?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 dataa) In the presence of trilinearity

Mixture

X + y

Standard

X

Rank=2 Rank=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=2 Rank=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

cx

cy

sx sy

cx

sx

= =

Mixture

X + y

Standard

X

=

cx

cx

cy

0

sx sy

Mixture

X + y

Standard

X

cx

cx

cy

sx sy0 sx

00

=

Free study

Rank Annihilation Correction for the Amendment of Instrumental

InconsistenciesAnal. Chim. Acta464, 249-259,2002

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-]

[HB] [B-] HA

A-

HBB-

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

Rank=3 Rank=2

Unknown sample

HA A- + H+

HB B- + H+

C0HA=1

C0HB=2

Standard sample

HA A- + H+

C0HA=1

C0HB=0

HA A- + H+

[HA] =

Ct1 [H+][H+] + Ka1

[A-] =

Ct1 Ka1

[H+] + Ka1

[HA] + [A-] = ([HB] + [B-])

Ct1 = Ct2

HB B- + H+

[H+] + Ka2

[HB] =

Ct2 [H+][A-] =

Ct2 Ka2

[H+] + Ka2

[HB] + [B-] = Ct2

Rank deficiency in a system with two independent chemical processes

Standard sample

C0HA=1

C0HB=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+

C0HA=1

C0HB=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

C0M=1

C0M’=2

M + L ML

M’ + L M’L Standard sample

Rank=2

C0M=1

C0M’=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 MLM’ + HL M’L + H

M’ + L M’L

[HL]

[L]

[M’L]

[M’]

[M][ML]

HLL

ML M’L

Spectrophotometric monitoring of pH-metric titration of mixture of metal ions and an acidic ligand

Spectrophotometric monitoring of pH-metric titration of mixture of metal ions and an acidic ligand

Unknown sample

Rank=3

C0M=1

C0M’=2

HL L + HM + HL ML + H

M + L ML

M’ + HL M’L + HM’ + L M’L

Standard sample

Rank=2

C0M=1

C0M’=0

HL L + HM + 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 MLM’ + HL M’L + H

M’ + L M’L