Chemistry

The Molecular Nature of Matter and Change

Silberberg 6th Edition

Chapter 5
Gases & The Kinetic
Molecular Theory
The way of the Wind is a strange, wild way.
-Ingram Crockett

Erik D. Woodbury
De Anza College
Cupertino, CA

Ch. 5 Outline
5.1 How are Gases different?
5.5 Kinetic Molecular Theory
5.2 Pressure
5.3 Gas Laws and Foundations
5.4 Applications of PV=NRT
5.6 Real gases are not imaginary

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 Ch. 5 Objectives
1. Understand and convert between pressure units.
2. Understand the basis of the gas laws and how to
use those laws.
3. Use the ideal gas law.
4. Understand gas density and molar mass
relationships.
5. Understand and apply the kinetic molecular theory
of gases to explain gas behavior.
6. Investigate non-ideal gas behavior: What causes
gases to deviate from ideal behavior?

Gases and their Behavior

Common Phenomena Related to this Chapter (or Why
We Care)
A bicycle tire ruptures if too much air is added
A aerosol can may explode if heated
A balloon lled with He oats while one with CO2 sinks in
the atmosphere.
A balloon lled with hot air rises in the atmosphere.
The smell of baking cookies or perfume spreads easily
through a room.
A balloon lled with helium slowly deates.

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 Characteristics of Gases
Solids (Rigid)
constant shape and volume
Liquids (Mobile)
Constant Volume, variable shape
Both liquids and solids are condensed matter:
atoms/molecules are all close together
Gases (Dynamic)
Widely separate atoms/molecules
Expand to fill their containers;
Are highly compressible;
Flow and diffuse easily
Have extremely low densities. ~0.001 g/mL
Form solutions in any proportions

Laws and Theories

Kinetic Molecular Theory (KMT) was developed in the mid-19th
century to help explain the various gas laws that hade been
derived from experimentation. It is based on a nanoscopic view
of gases.
Main Tenets
Gases consist of a large number of tiny particles in constant motion.
These particles move in a straight line until they hit something (a wall or
gas particle)
Collisions are elastic (no energy is gained or lost as a result)
The volume of a gas particle is negligible relative to the total volume of
the container.
The attractive or repulsive forces between particles is negligible.
Kinetic energy of the particles is proportional to temperature. The higher
the T, the faster they move. All particles have the same Kinetic
Energy at a given temperature.
Pressure results from particles colliding with the walls of the container

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 What is Pressure?
Force SI Unit = N/m2 = Pascal (Pa)
P= 1 N = 1 kg*m/s2 (SI for force)
Area
Equivalent Pressures atm mm torr bar Pascals (Pa) kPa Pounds per sq. in.
Hg (psi)

1 Atmosphere (atm) = 1 760 760 1.01325 101,325 101.325 14.70

Atmospheric pressure is the weight of air per unit of area.

Barometer: Measures atmospheric pressure by observing height of a mercury column in an
evacuated tube. Invented in 1643 by Torrecelli. Gave rise to unit mm Hg. Equivalent height of
water: 33.9 ft !!
Manometer: Measures the pressure difference of a closed sample from P atm as a height
difference of a liquid.
mm Hg are not a direct measure of pressure in the sense of F/A.
The height is proportional to the pressure measurement however.

Pressure
Pressure (Pa) exerted downward is proportional to height and density of a liquid or
gas in a tube.
P = pressure (N/m2); A = cross sectional area of tube (m2); m = mass (kg)
g = gravity (9.8 m/s2) h = height (m) d = density (kg/m3)

As P = F/A = m*g/A = h*d*A*g/A = h*g*d therefore: P = h*d*g

If the average density of air is 1.2x10-3 g/cm3, what is the height

of a column that gives a pressure of 1 atm?

A scuba diver descends to a depth of 150 ft. What is the

pressure of water above him?

A boiler has a pressure of 1401 psi. What is the pressure in

Torr?

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 Boyles Law: Pressure and Volume
The volume of a fixed quantity of gas at constant temperature is inversely
proportional to the pressure.
P 1/V or P1V1 = P2V2 or PV = k1
As V decreases, P increases and vice versa
Squeeze a balloon and what happens?
Hold your breath as you go deeper underwater.
Take a bag of chips up a mountain.

KMT and Boyles Law

The volume of a fixed quantity of gas at constant temperature is
inversely proportional to the pressure.
P 1/V or P1V1 = P2V2 or PV = k1
At a constant T, gas particles
maintain a constant Kinetic
Energy (KE) ~ speed.
As V decreases, distance
travelled before a collision
occurs decreases
# of collisions over time
increases.
More collisions=more
pressure
60 mph on highway vs. parking lot.

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 Charless Law: Volume and Temperature
The volume of a fixed quantity of gas at constant pressure is
directly proportional to the absolute temperature. (T in Kelvin!)
VT or V1/T1 = V2/T2 or V/T = k2
As T increases, V increases and vice versa

Heat a balloon in the

microwave
Cool it with liquid nitrogen.
Inflate a hot air balloon.

KMT and Charles Law

The volume of a fixed quantity of gas at constant pressure is
directly proportional to the absolute temperature. (T in Kelvin!)
VT or V1/T1 = V2/T2 or V/T = k2
Pressure increases with the
number of collisions.
If T increases, volume must also
increase to keep the number of
collisions constant.
Drive 30 mph vs. 100 mph.
Need more room to keep collisions
down.
This law helped Lord Kelvin
determine the value of absolute
zero.
(negative volumes are impossible)

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Temperature and Pressure: Gay-Lussacs Law
If, instead, the volume of a fixed quantity of a gas is held
constant, the pressure of that gas is directly proportional
to its temperature.
PT or P1/T1 = P2/T2
KMT: If T increases, speed increases. In a fixed volume,
this leads to more collisions. More pressure!

The Combined Gas Law

We can combine these expressions:
V/T = k2 and PV = k1
to get

P1V1/T1 = k1k2 = P2V2/T2

This equation relating volume, pressure and

temperature is known as the Combined Gas Law.

Good for calculating changes of a fixed amount of gas.

What happens when moles of gas particles change?

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 Avogadros Law
Avogadro hypothesized that equal volumes of gas at the
same temperature contain the same number of particles.
or
The volume of a gas at constant temperature and pressure
is directly proportional to the number of moles of the gas.
Vn or V1/n1 = V2/n2 or V/n = k3

Gay-Lussac made the original observation of combining volumes.

Avagadro interpreted it in a way that related it to the number of particles present.

KMT and Avogadros Law

The volume of a gas at constant temperature and pressure is
directly proportional to the number of moles of the gas.
Vn or V1/n1 = V2/n2 or V/n = k3
Increased moles of gas at a constant temperature will hit the
walls of the container more often if the volume is not increased.
Volume must therefore increase so that particles must travel
farther before hitting the walls of the container in order to
maintain the same pressure.

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 Ideal-Gas Equation
So far weve seen that
V 1/P (Boyles law) PV = k1
V T (Charless law) V/T = k2
V n (Avogadros law) V/n = k3
Combining these, we get
nT PV
V or
nT
= k1 k 2 k 3 = R
P
R is the universal gas constant. R = 0.08206
R may be listed with other units

Given that 1L*atm = 101.325 J, what is the value for R in J/(mol*K)?

Ideal-Gas Equation

This relationship is referred to as the Ideal Gas Equation

1. Using the Ideal Gas Law, find the pressure exerted by 2.5 g of
CO2 contained in a 150 mL flask at 20C

2. Standard Temperature and Pressure (STP) is defined as 1

atm and 0C (273.15 K). Given this, calculate the molar
volume of a gas at STP. Does the type of gas matter?

3. How many molecules are contained in a 1.0 L flask at STP?

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 Other Gas Calculations
1st type was knowing 3 variables and finding the 4th
(1st example last slide)
2nd type harkens back to our individual gas laws.

In these cases, 2 or 3 variables can change from state 1 to

state 2. The above equation can be rearranged to solve for any
of the listed variables.
P2= V2 = n2 = T2 =

Example Problems
1. An aerosol can contains a gas at 1.82 atm and 22 C. The
label on the can says that exposure to temperatures over
115C may cause it to burst. What is the pressure inside the
can at 115 C?

2. A 25.0 L container of Ne at 1.00 atm and 25 C is

compressed and heated. The temperature rises to 74 C and
the pressure increases to 4.50x103 torr. What is the new
volume?

3. The volume of a gas in increased by a factor of 5 while the

Kelvin temperature is increased by a factor of 3. By what
factor does the pressure change?

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 Densities of Gases
If we divide both sides of the ideal-gas equation by V
and by RT, we get
As temperature increases, what
n P happens to a gass density?
=
V RT
and as n=m n = moles
M = Molar Mass

m P = P
dRT
then =d= and
V RT
Note: One only needs to know the molecular mass, the pressure,
and the temperature to calculate the density of a gas.

Questions
1. A compressed gas cylinder of N2 has a pressure of 1800 psi at
20 C. What is the density of the N2 inside the cylinder?

2. Given that the atmosphere is 78.1 % nitrogen and 20.9 %

oxygen by volume, will a bubble filled with methane gas rise or
sink in the atmosphere?

3. Vapor for an unknown liquid whose empirical formula CH2 was

collected in a 262 mL flask at 0.9937 atm and 100.0 C. The
flask weighed 96.9197 g when empty and 97.6342 g when the
vapor condensed into a liquid. What is the molar mass and
molecular formula of the gas?

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 Volumes of Gases in Chemical Reactions

We can use P, V, and T data to determine the moles of a gas present.

Example Problem
How many grams of sodium azide are needed for an
automobile air bag to fully inflate if the nitrogen gas produced is
required to fill a 36 L bag at a pressure of 874 mm Hg at
26C?
2 NaN3 (s) 2 Na (s) + 3 N2 (g)
10 Na (s)+ 2 KNO3 (s) K2O (s) + 5 Na2O (s) + N2 (g)

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 Daltons Law of Partial Pressures
The total pressure of a mixture of gases equals the sum of the
pressures that each would exert if it were present alone.
KMT: each gas contributes a certain # of collisions/sec. The total number
of collisions is the total pressure.
Collisions from only one type of gas is the partial pressure of that gas.

In other words,
Ptotal = P1 + P2 + P3 +
Where P1, P2, and P3 are partial pressures of those particular gasses.

Yet another way, the ideal gas law can

be applied individually to each different
gas, or to the total gas in the container.

Gas Mixtures and Partial Pressure

Consider the apparatus in the picture and the following:

When the stopcock between the two containers is opened and

the gases are allowed to mix, what is the partial pressure of
each gas and the total pressure in the container after the
gasses mix?
Hint: Use Boyles then Daltons Law.

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 Mole Fraction and Partial Pressure
The mole fraction of a gas in a mixture is given by the symbol X,
(pronounced chi)

For a mixture of gases, the partial pressures and moles are proportional
because V and T are the same for each gas in the mixture. So we can derive
the following:

1. The mole percent of oxygen in dry atmospheric air is 20.95%. A weather

channel reports that the total air pressure is 29.7 in Hg on a dry day in Palm
Desert, California. What is the partial pressure in atmospheres of O 2 in the
air?

2. If 2.0 grams each of methane (CH4) and oxygen gas are mixed in a 2.0 L
container at 25 C, what is the mole fraction and partial pressure of each
gas? What is the total pressure of the system?

Collecting Gas Over Water

When one collects a gas over water, there is water vapor mixed
in with the gas. The pressure of the water vapor depends on
the temperature of the water. This pressure value can be found
in several literature sources, including the back of your book.
The total pressure of the gas collected is equal to the
atmospheric pressure in the lab.

Figure 10.16 Collecting a water-insoluble gas over water. (a) A solid is heated,
releasing a gas, which is bubbled through water into a collection bottle. (b) When
the gas has been collected, the bottle is raised or lowered so that the water levels
inside and outside the bottle are equal. The total pressure of the gases inside the
bottle is then equal to the atmospheric pressure.

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 Collecting Gas over Water
A 2.685 g sample of an alloy containing only aluminum and
copper is reacted with excess HCl(aq).The Al reacts completely
in a single replacement reaction that produces hydrogen gas.
Copper does not react with HCl(aq). The hydrogen gas
produced occupies a volume of 267 mL when collected over
water at 22C and an atmospheric pressure of 746.0 mm Hg.

What is the percent copper by mass in the alloy?

Distributions of Molecular Speeds

A sample of a gas has an average
kinetic energy, and so an average
speed. (defined by temperature and
molar mass)
Individual particles have a distribution
of speeds.
The average kinetic energy () of
a particle is related to the root mean
squared speed (rms, u) and particle
mass.
Note: rms is not
the same as average
speed, though the two are
m = mass in kg/particle, and u close. rms refers to the
in m/s n speed of a particle which
This gives our energy in J/particle has the average kinetic
energy.
This gives our energy in J/mol,
where M is our molar mass.

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 RMS Example problem
What is the average kinetic Energy in J/particle and J/mol of a
sample of CO2 (g) if the rms speed is 4.0x102 m/s?

Different Gases, Different Speeds

Distribution of molecular speeds for different gases at 25 C
According to KMT,
samples of gas at
the same T have the
same average KE
(1/2 mu2)
Gases have different
masses however, so
less massive gases
This relationship is governed by the equation must travel faster
than larger gases to
have the same
overall KE.
What effect does mass have on the shape of the curve?
What effect can be observed relative to the rms?
Where would ammonia gas fit in this figure?

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 KE and rms: A comparison
Calculate the average kinetic energy of any gas at 25 C

What happens to the average KE if the absolute temp (K)

doubles?

What happens to the rms if the absolute temp. doubles?

KE and rms: A comparison

As temperature increases, what happens to the shape of the curve?

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 Example problem
Given 2 flasks both at 25 C and 1 atm:
A: 1 mol H2 gas
B: 1 mol N2 gas

Compare:
Volume

Gas Density

Root-Mean-Square Speed

Frequency of collisions of the gas particles with the

container wall.

Effusion and Grahams Law

Effusion is when gas escapes
through a small hole.
Relative rates of effusion depend
on Molar Mass

This indicates that the lighter gas

effuses more quickly.
This is why balloons deflate.
This can be used to calculate
molar masses or purify gas
samples.

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 Diffusion
Diffusion is the spread of a gas
through space
The smell of cookies
The rate of diffusion depends on
molecular speed.
Hence, light gases diffuse more
rapidly than massive gases.

Given that gases travel very fast, why

does it take several minutes for smells
to reach our noses from another
room?
Mean free path (~ 60nm at seal level)

Real Gases
According to KMT:
Gas particles do not attract one another
Gas particle volume is negligible.

At room temp or above and at pressure less than a few

atmospheres, these assumptions are valid and gases obey the
ideal gas law well.

Under conditions of high pressure and/or low temp, these

assumptions no longer hold and gases deviate from behavior
as predicted by the ideal gas law.

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 Why is there Deviation?
2 major points:
At high P, gas particles are closer together,
so the volume of the particle itself becomes
significant. The actual volume available in
the container for the particles to move is
less than the measured volume of the
container because of this.

At low temp, gas particles are moving

slowly, and spend more time close to one
another. During this time, intermolecular
forces of attraction have more time to act, in
effect causing the particles to stick together,
or at least veer toward one another. This
results in fewer collisions with the walls of
the container, and hence a lower pressure
than expected.

Real Gases

Above we see
the deviations
from ideal To the left we
behavior at high see the
pressure across deviations from
several ideal behavior
temperatures. at high pressure
across several
gases.

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 Real Gases
We can account for these variations by using
the van der Waals equation

P- measured pressure
V measured volume
a&b experimentally determined constants for the
gas in question

n2a/V2 corrects for the net attractive force between

gas particles. This term increases the observed
pressure to the ideal pressure. a relates to
the strength of the attractive forces between
particles.
nb correscts for the volume occupied by the gas
particles themselves. This term decreases
the observed volume to the ideal.
b is related to the gas particle size
per mole

The van der Waals Equation

Values for a and b can be found in your textbook.

How does the magnitude of b relate

to the size of the gas particle?

How does the magnitude of a relate

to the factors that affect
intermolecular forces? (size and
polarity?)

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 Example Problem
Calculate the pressure that CO2 will exert at 50 C if 1.00
mol occupies 0.0700 L, assuming
a) Ideal behavior
b) Nonideal behavior
c) Is the observed (nonideal) behavior pressure a (+) or (-)
deviation?

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