Advanced Placement Chemistry

1990 Free Response Questions

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1) The solubility of iron(II) hydroxide, Fe(OH)2, is 1.43 x 103 gram per liter at 25 C.

(a) Write a balanced equation for the solubility equilibrium.

(b) Write the expression for the solubility product constant, Ksp, and calculate its value.

(c) Calculate the pH of the saturated solution of Fe(OH)2 at 25 C.

(d) A 50.0-milliliter sample of 3.00 x 103 molar FeSO4 solution is added to 50.0 milliliters of
4.00 x 106 molar NaOH solution. Does a precipitate of Fe(OH)2 form? Explain and show
calculations to support your answer.

2) A mixture of H2(g), O2(g), and 2 milliliters of H2O(l) is present in 0.500-liter rigid container at
25 C. The number of moles of H2 and the number of moles of O2 are equal. The total pressure is
1,146 millimeters of mercury. (The equilibrium vapor pressure of pure water is 24 millimeters
mercury.)

The mixture is sparked, and H2 and O2 react until one reactant is completely consumed.

(a) Identify the reactant remaining and calculate the number of moles of the reactant remaining.

(b) Calculate the total pressure in the container at the conclusion of the reaction if the final
temperature is 90 C.

(c) Calculate the number of moles of water present as vapor in the container at 90 C.

3)
The tables above contain information for determining thermodynamic properties of the reaction
below.

C2H5Cl(g) + Cl2(g) <===> C2H4Cl2 (g) + HCl(g)

(a) Calculate H for the reaction above, using the table of average bond dissociation energies.

(b) Calculate S for the reaction at 298 K, using data from either table as needed.

(c) Calculate the value for Keq for the reaction at 298 K.

(d) What is the effect of an increase in temperature on the value of the equilibrium constant?
Explain your answer.

4) Give the formulas to show the reactants and the products for FIVE of the following chemical
reactions. Each of the reactions occurs in aqueous solution unless otherwise indicated. Represent
substances in solution as ions if the substance is extensively ionized. Omit formulas for any ions
or molecules that are unchanged by the reaction. In all cases a reaction occurs. You need not
balance.

Example: A strip of magnesium is added to a solution of silver nitrate.

Mg + Ag+ ---> Mg2+ + Ag

(a) Solutions of sodium iodide and lead nitrate are mixed.

(b) A solution of ammonia is added to a solution of ferric chloride.

(c) A solution of hydrogen peroxide is heated.

(d) Solutions of silver nitrate and sodium chromate are mixed.

(e) Hydrogen sulfide gas is bubbled through a solution of potassium hydroxide.

(f) Solid dinitrogen pentoxide is added to water.

(g) A piece of solid bismuth is heated

(h) A strip of copper metal is added to a concentrated solution of sulfuric acid.

5) Use simple structure and bonding models to account for each of the following.

(a) The bond length between the two carbon atoms is shorter in C2H4 than in C2H6.

(b) The H - N - H bond angle is 107.5 in NH3.

(c) The bond lengths in SO3 are all identical and are shorter than a sulfur-oxygen single bond.

(d) The I3 ion is linear.

6)

The diagram shows the first ionization energies for the elements from Li to Ne. Briefly (in one to
three sentences) explain each of the following in terms of atomic structure.

(a) In general, there is an increase in the first ionization energy from Li to Ne.

(b) The first ionization energy of B is lower than that of Be.

(c) The first ionization energy of O is lower than that of N.

(d) Predict how the first ionization energy of Na compares to those of Li and of Ne. Explain.
7) Consider the following general equation for a chemical reaction.

A(g) + B(g) ---> C(g) + D(g)

(a) Describe the two factors that determine whether a collision between molecules of A and B
results in a reaction.

(b) How would a decrease in temperature affect the rate of the reaction shown above? Explain
your answer.

(c) Write the rate law expression that would result if the reaction proceeded by the mechanism
shown below.

A + B <===> [AB] (fast)

[AB] + B ---> C + D (slow)

(d) Explain why a catalyst increases the rate of a reaction but does not change the value of the
equilibrium constant for that reaction.

8) Give a brief explanation for each of the following.

(a) For the diprotic acid H2S, the first dissociation constant is larger than the second dissociation
constant by about 105 (K1 = 105 K2).

(b) In water, NaOH is a base, but HOCl is an acid.

(c) HCl and HI are equally strong acids in water but, in pure acetic acid, HI is a stronger acid
than HCl.

(d) When each is dissolved in water, HCl is a much stronger acid than HF.

9) An experiment is performed to determine the empirical formula of a copper iodide formed by

direct combination of elements. A clean strip of copper metal is weighed accurately. It is
suspended in a test tube containing iodine vapor generated by heating solid iodine, A white
compound forms on the strip of copper, coating it uniformly. The strip with the adhering
compound is weighed. Finally, the compound is washed completely from the surface of the metal
and the clean strip is dried and reweighed.

DATA TABLE
Mass of clean copper strip 1.2789 grams
Mass of copper strip and compound 1.2874 grams
 Mass of copper strip after washing 1.2748 grams

(a) State how you would use the data above to determine each of the following. (Calculations not
required.)

(1) The number of moles of iodine that reacted

(2) The number of moles of copper that reacted

(b) Explain how you would determine the empirical formula for the copper iodide.

(c) Explain how each of the following would affect the empirical formula that could be
calculated.

(1) Some unreacted iodine condensed on the strip.

(2) A small amount of the white compound flaked off before weighing.
 Advanced Placement Chemistry
1990 Free Response Answers

Notes

[delta] and [sigma] are used to indicate the capital Greek letters.
[square root] applies to the numbers enclosed in parenthesis immediately following
All simplifying assumptions are justified within 5%.
One point deduction for a significant figure or math error, applied only once per problem.
No credit earned for numerical answer without justification.
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1)

a) one point

Fe(OH)2 ------> Fe2+ + 2 OH

b) four points

Ksp = [Fe2+][OH]2

M.W. of Fe(OH)2 = 55.85 + 2(16.0) + 2(1.008) = 89.87

1.43 x 103 g. x 1 mol / 89.87 g. = 1.59 x 105 mole Fe(OH)2

this equals 1.59 x 105 mole Fe2+ and 3.18 x 105 mole OH

therefore the Ksp = (1.59 x 105) (3.18 x 105)2 = 1.6 x 1014

c) one point

[H+] = 1.0 x 1014 / [OH]

= 1.0 x 1014 / 3.18 x 105
= 3.14 x 1010

pH = - log [H+] = 9.50

OR

[pOH] = - log [OH] = - log (3.18 x 105) = 4.50

pH = 14 - pOH = 9.50

d) three points

50.0 mL of 3.0 x 103 M Fe2+ diluted to 100 ml = 1.5 x 103 M Fe2+

50.0 ml of 4.0 x 106 M OH diluted to 100 ml = 2.0 x 106 M OH

Q = [Fe2+][OH]2 = (1.5 x 103) (2.0 x 106)2 = 6.0 x 1015

Precepitate will NOT form since Q < Ksp

2)

a) six points

2 H2 + O2 ---> 2 H2O

moles H2 = moles O2 initially but 2 moles of H2 react for every mole of O2. O2 is left.

Ptot = PH2 + PO2 + PH2O

1146 = PH2 + PO2 + 24 (v.p. of H2O = 24 mmHg)

PH2 + PO2 = 1122 mm Hg

1122 mm / 4 = PO2 left (1/2 of initial O2 which is 1/2 total)

PO2 = 280.5 mm

P1V1 / T1 = P2V2 / T2

((280.5) (0.5 L)) / (298) = ((760 mm)V2) / (273)

V2 = 0.169 L therefore

n = 0.169 L / 22.4 L mol1 = 7.55 x 103 mol

OR

PV = nRT

((280.5 / 760)atm (0.5 L)) / ((0.0821 L atm/mol K) (298 K)) = n = 7.55 x 103 mol

b) two points

PO2 (@ 90C) / 363 = 280.5 / 298 = 342 mm Hg

OR

P = ((7.55 x 103 mol) (0.0821) (363)) / 0.5 = 0.45 atm = 342 mm Hg

therefore

Ptot = PO2 + PH2O = 342 + 526 = 868 mm Hg

c) one point

VH2O (@ STP) = ((526 mm Hg) (0.5) (273)) / ((760) (363)) = 0.260 L

mol. of H2O = 0.260 L / 22.4 L mol1 = 0.0116 mol

OR

n = ((526 / 750)atm (0.50)) / ((0.0821) (363) = 0.0116 mol

3)

a) two points

[delta]H = bonds broken minus bonds formed.

C2H5Cl + Cl-Cl ---> C2H4Cl2 + HCl

[delta]H
(2794 + 243) minus (2757 + 431)
=

[delta]H = 3037 - 3188 = - 151 kJ mol1

OR
 CH + Cl-Cl ---> C-Cl + HCl
[delta]H
(414 + 243) minus (377 + 431)
=

[delta]H = - 151 kJ mol1

b) four points

[delta]G = [[delta]Gf C2H4Cl2 + [delta]Gf HCl] - [[delta]Gf C2H5Cl + [delta]Gf Cl2]

= (- 80.3 - 95.3) - (- 60.5 + 0) = - 115 kJ

[delta]G = [delta]H - T[delta]S

[delta]S = ((- 151 kJ - (- 115 kJ)) / 298 = - 0.120 kJ mol1 K1

c) two points

[delta]G = - RT ln K

- ln K = - 11510 / (8.314 x 298)

ln K = 46.46

K = 1.50 x 1020

d) one point

Keq will decrease with an increase in T because the reverse (endothermic) reaction will be
favored with addition of heat

OR

[delta]G will be less negative with an increase in temperature (from [delta]G = [delta]H -
T[delta]S) which will cause K to decrease.

4)
a)* Pb2+ + 2I -----> PbI2

b) Fe3+ + NH3 + H2O ----> Fe(OH)3 + NH4+ (NH4OH is OK in place of NH3 + H2O)

Fe2+ + others above-----> Fe(OH)2 + NH4+ (given two points)

c) H2O2 -----> H2O + O2

d)* Ag+ + CrO42 -----> Ag2CrO4

e) H2S + OH -----> S2 (or HS) + H2O

f) N2O5 + H2O -----> H+ + NO3 (HNO3 = one point)

g) Bi + O2 -----> Bi2O3 (Bi2O5 = one point)

h) Cu + H+ + HSO4 (or SO42) -----> Cu2+ + SO2 + H2O (any two products is given one point;
all three must be there for 3 points; omitting H+ and/or H2O is minus one point)

(*Correct equation but wrong charge on ion(s) = one point)

5)

a) two points

C2H4 has a multiple bond; C2H6 has a single bond.

Multiple bonds are stronger and therefore shorter than single bonds.

b) two points

NH3 has 3 bonding pairs and 1 lone pair of electrons.

Bond pairs are forced together because the repulsion between the lone pair and the bond pairs is
greater than that netween bond pairs.

c) two points

The bonding in SO3 can be described as a combination of 3 resonance forms of 1 double and
single bonds.
The actual structure is intermediate between the 3 resonance forms, having 3 bonds which are
equal and stronger (therefore shorter) than a S-O single bond.

(Credit is given for three sulfur-oxygen double bonds @ 120 with explanation.)

d) two points

The central I atom has 3 lone pairs and 2 bond pairs around it. To minimize repulsion, the 3 lone
pairs are arranged in a trigonal plane at right angles to the I-I-I axis.

6)

a) two points

Across the period from Li to Ne the number of protons is increasing in the nucleus hence the
nuclear charge is increasing with a consequently stronger attraction for electrons and an increase
in I.E.

b) two points

The electron ionized in the case of Be is a 2s electron wheras in the case of B it is a 2p electron.
2p electrons are higher in energy than 2s electrons because 2p electrons penetrate the core to a
lesser degree.

c) two points

The electron ionized in O is paired with another electron in the same orbital, whereas in N the
electron comes from a singly-occupied orbital. The ionization energy of the O electron is less
because of the repulsion between two electrons in the same orbital.
d) two points

The ionization energy of Na will be less than those of both Li and Ne because the electron
removed comes from an orbital which is farther from the nucleus, therefore less tightly held.

7)

a) two points

1. the kinetic energy of the molecules

(A certain minimum energy is required for a reaction to occur (activation energy))
2. The orientation of the molecules relative to one another. Even very energetic collisions
may not lead to a reaction if the molecules are not oriented properly.

b) two points

1. A decrease in temperature would decrease the rate.

2. Fewer molecules would have the energy necessary to react. (Fewer effective collisions)

c) two points

Rate = [A][B]2

d) two points

1. Catalyst increases the rate by providing an alternate pathway which has a lower
activation energy.
2. The value of the equilibrium constant does not change as a catalyst does not affect the
energies (or concentrations) of the reactants and products.

8)

a) two points
After the first H+ is lost from H2S, the remaining species, HS, has a negative charge. This
increases the attraction of the S atom for the bonding electrons in HS. The bond is therefore
stronger, H+ is harder to remove, and K2 is lower.

b) two points

Polar H2O can separate ionic NaOH into Na+ (aq) and OH (aq) giving a basic solution. In
HOCl, chlorine has a high attraction for electrons due to its greater charge density. This draws
electrons in the H-O bond towards it and weakens the bond. H+ can be removed, making an acid
solution.

c) two points

Water is a more basic solvent (greater attraction for H+) and removes H+ from Cl and I
equally.

Acetic acid has little attraction for H+ but the H+ separates from the larger I easier than from the
smaller Cl.

d) two points

The bond between H and Cl is weaker than the bond between H and F. HCl is therefore a
stronger acid.

9)

a) four points

1. mass of Cu strip and compound minus mass of original clean Cu strip = mass of iodine
mass of iodine / atomic mass of iodine (126.9 g/mol) = moles iodine
2. mass of original clean Cu strip minus mass of strip after washing = mass of Cu
mass of copper / atomic mass of copper (63.54 g/mol) = moles of Cu

b) one point

The empirical formula is the ratio of mol. iodine to mol. copper ( or alternatively, mol. copper to
mol. iodine)
c) three points

1. Unreacted iodine would make the apparent mass of compound and the iodine too high.
Thus, the I:Cu ratio in the empirical formula would be too high.
2. If some of the compound flaked off, the mass of compound (and the iodine) would be too
low. Thus, the I:Cu ratio in the empirical formula would be too low.

In part (c) 2 points were awared for a correct response on either part (1) or part (2) that included
the prediction (1 pt.) and reason (1 pt.) An additional one point was awarded for the correct
prediction and reason in the other part.