Salwa A. Ahmed

Synthesis, characterization and structure effects on selectivity properties of silica gel covalently bonded diethylenetriamine mono- and bis-salicyaldehyde and naphthaldehyde Schiff,s bases towards some heavy metal ions

Four silica gel-immobilized new metal chelate Schiff(,)s bases were synthesized (I-IV). Silica gel chemically bonded diethylenetriamine mono-naphthaldehyde and mono-salicyaldehyde Schiffs bases (phases I and III) were produced via the interaction of silica gel-modified diethylenetriamine with naphthaldehyde and salicylaldehyde, respectively. However, phases II and IV arose through the interaction of bis-naphthaldehyde and bis-salicylaldehyde Schiff(,)s bases of diethylenetriamine with 3-chloropropyltrimethoxysilane modified silica gel. The characterization of such new phases, their capabilities towards selective extraction or separation of Fe(III), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) ions were studied and evaluated by both batch and column techniques as a function of pH and time of contact. Phases III and I showed high performance towards Cu(II) extraction, where their Cu(II) sorption determined to be 0.957 and 0.940 mmol g(-1), respectively. However, for phases IV and II, the great affinity was devoted to Fe(III) extraction followed by Cu(II) ions. The reactivity of metal ion sorption was discussed in the light of effects of bulkiness as well as orientation of immobilized chelate on sorbent reactivity. Donor sites of phases III and I (diethylenetriamine and azomethene nitrogens along with phenolic hydroxyl group oxygen) are fully active, whereas phases IV and II are partially active with only participation of oxygen and azomethene nitrogen. The order of increasing thermal stability (IV<II<I<III) and fastness of metal uptake equilibration process coincides satisfactorily with decreasing bulkiness of the chelate. Results of separation under dynamic conditions of binary mixtures containing Cu(II) with Ni(II), Zn(II), Cd(II) and Pb(II) using phase III are in accordance with its selectivity towards Cu(II) retention relative to the other coexisting ions.

Alumina physically loaded by thiosemicarbazide for selective preconcentration of mercury(II) ion from natural water samples.

The multifunctional ligand, thiosemicarbazide, was physically loaded on neutral alumina. The produced alumina-modified solid phase (SP) extractor named, alumina-modified thiosemicarbazide (AM-TSC), experienced high thermal and medium stability. This new phase was identified based on surface coverage determination by thermal desorption method to be 0.437+/-0.1 mmol g(-1). The selectivity of AM-TSC phase towards the uptake of different nine metal ions was checked using simple, fast and direct batch equilibration technique. AM-TSC was found to have the highest capacity in selective extraction of Hg(II) from aqueous solutions all over the range of pH used (1.0-7.0), compared to the other eight tested metal ions. So, Hg(II) uptake was 1.82 mmol g(-1) (distribution coefficient log K(d)=5.658) at pH 1.0 or 2.0 and 1.78, 1.73, 1.48, 1.28 and 1.28 mmol g(-1) (log K(d)=4.607, 4.265, 3.634, 3.372 and 3.372), at pH 3.0, 4.0, 5.0, 6.0 and 7.0, respectively. On the other hand, the metal ions Ca(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) showed low uptake values in range 0.009-0.720 mmol g(-1) (log K(d)<3.0) at their optimum pH values. A mechanism was suggested to explain the unique uptake of Hg(II) ions based on their binding as neutral and chloroanionic species predominate at pH values < or =3.0 of a medium rich in chloride ions. Application of the new phase for the preconcentration of ultratrace amounts of Hg(II) ions spiked natural water samples: doubly distilled water (DDW), drinking tap water (DTW) and Nile river water (NRW) using cold vapor atomic absorption spectroscopy (CV-AAS) was studied. The high recovery values obtained using AM-TSC (98.5+/-0.5, 98.0+/-0.5 and 103.0+/-1.0) for DDW, DTW and NRW samples, respectively based on excellent enrichment factor 1000, along with a good precision (R.S.D.% 0.51-0.97%, n=3) demonstrate the accuracy and validity of the new modified alumina sorbent for preconcentrating ultratrace amounts of Hg(II) with no matrix interference.

Alumina modified by dimethyl sulfoxide as a new selective solid phase extractor for separation and preconcentration of inorganic mercury(II)

Dimethyl sulfoxide (DMSO) was simply immobilized to neutral alumina via quite strong hydrogen bonding between sulfoxide oxygen and surface alumina hydroxo groups. The produced alumina-modified dimethyl sulfoxide (AMDMSO) solid phase (SP)-extractor experienced high thermal and medium stability. Moreover, the small and compact size of DMSO moiety permit high surface coverage evaluated to be 2.1+/-0.1 mmol g(-1) of alumina. Hg(II) uptake was 1.90 mmol g(-1)(distribution coefficient log K(d)=5.658) at pH 1.0 or 2.0, 1.68 mmol g(-1) (log K(d)=4.067) at pH 3.0 or 4.0 while the metal ions Ca(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) showed low values 0.513-0.118 mmol g(-1) (log K(d)<3.0) in the pH range 4.0-7.0. A mechanism was suggested to explain the unique uptake of Hg(II) ions by binding as neutral and chloroanionic species predominate at pH values< or =3.0 of a medium rich in chloride ions. A direct and fast batch separation mode was achieved successfully to retain selectively Hg(II) in presence of other eight coexisting metal ions. Thus, Hg(II) was completely retained; Ca(II), Co(II), Ni(II) and Cd(II) were not retained, while Pb(II), Cu(II), Zn(II) and Fe(III) exhibited very low percentage retention evaluated to be 0.42, 0.49, 1.4 and 5.43%, respectively. The utility of the new modified alumina sorbent for concentrating of ultratrace amounts of Hg(II) was performed by percolating 2l of doubly distilled water, drinking tap water, and Nile river water spiked with 10 ng/l over 100mg of the sorbent packed in a minicolumn used as a thin layer enrichment bed prior to the determination by CV-AAS. The high recovery values obtained (98.5+/-0.5, 98.5+/-0.5 and 103.0+/-1.0) based on excellent enrichment factor 1000, along with a good precision (R.S.D.% 0.51-0.97%, N=3) demonstrate the accuracy and validity of the new modified alumina sorbent for preconcentrating ultratrace amounts of Hg(II) with no matrix interference.

Reactivity of Thioglycolic Acid Physically and Chemically Bound to Silica Gel as New Selective Solid Phase Extractors for Removal of Heavy Metal Ions From Natural Water Samples

A method is presented for the immobilization of thioglycolic acid moiety on the surface of active silica gel via a simple and direct synthetic route and based on one step reaction procedure. Two-product solid phase extractors were successfully synthesized according to physical adsorption and chemical immobilization binding techniques, phases (I) and (II), respectively. The mode of interaction between the silanol group and the thioglycolic moiety was also discussed for both phases based on the infrared analysis studies. The thermal stability properties as well as the effect of buffer solutions on the percentage hydrolysis of the two silica gel phases were examined and revealed the high stability and superiority of silica phase (II) in these respects. The evaluation of the selectivity and metal uptake properties incorporated in these two silica gel phases were also studied and discussed for a series of divalent heavy metal ions under different controlling factors. The mmol/g values were found to be higher in case of phase (I). The selective removal and extraction of some heavy metal ions, viz . Cu(II), Zn(II), and Hg(II) from natural seawater samples was successfully accomplished with the percentage recovery values for the three tested metal ions in the range of 96.5-98.4 - 0.2-0.6%. The presence of higher concentrations of Na(I), K(I), Mg(II) and Ca(II) showed insignificant role or no matrix effect on such selective extraction process due to their 0% values of removal by these silica gel phases (I) and (II).

Selective separation of silver(I) and mercury(II) ions in natural water samples using alumina modified thiouracil derivatives as new solid phase extractors

A simple and reliable solid-phase extraction (SPE) method has been developed to synthesise two new sorbents: 6-propyl-2-thiouracil and 5,6-diamino-2-thiouracil physically loaded onto alumina surface, phases I and II, respectively. The synthesis of these new phases has been confirmed by IR-spectroscopy. The surface concentrations of the organic moieties were determined to be 0.182 and 0.562 mmol g−1 for phases I and II, respectively. The evaluation of the selectivity and metal uptake properties incorporated in these two alumina phases were also studied and discussed for 10 different metal ions: Ca(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Pb(II) and Ag(I) under different controlling factors. The data obtained clearly indicated that the new SP-extractors have the highest affinity for retention of Hg(II) ions. Selective separation of Hg(II) from Ag(I) as one of the most interfering ion, in addition to the other eight coexisting metal ions under investigation, was achieved successfully using the new sorbents at pH = 9.0 under static conditions. Therefore, Hg(II) exhibits major retention percentage (100.0%) using phase I or II. However, Ag(I) exhibits minor retention percentage equal to 1.33% using phase I and 0.67% using phase II. On the other hand, the retention percentage of the other eight metal ions ranged (0.0–3.08%) using phase I and (0.0–1.54%) using phase II at the same pH. The new phases were applied for separation and determination of trace amounts of Hg(II) and Ag(I) spiked natural water samples using cold vapour atomic absorption spectroscopy and atomic absorption spectroscopy with no matrix interference. The high recovery values of Hg(II) and Ag(I) obtained using phases I and II were ranged 98.9 ± 0.1–99.2 ± 0.05% along with a good precision (RSD% 0.01–0.502%, N = 3) demonstrate the accuracy and validity of the new sorbents for separation and determination of Hg(II) and Ag(I).

A Novel Hg(II) PVC Membrane Sensor Based on Simple Ionophore Ethylenediamine Bis‐Thiophenecarboxaldehyde

Abstract A mercury (II) ion‐selective polyvinyl chloride (PVC) membrane sensor based on ethylenediamine bisthiophenecarboxaldehyde (EDBT) as a novel nitrogen‐ and sulfur‐containing sensing material was successfully developed. The ionophore was produced through Schiffs base formation between ethylenediamine and 2‐thiophenecarboxaldehyde. These two reagents have the advantages of low cost and simple chemical compounds. Ortho‐nitro phenyl pentyl ether (o‐NPPE) as solvent and sodium tetraphenyl borate (NaTPB) as a lipophilic salt were chosen. The sensor exhibited a good linear response of 30.0±0.4 mV per decade within the concentration range of 10−7–10−2 and a detection limit of 7.0×10−8 mol L−1 Hg(II). The sensor showed good selectivity and fast response for the mercury (II) ion with respect to some alkali, alkaline earth, transition, and heavy metal ions. The EDBT–based sensor was suitable for aqueous solutions of pH range from 2.0 to 4.5. It can be used for about 3 months without any considerable divergence in potential. The formation constant of ionophore complex with Hg(II) ion was calculated by using the segmented sandwich membrane method. The structure of both the ionophore and its Hg(II) complex were examined using infrared spectra and elemental analysis. The proposed sensor was applied for the determination of Hg(II) content in some dental amulgum alloys and as an indicator electrode for potentiometric titration of Hg(II) ion with EDTA solution, as well as with I−, OH−, and IO3 − ions. In addition, the solubility products of the previous ions were determined by using this sensor.

Novel route for silylation of silica gel and aliphatic amines immobilization based on microwave-assisted solvent free synthesis and their applications for Cu(II) and Fe(III) removal from natural water samples

This article describes a new route for silica gel silylation and immobilization of aliphatic amines based on microwave-assisted solvent free synthesis to produce new solid phase extractors. The mode of synthesis was optimized under microwave conditions and achieved in a short time without using solvents. The produced phases named: silica gel- monoamine (SG-MA), silica gel- ethylenediamine (SG-EDA) and silica gel- diethylenetriamine (SG-DETA). The selectivity of these phases towards the uptake of Cu(II) and Fe(III) was checked using batch equilibration technique. Microwave radiation power and time of radiation were optimized to obtain the highest metal uptake values. The novel synthesized silica amine phases were characterized using Fourier transform infrared spectra and scanning electron microscope. The effects of different parameters including, hydrogen ion concentration, initial metal ion concentration, mass of the phase and shaking time on binding capacities of both Cu(II) and Fe(III) were explored. Results of sorption isotherms of the phases were better fitted with the Langmuir model (r2 ≥ 0.950). In addition, the kinetics data were best fitted with the pseudo–second-order type (r2 = 0.999). Application of SG-MA for removal of Cu(II)- and Fe(III)-spiked natural water samples was achieved satisfactorily using batch experiments. The results were found to refer to superior recovery percentages (90.0–97.01 ± 0.010–0.521%) with no significant matrix interferences.

New Trend for Acceleration Solid Phase Extraction Process Based on Using Magnetic Nano-adsorbents along with Surface Functionalization through Microwave Assisted Solvent-free Technique

The use of a microwave assisted solvent-free technique for silica coating of iron magnetic nanoparticles (Fe3O4-MNPs) and their functionalization with three aliphatic diamines: 1,2-ethylenediamine (1,2EDA), 1,5-pentanediamine (1,5PDA) and 1.8-octanediamine (1,8-ODA), were successfully achieved in a very short time. Only 60 min were needed for the nano-adsorbent modification as compared with more than 1000 min using conventional methods under reflux conditions. Their surface characteristics (observed by TEM, XRD and FT-IR), in addition to Cu(II) adsorption capacities (1.805, 1.928 and 2.116 mmol g(-1)) and time of equilibration (5 s) were almost the same. Thus, the time required to accomplish the solid phase extraction process is greatly reduced. On the other hand, the phenomenon of the fast equilibration kinetics was successfully extended on using the functionalized aliphatic diamines magnetic nano-adsorbents as precursors for further microwave treatment. Three selective magnetic nano-adsorbents (Fe3O4-MNPs-SiO2-1,2EDA-3FSA, Fe3O4-MNPs-SiO2-1,5PDA-3FSA and Fe3O4-MNPs-SiO2-1,8ODA-3FSA) were obtained via the reaction with 3-formayl salicylic acid (3FSA) as a selective reagent for Fe(III). At 5 s contact time, they exhibited maximum Fe(III) uptake equal to 4.512, 4.987 and 5.367 mmol g(-1), respectively. Furthermore, modeling of values of metal uptake capacity obtained at different shaking time intervals supports pseudo-second order kinetics.