Sample problem p p

A (non-rigid) diving bell has an air space of 3.0 m

3
when on the deck of
a small boat. What is the volume of the air space when the bell has been
l d t d th f 50 ? Th d it f t i 1 025
3
lowered to a depth of 50 m? The density of sea water is 1.025 g cm
-3
.
What do we need to assume?
Ideal gas behavior for air
Water temperature is unchanged at 50 m
Constant T so use Boyle: PV=const
Wh i i id i i f i ?
Constant T, so use Boyle: PV=cons t
Why is rigid important information?

1.0 atm
f i
p p gh gh = + = +
Real Gases
- Compressibility Z
PV PV
Z
- Compressibility, Z
PV PV
Z
nRT RT
= =
Z = 1 Ideal Gas behavior
Z < 1 PV less than expected Attractive forces
Z > 1 PV greater than expected Repulsive forces
Z

1
Ar
Ideal Gas Ideal Gas
P

Real Gases data!
Compressibility
PV
PV
Z
nRT RT
m
= =
Z = 1 at all P, T Ideal Gas Behavior
Now look at real gases
Ideal gas
g
at some temperature T
Look at a broader 0 800 atm region
We need new eq of state for each gas
These data are many gases at one T.
So next look at one gas at many T
Boyle Temperature, T
B
y p ,
B
T
B
is the temperature corresponding
( )
Z Z P T =
T
B
is the temperature corresponding
to the greatest extent
of near-ideal behavior.
( )
, Z Z P T
( )
( )
, cZ T P
f
We can determine T
B
analytically.
( )
( )
lim 0
,
0 t th B l t t
+

=
c
p
f T
P
df
T T 0 at , the Boyle temperature = =
B
f
T T
dT
van der Waals equation of state van der Waals equation of state
Physically-motivated corrections to Ideal Gas EoS. y y
For a real gas, both attractive and repulsive intermolecular
forces are present. Empirical terms were developed to help account
for both.
Excluded volume concept (nb)
nRT
P
V b
=
1. Repulsive forces: make pressure higher than ideal gas
Excluded volume concept (nb)
V nb
Volume of one molecule of radius r is V
mol
= (4/3) tr
3
Closest approach of two molecules with radius r is 2r Closest approach of two molecules with radius r is 2r.
ConcepTest #5 ConcepTest #5
Excluded volume
nRT
P =
Excluded volume
P
V nb
=

The volume of one molecule of radius r is V

mol
= 4/3 tr
3
Th l h f l l i h di i 2 The closest approach of two molecules with radius r is 2r.
What is the excluded volume for the two molecules?
A. 2V
mol
B 4V B. 4V
mol
C. 8V
mol
D 16 V D. 16 V
mol
van der Waals equation of state
Physically-motivated corrections to Ideal Gas EoS.
For a real gas, both attractive and repulsive intermolecular
forces are present Empirical terms were developed to help account forces are present. Empirical terms were developed to help account
for both.
1. Repulsive forces: make pressure higher than ideal gas
(or equivalently make the volume smaller)
Do the latter: Excluded volume
nRT
P =
(or, equivalently, make the volume smaller)
Do the latter Excluded volume
V nb
Volume of one molecule of radius r is V
mol
= 4/3 tr
3
Closest approach of two molecules with radius r is 2r Closest approach of two molecules with radius r is 2r.
The excluded volume V
exc
is 2
3
V
mol
= 8V
mol
for two molecules.
So we might estimate that
b 4V N ~
So we might estimate that
A mol
b 4V N ~
This assumes binary collisions only. Always true? NO!
van der Waals equation of state van der Waals equation of state
Physically-motivated corrections to Ideal Gas EoS. y y
For a real gas, both attractive and repulsive intermolecular
forces are present. Empirical terms were developed to help account
for both.
Pressure depends wall collisions, both on frequency
and their force
2. Attractive forces: make pressure lower than ideal gas
and their force.
Not easy to show, but we expect a pressure correction of the
form a(n/V)
2
, giving the van der Waals Equation of State
2
2 2
nRT an RT a
P
V b V V b V
= =
2 2
V nb V V b V
3D van der Waals eqn of state 3D van der Waals eqn of state
T= T/T
c
Real Gases CO
2
CO
2
Look at 20 C isotherm
Look at 50 C isotherm.
Behavior is near ideal gas
2
ABC Compression
At C, liquid condensation begins
Look at 20 C isotherm.
D liquid- vapor mixture at
P
vap
(20 C)
E l d E last vapor condenses
F Steep rise in pressure
A liquid or solid is much less A liquid or solid is much less
compressible than a gas
For T >T there is a single phase For T >T
c
, there is a single phase,
with no liquid formed.
van der Waals Isotherms near T
c
van der Waals Isotherms near T
c
v d W loops are v d W loops are
not physical. Why?
Patch up with Maxwell
construction
van der Waals Isotherms, T/T
c
van der Waals Isotherms near T
cc
Look at one of the van der Waals
isotherms at a temperat re of 0 9 T
1.5
G
isotherms at a temperature of 0.9 T
c
e
s
s
u
r
e
,

P
r
1.0
T
r
=0.9
B
A D compress the gas at constant T,
F G compress the liquid phase
R
e
d
u
c
e
d

P
r
e
0.5
D
B
F
C
A
g, l
(steep and not very compressible)
D F vapor condensing (gas and
liquid coexist)
Thesearestable states
R d d V l V
0.3 0.5 0.7 1 2 3 5 7 10
0.0
A
These are stable states
F C supercooled liquid
D B superheated gas
Th t t bl t t
Reduced Volume, V
r These are metastable states
C B a non-physical artifact of vdW
(patched up with Maxwell construction)
Metastable example:
Use a very clean glass. Add water and heat
for a while with a microwave oven (superheat)
(p p )
o aw ewt a c owaveove (supe eat)
Add a drop of sand or perhaps touch with a spoon.