Solid-Liquid Phase Diagram of Naphthalene-Diphenylamine Two-Component System

Michael Go, Nate Manaloto, Ronald Reyes* *Faculty, Ateneo de Manila University; email: ron_rxn24@yahoo.com

Abstract. The experiment aims to be able to construct a phase diagram of Naphthalene-Diphenylamine two-component system at constant atmospheric pressure for thermal analysis. From the phase diagram, the eutectic composition (XE) and eutectic temperature (TE) are determined and are compared with the literature value. Commercial Naphthalene is used to undergo this test, and see if it is of the same caliber as the standard Naphthalene.
Keywords. Naphthalene-Biphenylamine. Eutectic point. Newtons Law of Cooling. Thermal Arrest. Thermal Break.

Introduction. In investigating the heterogeneous equilibrium between solid and liquid phases of a twocomponent system, a phase diagram is constructed. In constructing phase diagrams, cooling curves forms the basis for thermal analysis. From the phase diagram, the eutectic composition (XE) and eutectic temperature (TE) are determined.

Figure 1. A Phase Diagram for a two component system in which the solids are partially miscible and the liquids are complete miscible.

The binary solid-liquid diagram in Figure 1 shows the stability of different phases as a function of temperature and composition. This example (Figure 1) shows a case where the solid components are partially miscible, +. (s) represents a solid state mixture predominantly composed of substance A, with B present as an impurity, and (s) represents the opposite case where A is an impurity. When a substance is dissolved in a liquid and the freezing point of the liquid is lowered, this is called freezing pint depression, a colligative property that depends on the number of solute particles present in the solvent. The shape of the phase boundaries between the ( + liquid region) + ( + liquid region), the liquidus curves, describes the freezing point depression for this mixture. The equation of the liquidus curves can be derived from the Clausius-Claperyon equation

under the assumption that the solution behaves ideally:

T(XA) = Tf.A. + ln(XA)RTFA2/dHA = TA-((1-XA) + (1-XA)2/2 + ) RTf.A2/dHA

Naphthalene followed by successive additions of Diphenylamine to the previous run; and a Diphenylamine-rich series similarly prepared with the Naphthalene-rich series*. Heat the mixture in water bath until completely melted, and then, remove the water bath and measure the temperature periodically (e.g. every 15 seconds for the first 5 minutes, 30 seconds for the next five minutes, and every minute for the latter parts until the eutectic temperature is reached) until the system is essentially solid. Table 1. Approximate range of composition for the two-component Naphthalene-Diphenylamine mixture Approximate Range of Composition Pure A Naphthalene: 10 g.
Run 1A 2A 3A 4A 5A B (g) 0.0 1.5 2.0 2.5 3.0 Wt. % A 100 87 74 63 51

Tf.A is the freezing point of compound A, and is also shown in Figure 2. dHA is the heat of fusion for compound A and XA is the mole fraction of compound A. An analogous equation can be written for compound B. The two liquidus curves intersect at the eutectic point, C. In the absence of a phase change, the rate of change in temperature follows Newtons Law of cooling. The Newtons Law of cooling predicts that there is an exponential approach to the ambient temperature. A solid is formed because the rate of cooling is changed as part of the heat exchanged with the surroundings that contributes to the phase transition. During the freezing point of a pure substance, when the temperature remains constant, this is called thermal arrest. In a two-component system, as the temperature is lowered, one component begins to freeze while the other component still remains in the liquid state. In this freezing process, the liquids concentration mixture changes as more and more solid forms, and this consequently changes the freezing point. For this reason, the rate of cooling is not constant, but is different from the rate of cooling of the original liquid. This change in the rate of cooling is known as thermal break. When the liquid reaches a certain ratio of the two components, a thermal arrest is observed. This temperature and concentration point is also known as the eutectic point. Experimental. The binary system will be

Pure B Diphenylamine: 10 g.
Run 1B 2B 3B 4B 5B A (g) 0.0 1.5 2.0 2.5 3.0 Wt. % B 100 87 74 63 51

Results.

Figure 2. The constructed phase diagram with the freezing points plotted, temperature (y-axis) and mole fraction of Naphthalene (x-axis). The best fitted curve is used and the eutectic point and temperature were determined. Eutectic composition (XE) = 0.76381045 Eutectic temperature (TE) = 21.8121115 Discussion: In the constructed phase diagram, a few changes were made. The best fitted curve was used in order to get the eutectic point. The experimental value

naphthalene-diphenylamine. Make two series of runs: a Naphthalene-rich series beginning with pure

of the eutectic point is 0.764 mole fraction composition of Naphthalene and 21.81C for the temperature. Comparing it with the values taken by other studies, it was found that the eutectic point is around 0.36-0.38 mole fraction of naphthalene, and the temperature roughly 31C. The high deviation of the results from the previous one can be seen in the experimental procedure, and the result itself. As can be seen in the results, the points were not successive and not complete. As such, there was a huge break and empty space between the 0.3 and 0.8 mole fraction of Naphthalene interval. As such, the eutectic point can only be roughly estimated by extending the best fitted curves. Having more points can lead to a more visualize-able and more accurate results. The recommendation for the experiment is that it can add more solutes for each runs that can extend the points further nearer the eutectic point, or if not change the five runs where the solute are added 1.5 g. each run instead of adding in a 0.5g increment. The major source of error in the experiment is temperature reading. Since the temperature is read not automatically by a machine, but manually by the experimenter. Furthermore, when the system is not stirred, the whole solution is not in equilibrium which leads to a deviation in temperature reading that eventually leads to supercooling of the system. Although this will eventually be eliminated, however, this could have been prevented if the system was stirred consistently. The recommendation is that an automatic stirrer can be used rather than a manual one. Acknowledgement.

We would like to acknowledge the Chemistry Department of the Ateneo de Manila University for supporting our project and providing us the equipments necessary for the completion of the project. References. University of Colorado. Binary Solid-Liquid Phase Diagram. BSL.pdf> Williams Diagram. College. Binary on Solid-Liquid October 6, Phase 2010. Accessed on October 6, 2010. <http://www.colorado.edu/Chemistry/chem4581_91/

Accessed

<http://www.williams.edu/chemistry/epeacock/EPL_ CHEM_366/366_LAB_WEB/Expt_5_BinaryPhases.p df>

Figure 1. A Phase Diagram for a two component system in which the solids are partially miscible and the liquids are complete miscible.

Figure 2. The constructed phase diagram with the freezing points plotted, temperature (y-axis) and mole fraction of Naphthalene (x-axis). The best fitted curve is used and the eutectic point and temperature were determined.

Figure 3. A run of Diphenylamine with 3 grams of Naphthalene as impurity, the graph illustrates the thermal break and the thermal arrest.