A study of irradiation effects in solids
- Authors: Brown, Michael Ewart
- Date: 1966
- Subjects: Decomposition (Chemistry) , Crystals -- Thermal properties , Oxalates -- Thermal properties , Solids -- Effect of radiation on
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4509 , http://hdl.handle.net/10962/d1013387
- Description: One of the primary objects of this research was to determine, if possible, the nature of the radiation damage prior to thermal decomposition. The X-ray study has not wholly achieved this although more information has been derived from it than from similar work on AgMnO₄ However, the diffuse reflections obtained do indicate, quite strongly, the creation of point defects during irradiation. This is of value since such assumptions have been made in the explanation of the kinetics of decomposition of a number of irradiated solids (BaN₆,CaN₆). In addition the X-ray work has suggested future research which should produce useful information; namely, a precise study of the diffuse reflections. Another object of the research was to attempt to determine what characteristics, if any, of the kinetics of the decomposition of an unirradiated solid would predetermine a marked irradiation effect. It is obvious that the type of nuclear growth which occurs e.g. branching chain, or power law, does not characterise a substance with regard to a possible irradiation effect . The photosensitivity, or otherwise, also does not determine whether there will be an irradiation effect. However, the one property that the substances which have been studied, have in common, is a polyatomic anion, but here again ammonium dichromate does not show an acceleration of the decomposition after irradiation. Consequently it is considered that it is not possible to say, a priori, whether a solid will undergo an accelerated decomposition after irradiation. Each new solid, unless it belongs to a particular class e.g. the alkaline earth azides , must be considered afresh. Nevertheless it does appear that the irradiation effect can take two forms: - (i) the production of an unstable compound e.g. nickel oxalate, the decomposition of which affects the normal pyrolysis; and (ii) the production of point defects which determine the nature of the subsequent thermal decomposition e.g . CaN₆ . It is possible that the effect requires an interaction of the created point defects with the existing line defects.
- Full Text:
- Date Issued: 1966
- Authors: Brown, Michael Ewart
- Date: 1966
- Subjects: Decomposition (Chemistry) , Crystals -- Thermal properties , Oxalates -- Thermal properties , Solids -- Effect of radiation on
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4509 , http://hdl.handle.net/10962/d1013387
- Description: One of the primary objects of this research was to determine, if possible, the nature of the radiation damage prior to thermal decomposition. The X-ray study has not wholly achieved this although more information has been derived from it than from similar work on AgMnO₄ However, the diffuse reflections obtained do indicate, quite strongly, the creation of point defects during irradiation. This is of value since such assumptions have been made in the explanation of the kinetics of decomposition of a number of irradiated solids (BaN₆,CaN₆). In addition the X-ray work has suggested future research which should produce useful information; namely, a precise study of the diffuse reflections. Another object of the research was to attempt to determine what characteristics, if any, of the kinetics of the decomposition of an unirradiated solid would predetermine a marked irradiation effect. It is obvious that the type of nuclear growth which occurs e.g. branching chain, or power law, does not characterise a substance with regard to a possible irradiation effect . The photosensitivity, or otherwise, also does not determine whether there will be an irradiation effect. However, the one property that the substances which have been studied, have in common, is a polyatomic anion, but here again ammonium dichromate does not show an acceleration of the decomposition after irradiation. Consequently it is considered that it is not possible to say, a priori, whether a solid will undergo an accelerated decomposition after irradiation. Each new solid, unless it belongs to a particular class e.g. the alkaline earth azides , must be considered afresh. Nevertheless it does appear that the irradiation effect can take two forms: - (i) the production of an unstable compound e.g. nickel oxalate, the decomposition of which affects the normal pyrolysis; and (ii) the production of point defects which determine the nature of the subsequent thermal decomposition e.g . CaN₆ . It is possible that the effect requires an interaction of the created point defects with the existing line defects.
- Full Text:
- Date Issued: 1966
An examination of the extractives of Leonotis species
- Authors: Kaplan, Errol R
- Date: 1966
- Subjects: Leonotis -- Analysis Botanical chemistry Chemistry, Analytic Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4481 , http://hdl.handle.net/10962/d1012628
- Description: Marrubiin and the other two diterpenoids, compounds X and Y, which had previously been isolated from Leonotus leonurus have been reinvestigated. Although the structure for marrubiin is well known its stereochemistry has been the subject of protracted discussion and is by no means secure except at C₅ and C₁₀ . N.M.R. spectral evidence showed that the lactone ring was cis-fused and β-orientated. Dehydration experiments carried out by previous workers were repeated, in order to resolve the residual uncertainty regarding the stereochemistry at C₉, an attempt was made to prepare iodoacetyl marrubic acid for X-ray crystallographic studies. Compound Y, C₂₀H₂₈0₃, a triply-unsaturated compound was shown by spectral studies to contain a furan ring and an α,β- unsaturated keto-group. It possesses a hydroxyl group incapable of acetylation, but readily removed by alkali and dehydrating agents to yield a tetraunsaturated compound, anhydro~Y; the hydroxyl is thus tertiary, Isolation of 1:2:5-trimethylnaphthalene on dehydrogenation indicated a relationship with the labdane diterpene group and supported the C₂₀ formula, The position of the α,β-unsaturated keto-group was resolved by interpretation of the ultraviolet spectra of degradation products and also by isolation of 1:2:3:5- trimethylnaphthalene on dehydrogenation of a suitable grignard product, The presence of a β-substituted furan was further indicated by colour reactions and confirmed by mass and n.m.r. spectra. The skeleton of compound Y is correlated with marrubiin via "iso-ambreinolide " and its stereochemistry is discussed. Further stereochemical assignments are postulated from the study of the n.m.r. spectra. Compound X, C₂₀H₂₈0₅, was shown by spectral and chemical evidence to be a diterpenoid dilactone containing an ether bridge between C₉ and C₁₃ Isolation of 1:2:5 trimethylnaphthal ene on dehydrogenation showed it to be closely related to marrubiin, This was supported by n.m.r. spectral results. A structure for compound X is proposed and the stereochemistry discussed. The aerial portions of Leonotis leonitis were also extracted and shown to contain a new compound, compound R. Preliminary investigation showed that it was a dilactone containing a furan ring, The n.m.r. spectrum of the compound is discussed.
- Full Text:
- Date Issued: 1966
- Authors: Kaplan, Errol R
- Date: 1966
- Subjects: Leonotis -- Analysis Botanical chemistry Chemistry, Analytic Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4481 , http://hdl.handle.net/10962/d1012628
- Description: Marrubiin and the other two diterpenoids, compounds X and Y, which had previously been isolated from Leonotus leonurus have been reinvestigated. Although the structure for marrubiin is well known its stereochemistry has been the subject of protracted discussion and is by no means secure except at C₅ and C₁₀ . N.M.R. spectral evidence showed that the lactone ring was cis-fused and β-orientated. Dehydration experiments carried out by previous workers were repeated, in order to resolve the residual uncertainty regarding the stereochemistry at C₉, an attempt was made to prepare iodoacetyl marrubic acid for X-ray crystallographic studies. Compound Y, C₂₀H₂₈0₃, a triply-unsaturated compound was shown by spectral studies to contain a furan ring and an α,β- unsaturated keto-group. It possesses a hydroxyl group incapable of acetylation, but readily removed by alkali and dehydrating agents to yield a tetraunsaturated compound, anhydro~Y; the hydroxyl is thus tertiary, Isolation of 1:2:5-trimethylnaphthalene on dehydrogenation indicated a relationship with the labdane diterpene group and supported the C₂₀ formula, The position of the α,β-unsaturated keto-group was resolved by interpretation of the ultraviolet spectra of degradation products and also by isolation of 1:2:3:5- trimethylnaphthalene on dehydrogenation of a suitable grignard product, The presence of a β-substituted furan was further indicated by colour reactions and confirmed by mass and n.m.r. spectra. The skeleton of compound Y is correlated with marrubiin via "iso-ambreinolide " and its stereochemistry is discussed. Further stereochemical assignments are postulated from the study of the n.m.r. spectra. Compound X, C₂₀H₂₈0₅, was shown by spectral and chemical evidence to be a diterpenoid dilactone containing an ether bridge between C₉ and C₁₃ Isolation of 1:2:5 trimethylnaphthal ene on dehydrogenation showed it to be closely related to marrubiin, This was supported by n.m.r. spectral results. A structure for compound X is proposed and the stereochemistry discussed. The aerial portions of Leonotis leonitis were also extracted and shown to contain a new compound, compound R. Preliminary investigation showed that it was a dilactone containing a furan ring, The n.m.r. spectrum of the compound is discussed.
- Full Text:
- Date Issued: 1966
The thermal decomposition of mercuric oxalate and inorganic azides
- Authors: Moore, D J
- Date: 1966
- Subjects: Decomposition (Chemistry) , Oxalates -- Thermal properties , Mercuric Oxide -- Azides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4483 , http://hdl.handle.net/10962/d1012878
- Description: The chemical reactivity of a solid is influenced to a marked degree by the presence of imperfections or defects in the solid. Bond strengths are considerably weaker at points of imperfection than elsewhere in the solid, and hence the initiation of reaction is favoured at these sites due to the relative ease of bond rupture. Line defects, such as edge or screw dislocations, jogs, Smekul cracks etc, are of prime importance in such changes. The surface of a solid or in intergranular boundaries, where a state of strain exists, are also favourable places for the initiation of a reaction, Point defects e.g. vacancies or interstitialions or atoms also play important roles in chemical change, often in conjuction with line defects.
- Full Text:
- Date Issued: 1966
- Authors: Moore, D J
- Date: 1966
- Subjects: Decomposition (Chemistry) , Oxalates -- Thermal properties , Mercuric Oxide -- Azides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4483 , http://hdl.handle.net/10962/d1012878
- Description: The chemical reactivity of a solid is influenced to a marked degree by the presence of imperfections or defects in the solid. Bond strengths are considerably weaker at points of imperfection than elsewhere in the solid, and hence the initiation of reaction is favoured at these sites due to the relative ease of bond rupture. Line defects, such as edge or screw dislocations, jogs, Smekul cracks etc, are of prime importance in such changes. The surface of a solid or in intergranular boundaries, where a state of strain exists, are also favourable places for the initiation of a reaction, Point defects e.g. vacancies or interstitialions or atoms also play important roles in chemical change, often in conjuction with line defects.
- Full Text:
- Date Issued: 1966
Prototypes of black wattle tannins and their stereochemistry
- Authors: Drewes, Siegfried Ernst
- Date: 1963
- Subjects: Tannins -- Anthocyanidis Stereochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4460 , http://hdl.handle.net/10962/d1011437
- Description: A number of interrelated flavonoid compounds, present in trace quantities in mature black wattle (Acacia mearnsii De Wild) bark, have been isolated and identified for the first time. They include a) the resorcinol-pyrogallol analogues, (+)-leuco-robinetinidin (7,5',4',5'-tetrahydroxyflavan-3,4-diol), dihydrorobinetin (7,5',4',5'-tetrahydroxyflavan-3-ol-4-one) and robtein (2',4',5,4,5- pentahydroxychalcone) and b) the resorcinol-catechol analogues, (+)-leuco-fisetinidin (7,3',4'-trihydroxyflavan-3,4-diol), fustin (7,3',4'-trihydroxyflavan-3-ol-4-one), (-)-fisetinidol (7,3',4'trihydroxyflavan- 3-ol), butein (2',4',3,4-tetrahydroxychalcone) and butin (7,5',4'-trihydroxyflavan-4-one). In addition, two flavonol glycosides, myricitrin (3,5,7,3',4',5'-hexahydroxyflavone-3-rhamnoside ) and quercitrin (5,5,7,5',4'-pentahydroxyflavone-3-rhamnoside), which belong to the phloroglucinol-pyrogallol and phloroglucinolcatechol class of flavonoids respectively, were isolated from immature bark. These represent the only glycosides isolated hitherto from wattle bark or heartwood extracts. Summary, p. i.
- Full Text:
- Date Issued: 1963
- Authors: Drewes, Siegfried Ernst
- Date: 1963
- Subjects: Tannins -- Anthocyanidis Stereochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4460 , http://hdl.handle.net/10962/d1011437
- Description: A number of interrelated flavonoid compounds, present in trace quantities in mature black wattle (Acacia mearnsii De Wild) bark, have been isolated and identified for the first time. They include a) the resorcinol-pyrogallol analogues, (+)-leuco-robinetinidin (7,5',4',5'-tetrahydroxyflavan-3,4-diol), dihydrorobinetin (7,5',4',5'-tetrahydroxyflavan-3-ol-4-one) and robtein (2',4',5,4,5- pentahydroxychalcone) and b) the resorcinol-catechol analogues, (+)-leuco-fisetinidin (7,3',4'-trihydroxyflavan-3,4-diol), fustin (7,3',4'-trihydroxyflavan-3-ol-4-one), (-)-fisetinidol (7,3',4'trihydroxyflavan- 3-ol), butein (2',4',3,4-tetrahydroxychalcone) and butin (7,5',4'-trihydroxyflavan-4-one). In addition, two flavonol glycosides, myricitrin (3,5,7,3',4',5'-hexahydroxyflavone-3-rhamnoside ) and quercitrin (5,5,7,5',4'-pentahydroxyflavone-3-rhamnoside), which belong to the phloroglucinol-pyrogallol and phloroglucinolcatechol class of flavonoids respectively, were isolated from immature bark. These represent the only glycosides isolated hitherto from wattle bark or heartwood extracts. Summary, p. i.
- Full Text:
- Date Issued: 1963
A comparative study of the catechin components in the barks of wattle species related to Acacia Mernsii
- Authors: Maihs, Edwin Alfred
- Date: 1962
- Subjects: Wattles (Plants) Acacia mearnsii Acacia
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4482 , http://hdl.handle.net/10962/d1012793
- Description: The distribution of flavonoid constituents in the barks of Acacia mearnsii De Wild.(black wattle) , A· decurens Willd. (green wattle), A. dealbata Link.(silver wattle) and A. pycnantha Benth.(golden wattle) has been studied. Bark extracts of the four wattle species have been fractionated into low molecular weight fractions containing mainly catechins and other low molecular weight constituents, and high molecular weight fractions containing the bulk of the polymerized tannins. The low molecular weight fractions have been further fractionated by "preparative paper chromatography". (-)-Robinetinidol, (-)-7:3': 4': 5'-tetrahydroxy flavan- 3-ol, a new naturally occurring catechin, (+)-catechin and (+)-gallocatechin have been isolated from the barks of A. mearnsii, A. dealbata and A. pycnantha. (-)-Epicatechin and (-)-epigallocatechin have been identified in the bark extracts of A. dealbata and A. pycnantha, but appeared to be absent in the barks of A. mearnsii and A. decurrens. (-)-Epicatechin has been isolated fron A. dealbata, and both (-}-epicatechin and (-)-epigallocatechin were isolated from A. pycnantha. (-)-Epicatechin gallate, (-)-epigallocatechin gallate and gallic acid were isolated from A. pycnantha only. These three constituents appeared to be absent in the barks of the three other wattle species. (-)-Epigallocatechin, (-)-epicatechin gallate and (-)-epigallocatechin gallate which were not available for direct comparison, were subsequently isolated from green tea where they are present as major phenolic constituents. A method for the quantitative estimation of polyphenolic substances on two dimensional paper chromatograms has been developed, and a photoelectric densitometer constructed. Two spray reagents, ammoniacal silver nitrate and bisdiazotised benzidine, were found to give straight line relationships of instrument deflection against log concentration for flavonoid substances. This estimation method for the first time supplied means for a detailed study of the concentration of catechin constituents in the bark extracts of A. mearnsii, A. decurrens, A. dealbata, A. pycnantha and of A. mearnsii x A. decurrens hybrids. The concentration of catechin constituents has been shown to vary considerably between species whereas variation within species was small. In the latter respect silver wattle is an exception. Taxonomic significance may possibly be attached to the distribution of catechin constituents in the bark of the four Acacia species. The concentration of (-)-robinetinidol, which appears to be the characteristic compound of these Acacias, progressively decreases in the sequence black-, black x green hybrid, green-, silver- and golden wattle, while the number of catechin constituents of the "phloroglucinol series" increases in the same sequence. It thus appears, that by the examination of their bark components, a differentiation between species of a subgenera may be possible. Two tannins, constituents D and B, which are related to the leuco-anthocyanidins (flavan-3:4-diols) have been found in the barks of the four wattle species. One of the two, constituent D, was isolated in a pure form from the barks of A. mearnsii and A. pycnantha. Constituent D was found to generate robinetinidin and an orange pigment, the structure of which has not yet been fully identified. Compound D and its acetyl- and methoxyl derivatives did not crystallize. From the results of alkaline-, acidic- and enzymatic degradations, colour reactions and light-absorption studies, combustion analysis of the compound and its derivatives and molecular weight estimations, constituent D is surmised to be a dimer of 7:3': 4': 5'-tetrahydroxyflavan-3:4-diol (leuco-robinetinidin), The isolation of this complex leuco-anthocyanidin tannin represents the first isolation of a flavonoid tannin from commercial vegetable tannin sources. The second tannin obtained from the bark of A.mearnsii, "constituent B" appears to consist of two overlapping substances, which have not yet been separated. The tannin (B) was found to have an average molecular weight of 676 and it is considered likely that both substances may be dimolecular. On heating with mineral acid robinetinidin, fisetinidin and an orange pigment are generated, the pigment being identical with the pigment generated from constituent D. It may therefore be assumed that "Constituent B" consists of a mixture of complex leuco-robinetinidins and leucofisetinidins. The distribution of complex leuco-anthocyanidins in the bark extracts of Acacia mearnsii, A. decurrens, A. dealbata and A. pycnantha has been examined. A correlation between the distribution of leuco-anthocyanidins in the bark of the four wattle species, and accepted systematics, does not, apparently, exist.
- Full Text:
- Date Issued: 1962
- Authors: Maihs, Edwin Alfred
- Date: 1962
- Subjects: Wattles (Plants) Acacia mearnsii Acacia
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4482 , http://hdl.handle.net/10962/d1012793
- Description: The distribution of flavonoid constituents in the barks of Acacia mearnsii De Wild.(black wattle) , A· decurens Willd. (green wattle), A. dealbata Link.(silver wattle) and A. pycnantha Benth.(golden wattle) has been studied. Bark extracts of the four wattle species have been fractionated into low molecular weight fractions containing mainly catechins and other low molecular weight constituents, and high molecular weight fractions containing the bulk of the polymerized tannins. The low molecular weight fractions have been further fractionated by "preparative paper chromatography". (-)-Robinetinidol, (-)-7:3': 4': 5'-tetrahydroxy flavan- 3-ol, a new naturally occurring catechin, (+)-catechin and (+)-gallocatechin have been isolated from the barks of A. mearnsii, A. dealbata and A. pycnantha. (-)-Epicatechin and (-)-epigallocatechin have been identified in the bark extracts of A. dealbata and A. pycnantha, but appeared to be absent in the barks of A. mearnsii and A. decurrens. (-)-Epicatechin has been isolated fron A. dealbata, and both (-}-epicatechin and (-)-epigallocatechin were isolated from A. pycnantha. (-)-Epicatechin gallate, (-)-epigallocatechin gallate and gallic acid were isolated from A. pycnantha only. These three constituents appeared to be absent in the barks of the three other wattle species. (-)-Epigallocatechin, (-)-epicatechin gallate and (-)-epigallocatechin gallate which were not available for direct comparison, were subsequently isolated from green tea where they are present as major phenolic constituents. A method for the quantitative estimation of polyphenolic substances on two dimensional paper chromatograms has been developed, and a photoelectric densitometer constructed. Two spray reagents, ammoniacal silver nitrate and bisdiazotised benzidine, were found to give straight line relationships of instrument deflection against log concentration for flavonoid substances. This estimation method for the first time supplied means for a detailed study of the concentration of catechin constituents in the bark extracts of A. mearnsii, A. decurrens, A. dealbata, A. pycnantha and of A. mearnsii x A. decurrens hybrids. The concentration of catechin constituents has been shown to vary considerably between species whereas variation within species was small. In the latter respect silver wattle is an exception. Taxonomic significance may possibly be attached to the distribution of catechin constituents in the bark of the four Acacia species. The concentration of (-)-robinetinidol, which appears to be the characteristic compound of these Acacias, progressively decreases in the sequence black-, black x green hybrid, green-, silver- and golden wattle, while the number of catechin constituents of the "phloroglucinol series" increases in the same sequence. It thus appears, that by the examination of their bark components, a differentiation between species of a subgenera may be possible. Two tannins, constituents D and B, which are related to the leuco-anthocyanidins (flavan-3:4-diols) have been found in the barks of the four wattle species. One of the two, constituent D, was isolated in a pure form from the barks of A. mearnsii and A. pycnantha. Constituent D was found to generate robinetinidin and an orange pigment, the structure of which has not yet been fully identified. Compound D and its acetyl- and methoxyl derivatives did not crystallize. From the results of alkaline-, acidic- and enzymatic degradations, colour reactions and light-absorption studies, combustion analysis of the compound and its derivatives and molecular weight estimations, constituent D is surmised to be a dimer of 7:3': 4': 5'-tetrahydroxyflavan-3:4-diol (leuco-robinetinidin), The isolation of this complex leuco-anthocyanidin tannin represents the first isolation of a flavonoid tannin from commercial vegetable tannin sources. The second tannin obtained from the bark of A.mearnsii, "constituent B" appears to consist of two overlapping substances, which have not yet been separated. The tannin (B) was found to have an average molecular weight of 676 and it is considered likely that both substances may be dimolecular. On heating with mineral acid robinetinidin, fisetinidin and an orange pigment are generated, the pigment being identical with the pigment generated from constituent D. It may therefore be assumed that "Constituent B" consists of a mixture of complex leuco-robinetinidins and leucofisetinidins. The distribution of complex leuco-anthocyanidins in the bark extracts of Acacia mearnsii, A. decurrens, A. dealbata and A. pycnantha has been examined. A correlation between the distribution of leuco-anthocyanidins in the bark of the four wattle species, and accepted systematics, does not, apparently, exist.
- Full Text:
- Date Issued: 1962
The spectrochemical determination of certain minor trace elements in plant material
- Authors: Eve, Desmond John
- Date: 1961
- Subjects: Trace elements Spectrum analysis Plants -- Analysis Plants -- Effect of trace elements on Trace elements in agriculture
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4469 , http://hdl.handle.net/10962/d1011773
- Description: A study has been made of three organic complexing reagents , namely dithizone, oxine and cupferron with a view to developing suitable methods for the separation and concentration of Zn, Co, Ni, Pb, Cu, Mn, Ti , V and Mo prior to the spectrometric determination of their concentrations. In particular the influence of pH on the chloroform extraction of ditihizonates, oxinates and cupferrates from aqueous tartrate and citrate solutions and the separation of iron by oxine extraction has been investigated. The development of a method for the chemical concentration and spectrcgraphic determination of Zn, Co, Ni, Pb, Ti, V and Mo is described and the possibility of determining Nn and Cu flame photometrically as part of the analysis scheme is demonstrated. A specially designed slide rule for the calculation of spectrographic results is described. A direct reading spectrometric method for the determination of Zn, Pb and Cu in plant material is presented. The analysis of plant ash for zinc using the 2138 . 6A spectrum line has been studied and a simple, rapid analysis method is described.
- Full Text:
- Date Issued: 1961
- Authors: Eve, Desmond John
- Date: 1961
- Subjects: Trace elements Spectrum analysis Plants -- Analysis Plants -- Effect of trace elements on Trace elements in agriculture
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4469 , http://hdl.handle.net/10962/d1011773
- Description: A study has been made of three organic complexing reagents , namely dithizone, oxine and cupferron with a view to developing suitable methods for the separation and concentration of Zn, Co, Ni, Pb, Cu, Mn, Ti , V and Mo prior to the spectrometric determination of their concentrations. In particular the influence of pH on the chloroform extraction of ditihizonates, oxinates and cupferrates from aqueous tartrate and citrate solutions and the separation of iron by oxine extraction has been investigated. The development of a method for the chemical concentration and spectrcgraphic determination of Zn, Co, Ni, Pb, Ti, V and Mo is described and the possibility of determining Nn and Cu flame photometrically as part of the analysis scheme is demonstrated. A specially designed slide rule for the calculation of spectrographic results is described. A direct reading spectrometric method for the determination of Zn, Pb and Cu in plant material is presented. The analysis of plant ash for zinc using the 2138 . 6A spectrum line has been studied and a simple, rapid analysis method is described.
- Full Text:
- Date Issued: 1961
A statistical study of the errors involved in the sampling and chemical analysis of soils and plants, with particular reference to citrus and pineapples
- Steyn, Willem Johannes Abraham
- Authors: Steyn, Willem Johannes Abraham
- Date: 1958
- Subjects: Soil chemistry , Plants -- Analysis , Soils -- Analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4506 , http://hdl.handle.net/10962/d1013291
- Description: 1. Accurate and reproducible methods for the determination of N and acid- extractable P in soils are described. The variations in N, P, and K found by intensive sampling of three different soil types are presented. 3. Suggestions for the adequate sampling of soils for various purposes arc given. 4. A study is presented of the preparative stages in leaf analysis (washing, drying, grinding and storage) as applied to citrus and pineapple leaf material. Likely errors are pointed out and procedures whereby these may be minimised are described. 5. A reliable wet-ashing procedure for obtaining leaf solutions is described. 6. Accurate and reproducible methods for the determination of total N, P,. K, Ca, Mg, Na, Fe, Mn, Zn and Cu in citrus and pineapple leaves are presented. 7. It is shown that diurnal variations in nutrient concentrations occur in citrus and pineapple leaves. 8. The variations in N, P, K, Ca, Mg, Na, Fe, Mn, Zn and Cu, occurring from tree to tree in 3 different Navel orange blocks are presented. It is shown that if all these elements are to be represented . to within 10% of the mean values on a 19 : 1 probability level, all the trees in the blocks would have to be sampled. Reasonable sampling procedures for various purposes are suggested. 9. The variations in N, P, K, Ca, Mg, Fe, Mn, Zn and Cu, occurring in 3 different Cayenne pineapple plantations are presented and described. Suitable sampling procedures are suggested.
- Full Text:
- Date Issued: 1958
- Authors: Steyn, Willem Johannes Abraham
- Date: 1958
- Subjects: Soil chemistry , Plants -- Analysis , Soils -- Analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4506 , http://hdl.handle.net/10962/d1013291
- Description: 1. Accurate and reproducible methods for the determination of N and acid- extractable P in soils are described. The variations in N, P, and K found by intensive sampling of three different soil types are presented. 3. Suggestions for the adequate sampling of soils for various purposes arc given. 4. A study is presented of the preparative stages in leaf analysis (washing, drying, grinding and storage) as applied to citrus and pineapple leaf material. Likely errors are pointed out and procedures whereby these may be minimised are described. 5. A reliable wet-ashing procedure for obtaining leaf solutions is described. 6. Accurate and reproducible methods for the determination of total N, P,. K, Ca, Mg, Na, Fe, Mn, Zn and Cu in citrus and pineapple leaves are presented. 7. It is shown that diurnal variations in nutrient concentrations occur in citrus and pineapple leaves. 8. The variations in N, P, K, Ca, Mg, Na, Fe, Mn, Zn and Cu, occurring from tree to tree in 3 different Navel orange blocks are presented. It is shown that if all these elements are to be represented . to within 10% of the mean values on a 19 : 1 probability level, all the trees in the blocks would have to be sampled. Reasonable sampling procedures for various purposes are suggested. 9. The variations in N, P, K, Ca, Mg, Fe, Mn, Zn and Cu, occurring in 3 different Cayenne pineapple plantations are presented and described. Suitable sampling procedures are suggested.
- Full Text:
- Date Issued: 1958
A conductimetric investigation of phenomena in extremely dilute aqueous solutions
- Authors: Faure, Pierre Knobel
- Date: 1957
- Subjects: Adsorption , Solution (Chemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4524 , http://hdl.handle.net/10962/d1014891
- Description: 1. The apparatus used in this investigation is fully described, and a new method is outlined for the calibration of bridge resistances "in situ". 2. A chart is given for the accurate correction of weights in air to weights in vacuum for a range of temperatures extending from 10° to 28°C, and for pressures from 690 to 730 mm. 3. An automatic recycling still has been designed for the continuous production of "ultra-pure" water. This still is capable of delivering daily, in routine operation, 16 l. of water of conductivity less than 100 nm/cm after aeration with "C0₂- and NH₃-free" air. 4. A very soluble layer appears to form on the surface of' glass when it is dried; this layer is readily removed on contact with water. 5. The removal of carbon dioxide and of ammonia from aqueous solution by aeration with an indifferent gas has been fully investigated, and it has been shown that these gases can be completely eliminated by such a process. Whereas the carbon dioxide is removed fairly rapidly, however, the ammonia, whether present alone or together with carbon dioxide, only goes out of solution rather slowly. 6. It has been shown that ammonia is adsorbed from aqueous solution on the glass walls of the cell. 7. There does not appear to be any ammonium bicarbonate in the residual impurity left in the "ultra-pure" water obtained from the still; the impurity can, in fact, be regarded as neutral salt with sufficient accuracy for most purposes. 8. The resistance change which accompanies any variation in the rate of bubbling of the stirring gas through the water has been investigated, but no solution has been found as to the cause of this change. 9. A comparison has been made of the efficiency of different gases for stirring purposes, and it seems that, for general work, nitrogen is by far the most suitable of the common gases. 10. The extrapolation to be used for converting resistances to their values at infinite frequency appears ...
- Full Text:
- Date Issued: 1957
- Authors: Faure, Pierre Knobel
- Date: 1957
- Subjects: Adsorption , Solution (Chemistry)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4524 , http://hdl.handle.net/10962/d1014891
- Description: 1. The apparatus used in this investigation is fully described, and a new method is outlined for the calibration of bridge resistances "in situ". 2. A chart is given for the accurate correction of weights in air to weights in vacuum for a range of temperatures extending from 10° to 28°C, and for pressures from 690 to 730 mm. 3. An automatic recycling still has been designed for the continuous production of "ultra-pure" water. This still is capable of delivering daily, in routine operation, 16 l. of water of conductivity less than 100 nm/cm after aeration with "C0₂- and NH₃-free" air. 4. A very soluble layer appears to form on the surface of' glass when it is dried; this layer is readily removed on contact with water. 5. The removal of carbon dioxide and of ammonia from aqueous solution by aeration with an indifferent gas has been fully investigated, and it has been shown that these gases can be completely eliminated by such a process. Whereas the carbon dioxide is removed fairly rapidly, however, the ammonia, whether present alone or together with carbon dioxide, only goes out of solution rather slowly. 6. It has been shown that ammonia is adsorbed from aqueous solution on the glass walls of the cell. 7. There does not appear to be any ammonium bicarbonate in the residual impurity left in the "ultra-pure" water obtained from the still; the impurity can, in fact, be regarded as neutral salt with sufficient accuracy for most purposes. 8. The resistance change which accompanies any variation in the rate of bubbling of the stirring gas through the water has been investigated, but no solution has been found as to the cause of this change. 9. A comparison has been made of the efficiency of different gases for stirring purposes, and it seems that, for general work, nitrogen is by far the most suitable of the common gases. 10. The extrapolation to be used for converting resistances to their values at infinite frequency appears ...
- Full Text:
- Date Issued: 1957
Measurements of the solubilities of some silver halides in water by electrical methods
- Authors: Malan, George McPherson
- Date: 1955
- Subjects: Silver halides -- Solubility , Silver halides -- Analysis , Conductometric analysis , Potentiometry , Silver halides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4515 , http://hdl.handle.net/10962/d1013502
- Description: [Introduction, p. 3] The solubilities of the silver halides cannot be determined by the conventional methods of analytical chemistry because they are too sparingly soluble (of the order 1 x 10⁻⁵ to 1 x 10⁻⁶ g . equiv./1. at 25°C.) However, electrical, and to a lesser extent optical methods, are admirably suited because of their greater sensitivity. The conductometric and potentiometric methods are the two most important electrical techniques for the measurement of the solubilities of sparingly soluble salts, and are the ones employed in this research. There are large discrepancies between the published values for the solubility of silver chloride. Results obtained by the conductometric and potentiometric methods disagree. In addition, figures quoted by independent authors using the same method differ by as much as 15%.
- Full Text:
- Date Issued: 1955
- Authors: Malan, George McPherson
- Date: 1955
- Subjects: Silver halides -- Solubility , Silver halides -- Analysis , Conductometric analysis , Potentiometry , Silver halides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4515 , http://hdl.handle.net/10962/d1013502
- Description: [Introduction, p. 3] The solubilities of the silver halides cannot be determined by the conventional methods of analytical chemistry because they are too sparingly soluble (of the order 1 x 10⁻⁵ to 1 x 10⁻⁶ g . equiv./1. at 25°C.) However, electrical, and to a lesser extent optical methods, are admirably suited because of their greater sensitivity. The conductometric and potentiometric methods are the two most important electrical techniques for the measurement of the solubilities of sparingly soluble salts, and are the ones employed in this research. There are large discrepancies between the published values for the solubility of silver chloride. Results obtained by the conductometric and potentiometric methods disagree. In addition, figures quoted by independent authors using the same method differ by as much as 15%.
- Full Text:
- Date Issued: 1955
Some measurements of the conductivities of dilute potassium chloride solutions
- Authors: Faure, Abraham
- Date: 1954
- Subjects: Potassium chloride
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4471 , http://hdl.handle.net/10962/d1011787
- Description: A constant temperature room has been constructed in which the thermoregulator is controlled by a temperature-sensitive resistance. A thermostat has been constructed in which the 0 temperature is controlled to within 0.001°C. A precision conductance bridge has been built in a very convenient form. Improvements include the replacement of the telephone as null detector by a cathode ray oscilloscope, and the use of a resistance-capacity phase-shift oscillator, which gives a good wave-form. An automatic recycling conductance water still has been built which regularly gives water with a conductivity less than 0.09 micromhos per cm. The conductivities of dilute KCl solutions have been measured, taking special care to prevent errors due to the adsorption of KCl on the surface of glass. Two cells were used for these measurements : a modified Jones cell, and a special conductimetric titration cell. The modified Jones cell has given results in good agreement with the generally-accepted values. The results of the conductimetric titration cell do not agree well with the generally-accepted values; the greatest difference (for the most dilute solution) is 0.4%. The reason for this is not known.
- Full Text:
- Date Issued: 1954
- Authors: Faure, Abraham
- Date: 1954
- Subjects: Potassium chloride
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4471 , http://hdl.handle.net/10962/d1011787
- Description: A constant temperature room has been constructed in which the thermoregulator is controlled by a temperature-sensitive resistance. A thermostat has been constructed in which the 0 temperature is controlled to within 0.001°C. A precision conductance bridge has been built in a very convenient form. Improvements include the replacement of the telephone as null detector by a cathode ray oscilloscope, and the use of a resistance-capacity phase-shift oscillator, which gives a good wave-form. An automatic recycling conductance water still has been built which regularly gives water with a conductivity less than 0.09 micromhos per cm. The conductivities of dilute KCl solutions have been measured, taking special care to prevent errors due to the adsorption of KCl on the surface of glass. Two cells were used for these measurements : a modified Jones cell, and a special conductimetric titration cell. The modified Jones cell has given results in good agreement with the generally-accepted values. The results of the conductimetric titration cell do not agree well with the generally-accepted values; the greatest difference (for the most dilute solution) is 0.4%. The reason for this is not known.
- Full Text:
- Date Issued: 1954
The chemistry of naturally occurring long chain unsaturated compounds
- Authors: Silk, M H
- Date: 1954
- Subjects: Compounds, Unsaturated
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4518 , http://hdl.handle.net/10962/d1014332
- Description: [From Introduction, p. 3] Raw marine oils are subject to considerable variation in composition with season and are moreover very unbalanced oils for direct use in the paint industry. Further refining is undertaken chiefly by Messrs Marine Oil Refiners of Africa Ltd., whose factory is situated at Simonstown. In their plant marine oils and others are treated by the Solexol process involving counter current extraction of the oil with liquid propane in a tower over which a temperature gradient is maintained. The process achieves the removal of a large proportion of the relatively saturated glycerides, the natural antitioxidants, and the relatively highly unsaturated components, all of which are detrimental to the eventual formation of good paint films. The segregated marine oil from the Solexol process is then bodied or polymerised at high temperatures to yield a "drying oil" which is used as a substitute for bodied linseed oil in paints. The chemical reactions taking place during the polymerisation and drying of these oils are of an exemely complex nature, and for their understanding it is necessary to have an accurate knowledge of the chemical nature of the component fatty acids in the natural glycerides ... The term "marine oils" in this work should be understood to mean marine fish body oils, marine mammal oils being excluded from consideration.
- Full Text:
- Date Issued: 1954
- Authors: Silk, M H
- Date: 1954
- Subjects: Compounds, Unsaturated
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4518 , http://hdl.handle.net/10962/d1014332
- Description: [From Introduction, p. 3] Raw marine oils are subject to considerable variation in composition with season and are moreover very unbalanced oils for direct use in the paint industry. Further refining is undertaken chiefly by Messrs Marine Oil Refiners of Africa Ltd., whose factory is situated at Simonstown. In their plant marine oils and others are treated by the Solexol process involving counter current extraction of the oil with liquid propane in a tower over which a temperature gradient is maintained. The process achieves the removal of a large proportion of the relatively saturated glycerides, the natural antitioxidants, and the relatively highly unsaturated components, all of which are detrimental to the eventual formation of good paint films. The segregated marine oil from the Solexol process is then bodied or polymerised at high temperatures to yield a "drying oil" which is used as a substitute for bodied linseed oil in paints. The chemical reactions taking place during the polymerisation and drying of these oils are of an exemely complex nature, and for their understanding it is necessary to have an accurate knowledge of the chemical nature of the component fatty acids in the natural glycerides ... The term "marine oils" in this work should be understood to mean marine fish body oils, marine mammal oils being excluded from consideration.
- Full Text:
- Date Issued: 1954
The chemistry of the wattle tannins
- Authors: Roux, David Gerhardus
- Date: 1953
- Subjects: Tannin plants , Tannins , Wattles (Plants)
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: vital:4492 , http://hdl.handle.net/10962/d1013098
- Description: Four species of acacia of Auatralian origin are associated with the wattle industry in South Africa. Black wattle, Acacia mollissima willd., is the most important of these and is today almost exclusively cultivated. The tree grows successfully only in a limited area of rich soil and high rainfall and is easily affected by adverse conditions caused by insect pests, frost damage and drought. Expansion of the area under cultivation is therefore, not feasible, although the world demand for vegetable extracts far exceeds the available supply. The remaining species such as green (Acacia decurrrens willd.) and silver wattles (Acacia dealbata Link.) possess many desirable characteristics which resist such adverse factors. Their barks, however, give reddish extracts, which are considered unsuitable for tannery usage because of the red colour they impart to the leather. Hybridisation studies, involving the crossing of green and silver wattle with the black, and aimed at produc1ng progenies containing many of the desirable characterlstics of the parent plants, are thus a natural result and have been in progress for a considerable period. Summary, p. i.
- Full Text:
- Date Issued: 1953
- Authors: Roux, David Gerhardus
- Date: 1953
- Subjects: Tannin plants , Tannins , Wattles (Plants)
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: vital:4492 , http://hdl.handle.net/10962/d1013098
- Description: Four species of acacia of Auatralian origin are associated with the wattle industry in South Africa. Black wattle, Acacia mollissima willd., is the most important of these and is today almost exclusively cultivated. The tree grows successfully only in a limited area of rich soil and high rainfall and is easily affected by adverse conditions caused by insect pests, frost damage and drought. Expansion of the area under cultivation is therefore, not feasible, although the world demand for vegetable extracts far exceeds the available supply. The remaining species such as green (Acacia decurrrens willd.) and silver wattles (Acacia dealbata Link.) possess many desirable characteristics which resist such adverse factors. Their barks, however, give reddish extracts, which are considered unsuitable for tannery usage because of the red colour they impart to the leather. Hybridisation studies, involving the crossing of green and silver wattle with the black, and aimed at produc1ng progenies containing many of the desirable characterlstics of the parent plants, are thus a natural result and have been in progress for a considerable period. Summary, p. i.
- Full Text:
- Date Issued: 1953