AP Chem Exam - 99

NH3(aq) + H2O(l) <==> NH4 +(aq) + OH (aq)

1.

In aqueous solution, ammonia reacts as represented above. In 0.0180 M

NH3(aq) at 25 C, the hydroxide ion concentration, [OH ] is 5.60104 M.
In answering the following, assume that temperature is constant at 25 C
and that volumes are additive.
(a) Write the equilibrium-constant expression for the reaction represented
above.
Kb =
(b) Determine the pH of 0.0180 M NH3(aq).
pOH = - log(5.60 x104) = 3.252
(c)

pH = 10.748

Determine the value of the base ionization constant, K b, of

NH3(aq).
Kb = = 1.80105

(d)

Determine the percent ionization of NH3 in 0.0180 M NH3(aq).

100% = 3.11%

(e) In an experiment, a 20.0 mL sample of 0.0180 M NH3(aq) was placed

in a flask and titrated to the equivalence point and beyond using
0.0120 M HCl(aq).
(i)Determine the volume of 0.0120 M HCl(aq) that was added to
reach the equivalence point.
(0.0120 N)(VA) = (0.0180 N)(20.0 mL) = 30.0 mL
(ii) Determine the pH of the solution in the flask after a total of
15.0 mL of 0.0120 M HCl(aq) was added.

at 15.0 mL it is half-titrated and [NH4+] = [NH3],

then the Kb = [OH] = 1.80x105.
pOH = - log(1.80 x105) = 4.745
pH = 9.255
(iii) Determine the pH of the solution in the flask after a total of 40.0
mL of 0.0120 M HCl(aq) was added.
at 40.0 mL, there is an excess of 10.0 mL of HCl past equivalence point,
(0.010 L)(0.0120 M) = 0.00012 mol H + ions
6.626x10
hc
=
E

34

= 0.00200M = [H +]

pH = 2.70
2. Answer the following questions regarding light and its interactions
with molecules, atoms, and ions.
(a) The longest wavelength of light with enough energy to break the ClCl
boned in Cl2(g) is 495 nm.
(i)

Calculate the frequency, in s1, of the light.

c = = 6.06 1014 waves/sec

(ii)

Calculate the energy, in J, of a photon of the light.

E = h= (6.631034 joule.s)(6.061014 s1) = 4.021019 J

(iii)

Calculate the minimum energy, in kJ mol1, of the ClCl

bond.

(4.02x1019 J)(6.02 x1023 mol1) = = 241,870 J = 242 kJ

(b) A certain line in the spectrum of atomic hydrogen is associated with
the electronic transition of the H atom from the sixth energy level (n
= 6) to the second energy level (n = 2).
(i)

Indicate whether the H atom emits energy or whether it

absorbs energy during the transition. Justify your answer.
emits energy. The n = 6 state is at a higher energy than n = 2,
the electron must release energy go to the lower state.

(ii)

Calculate the wavelength, in

associated with the spectral line.

nm,

of

the

radiation

E = 2.178 1018 ( ) J = 4.84 1019 J

= hc/E = = 411 nm
(iii) Account for the observation that the amount of energy
associated with the same electronic transition (n = 6 to n =
2) in the He + ion is greater than that associated with the
corresponding transition in the H atom.
The He + has a nuclear charge of 2 + vs H with a 1+,
therefore, it has a stronger hold on the electron. This
requires more energy for the electron to move to higher
energy levels and when the electron moves from higher to
lower energies, it releases more energy.

2 NO(g) + Br2(g) 2 NOBr(g)

3.

A rate study of the reaction represented above was conducted at 25 C.

The data that were obtained are shown in the table below.
Initial [NO]

Trial

(mol L1)

1
2
3

0.0160
0.0160
0.0320

Initial [Br2]

Initial Rate of Appearance of NOBr

(mol L-1)

(mol L1 s1)

0.0120
0.0240
0.0060

3.24104
6.38104
6.42104

(a) Calculate the initial rate of disappearance of Br 2(g) in experiment 1.

Since the disappearance of 1 Br2 produces 2 NOBr, then the rate
would be half as much or rate = - 1.62104.
(b) Determine the order of the reaction with respect to each
reactant, Br2(g)and NO(g). In each case, explain your reasoning.
[NO]2

[Br2]1

(c) For the reaction,

(i)

write the rate law that is consistent with the data

rate = k[NO]2[Br2]
(ii) calculate the value of the specific rate constant, k, and
specify units.
k= =

= 105 L2mol2s1

(d) The following mechanism was proposed for the reaction:

Br2(g) + NO(g) NOBr2(g)

slow

NOBr2(g) + NO(g) 2 NOBr(g)

fast

Is this mechanism consistent with the given experimental

observations? Justify your answer.
No; since the rate determining step is the slowest step (and in this
case, the first step), then the rate for this proposed mechanism
depends only on the cencentration of the reactants in the first step
and would be:
rate = k[NO][Br2]
4.(a) Calcium oxide powder is added to distilled water.
CaO + H2O Ca(OH)2 (or Ca 2+ + OH )
(b) Solid ammonium nitrate is heated to temperatures above 300 C.
NH4NO3 N2 + O2 + H2O (or N2O + H2O)
(c) Liquid bromine is shaken with 0.5M sodium iodide solution.
Br2 + I I2 (or I3 ) + Br
(d) solid lead(II) carbonate is added to a 0.5M sulfuric acid solution.
PbCO3 + H + + SO4 2 PbSO4 + CO2 + H2O
(e) A mixture of powdered iron (III) oxide and powdered aluminum
metal is heat strongly.

Fe2O3 + Al Al2O3 + Fe
(f) Methylamine gas is bubbled into distilled water.
(g)
CH3NH2 + H2O CH3NH3 + + OH
(h) Carbon dioxide gas is passed over hot, solid sodium oxide.
CO2 + Na2O Na2CO3
(i) A 0.2M barium nitrate solution is added to an alkaline 0.2M
potassium chromate solution.
Ba 2+ + CrO4 2 BaCrO4
D (Required)

5. A student performs an experiment to determine the molar mass of

an unknown gas. A small amount of the pure gas is released from a
pressured container and collected in a graduated tube over water at
room temperature, as shown in the diagram above. The collection
tube containing the gas is allowed to stand for several minutes, and
its depth is adjusted until the water levels inside and outside the
tube are the same. Assume that:

the gas is not appreciably soluble in water

the gas collected in the graduated tube and the water are in
thermal equilibrium

a barometer, a thermometer, and analytical balance, and a

table of the equilibrium vapor pressure of water at various
temperatures are also available.

(a) Write the equation(s) needed to calculate the molar mass of the
gas.
barometric pressure
vapor pressure water
= pressure of dry gas
mass of gas bottle, start
mass of gas bottle, end
= mass of gas in collection tube
mol of gas = n = ;

= molar mass

(b) List the measurements that must be made in order to calculate

the molar mass of the gas.
mass of gas bottle, start
mass of gas bottle, end
barometric pressure
volume of gas in collection tube
temperature of gas
look-up in handbook or table: equilibrium vapor pressure of
water at specific temperature and ideal gas constant, R
(c) Explain the purpose of equalizing the water levels inside and
outside the gas collection tube.
equilizing water levels equilizes the internal collection tube pressure
to the external barometric pressure.
(d) The student determines the molar mass of the gas to be 64 g
mol1. Write the expression (set-up) for calculating the percent
error in the experimental value, assuming that the unknown gas
is butane (molar mass 58 g mol 1). Calculations are not required.
100% = % error
(e) If the student fails to use information from the table of the
equilibrium vapor pressures of water in the calculation, the
calculated value for the molar mass of the unknown gas will be
smaller than the actual value. Explain.

if the water vapor pressure is not subtracted from the total pressure,
the apparent gas pressure is too large; this gives a larger value for the
number of moles; in turn, since the mass of the gas is divided by too
large a number of moles, the molar mass is too small.
D (Required)
6. Answer the following question in terms of thermodynamic principles
and concepts of kinetic molecular theory.
(a) Consider the reaction represented below, which is spontaneous
at 298 K.
CO2(g) + 2 NH3(g) CO(NH2)2(s) + H2O(l)

H298 = 134 kJ

(ii) For the reaction, indicate whether the standard entropy

change, S298, is positive, negative, or zero. Justify your
answer.
S is negative because three molecules of reactant make
two molecules of product (a decrease in entropy) and two
different gases make a solid and a liquid (both with smaller
entropies).
(ii) Which factor, the change in enthalpy, H298, or the change
in entropy, S298, provides the principle driving force for the
reaction at 298 K? Explain.
natural tendency to maximize entropy and since this reaction
decreases entropy and is spontaneous (-G), then H must
be negative to overcome the entropy change and drive this
reaction.
(iii) G = H TS ; a T increase the value of TS increases
and the value of G becomes a smaller negative number
(i.e., moves toward zero).
For the reaction, how is the value of the standard free energy
change, G, affected by an increase in temperature? Explain.

(b) Some reactions that are predicted by their sign of G to be

spontaneous at room temperature do not proceed at a measurable
rate at room temperature.
(i) Account for this apparent contradiction.
the sign of G (thermodynamics) does not account for
activation energy (kinetics); a large activation energy would
effectively prevent a reaction even though there is a
favorable free energy change.
(ii) A suitable catalyst increases the rate of such a reaction. What
effect does the catalyst have on G for the reaction? Explain.
a catalyst changes neither the H nor the S for a reaction,
therefore, it will have no effect on the G.

0.10M
NaF

0.10M
MgCl2

0.10M
C2H5OH

0.10M
CH3COOH

7. Answer the following questions, which refer to the 100 mL samples of

aqueous solutions at 25C in the stoppered flasks shown above.
(a) Which solution has the lowest electrical conductivity? Explain.
0.10 M C2H5OH, flask 3. It is the only solute that is not partially or
wholly ionized (or dissociated) since it is a covalently bonded
molecule. Ions are needed to conduct an electric current.
(b) Which solution has the lowest freezing point? Explain.
0.10 M MgCl2, flask 2. The freezing point depression is a colligative
property, and the magnesium chloride dissolves to give 3 particles
(ions) for each dissolved MgCl2. In effect, the solution acts more like a
0.3 M solution, the vant Hoff factor.
(c) Above which solution is the pressure of the water vapor greatest?
Explain.

0.10 M C2H5OH, flask 3. The vapor pressure is also a colligative

property. Since the other solutions give an effective concentration
greater than their measured molarity, the non-ionized ethyl alcohol
will allow the water to vaporize the easiest.
(d) Which solution has the highest pH? Explain.
0.10 M NaF, flask 1. HF is a weak acid and the F ion will react with
water to produce hydroxide ions and a pH greater than 7.
F + H2O HF + OH
The MgCl2 is essentially neutral as well as the C 2H5OH, the CH3COOH
is a weak acid and will give a pH less than 7.
8. Answer the following questions using principles of chemical bonding and
molecular structure.
(a) Consider the carbon dioxide molecule, CO 2, and the carbonate ion,
CO3 2.
(i) Draw the complete Lewis electron-dot structure for each
species.
O
C

O
C
-:

there are two other similar resonance structures for the

carbonate ion.
(ii) Account for the fact at the carbon-oxygen bond length in CO 3
2 is greater than the carbon-oxygen bond length in CO .
2
the pi O=C double bond in CO2 is shorter than a single O-C
resonance sigma-bond (all are identical and are about 1-1/3 bond)
found in a carbonate ion.
(b) Consider the molecules CF4 and SF4.
(i) Draw the complete Lewis electron-dot structure for each
molecule.

F
C
F

F
S
F

(ii) In terms of molecular geometry, account for the fact that the
CF4 molecule is nonpolar, whereas the SF4 molecule is polar.
in the tetrahedral CF4, the polar C-F bonds are cancelled out
by the equiangular pull of the 4 bonds. With an expanded
octet and trigonal bipyramidal structure, SF 4 has a pair of
unbonded electrons at the center of the bipyramid, this gives
a seasaw shape to the molecule and an uneven pull to the
polar S-F bonds.
F
S