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Chemistry 120B

Exam #3 3/27/09

Exam # A___

Instructions:
o Your cell phone must be off and all other materials must be put away
before beginning the exam.
o You are only allowed to use a SINGLE LINE NON-PROGRAMMABLE
CALCULATOR.
o Do not start the exam until you are told to do so.
o Print your name on the top of every page. One point will be removed
from your total score for every page on which you do not write your name.
o Read each problem carefully before you begin.
o Make sure you answer what the problem is asking.
o Answer each problem clearly and legibly.
o Check your work for errors.
 Always ask yourself Does this answer make sense?.
o Partial credit will be awarded for partial answers so always try!
o If there is any evidence of cheating (either during the exam or while it is
being graded) you will receive a zero for the exam and you will be
reported to the Dean of Students in the Office of Judicial Affairs.

This exam consists of this cover page, and 9 pages of problems. Make sure that all
10 pages are present.

Sign your name below and include the last four digits of your CWID (student ID
number). Failure to include the last four digits of your CWID will result in an automatic
score of zero.
Your signature indicates that you have read and understand these instructions.

Signature

Last 4 digits of CWID

Question # Points possible Your points


1
15
2
28
3
21
4
22
5
14

Hudson

Chemistry 120B Exam #3A

pg. 1 of 10

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Watch your units and significant figures.
1) Answer the following questions about acids and bases:

(15 points total)

a) Rank the following 0.1 M solutions in order of increasing acid strength. For each
compound, identify if the pH would be greater than, less than, or equal to 7.00.
(10 points)
Nitric acid (HNO3)
Potassium hydroxide (KOH)
Potassium fluoride (KF)
Sodium bromide (NaBr)
Ammonium bromide (NH4Br)
KOH (pH > 7.0) < KF (pH > 7.0) < NaBr (pH = 7.0) < NH4Br (pH < 7.0)< HNO3 (pH
< 7.0)
b) Is a 0.10 M solution of ammonium nitrite (NH4NO2) acidic, basic or neutral? Explain
your answer. (Kb, NH3 = 1.8 x 10-5, Ka, HNO2 = 4.6 x 10-4)
(5 points)
Ammonium nitrate breaks into NH4+ and NO2- in solution. The pH of the solution is
dependent on if NH4+ is a stronger acid or if NO2- is a stronger base.
If Kb, NH3 = 1.8 x 10-5, Ka, NH4+ = 1.0 x 10-14 / 1.8 x 10-5 = 5.55 x 10-10
If Ka, HNO2 = 4.6 x 10-4, Kb, NO2- = 1.0 x 10-14 / 4.6 x 10-4 = 2.2 x 10-11
Because Ka, NH4+ > Kb, NO2- the solution is acidic and has a pH < 7.0.

Hudson

Chemistry 120B Exam #3A

pg. 2 of 10

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2) Porphyrin (H2Por) can be considered as a weak diprotic acid. The ionization equilibria
for H2Por are shown as follows.
(28 points total)

H2Por(aq) + H2O(l)

HPor(aq) + H3O+(aq)

Ka1 = 5.6 10-6

HPor(aq) + H2O(l)

Por2(aq) + H3O+(aq)

Ka2 = 8.8 10-9

An aqueous solution of porphyrin is prepared by dissolving 0.25 mol of a porphyrin into


1.0 L of water.
a) Identify the correct conjugate acid/base pairs from the above equilibria.
Pairs
Acid
H2Por

Pairs
Conjugate base
HPor-

Base
H2 O

Conjugate base
Por2-

Base
H2 O

Pairs
Acid
HPor-

(6 points)

Conjugate Acid
H3 O+
Pairs
Conjugate Acid
H3 O+

b) Calculate the pH of the porphyrin solution prepared and justify if it is acidic, basic, or
neutral.
(8 points)
Because Ka1 >> Ka2, the majority of the [H3O+] comes from the loss of the first
proton.
H2Por (aq) + H2O (l)  HPor- (aq) + H3O+ (aq)
Initial
0.25 M
0
0
Change
-x
+x
+x
Equilibrium
0.25 x
x
x

Hudson

Chemistry 120B Exam #3A

pg. 3 of 10

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Watch your units and significant figures.
K a1 =

[ H 3O + ]eq [ HPor ]eq


[ H 2 Por ]eq

= 5.6 x10 6

x2
= 5.6 x10 6
0.25 x
assume x << 0.25
x2
= 5.6 x10 6
0.25
x = 1.18 x10 3 = 1.2 x10 3
check assumption
1.2 x10 3
x100% = 0.47% < 5%
0.25
assumption good !
x = 1.2 x 10-3 = [H3O+]
pH = -log[H3O+] = -log(1.2 x 10-3) = 2.92

This solution is acidic because pH < 7.


c) If 0.50 mol of HCl is added to the prepared porphyrin solution, what is the pH of the
solution after adding HCl? Note that the volume of HCl added is so small that you can
(6 points)
neglect.

Keep in mind that porphyrin is a weak diprotic acid. Therefore, this is a mixture of
a weak acid and a strong acid. The [H3O+] from a strong acid is the concentration
of the strong acid. This is a 1.0 L solution. 0.50 mol / 1.0 L = 0.50 M
pH = -log(0.50) = 0.30
d) Determine the equilibrium concentration of HPor in the porphyrin solution after
adding the HCl in part c. (If you could not calculate the [HCl] in part c, use 0.30 M.)
(8 points)
Because HCl is a strong acid, [HCl] = [H3O+]

H2Por (aq) + H2O (l)  HPor- (aq) + H3O+ (aq)


Initial
0.25 M
0
0.50 M
Change
-x
+x
+x
Equilibrium
0.25 x
x
0.50 + x

Hudson

Chemistry 120B Exam #3A

pg. 4 of 10

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Name:
Watch your units and significant figures.
K a1 =

[ H 3O + ]eq [ HPor ]eq


[ H 2 Por ]eq

= 5.6 x10 6

(0.50 + x)( x)
= 5.6 x10 6
0.25 x
assume x << 0.25, if x << 0.25 then x << 0.50
0.50 x
= 5.6 x10 6
0.25
x = 2.8 x10 6
check assumption
2.8 x10 6
x100% = 1.1x10 3% < 5%
0.25
assumption good !
[HPor-] = 2.8 x 10-6 M

Hudson

Chemistry 120B Exam #3A

pg. 5 of 10

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3) The role of a buffer solution is to control the pH of the solution over a narrow pH
range, to protect a solution against pH variations.
(21 points total)
a) Describe three methods of buffer preparation.

(6 points)

A buffer consists of a weak acid and its conjugate base. The [A-]/[HA] must range
from 0.10  10. The three methods to make a buffer are:
1) combine the weak acid and its conjugate base
2) combine a weak acid with a strong base
3) combine a weak base with a strong acid
b) If you prepare a solution by mixing substances in columns I and II together in equal
volume, predict if each of the following combinations is considered a buffer solution.
Why or why not? Explain or show your calculation clearly.
(15 points)

II

i)

0.10 M HCOOH

0.20 M HCOONa

ii)

0.25 M HCl

0.50 M CH3COOLi

iii)

0.66 M HBr

0.33 M Mg(OH)2

iv)

0.75 M HNO2

0.35 M KOH

v)

0.15 M C5H5N

3.0 M C5H5NHNO3

i) Yes, a buffer solution, weak conjugate acid/base pair with [A-]/[HA] = 2.


ii) Yes, a buffer solution, weak base + strong acid, will make a solution of 0.25 M
CH3COO- and 0.25 M CH3COOH, [A-]/[HA] = 1.
iii) No, not a buffer solution, strong acid + strong base
iv) Yes, a buffer solution, weak acid + strong base, will make a solution of 0.40 M
HNO2 and 0.35 M NO2-, [A-]/[HA] = 0.875.
v) No, not a buffer solution, weak conjugate acid/base pair BUT [A-]/[HA] = 0.05
which is NOT between 0.1 and 10.

Hudson

Chemistry 120B Exam #3A

pg. 6 of 10

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4) An unknown solution labeled 0.50 M is found on a lab bench. To determine the
composition of the solution you perform two potentiometric (pH meter) titrations, one
with a strong acid and the other with a strong base. The initial pH of the 0.50 M solution
in both experiments prior to adding strong acid or strong base is pH = 4.78. Below are
the plots of your results.
(22 points total)

pH

pH

pH = 4.78

pH = 4.78
mL titrant added

mL titrant added

a) Given the graphs above, and your knowledge of pH, is the unknown solution a weak
or strong acid or base? Identify which plot corresponds to the addition of strong acid
and which corresponds to the addition of strong base.
(4 points)

The unknown solution is a weak acid (pH < 7). The plot on the left is from the
addition of a strong acid (the pH just decreases is more acidic). The plot on the
right is from the addition of a strong base (the pH increases is more basic).
b) On the titration plot above, identify the buffer region(s) and the equivalence point(s).
Identify if the pH of the equivalence point is greater than, less than, or equal to 7.00.
(4 points)

Buffer
pH region
pH = 4.78

Equivalence
Point, pH > 7.0
mL titrant added

c) Using the data given in the problem, calculate the Ka of the unknown solution.
(8 points)

You have been given an initial concentration and an equilibrium concentration.


You need to calculate Ka. From the titration curve you know that this is a weak,
monoprotic acid.

Hudson

Chemistry 120B Exam #3A

pg. 7 of 10

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HA (aq) + H2O (l)  A- (aq) + H3O+ (aq)


Initial
0.50 M
0
0M
Change
-x
+x
+x
Equilibrium 0.50 x
x
x
+
4.78
pH = 4.78 [ H 3O ]eq = 10
x = 10 4.78
K a1 =
K a1 =

[ H 3O + ]eq [ A ]eq
[ HA]eq
(10 4.78 )(10 4.78 )
= 5.5 x10 10
4.78
0.50 10

d) Given your Ka and the information below, which of the following solutions exists in
the buffer region of the titration of the unknown solution? Identify the compound in the
unknown solution: (If you were unable to calculate a Ka, use Ka = 5.88 x 10-6) (6 points)
HOCl/OCl-

Ka = 2.9 x 10-8

HNO2/NO2-

Ka = 4.6 x 10-4

NH3/NH4+

Kb = 1.8 x 10-5

C5H5N/C5H5NH+

Kb = 1.7 x 10-9

If Ka = 5.5 x 10-10 then it doesnt match either HOCl or HNO2. Therefore, we need
to look at Kbs.
Kb = 1.0 x 10-14 / 5.5 x 10-10 = 1.8 x 10-5
The buffer present is NH3/NH4+. The solution contains NH4+.

Hudson

Chemistry 120B Exam #3A

pg. 8 of 10

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5) Answer the following solubility questions:

(14 points)

a) Determine the molar solubility of BaF2 in pure water (Ksp, BaF2 = 1.7 x 10-6)

(5 points)
Ksp = [Ba2+]eq[F-]2eq = 1.7 x 10-6
(s)(2s)2 = 1.7 x 10-6
4s3 = 1.7 x 10-6
s = 7.52 x 10-3 M
b) Qualitatively explain if the solubility of BaF2 would increase, decrease or not be
affected in the following solutions:
(9 points)
i)
0.0750 M solution of LiF

The solubility will decrease due to the addition of the common ion F-.
ii)

Solution with pH = 3.0

The solubility will increase because F- is a weakly basic anion. Solubility increases
as acidity increases (pH decreases).
iii)

0.0250 M solution of NaCl

The solubility will not change because NaCl does not have any interaction with
either Ba2+ or F-.

***10 pt BONUS PROBLEM:


Calculate the pH of the solution of BaF2 in part a. Ka, HF = 3.5 x 10-4.
[F-] = 2s = 2*7.5 x 10-3 = 1.5 x 10-2 M
F- (aq)
+ H2O (l)  HF (aq) + OH- (aq)
Initial
1.5 x 10-2 M
0
0
Change
-x
+x
+x
Equilibrium 1.5 x 10-2 x
x
x

Hudson

Chemistry 120B Exam #3A

pg. 9 of 10

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Kb =
Kb =

K w 1.0 x10 14
=
3.5 x10 4
Ka
[OH ]eq [ HF ]eq

[ F ]eq

= 2.86 x10 11

x2
= 2.86 x10 11
1.5 x10 2 x
assume x << 1.5 x10 2
x2
= 2.86 x10 11
2
1.5 x10
x = 6.547 x10 7 = 6.5 x10 7
check assumption
6.5 x10 7
x100% = 4.36 x10 3% < 5%
2
1.5 x10
assumption good !
[OH-] = 6.5 x 10-7 M
pOH = -log [OH-] = 6.18
pH = 14 pOH = 7.82

Hudson

Chemistry 120B Exam #3A

pg. 10 of 10