TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

PART I: EQUILIBRIUM
Part A: Formation of a Complex Ion

Anhydrous copper(II) sulfate is white, whereas hydrated copper(II) sulfate is blue. The
structure of the hydrated compound is more accurately represented by the chemical formula
[Cu(H2O)4]SO4•H2O, where four of the water molecules are bound directly to the copper(II) ion and
the fifth is a water of crystallization. When ammonia is added to a solution of the light blue
copper(II) cation, a deep blue color is formed immediately. The blue color is due to ligand exchange
between the water and the ammonia, as shown by the following equilibrium expression.

Cu(H2O + 4NH3  Cu(NH3 + 4H2O

The absorption spectrum of the

tetraamminecopper(II) cation, Cu(NH3 , is
shown to the left, and it is the primary copper
species in solution when up to 5M NH3 was been
achieved.

1. Identify the optimal wavelength of

absorption of the tetraamminecopper(II) cation.

620 nm (± 5 nm)

2. Identify the color of the visible spectrum

in which the cation absorbs the maximum
amount of energy.

Red to orange

3. Explain why the tetraamminecopper(II) solution appears blue.

The solution is absorbing the red/orange wavelengths of visible light and all of the
other colors pass through the solution; therefore, the eye would see a mixture of the
remaining colors (i.e. blue). Blue would be seen since it is the complementary color to
red-orange.
TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

4. Write the mass action expression for this equilibrium process.

Kf =

5. Explain how the addition of nitric acid will affect the equilibrium position in the formation
of the tetraamminecopper(II) cation, as shown on the previous page.

The H+ ions react with the ammonia in solution decreasing its concentration. The
equilibrium will therefore shift to the left, causing some of the
tetraamminecopper(II) ion to be consumed and the solution to become lighter.

OR

The H+ ions break up the tetraamminecopper(II) complex causing the formation of

NH4+ and Cu2+ ions. The reaction mixture will reestablish a new equilibrium position
based on the value of Kf since the concentrations of the reactants and products have
changed.

6. The formation constant, Kf, for the tetraamminecopper(II) ion is 2.1 x 1013 at 298K. What is
the concentration of Cu2+(aq) ions in a solution when 0.00150 mol of CuSO4 is added to
1.00L of 1.25 M NH3?

The Kf is huge; therefore, it can be assumed that all of the copper is used to form the
tetramminecopper(II) ion. However, we now this not to be true as a small degree of
dissociation will occur since an equilibrium position needs to be established.

Cu(H2O + 4NH3  Cu(NH3 + 4H2O

0 1.25 M – 0.00600 M 0.00150 M ----
+x +4x -x ----
x 1.25 – 0.00600 + 4x 0.00150 – x ----
≈ 1.25 M ≈ 0.00150 M

The initial concentration of the tetraamminecopper(II) ion will therefore be 0.00150

M. The initial concentration of the ammonia will be slightly less than the initial 1.25
M; however, since it is used in great excess, the concentration of the ammonia can be
approximated to be essentially the same as the initial amount.

Kf =

2.1 x 1013 =

[Cu2+] = 2.9 x 10-17 M

TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

7. The formation constant, Kf, of tetraamminecadmium(II) is 1.3 x 107 at 298K. In which of the
complex ions, Cu(NH3 or Cd(NH3 , are the ammonia ligands attached through stronger
coordinate covalent bonds to the center metal cation? Explain your answer.

The lower Kf value for tetraamminecadmium(II) indicates that a larger concentration

of ammonia molecules is present in the equilibrium mixture. This implies that the
degree of dissociation (the reverse reaction of formation) must be greater for the
tetraamminecadmium(II), so the coordinate covalent bonds must be weaker in this
complex. The tetraamminecopper(II) ion has the stronger coordinate covalent bonds.

Part B: Acid Rain

The pH value of pure water is 7.0, whereas natural rainwater is weakly acidic. This is caused
by dissolution of atmospheric carbon dioxide. In many areas, however, rainwater is more acidic.
This has many causes, some of which are natural and some of which derive from human activity. In
the atmosphere, sulfur dioxide and nitrogen monoxide are oxidized to sulfur trioxide and nitrogen
dioxide, respectively, which react with water to give sulfuric acid and nitric acid. The resulting so-
called “acid rain” has an average pH value of 4.5. Values as low as 1.7 have, however, been reported.
Sulfur dioxide is a diprotic acid in aqueous solution. At 25⁰C, the acidity constants are

SO2 + H2O  HS + H+ Ka1 = 1.20 x 10-2

HS S + H+ Ka2 = 6.61 x 10-8

The solubility of sulfur dioxide gas at 25⁰C is 33.9 liters in one liter of water at a sulfur dioxide
partial pressure of 0.987 atm. The pH of the saturated solution is 0.91.

8. Calculate the molar concentration of a saturated sulfur dioxide solution. Assume that the
change in volume due to the dissolution of SO2 is negligible.

PV = nRT

n=
⁄

M=
TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

9. Calculate the percentage of bisulfite ions in a saturated solution of sulfur dioxide.

The second dissociation will not occur as readily since Ka2 is much smaller than Ka1.

SO2 + H2O  HS + H+
1.37 M ----- 0 0
-x ----- +x X
1.37 – x ----- x x

One should not assume that the change in x will be negligible in this equilibrium
system, so the quadratic equation is needed, if solved through the equilibrium method.

x2 = 1.20 x 10-2(1.37 – x)
x2 = 0.0164 – 0.0120x
x + 0.0120x – 0.0164 = 0
2

x = 0.122 M HS
% comp =

N.B. The equilibrium method is not needed. One can use the pH, since the [H+] ≈
[HS ] in the saturated solution. [H+] = 10-0.91 = 0.123 M.

10. The dominant equilibrium in an aqueous solution of bisulfite ions is shown below:
2HS S + SO2 + H2O
Calculate the equilibrium constant for this equilibrium.

K = Ka2 x 1/Ka1 = (6.61 x 10-8)(1/1.20 x 10-2)

K = 5.51 x 10-6

11. Calculate the pH of a 0.0100 M aqueous solution of sodium sulfite.

Sulfite is the conjugate base of the bisulfite ion. Kb = Kw/Ka2 = 1.51 x 10-7

S + H2O  HS + O
0.0100 M ---- 0 0
-x ---- +x +x
0.0100 – x ---- x x
≈ 0.0100

[OH-] = 3.89 x 10-5

pOH = 4.41
pH = 14 – pOH = 9.59
TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

Part C: Titration
An unknown sample is titrated against a
0.40M NaOH solution. The titration curve is
to the right is collected..

12. What type of titration does this curve

represent?
a. A weak monoprotic acid by a
strong base.
b. A weak diprotic acid by a
strong base.
c. A weak triprotic acid by a
strong base.
d. A weak diprotic base by a
strong acid.
e. A strong monoprotic acid by a
strong base.

13. If point B has a pH of 1.85 and point D has a pH of 7.19, what is the concentration of the
major pH-determining species present at point C? Species = H+ from first dissociation
a. 1.41 x 10-2 M
b. 3.02 x 10-5 M pH at C = (pKa1 + pKa2)/2 which is (pt B + pt D)/2
c. 6.46 x 10-8 M
d. 6.21 x 10-10 M

14. If 20 mL of the 0.4 M titrant were added to reach point E, and the total volume at point E is
35 mL, what was the initial concentration of the unknown sample at point A?
a. 0.800 M
b. 0.533 M
c. 0.267 M Requires 0.008 mol OH- so 0.004 mol H2A must be present in 15 mL
d. 0.229 M
e. 0.114 M

15. A student is given a 0.10 M solution of the unknown sample. She uses 100 mL of the
unknown sample and titrates it completely with 0.1 M NaOH. A similar-shaped titration
curve, as shown above, is obtained. Calculate the pH at point E of this second titration.
a. 4.09
b. 7.50
c. 8.66
d. 9.85 Will need 200 mL equimolar base and the pKb2 (from question 13)
e. 10.1

Place the appropriate letter of the answer to the questions in the boxes below.
12. 13. 14. 15.
B B C D
TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

Part D: General Equilibrium Questions

16. CuO(s) + H2(g)  Cu(s) + H2O(g) + 2.0 kJ
When the substances in the equation above are at equilibrium at pressure P and
temperature T, the equilibrium can be shifted to favor the formation of the products by
a. increasing the pressure by means of a moving piston at constant temperature
b. increasing the pressure by adding an inert gas such as argon
c. decreasing the temperature of the system
d. allowing some gases to escape at constant pressure and temperature
e. adding a catalyst

17. Consider the following equilibrium system: C(s) + CO2(g)  2CO(g)

Given the data at constant volume below, which of the following statements about this
equilibrium process is false?
Temperature (⁰C) Percent CO(g) Percent CO2(g)
850 93.77 6.32
950 98.68 1.32
1050 99.63 0.37
1200 99.94 0.06
a. The reaction is endothermic.
b. The value of K is greater than 1 at all of the temperatures listed.
c. At 850⁰C, the value of K increases if the volume of the container is increased.
d. The value of K at 1200⁰C is larger than the value of K at 950⁰C.
e. None of the above statements are false.

18. The gaseous reaction N2(g) + 3H2(g)  2NH3(g) is at equilibrium when the volume is
suddenly doubled. Which is true of the reaction quotient Q relative to the equilibrium
constant K at the instant that the volume changes?
a. Q = 0.25K
b. Q = 0.50K
c. Q = K
d. Q = 2K
e. Q = 4K plug ½ concentration into mass action expression

19. At which of the points to the right can the

reaction be considered to be at equilibrium?

Place the appropriate letter of the answer to the questions in the boxes below.
16. 17. 18. 19.
C C E D
TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

Part E: Solubility of Calcium Hydroxide

20. Determine the solubility of calcium hydroxide under each of the following conditions. The
solubility-product constant of calcium hydroxide is 5.00 x 10-6 and its molar mass is 74.1
g/mol. Show any calculations in the space which follows the table.
pH = 12.00
Pure water 0.1 M Ca(NO3)2
buffer

Solubility
0.800 0.262 3.71
(g/L)

Ksp = [Ca2+][OH-]2

1. Ksp = x(2x)2 = 4x3 = 5.00 x 10-6

x = 0.0108 mol/L
(0.0108 mol/L)(74.1 g/mol) = 0.800 g/L

2. Ksp = (.1)(2x)2 = 5.00 x 10-6

x = 0.00354 mol/L
(0.00354 mol/L)(74.1 g/mol) = 0.262 g/L

3. Ksp = x(10-2)2 = 5.00 x 10-6

x = 0.050 M
(0.050 M)(74.1 g/L) = 3.71 g/L
TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

PART II: CHEMICAL REACTIONS & STOICHIOMETRY

Part A: Potassium Chlorate
Chlorates and perchlorates are used in manufacturing to produce such products as matches,
fireworks, and explosives. The first step in the production of potassium chlorate (KClO3) involves
the electrolysis of an aqueous solution of potassium chloride. At the anode, molecular chlorine is
produced. At the cathode, hydroxide ions are produced.

1. Write a balanced net ionic equation for the two electrode reactions.

Cathode: 2e- + 2H2O(ℓ)  2OH-(aq) + H2(g)

Anode: 2Cl-(aq)  Cl2(aq) + 2e-

2. The chlorine formed at the anode reacts with the hydroxide ions formed at the cathode to
form chlorate ions. Write a balanced net ionic reaction for the formation of chlorate ions
(and any other products) from molecular chlorine.

2e - + Cl2  2Cl-
6H2O + Cl2  2Cl + 10e- + 12H+  in base: 12OH- + Cl2  2 Cl + 10e- + 6H2O
Overall Equation: 3Cl2 + 6OH- 5Cl- + Cl + 3H2O

3. Calculate the mass of potassium chloride needed to produce 10 grams of potassium

chlorate.
1 mol Cl- would produce 1 mol Cl
moles KClO3 = (10 g)/(122.55 g/mol) = 0.0816 mol KClO3
∴ 0.0816 mol KCl needed to produce 10 grams of KClO3
mass KCl = (0.0816 mol)(74.55 g/mol) = 6.08 grams KCl

4. A student sets up an electrolytic cell with a saturated potassium chloride solution and
supplies an average current of 2.0 A. How many hours will it take for the student to prepare
10 grams of potassium chlorate?

0.0816 moles Cl produced from the removal of 6 electrons (1 electron to oxidize initial
chloride ion and 5 to oxidize the chlorine molecule to the chlorate ion)

moles of electrons = 6(0.0816 mol) = 0.490 mol e-

charge of electrons = (0.490 mol e-)(96485 C/mol e-) = 47278 C
t = q/I = (47278 C)/(2.0 C/s) = 23639 seconds
(23639 s)/(3600 s/hr) = 6.57 hours
TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

Part B: Unknown Solutions

You have been provided four unknown solutions, each containing one of the following solutes:
 calcium nitrate
 sodium carbonate
 sulfuric acid
 sodium chloride

Perform an experiment in order to identify each of the unknown solutions. You have been provided
only a pipette and a well plate to use for this portion of the examination.

5. Identify each of the solutions.

Solution A: Na2CO3

Solution B: NaCl

Solution C: H2SO4

Solution D: Ca(NO3)2

6. For any of the observed chemical reactions in your experiment, write the balanced net ionic
equation and identify the driving force for each reaction. Please note that not all of the
following boxes may be needed to answer the question.

Reaction #1: 2H+ + C  H2O + CO2 OR H+ + C HC

Driving Force Reaction #1: Formation of a gas (removal of ions from solution)

Reaction #2: Ca2+ + C  CaCO3

Driving Force Reaction #2: Formation of a precipitate (removal of ions from solution)

Reaction #3: Ca2+ + S  CaSO4

Driving Force Reaction #3: Formation of a precipitate (removal of ions from solution)

Reaction #4:

Driving Force Reaction #4:

TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

Part C: Types of Chemical Reactions

Questions 7-13 refer to the reactions represented below. The choices may be used more than once.
(A) A + 2S2  Ag(S2O3 +B
(B) C(s) + O2(g)  CO2(g)
(C) 2H2O2  2H2O + O2(g)
(D) 2Al(s) + 3CuSO4  Al2(SO4)3 + 3Cu(s)
(E) Ca2+ + Cr  CaCrO4(s)

7. A disproportionation reaction. (simultaneously oxidized and reduced)

8. A reaction in which the reaction rate could be increased in the presence of the enzyme
catalase.
9. Both a synthesis reaction and a redox reaction.
10. A combustion reaction.
11. A Lewis acid-base reaction resulting in a linear coordination complex.
12. A precipitation reaction.
13. A reaction in which a strong reducing agent forces a cation in solution to react.
14. A reaction which has resulted in an increase of a greenhouse gas in the lower atmosphere.

Place the appropriate letter of the answer to the questions in the boxes below.
7. 8. 9. 10.
C C B B

11. 12. 13. 14.

A E D B

Part D: Unknown Barium Compound

A student is given a barium halide compound in which she does not know the identity of the
halide ion. She dissolves 10.000-grams of the unknown barium compound in distilled water and
then dropwise adds a solution of sodium sulfate to form a precipitate. She continues adding the
sodium sulfate solution until no additional precipitate is observed. She filters and dries the
precipitate, whose mass is determined to be 11.132-grams.

15. Determine the identity of the halide ion. Your answer must include all relevant calculations.

Ba2+ + S  BaSO4
moles of BaSO4 = (11.132 grams)/(233.43 g/mol) = 0.0477 mol BaSO4
∴ 0.0477 mol Ba2+ must have been initially present in the unknown compound
Since the substance contains a halide, the formula would be BaX2, so the number of moles
of barium equals the number of moles of the original compound

molar mass of cmpd = (10.00 g)/(0.0477 mol) = 209.6 g/mol

mass of two halides = 209.6 – 137.33 = 72.3
mass of one halide = 72.3/2 = 36
The compound contains the chloride ion.

N.B. One can also determine the molecular mass by setting up a proportion between the two
given masses and the molar masses since the same ratio will exist between the two barium-
containing compounds.
TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

Part E: Unknown Ester

A student prepares a fragrant ester in lab which presents a pineapple-like odor. In order to
confirm the molecular formula of her ester, she performs the following two experiments.

Experiment #1: Combustion Analysis

The student places a 100.0-mg sample of the ester in a combustion chamber, as shown below.

In excess oxygen, the sample is combusted completely. The masses of the magnesium perchlorate
and sodium hydroxide sinks are given in the data table below.

Initial Mass of Magnesium Perchlorate Chamber 34.321 grams

Final Mass of Magnesium Perchlorate Chamber 34.414 grams
Initial Mass of Sodium Hydroxide Chamber 37.237 grams
Final Mass of Sodium Hydroxide Chamber 37.464 grams

Experiment #2: Mass Spectroscopy

The student obtained the following mass spectrum of her unknown ester sample.
TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________

16. Calculate the number of moles of water absorbed by the magnesium chlorate.

34.414 g – 34.321 g = 0.093 grams of water

moles of H2O = (0.093 g)/(18.02 g/mol) = 0.00517 mol H2O

17. Calculate the number of moles of carbon dioxide absorbed by the sodium hydroxide.

37.464 g – 37.237g = 0.227 grams of carbon dioxide

moles of CO2 = (0.227 g)/(44.01 g/mol) = 0.00516 mol CO2

18. Write a balanced chemical equation representing the reaction between the sodium
hydroxide pellets and the carbon dioxide gas. NET IONIC NOT NEEDED, BUT ACCEPTED

2NaOH + CO2  Na2CO3 + H2O OR NaOH + CO2  NaHCO3

19. Determine the empirical formula of the student’s ester. Recall that esters contain carbon,
hydrogen, and oxygen atoms.
(0.00517 mol H2O)( )( ) = 0.0104 grams H

(0.00516 mol CO2)( )( ) = 0.0620 grams C

mass of oxygen = 0.1000 g – (0.0104 g + 0.0620 g) = 0.0276 grams O

moles of O = (0.0276 g)/(16.00 g/mol) = 0.00173 mol O
C: (0.00516 mol C)/0.00173 = 3 mol C
H: (0.01034 mol H)/0.00173 = 6 mol H
O: 0.00173/0.00173 = 1 mol C
empirical formula: C3H6O

20. The student concludes that she has synthesized ethyl butanoate. Use evidence from the two
experiments to support or to refute her claim.

The peak of highest mass to charge ratio is approximately 116; therefore, the
unknown molecule would have a molecular mass of 116. Ethyl butanoate has the
chemical formula C6H12O2, which would have the same molecular mass seen from the
mass spectrum and the same empirical formula shown in the combustion analysis.

N.B. The two strong peaks at 71 and 43 provide support for the correct structure of
the ester as well. The analysis of the individual fragments is not needed for this
question; it is only provided for further clarification of the mass spectrum provided.
However, students should have been able to utilize the mass spectrum to determine
the molecular mass of the unknown ester by looking for the most massive m/z
fragment.
TEAM NAME: _____________________KEY_______________________ TEAM NUMBER: __________