The chemical resonance structures of the excited states are assumed to correspond to the type of polarization in each state. This theory can explain the absorption energies as the difference in the empirical resonance energies between the ground and excited states by an application of Carter’s empirical equations. Imaginary charges are introduced to estimate the number of resonance structures, thus eliminating the influence of cross-linking atoms; the meaning of the resonance hybride corresponding to each levels is easily interpreted in correlation with Platt’s theory. As a result,, the individual excited state can be represented as a chemical resonance hybride consisting of a group of simple polarized structures; this theory may be said to be adequate from the view-point of absorption energies and of absorption intensities in relation to the direction of electric dipoles.
1. The resistivity of microcrystalline selenium doped with chlorine was changed by heat treatment. The results were in fairly good accord with the measurements obtained by Schweickert. Selenium doped with chlorine had the same characteristics as that doped with iodine or bromine. 2. The results of microscopic observation showed that the grain size became smaller with the higher chlorine concentration. This tendency was similar to that found in iodineor bromine-doped selenium. 3. The resistivity variation with temperatures below room temperature was affected by the heat treatment of the specimen. The effect was greater for the specimen free from chlorine. 4. Carrier concentrations were obtained from the measurement of capacity and also from the thermoelectric power. These two methods gave results which were in agreement with each other. The concentrations were shown to be increased at low temperatures.
1) The cationic copolymerization of styrene and p-bromostyrene in liquid sulfur dioxide using boron trifluoride etherate as a catalyst has been carried out; the monomer reactivity ratios (MRR) have been found to be r1=0.8 and r2=0.4. The MRR value was independent of the temperature and of the quantity of the catalyst in the copolymerization. 2) The effect of added solvents in liquid sulfur dioxide has also been examined. However, the MRR’s have been little affected by the added solvents, the rates of the copolymerization have largely been depressed, and the rates were not dependent on the dielectric constants of the added solvents, the rate in pure liquid sulfur dioxide being the fastest. 3) The same cationic copolymerization has been conducted in benzene, carbon tetrachloride, nitrobenzene and ethylene dichloride. The MRR’s were almost equal in all (r1=1.8 and r2=0.3).
Measurements have been made of the electrical conductivity and the viscosity of mixed solutions of sodium dodecyl sulfate (SDS) and dodecyl alcohol (DA). The addition of DA caused a lowering of the conductance, a phenomenon probably related to the formation of a complex composed of SDS and DA, but it did not essentially alter the form of the Λ−\sqrtc curves up to 0.3 mol. fraction of DA in SDS-DA. The Λ−\sqrtc curves of the mixed solution exhibit a break point which corresponds to a critical concentration of SDS, up to a 0.3 mol. fraction of DA in SDS-DA; the break point becomes obscure when the amount of DA present is larger than this value. The effect of the amount of DA on the critical concentration was not very large in this experiment. The variation of the conductance and viscosity with the temperature was measured on the solution of SDS with varying concentrations of DA. For the solution of SDS without DA, the product of the conductance and the viscosity is almost independent of the temperature, while for the mixed solutions the product is dependent on the temperature, especially in the case of the mixed solution containing a considerable amount of DA.
Tricyclohexylbutylsilane, tetracyclohexylsilane and tricyclohexylphenylsilane were prepared by hydrogenation of triphenylbutylsilane and phenyltricyclohexylsilane and partial hydrogenation of tetraphenylsilane, respectively. Preparation of tricyclohexylisopropylsilane and tricyclohexyl-t-butylsilane was unsuccessful due to failure of obtaining corresponding triphenyl derivatives. An attempt to obtain tricyclohexylcyclohexoxysilane by hydrogenating triphenylphenoxysilane was also unsuccessful. In preparation of highlysubstituted cyclohexylsilicon compounds, the steric factor is of less importance in the hydrogenation process, while it is very much enhanced in reactions with organolithium compounds.
Discrepancies among reported melting ponints for tetracyclohexylsilane and tricyclohexylbutylsilane were discussed. Tricyclohexylcyclohexoxysilane was obtained in 2∼5% yield in addition to tricyclohexylchlorosilane from the reaction of cyclohexyllithium with silicon tetrachloride. Petrov’s compound melting at 198°C is most likely to be tricyclohexylcyclohexoxysilane and not a stereoisomeric tetracyclohexylsilane. Tricyclohexylbutoxysilane, m. p. 133°C, was prepared by treating sodium butoxide with tricyclohexylchlorosilane, and it was pointed out that Petrov’s “tricyclohexylbutylsilane” is probably tricyclohexylbutoxysilane.
New complexes of salicylaldoxime (symbol: salmH2) and C-methyl-salicylaldoxime (symbol: Me-salmH2) with vanadium(V), [VO(OH)·(salmH)2] (A), [VO(O-Et)(salmH)2] (B), [VO·(OH)(Me-salmH)2] (C) and [V(OH)(Mesalm)2] (D) were prepared. A, B and C complexes were dark-colored, while the D complex was light-colored. The absorption spectra of A and C in dimethylformamide were determined. Based on the measurements of the visible, ultraviolet and infrared absorption spectra of these complexes, the following conclusions were drawn: 1) In benzene complex A has the trans structure, while in dimethylformamide it has the cis structure. 2) Complex C has the same properties as A. 3) The esterification of A does not cause any remarkable change in color. 4) The great difference between, the color of C and that of D comes from the difference in the donor atoms of the ligand. In the former the ligands are coordinated as N, O-chelates, and in the latter, as O, O-chelates.
A study of the effect of zinc chloride on the polymerization of vinyl acetate has been made. Zinc chloride can initiate the cationic polymerization of vinyl acetate at above room temperatures to yield the colored low-molecular weight polymer. However, in the low-temperature photopolymerization of vinyl acetate initiated by azobisisobutyronitrile, zinc chloride accelerates the radical polymerization and the colorless polymer which is insoluble in the monomer is obtained. Elementary analysis, infrared spectra and X-ray analyses show that the structure of this polymer after purification does not differ with that of ordinary poly-vinyl acetate and polyvinyl alcohol obtained through the hydrolysis of this polymer has no crystallinity superior to that of the ordinary sample.
3-(4′-Pentenyl)cyclopentene-1 (PCP) was prepared through the reaction of 1-pentenyl magnesium bromide and 3-chlorocyclopentene-1. An attempt was made for the polymerization and copolymerization of PCP. In the polymerizations by radical (azobisisobutyronitrile) and Ziegler [Al(i-Bu)3-TiCl4] initiators, a little brown methanol-soluble oil was obtained. By cationic initiator (BF3·OEt2), however, a trace of reddish brown polymer which did not dissolve in common organic solvents was formed. PCP was copolymerized with maleic anhydride by the use of a radical initiator. When the monomer mixture ratio of PCP to maleic anhydride was varied, no change was observed in the copolymer composition (the proportion of PCP to maleic anhydride being 1 to 2). In the infrared spectrum of the copolymer, the absorption bands of the vinyl type double bond and the unsaturated cyclopentene ring of PCP disappeared in the copolymer, so it was to be assumed that both double bonds participated in the copolymerization to form glassy gelled pale-yellow copolymer. These results indicate that an alternative copolymerization took place.
The optimum conditions for the chelatometry of calcium with EGTA have been deduced from the theoretical consideration of the equilibria involved. Some experimental results have been given on the chelatometry of calcium in the presence of magnesium using the Zn-EGTA-PAN system as an indicator. This proposed method seems to be better than earlier ones.
On the basis of observations on the induced decomposition of peroxides by radicals, it has been suggested that the interaction of the charge-transfer type, involving the highest occupied molecular orbital in an attacking radical and the 2pσu antibonding orbital around the oxygen to oxygen bond in a molecule of peroxide, contributes to a lowering of the activation energy of reaction. Possible extension of this idea to elucidation of the reactions of peroxides with other reagents has been pointed out.
On the phase transition of n-higher alcohols with odd carbon atoms from undecanol (C11) to heptatriacontanol (C37), thermal analyses and X-ray pattern measurements were made, with the following results: 1. Tridecanol (C13) shows an irreversible transition which appers only on cooling. A reversible transition sets in at pentadecanol (C15) and continues to the end member of the series (C37). 2. X-Ray pattern measurements indicated that, in the alcohols up to nonacosanol (C29), the transtition is β to α, while in the alcohols above C29 the transition is γ2 to α. 3. Presumably, the γ2 to α transition is gradual. 4. The properties of the α forms change gradually with an increase in the chain length. 5. The results of the present study and those of previous studies with the even series have been discussed from the configurations of the β and γ1 forms, as determined by X-ray structure analyses.
The intrinsic viscosities of sodium orthophosphates, pyrophosphate, tripolyphosphate and Graham salts of relatively low molecular weight (lower than 10300) were measured. The relation between the intrinsic viscosity at 25.5°C and the average molecular weight measured by the end group titration was [η]=6.9×10−4×M0.61 in a 0.035 N sodium bromide solution, and [η]=0.0348+0.112×10−4×M in a 0.07 N sodium bromide solution. Vanadium-containing Graham salts (sodium vanadate-phosphate copolymers) seemed to be hydrolyzed immediately by the dissolution. The intrinsic viscosity of the solution was much smaller than that of sodium polyphosphate of the corresponding degree of polymerization. The rate of the hydrolysis of branched sodium polyphosphate was proportional to the number of branchings, and the rate constant was 0.39 hr−1 at 25.5°C.