1.

4 Molecular basis of Pressure and Viscous stress tensor

Use a simple situation: gas molecules = hard spheres, no
interactions between molecules (Kinetic theory of gas)
Under such conditions, the the molecular velocities u of the gas
molecules is a distribution whose root square mean is dependent on

8kT
m
the temperature and is.
k = 8.314 J/(mol K) is the Boltzmann constant; T is in K; m is molar
mass in kg.
Exercise: Calculate the molecular velocities of the gas molecules in
your room.
u2

Note we use uto refer to the velocity of the molecules whereas v is

the fluid velocity, or the average molecular velocity at point. If you
are sitting in a classroom with no windows and no ducts and not fan
(no wind therefore) the velocity of the air is v 0 where are the
molecular velocity of say the CO2 in the room is u 400m/ sec. Is
there viscous force at any point in the room then? Is there a
pressure at any point in the room?

1.4.1 Molecular basis of Pressure in kinetic theory:

Pressure is momentum transferred to wall due to collisions of
molecule
Molecule moving with velocity vx will transfer 2mvx momentum
when it hits a plane with x normal. m is the mass of the molecule.
The momentum transferred to the wall is obtained by the difference
in the molecules momentum before and after collision (remember
that momentum is conserved within a system)
A molecule with velocity vx travelling in a cube of side L, will collide
with the x plane
vx/2L times.
Net momentum transferred to the x plane from a molecule
ux
2mux
travelling with velocity vx is 2L
.
u
Let N be the number of molecules in cube. If we consider all their x

x.
velocities: x
The net momentum transferred to the plane is the total force on the
plane

u2 Nu2

Pressure is force/area. Therefore Pressure on the plane is

N
mu2x nmu2x
3
L
, where n is the number of molecules per unit volume.
In a general situation only one third of the molecules move in the x
direction. Therefore

nmu2
3

where

u2

is the root mean square velocity and is given by

u2

the Maxwellian distribution. Substitute for

.
What are the parallels between the expression for P derived from
Kinetic theory and the Ideal Gas Law.
Exercise: Using the expression from Kinetic theory, describe how P
will change when you increase T and increase n. Is it in accordance
with the Ideal Gas Law.
Exercise: At a given temperature, the heavier molecule is expected
to move slower (why? See expression for average molecular velocity
from Kinetic Theory). You would therefore expect the pressure in a
cube to decrease if you increased the mass of all the molecules in it.
But the pressure does not decrease. Explain why using your
understanding of the molecular basis of pressure. Does the Ideal
Gas Law give the same dependence between Pressure and
molecular mass.
Exercise: If you hold out your hand in your classroom, what is the
average number of molecules that will collide? What is the pressure
you will feel? Is it close to the atmospheric pressure?
1.4.2 Molecular basis of viscosity, diffusion coefficient, and
thermal conductivity in transport of gas molecules

A gas molecule carries momentum, heat, and mass.

Momentum = mass*velocity of gas molecule = mv
Heat = heat capacity = cv
Mass is of course m.
Mean free path
Let our molecule be a hard sphere with diameter s, and moving at a
velocity v. It will collide with all similar gas molecules within a
distance d away from its path. Therefore its collision diameter is 2d.
Over a time t, our molecule will collide with all co-molecules present
2
2
within a cylinder of volume d vt d vt
If n is the number of molecules per unit volume in the gas, then our
2
guy will make d vtn collisions in time t.

The its mean free path = (distance travelled)/(number of collisions)

1
2
d n
=

If you consider the relative motion between molecules then the

expression for the mean free path becomes:
1

2 d2 n
Momentum flux across a plane

ux

In order to calculate the flux we need to know the number of

molecules that cross the plane from the top minus that which cross
the plane in the opposite direction from the bottom.
Now lets say that all molecules move with the velocity they got from
their last collision (explain this with Newtons law of motion)
Then lets say that on average the molecules crossing our plane y
had their last collision at the planes y+a or y-a depending on
whether they come from above or below our plane y, where a is
given by
y+
a
y
y-a

Now the force acting in the x-direction on a y-normal surface is yx

On the molecular level it is the flux of x-momentum across a ynormal plane.
Remember momentum is mv and there the x component of the
momentum is mvx
So lets derive the expression for the flux x-momentum across a xz
plane and see how the expression compares to the continuum
dv
yx x

dy
expression for yx , which is

vx

dvx
a
dy

vx
vx

dvx
a
dy

Molecules which had their last collision in the plane (y + a) will have
the average velocity of the molecules in that plane which is:

ux

vx

dvx
a
dy

Note that ux and the differential are calculated at plane y. Therefore

the average momentum of the particles having their last collision on
the (y + a) plane is:

m(vx

dvx
a)
dy

Similarly the average momentum of molecules having their last

dv
m(vx x a)
dy
collision in the plane (y - a) will be:
Now lets calculate how many molecules will be crossing the plane y
from above and below.
The average velocity of the molecules is v and we saw earlier that
it is determined by the temperature.
1/6th of the molecules above the plane y will be traveling in the y
direction with the velocity v. Similarly 1/6th of the molecules below
plane y will be traveling in the +y direction with the velocity v.
Now v is the distance travelled in unit time (say per unit second).
So all molecules that are present a vertical distance v above/below
the plane y (see the orange/green regions below), and travelling in
the ve/+ve y direction, will cross the plane within one sec.

ux
vx

y+
a
y
y-a

v
v

dvx
a
dy

vx
vx

dvx
a
dy

Therefore nv/6 molecules (no of molecules per unit area in the

orange box travelling in the y directions) will cross per unit area of
the y plane in 1 sec from above. A same number will cross from
below. The difference between the two will be the flux of molecules
across the plane (remember flux is flow per unit area per unit time).
If we were only thinking about mass flux at this point, the flux will
be zero. But we are considering the momentum flux, and it will not
be zero because there is a gradient in the x-velocity in the y
direction.

ux

The total momentum flux is the difference between the momentum

carried by molecules crossing the plane (per unit area in unit time)
from below (moving in the +y direction) minus the momentum
carried by molecules crossing from above (moving in y direction.
This is

nv
dv
dv
m vx x a vx x a
6
dy
dy

nv dvx
ma
yx
3
dy

Therefore if you compare the continuum and molecular expressions

for

yx

we get an expression for the viscosity in molecular terms:

nv
2nv
ma
m
3
9
Therefore viscosity is a transfer coefficient describes how easily the
x momentum transports in the y direction. It depends on the mean
free path, concentration of molecules n, and the average molecular
velocity v (which depend on temperature).
By similar argument you can derive the transfer coefficient for heat
and mass along a temperature and concentration gradient
respectively.
Note in the case of heat transfer, there is a gradient in temperature,
and the molecules will on average carry the heat in the plane they
last collided in. The heat carried by a molecule is it specific heat
capacity times the temperature.
9.3 in textbook for energy diffusion coefficient
17.3 in textbook for mass diffusion coefficient.

In both heat and momentum transfer, the concentration of

molecules in the same. In the case of mass transfer. There is a
gradient in the concentration. Therefore the number of molecules
coming crossing our plane from above and below are different. The
number of molecules crossing the plane in a direction will reflect the
concentration of their last collision plane.

1.4.3 Qualitative difference between viscosity in a fluid and

liquid

The big difference between a liquid and a gas is that interactions

between molecules are present in a fluid. These interactions can be
neglected in a gas.
As a consequence: the viscosity of a fluid decreases with
Temperature; whereas the viscosity of a gas increases with
Temperature
In the case of a fluid: Increase in temperature increases the energy
of fluid molecules; the molecules break inter-molecular forces, and
are able to take on the fluid velocity imparted by say a moving wall.
Therefore the viscosity decreases. That is, for the same amount of
shearing force, you will produce a larger strain (move the wall
further) at a higher temperature.
In the case of a gas: Increase in temperature increases the random
molecular velocity and increases the frequency with which any
imparted fluid velocity (say from a moving wall) is randomized.
Therefore the work done by a wall in imparting a shearing velocity is
less effective, or the viscosity increases. That is, for the same
amount of force, there is less shear strain produced in a gas when
the temperature is increased.