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Published byGriselda Burke Modified over 9 years ago
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? Investigate the effects of extent of spectral overlapping on the results of RAFA
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How the idea of RAFA can be used for quantitation in other systems? Unknown sample Standard sample Second order data Trilinearity HPLC-DAD FIA Kinetic Spectroscopic titrations
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RAFA and HPLC
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HPLC-DAD
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Three are some problems in using RAFA for mixture analysis based on HPLC measurements
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Trilinearity in HPLC-DAD data a) In the presence of trilinearity Mixture X + y Standard X Rank=2Rank=1 Augmentation Mixture X + y Standard X Rank=2 Mixture X + y Standard X Rank=2
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b) In the absence of trilinearity Mixture X + y Standard X Rank=2Rank=1 Augmentation Mixture X + y Standard X Rank=2 Mixture X + y Standard X Rank=3 Trilinearity in HPLC-DAD data
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Mixture X + y Standard X cxcx cycy sxsx sysy cxcx sxsx = = Mixture X + y Standard X = cxcx cxcx cycy 0 sxsx sysy Mixture X + y Standard X cxcx cxcx cycy sxsx sysy 0 sxsx 0 0 =
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Free study Rank Annihilation Correction for the Amendment of Instrumental Inconsistencies Anal. Chim. Acta 464, 249-259,2002
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RAFA and Spectrophotometric monitoring of pH-metric titration of mixture of acids or bases
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Spectrophotometric monitoring of pH-metric titration of mixture of acids or bases HA A - + H + HB B - + H + [HA] [A-][A-] [HB] [B-][B-] HA A-A- HB B-B-
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Spectrophotometric monitoring of pH-metric titration of mixture of acids or bases Rank=3 Rank=2 Unknown sample HA A - + H + HB B - + H + C 0 HA =1 C 0 HB =2 Standard sample HA A - + H + C 0 HA =1 C 0 HB =0
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HA A - + H + [HA] = C t1 [H + ] [H + ] + K a1 [A - ] = C t1 K a1 [H + ] + K a1 [HA] + [A - ] = ([HB] + [B - ]) C t1 = C t2 HB B - + H + [H + ] + K a2 [HB] = C t2 [H + ] [A - ] = C t2 K a2 [H + ] + K a2 [HB] + [B - ] = C t2 Rank deficiency in a system with two independent chemical processes
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Standard sample C 0 HA =1 C 0 HB =0 HA A - + H + Rank=3 Rank=2 RAFA for analysis of an acid in a mixture Unknown sample HA A - + H + HB B - + H + C 0 HA =1 C 0 HB =2
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RAFA1.m file Rank Annihilation Factor Analysis
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Simulation of spectrophotometric monitoring of pH metric titration of a binary acid mixture
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? Use RAFA for determination of a known acid in an unknown binary mixture
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? Use RAFA for determination of a known acid in an unknown binary mixture containing an inert chemical compound
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? Use RAFA for determination of a known acid in an unknown ternary mixture
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Three are some problems in using RAFA for mixture analysis based on equilibrium measurements
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Spectrophotometric monitoring of complexometric titration of mixture of metal ions M + L ML M’ + L M’L [M] [M’] [ML] [M’L] [L] ML M’L L
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Spectrophotometric monitoring of complexometric titration of mixture of metal ions Unknown sample Rank=3 C 0 M =1 C 0 M’ =2 M + L ML M’ + L M’L Standard sample Rank=2 C 0 M =1 C 0 M’ =0 M + L ML
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Spectrophotometric monitoring of pH-metric titration of mixture of metal ions and an acidic ligand HL L - + H + M + HL ML + H M + L ML M’ + HL M’L + H M’ + L M’L
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[HL] [L] [M’L] [M’] [M] [ML] HL L ML M’L Spectrophotometric monitoring of pH-metric titration of mixture of metal ions and an acidic ligand
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Unknown sample Rank=3 C 0 M =1 C 0 M’ =2 HL L + H M + HL ML + H M + L ML M’ + HL M’L + H M’ + L M’L Standard sample Rank=2 C 0 M =1 C 0 M’ =0 HL L + H M + HL ML + H M + L ML
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Write a m-file for modeling the concentration profiles of the following chemical system as a function of pH HL L - + H + M + HL ML + H M + L ML M’ + HL M’L + H M’ + L M’L
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