Di-imide: Some Physical and Chemical Properties, and the Kinetics and Stoichiometry of the Gas-phase Decomposition

1973 ◽  
Vol 51 (21) ◽  
pp. 3605-3619 ◽  
Author(s):  
C. Willis ◽  
R. A. Back

Preparation of di-imide by passing hydrazine vapor through a microwave discharge yields mixtures with NH3 containing typically about 15% N2H2, estimated from the gases evolved on decomposition. The behavior of the mixture (which melts at −65 °C) on warming from −196 to −30 °C suggests a strong interaction between the components. Measurements of magnetic susceptibility and e.p.r. experiments showed that N2H2 is not strongly paramagnetic, which with other observations points to a singlet rather than a triplet ground-state.Di-imide can be vaporized efficiently, together with NH3, by rapid warming, and the vapor is surprisingly long-lived, with a typical half-life of several minutes at room temperature. The near-u.v. (3200–4400 Å) absorption spectrum of the vapor was photographed; it shows well-defined but diffuse bands, with εmax = 6(± 3) at 3450 Å.Di-imide decomposes at room temperature in two ways:[Formula: see text][Formula: see text]Formation of NH3 was not observed but cannot be ruled out. The decomposition of the vapor is complicated by a sizeable and variable decomposition that occurs rapidly during the vaporization. The stoichiometry of this and the vapor-phase decomposition depends on total pressure and di-imide concentration. The kinetics of the decomposition of the vapor were studied from 22 to 200 °C by following the disappearance of N2H2 by absorption of light at 3450 Å, or the formation of N2H4 by absorption at 2400 Å, and by mass spectrometry. The kinetics are complex and can be either first- or second-order, or mixed, depending on surface conditions. The effect of olefin additives on the decomposition was studied, and is also complex.Mechanisms for the decomposition are discussed, including the possible role of trans-cis isomerization. The relatively long lifetime found for di-imide in the gas phase suggests that it may be an important intermediate in many reactions of hydronitrogen systems.

The electron spin resonance method was employed to study the nature, concentration and kinetics of the disappearance under varying conditions of radicals produced in polyethylene by fast electron irradiation at 77°K. The predominant radical species at 77°K is the alkyl radical —CH 2 —ĊH—CH 2 —. On being warmed to room temperature it disappears rapidly, revealing a more stable un­identified radical. The kinetics of the decay at room temperature of both radicals was observed. Their stabilities were found to vary in polyethylene samples of differing physical and chemical properties. G values for these radicals are given. Comparison was made with spectra obtained under similar conditions with two pure paraffins and a pure olefin to evaluate the effect of crystallinity branching, molecular weight and unsaturation. In the olefin there is evidence for a build-up of allyl radicals due to the encounter of an alkyl radical with main chain unsaturation. This supports the view that alkyl radicals are mobile, and cross-linking occurs when two such radicals meet.


2004 ◽  
Vol 49 (3) ◽  
pp. 165-172 ◽  
Author(s):  
M. Yazgan ◽  
A. Tanik

The study covers the investigation of pesticides in terms of consumption, toxicological classification and various intrinsic physical and chemical properties like DT50, KOC, GUS, solubility that describe the important mechanisms prevailing in soil, namely persistence and mobility. These mechanisms help to estimate the transportation pathways of pesticides on soil till they reach the receiving water after being applied on land. Classification is done in three groups, those likely to appear in surface flow, those that appear in groundwater and those that present transient conditions. Such an approach that also takes into account toxicological levels and annual consumption values of pesticides will act as a tool to prepare the priority list of pesticides that need special care during their transportation. The fate of pesticides is a difficult task to solve, however, such a methodology, puts forth a rough estimate on their behavior in spite of uncertainties in many of the parameters describing mechanisms like persistence and mobility. The agricultural areas of two watersheds of Istanbul are selected as target areas to describe the approach, which is also checked with another approach estimating pesticide pollution potential that considers various other properties of pesticides. Almost similar findings are depicted with 85% proximity. The methodology presented in the paper illustrates and emphasizes the significant role of pesticide properties in determining their fate in soil after being applied.


Author(s):  
John Evans

The chemical properties of the volatile elements in groups 15 to 18 are outlined, showing how the the periodicicty of the properties of the elements shapes their chemistry. The manufacture of hydrogen and chlorine is described, showing how mercury-free methods have been developed for the latter. The effect of the formation of atmospheric CO2 on atmospheric oxygen content is explained in terms of dissolution in the oceans. Remediation of the exhaust gases from internal combustion engines by catalysts to remove CO2, NOx and carbonaceous particulates is explained. Options for carbon capture and storage by physical and chemical processes are evaluated, and examples provided of these processes in operation. Exploitation of the atmosphere for energy capture using wind turbines has been aided by the development of high performance magnets. The basis of these magnets and the role of rare earth elements is explained.


Author(s):  
Anastasia Filtschew ◽  
Pablo Beato ◽  
Søren Birk Rasmussen ◽  
Christian Hess

The role of platinum on the room temperature NOx storage mechanism and the NOx desorption behavior of ceria was investigated by combining online FT-IR gas-phase analysis with in situ Raman...


1970 ◽  
Vol 25 (11) ◽  
pp. 1772
Author(s):  
T.S.R Ao ◽  
A. Patil

Abstract It has been shown that in kinetically first order gas phase reactions occuring under electric discharge, such as the decomposition of N2O, the application, at various initial pressures, of the same multiple of the respective starting potential ensures that the reaction occurs at the same specific rate.


2020 ◽  
Vol 166 ◽  
pp. 06007
Author(s):  
Myroslav Sanytsky ◽  
Tetiana Kropyvnytska ◽  
Stanislav Fic ◽  
Hanna Ivashchyshyn

Sustainable development depends on a consistency of interests, social, ecological and economic, and that the interests are evaluated in a balanced manner. In order to reduce CO2 emissions, the conception of decreasing clinker factor and increasing the role of supplementary cementitious materials (SCMs) in the cementitious materials has high economical and environmental efficiency. The performance of clinkerefficient blended cements with supplementary cementitious materials were examined. The influence of superfine zeolite with increased surface energy on the physical and chemical properties of low-carbon blended cements is shown. Increasing the dispersion of cementitious materials contributes to the growth of their strength activity index due to compaction of cement matrix and pozzolanic reactions in unclincker part. In consequence of the early structure formation and the directed formation of the microstructure of the cement matrix is solving the problem of obtaining clinker-efficient concretes. Shown that low-carbon blended cements with high volume of SCMs are suitable, in principle, for producing structural concretes.


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