AN EXPONENTIAL ATMOSPHERE

Let
us try to find the distribution of the molecules
in an atmosphere which is without the winds and
other kind of disturbances.
Consider a column of gas extending up to a great
height, and at thermal equilibrium.
It is different from our atmosphere because it gets
colder as we go up.
Take the number density, i.e., the number of
molecules per unit volume be .
We know that the gas satisfies,

or

 Its
intuitive that the pressure is not constant in
the column of the gas. It has to increase as the
altitude is decreased, since it has to hold the
weight of all the gas above it.
The temperature, however, is constant as per our
assumption.
Consider an area at height with pressure .
Also let the pressure at height be .
Note that has to be less than .

Each molecule experiences the gravitational force

mg, where is the mass of each molecule.
This infinitesimal column contains molecules. Thus
it has total weight .

 The
pressure difference has to take care of this
weight, thus

We have the gas equation,

as has been assumed to be constant.

Comparing the two equations we obtain,

 Thus
we have the differential equation,

This equation tells us the rate at which the

number density of gas molecules change with
height.
We could have got similar equation for as well.
Rearranging the terms in the above equation
Integrate this with the boundary condition at ,
which can be any level of our choice.

This gives
This suggests that number density decreases
exponentially with mass of the molecule and the
height.
For the same height the number of more massive
molecules dies out faster.
This, of course, is not what happens in our atmosphere,
as we have lot of disturbances, and its not isothermal.
Nevertheless, there is a tendency for lighter molecules,
like Hydrogen, to dominate at greater heights.

THE BOLTZMANN LAW

We
found the number density to be

If we examine the exponent, we can see a familiar

factor there:
, the potential energy of each molecule!
Now this could be an artifact of the particular choice
of our system. However, it turns out to be a more
general proposition.

THE BOLTZMANN LAW

It
turns out to be one of the very fundamental
principles of classical statistical mechanics, called the
Boltzmann Law or Boltzmann distribution or Gibbs
distribution or Gibbs-Boltzmann distribution.
This equation is what forms the basis of the MaxwellBoltzmann statistics.
For example, this implies that the probability of
finding the molecules in a given spatial arrangement
varies exponentially with the negative of the
potential energy of that arrangement, divided by kT.

Expressed in terms of (speed-squared) we have

f
This is the famous Maxwell-Boltzmann distribution law. f
gives the fraction of particles which have speed in the
range and .

Visit this webpage for a nice Java applet related to the above
distribution:

From the plot it is clear that at lower temperatures the

particles are selective, large fraction of the particles
have their speeds around a particular value (maxima of
the curve: Most probable speed).
As the temperature is increased this localization around
a particular value becomes less.

MOST PROBABLE
SPEED
It
is
the
speed
most
likely to be possessed by any

molecule (of the same massm) in the system. It is

the value at which the maximum of the distribution
curve occurs, i.e.,

The first value corresponds to the minimum, while

the second value gives the maximum.
Thus, the most probably speed is

MOST PROBABLE
SPEED
is the molar mass, i.e., mass of one mole of the

If

molecules, then
where is the Avogadro number.
Thus,

Here is the universal gas constant.

MEAN SPEED
Mean
speed can be obtained using

.
Note that it is the continuous analog of
.
with .
Thus,
The substitution leads to
.

MEAN SPEED
We can also express this in terms of the molar mass
and universal gas constant. We have

ROOT MEAN SQUARE (RMS) SPEED

RMS
speed can be obtained using

.
Note that above is the continuous analog of
.
with .
Thus,
The integral can be performed either using Gamma
function result or Gaussian integral result. We have,

ROOT MEAN SQUARE (RMS) SPEED

we obtain
Therefore,

This is in agreement with

Finally,

Macrostate vs Microstate
The thermodynamic state of the gas (which
characterizes the values of macroscopic
observables such as energy, pressure, volume, etc.)
corresponds to many possible configurations of the
constituents (molecules). These configurations of
the constituents are the microstates.
The macroscopic, thermodynamic state in this case
would be the macrostate.
For example, consider a gas. This is made of some
elementary constituents (molecules).

HEAT

Heat concerns with the transfer of energy from one

object to another as a result of their different
temperatures.
When we say two objects are in Thermal contact, that
means heat, and hence energy can flow between objects

T1 > T2

T1
U1

U2

T2

TFinal

TFinal

T1 > Tfinal>T2

Thermal equilibrium is established when objects in

thermal contact cease heat transfer: They are said to
be at the same temperature.

ZEROTH LAW OF THERMODYNAMICS

Thezeroth law of thermodynamicsstatesthatiftwo
systems(AandB)areinthermalequilibriumwithathird
system(C),they(AandB)arealsointhermal
equilibriumwitheachother.
A

The zeroth law of thermodynamics does not imply

that the intermediate temperature will be an
average of two temperatures.
It does not even imply a linear temperature scale.
The scale will be established in other means (3rd
law)

THE CONCEPT OF WORK

Work
is a Mechanical form of Energy: Its the product of
Force and displacement in the direction of the
applied force.

Force
Distance
x
Recalling the definition of pressure (Force per unit
area), we obtain
Thus work done is associated with volume change.

THE CONCEPT OF WORK

Changes in Volume Cause Work:
Work is performed when air expands
Work of Expansion:

dW 0

Occurs when a system performs work

(or exerts a force) on its environment.
Rising air parcels (or balloons) involve
expansion work
Since the environmental pressure decreases
with height, a rising parcel must expand to
maintain an equivalent pressure

THE CONCEPT OF WORK

Changes in Volume Cause Work:

Work is performed when air contracts

Work of Contraction:

dW 0

Occurs when an environment performs

work
(or exerts a force) on a system
Sinking air parcels (or balloons) involve
contraction work
Since the environmental pressure
decreases with height, a falling parcel must
contract with height
to maintain an equivalent pressure

PV DIAGRAMS
One of the ways of Depicting
Thermodynamic Processes:
p
f

pf

pi

Vi

Transformation from

Vf

if

PV DIAGRAMS
The work done can be found
using area under the curve.

W pdV

pf

pi

dW pdV

Vi

Vf

The work done is

the area under the
i f curve
(or gray area)

FIRST LAW OF THERMODYNAMICS

First law of thermodynamics is basically the
statement of Energy conservation in a broader
sense.
The totalenergyof an isolated system is
constant. Energy can be transformed from one
form to another, but cannot be created or
destroyed.

Energy (E) = Constant

FIRST LAW OF THERMODYNAMICS

Using Clausius sign convention this can be
expressed as,
Here signifies the change in internal energy of the
system. is the heat transferred to the system by the
environment and is the work done by the system on
the environment.
If is +ve ( is negative), that means work is being done
by the system on the environment. If is ve ( is +ve),
that means work is being done by the environment on
the system.
Note that for , U is negative if is +ve, i.e., if work is
done by the system on the environment. This is
reasonable as the internal energy of the system must
decrease in this process.
Similarly, if is ve, is +ve, i.e., systems internal
energy increases.

FIRST LAW OF THERMODYNAMICS

Using IUPAC sign convention first law is written as

Here signifies the change in internal energy of the

system. is the heat transferred to the system by the
environment and is the work done on the system by
the environment.
This convention considers all net energy transfers to
the system as positive and all net energy transfers
from the system as negative, irrespective of any use
for the system as an engine or other device.
If is +ve, that means work is being done on the
system by the environment. If is ve , that means
work is being done by the system on the environment.
Note that for , is positive if is +ve, i.e., if work is done
by the system on the environment. This is reasonable
as the internal energy of the system must increase in
this process. Similarly, if is ve, is -ve, i.e., systems

FIRST LAW OF THERMODYNAMICS

In
the differential form the first law is written as follows:
Clausius sign convention:
IUPAC sign convention:

The notation with and signify that they are path

functions, i.e., they depend on how the thermodynamic
system changes from the initial state to final state.
While is a state function it is independent of the path
taken to reach the final state from the initial.

THERMAL CAPACITIES (HEAT CAPACITY)

If
is a small amount of heat absorbed by a substance,
and dT is the accompanying small change in
temperature, then heat capacity is defined as

.
The heat capacity depends on the detailed nature of the
system. This means it is a physical property that scales
with the size of a physical system. Thus it is an extensive
property.
Two types of specific heat can be defined depending on
the conditions under which the material receives heat.
Constant volume:

Constant pressure:

SPECIFIC HEAT & MOLAR HEAT CAPACITY

Specific
Heat of a substance is the heat capacity per unit
mass
of the
substance. Consequently specific heat is
anintensive property- an intrinsic characteristic of a
particular substance.
It is usually represented by lower case , instead of upper
casefor the heat capacity. Sometimes is also used to
represent it.
As in the case of heat capacity, we have two kinds of
specific heat: Specific heat at constant volume () and
Specific heat at constant pressure ().
Molar heat capacity of a substance is the heat capacity
per mole of the substance. It is anintensive property. It
may be represented by the symbol .