Anharmonic Helmholtz free energy to O(lambdaâ ´) in the non- leading term approximation /|nby Leslie Wilk. -- 260 St. Catharines, Ont. : [s. n.],

Expressions for the anharmonic Helmholtz free energy contributions up to o( f ) ,valid for all temperatures, have been obtained using perturbation theory for a c r ystal in which every atom is on a site of inversion symmetry. Numerical calculations have been carried out in the high temperature limit and in the non-leading term approximation for a monatomic facecentred cubic crystal with nearest neighbour c entralforce interactions. The numbers obtained were seen to vary by a s much as 47% from thos e obtai.ned in the leading term approximati.on,indicating that the latter approximati on is not in general very good. The convergence to oct) of the perturbation series in the high temperature limit appears satisfactory.

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.

Education, sport and myth in the community of Glengarry, Ontario : the athletic career of Roderick R. McLennan. 260 St. Catharines, Ont. : Faculty of Education, Brock University ;

This study examined how the athletic career of Roderick R. McLennan contributed to the popularization and subsequent development of Caledonian games in Ontario during the latter nineteenth century. Initially, the development of Caledonian games during the 1800s was examined to provide a contextual framework for McLennan's career. This investigation revealed that the games emerged from rural athletic events at pioneer working bees in the first quarter of the nineteenth century to regional sporting events by the mid-1800s, and finally into annual federated Caledonian games in 1870. Noteworthy primary source material for this chapter included the John MacGillivray Papers at the National Archives of Canada, the Scottish American Journal (NY) and the files retained by the Glengarry Sport Hall of Fame in Maxville, Ontario. Following the investigation of Caledonian games, McLennan's early athletic career was studied. Analysis of the Roderick and Farquhar McLennan Papers at the Archives of Ontario and the newspapers from the period revealed that McLennan rose to popularity in 1865 through a "Championship of the World" hammer throwing match in Cornwall and two "Starring Tours". The next chapter examined the height of McLennan's career through an investigation of the Roderick McLennan versus Donald Dinnie rivalry of the early .. n 1870s. It was detennined that the rivalry between McLennan and Dinnie, the champion athlete of Highland games in Scotland, was a popular attraction and had an impact on the Toronto and Montreal games of 1870 and the Toronto games of 1872. Finally, the athletic records established by McLennan during the 1860s and 1870s were investigated. These records were examined through the context of a media controversy over McLennan's feats that developed in the early 1880s between two newspapers. This controversy erupted between the Toronto Mail and the Spirit of the Times. Caledonian games in Canada have only been briefly examined and a thorough examination of prominent Canadian figures in this context has yet to be undertaken. This study unearths a prominent Canadian athlete of Scottish decent and details his involvement in the Caledonian games of nineteenth century Ontario.

Radiation-induced changes in the export of photoassimilated carbon /|nBarry Jess Shelp. -- 260 0 St. Catharines, [Ont. : s. n.],

Low levels of ionizing radiation induce two translocation responses in soybean: a reduction in photoassimilate export from leaves and a change in the distribution pattern of exported photoassimilate within the plant. In this investigation these responses have been further studied specifically to ascertain the site of radiation damage and to better understand the physiological responses observed. Experimentally the primary data was obtained from studies in which a mature trifoliate leaf of a young soybean plant (Glycine ~ L. cultivar Harosoy '63) is isolated in a closed transparent chamber and allowed to photoassimilate 14C02 for 15 minutes. This is followed by an additional 45 ~_il'1;ute period before the plant is sectl.o ne d an d 14 C-ra dl' oactl.v.l ty d eterml. ne d'l n a 11 parts. Such 14c data provides one with the magnitude and distribution pattern of translocation. Further analyses were conducted to determine the relative levels of the major photosynthetic products using the techniques of paper chromatography and autoradiography. Since differences between control and irradiated P 1 ants were not 0 b serve d l' n t h e par tl't"lo nlng 0 f 14 C between the 80% ethanol-soluble and -insoluble fractions 14 or in the relative amounts of C-products of photosynthesis, the reduction in export in irradiated plants is not likely due to reduced availability of translocatable materials. Data presented in this thesis shows that photoassimilate export was not affected by gamma radiation until a threshold dose between 2.0 and 3.0 krads was reached. It was also observed that radiation-induced damage to the export process was capable of recovery in a period of 1 to 2 hours provided high light intensity was supplied. In contrast, the distribution pattern was shown to be extremely radiosensitive with a low threshold dose between .25 and .49 krads. Although this process was also capable of recovery,lt" occurred much earlier and was followed by a secondary effect which lasted at least for the duration of the experiments. The data presented in this thesis is interpreted to suggest that the sites of radiation action for the two translocation responses are different. In regards to photoassimilate export, the site of action of ionizing radiation is the leaf, quite possibly the process of photophosphorylation which may provide energy directly for phloem loading and for membrane integrity of the phloem tissue* In regards to the pattern of distribution of exported photoassimilate, the site is likely the apical sink, possibly the result of changes of levels of endogenous hormones. By the selection of radiation exposure dose and time post-irradiation, it is possible to affect independently these two processes suggesting that each may be regulated independent of the other and involves a distinct site.

Studies in the synthesis of 4, 5-disubu/stituted phenanthrenes /|nK. Ramakrishnan. -- 260 St. Catharines, Ont. : [s. n.],

The work described in t his thesis was initiated with the intention of exploring new routes for the synthesis of certain 4, 5-disubstituted phenanthrenes. A series of reactions have been investigated in detail and several 4, 5-disubstituted phenanthrenes have been prepared. Some of the methods employed were novel and the yields of products were comparable or even better than the existing routes . A major observation made during the course of this work was the stability of the seven-membered ring system bridging the 4 and 5 positions of the phenanthrene nucleus . It has been found t hat the unbridged structures are not preferred if the compound is capable of isomerising to a bridged form . We have explained this phenomenon in t erms of the stereochemistry of t he 4 and 5 positions of the phenanthrene nucleus as well as the geometry of the bridge . Low temperature NMR studies have been carried out to investigate the conformations of the benzylic hydrogens of some of the 4,5-bridged compounds. However, the results were not conclusive as more than one reason could be attributed t o the observations .

The application of gas liquid chromatography to the simultaneous analysis of sugars and sugar phosphates in biological samples /|nby David J. LeBlanc. -- 260 St. Catharines [Ont. : s. n.],

A study was undertaken' to determine the applicability of gas liquid chromatography to the simultaneous analysis of sugars and sugar phosphates from biological samples. A new method of silylation involving dimethylsulfoxide, hexamethyldisilazane, trimethylchlorosilane and cyclohexane (1:0.2:0.1:1) which rapidly silylated sugars and sugar phosphates was developed. Subsequent chromatography on a 5% SE-52 column gave good resolution of the sugar and sugar phosphate samples. Sugar phosphates decomposed during chromatography and were lost at the 7 x 10-3 ~mole level. Acidic ethanol extraction of yeast samples revealed background contamination from the yeast sample, the culture medium and the silylation reagents which would further limit the level of detection obtainable with the glc for sugars in biological samples to the 3 x 10-4 ~mole level.

The kinetics and mechanism of the thermal decomposition of sec-Butyl peroxide in liquid phase /|nby Sandor Szilagyi. -- 260 St. Catharines, Ont. : [s. n.],

Re~tes artd pJ~oducts of tllerma]. d,ecom.position of sec-butyl peroxide at 110 - 150°C i.n four solvents h,ave been determined. The d,ecompos i tion vJas sb.o\'\Tn to be tlnlmolecl.llar wi tho energies of activation in toluene, benzene, and cyclohexane of 36 .7-+ 1.0, 33.2 +- 1..0, 33.t~) +.. 1.0 I'(:cal/mol respectively. The activation energy of thermal decomposition for the d,et.1terated peroxide was found to be 37.2 4:- 1.0 KC8:1/1TIol in toluene. A.bo1J.t 70 - 80/~ ol~ tJJ.e' pl~od.1..1CtS could, be explained by kn01rJ11 reactions of free allcoxy raclicals J and very littJ...e, i.f allY, disPl"Opox~tiol'lation of tll10 sec-butoxy radica.ls in t116 solvent cage could be detected. The oth,er 20 - 30% of the peroxide yielded H2 and metb.:'ll etb..yl 1{etol1e. Tl1.e yield. o:f H2 "'lIas unafJ:'ected by the nature or the viscosity of the solvent, but H2 was not formed when s-t1U202 lrJaS phctolyzed. in tolttene at 35°C nor 'tl!Jrl.en the peroxide 1;'JaS tl1.ermally o..ecoJnposed. in the gas p11ase. ~pC-Dideutero-~-butYlperoxide was prepared and decomposed in toluene at 110 - 150°C. The yield of D2 was about ·•e1ne same 248 the yield. of I{2 from s-Bu202, bU.t th.e rate of decomposition (at 135°C) 1iJas only 1/1.55 as fast. Ivlecl1.anisms fOl') J:1ydrogen produ.ction are discussed, but none satisfactorily explains all the evidence.

The kinetics and mechanism of the thermal decomposition of bis diphenyl methyl and related peroxides in liquid phase /|nby C. Thankachan. -- 260 St. Catharines, Ont. : [s. n.],

Rates and products have been determined for the thermal decomposition of bis diphenyl methyl peroxide and diphenyl methyl tert* butyl peroxide at 110@~145@C* The decomposition was uniformly unimolecular with activation energies for the bis diphenyl methyl peroxide in tetrachloroethylene* toluene and nitrobenzene 26,6* 28*3f and 27 Kcals/mole respectively. Diphenyl methyl tert* butyl peroxide showed an activation energy of 38*6 Kcals/mole* About 80-90% of the products in the case of diphenyl methyl peroxide could be explained by the concerted process, this coupled with the negative entropies of activation obtained is a conclusive evidence for the reaction adopting a major concerted path* All the products in the case of diphenyl methyl peroxide could be explained by known reactions of alkoxy radicals* About 80-85% of tert butanol and benzophenone formed suggested far greater cage disproportionation than diffusing apart* Rates of bis triphenyl methyl peroxide have been determined in tetrachloroethylene at 100-120@C* The activation energy was found to be 31 Kcals/mole*

The problem of national integration in plural societies : a case study of Pakistan, 1947-71 /|nMuhammed A. Quddus. -- 260 St. Catharines [Ont. : s. n.],

Pakistan had a plural society per excellence. Its people were divided geographically between two separate regions, spoke different languages, had different cultures and economic structures. Like other plural societies elsewhere, Pakistan also faced the problem of national integration. Cleavages along the lines of traditional attachments are fundamental to any plural society, as they were in Pakistan. But their political manifestation could have been kept within managable limits if the Central Government, overwhelmingly composed of the West Pakistanis, was seriously committed to the task. All that Pakistan needed to maintain her integrated existence was deliberate, calculated and conscious efforts on the part of the Central Government to give the Bengalis, the majority linguistic and geographic group in the country, a partnership in the state of Pakistan, an effective power in the decision-making process of the country, a reasonable share from the economic resources of the country, and to show respect to their hopes and aspirations. In addition, Pakistan needed a national platform to bring her divergent linguistic and geographic groups toge~her for some common, national purpos~s. Political parties were the only institutions which could have served this purpose. Pakistan miserably failed to sustain national political parties and failed to satisfy Bengalis' demands. This failure eventually resulted in the falling apart of the political system of Pakistan in 1971.

The Smiles rearrangement in hydrazidic systems and related syntheses /|nG. A. Pawelchak. -- 260 St. Catharines, Ont. : [s. n.],

This research was directed towards the investigation of the Smiles rearrangement in hydrazidic systems and the synthesis of related heterocyclic compounds. The work can be conveniently divided into two main sections. Section 1 of the thesis relates to the synthesis and examination of the O+N migration of phenoxy- derivatives of hydrazidic halides. In general, hydrazidic halides were found to react with 2-nitrophenol and 4-nitrophenol to give corresponding a-nitrophenoxy- compounds. These a-nitrophenoxy- compounds were found to rearrange in warm base to give the corresponding N-benzoyl compounds via a proposed five-membered transition state. Experiments conducted in styrene revealed no radical contribution to the rearrangement. Cross-over product analysis indicated the rearrangement as intramolecular and consistent with the Smiles rearrangement. The preparation of N-a-chlorobenzylidene-N'-2-nitrophenyl- -N'-(2,4-dibromophenyl)hydrazine from N-benzoyl-N'-2-nitrophenyl- N'-(2,4-dibromophenyl)hydrazine was accomplished using phosphorus oxychloride. Examination of this hydrazidic chloride indicated a marked decrease .in reactivity as compared to the N-a-chlorobenzylidene-N'-phenylhydrazine case. Section 2 concerns itself with the preparation of heterocyclic compounds using an analogy of the five-membered transition state present in the Smiles rearrangement of a substituted benzylidene derivatives A new preparation of 2,4-phenyl1,3,4- oxadiazol-S-one using N-benzoyl-N'-phenylhydrazine and ethyl thiochloroformate is reported. Two new preparations of N-a-thiobenzoyl-N'-(2,4-dibromophenylhydrazine are reported using sodium hydrosulfide in conjunction with N-a-bromobenzylidene-N'-(2,4-dibromophenyl)hydrazine in the first, and phosphorus pentasulfide with N-benzoylN'-( 2,4-dibromophenyl)hydrazine in the second. The latter is preferred due to the formation of a sulfide co-product in the former. Two preparations of 2-phenyl-4-(2,4-dibromophenyl)-1,3,4- thiadiazol-S-one are reported using N-thiobenzoyl-N'-(2,4-dibromophenyl) hydrazine and ethyl chloroformate and ethyl thiochloroformate Two rapid and easy preparations of 2-phenyl-4-(2,4-dibromophenyl)- 1,3,4-triazol-S-one are reported using ethyl chloroformate and ethyl thiochloroformate. Sodium cyanate in conjunction with a-aminobenzylidene-N'-(2,4-dibromophenyl)hydrazine also provided 2-phenyl-4-(2,4-dibromophenyl)-1,3,4-triazol-S-one Section 2 concludes with an examination of two possible mechanistic routes to the prepared heterocycles.

A tour from the City of New-York, to Detroit, in the Michigan Territory, made between the 2d of May and the 22d of September, 1818 : the tour extends from New-York, by Albany, Schenectady, and Utica to Sacket's Harbor, and thence throught Lake Ontario, to St. Lawrence river, and down that stream to Hamilton village. Thence along both banks of the St. Lawrence, from Hamilton to the Thousand Islands; thence to Sacket's Harbor by water; from that place by the route of great Sodus, Geneva, Cananaigua and Batavia, to Buffalo; and from thence to Black Rock, Fort Erie, the Falls of Niagara, Queenston, Lewiston, and the memorable fields of Bridgewater and Chippewa after viewing the interesting place of Niagara, the author traversed the south shore of Lake Erie to the City of Detroit, and visited in the latter range, Dunkirk, Erie, Cleveland, Sandusky, and other places of less note. The tour is accompanied with a map upon which the route will be designated; a particular map of the Falls andRiver of Niagara, and the environs of the City of Detroit /

Errata slip inserted.

Some ecological factors affecting the input and population level of total and faecal coliforms and salmonella in Twelve Mile Creek, Lake Ontario and sewage waters near St. Catharines, Ontario

Some Ecological Factors Affecting the Input and Population Levels of Total and Faecal Coliforms and Salmonella in Twelve Mile Creek, Lake Ontario and Sewage Waters Near St. Catharines, Ontario. Supervisor: Dr. M. Helder. The present study was undertaken to investigate the role of some ecological factors on sewage-Dorne bacteria in waters near St. Catharines, Ontario. Total and faecal coliform levels and the presence of Salmonella were monitored for a period of a year along with determination of temperature, pH, dissolved oxygen, total dissolved solids, nitrate N, total phosphate P and ammonium N. Bacteriological tests for coliform analysis were done according to APHA Standard Methods by the membrane filtration technique. The grab sampling technique was employed for all sampling. Four sample sites were chosen in the Port Dalhousie beach area to determine what bacteriological or physical relationship the sites had to each other. The sample sites chosen were the sewage inflow to and the effluent from the St. Catharines (Port Dalhousie) Pollution Control Plant, Twelve Mile Creek below the sewage outfall and Lake Ontario at the Lakeside Park beach. The sewage outfall was located in Twelve Mile Creek, approximately 80 meters from the creek junction with the beach and piers on Lake Ontario. Twelve Mile Creek normally carried a large volume of water from the WeIland Canal which was diverted through the DeCew Generating Station located on the Niagara Escarpment. An additional sample site, which was thought to be free of industrial wastes, was chosen at Twenty Mile Creek, also in the Niagara Region of Ontarioo 3 There were marked variations in bacterial numbers at each site and between each site, but trends to lower_numbers were noted from the sewage inflow to Lake Ontario. Better correlations were noted between total and faecal coliform population levels and total phosphate P and ammonium N in Twenty Mile Creek. Other correlations were observed for other sample stations, however, these results also appeared to be random in nature. Salmonella isolations occurred more frequently during the winter and spring months when water temperatures were minimal at all sample stations except the sewage inflow. The frequency of Salmonella isolations appeared to be related to increased levels of total and faecal coli forms in the sewage effluent. However, no clear relationships were established in the other sample stations. Due to the presence of Salmonella and high levels of total and faecal coliform indicator organisms, the sanitary quality of Lake Ontario and Twelve Mile Creek at the sample sites seemed to be impaired over the major portion of the study period.

Using GPS, GIS & remote sensing to understand Niagara Terroir : Pinot noir in the Four Mile Creek & St. David's Bench sub-appellations

The relationships between vine water status, soil texture, and vine size were observed in four Niagara, Ontario Pinot noir vineyards in 2008 and 2009. The vineyards were divided into water status zones using geographic information systems (GIS) software to map the seasonal mean midday leaf water potential (,P), and dormant pruning shoot weights following the 2008 season. Fruit was harvested from all sentinel vines, bulked by water status zones and made into wine. Sensory analysis included a multidimensional sorting (MDS) task and descriptive analysis (DA) of the 2008 wines. Airborne multispectral images, with a spatial resolution of 38 cm, were captured four times in 2008 and three times in 2009, with the final flights around veraison. A semi-automatic process was developed to extract NDVI from the images, and a masking procedure was identified to create a vine-only NDVI image. 2008 and 2009 were cooler and wetter than mean years, and the range of water status zones was narrow. Yield per vine, vine size, anthocyanins and phenols were the least consistent variables. Divided by water status or vine size, there were no variables with differences between zones in all four vineyards in either year. Wines were not different between water status zones in any chemical analysis, and HPLC revealed that there were no differences in individual anthocyanins or phenolic compounds between water status zones within the vineyard sites. There were some notable correlations between vineyard and grape composition variables, and spatial trends were observed to be qualitatively related for many of the variables. The MDS task revealed that wines from each vineyard were more affected by random fermentation effects than water status effects. This was confirmed by the DA; there were no differences between wines from the water status zones within vineyard sites for any attribute. Remotely sensed NDVI (normalized difference vegetation index) correlated reasonably well with a number of grape composition variables, as well as soil type. Resampling to a lower spatial resolution did not appreciably affect the strength of correlations, and corresponded to the information contained in the masked images, while maintaining the range of values of NDVI. This study showed that in cool climates, there is the potential for using precision viticulture techniques to understand the variability in vineyards, but the variable weather presents a challenge for understanding the driving forces of that variability.

Restoration and succession of a bee community in southern St. Catharines, Ontario, within a ten-year study period

A wild bee community in southern St. Catharines, Ontario, Canada, was studied from 2003 to 2012 to analyze the effects of primary succession on abundance and diversity. At a former landfill site near Brock University, which previously contained no bees, the number of bees and bee species was expected to increase rapidly following measures to restore the site to grassy meadow habitat. The Intermediate Disturbance Hypothesis (IDH) states that over time, succession occurs. Abundance and diversity increase initially and peak when pioneers coexist with specialized species, then decline because of competitive exclusion. Alternatively, abundance and diversity may continue to increase and stabilize without declining. Bees were sampled repeatedly among years from newer restoration sites (revegetated in 2003), older restoration sites on the periphery of the former landfill (revegetated in 2000), and nearby low disturbance grassy field (i.e. control) sites. In the newer sites, bee abundance and diversity increased then decreased while in older restoration and control sites mainly decreased. This pattern of succession matches the general predictions of the IDH, although declines were at least partially related to drought. By 2006, total bee abundance levels converged among all sites, indicating rapid colonization and succession, and by 2012 diversity levels were similar among sites as well, suggesting that the bee community was fully restored or nearly so within the ten-year study period.