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AP Chemistry 1998 Free Response

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The passage discusses solubility equilibria, thermochemistry, kinetics, electrochemistry, and other chemistry concepts.

At higher altitudes, the lower atmospheric pressure causes water to boil at a lower temperature. This means it takes longer to reach the temperature needed to cook food when boiling water at high altitudes.

Initially, copper(II) ammonia complexes form as a precipitate. Upon further bubbling of ammonia, the complexes dissolve as the ammonia concentration increases, making the solution more basic.

Advanced Placement Chemistry: 1998 Free Response Questions

1)Solve the following problem related to the solubility equilibria of some metal hydroxides in
aqueous solution.

a) The solubility of Cu(OH)2 is 1.72 x 106 gram per 100. milliliters of solution at 25 C.
(i) Write the balanced chemical equation for the dissociation of Cu(OH) 2(s) in aqueous
solution.
(ii) Calculate the solubility (in moles per liter) of Cu(OH)2 at 25 C.
(iii) Calculate the value of the solubility-product constant, Ksp, for Cu(OH)2 at 25 C.

b) The value of the solubility-product constant, Ksp, for Zn(OH)2 is 7.7 x 1017 at 25C.
(i) Calculate the solubility (in moles per liter) of Zn(OH)2 at 25C in a solution with a pH
of 9.35.
(ii) At 25C, 50.0 milliliters of 0.100-molar Zn(NO 3)2 is mixed with 50.0 milliliters of
0.300-molar NaOH. Calculate the molar concentration of Zn 2+(aq) in the resulting
solution once equilibrium has been established. Assume that volumes are additive.

2) An unknown compound contains only the three elements C,H, and O. A pure sample of the
compound is analyzed and found to be 65.60 percent C and 9.44 percent H by mass.

(a) Determine the empirical formula of the compound.


(b) A solution of 1.570 grams of the compound in 16.08 grams of camphor is observed to
freeze at a temperature 15.2 Celsius degrees below the normal freezing point of pure
camphor. Determine the molar mass and apparent molecular formula of the compound.
(The molal freezing-point depression constant, Kf, for camphor is 40.0 kg-K-mol1.)
(c) When 1.570 grams of the compound is vaporized at 300 C and 1.00 atmosphere, the
gas occupies a volume of 577 milliliters. What is the molar mass of the compound based
on this result?
(d) Briefly describe what occurs in solution that accounts for the difference between the
results obtained in parts (b) and (c).
3) C6H5OH(s) + 7 O2(g) ---> 6 CO2(g) + 3H2O(l)

When a 2.000-gram sample of pure phenol, C6H5OH(s), is completely burned according to the
equation above, 64.98 kilojoules of heat is released. Use the information in the table below to
answer the questions that follow.

Standard Heat of
Absolute Entropy, S,
Substance Formation, Hf,
at 25C (J/mol-K)
at 25C (kJ/mol)
C(graphite) 0.00 5.69
CO2(g) -395.5 213.6
H2(g) 0.00 130.6
H2O(l) -285.85 69.91
O2(g) 0.00 205.0
C6H5OH(s) ? 144.0

(a) Calculate the molar heat of combustion of phenol in kilojoules per mole at 25C.

(b) Calculate the standard heat of formation, Hf, of phenol in kilojoules per mole at 25C.

(c) Calculate the value of the standard free-energy change, G for the combustion of phenol at
25C.

(d) If the volume of the combustion container is 10.0 liters, calculate the final pressure in the
container when the temperature is changed to 110C. (Assume no oxygen remains unreacted and
that all products are gaseous.)

4)

(a) Solutions of tin(II) chloride and iron(III) chloride are mixed.


(b) Solutions of cobalt(II) nitrate and sodium hydroxide are mixed.
(c) Ethene gas is burned air.
(d) Equal volumes of equimolar solutions of phosphoric acid and potassium hydroxide are
mixed.
(e) Solid calcium sulfite is heated in a vacuum.
(f) Excess hydrochloric acid is added to a solution of diamminesilver(I) nitrate.
(g) Solid sodium oxide is added to distilled water.
(h) A strip of zinc is added to a solution of 6.0-molar hydrobromic acid.
5) An approximately 0.1-molar solution of NaOH is to be standardized by titration. Assume that
the following materials are available.

Clean, dry 50 mL buret Analytical balance


250 mL Erlenmeyer flask Phenolphthalein indicator solution
Wash bottle filled with distilled water Potassium hydrogen phthalate, KHP, a pure solid
monoprotic acid (to be used as the primary standard)

(a) Briefly describe the steps you would take, using materials listed above, to standardize the
NaOH solution.

(b) Describe (i.e., set up) the calculations necessary to determine the concentration of the NaOH
solution.

(c) After the NaOH solutions has been standardized, it is used to titrate a weak monoprotic acid,
HX. The equivalence point is reached when 25.0 mL of NaOH solution has been added. In the
space provided at the right, sketch the titration curve, showing the pH changes that occur as the
volume of NaOH solution added increases from 0 to 35.0 mL. Clearly label the equivalence
point on the curve.

(d) Describe how the value of the acid-dissociation constant, K a, for the weak acid HX could be
determined from the titration curve in part (c).

(e) The graph below shows the results obtained by titrating a different weak acid, H 2Y, with the
standardized NaOH solution. Identify the negative ion that is present in the highest concentration
at the point in the titration represented by the letter A on the curve.
6) Answer the following questions regarding the kinetics of chemical reactions.

(a) The diagram below at right shows the energy pathway for the reaction O3 + NO --> NO2 + O2.
Clearly lebel the
Following directly on the
diagram.
(i) The activation energy
(Ea) for the forward reaction
(ii) The enthalpy change
(H) for the reaction

(b) The reaction 2 N2O5 --> 4 NO2 + O2 is first order with respect to N2O5.
(i)Using the axes at right, complete the graph that
represents the change in [N2O5] over time as the reaction
proceeds.
(ii) Describe how the graph in (i) could be used to
find the reaction rate at a given time, t.
(iii) Considering the rate law and the graph in (i),
describe how the value of the rate constant, k, could be determined.
(iv) If more N2O5 were added to the reaction mixture
at constant temperature, what would be the effect on
the rate constant, k? Explain.
(c) Data for the chemical reaction 2A --> B + C were collected by measuring the concentration of
A at 10-minute intervals for 80 minutes. The following graphs were generated from analysis of
data.

Use the information in the graphs above to answer the following.


(i) Write the rate-law expression for the reaction. Justify your answer.
(ii) Describe how to determine the value of the rate constant for the reaction.

7)
C(s) + H2O(g) <===> CO(g) + H2(g)
H = +131 kJ
A rigid container holds a mixture of graphite pellets (C(s)), H 2O(g), CO(g), and H2(g) at
equilibrium. State whether the number of moles of CO(g) in the container will increase,
decrease, or remain the same after each of the following disturbances is applied to the original
mixture. For each case, assume that all other variables remain constant except for the given
disturbance. Explain each answer with a short statement.
(a) Additional H2(g) is added to the equilibrium mixture at constant volume.
(b) The temperature of the equilibrium mixture is increased at constant volume.
(c) The volume of the container is decreased at constant temperature.
(d) The graphite pellets are pulverized.
8)

Answer the following questions regarding the electrochemical cell shown above.
(a) Write the balanced net-ionic equation for the spontaneous reaction that occurs as the
cell operates, and determine the cell voltage.

(b) In which direction do anions flow in the salt bridge as the cell operates? Justify your
answer.

(c) If 10.0 mL of 3.0-molar AgNO3 solution is added to the half-cell on the right, what
will happen to the cell voltage? Explain.

(d) If 1.0 grams of solid NaCl is added to each half-cell, what will happen to the cell
voltage? Explain.

(e) If 20.0 mL of distilled water is added to both half-cells, the cell voltage decreases.
Explain.
9) Answer each of the following using appropriate chemical principles.

(a) Why does it take longer to cook an egg in boiling water at high altitude than it does at
sea level?

(b) When NH3 gas is bubbled into an aqueous solution of CuCl2, a precipitate forms
initially. On further bubbling, the precipitate disappears. Explain these two observations.

(c) Dimethyl ether, H3C-O-CH3, is not very soluble in water. Draw a structural isomer of
dimethyl ether that is much more soluble in water and explain the basis of its increased
water solubility.

(d) Identify a chemical species that is

(i) capable of oxidizing Cl(aq) under standard conditions

(ii) capable of reducing Cl2(aq) under standard conditions. In each case, justify
your choice.

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