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1.
The oxidation of 3-O-methyl-d-glucopyranose (Glc3Me) by CrVI in acid medium yields CrIII, formic acid and 2-O-methyl-d-arabinose as final products when a 50-times or higher excess of Glc3Me over CrVI is used. The redox reaction takes place through the combination of CrVI  CrIV  CrII and CrVI  CrIV  CrIII pathways. Intermediacy of free radicals and CrII in the reaction was demonstrated by the observation of induced polymerization of acrylamide and detection of CrO22+ formed by reaction of CrII with O2. Intermediate oxo-CrV–Glc3Me species were detected by EPR spectroscopy. In 0.3–0.5 mol/L HClO4, intermediate CrV rapidly decompose to the reaction products, while, at pH 5.5–7.5, where the redox processes are very slow, five-coordinate CrV bis-chelates of the pyranose and furanose forms of Glc3Me remain more than 15 h in solution. The C1–C2 bond cleavage of Glc3Me upon reaction with CrVI distinguishes this derivative from glucose, which is oxidized to gluconic acid.  相似文献   

2.
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   

3.
A new amino acid ionic liquid (AAIL) [C3mim][Val] (1-propyl-3-methylimidazolium valine) was prepared by the neutralization method. Using the solution-reaction isoperibol calorimeter, molar solution enthalpies of the ionic liquid [C3mim][Val] with known amounts of water and with different concentrations in molality were measured at T = 298.15 K. In terms of standard addition method (SAM) and Archer’s method, the standard molar enthalpy of solution for [C3mim][Val] without water, ΔsHm = (−55.7 ± 0.4) kJ · mol−1, was obtained. The hydration enthalpy of the cation [C3mim]+, ΔH+ ([C3mim]+) = −226 kJ · mol−1, was estimated in terms of Glasser’s theory. Using the RD496-III heat conduction microcalorimeter, the molar enthalpies of dilution, ΔDHm(mi  mf), of aqueous [C3mim][Val] with various values of molality were measured. The values of ΔDHm(mi  mf) were fitted to Pitzer’s ion-interaction model and the values of apparent relative molar enthalpy, φL, calculated using Pitzer’s ion-interaction model.  相似文献   

4.
Thermodynamic properties of Mg(NH2)2 and LiNH2 were investigated by measurements of NH3 pressure-composition isotherms (PCI). Van’t Hoff plot of plateau pressures of PCI for decomposition of Mg(NH2)2 indicated the standard enthalpy and entropy change of the reactions were ΔH° = (120 ± 11) kJ · mol?1 (per unit amount of NH3) and ΔS° = (182 ± 19) J · mol?1 · K?1 for the reaction: Mg(NH2)2  MgNH + NH3, and ΔH° = 112 kJ · mol?1 and ΔSo = 157 J · mol?1 · K?1 for the reaction: MgNH  (1/3)Mg3N2 + (1/3)NH3. PCI measurements for formation of LiNH2 were carried out, and temperature dependence of plateau pressures indicated ΔH° = (?108 ± 15) kJ · mol?1 and ΔS° = (?143 ± 25) J · mol?1 · K?1 for the reaction: Li2NH + NH3  2LiNH2.  相似文献   

5.
The complex cis-Pt(Ph3Ge)2(PMe2Ph)2 underwent smooth isomerization to give the trans-isomer at room temperature via an associative five-coordinated intermediate. Thermodynamic parameters and activation energy for the cis to trans isomerization were obtained, ΔH# = 105 kJ mol−1, ΔS# = 12.5 J mol−1 K−1, and Ea = 107 kJ mol−1, respectively. Heating of trans-Pt(Ph3Ge)2(PMe2Ph)2 at 50 °C for 36 days produced trans-PtPh(Ph3Ge)(PMe2Ph)2 followed by the formation of trans-PtPh2(PMe2Ph)2, Pt(PMe2Ph)4, and Ph4Ge finally via elimination of the phenyl group from Ph3Ge ligand with liberation of the Ph2Ge unit and subsequent reductive elimination of the remaining Ph3Ge ligand at 80 °C for 1 month.  相似文献   

6.
We developed an electrochemical in situ cell for soft x-ray emission spectroscopy (XES) to accurately investigate the redox reaction and electronic structure of transition metals in the cathode materials for Li–ion battery. The in situ cell consists of a Li–metal counter electrode, an organic electrolyte solution, and a cathode on a membrane window which separates the liquid electrolyte from high vacuum and can pass the incoming and emitted photons. In this study, the Mn 3d electronic structure of LiMn2O4 thin-film electrode was clarified by the operando XES. At the charged state, the XES spectrum changed significantly from the open-circuit-voltage (OCV) state, suggesting oxidation of the Mn3 + component through Li–ion extraction. Upon discharge up to 3.0 V vs. Li/Li+, the XES spectrum almost returned to its profile at the OCV state with small difference, indicating the valence change of Mn: Mn3.6 +  Mn4 +  Mn3.3 + corresponding to the OCV, charged, and discharged states.  相似文献   

7.
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   

8.
Solid carbon was investigated as the fuel for an intermediate-temperature solid oxide fuel cell (IT-SOFC). An innovative, indirect operating method involving internal catalytic gasification of carbon to gaseous carbon monoxide via the reverse Boudouard reaction (C(s) + CO2(g)  2CO(g)) was proposed. The carbon gasification reaction rate was greatly enhanced by adopting FemOn–MxO (M = Li, K, Ca) as a catalyst. A peak power density of ~297 mW cm?2 was achieved at 850 °C for an anode-supported SOFC with scandium-stabilized zirconia electrolyte and a La0.8Sr0.2MnO3 cathode by applying a catalyst-loaded, activated carbon as fuel. This peak power density was only modestly lower than that obtained using gaseous hydrogen as the fuel.  相似文献   

9.
Molar calorimetric enthalpy changes ΔrHm(cal) have been measured for the biochemical reactions {cAMP(aq) + H2O(l)=AMP(aq)} and {PEP(aq) + H2O(l)=pyruvate(aq) + phosphate(aq)}. The reactions were catalyzed, respectively, by phosphodiesterase 3,5-cyclic nucleotide and by alkaline phosphatase. The results were analyzed by using a chemical equilibrium model to obtain values of standard molar enthalpies of reaction ΔrHm for the respective reference reactions {cAMP(aq) + H2O(l)=HAMP(aq)} and {PEP3−(aq) + H2O(l)=pyruvate(aq) + HPO2−4(aq)}. Literature values of the apparent equilibrium constants K for the reactions {ATP(aq)=cAMP(aq) + pyrophosphate(aq)}, {ATP(aq) + pyruvate(aq)=ADP(aq) + PEP(aq)}, and {ATP(aq) + pyruvate(aq) + phosphate(aq)=AMP(aq) + PEP(aq) + pyrophosphate(aq)} were also analyzed by using the chemical equilibrium model. These calculations yielded values of the equilibrium constants K and standard molar Gibbs free energy changes ΔrGm for ionic reference reactions that correspond to the overall biochemical reactions. Combination of the standard molar reaction property values (K, ΔrHm, and ΔrGm) with the standard molar formation properties of the AMP, ADP, ATP, pyrophosphate, and pyruvate species led to values of the standard molar enthalpy ΔfHm and Gibbs free energy of formation ΔfGm and the standard partial molar entropy Sm of the cAMP and PEP species. The thermochemical network appears to be reasonably well reinforced and thus lends some confidence to the accuracy of the calculated property values of the variety of species involved in the several reactions considered herein.  相似文献   

10.
We present a binder-free catalytic anode for highly efficient and stable oxygen evolution reaction in alkaline media. The catalyst consists of a thin film of buserite-type layered manganese dioxide (MnO2) intercalated with Co2 + ions, resulting from electrodeposition of the layered MnO2 film with tetrabutylammonium (Bu4N+) ions on a carbon cloth, followed by ion-exchange of the initially incorporated Bu4N+ with Co2 + in solution. The electrode is capable to produce a current density of 10 mA cm 2 at an overpotential (η) of 377 mV with a Tafel slope of 48 mV dec 1, much superior to the layered MnO2 without Co2 +.  相似文献   

11.
Transition metal oxides with composite xLi2MnO3 ·  (1  x)LiMO2 rocksalt structures (M = Mn, Ni, Co) are of interest as a new generation of cathode materials for high energy density lithium-ion batteries. After electrochemical activation to 4.6 or 4.8 V (vs. Li0) at 50 °C, xLi2MnO3 · (1  x)LiMn0.33Ni0.33Co0.33O2 (x = 0.5, 0.7) electrodes deliver initial discharge capacities (>300 mAh/g) at a low current rate (0.05 mA/cm2) that exceed the theoretical values for lithiation back to the rocksalt stoichiometry (240–260 mAh/g), at least during the early charge/discharge cycles of the cells. Attention is drawn to previous reports of similar, but unaccounted and unexplained anomalous behavior of these types of electrode materials. Possible reasons for this anomalous capacity are suggested. Indications are that electrodes in which M = Mn, Ni and Co do not cycle with the same stability at 50 °C as those without cobalt.  相似文献   

12.
A series of lithium–manganese–nickel-oxide compositions that can be represented in three-component notation, xLi[Mn1.5Ni0.5]O4 · (1  x){Li2MnO3 · Li(Mn0.5Ni0.5)O2}, in which a spinel component, Li[Mn1.5Ni0.5]O4, and two layered components, Li2MnO3 and Li(Mn0.5Ni0.5)O2, are structurally integrated in a highly complex manner, have been evaluated as electrodes in lithium cells for x = 1, 0.75, 0.50, 0.25 and 0. In this series of compounds, which is defined by the Li[Mn1.5Ni0.5]O4–{Li2MnO3 · Li(Mn0.5Ni0.5)O2} tie-line in the Li[Mn1.5Ni0.5]O4–Li2MnO3–Li(Mn0.5Ni0.5)O2 phase diagram, the Mn:Ni ratio in the spinel and the combined layered Li2MnO3 · Li(Mn0.5Ni0.5)O2 components is always 3:1. Powder X-ray diffraction patterns of the end members and the electrochemical profiles of cells with these electrodes are consistent with those expected for the spinel Li[Mn1.5Ni0.5]O4 (x = 1) and for ‘composite’ Li2MnO3 · Li(Mn0.5Ni0.5)O2 layered electrode structures (x = 0). Electrodes with intermediate values of x exhibit both spinel and layered character and yield extremely high capacities, reaching more than 250 mA h/g with good cycling stability between 2.0 V and 4.95 V vs. Li° at a current rate of 0.1 mA/cm2.  相似文献   

13.
A visible spectrophotometric method has been developed for the reaction kinetics of o-phenylenediamine in the presence of gold (III). The method is based on the measurement of the absorbance of the reaction o-phenylenediamine and gold (III). Optimum conditions for the reaction were established as pH 6 at λ = 466 nm.When the reaction kinetic of o-phenylenediamine by gold (III) was investigated, it was observed that the following rate formula was found as ln (A/A0) = kt, according to absorbance measurements. The activation energy Ea and Arrhenius constant A were calculated from the Arrhenius equation as 1.009 kJ · mol−1 and 3.46 · 10−2 s−1, respectively. Other activation thermodynamic parameters, entropy, ΔS (J · mol−1 · K−1), enthalpy, ΔH (kJ · mol−1), Gibbs free energy, ΔG (kJ · mol−1) and equilibrium constant, Ke were calculated at T = (283.2, 303.2, 323.2, and 343.2) K. The study was exothermic due to the decrease of entropy and was a non-spontaneous process during activation.  相似文献   

14.
The use of a convenient source of MnIII ions, namely the [Mn(OR)(O2CR′)2]n (R = H, Me, and R′ = Me, But) family of 1-D coordination polymers, afforded two new enneanuclear and decanuclear molecular clusters, homometallic [Mn9O7(O2CBut)13(MeCN)2] (3) and heterometallic [Mn10?xFex(OMe)20(O2CMe)10] (x < 10) (4), respectively. Compound 3 was synthesized by a solvent-induced structural transformation, whereas complex 4 resulted from the reaction of [Mn(OH)(O2CMe)2]n with an FeIII source. The core of 3 comprises two [Mn4O2]8+ butterfly units and a [Mn3O]7+ triangular unit fused together by sharing one Mn atom. Magnetic susceptibility measurements of 3 revealed dominant antiferromagnetic interactions within the molecule, and a ground state of S = 1 with many low-lying excited states. Complex 4 is a mixed FeIII/MnIII single-strand molecular wheel, which forms 3D nanotubular stacks arranged in a zig–zag fashion. The described work suggests that the [Mn(OR)(O2CR′)2]n compounds represent excellent starting materials for MnIII carboxylate cluster chemistry.  相似文献   

15.
A uniform transmembrane pressure (UTMP) crossflow microfiltration (CFMF) system maintains a low but uniform transmembrane pressure (ΔPTM) with high crossflow velocity (CFV), which reduces fouling and cake build-up, and improves the utilization of available filtration area. A CFMF system, with a 0.2 μm nominal pore size ceramic filter, filtration area 0.184 m2, was operated in both UTMP and non-UTMP modes. The two modes were compared for their effectiveness in maintaining a steady flux during the separation of casein micelles from skim milk up to a concentration factor (CF) 10 at 50°C. Experiments were performed at an average CFV of 7.2 m s−1 and ΔPTM from 89 to 380 kPa. Up to CF 4 the non-UTMP mode maintained a slightly better flux and process time than the UTMP mode, but reached the minimally acceptable flux (below 0.005 kg m−2 s−1) at CF 6. Depending upon the ΔPTM maintained, the UTMP mode approached the minimal flux at CF 7 or 10 depending upon the combination of ΔPTM and CFV used. Cake resistance (Rcm) was modified to include the effect of an increase in retentate viscosity with concentration. Rcm increased for the non-UTMP mode and decreased for the UTMP mode with a decrease in the ratio of permeation flux/wall shear stress (Jp/τw) (which occurred as the retentate gets concentrated). This indicated that the cake formed during the non-UTMP mode of operation was more compact and durable (harder to erode) than in the UTMP mode. A central composite rotatable design estimated the optimal operating region at a CFV of 7.1 m s−1 and ΔPTM of 241±10 kPa to achieve maximum flux and a high concentration.  相似文献   

16.
One common dilemma encountered in designing a supercapacitor electrode is that the specific capacitance (Cs) of the active material decreases significantly as the active-material loading (mass area? 1) increases. As a result, the geometric capacitance density (GCD; Farad area? 1) of the electrode does not scale up linearly but gradually levels off with increasing loading. For MnO2 supercapacitors, this problem has been solved to a great extent by introducing a superabsorbent polymer (SAP) binder, namely polyacrylic acid (PAA), to form composite particles with MnO2. Other than acting as a binder to bound together MnO2 particles, the SAP is believed to facilitate distribution of electrolyte throughout the active layer owing to its electrolyte-absorbing and swelling behaviors. The Cs of MnO2 remains almost unchanged as the oxide loading varies over a wide range (1.5–6.5 mg cm? 2) of heavy active-material loading. In addition, putting PAA throughout the entire active layer helps to magnify the specific interaction between PAA and MnO2 that is known to enhance the capacitance of individual MnO2 particles. The success in combining both high Cs and high active-material loading results in GCD of ca. 1.8–1.4 F cm? 2 even under very high current densities (ca. 35–260 mA cm? 2 or 5–40 A g? 1-MnO2).  相似文献   

17.
The kinetics of the oxidative degradation of dipeptide glycyl–glycine (Gly-Gly) by water-soluble colloidal MnO2 in acidic medium has been studied by employing visible spectrophotometer in the aqueous and micellar media at 35 °C. To obtain the rate constants as functions of [Gly-Gly], [MnO2] and [HClO4], pseudo-first-order conditions were maintained in each kinetic run. The first-order-rate is observed with respect to [MnO2], whereas fractional-order-rates are determined in both [Gly-Gly] and [HClO4]. The addition of sodium pyrophosphate and sodium fluoride has composite effects (catalytic and inhibition). The reaction proceeds through the fast adsorption of Gly-Gly on the surface of the colloidal MnO2. The observed results are discussed in terms of Michaelis–Menten/Langmuir–Hinshelwood model. The Arrhenius and Eyring equations are found valid for the reaction over a range of temperatures and different activation parameters have been evaluated. A probable reaction mechanism, in agreement with the observed kinetic results, has been proposed and discussed. The influence of changes in the surfactant concentrations on the observed rate constant is also investigated and the reaction followed the same type of kinetic behavior in micellar media. The pseudo-first-order rate constant (kψ) is found to increase about two-fold with increase in [TX-100]. The catalytic effect of nonionic surfactant TX-100 is explained in terms of the mathematical model proposed by Tuncay et al.  相似文献   

18.
The solubility of anthracene was measured in pure water and in sodium chloride aqueous solution (salt concentration, m/mol · kg?1 = 0.1006, 0.5056, and 0.6082) at temperatures between (278 and 333) K. Solubility of anthracene in pure water agrees fairly well with values reported in earlier similar studies. Solubility of anthracene in sodium chloride aqueous solutions ranged from (6 · 10?8 to 143 · 10?8) mol · kg?1. Sodium chloride had a salting-out effect on the solubility of anthracene. The salting-out coefficients did not vary significantly with temperature over the range studied. The average salting-out coefficient for anthracene was 0.256 kg · mol?1.The standard molar Gibbs free energies, ΔtrG°, enthalpies, ΔtrH°, and entropies, ΔtrS°, for the transfer of anthracene from pure water to sodium chloride aqueous solutions were also estimated. Most of the estimated ΔtrG° values were positive [(20 to 1230) J · mol?1]. The analysis of the thermodynamic parameters shows that the transfer of anthracene from pure water to sodium chloride aqueous solution is thermodynamically unfavorable, and that this unfavorable condition is caused by a decrease in entropy.  相似文献   

19.
Cavity ring-down spectroscopy is used to probe the optical absorption of the optical pseudo-two level system [Xe]4f13 Yb3+ in room temperature solution, a situation where the two-color pump-probe luminescence approach commonly used to study the other [Xe]4fn (2  n  12) trivalent lanthanide ions fails. A 1 m optical cavity constructed from two highly reflective mirrors is used to obtain ring-down signals as a function of wavelength from 1 mL samples contained in a quartz cuvette placed in the center of the cavity. Absorption spectra constructed from these signals characteristic of the 6H15/2  4F9/2 [Xe]4f5 Dy3+ and the 7F0  5D0 [Xe]4f6 Eu3+ transitions are presented and compared to the corresponding single pass absorption and two-color pump-probe luminescence spectra to obtain sensitivity estimates. Finally the spectrum for the 2F5/2  2F7/2 [Xe]4f13 Yb3+ transition for a model Yb3+ complex in room temperature solution is obtained using cavity ring-down spectroscopy for the first time.  相似文献   

20.
A novel cation exchanger (TFS-CE) having carboxylate functionality was prepared through graft copolymerization of hydroxyethylmethacrylate onto tamarind fruit shell (TFS) in the presence of N,N′-methylenebisacrylamide as a cross-linking agent using K2S2O8/Na2S2O3 initiator system, followed by functionalisation. The TFS-CE was used for the removal of Cu(II) from aqueous solutions. At fixed solid/solution ratio the various factors affecting adsorption such as pH, initial concentration, contact time, and temperature were investigated. Kinetic experiments showed that the amount of Cu(II) adsorbed increased with increase in Cu(II) concentration and equilibrium was attained at 1 h. The kinetics of adsorption follows pseudo-second-order model and the rate constant increases with increase in temperature indicating endothermic nature of adsorption. The Arrhenius and Eyring equations were used to obtain the kinetic parameters such as activation energy (Ea) and enthalpy (ΔH#), entropy (ΔS#) and free energy (ΔG#) of activation for the adsorption process. The value of Ea for adsorption was found to be 10.84 kJ · mol?1 and the adsorption involves diffusion controlled process. The equilibrium data were well fitted to the Langmuir isotherm. The maximum adsorption capacity for Cu(II) was 64 · 10 mg · g?1 at T = 303 K. The thermodynamic parameters such as changes in free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were derived to predict the nature of adsorption process. The isosteric heat of adsorption increases with increase in surface loading indicating some lateral interactions between the adsorbed metal ions.  相似文献   

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