Sample

p problem
p
A (non-rigid) diving bell has an air space of 3.0 m3 when on the deck of
a small boat. What is the volume of the air space when the bell has been
l
lowered
d to
t a depth
d th of f 50 m?? The
Th density
d it off sea water
t isi 1.025
1 025 g cm-33.

What do we need to assume? Ideal gas behavior for air

Water temperature is unchanged at 50 m
Constant T,
T so use Boyle: PV=cons’t
PV=cons t Wh is
Why i “rigid”
“ i id” important
i iinformation?
f i ?

 p  p   gh  1.0 atm   gh
f i
 Real Gases

 Compressibility, PV PV
Compressibility Z 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 Ar
1 Ideal Gas

P
 Real Gases – data!
PV PVm
Compressibility Z 
nRT RT
Z = 1 at all P, T  Ideal Gas Behavior

Ideal gas

Now look at real g

gases
at some temperature T

We need new eq of state for each gas

These data are many gases at one T.
Look at a broader 0 – 800 atm region So next look at one gas at many T
 Boyle
y Temperature,
p , TB

Z  Z  P ,T  TB is the temperature corresponding

to the greatest extent
of near-ideal behavior.
We can determine TB analytically.

Z T , P 
 f T 
P lim p 0

dff
 0 att T  TB , the
th Boyle
B l temperature
t t
dT
 van der Waals equation of state
y y
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
for both.
1. Repulsive forces: make pressure higher than ideal gas
nRT
Excluded volume concept (nb) P
V  nbb

Volume of one molecule of radius r is Vmol = (4/3) r3

Closest approach of two molecules with radius r is 2r.
2r
 ConcepTest #5
nRT
Excluded volume P
V  nb
The volume of one molecule of radius r is Vmol = 4/3 r3
Th closest
The l approachh of
f two molecules
l l withi h radius
di r iis 2
2r.
What is the excluded volume for the two molecules?

A. 2Vmol
B 4Vmol
B.
C. 8Vmol
D 16 Vmol
D.
 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.
present Empirical terms were developed to help account
for both.
1. Repulsive forces: make pressure higher than ideal gas
(or equivalently,
(or, equivalently make the volume smaller)

nRT
Do the latter:
latter Excluded volume P
V  nb
Volume of one molecule of radius r is Vmol = 4/3 r3
Closest approach of two molecules with radius r is 2r.
2r
The excluded volume Vexc is 23 Vmol = 8Vmol for two molecules.

So we might estimate that b  4VmolNA

This assumes binary collisions only. Always true? NO!

 van der Waals equation of state
y y
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
for both.
2. Attractive forces: make pressure lower than ideal gas
Pressure depends wall collisions, both on frequency
and their force.
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
nRT an RT a
P  2   2
V  nb
b V Vb V
3D van der Waals eqn of state

T= T/Tc
Real Gases – CO2
Look at 50 C isotherm.
Behavior is near ideal gas
CO2 Look at 20 C isotherm
isotherm.
ABC Compression
At C, liquid condensation begins
D – liquid- vapor mixture at
Pvap(20 C)
E – last
l vapor condenses
d
F – Steep rise in pressure
A liquid or solid is much less
compressible than a gas

For T >Tc, there is a single phase,

phase
with no liquid formed.
van der Waals Isotherms near Tc

v d W “loops”
loops are
not physical. Why?

Patch up with Maxwell

construction

van der Waals Isotherms, T/Tc

 van der Waals Isotherms near Tc
1.5
Look at one of the van der Waals G
isotherms at a temperature
temperat re of 0.9
0 9 Tc

essure, Pr
•A → D compress the gas at constant T, 1.0
•F → G compress the liquid phase Tr = 0.9
B

Reduced Pre
(steep and not very compressible)
•D → F vapor condensing (gas and F D
liquid coexist) 0.5 g, l
These are stable states C
A

F → C supercooled liquid 0.0

D → B superheated gas 0.3 0.5 0.7 1 2 3 5 7 10

Th
These are metastable
t t bl states
t t R d
Reduced
d Volume,
V l Vr

Metastable example:
C → B a non-physical artifact of vdW Use a very clean glass. Add water and heat
(patched up
(p p with Maxwell construction)) for
o a while
w e with
w t a microwave
c owave ove
oven (supe
(superheat)
eat)
Add a drop of sand or perhaps touch with a spoon.