Copper catalysis of 8-acetoxyquinoline hydrolysis

The hydrolysis of 8-acetoxyquinoline in dilute acid solution has been found to be subject to copper^II catalysis. The catalysed reaction is first order in 8-acetoxyquinoline (as the free base), first order in copper ion, and first order in hydroxide ion. It is proposed that a copper chelate is a reaction intermediate in the hydrolysis.     

Correlations between photoelectron and phosphorescence spectra of polycyclic hydrocarbons

Comparison of the first IP's obtained from the photoelectron spectra of polycyclic hydrocarbons with the phosphorescence bands and the p-, α- and β-bands in the absorption spectra shows that only the first IP's, the first p-bands and the first phosphorescence bands are related to each other. The first triplet level T can be calculated from the difference IP₁ ? E_t = T, where E_t is the energy of the first phosphorescence band. The first triplet level T approaches 4.9 eV which is the vertical IP of graphite. Any deviation from this value is strictly related to the number of aromatic sextets in polycyclic systems. This applies to kata- and peri-condensed hydrocarbons. The asymmetric annellation effects reported in earlier work are again supported by the phosphorescence spectra. Contrary to the observations with the α-, β- and p-bands, there is considerable interaction with the third branch in linear benzologues of triphenylene (starphenes) when the t-bands are formed, and the T level shifts towards higher energies (lower eV values).     

The complex formation-partition and partition-association models of solvent extraction of ions

Two models of the extraction process have been proposed. In the first model it is assumed that the partitioning neutral species is at first formed in the aqueous phase and then transferred into the organic phase. The second model is based on the assumption that equivalent amounts of cations and anions are at first transferred from the aqueous into the organic phase and then associated to form a neutral molecule. The role of the solubility parameter in extraction and the relation between the solubility of liquid organic substances in water and the partition of complexes have been discussed. The extraction of simple complexes and complexes with organic ligands has been discussed using the first model. Partition coefficients have been calculated theoretically and compared with experimental values in some very simple cases. The extraction of ion pairs has been discussed using the partition-association model and the concept of single-ion partition coefficients.     

Kinetics and mechanism of HCN evolution from nylon 66 and design of apparatus

The evolution of HCN from the oxidation of nylon 66 has been studied in three apparatuses of different design (all based on stream flow) over a temperature range from 390 to 700°C. Although the numerical values for rate constants (diffusion controlled) and energies of activation differ, the same mechanism is deduced from the results of the three designs. It is concluded that a simple horizontal tube in a furnace is the most efficient apparatus as far as sweeping out volatile products is concerned. The mechanism of thermal oxidative degradation has been evaluated in detail. It is shown that mechanisms where the first reaction step is not the slowest or the slowest one of first or second order all fit the experimental results. However, it is concluded that the mechanism where the first step is first order and the slowest one is the most likely one. The respective parameters have been evaluated for the results obtained from the horizontal tube apparatus.     

Synthesis of functionalized benzannulated compounds

Functionalized indane and naphthalene derivatives have been prepared according to two routes involving a nickel-catalyzed electrochemical arylation of activated olefins as the key step. The first method is a cascade process including the intramolecular nucleophilic addition of the first formed enolate intermediate. In the second method the cascade reaction is prevented by in situ protonation of the enolate, and the cyclization is further conducted chemically. This is an overall more efficient method than the first one, based on the electrochemical process.     

Ti-MWW催化氯丙烯环氧化反应动力学行为

以Ti-MWW分子筛为催化剂,以H2O2为氧化剂,系统研究了氯丙烯环氧化反应的动力学行为.结果表明,该反应速率与Ti-MWW分子筛的用量成正比,是1级反应.当H2O2浓度小于0.67 mol/L时,环氧化反应为1级反应;大于2 mol/L时,为0级反应.随着氯丙烯浓度的增加,环氧化反应级数从1级向0级转变;且只有当其浓...     

Theoretical Studies on the First Hyperpolarizabilities of One-dimensional Donor-bridge-acceptor Chromophores and New Applications of BLA in Determining Molecular First Hyperpolarizabilities

We present a quantum-chemical analysis of the relationship between the bond length alteration （BLA） and the static first hyperpolarizability of a series of one-dimensional （1D） chromophores with donor-bridge-acceptor （D-B-A） structures. The calculated results show that the parameter BLA can be considered as an indicator to evaluate the molecular first hyper- polarizability. Along the direction of molecular ground-state dipole moments, the evolutions of BLA can be classified into three categories： the first is a non-monotonic line, which represents most chromophores; the second is monotonic increasing; and the third, contrarily, is monotonic decreasing. On the whole, the first hyperpolarizabilities of these studied chromophores are the monotonic functions of BLA along the direction of dipole moments. Therefore, the first hyperpolarizability of these 1D chromophores can be preliminarily evaluated in terms of the development of BLA without a rigorous computation. In other words, one can roughly estimate the relative magnitude of the first hyperpolarizability according to the optimized geometry.     

Analysis of Adsorption Data of Graphitized Thermal Carbon Black with a DFT-Lattice Gas Theory

In this paper we analyzed the adsorption of gases and vapors on graphitised thermal carbon black by using a modified DFT-lattice theory, in which we assume that the behavior of the first layer in the adsorption film is different from those of second and higher layers. The effects of various parameters on the topology of the adsorption isotherm were first investigated, and the model was then applied in the analysis of adsorption data of numerous substances on carbon black. We have found that the first layer in the adsorption film behaves differently from the second and higher layers in such a way that the adsorbate-adsorbate interaction energy in the first layer is less than that of second and higher layers, and the same is observed for the partition function. Furthermore, the adsorbate-adsorbate and adsorbate-adsorbent interaction energies obtained from the fitting are consistently lower than the corresponding values obtained from the viscosity data and calculated from the Lorentz-Berthelot rule, respectively.     

The study of extrasolar planets: methods of detection,first discoveries and future perspectives

The discover of the first planets around a pulsar 1992 and a pulsar 1992 had around a main sequence star different from our Sun 1995 has opened, after centuries of speculation, a new era in astronomy. The motivations behind the search for ‘other worlds” are presented. A comperative review is made of different techniquess for their detection. Special attention is paid to the planet parameters which can be derived in each method. The first discoveries and their astrophysical consequences are coflined, A review of new ques-tions and future projects beyond these first discoveries is given.     

Effect of the relaxation of high-frequency vibrational modes on the kinetics of charge separation and recombination

The processes of intramolecular electron transfer from the second excited electron state accompanied by superfast reverse transfer to the first excited state are studied. The kinetics of the populations of the first and second excited states, along with that the charge-separated states, is calculated within the generalized stochastic model, taking into account the reorganization of the medium and intramolecular high-frequency vibrations. It is shown that variations in the relaxation rate of the high-frequency vibrational modes can change the population of the quenching products by a factor of two to three. It is established that in the case of the weak exothermicity of the charge separation process, the population of the charge-separated states declines upon an increase in the vibrational relaxation rate, while the population of the first excited state increases; in the region of high exothermicity, these dependences change to ones that are opposite. To reveal the scales of these effects in real systems, the kinetics of the photo-induced processes in the zinc-porphyrin derivatives, including electron-acceptor imide groups covalently coupled with porphyrin rings, are calculated. It is shown that the results from calculating the kinetics of the population of the first and the second excited states agree well with the experimental data on the kinetics of the fluorescence of these states. The absolute values of the population of the charge-separated state and the first excited state are determined. The key role of the hot electron transitions that occur in parallel with the relaxation of the medium and intramolecular vibrations in the considered process is shown.     

The chromic acid oxidation of oxalic acid : Evidence of chromium(IV) oxidation

In the chromic acid oxidation of oxalic acid in the range where the reaction is first order in the substrate, oxalic acid is very reactive toward chromium(IV) and rather unreactive toward chromium(V). A mechanism analogous to that of the chromic acid oxidation of alcohols and aldehydes is proposed for the first order kinetic term.     

A view about the short histories of the mole and Avogadro’s number

The mole and Avogadro’s number are two important concepts of science that provide a link between the properties of individual atoms or molecules and the properties of bulk matter. It is clear that an early theorist of the idea of these two concepts was Avogadro. However, the research literature shows that there is a controversy about the subjects of when and by whom the mole concept was first introduced into science and when and by whom Avogadro’s number was first calculated. Based on this point, the following five matters are taken into consideration in this paper. First, in order to base the subject matter on a strong ground, the historical development of understanding the particulate nature of matter is presented. Second, in 1811, Amedeo Avogadro built the theoretical foundations of the mole concept and the number 6.022 × 10²³ mol^?1. Third, in 1865, Johann Josef Loschmidt first estimated the number of molecules in a cubic centimetre of a gas under normal conditions as 1.83 × 10¹⁸. Fourth, in 1881, August Horstmann first introduced the concept of gram-molecular weight in the sense of today’s mole concept into chemistry and, in 1900, Wilhelm Ostwald first used the term mole instead of the term ‘gram-molecular weight’. Lastly, in 1889, Károly Than first determined the gram-molecular volume of gases under normal conditions as 22,330 cm³. Accordingly, the first value for Avogadro’s number in science history should be 4.09 × 10²² molecules/gram-molecular weight, which is calculated by multiplying Loschmidt’s 1.83 × 10¹⁸ molecules/cm³ by Than’s 22,330 cm³/gram-molecular weight. Hence, Avogadro is the originator of the ideas of the mole and the number 6.022 × 10²³ mol^?1, Horstmann first introduced the mole concept into science/chemistry, and Loschmidt and Than are the scientists who first calculated Avogadro’s number. However, in the science research literature, it is widely expressed that the mole concept was first introduced into chemistry by Ostwald in 1900 and that Avogadro’s number was first calculated by Jean Baptiste Perrin in 1908. As a result, in this study, it is particularly emphasised that Horstmann first introduced the mole concept into science/chemistry and the first value of Avogadro’s number in the history of science was 4.09 × 10²² molecules/gram-molecular weight and Loschmidt and Than together first calculated this number.     

Redox and photoisomerization switching of the second-order optical nonlinearity of a tetrathiafulvalene derivative of spiropyran across five states: a DFT study

Second-order nonlinear optical properties of a tetrathiafulvalene (TTF) derivative of spiropyran have been studied based on density functional theory (DFT) combined with the finite field (FF) calculations. Our DFT-FF calculations confirm a switching behavior of the static first hyperpolarizability caused by the redox and photochromic reaction. The photochromic reaction generates spiropyran-merocyanine conversion by reversible cleavage of the C-O bond, which is relative to the close- and open-ring forms 1-c and 1-o. The open-ring form 1-o displays the large static first hyperpolarizability relative to its close-ring form 1-c according to our DFT-FF calculations with three functionals. The electronic structure analysis and spin unrestricted calculations show that the redox processes significantly affect the geometrical structure of the TTF unit, and thus enhance the static first hyperpolarizabilities. The one-electron-oxidized species having good planar structure of the TTF unit are ~30 and ~200 times as large as that of the neutral compounds 1-c and 1-o, respectively. But the difference in the static first hyperpolarizability between one- and two-electron-oxidized states of spiropyran species is not substantial according to our DFT-FF calculations, and the spiropyran-merocyanine conversion of two-electron-oxidized species does not largely affect their static first hyperpolarizability. On the basis of the large change in the static first hyperpolarizability, our DFT-FF calculations support a five-state switching of the static first hyperpolarizability based on the redox and photoisomerization.     

Micellar Catalysis of Composite Reactions II. The Effect of CTAB Micelles on the Alkaline Fading of Malachite Green

The alkaline fading of malachite green, which is interpreted as parallel first order and second order reactions, has been studied in cetyltrimethylammonium bromide (CTAB) micellar solution at 25°C using spectrophotometry. A micellar catalytic model is proposed in this paper for constant concentration of hydroxideion. For this model, the first order and the second order rate constants in CTAB micellar phase,k_1m and k_2m have been obtained.

The experimental results indicate that the first order reaction of malachite green cation with water is catalysed by CTAB micelles while the second order reaction of malachite green cation with hydroxide ion is inhibited by CTAB micelles. The first order rate constant in CTAB micellar phase, k_1m , is 210 times of that in the bulk phase, but the second order rate constant in CTAB micellar phase, k_2m , is 0. 166 time of that in the bulk phase. The results are interpreted mostly in relation to the micellar micropolarity and electrostatic interaction. @Keywords: Micelle, Micellar catalysis, Parallel first order and seond order reactions, Malachite green     

Study on Separation Method of Overlapped Peaks in Differential Thermal Analysis with Computer Simulation

With the computer simulations, it has been found that in Differential Thermal Analysis (DTA) the overlapped peaks do not satisfy the linear overlapping principle, and the relationship between the overlapped peaks is rather complex that is a function of sample thermal conductivity, specific heat, quantity and latent heats, etc. If the first point where the two peaks begin to overlap is at the posterior half of the first peak curve and the two overlapped peaks can be identified by two different peaks, from the curve of overlapped peaks we can know that the temperature corresponding to the first point deviating from the sample's first phase change curve is the sample's second phase change temperature. This revised version was published online in August 2006 with corrections to the Cover Date.     

A first principles molecular dynamics study of lithium atom solvation in binary liquid mixture of water and ammonia: structural, electronic, and dynamical properties

The preferential solvation of solutes in mixed solvent systems is an interesting phenomenon that plays important roles in solubility and kinetics. In the present study, solvation of a lithium atom in aqueous ammonia solution has been investigated from first principles molecular dynamics simulations. Solvation of alkali metal atoms, like lithium, in aqueous and ammonia media is particularly interesting because the alkali metal atoms release their valence electrons in these media so as to produce solvated electrons and metal counterions. In the present work, first principles simulations are performed employing the Car-Parrinello molecular dynamics method. Spontaneous ionization of the Li atom is found to occur in the mixed solvent system. From the radial distribution functions, it is found that the Li(+) ion is preferentially solvated by water and the coordination number is mostly four in its first solvation shell and exchange of water molecules between the first and second solvation shells is essentially negligible in the time scale of our simulations. The Li(+) ion and the unbound electron are well separated and screened by the polar solvent molecules. Also the unbound electron is primarily captured by the hydrogens of water molecules. The diffusion rates of Li(+) ion and water molecules in its first solvation shell are found to be rather slow. In the bulk phase, the diffusion of water is found to be slower than that of ammonia molecules because of strong ammonia-water hydrogen bonds that participate in solvating ammonia molecules in the mixture. The ratio of first and second rank orientational correlation functions deviate from 3, which suggests a deviation from the ideal Debye-type orientational diffusion. It is found that the hydrogen bond lifetimes of ammonia-ammonia pairs is very short. However, ammonia-water H-bonds are found to be quite strong when ammonia acts as an acceptor and these hydrogen bonds are found to live longer than even water-water hydrogen bonds.     

Application of internal standard for derivative-spectrophotometric determination of azinphos-methyl in commercial formulations

The use of an internal standard is proposed in this work for first derivative spectrophotometric determination of azinphos in formulations. Generally, the spectrophotometric procedure is simpler and less expensive than chromatographic techniques recommended for the analysis of pesticides. However, while determining the pesticide in commercial formulations the, many-fold dilution required for such sensitive detection is a serious source of analytical error. It is known that an internal standard (IS), if properly chosen, can help eliminate this type of problem. A mixture of acetophenone (used as an IS in the high performance liquid chromatography (HPLC) procedure) and the blue dye Erioglaucine (A) was applied for the determination of azinphos-methyl in commercial formulations. To ensure the best conditions for the zero-crossing technique, the composition of the mixture was optimized to obtain the zero value of the first derivative absorbance of the IS at a minimum of the azinphos-methyl first derivative absorbance. Also, at the maximum of the first derivative spectrum of the IS, the differential absorption signal of the analyte was negligible. Analytical characteristics for the first derivative spectrophotometric procedure proposed were evaluated (r(2) = 0.9998, detection limit = 0.043 mg, quantification limit = 0.143 mg) and the analytical results obtained (35.02 +/- 0.20% of azinphos-methyl in the formulation) were in good agreement with the results obtained using the official HPLC method (35.44 +/- 0.32%).     

Many-photon dynamics of photobleaching

A detailed dynamical theory of photobleaching by periodical sequences of laser pulses is presented. The theory is used for interpretation of recent experiments with pyrylium salts. Our simulations are based on first-principles simulations of photoabsorption cross-sections and on empirical rate constants. Two competitive channels of photobleaching, namely, photobleaching from the lowest excited singlet and triplet states and from higher excited states, are found to explain different intensity dependences of the photobleaching rates in different samples. The process includes two-photon excitation from the ground state to the first or second excited singlet states and one-photon excitation from the first singlet or triplet states to higher excited states. The fluorescence follows double-exponential dynamics with two characteristic times. The first and the shorter one is the equilibrium settling time between the ground and the lowest triplet states. The second characteristic time, the time of photobleaching, is responsible for the long-term dynamics. The effective rate of photobleaching from the first excited singlet and lowest triplet states depends differently on the irradiance in comparison with the photobleaching in higher states. The first channel is characterized by a quadratic intensity dependence in contrast to the second channel that shows a cubic dependence. The competition between these photobleaching channels is very sensitive to the rate constants as well as to the repetition rate, the pulse duration, and the peak intensity. The double-exponential decay of the fluorescence is explained by the spatial inhomogeneity of the light beam. The findings in this work are discussed in terms of the possibility of using many-photon-induced photobleaching for new three-dimensional read-write devices.     

Beginnings of chemical science in Russia

The genesis and advancement of chemistry in Russia is tracked during the 18th century marked by founding the Russian Academy of Sciences. The role of M.V. Lomonosov and other first Russian chemists is characterized in formation of basic concepts of chemical science. The creation of the first Russian scientific chemical laboratory and its achievements are described.