Fluid Phase Equilibria, 1 (1977) 13-26 D Elsevier Scientific Publishing Company,

13 Amsterdam - Printed in The Netherlands

VAPOUR-LIQUID EQUILIBRIUM DATA FOR THE SYSTEMS C,H, + Nz, C&Hz,+ Nz, C3H8 + Nz, and CsHs + N,

LOUIS Instituttet

GRAUSQ,

AAGE

FREDENSLUND Danmarks 1976)

and JBRGEN H&jskole,

MOLLERUP DK-2800 Lyngby (Denmark)

for Kemiteknik, September 27th,

Tekniske

(Received

ABSTRACT Grausi, L., Fredenslund, A. and Mollerup, J., 1977. Vapour-liquid equilibrium data for the systems C,H, + N,, C,H, + N,, C,H, + N,, and C,H, + N,. Fluid Phase Equilibria, 1: 13-26. High pressure vapour-liquid equilibrium data for the C,H, + N,, C,H, + N,, C,H, + N,, and C,H, + N, systems are presented. The data are obtained isothermally in the range from 200 K to 290 K. For each point of data, temperature, pressure and liquid and vapour phase mole fractions are measured. Values for the vapour phase mole fractions are calculated from the obtained pressure, temperature and liquid phase mole fractions. The calculated values are compared with the experimental results, and it is found that the average mean deviation between calculated and experimental mole fractions is less than 0.009 for the systems considered in this work.

INTRODUCTION

All the binary, isothermal Nz + hydrocarbon vapour-liquid equilibrium (VLE) data available in the literature have been subjected to a thermodynamic consistency test involving comparison between calculated and experimental vapour phase mole fractions (yi). For the systems considered, the hydrocarbon is subcritical and pT, is supercritical. Therefore, as explained in Section 3, Henrys constant for N2 dissolved in hydrocarbons is evaluated in the course of calculating yi from the isothermal pressure (P)-temperature (T)-liquid phase mole fraction (xi) data. A summary of these calculations is shown in Fig. 1, which for each binary gives (1) calculated Henrys constants as functions of temperature and (2) average mean deviations between yi(exp) and yi(calc) for each isotherm. The latter are not given for the lower isotherms where yN,(exp) and y,*(calc) are almost one. The numerical procedure used (see Section 3) gives rise to an estimated uncertainty of 2% maximum value in the calculated Henrys constants. We base this estimate on experience in fitting the isothermal P--Xi data to a large number of different polynomials. Since the pressure in the vicinity of pure solvent is relatively low, the thermodynamic properties needed in evaluating

z 600. . 500 z 400. (D z g 300. 0 " zooa

E 800

0.
l

13

n
x.

N,-n-&H,, 69 *": 103

"s" F N,-CSHI "." ".'

; :
loo-"""""""

200

300

400
1'

800
600 t 500 400 v v T 6 46 0 A 0

N,-n-CSH,, ; Id 0

N,-C,",

200

300

Temperature,K

Fig. 1. Henrys

constant

as functions

of temperature

for some nitrogen-alkane

system.

Experimental values: 0 N, +C,H, Stryjek et al. (1974) v N, + C&H, This work This work q N, + C,H, x N,+ C,H, Poon and Lu (1974) A N, + C,H, Schindler et al. (1966) This work q N,+C,H, This work e N,+ C,H, Skripka et al. (1969) s N,+C,H,, Akers et al. (1954) A N, + C,H,, Lehigh et al. (1966) X N, +C,H,, McKetta and Roberts (1961) n N,+C,H,, Kurata and Swift (197 1) v N, + C,H,, Robinson (1973) 0 N,+C,H,, The numbers near some of the experimental points correspond 10,000. iyN2(calc) - y~,(exp) I for the given isotherm. to the average
value of

15

the Henrys constants can be estimated with relatively good accuracy. the scatter shown on Fig. 1 is largely due to experimental errors.

Hence

One may conclude from Fig. 1 that Nz + hydrocarbon VLE are generally not internally consistent and that the data are mutually conflicting. We therefore decided to measure Nz + hydrocarbon VLE data in our laboratory.
2. EXPERIMENTAL RESULTS

The experimental apparatus used in this investigation is described in detail elsewhere (Fredenslund et al., 1973) and (Fredenslund and Mollerup, 1974). A schematic diagram of the apparatus, which is of the vapour recirculation type, is shown in Fig. 2. A diaphragm compressor circulates the vapour through a stationary liquid in the equilibrium cell. Upon equilibration, the temperature, pressure, vapour composition, and liquid composition are observed. Temperature observation and control are within 0.01 K, pressure measurement (with dead-weight gauges) is within 0.02%, and composition reproducibility on the gas chromatograph is within 0.003 mole fraction. The

Cooling L N,

SUPPlY

Fig. :1. Vapour recirculation apparatus.

A B C D E F G H I DPI GSV LSV

diaphragm compressur
precision comparison bridge used for temperature measurement and dead-weight piston gauges gas chromatograph platinum resistance thermometer stop valve for compression vacuum valve ventilation valve pressure gauges differential pressure indicator gas sampling valve liquid sampling valve

control

16

TABLE

1 specifications column length (m) 1 1 1 1 diameter (mm) 3 3 3 3

Pure gas and gas chromatograph G&3 GZIS purity

Gas chromatograph Packing material Porapak Silicagel Porapak Porapak

N, CR, CR, CJI, CJ&

99.998% 99.95% 99.95% 99.95% 99.99%

Q (SO-100 mesh) (60-80 mesh) Q (SO-100 mesh) Q (80-100 mesh)

pressure change each point) was The purity of is given in Table

C2& + N2

upon sampling (three vapour and three liquid samples for less than 0.05%. the gases and a description of the gas chromatograph column 1. The gases received no additional purification.

Vapour-liquid equilibrium of the C2H6 + N2 has been studied by Stryjek et al. (1974), Chang and Lu (1967), and Cheung and Wang (1964):
Reference Chang and Lu (1967) Cheung and Wang (1964) Stryjek et al. (1974) Data Isothermal Isothermal Isothermal VLE data P, T, x, y VLE data P, 2. x VLE data P, T, x, y Range 171.48 K, 122.04 K (no y-values) 92.8 K 138.71 K, 149.82 K, 172.04 K, and 192.04

In this work isothermal VLE data at the temperature and 290.0 K are given.
C2H4 + N2

200.0, 230.0,260.0,

To our knowledge, no VLE data have previously been reported for the C2H4 + N2 system. In this work we show data for the 200.0 and 260.0 K isotherms.
C3H, + N2

For the system C3H6 + N2 Yorizane et al. (1968) (1965) have reported VLE data:

and Blagoi and Orobinskii

17

Reference Blagoi, Orobinskii (1965) Yorizane et al. (1968)

Data Bubble points Isothermal VLE data P, T, x, y

Range Temperature 78 K-91 K 194.65 K, 218.45 K, 295.65

VLE data for the 290.0

K and 260.0

K isotherms are presented here.

This system has been treated by Cheung and Wang (1964), (1967), Schindler et al. (1966), and Poon and Lu (1974):
Reference Cheung and Wang (1964) Poon and Lu (1974) Roof and Baron (1967) Schindler et al. (1966) Data Bubble points Isothermal VLE data P, T, x, y Critical loci Isothermal VLE data P, T, x, y Range

Roof and Baron

91.7 K-128.4 K 114.1 K, 118.3 K, and 122.2 K 312 K-365 K 173.15 K, 198.15 K, 223.15 K, 248.15 K, 273.15 K, 298.15 K, 323.15 K, 333.15 K, 343.15 K. and 353.15

VLE data at 230.0 and 260.0, and 290.0 K are presented in this paper. The data we measured in our laboratory for the systems mentioned above are given in Table 2. All data are raw data and have not been smoothed in any way. Figures 3-6 show the equilibrium ratio Ki = yi/Xi as a function of pressure and temperature for the four binary mixtures.

60 40

10

20

40

60

100

200

400 ATM.

PRESSURE,

Fig. 3. Equilibrium

ratios for the system

C,H,

+ N,. o 200 K,

230 K, A 260 K, A 290 K.

3 = a: m 1 0 5 u

6 4 2 1 0.6 0.4

10

20

40

60

100

200

400 ATM.

PRESSURE,

Fig. 4. Equilibrium

ratios for the system C,H, + N,. o 200 K, a 260 K.

10 o F d 6 4 2

10

20

40

60

100

200

400 ATM.
l

PRESSURE,

Fig. 5. Equilibrium

ratios for the system C,H, + N,.

230 K, fi 260 K, A 290 K.

20 ; : z 3 t? 0 m 3 5 IO6 4

N*

2 ;\ 1 0.6 &He

1:

OoL

, 10

w 20 40 60 100 200 PRESSURE, 400

ATM.

Fig. 6. Equilibrium

ratios for the system C,H, + N,. A 260 K, * 290 K.

19

TABLE2 UnsmoothedisothermalVLE datafornitrogen hydrocarbonsystems + P,atm

System

x~,
N, + C,H,,

yN,
temperature

P, atm 200.0 K
System 29.62

%
N, + C,H,, 0.0

YN,
temperature 0.0

260.0 K

2.153 6.57 10.29 20.89 41.00 60.19 79.43 101.08 123.16 130.22
System

0.0 0.0137 0.0264 0.0647 0.1360 0.2063 0.2764 0.3751 0.5112 0.5738

0.0 0.6389 0.7533 0.8568 0.9029 0.9064 0.8981 0.8716 0.8116 0.7620
temperature

36.32 43.09 51.72 61.31 69.99 75.84

0.0199 0.0413 0.0716 0.1080 0.1498 0.1939

0.1144 0.1949 0.2595 0.3007 0.3139 0.2932

temperature 0.0

System N, + C,H,, 0.953* 0.0

230.0 K

N, + C,H,,

230.0 K

6.913 10.40 15.49 21.28 34.07 53.34 79.66 100.44 118.02 123.13
System

0.0 0.0094 0.0240 0.0399 0.0776 0.1372 0.2265 0.3120 0.4110 0.4543

0.0 0.2927 0.4889 0.6029 0.7129 0.7660 0.7796 0.7566 0.7047 0.6650
temperature

4.03 19.40 36.36 60.37 82.07 106.38 133.14 167.22 192.29 210.76
System

_** 0.0337 0.0745 0.1251 0.1676 0.2070 0.2635 0.3244 0.3774 0.4193
N, + C!,H,,

0.7498 0.9343 0.9556 0.9608 0.9601 0.9545 0.9445 0.9261 0.9071 0.8882
temperature

260.0 K

N, + C,H,,

260.0 K

16.90 25.38 30.74 44.24 55.72 70.13 87.33 99.24

System

0.0 0.0235 0.0393 0.0796 0.1160 0.1647 0.2373 0.3077

N, + C,H,,

0.0 0.2562 0.3478 0.4753 0.5287 0.5576 0.5558 0.5209

temperature 290.0 K

3.062 11.73 21.04 32.33 50.56 75.12 102.17 120.55 150.31 177.48 216.32
System

0.0 0.0183 0.0376 0.0554 0.0903 0.1389 0.1939 0.2354 0.2993 0.3721 0.5280

0.0 0.7116 0.8225 0.8623 0.8909 0.9024 0.8997 0.8939 0.8756 0.8478 0.7524
temperature 290.0 K

34.67 42.12 48.89 54.76 60.50 67.43 69.26

System

0.0 0.0242 0.0464 0.0709 0.0936 0.1322 0.1594

N, + C,H,,

0.0 0.0970 0.1586 0.1940 0.2163 0.2196 0.2115

temperature

N, + C,H,,

200.0 K

4.484 15.21 28.56 39.05 59.54 80.76 101.30 108.94

0.0 0.0307 0.0714 0.1058 0.1811 0.2742 0.3940 0.4735

0.0 0.6504 0.7762 0.8121 0.8294 0.8158 0.7654 0.7133

7.591 19.85 29.08 45.11 55.95 74.80 84.18 92.01 98.79 110.44 122.39 135.34 148.30 156.95

0.0 0.0238 0.0432 0.0746 0.0968 0.1379 0.1603 0.1780 0.1932 0.2216 0.2539 0.2908 0.3310 0.3617

0.0 0.5438 0.6583 0.7423 0.7684 0.7904 0.7948 0.7966 0.7978 0.7938 0.7874 0.7742 0.7580 0.7410

20

P, atm

YN,

P, atm

-*

YN*

System N, + C,H,, 3.779 0.0 16.94 0.0234 36.22 0.0595 55.96 0.0966 85.19 0.1636 117.39 0.2195 147.90 0.2874 170.77 0.3448 188.61 0.3945 0.4882 211.64

temperature 260.0 0.0 0.7382 0.8461 0.8764 0.8869 0.8790 0.8617 0.8393 0.8129 0.7503

System N, + C,H,, 9.247 0.0 17.09 0.0144 22.81 0.0248 0.0413 31.55 0.0604 42.08 0.0855 54.65 0.1148 69.52 0.1473 85.07 0.2028 109.92 131.40 0.2589 148.11 0.3171 163.23 0.3734

temperature 290.0 0.0 0.3843 0.5068 0.6069 0.6734 0.7122 0.7399 0.7500 0.7505 0.7335 0.7104 0.6677

*The vapour pressure is taken from Eubank et al. (1973). **Reproduction of the liquid phase mole fraction was not possible.

3. THE CONSISTENCY

TEST

All the available isothermal N2 + hydrocarbon VLE-data, including those presented in this work, have been subjected to the thermodynamic consistency test given by Christiansen and Fredenslund (1975). The consistency test involves calculating yi from the isothermal P-i data in the following manner: Application of the condition for phase equilibrium and the isothermal, non-isobaric Gibbs-Duhem equation to binary vapour-liquid equilibria results in the relationship
P=Y,P+Y,P=xlfPY1l~,+x,f,OY2/~P2 P = (xl fP/vdexpCg + (x2f,lcpdexp{gg + x2(dgl~l), x,(dgldxd, (x2 VEIRT)(W~lL + (~1 VE/RT)(Wdx~), I + I (1)

is the reduced excess Gibbs free energy, G EfRT. The subscript u denotes along the saturation line. Component 2 is the less volatile component. VE is the excess volume, fzFthe reference fugacity, and @pi the vapour phase fugacity coefficient of component i. The excess is that relative to the components in their standard states. For all systems tested here, N2 is non-condensable. This means that
J

fi=Pytcpytexp

v* dP

fi=H1,2exp

psat 2

p s v,-aP
RT

psat RT I

(2)

(3)

21

VE=V-XJq-x*V2
where Henrys constant, H1, 2 is defined by

(4)

Equations (2) to (5) are tantamount to the so-called unsymmetric normalization of the activity coefficients. The differential equation (1) is solved numerically using Legendre polynomials as test functions for g. g =

GEIRT = (XI/X,, ma2 g

k=o

ak Lk[(xhl,

rt~ax)~]

(6)

where xi max is the largest value of X1 in the data set; it is the highest order polynomial used, usually not higher than six &(X) L,(x) = { (2h = 1 1)(2X L,(x) I)& _ i(X) - (h 1 I)& _ 2(X) }/h

= 2X -

The polynomial coefficients are obtained either by the method of orthogonal collocation (Christiansen and Fredenslund, 1975) or by a least squares fit of eqns. (l)-(6) to the isothermal P--Xi data (Fredenslund, 1975). The order of the polynomials used must be high enough to represent the data within experimental uncertainty. Values for fi (the hydrocarbon reference fugacity), pi, and VE are calculated here using the Prausnitz-Chueh correlation (Prausnitz and Chueh, 1968). In Tables 3 and 4 are shown the pure component physical properties and the binary interaction parameters. The result of the numerical procedure is a set of calculated vapour phase mole fractions and a Henrys constant, which are thermodynamically consistent with the P-Xi data. Comparison between yi(exp) and yi(calc) furnishes a reliable consistency test of the P-i-i data provided the calculated fugacity coefficients are correct. The procedure to calculate the consistency test is as follows: 1. Obtain an analytical expression for the P-X data. This is convenient (a) to allow the calculation of (dP/dx) and (b) because it may be best to solve eqn. (1) at points different from the data points. 2. Calculate VE, fr, and vi as indicated above. Since yi enter into the calculation of pi, an initial estimate of qi must be made, here pi = 1. 3. Solve eqn. (1) for g. This gives the activity coefficients, and values of yi(CalC) follow from yi = fiXj yj/Ppi. 4. Henrys constant is obtained from:

f, = HI,

2 =

x, + 0

lim

(fl/xl) = lim (v~YIP/XI)

x, + 0

(7)

22

TABLE

3 physical properties N, C,H, 283.06 50.50 124.0 0.2696 0.097 0.0876 0.4323 0.429 0.0815 C& 305.42 48.20 146.2 0.2812 0.103 0.088 0.437 0.4347 0.0827 CJ-b 365.1 45.40 181.0 0.274 0.139 0.0889 0.437 0.413 0.0803 CJ-b 369.97 42.01 200.0 0.2767 0.152 0.0889 0.438 0.4138 0.0802

Pure component

T,,B PC, atm

126.26 33.54 90.10 0.29168 0.04 0.087 0.429 0.454 0.0875

V,, crn3/mole
2, w :; G naL fik

TABLE 4 Binary interaction parameters used in the Prausnitz-Chueh method for calculating vapourphase fugacity coefficients

N, + C,H,
N, + C,B, N, + CJL, N, + W-b

0.08 0.05 0.08 0.05

-91.0 -40.5 -81.3 -100.9

32.7 41.0 66.3 68.2

5. Calculate new values of cpiusing yi(calc) from step 3 and, when appropriate, H from step 4. Repeat 2-5 until successive values of yi(calc) agree to w%in 10e6. The end result is a set of values yip yi(calc), and HI, z, which are thermodynamically consistent with the P-xi data. 6. Compare the experimentally obtained values of yi with calculated values. If the following empirical criterion is met (see Christiansen, 1974): lyi(calc) - yi(exp)I < AXi + Ayi (3)

where AXi and Ayi are the experimental uncertainties in the liquid and vapour mole fractions, the data points are said to be thermodynamically consistent. If IYi(CalC) - yi(exp)l > AX~ + A\yi

two possibilities exist: (a) the data point is inconsistent, or (b) the methods of calculating fugacities or molar volumes are erroneous. The results of the consistency tests for the data of this work are summarized in Table 5. The detailed results for Nz + C2H, system at 200 K are shown in Table 6, and similar detailed results for the other systems will be published in

23

TABLE Summary System N, Nz N, N, N, N, N, N, N, N, N, + + + + + + + + + + +

5 of results from the thermodynamic T, K 200 230 260 290 200 260 230 260 290 260 290 ly(exp) 0.008 0.009 0.003 0.005 0.005 0.009 0.006 0.006 0.006 * * Y(cak)
IAVG

consistency Henry s 307.6 377.2 303.6 245.7 311.6 265.9 495.5 446.1 471.7 516.8 532.7

test constant, -_____ atm

C,H, GH, C,H, C,H, C,H, C,H, C,H, C,H, C,H, C,H, C,R,

*Not available. The fugacity coefficients could not be correctly Henry constants is therefore not exact. s TABLE Results 200 K 6 from the thermodynamic consistency

estimated.

The value of

test for the system nitrogen

+ ethylene

at

Experimental P,

values
xN,

Calculated

values

atm

YN,
0.0000 0.6504 0.7762 0.8121 0.8294 0.8158 0.7654 0.7133
=

%H,
0.0000 0.6472 0.7785 0.8132 0.8319 0.8198 0.7724 0.7339 1.0279 0.9813 0.9483 0.9264 0.8924 0.8722 0.8841 0.9148 0.9199 0.7920 0.6620 0.5703 0.4183 0.2931 0.1865 0.1492

4.484 15.21 28.56 39.05 59.54 80.76 101.30 108.94 ly(exp) Henry s -

0.0000 0.0307 0.0714 0.1058 0.1811 0.2742 0.3940 0.4735

Y(C&)IAVG

0.005

constant

311.6

atm

GrausqS(1977). The largest mean deviation between yi(calc) and yi(exp) is 0.009 (see Table 5). The value of 0.009 is somewhat larger than AXi + Ayi = 0.006. We believe, however, that the remainder of the deviation can be attributed to uncertainties in the calculation of fugacity coefficients in the highly critical region.

24

4. CONCLUSION

Vapour-liquid equilibrium data for the Nz + CzH4, N2 + C2H6, N2 + C3Hdr and Nz + C3Hs systems have been measured in the temperature range 200 K to 290 K and the obtained data have been tested for thermodynamic consistency. For the systems N, + CzH4, Nz + CzH6, and Nz + C3Hs all measured isotherms have been found to be consistent. For the Nz + C3H6 system the consistency test could not be performed because of incorrectly estimated fugacity coefficients in the highly critical region. We believe, however, that these isotherms are measured as accurately as those at the lower temperatures.
ACKNOWLEDGMENTS

The authors are grateful to generous financial support from Statens TekniskVidenskabelige Forskningsrgd. The authors also appreciate the assistance of Mr. Bent Johnsen and Mrs. Ellen Pedersen.
SYMBOLS ak USED

f
g

G H K
Lk

P R T V X Y
z
Y

rp
w
K

v
7

aas fib
Subscripts

Legendre coefficients fugacity reduced excess Gibbs free energy GEIRT Gibbs free energy Henrys constant equilibrium ratio Legendre polynomial of degree h pressure gas constant temperature volume liquid-phase mole fraction vapour-phase mole fraction compressibility factor activity coefficient fugacity coefficient acentric factor deviation from geometric mean temperature correlation parameter for mixture critical volume correlation parameter for mixture critical temperature constants in Redlich-Kwong equation of state

1, 2, i, j 0

components along the saturation loop

25

exp
CdC

AVG Superscripts E L G 0 m sat

critical property experimental value calculated value average value

excess property liquid phase property vapour phase property standard state partial molal property infinite solution saturated condition

REFERENCES Akers, W.W., Atwell, L.L. and Robinson, J.A., 1954. Nitrogen-butane system. Ind. Eng. Chem., 46: 2539. Blagoi, Yu.P. and Orobinskii, N.A., 1965, Liquid-vapor phase equilibrium in the propenenitrogen system. Russ. J. Phys. Chem., 39(8): 1073; Transl. of Zh. Fiz. Khim., 39(8): 2022. Chang, S.-D. and Lu, B.C.-Y., 1967. Vapor-liquid equilibria in the nitrogen-methaneethane system. Chem. Eng. Progr. Symp. Ser., 63(81): 18. Cheung, H. and Wang, D.I.-J., 1964. Solubility of volatile gases in hydrocarbon solvents at cryogenic temperatures. Ind. Eng. Chem. Fundam., 3: 355. Christiansen, L.J. and Fredenslund, A., 1975. Thermodynamic consistency using orthogonal collocation or computation of equilibrium vapor compositions at high pressures. AIChE J., 21(l): 49. Christiansen, L.J., 1974. Vapour-liquid equilibria in the normal and critical region. Dissertation. Eubank, P.T. and Das, T.R., 1973. Thermodynamic properties of propane-vapor-liquid coexistence curve. Advances in Cryogenic Eng., 18: 208. Fredenslund, A., Mollerup, J. and Christiansen, L.J., 1973. Vapor-liquid equilibrium of the CH,-Ar, CH,--CO, Ar-CO systems at elevated pressures. Cryogenics, 13: 405. Fredenslund, A. and Mollerup, J., 1974. Measurement and prediction of equilibrium ratios for the C,H,-CO, system. J. Chem. Sot. Faraday I, 70: 1653. Fredenslund, A., 1975. Thermodynamic consistency of high-pressure vapour-liquid equilibrium data. VLE Research Seminar, Jablonna, Poland. Graus$, L., 1977. Dissertation to be published. Kurata, F. and Swift, G.W., 1971. Experimental measurements of VLE-data for the ethanecarbon dioxide and nitrogen-n-pentane binary system. National Gas Processors Assoc., Research Report, RR-5. Lehigh, W.R. and McKetta, J.J., Vapor-liquid equilibrium in the ethane-n-butane-nitrogen system. J. Chem. Eng. Data, 11: 180. McKetta, J.J. and Roberts, L.R., 1961. Vapor-liquid equilibrium in the n-butane-nitrogen system. AIChE J., 7: 173. Poon, D.P.L. and Lu, B.C.-Y., 1974. Phase equilibria for systems containing nitrogen, methane and propane. Adv. in Cryogenic Eng., 19: 292.

26

Prausnitz, J.M. and Chueh, P.L., 1968. Computer Calculations for High-Pressure VaporLiquid Equilibria. Prentice-Hall, New York. Robinson, D.B., 1973. The equilibrium phase properties of the n-pentane-nitrogen system. CNPGA Progress Report. Roof, J.G. and Baron, J.D., 1967. Critical loci of binary mixtures of propane with methane, carbon dioxide and nitrogen, J. Chem. Eng. Data, 12(3): 292. Schindler, D.L., Swift, G.W. and Kurata, F., 1966. More low temperature V-L design data. Hydrocarb. Process., 45: 205. Skripka, V.G., Barsuk, SD., Nikitina, I.E., Gupkina, G.F. and Benyaminovich, O.A., 1969. Liquid-vapor equilibrium in the nitrogen--butane system. Gazov Prom., 14: 41. Stryjek, R., Chappelear, P.S. and Kobayashi, R., 1974. Low-temperature vapor-liquid equilibria of nitrogen-ethane system. J. Chem. Eng. Data, 19 : 340. Yorizane, M., Sadamoto, S., Yoshimura, S. et al., 1967. Low temperature vapor-liquid equilibria. Nitrogen-propylene and carbon monoxide-methane systems. Kagaku Kogaku, 32(3): 257.