Lab report on solid liquid equilibrium in a binary system

Background Introduction
Cooling curves can be used to create a phase diagram. In this experiment, a phase diagram was
constructed from a binary system's cooling angles containing naphthalene and biphenyl. The
cooling curves were created from pure naphthalene, pure biphenyl, and mixtures of the pure
substances from about 20% to 80% composition by mole. The samples at room temperature
were solids. The samples were heated until the model had changed entirely to a liquid phase.
The pieces were allowed to cool back to its solid form, and the temperature of the system was
measured and plotted against time. This plot is known as the cooling curve. The computer
software used was a data logger, and the weather was measured with a thermocouple.

Figure 1 - The T-X diagram for the binary biphenyl naphthalene. The y-axis represents the
temperature, and the x-axis is for the percent mole composition of naphthalene in the liquid
phase of the solution. The blue curve is from the plot of each solution's first fusion temperatures,
and the red points are from the points plotted of the second fusion points. The green like at the
bottom represents the Eutectic temperature from the average of the dual fusion points.

70
Solid-Liquid Phase Diagram of Naphthalene Biphenyl Mixture

65

60

55
Temperature oC

50 First Fusion Temperature

Second Fusion Temperature
Eutectic Temperature
45

40

35

30
0 10 20 30 40 50 60 70 80 90 100
Solution Percent Mole Compsotion of Napthalene

Figure 2- The plot on the left is the T-X phase diagram, and the story contains three different
cooling curves. On the cooling curve plot, I represents the cooling of a pure substance; II
represents the cooling of a mixture containing component A and B of mole fraction X 1 of
component B. III Represents a cooling curve of where the mole fraction of B in the liquid phase
is equivalent to that of the eutectic composition. The cooling curve's arrest and breakpoints were
plotted to create the t-x phase diagram represented by the dashed line crossing between the two
plots. TA is the freezing point of pure A, T1 is the temperature of the first fusion event of the
solution shown in II. T2, T3...Ti shows the fusion temperature point or solubility of component B
when the solution has a concentration of X2 X3, ...Xi of B. On the left plot, where the function on
the left intersects with the right process, the eutectic composition and temperature can be
predicted, marked by III and TE, respectively.

[8]

Gibbs's phase rule determined how the experiment was set up to obtain useful information and
why it can be plotted. The phase rule gives the number of parameters, intensive variables that can
be varied independently while the number of phases in equilibrium is preserved. The four
intensive variables that can describe the experiment's system are temperature, pressure, and each
component's mole fractions in the liquid mixture.

Figure 3- The model is the phase diagram with the corresponding degrees of freedom. The
temperature is plotted against the fusion temperatures against the mole fraction of component A.
The mole fraction of an increase from the 0 on the left side of the graph to pure A on the right
side. The region where the degrees of freedom are zero is the eutectic temperature and
composition. On the left side of this point, the curve describes the equilibrium containing the
mixture of components A and B in a homogenous liquid phase and substantial component B. On
the right side of the eutectic point; the curve describes the equilibrium containing the mixture of
components A and B in a homogenous liquid phase and substantial component A.

[4]

At constant pressure, the ideal temperature of fusion for each composition can be predicted by
equation 2.

Equation 1 The change in Gibb's free energy

dG=dH-TdS

Where dG is the change in Gibbs free energy, DH is the enthalpy changes, T is the temperature,
and dS is the change in the system's entropy. If the change in free energy is negative, a process
will be spontaneous, and if the change in free energy is zero, the system is at equilibrium.

At the fusion temperature of a component, the change in free energy, called the molar Gibb's
energy of fusion, is equivalent to potential chemical differences between the solid and liquid
phases.

Equation 2- Describes the potential chemical relationship at temperature T and pressure P at

equilibrium between the solid and liquid phases of a component.
Where uA (s) is the chemical potential, the solid of component A, u A (l) is the liquid's chemical
potential.

A system containing two different components, A and B, in an ideal homogeneous solution

chemical potential of solid A in the mixture is said to be the same as pure solid A at the same
temperature and pressure.

Equation 3 Describes the relationship between the chemical potential of pure solid A and solid
A in the mixture.

The chemical potential of a liquid, an ideal solution at equilibrium, can be described with an
equation derived from Raoult's law in terms of its activity.

Observations
When heated, the solids melted into a clear liquid. When the naphthalene and biphenyl solids
were mixed and were heated together, they melted entirely into a liquid. As the solutions cooled,
the solid precipitate formed, and the nucleation started at the bottom of the glass and the
meniscus. The solutions cooled to room temperature, and eventually, all of the liquid turned
onto a white solid.

Calculation and Results

Calculation 1 Experimental results of cooling curves of a naphthalene-biphenyl binary

system2

Mole Fraction Percent 1st Fusion Temperature 2nd Fusion Temperature

o o
Naphthalene C C

0% 59.1 none

23.26% 46.5 35.1

44.50% 33.7 33.1

64.21% 46.2 34.8

82.68% 58.9 34.2

 100% 67.8 none

Calculation 2- This demonstrates how the result of the bottom two rows right column of table
3. Were calculated. The left curve is a second-degree polynomial fit of the solutions containing
pure biphenyl with a percent mole fraction of 0% naphthalene to the solution containing 44.50%
naphthalene. The curve on the right, a second-degree polynomial fit, answers a percent mole
fraction of 64.21% naphthalene to the solution containing 100% pure naphthalene. The eutectic
composition and temperature values were taken to be the point of intersection of the two-second
degree polynomial fits.

80
Polynomial Fits of T-X Phase Diagram
70

60
TemperatureoC

50

40

30 y = -13.721x2 - 50.977x + 59.1 y = -48.579x2 + 140.12x - 23.742

R² = 1 R² = 1
20

10

0
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Percent Moles Napthalene

Calculation 3 - Percent error

Percent error= Absolute Value (Experimental Value-Ideal Value)/Ideal value

The percent error of pure biphenyl= |(59.1-69.8|/69.8= 15.33%

Discussion

To determine the quality of this experiment, it will be compared to Lee and Warner's paper
results. Their main conclusion was that the naphthalene biphenyl system behaved ideally. In this
experiment, the first indication that the naphthalene biphenyl system was ideal is that the liquid
mixture was a perfect solution. It was observed when a variety at any biphenyl and naphthalene
composition was heated until all the solid melted into a liquid. There was only one phase
followed, and the solution was clear. This is an indication of a homogeneous mixture, which is a
property of an ideal combination. Even as the solution cooled to the eutectic point and
precipitated formed, the answer appeared to be homogenous, and no additional phases were
observed.

Figure 10 shows the t-x phase diagram of the ideal results calculated from Raoult's law's
derivation. The black circles indicate the calculated outstanding points. Lee and Warner's results
closely follow the superior calculated values. The experimental data has a similarly shaped
curve, like the one created from the perfect deals. If the mixture did not follow Raoult's law,
changes in the arc's shape and the turn would be more difficult to predict. Solutions that do not
follow Raoult's law may have a may change from a concave down curve to a concave up angle,
or the curvature of the curve could increase. The difference is the experimental values, and the
ideal amounts most likely result from both determinate and indeterminate errors.

Conclusion
The experiment was successful in terms of precision, and the results showed trends that were
seen in literature, but the results lacked a high degree of accuracy. The cooling curves and phase
diagram of the binary system of naphthalene and biphenyl at substantial liquid equilibrium had
curves had similar shapes as the literature; the cooling curves displayed the correct amount of
fusion events. The results contained a moderate amount of precision, which was evident by the
fusion temperatures, which were consistently lower than the ideal values. The results showed
evidence of a source of systematic error that interfered with the experiment's accuracy.

There are possible expiations for the source of the error. The thermocouple measuring device
may not have been appropriately calibrated. The low temperature of the fusion events was
consistently low, but not necessarily by the same degree, which means there were other possible
error sources. Any impurities or chemical alterations to the reagents would skew the results.
Another possibility comes from the method used. The solids were heated to liquids, then capped
and sealed by the thermocouple. The experiment assumed that the pressure was at standard
pressure and that the pressure was constant. A decrease in temperature in the test tube's closed
system could have resulted in force, affecting the climate of the fusion events. The high
temperatures used to melt the liquid could also have caused some gas to dissolve in the liquid
solution and cause additional depression.

In the future, this experiment could be improved by taking measures to eliminate determinate
errors. The temperature measuring device could be calibrated before the experiment; new
reagents could be used, steps could be taken to ensure constant pressure, and controlling the
samples' gas atmosphere could ensure that any gasses are not dissolved in the liquids.

References

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2. Gallus, Jürgen, Qiong Lin, Andreas Zumbühl, Sebastian D. Friess, Rudolf Hartmann, and
Erich C. Meister. "Binary Solid-Liquid Phase Diagrams of Selected Organic Compounds.
A Complete Listing of 15 Binary Phase Diagrams." Journal of Chemical Education 78.7
(2001): 961. Print.
3. Halpern, Arthur M., and George Clyde. McBane. Experimental Physical Chemistry: A
Laboratory Textbook. New York: W.H. Freeman, 2006. Print.
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<http://www.colby.edu/chemistry/PChem/notes/GibbsPhaseRule.pdf>.
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Ideal Binary and Ternary Systems." CONTRIBUTIOFRNO M THE CHEMISTRLYA
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