UCRL-52226

HYDROGEN VAPOR PRESSURES FROM 4 TO 30 K:

A REVIEW

P. C. Souers, C. K. Briggs.
J. W. Pyper and R. T. Taugawa

February 18, 1977

Prepared for U.S. Energy Research & Development

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UCRL-52226

HYDROGEN VAPOR PRESSURES FROM 4 TO 30 K:

A REVIEW
P. C. Souers, C. K. Briggs,
J. W. Pyper, and R. T. Tsugawa

MS date: February 18, 1977

piPTrilWIT!"..
 Contents
Abstract 1
Introduction 1
The Clausius-Clapeyron Equation 2
The Saturated Liquid-Gas Vapor Pressure 3
Virial Coefficients 9
Saturated Solid and Liquid Densities 13
Saturated Vapor Pressure of the Solid Hydrogens 15
Binary Hydrogen Mixtures 1?
Acknowledgments 23
References 24
Appendix. List of Symbols 30

-iii-
 HYDROGEN VAPOR PRESSIRES FROM 4 TO 30 K:
A REVIEW
Abstract
In this report, we review the
following properties for the hydro
gens from 4 to 30 K: liquid-gas and
solid-gns vapor pressures, triple-
point values, virial coefficients,
liquid and solid densities, and
heats of transformation. We have
correlated these properties with as
much consistency as the data allow.
Empirical equations are given for
virial coefficients and densities.
Introduction
The current research programs in
hydrogen fusion (e.g., magnetic con
finement, electron beams, heavy ions,
plasma focus, and lasers) all use a
D -DT-T mixture as thermonuclear
fuel. Most of these programs plan
eventually to use the D-T in cryogenic
conditions, either for cryopumping,
tritium recovery, or fuel pellet
manufacture. Therefore, we have
embarked on a series of review and
extrapolation reports in an attempt
to provide information on the physical
and chemical properties of heavy
hydrogen. In this paper, we con
sider the saturated-vapor pressure of
the hydrogens from 4.2 to 30 K.
The vapor pressure along the solid-
gas and liquid-gas phase boundaries
Clausius-CI -ipeyron equations relate
vapor press-are and temperature with
the other properties. Data are
frequently available with H and X)
and are scmetinves available for HD
and T. We have, therefore, esti
mated HT and DT values to complete
the set. We have also reviewed work
on binary H-D mixtures and have esti
mated the expected behavior for H-T
and D-T systems.
is perhaps the most basic property
of cryogenic hydrogen. It is cer
tainly the most measured property
and a staggering amount of information
exists. Much of this has been sum
marized in recent cryogenic hydrogen
8,9
surveys.
However, the literature on vapor
pressure is quite confusing. Even the
better reviews have made no attempt
to correlate the data throughout the
isotopes or across the triple point
from liquid tc solid. In addition,
much of the data in the reviews are
obsolete; scattered errors propagate
down through the years. The most
recent papers containing the best data
are written in stark outline, pre
sumably for a narrow and already
well-informed audience. To the out chaotic; In this report, we shall try
sider, however, the field appears to bring some order to this chaos.

The Clausius-Clapcjron Equation

The saturated-vapor pressure is where the entropy difference is con

usually given some theoretical sub
stance with the Clausius-Clapeyron
equation. This equaces the free
energy, G, of two phases in equilib
rium (e.g., liquid and gas
pure component;
verted into the heat of vaporization,
H , divided by the temperature. The
subscripts g and i again denote gas
and liquid. We use the gas equation
) for a to substitute for the gas volume, V ,
and obtain,

(#)/'* (fl | PH
(5)

H)
dT"
ZRT

(
3G\
dP +
(C dT
g
(1)

where Z is the compressibility and R

where P is the pressure, T i= the is the gas constant. Inverting the

temperature, and the letters I and g volumes to densities, we find

denote liquid and gas. We can now use

dlnP H
the thermodynamic identities, (6)

f9
dT
RT

l V, (2)

If we had a perfect gas with Z = 1

and
and if p p., then we could easily
integrate Eq. (6) to obtain P.
(II (3)
Although the constants of integration
must be determined experimentally, we
where V is the volume and S is the
have nevertheless related P and H .
entropy. From this we obtain v
We replace the real heat of vapor
dP ll
-fi ization, H , with an "effective" one,
dT T(V -
g V w H (eff), where
v

-2-
 From a practical point of view, we
H (eff) = (7) would like to know what H (eff) or

H) v
H (eff) look like. We may, therefore,
s
take experimental data points that
and also, are close together and use a varia
tion of Eq. (8);

2
H (eff) - RT 4iSE f8) / lnP
2 - l n P
l\
v dl H (eff) = R(T)' (9)
T T
\ 2 - l /

For solids and gases in equilibrium, The subscripts 1 and 2 refer to the
we use the corresponding solid den data points in a pair. The T is an
sity, p , and the heats of sublimation, average between T and T . If (T. -
H and H (eff). We consider only the T.) is small (i.e., a Kelvin or less),
s s '
solid-liquid equilibrium and just at a linear average may be used without

the triple point. Again, we may use great error. (After presenting our

the Clausius-Clapeyron equation with sources of data, we use Eq. (9) for

the heat of fusion, H . the analysis.)

f

The Saturated Liquid-Gas Vapor Pressure

The literature is extensive and, International Practical Temperature

24
unfortunately, most of it is obsolete. Scale of 1968. This is a strange
In this latter category, we include paper, the product of the Comite
the following references from 1948 to International des Poids et Mesures.
the present: eH (Refs. 11-18), nH It is obviously the work of many
(Refs. 11, 13, 16, 19), HD (Ref. 12), people but only the communicator's
and D (Refs. 12, 20-22). We also name is given. However, neither
include an early effort to use H and details nor references are given so
nH liquid-gas vapor pressures as that it is impossible to trace its
23
part of the temperature scale. continuity with earlier work. Pre
Selecting the best data is not ceding the temperature scale work,
easy because the differences are the paper with the greatest reported
subtle and the background data are detail was written in 1967 by the
18
sparse. For eH- and nH,, we select Dutch ; yet, their work does not
the equations listed as part of the appear to have been incorporated to

-3-
any degree into the 1968 temperature
scale. Moreover, the 1575 temperature-
measurement conference" includes even
less of the work of the Dutch. The
nH, data are not repeated and there
are no vapor pressure curves. Three
fixed points from 13.8 to 30.3 K are
listed for eH,; these are obviously
from the 1968 temperature scale.
Returning to the 1968 temperature
scale work for our hydrogen vapor
24
pressures, we conclude that, from
the triple point to 23 K, the eH
data are valid. They are almost
certainly as good as enybody else's
up to 30 K because they are a close
derivative of the triple point to 30-K
equation of the famous 1948 Woolley
review. The nH, data, only slightly
different, are listed to apply from
24
the triple point to 30 K. These,
too, are similar Co the old Woolley
equation.
For the HD data, there are only
12
two choices available and we select
the 1948 data of Woolley. For the
D. data, we select the 1951 data of
Grilly. The later review of Prydz
does not seem to us to be internally
22
consistent. For T_, we select some
1975 data by Sherman and Grilly of
27
Los Alamos. These are partly re-
measured data by Sherman and partly26
the readjusted 1951 data of Grilly
The D data are normal and the dif
ference between these and the equi
librium form is probably less than
their accuracy. The T value is
listed as normal but. could be equi
librium because it could have been
converted during the experiment by
J8 '9
beta-particle catalysis.
Now, we consider the form of the
effective heat of vaporization,
H (eff), as a function of temperature.
We have taken the data on H, HD, and
D_ from the sources listed above and
have processed pairs of adjacent data
points according to Eq. (9). Figure
1 shows the resultant H (eff) vs
v
temperature curves from the triple -.
points to 30 K.
At first glance, the form of
H (eff) appears to be linear with a
quadratic component,
2
H (eff) = R[-B + B'T + C T ] , (10)
where B, B', and C are constants and
B is a negative number. We substitute
for H (eff) in Eq. (8) and integrate
to obtain
lnP A + | + B'lnT + CT , (11)
where A is the constant of integra
tion. The term P denotes the sat
uration liquid-gas, pure-component
vapor pressure. This equation pro
duces a fairly self-consistent set of
constants for H, HD, D, and T
(see Ref. 3 ) .
However, liquid-gas vapor pressures
have not been cast in the form of
 1 T r
~W Triple
15 point

14
''!# v

t? 13

SP Triple * oo
point # . 0 0
12
HD

<P

11 0cd&
o o

o Triple
Solid point . &o 0

w 10
<^P o
o ft*

Liquid

8 - waso
J I 1 I I I
5 10 15 20 25 30 35 40
Temperature K

Fig. 1. Effective heats of sublimation and vaporization for H , HD, and D 2 2

from many sources. Most of the strings of points contain unknown amounts
of smoothing. Here, * = eH,, 0 = nH,, HD, and v = D . ?

-5-
Eq. ( 1 1 ) . From Woolley's 1948 review values as well as constants A ami B
to the present, the accepted form has follow a smooth sequence through the

been isotopes; however, C and D do not.

For the present, we will have to live

2 3
27
H (eff) = R[-B + C T + 2DT ] ,(12) with these discrepancies. Sherman
at Los Alamos Scientific Laboratory
where B, C, and D are constants and B, is currently working on the H , D , ?

again, is a negative number. This and T , vapor pressures and hopefully

integrates to he will be able to smooth the sequence

of equations.
2
lnP = A + | + CT + D T ; (13) The equations of Table 1 m u s t , of

course, yield the proper triple-point

again, A is the constant of integra temperatures and pressures. These
tion. This is the form used in all are: e H , = 13.81 K and 7030 Pa
24
our selected references, including (52.73 T o r r ) , nH,, = 13.956 K and
the 1968 temperature scale; we shall, 7199 Pa (54.00 T o r r ) , 2 4
HD = 16.604 K
therefore, also follow the form of and 12400 Pa (92.8 T o r r ) , 1 1
nD 2 =
Eq. ( 1 3 ) .
26
18.73 K and 17140 Pa (128.6 Torr)
The actual constants for e H , n H , 9 and T , = 20.63 K and 21600 Pa
27
HD, D , and T are listed in Table 1. (162.0 T o r r ) . The normal boiling
We see that the H , H D , D , and T points at one atmosphere that fit

Table 1. Saturated liquid-gas vapor pressures of the pure-component hydrogens

from the triple point to 30 K. The HT and DT pressures are estimated
from the rule of the Geometric Mean.

Hydrogen
Isotope A (Pa) A(Torr)

15.46688 10.57411 -1.013378 * 10 5.432005 x 10 -1.105632 x 10

nH 2 15.52059 10.62782 -1.027498 " 10 5 .338981 -1.105632 x 10,-4

HD 16.52000 11.62723 -1.272167 x 1 0 2

3..405523 0

nD 18.89988 14.00711 -1.612823 x 1 0 2

-4 .861678 -2 10.56887 x 10
2

r, 19.11365 14.22088 -1.820038 x 1 0 2

-2..560401 5.133943 x io"
these equations are: eH 9 20.280 K,
P / P P 5
Mil, 20. 197 K, HI) = 22. 13 K, nl)., XY " X, ' V 2 ' '
21.fih K, and T., = 25.04 K. liocause

these values arc taken from different
sources, they are not comp'.^ely con
sistent as a set. The H
peratures are set to the 1968 tempera
ture scale; the HI) and D
not and could be 0.01 K higher.
Mittelhouscr and Thodos analyzed the
data of tiie day and decided that -in.
and T 7 tem (15) is true to within 0.52, although
here is a 1.1? deviation at 19 K.
values have They used Eq, (15) to find the normal
boiling point of the unknown species,

Now the problem arises: What XY. Then they plotted a normal

shall we do with HT and DT? These boiling-point vs triple-point curve

have never been isolated in bulk and interpolated to obtain the XY

quantities as pure components and triple-point temperature. At that

their vapor pressures have never been temperature, Eq. (15) gave them the

measured. Mittelhauser and Thodos corresponding pressure. They then

studied the question and used the

derived equations for HT and DT like
30 those of Table 1. Their final esti
following method. They possessed

an older version of the triple-point

mated XY pressures were only a few

and normal boiling-point data for H,

tenths of a percent below those of

HD, D , and T. They also knew that,

the Geometric Mean. Their triple-
9

experimentally, HT has a lower iso

point estimates were: HT = 17.62 K

thermal vapor pressure than does D ;

and 14600 Pa (10S.5 Torr) and DT =
31 19.71 K and 19420 Pa (145.7 Torr).
both have the same mass. They then
These values have been taken as offi
used the rule of the Geometric Mean
cial ever since, including by us.
to obtain the vapor pressures of HT
They have never been measured, and,
and DT. This rule applies to hydrogen
as we shall see, could be somewhat in
species in isothermal chemical equil
error.
ibrium. Thus, for the chemical

reaction, We shall use the rule of the

Geometric Mean to calculate HT and DT
X + V ^ 2XY, (14)
2 2
vapor pressures. This procedure is
also recommended by Sherman at Los
where
27
Alamos. However, our accepted H.,
X,Y = H,D,T,
D,, and T, vapor pressures are slightly
the law of the Geometric Mean pro different from those used by Mittel
poses the purs-component vapor pres hauser and Thodos. If we generate
sure relation, vapor pressures from Table 1, we find
 that the measured HD values are con
sistently less than those calculated
from the Geometric Mean. Figure 2
shows that these results vary
from 3% deviation at the HD triple
point to 1.3% at 30 K. We do not
know if this is a real effect, and,
therefore, have not made any cor
rection for the observed deviation.
Let us suppose that the deviation
from the Geometric Mean is a real
effect. It will probably be larger
for HT where the two masses are the
most different. In Fig. 2, we have

o
^
CD +3
rtJ
1-3
t-l

CD <U
S- 03
3 E

10 15 20 25 30
Temperature K

Fig. 2. Deviation of vapor pressures from the rule of the Geometric Mean. The
HD data are taken from Table 1; other daca are estimates.
estimated an HT value from the rela
tive difference of H-T and H.,-n
triple-point temperature differences.
We find a possible deviation of 4.5%
which could change the triple-point
temperature by as much as 0.2 K. For
Virial Coefficients
As seen in Fig. 1, there is not
much data on the solid-gas vapor
pressures. Good low-temperature data
have appeared only in the past five
years. The strings of points in Fig.
1 represent previous smoothings, the
validity of which is uncertain. The
data must also connect across the
triple points.
To work our way from liquid to
solid vapor pressures, we have col
lected several peripheral bits of
data. The effective heat of vapori
zation must be converted into a real
heat. This requires, first, a value
for the compressibility of the gas.
In this section, we derive virial
coefficients for use along the satura
tion line.
We write the compressibility, Z, as
Z = l + Bp +Cp (16)
g 8 8 g
-9-
DT, the effect will be smaller,
perhaps IX or less. This effect is
important when analyzing mixtures
of isotopes where nonidealities of
mixing are expected to be a few
percent.
where p is the gas density, B is the
second virial coefficient, and C is
8
the third virial coefficient.
Second virial coefficients for the
hydrogens have been neasured for:
eH (Refs. 32-34), probably eH. .Kef.
11), n H 2 (Refs. 13,35-36), HD (Refs.
13,36), and n0, (Refs. 13,36). A
plot of these data is shown in Fig. 3
from the triple point to 30 K. The
reported difference between eH and
l
, 37
nH is about l/o, which is less than
?
the scatter of the data. We have,
therefore, drawn a single H. curve
and describe these curves with the
empirical equation,
B = 0 (17)
where B and n are constants. See
Table 2 for a list of these constants
and for estimates of HT, DT, and T .
 -0.5

20 24 32
Temperature - K

Fig. 3. Second virial coefficient data for hydrogen gas from 14 to 30 K.

Here, A = eH,, o nH = HD, and A
"2"

-10-
 Table 2. Second virial coefficients of the hydrogens from 14 to 30 K.
Estimates, as derived from a triple-point temperature plot, are
in parentheses.

n
B - B /T
g 0
Hydrogen _, ,
Isotope B , 10 m K /mol n

H, -11,178 .1.44

HD -16,170 1.53

HT (-20,468) (1.59)

D -25,168 1.64

DT (-29,310) (1.705)

T 2 (-33,189) (1.765)

These estimates are obtained by plot
ting the constants vs the triple-
it
point temperature and extrapolating.
The third virial coefficient has
been measured for eH_ and nH (Refs.
11,33,35). We do not include the
22
Prydz review data for D, for either
virial coefficient. The third virial
coefficient data are shown in Fig. 4
*This empirical method accounts for
the saturation of a given property,
progressing from H2 to T2. It also
accounts for the probable differences
expected (from the vapor pressure)
for HT and D2. It is, actually,
almost equivalent to plotting a
property vs the reduced mass of the
isotope.
and the data extend in two opposite
directions. The Woolley data are
probably the more correct. However,
we need only concern ourselves with
the high-temperature end of the satur
ation curve. He use the C -limiting
- 1 3 2
value of 1600 x 1 0 " (m /mol) ; at
30 K, both sets of data approach this
value. At lower temperatures, the
saturation pressure falls so rapidly
that the effect of the third virial
coefficient, whatever its value, may
be ignored. Thus, we have calculated
the compressibility and gas density
at the triple points of the hydrogens
and present the data in Table 3.

-11-
Table 3. Hydrogen heats of transformation at the triple points. Estimates are
in parentheses. For purposes of calculation, more digits than the
true accuracy are given.

Hydrogen
isotope T (K) ITorr) iraol/tn )3
U *,:!) \ J

eH, 13.810 52.73 62.213 0.9841 923.85 0.9S25 907.7 117.3 102 5.11 0.982.' 104 1.0

nH, 13.956 54.00 63.043 0.9842 935.76 0.9826 919.5 ['.2 1(136.7 0.9K26 (054.H

rlD 16.604 92.8 91.498 0.9799 1133.78 0.9777 1110.5 155.4 1769.9 0.9779 1246.6

HT (17.62) (109.5) (101.87) (0.9782) (1246.57) (0.9758) (1216.4) (176) (1192.4) (0.9761) (1426.5)

nD, 18.731 128.6 112.67 0.9768 1314.63 0.9742 1280.7 Wh.6 1477.S 0.9745 1516.0

DT (19.71) (145.7) (121.20) (0.9780) (1417.31) U).975)) (1382.5) 1215) (1597.)) (0.9>56) U 6 J 7 . J)

T
20.627 162.0 (128.56) (0.9796) (1497.59) (0.9768) (1462.8) 12J2) (1694.8) (0.97711 (1714.6)
2

Fig. 4. Third virial coefficient data for hydrogen gas from 14 to 30 K.

Here, = data from Ref. 11, o = data from Ref. 33, and A = data from Ref. 35.

1 1

- -

4-


- -


A


D
D
D ([ ]
D
D

1 1 1
10 15 20 25 30
Temperature K

-12-
 Saturated Solid and Liquid Densities

As we can see in Eq. (7), the next deviate from 0.5% above 26 K and is
item needed (in addition to gas com off by 5% at 30 K. The other measured
pressibility and density) to relate isotopes should have densities to 0.5%
H and H (eff) is the liquid (or up to 30 K. We have interpolated for
v v ^
solid) density. The available liquid- HT and DT by plotting p (at constant

density data taken for H,, HD, D , T ) , A. and B vs the triple-point

and T, (Refs. 17,22,38-40) are prob temperature, and smooching.

ably good to 0.5%. We use the fol The density data for solid H, HD,

lowing empirical equation for the D, and T_ are extremely scattered.

saturated liquid density, p.: Measurements have been taken by both

, ,,11,41-42 ,,,..
bulk and lattice parameter
p = A - BT 2
, (18) 43-52
techniques. The data are shown
in Fig. 5 for both the hexagonal
where A. and B are constants for each close-packed fsnd face-centered cubic
isotope. The constants are listed in phases. The error in the data is much
Table 4. The H equation begins to larger than the 0.5% volume change

Table 4. Equations for saturated solid and liquid densities of the hydrogens.
Estimates are in parentheses.

SOLID LIQUID
3
B T
p
s =
'I- s H * - v
A 2

Hydrogen Ps 43
B
s
3 3
4 3 H 3 2
Isotope (10 mol/m ) (mol/m -K ) (10 mol/m ) (mol/m <K )

eH 2 4.434 0.5483 4.093 14.30

nH 2 4.434 0.4887 4.109 14.34

HD 4.742 0.3556 4.420 13.35

HT 4.892 0.3188 4.580 13.25

m> 2 5.072 0.2886 4.778 13.20

DT (5.219) (0.2642) (4.900) (13.36)

T 5.368 0.2450 5.116 13.68

2

-13-
 10
Temperature - K

Fig. 5. Densities of the solid hydrogen isotopes as a function of temperature.

The open symbols represent data obtained in bulk determinations; the solid
symbols are data obtained in lattice parameter determinations.

that occurs in the crystallographic We have modified our opinion of

transition in the 2- to 4-K range. 53 the single T, x-ray diffraction point
We use another empirical equation from that expressed in earlier
for the saturated solid density, p : 3 5
papers. ' This density was first
reported by the Soviets as 5.36 x
3 4 3
P " Ps " V
S (19) 10 mol/m for an incorrect tetra
43
gonal structure The authors then
where p and B are constants for revised it to 5.49 x 104 mol/m 3 for
s s
each isotope (see Table 4). The the correct hexagonal structure.44
constant p is the solid density at The first value is probably more
0 K. The cubed exponent is set by correct because the second is too
the few H, and D, points in the 10- large to fit into any isotopic se
to 13-K range and, quite possibly, is quence. We use the first value,
not the correct power. 5.36 x 10 mol/m . In any case, we
-14-
Table 5. Solid and liquid hydrogen densities at 0 ", 4.2 K, and the triple
points (TP). Estimates arL: in parentheses.

Densiity
3
(10 mol/m ) Density Ratios

Hydrogen Solid Solid Solid Liquid 4.2 K solid TP solid

Isotope 0 K 4.216 K TP TP TP liquid TP liquid

eH 2 (4.434) 4.430 4.290 3.820 1.1594 1.1227

nH 2 (4.434) 4.430 4.301 3.830 1.1567 1.1230

HD (4.742) (4.739) 4.579 4.063 (1.1664) 1.1270

HT (4.892) (4.890) (4.718) (4.179) (1.1702) (1.1290)

nD_ (5.072) 5.070 4.883 4.316 1.1747 1.1314

DT (5.219) (5.217) (5.017) (4.425) (1.1790) (1.1337)

T (5.368) (5.366) (5.153) 4.535 (1.1832) (1.1362)

2

see that the HD and T, curves basi desirable to have better experimental
cally are estimates, to say nothing values for all these isotopes.
of the HT and DT values. We have, In Table 5, we have collected the
therefore, used the same triple- equation-derived densities for the
point temperature plot, fixed mainly solid hydrogens at 0 K, 4.2 K, and
on H and D_ values, to obtain all at the triple point as well as for
solid density curves. It would be the liquid at the triple point.

Saturated Vapor Pressure of the Solid Hydrogens

We can now consider the deviation point heat of fusion to find the heat
of the solid-hydrogen vapor pressures. of sublimation. We use the measured
We start with the effective heat of values of e H 2 = 117.3 J/mol, nH. =
55
vaporization, H (eff), for the liquid 117.2 J/mol, HD 159.4 J/mol, * 11

at the triple point. We multiply it

by Z(l - p / p . ) , as shown in Eq. (7),
8 ~ *The earlier value of 154.8 J/mol for
5
HD " does not form a smooth sequence
to obtain the true heat of vaporiza
with the other isotopes.
tion. We now add to it the triple-
-15-
and nD, = 196.6 J/mol. These form is apparent that i!,(eff) is at
a good sequence when plotted empir least a straight line with temper
ically vs the triple-point tempera ature. It may even be concave
tures. We, therefore, estimate other downward (rather than concave upward
2
triple-point heats of fusion as: like T ) . He assume H.(eff) to be
HT = 176 J/mol, DT = 215 J/mol, and a linear function of temperature,
T. - 232 J/mol. We add the heats of at least from 4 K to the triple
fusion and vaporization to obtain the point. We use Eq. (10) with constant
true heat of sublimation, H . We C = 0. We find
s
then divide H by Z(l - p /p ) to H (eff) = R[-B + B'T) . (10a)
s g s
finally obtain the effective heat of
sublimation, H (eff), at the triple We need two points to calculate
the constants B and B'. We already
point. All these steps are shown for
have the H (eff) triple-point
the isotopes in Table 3.
values. From Lee's work, we take
Now, we consider the form of H (eff)
s average values of 818 J/mol at 4 K
as a function of temperature. Many for nH, and 1224.5 J/mol at 4.5 K
sources from Woolley have used Eq. 58
(12) with constant D = 0; i.e., they for nD. The third good refer
have a quadratic temperature increase ence is Woolley's HD value of
1 1

for H (eff). Using this equation 1155 J/mol at 10 K . Woolley's

does not produce a good sequence of
constants B and C for the measured
isotopes H,, HD, and D . The reason
can be seen in Fig. 1, which plots
the good solid-gas data (Refs. 11, 57,
58) with the obsolete references for
eH 2 (Refs. 11,14), n H 2 (Refs. 11, 59-
61), and D 2 (Refs. 11,26),
not included the solid-T, data in
the plot because the scatter is
considerable.
The good data in Fig. 1 are the
two clusters about 4 K by Lee for
57 58
nH, and nD, . The precision of
these points is outstanding, even con
sidering the smoothed data nearby.
point is not of the quality of Lee's
data but it is all we have for HD.
For eH,, we assume the same slope
as nH,, i.e., we expect a value
of 806.2 J/mol at 4 K. For HT, DT,
and T,, we must use our usual
triple-point temperature estimates.
As an aid, we have Grilly's
We have triple-point T, values for H (eff)
and H (eff) of 1700 and 1500 J/mol
26
(each 50 J/mol, respectively.
Next, we integrate Eq. (8) to
obtain the pressure,
lnQ = A + ^ + B'lnT (11a)
It

-16-
 Table 6. Saturated solid-gas vapor pressure of the hydrogens. Estimates are
in parentheses.

lnQ = A
+ h B' InT
Hydrogen
Isotope A(Pa) A(Torr) B B'

eH 2 7.416223 2.523453 -85.35199 2.903253

nH 2 7.570953 2.678183 -86.94152 2.860678

HD 8.866980 3.974210 -112.7637 2.615288

HT (9.451935) (4.559165) (-126.6) (2.552)

nD * 2 9.801089 4.908319 -136.1893 2.463629

DT (10.32667) (5.433901) (-149.7) (2.396)

T (10.73882) (5.846049) (-160.7) (2.3235)

2

Here, the term Q denotes the satur integration, A, is obtained by

ated solid-gas, pure-component vapor substituting the triple-point
pressure. The use of T for liquid- temperatures and pressures. The
gas and Q for solid-gas will prove solid-gas, vapor-pressure constants
to be convenient when discussing for the isotopes are listed in
hydrogen mixtures. The constant of Table 4.

Binary Hydrogen Mixtures

All work with mixtures of hydrogens Soviets, mostly on eH-eD , but partly
has been done with binary combinations. on H -HD and H D - D . "
2 2
6 4 6 7
Much of
The first substantial work concerned this work also involved the three-
the liquid-gas equilibria of H.-HD and phase region.
H.-D, mixtures. Some H_-L/ liquid- The three-phase eH-eD phase dia
solid work was done, primarily to de gram is shown in the temperature-
monstrate the absence of a phase sep composition plot of Fig. 6. '
aration down to 8 K. This was fol The solid-line data were taken by
lowed by considerable work by the melting a slowly-frozen sample, i.e.,

-17-
 19

I i 1 i I i I i I i I
0 0.2 0.4 0.6 0.8 1.0
Mole fraction of D,

Fig. 6. Three-phase, temperature-composition diagram for eH2~eD2. Here,

= corrected calorimetr'c freezing of liquid-gas," = corrected
calorimetric melting of solid-gas,3 = calorimetric freezing,"' and
0

A = volume shrinkage upon freezing. '

-18-
one that fractionated away from the H.-HD and HD-D , respectively. If we
known input composition. Hence, the correlate these with the difference
experimental values were extensively in triple-point temperatures of the
corrected to produce those shown in pure components, 6, - ., we find
Fi>;. 6. The gas line is our that the temperature spread increases
Raoult's-Law calculation. as approximately the 2.2 power. The

In l-'ig. 6, the binary phase dia composition spread increases as the

gram resembles a "cigar" that closes 1.2 to 1.5 power. All mixtures are

at each end at the triple-point tem assumed to be completely miscible.

perature, ''). (for the ith species). Assuming that these mixtures are
U'e use the center line, connecting essentially ideal, we consider the
the two triple points, as our refer following relations. Raoult's Law,
ence. For a two-phase system (e.g., generalized for three equilibrated
liquid and gas), about half of the phases with components i and j ,
cigar is above and half is below this becomes
center line. We may imagine two such
two-phase cigars, liquid-gas and (20)
h^l
solid-liquid (from the melting curve),
overlapping almost completely. The and
liquid line then moves almost onto
the center line. For H -D , the _i
po
(21)
vertical-temperature spread of the
liquid-solid cigar at 0.5 mole frac
where
tion, AT , is 0.6 K with less than
20% of this above the center line.
The corresponding horizontal- LP! (22)
x I
composition spread occurs at the tem i=l
perature where the center line and
Here, the mole fractions of component
the AT line intersect (point 0 in
i in the gas, liquid, and solid
Fig. 6 ) . This spread, (s. - I ) ,
phases are g., I., and s.. Also, P
I I I i
for H -D is 0.12. Similar liquid-
is the ith pure-component, liquid-
solid cigars have been measured for
vapor pressure, derived in the last
64
H -HD and HD-D .
2 2 It is difficult section after much effort and 0. is
to measure the cigar widths from the l

small graph, but we obtain AT_ ^ val
ues of 0.17 and 0.10 K and (s
..). - values of 0.052 and 0.038 for
the same for the solid code. Lastly,
- P. is the partial pressure of com
ponent i in the mixture and P is the
Raoult's Law total pressure of the
-19-
mixture. We substract S..Q? from each 6
1 1
T - 7) i.e. , (25)
side of Eq. (20) to obtain the compo
sition spread at a given temperature.
and

V (H (23)
( s , - . ) = 0 . 0 6 8 IA, ( 6 .
l i i j i -v (26)

Using the codes of this report* we

have plotted (P/Q? - 1) as a function
of T - 6. in Fig. 7. The farcher we
move from the ith component's triple
point, the more (P*/Q? - 1) will
diverge. For most of the isotopes,
temperatures both below and above the
triple points must be considered
because all conceivable mixtures can
exist between the lowest Q. of 13.81K
l equal to the ratio of (6
for eH, and the highest Q. of 20.63 K
for T_. Ihis necessitates extrapolat
ing our pure component codes into
nonphysical regions with unknown
error. Because both the liquid and
solid codes are used over the entire
three-phase hydrogen range from 13.81
to 20.63 K, the two symbols P? and q?
are used to avoid confusion.
From Fig. 7, we find that
1 ,0.8-1.2
i- - (24)
For eH -eD , (6. - 8.) is 4.92 K and
we calculate (s. - .)., _ to be
0.084, compared to the measured value
of 0.12. If we return to the phase
diagram in Fig. 6, we see that for a
thin cigar, we may derive the follow
ing approximate statement. At the
0.50-mole fraction point, the ratio
AT. ./(s. - i.) is approximately
- 9.) divided
by the total composition range, which
is always one. From Eq. (26), we see
that the temperature spread of the
liquid-solid cigar, AT, will follow
the square of (Q. - 6.).
i J
We calculate AT. . to be 0.41 K,
compared to 0.6 K for the experimental
value. We may roughly summarize the
three H-D binary systems by empiri
cally changing the coefficient assigned
to Eq. (26).
We. have

( s - ^ ) -0.09 iS,. ( e - e . ) , (26a)

i i

The relationship is close to linear

and a coefficient equal to 0.068 may and
be obtained from Fig. 7. If we AT = 0.09 I.S.. (6. J (27)
equate the liquid line and center
line, then the temperature may be We may now estimate values for systems
found to approximate that have not yet been measured. For

-20-
 ' below TP
Average of Eq. ( 2 4 )
eH above TP
2

4<
v
: n H above TP

Absolute value of temperature difference from the t r i p l e point,

IT - 6,1

Fig. 7. Fractional difference of the pure-component liquid and solid vapor

pressures as a function of the distance from the tripla-point temperature.

-21-
D.-T-, (6. - 9.) is 1.90 K and we to 18.73 K. The pressure peaks at
calculate (s - l )
i Q b to be 0.043 approximately 0.83 mole, fraction D
(i.e., 50% liquid T yields 54% solid (17.90 K). The two lower curves
T ).
9 Also, we calculate AT. _ to be are for two-phase, liquid-gas equi
0.081, quite a thin phase-diagram librium, taken from the boiling-point
cigar. For H~-T 2 (providing there is table of Ref. 62 where the liquid
no phase separation) we calculate mole fractions are given. The two
(e^-6^, (s - i ) 1 0 > 5 , and A T Q > 5 to curves are isobarLC in terms of the
be 6.82 K, 0.15 mole fraction, and Raoult's-Law pressure, F. They are
1.05 K, respectively. not isothermal and the temperatures
We now turn to the percent devia are not given. Thus, it is impossible
tion of the mixture vapor pressure, I, to modify the data (or use the au
from Raoult's Law. This is defined thors' dew-point table). On each of
as the lower curves, the temperature
obviously increases with the mole
(VT) fractions of D . Also, the 2500-Torr
I(T ) = - - (100) , (28)
m P
m curve represents higher temperatures
than the 500-Torr line. There are
where P is the measured total pres-
m
two major features of the Raoult's-
sure of the mixture and I is calculated
Law, mixed-vapor pressure data. The
at the measured temperature, T . We
data are peaked towards the D side,
see that I has an empirical aspect in
about at the gas mole fraction of 0.5.
that T may be shifted from the ideal
m ' Secondly, I increases with decreasing

(but unknown) temperature. Figure 8 temperature. This seems surprising

shows available data for H^-D,. The because the gas pressure drops rapidly

highest curve is in the three-phase as the temperature falls. The gas

equilibrium data, taken for freezing becomes more nearly ideal in the sense

liquid where we know the composition of the Perfect Gas Law, even while it

and for freezing gas where the Raoult's is becoming more nonideal with respect

Law is used to estimate the liquid to Raoult's Law. There are also some

mole fraction. We have used our H -HD liquid-gas data of P values

CO
vapor pressure codes to expand the
from 500 to 2500 Torr. These show
Soviet raw data into this form. The
the same general form but are lower
three-phase curve is neither isothermal
than the corresponding H-D, points
nor isobaric. The temperature in
by a factor of 0.34 to 0.87.
creases left to right from 13.81 K

-22-
 10

Three-phase'

7
S ^Cr" 2500 T o r r - ^ ^ \

0.2 0.4 0.6 0.8

Liquid mole fraction D 2

Fig. 8. Percent deviation from Raoult's Law for H2-D2 mixtures. The two-
phase pressures are Raoult's Law values, Pf. Here, = calorimetric freezing
of liquid-gas,*>? o volume shinkage upon freezing,6? and = two-phase
boiling points.^2

Acknowledgments

We thank Jack Frazer, Lee of the Cryogenic DT Properties

Roberts, Bob Hickman, and Terry Progr-im out of the Chemistry Research
Galloway for their continued support fund.

-23-
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and H, + D Mixtures Between 18 and 28K," Trans. Faraday Soc. S4,
1481-1491 (1958).

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63. D. White and J. R. Gaines, "Liquid-Solid Phase Equilibria in the Hydrogen-
Deuterium System," J. Chen. Pky.-. ;
si , 4152-4158 (1965).
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Kogan, "Melting Diagram of the pH^-oD,, pH -HD, and oD-HD Systems,"
9

Soviet Phys. -JETP SO, 1048-1049 (1970).

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2

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Phys. JETP S2,
838-840 (1971).
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PLL/gw/vt

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 Appendix. List of Symbols
D Constants for vapor pressure, temperature equations.

Constants for liquid density, temperature equations.

Second and third vlrial coefficient for gas.

Constant for the solid density, temperature equation.

Constant for the second virial coefficient, temperature

equation.

Gibbn free energy (J/mol).

g Mole fractions of the D,, H, 1 , and j components in the

gaseous phase of a mixture.

Real heats of fusion, sublimation, and vaporization (J/mol).

f) Effective heats of sublimation and vaporization (J/mol).

Percent deviation of gas pressure from Raoult's Law.

$,. Mole fraction of the D_, H , i , and j components in the

liquid phase of a mixture.

Constant for the second virial coefficient, temperature

equation.

Partial pressure of the i component in a mixture (Torr).

Measured total vapor pressure of a mixture (Torr).

Pure component, saturated, liquid-gas vapor pressure.

Subscripts D,, H, X,, XY, and Y_ refer to specific hydrogen
species. Subscript i refers to the i component in a
mixture. Subscripts 1 and 2 refer to two consecutive data
points in a series (Torr).

Raoult's Law total-vapor pressure of a mixture (Torr).

Pure component, saturated, solid-gas vapor pressure.

Subscript i refers to the i component in a mixture (Torr).

Gas constant (8.314 J/mol-K or 62.361 Torr-litres).

Entropy. Subscripts g and I refer to gas and liquid (J/mol-K).

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Mole fraction of the i component of a mixture in the solid
phase.

Difference in solid and liquid mole fractions for the i

component of a mixture at the temperature of the center line-
0.5-mole fraction intersection.

Temperature, average temperature between two data points.

Subscripts 1 and 2 refer to temperatures of two consecutive
data points of a series (K).

Temperature difference between solid and liquid lines at

0.5-mole fraction (K).
3
Volume. Subscripts g and I refer to gas and liquid (m ) .

Diatomic hydrogen species (H, D, T ) .

Compressibility of gas.
3
Density of gas, liquid (mol/ra ) .

Triple-point temperatures of the i and j hydrogens (K).

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