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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.
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Hudson
pg. 1 of 10
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
pg. 2 of 10
H2Por(aq) + H2O(l)
HPor(aq) + H3O+(aq)
HPor(aq) + H2O(l)
Por2(aq) + H3O+(aq)
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
pg. 3 of 10
= 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
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+]
Hudson
pg. 4 of 10
= 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
pg. 5 of 10
(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
Hudson
pg. 6 of 10
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)
Hudson
pg. 7 of 10
[ 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
pg. 8 of 10
(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)
The solubility will increase because F- is a weakly basic anion. Solubility increases
as acidity increases (pH decreases).
iii)
The solubility will not change because NaCl does not have any interaction with
either Ba2+ or F-.
Hudson
pg. 9 of 10
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
pg. 10 of 10