Module 8
Module 8
Chem 170
Stoichiometric Calculations
Module Eight
Including Gases in Stoichiometric Calculations
Fortunately there are other ways to determine the quantity of a reagent in the gas phase.
In this module you will learn of the ideal gas law, which provides a relationship between
the moles of gas and three variables – pressure, volume, and temperature – that are easily
measured. Using the ideal gas law, you will then solve stoichiometry problems in which
the amount of a gas is given in terms of its pressure, volume, and temperature. In
completing this module you will master the following objectives:
• to use the ideal gas law to evaluate how a change in conditions affects a gas
• to use the ideal gas law to find either the moles, pressure, volume, or
temperature of a gas given values for the other three quantities
Properties of Gases
You are well aware from your experiences that matter can take one of three common
forms: solid, liquid, and gas. Water, for example, is a solid (ice) at temperatures below
0oC, a gas (steam or water vapor) at temperatures above 100oC, and a liquid at all
temperatures in between. †
There are several ways in which these forms of water differ from each other. Ice cubes,
when placed in a bottle, maintain their shape and volume. Although its volume remains
unchanged, when liquid water is placed in a bottle it takes on the shape of that part of the
bottle it occupies, conforming to the bottle’s curves. Water vapor, however, fills the
bottle, assuming both its shape and its volume.
The molecules of water in an ice cube are in an ordered arrangement in which they have
relatively little freedom to move, which is why an ice cube maintains its shape. In its
liquid state, water molecules are more disordered and are free to move around, although
the attractive forces between the molecules prevent them from separating from each
other. Molecules of water in the gas phase, however, have no order (which is why a gas
expands to fill its container) and move independently of each other. This lack of a
specific volume for a gas is an important property and accounts for the fact that gases,
unlike solids and liquids, do not have a constant density at a fixed temperature.
Because gas molecules are free to move about their container, they must, of course,
collide with each other and with the container’s walls. The force of a gas molecule’s
collisions with the container’s wall is called its pressure. The SI unit for pressure is the
pascal (Pa), which is equivalent to a force of 1 newton applied to an area of 1 square
meter. Standard atmospheric pressure, therefore, is the weight of a column of air
extending above a surface with an area of 1 m2 at 0oC and an elevation of sea level. In SI
units the standard atmospheric pressure is 101,325 Pa. For historical reasons, pressure is
usually reported using one of several common non-SI units. One such unit is the
atmosphere (atm), where standard atmospheric pressure is defined as 1 atm; thus
1 atm = 101,325 Pa
Another non-SI unit for pressure is the torr, which is equivalent to the pressure exerted by
a 1-mm column of mercury. A column of mercury whose height is 760 mm has a
pressure equivalent to standard atmospheric pressure; thus
Anything that increases the frequency of collisions – more gas molecules, a decrease in
volume, or faster moving molecules – produces an increase in pressure. Not surprisingly,
pressure, volume, moles, and temperature (which affect the speed with which gas
†
These temperatures are valid for a pressure of 1 atmosphere. As we shall see shortly, the properties of a
gas also depend on its pressure.
molecules move) are interrelated. The next few sections consider several quantitative
relationships between pairs of these parameters and a quantitative relationship between
all four parameters.
Boyle’s Law
In the 17th century, Robert Boyle studied the relationship between the pressure exerted
on a fixed amount of gas and its volume at constant temperature. Specifically, Boyle
noted that pressure and volume are inversely proportional; that is, if the pressure applied
to a gas is doubled, its volume is cut in half. We express this mathematically as
PV = kb
where P is the pressure, V is the volume, and kb is a constant. Because the product of
pressure and volume is constant for a fixed amount of gas at a constant temperature, we
can easily calculate how a change in the pressure or volume of a gas must affect its
volume or pressure; thus
P1V1 = P2V2
Charles’s Law
Here are two observations about gases: hot air balloons rise because heated air expands
and becomes less dense and placing a balloon in a freezer will cause it to shrink. Clearly
the volume a gas occupies is directly proportional to its temperature. Jacques Charles,
who showed that for any gas a plot of volume vs. temperature is a straight-line, first
studied this relationship in the late 18th century. Interestingly, when similar plots for
different gases, or for the same gas at different pressures, are superimposed and
extrapolated to a volume of zero, each extrapolates to the same temperature. This
temperature of -273.15 oC or 0 K, is called absolute zero. When using the Kelvin scale
for temperature the following relationship holds for a fixed amount of gas at a constant
pressure
V
= kc
T
where V is the volume of gas, T is the absolute temperature (Kelvin, not Celsius!), and kc
is a constant. Because the ratio of volume and absolute temperature is constant for a
fixed amount of gas at a constant pressure, we can easily calculate how a change in the
volume or the temperature of a gas must affect its temperature or volume; thus
V1 V2
=
T1 T2
Example 2. A balloon is filled with air so that it has a volume of 4.50 L at a temperature
of 25oC. It is then placed in a freezer where its temperature is -10oC. What volume of air
does the balloon now contain?
Solution. First we must convert the temperatures from the Celsius scale to the Kelvin
scale; thus the temperature outside the freezer is
25 + 273.15 = 298 K
V1 4.50 L
V2 = × T2 = × 263 K = 3.97L
T1 298 K
Avogadro’s Law
At the beginning of the 19th century, Joseph Louis Guy-Lussac noted that for a fixed
pressure and temperature the volumes of two gases reacting together were always in the
ratio of simple whole numbers. For example, two volumes of hydrogen gas react with
one volume of oxygen gas, producing two volumes of water. Amedeo Avogadro
interpreted this result by suggesting that equal volumes of gas at the same temperature
and pressure must contain the same number of molecules (or moles) of gas. This is
known as Avogadro’s law, which we express mathematically as
V
= ka
n
where V is the volume the gas occupies, n is the moles of gas, and ka is a constant.
1
V∝ V ∝T V ∝n
P
nT nT
V∝ =R
P P
PV = nRT
The term R, which is the proportionality constant, is called the gas constant and has a
value of
L ⋅ atm
R = 0.082057
mol ⋅ K
although rounding off to three significant figures (0.0821 L•atm/mol•K) is appropriate for
many problems.
The equation PV = nRT is called the ideal gas law. Including the word “ideal” should set
off alarm bells suggesting that this equation applies to “ideal” gases, not real gases. †
This is, in fact, the case. The ideal gas law is an example of a limiting law; that is, it
more accurately predicts the behavior of a gas at the limits of relatively low pressure and
relatively high temperature. As long as we limit ourselves to such conditions, we may
†
The van der Waals equation provides a better approximation for the behavior of real gases. This
equation takes into account the interactions between gas molecules, which affects their motion, and the
volume occupied by the molecules themselves, which decreases the volume of space in which the
molecules can move. The equation is
⎛ an 2 ⎞
⎜P +
V ⎠
( )
⎟ V − nb = nRT
⎝
where a and b are constants whose values depend on the gas. For this course we will stick with the ideal
gas law.
use the ideal gas law as an approximation with errors of less than ±2% in our
calculations.
Because the ideal gas law incorporates Boyle’s law and Charles’s law, we can use it to
solve problems similar to those in Examples 1 and 2. It is also a more powerful equation
because we can use it to evaluate the change in one parameter when two or three of the
remaining parameters change. Solving the ideal gas law for the gas constant gives
PV
R=
nT
P1V1 P2 V2
=
n1 T1 n2 T2
Example 3. A small bubble of methane, CH4, with a volume of 0.65 mL rises from the
bottom of swamp where the temperature is 15oC and the pressure is 2.8 atm, to the
swamp’s surface where the pressure is 1.0 atm and the temperature is 31oC. What is the
bubble’s volume when it reaches the swamp’s surface?
Solution. Because the moles of methane remains unchanged (n1 = n2) we may eliminate
n from our equation; thus
P1V1 P2 V2
=
T1 T2
T1 = 15 + 273.15 = 288 K
T
T2 = 31 + 273.15 = 304 K
T
Solving for V2 and making appropriate substitutions, gives the bubble’s volume as
PV
n=
RT
Example 4. In the course of an industrial reaction 2.5 × 105 L of carbon dioxide, CO2, are
added to a reaction mixture at a pressure of 1.2 atm and a temperature of 330oC. How
many moles of CO2 were added?
Solution. First, we covert the temperature from the Celsius to the Kelvin scale
Making appropriate substitutions into the ideal gas law gives the moles of CO2 as
The same approach can be used to calculate any one of the other variables (pressure,
volume, and temperature) given the moles of gas and values for the remaining variables.
Solution. Solving the ideal gas law for pressure and making appropriate substitutions
gives
L ⋅ atm
1.53 mol × 0.0821 × 298 K
P=
nRT
= mol ⋅K = 10.8 atm
V 3.47 L
As shown in the next example, we can turn this around and calculate the mass of LiOH
needed to remove all the CO2 in an enclosed space.
Example 6. How many grams of LiOH are needed to remove all the CO2 from the
enclosed space of a spaceship whose volume is 2.4× 105 L? The partial pressure of CO2
is 7.9× 10-3 atm † and the temperature is 296 K.
Solution. We begin by using the ideal gas law to calculate the moles of CO2 needing
removal; thus
Next, we use the reaction’s stoichiometry to determine the required moles of LiOH
This same approach can be applied to any of the stoichiometry problems described in
Modules 5 and 6.
†
Perhaps you are wondering why we can state just the pressure of CO2, ignoring the presence of other
gases (including the O2 the astronauts need to breathe) that must be present. The answer is that gases in
a mixture behave independently of each other. The total pressure, therefore, is a simple summation of
the pressures associated with each gas; thus
Ptotal = Pa + Pb + ••••• + Pn
where Pa, Pb, and Pn are the partial pressures associated with each gas. Because we are interested only
in the pressure of one gas, in this case CO2, we may ignore the pressures of other gases.
Example 7. Ammonium sulfate, (NH4)2SO4, is used as a fertilizer. One method for its
synthesis is by reacting gaseous ammonia, NH3, with sulfuric acid, H2SO4
How many grams of (NH4)2SO4 can be prepared by the reaction of 25.0 L of 3.0 M
H2SO4 with 3.1× 103 L of NH3 at a pressure of 1.0 atm and a temperature of 298 K?
Solution. To find the reaction’s limiting reagent, we first must determine the moles of
H2SO4 and NH3; thus
3.0 moles H2 SO 4
25.0 L × = 75.0 mol H 2SO 4
L
(
1.0 atm × 3.1× 10 L
3
)
= 127 mol NH3
L ⋅ atm
0.0821 × 298 K
mol ⋅ K
Using the reaction’s stoichiometry, 75.0 mol H2SO4 requires 150 mol NH3 to react
completely. Because we have less NH3 than needed, it is the limiting reagent. The
theoretical yield of ammonium sulfate, therefore, is
Practice Problems
The following problems provide practice in meeting this module’s objectives. Answers
are provided on the last page. Be sure to seek assistance if you experience difficulty with
any of these problems. When you are ready, schedule an appointment for the module
exam.
2. The gas evolved during the fermentation of glucose has a volume of 0.788 L at a
temperature of 22.8oC. What was the original volume of gas at the fermentation
temperature of 36.5oC? Assume that the pressure remains constant.
3. A gas-filled balloon with a volume of 2.8 L at 0.98 atm and a temperature of 25oC is
allowed to rise to the earth’s stratosphere where the temperature is -23oC and the
pressure is 0.00300 atm. What is the balloon’s new volume?
4. Workers at a research station in Antarctica collect a sample of air to test for airborne
pollutants. To collect the sample they use a 1.00-L container, acquiring the sample
when the air pressure is 1.03 atm at a temperature of -20oC. What is the pressure in
the container when the sample is opened up in a lab in South Carolina where the
temperature is 22oC?
6. Dry ice is solid carbon dioxide. Suppose that a 0.055-g sample of dry ice is placed
inside a 4.2-L container at 25.6oC. What is the partial pressure of CO2 in the
container after all the dry ice is converted to gaseous CO2?
Among its many uses, sodium bicarbonate, which is also known as baking soda, is
used as a leavening agent when making doughnuts and quick breads. Calculate the
volume of CO2 produced when 2.35 g NaHCO3 decompose at a temperature of 350oC
and a pressure of 1.05 atm.
How many nanograms of Mg are required to remove 4.6 × 10-9 atm of O2 in a 0.426-L
vacuum device at a temperature of 24.5oC?
9. In the metallurgical process for refining nickel, reacting it with carbon monoxide
volatilizes the metal.
The product, tetracarbonylnickel, is a gas that can be removed from the reaction
mixture. Further work-up allows the recovery of nickel metal, but without any of the
impurities present in the original sample. If a sample of impure nickel contains 77.4
g Ni, calculate the pressure of Ni(CO)4 collected in a 4.00-L storage tank at a
temperature of 43oC. Assume that carbon monoxide is present in excess.
10. The air bags in automobiles are inflated by nitrogen gas generated by the rapid
decomposition of sodium azide, NaN3, in the presence of excess iron oxide, Fe2O3
A typical air bag is designed to contain 37 L of nitrogen at a pressure of 1.15 atm and
a temperature of 26oC. How many grams of sodium azide are needed to completely
react all the N2?
11. There are several ways to generate oxygen gas for people working in submarines.
One method is to react carbon dioxide, CO2, with sodium peroxide, Na2O2, forming
sodium carbonate, Na2CO3, and oxygen, O2, as products
Assuming that the typical person exhales an average of 0.15 L of CO2 each minute (at
a pressure of 1.0 atm and a temperature of 25oC), how many kilograms of sodium
peroxide are needed to remove all the CO2 released by one person in a single day?
12. One method for generating chlorine gas, Cl2, is by reacting potassium permanganate,
KMnO4, and hydrochloric acid, HCl
How many liters of Cl2 at 40oC and a pressure of 1.05 atm can be produced by the
reaction of 6.23 g KMnO4 with 45.0 mL of 6.00 M HCl?
14. One method for determining the amount of pyruvic acid, C3H4O3, is to catalyze its
decomposition using a yeast enzyme. The reaction
produces carbon dioxide, which can be collected and used to determine the amount of
pyruvic acid in the original sample. In a typical analysis, 10.7 mL of CO2 are
obtained at a pressure of 0.983 atm and a temperature of 31oC. How many grams of
pyruvic acid were in the original sample?
Balance the reaction and determine the partial pressure of SO2 in a room with a
volume of 2.04 × 104 L and a temperature of 24.8oC following the lighting of a box of
matches whose combined mass of P4S3 is 0.800 g?
2. 0.824 L
3. 7.7 × 102 L
4. 1.20 atm
7. 0.681 L
8. 3.9 ng Mg
9. 8.55 atm
10. 75 g NaN3
12. 2.06 L
13. 56 g (NH2)2CO