SCGS 6115 : Atomic Spectroscopic Analysis 2013

Tutorial 1 Topic: Atomic Spectroscopy

1. Define a. Atomic spectroscopy Atomic spectroscopy is the technique for determining the elemental composition of an analyte by its electromagnetic or mass spectrum. Several analytical techniques are available, and selecting the most appropriate one is the key to achieving accurate, reliable, real-world results. b. Absorptivity The proportionality constant in the Beers Law equation, A=abc, where b is the path length of radiation and c is the concentration of the absorbing species. Thus a has units of length-1 concentration -1. c. Transmittance The ratio of the power, P, of the beam of radiation after its has traversed an absorption medium to its original power often expressed as a percentage. Often expressed as a percentage:%T= (P/P0) x 100% d. Atomization Atomization is a process in which a sample is converted into gas-phase atoms or elementary ions. e. pressure broadening An effect that increases the width of an atomic spectral line which caused by collision among the atoms that result in slight variations in their energy. 2. What determines the natural line widths from atomic emission and absorption lines? How broad are these widths? Natural line widths in atomic spectroscopy are the widths of lines when only the uncertainty principle, and not Doppler or pressure broadening, contribute to the broadening. The widths are then determined by the lifetime of the excited state. 3. What are the factors which affect line broadening? Discuss each of the factors Factor that affect line broadening are:a. Natural Broadening: The natural line width of an atomic spectral line is determined by the lifetime of the excited state and Heisenbergs uncertainty principle. The shorter the lifetime, the broader the line and vice versa. Typical radiative lifetimes of atoms are on the order of 10-8s, which leads to natural line widths on the order of 10-5nm.

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SCGS 6115 : Atomic Spectroscopic Analysis 2013

b. Collisional/Pressure Broadening: collisions between atoms and molecules in the gas phase lead to deactivation of the excited state and thus broadening of the spectral line. The amount of broadening increases with the concentration (pressure) of the collision partners. Pressure broadening increases with increasing temperature. Collisional broadening is brightly dependent on the gaseous medium. For Na atoms in flames, such broadening can be as large as 3X 103nm. In energetic media, collisional broadening greatly exceeds natural broadening. c. Doppler Broadening: Doppler broadening results from the rapid motion of atoms as they emit or absorb radiation. Atoms moving toward the detector emit wavelength that are slightly shorter than the wavelength emitted by atoms moving at right angles to the detector. This difference is a manifestation of the well-known Doppler shift; the effect is reversed for atoms moving away from the detector. The effect is an increase in the width of the emission line. Doppler Effect also causes broadening of absorption lines. This type of broadening becomes more pronounced as flame temperature increases because of the increased velocity of atoms. Doppler broadening can be a major contributor to overall line widths 4. What is a transducer in an analytical instrument? Describe and discuss the types of transducers Transducers are the instruments which converts non-electric signals into an electric signal. Any transducer is based on a simple concept that physical property of a sensor must be altered by an external stimulus to cause that property either to produce an electric signal or to modulate an external electric signal. The transducers are classified into two main types: active transducers and passive transducers. The active transducer generates its own electrical voltage during conversion. Thus it does not require any battery supply for conversion Examples Solar cell when it is exposed to strong sunlight or any other light, it converts light energy into proportional DC voltage. Piezo electric crystal when it is subjected to changing pressure it produces proportional AC voltage.

In passive transducer, it requires external battery supply. It only changes its parameter during conversion like change in resistance or capacitance etc. Examples LDR (Light Dependent Resistor) when LDR is exposed to light, its resistance decreases (less than 10W) proportionally & when it is dark its resistance is very high (several MW).

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SCGS 6115 : Atomic Spectroscopic Analysis 2013

Thermistor when thermistor is exposed to heat its resistance decreases and when it is cooled its resistance increases.

According to working principle of transducers they are classified into four main types Mechanical transducers for example strain gauge, LVDT etc. Thermal transducers for example thermistor, thermocouple etc. Magnetic transducers for example search coil etc. Radiation transducers for example solar cell, photo diode etc.

5. Explain what is meant by spectral, chemical, ionization interferences. Spectral Interferences: A spectral interference can occur when an absorbing wavelength of an element present in the sample but not being determined falls within the bandwidth of the absorption line of the element of interest. The results of the determination will then be erroneously high, due to the contribution of the interfering element to the atomic absorption signal. When multi element lamps are being used, a combination of elements may exist that will generate the possibility of a spectral interference. The slit width normally used with single-element lamps may be large enough to pass an absorbing wavelength of another element present in a multi element lamp. This can be overcome by using a smaller slit or selecting an alternate wavelength. Chemical Interferences: The most common interferences in atomic absorption are chemical interferences. If the sample being analyzed contains a thermally stable compound with the analyte that is not totally decomposed by the energy of the flame, a chemical interference exists. As a result, the number of atoms in the flame capable of absorbing light is reduced. Chemical interferences can normally be overcome or controlled in two ways: the use of a higher temperature flame or the addition of a releasing agent to the sample (or standard) solution. A releasing agent, or competing cation, when added to the sample solution will preferentially react with the interferent releasing the analyte and thus removing the interference. A higher temperature flame will provide additional energy to break down a compound which is stable in a lower temperature flame. Ionization Interferences: Ionization interferences occur when the flame temperature has enough energy to cause the removal of an electron from the atom, creating an ion. As these electronic rearrangements deplete the number of ground state atoms, atomic absorption is reduced. Ionization interferences can be controlled by the addition of an excess of an easily ionized element to the blank, standards, and samples. For this purpose, the alkali metals (K, Na, Rb, Cs) which have very low ionization potentials, are normally used. 6. The emission intensities of sodium lines are greater in a sample solution which contains KCl than when this compound is absent. Suggest an explanation

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SCGS 6115 : Atomic Spectroscopic Analysis 2013

In the presence of KCI, ionization of sodium is suppressed because of the high concentration of electrons from the ionization of potassium. In the absence of KCl, some of the Sodium atoms are ionized, which leads to a lower emission intensity for atomic Na.

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SCGS 6115 : Atomic Spectroscopic Analysis 2013

Reference : Douglas A. Skoog, D. M. ( 2004). Fundamentals of Analytical Chemistry . Canada: Thomson Brooks/Cole. Elmer, P. (1996). Analytical Methods for Atomic Absorption Spectroscopy. USA: Perkin Elmer. Michael, R. G. (n.d.). RMGLab. Retrieved September 20, 2013, from http://chemweb.chem.uconn.edu/: http://chemweb.chem.uconn.edu/teaching/chem232/Lecture_Notes/AT_reviewRGM.pdf Vidyasagar. (n.d.). Vidyasagar Sirs Web. Retrieved September 20, 2013, from http://vsagar.com/2011/12/what-is-transducer-how-it-is-used-in-electronic-circuits/

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