1993

#3
I. 2Mn2+ + 4OH¯ + O2(g) ---> 2MnO2(s) + 2H2O
II. MnO2(s) + 2I¯ + 4H+ ---> Mn2+ + I2(aq) + 2H2O
III. 2S2O32¯ + I2(aq) ---> S4O62¯ + 2I¯

The amount of oxygen, O2, dissolved in water can be determined by titration. First, MnSO 4 and NaOH are
added to a sample of water to convert all of the dissolved O 2 to MnO2, as shown in equation I above. Then
H2SO4 and KI are added and the reaction represented by equation II proceeds. Finally, the I 2 that is
formed is titrated with standard sodium thiosulfate, Na2S2O3, according to equation III.

(a) According to the equations above, how many moles of S2O32¯ are required for analyzing 1.00 mole of
O2 dissolved in water?
(b) A student found that a 50.0 milliliter sample of water required 4.86 milliliters of 0.0112 molar
Na2S2O3 to reach the equivalence point. Calculate the number of moles of O 2 dissolved in this sample.
(c) How would the results in (b) be affected if some I 2 were lost before the S2O32¯ was added? Explain.
(d) Name an appropriate indicator for the reaction shown in equation III and describe the change you
would observe at the end point of the titration.

#5
The following observations are made about reactions of sulfuric acid, H 2SO4. Discuss the chemical
processes involved in each case. Use principles from acid-base theory, oxidation-reduction, and bonding
and/or intermolecular forces to support your answers.

(a) When zinc metal is added to a solution of dilute H2SO4, bubbles of gas are formed and the zinc
disappears.
(b) As concentrated H2SO4 is added to water, the temperature of the resulting mixture rises.
(c) When a solution of Ba(OH)2 is added to a dilute H2SO4 solution. the electrical conductivity decreases
and a white precipitate forms.
(d) When about 10 milliliters of 0.10 molar H2SO4 is added to 40 milliliters of 0.10 molar NaOH the pH
changes only by about 0.5 unit. After 10 more milliliters of 0.10 molar H 2SO4 is added, the pH changes
by about 6 units.

#6
Account for each of the following in terms of principles of atomic structure, including the number,
properties, and arrangements of subatomic particles.

(a) The second ionization energy of sodium is about three time greater than the second ionization energy
of magnesium.
(b) The difference between the atomic radii of Na and K is relatively large compared to the difference
between the atomic radii of Rb and Cs.
(c) A sample of solid nickel chloride is attracted into a magnetic field, whereas a sample of solid zinc
chloride is not.
(d) Phosphorus forms the fluorides PF3 and PF5, whereas nitrogen forms only NF3.
1993 (Continued)
#9
Observations about real gases can be explained at the molecular level according to the kinetic molecular
theory of gases and ideas about intermolecular forces. Explain how each of the following observations
can be interpreted according to these concepts, including how the observation supports the correctness of
these theories.

(a) When a gas-filled balloon is cooled, if shrinks in volume; this occurs no matter what gas is originally
placed in the balloon.
(b) When the balloon described in part (a) is cooled further, the volume does not become zero; rather, the
gas becomes a liquid or solid.
(c) When NH3 gas is introduced at one end of a long tube while HCl gas is introduced simultaneously at
the other end, a ring of white ammonium chloride is observed to form in the tube after a few minutes.
This ring is closer to the HCl end of the tube than the NH 3 end.
(d) A flag waves in the wind.

1995
#7
Explain the following in terms of the electronic structure and bonding of the compounds considered.

(a) Liquid oxygen is attracted to a strong magnet, whereas liquid nitrogen is not.
(b) The SO2 molecule has a dipole moment, whereas the CO 2 molecule has no dipole moment. Include the
Lewis (electron-dot) structures in your explanation.
(c) Halides of cobalt(II) are colored, whereas halides of zinc(II) are colorless.
(d) A crystal of high purity silicon is a poor conductor of electricity; however, the conductivity increases
when a small amount of arsenic is incorporated (doped) into the crystal.

1996
#4
Concentrated sulfuric acid (18.4-molar H2SO4) has a density of 1.84 grams per milliliter. After dilution
with water to 5.20-molar, the solution has a density of 1.38 grams per milliliter and can be used as an
electrolyte in lead storage batteries for automobiles.

(a) Calculate the volume of concentrated acid required to prepare 1.00 liter of 5.20-molar H 2SO4.
(b) Determine the mass percent of H2SO4 in the original concentrated solution.
(c) Calculate the volume of 5.20-molar H2SO4 that can be completely neutralized with 10.5 grams of
sodium bicarbonate NaHCO3.
2001
#5
Answer the questions below that related to the five aqueous solutions at 25 oC shown below.

a) Which solution has the highest boiling point? Explain.

b) Which solution has the highest pH? Explain.
c) Identify a pair of the solutions that would produce a precipitate when mixed together. Write the
formula of the precipitate.
d) Which solution could be used to oxidize the Cl-(aq) ion? Identify the product of the oxidation.
e) Which solution would be the least effective conductor of electricity? Explain.

2011
#5
Hydrazine is an inorganic compound with the formula N2H4.
a.) In the box below, complete the Lewis electron-dot diagram for the N2H4 molecule by drawing in
all the electron pairs.

b.) On the basis of the diagram you complete in part (a), do all six atoms in the N2H4 molecule lie in
the same plane? Explain.
c.) The normal boiling point of N2H4 is 114 oC, whereas the normal boiling point of C2H6 is
-89 oC. Explain, in terms of the intermolecular forces present in each liquid, which the boiling
point of N2H4 is so much higher than that of C2H6.

d.) Write a balanced chemical equation for the reaction between N2H4 and H2O that explains why a
solution of hydrazine in water has a pH greater than 7.

N2H4 reacts in air according to the equation below.

N2H4(l) + O2(g)  N2(g) + 2 H2O(g) ΔHo = -534 kJ mol-1
e.) Is the reaction an oxidation-reduction, acid-base, or decomposition reaction? Justify your answer.
f.) Predict the sign of the entropy change, ΔS, for the reaction. Justify your prediction.
g.) Indicate whether the statement written below is true or false. Justify your answer.
The large negative ΔHo for the combustion of hydrazine results from the large release of energy
that occurs when the strong bonds of the reactants are broken.
2011 (B)
#2
An 8.55 mol sample of methanol, CH3OH, is placed in a 15.0 L evacuated rigid tank and heated to 327 oC. At that
temperature, all of the methanol is vaporized and some of the methanol decomposes to form carbon monoxide gas
and hydrogen gas, as represented in the equation below.
CH3OH(g)  CO(g) + 2 H2(g)
a.) The reaction mixture contains 6.30 mol of CO(g) at equilibrium at 327 oC.
i.) Calculate the number of moles of H2(g) in the tank.
ii.) Calculate the number of grams of CH3OH(g) remaining in the tank.
iii.) Calculate the mole fraction of H2(g) in the tank.
iv.) Calculate the total pressure, in atm, in the tank at 327 oC.
b.) Consider the three gases in the tank at 327 oC: CH3OH(g), CO(g), and H2(g).
i.) How do the average kinetic energies of the molecules of the gases compare? Explain.
ii.) Which gas has the highest average molecular speed? Explain.

2012
#2
A sample of a pure, gaseous hydrocarbon is introduced into a previously evacuated rigid 1.00 L vessel. The
pressure of the gas is 0.200 atm at a temperature of 127 oC.
a) Calculate the number of moles of the hydrocarbon in the vessel.
b) O2(g) is introduced into the same vessel containing the hydrocarbon. After the addition of the
O2(g), the total pressure of the gas mixture in the vessel is 1.40 atm at 127 oC. Calculate the
partial pressure of O2(g) in the vessel.
The mixture of the hydrocarbon and oxygen is sparked so that a complete combustion reaction occurs, producing
CO2(g) and H2O(g). The partial pressures of these gases at 127 oC are 0.600 atm for CO2(g) and 0.800 atm for
H2O(g). There is O2(g) remaining in the container after the reaction is complete.
c) Use the partial pressures of CO2(g) and H2O(g) to calculate the partial pressure of the O2(g)
consumed in the combustion.
d) On the basis of your answers above, write the balanced chemical equation for the combustion
reaction and determine the formula of the hydrocarbon.
e) Calculate the mass of the hydrocarbon that was combusted.
f) As the vessel cools to room temperature, droplets of liquid water form on the inside walls of the
container. Predict whether the pH of the water in the vessel is less than 7, equal to 7, or greater
than 7. Explain your prediction.