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Test 1 2012 - Midterm 1 2012

Introductory Chemistry II (McMaster University)

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Chemistry 1AA3 Test 1 January 27, 2012

McMaster University VERSION 1
Instructors: P. Berti, J. Landry, P. Lock, H. Stöver
Duration: 100 min.

This test contains 18 numbered pages printed on both sides. There are 24 multiple-choice
questions appearing on pages numbered 3 to 15. Page 16 is extra space for rough work. Page
17 includes some useful data and equations. There is a periodic table on page 18. You may
tear off the last page to view the periodic table and to do your rough work.

You must enter your name and student number on the question sheets, as well as on the
answer sheet. Your invigilator will be checking your student card for identification.

You are responsible for ensuring that your copy of the question paper is complete. Bring any
discrepancy to the attention of your invigilator.

All questions are worth 2 marks each; the total marks available are 48. There is no additional
penalty for incorrect answers.

BE SURE TO ENTER THE CORRECT VERSION OF YOUR TEST (shown near the top of page
1), IN THE SPACE PROVIDED ON THE ANSWER SHEET.

ANSWER ALL QUESTIONS ON THE ANSWER SHEET, IN PENCIL.

Instructions for entering multiple-choice answers are given on page 2.

SELECT ONE AND ONLY ONE ANSWER FOR EACH QUESTION from the answers (A)
through (E). No work written on the question sheets will be marked. The question sheets may
be collected and reviewed in cases of suspected academic dishonesty.

Academic dishonesty may include, among other actions, communication of any kind (verbal,
visual, etc.) between students, sharing of materials between students, copying or looking at
other students’ work. If you have a problem, please ask the invigilator to deal with it for you. Do
not make contact with other students directly. Keep your eyes on your own paper – looking
around the room may be interpreted as an attempt to copy.

Only Casio FX 991 MS electronic calculators may be used; but they must NOT be transferred
between students. Use of periodic tables or any aids, other than those provided, is not allowed.

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OMR EXAMINATION – STUDENT INSTRUCTIONS

NOTE: IT IS YOUR RESPONSIBILITY TO ENSURE THAT THE ANSWER SHEET IS

PROPERLY COMPLETED: YOUT EXAMINIATION RESULT DEPENDS UPON
PROPER ATTENTION TO THESE INSTRUCTIONS.

The scanner, which reads the sheets, senses the bubble shaded areas by their non-
reflection of light. A heavy mark must be made, completely filling the circular bubble,
with an HB pencil. Marks made with a pen will NOT be sensed. Erasures must be
thorough or the scanner will still sense a mark. Do NOT use correction fluid on the
sheets. Do NOT put any unnecessary marks or writing on the sheet.
1. On SIDE 1 (red side) of the form, in the top box, in pen, print your student number,
name, course name, and the date in the spaces provided. Then you MUST write
your signature, in the space marked SIGNATURE.
2. In the second box, with a pencil, mark your student number, exam version number in
the space provided and fill in the corresponding bubble numbers underneath.
3. Answers: mark only ONE choice from the alternatives (A,B,C,D,E) provided for each
question. The question number is to the left of the bubbles. Make sure that the
number of the question on the scan sheet is the same as the number on the test
paper.
4. Pay particular attention to the Marking+ Directions on the form.
5. Begin answering the question using the first set of bubbles, marked “1”.

Version number

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VERSION 1.
Enter your version number in the correct column on
your scan sheet (see p. 2 for details).

1. The pH of a 0.01 M aqueous solution of a strong base is:

A) 3
B) 13
C) 12
D) 1
E) 7

2. Which of the following combinations of aqueous solutions would give a buffer? (All
solutions are 1.0 M).

A) 10 mL HClO4 + 20 mL KClO2
B) 15 mL HClO4 + 15 mL KClO4
C) 20 mL HClO4 + 10 mL KOH
D) 20 mL HClO2 + 10 mL KClO4
E) 10 mL HClO2 + 20 mL KOH

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3. Which of the following compounds will produce a basic solution when placed into
water?

(i) Na2O (ii) NH4Cl (iii) LiBr (iv) CH3COOK (v) CH3NH2

A) iii, v
B) i, ii
C) ii, iii, iv
D) ii, iv
E) i, iv, v

4. MES is a common buffer in chemical biology. At pH 6.5, the ratio of MES, a weak
base, to its conjugate acid, MESH+, is [MES]/[MESH+] = 2.19. What is the pKa of
MESH+?

A) 7.17
B) 7.47
C) 6.76
D) 5.65
E) 6.16

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5. Which of the following statements about buffers is false?

A) The percent ionization of the weak acid or weak base in a buffer is negligible
(close to zero).
B) Weak acid-strong base titration curves show a buffer region right up until the
equivalence point.
C) Buffers resist changes in pH by converting strong base into weak base, or strong
acid into weak acid.
D) The buffer capacity for a weak acid (HA) / weak base (A) system is at a maximum
when [HA] and [A] are equal.
E) A buffer's capacity can be exceeded by adding excess amounts of strong acid.

6. What is [H3O+] (in M) in 1.0 M CH3COOH(aq)?

Data:
Ka(CH3COOH) = 1.8 × 105

A) 1.66 × 103
B) 1.34 × 103
C) 3.22 × 103
D) 4.24 × 103
E) 7.18 × 103

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7. A buffer is made using only Tris (weak base) and TrisHCl (weak acid). What mass
(in g) of solid TrisHCl would be used to make 0.20 L of a buffer solution with a total
buffer concentration ([Tris] + [TrisH+]) of 0.050 M, and pH 7.80?

TrisH+ + H2O Tris + H3O+

Data:
pKa(TrisH+) = 8.30
mol wt(TrisHCl) = 157.6 g/mol
mol wt(Tris) = 121.1 g/mol

A) 10.5
B) 2.80
C) 1.20
D) 1.50
E) 0.80

8. What is the pH of the solution that results when the following substances are added to
water to create 1.00 L of solution?

0.100 mol HNO3

0.100 mol HNO2
0.300 mol NaNO2

Data:
Ka(HNO2) = 7.2 × 104

A) 3.53
B) 4.65
C) 6.04
D) 2.30
E) 3.14

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9. Bromophenol blue is an acid-base indicator with a pKa of 4.0. The acidic form is
yellow and the basic form is blue-violet. A few drops of this indicator are added to the
titration of benzoic acid (beaker, pKa = 4.20) with NaOH(aq) (buret). Find the false
statement(s) about this titration experiment.

(i) The indicator starts to change from yellow to blue-violet at about pH 3 and
completes the change from to blue-violet at about pH 5.
(ii) The indicator will be yellow over the entire buffer region of the titration curve.
(iii) The bromophenol blue indicator is not an appropriate choice for locating the
equivalence point of this titration.

A) No statements are false

B) i
C) ii
D) iii
E) i, iii

10. Which would be the best pH indicator to find the endpoint in a titration of 0.050 M
cacodylic acid with 0.100 M LiOH? (Cacodylic acid is a monoprotic acid.)

Data:
Ka(cacodylic acid) = 5.7 × 10-7

Indicator Colour change range (pH)

A) Methyl orange 3.1 - 4.4
B) Thymolphthalein 9.3 - 10.5
C) Cresol red 7.2 - 8.8
D) Bromophenol blue 3.0 - 4.6
E) Bromothymol blue 6.0 - 7.6

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11. Some parts of human cells, like the endosomes, are acidic, with pH  5.5. Which of the
following weak acids would be the most effective acid component of a buffer to
maintain pH 5.5 (assuming equal concentrations of all buffers)?

Weak acid Ka
A) glycine 4.6 × 10-3
B) lactic acid 1.4 × 10-4
C) H2PO4- 6.3 × 10-8
D) H2CO3 4.5 × 10-7
E) NH4+ 5.5 × 10-10

12. If the pH indicator cresol red (yellow at low pH, purple at high pH) is placed in a buffer
solution with pH 7.40, what percentage of the indicator would be in the protonated
(HIn) form?

Data:
pKHIn(cresol red) = 8.32

A) 19%
B) 79%
C) 9%
D) 39%
E) 89%

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13. Which of the following titration graphs is completely accurate?

Data:
Ka(benzoic acid) = 6.3 × 10-5
Kb(ammonia) = 1.8 × 10-5

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14. The titration of 10.00 mL of a weak base with a 0.180 M HCl(aq) solution reaches the
half-equivalence point after adding 4.75 mL of acid. The pH at the half-equivalence
point is 9.42. Calculate the initial concentration of the base and its Kb value.

A) 0.187 M Kb = 2.6 × 10-10

B) 0.171 M Kb = 2.6 × 10-5
C) 0.187 M Kb = 2.6 × 10-5
D) 0.171 M Kb = 3.8 × 10-10
E) 0.200 M Kb = 3.8 × 10-10

15. In a titration of 0.050 M NaOH (beaker) with 0.20 M HCl (buret), what is the pH at the
half-equivalence point?

A) 2.53
B) 3.33
C) 7.00
D) 11.55
E) 12.35

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16. A 1.00 L solution of a HCOOH/HCOONa buffer has pH 3.60, and

[HCOONa] = 0.68 M. After 50.0 mL of 1.00 M HCl are added, what is the new pH?

Data:
Ka(HCOOH) = 1.8 × 104

A) 3.49
B) 3.39
C) 3.44
D) 3.54
E) 3.61

17. A student titrates a weak acid (beaker, 20. mL, 0.22 M, Ka = 1.0 × 10-4) with NaOH
(buret, 0.12 M). Which of the following statements would be incorrect regarding this
titration?

A) The initial pH of the solution in the beaker would be below 4.

B) The equivalence point should occur at 37 mL of added NaOH.
C) The buffer region would occur at a pH above 7.
D) The half equivalence point would occur at pH 4.
E) At the equivalence point, the pH of the solution would be basic.

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18. Which statement is incorrect regarding the pseudo-zero order reaction A  G?

A) A graph of v0 vs. [A] is a horizontal line.

B) v = k[A]
C) average rate = -[A]/t
D) A graph of [A] vs. time is linear.
E) The plot of v vs. time is a horizontal line.

19. The table below shows the rate of formation of G during the reaction A  2G. What is
the rate constant for this reaction?
time (h) [G] (M)
1.0 0.12
2.0 0.24
4.0 0.48

A) 3.0 × 10-2 h-1

B) 6.0 × 10-2 M h-1
C) 3.0 M h-1
D) 0.030 M h-1
E) 0.060 h-1

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20. Which statement regarding the rate of the reaction 2A + B G + H is incorrect?

A) The reaction rate can be described as: average rate = [H]/t.

B) The reaction rate can be described as: average rate = –(1/2 × [A])/t.
C) The instantaneous reaction rate can be described as: v = –d[B]/dt.
D) If the reaction rate doubles with a doubling of either [A] or [B], then the rate law
may written as v = k[A][B].
E) The reaction order can be determined from the reaction stoichiometry shown
above.

21. Based on the observed rates, what is the rate law for the reaction A + B  G?
[A] (M) [B] (M) v0 (M/s)
0.1 0.1 0.4
0.1 0.3 1.2
0.2 0.2 3.2

A) v0 = k[A][B]
B) v0 = k[A]2[B]
C) v0 = k[A][B]2
D) v0 = k[A]0[B]
E) v0 = k[A]0[B]2

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22. Which statement regarding reaction rates is incorrect?

A) Initial rates can be approximated by measuring average rates at closely spaced time
points, and as close to time t = 0 as possible.
B) Instantaneous rates at time t can be approximated by measuring average rates over
a very small time interval about t.
C) Experimentally determined rates are always average rates.
D) Two reactions that have identical average rates over one time period must have
identical average rates over all subsequent time periods.
E) An instantaneous rate describes the rate of a reaction at a specific time, t.

23. The rate law for the reaction A + 2B  2C was determined to be v = k[A][B]2, with a
rate constant k = 1.2 × 10-2 M-2s-1 at 20°C. What is the reaction rate (in Ms-1) when
[A] = 0.1 M and [B] = 0.2 M?

A) 2.6 × 10-4
B) 4.4 × 10-4
C) 4.8 × 10-5
D) 1.2 × 10-5
E) 2.2 × 10-5

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24. Which of the following reactions is not third order overall?

A) v0 = k[B]2[C]0[D]
B) v0 = k[B][C][D]
C) v0 = k[B]3[C]0[D]0
D) v0 = k[A]2[C][D]
E) v0 = k[A][C]2[D]0

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Extra space for rough work.

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General data and equations. Other data appear with the questions.

There is a periodic table on the next page.

STP = 273.15 K, 1 atm F = 96485 C/mol

R = 8.3145 J/Kmol = 0.08206 Latm/Kmol NA = 6.022  1023 mol1
1 atm = 760 mm Hg = 101.325 kPa 0C = 273.15 K
1 J = 1 kg m2 s2 = 1 kPa·L = 1 Pa·m3 1 m = 109 nm = 1010 Å
1 cm3 = 1 mL 1 g = 103 mg

Kw = 1.0  1014

1 [A] 1 [G] lim 1 Δ[G] 1 d[G]

average rate  -   v  
a t g t t  0 g Δt g dt
v0 = k[A]m[B]n

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VERSION 1.
Enter your version number in the correct column on
your scan sheet (see p. 2 for details).

The correct answers are highlighted in blue.

The answer key is at the end.

1. The pH of a 0.01 M aqueous solution of a strong base is:

A) 3
B) 13
C) 12
D) 1
E) 7

With a strong base, [HO-] = [base].

[HO-] = 0.01 M.

pOH = -log(0.01)
=2

pH = 14 - pOH
= 12

2. Which of the following combinations of aqueous solutions would give a buffer? (All
solutions are 1.0 M).

A) 10 mL HClO4 + 20 mL KClO2
B) 15 mL HClO4 + 15 mL KClO4
C) 20 mL HClO4 + 10 mL KOH
D) 20 mL HClO2 + 10 mL KClO4
E) 10 mL HClO2 + 20 mL KOH

A) Limiting strong acid (HClO4) plus weak base (KClO2) gives a buffer.

B) Strong acid (HClO4) plus neutral salt (KClO4) gives a strong acid solution.

C) Strong acid (HClO4) plus limiting strong base (KOH) gives a strong acid
solution.

D) Weak acid (HClO2) plus neutral salt (KClO4) gives a weak acid solution.

E) Weak acid (HClO2) plus excess strong base (KOH) gives a solution of a weak
base salt (which has a negligible effect on pH) plus a strong base solution.
Overall, it is a strong base solution.

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3. Which of the following compounds will produce a basic solution when placed into
water?

(i) Na2O (ii) NH4Cl (iii) LiBr (iv) CH3COOK (v) CH3NH2

A) iii, v
B) i, ii
C) ii, iii, iv
D) ii, iv
E) i, iv, v

(i) Strong base (O2-)

(ii) Weak acid (NH4+)

(iii) Neutral salt (Li+ and Br -)

(iv) Weak base salt (CH3COO-)

(v) Weak base (an amine, R-NH2)

4. MES is a common buffer in chemical biology. At pH 6.5, the ratio of MES, a weak
base, to its conjugate acid, MESH+, is [MES]/[MESH+] = 2.19. What is the pKa of
MESH+?

A) 7.17
B) 7.47
C) 6.76
D) 5.65
E) 6.16

Henderson-Hasselbalch equation: pH = pKa + log([A-]/[HA])

Rearrange:
pKa = pH - log([A-]/[HA])
= 6.5 - log(2.19)
= 6.16

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5. Which of the following statements about buffers is false?

A) The percent ionization of the weak acid or weak base in a buffer is negligible
(close to zero).
B) Weak acid-strong base titration curves show a buffer region right up until the
equivalence point.
C) Buffers resist changes in pH by converting strong base into weak base, or strong
acid into weak acid.
D) The buffer capacity for a weak acid (HA) / weak base (A−) system is at a maximum
when [HA] and [A−] are equal.
E) A buffer's capacity can be exceeded by adding excess amounts of strong acid.

(A) True. This is already true for a weak acid or a weak base alone, but in a
buffer, the common ion effect further suppresses ionization.

(B) False. Our definition of a buffer includes the requirement that 0.1 < [A-]/[HA]
< 10. As a weak acid/strong base titration nears the equivalence point, there
is a region before the equivalence point where [A-]/[HA] > 10. There is too
little remaining HA for the solution to be an effective buffer.

(C) True. For example, when a limiting amount of NaOH is added to a benzoic
acid/benzoate buffer, HO- reacts with benzoic acid to produce an equal
amount of benzoate ion.

(D) True. The buffer capacity is maximal when the concentrations of both A- and
HA are large and equal.

(E) True. Once one equivalent of strong acid has been added, the solution is now
a weak acid solution, not a buffer. Any further addition of strong acid makes it
a strong acid solution.

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6. What is [H3O+] (in M) in 1.0 M CH3COOH(aq)?

Data:
Ka(CH3COOH) = 1.8 × 10−5

A) 1.66 × 10−3
B) 1.34 × 10−3
C) 3.22 × 10−3
D) 4.24 × 10−3
E) 7.18 × 10−3

This is a weak acid problem.

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

I 1.0 M - 0M 0M
C -xM - +xM +xM
E (1.0 - x) M - xM xM

Make the small x assumption (i.e., x << 1.0)

Ka = [A-][H3O+]/[HA] = x2/[HA].

Therefore:
x = √{Ka×[HA]}
= √{1.8 × 10-5 * 1.0}
= 4.24 × 10-3 M

[H3O+] = 4.24 × 10-3 M

7. A buffer is made using only Tris (weak base) and TrisHCl (weak acid). What mass
(in g) of solid TrisHCl would be used to make 0.20 L of a buffer solution with a total
buffer concentration ([Tris] + [TrisH+]) of 0.050 M, and pH 7.80?

TrisH+ + H2O Tris + H3O+

Data:
pKa(TrisH+) = 8.30
mol wt(TrisHCl) = 157.6 g/mol
mol wt(Tris) = 121.1 g/mol

A) 10.5
B) 2.80
C) 1.20
D) 1.50
E) 0.80

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First, calculate the required concentration of TrisHCl (HA) from the [A-]/[HA] ratio
(Henderson-Hasselbalch equation) and the total required concentration of ([A-]+
[HA]):

[A-]/[HA] = 10(pH-pKa)
= 10(7.8-8.3)
= 0.316

Therefore:
[A-] = 0.316[HA]

and

[A-] + [HA] = 0.05 M

so

1.316[HA] = 0.05 M

and

[HA] = 0.038 M

We require a 0.2 L solution, so:

n(TrisHCl) = 0.038 mol/L * 0.2 L
= 0.0076 mol

mass(TrisHCl) = 0.0076 mol * 157.25 g/mol

= 1.20 g

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8. What is the pH of the solution that results when the following substances are added to
water to create 1.00 L of solution?

0.100 mol HNO3

0.100 mol HNO2
0.300 mol NaNO2

Data:
Ka(HNO2) = 7.2 × 10−4

A) 3.53
B) 4.65
C) 6.04
D) 2.30
E) 3.14

If we consider that the strong acid (HNO3) will react with the weak base (NaNO2)
then we can construct the following mol table:

HNO3 NaNO2 Æ HNO2 NaNO3

before 0.100 0.300 0.100 0
after 0 0.200 0.200 0.100

HNO3 is completely consumed, forming NaNO3, a neutral salt. The remaining

solution is a buffer.

Use the Henderson-Hasselbalch equation:

pKa = -log(7.2 × 10−4) = 3.14

pH = pKa + log([A-]/[HA])
= 3.14 + log(0.200/0.200)
= 3.14

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9. Bromophenol blue is an acid-base indicator with a pKa of 4.0. The acidic form is
yellow and the basic form is blue-violet. A few drops of this indicator are added to the
titration of benzoic acid (beaker, pKa = 4.20) with NaOH(aq) (buret). Find the false
statement(s) about this titration experiment.

(i) The indicator starts to change from yellow to blue-violet at about pH 3 and
completes the change from to blue-violet at about pH 5.
(ii) The indicator will be yellow over the entire buffer region of the titration curve.
(iii) The bromophenol blue indicator is not an appropriate choice for locating the
equivalence point of this titration.

A) No statements are false

B) i
C) ii
D) iii
E) i, iii

(i) True. A pH indicator changes colour over the range of pH = pKHIn - 1 to

pH = pKHIn + 1.

(ii) False. Benzoic acid is a buffer in the region pH = pKa ± 1, or 3.2 to 5.2. At pH
5.2, bromophenol blue will be blue-violet.

(iii) True. An appropriate indicator would have pKHIn close to the pH at the
equivalence point, which would be > 7 in a weak acid/strong base titration.

10. Which would be the best pH indicator to find the endpoint in a titration of 0.050 M
cacodylic acid with 0.100 M LiOH? (Cacodylic acid is a monoprotic acid.)

Data:
Ka(cacodylic acid) = 5.7 × 10-7

Indicator Colour change range (pH)

A) Methyl orange 3.1 - 4.4
B) Thymolphthalein 9.3 - 10.5
C) Cresol red 7.2 - 8.8
D) Bromophenol blue 3.0 - 4.6
E) Bromothymol blue 6.0 - 7.6

We need to know the pH at the equivalence point before deciding on an

appropriate pH indicator.

In a weak acid/strong base titration, the product at the equivalence point will be a
weak base salt. Given the relative concentrations of cacodylic acid and LiOH, it
will take 1/2 of a volume of LiOH to neutralize the weak acid. The final volume will
be 1.5 times the starting volume, and the lithium cacodylate concentration will be
0.05 M ÷ 1.5 = 0.033 M.

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We need the Kb value to solve the equation for a weak base:

Kb(lithium cacodylate) = Kw/Ka(cacodylic acid)

= 10-14 / 5.7 × 10-7
= 1.75 × 10-8

We now set up an ICE table, with A- = cacodylate- and HA = cacodylic acid:

A- (aq) + H2O(l) HA(aq) + OH-(aq)

I 0.033 M - 0M 0M
C -xM - +xM +xM
E (0.033 - x) M - xM xM

Make the small x assumption (i.e., x << 0.033):

Kb = [HA][HO-]/[A-] = x2/[A-].

Therefore:
x = √{Kb×[A-]}
= √{1.75 × 10-8 * 0.033}
= 2.41 × 10-5 M
= [HO-]

pH = 14 - pOH
= 14 - (-log(2.41 × 10-5))
= 9.38

Thymolphthalein is the only indicator whose colour change occurs at close to the
equivalence point.

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11. Some parts of human cells, like the endosomes, are acidic, with pH ≈ 5.5. Which of the
following weak acids would be the most effective acid component of a buffer to
maintain pH 5.5 (assuming equal concentrations of all buffers)?

Weak acid Ka
A) glycine 4.6 × 10-3
B) lactic acid 1.4 × 10-4
C) H2PO4- 6.3 × 10-8
D) H2CO3 4.5 × 10-7
E) NH4+ 5.5 × 10-10

The best buffer will be the one with pKa closest to 5.5.

Weak acid pKa

glycine 2.34
lactic acid 3.85
H2PO4- 7.20
H2CO3 6.35
NH4+ 9.26

Only carbonic acid has a pKa within 1 pH unit of the target pH.

12. If the pH indicator cresol red (yellow at low pH, purple at high pH) is placed in a buffer
solution with pH 7.40, what percentage of the indicator would be in the protonated
(HIn) form?

Data:
pKHIn(cresol red) = 8.32

A) 19%
B) 79%
C) 9%
D) 39%
E) 89%

This is can be answered like a buffer question because pH indicators are weak
acids/bases.

Rearrange the Henderson-Hasselbalch equation (pH = pKa + log([A-]/[HA])):

[A-]/[HA] = 10(pH-pKa)
= 10(7.4-8.32)
= 0.12
or
[A-] = 0.12[HA]

We want to know the percent of the HA form:

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% HA = [HA]/([A-] + [HA]) * 100%

= [HA]/(0.12[HA] + [HA]) * 100%
= 1/1.12 * 100%
= 89%

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13. Which of the following titration graphs is completely accurate?

Data:
Ka(benzoic acid) = 6.3 × 10-5
Kb(ammonia) = 1.8 × 10-5

(A) Correct.
(B) Incorrect. The 1/2-equivalence point
should be at the pKa (4.2), not pH 7.
(C) Incorrect. Titrating a weak acid with a
strong acid.
(D) Incorrect. At the 1/2-equivalence
point pH = pKa = 4.2, not pH 9.
(E) Incorrect. The graph shows a strong
base/strong acid titration with no buffer
region. The 1/2-equivalence point for an
NH3/HCl titration would be at pKa(NH4+)
= 9.26.

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In versions 2 and 4, the x-axes (abscissa) in parts A and C were incorrectly

labelled, as announced during the test. The titles were correct. In part A, the
abscissa should have been "vol HCl (mL)", and in part C, it should have been "vol
NaOH (mL)". It is now apparent that this announcement was not clear in all test
rooms, and so answer A will also be awarded full marks in order to account for
those who changed the question titles to match the titration curve axes. Students
in the early/alternative write rooms did not receive any announcement, thus they
will receive full marks for any answer because of the time investment in the
question and lack of correct answer in the absence of the announcement.

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14. The titration of 10.00 mL of a weak base with a 0.180 M HCl(aq) solution reaches the
half-equivalence point after adding 4.75 mL of acid. The pH at the half-equivalence
point is 9.42. Calculate the initial concentration of the base and its Kb value.

A) 0.187 M Kb = 2.6 × 10-10

B) 0.171 M Kb = 2.6 × 10-5
C) 0.187 M Kb = 2.6 × 10-5
D) 0.171 M Kb = 3.8 × 10-10
E) 0.200 M Kb = 3.8 × 10-10

n(HCl) required to reach the 1/2-equivalence point:

n(HCl) = 0.180 mol/L * 4.75 × 10-3 L (or 0.180 mol/L * 4.75 mL * L/1000 mL)
= 8.55 × 10-4 mol

At the 1/2-equivalence point, [A-] = [HA], so the original n(base) is double that:

n(base) = 2 × 8.55 × 10-4 mol

= 1.71 × 10-3 mol

[base] = 1.71 × 10-3 mol / 0.01000 L

= 0.171 M

At the 1/2-equivalence point, pH = pKa = 9.42, therefore:

pKb = 14 - pKa
= 4.58

Kb = 10-pKb
= 10-4.58
= 2.6 × 10-5

15. In a titration of 0.050 M NaOH (beaker) with 0.20 M HCl (buret), what is the pH at the
half-equivalence point?

A) 2.53
B) 3.33
C) 7.00
D) 11.55
E) 12.35

We are not given the volumes of each solution, so we will solve this using relative
volumes. If the original volume of NaOH is v1, reaching the 1/2-equivalence point,
it would require:

vadded = v1(c1/c2) * 0.5 (for 1/2-equiv.)

= 0.050 M / 0.20 M * 0.5 * v1
= 0.125v1

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Therefore:
v2 = v1 + vadded
= 1.125v1

At the 1/2-equivalence point:

[NaOH] = 0.5 × c1 × v1/v2

= 0.5 × 0.05 M × 1/1.125
= 0.022 M
= [HO-]

pOH = -log(0.022)
= 1.65

pH = 14 - pOH
= 12.35

16. A 1.00 L solution of a HCOOH/HCOONa buffer has pH 3.60, and

[HCOONa] = 0.68 M. After 50.0 mL of 1.00 M HCl are added, what is the new pH?

Data:
Ka(HCOOH) = 1.8 × 10−4

A) 3.49
B) 3.39
C) 3.44
D) 3.54
E) 3.61

pKa(HCOOH) = -log(1.8 × 10-4)

= 3.74

Rearrange the Henderson-Hasselbalch equation as in question 12:

[A-]/[HA] = 10(pH-pKa)

or

[HA] = [A-]/10(pH-pKa)
= 0.68 M/10(3.60 - 3.74)
= 0.95 M

n(HCl) = 0.0500 L * 1.00 mol/L

= 0.0500 mol

Create a mol table to see how much weak base is converted to weak acid. We
started with a 1.00 L solution, so n(HCOOH) = [HCOOH], and
n(HCOONa) = [HCOONa].

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mol table:

HCOONa + HCl → HCOOH + NaCl

before 0.68 0.0500 0.95 0
after 0.63 0 1.00 0.05

pH = pKa + log([HCOONa]/[HCOOH])
= 3.74 + log(0.63/1.00)
= 3.54

17. A student titrates a weak acid (beaker, 20. mL, 0.22 M, Ka = 1.0 × 10-4) with NaOH
(buret, 0.12 M). Which of the following statements would be incorrect regarding this
titration?

A) The initial pH of the solution in the beaker would be below 4.

B) The equivalence point should occur at 37 mL of added NaOH.
C) The buffer region would occur at a pH above 7.
D) The half equivalence point would occur at pH 4.
E) At the equivalence point, the pH of the solution would be basic.

(A) Correct. This is a weak acid solution, pH = 2.33. (Solve as for question 6.)

(B) Correct. n(weak acid) = 0.02 L * 0.22 mol/L = 0.0044 mol

vol(NaOH) = 0.0044 mol / 0.12 mol/L = 0.037 L, or 37 mL.

(C) Incorrect. pKa = -log(1.0 × 10-4) = 4.0

Therefore, the buffer region will be pH 3.0 to 5.0.

(D) Correct. At the 1/2-equivalence point, pH = pKa = 4.0 (see part C).

(E) Correct. At the equivalence point, the weak acid would have been converted
to a weak basic salt solution, with pH > 7.

18. Which statement is incorrect regarding the pseudo-zero order reaction A → G?

A) A graph of v0 vs. [A] is a horizontal line.

B) v = k[A]
C) average rate = -Δ[A]/Δt
D) A graph of [A] vs. time is linear.
E) The plot of v vs. time is a horizontal line.

(A) Correct. v0 does not vary with [A], so the plot will be a horizontal line.

(B) Incorrect. v = k; it does not depend on [A].

(C) Correct. The negative sign is used because we're following the decrease in
reactant, A.

(D) Correct. The rate does not vary with [A], so [A] decreases at a constant

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(linear) rate as a function of time.

(E) Correct. v does not change with time, so the plot is horizontal.

19. The table below shows the rate of formation of G during the reaction A → 2G. What is
the rate constant for this reaction?
time (h) [G] (M)
1.0 0.12
2.0 0.24
4.0 0.48

A) 3.0 × 10-2 h-1

B) 6.0 × 10-2 M h-1
C) 3.0 M h-1
D) 0.030 M h-1
E) 0.060 h-1

[G] increases linearly with time (always 0.12 M/h), so this is a zero order reaction.
For a zero order reaction v = k.

k = v = 1/g × ΔG/Δt
= ½×0.12 M / 1.0 h
= 0.06 M/h or 6.0 × 10-2 M h-1.

20. Which statement regarding the rate of the reaction 2A + B → G + H is incorrect?

A) The reaction rate can be described as: average rate = Δ[H]/Δt.

B) The reaction rate can be described as: average rate = –(1/2 × Δ[A])/Δt.
C) The instantaneous reaction rate can be described as: v = –d[B]/dt.
D) If the reaction rate doubles with a doubling of either [A] or [B], then the rate law
may written as v = k[A][B].
E) The reaction order can be determined from the reaction stoichiometry shown
above.

(A) Correct. The symbol Δ is used for average rates to denote finite differences
in time.

(B) Correct. It is negative because we are following the decrease in reactant

concentration, and 1/2 because the stoichiometry is 2 equivalents of
A per equivalent of B.

(C) Correct. "d" is used to indicate the limit as Δt → 0.

(D) Correct. The reaction is first order with respect to (w.r.t.) both A and B, and
second order overall.

(E) Incorrect. There is not (necessarily) any relationship between stoichiometry

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and the rate law.

21. Based on the observed rates, what is the rate law for the reaction A + B → G?
[A] (M) [B] (M) v0 (M/s)
0.1 0.1 0.4
0.1 0.3 1.2
0.2 0.2 3.2

A) v0 = k[A][B]
B) v0 = k[A]2[B]
C) v0 = k[A][B]2
D) v0 = k[A]0[B]
E) v0 = k[A]0[B]2

Comparing lines 1 and 2, the rate triples when [B] triples, so the reaction is first
order with respect to (w.r.t.) [B].

Given the fact that the reaction is first order w.r.t. [B], the reaction rate would be
0.8 M/s in line 3 if the reaction were zero order w.r.t. [A]. However, doubling [A]
further quadrupled v0 to 3.2 M/s, meaning that the reaction is second order w.r.t.
[A].

More formally:

v0(line3)/v0(line 1) = k[A3]m[B3]1/ k[A1]m[B1]1 (cancel k's)

3.2 M/s / 0.4 M/s = {(0.2 M)m × (0.2 M)1 } / {(0.1 M)m × (0.1 M)1 }

8 = 2m ×2 (the A and B terms must be

treated separately because if m
and n are not equal, then the
units (M2 and M) will not be
equal)

therefore:

m=2

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22. Which statement regarding reaction rates is incorrect?

A) Initial rates can be approximated by measuring average rates at closely spaced time
points, and as close to time t = 0 as possible.
B) Instantaneous rates at time t can be approximated by measuring average rates over
a very small time interval about t.
C) Experimentally determined rates are always average rates.
D) Two reactions that have identical average rates over one time period must have
identical average rates over all subsequent time periods.
E) An instantaneous rate describes the rate of a reaction at a specific time, t.

(A) Correct.

(B) Correct.

(C) Correct.

(D) Incorrect. As seen in the notes, many reactions can have an average rate of
1 M/min over the first minute, but different rates over other time
periods, depending on the order of the reaction.

(E) Correct.

23. The rate law for the reaction A + 2B → 2C was determined to be v = k[A][B]2, with a
rate constant k = 1.2 × 10-2 M-2s-1 at 20°C. What is the reaction rate (in Ms-1) when
[A] = 0.1 M and [B] = 0.2 M?

A) 2.6 × 10-4
B) 4.4 × 10-4
C) 4.8 × 10-5
D) 1.2 × 10-5
E) 2.2 × 10-5

v0 = k[A][B]2
= (1.2 × 10-2 M-2s-1) * (0.1 M) * (0.2 M)2
= 4.8 × 10-5 Ms-1

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24. Which of the following reactions is not third order overall?

A) v0 = k[B]2[C]0[D]
B) v0 = k[B][C][D]
C) v0 = k[B]3[C]0[D]0
D) v0 = k[A]2[C][D]
E) v0 = k[A][C]2[D]0

(D) Is 4th order overall: v0 = k[A]2[C][D]

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Answer key, version 1.

1. C
2. A
3. E
4. E
5. B
6. D
7. C
8. E
9. C
10. B
11. D
12. E
13. A
14. B
15. E
16. D
17. C
18. B
19. B
20. E
21. B
22. D
23. C
24. D

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Answer key, version 2.

1. A
2. D
3. A
4. A
5. E
6. E
7. C (full marks will be awarded for answer A also)
8. B
9. A
10. B
11. D
12. E
13. D
14. B
15. A
16. D
17. A
18. E
19. D
20. A
21. E
22. B
23. A
24. C

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Answer key, version 3.

1. D
2. D
3. A
4. B
5. B
6. E
7. A
8. A
9. C
10. D
11. C
12. A
13. C
14. B
15. E
16. B
17. C
18. B
19. B
20. D
21. B
22. A
23. B
24. E

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Answer key, version 4.

1. E
2. B
3. A
4. C
5. C
6. E
7. C (full marks will be awarded for answer A also)
8. E
9. B
10. A
11. E
12. B
13. E
14. A
15. C
16. E
17. B
18. E
19. D
20. D
21. E
22. A
23. C
24. B

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