Hightemperature calorimeter for the measurement of vapor pressure and enthalpy of

vaporization
G. Natarajan and D. S. Viswanath

Citation: Review of Scientific Instruments 54, 1175 (1983); doi: 10.1063/1.1137545

View online: http://dx.doi.org/10.1063/1.1137545
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 High-temperature calorimeter for the measurement of vapor pressure and
enthalpy of vaporization
G. Natarajan and D. S. Viswanath
Department of Chemical Engineering, University of Missouri, Columbia, Missouri 65211
(Received 7 December 1982; accepted for publication 24 May 1983)

An adiabatic calorimeter for the simultaneous measurement of enthalpies of vaporization and

vapor pressures of certain coal chemicals is described. The calorimeter was tested using benzene
for which accurate experimental data exists in the literature. Benzene is one of the substances
recommended by IUPAC as a reference substance for calorimetric studies. The uncertainty in the
benzene data is ± 5 J/mole in the temperature range of 350 K (very close to the boiling point) to
480 K (around 0.85 times the critical temperature). Both vapor pressure and enthalpies of
vaporization of benzene showed excellent agreement with the available literature data.
PACS numbers: 07.20.Fw, 51.30. + i, 65.50. + m, 64.70.Fx

INTRODUCTION
Vapor pressure and enthalpies of vaporization are two im-
portant basic thermophysical properties useful in process de-
sign. For the evaluation of other thermodynamic data such
as second virial coefficients
B = (jjHvIT)(dT IdP) + VI - (RT IP), (I)
enthalpies of vaporization and vapor pressure data obtained
in a flow calorimeter offer a better alternative to PVT data
especially when adsorption effects become important. It is
also possible to evaluate saturated liquid and vapor volumes
using the relations
PVg =RT+BP (2)
and
(3)
In addition very few calorimetric and even vapor pressure
data are available for coal chemicals. Industrial processes
are generally carried out at pressures ranging from few bars
to 30-40 bars and the enthalpies of vaporization vary from
25 to 40 kJ/mole at 1 bar to zero at the critical pressure, the
critical pressure varying between 25 to 40 bars for most of
the substances. Thus, there is an urgent need for such data
both for process design and for testing theoretical models.
I. APPARATUS AND PROCEDURE
its dew point T2 (in the case of a pure substance T, = T 2 ) can
be obtained using an apparatus as shown in Fig. 2. The path
"abcd" in Fig. 1 shows that a cyclic process is necessary with
two major pieces of equipment operating at T, and T2 with a
condenser interposed between them to make the process
thermally balanced and to achieve the equilibrium. In Fig. 2
the reservoir is at T and calorimeter at T2 which corre-
" temperature.
sponds to the saturation
B. Description of the apparatus
The principal components of the apparatus are the res-
ervoir, calorimeter, condenser, and the liquid meter.
The reservoir is a thick-walled cylindrical vessel made
of 316 stainless steel and it contains 90% of the liquid. The
vessel is designed to withstand a pressure of 100 bars in the
temperature range of 260--720 K. The reservoir is heated
PI ' 2
CRITICAL
POINT
.....
..J
C
...z:a::
I&J

The experimental apparatus employed in the present

study is similar in functional details to the all-glass setup T, Tz
TEMPERATURE
used by Viswanath and co-workers. 1-4 The earlier design of
lei
Dana5 has been modified by several workers6-" and have
been used mainly for low-temperature work. The apparatus
can be used both for pure substances and mixtures.

A. Basic principles
X, X, X2
The vaporization process and the basis for the design of A 8
the apparatus can be seen from Fig. 1 which shows the P-T- CONCENTRATION
Ibl
x and H-T-x models for a completely miscible binary sys-
tem. The enthalpy difference between states a and c for a FIG. 1. Space model for binary phase equilibrium: (A T) triple point of A,
liquid at its bubble point T and the corresponding vapor at (Br) triple point ofB, (0) gas phase, and (L) liquid phase.
"
1175 Rev. Scl.lnstrum. 54 (9), September 19830034-6748/83/091175-05$01.30 © 1983 American Institute of Physics 1175

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 HEISE -PRESSURE GAUGE
NITROGEN
CYLINDER
with an insulated nichrome heating coil (17.0 11 1m). The
energy input was regulated through dimmers tats and the
reservoir was lagged to minimize heat losses. Provision is
made to measure the temperature of the liquid using
thermowells. The physical dimensions of this vessel are:
7.62-cm i.d. (lO.16-cm 0.d.)X9.525 cm.
The calorimeter is a 6.35-cm-o.d. cylindrical vessel.
The volume of the liquid in this 316 stainless-steel is approxi-
mately 35 ml. The remaining part of the vessel volume,
2.223-cm i.d. X 16.50 cm, is occupied by the saturated vapor.
The thermowell provided with the vessel aids in monitoring
the saturation temperatures. A small heater made of 19-11 I
m nichrome wire and wound on a Teflon bobin is kept im-
mersed in the calorimeter liquid. The electrical connections
for the internal heater are Conax connectors (supplied by
Conax Company, Buffalo, New York). Insulated nichrome
wire (17.011 1m) provided around the calorimeter keeps the
liquid at its saturation temperature and the internal heater
supplied the energy for vaporization at this temperature.
The liquid meter is a glass vessel which siphons out the
calibrated volume precisely without any dripping. The liq-
uid meter was calibrated for volume using triple-distilled
mercury (impurity less than 1 ppm) and the calibration was
carried out from 24 to 140 .c. The volume of the liquid meter
followed the relation
v= Vo[1 + a(t - to)],
where a = 0.000025 ·C- I , to = 24°C, and Vo = 4.8067
± 0.0001 ml. A 316 stainless-steel vessel was used as a pro-
tective casing for the siphon vessel. Three windows provided
on the sides of the metal casing enabled easy viewing during
the monitoring of evaporation rate.
It is essential to remove all the vapors formed in the
calorimeter and recycle it back to the reservoir as a liquid.
This ensures absence of differential pressure in the closed
high-pressure circuit. This also enables the system to attain
1176 Rev. Scl.lnstrum., Vol. 54, No.9, September 1983
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FIG. 2. Schematic diagram of the experi-
mental apparatus: (I to m) vapor line
heater, (m to n) calorimeter external
heater, (n to 0) reservoir heater, (D) dim-
10 TI
9 merstat, (VI) pressurizing valve, (V,) de-
compression valve, (V,) liquid purging
~ T2
valve, (IB) ice box, and (TW)
2
I thermowell.
4
3 V
MULTI-PIN
RECORDER
fLUKE - MULTIMETER
MODEL 8300 A
equilibrium over a short period of time and maintain the
condition over a longer period of time. This was achieved by
a proper condenser of effective area 130 X lO-4 m2 and keep-
ing the coolant inlet temperature not too far (within 1~
15°C) from the condensing vapor temperature.
Temperatures were measured using NBS certified ther-
mometers and copper-constantan thermocouples calibrated
according to IPTS-68. The accuracy of temperature mea-
surement is ± lO mK. A high-precision Heise gauge cali-
brated against Amthor dead-weight gauge model 460 was
used for pressure measurements. The Heise gauge had no
hysteresis and there was a one-to-one correspondence
between the dead-weight gauge and the Heise gauge over the
entire range of ~ 1500 psig. The accuracy of the gauge is
better than ± 0.1 % of span and the pressures could be read
to better than 0.5 psi using magnifying glass-vernier ar-
rangement. The gauge itself is marked to 1 psi. With these
the uncertainties in the pressure measurement are expected
to be less than 6X lO-4 p.
C. Procedure
The reservoir and the calorimeter were filled with 375
ml of pure compound. A cyclic operation of filling the high-
pressure circuit with nitrogen and subsequently evacuating
it was carried out a few times. The apparatus was pressurized
to the experimental value using nitrogen. The external
(4)
heaters wound over the reservoir and the calorimeter (1711 I
m) heat the liquid. As the temperature increased nitrogen
was purged periodically until near saturation conditions
were attained. In addition, the solubility of nitrogen in ben-
zene has a negligible effect on the measurements. The heat
input was controlled by "minitrol" controllers supplied by
Glas-Col Co., Inc. The liquid supplied by gravity from the
reservoir to the calorimeter corresponds to the saturation
temperature. The internal heater supplies the enthalpy of
vaporization to the liquid in the calorimeter. At steady state,
rate of evaporation was measured by condensing the vapor in
High-temperature calorimeter 1176
 the condenser. The time (t) taken for the liquid to fill the 6

precalibrated volume (V) of the siphon vessel, the voltage (E ), (3) (5) (5)

and the current (I) passed through the internal heater were 4 (4)

used to evaluate enthalpies of vaporation:

(3)
(3) (3)
3
(LiB /kJ mole-I) = (E /V)(I / A)(t /s)(M)(10- ). (5)
" (p/g cm- 3 )(Vlem 3 ) '".,
>- 0
~ 350 400 450 50 o
The saturated liquid density of benzene from different z
c
sources 12- 20 were analyzed for the accuracy and used to ob- Ir -2
tain a density-temperature relation. The data fitted the '"uz
:::>
equation -4

(6)
-6

with an average absolute percent deviation of 0.26, where

Z = 0.26967 and the reduced temperature T, = (T /K)I
562.15.
The corrections that have to be made on the experimen-
tal LiB" values arise due to:
(i) Corrections for sensible heat: The temperatures T)
and T2 were controlled in such a manner that they corre-
sponded to the boiling temperature. It was also observed that
for steady-state conditions, it was essential that the tempera-
tures T) and T2 are equal. This made the sensible heat correc-
tion negligible.
(ii) Correction for unused internal heater resistance: If
the full length of the internal heater was not completely im-
mersed in the calorimeter liquid, the energy supplied to the
heater should be proportionally scaled. The volume of the
initial feed liquid and the gravitational flow of liquid from
the reservoir to the calorimeter ensured complete immersion
of the internal heater in the calorimeter before, during, and
after the evaporation process. Hence there was no correction
from this source.
(iii) Correction for condensation of liquid in the vapor
line: This is estimated to be zero because of lagging of the
vapor lines, use of vapor line heaters, and continuous moni-
toring of temperature and pressure which were perfectly
constant at a particular value once the steady-state condi-
tions were attained.
(iv) Correction for heat leakage: The calorimeter vol-
ume, about 40 cm 3 , was small and there was no loss of mass
either from the calorimeter or from the system (flow calori-
meter with recycling of liquid to the reservoir without any
TEMPERATURE (OK)
FIG. 3. Uncertainty in experimental data as a function of temperature for
benzene: (n) indicates number of data considered.
a zero/negligible correction for heat loss.
The accuracy in LiBv values due to the accuracy of the
various measuring instruments is estimated to be 2 to 3 J/
mole. Data for benzene are reported in this paper. However,
data collected for other substances, toluene, p-xylene, and
tetralin, will be reported elsewhere. The uncertainty due to
random error for all the substances was less than ± 15 J/
mole. Figure 3 shows the uncertainties in experimental data
for benzene.
II. RESULTS AND DISCUSSION
The vapor pressure data of benzene is presented in Ta-
ble I. The data were compared with literature val-
ues. 12.13.20-22 Most of the published values are smoothed data
and they deviate from one another within a range for average
absolute deviation of 0.12%-0.28%. The precision of our
work and hence the accuracy of our data are superior to the
earlier measurements. The data were fitted to polynomial
equations of different order and the best fit by least-squares
technique resulted in
4

removal ofliquid or vapor from the apparatus). The amount
ofliquid vaporized from the calorimeter was instantaneous-
ly replenished by gravitational force from the liquid in the
reservoir. The liquid feed also assists a thorough mixing of
the small volume ofthe liquid in the calorimeter. The trans-
port of vapor bubbles by the buoyancy effects from the sur-
face of the internal heater to the vapor-liquid interface also
mixes the calorimeter liquid. Therefore, a uniform tempera-
ture was maintained all around the internal heater. The ca-
lorimeter liquid was surrounded by a metal wall with a tem-
perature equal to the temperature of the liquid. This
isothermal wall was insulated with 1.6 cm of asbestos (ther-
mal conductivity 0.113 Wm -'K -I) and 2.5 cm of glass wool
(thermal conductivity 0.035 Wm-)K- 1). The calculated
amount of heat transferred through the insulation suggested
In[(po/bars)lPcJ = 2:,AJ562.09/(TIK)-lr/2 , (7)
i=O
where Ao = - 4.12556, Al = 22.8275, A2 = - 49.6993,
A3 = 31.8597, andA4 = - 6.7767. The calculated values of
po using Eq. (7) are presented in Table I along with the per-
cent deviation from experimental values. Equation (7) fitted
the experimental data with an average absolute deviation of
0.28% and standard deviation of 0.02 bars. The value of Pc
used is 48.94 bars. In Table II the present data on enthalpy of
vaporization are compared with the published values. The
accurate work of Todd et al. 23 compared with our values
within 0.41 to 0.57 per cent. The calculated values of Organ-
ick and Studhalter24 using PVT data yields 0.79% average
absolute percent deviation from our experimental values.
Our measured LiBv fit the equation

1177 Rev. ScI. Instrum., Vol. 54, No.9, September 1983 High-temperature calorimeter 1177

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 TABLE I. Vapor pressure of benzene.

Temp. Expt.po Calc. po Bender et al. b Gornowski et al. C Glanville et al. d Kalafati et at.' Zmaczynski'
No. (K) (bar) (bar) %dev .. (bar) (bar) (bar) (bar) (bar)

351. 79 1.006 1.008 -0.22 0.971 0.963 0.956 0.980 0.963

2 360.46 1.282 1.279 0.23 1.260 1.254 1.239 1.275 1.258
3 365.66 1.483 1.472 0.73 1.463 1.457 1.438 1.438 1.462
4 371.61 1.714 1.724 -0.61 1.727 1.721 1.694 1.754 1.727
5 375.35 1.897 1.902 -0.26 1.910 1.905 1.873 1.942 1.911
6 376.95 1.981 1.983 -0.12 1.993 1.987 1.953 2.028 1.995
7 385.45 2.467 2.467 -0.02 2.481 2.473 2.427 2.531 2.486
8 393.99 3.057 3.054 0.10 3.059 3.046 2.989 3.127 3.067
9 399.25 3.482 3.471 0.31 3.463 3.446 3.382 3.543 3.469
10 406.25 4.106 4.099 0.16 4.062 4.037 3.964 4.161
II 419.75 5.533 5.567 -0.61 5.432 5.387 5.303 5.571
12 439.47 8.410 8.365 0.54 8.019 7.931 7.845 8.220
13 455.25 11.102 11.122 -0.18 10.667 10.540 10.455 10.913
14 459.07 11.826 11.840 -0.12 11.395 11.258 11.170 11.648
15 477.75 15.411 15.402 0.05 15.485 15.309 15.145 15.783
Average absolute deviation, 0.28%
Standard deviation (bar), 0.02

a%dev. = Expt. pO - calc. pO X 100.

Expt.p()
b Reference 20.
c Reference 12.
d Reference 13.

'Reference 21.
'Reference 22.

In [(.tJH"/kJ mole-I)] ed in Table II.

3 The good agreement of the experimental data with the
= IA,ln!562.09/[562.09-(TIK)]J'/3, (8) published values established the reliability of the data and
i=O
also the design of the apparatus employed. Our statistical
with Ao = 0.98407, A I = 7.81692, Az = - 7.18074, and analysis of the data yields a very low standard deviation 0.08
A, = 1.80504. kJ/mole, and it proves for the internal consistency of the
The least-squares regression estimate for this fit was an data collected. The uncertainty of data reported on .tJHv was
average absolute percent deviation of 0.22 and a standard estimated as recommended by IUPAC 27 and it is presented
deviation of 0.08 kJ/mole. The calculated .tJHv are present- as a function of temperature in Fig. 3.

TABLE II. Comparison of experimental AH v with literature values for benzene.

PVT
Temp. Expt.AHv Calc. AHv (kJ/mole) Literature AH v
No. (K) (kJ/mole) (kJ/mole) % dev. (Ref. 24) (kJ/mole) Ref.

351.79 30.831 30.928 -0.31 31.103

2 360.46 30.495 30.441 0.18 30.383

3 365.66 30.205 30.139 0.22 29.991 30.726 (353.24K) 23
4 371.61 29.868 29.785 0.28 29.568 29.255 (377.58K) 23
5 375.35 29.489 29.557 - 0.23 29.311
6 376.95 29.465 29.459 0.02 29.205 30.769 (353.15K) 25
7 385.45 28.851 28.925 -0.25 28.644 28.926 (383.15K) 25
8 393.99 28.552 28.369 0.64 28.090 25.983 (433.15K) 26
9 399.25 27.898 28.016 -0.43 27.747 23.258 (470.95K) 26
10 406.25 27.514 27.536 - 0.08 27.286
II 419.75 26.521 26.572 -0.19 26.362
12 439.47 25.071 25.069 0.01 24.900
13 455.25 23.846 23.778 0.28 23.614
14 459.07 23.436 23.453 - 0.07 23.286
15 477.75 21.766 21.782 - 0.07 21.590
Average absolute deviation, 0.22%
Standard deviation (kJ/mole), 0.08

1178 Rev. Sci.lnstrum., Vol. 54, No.9, September 1983 High-temperature calorimeter 1178

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 ACKNOWLEDGMENTS
The authors thank the Research Council of the Univer-
sity of Missouri-Columbia for partial support for this pro-
ject and Bob Chaney for his help in the fabrication of the
apparatus.
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High-temperature calorimeter 1179