Chlorophosphonation of η-alkanenitrile having C1C6 alkyl chain was carried out at the condition of the reactant ratio 1 : 5 of the nitrile to PCl3, in oxygen gas flow rate of 200ml/min, at -150°C, for 3hrs. The distributions of the product isomers were determined by GLC using Ucon LB 550X column, 3m×3mmφ, with nitrogen gas carrier. The addition product (RCCl=NPOCl2) was also obtained. The relative reactivities of the C-H bond of the alkanenitrile (RC≡N) to the terminal methyl were as follows. _??_* These values are expressed as relative yield to the yields of the products, substituted on the terminal methyl group.
In previous paper, the authors reported that, one exothermic peak was observed in the DTA curves of monolaurin and monomyristin by quenced sample, but such a phenomenon was not observed in monopalmitin and monostearin. In the present work, structure of this exothermic peak was elucidated by DSC and dilatometry using monomyristin. Examinations were also made on the relationship between free energy and temperature in polymorphism by determination of thermodynamic data from DSC. 1) Exothermic phenomenon in DSC is determined apparently by the competitive action of the transition rate from α-type or its fused state to β'-type and melting rate to α-type. Therefore, contraction of the specific volume and exothermic peak appear when heating rate is slow. 2) Correlation among the melting point, melting enthalpy (ΔH), and melting entropy (ΔSm) decreases in the order of β>α>sub-α type, and the melting point is proportional to ΔH andΔSm. 3) Specific heat decreases in the order of α<sub-α>β ptype, and this showed the same tendency as well with the order of specific volume of each crystal system. 4) Relationship between free energy of polymorphism and temperature as indicated in Fig.-5, shows that sub-α type is more stable than α-type in temperature ranges below 36°C, and it was found that transition in this temperature range proceeds to β' and β type without passing through α-type.
Effects of nonionic polymers on deposition rate of carbon black particles in nonaqueous solution were investigated in relation to those molecular weights. Polyethylene glycols and polypropylene glycols were used as materials. Depositions of two kinds of carbon black particles, hydrophilic (treated with damp ozone) and hydrophobic (untreated), on wool or cotton fabrics were examined in tetrachloroethylene solution of the polymer. The effects of polyethylene glycols on deposition rate of hydrophilic carbon black particles were observed markedly in comparison to hydrophobic ones. In polypropylene glycols, its effects were obvious in hydrophobic carbon black. The deposition rate decreased, as molecular weight of polymer increased. On the other hand, stability of carbon black suspension in the nonaqueous solution decreased by addition of polymer. These results will be explained as follows; it seems that the effects of polymer on deposition rate of carbon black in nonaqueous solution are attributed to increase in the affinity of carbon black to solvent, by adsorbing the polymers on the surface of carbon black particles.
Purposeing for establishing a standard method for the gas chromatographic determination of fatty acid composition, collaborative study team has carried out a replicate analysis of specified samples by using gas chromatographs with flame ionization detectors, and examined the entire set of the experimental data by a statistical method. In the collaborative studies, standard mixtures containing five fatty acid methyl esters (C12 : 0, C14 : 0, C16 : 0, C18 : 0 and trans-C18 : 1) were used as samples for analyses. Through three times of the collaborative studies, the conclusion obtained was as follows : (1) The correction factors which showed a certain regularity for the analyses of four samples were observed in the results obtained by sixty percent of all laboratories. The deviations and interlaboratory scattering of these results could be reduced considerably by applying the correction. factors. (2) For the determination of the correction factors, it is desirable to analyse known mixture having composition similar to that of the unknown sample using the same instrument under the same operating conditions as those for analysis of the unknown. (3) By injecting constant amount of sample, intrrlaboratory scattering was decreased while interlaboratory scattering was not decreased. From this collaborative study it is recommended that a 0.5 to 1.0μl of 20% solution is to be injected.
Collaborative analyses were carried out to examine the effect of application of the correction factors on the determination of fatty acid composition by gas chromatograph with thermal conductivity detector. The appropriate use of the correction factors gave a good result, that is, the corrected value approached closely to the known values and the interlaboratory scattering was considerably decreased. It was observed that the correction factor was affected by the operating conditions and the fatty acid composition of the reference mixture as well as by the number of carbon atoms in the methyl ester. Accordingly, for the precise determination it is recommended to apply the correction factors which have been determined not only by analysing a reference mixture having a similar composition to that of an unknown but by using the same instrument under the same operating conditions as those for the analysis of the unknown.