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Pengenalan Analisis Dengan Metode Spektroskopi Sejarah istilah spektroskopi berdasarkan pada cabang ilmu pengetahuan alam dimana

cahaya(dalam hal ini radiasi sinar tampak) telah diuraikan menjadi komponen panjang gelombang untuk menghasilkan spektra. Sifat Radiasi Elektromagnetik Radiasi elektro magnetik merupakan tipe energi berupa terusan gelombang berjarak dengan kecepatan yang sangat besar. Banyak sifat dari radiasi elektromagnetik dapat dijelaskan dengan sangat baik dengan menggunakan model gelombang klasik seperti parameter panjang gelombang, frekwensi, kecepatan dan amplitudo. Model gelombang penentu nilai untuk menghubungkan fenomena absorbsi atau emisi pancaran energi. radiasielektromagnetik harus bisa ditampilkan sebagai urutanurutan partikel energi yang berlainandisebut foton,dengan energi foton menjadi sesuai dengan frekwensi radiasi. Sifat Gelombang Untuk banyak tujuan, radiasi elektromagnetik sangat baik di gambarkan sebagai sebuah medan listrik dimana undergoes sinusoidal oscllation in space. Gambar 8-1adalah gambarandua dimensi sinar monokromatik,bidang polarisasi radiasi. Istilah bidang polarisasi menyatakan secara tidak langsunggetaran medan listrik pada bidang tunggal. Medan listrik dinyatakan sebagai vektor yang panjangnya sesuai dengan kuat medan. Parameter Gelombang Dalam gambar 18-1, amplitdo A dari gelombang sinusoidal menunjukan bahwa panjang vektor elektik berada pada gelombang maksimum. Waktu yang dibutuhkan untuk perjalanan titik maksimum (atau minimum) lembah titik pertemuan jarak disebut periode (p) dari radiasi. Frekuensi (v) adalah jumlah getaran medan per detik dan ini setara dengan 1/p.

Wave properties For many purposes, electromagnetic radiation is conveniently pictured as an electric field that undergoes sinusoidal oscillations in space. Figure 18-1 is a two dimentional representation of a beam of monocromatic ( that is, single wavelength ), [plane =bidang] polarized radiation. The term plane polarized implies that the ocsilation of the electric field are in a single palne. The electric field is represented as a vector whose length is proportional to the field strength. The abscissa in this plot is either time as the radiation passes a fixed point in space or distance. Note that the direction in which the field osillater is perpendicular to the direction in which the radiation is being propagated. Wave parameters. In figure 18-8, the amplitude A of the sinusoidal wave is defined as the length of the electrical vector at the maximum in the wave. The time required for the passage of the successive maxima ( or minima) trought a fixed point in space is called the period p of the radiation. The frequency v is the number of oscillations of the field per second and is equal to 1/p. Its importen to realize the frequency is the termined by the source and remains invariant regardless of the medium draversed by the radiation. In contrast the velocity of progation v1, the rate at which the wave front moves trough a medium, is dependence upon both the medium and the frequency; the subscript i is employed to indicate this frequency dependence between successive maxima or minima of a wave. Multiplication of the frequency in waves per second by the wavelength in centimeter gives the velocity of propagation in centimeter per second: In a vacuum, the velocity of radiation propagation becomes independent of wavelength and is at its maximum. This velocity, which is given the symbol c, has been determined to be 2.99792 X 10 10 cm/s. The velocity of radiation in air differs only slightly from c (it is about 0.03 % less). Thus, to three significant figures. Equation 18-2 is equally applicable in air or vacuum: The rate of propagation of radiation is less than c in a medium containing matter because the electromagnetic field of the radiation interacts with the electrons in the atoms or molecules of the medium and is slowed as a consequence. Since the radiant trequency is in variant and fixed by the source, the wavelength of radiation must descrease as it passes from a vacuum to a medium containing matter (Equation 18-1). This effect is illustrated in figure 182 for a beam of visible radiation. Note that the wavelength shortens nearly 200 nm, or more than 30% as the radiation passes from air into glass; a reverse change occurs when the radiation again enters air. The wave number , defined as the wavelength in centimeters (1/), iss yet another way of describing electromagnetic radiation. Or dinarily, the unit for is cm-1, which is the number of waves of a particular frequency in a distance of 1 cm. Radiant power and intensity

The power P of radiation is the energy of the beam that reaches a given area per second: the intensity I is the power per unit solid angle. These quantities are related of the square of the amplitude A (figure 18-1). Although it is not strictly correct to do so. Power and intensity are often used synonymously. The particle properties of radiation The energy of electromagneric radiation To understand many of the interaction between radiation and matter, it is necessary to postulate that electromagnetic radiation is made up of packrets of energy called photons (or quanta). The energy of a photon depends upon the frequency of the radiation and is given by Where isplancks constant (6.63 X 10-34 Js). In terms of wavelength and wavenumber,

Note that wave number, like frequency, is direcly proportional to energy. The electromagnetic spectrum The electromagnetic spectrum encompasses an anormous range of wavelength and energies. For example, an X-ray photon ( ) is approximately 10.000 times more energetic than a photon emitted by an incandescent tungsten wire( ) and 1011 times more energetic than a photon in the radiation frequency range. The major divisions of the electromagnetic spectrum are depicted in the color plate located inside the front cover of the book. Note that both the frequency and the wavelength scales are logarithmic; note also that the region to which the human eye is perseptive (the visible spectrum) is but a minute part of the whole spectrum. Such diverse radiation as gamma rays or radio waves differ from visible light only the matter of frequency and hance, energy. Figure 18-3 indicates the regions of the spectrum that the useful for analytical spectroscopy and the molecule or atomic transition responsible for absorbtion or emission of radiation in each region. Absorption of radiation In spectroscopic nomenclature, absorption is a process in which a chemical species in a transparent medium selectively aitenuates (decreases the intensity of) certain frequencies of electromagnetic radiation. According to quantum theory, every elementary particle (atom, ion or molecule) has a unique set of energy states, the lowest of which is the ground state; at room temperature, most elementary particles exist in their ground state. When a photon of radiation passes near an elementary particle, absorption becomes probable if (and only if) the energy of the photon matches exacly the energy difference between the ground state and one of the higer energy state of the particle. Under these circumstances, the energyof the photon is transferred to the atom, ion, or molecule, converting it to the higher energy state, which is termed an excited

state. Excitation of a species M to its excited state M* can be depicted by the equation M+ hv M* After a brief period (10-6 to 10-9 ), the excited species relaxed to its original, or ground state, transferring its excess energy to other atoms or molecules in the medium. This process, which causes a small rise in temperature of the surroundings, is describe by the equation M* M + heat Relaxation may also occur by photochemical decomposition of M* to form new species or by the fluorescent or phosphorescent reemission of radiation. It is important to note that the lifetime of M* is so very short that its concentration at any instant is ordinarily negligible. Furthermore, the amount of thermal energy released during relaxation is usually so small as to be undetectable. Thus, absorption measurements have the advantage of creating minimal disturbance of the system under study. The absorbing characteristics of a species are conveniently described by meansof an absorption spectrum, which is a plot of some function of the attenuation of a beam of radiation versus wavelength, frequency, or wavenumber. Ultraviolet and visible absorption spectra are usually obtained on a gaseous sample of the analyte or on a dilute solution of the analyte in a transpatent solvent. Atomic absorption When a beam of polychromatic ultraviolet or visible radiation passes through a medium containing gaseous atoms, only a few frequencies are attenuated by absorption, and the spectrum is made up of a number of very narrow (about 0.005 nm) absorption line. Figure 18-4a is an ultraviolet/visible absorption spectrum for gaseous sodium atoms. The ordinate is absorbance, which is measure of the degree of attenuation of the beam (section 18C-4) Figure 18-4b is a partial energy diagram for sodium showing the transition responsible for the three absorption lines in (a). The transitions involve excitation of the single outer electron of sodium from its room temperature or ground state 3s orbital to the 3p,4p and 5p orbitals. These excitations are brought on by absorption of photons of radiation whose energies exactly mach the differences in energies between the excited states and the 3s ground state. The energy difference between the 3p and the 3s orbitals in figure 18-4b is 2.107 eV. Calculate the wavelength of radiation that would be absorbed in exciting the 3s electron to the 3p state (1 eV= 1.60 X 10-19J). Rearranging equation 18-4 give

Absorption spectra for the alkali metal atoms are a good deal simpler than those of elements with additional outer electrons. The transition metal

atomic spectra are particularly rich in lines with some elements exhibiting several thousand lines. Molecular absorption Figure 18-5a is a partial energy level diagram that depicts some of theprocesses occur when a polyatomic species absorbs infrared, visible, and ultraviolet radiation. The energies E1 and E2, two of the several electronically excited state of a molecule, are shown relative to the energy of its groundstate E0. In addition, the relative energies of a few of the many vibrational states associated with each electronic state are indicated by the lighter horizontal lines. An idea as to the nature -=of vibrational states can be gained by picturing a bond in a molecule as a vibrating spring with atoms attached to both ends. With each vibration, the atoms periodically approach and move away from one another. The potential energy of such a system at any instant depents upon the extent to wich the spring is stretched or compressed. For an ordinaryspring, the energy of the system varies continuously and reaches a maximumwhen the spring is fullystretched fully compressed. In contrast, the energy of spring system of atomic dimensions can assume only certain discrete energies called vibrational energy levels. Some of the vibrational energy levels associated with each of the electronic states of a molecule are depicted by the lines lebeled 1,2,3,and 4 in figure 18-5a(the lowest vibrational state are significantly smaller than among energy levels of the electronic states ( typicaly, an other of magnitude smaller). Although they are not shown, a set of rational energy state is super imposed an each of the vibrational states shown in the energy diagram. The energy diffrences among these states are smaller than those among vibrational states by an other of magnitude. Infrared absorption. Infrared radiation generaly is not sufficiently energetic to cause electronic transition but can induce transitions in the vibrational and rotational states associated with the ground electronic state of the molecule. Four of these transition are depicted in the lower left part of figure 18-5a. For absorption to accur, the source has to emit radiational of frequencies corresponding exactly to the energies indicated by the lengths of the four arrows; infrared radiation of only those four frequencies is then absorbed by a collection of these molecule. Absorption of ultraviolet and visible radiation The center arrow in figure 18-5a suggest that the molecules under considereration absorb visible radiation of five wavelengths, thereby promoting electrons to the five vibrational levels of the excited electronic level E1. Ultraviolet photonsthat are more energetic are required to produce the absorption indicated by five arrows to the right. As suggested by figure 18-5a, molecular absorption in the ultraviolet and visible regions consists of absorption bands made up of closely spaced line. (a real molecule has many more energy levels than shown here; thusthe typical absorption band cinsistsof a multitude of line). In a solution, the absorbing

species are surrounded by solvent, and the band nature of molecular absorption often becomes blurred because collisions tend to spread the energies of the quantum states, thus giving smooth and continuous absorption peaks. Relaxation processes As note earlier, the lifetime of an excited species is brief because several mecanisms exist whereby an excited atom or molecule can give up its excess energy and relax to its ground state. Two of the most important of these mechanisms, nonradiative relaxation and flourescencent, are illustrated in figure 18-5b and c. Two types of nonradiative relaxation are shown in figure 18-5b. Vibrational deaktivation or relaxation, depcted by the short wavy arrow between vibrational energy level, take place during collisions between excited molecules and molecules of the solvent. During the collisions, the excessvibrational energy is transferred to solvent molecules in a series of stepsas indicated in the figure. The gain in vibrational energyof the solvent is reflected in an increase in the temperature of the medium. Vibrational relaxation is such an efficient process that the average lifetime of an excited vibrational state is only about 10 -15 s. Nonradiative relaxation between the lowest vibrational level of an excited electronic state and the upper vibrational level of another electronic state can also occur. This type of relaxation, depicted by the two longer wavy arrows in Figure 18-5b, is much less efficient than vibrational relaxation so that the average lifetime of an electronic excited stateis between 10-6 and 10-9 s. The mechanism by whichthis type of relaxation occur are not fully of the medium. Figure 18-5c depicts another relaxation process: flourescence. Molecular fluorescence is discussed in section 18D-2 and 20C. Terms employed in absorption spectroscopy Table 18-1lists the common terms and symbols used in absorption spectroscopy. This momenclature is recommended by the american society for testing materials as well as the american chemical society. Column 3 contains alternative symbols encountered in the older literature. Because a standard nomenclature is highly desirable in order to avoid ambiguities, yhe reader is Important terms and symbols employed in absorption measurement Term and symbol Definition Alternative name and symbol Radiant power P,P0 Energy of radiation(in Radiation intensity I,I0 ergs) impinging on a 1cm2 area of a detector per second Absorbance A Optical density D; extinction E Transmitance T Transmission T Path length of radiation b l,d

Absorptivity Molar absorptivity

Extinction coefficient k Molar coefficient extinction

Urged to lern and use the recommended terms and symbols and avoid those in column 3. Transmittance Figur 18-6 depicts a beam of parallel radiation before and after it has passed through a layer of solution with a thickness cm and a concentration of an absorbing sspecies. As a consequence of interactions between the photons andabsorbing particles, the power of the beam is attenuated from P0 to P. The transmittance Toof the solution isdefined as the fraction of incident radiation transmitted by the solution: Transmittanceis often expressed as a percentage Absorbance The absorbance of a solution is defined by the equation Note that, in contrast to transmittance, the absorbance of a solution increases as the attenuation of the becomes of the beam becomes greater. The relationship between absorbance and concentration The functional relationship between the quantity a measured in an absorption method (A) and the quantity sought (the analyte concentration c) is known as beers law and can be writen Where is a proportionality constan called the absorptivity and is the path length of the radiation through the absorbing mediun. Since absorbance is a unitless quantity, the absorbtivity has units that render the right side of the equation dimention les s. When concentration in equation 18-7 is expressed in moles per liter and is in centimeters. The proportionality canstant is called the molar absorptivity and is given the special simbol . Thuse, has the units of Lcm-1mol-1 Beers law can be rationalized by concidering the fate ao a beam of parallel monochromatic radiation with power P0 after it enters a layer of absorbing matter( solid, liquid, or gass) at a normal angle, as shown in figure 18-7. After passing through a length of the material, which contains n absorbing particless ( atoms, ions or molecules). The power of the radiation is decreased to P as a result of absorption. Concider now a cross section of the layer that has an area S and an infinitesimal thickness dx and that contains dn absorbingm particles. Associated with each particle, we can imagin a surface at Where

which photon capture occurs. That is if a photon reaches one of these areas by chance, absorption follows imedietaly. The total projected area of these capture surfaces with in the section of thickness dx is the signated dS. The ratio of the capture area to the total area is then dS/S. On a statical average, this ratio represents the probability for photon capture with in the section The power of the beam entering the section Px is proportional to the number of photons per square cm per second, and dP x represents the quantity remuved per second with in the section. The fraction absorbed is than dPx/Px, and this ratio also equals the average probability for capture. The trem is given a minus sign to indicate that P undergoes a the crease. Thus Recall that dS is the suum of the capture areas fofr particles within the secctions, whics must be proportional to the number of particles, or Where is the numbers of particles and is a proportionality constant that can be called the capture cross section. Combining Equations 18-9 and 18-10 and intergrating over the interval between zero and n, we obtain

When the integrals are evaluted, we find Upon coverting to base -10 logarithmes and inferting the fraction to change the sign, we obtain Where is the total number of particles within the block shown in figure 18-7. The cross-sectional areas S can be expressed in terms of the volume of the block V and its length : Subtitution of this quantity into equation 18-11 yields

Note that / has the units of contrationn (that is numbber of perticles per cubic centimeter) which is readily converted to moles per liter:

Combining this relationship with equation 18-12 yields ( ) Finally, the constant in this equation can be collected in to a single factor give Which is a statement of Beers law to

The experimental measurement of transmittance and absorbance The relationships given by Equation 18-7 and 18-8 are not direcly applicable in the laboratory because the power of the attenuated beam P cannotbe determined in a straightforward way. The difficulty has its origin in the need to hold the sample whose absorbance is soughtin some short of container with transparent windows. Interaction between the radiation and the windows is inevitabel, leading to a lossby reaction at eachair to window interface as well as each window to sample interface. Typical losses can be appreciable. For example, about 4% of a beam is reflected upon vertical passeg of visible radiation across eachof the four interfaces associated with the two windowsof a glass container. Moreover, significantabsorption may accur within the container walls. Finally, the beam may suffer a diminuton in power during its passage through the solvent as a result of scattering by large molecules of inhomogeneities. In order to compensate for these effects, the power of the beam transmitted through a cell containing an absorbing solution is generally compared with that of a bem that passes through an identical cell containing only solvent. An experimental absorbance is then defined by the equation.

Such experimental absorbances obey beers law and are presumably good approximations of trueabsorbances. Henceforth, the term absorbance will refer to the ratio defined by Equation 18-13, P0 being the power of radiation after passage through a cell containing only the solvent, and P being the power after passage through an identical cell containing a solution of the analyte. The application of beers law to mixtures Beers law also applies to solutionscontaining more than one kind of absorbing substance. Provided no interaction occurs among the various species, the total absorbance for a milticomponent system is Where the subscripts refer to absorbing components 1,2,....,n. Limitations to the applicability of beers law The linear relationship between absorbance and path length at a fixed concentration of an absorbing substance is generalization for which no exception are know. Deviations from the direct proportionality between absorbance and contrentration at constanta b are frequently encountered, however some of these deviations are fundamental and represent real limitations to the law. Others occur as a consequence of the manner in which the absorbance measurements are made( instrumental deviation) or as a result of chemical changes associated with concentration changes (chemical deviations). Real limitations Beers law is successful in describing the absorpsion behavior of dilute solutions only and in this sense is a limiting law. At hight concentrations (usually

>0,01 M), the average distances between particles of the absorbing species are diminished to the point where each particle effects the charge distribution of its neighbors. This interaction can alter their ability to absorb a given wavelength of radiation. Because the extent of interaction depends upon concentration, the occurenceof this phenomenon causes deviation from the linear relationship between absorbance and concentration. A similar effect is sometimes encountered in dilute solution of absorbers that contain hight concoentrations of the species, particularly electrolytes. The close proximity of ions to the absorber alter the molar absorptivityof the latter by electrostatic interaction, which leads to departures from beerslaw. While the effect of molecular interaction is ordinarily not significantat concentrations below 0.01, some exceptions are encountered among certain large organic ions or molecules. For example, the molar absorptivity at 436 nm for the cation of methylene blue is reported to increase by 88% as the dye concentration is increased from 10-3 to 10-2 M; even bellow 10-6M, strict adherence to beers law is not observed. Deviations from Beers law also arise beccause molar absorptivity is dependent upon the refractive index of the solution. Thus, if concentration changes cause significant atleration in the refraktive index of asolution departures fron beers law are observed. In general, this effec is small and rarely significant at concentration less than 0,01 M. Chemical Deviation Apparent deviations from beers law are frequently encountered as a consequence of association, dissociation, or reaction of the absorbing species with the solvent. These deviations result from shiftsin chemical equilibria and not from changes in molar absorptivies. As shown by rhe following example, apparent departurrs from Beers law are readily predicted from the equilibrium constants for the reactions and the molar absorptivities of the solute. EXAMPLE A series of solutions containing various concentrations of the acidic indicator Hln (K4 = 1.42 x 10-5) was prepared in 0.1 M HCl and 0.1 M NaOH. In both media, a linear relationship between absorbance and concentration was observed at 430 and 570 nm. From the magnitude of the acid association constant, it is apparent that, for all practical purpose, the indicator is entirely in the undissociated from (Hln) in the HCl solution and completely dissociated as In- in NaOH. The molar absorptivities at the two wavelengths to be:

Derive absorbance data ( 1.00-cm cell) at the two wavelengths for unbuffered solutions with indicator concentrations ranging from 2 x 10-5 to 16x10-5 M. Plot the data. Let us calculate the contration of Hln and ln- an unbuffered 2.00 x 10-5 M solution of the indicator. From the equation for the dissociation reaction, it is apparent that:

Figure 18-8 is a plot of the data derived i the foregoing example and illustrates the types of deviation equilibrium. Note that the direction of curvature is opposite at the two wavelengths. Instrumental deviation with polycromatic radiation Beers law is also limiting in the sanse that it appliesonly when absorbance is measured with monocromatic radiation. Truly monochromatic sources, such as lasers, are not practical for routine analytical instrumen, however. Instead, a polychromatic continuous source is employed in conjunction with a garating or a filter that isolates a more or less symmetric band of wavelengths around the desired one. The following derivation illusrtrates how such a source may lead to deviations from beers law. Consider a beam made up oof just two wavelengths and , and assume that beers law applies strictly to each. With this assumption, we can write for radiation

When an absorbance measurement is made with radiation composed of both wavelengths, the power of the beam emerging from the solutionis given by P+P that of the beam emerging from the solvent by P 0 +P0. Therefore, the measusured absorbance is And beers law is followed. As shown figure 18-9, greater as adifference between however, the relationship between Am and concentration is no longer linear when the molar absorpsivities differ. Moreover, departures from linearity become and increases. When this treatment is expanded to include additional wavelengths, the effectremains the same. It is an experimental fact that deviations from Beers law resulting from the use of a polycromatic beam are not appreciable, provided the radiation used does not an compass a spectral region in which the abserber exhibits large changes in absorbance as afuncttion of wavelength. This observation is illustrated in figure 18-10. Instrumental deviation in the presence of stray radiation The radiation employed for absorbance measurements is usually contaminated with small amounts of stray radiation due to instrumental imperfections. Stray radiation arises from scattering phenomena off the surfaces of prisms, lenses, filters, and windows. It often differs greatly in wavelength from the principal radiation and, in addition, may not have passed throughtthe sample or solvent. When measurements are made in the presence of stray radiational, the observed absorbance is given by Where Ps is the power of the stray radiation. Figure 18-11 shows a plot of A versus concenfor various levels of Ps relative P0.

Note that the instrumental deviational illustrated in figure 18-10 and 1811 result in absorbances that are smaller thhan theoretical. It can be shown that instrumental deviations always lead to negative absorbance errors. Emission of electromagnetic radiation Atoms,ions, and molecules can be excited to one or more higher energy levels by any of several processes, including bombardment with electrons or other elementary particles, exposure to a hight voltage ac spark, heat treatment in a flame or arc, or exposure to a source of electromagnetic radiation. The lifetime of an excited species is generally transitory (10-6 to 10-9 s), and relaxation to a lower energy level or the ground state take place with a release of the excess energy in the form of electromagnetic radiation, heat , or perhaps both. Emission spectra Radiation from a sourceis convenienly characterized by means of an emission spectrum, which usually take the form of a plot of the relative power of the emitted radiation as a function of wavelength or frequency. Fugure 18-12 illustrates a typical emission spectrum which was obtained by aspirating abriner solution into an oxyhydrogen flame. Three types ofspectraare evident in the figure: line, band, and continous. The line spectrum is made up of aseries of sharp, well-defined peaks arising from from the excitation of indifidual atoms. The band spectrum consists of several groups of lines so closely spaced that they are not completely resolved. The source of the band are small molecules or radicals. Finally, the continuous spectrum is responsible for the increase in the background that becomes evident above about 350 nm. The line and band spectra are superimposed on this continuum. The source of the continuum is described on page 476. Line Spectra line spectra are encountered when the radiating species are individual atomic particles that are well separated, as in a gas. The individual particles in a gaseous medium behave independently of one another, and the spectrum consists of a series of sharp lines widths of abaout 10 -4 . in figure 18-12, lines for sodium, potassium, strontium, and calcium are identified. The energy level diagram in figure 18-13a shows the source of two of the lines in a typical emission spectrum of and element. The horizontal line labeled E0 coresssponds to the lowest, or ground state, energy of the atom. The horizontal lines labeled E1 and E2 are two higher energy electronic levels of the species. For example, the single outer electron in the ground state E 0 for a sodium atom is located in the 3s orbital. Energy level E 1 then represents the energy of the atom when this electron has been promoted to the 3p state by absorption of thermal, electrical or radiant energy (see also figure 18-4). The promotion is depicted by the shorter wavy arrow on the left in figure 18-13a. After perhaps 10-8 s, the atom returns to the ground state, emitting a photon whose frequency and wavelength are given by equation 18-3 and 18-4:

v1 = (E1-E0)/h

1 = hc/(E1-E0) this emissision process illustrated by the shorter straight arrow on the right in figur 18-13a. For the sodium atom, E2 in the figur corresponds to the more energetic 4p state ; the resulting radiation 2 would then appearat the shorter wavelength. The line appearing at about 330 nm in figure 18-12 results fromthis transition; the 3p to 3stransition provides a line at about 590 nm. It is importantto note that the emitted wavelengths are identicalto the wavelengths of the absorption peaks for sodium (figure 18-4) because the transitions involved arebetween the same two states. Band spectra Band spectra are often encountered in spectral source because of the presence of gaseous radicals or small molecules. For example figure 1812 bands for OH ,MgOH, and MgO are lebeled and consist of a series of closelspecly spaced lines not fully resolved by the instrument used to obtain the spectrum. Banda arise from the numerous quantized vibrational levels that are superimposed on the ground-state electronic energy level of a molecule. Figure 18-13 is a partial energy-level diagram for a molecule showing its ground state E0 and two of its sevveral excited electronic state, E1 and E2. A few of the many vibrational levels associated with the ground state are also shown, but those associated with the two excited states have been omitted because the lifetime of an excited vibrational states is brief compared with that of an electronically excited states (about 10-15 s versus 10-8 s).A consequence of this tremendous diffrence in lifetimes is that when an electron is excited to one of the higher vibrational levels of an electronic states, relaxation to the lowest vibrational level of that state occurs before an electronic transition to the ground state can occur. Therefore , the radiation produced by the electrical or thermal excitation of polyatomic species nearly always involves a transition from the lowest vibrational level of an excited electronic states to any of the several vibrational levels of the ground state. The mechanism by which a vibrationally excited species relaxed to the nearest electronic state involves a transfer of its excess energy to other atoms in the system through a series of collisions. As noted, this process takes place at an enormous speed. Relaxsation from one electronic state to another can also occur by collisional transfers of energy, but the rate of this process is slow enough that relaxation by photon release is favored. The energy level diagram in figure 18-13b illustrates the mechanism by wich to radiation bands consisting of five closely spaced lines are emitted by a molecule excited by thermal or lectrical energy. For a real molecule, the number of individual lines in wich larger because the ground state contains many more vibrational level than shown. In addition, a multitude of rotational states would superimposed on each of vibrational levels. The diffrences in energy among the rotational levels is perhaps an order of magnitude smaller than that for vibrational states. Thus, a real molecular band would be made up of many more lines than shown in figure 18-13b, and these lines would be much more closely spaced.

Continuous spectra As shown in figure 18-14, truly continuous radiation is produced when solids are heated to incandescence. Thermal radiation of this kind, which is called blackbody radiation, is more characteristic of the temperature of the emitting surface than of the material of which that surface is composed. Blackbody radiation is peoduced by the innumerable atomic and molecular oscillations, excited in the condensed solid by the thermal energy. Note that the energy peaks figure 18-14 shift to shorter wavelength with increasing temperature. It is clearthat very high temperatures are needed to cause a thermally excited source to emit a subtansial fraction of its energy as ultraviolet radiation. As noted earlier, part of the continuous background radiation exhibited in the flame spectrum shown in figure 18-12 is probably thermal emission from icandescent particles in this flame. Note that this background decreases rapidly as the ultraviolet region is approached. Heated solids, are important sources of ifrared, visible, and longer wavelength ultraviolet radiation for anlytical instruments. The effect of concentration of line and band spectra. The radiant power P of a line or a band depends directly upon the number of excited atoms or moleculer, which it turn is proportional to the total concentration c of the species present in the source. Thus we can write: P=kc Where k is a proportionality constant. This relationship is the basis of quantitative emission spectroscopy. Emission by Flourescence and Phosphorescence Flourescence and phosphorescence are analytically important emission prosses in which atoms or molecules are excited by the absorption of a beam or electromagnetic radiation. The excited species then relax to the ground state, giving up teheir excces energy as photons. Flouresscence takes place much more rapidly than phosphorescence and is generally complete in about 10-5 s (or less) ffrom the time of ectitation. Phosphorescence emission may exstend for minute or even hours after irradiation has ceased. Flourescence is considerably more importent than phosphorescence in analytical chemistry. Thus our dicussions focus largely on the former.

Atomic flourescence Gaseous atoms flouresce when they are exposed to radiation that has a wavelengththat exctly matchesthat of one of the absorption (or emission) line of the elemen in question. For example, gaseous sodium atoms are promoted to the excited energy state E1 shown in figure 18-13b through absorption of 590 nm radiation. Relaxation may than take place by flourescent reemission of radiation of the identical wavelength.flourescence in which the excitation and emission wavelengths are the same is termed resonance flourescence. Sodium atomscould also exhibit resonance flourescence when exposed to 330 nm radiation. In addition,however,the elemen could also produce nonresonance

flourescence by first relaxing to energy level E1 through a series of nonradiative collisions with other species in the medium. Further relaxation to the ground state can then take place either by the emission of a 590 nm photon or by further collisional deactivation. Resonance flourescence is commonly is encountered with atoms and to a lesser with molecular species. Molekolar Flouresence The nimber of molekules that flouresce is relatively small because flourescence require structural features thats slow the rate of the nonradiative relaxation processes illustrated in figure18-5b and enhance the rate of flourescence relaxation shown in figure 18-5c. Most molecules lack these features and undergo nonradiative relaxation at a rate that is significantly greater than the radiative relaxation rate; thus flourescence is precluded. As shown in figure 18-5c, bands of radiation a produced when molecules flouresce. Like moleculer absoption bands, molecular flourescence bands made up of a multitude of closely spaced lines thats a often difficult to resolve. note that the lines that terminate the two flourescence bans on the short-wavelength, of high-energy, side (1 and 1) are resonance line. This is molecular flourescence bands consist largely of line that are longer in wavelength than the band of absorbed radiations responsible for their excitation. This shift in wavelength is sometimes called the stokes shift. To understand te source of stokes shifts, let us consider what accures when the molecule under consideration is irradiated by a single wavelength 5. As shown in figure 18-5a.absorption of this radiation promotes an electron into vibrationallevel 4 of the second excited electronic state E2. In 10-15s or less, relaxation can to the zero vibrational level occurs (figure 185b). At this point further relaxation can follow either the nonradiative route depicted in figure 185b or the radiative route shown in figure 18-5c. If the latter is followed, relaxation to any of the several vibrational level of the ground state can take place, giving a band of emitted wavelength as shown. Note that all these lines are lower in energy, or longer in wavelength, than the excitation line 5. Let as now turn to those molecules in excited state E 2 that undergo nonradiative relaxation to electrinic state E1. As before, further relaxation can take a non rediative or a radiative route to the ground state. In the latter case, band 1 of flourescence is produced. Note that in this case the stokes shift is from ultraviolet radiation to visible. Note also that band 1 can be produced not only by the mechanism just described but also by the absorption of visible radiation of wavelength 1 through 5.( figure 18-5a). A detail discussion of the applications of molecular flourescence is given in section 20C.