Chapter 5: Gases (Ch 10 in Jespersen, Ch 5 in Chang)

Elements that exist as gases (at 25 oC and 1atm) are shown in blue.

Our atmosphere is: Nitrogen 78%, Oxygen 21%, Argon 0.9%, Carbon Dioxide 0.03%, Water vapor 0.0 to 4.0%.

Trace gases include neon, helium, krypton, and xenon.

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Characteristics of Gases

• expand to fill container.

• can be expanded or compressed.

• form homogeneous mixtures (e.g. air).

• have much lower densities than liquids and solids.

• gases only occupy a small fraction of the total volume; they behave as if the other molecules were absent.

• they can exert a pressure (e.g. balloons).

• the pressure depends on the amount of confined gas.

• the pressure will rise and fall with temperature.

The fact that gases are readily compressible and immediately fill the space available to them suggests that
molecules of gases are widely separated and in ceaseless chaotic motion.

Even though gases can vary tremendously in their chemical properties, essentially all gases obey the same set of
physical properties.

These four inter-related physical properties are Pressure, Volume, Temperature and Amount.

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Pressure (P)

Pressure is a force per unit area.

Force = mass (kg) x acceleration (ms-2).

The SI unit of force is the Newton, N.

The SI unit of Pressure is the Pascal, Pa.

Pressures can also be expressed as pressures that can support a certain sized column of mercury (at a given
elevation and temperature).

Standard atmospheric pressure (1 atm) is the pressure that supports a column of mercury 760 mm high at 0 oC at
sea level.

1 atm = 760 mmHg = 760 torr = 1.01325 × 105 Pa = 101.325 kPa = 29.92 inHg = 14.696 psi

1 torr = 1 mmHg 1 bar = 105 Pa 1 bar ≈ 1 atm.

Named after Torricelli who invented the barometer - a barometer is an instrument that measures atmospheric
pressure.

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Mt Everest 29000 ft 253 mmHg (low pressure)

Denver 5,690 ft 620 mmHg

Dead Sea 1,407 ft below sea level 799 mmHg (high pressure)

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A manometer is an instrument that can measure pressure (of gases other than the atmosphere).

Either they are (a) closed tube (to measure pressure below atmospheric), or

(b) open tube (to measure pressure equal or greater than atmospheric pressure).

Mercury is used since it has such a high density (1.36 g/mL).

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 The Gas Laws

The gas laws were developed at the end of the 18th century, when scientists (through experimental observations)
began to realize that relationships between the pressure, volume and temperature of a sample of gas could be
obtained which would hold to a good approximation for all gases. Gases behave in a similar way over a wide
variety of conditions because they all have molecules which are widely spaced.

Previously: these four inter-related physical properties are Pressure, Volume, Temperature and Amount.

Boyle’s Law (the Pressure/Volume Relationship – the 1600’s)

The pressure of a fixed amount of gas maintained at constant temperature is inversely proportional to the volume.

𝟏
P∝
𝐕

1
Also: P = k ×
V

or

PV = k where k = constant.

Smaller Volume  Larger Pressure

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Charles's Law (the Volume/Temperature Relationship – in the 1700’s).

The volume of a fixed amount of gas maintained at constant pressure is directly proportional to its absolute
temperature.

V∝T

or

V=k×T

or

V
=k
T

At any pressure, the plot of volume versus temperature gave a straight line.

By extending the line to zero volume, every line gave the same intercept on the temperature axis.

In 1848, Kelvin identified this temperature as absolute zero (set as 0 K on the absolute temperature scale), the
theoretically lowest attainable temperature.

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Gay-Lussac’s Law (the Pressure/Temperature Relationship – in the 1800’s).

The pressure of a fixed amount of gas maintained at constant volume is directly proportional to its absolute
temperature.

P∝T

or

P=k×T

or

P
=k
T

Pressure increases as temperature increases.

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Avogadro’s Law (the Volume/Amount relationship - 1811)

At constant pressure and temperature, the volume of a gas is directly proportional to the number of moles of the
gas present.

V∝n (n = amount of substance)

Or V=k×n

V
So = k = Vm or V = nVm
n
L
Where Vm is the molar volume = 22.4 (more on this later)
mol

(Equal volumes of gases at the same temperature and pressure contain equal numbers of molecules).

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The Ideal Gas Equation
1
Boyle’s law (constant n and T) V∝
P

Charles’s Law (constant n and P) V∝T

Avogadro’s Law (constant P and T) V∝n

nT
So if R is a (the Gas) constant: V=R
P

PV = nRT Ideal Gas Law

An ideal gas is a hypothetical gas whose pressure-volume-temperature behavior can be completely accounted for
by the ideal gas equation. (Ideal behavior is seen at lower pressures and higher temperatures).

For an ideal gas we pretend:

• Molecules of an ideal gas do not attract or repel one another.

• They have negligible volume compared to the container.

PV=nRT is the equation of state of a gas.

If we know three of the 4 variables, we can calculate the fourth.

We can define the state of a gas by defining three of these values. (See Ch 6 in my notes for more on “states”).
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The Gas Constant

If we apply PV=nRT at 0 oC (273.15 K), using 1 mol of ideal gas occupying 22.4 L (established by experiment),
we get the value of R:
L⋅atm
R = 0.08206
mol⋅K

J
Beware of units – R is sometimes expressed as R = 8.314
mol⋅K

Standard Temperature and Pressure (STP) is defined as:

STP T = 273.15 K = 0 °C P = 1.0000 atm

All of the other gas laws can be derived from the ideal gas law…

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So we have: PV = nRT where R is a constant.

In Chemistry we often deal with changes or modifications:

P1 V1 P2 V2
R= (before the change) and R= (after the change)
n1 T1 n2 T2

P1 V1 P2 V2
Therefore: = This is called the Combined Gas Law.
n1 T1 n2 T2

If the number of moles doesn't change (common for gas experiments, n 1 = n2)
P1 V1 P2 V2
then: =
T1 T2

If other variables are constant we get these useful forms:

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Problem: An inflated balloon has a volume of 6.0 L at sea level (1.0 atm) and is allowed to ascend in altitude until
the pressure is 0.45 atm. During the ascent the temperature of the gas falls from 22 °C to −21 °C.

Calculate the volume of the balloon at its final altitude.

So we know: V1 = 6.0 L V2 = ?

P1 = 1.0 atm P2 = 0.45 atm

T1 = 22 oC T2 = −21 oC

Use KELVINS in Gas problems! T1 = 295 K T2 = 252 K

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Problem: Calculate the volume occupied by 0.54 mol of N2 at 15 °C and 0.976 atm.

If given moles, use the ideal-gas law: PV = nRT

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When to use the Ideal Gas Law, or the Combined Gas Law ?

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Stoichiometry: Stoichiometric connections can be included in gas law type problems:

Problem: What is the pressure in atmospheres in a 35.0 L balloon at 25.0 °C filled with dried hydrogen gas
produced by the reaction of 39.8 g of NaH with water?

We need to find the number of moles of hydrogen from the balanced equation:

NaH(s) + H2O(l) → NaOH(aq) + H2(g)

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Further Applications of the Ideal-Gas Equation (to determine molecular weights)
n P
= if we multiply both sides by the Molecular Weight, M, of the gas:
V RT

nM PM nM moles grams grams

= but = ⋅ = = density (of a gas), d
V RT V liter mole liter

PM 𝐝𝐑𝐓
d= rearranged is M=
RT 𝐏

Problem: If a 2.00 L flask contains 3.11 g of cyclopropane gas at 684 torr and 23.0 °C, what is the molecular
weight of cyclopropane? (R = 0.08206 L⋅atm/mol⋅K)

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An alternative solution could find the number of moles, and then use that to find the MW:

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 Gas Mixtures and Partial Pressures

So far we have talked about pure gaseous substances – but in reality we will encounter mixtures of gases.

Dalton’s Law of Partial Pressures (1801) – the total pressure of a mixture of (non-reacting) gases equals the sum
of the pressures that each would exert if it were present alone.

The total pressure is the same as the sum of the grey pressure and the red pressure.
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We can express this mathematically:

(Assuming each gas behaves ideally)

Xi is the mole fraction of i, which is a dimensionless quantity that expresses the ratio of the number of moles of
one component to the total number of moles of all the components present.

Sometimes mole fraction is also expressed as Mole Percent:

Mole % = Xa × 100%

Xa = ½  mole percent = 50%.

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This is useful for gases collected over water. E.g. If oxygen is collected over water, then the total pressure is:

The pressure of gas in the bottle is not only due to O2, but also to water vapor. The vapor pressure of water varies
with temperature. If we are to calibrate the bottle (for amount of O2 produced), we must take this into account.

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Problem: A mixture of gases contains 0.75 mol N2, 0.30 mol O2, and 0.15 mol CO2.

If the total pressure is 1.56 atm, what is the partial pressure of each component?

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Problem: At an underwater depth of 250 ft, the pressure is 8.38 atm. What should the mole percent of oxygen be
in the diving gas for the partial pressure of oxygen in the mixture to be 0.21 atm, the same as in air at 1 atm?

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Kinetic-Molecular Theory (Boltzmann and Maxwell – Late 1800’s)

The kinetic (molecular) theory describes a gas as a large number of submicroscopic particles (atoms or molecules),
all of which are in constant, rapid motion that have randomness arising from their many collisions with each other
and with the walls of the container.

Kinetic theory explains macroscopic properties of gases, such as pressure, temperature, viscosity, thermal
conductivity, and volume, by considering their molecular composition and motion.

The theory posits that gas pressure is due to the impacts on the walls of a container, of molecules or atoms moving
at different velocities.

Assumptions made:

1. Gases are collections of molecules in continuous random motion.

2. Gas molecules are infinitesimally small particles.

3. Particles move in straight lines until they collide.

4. Molecules do not influence one another except when they collide.

5. The average kinetic energy of the molecules is proportional to the absolute temperature. (At any given
temperature the molecules of all gases have the same kinetic energy).

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Kinetic-Molecular Theory gives us an understanding of pressure and temperature on the molecular level.

• Pressure results from collisions of molecules with the walls of the container.

• The magnitude of pressure is determined by how often and how hard the molecules strike the walls of the
container.

• Absolute temperature of a gas is a measure of the average kinetic energy of the molecules.

• Some molecules will have less kinetic energy and some will have more kinetic energy than the average
(distribution).

Visual Illustrations

More wall collisions = Higher P Less wall collisions = Lower P

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Lower T = slower motion (softer collisions)= Lower P Higher T = more ke = harder collisions= Higher P

Lower T = slower motion, need smaller V to maintain P. Higher T = more motion, need larger V to keep P

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Less molecules means need smaller V to maintain P. More molecules means need bigger V to keep P.

We now are able to address gaseous motion, and there are two different types: diffusion and effusion…

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Diffusion is the gradual mixing of molecules
of one gas with molecules of another,
by virtue of their kinetic properties.

(E.g. smelling your food).

Effusion is the process by which a gas under pressure

escapes from one compartment of a container to another
by passing through a small opening.

Effusion is the process in which a gas escapes through a

hole of diameter considerably smaller than the mean
free path of the molecules.

(The mean free path is the average distance traveled by a gas molecule between collisions. At sea level, the mean
free path for air molecules is about 6 × 10-6 cm).
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Graham’s Law of Effusion (1832)

Graham studied the rates of effusion (and diffusion) of gases, and their relationship to molecular weight.

He found that the rate of effusion is inversely proportional to the (square root of the) molecular weight of the gas.

Graham’s Law is usually used to compare the rates of effusion of two different gases:

For two gasses A and B (at the same Temperature and Pressure):

The rate of effusion is the number of molecules passing through a point in a given time. The longer the time it
takes, the slower is the rate. Therefore the rate is inversely proportional to the time required for effusion.

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Distribution of Molecular Speeds

We previously said the absolute temperature of a gas is a measure of the average kinetic energy of the molecules,
𝟏
which is related to the speed of the molecules (ke = mv2).
𝟐

This Maxwell speed distribution curve is for N2 at

three different temperatures, displaying the number
of molecules moving at a certain speed.

The speed at the top of the curve is called the most

probable speed because the largest number of
molecules have that speed.

At lower temperatures, the molecules have less

energy. Therefore, the speeds of the molecules are
lower and the distribution has a smaller range.

As the temperature of the molecules increases, the

distribution flattens out. Since the molecules have
greater energy at higher temperature, the molecules
are moving faster.

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This graph shows the speed distribution of three
different gases at the same temperature.

On average, heavier molecules move more slowly than

lighter molecules.
(Lighter molecules move faster, on average, than
heavier molecules).

Therefore, heavier molecules will have a smaller speed

distribution, while lighter molecules will have a speed
distribution that is more spread out.

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Problem: Arsenic (III) sulfide sublimes readily. The molecules of the vapor phase are found to effuse through a
tiny hole at 0.28 times the rate of effusion of Ar atoms under the same conditions of temperature and pressure.
What is the molecular formula of arsenic (III) sulfide in the gas phase?

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Real Gases: Deviations from Ideal Behavior

Assumptions for Ideal Behavior included:

• Gas molecules do not exert forces, attractive or repulsive, on each other.

• The volume of the molecules is negligibly small compared with the volume of the container.

Ideal behavior is seen at lower pressures and higher temperatures.

But if we move away from these conditions, we observe that gases exhibit more non-ideal behavior at higher
pressures and lower temperatures.

The van der Waals equation (or van der Waals equation of state, 1873) can be viewed as an adjustment to the ideal
gas law that takes into account the non-zero volume of gas molecules, which are subject to an inter-particle
attraction.

We know ideally that PV = nRT, but we can correct for molecular attraction, and volume of molecules:

a – magnitude of a reflects how strongly the gas molecules attract each other; has units of L2·atm/mol2

b – a measure of actual intrinsic volume occupied by a mole of gas molecules; has units of L/mol.

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