Bondoc, Kristopher Jayson C.

14 September 2012
CH 45 A: Physical Chemistry 1, Laboratory Instructor: Erwin P. Enriquez, Ph.D.

Experiment 7: Solid-Liquid Equilibrium in Two-Component Systems

Derived Data Tables

naph (g) 20.0152 20.0152 20.0152 20.0152 0 3.0791 7.1233 12.2139

biph (g) 0 3.0126 7.0259 12.0408 20.0056 20.0056 20.0056 20.0056
weight
fraction 1 0.84937 0.648705 0.39796 0 0.133383 0.262572 0.3790841
minutes seconds 1A 2A 3A 4A 1B 2B 3B 4B
0 82 81 81 80 75.2 74 75 75.3
15 81.9 79.9 80.5 70 75 74 74.5 75
30 81.5 79.5 78 65.2 73.5 73 73 73.5
45 81.2 78.5 73 62 72 72 72 72
60 81 77.7 71.2 60 70.5 71 71.1 71
75 81 76.5 70.5 59.5 69.5 70 70 69.5
90 81 76 70 59.5 68.9 68.5 68.5 68.3
105 80.9 75.5 69.4 59.5 68 67.5 67.3 67
120 80.5 75.1 69 60.5 67.5 66.5 66.4 66
135 80.5 75 68.5 60.5 67 65.5 65.5 65
150 80.5 75 68.2 60.5 66.5 64.5 64.5 63.8
165 80.2 75 68 60.5 66 63.5 63.2 63
180 80 75 68 60.2 66 62 62.5 62
195 80 75 67.7 60 66 61.5 61.3 60.9
210 80 75 67.2 59 65.8 60.5 60.7 60.1
225 80 74.9 67 59 65.8 59.5 60 59
240 80 74.9 67 58.9 65.7 59 59 58
255 79.9 74.9 67 58.9 65.7 58 58 57.1
270 79.5 74.9 67 58.5 65 57.2 57.2 56.1
285 79.5 74.9 66.1 58 65 56.5 56.5 55.4
300 79.3 74.9 66 58 64.5 56 55.4 54.8
6 360 78.9 74.2 63.2 54.9 64 55 52.5 51.9
7 420 77 74 60 53 63 55 50 49.1
8 480 75.2 73.9 55 50 62 55 47.5 47
9 540 73.5 73.5 50 46 61 55 45 44.5
10 600 71.3 73 46.3 43.8 60 55 43 42.5
11 660 72.2 43 41.8 54.5 42 38
12 720 71.5 41 41.5 54 42 31.5
13 780 71 39.9 40.5 52 42 30
14 840 70 39 39 49 42 30
15 900 68.5 39 38.2 45 41.9 31.1
16 960 67.7 38.8 38 41.2 40.9 33
17 1020 65.4 38.8 37.5 38 39.8 33.9
18 1080 63.1 38.5 35 36 37.9 34.3
19 1140 60.8 38 33 35 36 35
20 1200 59 38 29 35 35 35
21 1260 56 37 27 35 34 35
22 1320 51 35 25 34 33 35
23 1380 44.4 32 24 32.5 31 35
24 1440 38 28 23 29.5 28.2 34.5
25 1500 35.1 25 22.5 26 25 34
26 1560 32.5 23.5 23.5 34
27 1620 30.8 22.2 33
28 1680 28 22 31
29 1740 26 21.5 29
30 1800 24 21.5 28
31 1860 24 21.5
32 1920 24 21.5
33 1980 24 21.5
34 2040 23.5

LEGEND FOR WT FRACTIONS

room temp 0 = pure biphenyl
water bath at room temp 1 = pure naphthalene
cold water

Cooling Curve for Pure Samples

85

80
Temperature/°C

75

70 1A
1B
65

60
0 50 100 150 200 250 300 350 400 450 500 550 600
Time/s
 Cooling Curves for Naphthalene-Rich
Samples
90
80

Temperature/°C 70
60
2A
50
3A
40
4A
30
20
0 250 500 750 1000 1250 1500 1750 2000
Time/s

Cooling Curves for Biphenyl-Rich Samples

80

70
temperature/°C

60

50 3B

40 4B
2B
30

20
0 250 500 750 1000 1250 1500 1750 2000
Time/s

FP
RUN WT FRC 1/T ln X
onset
1b 0 66 0.015152 0
2b 0.133383 57.1 0.017513 0.156248
3b 0.262572 55 0.018182 0.299919
4b 0.379084 42 0.02381 0.423486
4a 0.398417 62 0.016129 0.666667
3a 0.648972 65.2 0.015337 0.774142
2a 0.849484 73 0.013699 0.88881
1a 1 80 0.0125 1
 Naphthalene-Biphenyl Phase Diagram
90

80
One liquid phase of A and B

Temperature/°C)
70

60

50

40

30
0 0.2 0.4 0.6 0.8 1
Weight Fraction (0=pure biph; 1=pure naph)

The simplest possible two-component phase diagram is one in which no solid solutions or
compounds occur. This diagram can be interpreted as a freezing point curve or as a solubility
curve. In this experiment, the two components used to construct a phase diagram are naphthalene
and biphenyl.

From the data obtained, cooling curves of naphthalene-biphenyl solutions at various weight
fractions were constructed. Using these cooling curves, the phase diagram was constructed by
taking the following data:

1. The first observable inflection point (Freezing Point Onset) for every cooling curve of a
non-pure system (mixture of naphthalene and biphenyl)
2. The experimental freezing point of biphenyl and naphthalene as seen on their cooling
curves.
3. The observed eutectic temperatures for non-pure systems.

In terms of solubility, the solubility of solute A expressed in mole fraction is the same in all
solvents, and that the solubility depends only on two properties of solute A: its heat of fusion and
its melting point. Mathematically,

The relationship between the phase diagram and the cooling curves can be established. For a
pure compound, its cooling curve can provide a point in the phase diagram by taking note of the
freezing point which can be seen in the cooling curve as a flat horizontal line. For other points on
the phase diagram, non-pure sample systems must be taken into account. Their cooling curves
show a particular point wherein the rate of cooling becomes slower, thus, the curve bends at that
particular point.
Another bending of a cooling curve of a non-pure system occurs when it reaches the eutectic
condition. At the eutectic point, there are three distinct phases in equilibrium: liquid solution,
pure solid A, and pure solid B. At constant pressure, the eutectic point is fixed and has no
degrees of freedom remaining. A second break in the cooling curve appears at TE, the
eutectic temperature. The horizontal portion of the cooling curve corresponds to the
solidification of the eutectic mixture. It has the same appearance as the curve for the
solidification of the pure compound. In fact, eutectic mixtures give the appearance of pure
compounds. They have constant freezing points, and the solid eutectic mass is a very fine
grained mixture of the two components. The horizontal portion corresponding to the freezing
of the eutectic is known as the eutectic halt. When the last of the eutectic has solidified, the
cooling curve again begins its downward trend.1

Based on the phase diagram, the eutectic temperature is equal to 42 degrees Celsius and the
eutectic composition is equal to 0.379 (weight fraction) = 12.2139 g naphthalene and
20.0056 g biphenyl.

Given the relationship established in equation 1, the experimental heats of fusion of

naphthalene and biphenyl can be computed by plotting their 1/T vs ln X. These two
quantities are linearly dependent on each other:

1/T vs ln X y = 45.94x - 0.6375

0.5 R² = 0.8498
0.45
0.4 y = -87.735x + 2.0972
R² = 0.9873
0.35
0.3 naphthalene
ln X

0.25
0.2 biphenyl
0.15 Linear (naphthalene)
0.1
Linear (biphenyl)
0.05
0
0.01 0.015 0.02 0.025
1/T

Fro Eq. 1, we can calculate for the enthalpy of fusion:

FP
WT FRC onset 1/T ln X solute (1/To)-(1/T) H fus Average UNC
1b 0 66 0.015152 0 -0.00366953 0
2b 0.133383 57.1 0.017513 0.15624761 -0.00287792 -451.383 0.01

1
LIQUID-SOLID PHASE DIAGRAMS; SIMPLE EUTECTICS.< http://www-
ec.njit.edu/~grow/phasedigram/BiphaseDig.html>. Accessed 14 Sept. 2012.
 3b 0.262572 55 0.018182 0.29991906 -0.00123912 -2012.33 0.02
-
4b 0.379084 42 0.02381 0.42348585 -4.0493E-05 -86949 22353.2 0.02
4a 0.398417 62 0.016129 0.33333295 -0.00167817 -1651.4 0.02
3a 0.648972 65.2 0.015337 0.22585841 -0.00088656 -2118.07 0.03
2a 0.849484 73 0.013699 0.11118968 0.000752237 1228.909 0.05
-
1a 1 80 0.0125 0 0.001950867 0 635.141

Some sources of errors might be due to the fact that naphthalene used is not reagent grade.
And the timing systems is not that accurate since at some parts of the cooling curve, the
cooling rate is so fast that it might be possible to say that some significant curves have been
neglected. This can be improved by using an automated timing machine that simultaneously
plots temperature as a function of time.

It can be concluded that in this experiment, we can investigate the properties of a solid-liquid
equilibrium by using a phase diagram. In fact, phase diagrams in general are very useful. For
example, the analysis of problems involving the casting of alloys requires a complex blend of
fluid mechanics, heat flow, chemical diffusion and solid mechanics. However, the phase
diagram, especially when applied to the character of a material at a given position and time (local
equilibrium), provides the basic constitutive relation regarding the physical state of the alloy.
The information from a phase diagram must be placed upon a framework of mass, momentum
and energy balance equations that describe the kinetics of a given situation.i

Calculations are done using Microsoft Excel.

i
Phase Diagrams and Computanional Thermodynamics.
http://www.metallurgy.nist.gov/phase/papers/applic_sol.html