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Shock Compression of Liquid Carbon Monoxide

and Methane to 90 GPa (900 kbar)

ARTICLE in THE JOURNAL OF CHEMICAL PHYSICS · SEPTEMBER 1981

Impact Factor: 2.95 · DOI: 10.1063/1.442401

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 Shock compression of liquid carbon monoxide and
methane to 90 GPa (900 kbar)a)
W. J. Nellis, F. H. Ree, M. van Thiel, and A. C. Mitchell
University of California, Lawrence Livermore National Laboratory, Livermore, California 94550
(Received 16 March 1981; accepted 26 May 1981)

Dynamic equation-of-state data for liquid CO and CH, were measured in the shock pressure range 5-92 GPa
(50--920 kbar) using a two-stage light-gas gun. The liquids were shocked from initial states near their
saturation curves at 77 and III K for CO and CH" respectively. The experimental technique used to double-
shock CH, is described. The CO data were examined by using three theoretical models: (I) a chemically
nonreactive model, (2) a quasi-chemical-equilibrium model that allows CO to dissociate into gaseous species
and graphite, and (3) a chemical-equilibrium model that also includes a dense carbon phase which exists at
higher pressures and temperatures than graphite. This dense phase is assumed to be diamond. Our analysis
shows that at loW pressure chemical equilibrium takes much longer than a typical shock passage time. As a
consequence, the experimental data initially follow the nonreactive Hugoniot to pressures well beyond the
chemical dissociation limit. Both the experimental data and the Hugoniot computed with case (3) agree
satisfactorily at high pressure. Further consequences of these observations to high-explosive studies are
discussed. The theoretical analysis for the CH, data was presented in an earlier paper.

I. INTRODUCTION ture of carbon (graphite or diamond), Oz, and CO2 could

The physical properties of methane (CH 4 ) and carbon
monoxide (CO) at high densities, temperatures, and
pressures are of both scientific and technological in-
terest. CH 4, for example, is a major constitutent of
the outer planets and knowledge of its equation of state
is necessary for theoretical modeling of the compOSition
of these planets. 1 CH 4 is a hydrocarbon and experi-
mentalZ- 4 and theoretical5 results indicate that this class
of materials decomposes into condensed carbon, mole-
cular hydrogen, and other gases at the high pressures
and temperatures achieved in a shock wave. CO is a
major constituent of reacted high explosives and thus
knowledge of its equation of state is useful in developing
a reliable mixture equation of state of detonation pro-
ducts. 6, 7 It is also interesting to compare the shock
compression properties of CO with the correspond-
ing properties of N2 which is isoelectronic with
CO. In the fluid phase these two compounds have simi-
lar physical properties such as the same saturated liquid
density, critical point parameters, etc. However, as
will be shown later, these two apparently similar fluids
behave in a widely different manner under strong shock
compression. Such a comparison provides a new insight
into the physical phenomena that occur at high denSity
and temperature. For example, the shock compression
or Hugoniot curve8• 9 for liquid Nz up to 40 GPa can be
interpreted by a theoretical model which includes inter-
molecular repulsion and molecular rotation and vibra-
tion. 10 Molecular dissociation probably becomes signi-
ficant only when shock pressures exceedS' 40 GPa (400
kbar). On the other hand, if carbon condenses out of
CO in the shock state, as it has been proposed to do in
shocked hydrocarbons, then the Hugoniot of liquid CO
would be expected to become more compressible than
that of Nz• That is, conversion of CO into a fluid mix-
significantly increase the density of this mixture with
respect to that of CO because the denSities of the decom-
position products are significantly higher than that of
liquid CO at atmospheric pressure.
For all these reasons we have performed the first
reported dynamic equation of state measurements on
liquid CH4 and CO. The shock pressure range is 4-90
GPa with compressions up to fourfold over starting
liquid density. A preHminary discussion of the CH 4 data
has been presented, 11 and an earlier paper discussed
the theoretical treatment of the CH 4 data. 10 The theory
for CO will be presented in this paper.
II. EXPERIMENT
The experiments were performed using the same
shock-wave technique used previously9 to study liquid
Ar, N z, and Oz. The method is based on the Rankine-
Hugoniot relations which relate measured kinematic
parameters to thermodynamic variables. These rela-
tions are
P -Po =Po(u. -Uo) (Up -uo) , (la)
V = Va [1 - (up - Uo)/(u. - Uo)] , (lb)
and
(lc)
where Po, Po, Eo, and Uo are respectively the initial
pressure, denSity, specific internal energy, and veloci-
ty of the material, Vo =1/Po is the initial specific VOlume,
P, V, E are, respectively, the final shock pressure,
specific volume, and specific internal energy, u.. is the
velocity of the shOCk wave, and Up is the mass velocity
behind the shock front. For a single strong shock Uo
=0, Po«P, Eo«E and the Hugoniot equations take the
form

a)Work performed under the auspices of the U. S. Department P 1 =POus l Upl , (2a)
of Energy by Lawrence Livermore National Laboratory under
VI =Vo(I-Up1/ud) ' (2b)
contract #W-7405-Eng-48, with partial support from the Of-
fice of Navy Technology. and

J. Chern. Phys. 75(6), 15 Sept. 1981 0021-9606/81/183055-09$01.00 © 1981 American Institute of Physics 3055

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 3056 Nellis, Ree, van Thiel, and Mitchell: Shock compression of CO and CH 4

(2c)
where the subscript 1 refers to the first shock state.
Strong shock waves were generated by accelerating
a planar projectile to a velocity in the range 2.5-7.2
km/s using a two-stage light-gas gun described pre-
viously12 and impacting the projectile onto a cryogenic
target assembly. 9 Liquid CH 4 was used as the coolant
for the CH 4 specimens. Liquid N2 was the coolant for
the CO experiments, which were performed analogously
to those for 02' Gas samples were taken and chemically
analyzed for both coolant and sample, which were of
purity 99.5% and 99.9% or better, respectively. Initial
liquid density was obtained by measuring sample tem-
perature and using the known density for CO and CH 4
along their saturation curves. 13,14 The two lowest-
pressure data points for each liquid were obtained by
using piezoelectric crystal detectors, while the rest of
the data was obtained by using self-shorting electrical
detectors. Typical oscillograms are shown in Ref.
12.
An experiment was also performed to double-shock
CH 4 to more extreme thermodynamic conditions than
could be achieved by a single shock. Double-shocking
is achieved by passing the first shock through the liquid
sample and reflecting this first shock off a high-shock-
impedance anvil. Shock velocity was measured only in
the anvil as illustrated in Fig. 1 because no space was
available to measure the shock velOCities to sufficient
accuracy in the liquid and wall, or baseplate, as well.
The method of analysis, illustrated in Fig. 2, is
called shock impedance matching and is based on the
fact that pressure and mass velocity are continuous
across an interface between two materials. The princi-
pal Hugoniots of the impactor, base plate or wall,
liquid sample, and anvil and the release isentrope of the
wall must be known. The Hugoniots of the metals initial-
ly at room temperature were measured in separate ex-
periments and have the form
Us =c +Su" • (3)
Impactor
plate
Anvil
Liquid Detectors
.-----r--..l,-4r-)~ ( (6)
Impactor
Hugoniot
Hugoniot
Wall release
isentrope
Mass velocity
FIG. 2. Graphical illustration of the method of shock-impedance
matching for double-shock experiments.
A first order correction was applied to the coefficients
C and S to obtain the Hugoniot for aluminum (alloy 1100)
and copper shocked from cryogenic temperatures. 9 The
release isentrope of the aluminum base plate or wall
was obtained by making a first order correction to the
Hugoniot. 9 The Hugoniots used in the shock impedance
matching to obtain mass velocity are listed in Table I.
In Fig. 2 state I is achieved in impactor and wall on
impact at velocity u/. When the shock reaches the wall-
liquid interface, a shock of lower amplitude is trans-
mitted because the liquid has a lower shock impendance
than the wall. Thus, the pressure in the wall releases
isentropically down to the first shock state u,,1 and P1
in the liquid, state 1 in Fig. 2. When the first shock
reaches the liquid-anvil interface, a shock of higher
amplitude is both transmitted into the anvil and also
reflected back into the liquid because the anvil is of
higher shock impedance than the liquid. The reflected
Hugoniot is the locus of states obtained by shocking to
successively higher pressures from state 1. By mea-
suring the shock velocity in the anvil the pressure and
mass velocity u"z and P 2 in the anvil are obtained from
the known Hugoniot of the anvil. By continuity of pres-
sure and mass velOCity this state must lie on the re-

(6)
TABLE I. Coefficients C and S, where U s = C
(1) + Sup. for the Hugoniots of Al (alloy 1100). Cu.
Ta. and CH4 used in the data analysis.

Material T~ (K) C (cm/J.lsec) S

Ala 300 0.5386 1.339
Alb 80-110 0.5420 1.334
Second Cu 110 0.3960 1.500
Base
First plane plane Taa 300 0.3293 1.307
plate
CH 4 111.5 0.2B41 1.16B
FIG. 1. Cross sectional view of projectile, target. and detec-
tors used in shock-velocity measurements on double-shocked aReference 16.
liquid samples. bReference 9.

J. Chern. Phys.• Vol. 75, No.6, 15 September 1981

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 Nellis, Ree, van Thiel, and Mitchell: Shock compression of CO and CH4 3057

second plane were spring-loaded against the anvil and

____- r__ ~--+-I'---~or:~-:r-a-nc-e----_+--;vr~~"O"i"9 were equally spaced on a 3 mm-radius circle. These
detectors were 0.75 mm-diameter aluminum rods whose
I rounded tips were anodized to a depth of 1-2 }lm. This
I thin, anodization in the tips of the shorting detectors
I performs the same function as the 6 }lm thick Mylar 15
Macor I
positioning I sheet used in shock arrival time measurements in me-
block I tals. 18 The angular positions of the detectors are the
1\ same as shown in Fig. 1 of Ref. 9.
I
I The details of detector positioning are shown in Fig.
I 3. Since the anvil is thin (-1 mm), brass collets were
Spring vacuum-sealed with low-melting pure indium solder to the
copper anvil. The self-shorting detectors were then
vacuum-sealed with Varian Torr-Seal epoxy to the brass.
The brass collet provides increased surface area for
mechanical strength and for vacuum sealer. The short-
ing detectors were spring-loaded by pressing a brass
collet on the detector and then loading a spring between
the collet and a positioning block. Thirteen holes for
the detector array were drilled in this block. The holes
1mm for the spring-loaded detectors had minimum clearance;
-I that is, these were positioning holes. The holes for the
self -shorting detectors were larger diameter clearance
holes. The cylindrical positioning block was made of
FIG. 3. Cross sectional view of detector positioning techniques
for shock-velocity measurements across a metal anvil.
Macor, a machineable glass ceramic made by Corning
Glass.
The shock transit time in the anvil was obtained by
flected Hugoniot or double-shocked state in the liquid, measuring the interplanar shock transit time between
state 2 in Fig. 2. the first plane and the second plane 9 (see Fig. 1) and
Shock velocity u aa was measured in a copper anvil after then correcting for the shock transit time in liquid CH 4
the shock traversed a thickness of CH4 • The mass ve- from the first plane to the anvil. The original thickness
locity Upa and the pressure P a in the second shock state and density of the anvil measured at room temperature
in the liquid and the shock state in the anvil are given were corrected for thermal contraction to 110 K.
by In these experiments pure tantalum impactors were nomi-
_ Usq - C. nally 1.0 or 1.5 mm thick. Aluminum impactors were
u,,2 - (4)
S. 3.0 mm thick. Aluminum base plates were 2.0 mm
and thick. The interplanar detector spacing for the single-
shock experiments was 2.2-2.5 mm with a 0.25 mm
P 2 =Po. us. u,,2 , (5) standoff of the first-plane detectors from the wall.
where C. and S. are the linear u. - u" coefficients for the For the double-shock experiment the CH 4 thickness was
anvil and Po. is the initial anvil density. The volume 2.8 mm and the copper anvil was 0.9 mm thick.
Va and internal energy Ea of the second shock state in
the liquid are obtained from the Hugoniot relations: III. RESULTS
The Hugoniot or shock-compression data for liquid
Va =V1 _ (Up1 - u"af (6) CO and CH4 are plotted in Fig. 4 as shock velocity
P a -P 1
versus mass velocity. The four highest-pressure data
and paints for CH 4 have a linear Us - up relationship. The
linear fit to these points has been drawn ttlrough the
data and extrapolated as the dashed line in Fig. 4. The
The values of UH' Ph Vh and E1 were obtained by shock fit coeffiCients are listed in Table I for 3. 5 < up < 8.4
impedance matching using the known equations of state km/s. The Us - Up data for liquid CO exhibits curvature
and the measured impactor velocity UI. throughout the range of the data. Table II lists the
To measure shock velocity in the anvil, shock-wave single-shock data for CO and CH 4 • Table III lists the
detectors were placed on each of two planes. In the experimental parameters for the double shock experi-
first plane (see Fig. 1) six self-shorting electrical de.- ment and Table IV lists the equation of state data for
tectors were equally spaced on a 5 mm-radius circle double-shocked CH 4 • The error analysis is discussed
and a seventh detector was placed on axis. These de- in the Appendix.
tectors were inserted about 25 }lm into the sample cavity
(see Fig. 3). The positions of the tips of these detectors IV. THEORY
were measured with an optical system described previ- High temperatures generated by shock waves induce
ously.9 The six electrical shorting detectors on the CO and CH 4 molecules to thermaUy dissociate through

J. Chern. Phys., Vol. 75, No.6, 15 September 1981

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 3058 Nellis, Ree, van Thiel, and Mitchell: Shock compression of CO and CH 4

TABLE II. Hugoniot data for liquid CO and CH4 • The average initial densities for the Al impactors were 2.710
g/cm 3, for the Al base plates 2.742 g/cm 3, and for the Ta impactors 16.67 g/cm 3• The difference in density be-
tween the Al (alloy 1100) impactors and base plates is caused by thermal contraction of the base plates at To.

u/ To Po up Us p V
Shot Impactor (km/s) (K) (g/cm 3) (km/s) (km/s) (GPa)a (cm 3/mole)
LC08 Al 2.031 77.26 0.8076 1. 692 ± 0.010 3.907 ± O. 048 5. 34± 0.09 19. 66± o. 26
LC09 Al 3.058 77.41 0.8070 2.471 ± 0.014 4. 995 ± O. 030 9.96±0.11 17.54±0.19
LC03 Al 5.737 77.48 0.8067 4.483 ± O. 024 6.978 ± O. 038 25. 24± 0.26 12.41 ± O. 22
LC02 Al 7.275 77.43 0.8069 5.608 ±O. 031 8.045 ± 0.055 36. 40±0. 41 10. 52± O. 26
LC06 Ta 5.652 77.48 0.8067 6.441 ± O. 042 8.971 ± O. 060 46. 61± O. 57 9.79 ±O. 29
LC01 Ta 6.649 77.36 0.8072 7.446±0.056 10. 30± O. 07 61. 90 ± 0.80 9. 62± O. 31
LC07 Ta 7.101 77.21 0.8078 7. 920± O. 055 10. 76± 0.07 68. 84±0. 88 9.15±0.31
CH47 Al 2.531 111. 56 0.4227 2.222 ± 0.012 5.182 ± 0.048 4.87 ± 0.07 21. 68 ±O. 23
CH46 Al 4.165 111.50 0.4228 3.568 ± o. 018 6.994 ± O. 039 10.55±0.1l 18. 58± O. 20
CH44 Al 6.871 111.46 0.4229 5.740 ± 0.035 9.601 ± 0.141 23. 30±0. 44 15.26 ± O. 42
CH43 Ta 5.805 111.56 0.4227 7.165±0.047 11.24±0.11 34. 04± 0.51 13. 76± O. 36
CH41 Ta 6.820 111. 27 0.4232 8.341 ± O. 056 12.55±0.12 44.30±0.66 12.71±0.36

a1 GPa= 10 kbar.

bond scission. The high shock-pressure will also force
the dissociated carbon atoms to precipitate as some
sort of solid residue. This has been experimentally
shown to OCcur in both static 2 and dynamic 3 compres-
sion measurements on hydrocarbons. A theoretical
analysis of the shock wave data for CH 4 reported here
was presented in an earlier paper. 10 The analysis
showed that up to 23 GPa the experimental Hugoniot
data are in excellent agreement with the theory of cor-
responding states; a fundamental assumption of this
theory is that the molecule does not dissociate. Above
23 GPa the experimental Hugoniot pressures become
less than those calculated with this theory. At higher
13
12 /-
•
11 -
pressures and temperatures the CH4 data was analyzed
by the same method which was used for other hydrocar-
bons. 5 That is, satisfactory agreement with the experi-
mental data was achieved by using a theory which as-
sumes that CH4 decomposes into a mixture of diamond-
phase carbon and condensed H2 for p~ 10 GPa and T
~ 1000 K. Chemical-equilibrium calculations showed
that other gaseous chemical species such as C, CH, CH 2 ,
CH 3 , and C2H2 were present but in concentrations too
small to influence shock-wave thermodynamic data. It
should be noted that the term "diamond phase" used
here denotes a dense phase of carbon, like diamond,
which exists at higher pressures and temperatures than
graphite. This dense phase is treated here theoretically
as diamond.
,
A theoretical analysis of the shock wave data of liquid
CO is far more complicated than the situation for CH 4 •
More chemical species appear along the CO Hugoniot and

/ -/-
their concentrations vary sensitively with the Hugoniot
pressure. The present analysis utilizes three gaseous

CH'~/
10 products (CO, CO2 , 02) and two solid carbon phases-
graphite and diamond-hereafter, referred to as C(g)
9 and C(d), respectively. A similar but approximate cal-
~
'"
E / culation has shown that no more chemical species such
.x

~
u
8

7
_ ./\co as 0, C2, Cs , etc. need be considered for the present
problem, since they are present in negligible amounts
over the entire experimental pressure range. The Gibbs

#
0
Qj
>
.x 6 free energy, G, for {n i} moles of the reacting chemical
u
0
.<:
species, where nj is the concentration of species i and
(/)
5 {nj} is the set of all concentrations, is expressed as
/1
4

3
- TABLE III. Experimental parameters for the double-shock
experiment of liquid CH4, shot CH45, using an Al impactor of
denSity 2.714 g/cm 3 and an Al base plate of denSity 2.742 g/
2
cm 3•

U/ To Usin Cu Po of Cu at To
4 5 9 (km/s) (K) (km/s) (g/cm 3)
Mass velocity (km/s)
7.190 111. 39 0.4230 6.361 ± O. 062 9.002
FIG. 4. Shock velocity vs mass velocity for liqUid CO and CH 4•

J. Chem. Phys., Vol. 75, No.6, 15 September 1981

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 Nellis, Ree, van Thiel, and Mitchell: Shock compression of CO and CH4 3059

TABLE IV. First-shock and second-shock states for shot CH45. The first-shock state was obtained by impedance
matching.

Upi EI-EO Up2 E2- E O

(km/s) (\{.}/mol) (km/s) (kJ/mol)
6.033 ± 0.035 25.22 ± O. 29 14. 78±0. 08 291. 9± 3. 4 1. 601 ± O. 058 91.66±4.20 10. 04± O. 54 569. 2± 22.8

a1 GPa=10 kbar.

4
C(P, T, {nj}) = lJ.oo nco + IJ.cozncoz + iJo Zno
2
Cp/R=L b1T 1 , (12b)
+ IJ.C( g) nC( III + IJ.C( d) n C( d) • (8) 1=0

The chemical potentials {IJ.I} for the gaseous and the solid depending on whether T'?1900 K or T< 1900 K, re-
species are given, respectively, by spectively. The functional expressions Eqs. (11)-(12)
for Cp were used in a new chemical equilibrium code
IJ.d{n J }, P, T)=IJ.~(T)+RTlnPYI , (9)
developed recently by Levine. 17(0) The code is based
IJ./(.P, T)=IJ.~(T)+ SP V/(P)dP. (10)
on an improved version of the extent-of-reaction variable
method. 17(b)
1 atm

The first terms in the right-hand side of Eqs. (9) and Table V lists the information relevant to the computa-
(10) represent the chemical potentials at 1 atm. These tion of IJ.~(T). The solid molar volume yep) in Eq. (10)
terms can be expressed in terms of available experi- is represented by the Murnaghan equation
mental and theoretical information on the specific heat
at 1 atm, the heat of formation AH~98.15 and the entropy (13)
values S 298. 15 at 1 atm and 298. 15 K. The spec ific heat
where the subscript 0 refers to the 1 atm and room-
at constant pressure for Oz, CO2 , C(g), and C(d) is ex-
pressed as temperature values. Numerical data on the bulk modulus
3 3
B o, its pressure -derivative B 0, and Vo for graphite and
diamond are also summarized in Table V.
Cp/R = La/xl + L blx- I , (11)
1=0 1=1
The fugacity coefficient 1'1 in Eq. (9) is computed from
where x=T/I000 and T is in Kelvins. For CO the one -fluid van der Waals theory. 18 According to this
4
theory, the total potential energy of the mixture is re-
I
Cp/R =LaIT (12a) placed by an "effective" one-component pair potential
1=0
cp(r), which has an identical functional form as that be-
or tween indiVidual pairs of molecules, given by

TABLE V. Input parameters required for computation of the theoretical Hugoniots discussed in the text. .o.H',298.15 and
5298.15 are, respectively, the heat of formation and the entropy at 298.15 K and 1 atm; 8 0 and 8 0represent the bulk
modulus and its pressure derivative, respectively.

c V·,!
.o.H',298.l5 ,d 5298.15c ,d 0 Bo •
0 1 ·2 3 (kcal/mol) (cal/molK) (cc/mol) (GPa) B'0 •
a
02 al 4.3541 0.2526 - 9.0258 X 10-3 -1.326 x 10-3 0 49.00
01 -0.5200 9.1805 x 10-2 - 4.857 X 10-3
C0 2a a/ 8.7324 -0.2669 ,3. 5163x 10-2 - 9. 524 X 10-4 -94.054 51.07
01 -2.3412 0.3983 - 2.162 X 10-2
C(g)a a/ 4.4928 - O. 5742 0.1076 - 6.173x 10-3 0 1. 359 5.343 51.1 5
01 -1.6551 0.2381 -1.150x 10-2
C(d)b al 1. 1000 1. 5900 0 0 0.453 0.555 3.423 519 3
0/ 0 -0.0745 0

.o.Hf,298.15 c,! c
5298.15
0 1 2 3 4 (kcal/mol) (cal/mol/K)
COa a, 3.8367 3. 849x 10-4 -7.159 x 10-8 4.561 X 10-12 5.635 X 10-17
-26.42 47.21
111 3.7096 - 1. 664 X 10- 3 3.998xl0- 6 -2.602xl0-8 5. 535x 10-13

"Reference 17(a) and the numerical values of aj and 0/ are given in the input library of LeVine's codes (to be published).
1I:r.
Barin and O. Knucke, Thermochemical Properties of Inorganic Suostances (Springer, Berlin, 1973), p. 117.
c"JANAF Thermochemical Data," edited by D~ R. Stull and H. Prophets, Natl. Stand. Ref. Data Ser. -Natl. Bur. Stand. 37
(1971).
~. Hultgren, P. Desai, D. Hawkins, M. Gleiser, K. Kelley, and D. Wagnan, Selected Values of the Thermodynamic
Properties of Elements (American Society for Metals, Menlo Park, 1973), p. 93.
~eferences 23 and 26.
fReference 27.

J. Chem. Phys., Vol. 75, No.6, 15 September 1981

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 3060 Nellis, Ree, van Thiel, and Mitchell: Shock compression of CO and CH 4

(14) 70

However, its energy- and distance-scaling parameters 1. Non-reactive CO

(E, r*) are now dependent on {n;} by the following rela- 60
tions:
\
50
(15) 4- 2.Quasi-equilibrium
m \ (graphite)
!l..
(16) t? 40 \
~ 1-
::J
In Eqs. (15) and (16) the summations extend only over the CI)
CI)
30
\
Q)
gaseous species. The present calculations approximate '-
a.. \
rjJ by (r;"; +r1J)/2 and EiJ by ~ if i ¢j. Henderson
and his co-workers 18 have performed an extensive Monte 20
,
\-+-

Carlo computer study of both the Lennard-Jones and

hard-sphere mixture systems. Their study shows that
3.Eq,;I;b';'m } , , ' , "-
the one -fluid van der Waals theory is adequate to de-
scribe thermodynamic properties such as (P, V, E, T)
relevant to the present shock-wave study. One can
10

0
8
(graphite +
diamond)

derive an expression for the fugacity coefficient y by
relating y; to BAlan;, in which A, the Helmholtz f~ee
energy, is evaluated by means of the one-fluid van der
Waals mixture model, represented by Eqs. (14)-(16).
The final expression 19 for y, which is a complex func-
tion of {nj}, P, and T, will ~ot be presented here. One
point worthy to note here is: G [Eq. (8)] has P as an in-
dependent variable, while the computation of Yj by means
of A requires p as an independent variable. The con-
version from the variable P to p is not so trivial and
was done by an implicit iterative program.
The excess Helmholtz free energy, after subtracting
the ideal-gas contribution, is computed from the
Mansoori-Carnahan-Ross procedure Zo,21 by minimizing
the right-hand side of
by using the hard-sphere diameter as a variational pa-
rameter. The hard -sphere diameter appears in the
excess hard-sphere Helmholtz free energy (AHS), the
hard-sphere radial distribution function (gHS), and a
correction term F introduced by Ross. 22 Ross has shown
that inclusion of F in Eq. (17) is necessary to bring the
computed P and E to agree with the corresponding Monte
Carlo data within the numerical accuracy of the latter
for a widely different class of potentials.
The potential cp(r) appropriate for the present shock-
wave study is the so-called exponential-six potential
cp (r) :; E { a : 6 exp [ a (1 - r: ) ] - a ~ 6 (rr* )
with a:; 13. We showed earlier that this potential pro-
duces reliable Hugoniots for CO2, N z, O2 , and heavy in-
ert gases. 10,22 Numerical values of Elk (in Kelvin) and
r* (in angstrom) are: (E/k, r*) =(108. 3, 4.09), (245.6,
4.17), and (125.0, 3.84) for CO, CO2 , and O2 , re-
spectively.10
We need still to determine concentrations {nj} of
the chemical species. This was done by searching for
a set {nj} which minimizes G (P, T, {nj}) at fixed P and
16
-
.....................,.;..
....... ..:::::- _
..:::-
18 20
Molar volume (cc/mole)
FIG. 5. Shock pressure vs molar volume for liquid CO.
Three theoretical curves described in the text are also shown.
T. The mixture model discussed so far was imple-
mented in the chemical-equilibrium code 17(") as sub-
routines. The resulting solution {nj} was used to com-
pute V and E by numerically differentiating C(P, T,
{n i }) with respect to P and T.
V. NUMERICAL RESULTS AND DISCUSSION
A theoretical Hugoniot point is computed at each tem-
perature by finding a set of thermodynamic variables
(17)
{p, T, E(P, T), ViP, T)} which satisfies the Hugoniot
condition [Eq. (lc)].
Three different theoretical Hugoniots are considered;
Hugoniot 1 which is a chemically nonreactive case,
using corresponding states theory, Hugoniot 2 which al-
lows chemical reactions but without the formation of
the diamond phase, and Hugoniot 3 which assumes com-
plete chemical equilibrium. Thus, along Hugoniot 3,
formations of both the graphite and the diamond phases
are permitted. Figure 5 compares these Hugoniots with
the experimental Hugoniot data obtained in this work.
There are several noteworthy features in Fig. 5.
First, at high pressure (::; 30 GPa) the experimental
8 } ,
Hugoniot data lie close to Hugoniot 3. At this pres-
sure range the Hugoniot temperature shown in Fig. 6
(18) exceeds 7000 K. Thus, a characteristic time for the
chemical equilibrium is enormously reduced (- ex-
ponentially by a Boltzmann factor) from that at the low-
temperature condition. A satisfactory agreement be-
tween the theoretical and the experimental results im-
plies that chemical equilibrium behind the shock front
has been established much faster than the experimental
time scale. At this pressure range, the calculation
shows that aU condensed carbon atoms are in the dia-
mond phase. Along Hugoniot 3 at 30 GPa, for example,
one mole of CO is dissociated into 0.03 mol O2 , 0.38

J. Chern. Phys., Vol. 75, No.6, 15 September 1981

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 Nellis, Ree, van Thiel, and Mitchell: Shock compression of CO and CH 4
11x103
10
2. Quasi-
9
Q 8
...
cu
7 tendency to resist an expected transformation has also
....::Jco
...cu 3. Equilibrium
a. 6 (graphite +
E
QI
I-
diamond)
5 quartz or graphite contains small nucleation sites (i. e.,
4 by a shock wave of a pressure corresponding to the static
1. Non·reactive CO
3 no transformation occurs. The quartz (or graphite) is
2
0 10 20 30 40 50
Pressure (GPa)
FIG. 6. Calculated shock temperatures vs shock pressure for
liquid co for the three theoretical models discussed in the text.
mol CO 2 , 0.19 mol CO, and 0.43 mol of diamond. Ex-
perimental data at the high pressure end (60-70 GPa)
in Fig. 5 appears to become slightly stiffer than both
the present theoretical prediction and the extrapolated
data from the lower pressure experimental points.
Better agreement with the data may be obtained by in-
cluding a temperature dependence in the equation of state
of diamond in Eq. (13). The possibility that this may be
due to a new, yet unknown high-pressure phase of car-
bon also cannot be ruled out. At 60 GPa, for example,
the estimated Hugoniot temperature is about 10000 K.
Both Grover's23 and van Vechten's24 theoretical phase
diagrams of carbon suggest that the point (60 GPa,
10000 K) is well within the liquid metallic phase. It
is theoretically possible to include the liquid and solid
metallic phases of carbon into the present theoretical
framework. However, in practice, it would not be too
useful to do so, since reliable information on these
phases are currently not available.
A second feature that is noteworthy in Fig. 5 is that
the experimental Hugoniot data at low pressure is close
to the chemically nonreactive Hugoniot 1 to at least 10
GPa. This means that the shocked CO is in a metastable
state because, if the shocked CO sample has attained
either a quasi- or complete chemical equilibrium, one
would expect the data to follow Hugoniot 2 or 3. At this
pressure range there is a considerable difference be-
tween the experimental data (or Hugoniot 1) and Hugoniot
2 or 3. The change of concentrations of the chemical
species along Hugoniot 3 is equally significant. At 3 GPa
concentrations are about 0.33 mol each for CO, CO2 ,
and C(g), negligibly small for Oz, and no diamond is
present. At 6 GPa, however, about 37% of carbon atoms
present in the original CO sample is predicted to be in
the diamond phase. No graphite phase is present at this
pressure. Similar calculations (but without the dia-
mond phase) were carried out by Mader 6 by using dif-
J. Chern. Phys., Vol. 75, No.6, 15 September 1981
Downloaded 28 May 2011 to 128.103.149.52. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
3061
ferent mixture equations of state (BKW and the LJD)
and by us by means of the JCZ3 euqation. 25 All the the-
oretical calculations predict that a substantial amount
of carbon will be preCipitated in the range 5 ~ P ~ 10
GPa, contrary to the experimental shock-wave data
points.
In this respect, it is worthwhile to pOint out that a
similar but more pronounced evidence for a material's
been observed in the Hugoniots of graphites 26t27 and
quartz. 28 • 29 The Hugoniot behavior of these materials
can be explained as fOllows 30 : a near-crystal-density
lattice defects), and, at the shOCk temperature generated
transformation pressure, these sites grow so slowly that
transformed to stishovite (or diamond) only if a shock
60 wave of sufficient strength to provide adequate over-
driving pressure (and high temperature) passes through
these materials. In the case of the CO Hugoniot, the
predicted shock temperature along Hugoniot 1 is about
1000 K at 4.5 GPa and is 2000 K at 10 GPa. These
temperatures are much lower than the temperature along
Hugoniot 2 or 3 (See Fig. 5). At this temperature, the
time required for the C-O bond breakage and the subse-
quent crystallization of the dissociated carbon atoms is
conceivably much longer than a typical shock-passage
time (- 200 ns) in the present experiments. According-
ly, we draw a tentative conclusion that the difference
between the experimental Hugoniot pressure and Hugoniot
3 is a manifestation of a nonequilibrium, metastable
phenomenon. At low pressure (:S 10 GPa) the Hugoniot
data (which matches with Hugoniot 1) will likely remain
insensitive to a large range of the experimentally ac-
cessible shock transit time. Therefore, this phenome-
non may be regarded as an essentially time-independent,
metastable event as far as dynamiC measurements are
concerned. However, at higher shock pressures in the
range 10:P~30 GPa the shock temperature will be
correspondingly higher. So, chemical equilibrium will
set in faster, but not necessarily fast enough to achieve
equilibrium in the time of the experiment. In order to
determine the actual time scale for thermal and chemi-
cal equilibrium to be established and in particular if
this time scale is comparable to the experimental time,
additional experiments would be useful. These include
time-resolved spectra of the thermal radiation emitted
from shocked CO and time-resolved stress or mass
velocity measurements.
Our last observation in Fig. 5 is connected with
Hugoniot 2. Recall that the diamond formation is not
permitted along this Hugoniot. Figure 5 shows that
such a restriction gives a generally poor result. This
may be potentially Significant for some theoretical
calculations related to the post-detonation behavior
(the Chapman-Jouget point, concentrations of detonation
products, release adiabats, etc.). In a situation where
a high explosive contains carbon as a constituent, avail-
able theoretical models 6t 7 assume that carbon atoms
may condense only into the graphite phase or into an
"amorphous" phase, which has graphite-like physical
 3062 Nellis, Ree, van Thiel, and Mitchell: Shock compression of CO and CH 4
properties but a slightly different heat of formation.
In the preceding analysis we have shown that it is im-
portant to include the diamond-like phase. Furthermore,
since the Chapman-Jouget temperature of most available
high explosives is less than 5000 K, additional theoreti-
cal complications found here, namely, possible time-
dependent effects and metastability, may have to be con-
sidered simultaneously in studying the post-detonation
behavior.
ACKNOWLEDGMENTS
We acknowledge the support provided by R. N. Keeler
of the Office of Navy Technology to perform the initial
methane experiments. We acknowledge R. E. Neather-
land, M. A. Brooks, and M. A. Benapfl for assembling
the cryogenic target holders. We thank D. E. Bakker
and M. A. Brooks for firing and maintaining the two-
stage gun, J. Samuels and H. R. Martinez for assistance
with the electronic measurements, and J. Chmielewski
for fabricating the projectiles. We wish to thank N.
Brown of Specialty Engineering Associates for providing
the shock wave detectors. We acknowledge the con-
tributions of G. J. Devine and V. W. Morasch to the
cyrogenic system to handle liquid methane. We thank
Pacific Oxygen Company and Lawrence Berkeley Labora-
tory for supplying the liquid methane. We are grateful
to M. Ross for making his computer code available to
solve Eq. (17).
APPENDIX-ERROR ANALYSIS
The uncertainties in the single-shock experiments
were calculated by the method described previously. 9,16
This method was extended to the calculation of the un-
certainties in the double-shock experiment. For any
given experimentally determined parameter the total
uncertainty is the sum of the uncertainty due to experi-
mental uncertainties in measured quantities and the uncer-
tainty arising from a systematic bias in the data analYSis.
As an example of the latter, there is an uncertainty in the
Hugoniots of standard materials due to uncertainties in
the data for these materials. In a double-shock liquid
exper iment four measured Hugoniot curves are used for
impactor, wall, liquid, and anvil, as well as a calculated
release isentrope for the A1 wall. Use of these curves
introduces a systematic bias into the data analysis.
The mass velocity Upz in the anvil and thus in the
double-shocked liquid is given by
usa - Ca (4)
Upz =
Sa
where usa is the shock velocity in the anvil and Ca and
Sa are the linear u. - Up coefficients for the anvil
.
Hugoniot. Therefore, the uncertainty in Upa is given by
oUpa =otlpz + ~
S ' (19)
• yet; but its main idea is outlined in H. B •. Levine, "A Project
where oU:z is the systematic bias due to the uncertainty
in the Hugoniot of the anvil and oua• Is. is the uncertain-
ty in Upz due to the experimental uncertainty in the mea-
sured shock velocity in the anvil. The pressure P 2 in
the anvil and thus in the double-shocked liquid is
(5)
J. Chern. Phys., Vol. 75, No.6, 15 September 1981'
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where Po. is the initial denSity of the anvil. Therefore,
~=I~I+
Pz Upa
(20)
The systematic uncertainty ot4a is obtained by calculat-
ing 20"o(u,z) given in Ref. 16 as the systematic error in Us
calculated at Upz for the anvil Hugoniot, adding 20"o(Upz)
to C a , and calculating a new mass velocity, say u~a.
Then lot4al = IU;2-Upz l. For shot CH45, opo IPo""0.001
oua• Ius. =0. 0098 and (2u s - Ca)/(u s - C.) =3.65. Thus,
the experimental uncertainty in P 2 is 3.58%; the sys-
temmatic bias is 1.00%. The total uncertainty in P a
is 4,6% which is also 4.6 times the experimental un-
certainty in the shock velocity measurement.
The systemmatic uncertainties in Va and E2 - Eo are
given by the sum of terms proportional to I ot411 and to
I ot4al. The experimental uncertainties are given by
square roots of the sum of squared terms proportional
to experimental uncertainties in measured quantities.
The expressions were derived in the same manner il-
lustrated in Ref. 16 for calculating uncertainties in
single-shock experiments.
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proval or recommendation of the product by the University of
California or the U. S. Department of Energy to the exclusion
of others that may be suitable.
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J. Chern. Phys., Vol. 75, No.6, 15 September 1981

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