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1.
Conclusions The rate constants for the addition of triethylsilyl radicals to -phenyl-N-tert-butylnitrone (kadd=(11±5)·106 liter/mole·sec) and 2,4,6-tri-tert-butylnitrosobenzene (kadd= (1.5±0.3)·109 liter/mole·sec) at 20°C were determined by the EPR method.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 938–941, April, 1984.  相似文献   

2.
The time resolved fluorescence of Xe 2 * excimers in pure xenon and Xe-M (M=H2,N2,N2O,CO2) mixtures has been observed. The formation rate constant of Xe 2 * , k2=(1.1±0.1)·10–30 cm6/s and the lifetime of the excimer precursors, 0(100 ± 40) ns were evaluated. The quenching rate coefficients of Xe(6p) states by M have been found to be in the range of (0.5–1.3)·10–9 cm3/s. The basic parameters and operating characteristics of the newly constructed pulse radiolysis set up based on SINUS-5 electron accelerator are also presented.  相似文献   

3.
It is shown by pulse radiolysis that in aqueous solutions of hydrazine containing oxygen the radical N2H3 reduces oxygen to O2 at pH > 7 (k 3·109 dm3· mole–1·sec–1), while this reaction does not occur for the protonated form N2H4 + at pH < 7 (k, 5·106 dm3·mole–1·sec–1). The rate constants for the disappearance of O2 have been determined in the pH range from 4 to 12. Rate constants have been calculated for the reaction of O with N2H4 [k=(1.6 ±0.2)·109 dm3·mole–1·sec–1] and of O3with N2H4 [k=(1.2 ±0.2)·106 dm3· mole–1·sec–1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 341–345, February, 1991.  相似文献   

4.
The aggregation of dodecyltrimethylammonium hydroxide (DTAOH) aqueous solutions has been studied by several methods. It is stepwise and four critical points were found. AtC T=(2.51±0.10)×10–4 mol · dm–3 the surface excess becomes zero, atC T=(1.300±0.041)×10–3 mol · dm–3 small aggregates from, which grow with concentration. AtC T=(1.108±0.010)×10–2 mol · dm–3 true micelles form (CMC) and at (3.02±0.28)×10–2 mol · dm–3 the structure of micelles probably changes affecting their properties. The DTAOH micelles are highly ionized (=0.8) at the CMC, and decreases to reach very small values when the total concentration increases.  相似文献   

5.
The oxidation-reduction reaction between U(VI) and Ti(III) in HCl solution was studied spectrophotometrically. The reaction is second-order at all concentrations of reactants, HCl, ferrous chloride and mannitol used in this work. In 5M HCl the rate constantk increases with increasing Ti(III) concentration, whereas it decreases with increasing U(VI) concentration, with increasing HCl concentration from 1.00M to 7.17M and increases thereafter from 7.17M to 11.79M. The addition of mannitol causes a consistent decrease in the rate of reaction, whereas ferrous chloride has no effect. The activation energy for this oxidation-reduction reaction was 47.90±0.11 kJ·mol–1. The values of H , G and S were 45.40±0.11 kJ·mol–1, 72.50±0.17 kJ·mol–1 and –91.10±0.22J·k–1·mol–1, respectively. The mode of reaction is discussed in the light of kinetic results.  相似文献   

6.
The observed rate constant ratio,k 1obs/k 2 obs, for the sequential iodination of L-tyrosine was determined in the concentration range 1.84·10–3 to 1·10–6 M by the use of3H- and14C-labels and product analysis by HPLC. Iodinations by chloramine-T/I gave (k 1 obs/k 2 obs)· values (=the pH dependent factor) in the range 72±3 to 55±2 and molecular iodine iodinations gave values in the range 64±5 to 39±10. It is concluded that molecular iodine is the iodinating species in both cases.  相似文献   

7.
Summary. A new selective, sensitive, and simple kinetic method is developed for the determination of trace amounts of chromium (VI). The method is based on the catalytic effect of Cr(VI) on the reaction of sodium pyrogallol-5-sulphonate (PS) with hydrogen peroxide. The reaction is followed spectrophotometrically by tracing the oxidation product at 437nm within 1min after addition of H2O2. The optimum reaction conditions are PS (1.32·10–3mol·dm–3), H2O2 (0.32mol·dm–3), HClO4 (2.6·10–3mol·dm–3) at 25°C. Following this procedure, chromium (VI) can be determined with a linear calibration graph up to 0.25ng·cm–3 and a detection limit of 0.024ng·cm–3, based on the 3 criterion. The interference effect of several species was also investigated and it was found that the most common cations and anions do not interfere with the determination. The developed procedure was successfully applied to the determination of Cr(VI) and total Cr in river waters and total Cr in herbal samples.  相似文献   

8.
Summary The kinetics of the thermal and photochemical decomposition of aquapentacyanoferrate(III) ion in aqueous solution in the presence ofo-phenanthroline was studied spectrophotometrically. The first-order rate constant (k ) at 30° C [I=1 M(NaCl)] for the thermal reaction is (1.49±0.13)×10–6 s–1 with H =(158±7)kJ mol–1 and S=(42±4) JK–1 mol–1. The initial quantum yield for the photochemical reaction at pH=7 is independent of the light intensity and is (1.49±0.33)×10–2 mol einstein–1.A communication on this subject was presented at the XVI Latinamerican Chemistry Congress held at Rio de Janeiro. Brasil, October 14–20, 1984.  相似文献   

9.
A new selective, sensitive, and simple kinetic method is developed for the determination of trace amounts of chromium (VI). The method is based on the catalytic effect of Cr(VI) on the reaction of sodium pyrogallol-5-sulphonate (PS) with hydrogen peroxide. The reaction is followed spectrophotometrically by tracing the oxidation product at 437nm within 1min after addition of H2O2. The optimum reaction conditions are PS (1.32·10–3mol·dm–3), H2O2 (0.32mol·dm–3), HClO4 (2.6·10–3mol·dm–3) at 25°C. Following this procedure, chromium (VI) can be determined with a linear calibration graph up to 0.25ng·cm–3 and a detection limit of 0.024ng·cm–3, based on the 3 criterion. The interference effect of several species was also investigated and it was found that the most common cations and anions do not interfere with the determination. The developed procedure was successfully applied to the determination of Cr(VI) and total Cr in river waters and total Cr in herbal samples.  相似文献   

10.
The following extraction systems have been studied: (Ce3++Eu3+) (NO3)-(EDTA, DCTA, DTPA)/TBP in n-alkane and (Ce3++Eu3+)(NO3)/DEHPA in n-alkane at concentration ratios as follows: [Ce3+]=trace –1 mol·dm–3, [Eu3+]=trace –0.1 mol·dm–3. [TBP]=(0.183–1.83) mol·dm–3, [DEHPA]=(5·10–3–0.1) mol·dm–3, [(H, Na)NO3]=(0.1–6) mol·dm–3, [Eu3+]: [EDTA, DCTA, DTPA]=11–110. The initial concentration of Eu3+ in aqueous phase in the extraction system containing a mixture of Ce3+ and Eu3+ was trace, 1% and 10% compared with the Ce3+ concentration. The distribution of the elements between the phases was observed radiometrically using141Ce,152Eu and154Eu. The results are documented by the distribution ratios DCe, DEu and separation factor =DEu/DCe as functions of variable parameters of the systems.  相似文献   

11.
Summary Cyanide ion reacts with [Fe(Par)2]2–,i.e. Par=4-(2-pyridylazo)resorcinol to form a 113 mixed cyanocomplex. The reaction has been studied spectrophotometrically at 720 nm max, pH=11.5±0.02, and I=0.1 M (NaClO4) at 25±0.1°C. The order with respect to cyanide varies from one to two at high and low cyanide concentrations respectively. The rate constants for respective reactions are k1=(6.1±0.3)×10–2 M–1 s–1, k2=(12.6±1.0) M–2 s–1. The reverse reaction does not occur at a measurable rate even in presence of a large excess of Par. These observations suggest that [Fe(Par)2]2– forms a mixed [FePar(CN)3]3– complex in presence of an excess of cyanide ion. The activation parameters for the reaction have been calculated and used to support a three step mechanism consistent with these results. The effect of ionic strength tends further support to the mechanism.  相似文献   

12.
The kinetics of reaction of indium(III)ion with EDTA (H4 edta) has been studied in aqueous acidic solutions using carrier-free111In and low concentrations of EDTA. The reaction takes place predominatly between indium(III) and H3 edta. The rate constant k3 is determined to be k3=(1.3±0.1)·105 dm3 mol–1 s–1 (25 °C).  相似文献   

13.
The regularities of vapor-phase nitration of cellulose with HNO3 under conditions of natural convection and hindered heat removal in the absence of air were studied using the nonisothermal kinetic method. It was established that the nitration rate at the depth of conversion of 0.08 to 0.7 is described by the kinetic law d/dt =k 1 p/(1+), wherek 1 = 104.49±0.6 exp(–A/RT) s–1 atm–1, = 10–35.5±15.7exp(B/RT),A = 36.6±3.8 kl mol–1, andB = 203±88 kJ mol–1. The diffusion mechanism of vapor-phase nitration of cellulose, which explains the high value of activation energies, is discussed. The effective diffusion coefficient of HNO3 in cellulose at 25 °3.7 · 10–7 cm2 s–1) and the activation energy of diffusion (38.3±4.2 kJ mol–1) were estimated.For Part 1, see Ref. l.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1981–1985, August, 1996.  相似文献   

14.
The reaction of iodine monoxide with chlorine monoxide resulting in atom escape to the gas phase is studied at T = (303 ± 5) K and P = 2.5 Torr using a flow setup for measuring the resonance fluorescence signals of atomic iodine and chlorine. The heterogeneous reaction between chlorine monoxide and iodine monoxide occurring at the reactor surface covered with an F32-L Teflon-like compound and treated by the reaction products is characterized by the rate constant k = (4.9 ± 0.2) × 10–11 cm3 molecule–1 s–1. This value is substantially higher than the rate constant for the homogeneous reaction IO· + ClO· (k 1 1 × 10–12 cm3 molecule–1 s–1).  相似文献   

15.
The -propionic acid methyl ester radical was produced in dissociative electron capture reaction of 2-chloropropionic acid methyl ester. The absorption maxima of the radical are at 310 and 300 nm in cyclohexane and water with extinction coefficients of 440±50 and 400±50 mol–1 dm3 cm–1. The second order decay rate parameter in water is (2.3±0.5)×109 mol–1 dm3 s–1. The peroxy radicals have the characteristics: max=265–270 nm, max=700–900 mol–1 dm3 and 2k=(7±2)·108 mol–1 dm3 s–1.  相似文献   

16.
Apparent equilibrium constants and calorimetric enthalpies of reaction have been measured for the reaction L-tryptophan(aq) + H2O(l) = indole(aq) + pyruvate(aq) + ammonia(aq) which is catalyzed by L-tryptophanase. High-pressure liquid-chromatography and microcalorimetery were used to perform these measurements. The equilibrium measurements were performed as a function of pH, temperature, and ionic strength. The results have been interpreted with a chemical equilibrium model to obtain thermodynamic quantities for the reference reaction: L-tryptophan(aq) + H2O(l) = indole(aq) + pyruvate(aq) + NH 4 + (aq). At T=25°C and Im=O the results for this reaction are: Ko=(1.05±0.13)×10–4, G°=(22.71±0.33) kJ-mol–1, H°=(62.0±2.3) kJ-mol–1, and S°=(132±8) J-K–1-mol–1. These results have been used together with thermodynamic results from the literature to calculate standard Gibbs energies of formation, standard enthalpies of formation, standard molar entropies, standard molar heat capacities, and standard transformed formation properties for the substances participating in this reaction.Presented at the Symposium, 76th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65th birthday.  相似文献   

17.
The title reaction has been studied spectrophotometrically in aqueous medium as a function of [substrate complex], [ligand], pH and temperature at constant ionic strength. At the physiological pH (7.4) the interaction with azide shows two distinct consecutive steps, i.e., it shows a non-linear dependence on the concentration of N3 ; both processes are [ligand]-dependent. The rate constant for the processes are: k 110–3 s–1 and k 210–5 s–1. The activation parameters calculated from Eyring plots are: H 1 = 14.8 ± 1 kJ mol–1, S 1 = –240 ± 3 J K–1 mol–1, H 2 = 44.0 ± 1.5 kJ mol–1 and S 2 = –190 ± 4 J K–1 mol–1. Based on the kinetic and activation parameters an associative interchange mechanism is proposed for the interaction process. From the temperature dependence of the outersphere association equilibrium constant, the thermodynamic parameters calculated are: H 1 0 = 4.4 ± 0.9 kJ mol–1, S 1 0 = 64 ± 3 J K–1 mol–1 and H 2 0 = 14.2 ± 2.9 kJ mol–1, S 2 0 = 90 ± 9 J K–1 mol–1, which gives a negative G 0 value at all temperatures studied, supporting the spontaneous formation of an outersphere association complex.  相似文献   

18.
The solvent used was dimethylformamide at neutral and alkaline pH. The equilibrium constants are determined by spectrophotometry. The rate of proton exchange has been measured as a function of temperature and concentration. The rate constants and activation energies have been measured; for uncatalyzed exchange kn=(1.5±0.5) ·· 103 M–1 sec–1, E=8±1 kcal/mole, while base-catalyzed exchange has k=(0.3±0.1) · 106 M–1 sec–1 and E=6±1 kcal/mole.We are indebted to A. I. Brodskii for assistance in this work, and to V. I. Oshkaderov and L. A. Kichakova for recording the NMR spectra.  相似文献   

19.
In view ofHammond's warning6 about the Conspiracy of errors, found in the case of low values of equilibrium constants of charge-transfer complexes a case is made out for redetermining the values for the system hexamethylbenzene—2,3-dichloro-1,4-naphthoquinone. Uncertainties in the parameters were estimated using theLiptay 8 matrix procedure. The solvent used was dichloromethane. The following data were obtained at 25°C: vC T = 22,220 cm–1;E A=0.99 eV;K =2599±57 l2·cm–1·mol–2. max= 1020 ± 148 cm–1··1;K=2.55±0.37 l·mol–1; –H=2.7±0.3 kcal·mol–1.With 1 Figure  相似文献   

20.
The oxidation of -terpinene by molecular oxygen is shown to occur by a radical chain mechanism involving hydroperoxy radicals. The principal molecular reaction products are H2O2 and 1-methyl-4-isopropylbenzene. The rate constants for chain propagation and chain breaking measured at 35–70°C are (liter/mol·s) lgk3 = 7.10– (6700±400)/4.57T and lgk5 = 9.80– (2700±300)/4.57T respectively.Translated from Teoreticheskaya Éksperimental'naya Khimiya, Vol. 30, No. 3, pp. 143–146, May–June, 1994The authors thank the Ukraine National Committee for the Basic Research Fund for financing this work.  相似文献   

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