CHEMISTRY 2e

Chapter 9 GASES
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Gas Pressure

• Pressure is defined as the force exerted on a given area.

• Gas pressure is a result of the force exerted by gas molecules

colliding with the surface of objects.

• English system units for pressure: pounds per square inch (psi)

• A mercury barometer is a device used to measure the atmospheric

pressure.
Figure 9.3

Although (a) an elephant’s weight is large, creating a very large force on the ground, (b) the
figure skater exerts a much higher pressure on the ice due to the small surface area of her
skates.
(credit a: modification of work by Guido da Rozze; credit b: modification of work by
Ryosuke Yagi)
Units of Pressure

• Due to the way gas pressure is measured, millimeters of mercury

(mm Hg) is a commonly used unit of pressure.

• Probably the most common unit of gas pressure is the atmosphere

(atm).
• 1 atm is the “normal atmospheric pressure”
• 1 atm = 760 mm Hg
Units of Pressure

• SI unit for pressure is the Pascal (Pa).

• 1 Pa is defined as the pressure exerted by a 0.1 mm high film of water on the
surface beneath it.
• Kilopascal (kPa)

• A related unit of pressure is the bar.

• 1 bar = 105 Pa

• Pressure conversions:
• 1.013 bar = 1 atm = 760 mm Hg = 760 torr
• = 14.7 psi = 101.3 kPa
Measuring Atmospheric Pressure

• The barometer measures pressure in terms of the height of a column

of liquid mercury.

• The atmosphere exerts a force on the liquid mercury causing it to

rise.

• Commonly, the pressure of the atmosphere at sea level pushes the

column of mercury ~760 mm high.

• The pressure exerted by a fluid due to gravity is known as hydrostatic

pressure, p:
P = h.ρ.g

where h is the height of the fluid, ρ is the density of the fluid,

and g is acceleration due to gravity.
Figure 9.4

In a barometer, the height, h, of the

column of liquid is used as a
measurement of the air pressure.
Using very dense liquid mercury
(left) permits the construction of
reasonably sized barometers,
whereas using water (right) would
require a barometer more than 30
feet tall.
Atmospheric Pressure and Altitude

• Pressure varies with the height of the column of air above.

• We don’t notice atmospheric pressure but do notice changes in

atmospheric pressure
Measuring the Pressure of a Confined Gas—The Manometer

• The force of the gas in the flask is measured relative to the force of
the atmosphere (atmospheric pressure).

• The distance and direction that the Hg travels is related to the

pressure of the gas.
Figure 9.5

A manometer can be used to measure the pressure of a gas. The (difference in) height
between the liquid levels (h) is a measure of the pressure. Mercury is usually used because
of its large density.
Example 9.3
Example 9.4
Volume of a Gas

• At constant temperature and pressure, a gas expands uniformly to fill

the container in which it is contained.
Relating Pressure, Volume, Amount, Temperature:
The Ideal Gas Law
• There are many different types of gases.
• Elements: Ar, He, H2, N2, O2
• Compounds: CO2, CO, H2O, NH3

• All gases have the same dependence on those four properties.

• Volume
• Amount
• Temperature
• Pressure
Figure 9.10

The effect of temperature on gas pressure: When the hot plate is off, the pressure of the
gas in the sphere is relatively low. As the gas is heated, the pressure of the gas in the
sphere increases.
Pressure and Temperature

• The pressure of a gas is directly proportional to its temperature in K.

• At constant V and n

P = kT (P/T = k)

• This is Amonton’s Law or Gay-Lussac’s Law.

Figure 9.11

For a constant volume and amount of air, the pressure and temperature are directly
proportional, provided the temperature is in kelvin. (Measurements cannot be made at
lower temperatures because of the condensation of the gas.) When this line is extrapolated
to lower pressures, it reaches a pressure of 0 at –273 °C, which is 0 on the kelvin scale and
the lowest possible temperature, called absolute zero.
Volume and Temperature

• The volume of a gas is directly proportional to its temperature in K.

• At constant P and n

V = kT (V/T = k)

• This is Charles’s Law.

Figure 9.12

The volume and temperature are linearly related for 1 mole of methane gas at a constant
pressure of 1 atm. If the temperature is in kelvin, volume and temperature are directly
proportional. The line stops at 111 K because methane liquefies at this temperature; when
extrapolated, it intersects the graph’s origin, representing a temperature of absolute zero.
Volume and Pressure

• The volume of a gas is inversely proportional to its pressure.

• At constant T and n

k
V= (P.V = k)
P
• This is Boyle’s Law.
Figure 9.13
Volume and Amount (Moles)

• The volume of a gas is directly proportional to its amount (moles of

gas).

• At constant T and P

V = kn (V/n = k)

• This is Avogadro’s Law.

The Ideal Gas Law

k
P = kT V = kT V= V = kn
P
• These four equations can be combined into a single law consisting of
all four properties.

• The Ideal Gas Law: PV = nRT

• The four constants (k) were combined into a new constant, R, called
the ideal gas constant.
The Ideal Gas Law

PV = nRT
• P is the pressure in atm.
• V is the volume in L.
• n is the moles of gas.
• T is the temperature in K.
• R is the ideal gas constant.

L × atm
𝑅 = 0.08206
mol × K
The Ideal Gas Law

PV = nRT
• The ideal gas law accurately describes the properties of an ideal gas.

• What is an ideal gas? What assumptions are being made?

A gas that behaves ideally (more details later).
This assumption is only reasonable for gases under conditions of
relatively low pressure and high temperature.
Modified Ideal Gas Law

PV = nRT
• Modified version of the ideal gas law:
• Moles kept constant (PV/T = nR = k)
• But other properties change (two different sets of conditions)

• Combined Gas Law:

Standard Temperature and Pressure

• Sometimes it is important to define standard conditions.

• Standard temperature and pressure (STP)

• 0 oC = 273 K
• 1 atm

Note: The IUPAC recommended value of standard pressure was changed to 1

bar in 1982, but many texts continue to use the 1 atm value.

• At STP, the volume of one mole of any gas can be calculated.

Figure 9.18

Regardless of its chemical identity, one mole of gas behaving ideally occupies a volume of
~22.4 L at STP.
Calculating the Density of a Gas

• Recall, the density of a substance

mass
𝑑=
𝑉
• We can rearrange the following equation (Ideal Gas Law)

grams
𝑃𝑉 = 𝑅𝑇
ℳ
• Substitute into the density equation to obtain

ℳ𝑃
𝑑=
𝑅𝑇
Density of Gases

ℳ𝑃
𝑑=
𝑅𝑇
• Recall that density is an intensive property.
• Does not depend on the amount of substance

• But, the density of a gas does depend on

• Pressure
• Temperature
• Molar mass
Calculating the Molar Mass of a Gas

• Recall, the molar mass ( ℳ ) of a substance.

𝑔𝑟𝑎𝑚𝑠 𝑚
ℳ= =
𝑚𝑜𝑙𝑒 𝑛

• This expression can be rearranged.

𝑚
𝑛=
ℳ

• And then substituted into the Ideal Gas Law.

𝑚
𝑃𝑉 = 𝑅𝑇
ℳ
Dalton’s Law

• The ideal gas law also applies to mixtures of gases if the gases don’t
react with each other.

• Dalton’s law of partial pressure: The total pressure of a mixture of

ideal gases is equal to the sum of the partial pressures of the
component gases.

PT = PA + PB + PC …
Dalton’s Law of Partial Pressure

PT = PA + PB + PC …

• For a mixture of gases A, B, C, …

• PT is the total pressure of the gas mixture
• PA is the partial pressure of gas A
• PB is the partial pressure of gas B
• PC is the partial pressure of gas C

• The pressure exerted by each individual gas in a mixture is called its

partial pressure.
• The partial pressure is equal to the pressure that the gas would exert if it
were by itself.
Figure 9.20

If equal-volume cylinders containing gas A at a pressure of 300 kPa, gas B at a pressure of

600 kPa, and gas C at a pressure of 450 kPa are all combined in the same-size cylinder, the
total pressure of the mixture is 1350 kPa.
Partial Pressure and Mole Fraction

• We can express the partial pressure of a gas in a mixture in terms of

its mole fraction.

• Consider a mixture of gases A and B.

PA = X A PT PB = X B PT
• The mole fraction of gas A (ΧA) is the number of moles of A divided by
the total number of moles of gas in the mixture.
Collecting a Gas Over Water

• A common way to collect and quantify a gas produced in a chemical

reaction is to capture the gas in an inverted bottle that had been
filled with water.

• The volume of water displaced can then be related back to the

amount of gas produced.

• As the gas travels through the water, it picks up water vapor, H2O (g).

• The collected gas mixture has a PT equal to the atmospheric pressure.

Figure 9.21

When 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).
Wet Gases

• We refer to the gas collected over water as a wet gas mixture.

• Say, for example, that the gas being collected was H2.

PT = PH 2O + PH 2
• PT is the atmospheric pressure.

• PH2 is the partial pressure of the H2 (g) collected.

• PH2O is the vapor pressure of water.

Vapor Pressure
• Vapor pressure of water: The pressure exerted by water vapor in
equilibrium with liquid water in a closed container.

• Intensive property—does not depend on the amount of water

• Temperature dependent
Stoichiometry in Gaseous Reactions

• Gases may appear as reactants or products in a chemical reaction.

• The ideal gas law and a balanced chemical equation can be used to
relate the P, V, T, n, and grams of a gas that takes part in a chemical
reaction.

• Stoichiometric factors can be used to relate the moles of one

substance to the moles of any other substance in a balanced
chemical equation.
Stoichiometry with Gas Volumes

• The volume ratio of any two gases in a reaction at constant

temperature and pressure is the same as the stoichiometric ratio
(mole ratio) in the balanced chemical equation.

• Recall that V = kn (constant T, P). The volume of a gas is directly

proportional to the moles of gas.
Figure 9.23

One volume of N2 combines with three volumes of H2 to form two volumes of NH3.
Figure 9.27

(a) Two gases, H2 and O2, are initially separated. (b) When the stopcock is opened, they mix
together. The lighter gas, H2, passes through the opening faster than O2, so just after the
stopcock is opened, more H2 molecules move to the O2 side than O2 molecules move to the
H2 side. (c) After a short time, both the slower-moving O2 molecules and the faster-moving
H2 molecules have distributed themselves evenly on both sides of the vessel.
Figure 9.28

Diffusion occurs when gas molecules disperse throughout a container. Effusion occurs
when a gas passes through an opening that is smaller than the mean free path of the
particles, that is, the average distance traveled between collisions. Effectively, this means
that only one particle passes through at a time.
Graham’s Law of Effusion
Figure 9.29

The left photograph shows two balloons inflated with different gases, helium (orange) and
argon (blue). The right-side photograph shows the balloons approximately 12 hours after
being filled, at which time the helium balloon has become noticeably more deflated than
the argon balloon, due to the greater effusion rate of the lighter helium gas. (credit:
modification of work by Paul Flowers)
Figure 9.33

The molecular speed distribution for nitrogen gas (N2) shifts to the right and flattens as the
temperature increases; it shifts to the left and heightens as the temperature decreases.
Figure 9.34

Molecular velocity is directly related to molecular mass. At a given temperature, lighter

molecules move faster on average than heavier molecules.
The van der Waals equation