Fluid Phase Equilibria 148 1998.

147160

A new method for measuring solidliquid equilibrium phase diagrams

using calorimetry
Joao
A.P. Coutinho
a

a, )

, Veronique
Ruffier-Meray

Centro de Inestigacao
Departamento de Qumica,
Faculdade de Ciencias,
Rua do Campo Alegre,
em Qumica,

687. 4150 Porto, Portugal

b
Institut Francais du Petrole,
1 and 4 A. du Bois-Preau.

BP 311, 92506 Rueil-Malmaison CEDEX, France

Received 21 July 1997; accepted 27 January 1998

Abstract
A new experimental technique using calorimetric measurements to establish solidliquid equilibrium SLE.
phase diagrams of binary systems of organic compounds with complete immiscibility in the solid phase is
presented. Unlike some methods previously reported in the literature it is not based in the identification of the
phase transition temperatures at different compositions of the mixture. Instead it measures the changes on the
relative size of the liquid phase during the fusion of a mixture, that is later converted into a phase diagram using
the lever rule. This technique, while somewhat less accurate than some processes based in the direct detection of
phase transitions for measuring SLE phase diagrams, is much faster and presents an accuracy similar to other
calorimetric techniques. It also makes possible to define the position of invariant points, such as the eutectic or
peritectic, both in composition and temperature, or the composition of intermediate compounds, with a single
calorimetric measurement. q 1998 Elsevier Science B.V. All rights reserved.
Keywords: Experimental technique; Solidliquid equilibrium; Crystallisation; Phase diagram; Calorimetry; DSC

1. Introduction
The importance of knowing the phase diagram for a mixture in designing separation processes is
well known, but the measurement of phase diagrams is costly and time consuming, restricting the
amount of experimental information available. Crystallisation is a purification process particularly
well suited for biological molecules for they tend to be heat sensitive, decomposing at high
temperatures. Unfortunately, for complex molecules like biological products, the data are very scarce
and the standard predictive models like UNIFAC proved to be very unreliable or of limited
)

Corresponding author.

0378-3812r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.

PII S 0 3 7 8 - 3 8 1 2 9 8 . 0 0 1 9 6 - 4

148

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

applicability w1x. Many different techniques have been presented in the literature for measuring
solidliquid equilibrium SLE. phase diagrams in several different conditions w2x, and among these
some calorimetric methods such as differential scanning calorimetry DSC. and differential thermal
analysis DTA. . Some alternative processes, making use of the specificity of differential calorimetry,
have been reported w3x but traditionally DSC is used in the same way as DTA to directly identify the
temperatures of phase transition. The phase diagram is established by preparing a number of mixtures
covering a part, or the entire composition range, and measuring the phase transitions for each mixture
w47x. This is a very strong and flexible method for it allows the measurement of complex phase
diagrams for binary or multicomponent systems with total or partial miscibility in any of the phases.
For the systems presenting simple binary solidrliquid phase diagrams with complete immiscibility in
the solid phase, which are about 1r3 of the systems with organic compounds w8x, a much simpler
approach can be used as presented here.
A whole range of compositions, theoretically the entire range between two invariant points, is
measured in a single run making the phase diagram measurement procedure a lot faster and cheaper
for it is time and material consuming. Instead of a direct measurement of phase transitions, the
fraction of liquid forming during the melting of a sample is measured and then converted into phase
boundaries using the lever rule. Recently, this idea has been applied to DTA measurements w9x for
eutectic systems making use of several simplifications and some restrictive hypothesis. Here, a
general thermodynamic derivation of the method will be presented showing that it can be applied to
all systems showing no solubility in the solid phase, with or without the formation of intermediate
compounds. This method has the limitations of the calorimetric techniques used, thus being a bit less
accurate than other methods based on the visual detection of phase transitions w2,10x. However, its
accuracy should not be much lower than that of other methods based in the interpretation of peaks
issued from calorimetric measurements.
The thermodynamical background of this technique is developed and presented. The hypothesis
used and the simplifications performed help to recognise the limits of validity and the reliability of the
method. It is shown how to completely define the position of the invariant points, eutectic, peritectic
and intermediate compounds, both in composition and temperature, with a single calorimetric
measurement. A couple of experimental examples are presented showing the performance of the
proposed technique in comparison with data obtained from alternative procedures w11x. The reader
interested in this subject should also notice the work by Muller
and Borchard w12x that was published
during the revision of this work.

2. Thermodynamical background
2.1. Systems with an eutectic point and no intermediate compounds
As indicated before, this phase diagram measurement technique is not based on a direct measurement of the phase boundaries by means of some process of phase transition detection, but instead
based on the measurement of the enthalpy variation upon heating, which allows the determination of
the relative size of the liquid fraction, later converted into a phase diagram using the lever rule.
Consider a binary system presenting no solubility in the solid phase and complete miscibility in the
liquid phase having the phase diagram sketched in Fig. 1. A mixture of composition W in component

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

149

Fig. 1. Solidliquid phase diagram with an eutectic point and complete immiscibility in the solid phase.

B, at a temperature T0 inferior to TEut is heated until complete fusion. Unless otherwise stated the
compositions throughout this work always refer to component B.. The enthalpy variation with the
temperature during the process is recorded and presented in Fig. 2.
The first step in the calorimetric analysis would be to check the position of the mixture relatively to
the eutectic. The procedure to use for that purpose will be described later. For the moment it is
assumed that 0 - W - WEut . The enthalpy plot can be described by:
h T . s ha T - T Eut . q hb T s T Eut . q h c TEut - T F TCr . q hd TCr - T .
1.
with
ha s mtotal
A

HT C

S
total
pAdT q m B

HT C

S
pB dT

2.

LEut
E
hb s mALEut h m ATEut :q mtotal
q mtot
B h m B T Eut :q mA
B .h

h c s mtotal
B

HT

L
CpB
dT q

Eut

HT

S
mAS CpA
dT q

Eut

HT

L
mAL CpA
dT q

Eut

3.
T

HT

Eut

L :
E
total
LEut
q mtotal
. hE
B q mA T . h y m B q mA

hd s mtotal
A

HT

L
CpA
dT q mtotal
B

Cr

HT

L
CpB
dT

hmA

d mAL
dT

dT

4.
5.

Cr

Where P T : is the value of the property at temperature T. The meaning of the other symbols is the
usual or is described in the nomenclature section. The effects due to the excess heat capacities in the
liquid phase are neglected.
The goal is to measure:
L
T d mA
dT
mAL
T Eut dT
L
aA s
s total
6.
L
mA
TCr d mA
dT
T Eut dT

that is easily converted in phase boundaries using the lever rule.

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

150

Fig. 2. Temperature dependence of the enthalpy of the mixture which phase diagram is shown in Fig. 1.

The fusion of component A occurs in two steps: a portion melts at the eutectic point, mALEut , and
another between T Eut and TC , mAL ) T .. Two accessory liquid fractions will thus be defined:

LEut
s
A

L)
A s

mALEut

7.

mtotal
A
mAL )

8.

mASEut

LEut
where mASEut s mtotal
A y mA . The relation between these three liquid fractions is simply given by:

aAL s aALEut q aAL ) 1 y aALEut .

9.

The estimation of aAL ) is first considered. Using calorimetry only enthalpic rather than mass
variations can be accounted for. What can be measured is the ratio between the energy required to the
fusion of the amount of component A that melts between the eutectic point and temperature T,
mAL ) T : , and the energy required to complete fusion of the fraction of component A that remains
solid at the eutectic, mASEut s mAL ) TCr : :
T

L))
s
A

HT

hmA

d mAL

Eut

dT

TCr

d mAL

HT

Eut

hmA

dT

dT

q T :
s

dT

qtotal

10.

The melting enthalpies at a generic temperature T are related with melting enthalpies at the melting
temperature by:
h m T . s h m Tm : q

HT C

S
L
p y Cp

/ dT

11.

but since the difference of heat capacities between the two phases is much smaller than the enthalpies
of melting it can be assumed that the melting enthalpies are, to a fair extent, temperature independent,
therefore aAL ) ) can be considered equivalent to aAL ) .

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

151

Unfortunately, it is not possible to access directly by a calorimetric measurement the energies

defined as q T : and qtotal . Together with the heat used for melting the solute, the energy for heating
the solution, and heat effects associated to the mixing in the liquid phase are also measured. It is thus
necessary to isolate the energy used for melting the solute from the other two.
Eq. 8. can thus be related to the measured enthalpy variations by:

aAL ) s aAL ) ) s

hT . y I T .

12.

h TCr . y I TCr .

where I T . is:
I T . s hT Eut :q mtotal
B

HT

L
CpB
dT q

Eut

HT

S
mAS CpA
dT q

Eut

HT

L
L :
E
mAL CpA
dT q mtotal
B q mA T . h

13.

Eut

The I represents the energy required to heat the mixture from the eutectic point to temperature T
and the heat effects associated to the mixing of solute and solvent in the liquid phase. It cannot be
calculated because even if the composition of the solution, the excess enthalpy and the heat capacities
were known, and they seldom are, the masses of solute in the solid and liquid phases at each
temperature would still be unknown. To estimate I from the measured data another approach will be
followed.
A straight line, w , tangent to the curve just above the eutectic point is drawn. It describes the
energy required to heat the mixture present at the eutectic point:
L
SEut S
LEut L
w T . s hTEut :q mtotal
CpAT Eut :/ T y T Eut .
B C pB T Eut :q mA C pA T Eut :q mA

14.

Another straight line, c , is drawn just above the temperature of disappearing of the last crystal, the
cloud point temperature, TCr . It represents the energy used to heat the solution above the TCr :
L
total L
c T . s hTCr :q mtotal
B C pB TCr :q mA C pA TCr :/ T y TCr .

15.

If the heat capacities are assumed to be approximately temperature independent it is possible to show
that:
dw

dI
s
dT

dT

q aAL )

dc

dw
y

dT

dT

d aAL )

aAL )

dT

h E mtotal
B

16.

For athermal solutions or solutions with a low heat of mixing, the last term of d IrdT can be
neglected without a significant effect on aAL ) . For mixtures with higher excess enthalpies this term is
also usually negligible because h E and 1raAL ) = d aAL ) rdT . present opposite variations with the
temperature and tend to cancel each other.
If the last term is neglected, knowing that I T Eut : s h T Eut : the numerical integration of d IrdT
can be readily performed and with a simple iterative procedure the value of aAL ) calculated. The
assumption of temperature independent heat capacities made above affects only the term d wrdT y
d crdT .. However, the slopes of the two straight lines are usually not very different. Moreover, aAL )
ranges from 0 to 1 further reducing its effect. Normally, assuming temperature independent heat
capacities does not affect the value of d IrdT by more than 2% and influences the estimation of aAL )
by less than 0.1% for aAL ) ) 0.01.

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

152

When the slopes of w and c do not differ more than 20% making I s w would introduce a
relative error inferior to 2.5% in aAL ) for aAL ) ) 0.01 very much simplifying the calculation
procedure. Although this simplification may not always be acceptable, it always provides a good
starting point for the iteration of aAL ) .
With aAL ) known, the next step is to calculate aALEut to obtain aAL from Eq. 9.. The definition of
LEut
a total liquid fraction at the eutectic temperature, a total
:

LEut
total s

mALEut q mtotal
B
total
mtotal
A q mB

17.

is helpful because this quantity is related with aALEut by:

LEut
s
A

LEut
a total
yW

18.
1yW
and from Eqs. 3. and 17. it is possible to show that it can be estimated from the measured quantities
as:
hb

LEut
total s

m total

y W hm B y hmA.
h m A q hE

19.

where m total is the mass of the sample being analysed and the heats of fusion are those at the eutectic
temperature. Since normally h m A 4 h E the total liquid fraction at the eutectic point can immediately
LEut
be calculated and from it aAL . But a total
presents also another interest. If the lever rule is applied to
LEut
the eutectic point, using Eq. 17. and some algebraic manipulation, it is possible to relate a total
to the
composition of the eutectic point:
WEut s

20.

LEut
a total

This means that with a single calorimetric measurement the eutectic point is completely defined, its
temperature being obtained from the jump on the curve of Fig. 2 and the composition from the total
LEut
liquid fraction at the eutectic point, a total
, as given by Eq. 20..
Please note that these equations like all the others presented before are valid only for 0 - W - WEut .
For this reason before making the analysis of a calorimetric measurement the eutectic point must be
located to know how to perform the analysis correctly. This is done using the Eqs. 19. and 20.
above, together with the following couple of equations valid for WEut - W - 1:
hb

LEut
total s

m total

q 1 y W . h m B y h mA.
h m B q hE

21.

and
WEut s

1 y W .
LEut
a total

22.

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

153

Using these four equations it is possible to calculate the composition at the eutectic point since only
one of the couples will produce a physically meaningful result. The placement of the mixture
relatively to the eutectic point indicates the procedure to be used in the estimation of aAL . If
WEut - W - 1 the method is by all means similar to that described before but the indexes referring to
the compounds have to be changed.
The phase boundaries are obtained with no difficulties from aAL using the lever rule. The relation
between the composition at the phase boundaries, W L , and the liquid fraction, aAL , is given by:
W Ls
L

W s

W
W q 1 y W . aAL

a BL W
1 q W a BL y 1 .

for 0 - W - WEut
for WEut - W - 1

23.
24.

2.2. System with an intermediate compound with a congruent melting point

Systems that present the formation of an intermediate compound with a congruent melting point
can also be treated with the formalism described. Consider the binary system with the phase diagram
sketched in Fig. 3. Beside the pure compounds it presents three other invariant points, WE1, WE2 and
WAB . This last is the composition of the A x B y intermediate compound from now on to be referred as
AB. Two mixtures of compositions Wi and Wii in component B are to be used in the measurement
covering the composition range 0 - W - WAB of the phase diagram. The range WAB - W - 1 is
treated identically.
Again, as it was done before, the melting of the samples is treated in two steps: the melting at the
eutectic point and the melting at temperatures above the eutectic. The estimation of aAL ) is identical
LEut
to the preceding case. The difference lies in the estimation of a total
. This is not as simple as before
due to the presence of the intermediate compound AB. Two measures, at Wi and Wii are required to
provide information simultaneously on WE1, WAB .

Fig. 3. Solidliquid phase diagram for a system with an intermediate compound A x B y stable up to the melting point.

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

154

For the measurement at Wi , the total liquid fraction at the eutectic is obtained from the measured
enthalpy variation as:
hb

hm

LEut
total s

m total

WAB

AB

y hmA.

25.

h m A q hE

being related with the eutectic composition by:

WEut s

26.

LEut
a total

For the measurement at Wii , the total liquid fraction at the eutectic is given by:
hb

LEut
total s

m total

q 1y

W
WAB

h m A y h m AB .

27.

h m AB q hE

and the composition of the intermediate compound is obtained from the lever rule as:
WAB s W q

LEut
a total
LEut
1 y a total

W y W E .

28.

Using the experimental data from the two measurements and the Eqs. 25. 28. WAB and WE1 are
obtained. Since WAB cannot be any arbitrary composition because x and y have to be integers, its
value will be correctly known reducing the uncertainties associated to the experimental measurements
and the calculation procedure.
LEut
LEut
and aAB
for the sample at Wi is the same presented before in Eq.
The relation between a total
18.. For the sample at Wii is somewhat different due to the presence of compound AB:
LEut
aAB
s WAB

LEut
a total
y 1 y W .

1 y WAB
WAB

29.

being the relation between the different liquid fractions:

L
LEut
L)
LEut
aAB
s aAB
q aAB
1 y aAB
.

30.

2.3. System with an intermediate compound with an incongruent melting point. Peritectic point
The case of a system with a peritectic point is discussed now. The phase diagram for such a system
is presented in Fig. 4 w2x. The region 0 - W - WPer presents no differences to the case studied in the
previous section being possible from measurements at Wi and Wii to measure that region of the phase
diagram and define also the composition of WAB . Another measurement at Wiii will provide the
description of the remaining portion of the phase diagram and the composition of the peritectic point
WPer .

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

155

Fig. 4. Solidliquid phase diagram for a system with a peritectic point.

Again the fusion is to be split into two parts, a fusion at the peritectic point, a BLPer, and the
remaining above this temperature, a BL ) , being the liquid fractions related with the total liquid
fraction, a BL , by:

a BL s a BLPer q a BL ) 1 y a BLPer .

31.

As before the estimation of a BL ) is identical to what was done for the simple eutectic system, and
LPer
a BLPer is related to the total liquid fraction at the peritectic point, a total
, by:

a BLPer s

LPer
a total
y 1 y W .

32.

This liquid fraction is obtained from the enthalpy variation at the eutectic point, hb, and the melting
enthalpies of the pure compounds according to:
hb
y

LPer
total s

m total

1yW
1 y WAB

h m AB y h m B .

h m B q hE

33.

from where the composition of the peritectic point, WPer , is obtained:

WPer s 1 y

1yW
LPer
a total

34.

This procedure allows the conversion of calorimetric measurements into SLE phase diagrams. It
shows that a lot more of information can be drawn from the calorimetric results than just the transition
temperatures andror the enthalpies of phase transition. Whenever a system is suspected to be a simple
eutectic, be it from calorimetric experiments or because the phase diagrams for compounds in the
same family present a simple eutectic, and this is a very common situation among organic compounds
where more than 25% of the solidrliquid phase diagrams are of this kind w8x, the phase diagram can
be immediately established with a couple of measurements that should not take longer than a few

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

156

Table 1
Enthalpy variation for a sample of n-C 19 H 40 rethylbenzene Wn - C 19 H 40 s 0.2247.
T K.

h mJ.

T K.

h mJ.

T K.

h mJ.

T K.

h mJ.

158.73
159.59
160.46
161.33
162.19
163.06
163.93
164.79
165.66
166.52
167.39
168.25
169.12
169.99
170.85
171.72
172.59
173.45
174.32
175.19
176.05
176.92
177.78
178.65
179.51
180.36
181.20
182.00
182.62
182.93
183.08
183.22
183.47
183.89
184.59
185.68
187.64
189.92
191.29
192.33
193.26
194.14
195.02
195.89

0
0.679
2.031
3.895
5.608
7.163
9.316
11.06
12.98
15.64
17.83
20.49
24.06
27.29
30.06
32.49
34.89
38.23
42.73
47.04
50.94
55.32
60.99
67.70
75.36
85.81
102.43
134.25
216.92
426.32
831.10
1452.9
2273.3
3249.5
4312.6
5358.0
6186.6
6636.3
6815.7
6901.2
6954.3
6996.1
7033.4
7068.6

196.76
197.63
198.50
199.37
200.23
201.10
201.97
202.83
203.70
204.57
205.43
206.30
207.17
208.03
208.90
209.77
210.63
211.50
212.37
213.23
214.10
214.97
215.83
216.70
217.57
218.43
219.30
220.17
221.03
221.90
222.77
223.63
224.50
225.37
226.23
227.10
227.97
228.83
229.70
230.57
231.43
232.30
233.17
234.03

7102.7
7136.4
7170.0
7203.2
7236.5
7269.8
7303.1
7336.3
7369.6
7402.9
7436.1
7469.4
7502.7
7536.0
7569.2
7602.5
7635.8
7669.0
7702.3
7735.6
7768.9
7802.1
7836.0
7870.4
7904.5
7938.9
7974.2
8009.9
8045.6
8081.6
8117.5
8153.9
8190.6
8227.2
8264.1
8300.8
8337.8
8374.9
8412.2
8449.9
8487.7
8525.8
8564.4
8603.8

234.90
235.77
236.63
237.50
238.36
239.23
240.10
240.96
241.83
242.70
243.56
244.43
245.30
246.16
247.03
247.90
248.76
249.63
250.50
251.36
252.23
253.06
253.93
254.80
255.65
256.51
257.37
258.23
259.09
259.94
260.80
261.66
262.51
263.37
264.22
265.07
265.92
266.76
267.61
268.44
269.29
270.12
270.95
271.78

8643.1
8682.0
8721.4
8761.3
8801.8
8842.6
8883.6
8924.9
8966.6
9008.9
9051.8
9095.2
9139.0
9183.8
9229.5
9276.0
9323.1
9371.0
9419.8
9469.5
9520.7
9573.7
9628.7
9685.3
9743.2
9803.3
9866.3
9932.0
10,000
10,071
10,146
10,224
10,306
10,393
10,484
10,581
10,684
10,795
10,913
11,038
11,173
11,319
11,476
11,646

272.61
273.44
274.27
275.08
275.90
276.70
277.50
278.30
279.09
279.89
280.69
281.54
282.50
283.68
284.90
285.93
286.86
287.75
288.62
289.49
290.36
291.23
292.09
292.96
293.83
294.69
295.56
296.43
297.29
298.16
299.03
299.89
300.76
301.63
302.49
303.36
304.22
305.09
305.96
306.82
307.69
308.56
309.42
310.29

11,828
12,022
12,230
12,454
12,696
12,960
13,246
13,555
13,889
14,247
14,628
15,023
15,402
15,708
15,901
16,009
16,081
16,139
16,192
16,244
16,296
16,347
16,399
16,451
16,503
16,556
16,611
16,665
16,719
16,774
16,829
16,884
16,939
16,994
17,049
17,105
17,161
17,216
17,272
17,330
17,386
17,444
17,502
17,560

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

157

Table 2
Enthalpy variation for a sample of n-C 22 H 46 rethylbenzene Wn - C 22 H 46 s 0.2144.
T K.

h mJ.

T K.

h mJ.

T K.

h mJ.

T K.

h mJ.

T K.

h mJ.

153.15
153.90
154.65
155.40
156.15
156.90
157.65
158.40
159.15
159.90
160.65
161.40
162.15
162.90
163.65
164.40
165.15
165.90
166.65
167.40
168.15
168.90
169.65
170.40
171.15
171.90
172.65
173.40
174.15
174.90
175.65
176.40
177.15
177.90
178.65
179.40
180.15
180.90
181.65
182.40
183.15
183.90
184.65
185.40

0
50.841
99.422
147.44
195.78
243.63
291.38
340.19
389.60
439.99
490.42
540.54
591.26
642.10
693.09
742.39
792.39
842.65
893.96
945.38
996.39
1047.4
1097.7
1149.5
1199.7
1252.0
1303.5
1354.0
1403.2
1453.4
1503.4
1553.4
1604.1
1653.5
1704.7
1756.8
1808.8
1862.9
1920.8
2000.7
4322.8
5658.0
6195.6
6399.8

186.15
186.90
187.65
188.40
189.15
189.90
190.65
191.40
192.15
192.90
193.65
194.40
195.15
195.90
196.65
197.40
198.15
198.90
199.65
200.40
201.15
201.90
202.65
203.40
204.15
204.90
205.65
206.40
207.15
207.90
208.65
209.40
210.15
210.90
211.65
212.40
213.15
213.90
214.65
215.40
216.15
216.90
217.65
218.40

6527.4
6644.0
6755.7
6859.7
6955.2
7037.8
7110.3
7182.2
7253.7
7324.1
7393.2
7461.3
7531.7
7601.2
7670.9
7739.9
7809.5
7880.0
7948.6
8016.4
8086.3
8155.7
8225.4
8295.1
8364.7
8432.6
8501.8
8571.1
8639.7
8709.6
8779.2
8849.3
8921.5
8990.6
9060.1
9129.8
9200.0
9269.1
9339.1
9408.8
9477.4
9549.0
9618.7
9689.2

219.15
219.90
220.65
221.40
222.15
222.90
223.65
224.40
225.15
225.90
226.65
227.40
228.15
228.90
229.65
230.40
231.15
231.90
232.65
233.40
234.15
234.90
235.65
236.40
237.15
237.90
238.65
239.40
240.15
240.90
241.65
242.40
243.15
243.90
244.65
245.40
246.15
246.90
247.65
248.40
249.15
249.90
250.65
251.40

9758.7
9827.9
9898.2
9967.0
10,038
10,107
10,175
10,244
10,314
10,384
10,453
10,522
10,592
10,661
10,730
10,800
10,871
10,941
11,010
11,080
11,151
11,220
11,291
11,360
11,432
11,500
11,569
11,638
11,707
11,776
11,847
11,916
11,985
12,054
12,125
12,195
12,265
12,336
12,406
12,477
12,546
12,616
12,686
12,757

252.15
252.90
253.65
254.40
255.15
255.90
256.65
257.40
258.15
258.90
259.65
260.40
261.15
261.90
262.65
263.40
264.15
264.90
265.65
266.40
267.15
267.90
268.65
269.40
270.15
270.90
271.65
272.40
273.15
273.90
274.65
275.40
276.15
276.90
277.65
278.40
279.15
279.90
280.65
281.40
282.15
282.90
283.65
284.40

12,828
12,900
12,972
13,043
13,115
13,187
13,260
13,332
13,405
13,478
13,551
13,626
13,702
13,778
13,854
13,931
14,008
14,086
14,165
14,244
14,322
14,404
14,486
14,568
14,652
14,739
14,826
14,914
15,003
15,094
15,189
15,284
15,381
15,481
15,585
15,692
15,802
15,919
16,041
16,170
16,302
16,442
16,589
16,746

285.15
285.90
286.65
287.40
288.15
288.90
289.65
290.40
291.15
291.90
292.65
293.40
294.15
294.90
295.65
296.40
297.15
297.90
298.65
299.40
300.15
300.90
301.65
302.40
303.15
303.90
304.65
305.40
306.15
306.90
307.65
308.40
309.15
309.90
310.65
311.40
312.15
312.90
313.65
314.40
315.15
315.90
316.65
317.40

16,913
17,089
17,278
17,477
17,688
17,915
18,160
18,420
18,704
19,006
19,329
19,632
19,888
20,035
20,138
20,225
20,304
20,379
20,453
20,529
20,605
20,683
20,757
20,833
20,908
20,983
21,058
21,133
21,207
21,283
21,358
21,434
21,510
21,586
21,663
21,738
21,814
21,890
21,967
22,043
22,119
22,195
22,272
22,349

158

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

hours or use more than some milligrams of compound. If an intermediate compound exists the
procedure becomes somewhat more complex, more measurements are needed as well as the enthalpy
of melting of this new compound. Yet the same approach is applicable in the search for the invariant
points of the phase diagrams and to establish the phase boundaries. This technique can also be used as
a complement to some other phase diagram measurement techniques helping to establish the
coherence of the measurements, identify and eliminate systematic deviations, or to speed up these
measurements by identifying the composition of the invariant points, such as the eutectics, peritectics,
or the intermediate compounds compositions. The presence of solid phase transitions is not a
limitation to the applicability of this technique that can easily be extended to pseudo-binaries where
the solubility of a solute in a mixture of solvents is to be studied.
3. Experimental measurements
To test the performance of the proposed technique, two solutions, one of nonadecane and the other
of docosane Fluka with a purity of at least 99%. in ethylbenzene Aldrich, 99.8%. were prepared and
their phase diagrams measured. Aluminium pans of 150 m l were filled up to 2r3 with the solutions
and analysed in a Mettler TA 3000 DSC. The calorimeter has a refrigeration system using liquid
nitrogen that allows measurements to be done at temperatures down to 150 K and provides a very
precise temperature control. The sample is heated from 150 K up to 320 K at a rate of 1 Krmin. The
use of a low heating rate is very important to assure an equilibrium state during the heating. The
enthalpy changes were registered every 0.75 K between the starting and final temperatures. They are
presented in Tables 1 and 2 and were treated according to the procedure proposed in the previous
section.
The analysis of the position of the eutectic point indicates that WEB Eut ) 0.99. For calculation
purposes it was considered that WEB s 1. The measured phase diagrams are shown in Fig. 5. Data for
the system nonadecanerethylbenzene were previously unavailable in the literature, for the system
docosanerethylbenzene a comparison with data by Ghogomu et al. w11x is presented. There is a very

Fig. 5. Solidliquid phase diagrams for nonadecanerethylbenzene and docosanerethylbenzene measured by DSC using the
proposed technique.

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

159

good agreement between the two sets of data showing the potential of the proposed technique in
solidrliquid phase diagram measurements.

4. Conclusions
A new technique using calorimetry for measuring solidrliquid phase diagrams of binary mixtures
completely immiscible in the solid phase, with or without the formation of intermediate compounds,
and to locate the invariant points, is presented.
Unlike other methods for phase diagram measurement reported in the literature, this method does
not perform a direct determination of the phase transition temperatures. Instead it measures the
fraction of melted solution, that converts into a phase diagram using the lever rule. While being of a
more limited applicability and somewhat lower accuracy than other methods currently used, the
proposed technique is much faster and cheaper since a single measurement is enough to define the
phase diagram in the region between two invariant points. It can either be used to directly establish a
phase diagram or as a complement to any other phase diagram measurement technique helping to
establish the coherence of the measurements, identify and eliminate systematic deviations, or to speed
up these measurements by identifying the composition of the invariant points, such as the eutectics,
peritectics, or the intermediate compounds compositions.
It is shown that a lot more of information can be drawn from the calorimetric results than just the
transition temperatures andror the enthalpies of phase transition. Measurements using this new
technique show a very good agreement with data by other authors showing the potentialities of the
proposed technique.

5. Nomenclature
Cp
h
hE
hm
m
q
Tc
T Eut
Tm
T0
V
W

heat capacity
enthalpy
excess enthalpy
melting enthalpy
mass
energy
cloud point temperature
eutectic point temperature
melting point
starting temperature
molar volume
mass fraction

Greek letters
aL
aS

fraction of component melted

fraction of component crystallised

J.A.P. Coutinho, V. Ruffier-Merayr Fluid Phase Equilibria 148 (1998) 147160

160

w
c

straight line defined in Eq. 14.

straight line defined in Eq. 15.

Subscripts and superscripts

A
B
AB
Eut
liq
L
m
Per
S
total

component A
component B
component A x B y
relative to the eutectic point
liquid
liquid
melting
relative to the peritectic point
solid
total

References
w1x
w2x
w3x
w4x
w5x
w6x
w7x
w8x
w9x
w10x
w11x
w12x

A.M. Peres, E.A. Macedo, Submitted to Fluid Phase Equilibria, 1997.

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M.E. Brown, Introduction to Thermal Analysis, Chapman & Hall, London, 1988.
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U. Wiesner, W. Bieger, G. Krabbes, Thermochim. Acta 290 1996. 115.
U. Domanska, Fluid Phase Equilibria 114 1996. 175.
P.M. Ghogomu, J. Dellacherie, D. Balesdent, J. Chem. Thermodynamics 21 1989. 925.
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