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

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

RAFA and HPLC

HPLC-DAD

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

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

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

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 =

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

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

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-

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

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

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

RAFA1.m file Rank Annihilation Factor Analysis

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

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

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

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

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

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

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

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

[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

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

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