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1.
Reartes GB  Liberman SJ  Blesa MA 《Talanta》1987,34(12):1039-1042
The acidity constants of benzidine (Bz) in aqueous solutions determined potentiometrically at 25° were Ka1 = (1.11 ± 0.08) × 10−5, Ka2 = (1.45 ± 0.12) × 10−4. The apparent mixed constants in 0.1M sodium nitrate are Ka1 = (5.37 ± 0.28) × 10−6 and Ka2 = (1.14 ± 0.09) × 10−4. The ultraviolet spectra were recorded as a function of pH and analysed with these constants to obtain the absorption spectra of H2Bz2+, HBz+ and Bz; the corresponding wavelengths of maximal absorption are 247, 273 and 278 nm, and molar absorptivities 1.63 × 104, 1.76 × 104 and 2.26 × 104 1.mole−1.cm−1.  相似文献   

2.
Micellar-catalyzed alkaline hydrolysis of 2,4-dinitrochlorobenzene (DNCB) in the presence of a conventional cationic surfactant CTAB or a cationic gemini surfactant 1,2-ethane bis(dimethyldodecylammonium bromide) (12-2-12) were studied spectrophotometrically at 25 °C. It was found that both CTAB and 12-2-12 micelles accelerated the alkaline hydrolysis of DNCB, and the binding constant of the substrate to the micelle, KS, for 12-2-12 (KS = 310 M−1) was larger than that for CTAB (85 M−1), which suggested that DNCB molecules bound with gemini micelles more easily than with CTAB. However, the second-order rate constant in micellar pseudophase (kM = 1.22 × 10−3 s−1) for 12-2-12 was lower than kM for CTAB (4.01 × 10−3 s−1) because the substrate may enter the interior of the 12-2-12 micelles. It was found also that 12-2-12 had a similar catalysis mechanism to CTAB when the concentration of 12-2-12 was relatively low (ca. <5 mM). However, above this concentration, higher microviscosity and significant increases in aggregation number and micelle size with increased surfactant concentration may remarkably influence the hydrolysis reaction.  相似文献   

3.
The mononuclear [Mn(indH)Cl2](CH3OH) (indH: 1,3-bis(2′-pyridylimino)-isoindoline) complex has been prepared and characterized by various techniques such as elemental analysis, IR, UV–vis, ESR spectroscopy and X-ray diffraction. The title compound in the presence of a base such as 1-methylimidazole, imidazole or pyridine is efficient catalyst for the disproportionation of H2O2 in CH3CN. Among the various nitrogenous bases investigated in this study imidazole and substituted imidazoles with strong π-donating ability show better co-catalytic effect.

In case of aqueous solution the complex [Mn(indH)Cl2](CH3OH) shows much higher catalytic activity, and the initial rate of the disproportionation of H2O2 increases with increasing pH and goes through a maximum, which was found at pH  9.6. In this pH value the reaction shows first-order dependence on the catalyst, and saturation kinetics on [H2O2] with Vmax = 8.1 × 10−3 Ms−1, KM = 489 mM, kcat = 38 ± 2 s−1 and k2(kcat/KM) = 79 ± 4 M−1s−1.  相似文献   


4.
The rate constants, k1 and k2 for the reactions of C2F5OC(O)H and n-C3F7OC(O)H with OH radicals were measured using an FT-IR technique at 253–328 K. k1 and k2 were determined as (9.24 ± 1.33) × 10−13 exp[−(1230 ± 40)/T] and (1.41 ± 0.26) × 10−12 exp[−(1260 ± 50)/T] cm3 molecule−1 s−1. The random errors reported are ±2 σ, and potential systematic errors of 10% could add to the k1 and k2. The atmospheric lifetimes of C2F5OC(O)H and n-C3F7OC(O)H with respect to reaction with OH radicals were estimated at 3.6 and 2.6 years, respectively.  相似文献   

5.
J. Femi Iyun  Ade Adegite 《Polyhedron》1989,8(24):2883-2888
At 25°C, I = 1.0 M (CF3SO3Li++CF3SO3H), [H+] = 0.034–0.274 M and λ = 453 nm, the rate equation for the oxidation of Ti(H2O), 63+ by bromine was found to be: −d/[Br2]T/dt=kK/[Br2][TiIII]/[H+]+K+kK/[Br3][TiIII]/[H++K, where k = 9.2 × 10−3 M −1 s −1 and K = 4.5 × 10−3 M. At [H+] = 1.0 M, [Br] = 0.05–0.4 M, the apparent second-order rate constant decreases as [Br] increases.

The pH-dependence of the oxidation of TiIII-edta by bromine is interpreted in terms of the change in identity of the TiIII-edta species as the pH of the reaction medium changes. The second-order rate constants were fitted using a non-linear least-square computer program with (1/k0edta)2 weighting into an equation of the form: k0edta =k1+k2K1[H+]−1+k3K1K2[H+]−2/1+K1[H+[H+−1+K1K2[H+]−2, with K1 and K2 fixed as earlier determined at 9.55 × 10−3 and 2.29 × 10−9 M, respectively, for the oxidation of bromine. k1=k2=(3.1±0.32)×103M−1s−1 k3=(2.3±0.45)×106N−1s−1.

It is proposed that these electron transfer reactions proceed by univalent changes with the production of Br2.− as a transient intermediate. An outer-sphere mechanism is proposed for these reactions. The homonuclear exchange rate for TiIII-edta+TiIV-edta is estimated at 32 M−1 s−1.  相似文献   


6.
The hydrogen abstraction reactions of C2F5CHO with OH radicals and Cl atoms have been investigated theoretically by a dual-level direct dynamics method. In this study, the optimized geometries and frequencies of the stationary points are calculated at the MP2/cc-pVDZ level of theory. The energies of the stationery points and the selected points along the minimum energy paths are further refined at the MC-QCISD level using the MP2 geometries. Complexes with energies less than those of the reactants or products are located at the entrance or the exit channels of the two reactions. This result indicates that both of reactions proceed via indirect reaction mechanisms. The enthalpies of formation for the reactant C2F5CHO and the product radical C2F5CO are estimated by isodesmic reactions at the MC-QCISD//MP2/cc-pVDZ level. At the same level, the rate constants are calculated by canonical variational transition state theory (CVT) incorporating with the small-curvature tunneling correction (SCT) in the temperature range 200–1000 K. Good agreement between the calculated and experimental rate constants is obtained at the room temperature. Due to the lack of the kinetic data of these reactions, the fitted three-parameter expressions based on the CVT/SCT rate constants within 200–1000 K are k1 = 1.64 × 10−24 T4.33 exp (−566.1/T) and k2 = 6.33 × 10−15 T1.35 exp (550.3/T) cm3 molecule−1 s−1, respectively.  相似文献   

7.
Excitation of solutions of Fe(bipy)2(CN)2 by a 266-nm laser pulse produces a hydrated electron and the oxidized complex, Fe(bipy)2 (CN)2+, in the primary photochemical step, in homogeneous aqueous solution as well as in aqueous solutions containing cetyltrimethylammonium bromide (CTAB) or sodium dodecyl sulfate (SDS) micelles. In all cases nascent hydrated electrons react with ground state Fe(bipy)2(CN)2 to form Fe(bipy)2(CN)2, and comparison of the decay constants in the three media (H2O: k = 2.8 × 1010 M−1 s−1; CTAB: k = 2.9 × 1010 M−1 s−1; SDS: k = 5.5 × 109 M−1 s−1), shows that the reaction is essentially unaffected by CTAB micelles but is much slower in SDS solution. Similar micellar effects were found for the back reaction between eaq and Fe(bpy)2(CN)2+. Rate constants for the scavenging of the photogenerated hydrated electrons by methyl viologen (MV2+) cations and NO3 anions were measured in the three systems, and the results indicate that for scavenging by MV2+ the rate constants are decreased in the micelle systems (k in H2O, 8.4 × 1010; CTAB, 3.5 × 1010 and SDS, 1.58 × 1010 M−1 s−1), whereas for NO3 the CTAB micelle decreases while the SDS micelle enhances the scavenging compared to water solution (k in H2O, 8.3 × 109; CTAB, 7 × 108; and SDS, 2.05 × 1010 M−1 s−1). For the comproportionation reaction between Fe(bipy)2(CN)2+ and Fe(bipy)2(CN)2 both micelles reduce the rate (k in H2O, 3.3 × 1010; CTAB, 2.3 × 1010; and SDS, 1.05 × 1010 M−1s−1), but while the reaction of Fe(bipy)2(CN)2+ with MV+ is increased in CTAB compared to water, it is slowed in SDS (k in H2O, 2.4 × 1010; CTAB, 8.9 × 1010; and SDS, 1.8 × 1010 M−1s−1). All effects observed in these microheterogeneous systems can be uniformly interpreted in terms of Coulombic interactions between the actual reactants and the charged surface of the micelles.  相似文献   

8.
The photocatalytic removal of the insecticide fenitrothion (IUPAC name: O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), C9H12NO5PS, from water suspension of TiO2, was investigated by following the disappearance of the original substance along with the formation and disappearance of intermediates via recording NMR (1H and 31P) and UV spectra, as well as by pH measurements. Based on the obtained data, a possible reaction mechanism was proposed. It was found that 31P-NMR spectrometry can be successfully used to follow the kinetics of transforming organic into inorganic phosphorus in the course of the degradation (ka=9.2×10−7 mol dm−3 min−1, r=0.980 for the illumination period after 15 h). The rate of fenitrothion aromatic ring decomposition was followed by UV spectrometry during the illumination (ka=3.1×10−6 mol dm−3 min−1, r=0.989). The complete mineralization was attained after about 66 h of irradiation.  相似文献   

9.
We have applied cavity ring-down spectroscopy to a kinetic study of the reaction of NO3 with CH2I2 in 25–100 Torr of N2 diluent at 298 K. The rate constant of reaction of NO3 + CH2I2 is determined to be (4.0 ± 1.2) × 10−13 cm3 molecule−1 s−1 in 100 Torr of N2 diluent at 298 K. The rate constant increases with increasing pressure of buffer gas below 100 Torr. The reaction of CH2I2 with NO3 has the potential importance at nighttime in the atmosphere.  相似文献   

10.
Intramolecular photoinduced electron transfer (PET) processes occurring in dyads with a free base porphyrin-tetraazaanthracene donor (P) and either a tetracyanonaphthoquinidodimethane (TCQ) or benzoquinone (BQ) acceptor linked by a rigid six σ-bond polynorbornane bridge ([6]) have been investigated. For P[6]BQ, PET in the polar solvent benzonitrile (s = 25.9) occurs with a rate constant (kPET) of 1.6 × 108 s−1 but is not evident in solvents less polar than tetrahydrofuran (s = 7.52). For P[6]TCQ, highly efficient forward PET occurs in both polar and non-polar solvents (kPET > 2 × 1010 s−1). For P[6]TCQ the lifetime of the resulting charge-separated state decreases markedly with increasing solvent polarity. The results are discussed in the context of the likely mechanisms for electronic coupling and current theories for PET processes in such linked molecular systems.  相似文献   

11.
The parameters of enzymatic hydrolysis of novel lipid-like substrates assembled in monolayers at water–air interface were estimated by a simple method. The method is based on measurement of the initial velocity of the reaction registered by the decrease of the monolayer area (caused by the enzymatic hydrolysis) at surface pressure of 10 mN/m in a single–compartment trough. Hydrolysis of trilaurin and three 1,3-dilaurylpseudoglycerides acylated by phenylalanine, leucine and valine was characterized by catalytic constants kcat and apparent Michael's constants Km(app) (using lipase from Pseudomonas fluorescens as catalyst). It was found that kcat of the synthetic pseudoglycerides (7–13 per s) are higher than kcat of trilaurin (4 per s) that can be explained by the presence of positively charged primary aminogroups in the substrates. Km(app) values were found to be similar for all the substrates studied (ca. 2×10−6 M). The proposed method allows estimation of the kinetic constants in traditional dimensions.  相似文献   

12.
The reaction: F + HCl→ HF (v 3) + Cl (1), has been initiated by photolysing F2 using the fourth-harmonic output at 266 nm from a repetitively pulsed Nd: YAG laser By analysing the time-dependence of the HF(3,0) vibrational chemiluminescence, rate constants have been determined at (296 ± 5) K for reaction (1), k1 = (7.0 ± 0.5) × 10−12 cm3 molecule−1 s−1, and for the relaxation of HF(v = 3) by HCl, CO2, N2O, CO, N2 and O2: kHCl = (1.18 ±0.14) × 10−11 kCO2 = (1.04 ± 0. 13) × 10−12, kN2O = (1.41 ± 0.13) × 10−11 kCO = (2.9 ± 0.3) × (10−12, kN2 = (7.1 ± 0.6) × 10−14 and kO2 = (1.9 ± 0.6) × 10−14 cm3molecule−1s−1.  相似文献   

13.
Gold nanoparticles were self-assembled to the modified glassy carbon electrode (GC) with cysteamine (CA) to prepare the nano-Au/CA/GC modified electrode. The electrochemical behavior of epinephrine (EP) on the modified electrode was explored with cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Epinephrine gave a pair of redox peaks at Epa = 0.190 mV and Epc = −0.224 mV (versus SCE), respectively. The nano-Au/CA/GC modified electrode shows an excellent electrocatalytic activity for the oxidation of EP. The modified electrode could be used to determine EP in the presence of ascorbic acid (AA). The response of catalytic current with EP concentration shows a linear relation in the range of 1.0 × 10−7 to 5.0 × 10−4 mol L−1 with the correlation coefficient of 0.998. The detection limit is 4.0 × 10−8 mol L−1. The modified electrode exhibited a good reproducibility, sensitivity and stability for the determination of EP injection.  相似文献   

14.
Li Liu  Jun-feng Song  Peng-fei Yu  Bin Cui 《Talanta》2007,71(5):1842-1848
A novel voltammetric method for the determination of β-d-glucose (GO) is proposed based on the reduction of Cu(II) ion in Cu(II)(NH3)42+–GO complex at lanthanum(III) hydroxide nanowires (LNWs) modified carbon paste electrode (LNWs/CPE). In 0.1 mol L−1 NH3·H2O–NH4Cl (pH 9.8) buffer containing 5.0 × 10−5 mol L−1 Cu(II) ion, the sensitive reduction peak of Cu(II)(NH3)42+–GO complex was observed at −0.17 V (versus, SCE), which was mainly ascribed to both the increase of efficient electrode surface and the selective coordination of La(III) in LNW to GO. The increment of peak current obtained by deducting the reduction peak current of the Cu(II) ion from that of the Cu(II)(NH3)42+–GO complex was rectilinear with GO concentration in the range of 8.0 × 10−7 to 2.0 × 10−5 mol L−1, with a detection limit of 3.5 × 10−7 mol L−1. A 500-fold of sucrose and amylam, 100-fold of ascorbic acid, 120-fold of uric acid as well as gluconic acid did not interfere with 1.0 × 10−5 mol L−1 GO determination.  相似文献   

15.
The hydrogen permeation and stability of tubular palladium alloy (Pd–23%Ag) composite membranes have been investigated at elevated temperatures and pressures. In our analysis we differentiate between dilution of hydrogen by other gas components, hydrogen depletion along the membrane length, concentration polarization adjacent to the membrane surface, and effects due to surface adsorption, on the hydrogen flux. A maximum H2 flux of 1223 mL cm−2 min−1 or 8.4 mol m−2 s−1 was obtained at 400 °C and 26 bar hydrogen feed pressure, corresponding to a permeance of 6.4 × 10−3 mol m−2 s−1 Pa−0.5. A good linear relationship was found between hydrogen flux and pressure as predicted for rate controlling bulk diffusion. In a mixture of 50% H2 + 50% N2 a maximum H2 flux of 230 mL cm−2 min−1 and separation factor of 1400 were achieved at 26 bar. The large reduction in hydrogen flux is mainly caused by the build-up of a hydrogen-depleted concentration polarization layer adjacent to the membrane due to insufficient mass transport in the gas phase. Substituting N2 with CO2 results in further reduction of flux, but not as large as for CO where adsorption prevail as the dominating flow controlling factor. In WGS conditions (57.5% H2, 18.7% CO2, 3.8% CO, 1.2% CH4 and 18.7% steam), a H2 permeance of 1.1 × 10−3 mol m−2 s−1 Pa−0.5 was found at 400 °C and 26 bar feed pressure. Operating the membrane for 500 h under various conditions (WGS and H2 + N2 mixtures) at 26 bars indicated no membrane failure, but a small decrease in flux. A peculiar flux inhibiting effect of long term exposure to high concentration of N2 was observed. The membrane surface was deformed and expanded after operation, mainly following the topography of the macroporous support.  相似文献   

16.
The cysteamine (CA) was bound onto surface of the pretreated glassy carbon electrode (GC) with cyclic voltammetry (CV). Gold nanoparticles were self-assembled to the electrode binding with cysteamine via strong AuS covalent bond to fabricate the nano-Au self-assembled modified electrode (nano-Au/CA/GC). The modified electrode was characterized with cyclic voltammetric and ac impedance methods. The electrochemical behavior of dopamine (DA) on the modified electrode was investigated with cyclic voltammetry and differential pulse voltammetry (DPV). A well-defined redox peaks of DA on the nano-Au/CA/GC electrode were obtained at Epa = 0.175 V and Epc = 0.146 V (vs. SCE), respectively. The peak current of DA is linear with the concentration of DA in the range of 1.0 × 10−8 mol L−1 to 2.5 × 10−5 mol L−1, with the correlation coefficient of 0.998. The detection limit is 4.0 × 10−9 mol L−1 (S/N = 3). The modified electrode exhibited an excellent reproducibility, sensibility and stability for determination of DA in the presence of high concentration AA, and can be applied to determinate dopamine injection, with satisfied result.  相似文献   

17.
Pentaerythrityl tetraethylenediamine (PETEDA) dendrimer was synthesized from pentaerythrityl tetrabromide and ethylenediamine. Its molecular structure was characterized by elemental analysis, Fourier transform infrared resonance (FT-IR) and hydrogen nuclear magnetic resonance (1H NMR) spectroscopy. The composite membranes for selectively permeating CO2 were prepared by using PETEDA-PVA blend polymer as the active layer and polyethersulfone (PES) ultrafiltration membrane as the support layer and their permselectivity was tested by pure CO2 and CH4 gases and the gas mixture containing 10 vol.% CO2 and 90 vol.% CH4, respectively. For pure gases, the membrane containing 78.6 wt% PETEDA and 21.4 wt% PVA in the blend has a CO2 permeance of 8.14 × 10−5 cm3 (STP) cm−2 s−1 cmHg−1 and CO2/CH4 selectivity of 52 at 143.5 cmHg feed gas pressure. While feed gas pressure is 991.2 cmHg, CO2 permeance reaches 3.56 × 10−5 cm3 (STP) cm−2 s−1 cmHg−1 and CO2/CH4 selectivity is 19. For the gas mixture, the membrane has a CO2 permeance of 6.94 × 10−5 cm3 (STP) cm−2 s−1 cmHg−1 with a CO2/CH4 selectivity of 33 at 188.5 cmHg feed gas pressure, and a CO2 permeance of 3.29 × 10−5 cm3 (STP) cm−2 s−1 cmHg−1 with a CO2/CH4 selectivity of 7.5 at a higher feed gas pressure of 1164 cmHg. A possible gas transport mechanism in the composite membranes is proposed by investigating the permeating behavior of pure gases and the gas mixture and analyzing possible reactions between CO2/CH4 gases and the PETEDA-PVA blend polymer. The effect of PETEDA content in the blend polymer on permselectivity of the composite membranes was investigated, presenting that CO2 permeance and CO2/CH4 selectivity increase and CH4 permeance decreases, respectively with PETEDA content. This is explained by that with increasing PETEDA content, the carrier content increases, and the crystallinity and free volume of the PETEDA-PVA blend decrease that were confirmed by the experimental results of X-ray diffraction spectra (XRD) and positron annihilation lifetime spectroscopy (PALS).  相似文献   

18.
Rate coefficients for the reactions of cyclohexadienyl (c-C6H7) radicals with O2 and NO were measured at 296 ± 2 K. The c-C6H7 radicals were detected selectively by laser-induced fluorescence. The rate coefficient for the reaction of c-C6H7 with O2, (4.4 ± 0.5) × 10−14 cm3 molecule−1 s−1, was independent of the bath-gas (He) pressure (13–80 Torr). In the reaction of c-C6H7 with NO, thermal equilibrium among c-C6H7, NO, and C6H7NO was observed. The forward and reverse reactions were in the falloff region, and the equilibrium constant was (1.5 ± 0.6) × 10−15 cm3 molecule−1.  相似文献   

19.
A new sensitive and selective preconcentration-fluorimetric method for determination of terazosin based on its native fluorescence was developed. The analyte, initially present in aqueous matrix, was treated with an extractive non-ionic surfactant solution and separated by the clouding phenomenon. The optimum analytical conditions for terazosin assay were established. Under these conditions, linear calibration curves were obtained over the range of 1 × 10−5 to 7.0 μg mL−1 with detection and quantification limits of 1.11 × 10−5 and 3.7 × 10−5 μg mL−1, respectively. Additionally, the binding constant (KB) for the terazosin-PONPE 7.5 system was determined given a value of 1028 L mol−1. The developed coupled methodology, which thoroughly satisfies the typical requirements for pharmaceutical control processes, was proved to be appropriate for monitoring terazosin in actual pharmaceutical formulations and biological fluid sample. The results were validated by recovery test and by comparison with other reported methods, being highly satisfactory.  相似文献   

20.
Electrochemical studies of famotidine were carried out using voltammetric techniques: cyclic voltammetry, linear sweep and square wave adsorptive stripping voltammetry. The dependence of the current on pH, buffer concentration, nature of the buffer, and scan rate was investigated. The best results for the determination of famotidine were obtained in MOPS buffer solution at pH 6.7. This electroanalytical procedure enabled to determine famotidine in the concentration range 1 × 10−9–4 × 10−8 mol L−1 by linear sweep adsorptive stripping voltammetry (LS AdSV) and 5 × 10−10–6 × 10−8 mol L−1 by square wave adsorptive stripping voltammetry (SW AdSV). Repeatability, precision and accuracy of the developed methods were checked. The detection and quantification limits were found to be 1.8 × 10−10 and 6.2 × 10−10 mol L−1 for LS AdSV and 4.9 × 10−11 and 1.6 × 10−10 mol L−1 for SW AdSV, respectively. The method was applied for the determination of famotidine in urine.  相似文献   

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