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NATIONAL BUREAU OF STANDARDS REPORT
R. D. McCarty
Cryogenics Division
IMPORTANT NOTICE
NATIONAL BUREAU OF STANDARDS REPORTS are usually preliminary or progress accounting documents intended
for use within the Government Before material in the reports is formally published it is subjected to additional evaluation
and review For this reason, the publication, reprinting, reproduction, or open-literature listing of this Report, either in
whole or in part, is not authorized unless permission is obtained in writing from the Office of the Director, National
Bureau of Standards, Washington, DC 20234 Such permission is not needed, however, by the Government agency for which
the Report has been specifically prepared if that agency wishes to teproduce additional copies for its own use
TABLE OF CONTENTS
Page
iii
LIST OF TABLES
Page
iv
LIST OF FIGURES
Figure Pg
1 A comparison of experimental P-V-T data. . . . 23
Z Deviation plot of the 1958 helium vapor
pressure temperature scale ........ ....... 24
3 Deviation plot of saturation densities . ...... 25
4 Deviation plot of entropies of vaporization . . . Z6
5 Deviation plot between P-V-T data by
Sullivan [14] and equation of state....... .. 27
6 Deviation plot between P-V-T data by
Canfield et al [13] and equation of state. ..... 28
v
FOREWORD
vI
PROVISIONAL THERMODYNAMIC FUNCTIONS FOR HELIUM 4
by
I. D. McCarty
ABSTRACT
List of Symbols
P - absolute pressure
T - absolute temperature
V - specific volume
p - density = i/V
R - universal gas constant= .0820558 I atm/mol. K
Z - compressibility factor = PV/RT
U - specific internal energy
H - specific enthalpy
S - specific entropy
CP - specific heat capacity at constant pressure
Cv - specific heat capacity at constant volume
w - speed of sound
B - second virial coefficient
G - Gibbs function
bi - parameters for the second virial coefficient expression
Sgi - parameters for the saturated density equation (vapor)
Sli - parameters for the saturated density equation (liquid)
nki - parameters for the equation of state
fi parameters for the vapor pressure equation (1)
a1 - parameters for the vapor pressure equation (2)
Superscripts
0 - ideal gas property
Subscripts
c - critical point
lambda point density (liquid) = 36. 514 mol/I (. 14615 g/cmr) [41
A. Vapor Pressure
The 1958 helium vapor pressure temperature scale [31 is repre
sented by the following two equations.
10
In P -fT(Z - i)
i= 1 (1)
In P --FaiT~z i (2)
ip=14 (2-i)(2
j= 1
where T and P are in the same units as equation (1) but the range of
validity is 2. 172 to 0.5 K.
Equation (1) was fit to 611 smoothed points from [31 taken every
0. 005 K between 2. 172 and 5. 1994 1. In addition to the 611 data points,
six constraints were imposed on the least squares estimate of the
parameters. These constraints are listed in table 1.
Table 1
Constraints on Equation 1
1. P = 37800. at T = 2. 17Z
z. P = 760000. at T = 4. Z15
3. P = 1718000. at T = 5. 1994
4. dp/dt = 9Z960. at T = 2. 17
5. dp/dt = 717100. at T = 4. Z2
6. dp/dt = 1267000. at T = 5. 2
-7'
Equation (2) was fit to 333 points taken every 0.005K from 0.5 K to
2. 172 K. [31 In addition to the 333 data points, two constraints were im
posed on the least squares estimate of the parameters. See table 2.
Table Z
Constraints on Equation 2
Table 3 Table 4
Coefficients for Equation 1 Coefficients for Equation 2
f = -3.9394635287 a, = -4.9510540356 X 101
f = 1.4127497598 X 102 a2 = 6. 5192364170 X 102
fs = -1.6407741565 x 103 as = -3.7075430856 x 108
f4= 1.1974557102 x104 a4 = 1.2880673491 x 104
fs= -5. 5283309818 X i04 as = -3.0048545554 x i0
= 1.6621956504 x Jos
fs as = 4.9532267436 x 104
f7 = -3. 2521282840 x105 a7 = -5.9337558548 x 10
fe= 3.9884322750 x 105 as = 5.2311296025 X 104
fs = -2. 7771806992 X 105 as = -3.3950233134 X l0
fIO= 8. 3395204183 X 10 a 1 o= 1.6028674003 X 10
ala = -5. 3541038967 X i0a
a1 a= 1. 1990301906 X 103
ao= -1.6 14 6 3 6 2 9 5 9 X IOs
aj 4 = 9.8811553386
The 1958 helium temperature scale [31 has been under intensive
scrutiny in recent years. Many investigators have published experimen
tal results which indicate the 1958 helium scale is in error by a detect
able amount. Without exception, the pertinent analysis carried out for
this correlation by the author to date indicates two things. First, the
critical pressure of helium 4 is about 10 millimeters of mercury lower
than is reported in the 1958 helium scale, and second, the temperatures
in the 1958 helium scale are lower than the actual thermodynamic scale.
These findings are consistent with recent experimental work. [5, 101.
On the basis of the present correlationr all temperatures below
5. 2 K were adjusted according to:
* The work of Plumb and co-workers [5) was given heavy weight in
this determination.
** The work of Edwards [11 and Roach [111 served as a basis for this
estimate.
9
temperature were omitted. The average deviation for the liquid equa
tion was 0. 027% with a maximum of 0. 1% ( in density) at 4. 4 K. The
average deviation for the vapor equation was 0. 10 with a maximum of
0.4% (in density) at 2. Z K. See figure 2. The range of the liquid equa
tion is from the lambda point to the critical point and the range of the
vapor equation is from 2. 2 K to the critical point.
Table 5
Equation 4 Equation 5
sga
= -1. 2925325530 x I0 - 1 s = -4.3128217346 X 10-1
s = 3.5809505624 X 10-
1 sis = 3.0344215824
sgs = -1. 1315580397 X 10-
1 s = -1. 098 1289602
10
bs = -5. 3143174768 X 10 - 1
The number of significant figures listed for these and all other tab
ulations of coefficients for the various equations are in no way indica
tive of the accuracy of the properties calculated from the equations.
However the number of significant figures given are necessary to avoid
arithmetic errors.
11
Table 7.
3 -i) 3 2 1 0-3)
+ L
i= 1
n. pseYp TIL0
41
+
i=-
ns ip
E
s e' p T I
+ E
i=1
niP - ). (7)
12
Table 8.
Y = -0.0005
13
P~satl i ____
= 0 = -- )dp (8)
G -Gg
1
r-p
T Psat
T8
g
9 ("IT) (Vg - ) =
p
atg
s
sat
1 (sa p
As a result of including the above two equations in the actual
least squares estimation procedure, only one equation is needed to
calculate a given derived property in both the gaseous and liquid states.
In all the equation of state work done at this laboratory in the past this
has not been possible. Previously, derived properties in the compressed
liquid region (T < Tc, p > psat ) were calculated in some other manner
which always created a matching problem at T for all p > Pc" Using
the above technique eliminates this problem as only one equation is
used over the entire region.
The final least squares fit of the data described above was con
strained at the critical point to
(_>) (_> = 0
14
0 C
T (11)Z
+P$- IT + T CP ld)
0
P 1
0 P
VT sp
CP
(ap C
2(13) T
W [( -)(PPE,(14)
In all cases the input variable pairwas pressure (P) and tem
perature (T). This requires an iterative solution to equation (7). In
the course of preparing the tabulations it was learned that in
solving equation (7) for density for all pressures at temperatures below
20 K, it is important to begin the iteration with a reasonable guess. The
reason is that a whole set of unwanted solutions exist in the liquid
vapor coexistence region and another set exist at densities slightly
larger than the solid densities at temperatures to 20 K.
15
There are about three regions of P-T where new P-V-T meas
urements are needed. In the order of their importance they are:
1. The area of the P-V-T surface from about 2. -K to Z0 K with
pressures to at least 350 atmospheres. At the present time only one
,source of experimental data exists which covers even part of this range
and wphich is extensive enough to be of value. [7] Unfortunately these
16
data have some serious shortcomings which have hampered the present
correlation. First these data do not include the saturated liquid and
the saturated vapor, which means that saturation data must be added
from some other source. This immediately introduces consistency'
problems. Secbnd, when these data are compared to other experimen
tal data at 100 atm, the two disagree by about 1. 3% in density. This
corresponds to a 7% error in pressure. See figure 1. Since no other
source exists with which to compare the two sets of data, one has no
choice but to assign a 1. 5% uncertainty in density to the two sets and
therefore the same uncertainty to the calculated values from the equa
tion of state.
It is difficult to tell from Lounasmaas' thesis [71 exactly what his
temperature scale was between 4. Z and 12 K, and conversion to what is
now the best estimate of absolute temperatures in this range of temper
ature is impossible.
2. Low pressure, isothermal measurements from 4.2 to 70 K
would be very helpful. If these measurements are to be of value, they
must be of high accuracy. The measurements are needed to check the
NBS accoustical measurements.
3. P-V-T measurements are needed in the 20 to 70 K region
from low pressures to 1000 atm. Some high pressure measurements
exist in this region [81, but their accuracy is poor, making them of
little use to the correlator.
4. In addition to the P-V-T measurements, specific heat and
speed of sound measurements should be made over the same regions
of pressure and temperature. Ideally, all of the measurements should
be made at the same laboratory in one continuous experimental pro
gram.
IT
19
[12] El Haddi, Z. E. H. A., Dureux, M., and Van Dijk, H., The density
of liquid 4 He under its saturated vapour pressure; and El Haddi,
Z. E. H. A. and Durieux, M. , The density of the saturated vapour
of 'He, Physica 41, 289-304 (1969).
[15] White, D., Rubin, T., Camky, P., and Johnston, I-L L., The
virial coefficients of helium from 20 to 300 K, J. Phys. Chem.,
Vol. 64, No. 11, pp. 1607-1612 (Noy, 1960).
z0
[19] Wiebe, R., Gaddy, V. L., and Heins, C., Jr., The compressi
bility isotherms of helium at temperatures from -70 to 200 degrees
at pressure to 1000 atm. , J. Am. Chem. Soc. , Vol. 53, No. 5,
11. 1721-1725 (May 1931).
z1
X. APPENDIX A
Deviation Plots
zz
120
SGicassfard, Smith
Lounasmaa
80
n
U)
IO
40
.Bo . - 1.8 7 2.04 2 2
DENSITY IN G/CC ,1o
g'ttVjl
23
I -4
Ld
Li
IL
LL
A
o 8II
'
,i0
PRESSURE, MICRONS
24
0.4 I ,
00
2( 0
0
0 2
> 00
a0
F 0. 0 a
0. 0 o
20 28 44 52
TEMPERATURE, K
25
04
VV
V
V
0 0 VV
Z
0
2v
<
I-I
4 V
Z
Lii
U V
!8G4, 4 5.2
TEMPERATURE, K
"21.1 Figure 4. Deviaton Plot of Entropies of Vaporization.
Z6
1.0 P
00
Oo
00
z 1.2,g
0
z
IX-0.2
w.l
-0 2
a-10 2D
- $oQ
B
PRESSURE (ATM)
27
0
0
0.4 0A
0.2 E
z
o E)
A A 0
> B
i
z
W
U
Ld A
-0.2
-0. 4
0 ,oo 200 40 0
:to to0 goo
PRESSURE (ATM)
Z8
A A
Ak
A
0.4 0
z
F
-
> B
-0.4
z
U a
-1.2
-2. 0
0 20o go
PRESSURE (ATM)
IWgPne Figure 7. Deviation Plot between P-V-.T Data by
Lounasmaa [7] and Equation of State.
29
TABLE 9. SATURATION PROPERTIES
TEMP PRESSURE
PRESSURE
DENSITY
ENTHALPY
ENTROPY
oP
CV
SPEED OF SOUND
K MN/H 3
ATH
MOL/LITER
J/HDL
J/MOL-K
J/MOL-K
J/HOL-K
H/S
VAPOR
LIQUID
VAPOR
LIQUID
VAPOR
LIQUID
VAPOR
LIQUID
VAPOR LIQUID
VAPOR LIQUID
2.0 0.0031232
0.030823
0.1956
98.8
50.06
60.11
12.70
135
2.1 0.0041331
0.040790
0.2485
100,5
46.67
60.43
12.74
2.2 137
0.0053256
0.052559
0.3081
36.493
102.1
13.38
47.44
6.84
60.75
33.90
12.77 8.40
139 413
2.3 0.0067169
0.066290
0.3750
36.392
103.8
14.27
46.35
7.22
61.06
32.95
12.80 8.13
2.4 0.0083375
141 410
0.082285
0.4502
36.273
105.4
15.17
45.35
7.58
61.38
32.65
12.82 8.02
143 407
2.5 0.0102102
B.100767
0.5345
36.138
106.9
16.08
44.42
7.93
61.71
32.75
12.84 8.00
145 403
2.6 0.0123547
0.121932
0.6284
35.987
108.4
17.02
43.55
8.28
62.05
33.11
12.86 8.04
2.7 0.0147894
146 399
0.145960
0.7324
35.822
109.8
17.99
42.73
8.62
62.4D
33.62
12.87 8.12
146 394
2.8 0.0175327
0.173034
0.8471
35.643
111.1
18.99
41.96
8.95
62.77
34.22
12.88 8.21
3.3 0.0365484
151 362
0.360705
1.6048
34.549
116.9
24.66
38.61
±0.63
65.00
37.76
±2.89 8.74
152 354
3.4 0.0415462
0.410029
1.7993
34.489
117.9
25.94
38.01
10.97
65.57
38.54
12.88 8.84
3.5 0.0469862
152 346
0.463718
2.0106
34.03
118.7
27.27
37.42
11.31
66.21
39.36
12.87 8.94
151 338
3.6 0.0528867
0.521951
2.2406
33.721
119.4
28.66
36.85
11.65
66.94
40.23
12.86 9.03
151 329
3.7 0.0592660
0.584910
2.4903
33.412
120.1
30.11
36.28
12.00
67.77
41.16
12.85 9.13
4.1 0.0899520
147 289
0.887758
3.7344
31.953
121.4
36.69
34.05
13.44
72.73
46.00
12.76 9.51
145 278
4.2 0.0990178
0.977230
4.1234
31.518
121.3
38.56
33.48
13.83
74.66
47.67
12.74 9.61
4.7 0.1538937
±31 216
1.518813
6.8945
28.588
117.3
50,29
30.27
16.05
97.97
64.81
12.55 10.18
127 20
4.8 0.1669675
1.647841
7.7360
27.738
115.3
53.42
29.47
16.61
110.75
73.16
12.49 10.32
123 187
4.9 0.1808082
1.784438
8.7701
26.709
112.6
57.06
28.55
17.25
133.37
87.09
12.42 10.48
5.0 0.1954458
118 171
1.928900
0.1192
25.383
108.6
61.53
27.45
18.04
182.69
±15.12
12.32 10.68
12 54
5.1 0,2109099
2.081519
12.1070
23.443
102.5
67.74
25.96
19.15
355.38
200.12
±2.16 10.95
108 135
TABLE 10
Provisional Thermodynamic Properties for Helium-4
(pressure in MN/rn5 )
31
32
J/MOL M/S
33
PHASE CHANGE
34
35
J/MOL MIS
PHASE CHANGE
36
J/MOL H/S
37
J/HOL H/S
PHASE CHANGE
38
J/MOL M/S
39
J/MOL HIS
PHASE CHANGE
40
J/HOL M/S
41
J/MOL N/S
PHASE CHANGE
4Z
J/MOL H/S
43
J/MOL M/S
PHASE CHANGE
44
J/MOL M/S
45
PHASE CHANGE
46
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
47
J/HOL H/S
PHASE CHANGE
48
J/HOL H/S
49
JINOL /S
PHASE CHANGE
50
51
PHASE CHANGE
52
53
J/MOL K/S
PHASE CHANGE
54
0:
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
J/MOL H/S
55
J/HOL N/S
PHASE CHANGE
56
57
PHASE CHANGE
58
59
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
J/OL H/S
60
J/MOL MIS
61
J/MOL MIS
62
J/MOL H/S
63
64
J/HOL H/S
65
ISOBAR
J/MOL MfS
66
J/MOL MIS
67
J/MOL M/S
2*5 38.88471
7.41 30°5 15.0 7.34 6.85 272
6.5 24.00910
21.54 98.0 73,0 45.00 11.13 164
9.5 9.41349
35.98 21g.1 146.3 28.93 12.29- 178
12.0 6.63302
42.20 276.4 185.9 24.92 12.43 204
24.0 2.99560
58.02 548.4 348.1 21.67 12.53 295
68
69
PROVISIONAL THERMODY4AMIC PROPERTIES OF HELIUH-4
70
J/MOL K/S
71
72
73
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
74
J/HOL H/S
25
76
J/MOL H/S
77
78
79
80
J/MOL M/S
81
J/MOL M/S
3.0 43.17343
7.66 77.2 19.3 7.43 6.76 383
7.5 37.63190
17.31 127.0 60.5 15.27 10.25 322
10.0 31.72968
22.82 175.4 96.6 23.82 11.50 286
34.0 8.36027
53.11 756.5 457.5 22.22 12.66 375
38.0 7.47909
55.56 844.9 510.6 21.96 12.64 393
45.0 6.32627
59.25 997.4 602.2 21.64 12.62 424
82
J/MOL miS
83
J/HOL flS
84
J/MOL M/S
85
86
J/MOL N/S
87
88
J/MOL MIS
89
90
91
92
93
94
J/MOL MIS
95
96
J/HOL H/S
97
98
99
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
100
101
J/MOL M/S
102
103
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
104
105
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
J/MOL H/S
106
107
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
108
109
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
110
111
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
112
113
0
TABLE 11
(pressure in atmospheres)
115
116
117
PHASE CHANGE
118
119
PHASE CHANGE
122
123
PHASE CHANGE
124
125
PHASE CHANGE
126
127
PHASE CHANGE
IZ8
1Z9
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
PHASE CHANGE
130
131
PHASE CHANGE
132
133
PHASE CHANGE
134
135
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
PHASE CHANGE
136
137
PHASE CHANGE
138
139
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
5 ATMOSPHERE ISOBAR
141
PHASE CHANGE
142
143
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
144
145
146
147
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
148
149
150
151
152
153
154
155
156
157
158
159
10 ATMOSPHERE ISOBAR
160
10 ATMOSPHERE ISOBAR
161
15 ATMOSPHERE ISOBAR
162
15 ATMOSPHERE ISOBAR
163
20 ATMOSPHERE ISOBAR
164
20 ATMOSPHERE ISOBAR
165
25 ATMOSPHERE ISOBAR
166
25 ATMOSPHERE ISOBAR
167
30 ATMOSPHERE ISOBAR
168
30 ATMOSPHERE ISOBAR
169
40 ATMOSPHERE ISOBAR
170
40 ATMOSPHERE ISOBAR
171
50 ATMOSPHERE ISOBAR
172
50 ATMOSPHERE ISOBAR
173
0
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
60 ATMOSPHERE ISOBAR
174
60 ATMOSPHERE ISOBAR
175
70 ATMOSPHERE ISOBAR
176
70 ATMOSPHERE ISOBAR
177
80 ATMOSPHERE ISOBAR
178
80 ATMOSPHERE ISOBAR
179
90 ATMOSPHERE ISOBAR
180
90 ATMOSPHERE ISOBAR
181
18Z
183
184
185
186
187
J/KOL M/S
188
189
190
191
PROVISIONAL THERMODYNAMIC PROPERTIES OF HELIUM-4
192
193
194
195
196
Washington, D C 20402