Mössbauer studies of the corrosion products of iron formed in aqueous ammonium nitrate solution

The products of corrosion reaction of electrolytic iron in 45% ammonium nitrate solution formed under various conditions of time, temperature and pH have been analysed mainly by Mössbauer spectroscopy, in combination with X-ray diffraction, infrared absorption and electron microscopy techniques. γ-Fe00H is found to be the major product of hydrolytic precipitation at pH > 5.6 while only α-FeOOH is formed at pH < 3.0. In the pH range 3.0 < pH < 5.0, α-Fe00H and ferrihydrite are both formed. However, once the nuclei of α-Fe00H are formed under low pH conditions, their growth is favoured even in the otherwise unfavourable slightly acidic medium, resulting in a hydrous α-Fe00H which has two distinct hyperfine fields at the 57Fe nucleus. Magnetite is always formed in the vicinity of the metal and its rate of formation on the surface increases with temperature. α-Fe203 is the major product of hydrolytic precipitation at temperatures >80C. The possible mechanisms for the formation of each of the corrosion products are discussed.

Dynamics of the ammonium ion in the ferroelectric transition in sodium ammonium selenate, NaNH4SeO4·2H2O-an E.S.R. study

E.S.R. investigations of γ-irradiated ferroelectric Sodium ammonium selenate, NaNH4SeO4•2H2O and its deuteriated analogue in powder and single crystal forms have led to a deeper understanding of the nature of the ferroelectric transition of 180 K. A number of paramagnetic species formed due to γ-irradiation have been identified on the basis of their g-factors and hyperfine features from 77Se. The radical SeO4 has been used as a microprobe in studying the phase transition.

The structures of the ammonium halides

A comparison with the alkali halides suggests that all the ammonium halides should occur in the NaCl centre-of-mass structure. Experimentally, at room temperature and atmospheric pressure, only NH4I crystallizes in this structure, while NH4F is found in the ZnO structure, and NH4C1 and NH4Br occur in the CsCl structure. We show that a distributed charge on the NH4+ ion can explain these structures. Taking charges of + 0.2e on each of the five atoms in NH4+, as suggested by other studies, we have recomputed the Madelung energy in the cases of interest. A full ionic theory including electrostatic, van der Waals and repulsive interactions then explains the centre-of-mass structures of all the four ammonium halides. The thermal and pressure transitions are also explained reasonably well. The calculated phase diagram of NH4F compares well with experiment. Barring the poorly understood NH4F(II) phase, which is beyond the scope of this work, the other features are in qualitative agreement. In particular, the theory correctly predicts a pressure transition at room temperature from the ZnO structure directly to the CsCl structure without an intermediate NaCl phase. A feature of our approach is that we do not need to invoke hydrogen bonding in NH4F.

Phase transition in ammonium aluminium and ammonium chromium alums-A high pressure EPR study

An investigation of the phase transitions at high pressures in the alums mentioned in the title has been carried out using EPR of the Cr3+ ion (at the trivalent metal ion site). It is observed that at ambient as well as at high pressures there is a change of slope in the linear variations of the zero field splitting with temperature and that the low temperature phase is characterised by a large number of lines in the EPR spectra. The transition temperature shows a large positive shift with pressure, for both the alums. All these facts are explained in terms of our model of the origin of the trigonal field at the trivalent metal ion site as well as the details of the motion of NH4+ ion.

Ammonium ions prevent methylation of uridine to ribothymidine in Azotobacter vinelandii tRNA

It was shown that tRNA from Azotobacter vinelandii grown in the presence of ammonium chloride lacks ribothymidine while that grown in the absence of the ammonium salt contains this modified nucleoside. [32P]-Labelled tRNA from this organism grown in a medium containing the ammonium salt was digested with RNase T1 and the pseudouridinecontaining tetranucleotide, common to all tRNAs was isolated and analysed for the nucleoside replacing the ribothymidine. It was found to be uridine. Cells previously labelled with [32P]- phosphate in the ammonium salt medium were washed and incubated in the ammonium saltfree medium to test whether ribothymidine would be formed upon removal of the ammoniumions. Methylation of the uridine did not take place.

The structures of the ammonium halides

A comparison with the alkali halides suggests that all the ammonium halides should occur in the NaCl centre-of-mass structure. Experimentally, at room temperature and atmospheric pressure, only NH,1 crystallizes in this structure, while NH,F is found in the ZnO structure, and NH&I and NH,Br occur in the CsCl structure. We show that a distributed charge on the NH,+ ion can explain these structures. Taking charges of + 0.2e on each of the five atoms in NH,+, as suggested by other studies, we have recomputed the Madelung energy in the cases of interest. A full ionic theory including electrostatic, van der Waals and repulsive interactions then explains the centre-of-mass structures of all the four ammonium halides. The thermal and pressure transitions are also explained reasonably well. The calculated phase diagram of NH,F compares well with experiment. Barring the poorly understood NH,F(II) phase, which is beyond the scope of this work, the other features are in qualitative agreement. In particular, the theory correctly predicts a pressure transition at room temperature from the ZnO structure directly to the CsCl structure without an intermediate NaCl phase. A feature of our approach is that we do not need to invoke hydrogen bonding in NH,F.

An elegant direct route for the preparation of pyridinium, ammonium and alkali metal hexafluorotitanates (IV)

Pyridinium hexafluorotitanate (IV) has been prepared by a one step procedure. Addition of titanium tetrachloride to pyridinium poly(hydrogen fluoride) yields nearly quantitative amounts of pyridinium hexafluorotitanate(IV). Making use of pyridinium hexafluorotitanate as precursor, ammonium and alkali metal (Na, K, Rb, and Cs) hexafluorotitanates have been prepared in good yields. These salts have been characterised by IR, N.M.R. (1H, 13C and 19F), X-ray powder diffraction data and chemical analysis.

Esr study of (SO4)2- dynamics in relation to the ferroelectric phase transition in ammonium sulfate

Ferroelectric phase transition in ammonium sulfate has been studied by ESR of CrO43- radical substituting for SO42- ion in (NH4)2SO4. In addition to discontinuous changes at Tc, certain continuous changes are observed in ESR parameters of this probe below Tc, which reflect the role of the sulfate ion in the phase transition. A microscopic mechanism of the phase transition is proposed and discussed in terms of the change of orientation of the sulfate tetrahedron through a finite angle. The degree of the change of orientation below Tc is thought to be the possible order parameter of the phase transition.

Kinetics and mechanism of anodic oxidation of chlorate ion to perchlorate ion on lead dioxide electrodes

The kinetics and mechanism of anodic oxidation of chlorate ion to perchlorate ion on titanium-substrate lead dioxide electrodes have been investigated experimentally and theoretically. It has been demonstrated that the ionic strength of the solution has a marked effect on the rate of perchlorate formation, whereas the pH of the solution does not influence the reaction rate. Experimental data have also been obtained on the dependence of the reaction rate on the concentration of chlorate ion in the solution at constant ionic strength. With these data, diagnostic kinetic criteria have been deduced and compared with corresponding quantities predicted for various possible mechanisms including double layer effects on electrode kinetics. It has thus been shown that the most probable mechanisms for anodic chlorate oxidation on lead dioxide anodes involve the discharge of a water molecule in a one-electron transfer step to give an adsorbed hydroxyl radical as the rate-determining step for the overall reaction.

NMR studies of phase transition in ammonium hydrogen bischloroacetate, NH4H(CH2ClCOOO)2

Proton second moment (M2) and spin-lattice relaxation time (T1) of Ammonium Hydrogen Bischloroacetate (ABCA) have been measured in the range 77-350 K. A value of 6.5 G2 has been observed for the second moment at room temperature, which is typical of NH4+ reorientation and also a second moment transition in the range 170-145 K indicates the freezing of NH4+ motion. The NMR signal disappears dicontinuously at 128 K. Proton spin-lattice relaxation time (T1) Vs temperature, yielded only one sharp miniumum of 1.9 msec which is again typical of NH4+ reorientation. A slope change at 250 K is also observed, prbably due to CH2 motion. Further, the FID signal disappears at 128 K. Thus the Tc appears to be 128 K (of two reported values 120 K and 128 K). Activation energies have been calculated and the mechanism of the phase transition is discussed.

Equilibrium studies of ammonium exchange with Australian natural zeolites

This paper is concerned with the study of the equilibrium exchange of ammonium ions with two natural zeolite samples sourced in Australia from Castle Mountain Zeolites and Zeolite Australia. A range of sorption models including Langmuir Vageler, Competitive Langmuir, Freundlich, Temkin, Dubinin Astakhov and Brouers–Sotolongo were applied in order to gain an insight as to the exchange process. In contrast to most previous studies, non-linear regression was used in all instances to determine the best fit of the experimental data. Castle Mountain natural zeolite was found to exhibit higher ammonium capacity than Zeolite Australia material when in the freshly received state, and this behavior was related to the greater amount of sodium ions present relative to calcium ions on the zeolite exchange sites. The zeolite capacity for ammonium ions was also found to be dependent on the solution normality, with 35–60% increase inuptake noted when increasing the ammonium concentration from 250 to 1000 mg/L. The optimal fit ofthe equilibrium data was achieved by the Freundlich expression as confirmed by use of Akaikes Information Criteria. It was emphasized that the bottle-point method chosen influenced the isotherm profile in several ways, and could lead to misleading interpretation of experiments, especially if the constant zeolite mass approach was followed. Pre-treatment of natural zeolite with acid and subsequently sodium hydroxide promoted the uptake of ammonium species by at least 90%. This paper highlighted the factors which should be taken into account when investigating ammonium ion exchange with natural zeolites.

Ternary metal complexes of anionic and neutral pyridoxine (vitamin B6) with 2,2'-bipyridine. Syntheses and x-ray structures of (pyridoxinato)bis(2,2'-bipyridyl)cobalt(III) perchlorate and chloro(2,2'-bipyridyl)(pyridoxine)copper(II) perchlorate hydrate

Ternary metal complexes involving vitamin B6 with formulas [CO",(PN-H)](anCdI [OC)'(bpy)(PN)Cl]C10(.bpHy 0 = 2,2'-bipyridine, PN = neutral pyridoxine, PN-H = anionic pyridoxine) have been prepared for the first time and characterized by means of magnetic and spectroscopic measurements. The crystal structures of the compounds have also been determined. [CO(PN-H)](CcryIsOta,l)lize s in the space group P2,/c with a = 18.900 (3) A, b = 8.764 (1) A, c = 20.041 (2) A,p = 116.05 (l)', and Z = 4 and [Cu(bpy)(PN)C1]C104-H20in the space group Pi with a = 12.136 (5) A, b = 13.283 (4) A,c = 7.195 (2) A, a = 96.91 (Z)', 0 = 91.25 (3)', y = 71.63 (3)', and Z = 2. The structures were solved by the heavy-atom method and refined by least-squares techniques to R values of 0.080 and 0.042 for 3401 and 2094 independent reflections, respectively. Both structures consist of monomeric units. The geometry around Co(II1) is octahedral and around Cu(I1) is distorted square pyramidal. In [CO(PN-H)]t(wCo IoxOy~ge)n~s ,fro m phenolic and 4-(hydroxymethyl) groups of PN-H and two nitrogens from each of two bpy's form the coordination sphere. In [Cu(bpy)(PN)C1]C104.H20o ne PN and one bpy, with the same donor sites, act as bidentate chelates in the basal plane, with a chloride ion occupying the apical position. In both structures PN and PN-H exist in the tautomeric form wherein pyridine N is protonated and phenolic 0 is deprotonated. However, a novel feature of the cobalt compound is that PN-H is anionic due to the deprotonation of the 4-(hydroxymethyl) group. The packing in both structures is governed by hydrogen bonds, and in the copper compound partial stacking of bpy's at a distance of -3.55 also adds to the stability of the system. Infrared, NMR, and ligand field spectroscopic results and magnetic measurements are interpreted in light of the structures.

Proton Spin-Lattice Relaxation in Sodium Ammonium Selenate Dihydrate:NaNHaSeOa.2He0

Proton spin-lattice relaxation studies in sodium ammonium selenate dihydrate carried out in the temperature range 130 to 300 K at 10 MHz show a continuous change in T, at T, indicating a second order phase transition. This compound is a typical case of a highly hindered solid wherein the thermally activated reorientations of ammonium ions freeze well above 77 K, as seen by NMR.Untersuchimgen der Protonen-Spin-Gitter-Relaxation in Natriuni-Ammoniumselenat-Dihydrat bei 10 MHz im Temperaturbereich 130 bis 300 K zeigen eine kontinuierliche Andernng in TI bei T, und ergeben einen Phasenubergang zweiter Art. Diese Verbindung ist ein typischer Fall eines stark ,,behinderten" Festkarpers, in dein die thermisch aktivierten Reorientierungen der Ammoniumionen weit oberhalb 77 H einfrieren, wie die NMR-Ergebnisse zeigen.

Differential thermal analysis of potassium perchlorate

A study has been made of the differential thermal analysis of (i) potassium perchlorate in powdered form, (ii) potassium perchlorate in pelletized form, (iii) potassium perchlorate recrystallized from liquid NH3, and (iv) potassium perchlorate preheated for 24 hours at 375°. Pretreatment of potassium perchlorate leads to a desensitization of both endothermic and exothermic processes. Additionally, the pretreatment tends to convert the symmetric exotherm into an asymmetric exotherm due to merging of the two exotherms. An analysis of the factors causing asymmetry in the exotherm has thrown fresh light on the mechanism of thermal decomposition of potassium perchlorate.

Lanthanide perchlorate complexes of 4-cyano pyridine-N-oxide, 4-chloro 2-picoline-N-oxide and 4-dimethyl amino-2-picoline-N-oxide

Complexes of lanthanide perchlorates with 4-cyano pyridine-1-oxide, 4-chloro 2-picoline-1-oxide and 4-dimethyl-amino 2-picoline-1-oxide have been isolated for the first time and characterized by analysis, conductance, infrared, NMR and electronic spectra. The complexes of 4-cyano pyridine-1-oxides have the composition Ln(CyPO)6(ClO4)3. 2H2O (Ln=La, Sm, Dy and Ho); Ln(CyPO)7 (ClO4)3. 2H2O (Ln=Pr, Nd, Er and Yb); and Ln(CyPO)5 (ClO4)3. 2H2O (Ln=Gd and Tb). The complexes of 4-chloro 2-picoline-1-oxide analyse for the formulae Ln(CpicO)6 (ClO4)3 (Ln=La, Pr, Nd and Ho); and Ln (CpicO)5 (ClO4)3 (Ln=Er and Yb), and those of 4-dimethylamino 2-picoline-1-oxide for Ln(DMPicO)6 (ClO4)3 (Ln=La and Nd); Ln(DMPicO)7 (ClO4)3 (Ln=Gd, Er and Yb); and Ln(DMPicO)8 (ClO4)3 (Ln=Dy and Ho).