Atomic Absorption Spectroscopy

Atomic Absorption Spectroscopy

AAS is commonly used for metal analysis A solution of a metal compound is sprayed into a flame and vaporises The metal atoms absorb light of a specific frequency, and the amount of light absorbed is a direct measure of the number of atoms of the metal in the solution

The Electromagnetic Spectrum

Names of the regions are historical. There is no abrupt or fundamental change in going from one region to the next. Visible light represents only a very small fraction of the electromagnetic spectrum.
Frequency (Hz) 1020 -rays 10-11 Wavelength (m) 1018 X-rays 10-8 1016 UV 10-6 Visible 400 500 600 700 800 nm 1014 IR 10-3 1012 108 Microwave

Absorption of Light
When a molecule absorbs a photon, the energy of the molecule increases. photon Ground Excited state state

Microwave radiation stimulates rotations Infrared radiation stimulates vibrations UV/VIS radiation stimulates electronic transitions X-rays break chemical bonds and ionize molecules

Absorption of Light
When light is absorbed by a sample, the radiant power P (energy per unit time per unit area) of the beam of light decreases. The energy absorbed may stimulate rotation, vibration or electronic transition depending on the wavelength of the incident light.

Atomic Absorption Spectroscopy

Uses absorption of light to measure the concentration of gas-phase atoms. Since samples are usually liquids or solids, the analyte atoms must be vapourised in a flame (or graphite furnace).

Absorption and Emission

Excited States

Ground State Absorption

Emission

Multiple Transitions

Atomic Absorption
When atoms absorb light, the incoming energy excites an electron to a higher energy level. Electronic transitions are usually observed in the visible or ultraviolet regions of the electromagnetic spectrum.

Atomic Absorption Spectrum

An absorption spectrum is the absorption of light as a function of wavelength. The spectrum of an atom depends on its energy level structure. Absorption spectra are useful for identifying species.

Atomic Absorption Spectroscopy

The analyte concentration is determined from the amount of absorption.

Atomic Absorption Spectroscopy

cathode lamp produces light frequencies unique to the element under investigation When focussed through the flame these frequencies are readily absorbed by the test element The excited atoms are unstable- energy is emitted in all directions hence the intensity of the focussed beam that hits the detector plate is diminished The degree of absorbance indicates the amount of element present

Atomic Absorption Spectroscopy

It is possible to measure the concentration of an absorbing species in a sample by applying the BeerLambert Law:

Abs = cb

I A b s= lo g Io
= extinction coefficient

Atomic Absorption Spectroscopy

But what if is unknown? Concentration measurements can be made from a working curve after calibrating the instrument with standards of known concentration.

AAS - Calibration Curve

The instrument is calibrated before use by testing the absorbance with solutions of known concentration. Consider that you wanted to test the sodium content of bottled water. The following data was collected using solutions of sodium chloride of known concentration Concentration (ppm) 2 4 6 8 Absorbance 0.18 0.38 0.52 0.76

Calibration Curve for Sodium

A b s o r b a n c e

1.0

0.8

0.6

0.4

0.2

Concentration (ppm)

Use of Calibration curve to determine sodium concentration {sample absorbance = 0.65}

A b s o r b a n c e
1.0

0.8

0.6

0.4

0.2

Concentration Na+ = 7.3ppm

2 4 6 8

Concentration (ppm)

Atomic Absorption Spectroscopy

Instrumentation Light Sources Atomisation Detection Methods

Light Sources
Hollow-Cathode Lamps (most common). Lasers (more specialised). Hollow-cathode lamps can be used to detect one or several atomic species simultaneously. Lasers, while more sensitive, have the disadvantage that they can detect only one element at a time.

Hollow-Cathode Lamps
Hollow-cathode lamps are a type of discharge lamp that produce narrow emission from atomic species. They get their name from the cup-shaped cathode, which is made from the element(s) of interest.

Hollow-Cathode Lamps

The electric discharge ionises rare gas (Ne or Ar usually) atoms, which in turn, are accelerated into the cathode and sputter metal atoms into the gas phase.

Hollow-Cathode Lamps

Hollow-Cathode Lamps
The gas-phase metal atoms collide with other atoms (or electrons) and are excited to higher energy levels. The excited atoms decay by emitting light. The emitted wavelengths are characteristic for each atom.

Hollow-Cathode Lamps
M*

collision-induced excitation
M M*

M+e M + Ar*

M* M*

spontaneous emission
M

M*

M + hn

Atomisation
Atomic Absorption Spectroscopy (AAS) requires that the analyte atoms be in the gas phase. Vapourisation is usually performed by: Flames Furnaces Plasmas

Flame Atomisation
Flame AAS can only analyse solutions. A slot-type burner is used to increase the absorption path length (recall Beer-Lambert Law). Solutions are aspirated with the gas flow into a nebulising/mixing chamber to form small droplets prior to entering the flame.

Flame Atomisation

Furnaces
Improved sensitivity over flame sources. (Hence) less sample is required. Generally, the same temp range as flames. More difficult to use, but with operator skill at the atomisation step, more precise measurements can be obtained.

Furnaces

1) The elements must be reduced to the elemental, neutral state by the flame. 2) The elements must be in vaporized state. 3) The elements must be imposed in the beam of radiation source.

ground

from the

Advantages:

Very sensitive. Fast.

Disadvantages:

Hollow cathode lamp for each element. Expensive element.

Thats All Folks!

Thank You.