UNIT 1:

GASES
1
OUTLINE
▪ Properties of Gases
▪ Gas Pressure and Its measurement
▪ The Gas Laws and Their Experimental Foundations
▪ The Ideal Gas Equation
▪ The Kinetic Molecular Theory: A Model for Gas Behavior
▪ Real Gases: Deviations from Ideal Behavior

2
 Properties of Gases

Gase
s
© 2015 Pearson Education, Inc.
 Figure 5.1 The three states of matter.

Gase
s
© 2015 Pearson Education, Inc.
 Characteristics of Gases
• Physical properties of gases are all similar.

• Composed mainly of nonmetallic elements with simple

formulas and low molar masses.

• Unlike liquids and solids, gases

⮚ expand to fill their containers.
⮚ are highly compressible.
⮚ have extremely low densities.

• Two or more gases form a homogeneous mixture.

Gase
s
© 2015 Pearson Education, Inc.
 Properties Which Define the State of a
Gas Sample (Variables of State)

1) Pressure
2) Temperature
3) Volume
4) Amount of gas, usually expressed as
number of moles

Gase
s
© 2015 Pearson Education, Inc.
 Gas Pressure and Its Measurement
• Pressure is the amount
of force applied to an
area:

F
P=
A
• Atmospheric
pressure is the
weight of air per unit
of area; decreases
with altitude
Gase
s
© 2015 Pearson Education, Inc.
 Units of Pressure

Gase
s
© 2015 Pearson Education, Inc.
 Measuring Pressure

The barometer is a device used to The manometer is used to measure the difference
measure atmospheric pressure in pressure between atmospheric pressure and that
of a gas in a vessel. (The barometer seen on the
last slide is used to measure the pressure in the
atmosphere at any given time.) Gase
s
© 2015 Pearson Education, Inc.
 Standard Pressure
• Normal atmospheric pressure at sea level is referred
to as standard atmospheric pressure.

1.00 atm = 760 torr (760 mmHg) = 101.325 kPa

Pressure exerted by a column of liquid

𝐹 𝜌𝐴ℎ𝑔
𝑝= = = 𝜌𝑔ℎ
𝐴 𝐴
Exercise: Calculate the pressure of a column of mercury with a
height of 760 mm. 𝝆 = 13.5951 g/mL

Gase
s
© 2015 Pearson Education, Inc.
 Effect of atmospheric pressure.

Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 1 Converting Units of Pressure

PROBLEM: A geochemist heats a limestone (CaCO3) sample and

collects the CO2 released in an evacuated flask attached
to a closed-end manometer. After the system comes to
room temperature, Δh = 291.4 mm Hg. Calculate the CO2
pressure in torrs, atmospheres, and kilopascals.

PLAN: Construct conversion factors to find the other units of pressure.

SOLUTION: 291.4 mmHg x 1torr

= 291.4 torr
1 mmHg

291.4 torr x 1 atm = 0.3834 atm

760 torr

0.3834 atm x 101.325 kPa = 38.85 kPa

1 atm
Gase
s
© 2015 Pearson Education, Inc.
 The Gas Laws and
Their Experimental
Foundations

Gase
s
© 2015 Pearson Education, Inc.
 The Gas Laws

• The gas laws describe the physical behavior of gases in

terms of 4 variables:
– pressure (P)
– temperature (T)
– volume (V)
– amount (number of moles, n)
• An ideal gas is a gas that exhibits linear relationships
among these variables.

• No ideal gas actually exists, but most simple gases

behave nearly ideally at ordinary temperatures and
pressures.
Gase
s
© 2015 Pearson Education, Inc.
The Dependence of the Volume of a Gas
on Pressure: Boyle’s Law
In the 1660s, Robert Boyle performed a series of experiments as
illustrated:

The volume of a fixed quantity of gas at constant temperature varies Gase

s
inversely with the pressure.
© 2015 Pearson Education, Inc.
 Boyle’s Law

The volume of a fixed quantity of gas at constant

temperature is inversely proportional to the pressure..

V 1 or PV = constant
P
▪ This means, if we compare two conditions:
P1V1 = P2V2 (constant T and n)
Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 2 Applying the Volume-Pressure Relationship

PROBLEM: Boyle’s apprentice finds that the air trapped in a J tube

occupies 24.8 cm3 at 1.12 atm. By adding mercury to the
tube, he increases the pressure on the trapped air to
2.64 atm. Assuming constant temperature, what is the new
volume of air (in L)?
PLAN: The temperature and amount of gas are fixed, so this
problem involves a change in pressure and volume only.
SOLUTION:
V1 (cm3)
1 cm3 = 1 mL
P1 = 1.12 atm P2 = 2.64 atm n and T are constant
V1 = 24.8 cm3 V2 = unknown
V1 (mL)
1000 mL = 1L
V2 = V1 x P1 = 0.0248 L x 1.12 atm
V1 (L) P2 2.64 atm
multiply by P1/P2
= 0.0105 L
V2 (L) Gase
s
© 2015 Pearson Education, Inc.
The relationship between the volume and
temperature of a gas: Charles’ Law

Gase
s
© 2015 Pearson Education, Inc.
 Charles’s Law (Gay-Lussac’s Law)
At constant pressure, the volume occupied by a
fixed amount of gas is directly proportional to its
absolute (Kelvin) temperature.
V
VT or = constant
T
At fixed P and n,
V decreases as T decreases
V increases as T increases

▪ This means, if we compare two conditions:

𝑽𝟏 𝑽𝟐
= (constant P and n)
𝑻𝟏 𝑻𝟐
Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 3 Applying the Volume-Temperature and
Pressure-Temperature Relationships

PROBLEM: A balloon is filled with 1.95 L of air at 25ºC and then

placed in a car in the sun. What is the volume of the
balloon when the temperature in the car reaches 90ºC?

PLAN: We know the initial volume (V1) and the initial (T1) and final
temperatures (T2) of the gas; we must find the final volume (V2).
The pressure of the gas is fixed since the balloon is subjected to
atmospheric pressure and n is fixed since air cannot escape or
enter the balloon. We convert both T values to degrees Kelvin,
rearrange the ideal gas law, and solve for V2.

Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 3

T1 and T2 (ºC)
ºC + 273.15 = K

V1 (L) T1 and T2 (K)

multiply by T2/T1

V2 (L)

SOLUTION: Summarizing the gas variables:

V1 = 1.95 L V2 = 1.95 L
T1 = 25ºC (convert to K) T2 = 90ºC (convert to K)
P and n remain constant
Converting T from ºC to K:
T1 (K) = 25ºC + 273.15 = 298 K T2 (K) = 90ºC + 273.15 = 363 K

Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 3
SOLUTION (continued):
Rearranging the generalized ideal gas equation and solving for V2:
At fixed n and P, we have

P1V1 P2V2 V1 V2
= or =
n1T1 n2T2 T1 T2

T2 363 K
V2 = V1 x T1 = 1.95 L x = 2.38 L
298 K

CHECK: Let’s predict the change to check the math: Because T2 > T1, we
expect V2 > V1. Thus, the temperature ratio should be > 1 (T2 in the
Numerator). The T ratio (363/298) is about 1.2, so the V ratio should also be
about 1.2 (2.4/2.0).

Gase
s
© 2015 Pearson Education, Inc.
 The relationship between the volume and
amount of a gas: Avogadro’s Law
At fixed temperature and pressure, the volume occupied by a gas is
directly proportional to the amount of gas.

Avogadro’s Law: at fixed temperature and pressure, equal

volumes of any ideal gas contain equal numbers of particles (or
moles).
Gase
s
© 2015 Pearson Education, Inc.
 Avogadro’s Law
• The volume of a gas at constant temperature and pressure is
directly proportional to the number of moles of the gas.

STP or standard temperature and pressure specifies a pressure of

1 atm (760 torr) and a temperature of 0°C (273.15 K).

The standard molar volume is the volume of 1 mol of an ideal gas at

STP. Standard molar volume = 22.4141 L or 22.4 L

• Mathematically:
V = constant × n, or
𝑽𝟏 𝑽𝟐
= (constant P and n)
𝒏𝟏 𝒏𝟐
Gase
s
© 2015 Pearson Education, Inc.
 Standard Molar Volume

Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 4 Applying the Volume-Amount Relationship

PROBLEM: A scale model of a blimp rises when it is filled with helium to a

volume of 55.0 dm3. When 1.10 mol of He is added to the blimp,
the volume is 26.2 dm3. How many more grams of He must be
added to make it rise? Assume constant T and P.

PLAN: The initial amount of helium (n1) is given, as well as the initial
volume (V1) and the volume needed to make it rise (V2). We need to
calculate n2, and hence the mass of He to be added.

n1 (mol) of He
multiply by V2 /V1

n2 (mol) of He
subtract n1

mol to be added
multiply by M

g to be added
Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 4

SOLUTION:
n1 = 1.10 mol n2 = unknown
V1 = 26.2 dm3 V2 = 55.0 dm3 T and P are constant

P1V1 P2V2 V1 V2
= =
n1T1 n2T2 n1 n2

n2 = n1 x V2 = 1.10 mol x 55.0 dm

3
= 2.31 mol He
V1 26.2 dm3

Additional amount of He needed = 2.31 mol – 1.10 mol = 1.21 mol He

4.003 g He
1.21 mol He x = 4.84 g He
1 mol He
Gase
s
© 2015 Pearson Education, Inc.
 The Ideal Gas Equation

Gase
s
© 2015 Pearson Education, Inc.
 So far we’ve seen that
V ∝ 1/P (Boyle’s law)
V ∝ T (Charles’ law)
V ∝ n (Avogadro’s law)

Combining these, we get nT

V∝ P

Finally, to make it an equality, we use a constant of

proportionality (R) and reorganize
nT nT
V = constant x V=Rx
P P

this gives the Ideal-Gas Equation: PV = nRT.

Gase
s
© 2015 Pearson Education, Inc.
 The Gas Constant, R
▪ For 1 mol of gas at STP
PV 1 atm x 22.414 L 0.0821 atm·L
R= = =
nT 1 mol x 273.15 K mol·K

R is the universal gas constant;

the numerical value of R
depends on the units used.

Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 5 Applying the Volume-Pressure-Temperature
Relationship
PROBLEM: A helium-filled balloon has a volume of 15.8 L at a pressure of
0.980 atm and 22ºC. What is its volume on the top of Mt. Hood,
Oregon’s highest mountain, where the atmospheric pressure is
532 mmHg and the temperature is 0ºC?
PLAN: We know the initial volume (V1), pressure (P1), and temperature (T1) of the
gas; we also know the final pressure (P2) and temperature (T2) and we must
find the final volume (V2). Since the amount of helium in the balloon does not
change, n is fixed. We convert both T values to degrees Kelvin, the final
pressure to atm, rearrange the generalized ideal gas equation, and solve for
V2.

SOLUTION: Summarizing the gas variables:

V1 = 15.8 L V2 = unknown
T1 = 22ºC (convert to K) T2 = 0ºC (convert to K)
P1 = 0.980 atm P2 = 523 mmHg (convert to atm)
n remains constant

Converting T from ºC to K:
T1 (K) = 22ºC + 273.15 = 295 K T2 (K) = 0ºC + 273.15 = 273 K Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 5
SOLUTION (continued):
1 atm
P2 (atm) = 532 mmHg x = 0.700 atm
Converting P2 to atm: 760 mmHg
Rearranging the generalized ideal gas equation and solving for V2:
At fixed n, we have
P1V1 P2V2 P1V1 P2V2
= or =
n1 T1 n2T2 T1 T2

P1T2 (0.980 atm) (273 K)

V2 = V1 x = 15.8 L x = 20.5 L
P2T1 (0.700 atm) (295 K)

CHECK: Let’s predict the change to check the math: Because T2 < T1, we
expect V2 < V1; but because P2 < P1, we expect V2 > V1. The temperature ratio
(T2 in the numerator) is about 0.93 (273/295) and the pressure ratio (P1 in the
numerator) is about 1.4 (0.980/0.700), so the V ratio should be about 0.93 x 1.4 or
1.3 (20.5/15.8 ≈ 1.3). The pressure decreased by a larger factor than the
temperature increased, so there is an overall increase in volume.
Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 6 Solving for an Unknown Gas Variable at
Fixed Conditions
PROBLEM: A steel tank has a volume of 438 L and is filled with
0.885 kg of O2. Calculate the pressure of O2 at 21ºC.
PLAN: We are given V, T, and mass, which can be converted to
moles (n). Use the ideal gas law to find P.

SOLUTION: V = 438 L T = 21ºC = 294 K

n = 0.885 kg O2 (convert to mol) P is unknown
3
0.885 kg O2 x 10 g x 1 mol O2
= 27.7 mol O2
1 kg 32.00 g O2

atm·L
27.7 mol x 0.0821 x 294 K
nRT mol·K
P= = = 1.53 atm
V
438 L
Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 7 Using Gas Laws to Determine a Balanced
Equation

PROBLEM: The piston-cylinder is depicted before and after a gaseous

reaction that is carried out at constant pressure. The
temperature is 150 K before the reaction and 300 K after
the reaction. (Assume the cylinder is insulated.)

Which of the following balanced equations describes the reaction?

(1) A2 (g) + B2 (g) → 2AB (g) (2) 2AB (g) + B2 (g) → 2AB2 (g)
(3) A (g) + B2 (g) → AB2 (g) (4) 2AB2 (g) → A2 (g) + 2B2 (g)
Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 7

PLAN: We are told that P is constant for this system, and the depiction
shows that V does not change either. Since T changes, the
volume could not remain the same unless the amount of gas in the
system also changes.

n2 T1 150 K
SOLUTION: n1T1 = n2T2 = = =½
n1 T2 300 K

Since T doubles, the total number of moles of gas must halve –

i.e., the moles of product must be half the moles of reactant.
This relationship is shown by equation (3).

A (g) + B2 (g) → AB2 (g)

Gase
s
© 2015 Pearson Education, Inc.
 Gas Density and Molar Mass from the
Ideal Gas Equation
➢ The density of a gas is directly ➢ Molar Mass
proportional to its molar mass
and inversely proportional to its m PV
temperature. n= =
M RT
m m
density = and moles,n = mRT
V M M=
PV
m
PV = RT
M

m M xP
=d=
V RT
Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 8 Calculating Gas Density

PROBLEM: Find the density (in g/L) of CO2 (g)

(a) at STP and (b) at room conditions (20. ºC and 1.00 atm).

PLAN: We can use the molar mass of CO2 to find its density from
the ideal gas equation.

SOLUTION: (a) At STP, or 273 K and 1.00 atm:

M xP 44.01 g/mol x 1.00 atm

d= = = 1.96 g/L
RT atm·L
0.0821 x 273 K
mol·K

(b) At 20. ºC and 1.00 atm:

M xP 44.01 g/mol x 1.00 atm

d= = = 1.83 g/L
RT atm·L
0.0821 x 293 K Gase
mol·K s
© 2015 Pearson Education, Inc.
 Sample Problem 9 Finding the Molar Mass of a Volatile Liquid

PROBLEM: An organic chemist isolates a colorless liquid from a

petroleum sample. She places the liquid in a preweighed
flask and puts the flask in boiling water, causing the liquid
to vaporize and fill the flask with gas. She closes the flask
and reweighs it. She obtains the following data:

Volume (V) of flask = 213 mL T = 100.0ºC P = 754 torr

mass of flask + gas = 78.416 g mass of flask = 77.834 g

Calculate the molar mass of the liquid.

PLAN: The variables V, T and P are given. We find the mass of the
gas by subtracting the mass of the flask from the mass of
the flask with the gas in it, and use this information to
calculate M.
Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 9

SOLUTION: m of gas = (78.416 - 77.834) = 0.582 g

V = 213 mL x 1 L = 0.213 L T = 100.0ºC + 273.15 = 373.2 K

103 mL

P = 754 torr x 1 atm = 0.992 atm

760 torr

atm·L
0.582 g x 0.0821 x 373.2 K
mRT mol·K
M= = = 84.4 g/mol
PV 0.213 L x 0.992 atm

Gase
s
© 2015 Pearson Education, Inc.
 Volume and Chemical Reactions

• The balanced equation tells us relative amounts of moles in

a reaction, whether the compared materials are products or
reactants.
• PV = nRT
• So, we can relate volume for gases, as well.
• For example: use (PV = nRT) for substance A to get moles
A; use the mole ratio from the balanced equation to get
moles B; and (PV = nRT) for substance B to get volume of
B.

Gase
s
© 2015 Pearson Education, Inc.
 The Ideal Gas Law and Stoichiometry

P, V, T P, V, T
of gas A of gas B

Amount (mol) Amount (mol)

of gas A of gas B

The relationships among the amount (mol, n) of gaseous

reactant (or product) and the gas pressure (P), volume (V),
and temperature (T).
Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 10 Using Gas Variables to Find Amounts of
Reactants and Products I

PROBLEM: What volume of H2 gas at 765 torr and 225ºC is needed

to reduce 35.5 g of copper(II) oxide to form pure copper
and water?

PLAN: Write a balanced equation. Convert the mass of copper(II) oxide

to moles and find the moles of H2, using the mole ratio from the
balanced equation. Calculate the corresponding volume of H2
using the ideal gas law.
mass (g) of CuO
divide by M

mol CuO
use mole ratio

mol H2 volume of H2
ideal gas law
Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 10

SOLUTION: CuO (s) + H2 (g) → Cu (s) + H2O (g)

35.5 g CuO x 1 mol CuO x 1 mol H2 = 0.446 mol H

2
79.55 g CuO 1 mol CuO

1 atm
P = 765 torr x = 1.01 atm T = 225ºC + 273.15 K = 498 K
760 torr

atm·L
0.446 mol H2 x 0.0821 x 498 K
nRT mol·K
V= = = 18.1 L H2
P
1.01 atm

Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 11 Using Gas Variables to Find Amounts of
Reactants and Products II

PROBLEM: What mass of potassium chloride forms when 5.25 L of

chlorine gas at 0.950 atm and 293 K reacts with 17.0 g of
potassium metal?

PLAN: First we must write a balanced equation. Since the quantities of

both reactants are given, we must next determine which reactant
is limiting. We will use the ideal gas law to calculate the moles of
Cl2 present.

SOLUTION: The balanced equation is Cl2 (g) + 2K (s) → 2KCl (s)

For Cl2:
P = 0.950 atm V = 5.25 L
T = 293 K n = unknown
Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 11

n PV 0.950 atm x 5.25 L

Cl2 = RT
=
atm·L = 0.207 mol Cl2
0.0821 x 293 K
mol·K

For Cl2: 0.207 mol Cl2 x 2 mol KCl

= 0.414 mol KCl
1 mol Cl2

For K: 17.0 g K x 1 mol K x 2 mol KCl = 0.435 KCl

39.10 g K 2 mol K

Cl2 is the limiting reactant because the given amount

produces less KCl.

0.414 mol KCl x 74.55 g KCl = 30.9 g KCl

1 mol KCl

Gase
s
© 2015 Pearson Education, Inc.
 Dalton’s Law of Partial Pressures
• If two gases that don’t react are combined in a
container, they act as if they are alone in the
container.
• The total pressure of a mixture of gases equals the
sum of the pressures that each would exert if it
were present alone.
• In other words,

Ptotal = p1 + p2 + p3 + …

• The pressure exerted by each gas in a mixture is

called its partial pressure. Gase
s
© 2015 Pearson Education, Inc.
 Mole Fraction
• Because each gas in a mixture acts as if it is alone,
we can relate amount in a mixture to partial pressures:

• That ratio of moles of a substance to total moles is

called the mole fraction, χ.

• The end result is

Gase
s
© 2015 Pearson Education, Inc.
 Sample Problem 12 Applying Dalton’s Law of Partial Pressures

PROBLEM: In a study of O2 uptake by muscle at high altitude, a

physiologist prepares an atmosphere consisting of 79 mole %
N2, 17 mole % 16O2, and 4.0 mole % 18O2. (The isotope 18O
will be measured to determine the O2 uptake.) The total
pressure of the mixture is 0.75 atm to simulate high altitude.
Calculate the mole fraction and partial pressure of 18O2 in the
mixture.
PLAN: Find X 18O2 and P18O2 from Ptotal and mol % 18O2.

mole % 18O2
divide by 100

mole fraction, X 18
O2
multiply by Ptotal

partial pressure P18

O2
Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 12

SOLUTION:

4.0 mol % 18O2

X 18O2 = = 0.040
100

P18O = X 18O x Ptotal = 0.040 x 0.75 atm = 0.030 atm

2 2

Gase
s
© 2015 Pearson Education, Inc.
 The Kinetic Molecular Theory:
A Model for Gas Behavior

Gase
s
© 2015 Pearson Education, Inc.
 Kinetic-Molecular Theory
⮚ Laws tell us what happens in
nature. Each of the gas laws
we have discussed tell us what
is observed under certain
conditions.

⮚ Why are these laws observed?

We will discuss a theory to
explain our observations.

Gase
s
© 2015 Pearson Education, Inc.
 The Kinetic-Molecular Theory:
A Model for Gas Behavior
Postulate 1:
Gas particles are tiny with large spaces between them. The volume
of each particle is so small compared to the total volume of the gas
that it is assumed to be zero.

Postulate 2:
Gas particles are in constant, random, straight-line motion except
when they collide with each other or with the container walls.

Postulate 3:
Collisions are elastic, meaning that colliding particles exchange
energy but do not lose any energy due to friction. Their total kinetic
energy is constant. Between collisions the particles do not influence
each other by attractive or repulsive forces.
Gase
s
© 2015 Pearson Education, Inc.
 Postulate 4:
Energy can be transferred between
molecules during collisions, but the
average kinetic energy of the molecules
does not change with time, as long as the
temperature of the gas remains constant.

Postulate 5:
The average kinetic energy of the
molecules is proportional to the absolute
temperature.

Gase
s
© 2015 Pearson Education, Inc.
 Pressure arise from countless collisions between gas particles
and walls.

Gase
s
© 2015 Pearson Education, Inc.
 A molecular view of Boyle’s law.

Pext increases,
T and n fixed

At any T, Pgas = Pext as Higher Pext causes lower V, which results in

particles hit the walls from more collisions, because particles hit the
an average distance, d1. walls from a shorter average distance (d2 <
d1). As a result, Pgas = Pext again.

Gase
s
© 2015 Pearson Education, Inc.
 A molecular view of Charles’s law.

At T1, Pgas = Patm. Higher T increases Thus, V increases until Pgas

collision frequency, so Pgas = Patm at T2.
> Patm.

Gase
s
© 2015 Pearson Education, Inc.
 A molecular view of Avogadro’s law.

For a given amount, n1, of When gas is added to reach n2 As a result, V increases until
gas, Pgas = Patm. the collision frequency of the Pgas = Patm again.
particles increases, so Pgas > Patm.

Gase
s
© 2015 Pearson Education, Inc.
 A molecular view of Dalton’s law.

Gase
s
© 2015 Pearson Education, Inc.
 How Fast Do Gas Molecules Move?
▪ Temperature is related to their average kinetic.
▪ Individual molecules can have different speeds of motion.

Gase
Maxwell-Boltzmann Distribution of Molecular Speeds s
© 2015 Pearson Education, Inc.
 u rms and Molecular Mass
▪ At any given temperature, the average kinetic energy of molecules is the
same.

▪ So, ½ m (urms)2 is the same for two gases at the same temperature.

▪ If a gas has a low mass, its speed will be greater than for a heavier
molecule.

Gase
s
© 2015 Pearson Education, Inc.
 Kinetic Energy and Gas Behavior

At a given T, all gases in a sample have the same

average kinetic energy.

1
Ek = mass x speed2
2

Kinetic energy depends on both the mass and the

speed of a particle.
At the same T, a heavier gas particle moves more
slowly than a lighter one.

Gase
s
© 2015 Pearson Education, Inc.
 Effusion & Diffusion
Effusion is the escape of Diffusion is the spread of
gas molecules through a one substance throughout
tiny hole into an a space or a second
evacuated space. substance.

Gase
s
© 2015 Pearson Education, Inc.
 Graham’s Law of Effusion
Effusion is the process by which a gas escapes
through a small hole in its container into an evacuated
space.

Graham’s law of effusion states that the rate of effusion

of a gas is inversely proportional to the square root of its
molar mass.
A lighter gas moves more quickly and therefore has a
higher rate of effusion than a heavier gas at the same T.

1
Rate of effusion 
√M
Gase
s
© 2015 Pearson Education, Inc.
 Graham’s Law Describes
Diffusion & Effusion

• Graham’s Law relates the molar mass

of two gases to their rate of speed of
travel.
• The “lighter” gas always has a faster
rate of speed.

Gase
s
© 2015 Pearson Education, Inc.
Figure 5.21 Effusion. Lighter (black) particles effuse faster than
heavier (red) particles.

Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 13 Applying Graham’s Law of Effusion

PROBLEM: A mixture of helium (He) and methane (CH4) is placed in an

effusion apparatus. Calculate the ratio of their effusion rates.

PLAN: The effusion rate is inversely proportional to √M for each gas,

so we find the molar mass for each substance using its formula
and take the square root. The ratio of the effusion rates is the
inverse of the ratio of these square roots.

SOLUTION: M of CH4 = 16.04 g/mol M of He = 4.003 g/mol

rate
√ 4.003
16.04
He
= = 2.002
rate CH4

Gase
s
© 2015 Pearson Education, Inc.
Seatwork

PROBLEM: Calculate the mass of water vapor present in a room of

volume 250 m3 that contains air at 30°C on a day when the
relative humidity is 53 per cent.

Vapor Pressure of Water (P H2O ) at Different T

T(ºC) P (torr) T(ºC) P (torr)
H2O H2O

0 4.6 40 55.3
5 6.5 45 71.9
10 9.2 50 92.5
12 10.5 55 118.0
14 12.0 60 149.4
16 13.6 65 187.5
18 15.5 70 233.7
20 17.5 75 289.1
22 19.8 80 355.1
24 22.4 85 433.6
26 25.2 90 525.8
28 28.3 95 633.9
30 31.8 100 760.0 Gase
35 42.2 s
© 2015 Pearson Education, Inc.
 Real Gases:
Deviations from Ideal
Behavior

Gase
s
© 2015 Pearson Education, Inc.
 Real Gases
⮚ In the real world, the behavior of gases only conforms to the
ideal-gas equation at relatively high temperature and low
pressure.
⮚ Even the same gas will show wildly different behavior under
high pressure at different temperatures.

Gase
s
© 2015 Pearson Education, Inc.
 Deviations from Ideal Behavior

The assumptions made in the kinetic-molecular model

(negligible volume of gas molecules themselves, no
attractive forces between gas molecules, etc.) break down
at high pressure and/or low temperature.
Gase
s
© 2015 Pearson Education, Inc.
 Real Gases: Deviations from Ideal Behavior

▪ The kinetic-molecular model describes the behavior

of ideal gases. Real gases deviate from this
behavior.

▪ Real gases have real volume.

➢ Gas particles are not points of mass, but have volumes
determined by the sizes of their atoms and the bonds
between them.

▪ Real gases do experience attractive and repulsive

forces between their particles.

▪ Real gases deviate most from ideal behavior at low

temperature and high pressure. Gase
s
© 2015 Pearson Education, Inc.
 Corrections for Nonideal Behavior
• The ideal-gas equation can be adjusted to take
these deviations from ideal behavior into account.

• The corrected ideal-gas equation is known as the

van der Waals equation.

The pressure adjustment is The volume adjustment is

due to the fact that due to the fact that molecules
molecules attract and repel occupy some space on
each other. their own.
Gase
s
© 2015 Pearson Education, Inc.
 Molar Volume of Some Common Gases at STP
(0ºC and 1 atm)

Molar Volume Boiling Point

Gas (L/mol) (oC)

He 22.435 -268.9
H2 22.432 -252.8
Ne 22.422 -246.1
Ideal gas 22.414 ‒
Ar 22.397 -185.9
N2 22.396 -195.8
O2 22.390 -183.0
CO 22.388 -191.5
Cl2 22.184 -34.0
NH3 22.079 -33.4

Gase
s
© 2015 Pearson Education, Inc.
 The van der Waals equation

• The van der Waals equation adjusts the ideal gas law to
take into account
– the real volume of the gas particles and
– the effect of interparticle attractions.

Van der Waals equation for n2a

n moles of a real gas (P + 2 )(V - nb) = nRT
V

The constant a relates to The constant b relates to

factors that influence the particle volume.
attraction between particles.

Gase
s
© 2015 Pearson Education, Inc.
 The van der Waals Equation

Gase
s
© 2015 Pearson Education, Inc.
 Compressibility Factor, z

▪ Deviation from ideality is conveniently shown by plotting

𝑃𝑉
the ratio 𝑚 or z.
𝑅𝑇
▪ This ratio will be unity for all P and T for ideal behavior

Real gases
▪ At high pressures, Z > 1 signifying that they have a larger
molar volume than a perfect gas.
▪ Repulsive forces are dominant
▪ At intermediate pressures, most gases have Z < 1,
indicating that the attractive forces are reducing the molar
volume relative to that of a perfect gas.

Gase
s
© 2015 Pearson Education, Inc.
 Deviations from ideal behavior with increasing external
pressure.

Gase
s
© 2015 Pearson Education, Inc.
 Compressibility Factor, z

▪ Analytical expressions to represent non-ideal behaviors

like in the figure below can be written as a power series of
the variable p

Which is called a virial equation of state

Gase
s
© 2015 Pearson Education, Inc.
 The effect of interparticle attractions on measured gas pressure.

Gase
s
© 2015 Pearson Education, Inc.
 The effect of particle volume on measured gas volume.

Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 14 Applying the van der Waals Equation

PROBLEM: You are in charge of the manufacture of cylinders of

compressed gas at a small company. Your company president would like
to offer a 4.0 L cylinder containing 0.500 kg of chlorine in the new catalog.
The cylinders you have on hand have a rupture pressure of 40 atm. Use
both the (a) ideal gas law and the (b) van der Waals equation to calculate
the pressure in a cylinder at 25°C. Is this cylinder likely to be safe against
sudden rupture (which would be disastrous because chlorine gas is highly
toxic)?
1 𝑚𝑜𝑙
SOLUTION: a) 𝑛Cl2 = 500 𝑔 ×
70.609 𝑔
= 7.08 mol

𝐿 − 𝑎𝑡𝑚
7.08 𝑚𝑜𝑙 × 0.08206 × 298 𝐾
𝑝= 𝑚𝑜𝑙 ∙ 𝐾 = 𝟒𝟑. 𝟑 𝒂𝒕𝒎
4.0 𝐿 Gase
s
© 2015 Pearson Education, Inc.
Sample Problem 14 Applying the van der Waals Equation
𝐿2 ∙𝑎𝑡𝑚 𝐿
SOLUTION: b) for chlorine gas, 𝑎 = 6.49 and 𝑏 = 0.0562
𝑚𝑜𝑙 2 𝑚𝑜𝑙

𝐿 ∙ 𝑎𝑡𝑚 𝐿2 ∙ 𝑎𝑡𝑚
(7.08 𝑚𝑜𝑙)(0.08206 )(298 𝐾) (6.42 2 )(7.08 𝑚𝑜𝑙)2
𝑝= 𝑚𝑜𝑙 ∙ 𝐾 − 𝑚𝑜𝑙
𝐿 (4.0 𝐿)2
[4.0 𝐿 − 7.08 𝑚𝑜𝑙 × 0.0562 ]
𝑚𝑜𝑙
= 28 𝑎𝑡𝑚

This pressure is well within the safety limits of the cylinder. The ideal
gas law predicts a pressure 15 atm higher than that of the van der
Waals equation.

Gase
s
© 2015 Pearson Education, Inc.