -210 0.464 0.818 0.809 0.801 0.793 0.788 0.781 0.776 0.772 -200 0.464 0.838 0.826 0.814 0.803 0.796 0.787 0.783 0.778 -190 0.465 0.862 o.844 0.830. 816 0. 806 0. 796 0.790 0.785 -180 o.,466 0.888 o.866 0.847 0.831 0.820 0.808 0.802 0.793 -170 0.466 0,927 0.894 0.871 0.849 0.837 0.824 0.812 0.803 -160 0.467 0.928. 897 0.872 0.859 0.842 0.832 0.815 -150 o.468 0.972 0,.936.g901 0.889 0.862 0.847 0.827 -140 o.469 1.037 0.981 0.938 0.922 0.884 0. 867 0.842 -130 0.470 1.182 1.041 o.986 0.958. 908 0.887 0.858 -120 0.471 1.127 1.051 1.003 0.937 0.910 0.876 -110 0.472 1. 268 1.155 1.062 0.976 0. 944 0.897 -100 0.473 1.330 1.144 1.026 0. 982 0.921 - 90 0.474 1.618 1.292 1.087 1.027 0.950 - 80 0.475 2.281 1.499 1.159 1.080 0.983 - 71.8 2.513 - 70 0.477 2.467 1.725 1.257 1.128 1.018 - 60 0.478 1.930 1,849 1.357 1.188 1.054 - 59.6 1.849 - 50 o.480 0.557 1.470 1.723 1.414 1.245 1.087 - 44.6 1.426 - 40 0.482 0.550 0.645 1.223 1.470 1.421 1.280 1.116 - 36.2 1.283 - 30 0.484 0.544 0.632 0.773 1.066 1.229 1.367 1.275 1.137 - 25 1.140 - 20 0.487 0.539 0.620 0.747 0.949 1,073 1.269 1.234 1.138 - 10 0.489 0.536 0.609 0.717 0.871 0.986 1.164 1.176 1.121 0 0.491 0.534 0.600 0.690 0.817 0.936 1.069 1.118 1.090 10 0.494 0.534 0.593 0.674 0.777 0.868 0.990 1.054 1.054 20 0.497 0.535 0.588 0.658 0.746 0.820 0.929 0.993 1.014 30 0.500 0.536 0.583 0.646 0.721 0.789 0.881 0.939 0. 974 40 0.503 0.537 0.581 0.635 0.703 0.760. 840 0.899 0.935 50 0.506 0.537 0.579 0.629 0.689 0. 734 0.806 0.863 o.896 60 0.509 0.538 0.578 0.625 0.677 0.719 0,.779 0.815 o.865 70 0.512 0.540 0.577 0.621 0.668 0.706 0.759 0.792 0.840 80 0.516 0,.543 0.577 0.618 o.660 0.694 0.743 0.774 0.818 90 0.519 0.546 0.577 0.615 o.653 0.684 0,.730 0.758 0.799 100 0.523 0.548 0.578 0. 612. 647 0.676 0.718 0.744 0.783 110 0.527 0.551 0.579 0.609 0. 642 0.669 0.709 0.733 0.769 120 0.531 0.554 0.580 0.608 0.638 0.,663 0,700 0.723 0.757 130 0.535 0.558 0.582 0.607 0.635 0.659 0,.693 0.714 0.745 140 0.539 0.561 0.584 0.608 0.633 0.655 o.687 0.707 0.735 150 0.543 0.564 0.586 0,608 0.632 0. 652 0.682 0.700 0.727 160 0.547 0. 567 0.588 0.609 0.631 0.650 0.678 0.695 0.719 170 0.552 0.571 0.590 0.610 0.630 0.648 0.674 0,.690 0.713 180 0.556 0.574 0.593 0.612 0.631 0,.647 0,.672 0.687 0.708 190 0.560 0.578 0.596 0.614 0,.632 0.647 0,670 0,.684 0.704 200 0.565 0.582 0.599 0.616 0,.633 0.647 0.668 0. 681 0,.701 210 0.570 0.586 0.602 0.618 0.634 0.647 0.667 0.680 0.699 220 0.574 0.590 0.606 0.621 0.636 0.648 0,.667 0.679. 697 230 0.579 0. 594 0. 609 0. 623 0. 638 0, 649 0. 667 0. 678 0.696 240 o.584 0.598 0.612 0.626 0.640 0.651 0.668 0.679 0.695 250 0.588 0.602 0,616 0,629 0.643 0.653 0.669 0.679 0.695 260 0.593 0o. 606 0.619 0.632 0. 645 0, 655 0. 670 0. 680 0.695 270 0. 598 0. 611 0. 623 0, 635 0, 647 0. 657 0. 672 0.681 0. 696 280 0.603 0o. 614 0. 626 0. 638 0. 650 0, 660 0. 674 0. 683 0. 696 290 0.608 0o. 619 0, 630 0. 641 0. 653 0. 663 0. 677 0, 685 0. 696 300 0. 613 0o. 623 0.634 0.644 0, 655 0, 665 0, 680 0.688 0. 697

.720 METHANE -PROPANE MOLE FRACTION PROPANE 0.05.700 - MOLE FRACTION METHANE 0.95 TEMPERATURE: 2000 F.680 LL.660 -o 2.640.620.600 1 0 Rossini etcl/,.API 44 (1953) 0 This Work.580.560 0 500 1000 1500 2000 PRESSURE (PSIA) Figure 5. The Heat Capacity of the Nominal 5 Percent Mixture as a Function of Pressure

2000 o. ' 1600 ae Q..OV -250 -200 -150 -100 -50 0 50 100 150 200 250 Temperature (F) Figure 6. Range of Experimental Measurements on the Nominal 12 Percent Mi xture

to be in error. In May 1965 the system gas was completely remixed until a stable composition was attained. The joints connecting the flow meter to the system were either silver soldered or replaced by compression fittings to remove the source of contamination to the flow meter and the flow element was cleaned ultrasonically. The flow meter was calibrated and the enthalpy determinations reported here were made. A record of the composition during the course of the experimental work is presented in Figure 7. Although some variation is noted, there is no indication of a change in average composition with time. A sample of the nominal 12 percent propane mixture was independently analyzed at the Continental Oil Company in Ponca City, Oklahoma and at the Phillips Petroleum Company, Bartlesville, Oklahoma. The same sample was analyzed with the gas chromatograph of the laboratory and the mass spectrometer at the University of Michigan, A comparison of the results is presented in Table IX. TABLE IX COMPARISON OF ANALYSES OF INOMINITAL 12 PERCENT MIXTURE Chromatograph Mass Spectrometer Phillips Conoco U of M U of M 02/Ar ---- 0.01 N2 0,09 0,09 } 0.13 } 0.13 C2H6 C2H6 0,07 0.07 CO2 0.05.... 0.03 CH14 88.07 88.38 88.12 88.02 c3H8 11.72 11.46 11.71 11.85 + 0.37 Gas Processing Group -4 3 -

o After Calorimeter * Before Calorimeter 12.0 0 % 0 ~ '11.58~00 o 0 ~ Sr- o mSc~ o _ o o 0 0 0 0 C:dt I L co o ODj0 00. 11.5 0 0 U~~~~~~~~~~~~ L. To 11.0 April 1 May 1 June 1 July 1 1965 ~~~~~~~~~~~~~~~~~JlA_ I I1I6I 500 400 500 600 700 Compressor Hours Figure 7. Composition of the Nominal 12 Percent Mixture as a Function of Time

The three chromatographic analyses are seen to be in good agreement and the mass spectrometer value in agreement within its limits of error. Consideration of the numerous analyses and the independent checks led to the selection of the composition shown in Table X for the nominal 12 percent mixture. TABLE X CO'1MPOSITION OF NOMINAL 12 PERCENT MIXTJRE Mole Fraction Methane 0.8812 * Propane 0.117 +.001 Carbon Dioxide 0.0003 Ethane } 0,0013 Nitrogen Oxygen/Argon 0.0001 1, 0000 * by difference The flow meter was recalibrated twice during the course of the experimental work reported here. The recalibrations are in good agreement with the calibration of May 1965 and a cubic equation fits all 34 calibration points with an average deviation of 0.15 percent. The calibration data are given in Table XXXVIII of Appendix B and are plotted in Figure 48. The experimental data for this mixture are presented in Table XLIV of Appendix D. Isobaric heat capacities were derived from the experimental enthalpy data and are presented in Table XI. Again entries in italic type represent interpolated or extrapolated values. Enthalpy data in the two-phase region were interpreted to yield - 45 -

TABLE XI TABULATED VALUES OF ISOBARIC HEAT CAPACITIES FOR THE NIOMINAL 12 PERCENT MIXTURE C (Btu/lb OF) Temperature Pressure psia OF 0 500 1000 1500 2000 -280 0.423 0.677 0.706 -270 0.424 0.686 0.708 -260 o,425 0.697 0.712 0.704 -250 0.,427 0.707 0.716 0.709 -240 0.428 0,718 0,720 0.715 0. 723 -230 0.429 0.728 0,727 0.720 0.726 -220 0.430 0.740 0.732 0,027 0.729 -210 0.431 0.751 0.739 0.730 0.733 -200 0.432 0.762 0.747 0.735 0,.738 -190 0.434 0.774 0,758 0.741 0,742 -180 0.435 0.789 0,771 0.748 0,747 -170 0.436 0.,805 0.788 0.755 0,752 -160 0 437 0.825 0,808 0,765 0.758 -150 0,438 o,850 0,834 0,777 0,764 -14o o.440 0,887 o,865 0.790 0.771 -130 o.441 0,942 0,.903 0,.807 0,780 -120 0.443 1.034 0.91;7 0,827 0,.790 -110 O,444 1.000 0,851 0,806 -100 o,446 1.060 0,880 0.825 - 90 0),l48 1,134 0.916 o,846 - 46 -

TABLE XI - (Cont.) Temperature Pressure psia 0F 0 500 1000 1500 2000 80 0.450 1.237 0.962 0,872 70 0.452 1.500 1,018 o,o900 - 60 0,454 1.083 0.932 - 50 0.456 1.161 0.963 - 40 0.459 1,247 0.993 - 30 0o.461 1.300 1.022 - 24 1.313 - 20 0.464 1.309 1.051 - 10 O,467 1.059 1.493 1,271 1.068 0 o,470 0.890 1.106 1.224 1.075 2 1.076 10 0,73 0,784 0.985 1.167 1,068 20 0.476 0.713 o.896 1.099 1.047 30 o.479 0.662 0,828 1.030 1.022 40 0.483 o,623 0.776 o.965. 994 50 o.486 0.594 0.736 0.910 o,964 60 o,490, 572 0.707 0.863. 934 70 0.494 0,570 0,691 0,824, 90go 80 o.498 0.551 o,679 0.793 0.878 90 0,502 o,546 o.668 0,770 0,.853 100 o.50o6 o,544 0.65.9 0.752 0.828 11O510 O. s548 0. G52 0,736 0,809 - 47 -

TABLE XI - (Cont.) Temperature Pressure psia OF 0 500 1000 1500 2000 120 0.514 0.554 0.646 0.723 0.791 130 0.518 0.560 0.641 0.712 0.775 140 0.523 0.568 0.637 0.705 0.762 150 0.527 0.575 0,634 0.697 0. 750 160 0.532 0.577 0. 632 0. 690 0. 740 170 0.537 0,580 0.630 0.684 0. 731 180 0.541 0.582 0.630 0.680 0.724 190 0.5546 0.585 0.629 0.676 0.718 200 0,551 0, 588 0. 630 0. 673 0. 713 210 0.556 0.591 0.630 0.671 0.708 220 0.561 0.594 0. 631 0.670 0. 705 230 0.565 0.597 0.633 0,669 0.702 240 0.570 0.601 0.634 0.669 0.700 250 0.575 0,605 0.636 0,.669 0.698 260 0.580 0.608 0.639 0. 669 0.697 270 o.586 0,612 0.641 0,670 0.697 280 0.591 0.616 0.643 0.671 0. 697 290 0.596 0.620 0.646 0.673 0.697 300 0.601 0.624 0.649 0,674 0.697 - 48 -

values of the integral isobaric heat of vaporization, The inlet temperature for such traverses was always in' the liquid region. From this base successive additions of electrical energy were made to obtain data in the liquid, two-phase, and vapor regions. A plot of the enthalpy change versus temperature such as Figure 8 was prepared and values of the bubble and dew points as well as the integral isobaric heat of vaporization obtained. The results are presented in Table XII. TABLE XII HEATS OF VAPORIZATION OF NOMINAL 12 PERCENT MIXTURE Pressure Bubble Point Dew Point Aa (psia) (OF) (OF) (Btu/lb) 500 -123.4 3.3 200.3 800 - 89.2 10.0 156.7 1000 - 65.9 10.7 114.5 Nominal 28 Percent Propane in Methane Mixture Isobaric enthalpy determinations on this mixture were made in the single and two-phase regions in the temperature range -240O0F to 1400F at pressures from 250 to 2000 psia. The range of individual runs is indicated by the horizontal lines in Figure 9. The composition of the circulating gas misture was analysed during the course of the experiments with the chromatograph and a record of the analyses is shown in Figure 10. There does not appear to be a significant deviation from the average composition selected for this mixture given in Table XIII.

30 20 - 800 Psia To = -97.6 ~F I I10 Mole Fraction C3 H8=.117 Mole Fraction CH4 =.883 O - o Run 16 * Run 40 -10 - -20 -:D - -30 - 00 -50 I o 0. -70o- '+ b = -V I 0?~~~~~~~~~~~~~~~~~~~~I - -90 -170 120 1300 140 ISO 60 {0 ao 1 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 50 160 170 80 190 W (POWER INPUT, BTU/MIN F FLOW RATE, LB/MIN Figure 8. Enthalpy Traverse of the Two-Phase Region

2,000 1,600 _ U) 1,200 CL 800\ Cn 0L 400 0. -250 -200 -150 -100 -50 0 50 100 150 200 250 TEMPERATURE (OF) Figure 9. Range of Experimental Measurements on the Nominal 28 Percent Mixture

29.0 bJ z Z o o < 0 0 0 0 (Z 0 0 - D 0 o o0 C9I 0 CD 0 0 CD 0 0 00 Z 28.0 00L)00 00000 C~00 ~ o o ~oaY 00~D% 0 ~ ~0 0 0 W 0 06 280 o 0 0 0800 o O o o o0 xo 0 0 O 0 w 0 27.0 May I June I July 1 1966 1600 1700 1800 1900 2000 COMPRESSOR HOURS Figure 10. Composition of the Nominal 28 Percent Mixture as a Function of Time

TABLE XIII OIMPOSITION OF NOMINAL 28 PERCENT MIXTURE Mole Fraction Methane 0.7181 * Propane 0.280 +. 001 Carbon Dioxide 0.0003 Ethane 0.0005 Nitrogen 0.0010 Oxygen/Argon 0.0001 1.0000 * by difference In order to ensure the accuracy of the results, it is standard practice to calibrate the flowmeter with the mixture under study before any runs are made and after every 10 runs are complete. Unfortunately the remarkable success in calibration experienced with all the other mixtures was not achieved when working with the mixture of 28 mole percent propane in methane. Ten complete sets of calibration runs were made. The results of the calibration runs are summarized in Figure 11. Calibration Sets 10 and 80 are believed to be in error as the result of oil in the flowmeter and/or water in the manometer leads. Ignoring these results but taking all other sets into account yields a calibration curve which fits all calibration points with an average deviation of one percent. Individual sets are fit with the straight lines on Figure 11 with average deviations not exceeding 0,25 percent. Therefore an attempt was made to match individual calibrations with experimental runs on a chronological basis. No reliable calibration is available for interpretation of Runs 1 - 53 -

0.14 60 70 20 0..2 0.13 CZ 0 o j E 80 I a_~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~a U-~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~z CLL 0.12 40 / 90 100 0 6 8 10 12 14 16 18 20 22 24 26 F 104(lb/min. /~ ~~) /J \micropoise Figure 11. Flow Meter Calibrations with Nominal 28 Percent Mixture

through 19. Flow rates for Runs 20 and 21 were calculated from Calibration Set 40, and for Runs 23 and 24, Calibration Set 50 was employed. Runs 25 through 28 used Calibration Set 60 while the remaining Runs 30 through 48 used combined Sets 60 and 70. The last three runs, 49-51, used combined Sets 90 and 100. The error introduced by this procedure is believed to be considerally less than one percent in the point value of heat capacity, Cp, obtained from these data. The experimental data for this mixture are presented in Table XLV of Appendix D. Values of heat capacity derived from the experimental enthalpy data are given in Table XIV. The enthalpy traverses across the twophase region were used to obtain values of the bubble and dew points and the isobaric heat of vaporization. These results are presented in Table XV. The values of the dew points at 500 and 700 psia may be in error because few data points were obtained in the region of the saturated vapor envelope. TABLE XV HEATS OF VAPORIZATION OF NOMINAL 28 PERCENT MIXTURE Pressure Bubble Point Dew Point AH (psia) (~F) (~F) (Btu/lb) 500 -110,5 59 226.5 700 - 82,3 "72 202.5 1000 - 46.o 79.3 155.3 - 55 -

TABLE XIV TABULATED VALUES OF ISOBARIC HEAT CAPACITIES FOR THE NOMINAL 28 PERCENT MIXTURE C (Btu/lb - ~F) Temperature Pressure, psia 0F 0 500 1000 1500 2000 -280 0.355 0.625 0.621 0. 623 -270 0.357 0.627 0.623 0.624 -260 0.359 0,629 0,625 0,625 -250 0.362 0.631 0.628 0.626 -240 0.364 0,633 0,630 0.628 -230 0.366 0.636 0.633 0.630 -220 0,369 o.64o 0.636 0.633 0.630 -210 0,371 0,644 0.639 0.635 0.632 -200 0.373 0.648 0.643 o.637 0.634 -190 0,375 0,654 o.648 0.641 0.637 -18o 0,378 o.660 0.653 o.,646 0.641 -170 0.380 0,667 0.659 0,650 0.644 -160 0.382 0,675 o.666 0,656 0.,649 -150 0,384 o.684 0,.673 0,662 0.654 -140 0.386 0.695 0,681 o.669 o.660 -130 0.389 0.709 0.691 o.678 o.666 -120 0,391 0,725 0,702 0.688 0.673 -110 0.394 0.747 0,.715 o,698 0,680 -100 0.396 0,730 0.708 o.688 - 90 0.399 0,748 0.718 o0.697 - 56 -

TABLE XIV - (Cont.) Temperature Pressure, psia ~F 0 500 1000 1500 2000 - 80 0,402 0,770 0.732 0,708 - 70 0.405 0o.798 0,749 0,.720 - 60 o.409 0,834 0.770 0,733 - 50 0,412 o.88o 0.794 0.748 - 40 0.415 0.823 0.764 - 30 0.419 0.854 0.783 - 20 0.423 O,893 0.803 10 0,427 0.938 0,824 0 0.430 0.,986 o.846 10 0.434 10 40 o 0,868 20 0,438 1,093 o,890 30 0.443 1.126 0.913 40 0.447 1.135 0.935 50 0,451 0,637 1.128 0.952 60 0.455 0,616 1.110 0.961 65 0.961 70 0, 460 o.600 1,082 O,960 80 o0,464 0.588 1.034 0.955 90 o,469 0.579 0.795 0.984 0,.944 100 0.474 0.572 0.754 0.934 0.924 110 0. 1,479 0,569 0,726 0,889 0,904 120.0,484 0,567 0,706 0,854 0,885 - 57 -

TABLE XIV - (Cont.) Temperature Pressure, psia OF 0 500 1000 1500 2000 130 o0.489 0.566 0.689 0.823 o. 867 14o 0.494 0,566 0.677 0.797 0o 849 150 0.499 0.566 0.668 0.776 0.833 16o 0.504 0.567 0.660 0.759 0.817 170 0.509 0.569 0.654 0O744 0,803 180 0.514 0. 571 0.649 0,732 0.789 190 0,519 0.573 0.646 0,721 0.777 200 0.525 0,576 0.643 0. 713 0.766 210 0.530 0. 578 0.641 0.705 0.756 220 0.535 0,581 0.639 0,700 0. 747 230 0.541 0.585 0,638 0,.695 0.740 240 0.546 0.588 0.638 0.691 0.734 250 0.551 0.591 0.638 0,687 0. 729 260 0.557 0 594 0.639 0.684 0,724 270 0.562 0,597 0.639 0.683 0.720 280 0. 567 0. 601 0.640 0. 682 0. 717 290 0.573 0.604 0. 642 0. 682 0.715 300 0.578 0.609 0,644 0,.681 0.713 - 58 -

Experimental Data on Nominal 243 Percent Nitrogen in Methane Mixture Isobaric enthalpy determinations of this mixture were obtained in the liquid, two-phase, and gaseous regions at temperatures from -2400F. to 1400F. at pressures from 250 to 2000 psia. The locations of the experimental determinations are shown in Figure 12. Accurate determination of the composition of this mixture proved to be a problem. Initial analyses made with the chromatograph and the mass spectrometer at The 'Tniversity of Michigan are compared in Table XVI with independent analyses of the same sample (chromatograph standard) by the Continental Oil Company and the Phillips Petroleum Company in 1965. TABLE XVI COMPARISON OF ANALYSES OF THE METHANE-NITROGEN MIXTURE (1965_) Chromatograph Mass Spectrometer Ph/illips, Conoco ' U of M.U of M 02/Ar 0.02 44,.32 44.31 43.10 43-.40 2 C2H6 0,05 0.04 0.05 CO2 003 - - ~C;4 55.60 55.65 56,83 56.60 C3H8 0.0 0.0 1 Gas Processing Group The agreement was less than desired and a chromatographic analysis based on comparison with four mixtures prepared by weight in - 59 -

2000 1600 1200 C{D Temperature (F,-, 800 400 C - o'/ -250 -200 -150 -100 -50 0 50 100 150 200 Temperature ( F ) Figure 12. Range of Experimental Measurements on the Nominal 43 Percent Mixture

small sample bombs gave 43.3 mole percent nitrogen in the mixture. To resolve this discrepancy, another three mixtures were prepared by weight using ultra-high purity methane and analyzed along with the mixture on another molecular sieve column. The result was 43.4 mole percent nitrogen. Another reanalysis of the sample by mass spectrometer at this time gave 43.2 mole percent nitrogen, so Continental Oil Company was requested to reanalyze this sample. The results of analyses obtained in 1967 are shown in Table XVII. TABLE XVII COMPARISON OF ANALYSES OF THE METHANE-NITROGEN MIXTURE_ (1967) Chromatoegraph M..ass Spectrometer Conoco; ConocoL U of M U of M 02/Ar ----. — 0.01 - N2 44.31 42.69 43.42 43.20 C2H6 0.05 0.05 0.05 CO2 0.02 0.03 CH4 55.61 57.23 56.52 556.80 C3H8 0.01.... 1 Gas Processing Group. 2 Analytical Group. It appears that the discrepancy between the independent analyses and the analyses of this mixture at the University of Michigan has still not been resolved. A record of the composition during the experimental measurements (obtained by comparison with the chromatograph standard taken as 43,3 mole percent nitrogen) is shown in Figure 13. From a consideration of the numerous analyses and checks, the composition of - 61 -

44.0 0 cu 0. 0 L 0 z 4- 0 () 43.5 o o0 o 00 0 a _ o o0 oo octo 0 ' 0 00 0 coO0 000 00 000 0 0 0 00 0 0000Q 00 August 1 September 1 October 1 1965 0 August 1 September 1 October 1 1965 43.0 800 900 1000 1100 1200 Compressor Hours Figure 13. Composition of the Nominal 43 Percent Mixture as a Function of Time

the methane-nitrogen mixture was taken to be that given in Table XVIII. TABLE XVIII COMPOSITION OF NOMINAL 43 PERCENT MIXTURE Mole Fraction Methane.5652 * Propane Carbon Dioxide.0002 Ethane.0005 Nitrogen.434 Oxygen/Argon.0001 1.0000 * by difference Three sets of calibration runs were obtained on the flow meter during the course of the experiments on this mixture. The average deviation of the 30 calibration points from the cubic equation fit to them was 0.13 percent. The calibration data are given in Table XXXIX of Appendix B and are plotted in Figure 49, The experimental data for this mixture are presented in Table XLVI of Appendix D. Isobaric heat capacities derived from the experimental data are tabulated in Table XIX. As with the other mixtures the experimental data were extrapolated from the lowest experimental temperature down to -280 F. The heat capacities at highest experimental temperatures were blended into calculations of Cp made with the B-W-R equation of state up to 3000F. A plot of the heat capacity at 1500 psia as a function of temperature is shown in Figure 14. The data are presented as solid bars and the enthalpy differences obtained from the basic data having - 63 -

TABLE XIX TABULATED VALUES OF ISOBARIC HFEAT CAPACITIES FOR THE NOMINAL 43 PERCENT MIXTURE Cp (Btu/lb - OF) Temperature Pressure, psia OF 0 250 500 1000 1500 2000 -280 0.354 0.550 0.597 0.588 -270 0.354 0.573 0.606 0.596 -260 0.354 0,597 0. 615 0. 604 -250 0.354 0,621 0,624 0.612 -240 0.354 0,647 0.636 0.621 -230 0.354 0.673 0.,647 0.630 -220 0 354 0.700 0.661 0, 640 -210 0,354 0.728 0.676. 650 -200 0,354 0,761 0.693 0.661 -190 0.354 o.0806 0,715 0.673 -180 0.354 0,872 0,746 o.687 -170 0,354 0.992 0.784 0.705 -160 0.355 0o450 1,274 0.836 0.731 -150 0.355 0.435 1.406 0,900 0.756 -143 1,413 -140 O.355 o,424 1.411 0.953 0,.779 -130 0.355 0,416 1,370 0.985 0.800 -128 0.986 -120 0,355 0.410 1,080 0,973 0.813

TABLE XIX - (Cont.) Temperature Pressure, psia ~F 0 250 500 1000 1500 2000 -110 0.355 o.406 0.870 0.954 o.818 -100 0,356 0,403 o,.472 0,733 o, 901 0,813 - 90 0.356 o,400 o.461 0.657 0.833 0.792 - 80 0.356 0.397 o.450 o.607 0,.765 0.766 - 70 0.357 0.395 0.437 0.572 0.706 0.739 - 60 0.357 0.393 0.431 0.544 0.663 0.712 -50 0.358 0.391 0,.423 0,524 0.627 0.683 40 0,358 0*389 0,418 0.508 0,594 o.6654 - 30 0,359 0.387 0,415 0,495 0,569 0.627 - 20 0,359 0,386 0.412 o.484.s550 o.,602 10 0.360 0,384 o,410o o,474 0,538 0,581 0 0,361 0.383 o.1408 o,1466 0.527 0.562 10 0.362 0.382 o,406.459 0. 517 0.547 20 0.363 0.383 o,405 0o,453 0,50o6 0,534 30 0.364 0,383 o.o404 o,448 o.1496 0.523 40 0.365 0,.384 o 0402 o.,443 o,487 0, 514 50 0.366 0,384 0. 401 o,439 o.477 0.505 60 0.367 0.385 o.400 0,435 o,469 o.g498 70 0,369 0,385 o.400 0,431 o,463 o.491 80 0,370 0 386 0,399 0. 428 o. 458 o. 484 90 0.371 0.386 o.o400 0.426 o.1454 0.478 100 0.373 0,387 o,.400 0.424 0.451 0.473 - 65 -

TABLE XIX - (Cont.) Temperature Pressure, psia OF 0 250 500 1000 1500 2000 110 0.374 0.387 o.400 0.423 o.449 0.470 120 0.376 0, 388 0.400o 0.422 0.446 0. 467 130 0.378 0.389 0. 400 0, 422 0.444 0,464 140 0.379 0.389 0. 400 0.421 0.442 0.461 150 0.381 0.391 0. 400 0.421 0.440 0. 458 160 0.383 0.392 0. 401 0.421 0. 439 0.456 170 0.384 0.393 0.402 0.421 0.438 0.455 180 0.386 0.395 0,403 0.421 0.438 0.453 190 0,388 0.396 0.404 0,421 0.437 0.452 200 0.390 0.398 0.406 0.421 0.437 0.451 210 0.392 0.399 0.407 0.422 0, 437 0. 450 220 0.394 0. 401 0,408 0.423 0.437 0.450 230 0.396 0.403 0,410 0*423 0.437 0.449 240 0.398 0.404 0.411 0.424 0.437 0, 449 250 0.400 0.406 0.413 0,425 0,.438 0.449 260 0.402 0.408 0.414 0.427 0,438 0.449 270 0.1404 0.410 0.416 0.428 0.439 0.450 280. 406 0. 412 0.417 0,.429 - 0440 0.450 290 0.408 0.414 0.419 0.430 0.441 0.450 300 0.410 0.416 0.421 0,432 0,.442 0.451 - 66 -

1.0 - Pressure 1500 PSIA.9- Mole Fraction Nitrogen 0.434 Mole Fraction Methane 0.566.8.6 -.4 Data Points Q. Difference Points O.3.2 - 0 I I I I I I I I I I I -280-260 -240 -220 -200 -180 -160 -140 -120 -100 -80 -60 -40 -20 0 20 40 60 80 100 120 140 TEMPERATURE (OF) Figure 14. Heat Capacity of the Nominal 43 Percent Mixture at 1500 psia

the same initial temperature are shown as broken lines. The use of difference points facilitates the drawing of the equal-area curve to obtain point values of heat capacity. In this example the location of the maximum in heat capacity is determined using the differenced data. This maximum in heat capacity is characteristic of data obtained at pressures 123 above the critical pressure and Manker used the locus of these maxima to estimate the critical point of a mixture. The three enthalpy traverses across the two-phase region yielded the values of the bubble points, dew points, and latent heats of vaporization at constant pressure given in Table XX. TABLE XX HEATS OF VAPORIZATION OF NOMINAL 43 PERCEIJT MIXTURE Pressure Bubble Point Dew Point AH (psia) (~F) (~F) (Btu/lb) 250 -231.0 ~-190.7 120.2 400 -208.0 -176.1 98' 9 600 -183.1 -157.3 71*3 Experimental_ Data on Nitroen to Evaluate Heat Leak In the reduction of all the isobaric data using Equation (2) the assumption is made that the calorimeter is adiabatic, that is, the heat leak Q is assumed to be negligible. This assumption is based on the results of extensive tests of vacuum level,guard heater mismatch and rate of conduction in the calorimeter conducted by Manker 12 He concluded that the heat leak error wras under 0,02 percent, much smaller than the estimated accuracy of the enthalpy measurements. - 68 -

Montgomery and DeVries135 have established that the heat leak is zero if the heat capacity determined by the calorimeter is independent of the flow rate. With each of the mixtures studied with the isobaric calorimeter, one run was made to test this assumption, The plots of heat capacity versus 1/F are shown in Figures 15 and 16 for the mixtures. While the heat capacity appears to be independent of the flow rate within the precision of the measurements (+ 0.2 percent), lines indicating heat leak can easily be drawn through the data. A disturbing feature is the fact that the sign of the heat leak (slope of the line) appears to vary from one run to another. The latent heat of vaporization data obtained on the nominal 28 percent mixture raised doubts that the heat leak could be neglected, In the construction of a preliminary enthalpy diagram for this mixture131 the latent heats at 500 and 700 psia appeared to be high by 5 to 6 percent. These enthalpy traverses across the two-phase region involved temperature rises of up to 170~F and the assumption of adiabatic conditions with very large temperature differences had not been checked. Nitrogen was selected as the test gas because large temperature rises could be obtained without overloading the DC power supply. Isobaric enthalpy data were obtained from the inlet conditions of -1960F at 1000 psia with temperature rises of 24, 45, 85, 158, and 229~F at various flow rates, The experimental data are presented in Table XLVII of Appendix D. Plots made of the mean heat capacity as a function of reciprocal flow rate to establish the magnitude of the heat leak are shown in Figure 17. The precision of these data is poorer than normal and the range of flow rates is smaller than desirable. However, estimates of the heat leak were made using the equation:

- 70 -LL 01 - r QD 0.695 0 2 4 6 8 10 12 14 16 18 20 22 <0 S \ \ ~~~~Run 22 Pressure 2 000 PsiA o 0.71500 _ Inlet Temperature 20051F - -0.2 Outlet Temperature 257~ F uJ n\ 0.69 2 - 0 2 4 6 8 10 12 14 16 18 20 22 RECIPROCAL MASS FLOW RATE (MIN/LB) Run 22 Pressure 1000PSIA 0.715 N Inlet Temperature 51~F "~t~ I Outlet Temperature 63.50F I \ - 0.2% * * Average 0.7108 0.710 -0.2%,2 Nominal 12 % Propane ~~~~~~~~~~~~~~~0.705 in Methane Mixture 0.705 0 2 4 6 8 10 12 14 16 18 20 Reciprocal Mass Flow Rate min I lb Figure 15. Heat Capacity as a Function of Reciprocal Flow Rate for Nominal 5 and 12 Percent Mixtures

- 71 - Nominal 28 % Propane in Methone Mixture LL 0.715 m +0.2% __ _-_ _ -—,, ~ Average.7112.710 - -0.2% M.705...440 - <0 C: RPressure 1000 PSIA Inlet temperature-124 ~F.0 Outlet temperature -69 ~F,, I, I I I 0 2 4 6 8 10 12 14 16 18 20 22 RECIPROCAL MASS FLOW RATE (min /Ib).440Nominal 28 and 43 Percent Mixtures a Nominal 43 % Nitrogen in Methane Mixture 4 -- C — -— 0. - _ - I - Pressure 1000 PSIA Inlet Temperature 51~F.430 _ Outlet Temperature 74~F 0 2 4 6 8 10 12 14 16 18 20 22 Reciprocal Mass Flow Rate (min/l Ib} Figure 16. Heat Capacity as a Function of Reciprocal Flow Rate for Nominal 28 and 43 Percent Mixtures

- 72 -.726 432 - T LL IO/1 L.722 ~.428.7186 0 10 20 30 0 5 10 15 71/ '. 424-..714 T:f20 - ATx 18~F I i 0 0 20 3015 0 5 10 15 I/F (MIN/LB) I/F (MIN/LB).516 - \" T 1% NITROGEN _.512 i \ \ 1 Inlet Temperoture:-1960F _ = \-^\~\~ ~- All Bands + 0.3% =.508 / 382.504. I I I I 0 5 10 15 I/F (MIN/LB) I/F (MIN/LB).5igure 17. Heat Capacity as a Function of Reciprocal Flow Rate for Nitrogen

p Cp FAT (22) where C is the mean heat capacity calculated from Equation (2) and C X is the intercept on the ordinate at infinite flow rate. The estimates are plotted in Figure 18 as a function of the temperature rvise across the calorimeter. Also included on this plot are values taken from Figures 15 and i6 for the mixtures. There appears to be no direct correlation and it is concluded that heat leak effects are less than one percent even with temperature rises of 200~F. - 73 -

0.08 C x x Nitrogen.~0 o 5% Propane in Methane ~ 12% Propane in Methane " 28% Propane in Methane 0.04 U N 43% Nitrogen in Methane Btu 0T~F min |100 200 300 o x -0.04 x -0o08 Figure 18. Apparent Heat Leak as a Function of Temperature Rise Across the Calorimeter

SECTION III-THE ISOTHERMAL EFFECT OF PRESSURE ON ENTHALPY Previous work employing isothermal throttling calorimeters is reviewed and the design of a new throttling calorimeter is discussed here. The new calorimeter was used to obtain data on nitrogen and a nominal 5 percent propane in methane mixture. These data are compared with other direct measurements, Joule-Thomson data, and calculated values from correlations and compressibility data. Background in Isothermal Throttling Calorimetry All methods for measuring the isothermal effect of pressure on enthalpy involve some means for the production of a pressure drop and a source of energy to compensate for the cooling effect resulting from the pressure drop. Hence, the methods are suitable only where 4 is negative and no isothermal calorimeters have been designed to abstract energy if the fluid warms on expansion. The porous plug method of Joule-Thomson measurements is well-known, and Buckingham2 first proposed the measurement of the isothermal throttling coefficient by embedding a heating coil in the plug of an ordinary Joule-Thomson experiment. However, no devices utilizing this method have been used for isothermal throttling measurements. The throttling devices which have been used are the capillary, the valve throttle and the orifice. 100 Keyes and Collins described an apparatus consisting of a platinum capillary which caused the pressure drop and also served as the resistance heater. Some data on carbon dioxide and ammonia were obtained at low 30931 pressures and room temperature. In later models, [Collins and Keyes ], a heating element consisting of resistance wire supported upon pyrex tubes was inserted into a short length of tubing. Substantially all the flow resistance of the calorimeter was caused by the heater. Measurements were made on steam and on nitrogen at low pressures (inlet pressure less than - 75 -

3 atm.) and both p and 4 were determined. Independently, in Germany, Eucken, Clusius, and Berger reported a different apparatus for determining 4. A throttle valve was used to cause the pressure drop and the gas, after expansion, was passed over heating wires to bring the outlet temperature back to that of the inlet. The first measurements were made with air as the test gas. A second throttle valve, which unlike the first could be adjusted 56 without dismantling, was used by Eucken and Berger for measurements on methane at temperatures from 1650 to 293 K at pressures up to 100 atm. Measurements of the latent heat of vaporization were attempted but twophase flow through the valve resulted in instability and no results could be obtained. Three measurements of the integral isothermal throttle effect of methane (Ap%30 - 50 atm) above the critical were made to aid in 57. the preparation of the enthalpy-pressure-temperature diagram Another 100 throttle, similar to that of Keyes and Collins, consisting of a nickelsilver capillary was used to obtain data for carbon dioxide at 0 C. For unspecified reasons, no measurements with this capillary coil were made on methane. Gusak employing a copy of the Eucken device obtained data for nitrogen between 1150 and 2920 K at pressures from 60 to 200 atm. 89 The Russian workers, Ishkin and Kaganer employing essentially the same apparatus as Gusak obtained data on air and nitrogen at pressures up to 50 atm. at temperatures from -183~ to +30 C. Data were obtained at closely spaced intervals in the critical region. The results were used to prepare enthalpy diagrams for air and for nitrogen. Later experiments were made on argon and mixtures of argon and nitrogen by Ishkin and 90 Rogovaya. 7 t

Recently other Russian workers, using an improved throttle valve, have published results on mixtures of nitrogen and hydrogen (Bolshakov et al. ), methane and hydrogen (Gelperin et al.6), and methane with nitrogen 26 A throttling valve was used by Charnley, Isles, and Townley for measurements on nitrogen, ethylene, carbon dioxide, and nitrous oxide. The pressure drop was a few atmospheres and absolute pressures up to 50 atm. at temperatures between 00 and 45 C were used. The range was restricted by the use of plastic materials of construction. Using this apparatus, Charnley, Rowlinson, Sutton and Townley27 made measurements bn the binary mixtures carbon dioxide + nitrous oxide, carbon dioxide + ethylene, nitrous oxide + ethylene, and nitrous oxide + nitrogen. Interaction virial coefficients were derived from the zero-pressure data for the mixtures, Francis, McGlashan, and Wormald63 describe an apparatus operating below atmospheric pressure designed to obtain all three of the partial derivatives in Equation (8), but results were presented only for O of benzene from 600 to 1300C. Andersen3 used an orifice to cause the pressure drop, followed by a heater to bring the gas back to the inlet temperature. The apparatus was designed to operate up to 4 atm. at temperatures between 00 and 300C and values were obtained for air in this region. Stribolt and Lydersen made measurements on steam using a removable orifice to cause the pressure drop and the gas was passed over a heater to bring the outlet temperature back to that of the inlet. Except for the three measurements of Eucken and Berger57 all the data described above can be called differential values of ~, since the pressure drop was only a few atmospheres and the values of f were easily obtained from the values of (AH/AP)T. Gilliland and Lukes constructed a device for the measurement of the integral isothermal throttling effect, the enthalpy departure from the ideal gas state. - 77 -

The throttle was a stainless steel capillary which also served as the 100 resistance element, as in the Keyes and Collins design. Capillaries of different lengths were used to obtain different pressure drops. Inlet pressures ranged up to 2800 psia while the outlet pressure was always near atmospheric. The equipment was later used to study n-pentane, n-heptane, 142 and isooctane as well as mixtures of benzene and n-heptane by Parekh Only the pure component results were published by Gilliland and Parekh70 Yarborough198 constructed a calorimeter similar to that used by Gilli69 land and Lukes. Data were obtained on propane, benzene, and three mixtures of propane and benzene with inlet pressures up to 1000 psia in the temperature range 200 to 400 0F. The results are reported in a paper by Yarborough and Edmister 9. This calorimeter was used by Dillard to study methane and a mixture of methane in propane at inlet pressures up to 2000 psia at temperatures of 90, 150 and 200 F. The calorimeter designed by Dolan44 consists of a capillary coil to cause the pressure drop and the heat required is determined from the difference in the amount of energy expended in heating the bath of boiling Freon surrounding the coil and the amount of energy abstracted in the Freon evaporated. Data were obtained with nitrogen at 74.5 F at inlet pressures up to 1500 psia. Design of Isothermal Throttling Calorimeter The first requirement in the design of the present calorimeter was that it operate over a wide range of temperatures, from -250o F. to 3000 F. and at any pressure in this temperature range from 100 to 2000 psia. Type 304 stainless steel was selected as the material of construction because of its strength at low temperatures and the possibility of experimental work with corrosive fluids. - 78 -

The instability of two-phase flow through a valve caused by alternate slugs of liquid and vapor prevents accurate thermodynamic measurements so the use of a throttling valve was abandoned since the design was to allow for the possibility of measuring isothermal enthalpy changes across the twophase region. An orifice also tends to be unstable in two-phase flow and the high velocity at the throat must be dissipated before accurate temperature measurements can be made. Heat leakage resulting from the difference in temperature between the walls and the jet may be significant unless elaborate precautions are taken to isolate the throttle from the surroundings. A capillary was considered to be the best configuration for the throttle because the expansion is smooth and if energy is added to the fluid during expansion, the process will be almost isothermal. It should be noted that it is not necessary for the expansion to be isothermal; since enthalpy is a point function, the change in enthalpy between the inlet and outlet is determined only by the conditions at these points and does not depend upon the path of the fluid. However, by making the path as nearly isothermal as possible, heat leakage from the surroundings to the system is minimized. The disadvantage of a capillary throttle is that it is not possible to vary flow rate and pressure drop independently. In this present design this is offset somewhat by making the capillary removable so various combinations of pressure drop and flow rate may be obtained. Some earlier designs using a capillary as a throttle also used the capillary itself as a resistance heater. The relatively large flow rates in the recycle system into which the isothermal calorimeter was to be installed required the use of reasonably large diameter capillaries. - 79 -

These capillaries have a low electrical resistance and require large currents to dissipate the energy input. In low temperature calorimetry, it is desirable to make power input leads as small as possible to minimize conduction from the surroundings, but with currents of the order of 10 amperes, large leads must be used to minimize lead losses. The heater of the present calorimeter is an insulated Nichrome wire which passes inside the capillary for its entire length. The Nichrome wire is grounded at the outlet of the capillary and a copper power lead is connected to the heater wire at the inlet to the capillary. The combination of heater wire size and capillary size allows different pressure drop-power input relations. With this arrangement, currents were kept below one ampere. The calorimeter developed here is designed for operation over a wide range of conditions and can be used in the liquid, two-phase, or gaseous regions. It can be used with relatively small pressure drops to measure ~ or with large pressure drops to obtain integral values of the enthalpy change with pressure. The incorporation of the heater inside the flow resistance minimizes the temperature gradients in the system thus reducing the possibility of heat leaks. Description of Calorimeter The isothermal throttling calorimeter is part of the recycle system described earlier under isobaric measurements. Both isothermal and isobaric calorimeters are located in a constant temperature bath controlled to about 0.10 F. Four packless valves with stainless steel bellows located within the bath make it possible to operate either calorimeter with only minor adjustments. The isothermal throttling calorimeter is shown in Figure 19. The fluid enters the upper portion of the calorimeter vacuum jacket from the constant temperature bath. Here the pressure tap (9) and thermowell (1) - 80 -

/9 7 ' I. Entrance Thermocouple Well, 2. Mechanical Partition 3. Calorimeter Heater Capsule 4. Calorimeter Baffles 5. Exit Thermocouple Well 6. Radiation Shield 7. Conax Heater Lead Gland 8. Capillary 9. Entrance Pressure Tap 10. Exit Pressure Tap 12 II. Vacuum Line 12. Temperature Compensated Coupling A-H Difference Thermocouple Locations G ('P ~ ~~~~~~~H 1 0 I Inch E 6 3 Figure 19. Isothermal Throttling Calorimeter

serve to measure the inlet conditions of the fluid before it passes to the throttle chamber (3). Inside the chamber is a removable capillary coil (8) which causes the pressure drop in the fluid. In this work, three different capillary sizes were employed of 16 BWG, 17 BWG, and 19 BWG hypodermic tubing, all about 10 feet in length. The nominal ID of these capillaries is.047,.042, and.027 inches respectively. The chamber closure is a temperature compensated coupling (12) using a stainless steel O-ring. Although this closure was initially successful, the seal was found to leak after it had been opened and closed a number of times. It was necessary to use 1 mil Mylar gaskets on both sides of the O-ring for subsequent experiments to obtain a seal. To offset the cooling effect as the pressure drops, electrical energy is added to the flowing fluid by the insulated Nichrome resistance wire (36 B&S, nominal.005'"0.D,)inside the capillary. The lead wire for this heater is brought from the vacuum jacket into the pressure capsule through a Conax gland (7), which uses a Teflon sealant. The other end of the heater wire is soldered to the low pressure end of the capillary to ground it electrically. The fluid jetting from the capillary is passed back and forth through three copper baffles (4) to reduce kinetic energy effects and smooth out temperature fluctuations before passing to the exit thermowell (5) and the exit pressure tap (10). The line in which the fluid leaves the calorimeter is enclosed by a vacuum tube for a distance of three feet after leaving the calorimeter to minimize heat conduction back from the surroundings. Other efforts were made to reduce heat transfer to the surroundings. A radiation shield (6) completely encloses the calorimeter capsule. The lead wires to the heater are brought into contact with the vacuum jacket to elimi

nate heat transfer in the leads. The thermocouple lead wires are wrapped around a massive copper thermal equalization block before passing to the thermowells and the outlet thermopile leads are bonded to the outlet line with Apiezon grease. The entire jacket is evacuated to 1 to 5 microns through the vacuum line (11), which is bent under the surface of the bath fluid so that the contents of the upper portion of the calorimeter do not see a surface at temperature different from that of the bath. Singlejunction copper-Constantan difference. thermocouples are attached to the skin of the calorimeter at various points (A through H in Figure 19) to indicate the temperature profile along the calorimeter. Measuring Instruments 1. The inlet pressure to the calorimeter is measured with the dead weight gauge used for some of the isobaric experiments. 2. The pressure drop across the calorimeter is measured by the differential pressure balance of Roebuck. Leather packings were originally used as the seal on the piston of this instrument. Difficulties in operation led to the replacement of the leather with an O-ring seal using Viton O-rings. The piston in this device was replaced by Manker and the conversion of the mass on the piston to pressure drop in psi was given as 19.998 psi/lb. mass. The pressure is transmitted from the calorimeter fluid to the oil in the pressure measuring system by means of the Ruska differential pressure indicator for the inlet pressure and through a mercury U-leg for the outlet pressure. The level of mercury in the U-leg is sensed by electrical phobes sealed into each leg. Although the Roebuck pressure balance is accurate to about 0.1 to 0.2 percent, the imbalance in the mercury U-leg could be as much as 0.5 inches because of the position of the electrical probes. It was found that the 83 -

sensitivity of the pressure measuring system was about 0.05 lb mass on the pressure balance or about 1 psi. This limited the lower pressure drop measurements to an accuracy of about 1 percent. 3. The electrical energy is supplied to the heater by the DC power supply used for isobaric experiments. Essentially the same circuitry (standard resistors, potentiometer) is used to determine the power input to the calorimeter as in the isobaric experiments. 4. The flow rate of fluid is determined by the laminar flow meter as in the isobaric experiments. 5. Any temperature difference between the entrance and exit thermowells is sensed by duplicate six-junction copper-Constantan differential thermopiles using the K-3 potentiometer. The thermopiles were calibrated by the National Bureau of Standards and the results are given in Table XXXIV of Appendix B. Thermopile A was fabricated from 40 AWG copper wire and 36 AWG Constantan wire, while both copper and Constantan wires of thermopile C were 40 AWG. 6. The inlet temperature to the calorimeter is assumed to be the temperature of the calorimeter bath, which is measured by the platinum resistance thermometer as in the isobaric experiments. The basic measurements affecting the accuracy of the isothermal enthalpy data obtained in this work are the power input to the calorimeter, the flow rate of fluid and the pressure drop across the calorimeter. The estimated errors for those measurements and the most probable error of the enthalpy measurements are listed in Table XXI. - 84 -

TABLE XXI ACCURACY OF ISOTHERMAL MEASUREMENTS Low AP High AP Power Input 0.05% 0.05% Pressure Drop Across Calorimeter 1.0 % 0.3 % Flow Rate 0.2 % 0.2 % Z E 7 1.02% 0.37% i i Procedure for Isothermal Measurements Using the recycle system, the fluid is brought to the desired conditions of pressure and temperature at the inlet to the calorimeter. A pressure drop of 100 to 300 psi is obtained by adjustment of the flow rate of fluid through the calorimeter section. The voltage supplied to the calorimeter heater wire is adjusted manually until the temperature difference between the inlet and outlet, sensed by the differential thermopiles is less than 5 microvolts (about 0.050 F). When steady state is reached, as indicated by the constancy of the pressure drop and the temperature difference across the calorimeter, the values of the variables are recorded. The time of approach to steady state is of the order of one hour. Experimental Results with Nitrogen Nitrogen was selected as the test gas because of the large amount of data for this element which are available for comparison. Data in both the isothermal and isenthalpic modes were obtained over about 100 psi pressure drops at three temperature levels, -147.10F, +32.60F, and +201.3F using the 17 BWG capillary coil. The location of the experimental runs is shown 85 -

-147.1 ~F 32.6 F 201.30F 2000 1500 o) w 1000 500 ENTHALPY (Btu /Ibm) Figure 20. Range of Experimental Measurements on Nitrogen

in Figure 20 and extend from 100 to.2000 psia. The data are given in Tables XLVIII and XLIX of Appendix D. Three sets of calibration runs on the flow meter were made in the course of the experiments on nitrogen. The cubic equation fits all 26 calibration points with an average deviation of 0.22 percent. The calibration data are given in Table XL of Appendix B and are plotted as Figure 50. Analysis of Results with Nitrogen The isenthalpic (Joule-Thomson) data obtained on nitrogen are plotted in Figure 21 for the three initial temperatures. Note that the horizontal bars representing the experimental data appear in pairs because the two six-junction thermopiles indicated significantly different values of the temperature drop across the calorimeter. This was not the case during isothermal operation nor has it been the case in experiments with the isobaric calorimeter. The difference in thermopile readings was interpreted to be the result of heat transfer (combined radiation and conduction) from the calorimeter bath to the pressure capsule. Heat transfer occurs because the pressure capsule attains the temperature of the outlet fluid which is lower than that of the bath. This is shown by the temperature change recorded during an isenthalpic run by the difference thermocouples attached to the skin of the calorimeter which are given in Table XXII. The radiation shield is seen to attain a temperature between that of the bath and that of the calorimeter pressure capsule. More radiation shields would reduce heat transfer but an analysis of heat transfer with increasing number of shields shows that the incremental reduction in heat transfer of shields after the first few is slight. 87 -

- 88 -.08 NITROGEN.07- = <, INITIAL TEMPERATURE - 147. 1 IOF.06 -.05 -.045.03 - * ROEBUCK 8 OSTERBERG (1935).02.01 - 0 500 1000 1500 2000 — * ~PRESSURE (PSIA) NITROGEN INITIAL TEMPERATURE = 32.6 F.025 -,.020 *ROEBUCK a OSTERBERG (1935).015 O 500 1000 1500 2000 PRESSURE (PSIA).014 -.013 - \.~- NITROGEN 012 \ INITIAL TEMPERATURE= 201.30F.01 1.010.009 * ROEBUCK a OSTERBERG (1935).008.007 0 500 1000 1500 2000 PRESSURE (PSIAI Figure 21. Isenthalpic (Joule-Thomson) Data on Nitrogen

TABLE XXII COMPARISON OF DIFFERENCE THERMOCOUPLE READINGS Thermocouple Pair Location Thermocouple Output (microvolts) Isenthalpic Run Isothermal Run A-B Inlet Thermowell + 0.5 -0.8 A-C Inlet Tee + 0.7 -0.4 A-D Top of Heater Capsule -175.2 0.0 A-E Middle of Heater Capsule -184.5 -0.1 A-F Bottom of Heater Capsule -195.0 -0.5 A-G Outlet Thermowell -195.3 -0.6 A-H Radiation Shield - 49.6 -1.0 The isenthalpic data are compared with the corrected results of Roebuck 157 & Osterberg in Figure 21. The present results were obtained at constant inlet temperatures as shown in Figure 22 for the measurements at -147.1 F. Hence the smooth curves drawn on Figure 21 trace the locus of points of increasingly lower temperatures at lower pressures. The data are not in good agreement with those of Roebuck and Osterberg except at the lowest temperature where radiation is less significant. From these observations, it was concluded that the isothermal throttling calorimeter is not suitable for isenthalpic determinations unless the fluid warms upon expansion. In this case it would be possible to heat the radiation shield to the temperature of the exit fluid. The isothermal data for nitrogen at the three themperatures are plotted as a function of pressure in Figures 23 through 25. An equal-area curve is passed through the bars to obtain point values of ~. The data bars indicate 89 -

-140 / / / / -140 / LI // // / / _ /, 150 /1 X / // / / Nitrogen,o -160 uJ160 / / / This Work / H f I / / / --- Roebuck 8 Osterberg / / / (1935) / / -170 / / / / 0 500 1000 1500 2000 2500 PRESSURE (PSIA) Figure 22. Comparison of the Types of Joule-Thomson Experiments

NITROGEN TEMPERATURE = -147. 1 F -.020 IaIJ E - 015 % -.010 0 500 1000 1500 2000 PRESSURE (PSIA) Figure 23. Isothermal Data on Nitrogen at -147.1 F

NITROGEN TEMPERATURE 32.6 OF -.007 0.cn 1% 'E PD<~j< -.006 -.005 0 500 1Q00 1500 PRESSURE (PSIA) Figure 24. Isothermal Data on Nitrogen at 32.60 F

NITROGEN TEMPERATURE = 201.3 ~F -.004 QD. E -.003. -.003\ -.002 0 500 1000 1500 2000 PRESSURE (PSIA) Figure 25. Isothermal Data on Nitrogen at 201.30 F

a precision of about + 1/2 percent and a band of this size is drawn on Figure 26 for comparison with other experimental data. The data of Ishkin and Kaganer are believed to be high by as much as 5 percent [see Bolshakov et 17 al. ]. Values of ~ calculated from the Joule-Thomson data of Roebuck & 157 94 Osterberg combined with the heat capacities of Jones at the lower tem118 peratures and those of Mackey & Krase at the highest temperature are also plotted. The present data appear to be somewhat lower than other experimental values. Values of 4 can be calculated from an equation of state using Equation (9). The Benedict-Webb-Rubin equation is frequently used for calculation of thermodynamic properties. For nitrogen, two sets of constants for this equation 179 are available, the earlier set of Stotler & Benedict and the recent values of Crain & Sonntag 36 Bloomer and Rao15 modified the B-W-R equation of state by the addition of two more constants to represent the low temperature volumetric data with greater accuracy. The equations used to calculate thermodynamic properties from these equations of state are presented in Appendix C. The results of equation of state calculations are compared with the experimental band in Figure 27. None of the equations represent the experimental band accurately at all temperatures over the range of pressure. A number of tabulations contain values of enthalpy for nitrogen, which usually have been derived from volumetric data. The tabulated values of enthalpy were differenced to give values of 4 for comparison with the experimental data. - 94 -

-.025 NITROGEN 0 TEMPERATURE = -147.1 ~F mE 1 n -.015 4 "rlr ' THIS WORK 4 O ISHKIN a KAGANER (1956) - LCp- ROEBUCK a OSTERBERG (1935) JONES (1961) -.010 0 500 1000 1500 2000 PRESSURE (PSIA) -.008 - - NITROGEN 0a TEMPERATURE 32.6~F -.007 - E 0 -006 < 00 l i = THIS WORK E ISHKIN 8 KAGANER (1956) O GUSAK (1937) -LCp ROEBUCK a OSTERBERG (1935) JONES (1961) -.005 O 500 1000 1500 2000 PRESSURE (PSIA) -.004 - E6 ~~~~ I NITROGEN TEMPERATURE = 201.3~F -.003 1% H= 0 "I a. -.', - THIS WORK - -Cp ROEBUCK a OSTERBERG (1935) MACKEY a KRASE (1930) -.002 - 0 500 1000 1500 2000 PRESSURE (PSIA) Figure 26. Comparison of Isothermal Data With Other Experimental Data

-.025 - NITROGEN TEMPERATURE =- 147.1 OF r" 0 O -.020 -- E 0 -.015 -..... THIS WORK.a BWR-STOTLER & BENEDICT (1953) 0 BWR-CRAIN & SONNTAG (1967) _ 010 MODIFIED BWR - BLOOMER & RAO (1952) -.01O 0 500 1000 1500 2000 PRESSURE (PSIA) -.008 NITROGEN TEMPERATURE =32.60F -.007- 0 IE I II O 500 1000 1500 2000 2 m -o -.006 2 77777-77 THIS WORK ~... BWR - STOTLER 8 BENEDICT(1953) MODIFIED BWR - BLOOMER 8 RAO (1952) O BWR- CRAIN & SONNTAG (1967) ~ -.005 0 500 1000 1500 2000 PRESSURE (PSIA) -.004 -- '0. V) '~~I NITROGEN TEMPERATURE= 201,3 ~f " 0'. 1% o 0o 7? 77= THIS WORK I

in43 113 Enthalpies were obtained from Din, Lunbeck, Michels, & Wolkers 79 182 146 Hilsenrath et al, Strobridge and Pfenning, Canfield, & Kobayashi. The values of 4 derived from these compilations are compared with the experimental data in Figures 28 through 30 and are seen to be in agreement within about 4 percent. It is apparent that the tests made with nitrogen to establish the accuracy of the calorimeter are inconclusive since the published data are not in agreement among themselves within the precision of the present experiments. Enthalpy departures were calculated from the experimental data by integration with respect to pressure. The results for the three isotherms of this work are compared with other compilations in Table XXIII. The present data are at least as accurate as the most recent values in the literature. The zero-pressure values of 4 are directly related to the coefficients of the virial equation of state by Equation (15). The experimental values of 4 were extrapolated to zero pressure for comparison with values of 4o from the literature. The results are shown in Figure 31 where the present data are in good agreement with values calculated from zero pressure Joule-Thomson data together with values of the ideal gas heat capacity, Cp, other isothermal throttling data, and the virial equation of state. The consistency of the low temperature nitrogen data was tested by 94 loop checks with the isobaric data of Jones. Deviations were less than one percent and the results are given in Appendix C. - 97 -

-.025 +'+' d- i+'+. + \ NITROGEN -I-;'~ XTEMPERATURE =-147.1 F ~~E~~~~~~\. -.020 - o+ -t I I —' /11tIEEILEE THIS WORK.... DIN (1961) \ -.015...STROBRIDGE (1962) + -4-+++ PFENNING, CANFIELD 8aKOBAYASHI (1965).... - LUNBECK, MICHELS & WOLKERS (1952) -.010 0 500 1000 1500 2000 PRESSURE (PSiA) Figure 28. Comparison of Isothermal Data at -147.1 F with Values from Compilations

-.008 NITROGEN TEMPERATURE: 32.6~F +- + 'E. STROBRIDGE (1962) +' | HL'SENRATH et al. (1955).. 1% -.006 - ' -iiI THIS WORK DIN (1961) 0 500 1000 1500 2000 PRESSURE (PSIA) Figure 29. Comparison of Isothermal Data at 32.60 F with Values from Compilations

N ITROGEN TEMPERATURE = 201.3 OF -004 0. E.0 -.003 % 1 I I THIS WORK o HILSENRATH et al. (1955). - - DIN (1961) - -` —' — LUNBECK, MICHELS, a WOLKERS (1952) -.002 0 500 1000 1500 2000 PRESSURE (PSIA) Figure 30. Comparison of Isothermal Data at 201.3 F with Values from Compilations

TABLE XXI II COMPARISON OF EXPERIMENTAL ENTHALPY DEPARTURES FOR NITROGEN WITH VALUES FROM OTHER SOURCES Temperature Pressure (0F) (psia) (Ho0- HP (Btu/lb) This work Ma BWRb BWR IGT Dine LMWf H9 Sh PC 201.3 500 1.89 --- 2.0 1.9 2.0 1.9 1.8 2.1 1000 3.55 3.7 3.5 3.8 3.6 3.5 3.7 1500 4.99 5.2 4.8 5.3 5.1 4.9 5.2 2000 6.18 6.5 5.9 6.6 6.4 6.0 32.6 500 3.89 4.0 3.8 3.5 3.9 3.9 4.0 4.2 3.5 3.8 1000 7.33 7.6 7.4 6.7 7.5 7.5 7.7 7.6 6.9 7.3 1500 10.47 10.9 10.7 9.6 10.7 10.9 10.9 10.9 10.0 10.5 2000 13.17 13.7 13.5 12.0 13.6 13.7 13.1 12.7 13.2 -147.1 500 9.87 9.5 10.1 9.5 9.9 9.3 10.9 - 10.1 10.0 1000 20.83 21.0 21.3 20.2 21.0 20.9 22.2 21.3 20.9 1500 30.77 31.8 31.1 29.7 31.1 30.9 31.6 31.3 31.1 2000 37.20 37.6 37.0 35.9 37.7 35.6 37.6 37.8 37.5 a Mage et al.119 b Benedict, Webb, and Rubin Equation —constants of Stotler & Benedict'79 c Benedict, Webb, and Rubin Equation —constants of Crain & Sonntag36 d Bloomer & Rao15 g Hilsenrath et a179 e Din43 h Strobridge'82 f Lunbeck, Michels', & Wolkers'13 i PfenningC io a y P ~~~~~~~~i Hfenning, Canfield, & Kobayashil46

- 102 - -20 -30 0 -40- l7 -50 -60 -70 -80 -o -90 E - I00 E THIS WORK -200: ISHKIN a KAGANER X ISLES -300 (o/0L ROEBUCK a OSTERBERG -L Cp +1L GROSSMANN -400 Ic" GOFF a GRATCH d.B. STROBRIDGE B -T d T WOOD et. /. dT -1000L 200 300 400 TEMPERATURE (~K) Figure 31. Compaiison of Zero-Pressure Isothermal Throttling Coefficients for Nitrogen

Experimental Results for a Nominal 5 Percent Propane in Methane Mixture The nominal 5 percent propane in methane mixture was studied in the isothermal mode only. Data were obtained with both the 17 BWG and 16 BWG coils at 2000 F to test the effect of possible flow rate dependence. The 16 BWG coil was used to obtain data at 91.60 and -27~F in the gaseous region. In the compressed liquid region, at -147.4 F, data were obtained with a 19 BWG coil. The location of the experimental runs is shown in Figure 2 in the isobaric data section. The isothermal data for this mixture are given in Table L of Appendix D. Analysis of Results (Nominal 5 Percent Mixture) The isothermal data for the nominal 5 percent mixture were plotted as a function of pressure and equal-area curves passed through the data bars to obtain point values of 4. Values obtained from these plots are given in Table XXIV for the four isotherms. The two runs made at 2000 F. in different coils are shown in Figure 32. The agreement between the two runs is good at high and low pressures with a difference of about two percent at mid-range. This difference is consistent with the probable error given in Table XXI. A band representing the data of Figure 32 is plotted in Figure 33 for comparison with other data. - 103 -

-.023 METHANE - PROPANE MOLE FRACTION C3H8 0.05 MOLE FRACTION CH4 0.95 TEMPERATURE = 2000 F -.021 - 'E -.020 _ % -o % C -.019 -.018 -.017 - -,, — 16 BWG CAPILLARY 0 —17 BWG CAPILLARY COMBIN ED DATA -.016 0 500 1000 1500 2000 PRESSURE (PSIA) Figure 32. Comparison of Isothermal Data Obtained with Different Capillaries

TABLE XXIV ISOTHERMAL THROTTLING COEFFICIENTS FOR THE NOMINAL 5 PERCENT MIXTURE 4 (Btu/lb-psi) Temperature (OF) Pressure (Psia) -147.4 -27.0 91.6 200.0 0 -.044 -. 0294 -.0215 100 -.047 -.0297 -.0214 200 -.050 -.0301 -.0214 300 -.053 -.0304 -.0213 400 -.056 -.0308 -.0212 500..0023 -.060 -.0311 -.0211 600 -.0018 -.063 -.0313 -.0210 700 -.0014 -.067 -. 0315 -. 0209 800 -.0009 -.070 -.0316 -.0207 900 -.0005 -.075 -.0317 -.0206 1000 -.0002 -.078 -.0317 -.0204 1100.0002 -.080 -.0316 -.0201 1200.0004 -.078 -.0315 -.0199 1300.0006 -.074 -.0312 -.0196 1400.0008 -.066 -.0307 -.0193 1500.0011 -.057 -.0302 -.0190 1600.0013 -.049 -.0296 -.0187 1700.0015 -.041 -.0288 -.0183 1800.0017 -. 034 -.0279 -.0178 1900.0019 -.028 -.0268 -.0172 2000,0022 -.022 -.0255 -. 0106 - o105 -

Dillard determined values of the enthalpy departure from the ideal gas state to pressures of 500, 1000, 1500, and 2000 psia for a nominal 5 percent mixture. These results are not precise, but at most conditions a number of runs were made and the average value may be meaningful. Some of the data of Dillard are plotted in Figure 33. The values from 0 to 500 psia represent the experimental data while the values from 1000 to 1500 psia and from 1500 to 2000 psia represent differences between the experimental enthalpy departures. No values are plotted between 500 and 1000 psia because a number of values can be obtained depending upon which departure at 500 psia is chosen to calculate the difference. The data of Dillard are not precise. Within the limits of their precision, however, they agree with the present work. Values of ~ calculated from Equation (9) using the Joule-Thomson data of 23 Budenholzer et al. together with the heat capacity data of this work (See Section II) are shown in Figure 33. The results agree with the experimental band within a few percent. At low pressures the Joule-Thomson data of Sage 124 and co-workers are believed to be inaccurate [See Manning & Canjar ], and this may account for the shape of the curve as the pressure approaches zero. Figure 33 also shows values of 4 calculated using the Benedict-WebbRubin equation of state with constants for methane and propane from the.10 11 original article and mixing rules recommended by the same authors. The agreement with the experimental band is generally within a few percent. Enthalpy departures were calculated from the experimental ~ data by integration with respect to pressure. The values obtained are compared with other data and with correlations in Table XXV. The direct determinations of Dillard have already been mentioned. The B-W-R equation was used as an example of an equation of state. Edmister & Yarborough52 used the P-V-T data of Reamer, Sage, and Lacy to derive values of the enthalpy depar

METHANE -PROPANE MOLE FRACTION C3H8 0.05 MOLE FRACTION CH4 0.95 TEMPERATURE= 2000F -.025 1% a. 4) THIS WORK 4i DILLARD (1966) -/Cp - - --,BUDENHOLZER et al.(1942) Cp, THIS WORK -.015 V-TIcV' ~ ~ - - BENEDICT, WEBB, a RUBIN (1940) \ OT/p 6I p 0 500 1000 1500 2000 PRESSURE (PSIA) Figure 33. Comparison of Isothermal Data at 200~ F with Other Experimental Data

114 ture. The correlations of Lydersen, Greenkorn, and Hougen, Curl & 38 201 Pitzer, and the recent revision of the L-G-H method by Yen were used to calculate enthalpy departures. The average values of Dillard are generally within a few percent except at 2000 F. and 2000 psia. The B-W-R equation of state is in closer agreement with the experimental values than the generalized correlations or values derived from P-V-T data. TABLE XXV COMPARISON OF EXPERIMIENTAL EiTHALPY DEPARTURES WITH VALUES FROM OTHER SOURCES Temp. Pressure (H -H ) (OF) (psia) (Btu/lb) This work Da BWRb Eyc LGHd Yene CP -27 500 25.87 -- 26.2 -- 21.4 25.7 24.1 1000 60.27 -- 61.1 -- 55.2 58.4 56.9 1500 96.89 -- 98.0 -- 83.7 89.3 90.7 2000 116.01 -- 117.5 -- 100.9 108.6 111.2 91.6 500 15.13 14.9 15.0 14.0 11.2 15.2 14.6 1000 30.89 30.2 30.8 29.8 26.8 29.4 29.7 1500 46.49 45.6 46.5 46.2 39.8 45.1 46.4 2000 60.58 60.2 60.8 62.9 51.1 58.8 60.5 200 500 10.66 10.0 10.4 10.6 7.2 10.4 11.1 1000 21.05 19.8 20.7 21.3 17.1 20.8 21.5 1500 30.91 29.1 30.6 31.4 25.5 31.1 31.3 2000 39.88 35.8 39.7 40.6 32.5 39.6 39.6 a Dillard41 b Benedict, Webb and Rubin c Edmister and Yarborough52 d Lydersen, Greenkorn and Hougen e Yen201 f Curl and Pitzer I- o8

The experimental values of 4 were extrapolated to zero pressure in order to compare with values calculated from published virial coefficients. Data for the second virial coefficient of methane [Huff & Reed 85, Douslin et al. ], propane [Dawson & McKetta, Huff & Reed8] and mixtures of methane and propane [Huff & Reed] were graphically differentiated to obtain dB/dT. The results are given in Table XXVI together with values of ~o calculated from Equation (15) and values obtained by linear extrapolation of the experimental data to zero pressure. The agreement between the calculated and experimental results is fair. TABLE XXVI Calculation of Zero-Pressure Isothermal Throttling Coefficients from Virial Coefficient Data T B dB/dT o (Eqn. 15) o (Experimental) (OF) (cc/mole) (cc/mole- K) (Btu/lb - psi) (Btu/lb - psi) x 10-2 x 10-2 200 CH4 - 20.4 0.30 C3Hg -247 1.22 -2.45 -2.15 CH4-C H8 - 85.4 0.49 91.6 CH4 - 39.7 0.35 C H -375 2.97 -2.90 -2.94 3 8 CH4-C3H8 -125.8 0.84 109 -

SECTION IV-ENTHALPY TABLES AND DIAGRAMS The experimental data on the effect of temperature and pressure on enthalpy of Sections II and III has been used to prepare skeleton enthalPY tables and diagrams. New tables and diagrams are presented for the nominal 5, 12, and 28 percent propane in methane mixtures, and the nominal 43 percent nitrogen in methane mixture. Comparisons are made with vapor-liquid equilibrium data, calculations of the latent heat of vaporization and enthalpy data from the literature. Nominal 5 Percent Propane in Methane Mixture A skeleton enthalpy table and a pressure.enthalpy-temperature diagram for this mixture have been prepared which are based almost entirely on experimental calorimetric data obtained in the Thermal Properties Laboratory of the University of Michigan. The following procedure was used in preparing the diagram and table: 1) Reference states of 0 Btu/lb were taken to be the pure components as saturated liquids under their own vapor pressure at -280 F. This choice is consistent with that previously used for methane and the previous diagram for this mixture 2) The enthalpy of pure methane as a gas at zero pressure and 2000 F. was calculated using the data on the heat of vaporization at 64 5 psia of Frank and Clusius6, the B-W-R equation of state to correct from 5 psia to zero pressure, and values of the ideal gas enthalpies from Rossini 61 The following results were obtained: Enthalpy, Btu/lb Latent heat of vaporization at -280 F. 228.27 Effect of pressure on enthalpy (0 to 5 psia) 1.43 Ideal gas enthalpy (-280 F to 200 F.) 248.09 477.79 - 110 -

Colwell, Gill, and Morrison32 have recently measured the latent heat of vaporization at 1000 K which agrees with Frank and Clusius to within 0.25 percent. 3) The enthalpy of pure propane as a gas at zero pressure and 2000 F. was calculated using liquid phase heat capacity data and the latent heat of vaporization at one atmosphere from Kemp and Egan 98, the B-W-R equation of state to correct from one atmosphere to zero pressure 161 and values of the ideal gas enthalpies from Rossini. The following results were obtained: Enthalpy, Btu/lb Liquid heat capacity (-280~ F to -43.7 F) 115.30 Latent heat of vaporization at -43.70 F 183.17 Effect of pressure on enthalpy (0 to 94.7 psia) 2.70 Ideal gas enthalpy (-43.7 to 200 F) 97.51 398.68 4) The enthalpy of the methane-propane mixture at zero pressure and 200 F was calculated assuming zero heat of mixing under these conditions. Hmix = 0.131 (398.68) + 0.869 (477.79) = 467.43 Btu/lb. 5) The isothermal effect of pressure on enthalpy at -270 F, 91.60 F and 2000 F. was obtained from the integrated ~ data of Section III at pressures from 0 to 2000 psia. In the previous diagram for this mixture prepared by Manker, the effect of pressure on enthalpy at 70 F was estimated from approximate Joule-Thomson measurements made with the isobaric calorimeter combined with experimental heat capacity data. The enthalpy departure at 2000 psia obtained in this way agreed within 3 percent with the integration of the Joule-Thomson data of Budenholzer et 23 al. combined with the experimental heat capacities. The Joule-Thomson 411

data of Budenholzer et al. extend only to 1500 psia and an extrapolation to 2000 psia was necessary to make this comparison. The enthalpy departures for this mixture are presented as a function of temperature in Figure 34. A comparison is shown between the measured 41 isothermal data of this work, the isothermal data of Dillard and the 23 Joule-Thomson data of Budenholzer et al. combined with experimental heat capacities of this work. It appears that the values calculated from the Joule-Thomson data are in error at 1500 psia and the extrapolation to 2000 psia only compounds the error. The B-W-R equation is seen to predict departures in excellent agreement with the measured isothermal data of this work. 6) The isobaric enthalpy data of this work and that of Manker123 were used to determine the isobaric effect of temperature on enthalpy in both the gaseous and liquid regions as well as within the two-phase envelope. The limits of the two-phase region were determined using results of the traverses of the two phase region made by Manker, supplemented by 151 the data of Price and Kobayashi Since enthalpy is a property, changes in enthalpy are independent of the path chosen and the consistency of the experimental data can be tested by making loop checks. A grid consisting of 11 loops was constructed and the enthalpy change around each loop evaluated. In all but one case the closure, defined as the difference in the enthalpy change by the two paths, was less than one percent. The grid is shown as Figure 52 of Appendix C together with the values of the enthalpy change along each path. In most cases, a loop with a positive closure was adjacent to one with a negative closure. The enthalpy difference common to both loops was adjusted to close each loop. This adjustment was made until all eleven loops closed exactly. - 112 -

- 113 - 120 \ Methane - Propane Mole Fraction C3H8,:0.05 I \ \ Mole Fraction CH4:0.95 100 100 This Work \90 \2000 PSIA 0 Dillard (1966) o \L-Budenholzer ef a/(1942) Cp - This Work Benedict, Webb, & Rubin ~4 ~ ~1500 (1940,1942) 70 60 50 O L l I I II I I I I I I I I 4o 30 - 20 -40 -20 0 20 40 60 80 100 120 140 160 180 200 220 TEMPERATURE ( F) Figure 34. Enthalpy Departures for the Nominal 5 Percent Mixture

7) A smooth plot of the results was prepared and is shown in Figure 35. The shape of the isotherms in the liquid region is chosen so as to allow the -2800 F isotherm to be drawn to the value of 0.3 Btu/lb for the heat of mixing of methane and propane at -2800 F calculated 39 from the data of Cutler and Morrison 8) The values of enthalpy are given in Table XXVII. The chief differences between this diagram and the one pre123 130 sented by Manker or the later revision are: i) The effect of pressure on enthalpy is based on experimentally determined values of 4. ii) The diagram has been extended to 3000 F by additional experimental data to 250 F and calculations from the B-W-R equation of state. Nominal 12 Percent Propane in Methane Mixture A skeleton enthalpy table and a pressure-enthalpy-temperature diagram for this mixture have been prepared. In a previous report of this work130 the effect of pressure was determined from the integration of the Joule-Thomson coefficients of Budenholzer et al. together with the experimentally determined heat capacities. The experimental results on the nominal 5 percent mixture indicated that the effect of pressure on enthalpy estimated in this way is likely to be in error at pressures above about 1000 psia and that the extrapolation to 2000 psia is not desirable (See Figure 34). Enthalpy departures calculated by the B-W-R equation, experimental values of 42 Dillard et al., and values obtained by combining u from Budenholzer 23 et al. with the experimental C are compared in Figure 36. Again the dotted squares represent departures calculated from ip data which were

9 -Leu-EwON iq4 a0J- uea-2,e-rg Sd-[-eq4u2j--xn4i wvnie) Ad7lVHiN3 '099 Ot?9 029 OZ9 019 009 06V 08V 02-V 09V 09t Ott 02V OZV Olt OOV 062 082 1 7 1 L HI L I I 1::F- — 7 -I — J-961 NVOIHOIVY AO 7.kiIS83AINn III. a 11%) N N 11 110 0 3Hi 0 0 0 0 7- liE J F-A -I L-1 I J I ',I O=H J.083-1 iv sainon (13innivs: 3NVdO8d CINV 3NVHi3VY 38nd — vynivcl. 1760 HO NOliOV8J 3-lovy All I Al, W I il l 11 It Z900 H 0 NOUOV8 A 3-1OVY NVdO8d - Vi I.J. II T777 I L-2 i -1-1. I -1 EF4ffp'*

2000 I T I T-T IT 7 -1900 14 I1800 441F 7 T4 I I II i-F t r7 I I I I I I I I! _F 4. '41 1700 -T T-, 7_1 T-T -t.H - 1 I I l.m I I;, Go Et -H] 0 1 -0: V 0 0 0 1600 r) Cy 0 m to: WO I cm CY CY - W 11) c1J A., II-7 i ++. 'A I + 1500 J LL -4 14 4 LJ I I 1400 I I I F- --- 44 METHANE - PROPANE 1300 H MOLE FRACTION C H 0052 3 8 4-H I II++ 1200 MOLE FRACTION CH Q948 4- PF It + I 100, DATUM 4 oil _r. PURE METHANE AND PROPANE L.Li 1000 SATURATED LIQUIDS AT goo -280OF H=O if + i- — H I I I I I L-I I ui TAFT! [-A FIFF +14 -I- FT 800 — 4- -.44- I I t I THE I T-F — F -H700 T-F UNIVERSITY t__ 4 -OF 6 0 0 - 1 I - Ill I I 1111 -1 1 1 + 44 MICHIGAN i7 -4- - -4 --ITT-4 iolT+. 1 T 500 1967 t 444 -4 -400 I T I 1 ++ t-LI tT UL 1 '' I i; - 4LI If. TT' 300 It 1:1 +IJI T- a 4+ LL-1 01 + 200 7+ -L 4! 100 4-11. T 1__L I.-L I I LJ L-1 11 -H44+4 -0 0 10 20 30 40 50 60 70 80 90 inin nin i9in r;,in ian i;;n i,

- 117 - TABLE XXVII TABULATED VALUES OF ENTHALPY FOR THE NOMINAL 5 PERCENT MIXTURE Temperature, ~F Saturated Saturated Latent Heat of Pressure Bubble Dew Liquid Enthalpy Vapor Enthalpy Vaporization (psia) Point Point (Btu/lb) (Btu/lb) (Btu/lb) 100 -208 -92 63.1 311.4 248.3 200 -178 -66 88.5 318.1 229.6 300 -159 -56 106.6 317.9 211.3 400 -142 -49 122.0 316.0 194.0 500 -129 -42 135.9 313.5 177.6 600 -117 -39 149.4 308.9 159.5 700 -107 -38 164.0 302.1 138.1 800 -95 -38 180.1 294.1 114.0 900 -84 -42 200.2 281.8 81.6 H (Btu/lb) Temperature Pressure, psia (OF) 0 250 500 750 1000 1250 1500 1750 2000 -280 230.5 5.0 7.0 8.Z 9.0 ZO.5 ll.Z Z2.2 23.2 -270 235.1 Z2.6 Z4.5 Z5.6 Z6.6 Z7.9 Z8.9 20.0 2Z.0 -260 239.7 20.6 22.0 23.Z 24.3 25.5 26.5 27.6 28.6 -250 244.3 29.9 31.Z 3Z.9 32.5 33.4 34.Z 35.0 35.8 -240 248.9 38.0 39.1 39.8 40.6 4Z.5 42.4 43.Z 44.0 -230 253.5 45.7 46.6 47.5 48.3 49.2 50.1 50.6 5Z.5 -220 258.2 53.7 54.4 55.Z 55.9 56.5 57.3 58.0 58.6 -210 262.8 6Z.7 62.4 63.Z 63.9 63.5 65.2 65.9 66.4 -200 267.5 69.9 70.6 7Z.3 72.0 72.6 73.2 73.9 74.4 -190 272.1 78.0 78.5 79.2 79.8 80.4 80.9 8Z.5 82.2 -180 276.7 85.7 86.3 86.9 87.5 88.3 88.8 89.4 90.0 -170 281.4 96.3 96.4 96.7 97.0 97.3 97.5 97.8 98.0 -160 286.1 196.5 103.7 Z03.6 104.0 Z04.4 105.0 Z05.5 105.9 -150 290.8 211.0 113.1 ZZ3.0 112.8 1Z2.8 113.2 ZZ3.8 114.0 -147.4 292.0 115.6 115.1 115.1 115.3 115.5 116.1 -140 295.5 237.9 123.2 Z22.2 121.9 Z2Z.8 121.8 Z22.0 122.3 -130 300.2 251.0 134.3 Z32.5 131.4 Z3Z.0 130.6 Z30.6 130.9 -120 304.9 262.2 212.9 Z43.8 141.5 Z40.Z 139.4 Z39.5 139.5 -110 309.6 272.3 237.5 Z56.Z 152.3 Z50.2 149.0 Z48.5 148.3 -100 314.3 281.8 251.9 Z75.0 164.5 Z60.7 158.9 Z57.9 157.3 -90 319.1 290.4 263.7 224.6 179.1 172.5 169.5 Z67.9 166.5 -80 323.8 299.1 274.4 245.0 198.3 Z83.8 180.7 Z78.4 176.3 -70 328.6 308.5 284.8 260.9 222.7 Z99.3 192.8 Z88.6 186.3 -60 333.4 318.5 294.5 273.2 244.5 2Z5.6 205.9 200.2 196.7 -50 338.2 324.8 305.0 285.9 261.3 233.0 219.9 2Z2.Z 207.4 -40 343.0 330.2 315.2 296.8 274.5 249.0 234.2 224.5 218.5 -30 348.7 335.7 321.5 305.5 285.9 264.4 248.3 237.Z 229.8 -27 349.3 337.3 323.4 307.3 289.0 269.0 252.4 240.7 233.3 -20 352.7 341.1 327.8 3Z2.4 295.9 277.8 261.5 249.2 241.1 -10 357.5 346.5 333.9 3Z9.4 304.9 288.7 273.7 26Z.2 252.4 0 362.5 351.9 340.0 327.3 313.3 298.2 284.9 273.Z 269.5 10 367.4 357.2 346.0 334.Z 321.2 307.8 295.1 284. Z 274.4 20 372.3 362.6 351.9 340.8 328.8 3Z6.4 304.7 294.0 284.7 30 377.3 367.9 357.8 347.3 336.1 325.0 313.7 304.0 294.7 40 382.3 373.3 363.6 353.6 343.2 332.6 322.3 3Z2.8 304.2 50 387.4 378.7 369.5 360.Z 350.1 340.2 330.6 32Z.8 313.4 60 392.5 384.1 375.2 366.2 356.9 347.6 338.5 330.0 322.2 70 397.6 389.5 381.0 372.7 363.6 354.9 346.2 338.3 330.7 80 402.7 394.9 386.8 378.8 370.2 36Z.8 353.7 346.0 338.8 90 407.9 400.4 392.6 384.7 376.7 368.9 361.1 353.8 346.9 91.6 408.7 401.3 393.5 385.6 377.8 370.2 362.2 355.2 348.2 100 413.1 405.9 398.4 390.6 383.3 375.5 368.3 36Z.0 354.8 110 418.3 4ZZ.9 404.1 396.8 389.7 382.4 375.4 368.8 362.5 120 423.6 4Z7.Z 409.9 402.6 396.1 388.9 382.5 376.9 370.2 130 428.9 422.7 415.7 408.9 402.4 395.8 389.5 383.5 377.7 140 434.3 428.2 421.6 4Z5.4 408.8 402.3 396.3 390.9 385.1 150 439.7 433.5 427.4 42Z.8 415.1 409.4 403.2 397.5 392.3 160 445.1 439.3 433.3 427.4 421.4 4Z5.5 410.0 404.5 399.6 170 450.6 444.6 439.2 433.6 427.7 42Z.5 416.7 4ZZ.5 406.7 180 456.2 450.5 445.1 439.7 434.0 428.6 423.5 4Z8.5 413.8 190 461.8 456.4 451.1 445.3 440.3 434.8 430.2 425.4 420.9 200 467.4 462.2 457.0 451.8 446.6 441.6 436.9 432.5 427.9 210 473.1 468.0 463.0 458.1 453.0 448.Z 443.5 439.0 434.9 220 478.8 474.0 469.5. 464.Z 459.3 454.4 450.2 446.2 441.9 230 484.6 479.7 475.Z 470.3 465.7 460.8 456.9 453.Z 448.9 240 490.4 486.Z 48Z.3 47C.6 472.Z 467.6 463.5 459.9 455.9 250 496.3 492.1 487.4 482.7 478.5 474.4 470.2 466.6 462.9 260 502.2 498.0 493.6 489.3 484.9 485.5 476.9 473.4 469.9 270 508.1 504.5 499.8 ~95.Z 491.4 487.2 483.6 480.5 476.8 280 514.1 5101 3 506.0 505.8 497.9 494.2 490.4 487.5 483.8 290 520.2 556.3 552.3 508.3 504.4 500.6 497.5 493.9 490.7 300 526.3 522.4 558.6 554.7 5Z0.9 507.3 503.9 500.6 497.7

extrapolated to 2000 psia. On the basis of the results for the 5 percent mixture and the comparison of Figure 36,' the isothermal effect of pressure on enthalpy for this mixture was estimated using the B-W-R equation of state. The data were extended down to -280 F from the lower experimental limit of -240 0F by extrapolating plots of C versus T prepared from p the experimental data. The change in C is relatively small over this range of temperature. The data were extended up to 300 F from the upper experimental limit of +140 F by blending experimental C data p with values calculated using the B-W-R equation at higher temperatures. Enthalpies are tabulated in Table XXVIII and the diagram is presented as Figure 37. Nominal 28 Percent Propane in Methane Mixture A skeleton enthalpy table and a pressure-enthalpy-temperature diagram for the nominal 28 mole percent propane in methane mixture have been prepared and are presented as Table XXIX and Figure 38. The procedure followed in preparing this table was identical to that used for the nominal 5 percent mixture except that the isothermal effect of pressure on enthalpy was estimated using the B-W-R equation at 1300 F. 131 In a previous report of the work on the nominal 28 percent mixture, the effect of pressure on enthalpy was determined from the integration of the Joule-Thomson coefficients of Budenholzer et al.23 together with the experimentally determined heat capacities at 130 F. As shown in the construction of the enthalpy diagrams for the nominal 5 and 12 percent mixtures, the Joule-Thomson data are believed to be in error and it was decided to use the B-W-R equation of state which predicts heat capacities at this temperature at pressures up to 2000 psia within two percent. - 118 -

Metone- ropone 17 MoteFrotion C3H811 roe fction C 0.C88 90 0 Dil11rd etaI. (e966a 0WPL-Budenholzer et 2) SC) cp.-. -This worW Benei~tWebba Rubin ___ ~~(1940,1942.) 60 3 60~~~~- ~~ ~~ 2000 pSIA c~50 l0 1500 60~o~ ~ 80 00 120 140 160 180 ZOO An so -TEMPE:RATURE (F piue36. EnthalPY Departures for the Nominal 12 Percent M4jxture

PRESSURE (PSIA) N N CM 00 (.0 0 - N _q 00 (O 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 No 0 0 0 0 0 0 0 0 0 0 O 0 0 0 0 0 0 0 0 0 0 11 --- 11111......... At I op I LIJ 10D. 7 0 0, _++ O I IN -- LI, O 7 -WI ff IIA A 0 0 __ - 9 Jr N) OD I Al WI 7 r -— Al O A -FO, I -------- 00 d N) I N I I J. I -. F... r I N I I I 00 -OPI (A I.Aw 0 50 II tl A I Irl I O I-TJ rl 10 Ir 0 la I I I;O 1A. Fj Uj AO III -PF ip P-0 NO;io L - olT (D _jo_ R I Po _rrr C.0 (J UJ 0 Uj I F 11 I Fl I opr I 0 7 _0 I I -1 I I 0 7 — U) - I t 0 r-r-T-1 C( (J Cn PI 'OD Fj (D I Jill jo(J I I I-op-I I I I-jopr I I I Or p FJ- (D 10 0 — pr I L..bpr_ I I I I I I I L. Or I I -JO I CD - I -L.Aoprl Or- I -.0 -1 I I 11 I 0 (D D IIII 09!_ z (A Z..Opp (D 00 H (D I -L. -Pr> co Fj 0 IJ.Apr_ Poe CD I IIt I _.o II _7 ------ psaf I -.O I -.A.Pr, Ljoll 0 -I I -.o-r -4 4s T! 7 jj,.o 0

II lotI 11 1W I ElI III otI I~II I II I 1 11 111 1IsI III I I IEII II IE II I I 1 900 1800- l (680'tt El' I t iStK I ml I I II. 4 I I'll Iflt~t~~tfR SHHt~ f A 1 7 0 0a 1I 0 CM 0.POPI\E' 1300i~ OLE4)D DO 'CD~ A1 tOL CY cm-H~i88 (n 1100~~~~~~~~~~~~~~~~~~~~II 1Ill 1500 I11 0 F H I 14n 00' METH ANE~ TH a of~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ i 1300 MOLE FRACTION C3 H J1 1200. I100 LL 0 00 -SATURATED LIQUIDS AT3 1015 6017 801020 1 20232420202728 900 lilt Ills lilt THE'TALY (TIILB lilt 1111 1 21Pesue-em rtueE-thly igamfrth oinl1 Pecn 800 UNIVERSITYMxtre(Lw emertue

- 122 - TABLE XXVIII TABULATED VALUES OF ENTHALPY FOR THE NOMINAL 12 PERCENT MIXTURE Temperature, ~F Saturated Saturated Latent Heat of Presaure Bubble Dew Liquid Enthalpy Vapor Enthalpy Vaporization (psia) Point Point (Btu/lb) (Btu/lb) (Btu/lb) 100 -209 -63 51.0 319.3 268.3 200 -172 -34 79.5 327.9 248.4 300 -150 -18 99.2 329.4 230.2 400 -136 -5 115.0 329.0 214.0 500 -124 4 127.8 327.9 200.1 600 -112 8 138.9 325.4 186.5 700 -101 10 149.6 322.1 172.5 800 -89 11 160.7 317.9 157.2 900 -77 12 174.4 311.5 137.1 1000 -65 10 188.7 303.0 114.3 1100 -49 4 205.5 287.5 82.0 H (Btu/lb) Temperature Pressure, psia (~F) 0 250 500 750 1000 1250 1500 1750 2000 -280 231.3 Z.5 2.7 4.0 5.3 6.5 7.7 9.0 ZO.Z -270 235.5 7.7 9.0 Z10.5 ZZ.8 Z3.2 Z4.5 Z5.9 Z7.Z -260 239.8 Z4.5 Z6.1Z 7.5 Z8.9 20.4 21.8 23.2 24.5 -250 244.1 2Z.5 23.1 24.5 26.0 27.4 28.8 30.1 3Z.5 -240 248.3 28.8 30.2 31.8 33.2 34.6 36.1 37.5 38.9 -230 252.6 36.2 37.4 39.0 40.4 41.8 43.2 44.5 45.8 -220 256.9 43.2 44.8 46.0 47.6 49.0 50.5 5Z.8 53.0 -210 261.2 5Z.0 52.2 53.7 55.0 56.4 57.6 58.9 60.1 -200 265.5 58.4 59.8 6Z.0 62.4 63.6 65.0 66.2 67.5 -190 269.9 66.2 67.5 68.7 70.0 7Z.4 72.5 73.8 75.0 -180 274.1 74.0 75.3 76.5 77.8 79.0 80.2 81.4 82.5 -170 278.3 82.2 83.3 84.5 85.6 86.8 87.9 89.0 90.1 -160 282.9 90.5 91.6 92.6 93.6 94.5 95.5 96.5 97.4 -150 287.3 99.9 Z00.9 101.8 Z02.6 103.5 Z04.4 105.1 -140 291.7 109.8 Z09.6 110.0 ZZ0.6 111.3 ZZZ.8 112.4 -130 296.1 119.5 ZZ118.4 118.4 ZZ118.8 119.3 ZZ119.5 120.1 -120 300.5 2Z8.9 152.8 Z29.0 127.6 Z27.5 127.5 Z27.7 127.9 -110 305.0 237.7 193.1 Z38.9 136.5 Z36.0 135.8 Z35.9 135.9 -100 309.5 249.4 213.1 Z49.1 145.7 Z44.9 144.5 Z44.3 144.1 -90 313.9 259.7 226.8 Z76.5 156.3 Z54.2 153.5 Z53.0 152.4 -80 318.4 267.5 238.1 203.5 168.1 Z64.7 162.8 161.7 161.0 -70 322.9 280.0 248.3 222.3 181.6 Z76.0 172.7 171.1 169.9 -60 327.5 290.8 258.1 236.7 205.0 Z87.1 183.2 181.0 179.0 -50 332.1 299.5 268.3 250.5 225.2 Z99.0 194.4 191.4 188.5 -40 336.6 309.7 279.1 262.3 240.6 2Z3.1 206.4 202.2 198.2 -30 341.2 321.7 290.3 273.5 252.5 229.2 219.3 2Z3.0 208.3 -20 345.8 33Z.9 302.1 284.9 266.5 243.4 232.3 224.4 218.7 -10 350.5 337.Z 313.6 297.0 280.1 257.8 245.3 236.Z 229.3 0 355.2 342.3 324.6 308.0 291.9 27Z.4 257.7 248.0 240.0 10 359.9 347.2 332.6 3Z9.0 302.3 284.0 269.7 259.4 250.7 20 364.6 353.0 340.0 327.2 311.7 295.2 281.1 270.5 261.3 30 369.4 359.0 346.9 334.5 320.3 305.2 291.7 28Z.3 271.7 40 374.2 364.4 353.3 341.0 328.3 3Z4.2 301.7 291.1 281.7 50 379.1 369.3 359.4 348.3 335.9 322.5 311.0 300.8 291.5 60 383.9 374.5 365.2 354.6 343.1 33Z.0 319.9 310.2 301.0 70 388.9 379.8 370.9 360.6 350.0 338.5 328.3 3Z8.9 310.2 80 393.8 385.2 376.4 366.2 356.7 346.1 336.4 327.6 319.1 90 398.8 390.4 381.9 372.8 363.3 353.4 344.2 335.5 327.7 100 403.9 395.8 387.3 378.7 369.7 360.6 351.8 343.9 336.1 110 408.9 401.1 393.1 384.6 376.2 367.5 359.3 351.6 344.2 120 414.0 406.5 398.8 390.8 382.7 374.5 366.6 359.4 352.2 130 419.2 411.8 404.5 396.9 389.1 381.2 373.8 367.0 360.0 140 424.4 4Z7.5 4Z0.2 402.9 395.5 388.1 380.9 374.2 367.7 150 429.7 422.8 4Z6.0 409.1 401.8 394.8 387.9 381.5 375.3 160 435.0 428.6 421.7 4Z5.0 408.1 401.5 394.9 388.8 382.7 170 440.3 434.0 427.5 421.1 4Z4.5 408.0 401.7 396.0 390.Z 180 445.7 439.5 433.3 427.0 420.7 4Z4.8 408.5 402.7 397.3 190 451.1 445.2 439.1 433.1 427.1 421.1 4Z5.3 4Z0.0 404.5 200 456.6 450.8 445.0 439.2 433.3 427.6 422.1 4Z6.9 4ZZ11.7 210 462.1 456.5 450.9 445.3 439.7 434.Z 428.8 423.6 4Z8.8 220 467.7 462.4 456.8 451.4 446.0 440.6 435.5 430.6 425.9 230 473.4 468.0 462.8 457.5 452.3 447.0 442.2 437.5 432.9 240 479.0 474.0 468.8 463.7 458.6 453.9 448.9 444.0 439.9 250 484.8 479.7 474.8 469.8 465.0 460.2 455.6 451.2 446.9 260 490.6 485.8 480.9 476.0 471.3 466.7 462.3 458.0 453.9 270 496.4 491.6 487.0 482.4 477.7 473.2 468.9 464.9 460.9 280 502.3 497.7 493.1 488.8 484.2 479.8 475.7 471.2 467.8 290 508.2 503.8 499.3 495.0 490.6 486.5 482.4 478.4 474.8 300 514.2 509.9 505.5 501.3 497.1 493.1 489.1 485.4 481.7

PRESSURE (PSIA) N) uj -f O OD 0 No (J oI OD r.0 >ia e 3s@ < 8 W 0Su~~audLA je~~kS~tA gk 0 | X X X X t 2 W g A 4 > n f <; t B 20 0 5 S: 3 0 30[Et S S S g-3 0 *~~~~~~~~~~~~j ff S: p0 T i t11 <11 Ljo Lmo 5 5 i ~ g g~~~~~~~40 t TL L e. m < ~ 1 -g JW' -< ' ' I t A < B M~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~. r R < 1\ 1 t R: g e S 010 S e g + t: k t: > + C3~~~~~~~~~~~~~~~-0 0 i E > C~~~~4i L ) > > < V2 0 00oPlue LtL<itEL<L L U; <IXt' L<L > O mF L~~~rn~nmT<Rm>Xfl-l A260<1 1 XHM1~~vl z~~~~~~~~~~~~~~ El, 1 T.:1 w O f.,, T [>ST'I17 - 1 I Lorl ll,l II I I 1' 1:'1-;:1T t -1x taL <: 1 _ 4 T T be.14.,1 1 10f L~~~~~~~~~~~~~~~~~~~~~~~~~~l l -10 H >~8 - -I ~ A; ]W@DO 0; ~|!;11t a11 W mX1i- lit| V X1Xv~r~r tX 14~ Z00011i 10,1 (D~ i 111T T mW TT [X~ -Fi S~~~~~~I i " '11 '"l: OOOO4eS,,X e

PRESSURE (PSIA) N cm w 0 clW w 0 FD 3 0 0 0 23 0 F3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.0 0 0 8 0 0 0 0 0 0 0 0 0 0.......... _14- r D_ rTr JAI-1 —l-w- _4_1_1_41 _717., _7 7.7, 7....... i. 114 -0 +; 250 + ---i i-A c M A m M -FrTT T 17T- 2 4 0 Ti _1 j _FT- T 411 7_7 T_, CZ -0 'R'f-220 J.J. z 4 -4 TI+ 01 z z Ti-6, < 210 --C) m 4+ _+7 (.0 0 M C: C) C-) >P, ii-A 1-,Hdl,m I T — M z 4 > (D 4111 -180 Fl 00 00 I 1 1' A-Li OD OD N > 0 i- ji+ _i_ 7 0 I 0 z J-d -T-r- A-i H- Fj (D -F -;4 -1 1 —! I rt (J) 4 -C03 11-4- -4-A(D Fj -H-[+-H ----,'+ -H fl-Al 4MI-11-M-4-1- -+i+ 41 CD t7i 1-3 -H::3 --- --- Fa ----- - (D (D Fj T- 1-44 10' N) (D S= Fj P) -t- - I -4t -41 4 D (D J rt. m I IA -.14 4 -14- -4 4 - t!rj z — fl-i — A it-1 - -.1 I Fj Z + (D rf- 'T T HF J+ T tj -ITT7 E TM -I,, w-V441-T- J, y _< Ol Cl ------ I J. +T-F I rttlorq 5 Fj C: I I.u -T-1 _F...... 4 1 -4- Jfl*fl-H 4 —r — 0 4-IR:a - TT_ Tf F J n 4H)~L-L _4 -1-1; I -1

- 125 - TABLE XXIX TABULATED VALUES OF ENTHALPY FOR THE NOMINAL 28 PERCENT MIXTURE Temperature. ~F Saturated Saturated Latent Heat of presaue ' Bubble Dew Liquid Enthalpy Vapor Enthalpy Vaporization (psia) Point Point (Btu/lb) (Btu/lb) (Btu/lb) 100 -202 -25 50.0 323.5 273.5 200 -167 11 74.5 334.1 259.6 300 -145 30 91.1 336.6 245.5 400 -126 43 104.3 337.7 233.4 500 -110 55 116.0 337.9 221.9 600 -96 64 126.9 337.1 210.2 700 -84 71 137.0 335.9 198.9 800 -72 78 147.0 331.1 184.1 900 -59 80 156.9 328.4 171.5 1000 -47 79 166.5 321.5 155.0 1100 -36 77 177.0 312.5 135.5 1200 -21 74 189.3 300.5 111.2 1300 -4 64 205.0 283.0 78.0 H (Btu/lb) Temperature Pressure, psia (~F) 0 250 500 750 1000 1250 1500 1750 2000 -280 232.8 2.5 3.3 4.0 4.9 5.8 6.5 7.8 9.0 -270 236.4 7.4 8.6 9.8 Z0.9 Z2.1 13.4 14.5 Z5.8 -260 240.0 Z3.6 Z4.8 Z6.0 Z7.Z Z8.4 Z9.5 20.6 21.9 -250 243.6 20.0 21.0 22.4 23.5 24.6 26.0 27.3 28.5 -240 247.2 26.4 27.5 28.6 29.8 3Z.0 32.1 33.3 34.4 -230 250.9 33.2 34.3 35.3 36.4 37.4 38.5 39.5 40.5 -220 254.6 38.9 40.2 41.4 42.5 43.6 44.8 45.9 47.0 -210 258.3 45.6 46.8 47.9 49.0 50. 51.2 52.4 53.4 -200 262.0 52.0 53.0 54.Z 55.2 56.3 57.3 58.5 59.4 -190 265.7 58.4 59.4 60.6 61.6 62.8 63.8 64.9 66.0 -180 269.5 66.0 66.7 67.6 68.5 69.3 70.1 7Z.0 7Z.8 -170 273.3 72.3 73.1 73.9 74.7 75.6 76.4 77.Z 78.0 -160 277.1 79.1 79.8 80.6 81.5 82.2 83.0 83.8 84.5 -150 280.9 101.4 87.5 88.Z 88.6 89.4 90.0 90.6 91.3 -140 284.8 135.6 94.2 94.7 95.3 95.8 96.3 97.0 97.5 -130 288.7 101.0 Z01.5 101.9 Z02.5 103.0 Z03.5 103.9 -120 292.6 108.4 Z08.7 108.9 Z09.5 109.9 ZZ0.4 110.7 -110 296.5 116.0 ZZ116.3 116.5 ZZ6.8 117.0 117.3 117.5 -100 300.5 198.7 143.7 Z23.4 123.5 Z23.7 124.0 Z24.1 124.3 -90 304.5 207.3 161.3 131.2 131.0 Z13.0 131.0 131.0 131.0 -80 308.5 2Z4.2 174.3 139.5 138.2 138.0 138.0 Z38.0 138.0 -70 312.5 222.6 186.0 Z56.2 146.5 Z45.4 145.5 Z45.4 145.4 -60 316.6 230.1 195.2 171.0 154.9 Z53.0 152.7 Z52.7 152.8 -50 320.7 241.4 205.5 Z82.8 163.0 161.2 160.5 Z60.3 160.2 -40 324.9 25Z.4 215.3 Z95.0 177.7 Z70.5 168.5 Z68.0 167.8 -30 329.1 261.3 225.1 206.0 191.0 Z79.5 177.0 Z76.1 175.5 -20 333.3 27Z.0 235.7 2Z7.3 203.2 189.5 185.6 Z83.7 183.4 -10 337.5 280.0 246.4 228.9 215.4 200.8 194.7 Z92.8 191.5 0 341.8 287.5 256.9 240.5 226.2 2ZZ11.9 204.4 201.5 199.9 10 346.1 306.5 268.1 251.1 237.6 223.9 214.5 2ZZ11.0 208.5 20 350.5 333.9 280.7 263.0 248.9 235.3 225.2 220.9 217.3 30 354.9 340.3 295.7 275.0 260.2 247.1 236.3 231.0 226.3 40 359.3 345.5 310.2 287.3 271.9 258.1 247.6 24Z1. 235.5 50 363.8 350.6 326.7 301.2 283.7 269.0 259.0 25Z.9 244.9 60 368.3 355.8 341.2 3Z5.5 296.1 280.6 270.2 261.6 254.5 70 372.9 360.9 347.3 330.7 309.4 293.Z 281.1 272.5 264.1 80 377.5 366.1 353.2 338.2 321.7 305.5 291.6 282.Z 273.7 90 382.2 371.2 359.1 345.4 330.4 3Z5.0 301.6 29Z.5 283.2 100 386.9 376.4 364.8 351.7 338.2 323.5 311.1 301.4 292.6 110 391.7 381.5 370.5 358.6 345.6 332.2 320.1 3Z0.1 301.7 120 396.5 386.7 376.2 364.9 352.7 340.2 328.8 3Z9.1 310.7 130 401.4 391.9 381.8 371.1 359.7 348.3 337.2 327.5 319.4 140 406.3 397.2 387.5 377.4 366.5 355.6 345.3 336.5 328.2 150 411.2 402.5 393.2 383.4 373.3 363.5 354.1 345.2 336.7 160 416.2 407.8 398.9 389.4 379.9 370.5 361.8 353.5 345.2 170 421.3 413.1 404.6 395.6 386.5 377.6 369.3 361.5 353.4 180 426.4 4Z8.5 410.3 401.6 393.0 384.6 376.7 369.0 36Z.5 190 431.6 423.9 4Z6.1 407.9 399.5 39Z.6 384.0 376.8 369.5 200 436.8 429.4 421.8 413.7 405.9 398.Z 39Z.2 384.2 377.3 210 442.1 434.9 427.6 420.0 4Z2.3 405.0 398.3 391.5 385.0 220 447.4 440.4 433.4 425.9 418.7 411.8 405.3 398.9 392.6 230 452.8 446.0 439.3 432.0 425.1 418.4 4Z2.3 406.2 400.1 240 458.2 451.7 445.1 438.3 431.5 425.0 419.2 4Z3.4 407.6 250 463.7 457.3 451.0 444.4 437.9 431.7 426.1 420.4 414.9 260 469.3 463.1 456.9 450.5 444.2 438.4 432.9 427.5 422.3 270 474.9 468.8 462.9 456.6 450.6 445.2 439.7 434.7 429.5 280 480.5 474.6 468.9 462.9 457.0 451.5 446.6 441.5 436.7 290 486.2 480.5 474.9 469.2 463.4 458.4 453.4 448.7 443.9 300 491.9 486.4 481.0 475.0 469.9 464.8 460.2 455.8 451.1

In the previous report difficulty in reconciling the enthalpy traverses across the two-phase region at 500 and 700 psia with the rest of the enthalpy data was encountered. The enthalpy difference across the two-phase region at these pressures was 5 to 6 percent high. In reworking the data, arithmetic errors were found in the tabulations of enthalpy differences for these two pressures and the corrected data were found to be consistent with the other enthalpy data. As in the case of the nominal 12 percent mixture, the data were extended domwn to -280~ F by extrapolation and up to +3000 F by blending the experimental heat capacities with those calculated from the B-W-R equation of state. Nominal 43 Percent Nitrogen in Methane Mixture A skeleton enthalpy table and a pressure-enthalpy-temperature diagram for this mixture have been prepared. The following procedure was used in preparing the table and diagram: 1) Reference states of 0 Btu/lb were taken to be the pure components as saturated liquids under their own vapor pressure at -280 F. 2) The enthalpy of pure methane as a gas at zero pressure and 100 0F was calculated using the data on the heat of vaporization at 5 psia of Frank and Clusius, the B-W-R equation of state to correct from 5 psia to zero pressure and values of the ideal gas heat capacities from Rossini161 The enthalpy of methane at 100 F and zero pressure was found to be 421.97 Btu/lb. 3) The enthalpy of pure nitrogen as a gas at zero pressure and 100 F was calculated using a value of the latent heat at 111 psia (-280 F) from Bloomer and Rao15, data from their report for the enthalpy difference between 111 psia and zero pressure and values of the ideal gas heat - 126 -

161 capacities from Rossini. The following results were obtained: Enthalpy, Btu/lb Latent heat of vaporization at -280~ F 69.45 Effect of pressure on enthalpy (0 to 111 psia) 7.08 Ideal gas enthalpy (-280~ F to 1000 F) 94.36 170.89 (The B-W-R equation gave 7.46 Btu/lb for the effect of pressure on enthalpy) 4) The enthalpy of the methane-nitrogen mixture at zero pressure and 100 F was calculated assuming zero heat of mixing. Hmix = 0.5725 (170.89) + 0.4275 (421.97) = 278.23 Btu/lb 5) The isothermal effect of pressure on enthalpy at 100 F was estimated using the B-W-R equation of state with constants for nitrogen given by Stotler and Benedict 9 and the mixing rules originally pro11 posed by Benedict, Webb, and Rubin. 6) The isobaric effect of temperature on enthalpy was determined in the gaseous, two-phase, and liquid regions using the data of this work. The phase boundaries were determined using results of traverses made during this research, together with data from Bloomer and Parent14 and Cines et al. 29 7) A smooth plot of the results was prepared and is shown in Figure 39. The values of enthalpy are given in Table XXX. These values are compared with results of calculations using the B-W-R equation of 161 state combined with enthalpy data of Rossini at zero pressure in Table XXXI. The agreement between the calculated and experimental en- 127 -

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(aan~paadwaj moq) banlxxi 4uuDaJd iIt Teu-ruwoN aq4 aoj wpa d-~y~~-rnPTG a~-a~s.T n6 am~ij (e-i/nie) )w-1vliN ooz 061 081 OLI 091 091 Ot~l 021 OZ I 01 I 001i 06 08 OL 09 09 OV 02 OZ 01 0 001 i_.. 1 ~~~~~~008 I:: Irl~~~~~~~~~~~~~~IJ I~~~~~~~~~~~~~~~~~~I xLL 5 I~~~~~~~~~~~~~~~~~~~~~~~~~~~~L 'U ~~~~H 00V.-7.IYI.-.h 7- 5. *416- -7 -+t001 IL T -- ~ ~l-;;:"I CCC I+ CI 3 i - -------- 0 I r- r~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ i r~~mT~~;TT-;TiT:~~~~1TR~~.T- --- - _7 I 3_731l Hlri -- min~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~:T~~~~~~~~~~~l 7 -10IN~~~~~~~~~~~~~~~~~~~~~~~~ -tt — l$-+~-)itSttt m~~~~~~~~~~~~~~~~~~~~~~~01 I-r ~ ~ ~ ~ ~ - I~~~~0 U A _A_-1-t-t — ~~ — r — R — ii- 00 -1 rW W P IQ " Li- -O i W~L - I ) ) -.- U IU C rC~)r70 9 0 0 -. OOO O -1 ~JO O O O I IW- IQO Q 4- ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 3 M co r~~~~~~~~~ rv T4.L~,~I co C~~~~~~~~~~~~~~~~~~~~~~~~~ N 0091~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ ~-; o CD.~~~~~~~~~~~~~~~~~~~~~~~~~~~~0 0 0 -0~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~..i.1.1.;.L111

- 130 - TABLE XXX TABULATED VALUES OF ENTHALPY FOR THE NOMINAL 43 PERCENT MIXTURE Temperature, ~F Saturated Saturated Latent Heat of Pressure Bubble Dew Liquid Enthalpy Vapor Enthalpy Vaporization Point Point (Btu/lb) (Btu/lb) (Btu/lb) 100 -268 -225 8.8 152.5 143.7 200 -243 -202 27.5 154.9 127.4 300 -224 -186 41.0 154.1 113.1 400 -208 -175 53.4 152.0 98.6 500 -197 -166 65.0 149.7 84.7 600 -184 -157 76.0 147.0 71.0 700 -171 -152 92.0 138.5 46.5 H (Btu/lb) Temperature Pressure, psia (~F) 0 250 500 750 1000 1250 1500 1750 2000 -280 142.0 4.2 4.6 5.3 5.9 6.7 7.Z 7.7 8.3 -270 145.5 30.5 Z0.9 ZZ.5 Z2.0 Z2.5 Z3.1 33.5 Z4.3 -260 149.1 36.8 Z7.3 Z7.7 Z8.3 Z8.8 Z9.2 Z9.8 20.3 -250 152.6 23.0 23.3 23.8 24.3 24.8 25.4 25.9 26.3 -240 156.1 29.2 29.7 30.Z 30.5 3Z.0 31.7 32.Z 32.5 -230 159.7 38.2 37.0 37.3 37.4 38.0 38.1 38.5 38.8 -220 163.2 66.9 43.9 44.0 44.3 44.5 44.7 44.9 45.1 -210 166.8 93.9 5Z.3 5Z.2 51.2 5Z.3 51.4 5Z.4 51.5 -200 170.3 Z26.4 60.0 58.3 58.3 58.2 58.2 58.2 58.1 -190 173.9 Z55.6 82.2 66.Z 65.7 65.5 65.2 65.0 64.8 -180 177.4 162.0 Z08.6 76.8 73.8 73.0 72.5 72.0 71.6 -170 180.9 Z67.4 140.6 90.2 83.0 8Z.0 80.2 79.Z 78.5 -160 184.5 172.0 Z54.Z 3Z3.l 94.2 90.3 88.2 87.0 85.7 -150 188.0 176.4 Z6Z. Z Z35.0 108.0 99.4 96.9 94.7 93.1 -140 191.6 180.7 167.6 Z49.4 122.1 ZZ0.4 106.2 Z03.3 100.8 -130 195.1 184.9 Z73.Z 158.4 136.1 Z22.7 115.9 ZZZ.4 108.7 -120 198.7 189.1 Z78.8 Z65.0 148.3 Z34.7 125.6 Z20.2 116.8 -110 202.2 193.1 Z83.2 Z72.0 157.9 Z45.Z 135.3 Z29.3 124.9 -100 205.8 197.2 Z88.2 Z78.Z 165.9 Z54.0 144.6 Z38.0 133.1 -90 209.3 201.2 192.8 Z83.2 172.8 162.2 153.3 Z46.7 141.1 -80 212.9 205.2 197.4 Z88.5 179.1 Z69.5 161.3 Z55.3 148.9 -70 216.5 209.1 201.8 Z93.4 185.0 Z76.2 168.6 Z62.4 156.5 -60 220.0 213.1 206.2 Z98.6 190.6 Z82.6 175.4 Z69.5 163.7 -50 223.6 217.0 210.5 203.5 195.9 Z88.3 181.9 Z76.4 170.7 -40 227.2 220.9 214.7 207.8 201.1 Z94.Z 187.9 Z82.8 177.4 -30 230.8 224.8 218.8 2Z2.4 206.1 Z99.8 193.7 Z88.9 183.8 -20 234.3 228.6 223.0 2Z7.Z 211.0 204.8 199.3 Z94.5 189.9 -10 238.0 232.5 227.1 22Z.5 215.8 209.9 204.8 200.0 195.9 0 241.6 236.3 231.1 225.9 220.5 2Z5.0 210.1 205.6 201.6 10 245.2 240.1 235.2 230.2 225.1 2Z9.8 215.3 2ZZ.2 207.1 20 248.8 244.0 239.3 234.5 229.7 225.2 220.4 2Z6.5 212.5 30 252.5 247.8 243.3 238.7 234.2 229.5 225.4 22Z.5 217.8 40 256.1 251.6 247.3 242.8 238.6 234.0 230.3 226.2 223.0 50 259.7 255.5 251.4 247. 243.0 238.9 235.1 23Z.5 228.1 60 263.4 259.3 255.4 25Z.2 247.4 243.4 239.9 236.Z 233.1 70 267.1 263.1 259.4 255.4 251.7 247.9 244.5 24Z.4 238.0 80 270.8 267.0 263.3 259.6 256.0 252.4 249.1 246.0 242.9 90 274.5 270.9 267.3 263.7 260.3 256.9 253.7 250.8 247.7 100 278.2 274.7 271.3 268.0 264.5 26Z.4 258.2 255.4 252.5 110 282.0 278.6 275.3 272.Z 268.8 265.6 262.7 260.2 257.2 120 285.7 282.5 279.2 276.2 273.0 270.0 267.Z 264.8 26Z.9 130 289.5 286.4 283.2 280.Z 277.2 274.2 27Z.6 269.3 266.5 140 293.3 290.3 287.2 284.4 281.4 278.8 276.0 273.6 27Z.Z 150 297.1 294.2 29Z.2 288.Z 285.6 283.0 280.4 278.2 275.7 160 300.9 298.0 295.2 292.4 289.8 287.3 284.8 282.5 280.3 170 304.7 30Z.9 299.2 296.8 294.0 291.7 289.2 287.0 284.9 180 308.6 305.9 303.3 300.7 298.2 296.0 293.6 29Z.4 289.4 190 312.4 309.8 307.3 304.8 302.5 300.2 298.0 295.8 293.9 200 316.3 3Z3.8 3ZZ.3 309.Z 306.7 304.6 302.3 300.4 298.5 210 320.3 3Z7.8 3Z5.4 3Z3.Z 3Z0.9 308.8 306.7 304.7 303.0 220 324.2 32Z.8 3Z9.5 3Z7.4 3Z5.Z 3Z3.Z 3ZZ.Z 309.3 307.5 230 328.1 325.8 323.6 32Z.5 3Z9.3 3Z7.5 3Z5.5 3Z3.9 3Z2.0 240 332.1 329.9 327.7 325.6 323.6 32Z.7 3Z9.8 3Z8.0 3Z6.5 250 336.1 333.9 33Z.8 329.7 327.8 326.Z 324.2 322.6 320.9 260 340.1 338.0 335.9 334.0 332., 330.4 328.6 327.0 325.4 270 344.1 342.Z 340.Z 338.3 336.4 334.6 333.0 33Z.5 329.9 280 348.2 346.2 344.3 342.5 340.7 339.0 337.4 335.8 334.4 290 352.2 350.3 348.4 346.5 344.9 343.3 34Z.8 340.5 338.9 300 356.3 354.5 352.6 35Z.0 349.3 347.7 346.2 344.9 343.4

thalpies is within one percent at temperatures as low as -1000F. Below this temperature significant deviations are noted, especially at elevated pressures. TABLE XXXI COMPARISON OF ENTHALPIES PREDICTED BY BWR EQUATION OF STATE WITH EXPERIMENTAL RESULTS DATUM: H = 0 for saturated liquid methane and saturated liquid nitrogen at -280~F H T P (Btu/lb) (OF) (psia) BWR Experimental 100 250 274.7 274.7* 50 250 255.6 255.5 0 250 236.4 236.3 - 50 250 217.7 217.0 -100 250 197.3 197.2 -150 250 176.0 176.4 -200 250 150.6 126.4 -250 250 4.6 23.0 100 500 271.3 271.3* 50 500 251.3 251.4 0, 500 231.2 231.1 - 50 500 210.3 210.5 -100 500 187.7 188.2 100 1000 264.5 264.5* 50 1000 243.0 243.0 0 1000 220.5 220.5 - 50 1000 195.7 195.9 -100 1000 164.7 165.9 -150 1000 104.5 108.0 -200 1000 55.2 58.3 -250 1000 6.4 24.3 100 1500 258.2 258.2* 50 1500 235.1 235.1 0 1500 210.1 210.1 - 50 1500 181.3 181.9 -100 1500 142.8 144.6 -150 1500 95.9 96.9 -200 1500 55.9 58.2 -250 1500 8.1 25.4 100 2000 252.5 252.5* 50 2000 227.9 228.1 0 2000 201.1 201.6 - 50 2000 169.8 170.7 -100 2000 132.1 133.1 -150 2000 93.9 93.1 -200 2000 56.7 58.1 -250 2000 9.6 26.3 * Isotherm at 100~F is the reference line. 131 -

Comparison of Methane-Nitrogen Mixture Enthalpy Data In the methane-propane system the two-phase region covers a large portion of the experimentally accessible P-T surface and comparisons of enthalpies as function of composition are difficult because one component is a liquid and the other is a gas under most conditions. With the methane-nitrogen system, however, most of the data are obtained in the gaseous region and comparisons where all mixtures and the pure components are gaseous are possible. The heat of mixing or excess enthalpy for the nominal 43 percent mixture was calculated at high pressures from the data of Table XXX together with the methane data of Jones and the nitrogen data of 120 Mage. The heats of mixing are presented in Figure 40 as a function of temperature. It can be seen that in the region above the critical point large deviations from ideal mixing exist. Also shown in this 188 Figure are the heat of mixing data of Van Eijnsbergen, directly determined using a flow calorimeter. The agreement is very good except at the highest temperature. Here the values calculated from mixture and pure component data may be in error because of the small differences between large numbers which are involved. A comparison can be made with other enthalpy data on the methanenitrogen system. Isothermal enthalpy changes at low and high temperatures and isobaric enthalpy changes at low and high pressure were selected as representative checks of the data of this work with other published data. The isothermal comparisons at -100 F and 100~F are shown in Figures 41 and 42. The isobaric comparisons at 500 psia and 1500 psia are shown in Figures 43 and 44. Straight lines joining the pure component values on this type of graph define ideal mixing [the excess - 132 -

25 P= 1000 psia 20 Mole Fraction Nitrogen-.434 Mole Fraction Methane-. 566 15 P-| \O P 1500 psia 10 / -J. 5' 0 -* Von Eijnsbergen (1966) I I I I I I I I -280 -240 - 200 -160 - 120 -80 -40 0 40 TEMPERATURE OF Figure 40. Heats of Mixing at High Pressure

- 134 - 700 - AHT(O to 500 Psia) Temperature - 100 ~ F * This Work o Bloomer efa/.(1955) 600 0 Jones (1961) 0 Bloomer & Rao (1952) v Matthews & Hurd (1946) A Bolshakov et a/. (1967) v Tester (1961) Din (1961) + Mage (1964) J _~ 400 -Ideal Mixing <I 300 - 200 0 0.2 0.4 0.6 0.8 MOLE FRACTION NITROGEN Figure 41. Isothermal Enthalpy Comparison at Low Temperature

700 AHT ( to 1500 Psia) Temperature +100~F 600 - 0 This Work O Bloomer etal (1955) v Matthews a Hurd(1946) O Bloomer & Rao (1952) W \ \ v Tester (1961) o 500 A Din (1961) IJ INm \ \Ideal Mixing 400 - 300 0 0.2 0.4 0.6 0.8 MOLE FRACTION NITROGEN Figure 42. Isothermal Enthalpy Comparison at High Temperature

1100 Pressure 500 Psia 4 {~~~~~~~~* ~This Work 0wz 0 Bloomer eta! (1955) 0 Bloomer & Rao (1952) O Jones (1961) -IOO- \ 000F to 00F V Matthews 8 Hurd (1946) _. sj \ 0 \ A Bolshakov eta/ (1967) w _ V Tester (1961) 0 E Ideal Mixing A Din (1961) ' + 9Mage (1964) O~F to+10 _ \ | aII MIdeal Mixing a 800 - 0 0.2 0.4 0.6 0.8 1.0 MOLE FRACTION NITROGEN Figure 43. Isobaric Enthalpy Comparisons at 500 psia

- 137 - 2100 2000 \\o Pressure 1500 Psia 1900 - \ This Work o Bloomer et oa. (1955) \O Jones (1961) 1800 0 Bloomer & Rao (1952) + Mage (1964) 1700 \ \-100~F to 0F v Matthews a Hurd (1946) \ o \ v Tester (1961) A Din (1961) 1600 - -j 0 2 1500 -Ideal Mixing m 1400 -<i 1300 120 0 11 Figure 44 Enthapy Comparisons at 00 psia I000 -0 to +100 OF 900 -0 0.2 0.4 0.6 0.8 1.0 MOLE FRACTION NITROGEN Figure 44. Isobaric Enthalpy Comparisons at 1500 psia

enthalpy, Equation (19), is zero]. The lines showing actual mixing are biased to include the nominal 43 percent nitrogen mixture and the points for methane of Jones and nitrogen of Mage if these were 18 available. It can be seen that the data of Bolshakov et al. are not in agreement with the present work and the tabulation of Bloomer et al.16 is in fair agreement. The values for methane from the three tabulations are in poor agreement with discrepancies as high as 7 to 10 percent. It appears that more work on methane to resolve these discrepancies would be desirable. Vapor-Liquid Equilibria In the course of measurements across the two-phase region, it is possible to obtain estimates of the bubble and dew points from abrupt changes in the curvature of a plot of energy added versus temperature like Figure 8. Table XXXII compares the results for the three methanepropane mixtures and the methane-nitrogen mixture with data from the literature. TABLE XXXII COMPARISON OF PHASE EQUILIBRIA OBTAINED FROM ENTHALPY TRAVERSES WITH VAPOR-LIQUID EQUILIBRIUM DATA Methane-Propane a) Nominal 5% Propane Mixture Bubble Point Dew Point (OF) (OF)Price and Price and Pressure Manker Kobayashi Manker Kobayashi (psia) 250 -166 -167 -58 -61 400 -142 -143 -50 -50 500 -128 -130 -42 -44 600 -117 -118 -39 -41 650 -112 -113 -39 -40 800 - 96 - 97 -38 -40 - 138 -

b) Nominal 12% Propane Mixture Pressure Bubble Point Dew Point (Psia) (OF) (OF) Price & Price & This work Kobayashi This work Kobayashi151 500 -123 -124 3 - 2 800 - 89 - 88 10 10 1000 - 66 - 64 11 7.5 c) Nominal 28% Propane Mixture 500 -111 -116 59 54 700 - 83 - 87 72 69 1000 - 46 - 47.5 79 83 Methane-Nitrogen, a) Nominal 43% Nitrogen Mixture Bubble Point Dew Point (OF) (OF) Pressure This work Bloomer & This work Bloomer & (psia) Parent14 Parent14 250 -231 -232 -191 -196 400 -208 -208 -176 -177 600 -183 -183 -157 -163 It can be seen that, in general, the direct vapor-liquid equilibrium measurements and the values derived from the enthalpy traverses agree 120 within a few degrees. Mage also found this to be the case with the dew points of the helium-nitrogen system. Heats of Vaporization In many instances the latent heat of vaporization comprises the major portion of a particular heat duty. It is important then, to be able to estimate values of the integral isobaric heat of vaporization accurately Manker123 accurately. Manker compared the latent heats determined on the nominal 5 percent mixture and concluded that the method of Peters1 gave the best estimates of the latent heat. A number of the methods for estimating enthalpies in Table II and specifically those intended 139 -

for latent heats were used to compare with the experimental results for the methane-propane and methane-nitrogen mixtures. The results are compared in Table XXXII and it is seen that the method of Peters appears to predict the trend of latent heat with pressure reliably. Values calculated by the method of Stevens and Thodos for the nominal 12 percent mixture appear to be badly in error. The method of Edmister, although specifically derived for hydrocarbons, gives reasonable results for the methane-nitrogen mixture. No method of predicting the isobaric latent heat compared here is completely satisfactory and further work in this area of prediction is necessary. - IlO -

TABLE XXXII I CALCULATED AND EXPERIMENTAL ISOBARIC HEATS OF VAPORIZATION 49 13 145 This Work Stevens Scheibel Edmister Maxwell anjar Peters145 & Thodos76 & Jenny167 & Peterka a) Nominal 12 Percent Propane in Methane Pressure (psia) 500 200 173 245 229 196 222 203 800 173 73 205 188 162 161 165 1000 111 46 170 174 142 163 122 b) Nominal 28 Percent Propane in Methane 500 227 214 245 244 208 237 214 700 196 187 222 207 200 218 200 1000 153 142 180 172' 182 181 166 c) Nominal 43 Percent Nitrogen in Methane This work Edmister49 Curl & Pitzer Yen 250 120 126 118 115 400 99 102 95 108 600 71 89 61 36 - 141 -

Summary and Conclusions 1. The recycle system originally designed by Faulkner was modified to allow measurements under conditions different from those for which the equipment was designed. 2. Isobaric data on the effect of temperature on enthalpy were obtained for nominal mixtures of 12 percent propane in methane, 28 percent propane in methane, and 43 percent nitrogen in methane. These data cover the liquid, two-phase, and gaseous regions at temperatures from -240 F to +140 F at pressures from 250 to 2000 psia. 3. Skeleton enthalpy tables and enthalpy-pressure-temperature diagrams for those three mixtures were prepared using supplemental data from the literature. 4. An isothermal throttling calorimeter for the direct determination of the effect of pressure on enthalpy was designed, fabricated, and tested. 5. Measurements of the effect of pressure on enthalpy were made on nitrogen at -147 F, 330F, and 201 F at pressures from 2000 to 100 psia. The data are in fair agreement with literature values, considering that the disagreement among the literature values is up to 4 percent. 6. Measurements of the effect of pressure on enthalpy were made on a nominal mixture of 5 percent propane in methane at -147 0F, -270F, 93 F, and 200 F. Isobaric experiments were also made on this mixture to extend the data of Manker from 70 F. to 250 F. 7. A skeleton enthalpy table and an enthalpy-pressure-temperature diagram for the nominal 5 percent mixture covering the range -280 F to +300 F at pressures up to 2000 psia was prepared which is based almost entirely on direct experimental determinations.. )4

Recommendations for Future Work 1. The Roebuck pressure balance should be replaced with transducers to allow more accurate readings of the pressures and pressure drops and eliminate the problem of fluid of variable density and composition in the lead lines. 2. The substitution of electrical measurements for mechanical devices in the flow rate and pressure drop determinations to eliminate water and mercury from the system and improve the precision of the measurements is recommended. 3. Use of an automatic controller on the electrical energy input to the guard heater of the isobaric calorimeter and the energy input to the isothermal throttling calorimeter would facilitate precise control in these variables and minimize corrections to the data. 4. A Joule-Thomson device should be constructed to provide an independent check on the data of this laboratory. 5. Numerical techniques for the smoothing and interpolation of the data should be developed to minimize the time spent in working up of data into tables and charts. When data for the complete composition range of the methane-propane system become available, tables and diagrams smoothed with respect to composition, temperature, and pressure should be compiled. At this time, the basis for enthalpy should be changed to the pure components as perfect crystals at O0K. 6. A thorough study of the prediction methods for thermodynamic properties should be made with the goal of devising a new method with improved accuracy. Data of the type presented here will be useful in developing and testing such a new correlation method. 143 -

APPENDIX A CALORIMETER DRAWINGS - 1144 -

TOP VIEW OF TOP VIEW OF TOUP~PVIEWR POFRTION LOWER PORTION UPPER PORTION THERMOCOUPLES MAIN SOFT THERMOCOUPLES SOLDER 1. Inlet Thermowell 10 SOLDER 2. Outlet Thermowell 3. Exit Tube A 4. Baffles --— =, 7 i 5. Exit Tube B GYROLOK BUT 6. Radiation Shield WELD ELBOWS1 7. Conax Seal 4-LBW2-316 21/32DRILL THROUGH 1/32 DRILL THROUGH 9. Upper Case FIRST HOLE 1/8 FROM i EInr Tb B LOSEL END ' 9 - 10. Cover 20ance Tube A ' 21. VSocuum Line e f I..13 Spherical Cap WAEK 14. Extension 15. Baffle Mount 16 1/32 DRILL 16. Lower CaseS THROUGH ISOTHERMAL I7. a J L 1S H1 X r 1n THROTTLING CALORIMETER 5 HOLES 3/32 ~~~17. ~ Temperature Compensation Coupling a~2,~PCSPACING FIRST 18. Thermal Equalization Block HOLE FRrimeter 19. Entrance Tube B 20. Entrance Tube A 21. Socket Weld Tee 6 C~ I ~ tli.6 SWAGE LOK TO SOCKET WELD UNION 600-6-6SW- 316 ISOTHERMAL THROTTLING CALORIMETER ALL FABRICATION SYMBOLS ASSEMBLY DRAWING UNLESS OTHERWISE FULL SIZE SPECIFIED......... A. E. MATHER 1 8 JULY, I967 Figure 45. Assembly Drawing for Isothermal Throttling Calorimeter

- 146 - '43(0.089) DRILL D12 HOLES EQUALLY SPACED I/S 18 4 47// 32 1/8//'x/xxxxx/// -I 3 - I/ DIA PINS (347 S. S. ROD) LOWER CASE 304 SS. Figure 46. Detail Drawings for Isothermal Throttling Calorimeter

//8 DRILL 1/4 DRILL 13/16 1/2DRILL SLIP FIT 81/2 4 5/8 DILA. -~~~r 4 '~U 1 m u J ~3/16 4 - 1/16 DIA. PINS RADIATION SHIELD.02 COPPER SHEET CHROME PLATED Figure 46. Detail Drawings (Continued)

- 148 - 643(0.089) DRILL #4-40NC-2 8-HOLES EQUALLY SPACED ADPE A 6"DRILL 3 /16./SSHOW N IN i 76I5 R1/8{IA 5 — 3 /4 Scole 4:1 ~~~~~~~~~3(11/16 0 DRILL 3/16 304 S. S3 Figure 46. Detail Drawings (Continued) Figure 46. Detail Drawings (Continued)

3/8 DIA. REF FIT TO TUBING / 31 (0.120) DRILL 8 HOLES EOUALLY SPACED 3/16 x.028 _- \ 1 9/16 ot~~~~Z~ tX ~~~~~~~WALL TUBING i/lr.2 - 2 1 f 1 I /ID 71il F,4z~,~ —,~/ - -3' - - 37../32 DIA /11/DID6SCALE: Double SRze COVER 1/1 0Cb 304 SS. Scale 4:1 OUTLET THERMOWELL 304 S.S. 1 REQ'D 1/8 3 3/8 R DIA3 TEFLON 12 REQ'D NOTE TRUE POSITION OF 7A. REF 7/16- 3/8 HOLES 3/16 x.028 SCALE: DoFIT TO A TEFLON I/// REO'D 20 4-40ONC-2 x 5/8 SOCKET HD. CP SCR (S. STEEL) INLET THERMOWELL 304 SS. REQ' D Figure 46. Detail Drawings (Continued) Figure 46. Det~~~~~~~~~~ ai Dr wig (Cntiud

- 150 - SOLDER LAST TURN OF TUBING TO SPACER GYROLOK - PLUG SOLDER NICHROME WIRE NICHROME WIRE 3P-316 TO SPACER AFTER IT TO EXTEND 1 INCH LEAVES CAPILLARY COIL 10 FEET OF TUBING MNMMFONU ON 7/16 MANDREL REQ'D 1 4-40NC-2x 1/4 ON 7/16 MANDREL BRASS ROUND HD. MACH SCR. NUT -316- S. S.~ 3_ -Q D 1 367/16 - NO 2E:NICHROM E '/2 — AND S1/32 L 43 (0.089 DRILL) DRILL PLUG 1 4-40 NC-2 AND SILVER 9I6lV SOLDER TUBING 5 V/2 SCALE: Double Size SPACER BRASS 1 REQ'D CAPILLARY NO. TUBING WIRE TUBING-304 S.S GAUGE GAUGE NUT - F316 S.4S. 3 REQ'D 1 17 BWG 36 B&S NOTE: NICHROME WIRE TO BE 2 16 BWG 36 BS INSERTED IN TUBING AFTER 3 19 BWG 36B&S SILVER SOLDERING BUT BEFORE FORMING COIL 1/8 15/R 90 36 ---- 3/B DIA. 3/16 R 304 S.S. TUBING 1 REQ'D 3/BOIA EXIT TUBE A EXIT TUBE B 304 S.S. 1 REO'D Figure 46. Detail Drawings (Continued)

NOTE: INTERNAL THREADS OF BAFFLES ARE NF (SHALLOW) WITH 40 THREADS/INCH TO FIT MALE SECTION OF BAFFLE MOUNT O.750D1. 0.875DIA 1.000 IOODIA. 0.710 0.835 0.960 1/4 7/32 7/32 7/32 5/8 12- 1/16 HOLES EQUALLY SPACED 12-1/16 HOLES EQUALLY SPACED 6 5/32 5 25/32 5 31/32 5/32 HOLE/ BAFFLES 1-3 COPPER Scale: Double Size Figure 46. Detail Drawings (Continued)

152 CONAX POWER LEAD PRESSUR SEAL PL-18-AI 303 S. S. SO WRENCH PLAT SEATS ON rEE MACHINE TO LENGTH SHOWN 113/32, CAJON SOCKET WELD TEE 63SW-3-304L / 2 ~371/20~~~~~~~~~~~1/32 R5PtI/2~ SCOIB 4:1 s/16 O 1/32 ~304 /2S. 1 f I0 PIPE~ ~3/8 DIA. ENTRANCE T UB E EXTENSION J -o -,or- -A 304 S.s. TUBING REEQ 'D 304 S. S. Detai Drawings 'D 1/16Continu 7 1/2' Scale 4'1 RSP 5/16 FIT TO TUBING 304 SS. TUBING I REQ'D Figure 46. Detail Drawings (Continued)

- 153 - #25(0.1495) DRILL 1/8 DIA. COPPER PEG ' PRESS FIT 3/8 II3 7/8 DIA ---~S,,.730- - 5/8B 1 /80 1/32 THERMAL EUALIZATION BLOCKBAFFLE MOUNT COPPER 1 REQ'DQ' 0.85536 (0.1065) DA.LL r'- 1.097 DIA. ~ Scale: Double Size f 1- I — I BAFFLE MOUNT 304 S.S. 1 REQ'D #36 (0.'065)DRILL 6 -32 NC-2 5/32 MOUNT BRASS ROD 1 REQ' D /MACHINE THREADS SO CONNECTOR CAN BE INSERTED 5/32 INTO MOUNT GYROLOK MALE CONNECTOR MACHINE FEMALE FLANGE TO LENGTH SHOWN 3 CM2-316 (LESS NUT) 27/32 FEMALE FLANGE-TEMPERATURE COMPENSATING COUPLING DS.D. -A-P-10-16 304 S.S. Figure 46. Detail Drawings (Continued)

APPENDIX B CALIBRAT IONS - 154 -

TABLE XXXIV MAIN THERMOPILE CALIBRATIONS T EMF (~C) (microvolts) Isobaric Calorimeter Isothermal Calorimeter G-32321 G-36972 A G-36972 C -196 -33342 -195 ---- -33239 -33275 -183 -32018 -31988 -32018 -120 -23626 -23616 -23616 -100 -20347 -20340 -20336 - 80 -16786 -16782 -16772 - 60 -12962 -12958 -12946 - 40 - 8880 -8878 - 8868 -20 - 4557 -4556 - 4550 0 0 0 0 + 20 4772 4776 4771 40 9760 9764 9752 60 14947 14949 14933 80 20326 20328 20302 100 25882 25880 25855 120 31612 31606 31578 140 37501 37498 37464 150 40508 40504 40468 - 155 -

TABLE XXXV CALIBRATION OF HIGH PRESSURE GAUGE H-41060 Actual Pressure Heise Gauge (psi) Up Down 100 97 98 200 198 199 300 298 298 400 398 398 500 497 498 600 598 599 700 698 698 800 799 799 900 899 899 1000 999 999.5 1100 1099 1100 1200 1198.5 1199 1300 1299.5 1300 1400 1400 1400 1500 1500 1500 1600 1600 1601 1700 1701 1702 1800 1801 1801 1900 1902 1902.5 2000 2002 2002 - 156 -

TABLE XXXVI CALIBRATION OF DEAD WEIGHT GAUGE Type Mansfield and Green, Model 26 Q Serial No. 1707 Nominal Pressure True Pressure Percent (psi) (psi) Deviation 200 200.03 +.016 400 400.07.017 600 600.10.016 800 800.13.017 1000 1000.14.014 1200 1200.16.014 1400 1400.19.013 1600 1600.21.013 1800 1800.22.012 2000 2000.23.011 2200 2200.24.011 2400 2400.24.010 2600 2600.25.009 - 157 -

TABLE XXXVII FLOW METER CALIBRATION DATA FOR THE NOMINAL 5 PERCENT MIXTURE r(lEFFICIENTS OF PCWEP SFRIES B =.1429332E+CC A ---.182E46EE+C2 C = -.25382477E+C4 = -.';"72631c94E+0O6 F/1 E- (Experimental) _ ____.121P071F-C2?.1238 cEo. 1382 CCE+O.14C7fS4E+CO.1CC71255E-02.1206742EE+CC.12CE774SE+CC. 1CC7323CE-02.12C71i11E+CC.12CEEC53E+CC.144PE375E-02.1275747EE+CC.12766827E+CC.16C74577E-C2.129$462EE+CO.1.-01462CE+CC.16CS4896E-02.12PE888CE+CC.1C 17822E+CC.17286645E-02.13194371E+OC.1?2C7145E+00.12152859E-C2.12371387F+CC.124C7147E+CO.4C525619E-03.1115714CE+00.1113355CE+CC.40631 17E-C3.11145261E+OC.11 13313E+CC. 805c5C8E-C3.117877C4E+00C.117748SE+CC.8C34469CE-03.11793558E+CC.11772372E+CC.1 224C88F-02.12525354E+CC.1251C153E+C0.15,47820F-02.13CC8E84EE+O 15S78940E+CO.1c155q83E-C2.1352835E+CC ' 13511423E+CC.19117513E-C2.135C5512F+00.-; —C5015E+CC.21383972E-C2.13868C4:E+CC.138E924SE+OO.21423645E-C2.13R88C2EE+CC.1 —8S6153E+CC.4C525620F-03.11144223F+CC.1113355CE+CC ~ 4C631 '53 E-C3. 1 1Ce222E+CC i1135313E+CC. CC5CllE-C3.117 5274E+CC 117i4e SE+CC.80344694F-C3.11763(45E+CC.11772372E+CC.12824Ce8F-C2.124q$732E+OC.1510C153E+CO. 18-47P21F-C2.12$8116CE+OC.12c 784CE+CO _..... ~.-.:: i:_. _:. 62634C65F-C3.115144C 1E+CC 1142c5BEE+ CC. -2?55376E-C3.115C3828E+OC.114C17C2E+CC ~95'C63S43E-C3.1202C746E+CC.120C072EE+CC.94$$7649F-03.12021732F+OC.11SCS7C6E+CC.14426247E-02.12774611E+OC.121771 S7E+CG.14425444E-02.1277CS11E+OC.12757072E+CC ~ 18097748 E-02.1334S18 E+C0.1333795CE+OO.1 E0732 87F-.2.13348;56E+CC.13333,7-E+CC ~ 20287652E-C2.13705551E+O0.1. 7010C1E+CC.202C8159E-C2.137C 3207E+CC,1'6 E7534E+OC.a..A GE DEVIATION =.17 PERCENT

.140 Oc.130... |Methane- Propane my: |8~ /r-i~~~~~~ 1Nominal 5%/o Mixture <zILLeta~~~~~~.120 /o March 1,1967 o March22,1967 A April 21,1967.110 0 / 4 6 8 10 12 14 16 18 20 22 F.104 l(b/min XL nmicropoise Figure 47. Flow Meter Calibration for Nominal 5 Percent Mixture

- 160 - TABLE XXXVIII FLOW METER CALIBRATION DATA FOR THE NOMINAL 12 PERCENT MIXTURE COEFFICIENTS OF POWER SERIES B =.1C386 161E+OC A =.16766623E+02 C -.13278800E*04 D =,.38507479E+06 F/P pP (Experimental) A (Calculated).18039820E-02. 13193017E+00.13204760E+00 i8p54526E-02'.13192652E+00.13207074E+00 15,907 346E-0 2.12858312E+00.12872276E+00.1380835SE-02.12529S27E+00.12549553E+00.13,804297E-02.12534351E+00.12548931E+00.6,8974 047E-03.11506218E+00.11492086E+00.68961348E-03.11501919E+00.11491889E+00.9,2717181E-03.11862950E+00.11857256E+00.9,2650254E-03. 11864523E+00.11856232E+00.571184905E-03.11213967E+00.11214734,E+00.9f3095375E-03.11815414E+00.11863041E+00.93204147E-03.11871489E+00.11864705E+00.13,906675E-02.125670C9E+00.12564600E+00.13/896230E-02.12568149E+00.12563001E+00 16,44788SE-02. 13016168E+00.12956028E+00.6,0830 638E-03.11338979E+00. 11365617E+00.6r0905811E-03.11350080E+00.11366788E+00 *112.14573E-02.12137351E+00.12153775E+00.11217180E-02.12145351E+00.121,54172E+00..15,131303E-02.12767217E+00.12752548E+00 15178077E-02.12744414E+ 00.12759749E+00.14944095E-02.13024351E+00.13033203E+00 ~1893985 5E-02. 13340699E+00.13347023E+00.18,942446E-02.13346861E+00.13347434E+00 *5.8222119E-03.11324685E+00 ~1329337If+00 _a2Z394 8E_03 _.11332691E+00.11324653E+O0 79914694E-03.11685977E+O0.11660910E+00.79874659Ej-03.11688086E+00. 11660294E+00.12566991E-02 12373478E+00.12359935E+00.12558 574E-02.12360021E+00.12358651E+00 _6,687 066E-02 *.12996661E+00.12993190E+00.16'75259E-02.12997585E+00.12991354E+00.18277858E-02.13253059E+00.13242259E+00.18274578E-02.13241039E+00.13241742E+00 AVERAGE DEVJATION=.18 _18 PERCENT

.14 o 'a.13 CL) At.12 - Methane- Propane ~<::1~~~~1 '1~~ /Nominal 12%/ Mixture o May 1965 o June 1965 a July 1965.11 0 2 4 6 8 10 12 14 16 18 20 F.104 lIb/min IzL \ micropoise] Figure 48. Flow Meter Calibration for Nominal 12 Percent Mixture

- 162 - TABLE XXXIX FLOW METER CALIBRATION DATA FOR THE NOMINAL 43 PERCENT MIXTURE COEFFICIENTS OF POWER SERIES B =.1C067089E+00 A =.852506C9E+O1 C =.11651994E+05 D = -.58634480E+07 F/P pap (Experimental) (Calculated) E~J~FP (Calculated).42690457E-03.1C606186E+00.1C597763F+r00'.42592783E-03.10603690E+00.1596273F+rn.27921277E-03.10402569E+ 00.10383195F+''C.27955479E-03.1C3763CSE+00.1038366?E+Cr.66486751E-03.10)93819E+00.10976639F+00.66475715E-03.10994463E+00.19 76459E+C0.90656413E-03.11358703E+00.11360703F+00.90524C73E-03.11367214E+nO.11358691E+00.11389194E-02.11696768E+00.11683221E+00.1136942 1E-C2.11697271E+00.1168C795E+OQ.30413977E-03.10399112F+00.10417656E+00.30241248E-03.10402783E+0O0.10415242E+00.53689645E-C03.1746613E+O(.10769929E+00.53668284E-03.10741450E+00.10769588E+00.76631544E-0C.1113C106F+00.11140767E+00.76595315E-03.11128002E+O0.11140186F+CO.10209598E-02.11509553E+00.11528027E+00.10198925E-02.11527714E+00.11526534E+00.11625529E-02.11698900E+00.11711694E+00.11631606E-02.11684887E+00.11712414E+nO.27697935E-03.10382947E+00.1t0380147E+0C0.27594865E-03.10390651E+00.10378743E+nO *55502090E-03.10811915E+00.10798936F+On.555404CCE-03.10801977E+00.10799551F+Or.78626323E-03.11184506E+00.11172713E+f0O.78446160E-03.11178402E+00.11169834E+C0.10054930E-02.11500985E+00. 11506253F+o('n.10015507E-02.11495840E+00.115nO656F+C0.11790895E-02.11738896E+00.11731036F+0O.11753148E-02.11741785E+00.11726664F+Cn AVERAGE DEVIATION =.127 PERCENT

.125 - 0 o.0 ~-~.120 no at 5 Methane -Nitrogen <j o August 1965 September 1965 ~ 115 -, October 1965 3 4 5 6 7 8 9 10 11 12 F.104 lb/min Fuure micropoise Figure 49. Flow Meter Calibration for Nominal 43 Percent Mixture

- 164 - TABLE XL FLOW METER CALIBRATION DATA FOR NITROGEN CfEFFICIENTS OF POWER SERIES B =.1056743CE+00 A =.1125477SF+C2 C =.52cC61SE+C4 D -.19=771 36E 07 pA~pen (Calculated) pap (Experimental) Pap (Calculated). 25C6295F-0. 1C9CO6-E+CC.I1Cc;C5 EE+C CC.2 5939652 F-OA. C88C96E+00 1 C8S'5819E+CC.4c7071 C7E-03.1123417CE+CC.1124SCE6E+CC 4c -71342 F-C3.1 1 227C95E+00. 112 5COC S3E+CC.70573235E-C3.1 1c33 62F+C C.11587523E+CC.92211015E-03.11941C12E+OC.11954366E+OC.92434654E-C3. 1137CE18E+OC. 11952C1E+CC. 1C322788E-02.1211 l1CE+CC.12143554E+CC.10357567E-02. l 1211017CE+CC.12149527E+00 170?C735E-C3.1103418(-E+CC. IIO'S531E+CC -37303991E-C3.1 1C30025E+00.11C5523E+CC.5C5S7636E-03.112604C5E+CC *112f3C16E+CO.5C547236E-C!.11247773F+CC 112622E3E+CC - 6Cil16CqE-C3.113eS254E+CC. 1141851EE+CC.717C4447E-03.116C5C6E+CC.11Cf4C1E+CC.71834207E-C3.116C5CC6F+CC.1 16CE57CE+00.8280671 8E-C3.11787468E+CC.1 17S36S3E+CC.82729270E-03.117E3567E+OC.117S2375E+CC.3e8C6998E-01.11117831E+0C. lC 71325E+OC.38C'81578E-03 * 11lC7f3SE+ OC 11C11CS5E+C O. 6C736357E-C3.111473771E+CC. 14 254124E+CC.82002?12E-C3.1 8383EE +CC. 1 178002sE+CC. 1015C260E-02.121'7512E+CC.iZ2113S17E+00.10181365E-02.12143421E+CO.*121126 F+OC.11114738E-02.12293422E+CC.12217353E+CC.11.128751E-02.22 lE+a 122175C4E+CC PVERACE DEVIATION =.224 PERCENT

CD.120 - 0._ 0 E D.115 Nitrogen o1 z/~0o December 1966 0 January 1967 / February 1967.110 2 3 4 5 6 7 8 9 10 11 12 F. 104 lb/min ft micropoise Figure 50. Flow Meter Calibration for Nitrogen

APPENDIX C ENTHALPY FORMULAE and LOOP CHECKS - 166 -

I FORMULAE USED IN CALCULATION OF PROPERTIES FROM EQUATIONS OF STATE 1. Benedict-Webb-Rubin Equation (a) Enthalpy Departure ~4C 5 22 2 4Ce _ 2 o 4 ce-Yo ) e-Yo 2 25 (B RT- 2A (2bRT - 3a)p + 6aap 5p+yp 2yp C 2 5 ce- 2 2 26 RT + 2p(BRT - Ao -) + 3p (bRT - a) + 6aap + 3p(1+yp2) - 2yp 0 0 T2 T (c) Heat Capacity R6C p 6c 2 2 C C - R + - + ( - + ) eYp P P 3 3 ], o[ B Rp + bRpR + c[ + YP 2) yp ] 0 T3 T T2 P + p(2B - T2 -) + P (3bR - 3a) + - p) e

2. IGT Modified B-W-R Equation (a) Enthalpy Departure 2 2 4C 6D 5 2 2yp -YP (B R 3a 2 + 3 e ) YP - (B RT2A0 0 T T )p + (bRT T)P + 2 2 2 2 2 2 2 5 -e + ype T4 2 2 (b) Isothermal Throttling Coefficient 2 4C 6D 2 0 0 +(bT-3p+6ap4 ce ~ + y3 2 (B RT - 2A - + (2bRT - 3a)p + +aap + [5p + 5yp - 2y p 0 o T T T + [.7p + 7yp3- 2y 2p5 C D 2 RT + 2p(B RT - A - - - + 3p2(R a) + 6a + e-y' [32p 2y26 C+ 2 (bRT 6acp5 e 4(1+ yp ) - p ] [ ] T T T T

II. Thermodynamic Consistency Checks 1. Nitrogen The isothermal data of this work were used in conjunction with the 94 isobaric lata of Jones to test the consistency of the experimental data at low temperatures. Two loops are shown in Figure 51, and the experimental enthalpy changes along different paths are given in Table XLI. TABLE XLI CONSISTENCY CHECKS ON NITROGEN Path AH Percent (Btu/lb) Deviation A. 1-2-5 64.53 0.78 1-4-5 65.04 B. 2-3-6 63.24 0.22 2-5-6 63.38 2. Nominal 5 Percent Mixture The isothermal data of this work and the isobaric data of Manker were used to make consistency checks of the experimental data. The location of the loops is shown in Figure 52 and the enthalpy changes along different paths are given in Table XLII.

- 170 - 3000 I I 8 NITROGEN 2500 I II I I\ I I V) 21500 1 LU 1176 psia I 5 2 1000 04588 psia \ 500 0 20 40 60 80 100 120 140 160 ENTHALPY Btu I lb Figure 51. Location of Experimental Loops for Nitrogen

- 171 - 2000 19 15o 0 5 18 14 9 4 1500 nr 1-/00 117 13 8 2 0.~1 6 2 500 ENTHALPY (BTU/LB) Figure 52. Location of Experimental Loops for Nominal 5 Percent Mixture

TABLE XLII CONSISTENCY CHECKS ON THE NOMINAL 5 PERCENT MIXTURE Path AH (Btu/lb) Percent Deviation A. 1- 2- 7 74.16 0.46 1- 6- 7 73.82 B. 2- 3- 8 79.24 0.01 2- 7- 8 79.25 C. 3- 4- 9 84.50 0.05 3- 8- 9 84.46 D. 4- 5-10 88.82 0.10 4- 9-10 88.73 E. 6- 7-12 85.21 0.12 6-11-12 85.31 F. 7- 8-13 104.92 0.42 7-12-13 104.48 G. 8- 9-14 125.47 0.25 8-13-14 125.79 H. 14-15-19 129.07 0.07 14-18-19 128.98 I. 12-13-17 209.60 1.45 12-16-17 206.58 J. 13-14-18 173.37 0.91 13-17-18 174.96 K. 14-15-19 136.52 0.43 14-18-19 135.94 - 172 -

APPENDIX D EXPERIMENTAL DATA - 173 -

- 174 - TABLE XLIII TABULATED EXPERIMENTAL ISOBARIC DATA FOR THE NOMINAL 5 PERCENT MIXTURE Mole Inlet Inlet 'OutletT Power Flow p (A/T)p Run Fraction Pressure Temperature (Temprature (*F) (Btu/mn) (lb/mi) (lb (Btu/lab) (Btu/1b-F) C3Hs18 (*a I ('F) (-F (Btu/lb) 2.02C.CS? 1465.2 151.55 2C4.54 12. ' 1.167.135.CC( 6.68.665C 3.0,.I02 _7 1945.7 11.57 5.36.7.613.1355.006 4.517.6653 4.010.'5?2 501.2 1 C1.5C 1q8.10 f.57.6C7.1551.C2F 3.FEE.5567 4.C21.052 5C0.C l11.6? 2C4.7C 1].07 1.21F.1A54.C27 7.P4C.5557 4.020.C5? 5C0.0 1l1.64 2C4.73 13.OC 1.216F.IC.C2F 7.825.5582 5.01C.C52 100C.2 1S1.61 158.16 6.55.646.154.C13 4.155.6345 5.020.052 1 CCC.7 191.61 2C4.7C 13.12 1.?'5.16C1.C01 8.126.6344 h6.10. _.0.7 14$5.8 87.52 S4.86 7.37.875.161.CC5 5.319.7323 6.02C.0521. 15C2.2 F.54 1C2.C3 14.49 1.72C.161.00CF 1C.612.7322 6.C7C.052 15CC.9 87.54 123.4 35.55 4. 16.1617.CCS 25.7?9.7159 6.C41.0%2 15C(.8 67.54 15C.62 f3.C8 7.15?.1615.CC 44.521.7C5E 6.C40.052 15C1.1 67.4 150.59 6. 10 7.14.1616.00CC5 44.506.7C53 7.010.052 5C1.C R7.51 54.PP 7.37.655.1614.C04 4.265.5794 7.020.05- CC. 7.41 10C1.84 14.47 1.345.16CS.C34 e.351.5787 7.C3C.052 C1. ' P7.u2 127.46 75.54 3.165.161C.011 2C.67C.5EC6 7.041.052 500.3 F6.83 150.03 63.20 5.0CC.1C06.C3C 36.700.5EC7 7.C4C.05? cCO.5 67.58 15C.P2 63.26 5.SC1.16C'.C031?6.744.5810 8.01C.052 2CC1.C 87.45 54.92 7.48.586.16.5.CC5 5.S65.7576 8.0?C.C57 700?.7 F7.47 ICl.c, 14.45 1.6SC.16f6.CC5 11.463.7532 8.03C.052?CC1.5 87.47 12?.16?5.69 4.6C0.165E.OC 27.745.7775 8.041.052 2CC2.5 67.45 16].64 76.15 5.416.16?7.CC5 57.5CC.7547 8.040.052 2CC002.1 87.47 163.7$ 76.'2 5.416.1634.005 57.611.7545 9.C1C.05? 2002.2 2CC.47 257.17 56.71 1.EC2. CCC 40.14.7C56 S.02C.2C52 1999.3 2CC.50 257.22 56.73 6.525.16.41.CC5 39.792.7015 9.0?1.C52 2CCC.6 2CC.52 757.2P 56.76 8.8O0.223C.CC,0 39.8C.7C13 9.030.052 2002.0 200.50 257.31 56.80 8.880.2229.CCS 35.825.7C12 9.01 9.052 20 C 2. 2 2CC 4 47 257.17 56.71 1.8C2.C45 C.CC 40.C33.7C6C.0C25.052 1999.3 2CC.5C 257.22 56.7?3 6.52.164C.0CC 39.805.7C17

- 175 - TABLE XLIV TABULATED EXPERIMENTAL ISOBARIC DATA FOR THE NOMINAL 12 PERCENT MIXTURE Mole Inlet Inlet Outlet Run Fraction Pressure Temperature Temperature AT Power Flow AHp (AH/&T)p ~ (~) p O~H8 (psia) ('F) ('F) ('F) (Btu/min) (lb/rain) Td (Btul] b-'F ' (Btu/]b) (Btu/lb) 22.O 10.117 1000.3 51.23 63.55 12.32 1. 327.1510.002 8. 787.7130 22.011.117 1000.3 51.25 63.58 12.33 1.327.1511.003 8.783.7123 22.020.11 i 1002.3 51.23 63.56 12.32 1. 044.1185.011 8. 774.7121 22.021.117 1000.3 51.23 63.55 12.32 1.044.1190.015 8.762.7111 22.030.117 1000.3 51.24 63.54 12.30.803.0918.019 8.725.7094 22.0 31 ~ 117 1000.3 51.23 63.52 12.29.803; 0918.022 8.721.7093 22.040 ~ 117 1000.3 51 ~ 21 63 ~ 58 12 ~ 37.604.0685.033 8. 779.7099 22. 041 ~ 117 1000.3 51 ~ 22 63.59 12 ~ 37.604.0684.033 8. 784.7100 22.042 ~ 117 1000.3 51 ~ 21 63.55 12 ~ 34.60 3 ~ 0685.003 8. 804 ~ 7134 23.010 ~ 117 512.3 50.24 55 ~ 16 4.92 ~ 425.1478.000 2. 875.5844 23.011.117 512.3 50.21 55.13 4.92.425.1478.000 2. 873.5835 23.020.117 512.3 50.21 61 ~ 43 11 ~ 23.962.1479.006 6. 499.5788 23.021.117 512.3 50.22 61.44 11.22.962.1480.no7 6.490.5783 23,030.117 512.3 50.27 77.49 27.22 2. 316.1478.007 15.658,5753 23.0 31 ~ 117 512.3 50.22 77.45 27.24 2.317 ~ 1478.007 15.666 ~ 575 2 24.010.117 503.8 148.70 -146.15 2.55.196.0903 -.Or)(' 2.176.~530 24.020 ~ 117 496.2 -148.70 -136.13 12 ~ 56.976.0891 ~ ~gO 1n ~ 953.871 8 24.030.117 500.8 -148.71 -128.97 19.74 1.578.0899.002.... 17.547.888R 24.040.117 498.6 -148.71 -123,05 25.65 2. 550.0892.On3 28. 584 1 ~ 1142 24.0 50 ~ 1 17 497.6 -149 ~ 15 -123.96 25.19 2.02 5.0891. Oq5 22.724.9n20 25.0 2C.11q 15C2,2 -22n. 52 -20a.69 11.a~.977.1126 -.or2 8.631.7293 25.0 30.11 q 15o 2.9 -22 ~. 5? - 144.44 26. Ca 2.! 67.11 31 -.?C 3 19.155.7345 25.04C. 11G 15 C5. (' -22 1. Oq -159.96 6 1.12 4.84C.107 1 -.nrTt 45,2ii.7i97 25.05C.11 9 1504.2 -22C. 5~ -137.12 8 3.41 6. 727.107C -.002 62.889.7540 26.010 - _.CP 1265 - ( 6 765 7239.118 2C17.2 23?.47 -2 f)g+.........Q,3~.........85P..mr~ ~ ~ 26.0 2C.118 27!5.1 -71?. 4% -192.26 21.17 I. 965.1267 -. Or] 15.51 1.7329 -- 26'030.118 2014.1 -21~.41 -l&a.r.~ 45.41 4. 254.1270 -.0C2 33.5~.7379 26.040 ~ 11 ~ 2 O16.1 -21 ~. 47 -!45. Q4 67.48 6.3 ~.1268 -. nC2 50. 369.7465 26.050 ~ 118 2018.1 -21B. 43 -126.94 IRA.49 8. pt,~.127 I -.00~ 64 '864 —.7500 26.060.118 2014.1 -21 3.39 -lr2.18 11 1.21 ] C. 7aB.1267 -.aC 1 R4.785.7624...................... ~......._ _ 27.010.116 498.3 -129.61 -124.00 5 ~ 60.441.0506. CnO 8.714 1. 5554 27.020.116 496.3 -128.92 -122.57 6.35.867.0505 -.r'01 17.189 2.7e)87 2.7.030 ~ 116 498.3 -128.90 -1 19.34 9.56 1. 964.0508 -.000 38. 697 4,0464 27.040.116..........501.3 '128.92 -105.80 23.12 4.296.051n.bob.... 84.227.......3.64~3~~7.050.116 494.3 -128.92 -50.33 78.59 7.52 q.0503 -. 005 149. 798 1.90 61 27.060.116 494.3 -129.11 -9.84 119.27 9.898.0506.045 195.386 1.6382 ~7.070.1 16 494.3 -128.71 20.77 149.48 11. 185.0505.029 221. 372 1. 4810 27.080.116 500.3 - 129.42 3.27 132.69 19.622.0506.059 209.968 i 5823 28.010.118 — ~ 9 q. 7-~2006.1 -92.49 7.27.8C3.1470.CCC -— %. O —~.8352 28.020.118 2008.1 -09.75 -83.52 16.74 2.012.1462.000 13.762.8476 28.030....]18 2005' 1 -cq.7q -75.S0 24.20 ~.C94.1471.00G............20-. 62 C.8520 28.040.118 2003.1 -9q.al -65.92?3.qg 4.317.1473.002 25.~16.8650 ~8.o5o.~18 2oo3.1 -~,,~. 79 -5~.74 47.5s e.~qv.147c.oo7 41.~44 882i 28.060.118?-007.1 -99.84 -31.0~ 68.76 c.17q.1458.0!3 62.956.9155 79.010.11,q '~Oe6.2 -46.70 -41.82 4.3~q.674.1594.3CC 4.255.9725 29.011.118 2004.2 -46.15 -41.77 4.38 674.1581 -.00C 4.262.9733 29.020.118 70n6.?- -46.16 -73.16!3.)0 2.C3a.15c~8.004.........12.'827.......9863 29.030.118 2004.2 -4&.19 -18.67 27.52 4.3~5.1579.015 27.76C 1.0089 ~_9.040.]18 2004.2 -46.18.61 46.79 7.628.157c.026 48.285 1.0320 ~9.050.]18 70~4.2 -46.18?O.ln 6&.28 10.908.1578.032 65.077 1.0422 2g.051.118 2054.2 -4~.18 20.14 66.32 10.907.1577.032 69.134 1;0424 30.010.117!706.2 -40.09 -43.1l 5.97.931.1459.000 6.379 1,0678 ~0,~020 117 1702. 2 -4c. 06 -36.29 12.87?.041.1461.002 13.474 1.0861 ~0.030.117 1706.2 -49.97 -76.95 22. 12 3.57.3.1455.;3a9 ~4.544 1.1095 30.040.117 1704. 3 -4q.01 -15 20 33.77 5.561.1455.917 38.2C6 1,i330 30. 041.117 1 702.3 -4c. 05 -15.3 3 33.7~ 5. 560 ~ 145 1.011 38.297 1.1355 30.050.1 17 1702.3 -49.06 6.07 55.13 9.260. la51.02P 63. 772 1.1568 30.060.117 1704,3 -40.11 34.20 ~3.40 13.7s6.145~.547 94.603 1.1344 3i 010 lib.....i5C3.2 -69.20 -62.01 7.19 1.CTq.1446.OCC.....?,465......... i.-0378:~1.020.! 18 14c8.2 -69.09 -54.76 14.8? 2. 287.1445.000 15.82~ 1,0676 ~1.030.tip!~00.2 -6c 07 -44.49 24.5~ 3.c11.14~9.OC% 27.170 1.1048 ql ~ 041. ] 1 lq 1500. 2 -6c. 06 -~l. 12 37.94 6.3 ] '~.1442. OCC q ~. 743 1 ~ 1543 31.040 ~ 118 1500.2 -69. 15 -31.24 77.9! 6:f l B.1442. OCO 43.77C 1.154'7 ~1.050.118!500.2 -6q.06 -19.~ 58.23 10.168.I24~.CCC 70.442 1.2097 31.060.118 1500,2 -6c.11 4.07 73.17 12.88~.1445.005 89,158 1.2184 32.010.116 2002.1 1.34 6.79 5.44.984.1674.000 5.876 1.0792 32.022.116 2002.1 1.34 13.38 12.04 2.176.1675.004 12.986 1.0784 32.021.116 2006.1 1.40 13.44 12.05 2.178.1678.024 i2.i}57 ' i,,0756 32.020.116 2004.1 1.40 13.48 12.09 2.178.1674.025 12.984 1.0742 32.030.116 2003.1 1.40 27.07 25.68 4.579.1669.045 27.390 1.0667 32.040.116 2004.1 1.35 51.61 50.26 8.670.1664.046 52.044 1.0355 33.010.117 1502.2 1.40 6.43 5.03 1.012.1662.000 6.089 1.2110 33.020.117 1502.2 1.42 12.55 11.12 2.196.1665.000 I3.193 1.I859 33.031.117 1498.2 1.44 25.42 23.98 4.520.1660.000 "2"~,~:22 6....1..135 5...... 33.030.117 1498.2 1.43 25.43 24.00 4.519.1659.000 27.248 1.1353 33.041.117 1498.2 1.43 51.35 49.92 8.659.1657.000 52.239 1.0464 33.040.117 1501.2 1.47 51.20 49.74 8.654.1663.004 52.033 1.0462

-176 - TABLE XLIV 'Continued) Mole Inlet Inlet Outlet O AT Power lrlow AP;)d Hp (AH/AT)p C38 (psia) (~F) (~F) /b 34..01-1.11 7 2004.2 5 1.25 57.44 6.18.995.1694.000 5. 873.9497 34..010.117 2003.2 51. 24 57.41 6.17.995.1695, 000 5. 869.9507 34.020.117 2002.2 51.25 64.94 13.69 2. 171.1691.006 12.832.9376 34.030.117 2002.2 51. 27 80. 24 2 8.97 4.479.1692.007 26.461.9134 34..041.117 2002.2 51. 30 109. 49 58. 19 8. 597.1691.012 50.- 81~...8733 34.040.117 2002.2 51. 32 109. 36 5 8.04 8,,594.1695.012 50.705.8735 35.010.116 1502.2[ 51.32 58.80 7.48.995.1512.000 6.577.8792 35.020.116 1502.2 51.34 -67.85 16.51.2.148.1511 -.000 --— 14.2116.8609 35.030.116 1502.3 51.39 86.88 35.48 4.457.1515-....0 0.....29.4+12 ------.8289 -35.031. 116 1503.3 51.39 86.85 35.45 4.457.1517.007 29.366.8283 35.040. 16 1502.3 51.33 103.20 51.87 6.336.1514.007 41-.844.8067 -35.050.116 1500.2 51.39 123.45 72.07 8.556.1512.006 56.592.7853 "l'g"Ol — ~ 117 250.3 5 1.25 62.19 10.95.986.16'-9.. 'dOY.......0 36.020.117 249.3 51.28 70.69 19.41 1.7 3 6.-1692 --.000 10.263.5288 36.030.117 249.3 51.29 81.98 30.69 2.744.1690.000 16.239, 5291 36.041.117 248.3 5 1.32 101.30 49.98 4.464.1684.000 26.515.5305 36.040.117 248.3 51.30 101.34 50.04 4.464.1681.000...26.55 4...506 36.051.117 250.3 51.30 124.77 73.47 6.630.1693.000 39.1!49.....5328 -36.050 ~ 117 249.3 51.26 124.76 73.50 6. 630.1692.000 39.181.31 37.020 ~ 117 998.3 51.24 58.66 7.42.790.1487.000 5.313.7160 37.030.117 1000.3 51.29 65.23 13.94 1.473.1488.007 9.892.7094+ 37.04,0.117 998.3 51.26 85.67 34.41 3.539.1486.007 23,811....6920 38,010 — 117 1000.2 -73.98 -71.50 2.48. 2 55 _ 0690-.o00 3.699 1.4909" 38.020 ~ 117 999.1 -74.02 -68.50 5.~52. 596. 0713-. 015 8.346 1.~511 7 38.030 ~ 117 1000.2 -73.~99 -66.~64 7.~36. 826 ~ 0707.015 11.670 1. 585 8, 38-.04.0-.117- 998.2 -73.98 -65.49 8.50 1.0-86.0698. 016 15.538.28-1 38.050.117 998.2 -74.02 -66.C3 7.99.966.0684.016 14.094 1.7649 38.060.117 --- 998.1 -74.02 -61.33 12.69 1.913.0723,025 26.4.0833 38,070.117 1002.1 -73.95 -23.48 50.46 6.196.0732. 028 84.600 1.6764 38.080.117 1002.1 —:7-3(-t —.c - 12.14 86.1i 9. -167.070. 25 127.299 1.4782 38.090.117 1002.1 -73.95 25.36 99.30 9.982. 0715.015 139.569 1.4055 189.100 —.-117 i 000.1 -73.98.81 74.79 8. 134.0702.020- ' i1 5.9-19- 1.5499( 39.010.117 1498.1 -139.03 -132.215 6.78.699.1281 -.000 5.461.8060 39.020. 117- 1498.1 -139.01 -120.80 18.20 1.905.1284 -.000 I4.8381 39.030. 117 1498. 1 -13F. q8 -100.79 38.19 4.125.12134.00C 31.871.8344 3~9.040 'II7 1502.1 -139.00 -88.98 50.03 5.544.1300.002 42.637.8523 '39.041. 117 1502.1 -139.02 - 88.891 50.21 5.544. 129~. CC2 42.865.8537 19.050.117! 502.1 -1i39.0o...;84 0 5.....5 1 8.....0?6.3 88 a4O.010.116 8'02.2 -97.60 -90.94 6.66.473. 098. 9O 7.916 1.180~4 4 0.0-2a. 116 80i1.2 -97.55 -87.95 9.60.904.0601 -.0103 15.0-38- 1 56 68 -40.030. 116 800.2 -97.57 -88.51 9.06.757.0602 -.006 12.585- 1.3894 -40.040.116 ~ 798.2- '7.56- f 83-.0 o I4, 57,6....... 2 11.0603 -. 004+ 36.685 2.5198 40.050.116 798.2 -97.58 -63.72 33.86 4.618.0598 -.004 77.171 2.2794 4.06. --.116...798.2 -97.55 -7.42 90.13 8.700.0599 '-.021 145.251 1.6116 4.0.070.116 798.2 -97.56 16.92 114.49 10.311.0601 -.Oil 171.627 1.499 1 4 0.80 —.116 799.2 -97.55 1. 8 2. 71067.0593.017 181.612 — 1.4108 4,0,090.116 801.2 -97.59 5.36 102.94 9.565.0596.042 160.550 1.5596 4i01. 11 -,1000.2 -177.86 -168'22 9.64.921.1241' - 000 7....7424.7699 41.020.117~l.. 999.2 - 17 7.86 -156.91 20.94 2.026. 12 38 -.000 16.366.7814. 41.030.117 998.2 -177.84 -136.32 41.52 4.094.1235.000 33.159.7986 91.040.117 1000.2 ~~~~~~~-177.85 -11)'.28 6 0.58. 1 7.1239.000 49.693.8203 41.050. 117 1000.2 -177.86 -98.20 79.66 8.397.1239.001 67.755.8506 4 1.0 51.117 1 00 0.2 - - 1177. 86 -98.40 79.45 8. 398.1242.002 67.607,8509 -41..060.117 999.2 -177.87 -86.14 91.73 9. 968.1237 4,010 80.551.8781 42.010. 11i003.3 -235.98 -229.77 6.21.476.1067 -000 4.463.7187 42.011.117 1002.3 -235.99 -229.79 6.19.476.1069 -.000 4.456.7194. 22.020.117 1000'~~~003- -2 3 5.97 - 1.519.22 1.492.1066 -.000 13.993.7281 42.020.117 999.3 - 23 5.95 -193.79 42.16 3.3 08.1066 -.003 31.042, 7363 42.040.117 1001.2 -235.98 -170.59 65.38' 5.225.1071 -.000 48.804.74.64 43.01J.117 500.3 -235.98 -226.42 9.56.657.0944 -.000 6.955,,7275 4 3 0 20.1t-7.....502,3 -235.93 -215.21 20.72 1.442.0935 —,000 15.420.744.1 43.030.117 497.2 -235.98 -192.45 43. 5-2 3.047.0943 —.000 32,,303.74.22 -44 -,0 01......-116......35 -178. 05.....-16-6.8 2 -1i'23:.742.0818.000 9.066.8072 44.020.1i16 3 52.2 -178.04 -163.01 15.03.990.0815.004 12.144.8079 44.030.116 355.2 -178.01 -156.49 21.52 1.436.0818.010 17.542.8151 44.040.116 351.2 -178.06 -148.88 29.18 1.955.0810.020 24.108.8261 ~5,;010 ~;;IIT — ~2IO.~J --- — ~~-64.53 -57.83 6.7I-.709.0790.000 8.973-, I 337~q 4.00.117 1201.3 — 645 -47.8 -' 16.99 45.020 -::-6 —4.5 3 -47.84., ~~~~16 899.0792.000 23. 965 1. 4357 45.030. 117 1200.3 -64.51 -38.~22 26.28 316.72.0 975 151 — ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~~~~.4. 0792-.004 595.72 15. 5443 45.040.117 1200.3- '64.53 ' 28.45 3608 4 19.0798416 154 45.5050.117 1201.3 -64.54 -15.89 486 589 0 4.13 — 45.060.11 -— 64 -5 --- — -— 247 62.06- 7.258.0789.043 91.897 1.4804 45.070.117 1198.3 -64.52 _ 2_6_.27.....9_0*79 9.65.078.05 2.81.3417

- l?? - TABLE XLV TABULATED EXPERIMENTAL ISOBARIC DATA FOR THE NOMINAL 28 PERCENT MIXTURE Mole Inlet Inlet Outlet fP2 (~H) dP AHp (AH/AT)p Run Fraction Pressure Temperature AT Power Flow Temperature CsH8 (psia) ('F) (~F) (Btu/min) (lb/rain),E1 ur T (Btu/]bi (Btu/]b-~F1 ("F) 20.019.280 999.3 z 96.20 86.36 9.84 1.609.2074 ~015 7.744.7870 20.0 20. 2 80 998. 3 86 ~ 30 106 ~ 44 20 ~ 15 3. 239. 2095. 015 15.443. 7666 20.0 30 ~ 2 79 1000.3 86. 31 121.01 34.70 5.428 ~ 2092. 014 25. 934.7475 20. 041. 279 1001 ~ 3 86. 29 143. O~ 56. 73 8. 602 ~ 2 090.012 41. 13 8. 7251 20.049 ~ 2 79 1000 ~ 3 86.31 143 ~ 14 56 ~ 83 8. 604. 2090 ~ 012 41 ~ 154 ~ 7241 21.010.280 1998.2 86.31 96.29 9.98 1.988.2110 ~004 9.417.9435...... 21,020. 280 2000.2 86.29 105.31 19.02 3. 750. 2111. 003 17. 762.9338 21.0 30 ~ 2 80 1998 ~ 2 86 ~ 28 121 ~ 13 34 ~ 85 6. 793 ~ 2121.003 32 ~ 024.~I89 2 1.040 ~ 2 80 2002 ~ 2 86. 30 140 ~ 16 53. 86 10. 262 ~ 2138. 002 48. 007. 8913 23,010.281 1502.3 86.25 95.98 9.73 2.010.2610.006 7.695.7907 23.020.281 1502.3 86.55 1 10.89 24.34 4.911.2658 ~006 18.473.7588 23.030. 281 1501. 3 86. 48 130.29 43.81 8. 337. 2618.006 31 ~ 843. 7269 23.0 40. 2 81 1500 ~ 3 86. 43 144.84 58.40 10. 815. 2609.005 41.445. 7096 24.010 ~ 281 2002. 0 86.46 97.31 10.84 2 ~ 184. 2650.003 8.239.7599 24.020.281 1999.0 86.45 104.25 17.80 3.506.2581.003 13.579.7627 24.030 ~ 2~1 2000.1 85. 93 121. 36 35.43 6. 793. 2554.001 26. 599.7508 24.042. 281 1998.1 86.43 144.50 58.07 10.738.2504.001 42.879.7384 24.041 ~ 281 1997.1 86. 43 144 ~ 75 58. 32 10. 737. 2491. 001 43.103.7390 24.040 ~ 281 2003.1 86.42 144.50 58.08 10. 737 ~ 2508.001 42. 802.7370 25.010 ~ 278 1001. I 86.35 97.70 11.35 1. 856. 2087.016 8. 877.7822 25.020. 278 998.2 86.42 104.89 18.47 2 ~ 884 ~ 2035.015 14. 157.7664 25.030. 278 998.2 86. 44 121. 16 34.72 5. 216 ~ 2015.014 25. 869.7450 25 ~ 040 ~ 2 78 1002 ~ 2 86 ~ 45 143 ~ 81 57. 36 8.36 7 ~ 2021 ~ 012 41, 398. 7218 26.010 ~ 278 501.2 86.44 99, 08 12.64 l. 529 ~ 2102.034 7.240.5728 26.020 278 502.2 86.35 112.11 25.76 3.102.2100.032 14. 740......5722....... 26.030. 278 502.2 86.35 129.79 43.44 5. 210 ~ 2101.031 24. 766. 5701 26.040. 278 501.2 86.37 1 43.69 57. 32 6. 837. 2093.030 32. 629.5692 27.012. 281 252.2 86. 39 1 O0.70 14.30 I ~ 663 ~ 2253. 079 7. 303. 5106 27.011. 281 252.2 86. 39 100 ~ 63 14.23 1 ~ 663. 2264.079 7. 266. 5104 27.010 ~ 281 2 54.2 86.40 100.58 14 ~ 18 1 ~ 663 ~ 2272. 079 7. 240. 5106 2F.021.281 251.2 86.42 113.10 26.68 3.089.2246.074 13.682.5128 27.020.281 251.2 86.40 113.04 26.54 3,089.2248.074 13.667.5131 27.031.281 253.2 86.38 125.93 39.55 4.614.2258.076 20.357.5147 27.030.281 253.2 86.41 125.86 39.45 4.615.2265.077 20.293.5144 27.041.281 254.2 86.40 144.47 58.07 6.849.2277.076 30.003.5167 27.040.281 253.2 86.37 144.92 58.55 6.844.2254.075 30.283.5172 28.010.280...... 2000.1 1.53 16.05 14.52 2.643.2103.061......12.568.8653 - 28.020.280 2000.1 1.52 24.94 23.42 4.319.2107.001 20.499.8753 28.030.280 1999.1 1.41 45.19 43.79 8.306.2107.002 39.426.9004 28,040.280 1999.1 1.40 61.58 60.19 11.704.2123.001 55.125.9159 __ 29.n10.2~0 1497.1 1.36 13.85 ] 2.60 2.65?.2103.nO2 12.60~ 1.0009 29.021 ~ 2 8n 1KO2.1 1.56 27.51 25.95 5.8 ~a.2112.004 37.697 1 ~ 0673 29.r 20 ~ 2 8n 1498.1 1. ~P 77. ~9 26.n 1 5. 850.2104. r'a4?7 ~800 1.0688 30.0 lC.282 1498.2 1.41 14.1~ 12.60 2.275.1738.0~4!3.087 1.0313 30.011.283 15r'0.2 1.30 14.~2 12.63 2.274.1748.~4 13.Cll 1.0304?0,020.282 1498.2 1.5n?5.92 23.52 4.7('3.1886.CC6 24.929 1.0599.... 30. 821.28? 149R. 2 1.5f' 27. In 25.59 4.702.1725.~07 27,254 1.0649 30.C ~r'.? ~? ] 498.2 1.4l 42. ~ 7 4C.96 8.%94. 188C. n C9 a4.637 1.0899 3n.r' 40 ~ 292, z~ o8.2 ]. 41 ~. 80 '~9.47 12.$68 ~ 1971. "09 65.548 1 ~ 1021 3n.041.o~? ]ao~.2 1.44 60.96 59.52 12.2&8.1871.0C9 65.559 1.1014 31.0 1C a ~! L~9.? -! 5 a. 21 -135.87 14.95 1.932.2~ 20.~ 18 9.545.6652 31.~20 ~ ~qr 1z~'~q. 2 -15 ~. 21 -122.99 27.31 3.681 ~ 27 11.'~ 19 18.281.6695 31. 021. Par 18o7.? -! 5 ". 86 -123.~7 27.49 3.681.2m06.019 18. 333.6669 31.C4C ~?a~ l 5 ~ ~.? - 150.21 -61.77 88.44 12.383.1993 -.~OC 62.1 17.7024 31.041,29~' ) 4nq. 2 - 15~'. 16 -61.7a 88.39 12.382.1994 -.nCC 62.1 11.7027 31.'~ 30.? 8 F', I z~ o8.2 - 15 '~. 22 - 1 nl. 47 a-8.74 6. 668.2C 0? _. t- O[' 33.3 05.6833 32.r' 11.?a~ Pr~2. 1 -14~. aB -134.1 1 14.72 1.930.1994 -.~1 9,680 '.6575 33. C 1 ~'. ~8 r 2~ no. ] -14 ~t. 79 - 1 ~4.0 3 14.76 1 ~ 930.1984 -.001 9.726.6592 32.020.78Q 19q8. I -1 4~. 77 -1?l.r'8 27.70 3. 669.1997 -.toO1 18. 369.6632 32.031.288 2a~!. 1 -14 q. 7~ -1'~1.~5 47.41 6,314.199C -.~C1 31.725.6692 32.C3(~.29? on,~. 1 - 148. 79 -1 '~1. ze 47.31 6.316. 1993 -.Oc1 31.688.6698 32.0 41. '~ R" 2c~n. ] -~ z, 9.?~ -71..1 I 78.10 19.595. 1999 -. COl 53.903.6787 32.040.28c?f'c^. 1 i4P 7C — 7a.07 77.~3 1~.595.199q -.Onl 53.096.6822: 33.010.28~ co9.? -!49. 11 -l~5 "7 14.84 1.o54.2"51 -.n~l 9.531.6790. _ 33.02C.28~ 1 0'" 1 -~4C.l! -177.77 26.~q 3.691.2041 -.COl 18.084.6853 33;C31.28n!nn!. 7 -140. 1? -qR.%a 5n.54 7.944.1994 -.~f'l 35.332.6989 33.030.2pn c99. ] - 14c. 11 98.52 5n, K9 7.'~48. 1991 -. ~ ] 35.402.6998 33,949.?am ]~'2.1 -149.13 -74.44 74.68 lO.665.199a -. ~'~. 53.587.7175 34.01C.270 1 On 1 ~ 2 -54.19 -49.44 4.75.511.12 36 ~ r~O 1 4.134.8704 34:02~.27q lCnl.2 -54.19 -46.40 7.70.~7.1237.0~1 6.765 8786 34.930.279 1COl.? -54.21 -43.77 10.49 1,495.1235.002 11.374 1.0847 34.A40.279 999.1 -54.21 -33.~3........20.57........3.]93........1189.O"l 26.854 1.3053 34.050.279 ~98.1 -54.15 -41.85 12.30 1.746.119n.001 14.676 1.1936 34,060.279 iooo. ] -54.16 -6.14 48.82 7.018.1163.0~6 60.354 1,2570 34.07C.279 098.1 -54.21 14.55 68.76 9.7o4.1171.010 83.646 1.2166 34.0 81.2 79 998.1 -54.25 42. O 1 96.27 13.3~,4 ~ 1160.005 114.992 1.1945 34.080.279 1~'90.1 -54. lq 4n.~'3 94.21 13.340.1184.922 112,623 1.1954

- 178 -TABLE XL~ (Continued) Mole Inlet Inlet Out let -P2 ~ ~ tl, d? (AH/AT) p Run Fraction Pressure Temperature Temperature AT Power Flow AHp fp} ~y9 C~H8 (psia) (~F)' (~F) (~F) (Btu/mtn) (lb/min) (Btu/lbT (Btu/]b) (Btu/]b-~F) 34.090.279 0o8.1 -5~.21 62.94 117~]5 16.644.1181 --.010 14C.907 1.2028 34. leo.279 gq9.1 -54.19 73.51 127.69 18.245 ~ 117<~.007 154.76c3!.2121 34.111.279 998.1 -54.19 77.82 131.21 ] 8.800.1178.007 159.635 1.2166 34.110. ~7~ o97. I -54.17 77. ]4 131.31!8.706 ~ ] 179.007 159.378 1.2138 34.12 ].27 9 Qq8.1 - 54. qn 88. C9 142.09 19.942.1176 ~ 007 169.553 1 ~ 1933 34.1 2C.2 79 098.1 -54.1,9 88.24 142.41 19.946.1175.007 169.695 1.1916 34.130.279 9q8.~ -54.2Q 95.52 149.72 20.604.1175.nO6 175.420 1.1716 34.140.279 998. ] -54.18 82.83 137.01 19.3~7.1173.998 165.212 1.2058 35. O11.279 1998.2 -74.41 -61.45 12.96 1.928.2056 -.~aC 9.377.7236 35.010.279 2~02.2 -74.42 -6~.47 12.95!.928.2058.nO] 9.368.7235 35.O 20.27 o 1999. P_ - 7/,. 40 -50.15 24.25 3.700.20 65 -.OCO 17.918.7388 35.03m.27 9 2~nC. 2 -74.35 -28.82 45.53 7.085.2087.~NC 33.952.7457 35.040.279 1908.? -74.22 -9.67 64.55 10.2~5.2072 ~ OC1 49.242.7629 36.011.27'7 15 ~r). 2 -74.30 -61.62 12.69 1.975.2040 -.COC 9.681.7631 36.010.279 t499.2 -74.29 -61.57 12.71 1.975.2034 -.nO0 9.711.7638 36.021. ~7 O 1498.2 - 74.27 -47.25 27.02 4. 244.2041 -. 900 20.796.7696 36. C 20.279 1408.2 -74.26 -47.28 26.98 4.244.2044 -.000 20.763 o7695 ~6.030.279 1409. q -74.22 -3~. 28 83.94 7.090.2040.001 34.76!.7911 36] 04].......279 14q9.3 -74.2R -ln.37 63.91 10.736.2041.002 52.589.8229 36.040.279 14q8.3 -74.24 -lO. 3~ 63.9~ 10.737.2042.toO2 52.57~.8227 37.n 1C.281 6~9.3 -99.34 -9~.Sn ~.84.537.1213 -.900 4.430.7579 37.P21.281 698.3 -95.79 -89.34 lO.45.971.1216 -.nO0 7.987.7644 37.020.281 7n2.3 -99.79 -qq. ~3!0.46.971.1223 -.nO0 7.941.7594 37.030.281 699.3 -09.73 -85.o6 13.78 1.282.1215 -.000 10.556.7662 37.07~ C '- 280 698.3 -99.67 -83.42 16.26 1.6].0.1210 -.nO0 13.305.8185 37.050.280 7nO. 3 -99.7n -82.18 17.52 1.956.1217 -.~OC 16.074.9172 37.061.280 701.3 -99.71 -79.96 19.75 2.'575. ]217 -.000 21.164 1.0714 37.060.280 7nl.? -99.70 -79.99 19.71 2. 575.1218 -.900 21.144 1.0725 37.070.28n 700.3 -9q. 67 -70.53 29.14 4. 821 ~ 1219 -.000 39.541 1.3568 37.081.280 699.3 -99.72 -40. Q l 50.71 8.216 ~ 1196.OO1 68.718 1.3550 37,080.280 698.3 -09.71 -48.85 5n.87 8.216.1195.nCl 68.776 i.3521 37.090.280 702.3 -99.68 -1o. 53 80.15 12.082.1210.031 99.799 1.2452 37.100.280 70n.3 -9q.67 8.84 108.51 15.741.1209.027 130.173 1.1996 37.110.289 698.3 -gg. 66 33.00 132.66 18.871.1196.01C 157.737 1 ~ 1890 37.120.280 698.3 -9c. 70 48.34 148.04 21.254 ~ 1191.n25 178.414 1.2051 37.130.279 698.3, -99.81 59.20 159.91 23.097.1!85.n18 194.862 1.2255 37.i40.f79 ' 698.3 -99.78 69.45 169.~4 25.018.1185.C13 211.053 1.247i 37.150.279 6q9.3 -99.82 6q.92 165.74 24.412.1188.018 205.542 t.2401 37.160.27~ 609.3 -09.82 76.50 176.41 25.761.1!86.n14 217.113 1.2307 38.C10.28n 499.3 -122.9~ -117.63 6.29.537.1180 -.OCO 4.546.7230 38.020.280 499.3 -12~. 87 -113.03 10.84.915.1160 -.DO0 7.888.7280 38.021.230 499.3 -12~. 83 -112.94 10.89.915.1163 -.OCO 7.864.7221 ~8.~30.......28n 490.3 -124.01 -!lO.C5 13.06 1.436.1165 -.000 12.327.8830 38.C40.280 498.3 -12 3.99 -lO8.85 15.14 1.952.1162 -.000 16.801 1.1100 38.050.279 500.3 -123.93 -].0].22 22.71 4.230.1157 -.000 36.550 1.6097 38.061.279 497.3 -123.90 -87.88 96.02 6.705 ~ 1120 -.000 59.876 1.6621 38.060.279 498.3 -1)3.87 -87.78 36.09 g. 705.1121 -.00C 59.800 1.6569 38.07!.2 8r 498.3 -123.97 -70.] 8 53.79 8.953.1102.OOO 81.238 1.5103 38.070.289 498.3 -123.96 -69.60 54.36 8.954.1099.000 81.456 1.4984 38.nso.280 499.3 -123.9n -47.5? 76.38 11. 522.1118.001 1 C3.086 1.3497 38.090.280 501.3 -123.90 -24.16 99.74 14.370.1134.907 126.712 1.2704 38. lnQ.279 498.3 -123.90.87 124.77 17.318.1127.060 153.604 1.2311 38.11n.279 499.3 -123.91 25.51 149.42 20.739.1128.n28 183.879 1.2306 38.120.279 499.3 -lP~.91 35.91 159.82 22.425.1125.022 199.317 1.2471 -3~. 130.279 4q9.3 -123.83 46.83 170.70 24.348.1123.021 216.796 1.2700 38.140.280 499.3 -123.83 53.87 177.69 25.600. I123.023 227.875 1.2824 38.150.280 409.3 -! 23.83 59.!O 182.92 26.424 ~ 1119.025 236. 087 1.2906 38.160.280 499.3 -123.95 66.23 190.18 27.076.1125.n24 240. 700 1.2656 30. 040.2~ O 1583.? -123.99 -69.C 5 54.94 8 ~ 550.2186 -. nOC 39.109.7119 39.041.280 1498.2 -1?4.05 -69.12 54.93 8.550.2186 -. OnC 39.1 10.7120 99.n30.280 1498.2 -124.00 -68.88 55.12 6.802.1736 -.001 39.186.7109 39.020.2A 0 14~8.2 - 129 ~ 98 -69.04 54.94 4. 962.1267 -.0 O0 39.168.7129 39.O 10.280 149R. 2 -124.06 -69.05 55.91 2 ~ 563.0658 -.000 38. 966.7083 40. 049.28n 1998.2 -22 7.8R -12~.94 98.94 14 ~ 674.2002 -.OO 1 73.294.7408 40.030.280 20nl. 2 -227.8R -160.32 67.56 9.996.2016 -.001 49.595.7340 49.020.2 8m ]998.2 -227.98 -! Q~ ~ 22 29.76 4.338.2011 -. 001 21.570.7247 ' 40-'-~' 1C.2RC 1998.~ -.227.8.~ -213.27 14.61 2.024.2020 -.nO1 10.020.6858 41.~40.2 Br' 1490.2 -22 8.17 -132.1 3 96.04 11.837.1899 -. 901 62.348.6492 41.041.2~ 0 1500.2 -229.15 - ] 32.2? 05.93 11 ~ 937.1902 -.00 ] 62. 249.6489 41.0 30.?89 15c 0.? -P2 8.09 - 164.64 63.45 7.739.1902 -.001 40. 690.6413 41.n20.280 1498.? -228.12 -192. C3 36.08 4. 385.1913 -.001 22. 929.6355 41.010.? 8? 14q8.2 -22 7.9! -210.96 16 ~ 95 2.048.1908 -.001 10.732.6331 a~.Q40.280 19nO. 3 -228.27 -131.41 96.86 11.923 ~ 1877 -.001 63.536.6560 42.0 30 ~ 280 998.3 -22 q. 61 -170.43 58.18 7. 092.1890 - ~ OO1 37.532.6451 42.031.28~' ~98.3 -22 B. 64 -170.80 57.83 7.093.1902 -.001 37.284.6447 42.020.28C 1CNO. 3 -22 R.05 -196.46 31 ~ 59 3.Q05.1935 -.001 20.178.6387 42.0 21.? 80 999.3 -22 7.99 -196.39 31.6! 3.905 ~ 1933 -.001 20.206.6393 42.01n.280 1CQO. 3 -22P. 13 -214.11 14.03 1.739.1949 -.001 8.925.6363 '- 43 04n.28~ 500.3 -228.35 -]25.84 ln2.5] 1.4.770.2166 -.001 68.201.6653 43.03n.280 49~. 3 -228.37 -154.72 73.65 lO.257 ~ 2128 -.001 48.210.6545 43.020.280 498. ~ -22 9.33 -177.96 50.37 7.n30.2155 -.001 32.620.6476 43.010.280 5Ol. 3 -228.16 -lO9.97 28.19 3.927.2169 -.001 18.105.6422

- 179 - TABLE XLV (Continued) Mole Inlet Inlet Outlet ~ Run -P2 ~ ~H, dP Fraction Pressure Temperature Temperature AT Power Flow AHp (AH/AT)p C~H8 (psia) (~F) (~F) (~F) (Btu/min) (lb/min) ]P1 ~)T (Btu/] b) (Btu/]b-~F) (Btu/lb) 44.040.?77 248.3 -2~8.44 -152.36 76.0R 12.926.2068 --.-~00 -- 62.503.8215 44.030.277 249.3 -228.18 -169.07 59.11 8.579.2216 -.nO1 38.723.6550 44.020.277 249.3 -22~J66 i9~,.03 -- r 25.63 5,i4:3......2-2~8-....... —~.OL~[....~~.......~ 8-0 -44.010.277 249.3 -228.23 -210.75 17.48 2.544.2257 -.001 11.270.6447 45.010.279 251.3 -159.01 -15~.07 3.94........640 -.2367 J.O~02 2.7~ --.6879 45.020.279 25?.3 -159.03 -153.5~ 5.50 1.277.2361 -.001 5.409.9843 45.0~0.279 252.3 -159.m3 -153.98 5.05.885.2342 -.001 3.777.7482 45.040.279 250.3 -159.0~ -153.30 5.73 1.982.2332 -.001 8.501 1.4831 45.C50.279 250.3 -159.03 -151.05..... 7.r98....4~ 507 — -— /23. 353 -.C01 19.155 2.4017 45.060.279 249.3 - 159.02 -147.2'~ 11.77 8.618.2383 -.0~1 36.170 3.0733 45~070.278 248.3 -150.r~l -134.66 24.35 13.966.2061.019 67.762 2,7826 46.010.281 250.3 41.21 54.89 13.68 1.618.2265.168 6.976.5100 46' 020.28 1 248. ~ 41.20 66.6~ 25.46 2 ~ 991.2277.335 12.799.5028 46. 030 ~ 281 248.3 41.20 81 ~ 91 40.7 1 4. 762.2273 ~ 159 20.786.5105 46.041.281 297.3 41.19 9a.l~ -- ~6.99 6.659.2275.155 29.120.5110 46.040 ~ 281 259.3 41.19 97.78 56.59 6.658.2290 ~ 1 56 28.913.5110 46.050.281 260.3 41.20 109.80 68.60 8.103.2297.153 35.119 '5120 47.012.280 999.2 86.35 100.?Q 13.94 2.115.1937.024 10.894.7817 47,nll.2R0 998.2 86.34 100.31 13.97 2.115.1932.024 10.922 —.7818 47.C10.280 1?91.2 R6.34 1N0.20 1'3.86 2.115.1936.024 10.903.7868 47.024.280 998.2 86. 34...........!] 1. i~........24.84 3.681.1935.025 18.995.7645 47.023 ~ 280 998.2 86.39 111.30 24.9c~ 3.6S 1.1934.027 19.013.7635 47.022.2 80 qo8.2 96.38 111.25 24.87 3.682.1932.025 19.032.7653 47.021.280 998.2 86.37 111.20 24.83 3.682.1935.027 18.996.7651 47.020.289 1092.2 8~. 32 1 1~.01 24.69 3.682.1944.027 18.908.7658 47.031.280 1001.2 86.31 125.23 38.91 5.625.1935.024 29.040.7463 47.030.280 1002.2 86.31 ~ 25.15.........38.84 5.624.1937.024 29.007.7468 47.042.280 1 oO0.2 86.34 146.94 60.60 8.473.1932.024 43.839.7234 47.041.280..... 998.2 86.35 147.12 60.77 8.472.1928.023 43.914.7226 i7.040.280 998.2 86.37 147.21 6m.R4 8.471.1928.023 43.917.7218 48.010.281 i300' 2 -14. C5 -7.78 6.27.865.1359 -.000 6. 365 1.0155 48.020.281 1390.2 -14.06 -3.99 10.07 1.429.1360.000 10.506 1.0435 18.030.281 1298.2 -14.01.h9 -- i4.50 2.125.1358.000 15.644 1.0790 ~8.040.281 1298.2 -14.01 '~.99 17.99 2.739 ~ 1358.000 20.170 1.1209 48.050.281 1298.2 -14.00 8.OR 22.09 3.443.1358.OCO 25.359 1.1482 48.060.281 13m2.2 -14.02 23.7o 37.72 6.009.1368.000 43.917 1.1642 48. C70 ~ 28 1 12 q9.2 -14.02 34.65 48.66 7. 759.1363.000 56.926 1 ~ 1698 48. 080.281 1298.2 -14.07 44.3n 58.36 9. 301.1362.000 6.8.2 70 1.1697 i8.091.281 1298.2 -13.92 60.45 74.36 11.925.1364.001 87.439 1.1758 ',8:090.281 13 O 1.6 - 14.05 60.25 74.30 13. 248.1369.000 96.752 1. 3021 49.010.281 1998.0 41.94 50.46 8.52 1. 757.2180.004 8.n 52.9448 49.021.28 1 2000.0 41.93 56.34 14.40 2.995 ~ 2188.005 13 ~ 681.9498 49.0 20 ~ 281 1998. Q 41.93 56.41 14.48 2. 995 ~ 2178.005 13. 748.9495 49.030.281 1999.0 41.87 64.81 22.94 4.770.2178.005 21.897.9546 i9.0 41.2 81 1998.0 41.93 72.6n 30.67 6. 354.21 67.006 29.3 20.9558 '~9. 040 ~ 281 1998.0 41.93 72.61 30.69 6. 344 ~ 2165.006 29.29!.9545 49.9 51 ~ 2 81 1998.0 41.96 79.44 37.47 7. 732 ~ 2157.0 05 35. 835.9563 49.050.281 1999. n 41.87 79.33 37.46 7.733.2159.005 35. 814.9561 49.060.281 1999.0 41.89 87.04 45.15 9. 307 ~ 2156.006 4 3.162.9560 ~ 49.0 70.281 1998.0 41.93 9~. 8R 51.95 10.635.2144.006 49.610.9549 49.081.281 1999.0 41.95 100.30 58.35 11.9 35 ~ 2148.0 05 55.545.9520 ~9.0 80 ~ 2 81 1998.0 41.97 100.46 58.49 11.935 ~ 2143.006 55.675.9519 49.091.281 1996.0 41.nO 107.75 66.75 13.532.2141.005 63.207.9470 49.090 ~ 281 2ran0.0 41.93 108.54 66.61 13 ~ 532 ~ 2144.004 63.115.9476 49.100.28 1 1999. n 41.83 118.92 77.10 15. 579.2143.004 72.683.9428 50.010.279 1498.2 -lO. lm 10.81 20.91 4.447.2147.005 20.704.9900 50.020.279 1591.2 -8.67 30.84 39.51 8.908.2157.008 41.302 1.0455 50.0 30.279 1498.2 -8.64 41.70 50.34 11.471 ~ 214n ~ '~ 10 53.582 1.0 643 30.040.279 1591.2 -8.63 52.32 60.95 13.834 ~ 2110.011 65.549 1.0755 50.051.279 1497.2 -8.67 62.58 71.25 15.636.20 27.010 77.129 1.0826 50.050.279 1499.2 -8.67 6 2.~, 1 71.28 15.6 36.2029.01C 77. 053 1.0810 50.060.279 1498.2 -8.62 71.82 80.44 17. 621.2022. O 10 87.138 1.0833 50.0 70.279 14o8.2 - 8.66 92.20 100.86 22.n 15.2~42.N 10 ] ~7.822 1. 0690 50.082.279 1498.2 -8.68 111 ~ a9 120.17 25. 873.20 59.009 125.664 1.0457 50.081.279 1499.2 -8.75 111.42 120.17 25.889.2062.010 125.555 1.0448 50.080.279 1498.2 -8.75 11 1.38 120.13 25.872.2063.010 125.396 1.0438 51.0 10.279 1N6o. 3 -1 &. 07 -3.93 10.14 1.487.1391.GOB 10.682 1.0531 51.020.279 1259.3 -14. ~7 6.12 20.19 3.215.13 86.002 23.1 91 1.1486 51.030.279 125o. 2 -14.05 16.46 30.51 5.047.1414.006 35.679 1.1692 51.040.279 1258.2 -14.05 26.14 40.19 6.636.1499. ~04 47.090 1.1716 51.0 50.279 1261.2 -14.02 35.68 49.70 8.160.1407.0')7 57.979 I ~ 1667 51.061.279 1259.? -14.08 45.58 50.66 9.709.1389.003 69. 882 1.1713 51.060.279 12 58.2 -14.10 45.43 59.5~ 9. 710.1395.'~06 69.607 1 ~ 1692 51.071.279 1259.2 -14.06 54.43 68.49 11.166.1390.002 89.303 1.1725 51.070.279 1258.2 -14.08 54.41 68.48 11.169.!391.~05 80.274 1.1722 51.0 81.279 1259.2 - 14.06 63.17 77.22 12.6 36.13 9~'.002 90.881 1 ~ 1769 51.080.279 1258.2 -14.06 63.25 77.31 12.637.1390.003 99.923 1.1761

-i8o - TABLE XLVI TABULATED EXPERIMENTAL ISOBARIC DATA FOR THE NOMINAL 43 PERCENT MIXTURE KolA Inlet Inlet Outlet P H unFra Ction Pressure Temperature Temperature A oe lw f (p P(&/&~ Run (OF) ~~~~~~~~~~~~~~~~~(Btu/min) (lb/rain) PI T (Btu/lb) (Btu/]b-?F) N (psia) (OF) (OF) ~~~~~~~~~~~~~~~~(Btu/lb) 1.lOr;6-.434 1001. 3 5 1.68 59. 96 8. 7. 4 0 ~ 3 2. 0 2.59. 34 [ ~ 020. 434 100 2. 2 51 ~ 61 717 ~ 7 20 ~ 16 1.~192 ~ 13 62. 002 8 ~746.4339 1. 030.... 434 1001.2 50.88 96. 96 46. 08 2.699.1361.002 19.829.4304 1.031.434 1001.2 51.05 96.96 45.90 2.701.1364.002 19.808.4315 2.010.434 2000.1 53.15 60.46 7.31.489.1338.001 3.652.4999 2.020.434 1999.1 5 3. 23 71.17 17.94 1.188. 13 35.001 8.898.4959 2.030.434 1999.1 53.20 81.84 28.64 1.874.1329.001 14.103.4925 2.040.43-4 1998.1- 53.22 1C1.20 47.97 3.109.1327.001 23.422.4882. -2.0 50.....434 1998.1 53.25 116.93, 63.69 4.088.1327.001 30.,807.4837.. 3.010.434 1501.1 53.49 61.70 8.21.484.1255.001 3.858.4701 3.020. 434 15 O1.1 53.73 73.78 20.05 1.181. 1266. 001 9.331.4654 3.030. 434 1501.1 54.02 85. 66 31.64 1.~865. 1269.001 14.694.4644 3.040. 434 1501.1 54.06 115.38 61.31 3. 538. 1259.001 28.099.4583 4.0O10.434 499.2 5 1.79 62.30 10.51.484. 1151.004 4.204.3999 4.020.434 498.2...51.71 77.83 26.12 1.205.1147.003 10.498.4019... 4.030.434 499.2 51.70 93.19 41.49 1.915. 1148.003 16.677 41 4.031.434 499.2 51.70 93.21 41.51 1.914. 1146.003 16.689.4020 4.0 40. 434 498.2 51.~56 124.16 72.~60 3.~330 ~ 1145.003 2.7 40 5.010 ~ 434 249.3 51.~16 59.05 7.90.485. 1562.012 3.092.3914 5.020.434 249.3 51.30 70.72 19.41 1.~185. 1560.014 7.580.3905 5.~030. 434 250.~2 51.37 82.07 30.~70 1.~876. 1567.012 11[.958.38945 5. 040.434 251.~2 51.63 105.7?5 54.12 3.~320 ~ 1572. O11 21.105.3899 5.041.434 251.2 51.66 105.81 54.15 3.~320. 1573.011 21.091.3895 6.010. 434 501.~2 -99.06 -91.92 7. 14.476. 1429.008 3.323.4653 6.020.434 502.~2 -99.14 -76.40 22.73 i 1.481.1I420.007 10.424.4585 6. 030.434 501.~2 -99.13 -57.99 41.14 2.~618. 1414.007 18.508.4499 6.040.434 501.2 -99.11 l -14.72 8. 9 5. 8. 4 1. 0 5 3. 0.32 7.010.433 999.2 -98o79 -91.40 7.39.766.1499.006 5.104.6906 7.020.433 998.2 -98.79 -82.32 16.48 1.637.1500.006 10.907.6620 7.030.433 1003.2 -98.81 -63.98 34.83 3. 274.1504.005 21.761.6248 7.040.433 1002.2 -98.80 -23.05 75.76 6.444.1502.004 42.887.5661 8.010.433 1499.1 -98.82 - 92.86 5.96.792.1517.005 5.2 19.8757 8.020.433 1499.1 -098.83 -83.10 15.73 2.006.1517.005 13'.217 '8.405 -8.030.433 1498.1 -98.79 -62.54 36.24 4.265.1514.004 28.172.7773 8.040.433 1498.1 -98.81 -18'.99 79.82 8.240.1511.002 54.528.6832 9.010.433 1998.0 -98.78 -90.56 8.22.9135.i501.003 6.624 ~8055 9.020.433 1998.1 -98.77 -80.55 18.22 2.178.1501.003 14.505 75 9.030.433 1998.1 -98.76 -62.05 36.71 4.253.1501.002 28.333 71 9.040.433 1998.0 -98.77 -21.50 77.26 8.925.50.01 5 0 2 72 1O.010.434 247.2 -98.75. 85.63 13.12.752.1431.013 5.239. 39 10.020.434 247.2 -98.76 -70.54 28.22 1.604.1427.012 11.230.3990 10.030.434 248.2 -98.76 -46.13 52.63 2.987.1436.012 2.9 35 10.040.434 247.2 -98.76 -18.65 ~~~~~~~~~~80719.09.44.1 3.31.3953 10.041.434 247.2 -98.76 -18.49 80.27 4.513.1432.011 31.5411.3925 [0.041~~~~~~~~~~~~~~~~~~~6.4 247. -3.7 -.4 80.7451 13.01 1.471649 -1.41.3-3 9-9.2 -1i8.q-c-0 -10.82 8.8 11.020.433 999.? -18.33 -1.21 17.13 1.20 2.1475.0.4 45 11.030.433 999.2 -18.88 1 i.32 30.20 2.083.1475 02 1 13.47 11.041.433 999.1 -1 8. 81 37.43 56.2 4 3.819 17.02590.4 5 11.040.433 999.1 -18.86 37.44 56.30 3.820.1474 02591.4 3 12.010.433 1499.1 -18.87 -11.13 7.74.586.1427.002410 5 6 12.020.433 1499.1 -18.88 -3.40 15. ',8 1.191.43.0.6 50 12.030.433 1500.1 -18.88 16.69 35.57 21.663 12.02871.56 12.040.433 1501.! -18.83 45.02 63.85 4.660.1425 01 3 69.52 13.010.434 1998.9 -18.85 -10.86 7.99.679.44.0.2 51 13.011.434 1998.9 -18.83 -10.82 8.01.7 13 C.2 59 13.020.434 2000.9 -18.80 -.90 17.90 1.495.1439 02 1 38.5 3 13.031.434 2000.0 -18.87 19.14 '38.01 3.080 13.0 2 47.5 0 13.030.434 2001.0 -18.84 19.17 38.01 3.080.1434 01 2 47.5 9 13.040.434 2002.0 -18.83 47.52 66.35 5.205.1436 01 3 24.56 14.010.435 501.3 -18.83 -9.04 9.79 57 146. 0397.3 1 14.021.435 501.3 -18.79 1.70 20.49 114.46.0.6 38 14.020.435 501.3 -18.80 1.15- 19.94 1.164.46.0.6 49 14.030.435 500.3 -18.98 23.15 42.13 2.439 12.05 714.06 14.040.435 500.?- -18.81 42.37 61.18 3.532.1423 05 2 84.08 15.010.435 247.3 -18.80 -10.53 8.27.462.42.1.7 33 15.020.433 247.8 -18.77 -%.35 18.43 1.028.41.1.7 33 15.030.433 247.3 -1 8.73 20.94 39.68 2.204 14.0 523.82 15.040.433 247.8 - 18,80 40.12 58.92 3.274 14.0 2 58.3 4 16.010,433 1501.1 -168.94 -163.59 5.315 67.51.0.8 8 16.020.433 1501.1 -160.00 -148.198 20.02 2.660 18.02 681.42 16.030.433 1502.1 -169.02 -125.81 43.20 6.159 18.04 3 94.02 16.040.433 1500.1 -169.01 -88.74 80.27 1].640.51.0 1.4 91 17.010.434 2000.1, -168.87 -159.48 9.39 1.062.59.0.7 70 17.020.434 j999.0 -168.87 -142.48 26.39 '3.064.57.0 1.5 70 17.030.434 1999.0 -168.89 -122.65 46.24 548 1 7.0 3 26.66 17.040,434 1999.1I -168.87 -90.30 78.57 9.561 15.02 6 54.73

TABLE XLVI (Continued) ~le Inlet Inlet OutIet Rwa w~laction Pressure Temperature Temperature AT Power Flor ( )/? AHp (AH/AT)p N2 ~: ~pH (psi&) ~F) (~F) (~F) (Btu/min) (lb/rain) (Btu/]b) (Btu/]b-eF)1 (Btu/lb) ]~.010 —.433 999.2..... -169.09 ii62.12 6.9~;!.! 89.15,s —.012 7.668 1.0996 18.020 -"'~. 3 ~000.2 -169.04 -149.47~~ ~ 56 3. 850 ~548~ ~ -- 24.863 -- 1~1~ 18. 030. 433 999.2 -168.86 -120.02 48. 84 9.970. 1550.009 64.308 1. 3167 18. 041.433 1003.2 -168.84 -66.3I 102.53 15.878. 1556.003 102.061.9955 ' 18 ~ 040. 433 1003 ~ 2 - 168. 82 -66. 43 102 ~ 39 15 ~ 881 ~ 1558 ~ 003 101 ~ 938.9956 18,050.433 1001.2 -168.83 -98.91 69.91 12.686. 1555 004 81.592 1.1671 19.010. 437 252. 3 -16 9. 03 - 153.96 15.07 1. 046 ~ 1535 ~ 0 20 6. 791.4506 19.020 ~ 437 250.3 -166.74 -136.39 30.35 2.034. 1526.017 13 ~ 314.4387 19.030.437 249.2 -169.37 -! 18.80 50 ~ 56 3.307. 1516.017 21. 795.4310 19.040. 437 250.2 -169.36 -88.08 81 ~ 28 5. 199 ~ 15 17.015 34.255.4214 20.010. 434 1499. 2 -247.28 -239.60 7. 69, 769 --- —--. 1583 -. 001 4. 856.63! 7 20.020.434 1499.2 -247.22 -215.18 32.05 3.294.1589 -.001 20.735.6470 20.030.434 1501.2 -247.14 -191.82 55.32 5.8 14. 1585 -.000 36.684 ~ 6631 ~0. 040. 434 1499.2 - 246 ~ 96 -154.83 92. 12 10 ~ 400. 15 87. 001 65. 516.7112 - 21.010.434 396.3 -229.02 -225.40 3.63. 229. 0893 -.001 2. 566. 7075 21.020.434 397.3 -228.08 -219.58 8.49.546.0896.001 6,996.....,7176 21.030.434 398.2 -228.65 -212.83 15.82 1.020.0852 -.000 11.969.7566 21.040. 434 398. 2 -228.89 -206. 88 22.01 1 ~ 621. 0848. 025 19. 094. 8674 21.050.434 401.2 -228.81 -204.22 24.59 2. 246,0857.013 26.182 1. 0649 21.060.434 401.2 -228.88 -194,03 34.85 4.643.0859.020 54.053 1.5512 21.070. 434 3 99.2 -228.85 -185 ~ 11 43.75 6. 860.0844 -. 004 81 ~ 308 t ~ 8586 21.080.434 400.2 -228.92 -177.61 51.31 9.216.0848.008 108.661 2.1177 21.090.434 400.2 -228.88 -161.57 67.31 10.459.0842.000 124.271 1.8463 21 ~ 100. 434 399.2 -22 8.90 -170.19 58. 71 9. 994. 0841.003 118. 866 2. 0246 21.110. 434 399.2 -228.99 - 174.21 54.78 9. 756.0839.002 116. 275 2.1224 22.010.434~........999.1 -242.50 -233.08 9.42.806...... 1'304 -.001 6.182.6562 22.020. 434 1001. 1 -242.51 -207.49 35.03 3. 133. 1307 -.001 23.964.6842 22.030.434 1001.1 -242.36 -188.67 53.69 5.010.1310 -.000..... 38.257,7126..... 22. 040. 434 999. 1 - 242.35 -1 54 ~ 34 88.01 9. 683 ~ 1306. 014 74 ~ 149. 8425 23.010. 434 599.2 -197.94 - 188. 22 9.72. 597. 0638 ~ 092 9i 357, 9628 23.020.434 602.2 -197.93 -182.14 15.79 1.083. 0639.001 16. 932 1.0720 23.030.....434 602.2 -197.90 -178.73 19.17 1.700.0639..069 26.526 1.38~5 23.040. 434 600.2 -197.97 -172.08 25.89 2. 941.0636.027 46.215 1.785 2 23.050.434 600.2 -197.69 -158.26 39.43 5. 322.0637.004 83.551 2.1190 23.061 ~ 434 602.2 - 197. 89 -126. 37 71 ~ 53 6. 935. 0640. OO0 108. 364 I ~ 515 0 a3.060.434 603.2 -197.91 -126.42 71.49 6. 935. 0641. 009 108.182 1. 513? 23. 070. 4 34 601 ~ 2 -197.89 -139 ~ 79 58 ~ 10 6. 347. 0638. 091` 99, 505 1 ~ 7126 -~3~ 90 -. 0 O0 89. 172 1 ~ 98&6.......434 600.2..... -197.88 -153.00 44.89 5.683.0637 ~4.010. 434 800.3 - 198. 57 - 190 ~ 47 8. 10. 578. 0857. 042 6. 745. 832 7 ~4.020. 434 798.3 -198. 52 -171. 13 27.39 2. 293. 0855.004 26. 799.9784 ~4.030.434 800.3 -198.51 -154.81 43.70 5. O1 8. 0856.024 58. 604 1.341 1 24.040.434 799.3 -198.42 -93.69 104.73 10.187. 0856.001 1 18. 959 1.1358 24.0 50. 434 799. 3 - 198.52 - 137. 26 61 ~ 26 7. 437. 0853. 002 87. 15? 1, 4227 24.060.434 798.3...... -198.52 -115.35 83.17 9.006.0852........091 105.676 1.27{J6...... 25.0 10.434 1997.2 -243.49 -231.32 12 ~ 17. 830. 1202 -. 002 6.905. 5676 25.020.434 2001.2 -244. O1 -210.84 33.17 2. 518. 1201 -.092 20 965.6320 25.0 30. 434 1999.2 -243.82 -185 ~ 88 57.93 4. 488. 1199 -. 000 37. 434. 6461 25.040.434 2000.2 -243.82 -151.86 91.96 7.410. 1201.001 61.702.6710 __ 26. 010.433 248,9 51 ~ 61 62.02 i0.42.626.1561.010 3.999.3838 26.020.433 248.9 51.61 ___ 70.775.........1` 9.!4......!-150.1561.010 7.357.3844 26.030.43~ 248.9 51.55 84.31 32.75 1.969.1560.010 12.611.3850 26.041.433 249.0 51.55 108.56 57.00 3.436.1561.010....21.996.3859 26.040 --.433 249.0 51.59 108.~8 57.09 3.437.1560.010 22.014.3856 27.011.434 999.2 50.52 74.05 23.53.474.0462. OOO 10. ~57.4357..... Z7.010,454 999.2 5C.51 74.11 23.60.474.0462.000 10.257.4347 27.020,434 998.2 50.52 73.96......23.44.870.......0856.00~ 10.160.4a35 27.030.434 998.2 50.76 74.27 23.51 1.265.1243.001 10.181.4331 27.040.434 998.2 50.76 74.48 23 ~ 71 1.626.1580.002 10. 288.4338 28.010.434 ' 249.2 -237.39 -232.45 4.93.501.1405.104 3.457.7o07 28,~20.436 249.2 -238.24 -230.30 7.g4 1.072....,1408..........043........7.571.4532 28.0 30.436 250.2 -238.23 -227 ~ 52 10.71 2. 292.1412.018 16.211 1. 5139 28.040.43 6 249 ~ 2 -237.47 -220.86 16.61 4. 749.1413.039 33. 571 2. 0216 28.050.436 248.8 -238.28 -211 ~ 19 27.09 8. 546.14,99.012 60.631 2.2378 28.060.436 247,2 -238.55 -203.69 34.87 11.919.1403,027 84.915 2,4353 28.070.436 249.2 -238.57 -191.34 47.23 17.862.141`4.014 126.298?.6740 28~ 081.....-436.........248.2 -238.45 -182,98 55,4? 18.36/+.....1404.........012......130.770....2 3577 28,080.436 247.2 -238.79 -182..77 56,03 18,374.1402.012 131.012 2.3384 29.010.436 1498.2 -198.14 -189.72 8.42.971.1629 -.000 5.961.7079 ':29,0'20.433 1498.2 -198.16 -167.61 30.55 3.690.1624.001 22.723.7437 29. 030.433 1498 ~ 2 - 198.22 - 145 ~ 89 52.33 6. 705.16 22. O02 41. 340 ~ 7900 29.040.433 1498.2 - 198.23 -1 17.81 80.42 11 ~ 140.1622.004 68.659 ~ 8537 30.010.433 501.2 50.72 56.97 6.25.371.1478.00s?. 503.4006 30.021.433 501.2 5C. 70 72.53 21 ~ 83 1 ~ 292 ~ 1479.004 8. 733.4000 30.020.433...... 500.8 50.70 72.58 21.88 1.292.1475.004 8.755 -.400i.30.030.433 501.2 50.70 84.57 33.87 2.006.1481.004 13.537.3996

- 182 - TABLE XLVII TABULATED EXPERIMENTAL ISOBARIC DATA FOR NITROGEN nletH nle t Outlet P F AH (b&/,T)p AT Power Flow 2H dP _pT Run Pressure Temperature Temperature (FP1 T' T (t/b (Btu (b-`F) (Psia (~F) (Btu/min) (lb/min)' ~P1 JT(Btu/lb) B) (Btu/lb-F) (psia) ('F) ('F) Iii Bul Y/ 2.010 1001.9 -196.07 -172.23 23.83.845.0492.000 17.170.7204 2.020 1001.4 -196.07 -172.40 23.67 1.526.0899.001 16.981.7173 2.030 1000.4 -196.08 -172.12 23.96 2.268.1324.003 17.125.7146 2.040 1000.4 -196.06 -172.36 23.70 2.805.1646.003 17.042.7191 2.050 999.4 -196.06 -172.22 23.83 3.292.1919.006 17.148.7195 2.060 1000.4 -196.05 -150.44 45.60 2.505.0893.001 28.041.6149 2.070 1000.4 -196.05 -150.53 45.53 3.551.1277.002 27.805.6108 2.080 1001.4 -196.01 -111.31 84.70 3.703.0861.001 43.004.5077 2.090 1000.4 -196.08 -111.05 85.03 5.562.1281.003 43.402.5104 2.101 1001.4 -196.07 -37.94 158.13 5.977.0878.001 68.079.4305 2.100 1001.4 -196.04 -37.68 158.36 5.926.0881.001 67.226.4245 2.110 999.4 -196.03 -37.53 158.50 8.704.1297.002 67.122.4235 2.120 1000.4 -196.04 33.38 229.42 11.403.1297.002 87.922.3832 2.130 1001.4 -196.03 33.31 229.34 7.830.0887.001 88.272.3849 TABLE XLVIII TABULATED EXPERIMENTAL ISENTHALPIC DATA FOR NITROGEN Inlet Inlet Pressure (T/P ~ CP Inlet Inlet Pressure ATA ATC Flow T2 (ATA/AP) (ATc/AP) Rum Temperature Pre s ste Drop, Run Temperature Pressure Drop ('F) ('F) (lb/min) T1CpdT ('F/psi) ('F/psi) ('F) (psia) (psi) 1 -.01- -147.1' JT996. 3 37.6 -.654 -.62-6.J ---L --- - 6-.32c.01799.C1666 2.020 -147.1 1996.4 115.8 -2. 181 -2. 185.1919 -1.11E.01884.01887 3.010 -147.1 18F6.3 116.0 -2.465 -2.480.1914 -1.259.02125.C2138 3.040 -147.1 1793.3 120.2 -2.882 -2.881.1909 -1.458.02398.02397 3.050 -147.1 1677.3 127.6 -3.46C -3.477.1902 -1.738.02712 C2726 3.070 -147.1 1570.3 143.4 -4.450 -4.473.1958 -2.208.03103.03119 3.1CC -147.1 1436.3 147.6 -5.310 -5.354.1897 -2.5C1. 03598.C3628 3.110 -147.1 1303.8 176.6 -7.385 -7.469.1967 -3.462.04184.C4230 3.140 -147.1 1152.2 2C1.4 -9. 826 -9.931.1950 -4.179.C4879. C4931 3.150 -147.1 62. 2 189.0 -1C.570 -10.69C.1673 -3.997.05593. C5657 4.010 -147.1 837.2 151.8 -8.942 -9.035.1365 -3.173.05891.C5952 4.040 -147.1 690.2 1FS.2 -12.133 -12.299.1329 -3.860.06413.C6501 4.050 -147.1 504.2 22C.8 -15.411 -15.608.1130 -4.343.C6980.C707C 5.010 32.6 1995.3 1f5.6 -2.956 -3.015.1689 -.911.C1593.C1625 5.040 32.6 1832.3 212.8 -. 683 -3.736.1738 -' 113.01731 C1756 5.050 32.6 1628.2 205.6 -?.8P4 -3.943.1607 -1.151.0189.C1918 5.080 32.6 144. 2 243.0 -4.983 -5.062.1638 -1.441.02C51.C2Ce3 5.090 32.6 1. 23.2 2C6.0 -4.673 -4.747.1403 -1.328.02269. C2305 5.120 32.7 1225.2 392.8 -9.063 -9.198.1E65 -2.511.02308.02342 5.130 32.6 848.2 282.8 -7.315 -7.425.1294 -1.968.02587.02626 5. 160 32.6 749.6 515.4 -14.281 -14.475.1467 -3.6.02771.02809 6.010 201.4 1 999.3 236.0 -1.788 -1.842.1583 -.494.00758. C0780 6.040 201.3 1 878.3 292.4 -2.36? -2.469.1730 -.650.00808. C0845 6.050 201.4 1585.9 417.6 -3.999 -4.153.1871 -1.068.00958. C0995 6.080 201.3 1202.4 38EC.2 -4.104 -4.269.1525 -1.084.01080.01123 6.090 201.4 878.4 39C.4 -4.691 -4.878.1261 -1.215.01202.01250 6.120 201,4 581.4 475.8 -6.246 -6.510.0970 -1.5EE88.01313,01368 TABLE XLIX TABULATED EXPERIMENTAL ISOTHERMAL DATA FOR NITROGEN Inlet Inlet Pressure Power Flow~~~~~cp AHTi (AH~AP)T Run Temperature Pressure Drop, 1AP)T ('F) (psia) (psi) (Btu/min) (lb/mn) (Btu/lb) (Btu/lb) (Btu/lb-psi) ~~~~~~~~~~~~~~~~~~~(Bt/F) (Bt/bpsia) (P 2.030 -147.1 1996.4. 117.4..229.1920.007 1.184 -.010087 _3.020 -147.1 1888.3 117.8.260.1915 -.003 1.358 -.011532 3.030 -147.1 1794.3 121.6.300.1911 -.004 1.577 -.012969 3.060 -147.1 1679.3 130.6.363.1903 -.000 1.909 -.014620 3.080 -147.1 1572.3 147.6.481.1956.003 2.455 -.016636 3.090 -147.1 1437.3 152.6.541.1890.005 2.855 -.018710 3.120 -147.1 1306.8 184.6.743.1957,o01 3.795 -.020557 3.130 -147.1 1155.3 212.6.893.1932 -.016 4.635 -.021804 3.160 -147.1 965.2 198.4.734.1659.002 4.421 -.022288 4.020 -147.1 839.2 159.0.470.1354 -.002 3.471 -.021830 4.030 -147.1 692.2 197.2.555.1312 -.003 4.232 -.021462 4.060 -147.1 507.2 229.4.521.1108.002 4.696 -.020475 5.020 32.6 1989.3 184.4.161.1683.011.944 -.005120 5.030 32.7 1833.3 213.6.203.1737 -.000 1.169 -.005473 5.060 32.6 1629.2 207.4.194.1606 -.003 1.210 -.005837 5.070 32.6 1446.2 245.4.250.1635.008 1.519 -.006189 5.100 32.6 1227.2 210.0.189.1387.002 1.363 -.006492 5.110 32.6 1226.2 398.0.495.1855 -.001 2.669 -.006707 5.141 32.6 851.2 289.8.265.1292 -.002 2.055 -.007090 5.140 32.6 852.2 289.8.265.1294 -.009 2.059 -.007106 5.150 32.5 750.6 520.2.558.1448.007 3.850 -.007402 6.020 201.3 2037.3 236.6.084.1618 -.004.523 -.002209 6.033 201. 3 1883.3 292.4.123.1734 -.002.713 -.002440 6.060 201.3 1590.4 420.8.218.1873 -.001 1.166 -.002772 6.070 201.3 1206.9 383.8.182.1528 -.005 1.195 -.003114 6.100 201.4 879.4 391.4.167.1258.002 1.325 -.003385 6.110 201.4 581.4 475.6.169.0962.003 1.754 -.003688

- 183 - TABLE L TABULATED EXPERIMENTAL ISOTHERMAL DATA FOR THE NOMINAL $ PERCENT MIXTURE T2 Mole Inlet Inlet Prower Flow T1CpdT AA Run Fraction Temperature Pressure Drop (Btu/min) (Fb/miR) (Btu/lb) (Btu/lb( t/-) C3H8 (psla) (psi) C~s~ -~T~ S~7~-.O0. 0"2 1';9.S l3i.e -~5. le.023.itc2. C17 2 ~]2 -.2i72,2 7.011.05' ]cc. 1`59. 16r,.0.372. 11C2.C_1- 2.06 -.017612 7.020.052 119.9. 176~.2 169.0.?43.1C77. C31?.155 -.018672 7.021..052 l C9.c 176?.4 169.0.-43.1072.~=4 -.165 -.C1)7]~ 7.070.C52 199.9 158C.7 1 81.4.368.1044.C20 3.500 -.019294 7.031.052 ] G9.q 1577.5 181.6.368.1042.C3S 3.48e.019212 7.040.052 199. q 391.9 283.4.6e;8.1213. Co1,.753 -. C20303 7.041.052 Icc. c p8.? 2~.4.0.6c,3.1210. C08 5.721 -.020i46 7.050.052 199.9 112S.2 325.4.759.1172.el? 6.6;4 -.020573 7.C51.052 lC;9. 1127.8 324.2.757.1128. CC 6.6S6 -.020657 7.060.052 199.9 P24. q:28. 6.526. C873.C10 f.C16 -.020994 7.061 C057 199.9 81F.5 284.2.518.0866.C17 5.061 -.020978 7.070.052 lC9.q 554.9 217.C.277.C507.012 4.630:-.C21339 7.071.052 llq,., $51.7 216.6.274.C503. C21 4.604 -.021260 7.080.052 l C,.c 554.7 451.2.719.0747.C11 S.612 -.C21305 7.081.O;? lq9.q r_51.7 450.4.715.C744. C06 S.59(; -.021315 7.09C.052 199.~ 1120.5 37C.4.914.1191. CC4 7.670 -.020710 7.091.052 199.9 1119.5 3tq.6.914.1187.CO3 -.6S6 -.020823 8.010. C51 20C.q 1q7.O0 qq.2.232.1381 -.C0 7 ].6et6 -.0169S6 8.019.051 2CC.S 1 978.0 99.2.232.13E1 -.C07.6-C7 CC5 8.020.051 200.c, 1910.6 241.0. S40.2158.C12 4.345 -.018033 8.030.051 200.q 171'.F 218.0.782.192C' -.C02 4.C56 -.018608 8.039.051 200. c 1715.8 218.0.782.1920 -.C02 4.C52 -.018588 8.04C.051 200.9 1504.C 1ql.4.612.16768 - 019121 8.050.051 200.9 1315.0 244.4. F46.1747 -.007 4.E4; -.019843 8.,060.051 2CC.S 111=.5 2C9.4.621.146c -.C02 4. 227.. '02i-88 8.061.051 2CO.1 111.4.4 2C8.8.621.1467 -.CO0 4.231 -.020265 8.070.051 20C.S c Cq.7 206.8.553.1201.CO1 4,281 -. 02070}1 8.071 C051 200.9 C;c,, c 206.8.553.12S1.C04 4.277 -.020684 8.080.051 200.9 704.5 227.A. 549.1147. C09 4.773 -, 02i000 -8.081.051 200.c; 7C7.0 228.7.553.1152.0-131? 4.7 e8 -.020937 8.090.051 200. q 514.8 254.9.521. C367,.Cci...5.379 -.C211C5 8.091.051 200.c 512.9 254.2.520. CC64.013 5.384 _ -—.021 181 8.100.051 200.c 31c.2 218.2.301.0636.C18 4-710 -.0215E6 a.101.051 200.c 317.5 218.2.294.0637 -.C1 3 4.657 -.0 21345- 9.010.051 91.6 l99.5 91.0.37`.1592. ClO 2.373 -.026082 q.011.051 91.6 200C,3 Cl.4.379.15<.2.CIC 2.374 -.025975 9.0 20.051 91.7 1}32.3 148.4. e20.?C24 17 4034 -.C27183 9.021.051 Cl.7 1$32.1 148.6.820.2024.C05 4.C46...027233 9.030.051 91.6 18C2.3 17q.0 1.095.2143. 004 5.105 -,,28521 9.o31.051 <1.6 1802.6 178.6 1.095.2144.Cec..108 -.0286C4 q.040, 051 91.6 1620.c 217.2 1.451.2217. C03 6.543...30125 9.041.051 91.6 1621.4 217.2 1.445.2217 -.00 1.........C.o._! 7...6.... -.c30009 9.050.051 q1 6 1440.0 240.8 1~622.2171 -. C2 7. 478 -.C31057 9.051.051 c;1.7 144C.8 239.8 1.617.2168.Cll 7.446 -.0=_1056 9.060.051. 12345 266.6 1.737. 2067.CO1 F,4Cg..031534 13.061.051 91.6 1235.4 265.8 1.730.2067 -.011 E.381 -.0 31535 q.070.051 91.6 970.2 215.6!. C90.1600.C11 6.804:.03156i9.071.051 91.6 968.4 215.4 ].Cqe.15 8~.013 6.807 -.0316C3 9.080.051 C786. 209.6 ~ CP.1377.C12 6.583 -.C314CS 9.081.051 <1.6 786.0 209.4.Ioe.1377. 002 6. 92 -.C314e5 9.090.051 91.6 58C.7 23`3.8. 82.1167 -.CO1 7.434 -.0310C2 9.091.051 91.6 5C.14 23c.4.8R2.!1F6 -.CO1 7.437 -:0?1070 9.10C.051 91.6 346.3 241.4.581.0801 -.CC5 7.265 -.0300S6 `,101.051 91.6 345.6 241.4.586.0800 C1.4.3_06 -.030268 ]0.010.051 -27.0 1941.5 86.4.514.2123 -.C20 2.44C -.028244 10.011.051 -27. C 1943.9 86.8.518.212cj -.C19 2.452 -.028246 10.020.051 -27.C 1886.1 100.2, 722.2267. CO1 3.184 -.031175

- 184 - TABLE L (Contri nleft) Mole Inlet Inlet Pressure 2Power Flow Power Flow LT1CPdLT ART (Afi/AP)T Run Fraction Temperature Pressure Drop Run Fraction Temperature Pressure Drop (Btu/min) (lb/min) (Btu/lb) (Btu/lb) (Btu/lb-psi) C3H8 (.F) (psia) (psi) 10.C021.01 - 7. C 1 7.7 100.0.722.22f 1.C?1 3.161 -.C-161 1C. 00. ( -27. C 130. 2 1CC.4. 80.??0 C C12 3.71C -.0 6 951 13.01I.5 -?7.C 17SS.6 1C0.7. F3.2228.CO1 3.724 -.C37171 13.040. -'7. C 17C4. 107.0 1.C67.7242.C13 L.744 -.C4433c 10.041.0 -7. C 1704.? 106.8 1.C61.2 38.C25. 716 -.C44164!90. 050,1 -? 7. C 1597.8 121.0 1. 12. 23C6,C19 6.540 -.054C55 1!.051.05! -27. 1c6.2 121.? 1.512.23C0 -.CC8 (. 6c -.C 42Ce 1 C C. -?7. C 147.8 127.r 1.858.22C.C16 E. 41 -.,06489 1.0. ].! -?7.C 147,.C 127.? 1.88.224$.007 E.?55 -.C64SC0 10.070. -'7. 0 1362.4 139.4 2.281.7216 -. CC5 1C.?C? -.07?SC8 10 7. 057 -'7.C I 61.8 1?9.4 2.2PC80.2214,CC7 1C.295 -. 0786C I i0.05 I -27. C I1 54.8 159.8 2.781.2212.C28 12. 54 -.076517 i.0An1. 91 -?7.C 1?51.4 1 59.4 2.76.27C?5.C32 12. C2 -.C78436 1. C.1 -?7.0 1 12 c.c 174.0 2.4.2111 CC1 13.66. - C C78511.10.lI 07.I 1127.2 174.? 2.84.?IC6.013 13.634 -,C78274 11.01 -?7.1 1013.1 I 146.4 1.979.171.C18 11.09 C -.C75771 11.01 1.Ol ->7. 1 10! 2.9 146.4 ].979.17P1.C22 11.C88 -.C75742 11.020.5cl -27.1 837.6 145.0 1.520C.1527.C19 S. SS8 -.C6895% 11.C? I. 5 -7.1 8P7., 145.? 1.530.1526.C18 1C.CC0 -C689 17 i.03C. -7.1 707.7 177.0 1.628.14(0 -.CC5 11. 151 -.06?CC4 11,0 1 -?7.1 7C2,3 177,0 ]. 628.146C -.C01 11. 148 -.C62989 11.040.51 -'7.1?.q9 723.2 1.6'5.1311 -.C11 12.561 -.C552E2 1.41 7.1 1 -7. 22.8 1.,645.1C8.CC8 12. 561 -.C56361 1I.01. -?7. 1 325,1 199.6.8C06.C8C.C10 c.989 -.C5CC48 _1.q51.051 27. 1 C4.6 199.4.e0o.CEC5.C13 c.993 -.050122 11. 6I.051 -?7.1 llC9.3 16.2.117.214. C21 14.C9 -. C7727 11.. C! -7. 1 110. 186.0 106.2142.17 14.483 -.C 77872 12?. 10C.2 8 -147.4 1791., C.000.1129.637 -.637.CC1C54 12.011. -1 47.4 1787.4 C5.3.CCC 11 27 63C -. 6C CC.0010C41.I D2., 1.O! -14 7. 4 1 747.1 223..0 C0.C669.304 -.304.C0C13 5 12.21l -147.4 1744.9 274.0.000.C668.3C1 -.3C1.CC1345 12.03C Cl -147.4 1C90.3 2 84.?.000.07C.Ce3 -. C083.CCC23! ~ 31 I (51 - 147.4 1 2 2.1 2 5.6.000.0753. C75 -.075.003263 12.040.05! -147.4 1307.5 510.0.000.1023 -.C14.C14 -.OC0028 17.n41.051 -147. 5 1305.1 509.4.CCC.1021 -.C18.C18 -,CCCC35 12.050.,Ol. -147. 4 11C. 1 78.8.047.126C.C02.37C -.CCC488 2' 051.05 -147.4 1312.6 757.0.C47.1259 -. CO.373 -.C0C4C3

TABLE LI CONSTANTS FOR BENEDICT-WEBB-RUBIN EQUATIONS OF STATE Units: atmospheres, litres, gram-moles, OK R = 0.08206 T(~K) = 273.15 + T(~C) 10 10 Methane10 Propane Nitrogen Stotler b79 Crain &36 Bloomer Benedict Sonntag & Rao15 A 1.855 6.87225 1.1925 0.872086 1.27389 0o B 0.0426 0.097313 0.0458 0.0281066 0.0484824 0 C 22570. 508256. 5889.07 7813.75 4273. 0 a 0.0494 0.9477 0.0149 0.0312319 0.0178444 b.00338004 0.0225 0.00198154 0.0032351 0.00232373 c 2545. 129000. 548.064 547.364 475. a 0.000124359 0.000607175 0.000291545 0.0000709232 0.000153 y 0.006 0.022 0.0075 0.0045 0.0065 D 7617810. 832000. -185 -

TABLE LII COMBINING RULES FOR CONSTANTS IN THE B-W-R EQUATION OF STATE A = ( x. A 1/2) o mix i1 i. i 1 1 Z x.x (B 1/3 1/3) B EC X. (B + B o mix 8 1 o. o. i j 1 J C. = (E X. C 1/2) o mix. 1 0. i 1 1/3 a = ( x.a. ) mix 1 1 1/3 b ( x.b. ) b 1 1 mix i 1/3 3 c. = ( xc. c ) mix i 1 1 oa = (I x. a. ) mix 1 1 1/2 y = (Z xi Yi ) mix i - 186 -

SAMPLE CALCULATION The conditions chosen are 1500 psia and 500F for the nominal 43 mole percent nitrogen in methane mixture. The following procedure was used to obtained the enthalpy tabulated in Table XXX: 1. The enthalpy of the ideal gas mixture of 1000F and zero pressure was calculated from the values of Rossini adjusted to the enthalpy datum of the present work. This calculation is given on Page 127 and results in a value of 278.23 BTU/lb. 2. The effect of pressure on enthalpy from zero pressure to 1500 psia was estimated using the Benedict-Webb-Rubin equation for the enthalpy departure given on Page 167 with the constants for nitrogen of Stotler and Benedict and those for methane of Benedict, Webb, and Rubin given in Table LI. The constants for the mixture were determined using the combining rules given in Table LII. This calculation resulted in an enthalpy departure of 20.05 BTU/lb. making the enthalpy at 1500 psia and 100~F equal to 258.18/lb. 3. The experimental data of (AH/AT)P for Run 3 given on Page 180 were plotted as shown in Figure 14 and a smooth curve drawn through the data bars in the region of 50 to 1150F. 4. Integration of the smooth curve with respect to temperature between 50~F and 100~F gave a value of the enthalpy difference of 23.04 BTU/lb. 5. The enthalpy at 1500 psia and 500F was calculated by subtracting 23.04 BTU/lb from the value at 1500 psia and 1000F of 258.18 to give 235.14 BTU/lb. 6. This value, rounded off, is listed in Table XXX for this mixture at 1500 psia and 500F. - 187 -

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UNIVERSITY OF MICHIGAN 3 901 5 03483 75941111111 3 9015 03483 7594