II III lliillili iiliiii III i III ifill II

NBSIR 75-763^

Thermodynamic and Transport

Properties of Ethylene and Propylene

D. M. Vashchenko, Yu. F, Voinov, B. V. Voityuk,

E. K. Dregulyas, A. Ya. Kolomiets, S. D. Labinov,

A, A. Morozov, I. A» Neduzhii (Principal Author),

V. P. Provotar, Yu, A. Soldatenko, E. I. Storozhenko,

Yu. I. Khmara

State Office of Standards and Reference Data

U.S.S.R.

June 1972

Final

\

I

Prepared for

Office of Standard Reference Data, NBS

\/oo

I 75"- 7^3

NBSIR 75-763

THERMODYNAMIC AND TRANSPORT

PROPERTIES OF ETHYLENE AND PROPYLENE

D. M, Vashchenko, Yu. F. Voinov, B. V. Voityuk,

E. K. Dregulyas, A. Ya. Kolomiets, S. D. Labinov,

A. A. Morozov, I. A. Neduzhii (Principal Author),

V. P. Provotar, Yu, A. Soldatenko, E, I. Storozhenko,

Yu. I. Khmara

State Office of Standards and Reference Data

U,S.S.R.

June 1972

Final

Prepared for

Office of Standard Reference Data, NBS

/ V ^

* 1—i,'^ f

•"•c.u o« '

U.S. DEPARTMENT OF COMMERCE, Rogers C.B. Morton, Secretary

James A. Baker, III, Under Secretary

Dr. Betsy Ancker-Johnson. Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Acting Director

Foreword

The thermophysical properties of ethylene and proplylene are of considerable

interest because of the widespread use of these compounds as starting

materials in chemical syntheses. The Office of Standard Reference Data

of the National Bureau of Standards, with support from a number of industrial

firms, has undertaken a program to establish definitive values for the

equation of state and thermodynamic properties of ethylene. As one of inputs

to this program, the book, "Thermodynamic and Transport Properties of Ethylene

and Propylene," has been translated from the Russian. This translation is

being made available to interested parties by issuing it as an NBS Internal

Report.

For further information on the ethylene program, please contact:

Dr. H. J. White, Jr.

Office of Standard Reference Data

National Bureau of Standards

Washington, D. C. 20234

THERMODYNAMIC AND TRANSPORT PROPERTIES OF ETHYLENE AND PROPYLENE

[Book; Moscow, Termodinamicheskiye i Transportnyye Svoystva Etilena i

Propilena , Russian, 1971, Standards Publishing House, signed to press 23 June

1971, 182 pages]

Table of Contents

Page

Preface 1 Symbols Employed in Manual 3

PART I. REVIEW AND ANALYSIS OF EXISTING DATA ON THERMOPHYSICAL

PROPERTIES OF ETHYLENE AND PROPYLENE

Chapter I. Thermal Properties of Gaseous Ethylene and Propylene 5

Review of Experimental Data on Density of Gaseous Ethylene

and Propylene 5

Analysis of Thermal Equations of State for Gaseous Ethylene

and Propylene 7

Thermal Equations of State of Gaseous Ethylene and Propylene 12

Review of Data on Second Virial Coefficient 25

Determination of Second Virial Coefficient of Ethylene and

Propylene According to Experimental Data on Speed of Sound . . 29

Determination of Second Virial Coefficients of Ethylene and

Propylene According to Compressibility Data. Recommended Values 32

Recommended Values of Specific Volume, Enthalpy, Entropy,

Isobaric Heat Capacity of Gaseous Ethylene and Propylene ... 37

Chapter II. Specific Volume of Liquid Ethylene and Propylene

Review of Experimental Data 39

Recommended Specific Volumes of Liquid Ethylene and Propylene. 45

Chapter III. Properties of Ethylene and Propylene on Saturation Curve 47

Pressure and Density of Saturated Vapor and Liquid 47

Heat of Evaporation 55

-a-
Critical Parameters 57

Chapter IV. Thermodynamic Functions of Ethylene and Propylene in

Perfect-Cas State 61

Review of Data 61

Recommended Isobaric Heat Capacity, Entropy and Enthalpy of

Ethylene and Propylene in Perfect-Gas State 67

Chapter V. Speed of Sound and Heat Capacities of Gaseous Ethylene and

Propylene 69

Review of Data on Heat Capacities of Gaseous Ethylene and

Propylene 69

Review of Experimental Data on Speed of Sound in Gaseous

Ethylene and Propylene 71

Recommended Thermodynamic Speeds of Sound, Adiabatics Index,

Heat Capacity Ratios and Isobaric Heat Capacity of Gaseous

Ethylene and Propylene 80

Chapter VI. Caloric Properties of Ethylene and Propylene in Condensed

State 85

Review of Experimental Data 85

Recommended Caloric Properties of Ethylene and Propylene in

Condensed State 95

Chapter VII. Viscosity of Ethylene and Propylene 99

Viscosity of Gaseous Ethylene and Propylene at Atmospheric

Pressure 99

Viscosity of Gaseous Ethylene and Propylene at High Pressures. 105

Viscosity of Ethylene and Propylene on Saturation Curve. . . . 109

Viscosity of Liquid Ethylene and Propylene at High Pressures . 115

Chapter VIII. Thermal Conductivity of Ethylene and Propylene 116

Thermal Conductivity of Ethylene and Propylene at Atmospheric

Pressure 116

Thermal Conductivity of Ethylene and Propylene at High

Pressures 123

Thermal Conductivity of Liquid Ethylene 129

PART II. TABLES OF THERMODYNAMIC AND TRANSPORT PROPERTIES OF

ETHYLENE AND PROPYLENE 130

Units of Measurements Used in Tables 130

Table I. Thermodynamic Properties p, v, i, r, s, C of

Ethylene on Saturation Line as Functions of Temperature. . . . 131

Table II. Thermodynamic Properties v, i, s, C of Ethylene . . 132

Table III. Specific Volume of Liquid Ethylene? 155

Table IV. Velocity of Sound w. Index of Adiabatics k^, Ratio

of Heat Capacities k of Gaseous Ethylene 155

-b-
Table V. Thermodynamic Properties p, v, i, r, s, of

Propylene on Saturation Line as Functions of Temperature. . , 160

Table VI. Thermodynamic Properties v, i, s, of Propylene . 161

Table VII. Specific Volume of Liquid Propylene 181

Table VIII. Velocity of Sound w. Index of Adiabatics k , Ratio

of Heat Capacities of Gaseous Propylene k.. 182

Table IX. Viscosity n'lO^ and Thermoconductivity X'lO^ of

Ethylene and Propylene on Saturation Line as Functions of

Temperature 185

Table X. Viscosity of Gaseous Ethylene ri^'lO^ and Propylene

ri2*10® at Atmospheric Pressure 186

Table XI. Viscosity n'lO^ and Thermoconductivity A«10^ of

Ethylene 187

Table XII. Viscosity n'lO^ and Thermoconductivity A'lO^ of

Propylene 189

BIBLIOGRAPHY 191

-c-
UDC 536. 7:547. 313. 2/.

3

ANNOTATION

This reference monograph contains tables of density, enthalpy, entropy,

isobaric heat capacity, heat capacity ratios, velocity of sound, index of

adiabatics, viscosity and thermal conductivity of ethylene and propylene in

the temperature and pressure ranges encompassed by the experiment. The tables

are preceded by a review and analysis of experimental data appearing in the

literature.

The book is intended for a large community of engineers, working on

problems of calculation, planning and operation of petrochemical industries.

It may also be of use to scientists investigating the thermophysical

properties of compounds and allied problems.

The monograph contains 76 tables, 227 bibliographic references and

23 illustrations.

Staff of authors: D. M. Vashchenko, Yu. F. Voynov, B. V. Voytyuk,

E. K. Dregulyas, A. Ya. Kolomiyets, S. D. Labinov, A. A. Morozov, I. A.

Neduzhiy (supervisor of the author staff), V. P. Provotar, Yu. A. Soldatenko,

Ye. I. Storozhenko, and Yu. I. Khmara.

-d-
PREFACE

This book is dedicated to the founder of the problem

laboratory of engineering thermophysics of KTILP [Kiyevskiy

tekhnologicheskiy institut legkoy promyshlennosti ; Kiev

Technological Institute of Light Industry] professor N. V.

Pavlovich.

The use of ethylene and propylene in the organic synthesis industry

and the high rates of expansion of the capacities of planned mass production

gas fractionation plants for ethylene and propylene production stimulated a need for the development of detailed tables of the thermodynamic and transport properties of these compounds, essential for technological calculations

in the planning of equipment and apparatus.

Previously published manuals contained thermodynamical ly contradictory

data on the various properties of ethylene and propylene for a narrow range

of temperatures and pressures, and often in a form unsuitable for use in

engineering practice.

An attempt is made in this work to systematize existing experimental

data on the thermodynamic and transport properties of ethylene and propylene

and to create thermodynamical ly concordant tables of these properties in the

temperature and pressure ranges that are of interest in technological

applications. The solution of this problem required the organization of

additional experimental and theoretical investigations of the properties of

ethylene and propylene, which were carried out by the authors in the problems

laboratory of engineering thermophysics of the Kiev Technological Institute

of Light Industry from 1963-1968.

The properties measured included the density of the liquid phase,

density of the vapor and of the liquid on the saturation line, isobaric

heat capacity of the liquid, velocity of sound in gaseous ethylene and

propylene, viscosity and thermal conductivity of ethylene and propylene,

and thermal equations of state of gaseous ethylene and propylene were derived

on the basis of more reliable data on compressibility.

-1-
Part One of the book contains a review and analysis of existing data

on thermodynamic and transport properties of ethylene and propylene, as well

as the results of investigations performed by the authors; the method of

processing data on the various properties and the method by which the tables

were compiled^ are described in detail.

Part Two contains tables of the thermophysical properties of ethylene

and propylene. The tables of the thermodynamic properties contain:

properties on the liquid-vapor equilibrium line in the temperature range

from 160°K to the critical point; specific volume, enthalpy, entropy and

isobaric heat capacity of the liquid at pressures up to 60 bar, of the

heated vapor up to 2,000 bar and 450°K; data on the density of liquid

propylene at pressures of 65-600 bar and at temperatures of 270-360°K; data

on the density of liquid ethylene at pressures of 70-500 bar and at

temperatures of 180-270°K.

Tables of speed of sound, heat capacity ratio and adiabatics index

are given for gaseous ethylene and propylene in the 210-470° K temperature

range at pressures up to 100 bar.

The tables of the transfer coefficients contain: data on viscosity

and thermal conductivity of ethylene in the 170-450°K temperature range at

pressures up to 1,000 bar (viscosity) and 3,000 bar (thermal conductivity);

data on viscosity and thermal conductivity of propylene at 270-450°K at

pressures up to 1,000 bar (viscosity) and 50 bar (thermal conductivity), and

also data on these properties of ethylene and propylene on the liquid-vapor

equilibrium line.

Chapter I was written by V. P. Provotar, S. D. Labinov and Ye. 1.

Storozhenko; section 1.5 of this chapter was written by Yu. A. Soldatenko

and E. K. Dregulyas; Chapter II was written by B. V. Voytyuk and S. D.

Labinov; Chapter III by Yu. F. Voynov and S. D. Labinov; Chapters IV-VI

by Yu. A. Soldatenko, A. A. Morozov, E. K. Dregulyas and D. M. Vashchenko;

Chapter VII by I. A. Neduzhiy and Yu. I. Khmara, and Chapter VIII by

I. A. Neduzhiy and A. Ya. Kolomiyets.

Yu. I. Khmara and Yu. A. Soldatenko contributed greatly to the

preparation of the manuscript.

The authors gratefully acknowledge N. A. Khanmurzinaya , M. E. Aerov

and V. A. Kulikova for their cooperation in the investigations and also

doctor of technical sciences professor V. A. Zagoruchenko for his review

and esteemed advice.

The authors invite the critical comments and requests pertaining to

the material in the monograph, and request that they be mailed to: Moscow,

K-1, ul . Shchuseva, d. 4, Standards Publishing House.

^The authors used literature data published prior to 1969.

-2-
I

SYMBOLS EMPLOYED IN MANUAL

B(T) -- second Virial coefficient in expansion in terms of density;

C , C -- isobaric and isochoric heat capacities;

p V

r '

f -- vibration frequency;

H°-H° -- change of enthalpy of compound in standard state from 0 to

T 0 ^ o^.

i -- enthalpy;

i^ -- enthalpy in perfect-gas state at temperature T, measured from

the crystalline state at 0°K;

I -- electric current;

k -- Boltzmann constant;

-- adiabatics index of real gas in equation;

M -- molecular weight;

p

-- pressure;

Q, q

-- heat;

R -- gas constant;

-- universal gas constant, equal to 8.3143 kJ/ (kmole'deg)

;

r -- heat of vaporization, linear distances;

S -- entropy;

S° entropy in perfect -gas state at temperature T °K;

T -- absolute temperature, °K;

kT

T* = reduced temperature;

t -- temperature on Celcius scale;

U -- voltage of electric current;

V, V -- mole and specific volumes;

w -- speed of sound;

-3-
1

Z = ^ -- compressibility coefficient;

A -- finite change of property, absolute error;

6 -- relative error;

£ -- depth of potential well;

ri -- dynamic viscosity coefficient;

a -- effective diameter of molecular interaction;

X -- thermal conductivity coefficient, heat of fusion;

7T = E reduced pressure;

Pk

p -- density;

T

T = — reduced temperature;

^k

T -- time;

cj)(r) -- potential function of molecular interaction;

C

K = ^ -- heat capacity ratio;

v

-- reduced density.

-4-
PART I. REVIEW AND ANALYSIS OF EXISTING DATA ON THERMOPHYSICAL

PROPERTIES OF ETHYLENE AND PROPYLENE

CHAPTER I. THERMAL PROPERTIES OF GASEOUS ETHYLENE AND PROPYLENE

Review of Experimental Data on Density of Gaseous Ethylene and Propylene

The works cited in Table 1 pertain to experimental analysis of p, v,

T-dependence of gaseous ethylene.

Systematic analysis of the density of ethylene was first done by

Amagat [1] . His work is now of historical importance only, despite the

rather high accuracy of 0.2-0.3% of the results, since more recent data are

now available [4, 5], distinguished by the maximum accuracy for the

contemporary level of investigations.

The experimental results [2, 3, 6, 12, 13] are fragmentary. The most

noteworthy among them are the data of Walters and coworkers [6] . Agreement

of the data of Walters and Michels falls within the range of error of

0.5-0.3%, as stated in [6].

Data on the density of gaseous ethylene and propylene at low pressures

are found in [11, 13]. The data of both works coincide, since they were

obtained on the same experimental apparatus. These works are of importance

in determining the second Virial coefficient.

In [7, 8, 9, 10] are found p, v, T-data obtained by means of graphoanalytical processing of experimental data. Dick and Hedley [8] did correct

smoothing of Michels' data [5].

Presented in Table 2 is a list and brief description of investigations

of the p, V, T-properties of propylene.

The compressibility of propylene was first subjected to systematic

analysis by Vaughan and Graves [17]

.

The pressure range was expanded to 700 bar by Farrington and Sage [18]

.

The accuracy of the experiment, according to the authors, is 0.3%. Data of

-5-
Table 1. List of Works Containing Data on the p, v, T-Function

of Ethylene

1)

ABTOpU

2) |3)n„:.

T. C

iian.T30ii UdD,ie>HU'\ ,1, 6ap

AMara [1] MeccoH 11 Ro.i.iH

(2]

/laiiiKviL II Cto.1l- ueiiocpr 1 3]

MHxe.-.bc II JIhcceii [4] Miixe.ibc II FejiAepMiJiic [5] Ba;ib repc ii ;;p. [6]

KpaMep [7)

linK 11 Xo;i.nii (8] Saropv'it-HKo

(9. '10]

Typ.lHHrTOII,

MauKeiTa [11]

ToMai: H UaiiAcp

|12J

Keira [13]

1P03

132o

ly29

19J6

1942

0-190

24,95

0—150

0—150

1954 !(_7)— ( 4-:

1955

1956

1959

19G1

19G6

1957

0-150

(-lOOj -

(4 300)

(--^.:0)-

(-1-301 0-50

32,2; 48,8;

(18,9

-100

-125

21—202

20-70

16—3000

3—40

1—2500

0,5—20u0

0,5—1.5

0—2i 1—2

[li

|2]

[3]

[li]

|14J

}

ni):'C'

i i ) 06pa6oTKa

,aaiiubix >Ke

'ler no

y]?aBiieHHio

COCTOMKIiq

[15]

[16]

[15]

^1

I .orpruiiPCTb

ICTOxa HCCJieAOBSllHOl '> ra3a, %

AT ^ 0,PC

Av 0,5%

Ap T--. 0,1 Cap

0.01%

0.01 %

0.5%

0.1 ?6

0.1%

97.8

11)

N,-0,2; Apyrue raau 0,2

99.9

KEY: 1. Authors

Amagat [1]

Mas son and Dolly [2]

Dannell and Stolzenberg [3]

Michels and Niesen [4]

Michels and Geldermans [5]

Walters, et al [6]

Cramer [7]

Dick and Hedley [8]

Zagoruchenko [9, 10]

Turlington and McKetta [11]

Thomas and Zander [12]

Pfennig and McKetta [13]

2. Year

3. Temperature range T, °C

4. Pressure range p, bar

5. Method

6. Error

7. Purity of investigated gas, %

8. Data processing

9 . Same

10. Calculation by equation of state

11. N -- 0.2; other gases 0.2

Marchman, Prengle and Motard [19] coincide with an accuracy of 0.3% with data

of Farrington and Sage. Results of Vaughn and Graves for low pressures agree

satisfactorily with Marchman 's data. At high pressures, however, deviations

reach 1-2.7%.

Michels and coworkers [21] published data in the 0-150°C temperature

range and 6-2,800 bar pressure range. The error is 0.03%. They investigated high-purity propylene.

Data [17, 18, 19] at pressures to 20-30 bar coincide with Michels'

results within 0.3-0.5%. At higher pressures the discrepancies reach 3-3.5%.

-6-
Table 2. List of Works Containing Data on the p, v, T-Function

of Propylene

1)

AuTOpbl

Boyrc-ii h Ficw: j 17j

ffcappHHrxoii II Cci'f.iiiv \\S]

'>\ap4Maii, [Ijx'Kr.'ib, A\oinp;t

(19]

Kam.-'^p, fo,'i;iMcin. Alaji'i- Mair(201

Miix-'^.ii.c ii roTpyjiiiiKii [21 | n4)t'HllHr, AiaKKCTTJ (]3|

KaHbnp H coipyvmnKi; f22J

ilHir.iap 11 Cly;ibu

1 o.; cnyb:iii>i II

3;

ii'Mii'.p-'ryp /. -(.;

:!0

19;

I0i;3

0—300

\WJ I 4—?82

30—2o0

(—10) -

(+200)

3—150

32,2; 48,.'!;

.'13 ll.^i 'M .1 i u. oaf)

1962 100,110,120,

I 130.140

5)

A\i'To;; ;i-,cne-

-SO -689

0—215

[17]

118]

(24)

1—200 ^) Po^iier no

ypabiiciiiiio C0CTO;ililIH 6—2830 1 15) 1—2 |23j — ^ ) OupafxjTKa

GO— 1000 i —

pcLUliOCTb,

icTora

Baiiiioro rasa. %

10,3

0,25

0,03

0,1

0)-

npiiMecefi

0,11

99,7

99.7

KEY: 1. Authors

Vaughan and Graves [17]

Farrington and Sage [18]

Marchman, Prengle, Motard [19]

Michels, et al [21]

Pfennig and McKetta [13]

Canjar, et al [22]

Ditmar and Schultz

2 . Year published

3. Temperature range T, °C

4. Pressure range p, bar

5. Experimental method

6. Error, %

7. Purity of investigated gas, %

8. Calculation by equation of state

9. Data processing

10. Impurities

Published in [20] are data obtained by calculation according to the

Benedict-Webb-Rubin equation, the constants of which were determined by

Marchman on the basis of experimental data.

It follows from the above review that highly accurate experimental

data exist for gaseous ethylene and propylene in a rather wide pressure

range, but in a narrow temperature range of 0-150°C. Experimental data

[6, 11, 13] for ethylene can also be recommended as reference material.

The range of the gas adjacent to the right boundary of the curve is not

experimentally investigated.

Analysis of Thermal Equations of State for Gaseous Ethylene and Propylene

Numerous equations of state, derived on the basis of existing

experimental p, v, T-data for ethylene and propylene, have been published

in Soviet and foreign literature.

The constants of the Benedict-Webb-Rubin (B-W-R) equation are given

in [23, 25, 26]. In addition, Michels' equations of experimental isotherms

are given in [5, 21]. Most recent are V. A. Zagoruchenko ' s equations of

-7-
state [9, 27] and those o£ Ya. Z. Kazavchinskiy and V. A. Zagoruchenko [28].

The Martin-Hou [29] and Bentzler [30] equations are used to a lesser extent.

The equations of state describe the p, v, T-surface of ethylene and

propylene with various accuracy, depending on the pressures and temperatures

Tables of reference data were compiled on the basis of the experimental data

of Michels [5, 21] and Walters [6] for analysis of these equations, and were

later used for checking the equations with the computer. Calculation

results are presented in the form of nomograms in Figure 1.

The region encompassed by the experiment is cross hatched in the

nomograms. The area of the nomograms is divided into regions by pressures,

in which they are given with a constant step. The mean and maximum deviations of the experimental and calculated data are stated on the isotherms

for each region, as are the average deviations for the entire region. The

measure of deviation is the relation

6 = ^^^P " ^^^^^

. 100%.

p^exp

The B-W-R equation (Figure la) can be used with confidence with a mean error not exceeding 0.1% for interpolation of the p, v, T-properties

of ethylene to a pressure of the order of 20 bar at temperatures of

270-440°K. Here the maximum deviation does not exceed 0.2%. The maximum

deviations occur in the region next to the saturation line.

The B-W-R equation describes the p, v, T-properties of propylene

(Figure lb) with lesser accuracy, but at pressures up to 10 bar the maximum

deviations are 0.3-0.4% and the mean deviation for the given region of

parameters is 0.19%. In the 10-100 bar pressure range the accuracy decreases

the mean deviation for the given region is 0.74%, whereas the maximum deviation near the saturation line is 5.5%.

Zagoruchenko ' s equation [9] for ethylene quite accurately describes

the p, V, T-data (Figure Ic) in the 1-200 bar pressure range and 270-400°K

temperature range, where the mean error does not exceed 0.2%. Here the

maximum deviations up to a pressure of 20 bar fall within the limits of 0.2%.

At higher pressures (300-1,800 and 1,500-3,000 bar) the mean deviation for

the region is 2-3%, i.e., substantially exceeds the experimental error. The

equation may be used for calculations in the 1-200 bar pressure range and

270-400°K temperature range.

The Kazavchinskiy-Zagoruchenko equation [28] (Figure Id) should be

considered unsuitable for describing the p, v, T-function of propylene,

since it gives deviations exceeding the error of experimental determination

of the p, V, T-data in the entire range of parameters (p = 1-3,000 bar and

T = 270-440°K).

-8-
1)

2)

1) -.^

2)

1)

2)

1)

2)

1)

2)

1)

2^

ICO

2)

1

) loon

2)

/\ ^ 0.035

• ','/ ^ , .' / ^ / /

Z/////y//////, //

/ ///////.// // . /.

y///y/y////7///. '//// -e.^ ^///

JOOO

KEY: 1) Mean deviation

2) Maximum deviation

r, °K

0

w

—[ ' 151

'\ '1 -1 1

_ / / / //

—y—7—7

llllij-irMSiiiMIlIli

1)

2)

1)

2)

1)

2)

1}

2)

1)

2)

Figure 1. Field of errors of thermal equations of state for

ethylene and propylene: a -- field of errors of the BenedictWebb-Rubin equation for ethylene [23, 25, 26]; b -- field of

errors of Benedict-Webb-Rubin equation for propylene [23, 25, 26];

c -- field of errors of Zagoruchenko' s equation for ethylene [9];

d -- field of errors of the Kazavchinskiy-Zagoruchenko equation

for propylene [28]; e -- field of errors of Zagoruchenko ' s equation

for propylene [27]; f field of errors of Zagoruchenko' s equation

for liquid propylene [27] ; density and equation of state of gaseous

phase. [Continued on next page].

-9-
r,°K

Figure 1

.

[Continued on next page]

-10-
Figure 1.

The Zagoruchenko equation [27] (Figure le) should be considered most

accurate for propylene. Its maximum deviation in the near-critical region,

however, reaches 3.8%. Here the path of the isotherm in p, v-coordinates

does not correspond to the path of the experimental isotherms in the supercritical region. Equation [27] describes the range of the liquid state of

propylene (Figure If)

.

-11-
It can be concluded on the basis of analysis of the existing equations j of state of ethylene and propylene that none of the examined equations i describes the experimental data in the entire, rather wide pressure range.

The authors of this reference manual, therefore, attempted to derive equations of state for the entire gaseous range, for which experimental informa- i tion exists for the p, v, T-data of ethylene and propylene.

Thermal Equations of State of Gaseous Ethylene and Propylene j

Several methods are now being used [31, 32, 33] for formulating the

equation of state on the basis of experimental data using polynomial

theories. Approximation of the p, v, T-plane with the aid of orthogonal

polynomials, as shown in the work of Pings and Sage [31], has certain

advantages over other methods.

In the usual method of least squares the matrix of the linear equation

system is usually poorly defined. The situation gets worse as the degree of

approximation of the polynomial and the number of experimental points used

for the approximation increase. In view of this the matrix inversion operation leads to considerable difficulties in the calculations.

When orthogonal polynomials are used the matrix becomes diagonal and

the inversion operation is obviated.

The use of orthogonal polynomials increases the power of the

approximating polynomial without repeated calculation of the coefficients,

which were determined earlier for a lower power. However, the use of first

and second order Chebyshev polynomials [31] for the given problem involves

certain inconveniences. Specifically, the experimental data must be represented as a special matrix, where the roots of the stated polynomials are

taken as the nodes of approximation, and this entails graphic processing of

the data, which inevitably leads to loss of accuracy.

The essence of the proposed method of approximation consists in

application of the Forsythe algorithm [34] to the case of the function of

two variables. The advantage here is that it is not necessary to use a special lattice for representing the experimental data. If f(x, y) is

integrable with weight R(x, y) in rectangle a<_x<_b, c<_y<_d, then to

it can be compared the Fourier series

fix. y) = EQfcO),fe(.v. y), (1)

, i.k

where

oXkix, ij) - fPi(x)Mf^ (ij), ^2)

and (j). (x) , ^, (y) are the orthogonals in the intervals a < x < b and c <_ y <_ d,

1 K

respectively.

-12-
to —

T l ."3 O

O O (>J (M O C o o

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-13-
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I I I I I I I J I I I

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CO r~ o lO o r: r -•• x cT/ c-i x ci -r c; n » oo — ^ to — "-^ co o o ci — o o co oocr>C)Oc-:.~-ri— ox — o — x-c^rcMiTi^'MCMor^iO'Ocix-ox-rro — CO o — X CT) c J r. c~. — t~- c-1 CI I ~ I - I J -r cr. — 'O — >ir X -r -?• -o CM — CO 00 lO

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CO c^j CO CO CO rc C-"; ^ *r T' vr ^ ^ ^ ^ to 1^./ lO lO lO lO uO LO lO lO U3 O <0

-14-
The system of orthogonal functions 0^(x) is constructed in the

examined range of change of the argument by means of orthogonalization of

the system of power functions 1, x, x'^, ... with unit weight.

The polynomials (})^(x) satisfy the recurrent relations

(Pi = a; -f a?

(P2 = 4- rti) (pi 4- G2(po (3)

<p3 = (-»^ + al) ^>2 + alfpi

where the coefficients a* and a° are determined from the conditions of

orthogonality

((()., 4).) = 0, if i (4)

The condition of orthogonality of polynomials <t>^ is determined on the

discrete set of values of the argument x. Such a set, in particular, may be

temperatures at which the experimental investigations were conducted.

The coefficients a^ and a° of the polynomials (J)^(x) and ^j^Cy) are

thus defined by the equations:

1=1

A'

The coefficients C^j^ in equation (1) are determined from the condition

of the minimum mean square deviation of series (1) from the function f(x, y)

M.N

Vx2Si.p ^ mill, (7)

m,n

where 6 . = f(x , y.) - S C oo., (x , yo) ; m, n are the maximum powers of

0(, , p Ot p .1 IK IK Ot p

1 ,K

-15-
the expansions in terms of the variables x and y, respectively; M, N are the

numbers of values of the arguments x and y, respectively, according to which

the orthogonal functions cj>- (x) and \ (y) are constructed.

— 2 V [/ {Xa, IJ?^) — V C,,a),; [Xa, (Oj-fc (Xa, ^Tp) = O',

f'.h' Af.A'

a,P a.H

o/t = —

(8)

M.N

2

a.P

In our work the variables were selected as follows:

y T

fix, y) = {-^f-\]v (9)

The program that executed the described algorithm was written in the

command system of the BESM-3M computer^.

To calculate the coefficients of the polynomials and C^^^ we

used experimental data of Michels [5, 21], presented in Tables 3 and 4.

Table 4. Michels' [21] Experimental Data on Propylene

f(x, y) -(•If-')';''"

p. li£,lM' Date for T, °K

..l.''..i6 323,15 348,15

12,4233

15,9476

19,4701

23,1491

37,5319

31,0289

35,0957

37,3n27

43,9004

—0.008 1-: 2040 —o.oo'ii 1 ;'i05 —0,0nM}s7200

—0.00805: 670 —0,no.>022750 —0.0(!7'J871()0 —0,00: 954700

—0.007943500

—0.007888800

—0,007059020 —0.0070 U'lOO —o,cu;o;)0,:90 —0,006':'6kI)50 —0.00u-.'29450 —0,006.s:'0240 —C.0078o20IO

—0.00'i8 12220

—0,006/82570

-0.006824940

—0,006795350

—0.006762940

—0,006727450

—0,006683050

—0.006638430

—0,006612500 —0.006581410

—0.006524020

—0,005757110

—0,005761340

—0,005733210

—0,005698640

—0,005657940

—0,005616470

—0,005585090

—0,005561000

—0.005492450

[Continued on next page]

The authors gratefully acknowledge the cooperation of S. A. Mednikova of

the NIIASS [Nauchno-issledovatel • skiy institut avtomatizatsii sistem

planirovaniya i upravleniya stroitel 'stvom; Scientific-Research Institute of

Automation of Construction Planning and Control Systems] , Gosstroy

[Gosudarstvennyy komitet po delam stroitel ' stva ; State Committee for

Construction] Ukrainian SSR in the writing of the program.

-16-
Table 4 (Continued)

Data for T . °K

p. Ki/.ll-' JV3.15 423.15

12,4233 —0,001962120 —0,004290550 —0,003732490

15,9-'. 76 —0,004940160 —0.004270200 —0,003711970

i9,;701 —0,004915570 —0,004247620 —0,003688400

23,1-191 —0,004885230 —0,004220770 —0,003663540

27,5319 —0,004847380 —0,004186510 —0,003632940

31,0289 —0,001809250 —0.004154600 —0,003600700

35,0957 —0,004779940 —0,004124790 —0.003574840

37,3027 —0.004760250 —0,004106960 —o!o03558860

43,9904 —0,004694800 —0,004047790 —0!003506590

52,8920 —0,004610220 —0,003971950 —o!0O3438I98

61,5180 —0,004527-1 :50 —0,003898150 —o!o03371820

70,6220 —0,004439900 —0,003819860 —0i003302120

79,6525 —0!004353160 —0,003743200 —o!o03233700

81,0886 —0.004339190 —0,003730270 —0^003223200

88,3320 —0,004269306 —0,003669145 —0!o03 167406

90,4061 —0.004248 <70 —0,003650646 —o!o03 152033

97,4213 —0,004180899 —0,003591424 —o!o0.3098313

100,6545 —0,004149677 —0,003563372 —0'003074903

110,4019 —0!004055528 —0,003480733 —o!c0.30 13851

120,88G9 —0.003954789 —0.003392546 —0,092923342

126,7396 —o!oC3898SG7 —0.003344120 —0,002879851

130,4939 —0.00386.-!2 ".4 —0.003313040 - -0.002852312

140,6308 —0.00.4/67124 —0.003230031 —0,002778148

141,3968 —0,003 759! 130 —0,00322.(810 —0,092772800

150,8833 —0,003671041 —0,003147013 —0,002704459

157.32C2 —0,00361 1516 —0.003095750 —0.002658556

172,5556 —0,003472976 —0.002976295 —0,002551512

183,1000 —0.003379121 —0.0028'. K'..} 4 8 —0,002478264

188,9419 —0.003327957 —0,00-.'851226 —0.002437862

203,9584 —0.OU3199102 —0,002739256 —0,002335080

204,2748 —o!o03196U,6 —0,0027:;6923 - 0,002332858

2)9,8116 —o!oO306S]Ol —0!c02f'i2.i556 —0,002274196

227,2808 —o!o030C0793 —0.00256903S —0.002176840

235,fc269 —0,002940571 -0,00250.Vi7l —0,0021 19053

2-.' 9,2921 —0!0028.372:'6 - -0!o024 13168 —0,002027679

272.9678 —o!o026626i6. —0,0022-16114 — 0,001864452

277,1274 —0,0026325-19 —0,002217066 —0,001835143

291,6654 —0,00250727

1

—0.002091 136 —0,001708965

309,1 ?09 —o!oo2--02.- -:2 —0.001981736 —0,001599899

311,3877 —0',0023e69.'-'« -0,001968078 —0,0015830.50

317,5738 —0,00234 19._ 9 --0,001 92 O.SOO —0,001534271

340,7207 —0[002 166257 —0,001734836 —0,001341329

3-14,0120 —0.002 13f)S',)4 —0,00170714.1 — 0,001312372

347,41 15 —o!o02l 12652 0 001677987 - 0,001281994

377,3512 —0.001847991 0 00 1 3'^15'^06 —o!o00986096

- 386,5670 —0,001 7566' i9 —0 001297730 —0,000885584

402,2800 —0 001586016 0 001 1 17*^88 —0.000698908

4 1 3,2332 —0,001455716 —0 0009.^'0'^0'> —-o!o0055666!

424,0634 —0,00!31627(j 0 000iS3427'> — o!o004071 16 446,1533 —0 000993O'^7 —0 00049^69'? — 0 000064«50

448,9080 —0 00094 Ol io 0 00015.1476 0 coo 196579

464,4563 —O.O0OG82212 —0,000181321 —0,0002.57318

480.9735 —0,000363010 —0,00914230:.! —0,000583.351

499,7097 —0.000048175 -0,000555590 —0,000998587

501.5707 —0.0000921 14 —0,000599570 —0,001041855

516,2530 —0.0C0459127 —0,000965308 —0.001404222

540,9137 —0,001181318 —0,001661405 -0,002031397

548,5700 —0,001401^07 —0 0018"S789 —0,002324141

580,9129 —0.002558v!(i --0,003027422 —0.003427535

601.5930 —0,00341870! —0,003863837 —0,004238065

650,9040 —0,005905562 —0,006264682 —0,006556777

-17-
The equation of state is written in the form

from which it is easy to convert to the Virial form by reduction of like

terms

.

The conversion to the Virial form is provided for by the program and

is executed after calculation of the coefficients of the polynomials (j)^ , ip^^ and coefficients C, . ik

In the theory of approximation of the functions of two variables

there is no explicit criterion for determining the optimum number of powers

of the expansion with respect to each of the variables. Therefore the

optimum power of the expansion in terms of 1/v and 1/T was found as a set

of powers. Here the deviations at the points and the minimum sum of squares

of deviations were the criterion.

Equation (10) is written in Virial form as

ri , ;j -w-^'^'lvl'^^'yTj' (11)

This method requires a rectangular network of experimental data. For

this reason the field of p, v, T-data of propylene is broken down into two

regions, for each of which is constructed an equation of the form (11).

The constants determined by the above-described method for the equations are presented below.

Ethylene iP = I — 3000 bar. T - 250 —450° K)

+ 0,760072429 C02 — 0,548705429 • 10-'

Cu — 0,134563818 • 10^ C12 -\- 0,972058755 • 10'-

c„ + 0,9500G:)6 IG • 10" C22 — 0,686258650 • 10=^ — 0,331667515 • lO'' C32 -i- 0,2 11393035 • 10*

C41 + 0,587269730 . 10" C42 — 0,423108315 • 10'"

C51 — 0,410898360 . 10'^ C52 -1- 0,295678870 • 10'=

Co3 + 0,132142978 . 10-^ Coi — 0,144380734 • 10""

C,3 — 0,233803377 10' Cu + 0,255267906 • 10-'

C23 + 0,164875060 . 10" C24 — 0.179881158 . 10^

C33 — 0,579326847 10' C34 + 0,631603632 • 10"

[Continued on next page]

-18-
C43 + 0,101441262 • 10' C44 — 0.110517516 . 10'

c„ — 0,708228885 • 10'° C54 = + 0.771067345 • 10^ — -1- 0,831940857 • 10-' = —0,269842664 • 10-'

Cl5 = — 0,147018406 . 10~^ = + 0.476717255 • 10-^

C25 + 0,103550508 C26 — 0.335666604 • 10"^

C35 — 0,303412433 • 10' C36 + 0,117765335

Q5 + 0,63558120,0 • 10^ C46 — 0,2055894276 • 10'^

Cos = — 0,443212965 • 10' C56 + 0,143526876 • 10^

+ 0,494436598 • 10-'^

Cos — 0,476946020 • 10-'^

C,7 — 0.873357290 10-' C18 + 0,842422128 • 10-'^

C27 + 0,614844932 • 10-' C2S — 0,593032017 • 10-'

C37 — 0.215673041 10-"^ C3S + 0,208007008 • 10-^

C47 + 0.376996322 • 10-' C48 — 0,363565579 • 10-^

C57 — 0.262743658 10' + 0,253357565 • 10"^

+ 0,188031735 • 10""* — 0,332130351 • 10"'^

+ 0,233813590-10-'^ — 0.820120622 • 10"'°

+ 0,143345912 • 10"^ — 0.998924485 • lO""*'

Propylene. (T = 270 — 450° K, p - I — 30 bar)

Coi = —0,396637152

Cn - + 0.678436327

Cn, = — 0,463021591

C31 = +0,157557275

C41 - —0,207451170

Cc,, = +0,181147750

Co3 = —0.634256919

Ci3 = +0,109085668

C23 = —0,748515689

C33 = +0,256142088

[Continued on next page]

Co9 =

^19 =

C29 ===

C40 =

r C59 =

10' C02 + 0.860745715

10^ C12 — 0,147721665 • 10^

10^ C22 + 0,101 148055 10^

10'° C32 — 0,345410258 • 10'

10'^ C43 + 0,588277177 10"

10'^ C52 — 0,399749543 • 10'^

10-' Co4 + 0,189023628 • 10-

10^ Cm — 0,325404985 • 10'

10^ C24 + 0,223489403 • 10"

10^ C34 — 0,765471148 10^

-19-
'43 0.437127355 • 10

10

n.891 006876- 10

CiA = -[- 0.130749631 • 10

Cr,-. - 4- 0,297025345 • lo'^ C51 -

< „r. — (I, I ') in I / I ill

Ci5 - -1- 0.3342;:G852 •

C25 = —0,229744935 •

C35 = + 0,787500243 •

C45 = —0,134615528 •

C55 - + 0,918055308 •

Propylene {T = 370 — 450=^ K, p

!0

10

nr

10^

10^

10^

10^

1 — 3000 bar)

Coi = 0,65985925 • 10"-3 ^02 ~ -f- 0,440437102 • 10"-4

Cii —0 1076759'^7 Co012 —— n 3-13n'^77'^7 .

1 u

-1

—0,761754943 • 10' ^22 — + 0,758758270 • 10'

Cos = — 0.7078394G2 10--6 Co4 ~ + 0,199772917 • 10"-8

c, - -f 0.586824620 • 10" -3 Cm- — 0,202807342 10"-5 — 0,1 14054261 C24 - 4- 0,433482162 • 10"-3

Cos ~ + 0,238533263 10"-11- Cog — 0,169756637 • 10"-12 — 0,166153171 10"-7 ClG -= + 0,129786612 10~9

Ct.^ -1- 0,309699415 10"-5 C2r, — 0,255484795 • 10"-7

Co7 - -t- 0,434039867 10"-IF) Cos = — 0,500738055 • 10"-IS

C,7- — 0,340025191 • 10^ 1? C18 — -f 0.396632938 • 10"-15

C27 + 0,680235151 10"-10 C2S — 0,799576203 • 10" 13

CoJ — + 0,2 1S934207 • 10-^'

Co9- —0/174502194 10"

C29 - -h 0,3532Gi;277 • 10

-18

-IG

The deviations at the points, i.e., the differences between the

experimental values of f(x, y) and those calculated according to the equations, are listed in Tables 5 and 6.

The. mean pressure deviations on the isotherm

6 = calc

100%

exp

in the entire region of states covered by the experiment on ethylene [5] and

propylene [21], are found within the limits of 0.1-0.2%.

The proposed method of writing the interpolation equations of state

is suitable for the description of the p, v, T-data in wide temperature and

-20-
4-> UJ

<4-l o

0

!-> nJ

+-> c/5

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•p

tu

<4-l O

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tJJ

<4-l o

X)

1—

I

<D •H

tL.

LO0

r-Ha

o

+->

X

5 'r^

03

X

X

II

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-21-
lO k^' ifi O tQ o o o

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I -22-
Table 6. Field of Errors of Equations of State of Propylene

A = f(x, y) - ffx, y) ^

Field of errors at T°K

1 298,15 318.15 323,15 348,15

12,4233 —0.1228- 10 0,1646- 10

-5 —0,16i9- 10 -5

0,1639- 10-^

15.9476 —0,2798- 10~^ —0,3097.10"-6 -0.8453-10' -6 —0,1853- 10'-^

19,470! —0,1861 - 10"" —0.5650- 10"-G 0,1120-10--6

0,9076 1Q-.6

23,1491 —0 2773- 10""^ —0,8692 -10'-0 0,8404-10'-6

0,7853- 10~^

27,5319 -0,6705-10"'^ —0,2363- 10"-5 0,3370-10'—5 —0,1737- 10-5

31,8333 —0.8757.10-'^ —0.3182- 10" 5

0,7404-10"-5 —0,3007 10-5

35.C9j7 —0,4300-10"'^ —0,5021-10"- 5 -0,3086-10"-5 —0,3934 10-5

37,3027 —0,2065- 10"^ —0,5360 • 10"-5 —0.1336-10"—

1

—0,1790- lo-"^ 43,9904 —0,4020- lO'-'^ —0.4503- 10"-5 0,5282-10'-5 —0,3010- 10-5

Field of errors at T°K

p. kz/m'

373.15 398,15 423.15

•

1-2,4233 0.79 1 1

- 10 0,6272-10-5 — i

0,2813 - lO-''

15,9476 0,1294 10-5 0.9871-10-^ —0.4811-10-^

19,4701 —0,2884 10-5 —U,ZijU/ • lU —U.oo/0- I (J 23 1491 —0,3525 10-5 -- 0.3374-10-5 —0,1328. 10-5

27.53)9 - 0,3401 10-5 —0,3160.10-5 —0,2598. 10-5

31,8333 —0,3070 10' "5 —0,2392- 10-5 -0.1714-10-5

35.0r'57 —0.2886 10-5 —0,1900-10-5 0.4553- 10-^

37.3027 -0.3101- 10-5 -0,2057- 10-5 -0,4118-10-5

43,9901 0,1126 10-5 0.1826- 10-5 0,4506-10-5

52,8926 0,2479 10-5 0,2643- 10-5 0.1903-10-5

61,5480 0,2901 10-5 0.2433- 10-5 0,1737-10-5

70,6220 0,2996 10-5 0,2490-10-5 0.1434-10-5

79,6525 0.2006 10-5 0.104 1-10-5 0.3246- 10"-°

81,08,<::C- 0.1982- 10-5 0 1549-10-5 —0.2028-10-5

88,3320 0.1082- 10-5 0.9312- 10-'

0,1 135 -10-5

90.4661 0,1274- 10-5 0,1894-10-^' —0,7566-10-'^

97,4213

0,8191- 10-'' —0,3980- 10-*^ 0,1583-10-"^

100,6545

0,4894- 10-*^ —0,4531 -10"-^ —0.8486- lO-*^ 110.4019

—0,2582- 10"-^ —0,1114 10-'' —0,1286- 10-^

120.8863

—0.9827- 10-5 —0,5099- 10-'^ -0.1370- 10-'

i:'G,73fj6

-0,1326- 10-5 —0,8635-10-'' —0.6104-10-"'^

130.4938

-0,1G09. 10-5 —0,3029. lO'-*' —0,8057-10-5

140,6366

—0,1764- 10-5 —0.9755.10-'^ —0.1737-10-5

141,3965

—0,1733- IU-5 . —0,9309-10-'' 0.1655-10-5

[Continued on next page]

-23-
Table 6 (Continued)

Field of errors at T °K

373, 15 398.15 423. 15

1 OOO 1 loO.oooI A AO^Q I ft—

6

0,2362-10

l5/,3202 —u,iDiy- JU A AAOO 1 A—

—u,ouoy- JU 0,2805-10 ^

1 1 2,555o —u, J o^y • lu A TOAO 1 ft —

S

0,3470-10 "

183,1002 —u.cDDo- JU A o^ni 1 ft—

0,3958-10

j8o,y419 —U,<jDoo- JU ft 1 fi^^S 1 ft—

0,4299- IQ—

203,95o4 U.oU/^- JU ft I ft—

0,4730-10 ^

204,2/48 n 4Q70 in

^ A QJ ft a 1 A—

7

0,4802-10""^

219,81 14 u.i^oy • JU U,0-i-t / - 1 U 0,4187-10

227,2805 A 1 AC7 1 n—

U,Iuo/ • JU A fit o I in—

6

0,4859- lO""^

235,8269 U,<iUoZ • J U ft fiQft^ 1 ft

^ 0,4575-10—^

249,29.'?4 (\ 01 4/1 1ft—

U,zl4fl-JU ft 874Q. in~'' 0,4100- IQ—^

272,9678

A 1 000 1 ft—

ft =iS77. in~''^ 0,25/6-10

277,1274 ft 1 1 fij . 1 ri~^ 0 37'18- 10""^ 0,2441-10

294,6654 A OOC^l 1 ft —

U,401 U * I u A f^f^OO I A*"--* U.UDZj- lu

309,1809 —0,1 140-1

0~^ —0,7522- 10"^ A OA*?! 1 A—

O

0,2071-10

311,3877 —0,1411-10-^ —0,7704-10-* —0,1153-10-^

317,5738 - 0,1860- ]0~'' —0,7825-10"'' —0,1796-10-^

340.7294 —0,2633- 10--' —0,1147.10-^ - 0.9285-10-^

o4-i,UlZ>J —0,24S5-

10"^'' —0,1423- 10~^ —0,1152-10-^

—0,2595- lO'

"'" -0,160-!- 10""' —0,1100- 10—'

—0,1209- 10^^ —9,101 ?- 10~" -0.9384-20-'' —(),77l)9- 10"^ —0,7607- 10~* - 0,8559-10-^

—0,1006- 10"- 0,8753-

10""'' —0,5512-10-^

0 1G70- '0~^ 0 3783- 10""'' 0.2490-10"^

4 9.1 n'i3-1 0 1943- 1 0"'' 0,5329- 10 —0,9963-10-' »

44G 1533 0,2698- 1.0" ^ 0,1291 - IQ—

0,9934-10—^

148 9C80 0 2373- 10""^

0,1 132- 10""^ 0,4231 - IQ—

''64 4563 ft 1504- ]0~^ 0 I l.jjj- 10~^

0 3018-10—^

480,9735 —0 2317-10"''' 0 5790- lO"*^ 0 3882- 10—'

499,7094 —0,2829- 10~'^ ft 3955- 0 1 190- IQ—

501,5701 —0,3039-10"-^ -0,3187-10-'^ 0 6349- IQ-

515,2524 —U,4 / 1 y i U —0,bJ2J- 10 —0,7662- 10-^

fiiD 0 1 97 —0,1281-10—' —0,5311-10-" —0,2803-10

548,5700 —0,6549-10-^ —0.1031-10-^ —0, 1196- 10-^

580,9)29 —0,2958-10-'' —0,5599- 10-^ 0,5977-10-'

001,5949 0,2528-10-^ 0.1579- 10-^ 0,5894-10-^

650,9030 —0,3294-10-* —0,309-1-10-^ —0,9953-10-^

-24-
pressure ranges with an accuracy close to the error of the experimental data,

and can be used for the construction of tables of the thermodynamic properties .

The high accuracy of description of these data by the equations

derived ensures the required accuracy of calculated caloric values.

Review of Data on Second Virial Coefficient

The Virial form of equation of state is now considered theoretically

founded. Despite the difficulties encountered in the extraction of the

Virial coefficients of the equation of state from various types of experimental data, several methods have been worked out in recent years for

derivation of the equation of state in Virial form.

Data on the second Virial coefficient of ethylene, published by

various investigators, are presented in Table 7 and Figure 2. As seen in

Figure 2, the existing data display considerable scattering. Data of

Roper [35], Turlington and McKetta [11], Pfennig [13], Ratzsh and Bittrich

[36] , were obtained from measurements of compressibility at low pressures

(to 2 bar)

.

Figure 2. Second Virial coefficient of ethylene according to

the following data: 1 -- authors of present book (from data

on compressibility) and of Michels [5] ; 2 -- Roper [35] ; 3 -- Walters and coworkers [6]; 4 -- Thomas and Zander [12]; 5 -- Pfennig and McKetta [13] ; 6 -- calculated according to the

Leonard-Jones potential [25]; 7 -- Turlington and McKetta [11];

8 -- Pfennig [13]; 9 -- Ratzsh and Bittrich [36]; 10 -- calculated according to the Corner potential [38] ; 11 -- David

and Hamman [39] ; 12 -- authors of present work (from data on

speed of sound) ; 13 -- Butcher and Dadson [37] ; 14 -- calculated by equation [33]

.

I

-25-
Table 7. Second Virial Coefficient of Ethylene According to Various Data

Ponep 1 35]

200.00

210.00

220,00

230,00

240,00

250,00

260,00

270,00

298,15

323,15

1,10029

1,00752

0,925809

0,853511

0,789237

0,731862

0,C80H3

0,634182

0,526397

0,451925

2) TypjiHHfTOH II MaKKCTTa [11]

243,15

258,15

273,15

288,15

303,15

3)

305,35

310,95

316,55

321,95

327,55

333,15

338,65

n(f)CH!inr [13]

0,6672

0,6358

0,5984

0,5019

0,5019

0,5002

0,4775

0,4630

0,4473

0,4312

0,4190

0,4081

4) Perm ii 5nTTpnx (36)

293,15

303,15

313,15

323,15

0,5205

0,4812

0,4492

0,4070

5) Ba.ibTepc h ,ip- [6]

244,26

249,82

255,37

260,93

265,43

272,01

277,59

283,15

0,7830

0,7481

0,7 i 18 0,6836

0,65-10

0,6269

0,6013

0,5770

6) RSBHA i XCMMCH (39)

250,00 0,5846

290,00 0,5490

300,00 0,5098

310,00 0,4741

320,00 0,4420

330,00 0,4099

340,00 0,3779

350,00 0,3518

400,00 0,2524

7) MHxcnbc [5]

273,15

298,15

323,15

348,15

373,15

398,15

423,15

8) n(f>eHHHr

305,37

322,04

338.71

9 ) ToMac

273,15

283,15

293,15

303,15

313,15

323,15

10) Damep

263,15

273,15

283,15

299,10

313,15

323,15

333,15

343,15 •

353,15

363,15

373,15

423,15

473,15

0,5985

0,5004

0,4207

0,3557

0,3028

0,2579

0,2221

H Ma.KKCTTa (13]

0,50201

0.45028

0,40820

H Ua'wep [13]

0,575744

0,533836

0,503694

0,473599

0,444738

0,418603

H Zla;icoH (37 J 0,615999

0,575360

0,537930

0,480536

0,439:<41

0,410309

0,384999

0,360758

0,33f;657

0,315842

0,296592

0,213176

0,152930

KEY: 1. Roper [35] 6.

2. Turlington and McKetta [11] 7.

3. Pfennig [13] 8.

4. Ratzsh and Bittrich [36] 9.

5. Walters, et al [6] 10.

David and Hamman [39]

Michels [5]

Pfennig and McKetta [13]

Tliomas and Zander [12]

Butcher and Dadson [37]

The data of Turlington and McKetta agree with those of Pfennig, but

the temperature dependence B given in these works differs from the

temperature dependence according to other authors. The data of Thomas and

Zander [12], and those of Butcher and Dadson [37], were obtained from

-26-
measurements of compressibility by the Burnett method in the pressure range

up to 20 bar. Their values of B agree, but are somewhat higher than the

values of B obtained by other authors. The data of Roper [35], Ratzsh and

Bittrich [36] and Michels and Geldermans [5] , who obtained values of B by

expanding the compressibility at low densities into a series by powers of

1/v, the coefficients of which were determined by the method of least

squares, agree quite satisfactorily.

David and Hamman [39] found that the values of B for many compounds

can be described by a third-power polynomial in terms of reduced temperature

i3-.a+i- +

-J-

+ ^, (12)

where

[kp=cr] fKp ' V'^,,

•

v^^ = 129 cm^/mole; T^^ = 282. 4°K is the critical temperature.

The constants for ethylene have the following values: a = -4.912,

3 = 18.575, Y

= -23.892, 5 = 8.975.

Walters and coworkers [6] represented the results of their experimental investigations at low pressures up to 45 bar as polynomials by powers

of 1/v. The values of the coefficients for 1/v are somewhat lower than the

data of Roper and Michels.

It is noteworthy that when compressibility is expanded into the series

7 - 1 J V MJ)

the coefficient for 1/v can be equated to the second Virial coefficient under

completely determined conditions, as shown in [40].

Roper's values [35] of the second Virial coefficient for ethylene

are described by a polynomial of the third power of the inverse temperature

in the 199-343°K range

D 16,036

12 — 9^3.58 10^ ^3,3855 • 10'

Roper's data for temperatures below 270° K fall on a smooth continuation

of the curve plotted according to the data of Michels, Ratzsh and Bittrich.

At temperatures above 270°K the deviation of Roper's data increases with

temperature. This is apparently caused by the fact that the error of Roper's

determination of the specific volume of ethylene increases as the

temperature increases.

-27-
Table 8. Second Virial Coefficient of Propylene According

to Data of Different Investigators

T-\ K - li- 10". r^ K

-«-lo«. !j — S•lo^

M*/K2 — fl-IO'. M*/Ke

1) Por

220

230

240

250

260

270

280

lep |35]

1,4687

1,33050 2

1,212031

1,070198

1,020919

1,943270

298,15

318,15

323,15

348,15

280

290

300

310

0,825304

0,721790

0,699533

0,603162

XeMMCK [39]

0,9240

0.8722

0,8270

0,7629

320

330

340

1 350

400

450

298,15

318,15

0,7163

0.6702

n C07J. UiO-i' "I 0,5894

0,4349

0,3280

c H jp. |21j

0,8241

0,7175

323,15

348,15

398,15

423,15

.^<})cniiiir

305,37

322,04

338,71

0,6942

0,5887

0,oUot)

0,4374

0,3811 n MaKKCTva

[13]

0,76819

0,674490

0,599090

KEY: 1. Roper [35]

2. David and Hamman [39]

3. Micliels, et al

4. Pfennig and McKetta [13]

The values of B calculated according to tlie Leonard- Jones potential

[6-12] with the parameters: e/k = 199. 2°K, = 116.7 cmVmole [25] and

according to the Corner potential for long molecules [38] with the parameters :

'l/a = 0.21, e = 192°K,

c

= 4.1 A, are presented in Figure 2

The values of B calculated by the Leonard- Jones potential agree with

Michels '• data. Such agreement is quite understandable, considering that

the stated constants were determined from values of B obtained in Michels'

work [5]. The Corner potential with the stated parameters, which he himself

obtained [38] , does not yield the correct values for the second Virial

coefficient of ethylene.

Published data on the second Virial coefficient of propylene are

presented in Table 8 and Figure 3.

It is clear from the table and figure that there is good agreement

of data obtained by the various authors. The exceptions are the data of

Pfennig and McKetta [13], which are higher than the others.

Roper [35] proposes a polynomial that describes the dependence of B

of propylene on temperature:

6,81 J^CP _ 31,35 • 10^

7 CM^lMOAb. (15)

The deviations of Roper's data from those of the other authors are

analogous to the deviations in the case of ethylene.

Presented in Figure 3 are the values of B calculated according to

the Leonard- Jones potential. The parameters of the potential are determined from the critical data are: e/k = 0.77 • T = 281°K:

cr

-28-
= 18.4, T /p = 147.95 cm /mole and for the Corner potential they are:

0 cr ^cr < ^ f J l/a = 0.26, e = 220°K; a = 4.9 A.

c c

The values of B determined according to the Corner potential are

considerably closer to the actual values than in the case of ethylene. The

Corner potential model is apparently more valid for propylene than it is

for ethylene.

8,

-0.05

-0,09

-Oil

~0J5.

1 ^

r o

o ; A 2

• J

«> if A 5

o 6

» 7

e 8

o

-r 0^

Figure 3. Second Virial coefficient of propylene according

to the following data: 1 -- authors of present book (from

results on compressibility); 2 -- David and Hamman [39];

3 -- Michels [21] ; 4 -- calculated according to the LeonardJones potential (6-12) . a and e/k determined by critical

parameters; 5 -- Roper [35]; 6 -- calculated according to

the Corner potential [38] ; 7 -- Pfennig and McKetta [13]

;

8 -- authors of present book (from data on speed of sound)

.

Determination of Second Virial Coefficients of Ethylene and Propylene

According to Experimental Data on the Speed of Sound

In the range of low pressures, in which the volumetric behavior of

gas is described with sufficient accuracy by the equation of state with

the second Virial coefficient

the thermodynamic speed of sound is determined through the equation

1 +2p!5 + (Xo

(16)

dB

dT

(>'-o- 1)-' d'-B \ 'Tn j (17)

It follows from this equation that the isotherms of the square of the speed

of sound in coordinates w^ - p are straight lines in the above-mentioned

range of states, and the angle of inclination of these lines is determined

by the second Virial coefficient and its temperature derivatives.

Differentiation with respect to pressure and passage to the limit for

p ^ 0 gives equation (17) the form

-29-
(18)

The analogous equations are described in the literature and are used

for calculating the second Virial coefficients of gases according to

acoustical data.

The dependence of the second Virial coefficient is quite well transmitted in a sufficiently broad temperature range by an equation of the type

B A.-i- A, (19)

From expressions (18) and (19) we have

d

(20)

For a given slope of the isotherm of the square of the speed of sound

equation (20) contains the unknowns A^, A^, A^,

The accuracy of calculation of the second Virial coefficient by the

examined method depends on the accuracy of determination of the angle of

inclination of the isotherms of the square of the speed of sound and on the

number of experimental isotherms in the investigated temperature range.

The accuracy of determination of the angle of inclination, in turn,

depends on the accuracy of the initial experimental data on the speed of

sound, number of experimental points on each isotherm of the investigated

pressure range and method of determining the angle of inclination of the

isotherms on the basis of experimental data.

The analytical method in which the isotherms of the speed of sound

are approximated, yields the best accuracy in determination of the angle of

inclination of the isotherms. Used for calculating the second Virial

coefficients is an approximating function of the form

w~ = Wo + ap hp^, (21)

where w^ = /RTk^ is the perfect-gas speed of sound.

As indicated by analysis of experimental data, function (21) is most

suitable for approximating the speed of sound in a rather broad pressure

range

.

The essence of the method used for calculating the second Virial

coefficient on the basis of acoustical data consists in the following. The

experimental isotherms for the speed of sound in gas are approximated by

the method of least squares by polynomials (21) , with the result that the

slope is determined for each isotherm:

-30-
'dp \ Tif^) T. p-'C

wfiere a is the coefficient of polynomial (24) at the pressure in the first

power.

The unknowns , A^, A^ are found from the condition of the minimum

sum of squares of relative deviations of the experimentally determined

angles of inclination of the isotherms from the calculated according to the

equation i = tnin,

where

(22)

is the absolute error of set Y. . 1 Data on the speed of sound, obtained by Yu. A. Soldatenko and E. I.

Dregulyas (see Chapter V) in the 190-480°K temperature range on 18 isotherms

by acoustical interferometry , the accuracy of which is characterized by the

maximum possible error of ±0.15%, were used for calculating the second

Virial coefficient for ethylene and propylene. The pressure range for each

isotherm, in which the experimental data are described within the limits of

accuracy of the experiment by a polynomial of type (21) , were determined by

trial and error.

Data (Chapter IV) on the perfect-gas heat capacities of ethylene and

propylene, and values of w^ determined on the basis of measurements of the

speed of sound, were used in the calculations.

The following analytical dependences B(T) were obtained for ethylene

in the 230-470° K temperature range:

R- nnn/inn-^ ^/Go 38.172 2.S5i.io«

IS ^ 0,00400o — - -t- ; (23)

for propylene in the 190-170°K range:

2 519 9 266 -10*

B = 0,003256 - . (24)

The scattering of the angles of inclination of the isotherms of the

square of the speed of sound relative to the smooth curves, calculated

according to formula (20) using expressions (22) and (24) , does not

-31-
exceed ±3.5%. This indicates that the dependence of the second Virial

coefficient of ethylene and propylene is satisfactorily transmitted in the

investigated temperature range by these equations. The theoretical values

(jf the second Virial coefficient of ethylene and propylene agree with most

of the published values within the limits of 0.0005 m^/kg.

Determination of Second Virial Coefficients of Ethylene and Propylene

According to Compressibility Data. Recommended Values

There are several methods of finding the Virial coefficients from

experimental compressibility data.

The method most commonly used is calculation of the Virial

coefficients according to low pressure data. Since

{Z-\)v ^B-\--^+ (25)

the second Virial coefficient can be determined by means of limit transition

lim (Z— l)y Z?. ("25^

The contribution of the third and subsequent Virial coefficients to

the compressibility of a gas is presumably negligible at low pressures up

to 2-3 bar, since at low pressures Z ^ 1, the small error in the experimental determination of Z leads to large errors in the determination of B.

Limit (26) is usually found graphically in coordinates (Z - l)v, 1/v. This

method is discussed in detail in [25] and [41] . The Virial coefficients

are found, as a rule, to be somewhat higher than in the case of other methods

(see Figures 2 and 3)

.

Methods of extracting the Virial coefficients from experimental data

on compressibility in a wide range of densities [40, 42, 43] have been

worked out in recent years. A method is proposed in [42] based on representation of compressibility as a series by powers of 1/v or p. The

coefficients of this series are calculated by the method of least squares

using the experimental data at moderate pressures. Since the solution

obtained by the method of least squares is not unique, the authors examined

such polynomials, the slope (-^ or gj^y^) and curvature

8 (1/v)

of which correspond to the slope and curvature of the compressibility

isotherms in the corresponding coordinates. The coefficients of such a polynomial are taken as the Virial coefficients. The stated conditions

are by no means sufficient. This is convincingly shown in the works of

Michels and coworkers [40] , Hall and Canfield [43]

.

Michels, Abels and Ten Seldam [40] studied in detail the feasibility

of extracting the Virial coefficients from the experimental data p, v, T in

a wide density range. The essence of the method of Michels and coworkers

-32-
consists in the following. The compressibility factor Z is represented as

a polynomial by powers of density. The investigated density range is

broken down into subranges, for each of which is found, by the method of

least squares, a polynomial that approximates the experimental data. It is

shown that some of the first coefficients of the polynomials constructed

for the various subranges with the corresponding density powers-, coincide

within the limits of accuracy of their determination, which is, in turn, a function of the experimental error. This confirms the feasibility of

unique representation of Z as a series by powers of density.

Suppose the experimental data, contain an error, which is random in

character and obeys the Gauss distribution. This means that the set of

experimental points obtained is one of a number of possible sets, for each

of which can be found an approximating polynomial by the method of least

squares. The coefficients of the polynomials thus obtained display

scattering, which is a function of the error of the experiment. It is

further shown that the coefficients of the polynomial (of the model function) will be close to the coefficients of the true Virial series.

For the proof a criterion is introduced, the essence of which consists

in the fact that if the sum of squares of deviations [40] is small compared

with the experimental error, the deviations of the polynomial coefficients

from the coefficients of the true series will be small compared with the

scattering of polynomial coefficients.

In the work are presented relations that permit the relation between

the error of the experimental data and errors of the "model" polynomial

coefficients to be established.

The proposed method [40] is suitable for calculating several of the

first Virial coefficients of carbon dioxide on the 49.712°C isotherm. It

can be concluded from the results obtained that this method makes it

possible to calculate with acceptable accuracy only the second and third

Virial coefficients. The error in the calculation of the fourth

coefficient is comparable with the magnitude of the coefficient itself.

It is noteworthy here that the Virial coefficients obtained by means of

the above-described very complex and laborious computational procedure are

close to the coefficients presented in [44] . The Virial coefficients were

calculated in the cited work for carbon dioxide in a narrow density range

by the method of least squares.

Hall and Canfield [43] proposed a somewhat different approach to

the problem of determining the Virial coefficients on the basis of

compressibility data.

Hall and Canfield used the method of least squares for calculating

the coefficients of the polynomials. This method employs orthogonal systems

of functions and has considerable advantages over the method of least

squares in the usual form.

-33-
A more stringent criterion was developed for identification of the

coefficients of the approximating polynomial with the true Virial

coefficients. They call it the series cut-off criterion, which takes into

account the fact that an infinite Virial series is approximated by a finite

polynomial.

The method of optimal determination of the Virial coefficients is

illustrated by Hall and Canfield in two examples. As the first example

they calculate the coefficients of some function, selected as an infinite

series with known coefficients. Using this function they simulate the

path of compressibility isotherms. The computed coefficients of the polynomial, approximating the selected function, are found to agree satisfactorily with the true coefficients.

\

^ Also, the Virial coefficients of carbon dioxide were calculated [43]

on the 49.712°C isotherm, for which there are the coefficients computed by

Michels and coworkers.

The Virial coefficients and their errors, obtained by Hall and

Canfield and by Michels, practically coincide. This is evidence of equal

effectiveness of both methods.

The Hall-Canfield method requires considerably fewer computational

operations.

The method of extracting the second Virial coefficients employed by

the authors of the present work is a compromise between Michels and the

Hall-Canfield methods in the sense that the coefficients of the approximating polynomial were calculated using orthogonal polynomials, and the

errors of the calculated coefficients are determined by a method which is

somewhat similar to the proposed by Michels.

The Forsythe algorithm [34] is used for approximation of the isotherms

for the case of one variable. The function f = - l)v was approximated as

1 a function of density p = —

.

' V

The Virial form of the isotherm equation was found by reducing

similar terms for identical powers of

The program for approximation was written in the command system of

the BESM-3M computer.

The program finds 10 powers of the expansion. The deviations at

points 6^, sum of squares of deviations Z6? and coefficients of the Virial

form of the isotherm equation are read out on the printout system of the

computer

.

The program was written as a standard program that can be used for

approximating any tabulated function.

-34-
Table 9. Values of Second Virial Coefficient B, Calculated for

Various Density Ranges and Various Expansion Powers on

348.15°K Isotherm of Ethylene

-zi-io'. mVkg for n, equal to

I,: 12 30 43 64

0 0,3079 0,2397 0,1872 0,1026

1 0,3555 0,3557 • 0,3630 0,4174 0,4609

2 0,3555 0,:543 0.3452 0,3130 0,2941

0,3547* 0,35G5 0,3025 0,3763 0,3802

A 0,'-555 * 0,3504 * 0,3534 0,3574 0,3613

5 0,3510 0.35G2 * 0,3555 * 0,3519 0,3513

6 0,3430 0,3563 * 0,3559 * 0,3546* 0,3536 *

7 0.3328 0.3620 0,3503 0,3594 * 0,3585 * 8 0,3221 0,3671 0,3445 0,3039 0,3630

9 0,3113 0,3720 0,3385 0.3G83 0,3073

10 0,3001 0,3769 0,3.324 0,3725 0,3714

*The asterisk denotes the region in which B acquires approximatel,y constant values and is shifted toward higher powers

as the number of experimental points used for the approximation is increased.

The coefficients of a series for the experimental isotherms of

ethylene and propylene were computed with the program for various density

ranges

.

Listed in Table 9 by way of example are the calculations of the

second Virial coefficient of ethylene on the 348.15°K isotherm. The number

denotes the number of experimental points, read from the beginning of the

isotherm. The initial experimental data for ethylene and propylene are

presented in Tables 3 and 4.

As seen in the table, the second Virial coefficient, starting at

some power, does not depend on the number of expansion powers m.

For the purpose of identifying the values of B obtained for the

various powers of the expansion and various density ranges with "true"

values, the results obtained were statistically processed to enable

evaluation of the error (confidence interval) of the calculated second

Virial coefficients.

Using Michels' experimental data they calculated the error

A'

where

n. = f - f , ; (28)

1 exp calc

-35-
m is the power of the approximating polynomial; N is the number of experimental points.

Twelve samplings were made with the aid of random numbers tables and

in consideration of the values o:^ a obtained, for each isotherm, each of

which, within the limits of error, is an experimental set of data. The

approximating polynomial was formulated for each sampling. The final values

of the coefficient were obtained as the most probable values on the

stability segment. The values of B and AB, given in Table 10, were obtained

by statistical evaluation of the parameters of the normal law (confidence

interval)

A/? ==..1.088 5a; . (29)

where n is the number of samplings.

The significance of the band AB is that the probability of the

calculated AB falling within this band is 70%.

Table 10. Virial Coefficients of Ethylene and Propylene

According to Data of the Authors

T.'K r. °K h, M'/Ke AS. m'/kz

Ethylene Propylene

208,15

323.15

348,15

373.15

398,15

423,15

—0,005014

—0,00120?

—0,003551

—0,003032

—0,002584

—0,002224

±0,000023

±0,000054

±0,000012

±0,000018

±0,000021

±0,000037

298.15

318.15

323.15

.348.15 375.15

398.15

423,15

—0,008242

—0,007183

—0,006903

—0,005901

—0,005027

—0,004328

—0,003829

±0,000010

±0,000091

±0,000052

±0,000074

±0,000095

±0.000083

±0,000093

On the basis of the above review of analysis of published data and

of calculations done by the authors on compressibility and the speed of

sound, the most reliable data were selected, and were then approximated by

the polynomials:

B (T) =^ 0,02OS4G81 - 0,3325105 ~^ - 0,2079736 — 0,6639566 +

-fOJ003753~-— 0,5853397 — (for ethylene) ; (30)

b m - _ 0,08480S03 + 0,128800 ~- — 0,7710073 ~+

0,22 1 5 1 92 4-r - 0,31 -12363 + 0, 1 7366099 4^'

(for propylene)

.

-36-
The recommended second Virial coefficients and their first derivatives,

calculated on the basis of polynomials (30) and (31), are listed in Table 11.

Table 11. Recommended Values of Second Virial Coefficients

Their First Derivatives for Ethylene and Propylene

and

7', K dBldT dBldT

Ethylene Propylene

200 0,01 101

1

0,0037776 200 0,020.0 19 0,0219912

210 0,010054 0,0031971 210 0,018292 0,0168845

220 CoC'^riG 0,0030131 220 0,016321 0,0130191

230 O.OOJS'^'P 0,0023545 230 0,0146.39 0,01020bo

2-10 O,n07'i'2''' 0,0020177 240 0,013224 0,0080745

25(^ 0,007.< J6 0,0017950 250 0,012031 0,0064572

260 0,00ij7iii< 0,0015869 260 0,01 1018 0,00521 10 270 O,00G2Ni 0,0014125 270 0,010147 0,0042432

280 0,0058 0,001265 280 0,009389 0,0034826

2S0 0,0053; '3 0,001 1411 290 0,008720 0,0028798

300 0,005003 0,0010345 300 0,008120 0,0023982

310 0,001016 0,0009607 310 t), 007577 0,0020104

320 0,001321 0,0008632 320 0,007082 0,0016956

330 0 fin -(074 0 0007937 330 0 0066''^G 0 0014383

340 0,003704 0,0007330 340 0,006364 0,0012266

350 0,003509 0,0006788 350 0,005819 0,0010512

360 0,0032^s-1 0,0006309 300 0,00.5461 0,0009051

370 0,003079 0,000.5881 370 0,005132 0,000782

380 0.002891 0,0005498 380 0,004829 0,0006730

390 0,002718 0,0005153 3Ju 0,004552 0,0005918

400 0,001558 0.;)001840 !00 0,004.302 0,000517

410 0,002409 0.0001557 410 0,004076 0,0004535

420 0,00227! 0,0004299 420 0,003874 0,0003961

430 0.0021 12 0,0004062 430 0,003697 0,000351

440 0,002090 0,0003841 410 0,003.542 0,0002809

450 0,00 1 90G 0,000..;646 450 0,0034 1

1

0,0002743

460 0,00 1 7! i: 0,000,>162 41.0 0,003.302 0,0002441

470 0,00 1 G'' i 0,!;C03292 470 0.00.3214 '0,0002156

•J 80

490

0,00 1 im "0,0ij0.<135 1 4MJ 0,003148 0,0001914

0,001 4fiL. 0.000290S 490 0,003102 0,0001701

500 O.OOMO:; 0.0002852 500 0,003075 0.0001511

Recommended Values of Specific Volume, Enthalpy, Entropy, Isobaric Heat

Capacity of Gaseous Ethylene and Propylene

The recommended specific volumes of ethylene and propylene were

calculated using equations of state of the form (11), the coefficients of

which are given on page 18. The roots of the equation were determined by

methods of iterations and half division using the BESM-3M computer^.

The specific volumes in the 200-270°K temperature range and

0.5-20 bar pressure range were computed by an equation with the true

second Virial coefficient:

The authors gratefully acknowledge the cooperation of N. S. Levchuk and

K. A. Lensyurovskaya of NIIASS Gosstroy Ukrainian SSR in the writing of

the programs and execution of the calculations in the computer.

-37-
The second Virial coefficients of ethylene and propylene are listed

in Table 11.

The enthalpy, entropy and heat capacity were calculated on the

same computer in accordance with equations derived on the basis of thermal

equations of state. The enthalpy was measured from the 0°K crystalline

state

A/ - RT

AS= R

S = St~ A5;

C, = C,+ R

= Cl — R

1 +

In these equations are the "Virial coefficients" of the equations

of state of ethylene and propylene.

•V ' 1

/!=0 '

dAi _ V r'

^

d^Ai _ V r'

Given in Tables II and VI are the i'sobaric heat capacities C of

P

ethylene and propylene, calculated by the above-mentioned method, for

pressures above 100 bar. The isobaric heat capacities in the range of

parameters of state near the saturation curve and in the supercritical

region to a pressure of 100 bar were calculated on the basis of experimental

data on the speed of sound. These data agree well (deviation up to 3% in

the region of peak heat capacity C^) with data calculated by the equations

of state. This fact and the high accuracy of description of the p, V, Tdata confirm the reliability of the computed caloric properties of gaseous

ethylene and propylene with the aid of the thermal equations of state

offered on pp. 18-20.

-38-
CHAPTER II. SPECIFIC VOLUME OF LIQUID ETHYLENE AND PROPYLENE

Review of Experimental Data

Three works have been published to date on experimental determination

of the specific volume of liquid ethylene. Michels and Gelderman [1] did

investigations on the 273.15°K isotherm at pressures up to 2,696 bar. The

accuracy of these data is 0.01%. The specific volumes obtained in [1] are

listed below:

p , bar p , bar V, CM^/e

43..'^7 2,8738 330,81 2.1138

2,7919 353.11 2,0961

54,52 2,7187 494.72 2,0072

61.52 2.6582 527.24 1,9908

69,27 2.6055 729,04 1,9076

77,8G 2,5584 774,79 1,8922

86.33 2.5195 1053.43 1,8152

87.24 2.5157 1116,12 1,8010 . 91.78 2,4975 1130,42 1,7977

335.57 2.3690 1450,80 1,7365

144,82 2,3486 1532.15 1,7231

215.57 2.2320 '769,7? 1,6883

230.53 2.2130 2695.80 1,5878

N. V. Boyko and B. V. Voytyuk [2] investigated the specific volume of

liquid ethylene at temperatures from 180 to 273°K and pressures up to 60 bar

by the method of hydrostatic weighing using strain gauges. The error of the

data, according to the authors, was 0.5%. Considering the low purity of the

investigated compound (99.7%), these data should be considered preliminary.

Later on, after improvement of experimental method, the specific volume of

liquid ethylene with the same parameters was investigated by B. V. Voytyuk

for a specimen containing 99.99% ethylene. The data obtained, the accuracy

of which is 0.15%, are presented in Table 12.

The main procedural element of this work is consideration of the

correction for heat transfer in the weighing head. Since high-density

current (55 A/mm^) passes through the strain gauge, the latter is a heating

element. The conditions of heat exchange between the strain gauge and the

investigated gas are governed, assuming other conditions to be equal, by the

nature and density of the gas, which varies as the pressure in the system

changes

.

-39-
Table 12. Experimental Data on Specific Volume of Liquid Ethylene

(Ethylene -- 99.99% by Volume, Ethane -- 0.01% by Volume)

V, cmVg 'at' t, °C

d

0 —5 —10 —20 —30 —45 -60 -70 —80 —90

— — — 1

1 .oou s?n

If) 2,005 1,938 I .o._o IS 2,124 2,001 —

20 2,285 2,116 1,997 1,931 1 874 I 8''4 25 2,273 2,109 — —

30 . 2,406 2',260 2,103 1,989 1,925 I 869 1 820

35 2,595 2!388 2^250 2,096 — —

39 2,731

40 2,561 2,371 2,239 2,091 1,982 1,920

42 2,921 2,699

45 2,8G3 2,670 2,531 2,J07 2,230 2,086

48 2,8:3 2,643

50 2,506 2,343 2,221 2,080 1,975 1.914 1.860 1,813

51 2,771 2,619

54 2,733 2,597

55 2,483 2,329 2.212 2,076

57 2,701 2,577

60 2.6^5 2,558 2,462 2,315 2,204 2,071 1,969 1,909 1.855 1,810

The required correction for fluctuation of heat transfer conditions

was determined by finding the dependence of the readings of the strain gauge

installed on the top and bottom locking devices, on the pressure at a strictly fixed weighing unit temperature.

Both dependences, as it turned out, coincide for the same compound,

and this is reason to consider them uniquely when the strain gauge is

operating normally. The correction for heat transfer is 2% of the measured

specific volume, and the error of determination of the correction does not

exceed 2.5%.

During determination of the density of liquid ethylene the pressure

in the system was created by the gas of the investigated compound, since the

temperature of the weighing head was maintained at 323.15°K. The critical

temperature of ethylene is 283.05°K.

Data on the specific volume of liquid ethylene on the saturation

curve at temperatures of 183. 15-273. 15°K were obtained by extrapolating

the experimental isotherms to saturation pressure [3] . Analysis of these

data (see Chapter III) confirms their high accuracy.

The specific volume of liquid ethylene was investigated by Ye. A.

Golovskiy, V. A. Yelema, V. A. Zagoruchenko and V. A. Tsymarnyy [4]

(Table 13) by constant quantity piezometry in the temperature range from

202°K to the critical point at pressures up to 600 bar. The authors give

the following measurement errors: Ap = 0.04-0.16 bar, 6V = 0.06%, 6G = = 0.009% and AT = 0.08 deg.

Noteworthy is the work of Dick and Hedley [5], in which Michels' data

[1] are smoothed for rounded off pressures.

-40-
Table 13. Experimental Data of Golovskiy, Yelema, Zagoruchenko and

Tsymarnyy [4] on Density of Liquid Ethylene (Ethylene -- 99.66%, Ethane -- 0.34%)

T\ K p, Kec/CM' p. 1/CM' T", K p. mc/cM' p. a/cM*

235,62 51,05

1 0,4668 259,37 113,52 0,4400

240,00 80,G3 0.4667 263.77 138,08 0,4400

245,28 115,63 0,4666 270,34 174.29 0,4398

249,01 144,69 0,4665 276.31 207,17 0,4396

255,66 185,95 0,4063 281,05 233,35 0.4395

263,22 234.23 0,4661 278,64 220,14 0.4396

270.61 282,55 0,4659 286,25 261,82 0,4394

270,48 282,39 0,4659 290,87 287,28 0.4393

278,79 331,21 0,4657 290,55 318,06 0.4.391 285,09 371.41 0,4655 301,52 348,14 0,4390

2yi,97 415,21 0,4653 254.43 37,66 0,4171

299,29 461,95 0,4651 260,08 64,76 0,4170

306,83 508,85 0,4650 205.79 91,70 0,4169

202,57 298,33 0,5542 270,05 111,90 0,4168

207,62 357,33 0,5540 272,54 121,82 0,4167

212,80 417,53 0,5538 2^8,88 151,86 0,4166

218,21 479,73 0,5536 284,87 180,11 0,4164

223,39 538.53 0,5534 2J0,44 206,63 0.4163

228,99 599,97 0,5532 :'95,83 231.83 0.4162

218,57 13,79 0,4900 i 202,02 512,44 0,4160

221,18 34,18 0,4899 ; 202,11 513,24 0,5723

228,93 94,82 0,4897 1 305,24 276,43 0,5723

234,00 134,48 0,4895 305,51 277,63 0,4160

241,10 189,96 0.4893 -505,27 42,75 0,3354

246,23 229,15 0,4891 208,11 53,33 0,3852

250,79 264.08 0,4890 271,48 67,35 0,3852

254,36 291,24 0,4889 276,39 82,81 0,3851

262,07 348,84 0,4837 282,28 105,03 0,3850

266,52 382.36 0,4885 287,36 124,25 0,3849

270,41 411,29 n 4884 293.87 149,23 0,3848

278,60 471,85} 0;4SS2 300,01 1 72,53 0,3846

286,25 527,92 0,4880 304,86 191,27 0,3845

293,93 583,36 0,4S77 .304,89 191,39 0,3845

207,86 26,87 0,5121 200,69 390.53 0,5642

211,43 59,55 0,5120 206,45 460,81 0,5640

217,42 114,17 0,5118 211,47 521,84 0,5638

223,33 167,10 0,5116 218,63 605,13 0,5635

228,19 210,40 0,5114 218,52 605,33 0,5635

228,34 211,72 0,5111 200,28 200,70 0,5460

236,15 280,78 0,51 12 206,30 256,82 0,5458

242,13 332,95 0,5110 211,56 315,96 0,5456

245,99 366,24 0,5109 216,97 375,52 0,5454

207,36 581,44 0,5722 222,57 436,36 0,5452

209,15 604,08 0,5721 227,37 486,7) 0,5450

242,79 21,87 0,4105 2 32,60 542,18 0,5448

247,45 48,32 0,4404 238,06 599,27 0,5447

253,63 82,9!^ 0,4402

A list of experimental works pertaining to investigation of the density

of liquid propylene is given in Table 14.

Vanghan and Graves [6] investigated density by constant quantity

piezometry with an accuracy of ±1%. Their data are presented in Table 15.

1 Farrington and Sage, using a method described in [7], measured the

specific volume of liquid propylene with an accuracy of 0,3%. Their data

are given in Table 16.

-41-
Table 14. List of Experimental Works on Density of Liquid Propylene

1)

Ai;T..i<u

Boyre;i h FpoBC [6] ftappiiiiiroH H CeiiA>K [7J MiixcHbc 11 corpyAiiHKH [8] jliiTMap, lily;ibu ii lilrpecce [9] BOKTIOK

2)

1940

1949

1953

1962

19C7

ri.Ty;j. C

n mi;i, 6up

0—91,4

4.44—87,78

66,3—88,2

(0) -(-1-90)

(—90) _ (4-39,3)

6.9-82,8

0,9—689,5

36,26—2192,86

19,0-1028.7

5—60

KEY: 1. Authors 2. Year

Vanghan and Graves [6] 3. Temperature range, °C

Farrington and Sage [7] 4. Pressure range, bar

Michels, et al [8]

Dittmar, Schulz and Stresse [9]

Voytyuk

Table 15. Compressibility Factor Z for Liquid Propylene According to

Vanghan and Graves [6] for P^^ = 45.4 atm, t^^ = 91.4°C, p^^ = 0.233 g/cm^ I

p. 6ap

z at t. "c

0 50 75 91.4

0,15 6,90 0,022

0.20 9.20 0,028

0,25 11,50 0,035

0.30 15,64 0,042 0,043

0.40 18,40 0,055 0,057

0,50 23,00 0.069 0,071 0,075

0,60 27,60 0.083 0,085 0,090

0,70 32,20 0.097 0.099 0,104

0,80 36,80 0.109 0,113 0.119 0.131 0,90 41,40 0.124 0,127 0,133 0,144

1.00 46,00 0.138 0,141 0,147 0,157 0.273

1,02 46,92 0,210

1,10 50,60 1,151 0,155 0,161 0.171 0,202

1,20 55,20 0,165 0,169 0,175 0.184 0,209

1,30 59.80 0,179 0,183 0,188 0.197 0,219

1,40 64.40 0.211 0,230

1,50 69,00 0,242

1.60 73,60 0,254

1,70 78.20 0.266

1.80 82,80 0.278

The results of experimental investigation of Michels and coworkers [8]

on the 66.3, 74.8, 82.8 and 88.2°C isotherms at pressures up to 2,000 atm,

were published in 1953. The error of the data was estimated by the authors

to be 0.03%. The results of studies [8] are presented in Table 17.

A rather detailed investigation of the specific volume of liquid

propylene by means of a constant volume piezometer relieved of pressure was

done by Dittmar, Schulz and Stresse [9] . The authors do not give a conclusive evaluation of the accuracy of their data, but state only the

errors of measurement of temperature (0.01°C), pressure (0.06%) and volume

of the measurement bomb (0.1%). The experimental data [9] are presented in

Table 18.

-42-
Table 16. Experimental Data of Farrington and Sage [7] on Specific

Volume of Liquid Propylene

V. c.\i'U ii|iu /. "C

p. Cap

4,44 21.11

1

37.78 £4.14 71.11 82.22 87,78

=

1,8529 A filQ 1,8516 ~i—

Ifl "^JT 1 U,OT ^ 1,8510 . 1,8479 1,9447 zu»uoo 1,8429 1 ,9365 2,0620 . _ 1,8379 1.9290 2,0501 2,2181

1,8329 1.9215 2,0383 2,1981 2,4659

41.370 1,8279 1,9147 2,0277 2,1794 2.4116 2.7250

<JD, J ou 1,8192 1.9016 2,0077 2.1457 2.3348 2,5302 2,6763

Aft OsH Do,you 1,8104 1,8891 1.9890 2,1169 2,2786 2,4322 2,5283

00,lo6 1.7992 1.8735 1 .9684 2,0832 2,2237 2,3442 2.4 1 60

J (JoWzj 1.7892 1.8001 1,9490 2,0545 2,1800 2^2817 2^3410

1 0A i^r^

)

1,7792 1,8485 1,9315 2.0293 2,1444 2,2343 9 9«55

io/,yuu 1.7705 1.8373 i;J159 2,0077 2.1 126 2! 1975 9 9443

1 c r I oo 156, 13»

172,3 / ,»

1,7617 1,8273 1/9022 I i9883 2.0895 2, 1 663 9 9068

1.7536 1.8179 U8891 1,9709 2,0664 2!l400 2,1762

loy.ui J 1,7455 1.8085 l!8772 1 ,9552 2,0451 2ill38 2! 1481

1,7380 1,7998 1,8666 1,9403 2.0258 .2,0913 2! 1232

Oil "50 "^ 1,7213 1,7829 l..*-'- 172 1,9147 1 9'' 1 1 £L,\J i JO 275,800 1J118 UGSO |!82'j8 U8922 1,9621 2,0189 2.0420

31 0,2 /o 1,7005 1.7542 1.8142 1,8728 1,9365 1,9890 2.0102

344.730 1,6899 1.7417 1,8010 1,8547 1,9140 1,9634 1.9821 413,700 1,6712 1,7199 1.7730 1,8241 1,8766 1,9203 1.9353

482.650 1,6556 1.7012 1.7486 1,7967 1.8441 1,8803 1,8953

551,600 1.6418 1,6830 !,7268 1 ,7705 i,8160 1.8479 1,8016

620,55 1,6294 1,6608 !,7068 1,7474 1,7910 1.8192 1.8316

689,500 1,6175 1,6512 1,6862 1,7249 1,7667 1,7936 1,8073

1

Table 17. Experimental Data of Michels and Coworkers on Specific

Volume of Liquid Propylene

p, bar at' t, °C

0, CM*IZ

66.3 74.8 82,8 88.2

3,1461 43,504

2.9326 46.212

2.6477 46,967

2,4834 42,034 62,610 76,777

2,4176 50.788 73.114

2=?555 o6,256

2,2390 64,142 94,319 122,745

2,2253 68,692 99.404 128.486 148,278

2,0772 142.769 181,395 217,317

1,9989 209.522 293.405 321,030

1,9^47 285,783 333,883 379,081

1.8468 435.967

1,8212 492,742 550,942 605,445 642.023

1.7203 798,796

1,6615 1059,397 : 1 36.362 1208,575 1256.802

1,5363 1910.154 2039.289 ,2131.009 2192.857

-43-
Table 18. Experimental Data of Dittmar, Schulz and Stresse [9] on

Specific Volume of Liquid Propylene

---

t:. cm' /e

L>j t J

(•

0 10 20 30 40 50 60 70 80 90

1,5873 757,1 868,9 977,7

1,6129 620,8 725,7 828,7 929,7 1028.7 1,6393 497.2 599,2 699,2 798,3 894,4 988,5 — — — —

J. 6666 388.3 484,4 579,6 672,7 764.9 856,1 945.5 —

1,6949 291,3 382,5 472.7 561,9 649,2 735,5 820,8 905,2 989,5 —

1,7241 205,9 292,2 377,6 461.9 545,2 628,6 711,0 792,4 874,8 956,1

1,7543 134,4 214,8 295,2 374,6 454,0 532,5 611,0 684,4 766,9 843,4

1,7857 73,5 148.1 222,6 297,1 37 i,

7

445,2 518,8 591.3 662,9 734.5

1.8181 19,6 90,2 1(;0,8 220,6 300.1 .369,7 438,4 507,0 575.7 643,3

1,8518 — 41,2 106,9 172,6 237,3 302.0 366,8 431.5 496,2 560,0

1,8867 — — 61.8 123,6 184,4 245.2 305,9 367.7 428,6 488,4

1,9230 — — 26.5 83,4 140,2 196.1 253,0 309,9 366,8 423,6

1.9607 — — — 48,1 101,0 154,0 207,9 261,8 314,8 367,7

1,9999 19,6 69.6 119.6 169,7 219,7 269,7 319,7

2,0833 — — — 19,6 63.7 107.9 152.0 196,1 240,3

OZ.O lUz.U 14(J,J 1 / o,0

2,2727 (56,7 101,0 135,3

2,3S09 44.1 73,5 103,0

2.4999 55,9 81,4

2,6315 44,1 66,7

2.7777 56,9

2.9411 50,0

The experimental data are generalized in Lehman's review [10]. The

tables which he compiled are based on the results of Vanghan and Graves [6]

,

Farrington and Sage [7] and the data of Poll and Maas [11], Hanson [12],

Lu, Newitt and Ruhemann [13] on the specific volume of the liquid on the

saturation curve.

Table 19. Experimental Data of Authors on Specific Volume of Liquid

Propylene (Propylene -- 99.80% by Volume, Propane -- 0.15% by Volume,

Ethane -- 0.01% by Volume, Ethylene -- 0.04% by Volume)

V. cmVg at p, kg/cm^

t. °c

—90

—80

—70

—60

—50

—40

—30

—20

—10

0

14.27 16.58 25.83

32.23

39.31

1,515

1.543

1.572

1.602 1.634 1,666

1.701

1.741 1,790

10

1,514

1,542

1,571

1,601

1,632

1,664

1,699

1,739

1,787

1,837 1.913 1,926

20

1.513

1.540

1,568

1.598 1.629 1.660

1.695

1.735 1.780

1,828

1,903

1,916

1,976

2.027

2,086

30

1,512

1,539

1,566

1.596 1,626

1,657

1.692

1,730

1,774

1,820

1,894

1.907 1,964

2.013

2.067

40

1,511 1.538

1.564

1,593

1.624

1.654 1.688

1,726 1.768

1,813 1.886

1,899

1.953

1.999 2.050

50

1,510

1,537

1.562

1.591

1.621 1,651

1,685

1,722

1,762

1.806

1,877

1,891

1,942

1,985

2.034

60

1,509

1,535

1,560

1,589

1,619

1,649

1,682

1,718

1,757 1.800

1,869

1.883

1,931 1.973 2,020

-44-
B. V. Voytyuk, using a method described in [2] , did experimental

investigations of the specific volume of liquid propylene at temperatures

from +4n°C to -90°C and at pressures up to 60 atm. Pressure in the system

was created by nitrogen, since the critical point of propylene is 365.05°K.

In this case nitrogen and liquid propylene came into contact in a

connective tube 10 mm in diameter, which minimized the dissolving of

nitrogen in the investigated liquid. An experiment was done at -45°C for

liquid ethylene to determine the possible solubility of nitrogen in hydrocarbons. The pressure in the system was created first with gaseous

ethylene and then with nitrogen. The scattering of experimental data did

not exceed oAs%. Analysis of the composition of the investigated liquid

in a KhL-4 chromatograph revealed no notable concentration of nitrogen.

The accuracy of data on the specific volume of propylene is 0.15%. The

data are listed in Table 19.

Recommended Specific Volumes of Liquid Ethylene and Propylene

The recommended specific volumes of liquid ethylene were found on the

basis of experimental data [1, 4] and of the authors' present work.

Results [4] agree quite well with. Michels ' data [1] on the 273.15°K

isotherm. The data in the present work agree with the data in [1] with an

accuracy of 0.15%.

In view of the fact that data [4] are limited to comparatively high

pressures it is difficult to check their concordance with the authors'

data (see Table 12) by direct comparison.

V. A. Zagoruchenko and V. A. Tsymarnyy reported at the Third

Thermophysical Conference on the High-Temperature Properties of Matter

(Baku, 1968) about the thermal equation of state of liquid ethylene, formulated on the basis of data [4] . The equation is

pV^A(T) + BiT},y' + C(T)p\

^ (36)

where A (7) = 427 505 — 969 968 • lO' • T~' + 826 658 • lO'T"' — 84 221 x

X 10~'r + 6447.5 . lO'-'r^; B (?) = —37,4967 + 132.707 • 10'r~' —

~ 166,370 • 10^7^^ + 3,308 • lO""?; C (T) = 0,5739 — 2,8167 X

X 10V~' + 4,4402 . 10Y~'; (pi = kmole/m'; [pV] - kJ/kmole.

The agreement of data [4] with the data presented in this monograph

was checked with the aid of this equation. The discrepancy increases

monotonically on the 60 bar isobar from 0 at 180 to 0.25% at 270*'K. Near

the saturation curve the data calculated on the basis of specific volume

are overstated by up to 0.6% .compared with the data of the authors, and

the deviations decrease as the temperature drops. Thus, in the range of

parameters of state where equation (36) is interpolated, satisfactory

agreement of the results obtained by the authors of the present monograph

and of results [4] is confirmed.

-45-
The specific volumes of liquid ethylene at pressures below 60 bar, ' found by graphic processing of experimental data of the authors of the j present book, are presented in Table II. The values at pressures from 70 i to 500 bar (see Table III) were calculated according to thermal equation

of state (36) .

j Comparison and analysis of the experimental data on the basis of ; the specific volume of liquid propylene revealed that the data of Dittmar,

Schulz and Stresse [9] in overlapping temperature and pressure ranges | deviate from the data of Michels and coworkers [8] by 0.5-0.6%. Only on i the 50 bar isobar at temperatures above 350°K do the deviations exceed 0.6,

and reach 3.6% near the critical point.

The deviations of the data of Farrington and Sage [7] from the data | of Michels and coworkers is 0.3% on the 700 bar isobar and drops considerably as pressure decreases. Near the critical point, however, the deviations i reach 1%. '

j The data of Vanghan and Graves [6] are considerably inferior in terms | of accuracy to the data in [7, 8, 9]. In the overlapping temperature range i of 280-310°K the experimental results of the authors of this work agree with ,' the results of Farrington and Sage within the limits of 0.3-0.40%, and the

deviations decrease as temperature drops. Deviations from the data of

Dittmar, Schulz and Stresse in the same temperature range amount to 0.5-0.6%.

j There is good agreement between the experimental data of Farrington

j and Sage and test data on the saturation curve [11, 12, 13] in Lehman's

review [10] . By extrapolating the experimental isotherms to the saturation

pressures [10] the authors obtained data on the specific volume of liquid

[ propylene at temperatures from 183.15 to 313.15°K. Analysis of these data

| (see Chapter III) confirm their high accuracy. j

I

j The data of Michels and coworkers [8] , Farrington and Sage [7] , and

| of the authors of this book were used on the basis of what has been stated

j above for compilation of Table VII of recommended specific volumes of | liquid propylene. The accuracy of the data is 0.15% for pressures below | 60 bar, 0.3-0.5% for pressures above 60 bar.

1

-46-
CHAPTER III. PROPERTIES OF ETHYLENE AND PROPYLENE ON SATURATION CURVE

Pressure and Density of Saturated Vapor and Liquid

Experimental investigation of the thermal properties of ethylene and

propylene on the liquid-vapor equilibrium curve is the subject of a series

of works, enumerated in Table 20.

The data presented in the cited works are given in Tables 21 and 22.

Experimental data on the pressure of saturated vapor of ethylene,

found in the works of Michels and Wassenaar [8], Mathias, et al [5], Henning

and Stock [1] , agree satisfactorily. The average divergence between them

does not exceed 0.2%. The data of Egan and Kemp [6] are understated relative

to the data of Michels by an average of 0.5%, and the data of Crommelin and

Watts [3] are 0.9% higher than the data of Michels. The specific volume of

saturated liquid ethylene was determined by Maass, Wrigt [2] and Mathias

and coworkers [4] . Their data practically coincide at a temperature of

165°K. In the 170-200°K temperature interval, however, interpolation of

Mathias' data yields specific volumes of the liquid up to 0.4% overstated

in comparison with Maass' data. The specific volume of saturated ethylene

vapor was investigated by Mathias and coworkers [4] . Deviations of the

experimental points obtained in this work from the smooth curve amount to

an average of 2%. It is noteworthy that not all thermal parameters were

determined in [1-8] on the saturation curve. The data of B. V. Voytyuk on

the specific volume of the liquid were obtained by extrapolating the

experimental isotherms of compressibility (see Chapter II) to the saturation

pressures of the vapors. The experimental data of Yu. F. Voynov, N. V.

Pavlovich, D. L. Timrot [17] were obtained by direct measurement of the

pressure of saturated vapors and specific volumes of equilibrium liquid and

vapor. The specific volumes of the liquid and vapor were determined by

hydrostatic weighing with the aid of double strain gauges. In this case

the difference method of weighing was employed (quartz float and calibrated

weight, placed in the investigated phase, were weighed), which excluded the

effect of changing conditions of heat exchange in the weighing head. The

limit relative error of determination of the specific volume of the vapor,

attributed to errors in weighing and determination of the volume of the
float, is 0.02-0.12%, and the limiting error of determination of the specific

volume of the liquid is 0.06-0.7%. The maximum errors correspond to minimum

densities.

Table 20. List of Works Pertaining to Experimental Investigation of

Thermal Properties of Ethylene and Propylene on Saturation Curve

1)

ABTOpU

5 ) Sthjich

7)

XeHHIIHT, UlroK [1] Maacc, Pafir |2|

KpoMMejiiiHr, yoTc [3j

AiarnriC, XpoMMCintir, Votc [4] .MaTcac, KpoMMe.niinr, i'oTc i5] 3raH, Ke.Mn (6|

JlaM6, Poiiep [7] Mnxe-ibc h jp. [8] BoflTIOK BOHHOP. H flp. ;

8)

Maac, PaAT [2]

riayeJi.i, R-A:av,oK [9|

Boyren, Tpeuc [10)

Jlavio, Ponep (7J Jly, Hbrom, PyxMaH (Ml

TexHHMecKHii Komhtct NGAA [12]

Aiapw.MaH H jip. 1 13|

<I>appii:!rron, CeiLl-K [I4J

A\nxo.^i-c II ;:p. (15)

.MopeKpc(})T [16]

Bo'lThiK

BOHfiOB )i ^p. [17]

6) ripOIlIMfcH

1921

1939

1940

1940

194! 1942

1949

1949

1953

1958

1967

1965-1967

31

J) Typa.

1921 P

v' 131—162

1921 164—203

1927 P

V', V' 208—276209—282

1927 v' 128—170

1929 p 203—281

1937 p 123—170

1940 p 147—173

1950 p

v' 149—280

1967 183—273

19G5— 1967 p. I)', v" 163—280

p

v'p

V

P, V

?. v.

P

v'

v'

235—283

194—292

165—225

273—364

151—235

243—365

260—283

303—348

277—360

297—363

273—348

183—313

173—362

KEY: 1. Authors

2. Year

3. Measured parameter

4. Temperature, °K

5. Ethylene

6. Propylene

7. Henning, Stock [1]

Maass, Wrigt [2]

Crommelin, Watts, [3]

Mathias, Crommelin, Watts [4]

Mathias, Crommelin, Watts [5]

Egan, Kemp [6]

Lamb, Roper [7]

Michels, et al [8]

Voytyuk

Voynov, et al

8. Maass, Wrigt [2]

Powell, Giaque [9]

Voughan, Graves [10]

Lamb, Roper [7]

Lu, Newitt, Ruheman [11]

Technical Committee NGAA [12]

Marchman, et al [13]

Farrington, Sage [14]

Michels, et al [15]

Morecroft [16]

Voytyuk

Voynov, et al [17]

-48-
The recommended thermal parameters of ethylene and propylene on the

saturation curve (Tables I, V) were found by graphic analysis of the

experimental data listed in Tables 21 and 22. The data on the pressure of

the saturation vapors of ethylene thus obtained coincide with an accuracy

of 0.2% with the experimental data of Michels [8], Mathias [5], Henning

and Stock [1] and of the authors of the present work. The data of

Crommelin and Watts [3] are 1% overstated compared with the recommended

values, and the data of Egan and Kemp [6] are 0.6% understated.

Deviations of the recommended specific volumes of liquid ethylene

from the experimental data of Maass [2] , Mathias [4] and the authors of

the present work, fall within the limits of 0.5%. The data of B. V. Voytyuk

and Yu. F. Voynov, et al, agree, also within the limits of 0.5%.

Table 21. Experimental Data of Various Authors on Properties

of Ethylene on Saturation Curve

1)

3) XeiiHHHr. I'Jtok (1

1

4) Maacc, Pafir [2]

5) KpoMMe;innr, Yore [3]

2)

1921

1921

1927

6) AiaTHiiC, KpoMv,c.iiii;r, 1927

VoTC [4] I

131,69

143.09

152.13

162,82

164,45

168.45

171,10

178,85

183,75

IS9,10

198,95

203,70

208,11

210,65

223,60

237.38

217.88

258,14

204.37

209,58

276,60

128,08

153.25

p. oap

0,05235

0.1553

0,3217

0.6775

6,314

8.602

1 1 .997 16.597

22.17

28.82

33.39

38,45

41.80

a'. At' /He

0,001735

0,001756

0,001776

0,001799

0.001824

0.001852

0,001906

0,001933

0,001601

0.001654

[Continued on next page]

KEY: 1. Authors

2. Year

3. Henning, Stock [1]

4. Maass, Wrigt [2]

5. Crommelin, Watts [3]

6. Mathias, Crommelin, Watts [4]

7. Mathias, Crommelin, Watts [4]

8. Mathias, Crommelin, Watts [5]

9. Lamb, Roper [7]

10. Egan, Kemp [6]

11. Michels, Wassenaar, Louwerse [8]

12. Michels, Wassenaar, Louwerse [8]

13. Voytyuk

14. Voynov, Pavlovich, Timrot

-49-
Table 21 (Continued)

7) M.irn3c, KpoMMe;iHHr,

yoTC (4J

1927

8) MaTtiac, KpoMMe.niHr,

yoTC 15]

9) JlaMfi. Ponep [7]

10) Bran, KeMn [6]

11) MKxe-nbc, BecccHap, Jloy- uepse [8j

[Continued on next page]

1929

1940

1937

1950

158,-i6

r/0,14

209,74

225,00

236.02

248,82

253,95

258.97

262,23

265,45

278,99

279.65

281.13

282,65

203.88

212.25

221,06

232.14

242.62

253,14

263.14

265,61

273.15

281,05

147.88

154,91 163.12 168.30

170.16

173,24

123,51

128..59 135.96

140.93

145,59

151.05

156,21

161,67

165.15

167.80

170,40

149.35

156.11 159.74 163,60

166.61 169.03 169.03

169.04

169.71 169.70

169.70

172.44

179.77

. 183.96

-188.56 196.60

204,23

213.61 223.33

233,10

243.07

5.329

7.301 9.903

14.091

19,101

25,235

32,395

34,372

40.810

48,800

0,2318

0,3946

0,6973

0.9517

1,0587

1.2640

0.02102

0.03781

0,0c082

0,12SG4

0.1914 0,2954

0,4313

0,6253

0,7812

0,9179

1 .0702 0.26030

0,43040

0.55264

0.71116

0.85894

0.99.158 0.99368

0.99377

1.0338 1.0338

1,0339

1,2101

1,7983

2.2196

2,7661

3,9575

5,4086

7,6782

10.688

14,501

19,314

0,001713

0.001762

0.001977

0.002091

0,002192

0.002344

0.002421

0.002509

0.002576

0,002651

0.003242

0,003296

0.003481

0.004630

0,07946

0.04899

0,03394

0.02389

0.01955

0.01668

0,01488

0.01315

0,007538

0.007291

0.006550

0.004630

-50-
Table 21 (Continued)

1)

p. Oao

12)MHxe;ihc, BacceHap, JloyBepae (8J

13)B0HTlOK

14)liOHHOB, riaB.nonii'i, TiiMpoi

1950

1967

1965

1967

1965

19G7

1966

1967

19C6

1967

1966

19(.7 1965

1967

1965

1966

1967

1965

1967

1965

1966

1967

1965

1966

1967

1965

1965

1967

1965

1965

1965

1965

249.67

255,26

261,89

267.84

273,59

277,30

279,61

280,54

183,15

193,15

203,15

213,15

223,15

233,15

243,15

253,15

263,15

268,15

273,15

163.3 173,15

178.15

183,1

183,15

188,15

193.15

193.15

198,15

203,15

208,15

213,15

218.15

223,15

228,15

233,15

233.15

238.15

243,15

243,15

247,4

248.15

252,8

253.15

253.15

257,2

258.15

261.8

263.15

263.15

264,7

267,2

268,15

268,15

269,8

272.2

273,15

274.4

276,1

277.8

280.9

23,087

26,677

31,438

36,231

41,354

44,946

47,306

48,279

1,265

1 .659

2,137

3.409

3,409

4,224

5,178

6,273

7.518

8,973

10,61 12.46

I 1 ,52

14.-19 16.78

19,35

19,34

21,73

22,12

25,06

25.28

25,25

27,99

28,67

31, .13 32,45

32,35

33,65

35,64

36,53

36,51

37,84

39,99

40,89

43,75

45,39

48.64

0,001831

0,001883

0,001941

0,002007

0,002084

0,002175

0,002286

0,002422

0,002610

0,002752

0,002934

0,001732

0,001785

0,001808

0,001824

0,001832

0,001856

0,001873

0,001883

0,00)911

0,00I'^41

0,001972

0,002006

0,002042

0,001'OSl

0,002123

0,002163

0,002158

0,002221

0,002272

0,002279

0,002317

0,002345

0,002401

0,002412

0,002420

0,002475

0,002510

0,002562

0,002607

0,002622

0,002628

0,002688

0,002738

0.002771

0.002764

0.002842

0.002965

0.002924

0,00:^009

0,003111

0,003455

0,6757

0,3891

0,3023

0,2357

0,2381

0,1899

0,1541

0,1531

0,1250

0,1028

0,08554

0,07179

0,06064

0,05171

0.04427

0,03755

0,03788

0,03239

0,02754

0,02775

0,02424

0,02375

0,02056

0,02029

0,02025

0,01799

0,01726

0.01554

0.01485

0,01466

0.0141!

0,01279

0,01264

0,01191

0,01090

0.00992

0.00912

0.00834

0,00666

-51-
Table 22 Experimental Data of Various Authors on Properties

of Propylene on Saturation Curve

1)

AsTopbl

2)

Foa p. 6a

p

v' , ju'/Ke

3) ;iiaacc. PaHT (2)

4) DayeJiJi, JhaaiioK [9]

1921

1939

5) BoyreH, FpcBC [10] 1940

6) JlasiG, Poncp |7J

7) Jly, HbK)HT. PyAMaH[ll]

8) TcXHIiqcCKHfl KOMHTCT

NGAA I]2J

1940

1941

1942

235,70

238.75

246.10

257.50

273,25

278,90

280.65

283.15

194,95

214.65

224.65

235.70

238.75

245,50

257.50

273.15

292.15

165.81 172,77

17G,52

180.00

184.51 189,50

195.63 202.72

207.45

213.39

220,28

225,98

273,15

298,15

323.15

348.15

363. 1

5

364.15

364.55

151.72 185.08

198.47

212,51

222,52

227,58

2.35.42 243.15

253.17

203.15

273.15

283,15

293.15

303,15

313,15

323,15

333,15

343,15

353.15 . 363,15

365,25

260,92

266.48

277,59

283,15

[Continued on next page; key on page 54]

1,480

1,742

2,228

3,426

5.679

6,986

7.359

7.919

0,02130

0,03921

0,05322

0,CG975

0.09768

0,1380

0,2060

0,3164

0,4132

0,5672

0.7977

1,0398

5.83

1 1 .53 20.55

33,94

44.76

45.68

46,00

0.005159

0,1010

0.2445

0.5394

0,8S36

1,1 !22

1.552! 2,097

3,010

4,306

5,807

7,731 10.26

13.19

16.54 20.66

25.20

.30.40 36.73

44,60

40.00

0,001542

0,001601

0,001037

0.001674

0.001684

0.001708

0.001752

0.00)827

0.001929

0.001695

0,001802

0.002092

0,002519

0,003401

0.00.^610 0,C04292

0.001703

0 001742

0.001779

0,00183!

0,00 1 883

0,001938

0,002020

0.002101

0:o02i 83

0.002288

0,002451

0.002703

0,004167

0,001775

0,001801

0,001856

0,001886

ti', M'iKe

0,08130

0,04065

0,02183

0,01 124 0,005747

0,005291

0,004292

0,1462

0,1096

0.08130

0.06211

0.04717

0.03610

0.02833

0.02188

0,01683

0.01312

0,01000

0.007299

0.004167

-52-
Table 22 (Continued)

[Continued on next page]

n "2)

10,1 p. I'.av

A\iipHM3H, IIpCiir.Tbt AloTap;i,

1919 303. 1

5

13,00 0.03604

323,15

348,15

20,56

33,92

0,02182

, 0,01 122

„ rid QappiiiinoH, Le)iA>K [14J 1949 277,59 6.722 0,001853 007009

291,26 10^49 0,001948 0,04499

310,93 15,67 0,002071 0,02945

327,59 22^55 0!002230 0,01941

344,26 31,48 0,002486 0 01250

355,37 38 75 0 002810 0 008765

360,93 42*89 0 003121 0 006792

MiixciiiC, bcccoiiap, .ioy- 1953 297.93 1 1.494 Depsc 1 15] 317.28 18J03

339.48

347,91

28.735

33' 755

355,93 39.139

361 !o2 42,910

361 ,43 43'.274 36 1 56 !3!368

363,13 44.626

1 Joo 27.3, 1

5

0,001825

235,95 0,001896

298,15 0,001975

313,15 0,002090

323.15 0,002178

333, 1

5

O.OO23GO

343,15 0,002479

348,15 0.002598

Ri"^ Ti Tir>v 183,15 0,001506

193,15 0 00 1 533

203,15 0 00156'^ 213,15 0 00 1 593

223.15 uU , 001P'>6 v/ J 1 \> *i. vj 233, 1

5

_ 0 00ifi(jl

243,15 0 00 1 698

253. 15 0 001 739

263,15 0 00 1 783

273,15 — 0,001832

283,15 0 00 1 1^86 293,15 0 001946

303,15 0 0(V^ni 4 313.15 0 002094

17ji,2 0 00 1 498

\TX1

203,2

0 00 1 479

0 00 1 572

8,332

213,15 0.5591 0 00 1 596 0,7337

218,15 0.7190 0 001619 0,5787

223! 1

5

0,9131 0,001629 0,4632

228,15 1.14G 0 00 1 646 0*3781

233.15 1.420 0 00 1 G6 4 0 3094

238,15 1,744 0 00 1 683 0.2560

243,15 2,122 0 001701 0^2136

19G5 243,2 0 00 1 70*? 0,2141

248,15 2,557 0 001720 0, 1 790

253! 1

5

3'059 0 00 1 7 1

1

0,1509

258,15 3.G29 0 00 1 76

1

0,1284

263.' 15 4!275 0,001781 o!l097

268,15 5,009 0,001808 0,09434

273.15 5.831 0,001831 0,08137

I9G5 273.2 0.001829 0,08038

1967 278,15 6,757 0.001858 0.07042

1966 2C,3,I5 7.7&3 0.001884 0,06109

285,00 8.22 C.001888 0.05767

-53-
Table 22 (Continued)

2)

Abvopu r "K V. 6ap u'. M'iKi:

^oflHOB, naB^lOBHM, TllMpOT 1967 288.15 8,913 0.0OI9I4 0,05319

l'J6G 290,00 9,39 0.001928 —

1967 293.15 10,17 0,001943 0,04651

1966 295.00 10,69 0.001954 0,04427

1967 298.15 11,56 0.001578 0,04080

1966 300,00 12,11 — 0,03889

1967 303.15 13,08 0.002011 0,03597

1965 303.5 — 0.002014 0,03592

1966 305,00 13,65 0.002018 0.03436

1967 308.15 14,72 0,002051 0.03172

1965 309,6 — 0,002054 0.03050

1966 310,00 15.35 0.002061 0,0.':027 1967 313.15 16,51 0.002091 0,02803

1966 315,00 17.18 0,002094 0,02679

1965 31,5,6 — 0,002)09 0.02003

1967 318.15 18 45 0,002135 0,024?2

1966 320,00 19,19 — 0.02356

1965 322,0 — 0,002169 0.02233

1967 32:3.15 20,55 0.002185 0,02195

1966 325,00 21.33 0.002193 0.02084

1967 328,15 22,82 0,002239 0,01935

19G5 328,5 — 0.00V239 0,01904

1966 330,00 23,77 0,002254 —

1967 333.15 25,30 0,002305 0,01708

1965 334.4 — 0.002323 0,01624

1966 335,00 26,24 0,0023.33 0,01629

1907 338.15 27,95 0,002374 0,01491

1966 340,00 28,97 0.002415 0,01422

1965 340.7 — 0,002424 0,01371

1967 343,15 30,80 0,002460 0,01297

19G6 345,00 31,84 0,002518 0,01236

1965 347,0 — 0,002547 0,01155

1967 348,15 0,002574 0,01112

1 960 350,00 35,08 0,002630 0,01054

1965 353.1 0,002722 0.009515

1907 353.15 37.18 0.002734 0,009311

I yoo

or.r. nn JJO.UU U,00//OU l),L)Uo/8/ 1905 355,6 0,002815 0,008680

358.0 • 0,002936 0,007825

.359.2 0,00.3006 0,007423

360,4 0,003101 0,006973

361,5 0,003210 0,006565

362,8 0,003389 0,005977

KEY: 1. Authors

2. Year

3. Maass, Wrigt [2]

4. Powell, Giaque [9]

5. Voughan, Graves [10]

6. Lamb, Roper [7]

7. Lu, Newitt, Ruheman [11]

8. Technical Conmittee NGAA [12]

9. Marchman, Prengie, Motard [13]

10. Harrington, Sage [14]

11. Michels, Wassenaar, Louwerse [15

12. Morecroft [16]

13. Voytyuk

14. Voynov, Pavlovich, Timrot

15. Voynov, Pavlovich, Timrot

with

up to

The recommended specific volumes of ethylene vapor coincide to 0.6%

the experimental data of the authors of the present book and diverge

3% from Mathias' data [4]. All thermal parameters on the saturation

-54-
curve of propylene were investigated in [10, 11, 13, 14]. The other works

pertain to investigation of the thermal dependences of the saturation

pressure of the vapors and specific volume of the liquid. Data on the

saturation vapor pressure, obtained by Michels and coworkers [15] , Voughan

and Graves [10], Farrington and Sage [14] and Marchman and coworkers [13],

agree satisfactorily. The average scattering among them does not exceed

0.2%. The data of Lu, Newitt, Ruheman [11] differ by up to 1% from the

data in [10, 13, 14, 15], and the data of Maass and Wrigt [2], by more

than 2%. The data of Powell and Giaque [9] agree with the data of Lamb

and Roper [7] with an accuracy of 0.5%. The discrepancies between the

individual volumes of the liquid, obtained in the works of Maass and Wrigt

[2] , NGAA Technical Committee [12] , Farrington and Sage [14] , Morecroft

[16], do not exceed 0.2% on the average. The data of Lu, Newitt and

Ruheman [11] far from the critical point agree satisfactorily with the

data in [10, 13, 14, 15]. The scattering does not exceed 0.5%. Near the

critical point, however, the discrepancies between the data of Farrington

and Sage reach 0.8%, and Morecroft 's data more than 1%. The data of

Voughan and Graves [10] on the specific volumes of the saturated liquid are

strongly understated and deviations of the relative data of Farrington and

Sage [14] and of the authors of [11, 12, 13, 16] reach up to 7%. The

disagreement of the specific volumes of the saturated vapor obtained in [13,

14, 10] averages 0.5% with maximum deviations up to 2%. In terms of the

pressure of saturated propylene vapors the recommended values coincide to

0.2% with the data of Marchman [13], Farrington [14], Michels [15], and

the authors of this book. Disagreement with the data of Maass [2] reaches

6%, with the data of Voughan and Graves [10] and data of Powell [9], 0.4%.

In terms of the specific volume of liquid propylene the data of

Voughan and Graves [10] are up to 7% lower than recommended and the data of

the other authors coincide with the recommended values with an accuracy

of 0.5%. The data of B. V. Voytyuk , Yu. F. Voynov, et al [17] coincide

within the same limits. In terms of the specific volumes of propylene

vapor the recommended values coincide to 0.6% with the experimental data

of Voughan and Graves [10] , Farrington [14] , Marchman [13] and the authors

of this book.

Heat of Evaporation

Experimental works on the heat of evaporation of ethylene and

propylene are listed in Table 23.

Experimental data on the heat of evaporation near the normal boiling

point were found by Egan and Kemp [6] (r = 483.1 ±0.4 kJ/kg at T = 169.45°K)

and for propylene by Powell and Giaque [9] (r = 438.0 ± 0.3 kJ/kg at T =

= 225.40°K). The heats of evaporation of ethylene and propylene were

measured by Clusius and Konnertz [18]. The other works listed in Table 23

contain theoretical data. The discrepancies among the various authors

reach 3%.

Our heat of evaporation (Table I) was calculated according to the

Clapeirone-Clusius equation using the recommended p, v, T-data on the

-55-
saturation curve. To determine the pressure derivative in terms of

temperature for ethylene we used the equation

Ig/; - 3U/1 7713+ 0,01102007 • ll,21392o -IgT— — (-34^

which describes our experimental data on the pressure of the saturated

vapors with an accuracy of 0.2%. The pressure derivative in terms of

temperature was determined for propylene by the graphoanalytic method. For

the 160-250°K temperature range we used the equation

Igp =^ 3.94400- ^-3^-1^3 + A, CO; (353

for temperatures above 250°K we used the equation

Ig^ - 11,53578 + 0,00208316. r- 2.90052. Igr— ---J.^ + A2 (7), (35)

where p is pressure, bar; T is temperature, °K.

Table 23. List of Works Containing Data on the Heats of

Evaporation of Ethylene and Propylene

Authors Temperature

range, °K

1)

A\aTnac II ,\p. [5] 3raH, Ke.Mii \C>] Kjiyanyc, KoiiKcpru, [18] Tn.nimeeEi 1 19|

Kpa.Mcp (20j

32ropy<ienKO I2Ij

Ethylene

1929

1937

1946

1951 1955

1959

128—281

169

143—254

113—273

123—281

153—282

2)

1 hyejiJi, H>K;;rioK [9] BoyrcH, fpcBC [10]

KJiysnyc, KomicpTu [ Oappmir roil, CeiiAK

Kaiib5:p M ;ij> (22]

T)i.'iimi:eH |)9]

.Tc'.ian 1 23

1

Propylene

18] 14j

1939

1940

1946

1949

1951

1951 1962

225

273—364

193—288

277—361

225-361

93—363

163—363

KEY: 1. Mathias, et al [5]

Egan, Kemp [6]

Clusius, Konnertz [18]

Tilicheyev [19]

Cramer [20]

Zagoruchenko [21]

2. Powell, Giaque [9]

Voughan, Graves [10]

Clusius, Konnertz [18]

Harrington, Sage [14]

Canjar, et al [22]

Tilicheyev [19]

Lehman [23]

-56-
The functions (T) and A^CT) were determined from the recommended

saturation pressures according to Table V. The derivatives of the functions

A^ (T) and A^CT) were found graphically. Near the normal boiling point of

ethylene for T = 169.45°K interpolation of our data yields a heat of

evaporation of ethylene r = 481.3 kJ/kg, which coincides with an accuracy

of 0.4% with the r obtained experimentally by Egan and Kemp [6]. The

experimental data of Clusius and Konnertz [18] coincide with the recommended

data at temperatures of 177 and 226°K. At 210°K data [18] exceed the

recommended values by 2%. At temperatures above 226°K the deviations

change sign and reach 3-4% near the critical point.

Our data coincide with an accuracy up to 1% with Zagoruchenko '

s

data [21] in the entire investigated temperature range. The deviation of

the data of M. D. Tilicheyev [19] and Cramer [20] is analogous to those of

Clusius and Konnertz [18]. Mathias' data [5] are lower than the recommended,

the deviations do not exceed 2-3% and the mean deviation is 1.5%. Near the

normal boiling point of propylene for T = 225.40°K interpolation of our data

yields a heat of evaporation of propylene r = 437.2 kJ/kg, which coincides

with an accuracy of 0.2% with the r obtained experimentally by Powell and

Giaque [9]. The experimental data of Clusius and Konnertz [18] are 0.5-1.5%

higher than the recommended. In the 210-320°K temperature range the

discrepancies between the recommended data and the data of Voughan, Graves

[10], M. D. Tilicheyev [19] and Canjar [22] do not exceed 1%. At 350°K

our data coincide with the data of Farrington and Sage [14]; Lehman's

data [23] fall 1.5% below, and Voughan and Graves' data [10] and those of

M. D. Tilicheyev [19], 1.5% above our data.

Analysis of the method of calculating our heats of evaporation of

ethylene and propylene and the character of the difference of these data

from the data of other authors made it possible to evaluate the accuracy

of the recommended heats of evaporation of ethylene and propylene as not

worse than ±1% in the temperature range from 160°K to the critical point.

Critical Parameters

The critical parameters of ethylene and propylene were determined in

the works listed in Tables 24 and 25. The specific difficulties of experimental analysis of the critical parameters are the cause of considerable

difference among the results obtained by the various authors. Detailed

analysis of the methods and results of investigation of the critical

parameters of ethylene and propylene is done in the work of Kobe and

Lynn [38].

The critical pressure and temperature can be measured directly. The

critical specific volume, however, because of the infinite compressibility

of the compound in the critical state and difficulty of reaching thermodynamic equilibrium, is determined experimentally with great errors.

Various empirical principles [28, 47, 48] yield more accurate results.

-57-
Table 24. Critical Parameters of Ethylene According to Various Authors

Authors Year r. p. Cap

Tr

^^^-=—

Ban Aep Baa.Tbc [24] 1^80 282.35 58.77 0,00278

Cappay [25] 1882 274.C5 44.08 0,00676

Ka^b'-Tc-T [20] 1S82 280.15 — —

Abioap [271 1881 283,25 51.67 —

KavTbCTei, AlaiHac [25] 1885 285,65 — 0,004762

O.TbiiieBCKiifi i'2rtj 18')5 283,15 51.67 —

Bii.a.iapj (30

1

1897 283.15 — —

Kapaoao, y\|.;"i (31) 1912 282,65 51.32 —

Maarc, Te.i.^ec ( j2j !937 282.65 50,64 0.004212

/i'iacc, Poi'-.r (21 1921 283,05 — —

Whk HiiTOii;, i'MJuicc [33] 19iS 282.05 — —

AiaK Hhtoui h ^ip. [3 i] 1939 233,05 51.17 0.00440

HaJib.if^T, Kc.ncc [35] 1940 282,36 — —

Keii [36] 1948 282,40 50.71

rieppii [37] 1950 282.85 51.57 0.00154.5 Ko5c, Jlnnn |3S] 19 ")2 283.05 51.17 0,001405

/iiiii [30] 1956 282.65 50.04 0.004550

Craiun, To.vjc [-lOJ 19-H 282,4 50,60

O.niiHH, Torioc [1 ;

)

1962 283,1 0.004406

Baprad^TiiK [12j 1963 283,05 50,97 0.004739

Karu i; ap. [ iS] 1965 283.05 51.17 0.004402

ripilHHTbiC 3iia'IeHll.l 283,05 51,0 0.00409

KEY: 1. Van der Waals [24]

Sarrau [25]

Cailletet [26]

Dewar [27]

Cailletet, Mathias [28]

Olszewski [29]

Villard [30]

Cardoso, Arni [31]

Maass, Geddes [32]

Maass, Wrigt [2]

Mcintosh, Maass [33]

Mcintosh, et al [34]

Naldrett, Maass [35]

Kay [36]

Perry [37]

Kobe, Lynn [38]

Din [39]

Stiel, Thodos [40]

Flynn, Thodos [41]

Vargaftik [42]

Katts, et al [43]

Accepted values

The p, V, T-data of ethylene and propylene on the saturation curve

which we recommend agree satisfactorily with the following critical parameters: for ethylene T^ = 283.05°K, p^ = 51.0 bar, v^ = 0.00469 mVkg; for

propylene T^ = 365.05°K, p^ = 46.4 bar, v^ = 0.00434 mVkg.

These data were obtained in the following manner. The critical

temperatures were taken from [42] . The critical pressures were found by

graphic extrapolation to T^ of the recommended data in terms of the

saturation pressure of the vapors. The critical volumes were determined

according to the empirical law of averages. According to this rule the

graphs of the functions

2

V' -f- V- /(Ig P )

-58-
in the range of temperatures from critical to a temperature 50°K below

critical are linear to 0.5%, and the point of intersection of these curves

d' + d" I with log -—^

- log /p'*p" corresponds to the logarithm of the critical

density (Figure 4)

.

2,7

2/

1.S

^ 13

1.1

1.0.2.r 2.2 2,3

—7

2

A'' / a /

±J

J 1

/1 1 2.^ 2.S 2,6 IgV^

Figure 4. Critical volumes: 1 -- ethylene; 2 -- propylene;

3 -- water; 4 -- carbon dioxide gas.

The mean deviations between the

of other authors are: for pressure for

for specific volumes for ethylene 3.8,

data which we recommend and the data

ethylene 0.2, for propylene 0.9%,

and for propylene 0.07%.

-59-
Table 25. Critical Parameters of Propylene According to Various Authors

Year T, "K D, tap e. M*lia

1— " —

Ha,ie/i<AHH (44) 1 1883 370,15 — —

3H6epT, Byppe^ib ]4o\ 1915 365,75 45,94 —

iMaacc, Pain |2| 1921 365,25 — —

BnHK;iep, Maacc |46J 1933 365,15 — —

Boyrei), fjyeBC [10| 1940 364,55 46,00 0,004292

Baiaepc (lOj 1940 365,05 45,19 0.004273

ny, HeaiiT ( 1

1

1

1941 365,25 46,00 —

,\\apMMan 11 Ap- (13] 1949 364,91 46,21 0.004539

OappHHrTOH, Cei(.i/K |14| 1949 364,82 46.06 0,004335

rieppii [37] 1950 365,45 45.60

Kooe, J\mn (38| 1953 364,95 46,20 0,004292

Cran.!, Toaoc (40)

«lJ."inHii, Toaoc [41)

1961 365,1 46.00

1962 306,0 0.004292

Bapra^jTiiK [42] 1963 365,05 46,00 0,004292

Karn II ;ip. (43) 1965 365.03 45.99 0,004430

npuHHTbje 3fiaMeiifia

1

365,05 46.4 0.00434

KEY: 1. Nadeydine [44]

Siebert, Burell [45]

Maass, Wrigt [2]

Winkler, Maass [46]

Voughan, Graves [10]

Zayders [10]

Lu, Newitt [11]

Marchman, et al [13]

Harrington , Sage [14]

Perry [37]

Kobe, Lynn [38]

Stiel, Thodos [40]

Flynn, Thodos [41]

Vargaftik [42]

Katts, et al [43]

Accepted values

-60-
CHAPTER IV. THERMODYNAMIC FUNCTIONS OF ETHYLENE AND PROPYLENE IN PERFECT-GAS

STATE

Review of Data

The perfect-gas functions of ethylene and propylene presented in

various sources were obtained on the basis of experimental measurements of

the heat capacity of these compounds at atmospheric pressure or by means

of calculation on the basis of spectroscopic data. The primary sources,

which contain either experimental data on heat capacity or the results of

original calculation of the perfect-gas functions according to spectroscopic

data for ethylene and propylene, are listed in Table 26. In the range of

temperatures above 273° K the most reliable are considered the functions

derived on the basis of spectroscopic data. At lower temperatures the only

source of information concerning the perfect-gas functions of ethylene and

propylene are experimental data on heat capacity.

The works of House [1] , Eucken and Parts [2] , Burcik and coauthors

[3] , Egan and Kemp [4] pertain to experimental analysis of the heat

capacity of ethylene at low pressures.

Heuse [1] determined the heat capacity of ethylene at atmospheric

pressure in the 182-291°K temperature range by the flow method. The data

of Eucken and Parts [2] were obtained by adiabatic expansion in accordance

with the Lummer-Pringsteim method.

at temperatures of 270.7, 300.0 and 320. 7° K by the same method. The

essence of the method consists in determination of the change of

temperature and pressure during adiabatic expansion of the gas. The heat

capacity in the perfect-gas state is calculated according to the measured

values using the known thermodynamic relations according to the equation

Burcik and coworkers [3] determined the heat capacity C of ethylene

[H=in; k=f;

kp=cr]

(37)

-61-
I

where p. , T. are the initial pressure and temperature; p-, are the m " ''t t

final pressure and temperature; is the second Virial coefficient

according to Keyes [17]

.

Burcik and coworkers [3] analyzed and compared the results of all

the listed works. Approximation of the experimental data is done in the

very same work. The deviation of the experimental data from the dependence

expressed by the equation I

Cp = 9,638 - 3, 109. 10"' 7 i- 1.551 • 10-' 7-2-1,426 • 10"^

(-jg^ ;

where T is temperature in °K, C° is heat capacity in cal/ (mole'deg) in

j the 200-300°K temperature range, does not exceed 1%.

i Eucken and Parts [2] determined the heat capacities at T equal to j 178,6, 192.8, 210.8, 231.4, 250.9, 272.1, 293.5 and 464. 0°K, equal i respectively to 8.293, 8.450, 8.86"0, 9.001, 9.332, 9.809, 10.257 and \ 14.161 cal/ (mole'deg) . Burcik and coworkers [3] determined the heat \ capacities for T equal to 270.7, 300.0 and 320. 7°K, equal respectively to ! 9.74, 10.39 and 10.99 cal/ (mole'deg) and House [1] determined the heat | capacities for T equal to 182.2, 205.2, 237.2 and 291.2, equal respectively [ to 8.28, 8.54, 9.02 and 10.14. !

! One of the first studies on calculation of the thermodynamic functions'

according to spectroscopic data was Kassel's work [9] -, in which is described

j a method of calculating the entropy for multiatomic gases, and also the free | energy of ethylene in the 300-3, 000°K temperature range. The spectroscopic i data of Mecke [18] were analyzed in the work.

The entropy of ethylene at the critical point T = 169.40°K was

calculated by Egan and Kemp [4] on the basis of calorimetric measurements

and was found to be = 47.36 cal/(mole*deg) . The entropies at the

two temperatures were also calculated in this work on the basis of vibration frequencies: S° = 47.35 and S°^gg = 52.47 cal/ (mole 'deg)

.

Later on Thompson [10] , using the data of Conn and Sutherland [20]

,

determined the heat capacity, entropy and enthalpy change of ethylene in

the perfect-gas state. These data were subsequently refined by Kilpatrick

and Pitzer [13]

.

The thermodynamic functions of ethylene and propylene, calculated on

the basis of spectroscopic data of Callaway and Barker [21] , are given in

[13] . The heat capacity, entropy and enthalpy change determined by

Kilpatrick and Pitzer [13] were used as the basis of tables on the caloric

properties of ethylene and propylene presented in [22]

.

Later on L. V. Curvich and coworkers [12] determined the new entropy

and enthalpy change of ethylene in connection with more accurate spectroscopic data, presented in [23, 24, 25].

-62-
Table 26

1)

AUTOPU

Xefiae (1|

9iiK0H II rinpTc [2] BypciiK 11 cuaDTopbi |3| 3raii H Ks-,n |1|

KHc;>ii{oucKiiri, Pai'ic [5] KHcinKOBCKin'i, /laxan,

P^HiOM |G|

Te^hcjcp 1 7)

riaytvi.T li Jln\'d\\cK |8|

Kaccc;ib (9)

TOMITCOH flOl

rpaw]'op,i 1 1 ! 1 rypnii>( 11 co.iHioDij [12|

KHJinarpnK, IlHTuep ; 13]

CTajw (I (Maii({)n.i,i

CneHcep [15]

ByKa.noBHM >< coaoTopu

(161

2) _3)

/iiiKOiin- HHH

1 (I'M'JitUH.IMH'lCCKHr JjyHKUllH

4) 5)

ntx)niweHa

6)

HiiTe)ina^ TeMne- pnxyp 7'. °K

1919

193'j !S1! 193/

1910

1940

1942

1939

1933

1941

1 939

I9!,2

194G

1943

1948

1953

Cp (3KCfICpMMeHf

)

To -AiL- 8)

/ ' 9)

ncpHMl'llT, paCMCT)

10)

PaCMCT H3MeHei!i(5l

BHyTpeiineii sHepriiii

(pacMci) 11)

(pacHCT) 11")

fr-lCM'JT) 11 J C^, (pacMfT) 11)

3,\ii;iipi!<i'ec'\i:K;

'^ypaiiHeiiiic ,Mr/

(prc':::r) H)

(SKCIiepMM'.'HT)

8)

p To >i<e

' 9)

5" (SKCnCpUMCHT H

paciier)

S° (pac'ier) H)

PaCMCT 11)

To H<c 8)

iMiiHpnqecKoe 12)

ypaBiiemte n.Jin C

.3 y , .0 C- S;.H„^~fI,

(pacHf-T) 11)

182—291

178—464

270—321

1 09.4—298.1

272—366

148—259

270—510

225—298

300—3000

291 —1500

298,15

293—6000

298—1500

250—1500

298—1500

273—1473

KEY: 1. Authors

Heuse [1]

Eucken and Parts [2]

Burcik, et al [3]

Eg an and Kemp [4]

Kistiakowsky and Rice [5]

Kistiakowsky, et al [6]

Telfair [7]

Powell and Giaque [8]

Kassel [9]

Thompson [10]

Crawford [11]

Gurvich, et al [12]

Kilpatzick, Pitzer [13]

Stull, Mayfield [14]

Spenser [15]

Vukalovich, et al [16]

2. Year of publication

3. Thermodynamic functions

4. Ethylene

5. Propylene

6. Temperature range T, °K

7. C° (experiment)

8 . Same

9. (experiment, calculation)

10. Calculation of change of

internal energy

11. (calculation)

12. Empirical equation for

Deviations of the data from the values presented in [13] do not exceed

0.4%. Interpolation equations are also presented in [12] for determining the

entropy and enthalpy change in the 293-1, 600° K temperature range. The

-63-
perfect-gas functions of ethylene, calculated on the basis of spectroscopic

data, are presented in Tables 27, 28, and 29.

Experimental data on the caloric properties of propylene are found

in works by Kistiakowsky and Rice [5], Powell and Giaque [8], Kistiakowsky

,

Lachar and Ransom [6] , and Telfair [7]

.

Kistiakowsky and Rice [5] analyzed the heat capacity of propylene

at 272-367°K by the Lummer-Pringsteim method. Kistiakowskiy , et al [6]

determined the heat capacity of propylene at temperatures below 273°K by

the relative heated wire method.

The heat capacity of propylene according to Telfair [7] was calculated on the basis of data on the speed of sound in propylene.

Telfair's data agree satisfactorily with the experimental heat

capacity values determined by Kistiakowsky, et al [5, 6]. The deviations

of the experimental data from, the smooth curve do not exceed 0.5%.

Table 27. Heat Capacity of Ethylene and Propylene According

to Various Authors

T. "K

1) c°. KaJl/(MC.l' •jix:o) no aaiiHbiM

2)

Ki: 'ini.rpHK.'.. nnTr(epa [13] ii Poi - ClIHH 1 1:- 1 3) '/riM.T.. . AiarKt/ii.iaa [14]. "iO!.;ncoiia [10]

5) 4) 5)

npon:<.ieii

4)

3TH.ieii

250 9,53 13,76

29i,!ti 10,23 298. IG 10,41 15,27 10,45

300 10.45 15,34 10.48 15,43 10.50 350 11.56 17,24 1 1 ,67

400 12.90 19,10 12,69 19,11 12,95

450 13,81 20,93 14,11

500 15.1*j 22,62 14,89 22,68 15,21

550 16,22

600 17.10 25,70 16.87 25.83 17,15

650 18,01

700 18.76 2»,37 18,61 28,55 18,30

800 20, -20 30,58 19,96 30.92 20,20

900 21,10 32.70 21,45 32,97 21,50

1000 22,57 3-!.46 22,62 34.75 22,60

lICO 23.5-t 35,99 23.63 36,29 23,60

1200 24.39 37,32 24,51 37,63 24,40

1300 25,14 38,49 25,26 3S,79 25,20

1400 25.79 39,51 25,92 39,79 25,80

1500 26,3d 40.39 26,50 40.60 26.40

KEY: 1. C^, cal/(mole-deg) according to data 4. Ethylene

P r -, , . . r^-^-, 5. Propylene

2. Kilpatrick, Pitzer [13] and Rossini [22]

3. Stull, Mayfield [14], Thompson [10]

-64-
Table 28. Entropy of Ethylene and Propylene in Perfect-Gas State

According to Various Authors

TT S , K.IA/[MUA'- -^I'llO) II', .I'lmiUM

2XKJinaTpHi;a. I'MTUepj ii I'oc(.mh» (2?! , gypM iicoi i [lOj. ry;>F,ii>ia ii ooasTopoB [12]

0 1/ / , K ^ J 5) 4)

Sth.ich

L'Ol.lG —

2'JJ,)0

298, J b 52,45 C-3,80 ^9 d. 1 9

300 52,51 63,90

350

400 55,89 68,86 00, /OO

450 57,48

50U 58,98 73,47 59,05 58,841

5[>0 60,52

600 61,92 77.82 61,97 61,740

G50 63,38

700 G4,G.S 62,04 64,73 64,473

too 67,2.> 85,98 67,35 67,050

900 69,74 S9,72 09.71 69,487

ICOO 72,0'j 9X26 72,13 71,792

1)00 74,2') 96,61 74,34 73,978

1200 76,0} 99,80 76,33 76.054

1300 78,32 102,84 78,40 78,028

MOO S0,21 105,98 80„30 79,908

1500 82,01 108,48 82,11 81,702

KEY: 1. S°, cal/ (mole -deg) according to data 4. Ethylene

2. Kilpatrick, Pitzer [13], Rossini [22] 5. Propylene

3. Thompson [10], Gurvich, et al [12]

Table 29. Enthalpy of Ethylene and Propylene in Perfect-Gas State

According to Various Authors

T. °K

1) ;/

o- - - .'/,,, K,tA:'M 'Ab

2yn^naTprK;i. I'MTL'^r-na [I3j i; I-.X.-HIIH (L'l;'! 3}o. isa H coabropOB [12]

4) 3 in.'; OH 5) I Ico;;h.im: 4)

3tjI.tch

291,16 2456

29:^ 1

6

2465

298,16 2525 3237 2527 2516

300 2544 3265 2548

350 3100

400 3711 4990 8720 .3684 450 4100

500 5117 7076 51.30 5067

550 5920

600 6732 9492 6750 6661

650 7630

'/OO 8527 12200 8550 8436

800 10180 15150 10500 10367

900 12560 LS320 12500 12438

1000 1476') 21 ',90 14800 14626

1100 17070 2:2i0 171 10 16920

1200 19470 2 •iSO 19450 19306

1300 219.50 32760 21970 21774

1400 24490 30570 24J20 24311

1500 27100 40570 27160 26912

KEY: 1 . H° - H° cal/mole according to data 2-5. Same as Table 28

-65-
Tables of the heat capacity of propylene, tabulated on the basis of

processing of experimental and theoretical data, are also presented in

Lehman's work [26] for the 220-1, 270°K temperature range. Experimental

data on the heat capacity of propylene in the perfect-gas state are given

in Table 30.

Table 30. Experimental Data on Heat Capacity of Propylene

in Perfect-Gas State

r. "K T)

X epad)

Ka.ili X cpjd)

U li r. "K 1)

Cp, KaA/(jUOAb X

X zpad)

2) Tejib(f)e)) |7| >X'!CTnKOBCKnri, vlnxap, PainoM [6]l

270

280

290

300

310

320

330

340

350

360

380

390

400

410

420

430

440

450

460

470

480

490

500

510

12,30

12,70

i3.o:» 13,48

13,36

14,34

14,62

14,99

15,36

15,73

16,45

16,81 17.17

17,53

17,89

18,24

18,59

18,94

19,29

19,63

19,98

20,32

20,33

21,00

148,1

148,3

157,3

157,6 158.0 212.3

212,9

219,9

220,2

223,4

256,4

258.3

258.4

259,0

291.1

10,63

10.64 10,86

10,86

10,87

12,46

12.50

12.68 12,70

12,82

13,90

13,97

13,98

14,04

15,16,

4) Paiic [5] 272,29 f 14.36

299.33 15.47 333,86 16.74 367.11 17,93

KEY: 1. cal/ (mole-deg) 3. Kistiakowsky , Lachar, Ransom [6]

2. Telfair [7] 4. Rice [5]

The entropy of propylene at the boiling point T = 225,39°K was determined directly by caloric measurements by Powell and Giaque [8] and was

found to be 59.93 cal/ (mole'deg) . This same researcher calculated the

entropy of propylene on the basis of spectroscopic data for two temperatures

^225 35 ^^'^ ~ ^"^ ^298 " ^'^•lO cal/ (mole'deg) . Crawford and

coworkers [11], using the corrected vibration frequencies, obtained the

following entropy for propylene at the boiling point: S"^^ ^5

~ 59.87

cal/ (mole'deg)

.

Of great importance in addition to the cited works are calculations

on the basis of spectroscopic data by M. P. Vukalovich and coworkers [16],

Stull and Mayfield [14] , in which the thermodynamic functions of a large

number of gases, including ethylene and propylene, are determined. The

comparisons of the results with existing literature data on the perfect-gas

temperature of ethylene [2, 3, 10] made by Stull and Mayfield revealed that

-66-
the maximum deviations are, respectively, 0.7, 0.9 and 2.1%. The theoretical

heat capacities of propylene were compared with the data in [5, 7]. The

maximum deviations here are, respectively, 0.8 and 0.3%.

M. P. Vukalovich and coworkers [16] give the perfect-gas heat

capacities, enthalpies and entropies of ethylene and propylene at

273-1 ,473''K. The perfect-gas functions of ethylene and propylene, determined by various authors on the basis of spectroscopic data, are presented

in Tables 27, 28, 29.

Recommended Isobaric Heat Capacity, Entropy and Enthalpy of Ethylene and

Propylene in Perfect-Gas State

At the present time the most reliable data on the entropy and

enthalpy change of ethylene in the perfect-gas state are those of L. V.

Gurvich and coworkers [12] . The entropy and enthalpy change of ethylene

were calculated in the same work using current data on the ground frequencies

and rotation constants of the ethylene molecule. Also given there are

interpolation equations for calculating the entropy and enthalpy change of

ethylene in the 293-6, 000°K temperature range.

If the heat capacity of ethylene is calculated by converting the

interpolation equation for entropy, the results obtained at temperatures

above 700°K agree satisfactorily with M. P. Vukalovich' s data [16] and

those of Kilpatrick [13]. The discrepancy does not exceed 0.5%. At

temperatures of 298-500°K, however, the heat capacity of ethylene, calculated according to the converted equation, differs from the heat capacity

given in [13, 16] by more than 5%.

Considering that the heat capacities of ethylene were computed

directly in [13, 16] on the basis of spectroscopic data, these data were

preferred for tabulation of the perfect-gas heat capacities in the

280-500°K temperature range (Tables II, VI). Data [13, 16] at these

temperatures are quite satisfactorily transmitted (±0.4%) by the Spenser

interpolation equation [15] presented below:

Cl a -i- bT + -i- dT\ (39)

where a = 1.003, b = 36.948*10"^ c = -193,81-10"^, d = 4.019*10"^

Using the known thermodynamic relations we find from equation (39)

the expressions for the entropy of ethylene and for enthalpy change in

the perfect-gas state:

-h Si. (40)

o o /,ra c7'3 rfT" f bfl cTi dXi (41)

-67-
The thermodynamic functions of ethylene, computed through equations

(40) and (41) for the 280-500°K temperatures, differ from the data of

L. V. Gurvich [12] in the case of entropy by 0.4%, and in the case of

enthalpy by 0.7% (see Tables 28 and 29).

The most recent works in which the thermodynamic functions of

propylene are analyzed are those of M. P. Vukalovich and coworkers [16]

and of Kilpatrick [13]. The heat capacity of propylene, computed from an

equation of the type (39) in the 280-500°K temperature range for a = 0.790,

b = 56.372, c = -281.07-10"^ d = 3.427'10"^ differs from the data of

M. P. Vukalovich, et al [16] by not more than 0.5%. The entropy and

enthalpy change obtained from equations of the type (40) and (41) , also

agree satisfactorily with the data of M. P. Vukalovich and coworkers [16].

The deviations do not exceed 0.4%.

The thermodynamic functions in the perfect-gas state, calculated

according to equations (39), (40) and (41), were used by us for compiling

Tables II and VI of the thermodynamic properties of ethylene and propylene

at temperatures of 280-500°K.

Spectroscopic data do not exist for temperatures below 273°K, and

the only source of information about the perfect-gas functions of ethylene

and propylene are the results of experimental measurements of the heat

capacity or speed of sound in these gases at small pressures. The accuracy

of such data is considerably less than that of the data calculated on the

basis of spectroscopic data. In the 200-280°K range equation (41) of

Burcik and coworkers [3] is recommended; for propylene (T = 148-291°K) the

experimental data of Kistiakowsky and coworkers [6], presented in Table 30,

are recommended.

-68-
CHAPTER V. SPEED OF SOUND AND HEAT CAPACITIES OF GASEOUS ETHYLENE AND PROPYLENE

Review of Data on Heat Capacities of Gaseous Ethylene and Propylene

The isochoric heat capacity of ethylene and propylene in a

comparatively narrow temperature range and pressure range was measured by

Nevers and Martin [1], Pall, Broughton and Maass [2].

Nevers and Martin [1] did their study in the 340-420°K temperature

range for reduced densities oo equal to 0.218-0.726, in order to check the

suitability of the Benedict-Webb-Rubin [3] and Martin-Hou [4] equations of

state for calculating the isochoric heat capacity of propylene in the stated

range of states. The investigated specimen of propylene was 99.0 mole %

pure; the heat capacity was measured in a constant-volume adiabatic

calorimeter of original design with a blower (mixer) , resistance heater and

thermometer installed inside the calorimeter. The calorimeter was calibrated for filling with propylene at low pressure. The perfect-gas heat

capacity of propylene C^ was determined by the Kilpatrick-Pitzer method,

and the small pressure correction factor was calculated on the basis of the

Martin-Hou thermal equation of state. The heat capacity of propylene was

7% of the total heat capacity of the reactor and contents; the pressure

correction factor AC was 0.1% of this value. The error in determination

Vo

of the calorimeter constant, according to the authors, did not exceed ±0.8%,

and the scattering of individual measurements did not exceed ±0.4%. The

calorimeter was filled from a light-weight steel container, which was

weighed before and after filling of the apparatus. The density of the

investigated compound in the calorimeter was determined with an error not

exceeding ±0.3%. The temperature drift of the calorimeter, occurring

during operation of the mixture and with the resistance thermometer turned

on, a value of -0.002 deg/min, was taken into account in the processing of

the results of the calorimetric experiment. The error of the isochoric

heat capacity obtained for propylene as a function of the density of the

investigated compound was ±1.1-3.2%. The experimental data obtained in [1]

are presented in Table 31,

The authors found [1] as a result of comparing the experimental data

-69-
on isochoric heat capacity with the theoretical according to the abovedescribed equations that the discrepancy in the investigated range of the

compounds does not exceed 6.7% of the pressure correction factor AC^ for

the perfect-gas heat capacity, but the isotherms of heat capacity in heat

capacity-density coordinates haVe a varying qualitative path. The isotherms plotted on the basis of experimental data have a positive second

pressure derivative in the low pressure range and in the entire density

range

.

Table 31. Experimental Data [1]

IK

0, e/cM' p. ejcj>i' I. °c p. 2/cm' t. "C

e-spad e-epad

0,04814 G7.I5 0,3903 0,09228 84,64 0,4380 0,1404 93,17 0,4842

82,14 0,3952 92,91 0,4337 99,58 0,4710

98.45 0,4047 103,71 0.4341 106,68 0,4659

111,62 0,4!59 115.36 0.4385 112.47 0.463S

123.90 G,4226 125,32 0.4439

140,21 0.4357

0.07219 75,09 0.41f30 0,1102 90,71 0,4486 0,1609 94.92 0.4991

85,2! 0,4163 95,75 0.4460 99.51 0,4840

99,93 0,4208 101.28 0,443S 104.51 0,4761

117,06 0,4:S05 107.59 0,4439 103.74 0.4768

133.72 0,44 12 113,37 0,4438 108.41 0.4704

145.92 0.4485

KEY: 1. C^, cal/Cg-deg)

The theoretical data on the caloric properties and thermodynamic

diagrams of ethylene and propylene at high pressures, presented in [5-9],

were obtained on the basis of experimental p, v, T-data of Michels and

coworkers [10, 11], or on the basis of thermal equations of state whose

derivation was based on these p, v, T-data.

Calculation of the isobaric and isochoric heat capacities and their

ratio on the basis of the results of analysis of thermal properties

necessitates, as we know, determination of the second derivatives of the

thermal functions, which leads to considerable loss of accuracy, particularly

in the near-critical and supercritical regions of state. As a rule, the

errors of such calculations exceed by more than one order of magnitude

the errors of the initial thermal data. In the range of state parameters

where the heat capacities peak, the various equations of state, which

describe the experimental p, v, T-data with the same accuracy, lead to

heat capacities that differ by 30-60%. Calculation using the experimental

data on the speed of sound occupies a special place, among the indirect

methods of determining the heat capacity of gases.

The use of p, v, T-data and the speed of sound, which are presently

the most accurate measured properties of matter, in calculations of heat

capacities C and C , their ratio k and adiabatics index k , makes it ^ p V V

-70-
possible to find the stated parameters with an accuracy much better than

that of calculation simply on the basis of p, v, T-data.

Review of Experimental Data on Speed of Sound in Gaseous Ethylene and

Propylene

Works pertaining to experimental analysis of the speed of sound in

gaseous ethylene and propylene are listed in Table 32.

Herget measured the speed of sound by acoustical interferometry on

the frequencies 274.1 and 598 kHz at pressures of 35-70 bar on the 9.7,

18.7 and 23°C isotherms. The investigated ethylene was 99.7% pure. The

pressure was measured with a class 0.5 piston manometer. The results of

the measurements are presented in Table 33.

The experimental data, in Herget 's opinion, have an accuracy of

±0.05% in the entire range of investigation, with the exception of range

of minimum speed of sound on the 9.7°C isotherm, where the error of the

data is estimated at ±3.5%. The information in the work is not enough

for analysis of the accuracy of the speeds of sound presented. Graphic

processing of the measurement results, however, shows that the scattering

of the experimental points exceeds the stated error and averages ±0.2%.

Table 32

1 ) AriTopu

Xcprer [12)

nap6pyK H Pii'iapAcon (13)

M'XwpcH H Hypii 114)

Co'ijareHKO, /Iper^.anc

(15, 16J

Te;ih4>eHp [17]

&).W.rcnKO, JXpQryjinc

[15. 181

pna.n KCC^eAOBaiiiibix TenncpaTyp ii flaiuiciimi

4) 3TH;ieH

( = 9.7—23° C; p — 33—70 Cap

t =- 7— 1S.7" C

p 1 —100 Gap

t =--=: 25—50^C

p 30—1000 6ap

T - 190—470^ K

p 1- 100 6ap

5) nponii;ieH

/=--L'—217'^C;

p -= I 6ap

T = 190—470' K; p = 0.1 —100 Gap

3 k..pMa npeflCT.nu;ieiiHH pfsyjibTaroB

ncc.^e.1onaHH^l

6)Ta{3;THUbi 3KcncpiiMenTajibHbix 3Ha7)Ma.no(}x)pMaTiiL.iri rpa(pnK

7)To >Ke

6)TaG.iimbi SKcncpHMeHTa.ibnux snaMCHHfl

8)Ta6;iHUbi TcnJiocMKocTH, paccMiiTaHHue no CKopocm snyKa

6)TaOjiHUbi iKciiepiiMeHTa.abnbix 3HaKEY: 1. Authors

Herget [12]

Parbrook, Richardson [13]

McHirsi, Houry [14]

Soldatenko, Dregulyas [15, 16]

Telfair [17]

, Soldatenko, Dregulyas [15, 18]

2. Range of investigated

temperatures and pressures

3. Form of presentation of results

4. Ethylene

5. Propylene

6. Tables of experimental values

7. Small-scale graphs

8. Tables of heat capacity,

calculated by speed of sound

-71-
Table 33

p. (>up w, MiceK p. 6ap w, M/ceK P. (>cip ttl, M/ceK

9,7" C t — 18.7° C t 23,0° C

35.73 265.3 36, io 276.8 36,2) 281,6

43,03 247.6 44,23 261,5 38.17 278,6

45,8 i 239.1 51,38 247.2 39,71 276,1

49,S1 222.0 55,73 236.8 41.1

1

273.6

51,32 202.8 58.96 230.6 4 1 .88 272.1 51,43 193,0 1 59.59 229,6 42,47 271,1

51.'55 I(')0.0 60.4

1

228,7 45.19 266,4

5!.73 162,0 61,16 229,3 48.06 261,5

51,73 165,0 61,94 232,4 48,2! 261,1

51.94 196,2 62 25 234,1 50,34 257.4

52.35 2:>5,0 63 04 240,4 52.52 253,1

53.G5 263,0 63.73 246,5 53,50 256,1 54.11 280,8 64.46 254.8 54.90 249,0

54,08 290,0 66.48 275,5 57.73 244,2

55.31 298,6 68.68 300.3 60,28 240,7

5G,03 309,0 69,38 306.5 61.86 238.4

0/,. 2 ol o,U /U.IO Oil r 31 1 ,5 62,48 237.2

59,25 348,5 71,31 322,8 63.71 237.7

71.48 325.6 65,23 240,3

72.72 65.8(i 242,1

67,05 246,3

67.66 249.9

Parbrook and Richardson [13] studied the speed of sound in ethylene

by means of interferometry with a mobile reflector on frequencies 0.5 and

2 MHz. The measurements were done at 7°C in the 25-50 bar pressure range

and at pressures from atmospheric to 100 bar on 18.7°C isotherm, on which

the dispersion at atmospheric pressure was observed. The accuracy of the

data obtained by the authors is not stated, and the published data do not

permit evaluation of the possible error,

McHirsi and Noury [14] measured the speed of sound in the 30 to

1,000 bar pressure range at 25 and 50°C by the light diffraction method on

an ultrasonic network at 865, 2,590 and 4,320 kHz. According to the authors

tiiere was no dispersion of the speed of sound and the maximum measurement

error was ±1%.

The results of the investigations [13, 14] are presented in the form

of small-scale graphs, which hampers their use in the calculation of the

thermodynamic functions.

Yu. A. Soldatenko and E. K. Dregulyas [15, 16, 18] measured the

speed of sound in ethylene and propylene by acoustic interferometry with

variable emitter-reflector distance, ensuring high accuracy of measurements

in the investigated range of state parameters.

-72-
Table 34. Speed of Sound in Ethylene According to Data of

Yu. A. Soldatenko and E. K. Dregulyas

1 p. Cop W, MjCtf. P. Cap W. MlCCK p. 6ap w, m/cck

7= 193.15° K

0.61 274,8

0,88 274,0

1,01 273,3

1,75 269,0

1,95 267,8

2,76 264,4

2,97 262.8

3,35 262.3

3,40 261,1 r-r 213,15° K

1,49 284,2

5.22 273,4

6,30 270,3

T1,48

2,40

5,22

9,73

13,06

T:

0,80

3,35

10,6i

17,87

21,59

T0,59

3,35

7,28

11,74

19,83

27,09

31,40

32,38

T0,84

1,57

2,97

5,41

11,05

18.16

24,63

25,22

31,30

32,53

34,&3

37,19

39,34

39,50

39,93

40,91r =

0,72

1,00

1,04

233,15° K

295,0

291,8

285,<S 275,7

265,0

247,48" K

307,6

301,4

281,9

264,8

252,5

263, 1 5° K

315,4

309.3

302,8

294,1

277,2

257,6

240,8

236.3

273,15° K

322.2

3! 9,9

316,1

311,3

302,5

290,0

276.6

275,4

260.G

257,3

250,8

243,1

234,8

231,1

232,0

224,8

283,32° K

327,2

328,1

326,4

7 =

3,95

4,68

10,59

10,82

12,88

16.31 23.06

29,55

35,03

39,05

39,32

43,22

46,11

47,49

49,44

49.85

50,44

.S0,50

51,6i

52,00

52,12

52,59

52,88

52.89

53.38

54,53

54,93

55,03

57.94

59,33

59,84

60,78

65,13

69,93

76.06

76,11

89,47

99,37

1,01 1,83

1,99

3,95

4,G8

6,97

13,36

19,82

26,07

29,53

36,05

40,8,5 46,09

50,52

51,50

53,47

5'i,53

50,11

57.17

283,32" K

319,3

317,9

309,5

308,9

306.2

300.5

289.2

278.4

267,5

257,8

258,4

248,7

239,6

235,1

226,5

223.2

219,8

217,9

205,6

18^4

188,5

203,3

211,8

228.1 231,5

241,1

271,2

283,7

282,2

326,6

339.8

346,4

35,5,1 3t^8,7 422.4

454.9

456.3

512,0

547,5

292,89° K

331,4

328,2

327,3

323,5

322,6

319,4

311,6

302,7

293,1

287,9

277,1

26S,8

253,8

249,6

248,3

244,5

241.5

238.5

235,5

T58,57

59,64

60,82

61,16

61,56

62,53

63,57

63,65

65,76

68,57

70,71

73,36

79.63

90.24

99.39

1,66

2,76

4,91

8,84

12.77

15,22

19,63

29,87

39,34

46,80

47,48

51,41

55,43

59,45

63,22

64,64

66,70

67,24

68,76

69,65

71,21

74,55

82,10

91,91

92,00

99,66

r =

3,45

10,00

25,52

29,44

36,89

47,48

59,94

67.88

69.22

73,08

74,53

77,39

79,40

80,29

81,32

292,89° K

233,3

232,3

230,7

230,9

231,4

233,4

2.38,1 240,0

258,3

286.2

307,4

329,0

371,4

427,2

469,2

303,1 5»K

333,4

331,9

328,0

323,4

319.7

316,6

310,7

297,3

283,8

272,5

271,8

266,3

260,5

255,2

251,2

250,2

249,0

249,5

250,3

250.5

253,3

263,6

301,3

353,7

353,3

389,7

308,67° K

333,5

325,4

306,7

302,0

291,5

278,3

265.2

258,2

258,0

258,0

259,2

263,5

269,4

273,2

276,3

[Continued on next page]

-73-
Table 34 (Continued)

T - 308,G7^K

82,83 282.8

86,37 300,0

90,53 326.0

95,24 343.0

r = 343.15' K

1,89 351.6

3,45 349,6

3,65 34£,9

5,40 347,6

8,84 315,2

9,82 344.7

23,95 332,6

39.7< 320,4

54,35 309,1

69,64 30 i,

2

80,29 298,9

88,33 300.4

98,33 305,7 rr= 363,15= K

1,03 362,5

1,98 359,5

2.86 357.9

4,63 356,5

6,88 355.9

12.77 352,0

18,35 349,4

27.37 343,8

44,44 333.0

r-= 363.15" K

64.55

81.90

99,21

1,00

3,84

6,59

13,32

23,75

41,60

57,98

79,99

87,54

93,77

99.12

0,73

1.20 4,33

11,49

26.99

43.46

63.57

84.06

98,28

T

0.96

1.52 S.6I

322,1

316.8

317,8

T = 385.84° K

370.5

366,9

36(;,1 362.7

358,0

349,5

3-12,6 337,7

330,6

336,8

338,2

r= 407.54° K

380.0

378.2

37h.3

373.3

368.0

362,0

356,5

353,4

352.9

429.53° K

385,6

385,0

384,0

r

19,73

34,83

59,45

78,86

95,73

T

4,25

10,71

15,81

24,54

37,48

50.43

59,74

75,68

76,90

83,67

88,97

98,02

T

1,21

1.79

16.41 27,00

39,84

52,97

68,38

84.72

94,07

98,09

- 429.53'^ K

381.1 375,9

370,5

368,6

368,1 = 448,62° K

392,9

391,2

389,5

388,3

385,4

383,8

381,9

380,3

379,5

378,9

379,3

378,9

473,15° K

403.0

403,5

400,6

399,1

397,3

395,5

394,5

393,7

393,5

393.7

The purity of the investigated compounds was determined by chromatographic analysis. The ethylene specimen contained 99.97% of the basic

component and 0.03% ethane; the propylene was 99.50% pure and the propane

and ethane impurities amounted to 0.3 and 0.2%, respectively. The compound

was not subjected to additional purification.

The experimental investigations of the speed of sound in ethylene

encompass the 193 to 473°K temperature and 1 to 100 bar pressure ranges.

In this range of parameters, including the subcritical, near-critical and

supercritical states of ethylene, 273 experimental points were obtained,

measured on 18 isotherms and the liquid-vapor phase equilibrium line.

The subcritical region of state was investigated on the saturation

line and six isotherms, on which the speed of sound was measured at

temperatures of 193 . 15-273 . 15°K and from atmospheric pressure to the vapor

saturation pressure at the experimental temperature.

The near-critical and supercritical regions of state were investigated on 12 isotherms in the 1-100 bar pressure range. The rather large

-74-
number of points on each isotherm and the use of the variable pressure

step for the measurement made it possible to determine reliably the

coordinates of the characteristic points of the speed of sound isotherms

(the position of the minimum and points of inflection)

.

The results of the measurements of the speed of sound on the isotherms are presented in Table 34 and Figure 5. The maximum scattering of

the experimental points relative to the smooth curve does not exceed

±0.4 m/sec. Usually not more than 1-2 points with such scattering appeared

on an isotherm. The mean scattering of the points is ±0.2 m/sec.

0 W 20 30 ^0 so 60 70 60 90 pjap

Figure 5. Speed of sound in ethylene as function of

temperature and pressure according to data: 1 -- authors

of present book; 2 -- Herget [12].

The speed of sound on the liquid-vapor phase equilibrium line was

investigated at 10 experimental points from temperatures of 193.15 to

282.15°K.

The results of the measurements on the liquid-vapor phase equilibrium

line are presented in Figure 5 and in Table 35.

-75-
Table 35. Experimental Speeds of Sound in Ethylene on Saturation

Curve According to Soldatenko and Dregulyas

r. °K p. 6ap

1

1 w, M/ceK T. °K p. 6ap w, M/ceK

193,15 3,40 261,1 263.15 32,38 263,3

203,15 5,12 264,2 273,15 40,91 224,8

223,15 10,61 262,7 277,29 44,98 218,0

243,15 19,29 254,0 280,53 48,22 210.5

253,15 ' 25,30 246,4 282.15 50,13 203,2

Yu. A. Soldatenko and E. K. Dregulyas measured speed of sound at

several points of the isotherms investigated by Herget for the purpose of

direct comparison of the measurement results with Herget's data [12]. The

results of the measurements are ' presented in Table 36.

Table 36

P, (jap

1 w, M/ceK

j

p, 6ap w, m/cck p. dap w, M/ceK

51,21 200,2

18,7° C

31.79 283,4

37,77 273,0

43.66 262,2

55,36 237.0

t= 18.7° C / = 23''C

60.28 229,6 44,64 266,9

62,28 235,9 52,92 252,0

63.42 246,0 65,18 241,3

65,63 269,9 65,63 241,9

69.55 310,2 67,77 251.1

72,52 334,3

Considering that the compared measurements were done in the ranges

of temperatures and pressures close to critical, the discrepancies can be

attributed to the different purities of the investigated specimens of

ethylene or to the presence of systematic error in temperature measurements.

This is confirmed by the fact that the least deviations take place at the

point on the 23°C isotherm farthest from the critical point, and the

discrepancies on the 18.7°C isotherm reach maximum values (1%) in the

vicinity of the minimum speed of sound as pressure increases, and diminish

with a further increase of pressure. Such character of deviations can be

explained by the different purities of the compounds used for the experiments .

The results of measurements [13, 14] coincide within the limits of

accuracy of their graphic representation with the data of Yu. A. Soldatenko

and E. K. Dregulyas [15, 16].

Telfair [17] measured the speed of sound in gaseous propylene at

atmospheric pressure and at temperatures of 273-490°K. The experimental

speeds of sound were not given in the publication.

-76-
Yu. A. Soldatenko and E. K. Dregulyas also did measurements in

propylene [15, 18] in the 193-473°K temperature and 0.1-100 bar pressure

ranges

.

The speed of sound was' measured on 19 isotherms and on the liquidvapor phase equilibrium curve. The results of the measurements are shown

in Figure 6 and in Tables 37 and 38. The experimental points have a

scattering relative to the smooth curves of ±0.2 m/sec.

Figure 6. Speed of sound in propylene as function of

temperature and pressure according to Soldatenko and

Dregulyas

.

Table 37. Speed of Sound in Propylene on Saturation Curve According

to Soldatenko and Dregulyas

T, *K p. Cap W, MlCtK r, °K p. Cap W, HiCtK

193,15 0.164 214,1 353,15 37,47 172,9

233.15 1,41 225.3 300,15 42,42 161.8 313.15 16,46 212,4 363,15 44,84 153,4

333,15 25,38 196,4 363.15 44.88 153,1

-77-

I
The maximum absolute error of measurement of the speed of sound in

ethylene and propylene, calculated by the generally accepted method from

the theoretical equation, is ±0.5 m/sec.

The speeds of sound, as we know, can be used for calculating the

thermodynamic functions only if they do not depend on frequency. In this

connection discussion of the measurement results must start with definition

of the boundaries of the region of dispersion of the speed of sound in the

investigated compound.

Table 38. Speed of Sound in Propylene According to Soldatenko

and Dregulyas

1

p. 6ap <i), .v.jceK \ p. tap ,1). MiceK p. Gap (1), MjceK

T — 193,15

0,081 215,0

0,092 214,8

0,164 214,4

T = 213,15'^K n o'Xi yj ,zoi 223,1

222,8

0,445 221,4

0,537 221,1

T = 233,15° K

n 1 1 0 232,8

U,ioz 232,6

232,1

f\ ceo 0,553 230.4

1,00 227,6

1,23 220,3

1 At 1,41 225,3

250,9/

0,102 240.5

0,547 23S,ii

1,244 235,0

1,97 231,4

2,46 228,8

2,53 229.1 T = 263,15 'K

0,171 245.3

0,570 244,2

1,144 241,2

2,17 237,3

3,14 233,0

3,69 230,6

4,13 22S.7

r = 273.15 = K

0,141 250,0

0,501 248,4

0,991 247,2

1,902 243.8

2,77 240,3

3,00 239.6

3.92 236,2

4,10 235,0

4.90 231.9

5,35 229,8

5,59 227,7

7" = 298,15= K

1,00 257.5

1,39 256,3

2,37 253,2

5,71 243,8

6,00 242,2

9,24 230.7

9,97 227,9

7 = 323,15° K

1,00 267,8

2,37 264,4

5.17 258,1

9,09 247,4

10,22 245,1

14,73 231.1 14,93 230,1

18,65 215.6

20,09 207.3 r = 348,15° K

1,01 277,1

1,98 275.3

2,86 273,1

3,26 273,0

G,79 265.3

6,79 205,7

10,22 238,4

11,05 250,2

11,54 255,3

16,89 241,9

17,38 240,2

18,55 237.4

21.84 228.9

26.50 2! 3,7

30,10 199.1 32,44 188.5 33,17 184,2 r = 360,15° K

1.00 281.6

1,98 279.7

5,71 272,6

10,32 264,0

I7,J8 249.7

24,29 233,3

30,08 217,2

35,62 19S,6

40,72 174.0 42,42 162.1

r= 365,15° K

1,01 283,4

2,48 280,5

4,68 276.7

13.86 259,4

26,80 231,7

33.07 212,7

40,14 189,8

42,29 179.8 43,87 171,8

44,65 165,6

45,63 157.5 45,63 158,3

46,02 153,2

46,34 144,6

46,61 160,6

4G,86 108,4

47,79 192,9

48,02 209,1 50.04 227,2

55,28 281,8

60.78 325,9

69,61 372.1 79,02 412,0

91,48 455,0

95,89 466,8

98,78 474,5

373,15° K

1,01 286,3

1,99 285,2

6,80 276,6

12,68 266,4

24,45 243,8

33,07 227,6

41,02 202,4

46,12 186,0

47,94 178,7

48,17 178,6

50,53 170,0

50,73 169,5

51,52 166,4

52.00 164,1

52,69 164.5 53,4S 173,3

53,97 177,4

57,30 217,3

58,97 233,7

70.34 313,2

[Continued on next pagej

-78-
Table 38 (Continued)

p. 6ap 0). MiCtK P. Oap

1

10, M/ceK

j

p. Oap 01, At/ceK

r = 373,15° K

81.-13 90.9G

96,82

98.34

368,7

403,3

423,1

428,0

7 = 383.15° K

1.00 289,6

1.59 288,7

2,47 2S7.8

7.78 279,2

19,83 259,5

32,14 236.3

40,52 218,5

51,01 193,8

56,89 181,0

58,76 180,6

60,14 182.4 61.12 184,7

62,05 188,1

67,74 223.C. 75,95 276,0

84,30 318,1

92,20 350.8

97.84 372,1

2' = 398,15° K

1.72 294,0

8,27 285,4

18,76 270,1

34,26 245,4

49,65 218,9

57.10 205,8

61,21 202.0

63,57 199,8

65,34 199,4

67.74 200,6

70,25 203,1

73,48 210,2

79.41 230,1

87.70 263,7

r =398,1 5" K

88,05 264,6

94,86 291,8

98,98 311,6

T = 403,15° K

0,41 297,3

0,74 296,6

0,93 297,3

1,56 296,3

5,17 291,7

15,81 277,1

28,07 259,5

41,50 238,0

51.80 222,0

62,05 208,5

67,70 205,8

69,35 206,1

73,27 208.2

80,53 223,4

91,07 261,5

97,30 284,1

r= 423,15° K

0,226 304,6

0,333 304,5

0,549 304.4

0.902 303,9

1,57 303,4

5,18 299.2

7,97 296,0

15,23 287,4

25,76 274.3

42,10 25i,2

53,48 241,5

64,07 231,5

74,07 226.0

79,41 226,0

83.78 227,9

89,66 233,5

95,06 242,6

98,88 252,0

T--=

5,28

11,94

25,04

36,02

46.22

59.16

71,13

83.68

93,58

98,34

T

443.04= K

305,8

292,2

286',5

274,9

264,9

254,0

245,8

243,9

247,0

251.3

448.15° K

1,11 311.8

2,86 310.4

4,78 308,3

16,40 297,6

29,44 284,5

41,80 272,7

54,45 261,4

69,35 252,2

79,40 248,3

83,29 248,3

92.84 250,1

98,87 254,2

T = 473,15° K

1,01 319,9

1,60 319,3

7,97 314,6

15,23 308,5

22,98 303.1 30,92 296,7

43,57 287,0

58,67 277,6

74,51 270,4

83,68 269,0

95,25 269,1

95,76 269,0

98,69 268.8

Analysis of the results of measurements in ethylene reveals that

experimental points of the isotherms fall above the smooth curves, which

pass through the speed of sound values corresponding to the perfect-gas

state, in the investigated temperature range at pressures less than

3-4 bar (see Figure 5) . Deviations increase nonlinearly as pressure

decreases and at 1 bar they amount to 2-3 m/sec. Such a form of dependence

of the speed of sound on pressure, as we know, indicates that there is

dispersion of the speed of sound in the range of pressures below 4 bar, and

the lower boundary of the dispersion region, corresponding to "freezing" of

vibration degrees of freedom of only part of the molecules, takes place for

f/p 175 kHz/bar.

These data agree satisfactorily with the results of experimental

investigations of the speed of sound in ethylene, carried out by the

-79-
1

acoustical interferometry method by Namoto and coworkers [19] and by

Richardson and Reid [20]. According to the data of these works, the dispersion caused by relaxation of the vibration degrees of freedom, occurs in

the range of values of f/p from 180 to 5,000 kHz/bar. The time of vibration

relaxation at atmospheric pressure is 2.15 x 10 sec at 27°C according to

[19] and 2.38 x lO" sec at 30°C according to [20]. The measured speed of

sound in ethylene is thermodynamic, with the exception of that measured at

pressures below 4 bar.

The dispersion of the speed of sound in propylene was investigated

by Pusat and coworkers [21] . The experimentally determined region of

dispersion is bounded by values of f/p equal to 10-148 MHz/bar. The time

of vibration relaxation at 30°C and at atmospheric pressure is 1.48 x

X 10'^ sec.

Investigations [15, 18] indicate the absence of dispersion at

690 kHz in the investigated range of pressures, which agrees completely

with the conclusions of [21]

.

Recommended Thermodynamic Speeds of Sound, Adiabatics Index, Heat Capacity

Ratios and Isobaric Heat Capacity of Gaseous Ethylene and Propylene

Detennination of the heat capacity ratio and adiabatics index on

the basis of the speed of sound is most accurate of the known methods.

Calculation of k and k is based on the Laplace equation for the speed of

sound:

(42)

Using the known thermodynamic relations (3^) = k(^)^ and the ' dp S dp T

equation of the adiabatics of a real gas in the form pv = const, it is

possible to derive calculation equations for determination of k and k_^

on the basis of experimentally measured speeds of sound and p, v, T-data

or using the thermal equation of state:

X^jjf—; (43)

7^' (44)

It is obvious from (43) and (44) that the speed of sound, density

and the first derivatives of the temperature functions must be known in

order to do the calculation.

Equation (43) , together with the known thermodynamic relation

-80-
Q ~ a.

gives expressions for calculating heat capacities:

c =

Op —

I If (47)

8T d where R is universal gas constant; Y = is a dimensionless value.

In order to calculate the heat capacities, as follows from equations

(46) and (47) , it is essential to have data on the speed of sound and the

first derivatives of the thermal functions.

The method of calculation set forth herein makes it possible to

determine the heat capacities with a higher accuracy than and

calculated with the aid of the p, v, T-data and heat capacities in the

perfect-gas state. Moreover, as follows from expressions (46) and (47),

the contribution of the measurement error of the speed of sound to the

overall error of determination of the heat capacities decreases by measure

of approach to the region of their maximums. The accuracy of the values

and in this region is limited basically by errors of determination of

the derivative and complex Y.

The recommended adiabatics indices, heat capacity ratios and

isobaric heat capacity (Tables II, IV, VI, VIII), computed according to

data on the speed of sound, were obtained by Yu. A. Soldatenko and E. K.

Dregulyas. The thermal functions and their first derivatives, required

for the calculation, were taken from the works of Michels and coworkers

[10, 11] and were calculated according to the thermal equations of state.

Comparison of the isochoric heat capacity of propylene with the

heat capacities found by Nevers and Martin [1] revealed that they agree in

overlapping temperature and pressure ranges within the limits of experimental error.

The isobaric heat capacity and heat capacity ratio calculated

according to p, v, T-data of Michels and coworkers [10, 11] are presented

in [4, 7].

As seen in Figures 7, 8, 9, 10, these data agree with the values

calculated on the basis of the speed of sound within the limits of a few

percent. Maximum discrepancies occur in the region of extremal change of

the compared values. The heat capacities at pressures above 100 bar in

Tables II and VI were calculated from the thermal equations of state used

in Chapter I

.

-81-
o 1

*

1—

1

r—

(

f-l

t/i u (/) 4-* vU

5-1 KA

4-1 r-* •H O • H

o C u 1

• H 03 o 1 (-> o

03 0 o CN

5-1

• •y X -P to

+-> 03 §

u

•H U o

O Q) •H

03 +-> Ph E 03 +-> 03 (D i-H o +-> o tn •M 4-1 (D

OS O 03 Sh o Pu

o: c

o 4-1 H O O

00 +Jo

CD C

5-1 3

• H (/) tu o3

(/) V)

+-> ?H

.-H O

V) +->

Di 03

-82-
-83-
12 Vj: i3 5 o, -j^ f-. t-? ^ — •> ^

3

oc:

f\ ^> est CXj ^Ci-Vj

0)

to

100

P<

05

(Du

+J

oJ

<UPh

e

+->

O

o

•HO

c

I—

1

I/) i-H

t 1

(/) t—

1

0

rHX o

Ph •H o IS

Ph 1

1 o rsi

•H o

o o

05

p-1 05U c

(U

+-> l/l Oj <D (D ^<Ph

O

• H o

f-1 05

4=1O o

t/l X l-H 4->

OS O>—

1

0)

1—4

•H o

-84-
CHAPTER VI,. CALORIC PROPERTIES OF ETHYLENE AND PROPYLENE IN CONDENSED STATE

Review of Experimental Data

The experimental measurements of the isobaric heat capacity of

ethylene and propylene and the heats of phase transitions are based on the

determination of the caloric properties of these compounds in the solid and

liquid states. The works containing the results of such analyses are

listed in Table 39.

Table 39. Caloric Properties of Solid and Liquid Ethylene and Propylene

1)

ABTOptJ

2)

Von

Shkch II FayK [Ij

3raH H KcMn [2]

KocrpioKOB c corpyaHHKaMli (3)

ry({)MaH H riapKC (4]

riaye^i^ h /I>Kar)OK |5)

AyepSax, Ceri;i>K ii JlecH [6J

1928

1937

1954

1931

1939

1950

repBa.T iic- c..''aoaaiii:iJ.\ v^;>inepaT> p, 4)

3ea;ecTB0 h ero HswepeHHae cBoiXTBa

80—170

16— 1G9

35—115

68—210

14—225

300—330

B) 3tii.ioii, n3o6apHa5J len.iocMKOCTb k Ten;io- ra n.iat ,.icM'H5i 5) Stimoh, ii3o6apfia5i Tcn^iocMKocTb, TciiJiora

njiaujieiiiia n iiapooopajonaiiiis

7) Slil.ieH, H306apHa5T TCn^lOe.MKOCTb

i) nponiKicH. n3o6apHa5i lenjioeMKocTb ii ren-

/lora n.'iaH.ncHHa 3) riponii.nc'H, n3o6apHas] Ten^noeMKOCTb, renjiora ri.iau.ieHHH n n,'ipooopa30BaHH5i

LO Jnponiuen, n3o6apHa5i len^ioeMKocTb

KEY: 1. Authors

Eucken and Hauck [1]

Egan and Kemp [2]

Kostryukov, et al [3]

Huffman and Parks [4]

Powell and Giaque [5]

Auerbach, Sage, Laccey [6]

2. Year

3. Range of investigated

temperatures, °K

4. Compound and its measured

properties

5. Ethylene, is

and heat of

6. Ethylene, is

heat of fusi

ration

7. Ethylene, is

8. Propylene, i

and heat of

9. Propylene, i

heat of fusi

ration

10. Propylene, i

obaric heat capacity

fusion

obaric heat capacity,

on and heat of evapoobaric heat capacity

sobaric heat capacity

fusion

sobaric heat capacity,

on and heat of evaposobaric heat capacity

-85-
All the works listed in the table were carried out by direct heating

of the investigated compound in a constant -volume adiabatic calorimeter

with a free interface between the gas and condensed phases in the calorimetric vessel. The ratio of the heats applied to the investigated compound

to the rise of temperature, measured in such tests, as we know, is related

to the thermodynamic functions of the compound by the expression

IT ^r-"'A+„,.Cs + ^.r. (48,

where is the heat capacity of the liquid on the saturation curve; Cy

is the heat capacity of the vapor on the saturation curve; r is the heat of

evaporation; "^-^^i the masses of the liquid and vapor phases,

respectively, of the investigated compound.

The desired isobaric heat capacity of the liquid is calculated by

one of equations (48) of heat capacity on the saturation curve using the

known thermodynamic relation

(49)

where v^^^ is the specific volume of the liquid.

In the region of states far from critical all correction factors

which, according to equations (48) and (49), must be reduced to the values

measured in the experiment for determination of Cp^^, are negligibly small.

At temperatures exceeding the normal boiling point, however, exact calculation of the isobaric heat capacity according to these relations requires

extremely reliable data on the thermal properties of the investigated

liquid, its vapor and heat of evaporation.

The heat capacity of ethylene in the condensed phase is measured by

Eucken and Hauck [1], Egan and Kemp [2] at temperatures from 16°K to the

normal boiling point 170. 4°K. The results of these investigations vary

substantially both in the solid (up to 28%) and in the liquid (up to 17%)

states and give a different temperature curve for the heat capacity of

ethylene in the liquid state (Figure 11). Eucken and Hauck obtained four

experimental points for the heat capacity of solid ethylene and 11 points

for the liquid. They are all presented in [1] in the form of a small

graph. The smooth values of heat capacity obtained in this work are: for

solid ethylene 14.80, 15.35 and 16.00 cal/ (mole -deg) at 80, 90 and 100°K,

respectively; for liquid ethylene 17.40, 17.80, 18.17, 18.50, 18.80 and

18.80 cal/ (mole -deg) at 110, 120, 130, 140, 150, 160 and 170°K,

respectively

The authors [1] estimate the accuracy of their data as ±1%.

-86-

i

I
6

P-Z

• -J

• • •

90 W 170 2W 250 7^

Figure 11. Isobaric heat capacity of ethylene on saturation

curve according to: 1 -- Eucken and Hauck [1]; 2 -- Egan

and Kemp [2] ; 3 -- Soldatenko and Vashchenko [10]

.

Direct measurements are not given in [1] , in which connection it is

impossible to establish the possible error or systematic error in the

measurements and in the processing of the experimental data. Another

important deficiency of the cited work is the absence of chemical analysis

of the ethylene employed in the tests.

Egan and Kemp [2] used 99.5% pure ethylene. They further purified it

by drying over phosphorous pentoxide and distillation at low pressure

(100-200 mm Hg) and pumping of the vapors over the solid phase, before

filling the apparatus with it. The purity of the. thus prepared specimen

was determined cryoscopical ly on the basis of residual impurities, amounting

to not more than 0.001 mole %.

The experimental data [2] on the isobaric heat capacity of ethylene

are presented in Table 40.

The same values are used as recommended values for technical

calculations in many manuals, [7, 8] for instance. The heat of fusion of

ethylene (X = 800.8 ± 0.8 cal/mole) and heat of evaporation (r = 3,237 ±

± 3 cal/mole) at normal pressure of 760 mm Hg, measured calorimetrically

,

are also given in [2]

.

The heats of evaporation stated above agree satisfactorily with

those calculated by the authors (r = 3,222 cal/mole) according to the

saturation pressure of the vapors.

Egan and Kemp, on the basis of caloric data, calculated the entropy

of ethylene in the perfect-gas state at the normal boiling point S°^g

It is 47.36 ± 0.10 cal/ (mole'deg) and agrees very well with the results of

later calculations on the basis of spectroscopic data. The entropy of

ethylene in this state, according to [2], is 47.354 cal/ (mole'deg) . The

-87-
Table 40. Experimental Data of Egan and Kemp [2] on Isobaric

Heat Capacity of Ethylene

/ K X ep.''')

/ • K

Cp, KQAHMtAh /.

i X eprt/)

j

T" K

Cp, KaxKMAb X

1 ) TBep;ioe cocTOflHiis 1 ) TtepAoc cocTOHHHe 1 ) TBepAoe cxiCToaHHe

1 D,UU Kfl 7Q 1 1 ,/ u 103,81 1 34,96

18.81 1,299 86,77 12,65 2) )KHAKOe COCTOHHHe

21,91 1,921 92,11 13,83 106,69 16,51

25,17 2,556 94.40 74,55 108,58 16,49

29.10 3,362 95,48 14,94 112,28 16,43

33,16 4,288 98,10 16,03 119,03 16,33

37,35 5.187 98,99 16,44 125,90 16.28 43,08 6,045 100,94 17,65 132,60 16,21

47.29 6,932 101,39 17.97 139,08 16,11

52.52 7,809 101,90 18,48 145,38 16,09

57.60 8,598 102,28 18,59 151,88 16.08 62,80 9,279 103.03 19,52 1 158,55 16,03

68,41 9,980 103,36 20,77 164,23 16,04

74,70 10,79 103,59 20,58 j 168,71 16,09

KEY: 1. Solid state 2. Liquid state

coincidence of the stated entropy values is indirect proof of the reliability

of the experimental data on the calorimetric properties of ethylene

presented in [2]

.

Some experimental points on the thermal capacity of ethylene are given

by V. N. Kostryukov, et al [3] in graphic form. These values were obtained

at the request of the authors during trial measurements, in which the operation of the experimental apparatus was checked. The data obtained practicall|

coincide with the data of Egan and Kemp [2], with the exception of the region;,

very close to the melting point, where the authors [3] observed a very sharp j (4-5-fold) increase in the heat capacity. The authors [3] attribute the

|

increase in heat capacity to the insufficient purity of the investigated J

ethylene specimen. '

The isobaric heat capacity of propylene in the condensed state was

measured to the normal boiling point by Huffman, Parks, Barmore [4] and

Powell and Giaque [5] . The purity of the investigated specimen of propylene

in [4] was characterized by the presence of 0.1 mole % impurities, and in

[5] the purity of the main component was 99.98%. i

The experimental data obtained on isobaric heat capacity of propylene

agree within the limits of the accuracy of experimental measurements of ±1%, , as requested by the authors, and the data in [4] are understated in relation to the data in [5] within the limits of systematic error in the liquid 1

state. The experimental data derived from these investigations are listed f

in Tables 41 and 42. j

The data on the heat of fusion of propylene, measured in the cited

works, diverge to a somewhat greater extent.

-88-
Table 41. Experimental Data of Huffman, Parks and Barmore [4] on

» Isobaric Heat Capacity of Propylene

r°, K Cp. Katl(e-zpadi l\ K Cp, Ka.iHe-epad) r°. K

• Cp. KaAl(a-epad)

1) TflepAUii sTHJieH 2) >KHAKHH STH.ieU

68,9 0.273 93,1 0,523 153.9 0.490

72,0 0,280 93,5 0.522 165,3 0,492

73,5 0,286 98.6 0.516 189,5 0,502

76,5 0.296 108.7 0.504 210,3 0,512

76.7 0,295 125.2 0.494

81.6 0.317 144.6 0.490

KEY: 1. Solid ethylene 2. Liquid ethylene

Table 42. Isobaric Heat Capacity of Propylene, Experimental Data

of Powell and Giaque [5]

T". K

Cp, Ka.:f{c • epad) ! T\ K

Cp. kqaKc • cpad)

j

T\ K

Cp, KaAl(i-apad)

G1.25

66.61

0,2438 115,64 0,5024

i ) I Bep,f^LJH npGi!n,neH 0,2609 128,09 0,4988

14,18 0.0271 71.46 0,2759 134,56 0,4974

16,66 0,0377 76.49 0,2920 141,21 0,4945

19,63 0,0523 76,59 0,2949 154,97 0,4950

22.81 0.0726 . S1.6-J 0,3184 161,88 0,4948

26.23 0.0924 ' .^i.37 0,3374 169,01 0,4960

29,87 0,1113 ! f:6,i;' 0,3826 176,71 0,4986

33,62 0,1332 2) HuiaKiiii nponiivien 187,77 0,5005

37,46 0,1537 194.66 0,5036

41,29 0,1705 93,91 0.5235 201,77 0,5090

45,53 0,1865 98,66 0,517! 209,18 0,5121 ,. 50,66 0,2069 104.18 0,5107 216,41 0,5136

55,96 0,2243 109,98 0.5073 223,40

1 0,5195

KEY: 1. Solid Propylene 2. Liquid propylene

According to measurements [4] the heat of fusion is 701.4 cal/mole,

and in [5] it is 717.6 cal/mole. The 2% discrepancy in the heat of fusion

is obviously related to the purity of the investigated specimens, as well

as to the fact that the sharp increase in heat capacity of the solid

propylene near the melting point, observed in [5] at temperatures from

82°K to the melting point (87.70°K) was taken into account in [4] during

processing of the experimental data on the heat of fusion. The last

experimental point in [4] in the region of the solid state was determined

at T = 81.6°K. Thus, the heat of fusion of propylene A = 717.6 cal/mole,

obtained in [5], should be considered more reliable.

The heat of evaporation {x) of propylene at normal pressure was

measured in [5] by the calorimetric method and is equal to 4,402 ± 3 cal/mole.

The isobaric heat capacity of liquid propylene on the saturation

-89-
curve at temperatures above the normal boiling point were measured in a

narrow temperature range by Auerbach, Sage and Laccey [6] in a constantvolume adiabatic calorimeter with the presence of a free interface between

the liquid and gaseous phases. The isobaric heat capacity was calculated

on the basis of two series of calorimetric measurements, taken with

different concentrations of the investigated compound in the calorimetric

vessel at 308-339°K.

The basic calculation equation is

dVy>: \ dPs rp dPs

dT jp dT dT

AT, ATo ( V' — v' \

/Til — ni^

„ dv' . dv

V — V dT

+

dT rp (dVn\ dpi

\ dTjp dT

(5)

"^1 "^2 where (^) and (.jTy—) are the ratios of the heats applied to the calorimetric

1 2

system to the temperature rise, measured directly in the first and second

series of tests; m^ and m^ are the masses of propylene in the calorimeter

in the first and second series of tests.

The original propylene was 99.0% pure. It was subjected to

additional purification by fractionation at low temperature and at

atmospheric pressure in the ratio 40:1 before filling the apparatus, and

at the beginning of purification more than 15% of the specimen was discarded, and 20% at the end of the purification process. The specimen used

in the test changed temperature by not more than 0.05°K during evaporation

at atmospheric pressure.

'^l "^2 The difference

at~-^ required for calculating the isobaric heat

1 2

capacity of the liquid in accordance with equation (50) , was determined in

accordance with smooth curves plotted in coordinates q/AT - T for both

series of tests. During investigation of propylene the scattering of the

individual measurements in relation to the smooth curve constituted an

extremely large part (±5%) of the above-mentioned difference. A considerable drawback of the examined investigation, inherent to the experimental

procedure, is the extremely large correction factor related to the presence

of a two-phase system in the calorimeter, which must be reduced to values

measured in the test in order to calculate the isobaric heat capacity of

the liquid on the saturation curve (see equation (50)).

According to data in [6] , the correction factor in the given

temperature range is 16-45% of the isobaric heat capacity of the liquid.

It is also noteworthy that this correction, due to the insufficient

accuracy of the existing data on the thermal and caloric properties of

liquid and gaseous propylene, cannot be calculated with sufficient accuracy.

-90-
1 On the basis of what has just been said it can be concluded that the

accuracy referred to by the authors of [6] of data on the isobaric heat

capacity of liquid propylene on the saturation curve, ±3%, is hardly

justified, and the smooth data (see Table 43) are not reliable.

Yu. A. Soldatenko and D. M. Vashchenko [10] investigated in 1964-1968

the isobaric heat capacity of liquid ethylene and propylene at 170-280 and

170-360°K at pressures of 1 to 60 bar. The experimental apparatus used for

these purposes accomplishes direct heating of the investigated compound in

a calorimeter with an isothermic shell in the variation proposed by A. Ye..

Sheyndlin, S. G. Shleyfer and E. E. Shpil'rayn [11]. A characteristic

feature of the method is the absence of a free liquid surface in the

calorimeter, ensuring the capability of measuring the heat capacity of

unsaturated liquids under pressure. The pressure is created in the

apparatus by the vapors of the investigated liquid, and its free level

extends beyond the limits of the calorimetric vessel into a region of

higher temperatures than the temperature existing in the calorimeter. The

amount of the investigated compound is determined by the known volume of

the calorimetric vessel and the density of the liquid at the test

temperature and pressure. The experimental apparatus is described in

detail in [10]

.

Table 43. Isobaric Heat Capacity of Liquid Propylene on Saturation

Curve According to Auerbach, Sage and Laccey [6]

f F 7-° K

Cp, KOMic-zpad) r- F T" K

Cp. kqaIU • apad)

80 299,8 0,5615* 130 327.6 0.6607

90 305,4 0.5747 * 140 333,2 0,6985

100 310,9 0,5917 150 338.7 0,7607

110 316,5 0.6102 160 344.3 0.8608 * 120 322.0 0.6329

*Values extrapolated by the authors [6]

.

A new method of introducing the correction factor for heat exchange

between the calorimeter and the isothermic shell is original in the given

study. During calorimetry the temperature of the calorimeter is measured

both during the main period of the test, including the operating time of

the heater and time interval during which the temperature varies in the

calorimeter, and in the final period. Here the time of passage of the

"spot" of the galvanometer, hooked into the measurement circuit of a

platinum resistance thermometer, through the zero graduation when certain

a priori known temperatures are reached in the calorimeter, is recorded

with the aid of a two-hand type 51 -SD stop watch. The temperature pitch

between consecutive measurements was maintained constant.

The curve of change of calorimeter temperature in time, thus

obtained, was used for determining the "adiabatic" [13] temperature rise

of the calorimeter, which is determined with the expression

-91-
At = At' + 6t (51)

where At' is the observed temperature rise of the calorimeter on completion

of the main period of the test; 6t is the correction factor for heat

exchange between the calorimeter and the isothermic shell during the main

period.

The correction factor for heat exchange is found from the expression

where k is the rate of cooling of the calorimeter; t is current temperature;

tj^ is the convergence temperature [12] , equal in our case to the initial

calorimeter temperature; is the time of completion of the main test

period.

The accuracy of calculation of the correction factor for heat

exchange depends principally on the accuracy of determination of the

cooling rate k, calculation of which is now done by a new method with high

accuracy

.

The generally accepted methods of calculating the rate of cooling

[11, 12] are based on the assumption of linear change of calorimeter

temperature in the final test period, which, as shown by experience, is at

best a very rough approximation. Disregarding the nonlinearity of the

temperature curve of the calorimeter in the final test period causes

notable errors, particularly during testing in the negative temperature

range

.

A new method is based on the fact that at the end of the test the

temperature drop of the calorimeter is governed only by heat losses from

the calorimeter to the thermostat and consequently for any time interval

(t , - t ) of the final period the heat exchange correction factor 6t, n+1 n ^ ^ calculated according to equation (52) , is equal to the observed temperature

drop of the calorimeter:

6i = k

^ (t-t,)dT=it„-i,+r). (53)

Writing expression (53) for the entire final period from to (time of

completion of the test), we obtain

(54)

-92-

i

I
Equation (54) is used for calculating the rate of cooling k. For the

adiabatic rise of temperature of the calorimeter in the principal period

we have, with consideration of what has been said above,

J - /o) dx = (in - to) + (/. - t,) _

. (55)

^(t~lo)dx

The integrals in equation (55) are calculated by the trapezoid method

on the basis of calorimeter temperature measurements in the main and final

test periods.

The time of completion of the main period of the calorimetric test

is determined quite distinctly within the frameworks of the given method.

Actually, with consideration of the constant temperature pitch between

consecutive measurements and conditions (53) , we may write for any interval

of time between consecutive measurements in the final period, the following

relation:

^1+1

k \

(t — to) dx = iti — ti+i) = const.

Since the rate of cooling is constant for the entire calorimetric test it

follows from expression (56) that

f ii — t(,)dx = const, (57)

for the entire final period, or calculating the integral as the area of a

trapezoid, we obtain

At, = const.

^^g^

Consequently the point on the curve of change of temperature in time, after

which equation (58) is satisfied for all subsequent measurements, may be

taken as the completion of the main period. Its shift toward an increase

in time does not alter the results of the calculation by the equation

At J = At' + 6t.

ad

The isobaric heat capacity of liquid ethylene and propylene was

investigated at 170-280°K and 170-360°K at pressures from 1 to 60 bar.

Ethylene and propylene were supplied in metal cylinders. The

-93-
concentration of the main component according to the data of factory

chromatographic analysis in specimens taken from the cylinders is 99.98%

for ethylene and 99.7% for propylene. The investigated compounds were

not subjected to additional refining.

I

o-J

0-4

*-5

0-7

0-8

„-9

A

—.— ^

— ^

II <>—<>

V — Q_c — U T r 1 > »

10 10 30 ^0 SO P, 6a

p

Figure 12. Experimental data on isobaric heat capacity of

liquid ethylene at T equal to: 1 -- 168.90; 2 -- 196.65;

3 -- 232.65; 4 -- 249.65; 5 -- 257.25; 6 -- 262.65; 7 -- 266.65; 8 -- 270.35; 9 -- 273.65; 10 -- 277.65°K.

KEY: 1. Saturation curve.

Sixty-nine experimental points were obtained on the basis of the

isobaric heat capacity of ethylene. During the calorimetric test the

initial temperature of the specimen and the heat supplied were chosen from

the consideration that the average temperatures of the series of tests

conducted at different pressures be close to each other. Thus, the entire

series of measurements was conducted on the same isotherm. The small

correction factors that are inevitable in such a case at certain experimental points, for reduction to the temperature on the investigated

isotherm, did not exceed 0.3% of the measured isobaric heat capacity. The

correction factors were introduced by the successive approximation method

during processing of the series of isotherms.

Eleven isotherms were found for ethylene in the stated temperature

range, each of which included at least five experimental points. Most of

the experimental points were the result of averaging two identical measurements .

The experimental points and the smooth curves (isotherms) are

illustrated in Figure 12. Smoothing was done in the coordinates C^-p on

the basis of the isotherms and in the coordinates C -T on the basis of the

P

isobars. Deviations of the experimental points from the smooth curves do

-94-

1
not exceed ±1%. The isobaric heat capacity on the saturation curve was

determined by extrapolating the isotherms to the saturation pressure, which

was taken on the basis of the data in [7] . Seventy experimental points on

10 isotherms were obtained in the above-stated temperature and pressure

ranges in terms of the isobaric heat capacity of propylene. The deviations

of the experimental points from the smooth curves did not exceed ±1%. The

experimental points and smooth curves (isotherms) are illustrated in

Figure 13.

Figure 13. Experimental data on isobaric heat capacity of

liquid propylene at T equal to: 1 -- 360.35; 2 -- 358.65;

3 -- 355.15; 4 -- 352.55; 5 -- 344.64; 6 -- 335.15; 7 -- 325.65; 8 -- 301.65; 9 -- 274.57; 10 -- 197.55; 11 -- 164.65°K.

KEY: 1. Saturation curve.

Detailed analysis of the accuracy of experimental determination of

the isobaric heat capacity yields a maximum possible error equal to ±1.5%.

The accuracy of the extrapolated values of heat capacity on the saturation

curve, by our estimate, is ±(2.5-3)% in the high-temperature range.

Recommended Caloric Properties of Ethylene and Propylene in Condensed State

Ethylene

The review and comparison of existing experimental data on the

isobaric heat capacity and heat of phase transitions of ethylene, presented

in the preceding section, make it possible to recommend the following

initial data as the most reliable:

a) Egan and Kemp [2], presented in Table 44, on the isobaric heat

capacity in the solid state from 15°K to the melting point (103.95°K) and

on the heat capacity of the liquid in the range of temperatures from the

melting point to the normal boiling point (169.37°K).

-95-
The heats of phase transitions, found by the same authors, for the

heat of fusion X = 119.26 ± 0.41 kJ/kg and heats of evaporation r = 483,

144 + 0.3 2 kJ/kg at the normal boiling point for p = 760 mm Hg, are also

the must reliable values.

b) Yu. A. Soldatenko and D. M. Vashchenko on the isobaric heat

capacity of liquid ethylene in the temperature range above the normal

boiling point, the results of which are presented in the preceding section

(see Figure 12)

.

The data of Egan and Kemp were used in the present work for

calculating the enthalpy and entropy of liquid ethylene at the normal

boiling point, measured from the crystal state at 0°K.

Heat capacity below 15°K was found by extrapolating to 0°K

according to the Debye theory [13] and agrees at 15°K with the data of

Egan and Kemp.

The enthalpy and entropy were obtained by graphic integration of

the data on isobaric heat capacity.

The heat of fusion was found on the basis of data [2] . The results

of the values in the most characteristic points are presented in Table 44.

Table 44. Heat of Fusion According to [2]

1) TeMneparypa 2) l^3MeHenne SMTa/ibniiH. uriyKlK? inMeiieHiic aiiTponnH. KdM/lKe-epadi

O'K— 15° K '15° K — 'o- K = ^ = 0.0357

15" K - '103,95=" K ~'l5° K ^ 115.86

119.53 ?./r„,= 1.149 Tn.n —TH.K he^.v K '103.95° K " 158.204 •^169,37° K ~ "^lOi.gS' K

=^ '-'^^

CvMMa ' 169.37° K — 'o° K ~ 394,00

^169.37^K = 4.214

KEY: 1. Temperature 4. Total

2. Enthalpy change, kJ/kg 1^ = melt.

3. Entropy change, kJ/(kg-deg) H.k = normal boiling

The enthalpy of gaseous ethylene, given in Table II, was also

measured from the crystal state at 0°K. Conversion of the enthalpy change

measured from the gas state at 0°K, to the zero reading employed, was done

at the normal boiling point using the value i^^g 37°K P^^^ented above.

It was found that

t«r= +662.4), kJ/kg (59)

-96-
where is the enthalpy at T and p = 0, measured from the crystal state at

0

0°K; (H^ - 11^) is the enthalpy of the gas in the same state, measured from

the gaseous state at 0°K.

The data of Yu, A. Soldatenko and D. M. Vashchenko were used for

tabulating the isobaric heat capacity, enthalpy and entropy of liquid

ethylene in the temperature i range above the normal boiling point and at

pressures of 0.5-60 bar (Table II). The tabulated values of enthalpy and

entropy were obtained by graphic integration of the smooth isobaric heat

capacities in the temperature range from 169.37°K to the given tabular

temperature every 10° (Table II)

.

The enthalpy and entropy of the saturated liquid were determined by

the same method with integration to the saturation temperature on the

given isobar. The enthalpy and entropy of the saturated vapor were calculated with consideration of the heat of evaporation at the given pressure.

The enthalpy and entropy at the critical point were determined by

extrapolating the top and bottom boundary curves in coordinates T - i and

T - S to mutual intersection at T and in coordinates p - i and p - S to

cr r r intersection at p . The tie-in of i and S was checked in coordinates

^cr cr cr

1 - S.

Propylene

The data of Powell and Giaque [5], presented in Table 42, are

recommended on the basis of the isobaric heat capacity in the solid state

from 15°K to the melting point (87.85°K) and on the basis of the heat

capacity of the saturated liquid in the temperature range from the melting

point to the normal boiling point (225.35®K).

Also considered most reliable are data on the heat of fusion X =

= 71.402 kJ/kg and heat of evaporation at the normal boiling point at p

=

= 760 mm Hg, r = 438.00 ± 0.3 kJ'kg.

At temperatures above the normal boiling point the isobaric heat

capacities obtained by Yu. A. Soldatenko and D. M. Vashchenko are used,

both for the saturated and unsaturated liquid.

The recommended values are compared with data in [6] in Figure 14.

The comparison can be done only on the saturation curve, since data on the

isobaric heat capacity of the liquid under pressure are found only in [10].

The data of [6], as seen in Figure 14, were obtained for 300-345°K, and

are 12-18% lower than the data of [7]. Possible reasons for such great

discrepancies are discussed in the preceding section.

Powell's results [5] were used in our work for calculating the

enthalpy and entropy of liquid propylene at the normal boiling point,

measured from the 0°K crystal state.

-97-
6

330 T,°K

Figure 14. Isobaric heat capacity of propylene on saturation

curve according to: 1 -- Powell [5]; 2 -- Huffman, Parks [4];

3 -- Yu. A. Soldatenko, D. M. Vashchenko [7]; 4 -- Auerbach,

Sage, Laccey [6]

.

Table 45. Heat, Enthalpy and Entropy

1 ) TeMncparypa 2) MsMeHCHiit; 3) ibMeHeiiiio siirpomiii, Kdx/iKa.epad)

0°K — 15=K S,5»K = 0.019

'87.90'= K

"-1,3 =G0.958 •^r,,^ —5,5.^ = 1,159

X = 71.402 Vr„^ = 0.812

' nji H.K '22.5. 45'K ~" '87.90' K ~ 292,04 '^F7.90'K ~ 1-985

4) . Cy.MMa '225,45 K -«0K = 424.40 5225.45°K = 4.005

KEY: 1. Temperature 4. Total

2. Enthalpy change, kJ/kg nf^ = melt

3. Entropy change, kJ/(kg-deg) H.k = normal boiling

The heat, enthalpy and entropy at the most characteristic points are

given in Table 45. The enthalpy change in the perfect-gas state was converted to the employed zero according to the equation

i'^ = KHr ~ Ho) + 635,3], kJ/kg . (60)

All other data in Table VI were calculated by the same methods used

for ethylene.

-98-
CHAPTER VII. VISCOSITY OF ETHYLENE AND PROPYLENE

Viscosity of Gaseous Ethylene and Propylene at Atmospheric Pressure

The viscosity of gaseous ethylene and propylene at atmospheric pressure

has been thoroughly investigated. Studies pertaining to the experimental

determination of the dynamic viscosity coefficient of gaseous ethylene and

propylene at atmospheric pressure are given in Table 46 and the numerical

values of these coefficients are listed in Table 47 and Table 48. Noteworthy are the calculated data of Trautz [17] for ethylene. On the basis

of his measurements he calculated the dynamic viscosity coefficients of

ethylene at atmospheric pressure at temperatures T = 1,165°K (ri = 2917 x

X 10'^ N*sec/m^) and T = 1,270°K (n = 3060- lO"^ N'sec/m^) . The smoothed

dynamic viscosity coefficients of gaseous ethylene at atmospheric pressure

are presented in I . F. Golubev's review [13] for the 223°K to 773°K

temperature range, and are given below:

T, °K Tl-10 ^,H-CeKlM- \\-\0-^.H-ceKlM'^

223,15 792 373,15 . 1260

248,15 864 423,15 1405

273,15 941 473,15 1545

293,15 1010 523,15 1670

298,15 1027 573,15 1810

323.15 1108 673,15 2049

348,15 1180 773,15 2260

These values were found as a result of processing experimental data of

Trautz and coworkers [2, 3, 5 and 6] and data published in [1, 4]. The

results of Braune and coworkers [18, 19] on the viscosity of gaseous NH^,

H2O, HCN, I^, CI2, CHjCl, CH2CI2, CHCl^, HgCl2, HgBr2, Hgl^, SnCl^, Br2

and air at atmospheric pressure were used in the calculations. These

investigators demonstrated that the experimental data for the above-listed

compounds in the 270-900°K temperature range are described with high

accuracy (mean deviations of the order of 0.2% with maximum up to 1.5%)

by the Sutherland equation [20].

The smoothed dynamic viscosity coefficients of gaseoUs propylene at

-99-
atmospheric pressure for the 193 . 15-1 , 273 . 15°K temperature range (see

Table 49) are presented in Lehmart's review [21]. The author of the review

asserts that they were obtained on the basis of numerous existing experimental data, but does not cite the sources.

Table 46. List of Experimental Studies of Dynamic Viscosity Coefficient

of Gaseous Ethylene and Propylene at Atmospheric Pressure

1 ) ABTOpfal

7)

OoepManep fl] BpeHxeiiuax [1] SiiMMep (

1

] TpayTU, Hapar [2] TpavTU, Ciaycji [3) TiiiaHii [4] TpavTU, Aiaibciep [5] Tpayxu, FeGcpnunr [6) BaH Kjihb, Maacc [7|

KoM-'iHTc, MaiLiaHji, Stjih [8] FpaneH, JlaMoepx [9] 3eH<})T;ie5ei! llOj

ro.nv6eB, lleipoB [11]

JlaMoepi |I2j

Fo.TyCeB [13] M-.iSKK [14]

He;iyHCHH, X.Mapa [15J

8)

Tm-aHH [4] Tpaym, XycefiH!! [16]

Ban K-xiiD, Maacc [7] FpaBen, JIn\i6epT [9] SeHcJjT.ieecH (10)

.JlaMoepr [12)

FoJiyoee [13|

HeavHiiiii, X.Niapa [15]

5) 3-ni.aen

6) npoiniweK

2) rofl

T) --n

TeMrieparypa. I ^i^.o/iimecTBo

"[^ I iKcnepHMeHTa.iibi(bi.\ ToqeK

1

1 87^ o/ o 1 OZO QO ZO i —0 /

0

c0

1 Q1 9 1 Q7 oftf^ 4

1 cion

i yzL) 1 OA O^'A

J yo—zoD 5

1 Q9Q 1 no ::;o ^ 13

I QOQ 6

1930 292—374 3 1931 291—523 10 1935 192—296 11 1944 303—368 5 1951 193—523 5 1953 303 1 1953 313 1 1955 308—3.64 9

1959 297—423 4

1961 293—523 5

1967 193—297 6

1929 293—393 7 1934 289—521 10 1935 193—297 13 1951 293—523 4 1953 303 . 1 1955 308—353 9

1959 291—523 7 1967 210—310 6

KEY: 1. Authors

2. Year

3. Temperature, °K

4. Number of experimental points

5. Ethylene

6. Propylene

7. Obermayer [1]

Breitenbach [1]

Zimmer, [1]

Trautz, Narath [2]

Trautz, Stauf [3]

Titani [4]

Trautz, Melster [5]

Trautz, Heberling [6]

Van Cleave, Maass [7]

Comings, Mayland, Egly [8]

Graven, Lambert [9]

Senftleben [10]

Golubev, Petrov [11]

Lambert [12]

Golubev [13]

Misic [14]

Neduzhiy, Khmara [15]

Titani [4]

Trautz, Husseini [16]

Van Cleave, Maass [7]

Graven, Lambert [9]

Senftleben [10]

Lambert [12]

Golubev [13]

Neduzhiy, Khmara [15]

-100-
It is well known that the viscosity of gases at atmospheric pressure

in the moderate temperature range (up to T < 1,000°K) can be described with

sufficient accuracy by means of equations of kinetic theory. At the

present time the Girshfel'der equation [22], derived through the solution

of the Boltzmann equation by Enskog's method for model of spherically

symmetrical molecules with the Leonard-Jones potential (6-12) is considered

most rigorous. When describing the viscosity of gases the parameters of

the Leonard-Jones potential (6-12) are determined directly from the experimental data and depend on the temperature range due to scattering of the

experimental data. For this reason the Girshfel'der equation, like other

equations of kinetic theory, can be used only for interpolation and analysis

of existing experimental data.

The force constants of the Leonard-Jones potential (6-12), calculated

through the Girshfel'der equation, yielded values e/k = 228°K and a =

= 4.1385 A for ethylene; e/k = 296. 0°K and a = 4.5945 X for propylene.

The deviations of the dynamic viscosity coefficients of ethylene

and propylene at atmospheric pressure from the values obtained as a result

of graphoanalytic processing of data [1-17, 21] are presented in Table 50.

As seen, the force constants of the Leonard-Jones potential (6-12) can be

considered as not depending on temperature and the values recommended for

the calculations are presented in Table 50.

The following values were obtained during calculation of the force

constants by the Sutherland equation: i^ij) e/k = 236. 0°K, a = 3.895 X

for ethylene; i (y) e/k = 320. 0°K, a = 4.387 X for propylene.

The results of such calculations by the Sutherland equation [20]

are presented in Table 51. It is obvious from the table that the force

constants of the Sutherland potential also do not depend on temperature,

and the Sutherland equation [20] is just as good in terms of the accuracy

of description of experimental data as the Girshfel'der equation [22].

On this basis the Sutherland equation was used, being more convenient

for the calculations than the Girshfel'der equation, for compiling Table X

of recommended dynamic viscosity coefficients of gaseous ethylene and

propylene at atmospheric pressure. Scattering of existing data relative

to the smooth values is comparatively low. The following results were

obtained from comparison of the recommended dynamic viscosity coefficients

with the experimental data. The mean deviations of the experimental data

[3, 5-8, 10, 13, 14] on the viscosity of gaseous ethylene at atmospheric

pressure do not exceed 0.6%. The mean deviations of data [12, 15] do not

exceed 0.8%. The mean deviations of data [1, 2, 4, 7, 9, 11] are about

2-2.5%. The maximum deviations are comparatively low. They do not exceed

2-4.5%, with the exception only of one point obtained by Trautz and Narath

[2] at 244. 6°K, where the deviation is 7.9%.

-101-
Table 47. Experimental Data on Viscosity of Gaseous Ethyl

at Atmospheric Pressure

261.65

293.75

326,65

2)

251,95

288.15

372,40

455,55

575,75

3)

197,45

6)

295,15

-313,15

333,15

353,15

373,15

393,15

OSepMafiep

BpefiTeH6ax

SiiMNiep

851

989

1096

891 1016

1278

1530

1826

699.3

229,07 768,5

234,55 784.5

286,87 954,2

4) Tpaym, Hapai

196,16 097

229,15 766

244,65 782

273,15 903

287,15 950

5) Tpayru, Ciaycj)

193,85 716

235,45 816

271,35 940

287,15 990

289,25 996

291,35 1008

292,25 1007

294,95 1018

324,15 1109

373,75 1266

422,35 1405

470.55 1539

525,45 16B7

TllTaHH

970

1036

J108

1154

12-:'0 127'j

7) Tpayru, Me.ibCTep

292,75 1008

324,15 1109

374,15 1262

8) Tpaym, rcCcp.iiinr

291.75 1003

299.45 1027

323.75 1105

373.05 1256

373,15 125S

423.35 J 404

472,35 1539

472.95 1540

523.65 1668

523.85 1667

9) BaH K/iHB. Maacc

192,29 652.1 204,63 697.2

212,77 704,2

220,65 752,3

235,15 802,5

250,56 856,0

264,13 900.8

273.08 932,2

284,38 969.6

290.33 990.7

296,50 1010.6

10)\oMHHrc, Mefwafu, 3r.iH

303,15 1054

323,15 1093

343,15 1172

368,15 1255

11)

193.15

273.15

323.15

423,15

523.15

12)

308,15

323.15

334.75

338,15

339,15

343,65

350,95

353,35

361,35

13)

297.15

323.15

373,15

423,15

14)

293.15

323.15

373.15

473,15

523,15

15)

193,15

213.15

233,15

253,15

273,15

297.15

FpaaeH, VlaMGepr

Jla.MSepT

roJiy6eB

MU3HK

714

945

H06

1407

1680

1059

1110

1157

1163

1168

1187

1209

1217

1251

1023

1108

1260

1405

1008

1103

1257

1541

1666

He;;yjKiiri. XMapa

695

75!

808

868

949

1023

[Key on next page]

-102-
KEY: 1. Obermayer

2. Rreitenbach

!, . Z i III in o r 4. Trautz, Narath

5. Trautz, Stauf

6. Titani

7. Trautz, Melster

8. Trautz, Heberling

9. Van Cleave, Maass

10. Comings, Mayland, Egly

11. Graven, Lambert

12. Lambert

13. Golubev

14. Misic

15. Neduzhiy, Khmara

Table 48. Experimental Data on Viscosity of Gaseous Propylene

at Atmospheric Pressure

10- H-ceKlM- T)- 10—8

1) TnTai!ii

293,15 833

294,65 856

313.15 843

313,15 959

353,15 1023

373,15 1071 393.15 1122

27 payTM, Xyceftim

. 289,9 834

293,1 844

296,2 854

323,1 935

329,5 951

373.3 1076

423,1 1211 425,9 1219

472,6 1338

521,7 1464

3) Ban Kjihb, Maacc

193.43 561,5

197,45 572,4

202,26 582,6

212,45 611,9

217,52 623,6

234,40 670,4

247,34 709,3

_-^61,36 750,0

273,0 78,3,9

273,15 784,1

282,51 813,3

291,84 840,6

297.31 858,3

293,15

323,15

423,15

523,15

4)rpaBeH, JIa.M6epT

843

933

1210

1467

5 ) 3eH4)T,neCeii

303,15 I 898

6 ) .na.M6epT

308,15 922

323,15 954

333,05 991

338,15 986

339,15 1000

344,15 1024

350,95 1023

354,35 1056

363.95 1080

7) ro.ny6eB

291,15 839

326,15 942

358.15 1032

373,15 1075

423,15 1212

473,15 1340

523.15 1408

8) HeflyjKHH, Xxiapa

210

230

250

270

29/) 310

586

640

736

800

828

904

KEY: 1. Titani

2. Trautz, Husseini

3. Van Cleave, Maass

4. Graven, Lambert

5. Senftleben

6. Lambert

7. Golubev

8. Neduzhiy, Khmara

Deviations of the experimental data on the viscosity of gaseous

propylene at atmospheric pressure from the recommended values are of the

same order of magnitude. The experimental data [4, 16, 9, 13, 15] have a mean deviation of 0.4%. The maximum deviations do not exceed 3.6%.

-103-
Table 49. Smooth Data on Viscosity of Gaseous Propylene at

Atmospheric Pressure, Presented in Lehman's Review [21]

r," K • 10—^, h-cck/m' \\ r." K

ll

T) • 10—8, H-ceK/Mt 1 T.° K

:93,15

223,15

253,15

273,15

293,15

323,15

373.15

560 423,15

639 1 473,15

726 1 523,15

784 573.15

845 673,15

933 773,15

978 i 873.15

i

1220

1342

1468

1590

1816

1970

2235

973,15

1073,15

1173,15

1273.15

2123

2615

2785

2947

Table 50. Calculation of Numerical Constants According to

Girshfel 'der ' s Equation

T." K

ij

«. % T," K

1)

S 0/

/ 3) 1 F, ^rH;ieH -|-=228.0°K; a =--4,1385 Aj Hponiwen ^= 296,0"K; a=4,5945 Aj

220 770 —1.61 220 624 —1.21

260 903 —0,2 260 1748 +0,08

300 1033 —0,62 300 863 +0,02

400 1336 —0.29 400 1148 +0,47

500 1622 —0,03 500 1413 +0,52

600 1879 —0,12 600 1652 +0,28

800 2312 —1,36 800 2085 +0.13

1000 2465 —0,35

KEY: 1. n u'lO'^ N'sec/ graph

Table 51. Calculation of Force Constants by Sutherland Equation

1)

, 1)

T.° K i. % T." K 10—^, H-CeKlM- 5. %

2) 3TH,aeH (/2 (7) zjk = 236.0^ K. o = 3,895 A) r^onH;ieH ( 2 (Y) e/'t = 320,0° K. 0 == 4,387 A)

220 270 +0,61 220 624 —0,01

260 903 —0,10 2G0 747 +0,08

300 1033 —0,38 300 863 —0,31

400 1336 —0,71 400 1148 +0,03

500 1622 —0,18 500 1413 +0,034

600 1879 —0,07 GOO 1652 +0,14

800 2312 —1,03 800 2085 —0,07

1000 2465 0,38

2. Ethylene

3. Propylene

KEY: 1. n , '10 \ N'sec/m^ 2. Ethylene

graph _ _, ^ ^ ^ 3. Propylene

The smooth data on the viscosity of gaseous ethylene at atmospheric

pressure, presented in I. F. Golubev's review [13], have a mean deviation

-104-
of 0.3% from the recommended values; the maximum deviation is +2.25%. The

smooth data on the viscosity of gaseous propylene at atmospheric pressure

according to Lehman [21] deviate by 0.35% on the average if one clearly

falling point is excluded from the examination (T = 373.15°K, n = 978 x

X lO'^ N*sec/m^; n = -9.0%); the maximum deviation is 3.6%.

The error of the recommended data (Table X) is 2%.

Viscosity of Gaseous Ethylene and Propylene at High Pressures

The viscosity of ethylene was measured by Comings, Mayland and Egly

[8] in the 303.15 to 368.15°K temperature range at pressures up to 173.3

bar. A capillary viscometer of the Renkin design was used for the measurements. Fifty experimental points were obtained (see Table 52); the

measurement error did not exceed ±1.3%.

I. F. Golubev and V. A. Petrov [11] and I. F. Golubev [13] investigated the viscosity of ethylene with capillary viscometers of original

design. These viscometers, in addition to ease of handling, provide high

measurement accuracy. The error is of the order of ±(l-2)%. The authors

[11] analyzed experimentally the viscosity of ethylene at 313. 15°K at

pressures up to 137.1 atm (10 experimental points). Investigations [13]

were conducted at 297 . 15-423 . 15°K at pressures up to 810.6 bar (76

experimental points). Data [11] for t = 40°C are presented below:

p, arrxM p, ani.H 11-10-8 H

1 IC93 67,4 1620

4.4 1101 79,3 2030

28,2 1192 89,5 2500

48,6 1330 103,1 2980

55,5 1410 137,1 3790

Data [13] are listed in Table 53. The viscosity of gaseous ethylene

at 297.15°K at pressures up to 1,000 bar was investigated by M. G.

Gonikberg and L. F. Vereshchagin [23] (10 experimental points). Measurement was done with an oscillating disc viscometer; the dynamic viscosity

coefficient was calculated with the Macwood equations [24] . According to

the authors' calculations the measurement error did not exceed ±2%. Their

data on the dynamic viscosity coefficient of ethylene are presented below:

p. aniM T1- JO H-ceKl.^i- p, amM

100 3800 600 9-100 200 5500 700 10 160

300 G810 800 10 940

400 7820 900 11 710

500 8G20 1000 12 430

The viscosity of gaseous ethylene at 193 . 15-297 . 15°K at pressures up

to 39.2 bar was investigated experimentally by I. A. Neduzhiy and Yu. I.

Khmara [15] (Table 54). The investigations were done with a capillary

viscometer with annular weights of the Timrot design. The measurement

error was ±3%.

-105-
The experimental data found in the present literature can be used as the basis for comparing tables of the dynamic viscosity coefficients of

gaseous ethylene to densities p = 490 kg/m^.

The viscosity of compressed gaseous propylene was investigated

experimentally by I. F. Golubev [13] at 291 . 15-523 . 15°K and 1-800 atm

(96 experimental points). I. A. Neduzhiy and Yu. I. Khmara [15] experimentally found the viscosity of gaseous propylene at 210-310°K at pressures

up to 8 atm. The experimental data [13, 15] are presented in Tables 55

and 56. These data can be used as the basis for comparing the dynamic

viscosity coefficients of propylene to density p = 620 kg/m^ . The results

of Enskog's theory [25] were used for explaining the question of reliability

of the experimental data.

s As pointed out in [26] , there are certain dependences of the effective

diameters of collisions of molecules on temperature and pressure.

Table 52, Experimental Data of Comings, Mayland and Egly [8] on

Viscosity of Ethylene

T, . 10—^. H-CCK/M' npH /, C

p. am

30 50 70 95

1,00 1054 1074 1093 1172 1255

5,08 lOGO lOSO 1099 1180 1258

28,2 1131 1150 1192 1243 1295

48,6 1299 1306 1305 1336 1389

55,6 1406 1369 1362 1381 1426

67.3 1775 1592 1505 1474 1498

79,1 2545 2003 1721 1606 1589

89.3 3047 2483 1975 1736 1681

103.1 3592 2997 2396 1919 1818

137.0 4347 3203 2558 2265

171,0 2773

Table 53. Experimental Data of I . F. Golubev [13] on Viscosity of Ethylene

p, arrxM 10—^. H-ctKiM^ npii /.

04 50 100 130 b, aniM 24 50 !00 150

1 1023 1108 1260 1403 150 4885 3670 2380 2150

25 1096 1175 1290 1470 200 5524 4380 3027 2600

50 1410 1310 1395 1560 300 6520 5380 4095 3415

60 1813 1400 1600 400 7323 6180 4863 4150

70 2820 15(.0 1500 1640 500 8090 6890 5440 4770

80 3357 1760 1575 1685 000 8S20 7560 6147 5330

90 3667 2004 1730 700 9440 8140 6713 5860

100 3906 2VH} 1734 1760 800 9950 8670 7255 6360

125 4420 3010 2040 1950 ~ i

-106-
I Table 54. Experimental Data of I . A. Neduzhiy and Yu. I. Khmara

[15] on Viscosity of Ethylene

1 • 10— ^ H-ceKiM' npii 7". '-K

-

193.15 213. i:, 233, 15 iV3 15 •.1 Ot ' o 297,15

695 1 o\ 808 868 949 f noo IUJ3

4,90 799 835 898 968 1026

9,61 869 922 1009 1034

13,73 889 939 1021 1049

19,61 970 1045 J 069

24,52 1018 1074 1096

29,42 1099 1128

34,32 1175 1172

39,23 1273 1231

." Table 55. Experimental Data of I . F. Golubev [13] on Viscosity of Propylene

Tl • 10—8. H •cck/m' npH I. "O

p, amM

* „. , , ,. )8 53 85 100 150 200 250

1 839 942 1032 1075 1212 1340 1468

25 10 6S0 1192 1312 1423 1530

50 11 IGO 7780 5140 2805 1.550 1547 1600

75 11 620 8280 5880 4970 2400 1853 1820

100 12 050 8700 6400 5500 3405 2294 2060

125 12 480 9080 6570 6030 4100 2782 2350

150 12 880 9440 7280 6470 4600 3280 2695

200 13 650 10 130 8030 7240 5440 4085 3380

300 15 100 1 1 460 9350 8520 6740 5330 4465

400 16 400 12 700 10 460 9050 7850 6350 5420

500 17 700 13 900 1 1 500 10 680 8770 7270 6300

600 18 940 15 000 12 300 1 1 620 9670 8055 7050

700 20 120 16 100 13 460 12 500 10 480 8S05 7740

800 21 300 17 100 14 400 13 370 11 250 9500 8450

The calculations were done for ethylene and propylene using the

experimental data on viscosi'^.y [13] and data on density and thermal pressure,

found from the thermal equations of state [27, 28], derived by V. A.

Zagoruchenko. It is obvious from Figure 15 that the character of dependence

of the effective diameters of collisions a on temperature is identical for

all pressures, and the ratio cf/a^ (a^ is the effective collision diameter

at atmospheric pressure) is constant at pressures above 100 bar. At

pressures below 100 bar the ratio diminishes monotonically from unity at

atmospheric pressure to 0.92 for ethylene and 0.93 for propylene. The

observed scattering of cy/a^ is attributed to errors in the experimental data

on viscosity and to errors in the determination of the thermal pressure.

Since the scattering of points is asymmetric and falls within the limits

of possible errors, it can be concluded that the experimental data of

I. F. Golubev are reliable and that these data can be used as references

for compiling tables of the recommended dynamic viscosity coefficients of

compressed gaseous ethylene and propylene. The experimental data of

-107-
I. F. Golubev and V. A. Petrov [11] agree with I. F. Golubev's data within

the limits of deviations up to 3.5%. The data of M. G. Gonikberg and

L. F. Vereshchagin [23] deviate from I. F. Golubev's data [13] by up to

10%. The experimental data of Comings, Mayland and Egly [8] for ethylene

are 5-7% understated in comparison with I. F. Golubev's data at 300.15°K,

and 5% overstated at 103.1 atm and 368.15°K. The experimental data of

I. A. Neduzhiy and Yu. I. Khmara [15] on the 297. 1°K isotherm coincide

with I. F. Golubev's data [13] to 0.5%. These data confirm the uniqueness

of the excess viscosity as a function of density for ethylene at

temperatures below critical. The results of the measurements of I . A.

Neduzhiy and Yu. I. Khmara [15] for gaseous propylene agree satisfactorily

(deviations up to 2% in conversion to the dynamic viscosity coefficient)

with I. F. Golubev's data [13] in these coordinates.

Table 56. Experimental Data of Neduzhiy and Khmara [15] on

Viscosity of Propylene

p. Cap

1 lO'"'', H-CCKiM- Iipil r, "K

210 230 250 270 290 310

0,98 586 640 736 800 828 904

1.96 808 835 909

'

3.92 824 846 920

5.88 860 931

7.84 875 944

Experimental data [13, 15] were used for plotting the analytic

dependence of "excess viscosity" of ethylene and propylene on density. The

approximating polynomials were found by computer using the method of least

squares

All = 2,20841 • 10=^p + 7.26137 KPo^ + 7,63700 • lO'V — 2.72752 • lOy -f

+ 4.68144 • lOV— 1,25904 • 10^;

At] = 5,36654- lO'p — 4.49091 • 10^ + 4.41389 -lOy —

- 1.16544 lOy + 1,10455 • loy.

(61)

(62)

where An = lO"^ N'sec/m^; p = 10^ kg/m^

Polynomial (61) describes experimental data for ethylene in the

density range p = 0-490 kg/m^ with an average error of 0.6%. For the

calculation 129 points were used.

Polynomial (62) describes the experimental data for propylene in the

density range p = 0-620 kg/m^ with an average error of 1.6%. The approximation was done on the basis of 88 points.

Polynomials (61) and (62) were used for compilation of Tables XI

and XII of recommended viscosity. The error of the data is 2-3%.

-108-
6/6,

0,99

0.97

Q9S

0,93

0.91

0.90

• •

(

Ethylene Propylene

o-/

s-2 e-7

®-J . *>'8 a-4

c

<

:

»

s

•

o

a'

>

>

<

1

1

• o

( e

e a oeo

e <

c

o

> 1

> —

i

!> 1 --

\

. \

>

, 1

o o e

1.

•

< >~

wo 200 300 400 500 600 700 p, dap

Figure 15. Ratio cj/a^ for ethylene and propylene according to

I. F. Golubev [13]: 1 -- 293.15; 2 -- 333.15; 3 -- 373.15;

4 -- 410.15; 5 -- 433.15°K (ethylene); 6 -- 370; 7 -- 420;

8 -- 440°K (propylene)

.

Viscosity of Ethylene and Propylene on Saturation Curve

Experimental works on the viscosity of liquid ethylene and propylene

near the saturation curve are listed in Table 57. Studies [29, 31, 34]

were done by the capillary method. Studies [30, 32, 33] were done by the

oscillating cylinder method. The experimental values of the dynamic

viscosity coefficients are summarized in Tables 58 and 59. Data in

various source on the viscosity of liquid ethylene and propylene near the

saturation line are either repetition of data [29-33], or are the result

of smoothing of these data.

It follows from Tables 58 and 59 that ethylene is experimentally

investigated in the 105 . 0-289 . 9°K temperature range (the melting point of

ethylene T , = 104.0, and the critical point T^^ = 283.05°K); propylene

^ melt cr

is investigated in the T = 88 . 7-361 . 95°K temperature range (the melting

point of propylene T^^j^^ = 87.9 and the critical point T^^ = 365.05°K).

Since the existing experimental data are contradictory and are

characterized by substantial scattering, the possibility of constructing

tables of the dynamic viscosity coefficients without additional information is doubtful at the very least. This situation is not exceptional.

As pointed out in [26] , the dynamic viscosity coefficients can be determined with sufficient reliability for several n-paraffins if, in addition

to viscosity data, data on density of the liquid and saturation vapor

-109-
tension are used. The correlations obtained in [26] ensure an accuracy of

the order of 2-4% in the calculation of the dynamic viscosity coefficients

of n-paraffins in the liquid saturation state.

Table 57. List of Experimental Works on the Viscosity Coefficient of

Liquid Ethylene and Propylene near Saturation Curve

n

ABTOptJ

7)

PyACHKO [29]

P>WHKo [30]

Fept}), FajiKoi! [31]

ra.fiKOB, Fepc}) (32)

8)

Fepc}), Fa^HKOB [31]

Fa;iKOB, Fep(Ji [33]

HeayjKHH, X.Mapa [34]

6) npoiiH^icH

ion

31

CMneparypa. "K 4 )Co/iiiqecTBo r-rccncpHMeH1934 110,6—108,3 9

1939 169.3—280.3 6

1940 105.0—168,2 9

1941 183.8—273.1 5

1940 88.7—169.6 12

1941 119.0—174,8 5

1967 193,9—362.9 34

KEY: 1. Authors

2. Year

3. Temperature, °K

4. Number of experimental points

5. Ethylene

6. Propylene

Rudenko [29]

Rudenko [30]

Gerf, Galkov [31]

Galkov, Gerf [32]

Gerf, Galkov [31]

Galkov, Gerf [33]

Neduzhiy, Khmara [34]

Table 58. Experimental Data on Viscosity of Liquid Ethylene

T) . 10—6. H-CCKiM' ^^ K Tj • 10 ^, h-cck/mPyflCHKO Fepcj), Fa.'iKOB

110,5 522 105,0 660

126.0 402 108.0 600

127,2 388 110.4 553

128.1 369 129.8 334

134.1 333 138.4 282

141,2 261 148.8 231

155.0 215 156.8 197

160.0 207 168.2 164

168,3 181 183.8 135

169.3 167 204.6 115

206.1 96 226,4 92.0 233.9 77,5 252.2 72,0

240.9 75 273.1 64,0

273.1 65

280.9 02,5

-110-
Table 59. Experimental Data on Viscosity of Liquid Propylene

T.' K TJ . 10-^

1 ) rep({;.

88.7

89,8

90.)

94,3

98.0

102,6

111.1 141,6

141,9

150,0

159,8

169,6

119.0 123,0

134.2 173.0

174,8

ra;iKOB

14 660

12 730

12 400

7840

5370

35S0

2150

700

670

550

• 450

340

1550

1310

900

380

370

T, . 10—6

H • CeK/M' K

2) Hc;iy>KJu"i

193.92 198.09

202,53

20S,92

» 213,03

217,62

221.50

229.37

233,12

237,68

242.07

246,35

251.75

259,14

265.54

281,48

291,57

X.\:apa

278,6

264.2

238,2

219,9

214,0

208,8

197.3

179.4

173,4

162.4 155,9

148,0

143.3 132,5

123,6

105,1

93,98

291,57

291,94

292,19

294,86

297,45

299,33

301,i;3

304,3

307,36

311,48

315,43

315.61

329,07

340.68

354,23

355,21

362,86

n

. 10-6

99,9

99,8

92,2

93,7

91.7

89.0

88,4

82.9

82,4

78.7 76,2

74.6 63.7

52,4

43.6

42,8

32,7

KEY: 1. Gerf, Galkov

IS

10

0,^

d,%

J5

10

6

0

-s.OA

2. Neduzhiy, Khmara

o

B. 0-/

e-2 o-J

o ^

st-t-S—8-

©

0

o o o e o jo S eS~

OS .0,6 0,7a

0,8 09

o-J .

• '4

0-6

•

er-

•

•

•

1 o.s 0.6

'•I

0,8 0,9

Figure 16, Deviations of experimental data of specific volume

of ethylene (a) and propylene (b) from theoretical according

to: 1 -- Mathias, Crommelin, Wotts [35]; 2 -- V. A. Zagoruchenko

[27, 28]; 3 -- Voytyuk (see Chapters II and III); 4 -- Rossini

[37]; 5 -- Lehman [21]; 6 -- Morecroft [38].

As applies to ethylene and propylene, it is essential first of all to

check how accurately the experimental data on density agree with the

theoretical according to equations [26]

.

-Ill-
The deviations of the experimental values of specific volume on the

saturation curve from the theoretical are shown in Figure 16. As seen,

the data of Mathias, Crommelin and Wotts [35] are up to 0.9-0.4% understated in the range of reduced temperatures from t = 0.45 to t = 0.80,

agree with the theoretical from t = 0.80 to t = 0.90 and then increasingly

exceed the theoretical. The saturation parameters of ethylene were calculated by V. A. Zagoruchenko [27] and are presented in [36] . As seen in

Figure 16, these data have the same deviations from the theoretical as

data [35]. B. V. Voytyuk's experimental data (see Figure 16), obtained

by extrapolating experimental data on the density of the liquid to the

saturation curve, have a 0.2% deviation from the theoretical in the x =

= 0.65 to T = 0.90 temperature range. At higher temperatures the experimental specific volumes systematically exceed the theoretical.

And so, according to experimental data on the density of liquid

ethylene on the saturation curve, calculation using equations [26] is

justified within 1-1.5% for reduced temperatures t < 0.95, i.e., just as in the case of n-paraffins.

The experimental data of Farrington and Sage [40] and the calculated

data of Canjar, Goldman and Marchman [41] are generalized in Lehman's

review [21] . The specific volumes of liquid propylene presented in this

review are 0.05-0.6% overstated in the range of reduced temperatures from

T = 0.45 to T = 0.71, and the deviations are not systematic; in the

reduced temperature range of t = 0.71 to t = 0.90 they change sign and

amount to 0.25-1.1%. At higher temperatures the data have a certain

amount of scattering, but the deviations from the theoretical values are

characteristic of n-paraffin. Morecroft's data [38] on the density of

propylene are up to 0.35% overstated in the temperature range from t =

= 0.75 to T = 0.88; at x = 0.95 the data are 1.3% lower than the

theoretical. B. V. Voytyuk's experimental data are an average of 0.5%

higher than the theoretical in the range from x = 0.50 to x = 0.75, and

in the temperature range from x = 0.75 to x = 0.85 the deviations amount

to +0.2%.

For ethylene 3 = 0.5414, which is close to 6 = 0.5129 for ethane;

for propylene B = 0.5953, which is close to 3 = 0.6145 for propane.

These results enable us to proceed to analysis of the existing

experimental data on the viscosity of liquid ethylene and propylene on

the saturation curve and, in the final analysis, to calculate the dynamic

viscosity coefficients. According to [26] the viscosity of liquid

n-paraffins on the saturation curve is described by the expressions:

[kp=cr] '^^v^"-^ ! (63)

iKp

/

(t) = — 9.7404 + 40.795T — 1 1 4,647t2 + 1 94.005x3 i 67,925t* + ^^^^

4- 57.47lT^

-112-
where a = 0.3026 does not change with temperature; 3 is a constant in the

reduced temperature range from (0.35-0.45) to 0.95; n* is calculated

according to the Licht -Stechert equation [39], the applicability of which

is demonstrated in [26]

.

As seen in Figure 17, N. S. Rudenko's data [29, 30] on the viscosity

of ethylene are up to 27% overstated in the low temperature range, satisfy

the Bachinskiy equation with up to 6% scattering in the 155.0 to 240. 9°K

temperature range, and are substantially overstated at higher temperatures.

The experimental data of S. F. Gerf and G. I. Galkov [31, 32] on the

viscosity of ethylene have the same character, with the exception that

substantial overstatement of the data compared with the theoretical occurs

at a lower temperature (226. 4°K). Nevertheless the character of the curve

of the constant 3 as a function of the reduced temperature is noteworthy.

Its values are close to 0.541, found from data on density (this value is

shown in Figure 17 as a segment of a straight line, denoting the range

of temperatures where the Bachinskiy equation is used) . The same conclusions concerning the character of experimental data [29-35, 40, 41] can

be made on the basis of examination of the results of calculation presented

in Figure 18.

0.9

Q7

o~J

»-2

e-J

•

e

e

g>

\ —

•

••

•

> o

o

•

[ V' o

• , 0. o • eo aoo—r>0|i|—

; e

oTi^Jwr

1^

0-1 *«3!r-B }—Va

•

4J

£(2 0,3 0.5 0.6 0,7 0.8 0,9

Figure 17. Values of 3 in expression (63) according to:

1 -- N. S. Rudenko [29]; 2 -- N. S. Rudenko [30]; 3 --

S. F. Gerf and G. I. Galkov [31, 32] (ethylene); 4 --

S. F. Gerf and G. I. Galkov [31, 33]; 5 -- I. A. Neduzhiy

and Yu. I. Khmara [34] (propylene).

Experimental data [31, 33] on the viscosity of liquid propylene near

the saturation curve are up to 32% overstated at 111.1°K; at lower

temperatures a systematic increase of 3 is observed, characteristic of the

region near the solidification point. In the 193. 9-363. 0°K temperature

range the experimental data are given by I. A. Neduzhiy and Yu. I. Khmara

[34].

-113-
Figure 18. Values of functions f(T) in expression (64)

according to: 1 -- N. S. Rudenko [29]; 2 -- N. S. Rudenko

[30]; 3 -- S. F. Gerf and G. I. Galkov [31, 32] (ethylene);

4 -- S. F. Gerf and G. I. Galkov [31, 33]; 5 -- I. A.

Neduzhiy and Yu. I. Khmara [34].

As seen in Figures 17 and 18, the data satisfy both equations (63)

and the generalized relation (64) with a mean error of 2%. It follows

from these data that in order to calculate the viscosity of liquid propylene

on the saturation curve it is necessary to take 3 equal to 0.5953, found

from data on density. The data of S. F. Gerf and G. I. Galkov [31, 34] at

141 . 9-174 . 8°K also support this conclusion.

Thus, by comparing the experimental data on viscosity of liquid

ethylene and propylene near the saturation curve we can conclude that the

calculation procedure developed on the basis of analysis of the experimental

data for n-paraffins, is also applicable to ethylene and propylene. This

conclusion is also verified by the good agreement between the experimental

data on the viscosity of ethylene and propylene at high pressures and the

theoretical values for the saturation curve, if they are represented in the

form of excess viscosity as a function of density. Tables of the

recommended dynamic viscosity coefficients of ethylene and propylene in the

saturated liquid states have an accuracy of the order of 3-5% and were

compiled on the basis of equations (63) and (64) . The following critical

parameters were assumed [26]: ethylene -- p^^ = 50.97 bar, v = 0.00474 m^/kg,

T = 283.05°K; propylene -- p = 46.41 bar, v = 0.00433 mVkg, T

cr ' f fj r^^j. ^' cr

= 365.05°K.

In view of the lack of experimental data on the viscosity of gaseous

ethylene and propylene on the saturation curve we checked only the agreement

with data [15] on the viscosity of compressed gaseous ethylene and propylene

at temperatures below critical when we compiled the tables of recommended

values. The recommended values were computed according to polynomials (61)

and (62). The accuracy of the data is -3%.

-114-
Viscosity of Liquid Ethylene and Propylene at High Pressures

The viscosity of liquid ethylene at high pressures was not investigated.

Therefore to compile tables of recommended values we used the fact that in

view of the uniqueness of excess viscosity as a function of density it is

possible to extrapolate into the high-pressure region on the basis of isochors ; here we used the recommended dynamic viscosity coefficients of liquid

ethylene on the saturation curve (Table IX) as the reference data.

Extrapolation by isochors was done on the basis of thermal equation of state

(36) for liquid ethylene, which was reported by V. A. Zagoruchenko and

Tsymarnyy at the Third All -Union Conference on Thermophysical Properties of

Matter at High Temperatures (Baku, 1968) . The results of calculations are

presented in Table XI. The accuracy of the data is ~5%.

The -viscosity of liquid propylene at high pressures was investigated

by I. F. Golubev [13]. The measurement results are given in Table 55. We

used these data to construct interpolation polynomial (62) , on the basis of

which we compiled Table XII of recommended viscosities.

-115-
CHAPTER VIII. THERMAL CONDUCTIVITY OF ETHYLENE AND PROPYLENE

Thermal Conductivity of Ethylene and Propylene at Atmospheric Pressure

Experimental works pertaining to investigations of the thermal

conductivity of gaseous ethylene and propylene at atmospheric pressure are

listed in Table 60. The results of investigations are listed in Table 61.

Eucken [1, 2] measured the thermal conductivity of ethylene by the

relative wire heating method in an apparatus consisting of two measurement

tubes of different length for compensating the heat losses from the ends.

For air, used as the reference gas, = 237'10~'* W/(m*deg) at 273. 1°K at

1 atm. Eucken's data are the only data available for temperatures below

273°K.

Lambert, et al [7], for determining the thermal conductivity

coefficient of several hydrocarbon gases (including ethylene and propylene

at 339.15°K) also used the relative (in terms of air) hot wire method,

employing, like Eucken, a measurement cell with two wires of different

length. The thermal conductivity of air was assumed equal to 289*10 '* W/(m*deg) at 339.15°K. The thermal conductivity coefficient was calculated

by two methods on the basis of measurement data, showing agreement within

±0.5%. The deviations of the data from existing data on for certain

hydrocarbon gases, according to the authors, do not exceed ±(2-3)%.

The thermal conductivity of ethylene and propylene at 70°C was

determined by Senftleben and Gladisch [3] on the basis of a relation

containing the Nu, Gr and Pr criteria for determining the amount of heat

transmitted through a layer of gas between two horizontal coaxial cylinders

with different diameters. By altering the procedure somewhat Senftleben

[5, 10] determined the thermal conductivity of ethylene and propylene at

20-200°C at nearly atmospheric pressure. Equations of the thermal

conductivity coefficients as functions of temperature were derived on the

basis of experimental data for ethylene:

?.o= 175- 10-" + 122,7- 10-'/ + 147,8 10"' (65)

-116-
for propylene:

?to = 145,7 • 10-" + 105,9-10-' / + 180 • 10"'

(66)

where t is measured in °C and in W/(m*deg).

Table 60. List of Experimental Investigations of Thermal Conductivity

Coefficient of Gaseous Ethylene and Propylene at Atmospheric Pressure

1 ) ABTOpbl

7)

SiiKCH ( 1

)

SiiKGH (2) 3cH(j)iv]e6eH h Vjiajiuui [3] /leiiyap h Komhutc [4] ScH^JT^ieOen [5] KcHC |6)

JlaMfiepT H ap. [7] MafiKHH H MapKCDHM (8J Meynr h ap. {9]

3eH(})T/ie6eH (10]

He;;yjKHH, Kpaaeu, Kojiomhcu [I,

2) roa

3eii(})T;ie6cfi h fjiaflHUj [3] 3en(i)T;ie6eH [5] JlaMfiepT H up. [7] 3eHc})T;ie6eii [lO]

HeAy>KHH, Kpaneu, Ko;/OMneu [llj

5 ) 3ni;ieH

1913

1940

1949

1951

1953

1954

1955

1958

19G2

1964

1967

6) ripoiiii^ieii

1949

1953

1955

1964

1967

3)

TcMneparypa. "K

202—273

273

343

314; 340

303

345; 426

339

293—523

591

273—673

250—400

343

303

339

273—673

273—400

.in HeCTBO

TOncK

3

1

12

12

16

I8

16

1

1

19

14

KEY: 1. Authors

2 . Year

3. Temperature, °K

4. Number of points

5. Ethylene

6. Propylene

7. Eucken [1]

Eucken [2]

Senftleben, Gladisch [3]

Lenoir, Comings [4]

Senftleben [5]

Keyes [6]

8.

Lambert, et al [7]

Chaykin, Markevich [8]

Cheung [9]

Senftleben [10]

Neduzhiy, Kravets, Kolomiyets [11]

Senftleben, Gladisch [3]

Senftleben [5]

Lambert, et al [7]

Senftleben [10]

Neduzhiy, Kravets, Kolomiyets [11]

The values of given by equations (65) and (66) were extrapolated to

0, 300 and 400°C. The error of the published data up to 200°C, according to

the author, is less than ±1%, and at higher temperatures it may reach 3-4%.

A. M. Chaykin and A. M. Markevich [8] published six values of the

thermal conductivity coefficient of ethylene at temperatures of 293.15 to

523.15°K. The accuracy of these data, obtained with the aid of a simplified

glass model of the coaxial cylinders method without strict consideration of

all required corrections, was estimated by the authors themselves as ±5%.

-117-
Table 61. Experimental Data of Various Authors on Thermal ConductivityCoefficient of Ethylene and Propylene at Atmospheric Pressure

1) I)

T, "K .10<, em/(M- epad) T. "K X,.10«, am/(,M-epad)

2) Shkch (l)

202.0

235,8

273.1 2) Shkch (2]

273.1

108

136

171

173

9) MaHKHH, MapKCBHM [8]

3) Jlenyap h KoMHHrc,[41

314.3

' 221

340.4 256

4) Keflc (6)

345.4 425.7267

391

5^ J]aM6epT H ;ip. [7) 339,15 I 257

6) Meynr h ;ip. [9] 591.15

j 641

7) 3eH4)TJie6eH ii Vjiaauui (3J 343.15 I 265

8) 3eH4)T.ne6en [5] 303.15

I 209

8) 3eH(J)T;ie6eH [lOJ

175

206

240

273.15

298.15

323,15

423,15

473.15

573,15

673,15

392

479

674

904

293.15

323.15

373.15

423.15

503,15

523,15

10) HeayjKHH H flp.

250

260

270

280

290

300

310

320

330

340

350

360

370

380

390

400

[llj

197

247

310

368

477

515

1

148

159

170

181

193

204

217

229

242

255

269

282

296

310

325

340

riporiH.ieH

5) JIaM6epT H jp. (7] 10) He^y^HH H up. (Ill

339.15 219 273,15 150

7) 3eH({)T.ie6eH

343.15

303,15

H r.iaaHui (3) 220

178

280

290

300

310

157

167

178

188

8 )

3eH(j)T.i c6eH [10] 320 199

273,15 146 330 210

298,15 173 340 221

323,15 203

' 350 233

373,15 270 360 245

423,15 345 370 257

473.15 431 380 270

573,15 624 390 282

673,15 854 400 295

[Key on next page]

-118-
KEY: 1. ^n'lO"' W/(m«deg) 6. Cheung, et al

7. Senftleben and Gladisch

8. Senftleben

9. Chaykin, Markevich [8]

10. Neduzhiy, et al

2. Eucken

7). I,enoir, Comings

4 . Keyes

5. Lambert, et al

One experimental value of of ethylene at 318°C is presented in

the work of Cheung, et al [9], which pertains to investigation of the

thermal conductivity of binary and tertiary gaseous mixtures by the coaxial

cylinders method.

Experimental data on the thermal conductivity of ethylene and

propylene at atmospheric pressure are compared graphically in Figure 19.

As follows from the figure, the data of most authors agree within 4%. The

exceptions are Eucken 's point [1] at 202°K and the values obtained by

A. M. Chaykin and A. M. Markevich [8] and by Cheung [9] , the deviations of

which from the data of the other authors reach 8%.

The limited number of experimental points complicates generalization

of data on the of ethylene and propylene. For this reason we used the

conclusions of Owens and Thodos [12] for the purpose of matching them up

and correlating them. Owens and Thodos, by processing a large volume of

experimental data on the thermal conductivity of various hydrocarbon gases

and their derivatives at atmospheric pressure, discovered that the dependence

of the thermal conductivity coefficient in logarithmic coordinates on the

reduced temperature is expressed by a straight line with the same slope for

all hydrocarbons and their derivatives, excluding cyclic. The authors

thereby discovered the identical temperature dependence of X^ of these

gases at atmospheric pressure (the mean deviation for 414 experimental

points is 1 .6%)

.

Here, Owens and Thodos used N. V. Tsederberg's generalized method

[13] for representing data on the thermal conductivity of gases at

atmospheric pressure in dimensionless coordinates. The critical

temperature T^ and thermal conductivity corresponding to it X were used

cr

as the reduction parameters. A single common straight line was obtained

in logarithmic coordinates for all the gases they investigated, and this

line is described by the equation

[kp=cr] (67)

where n = 1.786.

-119-
Figure 19. Thermal conductivity coefficients of ethylene (I)

and propylene (II) at atmospheric pressure as functions of

temperature according to: 1 -- Eucken [1, 2]; 2 -- Lenoir,

Comings [4]; 3 -- A. M. Chaykin, A. M. Markevich [8]; 4 -- Keyes [6]; 5 -- Lambert, et al [7]; 6 -- Cheung, et al [9];

7 -- Senftleben, Gladisch [3]; 8 -- Senftleben [5]; 9 -- Senftleben [10]; 10 -- I. A. Neduzhiy, et al [11] (for

ethylene); 11 -- Senftleben [10]; 12 -- Senftleben, Gladisch

[3]; 13 -- Senftleben[5] ; 14 -- Lambert, et al [7]; 15 --

I. A. Neduzhiy, et al [11] (for propylene).

By converting expression (67) to an equation of the form

[kp=cr] ^Kp ^.Kp I T^Kp.' (68)

and using X = 504. 5*10"'* and A = 184. 2 •lO"'* W/(m'deg), Owens and Thodos

cr ^cr . derived a final equation for describing the thermal conductivity of

ethylene as a function of temperature at atmospheric pressure:

>^np = = 0.364 . t'-^* (69)

-120-
f

We used equation (67) for processing data on the thermal conductivity

of ethylene and propylene at atmospheric pressure, since equation (69)

introduces hard-to-determine A

cr

In equation

\ = A-t" (70)

the constant A = X /T^ is calculated by the method of least squares on

cr

the basis of experimental data for ethylene (with the exception of data

[8, 9]) and the power index is the same as in [12]. The result is the

equation

>^o = 0,775. 10-^ 7'''^.

(71)

where X^ is measured in W/(m'deg) and T in °K, as recommended for calculating

the thermal conductivity coefficient of ethylene at various temperatures and

atmospheric pressure.

The deviations of the experimental values of the thermal conductivity

coefficient of ethylene from those calculated using equation (71) are shown

in Figure 20. The data of all authors coincide only at temperatures close

to 273°K. As the temperature rises, the deviations increase. The greatest

deviations are found in the data of A. M. Chaykin and A. M. Markevich [8]

,

Cheung [9] and Eucken [1] at 202°K. Here the temperature dependence of

these data differ substantially from the most probable, described by

equation (71)

.

The deviations of the data of the other authors from the theoretical

do not exceed ±2%. Only the deviation of Senftleben's data of 1964 [10]

reaches +3.8% as temperature increases to 673°K, which otherwise coincides

with the accuracy specified by the author.

The reference thermal conductivity coefficients of ethylene at

atmospheric pressure [14, 15, 16, 17] were also compared.

These data are contradictory and substantially understated: to -12%

[14, 15]; from -5.8 to -32.7% at 273-1, 073°K [16], and from 3.3 to -23.6%

at 223-1, 273°K [17].

Thus it can be affirmed that equation (71) describes in the 200-700°K

temperature range the dependence of the coefficient of thermal conductivity

of ethylene at atmospheric pressure on temperature with a maximum error

of 4%. The actual deviations, however, should be considerably lower, since

the experimental data of most authors [1-7, 11] agree within ±2%.

When plotting the experimental data on the coefficient of thermal

conductivity of propylene at atmospheric pressure on the graph (see

Figure 19 and Table 61) what stands out most is the irregular temperature

-121-
r- • -

•

• • •

•

» • # ^ , e o-o——-

T

>

A-4(

e-5 o-/^

A

^—,

200 300 ' ' TiOO sod 600 7^

Figure 20. Deviations of 6 = (X - X , )/A ^ '100% of ^ exp theo theo

experimental values of thermal conductivity coefficient of

ethylene at atmospheric pressure from values computed by

equation (71) according to: 1 -- Eucken [1, 2]; 2 -- Lenoir

and Comings [4]; 3 -- A. M. Chaykin, A. M. Markevich [8];

4 -- Keyes [6]; 5 -- Lambert, et al [7]; 6 -- Cheung, et al

[9]; 7 -- Senftleben, Gladisch [3]; 8 -- Senftleben [5];

9 -- Senftleben [10]; 10 -- I. A. Neduzhiy, et al [11].

path of the data of Senftleben of 1964 [10] . This indicates that as the

molecular weight of the investigated gas increases, the accuracy of the

Senftleben method decreases. Therefore the constant A of equation (70)

was calculated for propylene only on the basis of the close experimental

data of [3, 5, 11]

.

The equation which we used for calculating the dependence of the

thermal conductivity coefficient of propylene at atmospheric pressure on

temperature has the form

?.o = 0,667. 10-' -T^-^"^. (72)

Comparison shows that the experimental point of Lambert, et al [7]

at 339. 2°K deviates from the theoretical curve by -0.5%. The data of

I. A. Neduzhiy, et al [11] deviate from +0.5 to -0.4% as the temperature

increases from 273 to 400°K. Senftleben's data of 1964 [10] are 6%

overstated even at 400°K, and 14% at 673°K.

The tabular values of the thermal conductivity coefficient of

propylene given by Lehman [18] and presented in [17], as for ethylene,

are substantially understated.

The divergence of data [18] , calculated with the Eucken equation,

is (+1 . 3) - (-10) % when the temperature is changed from 273 to 573°K.

-122-
The deviations of the data of propylene, published in [17], are

(-19.2)-(-13.S)% in the 223-1, 273°K range.

I'hc recommended thermal conductivity coefficients of gaseous

ethylene and propylene (Tables XI, XII) were calculated through equations

(71) and (72). The accuracy of the data is ~4%.

Thermal Conductivity of Ethylene and Propylene at High Pressures

The thermal conductivity of gaseous ethylene at high pressures was

investigated by Lenoir and Comings [14] . The investigations were done by

the relative coaxial cylinders method on the 314. 3°K isotherm at pressures

from 1 to 205.1 bar and on the 340. 4° K isotherm at pressures from 1 to

230 bar. Nitrogen, methane, carbon dioxide and helium were used as

standard gases. To prevent convections the conditions under which the

Gr-Pr product was less than 600 in all cases, were maintained in the

experiments. The absence of convection was checked by changing the

temperature difference in the gas layers. The thermal conductivity

coefficients were not changed in the process.

The error of the experimental data is from 1% at low to 3% at high

pressures

.

The experimental data of Lenoir and Comings [4] are summarized in

Table 62.

Table 62. Data of Lenoir and Comings [4] on Thermal Conductivity

of Gaseous Ethylene

p. Cap ) • ID*. em/(M- epaa) 1

'

P. 6ap 10«. em/(M-epad)

T = 314.3° K 7 = 340.4° K

1.01 222 1,01 256

19.6 241 21,7 272

41.9 277 50,5 313

60.2 339 62.7 336

83.6 530 89.3 434

104.4 659 104.7 492

124.7 729 131.3 590

146.9 794 163.1 698

166,3 850 206,0 801

179.2 884 229.0 845

205,7 967

The thermal conductivity of gaseous ethylene under pressure was also

investigated by Keyes [6], but in a considerably narrower pressure range.

The data were obtained by the relative vertical coaxial cylinders method at

345.4 and 425. 7°K:

T = 345.4" K

p. Cap k-lO*. ernfiM-epad)

0 267

10.5

15.7

274

281

T - 425,7°

Cap X-IO*.

0

5.0

9,0

em/(M-epad)

391

394

399

-123-
The error of the experimental data was not indicated.

Keyes offers an empirical equation of calculating the thermal

conductivity coefficient of ethylene at pressures up to 16 bar, derived on

the basis of his own experimental data:

^ = ^^0(1 +0.75 -f . 9,7"/^),

(73)

where p is measured in bar and T in °K.

The thermal conductivity of gaseous ethylene and propylene at

250-400°K and at pressures up to 40 bar was measured by I . A. Neduzhiy,

V. A. Kravets and A. Ya. Kolomiyets [11] by the regular method with an

apparatus with a spherical bicalorimeter (the diameter of the copper core

is 41.50 ± 0.01 mm and the thickness of the gap for the investigated gas

is 1.15 ± 0.01 mm). The inner core of the bicalorimeter was centered with

the aid of a rigidly attached tube of special construction, made of a heat

insulating material, through which differential copper-constantan

thermocouple is soldered inside the core. The surfaces bounding the layer

of the investigated compound were nickel-plated and carefully polished to

minimize heat losses.

The design features of the bicalorimeter, designed for investigation

under pressure, necessitated the introduction of a number of correction

factors, which are impossible to determine analytically. Therefore the

relative method was used to investigate the thermal conductivity

coefficient. The apparatus was calibrated on nitrogen using data [19],

which made it possible to determine its constant at various temperatures

and pressures.

Particular attention was devoted to preventing convection. The

tests were conducted under conditions such that the Gr-Pr product would

not exceed 1,000. The reproducibility of X values within 0.5-1% at

various temperatures and pressures was also evidence of the lack of

convection in the investigated gas. The results of the investigation are

summarized in Tables 63 and 64.

Comparison of the thermal conductivity coefficients of ethylene at

atmospheric pressure in [11] (see Figure 19) established that the

deviation of these data and the data of Lenoir and Comings [4], Lambert,

et al [7], Senftleben [5], does not exceed 1.5%. The data of Keyes [6],

Senftleben [10] (1964) and especially of A. M. Chaykin and A. M. Markevich

[8], Cheung, et al [9], deviate to a much greater extent from the data

in [11]. Data [11] on the thermal conductivity of ethylene at high

pressures agree satisfactorily (to ±1%) with the data of Lenoir and

Comings [4], where they overlap; somewhat less satisfactorily with Keyes'

data [6], which are somewhat higher than the data in [4, 11].

-124- !
Table 63. Thermal Conductivity Coefficient of Gaseous Ethylene According

to I. A. Neduzhiy, et al [11]

pt uCp

III*

250 260 270 2S0 '200 300 310 320 330 340 350 360 370 380 390 400

11 148 159 1 / 01 O 1 19 jOA 1 JO 1 217 229 242 255 269 O O A 282 OAA 29o O 1 A 310 325 O j< A 340

2 149 160 171 20o 218 230 243 256 270 o o o 283 OAT 29/ Oil

31

1

326 O /I 1 341

4 151 162 t "7 O 173 184 19o 207 219 231 244 257 271 284 298 312 327 O ^ A 342

6 154 165 175 186 197 209 220 233 245 258 272 ZOO 300 O 1 ,< 314 328 343

8 156 166 1 1/ 1S8 199 210 222 234 217 260 273 287 301 315 329 344

10 159 168 1 (

9

190 20 1\ 212 224 236 248 261 274 OO (J 288 302 316 O A 3o0 O 1 c 345

12 162 171 181 192 203 21 ! 226 238 250 263 276 OAA 290 304 318 '} OO 346

14 166 174 183 194 205 2)6 227 239 252 264 277 OA 1 300

O 1 A 319 O OO 34o

16 169 177 186 197 208 218 230 241 253 266 279 ono 30/ O O 1 321 OO c o4y

18 173 180 189 199 210 221 232 243 255 208 281 294 308 322 OO A 336 3ol

2J) 178 184 193 202 213 224 234 246 257 270 2S3 290 310 324 338 352

22 178 189 196 205 210 22(j 237 248 200 272 285 O AO 298 312 326 340 O C < 354

24 195 201 208 219 229 2-tO _'ol Oi37 JiS / 300 314 328 o -* o 342 o c 35o

26 z 202 206 213 223 233 243 253 264 276 289 302 315 329 343 357

28 213 218 228 237 246 256 207 279 291 304 3!8 331 345 358

30 220 223 233 241 250 260 270 281 294 307 320 333 347 360

32 230 238 245 253 263 273 284 296 309 322 336 349 362

34 237 243 249 257 266 276 286 299 312 325 338 35! 364

36 245 248 254 261 269 279 290 301 314 327 340 353 366

38 253 254 258 265 273 282 293 304 316 330 342 355 368

40 260 259 262 268 276 285 296 307 319 332 345 358 370

Table 64. Thermal Conductivity Coefficient of Gaseous Propylene According

to I. A. Neduzhiy, et al [11]

p. 6ap

am/(x epao) iipii T.

273. 15 280 290 300 310 320 3:,o 340 350 360 370 380 390 400

1 150 157 167 178 188 199 210 221 233 245 257 270 282 295

2 152 159 169 179 189 200 2ll 223 234 240 259 27] 284 297

4 156 163 172 182 192 203 214 226 237 249 262 274 286 299

6 167 176 186 190 207 217 229 240 252 204 276 289 302

8 181 190 200 211 221 232 243 255 207 279 292 304

10 195 205 215 224 235 246 258 270 282 295 307

12 210 220 229 239 249 262 273 285 298 310

14 216 220 233 243 253 2(j5 277 288 301 313

16 232 239 248 258 269 280 292 304 316

18. 245 254 204 274 285 290 308 320

20 254 261 270 279 290 301 312 323

22 264 270 278 285 290 307 317 327

24 281 287 293, 302 312 322 332

26 292 296 301 309 318 328 336

28 306 310 317 325 334 341 30 320 325 332 340 3.10 32 330 333 339 340 352

34 341 312 34H 352 358

36 352 351 353 358 304

Comparison of data [11] on the thermal conductivity of propylene at

atmospheric pressure shows an error of ±0.5% in relation to the experimental point of Lambert, et al [7]. Data [11] did not support Senftleben's

data [10] (1964). Deviations of results of the latter works are +(3-14)-o.

-125-
At higher pressures, in view of the lack of other experimental data

on the thermal conductivity of propylene, we did a comparison with the

diagram proposed by Owens and Thodos [12] for ethylene, illustrated in

Figure 21. The pseudocritical thermal conductivity of propylene, calculated on the basis of data at atmospheric pressure, is = 690 x

X lO"'* W/(m*deg). The deviation is 0.5-2.5%, which indicates the

reliability of the data obtained for the thermal conductivity of propylene.

Figure 21. Reduced ethylene thermal conductivity diagram of

Owens and Thodos [12]. The authors used the following:

T = 282. 4°K, p = 50.66 bar, X = 504. 5*10"'* W/(m'deg).

cr ^cr cr

The limited number of experimental data on the thermal conductivity

of ethylene and propylene, encompassing a narrow range of parameters, cannot

be used directly for compiling tables of the thermal conductivity

coefficients of these compounds without involving calculation methods.

-126-
Figure 22. Excess thermal conductivity AX = A - as function

of density according to: 1 -- Lenoir and Comings [4]; 2 -- Keyes [6]; 3 -- Ye. Borovik, et al [20]; 4 -- Ye. Borovik

[21]; 5 -- I. A. Neduzhiy, et al [11].

no

Figure 23. Excess thermal conductivity of propylene as function

of density according to I. A. Neduzhiy, et al [11].

When the coordinate system AX = (X - X^) , p is used for generalizing

the experimental conductivity coefficients, the experimental errors obey the

simplest law in the widest range of parameters and are described by a curve

that is common to the gaseous and liquid states.

-127-
A uniparametric dependence of excess thermal conductivity on density

is used in the vast majority of cases, since the question of deviation from

it has not yet been answered for thermal conductivity near the critical

point and near the saturation curve.

Experimental data [4, 6, 11] for gaseous and [20, 21] liquid

ethylene are presented in Figure 22 in the form of excess thermal conductivi

as a function of density; data [11] for gaseous propylene are given in

Figure 23.

The dependences of excess thermal conductivity on density are

approximated by computer by the method of least squares using orthogonal

polynomials

.

For ethylene is derived the equation

(74)

AX . 10^ - 0,5358 • p + 0,9365 • 10"V — 0,6809 • ]0~^ • p' -f- + 0,3635. 10-* -p*- 0,1056 10"' • p^ + 0,1550 • lO"" -p' —

— 0,8634 . 10~'^ p^

which is valid in the 0-650 kg/m^ density range; for propylene

AX . 10* = -0.984 + 0,8270 • p + 0,3419 • lO"' • p2 + 0,1406 • lO"" • p^ —

— 0,1374 • 10"' • pS

^"^^^

which is valid in the 2.5-80 kg/m density range.

The recommended thermal conductivity coefficients of gaseous ethylene

computed using equation (74) , are presented in Table XI for T = 180-450°K

and p = 1-3,000 bar. Considering the good agreement between the experimental data of various researchers, obtained by various methods (see

Figure 22) and the validity of the reference curve AX = f(p), it can be

assumed that the error of the tabular thermal conductivity coefficients of

ethylene is ±2 to ±6%.

Data on the thermal conductivity of gaseous propylene, computed by

equation (75), are presented in Table XII and encompass the 300-450°K

temperature range and 1-50 bar pressure range.

The reduced diagram of thermal conductivity for ethylene can be used

for determining the thermal conductivity of propylene at pressures above

50 bar (see Figure 21) . The pseudocritical conductivity of propylene is

XJ^ = 690* lO'"* W/(m»deg). Comparison of the data in Table XII with the

reduced diagram shows agreement within ±2.5%.

-128-
Thermal Conductivity of Liquid Ethylene

Experimental data on the thermal conductivity of liquid ethylene are

presented in [20, 21] (no data, are available for propylene).

Ye. Borovik, A. Matveyev and Ye. Panina [20] used the hot wire

method for studying the thermal conductivity of liquid ethylene. They

used two vertical measurement tubes of different length, made of copper,

to prevent end losses.

All measurements were done with different temperature drops between

a filament and tube wall, not exceeding, however, 0.5-1 deg, to prevent

convection.

The pressure of the investigated compounds was maintained a few

atmospheres above the saturation vapor pressure at the test temperature.

The thermal conductivity measurements encompass a wide range of

temperatures. The extreme measured points are 8.7 and 9.6 deg, respectively,

from the melting and critical points.

The experimental data are presented below

T, °K X, W/(m'deg)

112.65 0,254

144.15 0,222

172,15 0.184

199,15 0,156

244,35 0.126

273,45 0,080

The errors of the data are ±2.6%.

Borovik [21] measured the thermal conductivity of liquid ethylene

at 171.25°K using the parallel plate method, which creates the best conditions for the prevention of convection. The temperature in the instrument

was measured with calibrated resistance thermometers. The measurement

error was 1% for points far from the critical and up to 3% near the critical

point. The temperature drop in the tests was 0.3-3 deg.

The thermal conductivity coefficients of liquid ethylene at 171.25°K

and 4.97 and 52.99 bar, were found to be 0.182 and 0.185 W/(m'deg),

respectively.

Data [20, 21] on the thermal conductivity of liquid ethylene,

obtained by two different methods, agree satisfactorily, which confirms

their reliability.

Data [20, 21] were used for derivation of equation (77). Tables IX

and XI of the thermal conductivity coefficients of liquid ethylene,

including the liquid saturation state, were compiled with the aid of this

equation. The accuracy of the data is ±(3-6)%.

-129-
V

PART

TABLES OF THERMODYNAMIC AND

ETHYLENE AND

II

TRANSPORT PROPERTIES OF

PROPYLENE

Units of Measurements Used in Tables

Temperature, T, °K;

Pressure, p, bar;

Specific volume, v, m^/kg;

i, kJ/kg;

r, kJ/kg;

s, kJ/(kg'deg)

;

Specific heat C^, kJ/(kg*deg);

Speed of sound, w, m/sec;

Viscosity, rij N»sec/m^;

Thermoconductivity , X, W/(m*deg).

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-190-
BIBLIOGRAPHY

Chapter I

1. Amagat, E. H. , Ann. Chim. Phys., Vol. 29, pp. 68-196, 1893.

2. Masson, J. and L. D. Dolly, Proc . Roy. Soc. (London), A103, pp. 524-538,

1923.

3. Dannell, H. V., Munster and H. Stolzenberg, Z. Angew. Chemie, Vol. 42,

pp. 1121-1123, 1929.

4. Mich'els, A., J. De Grueter and F. Niesen, Physics, Vol. 3, pp. 346-351 , 1936.

5. Michels, A. and M. Geldermans, Physica, Vol. 3, pp. 967-973, 1942.

6. Walters, R. I., J. H. Tracht, E. B. Weinberger and I. R. Rodgers , Chem.

Eng. Progr. , Vol. 50, p. 511, 1954.

7. Cramer, F., Chem. Techn., Vol. 7, No. 2, p. 68, 1955.

8. Dick, W. F. and A. G. M. Hedley, Thermodynamic Functions of Gases,

ed. by Din, London, 1956.

9. Zagoruchenko , V. A., Izvestiya Vuzov, Neft ' i Gaz (News of Institutes of

Higher Learning, Oil and Gas), No. 2, 1959.

10. Zagoruchenko, V. A., Candidate dissertation, Odessa, 1959; Vargaftik,

N. B. , Spravochnik po Teplofi zicheskim Svoystvam Gazov i Zhidkostey

(Manual on Thermophysical Properties of Gases and Liquids), Moscow,

Fizmatgiz, 1963.

11. Turlington, B. L. and J. McKetta, Petrol. Refiner., Vol. 40, No. 5, 1961.

12. Thomas, W. and M. Zander, Z. angew. Physik, Vol. 20, No. 5, p. 417, 1966.

-191-
13. Pfennig, H. W. and J. McKetta, Petrol. Refiner., Vol. 36, 11, 309, 1957.

14. Michels, A., H. Wonters and J. de Boer, Physica, Vol. 1, p. 587, 1934.

15. Edwards, J. 0., Ind. Eng. Chem. , Vol. 9, p. 790, 1917.

16. Burnett, E. C, J. Appl. Mech., A136-A140, 1936.

17. Vaughan, W. E. and N. R. Graves, Ind. Eng. Chem., Vol. 32, No. 9,

p. 1252, 1940.

18. Farrington, P. S. and B. H. Sage, Ind. Eng. Chem., Vol. 32, No. 9,

p. 1252, 1940.

19. Marchman, H. , H. W. Prengle and R. L. Motard, Ind. Eng. Chem., Vol. 41,

No. 11, 1949.

20. Canjar, L. N. , M. Goldman and H. Marchman, Ind. Eng. Chem., Vol. 43,

No. 5, p. 1186, 1951.

21. Michels, A., T. Wassenaar , . P . Louwerse, R. I. Lunbeck and G. J. Wolkers,

Physica, Vol. 19, pp. 287-297, 1953.

22. Canjar, L. N. , G. R. Jonas and F. S. Mannig, Petrol. Refiner and HydroCarbon Processing, No. 10, 1963.

23. Benedict, M. , G. B. Webb and L. C. Rubin, J. Chem. Phys . , Vol. 47,

p. 419, 1951.

24. Cherney, B. J., H. Marchman and A. Jork, Ind. Eng. Chem., Vol. 41,

p. 2653, 1949.

25. Girshfel 'der , J., C. Curtiss and R. Berd, Molekulyarnaya Teoriya Gazov

i Zhidkostey (Molecular Theory of Gases and Liquids), Moscow, IIL

[Foreign Literature] Publishing House, 1961.

26. Benedict, M. , G. B. Webb and L. C. Rubin, J. Chem. Phys., Vol. 8,

p. 334, 1940.

27. Zagoruchenko, V. A., TVT [expansion unknown], 1965.

28. Kazavchinskiy , Ya. Z. and V. A. Zagoruchenko, ZhTF (Journal of Technical

Physics), Vol. 33, No. 3, 1959.

29. Martin, J. J. and Y. C. Hou, A. I. Ch. E. Journal, Vol. 1, p. 142, 1955.

30. Benzler, Mainzer Acad. Wiss., No. 1, 1954.

31. Pings, C. I. and B. H. Sage, Ind. Eng. Chem., Vol. 49, p. 1315, 1957.

-192-
32. Vukalovich, M, P., V. V. Altunin and G. A. Spiridonov, Teplofizika

Vysokikh Temperatur (High-Temperature Thermophysics) , No. 2, 1967.

33. Spiridonov, G. A., Candidate dissertation, Mosfcow, MEI (Moscow Power

Engineering Institute), 1967.

34. Forsythe, G., J. Soc. Ind. Appl . Math., Vol. 5, p. 74, 1957.

35. Roper, E. E., J. Phys . Chem. , Vol. 44, p. 835, 1940.

36. Ratzsh and U. I. Bittrich, Z. fur phys . -Chem, , 227, No. 1-2, 1964, DDR.

37. Butcher, E, G, and R, S, Dadson, Proc. Roy, Soc, (London), A277, p. 448,

1964, ^

38. Corner, I., Proc. Roy. Soc. (London), A192, p. 275, 1948.

39. David, U. G. and M, Hamman, Thermod. and Transp. Properties of Fluids,

London, 1957.

40. Michels, A., L, C, Abels, C, A. Ten Seldam and W. de Gaaff, Physica,

Vol. 6, No. 26, p. 381, 1960.

41. Vukalovich, M. P. and V. V. Altunin, Teplofizicheskiye Svoystva

Dvuokisi Ugleroda (Thermophysical Properties of Carbon Dioxide),

Moscow, Atomizdat, 1965.

42. Zaki, W. N. , H. R. Heichelheim, K. A. Kobe and J. J. McKetta, J. Chem.

Eng. Data, Vol. 5, No. 3, p. 343, 1960.

43. Hall,K. P. and F. B. Canfield, Physica, Vol. 33, pp. 481-502, 1967.

44. Michels, A. and C. Michels, Proc. Roy, Soc, (London), A160, p, 348, 1937.

Chapter II

1. Michels, A, and M, Geldermans, Physica, Vol. 3, pp. 967-973, 1942.

2 . Voyko , N . V . and B , V , Voytyuk , Teplofizicheskiye Kharakteristiki

Veshchestv (Thermophysical Properties of Matter) , GSSSD [State Service

for Standard Information Data] Collection, No. 1, Moscow, Standards

Publishing House, pp. 33-37, 1968.

3. Michels, A. and T. Wassenaar, Physica, Vol. 16, p. 221j 1950.

4. Golovskiy, Ye. A., V. A. Yelema, V. A. Zagoruchenko and V. A. Tsymarnyy,

Izvestiya Vuzov, Neft' i Gaz , No. 1, p. 83, 1969.

5. Dick, W. F. L. and A. G. M. Hedley, Thermod. Functions of Gases, edited

by Din, London, 1956.

-193-
6. Vanghan, W. E. and N. R. Graves, Ind. Eng. Chem. , Vol. 32, No. 9,

p. 1252, 1940.

7. Farrington, P. S. and B. H. Sage, Ind. Eng. Chem., Vol. 41, p. 1734,

1949.

8. Michels,'A., T. Wassenaar, P. Louwerse, R. Lunberk and G. I. Wolkers,

Physica, No. 19, p. 287, 1953.

9. Dittmar, P., F. Schulz and G. Stresse, Chem. Ing. Techn., Vol. 34, No. 6,

p. 437, 1962.

10. Lehman, H., Chem. Techn., Vol. 14, p. 132, 1962.

11. Poll, D. B. and 0. Maas, Canad. J. Res., B14, p. 96, 1936.

12. Hanson, G. H., Trans. Amer. Ind. Chem. Eng., Vol. 42, p. 956, 1946.

13. Lu, H. , D. M. Newitt and M. Ruhemann, Proc. Roy. Soc, London, A178,

p. 506, 1941.

Chapter III

1. Henning, F. and A. Stock, Z. Physik, Vol. 4, No. 2, pp. 226-240, 1921.

2. Maass, 0. and C. H. Wrigt, J. Am. Chem. Soc, Vol. 43, No. 5, pp.

1098-1111, 1921.

3. Crommelin, C. A. and H. G. Watts, Commun. physic. Lab. Univ. Leiden,

189b, 1927.

4. Mathias, E., C. A. Crommelin and H. G. Watts, Commun. physic. Lab.

Univ. Leiden, 189a, 1927.

5. Mathias, E., C. A. Crommelin and H. G. Watts, Ann. de Phys . , Vol. 11,

p. 343, 1929.

6. Egan, C. G. and J. D. Kemp, J. Am. Chem. Soc, Vol. 59, No. 7, pp.

1264-1268, 1937.

7. Lamb, A. B. and E. E. Roper, J. Am. Chem. Soc, Vol. 62, No. 4, pp.

806-814, 1940.

8. Michels, A. and T. Wassenaar, Physica, Vol. 16, pp. 221-224, 1950.

9. Powell, T. M. and W. F. Giaque, J. Am. Chem. Soc, Vol. 61, No. 9,

pp. 2366-2370, 1939.

10. Voughan, W. E. and N. R. Graves, Ind. Eng. Chem., Ind. Ed. 32, No. 9,

pp. 1252-1256, 1940.

-194-
11. Lu, H., D. M. Newitt and M. Ruheman, Proc. Roy. Soc. (London), Vol. 178

pp. 506-525, 1941.

12. Technical Committee, Natural Gasoline Association of America, Ind. Eng.

Chem., Ind. Ed. 34, No. 10, pp. 1240-1243, 1942.

13. Marchman, H., H. W. Prengle and R. L. Motard, Ind. Eng. Chem., Vol. 41,

No. 11, pp. 2658-2660, 1949.

14. Farrington, P. S. and B. H. Sage, Ind. Eng. Chem., Vol. 41, No. 8,

pp. 1734-1737, 1949.

15. Michels, A., T. Wassenaar, P. Louwerse, R. J. Lunbeck and G. J. Wolkers,

Physica, Vol. 19, pp. 287-297, 1953.

16. Morecroft, D. M. , Journal of the Institute of Petroleum, Vol. 44,

No. 420, pp. 433-434, 1958.

17. Voynov, Yu. F., N. V. Pavlovich and D. L. Timrot, Khimicheskaya

Promyshlennost ' Ukrain;y^ (Chemical Industry of the Ukraine) , No . 3,

pp. 51-54, 1967.

18. Clusius, K. and F. Konnertz, Naturforsch, Vol. 4a, No. 2, pp. 117-124,

1946.

19. Tilicheyev, M. D. , Fiziko-Khimicheskiye Svoystva Individual 'nykh

Uglevodorodov (Physico-Chemical Properties of Individual Hydrocarbons)

,

Moscow, Gostoptekhizdat , 1951.

20. Cramer, F., Chem. Techn., Vol. 7, No. 2, pp. 65-82, 1955.

21. Zagoruchenko , V. A., Candidate dissertation, Odessa, 1959.

22. Canjar, L. N., M. Goldman and H. Marchman, Ind. Eng. Chem., Vol. 43,

No. 5, pp. 1186-1193, 1951.

23. Lehman, H. , Chem. Techn., Vol. 14, No. 3, pp. 132-139, 1962.

24. Van der Waals, J. D., Beibl. Ann. Physik, Vol. 4, p. 704, 1880.

25. Sarrau, E., Compt. rend.. Vol. 94, p. 718, 1882.

26. Cailletet, L., Compt. rend.. Vol. 94, p. 1224, 1882.

27. Dewar, J., Phil. Mag., Vol. 18, p. 210, 1884.

28. Cailletet, L. and E. Mathias, Compt. rend., Vol. 102, p. 1202, 1886.

29. Olszewski, M. K. , Phil. Mag., Vol. 39, p. 188, 1895.

30. Villard, M. P., Ann. Chim. phys . , Vol. 10, p. 387, 1897.

-195-
31. Cardoso, E. and E. Arni , J. Chim. phys., Vol. 10, p. 504, 1912.

32. Maass, 0. and A. L. Geddes , Trans. Roy. Soc. (London), A236, p. 303, 1937.

33. Mcintosh, R. L. and 0. Maass,. Can. J. Research, 16B, p. 289, 1938.

34. Dacey, I. R. , R. L. Mcintosh and 0. Maass, Can. J. Research, Vol. 17B,

pp. 241-250, 1939.

35. Naldrett, S. N. and 0. Maass, Can. J. Research, Vol. 188, p. 118, 1940.

36. Kay, W. B. , Ind. Eng. Chem. , Vol. 40, p. 1459, 1948.

37. Perry, J. H. and P. D. Editor, Chemical Engineers Handbook, N. J.,

Toronto, London, 1950.

38. Kobe, K. A. and R. E. Lynn, Chem. Revs., Vol. 52, p. 117, 1953.

39. Din, F., Thermodynamic Functions of Gases, London, 1956.

40. Stiel, L. I. and G. Thodos , A. I. Ch. E. Journal, Vol. 7, No. 4, p. 611,

1961.

41. Flynn, L. W. and G. Thodos, A. I. Ch. E. Journal, Vol. 8, No. 3, pp.

362-365, 1962.

42. Vargaftik, N. B., Spravochnik po Teplofizicheskim Svoystvam Gazov i

Zhidkostey (Manual on Thermophysical Properties of Gases and Liquids)

Moscow, Fizmatgiz, 1963.

43. Kats, D. L. , et al , Rukovodstvo po Dobyche, Transportu i Pererabotke

Prirodnogo Gaza (Manual on Mining, Transportation and Processing of

'Natural Gas), "Nedra" Publishing House, Moscow, 1965.

44. Nadeydine, A., Russ. Phys. Chem. Soc, Vol. 15, p. 25, 1883.

45. Siebert, F. M. and G. A. Burell, J. Am. Chem. Soc, Vol. 37, No. 12,

pp. 2683-2691, 1915.

46. Winkler, C. A. and 0. Maass, Can. J. Research, Vol. 9, p. 610, 1933.

47. Cailletet, L. and E. Colardeau, Compt. rend.. Vol. 106, p. 1489, 1888.

48. Kazavchinskiy , Ya. Z. and V. I. Kudashev, IFZh [expansion unknown].

No. 4, pp. 31-34, 1962.

Chapter IV

1. Heuse, Ann. der Physik, Vol. 59, p. 86, 1919.

2. Eucken, A. and A. Parts, Z. Phys. Chem., B20, p. 184, 1933.

-196-
3. Burcik, E. I., E. H. Eyster and D. M. Cost, J. Chem. Phys., Vol. 9,

p. 118, 1941.

4. Egan, C. I. and I. D. Kemp, J. Am. Chem. Soc. , Vol. 59, p. 1264, 1937.

5. Kistiakowsky, G. B. and W. W. Rice, J. Chem. Phys., Vol. 8, p. 610,

1940.

6. Kistiakowsky, G. B. , et al , J. Chem. Phys., Vol. 8, p. 970, 1940.

7. Telfair, J. Chem. Phys., Vol. 10, p. 167, 1942.

8. Powell and Giaque, J. Am. Chem. Soc, Vol. 61, p. 2366, 1939.

9. Kassel, L. S. , J. Am. Chem. Soc, Vol. 55, p. 1351 , 1933.

10. Thompson, H. W. , Trans. Faraday Soc, Vol. 37, p. 344, 1941.

11. Crawford, J. Am. Chem. Soc, Vol. 61, p. 2980, 1939.

12. Gurvich, L. V., et al , Termodinamicheskiye Svoystva Individual 'nykh

Veshchestv (Thermodynamic Properties of Individual Compounds) , edited

by V. P. Glushko, Moscow, Fizmatgiz, 1962.

13. Kilpatrick, I. E. and K. S. Pitzer, J. Res. N. B. S., Vol. 37, p. 163,

1946.

14. Stull, D. R. and P. D. Mayfield, Ind. Eng. Chem., Vol. 35, p. 639, 1943.

15. Spenser, H. M. , Ind. Eng. Chem., Vol. 40, p. 2152, 1948.

16. Vukalovich, M. P. et al , Termodinamicheskiye Svoystva Gazov (Thermodynamic Properties of Gases), Moscow, Fizmatgiz, 1953.

17. Keyes, J. Am. Chem. Soc, Vol. 60, p. 1761 , 1938.

18. Mecke, Z. Phys. Chem., B17, p. 1, 1932.

19. Bonner, J. Am. Chem. Soc, Vol. 58, p. 34, 1936.

20. Conn, G. K. T. and G. B. Sutherland, Proc. Roy. Soc, A172, 1939.

21. Callaway, W. S. and E. F. Barker, J. Chem. Phys., Vol. 10, p. 88, 1942.

22. Rossini, F. D., et al , Selected Values of Physical and Thermodynamic

Properties of Hydrocarbons and Related Compounds, Pittsburgh, 1953.

23. Arnett, R. L. and B. L. Crawford, J. Chem. Phys., Vol. 18, p. 118, 1950.

24. Feldman, Romanko and Welsh, Canad. J. Phys., Vol. 34, p. 737, 1956.

-197-
25. Gertsberg, G. , Kolebatel ' nyye i Vrashchatel 'nyye Spektry Mnogoatomnykh

Molekul (Vibration and Rotation Spectra of Multiatomic Molecules)

,

Moscow, Fizmatgiz, 1949.

26. Lehman, H., Chem. Techn., B14, p. 132, 1962.

Chapter V

1. Nevers, N. and J. Martin, A. I. Ch. E. Journal, Vol. 6, No. 1, p. 43,

1960.

2. Pall, D. B. , J. W. Broughton and 0. Maass, Canadian Journal of

Research, Vol. 6, sec. B, p. 230, 1938.

3. Benedict, Webb and Rubin, J. Chem. Phys . , Vol. 8, p. 334, 1940; Vol. 10,

p. 747, 1942.

4. Martin, J. J. and J. Hou, C. A. 1. E. Ch. Journal, Vol. 1, p. 148, 1956.

5. Vargaftik, N. B. , Spravochnik po Teplofi zicheskim Svoystvam Gazov i

Zhidkostey , Moscow, Fizmatgiz, 1963.

6. Lehman, H., Chem. Techn. Vol. 14, No. 3, p. 132, 1962.

7. Din, F., Thermodynamic Functions of Gases, Vol. 2, London, 1958.

8. Canjar, L. N. et al , Hydrocarbon Processes and Petrol. Refiner., Vol. 44,

No. 9, 1955.

9. Canjar, L. N., H. Goldman and M. Marchman, Ind. Eng. Chem., Vol. 43,

No. 5, p. 1186, 1951.

10. Michels, A. et al , Physica, Vol. Xl'x, pp. 287-297, 1953.

11. Michels, A. et al , Physica, Vol. XII, p. 105, 1946.

12. Herget, K. M. , J. Chem. Phys., Vol. 8, pp. 437-542, 1940.

13. Parbrook, H. D. and E. G. Richardson, Proc. Phys. Soc, B65, p. 437,

1953.

14. McHirsi, A. and J. C. Noury, Acad. Sci. Vol. 244, No. 9, pp. 1169-1171,

1957.

15. Dregulyas, E, K. and Yu. A. Soldatenko, Sb . Trudov Novosibirskoy

Konferentsii po Teplofizicheskim Svoystvam Veshchestv (Transactions

of Novosibirsk Conference on Thermophysical Properties of Matter)

(1966), Moscow, Standards Publishing House, 1969.

16. Dregulyas, E. K. and Yu. A. Soldatenko, Teplofizicheskiye Svoystva

Veshchestv i Materialov (Thermophysical Properties of Compounds and

Materials) , No . I, Moscow, Standards Publishing House, 1968.

-198-
17. Telfair, D., J. Chem. Phys . , Vol. 10, p. 167, 1942.

18. Soldatenko, Yu. A. and E. K. Dregulyas, MVSSO [Ministry of Higher

Education and Secondary Special Education] UkrSSR collection

Teplofizicheskiye Svoystva Uglevodorodov i ikh Smesey (Thermophysical

Properties of Hydrocarbons and Their Mixtures), Kiev, Kiev Technological Institute of Light Industry Publishing House, 1967.

19. Namoto, 0., T. Ikeda and T. Kishimoto, J. Phys. Soc. Japan Vol 7

p. 117, 1952. ' '

20. Richards, W. T. and J. A. Reid, J. Chem. Phys., Vol. 2, p. 206, 1934.

21. Holmes, R., G. R. Jones and N. I. Pusat, J. Chem. Phys., Vol. 41,

No. 8, pp. 2518-2516, 1964.

Chapter VI

1. Eucken, A. and F. Hauck, Z. Phys. Chem., Vol. 134, p. 161, 1928.

2. Egan, I. and I. Kemp, J. Am. Chem. Soc, Vol. 59, p. 1264, 1937.

3. Kostryukov, V. N., R. A. Alikhanyants , B. N. Samoylov and P. G.

Strelkov, Fizicheskaya Khimiya (Physical Chemistry), No. 4, p. 650,

1954.

4. Huffman, Parks and Barmore, J. Am. Chem. Soc, Vol. 53, p. 3876, 1931.

5. Powell, W. and Giaque, J. Am. Chem. Soc, Vol. 61, p. 2366, 1939.

6. Auerbach, C, B. Sage and W. Laccey, Ind. Eng. Chem., Vol. 42, p. 110,

1950.

7. Vargaftik, N. B., Spravochnik po Teplofizicheskim Svoystvam Gazov i

Zhidkostey , Moscow, Fizmatgiz, 1963.

8. Timmermans , Physico-Chemical Constants of Pure Organic Compounds,

Vol. 4, 1950.

9. Gurvich, L. V. et al, Termodinamicheskiye Svoystva Individual ' nykh

Veshchestv , Moscow, Fizmatgiz, 1962.

10, Soldatenko, Yu. A. and D. M. Vashchenko, Teplofizicheskiye Svoystva

Veshchestv (Thermophysical Properties of Compounds), Kiev, "Naukova

dumka" Publishing House, 1966.

11. Kirillin, V. A. and A. Ye. Sheyndlin, Issledovaniye Termodinamicheskikh

Svoystv Veshchestv (Investigation of Thermodynamic Properties of

Matter), Moscow, Gosenergoi zdat , 1963.

-199-
12. Popov, M. M. , Kalorimetriya i Termometriya (Calorimetry and Thermometry),

Moscow, Moscow State University Publishing House, 1954.

IS.Karapet'yai^ts, M. Kh. , Khimicheskaya Termodinamika (Chemical Thermodynamics), Moscow, Goskhimizdat , 1953.

Chapter VII

1. Landolt-Bornstein, Phys.-Chem. Tabellen, Vol. I, Berlin, 1923 (Obermayer, A. V., Wien. Ber. , Vol. 71, p. 281, 1875; Breitenbach, Ann.

Phys., Vol. 5, p. 166, 1901; Zimmer, 0., Verh. D. pus. ges . , Vol. 14,

p. 471, 1912.

2. Trautz, M. and A. Narath, Ann. Phys., Vol. 79, p. 637, 1926.

3. Trautz, M. and W. Stauf, Ann. Phys., Vol. 2, p. 737, 1929.

4. Landolt-Bornstein, Phys.-Chem. Tabellen, Vol. I, Berlin, 1931 (T. Titani,

Bull. chem. soc. Japan, Vol. 4, p. 277, 1929.

5. Trautz, M. and A. Melster, Ann. Phys., Vol. 7, p. 409, 1930.

6. Trautz, M. and R. Heberling, Ann. Phys., Vol. 10, p. 155, 1931.

7. Van Cleave, A. B. and 0. Maass, Can. Journ. Res., Vol. 13, sec. B,

p. 140, 1935.

8. Comings, E. W. , B. J. Mayland and R. S. Egly, Univ. 111. Eng. Expt

.

Stand. Bull., Vol. 42, No. 15, 1944; E. W, Comings and R. S. Egly,

Ind. Eng. Chem., Vol. 33, p. 1224, 1941.

9. Graven, P. M. and J. D. Lambert, Proc. Roy. Soc, A205, p. 439, 1951.

10. Senftleben, H., Z. angew. Physik, Vol. 5, p. 33, 1953.

11. Golubev, I. F. and V. A. Petrov, Trudy GIAP (Proceedings of State

Scientific Research and Planning Institute of the Nitrogen Industry

and Products of Organic Synthesis), No. 2, 5, 1953; Golubev, I. F.,

Candidate dissertation, MEI, Moscow, 1946.

12. Lambert, J. D. Proc. Roy. Soc, A231, p. 280, 1955.

13. Golubev, I. F., Vyazkost' Gazov i Gazovykh Smesey (Viscosity of Gases

and Gaseous Mixtures), Moscow, Fizmatgiz, 1959.

14. Misic, D., A. I. Ch. E. Journ., Vol. 7, p. 264, 1961.

15. Neduzhiy, I. A. and Yu. I. Khmara, MVSSO UkrSSR collection Teplofizicheskiye Svoystva Uglevodorodov i Ikh Smesey , Kiev, Kiev Technological Institute of Light Industry Publishing House, 1967, p. 18.

-200-
16. Trautz, M. and I. Husseini, Ann. Phys . , Vol. 20, p. 121, 1934.

17. Trautz, M. , Ann. Phys., Vol. 16, p. 865, 1933.

18. Braune, H., R. Bach and W. Wentzel, Zs . fur phys. chemie, A137, p. 136,

1928.

19. Braune, H. and R. Linke, Zs . fur phys. Chemie, A148, p. 195, 1930.

20. Sutherland, W. , Phil. Mag., 5, 36, p. 507, 1893.

21. Lehman, H. , Chem. Techn. , Vol. 14, No. 3, p. 132, 1962.

22. Girshfel ' der , J., C. Curtiss and R. Berd, Molekulyarnaya Teoriya Gazov

i Zhidkostey (Molecular Theory of Gases and Liquids) , Moscow, IIL,

1961.

23. Gonikberg, M. G. and L. F. Vereshchagin , DAN SSSR (Reports of USSR

Academy of Sciences), Vol. 55, p. 813, 1947.

24. Macwood, G. E., Physica, Vol. 5, p. 374, 1938.

25. Chapman, S. and T. Cauling, Matematicheskaya Teoriya Neodnorodnykh

Gazov (Mathematical Theory of Heterogeneous Gases), Moscow, IIL, 1960.

26. Khmara, Yu. I., Dissertation, MEI , 1969.

27. Zagoruchenko , V. A., Izv. Vuzv. , Neft ' i Gaz , No. 2, 1959.

28. Zagoruchenko, V. A., TVT, No. 2, 1965.

29. Rudenko, N. S., Sow. Phys., Vol. 6, p. 470, 1934.

30. Rudenko, N. S., ZhETF (Journal of Experimental and Theoretical Physics),

Vol. 9, p. 10786, 1939.

31. Gerf, S. F. and G. I. Galkov, ZhTF (Journal of Technical Physics),

Vol. 10, p. 725, 1940.

32. Galkov, G. I. and S. F. Gerf, ZhTF, Vol. 11, p. 801, 1941.

33. Galkov, G. I. and S. F. Gerf, ZhTF, Vol. 11, p. 613, 1941.

34. Neduzhiy, I. A. and Yu. I. Khmara, GSSSD [State Service for Standard

Information Data] collection Teplofizicheskiye Kharakteristiki

Veshchestv (Thermophysical Properties of Matter), No. 1, Moscow,

Standards Publishing House, p. 158, 1968.

35. Mathias, E., C. A. Crommelin and H. G. Wotts, Compt. rend.. Vol. 185,

p. 1240.

-201-
36. Vargaftik, N. B., Spravochnik po Teplofi zicheskim Svoystvam Gazov i

Zhidkostey , Moscow, Fizmatgiz, 1963.

37. Rossini, F., ed.. Selected Values..., API Project 44, Pt., 1953.

1 38. Morecorft, D. W., Journ. Inst. Petrol., Vol. 44, No. 420, 1958.

39. Licht, W. and D. G. Stechert, Journ. Phys. Chem. , Vol. 48, p. 23, 1944.

40. Harrington, P. S. and B. H. Sage, Ind. Eng. Chem., Vol. 41, p. 1734,

1949.

41. Canjar, L., W. Goldman and G. Marchman, Ind. Eng. Chem., Vol. 43,

p. 5, 1951.

Chapter VIII

1. Eucken, A., Phys. Z., Vol. 14, p. 324, 1913.

2. Eucken, A., Forschung, Vol. 11, p. 6, 1940.

3. Senftleben, H. and H. Gladisch, Z. Phys., Vol. 125, p. 653, 1949.

4. Lenoir, J. M. and E. W. Comings, Chem. Eng. Progr. , Vol. 47, p. 223,

1951.

5. Senftleben, H. , Z. angew. Physik, Vol. 5, p. 33, 1953.

6. Keyes, F. G., Trans. ASME, Vol. 76, p. 809, 1954.

7. Lambert, J. D. et al , Proc. Roy. Soc. (London), A231, p. 280, 1955.

8. Chaykin, A. M. and A. M. Markevich, ZhFKh (Journal of Physical Chemistry),

Vol. 32, No. 1, 1958.

9. Cheung, H. et al , A. I. Ch. E. Journal, Vol. 8, p. 221, 1962.

10. Senftleben, H. , Z. angew. Physik, Vol. 17, p. 86, 1964.

11. Neduzhiy, I. A., V. A. Kravets and A. Ya. Colomiyets, MVSSO UkrSSR

collection Teplofizicheskiye Svoystva Uglevodorodov i Ikh Smesey , Kiev Technological Institute of Light Industry, Kiev, 1967.

12. Owens, E. I. and G. Thodos , A. I. Ch. E. Journal, Vol. 6, p. 676, 1960.

13. Tsederberg, N. V., Teploenergetika (Thermal Power), No. 7, 1956.

14. Bromleu, L. A., U. S. Atomic Energy Comm. Techn. Inform. Service,

UCRL -- 1852, 1955.

-202-
15. Perry, J. H. , Chemical Engineer's Handbook, New York, Toronto, London,

1963.

16. Spravochnik Khimika (Chemist's Manual), Vol. I, "Khimiya" Publishing

House, Moscow, 1962.

17 . Szhizhenyye Uglevodorodnyye Gazy. Trudy MINKh iGP im. Gubkina

(Compressed Hydrocarbon Gases. Proceedings of Moscow Institute of

the Petrochemical and Gas Industry im. I. N. Gubkin) , No. 64, Moscow,

"Nedra" Publishing House, 1967.

18. Lehman, H., Chem. Techn., No. 3, p. 139, 1962.

19. Vargaftik, N. B. , Spravochnik po Teplofizicheskim Svoystvam Gazov i

Zhidkostey , Moscow, Fizmatgiz, 1963.

20. Borovik, Ye., A. Matveyev and Ye. Panina, ZhTF , Vol. 10, p. 988, 1940.

21. Borovik, Ye., ZhTF , Vol. 17, p. 328, 1947.

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Thermodynamic and Transport Properties of Ethylene

and Propylene

5. Publication Date

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7. Al'rHOR(S)

I. A. Neduzhii (Principal Author)

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NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

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16. ABSTRACT (A 200-word or less factual summary of most sigriificant information. If document includes a significant

bibliography or literature survey, mention it here.)

A comprehensive review of the data on the thermodynamic and transport

properties of ethylene and propylene is given. Subjects covered include

equation of state for liquid and vapor, second virial coefficient, ethalpy,

etc., heat capacity, speed of sound, viscosity, and thermal conductivity.

New experimental measurements are given for several properties, especially

speed of sound, densities of the liquid and transport properties. Tables

of properties covering the temperature range from 160 K to 500 K are given.

The book has been translated into English from the original Russian.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name; separated by semicolons

)

Critically evaluated data; ethylene; propylene; thermodynamic properties data;

transport properties data

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