Simultaneous Kinetic‐Spectrophotometric Determination of Hydrazine and its Derivatives by Partial Least Squares and Principle Component Regression Methods

Abstract

Simultaneous kinetic-spectrophotometric determination of a ternary mixture of hydrazine (HZ) and its derivatives by principal component regression (PCR) and partial least squares (PLS) calibration is described. The methods were based on the difference observed in the reduction rate of iron(III) with HZ, thiosemicarbazide (TSCZ) and phenylhydrazine (PHZ) in the presence of 2,2¢-bipyridine (Bpy). The colored complex of [Fe(Bpy) 3 ] 2+ was formed in sodium dodecyl sulfate (SDS) as micellar media, and then monitored at 520 nm. The results showed that simultaneous determination of HZ, TSCZ and PHZ could be performed in their concentration ranges of 1.0-70.0, 0.2-6.0 and 0.1-10.0 µg mL -1 , respectively. The root mean squares errors of prediction (RMSEP) of HZ, TSCZ and PHZ were 0.719, 0.164 and 0.105 (for PLS) 0.788, 0.166 and 0.993 (for PCR), respectively. Both methods (PCR and PLS) were validated using a set of synthetic sample mixtures and then applied for simultaneous determination of HZ, TSCZ and PHZ in water samples. Apparatus and SoftwareA GBC UV-Visible Cintra 6 Spectrophotometer model with 1-cm glass cells was used for recording the kinetic spectrophotometric data. A Metrohm 780 pH-meter furnished with a combined glass-saturated calomel electrode was calibrated with at least two buffer solutions at pH 3.00 and 9.00. The data were treated in an AMD 2000 XP (256 Mb RAM) microcomputer using MATLAB software. PLS and PCR analyses were performed using PLS and PCR toolboxes in MATLAB program version 7.0. Reagents and Standard SolutionsAll chemicals were of analytical reagent grade and double distilled water was used throughout experiments. Stock solutions (1000 µg mL -1 ) of HZ, TSCZ and PHZ were prepared in 100-mL flasks by dissolving 0.4061 g of hydrazinium sulfate (Merck), 0.1000 g of thiosemicarbazide (Merck) and 0.1337 g of phenylhydrazinium choloride (Merck) in water and diluting with water to the mark. A 0.05 M Fe(III) solution was prepared in a 100-mL flask by dissolving 2.43 g of ammonium ferric sulfate in water and diluting to the mark. 2,2¢-Bipyridine (Bpy) solution (0.05 M) was prepared by dissolving 0.784 g of 2,2¢-bipyridine (Merck) in ethanol and diluting with water to 100-mL in a volumetric flask. A 0.2 M SDS solution was prepared by dissolving 5.76 g of SDS (Merck) in water and diluting to 100-mL with water. Acetate buffer solution (1.0 M, pH 3.0) was prepared using acetic acid and NaOH solutions and adjusting its pH with a pH meter.

Recent applications of kinetic methods in multi-component analysis

“…Thus, although HPSAM cannot be used for catalytic-based reactions, it can be used for the simultaneous analysis of binary mixtures in their first order, or pseudo first order, competition reactions. Table 1 presents the application of HPSAM for simultaneous kinetic analysis published during the years 2000-2007 [59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75].…”

Application of H-Point Standard Addition Method and Multivariate Calibration Methods to the Simultaneous Kinetic-Potentiometric Determination of Cerium(IV) and Dichoromate

“…The theories and applications of chemometrics methods such as PCR and PLS, to the analysis of multi-component mixtures, have been discussed by several workers [31][32][33][34][35]. PCR and PLS modeling are powerful multivariate statistical tools, which are successfully applied to the quantitative analysis of spectrochemical and electrochemical data [33][34][35][36]. The first step in the simultaneous determination of the species by PCR and PLS methodologies involves the construction of calibration matrix for the binary mixture of Ce 4+ and Cr 2 O 7 2-.…”

Application of H-Point Standard Addition Method and Partial Least Squares to the Simultaneous Kinetic-Potentiometric Determination of Hydrazine and Phenylhydrazine

“…28 Recently, we reported a kinetic-spectrophotometric determination of ternary mixture of HZ and its derivatives using PCR and PLS methods. 29 To the best of our knowledge, no one has reported any chemometric methods for the simultaneous determination of HZ and its derivatives in a mixture, based on the kinetic-potentiometric method in which ion-selective electrodes are used.This work reports the first application of HPSAM and PLS to the simultaneous kinetic-potentiometric determination of binary mixture of HZ and PHZ. The methods are based on the differences observed in the rate of production of chloride ion in the reactions of NCS with HZ and PHZ.…”

“…[18][19][20][21][22][23][24] H-point standard addition method (HPSAM) was reported for simultaneous determination of binaries of HZ and semicarbzide, 25 HZ and PHZ, 26 HZ and acetylhydrazine, 27 HZ and isoniazid. 28 Recently, we reported a kinetic-spectrophotometric determination of ternary mixture of HZ and its derivatives using PCR and PLS methods. 29 To the best of our knowledge, no one has reported any chemometric methods for the simultaneous determination of HZ and its derivatives in a mixture, based on the kinetic-potentiometric method in which ion-selective electrodes are used.…”

“…28 Recently, we reported a kinetic-spectrophotometric determination of ternary mixture of HZ and its derivatives using PCR and PLS methods. 29 To the best of our knowledge, no one has reported any chemometric methods for the simultaneous determination of HZ and its derivatives in a mixture, based on the kinetic-potentiometric method in which ion-selective electrodes are used.…”