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

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

2. Unknown sample Standard sample Second order data Trilinearity How the idea of RAFA can be used for quantitation in other systems? HPLC-DAD FIA Spectroscopic titrations Kinetic

3. RAFA and HPLC

4. HPLC-DAD

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

6. Mixture Standard X + y X Mixture Standard Mixture X + y X X + y Standard X Trilinearity in HPLC-DAD data a) In the presence of trilinearity Rank=2 Rank=1 Augmentation Rank=2 Rank=2

7. Mixture Standard X + y X Standard Mixture X X + y Trilinearity in HPLC-DAD data b) In the absence of trilinearity Rank=2 Rank=1 Augmentation Mixture X + y Standard Rank=3 X Rank=2

8. sx sx cx sy Mixture Standard cy cx X + y X sx cx sy Mixture cy X + y Standard 0 cx X sx 0 cx sy 0 Mixture Standard cx sx 0 cy X + y X = = = =

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-] HB HA B- [B-] [HB] A- HA A- + H+ HB B- + H+

12. Spectrophotometric monitoring of pH-metric titration of mixture of acids or bases C0HA=1 C0HA=1 C0HB=2 C0HB=0 HA A- + H+ HA A- + H+ Unknown sample Standard sample HB B- + H+ Rank=2 Rank=3

13. Rank deficiency in a system with two independent chemical processes HA A- + H+ HB B- + H+ Ct2 [H+] Ct2 Ka2 Ct1 [H+] [HB] = [A-] = Ct1 Ka1 [HA] = [H+] + Ka2 [A-] = [H+] + Ka2 [H+] + Ka1 [H+] + Ka1 [HB] + [B-] = Ct2 Ct1 = a Ct2 [HA] + [A-] = a ([HB] + [B-])

14. RAFA for analysis of an acid in a mixture C0HA=1 C0HB=2 HA A- + H+ Unknown sample HB B- + H+ C0HA=1 C0HB=0 HA A- + H+ Standard sample Rank=2 Rank=3

15. RAFA1.m file Rank Annihilation Factor Analysis

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

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’L] M’L ML [M’] [L] [M] [ML] L

32. Spectrophotometric monitoring of complexometric titration of mixture of metal ions C0M=1 C0M=1 C0M’=2 C0M’=0 M + L ML M + L ML Unknown sample Standard sample M’ + L M’L Rank=2 Rank=3

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. Spectrophotometric monitoring of pH-metric titration of mixture of metal ions and an acidic ligand ML [HL] [M’L] M’L HL L [ML] [M] [L] [M’]

35. C0M=1 C0M=1 C0M’=2 C0M’=0 HL L + H HL L + H M + HL ML + H M + HL ML + H M + L ML Unknown sample Standard sample M’ + HL M’L + H M + L ML M’ + L M’L Rank=2 Rank=3 Spectrophotometric monitoring of pH-metric titration of mixture of metal ions and an acidic ligand

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