Petrucci Harwood Herring Madura

GENERAL
CHEMISTRY

Ninth
Edition

Principles and Modern Applications

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Chapter 6: Gases
Philip Dutton
University of Windsor, Canada
Prentice-Hall 2007

Contents
6-1
6-2
6-3

Properties of Gases: Gas Pressure

The Simple Gas Laws
Combining the Gas Laws:
The Ideal Gas Equation and
The General Gas Equation
Applications of the Ideal Gas Equation
Gases in Chemical Reactions
Mixtures of Gases

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6-4
6-5
6-6

Contents
6-6
6-7
6-8

Mixtures of Gases
KineticMolecular Theory of Gases
Gas Properties Relating to the
KineticMolecular Theory
Nonideal (Real) Gases

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6-9

Focus On Earths Atmosphere

6-1 Properties of Gases: Gas Pressure

The gaseous states of three halogens.

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Most common gases are colorless
H2, O2, N2, CO and CO2

Properties of Common Gases

Despite wide differences in chemical
properties, ALL gases more or less obey the
same set of physical properties.
Four Physical Properties of Gases
Inter-related

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1.
2.
3.
4.

Pressure (P)
Volume (V)
Temperature (T)
Amount = moles (n)

The Concept of Pressure

The pressure exerted
by a solid.
Both cylinders have
the same mass
They have different
areas of contact

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Force (N)
P (Pa) =
Area (m2)

Force
Force vs.
vs. Pressure
Pressure
Consider a woman wearing flat shoes vs. high
"spike" heels
Weight of woman is same = 120 lbs.
Pressure on floor differs greatly

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Shoe
Flat

Area
10" x 3"
= 30 in2

Spike

0.4" x 0.4"
= 0.16 in2

Pressure

120 lbs
P
4 Psi
2
30 in
120 lbs
P
750 Psi
2
0.16 in

Why airline stewardesses cannot wear spike heels!

7

Liquid Pressure
The pressure exerted by
a liquid depends on:
The height of the
column of liquid.
The density of the
column of liquid.

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P = g h d

Barometric Pressure
Standard Atmospheric Pressure
1.00 atm, 760 mm Hg, 760 torr, 101.325 kPa, 1.01325 bar

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Manometers

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6-2 Simple Gas Laws

Boyle 1662

1
P
V

PV = constant

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EXAMPLE 6-4
Relating Gas Volume and Pressure Boyles Law. The
volume of a large irregularly shaped, closed tank can be
determined. The tank is first evacuated and then connected to a
50.0 L cylinder of compressed nitrogen gas. The gas pressure in
the cylinder, originally at 21.5 atm, falls to 1.55 atm after it is
connected to the evacuated tank. What is the volume of the
tank?

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EXAMPLE 6-4

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P1V1 = P2V2

P1V1
= 694 L
V2 =
P2

Vtank = 644 L

Charless Law
Charles 1787
Gay-Lussac 1802

VT

V=bT

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Standard Temperature and Pressure

Gas properties depend on conditions.
Define standard conditions of temperature
and pressure (STP).

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P = 1 atm = 760 mm Hg
T = 0C

= 273.15 K

Avogadros Law
Gay-Lussac 1808
Small volumes of gases react in the ratio of
small whole numbers.

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Avogadro 1811

Equal volumes of gases have equal numbers of

molecules and
Gas molecules may break up when they react.

Formation of Water

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Avogadros Law
At an a fixed temperature and pressure:
Vn

or

V=cn

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At STP

1 mol gas = 22.4 L gas

6-3 Combining the Gas Laws: The Ideal

Gas Equation and the General Gas
Equation
Boyles law

V 1/P

Charless law

VT

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Avogadros law V n

PV = nRT

nT
V
P

The Gas Constant

PV = nRT
PV
R=
nT

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= 0.082057 L atm mol-1 K-1
= 8.3145 m3 Pa mol-1 K-1
= 8.3145 J mol-1 K-1

Using the Gas Law

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The General Gas Equation

P1V1
P2V2
R=
=
n1T1
n2T2

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If we hold the amount and volume constant:

P1
T1

P2
T2

Using the Gas Laws

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6-4 Applications of the Ideal Gas Equation

Molar Mass Determination
PV = nRT

and

n=

m
M

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m
RT
PV =
M
m RT
M=
PV

EXAMPLE 6-10
Determining a Molar Mass with the Ideal Gas Equation.
Polypropylene is an important commercial chemical. It is used
in the synthesis of other organic chemicals and in plastics
production. A glass vessel weighs 40.1305 g when clean, dry
and evacuated; it weighs 138.2410 when filled with water at
25C (water = 0.9970 g cm-3) and 40.2959 g when filled with
propylene gas at 740.3 mm Hg and 24.0C. What is the molar
mass of polypropylene?

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Strategy:
Determine Vflask. Determine mgas. Use the Gas Equation.

EXAMPLE 6-10
Determine Vflask:
Vflask = mH2O dH2O = (138.2410 g 40.1305 g) (0.9970 g cm-3)

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= 98.41 cm3 = 0.09841 L

Determine mgas:

mgas = mfilled - mempty = (40.2959 g 40.1305 g)

= 0.1654 g

EXAMPLE 5-6
Use the Gas Equation:

PV = nRT

m
RT
PV =
M

m RT
M=
PV

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M=

(0.6145 g)(0.08206 L atm mol-1 K-1)(297.2 K)

(0.9741 atm)(0.09841 L)
M = 42.08 g/mol

Gas Densities
PV = nRT

and

m
m
, n=
d=
M
V

m
RT
PV =
M

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m
MP
=d=
V
RT

6-5 Gases in Chemical Reactions

Stoichiometric factors relate gas quantities to
quantities of other reactants or products.
Ideal gas equation relates the amount of a gas
to volume, temperature and pressure.
Law of combining volumes can be developed
using the gas law.

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EXAMPLE 6-12
Using the Ideal gas Equation in Reaction Stoichiometry
Calculations. The decomposition of sodium azide, NaN3, at
high temperatures produces N2(g). Together with the necessary
devices to initiate the reaction and trap the sodium metal formed,
this reaction is used in air-bag safety systems. What volume of
N2(g), measured at 735 mm Hg and 26C, is produced when 70.0
g NaN3 is decomposed?

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2 NaN3(s) 2 Na(l) + 3 N2(g)

EXAMPLE 6-12
Determine moles of N2:
nN2 = 70 g NaN3

1 mol NaN3
65.01 g NaN3

3 mol N2
2 mol NaN3

= 1.62 mol N2

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Determine volume of N2:
V=

nRT
P

(1.62 mol)(0.08206 L atm mol-1 K-1)(299 K)

(735 mm Hg)

1.00 atm
760 mm Hg

= 41.1 L

6-6 Mixtures of Gases

Gas laws apply to mixtures of gases.
Simplest approach is to use ntotal, but....

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Partial pressure

Each component of a gas mixture exerts a

pressure that it would exert if it were in the
container alone.

Daltons Law of Partial Pressure

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The total pressure of a mixture of gases is the sum of
the partial pressures of the components of the mixture.

Partial Pressure
Ptot = Pa + Pb +
Va = naRT/Ptot

and

Vtot = Va + Vb+

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na
naRT/Ptot
Va
=
=
n
RT/P
ntot
Vtot
tot
tot

na
naRT/Vtot
Pa
=
=
ntotRT/Vtot
ntot
Ptot

Recall

na
= a
ntot

Pneumatic Trough

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Ptot = Pbar = Pgas + PH2O

6-7 Kinetic Molecular Theory

Particles are point masses in constant,
random, straight line motion.
Particles are separated by great

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distances.

Collisions are rapid and elastic.

No force between particles.
Total energy remains constant.

Pressure Assessing Collision Forces

Translational kinetic energy,

1
e k mu 2
2

Frequency of collisions,

N
vu
V

Impulse or momentum transfer,

I mu

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Pressure proportional to
impulse times frequency

N
2
P mu
V

Pressure and Molecular Speed

Three dimensional systems lead to:

1N
P
m u2
3V

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um is the modal speed

uav is the simple average

urms

u2

Pressure
Assume one mole:

1
2
PV N A m u
3

PV=RT so:

3RT N A m u

NAm = M:

3RT M u

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Rearrange:

u rms

3RT
M

Distribution of Molecular Speeds

u rms

3RT
M

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Determining Molecular Speed

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Temperature
Modify:

1
2
1
2
2
PV N A m u N A ( m u )
3
3
2

PV=RT so:

2
RT N A ek
3

Solve for ek:

3 R
ek
(T)
2 NA

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Average kinetic energy is directly proportional to temperature!

6-8 Gas Properties Relating to the

Kinetic-Molecular Theory
Diffusion

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Net rate is proportional to
molecular speed.

Effusion

A related phenomenon.

Grahams Law
rate of effusion of A (u rms ) A

rate of effusion of B (u rms ) B

3RT/M A

3RT/MB

MB
MA

Only for gases at low pressure (natural escape, not a jet).

Tiny orifice (no collisions)
Does not apply to diffusion.

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Ratio used can be:
Rate of effusion (as above)
Molecular speeds
Effusion times

Distances traveled by molecules

Amounts of gas effused.

6-9 Nonideal (Real) Gases

Compressibility factor PV/nRT = 1
Deviations occur for real gases.
PV/nRT > 1 - molecular volume is significant.
PV/nRT < 1 intermolecular forces of attraction.

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Real Gases

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van der Waals Equation

n2a
P+
V2

V nb

= nRT

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End of Chapter Questions

A problem is like a knot in a ball of wool:
If you pull hard on any loop:
The knot will only tighten.
The solution (undoing the knot) will not be achieved.

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If you pull lightly on one loop and then another:
You gradually loosen the knot.
As more loops are loosened it becomes easier to
undo the subsequent ones.

Dont pull too hard on any one piece of

information in your problem, it tightens.