On the characterization of photovoltaic devices for concentrator purposes
- Authors: Vorster, Frederick Jacobus
- Date: 2007
- Subjects: Photovoltaic cells , Image processing , Solar cells
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10530 , http://hdl.handle.net/10948/639 , Photovoltaic cells , Image processing , Solar cells
- Description: This study originated from an evaluation of the performance of a commercially available high concentration point focus concentrator PV system. The effect of module design flaws was studied by using current-voltage (I-V) curves obtained from each module in the array. The position of reverse bias steps revealed the severity of mismatch in a string of series-connected cells. By understanding the effects of the various types of mismatch, power losses and damage to the solar cells resulting from hot spot formation can be minimized and several recommendations for improving the basic performance of similar systems were made. Concern over the extent and type of defect failure of the concentrator photovoltaic (CPV) cells prompted an investigation into the use of a light beam induced current (LBIC) technique to investigate the spatial distribution of defects. An overview of current and developing LBIC techniques revealed that the original standard LBIC techniques have found widespread application, and that far-reaching and important developments of the technique have taken place over the years. These developments are driven by natural progression as well as the availability of newly developed advanced measurement equipment. Several techniques such as Lock-in hermography and the use of infrared cameras have developed as complementary techniques to advanced LBIC techniques. As an accurate contactless evaluation tool that is able to image spatially distributed defects in cell material, the basis of this method seemed promising for the evaluation of concentrator cells.
- Full Text:
- Date Issued: 2007
On the microstructure and physical properties of hot pressed (Hf, Ti) C
- Authors: Heiligers, Christiané
- Date: 2007
- Subjects: Transition metal carbides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10532 , http://hdl.handle.net/10948/523 , http://hdl.handle.net/10948/d1011722 , Transition metal carbides
- Description: The microstructure and physical properties of hot pressed (Hf, Ti) C have been investigated with the aim of producing a cutting tool material with similar hardness to that of WC-Co and TiC-based cermets. Sintered samples were hot pressed from HfC0.7 and TiC0.9 powders using powder metallurgical techniques and the processing cycle was optimized for this system. Ni was used as a binder in selected samples and C black was added to compensate for sub-stoichiometry and to aid in the reduction of oxides formed during milling. Microstructural analyses were performed by scanning and transmission electron microscopy (SEM and TEM) and the composition was determined from X-ray diffraction (XRD) and energy dispersive X-ray spectrometry (EDS). The physical properties measured are density and Vickers hardness, and the indentation fracture toughness was determined using the Shetty formula. The fundamental interactions between HfC, TiC and Ni during hot pressing were investigated and the results obtained used to explain the microstructure that develops in samples made from powder mixtures. The interactions studied are the inter-diffusion of HfC and TiC through the solid state, and the dissolution and re-precipitation rate of the carbides in a liquid Ni binder. EDS analysis revealed that the rate at which Ti diffuses into HfC is higher than the rate at which Hf diffuses into TiC. Upper limits to the diffusion coefficients for these processes are determined and show that solid solution carbides will form from HfC + TiC powder mixtures at 2000 ºC in 1 hour if the average powder particle size is less than 5 μm. The diffusion rates decrease with a decrease in hot pressing temperature but mass transport between the phases can be enhanced by addition of a metallic binder. TEM and EDS analysis shows that Ni wets TiC more efficiently than HfC and that the solubility of TiC in Ni is also higher than that of HfC. The grain size of the carbide phases increases with an increase in the rate at which they dissolve into and re-precipitate from the liquid binder. The crystal structure of the binder phase depends on the concentration of Ti and Hf that remain in the binder after cooling and the carbide phase in which the binder is embedded. Analysis of TEM electron diffraction patterns show that the binder phase consists of cubic solid solutions as well as intermetallic and cubic phases in which atomic ordering is observed.
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- Date Issued: 2007
Prime near-ring modules and their links with the generalised group near-ring
- Authors: Juglal, Shaanraj
- Date: 2007
- Subjects: Near-rings
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10507 , http://hdl.handle.net/10948/714 , Near-rings
- Description: In view of the facts that the definition of a ring led to the definition of a near- ring, the definition of a ring module led to the definition of a near-ring module, prime rings resulted in investigations with respect to primeness in near-rings, one is naturally inclined to attempt to define the notion of a group near-ring seeing that the group ring had already been defined and investigated into by, interalia, Groenewald in [7] . However, in trying to define the group near-ring along the same lines as the group ring was defined, it was found that the resulting multiplication was, in general, not associative in the near-ring case due to the lack of one distributive property. In 1976, Meldrum [19] achieved success in defining the group near-ring. How- ever, in his definition, only distributively generated near-rings were considered and the distributive generators played a vital role in the construction. In 1989, Le Riche, Meldrum and van der Walt [17], adopted a similar approach to that which led to a successful and fruitful definition of matrix near-rings, and defined the group near-ring in a more general sense. In particular, they defined R[G], the group near-ring of a group G over a near-ring R, as a subnear-ring of M(RG), the near-ring of all mappings of the group RG into itself. More recently, Groenewald and Lee [14], further generalised the definition of R[G] to R[S : M], the generalised semigroup near-ring of a semigroup S over any faithful R-module M. Again, the natural thing to do would be to extend the results obtained for R[G] to R[S : M], and this they achieved with much success.
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- Date Issued: 2007
Rehabilitation of the Orange River Mouth Salt Marsh : seed, wind and sediment characteristics
- Authors: Shaw, Gregory Alan
- Date: 2007
- Subjects: Salt marshes -- Orange River , Rivers -- South Africa -- Environmental aspects , Orange River -- Ecology
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10626 , http://hdl.handle.net/10948/603 , http://hdl.handle.net/10948/d1012010 , Salt marshes -- Orange River , Rivers -- South Africa -- Environmental aspects , Orange River -- Ecology
- Description: The Orange River is an important source of freshwater and like many other wetlands in semi-arid regions, supports various social (Spurgeon, 1998), economic (Spurgeon, 1998; Bornman et al., 2005) and ecological functions. The saltmarsh at the Orange River Mouth has become degraded over time following numerous anthropogenic impacts. As a result the Transboundary RAMSAR site was placed on the Montreux record emphasising the importance for rehabilitation. The potential of the marsh for natural rehabilitation was assessed through three physical factors which were considered to have the most influence on the saltmarsh i.e. 1) sediment 2) water 3) wind. Three sampling areas were chosen to investigate the sediment characteristics of the ORM saltmarsh and the suitability for seed germination and adult survival. Site A was representative of the general marsh area, Site B was thought to have favourable sediment conditions for saltmarsh growth because of the large numbers of seedlings and Site C was prone to inundation by wind blown sediment. The sites were sampled in 2005 (dry conditions) and in 2006 after high rainfall and river flooding. Electrical conductivity (EC) of the sediment throughout the marsh was hypersaline in many instances above the tolerance range for S. pillansii (> 80 mS.cm-1) The freshwater event in 2006 lowered salinity significantly in two of the three sites. Differences in sediment characteristics were also compared for three habitats i.e. driftlines, open sites and under vegetation. Driftlines (C. coronopifolia = 872 seedlings m-2; S. pillansii = 1296 seedlings m-2) and the microhabitat associated with adult plants (C. coronopifolia = 803 seedlings m-2; S. pillansii = 721 seedlings m-2) created favourable conditions for seedling growth, however open unvegetated (C. coronopifolia = 56 seedlings m-2; S. pillansii = 49 seedlings m-2) areas had significantly lower seedling density. Due to the marsh currently being in a desertified state this study aimed to establish whether the remaining vegetation could produce enough seed to revegetate the marsh. Laboratory studies indicated that seeds of both species germinated best in freshwater (0 psu). The germination of S. pillansii seeds was 40 percent at 0 psu compared to 5 percent at 35 psu. After storage under hypersaline conditions (35 psu) C. coronopifolia showed 100 percent seed germination when returned to freshwater whereas storage at 70 psu decreased the viability of S. pillansii seeds. The plants are producing adequate seed that will allow for regrowth and rehabilitation if sediment and groundwater characteristics are suitable for seed germination, seedling growth and adult survival. However the increase in bare areas at the Orange River mouth as a result of salt marsh dieback has increased the available sediment source. The wind blown sediment has covered large areas of the remaining adult salt marsh vegetation, particularly in the northern corner at Site C, causing further die-back.
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- Date Issued: 2007
Reproductive co-existence among five sympatric single-stemmed aloes in the Gamtoos River Valley, Eastern Cape
- Authors: Botes, Christo
- Date: 2007
- Subjects: Aloe -- South Africa -- Gamtoos River Valley , Aloe -- South Africa -- Identification
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10628 , http://hdl.handle.net/10948/481 , Aloe -- South Africa -- Gamtoos River Valley , Aloe -- South Africa -- Identification
- Description: In this study I documented the convergence of five congeneric bird-pollinated plants (Aloe pluridens, A. lineata var. muirii, A. speciosa, A. africana, and A. ferox) into three functional groups based on size, shape, and the arrangements of flowers on the inflorescence, but also nectar rewards, pollen deposition sites on the bird-pollinators, and the degree to which bees play a role in their pollination. Individuals of similar functional groups were divergent in their peak flowering times and limited their degree of flowering overlap further by spatial aggregation and niche separation, within the Thicket of the Gamtoos River Valley. The nectar properties were especially useful in structuring the bird pollinator community, which resulted in greater ethological isolation and hence, greater reproductive assurance in the mixed co-flowering plant communities. Choice array experiments revealed that it was the fine scale aggregation of flowering individuals that ensured that bird-pollinators feed selectively, since when equal choice was available, interspecific visitation increased significantly compared to natural scenarios. Bird behaviour and the ecological intermediateness of one to the species explained its prominence in hybrid combinations. The spatial occurrence of hybrid individuals can be traced back to the energetics of foraging and its influence on bird floral constancy. The pollination ecology of similar South African Aloe species were extrapolated from these and recent findings by various authors, but emphasises the need for a robust natural phylogeny of the Aloaceae in order to draw comprehensive conclusions on the evolutionary radiation of this highly charismatic group.
- Full Text:
- Date Issued: 2007
Rhenium(V)-Imido complexes with potentially multidentate ligands containing the amino group
- Authors: Booysen, Irvin Noel
- Date: 2007
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10385 , http://hdl.handle.net/10948/479 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab=1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The complex trans-[Re(ada)Cl3(PPh3)2] (H2ada=2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. Surprisingly, the Re-Cl bond length trans to the Re=N bond is shorter than the two equatorial Re-Cl bond lengths. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux conditions led to the isolation of [C12H12N6O4] as only product. The [ReO4]- ion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of a twofold molar excess of H2apb (H2apb=2-(2-aminophenyl)-1Hbenzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of the formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonal-bipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. The complex has C2-symmetry. The two amino groups are singly deprotonated and provide a negative charge each, so that they are coordinated as amides. The oxo group provides two negative charges. In order to obtain electroneutrality for the rhenium(V) complex, the two coordinated imidazole nitrogens provide one negative charge. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps=N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans- [ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (which is present in trans- [Re(mps)Cl(PPh3)2](ReO4) as an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The [ReO4]- anion has approximately regular tetrahedral geometry. Two significant hydrogen bonds are formed between two of the perrhenyl oxygens and the water of crystallization. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The Xray crystal structure shows that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry around the rhenium(V) centre, with the two chlorides in cis positions.
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- Date Issued: 2007
Synthesis and characterization of symmetrical and unsymmetrical ferrocenyl ligands for use in the preparation of Redox Active Ruthenium Alkylidene Complexes
- Authors: Saku, Duduetsang
- Date: 2007
- Subjects: Ferrocene , Ligands , Asymmetric synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10403 , http://hdl.handle.net/10948/701 , Ferrocene , Ligands , Asymmetric synthesis
- Description: Oxidation of a ferrocenyl group in conjugation to another metal centre can alter the electron density at that metal centre and lead to a change in overall reactivity of a complex. Herein, the synthesis and characterization of redox active symmetrical and unsymmetrical ferrocenylalkene derivatives is described. A change in the standard redox potential of ferrocene (465 mV), to more positive potentials in vinylferrocene 1 (478 mV) and 4-phenylvinylferrocene 3 (499 mV), showed how manipulation of a redox potential can be effected on the ferrocenyl moiety by just using conjugation effects. A shift by +13 mV is observed in 1 and this potential more than doubled in 3 (+34 mV). Ferrocenylderived ruthenium alkylidene complexes were also prepared in a cross metathesis of 1 and 3 with Grubbs’ 1 (676.5 mV) to give complexes Ferrocenylidenebis( tricyclohexylphosphine)dichlororuthenium 14, 4-ferrocenylphenylidene-bis (tricyclohexylphosphine)dichlororuthenium 15 respectively. The extent of the electronic communication between the ferrocenyl group and the ruthenium centre was then estimated by looking at the positive or negative redox potential shifts of 14 and 15 as a result of 1 and 3. A large positive potential shift by 180 mV in 14 indicated that there was a strong electronic communication between the two metal centres, while the smaller, yet significant positive potential shift by 89.5 mV in 15 showed 3 to have a lesser effect on the ruthenium centre. Compounds 14 and 15 were tested in a Ring Closing Metathesis (RCM) of diethyldiallylmalonate showed enhanced reactivity.
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- Date Issued: 2007
Synthesis of P-Methane-3,8-Diol
- Authors: Mpuhlu, Batsho
- Date: 2007
- Subjects: Insect baits and repellents
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10411 , http://hdl.handle.net/10948/570 , http://hdl.handle.net/10948/d1011717 , Insect baits and repellents
- Description: The synthesis of para-menthane-3,8-diol in a batch reactor was investigated in some detail with the view to evaluate the potential of producing said p-menthane- 3,8-diol in a continuous-flow reactor from the results obtained from the batch process. The methodology used as base for this investigation was a published procedure by Takasago of Japan. The Takasago-method produced 92.3 percent Yield for the product para-menthane-3,8-diol, and 2.7 percent Yield of the by-product, acetal. The objective for this investigation was to produce a minimum p-menthane-3,8- diol content of 97.0 percent and a maximum content of 3.0 percent for the by-product acetal. The batch production process was evaluated in detail using statistical experimental design methodologies. Three process variables, namely catalyst loading, organic/aqueous phase ratio and reaction temperature were selected for the study. The experimental method was based on the Takasago procedure, however the substrate was added as a single slug as opposed to gradual addition method and the reaction period was reduced to 30 minutes. Apart from statistical analysis, mechanistic aspects were also used to interpret the following results. Using a central composite design, three response models (one for the conversion of citronellal, p-menthane-3,8-diol and acetal formation) were determined. An analysis of the response surfaces indicated that, to increase the citronellal conversion all three variables should be increased. To increase the amount of pmenthane- 3,8-diol, the reaction temperature and acid concentration should be increased, but the Aq/org ratio should be decreased as the acid catalyst concentration is increased. To minimize the amount of acetals formed during the reaction, the Aq/org ratio should be decreased; temperature and acid concentration can be decreased or increased. The reaction mechanism suggested that p-menthane-3,8-diol may be formed along two pathways: One pathway directly forms p-menthane-3,8-diol, whilst the second pathway forms the isopulegol first, then proceeds to form product by hydrolysis. The acetal is formed as result of the reaction between unreacted citronellal and p-menthane-3,8-diol. From the design experiments it was suggested that reaction time can be reduced to 8 minutes at reaction temperatures between, 80-85 0C The product and acetal were isolated by simple vacuum evaporation of the low boiling citronellal and isopulegol. Results from recycling the catalyst phase were similar to those of the initial process. The results of this investigation has clearly shown that with a proper understanding of the effect of process variables on the performance of the batch synthesis route, the conversion of this traditionally batch (actually semi-batch) process into a continuous process is quite feasible provided that suitable equipment is available. The most important features required for such equipment would be: Intense mixing throughout the reaction zone so as to maximise the surface area between the two immiscible phases, hence the rate of mass transfer between the two phases; and the ability to run reactions above the boiling point of water. Plans for the further study of the process are already well underway and sections of static mixing tubes have been acquired to build a continuous lab scale tubular reactor that would be capable of providing the level of mixing required.
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- Date Issued: 2007
Synthesis, properties and reactions of Novel Quinone Methides
- Authors: Taljaard, Jana Heloïse
- Date: 2007
- Subjects: Quinone , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10408 , http://hdl.handle.net/10948/616 , Quinone , Chemistry, Organic
- Description: Novel p-quinone methides have been synthesized by the dealkylation of 5-(p-alkyloxyaryl)- 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ols and related compounds. Aspects of the dealkylation reaction were investigated using computational methods in order to identify possible intermediates and postulate reasons for the observed reactivity patterns. This included studying the effect of varying the size of the central B-ring, changing the alkyloxy group, and altering the substitution pattern on the parent alcohols. We have assessed the relative energies of reaction intermediates and have also evaluated the influence of factors such as charge delocalisation, LUMO properties of the carbocations and thermodynamic factors on the dealkylation reaction. The use of different dealkylating reagents was also briefly investigated. Demethylation of 1,3- dimethyl-11-(4-methoxyphenyl)-6,11-dihydrodibenzo[b,e]oxepin-11-ol with pyridine hydrochloride led to acid-catalyzed ring-contraction of the parent alcohol to form a novel substituted anthraquinone, 9-(4-hydroxyphenyl)-1,3-dimethyl-anthracen-10-(9H)-one, in good yield. The general reactivity of the p-quinone methides of interest to us was explored by subjecting these compounds to reaction with a range of nucleophiles (bases, Grignard reagents and alcohols). A range of aryl Grignard reagents were reacted with the p-quinone methides, with the main product isolated in almost all cases being the aryl-coupled 1,2-addition product. The nucleophilic addition reactions of alcohols were supported by a computational study and a probable reaction mechanism has been postulated. A base-catalyzed rearrangement is proposed to account for the formation of products in which dehydrogenation of the ethane bridge was observed. These studies showed that in these p-quinone methides, chemical reactivity is strongly influenced by steric crowding, resulting in reversal of the normal 1,2- vs. 1,6- selectivities expected for nucleophilic addition. The ketalization process was explored further using diols and thiols. Products analogous to those obtained with the monohydric alcohols resulted from the diols, along with a series of novel bis-ethers. A range of miscellaneous reactions of 4-(dibenzo[a,d]cycloheptan-5-ylidene)cyclohexa-2,5,- dienone and related systems were investigated. Functionalization by epoxidation, dichlorocarbenation and Diels-Alder reactions, photochemical and [2+2] cycloaddition were attempted and reduction and oxidation reactions were also explored. Photochemical demethylation of an ortho-methoxyl substituent on the p-quinone methide system was observed to occur in good yield. The p-quinone methides underwent reductive coupling in the presence of Zn/AlCl3. The electronic spectra of highly conjugated carbocations were obtained and their potential as novel dyes evaluated. A low-temperature Grignard exchange reaction followed by spontaneous cyclization upon workup, was successful in synthesizing the lactone, spiro[10,11- dihydro-5H-dibenzo[a,d]cyclohepten-(3’,4’H)-phenyl-5,2’(5’H)-furan-5’-one], in one step from the starting ketone. A novel seven-membered Malachite Green dye analogue, 11-(4- dimethylamino-phenyl)-3-morpholin-4-yl-6,11-dihydro-dibenzo[b,e]oxepin-11-ol, was also synthesized and its electronic spectra compared to that of the unannulated Malachite Green dye series. All novel compounds synthesized were characterized using NMR, IR and HRMS-analysis.
- Full Text:
- Date Issued: 2007
The community structure and feeding ecology of the ichthyofauna in the Mngazana and Mngazi estuaries, Port St. Johns, South Africa
- Authors: Grant, Walter Lawrence
- Date: 2007
- Subjects: Estuarine fishes -- South Africa -- Eastern Cape , Fish communities -- South Africa -- Eastern Cape , Estuaries -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10713 , http://hdl.handle.net/10948/513 , http://hdl.handle.net/10948/d1012017 , Estuarine fishes -- South Africa -- Eastern Cape , Fish communities -- South Africa -- Eastern Cape , Estuaries -- South Africa -- Eastern Cape
- Description: The Mngazana and Mngazi estuaries are situated just south of Port St. Johns close to the biogeographical boundary between the warm temperate and subtropical zones along the east coast of Southern Africa. The Mngazana estuary is a permanently open estuary with three species of mangrove. The Mngazi estuary is a temporarily open/closed system. The ichthyofauna was sampled with seine nets and gillnets during June 2005, August 2005, November 2005, February 2006 and April 2006. The fish community structure was significantly different between the two estuaries with the differences being especially noticeable in the larger fish sampled with gillnets. There were significant differences in the fish community sampled with the seine net on both spatial and temporal scales in both of the estuaries. Certain warm temperate species were less abundant and certain subtropical species were more abundant at the Mngazana estuary than they were during a study conducted in 1975. Stomach content analysis revealed that most species had similar diets in the two estuaries with the only differences occurring among benthic feeding species. The diet of sub-adult piscivores comprised of a large proportion of penaeid prawns while the juveniles feed mainly on mysids. The zooplanktivorous fish feed mainly on copepods and mysids with the proportions varying between the species. Benthic feeding fishes showed the greatest variability in diet with plant material, detritus, crabs and copepods being the main food sources. Stable isotopes revealed that particulate organic matter and microphytobenthos were the most important carbon sources to fish in the Mngazi estuary. In the Mngazana estuary a combination of mangrove material, detritus, particulate organic matter and Zostera material were the most important carbon sources. The importance of each of these sources did, however, vary greatly between the different trophic guilds of the fish in the Mngazana estuary. The distribution of certain fish species was investigated in relation to physical parameters (temperature, salinity, turbidity and depth) and biological parameters (prey and predators) in the environment. It was found that most small fish (< 100 mm SL) were strongly correlated with turbidity where-as they showed weak correlations with their prey. Sub-adult piscivores fell into two groups, i.e. those that could tolerate turbid water and those that were only found in clear water. The group that also occurred in turbid water showed very strong correlations with their prey but the clear water group did not. It would appear that the small and thus vulnerable fish seemed to occur in areas that offered them protection rather than areas where their food supply is most abundant, where-as the piscivores were more influenced by prey distribution, as long as the physical conditions were tolerable to them.
- Full Text:
- Date Issued: 2007
The electrochemical synthesis of 3-tert-Butyl-4-Methoxybenzaldehyde
- Authors: Qusheka, Sivuyile Emmanuel
- Date: 2007
- Subjects: Oxidation
- Language: English
- Type: Thesis , Masters , MTech
- Identifier: vital:10410 , http://hdl.handle.net/10948/595 , Oxidation
- Description: This project was concerned with the evaluation of three potential synthetic routes for 3-tert-butyl-4-methoxybenzaldehyde, a useful fine chemical intermediate and ingredient in many sunscreen agents. The three synthetic routes all involved the selective oxidation of the 3-tert-butyl-4-methoxytoluene to the desired benzaldehyde by (a) catalytic air oxidation, (b) direct electrochemical oxidation, and (c) indirect electrochemical oxidation. In order to decide whether catalytic oxidation should precede the alkylation of 4-methoxytoluene, the selective oxidation using the well-known cobalt(II)- bromide catalyst system in acetic acid solutions were investigated with the view to determine whether increased electron density on the aromatic ring improves selectivity to the desired benzaldehyde or not. In addition, the effect of various important reaction variables was also investigated. These studies showed that increased electron density, hence increased substitution, increases the desired benzaldehyde selectivity. In addition, while reaction conditions such as reaction temperature, catalyst concentration, water concentration, etc. may be optimised for maximum 3-tert-butyl-4- methoxybenzaldehyde yields (~80 percent), such yields can only be achieved at relatively low (<40 percent) alkoxytoluene conversions. The direct electrochemical oxidation of 3-tert-butyl-4-methoxytoluene was investigated in methanol solutions containing various supporting electrolytes and using constant current electrolysis with the intention of optimizing the production of 3-tert-butyl-4-methoxybenzyl dimethyl acetal which can later be hydrolyzed using sulfuric acid to the 3-tert-butyl-4-methoxybenzaldehyde. In this study, various parameters such as supporting electrolyte and electrodes were studied. Previous studies showed undoubtedly that methanol as a solvent gave better results amongst the rest of the solvents. Indirect route was also studied as a method of synthesizing 3-tert-butyl-4- methoxybenzaldehyde and compared to the direct electro synthesis.
- Full Text:
- Date Issued: 2007
The evaluation of a pedagogical-program development environment for Novice programmers : a comparative study
- Authors: Vogts, Dieter
- Date: 2007
- Subjects: Computer programming -- Study and teaching , Programming languages (Electronic computers) , Web site development
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10477 , http://hdl.handle.net/10948/638 , Computer programming -- Study and teaching , Programming languages (Electronic computers) , Web site development
- Description: It is an acknowledged fact that many novice programmers experience difficulty in the process of learning to program. One of the contributing factors to this difficulty is the Program Development Environment (PDE). Professional-PDEs are those developed specifically for professional programmers, but are often used by educational institutions in the instruction of programming. It has long been accepted that such environments are inappropriate in the instruction of programming due to unnecessary complexity and lack of support for novice programmers in the learning process. Numerous pedagogical-PDEs supporting the mechanics of programming have been developed in response to this. A review of literature, however, indicates that very limited empirical studies comparing pedagogical-PDEs and professional-PDEs have been conducted. The current study investigates whether there are measurable benefits to using a pedagogical-PDE supporting the mechanics of programming in the instruction of programming instead of a professional-PDE. A comparative study of this nature requires a representative pedagogical-PDE and representative professional-PDE be compared with one another. The first part of the current study determines a set of requirements that a pedagogical- PDE should adhere to based on literature. A set of representative features for a pedagogical-PDE is derived by examining the features of existing PDEs in conjunction with the set of requirements. Based on these features, a pedagogical-PDE, known as SimplifIDE, is developed that implements the representative set of features and that meets are the requirements for a pedagogical-PDE. The second part of the current study is the specification and administration of an empirical experiment in which SimplifIDE and Borland© DelphiTM are compared with one another. A holistic approach in determining the differences between the PDEs is taken and three main areas are examined, namely academic performance, perceptions and programming behavior.
- Full Text:
- Date Issued: 2007
The kinetics and associated equilibria of high oxidation state osmium complexes
- Authors: McFadzean, Belinda Julie
- Date: 2007
- Subjects: Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10371 , http://hdl.handle.net/10948/732 , Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Description: The reduction of osmium tetroxide by a series of alcohols was studied spectrophotometrically. The reaction was observed to occur in two steps, unlike previously reported studies on this reaction. The identities of both reactants and products were established via a range of techniques. Equilibrium and kinetic data were gathered and reaction models were evaluated using equilibrium and kinetic modelling software. The following complexation reaction model emerged that simulates both the equilibrium and kinetic data. Os(VIII) + RCH2OHOs(VI) + RCHO2 Os(VIII) + Os(VI)k+2k1Complexk-2 Conditional rate constants and equilibrium constants were generated. Rate constants for the alcohol reactions were correlated with the Taft σ* constant. The ρ* value obtained (-1.4) is consistent with a hydride transfer mechanism coupled with synchronous removal of the hydroxyl proton. The identity of the osmium(VIII)-osmium(VI) complex has been suggested. Thermodynamic parameters were also reported. The rate constants for benzyl alcohol and 2-chloroethanol deviated from those predicted by the Taft plot. An explanation of enhanced resonance effects is offered for benzyl alcohol and an alternative reaction mechanism, involving proton abstraction, is offered for 2-chloroethanol. The reaction of the oxidation products of alcohols, namely ketones, with osmium tetroxide produced rate constants that were, perhaps surprisingly, far larger than those of the alcohols. A reaction mechanism for the oxidation of the ketones is suggested, which involves the enolate ion as the reactive starting reagent.
- Full Text:
- Date Issued: 2007
The role of pacC in Aspergillus flavus
- Authors: Suleman, Essa
- Date: 2007
- Subjects: Fungi -- Biotechnology , Pathogenic microorganisms
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10332 , http://hdl.handle.net/10948/612 , Fungi -- Biotechnology , Pathogenic microorganisms
- Description: Many microorganisms, and in particular fungi, are able to grow over a wide pH range. Thus, these microorganisms must possess some regulatory mechanism or system that senses the environmental pH signal and ensures that gene expression of certain molecules is tailored to the pH of the environment (Penalva and Arst, 2002). In Aspergillus species and several other fungi, pH regulation is mediated by seven genes viz. palA, palB, palC, palF, palH, palI and the global pH regulatory gene, pacC (MacAbe et al, 1996; Negrete-Urtasun, 1999; Denison, 2000). The activated form of the PacC protein activates genes that are required at alkaline pH, e.g. genes coding for alkaline phosphatases, and represses certain genes that are functional at acidic pH, e.g. genes encoding acid phosphatases (Negrete-Urtasun, 1999). PacC (and its homologues) also positively regulates genes involved in penicillin biosynthesis, e.g. the isopenicillin N synthase gene, ipnA, in A. nidulans (Penalva and Arst, 2002). It has also been hypothesised that pacC may negatively regulate aflatoxin biosynthesis, a carcinogenic secondary metabolite in several species of Aspergillus (Keller et al, 1997). To elucidate the role of pacC a novel method of post-transcriptional gene silencing known as RNA interference was utilized. This method involved the cloning of a partial pacC gene fragment first in the forward and then the reverse orientations in a fungal expression cassette to create an RNA interference (RNAi) vector. The unique structure of this vector would allow the cloned fragments to be expressed and the resulting RNA to immediately form a double stranded stem-loop structure or short hairpin RNA (shRNA; McDonald et al, 2005). The formation of this shRNA, in turn, would be responsible for activating the endogenous RNA degradation complexes that would lead to mRNA degradation and subsequent gene silencing (Liu et al, 2003; Kadotoni et al, 2003; McDonald et al, 2005). The results presented here have shown that confirmed pacC RNAi mutants produced aflatoxins irrespective of environmental pH (i.e. the mutants produce aflatoxins under acidic and alkaline conditions). Thus, pacC is essential for pH regulation of aflatoxin production in A. flavus. There are numerous other biological (e.g. presence of oxylipins, lipooxygenases) and non-biological factors (pH, carbon source etc.) which affect maize colonisation and aflatoxin production by A. flavus (Burrow et al, 1996; Wilson et al, 2001; Calvo et al; 2002; Tsitsigiannis et al, 2006). However, all the genetic mechanisms involved have as yet not been identified. It has been shown by Caracuel et al (2003) that pacC acts as a negative virulence regulator in plants and these workers have hypothesised that PacC prevents expression of genes that are important for infection and virulence of the pathogen. Therefore the physiological effects that pacC silencing had on the growth, conidiation and pathogenicity of A. flavus mutants were also investigated. The results of this study showed that pacC does not play a significant role in primary growth and development but does affect conidial production. SEM results showed that mutants have many “open ended” phialides and poorly developed conidiophores. This would suggest that pacC activation of conidial production genes is also required. Furthermore, pacC RNAi silencing severely impaired the ability of the A. flavus mutants to infect and cause damage on maize. The results obtained here are similar to that of pacC null mutants in A. nidulans, C. albicans and F. oxysporum which also exhibited low pathogenicity (Davis et al, 2000; Fonzi, W.A, 2002; Caracuel et al, 2003; Bignell et al, 2005 and Cornet et al, 2005). This study indicates that pathogenicity of A. flavus on maize is directly related to the structural integrity of conidia, which in turn is greatly influenced by PacC. This gene is a global transcriptional regulator and may either repress or activate one or many genes in each of the above pathways (Penalva and Arst, 2002). Studies on the genetic mechanisms of pacC regulation on these pathways are needed to elucidate the mechanisms of activation or repression of these genes.
- Full Text:
- Date Issued: 2007
The use of thermal modelling in improving rural subsistence aquaculture
- Authors: Bailey, Dylan Francis
- Date: 2007
- Subjects: Sustainable aquaculture -- South Africa , Aquaculture industry -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10715 , http://hdl.handle.net/10948/473 , Sustainable aquaculture -- South Africa , Aquaculture industry -- South Africa
- Description: There has been a long history of attempts to promote subsistence rural aquaculture within South Africa. Many of these attempts have failed due to inadequate support from government and support agencies. There has been a recent revived interest in promoting rural aquaculture development. Presented in this project are six scenarios demonstrating the potential application of thermal modelling techniques to improving subsistence rural aquaculture. These scenarios were based on a model validated against a real life system, and run with environmental data for the year 2005. Bovine manure, grass thatch, cereal straw and Typha spp. water reeds were tested for thermal performance. These results were then applied to the scenarios. The open and kraal enclosed pond scenarios yielded the widest deviation in temperatures throughout the year, with an average temperature of 3.8oC and 6.0oC above ambient and a temperature range of 10.6oC and 12.4oC for the year respectively. Eliminating solar radiation and reducing wind speed resulted in an average difference of 1.5oC below ambient and a temperature range of 7.5oC for the year. When completely enclosed in a well-sealed traditional Xhosa style hut, the pond had an average difference of 5.6oC below outside ambient temperature, with a range of 7.8oC for the year. A passive solar heating scenario added to the sealed hut scenario, which when run continuously maintained an average difference of 34.7oC above outside ambient temperatures, with a range of 56oC for the year. When a hypothetical 25oC temperature control was included in the model, the system maintained an average of 7.1oC above ambient outside temperatures, with a temperature range of 0.8oC throughout the year. The wider range of temperatures made available through the use of thermal modelling approaches provides a more diverse range of species available for subsistence rural aquaculture at any site, significantly improving its potential.
- Full Text:
- Date Issued: 2007
The zooplankton of Mngazana estuary
- Authors: Louw, Liezel
- Date: 2007
- Subjects: Marine zooplankton -- South Africa -- Mngazana Estuary , Mngazana Estuary (Eastern Cape, South Africa) , Estuarine ecology -- South Africa -- Mngazana Estuary , Estuarine area conservation -- South Africa -- Mngazana Estuary
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10707 , http://hdl.handle.net/10948/702 , Marine zooplankton -- South Africa -- Mngazana Estuary , Mngazana Estuary (Eastern Cape, South Africa) , Estuarine ecology -- South Africa -- Mngazana Estuary , Estuarine area conservation -- South Africa -- Mngazana Estuary
- Description: The zooplankton community of the main channel of the Mngazana estuary was investigated on six occasions over one year. Spatial and temporal variability in zooplankton abundance and distribution were sampled using two slightly modified WP2 plankton nets of 200 μm mesh and 57 cm mouth diameter. Nets were fitted with calibrated Kahlsico 005 WA 130 flow meters. A set of environmental variables were also measured at each site. The water column of the main channel of Mngazana estuary was stratified in summer but well mixed in winter. Temperature progressively increased from the lower stations to the upper reaches of the estuary. Maximum vertical temperature differences occurred in the middle estuarine reaches. Salinity progressively decreased from the lower reaches to the upper reaches, but was generally above 26 from Station 3 to Station 8. Only during November 2005, were salinity readings low due to heavy rains. Summer salinity values were always lower than the winter salinity values as a result of summer rainfall. A total of 76 zooplankton taxa were identified. The estuarine copepods Acartia natalensis and Pseudodiaptomus hessei dominated the assemblage, with maximum abundances in the middle to upper reaches. Acartia natalensis reached high densities in winter (> 50 000 m-3) although lowest abundances were recorded when maximum rainfall was received (November 2005). Wooldridge (1977) and Deyzel (2004) recorded maximum densities during summer. Pseudodiaptomus hessei reached high densities (> 17 000 m-3) during the highest rainfall month. Previous studies indicated that this pioneer species is able to recover quickly after a flood and subsequently increase rapidly in numbers. The mysid, Mesopodopsis africana reached high densities (> 5 000 m-3) in the middle estuarine reaches during summer. Ichtyofauna, brachyura and anomura were important contributors to the merozooplankton component of the community. The maximum number of species was recorded during winter in the lower estuarine reaches, when vertical differences in salinities were minimal.
- Full Text:
- Date Issued: 2007
Towards knowing through doing : improving the societal relevance of systematic conservation assessments
- Authors: Knight, Andrew Thomas
- Date: 2007
- Subjects: Conservation of natural resources -- Planning , Nature conservation -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10598 , http://hdl.handle.net/10948/711 , Conservation of natural resources -- Planning , Nature conservation -- South Africa
- Description: Systematic conservation assessments are spatially-explicit techniques for prioritising areas for the implementation of conservation action. There has been considerable reference in the peer-reviewed literature as to the usefulness of these tools, which appear to be primarily used by academics for theoretical research. A literature review and author survey reveals the peer-reviewed literature is largely theoretical, although conservation action results more frequently than reported. The effectiveness of these interventions is generally described as only ‘fairly effective’. This general trend, coupled with previous personal failures in translating systematic conservation assessments into effective conservation action triggered an explicit process of social learning implemented as action research. It examined the workings of the Subtropical Thicket Ecosystem Planning (STEP) project, which included development of a systematic conservation assessment. Systematic conservations assessments simply provide information on where action should be implemented, and so are only useful if situated within broader operational models for conservation planning. Most operational models presented in the peer-reviewed literature are primarily focused upon the testing ecological data, not upon the delivery of conservation action. A new operational model for conservation planning is presented which more accurately reflects the ‘real-world’ process of conservation planning. An implementation strategy is an essential complement to a systematic conservation assessment. It describes how specific, explicitly-stated goals will be achieved, who is accountable for undertaking these activities, and the resources required. As the Implementation Specialist for the STEP Project, I co-lead the collaborative development of an implementation strategy with stakeholders that aimed to mobilise resources towards achieving common goals. Whilst the development and initial uptake of the strategy was good, subsequent implementation has flounder. The reasons for this are explored. The ultimate pragmatic goal of a conservation planning process is the establishment of effective social learning institutions. These develop common visions, mobilise collective action, and adaptively learn and refine their conservation activities. Thicket Forum is one xi such institution established through the STEP Project. My involvement with Thicket Forum since 2004 in implementing an adaptive learning approach facilitates collaboration between land managers, government and research organisations. Systematic conservation assessments evolved in response to the ad hoc way in which protected areas were implemented, leaving unrepresentative, biased protected area networks. Most research is theoretical and without an intimate understanding of the social-ecological system of a planning region, notably opportunities and constraints for implementing conservation action. Highlighting the importance of an approach which is flexible, not only in space, but in time, which can capitalise upon implementation opportunities, is important for stemming the myth that opportunism is the nemesis of systematic conservation assessments. To this end, conservation planners have been slow to include factors influencing effective implementation in systematic conservation assessments. Many studies which identify candidate protected area networks, first, fail to identify the specific instrument(s) to be applied, and second, assume all intact land is available. Having mapped the willingness of land managers in the Albany District, South Africa, to sell their land, it is demonstrated the majority of targets fail to be achieved because land managers will not sell. Knowing this, the current focus of gathering ever-more ecological data is misplaced. Human, social and economic factors influence target achievement, efficiency and spatial configuration of priority areas. Selecting important areas for conservation, particularly at the local-scale, requires the mapping of factors which define opportunities for conservation. Land manager willingness to collaborate and participate, entrepreneurial orientation, conservation knowledge, social capital, and local champions were applied using a method of hierarchical clustering to identify land managers who represent conservation opportunities for private land conservation initiatives.
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- Date Issued: 2007
A comparison framework for server virtualisation systems a case study
- Authors: Van Tonder, Martin Stephen
- Date: 2006
- Subjects: Virtual computer systems -- South Africa Case studies , Virtual storage (Computer science) -- South Africa Case studies
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10481 , http://hdl.handle.net/10948/439 , http://hdl.handle.net/10948/d1012009 , Virtual computer systems -- South Africa Case studies , Virtual storage (Computer science) -- South Africa Case studies
- Description: Recent years have seen a revival of interest in virtualisation research. Although this term has been used to refer to various systems, the focus of this research is on systems which partition a single physical server into multiple virtual servers. It is difficult for researchers and practitioners to get a clear picture of the state of the art in server virtualisation. This is due in part to the large number of systems available. Another reason is that information about virtualisation systems lacks structure, and is dispersed among multiple sources. Practitioners, such as data centre managers and systems administrators, may be familiar with virtualisation systems from a specific vendor, but generally lack a broader view of the field. This makes it difficult to make informed decisions when selecting these systems. Researchers and vendors who are developing virtualisation systems also lack a standard framework for identifying the strengths and weaknesses of their systems, compared to competing systems. It is also time-consuming for researchers who are new to the field to learn about current virtualisation systems. The purpose of this research was to develop a framework to solve these problems. The objectives of the research correspond to the applications of the framework. These include conducting comparative evaluations of server virtualisation systems, identifying strengths and weaknesses of particular virtualisation systems, specifying virtualisation system requirements to facilitate system selection, and gathering information about current virtualisation systems in a structured form. These four objectives were satisfied. The design of this framework was also guided by six framework design principles. These principles, or secondary objectives, were also met. The framework was developed based on an extensive literature study of data centres, virtualisation and current virtualisation systems. Criteria were selected through an inductive process. The feasibility of conducting evaluations using the framework was demonstrated by means of literature-based evaluations, and a practical case study. The use of the framework to facilitate virtualisation system selection was also demonstrated by means of a case study featuring the NMMU Telkom CoE data centre. This framework has a number of practical applications, ranging from the facilitation of decision-making to identifying areas for improvement in current virtualisation systems. The information resulting from evaluations using the framework is also a valuable resource for researchers who are new to the field. The literature study which forms the theoretical foundation of this work is particularly useful in this regard. A future extension to this work would be to develop a decision support system based on the framework. Another possibility is to make the framework, and evaluations, available on-line as a resource for data center managers, vendors and researchers. This would also enable other researchers to provide additional feedback, enabling the framework to be further refined
- Full Text:
- Date Issued: 2006
A Hall-effect study of as-grown and hydrogenerated n-type ZnO layers grown by MOCVD
- Authors: Somhlahlo, Nomabali Nelisiwe
- Date: 2006
- Subjects: Hall effect , Electric currents
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10535 , http://hdl.handle.net/10948/444 , http://hdl.handle.net/10948/d1012014 , Hall effect , Electric currents
- Description: A series of as-grown ZnO layers have been electrically characterised by the temperature dependent (20 – 300 K) Hall-effect technique. The ZnO layers were grown by metal organic chemical vapour deposition (MOCVD) on glass substrates under various growth conditions. The temperature dependent Hall-effect technique produced mobility and carrier concentration measurements. These measurements were found to be reproducible and reliable. The carrier concentration data for the layers was fitted by the charge balance equation to accurately determine the donor level and corresponding donor concentration as well as the acceptor concentration for each sample. The measured donor levels were found to vary from sample to sample and there is evidence from the results that the variations are related to the differing growth conditions of the layers. The mobility data was also fitted to establish the dominant electron scattering mechanisms in the layers. The dominant scattering mechanisms were found to vary from sample to sample. For most of the layers studied, the dominant scattering mechanism was found to be both the ionised impurity scattering at low temperatures (20 – 100 K) and grain boundary scattering at higher temperatures (100 – 300 K). The effects of exposing the ZnO layers to hydrogen plasma were also investigated by the temperature dependent Hall-effect technique. Findings indicate that hydrogen is readily incorporated in ZnO, leading always to an increased carrier concentration. It was further noted that incorporating hydrogen into ZnO in some layers increased the mobility while in other layers it caused a decrease in the mobility. The hydrogenated samples were subsequently annealed at 600 °C for 1 hour in argon ambient resulting in the carrier concentration reducing to its original value. This effect is attributed to hydrogen diffusing out of ZnO.
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- Date Issued: 2006
A model for information architecture of government web sites in Southern Africa
- Authors: Bernardo, Tomás
- Date: 2006
- Subjects: Information storage and retrieval systems , Web sites -- Design , Government information -- South Africa
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10479 , http://hdl.handle.net/10948/459 , Information storage and retrieval systems , Web sites -- Design , Government information -- South Africa
- Description: The main purpose of this research is to investigate the Information Architecture (IA) of government web sites in Southern Africa. The government web sites of Mozambique and South Africa were selected for the purpose of this research. A further aim of this research was to derive a model for the IA of government web sites. The model was based on IA components and guidelines as well as on web site components and E-government requirements. The IA guidelines in the model were derived from general design guidelines and guidelines for government web sites. The IA guidelines in the proposed model were used to conduct an analytical and empirical evaluation of the selected sites. The selection of the sites was based on similarities in the Information and Communication Technology (ICT) strategies and policies, the annual Internet growth rates, the Internet user profiles and the Egovernment initiatives in both countries. Differences between the sites also contributed to their selection. Mozambique is one of the least developed countries in the world, while South Africa is one of the most developed countries in Africa. Heuristic evaluation was used for the analytical evaluation while questionnaires and user testing were used for the empirical evaluation. Some of the usability problems identified in the heuristic evaluation, such as incorrect organisation of information and navigation issues, were also identified in the empirical evaluation, confirming to the existence of these usability problems. The results of this research show that the IA of government web sites has an impact on user performance and satisfaction and that the proposed model can be used to design and evaluate the IA of government web sites in Southern Africa.
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- Date Issued: 2006