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1.
The kinetics of the diazotization reaction of procaine in the presence of anionic micelles of sodium dodecyl sulfate (SDS) and cationic micelles of cetyltrimethyl ammonium bromide (CTAB), dodecyltrimethyl ammonium bromide (DDTAB) and tetradecyltrimethyl ammonium bromide (TDTAB) were carried out spectrophotometrically at λmax = 289 nm. The values of the pseudo first order rate constant were found to be linearly dependent upon the [NaNO2] in the concentration range of 1.0 × 10−3 mol dm−3 to 12.0 × 10−3 mol dm−3 in the presence of 2.0 × 10−2 mol dm−3 acetic acid. The concentration of procaine was kept constant at 6.50 × 10−5 mol dm−3. The addition of the cationic surfactants increased the reaction rate and gave plateau like curve. The addition of SDS micelles to the reactants initially increased the rate of reaction and gave maximum like curve. The maximum value of the rate constant was found to be 9.44 × 10−3 s−1 at 2.00 × 10−3 mol dm−3 SDS concentration. The azo coupling of diazonium ion with β-naphthol (at λmax = 488) nm was found to linearly dependent upon [ProcN2+] in the presence of both the cationic micelles (CTAB, DDTAB and TDTAB) and anionic micelles (SDS). Both the cationic and anionic micelles inhibited the rate of reactions. The kinetic results in the presence of micelles are explained using the Berezin pseudophase model. This model was also used to determine the kinetic parameters e.g. km, Ks from the observed results of the variation of rate constant at different [surfactants].  相似文献   

2.
The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) on the interaction of dipeptide glycyl-tyrosine (Gly-Tyr) with ninhydrin under varying conditions has been studied spectrophotometrically at 70 °C and pH 5.0. The reaction followed first- and fractional-order kinetics with respect to [Gly-Tyr] and [ninhydrin], respectively. Increase in total concentration of CTAB from 0 to 70 × 10−3 mol dm−3 resulted in an increase in the pseudo-first-order rate constant (kψ) by a factor of ca. 3. Quantitative kinetic analysis of kψ  [CTAB] data was performed on the basis of pseudo-phase model of the micelles (proposed by Menger and Portnoy and developed by Bunton) and Piszkiewicz model. A possible mechanism has been proposed and the kinetic data have been used to evaluate the micellar binding constants KS (268 mol−1 dm3 for Gly-Tyr) and KN (64 mol−1 dm3 for ninhydrin).  相似文献   

3.
The photophysical and photochemical studies of a sulfonylurea herbicide, thifensulfuron-methyl (THM), have been investigated in a buffered aqueous solution. In the first part, the influence of pH on the spectroscopic properties was studied. This allowed the determination of the ground and excited state acidity constants, pKa = 4 and 4.4, respectively, thus exhibiting the potential existence of a photoinduced protonation in the singlet state. In the second part, the photolysis kinetics was studied at different pH and varying oxygen concentrations, using an HPK 125 W lamp and followed up by the identification of photoproducts formed under continuous photo-irradiation. The kinetics results suggest that the photolysis process is faster in acidic (k = 3 × 10?4 s?1) than in basic medium (k = 9.8 × 10?5 s?1). The photolysis products were identified by high performance liquid chromatography HPLC-DAD, HPLC–MS and HPLC–MS–MS. In order to obtain a better understanding of the photodegradation mechanism, a laser flash photolysis study was performed. By comparing the quenching rate constant (kq = 9.64 × 108 mol?1 l s?1) obtained from triplet state quenching by molecular oxygen and from the Stern–Volmer relation (kq = 0.41 × 108 mol?1 l s?1), the role of the singlet state in the photodegradation process was demonstrated. The photoproducts originating from both singlet and triplet excited states have been identified and hypothetical photodegradation pathways of the thifensulfuron-methyl in aqueous solution are proposed.  相似文献   

4.
Comprehensive (p, ρ, T) measurements on two gas mixtures of (0.9CH4 + 0.1N2) and (0.8CH4 + 0.2N2) have been carried out at six temperatures between 240 and 400 K and at pressures up to 20 MPa. A total of 108 (p, ρ, T) data for the first mixture and 134 for the second one are given. These measurements were performed using a compact single-sinker densimeter based on Archimedes’ buoyancy principle. The overall uncertainty in density ρ is estimated to be (1.5 · 10−4 · ρ + 2 · 10−3 kg · m−3) (coverage factor k = 2), the uncertainty in temperature T is estimated to be 0.006 K (coverage factor k = 2), and the uncertainty in pressure p is estimated to be 1 · 10−4·p (coverage factor k = 2). The equipment has been previously checked with pure nitrogen over the whole temperature and pressure working ranges and experimental results (35 values) are given and a comparison with the reference equation of state for nitrogen is presented.  相似文献   

5.
Electrolytic conductivities of some alkali metal halides, MX (M+ = Li+, Na+, and K+; X? = Cl?, Br?, and I?), NaBPh4 and Bu4NBr have been investigated in (20, 40, and 60) mass% {dimethyl sulfoxide (DMSO) in DMSO + acetonitrile} at T = 298.15 K. The conductance results have been analyzed by the Fuoss-conductance-concentration equation in terms of the limiting molar conductance Λ° the association constant KA and the association diameter R. The ionic contributions to the limiting molar conductance have been estimated using Bu4NBPh4 as the “reference electrolyte”. The association constant KA tends to increase in the order mass percent 20 < 40 < 60 DMSO in (DMSO + acetonitrile) which is explained by the thermodynamic parameter ΔG° and Walden product Λ°η. The results have been interpreted in terms of ion–solvent interactions and structural changes in the mixed solvents.  相似文献   

6.
The temperature dependence of the rate constant of the inversion substitution reactions CH3X + O2 → CH3O2? + X? (X = SH, NO2), can be expressed as k = 6.8 × 10–12(T/1000)1.49exp(–62816 cal mol–1/RT) cm3 s–1 (X = SH) and k = 6.8 × 10–12(T/1000)1.26 × × exp(–61319 cal mol–1/RT) cm3 s–1 (X = NO2), as found with the use of high-level quantum chemical methods and the transition state theory.  相似文献   

7.
A series of lanthanide complexes with the 2-chloro-4,5-difluorobenzoate (2-cl-4,5-dfba) and 1,10-phenanthroline (phen), have been synthesized with the formulae of [La(2-cl-4,5-dfba)3phen]n·nH2O (1), [Nd(2-cl-4,5-dfba)3phenH2O]2 (2), [Ln(2-cl-4,5-dfba)3phen]2 (Ln = Eu (3), Ho (4)). The complexes are characterized by elemental analysis, infrared and fluorescent spectra and X-ray single-crystal diffraction. The structures of the four complexes are very different. Complex 1 is an infinite 1D chain polymeric structure formed by the asymmetric units with the mirror growth pattern. Each La3+ ion is coordinated to four bridging carboxylic groups, two tridentate chelating–bridging carboxylic groups, simultaneous with one phen molecule, giving the coordination number of nine. In the molecular structures of complexes 2 and 3, two Ln3+ ions are linked by four carboxyl groups, forming two binuclear molecules. In addition, each Nd3+ ion in complex 2 is bonded to one H2O molecule and one carboxyl group by monodentate mode, one phen molecule by bidentate chelating, and each Eu3+ ion is also chelated to one phen molecule and one carboxyl group in complex 3. And in complex 4, the Ho3+ ion yields a eight-coordinated distorted square anti-prism coordination geometry. The three-dimensional IR accumulation spectra of gaseous products for complexes 1 to 4 are analyzed and further authenticated the thermal decomposition processes with TG-DTG curves. The heat capacities of complexes 2 to 4 are measured and fitted to a polynomial equation by the least squares method on the basis of the reduced temperature x (x = [T−(Tmax + Tmin)/2]/[(Tmax  Tmin)/2]). Then the smoothed molar heat capacities and thermodynamic functions of complexes 2 to 4 are calculated. The fluorescence intensity of complex 3 is markedly improved as well.  相似文献   

8.
A new polyoxomolybdophosphate 1, formulated as [Cu(phen)2][Cu(phen)H2O]2[Mo5P2O23]·3.5H2O (phen = 1,10-phenanthroline) has been synthesized under hydrothermal conditions. Compound 1 crystallizes in the triclinic space group P-1 with a = 12.2429(5) Å, b = 14.3543(5) Å, c = 20.0814(8) Å, α = 80.023 (1)°, β = 74.283 (1)°, γ = 66.452(1)°, V = 3105.8(2) Å3, R1 = 0.0375, wR2 = 0.0885, Z = 2 and GOF = 1.009. Compound 1 is constructed from diphosphopentamolybdate clusters coordinated to Cu(II)-phen units, and free water molecules, which are connected to a three-dimensional framework via π–π stacking interactions from the phen ligands. The single-crystal X-ray diffraction, FT-IR, TG-DTA, XPS, EPR and fluorescent spectra for this compound were determined. The electrochemical properties of compound 1 are studied using cyclic voltammogram, the results indicated that the compound 1 shows good electrocatalytic activity to NO2?.  相似文献   

9.
The kinetics of the reduction of water-soluble colloidal manganese dioxide by glycyl-leucine (Gly-Leu) has been investigated in the presence of perchloric acid both in aqueous as well as micellar media at 35 °C. The study was carried out as functions of [MnO2], [Gly-Leu] and [HClO4]. The first-order-rate is observed with respect to [MnO2], whereas fractional-order-rates are determined in both [Gly-Leu] and [HClO4]. Addition of sodium pyrophosphate and sodium fluoride enhanced the rate of the reaction. Further, the use of surfactant micelles is highlighted as, in favourable cases, the micelles help the redox reactions by bringing the reactants into a close proximity due to hydrogen bonding. While the ionic surfactants SDS and CTAB have not shown any effect on the reaction rate, the nonionic surfactant TX-100 has catalytic effect which is explained in terms of the mathematical model proposed by Tuncay et al. (1999). The Arrhenius and Eyring equations are valid for the reaction over the range of temperatures used and different activation parameters (Ea, ΔH#, ΔS# and ΔG#) have been evaluated. Kinetic studies show that the redox reaction between MnO2 and Gly-Leu proceeds through a mechanism combining one- and two-electron pathways: Mn(IV)  Mn(III)  Mn(II) and Mn(IV)  Mn(II). On the basis of the observed results, a possible mechanism has been proposed and discussed.  相似文献   

10.
In this Letter we report the results of the measurements of the rate coefficients for thermal attachment to several perfluoroethers namely perfluorodiglyme (C6F14O3), perfluorotriglyme (C8F18O4), perfluoropolyether (CF3–(OCF(CF3)CF2)n–(OCF2)m–OCF3) and perfluorocrownether ((C2F4O)5). Rate coefficients were obtained under thermal conditions in the temperature range 298–378 K. The increase of the rates with temperature follows the Arrhenius law and the activation energies have been obtained from the slope of the ln(k) vs. 1/T. The respective values of the rate coefficients (at 298 K) and activation energies are as follows: 7.7 ± 1.2 × 10?11 cm3 s?1 (0.18 ± 0.005 eV), 6.7 ± 2.1 × 10?11 cm3 s?1 (0.25 ± 0.004 eV), 2.1 ± 0.2 × 10?10 cm3 s?1 (0.16 ± 0.010 eV), 3.1 × 10?11 cm3 s?1 (0.27 ± 0.003 eV) for C6F14O3, C8F18O4, CF3–(OCF(CF3)CF2)n–(OCF2)m–OCF3 and (C2F4O)5.  相似文献   

11.
Recent years have witnessed burgeoning interest in plant flavonoids as novel therapeutic drugs targeting cellular membranes and proteins. Motivated by this scenario, we explored the binding of robinetin (3,7,3′,4′,5′-pentahydroxyflavone, a bioflavonoid with remarkable ‘two color’ intrinsic fluorescence properties), with egg yolk phosphatidylcholine (EYPC) liposomes and normal human hemoglobin (HbA), using steady state and time resolved fluorescence spectroscopy. Distinctive fluorescence signatures obtained for robinetin indicate its partitioning (Kp = 8.65 × 104) into the hydrophobic core of the membrane lipid bilayer. HbA–robinetin interaction was examined using both robinetin fluorescence and flavonoid-induced quenching of the protein tryptophan fluorescence. Specific interaction with HbA was confirmed from three lines of evidence: (a) bimolecular quenching constant Kq ? diffusion controlled limit; (b) closely matched values of Stern–Volmer quenching constant and binding constant; (c) τ0/τ = 1 (where τ0 and τ are the unquenched and quenched tryptophan fluorescence lifetimes, respectively). Absorption spectrophotometric assays reveal that robinetin inhibits EYPC membrane lipid peroxidation and HbA glycosylation with high efficiency.  相似文献   

12.
《Comptes Rendus Chimie》2014,17(7-8):801-807
Imidazole-2-carboxaldehyde (IC) reactivity in the presence of halide anions (Cl, Br, I) has been studied by laser flash photolysis in aqueous solution at room temperature. The absorption spectrum of the triplet state of IC has been measured with a maximum absorption at 330 nm and a weaker absorption band around 650 nm. Iodide anions proved to be efficient quenchers of the triplet state IC, with a rate coefficient kq of (5.33 ± 0.25) × 109 M−1 s−1. Quenching by bromide and chloride anions was less efficient, with kq values of (6.27 ± 0.53) × 106 M−1 s−1 and (1.31 ± 0.16) × 105 M−1 s−1, respectively. The halide (X) quenches the triplet state; the resulting transient absorption feature matches that of the corresponding radical anion (X2). We suggest that this type of quenching reactions is a driving force of oxidation reactions in the oceanic surface microlayer (SML) and a source of halogen atoms in the atmosphere.  相似文献   

13.
This study proposed that hybrid scrap cast iron particles (SIP)-aerobic biodegradation technology could enhance the biodegradability of toxic wastewater. SIP cleaved the azo linkages of Direct Green1 dye to form benzidine, 4-aminophenol, aniline and 1,2,7-triamino-8-hydroxynapthalene-3,6-disulfonic acid. SIP-mediated dye reduction was effective at wide pH range; however, kinetic analysis revealed fastest pseudo-first order dye reduction rate at acidic pH 3 (kd = 0.549 min−1) followed by pH 9 (kd = 0.383 min−1) and pH 7 (kd = 0.318 min−1). The daughter aromatic amines produced were partially adsorbed onto the SIP surface and maximally at neutral pH. The adsorption process followed pseudo-second order adsorption kinetics and Langmuir isotherm. Benzidine was adsorbed more than 4-aminophenol and aniline. BOD5 of the SIP-treated effluent increased from 0.93 to 12 mg/L showing improved biodegradability. The daughter amines were rapidly mineralized in the aerobic bioreactor within 6 h. Cost-effective SIP pre-treatment could accelerate mineralization and detoxification of recalcitrant wastewater.  相似文献   

14.
《Polyhedron》2007,26(9-11):2101-2104
The bimetallic ferromagnetic chain {[K(18-crown-6)][Mn(bpy)Cr(ox)3]} (1) has been synthesized and characterized. It crystallizes in the orthorhombic chiral space group P212121 [a = 9.0510(2) Å, b = 14.4710(3) Å, c = 26.8660(8) Å, V = 3510.97(1) Å3, Z = 2]. Compound 1 is made up by anionic [Mn(bpy)Cr(ox)3] 1D chains and cationic [K(18-crown-6)]+ complexes. The magnetic exchange within the chain is ferromagnetic [J = +7.8(7) cm−1]. In the solid state, the ferromagnetic chains are well isolated magnetically and no long range magnetic ordering has been observed above 2 K.  相似文献   

15.
The apparent molar volumes Vφ of glycine, alanine, valine, leucine, and lysine have been determined in aqueous solutions of 0.05, 0.5, 1.0 mol · kg−1 sodium dodecyl sulfate (SDS) and 1.0 mol · kg−1 cetyltrimethylammonium bromide (CTAB) by density measurements at T=298.15 K. The apparent molar volumes have also been determined for diglycine and triglycine in 1 mol · kg−1 SDS and CTAB solutions. These data have been used to calculate the infinite dilution apparent molar volumes V20 for the amino acids and peptides in aqueous SDS and CTAB and the standard partial molar volumes of transfer (ΔtrV2,m0) of the amino acids and peptides to these aqueous surfactant solutions. The linear correlation of V20 for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH3+, COO), CH2 group and other alkyl chains of the amino acids to V20. The results on the partial molar volumes of transfer from water to aqueous SDS and CTAB have been interpreted in terms of ion–ion, ion–polar and hydrophobic–hydrophobic group interactions. The volume of transfer data suggests that ion–ion or ion–hydrophilic group interactions of the amino acids and peptides are stronger with SDS compared to those with CTAB. Comparison of the hydration numbers of amino acids calculated in the present studies with those in other solvents from literature shows that these numbers are almost the same at 1 mol · kg−1 level of the cosolvent/cosolute. Increasing molality of the cosolvent/cosolute beyond 1 mol · kg−1 lowers the hydration number of the amino acids due to increased interactions with the solvent and reduced electrostriction.  相似文献   

16.
Transparent glasses were prepared by conventional melting–quenching method in the xMoO3·(100 ? x)[3B2O3·PbO] system where 0  x  15 mol%. By increasing the MoO3 content up to 20 mol% the PbMoO4 crystalline phase appears. These systems exhibit a photochromic effect which can be induced through laser exposures (λ = 633 nm) directly on the bulk sample. Structural investigations by FTIR spectroscopy show that the photosensitive effect is due to a reduction of Mo6+ to Mo4+ and/or Mo5+ promoted by the oxidation of Pb2+ and some structural changes of the borate network.  相似文献   

17.
The hydroesterification of cyclohexene is catalyzed by a preformed Pd(PPh3)2(TsO)2 complex I in methanol as solvent. The effect of PPh3, TsOH, and water on the TOF has been evaluated. The system I/PPh3/TsOH=1/6/8, in the presence of 800 ppm of H2O, at 373 K and under 2.0 MPa of CO leads to a TOF as high as 850 h−1. The increase of TOF observed adding a hydride source such as TsOH and H2O suggests that Pd-hydride species plays a key role in the first step of the catalytic cycle. The initial reaction rate increases linearly with the concentration of cyclohexene and of MeOH and passes through a maximum with increasing the pressure of CO. The rate equation r0=k1PCO (1+k2PCO+k3PCO2)−1 fits well the experimental data. The values of k1, k2, and k3 have been evaluated at different temperatures. From the plot ln k versus 1/T, E1=19.4 kcal/mol, E2=20.6 kcal/mol and E3=6.5 kcal/mol have been evaluated. On the basis of experimental evidences and of the kinetic study, a catalytic cycle mechanism has been proposed.  相似文献   

18.
The heterometallic photoinitiated electron collector [{(phen)2Ru(dpp)}2RhBr2](PF6)5 (phen = 1,10-phenanthroline, dpp = 2,3-bis(2-pyridyl)pyrazine) has been synthesized and studied by spectroscopic, photophysical, electrochemical, and photochemical techniques. Substitution of chloride with bromide in the previously reported [{(phen)2Ru(dpp)}2RhCl2](PF6)5 complex presents a new photoinitiated electron collector which can assist in understanding the functioning of our supramolecular systems [{(TL)2Ru(BL)}2RhX2](PF6)5 (TL = terminal ligand, BL = bridging ligand, X = halide) in the photoinitiated electron collection and generation of hydrogen through the reduction of water and a detailed comparison is presented. Both the bromide and chloride analogues of these supramolecular complexes contain low energy, emissive metal-to-ligand charge transfer (3MLCT) excited states that populate lower lying metal-to-metal charge transfer (3MMCT) excited states. The electrochemistry of these complexes showed an impact on the reduction of the central RhIII upon halide substitution with the bromide analogue [(phen)2Ru(dpp)}2RhBr2](PF6)5 having a slightly lower reduction potential than the corresponding chloride counterpart. The more positive reduction of RhIII to generate the RhI species in the bromide analogue impacts the photocatalytic properties upon photolysis in the presence of a sacrificial electron donor. The trimetallic complex [{(phen)2Ru(dpp)}2RhBr2](PF6)5 generates hydrogen through the reduction of water with higher yields than the chloride [{(phen)2Ru(dpp)}2RhCl2](PF6)5 analogue under the same conditions. Despite the longer lived 3MLCT state of both [(TL)2Ru(dpp)]2+ and [{(TL)2Ru}2(dpp)]4+ when TL = phen vs. bpy (bpy = 2,2′-bipyridine), the phen trimetallics with X = Cl? or Br? do not display longer lived 3MLCT states and show lower H2 yields than the analogous bpy trimetallic systems.  相似文献   

19.
《Polyhedron》2007,26(9-11):2121-2125
The hybrid organo-inorganic compounds [Cu4(bipy)4V4O11(PO4)2]nH2O (n  5) (1), [Cu2(phen)2(PO4)(H2PO4)2(VO2) · 2H2O] (2) and [Cu2(phen)2(O3PCH2PO3)(V2O5) (H2O)]H2O (3) which present different bridging forms of the phosphate/phosphonate group, show different bulk magnetic properties. We herein analyze the magnetic behaviour of these compounds in terms of their structural parameters. We also report a theoretical study for compound (1) assuming four different magnetic exchange pathways between the copper centres present in the tetranuclear unit. For compound (1) the following J values were obtained J1 = +3.29; J2 = −0.63; J3 = −2.23; J4 = −46.14 cm−1. Compound (2) presents a Curie–Weiss behaviour in the whole range of temperature (3–300 K), and compound (3) shows a maximum for the magnetic susceptibility at 64 K, typical for antiferromagnetic interactions. These data where fitted using a model previously reported in the literature, assuming two different magnetic exchange pathways between the four copper(II) centres, with J1 = −30.0 and J2 = −8.5 cm−1.  相似文献   

20.
Coordination compounds with general formula [Ln(L1)3phen], where Ln = Nd, Eu, Er, Yb, HL1 = N,N′-dipyrrolidine-N′′-trichloracetylphosphortriamide, phen = 1,10-phenanthroline; [Ln(L1)3bpm], where Ln = La, Nd, Eu, Gd, Er, Y, bpm = 2,2′-bipyrimidine and [{Ln(L2)3}2(μ-bpm)], where Ln = La, Nd, Eu, Gd, Er, Y, HL2 = dimethyl-N-trichloracetylamidophosphate have been synthesized and characterized by means of IR and UV–Vis spectroscopy. Crystal structures of [Nd(L1)3phen] (1), [Nd(L1)3bpm] (2) and [{Nd(L2)3}2(μ-bpm)] (3) have been determined. It was found, that in the deprotonated form the phosphoryl ligands (L1)? and (L2)? are coordinated to the neodymium atoms in a bidentate manner via the oxygen atoms of the phosphoryl and the carbonyl groups with formation of six-membered metallocycles. In the case of compounds 1 and 2 the 1,10-phenanthroline (or 2,2′-bipyrimidine) molecules are coordinated to the metals in a bidentate manner via the nitrogen atoms. In contrast 2,2′-bipyrimidine acts in the bidentate-bridge mode forming binuclear complex 3. Variable-temperature magnetic susceptibility measurements of 3 and [{Gd(L2)3}2(μ-bpm)] (4) reveal a weak antiferromagnetic interaction between the two magnetic centres, whereas in the case of [{Eu(L2)3}2(μ-bpm)] (5) the presence of spin–orbit coupling leads to a deviation from the Curie and Curie–Weiss laws.  相似文献   

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