MTX 311 Thermodynamics

Real Gases

Dr Axel Lexmond
2013

MTX 311 Thermodynamics

Dr Axel Lexmond

Lecture 3

Lecture 4

MTX 311 Thermodynamics

Dr Axel Lexmond

ideal gas

Molecules have finite mass but NO finite volume

No intermolecular forces
P~n/V mv
T~mv

P~nT/V

(P=nRT/V)
(PV=mRT)

Lecture 3

MTX 311 Thermodynamics

Dr Axel Lexmond

ideal gas

Molecules have finite mass but NO finite volume

No intermolecular forces
P~n/V mv
T~mv

P~nT/V

(P=nRT/V)
(PV=mRT)

Constant temperature =
Compression:
Intermolecular forces are 0: internal energy is not a function of pressure or volume
Compression:

= ( + )= + = 0

Lecture 3

MTX 311 Thermodynamics

Dr Axel Lexmond

ideal gas

Molecules have finite mass but NO finite volume

No intermolecular forces
Constant temperature S~n lnV
Compression:
s~ lnV ~ ln P
PV=RT

Lecture 3

MTX 311 Thermodynamics

Dr Axel Lexmond

ideal liquid

Molecules have finite mass and finite volume

Packing density depends on temperature but independent from external forces
Incompressible fluid: V= V(T) V(P)

Compression:

= 0 = 0

= + = =

Lecture 3

MTX 311 Thermodynamics

Dr Axel Lexmond

Lecture 3

What happens in a real gas?

Molecules have finite volume (results in larger specific volume than predicted by ideal gas)
Molecules attract each other (results in smaller specific volume than predicted by ideal gas

Small molecules at ambient conditions (air, water)

Average distance is about 10x diameter of the molecules

MTX 311 Thermodynamics

Dr Axel Lexmond

Lecture 3

What happens in a real gas?

P(V-V0)=RT

Finite volume of molecule

s~ ln(V V0 )

Higher pressures (at given T,V)

Lower entropy (at given T,V)

h and u are not affected

Molecule decelerates when getting out of the gas (to

the wall)smaller force on the wall lower pressure
Molecular attraction

Entropy is not affected

=

< 0

h and u will be smaller than h and u at 0 pressure

At very high pressure, molecules will start touching (repelling) each other
h and u will increase

MTX 311 Thermodynamics

Dr Axel Lexmond

real gases

Which relationships do NOT work any more:

PV=RT
Polytropic relationships
u=u(T), h=h(T)

V=V(P,T)
h=h(P,T)

u=h-PV=u(P,T)

Real gas
V=RT/p
h=h(T)=h0+Cp(T-T0)

Lecture 3

MTX 311 Thermodynamics

Dr Axel Lexmond

Lecture 3

How to describe a non-deal gas?

Experimental data
Tables
graphs
Substance specific correlations
Computer programs (e.g. Aspen)

Generic equations
F=Fig+ Fcf (Pr , Tr) (enthalpy, entropy)
F=F(Fig, Pr , Tr) (sp volume)

ig = ideal gas
cf correction factor
Pr= reduced pressure (Pr=P/ Pc)
Tr=reduced temperature (Tr=T/ Tc)

Limited accuracy

MTX 311 Thermodynamics

Dr Axel Lexmond

Lecture 3

Typical errors
Many ways to describe a real gas

Tables of measured data

digital databases
Substance-specific correlations:
virial equations

<1%

5%

Build your own general equations based on

reduced data from comparable substances

Might be difficult to
distinguish!

interpolation between substances by

digital databases
General equations that use only critical temperature and pressure
Redlich and Kwong
Up to 25%
compressibility factors (reduced coordinates)
van der Waals

Z=

Do you need correction?

MTX 311 Thermodynamics

Dr Axel Lexmond

You need correction when H, S and PVT-correlations deviate significantly for m ideal
gas correlations
IF one of these quantities deviates, usually all three do.
Method: check PVT (because that is simple)
If PVT data follows ideal gas, you can assume that enthaly and entropy also will
follow ideal gas correlations

Lecture 3

Do you need correction?

Method 1
use the reduced temperature and the reduced pressure

When Tr>2 OR Pr<0.2, you can assume ideal gas

MTX 311 Thermodynamics

Dr Axel Lexmond

Lecture 3

Do you need correction?

MTX 311 Thermodynamics

Dr Axel Lexmond

Lecture 3

Method 2
use the density / specific volume
Look up the density of the liquid
Divide this by the actual density of the fluid.

> 25

< 8

When T2Tc, positive deviation (from the size of the molecules) and negative deviations
(resulting from attractive forces) are equally large. This means that there is no net deviation
This temperature is called the Boyle temperature of the gas.
At higher temperatures, deviations from molecular volume dominate (Z>1, at lower
temperatures, attractive forces dominate (Z<1)

Do you need correction?

MTX 311 Thermodynamics

Dr Axel Lexmond

Method 3
use the reduced temperature and the reduced pressure

Look up compressibility factor (Z) in table D1

When Z is between 0.95 and 1.05, you can assume small (no) deviations
from ideal gas
When Z is smaller than 0.9 or larger than 1.1, you can assume large
deviations

Lecture 3

Compressibility factor

Z1 when Pr0
Z1 when Tr Tboyle (~ 2,5 )

MTX 311 Thermodynamics

Dr Axel Lexmond

Lecture 3

Do you need correction?

MTX 311 Thermodynamics

Dr Axel Lexmond

Method 4
use PVT tables
Look up the specific volume in the table
Estimate the specific volume suing ideal gas law:
Vig =

Z=V/Vig
When Z is between 0.95 and 1.05, you can assume small (no) deviations
from ideal gas
When Z is smaller than 0.9 or larger than 1.1, you can assume large
deviations

Lecture 3

Virial equation

MTX 311 Thermodynamics

Dr Axel Lexmond

Z=

Z=1+

()

()
2

()
3

Z = 1 + + 2 + 3 +
Not very good near the critical point
Constants are quite often presented in non-SI units (e.g. notes)

Lecture 3

MTX 311 Thermodynamics

v/d Waals equation

Dr Axel Lexmond

=
Due to molecular volume

Due to intermolecular forces

a and b can be calculated from critical point( = 0; = 0):

8
=
27

Advantages:
Disadvantage:

=
27

intuitive model
limited accuracy

Lecture 3

v/d Waals equation

In reduced form
+
=

8
27

=
27

= 3

Big advantage:
Disadvantage:

only critical constant necessary

not very accurate

MTX 311 Thermodynamics

Dr Axel Lexmond

Lecture 3

MTX 311 Thermodynamics

Tomorrow
Handout, problems 10.6

Dr Axel Lexmond

Lecture 3

We want to calculate the amount of air (nitrogen) which is present in a 50l diving tank
at 250 bar, 30C
Do we need to account for non-ideality?
What will be the specific volume?