Substituent effects on the addition of alcohols and anilines to organic isothiocyanates

The addition reactions of alcohols, ROH (R = CH3, C2H5 n-C3H7, i-C3H7 and t-C4H9), to p-bromophenylisothiocyanate show that the rates decrease in the order, CH3OH> C2H5OH> n-C3H7OH> i-C3H7OH> t-C4H9OH, although the basicities of the alcohols vary in the reverse order. The results indicate the greater importance of steric factors as compared with polar factors. Evidence is also presented for the formation of a complex between the isothiocyanate and the alcohol in the first stage of the addition reaction. In the addition of aniline to substituted phenylisothiocyanates the rate data give a satisfactory linear correlation with Hammett σ constants and the results clearly show that electron-withdrawing groups favour the addition reaction. The addition of aniline to alkyl isothiocyanates have been studied in order to find out the nature of alkyl group interaction in these derivatives. Kinetic studies on the addition of substituted anilines to phenylisothiocyanate show that the rate of reaction increases with the electron-donating ability of the substituents on the aniline as also the basicity of the aniline.

Cerimetry in non-aqueous media - Oxidation of oxalic acid through the intermediate formation of ceric oxalate

It was found that ceric oxalate is an intermediate product in the oxidation of oxalic acid by ammonium hexanitrato cerate in solvents such as acetonitrile, and a mixture of acetonitrile and glacial acetic acid. Conditions for the formation of ceric oxalate and its decomposition into carbon dioxide and cerous oxalate have been studied. An analytical method for the estimation of oxalic acid in non-aqueous media has been evolved based on this reaction.

Why Do Russians Support Censorship of the Media?

This article analyses support for censorship in Russia as part of the democratization process. Censorship has been an important part of Russian history and it was strengthened during the Soviet era. After the collapse of the Soviet system formal censorship was banned even though the reality has been different. Therefore it is not strange that many Russians would like to limit the freedom of the media and to censor certain topics. The views of Russians on censorship have been studied on the basis of a survey carried out in 2007. According to the results, three different dimensions of censorship were found. These dimensions include moral censorship, political censorship, and censorship of religious materials. Support for these dimensions varies on the basis of socio-demographic characteristics and media use. The article concludes that many Russians reject new phenomena, while support for the censorship of political criticism is not as high, but political censorship seems to enjoy more support among elites than among the common people.

Reciprocity relation in scattering by media subjected to an external magnetic field

Krishnan's reciprocity theorem in colloid optics, ρ{variant}u=1+l/ρ{variant}h/1+1/ρ{variant}v is generalised for the case when the scattering medium is subjected to an external orienting field. It is shown theoretically that a general relation of the type IBA=I′AB results in this case, where IBA is the intensity of the component of the scattered light having its electric vector inclined at an angle B to the vertical with the incident light polarised at an angle A to the vertical, the external field direction being parallel to the incident beam. I′AB is the corresponding intensity with the magnetic field parallel of the scattered ray. Experimental verification of the above generalisation is also given.

Stereoselectivity in the addition of hydrogen chloride to cyclohex-1-enecarbonitrile: Possible role of chlorine lone pair-nitrile π-orbital pseudoallylic A1, 3 interaction

The (overall trans) addition of hydrogen chloride to cyclohex-1- enecarbonitrile in anhydrous alcoholic media proceeds to give cis-2-chlorocyclohexanecarboxylate (together with some cis-2- chlorocyclohexanecarboxamide): no corresponding products with the trans-configuration are detectable. In anhydrous ether the addition proceeds to give a single isomer, presumably cis-, of 2-chlorocyclohexanecarbonitrile, indicating that the configuration of the products may not be equilibrium-controlled in alcoholic media. An examination of the steric factors indicates that the transition state for protonation of the presumed intermediate, 2-chlorocyclohexylidenemethylideneimine, leading to cis-product is favoured if interaction between the lateral π-orbital of the C-N double bond and the lone-pairs on the chlorine atom at the 2-position is large. Consideration of interactions in the transition states meets Zimmerman's criticism that invoking A1, 3 interaction existing in ground states to explain product configuration takes insufficient account of the Curtin-Hammett principle.

Disjunct eddy covariance measurements of volatile organic compound fluxes using proton transfer reaction mass spectrometry

Volatile organic compounds (VOCs) are emitted into the atmosphere from natural and anthropogenic sources, vegetation being the dominant source on a global scale. Some of these reactive compounds are deemed major contributors or inhibitors to aerosol particle formation and growth, thus making VOC measurements essential for current climate change research. This thesis discusses ecosystem scale VOC fluxes measured above a boreal Scots pine dominated forest in southern Finland. The flux measurements were performed using the micrometeorological disjunct eddy covariance (DEC) method combined with proton transfer reaction mass spectrometry (PTR-MS), which is an online technique for measuring VOC concentrations. The measurement, calibration, and calculation procedures developed in this work proved to be well suited to long-term VOC concentration and flux measurements with PTR-MS. A new averaging approach based on running averaged covariance functions improved the determination of the lag time between wind and concentration measurements, which is a common challenge in DEC when measuring fluxes near the detection limit. The ecosystem scale emissions of methanol, acetaldehyde, and acetone were substantial. These three oxygenated VOCs made up about half of the total emissions, with the rest comprised of monoterpenes. Contrary to the traditional assumption that monoterpene emissions from Scots pine originate mainly as evaporation from specialized storage pools, the DEC measurements indicated a significant contribution from de novo biosynthesis to the ecosystem scale monoterpene emissions. This thesis offers practical guidelines for long-term DEC measurements with PTR-MS. In particular, the new averaging approach to the lag time determination seems useful in the automation of DEC flux calculations. Seasonal variation in the monoterpene biosynthesis and the detailed structure of a revised hybrid algorithm, describing both de novo and pool emissions, should be determined in further studies to improve biological realism in the modelling of monoterpene emissions from Scots pine forests. The increasing number of DEC measurements of oxygenated VOCs will probably enable better estimates of the role of these compounds in plant physiology and tropospheric chemistry. Keywords: disjunct eddy covariance, lag time determination, long-term flux measurements, proton transfer reaction mass spectrometry, Scots pine forests, volatile organic compounds

Social Media as a Form of Organizational Knowledge Sharing

This study investigates the role of social media as a form of organizational knowledge sharing. Social media is investigated in terms of the Web 2.0 technologies that organizations provide their employees as tools of internal communication. This study is anchored in the theoretical understanding of social media as technologies which enable both knowledge collection and knowledge donation. This study investigates the factors influencing employees’ use of social media in their working environment. The study presents the multidisciplinary research tradition concerning knowledge sharing. Social media is analyzed especially in relation to internal communication and knowledge sharing. Based on previous studies, it is assumed that personal, organizational, and technological factors influence employees’ use of social media in their working environment. The research represents a case study focusing on the employees of the Finnish company Wärtsilä. Wärtsilä represents an eligible case organization for this study given that it puts in use several Web 2.0 tools in its intranet. The research is based on quantitative methods. In total 343 answers were obtained with the aid of an online survey which was available in Wärtsilä’s intranet. The associations between the variables are analyzed with the aid of correlations. Finally, with the aid of multiple linear regression analysis the causality between the assumed factors and the use of social media is tested. The analysis demonstrates that personal, organizational and technological factors influence the respondents’ use of social media. As strong predictive variables emerge the benefits that respondents expect to receive from using social media and respondents’ experience in using Web 2.0 in their private lives. Also organizational factors such as managers’ and colleagues’ activeness and organizational guidelines for using social media form a causal relationship with the use of social media. In addition, respondents’ understanding of their responsibilities affects their use of social media. The more social media is considered as a part of individual responsibilities, the more frequently social media is used. Finally, technological factors must be recognized. The more user-friendly social media tools are considered and the better technical skills respondents have, the more frequently social media is used in the working environment. The central references in relation to knowledge sharing include Chun Wei Choo’s (2006) work Knowing Organization, Ikujiro Nonaka and Hirotaka Takeuchi’s (1995) work The Knowledge Creating Company and Linda Argote’s (1999) work Organizational Learning.

Cerimetry in nonaqueous media - Oxidation of ascorbic acid

The reaction between ascorbic acid and ammonium hexa nitrato cerate was studied potentiometrically in the mixed solvent glacial acetic acid acetonitrile medium. It was found that one mole of ascorbic acid consumes four equivalents of cerate in non-aqueous medium. This reaction can be made use of to estimate potentiometrically ascorbic acid with ammonium nitrato cerate in non-aqueous media, using either glass or antimony as reference electrode and platinum as indicator electrode.

The Raman spectra of organic compounds -Part I. Methyl, ethyl, n-propyl and n-butyl alcohols

The Raman spectra of methyl alcohol, ethyl alcohol, n-propyl alcohol and n-butyl alcohol have been recorded using λ 2537 excitation. 35, 49, 45 and 51 Raman lines respectively have been identified in the spectra of these alcohols, in addition to the rotational 'wings'. In each case, a large number of additional lines have been recorded. The existence of Raman lines with frequency shifts greater than 3800 cm.-1, first reported by Bolla in the spectrum of ethyl alcohol, has been confirmed. Similar high-frequency shift Raman lines have also been recorded in the spectrum of methyl alcohol. They have been assigned as combinations. Proper assignments have been given for the prominent Raman lines appearing in the spectra of these alcohols.

E-learning in a rural context: Alternative media and contemporary applications

This report has been written as part of the E-ruralnet –project that addresses e-learning as a means for enhancing lifelong learning opportunities in rural areas, with emphasis on SMEs, micro-enterprises, self-employed and persons seeking employment. E-ruralnet is a European network project part-funded by the European Commission in the context of the Lifelong Learning Programme, Transversal projects-ICT. This report aims to address two issues identified as requiring attention in the previous Observatory study: firstly, access to e-learning for rural areas that have not adequate ICT infrastructure; and secondly new learning approaches introduced through new interactive ICT tools such as web 2.0., wikis, podcasts etc. The possibility of using alternative technology in addition to computers is examined (mobile telephones, DVDs) as well as new approaches to learning (simulation, serious games). The first part of the report examines existing literature on e-learning and what e-learning is all about. Institutional users, learners and instructors/teachers are all looked at separately. We then turn to the implementation of e-learning from the organizational point of view and focus on quality issues related to e-learning. The report includes a separate chapter or e-learning from the rural perspective since most of Europe is geographically speaking rural and the population in those areas is that which could most benefit from the possibilities introduced by the e-learning development. The section titled “Alternative media”, in accordance with the project terminology, looks at standalone technology that is of particular use to rural areas without proper internet connection. It also evaluates the use of new tools and media in e-learning and takes a look at m-learning. Finally, the use of games, serious games and simulations in learning is considered. Practical examples and cases are displayed in a box to facilitate pleasant reading.