Chapter 1.
The Properties of Gases
Thermodynamics
Contents
The Perfect Gas
1.1 The states of gases
1.2 The gas laws
Real Gases
1.3 Molecular interactions
1.4 The van der Waals equation
States of Matter
Gases – fill container, random rapid motion, never
coming to rest or clumping together. Motion is mainly
translational
Liquids – fixed volume, flow and assume shape of container,
only slightly compressible, stronger forces
hold molecules together. Motion is mainly translational
Solids – fixed volume, definite shape, generally less
compressible than liquids, forces hold particles in a fixed
shape. Motion is mainly vibrational
1.1 The states of gases
Physical State
1. Two samples of a substance that have the same
physical properties are in the same state
2. Physical Properties : V, n, p, and T
3. It is sufficient to specify only three of these
variables
4. p = f(T,V,n) : an equation of state
(e.g.) p = nRT/V for a perfect gas
1.1 The states of gases
(a) Pressure
• Defined as force, F, divided by the area, A
• p = F/A
Mechanical equilibrium
1.1 The states of gases
(b) The measurement of pressure
• barometer
• Hydrostatic pressure : P = ρgh
✓ ρ : the mass density of liquid
✓ g : gravitational acceleration
✓ h : height
1.1 The states of gases
(c) Temperature
• Indicates the direction of the flow of energy
through a thermally conducting rigid wall
• Types of boundary between two objects at
different temperatures
✓ Diathermic : a change of state is observed
✓ Adiabatic : no change occur
• Thermal equilibrium : No change of state
occurs when two objects are in contact through
a diathermic boundary
1.1 The states of gases
(c) Temperature
Thermal equilibrium
1.1 The states of gases
The Zeroth Law of thermodynamics
• If A is in thermal equilibrium with B, and B is in
thermal equilibrium with C, then C is also in
thermal equilibrium with A
• Justifies the concept of temperature and the use
of a thermometer
• Celcius scale :℃
• Thermodynamic temperature scale : K (kelvins)
T/K = θ/℃ + 273.15
1.2 The gas laws
(a) The perfect gas law
• Boyle’s law : pV = constant at constant n, T
• Charles’s law : V = constant × T at constant n, P
P = constant × T at constant n, V
• Avogadro’s principle : V = constant × n at
constant p, T
isotherm isobars isochores
1.2 The gas laws
(a) The perfect gas law
• pV = nRT : perfect gas law
• R : gas constant
• Perfect (ideal) gas vs. Real gas
1.2 The gas laws
(a) The perfect gas law
• pV = nRT : perfect gas law
• R : gas constant
• Perfect (ideal) gas vs. Real gas
• The perfect gas law is
important because it is used to
derive a wide range of
relations that are used
throughout thermodynamics
1.2 The gas laws
(b) The kinetic model of gases
1. The gas consists of molecules of mass m in
ceaseless random motion
2. The size of the molecules is negligible, in the
sense that their diameters are much smaller
than the average distance travelled between
collisions
3. The molecules interact only through brief,
infrequent, and elastic collisions
1.2 The gas laws
(b) The kinetic model of gases
1
pV = nMc 2
3
M : the molar mass of the molecules
c : the root mean-square speed of the molecules
1/2
2 1/2 æ 3RT ö
c= v =ç ÷
è M ø
pV = nRT
1.2 The gas laws
(c) Mixtures of gases
pJ = xJ p : partial pressure
nJ
xJ = : mole fraction
N
pA + pB + = (xA + xB + )p = p
• Dalton’s law : The pressure exerted by a
mixture of gases is the sum of the pressures that
each one would exert if it occupied the container
alone.
1.3 Molecular interactions
• Repulsive forces and
attractive forces assist
expansion and compression,
respectively
1. At low pressure, the
intermolecular forces play no
significant role
2. At moderate pressures, the
attractive forces dominate
3. At high pressures, the
repulsive forces dominate
1.3 Molecular interactions
(a) Compression factor
Vm pVm
Z= o = : Compression factor
Vm RT
1. At low pressure, Z ≈ 1
2. At moderate pressures, Z < 1
3. At high pressures, Z > 1
1.3 Molecular interactions
(b) Virial coefficients
The virial equation of state
pVm = RT (1+ B' p + C ' p 2 + )
æ B C ö
= RT ç1+ + 2 + ÷
è Vm Vm ø
= RTZ
dZ
= B'+ 2 pC '+ ® B ’ as p ® 0
dp
The virial coefficients depend on T
dZ/dp⟶ 0 as p⟶ 0 at Boyle
temperature
1.3 Molecular interactions
(c) Condensation
• A liquid appears
• The pressure is
vapor constant
pressure • Two phases exist
Deviate from
the perfect gas law
Relatively
ideal
Experimental Isotherms of carbon dioxide
1.3 Molecular interactions
(c) Critical constants
• At TC, a surface separating two
phases does not appear
• Critical Point : the volumes at each
end of the horizontal part of the
isotherm merge to a critical point
• TC : critical temperature
• pC : critical pressure
• VC : critical molar volume
• At T > TC, the supercritical fluid
Experimental Isotherms of carbon dioxide
1.4 The van der Waals equation
(a) Formulation of the equation
nRT n2 RT a
p= -a 2 = - 2
V - nb V Vm - b Vm
• a : the strength of attractive interactions
• b : the volume taken by molecules
1.4 The van der Waals equation
(b) The features
nRT n2 RT a
p= -a 2 = - 2
V - nb V Vm - b Vm
• Perfect gas isotherms are obtained at high T
and large molar volumes
• Liquid and gas coexist when cohesive and
dispersing effects are in balance
• The critical constants are related to a and b
The unrealistic Van der Waals loops need be
treated by the Maxwell construction
1.4 The van der Waals equation
(b) The features
nRT n2 RT a
p= -a 2 = - 2
V - nb V Vm - b Vm
• The critical constants are related to a and b
dp RT 2a
=- + 3 =0
dVm (Vm - b) Vm
2
d2 p 2RT 6a
= - 4 =0
dVm (Vm - b) Vm
2 3
a 8a
VC = 3b, pC = 2
, TC =
27b 27Rb
pV 3
ZC = C C =
RTC 8
1.4 The van der Waals equation
(b) The principle of corresponding states
nRT n2 RT a
p= -a 2 = - 2
V - nb V Vm - b Vm
• Reduced variables
Vm p T
Vr = , pr = , Tr =
VC pC TC
8Tr 3
pr = - 2
3Vr -1 Vr
• Real gases at the same reduced volume and
reduced temperature exert the same reduced
pressure