Investigate the effects of extent of spectral overlapping on the results of RAFA
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Transcript of Investigate the effects of extent of spectral overlapping on the results of RAFA
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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 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
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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
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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
=
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Free study
Rank Annihilation Correction for the Amendment of Instrumental
InconsistenciesAnal. Chim. Acta464, 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-]
[HB] [B-] HA
A-
HBB-
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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+
C0HA=1
C0HB=2
Standard sample
HA A- + H+
C0HA=1
C0HB=0
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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
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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
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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
C0M=1
C0M’=2
M + L ML
M’ + L M’L Standard sample
Rank=2
C0M=1
C0M’=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 MLM’ + HL M’L + H
M’ + L M’L
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[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
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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
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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 MLM’ + HL M’L + H
M’ + L M’L