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II III lliillili iiliiii III i III ifill^ II
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
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I
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
1971, 182 pages]
Table of Contents Page Preface 1 Symbols Employed in Manual^3
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
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
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
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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
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3
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.
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laboratory of engineering thermophysics^ of^ KTILP^ [Kiyevskiy
Pavlovich.
The use of ethylene and^ propylene in the organic synthesis industry
need for the development of^ detailed tables of the thermodynamic and^ trans- port properties of^ these compounds,^ essential for technological calculations
engineering practice.
An attempt is made in this work to systematize existing experimental
and to create thermodynamical (^) ly concordant tables of these properties in the temperature and pressure ranges that are of interest in technological
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.
on the basis of more reliable data on compressibility.
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I
B(T) --^ second^ Virial^ coefficient^ in expansion^ in terms of density; C , C --^ isobaric^ and^ isochoric^ heat^ capacities; p V^ r^ '
H°-H° --^ change of enthalpy of compound in standard state from 0 to T (^0) ^ o^.
i --^ enthalpy;
the crystalline state at 0°K;
I --^ electric^ current; k --^ Boltzmann constant; -- (^) adiabatics index of real gas in equation;
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;
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1
Z =^ ^ --^ compressibility^ coefficient; A --^ finite change of property, absolute error;
6 --^ relative error; £ --^ depth of potential well;
a --^ effective diameter^ of^ molecular^ interaction; X --^ thermal conductivity coefficient, heat of fusion;
7T = E^ reduced pressure; Pk p --^ density; T
^k T --^ time; cj)(r) --^ potential function of molecular interaction; C K =^ ^ --^ heat capacity ratio; v -- (^) reduced density.
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Table 1. List of^ Works^ Containing^ Data^ on^ the (^) p, v, T-Function of Ethylene
ABTOpU
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 JIhc- ceii (^) [4] Miixe.ibc II Feji- AepMiJiic (^) [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]
1P 132o ly
19J 1942
0- 24,
0— 0— (^1954) !(_7)— ( 4-: 1955 1956 1959
19G 19G 1957
0-
(4 300) (--^.:0)- (-1- 0- 32,2; 48,8; (18,
21—
20- 16— 3—
1— 0,5—20u
0,5—1. 0—2i 1— 2
[li |2] [3]
[li]
|14J
} ni):'C'
i i^ )^ 06pa6oTKa ,aaiiubix
Ke 'ler no y]?aBiieHHio COCTOMKIiq [15] [16] [15]
^ I .orpruiiPCTb ICTOxa (^) HC- CJieAOBSllHOl '> ra3a, (^) %
Av (^) 0,5% Ap T--.^ 0,1 Cap 0.01%
0.5%
0.1 (^)?
0.1%
N,-0,2; (^) Apy- rue raau 0,
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]
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 investi- gated 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%.
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of Propylene
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( Miix-'^.ii.c (^) ii roTpyjiiiiKii (^) [21 (^) | n4)t'HllHr, AiaKKCTTJ (^) (]3| KaHbnp H^ coipyvmnKi; (^) f22J ilHir.iap 11 Cly;ibu
1 o.; cny- b:iii>i II
3; ii'Mii'.p-'ryp /. -(.;
:!
19;
I0i;
0—
30—2o (—10) - (+200) 3— 32,2; 48,.'!;
.'13 ll.^i (^) 'M .1 (^) i u. oaf)
(^1962) 100,110,120, I^ 130.
A\i'To;; ;i-,cne-
-SO
0—
[17] 118] (24) 1—200 (^) ^) Po^iier (^) no ypabiiciiiiio C0CTO;ililIH 6—2830 (^1) 15) 1—2 (^) |23j
GO— (^1000) i^ —
pcLU- liOCTb,
icTora Baiiiioro rasa. (^) %
1 0, 0,
0, 0,
npiiMecefi 0, 99,
KEY: 1. Authors Vaughan and Graves (^) [17] Farrington and Sage (^) [18] Marchman, Prengle,^ Motard^ [19] Michels, et al (^) [21]
Canjar, et al (^) [22] Ditmar and Schultz
Published in (^) [20] are data obtained by calculation according to the
It follows from^ the above review that highly accurate^ experimental data exist for gaseous ethylene and propylene in a rather wide pressure
[6, 11,^ 13]^ for^ ethylene^ can^ also^ be^ recommended^ as^ reference^ material.
Analysis of Thermal Equations of State for Gaseous Ethylene and Propylene
Numerous equations^ of state, derived on the basis of existing
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
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-.^
2^
ICO
1 )^ loon
/\ ^^ 0.035^ •^ /','/ ^ ^^ /, /.'
JOOO
KEY: (^) 1) Mean deviation
r, °K
0
—
51 '\ '1 -1 (^1)
—y— 7 — 7
llllij-irMSiiiMIlIli
1}
Figure 1. Field of errors of (^) thermal equations of state for ethylene and propylene: a --^ field of errors of the Benedict-
c --^ field of^ errors of Zagoruchenko' s equation for ethylene (^) [9];
for propylene (^) [27]; f field of errors of Zagoruchenko' s equation
phase. [Continued on next page].
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r,°K
Figure 1
.
[Continued (^) on next page]
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