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Volume III

FOREWORD

This volume of the Pressurization Systems Design Guide has been

prepared under Contract NAS7-548 "Liquid Propellant Gas Absorption Study. "

The work was administered under the direction of the Jet Propulsion Zabo-

ratory_ Mr. Howard B. Stanford of JPL served as Technical Manager and Mr.

Frank E. Compitello of NASA Washington, Liquid Propulsion Systems, was

Project Manager.

This volume is an expansion of Section VI-D, Volume II-B of the report

originally prepared by Aerojet General under Contract NAS7-169 (September

1964, 'Revised December 1965 and July 1966).

The technical effort at Astropower Laboratory, McDonnell Douglas

Corporation was directed by Dr. W. David English, Chief, Propellant

Compatibility Section. Experimental studies that developed new data for

the report were carried out by Mr. W. A. Cannon and Dr. J. H. Robson.

Program supervision was carried out by Dr. D. R. Mash, succeeding


Dr N. A. Tiner.
v

In preparing this volume, extensive use has been made of the data

available in the literature, handbooks and textbooks. Acknowledgments

and credit are given throughout the volume for the use of this material.

The technical details of the experimental work carried out on this con-

tract are reported separately in a Final Summary Technical Report, "The

Solubility of Gases in Liquid Propellants," Report Number DAC-60510-FZ,

July 1968.

This report was prepared by J. H. Robson, W. A. Cannon and W. D.

English.

Report DAC-60510-FI Page iii


Volume III

ABS TRAC T

This volume of the Pressurization Systems Design Guide is a com-

pendium of information on the solubility of pressurant gases in liquid propel-

lants. Two main sections are presented: first, a theoretical discussion of

the nature of gas-liquid, two-component systems; second, a compilation of

available numerical data about the equilibrium solubility of pressurant gases

in liquid propellants. Data on rates of solution and evolution of the gases


are not available.

ACKNOWLEDGMENT

This volume is based on the report originally prepared by Aerojet-

General Corporation under the direction of William J. Flaherty. Much of

the theoretical presentation and discussion in this report was originally pre-

sented in the Aerojet-General report. The compilation of experimental data,

too, bears heavily on the compilation and style of presentation developed by

Aerojet-General. We gladly acknowledge their pioneering presentation.

However, this acknowledgment does not remove responsibility from

our own shoulders, and Astropower Laboratory, McDonnell Douglas Corpo-

ration, is solely responsible for misstatements, errors, and omissions in


the current volume.

Page iv Report DAC-60510-FI


Volume III

PRESSURIZATION SYSTEMS DESIGN GUIDE

VOLUME III

PRESSURANT GAS SOLUBILITY


IN LIQUID PROPELLANTS

CONTENTS

Page

I° INTRODUCTION I-l

II. THEORY OF GAS SOLUBILITY II- l

A. Literature Available If- l

B. Ideal Solutions II- l

C. Gas Solubility in Nonideal Solutions II- 2

D. Prediction of Solubilities II-4

1 Basic Concepts II-4


V

X Criteria for Equilibrium II- 5

3 Pure Liquid Phase in Equilibrium With Vapor II-7

4 The Virial Equation Of State II- 8

5 Solubility In The Liquid Phase If- 9

6 Comparison Of Theory With Experimental Data II- 10

7 Obtaining Virial Coefficients And P-V-T Data II- 13

E. Gas Solution and Evolution- Nonequilibriurn Systems II- 14

l ° Introduction II- 14

2. Rate of Solution If- 14

3. Experimental Studies II- 18

4. Rate of Evolution II-22

5. Certain System Effects Under Nonequilibrium


Conditions II- 23

Report DAC-60510-FI Page v


Volume III

CONTENTS (cont.)

Page

III. MEASUREMENT OF GAS SOLUBILITY III- 1

A. Methods of Solubility Measurement III- 1

B. Graphical Representation of Pressure, Temperature,


and Composition Relations III-1

Co Illustrative Phase Equilibria Data for the System


Normal Hydrogen-Helium III-8

D, Studies at McDonnell Douglas III-12

IV. PRESSURANT SOLUBILITIES IN PROPELLANTS IV- 1

A. Introduction IV- 1

B. Pressurant Gases IV- 2

C. Solubility Data for Pressurant Gases in Propellant


Oxidi z e r s IV- 5

, Chlorine Pentafluoride-Helium IV- 5

2. Chlorine Pentafluoride- Nitr ogen IV- 5

3. Chlorine Trifluoride-Helium IV- 9

4. Chlorine Trifluoride- Nitrogen IV- 9

5. Dioxygen Difluoride-Helium IV- 14

6. 70% F LOX-Helium IV- 20

7. Fluorine-Helium IV- 20

8. MON- 10- Helium IV- 23

9. Nitrogen Tetroxide-Argon IV- 23

10. Nitrogen Tetroxide-Helium IV- 23

Ii. Nitrogen Tetroxide-Oxygen IV- 27

iZ. Nitrogen Tetroxide- Nitrogen IV- 27

Page vi Report DAC-60510-FI


Volume III

CONTENTS (cont.)

13 Nitrogen Trifluoride-Helium IV- 27

14 Nitrogen Trifluoride- Nitrogen IV - 27

15 Nitryl Fluoride-Helium IV-35

16 Nitryl Fluoride-Nitrogen IV-35

17 Oxyg en-Helium IV - 36

18 Oxygen- Nitr og en IV -45

19 Oxygen Difluoride-Heliurn IV -45

20 Oxygen Difluoride-Nitrogen IV -45

21 Perchloryl Fluoride-Helium IV- 56

22. Perchloryl Fluoride-Nitrogen IV - 56

23 T etr afluor ohydr azine -Helium IV-6 l

24 T etr afluorhydr azine- Nitrogen IV-6 l

DQ Solubility Data for Pressurant Gases in Propellant Fuels IV - 66

I. Aerozine 50- Ammonia IV - 66

2 Aerozine 50-Helium IV - 66

3 Aerozine 50-Nitrogen IV - 66

4 Ammonia- Helium IV-66

5 Ammonia- Nitr og en IV - 66

6 Diborane-Helium IV- 75

7 Dibor ane- Nitr og en IV-75

8 Dibor ane- Hydr og en IV- 8O

9 Ethane -Helium IV - 8O

l0 Ethane- Nitr og en IV - 80

Report DAC-60510-FI Page vii


Volume III

CONTENTS (cont.)

ii. Ethane-Hydrogen IV - 83

12. Ethylene- Helium IV- 83

13. Ethylene - Nitr ogen IV- 83

14. Ethylene-Hydr ogen IV - 96

15. Sydrazine-Argon IV - 96

16. Hydrazine -Helium IV- 96

17. Hydra zin e- Nitr ogen IV- 96

18. Hydrogen (Norrnal)-Heliurn IV- 105

19. Hydr ogen (Equilib r ium) -Helium IV- 105

20. Methane-Helium IV- if4

21. Methane -Hydrogen IV- If4

22. Methane-Nitrogen IV- 114

23. M onornethylhydr azine- Ar gon IV- i 14

24. M onomethylhyd r azin e- Heliurn IV- 123

25. Monomethylhydr azine- Nitrogen IV- 123

26. Monornethylhydr azine Hydrate-Helium IV- 123

27. Pentaborane-Helium IV- 123

28. Pentabor ane- Hydr ogen IV- 132

29. Pentaborane- Nitrogen IV- 13Z

30. Propane - Helium IV- 132

31. Propane- Nitrogen IV- 132

32. Propane- Hydr ogen IV- 137

33. T rirn ethylb or ane- Helium IV- 146

Page viii Report DAC-60510-F I


Volume III

CONTENTS (cont.)

Page

IV- 146
34. T rimethylbor ane- Nitr og en

35. Unsymmetrical Dimethylhydrazine


IV-151
(UDMH)-Argon

36. Unsymmetrical Dimethylhydr aline


(UDMH) -Helium IV-151

37. Unsymmetrical Dimethylhydrazine


IV-151
(UDMH)- Nitrogen

REFERENCES V-i
Vo

Table Page

II- 1 II- 19
Rate of Solution of N 2 In N20 4

IV- l IV - 2
Properties of Selected Pressurant Gases

IV - 2 IV - 4
Physical Properties of Propellant Oxidizers

IV - 3 Solubility of Helium and Nitrogen in Liquid Chlorine


Pentafluoride IV- 5

IV - 4 Solubility of Helium and Nitrogen in Liquid Chlorine


Trifluoride IV - 9

IV - 5 IV- 14
Solubility of Helium in Liquid Dioxygen Difluoride

IV-6 IV - 20
Solubility of Ilelium in Liquid 70-F LOX

IV - 7 IV- Z3
Solubility of Helium in Liquid Fluorine

IV- 8 IV- 28
Solubilities of He, N 2, 0 2 , and Ar in Liquid NzO 4

IV - 9 Solubility of Helium and Nitrogen in Liquid Nitrogen


Tetroxide IV - 29

IV- 10 Solubility of Helium and Nitrogen in Liquid Nitrogen


Trifluoride IV- z9

IV-35
IV-I I Solubility of Helium and Nitrogen in Liquid Nitryl Fluoride

Report DAC-60510-F I Page ix


Volume III

CONTENTS (cont.)

Table

IV- 12 Solubility of Helium in Liquid Oxygen IV- 36

IV- 13 Solubility of Helium and Nitrogen in Liquid Oxygen


Difluoride IV-51

IV- 14 Solubility of Helium and Nitrogen in Liquid Perchloryl


Fluoride IV - 56

IV- 15 Solubility of Helium and Nitrogen in Liquid


Tetrafluor ohydrazine IV-61

IV- 16 Physical Properties of Propellant Fuels IV- 67

IV- 17 Solubility of Ammonia, Helium and Nitrogen in


Aerozine 50 IV- 68

IV-18 Solubility of Helium and Nitrogen in Liquid Ammonia IV- 68

IV- 19 Solubility of Helium and Nitrogen in Liquid Diborane IV- 75

IV- Z0 Solubility of Helium and Nitrogen in Liquid Ethane IV- 80

IV-21 Liquid-Vapor Equilibriurn Constants for the System


Ethane- Hydr og en IV- 88

IV- 22 Solubility of Helium and Nitrogen in Liquid Ethylene IV- 88

IV- 23 Liquid-Vapor Equilibrium Constants for the System


Ethylene - Hydrogen IV -98

IV -24 Solubilities of Argon, Helium and Nitrogen in Liquid


Hydrazine IV- 98

IV -25 Solubility of Helium in Normal Hydrogen IV- 106

IV -Z6 Experimental Liquid-Vapor Equilibrium Data for the


System Helium-Methane IV-II5

IV- 27 Solubilities of Argon, Helium and Nitrogen in Liquid


M onom e thylhydr azine IV- 124

IV- 28 Solubility of Helium and Nitrogen in Liquid Propane IV- 137

IV -29 Liquid-Vapor Equilibrium Constants for the System


Propane- Hydr og en IV- 142

Page x Report DAC-60510-FI


Volurne Ill

CONTENTS (cont.)

Table Page

IV - 30 Solubility of Helium and Nitrogen in Liquid


Trimethylbor ane IV-146

IV-31 Solubilities of Argon, Helium and Nitrogen in Liquid


Unsymmetrical Dimethylhydrazine IV-151

IV-32 Solubility of Helium and Nitrogen in UDMH IV-152

Report DAC-60510-FI Page xi


Volume III

SYMBOLS

Subs c r ipts

c critical property

f interface between two films

g gas phase

i,j,k c o mp on e nt

L liquid phase

m indicates property for a mixture

s saturated condition for property indicated

int. initial

Super scripts

property in a mixture, such as f. = fugacity of i in a mixture


1
0
o indicates pure component, such as Pi

yap, liq indicates component as vapor, liquid

Latin

A gas -liquid

B second virial coefficient


W
b U_
VL
C third virial coefficient

c mass concentration of gas dissolved in liquid phase

gas specific heat


Cp
D fourth virial coefficient

E enhancement factor, Py/Ps, also energy of vaporization in


Hildebrand solubility parameter equation

F film thickness

f fugacity

G initial rate of solution

H Henry's constant in equation Pi = Hxi

K y/x = equilibrium constant

L liquid

Page xii Report DAC-60510-FI


V olurn e III

M average mass velocity


n
empirical constant (in Equation Z7)
P pressure, total (= gas concentration)

P partial pressure, of component designated

R ideal gas law constant

r system radius

S solid

T temperature, absolute scale

U coefficient of escape of gas from liquid


V volume

V bubble radius

W weight of solute

X mole fraction in liquid phase

Y mole fraction in vapor phase

Z compressibility factor

Greek

7 liquid phase activity coefficient


6 Hildebrand solubility parameter, see Equation 22

q_ vapor phase fugacity coefficient

x diffusion coefficient

@ time

77 viscosity

_7 3. 1416

0 gas density

Report DAC-60510-F1 Page xiii


Volume Ill

I. INTRODUCTION TO VOLUME III

The purpose of this volume is to present some considerations of gas

solubility in liquid propellants as a guide to the designer of propellant handling

systems. A discussion of the behavior of two-phase, two-component systems

as they have been correlated theoretically and empirically is presented. This

supplies some guide lines for use of the data, and supplies background for

predicting solubilities under new conditions or in systems for which measure-

ments are unavailable.

The solubility data presentations are primarily in the form of isothermal

and isobaric graphs. Solubility figures on the ordinates are in terms of both

mole percent concentration of dissolved gas and STP volume of dissolved gas

per unit weight of liquid solution. This latter relation is of interest in con-

sidering problems of gas evolution downstream of the propellant tank.

The gas solubility data presented in this volume are for equilibrium

conditions. It is recognized that rate data would be very valuable to designers,

since most processes on a rocket vehicle occur under nonequilibrium condi-

tions. However, accurate rate data have not been reported for liquid propel-

lants. Solution and evolution rates for gases are very system-dependent;

they are effected by factors such as surface/volume ratio, speed of mixing,

suspended solid particles in the liquid, etc.

In practice, the use of nitrogen to pressurize liquid oxygen presents a

special case of the problem of rate of gas solution. It is possible to pres-

surize liquid oxygen tanks with nitrogen for very short times, perhaps i0

minutes, without exceeding the oxygen dilution limits (References i-4), and

this procedure is commonly followed. However, phase equilibria data

(Reference I) show that at 20 psia and -297°F liquid phase temperature the

nitrogen could comprise 32 weight percent (35 mole percent), the equilibrium

composition of this system. It is evident that one condition that permits the

pressurization of oxygen propellant tanks for limited short times (e.g. , as

can be acceptably employed in some static test stand work) is the use of

relatively warm nitrogen gas. The nitrogen gas delivered from a storage

Report DAC-60510-F1 Page I-1


Volume III

pressure bottle system usually is above -lO0°F, even with the cooling of

expansion, due to system heating effects. The nitrogen gas will rapidly cool

to its condensation temperature and go into solution in the liquid oxygen when

left pressurized for moderate-to-long periods. The rate of solution can be

minimized if desired, and is a function of the characteristics of the pressuri-

zation system (e. g. , the extent of circulation and mixing of the gas in the

ullage volume, the surface area, temperature and mass of the tank walls,

etc.). Conversely, pressurization of liquid oxygen propellant tanks with

gaseous nitrogen for long periods is generally unacceptable, because of con-

densation and solution of the nitrogen.

Pressurization design techniques are treated quantitatively in Section

III of Volume I, so that conclusions based on calculation can be made, for

example, on when acceptable performance can be expected with a given

pressurant or pressurizing system. Volume III is primarily concerned with

the equilibrium concentrations of various pressurants in propellants rather

than the rates of solution. Information on equilibrium solubility will show

the maximum solubility to be expected, and will also provide some of the

essential data needed for estimating pressure rise or fall in propellant tanks

over extended periods of operation. (Methods of estimating the pressure

rise or fall in propellant tanks are presented in Section III of Volume I,

methods for comparing pressurization systems are presented in Section II

of Volume I. )

Generalizations can be made about the solubility of gases in liquids.

One approximation found to be true over some temperature ranges is that,

for highly soluble gases, the solubility tends to decrease with rise in system

temperature, the reverse of the general trend for solubility of solids. How-

ever, even this generalization on gas solubility is found not to be applicable

for gases with low solubility or for many of the systems at the temperatures

and pressures of interest to the pressurization designer. For instance,

most helium systems and many other propellant-pressurant systems exhibit

reverse-order solubility. Further comments on gas solubilities, trends and

the phenomena that significantly determine solubility are presented in the

next sections.

Page I-2 Report DAC-60510-FI


Volun e III

II. FHEORY OF GAS SOLUBILITY

A. LITERATURE AVAILABLE

There are several treatises and reviews dealing with various

aspects of the subject of gas solubility. A very valuable article is that by

Battino and Clever, "The Solubility of Gases in Liquids" in Chemical

Reviews (Reference 5). Hildebrand and Scott wrote an excellent book dealing

with many facets of solubility (Reference 6). Glasstone's well known "Text

Book of Physical Chemistry" also has useful discussions (Reference 7).

B. IDEAL SOLUTIONS

The gas solubility [n ideal solutions can be estimated, but first

an ideal solution must be defined. Consideration of ideal solutions is worth-

while to establish approximate relations, also, very dilute solutions approach

the behavior of ideal solutions. An ideal solution is defined as one in which

the heat of mixing of the pure components is zero and there is no change in

total volume (Reference 6).

For such solutions, the relationship known as Raoult's Law (i.e.,


o
the vapor pressure Pi of component i equals the vapor pressure Pi of that
pure component times its liquid mole fraction x.) holds.
1

o
Pi = Pi x.I

Since vapor pressure increases as temperature increases, for an ideal

solution gas solubility decreases as the temperature increases.

Another relationship known as Henry's Law is then followed: that

is, the solubility of a gas is proportional to its gaseous phase partial pressure,

At any one temperature a gas with a higher critical temperature

and boiling point is more soluble than one with a lower critical temperature,
O .
since p is smaller for the former. (This approximation also is found to be

generally followed for solutions not following Raoult's Law.)

Report DAC-60510-FI Page II-I


Volume III

When these relationships are not followed for any reasons, the

liquid solution or the gas phase, or both, do not behave ideally. Departures

from ideality are due to a number of reasons, including the nature of the
molecules of the two components; their relative size, shape and intermolecular

forces; and tendencies for chemical compound formation. It is evident then

that the nature and magnitude of the atomic and molecular bonds play a sig-

nificant role in solubility values. Qualitatively, the equilibrium solubility can

be looked at as a balance between those forces encouraging solution and those

opposing it.

C. GAS SOLUBILITY IN NONIDEAL SOLUTIONS

The generalizations that may be made on the solubility of gases


in solutions with nonideal behavior can be related to departures from Raoult's

Law. In Figure II-1, the vapor pressure is plotted as afunction of the mol
fraction; the ideal situation is curve B, where Raoult's Law holds; deviations

are either positive as in curve A, or negative as in curve C. The solubility

of a gas exhibiting a positive deviation from Raoult's Law is seen to be less

at a given partial vapor pressure, here assumed to be 1 atm, for a saturated


solution of component, y. Conversely for a negative deviation from Raoult's

Law, curve C, the solubility is greater than if the system behaved ideally.

Much effort has resulted in establishing methods for predicting

solubilities from thermodynamic reasoning using expressions that consider

the forces believed to influence solubility, see References 6, 8 and 9. Polar-

ity, formation of hydrogen bonds, any ionic tendencies of the components or

tendency for chemical compound formation can be taken into account pro-

viding enough basic data are available. Correlations of solubilities have been

made mostly of gases in solvents at or near normal atmospheric conditions


on earth. The trends have been as predicted by theory, see for example

Table 4, page 243 of Reference 6 showing the solubility of ten nonpolar gases

in 15 different liquids at atmospheric pressure and temperature. Helium is


noted to be least soluble in each case. These results are mainly of theoretical

interest here because none of the liquids are propellants. The accuracy of

prediction, using the methods described by Hildebrand and Scott, approaches

Page II-2 Report DAC-60510-FI


Volunoe III

Py

A
1 arm.

I
I
I I
I I I
I l

x =0 x =i
Y Y

Concentration

cYfSi

Figure II-l. Deviations from Raoult's Law


(Reference 6)

Report DAC-60510-FI Page II-3


Volume III

10% of the measured values, particularly when data are known for several

analagous systems (Reference 6). Application of these predictions to some

representative cryogenic liquids are described in the next section. It should

be noted that available solubility data and theory predicts the tendency for

CO z and NO 2 to have high solubilities in some solvents due to specific chem-

ical interactions (e. g. , compounds containing carbonyl groups, etc. ). It is

considered worthwhile to estimate solubilities by theoretical techniques when

no experimental data can be obtained, e.g. , by using the Hildebrand solubility

parameter, 6, described in Reference 6. Corrections for nonideality in the

gas phase can also be made but accuracies of solubility predictions thus

obtainable seldom approach the desired goal of 10% of the measured values,

for reasons to be made more evident in the next section.

D. PREDICTION OF SOLUBILITIES

1. Basic Concepts

Vapor-liquid equilibrium data can be predicted with a degree

of accuracy for purposes of engineering calculations by the use of virial

equations of state for the vapor-phase fugacity coefficient (References 8 and

9) and Hildebrand's equations for liquid-phase activity coefficients (Reference

6). Such calculations are illustrated for the hydrogen-carbon monoxide-

propane system in Reference 10. The conditions were such that the virial

equation, truncated after the second virial coefficient, sufficed to describe

the vapor phase nonidealities, and the liquid phase was essentially pure.

Reference 8 illustrates the use of the foregoing relations in the calculation

of equilibrium concentration of oxygen in hydrogen at 100 psig and -370°F.

The two-parameter Redlich-Kwong equation has been found

to represent P-V-T data in the gas phase with good precision, even at high

gas densities. The application of the Redlich-Kwong equation of state to

correlations of methane-nitrogen and helium-hydrogen systems is shown in

Reference 11. (Comparisons of calculated and measured solubilities for the

hydrogen-helium system are discussed in References 12 and 13, the measured

data are presented in Section III-C following.)

Page II-4 Report DAC-60510-FI


Volume III

Raoult's Law states that the partial pressure Pi of component

i in the gas phase is directly proportional to the concentration of component i

in the liquid phase, and that the proportionality factor is the vapor pressure

= Pi o x..1 At low pressures,


of the pure component i at the temperature: Pi

where the gas phase is approximately ideal, the partial pressure of component

i, Pi' is equal to the mole fraction of i in the gas phase, Yi' times the total

pressure P. Thus

yi P = xiPi° (I)

or

Yi Pi
(2)
x. P
1

The equilibrium ratio Yi/x'l is frequently identified and used


as the constant K. (Note: Kmore properly should be referred to as a ratio

because it is single valued only at each single value of pressure and

temperature, thus having a range of values.)

When the liquid and gas phases cannot be considered as ideal,

this most simple expression must be modified. Henry's Law is one modifica-

tion.

Raoult's Law Pi = Pi °x'1 (3)

Henry's Law Pi = H x.1 (4}

In effect, Henry's "constant" is an adjusted vapor pressure for component i at

a given temperature.

2. Criteria for Equilibrium

It is a criterion for equilibrium between phases that at a given

temperature and pressure the fugacity or escaping tendency of a constituent will

be the same in each phase. The expression of equilibrium between a liquid and

a gas phase

Report DAC-60510-FI Page II-5


Volume III

Yi p = xiPi ° (5)

may be made more precise through use of fugacities. The fugacities of

component i in the two phases are equal.

f.vap = f.liq (6)


1 1

the fugacity of i in the vapor phase may be expressed as a product of the

fugacity coefficient, the concentration, and the total pressure.

f yap
i = q_i Yi p (7)

The fugacity coefficient of a given component, _0i, is a function of temperature,


pressure, and the concentrations of each of the components in the vapor phase,

that is to say, it is essentially a function of the interactions between the given

component and all of the components of the system. For the liquid phase, the

fugacity may be expressed as a product of the liquid phase activity coefficient,

the concentration, and the fugacity of the pure liquid at the same temperature

and at the total pressure of the mixture.

f liq oliq
i = 7i x'f'l 1 (8)

Since the fugacity of i in the two phases is the same at equilibrium,

_Pi Yi p = 7i x.1 f'l°liq (9)

or

Yi _i f" oliq
K - - _ (I0)
X.
I _Pip

which is the equilibrium ratio discussed above (also called K constant or

K-factor).

':"Fugacity is a special function which simplified the treatment of cases in which


the ideal-gas and ideal-solution laws do not apply. (For extremely dilute
solutions the fugacity of a component very nearly equals its pressure. )

Page II-6 Report DAC-60510-FI


Volume III

Equilibrium "constants" can thus be computed from such

expressions if the activity coefficient of i, the fugacity of pure component i

at the temperature and pressure of interest, and the fugacity coefficient of

component i in the vapor phase can be evaluated.

3. Pure Liquid Phase In Equilibrium With Vapor

The computation of the concentration of component i in the

vapor phase may be made through use of Equation l0 for the simplified case

when the liquid phase is essentially pure. In this case, x. %" 1.0 and T _ 1.0.
1
And

f.oliq
1

Yi- _i p (11)

In this expression, with Yi being the sought after concentra-

tion of i in the vapor phase and P the total system pressure it is now necessary

to evaluate foliql and _0i.

The value f oliq is the fugacity of the pure liquid component i


1

at the temperature of interest and at the total pressure of the system. This

pressure of the pure component, increases the fugacity of component i. The

increase of fugacity with pressure may be determined from

1 _ 1
(3 lnf.)
8P V.
RT (12)
T

if V.,
1 the molal volume in the liquid state, is known as a function of pressure

P P

RT In i . dP (13)
f. 2 / 2
pioliq VI
f'1 Pi °liq

and if V.1 is relatively noncompressible, its average molal volume between


oliq
Pi and P2 and at temperature T may be used to obtain

Report DAC-60510-FI Page II-7


Volume III

P
f. 2
RT In I oliq = Vi (Pz - Pioliq) (14)
Pi
f.
1
P
2
All is known except fi , which can now be cahulated.

The fugacity coefficient, _0, in Equation 11 is defined as the

ratio of that component's fugacity in the mixture to its partial pressure

f.oliq
1
In (#i = In (15)
Yi p

(16)
RTi / (V.i - Rp T) dP
O

Calculation of the fugacity coefficient from this equation requires a volume-

explicit equation of state.

4. The Virial Equation Of State

Thevirialequation of state, a power series in volume (or in

pressure or in density), may be used for evaluation of the fugacity coefficient

(Equation 17).

B C D
Z _ PV _ 1 +_ + m + m + ;:. _:_ (17)
m RT V 2 _

B, C, and D, the second, third, and fourth virial coefficients,

are functions of temperature. The equation of state for a mixture requires the

use of virial coefficients for the mixed gases. The second virial coefficient of

a mixture,Bin,is a quadratic function of the mole fraction

n n

m : /_ Yi Yj Bij (18)
i ]

and the third virial coefficient of a mixture C is a cubic function


m

Page II-8 Report DAC-60510-FI


Volume III

It can be shown that using the fundamental equation relating

fugacity to P-V-T properties, use of the virial equation of state to describe

these properties through use of the preceding mixing coefficients, and limiting

the expression to the second and third virial coefficients, that

n n n
(20)
in cpi V :_ ij' 2 yiy k Cij k In Z m
m j 2 V m j k

The restriction of using only the second and third virial coef-

ficients limits the expression to use in the pressure range up to about the

critical density. When terminated after the secondvirial coefficient, the

expression is reliable to about half the critical density.

5. Solubility In The Liquid Phase

It has been pointed out that the fugacity of a component in the

liquid phase may be written as the product of its activity coefficient, its con-

centration, and its fugacity in the pure liquid state at the same temperature

and total pressure in Equation 8.

f liq
i = _i x.1 f. oliq
I

The liquid-phase activity coefficient, Vi may be calculated

from Hildebrand's equation for regular solutions (Reference 6)

In 7i - VRTliq ( 6i - _n _ i 6.I ) 2
/ lt
i

The solubility parameter 6i is defined by

_- (zz)
6i AE i
v.liq /j 1/z
I J

Report DAC-60510-FI Page II-9


Volume III

where A E. is the energy of vaporization to the gas at zero pressure (i.e.,


1

infinite separation of the molecules) and V. liq is the liquid molal volume of
1

component i.

Using Equations 21 and 14, expression 8 may be evaluated and

equated to the fugacity of i in the gas phase or to the fugacity of the pure solid

or pure liquid.

It should be noted that the logarithm of the activity coefficient

varies with the square of the difference between the solubility parameters of

the component and of the solution, and that for moderate differences in solu-

bility parameters, the activity coefficients are sensitive to slight variations

in thermal data.

6. Comparison Of Theory With Experimental Data

Comparison of experimental data with theoretical calculations

shows that although solubilities can be predicted by analytical techniques, it

is best to measure solubilities when accuracies within 10_0 are desired.

Calculated and experimental vapor-liquid equilibrium ratios

for a ternary system, hydrogen-carbon monoxide-propane, at 340°F and 475

psia (Reference i0) are shown in Figure II-2.

Figures II-3 and II-4 show comparisons of calculated and

measured py/x equilibria values for hydrogen and helium. The correlations

for vapor-liquid equilibrium were obtained by means of a modified Redlich-

Kwong equation of state (Reference II).

It is interesting to note that the unusual decreases of py/x

of helium with increasing temperature is correctly predicted by the correla-

tion. Most materials show an increase of py/x with increasing temperature.

This representation of the special behavior of helium lends considerable

confidence to this correlation method.

A comparison of methods of predicting equilibrium gas phase

compositions in pressurized binary systems containing an essentially pure

condensed phase is given in Reference 9. Four methods were used to calculate

Page II-lO Report DAC-60510-FI


Volume I1, _

2.0--

1
lo0--
O 0
O
ol
O
>_× 0.8-
I
"
0
0.6- I
X_ 0.4-
I
o
4_ Experimental O
1
;Z Calculated -- I
0.2- I
1
.,-4

0.1_
L
0 4 8 2

cvU_
Mole Percent CO In Vapor

Figure II-2. Vapor- Liquid Equilibrium


Ratios in t{2-CO-C3H8
(Reference 10)

Report DAC-60510-F1 Page II-11


Volume III

i0

20.4°K
50

Hydrogen 17.4°K
PY/x
psia

I0 J
/
0 200 400 600 800 I000 1200 1400

Pr e s s ur e. p sia .r..j

Figure II-3. Comparison of Calculated and


Measured py/x of Hydrogen (Ref. 1 i)

lxl0 5

/_ 1 7.4°K
5xl 04 -
f

Helium
py/x
psia
21.8°K

lxlO 4 _

5x10 3 --

0 Z00 4_)0 6 0 8OO I0 0 1200 14 0

Pressure. psia

Figure II-4. Comparison of Calculated and Measured


py/x of Helium (Reference 11).

Page ll-lZ Report DAC-60510-FI


Volume Ill

phase equilibrium for methane-hydrogen. Comparison with experimental data


shows that the enhancement factor can be predicted within 25%. No single
equation agrees closely with the experimental data over the entire pressure
range considered (675 to 3000 psia, 25 to 200 atrn).

7. Obtaining Virial Coefficients And P-V-T Data

Attention is called to various experimental methods that have

been used for direct measurement of phase equilibria and also to methods for

the related virial coefficient and P-V-T measurements.

The virial coefficient equation of state is such a powerful

theoretical tool in phase equilibria work that much attention is given to the

improvement of virial coefficient data. The virial coefficients are functions

of temperature and of composition of mixtures. The coefficients for the pure

components and appropriate combining rules are required for treatment of the

binary ormulticomponent mixture. Prausnitz and Gunn (Reference 14) discuss

the virial equation and make an analysis of secondvirial coefficient data for

many systems. Prausnitz and Meyers (Reference 15) apply the Kihara para-

meters to the calculation of second virial coefficients for 16 cryogenic fluids.

Beenakker and Varekamp (Reference 16) describe an apparatus for the dif-

ferential determination of the second virial coefficient working with hydrogen

and its isotopes and experimentally measuring the difference between hydrogen

and helium. Thomaes and Van Steenwinkel (Reference 17) describe a very

accurate apparatus for measuring small differences in the second virial coef-

ficient of gases at low temperatures. The principle of the experimental method

consists of measuring the difference in volume expansions of two gases sub-

jected simultaneously to the same change in pressure.

Kurata and Kohn (Reference 18) describe a glass cell apparatus

that can be used at pressures up to 3000 psi for P-V-T measurements. Known

increments of gas are injected into the cell and the pressure rise noted.

White et al (Reference 19) measured the compressibility of

gaseous helium over a wide temperature and pressure range, and from the

resulting 22 experimental isotherms developed a virial equation of state.

Report DAC-60510-F1 Page II-13


Volume Ill

Mueller et al (Reference 20) obtained second virial coefficients from about

600 experimental points for the volumetric behavior of methane and methane-

hydrogen mixtures as obtained in a Burnett-type apparatus. Byrne and Thedos

(Reference 21) have used the critical compressibility factor for the correlation

of P-V-T behavior of several diatomic gases. Nelson and Obert (Reference

22) present a comprehensive bibliography of P-V-T data for 30 gases and

generalized compressibility charts.

E. GAS SOLUTION AND EVOLUTION-


NONEQUILIBRIUM SYSTEMS

1. Introduction

In normal practice, most of the functioning of pressurized

liquid propellant systems is at nonequilibrium conditions. Two main depart-

ures from equilibrium occur:

The fluid is unsaturated relative to the pressurant


conditions (solution still occurring).

The fluid is supersaturated relative to the pressurant


conditions (evolution may be occurring).

In real systems, these conditions may occur at the same time; in the fluid

tank saturation may not have been reached, but fluid is being withdrawn and

downstream of the tank, where the pressurant is not present in the gas phase,

the fluid is supersaturated and gas evolution can occur.

When systems are not at equilibrium and so are undergoing

changes, the most important way to characterize the condition is the rate of

change as a function of the operating variables.

2. Rate of Solution

A number of papers have been published on the rate of solution

of gases in liquids; however, no adequate reviews of the reports seem to exist.

The most important reference is a series of papers presented at an "Absorption

Symposium" of the American Chemical Society in 1924, and published in

Industrial and Engineering Chemistry that year (Reference 23). At that meeting,

Page 11-14 Report DAC-60510-FI


Volume III

a paper by Lewis and Whitman (Reference 24) presented a theoretical treatment


which has come to be called the "Two Film Theory." Almost all the papers
at the symposium and subsequent research have been found to confirm this
theory, and extend the definition of the parameters that enter it. However, it
may be mentioned that most of the reported studies do not relate to conditions
similar to those in propellant pressurization; instead the studies relate to
falling liquid films, bubbling gas mixtures through the liquid, and other dynamic
systems. This is not to say that the Two Film Theory is not applicable, but
only that most of the parameters that have been defined closely are not those
which are important in tank pressurization•
The Two Film Theory can be summarized in the following
fashion:

At a gas-liquid interface, on both the gas and liquid sides,


there are surface layers of gas and liquid that are effectively stationary,
since each is relatively free from mixing by convection or mechanical pro-
cesses. Generally, it can be assumed that the concentrations in the bulk gas
and liquid phases are essentially uniform, but this is not necessarily true in
the liquid phase if the bulk of the liquid is stagnant (Reference Z5), a condition
which tends to be true in propellant pressurization. Since the surface films
are quiescent, all mass transfer through the two films must occur by diffusion.
The diffusion rates in each film are functions of the concentration gradient
across them and the film thicknesses• An equation for the rate across the two
films is
dW
A d O -- × g (P g - Pf) = _ L (cf - CL) (23)

In systems where the gas is very soluble, Pf is negligible


relative to P Then
g
dW = × p (24)
Ad@ g g

and the liquid film is unimportant.

Report DAC-60510-FI Page II-15


Volume III

If the gas is relatively insoluble, P = Pf, and


g
dW
A d 8 = ×L (cf c L) (25)

and since cf is obviously the concentration in a film saturated at pressure P


g'
it is c
g

dW
A d @ - _tL(cg - c L) (26)

and the gas film can be neglected.

For intermediate solubility, the full equation must be

considered.

The physical existence of the stationary film was discussed by

Davis and Crandall (Reference 26), who measured it on quiet water at room

temperature, and found it 0.04 cm thick. When the water was stirred at 1000

rpm but the film was not broken, the thickness dropped to 0. 004 cm. Bubbles

rising through water have a film thickness of 0. 002 cm; presumably this is

the minimum that can be obtained.

Davis and Crandall explain the mechanism as follows: "When

a pure gas, oxygen for example, is suddenly admitted at atmospheric pressure

into contact with pure water from which all gases have been removed, the very

surface layer, perhaps monomolecular in thickness, instantaneously becomes

very nearly saturated with oxygen. This must be true, because an oxygen

pressure is at once exerted from the surface equal to the partial pressure

against it, which is the condition necessary for a saturated solution.

"The oxygen now begins to diffuse into the film at a tremen-

dous rate, for although the solubility of oxygen in water is small, 0. 0012 M,

the gradient from the surface is very steep. We wish to stress this point

because of its bearing on the rapid rates at which some olefinic gases are

absorbed by sulfuric acid, although they are quite insoluble therein.

"As diffusion proceeds the magnitude of this gradient quickly

grows less and the absorption slows down, soon reaching a constant value

Page II-16 Report DAC-60510-FI


Volume III

(initial absorption rate). At this stage the gradient is uniform and the same

quantity of oxygen is passed from the surface through each unit cross section

of the film into the main body of the liquid which is still practically free from

dis solved oxygen. "

Hanks and McAdams (Reference 27) studied the gas film by

using very soluble gases. They showed that the film thickness determined in

heat transfer studies was the same as that for mass transfer (gas diffusion),

and that an equation for deriving film thickness is

= (27)
F 2br(_g 2rMg In

The above discussions implicitly assume infinite reservoirs

of gas and liquid, and saturation of the liquid is not considered. This is

because most of the work relates to chemical process plants in which absorp-

tion of a continuously supplied gas to a continuously renewed liquid is of prime

interest.

In typical pressurization systems, the liquid cannot be regarded

as an infinite reservoir, and so the rate of absorption of gas at any time must

be affected by the concentration already present. Adeny and Becker (Reference

28) did consider this condition, and derived the equation

dW W
= G P - U- (281
AdO V L

This can be simplified to the form

W@ Wint -b0)
W - (100 - _ ) (1 - e (29)
S S

This equation predicts a logarithmic curve. Studies by Becker

(Reference 25) with a large number of gases dissolving in water substantiated

the equation. However another effect showed up which is not accounted for.

The initial rates for some gases fell off along alogarithmic curve, but the

asymptotic portion was well below the saturation concentration. It appears

Report DAC-60510-FI Page II-17


Volume III

that these gases form saturated upper layers and affect the viscosity and

density of these layers to reduce diffusion rates. The layers in effect become

thick liquid films. Gases that behaved in this fashion in water solution included

carbon dioxide, hydrogen, and hydrogen sulfide. Nitrous oxide, nitric oxide

and chlorine did not form such harrier films on water.

3. Experimental Studies

Only a few studies of the rate of solution of pressurant gases

in rocket propellants have been reported.

a. Nitrogen Tetroxide -- Nitrogen

In some undisclosed experiments carried out by M. M.

Calvert (Reference 29), the rate of pressure drop in a calibrated closed

system of nitrogen over undisturbed N204 was measured. From the pressure
decay, the amount of nitrogen dissolved in the propellant was calculated. The

experiments gave data of suprising consistency. A summary of the results of

four of the experiments is presented in Table H-1 and Figure 11-5. In another

experiment with only i/3 the volume of N204 in the same container, the
absorption levelled off at about 55g0 of saturation, and a brief shaking after

three hours caused completed saturation.

h. Ethane -- Helium

A brief study of the rate of solution of helium in ethane

at -50°F was conducted (Reference 30). Samples of the liquid phase were

withdrawn periodically for analysis after helium was admitted to the system.

The helium pressure was maintained constant. The eductor probe to withdraw

the specimens was located 5 cm below the surface of the liquid ethane, at the

bottom of the liquid phase.

The data are presented in graphic form in Figure 11-6.

They were fitted to Equation Z9, and b was calculated to he 0. 485. The value

for @ = 0 was also calculated from the equation. It was 0.99 hours after the

experiment started. This probably corresponds to the time necessary for the

first molecules of helium to reach the eductor probe opening.

Page II- 18 Report DAC-60510-FI


Volume III

TABLE II- 1

RATE OF SOLUTION OF N2 IN N204


(Initial N2 Pressure, 290 psig. System Volume, 512 ml)

Test Conditions, Nitrogen Pressure (psig)

Time 327 ml N204 320 ml NzO 4 330 ml N204 309 ml N204


(Minute s) 71 oF 74°F 78°F 96 °F

0 0 0 0 0

1 214 236 186 179

2 227 242 236 193

3 240 249 236 207

4 248

5 240 249 248

8 207

l0 248

13 221

17 240

18 Z35

35 Z48

44 240

58 26Z

66 262

70 248

82 276

I19 253

205 332":'"

Agitated slightly.

Report DAC-60510-FI Page II-19


Volume III

350 -

After
C
Agitation

300 -

- -25

71°F
250 -

v - -20
'13

> 200 -
0
o
tfl
.r-I

4.a
- -15
0
150- O
O
4_

(I/
u

0
--I0 n_

i00-

- 5
50-

0 -- 0

0 20 40 60 80 100 IZ0

Time (Minutes) a'Vf_

F igur e II-5. Rate of Solution of Nitrogen in Nitrogen-Tetroxide

Page II-20 Report DAC-60510-FI


Volume III

--- 1.00

8O

6O
/ ----0. 80

q9

o -- --0. 60
_9

t
09
J - --0. 40
_h I
I
I
I 0 Experimental
/ Values

I - --0.20

I
I
/
Value)

--0
0

o 1 2 3 4 5 6 7
m_8|$

Time - Hours

Figure II-6. Rate of Solution of Helium in Liquid Ethane at


-50°F and 720 Psi

Report DAC-60510-FI Page II-21


Volume III

c. Monomethylhydrazine -- Helium

The Marquardt Corporation has experienced difficulty in

tests at certain of its facilities, and these were traced to problems in insuring

complete saturation of propellant with helium in the run tanks. The problems

were much greater with MMH. A complex procedure was developed to insure

complete saturation, but the approach was specific to the particular facilities

involved (Reference 31). Since the tank geometries and conditions at the

facility are not detailed in the reference, general solubility rates cannot be

calculated.

4. Rate of Evolution

The equations presented for solution of gases should be

equally valid for evolution, since the concentration gradients can be in either

direction. Under conditions of vigorous stirring and mixing of gas and liquid

phases this assumption was shown to be true by Lewis and Whitman (Reference

24), using the data of Perman (Reference 32), and also of Whitman and Davis

(Reference 33).

Again, these studies were in infinite systems, and do not

relate directly to a propellant pressurization system. The rate of gas evolu-

tion from a relatively quiescent fluid depends on a number of other factors.

Gases frequently evolve from supersaturated liquids by form-

ing bubbles within the bulk of the fluid and at the container walls, in a manner

reminiscent of a liquid boiling. Thus nucleation phenomena must be considered.

However, no analyses or experiments relating nucleation to gas evolution have

been found. Epstein and Plesset (Reference 34) have analyzed the behavior

of bubbles once they are formed, relating growth, shrinkage, and translation

of bubbles to various system parameters. In this article, the volume growth

rate of bubbles immersed in a supersaturated solution is shown to be

d O
( Cint - Cs
1(
'÷ v (_.×0)
' 1/2
) (30)

Page II-ZZ Report DAC-60510-FI


Volume III

5. Certain System Effects Under Nonequilibrium


Condition s

Many of the problems in liquid propellant systems that arise

from dissolved gases have not been carefully studied, and some have only been

cursorily identified. But information is available on analagous situations that

arise in hydraulic systems. Such systems are frequently designed to have very

long service lives, and many types of interactions that can cause service

problems have been identified and evaluated.

An article by V. G. Magorien (Reference 35) includes both

a review of known factors and new experimental data. Among the information

presented by Magorien is the fact that 0. 17 Vol % entrained gas (air) reduces

the bulk modulus of a liquid by 50% (Figure II-7). A completely dissolved gas

has no effect on the bulk modulus. Another important observation is that the

presence of dissolved gases accelerates erosion and cavitation corrosion.

And dissolved air is released as bubbles which do not redissolve when the

liquid lineal velocity through a constriction is greater than 100 feet a second.

The drastic reduction in bulk modulus is one possible explanation for pressure

fluctuations and chugging in blowdown N204 -- UDMH ACS engines in several


rocket vehicles.

Report DAC-60510-FI Page II-Z3


Volume III

C_
LJ "

_ °r,l
o_

,_ _

(",,I
-_ _ _

o _ "_
t
--r¢_ t13

_0
u_
0 u_
0 o"
0
0

0
0 e_
0

-5---- I

0 0 0
u

C
0 0 0
0 0 0

o" o" o"


0 u_ 0

isd - snlnpoIA I gln_ _._q_.P'V

Page II-Z4 Report DAC-60510-FI


Volume III

III. MEASUREMENT OF GAS SOLUBILITY

A. METHODS OF SOLUBILITY MEASUREMENT

Phase equilibria measurements generally involve the intimate

and continued mixing of two phases until constancy of composition is attained

in each phase, followed by the separation or sampling of the phases, and

sample analysis. Liquid vapor equilibria at low temperatures have been

measured by many workers: the Dodge and Dunbar study (Reference l) of

the oxygen-nitrogen system; Maimone's work (Reference 36) with hydrogen-

nitrogen and deuterium-nitrogen; Akers' study (Reference 37) of the hydrogen-

nitrogen-carbon monoxide system; the study of the helium-hydrogen system

by Sonntag, Val Wylen, et al, (References 12 and 13); the Aerojet-General

studies by Flaherty et al on helium and nitrogen in N204, Aerozine 50 and

monomethylhydrazine (References 38 and 39), and the Stein etal (Reference I0)

phase equilibria apparatus are representative of the experimental procedures

which have been used to obtain liquid-vapor phase equilibria (L-V) data.

(Also see Reference 5. )

B. GRAPHICAL REPRESENTATION OF PRESSURE,


TEM PERATURE ,AND COM POSITION RE LATI ONS

For binary systems the phase rule shows that the equilibrium

liquid and vapor phase compositions are invariant at fixed pressure and

temperature. The data may be represented graphically by two surfaces

on a three -dimensional pressure-temperature-composition diagram, each

surface representing a single phase. The two surfaces merge along a

critical curve, consisting of points at which the two phases become indis-

tinguishable. It is customary to describe the equilibrium surfaces

graphically by showing their projections on one or more of the three P-T-x

coordinate planes. Presentations of experimental data include plots of

isotherms on a P-x diagram and isobars in the T-x plane. P-T diagrams

are obtained by cross-plotting data from P-x and T-x diagrams. Equilibrium

constants, the ratios of vapor-phase to liquid-phase mole fractions, may

be shown as a function of pressure for various isotherms.

Report DAC-60510-FI Page III-i


Volume III

The critical point of a pure substance has the following

char acte ri stic s:

1. The liquid and vapor phases are identical

2. The temperature is the maximum at which the


two phases can co-exist

3. The pressure is the maximum at which the two


phases can co-exist.

In the case of binary solutions these three phenomena no longer

appear at one point but are exhibited at three separate points. This can best

be shown on a pressure-temperature diagram such as Figure III-i. This

represents a section cut through a pressure-temperature-composition sur-

face by a plane of constant composition. It consists of two boundary curves,

- one for liquid and one for vapor of the same composition - enclosing the

field in which two phases can co-exist, and which meet at the critical point

C, where the two phases become identical. This point is the point of

tangency of the boundary curve and an envelope curve AB that joins the

critical points of the two pure components. Point C' is the maximum

temperature at which a vapor of this particular composition can be condensed

to a liquid, or the maximum temperature at which the two phases can co-exist

in a system of this particular total composition. This point is commonly

known as the "cricondentherm" (critical condensation temperature) (Refer-

ence 40) Point M represents the maximum pressure at which a system of

the given composition can exist in two phases. Also, DMC is the locus of

the bubble points, s,_ The curve DMC is most easily visualized as the vapor

pressure curve of the particular mixture. Similarly, EC'C is the locus of

the dew points :''_""


at a series of pressures. It is interesting to note that,

whereas the vapor pressure of a pure substance always increases with

temperature, in the case of a binary solution it may rise to a maximum and

then actually decrease as the temperature is increased in the vicinity of the

critical point. This phenomenon accounts in part for some of the deviation

of solutions from ideal solubility trends. Other causes for deviation are

discussed in the previous section on prediction of solubilities.

::-"
"Bubble point" - point of initial boiling

_=:x"Dew point" - point of initial condensation

Page III-2 Report DAC-60510-FI


Volume III

A
\ I
\
\ I

Liquid

'"\ B

D_vlpor
E

Temperature
,_¢,$.1"I

Figure III- I. Binary Pressure-Temperature at Constant Composition


(Reference 40).

Temperature _

Figure III-2. Binary Pressure-Temperature Curves at Constant


Composition (Reference 40).

Report DAC-60510-FI Page III-3


Volume III

Figure III-i is for a single composition. To represent com-


position as a variable one could use a system of three coordinates and obtain
a solid figure containing a P-x surface. In order to represent, at least
partly, all three variables on a plane surface, we can adopt the usual
expedient of taking a number of sections through this surface at constant
composition and projecting the resulting curves all onto one plane as illus-
trated by Figure III-2. Typical systems exhibiting the behavior illustrated
in this figure are CO2-SOZ and ethane-heptane (Reference 41). Curves l
and 7 are the vapor-pressure curves of the two pure components, and the
others are the typical curves for a mixture with a vapor and a liquid branch.
The points where the vapor branch of one curve intersect the liquid branch
of another represent coexisting phases in equilibrium (point A, for example).
It is clear that this must be so from the fact that a liquid and vapor phase
at the same pressure and temperature must be in equilibrium. Curve
CAC B is the envelope curve joining the critical points of the two pure com-
ponents, and it is the locus of the critical points of the mixtures. It is
designated the "critical curve". The form of this curve shown in Figure III-2
is one of the commonest, but not the only one that has been observed. Cases
have been investigated in which the critical curve exhibits a maximum and
also a minimum with respect to the temperature.

Figures III-3 through III-5 show the P-x, T-x andyz curves
respectively, for the type of system depicted on the P-T diagram in
Figure III-Z. In Figure III-3, in cross section I, the temperature is below
the critical of either pure component; in II and III, it is above the critical
temperature of the more volatile component but below that of the other
component. Mixtures richer in component Athan Xl(Cross section II) or
x 2 (cross section III) can no longer form two phases. In Figure III-4,

cross section I, the critical pressure is below that of either component;

in II it is above that of the less volatile one; in Ill, above the critical

pressures of both components. Corresponding curves on the yx diagram

at constant pressure are shown in Figure III-5.

Page III-4 Report DAC-60510-FI


Volume III

0 _

.r-I

.,-4

o_ =
0
< 0 'Z
G_
0
0
"0

_ "_ C)

=o
0

o_
_uu <D

4 ,A
__ I/ ._ I !
=
.e-4
I

o.In_._ adu.,o I oanssaa d


o
o °v-I

o_
<
0
o o (9 "_
o
_ -_._
0

_ _0 _
"= ,_mo

_ao
_ o

8 _o

, 0 _ _
A
< X 'uo_sodtuo D _
o o4
o I
H

,e.4

i:m

Report DAC-60510-FI Page III-5


Volume III

A very interesting phenomenon takes place when a mixture

whose composition lies between that of the critical point and of the cri-

condentherm point is isothermally compressed. In Figure III-6, which is

an enlargement of the critical region in Figure III-1, line AB represents

an isothermal compression at constant total composition, starting with a

vapor at A. At D the dew-point line is reached; and as compression is

continued, the amount of liquid at first increases, then passes through a

maximum and decreases, and finally disappears altogether as the dew-

point line is reached again at E. Further compression will produce no

separation into two phases. This phenomenon is known as "retrograde

condensation '_ and was first reported by J. P. Kuenen in 1892 (Reference 1

and 42).

The change in the relative amount of the two phases is more

easily visualized on the P-x diagram (Figure III-7) because any vertical

line through the two-phase region cuts the horizontal tie lines into segments

whose lengths are proportional to the amounts of the phases. Thus, for

example, HG/FH equals the ratio of the mass of liquid to the mass of vapor.

At D, this ratio is zero and again at E. Between these two points it

obviously passes through a maximum.

At any composition to the left of that of the critical point C, the

condensation phenomena are of the ordinary type, i.e. , the liquid phase

first formed at the dew point continues to increase until the whole system is

liquid at the bubble point. This may be seen by considering the path LN.

When the relative position of the points C and C' is as indicated

in Figure III-8, we have the peculiar situation that the line of isothermal

compression ADEB now reaches the liquid line at D and the phase which

separates would ordinarily be regarded as a vapor phase.* As compression

*In the critical region there is no clear-cut distinction between a liquid and
a vapor phase because the physical properties such as density and viscosity
are very nearly equal for each phase, and in the homogeneous region above
the critical point there is no difference at all. In the critical region it
might be better to refer to the two phases as the "less dense" and the
"more dense" phase.

Page III-6 Report DAC-60510-FI


Volume III

0
0r,4
4-)

b 0

o 0
0

o-- t_ •

0 o

0 _o

!
I--I

o_nssa_ d
°rt

.o_

,-_ _ .,_
0 _

o _
o 0
_: n_ _ "'_
o _ _._
•_ _ 0
0-___ m O_ _

oI_ _0,-_ 0

0
0
g
!

o_nssDl d

Report DAC-60510-FI Page III-7


Volume III

proceeds, this would increase in amount, pass through a maximum, and

then decrease to zero at E when the liquid line is again crossed. This

phenomenon was predicted by Kuenen and called by him "retrograde con-

densation of the second kind. " (This phenomenon is illustrated in the next

section for the system helium-hydrogen which illustrates retrograde con-

densation of the first kind and also the second kind. ) Similar phenomena

would be predicted for an isobaric process by using either the P-T or the
I-x diagrams except that in this case the composition would be one lying

between those of points C and M {Figure III-1) and the type of retrograde

condensation would depend on the relative position of these two points.

Use of these methods of representation are shown next for a typical pres-

surant and propellant.

C. ILLUSTRATIVE PHASE EQUILIBRIA DATA FOR THE


SYSTEM NORMAL HYDROGEN-HELIUM

Typical data plots are shown for the system normal hydrogen-

helium, taken from Reference 12 to illustrate the above described graphical

means of representation. The behavior of this system is seen to be typical

of binary systems in which the critical temperatures of the components are


relatively far apart. Similar behavior is exhibited, for example, by the

systems nitrogen-hydrogen and nitrogen-helium. The closed loops in

Figure III-9 represent temperatures for which the critical point occurs at

a pressure below 500psia. These loops showa region of retrograde con-

densation of the first kind, which is that portion of the loop lying to the right
of a vertical line through the critical point. The region in which the liquid

lines cross {Figure III-9 and III-10) is one of retrograde condensation of

the second kind. On the T-x diagrams, this appears as a region in which

individual liquid lines (isobars) have both a positive and a negative slope,

Figures III-11 and III-12. This region is seen to be restricted to helium

concentrations of 4 mole %or less, and to pressures below about 230 psia.

Over most of the range covered in this study, the data exhibit reverse order

solubility, which is defined as an increase in solubility of a constituent with

increasing temperature at constant pressure.

Page 111-8 Report DAC-60510-FI


Volume III

mm_ Critical Curve

Critical Point
%%%
% Liq. Yap.

500 - # 34.0

a
_"
I/l/
400
,,_._
o

N
Z7.2

-Ill/,
'_ _oo J o%

/
ZO.4

100
/
/ )
13,6

6.80

i
___.-
J _.//
0 10 20 30 40 50 60 70 80 90 ] 00

Mole % Helium _,_

Figure III-9. Isothermal Pressure--Composition Diagram for


the System Normal Hydrogen-Helium

c¢ He (5TPt IGrl, m Soln,

Ill lZO _Z6

I00

s. qo

f
_n

i
Mole _ He _n l.,qul,'l

Figure III- i 0. Isothermal Pressure-Composition Diagram for


the System Normal Hydrogen-Helium, showing
Liquid Region on Expanded Scale

Report DAC-60510-FI Page 111-9


Volume III

0
O

0
0"

.i-4

0
s_

0
0
I

t
U

! • ,-i I-i
0
!
_Z
0
0

o f
0
i
0

oO

Page III- I0 Report DAC-60510-FI


Volume III

cc He (STP) / Gram Soln.

220 430 634 830 1020

_4 I

32 \ m

3O
\ f

28
\ / f
J

/ J
I / J
26
_A/J / ,/
Q
24

22
,//'/
/i/z /

I/I/
16
g
1

0 1 2 3 4 5 6 7 8 q 10 11 12 13 14

Mole % Helium in Liquid _¢_

Figure III- 12. Isobaric nile:He Temperature-Composition


Diagram Sh_wing Liquid Region on Expanded
Scale

Report DAC-60510-FI Page lll-I i


Volume III

The critical curve locus indicated in Figures III-9, III-II and

III-!3 has been estimated from a study of the trend of the data on P-x,

T-x, and P-T plots. The loops at 31.00 and 31. 50°K were almost com-

pletely closed with experimental data points, which served to define the

shape of loops at nearby temperatures. The critical curve obtained from

this diagram was cross plotted on T-x and P-T diagrams and found to be

consistent with the data as it appears on those diagrams. On the P-T plot,

this critical curve or envelope is tangent to each of the curves of constant

composition, with the point of tangency representing the junction of the dew-

and bubble-point curves for that composition.

The equilibrium "constants, " K, the ratio s of the vapor-phase

to the liquid-phase tool fractions, are shown in Figure Ill-14.

The very accurate partial molal properties for each component

and other thermodynamic data, determined to the accuracy needed, were

not available to precisely calculate theoretical phase equilibria data for this

system. Further discussion on this point and a comparison of these

experimental data with other test data available in the literature are in

the reference from which this work is taken, Reference 12.

D. STUDIES AT McDONNELL DOUGLAS

In studies conducted at Astropower Laboratory, McDonnell

Douglas Corporation, a specially developed stainless steel apparatus was

used for saturation and sample selection. Gas chromatographic procedures

were used for analysis. The details of the procedures are reported in

Reference 46 and the numerical data are included in Section IV of this

report.

The apparatus used for determination of equilibrium gas

solubilities has gradually evolved after considerable investigation. The

basic operations involve condensing the propellant under investigation into

the evacuated bomb which is positioned inside a cryostat. The bomb and

its contents are brought to the desired temperature and then pressurized

to the desired level with the pressurant gas. The contents of the bomb

Page III-12 Report DAC-60510-FI


Volume IIl

50 I I I
_._ D_ Paint Curve (GII)

Bubble Point Curva (Liquid)

___ Cr_tte,i Curv* J k_

k
300
250
/
200

20 27 28 29 30 31 32 33 34 35

Temperature OK t _16•

Figure III-13. Pressure-Temperature Diagram for


Normal H2-He

1000.0

x ,ooo __-

o / oo ° _ Heh_

J_
Hydrolen

ZO ¢0 o
O_

_ 1707 o
%
is so o

0.01

0 100200 300 400 _00

Pressure, psia

Figure III-14. Equilibrium K-Values for


Normal H2-He

Report DAC-60510-FI Page Ill-13


Volume III

are agitated by shaking the bomb mechanically. As the pressurant gas goes

into solution, the pressure in the vapor phase decreases and it may be

necessary to repressurize periodically to the desired level.

The pressure vessel containing the solution is constructed of

stainless steel, nominally of l-liter capacity. A Vari-drive motor, operating

through a reducing gear at 4-6 rps, imparts a reciprocating motion of about

one-inch amplitude to the bomb by way of the support rod which screws into

the nut welded to the bomb lid. The bomb lid is equipped with three welded-

in flared-tube AN nipples. One accommodates a thermocouple which is

placed in a well extending into the liquid phase near the bottom of the bomb.

A second thermocouple located outside the bomb senses the Dewar bath

temperature and controls LN 2 or warm GN 2 addition. The cryostat is

insulated with glass wool at the top and covered with polyethylene sheet to

preserve a nitrogen blanket and keep out atmospheric moisture. The bomb

temperature stabilizes at about ± 0.5°F because of its large thermal inertia.

After attainment of equilibrium, a liquid sample is drawn out

through an eductor tube that extends into the liquid phase to the bottom of

the bomb. The liquid phase sample is withdrawn by opening the bleed valve

in the line, whereby the sample is forced out through the bleed valve,

flashed into a vapor and collected in an evacuated cylinder. The eductor

tube is designed to reduce the liquid volume in the line to a minimum;

nevertheless a preliminary purging of the line is necessary to clear the

eductor tube of any liquid phase not saturated with pressurant gas.

Once the representative gas sample has been collected in the

sample cylinder, it is analyzed to determine the concentration of pres-

surant gas. The operator is obliged to resample the liquid phase after

an appropriate additional time of equilibration to assure attainment of

true equilibrium.

Nitrogen is used as a carrier gas when samples are being

analyzed for helium, and helium is a carrier when nitrogen is being

analyzed. Instrument calibrations are made using standard certified gas

mixtures. Normally, a calibration sample is run after every 4th sample

analysis.

Page III-14 Report DAC-60510-FI


Volume III

Sample analysis is carried out by comparing the peak area

produced by the sample with the area produced by the appropriate calibra-

tion mixture. Suitable factors are introduced if the recorder attenuation

setting for a given sample size is different for the sample and calibration

mixture. A constant flow rate of carrier gas, usually 35 ml/minute, is

used for all analyses and calibrations.

Although the GC analysis became fairly standardized and routine,

each system under examination required special consideration with respect

to separation of the pressurant gas peak and considerable column experimen-

tation was required.

Some of the propellants produce oxygen by reaction with the

constituents of the column materials. This is not a problem if helium is

the constituent of analytical interest, as the oxygen peak is readily separated

from helium. However, if nitrogen is being analyzed, the oxygen cannot

readily be separated and it causes interference because of its higher thermal

conductivity. In some cases, it proved expeditious to use oxygen as a

carrier gas for nitrogen analysis when oxygen was formed in the GC column.

Because of the fairly small difference in thermal conductivity between

oxygen and nitrogen, this procedure is feasible only if the nitrogen content

of the sample is fairly high, viz., about 5% or more by volume.

Report DAC-60510-1_I Page III-15


Volume III

IV. PRESSURANT SOLUBILITIES IN PROPELLANTS

A. INTRODUCTION

Data for various pressurant, oxidizer, and fuel systems are pre-

sented in graphic and tabular form in the following subsections. See the

Table of Contents of this volume for a listing of the specific gas and propel-

lant systems for which data have been compiled.

The data in this Design Guide do not include all the available

solubility information of the systems listed. Material that is superseded by

more recent or accurate data has not been included unless the older material

presented information of specific value that was not adequately covered other-

wise. In nearly all cases the reader can be led to further information on a

specific system by consulting the references given here. The authors have

endeavored to cover both the open and classified literature up to July 1968.

For ease of reference, the material is organized into the fol-

lowing groups: pressurant gases, propellant oxidizers,and propellant fuels,

in the generally accepted sense of these terms. The order of propellants in

each group is alphabetical. For each group a table of pertinent physical

properties of the compounds involved is included in the preliminary discussion.

The data in most systems are presented in both isothermal and

isobaric composition diagrams for easy reference and interpolation in areas

of interest. Tables of experimental data are included where they may be of

further use (i.e. in preparing accurate expanded plots in specific pressure

regions). It should be noted that in all cases the pressures given are total

system pressures (not component partial pressures) unless otherwise stated.

On most of the isothermal pressure-composition diagrams (e.g. Figure IV-Z3)

the curves have been extended to zero concentration of pressurant gas, and

the x-axis intercept is the vapor pressure of the pure propellant at the tem-

perature of the isotherm.

Nomographic presentation of gas solubility data is rarely used in

practice, but it can be of great value where frequent references to a system

Report DAC-60510-FI Page IV-i


Volume III

are needed which involve tedious and inaccurate interpolation. As an example

of this technique, the Astropower Laboratory data for the fluorine-helium

system has been reduced to the pressure-temperature-composition nomo-

graph shown in Figure IV-1. The ease of making interpolations involving all

three variables, as illustrated in the key, is apparent. The reader is directed

to the book by Levens (Reference 43) for the mechanics of constructing such

diagrams for particular cases.

B. PRESSURANT GASES

Properties of ten selected pressurant gases are given in Table

IV-1. However, of these ten, helium and nitrogen are the only widely used

pressurant gases for propellant systems, although hydrogen, neon and argon

see occasional service.

TABLE IV- 1

PROPERTIES OF SELECTED PRESSURANT GASES (Reference 90)

Boiling Critical Properties Gas Specific Heat


7 Point at Cp-BTU/lb°R
Pressurant Cp/Cv Molecular 1 Arm Temperature Pressure Nominal Temp/
Gas (60°F) Weight (°R) (OR) (psia) Low Press.

Air 1.4 Z9 14Z 239 547 0.Z4


Ammonia I.Z8 17 43Z 730 1640 0.5Z3

Argon 1.67 39.9 15 Z71 706 0.125

Carbon dioxide 1.28 44 351 548 1073 0.18

Helium 1.66 4 8 I0 33 1,25

Hydrogen 1.4 Z 37 60 188 3.39


Methane 1.:_6 16 Z01 343 674 0.55

Neon 1.64 20. Z 50 80 394 0.25

Nitrogen 1.4 Z8 140 227 493 0.25

Propane 1.13 44. l 415 666 617 0.25

Since the binary system liquid nitrogen-helium has received

extensive study, its equilibrium composition data are also included in this

section.

Page IV-2 Report DAC-60510-FI


Volume Ill

O O O O O O O
O O O O C CD C3

O _
I I 7 t ] i r

©
O |Ill! I I
11111 1 I °r-I
0

i-=I

I I I I I

0,=l

°pi

.,=I

4=l

°,=I

,-=4

0
Z
0
_ Itt I t _ L , I
OCD O O O O O
>
@

m
.,--I
"\

\
>.

Report DAC-60510-FI Page IV-3


Volume III

_0 o,i N o o _ o- # _ o o- _ .-;

,,.0

a'.oO _0 01"_ O0".a',u"l


t.- oo I oo Z _ ,.o I t.- _ t_ ,.o
,--i

M
0 "_ e¢_ _ oO ¢'_
N

"_ 0
oO I

8
6
Z
< -_ 0_ _ _ -_ O0 O0 _ o'_ u_ _.-

_f u'_ ea _ _ I _ eq on .-( N _ e_
0

N 0 ,.O "_ 0", r'- O0 0" P.-

0 _ 0" _ _ "_ _ a" 0" O0 ¢"..1 C"


_o
M
0 0

<
0

M IA_I_'_O00 _l_ggOLl'ht'%]

0
0 0
2 _
_q
<
u _E _ _ 0 _ _ N O
N _ NE_ 0 N_ ._ N
_q ;_o , _ t z zzoouz .,..,

m
o_
cg

"_ C} o

,._ _ Q ,_ N
U
_'_ 0
0 _ ¢> _ ::I "d
N
.,,.(
,_ = _. o D >- r'_ U

_ _ 0

0 0 _ _ 0 _ _
._ ._ .... ._ _
uu_R-_ zzz _

Page IV-4 Report DAC-60510-FI


Volume III

Solubility data for helium in liquid nitrogen are given in Figure

IV-2. These data are taken from Reference 44. There is good agreement

between this work and the older work of Kharakhorin (Reference 45).

Kharakhorin's data are plotted in Figures IV-3 and IV-4 for pressures to

200 atm.

C. SOLUBILITY DATA FOR PRESSURANT GASES IN


PROPELLANT OXIDIZERS

Pertinent physical properties for the oxidizers considered here

are listed in Table IV-2. The tabulated solubility data and/or the data plots

for the oxidizer-pressurant systems which are available are presented in the

following sections.

i. Chlorine Pentafluoride - He lium

See Section 2.

2. Chlorine Pentafluor ide - Nitrogen

Solubilities of helium and nitrogen in liquid chlorine penta-

fluoride were measured by Astropower Laboratory for this Design Guide

under Contract NAS7-548. The solubility data for these two systems are

tabulated in Table IV-3; experimental details may be found in Reference 46.

TABLE IV- 3

SOLUBILITY OF HELIUM AND NITROGEN IN


LIQUID CHLORINE PENTAFLUORIDE

Mole Percent Concentration

Test Vapor Pressure He lium Nitr og en


Temperature of Propellant
OF psia(a) 300 psia 700 psia 300 psia 700 psia

-I00 0.59 0.120 0.300 3.53 8.17

-50 3.24 0.196 0.485 3.27 7.43

0 12.1 0.308 0.715 3.35 7.66

+50 34.8 0.412 O.99O 2.96 7.61

(a) Reference 47.

Report DAC-60510-FI Page IV-5


Volume III

A_,

I0 20 30 40 50 60 70 80
! I I I I_ I II

4O

32
4 /_ 270o F d
O
U]

0_

24 O

U]
v

(D
16

2 ../ 306OF O

/- 8
1 -_322OF

0 _ I I

0 300 600 900 1200

Total Pressure, psia t¥$L,

Figure IV-2. Isothermal Pressure - Composition Diagram


For the System Liquid Nitrogen-Helium

Page IV-6 Report DAC-60510-FI


Volume III

Temperature oR

130 140 150 160 170 180 190

.... I ........ I ........ I ........ I ....

trn

70 30

c'
_9
_Vapor Phase
0

_9

20 atm
_9
_9 L/
50 50
0 ¢9
_L

3O 70

2O 80

P-- 140 atm

IAquid Phas( atm

0 O0

7O 80 90 100 1 10

Tcmpcrature OK

Figure IV-3. Isobaric Equilibrium Concentration for the Binary


System Nitrogen-Helium

Report DAC-60510-FI Page IV-7


Volume Ill

Pressure, psia

1000 20OO 3000

I | I I i i r i i
r v _ , , _ ' ' 1 r , , , , i i i I
100
68. 0UK [ T 90. L°K

qo 10

8o 2O
I / r ,07°K := ._o

7O 3O

Vapor Phase

6O
l
4O

/,/
o

5O 5O

E
(,
_9

2
4O
// 6O

//
@

7O

/f
8O
go

Liquid Phase

l0
f 9O

T=I07OK T:q0. l°K


77. 3°K

0 0°K 100

0 50 100 150 200


r¢$To
Pressure, Atmospheres

Figure IV-4. Isothermal Equilibrium Concentration Diagram


for the Binary System Nitrogen-Helium

Page IV-8 Report DAC-60510-FI


Volume III

The results reported in the table are obtained from duplicate analyses for

two successive samples. Agreement of these values within experimental

error was accepted as indication that solution equilibrium had been attained.

These data are presented as isothermal pressure-

composition and isobaric temperature-composition plots in Figures IV-5,

IV-6, IV-7 and IV-8. Isobars at 150 and 500 psia have been constructed by

interpolation for each system.

3. Chlorine Trifluoride -Helium

See Section 4.

4. Chlorine Tr ifluoride - Nitrogen

Solubilities of helium and nitrogen in liquid chlorine tri-

fluoride were measured by Astropower Laboratory for this Design Guide,

under Contract NAS7-548. The solubility data for these two systems are

given in Table IV-4; experimental details 17nay be found in Reference 46.

TABLE IV-4

SOLUBILITY OF HELIUM AND NITROGEN IN


LIQUID CHLORINE TRIFLUORIDE

Mole Percent Concentration

Test Vapor Pressure He lium Nitr og en


Temperature of Propellant
OF psia(a) 300 psia 700 psia 300 psia 700 psia

-I00 0.20 0.025 O. O79 0. 770 1.91

-50 1.8 0.061 0.160 0. 915 1.85

0 4.4 0. I01 0.255 0. 896 2.07

+5O 13.9 0.154 0.340 1.07 2. 42

(a) Reference 48,

Report DAC-60510-FI Page IV-9


Volume III

"UlOS meT9 / (cIJ_S) aH aa

,_ e,_ 00 _i _

O
O 0,.._

O
O O
,.D .p4

.o
O
O
U_

O
o
,_=
o
O

I-4
_'_
g]
_._

o
O O
¢q
m

o 0
o o
o o _ o 0

O
0 [] 0 ,_
_d
0
0 !

0
°_,,i

0 O0 ._O _t _ e_

um_.IaH luaa.tacI alOl_I

Page IV-10 Report DAC-60510-F1


Volume III

"uI°S u-r_-_O / (dIi_) aH _

".D ¢q oo ,_

\
\
¢_"0

\ C_
0

o
0 o_

\ E_
\ 0

k_
0 o

_ cr
_'_

o
_ m
.,.-i
!

,-_ ¢o
\ o._
m

\
,.d
I

i:m

o co _D _ r_ o

u.mt.I_ H luo._ocI oIOIAI

Report DAC-60510-FI Page IV-II


Volume III

•_o$ ure.t 0 / (diS) ZM _

o0 _ o

o
o

0
o
o
_o

G) ._ o
o

o .o
0_ 0_..4

o_ 0

oo
, .=

0
O_
o
o o
o o _ o _
I m 0 u_ >_

o o [] 0 <]
o_

>

o co _o _I4 cq o
P-4
u_o.t$t N _u_.I_ct _lOF_l

Page IV-12 Report DAC-60510-FI


Volume III

• uIo ff me.I,) / (d&S) ZN D3

"-D tM
oO -q* o

o
D I LiD

I I _0

I I o O

I I L_
¢M
_z

I I
I I
I I O r_

<1
I ? " O

O
m
o;L
_0

I I (D
O ,,--4

I I O

I I k_
¢M

I I
I

F*
¢0

I ! To_
I o c;
-0 L_
! .,.._ ¢/]

I _oq
>-

I
lf5
t"
od
I I

>
!

00_ D
I
I o£
o
o
"7
o co ,.D ..-rp ¢"1 0

u_goa_T2 C :_uo3.Iact aIOlAI

Report DAC-40510-F1 Page IV-13


Volume III

The results reported in the table are obtained from duplicate analyses for

two successive samples; agreement of these values within experimental

error was accepted as indication that solution equilibrium had been attained.

These data are presented as isothermal pressure-composition

and isobaric temperature-composition plots in Figures IV-9, IV-10, IV-ll,

and IV-12. Isobars at 150 and 500 psia have been constructed for each system

by interpolation. It is noteworthy that the solubility of nitrogen is quite low

and shows an inverse temperature relationship; i.e. the solubility increases

with temperature.

5. Dioxygen Difluoride- Helium

The solubility of helium in liquid dioxygen difluoride was

measured by Astropower Laboratory for this Design Guide under Contract

NAS7-548. The Solubility data for this system is tabulated in Table IV-5;

experimental details may be found in Reference 46. The results reported in

the table are obtained from duplicate analyses for two successive samples;

agreement of these values within experimental error was accepted as indica-

tion that solution equilibrium had been attained.

TABLE IV- 5

SOLUBILITY OF HELIUM IN LIQUID DIOXYGEN DIFLUORIDE

Mole Percent
Concentration
Test Vapor Pressure He lium
Temperature of Propellant
OF torr (a) 300 psia 700 psia

-Z00.0 ° 4.5 0.018 0.041

-150.0 o 5O O. O6O 0.130

(a) Reference 49.

These data are presented in an isothermal pressure-

composition plot in Figure IV-13.

Page IV-14 Report DAC-60510-FI


Volume III

arm.

lO 2O 3O 4O

I I I 0.8
0._2

0.

0.24
Z8
O-i

O
00°F

_ 50°F

0°F
/ l
0.6

/
0.20
A 50°F

// A

//
O
tq

E
0.4
0.16 C
P_

0. 12

0.08
,//
/ 0.2

(}. 04 /-

0 100 200 %_ 0 400 %00 600

Total Pressure psia

Figure IV-9. Isothermal Pressure-Composition Diagram for


the Systme Liquid Chlorine Trifluoride-Helium

Report DAC-60510-FI Page IV-15


Volume III

0.32

A 150 psia (Calculated by lnter_ )olation)

O. 28
0

0
300

50O Calculated by /
/
Inte rpolation)
[] 700
5X)- 0.6
0.24
/
/

O, 20 /

o / /

_0.4
i
0

f
/

:_.=_0.16 /
0.12 / J

_Z

o. o8 r //--_

O. 04 _ "_'_

-100 -75 -50 -25 0 25 50


O
Temperature F
erls_

Figure IV-10. Isobaric Temperature-Composition Diagram for


the System Liquid Chlorine Trifluoride-Helium

Page IV- 16 Report DAC-60510-Fl


Volurne III

"ul°S ure-IO / (cI.LS) ZN _

b,

°
o -=
p,-

0 0 _ 0

,,.0 0.0 .,_,

0 0 "_
0 "_

o _

°r4

m_
0
m _"0

o _
o 0 _o
0 0 0 0
ur_ 0 Lt_
0 I I

0 I3 0 <1
o
o

°_,.(
0

ua_o=_!N _,ua.-_._ad alOIAI

Report DAC-60510-FI Page IV- 17


Volume III

"w[os urged / (cI&g) ZN na

,,.o o

\ O _
D_
o

U7
N _Z
I

I
C_ ,.,
I
I _o_ ,,,,,,,,4

0,-4

o_

O I O "_
t) o
,--4
0
....-4
0
I O

_h._h-- I I

I I
,1_ ,.o I I
I I o
[] 0 < '7_ >,
I

,--4 ,,,--I I o=
I
m I I
,q

o o o
I
l
,_0 0 El I
D_
o .,..4

u_ozJ, l.N _,u_ao d eIOFq

Page IV-18 Report DAC-60510-FI


Volume Ill

Arm.
10 2O 30 4O

I I I

0.12--
/
/

--0.3
0.10--i

]
0.08--i

/ ---4_

0.02
/ /

0 0

0 100 200 300 400 500 600 7OO

Temperature OF

Figure IV- 13. Isothermal Pressure- Composition Diagram For


the System Liquid Dioxygen Difluoride-Helium

Report DAC-60510-FI Page IV-19


Volume III

6. 70% FLOX-Helium

The solubility of helium in liquid 70% FLOX (70% by weight

of fluorine in oxygen) was measured by Astropower Laboratory for this Design

Guide, under Contract NAS7-548. The solubility data for this system is tab-

ulated in Table IV-6; experimental details may be found in Reference 46. The

results reported in the table are from duplicate analyses for two successive

samples; agreement of these values within experimental error was accepted

as indication that solution equilibrium had been attained.

TABLE IV-6

SOLUBILITY OF HELIUM IN LIQUID 70-FLOX

Mole Percent
Concentration
Test Vapor Pressure Helium
Temperature of Pr ope llant
OF psia(a) 300 psia 700 psia

-320 5 0.094 0.230

-300 20 0.217 0.579

-280 48 0.314 0.797

-260 120 0.354 1.15

(a) Reference 50.

These data are presented as isothermal pressure-composition

and isobaric temperature -composition plots in Figures IV- 14 and IV-15.

Isobars at 150 and 500 psia have been constructed for this system by inter-

polation.

7. Fluorine -Helium

The solubility of helium in liquid fluorine was measured by

Astropower Laboratory for this Design Guide, under Contract NAS7-548.

The solubility data for this system is tabulated in Table IV-7; experimental

details may be found in Reference 46. The results reported in the table are

Page IV-20 Report DAC-60510-FI


Volume III

'ulos u.r_.x9 / (_,LS) OH _

•,O ,_ o,a 0

D-

o
o

0 *,-I

_D
L_

u_
i 0
_D

O_
o
o
cq

0 O_

0 0 0 0 o
0 0 0 0
0 oO _D

I I I I

o 0 [] 0 ,_

o 4
I

>

o co _D _ _1 o

,Z c_ c_ c_ c_

umllaH lua-_=acI alOlN

Report DAC-60510-FI Page IV-21


Volume III

"ulos urezo / (d&S) OH oo

,.o o

o 0

\ !
E
\ !
\
\ 0,.._

\ I !

_o_
o

\ I
\ I .,-_

I
o
o
(J _n
i ,,..4

\ |
I
\
M
7
>
o

!
0,0

o
o o0 _ _ r,.I
- c_ c_ c_ d

umt.I_H _u_._o d _IOIN

Page IV-ZZ Report DAC-60510-FI


Volume III

from duplicate analyses for two successive samples; agreement of these

values within experimental error was accepted as indication that solution

equilibrium had been attained.

TABLE IV-7

SOLUBILITY OF HELIUM IN LIQUID FLUORINE

Mole Percent
Concentration
Test Vapor Pressure He Iium
Temperature of Propellant
OF psia(a) 300 psia 700 psia

-320 6 0. I01 0.242

-300 Z2 0.231 0.577

-280 52 0. 344 0.895

-260 140 0. 339 1.14

(a) Reference 47.

These data are presented as isothermal pressure-composition

and isobaric temperature-composition plots in Figures IV-16 and IV-17.

Isobars at 150 and 500 psia have been constructed for this system by inter-

polation.

8. MON- 10 -Helium

Figure IV-18 presents a selected summary of solubility data

for helium in MON-10 (mixed oxides of nitrogen containing 9. 23 wt. % nitric

oxide). The data cover a temperature range of 50 ° to 1Z0°F and pressures

of 300 to 720 psia (22 to 49 arm). These data were obtained from Reference 51.

9. Nitrogen Tetroxide-Argon

See Section 12.

i0. Nitrogen Tetroxide -Helium

See Section 12.

Report DAC-60510-F1 Page IV-23


Volume III

"uIO_ tu_-tO / (c[JuS) _H _

O
t,,%

.4m

O
¢q

um_.Ia H _uazz_acI aIOlAI

Page IV-24 Report DAC-60510-FI


Volume III

..o o

/
\ /
\
\ I o

\ 0
0 _
o

\
\
\

\
\

\ d
\ 7
>

i:m

u.mt.I_H lu_cI OlOIAI

"v

Report DAC-60510-FI Page IV-25


Volume Ill

2.0 -

[3 Lab Data

O Test Stand Data

1.5

o
O P__7Z0
O
- psia
l.O

0.5 ___
P= 320 psia

4O 6O 80 I00 120 4O

Temperature, OF
r_,O,

Figure IV-I 8. Isobaric Temperature - Composition


Diagram for the System
Liquid Mon lO-Helium

Page IV-26 Report DAC-60510-FI


Volume III

_x

II. Nitrogen Tetroxide - Oxygen

See Section 12.

12. Nitrogen Tetroxide-Nitrogen

The solubilities of argon, helium, oxygen and nitrogen in

nitrogen tetroxide in the low pressure region of 0.5 to 2 arm have been

reported by Chang and Gokcen (Reference 52). Their data are summarized

in Table IV-8.

Data for the solubility of helium and nitrogen in liquid nitrogen

tetroxide at slightly higher pressures have been determined by Bell Aero-

systems Co. (Reference 53), and are given in Table IV-9.

Solubilities of helium and nitrogen in this oxidizer have also

been determined at 300 and 700 psia by Aerojet-General Corporation (Refer-

ences 38 and 39), and these data are given in the isobaric temperature-

composition plots of Figures IV-19 and IV-20.

13. Nitrogen Tr ifluor ide - Helium

See Section 14.

14. Nitrogen Trifluoride- Nitrogen

The solubilities of helium and nitrogen in liquid nitrogen tri-

fluoride were measured by Astropower Laboratory for this Design Guide,

under Contract NAS 7-548. The solubility data for these two systems are

tabulated in Table IV-10; experimental details may be found in Reference 46.

The results are from duplicate analyses for two successive samples; agree-

ment of these values within experimental error was accepted as indication

that solution equilibrium had been attained.

These data are presented as isothermal pressure-composition

and isobaric temperature-composition plots in Figures IV-21, IV-22, IV-23,

and IV-24. Additional isobars at 150 and 500 psia have been constructed for

each system by interpolation.

Report DAC-60510-F1 Page IV-27


Volume III

_...,

0
z_
c_

Z
_w C_
<
C_
l
>

0
4
< z
$

0
- __
o_

g _ ....
×
II

__Z_Z ..
0
m
0

_-- O0 0_ 0
,.0

Page IV-28 Report DAC-60510-FI


Volume III

TABLE IV- 9

SOLUBILITY OF HELIUM AND NITROGEN


IN LIQUID NITROGEN TETROXIDE

Pre s sur izing Total Gas Pressure Temperature Solubility


Gas (psia) (°F) (wt%)

He Iium 54. 3 73 0.04±0.01

63 6O 0.02 ± 0.004

55.4 32 0.02 +0.01

63.7 70 0.20 ± 0.01


Nitrogen
64. 2 3Z 0.14±0.01

TABLE IV- i0

SOLUBILITY OF HELIUM AND NITROGEN


IN LIQUID NITROGEN TRIFLUORIDE

Mole Percent Concentration

Test Vapor Pressure He lium Nit r og en


Temperature of Propellant
OF psia( a ) 300 psia 700 psia 300 psia 700 psia

-320 <1 0. 020 0. 041 -- --

-250 3.0 0. 099 0. 324 -- --

-ZZ0 6.5 -- -- 43.8 --

-200 14.7 0. 341 0. 824 26. 5 72.2

-175 34 -- -- 18.5 52.8

70 0. 500 I. 56 13.5 38.3


-150

(a) Reference 54.

Report DAC-60510-FI Page IV-29


Volume III

Z.0 ---0.8

O
_O
1.5 - --0.6 ._
0
700 psi_

©
--0.4_
1.0

0.5 c- -0.2_
--O
O
_A
-o 300 psi,t )
O-

-- 0

0 25 0 75 I00 125 150 175 200

Temperature OF .-.e.

Figure IV-19. Isobaric Temperature-Composition Diagram for the


System Liquid Nitrogen Tetroxide-Heliurn

I0--

o 7 5-- 0
)

700 psia Z

© 0 ¢o
5.0-- f

0 _
F_

C_ 1.0 0
_2.5--
Z O-
300 psia
)
U

0 m
0

0 25 50 7 00 25 5O 75 200

rvf, F
Temperature oF

Figure IV- 20. Isobaric Temperature- Composition Diagram for the


System Liquid Nitrogen Tetroxide-Nitrogen

Page IV-30 Report DAC-60510-FI


V olurn e III

lO 3O 4O

I I
O " 320°F

[] - 250°F
/ 4.5

O - 200 °F /
/
A -147°F
1. _)_

/
2. Om

3.0

O
Oo U_

Q)
O.
/ 1.5
U_

O. (9
(9

0 I00 200 3 )0 400 500 600 700

Total Pressure psia

Figure IV-21. Isothermal Pressure-Composition Diagram for the


System Liquid Nitrogen Trifluoride-Heliurn

Report DAC-60510-FI Page IV-31


Volume III

"uI°s uI_-_O / (c_±S) OH _:_

] I J I I
o
c_

0,\ I

,.-.a
_z
.,_

,.-a

(3
¢',,1
°,.a !

.,.-i
o
t_ oo oo
c,_ Ln r"

o
_d
!
!

o
- _ c; d

um_Io H _uo_._o d oIOl _

Page IV-3Z Report DAC-60510-F1


Volume III

Atrn.

I0 20 30 40

I I I ,, I
7O

O -22°°F

i II /_
D -200°F
6O

0 -175°F

-150°F
50
@

zoo E

40
@

30

2O
/ // /// - 100
U_

Z
u
U

I0

0 100 200 300 400 500 600

Total Pressure, psia

Figure IV- 23. Isothermal Pressure-Composition Diagram for the


System Liquid Nitrogen Trifluoride-Nitrogen

Report DAC-60510-F 1 Page IV-33


Volume III

(ca I
lculated by I
interpolation) ,% I150 psia
70--
''_ I o 3oo
(Calculated by O 500
interpolation)

60--
__, []7oo

(U
50 O
b.O In
0

L_
_ 4o
U

5q

ed
"S 30 Z
O0

Zo-

lO-

-- 0

-200 -175 50

Temperature OF

Figure IV-24. Isobaric Temperature-Composition Diagram for


the System Liquid Nitrogen Trifluoride-Nitrogen

Page IV-34 Report DAC-60510-F 1


Volume III

Because of the very high solubility of nitrogen in nitrogen


trifluoride, Henry's Law is not obeyed and the corresponding isothermal plots
in Figure IV-23 are shown as curves. Due to experimental difficulties, no

data was obtained for this system above 300 psia at -220°F; consequently the

-2Z0°F isotherm is plotted as a straight line and can be considered as only

approximate.

15. Nitryl Fluor ide-Helium

See Section 16.

16. Nitryl Fluoride-Nitrogen

The solubilities of both helium and nitrogen in liquid nitryl

fluoride were measured by Astropower Laboratory for this Design Guide,

under Contract NAS7-548. The solubility data for these two systems are

tabulated in Table IV-l l; experimental details may be found in Reference 46.

The results reported in the table are obtained from duplicate analyses for

two successive samples; agreement of these values within experimental error

was accepted as indication that solution equilibrium had been attained.

TABLE IV- 11

SOLUBILITY OF HELIUM AND NITROGEN


IN LIQUID NITRYL FLUORIDE

Mole Percent Concentration

Test Vapor Pressure Helium Nitrogen


Temperature of Propellant
oF psia(al 300 psia 700 psia 300 psia 700 psia

-150 3 0. 054 0. 127 2.89 6.6Z

-100 14 0. 108 0. 248 1.98 4. 82

-50 6O 0. 176 0. 433 1.89 4.29 (b}

0 if8 0. 195 0. 666 1.37 4.Z4

(a} Reference 55.

(b) 680 psia.

Report DAC-60510-FI Page IV-35


Volume III

These data are presented as isothermal pressure-composition

and isobaric temperature-composition plots in Figures IV-25, IV-26, IV-27,

and IV-28. Additional isobars at 150 and 500 psia have been constructed for

each system by interpolation.

17. Oxygen-Helium

Figures IV-29 through IV-32 are taken from Reference 56.

Figure IV-29 is an isothermal pressure-liquid phase composition diagram

for this system at total pressures up to 200 atmospheres in the temperature

range of 70 ° to 150°K. The region of this plot from 0 to 70 atmosphere total

pressure is shown expanded in Figure IV-30. The corresponding data for the

vapor phase is given in terms of oxygen concentration in Figure IV-31. A

plot of equilibriumK factors (concentration ratios) for the major component

in each phase is included in Figure IV-32.

The solubility of helium in liquid oxygen was also measured

by Astropower Laboratory for this Design Guide, under Contract NAS 7-548.

The solubility data for this system are tabulated in Table IV-12; experimental

details may be found in Reference 46.

TABLE IV-IZ

SOLUBILITY OF HELIUM IN LIQUID OXYGEN

Mole Percent
Concentration
Test Vapor Pressure Helium
Te rope r atur e of Propellant
oF ps ia (a) 300 psia 700 psia

-320.0 + 0. 1 Z.5 0. 086 O. 194

-280.5 + 0.5 37 0.261 O. 658

-259.8 + 1.8 80 0. 427 1.09

-238.6 ± 1.4 160 0.311 1.35

(a) Reference 57.

Page IV-36 Report DAC-60510-FI


Volume III

Atra.

I0 20 30 40

I 1 I I! _

0.6
/
2
O - 150°F /

[] - 100°F /
0.5

O -50°F /

0.4
A O°F / !

_ 0.3

} ,
0.2 _

......._ _ o.s
0.1

0 100 200 300 400 500 600 700

Total Pressure, psia


r_'E#m

Figure IV-25. Isothermal Pressure-Composition Diagram for


the System Liquid Nitryl Fluoride-Helium

Report DAC-60510-F 1 Page IV-37


Volume III

| I ! !
150 psia (Calculated by Interpolation)

0.6
0 300 /
0 500 (Calculated by Inter )olation)
/
0.5

U
/ J
f
J
i _I.5 o

0.3 f
f _q
J

0.2 ,<
I ._r., t
,5

O. 1

0 0

t5q 25 - i00 -75 -50 -25 0

Temperature °F
¢_It,

Figure IV-26. Isobaric Temperature-Composition Diagram for


the System Liquid Nitryl Fluoride-Helium

Page IV-38 Report DAC-60510-F 1


Volume III

Atm.

i0 20 30 40

I I I I
O - 150°F

6 I-I - 100°F

O - 50°F 20

A 0°F
5
1

CD

O
4
Z

©
3 / 10 !
<D

2
/Jj - z_
_

0 0

0 i00 200 300 400 500 600 700

Total Pressure, psia ,,i,,

Figure IV-27, Isothermal Pressure- Composition Diagram for


the System Liquid Nitryl Fluoride-Nitrogen

Report DAC-60510-FI Page IV-39


Volume IlI

I I I I

\
(Calculated by Interpolation} L_ 150 psia

0 300

\ (Calculated by Interpolation} 0
E]
5OO

700 ---- 20

i
C
0

0
I
4 m
E
Z
0
G

lO

r_
Z

()

1 --

O--

50 -125 00 -75 -50 -25 0

Temperature OF cvfg]

Figure IV- 28. Isobaric Temperature-Composition Diagram for


the System Liquid Nitryl Fluoride-Nitrogen

Page IV-40 Report DAC-60510-F 1


Volume III

Total Pressure, psia


0 367 735 1102 1470 1837 2205 2573 2940
14 r 111.7

12 93.9

I0 76.7
d
o

£
_J
o

¢d

// y o e0

a:

/
o
6 ta

, 1 // .,o

70.
o 1 o.o
0 25 50 75 I00 125 150 175 200

Total Prt, ssure, A_m. .,_

Figure IV-29. Isothermal Pressure-Composition Diagram for


Oxygen-Helium in the Liquid Region

Report DAC-60510-FI Page IV-41


Volume III

"uIo9 tuezO/(d&S) OH _
-.D o -.D _ ,.D
O
4
ce_ N N ,-. rd o

o_
o
eq p..
0
o
o
o o

o
oo -.,o
o{3

oM
LN o

D-

_0

or.n
E 0
o0 <
co o
t_

.,-4

\ , o
_-
C
o

0
o _.1 "U

_0_
o
o-x

c_
r'e3
I

>

o
I:m

t_ c'3 ¢xl o

uan_.lO H luaaaacI alOI, X

Page IV-42 Report DAC-60510-FI


Volume III

Total Pressure, psia


0 367 735 1103 1470 1837 2205 2573 2940

!
! \
l • _ _ 14 ( ,91 OK
l
\ \
\ \

\
\

10 1 \
\ 1
>,

0
\
\
1.0 i \]

\
\
\ ---...
\

I
0.1
0 25 50 75 100 125 150 175

Total Pressure, Atm.

Figure IV-31. Isothermal Pressure-Composition Diagram


for Oxygen-Helium System in the Vapor
Region

Report DAC-60510-FI Page IV-43


Volume III

lo 3 \\\ He K-Factors

\ \ _. _ _ 70.80o;_

102

l0 --

_o_
o r
O
149. 91°K

\ -- 143 93oi<

i0 1_ _ 02 K-Factors
\
i 09.96°i<

_. 89 98°K

lO

I0
-B
__--

40
__

80 120
75. 9oK

69.9°K

160 200
I
Pressure, atm

Figure IV-32. Equilibrium K - Factors for


Oxygen-Helium System

Page IV-44 Report DAC-60510-F l


Volume III

The results reported in the table are obtained from duplicate analyses for

two successive samples; agreement of these values within experimental error

was accepted as indication that solution equilibrium had been attained. These

data are presented as isothermal pressure-composition and isobaric tempera-

ture-composition plots in Figures IV-33 and IV-34. Additional isobars at 200

and 500 psia have been constructed for each system by interpolation.

18. Oxygen-Nitrogen

Although the term "solubility, " as used in the present context,

does not apply to this binary system, equilibrium concentration data are pre-

sented here for their practical value.

The following graphs represent data on the equilibrium of

nitrogen in liquid oxygen taken from Reference 58 (the basic sources are also

listed below). Figures IV-35 and IV-36 are isothermal pressure-concentration

diagrams for nitrogen-oxygen mixtures. Figure IV-35 is based on values

obtained by Reference 59 for isotherms of 65°K, 70°K, and 77.5°K in the

pressure range of 1 psia to 15 psia (0. 1 - 1.02 atm). The equilibrium con-

centrations in Figure IV-36 for the 90.5°K, 99.94°K, ll0.05°K, 119.92°K,

and 125°K isotherms were taken from Reference 1 and the values for the 85°K

isotherm is from Reference 60. The pressure range for this data is 15 psia

to 470 psia (1 to 3Z atm). Figure IV-37 is an isobaric temperature-concen-

tration diagram for nitrogen-oxygen mixtures for three pressures, 15, 20

and 30 psia and is obtained from the data of References 60, 61 and 62.

19. Oxygen Difluor ide - He lium

See Section 20.

20. Oxygen Difluoride- Nitrogen

The solubilities of helium and nitrogen in liquid oxygen di-

fluoride were measured by Astropower Laboratory for this Design Guide,

under Contract NAS 7-548. The solubility data for these two systems are

tabulated in Table IV-13; experimental details may be found in Reference 46.

Report DAC-60510-FI Page IV-45


Volume III

Atrn.

10 Z0 30 40

I I I
O -3Z0°F
1.2 [] .280°F

O-260°F

/k. Z40°F

1.0

o
_6 u_
.r-q 0.8 E
rd

U
I..w 0.6
/ /4 u_

0.4

0.2

0 100 200 300 400 500 600 700


Total Pressure, psia

Figure IV-33. Isothermal Pressure-Composition Diagram for


the System Liquid Oxygen-Helium

Page IV-46 Report DAC-60510-F 1


Volume III

"uI°s turbo / (d_LS) eH oo

¢xl
I , f
Y
I / i I

\ / 0

\ r

o
ko ,.o
t_

\ % 1 !

m
O_

0 0 ,

0 o o
00
N
I
_'_ 0

I1)

o _

o 0 _
o
o
!

m L)
v
I
o o 0 o
o o o o
t--

<3oO []

o
N
ce_
!

_ o o
• °

umt.Ia H #ue_ecI _IOI_I

Report DAC-60510-FI Page IV-47


Volume III

Z 0 _uaoaa d alODI
0
0 0 0 0 O 0 0 o 0
{F,

I
A o!

%
\
\
'I
I
!
0

%
0
.ca
\
\ \
\
D.-
u
o

\ \ %
,,0
0
tO _a
m

°_..4

0_.._
oO --- N

J
& \
_a

D- o

o
0
H
._.,_
_Z

,,, .4
6 m!
>
(p
w

6 _
°F,4

gN luaaaad aI°I/_I

image IV-48 Report DAC-60510-FI


Volume III

,kv
70 _ua'Jad _1"1_

%,
X_ I
o
,i
I ,

\ \
\\
\- O
\ 4_

.,-4

\ \ \
.,-4

\ "- \ -
_o
O
_-_ O

.6

Report DAC-60510-Fl Page IV-49


Volume III

Temperature, °F
-320 -310 -300 -290

i i I I i l i I
, 1 I i
10o

90
_X io

80 20

\ \\
70

6O 40
N
z

U
_ 50
i/ 2 Atm

50
¢xl
O

¢J

\
0

40
\ \ , 60
0

\
3O
,\ X \ 7O

\
8O

10 |
9O
i

1oo

78 80 82 84 86 88 90 92 94 96 98

Temperature, OK e_m

Figure IV-37. Isobaric Equilibrium Concentrations


of Nitrogen-Oxygen Mixtures

Page IV-50 Report DAC-60510-F1


Volume III

TABLE IV- 13

SOLUBILITY OF HELIUM AND NITROGEN


IN LIQUID OXYGEN DIFLUORIDE

Mole Percent Concentration

Test Vapor Pressure He lium Nitr og en


Temperature of Propellant
oF psia(a) 300 psia 700 psia 300 psia 700 psia

-3Z0 <I 0. 024 0. 030

-270 1.5 0. O98 0. 203 i

-2Z0 29 0.25Z 0. 588 m

45 23.1 61. 5 (b)


-Z00

-170 i15 0. 344 1.08 14.1 49.9

-150 205 6.12 35.8

(a) Reference 63.

(b) 600 psia.

The results reported in the table are obtained from duplicate analyses for

two successive samples; agreement of these values within experimental error

was accepted as indication that solution equilibrium had been attained.

These data are presented as isothermal pressure-composition

and isobaric temperature-composition plots in Figures IV-38, IV-39, IV-40, and

IV-41. Additional isobars at 150 and 500 psia have been constructed for

these systems by interpolation.

In the system oxygen difluoride-nitrogen the useful operating

range is limited by the condensation of nitrogen (-226°F at 700 psia) and the

vapor pressure of the solvent (300 psia at -130°F). A further experimental

limitation was imposed by the very high solubility of nitrogen at the lower

temperatures. Consequently only the temperature range of -150 ° to -200°F

was investigated between 300 and 700 psia. The non-linear plots in Figure

IV-40 indicate considerable deviation from Henry's Law at these high pres-

surant gas concentrations.

Report DAC-60510-FI Page IV-51


Volume III

lO 3O 4O

I I I
1.O

O -320°F

0.8
[] -270°F

A
-220°F

_170°F
/ --36
O

_ o.6
/ i
O

¢)
'B 0.4

ml
0.2
I

_ -o

0 lO0 200 300 400 500 600 700

Total Pressure, psia ""

Figure IV-38. Isothermal Pressure -- Composition Diagram for


the System Liquid Oxygen Difluoride-Helium

Page IV-52 Report DAC-60510-FI


Volume III

].0 i
,/k 150 psia (Calculated by Interpolation) -- 4

0 300

0.8 0 500 (Calculated by Interpolation)

[3 700 __ 3 _

0.6_

,,./// 2 _v

_ 0.4
1/I"_

J
0.2--

-320 -295 -270 -245 -220 95 - [70

Femperature OF

Figure IV-39. Isobaric Temperature-Composition Diagram for


the System Liquid Oxygen Difluoride-Helium

Report DAC-60510-FI Page IV-53


V olurn e III

tm.

10 20 30 40

60

O-200°F

El- 175°F -- 300

50 -- -- A- 150°F

40 --
/ 200
0

/ /
0 _q

E
Z
0
30

I00
o 20
Z

10

0
/////
0 I00 200 30(] 400 500 600 700

Total Pressure, psia "'_'_

Figure IV-40. Isothermal Pressure-Composition Diagram for


the System Liquid Oxygen Difluoride-Nitrogen

_J

Page IV- 54 Report DAC-60510-F 1


Voluroe III

"uI°S uz_-IO / (diS) ZN :_0

o o o 0
0 0 0

i ,

I 0

0 _ 0
I '.D

I r I

/
/
/
/ 0
t',-

I 0
_
0,-_
°_'-I

0_
0

4_
(
0 _0
/ /
/ g
I

I
/ ...#

I U 0 ¢;

i/ 0
I"I
Q
I
0 0 0

/
4
!

/ O<]n
>

g / / Q;

/ .t. 0
0

0 0 0 0 0 0 0
•,0 un ,_ ce_ N

ugBo_1.bl _uoo_g¢ I _IOIAI

Report DAC-60510-FI image IV-55


Volume III

Zl. Per chloryl Fluoride-Helium

See Section 22.

22. Perchloryl Fluoride-Nitrogen

The solubilities of helium and nitrogen in liquid perchloryl

fluoride were measured by Astropower Laboratory for this Design Guide,

under Contract NAS7-548. The solubility data for these two systems are

tabulated in Table IV-14; experimental details may be found in Reference 46.

The results reported in the table are obtained from duplicate analyses for

two successive samples; agreement of these values within experimental error

was accepted as indication that solution equilibrium had been attained.

TABLE IV- 14

SOLUBILITY OF HELIUM AND NITROGEN


IN LIQUID PERCHLORYL FLUORIDE

Mole Percent Concentration

Test Vapor Pressure He lium Nit r og en


Temperature of Propellant
o F psia (a) 300 psia 700 psia 300 psia 700 psia

-150 0.5 0. 090 0. 284 5.75 12.9

-i00 3.5 0. 223 0.518 4.96 II.3

-50 16.7 0.298 0. 761 4.49 10.7

0 44 0. 438 1.21 3.89 9.53

(a) Reference 47.

These data are presented as isothermal pressure-composition

and isobaric temperature-composition plots in Figures IV-4Z, IV-43, IV-44,

and IV-45. Additional isobars at 150 and 500 psia have been constructed for

each system by interpolation.

Page IV-56 Report DAC-60510-FI


Volume HI

I0 30 40

I I
1.2

0 -150°F

-100°F

0 -50°F

A O°F
" 2.0 _

U /

1.0 _

100 200 300 400 500 600 700

Total Pressure, psia ,_.T

Figure IV-42. Isothermal Pressure-Composition Diagram for


the System Liquid Perchloryl Fluoride-Helium

Report DAC-60510-F 1 Page IV-57


Volume III

'ulos tu_-'O / (dZLS) _H _

0 _
_o
• ,-4 :3

o 0_
i

p_
4_ 4_

i
p

o
0

_d
U'5 I

>
"7
P

I
o

u_n_I_ H _u_o_ d elO]AI

Page IV-58 Report DAC-60510-FI


Volume HI

"UlOS u1_=O / (diLS) ZN 00

D--

0
0 0 _Z
,.0

.r-4

0 0

0
.r.i "'4
0
u'_
0,.._
.v-i
0

o 4
ul
m

0 _
0
_q
0

0
0

0
,.-4 0 0 0 0
0 0 0 0
t_ 0 tn
0 I

I I 0

o a 0 <_
.,.-4

0 O0 _ _ N 0

Report DAC-60510-FI Page IV-59


Volume III

"ulos u-'_O / (diS) ZN oo

,.o oo o

I o

°_,,,I |

0 _
• ,._ 0

o_

/ 0
0

I u
0

).(

o.

o
0
0

•,-_ [.']
0

.4
!

>

N o o0 ,.o "_ cq o

u_o=_. N _u_zod OlOY_

Page IV-60 Report DAC-60510-FI


Volume III

23. Tetrafluor ohydrazine-He lium


"-p_d

See Section 24.

24. Tetrafluor ohydrazine -Nitrogen

The solubilities of helium and nitrogen in liquid tetrafluoro-

hydrazine were measured by Astropower Laboratory for this Design Guide,

under Contract NAS7-548. The solubility data for these two systems are

tabulated in Table IV-15; experimental details may be found in Reference 46.

The results reported in the table are obtained from duplicate analyses for

two successive samples; agreement of these values within experimental error

was accepted as indication that solution equilibrium had been attained.

TABLE IV-15

SOLUBILITY OF HELIUM AND NITROGEN


IN LIQUID TETRAFLUOROHYDRAZINE

Mole Percent Concentration

Test Vapor Pressure Helium Nitrogen


Temperature of Propellant
oF psia( a ) 300 psia 700 psia 300 psia 700 psia

-200 0.7 0. 165 0. 405 18.6 42.3

-150 4.0 0. 303 0. 746 ll.2 24.8

-i00 14.7 0. 479 i. 24 8.93 20.9

-50 38 0. 652 1.73 6.24 16.6

(a) Reference 64.

These data are presented as isothermal pressure-composition

and isobaric temperature-composition plots in Figures IV-46, IV-47, IV-48,

and IV-49. Additional isobars at 150 and 500 psia have been constructed for

each system by interpolation.

Report DAC-60510-FI Page IV-61


Volume III

"uI°S u1_zO / (diS) eH _

oh _ ,-_ 0

I
_ _° ,_
oE

o
\ o

,,D
_._N
0 _

o 0 0


o o2
u_

u_

< _'_
o _o°_
('w

_ m

oo 0 _

I
o o 0 <] >
- ,_ °

um_.I_H _uooa_ d _IOIAI

Page IV-62 Report DAC-60510-F


Volume III

._ ,-_

0,_
_0

_o
o

jN
02 4_

g4 .,.4

_._

• r-I _$1

409

O 0)
V-4 4_

>
V--4
<] o 0 n

o
• .

tun.tlOH _uo_ao d _lOF_

Report DAC-60510-F1 Page IV-63


Volume III

"ulos u.z'e.zO/(cI_S)ZN _
o O
o 0

oo
\ 0 _

o
o _z
N

o_
o "._'o

o
\ .w,t

e0

j uN

<

o
¢q C _ _ .,-,
0

o
0

0
o
o

I
0
0
_.n

[]
0

0
o
o

I
0
o
Lr_

,q
oo
I

o _'_ _1_ ,.o


oo o

Page IV-64 Report DAC-60510-1_I


Volume III

"uloS _-IO / (c:ITS)ZN Do

0
0 0 LO
0

I / t_
0 _:_
o

0
u_
0
0
0
0
0
0
['.,..-
/ i !

_s
0 0 n / j 0 0"_

p < .11
0
•_ ,-_
o T m 0
o,...i
0 _
_o
o o
I I 0

,-=t
"i
4.J

° I
I
I
I
U 0

_'_ j _ #-- u_

I
/ /
/ /
u_

T
/ f >
!

..._J
.I / j 0
0 .,-,i

!
0
oO 0

u_o=_TN _u_=_cl _IO_

Report DAC-60510-F'I Page IV-65


Volume III

D. SOLUBILITY DATA FOR PRESSURANT GASES


IN PROPELLANT FUELS

Pertinent physical properties for the fuels considered here are

listed in Table IV-16. The tabulated solubility data and/or solubility data

plots for the fuel-pressurant systems that are available are presented in

the following sections.

I. Aer ozine 50 -Ammonia

See Section 3.

2. Aer ozine 50-Helium

See Section 3.

3. Aer ozine 50- Nitrogen

The solubility of helium, nitrogen, and ammonia in Aerozine-

50 fuel blend (50 wt_0 NzH 4 - 50 wt_0 UDMH) is shown in Table IV-17. These

data are from Reference 65. Figures IV-50 and IV-51 show data for helium

and nitrogen solubility at higher pressures, which were reported by Aerojet-

General Corporation (References 38 and 39).

4. Ammonia -Helium

See Section 5.

5. Ammonia - Nitrogen

The solubilities of both helium and nitrogen in liquid ammonia

were measured by Astropower Laboratory for this Design Guide, under

Contract NAS7-548. The solubility data for these two systems are tabulated

in Tavle IV-18; experimental details may be found in Reference 46. The

results reported in the table are obtained from duplicate analyses for two

successive samples; agreement of these values within experimental error

was accepted as indication that solution equilibrium had been attained.

These data are presented as isothermal pressure-composition

and isobaric temperature-composition plots in Figures IV-5Z, IV-53, IV-54,

Page IV-66 Report DAC-60510-FI


Volume III

I"_ I"- _ 0 ,_ I_- I_- 0 I_-


_I_ O0 O0

O'. O O'. N

_ oo_ e_
,--_ I"- eq o0 O,.1 O0 _'_ OO _1_ o0 ¢)
I I m ._v

o-. _ . od o _ c:; _ o', r<


-_O ..O O0 O u_ .-'4 O'. D- oo
i i ,.o I

M .--I
4-;,
m
m CO O0 O0 D- e¢_ Ox ¢)
v
M o N
.._ O"
Z I I ,.o ,o
<
,.O ,'_ _ I"_ O 1"- _ D.1 O0 O"

L_
,--_ _ ¢,q ee", O O'x 09 O u", 0
mo
0
_O
,--i
! m O0
> m _I _ O" _ O0 00 _1_ ¢'q ,-_ ¢'.1 _D oO 0 i_-
I
0
M 0 u_ 0 oO

<
> _ _ _ _ _ _ _ CO
0
_o_ooogoo

Z Z _
0
0

"_ m o o z N o m o m
©

._ ._
I

mJ _0 _I
0 I-_

O .-_ _._ _ 0

v_
_ o r_ _ _ 0

o _ _ _ _b, _ o _ _ _ ¢_
O _ _ m ,el O O O
_ .o _ _ _ _o _ _ _ _ o_ _..
v

Report DAC-60510-FI Page IV-67


Volume III

TABLE IV- 17

SOLUBILITY OF AMMONIA, HELIUM AND


NITROGEN IN AEROZINE 50

Pre ssurant Temperature Pressure Concentration


Gas OF psia Mole Percent

Ammonia 70.5 44.4 0.095 ± .004

Ammonia 57.5 38.0 0.098 ± .004

Helium 71.5 63.6 0.0011 ± .003

Helium 33.0 60.7 0.0007

Nitrogen 70.0 86.0 0.0030

Nitrogen 3Z.0 79.4 0.0030

TABLE IV-18

SOLUBILITY OF HELIUM AND NITROGEN


IN LIQUID AMMONIA

Mole Percent Concentration

Test Vapor Pressure He lium Nit r ogen


Temperature of Propellant
o F psia(a) 300 psia 700 psia 300 psia 700 ps ia

-I00 1.3 D D 0.030 0.070

-50 7.5 O.0O9 0.021 0. 067 0.136

0 30 0.015 0.044 0. I00 0.225

25 54 0.027 0.063

50 89 0.031 0.087 0.130 0.345

(a) Reference 57.

Page IV-68 Report DAC-60510-FI


Volume III

u.m.ti_ H _uo_.x_d _IOI, X

O I/3 O la_
tM
O
c_ d d d O

txl

t_
0

ld3

¢II

0
0
O

0._

0 I

o
O

I o
¢I1 0

O
tl,

4.a
I"- °_4 el0

0 0

i
¢',1

O
I
0 t_ t/_ u'3 O

"ulos farad / (dif_) _H _

Report DAC-60510-FI Page IV-69


Volume III

ue_o.=_3N _ue_-,g d eIOI_

°F.4

.,,.4

LF_

0 OU'_
l'- O
L,) ¢_

,_

o
al

•'_ _

0
U_

t_
>

-,,,4
0

0 O

_ c_

"UlOS uxe_o / (diS) _N _

Page IV-70 Report DAC-60510-F1


Volume III

"UlOS m-eaO / (diS) aH o0

u_ o
o Ln 0

o
o

o 0
o o

o .,.-i
o
°!
0,.-4
o
eq
°_.-_ 0 _

I _o
4_
m
m

o
e,l

1 m

o
o
¢xl
0
_) o_

o
o _ o o
o 0 laq o
u_ 0 6.1 LV_ o
o
!
_d
o [] 0 <l U'5
!

I:m
.r.4
o
0 0 0 0

c; c; c; c_ c_

um!IaH luo._aod OlOlN

Report DAC-60510-FI Page IV-71


Volume III

0.10--
-- 1.25
A 15o psia (Calculated by Interpolation)

O. 08 --
O

0
30O

5oo
/
/
(Calculated by Interpolation) __ 1.00
O
tn
[3 700

O. 06 -- ____0.75
,--4

u u3
0. 04 -- -- 0.50
Q) Q)

%)
%)
O

0.02 --
rr'" 0.25

---£x
_mlm

0__

-60 -40 -20 0 20 40 60

a_allf
Temperature OF

Figure IV-53. Isobaric Temperature-Composition Diagram For


The System Liquid Ammonia-Helium

Page IV-7Z Report DAC-60510-FI


Volume III

atrn.

I0 2O 3O 4O

0.35-- i 1 i

0.30--
I// -- 4.0

/
O - 100°F

[] -50°F
0.25 _
O 0°F
3.0
A 50°F
0
0.2O
Z E

2.0
0.15

C
Y F_

Z
0.10 r
C_

1.0

0.05

0 I00 200 300 400 500 600

Total Pressure psia

Figure IV-54. Isothermal Pressure-Composition Diagram for


the System Liquid Ammonia-Nitrogen

Report DAC-60510-FI Page IV-73


Volume III

"ulos _n_.IO / (cI,T.S)ZN oo

o o 0 o
o

m o
tn

\ I
\ 0

\ _0

\ .,-I

OD
o

0
.,--4
\ o

0
0

_'_
'

0 0

0 0 \ _ "!
(D
e4 0_ -_"0
o ! E ¢_ .,--4

o
F_
E_
o
cd \\ L o
uth
u o i
t_ c_

o o o o u%
un o o o _4
! t_
I

<] o 0 []

o
o

T
if1 o co o _ o ct_ o
e_ e4

uaNo_ M _uaoaacI alol_ I

Page IV-74 Report DAC-60510-FI


Volume III

and IV-55. Additional isobars at 150 and 500 psia have been constructed for

each system by interpolation.

6. Diborane =Helium

See Section 7.

7. Diborane =Nitrogen

The solubilities of both helium and nitrogen in liquid diborane

were measured byAstropower Laboratory for this Design Guide, under

Contract NAS7=548. The solubility data for these two systems are tabulated

in Table IV-19; experimental details may be found in Reference 46. The

results reported in the table are obtained from duplicate analyses for two

successive samples; agreement of these values within experimental error

was accepted as indication that solution equilibrium had been attained.

TABLE IV- 19

SOLUBILITY OF HELIUM AND NITROGEN


IN LIQUID DIBORANE

Mole Percent Concentration

Test Vapor Pressure Helium Nitrogen


Temperature of Propellant
o F psia(a) 300 psia 700 psia 300 psia 700 psia

=200 1 0. 084 0. 173 11.5 28.9

-150 9 0. 183 0. 468 7.78 19.6

-i00 43 0. 348 0. 929 5.97 16.6

=50 II0 0. 448 1.47 4.05 13.9

(a) Reference 66.

These data are presented as isothermal pressure-composition

and isobaric temperature-composition plots in Figures IV-56, IV-57, IV=58,

and IV=59. Additional isobars at 150 and 500 psia have been constructed for

Report DAC-60510-FI Page IV-75


Volume III

atm.

10 20 30 40

I i I
1.4 I
0 - 200°F

i0
E] 1%0°F

/
1.2

0 - I 00°F

A - 50°F
1o0 --

0.8
m / )

O
o
u3

o
O. 6 --

// _q

0.4

0.2

I00 200 300 400 500 600 700

Total Pressure psia .v,.,

Figure IV-56. Isothermal Pressure-Composition Diagram for


the System Liquid Diborane-Helium

Page IV-76 Report DAC-60510-FI


Volume III

I. 4 --

A 150 psia (Calculated by Interpolation)

0 300 I0

0 500 Calculated by Interpolation)

[] 700

0
[n

./
0 8--

F-
_- 0.6 [/3

(9

0.2

-200 -I 75 - 150 -125 -100 -75

Temperature OF

Figure IV-57. Isobaric Temperature-Composition Diagram for


the System Liquid Diborane-Helium

Report DAC-60510-FI Page IV-77


Volume III

"uI°S ua_.IO / (tilLS) ;_N _

0 0 0
0
0

o-_
! o t.
I_-

0
[_

, \
o,,_

t" _ o
C
ur
o_
.,.4 Z
0
oh 0
cd
.,._

0 _,o
p'o
0
c

0 0 0
\
0 0 0 0 r<
0 _ 0 0
0
| I I \
o [] 0 <1
c
I

u_o._. N _ue_e d _lOl_I

Page IV-78 Report DAC-60510-FI


Volume III

"uIOS tu_aO / (dZS) ZN _

0 0 0
0 un 0 0
0

, l
I
/ ]I
?/ "
0
i

0
Lr_
0
o o°
o / / ,
t_ u_
/ /
<_
0 o
0

o
°i /
/
I
I

°
o

, o

/
D
/ o_

0
i _E
_d
0 I

I I
i I
I1)

/ __t13
p_
E
t/3

I I

, /
I

/
0
--0

u_oa_ N _uooa_cI _IOiAI

Report DAC-60510-FI Page IV-79


Volume III

each system by interpolation. It is noted that the solubility of nitrogen in-

diborane appears to deviate from Henry's Law at the higher concentrations

of pressurant, and the -200°F plot in Figure IV-58 is curved.

8. Diborane..- Hydr ogen

The solubility of hydrogen in diborane has been reported

(Reference 67) in the temperature range of -260 ° to -130°F and the pressure

range of 100 to 600 psia. Data derived from this paper is presented in iso-

thermal and isoboric plots in Figures IV-60 and IV-61.

9. Ethane -Helium

See Section 10.

10. Ethane-Nitrogen

The solubilities of both helium and nitrogen in liquid ethane

were measured byAstropower Laboratory for this Design Guide, under

Contract NAS7-548. The solubility data for these two systems are tabulated

in Table IV-Z0; experimental details may be found in Reference 46. The

results reported in the table are obtained from duplicate analyses for two

successive samples; agreement of these values within experimental error

was accepted as indication that solution equilibrium had been attained.

TABLE IV-20

SOLUBILITY OF HELIUM AND NITROGEN IN LIQUID ETHANE

Mole Percent Concentration

Test Vapor Pressure He lium Nitr og en


Temperature of Propellant
oF psia(a) 300 psia 700 psia 300 psia 700 psia

-200 0.9 0.07 0.18 10.6 27.1

-150 7.1 0.15 0.33 7.40 17.7

-i00 31 0.27 0. 64 5.61 14.3

-50 91 O.38 1.09 4.71 12.3

(a) Reference 68.

Page IV-80 Report DAC-60510-FI


Volume II1

Arm.

10 20 30 40
2.8
[ 1 I I

-35
2.4- _ 132°F

Q 174°F-- -30

2.0 -
A
o
0
/ f 96° -
1.6 -
-25 !

I])
U
/// -20

1. 2 " /
O / 15

__/ / _236OF
/ _ f _56°F
0.8-

10

0.4 "

. -0

0 100 200 300 400 500 600 700

Total Pressure, psia


oIv_$

Figure IV-60. Isothermal Pressure- Composition Diagram For


the System lJiquid Diborane- Hydrogen

Report DAC-60510-FI Page IV-81


Volume III

"ul°S _-_0 / (cI.T,S)ZH _

u_ O tf_ C) U_ O
(Y3 (w3 N eq .-w u_ 0

I I
0 •_ 0

0
! 0,_

0
0
QO

oo E

_.0
!

I [ l I I I !

ua_o_pA H _ua_aa d alOF_

Page IV-8Z Report DAC-60510-F1


Volume III

These data are presented as isothermal pressure-composition


and isobaric temperature-composition plots in Figures IV-62, IV-63, IV-64,
and IV-65. Additional isobars at 150 and 500 psia have been constructed for
each system by interpolation.

11. Ethane -Hydrogen

This system has been studied by Katz et. al. (Reference 69}.

Their results are given in Figure IV-66 as an isothermal plot of liquid phase

composition versus pressure over the temperature range of -275 ° to +50°F

and pressure range of 300 to 8000 psia. Table IV-21 summarizes all their

experimental data in terms of equilibrium constants K* for both components,

between the two phases. This data has been used to construct isothermal

and isobaric solubility diagrams showing the expanded liquid phase region

below 2000 psia (Figures IV-67 and IV-68). The isothermal curves of Figure

IV-67 have been extrapolated to zero hydrogen concentration using ethane

vapor pressure data from Reference 92.

12. Ethylene-Helium

See Section 13.

13. Ethylene -Nitrogen

The solubilities of both helium and nitrogen in liquid ethylene

were measured by Astropower Laboratory for this Design Guide, under

Contract NAS7-548. The solubility data for these two systems are tabulated

in Table IV-22; experimental details may be found in Reference 46. The

results reported in the table are obtained from duplicate analyses for two

successive samples; agreement of these values within experimental error

was accepted as indication that solution equilibrium had been attained.

These data are presented as isothermal pressure-composition

and isobaric temperature-composition plots in Figures IV-69, IV-70, IV-71,

K A = Mole % A in vapor/Mole % A in liquid.

Report DAC-60510-FI Page IV-83


Volume III

"UlOS u-re-_O / (cIff, S) _H _

co ,.o ,_ o

\ 1 o
i_-

o 0
o o

o
o
i._

1
o
,,..i
o
.,-4 _

o_
ffl

\
o
o _1 °,-I

\ o
0

0 0 0
o 0 0 0 0
-- 0 _ 0 0 o_
I I I I
o
--o [] 0 q-- o

,,D
I

>

um_.I_H lu_d _IOF7

Page IV-84 Report DAC-60510-FI


Volume Ill

"UlOS uiw_O / (clJ_S)°H aa

oo ,.o ,q, t,4 o


o

r_

o°i
• ,.4 •

o o

_o_
(1) ._

['* o
°,-4

o_

,.D
!

7 >

o
o _M
!

u_m!Io H J,uo:,-_OcI alOlN

Report DAC-60510-FI Page IV-85


Volume III

atrn.

I0 20 30 40

I I T I 300
Z8

O "200°F

Z4 [] -150°F

C} "100°F
/
20 A -50°F / 200

/ O

E
a_
16 ]
O_ L)
0

0
12

__,oo 0_
E-,
U_

Z
L)
(,,j

/ 50

I. 0
0
0 I O0 2.00 300 4(10 5 )0 6q 0 700

Total Pressure psia


¢¥4_9

Figure IV-64. Isothermal Pressure-Composition Diagram for


the System Liquid Ethane-Nitrogen

Page IV-86 Report DAC-60510-F1


Volume III

"ulos Lu_o / (cI.T.S)ZiXlaa

0 0 CD
0 0 0 0 O_
u'h

o
I I
Y ' 'F' , 0

I
I bJO

/ !

I 0 _

o E_ °

/,i
__<_ 0 I:_' hi)
o_
7 oz
I O _
i

/ ¢) _ "Ul

/ I 1,1 _

U
°
,r-I

_ o ._m
/ _

I
I /
U3
t_
_
t

I /
/ O
0

!
xt' C) ,,O t'q cO

ua_o=_.Ixl _ua,_=acl alOe%!

Report DAC-60510-FI Page IV-87


Volume III

TABLE IV-21

LIQUID-VAPOR EQUILIBRIUM CONSTANTS FOR THE


SYSTEM ETHANE-HYDROGEN

Total Pressure, psia


Temperature
OF 250 500 1000 2000 4000 8000

+50 KH 2 12.1 6.45 3.21 z. 135 (2500)


KC2H 6 0. 922 0. 657 0. 567 0. 632 (2500)
0KH 48. 8 24.4 12.2 6.12 2.82 1. 853 (6000)
KC_H 6 0. 896 0. 534 0. 347 0. 264 0. 296 0.616 (6000)

- 50 KH 2 75.4 36.8 18.1 9.05 4.49 2.17


KCzH 6 0. 424 0. 246 0. 148 0.113 0. i16 0.219

- I00 KH 2 101.2 49.0 24.3 12.4 6.35 3.38


KC2H 6 0. 150 0. 0850 0. 0545 0. 0432 0. 0463 0. 0750

- 150 KH 2 124.4 62.2 31.3 16.3 8.75 4.86


KC2H 6 0. 0362 0. 0206 0. 0143 0. 0127 0. 0157 0. 0277

- 200 I<H 2 160 83. O 43. 2 23.6 13.1 7.45


0. 00462 0. 00314 0.00266 0. 00272 0. 00432 0. 00934
KC2H 6
-250 KH 2 238 129 7O. 8 40.0 22.7 13.5

-275 KH 2 320 179 i00 57.4 33.3 19.8

Values in parentheses show pressure for indicated K.

TABLE IV-22

SOLUBILITY OF HELIUM AND NITROGEN IN


LIQUID ETHYLENE

Mole Percent Concentration

Test Vapor Pressure Helium Nitrogen


Temperature of Propellant
oF psia (a) 300 psia 700 psia 300 psia 700 psia

-200 2.5 0. O56 O. 136 9.07 24.6

-150 16 0. 143 O. 323 6.52 16.4

-100 62 0. 220 O. 578 4.67 13.3

-50 176 0. 230 1.01 2.61 11.1

(a) Reference 70.

Page IV-88 Report DAC-60510-FI


Volume III

•tu_V

0
o ¢q ,.o
o t'4 ,.o
o0
,.o (-4 .-_ ,.o _ ,-- E
i:m

t/3 C_
o_ O _

,,D ._ 0

O_

0 i
0

_o
U3
0
O
E o O4
¢4 u_ P_
m
+
O

_n
,1= _')
t,4 0

(3
(3
\\\ ,.D

o_
,'%\ I%!
,.D

>
I

"\\&\
._..i

oo o o o o oo o o o o O
oo o o o o oo o o o o O
oo o o o o o 00 _ _ o_ e4 ,-.-i

_Isd _a lrts s a._cI

Report DAC-60510-FI Page IV-89


Volume III

"UTO_ uu'_.xO / (diS) ZH 0o


0 0 0 0 0
0 CM O

r I i
O
O
CD
0 ¢M
0

Lt_
\ O
O

O
O

O O _
._ O
O

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Page IV-90 Report DAC-60510-F1


Volume III

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Report DAC-60510-FI Page IV-91


Volume III

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Page IV-92 Report DAC-60510-FI


Volume III

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Report DAC-60510-FI Page IV-93


Volume III

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Page IV-94 Report DAC-60510-FI


Volume III

"UlOS tUeaD/(dJ_) ZN aa

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Report DAC-60510-FI Page IV-95


Volume III

and IV-72. Additional isobars at 200 and 500 psia have been constructed for

each system by interpolation.

14. Ethylene -Hydrogen

This system has been studied by Katz et. al. (Reference 69).

Their data are given in Figure IV-73 as an isothermal plot of liquid phase

composition versus pressure over the range of -Z50 ° to 0°F and 200 to 8000

psia. Table IV-Z3 summarizes all their data in terms of equilibrium constants

K _" for both components, between the two phases. This data has been used to

construct isothermal and isobaric solubility diagrams showing the expanded

liquid phase region below Z000 psia (Figures IV-74 and IV-75). The iso-

thermal curves of Figure IV-74 have been extrapolated to zero hydrogen

concentration using ethylene vapor pressure data from Reference 92.

15. Hydrazine-Argon

See Section 17.

16. Hydrazine -Helium

See Section 17.

17. Hydra z ine -Nitrogen

Solubility data for these three systems have been reported

(Reference 71) in the low pressure region of 15 to 30 psia, and are sum-
marized in Table IV-24.

The systems hydrazine-helium and hydrazine-nitrogen have

also been studied at pressures up to 700 psia (References 38 and 39). Iso-

baric solubility plots are shown in Figures IV-76 and IV-77. This same data

has been used to plot the isothermal pressure-composition diagram given in

Figures IV-78 and IV-79; note that all these isotherms extend essentially

from the origin because of the low vapor pressure of hydrazine at the tem-

peratures involved.

K A = mole % of A in vapor/mole % of A in liquid.

Page IV-96 Report DAC-60510-FI


Volume III

u_]V

0 ,.0
0 C'_ -.0
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_isd 'oanssoa d

Report DAC-60510-F1 Page IV-97


Volume III

TABLE IV-23
LIQUID-VAPOR EQUILIBRIUM CONSTANTS FOR THE
SYSTEM ETHYLENE-HYDROGEN

Pressure, psia
Temperature
oF 250 5O0 I000 2000 4000' 8OOO

0 KH 2 17.1 8.10 3.94 2. 15 (3000) 1.42 (3500)


KCzH 4 0. 863 0.600 0.496 0.581 (3000) 0. 764 (3500)

-25 KH 2 23.1 11.25 5.50 2.43 I. 53 (5000)


0.66O 0.431 0.338 0.408 0. 652(5000)
KC2H 4
KH 56.0 28.2 14.4 7.35 3.51 I. 50 (7000)
- 50 KC2H 4 0.764 0.452 0.284 0.214 0. 236 0. 543 (7000)
-I00 KH 84.2 41.3 21.2 10.8 5.75 2.91
KC2H4 0.320 0. 189 0.121 0.0924 O. 0883 0. 148

KH 123.6 62.0 31.8 16.5 8.82 4.95


-150 KCZH4z 0.0780 0. 0500 0.0346 0.0293 0.0305 0. 0456

KH 147 75.1 38.6 Z0. Z I0.9 6.25


- 175 KC_H 4 0.0408 0. 0268 0.0201 0.0179 0.0212 0. 0328

188 96.4 50.3 26.6 14.60 8.75


-200 KH 2
3O8 159 82.7 44.8 28.5 18.7
-250 KH 2
Values in parentheses show pressure for indicate, K°

TABLE IV-24

SOLUBILITIES OF ARGON, HELIUM AND


NITROGEN IN LIQUID HYDRAZINE

Argon Helium Nitrogen

Temp p(a) Mole % p(a) M°le3%0 p(a) Mole %


OF psia xl03 psia xl psia xl03

41.00 16.77 1.04 18.12 0.51 16. 82 0.56


31. 19 2.20 32.21 1.08 30.61 1.21

68.02 13.45 1.03 16.76 0.52 15.41 0.69


26.42 2.13 30.04 I. I0 16.33 0.71
28.97 1.45
30.29 1.51

95.05 15. 52 I. 44 16.01 O. 57 15.93 0. 84


29. 57 2.85 19.27 0.68 31.01 i. 8O
29.29 1.17
33.89 1.44

(a) Partial pressure of the pressurant gas.

Page IV-98 Report DAC-60510-FI


Volume III

•UlOS ua_aO / (dJi_) ZH _


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Report DAC-60510-FI Page IV-99


Volume Ill

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Page IV-100 Report DAC-60510-FI


Volume III

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Report DAC-60510-FI Page IV-101


V olume III

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Page IV-102 Report DAC-60510-FI


Volume III

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Report DAC-60510-FI Page IV-103


Volume III

¢q
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Page IV-104 Report DAC-60510-FI


Volume III

18. Hydrogen (Normal)-Helium

See Section 19.

19. .Hydrogen (Equilibrium) - He lium

Hydrogen exists in two modifications, ortho and para, which

have measurably different physical properties. In the liquid state these

forms give rise to two mixtures of practical significance; "normal" hydrogen

has a 75% ortho-25% p_ara composition representing the room temperature

gas equilibrium mixture, and "equilibrium" hydrogen has the composition

0. 21_/0 ortho-99.79% para which is stable at Z0.40°K. The solubility of

helium in both mixtures has been studied extensively by Sonntag et. al.,

(References 12 and 72) and the data used here is taken from them. These

authors also discuss critically the prior work on these systems.

For the purpose of this Design Guide, the _phase com-

positions of both normal and equilibrium hydrogen-helium systems were

found to be almost identical within experimental error, and solubility data

for the more extensively investigated normal system may be taken as repre-

sentative of both. However, measurable differences were found between the

vapor phase compositions of the two systems at higher temperatures, and

hence the equilibrium hydrogen data is included in the regions where these

differences exist.

Table IV-Z5 presents the experimental data, presumably

smoothed, for both phases of the normal hydrogen system. Figures IV-80

and IV-81 give complete isothermal and isobaric plots of these data; expanded

diagrams of the data in the liquid regions are shown in Figures IV-82 and

IV-83.

In the equilibrium hydrogen system, minor increases in the

helium vapor phase concentrations over those for normal hydrogen were

measured above 20.40°K, and are attributable to the slightly higher solvent

vapor pressures. The three graphs, IV-84 through IV-86, show comparative

isothermal plots for the two systems in the range of 20.40 ° to 31.00°K. It

Report DAC-60510-FI Page IV-105


Volume III

TABLE IV-25

SOLUBILITY OF HELIUM IN NORMAL HYDROGEN

Mole % He Mole % He
Temperature Pressure Tempe rature Pressure
(OK) (psia) Liquid Vapor (OK) {psia) Liquid Vapor

15.50 49.5 -- _3.78 29.00 127.0 0.91 14.03


75.0 0.29 95.51 151.0 1.50 21.92
100.0 0.46 96.31 175.0 2.20 27.75
125.0 0.51 96.77 200.0 3.07 32.93
150.0 0.55 97.02 250.0 4.59 39.54
175.0 0.64 97.14 300.0 6.21 43.70
200.0 0.71 97.29 400.0 9.63 47.95
250.0 0.82 97.41 500.0 13.35 49.20
300.0 0.87 97.48
30.60 300.0 7.29 30.32
17.07 56.5 0.36 89.67 400,0 13.24 32.60
75.0 0.43 91.86 450.0 17.95 30.36
I00.0 0.57 93.30
31.00 176.5 1.49 11.28
125.0 0.72 94.12
199.0 2.51 15.59
150.5 0.80 94.64
250.0 4.78 22.58
175.0 0.89 95.03
300.0 7.49 26.57
200.0 1.00 95.15 325.0 8.73 27.55
250,0 1.14 95.56
350.0 11.03 27.85
300,0 1.31 95.82
375.0 12.93 27.59
400.0 1.51 95.90
400.0 15.64 25.78
20.40 35.0 0.34 53.60 413.0 20.87 21.85
50.0 0.41 65.45
31.50 177.0 1.27 7.67
75.0 0.61 75.40
200.0 2.30 11.94
100,0 0.84 80.30 225.0 3.61 15.64
125.0 1.05 83.20
250.0 4.83 18.35
150.0 1.30 84.80
275.0 6.26 20.30
175.0 1.54 86.03
300.0 8.18 21.37
200.0 1.67 87.13 325.0 10.47 21.49
250.0 2.05 88.41
351.0 16.59 17.58
300.0 2.36 88.98
400.0 2.96 90.08 31.90 174.5 0.81 4.00
500.0 3.39 90.35 200.0 2.07 8.31
220.0 3.17 11.75
23.00 50.0 0.38 37.00
238.5 4.29 13.86
75.0 0.75 53.44
250.5 4.99 14.82
I00.0 1.15 62.90 261.5 -- 15.62
125.0 1.36 67.87
275.5 6.87 16.19
150.0 1.72 71.75
289.5 8.71 16.35
175.0 2.15 74.35
300.0 10.10 15.88
200.0 2.39 76.30
308.5 12.02 --
250.0 2.91 78.78
300.0 3.55 80.55 32.50 188.5 0.89 3.12
400.0 4.58 82.34 200.0 1.68 4.80
500.0 5.46 83.30 220.0 3.10 7.45
242.0 5. 09 --
26.00 81, 0 0.67 22.60
250. 0 5.99 --
100. 0 0.97 33.50 258.0 6.75 --
125. 0 1.43 43.37
150 0 1.92 49.77
200. 0 2.86 56.90
250. 0 3.64 62.67
300. 0 4.76 65.65
400. 0 6,64 68.58
500. 0 8.48 70.02

Page IV-106 Report DAC-60510-FI


Volume III

4 _: d _ oo

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Report DAC-60510-F1 Page IV- 107


Volume III

o
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Page IV- 108 Report DAC-60510-F 1


Volume III

cc He (STP) /Gram Soln.

111 220 326

150

t_

100 6.80

5O 3.40

Mole % He in Liquid

Figure IV- 82. Isothermal Pressure- Composition Diagram for


the System Normal Hydrogen-Helium, showing
Liquid Region on Expanded Scale

Report DAC-60510-FI Page IV-109


Volume III

cc He (STP) / Gram Soln.


22O 430 634 830 1020 1200

34
t I :I

32 r _ r

f
/ f
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f
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18

16

1
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Mole % Helium in Liquid

Figure IV-83. Isobaric Temperature-Composition Diagram for


the System Normal Hydrogen-Helium Showing
Liquid Region on Expanded Scale

Page IV-II0 Report DAC-60510-FI


Volume III

•u.qV

o _ _t _ _ o

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Report DAC-60510-F1 Page IV-Ill


Volume III

"ur4_

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Page IV-112 Report DAC-60510-FI


Volume Ill

cc He (STP) / Gram Soln.

533 1460 2240


5OO 34. 0

27.2

4oo _Z._
_--_ 20.4

300 Liquid/

_;.a'Vapor
13.6
200 -

100 6.80

O Equil. H 2

A Norm. H 2

0
10 I 20

Mole Percent Helium e_ay_

Figure IV-86. Comparison of Normal and


Equilibrium Hydrogen Data
at 31. 00°K.

Report DAC-60510-FI Page IV-II3


Volume III

may be noted that the authors felt that slight measured differences in liquid
phase helium concentration at 31.00 ° were above experimental error (note

Figure IV-86). They also indicated that ortho_ para conversion during the

experimental work would have been negligible and should not have perturbed
the results.

20. Methane -Helium

The system methane-helium has been extensively studied by

Heck and Hiza (Reference 73), from the methane triple point to near the

critical temperature of methane. Their complete experimental data is pre-


sented in Table IV-26.

Because the above compilation is so comprehensive, only


selected data of present interest, in the range of -290 to -180°F and0 to 700

psia, are given here in graphical form. These isothermal and isobaric com-

position plots are shown in Figures IV-87 and IV-88.

21. Methane-Hydrogen

The data of Katz et. al. (References 75 and 76) have been

used for this binary system. Complete two-phase isothermal and isobaric

composition diagrams are presented in Figures IV-89 and IV-90. Similar

plots showing their data for the liquid region on an expanded scale have also
been constructed (Figures IV-91 and IV-92).

22. Methane-Nitroge n

Isobaric equilibrium concentrations of the methane-nitrogen


system over the pressure range of 15 to 700 psia and between -320 and -120°F

are plotted in Figure IV-93. This graph, taken from Reference 58, employs
data from References 77 and 81, and has been used to construct the isothermal

pressure-composition diagram for the liquid phase in the region of 0-600 psia,

which is shown in Figure IV-94.

23. Monomethylhydrazine -Argon

See Section 25.

Page IV-I14 Report DAC-60510-FI


Volume III

•._l'--_l'_l,e_O i 0"-o0 i I_ . i • i . i i ....


........ _o_,_ :.d_ _4_
0 .,.4

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Report DAC-60510-F1 Page IV-ll5


V olu.n_eIII

•uio S tn_© / (cI.T,S) aH _0

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Page IV- 116 Report DAC-60510-F 1


Volume III

1.4

1.2

•r-_
1.0
"2
/ 15

J 0

I0 _
__u 0.8 /
J
u

o.6 _ __
0.4 f

0 0

-275 -250 -225 -200

Temperature OF ,_,xr

Figure IV-88. Isobaric Temperature - Composition Diagram for


the System Liquid Methane-Helium

Report DAC-60510-FI Page IV-If7


Volume III

7000

6000

/ \
5000 -'

,I / '
4000 . -

/
3000 -
Q)

2000 - i
1000"

Z: " j
0 I0 20304050607C, 8090100

Mole Percent Hydrogen


cV#$J

Figure IV-89. Isothermal Pre s sure - Composition


Diagram for the Binary System
M ethane -Hydro gen

-130 I l_,,J
-14o Ix,_ ,l'_x
-15o 131_1 iL,- D

-,oo-ll,hlK_.___:
•-ii'i'I ,i I:t n-i%"Oo
:.
-170 "- %÷-
V

l,_
-,8o
-190
illl#ll '"
o -200 lllI#ll /
-z,o Illllll I
Jlllil L
-zz0
11111/I (
-230
-24o II!11li
-_5o IIIII I
-2_o IIiil II
-_70 11111 II
-2_0 IIIli/1
-_-9o IIIJl l
lift l ":',4_'...
- 30')
100

Mole Percent Hydrogen


ev_

Figure IV-90. Isobaric Temperature - Composition


Diagram for the Binary System
Methane-Hydrogen

Page IV-118 Report DAC-60510-FI


Volume III

"UlO S tu_aD / (diS) ZH _

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O0 _0 04 0 O0 o
04

ua_o.tpX H luanzo d alOl/q

Report DAC-60510-F1 Page IV-119


Volume Ill

18

_.d)
16
c_
o
14
O / u_

>, 12

_) 10 50

_ 8 O3

0
o
2 6
U

4
5O

0 I I I I I l I I 0

-Z50 -ZOO - 150

Tempe ratur e o F ,v_vo

Figure IV-92. Isobaric Temperature -- Composition Diagram For


the System Liquid Methane-Hydrogen

Page IV-I20 Report DAC-60510-FI


Volume III

bo

C_

0
O_b0

0 _-_

!'

L} q._

I
>

bO

0
0 0 0 0 0 0 0 0 0 0
0 0 _ CO _ _0 '._ _t' ,'_ N

Report DAC-60510-FI Page IV-IZI


Volume III

"uTos m'es-O / (cl:TS) ZN _

o o o
o Lrl o
an
o

I I! I b.-

0
r_
0 0
o o
00 ,,o o t_
o

\
o ,,.o
°_

0
o
o
\ \ 0

\ o
o
o

\ \
url
0 '_

o .v-,4
an
t_

\ \ \ \
oo

< 0 \ \ \ tD
0
t'q \ ,, o
o N
I o
0

0
o
h

0
!

4
o_
!
>

u_o_l._NI luaaz:acI gIOF_I

Page IV-ig2 Report DAC-60510-FI


Volume III

24. Monomethylhydrazine -Helium

See Section 25.

25. Monomethylhydrazine -Nitrogen

Solubility data for these systems have been reported (Refer-

ence 71) at pressures of about 15 and 30 psia in the temperature range from

-4°F to 77°F. The available data are summarized in Table IV-27. (N. B.

The pressures given in this Table are partial pressures of the pressurant

gas, not total system pressures.)

The systems monomethylhydrazine-helium and monomethyl-

hydrazine-nitrogen have also been investigated at total pressures of 300 and

700 psia over the temperature range from 20°Fro 175°F (References 38 and

39). Isobaric solubility plots for these systems are presented in Figures

IV-95 and IV-96. Isothermal pressure-composition diagrams have been

plotted from this data and are shown in Figures IV-97 and IV-98.

More recent work (Reference 31) on the solubility of helium

in monomethylhydrazine is in essential agreement with that cited above.

26. Monomethylhydrazine Hydrate-Helium

Figure IV-99 gives the available solubility data for helium in

monomethylhydrazine hydrate (References 51 and 83). The corresponding

isothermal plots constructed from these data appear in Figure IV-100.

27. Pentaborane -Helium

The solubility of helium in pentaborane has been determined

at total pressures of 500 to 1500 psig and over the temperature range of 86 °

to 303°F (Reference 83). Isothermal and isobaric solubility plots have been

constructed from this data and are shown in Figures IV-101 and IV-102.

It should be noted, in the use of this data, that there may be

some uncertainty in these results because of decomposition of the pentaborane.

These reactions, which produce hydrogen, become appreciable above about

200°F. For this reason the isothermal diagram has been plotted only to 200°F.

Report DAC-60510-FI Page IV-123


Volume III

eo o
_o
.A _d _ M

_ u'3 •_ u3
u'5 ,,D

4 ,¢ _d 6
z
z
o
o
_ t'M _1_ O0
0 ,--_ t-- "_

_z
z_ o _ d 4

°T-I

t-- u'3 _ ,.D O


_ u'3 u'3 eel
e_
!
.A .-:

<
_ i/3 _ O O O
,,D t'-.- t.n ,,D O ,_
_O

o _ .-:.A
(",,1 e¢3

o O

!"- O ,_ ',D t/l


,._ Cr-

t.: oz

O
r_

O
O O O H

& 4 _d
! D-

Page IV-124 Report DAC-60510-FI


Volume III

1.0 0.20

0.75
C
0.15
700

0 o. 50 - 0.1

E
v 0.25_
.J f 0.05
O

0
300 psia
0-
O"
n

0 50 75 100 125 150 175 200


Tempe rature, OF cyst,

Figure IV-95. Isobaric Temperature-Composition Diagram for the


System Liquid Monomethylhydrazine- Helium

2.5

2.0 0.4

0
(/3

1.5 0.3

O J Q)
e_0
O

_" 1.0
j 0.2
4_

300 psia O
Z
u 0.5 0. I
o
Cr"

0 25 50 75 100 125 150 175


Temperature, OF

Figure IV-96. Isobaric Temperature-Composition Diagram for the


System Liquid Monomethylhydrazine- Nitrogen

Report DAC-60510-FI Page IV- 125


Volume III

Atrn.

0 10 20 30 40
0.8

0.7
/ 15

]7 5°F

O. _

/
0
_0
0.5 1 .5

//
09
cd

(9

¢d
0.4 a_

o5
0.3 L

0.

0.1 i

0 1 00 200 300 400 500 600 700

Total Pressure, psia -,,,,

Figure IV-97. Isothermal Pressure--Composition Diagram for


the System Liquid Monomethylhydrazine-Helium

Page IV-126 Report DAC-60510-FI


Volume III

uago.I:_._ N _uan.la d aIo]A[

u_ _l _ ee_ e.l
0
o
I , I t
o [ o_l
0 ,.+.4
r_

_ 4J
I:11)"_
_Z
O C. ._-,I I
o 121 _
_-,_N
._ _

O _ 0_

< _ 0

. ,_

0
o
I

i--t

I I:m
.pt
o 0 o o

•UlOS tueaD / (d_L_) _N _

Report DAC-60510-FI Page IV- 127


Volume III

[] Lab Data
O Test Stand Data 0. I

,,,-4
0 720 psia

2_
0° 2--
/ 0.05

_a
320 psia
0. i-- ,--4
O
q_
U

4O 60 80 1 00 120 140

Temperature, OF e_v

Figure IV-99. Isobaric Temperature-Composition Diagram


for the System Liquid Monomethylhydrazine
Hydrate -Helium.

Page IV-128 Report DAC-60510-FI


Volume III

tu_.IOH _uo_a_cl OlO;,_

O
\
o_
0
0
b.-

.,-_

O 0 _q
0 0
0 0

0
0
L_
E;
0

0
O B I c
0
g

m _
<

O
t'q --
\o m 0 _

_m
m

O m !
>
o

O o

"uI°S ui_-IO / (d,Lf-;i OH 3_

Report DAC-60510-FI Page IV-IZ9


Volume III

'UlO_ u.r_.iD/ (d,LS) eH _

o u'_ o
U'3 0

I i

0 o 0
0

0_

\ o

o
0

0
0

,l-i

I,w
m"O

<

t_ 0 _

\
o

>

tth

u-m3I_H % _I°]AI

Page IV-130 Report DAC-60510-FI


Volume III

"uI°S u-r_'_O / (dJLS) aH ao


0 tf_
0
Cq 0
LOb

%,

0 _L0 0 _
0 .,._ 0 .,-_ 0 • ,.-4 I_)
--0

\ o
0 _)

.f-i

0 0

0
__LN o _

0
.r-i
_,..]

_4.a

Ur_

0 0 _
--t.f3 _ 0

M
0

!
>
0
-0

t_

u'3 r,_ tM 0

um_.IaH :7. °I°IAI

Report DAC-60510-F1 Page IV-131


Volume III

28. Pentaborane -Hydrogen

The solubility of hydrogen in pentaborane has been determined

at total pressures of 500 to 1500 psig and over the temperature range of 86 °

to 303°F (Reference 83). Isothermal and isobaric solubility plots have been

constructed from this data and are shown in Figures IV-103 and IV-104.

It should be noted, in the use of this data, that there may be

some uncertainty in these results because of decomposition of the pentaborane.

These reactions, which produce hydrogen, become appreciable above about

200°F. For this reason the isothermal diagram has been plotted only to 200°F.

29. Pentaborane -Nitrogen

The solubility of nitrogen in pentaborane has been determined

at total pressures of 500 to 1500 psig and over the temperature range of 86 °

to 303°F (Reference 83). Isothermal and isobaric solubility plots have been

constructed from this data and are shown in Figures IV-105 and IV-106.

It should be noted, in the use of this data, that there may be

some uncertainty in these results because of decomposition of the pentaborane.

These reactions, which produce hydrogen, become appreciable above about

200°F. For this reason the isothermal diagram has been plotted only to 200°F.

30. Propane -Helium

See Section 31.

31. Propane-Nitrogen

The solubilities of helium and nitrogen in liquid propane were

measured by Astropower Laboratory for this Design Guide, under Contract

NAS7-548. The solubility data for these two systems are tabulated in Table

IV-28; experimental details may be found in Reference 46. The results

reported in the table are obtained from duplicate analyses for two successive

samples; agreement of these values within experimental error was accepted

as indication that solution equilibrium had been attained.

Page IV-132 Report DAC-60510-FI


Volume III

"uI°S ure.IO / (d_LS) ZH _

o o o
t_ N .-_ o

I
o
o
o
o

0
o

t_

m 0
O,.Q
o

_D
\\ v

,._ o _ \ cD

0
< F.
o 0 _
m 0

T
o

m,J

°_,,I

o
o

o a0 ,.o "_ e_ o

uaBo=p&H % alO]AI

Report DAC-60510-FI Page IV-133


Volume III

"uIos tu_-tO / (dJLS) ZH oo

o o o o
o_ (',.I ,-.

I l I
O
%

CD

o
oo o .,-4 (_

O'U

O
u'_ {n i
cq O _)

E_
0 k
0
O
0)

O
o

_._
_J
o [---' _
u_

0 _

oo 4o

.,-I
o
m _
o o

u_o.lp _!1_uoo.zad OlO_I

Page IV-134 Report DAC-60510-FI


Volume Ill

"ulos Lu_=o / (diS) ZN oo

0 0 0 0
0

I I
0
0
O C u%
0
O

0
u% 0
N
p=a
0 ._
_Z

o
t_
o_
oo o
0

I1) _)

{n

<
o
O
u_

0
u_

_4
o

0
u_
eg I1)

O 0

O0 ,.0 _ e,] 0

Report DAC-60510-FI Page IV-135


Volume III

"UlOg tuleaD / (d_LS) ZN _

0 0
o o o o

o
I e_

o,-_

0
0 o_
0

_D
.,-4
0_
.,=4
E_h
_n (n 0
0
t_, ¸
O O o
O O o
u'_
@

_'_

_E

0 _

o
L_
.S
o

"7
>

0
0

e4 0 O0 _D _1_ e4 0

u_o.*]_. N _uo_zocI alOIN

Page IV-136 Report DAC-60510-FI


Volume III

TABLE IV-28

SOLUBILITY OF HELIUM AND NITROGEN IN LIQUID PROPANE

Mole Percent Concentration

Test Vapor Pressure He lium Nitr og en


Temperature of Propellant
OF psia( a ) 300 psia 700 psia 300 psia 700 psia

-150 0. I 0.099 0.226 4.97 11.2

-100 3.4 0.205 0.412 4.07 10.6

-50 13.5 0.312 0.711 4.01 I0.6

0 41 0.432 1.11 3.44 9.73

(a) Reference 84.

These data are presented as isothermal pressure-composition

and isobaric temperature -composition plots in Figures IV- 107, IV- 108,

IV-109, and IV-110. Additional isobars at 150 and 500 psia have been con-

structed for each system by interpolation.

32. Propane -Hydrogen

The data for this system has been presented by Katz et al

(Reference 69) and Sage et. al. (Reference 85). The complete experimental

data obtained by Katz is given in Table IV-29 in terms of the equilibrium

constants K* for both components, between the two phases. The combined

data of both investigators is given in Figure IV-Ill as an isothermal plot of

liquid phase composition versus pressure over the temperature range of

-300 ° to 75°F and pressure range of 250 to 8000 psia. Selected data from

Table IV-29 (Reference 69) has been used to construct isothermal and isobaric

solubility diagrams showing the liquid range below 2000 psia (Figures IV-II2

and IV-113). The isothermal curves of Figure IV-112 have been extrapolated

to zero hydrogen concentration using propane vapor pressure data from

Reference 92.

"K A = mole percent A in vapor/mole percent A in liquid.

Report DAC-60510-FI Page IV-137


Volume III

'ulos m_=O / (d/IS) OH z_

\ O

O
t_

0 -_
.,=4

0 I

¢0

c_
0_

O
cq

4_
O

o o b_
0 0 0 .a

T --! u_!
0
0
\
O
,-w © [] ©
r-:
O O

T
>

Lrmtlo H luoa.:od OlOlN

Page IV-138 Report DAC-60510-FI


Volume III

"_os ux'_.zO / (cI.'r.s) OH :aa

I o
\
\
\ oq I_

\ 0
.p.4

O O m
o o_
,..4 ¸

o
\ 0

_
o
0

\ ' _1_, _'_

°,..4 i'_
__ o _
O o o o

<1 0 0 []

O4 0
. -

m _
o

um_.l_H _u_az_cl _lOD/

Report DAC-60510-F1 Page IV-139


Volume III

"uI°S m_o / (ctJ_S) ZNI -_a

0 0 0
,.0 _ eq 0

0
O
,.0

_s6
o
0

O
\ "g Z
0 i

t_
o
_o

\
O
£z
t'q

0 0 © ,..C
0
_ 0
I | I 0

O
0 [] 0 q
0
0

ua_o::l!NI luaaaa d alOlN

Page IV-140 Report DAC-60510-FI


Volume HI

"u'I°S ure.tO / (diS) ZI_ _

0 0 C_

It

T !

°_ •,-4 .,-4 -tl 0


_I °
O.
C_ 0 0 o!
Ub
u_
,--4
t-- °I ° ..,! I

/
c_ 0 0
*,.4
u_
() !

0 _o_
i 0

Ln

I [
t'-
!

_'_
0 C @
0
.,-d
4.t
0 o
----_j -_<
°_,4

4.J !
¢D _m
,1_ I)

ub
¢x]

,.-4 !
>
I° _J
.--4

7
t_ o 00 _o o

ue_o._:_.i,,I
_ue_.I_d _IOF_I

Report DAC-60510-F1- Page IV-141


Volume III

U3 N
0 eq t_ ,--I e_
0 e_.D o_o O0 O0 L_
0 00_ e,] --_ oo 0_0 _ O
O0 oo c_ d.4
;c; _dc;
M
m O0
D- 0
0 e_ O0 _O
0 l_ O_ ,._ 000 0 _D 0_ 0 _
0 ,-_ 0 _0 0"_0 O0 • O •
0
_c_ _c_ de;

O
.r,I ,,D O
0 c_ t'.- u'3
0 O',O L_ 0 O_ I._
0 00,-_ 00,-_ .O .O .O .O O
a2 O ,,.O N _4 _d N
zn _c_
O_
O_
e,] oK O
!
O ¢¢3
> 0 e_ 0,1 N
k-4
_z 0 e4,_ 00',D OIM _"O
0
M L_
.O -O • 0 • --
(J', ",D e_ -- --_ _D 0
_o _ G, N
m 4_

O
<
O0
C_
C_ 0
oo
0
e_
e_ 000 0 0
o_
0 .eq .0 .0 .0 .0 _l _ _ ,.D
L_ ,o
Nc_ _c_

< 0 O
e,3 u_ L_ 0
! 0 oo _ 00,-_ O
n .u% O0
e_ 0 O0 0
_nc_ 0 N _
c_
00 00
CO O0 o0 00 m m
0
m m m m N_ r,,1o_ N e4 (_4
U Z_U
t) _u _u
&
0 0 0 0 0
u% O O O 0 L_ 0 L_ 0
i/3 u%
+ + ! I I I I I

Page IV-142 Report DAC-60510-FI


V olurne III

• u._ V

0 N ,uD
O ¢q
.4
",D eq _D e4

0
00

_ o
0 _

,-..4
0
r_

_W
0

L)
U

4,,a
0 •

>

0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 O O O 0 0 00 _D on rq

_I.sd '_=nss_= d

Report DAC-60510-F 1 Page IV- 143


Volume III

'UlOS mead / (d J-S) ZH aa

0 0 0
,.D ._ eq 0

I I l
0

¢M _ 0

o0 0

0 o
0 --
o _,_
0 ._ >,

z _z
O_ '
,,_ E09

,k
m 0
i O
_ d 09u
i
t_
m

c _ 09 Cr

m
O
o 09 >,

0
\ co ._g]
O 09

,4D

09
o

o
O
¢M

I l I I I I O

tM O aC ,.D

uo_oapX H luaaaa d alolN

Page IV- 144 Report DAC-60510-F1


Volume III

"ulos u1_-IO / (cIJ.S) ZH _

(D 0 O
,,D e,_

t_
0

t_

o
t_

o
0 \ c c
Q
._

Q
o

1 1 l

O0 ,.0 _.4 e_
,--a

uo_oapA H _uo_:t_ d OlOIAI

Report DAC-60510-FI Page IV-145


Volume III

33. Tr imethylborane - He lium

See Section 34.

34. Trimethylborane -Nitrogen

The solubilities of both helium and nitrogen in liquid trimethyl-

borane were measured by Astropower Laboratory for this Design Guide, under

Contract NAS7-548. The solubility data for these two systems are tabulated

in Table IV-30, experimental details may be found in Reference 46. The

results reported in the table are obtained from duplicate analyses for two

successive samples; agreement of these values within experimental error

was accepted as indication that solution equilibrium had been attained.

TABLE IV-30

SOLUBILITY OF HELIUM AND NITROGEN


IN LIQUID TRIMETHYLBORANE

Mole Percent Concentration

Test Vapor Pressure Helium Nitrogen


Temperature of Propellant
OF psia(a) 300 psia 700 psia 300 psia 700 psia

-100 l 0. 196 0.416 3.98 8.67

-50 3 0. 3Z3 0. 746 3.68 8.44

0 16 0.467 1.16 3.73 8.23

+50 40 0. 689 1.68 3.51 9.06

(a) Reference 86.

These data are presented as isothermal pressure-composition

and isobaric temperature -composition plots in Figures IV-ll4, IV-If5,

IV-If6, and IV-If7. Additional isobars at 150 and 500 psia have been con-

structed for each system by interpolation.

Page IV-146 Report DAC-60510-FI


Volume III

atm.
10 20 3O 4O

I I
1.6 --

0 -1 O0 °F
/ ---6

/
[] - 50°F
1.4

0 °°F

1.2 f 50°F

1.O // O
U_

_J
O
0.8

0
U_

0.6

m 2 o
(9

0.4 f

0 _
I J 2 O 300 400 500 600 701

Total Pressure psia ,,',,,

Figure IV-114. Isothermal Pressure-Composition Diagram for the


System Liquid Trimethylborane-Helium

Report DAC-60510-F 1 Page IV- 147


Volume III

J
a 150 psia (Calculated by Interpolation) /

1.4 O 300 /

1.2
0

[]
500

700
(Calculated
Interpolation)
by

/
.,w
,...,

:z
C_
l.O / .I
J
/
-4 A
O

C_
L, L5
}.
C_

,.--w
© U3

_a

-- o
- 100 -75 -50 -25 25 50
"tempe rature OF

Figure IV-II5. Isobaric Temperature-Composition Diagram for


the System Liquid Trimethylborane-Helium

Page IV- 148 Report DAC-60510-FI


Volume III

"ulos u--'-e.ID
/ (oTIS) _N _

0 0 0
0

0
I I I 0
D'-

0
0
0

X
0
_t_ --

_Z
!

0
0
0
_o

0 o
°F-q

0
_.)
o_ .,._
n t_

r_

0 (
exl

0
0
6,]

0 o _
p-4 o o _ o
0 0 0 0
0
0
--o [] 0 <]
>

O0 ,,.D _ 6,] 0

UO_O._:_T. N :_U_'a_CI oIOI,y

Report DAC-60510-FI Page 1V-149


Volume III

"ups ul_aO/(dKS)ZN _

o o o o o

% • o
w i y I
I I
I I
I I ¢',,1 0

i I _0
I I _.,_

3 d o
=z
0 _
I
I I 0 0 0

>,
0
• ,-4 °_
i .,-4_ u_
cn 00
¢,,,1
CL i ¢)
ol
o o C o
,--4
.,-4 ¢)
4m

.--4
o u'_
0 o
u_
E i
(D ©
4_
_E
>, >,
_e

4.J
u_

2
7
>
o
j- o

o co -.o _ e4 o

uo_ozil, t.N luo_ao d aIoI,_

Page IV-150 Report DAC-60510-FI


Volume III

35. Unsymmetrical Dimethylhydrazine (UDMH)-Argon

See Section 37.

36. Unsymmetrical Dimethylhydrazine (UDMH)-HeI[um

See Section 37.

37. Unsymmetrical Dimethylhydrazine (UDMH)-Nitrogen

Solubility data for these three systems have been reported

(Reference 71) at pressures of about 15 and 30 psia, and in the temperature

range from -4°F to +86°F. The data are summarized in Table IV-31.

TABLE IV-31

SOLUBILITIES OF ARGON, HELIUM, AND NITROGEN IN


LIQUID UNSYMME TRICAL DIME THYLHYDRAZINE

Arg on Helium Nitr ogen

Temp p(a) Mole % p(a) Mole %


p(a) Mole _0
°F psia x 103 psia x 10 psia x 103

-4.0 14. 23 62.43 17.22 5.83 18. 12 36.64


28.58 125.2 29.90 I0.03 28. 95 58.44

32.0 17.03 76.35 20. iI 9. 19 14.70 32. 59


29.24 131.0 33.08 15.51 19.52 43.48
30.44 68. O8

68.0 14.09 65.84 21. 15 12.53 17.03 42.70


25.97 121.5 32.56 19.81 28.29 71.30

(a) Partial pressure of the pressurant gas m the vapor phase.

(N. B. Pressures are given as partial pressures of the pressurant gas, not

total system pressures.)

Additional data for the solubilities of helium and nitrogen in

unsymmetrical dimethylhydrazine (UDM_H) at moderate pressures are given

in Table IV-32. These data are from Reference 87.

Report DAC-60510-FI Page IV-151


Volume III

TABLE IV-32

SOLUBILITY OF HELIUM AND NITROGEN IN UDMH

Pressurizing Temperature Solubility Final Gas Pressure


Gas (oF) (wt%) (psia)

HeI ium 77.0 0.007 ± 0.005 79.2

57.1 0. 008 ± 0. 005 79.9

Nitr ogen 81.0 76.4

37.4 69.1

*These reported values of zero are believed low; further


test data are required.

The systems UDMH-helium and UDMH-nitrogen have been

studied at the higher pressure range of 300-700 psia (References 38 and 39).

Isobaric solubility plots are shown in Figures IV-118 and IV-119. Iso-

thermal pressure-composition diagrams have been plotted from this data and

are presented in Figures IV-120 and IV-121.

Page IV-152 Report DAC-60510-FI


Volume III

Z, 0 _,

o
u_

1.5 -- 700 psi

,-4
0.3
_ 1.0 --

U9 O.Z_
o

_ 0.5 -- J J
f
L_
O" 300 psia -- 0. I
,......-,o -_
O"
-- 0

50 75 i00 125 150 175 _.00

Temperature, OF

Figure IV-118. Isobaric Temperature- Composition Diagram for


the System Liquid UDMH-Helium

I0.0

A
o 7.5 --2.0
5q

o
"- 5.0--
Z
1.0
u_

_ 2.5__ o
Z
-------'0
%) --I0-
U 300 psia

_ 0

50 75 100 125 150 175 200

Tenaperature, OF

Figure IV-119. Isobaric Temperature-Composition Diagram for


the System Liquid UDMH-Nitrogen

Report DAC-60510-F i Page IV- 153


Volume III

u-m!IaH % °I°IAI

,,,0

,5 c; c; c_
I

0
e4

<D

"uI°S trreao / (clJ_S) OH _

Page IV-154 Report DAC-60510-F1


Volume III

arm.

10 20 30 40
o
I I I

/
6.0-

m 1.5

5.0_

//
0
r.n
4.0_

///
/// 1.0

0 Z
o

/24 ;
...--..

0
U')
v

¢q
Z
o
u
u 0.5

II

0 100 200 300 400 500 600 700

Total Pressure (psia) , "_"

Figure IV-121. Isothermal Pressure -Composition Diagram


for the System Liquid UDMH-Nitrogen.

Report DAC-60510-FI Page IV-155


Volume III

V° REFERENCES

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Volume llI

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6Z. J. Hilsenrath et. al., National Bureau of Standards, Circ. 564 (1955).

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80. M. R. Cines, J. T. Roach, R. J. Hogan, and C. H. Roland, Methane


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Page V-6 Report DAC-60510-FI