Coordination polymers for denitrogenation of fuel oils
- Authors: Dembaremba, Tendai O
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53630 , vital:45682
- Description: In this thesis, we present adsorptive removal of nitrogen-containing compounds from fuel oil as an alternative to complement conventional hydrotreatment to obtain ultra-low sulfur and nitrogen levels. This is in cognizance of the challenges nitrogen-containing compounds pose to the hydrotreatment process, particularly their inhibition and/or poisoning of the catalysts used in the process, of which basic nitrogen-containing compounds are the major culprits. Selectivity is the biggest challenge for adsorptive removal of nitrogen-containing compounds. We explore reticular synthesis of metal organic frameworks and the use of coordinatively unsaturated metal sites in 1-dimensional coordination polymers to achieve good selectivity for nitrogen-containing compounds. In the first part of the thesis, reticular synthesis of metal organic frameworks to control the size of the cavity, and strategically use the linkers and metal centres was envisaged. In this work we explored variation of the metal centres in the secondary building units (SBUs of the MOFs as the first step to the testing and implementation of the design strategies. Carbazole, representing carbazoles which the major compounds that remain in hydrotreated fuel, was the target compound. Four MOFs of zinc (Zn-CDC-bpe), copper (Cu-CDC-bpe), nickel (Ni-CDC-bpe) and cobalt (Co-CDC-bpe) based on the formation of a dinuclear metal paddlewheel SBUs with the ligand 9H-Carbazole-3,6-dicarboxylic acid (H2CDC) and occupation of the axial positions of the paddlewheel by 1,2-Bis(4-pyridyl)ethane (bpe) to form porous networks were synthesized. A fifth MOF containing only CDC which forms a [Zn4O(O2C-R)5(O2HC-R)] SBU was also synthesized (Zn-CDC). The ligand H2CDC was inspired by the possibility of improving selectivity for carbazole via π–π interactions through the more preferred parallel-offset stacking as well as the possibility for further substitution of the carbazole N-H to add groups that improve selectivity. The sizes of the MOF cavities can then be controlled by choosing different lengths of ligands analogous to 1,2-Bis(4-pyridyl)ethane (bpe), e.g. 4,4’-bipyridine and pyrazine. All the MOFs showed good selectivity of carbazole. The Zn-CDC MOF also had good selectivity for the basic nitrogen-containing compounds tested: quinoline, isoquinoline, quinaldine and 1-naphthylamine. Its uptake of carbazole was also slightly higher. This was attributed to the presence of an unsaturated Zn site in the SBU. Adsorption in all the MOFs was primarily due to physisorption. It was concluded that the role of the metal centre does not play a significant role in the adsorption of carbazole besides providing a template for reticular synthesis. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Full Text: false
- Date Issued: 2021-12
- Authors: Dembaremba, Tendai O
- Date: 2021-12
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10948/53630 , vital:45682
- Description: In this thesis, we present adsorptive removal of nitrogen-containing compounds from fuel oil as an alternative to complement conventional hydrotreatment to obtain ultra-low sulfur and nitrogen levels. This is in cognizance of the challenges nitrogen-containing compounds pose to the hydrotreatment process, particularly their inhibition and/or poisoning of the catalysts used in the process, of which basic nitrogen-containing compounds are the major culprits. Selectivity is the biggest challenge for adsorptive removal of nitrogen-containing compounds. We explore reticular synthesis of metal organic frameworks and the use of coordinatively unsaturated metal sites in 1-dimensional coordination polymers to achieve good selectivity for nitrogen-containing compounds. In the first part of the thesis, reticular synthesis of metal organic frameworks to control the size of the cavity, and strategically use the linkers and metal centres was envisaged. In this work we explored variation of the metal centres in the secondary building units (SBUs of the MOFs as the first step to the testing and implementation of the design strategies. Carbazole, representing carbazoles which the major compounds that remain in hydrotreated fuel, was the target compound. Four MOFs of zinc (Zn-CDC-bpe), copper (Cu-CDC-bpe), nickel (Ni-CDC-bpe) and cobalt (Co-CDC-bpe) based on the formation of a dinuclear metal paddlewheel SBUs with the ligand 9H-Carbazole-3,6-dicarboxylic acid (H2CDC) and occupation of the axial positions of the paddlewheel by 1,2-Bis(4-pyridyl)ethane (bpe) to form porous networks were synthesized. A fifth MOF containing only CDC which forms a [Zn4O(O2C-R)5(O2HC-R)] SBU was also synthesized (Zn-CDC). The ligand H2CDC was inspired by the possibility of improving selectivity for carbazole via π–π interactions through the more preferred parallel-offset stacking as well as the possibility for further substitution of the carbazole N-H to add groups that improve selectivity. The sizes of the MOF cavities can then be controlled by choosing different lengths of ligands analogous to 1,2-Bis(4-pyridyl)ethane (bpe), e.g. 4,4’-bipyridine and pyrazine. All the MOFs showed good selectivity of carbazole. The Zn-CDC MOF also had good selectivity for the basic nitrogen-containing compounds tested: quinoline, isoquinoline, quinaldine and 1-naphthylamine. Its uptake of carbazole was also slightly higher. This was attributed to the presence of an unsaturated Zn site in the SBU. Adsorption in all the MOFs was primarily due to physisorption. It was concluded that the role of the metal centre does not play a significant role in the adsorption of carbazole besides providing a template for reticular synthesis. , Thesis (PhD) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Full Text: false
- Date Issued: 2021-12
Optimising the uptake of [𝐈𝐫𝐂𝐥𝟔]𝟐− by a diammonium resin: HCl effect and resin performance
- Authors: Ngayeka, Mbokazi Zizipho
- Date: 2021-04
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/54089 , vital:46284
- Description: The separation of [IrCl6]2- from [RhCl5(H2O)]2- by silica microparticles functionalized with 1,10-diamindecane (C10) and quaternized with 4-nitrobenzylchloride (NO2Benz) in various hydrochloric acid mediums was investigated by continuous column studies. The sorbent materials were synthesized using three different routes: Synthesis route 1 (NaI catalyzed synthesis of diammonium functionalized silica microparticles), Synthesis Route 2 (via silylazation of silica followed by functionalization) and Synthesis Route 3 (silane-based sorbent material). The functionalized sorbent materials were characterized by NMR, Microanalysis, SEM-EDS, FT-IR, TGA and BET surface area. The separation efficiency of the quaternary diammonium cations was investigated under dynamic flow adsorption conditions. Preliminary ICP-OES runs were done, at 6 M HCl, to assess which synthesis route gave the best performing sorbent material. [IrCl6]2- selectivity of the sorbent materials was achieved by washing with an HCl solution to remove unadsorbed metal species, then stripping off the [RhCl5(H2O)]2- with 0.05 M of sodium chlorate and the iridium species was eluted with a 20% HCl solution. From the preliminary ICP-OES, loading capacities were calculated, and it was observed that the three sorbent materials from synthesis route 2 (13.89 mg/g for (4) SSC10NO2Benz-A, 1.44 mg/g for (5) SSC10NO2Benz-HoA, and 1.0859 mg/g for (6) SSC10NO2Benz-DoA) showed the highest uptake of [IrCl6]2- and route 1 (1.89 mg/g for (1) SSC10NO2Benz-A, 1.25 mg/g for (2) SSC10NO2Benz-HoA and 0.99 mg/g for (3) SSC10NO2Benz-DoA ) and Route 3 (0.55 mg/g for (7) SC10-AI and 0.755 mg/g for (8) SC10-ACl) materials did not perform efficiently enough, thus were not used further for the HCl study. Within synthesis route 2, three sorbent materials were evaluated, which had varying quantities of the cation: SSC10NO2Benz-A (having a quantity previously used in our research and denoted A), SSC10NO2Benz-HoA (having a quantity Half of A) and SSC10NO2Benz-DoA (having a quantity double of A). SSC10NO2Benz-A showed the highest loading capacity than SSC10NO2Benz-HoA and SSC10NO2Benz-DoA; HCl studies were carried out using SSC10NO2Benz-A. HCl solution having different concentrations (5, 5.5 , 6 , 6.6 and 6.8 M) were used to prepare the metal solutions. This was done to assess which HCl concentration gave the best metal solution containing high amounts of [IrCl6]2- and [RhCl5(H2O)]2-, which would result in a more efficient separation. An auto titrator was used to standardize the HCl concentrations, and the metal ion chloride species solutions were determined by UV-Vis, and their concentrations were confirmed with ICP-OES. Column sorption of iridium and rhodium on SSC10NO2Benz-A using these HCl solutions was carried out, and loading capacities of [IrCl6]2- were obtained. The loading capacities of the 5 M, 5.5 M, 6 M, 6,6 M and 6.8 M HCl solutions for [IrCl6]2- were 2.64, 4.01, 13.89, 18.15 and 7.23 mg/g, respectively. The optimum separation conditions were thus determined by investigating effective parameters such as the method of synthesis, silica to cation ratio, HCl concentration and flow rate. This thesis presents quaternary diammonium sorbent materials that could be applied in feed solutions from ore processing for iridium recovery. , Thesis (MSc) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Full Text:
- Date Issued: 2021-04
- Authors: Ngayeka, Mbokazi Zizipho
- Date: 2021-04
- Subjects: Port Elizabeth (South Africa) , Eastern Cape (South Africa) , South Africa
- Language: English
- Type: Master's theses , text
- Identifier: http://hdl.handle.net/10948/54089 , vital:46284
- Description: The separation of [IrCl6]2- from [RhCl5(H2O)]2- by silica microparticles functionalized with 1,10-diamindecane (C10) and quaternized with 4-nitrobenzylchloride (NO2Benz) in various hydrochloric acid mediums was investigated by continuous column studies. The sorbent materials were synthesized using three different routes: Synthesis route 1 (NaI catalyzed synthesis of diammonium functionalized silica microparticles), Synthesis Route 2 (via silylazation of silica followed by functionalization) and Synthesis Route 3 (silane-based sorbent material). The functionalized sorbent materials were characterized by NMR, Microanalysis, SEM-EDS, FT-IR, TGA and BET surface area. The separation efficiency of the quaternary diammonium cations was investigated under dynamic flow adsorption conditions. Preliminary ICP-OES runs were done, at 6 M HCl, to assess which synthesis route gave the best performing sorbent material. [IrCl6]2- selectivity of the sorbent materials was achieved by washing with an HCl solution to remove unadsorbed metal species, then stripping off the [RhCl5(H2O)]2- with 0.05 M of sodium chlorate and the iridium species was eluted with a 20% HCl solution. From the preliminary ICP-OES, loading capacities were calculated, and it was observed that the three sorbent materials from synthesis route 2 (13.89 mg/g for (4) SSC10NO2Benz-A, 1.44 mg/g for (5) SSC10NO2Benz-HoA, and 1.0859 mg/g for (6) SSC10NO2Benz-DoA) showed the highest uptake of [IrCl6]2- and route 1 (1.89 mg/g for (1) SSC10NO2Benz-A, 1.25 mg/g for (2) SSC10NO2Benz-HoA and 0.99 mg/g for (3) SSC10NO2Benz-DoA ) and Route 3 (0.55 mg/g for (7) SC10-AI and 0.755 mg/g for (8) SC10-ACl) materials did not perform efficiently enough, thus were not used further for the HCl study. Within synthesis route 2, three sorbent materials were evaluated, which had varying quantities of the cation: SSC10NO2Benz-A (having a quantity previously used in our research and denoted A), SSC10NO2Benz-HoA (having a quantity Half of A) and SSC10NO2Benz-DoA (having a quantity double of A). SSC10NO2Benz-A showed the highest loading capacity than SSC10NO2Benz-HoA and SSC10NO2Benz-DoA; HCl studies were carried out using SSC10NO2Benz-A. HCl solution having different concentrations (5, 5.5 , 6 , 6.6 and 6.8 M) were used to prepare the metal solutions. This was done to assess which HCl concentration gave the best metal solution containing high amounts of [IrCl6]2- and [RhCl5(H2O)]2-, which would result in a more efficient separation. An auto titrator was used to standardize the HCl concentrations, and the metal ion chloride species solutions were determined by UV-Vis, and their concentrations were confirmed with ICP-OES. Column sorption of iridium and rhodium on SSC10NO2Benz-A using these HCl solutions was carried out, and loading capacities of [IrCl6]2- were obtained. The loading capacities of the 5 M, 5.5 M, 6 M, 6,6 M and 6.8 M HCl solutions for [IrCl6]2- were 2.64, 4.01, 13.89, 18.15 and 7.23 mg/g, respectively. The optimum separation conditions were thus determined by investigating effective parameters such as the method of synthesis, silica to cation ratio, HCl concentration and flow rate. This thesis presents quaternary diammonium sorbent materials that could be applied in feed solutions from ore processing for iridium recovery. , Thesis (MSc) -- Faculty of Science, School of Biomolecular and Chemical Sciences, 2021
- Full Text:
- Date Issued: 2021-04
Oxidative desulfurization of fuel oils-catalytic oxidation and adsorptive removal of organosulfur compounds
- Authors: Ogunlaja, Adeniyi Sunday
- Date: 2014
- Subjects: Organosulfur compounds , Organosulfur compounds -- Oxidation , Organosulfur compounds -- Absorption and adsorption , Petroleum as fuel , Catalysis , Imprinted polymers , Molecular imprinting , Nanofibers , Electrospinning
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4498 , http://hdl.handle.net/10962/d1013152
- Description: The syntheses and evaluation of oxidovanadium(IV) complexes as catalysts for the oxidation of refractory organosulfur compounds in fuels is presented. The sulfones produced from the oxidation reaction were removed from fuel oils by employing molecularly imprinted polymers (MIPs). The oxidovanadium(IV) homogeneous catalyst, [V ͥ ͮ O(sal-HBPD)], as well as its heterogeneous polymer supported derivatives, poly[V ͥ ͮ O(sal-AHBPD)] and poly[V ͥ ͮ O(allylSB-co-EGDMA)], were synthesized and fully characterized by elemental analysis, FTIR, UV-Vis, XPS, AFM, SEM, BET and single crystal XRD for [V ͥ ͮ O(sal-HBPD)]. The MIPs were also characterized by elemental analysis, FTIR, SEM, EDX and BET. The catalyzed oxidation of fuel oil model sulfur compounds, thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), was conducted under batch and continuous flow processes at 40°C by using tert-butylhydroperoxide (t-BuOOH) as oxidant. The continuous flow oxidation process presented the highest overall conversions and very high selectivity for sulfones. Maximum oxidation conversions of 71%, 89%, 99% and 88% was achieved for TH, BT, DBT and 4,6-DMDBT respectively when poly[V ͥ ͮ O(allylSB-co-EGDMA)] was employed at a flow-rate of 1 mL/h with over 90% sulfone selectivity. The process was further applied to the oxidation of hydro-treated diesel containing 385 ± 4.6 ppm of sulfur (mainly dibenzothiophene and dibenzothiophene derivatives), and this resulted to a high sulfur oxidation yield (> 99%), thus producing polar sulfones which are extractible by polar solid phase extractants. Adsorption of the polar sulfone compounds was carried-out by employing MIPs which were fabricated through the formation of recognition sites complementary to oxidized sulfur-containing compounds (sulfones) on electrospun polybenzimidazole (PBI) nanofibers, cross-linked chitosan microspheres and electrospun chitosan nanofibers. Adsorption of benzothiophene sulfone (BTO₂), dibenzothiophene sulfone (DBTO₂) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO₂) on the various molecularly imprinted adsorbents presented a Freundlich (multi-layered) adsorption isotherm which indicated interaction of adsorbed organosulfur compounds. Maximum adsorption observed for BTO₂, DBTO₂ and 4,6-DMDBTO₂ respectively was 8.5 ± 0.6 mg/g, 7.0 ± 0.5 mg/g and 6.6 ± 0.7 mg/g when imprinted chitosan nanofibers were employed, 4.9 ± 0.5 mg/g, 4.2 ± 0.7 mg/g and 3.9 ± 0.6 mg/g on molecularly imprinted chitosan microspheres, and 28.5 ± 0.4 mg/g, 29.8 ± 2.2 mg/g and 20.1 ± 1.4 mg/g on molecularly imprinted PBI nanofibers. Application of electrospun chitosan nanofibers on oxidized hydro-treated diesel presented a sulfur removal capacity of 84%, leaving 62 ± 3.2 ppm S in the fuel, while imprinted PBI electrospun nanofibers displayed excellent sulfur removal, keeping sulfur in the fuel after the oxidation/adsorption below the determined limit of detection (LOD), which is 2.4 ppm S. The high level of sulfur removal displayed by imprinted PBI nanofibers was ascribed to hydrogen bonding effects, and π-π stacking between aromatic sulfone compounds and the benzimidazole ring which were confirmed by chemical modelling with density functional theory (DFT) as well as the imprinting effect. The home-made pressurized hot water extraction (PHWE) system was applied for extraction/desorption of sulfone compounds adsorbed on the PBI nanofibers at a flow rate of 1 mL/min and at 150°C with an applied pressure of 30 bars. Application of molecularly imprinted PBI nanofibers for the desulfurization of oxidized hydro-treated fuel showed potential for use in refining industries to reach ultra-low sulfur fuel level, which falls below the 10 ppm sulfur limit which is mandated by the environmental protection agency (EPA) from 2015.
- Full Text:
- Date Issued: 2014
- Authors: Ogunlaja, Adeniyi Sunday
- Date: 2014
- Subjects: Organosulfur compounds , Organosulfur compounds -- Oxidation , Organosulfur compounds -- Absorption and adsorption , Petroleum as fuel , Catalysis , Imprinted polymers , Molecular imprinting , Nanofibers , Electrospinning
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4498 , http://hdl.handle.net/10962/d1013152
- Description: The syntheses and evaluation of oxidovanadium(IV) complexes as catalysts for the oxidation of refractory organosulfur compounds in fuels is presented. The sulfones produced from the oxidation reaction were removed from fuel oils by employing molecularly imprinted polymers (MIPs). The oxidovanadium(IV) homogeneous catalyst, [V ͥ ͮ O(sal-HBPD)], as well as its heterogeneous polymer supported derivatives, poly[V ͥ ͮ O(sal-AHBPD)] and poly[V ͥ ͮ O(allylSB-co-EGDMA)], were synthesized and fully characterized by elemental analysis, FTIR, UV-Vis, XPS, AFM, SEM, BET and single crystal XRD for [V ͥ ͮ O(sal-HBPD)]. The MIPs were also characterized by elemental analysis, FTIR, SEM, EDX and BET. The catalyzed oxidation of fuel oil model sulfur compounds, thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), was conducted under batch and continuous flow processes at 40°C by using tert-butylhydroperoxide (t-BuOOH) as oxidant. The continuous flow oxidation process presented the highest overall conversions and very high selectivity for sulfones. Maximum oxidation conversions of 71%, 89%, 99% and 88% was achieved for TH, BT, DBT and 4,6-DMDBT respectively when poly[V ͥ ͮ O(allylSB-co-EGDMA)] was employed at a flow-rate of 1 mL/h with over 90% sulfone selectivity. The process was further applied to the oxidation of hydro-treated diesel containing 385 ± 4.6 ppm of sulfur (mainly dibenzothiophene and dibenzothiophene derivatives), and this resulted to a high sulfur oxidation yield (> 99%), thus producing polar sulfones which are extractible by polar solid phase extractants. Adsorption of the polar sulfone compounds was carried-out by employing MIPs which were fabricated through the formation of recognition sites complementary to oxidized sulfur-containing compounds (sulfones) on electrospun polybenzimidazole (PBI) nanofibers, cross-linked chitosan microspheres and electrospun chitosan nanofibers. Adsorption of benzothiophene sulfone (BTO₂), dibenzothiophene sulfone (DBTO₂) and 4,6-dimethyldibenzothiophene sulfone (4,6-DMDBTO₂) on the various molecularly imprinted adsorbents presented a Freundlich (multi-layered) adsorption isotherm which indicated interaction of adsorbed organosulfur compounds. Maximum adsorption observed for BTO₂, DBTO₂ and 4,6-DMDBTO₂ respectively was 8.5 ± 0.6 mg/g, 7.0 ± 0.5 mg/g and 6.6 ± 0.7 mg/g when imprinted chitosan nanofibers were employed, 4.9 ± 0.5 mg/g, 4.2 ± 0.7 mg/g and 3.9 ± 0.6 mg/g on molecularly imprinted chitosan microspheres, and 28.5 ± 0.4 mg/g, 29.8 ± 2.2 mg/g and 20.1 ± 1.4 mg/g on molecularly imprinted PBI nanofibers. Application of electrospun chitosan nanofibers on oxidized hydro-treated diesel presented a sulfur removal capacity of 84%, leaving 62 ± 3.2 ppm S in the fuel, while imprinted PBI electrospun nanofibers displayed excellent sulfur removal, keeping sulfur in the fuel after the oxidation/adsorption below the determined limit of detection (LOD), which is 2.4 ppm S. The high level of sulfur removal displayed by imprinted PBI nanofibers was ascribed to hydrogen bonding effects, and π-π stacking between aromatic sulfone compounds and the benzimidazole ring which were confirmed by chemical modelling with density functional theory (DFT) as well as the imprinting effect. The home-made pressurized hot water extraction (PHWE) system was applied for extraction/desorption of sulfone compounds adsorbed on the PBI nanofibers at a flow rate of 1 mL/min and at 150°C with an applied pressure of 30 bars. Application of molecularly imprinted PBI nanofibers for the desulfurization of oxidized hydro-treated fuel showed potential for use in refining industries to reach ultra-low sulfur fuel level, which falls below the 10 ppm sulfur limit which is mandated by the environmental protection agency (EPA) from 2015.
- Full Text:
- Date Issued: 2014
The coordination and extractive chemistry of the later 3d transition metal ions with N, N'-donor imidazole-based ligands
- Authors: Moleko, Pulleng
- Date: 2014
- Subjects: Solvent extraction , Coordination compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/8382 , vital:26352
- Description: The application of bidentate N,N'-donor ligands, such as 2,2'-biimidazole (BIIMH2) and 2,2'-pyridylimidazole (PIMH) and (1H-benzimidazol-2yl)-N-methylmethanamine (BIMAH), in the solvent extraction of base metal ions from an acidic sulfate/sulfonate medium was investigated. PIMH and BIMAH showed selectivity for Ni(II) with the only interfering ion being Cu(II) in the pH range 1.2-1.8 but BIIMH2 lacked selectivity. The extraction patterns observed were influenced by stereochemical aspects, and this agreed well with the envisaged design of nickel(II)-specific extractants through stereochemical “tailor-making” which is proposed in this study. The extraction patterns were explained from a coordination chemistry point of view using spectroscopic analysis and single crystal X-ray analysis to diagnose the geometry of the complexes formed from the interaction of the base metal ions with the ligands. The formation of the trigonal bipyrimidal [Cu(PIM)2(H2O)](SO4) complex, with a water molecule coordinated, while nickel(II) forms a square planar bisPIMH was put forward as the reason for extraction pattern observed with this ligand. Cobalt(II) also forms a bisPIMH complex but has two water molecules coordinated in the formation of a distorted octahedral complex, and this results in less extractable species. A similar observation as for PIMH was noticed in BIMAH complexation reactions. The BIIMH2 complexes were found to be distorted octahedral, through the bis-coordination of BIIMH2 and two sulfonate ions, resulting in lack of pH-metric separation of the later 3d metal ions. The stability constants data was in agreement with what was observed in the solvent extraction and coordination chemistry studies for the three ligand systems.
- Full Text:
- Date Issued: 2014
- Authors: Moleko, Pulleng
- Date: 2014
- Subjects: Solvent extraction , Coordination compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10948/8382 , vital:26352
- Description: The application of bidentate N,N'-donor ligands, such as 2,2'-biimidazole (BIIMH2) and 2,2'-pyridylimidazole (PIMH) and (1H-benzimidazol-2yl)-N-methylmethanamine (BIMAH), in the solvent extraction of base metal ions from an acidic sulfate/sulfonate medium was investigated. PIMH and BIMAH showed selectivity for Ni(II) with the only interfering ion being Cu(II) in the pH range 1.2-1.8 but BIIMH2 lacked selectivity. The extraction patterns observed were influenced by stereochemical aspects, and this agreed well with the envisaged design of nickel(II)-specific extractants through stereochemical “tailor-making” which is proposed in this study. The extraction patterns were explained from a coordination chemistry point of view using spectroscopic analysis and single crystal X-ray analysis to diagnose the geometry of the complexes formed from the interaction of the base metal ions with the ligands. The formation of the trigonal bipyrimidal [Cu(PIM)2(H2O)](SO4) complex, with a water molecule coordinated, while nickel(II) forms a square planar bisPIMH was put forward as the reason for extraction pattern observed with this ligand. Cobalt(II) also forms a bisPIMH complex but has two water molecules coordinated in the formation of a distorted octahedral complex, and this results in less extractable species. A similar observation as for PIMH was noticed in BIMAH complexation reactions. The BIIMH2 complexes were found to be distorted octahedral, through the bis-coordination of BIIMH2 and two sulfonate ions, resulting in lack of pH-metric separation of the later 3d metal ions. The stability constants data was in agreement with what was observed in the solvent extraction and coordination chemistry studies for the three ligand systems.
- Full Text:
- Date Issued: 2014
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