Atomic absorption

Lab Techniques
Dr. Maha Daghestani

Dr. Maha Daghestani

Divination
In analytical chemistry, Atomic absorption spectroscopy is a technique for determining the concentration of a particular metal element in a sample. Atomic absorption spectroscopy can be used to analyze the concentration of over 62 different metals in a solution.

Dr. Maha Daghestani

technique
. The technique typically makes use of a flame to atomize the sample, but other atomizers such as a graphite furnace are also used. Three steps are involved in turning a liquid sample into an atomic gas:

Dr. Maha Daghestani

steps
Three steps are involved in turning a liquid sample into an atomic gas: Desolvation the liquid solvent is evaporated, and the dry sample remains Vaporisation the solid sample vaporises to a gas Volatilization the compounds making up the sample are broken into free atoms .
Dr. Maha Daghestani

flame
The flame is arranged such that it is laterally long (usually 10cm) and not deep. The height of the flame must also be monitored by controlling the flow of the fuel mixture. A beam of light passes through this flame at its longest axis (the lateral axis) and hits a detector.

Dr. Maha Daghestani

The light
The light that is focused into the flame is produced by a hollow cathode lamp. Inside the lamp is a cylindrical metal cathode containing the metal for excitation, and an anode. When a high voltage is applied across the anode and cathode, the metal atoms in the cathode are excited into producing light with a certain emission spectrum.
Dr. Maha Daghestani

 The type of hollow cathode tube depends on the metal being analyzed. For analyzing the concentration of copper in an ore, a copper cathode tube would be used, and likewise for any other metal being analyzed. The electrons of the atoms in the flame can be promoted to higher orbitals for an instant by absorbing a set quantity of energy (a quantum).
Dr. Maha Daghestani

 This amount of energy is specific to a particular electron transition in a particular element. As the quantity of energy put into the flame is known, and the quantity remaining at the other side (at the detector) can be measured, it is possible to calculate how many of these transitions took place, and thus get a signal that is proportional to the concentration of the element being measured.
Dr. Maha Daghestani

Atomic Absorption Process

A neutral atom in the gaseous state can absorb radiation and transfer an electron to an excited state. Simple electronic transitions possible with no vibrational and rotational energy levels possible. Bandwidth much narrower! Occur at discreet Na(g) 3s 3p and 3p 5s as well as other transitions are possible at the correct photon energy a transition.
Chapter 8&9 - 10

THE FLAME AND EXCITED STATES

3 steps required before measurements are possible in an A.A. experiment: 1. vaporization 2. reduction to the elemental state and then 3. exposure to radiation. The first two steps are accomplished by a flame. Effect of flame temperature: Since flame is at high temperature might have an effect on fraction of atoms in excited state.

MEASURING ATOMIC ABSORPTION

Recall Beer's Law (A = log Po = bC ) is obeyed when line width small compared to absorption band. Atoms or molecules absorb radiation at discrete wavelengths. Broadband radiation contains photons of several wavelengths, some of which may be useful but many of which will not. This will make Po (= Pusable + Puseless) larger and the absorbance smaller than would be expected with only the usable portion of the light available for absorption. Besides the Pusable can be composed of wavelengths with different absorptivities i.e. the sample does not absorb all radiation to the same degree. Non-linear behavior observed when range of excitation source is greater than range of absorber; bandwidth of excitation source must be narrower than bandwidth of absorber.
P

Chapter 8&9 - 12

Linewidth of Atomic Transitions

Natural linewidth of an absorption spectrum is very small (104) but is broadened by
Doppler broadening: Random thermal motions of atoms relative to the detector Pressure broadening: In the atomic absorption experiment the pressure is large enough that atoms can undergo some interatomic collisions which cause small changes in the ground state levels.

Normal line width of excitation lines much greater than this line width Monochromator cannot be used to select range in AA (bandwidth few tenths of a nm).
Chapter 8&9 - 13

SOURCES
Solution to line width problem: Use atomic source of same material. e.g. For Na analysis Na vapor is used. Atoms are excited by electrical discharge; the excited atoms emit a characteristic . The bandwidth of the source << sample linewidth since it is generated under conditions where there is less broadening. Hollow Cathode Tube : Hollow cathode made of the material needed is vaporized and emits radiation of the characteristic wavelength. The ion current to the cathode controls photon intensity; Increasing the voltage between the anode and cathode will control the current and thus total photon flux. Optimum current for each lamp ( 1-20ma).

Chapter 8&9 - 14

FORMATION OF ATOMIC VAPOR

Four methods used to vaporize sample from solution: Ovens: Sample placed in an oven; after evaporating solvent, sample vaporized into irradiation area by rapidly increasing temperature. Electric arc or spark: Sample subjected to high current or high potential A.C. spark. Ion bombardment: Sample placed on cathode and bombarded with + ions (Ar+). Sputtering process dislodges them from cathode and directs them to irradiation region. Flame atomization: Sample sprayed into flame where it undergoes atomization and irradiation.
Chapter 8&9 - 15

FLAME ATOMIZERS
Total consumption burner: Separate channels bring sample, fuel, and oxidant to combustion area. All of the sample, that is carried into the burner, is burned; Sensitivity is greater than in a burner where the sample is not completely burned. extra turbulence in the flame from variations in droplet size increase noise.

Undergraduate Instrumental Analysis, Robinson, p. 267.

Chapter 8&9 - 16

Premix (laminar flow) burner

Sample, fuel, and oxidant mixed prior to entering flame. Turbulence drastically reduced by removing larger droplets. Mixing baffles insure only fine mist makes it through to burner.

Instrumental Methods of Chemical Analysis, Ewing, p. 110.

Chapter 8&9 - 17

ELECTROTHERMAL ATOMIZATION
all of the sample used is atomized in furnace (electrothermal) atomizer. detection limit is 100-1000x lower than with aspiration techniques. only a few mL of solution is used. Basic Principle:
sample container resistively heated to vaporize the metal atoms. sample dried (evaporate solvent) at 110C; ash sample called "burn off" (200300C); atomization.(2000-3000C) comparison with flame atomization:
Instrumental Methods of Analysis, Willard,Merritt, Dean and Settle, p. 147

interaction with sample matrix and electrode poorer reproducibility detection limits of 1010-1012g (or 1ppb) are possible.

Chapter 8&9 - 18

FUELS/OXIDANTS
Low T flames : easily reduced elements (Cu, Pb, Zn, Cd) High T flames: difficult to reduce elements (e.g. alkaline earths). Fuels: natural gas, propane, butane, H2, and acetylene; Oxidants- Air and O2 (low temperature flames). N2O (high temperature flames). Flame characteristics: Sample enters flame, is vaporized, reduced and eventually oxidized. Exact region of flame in which each of these occurs depends upon: flow rate, drop size, and oxidizability of sample. Optimum position for flame for many metals.

Chapter 8&9 - 19

MEASUREMENT OF AA
Ideally, the amount of light reaching the detector is given by Beers Law: P = Po10bC . several interferences can change this to: P = Po10bC + Pemission Pbackground Pscattering. Pemission is due to analyte emission in the flame eliminated from the absorbance by modulation of the light source: measures only AC levels; emission DC level. Pbackground, Pscattering: due to absorption by the flame or are induced by sample matrix and are independent of the analyte. Broad band in nature. Flame interferences nulled by comparing a blank with sample
Sample matrix is a problem. Caused by, for example, high salt content (e.g. NaCl or KI). These have broad band absorption spectrum in flame since they are not reduced by it. Most common approach uses secondary continuum source (e.g. D2 lamp): Each lamp (D2 and HCT) modulated but are 180 out of phase with each other. Detection system measures difference between two absorbance signals: AHCT = Asample + Abrdband while Acontinuum source = Abrd band. will be absorbance of sample.
Chapter 8&9 - 20

D2 Source Elimination of Background

Chapter 8&9 - 21

MONOCHROMATOR
Needed to choose one of several possible emission lines (emitted) associated with HCT. Since they are usually reasonably well separated from the line of interest, it is straightforward to use a monochromator to eliminate this interference.
Chapter 8&9 - 22

ANALYTICAL TECHNIQUES
Beer's law, A = kC, not always true making a calibration curve necessary. Standard addition method is used to minimize the effects from the matrix Anion- height of the absorbance peak is influenced by type and concentration of anion. It can reduce the number of atoms made. An unknown matrix is thus hard to correct for Cation: The presence of a second cation sometimes causes stable compounds to form with the cation being analyzed. e.g. Al + Mg produces low results for Mg due to the formation of an Al/Mg oxide.
Chapter 8&9 - 23

Sample Problem
The nickel content in river water was determined by AA analysis after 5.00 L was trapped by ion exchange. Rinsing the column with 25.0 mL of a salt solution released all of the nickel and the wash volume was adjusted to 75.00 mL; 10.00 mL aliquots of this solution were analyzed by AA after adding a volume of 0.0700 g Ni/mL to each. A plot of the results are shown below. Determine the concentration of the Ni in the river water.
Determination of Nickel Content by AA
120 y = 5.6x + 20 Absorbance Units 80

40

0 0 5 10 15 Volum e of Nickel Added(m L)

Chapter 8&9 - 24

Chapter 8&9 - 25

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