31 results for 1950, Doctoral

  • 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 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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  • 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 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 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 structure and stereochemistry of the diterpenes and the glycoalkaloid from solanum nigrum

    Davis, Brian Reeve (1957)

    Doctoral thesis
    The University of Auckland Library

    The diterpenoids are fairly widely distributed in nature. The best known members are the resin acids obtained from the non-volatile portion of many oleoresins, especially those obtained fram conifers. Diteppenoid acids, alcohols, lactones, phenols, and alkaloids have been obtained from a variety of sources. The hydrocarbons are more restricted in occurrence; all are found in New Zealand and all but two (camphorene and cupressene) in endemic species. Their reported occurrences are almost solely limited to countries bordering on the Pacific.

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  • The crystal structure of acetamidoxime

    Claridge, G. G. C. (1955)

    Doctoral thesis
    The University of Auckland Library

    The chemistry of the amidoximes (a) has long been of interest because of the possibility of tautomerism with hyroxyamidines (b)

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  • The crystal structures of the bromo and chloro derivatives of picrotoxinin / Bryan Maxwell Craven

    Craven, Bryan Maxwell (1957)

    Doctoral thesis
    The University of Auckland Library

    Picrotoxin is the bitter tasting convulsive poison, obtained from the cocculus berries, the fruit of the East Indian creepers, Menispermum cocculus and Anamirta paniculata. It has been used extensively in medicine as anti-barbiturate. Although picrotoxin was first isolated in 1812 by Boullay and has been the subject of exhaustive research since then, the problem of its structure is still incompletely solved.

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  • The Origins of the Maori wars of the Eighteen Sixties

    Sinclair, Keith (1954)

    Doctoral thesis
    The University of Auckland Library

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  • A thesis presented to the University of New Zealand for the Doctor of Science

    Green, Rowland Alfred Weldon (1953)

    Doctoral thesis
    The University of Auckland Library

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  • The colour isomerism and structure of some copper co-ordination compounds / T.N.M. Waters

    Waters, Thomas Neil Morris (1957)

    Doctoral thesis
    The University of Auckland Library

    Following the classical work of Werner whose co-ordination theory provided the first rational foundation for the study of transition metal complexes, chemists have endeavoured to discover the underlying principles involved in these compounds. Thus, while Werner noticed the directional property of the bonds between metal and ligand, it was not until Pauling (1931) and others were able to apply a wave mechanical treatment, that an explanation for the rigid stereochemical requirements of the metal was found. With this growth in fundamental knowledge the interpretation and use of the physical properties of complex compounds has become possible. For example, the magnetic susceptibility has been related to the electronic configuration of the metal atom, (Pauling loc. cit.) enabling predictions to be made about the type of metal-ligand bond.

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  • Time variations in cosmic ray extensive air showers.

    Storey, John Richard (1957)

    Doctoral thesis
    The University of Auckland Library

    Two motives are responsible for the investigation of cosmic rays. Firstly they provide the only source at present availabe of particles with extremely high energy. To study interactions between fundamental particles at energies greater than about 6 x 109 ev. therefore, one must turn to cosmic rays. Interest in geophysics and astrophysics provides the other motive. For example, a theory of the origin of cosmic rays must form an integral part of the astronomer's explnation of the universe. The prob1em of the origin of the cosmic radiation is still looking at satisfactory solution. Further, much information about the physics of the solar system and the earth may be obtained from a world wide distribution of cosmic ray observatories.

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  • A study of coordination compounds of nickel with some diamines.

    Curtis, Neil Ferguson (1954)

    Doctoral thesis
    The University of Auckland Library

    The coordination compounds of many transition metals can exist in two form with differing magnetic moments. As the paramagnetic susceptibility arises largely from the unpaired electrons present in the molecule, this means that the two classes of compound for any metal must have differing numbers of unpaired electrons. The first satisfactory explanation of the differing magnetic moments was given by Pauling who suggested that there were two fundamentally different types of coordination compound.

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  • A study of some of the factors concerned in the natural regeneration of the kauri (Agathis australis)

    Mirams, Rex Valentine, 1925- (1951)

    Doctoral thesis
    The University of Auckland Library

    New Zealand is a land with a unique and very diversified flora which, along with the great range of habitats to be found throughout the country, has given rise to some remarkable plant communities. As a result of a considerable volume of ecological research, mainly by the efforts of Cockayne, our plant associations are well known and delimited. There have, however, been few detailed analyses of their structure and of the factors operating in any of them, Cockayne's work being primarily descriptive. From the developmental point of view the general life-history of the Kauri forest has been known for many years, but nothing more detailed is known about the changes occuring. It is for the above reason that an attempt has been made in the present research to try and elucidate some of these factors while there are still considerable areas of Kauri forest in a more or less untouched state.

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  • Studies on the Biology of Soil Ciliates

    Stout, John David (1952)

    Doctoral thesis
    Victoria University of Wellington

    The soil ciliate fauna consists of at least three major groups: (a) Species found wholly or chiefly in granular soils and litters and which may also be found in moss or sphagnum. These species are often larger than other soil species and structurally more specialized. (b) Species also commonly fond in sewage, faeces or polluted water. These are chiefly small holotrichous ciliates which feed on bacteria. They tolerate a wide range of pH, salinity, temperature, oxygen and carbon dioxide tensions. They generally have a well developed cyst physiology. (c) Species of common fresh water genera which differ from the fresh water species chiefly in size. They are generally small holotrichous ciliates fairly widespread in soil although they have not yet been recorded from other habitats. Parasitic species such as Balantidium and anaerobic species such as Trimyema occur very rarely. Suctorians occur occasionally. In the laboratory most species grow best in a medium nearest their natural environment, viz. soil or peat extract. This is particularly true of the first and third groups. The second group grows well in enriched media which are not tolerated by the other species. In a laboratory culture most species are found associated with the bottom detritus but one species, Blepharisma steini, common in litters and occasionally pigmented, avoids the bottom of the culture and is found only at the surface. Soil ciliates are not affected by pH changes over a wide range. In a soil laboratory culture there is less variation than in ordinary laboratory infusions, pH and Eh are fairly stable, and after the first week the bacterial flora consists principally of Pseudomonas. The ciliate fauna is present for about six weeks, the first species appearing within a few days, the majority being present after the first week, and finally the carnivorous species Dileptus alone being present after twenty weeks. The rhizopod fauna does not appear until after the majority of ciliate species have disappeared. The effect of a heavy inoculation of bacteria into a mixed culture of protozoa causes the death of certain species, such as Euplotes aediculatus and the rapid growth of other species such as Paramecium caudstum, Cyclidum glaucoma and Vorticella microstoma which encyst or die when the bacteria are wholly consumed. Other species such as Vorticella striata neither die nor divide rapidly. Continued heavy inoculations of bacteria cause Veritcella microstoma to form unstable cysts due it is suggested to the accumulation of bacterial metabolites and the strongly reducing conditions. These cysts excyst when aerated. They are larger than the normal resting cyst which is formed on the exhaustion of food. Only a few species such as Colpoda steinii, Colpoda inflata and Colpoda cucullus survive anoxia for any length of time at room temperatures. These facultative anaerobes continue to feed and move although they cannot divide or excyst. Rarely they form unstable cysts. Other ciliates which also survive for some time are Stentor roeseli and Vorticella microstoma both normally sessile forms. The former becomes detached and swims freely in the medium with the aid of its peristomal cilia. Vorticella also becomes detached and forms a telotroch or swarmer which does not settle unless oxygen is present. The telotroch will survive in the absence of oxygen a little over two days. It cannot feed and it is suggested that the limited survival of these two ciliates is due partly to the exhaustion of their food reserves. Other species such as Stylonychia mytilus a common fresh water species and Halteria graudinella are extremely sensitive to anoxia. Colpoda steinii, Colpoda inflata and Paramecium caudatum are very resistant to high carbon dioxide tensions and C. steinii will continue to move though not feed or divide at very high carbon dioxide tensions. Halteria grandinella is moderately resistant but Coleps hirtus and Stylonychia mytilus are extremely sensitive. Vorticella microstoma in response to high carbon dioxide tensions forms a telotroch which survives a comparatively long time. The trophic ciliate is much more sensitive. Stentor also becomes detached in high carbon dioxide tensions. Colpoda steinii will grow in salinities up to 3% NaCl but division is progressively inhibited and unstable cysts are formed. Excystment takes place only if the environment is hypotonic to the ciliate. Growth of Colpoda steinii is most rapid at about 27 [degrees] c. At high and low temperatures division is inhibited and unstable cysts are formed. This unstable cyst is similar to the reproductive cyst but unlike that cyst remains inactive until the inhibiting factor, e.g. temperature or salinity, is removed. The factors which inhibit division also inhibit excystment and for this reason it is presumed that a common morphogenetic mechanism, identified with the 'activity' system found in other organisms, underlies them both. An interpretation of the physiology of Colpoda upon this assumption is used to explain the common effect of diverse environmental factors. Encystment and excystment are considered two distinct processes, contrary to the suggestion of Bridgeman (1948) who considered them complementary. Excystment of Vorticella microstoma may be stimulated by very low oxygen tensions but is normally dependent upon the presence of bacteria. Activation of the encysted Vorticella leads to two processes: the differentiation of the telotroch and the escape of the ciliate from the cyst membrane. Following imbibition of water the ciliate bursts through the cyst pore the aboral end foremost. The posterior ciliary wreath is normally differentiated after the ciliate escapes from the cyst membrane and assumes the elongated body form of the telotroch. Sometimes the ciliate fails to escape and a fully differentiated telotroch is formed within the cyst membrane. Following excystment the telotroch becomes free swimming and finally settles. It swims with the aboral end and the posterior ciliary wreath directed anteriorly. Telotrochs are normally formed during excystment or by division but anoxia or high carbon dioxide tensions will also cause the trophic ciliate to form a telotroch. It does not encyst under these conditions contrary to prevailing opinion (Brand, 1923). A consideration of the bionomics of ciliates shows that their ecology is determined in their behaviour, life history and physiology. Soil species, such as Colpoda, are distinguished by their small size, their tolerance of a wide range of soil conditions and the efficiency of their cyst physiology. Fresh water species are excluded from soil either because they are not tolerant of such environmental conditions as high carbon dioxide tensions, e.g. Coleps hirtus, or because they have a poorly developed cyst physiology, e.g. Paramecium.

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  • The Historical and Psychological Significance of the Unorganized Games of New Zealand Primary School Children

    Sutton-Smith, Brian (1953)

    Doctoral thesis
    Victoria University of Wellington

    In the Spring of 1948 while teaching at a primary school, I observed a small group of girls playing a game called "Tip the Finger". During the game one of the players chanted the following rhyme: "Draw a snake upon your back And this is the way it went North, South, East, West, Who tipped your finger?" I recognized immediately and with some surprise that this rhyme contained elements which were not invented by the children and were probably of some antiquity. I knew, for example, though only in a vague and unlearned manner, that the four pattern of the North, South, East and West and the Snake symbolism were recurrent motifs in mythology and folklore. I was aware also that there did not exits any specialized attempt to explain the part that games of this nature played in the lives of the players.

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  • The effect of a fused benzene ring on the reactivity of benzene derivatives

    Wilson, A. F. (1957)

    Doctoral thesis
    University of Canterbury Library

    In applying the Hammet equation the naphthyl derivatives, the fused benzene ring may be regarded as a group attached to a corresponding phenyl derivative, and its influence on reactivity may be discussed in terms of the Hammet substituent constant δ. Such discussion, in the case of a 1-naphthyl derivative is severely limited because the electronic effect (which is measured by δ) is masked by steric effects, the magnitude of which cannot normally be determined. Simple reactions of 2-naphthyl derivatives are free from such steric complication. The Analysis of date already published has revealed that, although the 3:4-benzo substituent has almost invariably been assigned a single δ value, there is apparently marked variation in the δ values required for different reactions. In the present investigation three reactions have been studied. The reactions were so chosen that (a) any past studies aided the interpretation of the present results and (b) the required δ values covered the range indicated by the analysis of data available in the literature. The reactions studied were as follows: (1) The reaction of benzoyl chloride with 1- and 2-naphthylanine in benzene was studied at 10°, 25°, 35°and 45°. (2) The solvolysis in ethanol of phenyl-1-naphthylcarbinyl chloride and of phenyl-2-naphthylcarbinyl chloride was examined at four temperatures over the range 5°-25°. For this reaction other data available were insufficient to obtain an accurate value of the reaction constant ρ, which is required for the calculation of a δ₃:₄-benzo value. Consequently the reaction kinetics of phenyl-m-bromophenyl-, phenyl-m-chlorophenyl-, phenyl-m-methylphenyl, phenyl-m-nitrophenyl- and diphenylcarbinyl chloride, were also examined in this reaction. These compounds were studied over the range 25°-75°. (3) The kinetics of the hydrolysis of ethyl 1-naphthyl-ethyl 2-naphthyl- and ethyl phenylacetate were investigated at four temperatures over the range of 20°-50°. It was clear from the present results, taken in conjunction with other data, that the δ values required for the 3:4-benzo substituent fall into significantly different classes. The difference may be linked ti the type and extent of conjugation possible between the substituent and the functional group in the reactant and transition states of these reactions. The reality of the differences in δ values, and the explanation for such differences, are discussed. For the reactions of 1-naphthyl derivatives studies in the present work, discussion of the 2:3-benzo substituent in terms of δ values is not meaningful without the accurate assessment of steric effects.

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