1

LAB 3: BINARY SOLID-LIQUID EQUILIBRIUM IN TWO-COMPONENT SYSTEM

SolidLiquid Phase Equilibrium (Ref: Gallus et. al. J.Chem. Ed., 78, 961-964, 2001.)
The theoretical background for solidliquid binary phase diagrams with no solid
solubilities is quite simple. A system with one or more compounds Ai in two phases (s) and ( l )
that are in mutual contact is in thermodynamic equilibrium if the chemical potentials i are the
same in both phases:
i ( s )( p, T ) = i (l)( p, T , xi (l))

(1)

In the following, we consider the compounds to be completely insoluble in the solid phase
i ( s )( p, T ) = i ( s )( p, T )

(2)

where i ( s )( p, T ) is the chemical potential of the pure solid compound Ai at pressure p and
temperature T. Complete miscibility in the liquid phase leads to
i (l)( p, T , xi (l)) = i (l)( p, T ) + RT ln( f i (l), xi (l))

(3)

where i (l)( p, T ) represents the chemical potential of the pure liquid compound Ai. While the
activity coefficients f i (l)( p, T , xi (l)) in real systems depend on the composition of the liquid
phase, in systems exhibiting nearly ideal behavior f i (l) 1, which, as a result of the experimental
findings, can be considered fulfilled in the following. The temperature T at which the two
coexisting phases are in equilibrium at constant pressure is then related to the mole fraction xi (l)
of the liquid melt by
1

R
T =
ln xi (l)

Ti m H i

(4)

where m H i = hi (l) hi ( s ) is the molar heat of fusion and Ti is the melting point of the pure
substance Ai. In deriving eq (4), m H i is considered to be constant in the temperature range
investigated. The coexistence curve between the liquid mixture and the pure solid Ai in the
(T , xi (l)) diagram extends from the pure substance to the eutectic composition; that is, 1 xi (l)
xi , E (l) for i = {1,2}.
The eutectic point ( xi , E (l), TE ) in an ideal binary system (where x1 (l) + x2 (l) = 1) with
given quantities Ti and m H i can be obtained by numerical analysis (e.g. using Maple or
Mathematica) or by a simple iterative approximation (Fig. 1).
The two liquidus curves described by eq (4) cross at the eutectic composition when
T ( x1 (l)) = T ( x2 (l )) . Table 2 lists eutectic compositions and temperatures that have been
calculated for our binary systems using the data of the pure components as given in Table 1. The
cryoscopic constant R (Ti ) 2 / m H i is the slope of the liquidus curve T ( xi (l )) at xi (l) = 1.

Figure 1. Calculated liquidus curves (bold lines) in an ideal binary solidliquid phase diagram assuming
no solid solubility. The two curves (dotted lines) described by eq. (4) intersect at the eutectic point at
x1, E (l) . The light solid straight lines show the asymptotic freezing point depression near the pure
components. This diagram represents the binary system p-dichlorobenzene (1)phenanthrene (2).

Table 1. Properties of some compounds

Table 2. Compositions and temperatures of all 15 eutectic binary systems

The Phase Rule

The simplest possible two-component phase diagram is one in which no solid solutions or

Temperature

compounds occur (Fig. 2).

S
Q

c3

Figure 2 Two solids and one liquid, no solid solutions.

According to the phase rule, a single phase in a two-component system may possess three degrees
of freedom:
F = CP+2 = 21+2 = 3

(5)

when F is the degree of freedom, C is the number of component, and P is the number of phase.
These are temperature, pressure, and the composition of one of the two components.
Since studies of solid-liquid equilibrium are nearly always carried out at constant
pressure, one degree of freedom is lost and the phase rule becomes
F = CP+1 = 2P+1 = 3P

(6)

Thus, temperature and the composition are the variables, and these may be plotted on ordinary
graph paper.

THERMODYNAMIC ANALYSIS
Let us continue with this point of view, and think of the system at point a2 as a saturated
solution of solid B in the solvent A. At point a2, then the following equilibrium is established
between solid B and a solution of mole fraction xB :
B

B (solid) = B (solution)

(7)

Since the system is at equilibrium, G = 0, so that we can write

G = 0 = GB (solution) GB (solid)
B

(8)

If we choose as the standard state a solution of unit mole fraction (xB = 1), then the
B

relationship between the free energy per mole at any xB and the free energy per mole in the
B

standard state is given by

o

GB (solution) = GB (solution) + RT ln xB
B

(9)

when Equation (6) is substituted in eq (8), the result is

o

GB (solution) GB (solution) = RT ln xB
B

(10)

This may be rearranged slightly to give

ln x B =

G B (solution)
RT

(11)

H
(G/T )
Recalling that
= 2 at constant pressure, we differentiate eq (11) to obtain
T
T P

H B (solution)
ln x B
=

RT 2
T p

(12)

Equation (12) may also be written in a slightly different from:

ln x B
H B (solution )

=
R
(1/T ) p

(13)

At this point let us write Equation (4) in two steps to indicate first the solution process
involving the fusion of the solute, and then the ideal mixing of the liquid solute with the already
liquid solvent, for which H (mix) = 0:
B (solid) = B (liquid) = B (solution)

(14)

H (fus) H (mix)

H (soln)

Heat of Solution
When the solution process is ideal, H (mix) = 0, so that H (solution) = H (fusion),
and eqn (13) can be written as
ln x B
H B (fusion )

=
R
(1/T ) p

(15)

Consequently, data from phase diagrams such as Fig. 1 can be used to determine heats of fusion
of both components,since a plot of ln xA against (1/T) gives a straight line of slope equal to the
heat of fusion of A, and a plot of ln xB against (1/T) gives a straight line of slope equal to the
B

heat of fusion of B (both divided by R). In this manner heats of fusion for many nonelectrolytes
and metals can be determined, if the two components form an ideal solution which is not
uncommon.

Ideal Solubility
Integration of Equation (13) leads to another interesting interpretation of ideal
solubilities:
ln x B
1
1

T o T

H B (fusion)
R

(16)

This may be written explicitly in terms of ln xB, where xB is the solubility of B in A at

B

temperature T, HB (fus) is the heat of fusion of B, and TBo is the melting point of pure B:
B

ln x B

H B (fusion) 1
1

T o T
R
B

(17)

What is remarkable about this equation is that it states that the solubility of B expressed in mole
fraction is the same in all solvents, and that the solubility depends only on two properties of the
solute B: the heat of fusion of B and the melting point of pure B. Whether A or B is considered
the solvent or solute is immaterial; it is conventional to look upon the substance present in the
larger amount as the solvent. Consequently, we can rewrite eq (17) for substance A:

ln x A =

H A (fusion) 1
1

T o T
R
A

(18)

Equations (17) and (18) are valid for ideal solutions. To check the validity of these equations, let
us examine the solubility of p-dibromobenzene in a number of solvents in which it forms nearly
ideal solutions, as shown in Table 3. The solubility in mole fraction agrees quite well with the
mole fraction calculated with eq (17). Not surprisingly, the agreement is best with bromobenzene
as solvent.
Table 3 Solubility of p-dibromobenzene at 25C [H (fusion) = 20.29 kJ/mol, T = 359.1 K ]
Solvent
CS2
C6H6
C6H5Br

Measured*
g/100g
xA
47.4
0.225

xA calculated with eq (17)

0.2497

45.6

0.217

0.2497

32.5
* Data from Stephen et al., 1963.

0.243

0.2497

Calculation of the Liquids Curve

Equations (17) and (18) as written might be described as giving the solubility ( xA or xB )
B

of a solute at temperature T. Alternatively, we can look at T as the temperature at which the solid
and liquid phases are in equilibrium (eq. (14)). The phase diagram is a plot of this temperature
against composition (mole fraction). Let us rearrange eqs (17) and (18) so that the solid-liquid
equilibrium temperature T is expressed explicitly in terms of composition and two properties of
the solvent-heat of fusion and melting point:

R ln x A

T = o

TA H A (fusion )

1
R ln (1 x A )

T = o

TB H B (fusion )

(19)

(20)

CHEMICALS AND APPARATUS

1. Component A: Naphthalene
2. Component B: Diphenylamine
3. Beaker (600 mL)
4. Test tubes ( 25200 mm)
5. Thermometer (0 - 110C)
6. Clamp and ring stand
7. Aluminum foil

Fig. 2 Some ideals of how to set-up the freezing-point apparatus

PROCEDURES
1. Make two series of runs: A-rich series, beginning with pure A, followed by systems made
by successive additions of B to the previous run beginning with pure A; and B-rich series
similarly prepared. Weight to 0.01 g. Some approximate weights are given in Table 4.
Table 4 Approximate Range of Compositions

Start: 3 g Pure A
Add B (g)
wt.% A
0.00
100
0.33
90
0.42
80
0.54
70
0.71
60
1.00
50

Run
1A
2A
3A
4A
5A
6A

Run
1B
2B
3B
4B
5B
6B

Start: 3 g pure B
Add A (g)
wt.% B
0.00
100
0.33
90
0.42
80
0.54
70
0.71
60
1.00
50

2. Heat the sample tube of mixture in a water bath until it is melted. Then remove the sample tube
from the water bath and measure the temperature periodically (e.g., every minute) until the
system is essentially solid. The relationship between the cooling curves and the phase
diagram is shown in Fig. 4.
3. When a pure substance cools, the temperature falls smoothly until the freezing point is reached;
then the temperature halts, as shown for curve 1 (Fig. 4a), when the solid A begins to
solidify.
Temperature

Liquid
cooling

Liquid
freezing
Solid
cooling
curve1

curve 2

(a) Cooling curves

(b)

Phase diagram

Fig. 4 (a) Cooling curves, and (b) Phase diagram (two solids and one liquid, no solid solutions).

For a one-component system, at constant pressure, the phase rule is

F =CP+1=2P
When two phases are in equilibrium, the system is invariant and the temperature is fixed, that is,
at the melting point. Above and below the melting point, there is only one phase, so F = 1, and
the temperature is no longer fixed; it varies and must be specified to fix the state of the system.
Runs 1A and 1B in Table 4 are of this type.
For a two-component system, at constant pressure, the phase rule is
F=CP+2=3P
When a homogeneous melt cools (curve 2 in Fig. 4a), a temperature is reached at which the
solution is saturated with respect to one of the components, A in this case. At this temperature, A
begins to precipitate out of the solution and the rate of cooling decreases. It decreases because
heat is given up to the system by the exothermic process:
A (solution) A (solid)

H is negative

(21)

Above the two-phase line, there is one phase, so that F = 3 1 = 2 .

Below the two-phase line, there are two phase in equilibrium, so that F = 3 2 = 1 .
However, at the eutectic temperature, the solution is not only saturated with respect to
A, but it is also saturated with respect to B, which now begins to precipitate out of solution
simultaneously with A. Since three phases are in equilibrium, F = 3 3 = 0, and the system is
invariant. The temperature is fixed and the cooling halts at the eutectic temperature.
The cooling curves for all the systems in Table 4 are of this type except those for runs
1A and 1B, which are one-component systems. Measuring the cooling curve for a two-component
system of known composition reveals the eutectic temperature as well as the temperature on the
two-phase curve. The cooling curves of all the two-component systems show a halt at the same
(eutectic) temperature. They also show an inflection point at a higher temperature, which depends
upon the composition.

10

TREATMENT OF RESULTS
1. Graph the cooling curves and phase diagram (the same as Fig. 4). Tabulate the compositions,
observed eutectic temperatures, and two-phase temperatures for the various runs.
2. Construct a phase diagram from your observations. Tabulate and plot ln x versus 1/T for both
A and B.
3. Calculate the heat of fusion.
4. Compare your heats of fusion with the literature values. With the literature values for the heat
of fusion and melting points of pure A and B, construct phase diagram based upon ideal
solution behavior (eqs 19 and 20).
5. Compare your observed phase diagram, eutectic temperature, and composition with the
calculated values and calculated phase diagram.

SAFETY CONSIDERATIONS
Some of the above compounds are known carcinogens and should not be allowed to
contact skin. Others smell bad and it may be advantageous to carry out the measurements in a
hood. Take care not to touch a hot test tube.

REFERENCES
1. J. Gallus, Q. Lin, A. Zumbhl, S.D. Friess, R. Hartmann, and E.C. Meister, Binary Solid
Liquid Phase Diagrams of Selected Organic Compounds, J.Chem. Ed., 78, 961-964, 2001.
2. D.P. Shoemaker, C.W. Garland, and J.W. Nibler, Experiments in Physical Chemistry, 5th
ed., McGraw-Hill, New York, 1994, pp. 195-197, 238-246; and 6th ed., pp. 179-182, 215222.
3. G.P. Matthews, Experimental Physical Chemistry, Clarendon Press, Oxford, 1985, pp. 4648, 52-53.
4. P.P. Blanchette, J. Chem. Ed., 64, 267-269, 1987.

11

Appendix

wt.%
Run
A

A = naphthalene
B = diphenylamine

1A
2A
3A
4A
5A
6A

90

A(l) + B(l)

Freezing point [ oC]

80
70
60

100
90
80
70
60
50

xB
0.00
0.08
0.16
0.25
0.34
0.43

wt.%
Run
B
1B
2B
3B
4B
5B
6B

100
90
80
70
60
50

xB
1.00
0.87
0.75
0.64
0.53
0.43

50
40

A(s) + l

30
20

B(s) + l

A(s) + B(s)

10

Near the
eutectic point

(0.62,
30.95)

eutectic point

0
0

0.2

0.4

0.6

0.8

mole fraction of diphenylamine, xB

Liquid-solid phase diagram for naphthalene-diphenylamine system

Data taken from: http://www.williams.edu/chemistry/epeacock/EPL_CHEM_366/
366_LAB_WEB/

12

90

eutectic
point ( B rich)
1/Tf ln xB

70
60
50
40
30

(0.62,
30.95)

20
10
0
0

0.2

0.4

0.6

0.8

mole fraction of diphenylamine, xB

H B (fus) 1 1
o
R
TB T
H B (fus) 1 H B (fus)

or ln xB =
+
o
R

T RTB
ln xB

Slope X

+ Y-intercept

Slope =

0
0.003
-0.1
ln x B

Freezing point [ C]

80

0.0031

0.0033

-0.2
-0.3
-0.4

y = -2093.9x + 6.4117
R2 = 0.999

-0.5

Slope =

0.0032

H B ( fus)
R

1/T [K-1]

H B (fus)
R

-8.314 J
H B (fus) =
(-2093.9 K ) = +17.4 kJ/mol
mol K

13

eutectic point
90
Freezing point [ oC]

80
70
60
50
40
30

(0.62,
30.95)

20
10
0
0

0.2

0.4

0.6

0.8

mole fraction of diphenylamine, xB

Y-axis

ln xA

H A (fus) 1 1
o X-axis
R
TA T

ln xA

0
0.0028
-0.2
-0.4

0.0029

0.003

0.0031

ln xA

0.0032

0.0033

H A (fus) 1 1
o
R
TA T

-0.6
-0.8

y = -2127.6x + 6.0237
2
R = 0.9989

-1

-8.314 J
H A (fus) =
(-2127.6 K ) = +17.7 kJ/mol
mol K

14

eutectic point
eutectic composition

ln x B

0
0.003
-0.2
-0.4

0.0031

0.0032

y = -1971.6x + 5.9249
2
R = 0.3443

-0.6
-0.8
1/T [K-1]

0.0033

0.0034