22C Absorption of Radiation Reflection losses a Scattering Tonses in \ 4 solution locident Emergent team. P, beam. i Figure 22-11 Reflection losses 7 aimeriaces Reflection and seattering losses. tn identical cell containing only solvent. Experimental transmittances and ab- sorbances that closely approximate the true transmittance and absorbance are then ‘obiained with the equations p= Pasae = F (22-10) Pave Po Py "0 A= tog Fit ~ tog 2240) The terms Pp and Pas used in the rest of this book. refer to the power of radiation 1s passed through cells containing the solvent and the analyte, respec Beer's law can be derived as follows.* Consider the block of absorbing mat- ter (old, liquid, or gas) shown in Figure 22-12. A beam of parallel mono- chromatic radiation with power Pa strikes the block perpendicular to a sur- face; after passing through a length b of the material, which contains 1 absorbing particles (atoms, ions, or molecules), its power is decreased to P asa result of absorption, Consider now a cross section ofthe block having fn area $ and an infinitesimal thickness dx. Within this section there are dt absorbing particles; associated with each panicle, we can imagine a surface at which photon capture will occur. That is if a photon reaches one of these areas by chance, absorption will follow immediately. The total projected «aea of these capture surfaces within the section is designated as d; the "he dncusion that follows is based on » paper by F.C. Strong, Anal, Chem, 1982, 24,338512 Chapter 22 An Introduction to Spectrochemical Methods ratio of the capture area to the total area, then, is dS/S. On a statistical aver? age, this ratio represents the probability forthe capture of photon within he) section. 4 ‘The power of the beam entering the section P, is proportional tothe num, ber of photons per square centimeter per second, and dP, represents the quantity removed per second within the section; the faction absorbed is then ~ dP,/P,, and this ratio also equals the average probability for capture: “The term is given a minus sign to indicate that P undergoes a decrease. Th -2.8 as Recall, now, that dS is the sum of the capture areas for particles within the section; it must therefore be proportional to the number of panicles, or aS = adn 2415 where dn is the number of particles and a is a proportionality constant, which can be called the capture cross section. Combining Equations 22-1 and 22-13 and summing over the interval between 0 and m, we obtain -[/#- Pe which, upon integration, gives Upon converting to base 10 logarithms and inverting the fraction to c the sign, we obtain hog £2 = —2 ©8’p ~ 23035 where n isthe total number of particles within the block shown in Figu 22-12. The cross-sectional area S can be expressed in terms of the voluf the block V in em? and its length b in em. Thus, sate em Substitution of this quantity into Equation 22-14 yields Pr log 2 = 2.303 V acentimeter); we can readily convert n/V to moles per liter. Thus, the jumber of moles is given by n panicles ‘umber mol 02 X 10 particles/mol dc in moV/L is given by 1000 cx? /L. Vent mol/L 02 x 105"! * = 1000. 602 x10 V relationship with Equation 22-15 yields Py _ 6.02 X 10° abe hs P 2.303 x 1000 (22-16) Figure 22-12 Attenuation of radiation with initial power Py by a solution containing c ‘moV/L of absorbing solute and a path length of b em (P < Po). 22C-7 The Application of Beer's Law to Mixtures Beer's law also applies to a medium containing more than one kind of absorbing _Absorbances are aie. substance. Provided there is no interaction among the various species, the total absorbance for a multicomponent system is given by 513