Académique Documents
Professionnel Documents
Culture Documents
Compiled by:
Gan Chin Heng / Shermon Ong
07S06G / 07S06H
Solid
Liquid
Critical point
Triple point
Gas
Temp
Mathematically
Using
equations of state
Relate state variables to describe property of
matter
Examples of state variables
Pressure
Volume
Temperature
Equations of state
Law
B
Boyles Law
C
Charles Law
Avogadros Law
24.0
dm3 at 298K
22.4 dm3 at 273K
Boyles Law
At constant temperature
and amounts
Gas volume
inversely
proportionate to pressure,
i.e. V 1/p
The product of V & p, which
is constant, increases with
temperature
Charles Law
At constant pressure
and amounts
Volume
proportionate to
temperature, i.e. V T
is in Kelvins
Note the extrapolated
lines (to be explained
later)
pV = nRT
Assumptions
very low
temperatures
Volume do not
decrease to zero
Gas liquefies instead
Remember the
extrapolated lines?
= RT
pVm
/ RT = 1
So how?
So in 1873
I can approximate
the behaviour of
fluids with an
equation
Scientific
community
ORLY?
YARLY!
Non-zero
effect)
Attractive forces between gas particles
(attractive effect)
Attractive effect
Pressure
Both
(n/V)2
Letting a be the constant relating p and
(n/V)2
Pressure term, p, in ideal gas equation
becomes [p+a(n/V)2]
Repulsive effect
Gas
n
p + a
V
[V-nb] = nRT
OR
a
p + 2
Vm
[Vm -b] = RT
Value of constant a
Gives
Water: 5.536
HCl: 3.716
Neon: 0.2135
Value of constant b
Gives
Benzene: 0.1154
Ethane: 0.0638
Helium: 0.0237
Critical temperature?
Given a p-V plot of a
real gas
At higher temperatures
T3 and T4, isotherm
resembles that of an
ideal gas
Critical temperature?
Critical temperature?
Critical temperature
At T > Tc, gas cant be compressed into
liquid
At Tc, isotherm in a p-V graph will have a
point of inflection
1st
a
p + 2 [Vm -b] = RT
Vm
RT
a
p=
- 2
Vm -b Vm
dp
0
dVm T
d p
0
2
dVm T
2
2
(Vm b) Vm
dVm T
d 2 p
2 RT
6a
2
3
dVm T (Vm b) Vm
Rearranging...
a
8a
Vm,c = 3b; p c =
; Tc =
2
27b
27Rb
pc Vm,c
3
Zc =
=
RTc
8
Qualitative trends
As
Real
values:
Water: 647K
Oxygen: 154.6K
Neon: 44.4K
Helium: 5.19K
Compressibility Factor
Compressibility Factor
Recall Z plot?
Z = pVm / RT; also called
the compressibility
factor
Z should be 1 at all
conditions for an ideal
gas
Compressibility Factor
For real gases, Z not
equals to 1
Z = Vm / Vm,id
Implications:
At
Compressibility Factor
At
intermediate p, Z <
1
Attractive forces
dominant
More significant for
gases with significant
IMF
Boyle Temperature
Z also varies with temperature
At a particular temperature
Boyle Temperature
Mathematical
implication
For
TB = a / Rb
Virial Equations
Virial Equations
= pVm/RT
Z1
Virial Equations
Form
pVm/RT
pVm/RT
= 1 + Bp + Cp2 + Dp3 +
dependent
Can be derived theoretically or experimentally
Virial Equations
Summary
Summary
Summary
Summary
Summary