Proton NMR of isomorphous paramagnetic and diamagnetic monohydrates MeSO4.1 H2O Me = Mn2+, Fe2+, Ni2+ AND Mg2+

Nuclear magnetic resonance of protons of crystallization water in isomorphous paramagnetic and diamagnetic monohydrates MeSO₄. 1 H₂O with Me = Mn²⁺, Fe²⁺, Ni²⁺ and Mg²⁺ is studied in the present paper. Proton NMR spectra in paramagnetic hydrates are asymmetric and their second moments, M₂, depend linearly on the square of the induction of the external magnetic field B₀. NMR spectrum of diamagnetic hydrate MgSO₄. 1 H₂O is symmetric and its shape and the second moment do not change with B₀. The parameters M₂₀ andK which characterize nuclear dipole-dipole interaction of protons and interaction of protons and paramagnetic ions, respectively, are derived from experimentally obtained dependences M₂ vs B ₀ ² and on the other hand, they are calculated by means of crystallographic data for substances studied. Calculations were realized in approximation where two nearest neighbour ions Me²⁺ to each water molecule are considered. The influence of the demagnetizing magnetic field of the sample was neglected.     

Study of magnetic interactions of the Fe2+ ions and the protons of crystallization water in FeSO4.n H2O hydrates

The paper deals with a study of interactions of protons in crystallization water of paramagnetic hydrates FeSO₄.n H₂O (wheren=1, 4, 5 and 7). The interaction of protons and paramagnetic ions Fe²⁺ and the nuclear dipole-dipole interaction of protons have been studied by means of the parameters expressing the dependence of the second moment of the proton nuclear magnetic resonance (NMR) spectrum on the external magnetic field, by means of the volume magnetic susceptibilities and the relaxation timesT ₁ of the investigated series of hydrates.We are grateful to Prof. Dr. hab. Z.Pajak, director of Department of Radiospectroscopy IF UAM in Poznan, and to his coworkers Dr. J.Kapturczak, Dr. K.Jurga, Dr. S.Glowinkowski and Mgr. F.Brych for facilitating our measurements mentioned in the paper as well as for a valuable discussion.     

Proton nuclear magnetic resonance in paramagnetic CoCl2.6 H2O

The present paper deals with a study of nuclear magnetic resonance (NMR) of protons of the crystal water of paramagnetic CoCl₂.6 H₂O. The measurements were carried out on powdered samples at room temperature, for values of the external magnetic field ranging from 0.3 to 1.0 T.The NMR signals of protons of the crystal water exhibit asymmetric shape which changes with the applied external magnetic field. We found that the second moment of the resonance line shows a linear dependence on the square of the induction of the externally applied magnetic field.Both the cause of the asymmetry of the NMR line of protons of the crystal water and the dependence of the second moment of the resonance line on the induction of external magnetic field are interpreted in the paper.     

Mößbauereffekt in FeCl2, FeSO4 und FeSO4 · 7 H2O

Mößbauereffect measurements were performed with FeCl₂, FeSO₄ and FeSO₄ · 7 H₂O in the temperature range between 5 and 300 ?K. The quadrupole splittings at 5 ?K were determined to be (1.300±0.027) mm/sec, (3.650±0.053) mm/sec, and (3.350±0.053) mm/sec respectively. From the temperature dependence of the quadrupole splittings it follows that in FeCl₂ the energy of the excited 3d-electron-level isδ=150 cm^?1, in FeSO₄ δ ₁=360 cm^?1 andδ ₂=1680 cm^?1 and in FeSO₄ · 7 H₂Oδ ₁=480 cm^?1 andδ ₂=1300 cm^?1. The magnitudes of the magnetic field at the iron nucleus at 5 ?K are (202±8) kOe for FeSO₄ and (0±4) kOe for FeCl₂.     

IR-Spectra of M2UO2F4.H2O Complexes

This work is devoted to the study of and Rb₂UO₂F₄.H₂O and Cs₂UO₂F₄. H₂O IR-spectra with the aim of obtaining a set of vibration frequencies characterising M₂U0₂F₄.H₂O complexe elucidating the role and nature of water bonds in the structures of the above-mentioned compounds; and receiving preliminary information on the structure of M₂UO₂F₄.H₂O. The investigated compounds were synthesized in accord with our previous paper¹. M₂UO₂D₂O and M₂UO₂F₄.HDO were obtained by recrystallizing M₂UO₂F₄.H₂O from D₂O and HDO respectively     

Field dependence of the thermal conductivity of K2CuCl4 · 2H2O near its ferromagnetic Curie temperature

The thermal conductivity of the ferromagnetic insulator K₂CuCl₄ · 2H₂O has been measured near its Curie temperature T_c. The measurements were made as a function of temperature in constant external magnetic field and as a function of field along isotherms. The results indicate a relaxation rate for magnetic critical scattering of phonons varies as H^?1/2.     

The hydrates and deuterates of ferrous sulfate (FeSO4): a Raman spectroscopic study

A comparative analysis has been carried out on the Raman spectra of FeSO₄·nH₂O (n = 1, 4, 7) including the ²D‐analogs. The effects of changing the degrees of hydration have been found from the lattice, SO₄²⁻ internal, and H₂O internal modes. Increasing degrees of hydration shift the intense ν₁(SO₄) peak to lower wavenumbers and reduce the amount of splitting on the ν₃(SO₄) peaks. Some of the water librational bands cause the broadening of the ν₄(SO₄) peaks in FeSO₄·7H₂O and the ν₂(SO₄) peaks in FeSO₄·7D₂O. The ν₂(H₂O) band in FeSO₄·H₂O is red‐shifted in excess of 100 cm⁻¹ relative to the unperturbed H₂O band. Between 240 and 190 K and between 140 and 90 K in the spectra of FeSO₄.4H₂O, two potential phase transitions have been identified from the changes in the lattice and water‐stretching regions. The resolution of the ν₁(H₂O) and ν₃(H₂O) bands in FeSO₄·4H₂O and FeSO₄·H₂O also improved sharply at low temperatures. The capability of distinguishing various forms of FeSO₄ hydrates unambiguously makes the Raman technique a potential analytical tool for the identification of sulfate minerals on planetary surfaces. Copyright © 2006 John Wiley & Sons, Ltd.     

Characteristics of mixed crystals Co(1−x)Fe x SO4· 7H2O

The characteristics of the mixed crystal (Fe,Co)SO₄·7H₂O (x=Fe/(Fe+Co)) are studied from the Mössbauer spectroscopy. They are quite similar atx>0.3 to those of FeSO₄·7H₂O. Whenx decreases from 0.2, the characteristics deviate from those of FeSO₄·7H₂O and approach gradually to those of CoSO₄·7H₂O.     

Exchange interactions and spin dynamics in a [CuNd2(C4O4)4(H2O)16]·2H2O crystal

Crystalline [CuNd₂(C₄O₄)₄(H₂O)₁₆]·2H₂O constructed of complexes of trivalent neodymium and divalent copper, has been synthesized and studied by EPR. The square anion groups (C₄O₄) enter as bridge ligands, forming chains of neodymium ions interconnected by (C₄O₄)Cu(C₄O₄) fragments. It is found that the relaxation rate of the neodymium subsystem at room temperature significantly exceeds the exchange interaction rate between copper and neodymium ions. Under these conditions the magnetic properties of the crystal are determined by two magnetically nonequivalent chains of copper ions, which do not interact. The intrachain exchange interaction via hydrogen bonds is estimated to be ∼0.1 cm⁻¹. As one proceeds from the high-temperature (250<T<300 K) to the low-temperature region (T<40 K), a substantial change in the nature of the interaction is revealed. An unusual magnetic structure given in a crystal is observed at low temperatures, which is determined by the presence of two magnetically nonequivalent “ribbons,” formed by the interacting copper and neodymium ions: chains of copper ions are framed on two sides by chains of neodymium ions. The magnitude of the parameter of the exchange interaction between the copper and neodymium ions is estimated as J ^Cu-Nd⩾0.2 cm⁻¹. An exchange interaction between magnetically nonequivalent neodymium ions is not revealed in the EPR spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 2057–2061 (November 1997)     

Die Eigenschwingungen des Metall-Hydratkomplexes in BeSO4·4H2O und BeSO4·4D2O

Infrared reflection spectra of single crystals of BeSO₄·4H₂O and BeSO₄·4D₂O have been obtained in polarized light at 300°K and at 14°K in the region between 4000 cm^?1 and 300 cm^?1. By a Kronig-Kramers analysis, the frequencies of the infrared active transitions have been calculated. These transitions are attributed to internal vibrations of the water molecules and sulfate ions and, in the region between 1000 cm^?1 and 300 cm^?1, especially to internal and external vibrations of the tetrahedral Be⁺⁺·4aqu-complexes. The vibrational modes of these complexes consist of a superposition of translational and librational modes of the water molecules and translational modes of the central Be⁺⁺-ion. The vibrational frequencies and normal modes of this complex have been calculated in a central-force model, and force-constants have been determined by fitting the calculated frequencies to the observed spectra. The calculations have shown that the modes, which comprise mainly translational motions of the water molecules, are strongly coupled with librational motions of the water molecules. On the other hand, there exist pure librational modes with practically no admixture of translational motions. The optimum sets of force constants for the BeSO₄·4H₂O crystal and the BeSO₄·4D₂O crystal differ in a manner which can be understood under the assumption that the dimensions of the Be(D₂O)₄ complex are about 0.1 Å larger than those of the Be(H₂O)₄ complex. Some arguments supporting this conclusion will be discussed.     

Infrared spectra and isomeric structures of hydroxide ion-water clusters OH- (H2O)1-5: a comparison with H3O (H2O)1-5

Size-selected hydroxide ion water tetramers and pentamers [OH-(H₂O)_4,5], produced by a supersonic expansion, have been investigated using vibrational predissociation spectroscopy in conjunction with ab initio calculations based on density functional theory (DFT). The observed spectra in the frequency range 2650–3850 cm^?1 show some broad absorption bands attributed to the free and hydrogen bonded OH stretches of OH-(H₂O)_4,5 at an estimated cluster temperature of 170 K. DFT calculations performed at the B3LYP/6-31 + G* level reveal five and eight possible low lying isomeric forms for OH-(H₂O)₄ and OH-(H₂O)₅, respectively. The global minimum isomer of the tetramer is tri-solvated cyclic, which is energetically more stable than the tetra-solvated wheel-shaped form with an OH- ion at its centre. Compact cage-like lowest energy structures are found for the pentamer, in which the water molecules can act either as a single-donor-single-acceptor, as a double-proton-donor, or as a double-donor-single-acceptor in both the firs1183t a1192nd the second solvation shell of the OH- ion core. Interconversion among the isomers appears to be rapid as manifested in the observed spectra dominated by broad and congested absorptions. To understand the nature of spectral broadening and congestion, systemic comparisons of the results are made against those of the corresponding protonated cations, H+(H₂O)_n|1 and the corresponding halide anions, X-(H²O)ⁿ X = F, Cl, Br, and I. It is suggested that the spectral complexities observed for OH-(H₂O)_4,5 are predominantly a result of sampling configurations with a large distribution of O_solvent-O_ion-O_solvent angles and O_solvent … H-O_solvent distances between water molecules in the firs1175t a1181nd/or second hydration shells, together with the existence of more than one isomer in the supersonic expanson and rapid isomeric interconversion among them.     

NMR proton relaxation and chemical exchange in the system H16 2O/H17 2O-[2H6]dimethylsulphoxide

NMR proton relaxation rates of normal and ¹⁷O enriched water in a mixture of 68 mol% water and 32 mol% [²H₆]dimethylsulphoxide were measured for temperatures between 298 K and 183 K. In the range between 240 K and 204 K the limit of fast proton-proton exchange between H¹⁶ ₂O and H¹⁷ ₂O is not obeyed, and relaxation curves deviate from mono-exponential behaviour. By fitting the relaxation curves to a model of NMR two-phase relaxation the proton-proton exchange rate within the aqueous component could be obtained. With decreasing temperature, proton-proton exchange slows down and a residence time of about 125 ms at 215 K is found, but it becomes faster again for still lower temperatures. From the phase-averaged relaxation rates of water in the ¹⁷O enriched mixtures, the ¹⁷O induced proton relaxation rate was derived as a function of temperature. This yields the rotational correlation times of the water molecule in the mixture and the dipolar spin-lattice coupling parameter. The latter is considerably lower than the one predicted from the geometry of water.     

Effect of water of crystallization on magnetic properties of MgSO4

The object of this paper has been to determine the effect of water of crystallization on magnetic properties of MgSO₄. Changes in the magnetic properties of MgSO₄ in depenedence on the number of waters of crystallization have been established from the magnetic susceptibility changes. The value obtained by measurement differs from that calculated by the additivity law. This disagreement can be explained by the presence of the thermally independent Van Vleck's polarization paramagnetism _p .The paper brings forward calculations of _p values for the individual hydrates of MgSO₄.i H₂O fori=0, 1, ..., 7. Besides, it examines what portion of the polarization paramagnetism _pi of the overall values of _pci is due to the effect of water of crystallization. On the basis of this information the deviation from the spherical symmetry, caused by hydration of the MgSO₄ molecule, has been interpreted.     

Magnetic susceptibility and magnetic-field behavior of CuB2O4 copper metaborate

An experimental study is reported regarding the temperature dependence of the magnetic susceptibility of a CuB₂O₄ tetragonal single crystal within the 4.2–200-K range. It has been established that the magnetic susceptibility exhibits anomalies at 21 and 10 K and depends strongly on crystal orientation in the magnetic field. A study has been carried out of the field dependences of the magnetization of CuB₂O₄ at various temperatures and crystal orientations. It is shown that for T>21 K, the crystal is in a paramagnetic state determined by Cu²⁺ copper ions with an effective magnetic moment of 1.77 μ_B. Within the 10–21 K interval, the field dependence of the magnetization is typical of a weak ferromagnet with magnetic moments of the two antiferromagnetically coupled sublattices lying in the tetragonal plane of the crystal. The spontaneous weakly-ferromagnetic moment is 0.56 emu/g at 10 K. The canting angle of the sublattice magnetic moments, determined by the Dzyaloshinski-Moriya interaction, is 0.49°. It is believed that below 10 K, the CuB₂O₄ crystal retains its easy-plane magnetic structure, but with a zero spontaneous magnetic moment.     

Mössbauer study of thermal conversion of FeSO4·7H2O

The aim of this study was to identify intermediary products and study of the oxidation level of FeSO₄·7H₂O in the temperature region from 200 to 600°C. The knowledge of the reaction process in this temperature region is important for the optimisation of the technology used in the red pigment manufacture.     

Water enrichment by H2O ortho-isomer: Four-photon and NMR spectroscopy

Ratio of H₂O ortho-/para-spin-isomers in water of different treatment procedures (distilled or cavitation fountain) were studied by both Rayleigh wing four-photon spectroscopy and ¹H nuclear magnetic resonance (NMR) spectroscopy. Low-frequency gas-like rotational resonances were observed in the 0.1–1.5 cm^?1 (3–45 GHz) spectral range and NMR proton density was measured in both water samples. We established that the intensity of ortho-isomer line (6₁₆?5₂₃)0.74 cm^?1 measured by four-photon spectroscopy increases by factor of ～3.5 after cavitation treatment of distilled water. Moreover, the proton density measured by NMR spectroscopy in the same sample grows on ～17%. We have suggested that the enrichment of the distilled water by ortho-H₂O molecules was achieved due to cavitation bubbles collapse when the water passes through the supercritical state.     

Magnetic properties of partially devitrified B2O3-MnFe2O4 glass

Crystallization processes of partially devitrifled glass obtained by rapid quenching of 0·17₅ MnO + 0·17₅. Fe₂O₃ + 0·65 B₂O₃ melt were studied by DTA and X-ray analyses and the temperature regions of nucleation, crystallization and decompozition of the spinel phase were established. The magnetization curves measured between 4·2 and 250 K in magnetic fields up to 42 kOe divided the samples into two groups: the original as cast glass and those annealed below the crystallization temperature, as well as above the decomposition temperature showed essentially paramagnetic behaviour, whereas those annealed closely above the crystallization temperature displayed a spontaneous magnetic moment. The former ones could not be classified as superparamagnetic but the temperature dependence of their susceptibility could be explained by interactions of the antiferromagnetic type. The comparison of lattice parameter and Curie temperature of the latter one with crystalline Mn _x Fe_3-x O₄, system indicated pronounced iron enrichment of the spinel phase formed during heat treatment.Based on a paper presented at the Conference of Socialist Countries on Magnetic Oxides and Compounds; Reinhardsbrunn bei Friedrichroda, GDR, October 22nd–27th, 1972.The authors thank Mrs. A.Hadincová for the help with the evaluation of the results.     

NQR Study of Phase Transition and Cationic Motion in 4-NH2C5H4NHBiBr4·H2O

Four ⁸¹Br NQR lines in 4-NH₂C₅H₄NHBiBr₄·H₂O were observed in the temperature range between 77 and ca. 380 K; with increasing temperatures the respective sets of higher and lower two resonance lines coalesced into single lines discontinuously at 274 K, showing the occurrence of a first-order type phase transition of this crystal. The transition was confirmed with heat anomaly on a DTA curve. Each higher and lower line of high-temperature phase is assignable to the terminal Br atoms and the bridging ones of one-dimensional poly anions (BiBr₄ ⁻) _n in the crystal structure (C2/c), which was investigated by a X-ray structure analysis at room temperature. The 1/T ₁ temperature dependence of ⁸¹Br NQR follows the usual T ² law in the temperature range between 77 and ca. 140 K, being explained by fluctuation of the EFG at Br nucleus due to lattice vibrations. The T ₁ vs. 1/T curve in the temperature range between about 160 and 190 K was describable by the exponential curves, allowing us the estimation of activation energies. These exponential behaviors of T ₁ of ⁸¹Br NQR are attributable to the fluctuations caused by the thermal motion of 4-NH₂C₅H₄H⁺ ions. Echo signals of the ⁸¹Br NQR could not be detected above 190 K owing to poor S/N with very short T ₂.     

NMRON studies of the quasi-2-dimensional ferromagnet 54Mn-Mn(COOCH3)2·4H2O

Pulsed and continuous wave NMRON, and NMR thermally detected by Nuclear Orientation have been used to investigate the magnetic properties of the quasi-2-dimensional ferromagnet ⁵⁴Mn-Mn(COOCH₃)·4H₂O. The NMR frequencies of both the ⁵⁴Mn spins and the abundant ⁵⁵Mn spins have been determined for the two crystalline lattice sites Mn1 and Mn2. The line widths of the ⁵⁴Mn resonances are homogeneously broadened to about 300 kHz, and the ⁵⁵Mn resonances are significantly pulled down in frequency. The spin-lattice relaxation times in low applied magnetic fields are short with T₁ for the Mn2 site being much less than the value for the Mn1 site. Level crossing is observed between the Mn1 and Mn2 resonances in an applied field of 2.6 T. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal contact between Na3[Ce(C7H3NO4)3] · 15H2O and liquid 3He at millikelvin temperatures

Very short thermal equilibrium times have been observed at millikelvin temperatures between powdered Na₃[Ce(C₇H₃NO₄)₃] · 15 H₂O, and pure ³He. Both a large increase in these times and a change in their temperature dependence occurs when 1% ⁴He. Both a large increase in these times and a change in their temperature dependence occurs when 1% ⁴He is added.