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Abstract
A spectra-kinetic approach was applied for the simultaneous determination of peroxyacetic acid (PAA) and hydrogen peroxide with multiple
linear regression (MLR) method, using the initial rates of their reaction with diphenylamine (DPA). The predictive ability of the MLR method
is based on the slight kinetic differences of these analytes occur at two wavelengths when react with DPA as a common ligand. A stopped flow
apparatus was used, and the time-resolved UVvis spectra were measured with a coupled charge device (CCD) spectrophotometer. This novel
instrumentation allowed to obtain high quality kinetic data at a maximum of many wavelengths simultaneously. The method was successfully
applied to the simultaneous determination of these peroxides in residues from a disinfection process in a beer brewery.
2004 Elsevier B.V. All rights reserved.
Keywords: Peracetic acid; Peroxides; Disinfectant determination; Chemometric spectra-kinetic analysis
1. Introduction
Peroxides, such as hydrogen peroxide and peroxyacetic
acid (PAA) find increasing use in industry for disinfection
and bleaching purposes due to their ecologically beneficial
properties. PAA is rapidly cidal at low concentrations
against a broad spectrum of microorganisms, including
gram-positive and gram-negative bacteria, yeasts, molds,
and algae under a wide variety of conditions. It is also
effective against anaerobic and spore-forming bacteria. PAA
is effective at killing biofilm microorganisms at low concentrations and short contact time [1]. It is also well suited as a
biocide in industrial cooling water and papermaking systems
[2]. Although PAA is a potent biocide, it is unique in that
it does not produce toxic byproducts and its decomposition
products (acetic acid, water, and oxygen) are innocuous and
environmentally acceptable. The technical synthesis of PAA
Corresponding author. Tel.: +30651 98406; fax: +30651 98407.
E-mail address: ipettas@cc.uoi.gr (I.A. Pettas).
0003-2670/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2004.07.010
276
I.A. Pettas, M.I. Karayannis / Analytica Chimica Acta 522 (2004) 275280
2. Theory
2.1. Multiple linear regression (MLR) method
It involves the application of MLR to the inverse expression of Beers law of spectroscopy [10]:
1
C=
(1)
An
n b
where C is the concentration of the constituent of interest,
the molar absorptivity, b the pathlength of the radiation in the
cell and A, the respective absorbance at a given wavelength,
n.
For the initial rate method [11,12], the initial rate of the reaction dAn /dt at wavelength n, replaced the absorbance value
An at Eq. (1), according to the equation:
1 dAn
(2)
C=
k
dt
where k is the reaction rate constant.
The matrix of concentrations of the analytes (C) are treated
as the dependent variables, whereas the responses of the detector (X; either absorbances or initial rates) are the independent variables during calibration (P) according to the model
equation:
C = PX
(3)
P = CXT (XXT )
(4)
For the prediction of the unknowns only one matrix multiplication is required:
Cunkwown = PXunknown
(5)
Examination of the method included fitting of the developed model to the calibration data, and the results were plotted and inspected visually.
3. Experimental
3.1. Apparatus
Spectra-kinetic measurements were made using an S2000
spectrophotometer with CCD detector (Optronics Inc.,
Florida) equipped with fiber optics. A stopped-flow module
supplied by Tri-tech Dynamic Instruments (Cantech Scientific Ltd., Canada), with an observation cell of 3 mm path
length, was fitted to the spectrophotometer. A MP-1035D
tungsten-halogen lamp (model MP-1035D), attached with the
aid of optical fibers, was used as light source. The solutions
in the module and the cell were kept at a constant temperature
of 25 C, by circulating water from a thermostated tank. The
data were acquired and edited using a Pentium III 750 MHz
personal computer with 256 MB of RAM. The initial rates
of the reactions were calculated, with a homemade algorithm
[11], after the data acquisition of the kinetic curves to the
PC. All algorithms were written in MATLAB version 5.x
environment, or used from PLS 2.11 Toolbox for MATLAB.
3.2. Reagents
All reagents were of analytical-reagent grade. A hydrogen
peroxide solution 30% (Merck) was utilized for the preparation of standard dilute solutions. An aqueous stock solution
of 1 mM of peroxyacetic acid (PAA) was prepared (Merck)
in distilled water. To minimize any analytical errors, spectra
were collected immediately after the preparation of all peroxide solutions. A stock solution of 10 mM of DPA was also
prepared in a mixture of 90% formic acid and 10% distilled
water (Riedel-De Haen). Copper(II) solution with a concentration of 0.1 mM was obtained by diluting CuCl2 , purchased
by Merck, in distilled water.
3.3. Safety considerations
3.3.1. Hazard identication
Strong oxidizer: stabilized peracetic acid under fire conditions intensifies the fire. The liquid phase and mist of peracetic and formic acid are corrosive (causing burns); direct
contact could cause irreversible damage to eyes. It will irritate nose, throat, and lungs but will usually subside when
exposure ceases.
3.3.2. Handling and storage of peroxyacetic and
formic acid
Transfer products from drums to process in closed
system. Use exhaust ventilation. Empty drum/container
as thoroughly as possible, rinse before disposal. Avoid
contamination. Never return to original container. Use
I.A. Pettas, M.I. Karayannis / Analytica Chimica Acta 522 (2004) 275280
277
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I.A. Pettas, M.I. Karayannis / Analytica Chimica Acta 522 (2004) 275280
Fig. 2. The initial rate of the reaction H2 O2 DPA at 350 nm, for mixtures
of formic acidwater of various proportions ([DPA] = 0.1 mM, [H2 O2 ] =
0.2 mM, [Cu(II)] = 10 mM, temp = 25 C).
Fig. 4. The effect of concentration of the DPA on the reaction rate, at 582 nm:
(a) [DPA] = 0.05 mM, (b) [DPA] = 0.1 mM, (c) [DPA] = 0.2 mM, (d) [DPA]
= 0.5 mM, ([Cu(II)] = 10 mM, [H2 O2 ] = 0.2 mM, temperature = 25 C).
I.A. Pettas, M.I. Karayannis / Analytica Chimica Acta 522 (2004) 275280
279
Fig. 5. Univariate calibration curves for PAA and H2 O2 at: (a) 582 nm, [H2 O2 ] = 0 mM, temp = 25 C, and (b) 350 nm, [H2 O2 ] = 0 mM, temp = 25 C, and
PAA at: (c) 582 nm, [PAA] = 0 mM, temp = 25 C, and (d) 350 nm, [PAA] = 0 mM, temp = 25 C ([DPA] = 0.1 mM, [Cu(II)]= 10 mM).
Table 1
The hydrogen peroxidePAA composition and the initial rates of 13 calibration mixtures used for multivariate calibration, at 350 and 582 nm
Sample number
[H2 O2 ] (mM)
[PAA] (mM)
1
2
3
4
5
6
7
8
9
10
11
12
13
0.20
0.74
0.34
0.24
0.34
0.39
0.20
0.15
0.29
0.55
0.15
0.20
0.24
0.04
0.04
0.05
0.03
0.03
0.05
0.06
0.06
0.07
0.07
0.08
0.05
0.08
0.0387
0.0793
0.0419
0.0301
0.0357
0.0401
0.0313
0.0319
0.0412
0.0610
0.0409
0.0325
0.0425
0.3197
0.8224
0.3290
0.2458
0.2551
0.2988
0.2490
0.2421
0.3146
0.6252
0.3064
0.2452
0.3221
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I.A. Pettas, M.I. Karayannis / Analytica Chimica Acta 522 (2004) 275280
Table 2
The spiking and the recoveries of 10 real samples used for prediction with MLR method
Number of mixtures
1
2
3
4
5
6
7
8
9
10
30:1
10:1.67
75:1
15:1
15:1
10:3.33
75:1
10:6.67
Estimated concentration
Predicted concentration
Recovery (%)
[H2 O2 ] (mM)
[PAA] (mM)
[H2 O2 ] (mM)
[PAA] (mM)
H 2 O2
0.30
0.30
0.75
0.75
0.15
0.15
0.30
0.00
0.75
0.15
0.01
0.05
0.01
0.05
0.01
0.05
0.00
0.01
0.01
0.10
0.3030
0.3060
0.7500
0.7950
0.1560
0.1485
0.2910
0.0000
0.7650
0.1530
0.0112
0.0490
0.0088
0.0520
0.0097
0.0425
0.0000
0.0104
0.0114
0.1000
101
102
100
106
104
99
97
106
102
102
PAA
112
98
88
104
97
85
98
104
114
100
[8]
[9]
[10]
5. Conclusions
One of the most salient features of the proposed method
is speed. Since the time required to obtain analytical data
is a few seconds, the initial rate method in combination with
MLR can be implemented to an automated on-line procedure,
and it is a useful, simple alternative to routine procedures for
the determination of these analytes.
References
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