No description available.

In this thesis, the process involved in the precipitations and separations of the metal of Group II and Group III studied. Suggestions have also been offered whereby students can make an analysis without loosing metals in the initial precepitation.

<P> A new preconcentration method had been developed for the determination of some trace-metal ions in lakewater. This method is based on the formation of their TPPS4 complexes at elevated temperatures in solution and adsorption of the complexes onto a column of the macroporous acrylic ester resin, XAD-7. The complexes are eluted with a methanolic solution and the metal concentration determined by graphitefurnace atomic absorption spectroscopy. Optimal conditions were established for the group preconcentration of Cd, Cu, Ni and Pb. The concentration of these trace metals in several lakewater samples were determined successfully, with a precision comparable to that of the accepted Chelex-100 method. Application of the method to natural seawater samples failed, largely because of aggregation in the highly saline medium. </p> <P> Adsorption isotherms of TPPS4 and its complexes on XAD resins were obtained. Adsorption onto XAD-2 and XAD-4 resins likely involves n-n interactions while adsorption onto XAD-7 is probably due to weak Van der Waals forces. The adsorption at high TPPS4 concentrations is complicated by aggregation. </p> <P> An attempt to create a simple chelating ion-exchange resin by adsorption of TPPS4 onto XAD resin failed. Similarly, the development of a rapid room-temperature preconcentration method specifically for Pb and Cd in natural waters was not successful. </p> / Thesis / Master of Science (MSc)

No description available.

No description available.

No description available.

A photolytic cell system suitable for the treatment of wastewater streams containing three pesticides, i) acephate, ii) glyphosate and iii) malathion is reported. The system is capable of destroying these three organic compounds, commonly present in wastewater streams originating from agrochemical industries in Malaysia, and can lead to complete mineralisation under the optimum conditions. The system is based on an advanced oxidation process and involves the production of hydroxyl free radicals in the presence of a UV source. The performance of the system, for the three pesticides, was optimised by investigating the effects of i) UV source, ii) pH of the solution, iii) initial concentration of the substrate, iv) addition of oxidants, v) hydrogen peroxide (H2O2) in the presence and absence of single and mixed metal ions. To monitor the degradation efficiency of the system, the residual concentrations of these organic compounds and metal ions were analysed using five analytical techniques i) total organic carbon (TOC), ii) high performance liquid chromatography (HPLC), iii) ion chromatography (IC), iv) UV/Visible spectroscopy (UV/Vis), and v) atomic absorption spectroscopy (AAS). The data show that the developed photolytic cell system is capable of achieving complete mineralisation of the three pesticides with the use of both 400 W and 600 W UV lamps. However, the 400W UV lamp was used, for economic reasons, to optimise the system for the remaining factors. Changes in the pH of aqueous solutions influenced the degradation efficiency and a complete degradation of the three pesticides was achieved at their self-pH values ranging from 5.0-5.5. The degradation of acephate increased and malathion decreased at their higher initial concentrations whereas no significant effect related to concentration was observed for glyphosate. Results show that the degradation followed a first order kinetics and the degradation rates were: malathion > acephate > glyphosate. The addition of 30 mg/L of H2O2 enhanced the degradation of the pesticides and after 5 hours irradiation these were 95.7%, 91.5% and 81.3% for malathion, acephate and glyphosate respectively. The presence of metal ions was observed to affect degradation (Table 1). With 5.0 mg/L of Fe(II) the degradation of all three pesticides increased, and in all cases acephate removal was improved. Removal of both malathion and glyphosate was negatively affected by copper, an effect that work with mixtures indicated was stronger than the positive effect of iron. The addition of H2O2, in the presence of single metal ions, increases the degradation. However, the addition of H2O2, in the presence of mixed metal ions, has no significant effect on the degradation of glyphosate and malathion. The effect of mixed metal ions on the three pesticides and the effect of Zn(II) ions on acephate and malathion are reported for the first time in this thesis. The developed photolytic cell system can be used for the treatment of wastewater streams originating from point sources, for example, agrochemical industries, under the optimum conditions. The synergistic combination of the developed system with the existing standard technologies is also proposed for the treatment of surface water at water treatment facilities in Malaysia. The application of the developed system can also be extended, with minimum modifications, for the treatment of wastewater streams originating from different manufacturing industries in Malaysia, for example, textile, paper/pulp, printing, coke, petroleum, paint, solvent, pharmaceuticals and wood-preserving chemicals. All these industries produce wastewater streams containing low concentrations of organic pollutants and heavy metal ions.

Thesis (MSc)--Stellenbosch University, 2003. / ENGLISH ABSTRACT: In this study, a number of mono- and di-substituted acyl(aroyl)thioureas were investigated for potential application as specific carriers (ionophores) for the transport and extraction of Ag(l) from a mixture of Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(lI) ions. The experimental arrangement for the transport experiments employed a liquid membrane set up involving a 3-phase system - 2 aqueous phases (source and receiving phase) separated by a chloroform membrane incorporating the ligand. Competitive metal ion transport experiments were conducted using the liquid membrane set up. The aqueous source and receiving phases were analyzed using Atomic Absorption Spectroscopy (AAS) and results were confirmed by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICPOES). The transport results show that the N,N-dialkyl-substituted-N'-acyl(aroyl) (HL) thioureas studied, with the exception of the N,N-di-(2-hydroxyethyl)-N'-benzoylthiourea (HL3 ) and N-piperidyl-N'-4-nitrobenzoylthiourea (HL9 ), were efficient and selective for Ag(I). HL9 was also selective for Ag(l) but not efficient. HL3 was selective for Cu(II). Under the experimental conditions employed, 13% Cu(lI) was transported by HL3 . Among the N,Ndialkyl- N'-aroylthioureas, maximum Ag(l) transport was obtained by using N,N-diethyl-N'-4- chlorobenzoylthiourea (HL5 ) and N,N-di-n-butyl-N'-benzoylthiourea (HL \ Under the experimental conditions employed, the percentages of Ag(l) transported by HL5 and HL 1 were 48% and 42% respectively. The transport selectivity and efficiency of 3,3,3' ,3'-tetraethyl-1 ,1'-isophthaloylbisthiourea (H2L12 ) and N,N-diethyl-N'-camphanoylthiourea (HL13)for Ag(l) were also studied. We were particularly interested, in comparing the Ag(l) transport and extraction efficiency of these ligands with that of the HL and H2L ligands. The experimental results reveal that, of all the ligands we investigated in this study, HL 13 was the most efficient and selective carrier for Ag(l) transport. The interesting result is that, depending on the ligand concentration used, HL 13 transported 71-81% of Ag(I). Competitive two-phase metal ion solvent extraction experiments were also performed under conditions similar to the transport studies. The results show that by varying the ligand concentration in the membrane phase, up to 100% Ag(l) can be selectively and efficiently extracted from the mixture of the seven metal ions. Finally, the N,N-di-(n)-butyl-N'-benzoylthiourea (HL1) ligand and its complex with Ag(l) were synthesized. Single crystals of the complex were grown for X-ray crystallography and the crystal and molecular structure of the complex was determined. The crystal structure showed that Ag(l) is bonded to the deprotonated ligand through the S,O atoms forming interesting cluster [Ag (L - S, 0)] 4 in the solid state. This structure is monoclinic and crystallizes in the space group P21!c with a = 17.805 (4) A, b = 21.759 (4) A, c = 36.438 (7) A, f3= 96.34(3)°, Z = 8 and a final R-factor of 5.4%. / AFRIKAANSE OPSOMMING: In hierdie proefskrif is 'n aantal mono- en di-gesubstitueerde asiel(ariel) tioureums ondersoek vir moontlike gebruik as ionofore (spesifieke draers) vir die transportasie en ekstraksie van Ag(l) vanuit 'n mengsel van Co(ll), Ni(II), Cu(II), Zn(II), Cd(II), Ag(l) en Pb(lI) ione. 'n Drie-fase selsisteem is gebruik vir die transportasie eksperimente, twee waterige fases (bron- en ontvang-fase) wat geskei is met die chloroform membraan fase wat die ligande bevat. Kompeterende metaalioon transportasie eksperimente is uitgevoer met behulp van hierdie vloeistof membraan stelsel. Die twee waterige fases is deur middel van Atoomabsorpsie Spektroskopie (AAS) ge-analiseer en resultate is bevestig met gebruik van Induktief-gekoppelde Plasma-Optiese Emissie Spektroskopie (IGP-OES). Die resultate het getoon dat elkeen van die N,N-dialkiel-gesubstitueerde-N'-asiel(ariel) (HL) tioureums, met uitsondering van N,N-di(2-hidroksie-etiel)-N'-benzieltioureum(HL 3) en Npiperidiel- N'-4-nitrobenzieltioureum(HL9 ), doeltreffend en selektief was vir Ag(l) transportasie. HL9 was selektief vir Ag(I), maar die transportasie waarde was nie hoog nie, dws. dit was nie doeltreffend nie. HL3 was selektief vir Cu(II). Met gebruik van ons eksperimentele kondisies is 13% Cu(lI) getransporteer deur HL 3. Van die N,N-dialkiel-N'- ariel tioureums, is maksimum transportasie van Ag(l) verkry met gebruik van N,N-dietiel- N'-4-chlorobenzieltioureum (HL5) en N,N-di-n-butiel-N'-benzieltioureum (HL1). Met gebruik van ons eksperimentele kondisies was die persentasie transportasie van Ag(l) deur HL5 en HL 1 48% en 42% onderskeidelik. Die selektiwiteit en doeltreffendheid van 3,3,3' ,3'-tetra-etiel-1 ,t-isoftaltelblstioureumtl+L 12) en N,N-di-etiel-N'-kamfonieltioureum (HL13) vir Ag(l) transportasie is ook onderneem. Ons was besonder ge-interesseerd om die Ag(l) transportasie en ekstraksie van hierdie ligande te vergelyk met dié van die HL en H2L tipe ligande. Die eksperimentele resultate het getoon dat van al die ligande wat bestudeer is, HL 13 die doeltreffendste en mees selektiewe ionofoor was. Van besondere, belang was dat, afhangend van die ligand konsentrasie wat gebruik is, HL13 71-81% Ag(l) getransporteer het. Kompeterende twee-fase metaalioon vloeistof-vloeistof ekstraksie eksperimente is ook uitgevoer onder toestande soortgelyk aan dié van die transportasie eksperimente. Die resultate toon dat met varierende ligand konsentrasie, tot soveel as 100% Ag(l) selektief en doeltreffend geëkstrakeer word vanuit 'n mengsel van die sewe metaal ione. N,N-di-n-butiel-N'-benzieltioureum (HL1 ) ligande en die kompleks daarvan met Ag(l) is ook gesintetiseer. Enkel-kristalle van die kompleks is verkry en X-straal kristallografiese analiese is onderneem. Die kristalstruktuur toon hoedat Ag(l) gebind is aan die gedeprotoneerde ligand deur die S en Q atome en toon ook interessante [Ag(L-S,Q)]4 groepe in die vaste toestand. Hierdie struktuur is monoklinies en kristaliseer in die ruimtegroep P21!c met a = 17.805(4) Á, b = 21.759(4)Á, c = 36.438(7)Á, P = 96.34(3t, z = 8 en 'n finale R-faktor van 5.4%.

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

The experimental work conducted in this thesis was aimed at determining the thermodynamic quantities associated with the formation of complexes formed between various metal ions and KELEX 100, a ligand which is used commercially for liquid - liquid extraction. In order to accomplish this, the beats of protonation of the ligand KELEX 100 were determined calorimetrically at 25°C in a partially aqueous medium of75% (v/v) l,4-dioxane and at an ionic strength of 0.1 mol dm·3• Extraneous heat effects that usually accompany complex formation were accounted for by measuring each heat contribution separately. The complexation of the lead (II), cadmium (II) and nickel (II) ions with KELEX 100 was studied in 75%(v/v) l,4-dioxane medium. The enthalpies of complexation were measured calorimetrically and calculated using the program LETAGROP KALLE. These results were combined with the values of the Gibbs free energies available in the literature for these systems to yield the entropies of complexation. In all calorimetric determinations a constant ionic strength of 0.1 mol dm'3 and a temperature of 25°C was maintained. The calculated enthalpies and entropies are discussed in terms of a number of factors that affect the thermodynamics of the systems. These factors include the structure of the ligand molecule, the nature of the donor atoms, the degree of substitution on the ligand and the properties of the metal atom such as charge and size, and the nature of the solvent. The cumulative enthalpies and entropies of formation of the metal-ligand complexes are favourable, Le. complexation is accompanied by a decrease in enthalpy and an increase in entropy. However, the enthalpy changes contribute more to the stability of the complexes and hence are the driving forces for complex formation. In the case of the Cd(II) ion, the enthalpy and entropy changes are similar. The cumulative enthalpies of formation increase (Le., become more exothermic) in the order: Ni > Pb > Cd while the reverse order is found for the entropies of formation. The smaller enthalpy change for the Cd(II) complex is possibly due to the weak interaction between the 'soft' Cd(II) ion and the 'hard' KELEX 100 ligand while the decrease in entropy for the Ni(II) may be due to the loss of fewer solvent molecules from the Ni(II) hydration sphere on complexation with the ligand. The stepwise entropy and enthalpy changes for the formation of the ML+ complexes are dependent on the ionic radius of the metal ion. However, no linear correlations exist between the cumulative entropy or enthalpy changes of formation of the ML complexes and the size of the metal ion. The stepwise and cumulative enthalpies of formation appear to be largely independent of steric effects of the bulky alkyl substituent on the KELEX 100 ligand. The increased steric hindrance of the substituent decreases the cumulative entropy change for the formation of the Ni(II) complexes. However, in the case of the Pb(II) complexes, steric effects do not appear to affect the cumulative entropies of complex formation. / Thesis (M.Sc.)-University of Natal, 1995.