Name: Test 3

150 points Chemistry 261

Dr. Jay H. Baltisberger May 6-8, 1998

Choose five of the following seven Mole Break First Second

problems for 30 points each: fraction B (˚C) halt (˚C) halt (˚C)
1. The table to the right gives the break 0.00 1100
and halt temperatures found in the 0.10 1060 700
cooling curves of two metals A and B. 0.20 1000 700
Construct a phase diagram (using 0.30 940 700 400
graph paper or other accurate means 0.40 850 700 400
of plotting) consistent with the data of 0.50 750 700 400
these curves. Label the regions of the 0.60 670 400
diagram, stating what phases and 0.70 550 400
substances are present. Give the 0.80 400
probable formulae of any compounds 0.90 450 400
that form. 1.00 500
SEE ATTACHED SHEETS

2. Draw the phase diagram (using graph paper or other accurate means of plotting) for the Mg/Cu
system given that Mg melts at 648 ˚C; Cu melts at 1080˚C; intermetallic compounds MgCu2
and Mg 2 Cu melt at 800˚C and 580˚C respectively. Eutectics of 10, 33 and 65 mass percent Mg
composition melt at 690˚C, 560˚C and 380˚C respectively. A sample of Mg/Cu allow
containing 25 mass percent Mg is prepared in a crucible heated to 800˚C in an inert
atmosphere. Describe what will be observed if the melt is cooled slowly to room temperature.
Specify composition and relative abundances of each phase at each point in time and sketch the
cooling curve.
SEE ATTACHED SHEETS

3. It is found that the boiling point of a binary solution of A and B with mole fraction A, xA =
0.6589, is 88˚C. At this temperature the vapour pressures of pure A and B are 957 and 379.5
torr, respectively. Is this solution ideal? What is the initial (before solution has boiled away)
composition of the vapour above this solution.
For ideal solution, V.P. = PA* xA + P B* xB = (957 torr) (0.6589) + (379.5 torr) (0.3411)
= 760.0 torr. This is the V.P. at the normal boiling point, therefore the solution must be ideal
(definition of normal boiling point is temperature where vapor pressure is 760 torr). This
vapor will have a composition of xA = (957 torr) (0.6589) / [ (957 torr) (0.6589) + (379.5 torr)
(0.3411) ] = 0.8297, indicating the vapor is rich in A as expected.

4. The vapour pressure of a 500.0 g sample of benzene was 400 torr at 60.6˚C, but it fell to 386
torr when 19.0 g of an unknown involatile organic compound was dissolved. Calculate the
molar mass of this compound.
Using Raoult’s law, PA = 386 torr = PA* x A = (400 torr) xA. Thus xA = 0.965, implying
that x B = 0.035 = ( 19.0 g / MWB ) / [ ( 19.0 g / MWB ) + ( 500.0 g / 78.1128 g mol–1 ) ]. We
may solve this for MWB = 81.839 g mol–1 .

5. At 25˚C and 1 atm, a 0.5000 mol/kg solution of NaCl in water has partial molar volumes of
18.63 cm3 /mol and 18.062 cm3 /mol for the NaCl and water respectively. Find the volume at
25˚C and 1 atm of a solution prepared by dissolving 0.2500 mol of NaCl in 0.5000 kg of water.
 Using formula for partial molar volumes V = VA,m nA + VB,m nB = (18.63 cm3 mol–1) (
0.2500 mol) + (18.062 cm3 mol–1) (500 g / 18.015 g mol–1) = 505.96 cm3 . The mass of this
solution is (0.2500 mol) (58.443 g mol–1) + 500.0 g = 514.61 g, giving a density of 0.983 g cm 3 .
Note that the water actually loses density as the sodium and chloride ions break up the
hydrogen bonding network.

6. Would a liquid mixture of two optical isomers of CHFClBr be an ideal solution? Explain.
The condition for ideal solutions is for the two molecules to be so similar in size, shape
and molecular interactions that mixing A with B will give A-A interactions which are nearly
identical to A-B and B-B interactions. Normally this is not the case, but for systems like
Benzene-Toluene, the interactions are similar enough to call the solution nearly ideal. In the
case of optical isomers, the structures are merely mirror images of one another, thereby having
identical interactions, size and shape. The only way to separate these molecules is using some
sort of chiral separation scheme, since the interactions are so similar. Given this, I would
define this mixture as nearly perfectly ideal.

7. In which solution would water have a lower activity (A) 0.0300 m NaCl, (B) 0.0200 m MgCl 2 ,
or (C) 0.0300 m MgO (assuming all are fully dissolved and none undergo ion pairing).
You can use the Davies equation to calculate the activity coefficients for each of these
solutions, or you can note that in all cases, the total number of ions in solution is identical.
Given that the activity of the solvent (water) is basically related to the vapor pressure of the
water, you can ask, which solution will bind water most tightly , preventing the molecules from
escaping the solution at the liquid/gas interface? Certainly the answer is the ions with the
highest charge (MgO) which will bind very strongly to the exiting water molecules, dragging
down the net activity of both the solute and the solvent. Thus answer (C) is the correct choice.