Photoionization of Ru(bpy)32+ ions in aqueous solutions containing sodium dodecyl sulfate. Influence of ion binding

Sodium dodecyl sulfate (SDS) augments the yield of biphotonic ionization of tris-2,2′-bipyridyl ruthenium(II) ions (3.75×10⁻⁵ mol dm⁻³) in aqueous solution at room temperature to different extents at two different concentration ranges: by a factor 4 at [SDS] just below the critical concentration for precipitation (4.5×10⁻⁴ mol dm⁻³) and by a factor 1.4 at [SDS] above the critical micellar concentration (8×10⁻³ mol dm⁻³). The augmentation of the photoionization yield is explained in terms of ion binding, i.e. electrostatic interaction between Ru(bpy)₃²⁺ ions and dodecyl sulfate ions which results in a partial charge neutralization with the consequence of a decrease in the ionization potential.     

Kinetics and mechanisms of the reactions of aluminium(III) with β-diketones in aqueous solution

The kinetics and mechanisms of the reactions of aluminium(III) with pentane-2,4-dione (Hpd), 1,1,1-trifluoro pentane-2,4-dione (Htfpd) and heptane-3,5-dione (Hhptd) have been investigated in aqueous solution at 25°C and ionic strength 0.5 mol dm⁻³ sodium perchlorate. The kinetic data are consistent with a mechanism in which aluminium(III) reacts with the β-diketones by two pathways, one of which is acid independent while the second exhibits a second-order inverse-acid dependence. The acid-independent pathway is ascribed to a mechanism in which [Al(H₂O)₆]³⁺ reacts with the enol tautomers of Hpd, Htfpd, and Hhptd with rate constants of 1.7(±1.3)×10⁻², 0.79(±0.21), and 7.5(±1.6)×10⁻³ dm³ mol⁻¹ s⁻¹, respectively. The inverse acid pathway is consistent with a mechanism in which [Al(H₂O)₅(OH)]²⁺ reacts with the enolate ions of Hpd, Htfpd, and Hhptd with rate constants of 4.32(±0.18)×10⁶, 5.84(±0.24)×10³, and 1.67(±0.05)×10⁷ dm³ mol⁻¹ s⁻¹, respectively. An alternative formulation involves a pathway in which [Al(H₂O)₄(OH)₂]⁺ reacts with the protonated enol tautomers of the ligands. This gives rate constants of 2.79(±0.12)×10⁴, 3.86(±0.16)×10⁵, and 8.98(±0.25)×10³ dm³ mol⁻¹ s⁻¹ for reaction with Hpd, Htfpd, and Hhptd, respectively. Consideration of the kinetic data reported here together with data from the literature, suggest that [Al(H₂O)₅(OH)]²⁺ reacts by an associative or associative-interchange mechanism. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 257–266, 1998.     

Metallophthalocyanines Bearing Polymerizable {[5‐({(1E)‐[4‐(Diethylamino)phenyl]methylene}amino)‐ 1‐naphthy1]oxy} Groups as Electrochemical Pesticide Sensor

The synthesis and characterization of novel metallophthalocyanines (MPcs(ea)) carrying {[5‐({(1E)‐[4‐(diethylamino)phenyl]methylene}amino)‐1‐naphthyl]oxy} groups on four peripheral positions have been reported. These complexes have been characterized by a combination of FT‐IR, ¹H and ¹³C NMR, mass and UV‐Vis spectroscopy techniques. Redox active metal centers in the core of the Pc rings (Co (II) [CoPc(ea)], Mn(III) [Cl–MnPc(ea)], and Ti(IV)O [TiOPc(ea)]) and electropolymerizable substituents on the peripheral positions of Pc rings were used to increase redox activity and electrochemically polymerization ability of the complexes. The redox properties of MPcs(ea) were determined with voltammetry and in situ spectroelectrochemistry techniques. Then, GCE/MPc(ea) electrodes were constructed with the electropolymerization of MPcs and these electrodes were tested as the pesticide sensors. Sensing studies indicated that type of the metal center of the complexes effectively influenced the sensing activities. While all complexes showed interaction abilities for the fenitrothion, parathion and eserine, GCE/CoPc(ea) electrode detected the parathion selectively with LOD value of 4.52×10⁻⁷ mol dm⁻³ among studied three pesticides. Moreover, GCE/MnClPc(ea) electrode selectively detected eserine with LOD value of 6.43×10⁻⁷ mol dm⁻³ and GCE/TiOPc(ea) electrode detected parathion with LOD value of 8.64×10⁻⁷ mol dm⁻³. All GCE/MPcs(ea) electrodes showed high sensitivity and wide linear ranges for those pesticides. These sensing data illustrated the usability of these modified electrodes in real samples such as seawater with good selectivity and sensitivity.     

Kinetics and mechanism of silver(I) catalyzed oxidation of water with bismuth(V) in HClO4?HF mixture

The kinetics of the oxidation of water with bismuth(V) in presence of silver(I) has been investigated in a mixture of HClO₄ (1.0 mol dm^?3) and HF (1.5 mol dm^?3). The reaction is second order, viz., first order with respect to bismuth(V) and silver(I), each, and the second order rate constant is (6.6 ± 0.7) × 10^?3 dm³ mol^?1 s^?1. However, rate is independent of hydrogen ion concentration. A comparative analysis of these results with the results obtained for pdp, pds, and Ce(IV), reactions with silver(I) has also been made to correlate the rate constants and the redox-potentials of the oxidant couples.     

Kinetics and mechanism of oxidation of ethylenediamine and related compounds by diperiodatoargentate (III) ion

The oxidation of ethylenediamine by diperiodatoargentate (III) ion has been studied by stopped‐flow spectrophotometry. Kinetics of this reaction involves two steps. The first step is the complexation of silver (III) with the substrate and is over in about 10 ms. This is followed by a redox reaction in the second step that occurs intramolecularly from the substrate to the silver (III) center. The rate of reduction of silver (III) species by ethylenediamine, ethanolamine, and 1,2‐ethanediol were observed to be 1.2 × 10⁴, 1.1 × 10², and 0.14 dm³ mol⁻¹ s⁻¹, respectively, at 20°C. The reaction rate shows an inverse dependence on [IO] and [OH⁻] in the low concentration range (≤1 × 10^‐3 mol dm⁻³). At higher [OH⁻] (>1 × 10⁻³ mol dm⁻³) the rate of reaction starts increasing and attains a limiting value at very high [OH⁻]. The rate of deamination of ethylenediamine is enhanced by its complexation with silver (III). The involvement of [Ag^III(H₂IO₆) (H₂O)₂] and [Ag^III(H₂IO₆) (OH)₂]²⁻ are suggested as the reactive silver (III) species kinetically in mild basic and basic conditions, respectively. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 286–293, 2000     

Kinetics of oxidation of glycine and related substrates by diperiodatoargentate (III)

The reactions of diperiodatoargentate(III) with glycine and related compounds have been examined. The monoperiodatosilver(III) species acts as an active oxidant in comparison to that of diperiodatosilver(III) species. These reactions consist of three kinetically distinguishable steps-induction period, complexation and oxidation. Complexation of these substrates takes place with a second order rate constant of (0.2–1.6)×10⁴ dm³ mol⁻¹ s⁻¹ whereas the redox process occurs at a rate of (0.3–6.0)×10² dm³ mol⁻¹ s⁻¹ except in case of cysteine with which these processes occurred by an order of magnitude faster. The rate of electron transfer from carboxylic acids to the silver(III) complex is observed to be several order of magnitude smaller in comparison to that of amino acids. Both the rate of complexation and electron transfer are influenced by the structure of the substrates. The aquated silver(III) species is found to be more reactive in comparison to the hydroxylated silver(III) species.     

Promotion of the fenton reaction by Cu2+ ions: Evidence for intermediates

The promotion of the Fenton reaction by Cu²⁺ ions has been investigated using a wide range of [Cu²⁺]. Both the disappearance of Fe²⁺ and the evolution of O₂ were followed as a function of time by quenching the reaction mixture with o‐phenanthroline or with excess Fe^{2 +} ions, respectively. Two series of experiments were performed. In one series [H₂O₂] was 5 × 10⁻⁴ mol dm⁻³, and in the other [H₂O₂] was reduced to 5 × 10⁻⁵ mol dm ⁻³. By stopping the reaction with excess Fe²⁺ ions, significant differences in the measured absorbance in the two series were observed. In the higher [H₂O₂] range, the absorbance decreased monotonically in time, due to O₂ formation during the reaction. In the lower range, an initial transient rise of the absorbance was observed, indicating the formation of spectroscopically distinct intermediates in the system. A mechanism involving the intermediates FeOCu⁴⁺ and FeOCu⁵⁺ has been set up. Rate constants of the mechanism have been determined. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 725–736, 2006     

Electroactivated Disposable Pencil Graphite Electrode – New,Cost-effective,and Sensitive Electrochemical Detection of Bioflavonoid Hesperidin

In this paper, for the first time, electroactivated disposable pencil graphite electrode (ePGE) was used for the detection of bioflavonoid hesperidin with cyclic and differential pulse voltammetry. The electroactivation efficiency of the pencil graphite electrode (PGE) was examined employing electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) and the enhancement of electron transfer kinetics of the PGE after the electroactivation was found. Hesperidin is irreversibly oxidized on the ePGE and its oxidation was the most pronounced at pH=5.0. Two electrode processes were detected, on one hand, a mixed diffusion and adsorption control was observed for the first electrode process. On the other hand, only diffusion control was observed in the second electrode process. Linear dependence between the peak current and the hesperidin concentration was obtained in the concentration range from 5×10⁻⁷ mol dm⁻³ to 1×10⁻⁵ mol dm⁻³ and the determined lower limit of detection (LOD) was 2×10⁻⁷ mol dm⁻³. Moreover, hesperidin in pharmaceutical formulation (containing active substance, hesperidin, and excipients) was quantified using ePGE. A good correlation was obtained between experimentally obtained hesperidin concentration by voltammetric analysis and concentration determined by standard HPLC technique (R²=0.9462).     

Ion-pair formation in the outer-sphere electron transfer reactions between tris-(1, 10) phenanthroline iron(II) and the halopentacyanocobaltate(III) complexes in aqueous acidic solutions

The kinetics of the reactions between Fe(phen) ₃ ²⁺ [phen = tris–(1,10) phenanthroline] and Co(CN)₅X³⁻ (X = Cl, Br or I) have been investigated in aqueous acidic solutions at I = 0.1 mol dm⁻³ (NaCl/HCl). The reactions were carried out at a fixed acid concentration ([H⁺] = 0.01 mol dm⁻³) and the second-order rate constants for the reactions at 25 °C were within the range of (0.151–1.117) dm³ mol⁻¹ s⁻¹. Ion-pair constants K _ip for these reactions, taking into consideration the protonation of the cobalt complexes, were 5.19 × 10⁴, 3.00 × 10² and 4.02 × 10⁴ mol⁻¹ dm⁻³ for X = Cl, Br and I, respectively. Activation parameters measured for these systems were as follows: ΔH* (kJ K⁻¹ mol⁻¹) = 94.3 ± 0.6, 97.3 ± 1.0 and 109.1 ± 0.4; ΔS* (J K⁻¹) = 69.1 ± 1.9, 74.9 ± 3.2 and 112.3 ± 1.3; ΔG* (kJ) = 73.7 ± 0.6, 75.0 ± 1.0 and 75.7 ± 0.4; E _a (kJ) = 96.9 ± 0.3, 99.8 ± 0.4, and 122.9 ± 0.3; A (dm³ mol⁻¹ s⁻¹) = (7.079 ± 0.035) × 10¹⁶, (1.413 ± 0.011) × 10¹⁷, and (9.772 ± 0.027) × 10²⁰ for X = Cl, Br, and I respectively. An outer – sphere mechanism is proposed for all the reactions.     

Nucleophilic and electrophilic promotion of ligand substitution reactions in oxo‐bridged,dinuclear chromium(III) complexes

Base hydrolysis reactions of [Cr(tmpa)(NCSe)]₂O²⁺, [Cr(tmpa)(N₃)]₂O²⁺, [Cr₂(tmpa)₂(μ−O)(μ−PhPO₄)]⁴⁺ and [Cr₂(tmpa)₂(μ−O)(μ−CO₃)]²⁺ follow the pseudo‐first‐order relationship (excess OH⁻): k_obsd=k_o+k_bQ_p[OH⁻]/(1+Q_p[OH⁻]). For the CO₃²⁻ complex, k_b(60°C)=(1.50±0.03)×10⁻² s⁻¹; ΔH‡=61±2 kJ/mol, ΔS‡=−99±7 J/mol K; Q_p(60°C)=(3.8±0.3)×10¹ M⁻¹; ΔH°=67±2 kJ/mol, ΔS°=230±7 J/mol K (I=1.0 M). An isokinetic relationship among k_OH(=k_bQ_p) activation parameters for five (tmpa)CrOCr(tmpa) complexes shows that all follow essentially the same pathway. Activated complex formation is thought to require nucleophilic attack of coordinated OH⁻ at the chromium‐leaving group bond in the k_b step, accompanied by reattachment of a tmpa pyridyl arm displaced by OH⁻ in the Q_p preequilibrium. Abstraction of both thiocyanate ligands was observed upon mixing [Cr(tmpa)(NCS)]₂O²⁺ with [Pd(CH₃CN)₄]²⁺ in CH₃CN solution. The proposed mechanism requires rapid complexation of both reactant thiocyanate ligands by Pd(II) (K_p(25°C)=(4.5±0.2)×10⁸ M⁻²; ΔH°=−32±6 kJ/mol, ΔS°=59±19 J/mol K) prior to rate‐limiting Cr NCS bond‐breaking (k₂(25°C)=(1.17±0.02)×10⁻³ s⁻¹; ΔH‡=98±2 kJ/mol, ΔS‡=27±5 J/mol K). Pd(II)‐assisted NCS⁻ abstraction is not driven by weakening of the Cr( )NCS⁻ bond through ligation of the sulfur atom to palladium, but rather by a favorable ΔS‡ resulting from the release of Pd(NCS)⁺ fragments and weak solvation of the activated complex in CH₃CN solution. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 351–356, 1999     

Application of Non‐Stop‐Flow Differential Pulse Voltammetry at a Tubular Detector of Silver Solid Amalgam for Electrochemical Determination of Lomustine (CCNU)

An application of the flow differential pulse voltammetry with tubular detector based on silver solid amalgam for determination of antineoplastic drug lomustine in pharmaceutical preparations is presented. The highest sensitivity was obtained in [0.10 mol dm^?3 MES; 2.00 mol dm^?3 NaCl; pH 6.0]:EtOH (9 : 1) with flow rate 0.50 mL min^?1, and the magnitude of the modulation amplitude ?0.070 V. The calibration dependence was linear in the range 1×10^?6–1 × 10^?4 mol dm^?3 (R²=0.999). The limit of detection was 1.5×10^?7 mol dm^?3. This method was successfully used for determination of lomustine in real samples of chemotherapy drug CeeNU Lomustine 40 mg.     

Cyclodextrin Modified Carbon Paste Based Electrodes as Sensors for the Determination of Carcinogenic Polycyclic Aromatic Amines

Voltammetric properties and possibility of the determination of carcinogenic aminoderivatives of polycyclic aromatic hydrocarbons, namely 1‐ and 2‐aminonaphthalene and 2‐aminobiphenyl, have been investigated. Carbon paste electrodes (CPE) modified with monomeric α‐, β‐ or γ‐cyclodextrin and carbon‐based screen‐printed electrodes (SPE) surface‐modified with a thin film of β‐cyclodextrin (β‐CDP) or carboxymethylated β‐cyclodextrin (β‐CDPA) condensation polymer were used for that purpose as simple electrochemical biosensors. Analytical procedure for the DPV determination of tested amines using these biosensors was proposed. Linear calibration plots within the concentration range of 2×10^?8 – 2×10^?7 mol dm^?3 and 2×10^?7–1×10^?6 mol dm^?3 with limits of quantification of the order of 10^?9 mol dm^?3 were obtained for the modified CPE and modified SPE.     

Carbonate ion electrode based on HTPP sites

Several quaternary phosphonium salts have been used as the site materials for construction of carbonate ion electrodes. Among them the electrode based on hexadecyltriphenylphosphonium salt showed best performance characteristics. The Nerstian response range of the electrode is from 1 × 10^?2 down to 6.3 × 10^?7 mol · dm^?3 with a detection limit of 1.8 × 10^?7 mol · dm³. The selectivity order of ions can be altered by the introduction of trifluoroacetyl-tert-butylbenzene as a solvent mediator. The strong solvatoin of the primary ion of interest in the membrane phase by the solvent mediator favors the improvement of the selectivity of the proposed electrode.     

Chloride and iodide mediated oxidation of antimony(III) by cerium(IV) in aqueous sulphuric acid medium

The micro amounts of iodide (10⁻⁷) (mol dm⁻³) and chloride (10⁻²) (mol dm⁻³) mediated oxidation of antimony(III) by cerium(IV) in an aqueous sulphuric acid medium have been studied spectrophotometrically at 25 °C and μ = 3.10 mol dm⁻³. The stoichiometry is 1:2 in chloride and iodide mediated reactions. i.e. one mole of antimony(III) requires two moles of cerium(IV). In the case of chloride mediated reaction, the reaction was first order in cerium(IV) and halide concentrations, whereas in the case of iodide mediated reaction the order with respect to [cerium(IV)] was unity and with respect to iodide concentrations was more than unity (ca. 1.4). In both chloride and iodide mediated reactions the order with respect to antimony(III) concentrations was less than unity. Increase in sulphuric acid concentration increased the rate. The order with respect to H⁺ ion concentration was less than unity. Added products, cerium(III) and antimony(V) did not have any significant effect on the reaction rate. The active species of oxidant was understood to be , whereas that of reductant as SbCl₃ in the case of chloride and SbI²⁺ in case of iodide mediated reactions. The possible reaction mechanisms were proposed and the activation parameters were determined and discussed.     

Poly(styrene‐b‐isobutylene) multiarm star‐block copolymers

Multiarm star‐branched polymers based on poly(styrene‐b‐isobutylene) (PS‐PIB) block copolymer arms were synthesized under controlled/living cationic polymerization conditions using the 2‐chloro‐2‐propylbenzene (CCl)/TiCl₄/pyridine (Py) initiating system and divinylbenzene (DVB) as gel‐core‐forming comonomer. To optimize the timing of isobutylene (IB) addition to living PS⊕, the kinetics of styrene (St) polymerization at −80°C were measured in both 60 : 40 (v : v) methyl cyclohexane (MCHx) : MeCl and 60 : 40 hexane : MeCl cosolvents. For either cosolvent system, it was found that the polymerizations followed first‐order kinetics with respect to the monomer and the number of actively growing chains remained invariant. The rate of polymerization was slower in MCHx : MeCl (k_app = 2.5 × 10⁻³ s⁻¹) compared with hexane : MeCl (k_app = 5.6 × 10⁻³ s⁻¹) ([CCl]_o = [TiCl₄]/15 = 3.64 × 10⁻³M; [Py] = 4 × 10⁻³M; [St]_o = 0.35M). Intermolecular alkylation reactions were observed at [St]_o = 0.93M but could be suppressed by avoiding very high St conversion and by setting [St]_o ≤ 0.35M. For St polymerization, k_app = 1.1 × 10⁻³ s⁻¹ ([CCl]_o = [TiCl₄]/15 = 1.82 × 10⁻³M; [Py] = 4 × 10⁻³M; [St]_o = 0.35M); this was significantly higher than that observed for IB polymerization (k_app = 3.0 × 10⁻⁴ s⁻¹; [CCl]_o = [Py] = [TiCl₄]/15 = 1.86 × 10⁻³M; [IB]_o = 1.0M). Blocking efficiencies were higher in hexane : MeCl compared with MCHx : MeCl cosolvent system. Star formation was faster with PS‐PIB arms compared with PIB homopolymer arms under similar conditions. Using [DVB] = 5.6 × 10⁻²M = 10 times chain end concentration, 92% of PS‐PIB arms (M_n,PS = 2600 and M_n,PIB = 13,400 g/mol) were linked within 1 h at −80°C with negligible star–star coupling. It was difficult to achieve complete linking of all the arms prior to the onset of star–star coupling. Apparently, the presence of the St block allows the PS‐PIB block copolymer arms to be incorporated into growing star polymers by an additional mechanism, namely, electrophilic aromatic substitution (EAS), which leads to increased rates of star formation and greater tendency toward star–star coupling. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1629–1641, 1999     

Discharge flow‐chemiluminescence study of the rate coefficients for O(3P) + CF2CCl2 and O(3P) + CF3CFCF2 reactions at 298 K

The kinetics of the reactions O(³P) + CF₂CCl₂ and O(³P) + CF₃CFCF₂ were studied at room temperature in a discharge flow tube system. The overall rate constants based on the measured afterglow reactions were (3.10 ± 0.40) × 10⁻¹³ and (3.00 ± 0.60) × 10⁻¹⁴ cm³ molecule⁻¹ s⁻¹, respectively. The experiments were carried out under pseudo‐first‐order conditions with [O(³P)]₀ ≪ [alkene]₀. These results are compared with previous relative measurements using different experimental techniques. The effect of substituent atoms or groups on the overall rate constants is analyzed in comparison with other alkenes in the literature. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 867–872, 1999     

Determination of the rate constants for the gas-phase reactions of methyl butenol with OH radicals,ozone, NO3 radicals,and Cl atoms

Using a relative rate method, rate constants for the gas-phase reactions of 2-methyl-3-buten-2-ol (MBO) with OH radicals, ozone, NO₃ radicals, and Cl atoms have been investigated using FTIR. The measured values for MBO at 298±2 K and 740±5 torr total pressure are: k_OH=(3.9±1.2)×10⁻¹¹ cm³ molecule⁻¹ s⁻¹, k_O3=(8.6±2.9)×10⁻¹⁸ cm³ molecule⁻¹ s⁻¹, k=(8.6±2.9)×10⁻¹⁵ cm³ molecule⁻¹ s⁻¹, and k_Cl=(4.7±1.0)×10⁻¹⁰ cm³ molecule⁻¹ s⁻¹. Atmospheric lifetimes have been estimated with respect to the reactions with OH, O₃, NO₃, and Cl. The atmospheric relevance of this compound as a precursor for acetone is, also, briefly discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 589–594, 1998     

Kinetics of the gas-phase reactions of indan,indene, fluorene,and 9,10-dihydroanthracene with OH radicals,NO3 radicals,and O3

The kinetics of the gas-phase reactions of OH radicals, NO₃ radicals, and O₃ with indan, indene, fluorene, and 9,10-dihydroanthracene have been studied at 297 ± 2 K and atmospheric pressure of air. The rate constants, or upper limits thereof, for the O₃ reactions were (in cm³ molecule⁻¹ s⁻¹ units): indan, < 3 × 10⁻¹⁹; indene, (1.7 ± 0.5) × 10⁻¹⁶, fluorene, < 2 × 10⁻¹⁹; and 9,10-dihydroanthracene, (9.0 ± 2.0) × 10⁻¹⁹. Using a relative rate method, the rate constants for the OH radical and NO₃ radical reactions, respectively, were (in cm³ molecule⁻¹ s⁻¹ units): indan, (1.9 ± 0.5) × 10⁻¹¹ and (6.6 ± 2.0) × 10⁻¹⁵; indene, (7.8 ± 2.0) × 10⁻¹¹ and (4.1 ± 1.5) × 10⁻¹²; fluorene, (1.6 ± 0.5) × 10⁻¹¹ and (3.5 ± 1.2) × 10⁻¹⁴; and 9,10-dihydroanthracene, (2.3 ± 0.6) × 10⁻¹¹ and (1.2 ± 0.4) × 10⁻¹². These kinetic data were used to assess the relative contributions of the various reaction pathways. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 299–309, 1997.     

The mechanism and kinetics of energy transfer processes in Xe–CCl4–M (M=CO,CO2) mixtures irradiated by xenon resonance light

The mechanism and kinetics of energy transfer from the Xe(6s[3/2]₁) resonance state to CO and CO₂ molecules have been investigated by XeCl(B–X) (λ_max=308 nm) fluorescence intensity measurements at stationary conditions in Xe–CCl₄–M systems. Steady-state analysis of the fluorescence intensity dependence on the xenon and M pressure at constant CCl₄ concentration shows that these processes occur in two- and three-body reactions: Xe(6s[3/2]₁⁰)+M→products; Xe(6s[3/2]₁⁰)+M+Xe→products. The two-body rate constants for above reactions have been found to be (0.7±0.2)×10⁻¹⁰ and (4.9±0.4)×10⁻¹⁰ cm³ s⁻¹ for CO and CO₂, respectively. The three-body rate constants have been found to be (3±1)×10⁻²⁹ and (2.4±0.3)×10⁻²⁸ cm⁶ s⁻¹ for CO and CO₂, respectively. It has been shown that the third order reaction is a very effective channel of xenon excited atoms decay at high xenon pressures (P(Xe)>50 Torr).     

Voltammetric Determination of Selected Aminoquinolines Using Carbon Paste Electrode

Optimum conditions have been found for voltammetric determination of mutagenic 5‐aminoquinoline, 6‐aminoquinoline and 3‐aminoquinoline by differential pulse voltammetry and adsorptive stripping differential pulse voltammetry on carbon paste electrode. The lowest limits of determination were found for adsorptive stripping differential pulse voltammetry in 0.1 mol dm^?3 H₃PO₄ (5×10^?7 mol dm^?3 , 1×10^?7 mol dm^?3, and 1×10^?7 mol dm^?3 for 5‐aminoquinoline, 6‐aminoquinoline and 3‐aminoquinoline, respectively). The possibility to determine mixtures of 8‐aminoquinoline with 3‐aminoquinoline or 5‐aminoquinoline or 6‐aminoquinoline, and mixtures of 5‐aminoquinoline with 3‐aminoquinoline or 6‐aminoquinoline by differential pulse voltammetry was verified. Binary mixtures of 8‐aminoquinoline with 3‐aminoquinoline or 6‐aminoquinoline, and of 3‐aminoquinoline with 5‐aminoquinoline could be successfully analyzed.