Worked-Out Solutions Final Exam Spring, 2012

1. If 35.0% reacts, then 65.0% remains, meaning ln

c = 0.65 co

c = -kt co

ln 0.65 = -k(20) Solving: k = 0.0215 min-1 Now use this value of k to calculate how long it would take for 90.0% to react. If c 90.0% reacts, then 10.0% remains, meaning = 0.10 co ln

c = -kt co
Solving: t = 107 minutes Choice B

ln 0.20 = -(0.0215)t

25.0g x

2.

! = MRT =

1mol 180g (0.0821)(298) = 13.6 atm 0.250 L

Choice A

3.

Ea2 + ln A where Ea2 is the activation energy with a catalyst. RT E ln k1 = - a1 + ln A where Ea1 is the activation energy without a catalyst. RT

ln k2 = -

Subtracting: ln k2 ln k1 = -

(E a 2 ! E a1 ) (E ! E a 2 ) k or ln 2 = a1 RT RT k1

(Ea1 - Ea2) represents the decrease of the activation energy using the catalyst. If the rate with a catalyst is 27 times faster than without a catalyst then

k2 = 27 k1

ln 27 =

(E a1 ! E a 2 ) J kJ Solving: Ea1 - Ea2 = 8470 or 8.47 . Choice D (8.314)(309) mol mol

4.

g g cm 3 x 1000 = 1203 3 cm L L This means 1203 gram per liter of solution. g Each liter also contains 1.562 mol CaCl2 x 111 = 173.4 g CaCl2 mol

The solution has a density of 1.203

So each liter contains (1203 173.4) = 1029.6 g of solvent (water), or 1.2096 kg water

Definition of molality:

molsolute kgsolvent

1.562 molCaCl2 = 1.517 molal Choice A 1.0296 kgsolvent

5.

First convert 4.4 mg in 100 mL into molarity

0.0044g x 1mol 32.0g = 1.375 x 10-3 M at 1.0 atm 0.100 L

Henrys Law: Solubility is proportional to partial pressure of the gas. 0.010 M at x atm (x to be calculated) 1.375 x 10-3 M at 1.0 atm x=

0.010 x 1.0 = 7.3 atm Choice C 1.375x10 !3

6.

ln

E 1 k2 1 = a( ) R T1 T2 k1 Ea 1 1 ( ) 8.314 298 310

k2 = 3.0 since the rate triples k1

ln 3 =

Solving: Ea = 70,300

J kJ or 70.3 mol mol

Choice A

7. Comparing experiments 1 and 2: [HgCl2] is constant 0.404 2.08 [C2O42-] goes up by: = 2.0 Rate goes up by = 4.0 0.202 0.52 This implies 2nd order for C2O42- since 2.02 = 4.0 Comparing experiments 3 and 2: [C2O42] is constant 0.0836 2.08 [HgCl2] goes up by = 2.0 Rate goes by = 2.0 0.0418 1.04 This implies 1st order for HgCl2 Rate law is: rate = k[HgCl2][C2O42-]2 Use data for any line to solve for k From 1st line: 0.52 x 10-4 = k(0.0836)(0.202)2 Solving: k = 0.01524 For experiment 4: Rate 0.01524(0.0627)(0.606)2 = 3.51 x 10-4 M/min Choice D 8. According to the energy profile, its a 2-step process with the 2nd step being the slow step, since the 2nd step has the highest activation energy. Choice E "Tf = iKf m Since molality is the same in all choices, we distinguish them based on the i factor. OF the choices, MgCl2 has the highest i factor (i = 3). This solution would have the highest "Tf, meaning the most depressed (or lowest) freezing point. Choice A The equation given for the rate law is 1st order, since rate = k[N2O5]1. The c integrated rate law for first-order is: ln = -kt This equation means that if you co plot ln c vs time, you get a straight line with slope = -k. Choice B

9.

10.

11.

You can think of the dissolving of an ionic salt, such as NaCl, as a two-step process, where first you convert the solid salt into gaseous ions (lattice energy required), and then the gaseous ions join with water to form ion-dipole bonds (hydration energy is released). This is represented as: "H = lattice energy of NaCl (expressed as a positive number_) + + Na (g) + Cl (g) # Na (aq) + Cl (aq) "H = hydration energy of Na+ and Cl(expressed as a negative number) Overall: NaCl(s) # Na+(aq) + Cl-(aq) "H = sum of positive lattice energy and negative hydration energy Since "H of solution is approximately zero, the energy needed to break down the lattice into gaseous ions (lattice energy) is about equal to the energy released when the gaseous ions bond with water (hydration energy). Choice C NaCl(s) # Na+(g) + Cl-(g)

12.

"Tb = Kb m
x (62.60 61.70) = 3.63 ( 406.9 ) 0.125

Solving: x = 12.6 g

Choice A

13.

H2C6H6O6(aq) # H+(aq) + HC6H6O6-(aq) 0.10-x x x

Ka1 = 8.0 x 10-5

For diprotic acids, usually Ka1 is much greater than Ka2, as is the case with H2C6H6O6. We then first solve for H+ and HC6H6O6- using the Ka1 equation only. Then we use the values equation from the Ka1 to calculate any further values in the Ka2 equation. Using the Ka1 equation above:
x2 = 8.0 x 10-5 0.10 ! x

Solving: x = [H+] = [HC6H6O6-] = 2.8 x 10-3 M

Using this value (0.0028 M) for both [H+] and [HC6H6O6-] in the Ka2 equation: HC6H6O6- ! H+ + C6H6O620.0028 y 0.0028+y y Ka2 = 1.6 x 10-12

(0.0028 + y)y = 1.6 x 10-12 (0.0028 ! y)

Making the usual approximation that y is small compared with 0.0028, we get a simple solution with the 0.0028 canceling in numerator and denominator, and the y value simply equals the value of Ka2. y = [C6H6O62-] = 1.6 x 10-12 M Choice E

14.

H2C2O4(aq) + H2PO4(aq) ! HC2O4(aq) + H3PO4(aq) stronger acid stronger base weaker base weaker acid In an acid/base reaction, an acid donates a proton to a base, forming, as products, the conjugate base of the acid and conjugate acid of the base. Since the problem states that at equilibrium, theres higher concentration of products (right side) than reactants (left side), this implies that the left side has the stronger acid and stronger base, with a bigger push to donate and accept H+ ions than the weaker acid/weaker base combination on the right side of the equation. Choice C

15.

An amphoteric species can act as both an acid or base HSO3-, HC2O4- and HPO3- can both donate and accept H+ ions. They are all amphoteric. Al2O3, although not a direct donor of H+ ions, is an amphoteric oxide in the sense that it can react with H+ ions (the O2- part of Al2O3 is a base) and can react with OHions in water to form the complex ion Al(OH)4- (see page 697 of text). CO32- is a base: it can accept H+ ions to form HCO3-, but CO32- cannot donate H+ ions or in any other way act as an acid. Choice A

16.

HX(aq) ! H+(aq) + X-(aq) 0.20 x x x

x2 = Ka 0.20 ! x

HX is 5.25% ionized, meaning x = 0.20(0.0525) =0.0105 M

Ka =

(0.0105)2 = 5.82 x 10-4 (0.20 ! 0.0105)

Choice A

17.

Kb is the equilibrium constant for an equation in which a base B in aqueous solution, accepts a proton from water, forming BH+ and water donates a proton to the base, leaving over OH-. If the base is CH3NH2, this would be represented by the equation: CH3NH2 + H2O ! CH3NH3+ + OHChoice D

18.

Since Kw increases with increasing temperature, this implies the reaction is endothermic. At 60 oC: H2O(") ! H+(aq) + OH-(aq) Kw [H+][OH-] = 1.0 x 10-13. x x At 60 oC: x2 = 1.0 x 10-13 Solving: x = 3.2 x 10-7 M pH = -log (3.2 x 10-7) = 6.5 Choice D

19.

pH 2 means [H+] = 0.010 M

pH 6 means [H+] = 0.0000010 M

Mixing 10 mL of 0.010 M H+ with 10 mL of 0.0000010 M H+:

mol mol + 0.010 L x 0.0000010 = 0.00010 mol L L 0.00010 mol Molarity = = 0.0050 M pH = -log (0.0050) = 2.30 Choice B 0.020 L

0.010 L x 0.010

20.

NH4HS(s) ! NH3(g) + H2S(g) Kp = 0.108 solid x x x2 = 0.108 x = 0.329 atm Choice C

21.

A Lewis acid is an electron pair acceptor. Boron compounds, such as BH3, have 3 bonds and no lone pairs. Theres an empty 2p orbital around the boron atom that can accept a lone pair of electrons. BH3 is a Lewis acid. Choice B NaNO2 dissolves to give Na+(aq) and NO2-(aq). NO2-(aq) is the conjugate base of the weak acid HNO2, meaning that NO2- is a weak base with the ability to attract a proton from water. NO2- + H2O ! HNO2 + OHOf the other choices: NaCl has neither acid nor basic properties in water. Cl- is the conjugate base of the strong acid HCl, meaning that Cl- has negligible base properties in water. NH4NO3 is acidic, since NH4+ is the conjugate acid of the weak base NH3. NO3is the conjugate base of the strong acid HNO3, meaning that NO3- has negligible base properties in water. KBr has neither aicd nor basic properties in water. Br- is the conjugate base of the strong acid HBr, meaning that Br- has negligible base properties in water. AlCl3 is acidic since the Al3+ ion exists in hydrated form as Al(H2O)63+, and this hydrated Al3+ can release an H+ ion to water: Al(H2O)63+ # H+ + Al(H2O)5OH2+ Choice B

22.

23.

NaNO2 dissolves to give Na+(aq) and NO2-(aq). NO2-(aq) is the conjugate base of the weak acid HNO2, meaning that NO2- is a weak base with the ability to attract a proton from water. NO2- + H2O ! HNO2 + OH0.25 x
x2 = Kb 0.25 ! x

Kb (of NO2-) =

Kw K a (of HNO 2 )

pH = 8.38 pOH = 14.00 8.38 = 5.62 x = [OH-] = 10-5.62 = 2.4 x 10-6 M Kb =

x2 (2.4 x10 !6 )2 = = 2.3 x 10-11 0.25 ! x 0.25 ! 2.4 x10 !6

Ka (of HNO2) =

Kw 1.0 x10 !14 = = 4.3 x 10-4 Choice D ! !11 K b (of NO 2 ) 2.3x10

24. Initial Change Equil

2SO2(g) + O2(g) ! 2SO3(g) 0.60 0.40 0.50

This chart summarizes what is directly given in the problem. The rest of the chart can be filled in by inference: 2SO2(g) + O2(g) ! 2SO3(g) Initial 0.60 0.40 Change -0.50 -0.25 +0.50 Equil 0.10 0.15 0.50

Kp =

(0.50)2 = 167 or 1.7 x 102 (0.10)2 (0.15)

Choice A

25.

Cd2+(aq) + 4CN-(aq) ! [Cd(CN)4]2-(aq) Kf = 7.1 ! 1016 Initial 0.015 0.25 RTC -0.015 -4(0.015) +0.015 RTC means react to completion Equil 0 0.19 0.015 Since K is large, first react to completion. The limiting reactant, Cd2+ goes down almost to zero, but there will be a small concentration remaining at equilibrium. The other concentrations 0.19 M for CN-, and 0.015 M for Cd(CN)42- are very close to equilibrium quantities, since the reverse reaction is so small. Instead of 0, let [Cd2+] = x

0.015 = 7.1 x 1016 4 x(0.19)

Solving: x = 1.6 x 10-16 M

Choice C

26.

CaCO3(s) ! CaO(s) + CO2(g) "Ho = 177.8

kJ mol

"So = 160.5

J molK

"Go = "Ho - T"So = 177.8 298 (

160.5 ) = 130.0 kJ or 129971 J (keeping extra digits) 1000

"Go = -RT ln K 129971 !G O ln K = == -52.46 (8.314)(298) RT K = e-52.46 = 1.6 x 10-23 Since everything else in the equation is a solid, K = pCO2 = 1.6 x 1023 atm Choice C

27. 0.500 L x 0.175

molHCl = 0.0875 mol HCl or 0.0875 mol H+ L molCa(OH)2 2 molOH ! x = 0.080 mol OHL molCa(OH)2

0.500 L x 0.080

H+ + OH- # H2O

Reaction goes to completion. Limiting reactant is OH-

Left over H+: 0.0875 0.080 = 0.0075 mol H+ left over

Theres a total of 500 mL + 500 mL or 1.00 L total. So 0.0075 mol of H+ is left over in a total of 1.00 L for a molarity of 0.0075 M pH = -log[H+] = -log (0.0075) = 2.12 Choice B

28.

Ag2S(s) ! 2Ag+(aq) + S2-(aq) Ag2S will be least soluble in solutions containing Ag+ or S2- (common ion effect). There are two choices , C and D, which contain Ag+ and S2- respectively, which would lower the solubility of Ag2S. Well evaluate them individually. Assuming 0.10 M AgNO3 (choice C) Ag2S(s) ! 2Ag+(aq) + S2-(aq) 0.10+2x x (0.10+2x)2 x = Ksp

Ignoring 2x compared with 0.10: x =

K sp 0.10 2

Assuming 0.10 M Na2S (choice D) Ag2S(s) ! 2Ag+(aq) + S2-(aq) 2x 0.10+x (2x)2 (0.10+x) = Ksp Ignoring x compared with 0.10: x2 =
K sp 0.40

x=

K sp 0.40

With the square root, the value of x is much larger for choice D than choice C. Hence choice C has the lowest solubility. This is because Ksp is a small number much less than oneso taking its square root gives a much large number. For example, using Ksp = 6.0 x 10-51 for Ag2S: Choice C gives: Choice D gives
6.0 x10 !51 = 6.0 x 10-49 2 0.10

6.0 x10 !51 = 1.2 x 10-25 0.40

Choice C

29.

Ag2SO4(s) ! 2Ag+(aq) + SO42-(aq) 2x 2.0 + x (2x)2(2.0 + x) = 1.7 x 10-5

Solving: x = 1.5 x 10-3 M 30.

Choice E

This is a reaction of a weak acid with a strong base, which goes to completion with a large value of K. HCN + OH- # HOH + CNStart with 0.010 L x 0.10 K =

Ka = 4.9 x 104 Kw

mol = 0.0010 mol NaOH = 0.0010 mol OHL mol Start with 0.050 L x 0.10 = 0.0050 mol HCN L

The limiting reactant is NaOH. After reacting to completion, we form 0.0010 mol of CN- and have (0.0050 0.0010) = 0.0040 mol of HCN left over. We recognize this as a buffer, which can be formed by the partial neutralization of a weak acid by a strong base, as is happening here. The total volume is 60 mL. 0.0040 mol In this buffer: [HCN] = = 0.0667 M 0.060 L 0.0010 mol [CN-] = = 0.0167 M 0.060 L Buffer relationship: [H+] = Ka

[HCN] 0.0667 = 4.9 x 10-10 ( ) = 1.96 x 10-9 ! [CN ] 0.0167

pH = -log(1.96 x 10-9) = 8.71 Alternatively, you can use the Henderson-Hasselbalch equation. pH = pKa + log
base acid

pH = -log(4.9 x 10-10) + log

0.0167 = 8.71 0.0667

Choice B

31.

Optical isomers are non-superimposable mirror images.

Choice E

32.

Linkage isomerism means that the ligand can have more than one location where it can attach (link) to the central metal cation. NO2- can have linkage isomerism. It can attach at the N atom where there is a lone pair, or either of the O atoms, where there are lone pairs. Choice B BaF2(s) ! Ba2+(aq) + 2F-(aq) Ksp = 1.7 x 10-6 PbF2(s) ! Pb2+(aq) + 2F-(aq) Ksp = 4.0 x 10-8 A precipitate occurs when Q >Ksp For BaF2, which is more soluble than PbF2, a precipitate will occur when: [F-]2 =

33.

K sp [Ba 2+ ]

1.7x10 !6 = 1.7 x 10-5 M 0.10

[F-] = 1.7x10 !5 = 0.00412 M Any F- molarity > 0.00412 M will cause precipitation of BaF2

4.0 x10 !8 At that point, [Pb ] = ! 2 = = 2.35 x 10-3 M !5 [F ] 1.7x10

2+

K sp

Percent Pb2+ remaining in solution:

2.35x10 !3 x 100 = 2.4 % Choice E 0.10

34.

A buffer may be formed by: Adding an acid to its conjugate base Adding a base to its conjugate acid Partially neutralizing a weak acid with a strong base (as in problem 30) Partially neutralizing a weak base with a strong acid. In this problem we start with 0.25 mole of HCl, a strong acid. This can be used to form a buffer by adding to a weak base, partially neutralizing that weak base. In the choices, the only weak base is methylamine, CH3NH2. Adding HCl to CH3NH2, we get the reaction: H+ + CH3NH2 # CH3NH3+ K=

Kb (goes to completion) Kw

Adding 0.25 moles of H+ (from HCl) to 0.50 mol of CH3NH2 will produce 0.25 mol of CH3NH3+ with 0.25 mol of CH3NH2 left over. This is a half-neutralization producing a 1:1 buffer of CH3NH2 and CH3NH3+. Choice D

35. Since the titration curve shows decreasing pH, we must be adding acid to a base. Since the pH at the equivalence point (the inflection point or middle of the steep section of the curve) is around pH 5, we must be added an acid to a weak base. If we started with NH3 (a weak base) and added HNO3 (a strong acid), we would get a curve looking like the curve in the question. Choice D 36. "H = (-212.5 + 80.3) (-296.8) = 164.6 kJ "S = (309.77 + 266.1) (2(223) + 248.1) = -118.23 J K-1 "G = "H - T"S = 164.6 298(
!118.23 ) = 199.8 kJ 1000

Choice D

37.

dN = kN dt

where -

dN is the instantaneous rate dt

k=

ln 2 ln 2 = = 1.54 x 10-10 years-1 t1/2 4.5x10 9

nuclei 1mol x 6.02 x 1023 = 2.53 x 1021 nuclei mol 238g

N = 1.0 g x
dN = kN dt

= (1.54 x 10-10)(2.53 x 1021)

nuclei sec

nuclei 1year x year 3.156 x10 7 sec

= 1.2 x 104

Choice A

38.

Control rods absorb excess neutrons and keep neutrons at the correct speed. Choice E

39.

The equation for the concentration cell would be: Al(s) + Al3+(1.25 M) # Al3+(0.050 M) + Al(s) Eo = 0 for a concentration cell, since under standard conditions, all concentrations would be 1.0 M and there would be no cell voltage. E = Eo 0.0592 log Q n

E=0-

0.0592 0.050 log = 0.028 volts 3 1.25

Choice D

40.

N neutron stands for the ratio in the nucleus Z proton

If this ratio is too high, there are too many neutrons for stability, and one of the neutrons converts into a proton emitting a beta particle (electron). Choice B 41. All Eo values are written as reduction half reactions, and are called reduction potentials. The substance on the left side with the highest reduction potential is the one most easily reduced, or the strongest oxidizing agent. The substance on the left side with the lowest reduction potential is the one least easily reduced, or the weakest oxidizing agent, or least easily reduced. Of the half reactions listed in the chart, the lowest reduction potential is Eo = -2.931, and the substance getting reduced (the weakest oxidizing agent) is K+. Choice C 42. To balance a nuclear equation, the sum of the bottom numbers (total charge) and the sum of the top numbers (mass number) must be equal on both sides of the equation.

In this equation, we start with a total charge of (2+4) or +6. We must end with +6 total charge. Since the neutron already on the right side has 0 charge, the remaining isotope must have a +6 charge. In this equation we start with a total mass of (4+9) or 13. We must end with a mass of 13. Since the neutron already on the right side has 1 amu, the remaining isotope must have 12 amu. The remaining isotope has a charge of 6 and mass of 12. It is
12 6

C. Choice A

43.

Copper is deposited at the cathode: Cu2+(aq) + 2e- # Cu(s) 18.2

coul g 1molelectrons 1molCu x 45(60) sec x x x 63.5 sec mol 96500 coul 2 molelectrons

= 16.2 g Cu 44.

Choice A

Difference of mass: (236.9970 + 4.0015) 241.0046 = -0.0061 amu 0.0061 amu is the mass lost, that is, converted to energy. E = mc2 = 0.0061 u x 1.66054 x 10-27
kg x (2.998 x 108)2 = 9.10 x 10-13 J u

This is the energy released for one nucleus. For a mole:

J nulei x 6.022 x 1023 = 5.5 x 1011 J Choice E nucleus mol Alternate solution: The original masses in u, can also be considered to be g/mol, since u/atom is equivalent to g/mol

9.10 x 10-13

Mass lost = 0.0061 g/mol or 6.1 x 10-6 kg/mol E = mc2 = 6.1 x 10-6 kg (2.998 x 108)2
m2 = 5.5 x 1011 J 2 sec

Choice E

45. The equation for the cell reaction is: Cu(s) + 2Ag+(aq) # 2Ag(s) + Cu2+(aq) If we wanted to calculate the cell voltage under non-standard conditions, we could use the Nernst equation: E = Eo 0.0592 log Q n

Anything which increases Q lowers the cell voltage Anything which decreases Q raises the cell voltage.

This is equivalent to saying: Any change which shifts the reaction to the left (which would increase the value of Q), lowers the cell voltage. Any change which shifts the reaction to the right (which would decrease the value of Q), raises the cell voltage. Adding NaCl to the cathode side of the compartment would precipitate AgCl, lowering the Ag+ concentration. This would shift the reaction to the left, decreaseing cell voltage The size of the copper electrode is irrelevant. Solids have constant composition, and the amount of solid does not affect equilibrium, cell voltage, or reaction spontaneity. Adding Na2S to the anode side of the compartment would precipitate CuS, lowering the Cu2+ concentration, which shifts the reaction to the right, increasing cell voltage. Choice C

46.

Nuclear fusion is not controllable as of 2013. Choice E The cell reaction is: 3Cu(s) + 2Au3+(aq) # 2Au(s) + 3Cu2+(aq) ___ M 1.20 M For this reaction, Eo = 1.50 0.34 = 1.16 volts For this particular cell with the concentrations given, E = 1.13 volts E = Eo 0.0592 log Q n 0.0592 1.20 3 log 6 x2

47.

1.13 = 1.16 -

Solving: x = 0.040 M Choice E

48.

Reduction half reaction: MnO4- + 8H+ + 5e- # Mn2+ + 4H2O Oxidation half reaction: 2I- # I2 + 2eAdding the half reactions, multiplying the reduction half reaction by 2 and the oxidation half reaction by 5, in order to cancel electrons: 2MnO4- + 16H+ + 10I- # 2Mn2+ + 8H2O + 5I2 Choice E