Excitation Equilibrium: Boltzmanns Equation

The equivalent width of the spectral line depends on directly upon

the no of atoms in the energy state from which the transition
occurs.

The number of photons of a given energy increases rapidly with

increasing temperature ( mv 2 / 2 = 3kT / 2 )

So absorption lines originating from excited levels tend to be

stronger in hot gases than in cool gases.

Consider a situation where thermal equilibrium prevails and the

average number of atoms in a given state remains unchanged in
time (steady state situation)

Each excitation is on the average balanced by a de-excitation

In this case number density of atoms in state B is related to the
number density in state A (B>A) by Bolltzmanns equation

N B / N A = ( g B / g A ) exp[( E A E B ) / kT ]

Where N is the number density in the level, g is the multiplicity of

the level and E is the energy level
NB
For E B > E A , increases with temperature.
NA
NB
For a given temperature, the excitation ratio increases as the
NA
excitation potential E B E A decreases between the two energy
levels.
As an example, consider a volume a volume of gas that contains
the same number of hydrogen and helium atoms at a temperature
the number of hydrogen atoms in the first excited state N 2 equals
one-tenth the number in the ground state N1

Or N 1 / N 2 = 0.1

On the other hand the ratio N 2 / N 1 for helium will be very low.
So at given temperature, the fraction of atoms in the second level
differs widely from element to element, depending on the
excitation potential. In this case absorption lines will be strong for
hydrogen and weak for helium.

The equivalent width of the line is a function of both the

abundance of the particular element and the temperature (in this
example we have ignored the ionization of atoms. For a complete
picture we should consider both ionization and excitation).

Ionization Equilibrium: Sahas Equation

As the temperature of a gas is increased, more and more energy

becomes available to ionize the atoms. In general, the hot gas
consists of neutral atoms, ions, and free electrons.

The greater the electron density, the greater the probability that an
ion will capture an electron and become a neutral atom.
These two competing processes, ionization and recombination are
written as
X < > X + + e
A steady state condition of ionization equilibrium is achieved in
the gas when the rate of ionization equals the rate of
recombination.
A quantitative expression of this ionization equilibrium is given by
Sahas equation.
N + / N 0 = [ A(kT ) 3 / 2 / N e ] exp(0 / kT )
N + is the number density of ions, N 0 is the number density of
neutral atoms in the ground state, the constant A includes several
atomic constants and incorporates the probability of different
states of ionization,T is the absolute temperature, N e is the
electron density and 0 is the ionization potential(in eV) from the
ground state of the neutral atom.

The Boltzmann excitation equation applies to any levels of

excitation, those of ion and those of a neutral atom.
Similarly Saha ionization equation can be generalized to give the
ratio N i +1 / N i for any stage of ionization i+1 and the next lower
stage i.
The appropriate form of Sahas equation is
N i +1 / N i = [ A(kT ) 3 / 2 / N e ] exp( i / kT )
Where i is the ionization potential of the lower stage (the energy
needed to ionize the particle in the i state to the i +1 state)

The Boltzmann and Saha equations combined

The Boltzmann equation gives the number of atoms in an excited

state relative to the number in any other state; this applies to both
neutral and ionized atoms. The Saha equation tells us the relative
population of two adjacent stages of ionization. We combine these
two equations to calculate the number of atoms available to make a
certain transition and so produce a spectral line.

Consider the Balmer absorption lines of neutral hydrogen. Their

strength is proportional to the number of atoms in the first excited
state N 2 of the neutral atom relative to the total number of
hydrogen atoms in all stages of ionization N.
Hydrogen has only two stages of ionization, neutral N 0 and singly
ionized N + .Hence we know that N = N0 + N+
N 2 / N is given
The proportion of
N 2 / N = N 2 /( N 0 + N + )
( N 2 / N 1 ) /[1 + ( N + / N 0 )]
Where we have used the reasonable approximation N 0 N1
(most neutral atoms are in the ground state).

The Boltzman equation yields N 2 / N 1 , the ration of neutral

atoms in the first excited state to those in the ground state and the
Saha equation gives
N + / N 0 , the ratio of the ionized to the neutral atoms.

A plot of N + / N 0 as a function of temperature shows that most of

the hydrogen is neutral at temperatures below 7000K, but at higher
temperatures ionization increases to the point where the number of
neutral atoms becomes negligible.
The exponential increase of N 2 / N 1 with increasing
temperatures is there fore countered by the lack of neutral atoms at
high temperatures.
As a result , the N 2 / N curve has a maximum around 10000 K
The strength of the Balmer absorption line of hydrogen is greatest
at nearly 10000K
The Boltzman and Saha equations have wide applications in
Astrophysics. Through them we may interpret stellar absorption
(and emission )spectra in order to reduce the surface temperatures
and pressures of stars.