3.

091 Introduction to Solid-State Chemistry - Fall 2012 Problem Set 11 Problem set quiz will not be scheduled for this homework set Problem 1 Silver sulfate dissolves in water according to the following reaction: Ag2SO4 2 Ag+ (aq) + SO42-(aq) for which the value of the solubility product, Ksp is 1.4 x 10-5. (a) Calculate the solubility of Ag2SO4 in water. Express your answer in moles Ag 2SO4/liter solution. (b) Calculate the solubility of Ag2SO4 in 1.00 M Na2SO4(aq). Express your answer in moles Ag2SO4/liter solution. Assume that Na2SO4(aq) is fully dissociated. Problem 2 (a) The solubility of bismuth iodide (BiI3) in water is 3.091 x 10-3 M. Calculate the value of the solubility product. The dissolution products are Bi3+(aq) and I- (aq). (b) Do you expect the solubility of BiI3 in 0.1 M NaCl(aq) to be equal to, greater than, or less than that of BiI3 in water? Explain. Problem 3 Silver arsenate (Ag3AsO4) dissolves in water according to Ag3AsO4 = 3 Ag+(aq) + AsO43-(aq) Ksp = 1.1 x 10-22 at 25C

Calculate the solubility of silver arsenate in 0.001 1 M AgNO3. Express your answer in moles of Ag3AsO4 per liter of solution. Problem 4 (a) Magnesium phosphate dissolves in water according to Mg3(PO4)2 = 3 Mg2+(aq) + 2 PO43-(aq) Ksp = 1.11 x 10-25 at 25C

Calculate the solubility of magnesium phosphate (Mg3(PO4)2) in pure water. Express your answer in moles Mg3(PO4)2 per liter of solution (M).

(b)

Calculate the solubility of magnesium phosphate (Mg3(PO4)2) in a 4.44 x 10-3 M magnesium carbonate (MgCO3) solution. Express your answer in moles Mg 3(PO4)2 per liter of solution (M).

Problem 5 (a) Lead chloride dissolves in water according to PbCl2(s) = Pb2+ (aq) + 2 Cl- (aq) The solubility in pure water has been measured to be 4.44 g L -1. Calculate the solubility product of lead chloride in pure water. (b) Calculate the solubility of lead chloride in a 3.091 x 10-4 M potassium chloride (KCl) solution. Express your answer in moles PbCl2 per liter of solution (M). Regardless of what answer you obtained in part (a), in this calculation use the value of 3.091 x 10-5 for Ksp of lead chloride. Problem 6 The following information is available from cooling experiments for the binary system Cu-Ni: Melt composition (atomic % Ni) 3 20 40 60 80 Composition of solid first formed on cooling (atomic % Ni) 10 37 57 73 87

T(C) 1100 1180 1260 1340 1410

(a)

Construct the T/composition diagram from these data and information provided in the Periodic Table.

(b)

For the following temperatures and compositions, what are the phases present and what are their respective compositions?

T(C) 1120 1200 1300

Composition (atomic % Ni) 15 55 60

Phase

Composition (atomic % Ni)

Problem 7 Given the triple point of copper (Cu) and data provided in the Periodic Table, sketch a reasonable P/T equilibrium phase diagram for copper. Triple point: TT = 1080C PT = 6.1 x 10-6 atm Problem 8 Draw schematic phase diagrams for binary systems with (a) complete liquid and solid solubility, (b) complete liquid but zero solid solubility, and (c) complete liquid and limited solid solubility. (In your sketches label phase fields and give characteristic temperatures.) Problem 9

The triple point of H2O is at 0.006 atm and 0.01C; knowing in addition the boiling and freezing point temperatures of H2O at 1 atm pressure: (a) (b) Draw a schematic phase diagram for H2O. Give the reasoning behind this statement: The diagram permits the conclusion that ice will most likely float on water! Problem 10 Given the triple point of copper (Cu) and data provided in the Period Table, sketch a reasonable P/T equilibrium phase diagram for Cu. (Triple point, TT = 1080C; PT = 6.1 x 10-6 atm) Problem 11 Given the schematic A-B binary phase diagram below:

(a) (b)

Label all phase regions on the schematic phase diagram. Draw a schematic cooling curve for a binary melt of 70 at.% B + 30 at.% A. Label characteristics temperatures and indicate the phases present in the various temperature regions.

(c)

What are the phases present and their compositions if the melt considered in (b) is cooled to T = 600C?

(d)

What fraction of the melt considered in (b) is solidified at the temperature of 550C?

Problem 12 a) Shown below is the Mg-Si phase diagram. Note that a magnified version of the Mg rich portion of the diagram is shown on the right. Label each region of the diagram (including the magnified portion).

b) Why do Mg and Si exhibit limited solubility in one another? c) Calculate the relative amount of each phase at room temperature in a sample with overall composition 0.80 mole fraction Si.

Problem 13 Naphthalene melts at 80 C and benzene melts at 5 C. The two materials form a completely miscible liquid at high temperature but have very little miscibility in the solid state. The following cooling curves are observed for various liquid compositions of naphthalene and benzene (X stands for mole fraction benzene). Draw the simplest phase diagram in the space provided that is consistent with the cooling curve data. Label each section of each cooling curve to indicate what phases are present.

Problem 14 The solubility of benzalphthalide in various solvents has been shown to be a function of their solubility parameter. This relationship is shown below.
40 35 30 solubility of benzalphthalide in various solvents

benzalphthalide

solubility (%)

25 20 15 10 5 0 5 7 9 11 13 15 solubility parameter of solvent

Solvents( from left to right): dimethicone, octane, MIBK, ethyl acetate, acetone, benzaldehyde, acetonitrile, benzyl alcohol, propylene carbonate

a) Hypothesize why the solubility goes through a maximum. b) Estimate what the solubility parameter of benzalphthalide