64 results for University of Canterbury Library, 1950

  • The improvement of light land under irrigation on the Canterbury Plains

    Moore, John Leslie Neville (1957)

    Masters thesis
    University of Canterbury Library

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  • The election of 1935 in New Zealand.

    Rollo, Carol Gertrude (1950)

    Masters thesis
    University of Canterbury Library

    Of all the elections in New Zealand's political history, only two qualify for the adjective momentous. In 1890 and in 1935, Governments came to power whose vigour and liberalism were not only to alter the lives of their. contemporaries, but also to make changes that had continual repercussions in this country and echoes in other nations' handling of social problems.

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  • The ultra-violet absorption spectra of certain ketimines and their related ketones

    Kaplan, Isaac R. (1952)

    Masters thesis
    University of Canterbury Library

    1. A review has been made of the preparation and properties of ketimines. At present no similar review exists in the chemical literature. 2. A discussion of the process of absorption, with particular reference to the carbonyl group has been offered. This discussion includes certain effects taking place, hyperconjugation being the most relevant to the thesis. 3. A series of diaryl ketones and ketimines have been prepared and studied by ultra violet spectroscopy; four of these compounds ( p-ethyl-, p-iso-propyl-, and p-tert.butyl-benzophenoneimine hydrochlorides, and p-tert.-butyl-benzophenone) have not been prepared before. The preparation and ultra violet absorption study of fenchone and fenchone-imine, have been described. 4. The Hilger Uvispek Spectrophotometer has been described and its limitations, with respect to accuracy, discussed.

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  • The heats of solution of rare gases in water

    Alexander, D. M. (1954)

    Doctoral thesis
    University of Canterbury Library

    The intercorrelation of data obtained from the measurement of quantities connected with the solution of gases in liquids has led to a number of empirical laws (e.g. Henry’s Law, Just’s Law) which in turn have led to attempts at theoretical justification. Attention has of course been devoted to the theoretical justification for deviation from these laws. The measurable quantities have been: (a) Solubility under various conditions (b) Molal volumes of gases in liquids These appear to have been the only quantities used. The limited scope of the data has the effect of placing great strain on the accuracy. Much of the data is discordant. Reviews of interrelationships of these quantities and the relation of the quantities to the properties of the pure components of the mixture have been published.

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  • The alkaline hydrolysis of some ethyl bromo-1-naphthoates

    Ogilvie, G. S. (1957)

    Masters thesis
    University of Canterbury Library

    3 Bromo-1-naphthoic acid, 4-bromo-1-naphthoic acid, 5-bromo-1-naphthoic acid, and their ethyl esters have been prepared. The kinetics of alkaline hydrolysis is ethanol-water (85:15 W/W) of these esters, together with the unsubstituted ester, have been studied, using stainless steel reaction vessels, over the temperature range 25-65°C. Arrhenius frequency factors and energies of activation have been determined. The frequency factors have been shown to be constant within a small experimental error. Relative free energies, heats, and entropies of activation for these hydrolyses have been evaluated and their significance discussed. Hammett substituent constants for the bromo-substituent in the 3, 4, and 5 positions of naphthalene have been calculated and discussed.

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  • An investigation of the effects of multiple spark ignition on performance of a high speed petrol spark ignition engine

    Walters, D. L. (1954)

    Masters thesis
    University of Canterbury Library

    At the present time ignition by high tension electric spark is almost universal on high speed reciprocating internal combustion engines other than the compression ignition type. The growing demands for greater efficiency, higher specific power output and increasing speed range with the associated high compression pressures has made greater demands on the ignition system. The modern magneto and coil, having progressed from the early hot wire and hot tube ignition, have been developed to a high stage of efficiency, although other systems have been suggested. Improvements in performance have been noted with dual ignition and this system is standard on aircraft engines, although in this case improved performance is only a secondary consideration to safety. With dual ignition, one set of plugs is connected to the first magneto and the other set to the second magneto, the sparks occurring simultaneously at the two plugs. As a result explosion is propagated from two points in the cylinder. The sparking plugs are usually placed as apart as possible and it was Swaine who suggested that better results might be obtained with sparking plugs placed very close together. As far as the author is aware, no experimental work has been carried out along these lines.

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  • New England whalers in New Zealand waters, 1800-1850

    Canham, P. G. (1959)

    Masters thesis
    University of Canterbury Library

    New Zealanders are constantly reminded of their whaling heritage. The numerous gates and arches formed by wholes' jaw-bones, the trypot prominently displayed in Timaru's Caroline Bay, the lingering fame of Dicky Barret in New Plymouth, the legends of the Bay of Islands, and the relics held by every museum, are some of the many remnants which emphasise the role of whaling in New Zealand’s history. Present-day events play their part, too; the continued success of the Tory Channel station, and the visits by Russian and Japanese fleets from the Antarctic, maintain the tradition of New Zealand as a centre of whaling. Possibly it is because of these present day examples that the tradition has become more legendary than factual in nature, for the Tory Channel party, with their fast chasers, and the Russian fleet, with its radar, sonar and helicopters, seem almost divorced from the old methods. Consequently, there has been a tendency to glamourise the men who rowed out after whales, risking death with every stroke, and, if successful, towing the carcass tedious miles back to the trying-works. While bravery and fortitude are always commendable, only the passage of a century could make heroes out of the old-time whalers. In a similar way, legend has distorted the size and significance of the old whaling industry. To take just one example, the editor of the Marsden papers goes out of his way to add to add this comment: "An old settler informed me in the 1880’s", writes Mr. S. Percy Smith, "that he had seen over sixty whale ships at one time anchored in the Kawakawa River opposite Opua".

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  • The development of an experimental method of obtaining an influence diagram for stress in structural frames

    Robinson, J. V. (1952)

    Doctoral thesis
    University of Canterbury Library

    The function of an engineering structure is to receive external and gravitational forces which must be transmitted and distributed to some external medium, and the structural efficiency is a measure of the utilization of the force resisting capacity of' the structure. Structural efficiency is, however, no overall criterion of structural suitability, for aesthetic, economic and constructional qualifications must also be considered. Originally the structural efficiency was limited severely by these latter three considerations. With the development of high grade materials and manufacturing processes with closely controlled quality and precisely predictable strength, and strength deformation characteristics, it has become economically and constructionally desirable to use them efficiently. The advent or arc welding and reinforced concrete has enabled these basically more efficient structures to be economically constructed. This increased structural efficiency introduces greater degrees of indeterminancy in the structure and requires more precision in the design which in their turn have resulted in a necessary examination of load prediction, factors of safety and design method. The external forces to be transmitted by a structure will generally be continuously variable and not precisely predictable, although in some instances the load may be quite specifically defined for the whole of the life of the structure. The life of a structure is rarely known for those exposed to natural forces such as flood, earthquake or wind loads, the design loads specified in the governing code of practice are based upon the phenomenon of certain severities being definitely cyclic, the longer the cycle the greater the severity. If these loadings are then accepted a probable life period is also accepted. Similarly, the live loading values for various type structures laid down in these codes are values which have been found by experience to be satisfactory or safe for the normal life period of buildings in the area concerned, and which may or may not be proved by involuntary full scale tests.

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  • The paradoxes of strict implication

    Bennett, J.F. (1952)

    Masters thesis
    University of Canterbury Library

    The problem in logic with which the present work is concerned has its roots in the Principia Mathematica of Whitehead and Russell. The authors of that work define 'p implies q' as 'It is not the case that p is true and q is false’, whence arises the conclusion that a true proposition is implied by any proposition and a false proposition implies any proposition. These paradoxical results have met with protest, and C. L. Lewis of Harvard has attempted to supply a definition of 'p implies q' which is adequate to 'implies' as generally understood.

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  • Heats of mixing

    Adcock, D. S. (1954)

    Doctoral thesis
    University of Canterbury Library

    The object of this investigation was to test some recent theories of the equilibrium behaviour of liquid mixtures. Much theoretical work has been done on this subject, but very few experimental measurements have been made on mixtures simple enough to be satisfactorily described by the models proposed. This work was undertaken to provide data for simple mixtures that could be expected to be reasonably well described by the theoretical models.

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  • The alkaline hydrolysis of ethyl 1-naphthoate, ethyl 3-methyl-1-naphthoate and ethyl 4-methyl-1-naphthoate in ethanol-water

    Packer, J. E. (1956)

    Masters thesis
    University of Canterbury Library

    3-Methyl-1-naphthoic acid, a compound not previously known, has been prepared. The kinetics of the alkaline hydrolysis of ethyl 1-naphthoate, ethyl 3-methyl-1-naphthoate, and ethyl 4-methyl-1-naphthoate in ethanol-water (85:15 by weight), have been studied at four temperatures, using a titration method; Arrhenius frequency factors and energies of activation have been determined. These values for ethyl 1-naphthoate were found to differ from those of a previous investigator, and the differences have been discussed. Relative free energies, heats, and entropies of activation for the alkaline hydrolysis of ethyl 3-methyl-, 4-methyl-, 2-nitro-, 3-nitro-, 4-nitro-, 5-nitro-, 6-nitro-, 8-nitro-, and 4:5-dinitro-1-naphthoates have been evaluated and their significance has been discussed. Hammett substituent constants for the methyl group in the 3- and 4- positions and for the nitro group in the 3-, 4-, 5- and 6- positions have been calculated.

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  • A microcalorimetric study of the intermediate complexes CdBr+. CuBr+ in aqueous solution

    Tennant, W. C. (1955)

    Masters thesis
    University of Canterbury Library

    Panckhurst has attempted to explain the observed stability trends for a series of halide complexes in solution with a given metal and also for various complexes with a given halide. He concludes that the stabilities relative to one another are dependent upon the relative magnitudes of the standard heats of formation and standard entropy changes but that the data available is inadequate and often subject to factors which make comparison difficult. In recent years, increasing interest has been shown in the physical chemistry of complex-ion formation. In particular, numerous measurements have been made of the stability constants of complex ions and hence their free energies of formation. If their heats of formation are also known the corresponding entropy changes can, of course, be evaluated. Usually however, either these heats of formation have not yet been determined, or else the only values available are those calculated from stability – constant measurements at more than one temperature. The reliability of such values often seems questionable, primarily because the range of temperatures over which the measurements were made has almost always been too small. It is undoubtedly better to measure the heats of formation calorimetrically, preferably under more or less the same conditions of concentration and ionic strength as those used in the measurement of the stability constants. We here report a microcalorimetric determination of the heats of formation of the complex ions CdBr+ and CuBr+ in aqueous solution. The apparatus and procedure employed are similar to those used previously in this college in work on the lead halide complexes. In the case of the CdBr+ complex we have extended the method to calculate a value of the equilibrium constant which we shall compare with other values from the available literature. We shall attempt in conclusion to throw some further light on the nature of complex species in solution and also to further explain the observed stability trends of these complexes.

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  • The X-ray structure analysis of phosphorus thioiodide

    Wright, D. A. (1958)

    Doctoral thesis
    University of Canterbury Library

    These compounds were studied by Ouvrand (1892), (1894), who came to the conclusion that three thioiodides existed, namely P₄S₃I₂, PSI and P₂SI₄. Three methods of preparation for P₄s₃I₂, one for PSI and four for P₂sI₄ were given, but Ouvrard mentions neither the precise conditions for their preparation, nor any means of characterization. The compound P₄S₃I₂ was also reported by Wolter (1907) as formed by the slow addition of iodine to P₄S₃, a method given by Ouvrard. The lack of any analogues to these compounds such as P₄O₃I₂, P₄ S₃Br₂ made it of considerable interest to confirm these early reports if possible, and find the inter-relationships between any thioiodides made. Accordingly an investigation was carried out in detail by Topsom and Wilkins (1956). Attempts to prepare P₂SI₄ and PSI by Ouvrard's methods were not successful. They could not be detected even as intermediates under the mildest conditions of reaction, and their existence is open to serious doubt. Two of the methods did in fact lead to a thioiodide, but this was shown to be P₄S₃I₂. Two of the three methods given by Ouvrard for the preparation of P₄S₃I₂ were successful, that one consisting of heating the elements in the ratio of 4P:3S:2I giving almost quantitative yield (see Section 2.1). The compound was easy to prepare and readily characterized. Topsom and Wilkins could not detect any other phosphorus thioiodide and infer that this is the only stable compound formed by these three elements.

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  • The alkaline hydrolysis of the ethyl and methyl esters of 1-naphthoic acid and 2-naphthoic acid

    Wilson, A. F. (1954)

    Masters thesis
    University of Canterbury Library

    Samples of the ethyl and methyl esters of 1-naphthoic acid and 2-naphthoic acid have been prepared and the kinetics of hydrolysis of these esters have been studied in alkaline solutions over the temperature range 30°C- 60°C. Aqueous methanol was employed as solvent for the methyl esters, and aqueous ethanol for the ethyl esters. Relative reactivities at the 1- and 2- positions as measured by this work are in line with theoretical prediction, and the relative rates of the methyl and ethyl esters have been discussed. Comments have been made on an earlier investigation by Bergmann and Hirshberg of the methyl compounds, the results of which appear to be anomalous. A value for the Hammet σ constant for the fused benzene ring has been derived and has been compared with values calculated by other investigators.

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  • The K-series emission spectrum of neon : a study on the excitation of X-radiation in some gaseous elements by means of an electrodeless discharge, and an analysis of the radiation, in the case of the inert gas neon, with a bent crystal vacuum spectrograph

    Moore, Horace Raymond (1954)

    Doctoral thesis
    University of Canterbury Library

    Experiments are reported in which the inert gases argon and neon were subjected to a high-voltage electrodeless discharge. The characteristics of the discharge were studied, and a theory of the mechanism of origin of the emitted x-radiation is proposed. The construction of a composite X-ray, incorporating both orthodox electrodes and an electrodeless discharge tube is described. This involved the building of a vacuum evaporating unit. Details are given of the construction of a photographically recording bent crystal vacuum spectrograph. Using a mica crystal, the working range of the instrument is about 5-19kX in the first order of reflection, the inverse linear dispersion being about 37 X/mm at 15 kX. A spectroscopic analysis of the X-radiation emitted by the inert gas neon is described. Twenty-one K-series lines were recorded, many of them for the first time. The majority of the lines have been identified and the wavelengths measured in all cases. The shapes of the main neon lines were obtained on an intensity scale, and their half-width values, uncorrected for possible diffraction breadth, were determined. As the result of these investigations certain conclusions are drawn.

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  • Some effects of desiccation of clays in relation to their compression

    Kidson, C. B. (1956)

    Doctoral thesis
    University of Canterbury Library

    Laboratory tests of compression, shrinkage under air drying conditions and measurements of negative pore water pressures were made on some clays in the natural and remoulded states, with a view to gaining information on the effects of desiccation on the compression characteristics of fine grained soils and the relationship between negative pore water and effective pressures.

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  • The effect of angularity on the shearing strength of sands

    Gentry, S. C. (1956)

    Doctoral thesis
    University of Canterbury Library

    An attempt has been made in this thesis to analyse the factors which affect the shearing strength of dry sand, as given by Coulomb’s Equation S = p tan φ. Experiments have been carried out using sands of varying angularities and comparing results with those for glass beads. Uniform and ungraded samples were also considered.

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  • The effect of alkyl substituent-groups on the base-catalysed hydrolysis of amides

    Thomson, A. L. (1954)

    Doctoral thesis
    University of Canterbury Library

    The alkaline hydrolysis of amides follows a simple two stage mechanism, the first stage being addition of a hydroxyl ion and the second being addition of a hydroxyl ion and the second being decomposition to form the reaction products. The mechanism may be represented wither as a addition and retrogression reaction or as a nucleophilic substitution reaction. The addition reaction requires an intermediate with definite independent existence while the substitution reaction requires a transition complex with no finite period of existence. Ingold has discussed this question and has concluded that the position actually assumed is probably between the two extremes with an intermediate stabilised by mesomerism. The existence of an intermediate with a finite life has been experimentally established in the case of ester hydrolysis which is in many ways a similar reaction. The status of the intermediate in the amide reaction, as a molecule, can be assumed by analogy. The reaction is thus not a simple substitution reaction but on the other hand it is not necessarily an addition reaction as normally understood. The most acceptable interpretation of experimental results appears to be given by assuming a resonant intermediate of the dual reaction mechanism as suggested by Ingold. The rate-controlling step in the reaction mechanism is the addition of the hydroxyl ion and it is thus found that electron-attracting substituent groups on the amide accelerate, and electron-repelling groups retard, the reaction. Bevan, Hughes and Ingold have found that in some nucleophilic substitution reactions the loss of the displaced group constitutes the rate-controlling step in the reaction but experimental evidence shows that this is not so for the base-catalysed hydrolysis of amides. Alkyl-groups are electron-repelling in nature and, as expected, are found to reduce the rate of hydrolysis when compared with the unsubstituted amide. The electronic properties of alkyl groups are the sum of two different effects brought about in different ways, an inductive effect and a hyperconjugative effect. In the series methyl, ethyl, iso-propyl and tert-butyl, the inductive effect increases while the hyperconjugative effect decreases through the series. Published data on similar compounds suggests that, in the simple aliphatic amides where the alkyl groups are directly bonded to the reacting group, the order of reactivity should be dictated almost entirely by the inductive effects of the alkyl groups. In the para-substituted benzamides on the other hand, where the amide group is separated from the substituent by the conjugated unsaturated system of the benzene ring, the conditions for hyperconjugation are comparatively much more favourable. The reactivity order may then be either inductive, hyperconjugative, or a mixture of both. All three of these reactivity series have been observed experimentally for different compounds which were not greatly different structurally from the p-alkylbenzamides. The actual reactivity order existing in these amides under a give set of experimental conditions cannot be forecast in any way. In p-alkyl-aromatic compounds, the order or reactivity as well as being considerably effected by minor structural changes may also be altered by changing experimental conditions. This has been observed in ethyl p-alkylbenzoates when the solvent was changed from aqueous ethanol to aqueous acetone. In the work here reported, as study of the kinetics of hydrolysis, in excess of sodium hydroxide in water, of alkyl-substituted acetamides and of p-alkylbenzamides has been carried out. The significance of the experimental results so obtained is discussed.

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  • The general mechanism of evaporation and production of saturated brine by natural evaporation of sea water in large ponds

    Teplitzky, D. R. (1954)


    University of Canterbury Library

    The principle of manufacturing salt from the sea is discussed. An examination of the literature indicates that the only relevant investigation which has been carried out is on the rate of evaporation from large bodies of water. A summary of the relevant methods of assessing the evaporation is made and it is concluded that the aerodynamic approach is the most promising. An approximate equation describing the evaporation from Lake Grassmere as a function of time and brine concentration is derived for average weather conditions. A qualitative discussion on the mechanism of natural evaporation of water from brine ponds by solar energy leads to energy balances which, it is suggested, should be completely investigated to produce an optimum depth of brine in a pond. Material balances are set up for the general case of flow in n ponds. These can not be solved, for the variation of flow with time and a stepwise procedure is adopted to allow calculation of the output of saturated brine under average weather conditions for one, two, more than two, and an infinite number of ponds in a system. The latter calculations are based on what is proved to be an invalid assumption so that the results are erroneous. For the one and two pond cases, an estimate of output of saturated brine under average weather conditions is made and the time required to reach the stage of maximum output assessed.

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  • The withdrawal of the British troops from New Zealand, 1864-1870 : a study in Imperial relations

    Hensley, Gerald C. (1957)

    Masters thesis
    University of Canterbury Library

    The Course of New Zealand history until 1870 was dominated by two themes in counterpoint: one was the Imperial Government’s responsibilities under the treaty of Waitangi, and the protectorate which it felt had then been assumed over the Maoris; the other was the demand which grew up in the Colony for responsible government. The two were incompatible – Imperial control and Colonial self-government could never be reconciled – and their antithesis, rooted in the very foundations of the Colony, was too strong not to cause some strain. The crisis which occurred in 1868 over the withdrawal of the Imperial forces from New Zealand was an accidental event only in its immediate details. In reality it was the culmination of a long process; the last, and certainly the most serious, of the tensions which sprang from that antithesis of forces. It was the culmination because, by marking the end of Imperial responsibilities within the Colony, it resolved a clash which had underlain New Zealand’s erratic constitutional development for thirty years. The proclamation of Imperial authority over New Zealand was immediately and inevitably challenged by the beginnings of agitation for self-government. Henceforth the changing balance between the two was to give the Colony’s politics its distinctive nature, until the gradual transition was completed by the withdrawal crisis and the consequent assumption by the Colony in 1870 of full responsibility for its own affairs. The first of these conflicting themes, in point of time, was the problem of Imperial control. New Zealand had been annexed, not to forestall the French or inflate the Empire, but to protect the Maoris. In the face of inevitable European colonisation, a Crown Colony seemed the only way to safeguard native rights, since it would be controlled by and be solely responsible to Great Britain. Having accepted certain obligations at Waitangi, the Imperial Government felt it essential to have a free hand to fulfil them. In return, it undertook responsibility for the Colony’s defence and, when a native war broke out (as in 1845), for the military operations necessary to restore peace. It was understood that while the Home Government directed the Colony’s affairs and controlled the treatment of the natives, it would bear all the accompanying expense. The only flaw in this system was that, adopted in the interests of the Maoris, it assumed that white settlers would be comparatively few or comparatively uninterested – neither of which was long to remain true. Auckland was the sole place where such a balance of natives and settlers prevailed for any time, and significantly Auckland, as late as 1868, would have liked to return to the Crown Colony system. For full Imperial control meant full Imperial liability, and the North’s regret for this comfortable arrangement lingered on to become an important strand in the withdrawal crisis.

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