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2) The nitro group, -NO2, is a powerful electron-withdrawing group. Knowing this,

arrange the following substituted benzoic acids from strongest to weakest.

a) C > D > A > B b) D > A > B > C c) A > B > C > D

d) D > B > C > A e) C > D > B > A

Two things to watch here are 1) the distance from the COOH group and 2) the number of electron-withdrawing
groups. On this basis, C is definitely the strongest ad A the weakest. B would be stronger than A since it is
closer and, finally, D falls in between C and B since it has two groups withdrawing electrons.

3) Calculate the molar solubility of calcium carbonate (CaCO3) in 0.10M

Na2CO3 (Ksp = 2.8 × 10-9 for calcium carbonate).
a) 1.3 × 10-8 b) 0.10 c) 2.8 × 10-8 d) 5.3 × 10-5
e) Cannot be calculated without knowing Ksp for the sodium carbonate.

For this, write out the equation for Ksp, rearrange, and solve for the calcium ion concentration (this would be the
molar solubility of calcium carbonate by definition). This is done below.

4) Examine the titration curve shown below. The volume of titrant required to reach
the stoichiometric point of the titration is approximately

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a) 10 mL b) 20 mL c) 30 mL d) 40 mL e) 90 mL

This is a simple reading of the graph! The volume at the place where the curve is most vertical would be the
stoichiometric end point. This would, of course, be a about 40 ml.

5) The common ion effect is an example of

a) le Châtelier's principle b) Trouton's rule c) Hess' law
d) the Heisenberg uncertainly principle e) None of these

Adding the common ion drives the reaction in the direction that removes excess ion to restore equilibrium. C'est
le Châtelier!

6) The strong acid, HCl, reacts with the equally strong base, CsOH. What
is the pK of this reaction?
a) -14.00 b) +14.00 c) -7.00 d) + 7.00 e) 1.0 × 10+14

A reaction of a strong acid with a strong base in aqueous solution is always just H+ + OH— ↔ H2O. This is the
reverse of autoprotolysis (the dissociation of water). Thus, pK = —pKw = —14.00. If this is not clear, review
your logarithms and the meaning of "p."

7) A buffer is prepared by mixing 0.100 moles of a weak acid (Ka = 4.6 × 10-7)
with 0.0300 moles of NaOH. What is the pH of the resulting solution?
a) 6.34 b) 7.00 c) 6.18 d) 6.71 e) 5.97

The 0.0300 moles of NaOH would removed 0.0300 moles of HA and leave 0.070 moles of the latter. (Would you
really need to write the reaction to do this?) So, we have [A—]/[HA] = 0.0300/0.070. In addition, we have pKa =
6.337. So, plugging into the Henderson-Hasselbalch equation gives us, simply, pH = 6.337 + log(0.0300/0.070) =
6.337 — 0.368 = 5.969.

8) Which of the following solutions would have the highest pH?

a) 0.10M sulfuric acid b) 0.10M ammonia c) 0.10M calcium hydroxide
d) 0.15M sodium hydroxide e) Cannot be determined

0.10M sulfuric acid would have a low pH! (d) would be 0.15M in hydroxide and (c) would be 0.20M in hydroxide
since it is a strong base and has the formula, Ca(OH)2. Ammonia is a weak base and (b) is thus out of the
running. (c) is the obvious correct answer.

9) If 555 mg of sodium acetate (82.04 g/mol) are added to 250.0 mL of 0.015M

Pb(NO3)2, will a precipitate form? (Ksp = 1.8 × 10-3 for lead acetate)
a) Yes, because Ksp > Q b) No, because Ksp > Q

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c) Yes, because Ksp < Q d) No, because Ksp < Q

e) No, since K sp = Q

The concentration of acetate (before reaction and thus in Q) would be (0.555 g)/[82.04 g/mol × 0.250L] =
0.02706M. So, Q = [Pb2+][OAc—]2 = (0.015)(0.02706)2 = 1.10 × 10-5. We see that K > Q; this means that the
reaction goes to the right which, in turn, means that no precipitate forms!

10) Which of the following is NOT a strong acid (aq solution)?

a) HCl b) HClO4 c) H2SO4 d) HI e) HF

If you have a valid excuse for missing this one, we'd sure like to know what it is!

11) A weak acid, HA, is 0.500% dissociated in the 0.400M solution of the acid.
What is K a of this acid?
a) 5.00 × 10-3 b) 1.01 × 10-5 c) 1.00 × 10-4 d) 0.0707 e) 14.00

The above is an example of where we get K from known concentrations. In this case, we know the percent
dissociation and that gives us the H+ and A- concentrations. (Note that, from stoichiometry, we must have [H+ ] =
[A- ].) Conservation of mass gives the needed value for [HA]. Note that a shortcut for getting this would have been
[HA] = 0.995[HA]0 (why?).

Compare this problem to #25. See if you understand the similarities and differences.

12) What is the pH of a 0.250M solution of acetic acid (Ka = 1.8 × 10-5, 25°C)?
a) 11.32 b) 11.30 c) 0.60 d) 2.70 e) 2.68

Iteration is the easiest but you can use any method you wish. Below is the solution worked out in detail by the
iteration method.

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13) How many of the following substances (0.10M, aq) would have pH > 7?
H2SO4 Na3PO4 NH3 NH4Cl KCN HNO3 KNO3
a) 0 b) 1 c) 2 d) 3 e) 4

We retype the list showing the pH values. We'll then let you count!

H2SO4(pH < 7) Na3PO4(pH > 7) NH3(pH > 7) NH4Cl(pH < 7) KCN(pH > 7) HNO3(pH <
7) KNO3(pH = 7)
(Strong acid) (Weak base) (Weak base) (Weak acid) (Weak base) (Strong
acid) (Neutral salt)

14) Examine the following titration curve. Which of the possibilities listed below
is the most likely for this curve to represent?

a) HCl titrated by NaOH b) HCl titrated by NH3 c) Ca(OH)2 titrated by HCl

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d) H2SO4 titrated by KOH e) NH3 titrated by HCl

From the shape of the curve, it should be obvious that this is a strong base titrated by a strong acid. (c) is, thus,
the obvious choice. (e) is out since ammonia would have pronounced "dip" at the start.

15) How many of the following substances can be either an acid or a base
(in the Brønsted-Lowry sense) in aqueous solution?
H3PO4 H2O H2PO42- HSO3-
a) 0 b) 1 c) 2 d) 3 e) 4

Phosphoric acid can only donate protons; it cannot accept them. The other three species can both donate and accept
protons. Thus, (d) is the answer.

16) The titration curve below is for a 100.0 mL sample of NaOH titrated by 0.20M HCl.
What is the best estimate for the concentration of the original solution (the molarity of
the NaOH)?

a) 0.010M b) 0.020M c) 0.0080M d) 0.040M e) 0.080M

The volume at neutralization is 40 mL. So, if we just plug in to the simple formula, we get [NaOH] =
(0.20)(40)/100.0 = 0.080M.

17) What is the correct Ksp expression for Ag2CrO4?

a) [Ag+ ]2[Cr3+][O2-]4 b) [Ag+ ]2[CrO42-] c) [Ag+ ][CrO42-]
d) [2Ag+ ]2[CrO42-] e) [Ag+ ][CrO42-]2

If you missed this, what is wrong with you? This is a direct quote of a simple definition!

18) How many of the following systems can be used to make a buffer?
{0.10 mol NaOH + 0.10 mol HCl}
{0.050 mol NaOH + 0.10 mol acetic acid}
{0.10 mol sodium acetate + 0.050 mol acetic acid}
{0.10 mol sulfuric acid + 0.050 mole acetic acid}
{0.10 mol ammonia + 0.050 mol nitric acid}
a) 0 b) 1 c) 2 d) 3 e) 4

The first is ruled out since a strong acid/strong base combination cannot be a buffer. The second is OK since equal
moles of acetic acid and acetate ion are present. The third is OK, too, since both acetic acid and its conjugate base
are present. The fourth is absurd since it is a mixture of two acids. The fifth, and last, is OK since you have equal
moles of ammonia and ammonium at equilibrium. So, counting up gives you 3 buffers.

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19) Aqueous solutions containing Al3+ ion are sour to the taste. Aluminum ion,
like many ions exists as a hexahydrate in solution (i.e., Al(H20)63+). Which
of the following is the most likely explanation of this phenomenon?
a) Aluminum ion is a Brønsted base.
b) Aluminum ion has an insoluble hydroxide, Al(OH)3.
c) Al(H2O)63+(aq) ↔ Al(H2O)5(OH- )2+(aq) + H+ (aq)
d) Al(OH)3(s) + OH- (aq) ↔ Al(OH)4- (aq)
e) None of these is a plausible explanation.

Acids are sour and aqueous solutions of acids contain H+ (which is what gives a sour taste). (c) clearly shows a
reaction that can account for this and is, in fact, what Lewis acid cations do when dissolved in water. This was a
problem involving you reaching a conclusion from a balanced chemical equation!

20) The pH of a 0.250M solution of barium hydroxide (pKw = 14.000) would be

a) 0.602 b) 13.398 c) 0.301 d) 13.699 e) Need K b of base to do this

Barium hydroxide, Ba(OH)2, is a strong base. Thus a 0.250M solution of this would have a 0.500M solution of
hydroxide. So, pH = pKw + log[OH- ] = 14.000 + (-0.301) = 13.699.

21) Which of the following is the best estimate for the pH value of a 0.388M
solution of HNO3?
a) 0.411 b) 0.589 c) -0.411 d) -0.589 e) 7.000

This is a strong acid. Thus, pH = -log(0.388) = +0.411.

22) For a given acid, pKa = 5.85. What is pKb of its acid anion?
a) 5.85 b) 8.15 c) 7.00 d) -5.85 e) None of these

pKb = pKw - pKa = 14.00 - 5.85 = 8.15. If you missed this, you are missing something!

23) What is the pH of a 0.250M solution of ammonia (Kb = 1.8 × 10-5, 25°C)?
a) 11.32 b) 11.30 c) 0.60 d) 2.70 e) 2.68

If this looks a lot like the solution to problem 12 (but with hydroxide instead of H+ ) you should not be surprised!
K a of acetic acid is the same value as Kb of ammonia and both solutions are at the same concentration. You could
have just use the answer from the other problem (subtracted from 14) to do this one! Anyway, for those who did
not notice that...

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Carefully compare this answer to the answer for problem #12. This is one of those cases where I cater to the
student quickest on his feet.

24) Examine the following titration curve. What is the best estimate of the pH at
equivalence (stoichiometric) point?

a) 5 b) 7 c) 1 d) 12 e) Cannot be determined.

There is more than one way to figure this out. First, you know that this is a strong base/strong acid titration curve
from the shape of the curve (and, for that matter, from some of the other problems (#16 in particular and #14 to a
lesser extent). For such a system, pH = 7 at the stoichiometric point. Another way to do this would be just to
read the graph. The only possible numbers for the pH from the list given are 5 and 7. 7 is more centrally located
and, thus, is really the most logical choice. Knowing either of the things just mentioned makes you fairly sure of
the answer; knowing both makes you absolutely sure!

25) Saccharin is a weak monoprotic acid. The pH of a 0.0150M solution of saccharin

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is 5.53. What is the Ka of this acid?

a) 2.0 × 10-4 b) 2.9 × 10-6 c) 5.8 × 10-10 d) 8.4 × 10-12 e) None of these

This one is another example (cf. problem #11) in which the concentrations are known (or can be deduced) and then
used to immediately calculate the equilibrium constant. You should see immediately that, for a monoprotic acid,
HA, we must have [H+ ] = [A- ]. The concentration of remaining acid, after dissociation, is just [HA]0 - [A- ] =
[HA]0 - [H+ ] = [HA]. We carry out the needed calculations below.

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