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Concepts, Instrumentation, and Techniques in ICP OE Spectrometry

By Charles B. Boss and Kenneth J Fredeen Chapter 1
Quantitative (concentration) is related to the amount of electromagnetic radiation that is emitted or absorbed Qualitative (what elements are present) is related to the wavelengths at which radiation is absorbed or emitted

(a,b) excitation c excitation d ionization e emission (e,f,g) atom emission

Figure 1-2 Energy level diagram depicting energy transitions (energy difference) = E = h =hc as E : h = Planks constant = frequency of wavelength c= speed of light

Every element has its own characteristic set of energy levels and thus its own unique set of absorption and emission wavelengths. UV / visible region (160 800nm) are the most commonly used region Atomic Absorption Spectrometry (AAS) light of a wavelength characteristic of the element of interest is shone through this atomic vapor. Some of the light is then absorbed by the atoms of that element. The amount of light that is absorbed by these atoms is then measured and used to determine the concentration of that element in the sample Optical Emission Spectrometry (OES) the sample is subjected to temperatures high enough to cause not only dissociation into atoms but cause significant amounts of collisional excitation (and ionization) of the sample atoms to take place. Once the atoms or ions are in their excited states, they can decay to lower states through thermal or radiative (emission) energy transitions. In OES intensity of the light emitted at specific wavelengths is measured and used to determine the concentrations of the elements of interest. Atomic Mass Spectrometry (AMS) measures the number of singly charged ions from elemental species from within a sample. A quadrapole MS separates the ions of various elements according to their mass to charge ratio. Plasma atomization is any form of matter that contains an appreciable fraction (>1%) of electrons and positive ions in addition to neutral atoms, radicals and molecules. Plasma characteristics include electrical conductivity and sensitivity to magnetic fields OES plasma are highly energetic, ionized gases. They are usually produced in inert gasses. The plasma discharges are considerable hotter than flames and furnaces and thus, are not only used to dissociate almost any type of sample but also to excite and ionize the atomic and ionic emission

Lab Notes

Anton Dias Perera

Last Revised: 08/18/2011

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Chapter 2
RF power (typically 700 to 1500 watts) is applied to the load coil. Most ICP instruments operate at 27 or 40MHz Inductive coupling - Adding energy to the electrons by the use of a coil The breaking down of argon gas to plasma containing argon atoms, electrons and argon ions is known as ICP discharge

Figure 2.2. Cross section of a ICP torch and load coil depicting an ignition sequence. A- Argon gas is swirled through the torch B RF power is applied to the load coil. C A spark produces some free electrons in the argon. D The free electrons are accelerated by the RF fields causing further ionization and forming plasma. E the sample aerosol-carrying nebulizer flow punches a hole in the plasma The body of the dreadnought is called the induction region (IR) because this is the region in which the inductive energy transfer from the load coil to the plasma takes place. This is also the area where the most of the white light, called argon continuum, is emitted

Figure 2.3. Zone in the ICP. IR Induction Region PHZ Preheating Zone IRZ Initial Radiation Zone NAZ Normal Analytical Zone Desolvate vaporization atomization (this processes takes palace predominantly in the PHZ) excitation + ionization (IRZ and NAZ) ICP Advantages Center of ICP is about 6400K while flames and furnaces operational temperature tops out at 3300K High ICP temperature reduces or eliminates chemical interferences found in flames and furnaces Sample exposed to high temperature for relatively longer time ( ~ 2ms) more uniformly Given aerosol introduction method, sample does not interfere with energy transfer from load coil to discharge

Lab Notes

Anton Dias Perera

Last Revised: 08/18/2011

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For rough quantitation (10%), it is recommended that an elements concentration should be at least 5 times higher than the detection limit. For accurate quantitation (2%), the concentration should be greater than 100 times the DL Elements that are not usually determined at trace levels Elements that are naturally entrained into the plasma from sources other than original sample. i.e. Argon, CO2 contamination often found in argon gas, H and O from water, C if organic solvents were used, H,N,O,C due to natural air Very high excitation energy requirements. i.e. halogens (Cl, Br, I) Man-made elements which are typically so radioactive or short-lived The upper limit of linear calibration for ICP-OES is usually 10 to 10 times the DL for a particular emission line. Linear Dynamic Range - the range of concentrations from DL to the upper limit Precision of analysis is usually in the 1% or less RSD range when the concentration is greater than 100 times the DL
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Chapter 3

Lab Notes

Anton Dias Perera

Last Revised: 08/18/2011