3.

091 Fall Term 2010

Test #3
Monday, November 22, 2010 11:05 a.m. 11:55 a.m.

Name: Recitation Instructor:

A complete test consists of 6 questions. Write your answers on these pages. State your assumptions and show calculations that support your conclusions. RESOURCES PERMITTED: PERIODIC TABLE OF THE ELEMENTS, TABLE OF CONSTANTS, AN AID SHEET (ONE PAGE 8" 11"), AND A CALCULATOR. NO BOOKS OR OTHER NOTES ALLOWED. USE OF WIRELESS COMMUNICATIONS DEVICES STRICTLY FORBIDDEN.

#1 #2 #3 #4 #5 #6

22% 23% 10% 19% 14% 12%

TOTAL

100%

3.091 Fall Term 2010 Test #3

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Problem #1 (22%)
The dominant defect in rutile (TiO2) is the Schottky disorder. (a) Write the reaction that represents the formation of a Schottky defect in TiO2.

null = VTi + 2 VO
(4%) (b) Calculate the fraction of vacant oxygen sites in a crystal of TiO2 at a temperature of 444 K. The enthalpy of Schottky defect formation, HS, has a value of 2.22 eV / defect, and the entropic prefactor, A, has a value of 1.11.

(8%)

(c) In a polycrystalline specimen of TiO2 how does the concentration of oxide vacancies in the bulk material (interior of a grain) compare to the concentration of oxide vacancies at the grain boundary? Explain. The interior of the grain is a more densely packed environment than the grain boundary so we expect that the activation energy for vacancies is much higher in the interior than at the grain boundary. Accordingly, we expect that the concentration of oxide vacancies is lower in the bulk material than at the grain boundary. (5%) (d) In a failed attempt to increase the population of oxide vacancies in TiO2 your lab partner suggests doping with niobium oxide (Nb2O5). Write the reaction showing that the incorporation of Nb2O5 into the TiO2 crystal creates titanium vacancies, not oxide vacancies. Your lab partner didnt study. (5%)

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Problem #2 (23%)
(a) The water dissociation equilibrium constant, Kw, expresses the relationship between hydronium and hydroxyl concentrations by the expression Kw = [H3O+][OH] Owing to the presence of dissolved salts the value of pKw for seawater is 13.776 (not 14.00 as it is for pure water), where pKw is defined as log10Kw. Calculate the concentration of hydronium ions in seawater at a pH of 3.091. Express your answer in moles H3O+ per liter of solution (M). (5%)

(b) Would seawater at a pH value of 7.00 be classified acidic, alkaline, or neutral? Explain. (6%) neutrality means [H3O+] = [OH] which occurs at pH = pKw / 2 = 6.89 since 7.00 > 6.89, seawater at this pH is alkaline

(c) Boric acid, B(OH)3, reacts with water according to B(OH)3(aq) + 2 H2O() H3O+(aq) + B(OH)4 (aq). (i) Identify the conjugate acid-base pairs in the above reaction. (4%) (ii) Can B(OH)4 act as a Brnsted-Lowry base? Explain. No. It is not a proton acceptor. (4%)

(iii) Can B(OH)4 act as a Lewis base? Explain. Yes. It is an electron-pair donor. (4%)

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Problem #3 (10%)
Silver arsenate (Ag3AsO4) dissolves in water according to Ag3AsO4 = 3 Ag+(aq) + AsO43(aq) Silver nitrate (AgNO3) dissolves in water according to AgNO3 = Ag+(aq) + NO3(aq) Ksp = 2.3 102 at 25C Calculate the solubility of Ag3AsO4 in 0.0003091 M AgNO3. Express your answer in moles of Ag3AsO4 per liter of solution. Ksp = 4.4 1022 at 25C

Problem #4 (19%)
(a) The formation of molecular iodine proceeds according to the following reaction I + I I2 conducted in carbon tetrachloride (CCl4) which is acting as a solvent. The rate of consumption of I is observed to vary with the square of the concentration of I. With an initial I concentration, co, of 3.091 102 mol L1 the time to reach co/2 is 77 s. How long does it take for the concentration of I to reach co/4? (10%)

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Problem #4 (continued)
(b) On the plot below, sketch the change in concentration of I with time for the following three situations: as described in part (a); at a temperature lower than that in part (a); at the same temperature as part (a) but in the presence of a catalyst (assume that the reaction pathway remains unchanged from what it is in the absence of a catalyst). In all three situations assume that the initial concentration of I is the same, co. (9%)

1/c

time Problem #5 (14%)

There is a differential ammonia (NH3) pressure across a furnace wall made of titanium measuring 4.44 mm in thickness. The concentration of ammonia at the inner surface of the wall is held constant at 7.77 kg m 3, while the concentration of ammonia at the outer surface of the wall is held constant at 2.22 kg m 3. The area of the wall is 6.66 m2, and the diffusivity of ammonia in titanium at the furnace operating temperature is DNH3 = 2.22 10 10 m2 s 1. (a) How long does it take for 11.1 g of ammonia to leak from the furnace? Assume steady state.

(10%)

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Problem #5 (continued)
(b) If the furnace wall were replaced with titanium of the same composition but with a dislocation density 10 lower than that of the metal used in part (a), how would the time to lose the same amount of ammonia change? Explain. No need for any calculation. Simply describe the effect. With a lower dislocation density we could expect that the effective diffusion coefficient would be lower than that in the material described in part (a). Dislocations represent void space in the crystal. The less well packed the crystal is, the easier it is for matter to diffuse through it. So we should expect that the time to lose the same amount of ammonia to increase. (4%)

Problem #6 (12%)
(a) Two specimens of glass-forming silicate melts are cooled at the same rate: SiO2 5% CaO; and SiO2 10% CaO. On the same graph below sketch the variation of molar volume with temperature for each. Be sure to indicate the glass transition temperature, Tg. (8%)

molar volume

temperature
(b) In which material is the diffusion coefficient of helium (He) greater crystalline quartz [SiO2 (xtalline)] or quartz glass [SiO2 (amorphous)]? Explain. Crystalline quartz is more tightly packed than the amorphous material of the same composition. The diffusion coefficient should scale inversely with packing density the greater the void fraction, the greater the diffusion coefficient. So expect that the diffusion coefficient of helium is greater in quartz glass. (4%)