AE/ME5102 Advanced Gas Dynamics: Notes1 Set 5

Instructor: J. Blandino
Worcester Polytechnic Institute, Fall 2015

Collision Frequency and Mean Free Path Revisited

We now want to revisit our previous evaluation of the collision frequency and mean
free path. Recall our earlier, simple analysis (molecules in a box) assumed a constant
speed for the molecules. Now we can use our results for the collision rate, which was
based on the molecules having a Maxwellian distribution, to obtain more accurate
results. Recall our previous results for the rates:
Bimolecular Collision Rate: Zab (with units of coll/unit time/unit volume)

Zab =

na nb d2ab

8kT
mab

1/2

Mutual Collision Rate: Zbb

n2
Zbb = b d2b
2

8kT
mbb

1/2

Collision Frequency:
Collision frequency of one molecule of type a per unit time with type b

Zab
ab =
= nb d2ab
na
1

8kT
mab

1/2

Notes are based on material from the course text, Ref. 1: Introduction to Physical Gas
Dynamics, Vincenti, W. and Kruger, C., Krieger Pub., Copyright 1965. Any figures used from
Ref.1 are so noted and copyrighted by Krieger Publishing Co.

We can also express the collision frequency of one molecule of type b with another
molecule of type b using the mutual collision rate.

Zbb
nb
bb =
= d2b
nb
2

8kT
mbb

1/2

2

|{z}

because each
collision is two
collisions of type
b molecules

So in general, we can write for mixture of species

ay =

ny d2ay

8kT
may

1/2
where y can represent any species.

In a mixture, total number of collisions/sec of type a with all other species present
will then be given by a summation:

a =

ay

= 8kT

s
!
X

ny d2ay
1
1
2
p
ny day
= 8kT
+
ma my
may
y
{z
}

all the terms

that depend ony
are here

Mean Free Path

For a Maxwellian distribution, the mean thermal speed is Ca =

8kT
ma

The mean distance travelled between collisions at this speed a will be


a = Ca

1
a

r 


8kT
1

q
=

P
1

ma 

2
+
n
d
8kT
y
ay
y
ma

a =

1
my

2
y ny day

q
1+

ma
my

If there is only one species present, then my = ma and ny = na

where the factor of

into account.

1
2d2 n

2 comes from our now having taken the velocity distribution

Compare this with our previous result of =

1
d2 n

Thermodynamics Review
Generally, thermodynamics is important to the understanding of chemically reacting
flow, regardless of the flow speed. From a gas dynamics standpoint, thermodynamics
is essential to understanding and characterizing high speed flows.
Low speed flows thermodynamics not needed
flow heat content  flow kinetic energy
T remains constant even if all kinetic energy is converted to thermal

High speed flows thermodynamics needed

Kinetic energy is greater or comparable to thermal energy
Variations in temperature can be large
So thermodynamics is essential for the study of high
speed gas flows

Review of Some Important Terms and Concepts

System
- quantity of matter separated from surroundings or environment

- Properties of system can be defined by state variables,

i.e. variables which depend on (thermodynamic) state
of system
- If system is left alone for sufficiently long time, it approaches equilibrium
- In equilibrium, macroscopically measurable quantities
become independent of time:
T (temperature) p (pressure) V (volume)
E (energy) H (enthalpy) S (entropy)

Intensive properties
- do not depend on total quantity of matter in system,
e.g. T , p

Extensive properties
- do depend on quantity of material
V = |{z}
v M

E = eM

S = sM

specific
values

where M is the total mass in the system of interest.

Thermodynamics
- establishes the relevant state variables
- establishes relations they must satisfy
- describes how changes of state occur by interactions
with the environment (heat flow and work)

Zeroth law
- introduces temperature as a variable of state
- two systems in thermal contact are in equilibrium only
if temperature is the same in both

First law
- introduces internal energy as a state variable
heat flow

E = E2 E1 =

W
|{z}

z}|{
Q

work (form
depends on
material

For infinitesimal process: dE = Q + W

d() denotes change in a state variable
() denotes change in a path-dependent, non-state variables

Second law
- introduces entropy as a state variable
S

R
1

Q
T

dS

Q
T

in general

dS =

Q
T

in a reversible process
|
{z
}
approached by a slow,
quasi-static process
to minimize dissipative
effects (thermal diffusion,
momentum diffusion)

dS 0 in an adiabatic process (Q = 0)
dS = 0 in adiabatic and reversible process. This is an
isentropic process.

We will limit discussion to simple systems (i.e. one work mode) neglect electric,
magnetic effects, also assumed to be isotropic, homogeneous in composition (multiple
phases can be present).
From the Gibbs Phase Rule, a simple system of r components (species) with a
single phase present, has r + 1 thermodynamic degrees of freedom only r + 1
independent, intensive parameters.

Review of Gibbs Phase Rule2

For a simple system with no chemical reactions:

variance (Number of
intensive properties
wich must be
specified to
completely fix
the state of system

P
|{z}

z}|{
V

r
|{z}

+2

# of components
present

# of phases
present

Few examples:
- pure substance, single phase (e.g. water vapor, gas
etc.), r = 1, P = 1 so V = 1 1 + 2 = 2
So one needs two intensive variables (e.g. p, T ) to specify
state.
- pure substance, two phases: (saturated liquid and saturated vapor)
r = 1, P = 2 V = 1 (T or p)
- at triple point:
r = 1, P = 3 V = 0
As long as their are no chemical reactions to change the
composition, air can be treated as a mixture of fixed
composition
r = 1, P = 1 and V = 2

See for example p. 879 of Fundamentals of Engineering Thermodynamics, 7th ed., Moran, M.
and Shapiro, H., Wiley Pub., Copyright 2011.

Work for a Compressible Substance

To proceed further with thermodynamic analysis, we need to describe the mode of
work for our particular system.
For gases:

Z
W =

F~ d~r =

pA( |{z}
~n

d~r) =

pdV

outward
unit normal

W > 0 if dV < 0 (work done on system)

W < 0 if dV > 0 (work done by system)

First law can be written in terms of state variables ( for reversible process)

dE = Q + |{z}
W
|{z}
T dS

pdV

[dE = T dS pdV ] E (S, V )

Note: when we talk about multicomponent systems (chemical reactions) then we
will have a chemical work term

Wch =

r
X
j=1

j dNj

where
Nj = number of moles of species j
j chemical potential
Equations of State
Thermal equation of state relates p to T and V
f (p, V, T ) = 0

Caloric equation of state relates E to T and V

f (E, V, T ) = 0

Thermal equation of state

It is found empirically that as p 0

pv
RT

When we study statistical mechanics, we will find that the ideal gas law is recovered
from a microscopic model.
In general,

pv
RT

= Z (p, T ), where Z is the compressibility factor

- at low pressure and moderate temperature, Z = 1 =
constant, and we have pv = RT which is often called
the perfect (or ideal) gas equation of state
- A gas that satisfies pv = RT (or p = RT ) is called
a perfect or ideal gas. As discussed earlier, R is gas
specific.

10

Deviations from Z = 1 result from actual behaviour of real gases.

For example,
At low temperature, and/or high pressure, intermolecular forces become important.
Van der Waals Equation of State:
a
RT
2
vb v
b corrects for volume occupied by molecules
p=

a
v2

corrects for intermolecular forces

Beattie-Bridgeman Equation of State:

p=


A = A0 1 av

B = B0 1 vb
 = vTc 3

RT (1 )
A
(v + B) 2
2
v
v

Virial Equation of State:

From statistical mechanics, with corrections based on
Virial Coefficients

Z=

pv
=
RT

B(T )
C(T )
1+
+ 2 + ...
v
| {z v }

first order
corrections to
non-ideality of gas

At low pressure and high temperature, dissociation (and ionization) become important:
11

Z = 1 + d (T )
where d = degree of dissociation

Some Additional Thermodynamic Functions

Enthalpy

H = E + pV

dH = dE + pdV + V dp = (T dS pdV ) +pdV + V dp

|
{z
}
1st law

[dH = T dS + V dp] H (S, p)

F = E TS

Helmholtz Function

dF = |{z}
dE T dS SdT
1st law

[dF = pdV SdT ] F (V, T )

12

G = H TS

Gibbs Function

dG = dH T dS SdT

[dG = V dp SdT ] G (p, T )

Note: i =

G
Ni

. This is the chemical potential

T,p

which we will use later in our discussion of chemically

reacting systems.
Specific Heat
Heat needed to raise the temperature of unit mass of
system by 1 degree. Has units of energy/unit mass/unit
temp change.
C=

q
dT

where q is the energy per unit mass transferred.

Usually defined with respect to thermodynamic process
(or path):

Cv =

Cp =

q
dT

q
dT


=T

13


=T
p

s
T

s
T