Vapor pressure and liquid heat capacity of perhydroacenaphthylene and perhydrophenanthrene

Article abstract of DOI:10.1021/je000130n

Saturated vapor pressures and liquid heat capacities have been measured for liquid perhydroacenaphthylene and perhydrophenanthrene by comparative ebulliometry over an approximate pressure range from (8 to 100) kPa and by heat conduction calorimetry over a temperature range from about (305 to 335) K. The obtained results for vapor pressures and for heat capacities have been represented within experimental uncertainties by the Antoine and the Cox equations and by an empirical polynomial equation, respectively, and compared with the data available in the literature.

Full text of DOI:10.1021/je000130n

J . Chem. Eng. Data 2000, 45, 1205-1210
1205
Va p or P r essu r e a n d Liqu id Hea t Ca p a city of
P er h yd r oa cen a p h th ylen e a n d P er h yd r op h en a n th r en e
Vla d isla v Roh a´cˇ,† Mir osla v Cˇ en sk y´,† Dia n a Za la ,‡ Vla stim il Ru˚ zˇicˇk a ,*,† Kveˇtosla v Ru˚ zˇicˇk a ,†
Ka r el Sp or k a ,§ a n d Ka r el Aim |
Department of Physical Chemistry and Department of Organic Technology, Institute of Chemical Technology,
166 28 Prague 6, Czech Republic, Ecole polytechnic fe´de´rale de Lausanne, Ecublens, CH - 1015 Lausanne,
Switzerland, and E.Ha´la Laboratory of Thermodynamics, Institute of Chemical Process Fundamentals,
Academy of Sciences of the Czech Republic, 165 02 Prague 6 - Suchdol, Czech Republic
Saturated vapor pressures and liquid heat capacities have been measured for liquid perhydroacenaph-
thylene and perhydrophenanthrene by comparative ebulliometry over an approximate pressure range
from (8 to 100) kPa and by heat conduction calorimetry over a temperature range from about (305 to
335) K. The obtained results for vapor pressures and for heat capacities have been represented within
experimental uncertainties by the Antoine and the Cox equations and by an empirical polynomial equation,
respectively, and compared with the data available in the literature.
Tricyclic perhydroaromatic substances have been of
interest for a long time to organic chemists, as they occur
widely in substances of nature.1-4 Cyclic substances orig-
inating by hydrogenation of aromatic hydrocarbons are
important as intermediates for the synthesis of chemical
specialties,5,6 as potential aircraft and missiles fuels,7 and
as substitutes for aromatic solvents because of increasingly
strict environmental legislation.8 The complete hydrogena-
tion of the aromatic skeleton can be accomplished by using
metal catalysts.9
The industrial significance of perhydroacenaphthylene
became more important recently when production of new
adamantane-based pharmaceuticals was initiated. A series
of reaction pathways begins with perhydroacenaphthylene,
leads to 1,3-dimethyladamantane as an intermediate, and
finally gives a desired pharmaceutical. As an isomerization
of a mixture of stereoisomers of perhydroacenaphthylene
results in 1,3-dimethyladamantane, it is ineffective to
separate individual stereoisomers.
In addition to finding suitable chemical reaction path-
ways for synthesizing polycyclic perhydrohydrocarbons, it
is also desirable to determine their basic physicochemical
properties. Vapor pressure belongs to properties required
for phase equilibria calculations as well as for modeling
the fate and distribution of substances in the compartments
of the environment.
This work has been concerned with measurement of
vapor pressure and liquid heat capacity of a mixture of
stereoisomers of tricyclo[7.2.1.05,12]dodecane (perhydroace-
naphthylene) and of a mixture of stereoisomers of tricyclo-
[8.4.0.02,7]tetradecane (perhydrophenanthrene).
DEZA a.s., Valasˇske´ Mezirˇ´ıcˇ´ı, minimum purity of 99%) in
cyclohexane solution on a commercial nickel catalyst (Ni-
NiO/Al2O3 catalyst type 6524, Leuna, Germany) at a
maximum temperature of 180 °C and pressure of 8 MPa.
Under these reaction conditions 1,2-dihydroacenaphthylene
was completely hydrogenated to perhydroacenaphthylene.
A detailed description of the hydrogenation procedure
has been given.10 The product of hydrogenation was
analyzed using the GC-MS technique and contained the
following mixture of stereoisomers: 70% cis,trans,trans, 7%
trans,trans,trans, 5% cis,cis,trans, and 18% cis,cis,cis,
respectively, cis,trans,cis. It was reported7 there were six
possible stereoisomers of perhydroacenaphthylene. Three
of them were synthesized, and MS spectral data were
reported.7
Perhydrophenanthrene was prepared by hydrogenation
of phenanthrene (product of DEZA a.s., Valasˇske´ Mezirˇ´ıcˇ´ı,
original purity of 90.5%) thoroughly purified by repeated
recrystallization. Hydrogenation was carried out in a
cyclohexane solution on a commercial nickel catalyst (Ni-
NiO/Al2O3 catalyst type 6524, Leuna, Germany) at a
maximum temperature of 250 °C and pressure of 4 MPa.
Under these reaction conditions phenanthrene was com-
pletely hydrogenated to perhydrophenanthrene. The prod-
uct of hydrogenation was analyzed by a GC-MS technique.
The mass spectral data showed the product contained a
mixture of five species with an identical molar mass of 192.
These species were assigned to stereoisomers of perhydro-
phenanthrene, and their relative amounts were as fol-
lows: 47% of isomer A, 21% of isomer B, 29% of isomer C,
3% of isomer D, 1% of isomer E. It has been reported1 that
there were six stereoisomers of perhydrophenanthrene. As
we found no spectral data for any of these, it was impossible
to identify the stereoisomers in the mixture obtained in
this work. However, the reaction conditions used in this
work determine uniquely the stereoisomeric composition
of the synthesized perhydrophenanthrene.
Exp er im en ta l Section
Ch em ica ls. Perhydroacenaphthylene was prepared by
hydrogenation of 1,2-dihydroacenaphthylene (product of
* Corresponding author. E-mail: vlastimil.ruzicka@vscht.cz.
† Department of Physical Chemistry, Institute of Chemical Technology.
‡ Ecole polytechnic fe´de´rale de Lausanne. On leave as an IAESTE
fellow.
Appa r a tu s a n d P r oced u r e for Va por P r essu r e Mea -
su r em en t. A modified ebulliometer and an apparatus
based on comparative ebulliometry have been used for the
vapor pressure measurements. The experimental arrange-
§ Department of Organic Technology, Institute of Chemical Technology.
| Academy of Sciences of the Czech Republic.
10.1021/je000130n CCC: $19.00 © 2000 American Chemical Society
Published on Web 10/25/2000

1206 J ournal of Chemical and Engineering Data, Vol. 45, No. 6, 2000
Ta ble 1. Va p or P r essu r e of P er h yd r oa cen a p h th ylen e
Antoine, eq 1
Cox, eq 5
T/K
pexp/kPa
∆T/K
∆p/kPa
100∆p/p
∆T/K
∆p/kPa
100∆p/p
422.072
430.559
437.807
443.983
444.006
450.351
457.082
463.527
469.800
469.963
475.900
475.900
482.070
491.890
501.290
511.580
513.930
8.449
11.210
14.089
17.002
17.000
20.527
24.847
29.719
35.193
35.187
41.181
41.172
48.101
60.822
75.424
94.172
99.173
0.010
0.015
-0.006
-0.013
0.001
0.014
0.024
0.014
0.036
0.007
-0.07
-0.12
0.01
0.08
0.14
0.07
0.14
0.02
-0.007
0.015
0.006
-0.001
-0.009
0.000
-0.011
-0.001
0.012
-0.024
0.007
0.005
0.012
0.001
0.002
-0.011
0.005
0.008
0.011
0.004
-0.013
-0.007
0.002
0.012
0.000
0.025
0.003
-0.039
0.084
-0.027
-0.020
-0.062
-0.009
-0.018
0.125
-0.059
0.030
0.051
0.05
-0.12
-0.05
0.01
0.07
0.00
0.10
0.01
-0.11
0.24
-0.07
-0.05
-0.13
-0.01
-0.02
0.13
-0.06
0.07
0.11
-0.001
-0.010
-0.017
-0.008
-0.016
-0.003
0.014
-0.023
0.012
0.010
0.020
0.009
0.006
-0.016
-0.003
0.011
-0.047
0.076
-0.13
0.21
-0.048
-0.041
-0.098
-0.060
-0.053
0.180
0.035
0.044
0.068
-0.12
-0.10
-0.20
-0.10
-0.07
0.19
0.04
0.11
0.13
mean absolute deviation
standard deviation
0.014
ment has been described in detail,11,12 and thus only a brief
characterization is given below.
were measured with a commercial heat-conduction C-80
Setaram calorimeter equipped with standard cells having
the inner volume of 9.5 cm3 reduced by a raised bottom. In
a typical heat capacity experiment, the temperature was
Two very similar ebulliometers essentially of the classical
Swietosławski design have been used. A reference ebulli-
ometer was filled with water as a reference fluid of known
vapor pressure and partly enclosed in a box that shielded
it from temperature fluctuations of the surroundings. The
measuring ebulliometer (all made of quartz) was filled with
about 60 cm3 of the investigated substance and placed in
an air thermostat, whose temperature was kept constant
to (1 K at a value about 15 K below the actual boiling
temperature. Both ebulliometers were connected in parallel
via cold traps to the pressure-controlling assembly, whose
main parts were two buffer reservoirs (connected in series
by a pneumatic resistor) and an air-thermostated mercury
manostat. The pressure control assembly made it possible
to maintain the pressure in the ebulliometric system
constant within less than (3 Pa at a series of evenly spaced
pressure values in the range from 3 kPa to over 100 kPa.
The boiling temperatures (of water and of a substance
investigated) in the two ebulliometers at a given pressure
were measured simultaneously by two 2850D-type probes
of the Hewlett-Packard quartz thermometer (Model HP-
2801A). Both probes had been repeatedly calibrated against
a Leeds & Northrup standard platinum 25 Ω resistance
thermometer (Model 8163-B) coupled in a four-wire con-
nection with a precision resistance bridge Model F17A
(Automatic Systems Laboratories, Milton Keynes, U.K.).
Overall accuracy in the measured boiling temperatures is
estimated to be better than (0.01 K within ITS-90 over
the whole investigated range.
increased in steps of 10 K with a heating rate of 3.3 mK‚s-1
.
The average heat capacity C for a given temperature step
T was obtained from the time integrals of the differential
thermopile signal for the filled and empty sample cells. As
the vapor pressure of all studied substances was below 5
kPa at all experimental temperatures, it was not necessary
to apply any correction for sample vaporization. The
temperature dependence of heat capacity for both studied
substances was close to linear; then the average heat
capacity over the individual temperature step could be
considered directly as the true heat capacity relating to the
mean temperature of the interval. The calorimeter was
calibrated with synthetic sapphire (R-Al2O3), NIST Stan-
dard Reference Material 720. The accuracy of heat capacity
measurements estimated from calibration and test experi-
ments with several substances of well-known heat capacity
values is (1% of the measured value. As all experimental
heat capacities determined in this work lie about 100 K
below the normal boiling temperature, the reported satura-
tion heat capacities are identical to isobaric heat capacities.
Resu lts a n d Discu ssion
Measured vapor pressures of perhydroacenaphthylene
and of perhydrophenanthrene are presented in Tables 1
and 2 together with the results of their representation by
the Antoine and the Cox equations.
The Antoine equation was employed in the form
From the boiling temperature of water the corresponding
equilibrium pressure in the system was calculated at each
point by using the accurate vapor pressure equation.13 The
accuracy in pressure determined in this manner is esti-
mated to be better than (0.1% of the measured pressure
value over the entire range studied. Nevertheless, due to
the fact that the samples investigated were mixtures of
stereoisomers rather than pure chemical species, certain
fluctuations in both temperature and pressure were ob-
served during the measurements. Accordingly, the uncer-
tainties assigned to the measured quantities had to be
larger compared to those used in our previous studies.14,15
Their values are specified below in the paragraphs describ-
ing the vapor pressure data processing.
log(p/kPa) ) A - B/[(T/K) - C]
(1)
where p and T denote the saturated vapor pressure and
temperature, respectively, and A, B, and C are adjustable
parameters characteristic of a substance.
The parameters A, B, and C in eq 1 were evaluated from
the experimental vapor pressure data by the method of
maximum likelihood,16,17 allowing for the fact that both the
measured variables are subject to experimental uncertain-
ties. A symmetric maximum likelihood objective function
was used in the form
-2
S ) Σ[(∆Ti)2(σT,i
)
+ (∆pi)2(σp,i)-2
]
(2)
Appa r a tu s a n d P r oced u r e for Hea t Ca pa city Mea -
su r em en t. Saturation heat capacities in the liquid phase
where the index in the summation runs over all experi-

J ournal of Chemical and Engineering Data, Vol. 45, No. 6, 2000 1207
Ta ble 2. Va p or P r essu r e of P er h yd r op h en a n th r en e
Antoine, eq 1
Cox, eq 5
T/K
pexp/kPa
∆T/K
∆p/kPa
100∆p/p
∆T/K
∆p/kPa
100∆p/p
454.684
455.090
463.522
463.710
471.070
471.140
477.110
477.570
483.870
484.220
490.960
491.250
497.710
498.110
498.120
504.380
504.790
510.950
511.210
517.730
528.150
528.150
538.120
548.840
551.610
8.292
8.438
-0.073
-0.037
0.058
0.005
0.019
-0.001
0.097
-0.016
0.058
0.045
0.023
-0.052
-0.004
-0.023
0.001
-0.142
0.023
-0.106
0.039
-0.085
0.077
-0.122
0.121
0.134
-0.139
0.148
-0.061
0.150
0.110
0.55
0.27
-0.47
-0.03
-0.16
0.00
-0.84
0.13
-0.52
0.19
-0.34
0.31
-0.41
0.41
0.45
-0.40
0.42
-0.15
0.36
0.23
-0.037
-0.003
0.056
0.000
0.000
-0.020
0.074
-0.038
0.039
0.022
0.002
-0.049
0.000
0.000
0.023
-0.110
0.056
-0.070
0.074
-0.059
0.103
-0.118
0.123
0.136
-0.171
0.115
0.27
0.02
-0.43
0.00
0.00
0.16
-0.64
0.33
-0.34
0.36
-0.24
0.41
-0.40
0.42
0.46
-0.48
0.33
11.208
11.207
14.087
14.085
16.999
17.005
20.522
20.532
24.860
24.845
29.718
29.718
29.709
35.185
35.185
41.188
41.186
48.109
60.846
60.857
75.413
94.142
99.533
-0.021
0.036
-0.041
0.025
-0.033
0.042
-0.042
-0.046
0.039
-0.044
0.040
-0.042
-0.047
0.048
-0.033
0.032
-0.017
0.002
0.004
0.005
0.001
-0.001
-0.004
0.026
-0.042
0.014
-0.136
0.073
-0.33
0.18
-0.035
-0.021
-0.021
-0.019
-0.010
0.019
0.028
0.033
0.042
-0.013
-0.025
-0.035
-0.014
0.012
0.049
0.064
0.088
-0.03
-0.04
-0.06
-0.02
0.01
0.05
0.24
0.33
0.140
0.132
0.085
-0.232
-0.357
0.102
0.23
0.22
0.11
-0.25
-0.36
0.31
mean absolute deviation
standard deviation
0.136
0.38
0.036
Ta ble 3. P a r a m eter s of th e An toin e Equ a tion (Eq 1)
and the standard deviations sT and sp, defined by
sX ) [Σ(Xcalc,i - Xexp,i)2/(n - m)]1/2
A
B
C
Tb/K
,
X ) T and p (4)
perhydroacenaphthylene 5.957 216 1710.212
perhydrophenanthrene
82.12819 514.93
552.74
5.480 736 1433.463 140.2354
where m is the number of parameters in the correlating
eq 3 and n is the number of experimental observations. It
is seen from the tables that the Antoine equation repre-
sents the experimental vapor pressure data within the
estimated experimental errors.
mental observations and σT,i and σP,i are estimated stan-
dard deviations in measured temperature and pressure for
the i-th observation, respectively. For computations with
the original data presented in this work, these were
assigned the values σT,i ) 0.02 K and σp,i ) 0.001pexp,i for
The Antoine equation is generally considered to be the
most appropriate for correlating vapor pressures over the
so-called medium-pressure region that spans the range
approximately from 1 kPa to 200 kPa. It should be noted,
however, that the Antoine equation is unsuitable for
extrapolation below the lower limit of experimental data
due to its low flexibility.18 We present the Antoine equation
parameters here, as it is often used in many different
standard program packages for the calculation of vapor
pressures close to the normal boiling temperature.
Since all studied substances are high-boiling, our concern
was to use for data fitting another relationship exhibiting
good extrapolation capability in the direction toward the
triple point and not requiring use of critical parameters.
Our previous tests have shown18 that the Cox equation is
a convenient option:
perhydroacenaphthylene and σT,i ) 0.04 K and σp,i
)
0.002pexp,i for perhydrophenanthrene, respectively, for all
observations as a priori estimated from the properties of
the experimental setup and substances investigated, as
well as from the observations made during the measure-
ments (as described above). The parameters of the cor-
relating eq 1 and the calculated values Tcalc,i and pcalc,i
corresponding to each observation were evaluated by
minimizing the objective function, as defined by eq 2, by a
robust iterative procedure (using the simplex method in
each of the alternating steps).
The resulting parameters of the Antoine equation (eq 1)
obtained for the present vapor pressure data on perhy-
droacenaphthylene and perhydrophenanthrene are given
in Table 3 along with the calculated normal boiling
temperatures. Tables 1 and 2 display also the correspond-
ing characteristics of the fit, namely the deviations
2
T0
p
ln
) 1 -
exp( AiTi)
(5)
∑
(p )
(
)
T
i)0
0
∆Ti ) Tcalc,i - Texp,i and ∆pi ) pcalc,i - pexp,i
where T0 and p0 relate to a reference temperature and to
the corresponding vapor pressure, respectively. In this
work, the normal boiling temperature T0 was used as a
reference point and was determined by a fit of the vapor
pressure data with eq 5, in which p0 ) 101.325 kPa and
A0, A1, A2, and T0 were adjustable parameters. The evalu-
ated parameters of the Cox equation (eq 5) are summarized
in Table 4 along with the normal boiling point. It is
documented from Tables 1 and 2 by comparing the mean
absolute and standard deviations that the Cox equation is
evaluated at the minimum of the objective function. The
deviations in percent of pressure are also displayed, since
the second term in the objective function (eq 2), with σp,i
specified as a constant multiple of the i-th pressure value,
just minimizes the percent deviations in pressure. Also
given in Tables 1 and 2 are the mean absolute deviations
aT and ap, given by
aX ) Σ|Xcalc,i - Xexp,i|/n, X ) T and p
(3)

1208 J ournal of Chemical and Engineering Data, Vol. 45, No. 6, 2000
Ta ble 4. P a r a m eter s of th e Cox Equ a tion (Eq 5)
A0
A1
A2
T0/K
p0/kPa
perhydroacenaphthylene
perhydrophenanthrene
2.487 00
4.546 89
1.741 07 × 10-4
-7.709 77 × 10-7
514.99
552.47
101.325
101.325
-8.019 71 × 10-3
7.508 66 × 10-6
pressure, which in all cases but one does not exceed 5 kPa;
(iii) several authors presented a boiling range rather than
a single boiling temperature value at a specified pressure.
In Figures 1 and 2 the boiling range is symbolized by
connecting the adjacent points with a dashed line.
For perhydroacenaphthylene we found in the literature
four sources of data. Except for the data by Grosse et al.,20
who reported a boiling temperature range at atmospheric
pressure determined when studying catalytic dehydroge-
nation of polycyclic naphthenes, all remaining reported
boiling point pressures lie below the lower limit of the vapor
pressure data determined in this work. As found in ref 18,
the Cox equation was suitable for extrapolation toward the
fusion temperature. Therefore, the comparison of literature
data with those calculated from the Cox equation is
considered to be qualitatively correct when extrapolating
about 50 K below the lower limit of the present data. The
data by Grosse et al.20 as well as the data by Schneider et
al.,21 who determined a boiling temperature range of a
mixture of four isomers at a single pressure during distil-
lation of products of hydrogenation of acenaphthene, agree
within less than 20% with the present vapor pressures even
though the data by Schneider et al. lie about 40 K below
the lower limit of the present data. The data by Zakharkin
et al.22 deviate substantially from the data obtained by a
long-range extrapolation of the Cox equation going to the
pressure of 1 kPa. Boldt et al.7 synthesized three of the six
possible stereoisomers of perhydroacenaphthylene and
reported their boiling points at a reduced pressure around
1 kPa obtained from temperature and pressure readings
during distillation of a reaction product. The boiling point
for the cis,cis,cis isomer differs significantly from the
present data; boiling points for the cis,cis,trans and
trans,trans,trans isomers exhibit smaller deviations from
the present data.
F igu r e 1. Percent in pressure deviation graph for the vapor
pressure of perhydroacenaphthylene with the zero line represent-
ing eq 5 with the parameters of Table 4 (∆p ) pCox - pexp): O,
this work; ], Grosse et al.;20 0, Schneider et al.;21 2, Zakharkin
et al.;22 b, Boldt et al.7 The dashed line connecting the adjacent
points symbolizes the boiling range at a given pressure reported
by the author.
F igu r e 2. Percent in pressure deviation graph for the vapor
pressure of perhydrophenanthrene with the zero line representing
eq 5 with the parameters of Table 4 (∆p ) pCox - pexp): O, this
work; ], Pinkney et al.;25 2, Durland and Adkins2; 0, Linstead
and Walpole3; /, Linstead;23 9, Grosse et al.;20 shaded triangle,
Boelhouwer et al.;28 4, Schneider et al.;21 shaded box, API RP 42;24
+, Eimasry and Gisvold;5 ×, Allinger et al.1; - - -, TRC Tables.19
The dashed line connecting the adjacent points symbolizes the
boiling range at a given pressure reported by the author.
For perhydrophenanthrene, in addition to the “TRC
equation”, we found in the literature 10 more sources of
data. With the exception of the “TRC equation”, all reported
boiling point pressures lie below the lower limit of the vapor
pressure data determined in this work. The data calculated
from the “TRC equation” deviate substantially from those
calculated from the Cox equation at their lower limit.
Durland and Adkins2 presented boiling points at three
pressures obtained by reading temperatures during distil-
lation of pure substances in the fractionating column.
Linstead and Walpole3 reported two boiling points at
slightly different pressures in a study of stereoisomerism
of perhydrophenanthrenes. Grosse et al.20 reported a
boiling temperature range in a pressure range determined
in a study of catalytic dehydrogenation of polycyclic naph-
thalenes that included perhydroacenaphthylene. Schneider
et al.21 determined a boiling temperature range of a
mixture of four isomers at a single pressure during distil-
lation of products of hydrogenation of phenanthrene. Al-
linger et al.1 in a conformational analysis study of perhy-
drophenanthrenes reported a boiling temperature range in
a vacuum distillation of a mixture of two isomers con-
sisting of 60% of the cis,syn,cis isomer and 40% of the
trans,syn,cis isomer. All the above-mentioned data de-
viate from the present experimental vapor pressures by less
than about 55%. Linstead et al.23 synthesized cis,syn,cis
perhydrophenanthrene by catalytic hydrogenation of
superior to the Antoine equation in describing the mea-
sured vapor pressures over the experimental temperature
range.
The Cox equation parameters are used as the zero
baseline in Figures 1 and 2, where comparisons of the
present vapor pressure data with literature data are given
in terms of percentage deviation plots, where ∆p ) pCox
-
pexp. Ebulliometric vapor pressure data determined in this
work are included in the deviation plots to show their
temperature range.
Some remarks of general validity are summarized be-
low: (i) there are no reliable experimental vapor pressure
data for any of the two substances, even though in the TRC
Thermodynamic Tables19 parameters of a correlating equa-
tion for a mixture of stereoisomers of perhydrophenan-
threne are presented in the table k-4700 based on unpub-
lished API data and the data by Durland and Adkins;2 (ii)
most literature data come from measurements of a boiling
point when distilling a reaction product at a reduced

J ournal of Chemical and Engineering Data, Vol. 45, No. 6, 2000 1209
n
Ta ble 5. Liqu id Hea t Ca p a cities of
P er h yd r oa cen a p h th ylen e a n d P er h yd r op h en a n th r en e
S ) (∆Ci/R)2(σC/R,i
)
(7)
-2
∑
T/K Cp,m/R T/K Cp,m/R
δra/% δra/%
i)1
Perhydroacenaphthylene Perhydrophenanthrene
where the variance σC/R,i was estimated for each value on
the basis of the assumed experimental error of the set of
data used in the correlation and n is the number of
experimental data points. The input information was the
percentage error of the experimental data σrC given by the
author for the whole data set. The variance of the i-th data
point was expressed as
307.9
307.9
308.0
315.4
317.8
317.9
320.3
325.3
327.8
34.5
34.6
34.6
35.1
35.3
35.3
35.5
36.0
36.1
-0.1
0.1
0.1
0.0
-0.2
0.0
0.1
0.2
-0.1
305.4
37.7
37.6
37.5
38.1
38.6
38.7
38.6
39.1
39.2
39.6
39.6
40.1
40.0
40.6
40.5
0.1
305.4
305.5
310.4
315.3
315.3
315.4
320.3
320.3
325.2
325.3
330.2
330.2
335.2
335.2
-0.1
-0.3
0.0
-0.1
0.2
0.1
0.1
0.2
-0.1
0.0
0.0
-0.1
0.1
-0.1
σC/R,i ) 10-2(C/R)iσrC
(8)
The parameters of eq 6 derived from the fit are given in
Table 6 along with the relative standard deviation of the
fit and an estimate of uncertainty, which reflects both the
uncertainty of the experimental data and the possible error
due to the fitting procedure.
R δr ) 100{Cp,m/R - Cp,m/R(calc)}/(Cp,m/R).
Only for perhydrophenanthrene are there other experi-
mental data for liquid heat capacities, namely four data
points for an unspecified stereoisomer covering the tem-
perature range from 313 K to 483 K published by Gudzi-
nowicz et al.26 and smoothed data by Nuzzi27 for three
specified stereoisomers, trans,anti,trans, cis,anti,trans,
cis,syn,trans, covering the merged temperature range from
283 K to 403 K (depending on the stereoisomer). As our
experimental data differ from those of Gudzinowicz et al.26
by more than 3%, which may be attributed to a different
composition of the mixture of stereoisomers, we correlated
our data separately. The parameters of eq 6 calculated from
the data by Gudzinowicz et al.26 are given in Table 6.
Obviously, the heat capacity data by Nuzzi27 differ mutu-
ally for each stereoisomer as well as from our data with
relative deviations from our data ranging from -13% to
12%.
9-phenantrol and reported its boiling range, differing from
the present data by an average of 80%. API data coming
from the API Research Project 4224 deviate from our data
substantially at their low-temperature end. However, the
origin of the data is unclear; the data may be estimated.
Pinkney et al.25 reported a boiling temperature range for
three fractions of perhydrophenanthrene prepared in a
study of its synthesis from dienynes. Only one range is
shown in Figure 2, as the remaining ranges overlap the
range of boiling points reported by Eimasry and Gisvold.5
Eimasry and Gisvold5 studied catalytic hydrogenation of
1,2,3,4,5,6,7,8-octahydrophenanthrene, which yielded a
crude perhydrophenanthrene distilled between 87 and 89
°C at 266 Pa. This boiling point differs from the data
calculated from the Cox equation by several hundred
percent.
A general remark may be drawn from Figures 1 and 2.
Boiling points measured by different authors agree in a
qualitative manner, defined by a (50% pressure deviation
margin from the present data, within the temperature
range and about 50 K below the lower limit of the present
data. Taking into account the complex nature of both
substances studied, each being a mixture of several stereo-
isomers, the (50% margin is acceptable.
Con clu sion
Two tricyclic perhydroaromatics, perhydroacenaphthyl-
ene and perhydrophenanthrene, were synthesized by hy-
drogenation on a nickel catalyst at an elevated temperature
and pressure. Their vapor pressure and liquid heat capacity
were measured by precision comparative ebulliometry and
heat conduction calorimetry, respectively. The Antoine and
the Cox equations within experimental uncertainty repre-
sented the results of vapor pressure measurements. Com-
parison of the present data with boiling points reported in
the literature showed a qualitative agreement in the
temperature range of the measurement and for tempera-
ture extrapolations about 50 K below the lower limit of the
present data. The experimental heat capacities for a
mixture of stereoisomers of perhydrophenanthrene agree
with the literature data within 3% whereas the present
measurement reports so far unavailable heat capacity data
for perhydroacenaphthylene. A conclusive analysis of pos-
sible causes of deviations between the present data and
most of the literature vapor pressure data is hindered by
The measured heat capacities of perhydroacenaphthyl-
ene and perhydrophenanthrene are presented in Table 5.
Results of repetitive experiments are given only if they
differed significantly. In Table 5 relative deviations are also
given between the experimental data and the data fitted
by the polynomial equation
k
Cp,m
i
T
)
ACi+1
(6)
∑
(
)
R
100
i)0
(R ) 8.314 51 J ‚K-1‚mol-1). The parameters of eq 6 were
determined by using the weighted least-squares method.
An objective function was used of the form
Ta ble 6. P a r a m eter s of Eq 6
parameters
temp range
C
C
a
substance
A1
A2
Tmin/K
Tmax/K
sr
uncertainty/%
perhydroacenaphthylene
9.961 15
7.659 13
9.601 03
7.979 31
9.817 04
9.634 00
307.9
305.4
313.2
327.8
335.2
483.2
0.1
0.1
0.5
1
1
3
perhydrophenanthrene, this work
perhydrophenanthrene, Gudzinowicz et al.26
sr ) 102(∑ni)1[[{Cp,m - Cp,m(calc)}/Cp,m]/(n - m)]2i )1/2, where n is the number of fitted data points and m is the number of independent
a
adjustable parameters.

1210 J ournal of Chemical and Engineering Data, Vol. 45, No. 6, 2000
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stances reported in terms of the relative amount of
stereoisomers is not available. Further, and very likely
even more important, is the fact that most of the literature
data were obtained by measurement of a boiling temper-
ature at a reduced pressure in studies of reaction pathways.
Such measurements provide only a very inaccurate value
of vapor pressure.
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Ack n ow led gm en t
We are grateful to Milan Za´bransky´ for his help in the
literature search and to Randolph Wilhoit for providing the
unpublished API vapor pressure data for perhydrophenan-
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Received for review May 1, 2000. Accepted September 11, 2000.
This work was supported by the Grant Agency of the Czech
Republic (Grant No. 213/96/1162) and by the Ministry of Education
of the Czech Republic (Grant No. CB MSM 22340008). Diana Zala
acknowledges the support of the IAESTE Czech Republic, ICT
Prague.
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