Kinetic determinations and some kinetic aspects of analytical chemistry

Mottola, Horacio A.; Mark, Harry B.

doi:10.1021/ac50055a005

Cited by 14 publications

(8 citation statements)

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“…Permittivity (dielectric constant) measurement has been exploited previously for the detection of eluted solutes from high-performance liquid chromatography (HPLC). The approach has been outlined by Haderka, together with the effects of dielectric loss and conductivity (1)(2)(3). A theoretical model to describe the behavior of a permittivity detector operating between 8 and 10 MHz (4) has been useful for furthering the development of permittivity monitors.…”

Section: Theorymentioning

confidence: 99%

“…where A is a cell dimension factor. Since both e and A are functions of temperature dCc _ dA , , de dT " Ce°dT + Ac°dT (2) Consider the effect of a small temperature change dT on the capacitance of a small parallel plate cell of plate radius r, plate area irr2, and plate spacing d, i.e., Cc = ttr2ee0/d The linear expansion coefficients of Teflon and steel are 1 X 4 and 1.7 X 10~6 K-1, respectively. (de/e)/dT, however, varies between 8 X 10"4 K"1 for cyclohexane and 6 X 1CT3 K"1 for methanol (8).…”

Section: Theorymentioning

confidence: 99%

“…In recent years, the kinetic approach to quantitative analytical chemistry has been widely employed as an alternative to the conventional equilibrium methods of analysis (1)(2)(3)(4). Although it is possible to utilize adequate reactions from a thermodynamic point of view to establish kinetic methods, their analytical characteristics are often limited by the complex nature of the system under study.…”

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confidence: 99%

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Kinetic fluorimetric determination of inorganic species by bromate oxidation of chelating agent and complexation with metal ions

Sánchez¹,

Dı́az²,

Laserna³

1983

Anal. Chem.

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Section: Theorymentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

mentioning

confidence: 99%

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Kinetic fluorimetric determination of inorganic species by bromate oxidation of chelating agent and complexation with metal ions

Sánchez¹,

Dı́az²,

Laserna³

1983

Anal. Chem.

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“…During the study of the kinetics of extraction of Be (II), Ga(III), Fe(III), and Cr(III) from aqueous perchlorate solutions with /3-diketones, Sekine (206) observed that when the organic solvent is of polar nature, the rate of extraction is dependent on the perchlorate concentration in the aqueous phase. The dependence of the rate of metal chelate extraction on perchlorate is explained on the basis that: (1) the metal ions are first extracted as ion-pairs (with C104~) and (2) the uncharged metal chelate complex is subsequently formed in the organic phase.…”

Section: Kinetics In Solvent Extraction Andmentioning

confidence: 99%

“…The basic organization of the 1980 Review (1) has been retained for this report. Papers included in this review have been selected from reports which appeared in the literature since the 1980 review through approximately November 1981.…”

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Kinetic determinations and some kinetic aspects of analytical chemistry

Mottola¹,

Mark²

1982

Anal. Chem.

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KINETIC ASPECTS OF ANALYTICAL CHEMISTRYHoraclo A. Mottola was born in Buenos Aires, Argentina, and received undergraduate and graduate education at the University of Buenos Aires. He earned Licentiate and Doctoral degrees from the University of Buenos Aires and did predoctoral work with Professor Ernest B. Sandell at the University of Minnesota (Minneapolis). He spent two years at the University of Arizona (Tucson) as a postdoctoral research fellow In Professor Henry Freiser's research group. After teaching for two years at the University ot the Pacific (Stockton, CA), he joined OSU in the fall of 1967. Dr. Mottola's research interests include studies on the role of kinetics in analytical chemistry (including reaction reate determinations), analytical separations (solvent extraction and liquid-liquid chromatography), continuousflow analysis, and analytical application of photochromism.

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Catalytic Kinetic Determinations: Nonenzymatic

Kawashima

Teshima

Nakano

2000

Encyclopedia of Analytical Chemistry

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Although a catalyst does not shift the position of equilibrium but it does markedly change the reaction rate, because the catalyst lowers the activation energy of a reaction providing an alternative favorable route for the formation of the products. The reacted catalyst is regenerated and is repeatedly involved in an indicator reaction. When the rate depends on the concentration of the catalyst, it can be determined by measuring the change in the physical properties of the reactants and/or products in the indicator reaction. The change in a physical property such as absorbance, fluorescence, chemiluminescence (CL) or electrode potential of a reaction system is usually monitored with time. This methodology is called catalytic methods or kinetic–catalytic methods of analysis. Kinetic–catalytic methods of analysis based on catalyzed reactions have progressed recently and have been applied to trace analyses for various catalysts (element) because of their extremely high sensitivity, low limit of detection and selectivity. Several reactions such as redox, ligand substitution and complexation reactions have been utilized as indicator reactions for the development of kinetic–catalytic methods of trace analyses. Most of the catalysts in redox reactions are metal ions or inorganic anions having different oxidation states such as cobalt, copper, chromium, iron, manganese, vanadium, selenium, iodide, bromide and nitrite. Oxidants capable of regenerating the catalyst are hydrogen peroxide, chlorate, bromate, periodate and dissolved oxygen. Reductants include ascorbic acid, hydroxylamine, hypophosphorous acid, alkali sulfides, dithiothreitol and tin(II). Certain substances significantly increase the rate of catalyzed reactions. These substances are referred to as activators and have been defined as substances that do not catalyze the indicator reaction but enhance the catalytic effect of the catalyst. Activators provide high sensitivity and selectivity in kinetic–catalytic methods. Such improved specificity can be expected to eliminate the preliminary separation in many instances. As the measurement includes time as an experimental variable, care is needed to ensure that mixing of reagents takes place at regular time intervals to obtain highly accurate results using a manual procedure. Such disadvantages in the manual system can be overcome by using flow‐injection analysis (FIA), in which the reaction time can easily be controlled by varying the flow rate of the solutions and the length of the reaction coil. Kinetic–catalytic methods allow the determination of various elements at nanogram and picogram levels (10 −11 M) with a simple and reasonable equipment. The detection limits (DLs) of the methods are of the order of picograms per milliliter with good accuracy and precision and are almost equal to those for inductively coupled plasma mass spectrometry (ICPMS). The application of catalytic effects of metal ions in titrimetry has been recognized for a long time. This methodology is called catalytic titration and involves two consecutive reactions, i.e. titration reaction and indicator reaction. The determinable concentration is almost 10 −6 M of the metal ions.

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Kinetic determinations and some kinetic aspects of analytical chemistry

Cited by 14 publications

References 81 publications

Kinetic fluorimetric determination of inorganic species by bromate oxidation of chelating agent and complexation with metal ions

Kinetic fluorimetric determination of inorganic species by bromate oxidation of chelating agent and complexation with metal ions

Kinetic determinations and some kinetic aspects of analytical chemistry

Catalytic Kinetic Determinations: Nonenzymatic

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