9.3 Stoichiometry of Gaseous Substances, Mixtures, and Reactions

The study of the chemical behavior of gases was part of the basis of perhaps the most fundamental chemical revolution in history. French nobleman Antoine Lavoisier, widely regarded as the “father of modern chemistry,” changed chemistry from a qualitative to a quantitative science through his work with gases. He discovered the law of conservation of matter, discovered the role of oxygen in combustion reactions, determined the composition of air, explained respiration in terms of chemical reactions, and more. He was a casualty of the French Revolution, guillotined in 1794. Of his death, mathematician and astronomer Joseph-Louis Lagrange said, “It took the mob only a moment to remove his head; a century will not suffice to reproduce it.” Much of the knowledge we do have about Lavoisier's contributions is due to his wife, Marie-Anne Paulze Lavoisier, who worked with him in his lab. A trained artist fluent in several languages, she created detailed illustrations of the equipment in his lab, and translated texts from foreign scientists to complement his knowledge. After his execution, she was instrumental in publishing Lavoisier's major treatise, which unified many concepts of chemistry and laid the groundwork for significant further study.

As described in an earlier chapter of this text, we can turn to chemical stoichiometry for answers to many of the questions that ask “How much?” The essential property involved in such use of stoichiometry is the amount of substance, typically measured in moles (n). For gases, molar amount can be derived from convenient experimental measurements of pressure, temperature, and volume. Therefore, these measurements are useful in assessing the stoichiometry of pure gases, gas mixtures, and chemical reactions involving gases. This section will not introduce any new material or ideas, but will provide examples of applications and ways to integrate concepts already discussed.

Gas Density and Molar Mass

The ideal gas law described previously in this chapter relates the properties of pressure P, volume V, temperature T, and molar amount n. This law is universal, relating these properties in identical fashion regardless of the chemical identity of the gas:

P V = n R T

The density d of a gas, on the other hand, is determined by its identity. As described in another chapter of this text, the density of a substance is a characteristic property that may be used to identify the substance.

d = \frac{m}{V}

Rearranging the ideal gas equation to isolate V and substituting into the density equation yields

d = \frac{m P}{n R T} = (\frac{m}{n}) \frac{P}{R T}

The ratio m/n is the definition of molar mass, ℳ:

M = \frac{m}{n}

The density equation can then be written

d = \frac{M P}{R T}

This relation may be used for calculating the densities of gases of known identities at specified values of pressure and temperature as demonstrated in Example 9.11.

When the identity of a gas is unknown, measurements of the mass, pressure, volume, and temperature of a sample can be used to calculate the molar mass of the gas (a useful property for identification purposes). Combining the ideal gas equation

P V = n R T

and the definition of molar mass

M = \frac{m}{n}

yields the following equation:

M = \frac{m R T}{P V}

Determining the molar mass of a gas via this approach is demonstrated in Example 9.12.

Example 9.12Determining the Molecular Formula of a Gas from its Molar Mass and Empirical Formula

Cyclopropane, a gas once used with oxygen as a general anesthetic, is composed of 85.7% carbon and 14.3% hydrogen by mass. Find the empirical formula. If 1.56 g of cyclopropane occupies a volume of 1.00 L at 0.984 atm and 50 °C, what is the molecular formula for cyclopropane?

Solution

First determine the empirical formula of the gas. Assume 100 g and convert the percentage of each element into grams. Determine the number of moles of carbon and hydrogen in the 100-g sample of cyclopropane. Divide by the smallest number of moles to relate the number of moles of carbon to the number of moles of hydrogen. In the last step, realize that the smallest whole number ratio is the empirical formula:

85.7 g C \times \frac{1 mol C}{12.01 g C} = 7.136 mol C \frac{7.136}{7.136} = 1.00 mol C

Example 9.13Determining the Molar Mass of a Volatile Liquid

The approximate molar mass of a volatile liquid can be determined by:

Heating a sample of the liquid in a flask with a tiny hole at the top, which converts the liquid into gas that may escape through the hole
Removing the flask from heat at the instant when the last bit of liquid becomes gas, at which time the flask will be filled with only gaseous sample at ambient pressure
Sealing the flask and permitting the gaseous sample to condense to liquid, and then weighing the flask to determine the sample’s mass (see Figure 9.19)

Figure 9.19When the volatile liquid in the flask is heated past its boiling point, it becomes gas and drives air out of the flask. At

t_{l ⟶ g},

the flask is filled with volatile liquid gas at the same pressure as the atmosphere. If the flask is then cooled to room temperature, the gas condenses and the mass of the gas that filled the flask, and is now liquid, can be measured. (credit: modification of work by Mark Ott)

The Pressure of a Mixture of Gases: Dalton’s Law

Unless they chemically react with each other, the individual gases in a mixture of gases do not affect each other’s pressure. Each individual gas in a mixture exerts the same pressure that it would exert if it were present alone in the container (Figure 9.20). The pressure exerted by each individual gas in a mixture is called its partial pressure. This observation is summarized by Dalton’s law of partial pressures: The total pressure of a mixture of ideal gases is equal to the sum of the partial pressures of the component gases:

P_{T o t a l} = P_{A} + P_{B} + P_{C} + ... = Σ_{i} P_{i}

In the equation P $_{T o t a l}$ is the total pressure of a mixture of gases, P $_{A}$ is the partial pressure of gas A; P $_{B}$ is the partial pressure of gas B; P $_{C}$ is the partial pressure of gas C; and so on.

This figure includes images of four gas-filled cylinders or tanks. Each has a valve at the top. The interior of the first cylinder is shaded blue. This region contains 5 small blue circles that are evenly distributed. The label “300 k P a” is on the cylinder. The second cylinder is shaded lavender. This region contains 8 small purple circles that are evenly distributed. The label “450 k P a” is on the cylinder. To the right of these cylinders is a third cylinder. Its interior is shaded pale yellow. This region contains 12 small yellow circles that are evenly distributed. The label “6000 k P a” is on this region of the cylinder. An arrow labeled “Total pressure combined” appears to the right of these three cylinders. This arrow points to a fourth cylinder. The interior of this cylinder is shaded a pale green. It contains evenly distributed small circles in the following quantities and colors; 5 blue, 8 purple, and 12 yellow. This cylinder is labeled “1350 k P a.” — Figure 9.20If equal-volume cylinders containing gasses at pressures of 300 kPa, 450 kPa, and 600 kPa are all combined in the same-size cylinder, the total pressure of the gas mixture is 1350 kPa.

The partial pressure of gas A is related to the total pressure of the gas mixture via its mole fraction (X), a unit of concentration defined as the number of moles of a component of a solution divided by the total number of moles of all components:

P_{A} = X_{A} \times P_{T o t a l} where X_{A} = \frac{n _{A}}{n _{T o t a l}}

where P $_{A}$ , X $_{A}$ , and n $_{A}$ are the partial pressure, mole fraction, and number of moles of gas A, respectively, and n $_{T o t a l}$ is the number of moles of all components in the mixture.

Here is another example of this concept, but dealing with mole fraction calculations.

Collection of Gases over Water

A simple way to collect gases that do not react with water is to capture them in a bottle that has been filled with water and inverted into a dish filled with water. The pressure of the gas inside the bottle can be made equal to the air pressure outside by raising or lowering the bottle. When the water level is the same both inside and outside the bottle (Figure 9.21), the pressure of the gas is equal to the atmospheric pressure, which can be measured with a barometer.

This figure shows a diagram of equipment used for collecting a gas over water. To the left is an Erlenmeyer flask. It is approximately two thirds full of a lavender colored liquid. Bubbles are evident in the liquid. The label “Reaction Producing Gas” appears below the flask. A line segment connects this label to the liquid in the flask. The flask has a stopper in it through which a single glass tube extends from the open region above the liquid in the flask up, through the stopper, to the right, then angles down into a pan that is nearly full of light blue water. This tube again extends right once it is well beneath the water’s surface. It then bends up into an inverted flask which is labeled “Collection Flask.” This collection flask is positioned with its mouth beneath the surface of the light blue water and appears approximately half full. Bubbles are evident in the water in the inverted flask. The open space above the water in the inverted flask is labeled “collected gas.” — Figure 9.21When a reaction produces a gas that is collected above water, the trapped gas is a mixture of the gas produced by the reaction and water vapor. If the collection flask is appropriately positioned to equalize the water levels both within and outside the flask, the pressure of the trapped gas mixture will equal the atmospheric pressure outside the flask (see the earlier discussion of manometers).

However, there is another factor we must consider when we measure the pressure of the gas by this method. Water evaporates and there is always gaseous water (water vapor) above a sample of liquid water. As a gas is collected over water, it becomes saturated with water vapor and the total pressure of the mixture equals the partial pressure of the gas plus the partial pressure of the water vapor. The pressure of the pure gas is therefore equal to the total pressure minus the pressure of the water vapor—this is referred to as the “dry” gas pressure, that is, the pressure of the gas only, without water vapor. The vapor pressure of water, which is the pressure exerted by water vapor in equilibrium with liquid water in a closed container, depends on the temperature (Figure 9.22); more detailed information on the temperature dependence of water vapor can be found in Table 9.2, and vapor pressure will be discussed in more detail in the next chapter on liquids.

A graph is shown. The horizontal axis is labeled “Temperature ( degrees C )” with markings and labels provided for multiples of 20 beginning at 0 and ending at 100. The vertical axis is labeled “Vapor pressure ( torr )” with marking and labels provided for multiples of 200, beginning at 0 and ending at 800. A smooth solid black curve extends from the origin up and to the right across the graph. The graph shows a positive trend with an increasing rate of change. On the vertical axis is ( 7 60) and an arrow pointing to it. The arrow is labeled, “Vapor pressure at ( 100 degrees C ).” — Figure 9.22This graph shows the vapor pressure of water at sea level as a function of temperature.

Table 9.2

Vapor Pressure of Ice and Water in Various Temperatures at Sea Level
Temperature (°C)	Pressure (torr)	Temperature (°C)	Pressure (torr)	Temperature (°C)	Pressure (torr)
–10	1.95	18	15.5	30	31.8
–5	3.0	19	16.5	35	42.2
–2	3.9	20	17.5	40	55.3
0	4.6	21	18.7	50

Chemical Stoichiometry and Gases

Chemical stoichiometry describes the quantitative relationships between reactants and products in chemical reactions.

We have previously measured quantities of reactants and products using masses for solids and volumes in conjunction with the molarity for solutions; now we can also use gas volumes to indicate quantities. If we know the volume, pressure, and temperature of a gas, we can use the ideal gas equation to calculate how many moles of the gas are present. If we know how many moles of a gas are involved, we can calculate the volume of a gas at any temperature and pressure.

Avogadro’s Law Revisited

Sometimes we can take advantage of a simplifying feature of the stoichiometry of gases that solids and solutions do not exhibit: All gases that show ideal behavior contain the same number of molecules in the same volume (at the same temperature and pressure). Thus, the ratios of volumes of gases involved in a chemical reaction are given by the coefficients in the equation for the reaction, provided that the gas volumes are measured at the same temperature and pressure.

We can extend Avogadro’s law (that the volume of a gas is directly proportional to the number of moles of the gas) to chemical reactions with gases: Gases combine, or react, in definite and simple proportions by volume, provided that all gas volumes are measured at the same temperature and pressure. For example, since nitrogen and hydrogen gases react to produce ammonia gas according to $N_{2} (g) + 3 H_{2} (g) ⟶ 2 NH_{3} (g),$ a given volume of nitrogen gas reacts with three times that volume of hydrogen gas to produce two times that volume of ammonia gas, if pressure and temperature remain constant.

The explanation for this is illustrated in Figure 9.23. According to Avogadro’s law, equal volumes of gaseous N₂, H₂, and NH₃, at the same temperature and pressure, contain the same number of molecules. Because one molecule of N₂ reacts with three molecules of H₂ to produce two molecules of NH₃, the volume of H₂ required is three times the volume of N₂, and the volume of NH₃ produced is two times the volume of N₂.

This diagram provided models of the chemical reaction written with formulas across the bottom of the figure. The reaction is written; N subscript 2 plus 3H subscript 2 followed by an arrow pointing right to NH subscript 3. Just above the formulas, space-filling models are provided. Above NH subscript 2, two blue spheres are bonded. Above 3H subscript 2, three pairs of two slightly smaller white spheres are bonded. Above NH subscript 3, two molecules are shown composed each of a central blue sphere to which three slightly smaller white spheres are bonded. Across the top of the diagram, the reaction is illustrated with balloons. To the left is a light blue balloon, which is labeled “N subscript 2”. This balloon contains a single space-filling model composed of two bonded blue spheres. This balloon is followed by a plus sign, then three grey balloons which are each labeled “H subscript 2.” Each of these balloons similarly contain a single space-filling model composed of two bonded white spheres. These white spheres are slightly smaller than the blue spheres. An arrow follows that points right to two light-green balloons, which are each labeled “2 NH subscript 3.” Each light-green balloon contains a space-filling model composed of a single central blue sphere to which three slightly smaller white spheres are bonded. — Figure 9.23One volume of N₂ combines with three volumes of H₂ to form two volumes of NH₃.

Greenhouse Gases and Climate Change

The thin skin of our atmosphere keeps the earth from being an ice planet and makes it habitable. In fact, this is due to less than 0.5% of the air molecules. Of the energy from the sun that reaches the earth, almost $\frac{1}{3}$ is reflected back into space, with the rest absorbed by the atmosphere and the surface of the earth. Some of the energy that the earth absorbs is re-emitted as infrared (IR) radiation, a portion of which passes back out through the atmosphere into space. Most of this IR radiation, however, is absorbed by certain atmospheric gases, effectively trapping heat within the atmosphere in a phenomenon known as the greenhouse effect. This effect maintains global temperatures within the range needed to sustain life on earth. Without our atmosphere, the earth's average temperature would be lower by more than 30 °C (nearly 60 °F). The major greenhouse gases (GHGs) are water vapor, carbon dioxide, methane, and ozone. Since the Industrial Revolution, human activity has been increasing the concentrations of GHGs, which have changed the energy balance and are significantly altering the earth’s climate (Figure 9.24).

Susan Solomon

Atmospheric and climate scientist Susan Solomon (Figure 9.26) is the author of one of The New York Times books of the year (The Coldest March, 2001), one of Time magazine’s 100 most influential people in the world (2008), and a working group leader of the Intergovernmental Panel on Climate Change (IPCC), which was the recipient of the 2007 Nobel Peace Prize. She helped determine and explain the cause of the formation of the ozone hole over Antarctica, and has authored many important papers on climate change. She has been awarded the top scientific honors in the US and France (the National Medal of Science and the Grande Medaille, respectively), and is a member of the National Academy of Sciences, the Royal Society, the French Academy of Sciences, and the European Academy of Sciences. Formerly a professor at the University of Colorado, she is now at MIT, and continues to work at NOAA.

For more information, watch this video about Susan Solomon.

Figure 9.26Susan Solomon’s research focuses on climate change and has been instrumental in determining the cause of the ozone hole over Antarctica. (credit: National Oceanic and Atmospheric Administration)

Key Concepts and Summary

The ideal gas law can be used to derive a number of convenient equations relating directly measured quantities to properties of interest for gaseous substances and mixtures. Appropriate rearrangement of the ideal gas equation may be made to permit the calculation of gas densities and molar masses. Dalton’s law of partial pressures may be used to relate measured gas pressures for gaseous mixtures to their compositions. Avogadro’s law may be used in stoichiometric computations for chemical reactions involving gaseous reactants or products.

Key Equations

P $_{T o t a l}$ = P $_{A}$ + P $_{B}$ + P $_{C}$ + … = Ʃ