Must-Known in CH.

8
 What is ideal gas? In what physical conditions?

 What is non-ideal gas? Can you explain its behaviors from the
opposite logic of the above physical conditions for the ideal
one?

 How can we analyze and describe the non-ideal behaviors?

→ van der Waals equation (A VERY Good try though partly fails)
→ polynomial approximation

 Idea gas: dG = RTd(lnP) →Non-ideal gas: dG = RTd(lnf)

 Lecturing will follow the sequence of the figures in the slices

 Superfluid
T>Tcr and P>Pcr

What’s the difference in

Pcr
the phase diagram above
and below Pcr?
vapor
 2 a 1
Pcr
D
C B

Tcr

See
Figure 8.1 for A →B →C →D
Figure 8.2 for 1→a→2
(1) (2) Critical point
Supercritical
fluid regime

4 d c b 3
 Increasing T

(PR=P/Pcr)

(TR=T/Tcr)
van der Waals model: Fix the problem in the ideal gas equation

1. Fix volume problem

2. Fix interaction n particles in volume V

n n
problem The interactions∝ V ∙ V
~ the probability they meet
 The inflection behavior can be observed!
i.e. the vdW equation successfully predicts REAL gas behavior at ≥Tcr
 a 12 ∙ cm3 ∙ energy 12 ∙ cm6 ∙ atm
2
= pressure！ a= or
V mole2 mole2
 Figure 8.9 Schematic representation of the variation, with pressure, of
liquid the molar Gibbs free energy of a van der Waals fluid at a constant
temperature lower than the critical temperature. Region FGHIJ is an
instability region. F and J demark the limits of phase stability, sometimes
called the spinodals.
vapor

liquid

Figure 8.8 The isothermal variation, with pressure, of the volume of a van
der Waals fluid at a temperature below the critical temperature. vapor

1 P has 3 states → Not reasonable！

 C I
The minimum Ｇ！

K
 E G

M
The minimum Ｇ！
 metastable metastable
Figure 8.9 Schematic representation of the variation, with pressure, of
the molar Gibbs free energy of a van der Waals fluid at a constant
temperature lower than the critical temperature. Region FGHIJ is an
instability region. F and J demark the limits of phase stability, sometimes
stable stable called the spinodals.

instable instable

Figure 8.8 The isothermal variation, with pressure, of the volume of a van
der Waals fluid at a temperature below the critical temperature.
Look at the lines (the stable states) and the dashed lines
(the metastable states) in the figures on the previous page
Ex 1. and Ex 2.

Remember Figure 8.4 the compressibility of real gases?

 δW = PdV for two isothermal expansions:
1. P1→P2
2. V1→V2

A constant displacement

Larger Vnon-id can get the same P that

the ideal gas shows at smaller V

Thinking what P means in an energy aspect. Then thinking “Shall ideal or non-ideal gases have higher energy?”