Chem 142B, HW 6 answer key, Fall 2005

Note: There is always more then one way to solve a given problem. A different method to solve then
indicated here, as well as different rounding at different points in the problem, may yield slightly different
answers. Also, all calculations have an extra digit carried through until the final answer, which is
expressed to the correct # of significant figures.
1. Discrepancies in the experimental values of the molar mass of nitrogen provided some of the first
exidence for the existance of the noble gases. If pure nitrogen is collected from the decomposition of
ammonium nitrate, its measured molar mass is 28.01.
NH4NO(s)

N2(g) + 2 H2O(g)

If O2, CO2, and H2O are removed from air, the remaining gas has an average molar mass of 28.15.
Assuming this discrepancy is solely a result of contamination with argon (atomic mass = 39.95), calculate
the ratio of moles of Ar to moles of N2 in air.
Solution: Here, were going to need to determine the mole fraction of nitrogen, and argon with respect to
each other. If we let x=mole fraction of nitrogen in the atmosphere, then the mole fraction of argon in the
atmosphere is going to be 1-x. This is because we have a binary system, and the total mole fraction must
be equal to 1. With this, we can solve for the mole fraction of both, and determine the molar ratio between
nitrogen and argon:
ave. molar mass = N 2 MM N 2 + Ar MM Ar = 24.02 x + 39.95(1 x ) = 28.15 g / mol
28.15 39.95
= 0.98827 = fraction N 2
28.01 39.95
fraction Ar = 1 0.98827 = 0.01173

x=

ratio Ar : N 2 =

0.01173
= 0.01186 = 0.0119
0.98827

2. Metallic molybdenum can be produced from the mineral molybdenite, MoS2. The mineral is first
oxidized in air to molybdenum trioxide and sulfur dioxide. Molybdenum trioxide is then reduced to
metallic molybdenum using hydrogen gas. The balanced equations are given below.
MoS2(s) + 7/2 O2(g)
MoO3(s) + 3 H2(g)

MoO3(s) + 2 SO2(g)
Mo(s) + 3 H2O(s)

Calculate the volumes of air and hydrogen gas at 30.C and 1.00 atm that are necessary to produce 1.00
103 kg of pure molybdenum from MoS2. Assume air contains 21% oxygen by volume and assume 100%
yield for each reaction.
Solution: first, were going to need to determine the amount of Mo in moles that we are going to be
dealing with. Once that is known, we can use the stoichiometry of the reaction to determine the moles of
oxygen (and thus air) needed and hydrogen needed to perform the conversion:

moles Mo =

1 .00 x10 6 g
= 1 .0423 x10 4 mol
95 .94 g / mol

mol MoO 3
moles O2 = 1 .042 x10 4 mol Mo
mol Mo
moles air =

3 .648 x10 4 mol O2

0 .21

3 .5 mol O2

mol
MoO 3

= 3 .648 x10 4 mol

O2

= 1 .74 x10 5 mol air

3 mol H 2
moles H 2 = 1 .042 x10 4 mol Mo
mol Mo

= 3 .127 x10 4 mol H

2

Now that we know how many moles of each are needed for the conversion, the ideal gas law, PV=nRT, can
be used to determine the volume of each gas:
nRT 1.74 x10 5 * 0.08206 * (273.15 + 30.)
=
= 4.32 x10 6 = 4.3 x10 6 Lair
P
1
= 3.127 x10 4 * .08206 * 303. = 7.775 x10 5 = 7.778 L H 2

Volumeair =
Volume H 2

3. Urea (H2NCONH2) is used extensively as a nitrogen source in fertilizers. It is produced commercially

from the reaction of ammonia and carbon dioxide.
2 NH3(g) + CO2(g)

H2NCONH2(s) + H2O(g)

Ammonia gas at 223C and 90. atm flows into a reactor at a rate of 500. L/min. Carbon dioxide at 223C
and 45 atm flows into the reactor at a rate of 600. L/min. What mass of urea is produced per minute by this
reaction assuming 100% yield?
Solution: first, were going to want to calculate the moles/minute we have flowing into the reactor using
the ideal gas law, then determine if theres a limiting reagent:
PV
90. * 500.
mol/min NH 3 =
=
= 1.11x10 3 mol / min
RT 0.08206 * (273.15 + 223)
45 * 600.
mol/minCO2 =
= 663 mol/min
0.08206 * (273.15 + 223)
the flow of ammonia is going to be the limiting reagent, since the number of moles is not twice that of the
carbon dioxide. Now, we can use the reaction stoichiometry between ammonia and urea to determine the
rate that urea is fromed:
molurea
4
4
* 60.06 g / mol
massurea = 1.11x10 3 mol NH 3
urea = 3.33 x10 = 3.3 x10 g urea / min
2 mol NH
3

4. The nitrogen content of organic compounds can be determined by the Dumas method. The compound in
question is first reacted by passage over hot CuO(s).
Compound

N2(g) + CO2(g) + H2O(g)

The gaseous products are then passed through a concentrated solution of KOH to remove the CO2. After
passage through the KOH solution, the gas contains N2 and is saturated with water vapor. In a given
experiment a 0.261 g sample of a compound produced 31.8 mL N2 saturated with water vapor at 25C and
722. torr. What is the mass percent of nitrogen in the compound? (The vapor pressure of water at 25C is
23.8 torr.)
Solution: Were going to need to determine the mass of nitrogen in the sample, as determined by the
amount of nitrogen recovered as gas. First, we need to take out the partial pressure of water vapor to
determine the partial pressure of nitrogen. Then we can use that in the ideal gas law to determine the
number of moles of nitrogen gas. The partial pressure of nitrogen is going to be found by subtracting the
vapor pressure of water vapor from the total pressure, ie 722-23.8=698.2 torrnitrogen. Of course, in the
ideal gas law, were going to need to convert to atmospheres, with the conversion factor of 760 torr=1 atm.
PV
698.2 * 0.0318
moles N 2 =
=
= 1.1941x10 3 mol
RT 760 * 0.08206 * (273.15 + 25)
mass N 2 = 1.1941x10 3 * 28.02 = 0.033458 g
%N 2 =

0.033458
* 100 = 12.81 = 12.8%
0.261

5. An organic compound contains C, H, N, and O. Combustion of 0.1023 g of the compound in excess

oxygen yielded 0.2766 g of CO2 and 0.0991 g of H2O. A sample of 0.4831 g of of the compound was

analyzed for nitrogen by the Dumas method. At STP, 27.6 mL of dry N2 was obtained. In a third
experiment the density of the compound as a gas was found to be 4.02 g/L at 127C and 256 torr. What are
the empirical formula and the molecular formula of the compound? (Type your answer using the format
CO2 for CO2.)
Solution: In order to determine the empirical formula, we need to first determine the mass percent of each
element in the compound from the information given above. To determine the % C and H, we need to use
the % mass of each in CO2 and H2O respectively, so that we can determine the actual mass of each from
the compound:
12.01 g C

0.2766 g CO2
44.01 g CO
2

%C =
= 73.79%
0.1023 g sample
2.016 g H

0.0991 g H 2O
18.016 g H O
2

%H =
= 10.84%
0.1023
Use the ideal gas law to determine the moles of nitrogen from the sample, convert to grams, and determine
the %N in the sample. STP is 1 atm, and 273K:
PV atm * 0.0276 L
mol N 2 =
=
= 0.0123 mol N 2
RT 0.08206 * 273
0.0123 * 28.02
%N =
= 7.14%
0.4831
Finally, the % mass of oxygen in the compound is the remainder, which ends up being 8.2%. Now, we
assume we have 100g of the compound, and determine the moles of each we have to determine what the
empirical formula is, after dividing everything through by the smallest number of moles:
73.79
10.84
7.14
8.20
mol C =
= 6.144; mol H =
= 10.75; mol N =
= 0.5096; mol O =
= 0.513
12.01
1.008
14.01
16.00
Which will give us an empirical formula of C12H21NO, when dividing through by about 0.51 (moles of O
and N).

Now, well use the density measurement to determine the molecular formula. We can rearrange the ideal
gas law to get at the MM of a compound from its density:
mRT
mRT dRT
, where d=density in terms of grams/L. Plugging in
PV = nRT =
=
, which gives MM =
MM
P
PV
what we know, we find the molar mass to be
dRT 4.02 * 400 * 0.08206
MM =
=
392 g / mol
P
256 / 760
molecular
392
mult factor =
=
2
emperical 12 * 12.01 + 21 * 1.008 + 16 + 14.01
So that the molecular formula is C24H42N2O2.
6. Consider a 1.0 L container of neon gas at STP. Will the average kinetic energy, root mean square
velocity, frequency of collisions of gas molecules with each other, frequency of collisions of gas molecules
with the walls of the container, and energy of impact of gas molecules with the container increase,
decrease, or remain the same under each of the following conditions?
(a) The temperature is increased to 100C.
(b) The temperature is decreased to -50C.
(c) The volume is decreased to 0.5 L at constant temperature.
(d) The number of moles of neon is doubled at constant temperature.
Solution: think about what the changes mean. A change in temperature automatically mean, according to
the kinetic theory of gases, that the kinetic energy of the gas is going to change, which will also correspond

to change in root mean square velocity (RMSV). Changing the temperature also will change the frequency
with which the particle runs into things, and also the energy it hits it with, leading to the results of a and b.
For C, if you keep the temp the same, the kinetic energy, RMSV, and impact energy must remain the same,
since they are dependent on the temp. However, the smaller the volume, the particles will run into things
more often then they were before, due to a smaller space to bounce around in. For d, adding more
particles is going to be the same as decreasing the volume. The more stuff there is in a container, the
smaller the available volume is.
KE
RMSV
freq col. Wall freq coll others impact E
a
increase increase
increase
increase
increase
b
decrease decrease
decrease
decrease
decrease
c
same
same
increase
increase
same
d
same
same
increase
increase
same
7. The effusion rate of an unknown gas is measured and found to be 31.50 mL/min. Under identical
experimental conditions the effusion rate of O2 is found to be 30.50 mL/min. Which of the following is the
unknown gas: CO, CH4, CO2, NO, or NO2?
Solution: the one that would be just a little bit faster then oxygen, would be the molecule with a molecular
weight just smaller then that for oxygen, in this case, its NO. According to the math, where the effusion
rate is inversely proportional to the molar mass:
2
rateO2
MM unk
MM unk
30.50
30.50
=
=
;
; MM unk =
* 32.00 = 30.00 g / mol
rateunk
MM O2
31.50
32.00
31.50
And since MMNO=30.01 g/mol, NO is the correct choice for the unknown gas.
8. (a) Calculate the pressure exerted by 0.5260 mol N2 in a 1.0000 L container at 25.6C using the ideal
gas law.
Solution: Plug and chug the values into the ideal gas law, solving for pressure:
nRT
Pideal =
= 0.5260 * 0.08206 * (273.15 + 25.6) = 12.89 atm
V
(b) Calculate the pressure exerted by 0.5260 mol N2 in a 1.0000 L container at 25.6C using the van der
Waals equation.
Solution: the van der Waals equation takes the non-ideality of gases into account, by introducing some
correction factors, which change between gases, to the ideal gas law:
nRT
0.5260 * 0.08206 * (273.15 + 25.6)
0.526
n
a =
1.39
= 12.78 atm
V
V nb
1

0
.
5260
*
0
.
0391

1
2

Preal =

(c) Compare the results. (Write the percentage difference between the results, based on the higher value
result.)
Solution: subtract the two values, and divide by the higher pressure to find the percentage:
12.89 12.78
%diff =
* 100 = 0.853 = 0.85%
12.89