Photoelectrochemical properties of sol–gel obtained titanium oxide

The photoelectrochemical properties of a sol–gel prepared titanium oxide coating applied onto a Ti substrate were investigated. The oxide coating was formed from an inorganic sol thermally treated in air at 350 °C. The coating consisted of agglomerates of narrow size distribution around 100 nm. The photoelectrochemical characteristics were evaluated by investigating the changes in the open circuit potential, current transients and impedance characteristics of a Ti/TiO2 electrode upon illumination by UV light in H2SO4 solution and in the oxidation of benzyl alcohol. The electrode was found to be active for photoelectrochemical reactions in the investigated solutions

Gas chromatographic retention indices for N-substituted amino s-triazines on capillary columns. Part V. Temperature dependence of the retention index

The temperature dependence of the retention index was studied for N-substituted amino s-triazines on DB-1, DB-5 and DB-WAX capillary columns within the temperature range 190230ºC. Two linear equations with the column temperature and its reciprocal as variables were studied. The first one shows a slightly better precision for 2,4-bis(alkylamino)-6-chloro-s-triazines and 2-alkylamino-4,6-dichloro-s-triazines, while the second one shows a better precision for 2,4-bis(cycloalkylamino)-6-chloro-s-triazines

The kinetics of the reaction of 6-substituted nicotinic acids and some p-substituted benzoic acids with diazodiphenylmethane in various alcohols

Rate constants have been determined for the reactions of diazodiphenylmethane with a number of 6-substituted nicotinic acids and p-substituted benzoic acids in twelve alcohols. A comparative study was used to evaluate and compare the Hammett r values and solvent effects. Multiple correlations of the log k values for the reactions of 6-substituted nicotinic acids and p-substituted benzoic acids in 12 alcohols with groups of suitable solvent parameters are very successful. The transmission of electronic effects through the pyridine ring system in compared with that in benzene

Kinetics of the reaction of 5-substituted orotic acids with diazodiphenylmethane

Rate konstants for the reaction of eight 5-substituted orotic acids with diazodiphenylmethane (DDM) in dimethylformamide (DMF) were determined at 30 ºC by the known spectrophotometric method. The determined rate constants were correlated with the equations: log k2 = as1 + bsR + h log k2 = as1 + bsR + yn + h to detect the presence and investigate the influence of both electrical and steric substituent effects. The obtained results show that the electrical effect (the localized field and delocalized resonance) is predominant and that the steric effect, althought present, is releatively small in this reaction

Investigations of the reactivity of pyridine carboxylic acids with diazodiphenylmethane in protic and aprotic solvents.

Rate constants for the reaction of diazodiphenylmethane with isomeric pyridine carboxylic acids were determined in chosen protic and aprotic solvents at 30 °C, using the well known UV spectrophotometric method. The values of the rate constants of the investigated acids in protic solvents were higher than those in aprotic solvents. The second order rate constants were correlated with solvent parameters using the Kamlet-Taft solvatochromic equation in the form: log k = log k0 + sp* + aa + bb . The correlation of the obtained kinetic data were performed by means of multiple linear regression analysis taking appropriate solvent parameters. The signs of the equation coefficients were in agreement with the postulated reaction mechanism. The mode of the influence of the solvent on the reaction rate in all the investigated acids are discussed on the basis of the correlation results

Investigation of the reactivity of 4-pyrimidinecarboxylic, 6-hydroxy-4-pyrimidinecarboxylic and 5-hydroxyorotic acids with diazodiphenylmethane in various alcohols. Part III

Rate constants for the reaction of diazodiphenylmethane (DDM) with 4-pyrimidinecarboxylic, 6-hydroxy-4-pyrimidinecarboxylic and 5-hydroxyorotic acids were determined in twelve protic solvents at 30 °C using the well known UV-spectrophotometric method. The second order rate contants for the examined acids were correlated using the appropriate solvent parameters by the equation log k = log k0 + af(e) + bs * + cngH were f(e) is the Kirkwood function of relative permittivity [(e–l)/(2e + 1 )], s * is the Taft polar constant for the alkyl group R in the alcohol ROH, and nyH is themumber of hydrogen atoms in the g-position in the alcohol. The results obtained for the investigated acids were compared with the corresponding results for benzoic, 2- and 3-hydroxybenzoic acids and the influence of the structure of the investigated acids on the reactivity in hydroxylic solvents is discussed. It was also possible to evaluate and distinguish the specific and non-specific solvent effects and their influence on the reaction rate

Substituent and structural effects on the kinetics of the reaction of N-(substituted phenylmethylene)-m- and -p-aminobenzoic acids with diazodiphenylmethane

The rate constants for the reaction of twenty-two N-(substituted phenyl methylene)-m- and -p-aminobenzoic acids with diazodiphenylmethane were determined in absolute ethanol at 30 °C. The effects of substituents on the reactivity of the investigated compounds were interpreted by correlation of the rate constants with LFER equations. The results of quantum mechanical calculations of the mole cular structure together with experimental results gave a better insight into the effects of structure on the transmission of electronic effects of the substituents. New σ constants for substituted benzylideneamino group were calculated

Infrared study of some 2-substituted-6-hydroxy-4-pyrimidine carboxylic acids. Correlation with MO-calculations

The IR spectra of a series of 2-substituted-6-hydroxy-4-pyrimidine carboxylic acids (substituent = OH, SH, CH3, CH3S and NH2) were studied from the aspect of the influence of the subsitutent on the polarizability of some bonds, keto-enol tautomerism and hydrogen bond formation. The spectra were taken using solids due to the low solubility of the acids. Theoretical calculations were done using the MNDO-AM1 semiempirical molecular-orbital method. The stabilities of various tautomers were calculated simulating the dielectric continuum using the COSMO facility of the MOPAC program package. Theoretical calculations were made for all the possible tautomers of the 2-substituted-6-hydroxy-4-pyrimidine carboxylic acids. For the most stable isomers, the vibrational spectra were calculated. For the majority of the compounds the most stable isomer was identified having the structure 2-Y-6-oxo-4-carboxy-3H-pyrimidine. Besides this structure, for the 2-amino-, and 2-methyl- derivatives the zwitterionic forms have very similar stability. The 2-hydroxy compound is most stable as the 2,6-dioxo-1H, 3H isomer. The calculated vibrations for the compounds with a single stable structure correlate very well with the experimental frequencies. For the 2-methyl- and 2-amino- compounds the correlation is considerably less satisfactory. The most probable reason for this deviation is the existence of two or more tautomets in equilibrium. The correlation of the measured frequencies and the pKa values of the acids, indicate that the same tautomers exist in the solid state and in the solution

Gas chromatograpic retention indices for N-substituted amino s-triazines on capillary columns. Part IV. Influence of column polarity on retention index

The retention index increment for the addition of a methylene group to the alkyl group of an analyte molecule is shown to be lower than 100 i.u. for N-substituted amino s-triazines. In temperature progammed gas chromatography, a linearly interpolated retention index I, determined from the linear regression equation, I = AZ + (GRF)z, with the number of atoms (Z) in the molecule as variable, was used to describe the retention of 25 N-substituted amino s-triazines, on DB-1, DB-5 and DB-WAX capillary columns, divided into five series according to the similarity of the alkyl groups in the particular series. In the above equation, A is the linear regression coefficient or the retention index increment per atom addition, Z the number of C, N and Cl atoms in the molecule, and (GRF)z the group retention factor or functionality constant for functional groups in the molecule, based on the number Z. It is possible to estimate the retention indices of an unknown member of the series from the Z, A and (GRF) values