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J. Phys. E: Sci. Instrum., Vol. 17. 1984. Printed in Great Britain

Three high-pressure optical cells for phase

eq u iI i bri u m investigations

E Brunner, S Maier and K Windhaber

BASF Aktiengesellschaft, D-6700 Ludwigshafen!Rhein, West
Germany

Received 8 March 1983, in final form 19 August 1983

Abstract. The construction of three high-pressure optical cells

of simple construction and large volume (30, 110 and 550 cm3) LL
is described, the total cell content being observable in the 30 and
110 c m 3 cells. In conjunction with a simple metering, stirring
and heating system, the cells permit rapid and precise
measurement of phase equilibria up to 200 MPa (30 cm' cells)
and 100 MPa (1 10 and 550 cm3 cells) and up to 350 "C.
according to the synthetic method, without additional analytical
1
effort. Using the 550 cm3 cell, the dew points of very sparingly
volatile substances can be determined up to concentrations of
0.0 I kg m - 3 with a relative error of about 0.05. The validity of
' a
i
the experimental technique has been tested on known systems.
Ibl
I n
and excellent agreement with literature values has been obtained.
The solubility of methane in cyclohexane has been measured
at 37.8 and 71.1 'C and up to about 18 MPa.

1. Introduction
Numerous examples of the construction of high-pressure
autoclaves with optical windows for the determination of phase
equilibria are to be found in the literature. Summaries have been
given, for example, by Tsiklis (1965, 1968, 1972): Tsiklis and
Rott (1967) and Schneider (1968, 1970). High-pressure optical
cells which can be employed up to 700 MPa are also available
from various companies (High Pressure Equipment C o t , Nova-
Werke AG$, Amincos).
-
a
50 mm 1 6 5 4 3

Figure 1. (a), High-pressure optical cell, 30 cm3, 200 MPa,

I

350°C; (b),high-pressure optical cell, 110 cm3, 70 MPa. 350°C.

2. Apparatus and procedure
2.1. Cotistruction characteristics ofthe cells
Figure 1 shows the construction of 30 and 110 cm3 cells. The
two cells differ essentially only in the fact that the larger cell has
been extended from 30 to 110 cm' by increasing the distance of
the windows and by a barrel-like enlargement of the internal
diameter of the autoclave volume. The total interior of the cell
can be observed through two high-pressure windows of
synthetic sapphire. the diameter of the free opening being
25 mm. The windows are sealed according to the unsupported-
area principle, also known as the Poulter principle. Sapphire
cylinder 6 (see figure 1) is pressed against the polished surface of
pressure-distributing ring 1. This means the cell becomes self-
sealing under pressure. Therefore in order to seal the window,
pressure screw 2 need only be tightened by hand. The close fit of
the Teflon seal rings makes it possible to carry out
measurements up to 350 "C. However, if the cell is cooled over a
1, Pressure-distributing ring (1 7 4 PH); 2. pressure screw
(Nimonic 90); 3, heating jacket; 4, 2 high-pressure seal rings
(PTFE): 5, pressure ring (Nimonic 90); 6, window (sapphire);
7 , pressure vessel (Nimonic 90).
relatively wide temperature range, it is necessary in general to
renew the Teflon seal rings at the windows. A dimensioned
sketch of the window assembly is shown in figure 2.
The windows consist of colourless synthetic sapphire with a
thickness of 16 mm and a diameter of 35 mm. The parallel faces
are very finely ground and polished, with the optical axis
perpendicular to the parallel faces. The edges of the windows are
bezelled to prevent damage to the edges. Suppliers of sapphire
windows are for instance: Badische Industrie- und
Edelsteingesellschaftf', Saphirwerk Industrieproduktet. The
same windows are employed in the large optical cell of 550 (3371'

t High Pressure Equipment Co. Inc. 1222 Linden Ave.

Pennsylvania 16505, USA t Badische Industrie- und Edelsteingesellschaft mbH, D-7807,
$ Nova-Werke AG, CH-8307 Effrektion, Switzerland Elzach, West Germany
5 Aminco American Instrument Company, Silver Spring, $ Saphirwerk Industrieprodukte AG, CM-2560 Nidau,
Maryland 209 10. USA Switzerland

0022-3735/84/030044 + 05 $02.25 1984 The Institute of Physics

High-pressure optical cells f o r phase equilibria

Plane parallel, very fineiy ground,

. edges bezelled, radius 0.5

Figure 2. Dimensioned sketch of the window assembly.

Dimensions are given in mm: M,metric screw; sw, spanner
width .

(see figure 3), but only the lower part of the autoclave content
can be observed. This cell is preferably employed for dew point
measurements on sparingly volatile components in fluid systems,
it being possible to measure dew point concentrations c down
to about 0.01 kg m - 3 with an estimated relative error of
Ac/c=O.O5. The range of use of the optical cells depends on
their volume and the yield point of the materials used, and
appropriate additional safety measures were employed when the
maximum operating pressure and the maximum operating
temperature were used. The characteristic data of the individual
high-pressure optical cells are summarised in table 1.
During operation of the apparatus the cells are always
installed so that the optical axis is horizontal. Depending on the
range of use, the materials of the cell bodies consist of highly
corrosion-resistant and highly heat-resistant alloys. / I ' \
1 ;
1
' '
$'
I '\
The windows are held over a plane-parallel supporting ring I /

(Armco 17-4 PH, equivalent to German standard material
1.4540) which is sealed by an 0 ring, and a pressure-distributing
ring ( 1 7 4 PH), by means of a supporting screw R M (equivalent
~ 1, 6. 8, 0 ring seal (Won): 2, 5, high-pressure seal (PTFE);
to German standard material 1.4021). T o facilitate sealing. a
thin Teflon film of 0.03 to 0.1 mm is placed between the
supporting ring and the level surface of the window. In addition,
it is also advantageous to place a film of this type between the
inner surface of the window and the cell body. Because of these
Teflon films the faces do not need to be optically flat.
In the present construction, the sapphire window can be
subjected to a pressure of 200 MPa with a fourfold safety
somm 56 11 10 9 8 I
Figure 3. High-pressure optical cell, 550 cm3. 100 MPa, 3OO3C.
3, heating jacket; 4, baffle plate as flow guide; 7, pressure
screw (Nimonic 90); 9, pressure-distributing ring (1 7-4 PH);
10. pressure ring (Nimonic 90): 11, window (sapphire);
12. pressure vessel (Nimonic 90); 13, locking nut (German
Standard 1.6580, 30 CrNiMo 8); 14, autoclave cover (Nimonic
90); 15, stirring device; 16, bar magnet.

Table 1.

Yield strength
0.2% offset Range of use Linear
Material at maximum Maximum Maximum thermal
Cell (equivalent operating operating operating expansion
volume to German temperature pressure temperature coefficient
V(cm3) standard) a(N mm-2) AMP4 tW) 106a(K-')

30 1.4580 145 70 300 18.0

2.4969a 685 200 350 13.5
2.46 l o b 220 70 350 12.0
Ta-1OW' 250 70 200 6.6

110 2.4969a 685 70 350 13.5

5 50 2.4669a 685 100 300 13.5

a Nimonic 90, heat-resistant Ni-base alloys (Henry Wiggins & Co. Ltd, Hereford, U K )
Hastelloy C4, Ni-base alloys (Stellite Division, Cabot Corp., Kokomo. Ind.. USA)
Tantalum with 10% tungsten (W C Heraeus GmbH, D-6450 Hanau. West Germany).

45
E Brunner. S Maier and K Windhaber

margin according to the calculations of the window. Three 1/4"

connections are located in the middle of the cell. perpendicular
to the optical axis. The 1.5 mm boreholes in the cell body can, if
required, be packed to reduce dead volumes. Depending on the
pressure range, 1/16" high-pressure valves (up to 100 MPa) or
118'' high-pressure valves (up to 200 MPa) are used. The relative
dead volumes Ac/t., based on the cell volume can be limited to
0.005 in the 30 c m 3 cell. and are correspondingly smaller in the
larger cells.
"I vvz
A heating jacket is welded on each of the bodies of the 30
and l 1 0 c m 3 cells, and this jacket can be connected to a
circulatory thermostat or cryostat. The choice of the welding
additive depends on the materials to be welded. Furthermore
care must be taken in the case of materials that tend to take up
oxygen during welding, such as for example tantalum, that the
atmosphere is free of oxygen when welding is being carried out.
Figure 4. Scheme of functioning of the equilibrium cell. V I , V 2
It is also important that the jacket and cell-body materials have
and V 3 , valves; M I and M1, manometers.
similar thermal expansion coefficients. The permissible operating
pressure of the heating mantle is 2 MPa. Since the cell windows
are located inside the heated cell body, uniform heating of the
cell space is ensured. To screen the autoclave windows from the
course also possible to investigate multi-component systems in
temperature of their surroundings, thin insulating windows can
this way if the degree of freedom is restricted by a procedure in
be mounted in addition on the inner side of the pressure screws.
which the mixtures 1 and 2 which constitute the pseudobinary
The cell content is stirred by means of a simple magnetic
system are metered separately into the cell. similarly to
laboratory stirrer and a Teflon-jacketed bar magnet. In the case
components 1 and 2. Whether in these complex phase equilibria
of the 550 cm3 cell, the bar magnet is attached to the lower end
the boiling point or dew point is present depends on whether the
of a shaft which is provided with stirring blades.
phase boundary vanishes above or below. or appears from
above or from below. when the second component or the second
2.2. Method of measurenient mixture is metered in. Boiling points and dew points may also be
In the determination of boiling points and dew points of binary observed by changing the temperature at a predetermined mass
systems. the essential characteristic of the measuring method ratio of the components.
(see figure 4) consists in metering into the measuring cell known In the measurement, it is possible in principle to meter in
masses of components 1 and 2 of the system to be investigated, either the more readily volatile or the more sparingly volatile
until, on thoroughly stirring the mixture at the same time, a component first. For experimental reasons, it is in general most
transition from the homogeneous to the heterogeneous state, or advantageous if the more readily volatile component is initially
cice cersa. is observed. introduced into the cell. Depending on the differences in
From the masses metered in and the temperature-corrected volatility, the system passes through curves of the type A or B in
cell volume, the boiling point or dew point as well as the figure 5(a) when the more sparingly volatile component is
corresponding densities are obtained in a simple manner. It is of subsequently metered in. First, the system passes from the

I /
1
0 I /

-- B -

Figure 5 . Guidelines for the measurement of binary systems, starting (a), from the more readily volatile component; (b),from the more
sparingly volatile component.

46
High-pressure optical cells f o r phase equilibria

homogeneous state to the heterogeneous state, and a dew point method of measurement, we have measured isothermal bubble
on the equilibrium curve is obtained; when the more sparingly point curves and the molar volume of the mixtures at 37.8 and
volatile component is metered in further, the liquid constituent in 71.1 'C. and have found excellent agreement with the values
general increases until, when the gas phase vanishes, the boiling obtained by Reamer et a1 (1958). The average deviation of our
point is reached. In particular cases, retrograde vaporisation or experimental data of bubble points and molar volumes from the
condensation may be observed directly. In these cases. two smoothed values obtained by Reamer et a1 (1958) is less than
boiling points or dew points are obtained in one measurement. 0.5%. The results are summarised in table 2. and are shown in
The determination of the mass of component 1 metered in is figure 6 together with the results of Reamer et al.
particularly simple if its p V T data for the experimental
temperature are known. Metering can be effected by means of
high-pressure screw presses, metering pumps, gas compressor
or, if required, directly from high-pressure gas cylinders. T o
determine the mass, the more sparingly volatile component 2
must virtually always be metered in by means of fluid metering
pumps or, more advantageously, by means of high-pressure
screw presses, T o avoid metering errors, the starting point and
end point of the screw press should be determined at the same
moderate pressure in each case.
If in the equilibrium determination the more sparingly
volatile component 2 is initially introduced into the cell, the
system first passes through the heterogeneous region in the
isothermal p x diagram when the more readily volatile
component 1 is added, and, depending on the mass of
component 2 initially introduced, a boiling point on the
equilibrium curve is obtained when the vapour phase vanishes,
and a dew point on the equilibrium curve is obtained when the
liquid phase vanishes (see figure 4(b)). If they cannot be metered
in the molten state, solids must in any case be initially
introduced into the cell.

3. Results
We have tested the validity of our experimental technique on the
known system methane + cyclohexane (Reamer e l a1 1958).
They investigated the vapour-liquid equilibrium and the molar
volume of the vapour and liquid phases of the system
C H , + C 6 H , , using a cell of variable volume. To test our 0.1 0.2 2.3 0.4 0 ,
MO: fraction CHI

Figure 6. CH, + C 6 H 1 2 system. (0.7)

this work.
Table 2. Vapour-liquid equilibrium of CHI + C 6 H 1 2 . (e,V)Reamer et a1 (1958).

The purities of the starting materials used in this work were

37.8 0.0214a 0 11 0 . j b 99.9Yo for C H 4 (Messer-Griesheim) and 99.999;o for
5.04 0.1465 102.5 cyclohexane (BASF). For the evaluation. we have used the p V T
10.95 0.304 1 93.1 data of methane which have been summarised by Angus et a1
13.48 0.365 1 89.8 (1978). The values of x(CH4) and V determined in this work are
16.15 0.4289 8 7.0 estimated to be correct to within 0.02 x(CH4) and 0.02 V . This
includes the experimental errors of measurement of pressure
71.1 0.073 7 a 0 1 l5.qb (&/p = 0.002) and temperature ( A T = 0.1 K). and the
3.05 0.08 14 1 1 1.4 determination of the cell volume and of the masses of C H , and
5.94 0.1597 106.9 C 6 H1 2 introduced into the cell.
8.95 0.2357 102.5
11.77 0.3023 97.8
15.57 0.3929 93.5 References
18.32 0.4555 89.9 Angus S, Armstrong B and de Reuck K M 1978 Methane.
International [hermod\ namic tables of the fluid state-5. IUPA C
a Vapour pressure of cyclohexane (ESDUt 1982) Chemical Data Series No. 16 (Oxford: Pergamon)
Volume of liquid cyclohexane (API: Proj. 44, 1953)
Reamer H H, Sage B H and Lacey W N 1958 Phase equilibria
t ESDU 1982 Vapour pressure and critical points of liquids
in hydrocarbon systems. Volumetric and phase behaviour of the
XXI: Cyclic hydrocarbons. item no 820 16 (London:
methane-cyclohexane system
Engineering Sciences Data Unit)
$ API Proj. 44. 1953 Selected values of properties of Chem. Eng. Data Ser. 3 240-5
hydrocarbons and related compounds, Table 23-2-(3.1110)d, Schneider G M 1968 Phase equilibria of liquid and gaseous
American Petroleum Institute Research Project 44 (Texas: mixtures at high pressures
Texas A & M University. College Station) Experimental Thermodynamics ed. B Le Neidre and B Vodar
(London: Butterworth) vol. 11, S. 787-801

47
E Brunner, S Maier and K Windhaber

Schneider G M 1970 Gas-Gas-Gleichgewichte

Fortschr. Chem. Forsch. 13 559-600
Tsiklis D S 1965 Techniques forphysicochemical studies under
high and super-high pressure 3rd edn (Moscow: Khimiya)
Tsiklis D S 1968 Handbook of techniques in highpressure
research and engineering (New York: Plenum)
Tsiklis D S 1972 Phasentrennung in Gasgemischen (Leipzig:
Deutscher Verlag fur Grundstoffindustrie)
Tsiklis D S and Rott L A 1967 Phase equilibria between
immiscible gaseous phases
Russ. Chern. Rev. 36 351-61

48