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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.
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
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
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.
T= T/Tc
Real Gases – CO2
Look at 50 C isotherm.
Behavior is near ideal gas
CO2 Look at 20 C isotherm
isotherm.
ABC 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
v d W “loops”
loops are
not physical. Why?
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
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.