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1.
The kinetics of the anation reaction of cis-diaquo-bis-oxalatochromate(III) ion by DL-alanine has been studied spectrophotometrically
in the pH range 3.8 to 7.3, where DL-alanine remains in zwitterionic form. A second-order rate law has been established. Reaction
rates in three different ethanol-water mixtures were measured. In each solvent medium the anation rate is higher as compared
to water exchange reaction at a particular temperature. The activation parameters (gDH# and ΔS#) in different ethanol-water mixtures were obtained from Eyring plots. ΔG#(ΔH# −TΔS
#) values were calculated in each solvent medium and compared with that of the isotopic water exchange process. A reaction
mechanism involving theS
N2 path has been suggested. 相似文献
2.
The reaction of 1-ethoxycarbonylmethyl-5,5,7,7-tetramethyl-2-oxo-tetrahydroimidazo[1,5-b]oxadiazol-6-oxyl with the weakly basic nucleophiles NaN3, NaCN, KF, KBr, KCl and NaNO2 has been studied. It was shown for the first time that, as in the case of NaOH and MeONa, the reaction occurs with opening
of the oxadiazolone ring to form exo-N-substituted amidines. It was shown that the weakly basic nucleophiles readily react
with substrates which contain a substituent sensitive to attack by such nucleophiles as NaOH or MeONa. The effect of the nature
of the nucleophiles on the reaction course for opening of the oxadiazolone ring was also studied. It was found that the reactivity
of the nucleophiles in DMSO changes in the series F− > CN− > N3– >NO2− > Cl− > Br− and qualitatively correlates with their basicities in this solvent. Examination of the effect of the ratio of the reagents
on the degree of conversion of the starting oxadiazolone has shown that a quantity of nucleophiles less than one equivalent
also allowed the cleavage reaction of the oxadiazolone heterocycle to go to completion through just increasing the reaction
time. The experimental data obtained lends support to the proposed reaction scheme.
Dedicated to Academician B. A. Trofimov in his 70th jubilee.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 71–78, January, 2009. 相似文献
3.
Oxidation of isatins (isatin, 5-methylisatin, 5-bromoisatin and 5-nitroisatin) to their anthranilic acids was performed efficiently
with sodium N-chlorobenzenesulfonamide or chloramine-B (CAB) in alkaline medium at 35±0.1°C. The reactions follow identical
kinetics for all the isatins, being first-order dependence each in [CAB]
o
and [Isatin]
o
and inverse fractional-order on [NaOH]. Addition of halide ions and benzenesulfonamide, reduction product of CAB, do not
significantly affect the rate. Variation of ionic strength of the medium had no effect on the rate, while the dielectric effect
is negative. The solvent isotope effect was studied using D2O. Activation parameters for the overall reaction have been computed. The rates satisfactorily correlate with the Hammett
σ relationship and the reaction constant ρ is −0.31 signifies that electron releasing groups accelerate the reaction while
the electron withdrawing groups retard the rate. Values of ΔH≠ and ΔS≠ are linearly related and an isokinetic relationship is observed with β=376 K, indicating the reaction is controlled by enthalpy.
The stoichiometry of the title reaction is found to be 1∶1. Oxidation products of isatins were identified as their corresponding
anthranilic acids and the yields were found to be around 90 %. The observed results have been explained by a plausible mechanism
and the related rate law deduced. This method offers several advantages including high yield of the products, short reaction
times, easier isolation of products, and stable, cost effective and relatively non-toxic reagents, which make the reaction
process simple and smooth. 相似文献
4.
The title cations were produced in aqueous solution by chemical initiation (solvolysis) of benzyl-gem-dihalides and benzyl-gem-diazides. The solvolysis reactions of benzyl-gem-dihalides and benzyl-gem-diazides in water proceed by a stepwise mechanism through α-halobenzyl carbocation and α-azidobenzyl carbocation intermediates,
which are captured by water to give the corresponding carbonyl compounds as the sole detectable products. Rate constant ratiok
x/ks(M−1) for partitioning of the carbocation between reaction with halide/azide ion and reaction with water is determined by analysis
of halide/azide common ion inhibition of the solvolysis reaction. The rate constantsk
s(s-1) for the reaction of the cation with solvent water were determined from the experimental values ofk
x/ks andk
solv, for the solvolysis of the benzyl-gem-dihalides and benzyl-gem-diazides respectively, usingk
x = 5 × 109M−1 s−1 for diffusion-limited reaction of halide/azide ion with α-substituted benzyl carbocations. The values of 1/k
s are thus the lifetimes of the α-halobenzyl carbocations and α-azidobenzyl carbocations respectively. 相似文献
5.
Miaoliang Huang Hongxun Yang Jihuai Wu Jianming Lin Zhang Lan Pingjiang Li Sancun Hao Peng Han Qiwei Jiang 《Journal of Sol-Gel Science and Technology》2007,42(1):65-70
Using poly(acrylonitrile-co-styrene) as polymer host, 1,2-propanediol carbonate, dimethyl carbonate and ethylene carbonate as mixture solvent, N-methyl-quinoline iodide and iodine as the source of I−/I3
−, a novel polymer gel electrolyte with ionic conductivity of 5.12 × 10−3 S· cm−1 at 25°C was prepared by sol-gel and hydrothermal methods. Based on the polymer gel electrolyte, a quasi-solid-state dye-sensitized
solar cell was fabricated. The solar cell possess better long-term stability and light-to-electrical energy conversion efficiency
of 4.04% under irradiation of 100 mW· cm−2. The influences of polymer host, solvent, N-methyl-quinoline iodide and temperature on ionic conductivity of the polymer gel electrolyte and the performance of the dye-sensitized
solar cell was discussed. 相似文献
6.
V. D. Kiselev E. A. Kashaeva L. N. Potapova A. I. Konovalov 《Russian Chemical Bulletin》2007,56(3):494-498
The effect of hydrostatic pressure below 1000 kg cm−2 on the rate of reactions of o-and p-nitrophenylsulfenyl chlorides with styrene and cyclohexene was studied. The activation and reaction volumes (cm3 mol−1) for the reactions of o-nitrophenylsulfenyl chloride with styrene in acetonitrile (−23.1 and −23.6), 1,2-dichloroethane (−29.2 and −24.7), chlorobenzene
(no, −20.2), and anisole (−25.1 and −21.2) and for the reaction of p-nitrophenylsulfenyl chloride with styrene in carbon tetrachloride (−39.5±1.5 and −22.0) were determined. In carbon tetrachloride
the activation volumes for the reactions of cyclohexene with o-and p-nitrophenylsulfenyl chlorides (−37.7±2.0 and −40.9±1.2 cm3 mol−1, respectively) are almost the same and coincide with the data for the reactions with styrene. The considerable decrease in
the volume of the transition state in the nonpolar solvent is considered as a consequence of the enhanced electrostriction
of carbon tetrachloride in the solvate sphere of the transition state of the reaction, which excludes the nonpolar transition
state of the sulfuran type.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 477–480, March, 2007. 相似文献
7.
The results of kinetic and equilibrium experiments with the set of reaction of proton abstraction from 4-nitrophenyl[bis(ethylsulphonyl)]methane
in acetonitrile are reported. Two strong organic bases are used: 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene
(MTBD).
The rates of proton transfer reaction have been measured by T-jump method in the presence of perchlorate of the appropriate
base as a common cation BH+ and supporting electrolyte-tetrabutylammonium perchlorate (TBAP) in the temperature range between 20–40°C are: k
H
=1.32×107−2.00×107 and 2.82×107−4.84×107 dm 3mol−1s−1 for MTBD and TBD respectively. The enthalpies of activation ΔH
MTBD
≠
=13.5 and ΔH
TBD
≠
=18.1 kJmol−1. The entropies of activation are negative: ΔS
MTBD
≠
=−62.3 and ΔS
TBD
≠
=−40.3 Jmol−1K−1.
The change of the absorbance of the anion of 4-nitrophenyl[bis9ethylsulphonyl)]methane at the temperature 25°C in the presence
of common cation BH+ gives the equilibrium constants K=705 and 906 M−1 for MTBD and TBD respectively.
Kinetic and equilibrium results are discussed. The possible mechanism of proton transfer reaction between 4-nitrophenyl[bis(ethylsulphonyl)]methane
and cyclic organic bases: MTBD and TBD in acetonitrile is proposed. 相似文献
8.
Shivamurti A. Chimatadar Shankar V. Madawale Sharanappa T. Nandibewoor 《Transition Metal Chemistry》2007,32(5):634-641
A minute quantity (10−6 mol dm−3) of iodide catalysed oxidation of l-glutamic acid by CeIV has been studied in H2SO4 and SO
4
2−
media. The reaction was first order each in [CeIV] and [I−]. The order with respect to [l-glutamic acid] was less than unity (0.71). Increase in [H2SO4] decreased the reaction rate. The added HSO
4
−
and SO
4
2−
decreased the rate of reaction. The added product, succinic acid, had no effect on the reaction rate, whereas added CeIII retarded the reaction. The ionic strength and dielectric constant did not have any significant effect on the rate of reaction.
The active species of oxidant was Ce(SO4)2. A suitable mechanism was proposed. The activation parameters were determined with respect to the slow step of the mechanism.
The thermodynamic quantities were also determined and discussed. 相似文献
9.
The effect of the concentration of water on the rate of reduction of molecular nitrogen to hydrazine by niobium(iii) hydroxide in alkaline H2O−MeOH and D2O−MeOD mixtures was studied. In both cases, the reaction rate is maximum when [H2O]=4 mol L−1, and the inverse isotopic effect (K
D/k
H>1) is observed when [H2O]<20 mol L−1. Similar regularity was observed for the reaction of hydrogen elimination. It was found that HD is formed in the H2O−MeOH system in the presence of D2. The conclusion was made that the ratedetermining stage in hydrazine formation is the transfer of a hydride ion to the dinitrogen
molecule coordinated to the binuclear NbIII center. A kinetic scheme satisfactorily explaining the effect of the concentration of water ([H2O]=1.5−49.0 mol L−1) on the reaction rate constant was proposed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1600–1604, September, 1997. 相似文献
10.
Kinetics of oxidation of acidic amino acids (glutamic acid (Glu) and aspartic acid (Asp)) by sodium N-bromobenzenesulphonamide
(bromamine-B or BAB) has been carried out in aqueous HClO4 medium at 30°C. The rate shows first-order dependence each on [BAB]o and [amino acid]o and inverse first-order on [H+]. At [H+] > 0·60 mol dm−3, the rate levelled off indicating zero-order dependence on [H+] and, under these conditions, the rate has fractional order dependence on [amino acid]. Succinic and malonic acids have been
identified as the products. Variation of ionic strength and addition of the reaction product benzenesulphonamide or halide
ions had no significant effect on the reaction rate. There is positive effect of dielectric constant of the solvent. Proton
inventory studies in H2O-D2O mixtures showed the involvement of a single exchangeable proton of the OH− ion in the transition state. Kinetic investigations have revealed that the order of reactivity is Asp > Glu. The rate laws
proposed and derived in agreement with experimental results are discussed. 相似文献
11.
Oxidation of acetylacetone (AA) by bromamine-B (BAB) in HC1 medium (0.1 to 0.6 mol dm−3) at constant ionic strength has been investigated at 40°C. The rate is first order in [BAB]0 and fractional order each in [AA]0 and [H+]. The reaction is also catalysed by chloride ion. Michaelis-Menten type of kinetics is observed. Decrease in dielectric constant
of medium increases the rate. A solvent isotope effect κ′H2O/κ′D2O = 0.96 has been noted. Activation parameters for the rate limiting step have been computed. The mechanism involves the enol
form of the diketone. 相似文献
12.
Because Nitrosomonas europaea contains ammonia-oxidizing enzyme, nitrite reductase, and nitrous oxide reductase, the conversion of ammonia to dinitrogen
was tried with different reaction conditions. In aerobic reaction conditions, ammonium was converted to nitrite (NO
2
−
), while under oxygen-limiting or oxygen-free conditions, NO
2
−
-N formed from ammonia oxidation by N. europaea was reduced to N2O and dinitrogen with 22% conversion. During denitrification, optimal pH for the production of N2O and dinitrogen was found to be 7.0–8.0. Dinitrogen was not produced in acidic pH<7.0. A low partial oxygen pressure as well
as oxygen-free conditions are favorable for high production of dinitrogen. 相似文献
13.
Ibrahim M. EI-Mehasseb Abd El-Motaleb M. Ramadan Raafat M. Issa 《Transition Metal Chemistry》2006,31(6):730-739
The oxidation of catechol by molecular oxygen in the presence of a catalytic amount of copper(II) complex with 2-methyl-3-amino-(3H)quinazoline-4-one (MAQ) and various anions (Cl−, Br−, ClO
4
−
, SCN−, NO
3
−
and SO
4
–
) was studied. The catecholase biomimetic catalytic activity of the copper(II) complexes has been determined spectrophotometrically
by monitoring the oxidative transformation of catechol to the corresponding light absorbing o-quinone (Q). The rate of the catalytic oxidation reaction was investigated and correlated with the catalyst structure, time,
concentration of catalyst and substrate and finally solvent effects. Addition of pyridine or Et3N showed a dramatic effect on the rate of oxidation reaction. Kinetic investigations demonstrate that the rate of oxidation
reaction has a first order dependence with respect to the catalyst and catechol concentration and obeying Michaelis–Menten
Kinetics. It was shown that the catalytic activity depends on the coordination environment of the catalyst created by the
nature of counter anions bound to copper(II) ion in the complex molecule and follows the order: Cl− > NO
3
−
> Br− > SO
4
–
> SCN− > ClO
4
−
. To further elucidate the catalytic activity of the complexes, their electrochemical properties were investigated and the
catecholase mimetic activity has been correlated with the redox potential of the Cu2+/Cu+ couple in the complexes. 相似文献
14.
Nikos G. Tsierkezos 《Journal of solution chemistry》2007,36(10):1301-1310
The reduction of benzophenone (Bzph) in 3-pentanone (PEN), acetone (ACE), N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), tetrahydrofuran (THF), acetonitrile (ACN) and dimethyl sulfoxide (DMSO) with n-tetrabutylammonium hexafluorophosphate (TBAPF6) as background electrolyte was studied using the technique of cyclic voltammetry at the temperature of 263.15 K. The half-wave
potentials (E
1/2) were extracted. The reduction of Bzph occurs in two successive one-electron steps to produce first the free radical anion
Bzph− and then the dianion Bzph2−. The results indicated that the radical anion Bzph− is reoxidized to Bzph in all investigated solvent media whereas the dianion Bzph2− is reoxidized to Bzph− only in THF. The heterogeneous electron-transfer rate constants (k
s
) were evaluated by employing the electrochemical rate equation proposed by Nicholson. The rate of electron transfer for the
Bzph/Bzph− couple was found to be relatively slow in all investigated solvent media. Consequently, the electron-transfer processes can
be recognized as quasi-reversible. The diffusion coefficients (D) of Bzph in the investigated solvent media have been calculated using the modified Randles-Sevcik equation. The effect of
the physical and chemical properties of the solvent medium on the electrochemical behavior of Bzph has been examined. 相似文献
15.
The temperature dependences of the equilibrium constants of two chain reversible reactions in quinonediimine (quinonemonoimine)—2,5-dichlorohydroquinone
systems in chlorobenzene were studied. The enthalpy of equilibrium of the reversible reaction of quinonediimine with 4-hydroxydiphenylamine
was estimated from these data (ΔH = − 14.4±1.6 kJ mol−1) and a more accurate value of the N-H bond dissociation energy in the 4-anilinodiphenylaminyl radical was determined (D
NH = 278.6±3.0 kJ mol−1). A chain mechanism was proposed for the reaction between quinonediimine and 2,5-dichlorohydroquinone, and the chain length
was estimated (ν = 300 units) at room temperature. Processing of published data on the rate constant of the reaction of styrylperoxy
radicals with 2,5-dichlorohydroquinone in the framework of the intersecting parabolas method gave the O-H bond dissociation
energy in 2,5-dichlorohydroquinone: D
OH = 362.4±0.9 kJ mol−1. Taking into account these data, the O-H bond dissociation energy in the 2,5-dichlorosemiquinone radical was found: D
OH = 253.6±1.9 kJ mol−1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1661–1666, October, 2006. 相似文献
16.
Kinetic data for the colloidal MnO2–thiourea redox system are reported for the first time. The reduction of water-soluble colloidal MnO2 by thiourea (sulfur containing reductant) in aqueous perchloric acid medium has shown that it proceeds in two stages, i.e., a fast stage followed by a relatively slow second stage. The log (absorbance) versus time plot deviates from linearity. The kinetics of both the stages was investigated spectrophotometrically. The first-order kinetics with respect to [thiourea] at low concentration shifts to zero-order at higher concentration. The reaction rate increases with [HClO4] and the kinetics reveals complex order dependence in [HClO4]. Addition of P2O
7
4−
and F− in the form of Na4P2O7 and NaF, respectively, has inhibitory effect on the reaction rate. The reaction proceeds through the fast adsorption of thiourea on the surface of the colloidal MnO2. A mechanism involving the protonated thiourea as the reactive reductant species is proposed. The observed results are discussed in terms of Michaelis–Menten/Langmuir–Hinshelwood model. From the observed kinetic data, colloidal MnO2–thiourea adsorption constant (K
ad1) and rate constant (k
1) were calculated to be 1.25×1010 mol−1 dm3 and 3.1×10−4 s−1, respectively. The variation of temperature does not have any effect on the reaction rate. 相似文献
17.
The oxidation of iron(II) with tert-butyl hydroperoxide was investigated in the absence of oxygen in water, methanol, and the dichloromethane—methanol solvent
mixture (φr = 2:1). The oxidation rate depends on solvent polarity; measured in the presence of SCN− at constant 0.8 mmol dm−3 HCl, the rate constant increases with the polarity decrease passing from water and methanol to the dichloromethane—methanol
solvent mixture. Further, in non-aqueous solutions at this acid concentration the rate constant was higher than the rate constant
in the presence of Cl− only. The oxidation rate measured in the [FeCl]2+ complex in dichloromethane—methanol was slow in acidic medium and increased by decreasing the acid concentration. Approaching
the physiological pH conditions the rate constant attained the value of an order of magnitude of 103 dm3 mol−1 s−1, while very little alteration of stoichiometry of the oxidation reaction was observed. The rate constant measured in the
presence of Cl− strongly depends on electrolyte concentration at concentrations less than 0.5 mmol dm−3 HCl, both in MeOH and the solvent mixture. Based on these results, a possible mechanism of the influence of solvent, acidity,
and ligand type on the rate constant is discussed. We assume that the oxidation proceeds by an inner-sphere mechanism considering
that the breakdown of the successor inner-sphere complex forming reactive alkoxyl radicals is probably the rate-limiting step.
Presented at the 20th International Conference on the Coordination and Bioinorganic Chemistry organized by the Slovak Chemical
Society, Slovak University of Technology, Comenius University, and the Slovak Academy of Sciences, Smolenice Castle, 5–10
June 2005. 相似文献
18.
Yue Zhang Natsumi Watanabe Yuuko Miyawaki Yutaka Mune Kenta Fujii Yasuhiro Umebayashi Shin-ichi Ishiguro 《Journal of solution chemistry》2005,34(12):1429-1443
Aprotic N,N-dimethylpropionamide (DMPA) and N,N,N′,N′-tetramethylurea (TMU) are both strong donor solvents and coordinate to metal ions through the carbonyl oxygen atom. These
solvents show a different conformational aspect in the bulk phase, i.e., DMPA exists as either a planar cis or a nonplanar staggered conformer, while TMU exists in a single planar cis conformer. It has been established that the manganese(II) ion is solvated by five molecules in both solvents. Interestingly,
although the planar cis conformer of DMPA is more favorable than the nonplanar staggered one in the bulk phase, the reverse is the case in the coordination
sphere of the metal ion, i.e., a conformational change occurs upon solvation. To reveal the thermodynamic aspect of this conformational change, the complexation
of Mn(II) with bromide ions in DMPA and TMU has been studied by titration calorimetry at 298 K. It was found that the Mn(II)
ion forms mono-, di- and tri-bromo complexes in both solvents, and their formation constants, enthalpies and entropies were
obtained. The Δ H∘1 value for MnBr+ strongly depends on the solvent, i.e., it is positive (19.4 kJ-mol−1) in DMPA and negative (−8.7 kJ-mol−1) in TMU, whereas the Δ H^∘2 and Δ H∘3 values for the stepwise formation of MnBr2 and MnBr3− are both small and negative. The enthalpy of transfer ΔtH∘ from DMPA to TMU, which is evaluated on the basis of the extrathermodynamic TATB assumption, is 25.5 kJ-mol−1 for Mn2+ and −3.6 kJ-mol−1 for MnBr+. These values indicate that the difference between the formation enthalpy of MnBr+ in the two solvents, Δ H^∘1 (DMPA) – Δ H∘1 (TMU), is mainly ascribed to the value of ΔtH∘(Mn2+). It is found that the metal ion is also five-coordinated in the monobromo complex, MnBr(DMPA)4+ . The enthalpy for the conformational change of DMPA from its planar cis to the nonplanar staggered form is evaluated to be −11 and −5.5 kJ-mol−1 for Mn(DMPA)52 + and MnBr(DMPA)4+, respectively. Note that these values are significantly smaller than the corresponding value (5.0 kJ-mol−1) in the bulk phase. We thus conclude that, although steric hindrance among solvent molecules is reduced by replacing one
DMPA of Mn(DMPA)52 + with the relatively small bromide ion, DMPA molecules are still sterically hindered in the MnBr(DMPA)4+ complex. 相似文献
19.
Nitrous acid is a key redox controlling factor, affecting the speciation of neptunium in the reprocessing of used nuclear
fuel by solvent extraction. The kinetics of the reduction of neptunium(VI) by nitrous acid in solutions of nitric acid was
investigated spectrophotometrically by the method of initial rates. The reaction is of first order with respect to Np(VI)
while the order with respect to HNO2 is 1.20 ± 0.04. The reaction rate is almost inversely proportional to the hydrogen ion concentration (reaction order −0.92 ± 0.06),
indicating that the reaction proceeds primarily through the reaction of neptunium(VI) with the nitrate anion. The experimental
value of the rate constant k for the rate law −d[Np(VI)]/dt = k·[Np(VI)]·[HNO2]1.2/[H+] is of (0.159 ± 0.014) M−0.2 s−1 in I = 4 M and at 20 °C. The activation energy is (−57.3 ± 1.6) kJ/mol, which is in agreement with previous data on this reaction
in perchloric acid. 相似文献
20.
The kinetics of ligand substitution between aquapentacyanoruthenate(II) ion, [Ru(CN)5H2O]3− and 4-cyanopyridine (4-CNpy) has been investigated spectrophotometrically in the presence of anionic surfactant micelle,
namely sodium dodecylsulphate (SDS) at 400 nm (λmax of the intense yellow product [Ru(CN)54-CNpy]3−) under pseudo-first-order conditions using at least 10% excess of 4-CNpy over [Ru(CN)5H2O]3−. The reaction was studied as a function of [Ru(CN)5H2O3−], [4-CNpy], [SDS], pH, ionic strength and temperature, by varying each of these variables one at a time. The reaction exhibited
overall second-order kinetics, being first order each in [4-CNpy] and [Ru(CN)5H2O3−] over a wide concentration range. Variation of ionic strength of the medium had a significant negative effect on the rate.
The SDS micelle, being negatively charged, does not reveal any regular effect except at or near its critical micelle concentration
(c.m.c). The rate of reaction was measured at different temperatures, and the activation parameters were computed using Arrhenius
and Eyring plots. A plausible mechanism consistent with the experimental results has been proposed. 相似文献