VISCOSITY OF HY DROGEN I N THE

GASEOUS AND LI QUI D STATES FOR

TEMPERATURES U P TO 5000" K.
L E O N A R D I . S T I E L ' A N D G E O R G E T H O D O S
.l'orthwestern Cj2wersity, Ecanston, Ill.
A viscosity correlation for hydrogen has been developed for reduced temperatures up to TR =75 and
reduced pressures up to P R =100. Experimental viscosities available in the literature for hydrogen at
moderate pressures were utilized to establish the atmospheric viscosity behavior of this substance. For
each experimental high density va!ue, the residual viscosity, p - p*, was determined from the atmospheric
pressure relcitionship and plotted against reduced density to produce a continuous curve for both the
gaseous and liquid regions. This information enabled a plot of viscosity against reduced temperature and
reduced pressure to be developed for this substance. Viscosity values of dissociating hydrogen for tem-
peratures up to 5000" K. were obtained from reported theoretical calculations and were plotted against
temperature for constant pressures.
HE increased importance of hydrogen in design applications
Tnecessitates the development of an accurate correlation for
the prediction of the viscosity of this substance. Thodos and
coivorkers ( d, 23, 28, 34, 36) have developed reduced state
correlations for the es1:imation of the transport properties of
individual substances, which have proved to be highly accurate.
For hydrogen! Schaefer and Thodos (33> 35) have developed
reduced state density and thermal conductivity correlations
from the experimental values of these properties available in
the literature. I n the present study, the approach used b>- the
previous investigators has been employed to develop a correla-
tion for the viscosity of hydrogen in the gaseous and liquid
states for pressures up to 1280 atm. and temperatures up to
5000O K.
Rogers. Zeigler, and Mcil'illiams (37) have recently de-
veloped equations relating the viscosity of hydrogen in the
gaseous and liquid states to the corresponding density for a wide
range of temperatures and pressures. from experimental values
available in the literature through an approach similar to that
utilized in the present investigation. However, their results
are not presented in a form which permits this property to be
readily established at any remperature and pressure, since the
density of hydrogen must be known at these conditions. Also,
in this investigation the high pressure viscosity data are analyzed
differently from those in the study of Rogers. Zeigler, and
Mcil'illiams (,37), and new theoretical calculations of the
transport properties of hydrogen at temperatures where dis-
sociation i s prevalent (52) now permit the viscosity behavior of
the substance in the high temperature region to be re-examined.
Viscosity Behavior at Normal Pressures
Experimental values of the viscosity at atmospheric pressure.
p * . reported by 43 investigators ( 7 > 1. 5-7, 9. 7 7 . 73: 75, 76,
78. 10-21, 24-17. 2 3 , 30: 37, 38-57. 53-55, 57-67) for
hydrogen lvere obtaiimd from the literature and plotted against
the corresponding temperature. The data for most of these
references were found to be consistent with each other and
permitted the moderate pressure viscosity behavior of hydrogen
to be established with a high degree of accuracy for tempera-
Present address, Syracuse University, Syracuse, N. Y .
rures up to llOOo K. I n Figure 1 rhe resulting relationship
bet\veen viscosiT and reduced temperature is presented: along
mith the experimental points of the most significant references
(7, 7 7 , 78, 30, 57). Below T, =1.00: the dependence of vis-
cosity on reduced temperature i s linear on log-log coordinates
and can be expressed analytically as follows :
(1)
The relationship of Figure 1 has been exrended to T, =75,
at which point dissociation becomes noticeable. For 5 6
T, <75, the viscosity dependence on temperature is again
linear and can be expressed as
(2)
Since no significanr difference exists bet\\.een the viscosity of
ortho- and parahydrogen ( 3) , Figure 1 can be used to establish
the viscosity behavior of hydrogen in eirher form.
p* =175 X 1 O- 5 7 $ . g M
p* =208 x 1 0 - 5 ~2 . ~
Viscosity Behavior i n the Dense Phase and l i qui d Regions
To establish the viscosity behavior of hydrogen in the dense
gaseous and liquid regions, a residual approach used success-
fully in previous investigations (4% 23. 28. .3J, 36) has been
employed. Experimental viscosity values of hydrogen in the
dense gaseous and liquid states were obtained from 11 refer-
ences (8, 70, 7 7 , 76, 77,24-27. 56, 58). For each experimental
point, the residual viscosity, p - w* > was calculated by the use
of the atmospheric viscosit): value at the same temperature
obtained from the relationship of Figure 1. These residual
viscosities were plotted against the corresponding reduced
density values obtained from the reduced state density corre-
lation of Schaefer and Thodos (33), as shown in Figure 2.
I t can be seen in Figure 2 that the dara of most of the in-
vestigators for the low density region are consistent and fall on
a single curve. The data of Michels, Schipper, and Rintoul
(27) for isotherms of 25'; 50, 75', loo', and 125' C. were
found to lie on this curve up to reduced densities of p R =1.50.
However, the data of these investigators for the 25' C. isotherm
in the dense gaseous region for pressures between 905 and 1900
atm. deviated from the relationship obtained by extending the
low density curve through the liquid points in a continuous
VOL . 2 NO. 3 A U G U S T 1 9 6 3 233
T
Reduced Temperature, T =-
Tc
Figure 1 . Relationship bet ween viscosity and temperature at moderat e pressures
fashion. Continuous relationships between the residual trans-
port properties and density exist for all of the other substances
investigated (4, 23, 28, 34, 36) and therefore it is felt that the
high density values of Michels et al . for the 25' C. isotherm do
not accurately represent the viscosity behavior of hydrogen in
this region, possibly because of diffusional effects at these
extreme pressures.
J ossi, Stiel, and Thodos (79) have shown that for nonpolar
gases, with the exception of hydrogen and helium? a unique
relationship exists between the group ( p - @* ) E and pR where
= Tc ~/ 6/ M~~2P, 2~3. By the use of viscosity values for deu-
terium in the dense gaseous region to 2150 atm. reported by
Michels, Schipper, and Rintoul (27) and for the liquid region
reported by van Itterbeek and van Paemel (56), the group
( p - p*) E for this substance was plotted against p R along with
values of this quantity for hydrogen. Atmospheric viscosities
for deuterium were obtained from Coremans et al . (7) and
Golubev and Petrov (77). Essentially a single curve resulted
for both substances; however, at high pressures in the dense
gaseous region, the data for deuterium began to curve upward
from the corresponding values for hydrogen, and the curve
through these points when extended appeared to coincide
properly with the liquid points. This behavior indicated that
a single continuous relationship should also exist for hydrogen
in the dense gaseous and liquid regions.
Rogers, Zeigler, and McWilliams (37) have accepted the
high density values of Michels e t al . and have presented qep arate
relationships for the viscosity of gaseous and liquid hydrogen.
However, if the viscosity behavior of hydrogen is not continuous
in the dense gaseous and liquid region, a plot of viscosity against
temperature for different pressures would exhibit discontinui-
ties which should not exist. Therefore, the low density curve
of Figure 2 was extended through the dense gaseous and liquid
region to include the liquid points, by plotting log ( p - p * ) us.
1 / p R and interpolating through this region. The relationship
of Figure 2 should be more dependable than the similar rela-
tionship presented by Brebach and Thodos ( d ) for hydrogen
because of the inclusion of the additional data of Golubev and
Petrov ( 7 7) in the present study. A further experimental study
is required to verify the viscosity behavior of hydrogen es-
tablished in this study for reduced densities in the range 1.5 6
pR <2.2.
Viscosity Correlation for Hydrogen
The residual viscosity plot of Figure 2 was used in conjunc-
tion with the atmospheric viscosity relationship of Figure 1
and the reduced density correlation presented by Schaefer and
Thodos (33) to establish viscosity values for isobars up to P, =
100 and reduced temperatures up to T, =7 5 , These vis-
234 I L E C F U N D A M E N T A L S
2000 1
8 Gibson
v Golubev and Petrov
n lwosoki
+J ohns
b Kestin and Leidenfrost
4 Kestin and Wang
x Kuss
Michels, Schipper, and Rintoul
+ van ltterbeek and van Paerner
t Verxhaffelt
A Gol UbeV
1500
.- 8
.- 2
1 ;
c
c
0) 0
r
i
HYDROGEN
T,=X&K ! =128at rn
pC= 0.0310 g/CC
Reduced Densrty, pl=- P
Pc
Figure 2. Relationship between p -- p* and ,oR for hydrogen
cosity values were plotted against the corresponding reduced
temperatures and pressures to produce the viscosity correlation
for hydrogen presented in Figure 3. The viscosity of hydrogen
at the critical point was found to be pc =303 X 10-5 centi-
poise. The isobars below PR =1.00 terminate at the satura-
tion envelope for the gaseous and liquid states. For PE =
1.00, each isobar of Figure 3 passes through a minimum value.
I t can be seen from this figure that at reduced temperatures
in the range 30 <T, <: 75, the viscosity behavior of hydrogen
is essentially independent of pressure.
Viscosity Behavior of IDissociating Hydrogen
Vanderslice, Weissnnan, Mason, and Fallon (52) have
recently calculated collision integrals for H-H, HZ-HZ in-
teraction potentials obtained from molecular beam experi-
ments. By the use of these collision integrals and the relation-
ship for the viscosity of a binary mixture presented by Hirsch-
felder, Curtiss, and Bird ( 7 4 , Vanderslice et al. (52) have
tabulated viscosity values for dissociated hydrogen for various
temperatures and compositions.
For the dissociation reaction of molecular hydrogen,
the equilibrium mole fraction of atomic hydrogen can be
calculated from the expression
(4)
where K =P n / d & is the equilibrium constant for the dis-
sociation reaction. From the values of K reported by Rossini
et al. (32), the equilibrium mole fraction of atomic hydrogen
was calculated from Equation 4 for isobars from 0.1 to 100
atm. and temperatures between 1500' and 5000' K.
From these equilibrium compositions, viscosity values for
hydrogen were obtained from the tabulation of Vanderslice
et al. (52) and plotted against temperature for constant pres-
sures, as shown in Figure 4. For temperatures below 2500' K.
these theoretical viscosity values coincided with those obtained
by extrapolating the experimental moderate pressure viscosities
up to these temperatures. Above 2500' K. dissociation effects
become noticeable. For each pressure the viscosity of the
dissociated gas is higher than the viscosity of pure molecular
hydrogen over a small temperature range, because the collision
integrals for the H-H interactions are abnormally large
compared to those for the H-H2 and Hz-H2 interactions
VOL. 2 NO. 3 A U G U S T 1 9 6 3 235
5000
4000
3000
2000
1000
800
600
500
400
300
=12.8 atm ( 188p.s.i.a.1
200
100
80
60
50
40
30
2 3 4 5 6 8 1 0 20 30 40 50 60 80 I
T
Reduced Temperature, T =-
0 2 03 04 0506 08 IO
Tc
Figure 3. Viscosity correlation for hydrogen in gaseous and liquid states
6000
v)
.- 8
.- g -
c
C
0,
0
i 4000
3000
2000
m 2000 3000 4000 5000
Temperature, "K
Viscosity of dissociating hydrogen up to 5000" K. Figure 4.
236 I h E C F U N D A M E N T A L S
(52). At higher temperatures the viscosity behavior of the
dissociated gas approaches that of pure atomic hydrogen.
Since at temperatures greater than 5000 K. ionization effects
Lvhich u ere not considered in the theoretical treatment of
Vdndershce et al. (52) lbecome significant, the curves of Figure
4 have been terminated at this temperature. Similar calcu-
lations which have been very recently presented for hydrogen
by Grier (72) agree with those of Vanderslice et al . to within
8% in this temperature range. A further theoretical study is
required before the viscosity behavior of hydrogen can be
accurately established for temperatures above 5000 K.
Nomenclature
I; =equilibrium constant for dissociation reaction
M =molecular weight
Pi? =partial pressure of atomic hydrogen. atm.
Pi?? =partial pressure of molecular hydrogen, atm.
P =pressure, atm.
P, =critical pressure. atm.
Pi: =reduced pressure, P/Pc
T =temperature, K.
T, =critical temperature, O K.
TR =reduced temperature, T/ Tc
Xi, =mole fraction of atomic hydrogen
GREEK LETTERS
p =viscosity, centipoises
p*
=viscosity at moderate pressure, centipoises
at critical point, centipoises
para meter, T,1/6/M !?Pc2 ! B
K =pressure. atm.
p =density, g./cc.
p c =critical density, g./cc.
p,: =reduced density, p i p c
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RECEIVED for review J une 4, 1962
ACCEPTED Februarv 15, 1963
Correction
THE CRI TI CAL RATI O
I n this article by Leo F. Epstein [IsD. ENG. CHEM. FUNDA-
MEXTALS 1, 123 (1962)], on page 123, the quantity z, should
be replaced by 1 z , in three places. I n the second column,
lines six and seven should read :
. . . properly of each gas rather than the value 112, =8/3
predicted by this simple theory. For most real nonpolar
gases 1 / z , is . . . The heading for the third column of the
tabulation at the bottom of the page should be l/zc.
AN EQUATION OF STATE INVOLV
VOL. 2 NO. 3 A U G U S T 1 9 6 3 237