48 results for University of Canterbury Library, 1930

  • A history of the political labour movement in New Zealand, 1850-1913

    Robinson, K.W. (1937)

    Masters thesis
    University of Canterbury Library

    A typically modern trend in democratic countries has been the entry of labour representatives into the political arena. New Zealand has proved no exception to the rule, but the history of her own labour movement, particularly in its earlier years, is still rather disconnected in the eyes of the general public. This thesis therefore attempts to recount the origins of that movement with the object of presenting a clearer idea of the nature of the beginnings of the party which constitutes the present government. It was at first intended to write of the Labour Party in later years, but preliminary investigation was sufficient to show that no such treatment could be adequate without a knowledge of the origins of the Party. Further investigation showed those origins to be worthy of separate study in themselves, and the history of the Labour Party is therefore left for other pens to write. The aim throughout has been to trace, not a party, but a movement, and to discover how much that movement was influenced by contemporary events and how much it was a natural and inevitable development. A thorough study of the subject, giving an exhaustive survey of opinions and incidents, individuals and groups in every centre of population, would have required intensive and prolonged research which the writer was not in a position to carry out. The extra work would doubtless have made the history more comprehensive, but it is certain that the general conclusions arrived at would not have been modified seriously. Newspapers are generally regarded as an unreliable source of evidence, but in this case exception can perhaps be claimed for making extensive use of one paper, since it gave expression to working-class opinions without displaying the fanaticism of purely labour publications. Thanks are due to the Central Office of the Labour Party in Wellington for the courtesy of the officials in placing material at my disposal. It is unfortunate that some of this material, which may have been of considerable value, went astray in the post, and was not traced. Thanks must also be expressed to the Hon. John Rigg, who was helpful in supplying newspaper cuttings and reminiscences dealing with the Political Labour League, and to Mr. E.J. Howard, M.P. for valuable advice. In some cases likely people who were approached, while showing keen interest, seemed unable to rely on their memories for anything definite; one supplied suggestions which were of no use; another, from whom much was expected, did not reply at all. During the whole period of research what impressed one most was the dearth of published material on the subject and the scant attention paid to the movement in general in comprehensive works. This made the task of constructing general outlines as a basis for work very difficult. The investigation has suggested that the early organised labour parties in New Zealand were striving not so much for something they did not possess as to maintain certain privileges which they felt were slipping from their grasp. Their aim appears to have been not so much an emancipation from the present as a safeguard for the future. This, at least, is apparent to the mind of the writer, and it is hoped that his efforts may be of some use in clearing the mist which shrouds the infancy of labour in this country.

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  • The history of the first and second sessions of the fourth New Zealand parliament, 1866-1867.

    Gallagher, Halsey Alexander William (1938)

    Masters thesis
    University of Canterbury Library

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  • An account of the systematics, anatomy and bionomics of Austroperla Cyrene Newman.

    Margaret Sutcliffe, Thomson (1934)

    Masters thesis
    University of Canterbury Library

    The black stonefly Austroperla cyrene Newman (P11) is the most abundant insect of its order in New Zealand. A study of its anatomy and bionomics is of interest, firstly because of the primitive nature of the insect itself, and secondly in its relationship to the fauna of mountain streams, which is again correlated with the question of trout food.

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  • An investigation of the methods for the preparation of methyl chloroform and an attempted condensation of methyl chloroform with malonic ester

    Adams, A. F. R. (1936)

    Masters thesis
    University of Canterbury Library

    Since the reports of the methyl chloroform or 1.1.1 trichlorethane given by various early workers, the methods of preparation have received very little attention. The early reports are summarized in “Beilstein’s Handbuch der Organischen Chemie,” 4th edition. Vol. 1 p. 85. By the action of chlorine on ethylidene dichloride, methyl chloroform and other products are obtained (Regnault, Ann. 1840. 33. 317) and Stadel. 1879. 195. 184). The chlorination, in light, of ethylidene dichloride (1.1 dichlorethane) gives a mixture of 1.1.1. and 1.1.2. trichlorethanes (A. 1978. 368) p. 84. The chlorination of ethylidene dichloride in light is more difficult than the chlorination of ethylene dichloride, and gives as first products both 1.1.1. trichlorethane and 1.1.2. trichlorethane (D’Ans. Kautzch. J. Pr. Chem. 1909 (2). 80. 312; A, 1909 (1). 754).

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  • An investigation of the heterogeneous equilibria involved in the systems (a) potassium chloride - mercuric chloride -acetone at 25 degrees C; (b)potassium chloride - mercuric chloride - ethyl alcohol at 25 degrees C; (c) mercuric chloride - acetone - water at 25 degrees C and 35 degrees C

    Wilkins, G. J. (1937)

    Masters thesis
    University of Canterbury Library

    It has long been realised that the mercuric halides, as salts, possessed remarkable properties. They are readily soluble in non-ionising solvents, have low melting points, and their solutions even in hydroxylic solvents are but feebly ionised. These peculiarities have more recently been attributed to the extreme difficulty with which the two valence electrons are lost by a mercury atom to form an ion.

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  • Some deliquent boys at school : a study of the school progress and behaviour of a group of boys brought to official notice of on charges of deliquency.

    Mullan, Molly Isobel (1937)

    Masters thesis
    University of Canterbury Library

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  • The organised activities of Christchurch children outside the school.

    Hart, Edith Muriel (1936)

    Masters thesis
    University of Canterbury Library

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  • The geology of the Kakahu district, South Canterbury, New Zealand

    Maling, P. B. (1933)

    Masters thesis
    University of Canterbury Library

    The Kakahu district is situated in South Canterbury, some ten miles west of the township of Geraldine. The area here dealt with is bounded to the south and west by the Opihi and Opuha rivers respectively; while to the north it is bounded by a spur of the Four Peaks’ range stretching northwest from Waitohi Hill. To the east the area extends as far as Hilton, where the uppermost tertiary bds dip beneath the gravels of the South Canterbury plains. The Kakahu river is a tributary of the Hae-HaeTe Moana which rises on the Four Peaks’ range and flows in a south-easterly direction, joining the Opihi river shortly before the latter reaches the sea. The area dealt with covers practically the whole of the watershed of the Kakahu river. The district is readily accessible, being reached by good roads from Geraldine, Temuka, Pleasant Point, Raincliff and Fairlie.

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  • Studies in catalytic hydrogenation: the system HCN + 2H2=CH3NH2

    Barrer, R. M. (1931)

    Masters thesis
    University of Canterbury Library

    Chemistry owes much to the catalytic forces which effect otherwise difficulty accomplished reactions. To catalysis Organic Chemistry owes the Grignard reagents, which have been employed not only for a multitude of simpler syntheses but also for the more complex syntheses of carbohydrates (Paal. Ber, 1905, 38 1656; 1906,39,1301,2823, 2827) Frankland and Twiss J.C.S. 1905, 87, 864), of terpenss (Perkin J.C.S. 1907, 91, 480, Hesse Ber. 1909, 42, 1127, Mills and Bain J.C.S. 1910, 97, 1866) and of organo-silicon compounds (Kipping J.C.S. 1901 to 1909). Pope and Peachy effected resolutions of tin compounds with its aid. Chlorination is effected catalytically by suitable carriers. The Friedel and Crafte reaction is effected also by suitable halides. Numerous condensations such as the Benzoin condensation, the Aldol condensation, the Claisen condensation, and also esterification are catalytically effected. Equilibria between dynamic isomerides, in racemisation, and in mutarotation, are promoted by catalysis. Technical chemistry has, through catalysis, reversed the economic standing of nations. Cases in point are the synthesis of indigo, a stage in which is the catalytic oxidation of Napthalene by Sulphuric acid and Mercury, and the manufacture of sulphuric acids, of Ammonia and of Nitrates. The manufacture of synthetic petrols, power alcohols, and the new utilisations of coal depend entirely upon catalysts for their successful functioning. Analytical chemistry employs catalysts in processes of gas absorption such as addition of Uranyl Sulphate to Sulphuric Acid in the absorption of Ethylene (Lebeau and Damiens Compt. Rand. 1913, 156, 557) or of Corrosive Sublimate to alhaline Pyrogallol to accelerate the absorption of Oxygen. (Stassana, Compt. Rend. Soc. Biol. 1905, 58, 96). Also in Oxidation, such as the permanganate titration of iron in the presence of Hydrochloric and of Manganese Salts (Kessler. Pogg. Am. 1863, 118, 48; 119, 225), or the ability of Ferrous Sulphate to promote interaction between Potassium Persilphate and Potassium Iodide (Price Z Phys. Chem. 1898, 27, 474); and Reduction as in the employment of a Zinc-Copper Couple for the reduction of Chlorates to Chlorates (Thorpe and Eccles J.C.S. 1873, 26, 541; Bothamley and Thompson Ibid 1888, 53, 164). Catalysts are also employed in Organic analysis, as for example the use of colloidal platinum metals to convert Halogen compounds into Hydrogenated products and Halogen acid in the presence of Hydrogen (Borshe and Heimburger, Ber. 1915, 48, 452, 850). In Inorganic Chemistry a large number of reactions are catalytically accelerated. One of the best known is the decomposition of Potassium Chlorate in the Presence of Manganese Dioxide. Numerous catalyses are cited in the work of Dhar. (Ann. Chim. 11, 130-223, 1919). Hydrogen peroxide, another example of classical importance in chemical kinetics is decomposed by numerous agents, such as glass wool, salts of heavy metals, colloidal platinum. In Electrochemistry one may cite such examples as the addition of Fluorides in the preparation of Persulphates or percarbonates, (Muller and Friedberger, Z. Elektrochem., 1902, 8, 230), or the use of Lead Peroxide anodes in the oxidation of Chromates to Dichromates (Z. Elektrochem, 1905, 11, 863). Para-nitrotoluene with platinum anodes yields p-nitro-benzoic acid almost quantitatively. An enormous number of reactions is accelerated by radiant energy, according to photo chemical laws. A typical example is the union of Hydrogen and Chlorine, whose mechanism has occupied the attention of numerous workers. The photocatalytic combination of carbon-monoxide and Chlorine, of Sulphur Dioxide and Chlorine, of saturated, unsaturated, and aromatic hydro-carbons, and of acids (much as Acetic acid) and Chlorine furnish still further examples. Such reactions are further sensitive to the presence of ordinary material catalysts or anti-catalysts (See Griffiths and McKeowan, (“Photochemistry” p. 626.)

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  • A study of the binary system, aniline-o-chlorophenol

    Ellyett, C. D. (1936)

    Masters thesis
    University of Canterbury Library

    When two organic liquids are missed the resulting physical properties of the solution nearly always differ from those calculated on the assumption of an additive relationship. The extent of these deviations varies widely with the nature of the liquids chosen, and where there is a large evolution of heat it is considered that molecular compound formation has occurred. Some binary mixtures of phenols with aromatic bases have been investigated by Bramley (1) and are of this type. Macleod (2) has derived an expression for the viscosity of a binary mixture which has undergone volume change and compound formation. The expression contains the factor Ma/Mc, where Mc is the calculated mean molecular weight of the constituents and Ma is the actual mean molecular weight after mixing. By using Bramley’s density and viscosity results Macleod has evaluated Ma/Mc for the binary system aniline – o-chlorophenol. Bramley has determined the freezing-poing curve for this system, showing the existence of an equimolecular compound, and so Macleod has been able to calculate the number of double molecules required to give the ratio Ma/Mc. He has also calculated the equilibrium constants for a number of temperatures; using the amount of compound formation found from the viscosity formula at the equimolecular percentage and assuming the law of mass action to hold. The object of this work is a determination of the heats of reaction of this mixture at several temperatures, enabling the equilibrium constants to be calculated directly. The comparison of these constants with those obtained by Macleod from viscosity data should afford a check on his equation for the viscosity of binary mixtures. The formula for the calculation of the heat of reaction from the temperature rise necessitated knowledge of the specific heat of the mixture. It was therefore necessary to determine the specific heat curves at definite temperatures. These results, besides being necessary for the heats of reaction, also enables the partial molal heat capacities to be calculated. Further, so investigation of the literature shows that there are at present several different theories as to the nature of the link in this of compound. As the various theories depend partly upon the refractive index, it was decided to measure this property for the mixture. This work, together with refractive index measurements in hydrated mixtures, forms the second part of the thesis.

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  • The hydrolysis of salts of weak acids and weak bases

    Skelton, P. R. (1930)

    Doctoral thesis
    University of Canterbury Library

    It has shown, from theoretical considerations, by R. O. Griffiths (Trans. Faraday Soc. 17,525, 1922) that the classical derivation of an equation connecting the degree of hydrolysis of salts formed from weak acids and weak bases with the dissociation constants of the acid and base respectively, is based on an assumption which in valid for moderately dilute solutions and for moderately weak acids and bases only. In very dilute solutions, or when the acid or base is very weak, the classical equation breaks down. Tizard’s deduction (Trans. Chem. Soc. 97, p.2477, 1910) that the concentration of hydrogen ions in a solution of a weak salt is constant, whatever the dilution, is, for the same reason, in error when the concentration is very low, or when hydrolysis is nearly complete. In the classical treatment it is assumed that, on the hydrolysis of a weak salt (B.A.) the concentration of free undissociated acid, and of free undissociated base in solution are equal, the ionisation of these two components being regarded as negligible, wherein lies the fallacy. The existence of the above erroneous assumption in the classical treatment has also been pointed out by E.W. Hullett (in a thesis presented last year – as yet unpublished). Hullett arrived at the same conclusions as Griffiths (loc. cit.) but, whereas Griffiths merely showed the necessity for defining the degree of hydrolysis of a weak salt more explicitly, Hullett did assign a definite meaning to the degree of hydrolysis, and, moreover, derived equations with which, from electrometric measurements of hydrogen ion concentration, and from knowledge of the dissociation constant of either acid or the base, it is possible to calculate the degree of hydrolysis of weak salt.

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  • An analysis of the influence of religion and of religious movements upon the course of New Zealand history since 1814

    Andrews, S. G. (1935)

    Masters thesis
    University of Canterbury Library

    The aim of this thesis, explained more fully in the introductory chapter, is to discover and to discuss the occasions, events and movements in the history of New Zealand, which have been influenced by religious motives, prejudices and ideals. The writer has emphasized not so much the proof of a definite succession of causes and effects, but rather the discovery and the demonstration of several broad trends, through which the influence referred to has affected various phases of development in New Zealand from about 1814. In this field of historical research perhaps wore than in any other, there is a danger of passing unwarranted moral judgments upon the actions of historical characters. It is difficult to form a moral judgment upon the actions and beliefs of individuals and groups, which no longer exist, except perhaps in the memories of an older generation. It involves a knowledge and understanding of the spirit of the age under consideration, which could be attained fully only by one who was quickened by the same ideals and thrilled by the same emotions as moved those who are the subject of one's study. In such a research as this, it must also be constantly borne in mind that the religious motive was seldom, if ever, the sole cause of any event, and only occasionally was it the most important one. Briefly summarised, the scope of this thesis includes a short introductory chapter, enquiring into the relation between religion and history; a brief account of the main religious movements in Great Britain which affected the development of New Zealand, with which is associated a consideration of the religious aspect of Maori life up to 1814; the temporary and permanent influence of the missionary movements on the Maori people and on the introduction of British authority up to 1840; the place of religion in the life of the early colonists, and its influence on colonial affairs up to 1870; the relation of religion to the political, social educational and general development from 1870 to 1905; the relation of modern conditions and modern trends of thought in religion to the contemporary influence of religion upon the people, and a discussion in this light, continuing the theme of the preceding section as far as 1955; and finally, a brief review of the influence of the Jews in New Zealand in relation to the main theme. This makes seven chapters in all, followed by several appendices, including a map illustrating the geographical aspect of the work. The consideration of the sources of the information used brings us to the main difficulty. There is no dearth of information relevant to the main topic, but much of this is only incidentally treated in the various works. The main difficulty concerns the criticism of the sources. There has been no general work on the history of religion in New Zealand; there are detailed church histories, none of them very recent in date, such as the works of Jacobs and of Purchas on the Anglican Church, of Morley and of Williams on Methodism, of Dickson on Presbyterianism, of Wilson on Roman Catholicism, and so on. But these are denominational histories, valuable for their purpose, but open to criticism by the student of the religious influence on the development of New Zealand. These works, so far as they are relevant have been considered mainly in relation to the queries: “Is this matter concerned with the influence of religion?” “Does this evidence treat New Zealand as its unit?” Purely local events have been included only when they affect the history of New Zealand as a whole, as in the case of the South Island ecclesiastical settlements or the “Pai Marire” movement, or when they illustrate the geographical distribution of the influence of a religious body, as the details in Father Poupinel's letter on Roman catholic mission stations in 1864. The most valuable source referred to in connection with the early part of the work is Professor J. R. Elder's volume of the “Letters and Journals of Samule Marsden”, supplemented by his second work on “Marsden's Lieutenants”. The former work presents Marsden's letters and journals in an easily accessible form, so that the writer was able to appreciate the motives of the early missionary, and to acquire an understanding of the growing success of missionary work, as well as the realization of some inadequacies. Reference was also bad to contemporary writers and to the works of others on this period, but none was found quite so valuable as the work of Elder. For a critical analysis of the missionary influence, recourse was had to Martin's “Missionaries and Annexation in the Pacific”, a small volume which presents a viewpoint independent of religious prejudice. For the periods after 1840, apart from church histories and such biographies as that of Selwyn by Curteis, no works deal exclusively with religious topics. The general histories such as that of Rusden and the Australasian volume of the Cambridge History, of the British Empire were considered from two aspects: first, their attitude towards the religious bodies in the country: secondly, their attitude towards such problems as native policy, in the solution of which the religious factor was an important one. The Canterbury and Otago settlements were treated also in the light of the ecclesiastical conditions in England and Scotland, as outlined by standard historians. Of the social, educational and political movements of the later decades of the century, and of more recent times, each has its own distinctive literature. Cocker and Murray have edited a history of the prohibition movement; the Bible in schools League has issued many pamphlets, whose evidence has been carefully and critically considered in preparing the sections on the relation between religion and education. The parliamentary records give some indication of the trend of opinion as the decades pass. The more recent pronouncements of denominational leaders and thinkers have also been considered, when the section on the relation of religion to modern inventions (for instance, wireless) and the labour problem was being framed. For the chapter on the Jews, insight into the question was gained by the perusal of the results achieved in the research of Miss Violette F. Balkind, and the general information was gathered from many sources. The other main difficulty has been the maintenance of an unbiassed and interdenominational viewpoint. The denominational histories, besides being criticised had to be correlated, and the general religious attitude on any particular question bad to be evolved from the study of several different views. The only way of arriving at an interdenominational attitude has appeared to be the rejection of any feature not common to the majority of views considered. Any view quoted which is not that of the majority is definitely stated to be so. It is sometimes necessary to quote the viewpoint of a single church body, especially when this body has been the precursor, in whose steps the other religious bodies have followed. An example to illustrate this is the case of the prohibition movement up to the founding of the New Zealand Alliance in 1886. The writer has to acknowledge the courtesy of many friends who have directed him to sources of information, and of others who have given time to the discussion of problems with him; especially, mention should be made of the Hon. L. M. Isitt, M. L. C., who not only granted an interview, but supplied several useful items of evidence in the form of pamphlets on the question of religious instruction in state schools; of Mr. J. Malton Murray, who extended similar courtesy with regard to the prohibition movement; of the Christchurch “Press”, who assisted in locating information; and of the Rev. M. A. Rugby Pratt, who made available the minutes of past Methodist conferences for the verification of several obscure references to the relations between that denomination and the prohibition movement.

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  • The sodio derivatives of ethyl malonate

    Lorimer, A. E. (1930)

    Masters thesis
    University of Canterbury Library

    Ethyl malonate belongs to the class of tautomeric compounds which exist in more than one structural form in equilibrium with one another. Ethyl malonate consists almost wholly of the ketonic form I. [Diagram] and contains not more than one .01 per cent of the enolic form (II.,) as determined by the bromine addition method. (Abs. A.C.S. 7, 1913. 2864-9). The dio-enolic form (III) is therefore likely to be present in minute quantity only (if at all) in the free ester. A reagent which reacts with the enolic form (II) would remove it from the equilibrium, and so cause a change of (I) into (II) and finally give rise to a derivative of the form (II). Thus by addition of one molecule of sodium ethoxide to one molecule of malonic ester in alcoholic solution, the mono sodio derivative in which one hydrogen is replaced by sodium is readily obtained. (Conrad Ber. 12, 1879. 750).

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  • New Zealand - a mandatory power

    Ockenden, Muriel (1935)

    Masters thesis
    University of Canterbury Library

    At a time when New Zealand's attempts to govern peacefully the mandated territory of Western Samoa are giving rise to comments and contentions in many parts of the world, and when her ability and indeed her right to administer the islands are being questioned, it seems not unnatural to enquire why New Zealand should have been given a mandate over Western Samoa. To answer this question it is necessary to go back to an early period in New Zealand history and trace the thread up to and through the maze of complexities which constitute the peace negotiations of 1918-1919. We see New Zealand emerge from the Peace Conference with a C mandate, not exactly her heart's desire, but something very nearly akin. At this stage another thought arises; has the “sacred trust” been accepted gladly or has New Zealand chafed at the restrictions and obligations of the mandate? In this thesis I have endeavoured to depict the part played by New Zealand in the establishment and working of the mandates system, by a consideration of the motives underlying her policy at the Peace Conference, her expressed intentions in regard to Western Samoa, and her attitude towards the whole system as shown by official despatches, and official utterances made to the League, the New Zealand Parliament and elsewhere. An assessment of the merit or demerit of her performance as a mandatory power has been sought in the opinions expressed by the League organs whose task it is to supervise her work. I feel that the years during which she is a mandatory power will constitute an important phase in New Zealand history, for while occupying this position she is being tested, not only in regard to her capabilities in the sphere of native administration but, what is more vital, in her ability to respond to the new ideal of trusteeship which has somehow managed to survive in a world where exploitation is the rule, and which is making definite claims on behalf of Western Samoa to those who will hearken in New Zealand.

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  • Congregation of Our Lady of Mercy in New Zealand

    Gaughan, B. (1939)

    Masters thesis
    University of Canterbury Library

    Sisters of Mercy in our different dioceses have often expressed regret that, so far, no one has written a historical sketch of the Order of Mercy in New Zealand. Time is steadily stealing from our midst those who were privileged to enjoy personal acquaintance with the first religious women – the Auckland Sisters of Mercy of 1850 - to come to this country. So, while there yet remain with us, five of the original band who in 1878 founded the first Convent of Mercy in the South Island, I have attempted to break the ice, however feebly, and thus free the current for more competent explorers. Owing to the lack of a central authority for the Order, the collecting of sources and other data has entailed much more research than one might infer from the size of the work. A considerable amount of detail was necessary but I have endeavoured to so use it as not to lose sight of the vivifying spirit of mercy, which embraces even the least works of the Order.

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  • A phase rule investigation of the three component system BaO - Ac₂O - H₂O at 50 ℃

    Blick, R. T. J. (1936)

    Masters thesis
    University of Canterbury Library

    The materials of Group IIA in the Periodic Table show a slight tendency to form complexes and hydrates, though this tendency becomes less marked on passing to the heavier elements of the Group. Increasing tendency to form hydrates is accompanied by increasing solubility of the salts in water, except in the cases of salts of the weak acids, in which cases the solubilities decrease. Thus one is led to expect some evidence of complex formation and hydration in the case of barium salts, but less marked than members of the Group of lower atomic weight would be expected to show. Salts produced by reaction of a weak acid like acetic acid , with a strong base like barium oxide, might be expected to hydrolyse in aqueous solutions. Reference to the literature on barium acetate, and acetic acid showed that work had been carried out bearing on the system BaO - Ac₂O - H₂O.

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  • The catalytic effect of acids on the rate of racemisation of 1-trans-α,γ-dimethylglutaconic acid ; The attempted resolution of α,β-dimethyl- and α,α,β-trimethyl-glutaconic acids. A preliminary investigation of decolorization of inferior honey

    Fitzgerald, J. S. F. (1931)

    Masters thesis
    University of Canterbury Library

    With the optical resolution of trans- (“normal”) αγ-dimethylglutaconic acid by McCombs, Packer and Thorpe (J.C.S. (1931) 134 547 – a reprint of this paper is attached) the question as to whether this compound should be represented as having a “normal” form (I) as has been held by Thorpe, or the conventional formula (II), was settled in favour of the latter. [Diagram] Since the “normal” formula is essentially symmetrical, the formula (II) (trans- configuration) is the only one on which all the properties of the acid may be explained.

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  • The methylation of the dimethyl glutaconic esters

    Hutchinson, R. L. (1935)

    Masters thesis
    University of Canterbury Library

    Up till recent times the glutaconic acids have presented a considerable problem in Organic Chemistry. One of the chief difficulties lay in the fact that those glutaconic acids possessing a hydrogen atom with potential three carbon mobility differed widely in their properties from those in which this type of hydrogen atom is absent, and also from those in which its movement is prevented by the saturation of the double bonds.

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  • The catalytic effect of alkalies on the rate of racemisation of 1-trans-αγ-dimethylglutaconic acid

    Bull, Joan E. (1933)

    Masters thesis
    University of Canterbury Library

    The mechanism of racemisation of 1-trans-αγ-dimethyl-glutaconic acid has been discussed by Thorpe in his Presidential Address to the Chemical Society (J.C.S., (1931) 134, 1011) where he suggests that the glutaconic acids are an example of cis-trans stereoisomerism modified by the special conditions attached to three carbon isomerism considered on the modern ionisation theory. Packer and Thorpe (J.S.C. (1926) 129, 1199) arrived at the conclusion that in symmetrically αγ-substituted glutaconic acids isomeric forms underwent the following changes – [Diagram] Since there is a tendency for like groups to take up positions as far apart as possible the traps form will show a greater tendency to interconversions (racemisation) than will the cis forms and this change may occur to the entire exclusion of the cis forms. Tautoneric change in the three-carbon system is represented by Thorpe as taking place by the removal of the mobile hydrogen ion as proton, giving a symmetrical glutaconic ion (III) which is probably only a passing phase in electromerisation.

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  • The thermodynamic dissociation constants of oxalic acid in water

    Gibbons, R. C. (1937)

    Masters thesis
    University of Canterbury Library

    The values given in literature for the first and second dissociation constants of oxalic acid at 25°C. vary considerably. For the first dissociation constant some of the vales given are; .038 (Chandler, by conductivity); .17 (Britton, by electrimeric titration; .057 (Drucker); 0.59 (Gane and Ingold, by electromeric titration), and .02 (GLastone), which do not show good agreement. Fir the second dissociation constant, values are; 4.9 x 10-⁵ (Chandler); 6.9 x 10-⁵ (Drucker), 13.8 x 10-⁵ (Britton), 6.4 x 10-⁵ (Gane and Ingold), 3 x 10-⁵ (Glastone) and 5 x 10-⁵ (Pilbrick) which also show poor agreement. In the present work an endeavour is made to determine by an accurate thermodynamic method the true second dissociation constant of oxalic acid at 25°C, 30°C, and 35°C. and the true first dissociation constant at 25°C.

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