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? Investigate the effects of extent of spectral overlapping on the results of RAFA.

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Presentation on theme: "? Investigate the effects of extent of spectral overlapping on the results of RAFA."— Presentation transcript:

1 ? Investigate the effects of extent of spectral overlapping on the results of RAFA

2 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

3 RAFA and HPLC

4 HPLC-DAD

5 Three are some problems in using RAFA for mixture analysis based on HPLC measurements

6 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

7 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

8 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 =

9 Free study Rank Annihilation Correction for the Amendment of Instrumental Inconsistencies Anal. Chim. Acta 464, 249-259,2002

10 RAFA and Spectrophotometric monitoring of pH-metric titration of mixture of acids or bases

11 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-

12 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

13 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

14 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

15 RAFA1.m file Rank Annihilation Factor Analysis

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20 Simulation of spectrophotometric monitoring of pH metric titration of a binary acid mixture

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27 ? Use RAFA for determination of a known acid in an unknown binary mixture

28 ? Use RAFA for determination of a known acid in an unknown binary mixture containing an inert chemical compound

29 ? Use RAFA for determination of a known acid in an unknown ternary mixture

30 Three are some problems in using RAFA for mixture analysis based on equilibrium measurements

31 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

32 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

33 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

34 [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

35 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

36 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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