A G. C./M. S. study of the reaction and decomposition products of pentafluorophenyl-grignard and lithium reagents

Decomposition and side reactions of, and the synthetic use of, pentafluorophenylmagnesium bromide and pentafluorophenyllithium have been investigated using G,C9/M.S, techniques• Their reactions with reagents such as CgF^X (X - H, F, CI, Br, 1), C6F4X2 (X - H, CI)f C6F3C13, C6H6. (CgX5)3P (X = H, F), (C6X5)3P=0 (X = H, F), (CgX5)Si (CH3)3 (X = H, F) and (CH0K SiCl , n = 1,2, in ether or ether/n-hexane were studied• In addition to the principal reaction of synthetic use, namely the replacement of a halogen by a pentafluorophenyl group, two types of side reactions were observed* These were (i) intermolecular loss of LiF via a nucleophilic substitution, and (ii) intramolecular loss of LiF, followed by the addition of either inorganic salts such as lithium or magnesium halides, or organometal compounds such as organolithium or organo-Grigaard* G.C«/M.S. techniques were routinely employed to study complicated reaction mixtures. Although mass spectrometry alone has disadvantages for the identification of isomers, deduction of the most probable pathway often helps overcome this problem.

The nature experiences of wilderness recreation leaders : throwing a stone

Through this descriptive exploratory study, the ways that wilderness recreation leaders experience nature are illuminated, deconstructing the assumed environmental benefits of and practices used in outdoor recreation (Haluza-Delay, 2001). This study also offers a foundation for advancing an environmental ethic among wilderness recreation leaders, participants, and organizations. With the continued degradation of and threats to natural environments, and the rising popularity of outdoor recreation participation, the outdoor recreation professional can be a leader in promoting human reconnections to the Earth (Henderson, 1999). Leaders of outdoor recreation experiences play an important role in encouraging these revived relationships to natural settings and can contribute to the necessary environmental consciousness shift needed within Western society (Hanna, 1995; Jordan, 1996). The purpose of this research was to describe the lived-experience in nature of wilderness recreation leaders. Specifically, a phenomenological method of inquiry was used to describe the meaning of nature, the connections and relationships to nature, and the behaviours and emotions experienced in nature by a group of wilderness canoe trip leaders employed by a residential summer camp. In addition to the implications of this research, achieving this outcome provides a rich descriptive understanding of wilderness leaders' experiences—a basis from which to extend future research endeavours and programmatic practices that promote effective environmental outcomes of outdoor recreation participation. Each of the five study participants was employed in the summer of 2003 by an Ontario residential summer camp organization that sponsors extended wilderness river canoe trips for youth. Two in-depth and semi-structured interviews were performed with each participant, asking them to reflect on the canoe trip that they led for the summer camp organization during 2003. Phenomenological data was analyzed according to Colaizzi's (1978) thematic analysis process. Consistent with van Manen's (1997) emphasis on phenomenological writing, the final result presents the essence of the nature experiences of wilderness recreation leaders in the format of a narrative description. This narrative piece is the culmination of this research effort. Throughout the journey, however, various foundations within the outdoor recreation field, such as minimum impact principles, environmentally responsible behaviours, anthropocentric and ecocentric worldviews, and effective leadership are deconstructed and discussed.

The essence of a tacit intersection : a heuristic inquiry into nature-based leisure and personal transformation

There are a considerable number of programs and agencies that count on the existence of a unique relationship between nature and human development. In addition, there are significant bodies of literature dedicated to understanding developmentally focused nature-based experiences. This research project was designed to flirther the understanding of this phenomenon. Consequently, the purpose of this research endeavour was to discover the essence ofthe intersection ofpersonal transformation and nature-based leisure, culminating in a rich and detailed account of this otherwise tacit phenomenon. As such, this research built on the assumption of this beneficial intersection of nature and personal transformation and contributes to the understanding ofhow this context is supporting or generating of selfactualization and positive development. Heuristic methods were employed because heuristics is concerned with the quality and essence of an experience, not causal relationships (Moustakas, 1990). Heuristic inquiry begins with the primary researcher and her personal experience and knowledge of the phenomenon. This study also involved four other coresearchers who had also experienced this phenomenon intensely. Co-researchers were found through purposeful and snowball sampling. Rich narrative descriptions of their experiences were gathered through in-depth, semi-structured interviews, and artifact elicitation was employed as a means to get at co-researchers' tacit knowledge. Each coresearcher was interviewed twice (the first interview focused on personal transformation, the second on nature) for approximately four and a half hours in total. Transcripts were read repeatedly to discern patterns that emerged from the study of the narratives and were coded accordingly. Individual narratives were consolidated to create a composite narrative of the experience. Finally, a creative synthesis was developed to represent the essence of this tacit experience. In conclusion the essence of the intersection of nature-based leisure and personal transformation was found to lie in the convergence of the lived experience of authenticity. The physical environment of nature was perceived and experienced to be a space and context of authenticity, leisure experiences were experienced as an engagement of authenticity, and individuals themselves encountered a true or authentic self that emanated from within. The implications of these findings are many, offering suggestions, considerations and implications from reconsidered approaches to environmental education to support for selfdirected human development.

A study of the thermal decomposition of allyl t-butyl peroxide and 3-hydroperoxy-1-propene (allyl hydroperoxide) in toluene /|nby Krishnankutty Nair V. G. -- 260 St. Catharines [Ont. : s. n.],

Kinetics and product studies of the decompositions of allyl-t-butyl peroxide and 3-hydroperoxy- l-propene (allyl hydroperoxide ) in tolune were investigated. Decompositions of allyl-t-butyl peroxide in toluene at 130-1600 followed first order kinetics with an activation energy of 32.8 K.cals/mol and a log A factor of 13.65. The rates of decomposition were lowered in presence of the radical trap~methyl styrene. By the radical trap method, the induced decomposition at 1300 is shown to be 12.5%. From the yield of 4-phenyl-l,2- epoxy butane the major path of induced decomposition is shown to be via an addition mechanism. On the other hand, di-t-butYl peroxyoxalate induced decomposition of this peroxide at 600 proceeded by an abstraction mechanism. Induced decomposition of peroxides and hydroperoxides containing the allyl system is proposed to occur mainly through an addition mechanism at these higher temperatures. Allyl hydroperoxide in toluene at 165-1850 decomposes following 3/2 order kinetics with an Ea of 30.2 K.cals per mole and log A of 10.6. Enormous production of radicals through chain branching may explain these relatively low values of E and log A. The complexity of the reaction is indicated a by the formation of various products of the decomposition. A study of the radical attack of the hydro peroxide at lower temperatures is suggested as a further work to throw more light on the nature of decomposition of this hydroperoxide.