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1998 AP Chemistry Scoring Guidelines 1.-9 points i.) Cu(OH)2(s) Cu2+(aq) + 2 OH-(aq) 1 point Correct stoichiometry and charges (but not phases) necessary No credit earned if water as a reactant or product ii) 1.72 10 6 g 1.763 10 8 mol Cu(OH) 2 1 97.57 g mol 1 point 1.763 108 mol Cu(OH) 2 1.76 107 mol L1 0.100 L One point earned for conversion of mass to moles (need not be computed explicitly) One point earned for calculation of moles per liter iii) [Cu2+] = 1.76 × 10-7 M [OH-] = 2 × (1.76 X 10-7 M) = 3.52 × 10-7 M 1 point 2+ - 2 -7 -7 2 -20 Ksp = [Cu ][OH ] = (1.76 × 10 )( 3.52 × 10 ) = 2.18 × 10 1 point One point earned for correct [Cu2+] and [OH-] One point for correct substitution into Ksp expression and answer Response need not include explicit statement of [OH-] if Ksp expression is written with correct values of [Cu2+] and [OH-] pH = 9.35 → pOH = 4.65 → [OH-] = 2.24 × 10-5 M 1 point 17 K 7.7 10 sp [ Zn 2 ] 1.5 10 7 M 2 5 2 [OH ] (2.24 10 ) One point earned for correct determination of [OH-] One point for correct answer (assume [Zn2+] equals solubility in moles per liter) No points earned if [OH-] is assumed equal to twice [Zn2+] b) i) ii) Zn2+ + 2OH- Zn(OH)2(s) initial final Zn2+ 0.0050 mol 0 mol OH0.0150 mol 0.0050 mol Zn(OH)2 (s) 0 mol 0.0050 mol or 0.0050 mol 0.050 M 0.100 L One point earned if precipitation reaction is clearly indicated and moles or concentration of OHis calculated correctly Zn(OH)2 Zn2+ + 2 OHx (0.050 + 2x) Ksp = 7.7 × 10-17 = [Zn2+][OH-]2 = (x) (0.050 + 2x)2 = (x)(0.050)2 [Zn2+] = x = 3.1 × 10-14 M 1 point OR [OH ] Zn(OH)2 Zn2+ + (0.050-x) 2 OH(0.150 - 2x) Ksp = 7.7× 10-17 = [Zn2+][OH-]2 = (0.050-x)(0.150-2x)2 Solve for x, then subtract x from 0.050 M to obtain [Zn2+] Question 2 a) Assume a 100 – gram sample (not necessary for credit): 1 mol C 65 g C 5.462 mol C 12.01 g C 1 mol H 9.44 g H 9.366 mol H 1.0079 g H Mass O = [100 – (65.60 + 9.44)] = 24.96 g O 1 mol O 24.96 g O 1.560 mol O 15.9994 g O C5.462H9.366O1.560 --> C3.5H6.0O1.0 --> C7H12O2 One point earned for determining moles of C and moles of H One point earned for determining moles of O One point earned for correct empirical formula 15.2 o C T m 0.380 mol kg 1 b) Kf 40.0 K kg mol 1 0.380 mol 0.01608 kg 0.00611 mol 1 kg 1.570 g molar mass 257 g mol 1 0.00611 mol One point earned for determination of molality One point earned for conversion of molality to molar mass OR T kg solvent moles solute 0.00611 mol Kf 1.570 g molar mass 257 g mol 1 0.00611 mol OR Kf molar mass mass 257 g mol 1 T kg solvent 1 point 1 point 1 point 1 point 1 point 1 point 1 point 1 point 1 point 2 points Empirical mass of C7H12O2 = 7(12) + 12(1) + 2(1) = 128 g mol-1 128 g mol-1 = ½ molar mass --> molecular formula = 2 × (empirical formula) --> molecular formula = C14H24O4 1 points One point earned if molecular formula is wrong but is consistent with empirical formula and molar mass c) d) No penalty for simply ignoring the van’t Hoff factor Only one point earned for part b if response indicates that ΔT = (15.2 + 273) = 288 K and molar mass = 13.6 g mol-1 1 atm0.577 L PV n 0.0123 mol 1 point RT 0.0821 L atm mol 1 K 1 573 K mass of sample 1.570 g molar mass 128 g mol 1 1 point moles of sample 0.0123 mol Only one point can be earned for part c if wrong value of R is used and / or T is not converted from C to K The compound must form a dimer in solution, because the molar mass in solution is twice that it is in the gas phase, OR, The compound must dissociate in the gas phase (A(g) --> 2 B(g)) because the molar mass in the gas phase is half that it is in solution One point earned for a reference to either or both the ideas of dimerization and dissociation No point earned for a “non-ideal behavior” argument Question 3 – 9 points 1 mol 0.02125 mol phenol 1 point 94.113 g 64.98 kJ 3,058 kJ mol 1 Heat released per mole 0.02125 mol Or, ΔHcomb = -3058 kJ mol-1 1 point Units not necessary b) ΔHcomb = -3058 kJ mol-1 1 point o -3058 kJ = [6(-395.5) + 3(-285.85)] – [ΔHf (phenol)] 1 point ΔHfo (phenol) = -161 kJ 1 point One point earned for correct sign of heat of combustion, one point for correct use of moles / coefficients, and one point for correct substitution c) ΔSo = [3(69.91) + 6(213.6)] [7(205.0) + 144.0] = -87.67 J!K 1 point ΔGo = ΔHo - TΔSo = 3058 kJ – (298 K)(-0.08767 kJ K-1) = -3032 kJ 1 point Units not necessary; no penalty if correct except for wrong ΔHcomb for part a d) moles gas = 9 × [moles from part a] = 9 (0.02125 mol) = 0.1913 moles gas nRT (0.1913 mol)(0.0821 L atm mol 1 K 1 )(383 K ) P 0.601 atm 1 point V 10.0 L Units necessary; no penalty for using Celcius temperature if also lost point in part c for same error a) 2.000 g Question 4 – 15 points a. Sn2+ + Fe2+ Sn4+ + Fe2+ Two points earned if only error is wrong symbol for tin (eg, Ti) b. Co2+ + OH- Co(OH)2 c. C2H4 + O2 CO2 + H2O No penalty for other oxidized forms of carbon as products (e.g. C, CO) d. H3PO4 + OH- H2PO4- + H2O One point earned for H+ + OH- H2O Two points earned for removal of H+ from any HxPyOz species and H2O as product e. CaSO3 CaO + SO2 Two points earned for CaSO4 CaO + SO3 f. H+ + Cl- + [Ag(NH3)2]+ AgCl + NH4+ Cl- + [Ag(NH3)2]+ AgCl + NH3 (or NH4+) earns two points H+ + [Ag(NH3)2]+ Ag+ + NH4+ earns two points g. Na2O + H2O Na+ + OHTwo points earned if reactants correct but only product is NaOH h. Zn + H+ Zn2+ + H2 Two points earned for Zn + H+ + Br- ZnBr2 + H2 Two points earned for Zn + HBr Zn2+ + Br- + H2 Question 5 (8 points) a. 4 essential steps 1) weigh KHP 2) fill buret with NaOH solution 3) add indicator (phenolphthalein) 4) titrate to endpoint (color change) Two points earned for all 4 steps; one point earned for 2 or 3 steps Titration of acid into base accepted if described correctly mass KHP moles KHP b. molar mass KHP moles OH moles KHP = moles OH- at equivalence and [OH ] liters NaOH Acceptable if some pars of part b appear in a c. Curve should have 3 important features 1) Curve begins above pH 1, but below 7 2) Equivalence point at 25 mL 3) Equivalence point above pH 7 Both points earned for all 3 features One point earned for any 2 of the 3 features d. At the half-way point in the titration, pH = pKa e. At point A in the titration, the anion in highest concentration is Y2Also accepted: Y2-, Y--, Y=, and specific anions such as SO42-, SO32HY-, Y- and “Y ion” not accepted Question 6 – 8 point a) Response must clearly indicate (and distinguish between) Eact and ΔHrxn on graph. Each earns one point (2 total) b) i. Response shows a softly curving line that approaches the time axis and whose slope changes continually No penalty if curve crosses time axis or levels out above time axis. Curve must drop initially and continually. No credit earned if [N2O5] increases. 2 points 1 point 1 point 2 points 1 point 1 point ii. Reaction Rate is the slope of the line tangent to any point on the curve. Rate must be tied somehow to slope of graph . Answer may be indicated directly on the graph . Instantaneous rate must be indicated rather than the average rate iii.) Since "rate = slope = k[N205J", the value of k can be determined algebraically from the slope at a known value of [N20S]. No penalty for "Rate =2k[N205] ", as reaction stoichiometry could suggest this answer. Point can be earned for rate constant = slope of graph of ln[N2O5] vs.. time since reaction is first order. Use of half-life or integrated rate law to solve for k can be accepted. iv. The value of the rate constant is independent of the reactant concentrations, so adding more reactant will not affect the value of k. No point earned for simply stating that value of k will not change . Response must distinguish between rate. and rate constant. i. Rate = k[A] or ln ([A]/[A]0) = -kt. Since graph of ln [A] vs. time is linear, it must be a first-order reaction. Either form of the rate law is acceptable, and both the equation and the brief justification are required to earn the point No point earned if response indicates first order because the first graph is not linear. ii. Determine the slope of the second graph and set “k= - slope” Response must indicate both the negative sign and the slope. Question 7 – 8 points a b. c. the number of moles of CO will decrease 1 point because adding H2 will make the reaction shift to the left OR, adding H2 will make the reaction quotient larger than K, thus the reaction shifts to the left 1 point The number of moles of CO will increase 1 point because since the reaction is endothermic, addition of heat (as a reactant) will drive the reaction to the right 1 point The number of moles of CO will decrease 1 point because there are more moles of gas (2) on the right than on the left (1), thus decreasing the volume which increases the pressure causing the reaction to shift to the left 1 point d. The number of moles of CO will stay the same 1 point because Solids are not involved in the equilibrium expression OR Solids have no effect on the equilibrium Question 8 (8 points) a) 2 Ag+(aq) + Cd(s) ~ 2 Ag(s) + Cd2+(aq) equation must be balanced and net ionic, phases not necessary reaction direction and ion charges must be correct 1 point 1 point 0.80 - (-0040) = 1.20 V evidence of where numbers came from should be present; if equation is exactly reversed, -1.20 V earns the point 1 point b) Anions (or N03- ions) will flow to the Cd2+ solution or from the Ag+ solution to balance the charges OR Anions will flow to the left to balance the positive charge of the new Cd:!+ ions both the correct direction and justification1 needed to earn this point direction may be indicated by arrow marked on diagram 1 point c) The cell voltage will increase. 1 point Ag+ is a reactant, so increasing [Ag+] will increase the driving force (stress) for the forward (spontaneous) reaction and the potential will increase OR 1 point 2+ Since Q = [Cd ]/[Ag+]2, increasing [Ag+] will decrease Q. According to the Nernst equation, E = E0 (0.0592 log Q / n , if Q decreases, then voltage increases. d.) The cell voltage will decrease. 1 point Adding NaCI will have no effect on the Cd cell, but will cause AgCI to precipitate in the Ag cell (Ag+ + Cl- AgCl). Thus [Ag+] decreases, and since Ag+ is a reactant, decreasing [Ag+] causes a decrease in voltage. 1 point Credit earned for" decreasing [Ag+] results in decreased voltage" or "opposite of part (c)" e) Since Q = [Cd2+]/ [Ag+/2 , diluting both solutions by the same amount will increase the value of Q. According to the Nernst equation, E = E0 - (0.0592 log Q )/n , if Q increases, then voltage decreases. , • No credit earned for "since the solutions are diluted, the voltage will decrease" Question 9 (8 points) a) At the higher altitude the ambient pressure is significantly less than 1.0 atm. 1 point Under reduced pressure, water boils at less than 100 oC 1 point Two points earned for "At the higher altitude water boils at less than JOO"C. and at the lower temperature the chemical physical processes (the "cooking ") take longer b) Cu2+(aq) + 2 OH-(aq) Cu(OH)2(s) 1 point Response must indicate that an insoluble hydroxide forms. but equation is not necessary Cu(OH)2(s) + 4NH3(aq) [Cu(NH3)4]2+(aq) 1 point Response must indicate some cationic ammine complex with a reasonable coordination number c) CH3CH2OH 1 point Response must indicate a clear ethanol structure (Lewis diagram not necessary) 1 point The hydroxyl group forms hydrogen bonds with water molecules. Response must mention/indicate involvement of hydroxyl group Point earned for "Ethanol is more polar than dimethyl ether", but no point earned for "dimethyl ether is linear (or nonpolar)" d.) Au3+, Co3+, or F2 These oxidants are below the CI/Cl- reduction half-reactions, so they would spontaneously oxidize CI to C12 1 point Any species to the right of the arrow and above the C12/Cl reduction half-reaction on the standard reduction potential table. 1 point Identification and justification needed to earn each point - justification should minimally make some reference to relative positions in the reduction potential table