Chapter 18: Thermal Properties of

Matter
Equations of State
Ideal Gas Equation
PV Diagrams
Kinetic-Molecular Model of
an Ideal Gas
Heat Capacities
Distribution of Molecular
Speeds
Phases of Matter
Topics for Discussion
Equations of State
State Variables
physical variables describing the
macroscopic state of the system:
P, V, T, n (or m)
Equation of State
a mathematical relationship linking these
variables
The Ideal Gas Equation
Properties of a gas is studied by
varying the macroscopic variables:
P, V, T, n and observing the result.
Observations:
1. e.g. an air pump
2. e.g. hot air balloon
3. e.g. hot closed spray can
4. e.g. birthday ballon
1 P V
V T
P T
V n
Ideal Gas Law (summary)
By putting all these observations together, we have
R Universal Gas Constant (R = 8.314 J /mol K)
(This is an important example of an Equation of State for a
gas at thermal equilibrium.)
(T has to be in Kelvin)
An Ideal Gas (diluted):
No molecular interactions besides elastic collisions
Molecular volume <<< volume of container
Most everyday gases ~Ideal!
PV nRT =
The Ideal Gas Law
Important Notes:
The relationship V vs. T (at
cont P) & P vs. T (at cont
V) are linear for all diluted
gases.
diluted gas ~Ideal
They both extrapolate to a
single zero point (absolute
zero).
T has to be in K!
-300 -200 -100 0 100 200
-300 -200 -100 0 100 200
T =-273.15
o
C
P
r
e
s
s
u
r
e
V
o
l
u
m
e
Temperature (
o
C)
P T
nR
V
=
V T
nR
P
=
The Ideal Gas Law (alternative form)
Instead of the number of moles (n), one can specify the
amount of gas by the actual number of molecules (N).
N = n N
A
where N
A
is the #of molecules in a mole of materials
(Avogadros number).
where k is the Boltzmann constant,
23
( 6.02214 10 / )
A
N molecules mole =
23
1.381 10 /
A
R
k J molecule K
N

= =
A
N
PV nRT PV RT NkT
N
= = =
Example 18.1 (V at STP)
What is the volume of a gas (one mole) at Standard
Temperature and Pressure (STP)?
STP: T = 0
o
C = 273.15K
P = 1 atm =
3
(1 )(8.314 / )(273.15 )
0.0224 22.4
5
1.013 10
nRT mole J mol K K
V m L
P
Pa

= = = =

5
1.013 10 Pa
Typical Usage for the Ideal Gas Law
For a fixed amount of gas (nR=const)
So, if we have a gas at two different states 1(before) and 2
(after), their state variables are related simply by:
We can use this relation to solve for any unknown variables
with the others being given.
PV
nR const
T
= =
1 1 2 2
1 2
PV PV
T T
=
(side note: absolute pressure =gauge +atmospheric)
Example 18.2
In an automobile engine, a mixture of air/gasoline is
being compressed before ignition.
Typical compression ration 1 to 9
Initial P = 1 atm and T = 27
o
C
Find the temperature of the compressed gas if we are
given the pressure after compression to be 21.7atm.
note
http://complex.gmu.edu/www-phys/phys262/soln/ex18.2.pdf
The van der Waals Equation
A more realistic Equation of States for gases which includes
corrections for the facts that molecules are not point particles,
that they have volume, and for the attraction/repulsion that
naturally exists between the adjacent atoms/molecules.
( )
2
2
an
P V n nRT
V
b
| |
+ =
|
\ .
Notes on Van Der Waals
The volume parameter b:
It makes sense that real gas as finite size hard spheres will reduce the
total volume of the gas by a term which is proportional to the number
of mole n.
The intra-molecular force parameter a:
Intra-molecular force tends to reduce the pressure of the gas onto the
wall by pulling the molecules toward the interior of the container
This intra-molecular force acts in pairs (to the lowest order of
approximation)
For a unit volume in front of the wall, this intra-molecular force will
depends on the number of pairs of molecules within this unit volume
The count of molecular pairs within this unit volume ~(n/V)
2
(Note: for N molecules, #pairs =N(N-1)/2; for N large, ~N
2
.)
( )
eff
nRT nRT
P
V V nb
= =

2 2
( )
( )
nRT n
P P a V nb nRT
V n V V
n
b
a
| |
| |
= + =
|
|
| |

\ .
|
\
\
.
.
The Ideal Gas Law (graphical view)
P,V,T relationship in the Ideal Gas Law can be visualize
graphically as a surface in 3D.
nRT
P
V
=
PV Diagrams
2D projections of the
previous 3D surface.
Evolution of a gas at
constant T will move
along these curves
called isotherms.
Gives P vs. V at a various T:
1
( ) P nRT
V
=
Phases of Matter (reading phase diagrams)
Kinetic-Molecular Model of an Ideal Gas
An example of a successful theoretical linkage between the
micro and macro descriptions for an ideal gas.
Explicit expressions of P & T in terms of microscopic
quantities!
Macroscopic description
of gases
P, V, T
Ideal Gas Law
Microscopic description
of gas molecules
v, p, F, KE
Newtons Eqs
Kinetic Theory
Kinetic Theory (assumptions)
A very large #N of identical molecules each with mass m in a container
with volume V
Molecules behaves as point particles:
Molecule sizes <<avg separate bet particles & dim of container
Molecules moves according to Newtons laws and they move randomly
with equal probability in all directions and with a fixed distribution f(v)
(histogram) of speed v
Molecules interact only with the walls and each others thru elastic
collisions and the container walls are perfectly rigid and infinitely massive
both KE and momentum are conserved
Fraction of molecules
moving in a given range of
speeds stays the same
f(v)
speed (v)
applet
Kinetic Theory (model)
L
A
Idea Gas in a box with V=AL
v
i
-v
x
-v
y
v
f
+v
x
-v
y
Left Wall
before collision
after collision
Pressure Exerted by an Ideal Gas
Pressure on left wall due to molecular
collisions
1. Momentum change in x-dir by a
molecule moving to the left at v
i
:
2. Duration, At, that this molecule
takes (on average) to collide with
the left wall again (diluted gas),
( ) ( ) 2
f i x x x
m P P mv mv mv A = = = v
2
x
L
t
v
A =
L
v
i
-v
x
-v
y
v
f
+v
x
-v
y
Left Wall
m
m
Pressure Exerted by an Ideal Gas
3. Force exerted by this molecule on the left wall:
4. With N molecules, total force on wall in At:
2
2 ( )
2
x x
x
mv mv m
F
t L v L
A
= = =
A
v
( )
( )
2 2 2
1 2
1
2
1
2
1
N
tot i x x Nx
i
N
ix x
a
i
v
m
F F v v v
L
m mN
v
L
N v
L N
=
=
= = + + +
| |
= =
|
\ .

( )
( )
2
2
:
x x
av
av
Note v v =
Invariant distribution implies will be the same when
experiment is repeated.
( )
av

Pressure of an Ideal Gas

5. Random direction (isotropic) assumption:
(v
x
2
)
av
= (v
y
2
)
av
= (v
z
2
)
av
(x,y,z are the same)
Since v
2
= v
x
2
+ v
y
2
+ v
z
2
, we have (v
2
)
av
= 3(v
x
2
)
av
This gives,
6. Finally, the pressure on the wall is:
2
( )
3
av
tot
v mN
F
L
=
2 2
( ) ( ) 1
3 3
tot av av
F v Nm v mN
P
A AL V
= = =
Pressure of an Ideal Gas
Rewriting, we have
This tells us that P inside a container with
fixed V:
is proportional to the #of molecules N
is proportional to the avg. KE of molecules
(These are microscopic properties of the gas.)
( )
( )
2
2 1 2
3 2 3
av
av
PV N m v N KE
| |
= =
|
\ .
(avg KE per molecule)