The bonded water molecule3ĪII: 180° Flips and diffusion

The proton spin-lattice relaxation time, T₁, is measured as a function of temperature in α -(COOH)₂·-2H₂O, K₂HgCl₄· H₂O and LiCHO·H₂O. The relaxation is caused by 180° flips of the water molecules about their 2-fold axes and good agreement is obtained between calculated and observed values of T₁. Empiricly the flip rate follows a classical Arrhenius equation: P· exp $\text{(? ΔH}\text{(RT))}$. A literature survey of values of P and ΔH obtained from similar investigations on other hydrates is given. The survey shows that the preexponential factor, P, is a function of the activation enthalpy, ΔH. P increases from 10¹² to 10¹⁷ Hz when ΔH changes from 2 to 17 $\text{kcal}\text{mole}$. Using a dynamical rate theory as formulated by Feit, we find the flip rate is given by: K₂· √(ΔH)· exp (K₁ΔH)· exp $\text{(?ΔH}\text{(RT>))}$. This expression can be fitted to the observed data using K₁ = 0.69 $\text{mole}\text{kcal}$ and K₂ = 2 × 10¹¹ Hz · $\text{(kcal}\text{mole)}$$\text{?1}\text{2}$. Thus both the frequency factor, K₂√ (ΔH), and the entropic factor, exp (K₁ΔH), have been obtained for flipping water molecules in hydrates. The values of K₁ and K₂ are shown to be physically reasonable.     

Structure,vibrational study and conductivity of the trihydrated uranyl bis(dihydrogenophosphate): UO2(H2PO4)2·3H2O

The X-ray structure (293 K) of UO₂(H₂PO₄)₂·3H₂O has been refined (R = 0.062): M_r = 518g, space group: P2₁/c (Z = 4); $\text{a = 10.816(1)}\text{A}\text{?}$, $\text{b = 13.896(2)}\text{A}\text{?}$, $\text{c = 7.481(1)}\text{A}\text{?}$, β = 105.65(1)^°, $\text{V = 1082.7(2)}\text{A}\text{?}{}^3$; D_c = 3.17 Mg m^?3. The structure consists of infinite chains along the (101) axis with U atoms bridged by two H₂PO₄ groups. The U atom is surrounded by a pentagonal bipyramid of oxygen atoms, one of them being an equatorial water molecule. The cohesion between the chains is ensured by hydrogen bonds involving the two last water molecules. An assignment of IR and Raman bands with isotopic substitution spectra is proposed. A phase transition at 128 K was made evident by DSC and spectroscopy. The room-temperature phase is characterized by a high disorder of the OH bond orientation while in the low-temperature phase H₂O and POH species appear well oriented. The conductivity seems to occur by proton transfer and protonic-species rotation at the POH-water molecular interface between the chains. ac conductivity has been determined by means of the complex-impedance method ($\text{σ}{}_{\mathrm{<mtext>RT</mtext>}}\text{～ (3?12) × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$; E ～ 0.20 eV).     

NMR investigation of the structure of NiZrF6·.6H2O at low temperatures

Previous studies have shown that NiZrF₆.6H₂O can be described by an axial spin Hamiltonian with parameters g = 2.33 and $\text{D}\text{k}\text{= ?3.14}\text{K}$, and exhibits ferromagnetic ordering at T_c = 164mK. Our room temperature X-ray measurements confirm that NiZrF₆·.6H₂O is isomorphous with NiSnCl₆·.6H₂O and give lattice parameters of $\text{a = 6.55}\text{A}\text{?}$ and α = 96°09′. Proton NMR measurements show that there exist important molecular motions at room temperature and that the space group remains $\text{R}\text{3}$ down to liquid helium temperatures. The positions of all twelve protons have been determined and are found to lie on a sphere of radius 2.9 Å centered on the nickel ion.     

Infrared and raman spectra of barium nitrite monohydrate

The low temperature infrared absorption and room temperature laser Raman spectra of polycrystalline Ba(NO₂)₂ · H₂O and its deuterated analogue are studied. The strongly bonded H-atom of the water molecule makes a highly bent H-bond while the weakly bonded H-atom exhibits a slightly bent (or possible bifurcated) bond consistent with recent structural data; the H-bond enthalpies are estimated to be 3.3 and 2.1 $\text{KCal}\text{mole}$ respectively. The wagging, twisting and rocking modes of the water molecule have been assigned using several well known criteria. The force constants of these modes have also been computed. The librational splittings observed at low temperature are consistent with polarization data, and are being attributed to infrared active factor group components.     

High-temperature specific heat and susceptibility of the quadratic S = 12 XY model. Comparison with data on CoCl2.6H2O and CoBr2.6H2O

This susceptibility of the quadratic, $\text{S =}\text{1}\text{2}$, XY model as determined by the high-temperature series expansion is presented and compared with experimental data on CoCl₂.6H₂O and CoBr₂.6H₂O. For the specific heat of CoCl₂.6H₂O a similar comparison is made. For kT/|J| > 1.5 a good agreement between theory and experiment is found, yielding J/k = ?2.05 ± 0.1 and ?2.45 ± 0.1 K for the intralayer exchange of the Cl and the Br salt, respectively. These values compare favourably with those available from other sources.     

The oxidation of methanol on a silver (110) catalyst

The oxidation of methanol was studied on a Ag(110) single-crystal by temperature programmed reaction spectroscopy. The Ag(110) surface was preoxidized with oxygen-18, and deuterated methanol, CH₃OD, was used to distinguish the hydroxyl hydrogen from the methyl hydrogens. Very little methanol chemisorbed on the oxygen-free Ag(110) surface, and the ability of the silver surface to dissociatively chemisorb methanol was greatly enhanced by surface oxygen. CH₃OD was selectively oxidized upon adsorption at 180 K to adsorbed CH₃O and D₂¹⁸O, and at high coverages the D₂¹⁸O was displaced from the Ag(110) surface. The methoxide species was the most abundant surface intermediate and decomposed via reaction channels at 250, 300 and 340 K to H₂CO and hydrogen. Adsorbed H₂CO also reacted with adsorbed CH₃O to form H₂COOCH₃which subsequently yielded HCOOCH₃ and hydrogen. The first-order rate constant for the dehydrogenation of D₂COOCH₃ to DCOOCH₃ and deuterium was found to be (2.4 ± 2.0) × 10¹¹ exp(?14.0 ± 0.5 $\text{kcal}\text{mole}$ · RT)sec^?1. This reaction is analogous to alkoxide transfer from metal alkoxides to aldehydes in the liquid phase. Excess surface oxygen atoms on the silver substrate resulted in the further oxidation of adsorbed H₂CO to carbon dioxide and water. The oxidation of methanol on Ag(110) is compared to the previous study on Cu(110).     

The decomposition of formic acid on Ni(100)

The decomposition of HCOOD was studied on Ni(100). Low temperature adsorption of HCOOD resulted in the desorption of D₂O, CO₂, CO, and H₂. The D₂O was evolved below room temperature. CO₂ and H₂ were evolved in coincident peaks at a temperature above that at which h₂ desorbed following H₂ adsorption and well above that for CO₂ desorption from CO₂ adsorption; CO desorbed primarily in a desorption limited step. The decomposition of formic acid on the clean surface was found to yield equal amounts of H₂, CO, and CO₂ within experimental error. The kinetics and mechanism of the decomposition of formic acid on Ni (110) and Ni(100) single crystal surfaces were compared. The reaction proceeded by the dehydration of formic acid to formic anhydride on both surfaces. The anhydride intermediate condensed into islands due to attractive dipole-dipole interactions. Within the islands the rate of the decomposition reaction to form CO₂ was given by:

$\text{Rate = 6 × 10}{}^{15}\text{exp{?[25,500 + ω(}\text{c}\text{c}{}_{\mathrm{sat}}\text{)]/RT} × c}$

, where c is the local surface concentration, c_sat is the saturation coverage for the particular crystal plane, and ω is the interaction potential. The interaction potential was determined to be 2.7 kcal/mole on Ni(110) and 1.4 kcal/mole on Ni(100); the difference observed was due to structural differences of the surfaces relating to the alignment of the dipole moments within the islands. These attractive interactions resulted in an autocatalytic reaction on Ni(110), whereas the interaction was not strong enough on Ni(100) to sustain the autocatalytic behavior. Formic acid decomposition oxidized the Ni(100) surface resulting in the formation of a stable surface oxide. The buildup of the oxide resulted in a change in the selectivity reducing the amount of CO formed. This trend indicated that on the oxide surface the decomposition proceeded via a formate intermediate as on Ni(110) O.     

Electronic-excitation transfer collisions in flames—V. Cross sections for quenching and doublet-mixing of K(42P)-doublet by N2, O2, H2 and H2O

Weighted average cross sections for quenching of the K(4²P)-doublet by N₂, H₂, O₂ and H₂O, measured in flames, show no significant temperature dependence in the range from 1500 to 2500K. Doublet mixing cross sections for K(4²P$\text{3}\text{2}$?4²P$\text{1}\text{2}$) transitions were measured at 1720K for N₂, O₂, H₂O. The ratios of both mixing cross sections were measured independently and were found to agree with the detailed balance condition within 2 per cent. It is shown that an ionic intermediate-state model cannot explain the large magnitude of N_2? mixing cross sections.     

Adsorption of CO on clean and oxygen covered Ni(111) surfaces

Adsorption of CO on Ni(111) surfaces was studied by means of LEED, UPS and thermal desorption spectroscopy. On an initially clean surface adsorbed CO forms a √3 × $\text{√3}\text{R30°}$ structure at θ = 0.33 whose unit cell is continuously compressed with increasing coverage leading to a c4 × 2-structure at θ = 0.5. Beyond this coverage a more weakly bound phase characterized by a $\text{√7}\text{2}$ × $\text{√7}\text{2R19°}$ LEED pattern is formed which is interpreted with a hexagonal close-packed arrangement (θ = 0.57) where all CO molecules are either in “bridge” or in single-site positions with a mutual distance of 3.3 Å. If CO is adsorbed on a surface precovered by oxygen (exhibiting an O 2 × 2 structure) a partially disordered coadsorbate 2 × 2 structure with θ_o = θ_co = 0.25 is formed where the CO adsorption energy is lowered by about 4 kcal/mole due to repulsive interactions. In this case the photoemission spectrum exhibits not a simple superposition of the features arising from the single-component adsorbates (i.e. maxima at 5.5 eV below the Fermi level with O_ad, and at 7.8 (5σ + 1π) and 10.6 eV (4σ) with CO_ad, respectively), but the peak derived from the CO 4σ level is shifted by about 0.3 eV towards higher ionization energies.     

The adsorption of CO,H2, H2, CO2 and H2O on carburized and graphitized Ni(110)

A study of the adsorption/desorption behavior of CO, H₂O, CO₂ and H₂ on Ni(110)(4 × 5)-C and Ni(110)-graphite was made in order to assess the importance of desorption as a rate-limiting step for the decomposition of formic acid and to identify available reaction channels for the decomposition. The carbide surface adsorbed CO and H₂O in amounts comparable to the clean surface, whereas this surface, unlike clean Ni(110), did not appreciably adsorb H₂. The binding energy of CO on the carbide was coverage sensitive, decreasing from 21 to 12 $\text{kcal}\text{mol}$ as the CO coverage approached 1.1 × 10¹⁵ molecules cm^?2 at 200K. The initial sticking probability and maximum coverage of CO on the carbide surface were close to that observed for clean Ni(110). The amount of H₂, CO, CO₂ and H₂O adsorbed on the graphitized surface was insignificant relative to the clean surface. The kinetics of adsorption/desorption of the states observed are discussed.     

Further neighbour interactions in the quasi b.c.c. Heisenberg ferromagnets M2 Cu X4 · 2H2 O (M = NH4, K,Rb or Cs; X = Cl or Br)

The Curie-Weiss constant θ of the quasi b.c.c., $\text{S =}\text{1}\text{2}$, Heisenberg ferromagnets, (NH₄)₂ Cu Br₄ · 2H₂ O and Rb₂ Cu Br₄ · 2H₂ O, have been derived from measurements of the susceptibility in the paramagnetic region (4.2 < T < 100 K) and of the high-field magnetization curves at $\text{T = 4.2}\text{K}\text{(}\text{T}\text{T}{}_{\mathrm{c}}\text{? 2.3)}$. The $\text{T}{}_{\mathrm{c}}\text{θ}$ values obtained point to the presence of further neighbour interactions considerably stronger than previously assumed. The effective number of equivalently interacting magnetic neighbours is estimated to be at least seventeen.     

High temperature thermodynamics of H2 and D2 in titanium,and in dilute titanium oxygen solid solutions

The Tian Calvet microcalorimetric method has been improved in order to determine Δ$\text{H}$_H(D), the partial molar enthalpy of mixing of hydrogen (deuterium) in the Ti-H₂(D₂) solid systems for compositions 0 < (H/Ti) < 1.85, at 713 K and in the α TiO_y + H₂ solid solutions (y = (O/Ti)) at 745 K. The combined calorimetric and equilibrium method allows a precise evaluation of the partial molar entropies. The results of this study differ substantially from earlier published data.     

Asymmetry in semi-inclusive annihilation

Interference between one- and two-photon processes for e⁺e^? annihilation into hadrons in a two-jet parton model leads to a charge asymmetry of detected final state hadrons along the directions of the incident leptons. The asymmetry near the lepton axis grows as $\text{2}\text{ln}{}^2\text{1}\text{2}\text{θ - 4}\text{ln}\text{1}\text{2}\text{θ}\text{ln}\text{s/ΔE}{}^2$, so that in spite of the O(α) suppression relative to the Born cross section, the asymmetry can amount to a 2% effect at θ = 2° for π^± or K^± inclusive measurements in a typical experiment. The precise size of the asymmetry depends on the parton charges. Our results are only meant to apply in the region ω ? 0.5,where the parton model appears to be relevant at present experimental energies.     

Antiferromagnetism in K2[FeCl5(H2O)] and its dependence upon hydrostatic pressure

We have measured the isothermal magnetization M of antiferromagnetic K₂[FeCl₅(H₂O)] as a function of applied magnetic field H, for fields up to 80 kOe and for several hydrostatic pressures up to P ～ 10 kbar. We obtained the P =1 atm exchange parameters of this material for an orthorhombic model. The spin-flop boundary of K₂[FeCl₅(H₂O)] was studied for several pressures. For the spin-flop fields H_SF, a relation of the form $\text{H}{}_{\mathrm{SF}}\text{(T) = H}{}_{\mathrm{SF}}\text{(0) (1 + BT}\text{3}\text{2}\text{+ CT}{}^2\text{+ DT}\text{5}\text{2}\text{)}$ adequately describes the experimental points up to relatively high temperatures, for all pressures. The isotherms H_SF vs. P show an abrupt change of slope at P ? 1 kbar, possibly due to a pressure-induced exchange of the intermediate and hard magnetic axes.     

The angular dependence of flux,mean energy and speed ratio for D2 molecules desorbing from a Ni(111) surface

Experimental data are presented for the angular dependence of the relative flux, the mean energy and the speed ratio of deuterium molecules desorbing from a Ni(111) crystal surface at a surface temperature of T_s = 1143 K and at sulphur coverages ranging between 30% and less than 2% of a monolayer.The angular flux distribution is sharply peaked in the forward direction (cos^dθwith 3 ? d ? 5) and the mean energy 〈E〉 of the desorbate depends strongly on the desorption angle θ. For normal desorption $\text{(θ = 0°)}\text{〈E〉}\text{2k}$ is about 700 K higher than T_s and for glancing angles (θ = 80°) it decreases to about 400 K below T_s The results obtained on sulphur free and sulphur covered Ni(111) surfaces are compared with our former data on polycrystalline nickel. The main differences in the kinetic features can be ascribed to the surface roughness. Accordingly, the angular distributions of flux, mean energy, and speed ratio, which deviate strongly from the Knudson and Maxwellian law, do not seem to depend considerably on sulphur coverage and surface structure. A qualitative explanation for these deviations is presented using the principle of detailed balancing.     

Electrical conductivity in amorphous Si(O or H)-Au films

SiO films obtained by sputtering in an ArO mixture with an oxygen partial pressure less than 3% are similar to a-Si films: the resistivity is proportional to exp (T₀/T)^{$\text{1}\text{4}$} and T₀ increases with oxygen content and decreases with increasing Au concentration (? 3.7 at.%). On the other hand, above an oxygen partial pressure of 5% one obtains insulating amorphous SiO₂ films. Conductivity appears in such films for Au? 13 at.% (? the percolation threshold) and then the resistivity is proportional to exp (T₀/T)^{$\text{1}\text{2}$}. The same behavior is observed when oxygen is replaced by hydrogen.     

Investigation of the diffusion of hydrogen in palladium by means of spin-lattice relaxation in the rotating frame

The diffusion of hydrogen in palladium $\text{(}\text{H}\text{Pd}\text{= 0.73)}$ has been investigated from 170 to 300K by measurements of the proton spin-lattice relaxation time in the rotating frame, T_1?. In contrast to previous T₁ measurements, a single activation energy of 0.225 eV is obtained, in agreement with the high-temperature T₁ data and with internal friction experiments at about 120K.     

Electrical resistance and magnetoresistance of amorphous alloys Gd67Co33 and Pd80Si20

In search for structural contributions to the low temperature anomaly we report high resolution resistance and magnetoresistance measurements ($\text{0.02}\text{K}\text{? T ? 20}\text{K}$) of amorphous splats of Gd₆₇Co₃₃ and Pd₈₀Si₂₀. For both alloys, the resistivity ?(H = 0, T) has a minimum at T ～ 10 K and increases with decreasing T. The ferromagnetic Gd₆₇Co₃₃ shows a strong negative field dependence of $\text{Δ?}\text{?(0)}$, saturating at H ～ 2T for T = 4.2 K but no measurable change in $\text{??}\text{?}\text{T}$ below 10 K is observed.The diamagnetic Pd₈₀Si₂₀ exhibits a positive field dependent magnetoresistance $\text{[Δ?}\text{?(0)]}\text{(}\text{H}\text{)}$ at low temperatures. Additionally, a field dependent part in $\text{??}\text{?}\text{T}$ is found which is probably due to paramagnetic impurities (～ 1 ppm Fe). However, there is also a field independent contribution in the amorphous state of Pd₈₀Si₂₀, which vanishes after crystallization. We attribute this to non-magnetic scattering induced by the disordered structure.     

Temperature jump method in molecular beam relaxation spectrometry applied to catalytic decomposition of CH3OH on polycrystalline Ni foil

A new modification of molecular beam relaxation spectrometry (MBRS) is described: the temperature jump method for studying catalytic surface processes on metal foils. The temperature of the catalyst foil is maintained by direct ohmic heating; a constant particle beam is directed towards the catalyst surface. A jump of the surface temperature caused by a high current pulse generates a response of the fluxes of desorption. The decay of the desorption intensity after the temperature jump contains the relaxation times of the elementary steps involved. The mathematical treatments of unimolecular and bimolecular surface reactions, of sequences of two and three unimolecular steps and of a sequential reaction accompanied by the redesorption of the reactant are given. The application of the new method is shown by a study of the catalytic decomposition of CH₃)OH on polycrystalline Ni: CO and H₂ are the sole reaction products. The limit of the catalytic activity — apart from the low sticking probability of the reactant — must be seen in the abstraction of the first methyl hydrogen from the transient methoxy species. In the temperature range between 320 and 550 K the reaction mechanism can be described as follows:

Rate constants in dependence from surface temperature T are: k₁ = 4.2 × 10⁴ exp$\text{(}\text{?22.4}\text{RT}$$\text{kJ}\text{mol}\text{)}$ s^?1; k₃ = 2.4 × 10⁹ exp$\text{(}\text{?75}\text{RT}$$\text{kJ}\text{mol}\text{)}$ s^?1; k₄ = 1.2 × 10¹³ exp$\text{(}\text{?104}\text{RT}$$\text{kJ}\text{mol}\text{)}$ s^?1; η = 0.2. Typical surface residence times of the intermediates are: 110 ? τ₁ ? 15 ms at 320 ? T ? 450 K; 210 ? τ₃ ? 6 ms at 450 ? T ? 550 K; 98 ? τ₄ ? 6 ms at 450 ? T ? 500 K.     

A neutron diffraction study of structural changes in one-dimensional K2Pt(CN)4Br0.3 · 3H2O from 77–323°K

Single crystal neutron diffraction measurements of K₂Pt(CN)₄Br_0.3 · 3H₂O (KCP) above room temperature, to the point of irreversible crystal breakdown (318–323°K), and at liquid nitrogen temperature (77°K), give no indication of a crystallographic phase change. Full three-dimensional data collected at 77°K ($\text{a = 9.848(5)}\text{A}\text{?}\text{, c = 5.714(3)}\text{A}\text{?}\text{,}\text{and space group}\text{P4mm}$) indicate that the structure is essentially unchanged from that at room temperature except for increased hydrogen bonding association between H₂O(2) and Br(1). The possible relationship between the hydrogen bonding changes and Br(1) site ordering is discussed.