Department of Chemistry Analytical and Environmental Chemistry (CH-204) Atomic Spectroscopy Michael J. Hynes

Atomic Spectroscopy Lecturer Michael J. Hynes Texts (1) Quantitative Chemical Analysis , by Daniel C. Harris Pub. Freeman. Chapter 21 (4th Edition) (2) Atomic Absorption and Emission Spectroscopy by E. Metcalfe & F.E. Prichard, Pub. Wiley (ACOL series). (3) Most Analytical Chemistry Textbooks. (4) Handout

Principle of Atomic Absorption pectroscopy Atomic Absorption (AA) is based on the principle that a ground state atom is capable of absorbing light of the same characteristic wavelength as it would emit if excited to a higher energy level. In flame AA, a cloud of ground state atoms is formed by aspirating a solution of the sample into a flame of a temperature sufficient to convert the element to its atomic state. The degree of absorption of characteristic radiation produced by a suitable source will be proportional to the population of ground state atoms in the flame, and hence to the concentration of the element in the analyte.

Heat Compound Atoms Spectra of atoms consist of SHARP LINES. Each element has a characteristic spectrum. Due to sharpness of lines, there is little overlap between the spectral lines of different elements. Therefore, there is little interference. Atomic Spectroscopy High Sample Vapour Temperature Measure absorbance or emission of the atomic vapour. Atomic spectroscopy deals with atoms. Fe2+ and Fe3+ will not be distinguished.

Sensitivity Atomic spectroscopy is very sensitive for most elements. Concentrations at the ppm level may be routinely determined using flame atomisation. Using electrothermal atomisation, concentrations at the ppb may be determined. 1 ppm = 10-6g/g or 1g/g The density of dilute aqueous solutions is approximately 1.00 so that: 1 g/g of aqueous solution = 1g/ml = 1 ppm 1 ppm Fe = 1 x 10-6 g Fe/ml = 1.79 x 10-5 mol dm-3 1 ppm = 1 second in 11.6 days 1 ppb = 1 second in 31.7 years.

Atomic Absorption Spectroscopy Absorbance = -log(It/I0) Io = incident radiation (on sample) It = transmitted radiation. Atomic Emission Spectroscopy Absorbance = -log(It/I0) I0 =intensity of radiation reaching detector in the absence of sample. It = intensity of radiation reaching detector when sample is being aspirated.

Both methods are used to determine the concentration of an element in solution. Both methods use a standard curve. Difference between UV and IR spectroscopy is that sample must be atomised. Sample may be atomised by: (1) A flame (2) Electrically heated furnace (3) A Plasma

Molecular Absorption Band x Abs W1/2 x  Band Width = W1/2 = width of band at half the height W1/2 = 0.003 nm Abs 25 nm+   Molecular Absorption Band Atomic Vapour Absorption Band

Atomic Absorption and Emission Lines Resonance Lines E3(Excited state) E2(Excited state) E1(Excited state) E Eo(Ground state) Absorption Emission Most Intense Line 3 Absorption Lines 6 Emission lines E = E1 - E0 = h = hc/

Comparison of the atomic emission spectrum of silicon compared with the molecular absorption spectrum of ethanal.

Laminar Flow Burner

EXAMPLES OF FLAME TEMPERATURES Acetylene flow rate: 1000 ml/minute Air flow rate: 5000 ml/minute Sample uptake: 2 ml/minute  80% of sample goes to waste. Therefore, dilution factor =  15,000 Highly inefficient!

Effect of temperature in atomic spectroscopy Boltzman Distribution E1 (g = 2) (Excited state) E1 E0 (g = 1) (Ground state) g is the multiplicity Na E1 = 3.37 x 10-19 J/atom At 2600 K At 2610 K N1/No = 1.74 x 10-4

Effect of Temperature on Sodium Atoms The effect of a 10 K temperature rise on the ground state population is negligible (0.02 %). In the excited state the fractional change is So!

Effect of Temperature Small changes in flame temperature (10 K) have little effect in atomic absorption but have significant effects in atomic emission spectroscopy. Must have good flame control in atomic emission spectroscopy.

Radiation Source Beer’s Law only applies to monochromatic radiation. In practice, monochromatic implies that the linewidth of the radiation being measured is less than the bandwidth of the absorbing species. Atomic absorption lines very sharp with an inherent linewidth of 0.0001 nm. Due to Doppler effect and pressure broadening, linewidths of atoms in a flame are typically 0.001 - 0.01 nm. Therefore, we require a source having a linewidth of less than 0.01 nm. Typical monochromator has a bandwidth of 1 nm i.e. x100 greater than the linewidth of the atom in a flame.

Hollow Cathode Lamp Used because of the requirement for a source of narrow lines of the correct frequency. Hollow Cathode lamp filled with argon or neon at a pressure of 130 - 170 Pa (1 - 5 torr)

Monochromator bandwidth (~100x greater than atomic lines

Hollow Cathode Lamp

Reactions in the Hollow Cathode Lamp Apply sufficiently high voltage between the cathode and the anode: (1) Ionization of the filler gas: Ne + e- = Ne+ + 2e- (2) Sputtering of the cathode element (M): M(s) + Ne+ = M(g) + Ne (3) Excitation of the cathode element (M) M(g) + Ne+ = M*(g) + Ne (4) Emission of radiation M*(g)  (M(g) + h

Hollow Cathode Lamp The cathode of the hollow cathode lamp (HCL) contains the element being analysed. Therefore the atomic radiation emitted by the HCL has the same frequency as that absorbed by the analyte atoms in the flame or furnace. The linewidth from the HCL is relatively narrow (compared to linewidths of atoms in the flame or furnace) because of low pressure in lamp and lower temperature in lamp (less Doppler broadening). Thus the linewidth from the HCL is nearly “monochromatic” (vs sample). Different lamp required for each element although some are mulit-element.

Hollow Cathode Lamp - The Filler Gas

Electrothermal Atomisation - Graphite Furnace Sample holder consists of a graphite tube. Tube is heated electrically Beam of light passes through the tube. Offers greater sensitivity than flames. Uses smaller volume of sample typically 5 - 50 l (0.005 - 0.05 ml). All of sample is atomised in the graphite tube. Atomised sample is confined to the optical path for several seconds (residence time in flame is very short). Uses a number of stages as shown on next slide.

Stages in a Graphite Furnace Typical conditions for Fe: Drying stage: 125o for 20 sec Ashing stage 1200o for 60 sec Atomisation 2700o for 10 sec Requires high level of operator skill. Method development difficult.

Schematic Diagram of a Graphite Furnace HCL

Advantages and Disadvantages of Flame AAS equipment relatively cheap easy to use (training easy compared to furnace) good precision high sample throughput relatively facile method development cheap to run Disadvantages lack of sensitivity (compared to furnace) problems with refractory elements require large sample size sample must be in solution

Advantages and Disadvantages of Electrothermal Atomisation very sensitive for many elements small sample size Disadvantages poor precision long cycle times means a low sample throughput expensive to purchase and run (argon, tubes) requires background correction method development lengthy and complicated requires a high degree of operator skill (compared to flame AAS)

Monochromator The operation and sensitivity of the atomic absorption spectrometer spectrometer depends on the spectral band width of the resonance line emitted by the primary radiation source (the hollow cathode lamp). The function of the monochromator is to isolate the resonance line from non-absorbing lines close to it in the source spectrum and from background continua and molecular emissions originating in the flame. Hollow cathode lamps emit a number of lines, in the case of multi-element lamps, the number can be quite large and it is necessary to isolate the line of interest.

Detector/Measuring System The intensity of the line source is measured with a photomultiplier, which produces an electrical signal proportional to the intensity of the incident light. This signal is amplified and processed electronically to produce an output which on older instruments was read on a digital or analogue meter in either absorbance or concentration mode. In modern instruments, the output is usually displayed on the computer screen of the PC controlling the instrument. In order to eliminate the unwanted emissions from the flame, the light source is modulated by a chopper which is located between the hollow cathode lamp and the flame. The amplifier which modifies the signal from the photomultiplier is tuned in to the same frequency . (Alternatively, the hollow cathode lamp may be modulated by applying an AC voltage at say 50 Hz.).

A B

Interferences Interference is any effect that changes the signal when analyte concentrations remain unchanged. While atomic absorption spectroscopy is relatively free from interferences, there are a number of interferences which must be dealt with.

Spectral Interference This refers to overlap of analyte signals with signals originating from other elements in the sample or with signals due to the flame or furnace. Example: Al 308.216 nm V 308.211 nm Solution: Separate elements or use a different line (which may be less sensitive).

Chemical Interference Formation of Stable or Refractory Compounds Elements that form very stable compounds are said to be refractory because they are not completely atomised at the temperature of the flame or furnace. Solution Use a higher flame temperature (nitrous oxide/acetylene) Use a release agent Use protective chelation

Examples Determination of calcium in the presence of sulfate or phosphate (e.g. in natural waters) 3Ca2+ + 2PO43- = Ca3(PO4)2 (stable compound) Release agent Add 1000 ppm of LaCl3 2LaCl3 + Ca3(PO4)2 = 3CaCl2 + 2La(PO4) CaCl2 readily dissociates Protective chelation Ca3(PO4)2+3EDTA = 3Ca(EDTA) + 2PO43- Ca(EDTA) dissociates readily.

Ionisation Interference M(g)  M+(g) + e- A problem in the analysis of alkali metal ions at low flame temperatures and other elements at higher temperatures. Because alkali metals have the lowest ionisation potentials, they are most extensively ionised in flames. At 2450 K and a pressure of 0.1 Pa, sodium is 5% ionised. Potassium is 33% ionised under the same conditions. Ionised atoms have energy levels which are different to the parent atoms therefore the analytical signal is reduced.

Solution Add an ionisation suppressor Add an easily ionised element such as Cs. Add 1000 ppm of CsCl when analysing Na or K. Cs is more readily ionised than either Na or K. This produces a high concentration of electrons in the flame.

Matrix effects The amount of sample reaching the flame is dependent on the physical properties of the solution: viscosity surface tension density solvent vapour pressure. To avoid differences in the amount of sample and standard reaching the flame, it is necessary that the physical properties of both be matched as closely as possible. Example: Analysis of blood

Non-Atomic Absorption Non-atomic absorption is caused by molecular absorption or light scattering by solid particles in the flame. The absorption measurement obtained with a hollow cathode lamp is the sum of the atomic absorption and the non-atomic absorption. The interference is corrected for by making a simultaneous measurement of the non-atomic absorption using a continuum source (usually deuterium) this is called background correction

Operational Parameters Sensitivity the concentration of an element which will reduce the transmission by 1% This corresponds to an absorption of 0.00436

Calculations For an absorbance of 1.0 we require 1.0/0.00436 = 230 times the sensitivity. For Cu, sensitivity = 0.05 ppm For an absorbance of 1 we require a concentration of 11.5 ppm. Using scale expansion of 10 we can usually obtain an absorbance of 1 using a 1 ppm solution of copper.

Detection Limit The concentration of an element that gives a signal equal to three times the peak to peak noise level of the baseline. Measure the baseline while aspirating a blank solution.

Terms to understand in atomic spectroscopy (1) Atomic absorption spectroscopy Atomic emission spectroscopy Atomisation Background correction Boltzman distribution Chemical interference Detection limit Graphite furnace Hollow-cathode lamp

Terms to understand in atomic spectroscopy (2) Inductively coupled plasma Ionisation interference Ionisation suppressor Matrix Matrix modifier Nebulisation Premix burner Releasing agent Spectral interference

Applications of AAS Agricultural analysis Clinical and biochemistry soils plants Clinical and biochemistry whole blood, plasma and serum Ca, Mg, Li, Na, K, Cu, Zn, Fe etc. Metallurgy ores, metals and alloys

Applications of AAS Lubricating oils Greases Ba, Ca, Mg and Zn additives Greases Li, Na, Ca

Applications of AAS Water and effluents Food Animal feedstuffs many elements e.g. Ca, Mg, Fe, Si, Al, Ba Food wide range of elements Animal feedstuffs Mn, Fe, Co, Cu, Zn, Cr, Se Medicines range of elements