Chapter 10

Gases

Barometers and Standard

Atmospheric Pressure

Barometers and Standard

Atmospheric Pressure
Standard atmospheric
pressure defined as the
pressure sufficient to support a
mercury column of 760mm
(units of mmHg, or torr).

Barometers and Standard

Atmospheric Pressure
Standard atmospheric
pressure defined as the
pressure sufficient to support a
mercury column of 760mm
(units of mmHg, or torr).
Another unit was introduced to
simplify things, the atmosphere
(1 atm = 760 mmHg).

Barometers and Standard

Atmospheric Pressure
Standard atmospheric
pressure defined as the
pressure sufficient to support a
mercury column of 760mm
(units of mmHg, or torr).
Another unit was introduced to
simplify things, the atmosphere
(1 atm = 760 mmHg).
1 atm = 760 mmHg = 760 torr =
101.325 kPa (page 262).

STP
standard temperature and pressure
Standard temperature

0C or 273 K

Standard pressure

1 atm (or equivalent)

 Pressure varies
inversely with volume
Volume varies inversely
with pressure
The volume of a sample of gas is inversely
proportional to its pressure, if temperature
remains constant.

Boyles Law

Boyles Law: Pressure & Volume

(Figure 10.6 (a) page 263)
P V
P V

Boyles Law: Pressure-Volume Relationships

Asampleofairoccupies73.3mLat98.7atmand0C.
Whatvolumewilltheairoccupyat4.02atmand0C?

1800 mL

Boyles Law: Pressure-Volume Relationships

Asampleofheliumoccupies535mLat988mmHgand
25C.Ifthesampleistransferredtoa1.05Lflaskat
25C,whatwillbethegaspressureintheflask?

503 mm Hg

 Effects of temperature on a
gas
Volume varies directly with
Temperature
The volume of a quantity of gas,
held at constant pressure, varies
directly with the Kelvin
temperature.

Charless Law

Charles Law: Volume and Temperature

(Figure 10.8 Page 266)

Charles Law and Absolute Zero

Extrapolation to
zero volume gives
a temperature of
-273C or 0 K

Charless Law: Temperature-Volume Relationships

A sample of oxygen gas occupies a volume of 2.10 L at 25 C.
What volume will this sample occupy at 150 C? (Assume no
change in pressure.)

2.98 L

Charless Law: Temperature-Volume Relationships

A sample of

oxygen gas occupies a volume of 2.10 L at 25 C.

At what Celsius temperature will the volume of oxygen
occupy 0.750 L? (Assume no change in pressure.)

-167C

Pressure vs. Temperature

Pressure varies directly with Temperature
If the temperature of a fixed volume of gas
doubles its pressure doubles.

Pressure vs. Temperature

The pressure exerted by a
gas is directly related to the
Kelvin temperature.
V is constant.

Pressure vs. Temperature

Example
A gas has a pressure of 645 torr at 128C. What is the
temperature in Celsius if the pressure increases to 1.50 atm?
Pi = 645 torr

Pf = 1.50 atm 760 torr = 1140 torr

1 atm

Ti = 128C + 273
= 401 K

Tf = ?K

Solution
T2 = 401 K x 1140 torr = 709K
645 torr
709K - 273 = 436C

Combined Gas Law Problem

A sample of helium gas has a volume of 0.180 L, a
pressure of 0.800 atm and a temperature of 29C.
What is the new temperature(C) of the gas at a
volume of 90.0 mL and a pressure of 3.20 atm?

Combined Gas Law Problem

A sample of helium gas has a volume of 0.180 L, a
pressure of 0.800 atm and a temperature of 29C.
What is the new temperature(C) of the gas at a
volume of 90.0 mL and a pressure of 3.20 atm?

302 K

3.20 atm x 90.0 mL = 604 K

0.800 atm 180.0 mL
604 K - 273 = 331 C

Combined Gas Law

A 10.0 cm3 volume of gas measured 75.6 kPa
and 60.0C is to be corrected to correspond
to the volume it would occupy at STP.

6.12 cm3

Gay-Lussacs Law
Gay-Lussacs Law of combining volumes: at a given
temperature and pressure, the volumes of gases which
react are ratios of small whole numbers.

How many liters of steam can be

formed from 8.60L of oxygen gas?

17.2 L

How many liters of hydrogen gas

will react with 1L of nitrogen gas to
form ammonia gas?

3L H2

How many mL of hydrogen are needed to

produce 13.98 mL of ammonia?

20.97 ml NH3

Avogadros Law: Equal volumes of gases at the same

temperature and pressure contain the same number of particles.

The molar volume of a gas at STP =

22.4L

22.4 L

Ideal Gas
An ideal gas is defined as one for which both the
volume of molecules and forces of attraction
between the molecules are so small that they have
no effect on the behavior of the gas.

Ideal Gas Equation

PV=nRT

R values

R values for atm and kPa

on Page 272 in book.

Calculate the volume occupied by 0.845 mol of

nitrogen gas at a pressure of 1.37 atm and a
temperature of 315 K.

15.9 L

Find the pressure in millimeters of mercury of a

0.154 g sample of helium gas at 32C and contained
in a 648 mL container.

1130 mm Hg

An experiment shows that a 113 mL gas

sample has a mass of 0.171 g at a pressure of
721 mm Hg and a temperature of 32C. What is
the molar mass (molecular weight) of the gas?

40.0 g/mol

Can the ideal gas equation be used to

determine the molar mass of a liquid?

Homework
Do the lab summary for The Molecular
Mass of a Volatile Liquid. It is due ____.
Attempt the pre-lab for The Molecular
Mass of a Volatile Liquid. It is due ____.

Problem: A volatile liquid is placed in a flask whose volume is 590.0 ml

and allowed to boil until all of the liquid is gone, and only vapor fills the
flask at a temperature of 100.0 oC and 736 mm Hg pressure. If the mass
of the flask before and after the experiment was 148.375g and 149.457 g,
what is the molar mass of the liquid?

57.9 g/mol

What is the density of methane gas (natural

gas), CH4, at 125oC and 3.50 atm?

1.71 g/L

Calculate the density in g/L of

O2 gas at STP.

1.43 g/L

Daltons Law of Partial Pressure

The total pressure in a container is the sum of the partial
pressures of all the gases in the container.
In a gaseous mixture, a gass partial pressure is the one the
gas would exert if it were by itself in the container.

Ptotal = P1 + P2 + P3
Ptotal = 100 KPa + 250 KPa + 200 KPa = 550 KPa

Two 1.0 L containers, A and B, contain gases

with 2.0 atm and 4.0 atm, respectively. Both
gases are forced into Container B. Find the total
pressure of the gas mixture in B.

2.0 atm

1.0 L

4.0 atm

1.0 L

Vmixture

P
2.0 atm

1.0 L

4.0 atm

Total = 6.0 atm

Daltons Law Problem

Air contains oxygen, nitrogen, carbon dioxide, and
trace amounts of other gases. What is the partial
pressure of oxygen at standard conditions if the
partial pressure of nitrogen, carbon dioxide, and
other gases are 79.1 KPa, 0.04 KPa, and 0.94 KPa
respectively?
Ptotal = PO + PN + PCO + POther gases
2

101.3 KPa = PO + 79.1 KPa + 0.04 KPa + 0.94KPa

2

PO = 101.3 KPa (79.1 KPa + 0.04 KPa + 0.94KPa)

2

PO = 21.2 KPa
2

Two 1.0 L containers, A and B, contain gases with

2.0 atm and 4.0 atm, respectively. Both gases are
forced into Container Z (vol. 2.0 L). Find the total
pressure of mixture in Z.

Two 1.0 L containers, A and B, contain gases with

2.0 atm and 4.0 atm, respectively. Both gases are
forced into Container Z (vol. 2.0 L). Find the total
pressure of mixture in Z.

PX

VX

2.0 atm

1.0 L

4.0 atm

1.0 L

VZ
2.0 L

PX,Z
1.0 atm
2.0 atm

Total = 3.0 atm

Find total pressure of the gas mixture in Container Z.

A
1.3 L
3.2 atm

B
2.6 L
1.4 atm

3.8 L
2.7 atm

2.3 L
X atm

Find total pressure of the gas mixture in Container Z.

1.3 L
3.2 atm

2.6 L
1.4 atm
PX

VX

3.2 atm

1.3 L

1.4 atm

2.6 L

2.7 atm

3.8 L

3.8 L
2.7 atm

2.3 L
X atm

VZ

PX,Z
1.8 atm

2.3 L

1.6 atm
4.5 atm

Total = 7.9 atm

Daltons Law

Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 422

Daltons Partial Pressures

Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 421

Daltons Law of Partial Pressures

The mole ratio in a mixture of gases determines each
gass partial pressure.
Total pressure of mixture (3.0 mol He and 4.0 mol Ne) is
97.4 kPa.
Find partial pressure of each gas

Daltons Law of Partial Pressures

Total pressure of mixture (3.0 mol He and 4.0 mol Ne) is 97.4 kPa.
Find partial pressure of each gas.

PHe

3 mol He
97.4 kPa

7 mol gas

41.7 kPa

PNe

4 mol Ne
97.4 kPa

7 mol gas

55.7 kPa

80.0 g each of He, Ne, and Ar are in a container. The total

pressure is 780 mm Hg. Find each gass partial pressure.

80.0 g each of He, Ne, and Ar are in a container. The total

pressure is 780 mm Hg. Find each gass partial pressure.

1 mol
80 g He
20 mol He
4g

1 mol
80 g Ne
4 mol Ne
20 g
1 mol
80 g Ar
2 mol Ar
40 g

PHe = 20/26
of total

Total:
26 mol gas

PNe = 4/26
of total

PAr = 2/26
of total

PHe 600 mm Hg, PNe 120 mm Hg, PAr 60 mm Hg

Example: A student generates oxygen

gas and collects it over water. If the
volume of the gas is 245 mL and the
barometric pressure is 758.0 torr at 25oC,
what is the volume of the dry oxygen
gas at STP? (Pwater = 23.8 torr at 25oC)
PO2 = PT - Pwater = 758.0 torr - 23.8 torr = 734.2 torr

Find the molar mass of an unknown gas if a 0.16 g sample of

the gas is collected over water and equalized to a pressure of
781.7 torr and a volume of 90.0 mL at a temperature of 28C .

Find the molar mass of an unknown gas if a 0.16 g sample of

the gas is collected over water and equalized to a pressure of
781.7 torr and a volume of 90.0 mL at a temperature of 28C .

44 g/mol

Homework
Do the AP sample problem (1999 Test
question #5) in notebook. It will be
included as part of your homework.
Dont forget the pre-lab and lab summary
for The Molecular Mass of a Volatile
Liquid.

Gas Diffusion and Effusion

Graham's Law:
governs the rate of effusion and diffusion of gas molecules.

Stink or Die
a

The Root Mean Square Speed

Fig. 10.17 Page 285

To use Grahams Law, both gases must be at same temperature.

diffusion:
diffusion particle movement
from
high to low concentration
NET MOVEMENT

effusion:
effusion diffusion of gas
particles
through an opening

For gases, rates of diffusion & effusion obey Grahams law:

more massive = slow; less massive = fast

Gas Diffusion and Effusion

Graham's Law:
governs the rate of effusion and diffusion of gas molecules.

Rate of A
molar mass of B

Rate of B
molar mass of A
Rate
Rateof
ofdiffusion/effusion
diffusion/effusionisis inversely
inversely
proportional
proportionalto
toits
itsmolar
molarmass.
mass.

35

36

Br

Grahams Law

79.904

Kr

83.80

Determine the relative rate of diffusion

for krypton and bromine.
The lightest gas is Gas A and the heavier gas is Gas B.
Relative rate means find the ratio vA/vB.

vA

vB
v Kr

v Br2

m Br2
m Kr

mB
mA
159.80 g/mol
1.381
83.80 g/mol

Kr diffuses 1.381 times faster than Br2.

Grahams Law

1.00794

15.9994

A molecule of oxygen gas has an average speed of 12.3

m/s at a given temp and pressure. What is the average
speed of hydrogen molecules at the same conditions?

vA

vB

mB
mA

vH 2
12.3 m/s

32.00 g/mol
2.02 g/mol

vH2

vH 2
vO2

mO2
mH 2

12.3 m/s

3.980

vH 2 49.0 m/s

H2

Grahams Law

2.0

15.9994

An unknown gas diffuses 4.0 times faster than O2.

Find its molar mass.
The lightest gas is Gas A and the heavier gas is Gas B.
The ratio vA/vB is 4.0.

vA

vB

mB
mA

vA

v O2

mO2
mA

32.00
g/mol
4.0

m AA

32.00 g/mol
16
mA

Square both
sides to get rid
of the square
root sign.

32.00 g/mol
2.0 g/mol
mA
16

Kinetic Molecular Theory

Theory developed to explain gas behavior.
Theory of moving molecules.
Assumptions:
Gases consist of a large number of molecules in constant
random motion.
Volume of individual molecules negligible compared to
volume of container.
Intermolecular forces (forces between gas molecules)
negligible.
Energy can be transferred between molecules, but total
kinetic energy is constant at constant temperature.
Average kinetic energy of molecules is proportional to
temperature.

Kinetic Molecular Theory

Kinetic molecular theory gives us an
understanding of pressure and
temperature on the molecular level.
Pressure of a gas results from the
number of collisions per unit time on the
walls of container.
Magnitude of pressure given by how
often and how hard the molecules
strike.
Gas molecules have an average kinetic
energy.
Each molecule has a different energy.

Kinetic Molecular Theory

There is a spread of
individual energies
of gas molecules
in any sample of
gas.
As the temperature
increases, the average
kinetic energy of the
gas molecules
increases

Kinetic Molecular Theory

As kinetic energy increases, the velocity of the gas
molecules increases.
Root mean square speed, u, is the speed of a gas
molecules having the certain average kinetic energy.
Average kinetic energy, , is related to root mean
square speed, u:

2
1
2 mu

Kinetic Molecular Theory

As kinetic energy increases, the velocity of the gas
molecules increases.
Root mean square speed, u, is the speed of a gas
molecules having the certain average kinetic energy.
Average kinetic energy, , is related to root mean
square speed, u:

2
1
2 mu

How does this theory explain Boyles Law?

As the volume of a container of gas increases at
constant temperature, the gas molecules have to travel
further to hit the walls of the container. There are
fewer collisions by the gas molecules with the walls
of the container. Therefore, pressure decreases.
If temperature increases at constant volume, the average
kinetic energy of the gas molecules increases.
Therefore, there are more collisions with the
container walls and the pressure increases.

How does this theory explain Charles Law?

If temperature increases at constant volume, the average
kinetic energy of the gas molecules increases and
they speed up. Therefore, there are more frequent
and more forceful collisions with the container walls
by the gas molecules and the pressure increases.

Ideal Gases vs. Real Gases

An ideal gas is an imaginary gas made
up of particles with negligible particle
volume and negligible attractive forces.

Ideal Gases vs. Real Gases

In a Real Gas the molecules of a gas do
have volume and the molecules do attract
each other.
Therefore anything that makes gas particles
more likely to stick together or stay close to
one another make them behave less ideally.

Real Gases: Deviations from Ideal Behavior

As the pressure on a gas increases, the molecules are forced
into a smaller volume.
As the volume becomes
smaller, the molecules get
closer together, and a
greater fraction of the
occupied space is actually
taken up by gas molecules.
Therefore, the higher the
pressure, the less the gas
resembles an ideal gas.

Real Gases: Deviations from Ideal Behavior

The smaller the distance between gas
molecules, the more likely attractive
forces will develop between the
molecules.
As temperature increases, the gas
molecules move faster and are
further apart.
Also, higher temperatures mean
more energy available to break
intermolecular forces.
Therefore,
the
higher
the
temperature, the more ideal the gas.

Real Gases and Ideal Behavior

A real gas typically exhibits behavior closest to
ideal gas behavior at low pressures and high
temperatures.

Real Gases: The van der Waals equation

We add two terms to the ideal gas equation one to correct for
volume of molecules and the other to correct for
intermolecular attractions
The correction terms generate the van der Waals equation:

nRT
n2a
P
2
V nb V
where a and b are empirical constants.
2

n
P a V nb nRT
2

a corrects for the effect of molecular attractions (van der

Waals forces), and b corrects for the molecular volume

Real Gases: The van der Waals equation

We add two terms to the ideal gas equation one to correct for
volume of molecules and the other to correct for intermolecular
attractions
The correction terms generate the van der Waals equation:
You will not be required to solve this equation but you should
know its form and which variables need to be corrected.

n 2a
V2

V nb nRT

a corrects for the effect of molecular attractions (van der

Waals forces), and b corrects for the molecular volume