Physical Chemistry Laboratory PHASE RULE: References:

Experiment II-2

TERNARY LIQUID SYSTEM

See relevant sections of text "Experiments in Physical Chemistry" O.F. Steinback and C. J. King, American Book Co., N.Y. (1950), pp. 124-129.

Background: Know the following and their interrelations: Phase rule: application to a two phase ternary system. Graphical representation and interpretation of triangular phase diagram. Conjugate phases (solutions). Tie line. Distribution ratio. a

Objectives: Determination of the solubility limits in a ternary system of water and two other liquids, one of which is completely miscible and the other is partly miscible with water. Construction of the solubility curve of the system being studied on triangular graph paper. Determination of the tie lines of several ternary conjugate solutions of the system being studied. Determination of the distribution ratio of the miscible component in the two immiscible phases.

Chemicals: Iso-propyl alcohol, benzene. Other pairs of liquids suitable for the experiment, may be suggested by the instructor. Apparatus: Stoppered Erlenmeyer flasks (125 ml) Constant temperature water bath (25.0 + 0.1oC) Refractometer

Experiment II-2 Procedure: I.

Physical Chemistry Laboratory

Determination of the solubility limits. 1) Prepare eleven mixtures of benzene and anhydrous isopropyl alcohol, of a wide range of composition (see Steinback and King: table 22, p. 127). Deliver the necessary amounts into clean dry stoppered Erlenmeyer flasks from burets. Place the flasks and one containing distilled water in a constant temperature water bath (25.0 + 0.1oC) and allow enough time to establish thermal equilibrium (15 to 20 minutes). Titrate each mixture, carefully and slowly, with distilled water (at 25.0 + 0.1oC) until the first permanent turbidity appears. The composition of this cloud point is on or near the solubility curve. It is important to shake the mixture vigorously after each addition with water. Air bubbles formed by shaking must not be confused with a cloud point. To expedite the titration, withhold about 1-2 mL of the alcohol from the initial mixture; titrate rapidly with distilled water until the cloud point is reached, then add the remaining alcohol and continue titration to the cloud point. Measure the refractive index of each titrated mixture. Save the titrated mixtures.

2)

3)

4)

II.Determination of the tie lines. 1) After completion of step I add excess distilled water, (about 2 ml) delivered by a buret, to at least six or seven of the titrated mixtures. Allow sufficient time, in a constant temperature water bath, for the two conjugate phases to separate into two layers (one hour and preferably longer). NOTE: The volumes of each layer must be large enough to sample for analysis, thus do not use the mixture with the smallest benzene amount. Alternately, Prepare conjugate solutions of a wide

Physical Chemistry Laboratory

Experiment II-2

range OF composition (see Steinback and King, table 23, p. 127). 2) Analyze each layer of each solution by measuring the refractive index. Samples may be removed from the conjugate solutions for refractive index measurements as follows: Upper layer - use a disposable pipet. Don't insert the dropper tip too close to the interface between the two layers. Lower layer - when inserting the pipet through the upper layer squeeze the bulb gently to prevent liquid from entering the dropper. Upon withdrawing likewise squeeze gently so that a small amount of the sample is lost into the upper layer. Transfer the samples into small vials and stopper the vials immediately. Treatment of results: I. Determination of the solubility curve 1) Calculate the composition, weight percent, of each mixture at the cloud point. in

2) Tabulate data including refractive index, volume and weight percent of each component in each mixture. 3) Construct the solubility on a triangular coordinate graph paper. curve

5) Interpret the meaning of the areas bounded by the curve and of various selected points marked clearly on the diagram. This would include points in the two regions, on the solubility curve and at the plait point. Apply the phase rule in your interpretation. II. Refractive Index - Composition Calibration Curve

1. Fasten a sheet of rectangular coordinate graph paper

Experiment II-2

Physical Chemistry Laboratory

to the triangular graph paper with the long side parallel and level with to the triangle base line. 2. Construct a refractive index scale on the y-axis of the rectangular paper. Maximize its range, but use only about half of the length of the vertical axis. 3. Plot the calibration curve points at the intersection of a vertical projection from each cloud point composition and its refractive index. 4. To determine the composition of a given solution, locate its refractive index on the calibration curve, and project downward to the solubility curve. III. The tie lines 1. Use the refractive index calibration curve and the refractive indices of the conjugate solutions to determine the intersection of the tie lines with the solubility curve. Follow the projection procedure in step II (4) and mark the compositions on the solubility curve. 2. Connect the two points of each conjugate pair solutions to obtain the corresponding tie line. of

3. On a separate graph paper plot the weight percent of alcohol in the benzene-rich layer as ordinate vs. the weight percent of alcohol in the water-rich layer as abscissa, for the conjugate solutions. Draw 45o line through the origin, it represents equal distribution. Comment on the distribution ratio in this system.