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PUBLICATIONS

NSRDS

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COMMERCE

National

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1170

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Phase Behavior in Binary

And Multicomponent Systems

At Elevated Pressures:

n-Pentane and

Methane-n-Pentane
NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards ' was established by an act of Congress March 3, 1901. Today,

in addition to serving as the Nation’s central measurement laboratory, the Bureau is a principal

’focal point in the Federal Government for assuring maximum application of the physical and

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THE INSTITUTE FOR BASIC STANDARDS provides the central basis within the United

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divisions:Applied Mathematics—Electricity—Metrology—Mechanics—Heat—Atomic and Molecular Physics—Radio Physics -—Radio Engineering 2—Time and Frequency 2—Astrophysics 2—Cryogenics.2 THE INSTITUTE FOR MATERIALS RESEARCH conducts materials research leading to improved methods of measurement standards, and data on the properties of well-characterized

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’ Headquarters and Laboratories at Gaithersburg, Maryland, unless otherwise noted; mailing address Washington, D.C. 20234.

- Located at Boulder. Colorado 80302.

:l Located at 5285 Port Royal Road, Springfield, Virginia 22151.
UNITED STATES DEPARTMENT OF COMMERCE

Maurice H. Stans, Secretary

NATIONAL BUREAU OF STANDARDS • Lewis M. Branscomb, Director

Phase Behavior in Binary and Multicomponent Systems

At Elevated Pressures: n-Pentane and Methane-n -Pentane

Virginia M. Berry and B. H. Sage

Chemical Engineering Laboratory

California Institute of Technology

Pasadena, California 91109

NSRDS-NBS 32

Nat. Stand. Ref. Data Ser., Nat Bur. Stand. (U.S.), 32, 73 pages (June 1970)

CODEN: NSRDA

Issued June 1970

For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402 (Order by SD Catalog No. C 13.48:32), Price 70 cent9
NATIONAL BUREAU Of STANDARDS

JUL 2 3 1970

no. /fln

/ 70

Cop

.

© 1970 by the Secretary of Commerce on behalf of the United States Government.

Library of Congress Catalog Card Number: 78-603442
Foreword

The National Standard Reference Data System provides effective access to the quantitative

data of physical science, critically evaluated and compiled for convenience, and readily accessible

through a variety of distribution channels. The System was established in 1963 by action of the

President’s Office of Science and Technology and the Federal Council for Science and Technology,

with responsibility to administer it assigned to the National Bureau of Standards.

The System now comprises a complex of data centers and other activities, carried on in

academic institutions and other laboratories both in and out of government. The independent

operational status of existing critical data projects is maintained and encouraged. Data centers

that are components of the NSRDS produce compilations of critically evaluated data, critical

reviews of the state of quantitative knowledge in specialized areas, and computations of useful

functions derived from standard reference data. In addition, the centers and projects establish

criteria for evaluation and compilation of data and make recommendations on needed improvements

in experimental techniques. They are normally closely associated with active research in the

relevant field. The technical scope of the NSRDS is indicated by the principal categories of data compilation

projects now active or being planned: nuclear properties, atomic and molecular properties, solid state properties, thermodynamic and transport properties, chemical kinetics, and colloid and

surface properties.

The NSRDS receives advice and planning assistance from the National Research Council of

the National Academy of Sciences-National Academy of Engineering. An overall Review Committee

considers the program as a whole and makes recommendations on policy, long-term planning, and

international collaboration. Advisory Panels, each concerned with a single technical area, meet

regularly to examine major portions of the program, assign relative priorities, and identify specific

key problems in need of further attention. For selected specific topics, the Advisory Panels sponsor

subpanels which make detailed studies of users’ needs, the present state of knowledge, and

existing data resources as a basis for recommending one or more data compilation activities. This

assembly of advisory services contributes greatly to the guidance of NSRDS activities.

The NSRDS-NBS series of publications is intended primarily to include evaluated reference

data and critical reviews of long-term interest to the scientific and technical community.

Lewis M. Branscomb, Director

ill
Preface

In 1966 support was received from the Office of Standard Reference Data of the National

Bureau of Standards for a program of data review undertaken in the Chemical Engineering Laboratory of the California Institute of Technology. Emphasis was directed to the volumetric and phase

behavior of the coexisting phases of pure paraffin hydrocarbons and their binary mixtures. An

effort was made to provide conservative estimates of the accuracy in contradistinction to the

precision of the tabulations presented. As a result of the withdrawal of B. H. Sage from active

research on July 1, 1969, the program has been limited to work completed at that time. The current

presentation covers a review of the methods employed, the volumetric and phase behavior of

n-pentane, and the volumetric and phase behavior in the methane-n-pentane system.

A number of the members of the staff of the Chemical Engineering Laboratory contributed

to the work and among these should be mentioned Donna Johnson, who aided in the tabulation of

the results and the preparation of the manuscript, and June Gray, who assisted the authors in the

preparation of the numerous diagrams associated with this activity.

IV
Contents

Page Foreword Ill Preface IV

List of figures V

List of tables V

Nomenclature and conversion factors., VII, VIII

1. Introduction 1 1.1. Measures of uncertainty 1 1.2. Residual methods 2

1.3. Dimensions and units 3

2. The n-pentane system 13

3. The methane-n-pentane system 22

4. References 66

List of Figures

Figure page

1.1. Variation in dew point volume of propane with temperature 4

1.2. Residual dew point volume of propane 5

1.3. Vapor pressure of propane 6

1.4. Vapor pressure-temperature diagram 7

2.1. Residual vapor pressure of re-pentane 15

2.2. Bubble point volume of n-pentane 16

2.3. Residual volume at dew point for re-pentane 17

3.1. Pressure-temperature diagram for methane-n-pentane system 24

3.2. Effect of pressure upon equilibrium ratio for methane-n-pentane system 25

3.3. Pressure-composition diagram for methane-n-pentane system 26

3.4. Pressure-temperature diagram for methane-n-pentane system, engineering units 27

3.5. Effect of pressure upon equilibirum ratio for methane-n-pentane system, engineering units 28

3.6. Pressure-composition diagram for methane-n-pentane system, engineering units 29

List of Tables

Table

1.1. Experimental values of dew point volume for propane

1.2. Residual specific volume of dew point gas for propane

1.3. Deviations of several sets of experimental data for specific volume of dew point gas for propane

1.4. Experimental values of vapor pressure for propane

1.5. Deviations in experimental values of vapor pressure for propane

2.1. Critical properties of n-pentane

2.2. Properties of the coexisting phases for re-pentane

2.3. Agreement of interpolated and experimental data for re-pentane

2.4. Critical properties of the n-pentane system, engineering units

2.5. Properties of the coexisting phases for re-pentane, engineering units

2.6. Agreement of interpolated and experimental data for re-pentane, engineering units

2.7. Accuracy of experimental background for re-pentane

2.8. Reviews of properties of the paraffin hydrocarbons

3.1. Properties of the coexisting phases in the methane-re-pentane system

3.2. Agreement of interpolated and experimental data for the methane-re-pentane system

3.3. Unique states for the methane-re-pentane system

3.4. Properties of the coexisting phases in the methane-n-pentane system, engineering units

3.5. Unique states for the methane-n-pentane system, engineering units

3.6. Agreement of interpolated and experimental data for the methane-re-pentane system, engineering units

3.7. Accuracy of experimental background for the methane-n-pentane system

Page8

9

10

11 1217

18

191920

21212230

46

4647

6565

6t>

V
,
CO,

C«

Nomenclature

B, C, D Coefficients

Variable

Molal equilibrium ratio, K — y\x

Number of points

Pressure, atm or psia

Residual pressure, atm or psia

Average deviation defined by

2 (Cm-Cm)IN

1 Absolute deviation defined by

^ (GeXp — Gsm )IN

1 Absolute temperature, K or °R

Temperature, °C or °F

Specific volume, liters/kg or ft 3/lb

Molal volume, liters/kg-mol or ft3 /lb-mol

V Residual volume, liters/kg

X Mole fraction liquid

y. Mole fraction gas

a Degrees of freedom

cr Standard error of estimate

{ X (^exp — Csm ) 2

1 /(/vSubscripts

exp Experimental

gr Graphical

k Component k

j Component j

r Reference

sm Smooth or predicted

Constants and Conversion Factors

Molecular Weight3

Methane 16.04303

Propane 44.09721

n-Pentane 72.15139

Physical Constants15

Force

1 pound (lb) avoirdupois

Length

1 U.S. inch (in)

Volume

1 liter (1)

Acceleration Due to Gravity— Standard

gc

Pressure

1 standard atmosphere (atm)

Temperature

1 degree centigrade (° C)

TIC

To F

= 453.59237 grams (g)

= 2.54 centimeters (cm)

= 1000 cm3

= 980.665 cm/sec2 = 32.1740 ft/sec2

= 1,013,250 dyne/cm2 = 101,325 N/m2

= 1.8 degrees Fahrenheit (°F) = 273.16 degrees Kelvin (°K) = 459.688 degrees Rankine (° R)

a Based on a Report of the International Commission on Atomic Weights, J. Am Chem. Soc. 84, 4175-97 (1962).

b Wilhoit, Randolph C. and Hathaway, Wayne, Tables of Conversion Factors Based on Accepted Constants as of 1965. Am Petroleum Inst., Project 44, Chemical Thermodynamic

Properties Center, Texas A & M Univ., College Station, Texas, Nov. 1965.

VII
Conversion Factors 3

Length

Units cm m in ft

1 cm 1 0.01 0.3937008 0.0328040

1 m 100 1 39.37008 3.280840

1 in 2.540000 0.02540000 1 0.08333333

1 ft 30.48000 0.3048000 12.0000 1

Area

Units cm2 m2 in2 ft 2

1 cm2 1 io-4 0.1550003 1.076391 x 10-3

1 m2 104 1 1550.0003 10.76391

1 in2 6.451600 6.451600 X 10-4

1 6.944444 X IO*3

1 ft 2 929.0304 0.09290304 144.0000 1 Volume

Units cm3 in3 ft 3 liter

1 cm3 1 0.06102374 3.531467 x 10-5 1.000 x io-3

1 in3 16.38706 1 5.787037 x 10~4 1.638661 X 10-2 1 ft3 28316.85 1728.000 1 28.31685

1 liter 1000.000 61.02375 0.0351467 1 Weight

Units g lb

1 g 1 2.204623 X IO-3

1 lb 453.5924 1

Specific Weight

Units g/cm3 g/ml lb/ft 3

1 g/cm3 1 1 62.42795

1 g/ml 1 1 62.42795

1 lb/ft 3 0.01601847 0.01601847 1

Pressure

Units atm kg/cm2 lb/in 2 Newton/m2

1 atm 1 1.033227 14.69595 1.013250 X 105

1 kg/cm2 0.9678411 1 14.22334 9806.650

1 lb/in2 0.06804596 0.07030696 1 6894.757

Newtons/

m

2 9.869233 X 10-6 1.019716 X 10-5 14.50377 X 10-5 1

a See footnote b on page VII.

VIII
Phase Behavior in Binary and Multicomponent Systems

At Elevated Pressures: n-Pentane and Methane-n-Pentane

Virginia M. Berry and B. H. Sage

This paper, which is concerned with the critical evaluation of data on the phase behavior of binary

systems, consists of three parts. In the first part the rationale of the evaluation process used is dis- cussed, in the second the behavior of n-pentane, and in the third the behavior of the system methane-npentane.

The properties of n-pentane considered are the critical constants and the vapor pressures and

densities of the saturated coexistent phases as functions of temperature. For the methane-n-pentane

system the compositions and densities of the coexisting phases are given as functions of temperature

and total pressure. Data for the unique states of the two-component system are also presented.

Discussions are given of the reliability of the selected values and of the differences between the selected values and various measured values.

Key words: Evaluated data; liquid-vapor equilibria; methane-n-pentane system; n-pentane;

thermodynamics.

1. Introduction

The critical review of experimental data in the

field of volumetric and phase behavior of pure

substances and mixtures involves, at best, certain

elements of judgment, particularly in regard to the

actual in contradistinction to the stated uncertainties of measurement. Probably historical evidence is the best evidence of the difference between the stated and actual uncertainties associated

with experimental observations. Often precision is confused with accuracy even though the author

has made a conscientious effort to appraise the

uncertainties in each of the primary experimental

variables involved. In this critical review and compilation, an effort was made to apply realistic and

conservative uncertainties to the tabulated values

which, to many readers, may seem unusually large

when the claims of the investigators are considered.

In the authors’ experience, the accepted intensive

properties of materials continue to change with the

passage of time by amounts which are many times

the original estimated uncertainties involved in the

experimental work. An example of such a situation

is the thermodynamic properties of water. Accurate

values of the thermodynamic properties of water

in both the liquid and gas phase are of importance

in the design of large steam turbines. Yet, within

the last 10 years, differences in the properties of

water employed in this country and in Russia re- sulted in significant differences in the prediction

of the efficiency of large steam turbines manufactured in the two countries. Even with unusual

international cooperation in this matter [l] 1 in- dividual nations still prepare their own tabulations

1 Figures in brackets indicate the literature references at the end of this paper.

of the thermodynamic properties of water which

differ somewhat in detail.

On the basis of such experience it is hoped that

the reader will understand the conservatism

employed in assigning rather large measures of

uncertainty to the individual experimental data as compared to that which has often been suggested

by the original experimental investigator. In addition, the uncertainties assigned to the recorded

values have been set forth on what is hoped to be

a realistic basis. It will remain for investigators

of the future to ascertain whether the somewhat

subjective assignment of uncertainty in connection

with the recorded values has been correct.

1.1. Measures of Uncertainty

In the following section a short discussion of the measures of uncertainty employed is presented.

No attempt has been made to justify the choice of

such measures but only to indicate in a specific

manner what was involved. The use of an example

is perhaps the best method to illustrate the fashion

in which the several measures of uncertainty can

be applied. In figure 1.1 2 is portrayed the variation

in the specific volume with temperature of the dew

point gas for propane. In addition, the various ex- perimental values upon which the critically chosen

fine was evaluated have been presented. There is set forth in table 1.1 the several results obtained by

different experimental methods. The points shown

in figure 1.1 are presented in the table together with

2 Figures and tables will be found at the end of the section to which they pertain.

372-701 0 - 70 -2

1
an estimate of the measure of uncertainty of each

set of experimental data.

In the example, presented in table 1.1, it has been

assumed that all of the uncertainty is in the specific

volume and none in the temperature. The curve was established by direct graphical inspection of

the data coupled with the application of “least

squares” methods of analysis to a particular

polynomial which will be presented later in the

discussion.

The greatest weight was given to the experimental

data which was assigned the smallest uncertainty

in table 1.1. Usually there is not as much experimental data as is indicated in figure 1.1 and the

choice of the smooth functional relation becomes,

in part, a matter of judgment. The average deviation

with regard and without regard to sign was established by use of the following expressions:

s = f(G-Gsm )IN, (1.1)

variable undergoes marked change from a low temperature to temperatures approaching that of the

critical state. In some circumstances it is desirable

to treat only portions of the range of the independent

variables as an independent statistical population.

This is particularly true when the data from different

investigators do not extend over the entire range of

the independent variable as is the case in figure 1.1. In many ways it would be advantageous to consider

the normal distance of the curve from the experimental points in question. However, this introduces

significant complexities in the evaluation of each

measure of uncertainty and for that reason has not

been adopted in the current tabulations.

1.2. Residual Methods

In many situations the combination of analytical

and graphical techniques is useful. For example,

it is possible to approximate the smooth curve shown in figure 1.1 by a polynomial of the following

form:

s '=2\G-Gm\IN. (1.2)

1 For the most part, the value of the average deviation

with regard to sign should be small and deviate

from zero primarily as a result of intentional bias

in locating the critically chosen value in order to favor the more accurate data. This is illustrated by

the values of the average deviation with regard to sign of the points shown in figure 1.1 which have

been tabulated in table 1.1 for each of the several

investigators.

As a second measure of uncertainty, the average

deviation without regard to sign was established

from eq (1.2) and is one useful measure of the

variability of the data from the smooth curve shown.

The results of applying eq (1.2) to the experimental

information presented in figure 1.1 are also recorded

in a portion of table 1.1. The average difference between deviations with regard to and without

regard to sign is evident.

For many purposes, the standard error of estimate

is a useful means of indicating the difference between a chosen continuous function such as the curve in figure 1.1 and the experimental points

involved. This quantity may be defined by eq (1.3):

a 2<c-csm v

i- l (N-a)}1' 2 (1.3)

The quantity a represents the degrees of freedom

associated with the system. In the case of a pure

substance it is one since the temperature fully

establishes all of the intensive properties of the two

coexisting phases. The values of the standard error

of estimate as established from eq (1.3) for each

of the experimental investigations are recorded

in a portion of table 1.1. All of these measures of uncertainty suffer from

the fact that the magnitude of the dependent

V=AT+ BT2 + CT3 + DT4 = 24.967T- 0.21184T

2 + 0.60276 X 10-3 P - 0.57430 X HU6 !

74 (1.4)

In this instance, the coefficients have been indicated

in both symbolic and numerical form. There is shown in figure 1.2 the smooth curve of figure 1.1 and the graphical representation of eq (1.4). Upon

a markedly enlarged scale the difference between

the analytical and graphical representation has been

depicted in a portion of figure 1.2. Such a difference

is called the residual specific volume of the dew

point which would be defined by:

V=V-Vr (1.5)

The value of the residual specific volume of the

dew-point gas may be evaluated for each of the ex- perimental points by application of eq (1.5). The

corresponding values of the analytical reference

values established from eq (1.4) for the temperature

of measurement as well as the values of the residual

specific volume of the dew-point gas are recorded

in a part of table 1.2 for each set of experimental

data. It is apparent from a review of table 1.2 that

the residual specific volumes do not undergo changes

in order of magnitude over the entire range of

temperature.

Smooth values of the residual specific volume for

each of the experimental points also are recorded in

table 1.2. It is evident that the graphical precision

realized by use of the residual techniques is much

greater than that feasible from direct plotting of the

data. Attempts to increase the scale of the graphical

operations invariably results in such wide spacing

of the experimental points as to render any marked

improvement in the precision of the graphical

operation difficult. In table 1.3 are shown the values obtained for

the average deviation with regard to sign, the

2
average deviation without regard to sign, and the

standard error of estimate as determined from large

plots, one such as is shown in figure 1.1 and a similar

sized plot involving the residual data shown in figure

1.2. It is believed that the comparison presented in

table 1.3 shows what can be gained by the use of

residual methods.

Such approaches are also useful in connection

with the smoothing of vapor pressure data. Under

such circumstances a form of the Antoine equation

[2] may be used as the reference expression for

vapor pressure. The reference vapor pressure may

be approximated by:

logioPr^+y (1.6)

Using propane as an example, the coefficients of

eq (1.6) become:

logic Pr = 4.294323 - 990

'p--- (1.7)

There is shown in table 1.4 experimental values of

the vapor pressure of propane based upon the meas- urements of several investigators. The corre- sponding reference vapor pressure calculated from

eq (1.7) is included along with the residual vapor

pressure defined by eq (1.8):

P = P-PT (1.8)

In figure 1.3 is depicted the vapor pressure as a function of temperature for propane with the ex- perimental data of table 1.4 included. In the lower

part of this figure is shown the residual vapor pres- sure with the same experimental data. The shape

of the residual vapor pressure curve is typical for

most paraffin hydrocarbons when a form of the

Antoine equation is employed as a reference. The

precision with which the measures of uncertainty can be established has been increased manyfold

by the use of the residual vapor pressure shown in

the lower part of figure 1.3. The results of the

evaluation by analytic methods of the average deviation with regard to sign, the average deviation

without regard to sign, and the standard error of

estimate are recorded in table 1.5 for each set of

experimental data.

Such residual techniques as have been described were employed in this review and tabulation whenever feasible. A certain amount of ingenuity is

required to utilize the most efficacious form of the

analytical expression to approximate the experimental behavior. The use of residual methods prevents a tendency to expand the scale of both the

independent and dependent variable in an attempt

to increase the precision of the direct interpolative

process. Often such attempts yield unsatisfactory

results because of the wide spacing of the experimental data. This is illustrated in figure 1.4 where

the vapor pressure data for propane have been

expanded on a large scale plot involving only a

portion of the temperature range. Physical separation of points on the diagram indicates the

uncertainties that are introduced in arriving at the

most probable curve to draw through the data.

1.3. Dimensions and Units 3

The greater part of the scientific literature is expressed in the mass-length-time system of dimensions. This system of dimensions will be used

throughout this compilation in the primary tabulations. However, in the interest of utility, pressures

will be expressed in atmospheres. A conversion

factor is available to permit the establishment of

the numerical value of the pressure expressed in

newtons per square meter if such should be desired.

Temperatures will be expressed in degrees kelvin

which are related to temperatures in degrees

Celsius by the following expression:

T=t + 273.16 (1.9)

The value of the constant in eq (1.9) is based upon

recent international agreement concerning the

temperature in degrees kelvin of the triple point of

water [3], The nomenclature employed together

with the dimensions and units involved are given

before the introduction on p. vil. A short table of

conversion factors for the common dimensions and

units used is also presented, p. VIII. A number of secondary tabulations have been

prepared involving the force-length-time system

of dimensions and engineering units. The appropriate conversion factors may be found in the abovementioned conversion table.

3 The NBS Office of Standard Reference Data, as administrator of the National Standard Reference Data System, has officially adopted the use of SI units for all NSRDS publications, in accordance with NBS practice. This publication does not use SI units because contractual commitments with the author predate establishment

of a firm policy on their use by NBS. However, conversion factors are given. We urge

that specialists and other users of data in this field accustom themselves to SI units as rapidly as possible.

3
o

CO

ro

O

ro

LlI (T

O 3

C\J hro <

cr

LlI CL

LJ

O H

ro

O

CO

C\J

lO

CVJ O

by\/ sjid\\\

LOn- o lo

LO C\J

3IAimOA

4

FIGURE

1.1.

Variation

in

dew

point

volume

of

propane

with

temperature.
VOLUME

liters

/kg

2.5

0

- 2.5

- 5.0

FIGURE 1.2. Residual dew point volume of propane.

5

RESIDUAL

VOLUME

liters

/

kg
VAPOR

PRESSURE

atm

0.25

0

- 0.25

280 300 320 340 360

TEMPERATURE K

FIGURE 1.3. Vapor pressure of propane.

6

RESIDUAL

VAPOR

PRESSURE

atm
VAPOR

PRESSURE

atm

TEMPERATURE K

Figure 1.4. Vapor pressure-temperature diagram.

7
Table 1.1. Experimental values of dew point volume a /or propane

Temperature

Reference

Temperature

Reference

Dana

[4]

Sage

[5]

Reamer

[6]

Helge- son b [7]

Dana

[4]

Sage

[5]

Reamer

[6]

Helge- son

b [7]

K K

255.4 169.2 343.5 15.4

260.9 141.7 344.3 15.2 15.4 266.5 118.6 346.4 14.3 272.0 99.9 346.9 14.0 277.6 85.5 82.8 349.8 13.2

283.2 73.7 72.7

350.1 12.7 288.7 63.1 62.3

352.7 12.1 293.9 52.4

353.1 11.6

294.3 55.1 53.7

355.4 11.3 299.8 48.1 46.4 355.9 10.6

301.1 43.3

305 4 42.0 40.2 358.3 10.2 307 5 37.0 358.6 9.6 310 9 3A 9 34. ft 34. Q 360.9 9.8 9.5 313.3 32.2 361.3 8.8 363.6 8.5 313.5 32.6

316.5 32.5 30.4 363 8 8 0

318.6 28.3 366 3 7.3 322.0 28.7 26.5 368 4 6.6

323.4 25.3 368 8 6.5 370.0 4.5 324.5 J 25.6

327 6 23.0 23.1

327.9 22.8

332.0 20.6 Estimated uncer332.1

333.2

20.5

20.2

tainty c

, percent 1.0 0.2 0.2 0.2

336.1 18.6 Deviation

338.7 17.6 absolute d 1.07 0.31 0.28 0.34

339.6 16.8 algebraic e 1.07 -0.27 0.22 0.07

339.9 16.9 standard f 1.4* 0.62 0.39 0.58

a Specific volumes expressed in liters/kg.

b Specific volume calculated by application of Clapeyron equation to latent heat of vaporization data.

c Estimated uncertainty in experimental measurements.

d Absolute deviation defined by eq (2).

e Average deviation defined by eq (1).

' Standard deviation defined by eq (3).

8
Table 1.2. Residual specific volume of dew point gas for propane

Temperature Reference

volume b

Residual volume a

, liters/kg

Dana [4] Sage [5] Reamer

[6]

Helgeson Smooth c

K

255.4 156.7 12.4 12.4 260.9 137.7 4.0 4.0 266.5 120.3 -1.7 -1.7

272.0 104.5 -4.6 -4.6

277.6 90.1 -5.4 -6.5 -5.4

283.2 77.3 -4.0 -5.3 -4.9

288.7 66.0 -3.4 -3.6 -3.6

293.9 56.7 -2.9 -2.3

294.3 56.1 -1.8 -2.3 -2.3

299.8 47.6 -1.2 -1.2 -1.1

301.1 45.8 -1.5 -0.9

305.4 40.3 -0.1 -0.2 -.1

307.5 37.8 -0.2 .1 310.9 34.2 .7 0.7 .5 .5 313.3 31.9 .5 .8

313.5 31.7 .7 .8 316.5 29.1 1.1 .7 1.0 318.6 27.5 .8 1.2 322.0 25.0 1.6 1.2 1.3 323.4 24.2 1.2 1.3

324.5 23.5 1.9 1.3 327.6 21.7 1.3 1.3 1.3 327.9 21.5 1.5 1.3 332.0 19.6 1.0 1.1 332.1 19.5 1.1 1.1

333.2 19.1 1.0 1.0 336.1 17.9 0.8 0.8 338.7 17.0 0.4 .5 339.6 16.6 0.4 .4 339.9 16.5 .5 .4

343.5 15.4 .1 -.1

344.3 15.1 -.3 -.3 -.2

346.4 14.5 -.4 -.4

346.9 14.3 -.2 -.5

349.8 13.5 -.7 -.8

350.1 13.4 -.6 -.8

352.7 12.6 -.9 -.9

353.1 12.5 -.8 -.9

355.4 11.8 -1.0 -1.0

355.9 11.6 -.9 -1.0

372-701 0 - 70 -3 9
Table 1.2. Residual specific volume of dew point gas for propane— Continued

Temperature Reference

volume b

Residual volume a liters/ kg

Dana [4] Sage [5] Reamer

[6]

Helgeson

[7]

Smooth c

K

358.3 10.8 -1.0 -1.0

358.6 10.6 — 0.8 -1.0

360.9 9.8 -1.1 -0.9 -0.8

361.3 9.6 -.7 - 8

363.6 8.6 -0.5 -.4

363.8 8.6 -.5 -.4

366.3 7.4 -.1 .0 368.4 6.3 .3 4

368.8 6.0 .6 .6 370.0 5.3 -.8 .8

a Residual specific volume defined by Fg,— Vr

. b Reference volume expressed in liters/kg and defined by eq (4).

c Critically chosen values of residual volume.

Table 1.3. Deviations of several sets of experimental data for

specific volume of dew point gas for propane

Deviation

Reference

Dana

[4]

Sage

[5]

Reamer

[6]

Helge- son [7]

Liters/ Liters/ Liters/ Liters/ kg kg kg kg

Absolute a 0.18 0.20 0.11 0.16

Algebraic b -.07 .02 .07 .08 Standard c .31 .27 .20 .32 Number of Points 13 20 14 16

a Absolute deviation defined by eq (2). b Average deviation defined by eq (1).

c Standard error of estimate defined by eq (3).

10
Table 1.4. Experimental values of vapor pressure for propane

Temperature

K

Reference

pressure, equation

(1.7)

Dana [4] Sage [5] Reamer [6] Helgeson [7]

Vapor

pressure

Residual

pressure

b Vapor

pressure

Residual

pressure b Vaporpressure

Residual

pressure b Vaporpressure

Residual

pressure b

255 4 2 604 2.599 -0.005

260 9 3 150 3.130 -.020

266 5 3 779 3.776 -.003

272 0 4 501 4.511 .010

277 6 5 323 5.308 -.015 5.376 0.053

283 2 6 254 6.247 -.007 6.314 .061 288 7 7.302 7.288 -.014 7.335 .033

293 9 8 403 8.506 0.103

294 3 8.477 8.438 -.039 8.506 .029

299 8 9 786 9.717 -.069 9.805 .019

301 1 10.107 10.207 .100

305 4 11.239 11.160 -.079 11.248 .009

307 5 11.830 11.908 .078

310.9 12.843 12.724 -.119 12.840 -0.003 12.840 -.003

313.3 13.582 13.609 .027

313 5 13.634 13.609 -.025

316.5 14.608 14.426 -.182 14.596 -.012

318.6 15.322 15.310 -.012

322.0 16.542 16.331 -.211 16.515 -.026

323.4 17.032 17.011 -.022

324.5 17.448 17.011 -.047

327.6 18.652 18.610 -.042 18.610 -.042

327.9 18.785 18.713 -.072

332.0 20.474 20.414 -.060

332.1 20.498 20.414 -.084

333.2 20.949 20.910 -.039

336.1 22.243 22.115 -.128

338.7 23.438 23.408 -.030

339.6 23.854 23.816 -.038

339.9 23.986 23.816 -.170

343.5 25.739 25.517 -.222

344.3 26.128 26.116 -.012 26.116 -.012

346.4 27.234 27.218 -.016

346.9 27.493 27.218 -.275

349.8 29.027 29.049 .021

350.1 29.178 28.919 -.259

352.7 30.619 30.621 .002

353.1 30.838 30.621 -.217

355.4 32.142 32.226 .084

355.9 32.433 32.322 -.111

358.3 33.849 34.023 .174

358.6 34.050 34.023 -.027

11
Table 1.4. Experimental values of vapor pressure for propane a — Continued

Temperature

K

Reference

pressure,

equation

(1.7)

Dana [4] Sage [5] Reamer [6] Helgeson [7]

Vapor

pressure

Residual

pressure b Vaporpressure

Residual

pressure b Vaporpressure

Residual

pressure b Vapor

pressure

Residual

pressure b

360.9

361.3

363.6

363.8

366.3

368.4

368.8

370.0

35.479

35.686

37.162

37.269

38.898

40.311

40.576

41.413

35.710 .231 35.710 .231 35.724 .038

37.425 .263

37.425

39.126

.156

.228

40.827 .516

40.827 .251 42.011 .598

Estimated uncertainty,

percent 1.0 0.2 0.2 0.2

3 Pressures expressed in atmospheres.

b Residual pressure calculated from eq (8).

Table 1.5. Deviations in experimental values of vapor pressure for propane

Deviation a Reference

Dana

[4]

Sage

[5]

Reamer

[6]

Helge- son [7 ]

atm atm atm atm

Absolute b 0.059 0.129 0.173 0.044

Algebraic c -0.058 -0.031 0.082 0.024

Standard d 0.094 0.173 0.166 0.071

Number of Points 13 20 14 16

3 Deviations between experimental and predicted values.

b Absolute deviation defined by eq (2).

c Average deviation defined by eq (1). d Standard error of estimate defined by eq (3).

12
2. The fi-Pentane System

The vapor pressure of re-pentane has been studied

by numerous investigators [8-13] and the critical

properties have been measured many times [8, 9,

12, 14, 15]. The older data suffer from limitations as to the purity of the samples of re-pentane employed. For this reason, primary emphasis has been

given to the latter measurements which have employed markedly purer materials than those available prior to 1945. Table 1 reports critical properties

of re-pentane as measured by several investigators.

The critically chosen values are recorded in the

lower part of the table along with estimated measures of uncertainty.

For the most part, the critically chosen values

follow closely those selected by the American

Petroleum Institute Project 44 [16]. It was thought

that Project 44 had an opportunity to review the

critical properties in somewhat greater detail than was done in the present instance. The rather large

estimated uncertainty in the critical temperature

resulted from the significant variation in the critical

temperature reported by Beattie [12] and Ambrose

[14]. Likewise, the critical pressure selected by

the American Petroleum Institute Project 44 was

significantly different from that established from

the experimental work of Beattie. For this reason an uncertainty of 0.2 atm was selected. Rather

close agreement in the critical volume as established

by Beattie [12] from direct volumetric measurement

and that selected by the American Petroleum

Institute Project 44 [16] resulted in a somewhat

smaller estimate of uncertainty than otherwise

would haive been the case. Following the graphical techniques that have

been described in the introduction to this compilation, the vapor pressure interpolated from the

experimental measurements [11-13, 16] is reported

in a portion of table 2.2 at 10 degree K. intervals.

The residual vapor pressure of re-pentane is shown

in figure 2.1. In this instance the reference vapor

pressure was established from:

log„Pr = 5.587347-

24^3 ' 45

(2.1)

The marked difference in the measurements of

Young [9] from those of the other investigators are

clearly indicated. Other measurements of Sage

[10, 11], Li [13], and Beattie [12] are in rather

good agreement. The average fractional deviation

and the standard deviation of each set of the ex- perimental data from the critically chosen values

are set forth for the vapor pressure of re-pentane in

the upper part of table 2.3. It is most likely that the

measurements of Beattie [12] and Li [13] represent

the most accurate measurements. However, the

paucity of experimental points made it necessary

to place some reliance upon the measurements of

Sage [11]. Young’s measurements were not given

much credence because of their large deviations

from the significant body of more recent experimental data which has accumulated. Again, the

current critically chosen data follow closely those

recommended by American Petroleum Institute

Project 44 [16]

.

Values of the specific volume of the saturated or bubble-point liquid and the saturated or dewpoint

gas also have been recorded in a part of table 2.2. These latter data were interpolated from selected

measurements [11-13],

Figure 2.2 depicts the bubble-point volume as a function of temperature and presents the data of

Li [13], Sage [10, 11], and Young [9]. The data

shown in figure 2.2 were based upon direct measure- ments of the volume in the condensed liquid extra- polated to the vapor pressure. In this instance, it was not necessary to utilize the residual techniques

as the variation in the specific or molal volume with

pressure was sufficiently small that direct graphical

operations were satisfactory. The agreement of the

several sets of data for the volume of the bubblepoint liquid in comparison with the critically chosen

values are set forth in the lower part of table 2.3. Values of the vapor pressure and the specific

volume of the saturated liquid, together with application of the Clapeyron equation to calorimetric meas- urements of the latent heat of vaporization of re- pentane [17], were used to establish the volume

of the saturated gas at temperatures below 350 °K.

Figure 2.3 depicts the residual volume at dew

point for re-pentane as established by several

methods. The volume of the gas was smoothed in

terms of the compressibility factor which is defined

by eq (2.2):

Z^ — PVJbkT (2.2)

In this instance, residual graphical methods were deemed sufficient to permit critically chosen values

to be established without the need of analytical

techniques. The reference volume at dew point was

established from:

Vr = bkT/P (2.3)

It is apparent that the calorimetric measurements of

Kozicki, et al. [17] and the volumemetric data of

Li and Canjar [13] are in good agreement while

some of the earlier measurements by Sage and

Lacey [10, 11] yielded larger values of the residual

volume.

After a review of the information presented in

figure 2.3, primary emphasis was placed upon the

measurements of Kozicki [17] and Li [13] although

the data by Young [9] and Sage [10, 11] at the

higher temperatures, for the most part, were in good

agreement with the critically chosen values. The

agreement of the results obtained from the calorimetric measurements of Kozicki [17] with the

13
directly measured values of Li [13] Young [9]

and Sage [10, 11] yields credence to the critically

chosen values.

The standard error of estimate of the smooth data

from the experimental values is recorded in table

2.3. This includes a comparison of the agreement

of the directly-measured specific volume of the

dew-point gas with values calculated from the application of the Clapeyron equation to the available

enthalpy changes upon vaporization established

from calorimetric measurements [17].

The same information presented in tables 2.1

and 2.2 is also depicted in tables 2.4 and 2.5 in the

force-length-time system of dimensions, and the

results tabulated in engineering units. The standard

errors of estimate are equal tor the data presented

in tables 2.1 and 2.2, and 2.4 and 2.5, respectively,

but they have been repeated in the different sets of dimensions and engineering units in table 2.6

for the convenience of the user. The graphical

methods employed in interpolating these data have

been applied with different levels of agreement at various ranges of temperature, thus requiring

separate measures of uncertainty for each range.

Accuracy— There is recorded in table 2.7 the esti- mated uncertainty for the vapor pressure, temperature, and volume of the saturated gas and saturated

liquid as measured by each of the several investigators. These have been evaluated by the current

authors for each of the several investigators, while

the over-all summary of the probable uncertainty

in the results reported in tables 2.1 and 2.2 is set forth in the lower part of table 2.7. It should be

recognized that a certain element of subjective

judgment is required in arriving at values of uncertainty which have been ascribed to the several

variables. For the most part, uncertainties several

times those assigned by the original investigators

have been reported in table 2.7. The measurements of Young resulted from techniques involving confinement of the hydrocarbon in

glass over mercury. Likewise, the methods of

measurement of pressure were considered to be

somewhat less accurate than had been stated by

Young. The sample purity was relatively poor by

present day standards but Young’s [9] measure- ments on the whole represented an outstanding

contribution to the knowledge of hydrocarbons at the time the work was completed. Somewhat later

measurements by Sage [10, 11], in the light of

this review, probably suffered in the gas phase from

adsorption on the walls of the steel pressure vessel

within which the hydrocarbon was confined.

The purity of the sample was inadequate to permit

the vapor pressure to be established within the un- certainty of the pressure measurements which

accounted for the somewhat larger measure of

uncertainty indicated in table 2.7 for the vapor

pressure than was originally reported by the authors

[4]. These measurements of vapor pressure by Li

[13] and Beattie [12] are probably as good as any

reported and the sample purities were adequate to permit the estimated accuracy of vapor pressure

measurements to be of the same order as that esti- mated by the author [12]. Some difficulties from

adsorption undoubtedly influenced the volumetric

measurements by Li [13] and Beattie [12] but

these were less serious than those found by Sage

[11]. The measurements of vapor pressure by

Beattie [12] with a sample of relatively high

purity are considered of good accuracy. The

volumetric studies by Li [13] were not considered

as satisfactory as Beattie’s [12] techniques and

for that reason a larger measure of uncertainty than

that indicated by the author has been assigned.

Kozicki’s [17] calorimetric measurements offered an interesting insight into the overall reliability of

the volumetric measurements of the dew-point

gas. However, since the first derivative of the vapor

pressure with respect to temperature was required

to establish the volume of the dew-point gas, a higher

uncertainty was assigned to the derived volumetric

behavior than existed in the original calorimetric

measurements.

There are a number of correlations and reviews

of the properties of the paraffin hydrocarbons that

include n-pentane which were not utilized in the

preparation of the tabular information submitted. In

table 2.8, however, the more useful reviews are described briefly [18-27].

14
300

TEMPERATURE K

350 400 450

(/) CL

LU

CC

3

CO

CO

LU

a:

CL

oco

CL

2

<

3Q

CO

LU

cr

5

4

3

2

0

2

-3

•4

1—

6

1—

API 44

1 ~T~ ~T~ n T~

rf

o-

?

-o •

BEATT

LI

SAGE

E

j YOUNG

&

0

0

-O J \ 0

r

^

-

-u

T

j _

CRITICAL k

0.35

030

0.25

0.20

0.15

0.10

0.05

0

- 0.05

- 0.10

- 0.15

- 0.25

- 0.30

00 200

TEMPERATURE

300

Figure 2.1. Residual vapor pressure of n-pentane.

15

RESIDUAL

VAPOR

PRESSURE

atm
BUBBLE

POINT

VOLUME

ft

3/

lb

300

TEMPERATURE

350

K

400 450

4.25

4.00

3.75

3.50

3.25

3.00

2.75

2.50

2.25

2.00

1.75

1.50

FIGURE 2.2. Bubble point volume of n -pentane.

16

BUBBLE

POINT

VOLUME

liter/

kg
RESIDUAL

DEW

POINT

VOLUME

ft

3

/lb

TEMPERATURE K

300 350 400 450

FIGURE 2.3. Residual volume at dew point for n-pentane.

TABLE 2.1. Critical properties of n-pentane

Source Temperature Pressure Volume

K Atm Liters/kg Liters/kg-mol

Young [9] 470.4 33.0 4.31 310.9

Sage [11] 470.4 33.6 4.36 314.6

Beattie [12] 469.8 33.31 4.09 295

Ambrose [14] 469.5

Partington [15] 469.6

API 44 [16] 469.49 33.16 4.08 295

Critically chosen value 469.49 33.16 4.08 294.6

Estimated uncertainty 0.7 0.2 0.04 2.9

Estimated uncertainty, percent 0.1 0.5 1.0

17

372-701 0 - 70 -4

RESIDUAL

DEW

POINT

VOLUME

liter/kg
Table 2.2 Properties of the coexisting phases for n-pentane

Temperature

Vapor

pressure a Volume

Dew point Bubble point

K Atm Liters/kg Liters/kg-mol Liters/kg Liters/kg-mol

280 0.32 970.9 70.06 X 10* 1.561 112.7

290 0.49 656.1 47.34 1.586 114.4

300 0.72 421.0 30.38 1.616 116.6

310 1.03 328.4 23.70 1.641 118.4

320 1.42 241.8 17.45 1.672 120.7

330 1.93 181.1 13.07 1.706 123.0

340 2.57 138.2 9.970 1.739 125.5

350 3.38 107.1 7.728 1.774 128.0

360 4.31 83.4 6.017 1.813 130.8

370 5.45 65.92 4.756 1.855 133.8

380 6.81 52.67 3.800 1.902 137.2

390 8.41 42.31 3.053 1.952 140.8

400 10.3 33.07 2.476 2.010 145.0

410 12.4 27.74 2.001 2.073 149.6

420 14.9 22.50 1.623 2.146 154.9

430 17.7 18.19 1.312 2.232 161.1

440 20.9 14.60 1.054 2.358 170.1

450 24.5 11.57 0.8347 2.525 1&2.2

460 28.6 7.791 .5621 2.792 201.4

469.49 b 33.16 4.08 .295 4.08 295

a (Atm) (1.013250 X 105

) = A'/m2 "Critical state [16]

18
TABLE 2.3. Agreement of interpolated and experimental data for n-pentane

Source Number of Average a Deviation Standard c

of points Fraction b

Vapor pressure, atm

Young [9] 24 -0.164 0.0102 0.248

Sage [11] 22 -.010 .0044 .019

Beattie [12] 4 .005 .0003 .010

Li [13] 2 .001 .0008

API 44 [16] 10 -.001 .0018 .003

Overall d 38 -.005 .0031 .015

Dew-point volume, liters/kg

Young e [9] .. 21 -0.27 0.0050 0.62

Sage [11] 23 .23 .0077 1.21 Li [13] 2 .08 .0056

Kozicki f [17] — | 11 -.42 .0024 0.97

Overall 57 -.08 .0056 .93

Bubble-point volume, liters/kg

Young e [9] 21 -0.0303 0.0124 0.002

Sage [11] 23 .00071 .0008 .062

Li [13] 2 -.0687 .0030

Overall 46 .0164 .0062 .041

“Average deviation defined by ^

(Gexp — Csm

) J/A

“Average fractional deviation defined by

j ^ [ (CexD — Ggm )/Gexp]}/^V

^ I

c Standard deviation defined by

jj ^ (Gexp —C,m) 2 J/(A— 1)J

1 ' 2 where G = pressure or volume

d Excluding Young’s vapor pressure data

e Values of deviations for Young not comparable since data employed had been smoothed.

'Calorimetric data for temperatures between 311 and 350 K.

Table 2.4. Critical properties of the n-pentane system, engineering units

Source Temperature Pressure Volume

° F psia cu ft/lb cu ft/lb-mol

Young [9] 386.96 485.4 0.0690 4.98

Sage [11] 387 494 .0699 5.04

Beattie [12] 385.95 489.5 .0655 4.73

Ambrose [14] 385 41

Partington [15] 385 5

API 44 [16] ..." 385.41 487.3 .0654 4.72

Critically chosen value 385.41 487.3 0.0654 4.72

Estimated uncertainty 0.4 3.0 0.0007 0.05

Estimated uncertainty, percent 0.1 0.5 1.0

19
Table 2.5. Properties of the coexisting phases for n-pentane, engineering units

Temperature

Vapor

pressure a Volume

Dew point Bubble point

°F psia cu ft!lb cu ft/lb-mol cu ft/lb cu ft/lb-mol

40 4.30 17.2 1240 0.02491 1.797

50 5.48 13.7 986 .02510 1.811

60 6.89 11.0 795 .02532 1.827

70 8.56 8.95 646 .02556 1.846

80 10.6 6.74 487 .02580 1.862

90 12.9 6.12 441 .02612 1.885

100 15.6 5.108 378.7 .02634 1.900

110 18.6 4.325 312.1 .02662 1.921

120 22.3 3.643 262.8 .02691 1.942

130 26.4 3.104 224.0 .02719 1.962

140 31.1 2.660 191.9 .02750 1.984

150 36.4 2.280 164.5 .02779 2.005

160 42.4 1.978 142.8 .02810 2.027

170 49.0 1.716 123.8 .02842 2.051

180 56.5 1.494 107.8 .02876 2.075

190 64.8 1.306 94.23 .02912 2.101

200 73.9 1.145 82.61 .02948 2.127

210 84.0 1.008 72.73 .02987 2.155

220 95.1 0.8886 64.11 .03028 2.185

230 107.2 .7877 56.83 .03072 2.216

240 120.4 .6966 50.26 .03143 2.268

250 134.7 .6184 44.62 .03166 2.284

260 150.3 .5498 39.67 .03219 2.323

270 167.3 .4892 35.30 .03273 2.362

280 185.6 .4353 31.41 .03333 2.405

290 205.4 .3875 27.96 .03396 2.450

300 226.7 .3452 24.91 .03467 2.501

310 249.7 .3067 22.13 .03548 2.560

320 274.3 .2718 19.61 .03641 2.627

330 300.8 .2405 17.35 .03752 2.707

340 329.1 .2118 15.28 .03884 2.802

350 359.4 .1853 13.37 .04043 2.917

360 392.0 .1600 11.54 .04246 3.064

370 426.8 .1348 9.726 .04548 3.281

380 461.3 .1106 2.980 .05109 3.686

385.41 b 487.3 .0654 4.73 .0654 4.72

‘ (Psia) (6.89475 x 103

) = /V/m 2

. b Critical state [16].

20
Table 2.6. Agreement of interpolated and experimental data for n-pentane, engineering units

Source

1 !

Number Average a Deviation Standard c of points fraction b

Vapor pressure, psia

Young [9] 24 -2.41 0.0102 3.65

Sage [11] 22 -0.15 .0044 0.28

Beattie [12] 4 .07 .0003 .14 Li [13] 2 .02 .0008

API 44 [16]... 10 -.02 .0018 .04 Overall d 38 -.08 .0031 .22

Dew-point volume, cu ft/lb

Young e [9] 21 -0.0043 0.0050 0.0099

Sage [11] 23 .0037 .0077 .0194

Li [13] 2 .0014 .0056

Kozicki f [17] 11 -.0067 .0024 .0156

Overall 57 -.0014 .0056 .0149

Bubble-point volume, cu ft/lb

Young e [9] 21 -0.00048 0.0124 0.00003

Sage [11] 23 .00011 .0008 .00100

Li [13] 2 -.0011 .0030

Overall 46 .00026 .0062 .00065

a Average deviation defined by (Gexp -Gsm )j/A.

b Average fractional deviation defined by

j ^

j\cexp — Gsm )/GexpjJ/A'.

c Standard deviation defined by

| j ^ (Gexp — Gsm ) z j/(1V— 1 ) where G = pressure or volume.

“Excluding Young’s vapor pressure data. “Values of deviations for Young not comparable since data employed had been smoothed.

'Calorimetric data for temperatures between 100 and 170 °F.

Table 2.7. Accuracy of experimental background for n-pentane

Quantity Units Young [9] Sage [11] Beattie [12] Li [13] Kozicki [17] a

Sample purity mole fr 0 95 0 9970 0.9985 0.9988 0.9998b Vapor pressure percent 5 3 .2 .2 Volumetric behavior percent .5 .5 .3 .4 .5

a Includes uncertainty in dew-point volume calculated from Clapeyron equation.

b Reported by vendor. The specific weight of the liquid and the index of refraction agree closely with critically chosen values. The reported purity seems higher than would be

expected.

21
Table 2.8. Reviews of properties of the paraffin hydrocarbons

Subject Treatment Reference

Vapor pressure

Vapor pressure

Vapor pressure

Critical constants

Critical constants Vapor pressure

Thermodynamic properties

Critical constants Vapor pressure

Physical constants

Correlation. Equation of state Review and re-evaluation of experimental data

Correlation. Empirical constants

Correlation. Van der Waals constants Review of experimental data

Correlation. Semi-empirical equation

Re-evaluation of experimental data

Correlation. Van der Waals constants

Correlation. Semi-empirical equation of state.. Correlation. Statistical theory of liquids

[18]

[ 19 ]

[ 20 ]

[ 21 ]

[ 22 ]

[ 23 ]

[ 24]

[ 25 ]

[ 26 ]

[ 27 ]

3. The Methane- n-Pentane System

The methane-n-pentane system has been subject

to significant experimental study at temperatures

above ambient. However, only a limited investigation is available for temperatures below 37.7 °C

[28],

The vapor pressure of methane has been studied

extensively [16, 29-32], and the critical state of

the hydrocarbon measured [16, 29, 33, 34]. Likewise, the vapor pressure of n-pentane was studied

by Young and others [8, 9, 12, 13], and the critical

properties determined [9, 12, 14, 16].

The phase behavior and the volumetric characteristics of the coexisting phases in the methanen-pentane system have been established [35-38].

A comparison of the phase behavior of several

hydrocarbon systems containing methane, with

particular emphasis on the critical states, also has

been presented [39]. In addition, a review was

made of the phase equilibria data for the methanen-pentane system, and of similar data for other

binary systems [40]. No new experimental data were included in either of the above reviews.

Utilizing the graphical techniques which have

been described in the introduction to this compilation, the aforementioned experimental data were smoothed with respect to pressure and temperature.

The composition and the specific volume of the co- existing phases also were interpolated as a function

of pressure and temperature. In table 3.1 are re- corded the composition, molal volumes, specific

volumes, and molal equilibrium ratios of the

coexisting phases for mixtures of methane and

n-pentane. The data are reported at temperatures

from 280 to 470 K. for pressures from the vapor

pressure of n-pentane to a maximum of 170 atmospheres. The data have been recorded for even values

of pressure expressed in atmospheres for each 10 K.

temperature interval. The standard error of estimate

of the smooth curves employed for interpolating

these data from the experimental results are set forth in table 3.2. The characteristics of the unique

states, including the critical state, the point of maximum temperature, and the maximum pressure for

mixtures of constant composition, aie listed in

table 3.3. These values of pressure and temperature

for each of the three unique states, as well as a rough estimate of the specific volume for the

critical state, are reported as a function of weight

fraction methane. The data recorded in table 3.3 were obtained by suitable graphical operations

based upon experimental volumetric and phase

equilibrium data. The estimated uncertainties for

each property have been included in the tabulation.

Since many persons having an occasion to utilize

this information are concerned with the forcelength-time system of dimensions, the above described data expressed in these dimensions are reported in conventional engineering units in tables

3.4 and 3.5. The composition and the specific

volume of the coexisting phases in the methanen-pentane system are reported in table 3.4, and the

properties of the unique states in table 3.5. The standard error of estimate of the smooth

curves used in the evaluation of these quantities

is identical with that reported in table 3.2. However, for the sake of completeness, it has been

presented in table 3.6 and expressed in the units

used in tables 3.4 and 3.5. In preparing the tabulations shown in tables 3.1 to 3.2, an effort has been

made to present the data in sufficient detail to permit

the use of four-point linear interpolation in order

to evaluate properties at any chosen temperature,

and pressure or composition with a precision at least equal to the accuracy of the data.

In order to illustrate the nature of the phase

behavior of this system, a pressure-temperature

diagram showing dew points and bubble points

for three mixtures of constant composition and the

vapor pressure of n-pentane is shown in figure 3.1. In figure 3.1 the effect of temperature upon the

critical state of the methane-n-pentane system

has also been shown. Since it was, from necessity,

estimated from the observed volumetric behavior

at states near the critical state, the data have been

indicated as an estimated quantity. The critical state

for a binary mixture can be considered to be that

22
state at which the properties of the coexisting phases

become continuously identical. For example, the

critical state can be approached by an increase in

temperature under isobaric conditions or by an

increase in pressure under isothermal conditions

or by any chosen polytropic path. In addition, the

estimated maximum pressure at which two phases

exist for a given temperature has been indicated.

This state often differs materially from the critical state for a mixture of the same composition, as is indicated for a mixture containing 0.50 mole fraction methane. However, this state has been called

“maxcondenbar” as being the maximum condensation pressure for a given mixture. It should be

recognized that the maxcondenbar becomes equa

to the critical pressure at the maximum two-phase

pressure for the system as a whole. The maximum

two-phase temperature for a mixture of a given

composition also has been shown and has been entitled the “maxcondentherm.” It is again emphasized that the loci of the maxcondenbar and the

maxcondentherm as well as the critical represent

estimated quantities established from measured

volumetric and phase behavior and not from direct

observation of these quantities.

In figure 3.2 is depicted the equilibrium ratio as a function of pressure for each of several temperatures. The product of the pressure and the equilibrium ratio was employed in figure 3.2 to permit the

data to be presented with greater precision.

The molal equilibrium ratio, K, is detined in the

nomenclature and represents the ratio of the mole

fraction of a given component in the gas phase to that in the coexisting liquid phase at the same

temperature and pressure. This quantity is often

employed to represent the phase behavior of the

system since the ratio can often be effectively

employed in phase equilibrium calculations to greater advantage than values of the compositions

of the coexisting phases.

It should be recognized that the equilibrium ratio

always is unity at the critical state, Thus in the case

of figure 3.2 the critical locus is identified by a line

crossing the diagram in such a fashion that the

product of the pressure and the equilibrium ratio

and the pressure are everywhere equal. It also

should be recognized that the equilibrium ratio

for the less volatile component becomes equal to unity when the pressure is equal to the vapor pres- sure of that component. The lower pressure

boundary of the heterogeneous region is thus

established by the vapor pressure of the less volatile

component.

The effect of pressure upon the composition of the

coexisting phases and upon the critical state has

been shown in figure 3.3. The curves shown in this

figure represent the phase behavior for a particular

temperature as the pressure is changed. The critical state in this instance represents the highest pressure

at which two phases may coexist for a given temperature. Such behavior can also be seen in figure

3.1. However, it must be recognized that in cases

of mixtures of a given composition the critical state

is neither the highest pressure nor the highest

temperature at which two phases can coexist

throughout most of the pressures and temperatures

where heterogeneous equilibrium exists. The esti- mated locus of maxcondenbar and maxcondentherm

have also been indicated in figure 3.3, and for a given

temperature represents the dew point gas, in this

instance, containing the largest mole fraction of

methane. Figures 3.4, 3.5, and 3.6 show the same

information in terms of the force-length-time system

of dimensions expressed in engineering units.

Accuracy — For those interested in the critical

evaluation of the experimental accuracy underlying

the information presented in tables 3.1 to 3.5, a

critical review of the uncertainties associated with

the measurements of the several investigators has

been made and is set forth in table 3.7. In any such

evaluation it is difficult to maintain objectivity. However, it is believed that the values of uncertainty

presented in table 3.7 have been arrived at by

conservative judgment and formal statistical

procedures, such as described in the introduction.

The uncertainties assigned to each of the variables

by the current authors are from two to four times

that reported by the original investigators.

It should be recognized that the majority of the

values reported in table 3.7 do not apply to the

behavior in the vicinity of the critical state where

the uncertainties may be many times as great, since

these states were not established by direct experimental observation. There is need for additional

experimental work involving the determination of

the critical state by visual observation and by

indirect measurements of the intensive properties

of the coexisting phases, in order to permit an

objective appraisal of the accuracy with which the

properties of the system near the critical state have

been established.

23
PRESSURE

atm

275 300 325 3 50 375 400 425 4 50 475

TEMPERATURE K

Figure 3.1. Pressure-temperature diagram for methane-n-pentane system.

24
PRESSURE

•

EQU I

LI

BRI

UM

RATIO

PRODUCT

atm

FIGURE 3.2. Effect of pressure upon equilibrium ratio for methane-n -pentane system.

372-701 0 - 70-5

25
PRESSURE

atm

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

MOLE FRACTION METHANE

FIGURE 3.3. Pressure-composition diagram for methane-n-pentane system.

26
PRESSURE

psiQ

Figure 3.4. Pressure-temperature diagram for methane-n-pentane system, engineering units.

27
PRESSURE-EQUILIBRIUM

RATIO

PRODUCT

FIGURE 3.5. Effect of pressure upon equilibirum ratio for methane-n-pentane system, engineering units.

28
PRESSURE

psia

0.1 0.2 03 0.4 0.5 0.6 0-7 0-8 0.9

MOLE FRACTION METHANE

FIGURE 3. 6. Pressure composition diagram for methane-n-pentane system, engineering units.

372-701 0 - 70 -6 29
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-<= CL. 2 1 t- z

«s

oc

GO

CM <M (Si CM CM (Si H H h pH o o o o o o o o o o o O O o o o o o O o o o o o o o o o O o o o 5

UJ o o o O O o o o o o o o O o o o o o o o o o o o o o o o O o o o o o O o o o o o o o o o o o o o

O' < LU UJ LU UJ LU LU UJ LU LU LU LU LU LU UJ UJ UJ LU UJ UJ UJ UJ UJ LU UJ UJ UJ UJ LU UJ UJ LU UJ UJ LU LU UJ UJ LU LU LU LU UJ UJ LU UJ LU UJ UJ

GO >0 O' O' CO O' GO o CM o 4

- 4

- GO O' 4

- 4

- in r- f4 in CO GO GO 4

- cn in o o >* m cn 4

- x GO 4- CO CM in O' cn >0 o <*- in o

LU O' •c O' in m O' 00 o o o o rn o cn 4

- ao GO o >* o o cn f4 O' h- o 4

- m CM o O' GO GO r- >0 x in 4- cn cn CVJ f4 o Z X CM H pH O' X 00 4 eg CM *H pH H O' ao o in n 4

- 4

- cn cn on CM CVJ cm CVJ 'N CM CM CM f4 H H pH H fH f4 rH

DC

0.

OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I ill in in iii hi iii i

| i iii iii ui ill in iii in in hi l 1 1 ill m in i.i iii m mi m in m ill m ill m in m m m in in hi m in tit in m iji omoo®f'-o4oaooomh'-*r— o®or-<\im®ir\®0'mof— .o<N4or— ®.or->or--Ln'Of,,'co4-r\j.JO

0>

>0 if» 4 mm<\l<\l<\|.-if«..©ir\ 44444 mmmmmri,>mmmrei 44444 K>in'0 f

,-® 0'-*>^«*^<\i<\im 4 -*

oo

o o 0 0 000000000 O 0 O O 0 O 0 0 0 0 OOO 0 0 0 O 0 O 0 0 0 c 0 O O O O O O O 0 0 0

LU LU UJ UJ uj 111 in in m .11 111 ui 111 LU LU LU UJ LU UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UI UJ UJ UJ UJ UJ UJ UJ LU LU UJ LU UI UJ UJ UJ UI UI

>0 >0 vO 0 '0 ^>0'0 ONNSCO O' O' O 0 H CM 4* m 00 0 ^ cn n >0 X 0 CM 4

- 0 O' H 4* 0 O m h- pH h- >* CM 4 n- 4 o in n n n nnnnnnnnn n n ~o •£> n0 4> -

0

>0 <0 r-F r^* r- X X X X X O' O' O' O 0 0 H pH CM m 4 n X H pH pH Hf4^f4HHHf4H pH *H pH H F^ f4 pH H H H pH H H »H H H H H f4 pH H CM M CM CM <M CM CM CM CM CM o o 6 6 oddddddoo O O O O 0 6 6 0 d O 066 O O O O d 0 0 d d d d O O 0 0 O O O O O O

cn cn in X m m cn m in rn m m cm CM CM CM CM CM CM CM CM CM <M CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM o o 0 0 000000000 0000 0 0 OOO O OOO O O O O O O O O OOO O O O O O O 0 OOO

_J

LU UJ UJ LU 111 111 111 111 111 111 i n m m UJ UJ UJ UJ UJ LU UJ UI UJ LU UJ UI UJ LU UJ UJ LU UJ LU UI LU UJ UI LU LU LU UI LU UJ JJ LU UJ UJ UJ

cn cn in CM CMCMCMCVJM^HOO' 00 GO n* 0 O 4

- cn h ao 4

- H S sO 4- CM pH O O' X h- X O' O cn >0 O' cm n- 4 r*- r- 4

o H iH pH pH f4 H H H f4 H f4 O 0 0 OOO O 0 0 O' ao in 4

- m CM H O X r- •0 n 4 m (\4 CM O O' O' X X X X O' z fH pH f4 f4 ^ f4 p4 f4 H f4 f4 fj H pH f4 f4 ^ f4 O' O' O' O' O' O' O' O' O' X X X X X X X X X X N h- r*- r- r- o

GO o 066000060666 0 O 6 6 6 0 d d d 0 066 0 O 0 0 0 0 0 0 OOO 0 0 0 0 O O 0 0 0 0

CM O O fh »h HH(M(MMlT\CDHfO O O' CM n ao in cn 0 x >0 m fh 0 O' X r*- x O' ^ cn 0 0 4 0 O H >

0

0 H CM cn o o o O OOOOOOO^^ pH fH CM CM IMff|4’UMfl >0 r- ao O' 0 O fH cm 4 n >o n- O' 0 pH cn 4* >0 X 0 CM n X n X n- o 0000000000000 O 0 0 0 0 OOO O OOO fH H pH *H pH pH pH pH fH rg CM CM CM <M CM m X m cn n in

LU • o 6 OOOOOOOOOOOO O O O O 0 0000 OOO O O O O O O n O OOO O OOO O 0 O 6 6 OOO z o c UJo

» o pH CM 4

- lA'ONcOON^'OCO O' pH CM m 4

- f4 H in CO H m 4^ n >0 vO >0 n0 ^iAin 4 cn CM cn X 0 n pH pH n- CM X

LU 00000000-<<\im4U1 >0 ao O' 0 fH 4

- >0 ^ <0 ao fh cn n h- O' pH cn n O' pH cn n h* O' H cn >0 X H >fr X >0 n

X o o o O OOOOOOOOO 0 O O H H f4 f-C CM CM CM cm CO cn CO cn m 4

- 4 4 4 4 n n n n n O v0 >0 >0 r- X X

1-< o O 0 6 0000066660 d d O O O 0 d O O OOOOO 0 0 0 O 0 0 0 0 0 0 0 0 O 0 0 0 O 0 0 O 0

UJa cn <n in cn cncnincninininincn CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM cm CM CM CM H H pH pH pH pH pH iH pH pH H H

•Oo

X o 0 0 0 0000000000 OOO O O 0 0 O O OOO 0 O 0 O 0 O O 0 0 O O O O O O O 0 0 O O O

UJ UJ UJ UJ m 111 uj 111 uj ip ui in 111 UJ UJ UJ uU UJ UJ UJ UJ LU LU UJ LU UJ UJ UI UJ LU UJ LU UJ UJ LU UJ UJ UJ UJ LU UJ LU UJ LU UJ UJ UJ E3

cn O CM i^N'O'tO'O'OiC® n O CM 00 CM pH O' O n O' H N CO fH ^ fC\ 4- n 0 O' X CM X n- O 'O 4 n >0 n- 4 n cn 4- r- (Mcom^o^co^H O' n n >0 O ao O' 4- n mo® r- n m CM «H 0 0 cn n- cm NO pH n- CM X 0 >0 CM X

05

ao >0 n U14444IM— O' 00 r*- >0 "0 m <n CM CM CM CM H F^ pH pH pH #H H •H H O' X X n- >0 >0 n n n 4 >* X

o 0 0 0 OOOOOOOOO 0 d d 0 0 0 OOO 0 600 O O O O O 0 O O 0 000 0 0 0 d 0 0 OOO

n n n n nnnnn-^'t^^ 4- 4- >1

* 4- m m m m cn m CO m cn cn CO cn cn m cn cn m cn cn x m CM CM CM CM o o o o OOOOOOOOO O O O OOO 0 0 0 0 OOO 0 0 0 0 0 0 0 0 0 OOO O 0 O OOO OOO

LU LU UJ LU 111 111 UJ in ui ui 111 1 U 111 UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ LU UJ UJ UJ UJ UJ UJ c cn >0 ®NH>ofCi>tinofn n h- pH O' ao >o r*- 0 m m h N X cn CM m >0 CM X >0 nO n- O' pH 4 pH n n 0 n

>0 GO CM S.D 4, M-lOh®fsj ao n m CM 0 n O O' F^ n O ® (M O' n m —a 0 x r*F v0 n cn cn CM H pH 0 0 4 X CM z n cn cm 'M «tH«iHFJinrc\(Mi\j pH pH H pH pH GO n n >* cn m CM M CM CM CM CM F^ pH pH «H‘ pH H pH pH H pH pH 0 O X X o 0 0 O OOOOOOOOO 0 0 0 OOO 0 0 0 0 OOO 0 0 O 0 O O 0 d OQOO O O O O O 0 0 d O

44 m'0 '0 '00>O 4 ®O®'0 ifiir\tfl-*®fsiFC0 mmp-®®®®P>-'0 ir\mO'0 F 4 ®in(Sja' 4 ®OOP'O'*<\J ®

o-*»-t(\i<Mmm 44 'Oi^fs-®«®®®®®®®®®®®«®®®®«®®®®®®®®®®r-p>-r>-r'-p~.oir' ®

• ••••••••••••••••••••••••••••••••••••••••••••••a • oooooooooooooooooooooooooooooooooooooooooooo'oooo o

OF-F.^mir\m®f\ii\i«mo'if\®'-«mir\®.-*m4mininir\ininifim44mf\i.-iO'r'-40'Of'gf'--<mp~p>-(\j<\j ui 0 '00 ® 40'mm® 0'(\j 44 Uiui'043 ,o.oh-r~r-h.f«-r»r“f>-r-r>-r^p>-F.r^F-p».0 '0 '0 '04iui 44 m<sj>'* 0'0 r~ «Hfninin ,0'Or-'*h»^XOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOX CT' • •••••••••••••••••••••••••••••••••••••••••••••a* • oo'oooooooooooooooooooooooooooooooooooooooooooooo O

• V) *0 4>0®0<N4<0®0000000000000000000000000000000000000000'0>®

OOO^-*^rfHN't<«ON'}, '0 ®Oi/'Oil'OiflOK'OK'OK'OinO^O^OU,'OlflOlflOK'O^Oi/'«®i/'

30

See

footnotes

at

the

end

of

this

table
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

H H H H H H H pH pH H rgrgrgrgrgpgrgrgrgnjrgrgrgrgrgrgpgrgpg rg rg rg cm rg rg rg rg ph pH pH pH pH pH pH pH pH O z ooooooooooooooooooooooooo O 000000 9 9 OOOOOOOOOOOOO

h- III 111 111 L1 J UJ LU UJ LU UJ LU LU UJ UJ ijj UJ UJ LU LU ill UJ UJ UJ LU UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ LU UJ UJ LU UJ LU UJ UJ UJ LU LU UJ z or\jooop> 4 oinp-p- NOMf*3 «OmoOOH 0 0 4- m in 0 45 rg O' m C30N 4 ro X pg •p in pi in rg O' OO PPI 4 O

a! O^^O’tO'Ul^iAO'ON^ 4- O ©inosinggg in 45 00 O' -- <M m X rg X rg O' f- x HN 4 43 S' CM m 0 0

o 1 h- Z

•«*

CSL

O' r*- in in 4 rO W h h co r- >0 -0 6 m in in 4- 4- 4- 4- 4- 4> 4- 4- 4- in in in in 45 4) r- r- X O' pH pH pH pH H CM rg CO in pH

or

CD

rg eg cm cm rg N »H H H H »h fj pH pH pH 0 0 0 O O O O O O O O O 0 0 0 0 O O 0 0 0 0 O 0 O 0 0 O O O 0 O — LU = z

o o o o o 00000 0 0 O 0 0 0 0 0 O O O O O O O O O 0 0 0 0 O O 0 0 0 0 O O O 0 0 O 0 O 0 O

O' 11,1 111 liJ ill LU LU UJ UJ UJ LU UJ LU UJ UJ LU UJ UJ UJ UJ LU LU UJ UJ LU UJ LU LU LU UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ UJ UJ UJ LU LU UJ UJ ^ pH pH ^ ^ pH 45 7* in in m m co in in 0 r- r- 00 r- 4) h- O CM H in m in 00 4- pH O' O' 0 0 CM in h- 0 4 r- 0 4 0 CO 4 0

UJ oo -« >0 4 rg O m g- rg oo *-4 h- 4 rg -h r- 00 pH 0 CM 4) rg oo in rg 0 00 43 m 4- rg pH 0 0 0 X h- r- X in in 4 CO CO CM ^H 0

3E rg <NJ •—

1

r-t h O' ® g oj rg p-4 H H pH d 00 r- 0 m 4- d ro m ro m CM pg rg rg rg CM CM rg pH pH pH H pH ^H pH pH pH pH pH ^H

H H rH H H H H pH ^4 H pH H pH pH pH p-4 pH •H pH pH ^H *H pH pH H pH pH H H pH pH pH pH pH ^H pH pH pH pH *H pH pH pH

T3 o o o o o 0 0 0 0 0 0 0 O O O O O 0 O O O O O O O O 0 0 0 O O 0 O O O O O 0 O O O O O O O O

O LU LU LU LU LU III 111 ill 111 HI UJ UJ UJ LU LU UJ UJ UJ LU UJ UJ UJ LU UJ UJ UJ UJ LU LU UJ LU UJ UJ LU UJ LU UJ LU LU LU UJ UJ UJ LU LU UJ

(jh ^ o O' S' O O O 0 O p-H rg rg co ro m >0 GO O' ph rg 4- in r- O' *H m in r- O' H 4 O CO ^H CO pg 0 O' rg X 4 o in in m in in in in in in x -0 43 4) 4) >

0

>0 >0 4> 4) 45 4) r- r- r- r- ao 00 ao X O' 0 O' O 0 0 pH pH rg co <0 in 43 O'

ft

LU

SE

H »H H H H f4 pH H ^4 H ^h H pH i»4 ^4 ^H pH pH <H *H ^H pH •H •H H pH H pH pH •H pH pH pg CM CM rg eg rg rg rg rg pg CM ooooooooooooo 0 0 6 0 6 O O O 0 0 0000 0 0 O O O O O O 0 0 0 6 6 0 0 6 0 0 O

_J5 ro co co ro m co co co co co <0 co co to to co co co fp> m m m cm rg INI IM (M CM cm cm cm rg rg rg rg rg pg PNJ cm rg rg cm rg rg PM CM o o o o o 00000 00000000 OOO 000000 0 0 0 0 O 0 0 O 0 0 0 O 0000000

h- o

—1 111 HI 111 UJ 111 111 111 III LU III UJ UJ UJ LU UJ UJ LU Ui UJ LU LU UJ UJ UJ UJ LU LU UJ LU LU UJ UJ UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ 44444444 fr'<n rg -1 -- O O' O' oo >o in 4* CM pH CO in ro -4 O O' 00 r- >0 4) X r— X O' *H 4 X 0 X H ^ cm m X O o ^ H H H H H H ^ H H —

1

pH O O O O 0 0 0 0 O' 00 45 in CO rg -- 0 O' X f*- 4) m m 4 co rg rg rg pH CM CM (O s H »H <H pH c=) ^4 -J «=J H H ^4 pH o=3 pH pH pH H pH pH pH O' O' O' O' O' O' O' O' O' X X X X X X X X X X X X X X X

_JCD

CDO

o

O' odd o 6 d 0 d 0 d 606666006 O O d O O 06606006 0 0 0 0 d d d dodo 0 6 6

CM o o O pH *h •h rg pnj g f*- O rg m oo 0 cO X co O in cm 0 GO >0 0 O O IM Cl X O' 4 O S' -> r- 43 CO X pH OOOOOOOOOO---- H ** (M rg rg co 4

- 4

" in 4) h» co O' 0 pH <m ro m 4^ X r- X O' O pH CO in X O' *H 4 X CO 4 INI *: o o o o o OOOOOOOOOO 0000 O O 00000---- »H H pH pH H pH pH rg pg pg pg rg rg CO ro ro 4 in in ^ UJ • 6 o o o o 0000000 000 006 d 0 0 0 0 d 000 0 d OOO 0 O O O OOOOOOOOOO 0 0

«< OJo

. UJ •» o CM rO m >0 r- cd 0 —4 m 4- in in x r- r- m 00 CO h- O m m r- O' 0 •H •H pH •H pH pH O O O' X X X 0 4 O' X 4 X 4 0

LU oooooooo<M<,i 4 in 43 h- GO 0 0 m m 00 0 m in O' pH 4

* 45 00 O rg 4- X X O CO m r*- 0 <m 4 r~ 0 co r- 4 CO

—1 QC o o o o o 00000 0 0 0 OO O pH p^ «H H CM rg rg rg rg m cn m m 4- 4

- 4- 4

- 4 in m m in in X X X X r- r- X X

o

z fr— < o o o o d 0 0 0 d d 0 0 0 d d 0 d 0 0 O O OOO O 0 06000 O d 0 O 0 0 0 00060 0 0 0 0 0

UJ

Q. co co en to co co co m <o co to co rg PM rg rg rg rg CM rg CM rg rg rg rg CM pg CM rg rg rg CM CM pH pH pH pH pH pH pH pH pH pH pH pH o z o o o o o 00000000 O O OOO O O O OOO O O 0 0 O 0 C O 0 0 O O O O O O OOO O 0 O

i— UJ UJ UJ UJ LU Uj UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ uj UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ LU LU LU UJ UJ UJ UJ UJ LU UJ LU UJ UJ UJ UJ LU UJ UJ O

g* o in -c co iyi g 4) 4) n 0 g H H f4 -4 co »H pH m 00 m 4

* pH ^H 4* 0 h- r- X O ro 4 in pH pH CO O' X x X O O' O' co (\J N ro o CD 43 g N 4

* 4- 4- 'C O' 00 O 4

- & 4) m pH O' r*» 4) 4* m rg pH pH O X 0 4 O' 4 0 4 O 43 rg O' 4 O' Q- to to <0 eg -h H O' 00 r- 4) in 4

- 4- m CM rg rg rg pH H pH H pH ^4 pH pH O' O' X h- h- X 43 x m in 4 4 CO

LUs

o o o d o d 0 d 0 0 d 0 O 0 d d 0 OOO O O O d 0 O O O O O O O O 0 0 d d O O O 0 0 0 O O O

_J§ in in in m in m m in 4 4 4

- 4 4 4 4- 4- m cn m ro m CO rT) m rr\ ro m m m m to CO ro <0 <0 CO CO ro CO CO 10 CO rg CM o o o o o 0000000 OOO O O 0 0 0 0 0 0 0 O 0 0 0 0 0 0 0 0 0 O 0 0 O 0 OOOO O O O

_l UJ UJ UJ LU UJ LU UJ LU UJ LU LU UJ UJ UJ LU UJ LU UJ UJ UJ UJ UJ UJ UJ UJ LU UJ UJ UJ UJ UJ UJ LU UJ UJ UJ LU UJ LU UJ UJ LU UJ UJ UJ UJ <c co h n g so m O' 0 cm p- O' O pH co rg in rg O' m pH r- pg 0 pH pH 4) 4

- 4- CM X X n n X r* O' rg in 33 rg r- pH in pH —

1

co O' m o no g p*g co 00 00 cO O' 43 4

- rg *»h 00 cn PM m f- rg N» 4

- pH GO 4D 4

- CM pH O' X h- X in 4 ro <0 rg pH pH O O in O' Q. s <0 rg rg —« -4 f4 H-4 incO rg rg p4 eH rH »-H rH oo r- >0 m 4- 4

- ro ro m pg rg rg CM <M <H pH pH pH *H pH ^H pH pH pH pH pH pH O' X

LUO

odooddoodd 0 0 O O O OOO O 0 0 O O 0 O odd O O O 0 0 0 d O O O O O O O 0 d 0 0

4 f«34 C0 Or^ 4 S'^S' rg O' m O' p-« O p-4 pH 4

- m 0 4- 4) J0 GO 00 CO 00 CO r- 4 pH X 0^4 4 PS) O X ^ in X ro 4 O' h- O'

Li_ pm oo co r- pg in O' rg 4* in -1 m X r- o o -h m 4

- m 45 43 0 43 45 45 45 4) 0 4) X 45 in in 4 CO rg pH O X r- in CO pH X CO 4 0

1— OOhhN rg rg <0 in x t>- p- r- GO 00 00 oo 00 oo 00 00 00 00 GO ao X CO X X X X X X X X X X r- r- h- X X in X ^ LUZ

c

o o o o o d 0 d 0 0 0 0 0 0 0 0 d O 0 0 d d 0 0 O 0 0 O 0 0 O O 0 0 0 0 0 0 0 odd O O 0 0 0 0

hUJ

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n

0 in go 4“ 0s h rg fn 4 4 4 m in >0 4) 4) 45 O 43 45 45 4) 4) 45 45 >0 X X 43 x m m in 4 4 ro co rg pH 0 X 4 X

_J

-- cm 4 4 m 4} 4) X CO GO O' O' 0 O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' O' S' O' O' O' O' O' O' O' O' O' O' O' X X O' o

2 6600006600 0 0 d d 0 0 0 0 0 0 0 0 d d 0 6 6 0 0 060 OOO 0 d 0 0 d 0 0 0 0 OOO 0

CT5 c V no LUZ >0 oo O rg g- 0 00 0 0 0 000 0 0 0 0 0 0 0 0 0000 O O O O 0 0 0 0 O 0 0 O 0 0 0 OOOO 0 0 co CO aP O O H H H <h .h eg 4 X OOOMtO 00 0 in 0 in 0 m 0 in 0 in 0 n 0 in 0 m 0 in 0 in 0 in 0 in 0 m 0 in 0 in X X X

to <r pH >-4 H »—h rg rg m 4

- 4- m in 4) >0 p- r- co X O' O' 0 O pH pH rg rg to CO 4 4 in m X X X X m

Cd

Q_

pH pH pH pH pH pH pH •H pH pH pH pH pH •H pH

31

See

footnotes

at

the

end

of

this

table
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEW

POINT

BUBBLE

POINT

PRESSURE

3

MOLE F

WTF

VOLUME

MOLE F

WTF

VOLUME

EQUILIBRIUM

RATIO b

ATM

METHANE

MOLAL

c

SPECIFIC

11

METHANE

MOLAL

c

SPECIFIC

11

METHANE

N-PENTANE

^,4.4p4*Hp4,4,4*4r4p4<MCM<M<MCM<M<MiMCMiMiMiM<M<M<M<MCMCMiMiMiM<MCMp4rHr4p4p4p4p4.4*4p4P40 oooooooooooooooooooooooooooooooooooooooooooooo I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I mmLlJmmLi^yjijjmujiiJtjjijjijj'jjijjyj^ixiLUlUUJIiJIJJLUUJlJJliJUMUU^UUJ^lULJJlUUJUJUJUJUJUJUJUJUJ ^o®'Oinaoi/M/iNO(Mfn 4

, NMin>oo^N'ONmto>0 'O^Mn^©otf> 0'irun®'tfMio«tinfOOff>o CDNOfONN^O«tNOcO^OiN(3'r^OMiMfl>ONOOO<NJ't'00'M'ON©l/>OH(M^'OflOHi/>^ 0®0

xr^xin-$->t, x<M^-4p4 00,00 h-o-xxxminintnininxxxxx^r,fc XXO'^*-<~*»4*4^cMCMX>frin*4

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LU LU LU LU LU LU LU UJ LU LU LU LU LU LU UJ UJ UJ UJ LU LU LU UJ LU LU LU LU UJ LU LU UJ LU LU LU UJ LU LU LU UJ UJ UJ UJ LU LU UJ LU LU

CM 00 00 p4 O' r- O >

0

H CM in X 00 0 CM h- -* in CM m CM x >0 H in h- <* in X 00 O cc\ -0 O' CM in r- O CM CM O

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O O O O O 0 O O 0 O O O O 0 0 O O O 0 0 O 0 O 0 O O 0 0 O O O 0 O O O O 0 0 0 O O 0 0 O 0

UJ LU UJ of LU UJ UJ LU UJ LU LU LU LU UJ UJ UJ UJ LU UJ UJ UJ LU LU UJ UJ LU LU LU LU LU UJ UJ LU UJ LU LU UJ UJ UJ LU UJ UJ UJ LU UJ

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cc\ x x x CO CO CO co CO CO CO CO CO co co CO <r\ r*i CO CO CO CO CO CM CM CM CM <M CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM 0 O 000000 0 0 C O O 0 0 000 0 OOO 0 O 0 0 O 0 0 O 0 0 O O OOO O O O 0 0 0 0 0

UJ UJ UJ UJ LU LU LU LU UJ LU LU LU LU UJ LU UU UJ UJ LU LU LU LU UJ LU LU UJ UJ UJ LU UJ UJ UJ LU UJ UJ UJ LU LU UJ UJ LU UJ LU LU UJ

•0 >0 0 -0 X <3 x in in >* CO CO CM CM *4 O O' 00 0 in CM O 0 O >0 n in -0 O- 00 O <M 'O H- 0 ^ H- h- in X

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p4 rH *4 *4 pH c=H pH p4 pH ^4 *4 H 4 p“4 p-4 *4 p-4 p-4 -1 O' O' 0 O' 0 O' O' O' O' <* CO 00 CO ao ao ao X X X X X X

OO

6 0 OOO 000 O 0 0 6 660066 0 0 0 6 0 0 0 6 0 6 0 OOOO 0 006 O OOOO 0 0 0 x

0 0 -• -• H H -c >4

* nO O' H- O' CM >fr h # in CM O' >0 >t CM O' 00 c CO CM CM cm CM CO in n 0 in 0 4 X 0 X X — 0 00000 0 0 0 O O *4 H i*4 ^4 (M CM CO co >* in in -a r- 00 ao O' O -* rsl rr\ in >0 GO O' p4 CM 00 0 H- X CM X * 00000000 O O 0 0 O O 000000 0 0 OOOO *4 p-4 ^4 4 -4 p-4 4 *4 p-4 CM <M CM CM CM X X X in H-

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N-< O 000 0 600 O 0 6 0 0 O 0 0 OOOO O O O O 0 0 0 O 0 O O 0 O 0 0 0 0 0 odd O 0 O 0 0 0

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CL X x x x co CO co co CO CO CO CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM 4 p-4 4 -4 p4 f4 p4 *4 *4 4 p4

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>* 00 CM CM co in O' >0 CM »4 j- O in 00 in ^4 (M in 0 in CO CO r* CM 0 O' O' O CM in in CO in *4 0 rO X >0 in in X 0 in

in CM O' h- in CO H H >0 CO *4 in CO co in O' 00 O -t 0 O cO P-4 O' r- >0 in CO <M CM *4 0 GO CM >0 4 O p4 >0 CM X 0 X 0

-i- h- x co CO CO CO CM pH p4 •-4 O' 00 0- vO in H- H- CO CO CM CM CM H 4 4 4 *-4 ^4 ^4 p-4 p-4 O' X ao O 0 in in in >* >* 0 O 6 0 O 0 O O O O O 0 0 0 0060 0 0 0 O 0 O 0 O 0 O 0 d O O 0 O 0 O 0 O O 0 0 0 0 0 0

in in m in in in in >t -t H- H- 4

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UJ UJ UJ UJ UJ LU LU LU UJ JJ LU UJ UJ LU UJ UJ LU UJ LU LU UJ UJ LU LU UJ UJ UJ LU UJ UJ UJ LU LU UJ LU UJ UJ LU UJ UJ UJ UJ UJ LU •JJ O' O' O' 0 CO O O O' CO CO 0- 00 r- 0 0 -4 O' t h- 0 vO CM O in X) 0 NO co OJ ^0 >0 >fr H- n O' CM >0 O' X r*- *4 in

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O- O X CO O' H s0 O' (M O >fr *-« p-4 0- O O' *-4 m 00 >0 CO in in n in in H- CO p-4 00 H- r- O CM co CM O 0 CM in in O' O' ^4

CM OO CM >0 O' CO in vO n CO 0- 1—

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inx

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32

See

footnotes

at

the

end

of

this

table,
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

“ a- © i

O' «C

<4 H *4 ^4 e4 ^4 H *4 H H H *4 H »4 e4 »4 4 <=a H •4 4 »4 H •4 r-4 •4 ^4 4 ^4 >4 *4 *4 •H 4 ^4 4 4

o O o o <n o o O o o o o o o o o o O o o o o o o O o o o o o o o o o o O o o o o o o o o O UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ Ul UJ Ul UJ UJ 4 4 4 4 4 in in >0 C** h- QO r- O' o <N co 4 <0 O' H co 4 <o 00 o OJ in h- o m <0 o 4 O' m Csl ^4 co o co m O >0 o •o 'O <o •o <0 o 'O >0 vO >0 >o O r- r- r«- f~ GO GO 00 CO co O' O' O' O' o O o 4 H H eg co 4 in e- O' co UJ H c=4 •4 H •4 H H 5=3 H r4 *4 -* <4 r4 4 4 H 4 4 H »4 *4 H 4 CM eg eg <NJ fVJ eg eg IM eg eg eg eg co

a.

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eg eg eg eg ^4 H 4 *4 4 r4 *4 H 4 o o o o o o o o o o o o O o o o o O o o o o o o o o o o o o o o O O O o o o o o o o o o o o o o o o o o o o o o O o O O o O o o o o o o o O o o o o o

Ul UJ Ul Ul UJ UJ UJ Ul UJ Ul UJ UJ UJ UJ UJ UJ Ul UJ Ul UJ UJ UJ Ul UJ UJ UJ UJ Ul UJ UJ Ul UJ UJ UJ Ul Ul Ul UJ UJ UJ UJ Ul UJ UJ

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33

See

footnotes

at

the

end

of

this

table
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEW

POINT

BUBBLE

POINT

PRESSURE

3

MOLEF

WTF

VOLUME

MOLE F

Ff

VOLUME

EQUILIBRIUM

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ATM

METHANE

MOLAL

c

SPECIFIC*

METHANE

MOLAL

c

SPECIFIC"

METHANE

N-PENTANE OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I 111 111 til in ii* m m ill m hi in m m ill m ii* ill m in ill ill m ill ill ill 111 ill 111 in in ill 111 ill 111 iii m iif ^ i

flp

CM eg H H pH pH pH H o o o o o o O o o o o O o o o o o O o o o o o o o o o o o o

o o o o o o o o o o o o o o o o o o O o o o o O o o O o o o o o o o o o o o o o o o

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

CO 0- CO O' in O' in O' 4 'I- co in in 4- CO eg CO e- 4- 4- r- CO <6 o x 4 co 4 f- m m O' 5 ® o

CNJ CO CO o 4> h- m 4 o o •c 4> co co O' o H H <0 h- 4- CM pH CM ro 4 o 00 O eg 4 o f- CO <o o

CM o O' fM 4 0" o 4 eg o o f*p CO •h in 00 in CM o CO h* in 4- CO CM ^H O O' 00 r- 4> 4> in 4 co eg pH o o

1. 9. 4 (O CM pH H pH H pH CO >0 in in 4- 4- 3.

co co m CM CM eg CM CM CM CM CM H pH H H -4 ^H

o o o o o o o o o o o o o O o o o o o O o o o o o o o o o o O o o o o O o o O o o pH o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o O o o o o o o

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ 4 4 m GO eg r~ H 43 -o CM p^ pH in o m o m CM p» 4 CM o o CO m o >0 m >0 H CO CM •o o eg eg h- o m o 4

f* h- e- e* CD CO O' o o o H fO 4 o h- o o eg co in h- o pH co m t- o m >o o CO 00 CO o co ao pH o o CO

>0 >0 <o o X <0 <o 43 h- e- P*» h- f» p^ CO co ® co co 00 o O o o o o o H •M eg co ro 4 43 CO o >0 <o 1. 1. 1. l. H H pH H H H pH c=4 pH pH H H 1. H eg eg 2, 2. 2. 2. 2.

eg CM eg eg (\j <n

3. 0.

CM CM eg eg eg eg eg eg CM eg eg eg eg eg eg eg eg CM CM eg eg cm eg eg eg pH H pH pH H pH H pH pH pH pH pH pH ^H CM fO o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ

43 lO o cei e* -H in o 4 co cn O >0 (p( pH CO 4) eg pH o o O -1 o CO *H CM c o o in r*- eg o eg oo P- o <0 CO o o o 0s ^ co co h* p» O in m cn eg ph o ® <0 m 4 cn eg m o eg CO m h- O eg 4 GO CO o o O' 4 h- -l o

eg eg CM pH pH pH pH pH pH pH pH H H H pH pH O O o o O o o o o o GO ^ >o m in 4 CO CO CO CO eg co 4 <0 O -H H pH pH pH pH *H pH <=} ^4 pH pH H pi H pH «=4 pH H pH H pH pH -H O o o ^ O' S' O' <y O' <7* ^ O ^ -i o &

^ 00000000000000000000000-*-^>^^-.>H^-*.-i^r\ir\j(Ncg<\|('<3(r*44<'^

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UJa

®a5r^ir\-fo^<Mf^tNjao(*>r-h-ino'®ooir>'0(Nr-®h-r~^irif~fMOrr\f^f^r^oif'rrico(M(M

» o^<M<\i<N<M-*-*ooff, i?'<\iifi®o<M4ir\in434N4<r'<Ni'-io<?'®®®®o,'»Hmo®04f>,-'0®rri uj ooo—<<M®44'iNor-r^®-gr'3ir\®o<M4-o®o<M4'0®o-grriir>r,-0'^44><?'-g4®f'JOOQ

as oooooooooooo»*i-i'^>*<\i<'g<N<\i<\ir*'immrnm 444444 'rii/'mu'v®®«or»f'-®f'- 3

h»< 0 0 o O O o 0 0 o o o o 0 0 o 0 0 O 0 0 0 0 0 o 0 0 o o o o o o o o 0 0 0 0 o o O o

UJ

a. cm eg eg CM eg eg ^H pH pH pH pH ^H H pH »H pH pH H pH pH pH pH pH ^H pH pH pH pH pH o o o o o O o o o o o O pH s o o O o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o n o o o o o o

1-=* UJ Ul UJ UJ Ul Ul UJ UJ (U UJ UJ UJ Ul UJ Ul UJ Ul Ul Ul UJ UJ UJ Ul UJ Ul UJ Ul UJ Ul UJ UJ UJ Ul UJ UJ UJ Ul UJ UJ UJ UJ UJ

eg co h- r- O' GO O' 00 o o o CO ® O' H O CM eg eg e* H O' 43 >0 o co CO o eg e- in o o eg CM CM O CD pH 4 00 4

eg >fr r- in eg O' 4 00 CO CO CO CO CM o oo in 4 4 CD <0 pH o pH eg 4 h- O O' •H CO oo o 4 pH o e- D pH eg CO co eg pH <0 co H >0 >* 4 h» pH >0 >o O* 4 O' 4> co -i O' >o in 4 co eg pH o o C0 CO eg e- CO ® 4 O' in pH O co

eg cm eg pH H ^H O' 00 0- o •a in 4 n CO CM CM eg eg ph pH pH pH *H H pH pH pH pH O'’ 00 oo e- n >0 >o in in in 4 4 o

4 4 4 CO CO co CO co CO CO CO CO eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg CO O O O o o o o O o o o o O o o o o o o o o o-o o O O o o o o o o o o O o O o o o o O

UJ UJ UJ UJ UJ Ul Ul UJ Ul UJ UJ Ul UJ Ul Ul UJ UJ Ul UJ UJ UJ UJ Ul UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ Ul UJ UJ UJ Ul UJ UJ Ul UJ

eg eg in 0- ^H CO o D CO •0 O' 00 (O o eg r- co o co co 4 CO o 0- o eg eg in pH O' in pH 4 M >

0

in e- eg 00 CO X CO

in 00 4 r*- o 4 pH 00 00 in e- CO eg eg o ® r- o ci 4 pH CO O O' CM co pH O' O' O pH m in CD ^H •n X eg CO o

in co eg eg pH H in O o- in CO eg 00 •H O' O' eg 0- <SJ ® in eg O' in 4 eg •H o co >o n co CO eg ^H o pH

i. pH i. 6. 4. 3. eg eg

1. i. i. i. O' 00 Dinin^M'cococoegeg rg eg 2.

eg eg i. i. i. i. i. i. i. pH ^H 1. pH 1. 0.

og04<\i<M4~<ff'CT''0-Hm®<Ni04-*ir\r-0'ooO'i3'®ir\<N®<\iinf^®®r-m<7'.<\iroo<y'44 o

(M4’r>®®ir\>4'fr^orriir\®^m^.ir\u>triin<o®ir\irti/>mtrt^'<ff'i<M>400, ®<oinm^r>^<® -o oooooooooooooooooooooooooooooooooooooooooo o

4Of-4-0<?'44>-.mir\4®r'-4®—•<\irri44444i'’'i ,N'*o«4Nn'i<?'4>-*-0'^443in-<®® 4

Q H ^ ^ N ^ 00 CO 00 CO 00 CO ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ CO 00 00 CO 00 CD ^ oooooooooooooooooooooooooooooooooooooooooo o

• V w ®®000000000000000000000000000000000000000®irif0

rtrtN^<ao(M<fj«oinoiftomoifioinoif>oifioinoiftOK'oiftOiftoinoiAOKMr'NN

34

See

footnotes

at

the

end

of

this

table
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THEMETHANE-N-PENTANE

SYSTEM

-

CONTINUED

CO o

CO

CO

o

UJQ

oc. 3

H-<

0£UJa

x

UJ

<\J H .4 •H *4 H H o o o o o o o o o o o o o O o o o o o o o o o o o o o o o

UJ o o O o O o o O o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

<c UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ Ul UJ UJ Ul UJ UJ UJ JU Ul Ul Ul UJ Ul UJ UJ X GO •o p- 4- O' o o> o O' CO CO >0 O' ^4 <o co O' CM 0- CM CM iH o in 00 •0 O' co 4- CM GO GO 4} 4> 4- o

UJ o m n- m CO O' -0 p* 4^ CM CO in O' in 00 00 CM o CM m ^4 GO o in 4" 4- in in <o 00 o ^4 CO in in 4- o z o o CO in o 4- CM ^4 o co CP O' CM >0 CM 00 in CO O' p- >0 4- CO CM *4 o O' oo p- sO 'O in 4- CO CM ^4 o

•4 in CO CM CM ^4 «-4 H H 00 >0 in in 4- <* 1*1 CO CO co CM CM CM CM CM CM CM CM H *4 »4 f4 ^4 r*4 *-4 *“4 ^4

o o o o o o o o o o o o o o o O o o O o O O O O O O O O o o o o o o o o o o f-4 o o o o o o o o o o o o o o o o o o o O o o o o O O o O O o o o o o o o o o o o o UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ Ul UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ UJ UJ

>0 o * 00 4^ oo 4- GO CO O' CM m o in o m H 00 in CO CO 4- >0 O' CO H *4 in CO o n P- in oo r- 00 f«4 o o CM CM CO CO 4- X* <0 p» O' o CM co in •O 00 o CM 4- <o GO ^4 4- P- o 4^ 00 CO oo in 4- in O' CM O' UJ

Qp- p» h- p* P- p*- P» P- r*- p- p- 00 00 00 00 oo 00 O' O' O' O' cp o o o •4 ^4 rW CM CM CO 4> m 4> O' CM CO - <4 -4 H *4 c—

«

H H -4 H *4 r*4 s4 h f4 c4 f=4 ^4 o=4 CM CM CM CM CM CM CM CM CM CM CM CM CM PO o

CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM *4 f4 f-4 f4 *4 *4 f4 f-4 t4 r4 CM CO O o O o o o o o O O O o O O O O O o O o O O O o O o o o o o o o o o o o o O O

_l UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ Ul UJ Ul UJ UJ Ul UJ UJ UJ UJ Ul Ul o 4- 00 cm p- .4 >o o 4- CP .0 CM o p- in CM o O' 00 oo OO O' o CM 4- p- P- O' P- in 4- 4- <o *o 4- 4> o PO CM ^ o o O' O' 00 p» m 4- CM h o O' p* o m 4- CO CO <M O O' CO p» O' CM 0- *0 o f4 00 CM H o 2 <N CM CM CM CM CM H H .-4 f4 <=4 •—4 o o o o o o O O o o O' O' 00 p» P- o «

0

>0 P* O' o *4

H H H H H H H H H H H H H H ^ H ^ »4 H H H H ^ H H H H ^ ^4 H f4 H »4 H ** f4 O ooooooooooooooooooooooooooooooooooooooo I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I III ill III i

ft f i^i qi III ill m m Hf 1 1 1 m ||| III ill III HI 111 til Hi til III III III 111 m III II* ill 1 1 1 I|f III H ^ III oortooo^(\M)oaonNooo'OinN^soaO(*un*j'rtNstojNNN*so

Jo^swosoin'tflNHrfOooo^rf-M'JN <N,r^ -tm-ON®ON.t®H^inoo

0<''J't'Oco»-f*>i/>F-oif'-<®4'0*“4--*coif'<\lOF-if><*if\ii-i-*-HfriF'-»*h-ift^i**<sjr'-.o4- OOOOOHWHrtNMn®^UMflONN®J'OOHNM'tK\^^®O^Cl®«IMI'O0' OOOOOOOOOOOOOOOOOOOOO-H-i—i-i-i-H.-i-i^.j<\|i\l<\l<\lcgf*ir<1 .1-<\| oooooooooooooooooooooooooooooooooooooooo

^O^0'(M«NHrtHNOHJ'n^N.f^^0^®O>0(fN+®HMflOmNN<|N

o-<-iNmj’in®f'aoNii>so'^rtrf\Nff'iHrti/\s®oN^®eoK>iA»oi,'®rtaift OOOOOOQOOO'<HrtHHniN(MNNK\®®mrt<'^*4’4, lfl®®lft«4).ONN4

0. o0, o O o o

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0. 0. 0. 0. 0. o o0. 0. 0, 0. 0. 0. 0. 0. 0. 0. o o

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CM CM CM CM ^4 ^4 f4 f4 ^4 f-4 1*4 f4 fH f=4 «4 •4 »4 e4 *4 f4 4 *4 f4 «4 f4 f4 O o o o o O O o o O o O *4 O O o O o o o o o o o o o o o o o o o o o o o o o o O o o o o o o o o o o o o

Ul UJ UJ Ul Ul UJ ULI Ul UJ UJ Ul Ul Ul Ul Ul UJ Ul UJ Ul Ul Ul UJ Ul Ul Ul UJ Ul UJ UJ UJ Ul Ul UJ UJ Ul Ul Ul UJ UJ

GO 00 4- in o h- CM in 00 f—4 X C0 CM o 4- 4- o o oo co 4) O' co f*- O' 'o PO in p- CO p- X p- PO 4 O' in 4

o in -4 co H O CM in oo O' -o *4 *4 CM o 4- CM co NO CM o o o *4 CO >0 4- >0 PO CM 4- X in 4- 4- CM O' 00 4^ (M r> o O' ^4 4- 00 co 4- 00 CO O >o CO ^4 O' >0 in CO P0 CM c=3 o O' CO CM P* CM p» co O' in **3 >0 CO 1. *4 •^4 O' r*- 6. 5. 5. 4

3. 3. 2. CM CM CM 4 *4 •4 i. *4 ^4 *4 *4 1. 9.

O' 8. X P» 7, o >0 in 5. 5. 0,

4- CO CO CO CO co PO CO CO CO CO CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM <M CM CM CM cm CM CM CM PO o O o O o o o O o o o o o o o O o o O o O o O O O o o o o O o O o O o o o O o

UJ UJ UJ UJ UJ Ul UJ Ul Ul Ul UJ Ul UJ Ul UJ UJ UJ UJ Ul Ul Ul UJ UJ Ul Ul UJ Ul Ul Ul UJ UJ UJ Ul UJ UJ Ul UJ UJ Ul CO 00 4- CM O' 00 O' oo o CM o *4 r*- O' h- f4 O' oo O' o oo 30 CO o >0 in o o 4- >o in PM X O' CM in 4- P-

>0 oo *4 >o PO CM O' CM P- f-4 *4 p- >0 p- h- m in O' p- GO >4 in ^4 X p- -0 >o p^ O' 4 co 43 O CO o

CM CO CM CM in CO in 4- CM o PO *4 f4 4- 00 CO O' o C0 o 00 n0 in co CM o O' X >0 n in 4- CO P0 CM f4 »4 4 N0 4- (O CM <M f4 f4 H *-4 1. 8. 7. >0 5. 4- 3. 3. 3. 3. 2. 2. CM cm CM 2. 1. 1. •4 i. i. *4 4 *4 1. 1. 4 o MO‘-<ONO'WirMflifiBMMHifi®ac®oo-<N^iri®-i(r.®sBifiPuao'ON® 0‘^Oa'f-®Sf-9'®®n^aO®(M®^NSN®^FlJ)ON4®®K>O®»(M»n® o«OMfla-<^'OBNirw'®ooH-i-i-iHri-i-HootMoi'iin4MOff'>o^<i

OOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOO

oif\*'sjf>-a'aD4-^ir\rri^-friooo>of^aoa'000'0'®r~ir\rooh-oo'^, oo<Mir\f^or'h- o in*jn-p*-xxxxxxxcpo'^o»O'O'a'<7'O'a‘(7'O'0'0'O‘<7'O'C7'XXxxxxxxnooooooooooooooooooooooooooooooooooooooo

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N^0®OIM't0®O®OKlOlfiOI/'Ol/'O®OU'O^O®O®O^O®O®OlOOi*)HO

35

See

footnotes

at

the

end

of

this

table.
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEW

POINT

BUBBLE

POINT

PRESSURE

3

MOLEF

WTF

VOLUME

MOLE F

WTF

VOLUME

"

EQUILIBRIUM

RATIO b

ATM

METHANE

MOLAL

c

SPEaFIC

d

METHANE

MOLAL

c

SPECIFIC

11

METHANE

N-PENTANE

H H »-4 H H H H *“4 H H H H H H H H H H H H H H H H H H H H H H H ^ H O oooooooooooooooooooooooooooooooooooooo I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I UJUJUJUJUJUJUJUJUJUiUJUiliJUiUJUJUJUJUiUillJUJUJUJUJUJUJUJUiUJUiUilUlilUiUiUiiiJ

H c—1 «=4 H H o o o o o O O O o o o o o o o o o O O o o o o o o o o o o

o o o o o o o O o o o o o o o o o o o o o o o o o o O O o o o o o o o o o o

UJ UJ UJ UJ Ui UJ UJ UJ UJ UJ Ui UJ UJ UJ UJ UJ UJ UJ UJ UI UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UI UJ UJ UJ UJ UJ UJ o o cm in m CO 4- —

1

o O' O' in m GO ^ o rr\ CM h- r- 4- CM GO CM O' O' o ift 4- O' in h* r** cm o

o in O' r*» m GO O 'O 4- ^4 m in CM in O' <\l CM •0 4- m ® <*) o GO •o o n in >0 <0 GO O' h *4 o a o H 4- in o r- 4- cr> •4 O 4- o o m h- «M O' <0 *»4 O' f- o m m CM *4 O O' GO r- ® in 4- 4- fOCMO o

m 3. eg <M -i H H H 8. h- •o in 4- 4- <»> 3. 3. 3. 2. 2. CM 2. 2. CM IM 2. 1. •4 H H ^4 *4 H H *4 H -4

o O O O o o o O o o o o o o o o O o O o o o o o o o o o o o o o o o O o o •H o o o o o o o o o o o o o o o o o o O o o o o o o o o o © o o o o o o o o o

UJ UJ UJ UJ UJ UI UJ UJ UI Ui UI UJ UJ UJ UJ UJ UJ UJ UI UJ UJ UI UJ UJ UI UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ m r- CM o in o in o 4* 1^ CM GO m H o m <M O o 4* GO 4- CM PO CO >0 H CM o 4- in O' * 4- in O'

4* 4> in in o >0 r* GO O' o CM m in GO o CM 4

* o GO o CM in GO ^4 4- GO m CO 4- p4 o CM 4 O' ^4 O' h- h- h- r- h- r- 00 00 00 GO GO GO O' O' O' O' O' o o o o *4 H CM CM m 4- in >0 GO O -o m

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r-4 .“H w—l ^ r4 ^4 «~4 f-i t—i ^ >—* w-4 *4 .—I **4 i-4 r—1 I *4 r-4 r-4 *4 *4 rH r~* ^4 "4 ^4 ~4 ^ ^ O

o4-

n"i HKtinNorg^«a404N«oiA'4coinrgai 4nHOMniAinr>^iAHOMON<f'00 OOOO^HHHHrgnn^^m41«MOaO'OHHM«l^in4CD9Hmv\arg9i nin ^ 000000000000000000000'*-H*H-*>H-H.^rH.--i-H<\|<\|<Mf\jm«>4, <\l

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'Z

See

footnotes

at

the

end

of

this

table
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEW

POINT

BUBBLE

POINT

PRESSURE

3

MOLEF

WTF

VOLUME

MOLE F

WTF

VOLUME

EQUILIBRIUM

RATIO b

ATM

METHANE

MOLAL

c

SPECIFIC

11

METHANE

MOLAL

c

SPECIFIC

11

METHANE

N-PENTANE

^4 ^4 pH pH H H H H H —4 H pH H H pH p4 pH H H H sd pH pH pH pH *4 H ^4 H pH pH p4 ^4 pH pH 0 009 0000 0 0 O O O O O O O O O OOOO O O O O O O O O 0 O O O 0 0 0

LU UJ UJ LU UJ UJ UJ UJ LU LU UJ UJ UJ UJ LU LU UJ LU UJ UJ UJ LU LU LU LU LU UJ UJ LU UJ LU LU UJ UJ UJ UJ UJ

un co eg 0 co r» eg >0 0 vO 0 ro 0 0 4 'O 30 *4 4 in —< o> ao O' 0 CO CO e- CO CM O' CO ^4 UN eg 0

r- ® ® >0 CO UN pH O UN 0 (M eg e- rO ^4 rsj lA ® (NI N pH p» 4 (A CO 4 ao LA >0 CO >0 0 O' UN 0

co c 4 -O i-H ® ® 4* eg O' 00 r** ® 0 0 0 o <ONN ao ao a* O H fNJ CO UN O CO CO CO eg CM 0

06 1n 4

3. 3. 2

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. eg

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40

See

footnotes

at

the

end

of

this

table,
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEW

POINT

BUBBLE

POINT

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3

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WTF

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Ff

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"

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MOLAL

c

SPECIFIC

d

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MOLAL

c

SPECIFIC

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41

See

footnotes

at

the

end

of

this

table.
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM -

CONTINUED

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42

See

footnotes

at

the

end

of

this

table
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM -

CONTINUED

DEW

POINT

BUBBLE

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O' HnmceoiM'f >0 oo oegmooego'egeg o o o o o O O ^4 ^4 ^4 ^4 eg eg eg eg eg m cn rn cn g* m o o 0. 0. 0. 0« o 0. 0. o 0. o o 0. 0. 0. 0. 0. 0. 0. 0, 0. 6 6 H H p-4 ^4 #4 ^4 ^4 »4 r4 *4 «p4 H ^4 *4 O O O O o O O O ^4 o o o o o o o o o o o o o o o o O o o O o O o

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

e- >o o e- eg eg cn in 4 m O' eg O' h- -o *4 r4 ^4 ro 00 O' in 00 in 4 4 eg m m ^4 o O' O O' m 00 4 4 m oo CO eg m o o in 4 rO •4 O' r*- in 4 eg eg o o 4 o o m 4 4

eg eg 2. 2. eg ^4 i.

H i. i. »-4 1. O' co GO 7. 6, 6. 5. 4 o

rn

mm

©

m eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg eg cn o o o o o o O o o o o o o o o O o o o o O o o

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ yy UJ yj UJ UJ C eg oo 4 o o in •4 eg m o ^4 O' o O in CO 4 m in 4 O O' eg O' in eg o eg o h- in £> CD eg 00 e- m eoo in 4 eg o oo g> O' m 00 m O' >0 -4 CO 4 eg o 00 ^4 H H 1. i. i 00 7. 6. 5. 5. 4 4. 3. 3. 3. 3. 2. 2.

eg eg eg ^4 C. ffi(fiWHH^ONS#® ,tO’OOO^NOOlflO oinr“®-*inino-*® — -*®-*®<MO'<\i4<M4in®

m

ni4-0®m®^<M4inp“«®0'0'0'®®^'®4''*0' O' OOOCiHHHNNrgMIMNIMNMftlNNNIMM^ f\) OOOOOOOOOOOOOOOOOOOOOOO o

f'inin<\|.»-<N—<0-0-—<-0f'-m0'O0'-00'a'4(\lrM.0 —I ®f“ 400 f^<\lin®^M® 44 m,*,$-mi\|»*(T-m(\| in o-*<Nr-i44ininin'0-0'0'0-0-0'0-0'0'0-0minin -o OOOOOOOOOOOOOOOOOOOOOOO o • Vi W 00000©0000000000000000'0»^4

^taomoino^oiAOinoiftoino^oiAooc1 o

rf ^,^oj<MOi^i^-^-unir\®vOi>^F^®®a'0'oo-i'-<®r~

43

See

footnotes

at

the

end

of

this

table.
o o

o o © o o o o o o o o o o o O o O o o o o o o o o o o o o o o o O o o

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

O' o o o * in o o ^4 co 4 4

- 4- o m O' o o CO o co o m UN sO <o UN <NJ 00 *0 o O o

*4 •o 4 4 h» (M cm •o O' O' UN O (NJ UN r*> m O' o <N m 4

- CO fNI in UN (NJ 00 CNJ (NJ o 4) o 4

- o

in 00 CM rsj m o p- in on CNJ CM cn 4 <£ 00 ^4 4) ^4 o © co CM 4

- O' m co (NJ •-4 (M «N m CNJ O o

• 9 • • • • • • • • • • 9 9 • • • • • • # • • • • • • • • • • • • • a O' 00 CO >

0

o m in in UN UN m in UN in 4) 4> r* © O' 00 r* 41 '

0

4) '

0

<0 o o <o 4) CO •4

^4 o o o o o o O o o o O o O O o o o o o o o o o o o O o o o O o o o o

o o o o o o o O o o o o o O O o o o o o o o o o o o o o o o O o o o o

UJ UJ UJ UJ UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

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UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ

00 p- UN CO CNJ O' O' -4 O' O' UN in ^4 00 CNJ 43 co in 00 m 4- CNJ o CM o *4 O' m CO 'o CM 4- p* 00

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CM CM CNJ CM PM CM CM CM CM CM CM CM CM CM CM CM CM CM co CM (M CM (M (M CM CM CM CM PM CM CM CM CM CM CO o o o o o o o o o o o o o o o o o o o O o o o O o o o o o o o o O o o

Ul Ul UJ UJ UJ UJ Ul Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ Ul UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

ib m 0 O' ® O' in o f- >0 00 •O l>- 4 >0 o >0 CM 00 o O CM <0 m UN O' 4 r- CO (O <0 p* ^4

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in in m m in m m m in 4 4 4 4 4 in ^ in oh •0 >0 •c o <0 in UN UN in <0 >

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1- o o o o o o o o o o o o o O o o

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M) O- O' o PN UN ^4 O' >0 ^4 ^4 ~0 4 00 co UN UN 00 CM 00 (M oo 0- O' UN 4 (M O' o o (M 4 CD

h- © CM in O o UN cn 4 UN >0 in in CM p- ^4 ^4 UN o #4 CO 00 UN UN UN >0 o 4 (O m CO CD h- O

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Ul UJ Ul UJ UJ Ul UJ Ul Ul 111 111 HI 111 111 in UJ UJ Ul UJ UJ UJ UJ Ul UJ Ul Ul UJ UJ UJ UJ UJ Ul UJ UJ UJ

in >o *o in f- ® o 4 ,h « ® in m 4 ^4 oo ao © o P^ o P^ © CO CM 44 CO CO O' <0 44 o MD ^ 4 «0 N UN N P^ CO in CM CO UN CM GO 00 co O' 00 (M fM CO 00 ^4 co UN ^4 CM o p- o

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44

See

footnotes

at

the

end

of

this

table,
TABLE

3.1.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THEMETHANE-N-PENTANE

SYSTEM

-

CONTINUED

DEWPOINT

BUBBLE

POINT

PRESSURE

3

MOLE F

WTF

VOLUME

MOLE F

WTF

VOLUME

"

EQUILIBRIUM

RATIO b

ATM

METHANE

MOLAL

c

SPEaFIC

d

METHANE

MOLAL

c

SPECIFIC

11

METHANE

N-PENTANE

o4-

4-

*

• O

aia

cc3

<

CC

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o eg eg in O' eg O ~g

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r*g eg co co co -g* 4- 4- 4- (O CO 4’ o »g H eg eg eg eg eg eg eg

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45
Table 3.2. Agreement of interpolated and experimental data for the methane-n-pentane system

Source Number

of points

Average a Deviation

fraction b Standard c

Composition d

Taylor [36] 14 0.0021 0.0042 0.0116

Dourson [37] — 4 .0078 .0198 .0164

Sage [38] 32 .0007 .0035 .0037

Pressure e

Sage [38] 34 -0.05 0.0054 0.33

Sage [35] 9 4.8 .0395 5.5

“ Average deviation defined by

£ ^

(Gt exp -Gk sm ]lN.

b Fractional deviation defined by

' Standard deviation defined by

l|[

([?

(C* exp Cfcsm ) /Gke .])«».

(^frexp ^sm) 2]/(AT— 1)|

111 where G = either composition or pressure.

d Composition in weight fraction methane.

e Pressure in atm. Table 3.3. Unique states for the methane-n-pentane system

Methane Critical Maxcondenbar Maxcondentherm

Mole

fraction

Weight

fraction Temperature Pressure a VolumeTemperature Pressure a Temperature Pressure a Molal b Specific c

K atm K atm K atm

0.0 0.0 d 469.49 33.16 294.6 4.08 469.49 33.16 469.49 33.16

.333 .1 439.9 75.9 218 4.08 408.4 91.5 446.6 58.6

.529 .2 409.7 111.3 173 4.08 355.9 133.5 427.0 70.9

.658 .3 380.6 139.0 144 4.08 328.4 152.4 408.6 76.7

.750 .4 351.4 156.4 122 4.04 310.8 162.4 390.0 78.9

.818 .5 311.7 166.5 99 3.78 e 294.7 167.5 371.5 78.4

.871 .6 e 275.0 169.2 275.3 169.2 353.3 75.8

.913 .7 253.0 167.0 253.0 167.0 333.8 71.2

.947 .8 232.3 155.9 232.3 155.9 e 309.7 64.4

.976 .9 211.2 129.4 211.2 129.4 279.3 55.7

1.0 1.0 d 190.63 45.57 99.3 6.18 190.6 45.5 190.6 45.5

.1 .024 462.8 44.2 272 4.08 457.9 46.1 463.8 41.4

.2 .053 454.2 57.0 249 4.08 439.9 63.1 456.7 49.2

.3 .087 443.8 70.7 226 4.08 417.0 83.5 449.4 56.4

.4 .129 430.9 86.7 203 4.08 390.3 106.4 440.7 63.2

.5 .182 414.8 105.1 180 4.08 362.9 128.2 430.3 69.3

.6 .250 394.7 126.6 157 4.08 339.7 144.9 417.8 74.4

.7 .342 368.6 147.5 134 4.08 320.7 157.1 400.7 78.0

.8 .471 327.5 164.0 106 3.90 e 299.5 166.6 376.9 78.7

.9 .667 260.2 168.4 260.2 168.4 340.2 73.0

Estimated

uncertainty f 1.0 1.0 3.0 2.0 4.0 2.0 3.0

d API 44 [16].

e Values at this and lower temperatures extrapolated. 'Estimated uncertainty expressed in percent.

a (Atm) (1.013250 X 105

) = N/m2

. "Volume expressed in liters/kg-mol.

c Volume expressed in liters/kg. 46
TABLE

3.4.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

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H.H

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1. in cn cm cm ^ i. -* -o •4- 3. 2. CM CM e-4

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47

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footnotes

at

the

end

of

this

table.
TABLE

14.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS -

CONTINUED

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48

See

footnotes

at

the

end

of

this

table,
TABLE 34..

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS -

CONTINUED

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49

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footnotes

at

the

end

of

this

table,
TABLE

14.

PROPERTI

ESOF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS -

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50

See

footnotes

at

the

end

of

this

table
TABLE

3.4.

PROPERTIESOF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS -

CONTINUED “ °r Si

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51

See

footnotes

at

the

end

of

this

table
TABLE

3.4.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS -

CONTINUED

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52

See

footnotes

at

the

end

of

this

table,
TABLE

14.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS -

CONTINUED

HH

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eg >* in re re re

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53

See

footnotes

at

the

end

of

this

table,
TABLE

14.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS -

CONTINUED

H pH p=l pH

HH pH

H •-4 CM CM CM CM CM pH pH pH pH pH pH

© o o o o o o o o o o o O O O oooooooo

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in r*- co >o

N ff1 s in 4 co cm pH

H in 4 o cm

m o o o o

9. 4 co cm

2. 1. 1. pH

H -i O' oo 8. 00 O'H pH pH CM cn 45 pH

CM pH pH pH pH pH ^H pH pH pH

© o © o ©O

©

O o ©© o O o o © o o o o o o © o o o o O o o © o o o

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

inm CM 00 in o © pH 4 in CM pH co 4 o CM

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pH O' <o *0 in 00 in a* o 4-

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UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

co CM CM >0 CM 00 CM o O CO pH >0in ao <o

m 4> o O h» OO OD o © O o >0 co o r- in in co ao co 00 pH

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co co

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UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

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pH cm r- CM CO <4- O' in pH hm in

mm >0 o >om >0 CO o H 4 >0 h- O' o CM 4“ O co 00 pH pH pH ^ pH ^ o O o o O O O pH vO © o co in ao m O' o' © o © o o o o o o o o o o © O pH pH ^H H CM CM 4 4m o o o 6 o 6 o o 6 b o boo o o o ooooo o

*4- O’ <\i f- in cm ao CO O' >4 ao r- ^ CM 00 CO O' CO cm ao ON4 O h- 40N CO o 4 "O in pH CO in m CM ir\ 9* o )*\ o © © pH CM CM co -4* >4- in >0 CM 00 4 O in o in H 4- >0 pH CM o o o o o O O O O O pH pH CM CO co 4- 4- in in >0 ao h- O © o O odd © o b o o o o o o o o boo o o o o o © o o o © o O pH pH pH pH pH H ^H H CM CM pH o o o o o o o o o O O o o © o o o o o o o o

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

>1* >0 O' -4-

m pH O' ao CO o o inm CO co co CO -4 cm co

O

ao 4 co O' o in in O' >o

m CM ao 4- (VI

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pH 4 00 CO

O 00 -o 4 co CM O' '©'4 4* CM 00 in CM

O©

© >0

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CM CM ^H pH pH pH pH pH pH pH o o O o o o o © o o pH o o o o o o o o o o o O o © o © o o o o o o

UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ UJ

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N 4) >4- >4 4 •4 O' o h- 4> 4- 4- >0 O' 4 CM

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O' 4 h* co ao ao pH >0 CM O' >4 CM CM CM in o -c CM O' f- pH

CM pH o in •4- 4 CO CO CM pH O' >o in 4 co co CM CM

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CO in >4- CM pH O' >o pH CO CM o >0 >6 CM CO ao OO O' ao (O © ao pH o >o •4- in pH CO CO O' CO ao © o 4> O CM pH 4 m fO

©

in CM co CO pH co in >0 pH (O CO 4- CO CO co CM pH O' in pH 4 o m o h- ao ao ao CO ao O' O' O' O' O' O' O' O' O' ao ao co O' • • • • • • • • • • • • • • • « • • • • • • • VJ o o O o o O © © o o © o O o o © o © © o o © C Vi W o o © O O © o o o o O o © o o o o o o o o ma m

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O IM 4 4 rn O' ^H pH pH H pH CM <M CM CM CM

54

See

footnotes

at

the

end

of

this

table
TABLE

3

4.

.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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cm 00 0 O' 4 o 00 0 4- 4- o 00 *4 © m o oo IO CO o o ro O' <o O' 4- *4 CO 0 4- IO O' H h- CO o CD IO CO o o

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55

See

footnotes

at

the

end

of

this

table.
TABLE

3

4.

.

PROPERTIESOF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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? UJ UJ UJ UJ UJ UJ UJ UJ UJ £

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56

See

footnotes

at

the

end

of

this

table,
TABLE

3.4.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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57

See

footnotes

at

the

end

of

this

table,
TABLE

14.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

-

CONTINUED

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58

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the

end

of

this

table.
TABLE

14.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS

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CONTINUED

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the

end

of

this

table,
TABLE

3.4.

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THE

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METHANE-N-PENTANE

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63

See

footnotes

at

the

end

of

this

table
TABLE

14.

PROPERTIES

OF

THE

COEXISTING

PHASES

IN

THE

METHANE-N-PENTANE

SYSTEM,

ENGINEERING

UNITS -

CONTINUED

DEW

POINT

BUBBLE

POINT

PRESSURE 3

MOLE F

Wt"f

VOLUME

MOLE F

WTf"

VOLUME

EQUILIBRIUM

RATIO b

PSIA

METHANE

MOLAL c

SPECIFIC 1

METHANE

MOLAL c

SPECIFIC* 1

METHANE

N-PENTANE

H

H ^ H

O o o o o o till iii iii m if i m ITOOCO NOO'OO M O' 00 O • • • • ® ^ CO H o o o o o o o o o o

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64
TABLE 3.5. Unique states for the methane-n-pentane system, engineering units

Methane Critical Maxcondenbar Maxcondentherm

Mole

fraction

Weight

fraction Temperature Pressure a Volume

Temperature Pressure a Temperature Pressure a Molal b Specific c

° F psia °F psia °F psia

0.0 0.0 d 385.41 487.3 4.72 0.0654 385.41 487.3 385.41 487.3

.333 .1 332.1 1115 3.50 .0654 275.5 1344 344.2 862

.529 .2 277.8 1635 2.78 .0654 181.0 1962 308.9 1042

.658 .3 225.4 2043 2.30 .0654 131.5 2240 275.7 1127

.750 .4 172.9 2298 1.95 .0648 99.8 2387 242.3 1159

.818 .5 101.3 2447 1.59 .0605 e 70.7 2462 209.0 1152

871 .6 e 35.4 2486 35.9 2486 176.3 1114

913 .7 -4.2 2454 -4.2 2454 141.2 1047

947 .8 -41.5 2291 -41.5 2291 e 97.8 947

976 .9 -79.5 1902 -79.5 1902 43.1 818

1.0 1.0 d -116.54 669.7 1.59 .0990 -116.54 669.7 -116.54 669.7

.1 .024 373.4 650 4.35 .0654 364.5 678 375.1 608

.2 .053 357.8 838 3.98 .0654 332.1 927 362.3 723

.3 .087 339.2 1039 3.62 .0654 291.0 1227 349.2 829

.4 .129 316.0 1274 3.25 .0654 242.8 1564 333.5 929

.5 .182 287.0 1545 2.88 .0654 193.6 1884 314.9 1018

.6 .250 250.7 1860 2.52 .0654 151.8 2129 292.4 1093

.7 .342 203.7 2168 2.15 .0653 117.6 2309 261.7 1146

.8 .471 129.8 2410 1.70 .0624 e 79.5 2448 218.8 1157

.9 .667 8.7 2475 8.7 2475 152.6 1073

Estimated

uncertainty f 1.0 1.0 3.0 2.0 4.0 2.0 3.0

“(Psia) (6.894757 Xl03

) = N/m2

. « API 44 [16].

b Volume expressed in cu ft/lb-mol. c Values at this and lower temperatures extrapolated.

c Volume expressed in cu ft/lb. ' Estimated uncertainty expressed in percent. TABLE 3.6. Agreement of interpolated and experimental data for the methane-n-pentane

system, engineering units

Source

Number

of points

Deviation

Average a Fraction b Standard c

1 Composition d

Taylor [36]

—

14 0.0021 0.0042 0.0116

Dourson [37] 4 .0078 .0198 .0164

Sage [38] 32 .0007 .0035 .0037

Pressure e

Sage [38] 34 -0.7 0.0054 4.9 Sage [35] 9 69.9 .0395 80.8

a Average deviation defined by I ^ (C* exp —Gk ,m) I//V.

1 ^

b Fractional deviation defined by

[ £

^(C* exp -C ,J/Gk exJ^IN.

c Standard deviation defined bv {j^ (Gk „B - Ck s J

2 j/(V-l)

j d Composition in weight methane.

e Pressure in psia.

1,2 where G — either composition or pressure.

65
Table 3.7. Accuracy of experimental background for the methane-n-pentane system

Quantity Units Taylor [36] Dourson [37] Sage [35] Sage [38]

Sample purity

Methane Mole 0.990 0.997 0.997 0.997

n-Pentane fraction .995 .995 .992 .992

Composition

Volumetric a Atm 0.2 Phase measurements Weight

fraction 0.01-0.02 0.005 .005

Volumetric behavior Percent 0.3-3.

0

0.4 0.5

Unique states Temperature K 1.0 Pressure Atm 0.8

Volume Percent 5

a Phase boundaries determined from first derivative of volume versus pressure. All error assumed to be in pressure.

4. References

[1] “Thermodynamic Property Values of Ordinary Water

Substance,” International Secretariat, Sixth Inter- national Conference on the Properties of Steam, American Society of Mechanical Engineers, United Engineering Center, New York 1967.

2] Antoine, Charles, Compt. Rend. 107 , 681—684 (1888). 3] Rossini, Frederick D., Pure and Applied Chemistry 9,

453-459 (1965). [4] Dana, L. I., Jenkins, A. C., Burdick, J. N. and Timm, R. C., Refrigerating Engineering 12, 387^405 (1926). [5] Sage, Bruce H., Schaafsma, J. G. and Lacey, William N.,

Ind. Eng. Chem. 26, 1218-1224 (1934). [6] Reamer, H. H., Sage, B. H. and Lacey, W. N., Ind. Eng.

Chem 4 1 482-484 H9491

[7] Helgeson, N.’ H. and Sage, B. H„ J. Chem. Eng. Data 12,

47-49 (1967). [8] Rose-Innes, J. and Young, Sydney, Phil. Mag. Ser. 5, 47,

353 (1899). [9] Young, Sydney, Sci. Proc. Roy. Dublin Soc. 12, No. 31,

374 (1910). [10] Sage, B. H., Lacey, W. N. and Schaafsma, J. G., Ind. Eng.

Chem. 27,48 (1935). [11] Sage, B. H. and Lacey, W. N., Ind. Eng. Chem. 34, 730

(1942). [12] Beattie, J. A., Levine, S. W. and Douslin, D. R., J. Am.

Chem. Soc. 73, 4431 (1951). [13] Li, Kun and Canjar, L. N., Chem. Eng. Progr. Symp Ser. No. 7, 49, 147 (1953). [14] Ambrose, D., Cox, J. D. and Townsend, R., Trans. Faraday

Soc. 56, 1452 (1960). [15] Partington, E. J., Rowlinson, J. S. and Weston, J. F., Trans. Faraday Soc. 56, 479 (1960). [16] Am. Petroleum Inst. Research Project 44, Chemical

Thermodynamic Properties Center, Texas A & M

University, “Selected Values of Properties of Hydrocarbons and Related Compounds.”

[17] Kozicki, W. and Sage, B. H., J. Chem. Eng. Data 5, No. 3, 331 (1960). [18] Benedict, M., Solomon, E., and Rubin, L. C., Ind. Eng.

Chem. 37, 55 (1945).

[19] Stull, Daniel R., Ind. Eng. Chem. 39, No. 4, 517 (1947). [20] Perry, R. E. and Thodos, George, Ind. Eng. Chem. 44

No. 7, 1649 (1952). [21] Michael, G. V. and Thodos, George, Chem. Eng. Progr.

Symp. Ser. No. 7, 49, 131 (1953). [22] Kobe, K. A. and Lynn, R. E., Jr., Chem. Rev. 52. 131 (1953). [23] Frost, A. A. and Kalkwarf, D. R., J. Chem. Phys. 21

No. 2, 264 (1953). [24] Brydon, J. W., Walen, N. and Canjar, L. N., Chem. Eng.

Progr. Symp. Ser. No. 7, 49, 151 (1953), [25] Thodos, George, A.I.Ch.E. J. 1 No. 2, 168 (1955). [26] Erpenbeck, J. J. and Miller, D. G., Ind. Eng. Chem. 51

No. 3, 329 (1959). [27] Nakanishi, K., Kurata, M. and Tamura, M., J. Chem.

Eng. Data 5, No. 2, 210 (1960). [28] Boomer, E. H., Johnson, C. A. and Piercey, A. G. A., Can.

J. Res. B 16, 319 (1938). [29] Armstrong, G. T., Brickwedde, F. G. and Scott, R. B., unpublished report (1954)

[30] Cardoso, E., J. Chim. Phys. 13, 312 (1915). [31] Keyes, F. G., Taylor, R. S. and Smith, L. B., J. Math. Phys.

1 211 (1922). [32] Volova, L. M., J. Phys. Chem. (USSR) 14, 268 (1940). [33] Bloomer, O. T. and Parent, J. D., Inst. Gas Tech. Bull. 17

(1952). [34] Bennewitz, K. and Andreewa, N., Z. Physik Chem. A 142

37 (1929). [35] Sage, B. H., Webster, D. C. and Lacey, W. N., Ind. Eng.

Chem. 28, 1045 (1936). [36] Taylor, H. S., Wald, G. W., Sage, B. H. and Lacey, W. N.,

Oil Gas J. August 10, 1939, 38, 46-49.

[37] Dourson, R. H., Sage, B. H. and Lacey, W. N., Am. Inst. Mining Met. Engrs. Tech. Pub. 1490 (1942). [38] Sage, B. H., Reamer, H. H., Olds, R. H. and Lacey, W. N.,

Ind. Eng. Chem. 34, 1108 (1942). [39] Velikovskii, A. S., Stepanova, G. S., and Vybornova, Ya I., Gaz Prom. (Gas Industiy) 9 No. 2, 1-6 (1964). [40] Savvina, Ya D. and Velikovskii, A. S., Gaz Prom. (Gas

Industry) No. 2 26, 1-6 (1957).

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