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NBS Technical Note 1249

Evaluation ofData Availability and Quality for Interaction

Second Virial Coefficients of Use to the Gas Industry

Bernard J. Van Wie, Mark A. Langenberg, Wayne C.-W. Chang, KesavaluH. Kumar,

and Kenneth E. Starling

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National Bureau ofStandards m

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TM he National Bureau of Standards' was established by an act of Congress on March 3, 1901. The Bureau's overall j^^ goal is to strengthen and advance the nation's science and technology and facilitate their effective application for public benefit. To this end, the Bureau conducts research to assure international competitiveness and leadership of U.S.

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RESEARCH INFORMATION CENTER

National Insti tute of

Standards and Technology

Gai thersburgi MD 200??

NBS Technical Note 1249

Evaluation ofData Availability and Quality for Interaction

Second Virial Coefficients of Use to the Gas Industry

Bernard J. Van Wie, Mark A. Langenberg, Wayne C.-W. Chang, Kesavalu H. Kumar,

and Kenneth E. Starling

The University of Oklahoma

School of Chemical Engineering

and Materials Science

The Energy Center

Norman, OK 73019

July 1988

•"•tAu of *

U.S. Department of Commerce

C. William Verity, Secretary

National Bureau of Standards

Ernest Ambler, Director
National Bureau of Standards U.S. Government Printing Office For sale by the Superintendent

Technical Note 1249 Washington: 1988 of Documents,

Natl. Bur. Stand. (U.S.), U.S. Government Printing Office,

Tech. Note 1249 Washington, DC 20402

104 pages (July 1988)

CODEN: NBTNAE
Foreword

The National Standard Reference Data System was established in 1963 for the purpose of promoting the critical evaluation and dissemination of numerical data of the physical sciences. The

program is coordinated by the Office of Standard Reference Data of the National Bureau of Stan- dards but involves the efforts of many groups in universities, government laboratories, and private

industry. The primary aim of the program is to provide compilations of critically evaluated physical and chemical property data. These tables are published in the Journal of Physical and Chemical

Reference Data, in the NSRDS-NBS series of the National Bureau of Standards, and through other

appropriate channels.

A necessary preliminary step to the critical evaluation process is the retrieval from the world

scientific literature of all papers reporting measurements on the property in question, followed by

the extraction and organization of the numerical data contained in these papers. The present Technical Note summarizes the available data on interaction second virial coefficients for hydrocarbons

and other compounds commonly present in natural and synthetic gas. We hope this summary will be useful to those engaged in correlation of such data and that it will stimulate new experimental

measurements on systems for which the existing data are inadequate.

Further information on NSRDS and the publications and computerized databases which form the

primary output of the program may be obtained by writing to the Office of Standard Reference

Data, National Bureau of Standards, Gaithersburg, MD 20899.

David R. Lide, Jr., Director

Office of Standard Reference Data

m
Table of Contents

Foreword iii Abstract 1

1. INTRODUCTION 1

2. PROCEDURES FOR ASSESSMENT OF DATA AVAILABILITY, QUALITY

AND NEEDS 2

2.1 Data Availability 2

2.2 Data Quality 3

2.3 Data Needs 5

3. SUMMARY OF DATA RANGES AND DATA QUALITY 6

4. EVALUATIONS FOR INDIVIDUAL BINARY SYSTEMS DATA 6

4.1 Methane Binaries 7

4.1.1 CH4-C2H6 7

4.1.2 CH4-C3H8 . 7

4.1.3 CH4-n-C4Hio 8

4.1.4 CH4-i-C4H:o 9

4.1.5 CH4-n-C5Hi2 10

4.1.6 CH4-i-C5Hi2 11

4.1.7 CH4-neo-C5Hi2 11

4.1.8 CH4-CO 11

4.1.9 CH4-CO2 12

4.1.10 CH4-N2 12

4.1.11 CH4-H2 12

4.1.12 CH4-H2O 13

4.1.13 CH4-H2S 13

4.1.14 CH4-He 13

4.1.15 CH4-NH3 13

4.2 Ethane Binaries 14

4.2.1 C2H6-C3H8 14

4.2.2 C2H6-n-C4Hio 14

4.2.3 CsHe-n-CsHn 15

4.2.4 C2H6-CO2 15

4.2.5 C2H6-N2 16

4.2.6 C2H6-H2 16

IV
4.2.7 C2H6-H2O 16

4.2.8 C2H6-H2S 17

4.3 Propane Binaries 17

4.3.1 C3H8-n-C4Hio 17

4.3.2 C3H8-n-C5Hi2 17

4.3.3 CsHg-i-CsHis 18

4.3.4 C3Ha-C02 18

4.3.5 C3H8-N2 18

4.3.6 C3H8-H2 19

4.3.7 CaHg-He 19

4.4 n-Butane Binaries 20

4.4.1 n-C4Hio-i-C4Hio 20

4.4.2 n-C4Hio-n-C5Hi2 20

4.4.3 n-C4Hio-C02 20

4.4.4 n-C4Hio-N2 21

4.4.5 n-C4Hio-H2 22

4.4.6 n-C4Hio-He 22

4.5 Isobutane Binaries 23

4.6 n-Pentane Binaries 23

4.6.1 n-C5Hi2-C02 23

4.6.2 n-C5Hi2-N2 24

4.6.3 n-C5Hi2-H2 24

4.7 Isopentane Binaries 24

4.7.1 i-C5Hi2-C02 24

4.7.2 i-C5Hi2-N2 25

4.7.3 i-C5Hi2-H2 25

4.8 Neopentane Binaries 25

4.8.1 neo-C5Hi2-N2 25

4.8.2 neo-C5Hi2-He 26

4.8.3 Other Neopentane Binaries 26

4.9 CO Binaries 26

4.9.1 CO-CO2 26

4.9.2 CO-H2 26
4.10 Carbon Dioxide Binaries 27

4.10.1 CO2-CS2 27

4.10.2 CO2-N2 27

4.10.3 CO2-H2 28

4.10.4 CO2-H2O 28

4.10.5 CO2-H2S 29

4.10.6 COs-He 29

4.11 CS2 Binaries 29

4.12 COS Binaries 29

4.13 Nitrogen Binaries 30

4.13.1 N2-H2 30

4.13.2 N2-H2O 30

4.13.3 N2-H2S - . 31

4.13.4 N2-He 31

4.13.5 N2-NH3 32

4.14 NOx Binaries 32

4.14.1 N2O-H2O 32

4.14.2 Other NO^ Binaries 33

4.15 Hydrogen Binaries 33

4.15.1 H2-H2O 33

4.15.2 H2-He 33

4.16 Hydrogen Cyanide Binaries 34

4.17 SOx Binaries 34

4.18 Ammonia Binaries 34

Acknowledgments 35

References 86

VI
List of Figures

Figure Page

1. Number of references for interaction second virial coefficient data for natural gas

and syngas components 45

2. Interaction second virial coefficient data needs for natural gas and syngas

components 45

3. Temperature dependence of interaction second virial coefficient for the CH4-C2H6

system 46

4. Temperature dependence of interaction second virial coefficient for the CH4-C3H8

system 46

5. Temperature dependence of interaction second virial coefficient for the CH4-n-C4Hio

system 47

6. Temperature dependence of interaction second virial coefficient for methaneparaffin hydrocarbon binary systems 47

7. Temperature dependence of interaction second virial coefficient for methaneparaffin hydrocarbon binary systems 48

8. Temperature dependence of interaction second virial coefficient for the CH4-i-C4Hio

system 48

9. Temperature dependence of interaction second virial coefficient for methaneparaffin hydrocarbon binary systems 49

10. Temperature dependence of interaction second virial coefficient for methane-paraffin

hydrocarbon binary systems 49

11. Temperature dependence of interaction second virial coefficient for the CH4-n-C5Hi2

system 50

12. Temperature dependence of interaction second virial coefficient for the CH4-i-C5Hi2

system 50

13. Temperature dependence of interaction second virial coefficient for methane-paraffin

hydrocarbon binary systems 51

vu
14. Temperature dependence of interaction second virial coefficient for the

CH4-neo-C5Hi2 system 51

15. Temperature dependence of interaction second virial coefficient for methane-paraffin

hydrocarbon binary systems 52

16. Temperature dependence of interaction second virial coefficient for the CH4-CO2

system 52

17. Temperature dependence of interaction second virial coefficient for carbon

dioxide-paraffin hydrocarbon binary systems 53

18. Temperature dependence of interaction second virial coefficient for the CH4-N2

system 53

19. Temperature dependence of interaction second virial coefficient for nitrogen-paraffin

hydrocarbon binary systems 54

20. Temperature dependence of interaction second virial coefficient for the CH4-H2

system 54

21. Temperature dependence of interaction second virial coefficient for the CH4-H2O

system 55

22. Temperature dependence of interaction second virial coefficient for the CH4-He

system 55

23. Temperature dependence of interaction second virial coefficient for the CH4-NH3

system. . 56

24. Temperature dependence of interaction second virial coefficient for the C2H6-C3H8

system 56

25. Temperature dependence of interaction second virial coefficient for ethane-paraffin

hydrocarbon binary systems 57

26. Temperature dependence of interaction second virial coefficient for the

C2H6-n-C4Hio system 57

27. Temperature dependence of interaction second virial coefficient for ethane-paraffin

hydrocarbon binary systems 58

VIU
28. Temperature dependence of interaction second virial coefficient for the

C2H6-n-C5Hi2 system 58

29. Temperature dependence of interaction second virial coefficient for ethane-paraffin

hydrocarbon binary systems 59

30. Temperature dependence of interaction second virial coefficient for the C2H6-CO2

system 59

31. Temperature dependence of interaction second virial coefficient for carbon

dioxide-paraffin hydrocarbon binary systems 60

32. Temperature dependence of interaction second virial coefficient for the C2H6-N2

system 60

33. Temperature dependence of interaction second virial coefficient for nitrogen-paraffin

hydrocarbon binary systems 61

34. Temperature dependence of interaction second virial coefficient for the C2H6-H2O

system 61

35. Temperature dependence of interaction second virial coefficient for water-paraffin

hydrocarbon binary systems 62

36. Temperature dependence of interaction second virial coefficient for the C2H6-H2S

system 62

37. Temperature dependence of interaction second virial coefficient for the

C3H8-n-C4Hio system 63

38. Temperature dependence of interaction second virial coefficient for propane-paraffin

hydrocarbon binary systems 63

39. Temperature dependence of interaction second virial coefficient for the

CaHg-n-CsHia system 64

40. Temperature dependence of interaction second virial coefficient for propane-paraffin

hydrocarbon binary systems 64

41. Temperature dependence of interaction second virial coefficient for the C3HS-CO2

system 65

IX
42. Temperature dependence of interaction second virial coefficient for carbon

dioxide-paraffin hydrocarbon binary systems 65

43. Temperature dependence of interaction second virial coefficient for nitrogen-paraffin

hydrocarbon binary systems 66

44. Temperature dependence of interaction second virial coefficient for the CaHg-He

system 66

45. Temperature dependence of interaction second virial coefficient for the

n-C4Hio-i-C4Hio system 67

46. Temperature dependence of interaction second virial coefficient for n-butaneparaffin hydrocarbon binary systems 67

47. Temperature dependence of interaction second virial coefficient for the

n-C4Hio-n-C5Hi2 system .68

48. Temperature dependence of interaction second virial coefficient for n-pentaneparaffin hydrocarbon binary systems 68

49. Temperature dependence of interaction second virial coefficient for the n-C4Hio-C02

system 69

50. Temperature dependence of interaction second virial coefficient for carbon

dioxide-paraffin hydrocarbon binary systems 69

51. Temperature dependence of interaction second virial coefficient for the n-C4Hio-N2

system 70

52. Temperature dependence of interaction second virial coefficient for nitrogen-paraffin

hydrocarbon binary systems 70

53. Temperature dependence of interaction second virial coefficient for the n-C4Hio-He

system 71

54. Temperature dependence of interaction second virial coefficient for the n-C5Hi2-C02

system 71

55. Temperature dependence of interaction second virial coefficient for carbon

dioxide-paraffin hydrocarbon binary systems 72

X
56. Temperature dependence of interaction second virial coefficient for the n-C5Hi2-N2

system 72

57. Temperature dependence of interaction second virial coefficient for the n-C5Hi2-H2

system 73

58. Temperature dependence of interaction second virial coefficient for carbon

dioxide-paraffin hydrocarbon binary systems 73

59. Temperature dependence of interaction second virial coefficient for the i-C5Hi2-N2

system 74

60. Temperature dependence of interaction second virial coefficient for nitrogen-paraffin

hydrocarbon binary systems 74

61. Temperature dependence of interaction second virial coefficient for the

neo-C5Hi2-N2 system 75

62. Temperature dependence of interaction second virial coefficient for nitrogen-paraffin

hydrocarbon binary systems 75

63. Temperature dependence of interaction second virial coefficient for the

neo-C5Hi2-He system 76

64. Temperature dependence of interaction second virial coefficient for the CO-CO2

system 76

65. Temperature dependence of interaction second virial coefficient for the CO-H2

system 77

66. Temperature dependence of interaction second virial coefficient for the CO2-N2

system 77

67. Temperature dependence of interaction second virial coefficient for the CO2-N2

system 78

68. Temperature dependence of interaction second virial coefficient for the CO2-H2

system 78

69. Temperature dependence of interaction second virial coefficient for the CO2-H2O

system 79

XI
70. Temperature dependence of interaction second virial coefficient for the C02-He

system 79

71. Temperature dependence of interaction second virial coefficient for the C02-He

system (datum on Edwards and Roseveare deleted) 80

72. Temperature dependence of interaction second virial coefficient for the N2-H2

system (36-323K temperature range) 80

73. Temperature dependence of interaction second virial coefficient for the N2-H2

system (148-323K temperature range) 81

74. Temperature dependence of interaction second virial coefficient for the N2-H2O

system 81

75. Temperature dependence of interaction second virial coefficient for the N2-He

system 82

76. Temperature dependence of interaction second virial coefficient for the N2-NH3

system 82

77. Temperature dependence of interaction second virial coefficient for the N2O-H2O

system 83

78. Temperature dependence of interaction second virial coefficient for the H2-He

system (14-448K temperature range) 83

79. Temperature dependence of interaction second virial coefficient for the H2-He

system (148-448K temperature range) 84

80. Temperature dependence of interaction second virial coefficient for the H2-He

system (14-90K temperature range) 84

xu
List of Tables

Table Page

1. Ranking Classification for Interaction Second Virial Coefficients 4

2. Interaction Second Virial Coefficient Data Ranges and Rank 36

3. Recommended Unlike Interaction Second Virial Coefficients 42

XUl

Abstract

Binary interaction second virial coefficient information useful to the

natural and syngas industries has been compiled and evaluated. An ex- tensive literature search has been conducted to obtain publicly available

information dating back to 1900. Assessments were made to determine

data availability, quality and to summarize data needs. No evaluations were made for values resulting from thermodynamic correlations; however, references containing such information are listed. Each binary gas

system has been individually evaluated and references containing the

highest quality and most abundant measurements have been listed in a table of recommended values.

1. INTRODUCTION

As one of four participants in a Gas Research Institute funded project, it has been

the task at the University of Oklahoma to assess the availability and quality of binary

interaction second virial coefficient, B12, data for the natural gas and syngas industries

and to project needs for new data. This paper focuses on data availability and quality

assessments. Suggestions for the procurement of new data are also made. Interaction

second virial coefficients, -Bi2's, can be used for describing real gas behavior of mixtures

and for this reason are of importance to the natural gas and syngas industries. Not only

are virial coefficients useful in describing PVT relationships through the virial form of

the equation of state, but also in describing thermodynamic properties such as fugacities,

internal energies, enthalpies, heat capacities, entropies, Joule-Thomson coefficients and

gas phase excess properties. The capability for accurate prediction of such properties is important to the gas industries for correlation development and plant design.

Specific instances in which interaction second virial coefficients may be of greatest

importance are in vapor-liquid equilibrium correlation development work where the component fugacities in the gas phase may be calculated using B12 data. These fugacities

in turn are used to test activity coefficient correlations for the liquid phase, and in the

development of mixture equations of state which have the theoretically correct composition dependence and are accurate in the lower density limit. Interaction second virial

coefficients also are used to determine intermolecular potential function parameters; this

application is of greater theoretical than industrial use. Little use has been made in the

gas industry of interaction second virial coefficients at extremely low temperatures for

two reasons: 1) the effect of higher virials becomes more important; and 2) there are fewer accurate interaction second virial coefficient data available due to the fact that the

range of pressure over which one can secure data gets smaller due to condensation as temperature is decreased. Therefore, one must depend upon equations of state in order to

obtain information about gas properties at temperatures where interaction second virial

coefficients are less available.

In the past, industry was able to rely on lower quality data, because financial inequities in custody transfer and excess plant costs due to overdesign were not exorbitant.

1
However, in an age of diminishing natural resources and an ever tightening economy,

industry is forced to be more conservative. Since accurate data are required for better

thermodynamic correlations and improved process designs, a critical look at data availability, accuracy and needs is important.

It is also important to look at data for the syngas industries. Basically the design and

operation of syngas plants and the storage and custody transfer of syngas requires the same

kinds of data as are needed for the natural gas industries. However, many components are present in syngas which are either nonexistent or are only minor constituents in natural

gas.

In many cases B12 data can be supplemented with B12 values calculated from existing

PVT data. Non-virial equations of state (if available and accurate) can also be used to

supply required properties information for the gas industries. However, where accurate

PVT and B12 data are lacking (and at pressures which are low enough for a virial equation

of state using only the second virial coefficient to be accurate) the measurement of new

B12 data is of significant industrial importance.

It should also be noted that the significance of data quality is relative to the particular

application for which the data are to be used. For instance, when gas properties are to be

predicted for a gas of predominately one component, the contributions to bulk properties

from unlike interactions with other components are minimal. Therefore, accurate B12

information is of little importance for bulk gas properties prediction for gases consisting

of predominately one component. In such cases even low quality data or rough estimates of

Bi2^s with the use of moderately reliable correlations are probably adequate for properties

predictions.

On the other hand accurate B12 information is critical in instances where one is interested in properties for gas processing such as in separations. Also accurate B12

information may be very important for custody transfer of gases containing large amounts

of carbon dioxide or nitrogen and for the custody transfer of syngas. One must also be

concerned with the pressure of the gas for which properties predictions are important. The

contributions of unlike interactions are more significant at higher pressures and therefore

higher quality data are more important at higher pressures. Also, one must be aware of

the fact that the effect of higher virials becomes more important as pressure increases and

therefore the existence of accurate Bi2^s alone may not be sufficient. A specific case in

which higher virials are important is in the design of compressors.

2. PROCEDURES FOR ASSESSMENT OF DATA AVAILABILITY,

QUALITY AND NEEDS

2.1 Data Availability

A literature search was performed to locate and retrieve available interaction second

virial coefficient information dating back to 1900 for all binaries of importance to the

natural gas and syngas industries. Extensive bibliographical and data range information
were also available through a compilation by Dymond and Smith, The Virial Coefficients

of Pure Gases and Mixtures,^ and from supplementary material to a publication by Hayden

and O'Connell appearing in Ind. Eng. Chem. Proc. Des. Dev? An additional source by Warowny and Stecki^, The Second Cross Virial Coefficients of Gaseous Mixtures^ is available and may be of use as a cross reference for investigators interested in doing their

own assessments. However, this text contains little additional information for systems

of interest in this paper. The compilation by Dymond and Smith contains information

about uncertainties for some data sets which served as an aid in making evaluations

of data reliability, and needs. However, none of the above references contain a critical

comparison between the data from individual authors, nor do they discuss data needs.

Hence, the present assessment is of great value.

As shown in Figure 1 the number of references for each binary system was placed

in the grid on a triangular data availability chart so that a quick assessment of available

data could be made. Blank grids in the data availability chart are representative of binary

systems for which no data references were found. Where a blank grid appears for a binary

system of high importance to the gas industry, a critical data need exists. In cases where

a large number of references are indicated in a grid for a particular binary system, data

needs are expected to be less critical, and the focus for that particular binary system can be shifted to determination of which of these references contain data of highest quality.

Binaries with the greatest abundance of references generally correspond to those

binaries which are of greatest importance to the gas industry (ie.: binaries involving

major constituents of pipeline quality gas and dehydrated sweet natural gas as it enters

the processing plant). There is a large number of B12 data references involving hydrogen,

in part due to the many industrial processes involving hydrogen. Helium binaries also have an abundance of references, which can be attributed in part to data needs for processes

for recovery of helium from natural gas. Binaries of H2S and H2O, which also are of

importance to the gas industry, have relatively fewer numbers of references, possibly

because of difficulties in experimental measurements, since H2S is poisonous and highly

corrosive, and adsorption problems in H2O systems cause difficulties in obtaining high

accuracy virial coefficient (and/or PVT) data. Also relatively few references are available

for a number of syngas binary systems.

2.2 Data Quality

In the present work, the rankings 'A', 'B', 'C and 'X' in Table 1 were used in order

to classify the available interaction second virial coefficient data or theoretical values of

different investigators. An 'A' ranking corresponds to data which are accurate to within

5% or 5 cm^/mol and are of quality sufficient for process design correlation development.

'B' ranked data are those which have inaccuracies greater than 5% or 5 cm^/mol, but less than 10% or 15 cm^/mol. The 'B' ranked data are sufficient for design purposes. A 'C

ranking corresponds to data which are inaccurate by more than 10% or 15 cm^/mol, and

are less than adequate for most industrial uses. An 'X' ranking corresponds to B12 values

which have been determined through the use of a correlation.
Table 1 Ranking Classification for Interaction Second Virial Coefficients

Rank Uncertainty in B12 Data [E] A [E] < 5% or 5 cm^/mol

B 5% or 5 cm^/mol < [E] < 10% or 15 cm^/mol

C 10% or 15 cm^/mol < [E] X Correlated B12 Values

Several methods were employed to aid in establishing the category, 'A', 'B' or 'C,

into which binary system data should be placed. An initial assessment of data quality

was often possible through authors' statements concerning the accuracy of their data.

Care must be taken not to rely entirely on an author's statements, however. Authors may

have either over estimated or under estimated the quality of their data. Uncertainties

in authors' statements were often resolved through the use of other accuracy assessment

techniques. These techniques included an evaluation of the accuracy or precision expected

from the experimental procedures for data measurement used by the various authors. The

compilation of Dymond and Smith^ contained some information regarding the assessment

of experimental techniques. This proved helpful in some instances. A more reliable

method for the determination of data quality was the comparison of plotted B12 data

versus inverse temperature for the various sources reporting data for a given binary system.

Such plots produced a nearly straight line for most of the high quality interaction second

virial coefficient data considered in this work. Lower quality data were often revealed by

scatter in the data or lack of consistency with expected trends of B12 versus ^

(and/or the

temperature derivative, dBi2/d{^)). Also, where two or more sources report data which

are in agreement (within 5% or 5 cm^/mol, whichever is the greater) and showed little scatter, these data sets were often regarded as top quality and assigned an 'A' ranking.

Where agreement of the data from one source was within 10% but not within 5% (or less

than 15 cm^/mol but greater than 5 cm^/mol) of that of a second source of data which are known to be accurate, the first data set was assigned a 'B' ranking. Data sets disagreeing

with high quality data by more than 10% (or more than 15 cm^/mol) or showing a large

amount of scatter and/or inconsistencies in trends were assigned a 'C ranking.

Measurements are scarce for some binaries and for some temperature ranges, making

the task of data assessment from plotted data more difficult. In some instances assess- ments could be inferred from a particular author's reputation. The data of reliable authors were often given a high ranking even when other data were not available for comparison.

On the other hand, several authors' data were determined to be consistently of lower

than 'A' quality (through comparison plots and the amount of scatter in their data).

Thus when data for these authors were encountered in other binary systems they were

not normally weighted as heavily in comparisons for data assessment as the measurements

made by authors determined to be more reliable.

In other instances where data are scarce or where there is significant disagreement

between the data from different sources, assessments were aided through a graphical comparison of plots of these data with quality data for similar binary systems. For instance, one would expect similar trends for B12 versus ^

(and for the temperature derivative,
dBi2/d{j;)) for all high quality data for binaries of paraffin hydrocarbons with other

paraffin hydrocarbons. Whether data for a particular binary either agreed or disagreed

with these general trends was helpful in determining data quality.

Statements with regard to the evaluation of data should be regarded with some caution. For instance, when the data from two sources receive an 'A' or 'B' ranking because

the data show excellent agreement, it is still possible (although unlikely) that both have

reported data which are substantially in error. Also, the fact that a particular author's

data are found to be either unreliable or reliable for one or more binaries, does not mean

that the same is necessarily true for all binary system.s measured by that particular author. In addition, new evidence may arise which would alter data rankings. Therefore, in

any case where extremely accurate data assessments are imperative, it is recommended

that the original papers be consulted and independent assessments be performed. Nevertheless this work will serve as a valuable resource in making initial quality assessments of

such data.

2.3 Data Needs

As shown in Figure 2 a triangular chart consisting of grids for each binary system was

also used to summarize data needs. Where data are accurate and adequately cover the full range of data requirements for current or anticipated future gas industry needs, the letter

'S' was entered into the appropriate grid for the corresponding binary system indicating

that data for this system are sufficient. In cases where existing data are insufficient for

current or projected future needs, the procurement of new data is recommended. Data

procurement is recommended at one of three priority levels. Priority level '1' is used

for cases where new data are imperative (ie.: in cases where procurement of such data

is of highest priority to the gas industry); Priority level '2' is used for cases where new

data are needed (ie., instances where at least 'B' quality data are in existence but 'A' quality data are desired, or when it is desired to expand the range over which data are

available, or when existing data are inadequate to m.eet anticipated high priority future

needs); Priority level '3' is used for cases where new data are desired (ie.: in cases where

data ranges need to be expanded for lower priority systems or in cases where additional

data are desired in order to clarify uncertainties in data rankings for binaries of moderate

priority).

As evidenced in Figure 2 there is a direct relationship between the abundance of

references and data needs. Where data are most abundant, such as for CH4 binaries with

CsHg, CaHg, n-C4Hio, n-CsHio, No and He, existing data are sufficient. In other cases, where the number of references are fewer for binary systems of importance to the gas

industry, there is usually a corresponding data need. Where at least a few references are

available for a particular binary of importance, the need for procurement of new data

usually has been set as priority level '3' rather than priority level '2'. The lower priority

levels are often an indication that new data are desired principally to verify data qualit}^ or to expand data ranges to other temperature regions.

The only imperative data need for new interaction second virial coefficients is for

the CH4-CO binary, which is a high priority binary for the syngas industry. Another
major need is for the CH4-CO2 binary at priority level '2'; these new data are necessary

to verify the quality of existing data. Since relatively few data are available for the CH4-

CO2 binary (which is of importance to both the natural gas and syngas industries), further

data procurement is recommended for this binary. Much of the needed B^ information for

the CH4-CO2 binary may be derivable from available PVT data, however, and therefore

procurement of new data is only recommended at priority level '2', rather than at priority

level '1'. Other needs at priority levels '2' and '3' exist for natural gas binaries and for

many of the syngas binaries of greater industrial importance. In cases where data are nonexistent for binaries of only very low industrial importance, no needs are specified.

3. SUMMARY OF DATA RANGES AND DATA QUALITY

Table 2 lists for each binary system the quality ranking and temperature ranges

for interaction second virial coefficient data or theoretical values for the corresponding

sources. A superscript 'f ' was used to indicate B12 data which were derived from information reported by another source. A superscript '|' was used to indicate data sets for

which data quality rankings are less certain or where data quality varies within a given

set.

Table 3 lists the recommended B12 data over different temperature ranges for each

binary system. The authors who measured the data and data rank are also listed. Where

two or more authors have each reported quality information for the same system and over a similar temperature range one of two approaches was taken in recommending data: 1)

both are listed when two or more authors have reported the same amount of data; 2) only one author is listed where one author has clearly measured more data points and/or data

over a broader temperature range than other authors. Where only 'B' quality data exist over a certain temperature range for a certain binary system the higher quality and more

abundant data are listed. However, it is not recommended that the 'B' data be used when

extremely reliable data are needed. Systems for which only 'C quality data are available

do not appear in Table 3.

4. EVALUATIONS FOR INDIVIDUAL BINARY SYSTEMS DATA

Evaluations in this section are arranged by binary system following the same order

as that used to organize the availability chart in Figure 1. For instance, methane binary

evaluations appear first beginning with the CH4-C2H6 system followed by the CH4-C3H8

system and proceeding vertically down the availability chart. After the discussion of

methane binaries, ethane binaries are discussed, followed by propane binaries and continuing by proceeding horizontally across the top of the availability chart with each successive

group of binary systems.

Several sources have reported correlated interaction second virial coefficient values

for several binary systems. For instance, Hayden and O'Connell^ have reported correlated

values for many binaries. However, these values usually showed significant deviations from

experimental values. Correlated values more consistent with experimental data have been

reported for several binary systems by Guggenheim and McGlashan;^ Huff and Reed;^
Vilcu et al.;^ Vilcu and Gainer;^ and Katayama et al.* These correlated values were often

not discussed in individual binary system evaluations since the plotting of these values

would detract from the evaluations of the actual data. However, property ranges are given

for the correlated values in Table 3. Data rank for the correlated values is indicated by

an 'X' to distinguish them from actual experimental data and from values derived from

experimental data.

4.1 Methane Binaries

4.1.1 CH4-C2H6

Figure 3 shows a plot of all available B12 data for the CH4-C2H6 binary in the

temperature range of 215 to 373 K (-73 to 212° F; ^=0.0047 to 0.0027). As exhibited in

this plot, the data of Dantzler et al.,^ the data of Michels and Nederbragt^° the data of

Wormald et al.,^^ the datum of Katayama et al.,* the values reported by Gunn^^ and the

datum reported by Mason and Eakin^^ show little scatter and consistent general trends of

B12 versus inverse absolute temperature. Because these data agree to within better than

5%, they are all regarded as being of 'A' quality. The 'A' ranking for these sources is supported by uncertainties reported in Dymond and Smith;^ ±2 cm^/mol for Dantzler et

al., less than 5% for Wormald et al. and ±5 cm^/mol for Mason and Eakin. It should be

mentioned that the values of Gunn were actually derived from the PVT data of Michels.

The reason Gunn's derived values do not coincide precisely with the data of Michels is that Gunn reported as his best values the average interaction second virial coefficients

calculated for methane-ethane mixtures of varying compositions. It is the present authors'

opinion that the interaction second virial coefficients derived from PVT data for a 50:50

mixture are more accurate and that Gunn should have taken weighted averages.

A smooth curve constructed from the data of Hoover et al.^'' is in considerable

disagreement with the general trends for B12 versus ^ and the temperature derivative,

dBi2/d{j;) for the other six investigators. Therefore the data of Hoover et al. are given an overall ranking of 'C'. However, it should be noted that the 273 K datum of Hoover et

al. is in good agreement with others' data. Also it is possible that the curvature expected

in the B12 versus ~ curve at lower temperatures may incorporate the lower temperature

datum of Hoover et al. at 215 K.

4.1.2 CH4-C3Hg

Of the four sources Dantzler et al.^ (Dantzler et al. also reported values which were

interpolated and extrapolated from the data of Gunn); Gunn^^ (Gunn's data were derived

from the PVT data of Sage and Lacey^^); Mason and Eakin;^^ and Wormald et al.^^ who

have reported B12 information for the CH4-C3H8 binary system, the data for the 245 to

511 K (-18.7 to 460° F; ^=0.0041 to 0.002) temperature range generally agree within 2%

as exhibited in Figure 4. Exceptions to this good agreement occurs at 373 K {211.TF;

^=0.0027) where the datum of Dantzler et al. disagrees with the values of Gunn by 6
cm^/mol, and at 298 K {77° F; ^=0.0033) where the datum of Dantzler et al. disagrees

with a curve constructed from the data of Wormald et al. by about 6%. (Note that an extrapolated value from the data of Gunn is in better agreement with the datum of

Dantzler et al. at 298 K, but the agreement of extrapolated values must be regarded with

caution because of uncertainties which are inherent in extrapolation techniques.)

Gunn's data at (about) 373 K and Wormald's datum at (about) 298 K are more

accurate than Dantzler's datum at 373 K and at 298 K respectively because Dantzler's

datum deviates from the smooth curve which would result from considering the data of

Wormald et al. and Gunn collectively. The smooth curve constructed from the combined

data of Gunn and Wormald et al. exhibits the same trends for B12 versus ^

(and for the

temperature derivative, dBi^j d{j.)) as other binaries of methane with paraffin hydrocarbons. The temperature derivative, dBi2/d{j;), of Dantzler's data disagrees with that of

Gunn's and Wormald's data . However, since Dantzler's data cross the curve which could

be constructed from Gunn's and Wormald's combined data sets, there is good agreement

(within 2%) for Dantzler's interior data points.

On the basis of these considerations, the CH4-C3Hg data of Wormald et al., the

values of Gunn and the datum of Mason and Eakin are of 'A' quality, while the data of

Dantzler et al. are of 'B' quality. The values which were interpolated and extrapolated

from the data of Gunn are given an 'X' ranking since these have not been experimentally

determined.

4.1.3 CH4-n-C4H10

Of five sources reporting data for the CH4-n-C4Hio binary (see Figure 5) over the

temperature range of 277 to 583 K (38.9 to 595°F; ^=0.0036 to 0.0017), the high temperature data of Gunn^^ (the high temperature data of Gunn designated by a triangle in

Figure 5 were derived from the PVT data of Tang,^^); the datum of Mason and Eakin, ^^ and the data of Wormald et al.^^ are considered more reliable than the data reported

by Beattie and Stockmayer,^^ and Dantzler et al.^ The reliability of Gunn's data, the

datum of Mason and Eakin and the data of Wormald is based on the following: 1) the

internal consistency of these data (with the exception of the 327 K (^==0.0031) and 314

K (^=0.0032) data of Wormald et al.); 2) the reliability of the data from these authors

for other similar alkane binaries (see Table 2); 3) the agreement of these data with the

general trends of B12 versus ^(and the temperature derivative {dBi2/d{^)) for the reli- able data of other similar binary alkane systems as shown in Figure 6, namely CH4-C2H6,

CH4-C3H8, CH4-i-C4Hio, CH4-n-C5Hi2 and CH4-neo-C5Hi2; and 4) Gunn and Wormald

et al. are in agreement at (about) 374 K (jr=0.027), and Mason and Eakin, and Wormald

are in agreement at (about) 289 K (j; =0.0035).

It should be mentioned that Wormald et al. who derived their data from excess

enthalpies, report uncertainties as large as 23%. This may explain the 314 and 327

K data points which deviate considerably from a smooth curve constructed from other

reliable data. The remaining data of Wormald et al., however, are considered reliable for

the reasons stated above.
On the other hand, the data of Dantzler et al., disagree with a curve constructed

from the combined data of Gunn, of Wormald et al. and of Mason and Eakin by as much

as 10%. Also the temperature derivative dBi2/d{j;) for a curve constructed from the data

of Dantzler et al. disagrees with a similar curve constructed from considering collectively

the data of Gunn, of Wormald et al. and of Mason and Eakin. Further evidence for the

lower quality ranking comes from an observation in Figure 6 where it is shown that a curve constructed from the the data of Dantzler et al. is approaching one that could be

constructed from quality methane-neopentane binary data as temperature is decreased

(as one moves toward larger values of ^). For all other systems in the present investigation

the general trends for quality data show a divergence as temperature is lowered for similar

binary systems. It should be mentioned that the higher temperature data of Dantzler et

al. appear to be in better agreement with other methane-n-butane binary data and are, therefore, regarded as being of better quality. All the data of Dantzler et al. appear to be

in good agreement with interpolated and extrapolated values from Gunn's data. However,

since Dantzler et al. performed the interpolations and extrapolations, these values may be

biased toward the data of Dantzler et al. Therefore, such values are not regarded highly

in the evaluation process.

The data of Beattie and Stockmayer not only exhibit a dissimilar trend from a smooth

curve constructed from other data, but also exhibit inconsistencies with the general trends

of the data for other methane paraffin binaries shown in Figure 6. For instance, Figure 6

reveals that general trends for methane binary data show a decrease in values for binary

interaction second virial coefficients as one looks at data for methane binaries with paraffin

hydrocarbons of increasing chain length. One would therefore expect decreasing values

for Bi2^s for methane-paraffin hydrocarbon binaries in the following order: CH4-C2H6,

CH4-C3H8, CH4-i-C4Hio, CH4-n-C4Hio, CH4-neo-C5Hi2 and CH4-n-C5Hi2. Contrary to

th^ general trend expected, the data of Beattie and Stockmayer for the CH4-n-C4Hio

binary have lower values than quality data at corresponding temperatures for methane

binaries with neopentane and n-pentane as shown in Figures 7. Based on the above considerations the data of Gunn, the datum of Mason and Eakin

and the data of Wormald et al. are ranked as 'A' quality; the data of Beattie and Stockmayer which deviate from Gunn's data by as much as 9.6 cm^/mol and the data of

Dantzler et al. are ranked as 'B' quality; and the values extrapolated and interpolated

from the data of Gunn by Dantzler et al. are given an 'X' ranking. It should be mentioned

that although the overall ranking of the data of Beattie, and of Dantzler et al. is 'B' the

higher temperature data of Dantzler et al. and the higher temperature data of Beattie et

al. are in agreement with the data of Gunn within 5% as shown in Figure 5 and therefore

these particular data points are of 'A' quality.

4.1.4 CH4-i-C4Hio

The interaction second virial coefficient data of Olds et al.^* and data of Gunn^^

for the CH4-i-C4Hio binary agree within 5% over the 344 to 511 K (159.5 to 460. TF;

^=0.0029 to 0.0020) temperature range as exhibited in Figure 8. The data of Olds et al.^* and the data of Gunn^" for the CH4-i-C4Hio are considered to be of high quality based

on: 1) the internal consistency of these data; 2) the agreement of these data with the
general trends of Bn versus ^

(and the temperature derivative dB^/dij;)) for methane

binaries with paraffin hydrocarbons as shown in Figure 9; and 3) the fact that Bu data

derived from PVT data from the laboratory where Olds measured his data (see Sage and

Lacey (1959)^^) have been shown to be of good quahty in other instances. While the Bi2's

of Gunn and of Olds et al. agree with the general trends exhibited for methane binaries

with other paraffin hydrocarbons, as shown in Figure 9, the B^ datum at 288 K (58.7° F;

57=0.0035) of Mason and Eakin^^ deviates significantly from what one would expect for

the CH4-i-C4Hio -B12 value at this temperature.

On the basis of the above considerations Gunn's data and the data of Olds et al. are ranked as 'A' quality, and the datum of Mason and Eakin as 'C' quality. It should also

be mentioned that where CH4-i-C4Hio binary data are needed, these data can be closely

approximated by CH4-n-C4Hio binary data as shown in Figure 9.

4.1.5 CH4-n-C5Hi2

Comparisons are made in Figure 10 for the CH4-n-C5Hi2 data reported by several sources (continuous lines join the data points of individual sources) with the high quality

data for other methane-paraffin hydrocarbon binary systems. General trends for all CH4-

paraffin hydrocarbon system data show a convergence at higher temperatures (lower values

of ^) for reliable data. Deviations from this general trend for sources reporting data for

the CH4-n-C5Hi2 binary reveal data sets which are of lower quality. A close comparison

of Figure 10 with the CH4-n-C5Hi2 data plotted in Figure 11, reveals that the data

which deviate more significantly from expected convergence trends are those of Massoudi

and King^° and those of Pecsok and Windsor.^^ Data showing less significant deviations

are those of Wormald et al.^^ and those of Dantzler et al.^ The data of Zaalishvili^^ show

good agreement with the general trends observed for other methane-paraffin hydrocarbon

systems.

The data of Zaalishvili are ranked as 'A' quality for the following reasons: 1) Zaalishvili's data agree with the general trends of B12 versus ^ and convergence of B12 values

at high temperatures as shown for other methane-paraffin hydrocarbon binaries; 2) the

data of Zaalishvili are internally consistent; and 3) the data of Zaalishvili have been shown

to be of good quality for other binaries in the present study (see Table 3). The data of

Dantzler et al. and the data of Wormald et al. are ranked as 'B' quality while the data of

Pecsok and Windsor and the datum of Massoudi are ranked as 'C' quality for the following reasons: 1) these authors have reported data which disagree with the general trends

of B12 versus ^

(and the temperature derivative di?i2/d(^)) for other methane-paraffin

hydrocarbon binaries; 2) these authors have reported values which disagree with a smooth

curve constructed from the refiable data of Zaalishvili by more than 5% for the 'B' quality data and more than 10% for the 'C' quality data; and 3) these authors have reported

data with large uncertainties,^ ±42 cm^/mol for the data of Pecsok and Windsor, ±13

cm^/mol for the data of Dantzler et al., ±12 cm^/mol for the data of Massoudi and King,

and ±20 cm^/mol for the data of Wormald. The datum reported by Mason and Eakin^^

at 298.15 K (77°F; ^=0.0034) is considered to of 'C' quality because the datum has a reported uncertainty of ±11 cm^/mol.

10
4.1.6 CH4-i-C5Hi2

As shown in Figure 12, Mason and Eakin/^ and Pecsok and Windsor^^ reported data

for the CH4-i-C5Hi2 binary system. The B12 data of Pecsok and Windsor for the CH4-

i-CsHis binary at 298 K [IT F) and 323 K (122° F) are of 'C quality because a smooth

curve which can be constructed by considering these data is in disagreement with the

general trends of B12 versus ^

(and the temperature derivative, dBi2/d{j;)) for methane

binaries with other paraffin hydrocarbons, and the general trend of decreasing B^ values

for i-C5Hi2 binaries with other paraffin hydrocarbons of increasing chain length as shown

in Figure 13. The datum of Mason and Eakin^^ at 289 K [61° F) is considered to be of 'A' quality ranking despite the lack of other CH4-i-C5Hi2 binary data with which to compare

at a similar temperature. The reason for this assessment is because of the agreement

of the datum of Mason and Eakin with the general trends for other methane-paraffin

hydrocarbon binaries, and the reported uncertainty of ±5 cm^/mol for this datum.

4.1.7 CH4-neo-C5Hi2

For the CH4-neo-C5Hi2 system the Data of Strein et al.,^^ having a reported accuracy

of ± 1% and good internal consistency as shown in Figure 14, are considered reliable.

Further verification of the accuracy of the data of Strein et al. comes from the agreement

of the general trends of this data with the trends shown for the quality data of the CH4-

n-C4Hio, CH4-i-C4Hio and CH4-n-C5Hi2 binary systems as shown in Figure 15. On the

other hand, the data of Hamann et al.^^ and the data of Bellm et al.^^ disagree significantly

with the general trends exhibited by the other binaries in that the data of Hamann et

al. and of Bellm et al. do not converge with the other data at higher temperatures (lower

values of ^). Therefore, the data of Hamann et al. and of BeUm et al. are considered to

be of lower quality. Further evidence that the data of Bellm et al. are of low quality is that these data received a low quality ranking by Dymond and Smith. ^ Also, the data of

Hamann et al. show a large amount of scatter which is an indication that these data are

in error. In addition, the data of Bellm et al. and of Hamann et al. deviate by as much

as 41% and 11% respectively from the data of Strein et al. The lower temperature data of Baughman et al.^^ have a reported uncertainty of 10%

and have a significantly different slope from that of an extrapolation of the data of Strein

to lower temperatures. Therefore, these data are considered to be of lower quality.

Based on the above considerations the data of Strein et al. are ranked as 'A' quality

and the data of BeUm et al., of Hamann et al. and of Baughman et al. are ranked as 'C

quality.

4.1.8 CH4-CO

The single available datum of Mason and Eakin^^ at 289 K (61° F; ^—0.0035) for the

CH'4-CO binary is considered to be of 'A' quality based on the reported accuracy of ±5

cm^/mol and the fact that in most cases the data of Mason and Eakin have been proven

to be of 'A' quality when reported to have an accuracy of ±5 cm^/mol.

11
4.1.9 CH4-CO2

Three sources report B12 information for the CH4-CO2 binary system covering the 289

to 511 K (100 to 460° F; ^=0.0032 to 0.002) temperature range. These are: Zaalishvili,^^

Katayama et al.* and Mason and Eakin.^^ The data of Zaalishvili are considered rehable

for the following reasons: 1) the internal consistency of Zaalishvili 's data as shown in

Figure 16; 2) the internal consistency of Zaahshvili's data for other binary systems for

which Zaalishvili measured data (ie. the C2H6-CO2 and the CH4-n-C5Hi2 binary systems); and 3) the agreement of the general trends for B^ versus ^

(and the temperature

derivative dBi2/d{^)) between Zaalishvili's CH4-CO2 data and the data for other CO2

binary systems with paraffin hydrocarbons as shown in Figure 17.

The datum of Katayama et al. and the datum of Mason and Eakin are also considered

to be of good quality because these data agree with an extrapolation of Zaalishvili's data to

lower temperatures (larger values of ^) within 5 cm^/mol, and have reported accuracies of

±0.4 and ±5 cm^/mol respectively. On the basis of the above considerations, Zaalishvili's

data, the datum of Katayama et al. and the datum of Mason and Eakin all are given 'A' rankings.

4.1.10 CH4-N2

The data Roe and SaviUe^^ for the CH4-N2 binary system over the 155 to 292 K (-181

to 66° F; :^ =0.0065 to 0.0034) temperature range are considered to be extremely reliable

for the following reasons: 1) the reported accuracy of Roe's data is within 2%; 2) a plot of

Roe's data in Figure 18 reveals that the data are internally consistent; and 3) a comparison

of Roe's data with the reliable data for similar nitrogen-paraffin hydrocarbon systems in

Figure 19 reveals that all three of these systems show similar trends of convergence of

B12 values at higher temperatures. Convergence of B12 values at higher temperatures for

similar systems is a common trend as is shown for other similar binary systems discussed

in other sections of this report. Roe's data have, therefore, been given a quality ranking

of 'A'.The datum of Mason and Eakin^^ at 289 K (60.53; ^=0.0035) deviates from the

datum of Roe at a similar temperature of 292 K (66° F; ^=0.0034) by 2.3 cm^/mol and,

therefore, is of the same quality as the data of Roe. The datum of Mason and Eakin is, therefore, given a quality ranking of 'A'.

4.1.11 CH4-H2

Interaction second virial coefficient data reported by Mueller et al.,^* the datum of

Mason and Eakin, ^^ and the datum reported by Vilcu et al.^ for the CH4-H2 binary

covering the 144 to 298 K (-200 to 77°F; ^=0.0069 to 0.0034) temperature range as shown in Figure 20 are ranked as 'A' quality. The 'A' ranking for the data of Mueller et

al. and the datum of Vilcu et al. is based on the internal consistency of the plotted data

as shown in Figure 20 and on the fact that the data of Mueller et al. were reported by

12
Dymond and Smith^ to be accurate within 1 cm^/mol. The datum of Mason and Eakin is ranked as 'A' quahty since it agrees with an extrapolation of a smooth curve constructed

from the data of Mueller et al. within 2 cm^/mole. Correlated values of Vilcu et al. at 298

K {77° F; 5^=0.0034) are in good agreement with a smooth curve constructed from the

data of Mueller et al. and datum of Vilcu et al. collectively. Much of the needed higher

temperature values can be derived from PVT measurements of Solbrig and EUington^^

which cover the 138 to 423 K temperature range.

4.1.12 CH4-H2O

The single available data set of Rigby et al.^° for the CH4-H2O binary system covering

the 298 to 511 K (77 to 460°^; ^=0.0034 to 0.002) temperature region as shown in

Figure 21 is ranked as 'B' quality based on the following: 1) these data have a reported

uncertainty of ±15 cm^/mol]^ and 2) although there is scatter in the data, all points

deviate by less than about 5 cm^/mol from a smooth curve which can be constructed

from the data.

4.1.13 CH4-H2S

There are no available interaction second virial coefficient values for the CH4-H2S

binary; however, the volumetric data of Reamer et al.,^^ covering the 280 to 400 K temperature range, may be used in deriving interaction second virial coefficients of accuracy

sufficient for design purposes.

4.1.14 CH4-He

The single available interaction second virial coefficient data set of Bell and Dunlop^^

for the CH4-He system covering the 292 to 320 K (66 to 116°F; ^=0.0034-0.0031) temperature range is plotted in Figure 22. Although the data of Bell and Dunlop are sparse

and there are no other CH4-He binary data with which to compare, the data are considered to be of 'A' quality based on the following reasons: 1) Bell and Dunlop report an

uncertainty for their data of ±0.3 cm^/mol] and 2) other measurements made by BeU and

Dunlop for the N2-He binary system compare weU with other quality data for the N2-He

binary system (see discussion for the N2-He binary system data).

4.1.15 CH4-NH3

The only available information for CH4-NH3 binary system are the smoothed values

of Lee et al.^^ covering the 423 to 573 K (302 to 572°F; ^=0.0024 to 0.0017) temperature

range as shown in Figure 23. These values are considered to be at least of 'B' quality

since the data of Lee et al. for both the CH4-NH3 and the N2-NH3 binaries are internally

consistent. The procurement of additional data may be helpful in verifying the quality of

these data.

13
4.2 Ethane Binaries

4.2.1 C2H6-C3H8

Two sources, Dantzler et al.^ and Mason and Eakin/^ have reported C2H6-C3Hg

interaction second virial coefficients covering the 288 to 373 K (59 to 212° F; ^=0.0035

to 0.0027) temperature range. The datum of Mason and Eakin is in good agreement with

the data of Dantzler et al. deviating from an extrapolation of the data of Dantzler et

al. by only 3% as shown in Figure 24. The data for these two investigators are considered

to be of 'A' quality for the following reasons: 1) the datum of Mason and Eakin is in good

agreement with an extrapolation of the data of Dantzler et al.; 2) the data of Dantzler et

al. are internally consistent for the C2H6-C3H8 binary as well as for all of the other binary

systems of concern in the present study (see discussions for the following binary systems:

CH4-C2H6, CH4-C3HS, CH4-n-C4Hio, CH4-n-C5Hi2, C2H6-C3HS, C2H6-n-C5Hi2); 3) the

data of Dantzler et al. have been shown to be of good quality for several other systems

of concern in the present study (see Table 2); and 4) a smooth curve constructed from

considering the data of Dantzler et al. and the datum of Mason and Eakin collectively

agrees with the general trends of B12 versus ^

(as well as for the temperature derivative,

dBi2/d{j;)) for other ethane-parafhn hydrocarbon binaries, and with the general trends of

decreasing B12 values for interactions of ethane with paraffin-hydrocarbons of increasing

chain length as shown in Figure 25.

4.2.2 C2H6-n-C4Hio

Of three sources reporting B12 information for the C2H6-n-C4Hio binary system, the

data of Dantzler et al.^ and the datum of Mason and Eakin^^ covering the 288 to 373

K (59 to 212° F; ^—0.0035 to 0.0027) temperature range are of better overall quality

than the data of Wormald et al.^^ which exist over the same temperature range. The

reliabihty of the data of Dantzler et al. and the datum of Mason and Eakin is based on

the following reasons: 1) the data of Dantzler et al. as shown in Figure 26 are internally

consistent. The datum of Mason and Eakin is consistent with an extrapolation of the

data of Dantzler down to lower temperatures; 2) the data of Dantzler et al. have been

shown to be of good quality for several other systems considered in the present study

(see Table 2); and 3) a smooth curve constructed from considering the data of Dantzler

et al. and the datum of Mason and Eakin collectively agrees with the general trends

of B12 versus ^

(and the temperature derivative, dBi2/d{^)) for other ethane-paraffin

hydrocarbon binary systems, and with the general trend of decreasing values for B12 for

ethane binaries with paraffin hydrocarbons of increasing chain length as shown in Figure

27. Based on the above the data of Dantzler et al. and the datum of Mason and Eakin

are considered to be of 'A' quality.

One of the three points reported by Wormald et al., the datum at 333 K (140°F;

^=0.003), shows a 16% deviation from a smooth curve constructed by considering the

data of Dantzler et al. and the datum of Mason and Eakin collectively. Therefore, this

14
datum is of 'C quality. However, the datum at 304.5 K (88°F; ^=0.0033) deviates from

the smooth curve by only 4% while the datum at 363 K (194°F; ^-r0.0028) falls on the

curve. Therefore, these two points are of 'A' quality.

4.2.3 C2H6-n-C5Hi2

Three sources, Dantzler et al.;^ Massoudi and King;^° and Pecsok and Windsor,^^

report data for the C2H6-n-C5Hi2 binary covering the temperature range of 288 to 373 K

(59 to 212° F; ^=0.0035 to 0.0027). The data of Dantzler et al. are ranked as 'A' quality

for the following reasons: 1) the data of Dantzler et al. are internally consistent as shown

in Figure 28; 2) the data of Dantzler et al. have been shown to be of good quality for

several other binary systems considered in the present study (See Table 2); and 3) the

data of Dantzler et al. are in agreement with the general trends of B12 versus ^

(and

the temperature derivative dBi2/d{j;)) and the general trend of decreasing B12 values for

ethane binaries with paraffin hydrocarbons of increasing chain length as shown in Figure

29.

The datum of Massoudi and King and the datum of Pecsok and Windsor at 298 K

(77° F; ^=0.0034), on the other hand, are ranked as 'C quality for the following reasons:

1) the datum of Massoudi and King has a reported accuracy of about 8% and deviates

from the smooth curve constructed from the data of Dantzler et al. by about 14%; 2) the

data of Massoudi and King have been shown to be of low quality for the n-C5Hi2-C02 and

the n-C5Hi2-N2 binary systems; and 3) the datum of Pecsok and Windsor has a reported

error of about ±41%^ and is in disagreement with the 298 K datum of Dantzler et al. by

about 8%.

4.2.4 C2H6-CO2

The data of Zaalishvili^^ for the C2H6-CO2 binary system which cover the temperature range of 311 to 500 K (100 to 460°F; ^=0.0032 to 0.002) are given an 'A' quahty

ranking for the following reasons: 1) Zaalishvili's data show good internal consistency for

the C2H6-CO2 binary data as shown in Figure 30; 2) there is good internal consistency for

other binary data which Zaalishvili has measured (ie., for the CH4-CO2 and CH4-n-C5Hi2

binary systems); 3) Zaalishvili's C2H6-CO2 interaction second virial coefficient data show

consistent trends for B12 versus 57 (and for the temperature derivative dBi2/d{j;) with

those of other reliable paraffin hydrocarbon-carbon dioxide data as shown in Figure 31.

It should be mentioned that the general trend for the second derivative of Zaalishvili's

data, d'^Bi2/d{j;Y, is not in agreement with the general trends for the second derivatives

for other paraflSn hydrocarbon-carbon dioxide binaries. The second derivative normally

is negative as indicated by a curve which is slightly concave downward. This is not the

case for Zaalishvili's data as shown in Figure 31. However, when considering a smooth

curve which could be constructed by considering the datum of Katayama et al.* at 298 K

(77°F; ^=0.0034) the datum of Mason and Eakin'^ at 289 K {61° F; ^-0.0035) and the

data of Zaalishvili collectively, none of the points deviate from the curve by more than

5%.

15
The datum of Katayama et al. and the datum of Mason and Eakin show agreement

with each other and with the general trends of B12 versus ^ expected for the C2H6-

CO2 binary when comparisons are made with other paraffin hydrocarbon-carbon dioxide

binary systems in Figure 31. Also, the reported accuracies of the datum of Katayama et

al. and the datum of of Mason and Eakin of ±7 and ±5 cm^/mol respectively indicate

these data are of high quality and therefore are given an 'A' ranking.

4.2.5 C2H6-N2

For the two sources, Gunn^^ (Gunn's data are derived from the PVT data of Sage

and Lacey^^); and Mason and Eakin, ^^ reporting B12 information covering the 277 to 511

K (39 to 460°F; |r=0.0036 to 0.02) temperature range for the C2H6-N2 binary system,

the data generally agree as shown in Figure 32. An exception to this agreement is Gunn's

datum at 311 K (100°F; ^=0.0032) which deviates by about 6 cm^/mol from a curve which could be constructed by considering the datum of Mason and Eakin and the data

of Gunn collectively.

It is possible, of course, that Gunn's datum at 311 K is more accurate while the two

surrounding data of Gunn and the datum of Mason and Eakin are less accurate. However,

it is more reasonable to assume that only Gunn's 311 K datum is inaccurate because of

the good agreement of the remaining values with a curve which could be constructed

through these values. All of the values do, however, agree with the general trends of

B12 versus ^

(and the temperature derivative, dBi2/d{^)) for the similar binary systems

CH4-N2 and n-C4Hio-N2 as shown in Figure 33. The agreement with these general trends

combined with the fact that Gunn's data and the data of Mason and Eakin have been

determined to be reliable for other binary systems, indicates that Gunn's values and the

datum of Mason and Eakin are of 'A' quality.

4-2.6 C2H6-H2

The datum of Mason and Eakin^^ at 289 K (61° F; ^=0.0035) is the only available

interaction second virial coefficient information for the C2H6-H2 binary. The datum of

Mason and Eakin is considered to be of 'A' quality because the datum has a reported

uncertainty of ±5 cm^/mol^ and the majority of the data of Mason and Eakin in this

report have been shown to be of good quality. Additional interaction second virial coefficient data may be useful in the future for the C2H6-H2 binary system for situations where

syngas is mixed with natural gas. However, at present such information is of low priority

to the gas industry and needed information can be derived from PVT data or calculated

from available correlations.

4.2.7 C2H6-H2O

Two sources, Coan and King;^'* and Rigby et al.,^ report interaction second virial

coefficients for the C2H6-H2O binary system covering the temperature range of 298 to 444

16
K (77 to 340°F; ^=0.0034-0.0023) as shown in Figure 34. Both data sets are in disagreement with the general trends of B12 versus ^

(and the temperature derivative, dBi2/d{^))

for the data set of Rigby et al.^° for the CH4-H2O binary (see Figure 35). Therefore, the

existing C2H6-H2O data is considered to be of 'C quality overall. Individual points may

be of better than 'C quality, but without additional data it is difficult to determine which

are more accurate.

4.2.8 C2H6-H2S

The interaction second virial coefficient data of Khoury and Robinson^^ covering the

323 to 398 K (122 to 257°F; ^=0.0031 to 0.0025) temperature range as shown in Figure 36

are the only available interaction second virial coefficient data for the C2H6-H2S binary

system. The data of Khoury and Robinson are internally consistent and therefore are considered to be of at least of 'B' quality. However, since there are no other interaction

second virial coefficient values with which to compare for the C2H6-H2S binary system or

for other H2S binaries with paraffin hydrocarbons, assessment of the quality of the data

of Khoury and Robinson is difficult and the 'B' quality ranking is somewhat uncertain.

4.3 Propane Binaries

4-3.1 C3Hg-n-C4Hio

Two sources, Dantzler et al.;^ and Mason and Eakin,^^ have reported interaction

second virial coefficients for the C3Hg-n-C4Hio binary covering the 288 to 373 K (59 to

212°F; ^=0.0035 to 0.0027) temperature range as shown in Figure 37. These data are

of 'A' quality and sufficient to meet most gas industry needs. This quality ranking was

given for the following reasons: 1) a curve constructed from the data of Dantzler et al. and

the datum of Mason and Eakin collectively shows good internal consistency; 2) the curve which can be constructed by considering the data of Dantzler et al. and the datum of

Mason and Eakin collectively is consistent with the general trends of B12 versus ^

(and

the temperature derivative, dBi2/d{^)) for other propane-paraffin hydrocarbon binary

systems data, and with the trend of decreasing values of B12 for propane binaries with

paraffin hydrocarbons of increasing chain length as shown in Figure 38; and 3) the data of

Dantzler et al. for other binary systems have been shown for all other binaries considered

in the present study to be of good quality (see Table 2).

4.3.2 C3Hs-n-C5Hi2

The single available data set of Dantzler et al.^ for the CaHg-n-CsHi^ binary system

covering the 298 to 373 K (77 to 212°F; ^=0.0034-0.0027) is considered to be of 'A' quality based on the following: 1) the data are internally consistent as shown in Figure

39; 2) the data of Dantzler et al. have been shown to be of good quality for all other

17
binary systems considered in the present study for which Dantzler et al. have measured

data; and 3) the data of Dantzler et al. are consistent with the general trends of B12 versus ^

(and the temperature derivative, dBi2/d{j;)) and the trend of decreasing B12 values for

propane binaries with other paraffin hydrocarbons of increasing chain length as shown in

Figure 40.

4.3.3 C3H8-i-C5Hi2

No interaction second virial coefficient information is available for the C3Hg-i-C5Hi2

system; however, the PVTx data measured over the 273 to 573 K (32 to 572° F) range by

Vaughn and Collins^^ should be useful for the determination of fairly reliable B12 values.

If these values prove to be accurate they will be sufficient for most needs.

4.3.4 C3Hg-C02

Four sources, Gunn^^ (Gunn's data are derived from the PVT data of Sage and

Lacey^^); Bougard and Jadot;^^ Mason and Eakin^^; and Sie et al.^* have reported interaction second virial coefficients for the C3HS-CO2 binary covering the temperature range

of 288 to 511 K (59 to 460 °F; ^=0.0035 to 0.002). Of the B^s for these four sources all with the exception of the datum of Sie et al. and the 344 K (150°F; ^=0.0029) datum

of Gunn, generally agree with the trends of B12 versus ^

(and the temperature derivative, dBi2/d{j;)) for all of the data and values considered collectively (see Figure 41).

The datum of Sie et al. disagrees by about 30% from a smooth curve which would result

from considering the others' B12 data collectively. The 344 K datum of Gunn disagrees

from the smooth curve by about 10%. Further observations through the comparison with

similar paraffin hydrocarbon-carbon dioxide binary systems in Figure 42, show that the

data from all sources with the exception of the datum of Sie et al. agree with the general

trends of B12 versus ^

(and the temperature derivative, dBi2/d{f)) and of decreasing B12

values with increasing hydrocarbon chain length.

Based on the above considerations the datum of Sie et al. is given a quality ranking of

'C. The remaining data are given a quality ranking of 'A' based on the following reasons:

1) the data are in agreement within 5% with a smooth curve constructed from all of the

data with the exception of 344 K datum of Gunn; 2) Gunn's data have been determined

to be of high accuracy for other natural gas binaries; and 3) the datum of Bougard has a reported accuracy of ±4% and the datum of Mason and Eakin has a reported accuracy

of ±5 cm^/mol.^

4.3.5 C3HS-N2

The datum of Mason and Eakin^^ is the only available B12 information for the CsHgN2 binary. The quality of the datum of Mason and Eakin is difficult to assess without

other C3Hg-N2 binary B12 information with which to compare. An examination of a

plot of all paraffin hydrocarbon-nitrogen binary systems data in Figure 43 does reveal,

18
however, that the datum of Mason and Eakin is in the correct range. As shown in Figure

43 the datum of Mason and Eakin falls between the Bi2^s for the C2H6-N2 and the n- C4H10-N2 binary systems. Bi^^s generally decrease for nitrogen binaries with paraffin

hydrocarbons of increasing chain length; therefore the location of the datum of Mason

and Eakin is where it would be expected. Also the datum of Mason and Eakin has a reported uncertainty of ±5 cm^ jmol. Therefore the datum is considered to be of 'A'

quality.

One could, therefore, make crude estimates of interaction second virial coefficient

values for the C3H8-N2 binary system by generating a line between the point where the

B12 values for the C2H6-N2 and n-C4Hio-N2 binary systems converge down to the datum of

Mason and Eakin. B12 information gained from generating values by this method may be

helpful in estimating properties for design purposes. However, where accurate properties

prediction is important, these generated values should not be relied upon. In such cases

it is recommended that one determine B12 values through the use of a correlation or from

existing PVT data until more accurate B^^ information for the C3Hg-N2 binary system is made available.

4.3.6 C3HS-H2

The datum of Mason and Eakin^^ at 289 K (61°F; ^=0.0035) is the only available

interaction second virial coefficient information for the C3H8-H2 binary system. The

datum of Mason and Eakin is ranked as 'A' quality because the datum has a reported

uncertainty of ±5 cm^/mol and much of the other data of Mason and Eakin have been

shown to be of 'A' quality. Additional interaction second virial coefficient information

may be useful for situations where syngas is mixed with natural gas. However, at present

such information is of low priority to the gas industry. Where values are desired these can be derived from available PVT data or calculated with a correlation.

4.3.7 C3H8-He

The scatter of as much as 8.5 cm^/mol shown in Figure 44 for the single available

data set of Warowny and Stecki^^ for the CsHg-He binary system indicate that these

data are of at best 'B' quality. No additional interaction second virial coefficient data

procurement is recommended for the C3H8-He binary system, however, since the system

is of low importance industrially and desired information may be derived from available

PVT data or calculated with a correlation.

19
4.4 n-Butane Binaries

4-4-^ n-C4Hio-i-C4Hio

The single data set of Connolly^° for the n-C4Hio-i-C4Hio binary covering the temperature range of 344 to 445 K (160 to 341°^; |r=0. 0029-0. 0022) is ranked as 'A' quaHty

based on the following reasons: 1) The data of Connolly are internally consistent as shown

in Figure 45; and 2) the data agree with the general trends of B12 versus ^

(and the temperature derivative {dBi2/d{j;)) for n-butane binaries with other paraffin hydrocarbons

and the trend of decreasing B12 values for n-butane binaries with paraffin hydrocarbons

of increasing chain length as shown in Figure 46; and 3) the data of Connolly are in close

agreement (within 6%) with the second virial coefficients for like interactions of n-butane

recommended by Dymond and Smith^ which are considered to be accurate within 5%.

Also estimates of design quality data can be obtained from the recommended values

of Dymond and Smith for the second virial coefficients for like interactions of n-butane at temperatures outside the range of Connolly's data.

4.4.2 n-C4Hio-n-C5Hi2

Of two sources reporting data for the n-C4Hio-n-C5Hi2 binary system covering the

298 to 373 K (77 to 212°F; ^=0.0034 to 0.0027) temperature range as shown in Figure

47, the data of Dantzler et al. are of 'A' quality while the datum of Jessen and Lightfoot^^

is of 'C quality. Justification for the ranking of the data of Dantzler et al. is based on

the following reasons: 1) the data of Dantzler et al. for the n-C5Hi2-n-C4Hio binary are

internally consistent; 2) the data of Dantzler et al. have been determined to be of good

quality for other systems considered in the present study for which Dantzler et al. have

measured data; 3) the data of Dantzler et al. are in agreement with the general trends

of B12 versus ^(and the temperature derivative, dBi2/d{j;)) and the general trend of

decreasing B12 values for n-pentane binaries with other paraffin hydrocarbons of increasing

chain length as shown in Figure 48. The datum of Jessen and Lightfoot at 303 K (86° F;

^=0.0033), on the other hand, is ranked as 'C quality because it deviates from the smooth

curve which can be constructed from the data of Dantzler by about 30% and the datum

of Jessen and Lightfoot falls in the range of the recommended values by Dymond and

Smith^ for like interactions of n-pentane molecules. As shown in Figure 48 the values for

like interactions of n-pentane molecules are consistently lower than the values of Dantzler

for unlike interactions between n-pentane and n-butane molecules.

4.4.3 n-C4Hio-C02

Of three sources reporting Bi2^s for the n-C4Hio-C02 binary system covering the

temperature range of 288 to 478 K (59 to 401°F; ^=0.0035 to 0.02), Gunn's data^^ which

have been calculated from the volumetric data of Sage and Lacey^^ and the datum of

20
Mason and Eakin^^ are considered reliable, while the datum of Sie et al.^* is of low quality.

The reliability of Gunn's data is based on the following: 1) the internal consistency of

Gunn's n-C4Hio-C02 data as shown in Figure 49 as well as the internal consistency of

Gunn's data calculated from the volumetric data of Sage and Lacey for the C3Hg-C02

binary system;^^ and 2) the agreement of Gunn's data with the general trends of B12 versus ^

(and the temperature derivative, dB12 1 d{^)) for other paraffin hydrocarbon-carbon

dioxide binaries and the general trend of decreasing B12S for carbon dioxide binaries with

paraffin hydrocarbons of increasing chain length as shown in Figure 50. Gunn's data are, therefore, ranked as 'A' quality.

The unreliability of the datum of Sie et al. is based on the fact that the datum is in disagreement with an extrapolation of Gunn's data by about 30% as shown in Figure

49 and on the fact that the datum of Sie et al. falls approximately in the range of where

data for binary interactions of carbon dioxide with propane are expected (see Figure 50).

The datum of Sie et al. is, therefore, ranked as 'C' quality.

The reliability of the datum of Mason and Eakin^^ is difficult to assess because there

are no other n-C4Hio-C02 data in a similar temperature range with which to compare.

However, the datum has a reported accuracy of ±5 cm^jmol. Also, the datum of Mason

and Eakin follows the general trend of decreasing values for binaries of carbon dioxide

with paraffin hydrocarbons of increasing chain length as shown in Figure 50. The data of

Mason and Eakin have also been determined to be of 'A' quality for many of the other

systems in this work. Therefore, the datum of Mason and Eakin for the n-C4Hio-C02

system is likely to be of 'A' quality, but certainly of at least 'B' quality.

The datum of Mason and Eakin may be used to aid in making crude estimations

of -Bi2's through interpolation between the datum of Mason and Eakin (289 K) and the

data of Gunn (378 to 478 A'). However, for accurate B12 values between 288 to 378 K

it is recommended that additional B12 information be measured or that one rely on PVT

data for the calculation of such information.

4.14 n-C4Hio-N2

Five sources, Cruikshank et al.;^^ Gunn^^ (Gunn's data actually are data derived from

the PVT data of Evans and Watson^^); Hicks et al.;'*'* Mason and Eakin;^^ and Young,'*^

have reported interaction second virial coefficients for the n-C4Hio-N2 binary system as shown in Figure 51. The data of Gunn covering the 427 to 478 K (309 to 401 °F\ ^=0.0023

to 0.0021) temperature range are ranked as 'A' quality based on the following: 1) Gunn's

data have been determined to be of good quality in cases where Gunn reported data for

other binaries considered in the present study; 2) the data of Gunn for the n-C4Hio-N2

binary are internally consistent as shown in Figure 51; and 3) as shown in Figure 52

Gunn's data for the n-C4Hio-N2 binary are consistent with the general trends for B12

versus ^

(and for the temperature derivative, dBio/dlj;)) and also for the general trends

of decreasing B12 values for nitrogen binaries with paraffin hydrocarbons of increasing

chain length.

The data of Cruikshank et al.; Hicks et al.; and Young covering the 303 to 333 A' (86 to 140° A; ^=0.0033 to 0.003) temperature range, are regarded as 'B' quaHty for the following

21
reasons: 1) the data are in agreement within 15 cm^/mol; 2) the reported uncertainties

for the data from these sources are larger than 5 cm^/mol but less than 15 cm^ jmol}

The uncertainty for the datum of Cruikshank et al. is ±9 cm^/mol, the uncertainty for

the data of Hicks et al. is ±12 cm^/mol, and the uncertainty for the datum of Young

is ±12 cm^/mol; and 3) the qualities of the data of these authors have been shown to

be less than 'A' for other binary systems considered iri the present study. For instance,

the data of Cruikshank et al, for the n-CsHia-Ni^ and the n-C5Hi2-H2 binaries; the data

of Hicks for the n-C5Hi2-N2 binary; and the data of Young for the n-C5Hi2-N2 and the

i-C5Hi2-N2 binaries all have been shown to be of low quality (see individual discussions

for these particular binaries).

The datum of Mason and Eakin at 289 K (61° F; :jr=0.0035) has a reported uncertainty of ±5 cm^/mol.^ The uncertainty of 5 cm^/mol would normally rank the datum

of Mason and Eakin in the 'A' category. One cannot in this case make such a judgment

with confidence, however, because there are no other quality data in the same temperature range with which to compare the datum of Mason and Eakin for the n-C4Hio-N2

binary. The datum of Mason and Eakin, however, follows the general trends of decreasing

Bi2 values for nitrogen binaries with paraffin of increasing chain length. Based on these

considerations the datum of Mason and Eakin is likely to be of 'A' quality, but certainly

is of at least 'B' quality. Therefor^, an interpolation between the datum of Mason and

Eakin (289 K) and the data of Gunn (428 to 478 K) may be useful in providing crude

estimates of B\i values in the temperature range of 289 to 438 K until additional quality

data are obtained. (Note: Such an interpolation would give more credence to the data of

Hicks et al.)

4.4-5 n-C4Hio-H2

The datum of Mason and Eakin^^ for the n-C4Hio-H2 binary system is the only

available interaction second virial coefficient information for this system. However^ the

datum of Mason and Eakin is ranked as 'A' quality based on the reported uncertainty of

±5 cm^/mol^ and on the fact that the data of Mason and Eakin have been shown to be

of good quality in most other cases in the present study.

4.4-6 n-C4Hio-He

The large amount of scatter of as much as 10 cm^/mol in the data of Jones and

Kay^ covering the 373 to 498 K (212 to 439°F; ^=0.027 to 0.002) temperature range as shown in Figure 53 for the n-C4Hio-H2 binary system is an indication that these data are

at best of 'B' quality. Note that all the data fall within a 10 cm^/mol band. There are no other available data for the n-C4Hio-He binary system. Other desired values can be

derived from available PVT data or determined with the use of a correlation.

22
4.5 Isobutane Binaries

With the exception of the CH4-i-C4Hio and n-C4Hio-i-C4Hio binaries for which B12

data are available, there are no interaction second virial coefficient data for other isobutane binary systems which are of importance for the gas industries. It has been shown,

however, in the discussions for the CH4-i-C4Hio and n-C4Hio-i-C4Hio binary data evaluations that these data could be closely approximated by the data for the CH4-n-C4Hio

binary interaction second virial coefficient data and the second virial coefficient values

for like interactions of n-C4Hio which were recommended by Dymond and Smith/ Thus,

where n-C4Hio binary data exist for binaries of industrial importance, these data may be

used to estimate the i-C4Hio binary system values. i-C4Hio binaries for which B12 values can be approximated by existing B12 data or values of corresponding n-C4Hio binaries are Hsted as follows: i-C4Hio-CH4, i-C4Hio-C02, i-C4Hio-N2, i-C4Hxo-C2H6, i-C4Hio-C3H8,

i-C4Hio-n-C5Hi2, i-C4Hio-i-C5Hi2, and i-C4Hio-neo-C5Hi2. This list includes all i-butane

binaries that are considered in this report to be of greatest importance to the gas industry.

4.6 n-Pentane Binaries

4.6.1 n-C5Hi2-C02

Four sources, Vigdergauz and Semkin;'^^ Massoudi and King;^° Sie;^ and Desty et al.^* have reported data for the n-C5Hi2-C02 binary covering the temperature range of 298 to

353 K (77 to 176°F; ^=0.0034-0.0028) as shown in Figure 54. The datum of Vigdergauz

and Semkin, the datum of Sie, and the datum of Desty are of low quality because they

are inconsistent with the general trends of B12 versus ^

(and the temperature derivative

of dBi2/d{j;)), and with the general trend of decreasing B12 values with carbon dioxide

binaries with paraffin hydrocarbons of increasing chain length as shown in Figure 55.

Further evidence indicating that these data are of low quality is given in the following

statements: The data of Vigdergauz and Semkin were given a low ranking through the

evaluations made by Dymond and Smith; ^ Sie's data have been shown to be of poor quality

for other binary systems as discussed in the evaluations of the CO2-C3H8 and C02-nC4H10 binary systems; and the datum of Desty for the n-C5Hi2-C02 binary system has an

uncertainty of ±17%.^ Based on the above considerations the datum of Vigdergauz and

Semkin, the datum of Sie and the datum of Desty are determined to be of 'C quality.

The datum of Massoudi and King, on the other hand, is consistent with the general

trend of decreasing B12 values for carbon dioxide binaries with paraffin hydrocarbons of

increasing chain length as shown in Figure 55 and the datum of Massoudi and King has a reported error of about 8% (1). The datum of Massoudi and King, therefore, is given a

quality ranking of 'B'.

23
4.6.2 n-C5Hi2-N2

Twelve sources have reported data for the n-C5Hi2-N2 binary system. For these data

there is a large amount of scatter as shown in Figure 56. Because the reported errors are greater than 10% or 15 cm^/mol^ for Desty et al.;^* Letcher and Marsicano;^^ Vigdergauz

and Semkin;'^^ and Young,^^ these data are given a quality ranking of 'C. Data reported

by all other sources have accuracies which would normally give them a quality ranking

of 'B' because these reported errors are less than 10% or 15 cm^/mol} These sources

are Cruikshank et al. (1966);'° Cruikshank et al. (1968);'' Everett;'' Gainey (1967);'^

Gainey and Pecsok (1970);'^ Hicks and Young;'"* Leung and Eichinger;'' and Massoudi

and King.'° It should be noted, however, that several of the reported data points are

in considerable disagreement at 298 K (77° jP; ^=0.0034). Sources reporting the data

in question are Cruikshank et al. (1966); Everett; Leung and Eichinger; and Massoudi

and King. These sources have reported data at 298 K which range between 75 and 105

cm^/mol, as shown in Figure 56. Since these data cover such a wide range the accuracy

of these data are uncertain and therefore the 'B' ranking for these data is questionable.

4.6.3 n-C5Hi2-H2

Four sources have reported interaction second virial coefficients for the n-C5Hi2-H2

binary system as shown in Figure 57. The datum of Cruikshank et al.,'° the datum of

Desty et al.,'* the datum of Everett'^ and the datum of Mason and Eakin'^ agree within

15 cm^/mol over the 288 to 298 K (59 to 77° F; |; =0.0035 to 0.0034) temperature range

and, therefore, are of at least 'B' quality. The datum of Mason and Eakin, however, is considered to be of better quality than the others' data since is has a reported uncertainty

of ±5 cm^/mol^ and data of Mason and Eakin have been shown to be reliable in most

other cases in the present study. Therefore, it is given an 'A' quality ranking.

The datum of Cruikshank et al. and the datum of Everett also have low reported

uncertainties, but the data for these authors have been shown to be less reliable for other

binaries in the present study. Therefore, the data of Cruikshank et al. and the datum of

Everett are ranked as 'B' quality. The datum of Desty et al. is probably not of greater than

'B' quality because of the low ranking these authors' data received for other systems in

this paper. Desired interaction second virial coefficient values for the n-C5Hi2-H2 binary

system may also be derived from available PVT data or determined with the use of a

correlation.

4.7 Isopentane Binaries

4.7.1 i-C5Hi2-C02

The datum of Desty et al.'* for the i-C5Hi2-C02 binary system at 298 K (77°F) is ranked as 'C quality because it is in disagreement with the general trends of decreasing

24
Bi2 values for CO2 binaries with paraffin hydrocarbons of increasing chain length as shown

in Figure 58. Figure 58 reveals that the datum of Desty et al. for the i-C5Hi2-C02 binary

roughly falls in the region where one would expect to find data for the C3Hg-C02 binary.

4.7.2 i-C5Hi2-N2

For the i-C5Hi2-N2 binary, Desty et al.,^* Gainey and Pecsok,^^ and Young'*^ measured

data over the 298 to 338 K (77 to 149° i^; ^=0.0034-0.003) temperature region as shown

in Figure 59. It is difficult to assess the quality of the datum of Gainey and Pecsok

and the datum of Desty et al. because of the lack of other quality data for either the i- C5H12-N2 binary or other paraffin hydrocarbon-nitrogen binaries. However, the reported

uncertainties of ±30 crnP/mol for the datum of Desty et al. and of 6 cm^/mol for the datum

of Gainey and Pecsok would place these data in the 'C' and 'B' categories, respectively.

Corresponding rankings for these authors for the n-C5Hi2-N2 binary would support the

above rankings.

The i-C5Hi2-N2 binary data of Young are given a 'C' ranking because of their disagreement with the general trends of the B12 versus j; (and the temperature derivative,

dBi2/d{^)) for other nitrogen binaries with paraffin hydrocarbons. Note that the |r dependency of the J5i2 data of Young has a positive slope in Figure 60 while the ^ dependency

for all other N2 binaries with paraffin hydrocarbons has a negative slope. Despite the lack

of data for isopentane binary systems the need for binary interaction virial coefficients

for isopentane binary systems can be supplemented with information for either n-pentane

binary systems or neopentane binary systems. A similar case was made for the isobutane

binaries where it was proposed that isobutane binary information be supplemented with

information for n-butane binaries.

4-7.3 i-C5Hi2-H2

The datum of Desty et al.^* at 298 K (77° F; ^=0.0034) is the only available interaction second virial coefficient information for the i-C5Hi2-H2 binary system. The datum

has a reported uncertainty of ±30 cm^/mol and, therefore, is given a 'C' ranking. Where

other interaction second virial coefficient values are desired for this system these may be

determined with the use of a correlation.

4.8 Neopentane Binaries

4.8.1 neo-C5Hi2-N2

The reported uncertainty for the interaction second virial coefficient data of Baughman et al.^^ covering the 199 to 258 K (-101 to 5°F; ^=0.005 to 0.0039) temperature

range for the neo-C5Hi2-N2 binary system is ±10%, which places these data on the borderline between 'B' and 'C' quality. However, since the three methods of analysis used

25
by Baughman et al. show fairly consistent trends (see Figure 61) the data are given a

'B' quality ranking. In addition these data are in agreement with the general trends of

Bi2 versus ^

(and the temperature derivative, dBi2/d{j;)) for other binaries with paraffin

hydrocarbons and the general trend of decreasing B12 values for nitrogen binaries with

paraffin hydrocarbons of increasing chain length as shown in Figure 62. Where other interaction second virial coefficient values are desired for this binary, these can be calculated

with the use of a correlation or estimated with the values for nitrogen binaries with other

pentane isomers.

4.8.2 neo-CsHis-He

The uncertainty reported for the interaction second virial coefficient data of Baughman et al.^^ for the neo-C5Hi2-He binary system is ±10%.^ However, since a plot of the

data of Baughman et al. in Figure 63 reveals a lack of consistency for the trend of B12

versus ^ with that shown for other similar binaries, the data of Baughman are ranked as 'C quality.

4.8.3 Other Neopentane Binaries

Interaction second virial coefficient information is not available for other neopentane

binaries of importance to the gas industry. In light of this neopentane B12 information can be estimated from the binary interaction second virial coefficient data for the corre- sponding pentane isomers. The rationale for this has been discussed in detail in previous

sections on isobutane and isopentane binary data.

4.9 CO Binaries

4.9.1 CO-CO2

The single available data set of Cottrell et al.,^^ covering the 303 to 363 K (86

to 194°F; ^=0.0033 to 0.0026) temperature range for the CO-CO2 binary system is considered to be of 'B' quality (see Figure 64). The 'B' quality ranking is based on the

fact that the CO-CO2 binary interaction second virial coefficient data points measured by

Cottrell et al., deviate from each other by less than 11 cm^/mol and the data measured

by either Cottrell, Hamilton and Taubinger, or Cottrell and Hamilton for all other binary

systems in the present study are of good quality.

4.9.2 CO-H2

Reuss and Beenakker;^^ Townend and Bhatt;^^ and Scott, ^'^ have reported 'A' quality

interaction second virial coefficient data for the H2-CO binary system. The data of

Reuss and Beenakker covering the 36 to 60 K (-395 to to 352° F; ^^0.028 to 0.017)

26
temperature range as shown in Figure 65 are given an 'A' quality ranking based on the

internal consistency of these data and on the internal consistency of other data measured

by Reuss and Beenakker for the N2-H2 binary. There are no other low temperature

interaction second virial coefficient data with which to compare the data of Reuss and

Beenakker. However, the solid-vapor equilibrium measurements made by Van Itterbeek

and Van Donimck^^ may be used to calculate interaction second virials with which to

compare the existing data of Reuss and Beenakker. It should be mentioned that although

the data of Reuss and Beenakker are given an 'A' ranking, low temperature data for the

CO-H2 binary system are of low importance to the syngas industry since all processing

and transport of these syngases takes place at higher temperatures.

The data of Townend and Bhatt and the data of Scott are ranked as 'A' quality

based on the good agreement (within 3 cm^/mol) between the two data sets at 298 K

(77°F; ^=0.0034).

4.10 Carbon Dioxide Binaries

4.10.1 CO2-CS2

The only available information for CO2-CS2 binary is the datum of Eucken and

Bresler^° at 273 K. Since there are no other data with which to compare the datum

of Eucken and Bresler no data ranking was given for this binary system. Since binaries

with CS2 are of relatively low importance to the syngas industry no additional data

procurement is recommended. However, available data may be used to test correlations

which in turn may be useful in providing desired CS2 binary data for industry.

4.10.2 CO2-N2

Seven sources, Cottrell et al.;^^ Edwards and Roseveare;^^ Gorski and Miller;^^

Gunn;^^ Mason and Eakin;^^ PfefFerle et al.;^^ and Yakimenko et al.^^ have reported interaction second virial coefficients covering the 110 to 298 K (-262 to IT F\ ^=0.0091 to

0.0034) temperature range for the CO2-N2 binary system as shown in Figure 66. Of these

data those reported by Gunn (Gunn's data actually were derived from the volumetric data

of Tang^^), the datum of Gorski and Miller and the datum of Pfefferle et al. are ranked

as 'A' quality for the following reasons: 1) the reported values of Gunn are internally

consistent as shown in Figure 67; 2) Gunn's value at 298 K {IT F\ ^=0.0034) is in good

agreement with the 298 K datum of Gorski and Miller and of Pfefferle et al. (Pfefferle

has also reported quality data for the C02-He and the N2-He binary systems); and 3)

Gunn's values have been of high quality for other binaries in this study.

The data of Cottrell et al. are ranked as 'B' quality for the following reasons: 1)

the data of Cottrell et al. disagree with a smooth curve constructed from Gunn's values

by as much as 5 cm^/mol; 2) a smooth curve constructed from the data of Cottrell et

al. disagrees with the general trends of B12 versus ^, (and the temperature derivative

27
dBi2/d{^)) for smooth curves constructed for other B12 data of the present study: and

3) the reported uncertainty in the data of Cottrell et al. is as high as 15%.

The datum of Edwards and Roseveare and the datum of Mason and Eakin are ranked

as 'A' quality because they agree within 5 cm^/mol of an extrapolation of a smooth curve constructed from other data determined to be reliable. The low temperature data of

Yakimenko et al. are considered to be of at least 'B' quality because the data are internally

consistent and appear to be in agreement with an extrapolation which could be made from

the data at higher temperatures.

4.10.3 CO2-H2

Two sources have reported B12 data for the CO2-H2 binary system covering the 298

to 363 K (77 to 194°F; ^=0.034 to 0.0028) temperature range as shown in Figure 68. The

data of Cottrell et al.^^ are of 'A' quality while the datum of Edwards and Roseveare^^

is of 'C quality. The data of Cottrell et al. are ranked as 'A' quality for the following

reasons: 1) the data of Cottrell et al. for the CO2-H2 binary are internally consistent

as shown in Figure 68; 2) the data have reported uncertainties of less than 5 cm^ /mol;^

and 3) other CO2 binary measurements made by Cottrell and Hamilton;^^ or Cottrell,

Hamilton and Taubinger^^ have also been determined to be of good quality as shown in

the evaluations of the data for the CO2-CO, CO2-N2 and C02-He binary systems.

The datum of Edwards and Roseveare has been given a quality ranking of 'C based

on the fact that the datum deviates from a smooth curve constructed from the data of

Cottrell et al. by about 32 cm^/mol as shown in Figure 68, and data measured by Edwards

and Roseveare have been shown to deviate significantly from other quality data in other

binary systems evaluations (see the evaluations for the N2-He and the C02-He binary

systems).

4.10.4 CO2-H2O

Of the two sources reporting data for the H2O-CO2 binary system covering the 298

to 373 K (77 to 212°F; ^=0.0034 to 0.0027) temperature range, the data of Coan and

King^'* are regarded as 'B' quality while the data of Pollitzer and Strebel^^ are regarded as 'C quality. The ranking for the data of Coan and King is based on the following: 1) The

data of Coan and King have a reported error of less than 10%;^ 2) the data of Coan and

King are internally consistent as shown in Figure 69; and 3) the data of Coan and King

have been shown to be of 'B' quality for other binary systems of interest in the present

study (see evaluations for the C2H6-H2O and N2O-H2O binary systems).

The data of Pollitzer and Strebel are ranked as 'C quality based on the fact that

they show a large deviation from the data of Coan and King as shown in Figure 69. Also,

when the two data points measured by Pollitzer and Strebel are considered collectively

they disagree with the general trends of B12 versus ^

(and the temperature derivative,

dBi2/d{j;)) for all other quality interaction second virial coefficient data for the binary

systems considered to be of importance in the present study.

28
4.10.5 CO2-H2S

No data are presently available for the CO2-H2S binary; however, the PVT data

of Bierlein and Kay^^ covering the 274 to 354 K temperature region may be useful in

calculating interaction second virial coefficients for this system.

4.10.6 C02-He

Of seven sources, Bell and Dunlop;^^ Cottrell and Hamilton;^^ Edwards and Roseveare;^^ Harper and Miller;^* Linshits et al.;^^ Pfefferle et al.;^ and Tsiklis et al.,TM'^'

reporting interaction second virial coefficient data for the C02-He binary covering the

292 to 423 K (66 to 302" F; ^=^0.0034 to 0.0024) all data but those of Edwards and

Roseveare are in fair agreement with a general trend of B12 versus j; as shown in Figure

70. Since the datum of Edwards and Roseveare disagrees by about 55 cm^/mol from the

data of the other sources, it is given a 'C quality ranking. An expanded plot of the data

for the six sources excluding the datum of Edwards and Roseveare in Figure 71 reveals

that a fair amount of scatter still exists for these data. Therefore, it is difficult to give an accurate ranking of the data for the remaining six sources. However, these data are of

at least 'B' quality since they agree within 15 cm^/mol. Where interaction second virial

coefficient values are desired for other temperature ranges for the C02-He binary system,

these can be derived from available PVT data or calculated using a correlation.

4.11 CS2 Binaries

CS2 binaries which are of greatest importance to the gas industry are those of CS2

with the major constituents of syngas. These binaries are CS2-CO2, CS2-H2, CS2-CO,

CS2-H2O, CS2-CH4 and CS2-N2. The only available data for CS2 binaries are those of

Eucken and Bresler^° who have measured a single datum for each of the CS2-CO2, CS2-

N2, and CS2-H2 binaries at 273 K. Since there are no other data with which to compare

the data of Eucken and Bresler no data rankings are given for these binary system data.

4.12 COS Binaries

COS is a minor constituent of syngas product streams and at present there are no

available data for COS binaries with syngas components. The COS binaries of highest

importance to the gas industry are those binaries with the major constituents of syngas,

COS-CO2, COS-H2, COS-CO, COS-HoO, COS-CH4 and COS-N2. Where COS binary

interaction second virial coefficient values are desired, these can be calculated using available correlations.

29
4.13 Nitrogen Binaries

4.13.1 N2-H2

Interaction second virial coefficient values for the N2-H2 binary system have been

reported by eiglit sources, Brewer and Vaughn;'^ Edwards and Roseveare;^^ Lunbeck;^^

Michels and Wassenaar;^'^ Ostronov et ai.;^^ Verschoyle;^^ Vilcu and Gainer;^ and Zandbergen and Beenakker" covering the 148 to 323 K (-193 to 122° F; ^=0.0067 to 0.0031)

temperature range as shown in Figures 72 and 73. Of the existing data for the N2-H2

binary system all the data with the exception of the data of Ostronov et al. are given an

'A' quality ranking.

The 'A' quality ranking for the data of Brewer and Vaughn and the data of Zandbergen and Beenakker at 270 K and below is based on the following reasons: 1) these

data are internally consistent as shown in Figure 73; and 2) the data for these two sources agree within 1 cm^/mol.

The data of Brewer and Vaughn above 273 K, the datum of Edwards and Roseveare,

the datum of Lunbeck, the datum of Michels and Wassenaar, the data of Verschoyle, and

the datum of Vilcu and Gainer are ranked as 'A' quality because they are in agreement

within at least 4 cm^/mol and they are in agreement with an extrapolation of the data

of Zandbergen and Beenakker within at least 4 cm^/mol.

The data of Ostronov et al., are ranked as 'B' quality for the following reasons:

1) the data of Ostronov et al. deviate by as much as 9 cm^/mol from a smooth curve constructed by considering the data of Zandbergen and Beenakker and the data of Brewer

and Vaughn collectively; and 2) the data of Ostronov et al. disagree with the general trends

of B12 versus ^

(and the temperature derivative, dBi2l d{^)) for the data of the remaining

sources considered collectively. The higher temperature data of Ostronov et al., however,

are in better agreement with the data from the other sources, and, are therefore, of better

quality.

Data of Reuss and Beenakker^^ covering the lower temperature region of 36 to 60 K

(-395 to -352°F; ^=0.028 to 0.017) shown in Figure 72 are of at least of 'B' quality since

the data of Reuss and Beenakker are internally consistent, and appear to be in agreement

with an extrapolation which could be made from a curve constructed from the higher

temperature data.

4.13.2 N2-H2O

Of two sources, Rigby et al.;^° and Richards et al.^* who have reported interaction

second virial coefficients for the N2-H2O binary system covering the 298 to 423 K {11 to

302° F; ^=0.0034 to 0.0024) temperature range as shown in Figure 74, both have reported

'A' quality data. The 'A' ranking is based on the following reasons: 1) the data for both

sources are internally consistent as shown in Figure 74; 2) a continuous smooth curve can be constructed from considering both the data of Richards et al. and the data of Rigby

30
et al. collectively; 3) the data of Rigby et al. have a reported uncertainty of less than 6

cm^/mol;^ and 4) Richards et al. have shown with the use of a theoretical analysis using

the Stockmayer potential that their data are in good agreement with the data of Rigby

et al. Figure 74 shows that the 400 K {26V F; |r ==0.0025) datum of Richards et al. is in

disagreement with a smooth curve which can be constructed from the data. However, the

disagreement from the smooth curve for the 400 K datum is less than 4 cm^/mol and

therefore, the 400 K datum is still considered to be of 'A' quality.

The existing data for the N2-H2O binary system may be supplemented with interaction second virial coefficients calculated from either the data for water solubility in

compressed nitrogen of Bartlett^^ covering the 298 to 323 K temperature range and the

measurements of the solubility of water in the compressed gas by Saddington and Krase.*°

Additional evaluation procedures would be necessary in order to assess the quality of B12

values derived from the data of Bartlett and the data of Saddington and Krase.

4.13.3 N2-H2S

No iiiteractioii second virial coefficient information is available for the N2-H2S binary.

However, the mixture virial coefficients, B(M), given by Robinson et al.,*^^ for the N2-H2S

binary system covering the 293 to 372 K temperature range are useful in calculating

interaction second virial coefficients where such information is needed.

4.13.4 Ns-He

Ten sources report interaction second virial coefficient data for the N2-He binary

system covering the 90 to 748 K (-262 to 887°F; ^=0.011 to 0.0013) temperature range

as shown in Figure 75. These sources are: Bell and Dunlop;^^ Brewer and Vaughn;^^

Canfield et al.;*^ Edwards and Roseveare;^^ Hall and Canfield;*^ Knobler et al.;** Kramer

and Miller;^^ Ku and Dodge;*^ Pfefferle et al.;^^ and Witonsky and Miller.*^

Six of the above sources, Canfield et al.; Brewer and Vaughn; Bell and Dunlop;

Kramer and Miller; Ku and Dodge; and Pfefferle et al. report data covering the 133 to

373 K (-220 to 212° F; ^=0.0075 to 0.0027) temperature region for the Na-He binary

systerfi Whieh are considered to be of 'A' quality. The 'A' ranking for the data of these

six sources is ba§ed on the following reasons: 1) these data are in good agreement with

a smooth curve constructed by considering all of the data collectively (having an average

deviation of less than 1 cm^/mol). The largest disagreement between any of the data

points for these six sources are for the 273 and 223 K data of Canfield et al. and the

273 and 223 K data points of Brewer and Vaughn which disagree by about 1.5 cm^/mol

from a smooth curve. However, all of the other data points are in considerably better

agreement with the smooth curve; and 2) several of the authors have measured data for

other systems for which their data received an 'A' quality ranking. For instance, the data

of Brewer and Vaughn have been shown to be of 'A' quality for the N2-H2 binary and of 'A' quality for the H2-He binary system; the data of Bell and Dunlop have been shown

to be of 'A' quality for the CH4-He binary system; and the data of Pfefferle et al. have

been shown to be of 'A' quality for the COj-He binary system.

31
The datum of Edwards and Roseveare at 298 K {77° F; ^=0.0034) and the data of

Hall and Canfield covering the at 103 to 113 K (-274 to 256°F; ^=0.0097 to 0.0088)

temperature range are ranked as 'B' quality. The datum of Edwards and Roseveare has

received a 'B' ranking because it deviates from other quality data by about 9 cm^/mol.

Although there are no other data with which to compare the data of Hall and Canfield, a 'B' ranking has been given to these data because they appear to be in fair agreement

with an extrapolation which can be made from other quality high temperature data down

to the lower temperature region. However, further data procurement may reveal that the

data of Hall and Canfield are of better quality. The datum of Knobler et al. is ranked

as 'C quality because it deviates significantly from an extrapolation which can be made

from quality higher temperature data down to lower temperatures.

The higher temperature data of Witonsky and Miller covering the 448 to 748 K (347

to 887°F; ^=0.0022 to 0.0013) temperature range at first appear to be of low quality

since a smooth curve constructed from the data of Witonsky and Miller disagrees with

the general trends of B12 versus ^(and the temperature derivative, dBi2/d{j;)) that are shown for the quality data at lower temperatures. However, second virial coefficient theory

shows that values asymptotically approach a single value as temperatures increase. This is most likely the case for the data of Witonsky and Miller since all of their data fall within a range of 3 cm^/mol. It should also be mentioned that the apparent large positive slope for

the data of Witonsky and Miller is deceiving since a plot of B12 versus inverse temperature

tends to bring points closer together as temperature is increased (ie. at smaller values of

^). For this reason the data of Witonsky and Miller are considered to be of at least 'B' quality. However, future procurement of additional data at high temperatures may be

helpful in verifying the reliability of these data.

4.13.5 N2-NH3

The only available data for N2-NH3 binary system are the data of Lee et al.^^ covering

the 318 to 673 K (113 to 752°F; ^=0.0031 to 0.0015) temperature range as shown in

Figure 76. These data are at least of 'B' quality since the data of Lee et al. for both

the N2-NH3 and the CH4-NH3 binaries are internally consistent. The procurement of

additional data may be helpful in verifying the quality of these data.

4.14 NO;f Binaries

4.14-1 N2O-H2O

The only existing interaction second virial coefficient data for the N2O-H2O binary

are those of Coan and King^' covering the 298 to 373 K (77 to 212°F; ^=0.0034 to 0.0027)

temperature range as shown in Figure 77. The data of Coan and King are given an 'A' quality ranking since the data are internally consistent, and these data have a reported

accuracy of about 5%.

32
4.14-2 Other NOat Binaries

The NOx binaries of greater importance to the gas industries are those of N2O,

NO, NO2, and N2O with the major syngas components H2, CO, H2O, CO2, CH4 and

N2. However, the only available information is that which has already been discussed for

the N2O-H2O system above. Other existing NOx mixture data from which interaction

second virial coefficient values can be derived are the data of Markham and Kobe** for the

percentage volume change on mixing for the N2O-CO2 and the N2O-N2 binary systems

at 298 K, the Joule-Thomson coefficients for the N2O-N2 and N2O-CO2 binary systems

determined by Charnley et al.*^ covering the 298 to 318 K temperature range, and the

volumetric behavior of the NO-NO2 binary system reported by Selleck et al.^° covering

the 280 to 440 K temperature range.

4.15 Hydrogen Binaries

4.15.1 H2-H2O

With the exception of the data of Bartlett^^ for water solubility in compressed hydrogen which can be used to derive interaction second virial coefficients, no interaction

second virial coefficient information is available for the H2-H2O binary system.

4.15.2 H2-He

Figure 78 shows a plot of B12 versus ^ for the H2-He binary system data covering the

14 to 448 K (-434 to 347°F; ^=0.07 to 0.0022) temperature range. This plot includes the

data from six sources, Beenakker et al.;^^ Brewer and Vaughn;^^ Gibby et al.;^^ Knobler

et al.; Tanner and Masson;^^ and Varekamp and Beenakker. ^"^ Two sources, Beenakker

et al.; and Varekamp and Beenakker have also reported data for binaries of helium with

hydrogen isotopes. As shown in Figure 78 the data for the isotopic binaries are in close

agreement with the data for the nonisotopic binaries. Figure 78 also reveals that an

extrapolation of the curve constructed from the low temperature data of Beenakker et

al. at 20 K (-423° F; ^=0.05) and the low temperature data of Varekamp and Beenakker

covering the 14 to 17 K (-434 to to 429)°F; ^==0.07 to 0.059) temperature range would be

in fair agreement with the higher temperature data covering the 90 to 448 K (-298-347° F;

|t=0.01 to 0.0022) temperature range of the remaining data. Therefore, intermediate

temperature values between 20 K and 248 K (-13°F; ^=0.0040) may be estimated from

the existing data. A quality ranking of 'A' is given to the data in the 148 to 448 K

temperature range since these data agree within 2% (see Figure 79). The data for the

lower temperature region (see Figure 80) agree within 5 cm^/mol from a curve which can be constructed by considering all of the low temperature data collectively and therefore

are regarded as 'A' quality. The 90 K datum of Knobler et al. is difficult to assess because

of the lack of similar data, but is regarded as being of of 'B' quality since it is in agreement

with an extrapolation of a smooth curve through the lower temperature range data (see

33
Figure 80). Note however, that the datum of Knobler et al. received a 'C ranking for the

N2-He binary and therefore, the 'B' ranking in the present case is suspect. Additional

data would help to clarify this question.

4.16 Hydrogen Cyanide Binaries

The HCN binaries of greater importance to the gas industries are those of HCN with

the major syngas constituents, H2, CO, H2O, CO2, CH4 and N2. At present there are no available interaction second virial coefficient data or values for these HCN binaries.

It is recommended that desired values for these systems be derived from other existing

thermodynamic data or calculated using an available correlation.

4.17 SOa Binaries

At present there are no available interaction second virial coefficient data or values

for SOA' binaries which are of importance to the gas industry. The most important SOx

binaries in the present study are those with the major constituents of syngas. These

binaries are SOA-H2, SOa-CO, SOa-HsO, S0a'-C02, SOX-CH4 and SOX-N2. It is recommended that desired values be derived from other existing thermodynamic data or calculated using an available correlation.

4.18 Ammonia Binaries

Since ammonia is a product of coal gasification processes, the ammonia binaries

which are of importance to the gas industry are those binaries involving ammonia with

the important constituents of syngas. These binaries include H2-NH3, CO-NH3, H2ONH3, CO2-NH3 and CH4-NH3. The only available data for any of these binaries are the

data of Lee et al. for the CH4-NH3 and the N2-NH3 binaries covering the 423 to 573

K (302 to 572°F; ^=0.0024 to 0.0017) and the 318 to 673 K (113 to 752°F; ^-0.0031

to 0.0015) temperature ranges respectively as shown in Figures 23 and 76. These data

have been discussed in previous sections. Data for ammonia binaries for other syngas

components may be derived from correlations.

34
Acknowledgments

This project was conducted with funds from the Gas Research Institute, Contract

No. 5081-360-0416.

35
Table 2

Interaction Second Virial Coefficient Data Ranges and Rank

System Data Temperature Range Source

Rank (K)

A 298.15/373.15 Dantzler^ (1968)

X 273/323 Guggenheim^ (1950)

At 273.15/323.15 Gunni2 (1958)

X 215.00/323.20 Hayden^ (1975)

CH4—C2H6 ct 215.00/273.15 Hoover^^ (1968)

X 273.2/323.2 Huff^ (1963)

A 298 Katayama* (1980)

A 288.7 Mason^^ (1961)

A 272/323 Michels^" (1939)

A 241.1/266.7 Wormald^i (1979)

Bt 298.15/373.15 Dantzler^ (1968)

X 298.15/373.15 Dantzler^ (1968)

At 310.90/510.90 Gunni2 (1958)

CH4-C3H8 X 298.20/510.90 Hayden^ (1975)

X 310.9/510.9 Huff^ (1963)

A 288.7 Mason^^ (^ggi)

A 243.2/302.2 Wormald^i (1979)

Bt 423.2/573.2 Beattiei^ (1941)

Bt 298.15/373.15 Dantzler^ (1968)

X 423/573 Guggenheim'' (1950)

X 298.15/373.15 Dantzler^ (1968)

CH4—n-C4Hio At 344.30/510.90 Gunn^2 (1958)

X 423.20/510.90 Hayden^ (1975)

X 344.3/510.9 Huff^ (1963)

A 228.70 Mason^^ (iggj)

At 277.0/394.3 Wormald^i (1979)

At 344.3/510.9 Gunni2 (1958)

X 344.30/510.90 Hayden^ (1975)

CH4—i-C4Hio X 344.3/510.9 Huff« (1963)

c 288.7 Masonic (1961)

A 344.30/510.90 Olds^* (1942)

B 298.15/373.15 Dantzler^ (1968)

X 298.15/323.20 Hayden^ (1975)

X 310.9/510.9 Huff (1963)

CH4—n-C5Hi2 ct 288.7 Mason^3 (1961)

c 298.15 Massoudi^o (1973)

c 298.2/323.2 Pecsok^i (1968)

B 318.5/403.5 Wormald^i (1979)

A 310.9/510.8 Zaalishvili22 (1956)

•Data derived from information reported by another author.

J- Data vary in quality or rankings somewhat uncertain.

36
Table 2. (continued)

System Data Temperature Range Source

Rank (K)

CH4-i-C5Hi2 At 288.7 Mason^3 (^gg^)

C 298.2/323.2 Pecsok^i (1968)

C 199.99/257.90 Baughman^e (1975)

c 300/550 Bellm^s (1974)

CH4-neo-C5Hi2 c 303.16/403.16 Hamann24 (1955)

X 303.16/403.16 Hayden^ (1975)

X 303.2/403.2 HuflF^ (1963)

A 296.15/492.6 Strein^^ (1971)

CH4-CO X 288.70 Hayden^ (1975)

At 288.7 Mason^^ (1961)

X 310.9/510.8 Hayden^ (1975)

X 310.9/510.8 Huff^ (1963)

CH4-CO2 A 298 Katayama* (1980)

A 288.7 Masonic (1961)

A 310.9/510.8 Zaalishvili22 (1956)

CH4-N2 A 288.7 Masonic (1961)

A 155.88/291.40 Roe27 (1980)

X 288.7 Hayden2 (1975)

A 288.7 Ma5on^3 (1961)

CH4—H2 A 144.3/283.2 Mueller^* (1961)

A 273.15 Vilcu^ (1977)

X 273.15 Vilcu^ (1977)

CH4-H2O X 298.15/510.90 Hayden^ (1975)

B 298.15/510.90 Rigby^o (1968)

CH4-He A 292.9/320.0 Bell32 (iggi)

CH4-NH3 X 423.00/523.00 Hayden^ (1975)

Bt 423.00/523.00 Lee^^ (1970)

A 298.15/373.15 Dantzler^ (1968)

C2H6-C3Hg X 298.20/373.20 Hayden2 (1975)

A 288.7 Mason^^ (1961)

A 298.15/373.15 Dantzler^ (1968)

C2H6—n-C4Hio X 298.20/373.20 Hayden2 (1975)

A 288.7 Mason^^ (1961)

ct 304.5/363.2 Wormald^i (1979)

A 298.15/373.15 Dantzler^ (1968)

C2H6-n-C5lIl2 X 298.20/373.20 Hayden^ (1975)

c 298.15 Massoudi^o (1973)

c 298.2 Pecsok^i (1968)

37
Table 2. (continued)

System Data Temperature Range Source

Rank (A')

X 310.9/510.8 Hayden^ (1975)

X 310.9/510.8 Huff5 (1963)

C2H6-CO2 A 298 Katayama* (1980)

A 288.7 Mason^^ (1961)

At 310.9/510.8 Zaalishvili22 (1956)

aU 277.6/510.9 Gunni2 (1958)

C2H6-N2 X 277.6/510.9 Hayden^ (1975)

X 277.6/510.8 Huff (1963)

A 288.7 Mason^^ (1961)

C2H6-H2 X 288.2 Hayden^ (1975)

At 288.7 Mason^^ (^gg^)

C 298.15/373.15 Coan^^ (1971)

C2H6—H2O X 298.15/444.30 Hayden^ (1975)

c 377.60/444.30 Rigby3° (1968)

C2H6—H2S X 323.20/398.20 Hayden^ (1975)

Bt 323.15/398.15 Khoury35 (1971)

A 298.15/373.15 Dantzler^ (1968)

CaHg—n-C4Hio X 298.20/373.20 Hayden2 (1975)

A 288.7 Mason^^ (1961)

CaHg—n-C5Hi2 A 298.15/373.15 Dantzler^ (1968)

X 298.20/373.20 Hayden^ (1975)

A 300.5 Bougard^^ (1976)

At.t 310.9/510.9 Gunni2 (1958)

CsHg—CO2 X 310.90/510.80 Hayden^ (1975)

X 310.9/510.9 Huff^ (1963)

A 288.7 Mason^^ (iggj)

C 313.2 Sie^* (1966)

C3H8-N2 At 288.7 Mason^^ (^ggj)

C3H8-H2 X 288.20 Hayden^ (1975)

At 288.7 Masonic (1961)

CsHg-He bJ 393.18/423.00 Warowny39 (1978)

n-C4Hio-i-C4Hio A 344.26/444.26 Connolly^" (1962)

X 344.30/444.30 Hayden^ (1975)

A 298.15/373.15 Dantzler^ (1968)

n-C4Hio-n-C5Hi2 X 298.20/373.20 Hayden^ (1975)

c 303.15 Jessen'*! (1938)

38
Table 2. (continued)

System Data Temperature Range Source

Rank (K)

At 377.6/477.6 Gunni2 (1958)

X 377.60/477.60 Hayden^ (1975)

n-C4Hio~"C02 X 377.6/477.6 Huff^ (1963)

At 288.7 Mason^^ (1961)

C 313.2 Sie3« (1966)

B 308.2 Cruikshank^2 (^ggg^

At 427.6/477.6 Gunni2 (1958)

X 427.60/477.60 Hayden^ (1975)

n-C4Hio-N2 X 427.6/477.6 Huff5 (1963)

B 303.2/323.2 Hicks^'* (1968)

At 288.7 Masonic (1961)

B 333.2 Young^^ (1968)

n-C4Hio-H2 X 288.20 Hayden2 (1975)

At 288.7 Masonic (1961)

n-C4Hio-He Bt 373.3/498.3 Jones^^ (1967)

C 298.2 Desty^* (1962)

n-CsHia-COz B 298.15 Massoudi^o (1973)

C 313.2 Sie^s (1966)

C 353.2 Vigdergauz^^ (1971)

B* 298.2 Cruikshank^" (1966)

B 308.15 Cruikshank^2 (jggg)

C 298.2 Desty^« (1962)

Bt 298.2 Everett^i (1965)

B 313.2 Gainey^2 (jggy)

B 313.2 Gainey53 (jg^Q)

n-C5Hi2-N2 X 298.20 Hayden^ (1975)

B 313.2/333.2 Hicks^^ (1968)

C 308.15 Letcher''^ (1974)

Bt 298.16 Leung^^ (1974)

Bt 298.15 Massoudi^o (1973)

C 353.2 Vigdergauz^^ (1971)

c 328.2/338.2 Young^^ (1968)

B 298.2 Cruikshank^o (1966)

B 298.2 Desty^* (1962)

n-C5Hi2—H2 B 298.2 Everett" (1965)

X 298.20 Hayden^ (1975)

At 288.7 Masonic (1961)

i-C5Hi2-C02 C 298.2 Desty^^ (1962)

39
Table 2. (continued)

System Data

Rank

Temperature Range Source

i-C5Hi2-N2

ct

Bt

C

298.2

313.2

328.2/338.2

Desty^* (1962)

Gainey^^ (1970)

Young^^ (1968)

i-C5Hi2-H2 ct 298.2 Desty^* (1962)

neo-C5Hi2-N2 B 199.99/257.86 Baughman^e (1975)

neo-C5Hi2-He C 199.99/230.00 Baughman^^ (1975)

CO-CO2 B

X

303.2/363.2

303.20/363.20

Cottrell^^ (1956)

Hayden^ (1975)

CO-H2

X

X

A

A

A

272/290

36.00/60.00

36/60

298.2

273.2/298.2

Guggenheim^ (1950)

Hayden^ (1975)

Reuss^^ (1956)

Scott^* (1929)

Tovvnend" (1932)

CO2-CS2 - 273.2 Eucken^° (1928)

CO2-N2

B

A

A

At

X

X

A

A

Bt

303.2/363.2

298.2

305.15

298.15/398.15

298.20/363.20

298.2/398.2

228.7

303.2

110.0/125.0

Cottrell^^ (1956)

Edwards^^ (1942)

Gorski«2 (1953)

Gunni2 (1958)

Hayden^ (1975)

Huff^ (1963)

Mason^^ (1961)

Pfefferle^3 (^944)

Yakimenko^^ (1977)

CO2-H2

X

At

C

303.20/363.20

303.2/363.2

298.2

Hayden^ (1975)

Cottrell^s (1956)

Edwards^i (1942)

CO2-H2O

X

B

C

298.20/373.20

298.157373.15

323/343.2

Hayden^ (1975)

Coan^'' (1971)

PoUitzer^^ (1924)

C02-He

Bt

Bt

C

Bt

X

Bt

Bt

Bt

Bt

292.9/320.0

303.2/363.2

298.2

303.2

303.20/363.20

323.2

303.2

373.2

423.2

Bell32 (1981)

Cottrell^^ (1956)

Edwards^i (1942)

Harper^* (1957)

Hayden^ (1975)

Linshits^^ (1975)

Pfefferle^^ (^944)

Tsiklis^o (1974a)

Tsiklis^i (1974b)

40
Table 2. (continued)

System Data Temperature Range Source

Rank (K)

CS2-N2 - 272.2 Eucken^o (1928)

CS2—H2 - 273.2 Eucken^° (1928)

A 148.15/323.15 Brewer^2 (^ggg)

A 298.2 Edwards^i (1942)

X 273/293 Guggenheim^ (1950)

X 148.20/293.20 Hayden^ (1975)

A 298.16 Lunbeck^^ (1951)

N2-H2 A 298.16 Michels^'' (1949)

bJ 198.15/273.15 Ostronov'^5 (1967)

Bt 36/60 Reuss^^ (1956)

A 273.2/293.2 Verschoyle^^ (1926)

A 298.16 Vilcu^ (1974)

X 298.16 Vilcu^ (1974)

A 170/270 Zandbergen^^ (1967)

X 298.20/373.20 Hayden^ (1975)

N2-H2O A 373.15/423.15 Richards^* (1979)

A 298.15/373.15 Rigby^o (1968)

A 292.9/321.7 Bell32 (1981)

A 148.15/323.15 Brewer^2 (jggg)

A 133.15/273.15 Canfield«2 (1963)

B 298.2 Edwards^^ (1942)

Bt 103.15/113.15 Hall*3 (1969)

Nz-He X 148.20/293.20 Hayden^ (1975)

c 90 Knobler*^ (1959)

A 303.20 Kramer*^ (1957)

A 311.7/373.2 Ku«6 (1967)

A 303.2 Pfefferle^^ (1944)

Bt 448.2/748.2 Witonsky*^ (1963)

N2-NH3 X 318.00/723.00 Hayden2 (1975)

Bt 318.00/723.00 Lee33 (1970)

N2O-H2O X 298.20/373.20 Hayden2 (1975)

A 298.15/373.15 Coan34 (1971)

A 20.4 Beenakker^i (1959)

A 148.15/323.15 Brewer^2 (jggg)

A 298.2/448.2 Gibby^2 (ig2g)

H2-He X 298/448 Huff^ (1963)

X 90.00/323.20 Hayden^ (1975)

Bt 90 Knobler*^ (1959)

A 298.2 Tanner^^ (1939)

A 14/17 Varekamp^^ (1959)

41
Table 3

Recommended Unlike Interaction Second Virial Coefficients

System Temperature

Range (/\

)

Recommended

5i 2 Values

Data

Rank

241.1/266.7 Wormaldii A

273/323 Michels^" A

CH4-C2H$ 288.7 Mason^^ A

298 Katayama* A

298.15/373.15 Dantzler^ A

CH4-C3H8 243.2/302.2

310.9/510.9

Wormald^i

Gunni2

A

A

CH4—n-C4Hio

277.0/394.3

344.30/510.90

423.2/573.2

Wormald^i

Gunni2

Beattie^'^

A

A

B

CH4—1-C4H10 344.3/510.9 Olds^* A

CH4—n-C5Hi2 298.15/373.15

310.9/510.8

Dantzler^

Zaalishvili^^

B

A

CH4-i-C5Hi2 288.7 Mason^^ A

CH4-neo-C5Hi2 296.15/492.6 Strein23 A

CH4-CO 288.7 Mason^^ A

CH4-CO2

288.7

298

310.9/510.8

Mason^^

Katayama*

Zaalishvili22

A

A

A

CH4-N2 155.88/291.40 Roe27 A

CH4—H2 144.3/283.2

288.7

Mueller^*

Mason^^

A

A

CH4-H2O 298.15/510.9 Rigby^o B

CH4-He 292.9/320.0 Bell32 A

CH4-NH3 423.00/523.00 Lee33 B

C2H6-C3Hg 288.7

298.15/373.15

Mason^^

Dantzler^

A

A

C2H6-n-C4Hio 288.7

298.15/373.15

Mason^^

Dantzler^

A

A

C2H6-n-C5Hi2 298.15/373.15 Dantzler^ A

C2H6—C02

288.7

298

310.9/510.9

Mason^^

Katayama*

Zaalishvili22

A

A

A

C2H6-N2 277.6/510.9 Gunni2 A

C2H6—H2 288.7 Mason^^ A

C2H6-H2S 323.15/398.15 Khoury^^ B

42
Table 3. (continued)

System Temperature

Range (K)

Recommended

Bi2Values

Data

Rank

C3H8-n-C4Hio 288.7

298.15/373.15

Mason^^

Dantzler^

A

A

C3H8-n-C5Hi2 298.15/373.15 Dantzler^ A

C3Hg-C02

288.7

300.5

310.9/510.9

Mason^^

Bougard^"^

Gunni2

A

A

A

C3H8-N2 288.7 Mason^^ A

C3H8-H2 288.7 Mason^^ A

CsHg-He 393.18/423.00 Warowny^^ B

n-C4H io-i-C4H 10 344.26/444.26 Connolly^o A

n-C4Hio—n-C5Hi2 298.15/373.15 Dantzler^ A

n-C4Hio-C02 288.7

377.6/477.6

Mason^^

Gunni2

A

A

n-C4Hio-N2

288.7

303.2/323.2

427.6/477.6

Mason^^

Hicks^^

Gunni2

A

B

A

n-C4Hio~H2 288.7 Mason^^ A

n-C4Hio-He 373.3/498.3 Jones^^ B

n-C5Hi2-C02 298.15 Massoudi^° B

n-C5Hi2-N2

298.15

298.16

298.2

298.2

308.15

313.2

313.2

313.2/333.2

Massoudi^°

Leung^"*

Cruikshank^o

Everett^^

Cruikshank'^^

Gainey^^

Gainey^^

Hicks^^

B

B

B

B

B

B

B

B

n-C5Hi2-H2

288.7

298.2

298.2

298.2

Mason^'^

Cruikshank^°

Desty'**

Everett^i

A

B

B

B

i-C5Hi2-N2 313.2 Gainey^^ B

neo-C5Hi2-N2 199.99/257.86 Baughman^^ B

CO-CO2 303.2/363.2 Cottrell^^ B

CO-H2 36/60

273.2/298.2

Reuss^^

Townend"

A

A

43
Table 3. (continued)

System Temperature

Range (/\)

Recommended

5i 2 Values

Data

Rank

CO2-N2

110.0/125.0

288.7

298.15/398.15

Yakimenko^^

Mason^^

Gunni2

B

A

A

CO2-H2 303.2/363.2 Cottrell^s A

CO2-H2O 298.15/373.15 Coan^^ B

COs-He

N2-H2

292.9/320.0 Bell32 B

303.2/363.2 Cottrell^s B

373.2 Tsiklis^° B

423.2 Tsiklis^^ B

36/60

148.15/323.15

170/270

Reuss^^

Brewer^^

Zandbergen^^

B

A

A

N2-H2O 298.15/373.15

373.15/423.15

Rigby^o

Richards'''* A

A

N2-He

03.15/113.15 Hall«3 B

33.15/273.15 Canfield*2 A

48.15/323.15 Brewer^^ A

311.7/373.2 Ku«6 A

448.2/748.2 Witonsky*^ B

N2-NH3

H20-N20

H2-He

318.00/723.00

298.15/373.15

Lee33

Coan^^

B

14/17 Varekamp^^ A

20.4 Beenakker^^ A

90 Knobler*^ B

48.15/323.15 Brewer^^ A

298.2/448.2 Gibby92 A

44
CH4 CH4C2H6 C2H6 10 C3H8 CjHb 7 3 nC4 nC4 7 4 3 iC4 iC4 5 2 nCs nCj 8 4 2 3 'Cs 'C5 2 ncoCs

nao-Cs 6 CO CO 2 coa CO2 5 5 6 5 4 1 2 cs2 CS2 1 COS COS N, N2 2 4 1 7 13 3 1 9 1 N02/N204

2/N204 NgO

N2O NC> NO Ha Hz 4 2 2 2 5 1 5 3 1 II H2O 2 3 T

2 " -' 3 3 2 H,SH2S 1 HCN HCN - soa

S02 SOj SO3

1 -~1 1 - - Ht H«

- - J — 10 II e NH3 NHj 2 2 J

Figure 1. Number of references for interaction second virial coefficient data

for natural gas and syngas components.

CH4 CH4

CzHe

C3H8

S

S

C2

3

He

C3

1 New data w% imperative ^ 2 New dato ore needed

3 New dota ore desired

!!^4 s Available data are sufficient nC4 Ss

sS

S

s

s

s iC4 BLANK No data are available and none are needed

iC4 S nCj

nCj

neoCs

s S

-

iCs

ne<)C5 CO CO 12

s

'3

2

3

3

S

33

S

3

S

S

s

-

S

3

coz CO2 S 2 CSz CS2 S COS

COS N, N2 s S 2 2 S N02/N204

N02/N204

2

"ss

S

33

--

S

NjO N2O

s 2

NC NO

2

Hz H2 S 2 HzO H2O 2 2 3 S 2 H2S H2S 2 3 3 2 2 HCN HCN SO2

SOz — SO3

SO3 -- S

~" — -

He He S - S S

S - - NHs NH3 J

Figure 2. Interaction second virial coefficient data needs for natural gas and

syngas components.

45
-60-

-80

o -100 E

EoN

00

120

•140

I60h

-180-

-200 L

SYSTEM CH4-C2H6 TEMP^2I5-373K

3|

AUTHOR OANTZLER (1968) HOOVER (1968) MASON (1961) WORMALO (1979) GUNN (1958) KATAYAMA (1980) MICHELS (1939)

00028 0.0034 00040

l/T(K)

0.0046

Figure 3. Temperature dependence of interaction second virial coefficient

for the CH4-C2H6 system.

-40

-60

-80

-.

-100 oE

•«^ -120

00 -140

-160

180

-200 Li

SYSTEM CH4-C3H8

TEMP- 243- 511 K

AUTHOR

I OANTZLER (1968) ^ D GUNN (1956) CAL'D BY OANTZLER (1968) ^

» WORMALO (1979) •

k GUNN (1956) cal'd by OANTZLER •

^ MASON (1961) •

_L

0.0016 0.0024 00032

l/T(K)

0.0040

Figure 4. Temperature dependence of interaction second virial coefficient

for the CH4-C3H8 system.

46
SYSTEM: CH4-nC4Hio TEMP 277-583

-40

-60

-80-

^ -100- o

E

jstoE

-120 u

CSi m -140

-ISO

180-

-200-

,

- ^

^

- A

-

-

- ". *

_

-

AUTHOR D *^^ BEATTIE (1941) v v

a GUNN (I958)CAL'0 BY DANTZLER (1968) • MASON (1961) A

DANTZLER (1968) A GUNN (1958) ^

WORMALD (1979) -

1 1 1 1 1 1 1 00018 00024

l/T (K)

00030 0O036

Figure 5. Temperature dependence of interaction second virial coefficient

for the CH4-n-C4Hio system.

-50-

-100-

150- o . E

.;^Eo

rT -200

CD

-250 -

-300 L

TEMP:243-5IIK ^vA/*^9v /^V^ 1

- /

^ H.

^-. ' K.

^ GUNN, MASON, Oa

WORMALD <55 s^ ^. dVV a

DANTZLER

/<y\t- \ SYSTEM "^

k

CH4-C2Hs a CH4-iC4H|0 OA

• CH4-nC4H|o

O CH4-neoC5Hi2 CH4- C3H8 A CH4-1C5H12 CH4-nC5H|2

1 1 1 1

1 1 0.0016 0O024 0.0032 l/T (K)

00040

Figure 6. Temiperature dependence of interaction second virial coefficient

for methane-paraffin hydrocarbon binary systems.

47
-50-

100-

o

E

E -150 u

00

200 -

250

X

TEMP : 298-583

K

- >A°7

- '^BEATTIE a"

-

_ ^A --

-

- SYSTEM

- CH4-nC4H|o a CH4-neoC5H|2

CH4-nC5H|2

j_ 1 1 . 11 1 0.0018 0.0024 0,0030

l/T(K)

0.0036

Figure 7. Temperature dependence of interaction second virial coefficient

for metliane-paraffin hydrocarbon binary systems.

-40 r

60

toE^ -100 N

CO

-120 -

-140 -

-160 L

AUTHOR GUNN (1958) a OLDS (1942) MASON (1961)

SYSTEM CH4- iC4H|o TEMP : 288- 511 K

00022 00028

l/T (K)

00034

Figure 8. Temperature dependence of interaction second virial coefficient

for the CH4-i-C4Hio system.

48
- A

TEMP 243 -511 K

-50 - sht

^— GUNN; OLDS ^

^,--'^

- °lK^ 1

-100

eA\ ^-.

o

.

<r ON

009c

E

V.E

-150 - A

o .>ff ^

M - MASON m \

'^§ \ •200 - AUTHOR

CH4- CaHs D CH4- 1C4H10 • CH4- nC4Hio 0^

O CH4- neoCj H 12 CH4- C3H8 -250 A CH4- 'C5H12 CH4- nCsHia

Zl 1

1 , ^ 1 0.0016 0.0024 0.0032 l/T (K)

0.0040

Figure 9. Temperature dependence of interaction second virial coefficient

for methane-paraffin hydrocarbon binary systems.

- Aa

TEMP 243-5IIK

-50 \\ 1

-100 ^

1

- 1^^

^

^*A

^ . E

E

-150 -

N - w "^

CD nV ^ -200 - AUTHOR

CH4- C2H6 \«

a CH4- rC4H|0 \

• CH4- nC4H|o \^

CH4- n«0C5H|2

A CH4- C3H8 -250 A "

CH4- CH4-

:

nCjHiz

1 1

, 0.0016 O0024 0.0032 l/T (K)

0.0040

Figure 10. .Temperature dependence of interaction second virial coefficient

for methane-paraffin hydrocarbon binary systems.

49
CQ

-50-

-100-

-150 -

-200-

-250 -

-300 -

SYSTEM CH4-nC5H|2

TEMP: 286-511 K

AUTHOR

DANTZLER (1968) a MASSOUDI (1973) • WORMALD (1979) MASON (1961) A PECSOK (1968) ZAALISHIVILI (1956)

_L 0.0022 0.0028 l/T (K)

0.0034

Figure 11. Temperature dependence of interaction second virial coefficient

for the CH4-n-C5Hi2 system.

SYSTEM^CH4-iC5Ht2

-120 >- TEMP=288-323K

. A

-130 -

-140 -

^-150

o|-I60

u

"lvj-170

00"

-

-

-180 -

-190

-200

AUTHOR

-210 - MASON (1961) PECSOK (1968)

-220 e-L 1 1 1 1 1 0.003150 0003300

I/T(K)

0.003450

Figure 12. Temperature dependence of interaction second virial coefficient

for the CH4-i-C5Hi2 system.

50
TEMP 243 -51 IK

-50-

-100

O

E« -150 oN

ffi -200

t

<%

PECSOK; MASON

AUTHOR

CH4- CgH^ D CH4-iC4Hio # CH4-nC4H|Q

O CH4-neoC5H|2 A CH4-C3He

-9«5n — ^ CH4-iC5H|2 ^^r- (^ CH4-nC5H,2

0.0016 0.0024 0.0032 l/T (K)

0.0040

Figure 13. Temperature dependence of interaction second virial coefficient for methane-paraffin hydrocarbon binary systems.

SYSTEM :CH4-neoC5H| 2

-60 l_

TEMPM99--550K

-120 r- AAc^

- ^

-180 ^

41°

3 - ^

E -240 -

03 -300 -

-360 - AUTHOR

BAUGHMAN (1975) aA

HAMANN (1955) BELLM (1974) -420

O.C

A STREIN (1971)

1 1 1 1 1 0100 0.00250 0.00400

l/KK)

Figure 14. Temperature dependence of interaction second virial coefficient

for the CH4-neo-C5Hi2 system.

51
200

1

TEMP = 298 -583K

SYSTEM

CH4 -iC4 H|0 a CH4 -nCj H|2 A CH4 - nC4 H|Q A CH4 - neoCsHig

0.0018 0.0024

l/T(K)

0.0030

Figure 15. Temperature dependence of interaction second virial coefficient

for methane-paraffin hydrocarbon binary systems.

SYSTEM=CH4-C02

TEMP=288-5IIK

-10

20

-5 -30 -

^ -40h

m

-50-

-60-

-70

AUTHOR

KATAYAMA (1980) O ZAALISHVILI (1956) MASON (1961)

J L 0.0022

J \ L

0.0028 l/T(K)

J Uk

00034

Figure 16. Temperature dependence of interaction second virial coefficient

for the CH4-CO2 system.

52
o

It)E

CD

-50

-100

-150-

-200 -

-250-

"300 L

TEMP 288- 510 K

ZAALISHVILI

A

SYSTEM

•A

A

CH4-CO2

C3Hg-C02

1C4HIO- C02 CaHg-coz

iC«n|2 ~ COo

0.0022 0.0028 l/T(K)

0.0034

Figure 17. Temperature dependence of interaction second virial coefficient

for carbon dioxide-paraffin hydrocarbon binary systems.

SYSTEM ••CH4-N2 TEMP=I55-292K

20-

— -40

E

V.

roEu

-ttO

CM 03

-80-

-100 AUTHOR

MASON (1961) ROE (1972)

-I20bd L J L J L

0.00325 0.00425 0.00525 l/T(K)

0.00625

Figure 18. Temperature dependence of interaction second virial coefficient

for the CH4-N2 system.

53
- A

TEMP 155-SIIK

r

^A

A

A

SYSTEM A CaHg -Nj

A nC4H,o-N2

CH4-N2

-20 r A \

— -40 o

E

J

"60

OQ

~

A

A

A

\

ROE Nw

-80 - A A

A A \

-100

:-l 1 1

1 1 1 0.0018 00036 0.0054

l/T (K)

Figure 19. Temperature dependence of interaction second virial coefficient

for nitrogen-paraffin hydrocarbon binary systems.

10-

8-

6- — 4 o

E

£"

od"

-6-

-8-

-lOti

SYSTEM- CH4-H2

TEMP=I44-289K

S

AUTHOR

MASON (1961) a MUELLER (1961) A VILCU(I977) A VILCU CAL'0(I977)

0.00300 0.00450 0.00600 l/T (K)

Figure 20. Temperature dependence of interaction second virial coefficient

for the CH4-H2 system.

54
E

toE.o

(^ m

- m

SYSTEM=CH4-H20

TEMP=293-51IK

-10 -

-20 -

-

-30 -

-

-40 -

-

-50 —

-60 -

AUTHOR

- RIGBY (1969)

-70 _j_ 1 1 1

1 > 1 1 1 . 1 0.0018 0.0024 0.0030 l/T{K)

Figure 21. Temperature dependence of interaction second virial coefficient

for the CH4-H2O system.

24.96 -

24.90 -

2 24.84 o

E

e 24.78

CQ 2472

24.66

2460

AUTHOR

BELL(I98I)

SYSTEM CH4-He

TEMP'292-320K

0,003100 0.003250

l/T (K)

0.003400

Figure 22. Temperature dependence of interaction second virial coefficient

for the CH4-He system.

55
-34 -

SYSTEM'CH4-NH3

TEMP=423-573K

-36 -

-38 —

-^o

E -40 ^

roo -42

^_

-^^ m

- UJ -44 —

-46 -

-48 - AUTHOR

LEE (1970)

-50 -1 1

1 1 IB 0.00175 0.00195 0.00215 l/T(K)

0.00235

Figure 23. Temperature dependence of interaction second virial coefficient

for the CH4-NH3 system.

-

SYSTEM=C2H6-C3He

TEMP=288-373K

-ISO

-

-2D0 —

— -220 E

ro

-

£-240 -

m

-

-260 —

-

-280 - AUTHOR

- 0ANTZLER(I968) MASON (1961) 300

L_ 1 1

1 1 0.0025 0.0029 0.0033

l/T (K)

Figure 24. Temperature dependence of interaction second virial coefficient

for the C2H6-C3H8 system.

56
TEMP^ 2IS-373K

-100

-200 o

E

•^

ico -300

CD

-400-

-500-

SYSTEM

CH4 -C2Hg n CaHg-CjHg • C2H6-nCflH|2 A C2H5 -C4HK) A ^z^t -nC4H|o

0.0020 0.0030

l/T (K)

0.0040

Figure 25. Temperature dependence of interaction second virial coefficient

for ethane-paraffin hydrocarbon binary systems.

SYSTEM: C2"6""C4H«3 TEMP: 288 -373 K -220 -

a

-240 ~

^

-260 -

"e -280 -

ij ^

OD -300

-320

-340

—

a a

_ AUTHOR

-360 - a

DANTZLER(I968) W0RMALD(I979) MASON (1961)

-380 t_ 1 11 1 1 0.0027 0.0031 00035

1/T(K)

Figure 26. Temperature dependence of interaction second virial coefficient

for the C2H6-n-C4Hio system.

57
TEMP ^ 215- 373K

A

A ' m

1

-100

- a A

-200 -

A

a

*-* o

E . I\

a

>^ '-i fO m \\

°D

a -300 — \

N • \ CD

- • \

A

SYSTEM •

-400 CH4- CgHs • a CzHe C3H9

• CaH, -nCaH,2 CzHe -C2H6 • A C2H6 ''C4H1Q

-500

1 1 1 L_ 1 1 0.0020 00030

l/T (K)

O0040

Figure 27. Temperature dependence of interaction second virial coefficient

for ethane-paraffin hydrocarbon binary systems.

-280

-300

-320

- -340

I

-360

03 -380

-400

-420

-440

SYSTEM CzHe- nC5H|2 TEMP 288 -373

K

AUTHOR DANTZLER (1968) D PECSOK (1968) A MASSOUOI (1973)

_L 0.00260 000290

l/T (K)

0.00320

Figure 28. Temperature dependence of interaction second virial coefficient

for the C2H6-n-C5Hi2 system.

58
. TEMP: 215. 373K

- A

A 1

-100

-

A

a

-200 - A

Q

A

o

E - A

A

a

E \ °a

_o -300 — y^V A

CM DANTZLER^ >

CD*

-400

-

SYSTEM

CH4-C2H6

N

\

A

a CaHg-CsHg • CaHg-nCsHij V

C2H6-C4H„

A CjHs -nC4H|o •

-500 -

1

1 _ , 1

1 1 0.0020 0.0030

l/T (K)

00040

Figure 29. Temperature dependence of interaction second virial coefficient

for ethane-paraffin hydrocarbon binary systems.

-30

-40-

-60 o

E

K^

E^ -80

GO

100

-120

SYSTEM C2H«-C02 TEMP: 273-511 K

AUTHOR

K ATA YAMA (1980) a ZAALISHIVILI (1956) A MASON (1961)

O0022 Q0028

l/T (K)

_L 00034

Figure 30. Temperature dependence of interaction second virial coefficient

for the C2H6-CO2 system.

59
Or

-50

-100 o

inE

CM

-150

-200

-250

-300

TEMP 288- 510 K

SYSTEM CH4-C02

CjHg-COa

"C4H10- COg

CgHs-cOa

CsHij-COj

nCjHij-COj

00022 0.0028 l/T(K)

0.0034

Figure 31. Temperature dependence of interaction second virial coefficient

for carbon dioxide-paraffin hydrocarbon binary systems.

SYSTEM CzHg-Na

TEMP: 277-511 K

m

-20 -

^ -40

toE

CD -60 -

-80 _

- AUTHOR

GUNN (1956) MASON (1961)

-100 1 1 1 1 1 0.0018 0.0024 0.0030 l/T (K)

0.0036

Figure 32. Temperature dependence of interaction second virial coefficient

for the C2H6-N2 system.

60
0-

-20-

^ -40- o

E

,;^ J

"60 H

cs -80-

-100-

TEMP: 155- 311 K

A

SYSTEM A CaHe-Nz A nC4H|o-N2

CH4-N2

A

A A

A

0.0018 Q0036 00054

l/T(K)

Figure 33. Temperature dependence of interaction second virial coefficient for nitrogen-paraffin hydrocarbon binary systems.

SYSTEM^ C2He-H20 TEMP ' 298 - 444 K A

-40

A

A

-60 -

E

,;^E

-80

00 -100

-120

-140

AUTHOR

COAN (1971) A RIGBY (1969)

1 1 1 0.0022 0.0026 00030

l/T (K)

00034

Figure 34. Temperature dependence of interaction second virial coefficient

for tlie C2H6-H2O system.

61
TEMP=298 -5IIK

-20 -

-40

o

r }

£ -60

RIGBY-^

- *v,^

^^-80 - ^N\

-100

SYSTEMS

COAN^ \

-120 HjO-CH* \

A HjO-CzHe

l 1

1 1 \

0.0018 0D024

I/T{K)

0.0030

Figure 35. Temperature dependence of interaction second virial coefficient

for water-paraffin hydrocarbon binary systems.

-80-

-90-

I

-100

EuN

°° -llOh

120

-130

AUTHOR

KHOURY (1971)

SYSTEM : C2H«- HeS TEMP 323-398

K

0.0026 0.0028 l/T (K)

0.0030

Figure 36. Temperature dependence of interaction second virial coefficient

for the C2H6-H2S system.

62
E

do"

-300 r- CsHg- nC4H|o TEMP 288- 373 K

-350 -

-400 -

-450 -

'

-500 -

-550 - AUTHOR

DANTZLER (1968) MASON (1961)

1 I 1 1 1 0.0027 0.0031 l/T (K)

0.0035

Figure 37. Temperature dependence of interaction second virial coefficient for the C3Hs-n-C4Hio system.

Or

-200-

-400

"oE

E

3. -600-

CD

-800-

•1000

TEMP: 243 -51 IK

SYSTEM

CjHg- CH4 a C3He-nC4H|0 A C3H9-C2H5 A C3H8-nC5H|2

0.0016 0.0024 0.0032 l/T(K)Q0040

Figure 38. Temperature dependence of interaction second virial coefficient

for propane-paraffin hydrocarbon binary systems.

63
-400

-450

o

E

E

500

550

-600

-650

-700

SYSTEM^ CsHe-nCsHij TEMP : 298 - 373 K

AUTHOR DANTZLER (1968)

000260 0.00290 l/T(K)

0.00320

Figure 39. Temperature dependence of interaction second virial coefficient

for the C3H8-n-C5Hi2 system.

_ TEMP : 243 -51 IK

-200

•

A

A

A

- a ^A

o

E

E

en

-400

-600

-800

-1000

SYSTEM C3H8-CH4 D C3H8-nC4H|0 A CsHj-CjHj

A CjHj-nCsHia

J 1

A

a

1

a

^ Q

A

1 , 1 0.0016 0.0024 0.0032 l/T(K)

0.0040

Figure 40. Temperature dependence of interaction second virial coefficient

for propane-paraffin hydrocarbon binary systems.

64
-40

-60

-80

"I -100

^-,20

CD

-140

-160

-180

-200

SYSTEM : CsHg-COe

TEMP: 288-511 K

AUTHOR

80UGARD (1976) a MASON (1961) GUNN (1958) A SIE (1966)

0.0022 0O028

l/T (K)

0.0034

Figure 41. Temperature dependence of interaction second virial coefficient for the C3H8-CO2 system.

Or

o

10E

ffi

-50

-100

-150

-200

-250

-300 L.

TEMP ZeS-SIOK

SYSTEM CH4-C02

CjHe-cOj

nC4H|o- COj

CaHg-coz

iCsHij-COj

nCjHij-COa

SIE

0.0022 0O028

l/T(K)

_L 0.0034

Figure 42. Temperature dependence of interaction second virial coefficient

for carbon dioxide-paraffin hydrocarbon binary systems.

65
-20-

--. -40- o

E

;^3 -60

CD

-80|-

-100-

TEMP: 155- 511 K

A

A

A

SYSTEM CjHe-Na A nC4H|Q-N2 CH4-N2 a CjHg-Na

A

^ A

^°A

0.0018 00036 00054

l/T(K)

Figure 43. Temperature dependence of interaction second virial coefficient

for nitrogen-paraffin hydrocarbon binary systems.

1

SYSTEM CsHs-Ht TEMP 393- 423

44 -

E

u

CVJ CD

42

40

1

38

-

36 AUTHOR WAROWNY (1978)

1 ... .L

1 1 000239 0.00247 l/T(K)

Q00255

Figure 44. Temperature dependence of interaction second virial coefficient

for the CaHg-He system.

66
o

E

,;^E

u

OQ

-250

.

SYSTEM nC4H|o- iC4HH3 TEMP 344-445

K

-300

-350

-400 -

~

-450 -

AUTHOR

CONNOLLY (1962)

-500 T 1 1 1 000220 0.00250

l/T(K)

0.00280

Figure 45. Temperature dependence of interaction second virial coefficient

for the n-C4Hio-i-C4Hio system.

-200

o

-40°

En

E3 -600

h

m

-800 -

-1000

-1200 L

TEMP: 250-583K

SYSTEM

nC4Hio - CH4

1 nC4 H|o - CjHa

i nC4 H|Q - nC4H|o

k nC4 H|o- CzHs ^ nC4 H|o - iC4H|o y nC4 H|o - nCjH|2

0.0016 0.0024 0.0032 l/T (K)0.004O

Figure 46. Temperature dependence of interaction second virial coefficient

for n-butane-paraffin hydrocarbon binary systems.

67
SYSTEM • nC4H|o- nCsHij TEMP 298 -373

-

-600 -

-700 -

-800 - o

E

-

E

oq"

-900

-1000

-1100

-

AUTHOR

OANTZLER (1968) A

JESSEN (1938) -1200

li. 1 1 , - 0.00260 0.00290

l/T{K)

0.00320

Figure 47. Temperature dependence of interaction second virial coefRcient

for the n-C4Hio-n-C5Hi2 system.

-200

-. -400 o« -600

E

o- -800

GQ

-1000

-1200

-1400 -

TEMP: 289 -550K

OANTZLER

SYSTEM

nC5H|2-CH4 a nCjHig-CjHg • nC5H|2-nC5H|2

nC5H|2-C2H6 A nCs H|2- nC4H|o

_L

JESSEN

0.0015 0.0021 0.0027 l/T (K)

00033

Figure 48. Temperature dependence of interaction second virial coefficient

for n-pentane-paraffin hydrocarbon binary systems.

68
-60

80

100

120 = -140- o

E

£ -160-

m

-180

-200

-220

240

SYSTEM nC4HK3-C02 TEMP^ 288-478 K

AUTHOR GUNN (1958)

(- a S IE (1966) A MASON (1961)

0.0020 00026

l/T (K)

00032

Figure 49. Temperature dependence of interaction second virial coefficient

for the n-C4Hio-C02 system.

Or TEMP 288- 510 K

-50

100 o« -150 o

CD -200

-250

-300 1

GUNN

SYSTEM CH4-C02 a CjHa-COz • nC4Hio-C02 CzHs-COz A iC5H|2-C02

nCjHig-COj

O0022 0.0028 l/T(K)

_L 0.0034

Figure 50. Temperature dependence of interaction second virial coefficient

for carbon dioxide-paraffin hydrocarbon binary systems.

69
Or

-20

o

E^ -40

Eu

CD -60

-80

-100

SYSTEM nC4Hio- f*2 TEMP 288 - 478 K

AUTHOR

CRUIKSHANK (1968) D HICKS (1968) • YOUNG (1958) GUNN (1958) A MASON (1961)

00020 0.0026l/T (K)

Q0032

Figure 51. Temperature dependence of interaction second virial coefficient

for the n-C4Hio-N2 system.

-20

--. -40 o

E

J

-60

N

OD

GUNN

-80

-100

^2

TEMP 135- 311 K

SYSTEM

0.0018 00036

CzHg-Nj A nC4H|o-N2

CH4-N2 a CjHj-Nj

_L O0054

l/T (K)

Figure 52. Temperature dependence of interaction second virial coefficient

for nitrogen-paraffin hydrocarbon binary systems.

70
56

54

oJ

E^ 50

m

48

46 -

AUTHOR

JONES (1967) SYSTEM : nC4H|0-H« TEMP 373- 498

K

0.00200

_L 0.00230

l/T (K)

000260

Figure 53. Temperature dependence of interaction second virial coefficient

for the n-C4Hio-He system.

-80-

-120

o

E

"^ -160 o

CO

-200 -

-240

-280 -

SYSTEM ^nCgHia-COa TEMP^ 298- 353 K

AUTHOR

DESTY (1962) D SIE (1966) MASSOUOI (1973) A VIGDERGAUZ (1971)

_L J

0.0028 0.0030 0.0032 l/T (K)

0.0034

Figure 54. Temperature dependence of interaction second virial coefficient for tiie n-C5Hi2-C02 system.

71
Of-

-50-

-100 o

rt -150-

m

-200

-250

-300

a

SYSTEM CH4-C02 a CjHa-cOj _ • nC4H|o- COa CzHs-coa A iC5H|2-C02

nCjHij-COg

TEMP 286- 910 K

VIGOERGAUZ

"^

MASSOUDI -

0.0022 0.0028 l/T (K)

0.0034

Figure 55, Temperature dependence of interaction second virial coefficient

for carbon dioxide-paraffin hydrocarbon binary systems.

o

E

u

tn

SYSTEM: nCjH, 2- N2 -60 r# TEMP298-353K

- o

-70 -

" «

-80 -

°

-90 _ *

AUTHOR • CRUIKSHANK (1966) O CRUIKSHANK (1968) GAINEY (1967) 100 _ a OESTY (1962) HICKS (1968) A EVERETT (1965) •

LETCHER (1974) a

GAINEY (1970) -no L * LEUNG (1974) MASSOUDI (1973) • VIGOERGAUZ (1971)

- O YOUNG (1968)

-120 1-

1 1 1 , 1 00028 00030 0D032 00034

1/T(K)

Figure 56. Temperature dependence of interaction second virial coefficient for the n-C5Hi2-N2 system.

72
lOr

8-

SYSTEM : nCsHfj-H, TEMP: 288-296 K

O

E

,^

E

o

CD 4 -

AUTHOR

CRUIKSHANK (1966) a EVERETT (1965) A DESTY (1962) A MASON (1961)

0.00335 000339 000343

l/T (K)

J

0.00347

Figure 57. Temperature dependence of interaction second virial coefficient

for the n-C5Hi2-H2 system.

Or

o

lOE

-50-

-100-

-150-

-200

-250

-300

TEMP' 288- 910 K A

a A

Q

SYSTEM CH4-C02

CsHg-CO,

nC4H|o- CTOz CaHe-coa

iCjHij-COj

nCjHij-COj

^

A

a

• a

OESTY

A A

I 0.0022 0.0028 l/T{K)

00034

Figure 58. Temperature dependence of interaction second virial coefficient

for carbon dioxide-paraffin hydrocarbon binary systems.

73
-60r

o

E

.;^E

m

-70

80

SYSTEM iCsH,2 -N2

TEMP: 298- 338 K

-90

AUTHOR

DESTY (1962) -100 \- a YOUNG (1968) GAINEY (1970)

0.002950 0.003100l/T(K)

0.003250

Figure 59. Temperature dependence of interaction second virial coefficient

for the i-C5Hi2-N2 system.

-20

^2 -40 o

E^ -60

TM -80

-100

-120-

YOUNG

-140

t-L

TEMP 156- 511 K

SYSTEM

CH4 -Ng C3H9 -N2 C2HS-N2

iCj H[2-N2

''C4H1Q-N2 nCjHg-Nj

0001

8

_L 0.0036 l/T (K) 0.0054

Figure 60. Temperature dependence of interaction second virial coefficient

for nitrogen-paraffin hydrocarbon binary systems.

74
-100

120

-140

-160

o

E

-180

>»

i*rE

ii -200

CM CD -220

-240

-260

-280L_L

SYSTEM •• ntoCsH|2- Hz TZMP- 199-258 K

£

Q

a A

a

AUTHOR BAUGHMAN I (1975) BAUGHMAN 2 (1975) a BAUGHMAN 3 (1975)

aA

_L O0038 00042 0.0046

l/T (K)

00050

Figure 61. Temperature dependence of interaction second virial coefficient for the neo-C5Hi2-N2 system.

o

E

Eo

CD

r TEMP: 155-511 K A

A

-50 Oa ^a

-100 8

8

-150

SYSTEM CH4-N2

So

200 - C3H8 -Nj • nC4H|o-N2 8

neoCjHij -Nj

A CgHs -Na A iC5H|2-N2 8

250 - nC5H,2-N2

- 1 1 L. 1 1 1 0.0018 0.0036

l/T (K)

00054

Figure 62. Temperature dependence of interaction second virial coefficient

for nitrogen-paraffin hydrocarbon binary systems.

75
76 -

SYSTEM neoC5H,2-H» TEMP 199-258 K AUTHOR BAUGHMAN (1975) 74 —

72 -

70 -

1 68

E

m

-

64 -

62 -

60 -

- 58 -L 1 1 1 1

, 1 0.0038 00042 00046

l/T (K)

00050

Figure 63. Temperature dependence of interaction second virial coefficient

for the neo-C5Hi2-He system.

-26-

-28

_ -30

"o£

to

CQ

-34

-36

-38

SYSTEM CO- COa TEMP' 303-363 K AUTHOR

COTTRELL (1956)

_L 0.00285 000305

l/T (K)

0.00325

Figure 64. Temperature dependence of interaction second virial coefficient

for the CO-CO2 system.

76
-50

o

e -100

o

"^

<D -150

-200

-250

300

SYSTEM=C0-H2

TEMP=36-298K

4

AUTHOR

REUSS 11956) a TOWNENO (19311 SCOTT (1929)

I 0.002 QOlO 0.018 1/T{K)

0.026

Figure 65. Temperature dependence of interaction second virial coefficient for the CO-H2 system.

-100

o

E

00

300-

-400

X

system: COj - Nj TEMP: II0-398K

00020

AUTHOR

COTTRELL (1956) a 60RSKI (1953) • MASON (1961) O YAKIMENKO (1977) EDWARDS (1942) A GUNN(I958) PFEFFERLE (1955)

_L 0.0050I/T(K)_L 00080

Figure 66. Temperature dependence of interaction second virial coefficient

for the CO2-N2 system.

77
-20.0

-25.0

o -300

Eom

•35.0

-40.0

-45.0 -

-50.0 k

SYSTEM^ C02-N2 TEMP 288 - 398 K

AUTHOR

COTTRELL (1956) GORSKI (1953) MASON (1961) EDWARDS (1942) GUNN (1958) PFEFFERLE (1955)

0.0027 0.0031 l/T (K)

0.0035

Figure 67, Temperature dependence of interaction second virial coefRcient

for the CO2-N2 system.

— -12 o

E

J -18 h

CO

-24 h

-30 -

-36

SYSTEM C02-H2 TEMP 298 - 363 K

AUTHOR

COTTRELL (1956) EDWARDS (1942)

_L. _L 0.0028 O0030

l/T (K)

00032

Figure 68, Temperature dependence of interaction second virial coefficient for the CO2-H2 system.

78
SYSTEMCOa-HgO

TEMP'288-373K

-

-100 -

-

-120 -

-140 —

£ -160 3

-

CD

-

-180 -

-200 - AUTHOR

A

r

C0AN(I97I) A

A P0LLITZER(l924r

-220

r_L 1 1

1 1 1 00260 000290 0.00320 1/T(K)

Figure 69. Temperature dependence of interaction second virial coefficient

for the CO2-H2O system.

30

20

10

o

£

J

-10-

CD -20

-30

-40-

-50t=.

SYSTEM'C02-He

TEMP292-423K

O •

t

AUTHOR

BELL (1981) EDWARDS (1942) LINSHITS (1975) TSIKLIS (19740) C0TTRELL(I956)

HfiRPER(l957)

TSIKLIS (1974 b) PFEFFERLE (1955)

1 I _L 00022 00026 00030 00034

/T(K)

Figure 70. Temperature dependence of interaction second virial coefficient

for the C02-He system.

79
28

^ 26

"3E

£u

"^ 24

oq'

22

20

SYSTEM^C02-He

TEMP^292-423K

AUTHOR

BELL(I98I) HARPER(I957)

PFEFFERLE(I955)

TSIKLIS (1974 b) C0TTRELL(1956)

LINSHITS (1975) TSIKLIS (1974a)

Q

X

0.0022 0.0026 0.0030

1/T(K)

0.0034

Figure 71. Temperature dependence of interaction second virial coefficient

for the COa-He system (datum on Edwards and Roseveare deleted).

-50

--. -100 o

E

-150

GQ

-200

-250

-300-

S.

SYSTEM : Ng-Hg TEMP: 36-323K

•tr-e,

AUTHOR BREWER (1969) VILCU CAL'O (1973) • OSTRONOV (1967) O LUNBECK(I95I) EDWARDS (1942) A MICHELS (1949) 4 ZANDBERGEN (1967) VERSCHOYLE (1926) • VILCU (1973)

Cr REUSS (1956)

0.002 0.010 0.018 l/T(K)

0.026

Figure 72. Temperature dependence of interaction second virial coefficient

for the N2-H2 system (36-323K temperature range).

80
15.0

IQO-

_ 5.0 "5E

m

-5.0

-10.0

-15.0

i

g

SYSTEM: N2-H2 TEMP: I48-323K

I

AUTHOR BREWER (1969) a VILCU-CAL'D (1973) • OSTRONOV (1967) O LUNBECK (1951) A EDWARDS (1942) A MICHELS (1949) ZANDBERGEN (1967) VERSCHOYLE (1926) • VILCU (1973)

0.00300 0.00450

l/T (K)

0D06O0

Figure 73. Temperature dependence of interaction second virial coefficient

for the N2-H2 system (148-323K temperature range).

o

E

E

m

-10.0 _

SYSTEM•^42-H20

TEMP' 298- 423 K

-150 -

-200 -

-25.0 - A

-30.0 -

-35.0 - AUTHOR

RICHARDS (1981) RtGBY(l968)

-400 .

1 1 1 1 1 A 1 0.0022 0.0026 0.0030

1/T(K)

00034

Figure 74. Temperature dependence of interaction second virial coefficient

for the N2-H2O system.

81
o

"Ium

system: N2 - H«

_

It TEMP-- 90- 748K

22bb

**^ ~ -ft V « •>

20 *

^A°

- A

18 - AO

- A

O

16 -

- Ad

14 - o

AUTHOR A

12 - SELL (1981) a KRAMER (1957) • HALL(I969) o CANFIELD (1963) •

10 - A BREWER (1969) A EDWARDS (1942)

- PfEFFERLE(l955) KNOBLER (1959) 8 - • KU (1967) 1* WITONSKY (1963) •

6 - 1 1 1 1 1 0.000 0004 0.008 1/T(K)

0.012

Figure 75. Temperature dependence of interaction second virial coefficient for the N2-He system.

30 r

20

10

o

«• -10 o

CD -20

•30-

40

-50

SYSTEM^ N2-NH3

TEMP:3I8-673K

AUTHOR

LEE (1970)

_1_ ODOIO 0.0016

_L 0.0022

J_ 0.0028 l/T(K)

Figure 76. Temperature dependence of interaction second virial coefficient

for the N2-NH3 system.

82
-100-

-120-

o

-1401-

(£"-160-

-180-

-200 tl

system: NaO -HjO

TEMp: 298-373

AUTHOR

COAN (1971 )

0.00260 00029 000320

1/T(K)

Figure 77. Temperature dependence of interaction second virial coefficient

for the N2O-H2O system.

o

E

E

CQ

SYSTEM

:

H2-H« 20 TEMP: 14 -448K |k

10 "

_

-10

AUTHOR Oi BREWER (1969) WL

20 _ D TANNER (1930) >

GIBBY (1929) *0 A BEENAKKER (1959) • BEENAKKER (1959) Oj O BEENAKKER (1959) HO *0

30 t^ KNOBLER (1959) VAREKAMP(I959)

k VAREKAMP (1959) Og

- -tr VAREKAMP (1959) HD

40 1 , 1 1

1 0.02 004

l/T (K)

0.06

Figure 78. Temperature dependence of interaction second virial coefficient

for the H2-He system (14-448K temperature range).

83
- a

SYSTEM: Hj-Ht TEMP: 148- 448

K

17.00 -

16.50 -

c: 16.00 o

E

>a 1550 N

CD

A A

15.00 -

14.50 AUTHOR BREWER (1969) a TANNER (1930) A GI8BY (1929)

14.00 3 1 J 1 1

1 00030 0.0048 l/T(K)

0.0066

Figure 79. Temperature dependence of interaction second virial coefficient

for the H2-He system (148-448K temperature range).

10

^ -10 o

E

,;^E -20 u

CD -30 h

-40 -

SYSTEM : Hj - He TEMP: I4-90K

8.

o

AUTHOR

BEENAKKER (1959) a BEENAKKER (1959) HO A BEENAKKER (1959)09 A KNOBLER (1959) • VAREKAMP (1959) O VAREKAMP (1959) HD VAREKAMP (1959)02

-50 Li

0.02 0.04 l/T (K)

0.06

Figure 80. Temperature dependence of interaction second virial coefficient

for the H2-He system (14-90K temperature range).

84
References

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89
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90
NBS-114A (REV. 2-ec) U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See instructions)

1. PUBLICATION OR

REPORT NO.

NBS/TN 1249

2. Performing Organ. Report NoJ 3. Publication Date

July 1988

4. TITLE AND SUBTITLE

Evaluation o£ Data Availability and Quality for Interaction Second Virial Coefficients of Use to the Gas Industry

'•^4ierna?d J. Van Wie; Mark A. Langenberg; Wayne C.-W. Chang; Kesavalu H. Kumar;

Kenneth E. Starling

6. PERFORMING ORGANIZATION (/rjo/nt or other than NBS. see instructions)

NATIONAL BUREAU OF STANDARDS

U.S. DEPARTMENT OF COMMERCE

GAITHERSBURG, MD 20899

7. Contract/Grant No.

8. Type of Report & Period Covered

Final

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State. ZIP)

Same as item #6 above.

10. SUPPLEMENTARY NOTES

\2Z\ Document describes a computer program; SF-185, FlPS Software Summary, is attached.

11. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a si gnificant

bibliography or literature survey, mention it here)

Binary interaction second virial coefficient information useful to the natural

and syngas industries has been compiled and evaluated. An extensive literature

search has been conducted to obtain publicly available information dating back

to 1900. Assessments were made to determine data availability, quality and to

summarize data needs. No evaluations were made for values resulting from thermodynamic correlations; however, references containing such information are listed,

Each binary gas system has been individually evaluated and references containing

the highest quality and most abundant measurements have been listed in a table

of recommended values.

12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolons)

binary interaction second virial coefficients; data quality assessment* natural

gas; syngas

13. AVAILABILITY

[]^ Unlimited

I I For Official Distribution. Do Not Release to NTIS

rxl Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C.

20402.

Q31 O''''^'' From National Technical Information Service (NTIS), Springfield, VA. 22161

14. NO. OF

PRINTED PAGES

104

15. Pnce

USCOMM-DC 8043-P80



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