Phenolic and tannin-based adhesive resins by reactions of coordinated metal ligands. I. Phenolic chelates

Bivalent and trivalent metallic ions, respectively, accelerate and inhibit the reaction of phenols with formaldehyde. The catalytic effect of these metallic ions is equivalent, though more marked, to that of hydrogen ions, and it is due to their stronger charge. Metallic ions/phenols/formaldehyde complexes are formed. The stability of these complexes and mainly their rate of metal exchange in solution are the determining factors in the accelerating or retarding action. Identified stable chromium (III)–resorcinol–formaldehyde and chromium (III)–phenol–formaldehyde complexes have slow rates of metal exchange and inhibit the resorcinol–formaldehyde and phenol–formaldehyde reactions. The opposite is valid for lead (II), zinc (II), and other bivalent metallic ions. A scale showing the order of the accelerating effect of a series of metallic ions is given. The presence of polymeric complexes has also been observed.     

Synthesis of polymer-supported metal-ion complexes and evaluation of their catalytic activities

Polymer-supported transition-metal-ion complexes of the N,N′-bis(o-hydroxy acetophenone) propylenediamine (HPPn) Schiff base were prepared by the complexation of iron(III), cobalt(II), and nickel(II) ions on a polymer-anchored N,N′-bis(5-amino-o-hydroxy acetophenone) propylenediamine Schiff base. The complexation of iron(III), cobalt(II), and nickel(II) ions on the polymer-anchored HPPn Schiff base was 83.44, 82.92, and 89.58 wt%, respectively, whereas the unsupported HPPn Schiff base showed 82.29, 81.18, and 87.29 wt % complexation of these metal ions. The iron(III) ion complexes of the HPPn Schiff base showed octahedral geometry, whereas the cobalt(II) and nickel(II) ion complexes were square planar in shape, as suggested by spectral and magnetic measurements. The thermal stability of the HPPn Schiff base increased with the complexation of metal ions, as evidenced by thermogravimetric analysis. The HPPn Schiff base showed a weight loss of 51.0 wt % at 500°C, but its iron(III), cobalt(II), and nickel(II) ion complexes showed weight losses of 27.0, 35.0, and 44.7 wt % at the same temperature. The catalytic activity of the unsupported and supported metal-ion complexes was analyzed by the study of the oxidation of phenol and epoxidation of cyclohexene in the presence of hydrogen peroxide. The supported HPPn Schiff base complexes of iron(III) ions showed a 73.0 wt % maximum conversion of phenol and 90.6 wt % epoxidation of cyclohexene, but unsupported complexes of iron(III) ions showed 63.8 wt % conversion of phenol and 83.2 wt % epoxidation of cyclohexene. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 93.1 wt % and 98.1 wt % with the supported HPPn Schiff base complexes of iron(III) ions, but it was low with the supported Schiff base complexes of cobalt(II) and nickel(II) ions. The selectivity for CTL and ECH varied with the molar ratio of the metal ions but remained unaffected by the molar ratio of hydrogen peroxide to the substrate. The energy of activation for the epoxidation of cyclohexene and oxidation of phenol with the polymer-supported Schiff base complexes of iron(III) ions was 10.0 and 12.7 kJ/mol, respectively, but it was found to be higher with the supported HPPn Schiff base complexes of cobalt(II) and nickel(II) ions and with the unsupported HPPn Schiff base complexes of iron(III), cobalt(II), and nickel(II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Poly(4-sodium styrene sulfonate-co-4-acryloylmorpholine). Synthesis,Characterization, and Metal Ion Retention Properties

Abstract

A novel resin poly(sodium 4-styrene sulfonate-co-4-acryloyl morpholine) was synthesized through a radical solution polymerization in solution and studied as an adsorbent under uncompetitive and competitive conditions by batch and column equilibrium procedures for the following divalent metal ions Cd(II), Zn(II), Pb(II), and Hg(II), and trivalent Cr(III). For all metal ions, the adsorption was strongly influenced by the pH. The maximum retention capacity, 3.29 mmol of metal ion/g, was obtained for Zn(II) at pH 5 by batch equilibrium procedure. For both the batch and column procedures, the retention behavior was similar for Cd(II), Cr(III), Zn(II), and Pb(II).     

Synthesis,characterization, and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid)–metal complexes

The metal‐ion complexation behavior and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid) were investigated. The polymeric ligand was prepared by solution polymerization. The metal‐ion complexation was studied with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal uptake followed the order: Cu(II) > Cr(III) > Mn(II) > Co(II) > Fe(III) > Zn(II) > Ni(II). The polymeric ligand and the metal complexes were characterized by various spectral methods. The catalytic activity of the metal complexes were investigated toward the hydrolysis of p‐nitrophenyl acetate (NPA). The Co(II) complexes exhibited high catalytic activity. The kinetics of catalysis was first order. The hydrolysis was controlled by pH, time, amount of catalyst, and temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 272–279, 2004     

Elution Behavior of Metal Ions with Mixed Glycine-Nitric Acid Eluents in Dowex 50W-X8 Column: Separation of Th(IV), Ce(IV), Bi(III), Fe(III), and Al(III)

Abstract

Distribution coefficients (K) determined by the batch technique in acidic glycine media using Dowex 50W-X8 cation exchanger (H⁺?form, 100–200 mesh size) revealed that this medium can effectively be employed to separate a number of tetravalent and trivalent metal ions from bivalent metal ions. In fixed glycine (0.40 M) and varying concentration of nitric acid (0.10 to 1.0 M), a number of mixtures containing two or three metal ions were resolved on columns using about 8 g of exchanger. In 0.40 M glycine-1.0 M HNO₃ medium, Th(IV)/Ce(IV) were separated from Al(III)/Fe(III)/Bi(III)/Co(II)/Ni(II)/Cu(II)/Zn(II)/Cd(II)/Hg(II)/Pb(II)/Ag(I) and also Al(III)/Bi(III) from a number of divalent metal ions. In 0.40 M glycine-0.50 M HNO₃ medium, the resolution of following ternary mixtures were also achieved: Th(IV)/Ce(IV)-Al(III)/Bi(III)-Fe(III)/Co(II)/Ni(II)/Cu(II)/Zn(II)/Cd(II)/Hg(II)/Pb(II)/Ag(I). Th(IV)/Al(III)/Fe(III)/Bi(III) were also separated from other divalent metal ions in 1.60 M glycine-0.50 M HNO₃ medium. The values of K, elution characteristics of metal ions, elution curves, and the results of the resolution of a number of mixtures of metal ions along with standard deviations are reported.     

Spectroscopic and Thermal Studies of Mn(II), Fe(III), Cr(III) and Zn(II) Complexes Derived from the Ligand Resulted by the Reaction Between 4-Acetyl Pyridine and Thiosemicarbazide

Transition metal complexes of Mn(II), Fe(III), Cr(III) and Zn(II) metal ions with a general formulas [Mn(L)₂(Cl)₂]·4H₂O (I), [Fe(L)₂(Cl)₂]·Cl·6H₂O (II), [Cr(L)₂(Cl)₂]·Cl·6H₂O (III) and [Zn(L)₂(Cl)₂]·2H₂O (IV) where L = 4-acetylpyridine thiosemicarbazone, have been synthesized and interpreted using CHN elemental analysis, magnetic susceptibility measurements, molar conductance, thermal analysis and spectroscopic techniques; i.e., infrared, electronic UV/vis, ¹H-NMR and mass. The manganese(II), ferric(III), chromium(III) and zinc(II) complexes have octahedral geometry. The molar conductance measurements reveal that the Mn(II) and Zn(II) chelates are non-electrolytes but Fe(III) and Cr(III) have an electrolytic behavior. The IR spectra show that the 4-acetylpyridine thiosemicarbazone free ligand is coordinated to the metal(II) chlorides as a neutral bidentate ligand through both of the lone pair of electrons of the C=N azomethine group and C=S group. X-ray powder diffraction gives an impression that the resulting complexes are amorphous and different from the start materials. The thermogravimetric studies indicate that uncoordinated water molecules are lost in the first and second decomposition steps. The activation thermodynamic parameters E*, ΔH*, ΔS* and ΔG* are estimated from the differential thermogravimetric analysis (DTG) curves using Horowitz–Metzger (HM) and Coats–Redfern (CR) methods. The ligand and its complexes have been screened for antibacterial and antifungal activities against two bacteria; i.e., Escherichia coli (Gram −ve) and Bacillus subtilis (Gram +ve) and two fungi, i.e., tricoderma and penicillium activities).     

Application of Chitosan Membranes in Separation of Heavy Metal Ions

Abstract

The authors present an application of chitosan membranes for the removal of heavy metal ions. Investigations covered membranes produced by phase inversion. Additionally, separation properties of acetylated membranes were tested. Low-viscous chitosan produced by the Sea Fisheries Institute—Poland was used in the experiments. The investigations were carried out for the transition metal ions Cr(VI), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II). A method for metal ions separation by means of chitosan membranes was proposed. The metal ions were complexed in the membrane during ultrafiltration of the solution. The separation ability of the membranes was investigated for individual metal ions and for a mixture. The effect of the pH of the solution on separation properties of membranes was determined. The concentration of metal ions was investigated by the method of inductively coupled plasma (ICP) atomic emission spectrometry. The investigations show the suitability of chitosan membranes produced by the phase inversion method for the removal of metal ions.     

Comparative Equilibrium Studies on the Sorption of Metal Ions with Macroporous Resins Containing a Liquid Ion-Exchanger

Abstract

The distribution of five metal ions (M ^m+) including Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) between dilute sulfate solutions and macroporous resins containing di(2-ethylhexyl) phosphoric acid (D2EHPA, HR) was investigated. Experiments were carried out as a function of aqueous pH, D2EHPA concentration in the resin phase, and temperature. The equilibrium data were numerically analyzed. It was shown that the sorption reaction could be described by assuming the formation of metal complexes with a general composition MR _m (HR) _n in the resin phase. For several systems a change of complex stoichiometry with temperature was observed and discussed. The apparent thermodynamic data for the formation of these complexes were also calculated.     

Water-soluble oxidized starch in complexation of Fe(III), Cu(II), Ni(II) and Zn(II) ions

The structure of the bromate-oxidized wheat starch (OS) contains partly opened glucose units with carbonyl and carboxyl groups at C2-, C3- or C6-positions. OS with a variable degree of oxidation (DO) was studied in alkaline conditions as a water-soluble complexing agent for Fe(III), Cu(II), Ni(II) and Zn(II) ions, which are common in various wastewaters. Complexation was studied by inductively coupled plasma-optical emission spectrometry (ICP–OES) in a single metal ion or multi-metal ion solutions. The DO affected the efficiency of the complexation with metal ions. OS with the high DO (carboxyl and carbonyl DO of 0.72 and 0.23, respectively) complexed and held Fe(III) or Zn(II) ions in a soluble form effectively in 0.5 mM single ion alkaline solution with the molar ratio of 0.65:1 of oxidized starch-to-metal ion (OS-to-M). The OS-to-M molar ratio of 1.3:1 was required to form a soluble complex with Cu(II) or Ni(II) ions. These complexes were thermally stable at the temperature range of 20–60 °C. OS with the low DO (carboxyl and carbonyl DO 0.47 and 0.17, respectively) complexed Zn(II) ions highly, Cu(II) and Ni(II) ions poorly and Fe(III) ions only partly. In the multi-metal ion solution of OS the solubility of these metal ions improved with the increasing DO of starch, which followed the same tendency as was observed in the single metal ion systems. The increased molar ratio of OS-to-M improved the complexation and solubility of the metal ions in all multi-metal ion series. As the soluble multi-metal ion complexes were reanalyzed after 7 days, all solutions had kept the high complexation and solubility of metal ions (ca. 90%). Complexation by OS did not show a selective binding of the ions in the multi-metal ion solution. It was concluded that the flexible, opened ring structure units of OS prevented the selective binding to metal ions but made the complexes highly stable. Titrimetric studies of OS–Fe(III) complexation showed that each anhydroglucose unit of OS had more than one coordination site and as the content of OS increased, the free sites coordinated to Fe(III) ions and formed cross-linked starch structures.     

Thin-Layer Chromatography of Metal Ions Complexed with Anils. Y. Detection,Separation, and Determination

Abstract

p-Diethylaminoanil of phenylglyoxal, a bidentate ligand, was used for complexation with Hg(II), UO₂(II), Au(III), Pt(IV), Mg(II), Bi(III), Sb(III), and Be(II) ions. The chelates were characterized by their analysis, molar conductance, and infrared spectra. TLC detection, separation, and determination of these complexes on starch-bound silica gel layers were studied. Long persisting dark colors of the complexes rendered the spots self-descernible and no locating agent was required. A maximum of four complexes could be resolved and identified. Errors in determinations and maximum separation limits were also deduced.     

Adsorptive Separation of Metal Ions onto Phosphorylated Orange Waste

Abstract

A highly selective and efficient biosorbent has been prepared from orange waste by introducing a phosphoric group at its polymer analog by simple chemical modification. Their adsorption behavior for several kinds of metal ions was studied and it was found to exhibit excellent selectivity towards several metal ions. As a typical example, a binary mixture of In(III) and Zn(II) was studied by using a packed column, indicating that In(III) ion can be selectively separated from its mixture with a concentration factor of 63 times. The maximum adsorption capacities evaluated in terms of mol/kg dry gel were 0.70 for In(III) and Ga(III), 0.97 for Cu(II), 1.15 for Pb(II) and Zr(IV), and 3.06 for Fe(III), respectively.     

Immobilized Phosphate Ligands with Enhanced Ionic Affinity through Supported Ligand Synergistic Interaction

Abstract

The ability of a secondary group to influence the metal ion affinities of a primary ligand immobilized on crosslinked polystyrene beads is reported. The secondary groups were glycol units, ‐(CH₂CH₂O)_1‐4‐, and their effect on phosphate ligands was studied. The affinities of Pb(II), Cd(II), Cu(II), Ni(II), Zn(II), Fe(III), Y(III), La(III), Eu(III), Lu(III), and U(VI) were quantified from HNO₃, HCl, and H₂SO₄ solutions in concentrations up to 4 N. Affinities were highest for U(VI) and the trivalent ions. The glycol units enhanced the extent of metal ion complexation by the phosphate ligands through coordination of the metal ion and not through an auxiliary group effect (where there would be a direct interaction between the glycol units and the phosphate ligand) as indicated by the similarity in the FTIR spectra of the four phosphorylated glycol resins. At least two glycol units are needed for synergistic cooperation between the glycol and phosphate in binding metal ions.     

UPTAKE OF METAL IONS BY A NEW CHELATING ION-EXCHANGE RESIN. PART 4 : KINETICS

Abstract

The rate of uptake of several actinide ions [Am(III), U(VI), Th(IV), Np(IV) and Pu(IV)] and of some transition-metal ions [Co(II), Zn(II), Fe(III) and Cr(III)] at tracer concentration level, from solutions of various compositions, by the new chelating ion-exchange resin, Diphonix^Tm, has been investigated. Diphonix is a polyfunctional resin containing sulfonic and gem-diphosphonic acid groups chemically bonded in a styrene-divinylbenzene polymeric network. It binds actinide and other ions through the formation of chelate complexes with the phosphoryl groups of the gem-diphosphonic acids. The experiments discussed in this work have allowed us to establish the paramount importance of the presence of the sulfonic groups in obtaining practically useful rates of metal ions uptake. Comparison of the kinetic behavior of Diphonix with that of commercial sulfonic-type resins has shown that Diphonix reacts with the investigated ions as rapidly as do the other resins. Conditions for efficient and rapid stripping of all the investigated cations, including Cr(III), have been found.     

EVALUATION OF A DIETHANOLAMINE CHELATING RESIN USING TWO-PHASE POTENTIOMETRY

ABSTRACT

The synthesis of a polystyrene resin functionalised with diethanolamine is described. Protonation of the resin and complexation of Pb(II), Cd(II), Hg(II), UO₂ ²⁺, Fe(III), Ca(n) and Nd(III) were studied using two-phase potentiometry. From these experiments, apparent formation constants could be calculated and distribution curves obtained. Predictions as to metal ion separations were then possible. Batch experiments with Eu(III) and Pu(IV) were also performed as well as a column experiment for Pb(II) and Ca(II) to test selectivity. The resin shows selectivity towards metal ions that are large and/or have a good affinity for nitrogen donor ligands. Metal ions susceptible to hydrolysis are well complexed by the resin due to its ability to suppress hydrolysis.     

Pecan Nutshell as Biosorbent to Remove Toxic Metals from Aqueous Solution

Abstract

In the present study we reported for the first time, the feasibility of pecan nutshell (PNS-Carya illinoensis) as an alternative biosorbent to remove Cr(III), Fe(III) and Zn(II) metallic ions from aqueous solutions. The ability of PNS to remove these metallic ions was investigated by using batch biosorption procedure. The effects, such as pH and the biosorbent dosage on the adsorption capacities of PNS were studied. Five kinetic models were tested, the adsorption kinetics being the better fitted one to the fractionary-order kinetic model.

The equilibrium data were fitted to Langmuir, Freundlich, Sips, and Redlich-Peterson isotherm models. Taking into account a statistical error function, the data were best fitted to Sips isotherm models. The maximum biosorption capacity of PNS were 93.01, 76.59, and 107.9 mg g^?1 for Cr(III), Fe(III), and Zn(II), respectively.     

Recovery and Separation of Lanthanum(III), Aluminum(III), Cobalt(II), and Nickel(II) from Misch Metal by Solvent Extraction Using Bis(2-ethylhexyl) phosphinic Acid

Abstract

This paper describes use of bis(2-ethylhexyl) phosphinic acid as a reagent for extraction and mutual separation of lanthanum(III), aluminum(II), cobalt(II), and nickel(II) in 1.0 mol/L sodium nitrate. The extraction and stripping behavior of the four metal ions has been investigated using the extractant in Solvesso #150 as a diluent. The mutual separation and recovery of the metal ions from their mixtures has been tested by multistage extraction with a conventional separator funnel. A set of separation schemes has also been proposed for a continuous countercurrent multistage extraction which is comprised of ten extraction stages, four scrubbing stages, and seven stripping stages. Lanthanum(III) and aluminum(III) are coextracted but separated by selective stripping into different concentrations of hydrochloric acid. Cobalt(II) can be extracted with the nickel(II)-preloaded extractant solution, whereas nickel(II) remains in the aqueous phase. The successful separation of these metal ions from a misch metal-simulated sample is presented.     

Multivariate optimization for removal of some heavy metals using novel inorganic–organic hybrid and calcined materials

ABSTRACT

Hybrid materials with organic–inorganic character have been receiving attention especially due to their unique properties and offer probability for many new applications in variable fields and industrial applications. One of these applications is heavy metal removal from aqueous solutions because the metal pollution is a matter of concern about environment. In this study, organic–inorganic hybrid materials on the basis of metal alkoxides and their calcined forms were synthesized, characterized, and applied firstly to remove Cu(II), Fe(III), Pb(II), and Zn(II) ions from aqueous solutions by adsorption process. Response surface methodology was applied to optimize metal ions removal.     

Influence of different pyrolysis methods on the sorption property of rice straw biochar

ABSTRACT

Rice straw presents a good potential as feedstock to prepare biochar. In this study, two different pyrolysis methods, that is, slow pyrolysis and direct pyrolysis are applied to carbonize the rice straw in muffle furnace. SEM and TEM images indicate that both samples display porous structure, while BET data confirm that biochars from direct pyrolysis process own higher specific surface area and pores volume than that from slow pyrolysis. Two samples are employed to metal ions Pb(II), Cu(II), Mn(II), and Cr(III) sorption from aqueous solution. The influence of reaction time, pH, and metal ions initial concentration on sorption are evaluated.     

Removal of Cu(II), Fe(III), and Cr(III) from Aqueous Solution by Aniline Grafted Silica Gel

Abstract

The aniline moiety was covalently grafted onto silica gel surface. The modified silica gel with aniline groups (SiAn) was used for removal of Cu(II), Fe(III), and Cr(III) ions from aqueous solution and industrial effluents using a batch adsorption procedure. The maximum adsorption of the transition metal ions took place at pH 4.5. The adsorption kinetics for all the adsorbates fitted better the pseudo second‐order kinetic model, obtaining the following adsorption rate constants (k₂): 1.233 · 10^?2, 1.902 · 10^?2, and 8.320 · 10^?3 g · mg^?1 min^?1 for Cr(III), Cu(II), and Fe(III), respectively. The adsorption of these transition metal ions were fitted to Langmuir, Freundlich, Sips, and Redlich‐Peterson isotherm models; however, the best isotherm model fitting which presented a lower difference of the q (amount adsorbed per gram of adsorbent) calculated by the model from the experimentally measured, was achieved by using the Sips model for all adsorbates chosen. The SiAn adsorbent was also employed for the removal of the transition metal ions Cr(III) (95%), Cu(II) (95%), and Fe(III) (94%) from industrial effluents, using the batch adsorption procedure.     

Polystyrene-supported thiosemicarbazone–transition metal complexes: synthesis and application as heterogeneous catalysts

Functionalized polymers are found to be highly efficient in immobilizing transition metal ions. Crosslinked polystyrene supported Schiff's base complexes of metal ions such as Fe(III), Co(II), Ni(II) and Cu(II) are very effective as heterogeneous catalysts. The catalytic activity of these metal complexes has been studied in the decomposition of H₂O₂ and in the epoxidation of cyclohexene and styrene. The reactions show a first order dependence on the concentration of both the substrates and the catalyst. The influence of the degree of crosslinking of the polymer support on the rate of reactions has been studied. The metal complexes show low catalytic activity at low crosslink density (2% and 5%) but 10% crosslinked resins show higher activity. A possible mechanism for the reactions is suggested. © 1999 Society of Chemical Industry