Experimental Determination of Solid-Liquid Equilibrium Phase

Diagrams of Different Organic and Inorganic Chemical Systems

On-line Number 0918
Martin K. S. Kwok 1, Alex H. C. Chan 2, Chak K. Chan 3, and Ka M. Ng 4.
Department of Chemical Engineering, Hong Kong University of Science and Technology, Clear Water Bay,
Kowloon, Hong Kong. Email: [email protected], [email protected], [email protected], [email protected].

ABSTRACT
Crystallization has been widely used for product separation and purification in the pharmaceutical, chemical
and food industries. To reduce the time and cost in synthesizing crystallization processes, a number of
systematic procedures have been established. However, the basis of these procedures requires the acquisition
of the solid-liquid equilibrium (SLE) phase diagrams of the chemical systems under consideration, which are
often not available in the literature. There is thus a great demand for determining SLE phase diagrams
through experimental means. This work aims at presenting a generic scheme that can be carried out to
experimentally construct the desired isobaric SLE phase diagram of a given system. Being driven by the
process objectives, the scheme helps to generate phase diagrams that contain specific data useful for the
development of the targeted process.

To demonstrate the implementation of the generic scheme, an experimental apparatus and technique have
been developed to measure the isobaric SLE phase diagrams of the ternary system phenol, bisphenol A and
water at 1 atm. The technique utilized is based on the solid-disappearance method, in which a point on the
saturation boundary is determined by detecting the temperature at which the last trace of solid in the sample
mixture disappears. To provide auxiliary information for the phase diagram, crystals are also sampled by
suction filtration and analyzed for identities. The resulting SLE phase diagram of the system is found to be in
a high degree of accuracy and from which the saturation region of BPA and phenol/BPA adduct can be
identified.

KEYWORDS
Generic scheme, SLE phase diagram, crystallization, solid-disappearance method

INTRODUCTION
In the recent decades, crystallization has received great attention in the pharmaceutical, chemical and
food industries because it is one of the few separation techniques capable of producing pure solid compounds
at ambient conditions. In addition, the lower energy requirement and smaller amount of solvents used during
the crystallization operation make it one of the best choices for meeting the increasing standards of
environmental friendliness, energy and economic efficiency in production processes. All these advantages,
together with the rising demand on high-purity drugs, chemicals and so on have promoted the need in
developing crystallization-based separation processes for a wide range of products, such as organic, inorganic
and biological chemicals. In view of this situation, systematic methods and procedures for designing,
synthesizing and optimizing various types of crystallization-based separation or purification processes have

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been established (Dye and Ng, 1995a, b; Berry and Ng, 1996, 1997; Berry et al., 1997; Samant and Ng, 1998;
Kelkar and Ng, 1999; Wibowo and Ng, 2000, 2002c; Schroer et al., 2001.).

In all these systematic synthesis methods, the starting point is to acquire reliable solid-liquid equilibrium
(SLE) data or phase behavior information of the chemical system involved in the crystallization process
(Wibowo and Ng, 2002c). Representation of the phase behavior in the form of SLE phase diagrams allows
graphical visualization of the thermodynamic boundaries that limit the crystallization operation. Once the
appropriate SLE phase diagram of a chemical system is available, proposed process paths can be drawn on it
and a flowsheet of the corresponding crystallization-based process can be generated accordingly (Wibowo
and Ng, 2000, 2002c). The use of SLE phase diagrams and systematic procedures rather than trial and error
practice would greatly reduce the process development cost and time.

Despite the availability of a considerable quantity of phase diagrams obtained by different researchers,
process engineers often find that the required SLE phase diagram of a chemical system, particularly for new
pharmaceutical entities, cannot be found in the literature. Even if the phase diagram of a system comprising
components similar to that of the system of interest is available, the data may have little or no use, since the
phase behavior (and thus the phase diagram) of a chemical system is strongly influenced by the individual
characteristics of each component present. To overcome this problem, two options are commonly employed.
The first one is to use standard thermodynamic models, such as UNIFAC, UNIQUAC etc. to calculate the
phase diagram. The other choice is to directly determine the phase diagram by conducting solid-liquid
equilibrium experiments. Since the use of the former method is often limited by the ability of obtaining
accurate thermodynamic parameters, on which the calculation heavily relies, SLE experiments are
indispensable in obtaining a reliable phase diagram.

In light of the huge demand for experimentally constructed SLE phase diagrams, this work aims at
providing an objective-driven generic scheme that assists scientists to systematically determine isobaric SLE
phase diagrams of any organic and inorganic systems through experiments. With the help of the practical
procedures for the visualization of high-dimensional phase diagrams (Wibowo and Ng, 2002a), the scheme is
applicable to multi-component systems and helps to construct visible cuts or projections of the original high-
dimensional phase diagrams. In addition, as the ultimate objective of generating SLE phase diagrams is for
process synthesis, the scheme focuses the experimental effort on determining and verifying important
features of the phase diagrams that are crucial for this objective, such as the boundary locations of
crystallization regions or compartments. In the following section, each step of the generic scheme will be
presented and briefly explained. After that, to clearly illustrate how the scheme is performed, the solid-
disappearance method will be utilized to construct the isobaric SLE phase diagram of phenol, Bisphenol A
and water at 1 atm by following the scheme developed.

STEPS OF THE GENERIC SCHEME

The entire scheme consists of four major steps.

Step 1. Specify the process objectives and define the chemical systems to be considered.

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 The first step in constructing the SLE phase diagram of any organic and/or inorganic system is to specify
the objectives of the crystallization-based processes. Based on these objectives, we can make qualitative and
quantitative decisions on the components of the system to be examined, as well as on the conditions (i.e.
temperature and pressure) under which the phase diagram of the system is determined. To have a SLE phase
diagram that is of utility for process synthesis, the system selected should theoretically include the same
components as those existing in the process streams. However, since almost all the practical processes
involve more than three components, it can be expected that high-dimensional SLE phase diagrams are
usually required, the construction of which are very complicated or even impossible. In order to strike a
balance between the representability of the system selected for study and the practicability of the
experimental measurement process, the system to be investigated should only comprise those components
that dominate the SLE behavior of the real process mixture. At this point, it is assumed that certain simple
preliminary tests have been conducted to compare the relative effect of each species on the SLE behavior.
For example, if there exists in the process stream some minor impurities that have little influence on the total
SLE behavior, they can be ignored and excluded from the system to be studied. In addition to the number of
components, temperature and pressure also contribute extra two dimensions to the phase diagram.
Nevertheless, because solid-liquid equilibrium is insensitive to the change in pressure, the effect of pressure
is often neglected to reduce the dimension of the phase diagram to be constructed. The scheme presented
here is designed for determining isobaric SLE phase diagrams at atmospheric pressure. With this convenient
simplification, one just needs to decide whether a polythermal or an isothermal phase diagram is required.

Step 2. Select an appropriate experimental technique to carry out the SLE measurement.

To choose a suitable experimental technique to perform the SLE measurement, a number of factors have
to be considered carefully. These factors include the system conditions selected, nature of the system
components, availability of equipment, cost, amount of sample obtained, accuracy of the phase diagram
required and so on. No single technique is found to be universally applicable for determining the SLE phase
diagrams of any systems. In some cases, the construction an accurate SLE phase diagram may require a
combination of two or even more different experimental techniques. The operating principles, advantages
and disadvantages of some commonly utilized SLE measurement technique have been extensively reviewed,
such as by Rossiter and Baetzold (1992) and Mullin (2001).

Step 3. Represent the general shape of the desired SLE phase diagram and devise an experimental
procedure to determine the saturation boundary or surface.

In order to construct the desired phase diagram through experiments, the saturation boundary or surface,
which separates the region of a single liquid phase from any other regions that contain solid component(s),
must be located. To do it in a systematic and efficient way, detailed experimental procedures are set up based
on the general shape of the desired SLE phase diagram. For a given system, the general shape of its phase
diagram can be determined by the Gibbs’ phase rule, which states that

F=C+2–P–s (1)

where ‘F’is the variance or the degree of freedom. ‘C’ represents the number of components in the system,
whereas ‘P’ stands for the number of phases present. ‘s’ is the number of extra constraints imposed on the
system, such as the occurrence of a chemical reaction among certain components in the system. The number

3
2 in the above equation corresponds particularly to the temperature and pressure of the system. By setting P =
1 (since there is at least one phase present in the system) and substituting the values of C, s and the
conditions of the selected system, the value of F will give the number of independent coordinates required to
represent the desired SLE phase diagram. If F is equal to 2 or 3, the desired SLE phase diagram can be
represented in the form of a 2-dimensional and a 3-dimensional figure respectively. However, if F is greater
than 3, the phase diagram of the system is a high-dimensional one and cannot be drawn on a piece of paper.
Under this circumstance, we can only visualize the general shape of the phase diagram by, for example,
fixing the concentration of certain species in the system or the system temperature, thus providing a series of
3-dimensional isoplethal cuts (i.e. cuts at constant composition). The exact concentration or the range of
concentrations at which the cuts are made depend on the process objectives specified in Step 1.

With the general shape of the phase diagram being sketched, a systematic procedure can be devised to
determine the saturation boundary or surface. The main idea and strategy in formulating the experimental
procedure is to first divide the general shape of the SLE phase diagram into a series of 2-dimensional planes
by, for example, producing constant composition cuts of a species and then determine the respective
saturation boundary on each of these cuts. After the saturation boundaries of a series of isoplethal cuts of
water have been determined, they can be placed together to form the desired isobaric SLE phase diagram of
the system. Having devised the procedure, experiments can be conducted to measure the dissolution points
and thus determine the saturation boundary or surface using the measurement technique selected in Step 2.

Step 4. Crystals are sampled to identify or confirm the crystallization regions of the targeted species
in the phase diagram.

Once the saturation boundary or surface has been experimentally determined in Step 3, the isobaric SLE
phase diagram of the selected system can be regarded as successfully constructed. However, in order to
facilitate the synthesis of crystallization process, it is always beneficial to identify the crystallization regions
of the targeted species. This is accomplished by first sampling out crystals from a slightly saturated
equilibrium mixture that is located immediately below the saturation boundary or surface determined and
then the collected crystals are analyzed for identities by using chemical analytical techniques such as
chromatography. Crystals sampling technique and devices are available in the literature such as the one given
by Nývlt (1977).

EXPERIMENTAL, RESULTS and DISCUSSION

To illustrate the implementation of the generic scheme, the example below shows step by step how the
isobaric SLE phase diagram of a ternary system containing phenol, bisphenol A and water are experimentally
constructed.

Example: Determination of the isobaric SLE phase diagram of phenol, bisphenol A and water at 1 atm

Step 1. In this illustrative example, the system to be studied includes three different components: phenol,
bisphenol A (BPA) and water. BPA is a valuable compound that serves primarily as the starting material for
the manufacture of polycarbonate and epoxy resins. The motivation for constructing the phase diagram of
phenol, bisphenol A and water is that such a phase diagram is useful for the design and synthesis of the

4
crystallization-based purification processes of bisphenol A. Bisphenol A, or 2,2-bis(4-hydroxyphenyl)-
propane in IUPAC notation, is generally produced by the condensation reaction between phenol and acetone
in the presence of an acidic catalyst such as HCl or AmberlystTM (Figure 1).

HCl or

Figure 1. Production of bisphenol A from phenol and acetone

In addition to the desired bisphenol A, the product mixture generated from the above reaction process also
contains a wide variety of impurities including the unconsumed phenol, acetone, as well as a number of
reaction by-products such as water and isomers of bisphenol A. To isolate the impurities from bisphenol A in
the product mixture, crystallization-based separation or purification schemes are often utilized. Although it is
impossible for constructing an SLE phase diagram involving all the substances present in the product mixture,
the required separation or purification schemes can still be synthesized based on the SLE phase diagram
entailing the few most abundant components in the product mixture. In this example, since a stoichiometric
excess amount of phenol with respect to acetone is always used in the reaction process, it is expected that the
product mixture should contain appreciable amount of unreacted phenol. This makes the determination of the
SLE phase diagram of phenol and BPA desirable. In addition, as water is generated from the reaction process
and some companies have tried to purify crude bisphenol A with water through crystallization (Patrascu et al.,
1996, 1998), obtaining the SLE phase diagram of the system phenol + bisphenol A + water is also
advantageous for the synthesis of the purification processes of bisphenol A. The phase diagram is decided to
be a polythermal plot being constructed at 1 atm.

Step 2. The experimental technique selected for constructing this phase diagram is called the solid-
disappearance method, in which the dissolution point of a chemical mixture is directly determined by
recording the temperature at which the last trace of solid disappears. This technique is chosen mainly because
of its simplicity and flexibility. In this technique, a solute/solvent mixture of known composition weighed
into a jacketed vessel is first subjected to a heating process until all the solute dissolves. The objective of this
step is to ensure the formation of a homogeneous solution. The mixture is then cooled, allowing crystals to
form, and finally, it is heated up again and the temperature corresponding to the disappearance of the last
solid is observed and recorded. Throughout the entire experiment, the equilibrium of the mixture is
accomplished by shaking or magnetic stirring.

The corresponding experimental apparatus specially built up is shown in Figure 2. The apparatus mainly
comprises an equilibrium glass vessel that is connected to a temperature bath by two Viton tubings. The glass
vessel, which was made in the glass blowing workshop of HKUST, consists of an inner tube for containing
the chemical mixtures and an outer jacket that allows the circulation of heat-transfer fluid. The inner tube of
the glass vessel is covered with a thermocouple adapter, which is composed of a Teflon-made body, a screw
cap with aperture and two Viton O-rings, is used to seal the inner tube of the vessel and at the same time,
allow the insertion of thermocouple. The temperature bath is a product of Huber Company (Model Unistat
360 HT) and has an operating temperature range of -75 oC to 300 oC. It can control the temperature in the

5
precision of ± 0.01 oC and is capable of providing a programmable heating/cooling profile in a rate as low as
0.01 oC/min. To measure the temperature of the sample mixture, a Digi-Sense J-T-E-K thermocouple
thermometer that is equipped with a K-type thermocouple is applied. The thermometer is calibrated with the
freezing point and boiling point of water and is able to give a temperature reading with the precision of ± 0.1
o
C. Thorough agitation is provided to the sample mixture by utilizing a combination of a magnetic stirrer
purchased from Heidolph Instrument Company (Model MR 3001) and a stir bar. If the apparatus is required
to operate at a temperature slightly below the room temperature, compressed air is allowed to blow on the
surface of the vessel to prevent the condensation of atmospheric moisture. In case that the measurement has
to be carried out at an even lower temperature, such as below 0 oC, an alternative glass vessel with an
additional vacuum jacket must be used.
Screw cap with
Teflon body aperture
Thermocouple
Temperature bath
adapter

O-ring Fluid
outlet
huber
Heat transfer
fluid Equilibrium
vessel

205

Unistat
360

Heidolph MR3001

Thermocouple Magnetic Magnetic

Viton tubing thermometer Fluid inlet stir bar
stirrer

Figure 2. Apparatus used for the measurement of dissolution temperature by solid-disappearance

method

Step 3. To sketch the general shape of the phase diagram, we consider the Gibbs’ phase rule. According to
phase rule, for the isobaric binary system containing phenol, BPA and water, the degree of freedom is:
F = C + 2 – P – s = 3 + (2 – 1) – P – s = 4 – P – s (2)
As there is at least one phase present and no additional constraints,
F=4–P–s=4–1–0=3 (3)
Three independent coordinates are thus necessary to completely represent the desired isobaric SLE phase
diagram of phenol, BPA and water. Temperature will occupy one of the coordinates, whereas the other two
will involve the mole fractions of any two chemical components in the system. In this situation, it can be
predicted that the isobaric SLE phase diagram phenol, BPA and water is a 3-dimensional temperature-
composition plot. The general shape of the phase diagram is like a triangular prism, with temperature as the
vertical axis and the composition of the system is read from a triangular bottom grid.

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To construct this phase diagram in a systematic way, the 3-dimensional temperature-composition plot is
divided into a series of 2-dimensional isoplethal cuts of water. In this way, the effect of water on the SLE
phase behavior of phenol and BPA can be clearly identified over a wide range of water composition. For
each isoplethal cut of water, a particular pseudo-binary system of phenol and BPA is formed. To construct
the entire SLE phase diagram, the starting point is to determine the saturation boundary of a pseudo-binary
system of phenol and BPA contained in an isoplethal cut of water. Mixtures of varying phenol-BPA
composition but of fixed mole fraction of water are prepared and their dissolution temperatures are measured
by the polythermal solid-disappearance method. When the saturation boundary of a particular isoplethal cut
has been located, the experimental procedures are repeated for other isoplethal cuts of water. After the
saturation boundaries of a series of isoplethal cuts of water have been determined, they can be placed
together to form the desired isobaric SLE phase diagram of the ternary system.

After devising the experimental procedure, measurement can be carried out. Bisphenol A used in the study
were obtained from the Mitsubishi Chemical Corporation with respective purities of greater than 99.5%,
whereas Phenol purchased from the GIBCO-BRL Company was of ultra pure grade (UltraPureTM Phenol)
and had a purity higher than 99.5%. These chemicals were used without further purification. The water
employed in the experiment was double deionized and had a resistivity of 18.2 Megohm-cm at room
temperature. Using these chemicals and based on the strategy described above, the saturation boundaries of
the isoplethal cuts at 0, 10 and 30-mole % water were determined and the results are listed in Table 1-3 and
depicted together in Figure 3.

Table 1. Experimental temperature-composition data of phenol + BPA + water system at the

isoplethal cut of 0 mole percentage of water

Mole % of BPA Dissolution Temperature (oC)

0.00 40.8
1.64 39.0
2.28 38.5
4.10 48.7
7.43 64.3
11.69 75.6
17.96 85.1
24.28 91.5
28.60 94.0
33.79 97.7
35.33 100.4
37.13 103.5
38.83 106.9
41.16 110.5
49.11 120.7
56.59 129.3
65.76 137.2
81.03 148.3
100.00 158.4

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Table 2. Experimental temperature-composition data of phenol + BPA + water system at the
isoplethal cut of 10 mole percentage of water

Absolute mole % Absolute mole % Relative mole % of BPA Dissolution

of phenol (1) of BPA (2) = (2)÷[(1)+(2)] Temperature (oC)
72.66 17.19 19.13 78.6
70.82 18.98 21.14 82.1
68.35 21.50 23.93 84.0
66.30 23.70 26.33 87.2
66.24 23.76 26.40 86.6
63.59 26.46 29.38 89.1
60.36 29.70 32.98 90.8
58.64 31.29 34.79 93.6
56.63 33.42 37.11 97.8
53.26 36.83 40.88 103.6
50.52 39.52 43.89 107.5
47.40 42.62 47.35 112.2

Table 3. Experimental temperature-composition data of phenol + BPA + water system at the

isoplethal cut of 30 mole percentage of water

Absolute mole % Absolute mole % Relative mole % of BPA Dissolution

of phenol (1) of BPA (2) = (2)÷[(1)+(2)] Temperature (oC)
54.77 15.18 21.71 68.5
51.51 18.41 26.32 73.1
49.52 20.38 29.15 76.0
47.19 22.81 32.59 78.5
46.56 23.43 33.48 79.6
45.61 24.38 34.83 80.7
45.03 24.99 35.69 81.3
44.68 25.34 36.19 81.4
44.54 25.44 36.36 81.3
43.96 26.05 37.21 83.1
42.71 27.19 38.90 85.4
40.70 29.34 41.89 90.5
37.65 32.37 46.23 96.8
34.14 35.80 51.19 103.6
30.49 39.47 56.42 109.8

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 160

140

120
Temperature ( C)
o

100

80

60 0 mole % water
10 mole % water
30 mole % water
40 Mixtures for crystals extraction
Wyrzykowska-Stankiewicz and Palczewska-Tulinska (1991)
Moyers (1986)
20
0 10 20 30 40 50 60 70 80 90 100
Phenol Mole % of BPA BPA
Figure 3. SLE temperature-composition data of phenol + BPA + water obtained in the present study

For the isoplethal cut of 0 mole % of water (i.e. phenol + BPA system), data points are obtained for the entire
composition range of phenol and BPA. If these data are used to compare with the literature data from Moyers
(1986) and Wyrzykowska-Stankiewicz and Palczewska-Tulińska (1991) in Figure 3, it can be seen that they
generally agree with each other, except with minor deviations near the peritectic point. This proves that the
experimental technique and apparatus developed in this study is reliable. Since the major objective for
constructing the SLE phase diagram is to facilitate the synthesis of crystallization-based separation or
purification process of bisphenol A, the most important feature of the phase diagram is the boundary between
BPA and phenol/BPA adduct saturation regions. Driven by this objective, data points for the isoplethal cuts
of 10 and 30 mole % of water are only obtained for phenol-BPA composition range where the discontinuous
change of the saturation boundary is believed to occur.

Step 4. Based on the results obtained from Step 3, we can already have a rough idea on the location of
the boundary between BPA and phenol/BPA adduct crystallization regions by tracing the point of
discontinuity of the saturation boundary for each isoplethal cut. To confirm the location of this boundary and
thus the crystallization region of BPA, crystals were extracted from mixtures that have composition
represented by black closed triangles indicated in Figure 3 through the technique of suction filtration. The
collected crystals were then dissolved into a solvent mixture comprising 45% water and 55% methanol by
volume to make up a solution ready for undergoing a high performance liquid chromatography test for
analyzing the identity. The HPLC tests were performed by a Waters Alliance HPLC System, which consisted
of a Waters 2695 Separations Module and a Waters 2996 Photodiode Array Detector. To conduct the analysis,

9
liquid samples carried by a mobile phase consisting of 45% water and 55% methanol by volume were
pumped through a Microsorb MV C18 column operated at 40oC. The emergence of chemicals from the
column was then perceived by the photodiode array UV detector. By comparing the HPLC results of the
sampled crystals with the HPLC chromatographs of the pure standard solution of BPA and phenol/BPA
adduct, it is confirmed that the region on the right of the point of discontinuity of the saturation boundary
belong to the crystallization region of BPA, whereas on the left is the crystallization region of adduct.

CONCLUSIONS
In this study, a generic scheme that can be used to determine the isobaric SLE phase diagram of any
organic and inorganic system at 1 atm has been presented. Since most of the decisions involved in
conducting the scheme are dependent on the objectives for crystallization process synthesis, the resulting
SLE phase diagram not only provides useful SLE data, but also visualization on the important features for
process synthesis, such as the crystallization region of the targeted species. The execution of this generic
scheme is illustrated by determining the isobaric SLE phase diagram of a system comprising phenol, BPA
and water.

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AIChE J., 43, 91 (1997).
Berry, D. A., and Ng, K. M., “Synthesis of Reactive Crystallization Processes,” AIChE J., 43, 1737 (1997).
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