Binary Solid—Liquid Diagram

Maricris Monica N. Cabreros Chem 112.1 – 1L

• There are three common phases of matter: solid, liquid and gas. A substance can exist in a particular phase or phases under a given set of conditions like temperature, pressure and composition.

Gibbs Phase Rule
• F=C–P+2
• F is the variance or number of degrees of freedom which can be varied without affecting the number of phases • C as the number of components present • P for the number of phases present

• In this exercise, the pressure was held constant and the system was considered to be condensed. Thus reducing the equation to: • F= C – P + 1

• also considered as pure solids and two component liquid system .Binary solid-liquid system • the two components are miscible with each other at liquid phase but are insoluble in one another as solids.

Thermal analysis • technique used to construct phase diagrams by relating it to the substances’ cooling curves • From this system. a eutectic temperature (TE) can be found at which the phases can co-exist in equilibrium at fixed pressure .

Binary Phase Diagram • A binary phase diagram is a temperature . .composition map which indicates the equilibrium phases present at a given temperature and composition.

.• The eutectic composition (XE) and eutectic temperature (TE) are given by the intersection of the two liquid curves.

.• The curves in graph (b) are plots of temperature against time obtained when liquid solutions of various compositions are allowed to cool.

thus arrest occurs. . component B begins to form together with A where the two continue to solidify at the eutectic temperature until no liquid remains.Arrest Temperature • When the composition of the system reached the eutectic composition.

Objectives • Construct cooling curves of naphthalenediphenylamine system • Construct Binary solid-liquid phase diagram for the naphthalene-diphenylamine system from cooling curves .

Objectives • Determine Breaks and arrest temperature from the phase diagram • Determine eutectic temperature and eutectic composition .

07 3 1.Methodology A amount of diphenylamine and B amount of naphthalene Place into a test-tube Place in a hot-bath to aid dissolution Run No.07 4 2.5 5.07 6 7 8 5.03 5.07 2 1 5.07 5 5 5.675 .01 0.03 0 1. mass of A mass of B 1 0 5.03 5.5 5.

fill with ice Read temperature every 10 seconds until 20o C or arrest curve is obtained * 90 C for runs 1-5.Maintain temperature for specific run * Place test-tube with thermometer into the set-up. 62 C for runs 68a .

use previous set-up and just add the necessary amounts A and B Record data Dispose set-up by reheating. until melted then dispose at appropriate waste bin .Repeat for two trials except for runs 4 and 5 For the next run.

up .Experimental Set .

5 36 53.5 72.5 72.72809 0.25 35 .25 70 68 53 50.5 2 0.81694 72 4 0. 1 2 3 4 5 6 7 8 Xb 1 0.5 36 53.5 70 68 53 55 77. C II average 77.57243 8 0 0.Results and Discussion Run No.150516 70 68 53 46 I Break T.25 35.87003 77.5 35 36 27 28 30.20956 2 0.5 I 79 27 29 30.5 34 Arrest T.5 36 53 35.5 27 27 30. C II average 76 77.

• Pure substance will have no breaks since it is only characteristic to mixtures so the cooling curves of naphthalene (run 1) and diphenylamine (run 6) consist of a single halt at the temperature corresponding to their melting point .


the rate of cooling is observed as slightly decreasing while the solids begin to fully form. • At this time. • At this point.Observation • As the liquid solution cools at fast pace until solid appear. the mixture approaches the eutectic composition. .

• The solid begins to cool leading to another increase in rate of cooling until the mixture has completely solidified and a second rate of cooling occurred. the rest of the solution solidifies which gives a constant temperature.Observation • When this point was reached. .





• From the various set of cooling curves. . a liquidus portion of a phase diagram was obtained by plotting the break temperature as a function of composition.

the euctectic composition was defined from the mutual intersection of the lines . • Then from a fit of the two liquidus curves and a fit of the eutectic temperature.• The halt from the curve then defines the eutectic temperature.

Determination of the eutectic temperature and composition .

.combinations of naphthalene (A) and diphenylamine (B) at temperatures just above their melting points. • Liquid A mixed homogeneously with liquid b • Solid B in heterogeneous equilibrium with solution • Solid A in heterogeneous equilibrium with solution • Solid A mixed with solid B.

Appearance of diphenylamine • occur at lower temperature than it will begin to occur in pure diphenylamine due to F. lowering • represents the maximum solubility of diphenylamine in naphthalene at given temperature .P.

Determination of the eutectic temperature and composition .

• the system is sufficiently diluted so it behaves ideally . that the components exist in their own separate pure phase in solid state.Assumptions • the system does not form solid solution.

Clausius-Clapeyron equation. mole fraction of substance.• the following equation can be used to relate the temperature. and even the enthalpy of fusion. .

• 1) vapor behaves as an ideal gas. and • 3) the enthalphy change accompanying the vaporization is independent of temperature applies . • 2) volume of the condensed phase is negligible in contrast to the volume of the vapor.

Theoretical Eutectic Temperature and Composition for A = diphenylamine .

for B = naphthalene .

654084107×10−4ln(1−𝑋𝐵)+3.• Since both equations are equal to 1/𝑇𝑒.06626192×10−3 .830055186×10−3 = −4.306549229×10−4ln𝑋𝐵+2. −4.

306549229×10−4 / 𝑋𝐵) +( 4.306549229×10−4lnXB + 2.654084107×10−4)/ 1−𝑋𝐵 .830055186×10−3 + 4.654084107×10−4ln(1−XB) − 3.• f(x) = −4.06626192×10−3 • f′(x) = 0 =( −4.

357957449 • XA=1−0.• Using Newton Raphson Method And assuming.3580 or XA=0.5 • Xn+1=x−(f(x) / f′(x)) • XB=0.642042551 . XB = 0.

5782036 K .• Te=305.

570613 -0. % 32 32.96875 Euctectic composition Mole Mole fraction of fraction of naphthalene diphenylami ne 0.64204255 9 1 0.Parameter Eutectic Temperature.36 0.31813 .64 0.35795744 0. 95 2. C Theoretical value Experimen tal value Percent error.

and • the liquid mixture. • solid the eutectic point • solid naphthalene. .

is equal to zero. • F= C – P + 1 • F=2-3+1 • F=0 . 0. so the eutectic point is therefore invariant at a fixed pressure. F.Gibbs Phase Rule • the degrees of freedom.

Importance of Phase Diagram • preparation of countless commercial chemical products in which great effort is taken to ensure that the final product is attractive practically and physically. .


a mixture of miscible liquids but completely immiscible solids illustrates the equilibrium relationship between phases of the mixture.Conclusion • The phase diagram of naphthalene and diphenylamine. .

• The eutectic point is the lowest melting point of the mixture in which three phases can be seen. F=0. or there is invariance at the eutectic point. solid diphenylamine and the liquid mixture. the solid naphthalene. From this. .

P consist of solid A and B . • The last region which is below the E. • Next is composed of solid A and liquid mixture. • The first consist of both liquid A and B. while the third id made of solid B and also liquid mixture. or regions in the diagram.There are four possible combinations of the mixture.

195-197. (6th edition. Experiments in Physical Chemistry. 238246. W. pp. 176. C. 1985. P. McGraw-Hill. pp. New York. New York: Oxford University Press.References • Atkins. • D.193. pp. 2006. Matthews. pp 179-182. 46-48.W. W. Physical Chemistry. P. Oxford.189. . Garland. Experimental Physical Chemistry.) • G. 5thEdition. 215• 222. Nibler. 52-53. 8th ed. and J. Clarendon Press. Shoemaker. 1994. P.

Sign up to vote on this title
UsefulNot useful