An investigation of ISO/IEC 27001 adoption in South Africa
- Authors: Coetzer, Christo
- Date: 2015
- Subjects: ISO 27001 Standard , Information technology -- Security measures , Computer security , Data protection
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4720 , http://hdl.handle.net/10962/d1018669
- Description: The research objective of this study is to investigate the low adoption of the ISO/IEC 27001 standard in South African organisations. This study does not differentiate between the ISO/IEC 27001:2005 and ISO/IEC 27001:2013 versions, as the focus is on adoption of the ISO/IEC 27001 standard. A survey-based research design was selected as the data collection method. The research instruments used in this study include a web-based questionnaire and in-person interviews with the participants. Based on the findings of this research, the organisations that participated in this study have an understanding of the ISO/IEC 27001 standard; however, fewer than a quarter of these have fully adopted the ISO/IEC 27001 standard. Furthermore, the main business objectives for organisations that have adopted the ISO/IEC 27001 standard were to ensure legal and regulatory compliance, and to fulfil client requirements. An Information Security Management System management guide based on the ISO/IEC 27001 Plan-Do-Check-Act model is developed to help organisations interested in the standard move towards ISO/IEC 27001 compliance.
- Full Text:
- Date Issued: 2015
- Authors: Coetzer, Christo
- Date: 2015
- Subjects: ISO 27001 Standard , Information technology -- Security measures , Computer security , Data protection
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4720 , http://hdl.handle.net/10962/d1018669
- Description: The research objective of this study is to investigate the low adoption of the ISO/IEC 27001 standard in South African organisations. This study does not differentiate between the ISO/IEC 27001:2005 and ISO/IEC 27001:2013 versions, as the focus is on adoption of the ISO/IEC 27001 standard. A survey-based research design was selected as the data collection method. The research instruments used in this study include a web-based questionnaire and in-person interviews with the participants. Based on the findings of this research, the organisations that participated in this study have an understanding of the ISO/IEC 27001 standard; however, fewer than a quarter of these have fully adopted the ISO/IEC 27001 standard. Furthermore, the main business objectives for organisations that have adopted the ISO/IEC 27001 standard were to ensure legal and regulatory compliance, and to fulfil client requirements. An Information Security Management System management guide based on the ISO/IEC 27001 Plan-Do-Check-Act model is developed to help organisations interested in the standard move towards ISO/IEC 27001 compliance.
- Full Text:
- Date Issued: 2015
Understanding development aid and state autonomy : the case of European Union budget support to Mozambique
- Authors: Ndlovu, Ana Admiração
- Date: 2014
- Subjects: Economic assistance, European -- Mozambique , Economic development -- Mozambique , Mozambique -- Economic conditions , Autonomy , Budget -- Mozambique
- Language: English
- Type: Thesis , Masters , MSocSc
- Identifier: vital:3378 , http://hdl.handle.net/10962/d1013218
- Description: Post-colonial states in Africa continue to pursue nation-building and socio-economic development. This process is taking place with the sustained support of global agencies in terms of development cooperation, assistance and aid. Insofar as an endogenous development path which speaks to national priorities can be formulated and implemented by post-colonial states, their relationship with these agencies raises serious questions about such a path if the relationship entails dependence and indeed subordination of post-colonial states. This raises important questions about state autonomy under post-colonial conditions and the possibility of autonomy being compromised. In this light, the thesis examines European Union budget support to Mozambique and, in particular, the relationship between EU budget support and Mozambique state autonomy in pursuing national development. This is particularly pertinent given the massive dependence of the Mozambican state on foreign funding (notably EU funding) with specific regard to the national budget. Despite the broad claims existing in the prevailing literature that nation-state autonomy is seriously undermined in and through the international development system, the thesis argues against reductionist arguments that simply posit post-colonial states as mere instruments of global forces. This system, including European Union budget support, does indeed set the conditions of existence for post-colonial states such as Mozambique. But autonomy is necessarily relative and is subject to different forms and degrees. Ultimately, it is through empirical investigation that the specific form and degree of autonomy can be pinpointed and understood. The thesis contributes to this endeavour and suggests that the relationship between European budget support and Mozambican state autonomy is more complex and tension-riddled than the prevailing literature would seem to suggest.
- Full Text:
- Date Issued: 2014
- Authors: Ndlovu, Ana Admiração
- Date: 2014
- Subjects: Economic assistance, European -- Mozambique , Economic development -- Mozambique , Mozambique -- Economic conditions , Autonomy , Budget -- Mozambique
- Language: English
- Type: Thesis , Masters , MSocSc
- Identifier: vital:3378 , http://hdl.handle.net/10962/d1013218
- Description: Post-colonial states in Africa continue to pursue nation-building and socio-economic development. This process is taking place with the sustained support of global agencies in terms of development cooperation, assistance and aid. Insofar as an endogenous development path which speaks to national priorities can be formulated and implemented by post-colonial states, their relationship with these agencies raises serious questions about such a path if the relationship entails dependence and indeed subordination of post-colonial states. This raises important questions about state autonomy under post-colonial conditions and the possibility of autonomy being compromised. In this light, the thesis examines European Union budget support to Mozambique and, in particular, the relationship between EU budget support and Mozambique state autonomy in pursuing national development. This is particularly pertinent given the massive dependence of the Mozambican state on foreign funding (notably EU funding) with specific regard to the national budget. Despite the broad claims existing in the prevailing literature that nation-state autonomy is seriously undermined in and through the international development system, the thesis argues against reductionist arguments that simply posit post-colonial states as mere instruments of global forces. This system, including European Union budget support, does indeed set the conditions of existence for post-colonial states such as Mozambique. But autonomy is necessarily relative and is subject to different forms and degrees. Ultimately, it is through empirical investigation that the specific form and degree of autonomy can be pinpointed and understood. The thesis contributes to this endeavour and suggests that the relationship between European budget support and Mozambican state autonomy is more complex and tension-riddled than the prevailing literature would seem to suggest.
- Full Text:
- Date Issued: 2014
The use of Landsat ETM imagery as a suitable data capture source for alien acacia species for the WFW programme
- Authors: Cobbing, Benedict Louis
- Date: 2007
- Subjects: Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4856 , http://hdl.handle.net/10962/d1005532 , Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Description: Geographic Information System technology today allows for the rapid analysis of vast amounts of spatial and non-spatial data. The power of a GIS can only be effected with the rapid collection of accurate input data. This is particularly true in the case of the South African National Working for Water (WFW) Programme where large volumes of spatial data on alien vegetation infestations are captured throughout the country. Alien vegetation clearing contracts cannot be generated, for WFW, without this data, so that the accurate capture of such data is crucial to the success of the programme. Mapping Invasive Alien Plant (IAP) data within WFW is a perennial problem (Coetzee, pers com, 2002), because not enough mapping is being done to meet the annual requirements of the programme in the various provinces. This is re-iterated by Richardson, 2004, who states that there is a shortage of accurate data on IAP abundance in South Africa. Therefore there is a need to investigate alternate methods of data capture; such as remote sensing, whilst working within the existing WFW data capture standards. The aim of this research was to investigate the use of Landsat ETM imagery as a data capture source for mapping alien vegetation for the WFW Programme in terms of their approved mapping methods, for both automated and manual classification techniques. The automated and manual classification results were compared to control data captured by differential Global Positioning Systems (DGPS). The research tested the various methods of data capture using Landsat ETM images over a range of study sites of varying complexity: a simple grassland area, a medium complexity grassy fynbos site and a complicated indigenous forest site. An important component of the research was to develop a mapping (classification) Ranking System based upon variables identified by WFW as fundamental in data capture decision making: spatial and positional accuracy, time constraints and cost constraints for three typical alien invaded areas. The mapping Ranking System compared the results of the various mapping methods for each factor for the study sites against each other. This provided an indication of which mapping method is the most efficient or suitable for a particular area.
- Full Text:
- Date Issued: 2007
- Authors: Cobbing, Benedict Louis
- Date: 2007
- Subjects: Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4856 , http://hdl.handle.net/10962/d1005532 , Geographic information systems , Global Positioning System , Landsat satellites , Agriculture -- Remote sensing , Geography -- Remote sensing
- Description: Geographic Information System technology today allows for the rapid analysis of vast amounts of spatial and non-spatial data. The power of a GIS can only be effected with the rapid collection of accurate input data. This is particularly true in the case of the South African National Working for Water (WFW) Programme where large volumes of spatial data on alien vegetation infestations are captured throughout the country. Alien vegetation clearing contracts cannot be generated, for WFW, without this data, so that the accurate capture of such data is crucial to the success of the programme. Mapping Invasive Alien Plant (IAP) data within WFW is a perennial problem (Coetzee, pers com, 2002), because not enough mapping is being done to meet the annual requirements of the programme in the various provinces. This is re-iterated by Richardson, 2004, who states that there is a shortage of accurate data on IAP abundance in South Africa. Therefore there is a need to investigate alternate methods of data capture; such as remote sensing, whilst working within the existing WFW data capture standards. The aim of this research was to investigate the use of Landsat ETM imagery as a data capture source for mapping alien vegetation for the WFW Programme in terms of their approved mapping methods, for both automated and manual classification techniques. The automated and manual classification results were compared to control data captured by differential Global Positioning Systems (DGPS). The research tested the various methods of data capture using Landsat ETM images over a range of study sites of varying complexity: a simple grassland area, a medium complexity grassy fynbos site and a complicated indigenous forest site. An important component of the research was to develop a mapping (classification) Ranking System based upon variables identified by WFW as fundamental in data capture decision making: spatial and positional accuracy, time constraints and cost constraints for three typical alien invaded areas. The mapping Ranking System compared the results of the various mapping methods for each factor for the study sites against each other. This provided an indication of which mapping method is the most efficient or suitable for a particular area.
- Full Text:
- Date Issued: 2007
A study of carbonate-rich brines from Sua Pan to characterize organic contaminants in the soda ash process
- Authors: Joseph, Manjusha
- Date: 2001
- Subjects: Sua Pan Soda Ash Project -- Botswana , Sodium carbonate -- Research , Biotic communities , Organic compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4031 , http://hdl.handle.net/10962/d1004091 , Sua Pan Soda Ash Project -- Botswana , Sodium carbonate -- Research , Biotic communities , Organic compounds
- Description: Botswana Ash (Pty) Ltd which is situated in Sua Pan, north east Bostwana, is one of Africa's largest suppliers of salt and soda ash. For a number of years, the company has been experiencing problems which have resulted in the final soda ash product being contaminated and discoloured. The problems experienced at Sua Pan have been reported also to occur in other salt works all over the world. It has been suggested that contamination in many salt works could be possibly be due to the microbial activity by halophilic algae and bacteria that grow in the solar ponds. This study was undertaken to investigate the nature of the contaminating organic compounds present in the brine, to identify the compounds, and to establish how these components vary during the various stages of the soda ash processing. For this study, two sets of brine samples were used; the first set was collected before the summer rains and the second set was collected after the summer rains. Solid bicarbonate and soda ash samples were also used. Extractions, desalting, UV and HPLC analysis and oxidative biotransformations using four enzymes, were used for developing profiles and characterizing the brine components. From these studies, we were able to confirm that the components of the brine are organic in nature. A thorough study of one of the compounds isolated,from solid bicarbonate and soda ash was conducted using UV, HPLC, IR, NMR, HPLC-MS, GC-MS and TLC. The results of these analyses, show that the. isolated compound was benzyl butyl phthalate which is generally regarded to be humic in nature. This compound was found to be present in all the brine samples collected after the summer rains including the well brine, suggesting this compound occurs naturally and is not formed during the processing.
- Full Text:
- Date Issued: 2001
- Authors: Joseph, Manjusha
- Date: 2001
- Subjects: Sua Pan Soda Ash Project -- Botswana , Sodium carbonate -- Research , Biotic communities , Organic compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4031 , http://hdl.handle.net/10962/d1004091 , Sua Pan Soda Ash Project -- Botswana , Sodium carbonate -- Research , Biotic communities , Organic compounds
- Description: Botswana Ash (Pty) Ltd which is situated in Sua Pan, north east Bostwana, is one of Africa's largest suppliers of salt and soda ash. For a number of years, the company has been experiencing problems which have resulted in the final soda ash product being contaminated and discoloured. The problems experienced at Sua Pan have been reported also to occur in other salt works all over the world. It has been suggested that contamination in many salt works could be possibly be due to the microbial activity by halophilic algae and bacteria that grow in the solar ponds. This study was undertaken to investigate the nature of the contaminating organic compounds present in the brine, to identify the compounds, and to establish how these components vary during the various stages of the soda ash processing. For this study, two sets of brine samples were used; the first set was collected before the summer rains and the second set was collected after the summer rains. Solid bicarbonate and soda ash samples were also used. Extractions, desalting, UV and HPLC analysis and oxidative biotransformations using four enzymes, were used for developing profiles and characterizing the brine components. From these studies, we were able to confirm that the components of the brine are organic in nature. A thorough study of one of the compounds isolated,from solid bicarbonate and soda ash was conducted using UV, HPLC, IR, NMR, HPLC-MS, GC-MS and TLC. The results of these analyses, show that the. isolated compound was benzyl butyl phthalate which is generally regarded to be humic in nature. This compound was found to be present in all the brine samples collected after the summer rains including the well brine, suggesting this compound occurs naturally and is not formed during the processing.
- Full Text:
- Date Issued: 2001
Minimal motion capture with inverse kinematics for articulated human figure animation
- Authors: Casanueva, Luis
- Date: 2000
- Subjects: Virtual reality , Image processing -- Digital techniques
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4620 , http://hdl.handle.net/10962/d1006485 , Virtual reality , Image processing -- Digital techniques
- Description: Animating an articulated figure usually requires expensive hardware in terms of motion capture equipment, processing power and rendering power. This implies a high cost system and thus eliminates the use of personal computers to drive avatars in virtual environments. We propose a system to animate an articulated human upper body in real-time, using minimal motion capture trackers to provide position and orientation for the limbs. The system has to drive an avatar in a virtual environment on a low-end computer. The cost of the motion capture equipment must be relatively low (hence the use of minimal trackers). We discuss the various types of motion capture equipment and decide to use electromagnetic trackers which are adequate for our requirements while being reasonably priced. We also discuss the use of inverse kinematics to solve for the articulated chains making up the topology of the articulated figure. Furthermore, we offer a method to describe articulated chains as well as a process to specify the reach of up to four link chains with various levels of redundancy for use in articulated figures. We then provide various types of constraints to reduce the redundancy of non-defined articulated chains, specifically for chains found in an articulated human upper body. Such methods include a way to solve for the redundancy in the orientation of the neck link, as well as three different methods to solve the redundancy of the articulated human arm. The first method involves eliminating a degree of freedom from the chain, thus reducing its redundancy. The second method calculates the elevation angle of the elbow position from the elevation angle of the hand. The third method determines the actual position of the elbow from an average of previous positions of the elbow according to the position and orientation of the hand. The previous positions of the elbow are captured during the calibration process. The redundancy of the neck is easily solved due to the small amount of redundancy in the chain. When solving the arm, the first method which should give a perfect result in theory, gives a poor result in practice due to the limitations of both the motion capture equipment and the design. The second method provides an adequate result for the position of the redundant elbow in most cases although fails in some cases. Still it benefits from a simple approach as well as very little need for calibration. The third method provides the most accurate method of the three for the position of the redundant elbow although it also fails in some cases. This method however requires a long calibration session for each user. The last two methods allow for the calibration data to be used in latter session, thus reducing considerably the calibration required. In combination with a virtual reality system, these processes allow for the real-time animation of an articulated figure to drive avatars in virtual environments or for low quality animation on a low-end computer.
- Full Text:
- Date Issued: 2000
- Authors: Casanueva, Luis
- Date: 2000
- Subjects: Virtual reality , Image processing -- Digital techniques
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4620 , http://hdl.handle.net/10962/d1006485 , Virtual reality , Image processing -- Digital techniques
- Description: Animating an articulated figure usually requires expensive hardware in terms of motion capture equipment, processing power and rendering power. This implies a high cost system and thus eliminates the use of personal computers to drive avatars in virtual environments. We propose a system to animate an articulated human upper body in real-time, using minimal motion capture trackers to provide position and orientation for the limbs. The system has to drive an avatar in a virtual environment on a low-end computer. The cost of the motion capture equipment must be relatively low (hence the use of minimal trackers). We discuss the various types of motion capture equipment and decide to use electromagnetic trackers which are adequate for our requirements while being reasonably priced. We also discuss the use of inverse kinematics to solve for the articulated chains making up the topology of the articulated figure. Furthermore, we offer a method to describe articulated chains as well as a process to specify the reach of up to four link chains with various levels of redundancy for use in articulated figures. We then provide various types of constraints to reduce the redundancy of non-defined articulated chains, specifically for chains found in an articulated human upper body. Such methods include a way to solve for the redundancy in the orientation of the neck link, as well as three different methods to solve the redundancy of the articulated human arm. The first method involves eliminating a degree of freedom from the chain, thus reducing its redundancy. The second method calculates the elevation angle of the elbow position from the elevation angle of the hand. The third method determines the actual position of the elbow from an average of previous positions of the elbow according to the position and orientation of the hand. The previous positions of the elbow are captured during the calibration process. The redundancy of the neck is easily solved due to the small amount of redundancy in the chain. When solving the arm, the first method which should give a perfect result in theory, gives a poor result in practice due to the limitations of both the motion capture equipment and the design. The second method provides an adequate result for the position of the redundant elbow in most cases although fails in some cases. Still it benefits from a simple approach as well as very little need for calibration. The third method provides the most accurate method of the three for the position of the redundant elbow although it also fails in some cases. This method however requires a long calibration session for each user. The last two methods allow for the calibration data to be used in latter session, thus reducing considerably the calibration required. In combination with a virtual reality system, these processes allow for the real-time animation of an articulated figure to drive avatars in virtual environments or for low quality animation on a low-end computer.
- Full Text:
- Date Issued: 2000
An investigation into the use of IEEE 1394 for audio and control data distribution in music studio environments
- Authors: Laubscher, Robert Alan
- Date: 1999 , 2011-11-10
- Subjects: Digital electronics , Sound -- Recording and reproducing -- Digital techniques , MIDI (Standard) , Music -- Data processing , Computer sound processing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4619 , http://hdl.handle.net/10962/d1006483 , Digital electronics , Sound -- Recording and reproducing -- Digital techniques , MIDI (Standard) , Music -- Data processing , Computer sound processing
- Description: This thesis investigates the feasibility of using a new digital interconnection technology, the IEEE-1394 High Performance Serial Bus, for audio and control data distribution in local and remote music recording studio environments. Current methods for connecting studio devices are described, and the need for a new digital interconnection technology explained. It is shown how this new interconnection technology and developing protocol standards make provision for multi-channel audio and control data distribution, routing, copyright protection, and device synchronisation. Feasibility is demonstrated by the implementation of a custom hardware and software solution. Remote music studio connectivity is considered, and the emerging standards and technologies for connecting future music studio utilising this new technology are discussed. , Microsoft Word , Adobe Acrobat 9.46 Paper Capture Plug-in
- Full Text:
- Date Issued: 1999
- Authors: Laubscher, Robert Alan
- Date: 1999 , 2011-11-10
- Subjects: Digital electronics , Sound -- Recording and reproducing -- Digital techniques , MIDI (Standard) , Music -- Data processing , Computer sound processing
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4619 , http://hdl.handle.net/10962/d1006483 , Digital electronics , Sound -- Recording and reproducing -- Digital techniques , MIDI (Standard) , Music -- Data processing , Computer sound processing
- Description: This thesis investigates the feasibility of using a new digital interconnection technology, the IEEE-1394 High Performance Serial Bus, for audio and control data distribution in local and remote music recording studio environments. Current methods for connecting studio devices are described, and the need for a new digital interconnection technology explained. It is shown how this new interconnection technology and developing protocol standards make provision for multi-channel audio and control data distribution, routing, copyright protection, and device synchronisation. Feasibility is demonstrated by the implementation of a custom hardware and software solution. Remote music studio connectivity is considered, and the emerging standards and technologies for connecting future music studio utilising this new technology are discussed. , Microsoft Word , Adobe Acrobat 9.46 Paper Capture Plug-in
- Full Text:
- Date Issued: 1999
A comparative kinetic study of the reaction between chromium nitrate solutions and the carboxyl groups of acetate and collage
- Authors: Russell, Allan Edward
- Date: 1962
- Subjects: Chemical kinetics , Chromium , Spectrophotometry , Electrophoresis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4493 , http://hdl.handle.net/10962/d1013101
- Description: The kinetics of the coordination reaction between the carboxyl group of the acetate radical and the trivalent chromium ion has been examined by independent methods at a temperature selected to yield reasonably accurate rate data. The study has been extended to an examination of the rate of chromium "fixation" by the carboxyl groups of hide collagen in a series of miniature tannages carried out under similar conditions for comparative purposes. The effect of olation of the chromium ions in solution on the kinetics of t he coordination reaction has also been examined. The rate of coordination of the acetate radical was followed by solvent extraction and spectrophotometric techniques over a range of concentration and pH levels. The rate data revealed a reaction having typical mass-action characteristics, the rate of reaction depending on the concentration levels of the chromium ion and the ionised acetate radical. An attempt made to distinguish a differential reaction rate in the case of a parallel reaction series using boiled and aged chromium nitrate reactant solutions, failed to reveal any significant differences between the series. The reactant solutions gave absorption spectra characteristic of the trivalent chromium ion with maxima in the 420 mµ and 570 mµ wavelength regions. The changes in optical density occurring in the vicinity of the maxima were followed spectrophotometrically, the height of the 570 mµ being found to increase during the course of reaction, while the height of the 420 mµ peak decreased. The variation in optical density at the 570 mµ peak was found to be directly related to the increase in concentration of the product complex in solution in accordance with the Baer-Bougher law, while the decrease in the height of the 420 mµ peak was related to the properties of unolated OH groups associated with the chromium complex as governed by pH and olation changes during the course of reaction. Boiled and aged chromium nitrate solutions gave reactant solutions having initial optical densities greater than those of the correspending fresh reactant solutions at the 570 mµ peak, and less than those of the fresh solutions at the 420 mµ peak. During the course of reaction, however, the two series converged to the same values. The equilibrium reaction solutions were subjected to paper electrophoretic study which indicated that all tho chromium was present in the form of cationic species. This finding was in accordance with stoicheiometric indications in the solvent extraction studies where coordination in a l : 1 ratio was reflected, giving rise to positively charged complex ions only. Making due allowance for band spreading the numbers of species predicted from the kinetic studies correspond with the electrophoretic patterns found. Application of the classical second order kinetic expression to the solvent extraction rate data, yielded plots having two distinctly linear sections, apparently indicating consecutive second order processes occurring in solution, contrary to the findings of previous workers who assign a first order mechanism to the reaction. This finding was consistent with the view that in the case of both the fresh and aged series, reaction consisted of successive coordination of an acetate radical to each chromium atom of a diol complex. Second order rate "constants" were calculated for each step and their dependency on pH level demonstrated. The findings of Hamm et al that these were first order reactions independent of acetate co'ncentration are believed to be due to their use of a large excess of acetate in their experiments. The kinetic study was further extended to an examination of the rate of "fixation"of trivalent chromium by the carboxyl groups of hide collagen under comparable conditions in a series of miniaturv tanning experiments in which the tannage substrate was provided in each of two physical forms:- (a) As hide powder where surface development was large, and (b) as prepared pelt pieces in which the fibrous weave pattern was retained. In view of the heterogeneity of the tannage systems, remarkable similarity was observed in the reaction course when compared with that of the acetate coordination studies, particularly in the case of the hide powder tannages. The dependency of the tannage rate data upon concentration and pH conditions was also found to be the same as in the case of the pure chemical system. The exact correlation between the rate data for the tannage and pure chemical systems was demonstrated by means of correlation plots. Close correlation was revealed in the case of hide powder tannage while the smaller degree of correlation observed in the case of the pelt tannage systems was attributed to the modifying effects of diffusion, particularly on the initial reaction velocity. The effect of using boiled and aged chromium solutions in the tannages was to increase the initial rate of chroniill!l "fixation" apparently due to tho coordination of a dial species at each coordination site. After the initial reaction period, the two series showed a tendency to converge as in the case of the spectrophotometric studies on the acetate reaction. The convergence trend was regarded as indicative of the tendency for the chromium in fresh solutions to under go rapid olation to the ame level as in the boiled and aged solutions. The experimental observations made on the various systems lead to the following conclusions:- (a) The mechanism of coordination of the acetate radical ttrivalent chromium appears to involve the successive coordination of ligand to each of the chromium atoms of a diol complex, both coordination steps proceeding by second order reaction mechanisms. (b) At the pH levels at which the reaction is carried out, the formation of elated bodios is rapid so that reaction in the case of both fresh and aged solutions essentially occurs between an elated species and the ionised acetate radical. (c) Modificati0ns in the absorption spectrum of the reactant solution at the 570 mµ peak are directly related to coordination, while changes at the 420 mµ peak are related to the formation of loosely-bound hydroxo chromium compounds, the concentrations of which depend on the pH level. (d) The mechanism of chromium fixation in hide is essentially similar to that operating in the case of coordination of the acetate radical to chromium, involving attachment of chromium to the side chain acid r sidues of collagen. (e ) The effect of olation is to enhance the rate of chromium fixation by hide protein during the initial reaction stages and to render possible bridge formation between adjacent side chains by secondary coordination during the latter reaction stages. (f) Where pelt pieces are used instead of hide powder, the initial rate of chromium fixation is dominated by the rate of diffusion of chromium into the fibrous structure. It should be stressed that the observations made on the various reaction systems cannot be regarded as exhaustive and the conclusions are subject to further confirmation. Consequently, the present study is essentially of a preliminary nature, but it is felt that the need for further investigation along similar lines has been demonstrated.
- Full Text:
- Date Issued: 1962
- Authors: Russell, Allan Edward
- Date: 1962
- Subjects: Chemical kinetics , Chromium , Spectrophotometry , Electrophoresis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4493 , http://hdl.handle.net/10962/d1013101
- Description: The kinetics of the coordination reaction between the carboxyl group of the acetate radical and the trivalent chromium ion has been examined by independent methods at a temperature selected to yield reasonably accurate rate data. The study has been extended to an examination of the rate of chromium "fixation" by the carboxyl groups of hide collagen in a series of miniature tannages carried out under similar conditions for comparative purposes. The effect of olation of the chromium ions in solution on the kinetics of t he coordination reaction has also been examined. The rate of coordination of the acetate radical was followed by solvent extraction and spectrophotometric techniques over a range of concentration and pH levels. The rate data revealed a reaction having typical mass-action characteristics, the rate of reaction depending on the concentration levels of the chromium ion and the ionised acetate radical. An attempt made to distinguish a differential reaction rate in the case of a parallel reaction series using boiled and aged chromium nitrate reactant solutions, failed to reveal any significant differences between the series. The reactant solutions gave absorption spectra characteristic of the trivalent chromium ion with maxima in the 420 mµ and 570 mµ wavelength regions. The changes in optical density occurring in the vicinity of the maxima were followed spectrophotometrically, the height of the 570 mµ being found to increase during the course of reaction, while the height of the 420 mµ peak decreased. The variation in optical density at the 570 mµ peak was found to be directly related to the increase in concentration of the product complex in solution in accordance with the Baer-Bougher law, while the decrease in the height of the 420 mµ peak was related to the properties of unolated OH groups associated with the chromium complex as governed by pH and olation changes during the course of reaction. Boiled and aged chromium nitrate solutions gave reactant solutions having initial optical densities greater than those of the correspending fresh reactant solutions at the 570 mµ peak, and less than those of the fresh solutions at the 420 mµ peak. During the course of reaction, however, the two series converged to the same values. The equilibrium reaction solutions were subjected to paper electrophoretic study which indicated that all tho chromium was present in the form of cationic species. This finding was in accordance with stoicheiometric indications in the solvent extraction studies where coordination in a l : 1 ratio was reflected, giving rise to positively charged complex ions only. Making due allowance for band spreading the numbers of species predicted from the kinetic studies correspond with the electrophoretic patterns found. Application of the classical second order kinetic expression to the solvent extraction rate data, yielded plots having two distinctly linear sections, apparently indicating consecutive second order processes occurring in solution, contrary to the findings of previous workers who assign a first order mechanism to the reaction. This finding was consistent with the view that in the case of both the fresh and aged series, reaction consisted of successive coordination of an acetate radical to each chromium atom of a diol complex. Second order rate "constants" were calculated for each step and their dependency on pH level demonstrated. The findings of Hamm et al that these were first order reactions independent of acetate co'ncentration are believed to be due to their use of a large excess of acetate in their experiments. The kinetic study was further extended to an examination of the rate of "fixation"of trivalent chromium by the carboxyl groups of hide collagen under comparable conditions in a series of miniaturv tanning experiments in which the tannage substrate was provided in each of two physical forms:- (a) As hide powder where surface development was large, and (b) as prepared pelt pieces in which the fibrous weave pattern was retained. In view of the heterogeneity of the tannage systems, remarkable similarity was observed in the reaction course when compared with that of the acetate coordination studies, particularly in the case of the hide powder tannages. The dependency of the tannage rate data upon concentration and pH conditions was also found to be the same as in the case of the pure chemical system. The exact correlation between the rate data for the tannage and pure chemical systems was demonstrated by means of correlation plots. Close correlation was revealed in the case of hide powder tannage while the smaller degree of correlation observed in the case of the pelt tannage systems was attributed to the modifying effects of diffusion, particularly on the initial reaction velocity. The effect of using boiled and aged chromium solutions in the tannages was to increase the initial rate of chroniill!l "fixation" apparently due to tho coordination of a dial species at each coordination site. After the initial reaction period, the two series showed a tendency to converge as in the case of the spectrophotometric studies on the acetate reaction. The convergence trend was regarded as indicative of the tendency for the chromium in fresh solutions to under go rapid olation to the ame level as in the boiled and aged solutions. The experimental observations made on the various systems lead to the following conclusions:- (a) The mechanism of coordination of the acetate radical ttrivalent chromium appears to involve the successive coordination of ligand to each of the chromium atoms of a diol complex, both coordination steps proceeding by second order reaction mechanisms. (b) At the pH levels at which the reaction is carried out, the formation of elated bodios is rapid so that reaction in the case of both fresh and aged solutions essentially occurs between an elated species and the ionised acetate radical. (c) Modificati0ns in the absorption spectrum of the reactant solution at the 570 mµ peak are directly related to coordination, while changes at the 420 mµ peak are related to the formation of loosely-bound hydroxo chromium compounds, the concentrations of which depend on the pH level. (d) The mechanism of chromium fixation in hide is essentially similar to that operating in the case of coordination of the acetate radical to chromium, involving attachment of chromium to the side chain acid r sidues of collagen. (e ) The effect of olation is to enhance the rate of chromium fixation by hide protein during the initial reaction stages and to render possible bridge formation between adjacent side chains by secondary coordination during the latter reaction stages. (f) Where pelt pieces are used instead of hide powder, the initial rate of chromium fixation is dominated by the rate of diffusion of chromium into the fibrous structure. It should be stressed that the observations made on the various reaction systems cannot be regarded as exhaustive and the conclusions are subject to further confirmation. Consequently, the present study is essentially of a preliminary nature, but it is felt that the need for further investigation along similar lines has been demonstrated.
- Full Text:
- Date Issued: 1962
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