The Effect of Temperature on Atomic Spectra

Atomic spectroscopic methods require the conversion of atoms to the gaseous state.
This requires the use of high temperatures (in the range from 2000-6000 oC). Thee
high temperature can be provided through a flame, electrical heating, an arc or a
plasma source. It is essential that the temperature be of enough value to convert atoms
of the different elements to gaseous atoms and, in some cases, provide energy
required for excitation. The temperature of a source should remain constant
throughout the analysis especially in atomic emission spectroscopy. Quantitative
assessment of the effect of temperature on the number of atoms in the excited state
can be derived from Boltzmann equation:

Nj/No = (Pj/Po) exp (- Ej/KT)

Where Nj is the number of atoms in excited state, No is the number of atoms in the
ground state, Pj and Po are constants determined by the number of states having equal
energy at each quantum level, Ej is the energy difference between excited and ground
states, K is the Boltzmann constant, and T is the absolute temperature. To understand
the application of this equation let us consider the situation of sodium atoms in the 3s
state (Po = 2) when excited to the 3p excited state (Pj = 6) at two different
temperatures 2500 and 2510K. Now let us apply the equation to calculate the relative
number of atoms in the ground and excited states:
Usually we use the average of the emission lines from the 3p to 3s where we have two
lines at 589.0 and 589.6 nm which is:

= (589.0+589.6)/2 = 589.3 nm
Ej = hc/
Ej = (6.6256x10-34 J s x 2.998x1010 cm s-1)/{(589.3 nm x (cm/ 107 nm)}
Ej = 3.37x10-19 J

Ne/No = (6/2) exp {(-3.37x10-19 J/(1.38x10-23 J K-1 x 2500 K)}

Ne/No = 1.72x10-4

Performing the same calculation at the other temperature (2510 oC) we get:
Ne/No = (6/2) exp {(-3.37x10-19 J/(1.38x10-23 J K-1 x 2510 K)}
Ne/No = 1.79x10-4

Therefore, at higher temperatures, the number of atoms in the excited state increases.
Let us calculate the percent increase in the number of atoms in the excited state as a
result of this increase in temperature of only 10 oC:

% increase = {(1.79x10-4 - 1.72x10-4)/ 1.72x10-4} x 100% = 4.1%

It is noteworthy that a relatively slight increase in temperature resulted in an

astonishing increase in the number of atoms in the excited state. This will necessitate
that the temperature should be constant throughout the analytical process with no
fluctuations, otherwise the noise will be intolerable.
Effect of Temperature on Atomic Absorption and Emission

The question here is which technique would be affected more as a result of

fluctuations in temperature? The answer to this important question is rather simple.
Atomic emission is the technique that will be severely affected by fluctuations in
temperature since signal is dependent on the number of atoms in the excited state.
This number is significantly affected by fluctuations in temperature as seen from the
example above. However, in the case of atomic absorption, the signal depends on the
number of atoms in ground state that will absorb energy. Always the number of atoms
in ground state is very high as related to the number of excited atoms:

Nj/No = 1.72x10-4
or
172 excited atoms for each 106 atoms in ground state

This suggests a very high population of the ground state even at high temperatures.
Therefore, atomic absorption will not be affected to any significant extent by
fluctuations in temperature, if compared to atomic emission spectroscopy. However,
there are some indirect effects of temperature on atomic absorption spectroscopy.
These effects can be summarized as:

1. Better sensitivities are obtained at higher temperatures since higher

temperatures can increase the number of vaporized atoms at ant time.
2. Higher temperatures will increase the velocities of gaseous atoms, thus
causing line broadening as a result of the Doppler and collisional effects.
3. High temperatures increase the number of ionized analyte and thus decrease
the number of atoms available for absorption.

Band and Continuum Spectra Associated with Atomic Spectra

When the atomization temperature is insufficient to cause atomization of all species in

the sample matrix, the existent molecular entities, at the temperature of the analysis,
impose very important problems on the results of atomic absorption and emission
spectroscopy. The background band spectrum should be removed for reasonable
determination of analytes. Otherwise, the sensitivity of the instrument will be
significantly decreased. Look at the following case where a band spectrum of matrix
components is superimposed on the analyte atomic line of interest:
 Emission Absorption
Abs. Continuum Continuum
Or
Emiss

Analyte
Line

When a correction blank is made, the matrix will give the continuum spectra shown
in the figure above. As the signal for the blank is considered zero and thus the
instrument is made to read zero, when the analyte is to be determined, it got to have
an absorbance greater than the highest point on the continuum and the instrument
will assume that the absorbance related to analyte is just the value exceeding the
background blank value. This will severely limit the sensitivity of the technique.
Putting this conclusion in other words we may say that if the analyte signal is less
than the background blank, the instrument will read it as zero. Therefore, it is very
important to correct for the background or simply eliminate it through use of very
high temperatures that will practically atomize all species in the matrix. We will
come to background correction methods in the next chapter.

Atomization Methods

It is essential, as we have seen from previous discussion, that all sample components
(including analytes, additives, etc.) should be atomized. The atoms in the gaseous
state absorb or emit radiation and can thus be determined. Many ionization methods
are available which will be detailed in the next two chapters. Generally, atomization
methods can be summarized below:

Atomizer Type Sample Introduction Typical Temperature, oC

Form, Mostly
Flames Solution 1700-3150, Depending of type
of fuel and oxidant
Electrothermal Atomizers Solution 1200-3000
Inductively Coupled Solution 4000-6000
Plasma
Direct Current Plasma Solution 4000-6000
Electric Arc Solid 4000-5000
Electric Spark Solid 40,000 ???

Sample Introduction Methods

The method of choice for a specific sample will mainly depend on whether the sample
is in solution or solid form. The method for sample introduction in atomic
spectroscopy affects the precision, accuracy and detection limit of the analytical
procedure.

Introduction of Solution Samples

1. Pneumatic Nebulizers

Samples in solution are usually easily introduced into the atomizer by a simple
nebulization, aspiration, process. Nebulization converts the solution into an aerosol of
very fine droplets using a jet of compressed gas. The flow of gas carries the aerosol
droplets to the atomization chamber or region. Several versions of nebulizers are
available and few are shown in the figure below:

High Pressure
Gas Flow

Solution
sample

Solution
High Pressure
sample
Gas Flow

2. Ultrasonic Nebulizers

In this case samples are pumped onto the surface of a piezoelectric crystal that
vibrates in the kHz to MHz range. Such vibrations convert samples into homogeneous
aerosols that can be driven into atomizers. Ultrasonic nebulization is preferred over
pneumatic nebulization since finer droplets and more homogeneous aerosols are
usually achieved. However, most instruments use pneumatic nebulization.

3. Electrothermal Vaporization

An accurately measured quantity of sample (few L) is introduced into an electrically

heated cylindrical chamber through which an inert gas flows. Usually, the cylinder is
made of pyrolytic carbon but tungsten cylinders are now available. The signal
produced by instruments which use electrothermal vaporization (ETV) is a discrete
signal for each sample injection. Electrothemal vaporizers are called discrete
atomizers to differentiate them from nebulizers which are called continuous
atomizers.

4. Hydride Generation Techniques

Samples that contain arsenic, antimony, tin, selenium, bismuth, and lead can be
vaporized by converting them to volatile hydrides by addition of sodium borohydride.
Volatile hydrides are then swept into the atomizer by a stream of an inert gas.