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• Assume a container
is a cube
Edges are length d
• Look at the motion
of the molecule in
terms of its velocity
components
• Look at its
momentum and the
average force
Pressure and Kinetic Energy
• Since the collision is elastic, the y -
component of molecule’s velocity
remains unchanged, while the x -
component reverses sign. Thus the
molecule undergoes the momentum
change of magnitude 2mvx.
mv x2
F i
F d m v 2
m v 2
P x
x
A A A Ad V
Pressure and Kinetic Energy
m v 2
mN v 2
P x
x
V V N
Since, x
v 2
is just the average of the squares of x –
components of velocities:
N
mN 2
P vx
V
Pressure and Kinetic Energy
Since, the molecules are moving in random directions the
average quantities 2
vx , v 2
y , and v 2
z must be
equal and the average of the molecular speed
v v v v
2 2
x
2
y
2
z
mN 2
P v
3V
Pressure and Kinetic Energy
mN 2 can be written:
• The relationship P v
3V
2N 1 ___
P m v
2
3V 2
• This tells us that pressure is proportional to the number
of molecules per unit volume (N/V) and to the average
translational kinetic energy of the molecules
Pressure and Kinetic Energy
2 N 1 2 Nk B T
P m v
3 V 2 V
2 2
• This can be applied to each direction,
1 ___2 1
m v x k BT
2 2
with similar expressions for vy and vz
A Microscopic Description of Temperature
1 ___2 3 3
K tot trans N m v Nk BT nRT
2 2 2
• If we have a gas with only translational energy, this is the
internal energy of the gas
• This tells us that the internal energy of an ideal gas
depends only on the temperature
Molar Specific Heat
• Several processes can
change the temperature of
an ideal gas
• Since ΔT is the same for
each process, ΔEint is also
the same
• The heat is different for the
different paths
• The heat associated with a
particular change in
temperature is not unique
Molar Specific Heat
• Solving
3
E in t nC V T nR T
2
for CV gives CV = 3/2 R = 12.5 J/mol . K for all
monatomic gases
• This is in good agreement with experimental
results for monatomic gases
Monatomic Gases
• In a constant-pressure process, ΔEint = Q + W and
E in t Q W n C P T P V
• Change in internal energy depends only on
temperature for an ideal gas and therefore are the
same for the constant volume process and for
constant pressure process
CP – CV = R
Monatomic Gases
CP – CV = R
• This also applies to any ideal gas
CP = 5/2 R = 20.8 J/mol . K
Ratio of Molar Specific Heats
nR nR 2Q 2Q 2 QV
V T
P P 5nR 5P 5 nRT
2 (4.40 103 J )(5L)
V 3.53L
5 J
(1mol) 8.314 (300 K )
mol K
V f Vi V 5.00L 3.53L 8.53L
Molar Specific Heats of Other Materials
• With complex
molecules, other
contributions to internal
energy must be taken
into account
• One possible way to
energy change is the
translational motion of
the center of mass
Equipartition of Energy
• Rotational motion
about the various axes
also contributes
We can neglect the
rotation around the y
axis since it is negligible
compared to the x and z
axes
Equipartition of Energy
• As T approaches 0,
the molar specific heat
approaches 0
• At high temperatures,
CV becomes a
constant at ~3R
Specific Heat and Molar Specific Heat of Some Solids and Liquids
Substance c, kJ/kg·K c*, J/mol·K
Aluminum 0.900 24.3
Bismuth 0.123 25.7
Copper 0.386 24.5
Gold 0.126 25.6
Ice (-100C) 2.05 36.9
Lead 0.128 26.4
Silver 0.233 24.9
Tungsten 0.134 24.8
Zink 0.387 25.2
Mercury 0.140 28.3
Water 4.18 75.2
The molar mass of copper is 63.5 g/mol. Use the
Dulong-Petit law to calculate the specific heat of
copper.
The molar mass of copper is 63.5 g/mol. Use the Dulong-
Petit law to calculate the specific heat of copper.
The molar specific heat is the heat capacity per mole:
C mc
c
*
Mc
n n
The Dulong-Petit law gives c* in terms of R:
c*= 3R
c *
3(8 .314 J / m ol K )
c 0 .392 J / g K 0 .392 k J / k g K
M 63 .5 g / m ol
v t 1
d v t nV d nV
2 2
Collision Frequency
ƒ d vn V
2