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1.
The thermodynamic activation parameters of hindered rotation of the CF3 group in the 4-nitrophenyltrifluoromethylsulfone radical anion in DMF were determined from the temperature dependence of the EPR line widths and spin density distributions calculated by the U-B3LYP method in the 6-31+G* basis set. In the range 293 > T > 199 K, the activation energy of hindered rotation E F depends on the temperature and changes in the range 9.67 < E F < 18.95 kJ·mol?1; the changes in the activation enthalpy and entropy are 7.23 < ΔH < 17.30 kJ·mol?1 and ?53.45 < ΔS < ?11.37 J·(mol·K)?1, respectively. Based on the suggested method for evaluating the inner product of the g tensor and the tensor of anisotropic hfi with the 14N nucleus for nitrobenzene radical anions in the liquid state we calculated the correlation time and determined the activation energy of rotational diffusion of the 4-nitrophenyltrifluoromethylsulfone radical anion in DMF, E r = 20.175±0.54 kJ·mol?1.  相似文献   

2.
This study was designed to examine the interaction of histamine H2-receptor antagonist drug ranitidine (RTN) with human serum albumin by multi-spectroscopic methods. The experimental results showed the involvement of dynamic quenching mechanism which was further confirmed by lifetime spectral studies. The binding constants (K a) at three temperatures (288, 298, and 308 K) were 2.058 ± 0.020, 4.160 ± 0.010 and 6.801 ± 0.011 × 104 dm3 mol?1, respectively, and the number of binding sites (m) were 1.169, respectively; thermodynamic parameters ΔH 0 (44.152 ± 0.047 kJ mol?1), ΔG 0 (?26.214 ± 0.040 kJ mol?1), and ΔS 0 (236.130 ± 0.025 J K?1 mol?1) were calculated. The distance r between donor and acceptor was obtained (r = 3.40 nm) according to the Förster theory of non-radiative energy transfer. Synchronous fluorescence, CD, AFM and 3D fluorescence spectral results revealed the changes in secondary structure of the protein upon interaction with RTN. A molecular modeling study further confirmed the binding mode obtained by the experimental studies.  相似文献   

3.
In this work, a 304 stainless steel (SS) was anodized to prepare nanoporous SS (NPSS) with an average size of about 75 nm and then filled with copper (Cu/NPSS) using pulsed electrodeposition method. Afterward, a nanostructural Pt and Pd film was deposited by galvanic replacement (GR) on the Cu/NPSS to prepare modified electrode (PtPd/Cu/NPSS) for hydrogen evolution reaction (HER) and formic acid electrooxidation (FAO). The electrocatalytic activity of the modified electrode and its structural characterization have been studied by voltammetric methods, electrochemical impedance spectroscopy (EIS), inductively coupled plasma optical emission spectrometry (ICP-OES), and field emission scanning electron microscopy (FESEM). The results show that the nanostructural Pt1Pd1/Cu/NPSS composition, with low Pt loading and suitable stability, has a good electrocatalytic performance toward HER (EOnset = + 12 mV vs. NHE) and FAO (EOnset = ?180 mV vs. NHE). For HER observed a high mass activity of noble metals (87.54 mA cm?2μg Pd+Pt ?1 ) in comparison with Pt deposited Cu/NPSS (41.5 mA cm?2 μg Pt ?1 ) at the same applied potential of ? 0.25 V versus NHE. Also, the fabricated electrocatalysts with more electrochemically active surface area in comparison with Pd/Cu/NPSS and Pt/Cu/NPSS revealed more resisting to the poisoning components and good stability for FAO.  相似文献   

4.
Interaction of ammonia with H-MCM-22 zeolite (Si/Al = 24.5) was investigated by temperature-programmed desorption technique in order to obtain information on thermodynamics of the process. Average activation energy for desorption of ammonia from Brønsted acid sites of H-MCM-22 zeolite was estimated from the data obtained under conditions varying in heating rate and also flow rate of carrier gas. It resulted in value of E d = 127 kJ mol?1 for heat rate variation method, whereas flow rate variation led to E d value of 111 kJ mol?1. Obtained E d values are compared with those reported in the literature for other zeolitic materials and discussed in the broader context of zeolite acidity. Comparison of E d values estimated here for H-MCM-22 zeolite with corresponding data for other protonic zeolites shows that H-MCM-22 displays mediocre/lower activation energy for ammonia compared with other high-silica zeolites.  相似文献   

5.
Adsorption of the gadolinium from H2O and HCl solutions on the ion-exchange resin C100 is investigated. The experiments were carried out by varying the acidity of the liquid phase, the amount of sorbent, and the temperature. The maximal sorption of the ions Gd3+ is observed from the solution 0–0.2 M HCl under optimal conditions, the sorption reaches more than 99.5%. Sorption of Gd3+ on C100 from H2O solution occurs most intensively during the first 3 min then for 30 min the system smoothly comes to equilibrium. The maximal sorption capacity of the resin C100 amounted to 1.2 ± 0.1 mmol g?1. The thermodynamic parameters of sorption: ΔG = ? 24.20 kJ mol?1, ΔS = ? 90.27 J mol?1 K?1, ?H = ? 50.93 kJ mol?1 were evaluated. It is shown that the sorption of gadolinium on the ion-exchange resin C100 is described by models of kinetically pseudo-first and pseudo-second order. It is established that the Gd3+ sorption on the C100 resin is reversible second order chemical reaction.  相似文献   

6.
A novel peroxy group-containing silane coupling agent was synthesized and anchored on the surface of titanium dioxide nanoparticles (nano-TiO2) to form an immobilized-initiator-modified nano-TiO2 species. In this study, the kinetic parameters of the peroxy group-containing silane were tested and assessed using DSC. The pre-exponential factor (Ad) was 8.973?×?108 and the activation energy (Ea) was 80.736 kJ mol?1. Moreover, the empirical Arrhenius equation was determined to be ln Kd?=???80.736/RT?+?ln(8.973?×?108). To obtain continuous polymers, acrylonitrile (AN) and methyl methacrylate (MMA) were polymerized using the novel peroxy group-containing silane and FeSO4 as an initiator system. The number average molecular weights (Mn of PAN?=?3×104 and Mn of PMMA?=?1.4?×?105) and polydispersity indexes (PDI of PAN?=?2.76 and PDI of PMMA?=?1.65) were determined by GPC. It was suggested that the redox initiation system can generate highly reactive species on the surfaces of inorganic nanoparticles. The nano-TiO2-grafted polymers were successfully obtained.  相似文献   

7.
Molecular structure, conformational stability and vibrational wave numbers for the rotational isomers of 2-furoyl chloride and 3-furoyl chloride have been computed using the B3LYP method with the 6-311++G(d,p) basis set. From computations, 2-furoyl chloride was predicated to exist predominantly in cis conformation with cistrans rotational barrier 40.40 kJ·mol?1, and 3-furoyl chloride was predicated to exist predominantly in the trans conformation with cistrans rotational barrier 30.17 kJ·mol?1. The effects of solvents on the conformational stability of all the molecules in nine different solvents (heptane, chloroform, tetrahydrofuran, dichloroethane, acetone, ethanol, methanol, dimethylsulfoxide and water) were investigated. The integral equation formalism of the polarizable continuum model was used for all solution phase computations. The vibrational wave numbers and the corresponding vibrational assignments of the molecules in C1 symmetry were examined and the simulated infrared spectra of the molecules are reported. The geometrical parameters, highest occupied and lowest unoccupied molecular orbitals, Infrared intensities, and molecular electrostatic potentials results are reported.  相似文献   

8.
The nanosized LiNiPO4 was successfully synthesized by a solid-state reaction between the new Ni3(PO4)2·8H2O precursor and Li3PO4 at 700 °C in air atmosphere. The formation of LiNiPO4 was generated via three thermal decomposition steps. The samples were characterized by Fourier transform infrared, X-ray diffraction, scanning electron microscopy, atomic absorption/atomic emission spectrophotometers, and thermogravimetric/differential thermal gravimetric/differential thermal analysis techniques. The activation energy (Eα) values of the three steps were calculated by Vyazovkin method and determined to be 90.39?±?5.79, 197.81?±?7.46, and 308.66?±?12.03 kJ mol?1, respectively. The average Eα values from this method are very close to Eα from KAS method. The most probable mechanism functions g(α) of three steps were evaluated by using the masterplots method and found to be the F1/3 (first step), F3/2 (second step), and D4 (final step), respectively. The pre-exponential factors (A) values of three steps were obtained based on the Eα and g(α). The kinetic triplet parameters of the formation of LiNiPO4 from the new precursor are reported in the first time.  相似文献   

9.
A new high-nitrogen complex [Cu(Hbta)2]·4H2O (H2bta = N,N-bis-(1(2)H-tetrazol-5-yl) amine) was synthesized and characterized by elemental analysis, single crystal X-ray diffraction and thermogravimetric analyses. X-ray structural analyses revealed that the crystal was monoclinic, space group P2(1)/c with lattice parameters a = 14.695(3) Å, b = 6.975(2) Å, c = 18.807(3) Å, β = 126.603(1)°, Z = 4, D c = 1.888 g cm?3, and F(000) = 892. The complex exhibits a 3D supermolecular structure which is built up from 1D zigzag chains. The enthalpy change of the reaction of formation for the complex was determined by an RD496–III microcalorimeter at 25 °C with the value of ?47.905 ± 0.021 kJ mol?1. In addition, the thermodynamics of the reaction of formation of the complex was investigated and the fundamental parameters k, E, n, \( \Updelta S_{ \ne }^{{{\uptheta}}} \), \( \Updelta H_{ \ne }^{{{\uptheta}}} \), and \( \Updelta G_{ \ne }^{{{\uptheta}}} \) were obtained. The effects of the complex on the thermal decomposition behaviors of the main component of solid propellant (HMX and RDX) indicated that the complex possessed good performance for HMX and RDX.  相似文献   

10.
11.
Zinc nitroprusside (ZnNP) nanoparticles were fabricated at the surface of zinc powder-doped carbon ceramic electrode (CCE) by a chemical derivatization process. This modified electrode was characterized by scanning electron microscopy, atomic force microscopy and cyclic voltammetry techniques. The charge transfer rate constant (k s) and charge transfer coefficient (α) were calculated for the electron exchange reaction of the ZnNP thin film. The ZnNP nanoparticle-modified CCE (ZnNP|CCE) showed good electrocatalytic activity toward hydrazine oxidation. The limit of detection (S/N = 3) and sensitivity were found to be 0.16 µM and 0.21 µA/µM, respectively. The mechanism of hydrazine electrooxidation at the electrode surface was studied. Finally, the ZnNP|CCE was successfully used for the determination of trace amount of hydrazine in different spiked and real samples.  相似文献   

12.
The present study was focused on the thermal degradation of Eulaliopsis binata biomass produced on a salt-affected soil without any fertilizer or pesticide applications. The plant biomass was subjected to thermal degradation experiments at three heating rates, 10, 30 and 50 K min?1. The kinetic analyses were performed through isoconversional models of Kissinger–Akahira–Sunose and Flynn–Wall–Ozawa, followed by the calculation of thermodynamic parameters of activation. The high heating value was calculated as 15.10 MJ mol?1. The activation energy values of the grass were shown to be ranging from 118 through 240 kJ mol?1. Energy difference of enthalpies of activation between the reagent and the activated complex was in accordance with activation energies. Pre-exponential factors indicated the reaction to follow first-order kinetics. Gibbs free energy for the grass was measured to be ranging from 171 to 174 kJ mol?1. Our data have shown that E. binata biomass offers remarkable potential as a low-cost biomass for bioenergy.  相似文献   

13.
Differential scanning calorimetry (DSC) was used to investigate the thermal behavior and non-isothermal crystallization kinetics of the Fe67Nb5B28 metallic glasses prepared by melt-spinning method. DSC traces exhibit that the crystallization takes place through a single exothermic reaction, and it processes a good thermal stability in thermodynamics. The activation energies for nucleation and grain growth processes were calculated to be 536 ± 22 and 559 ± 20 kJ mol?1 by Kissinger equation, respectively, and 551 ± 24 and 574 ± 20 kJ mol?1 by Ozawa equation, respectively. It means that the grain growth process is more difficult than the nucleation process. The variation of local Avrami exponent n(x) with crystallized fraction x demonstrates that the crystallization mechanism varies at different stages. The n(x) is larger than 2.5 at the initial stage of 0 < x < 0.3, implying a mechanism of diffusion-controlled three-dimensional growth with increasing nucleation rate. The n(x) decreases from 2.5 to 1.5 in the range of 0.3 < x < 0.65, suggesting that the crystallization belongs to three-dimensional nucleation and grain growth with decreasing nucleation rate. And n(x) lies between 1.0 and 1.5 in the range of 0.65 < x < 0.95, indicating that the crystallization corresponds to the growth of particles with an appreciable initial volume. Low-temperature annealing corresponds to the precipitation of α-Fe, Fe2B, and Fe23B6 phases, and further annealing leads to the formation of α-Fe, Fe2B, and FeNbB phases. The magnetic properties in relation to microstructure change of the Fe67Nb5B28 metallic glasses are discussed.  相似文献   

14.
The research shows theoretical calculations on the thermodynamics of digestion/gasification processes where glucose is used as a surrogate for biomass. The change in Enthalpy (?H) and Gibbs Free Energy (?G) is used to obtain the Attainable Region (AR) that shows the overall thermodynamic limits for digestion/gasification from 1 mol of glucose. Gibbs Free Energy and Enthalpy (GH) plots were calculated for the temperature range 25–1500 °C. The results show the effect of temperature on the AR for the processes when water is in both liquid and gas states using 25 °C, 1 bar as the reference state. The AR results show that the production of CO, H2, CH4 and CO2 are feasible at all temperatures studied. The minimum Gibbs Free Energy becomes more negative from ?418.68 kJ mol?1 at 25 °C to ?3024.34 kJ mol?1 at 1500 °C while the process shifts from exothermic (?141.90 kJ mol?1) to endothermic (1161.80 kJ mol?1) for the respective temperatures. Methane and carbon dioxide are favoured products (minimum Gibbs Free Energy) for temperatures up to about 600 °C, and this therefore includes Anaerobic Digestion. The process is exothermic below 500 °C, and thus Anaerobic Digestion requires heat removal. As the temperature continues to increase, hydrogen production becomes more favourable than methane production. The production of gas is endothermic above 500 °C, and it needs a supply of heat that could be done, either by combustion or by electricity (plasma gasification). The calculations show that glucose conversion at temperatures around 700 °C favours the production of carbon dioxide and hydrogen at minimum G. Generally, the results show that the gas from high-temperature gasification (>~800 °C) typically carries the energy mainly in syngas components CO and H2, whereas at low-temperature gasification (<500 °C) the energy is carried in CH4. The overall analysis for the temperature range (25–1500 °C) also suggests a close relationship between biogas production/digestion and gasification as biogas production can be referred to as a form of low-temperature gasification.  相似文献   

15.
Mononuclear Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Mg(II), Sr(II), Ba(II), Ca(II), Pt(IV), Au(III), and Pd(II) complexes of the drug amlodipine besylate (HL) have been synthesized and characterized by elemental analysis, spectroscopic technique (IR, UV–Vis, solid reflectance, scanning electron microscopy, X-ray powder diffraction, and 1H-NMR) and magnetic measurements. The elemental analyses of the complexes are confirmed by the stoichiometry of the types [M(HL)(X)2(H2O)]·nH2O [M = Mn(II), Co(II), Zn(II), Ni(II), Mg(II), Sr(II), Ba(II), and Ca(II); X = Cl? or NO3 ?], [Cd(HL)(H2O)]Cl2, [Pd(HL)2]Cl2, [Pt(L)2]Cl2, and [Au(L)2]Cl, respectively. Infrared data revealed that the amlodipine besylate drug ligand chelated as monobasic tridentate through NH2, oxygen (ether), and OH of besylate groups in Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Mg(II), Sr(II), Ba(II), Ca(II), and Au(III) complexes, but in Pt(IV) and Pd(II) complexes, the amlodipine besylate coordinates via NH2 and OH (besylate) groups. An octahedral geometry is proposed for all complexes except for the Cd(II), Pt(IV), and Pd(II) complexes. The amlodipine besylate free ligand and the transition and non-transition complexes showed antibacterial activity towards some Gram-positive and Gram-negative bacteria and the fungi (Aspergillus flavus and Candida albicans).  相似文献   

16.
From studies using different experimental techniques employed to determine the presence of aggregates e.g. isothermal titration calorimetry, surface tension, electrical conductivity, UV–Vis spectrophotometry, dynamic and static light scattering, it is clearly demonstrated that the compound [Cu(4, 4′-dimethyl-2, 2′-bipyridine)(acetylacetonato)H2O]NO3 (Casiopeína III-ia), promising member of a family of new generation compounds for cancer treatment, is able to auto associate in aqueous media. Physicochemical properties associated with the formation of the aggregates were determined in pure water and in phosphate buffer media in order to simulate physiological conditions. From isothermal titration calorimetry and electrical conductivity measurements we calculated the dissociation constant of the aggregates, K D . For pure water the values obtained in both techniques are 2.73 × 10?4 and 5.93 × 10?4 M respectively while for the buffer media we obtained 4.61 × 10?4 and 1.57 × 10?3 M. The enthalpy of dissociation, ?H D , calculated from the calorimetric data shows that the presence of the phosphate ions has an energetic effect on the aggregate stability since in pure water a value of 18.79 kJ mol?1 was obtained in comparison with the buffer media where a value 4 times bigger was found (70.48 kJ mol?1). With the data collected from these techniques the number of monomers calculated which participate in the formation of the aggregates is around two. From our surface tension, electrical conductivity and UV–Vis spectrophotometry measurements the critical aggregate concentration, cac, was determined. For each technique specific concentration ranges were obtained but we can summarize that the cac in pure water is between 3 and 3.5 mM and for the buffer media is between 3.5 and 4 mM. Dynamic light scattering measurements provide us with the hydrodynamic diameter of the aggregates and from static light scattering measurements we determined the molecular weight of the Casiopeína III-ia aggregates to be of 1000.015 g mol?1 which is two times the molecular weight of the Casiopeína III-ia molecule. This value is in agreement with the number of monomers which participate in the formation of the aggregates obtained from isothermal titration calorimetry and electrical conductivity data analysis.  相似文献   

17.
[Mn(NH3)6](NO3)2 crystallizes in the cubic, fluorite (C1) type crystal lattice structure (Fm \( \overline{3} \) m) with a = 11.0056 Å and Z = 4. Two phase transitions of the first-order type were detected. The first registered on DSC curves as a large anomaly at T C1 h  = 207.8 K and T C1 c  = 207.2 K, and the second registered as a smaller anomaly at T C2 h  = 184.4 K and T C2 c  = 160.8 K (where the upper indexes h and c denote heating and cooling of the sample, respectively). The temperature dependence of the full width at half maximum of the band associated with the δs(HNH)F1u mode suggests that the NH3 ligands in the high temperature and intermediate phase reorientate quickly with correlation times in the order of several picoseconds and with activation energy of 9.9 kJ mol?1. In the phase transition at T C2 c probably only a some of the NH3 ligands stop their reorientation, while the remainders continue to reorientate quickly with activation energy of 7.7 kJ mol?1. Thermal decomposition of the investigated compound starts at 305 K and continues up to 525 K in four main stages (I–IV). In stage I, 2/6 of all NH3 ligands were seceded. Stages II and III are connected with an abruption of the next 2/6 and 1/6 of total NH3, respectively, and [Mn(NH3)](NO3)2 is formed. The last molecule of NH3 per formula unit is freed at stage IV together with the simultaneous thermal decomposition of the resulting Mn(NO3)2 leading to the formation of gaseous products (O2, H2O, N2 and nitrogen oxides) and solid MnO2.  相似文献   

18.
Leachate samples from a sanitary landfill of Araraquara city and composting usine of Vila Leopoldina, São Paulo, Brazil were lyophilized to remove the water content. TG/DTG curves at different heating rates were recorded. The second step of the thermal decomposition of leachate from the Araraquara landfill (CB1), from the composting usine from Vila Leopoldina (CB2) from the organic phase extracted (FO) and aqueous phase (FA) were all kinetically evaluated using the non-isothermal method.By Flynn-Wall isoconversional method the following values were obtained: E=234±3.65 kJ mol?1 and logA=29.7±0.58 min?1 for CB1; E=129±1.66 kJ mol?1 and logA=11.8±0.10 min?1 for CB2; E=51.6±1.35 kJ mol?1 and logA=6.09±0.09 min?1 for FO and E=76.91±6.33 kJ mol?1 and logA=8.88±0.7 min?1 for FA with 95% confidence level. Applying the procedures of Málek and Koga, SB kinetic model (?esták-Berggren) is the most appropriate to describe the decomposition of CB1, CB2, FO and FA.  相似文献   

19.
A new three-dimensional platinum(II)–thallium(I) coordination polymer [{Pt(pda)(NHCOtBu)2}4Tl4][Pt(CN)4]2·2H 2 O (pda = 1,2-propyldiamine) has been prepared from the direct reaction of [Tl2Pt(CN)4] and [Pt(pda)(NHCOtBu)2] in water, and its structure was characterized by X-ray diffraction analysis. The compound crystallizes in monoclinic, space group Pn, a = 11.567(2) Å, b = 11.570(2) Å, c = 37.677(8)Å, β = 94.64(3)°, V = 5025.8(17) Å3, Z = 2, R1 = 0.0679 and wR2 = 0.1574 [I >  2σ (I)], Goodness-of-fit on F 2 = 1.055. The compound exhibits a novel 3D network structure consisting of [Pt(CN)4]2? connected 1D infinite Pt–Tl–Pt–Tl chains via strong Pt–Tl bonds.  相似文献   

20.
The heat capacities of 1-butyl-3-methylimidazolium lactate ionic liquids ([C4mim][Lact]) were measured with a highly accurate automatic adiabatic calorimeter over the temperature range from 79 to 406 K. And the experimental values of molar heat capacities were fitted to a polynomial equation using least square method in the appropriate temperature ranges. The standard molar heat capacity was determined to be 1734.46?±?5.12 J K?1 mol?1 at 298.15 K. The molar enthalpy and molar entropy of the transition were determined to be 15.575?±?0.045 and 64.44?±?0.14 J K?1 mol?1. Other thermodynamic properties, such as (HT???H298.15) and (ST???S298.15), were also calculated. Furthermore, when the temperature reaches 241.87 K, the strongest peaks appeared by analysis of the heat capacity curve. This phenomenon could be explained from the interionic interaction, which is the hydrogen bond between the anions and cations.  相似文献   

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