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Atomic Emission Spectrometry

In emission spectroscopy/spectrometry, a sample is excited by absorbing the thermal or electric energy instead of electromagnetic radiation. The radiation emitted by the excited sample is studied for both qualitative and quantitative analysis of metals. Types of spectra: i)Emission spectra ii)Absorption spectra

i)Emission spectra: -Upon heating of a substance to high temperature by thermal or electric means, the substance relaxes releasing the light . -The emitted radiation is passed through a prism or a grating & examined directly with a spectroscope. -The spectrum thus obtained is Emission spectrum Types of emission spectra: i)Continuous spectra ii)Band spectra iii)Line spectra i)Continuous spectra -Incandescent solid like iron or carbon emits a continuous spectra without sharp lines or discrete bands. ii)Band spectra -It is given by the excited molecules. -A band spectrum consists of close group of lines. iii)Line spectra -A line spectra consists of discrete irregular spaced lines. -Substances in atomic state give this spectra. -It depends upon the type of atom.

-A number of sources for sample atomization & excitation are employed. -These sources are flames/furnaces, electric arc & sparks, plasma etc. -Plasma, arc & spark emission spectrometry are advantageous than the flame emission & electro-thermal absorption methods. (low chemical interference;spectra of dozens of elemen,t simultaneously determination of trace amount of elements, even from refractory oxides of boron, phophorus etc; determination of nonmetals e.g. chlorine, bromine,iodine, suphur etc, handle concentration of several order of magnitudes) -On the basis of sources, atomic emission spectroscopy can be divided into three types 1)Flame based emission spectroscopy 2)Arc & spark based emission spectroscopy. 3)Plasma based emission spectroscopy 1)Flame based emission spectroscopy (Flame photometry) -Defined as the measurement of intensity of the light emitted. -The light emission takes place when alkali or alkaline earth metal is introduced into the flame. -So that it is flame emission spectroscopy. -Elements present determine the colours of the flame & emission spectra.

Theory/Principle: -The compounds of alkali & alkaline earth metals can be thermally dissociated in a flame. -Some of the atoms produced are excited to a higher energy level(0.01-1%). -Upon returning to the ground state, emission of radiation takes place which lies mainly in visible region of the spectrum. -Wavelength of the emitted radiation is specific for that element. -The intensity of the radiation is the function of the concentration of the element analysed. Resonance wavelengths & colours of emitted radiations of alkali/alkaline earth metals: --------------------------------------------------------------Element Emission wavelength(nm) Flame colour --------------------------------------------------------------Sodium(Na) 589 Yellow Potassium(K) 766 Violet Barium(Ba) 554 Lime green Calcium(Ca) 622 Orange Lithium(Li) 670 Red -----------------------------------------------------------------------------

Instrumentation/operation:

-Air at a given pressure is passed into a nebulizer/atomizer. -the suction this produces, draws a solution of the sample into the atomizer. -where it joins the air stream as a fine mist and passes into a mixing chamber where large droplets fall out and flow to waste through the drain tube. -fine mist mix with the fuel gas supplied. -The mixture at a given pressure passes into the burner. -Radiation from the resulting flame passes through a lens, and finally through an optical filter. -which permits only the radiation characteristic of the element under investigation to pass through the photocell. -The output from the photocell is measured on a suitable digital read-out system. Applications: i)Qualitative ii)Quantitative i)Qualitative: -Solutions of any alkali/alkaline earth metals shows their characteristic radiation colours in flame & their digital out put(when the respective filters are used). ii)Quantitative -For alkali/alkaline earth metals(having E less than 3ev)

a)Direct comparison or single point standardisation technique. b)Direct calibration. c)Standard addition -for determining very low concentrations of the elements present in the sample. -for overcoming anionic or physical interferences from certain substances in the sample that affect the efficiency of the emission of the element. Examples of flame photometric analysis: -Sodium/potassium in ORS. -Sodium/potassium/calcium in haemodialysis solution. -Sodium chloride injection etc. -Lithium carbonate capsules/tablets 2)Arc & spark based emission spectroscopy. -Arcs and sparks are generated by high voltage electricity. -The spectra(by arc & sparks) permits the qualitative and quantitative determination of metallic elements. -Receival , processing & recording of the signals/ spectra from the arc & spark sources are done by suitable spectrograph. -Electrodes are graphite rods. Upper is with pointed end & lower with a hollow out. -Small amount of sample is kept in the hollow of the lower rod(Anode). -Arc or spark is created between the electrodes by bringing them in contact. -or both electrodes are short-circuited by a third rod. a)Arc based emission spectroscopy. b)Spark based emission spectroscopy.

a)Arc based emission spectroscopy. -The source is called low-voltage D.C. arc. -Requires D.C. of 110-250volts. -Requires a regulating R to control the current(2-12A). -Requires an inductance L, helps to steady the arc & maintain a more constant voltage. -Arc temperature is 4000-8000K

b)Spark based emission spectroscopy: -The source is called high-voltage A.C.Spark. -It may be the simplest excitation source for many quantitative application. -It imparts lesser heating effects. So that: -Its less sensitive than D.C. Arc source. -But more reproducible & stable than the Arc & less material consumed.

-It is adapted for the analysis of low-melting materials. -High voltage transfer of 15KV across two electrodes gives spark. -Arc is generated at a distance 0.5-3mm -Condenser C is used to increase the current.

Equipment for emission analysis (D.C.Arc & A.C. Spark) Spectrographic analysis.

-Essential parts of a spectrograph are a slit, an optical system and a camera for recording. -The light from the source of radiation passes through the slit. -Then through the optical system. -An image or emission spectrum is recorded on a photographic plate. -Image is produced for each radiation having a specific wavelength. -The result is a series of vertical line images. -The lines constitute the spectrum of the element being investigated. -The spectrograph is provided with a scale graduated in wavelength. -The scale can be illuminated & printed directly on the spectrogram. -The optical system transmits radiation of both UV/Vis region(200-1000)nm. -The recorded photographic plate is developed and studied. For Arc & Spark emission spectroscopy: i)Qualitative spectrographic analysis: -The recorded photographic plate is developed and studied. -These are compared with that of RU (raies ultimes) mixture(Std. mixtures of metals in low conc.). -At least 55 elements can be identified under the normal condition of excitation. i)Quantitative spectrographic analysis: -The concentration of the unknown is measured from the blackening of the plate for certain lines in the spectrum. -The density of the image of the spectral line ideally proportional to concentration of the target element in the sample. -Microphotometer is used to measure the intensity of blackening.

3)Plasma based emission spectroscopy

-Developed largely in 1970s. -A plasma is an electrically conducting gaseous mixture containing a significant concentrations of cations & electrons (conc. both are equal, so that the net charge of plasma is zero). -In a plasma, over 1% of the total atoms in a gas are ionised. -Gas(usually argon) is ionised by the influence of a strong electric field. -Argon ions formed in plasma depends upon an external source to maintain the temperature. -Electric field is either created by D.C. or by radio frequency(R.F.). -Both types of discharge produce a plasma:

i)Direct current plasma(DCP) ii)Inductively coupled plasma(ICP) -Plasma sources operate at(7,000K-15,000K) -Measurement capability extends to ppb level. ii)Inductively coupled plasma(ICP)

-It comprises three concentric silica quartz tubes with opening at the top. -The argon stream carrying sample aerosol passes through the central tube. -For the initiation, the flowing argon is ionised by the spark from Tesla coil. -The ionised argon is electrically conducting.

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Sample introduction: -Sample usually in solution form. -Carried into the hot plasma by a nebuliser system. -The sample is forced into the mixing chamber at a flow rate of 1L/min. by the peristaltic pump. -It is nebulised by the stream of argon at flowing at about 1L/min. ICP instrumentation: Two basic types of instruments: 1)Simultaneous multi-element spectrometer: 2)Sequential spectrometer. 1)Simultaneous multi-element spectrometer:

-The radiation from plasma is reflected by a concave reflecting grating. -The component wavelengths reach a series of exit slit. -These slits isolate the selected emission lines for specific elements. -The light from the exit slit is directed to fall on the photomultiplier tube. -One for each spectral line.

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-The amplified light is sent to read-out system. -Voltage is converted into the Conc. of each element present. -This instrument capable of analysing 60 elements simultaneously. Applications of ICP: 1)Used in the trace metal analysis: e.g. Copper, iron, manganeses, magnesium & calcium. 2)Estimation of trace amount of aluminum in blood. 3)Estimation of trace amount of copper in the brain tissue. 4)Estimation of sodium in the breast milk.