A Spectrophotometric Study on Complex Formation of Chromium (VI) with Glycine Thymol Blue

The composition and stability of the complex formed between chromium (VI) and Glycine Thymol Blue (G. T. B.) has been investigated using a spectrophotometric method. The chelate is reddish brown in colour and has λ_max 570 nm against a reagent blank. The composition has been determined by different methods as 1: 1. The chelate gives maximum absorbance between pH 6.5 and 7.0. The values of log K as determined by two different methods are 5.21±0.1 and 5.24±0.1 and the values of ΔG° are ?7.08±0.1 and ?7.12±0.1 Kcal respectively at pH 6.8 and at 25°C.     

Spectrophotometric Determination of Uranium with Sorbohydroxamic Acid as Reagent

Sorbohydroxamic acid forms with uranium an orange red, water soluble complex. The mole ratio of uranyl ion to compound is 1 to 1 under the investigated conditions. The formation constant of this chelate was also determined by the Likussar—Boltz method at a constant ionic strength of 0.1 M at 30°C as 2.10×10². The recommended procedure obeys Beer's law between 3.98ppm and 166.6ppm of uranyl ion at pH 3.8±0.1. Tolerances to cerium (IV) and thorium have been investigated. The procedure for the determination of uranium are made more specific by applying preliminary extraction of uranium by ether.     

Extraction—spectrophotometric determination of traces of cadmium with 4-(2-pyridylazo)resorcinol and a long-chain quaternary ammonium salt

A simple and highly sensitive extraction—spectrophotometric determination of cadmium is described. The ion-associate formed between the cadmium-PAR anionic chelate and cetyldimethylbenzylammonium chloride (CDBA) is extracted with chloroform at pH 10. The absorption maximum of the extracted species occurs at 505 nm, the molar absorptivity being (9.82 ± 0.30) × 10⁴ l mol^-1 cm^-1. The optimal concentration range for measurements is 0.2–1.0 μg Cd ml^-1; Beer's law is obeyed. The composition of the ion-associate is estimated to be CdPAR₂-2CDBA. The conditional extraction constant is log K'_ex ≈ 8. The stability constant of the cadmium—PAR chelate in aqueous solution is log β₂ = 17.5 ± 0.3. Extraction with N-benzoyl-N-phenylhydroxylamine is used to avoid several interferences. Moderate amounts of zinc are masked with sodium hydroxide.     

Spectrophotometry Studies of Uranyl Chelate of 7-Iodo-8-Hydroxyquinoline-5-Sulphonic Acid

Uranyl chelate of 7-iodo-8-hydroxyquinoline-5-sulphonic acid (ferron) has been studied spectrophotometrically in aqueous solution at 25° and at an ionic strength of 0.1 M. The formation of this chelate was pH dependent, and the optimum pH range was between 5.4 to 5.9, Its mole ratio of ligand to uranyl ion was found to be 2 to 1 stoichiometry and the stability constant, log K, was determined as 13.32±0.08. By using the wave-length of 365 mu, determination of trace amount of uranyl ion with the sensitivity of 0.54 γ/cm² was possible.     

Spectrophotometric Studies on Ferron and Thorium (IV)-Ferron Chelate

The ionization constants of ferron (7-iodo-8-hydroxyquinoline-5-sulphonic acid) and the interaction between Th(IV) and ferron have been studied spectrophotometrically at 25° and ionic strength of 0.1. The ionization constants were found to be pK₁=2.41±0.01, pK₂=7.10±0.01. The Th(IV)-ferron chelate in aqueous solution of pH 5.0 exhibited a characteristic absorption maximum at 365 mμ. The composition of Th(IV)-ferron chelate was 1:4 mole ratio of Th(IV) ion and ferron, and the stability constant (log K_g) was 26.22±0.16.     

Complex Formation of Ytterbium (III) with Bromopyrogallol Red—A Spectrophotometric Study

The complex formation of Ytterbium (III) with Bromopyrogallol red has been studied. spectrophotometrically in an attempt to establish composition, stability, thermodynamic parameters and optimum conditions for determining small amounts of ytterbium. The violet complex of ytterbium has λ_max at 620nm against a reagent blank. The composition determined by different methods is 1:1 at pH 6.2±0.1. The mean value of log K, free energy (ΔG), the heat content (ΔH) and entropy (ΔS) changes, of the complex are found to be 6.0, —8.1.kcal/mole, —3.5 Kcal/mole and 15.53 e.U. respectively at 30°C. The net molar absorptivity and Sandell's sensitivity is 19850 and 0.0087 μg of ytterbium /cm². The effect of diverse ions was examined with thirteen cations and ten anions in the determination of ytterbium.     

Physicochemical Studies on Cu(II)-Ferron Complexes

Experiments were carried out at 25°C and μ of 0.1 M. Spectrophotometric and potentiometric methods gave the ionization constants of ferron, pK₁=2.50±0.02 and pK₂=7.12±0.02. Cu(II) and ferron form a sparingly soluble 1:1 complex, [Cu(H₂O)₂L]⁰ (L: ferronate ion) which in higher acidity media, protonates to give [Cu(H₂O)₂HL]⁺and in lower acidity media, ionizes to give [Cu(H₂O)(OH)L]^?. At pH 2.3, the 1:1 complex gives a minimum solubility and the intrinsic solubility was found to be 1.1×10^-4. The Job's continuous variation method and the molar ratio method gave a formation constant (–pK) for Cu²⁺+L^z??CuL, 10.8±0.1 in the pH range of 0.64 to 1.18 and in the pH range of 5.0 to 5.5 (optimum pH condition for formation of complex), the stoichiometry of the Cu(II)-ferron chelate is essentially 1:2 (Cu:L) but with slight tendency to form 1:1 chelate if [L]/[Cu] is less than 2. The overall formation constant (–pK) was determined to be 20.0±0.3.     

Spectrophotometric Studies of Cobalt (II) Chelate of P-(2-Hydroxy-1-Naphthylazo) Benzenesulphonate

Cobalt(II) chelate of p-(2-hydroxy-1-naphthylazo)benzenesulphonate (orange II) has been studied spectrophotometrically in aqueous solution at 25° and at an ionic strength of 0.10 M. The formation of this chelate is pH dependent, the optimum pH range is between 9.5 to 10.8. Its mole ratio of ligand to cobalt(II) is 3 to 1 stoichiometry and the formation constant, logK, is determined as 19.17±0.13. By using the wave-length of 357 mμ, determination of trace amount of cobalt(II) with the sensitivity of 0.077 y/cm² is possible.     

Galvanostatic Studies on Reduction of Oxygen at Silver Electrode

Galvanostatic studies with low current density in 0.1 N KNO₃ medium reveal that reduction of oxygen at silver electrode is totally irreversible and in the range of oxygen concentration studied, 2.2-306.3×10^?9 mole/cm³, the E-log [0₂] plot consists of two straight lines, one has a slope of 0.12 volts/decade (C>1 ppm up to air-saturated) and the other, 0.72 volts/decade (0.1<C<0.8 ppm). The transfer coefficient, α, the heterogeneous rate constants, k^o_fh and k^o_gh were evaluated to be 0.12, 2.8×10^?4, 1.6×10^?7 for the higher concentration range, and 0.02, 4.4×10^?4 for the lower concentration region respectively. A possible analytical method for tenths ppm level of oxygen is suggested.     

Kinetics of the gas‐phase reaction of n‐C6–C10 aldehydes with the nitrate radical

Rate coefficients for gas‐phase reaction between nitrate radicals and the n‐C₆–C₁₀ aldehydes have been determined by a relative rate technique. All experiments were carried out at 297 ± 2 K, 1020 ± 10 mbar and using synthetic air or nitrogen as the bath gas. The experiments were made with a collapsible sampling bag as reaction chamber, employing solid‐phase micro extraction for sampling and gas chromatography/flame ionization detection for analysis of the reaction mixtures. One limited set of experiments was carried out using a glass reactor and long‐path FTIR spectroscopy. The results show good agreement between the different techniques and conditions employed as well as with previous studies (where available). With butanal as reference compound, the determined values (in units of 10^?14 cm³ molecule^?1 s^?1) for each of the aldehydes were as follows: hexanal, 1.7 ± 0.1; heptanal, 2.1 ± 0.3; octanal, 1.5 ± 0.2; nonanal, 1.8 ± 0.2; and decanal, 2.2 ± 0.4. With propene as reference compound, the determined rate coefficients were as follows: heptanal, 1.9 ± 0.2; octanal, 2.0 ± 0.3; and nonanal, 2.2 ± 0.3. With 1‐butene as reference compound, the rate coefficients for hexanal and heptanal were 1.6 ± 0.2 and 1.8 ± 0.1, respectively. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 120–129, 2003     

Thermodynamic Complexation of Dopamine with Zinc(II) in Media with Different Dielectric Constants

The complexation of zinc(II) with dopamine has been investigated by spectrophotometric measurements in mixed solvent system at an ionic strength of 0.2 mol•dm－3 sodium chloride, employed at at (15±0.1), (25±0.1), (35±0.1) ℃ at inin a pH range of ca. 6 to ca. 7 with a high ratio of ligand to metal. The effect of solvent systems on protonation and complexation are was was discussed. Linear relationships are werewere observed by plotting lg K versus 1/D, where K and D show stability and dielectric constants, respectively.     

A Spectrophotometric Study on Complex Formation of Nickel (II) and Cobalt (II) with Bromopyrogallol Red

Nickel (II) and Cobalt (II) form in 50% ethanolic medium, a bluish violet complex with Bromopyrogallol Red (BPR) in the mole ratio of 1:1 (Ni(II)) and 1:2 (Co(II)), both having at 620 nm, stable in the pH ranges 6.0-7.5 and 5.5-7.0, respectively. The thermodynamic stability constants and overall changes in the free energy of formation, enthalpy and entropy have been determined in both the cases. Beer's law is obeyed over the concentration range 0.5-5.0 ppm of Nickel and 0.2-3.0 ppm of Cobalt at 620 nm. The net molar absorptivities are 1.6 × 10⁴ and 2.9 × 10⁴ and the sensitivities are 0.00367 and 0.00219 μg of Nickel and Cobalt per cm,/². The effect of diverse ions on the metal ions determination is also reported.     

LACK OF HEAVY ATOM EFFECT ON THE ACTIVATION PARAMETERS OF BROMINE SUBSTITUTED 1,2-DIOXETANES*

Abstract— The continuous temperature variation kinetic method was applied to the direct chemilu-minescence of tetramethyl-1,2-dioxetane ( 1a ), 3-bromomethyl-3,4,4-trimethyl-1,2-dioxetane ( 1b ), 3,3–bis-(bromomethyl-4,4–dimethyl-1,2–dioxetane ( 1c ) and 3,4–bis(bromomethyl)-3,4–dimethyl-1,2-dioxetane ( 1d ). The activation energies (Ea) were found to be 27.6 ± 0.1, 28.4 ± 0.1, 28.0 ± 0.2, and 27.6 ± 0.2 kcal/mol, respectively. These results show that the heavy atom effect by the bromine substituents on the activation energies is negligible, confirming previous conclusions that a diradical mechanism operates in the thermal decomposition of these dioxetanes.     

2-Methyl-1, 4-Naphthoquinone Thiosemicarbazone as a Sensitive and Selective Chromogenic Reagent for Microdetermination of Palladium (II)

A simple, sensitive and selective procedure has been developed for the spectrophotometric determination of palladium. Palladium (II) reacts with 2-methyl-1,4-naphthoquinone thiosemicarbazone to form an orange brown complex in the pH range 8.2–9.5. The sensitivity, in terms of Sandell's definition, is 0.0025 μg Pd/cm² at 500 nm. The system adheres to Beer's law upto 2.66 ppm of palladium and optimum concentration range for the determination of the metal is 0.3–2.29 ppm with molar absorbtivity of 4.2×10⁴ ? mole^?1 cm^?1. The complex has 1:1 molar composition, as deduced by Job's method. The determination of palladium has been carried out in presence of foreign ions especially in presence of eighth group metals.     

A novel solid-phase extraction method for separation and preconcentration of zirconium

This work assesses the use of modified natural clinoptilolite as an adsorptive material for separation and preconcentration of trace amounts of zirconium ions. A simple, rapid and economical method was developed for the preconcentration of trace amounts of zirconium in aqueous medium using 1-(2-pyridylazo)-2-naphthol as a complexing agent. Effect of sample pH, flow rate of sample and elution solutions, breakthrough volume and interference of several ions were studied. Determination of zirconium was made by ICP-AES technique. The sorption was quantitative in the pH range from 3.0 to 4.0, whereas quantitative desorption occurred instantaneously with 2 mol L^?1 hydrochloric acid. Linearity was maintained between 0.05 and 9.0 μg mL^?1. Relative standard deviations range from ±0.9% to ±2.3% (n?=?5). The detection limit was 0.1 ng mL^?1. Because of good recovery (>97%), this method is suitable for preconcentration and determination of zirconium in effluents containing trace amount of zirconium.     

Evaluation of the rate parameters from i-E polarographic characteristics—kinetic study of oxidation of the Mo(V)—EDTA complex by vanadyl chelate

The kinetics of the oxidation of Mo(V)—EDTA by vanadyl chelate has been studied by the catalytic current technique of dc polarography. The reaction order appears to be first order in both chelates and EDTA. The kinetic analysis of the current-potential curves combined with the current ratio technique has been successfully applied to interpretation of the data obtained from polarographic measurements. Agreement between theory and experiment obtained is quite satisfactory as regards the effect of the following catalytic reaction in the polarographic wave. The rate constant for oxidation of the Mo(V) chelate is log k=4.30±0.02 obtained by the catalytic to non-catalytic current ratio method, and log k=4.45±0.07 obtained from the half-wave potential shifts at t^o=25.0±0.1°C. The mechanism of the electrochemical reaction considered is also discussed.     

Determination of hydration numbers of acids in organic phase by IR spectrometry

By the precision infrared spectrometry the hydration numbers n were determined for a series of acids in 0.64 M tributyl phosphate (CCl₄) and acetonitrile at a concentration of free water 0.01–0.1 M. In tributyl phosphate n = 3.1±0.3 (HAuCl₄); 2.9±0.3 (HFeCl₄); 1.9±0.2 (HClO₄); 1.0±0.2 (HNO₃); 1.0±0.1 (HCl). In acetonitrile n = 3.1±0.7 (HAuCl₄); 1.1±0.4 (HFeCl₄); 2.1±0.2 (HClO₄), 0±0.05 (HNO₃); 0.1±0.15 (HCl).     

Catalytic Spectrophotometric Determination of Vanadium by Flow Injection Analysis

Determination of trace amount of vanadium in water was studied by flow injection analysis. Catalytic spectrophotometric detection was performed with bromate oxidation of o-phenylenediamine and by addition of tiron as an activator and also as a masking agent. Vanadium can be determined with sample rate of ca. 60–70 samples/hour with in a range of 0.01 ppm to 0.5 ppm V and with r.s.d. 0.555% for 0.1 ppm V and 0.37% for 0.3 ppm V. Interference by Fe(III) can be reduced by using 0.3% NH₄F as a carrier solution.     

Thermal stability of poly(vinyl bromide) and copolymers of vinyl bromide with methyl vinyl ketone

Thermal stability and degradation behaviour have been studied for PVB and VB-MVK copolymers spanning the whole composition range, using thermogravimetric analysis. The reactivity ratios in the radial copolymerization were determined by using an NMR technique, leading to r_i(VB) = 3.6 ± 0.2 and r₂(MVK) = 0.2 ± 0.1. The introduction of MVK units into the VB chain leads to an interaction with release of methyl bromide. The stability of the copolymers increases with increasing MVK concentration.     

Spectrophotometric Studies of Nickel(II) Chelate of 2-Picolylamine

Nickel(II) chelate of 2–picolylamine has been studied spectrophotometrically in aqueous solution at 25°C and at an ionic strength of 0.3 M. The formation of pink color chelate was pH dependent, and the optimum pH range was between 7.0 to 8.5. Its mole ratio of ligand to nickel(II) ion was found to be 3 to 1 stoichiometry and the formation constant, logK, was determined as 13.31 ± 0.10. By using the wavelength 535 run, determination of trace amount of nickel(II) ion with the sensitivity of 5.28 τ/Cm² was possible. Enthalpy and entropy changes characterizing the formation of the chelate have been calculated as follows: ΔG°=–8.15Kcal mole^-1, ΔH°=–9.65 Kcal mole^-1, ΔS°=28.5eu mole^-1.