Effect of Fe3O4 addition on removal of ammonium by zeolite NaA

Magnetic zeolite NaA with different Fe3O4 loadings was prepared by hydrothermal synthesis based on metakaolin and Fe3O4. The effect of added Fe3O4 on the removal of ammonium by zeolite NaA was investigated by varying the Fe3O4 loading, pH, adsorption temperature, initial concentration, adsorption time. Langmuir, Freundlich, and pseudo-second-order modeling were used to describe the nature and mechanism of ammonium ion exchange using both zeolite and magnetic zeolite. Thermodynamic parameters such as change in Gibbs free energy, enthalpy and entropy were calculated. The results show that all the selected factors affect the ammonium ion exchange by zeolite and magnetic zeolite, however, the added Fe3O4 apparently does not affect the ion exchange performance of zeolite to the ammonium ion. Freundlich model provides a better description of the adsorption process than Langmuir model. Moreover, kinetic analysis indicates the exchange of ammonium on the two materials follows a pseudosecond-order model. Thermodynamic analysis makes it clear that the adsorption process of ammonium is spontaneous and exothermic. Regardless of kinetic or thermodynamic analysis, all the results suggest that no considerable effect on the adsorption of the ammonium ion by zeolite is found after the addition of Fe3O4. According to the results, magnetic zeolite NaA can be used for the removal of ammonium due to the good adsorption performance and easy separation method from aqueous solution.

Hydrogen bonding in two ammonium salts of 5-sulfosalicylic acid : ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate and triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate

The structures of two ammonium salts of 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA) have been determined at 200 K. In the 1:1 hydrated salt, ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate, NH4+·C7H5O6S-·H2O, (I), the 5-SSA- monoanions give two types of head-to-tail laterally linked cyclic hydrogen-bonding associations, both with graph-set R44(20). The first involves both carboxylic acid O-HOwater and water O-HOsulfonate hydrogen bonds at one end, and ammonium N-HOsulfonate and N-HOcarboxy hydrogen bonds at the other. The second association is centrosymmetric, with end linkages through water O-HOsulfonate hydrogen bonds. These conjoined units form stacks down c and are extended into a three-dimensional framework structure through N-HO and water O-HO hydrogen bonds to sulfonate O-atom acceptors. Anhydrous triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate, 3NH4+·C7H4O6S2-·C7H5O6S-, (II), is unusual, having both dianionic 5-SSA2- and monoanionic 5-SSA- species. These are linked by a carboxylic acid O-HO hydrogen bond and, together with the three ammonium cations (two on general sites and the third comprising two independent half-cations lying on crystallographic twofold rotation axes), give a pseudo-centrosymmetric asymmetric unit. Cation-anion hydrogen bonding within this layered unit involves a cyclic R33(8) association which, together with extensive peripheral N-HO hydrogen bonding involving both sulfonate and carboxy/carboxylate acceptors, gives a three-dimensional framework structure. This work further demonstrates the utility of the 5-SSA- monoanion for the generation of stable hydrogen-bonded crystalline materials, and provides the structure of a dianionic 5-SSA2- species of which there are only a few examples in the crystallographic literature.

Practical applications for clay-derived zeolite N : an ammonium-selective ion exchanger for industry use

Over the past ten years, scaled-up utilisation of a previously under-exploited zeolite, Zeolite N1, has been demonstrated for selective ion exchange of ammonium and other ions in aqueous environments. As with many zeolite syntheses, the required source material should contain predictable levels of aluminium and silicon and, for full-scale industrial applications, kaolin and/or montmorillonite serve such a purpose. Field, pilot and commercial scale trials of kaolin-derived Zeolite N have focused on applications in agriculture and water treatment as these sectors are primary producers or users of ammonium. The format for the material – as fine powders, granules or extrudates – depends on the specific application albeit each has been evaluated.

Hydrogen-bonded two- and three-dimensional polymeric structures in the ammonium salts of 3,5-dinitrobenzoic acid, 4-nitrobenzoic acid and 2,4-dichlorobenzoic acid

The structures of the ammonium salts of 3,5-dinitrobenzoic acid, NH4+ C7H3N2O6- (I), 4-nitrobenzoic acid, NH4+ C7H4N2O4- . 2H2O (II) and 2,4-dichlorobenzoic acid, NH4+ C7H3Cl2O2- . 0.5H2O (III), have been determined and their hydrogen-bonded structures are described. All salts form hydrogen-bonded polymeric structures, three-dimensional in (I) and two-dimensional in (II) and (III). With (I), a primary cation-anion cyclic association is formed [graph set R3/4(10)] through N-H...O hydrogen bonds, involving a carboxyl O,O' group on one side and a single carboxyl O-atom on the other. Structure extension involves both N-H...O hydrogen bonds to both carboxyl and nitro O-atom acceptors. With structure (II), the primary inter-species interactions and structure extension into layers lying parallel to (0 0 1) are through conjoined cyclic hydrogen-bonding motifs: R3/4(10) [one cation, a carboxyl (O,O') group and two water molecules] and centrosymmetric R2/4(8) [two cations and two water molecules]. The structure of (III) also has conjoined R3/4(10) and centrosymmetric R2/4(8) motifs in the layered structure but these differ in that he first involves one cation, a carboxyl (O,O') as well as a carboxyl (O) group and one water molecule, the second, two cations and two carboxyl O-groups. The layers lie parallel to (1 0 0). The structures of the salt hydrates (II) and (III) reported in this work, giving two-dimensional layered arrays through conjoined hydrogen-bonded nets provide further illustrations of a previously indicated trend among ammonium salts of carboxylic acids, but the anhydrous three-dimensional structure of (I) is inconsistent.

Structural effects of ammonium and hydronium in jarosite minerals

This thesis resolved the structural ambiguity surrounding ammonium and hydronium ions in the jarosite mineral group. The vibrational spectra of these two minerals were rationalised with their crystal structures for the first time. In doing so, a theory for dealing with orientational disorder in crystals was proposed.

Two-dimensional hydrogen-bonded polymers in the crystal structures of the ammonium salts of phenoxyacetic acid, (4-fluorophenoxy)acetic acid and (4-chloro-2-methylphenoxy)acetic acid

The structures of the ammonium salts of phenoxyacetic acid, NH4+ C8H6O3- (I), (4-fluorophenoxy)acetic acid NH4+ C8H5FO3- (II) and the herbicidally active (4-chloro-2-methylphenoxy)acetic acid (MCPA), NH4+ C9H8ClO3-. 0.5(H2O) (III) have been determined. All have two-dimensional layered structures based on inter-species ammonium N-H...O hydrogen-bonding associations which give core substructures consisting primarily of conjoined cyclic motifs. Crystals of (I) and (II) are isomorphous with the core comprising R2/1(5), R2/1(4) and centrosymmetric R2/4(8) ring motifs, giving two-dimensional layers lying parallel to (100). In (III), the water molecule of solvation lies on a crystallographic twofold rotation axis and bridges two carboxyl O-atoms in an R4/4(12) hydrogen-bonded motif, creating two R3/4(10) rings which together with a conjoined centrosymmetric R2/4(8) ring incorporating both ammonium cations, generate two-dimensional layers lying parallel to (100). No pi-pi ring associations are present in any of the structures.

Removal characteristics of ammonium nitrogen from wastewater by modified Ca-bentonites

A modified inorganic bentonite (Na/Al) based on purified Ca-bentonite was prepared through exchanging Al and Na ions in the interlayer space of Ca-bentonite. The structural properties of purified and modified bentonites were characterized by XRD and SEM analysis. Batch experiments were performed for the adsorption of ammonium nitrogen and different experimental conditions were studied in order to investigate the optimum adsorption conditions. Comparative experiments were also carried out for natural Ca-bentonite (RB), unmodified purified bentonite (PB) and modified purified bentonite (MB). Through the thermodynamic analysis, the ammonium nitrogen adsorption process can be spontaneous, the standard heat was −41.46kJmol −1 , and the adsorption process based on ion exchange adsorption. The ammonium nitrogen adsorption capacity of MB (46.904mg/g) was improved compared to raw bentonite (RB) (26.631mg/g), which was among the highest values of ammonium nitrogen adsorption compared with other adsorbents according to the literatures. The described process provides a potential pathway for the removal of ammonium nitrogen at low concentrations encountered in most natural waters.

Crystal structure of ammonium (3,5-dichlorophenoxy)acetate hemihydrate

In the structure of the title hydrated salt, NH4+·C8H5Cl2O3-·0.5H2O, where the anion derives from (3,5-di­chloro­phen­oxy)acetic acid, the ammonium cation is involved in extensive N-H...O hydrogen bonding with both carboxyl­ate and ether O-atom acceptors giving sheet structures lying parallel to (100). The water mol­ecule of solvation lies on a crystallographic twofold rotation axis and is involved in intra-sheet O-H...Ocarboxyl­ate hydrogen-bonding inter­actions. In the anion, the oxoacetate side chain assumes an antiperiplanar conformation with the defining C-O-C-C torsion angle = -171.33 (15)°.

The three-dimensional hydrogen-bonded structures in the ammonium and sodium salt hydrates of 4-aminophenylarsonic acid

The structures of two hydrated salts of 4-aminophenylarsonic acid (p-arsanilic acid), namely ammonium 4-aminophenylarsonate monohydrate, NH4(+)·C6H7AsNO3(-)·H2O, (I), and the one-dimensional coordination polymer catena-poly[[(4-aminophenylarsonato-κO)diaquasodium]-μ-aqua], [Na(C6H7AsNO3)(H2O)3]n, (II), have been determined. In the structure of the ammonium salt, (I), the ammonium cations, arsonate anions and water molecules interact through inter-species N-H...O and arsonate and water O-H...O hydrogen bonds, giving the common two-dimensional layers lying parallel to (010). These layers are extended into three dimensions through bridging hydrogen-bonding interactions involving the para-amine group acting both as a donor and an acceptor. In the structure of the sodium salt, (II), the Na(+) cation is coordinated by five O-atom donors, one from a single monodentate arsonate ligand, two from monodentate water molecules and two from bridging water molecules, giving a very distorted square-pyramidal coordination environment. The water bridges generate one-dimensional chains extending along c and extensive interchain O-H...O and N-H...O hydrogen-bonding interactions link these chains, giving an overall three-dimensional structure. The two structures reported here are the first reported examples of salts of p-arsanilic acid.

Solute induced liquid crystalline behaviour of a quaternary ammonium salt and its application to structure determination

A new liquid crystalline phase, induced by the addition of small amounts of a non-mesogenic solute (such as dimethyl sulphoxide or methyl iodide) to a quaternary ammonium salt, N-methyl-N,N,N-trioctadecylammonium iodide (MTAI), has been detected by NMR and optical microscopic studies. In some cases, there is a coexistence of nematic and smectic phases. Information on the ordering of the phases in the magnetic field of the spectrometer has been derived from NMR spectra of a dissolved molecule, C-13-enriched methyl iodide. The low order parameter of the pure thermotropic nematic phase of the salt provides first-order spectra of the dissolved oriented molecules. Analyses of spectra of cis,cis-mucononitrile exemplifies the utility of the MTAI nematic phase in the determination of structural parameters of the solute.

Study of Ion Transport in Lithium Perchlorate-Succinonitrile Plastic Crystalline Electrolyte via Ionic Conductivity and in Situ Cryo-Crystallography

Ion transport mechanism in lithium perchlorate (LiClO4)-succinonitrile (SN), a prototype of plastic crystalline soft matter electrolyte is discussed in the context of solvent configurational isomerism and ion solvation. Contributions of both solvent configurational isomerism and ion solvation are reflected in the activation energy for ion conduction in 0-1 M LiClO4-SN samples. Activation energy due to solvent configurational changes, that is, trans-gauche isomerism is observed to be a function of salt content and decreases in presence of salt (except at high salt concentrations, e.g. 1 M LiClO4-SN). The remnant contribution to activation energy is attributed to ion-association. The X-ray diffraction of single crystals obtained using in situ cryo-crystallography confirms directly the observations of the ionic conductivity measurements. Fourier transform infrared spectroscopy and NMR line width measurements provide additional support to our proposition of ion transport in the prototype plastic crystalline electrolyte.

Structure of nonactin-calcium perchlorate, C40H64O12.Ca(ClO4)2, and a comparative study of metal-nonactin complexes

M r= 975.9, orthorhombic, Pnna, a = 20.262 (3), b= 15.717 (2), c= 15.038 (1)A, V= 4788.97 A 3, z = 4, D x = 1.35 Mg m -3, Cu Kct radiation, 2 = 1.5418 A, /t = 2.79 mm -1, F(000) -= 2072, T = 293 K, R = 0.08, 3335 observed reflections. The molecular structure and the crystal packing are similar to those observed in the nonactin complexes of sodium thiocyanate and potassium thiocyanate. The eight metal-O distances are nearly the same in the potassium complex whereas the four distances involving carbonyl O atoms are shorter than the remaining four involving the tetrahydrofuran-ring O atoms in the Na and the Ca complexes. This observation can be explained in terms of the small ionic radii of Na + and Ca 2+, and leads to a plausible structural rationale for the stronger affinity of nonactin for K + than for the other two metal ions.

Infrared spectroscopic study of the rotation of the NH 4+ ion in ammonium halides

Infrared correlation functions, have been obtained from the analysis of band shapes of the 1400 cm−1 bending mode of NH4Cl, NH4Br and NH4I in both the Pm3m and Fm3m phases. The NH 4 + ion seems to undergo relatively free rotation in the high temperature Fm3m phases of these halides.

Proton spin lattice relaxation in lithium ammonium sulphate LiNH4SO4

Lithium ammonium sulphate (LAS) undergoes a phase transition at TC1=459.5K from a paraelectric phase (phase I) to a ferroelectric phase (phase II) and again at TC2=283K to a polar ferroelastic phase (phase III). Proton spin lattice relaxation time measured at 10 MHz in powdered LAS in the temperature range 480 to 77K shows discontinuous changes at the two transitions.

Lanthanide perchlorate complexes of 4-nitroquinoline-1-oxide and 5-nitroisoquinoline-2-oxide

Novel complexes of lanthanide perchlorates with 4-nitroquinoline-1-oxide (NQNO) and 5-nitroisoquinoline-2-oxide (NIQNO) have been prepared and characterized. The complexes have the general formulaeLn(NQNO)8(ClO4)3 (whereLn=La-Nd), Ln(NQNO)7(ClO4)3 (whereLn=Gd-Yb),Ln(NIQNO)9(ClO4)3 (whereLn=La-Nd), andLn(NIQNO)7(ClO4)3 (whereLn=Gd-Yb). The IR, proton NMR spectral data indicate the coordination of the N—O group of the ligands to he lanthanide ions.