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Chem 155 Unit 10 Page 184 of 316Limitations to Beer’s Law cont.:Bigger graph, that’s all. Keep it simple.The Stray Radiation Problem:Light reaching the detector that a. does not come from thesource, b. does not go through the sample. or c. is not theintended wavelength contributes a background power,P STRAY that, in addition to making the absorbance deviatefrom Beer’s law.Does stray radiation make a positive or a negativedeviation from Beer’s law (A = εbC)Stray radiation can come from the source!In a conventional Czerny-Turner monochromator operatingin first order, if the monochromator setting is 700nm, 350nmradiation diffracted in second order will also fall on the exitslit! Order-sorting filters that are moved into the light beamaccording to the wavelength normally remove this but if afilter fails to remove all of the 350nm light then there will be aP STRAY component.P stray 0.05 A truei log P iP oA appi log P i P strayP o P stray0 1 2 3 4P i =A truei =A appi =1000.10.011·10 -31·10 -412340.8451.2431.3141.321A truei43210C iPage 184 of 316
Chem 155 Unit 10 Page 185 of 316Noise in Absorbance Calculations:A complex problem to treat exactly – hence ourmerciful, qualitative approach!Consider the signals P and Po – you actuallymeasure these, and they always contain noise.PBigger graph, that’s all. Keep it simple.Consider an alternative picture and simple statement.Po P PoPoPPA = A = A =Case 1.Hard to distinguish P and PoFor example:P=0.99±0.01Po=1.00±0.01Possible : Possible:1.000.99P/Po 1.01A=-Log(P/Po)NEGATIVECase 2.Hard to distinguish P and zeroFor example:P=0.01±0.01Possible :P = 0.00A = -Log(P/Po) Infinite!Page 185 of 316
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Full set of Notes with Fill-Ins - San Jose State University

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