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Annotated Quantum Circuit Diagrams for Quantum Algorithms, Study notes of Literature

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II III lliillili iiliiii III iIII 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. 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
75"- 7^3
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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^

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-

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^ trans- port 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-

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-

Table 1. List of^ Works^ Containing^ Data^ on^ the (^) p, v, T-Function of Ethylene

ABTOpU

  1. (^) |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 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-

(-lOOj -

(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, (^) %

AT ^ 0,PC

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]

  1. Year
  2. Temperature range (^) T, °C
  3. Pressure range (^) p, bar
  4. Method
  5. Error
  6. Purity of investigated gas, %
  7. Data processing
  8. Same
  9. Calculation by equation of state
  10. N --^ 0.2; other gases 0.

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%.

-6-

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

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—

\WJ I 4—?

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

— ^ ) OupafxjTKa

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]

Pfennig and McKetta [13]

Canjar, et al (^) [22] Ditmar and Schultz

2. Year published
  1. Temperature range (^) T, °C
  2. Pressure range (^) p, bar
5. Experimental method
  1. Error, %
  2. Purity of investigated gas, %
8. Calculation by equation of state
  1. Data processing
  2. 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-

  1. -.^

2^

ICO

1 )^ loon

/\ ^^ 0.035^ •^ /','/ ^ ^^ /, /.'

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

y///y/y////7///.

'//// -e.^ ^///

JOOO

KEY: (^) 1) Mean deviation

2) Maximum^ deviation

r, °K

0

w

—[ ' 1

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-

Webb-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-