Peter Atkins • Julio de Paula

Atkins’ Physical Chemistry

Eighth Edition

Chapter 1
The Properties of Gases

Copyright © 2006 by Peter Atkins and Julio de Paula

 Physical Characteristics of Gases
• Gases assume the volume and shape of their containers.
• Gases are the most compressible state of matter.
• Gases are miscible
• Gases have much lower densities than liquids and solids.
• Density of a gas given in g/L (vice g/mL for liquids)

NO2
 The Perfect Gas
• Each gas can be described by an equation of state:

• P = f(T, V, n) Pressure ≡ force / unit area

Fig 1.1
 Energy Changes in Chemical Reactions
Heat - the transfer of thermal energy between two bodies that
are at different temperatures

Temperature - a measure of the thermal energy

Temperature = Thermal Energy

(intensive) (extensive)

90 °C
40 °C
greater temperature greater thermal energy
Fig 1.2 Temperature ≡ the
direction of thermal energy flow
through a thermally conducting
rigid wall
 Thermal equilibrium ≡ no net heat flow between two objects
in contact through a diathermic boundary

Fig 1.3 Zeroth Law of

thermodynamics
 Temperature Scales

Perfect gas temperature scale

K = °C + 273.15
 The Gas Laws

 Pressure - Volume Relationship: Boyle’s Law

 Temperature - Volume Relationship: Charles’s

and Gay-Lussac’s Law

 Volume - Amount Relationship: Avogadro’s Law

 The Perfect (Ideal) Gas Law

Fig 1.4 Boyle’s Law

• PV = constant

• A limiting law
Fig 1.5 Charles’s Law

• V = constant ∙ T

• Another limiting law

Fig 1.6 Charles’s Law

• Variation of volume with

temperature at constant P
Fig 1.7 Charles’s Law

• Variation of pressure with

temperature at constant V
 Perfect Gas Equation
1
Boyle’s law: V∝ (at constant n and T)
P
Charles’ law: V∝T (at constant n and P)

Avogadro’s law: V∝n (at constant P and T)

V ∝ nT
P

nT nT
V = constant · =R R is the gas constant
P P

PV = nRT

What is the value of R?

 PV = nRT
PV (1.000 atm)(22.41 4 L)
R 
nT (1.000 mol)(273.1 5 K)

L  atm
R  0.08206
mol  K

The conditions 0 °C and 1 atm are called

standard temperature and pressure (STP).

Experiments show that at STP,

1 mole of an ideal gas
occupies 22.414 L:
 Comparison of Molar Volumes at STP

• One mole of an ideal gas occupies 22.414 L @ STP

• One mole of various real gases at STP occupy:

Fig 1.8 A region of a P-V-T surface of a perfect gas
Fig 1.8 Sections through P-V-T surface of a perfect gas
PV = nRT useful when P, V, n, and T do not change

Modify equation when P, V, and/or T change:

• Initial state (1) of gas:

P1V1 Combined Gas Law

R
n1T1
P1V1 P2 V2
• Final state (2) of gas: 
n1T1 n2 T2
P2 V2
R Eqn [1.12]
n2 T2
 Gas Mixtures and Partial Pressures

V and T
are
constant

P1 P2 Ptotal = P1 + P2

Dalton’s Law of Partial Pressures

Consider a case in which two gases, A and B, are in a
container of volume V at a total pressure PT

nART
PA = nA is the number of moles of A
V
nBRT nB is the number of moles of B
PB =
V
nA nB
PT = PA + PB XA = XB =
nA + nB nA + nB

PA = XA PT PB = XB PT

ni
Pi = Xi PT mole fraction (Xi) =
nT
Dalton’s Law of Partial Pressures