Atomic absorption

Lab Techniques
Dr. Maha Daghestani

Dr. Maha Daghestani

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

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

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 .steps • • • • Three steps are involved in turning a liquid sample into an atomic gas: Desolvation – the liquid solvent is evaporated. Dr. Maha Daghestani .

Maha Daghestani . A beam of light passes through this flame at its longest axis (the lateral axis) and hits a detector. Dr.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.

Maha Daghestani . Dr. the metal atoms in the cathode are excited into producing light with a certain emission spectrum. When a high voltage is applied across the anode and cathode. and an anode.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.

• The type of hollow cathode tube depends on the 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). For analyzing the concentration of copper in an ore. Maha Daghestani . a copper cathode tube would be used. Dr. and likewise for any other metal being analyzed.

Maha Daghestani . Dr.• 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 thus get a signal that is proportional to the concentration of the element being measured. it is possible to calculate how many of these transitions took place. and the quantity remaining at the other side (at the detector) can be measured.

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

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

P • • Chapter 8&9 .e. 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. Non-linear behavior observed when λ range of excitation source is greater than λ range of absorber. some of which may be useful but many of which will not. Atoms or molecules absorb radiation at discrete wavelengths.12 . the sample does not absorb all radiation to the same degree. Broadband radiation contains photons of several wavelengths.MEASURING ATOMIC ABSORPTION • • • Recall Beer's Law (A = log Po = εbC ) is obeyed when line width small compared to absorption band. bandwidth of excitation source must be narrower than bandwidth of absorber. Besides the Pusable can be composed of wavelengths with different absorptivities i.

• Normal line width of excitation lines much greater than this line width • Monochromator cannot be used to select λ range in AA (bandwidth ≈ few tenths of a nm).Linewidth of Atomic Transitions • Natural linewidth of an absorption spectrum is very small (10−4Å) 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.13 . Chapter 8&9 .

the excited atoms emit a characteristic λ. Chapter 8&9 . The bandwidth of the source << sample linewidth since it is generated under conditions where there is less broadening.g. Increasing the voltage between the anode and cathode will control the current and thus total photon flux. e.SOURCES • • • • • • Solution to line width problem: Use atomic source of same material. For Na analysis Na vapor is used. Optimum current for each lamp (≈ 1-20ma). Atoms are excited by electrical discharge. The ion current to the cathode controls photon intensity. Hollow Cathode Tube : Hollow cathode made of the material needed is vaporized and emits radiation of the characteristic wavelength.14 .

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

is burned. Robinson. fuel. and oxidant to combustion area.16 .FLAME ATOMIZERS • Total consumption burner: Separate channels bring sample. • Sensitivity is greater than in a burner where the sample is not completely burned. All of the sample. that is carried into the burner. • extra turbulence in the flame from variations in droplet size increase noise. 267. p. Undergraduate Instrumental Analysis. Chapter 8&9 .

110. and oxidant mixed prior to entering flame.17 . Ewing. Instrumental Methods of Chemical Analysis. p. fuel. • Mixing baffles insure only fine mist makes it through to burner. Chapter 8&9 . • Turbulence drastically reduced by removing larger droplets.Premix (laminar flow) burner • Sample.

Merritt. detection limit is ≈ 100-1000x lower than with aspiration techniques. sample dried (evaporate solvent) at ≈ 110°C.ELECTROTHERMAL ATOMIZATION • • • • all of the sample used is atomized in furnace (electrothermal) atomizer. Chapter 8&9 .18 . Dean and Settle. p. only a few mL of solution is used.(2000-3000°C) comparison with flame atomization: Instrumental Methods of Analysis. Basic Principle: – – – – – sample container resistively heated to vaporize the metal atoms. Willard. ash sample called "burn off" (200300°C). atomization. 147 • • • interaction with sample matrix and electrode poorer reproducibility detection limits of 10−10-10−12g (or 1ppb) are possible.

drop size. propane. and acetylene.19 .g. Fuels: natural gas. Flame characteristics: Sample enters flame. butane. reduced and eventually oxidized. Chapter 8&9 .Air and O2 (low temperature flames). Optimum position for flame for many metals. Exact region of flame in which each of these occurs depends upon: flow rate. Zn. Cd) High T flames: difficult to reduce elements (e. alkaline earths). Pb. Oxidants.FUELS/OXIDANTS • • • • • • • • • • • Low T flames : easily reduced elements (Cu. N2O (high temperature flames). and oxidizability of sample. H2. is vaporized.

NaCl or KI).g. These have broad band absorption spectrum in flame since they are not reduced by it. – Detection system measures difference between two absorbance signals: AHCT = Asample + Abrdband while Acontinuum source = Abrd band. high salt content (e.g. Flame interferences nulled by comparing a blank with sample – Sample matrix is a problem. the amount of light reaching the detector is given by Beers Law: P = Po×10−εbC . Broad band in nature. Most common approach uses secondary continuum source (e. for example. Pemission is due to analyte emission in the flame eliminated from the absorbance by modulation of the light source: measures only AC levels. Pbackground.20 . Caused by. emission DC level. D2 lamp): – Each lamp (D2 and HCT) modulated but are 180° out of phase with each other. Pscattering: due to absorption by the flame or are induced by sample matrix and are independent of the analyte. will be absorbance of sample. Chapter 8&9 . several interferences can change this to: P = Po×10−εbC + Pemission − Pbackground − Pscattering.MEASUREMENT OF AA • • • • • • • • Ideally.

D2 Source Elimination of Background Chapter 8&9 .21 .

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

not always true making a calibration curve necessary. A = k×C.g. Al + Mg produces low results for Mg due to the formation of an Al/Mg oxide. • 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. e. 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. Chapter 8&9 . It can reduce the number of atoms made.ANALYTICAL TECHNIQUES • Beer's law.23 .

Determination of Nickel Content by AA 120 y = 5. 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 L was trapped by ion exchange.24 .00 mL. A plot of the results are shown below. 10.00 mL aliquots of this solution were analyzed by AA after adding a volume of 0.6x + 20 Absorbance Units 80 40 0 0 5 10 15 Volum e of Nickel Added(m L) Chapter 8&9 . Determine the concentration of the Ni in the river water.Sample Problem • The nickel content in river water was determined by AA analysis after 5.0700 µg Ni/mL to each.

Chapter 8&9 .25 Return to Slide 10 .

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