The'Binary Liquid-Solid Phase Diagram of
klaphthalene-pdichlorobenzene
A Physical Chemistry Laboratory Experiment
Paul P. Blanchette
St. Mary's College of Maryland, St. Mary's City, MD 20686
The liquid-solid phase diagram of the binary system, manner using a modified Beckmann apparatus (1,8).
naphthalene-p-dichlorobenzene,is obtained quite easily by A total of 11samples of varying composition is sufficient
thermal analysis methods with minimum laboratory equip- to define the shape of the phase diagram. Convenient mole
ment. The advantages of this system over other suggested fractions for naphthalene are 1.00,0.95,0.90,0.75,0.55, and
systems (e.g., naphthalene-dipheuylamine (I), tin-lead (2), 0.45, while convenient mole fractions for p-dichlorobenzene,
and phenol-p-toluidine (3))include the use of inexpensive, include 1.00, 0.95, 0.90, 0.80, and 0.70. By performing the
stable, and relatively safe (4) chemicals and a temperature first determination on 5.00 g of pure solvent, for example,
range accessible with a mercury thermometer. naphthalene, other naphthalene-rich solutions can be pre-
In addition to obtaining the liquid-solid phase diagram, pared by successive additions of previously determined and
perhaps the real underlying beauty of this experiment is that accurately weighed portions of p-dichlorobenzene to the
i t ~rovidesa whole treasurv of thermodvnamic information. preceding sample. Paradichlorobenzene-rich solutions can
Specifically, the student can ohtain reasonable estimates of be prepared in an analogous fashion.
the heat or fusion (and differential hear of solution).
. . entrow
-. S a m ~ l ethat
s are too dilute do not contain enoueh solution
of fusion, freezing-point-depression constant, and solvent of euteitic composition in order to observe a euyectic halt.
activity coefficients for each component. The data may be However, intermediate solutions from Xnanh= 0.2 ~ 0 . 7 are 5
exploited further to yield estimations of purity and the suitable for such analysis and should be-&led long enough
"true" melting point (5). until a eutectic halt appears.
Theory Results and Discussion
The curve NE in the figure may be thought of as the The experimental phase diagram of the naphthalenep-
freezing point depression curve of naphthalene due to added dichlorobenzene system is shown in the figure. The points
p-dichlorobenzene, and i t may also be thought of as the shown are a pool of break and arrest temperatures extracted
solubility of naphthalene inp-dichlorobenzene as a function from cooling curves for various solution compositions. These
of temperature. Likewise, curve P E may be interpreted as data are a composite obtained by four experimenters. The
the freezing point depression of p-dichlorobenzene due to general appearance is that of a simple eutectic system with
added na~hthaleneas well as the solubilitv . of .o-dichloro- the eutectic point occurring a t 29.5 "C and XPDCB= 0.64.
benzene in naphthalene as a function of temperarure. Deri- Enthalpies and entropies of fusion, and freezing-point-
vation of a suitable eauation to descrihe curves such as NE depression constants for naphthalene and p-dichloroben-
or P E can be achievedby either approach (6, 7). zene are presented in Table 1.By method I the enthalpies of
When pure solid A is in equilibrium with a liquid solution fusion were calculated from the limiting slopes of curves NE
containing component A, the molar Gibbs free energy of A is and P E (I). Method I1 values were calculated with eq 2 using
the same in each phase. Thus, points extracted from a "best fit" curve to the composite
data set in the range X.,iWt = 1.0 to 0.9, where the solvent
GA(s)= GA(soln)= GA(l)+ RTlnrAXA (1) activity coefficient was assigned a value of unity.
where rA(s) and rA(l) are the molar Gibhs free energies of Methods I and I1 seem to yield reasonably accurate values
the pure solid and pure liquid, respectively, XA is the mote for a t f , although they tend to be slightly high. The rela-
fraction of component A in solution, and 7 A is the solvent tively large values of AfTfff calculated by Method I are re-
mole-fraction-scale activity coefficient.
Application of the Gibbs-Helmholtz equation to eq 1,
followed by integration and neglect of the temperature de-
pendence of the enthalpy of fusion yields:
R In YAXA - 1/T)
= A&us(Tm)(l/Tm (2)
where A~TE~(T,) is the heat of fusion of component A a t its
normal melting point, T,. Equation 2 can be used to obtain
the heat of fusion and activity coefficients for each compo-
nent.
The mold freezing-point-depressionconstant, k t for com-
ponent A can he calculated from
where MA is the molecular weight of A. I I
Experimental 0.0 0.5 1.0
M O L E FRACTION P D C B
Freezing points and eutectic halts are extracted from cool-
ing curves (temperature versus time) obtained in the usual Experimental phase diagram d naphthalene-~lchloroben~ene(PDCB)
Volume 64 Number 3 March 1967 267
Table 1. Calculated Values ol Thermodynamic Properties
A% (kJ/mai) kd°Clm)
Component Method I* Method ilb LitC Experimentala e it* A% (Jlmoi K)
Naphthalene 20.3 i 1.5 *
20.3 0.9 18.8 6.56 i 0.45 6.98 57.4 5 4.2
pDichiorobenrene 18.8 5 1.5 18.7 1 0 . 9 17.9 6.96 i 0.55 7.11 57.3 5 4.1
"From llmitlng slopes of cweo NE and PE.
'Fmm eq 2 at & >
, 0.9 a~, , ? =1
Ref 9.
*From eq 3.
vef ra.
sponsible for making the calculated A&, a little high and Table 2. Solvent Mole-Fraction-Scale Actlvlty Coefflclentsa
the calculated k f values a little low. The close agreement
between the entropies of fusion for the two components is Naphthalene pDichiombenzene
expected due to similarities in intermolecular interactions. Mole Fractlon Activity Coeff. Mole Fraction Activity Caeff.
Table 2 shows solvent mole-fraction-scale activity coeffi-
1.00 1.00 1.00 1.00
cients at selected compositions calculated with ea 2. Both 0.90 0.998 0.90 0.998
components, as solvents, seem to exhibit reasonably ideal 0.80 0.981 0.80 0.981
behavior at mole fractions above 0.9 hut tend to become less 0.70 0.948 0.70 0.946
ideal at lower concentrations. 0.60 0.914
0.50 0.874
Concluslon 0.40 0.838
The naphthalene-p-dichlorobenzene system lends itself
quite easily to thermal analysis methods and provides the
student with a wide variety of useful thermodynamic infor-
mation. 2. Saiebew,H. W.:sf al.Phydca1 ChsmialryLoborofory; Maanillan: New York, 1919:pp
392394.
Acknowledgment 3. Daniels, F.;et al. E~perimenfolPhysical Chemiafry; Mecraw-Hill: New York, 1962;
pp 116-121.
The author wishes to extend his sincerest thanks to his 4. Brotheriek, L., Ed. Hazard8 in the ChemieolLabomtory.The Royal Sodetyof Chem-
students, J. Bergmeister, C. Cline, W. Leonard. and S. Rand. istry: Landon. 1981.
5. Meyor, E.F.: Meyer, J. A. J. Chem. Edue. 1980,57,831.
for testing thisexperiment and providing the author with 6. Lewis, G. N.;Randall, M.: Pifper, K.S.; Brewer, L. Thermodywmica: MeGrsw-Hill:
suitable data. NewYork, 1961: pp 227.230,
7. k i n e . I. N. Physical Chemirfry; McCraw-Hill: New York, 1989: pp 309207.
Literature Clted 8. Skau, E. L.; Arthur, J. C., Jr.; Wickeharn. H. In Technique 01Orgonic Chemiacry:
Weiasbqer, Ed.: Interscience: New York. 1959: Vol. 1,Part 1. Chapter 3.
1. Sh-maker, D.P.: ef. al. Experiment. in Physic01 Chemistry; McCrsw-Hill: New 9. Hondbook olChomirtry ondPhyricr, 64th ed.: CRC Press: Boca Raton. FL.1983.
York, 1981;pp 216223. lo. Castellan,C. W.Physicol Chemistry; Addison-Wesley: Reading, MA,1967;p 258.
268 Journal of Chemical Education
