 |
(Trigonal) pyramid(al) |
 |
(Trigonal) bipyramid(al) |
Notes
1) Each reaction (students choose 5) is worth 3 points: 1 point earned for correct reactants, 2 points earned for correct product(s). Phases need not be designated and equations need not be balanced. Partial credit (1 point) can be earned for the products but not for the reactants.
(a) Al3+ + OH¯ ---> Al(OH)3
Other acceptable products: Al(OH)4¯; Al(OH)4(H2O)2¯; Al2O3; Al2O3 . xH2O; AlO2¯
(b) H+ + Br¯ + BrO3¯ ---> Br2 + H2O
(c) SO2 + H2O ---> H2SO3
other acceptable products: H+ + HSO3¯ or H+ + HSO3¯ + SO32¯
(d) PH3 + BCl3 ---> H3PBCl3
other acceptable products: PH3BCl3
(e) H2 + FeO ---> H2O + Fe
(f) KNH2 + H2O ---> NH3 + OH¯ + K+
other acceptable products: NH4OH + OH¯ + K+
(g) Mg + N2 ---> Mg3N2
(h) Ni2+ + S2¯ ---> NiS
or Ni2+ + H2S ---> NiS + H+
or Ni2+ + HS¯ ---> NiS + H+
2.
(a) 5.00 x 10¯3 mol H2C2O4 = 1.00 x 10¯2
mol H+ = 1.00 x 10¯2 mol OH¯
1.00 x 10¯2 mol OH¯ / 0.400 M = 0.0250L (25.0 mL).
Calculation from moles to volume; use of incorrect moles still earns point.
(b) There are two successive dissociations:
H2C2O4 <===> H+ + HC2O4¯ (equilibrium constant = K1)
HC2O4¯ <===> H+ + C2O42¯ (equilibrium constant = K2)
Acceptable alternatives are the use of H2O as reactant and H3O+ as product or writing of correct equilibrium constant expressions. Consistent errors (such as missing atoms or charges) are only penalized once.
K12 = K1 times K2, thus
K1 = K12 / K2 = 3.78 x 10¯4 / 6.40 x 10¯5 = 5.91 x 10¯2; one point
c)
pH = 0.5 therefore H+ = 0.32M (pH controls 1 sig. fig. in answer)
(This point also earned if conversion of K to pK is correct.)
K small therefore amount of dissociation small therefore assume [H2C2O4] = 0.015
K12= ([H+]2 [C2O42¯]) / [H2C2O4] ,
then [C2O42¯] = [(3.78 x 10¯ 6) (0.015)] / (0.32)2 = 6 x 10¯ 7 .
(Here 1, 2 , or 3 sig. fig.'s accepted) Two points for correct set-up with substitution and final calculation (-1 point for each error).
Alternative methods, included proper use of Henderson-Hasselbalch equation, can earn credit.
(d)
C2O42¯ + H2O <===> HC2O4¯
+ OH¯ is the only significant reaction,
so Kb= Kw / K2 = 1.00 x 10¯14 / 6.40 x 10¯ 5 = 1.56 x 10 ¯10
No credit earned if K1 or K 12 used; 1, 2 , or 3 sig. fig.'s accepted since number of significant figures for value of Kw not indicated in table on examination.
3
(a) 1 point
2Cl¯ ---> Cl2 + 2e¯ (equation need not be balanced)
(b) three points
(0.250 coul / sec x 7,2000 sec) / (96,500 coul / mol e¯) = 1,800 coul / (96,500 coul / mol e¯) = 0.01865 mol e¯
mol Fe = 0.521 g Fe / (55.85 g / mol Fe) = 0.00933 mol Fe
mol e¯ / mol Fe = 1.865 x 10¯2 mol e¯ / 9.33 x 10¯3 approx. equals 2 e¯ per Fe atom ---> FeCl2
(c) 1 point
Fe2+ + 2 Cl¯ ---> Fe + Cl2
Notes: "FeCl2(aq)" accepted for reactants. Any balanced equation corresponding to answer in part (b) earns 1 point.
(d) 1 point
moles Fe2+ = moles Cl2 = 9.33 x 10¯3 mol Cl2
V = nRT / P = (0.00933 mol Cl2 x 0.0821 L.atm.mol¯1.K¯1 x 298 K) / (750 / 760) atm = 0.231 L (or 231 mL)
(e) two points
(3.00 g Cl2 / 71 g mol¯1) / 3,600 sec = 0.0423 mol Cl2 / 3,600 sec = 1.17 x 10¯5 mol Cl2 / sec
current (in amperes) = (2 mol e¯ / mol Cl2) x (1.17 x 10¯5 mol Cl2 / sec) x (96,500 coul / 1 mol e¯) = 2.27 amp (or coul /sec)
alternate solution: 0.00933 mole Cl2 / 2 hrs = 0.662 g Cl2 / 2 hrs = 0.331 g Cl2 / hr
0.20 amp / 0.331 g Cl2 = x / 3.00 g Cl2
x = (3.00 g x 0.250 amp) / 0.331 g = 2.27 amp
4)
(a) three points
1.3 x 10¯3 / 4.3 x 10¯4 = k (0.75)x (0.75)y / k (0.25)x (0.75)y leads to 3 = (3)x leads to x = 1, first order in A
5.3 x 10¯3 / 1.3 x 10¯4 = k(1.50)(1.50)y/ k(0.75)(0.75)y => 4= 2(2)y => y=1 => First order in B
Notes; Verbal descriptions accepted, but no point earned for just "if A doubles, the rate doubles". If A given as second order, 2 points can be earned for showing that B must be zero order.
(b) two points
rate = k[A][B] (equation must be consistent with part (a))
k= 4.3 x 10¯4M min¯1 / (0.25M) (0.75M) = 2.3 x 10¯3 M¯ 1 min¯1
Note; Units must be correct to earn second point. If no part (a) shown, 1 point can be earned for a reasonable (first or second order) rate law.
(c) one point
D[A] / Dt = -2 (5.3 x 10¯3 M¯1 min¯1) = - 1.06 x 10¯2 M¯1 min¯ 1
Note; Units ignored; no penalty for ( ¯ ) sign.
(d) one point
8.0 x 10 ¯3 M¯1 min¯1 = (2.3 x 10¯2 M¯1 min¯1) (1.75 M) [B]
[B] = 2.0 M
Note; No penalty if answer is consistent with wrong part (b).
(e) two points
Mechanism 2 is consistent
rate proportional to [M][A] and [M] proportional to [B] => rate proportional to [A][B]
Notes; Verbal discussion accepted for second point. Mechanism must be consistent with rate law in part (b). Showing that mechanisms 1 and 3 are inconsistent is not required.
5)
| |
(Trigonal) pyramid(al) |
| |
(Trigonal) bipyramid(al) |
1 point for each structure
Note ; One point (total) deducted if lone pairs not shown on F atoms in either molecule.
(b) The PF3 molecule is polar
The three P-F dipoles do not cancel, or,
the lone pair on P leads to asymmetrical distribution of charge.
Note; "Molecule is not symmetrical" does not earn point. Both points can be earned if answer is consistent with incorrect (a).
(c) NF5 does not exist because no 2d orbitals exist for use in bonding, or,
N is too small to accommodate 5 bonding pairs
AsF5 does exist because 4d orbitals are available for use in bonding, or,
As can accommodate an expanded octet using d orbitals
Note; Response with two correct predictions with no explanations earns one point. Also, argument of "no expanded octet" vs. "expanded octet" alone does not earn expalnation point.
6)
a) Response must contain a cogent discussion of the forces between the nucleus and the outermost (or "ionized") electron. For example, a discussion of "the outermost electron on K..." should include one of the following:
i. it is farther from nucleus than the outermost electron on Li
ii. it is more shielded from the nucleus (or "experiences a lower effective nuclear charge") than the outermost electron on Li
iii. it is in a higher energy orbital (4s) than tne outermost electron on Li (2s)."
2 points for any one
Notes:"K is larger than Li" earns 1 point.
No points earned for "K electron is easier to remove" (or some other restatement).
b) Nitrogen has one less proton than oxygen 1 point
Nitride and oxide ions are isoelectronic 1 point
or,
In nitride ion the electron/proton ratio is greater, causing more repulsion; thus, nitride is the larger ion. 2 points
c) A Zn atom has more protons (10 more) than an atom of Ca 1 point
Electrons in d orbitals of Zn have a lower principal quantum number; thus, they are not in orbitals that are farther from the nucleus. 1 point
d) Correct identification of the orbitals involved (2s versus 2p) 1 point
Clear statement that the two orbitals have different energies 1 point
Note: Arguments that "the 2p orbital is farther out than the 2s orbital", or that "the Be atom has a filled subshell, which is a more stable configuration" earn no explanation point.
General note:For all parts (a) through (d), discussions of position in the periodic table earn no points.
7)
(a) DS° is positive (or "+", or ">0") 1 point
Moles products > moles reactants 1 point
Note; all species are gaseous, so (g) need not be indicated. To earn credit, number of particles (moles) must be discussed. No explanation point earned for just nothing that disorder increases, or that PCl5 is decomposing or dissociating.
(b) DG° will decrease (or become more negative, or become smaller). 1 point
DG° = DH° - TDS°
and since DS° is positive, TDS° is
positive ( > 0). Thus increasing T will result in a larger term being subtracted from DH°, or, DG° = -RT ln K and K is going
up in value since T is increasing.)
Note: full credit earned for part (b) if:
DS° < 0 in part (a) which leads to DG°
is increasing because TDS° is added to DH°,
or,
DS° = 0 in part (a) which leads to no change in DG°
(c) no change (one point)
PHe is not part of the a) reaction (He is not involved) or, b) law of mass action or, c) reaction quotient or, d) equilibrium constant expression; one point
hence altering PHe has no effect on the position at equilibrium
(d) moles of Cl2 will decrease (one point)
The decrease in volume leads to an increase in pressure (concentration), therefore the reaction shifts to the left because:
(one point for any of the following)
Q > Ksp (Q > Kc, or,
the rate of the reverse reaction increase more than the rate of the forward reaction, or,
the reaction shifts toward the lesser moles of gas.
Note: "LeChatelier's principle" alone is not sufficient to earn the explanation point. If response suggests that the number of moles of Cl2 is halved because the system is "cut" in half, only one point is earned.
8)
(a) 94-Pu-239 ---> 2-He-4 + 92-U-235
Notes; One point is earned for [He] (or a), one point for correct total mass number in products, and one point for consistent atomic numbers and symbols. Full credit is also earned for correct decay starting with Pu-234 (as was printed on the green insert)
(b) Missing mass is converted to energy (or "E=mc2")
Notes; No point earned for just mentioning "mass defect".
(c) In words, or drawn on diagram:
path of a particle bends toward negative (-) plate, 1 point
path of b particle bends toward positive (+) plate, 1 point
path of l ray is undeflected. 1 point
(d) Incineration (combustion, oxidation) is a chemical process AND as such it has no effect on a nuclear process (decay). 1 point
Notes; No point for thermodynamic, kinetic, or equilibrium arguments. No point earned for "dispersion of material is bad for the environment" or similar statements.
9)
a) 2 points Mix unknown and BaCl2(aq) as reactants
Collect precipitate / set up filtration
b) 2 points Mass of unknown salt as reactant
(sulfate="salt"=unknown salt, unless otherwise specified)
Mass BaSO4 (must be specified) as dried precipitate/product
Note: "Dried" must appear to earn all 4 points for (a) and (b)
c) 2 points
Mass BaSO4 --> moles SO42¯ --> mass SO42¯ (to be used in) -----> mass SO4 2¯ / mass unknown
Notes: A list alone is acceptable. Method, if correct, acceptable as list. Response must clearly distinguish between SO42¯, BaSO4, and unknown sulfate. Only one of two points earned if mass SO42¯ incorrect but fraction for percent clearly indicates part (of original salt) / whole (of original salt).
d) 2 points
MgCl2 is NOT an acceptable substitute for BaCl2.
MgCl2 is too soluble.
Note: 1 point earned if response indicates MgCl2 is acceptable and reason given is that Mg2+ behaves like Ba2+ to form an insoluble SO42¯ precipitate (response must previously specify BaSO4 as product)