Dynamical cage behaviour and hydrogen migration in hydrogen and hydrogen-tetrahydrofuran clathrate hydrates

Classical equilibrium molecular dynamics simulations have been performed to investigate dynamical properties of cage radial breathing modes and intra- and inter-cage hydrogen migration in both pure hydrogen and mixed hydrogen-tetrahydrofuran sII hydrates at 0.05 kbar and up to 250 K. For the mixed H(2)-THF system in which there is single H(2) occupation of the small cage (labelled "1SC 1LC"), we find that no H(2) migration occurs, and this is also the case for pure H(2) hydrate with single small-cavity occupation and quadruple occupancy for large cages (dubbed "1SC 4LC"). However, for the more densely filled H(2)-THF and pure-H(2) systems, in which there is double H(2) occupation in the small cage (dubbed "2SC 1LC" and "2SC 4LC," respectively), there is an onset of inter-cage H(2) migration events from the small cages to neighbouring cavities at around 200 K, with an approximate Arrhenius temperature-dependence for the migration rate from 200 to 250 K. It was found that these "cage hopping" events are facilitated by temporary openings of pentagonal small-cage faces with the relaxation and reformation of key stabilising hydrogen bonds during and following passage. The cages remain essentially intact up to 250 K, save for transient hydrogen bond weakening and reformation during and after inter-cage hydrogen diffusion events in the 200-250 K range. The "breathing modes," or underlying frequencies governing the variation in the cavities' radii, exhibit a certain overlap with THF rattling motion in the case of large cavities, while there is some overlap of small cages' radial breathing modes with lattice acoustic modes.     

Molecular-dynamics analysis of the diffusion of molecular hydrogen in all-silica sodalite

In order to investigate the technical feasibility of crystalline porous silicates as hydrogen storage materials, the self-diffusion of molecular hydrogen in all-silica sodalite is modeled using large-scale classical molecular-dynamics simulations employing full lattice flexibility. In the temperature range of 700-1200 K, the diffusion coefficient is found to range from 1.610(-10) to 1.810(-9) m(2)/s. The energy barrier for hydrogen diffusion is determined from the simulations allowing the application of transition state theory, which, together with the finding that the pre-exponential factor in the Arrhenius-type equation for the hopping rate is temperature-independent, enables extrapolation of our results to lower temperatures. Estimates based on mass penetration theory calculations indicate a promising hydrogen uptake rate at 573 K.     

Effect of cation distribution on self-diffusion of molecular hydrogen in Na3Al3Si3O12 sodalite: a molecular dynamics study

The diffusion of hydrogen in sodium aluminum sodalite (NaAlSi-SOD) is modeled using classical molecular dynamics, allowing for full flexibility of the host framework, in the temperature range 800-1200 K. From these simulations, the self-diffusion coefficient is determined as a function of temperature and the hydrogen uptake at low equilibrium hydrogen concentration is estimated at 573 K. The influence of the cation distribution over the framework on the hydrogen self-diffusion is investigated by comparing results employing a low energy fully ordered cation distribution with those obtained using a less ordered distribution. The cation distribution is found to have a surprisingly large influence on the diffusion, which appears to be due to the difference in framework flexibility for different cation distributions, the occurrence of correlated hopping in case of the ordered distribution, and the different nature of the diffusion processes in both systems. Compared to our previously reported calculations on all silica sodalite (all-Si-SOD), the hydrogen diffusion coefficient of sodium aluminum sodalite is higher in the case of the ordered distribution and lower in case of the disordered distribution. The hydrogen uptake rates of all-Si-SOD and NaSiAl-SOD are comparable at high temperatures (approximately 1000 K) and lower for all-Si-SOD at lower temperatures (approximately 400 K).     

Diffusion of gas molecules in the polystyrene matrix

We have studied the diffusion of gas molecules inside an amorphous polystyrene matrix. The diffusion constant of several gases at T = 450 K in polystyrene was computed. Particular attention was given to CO₂ for temperatures between 300 and 800 K. The temperature dependence of the diffusion constant and the relationship between the diffusion constant and the diameter of the gas molecule were analysed. We further examined the motion of the gas molecules on the short time scale not readily accessible to experimental observation. Here we used the cage overlap function which gives information on the typical cage sizes and distribution times. On the short time scale the gas molecules show a hopping behaviour. The distribution of the time period between hopping events, the distance between the cages and the size of the cages in the polystyrene matrix in the presence of guest molecules were calculated. Through the analyzing, we get a clearer picture from the behaviour of gas molecules on short time scale in the polymer matrix.     

Anhydrous and water-assisted proton mobility in phosphotungstic acid

Nonlocal gradient-corrected density functional theoretical calculations were used to determine the energetics associated with proton migration in phosphotungstic acid. The activation energy for anhydrous proton hopping between two oxygen atoms on the exterior of the molecular Keggin unit was calculated to be 103.3 kJ mol(-1). The quantum-tunneling effect on the rate of proton movement was determined using semiclassical transition-state theory and was found to be a major contributor to the overall rate of proton movement at temperatures below approximately 350 K. The adsorption of water on an acidic proton decreases the activation barrier for hopping to 11.2 kJ mol(-1) by facilitating proton transfer along hydrogen bonds. The overall rate constant for proton hopping was determined as a function of temperature and water partial pressure. Small amounts of water greatly enhance the overall rate of proton movement.     

Relevance of cage recombination in the plastic deformation of polymers

For a polymer in which permanent rupture of individual molecules is the rate-limiting process for plastic deformation, the kinetics of chain-end diffusion and secondary radical reactions should be compared with the kinetics of caged radical recombination in the calculation of activation parameters for plastic deformation. If mechanisms of cage escape are slower than those for cage recombination, the activation parameters for plastic deformation will differ from those for the initial bond-breaking process. For the case of polyethylene deformed in the vicinity of 250°K, the critical thermally activated event appears to involve scission of the polymer molecule near the site of an abstracted hydrogen atom. For this system the dominant cage-escape mechanism is diffusion, which is faster than either hydrogen abstraction or unzipping to the monomer. However, at low stresses the rate of cage recombination is expected to be higher than the rate of cage escape, so that the activation parameters for deformation should be the sum of those for chain scission and diffusion. The contribution of diffusion (ca. 15 kcal/mole) to the activation energy for deformation (E^*, extrapolated to zero stress conditions) is relatively modest. However, the calculated molar activation volume for deformation V^* increases by almost an order of magnitude, i.e., from ca. 10 to ca. 76 cm³/mole when diffusion is required. Consideration of experimental values of E^* and V^* for high molecular weight polyethylene indicates that, in the regime examined, chain scission plus chain-end diffusion is required to effect plastic deformation.     

Orientational dynamics of water in the nafion polymer electrolyte membrane and its relationship to proton transport

Orientational anisotropies are calculated from molecular dynamics simulations of bulk water and the Na(+) and H(+) forms of hydrated Nafion and then compared with corresponding experimental values. The extended jump model of Laage and Hynes is applied to water reorientations for each system, and the anisotropies are explored as a product of hydrogen bond restricted "wobble-in-a-cone" reorientations and that due to the discrete jumps of hydrogen bond reorganization. Additionally, the timescales of hydrogen bond switching and proton transport are presented for bulk water and the H(+) form of hydrated Nafion. The short time scale of proton hopping is found to be independent of Nafion water loading, suggesting the short time dynamics of proton hopping are relatively insensitive to the level of hydration. Furthermore, the long time decay for the forward rate of hydrogen bond switching is shown to be identical to the long time decay in the forward rate of proton hopping, for bulk water and all water loadings of Nafion investigated, suggesting a unified process.     

Quantum diffusion of hydrogen and muonium atoms in liquid water and hexagonal ice

We have used the ring polymer molecular dynamics method to study the diffusion of muonium, hydrogen, and deuterium atoms in liquid water and hexagonal ice over a wide temperature range (8-361 K). Quantum effects are found to dramatically reduce the diffusion of muonium in water relative to that predicted by classical simulation. This leads to a simple explanation for the lack of any significant isotope effect in the observed diffusion coefficients of these species in the room temperature liquid. Our results indicate that the mechanism of the diffusion in liquid water is similar to the intercavity hopping mechanism observed in ice, supplemented by the diffusion of the cavities in the liquid. Within the same model, we have also been able to simulate the observed crossover in the c-axis diffusion coefficients of hydrogen and deuterium in hexagonal ice. Finally, we have been able to obtain good agreement with experimental data on the diffusion of muonium in hexagonal ice at 8 K, where the process is entirely quantum mechanical.     

Rates of electronic excitation hopping in anisotropic ionic crystals of [Ru(2,2'-bipyridine)3]X2 (X = ClO4-, PF6-, SbF6-); Monte Carlo simulation of single- and multi-exponential emission decays

Emission decays of triplet metal-to-ligand charge transfer states in anisotropic crystals of [Ru(1 - x)Os(x)(bpy)(3)]X(2) (bpy = 2,2'-bipyridine, X = PF(6)-, ClO(4)-, SbF(6)-, and 0.115 > x > 0.001) at approximately 300 K were measured by means of time-correlated single-photon counting. Rates of excitation hopping calculated on the basis of an interaction between transition dipoles of a donor cation and an acceptor cation are insufficient to simulate the single-exponential decays (x = 0.0099) and the multiexponential decays (x = 0.060 and 0.115) of the PF(6)- salt crystals. A limiting rate of excitation hopping to an imaginary cation at the van der Waals distance via a super-exchange interaction between d orbitals through the bpy ligands was determined to be 0.83 x 10(10) s(-1) on average by means of a step-by-step Monte Carlo simulation, assuming an distance-attenuation factor, beta, of the exchange interaction of 10 nm-1. The total rate of excitation hopping via both a dipole-dipole mechanism and a super-exchange mechanism to the neighboring sites of the cation was calculated to be 5.4 x 10(9) s(-1) for the PF(6)- crystal. Anisotropic diffusion constants estimated from the hopping rates and lengths in the PF(6)- crystal are 9.3 x 10(-6), 9.1 x 10(-6), and 1.4 x 10(-6) cm(2)s(-1) along the a axis, the b axis, and the c axis, respectively, which are compared with an isotropic diffusion constant, 1.3 x 10(-6) cm(2) s(-1), estimated from the pseudo-bimolecular rate constant of excitation transfer to [Os(bpy)(3)](2+), using an isotropic Smoluchowski equation. A multiexponential emission decay of [Ru(0.885)Os(0.115)(bpy)(3)](PF(6))(2) was also simulated to determined the limiting rate of excitation transfer to [Os(bpy)(3)](2+) at the van der Waals distance (2.6 x 10(11) s(-1)). The magnitude of beta determined is 6.5 and 11.5 nm(-1) for the ClO(4)- and the SbF(6)- salt crystals, respectively, on reference to that of beta (10 nm(-1)) for the PF(6)- salt crystal.     

Testing the conformational hypothesis of passive membrane permeability using synthetic cyclic peptide diastereomers

Little is known about the effect of conformation on passive membrane diffusion rates in small molecules. Evidence suggests that intramolecular hydrogen bonding may play a role by reducing the energetic cost of desolvating hydrogen bond donors, especially amide N-H groups. We set out to test this hypothesis by investigating the passive membrane diffusion characteristics of a series of cyclic peptide diastereomers based on the sequence cyclo[Leu-Leu-Leu-Leu-Pro-Tyr]. We identified two cyclic hexapeptide diastereomers based on this sequence, whose membrane diffusion rates differed by nearly two log units. Results of solution NMR studies and hydrogen/deuterium (H/D) exchange experiments showed that membrane diffusion rates correlated with the degree of intramolecular hydrogen bonding and H/D exchange rates. The most permeable diastereomer, cyclo[d-Leu-d-Leu-Leu-d-Leu-Pro-Tyr] (1), exhibited a passive membrane diffusion rate comparable to that of the orally available drug cyclosporine A.     

Mechanistic study of proton transfer and HD exchange in ice films at low temperatures (100-140 K)

We have examined the elementary molecular processes responsible for proton transfer and HD exchange in thin ice films for the temperature range of 100-140 K. The ice films are made to have a structure of a bottom D(2)O layer and an upper H(2)O layer, with excess protons generated from HCl ionization trapped at the D(2)OH(2)O interface. The transport behavior of excess protons from the interfacial layer to the ice film surface and the progress of the HD exchange reaction in water molecules are examined with the techniques of low energy sputtering and Cs(+) reactive ion scattering. Three major processes are identified: the proton hopping relay, the hop-and-turn process, and molecular diffusion. The proton hopping relay can occur even at low temperatures (<120 K), and it transports a specific portion of embedded protons to the surface. The hop-and-turn mechanism, which involves the coupling of proton hopping and molecule reorientation, increases the proton transfer rate and causes the HD exchange of water molecules. The hop-and-turn mechanism is activated at temperatures above 125 K in the surface region. Diffusional mixing of H(2)O and D(2)O molecules additionally contributes to the HD exchange reaction at temperatures above 130 K. The hop-and-turn and molecular diffusion processes are activated at higher temperatures in the deeper region of ice films. The relative speeds of these processes are in the following order: hopping relay>hop and turn>molecule diffusion.     

One and two hydrogen molecules in the large cage of the structure II clathrate hydrate: quantum translation-rotation dynamics close to the cage wall

We have performed a rigorous theoretical study of the quantum translation-rotation (T-R) dynamics of one and two H2 and D2 molecules confined inside the large hexakaidecahedral (5(12)6(4)) cage of the sII clathrate hydrate. For a single encapsulated H2 and D2 molecule, accurate quantum five-dimensional calculations of the T-R energy levels and wave functions are performed that include explicitly, as fully coupled, all three translational and the two rotational degrees of freedom of the hydrogen molecule, while the cage is taken to be rigid. In addition, the ground-state properties, energetics, and spatial distribution of one and two p-H2 and o-D2 molecules in the large cage are calculated rigorously using the diffusion Monte Carlo method. These calculations reveal that the low-energy T-R dynamics of hydrogen molecules in the large cage are qualitatively different from that inside the small cage, studied by us recently. This is caused by the following: (i) The large cage has a cavity whose diameter is about twice that of the small cage for the hydrogen molecule. (ii) In the small cage, the potential energy surface (PES) for H2 is essentially flat in the central region, while in the large cage the PES has a prominent maximum at the cage center, whose height exceeds the T-R zero-point energy of H2/D2. As a result, the guest molecule is excluded from the central part of the large cage, its wave function localized around the off-center global minimum. Peculiar quantum dynamics of the hydrogen molecule squeezed between the central maximum and the cage wall manifests in the excited T-R states whose energies and wave functions differ greatly from those for the small cage. Moreover, they are sensitive to the variations in the hydrogen-bonding topology, which modulate the corrugation of the cage wall.     

A study of pore blockage in silicalite zeolite using free energy perturbation calculations

Binary systems consisting of large coadsorbed molecules (n-hexane, cyclohexane, and benzene) with smaller penetrant molecules (methane) were simulated to investigate the mechanisms of pore blockage in the zeolite silicalite. Benzene and cyclohexane trap the methane molecules in the zeolite channels on the time scales of molecular dynamics simulations. Minimum energy paths for methane diffusion past the blocking molecules were determined, and free energy perturbation calculations were carried out along the paths to get the rate constants of methane hopping past coadsorbed benzene and cyclohexane molecules, which adsorb in the channel intersections. Three principal diffusion pathways were found in both the methane/benzene and methane/cyclohexane systems. Minima which were connected by low-energy pathways were grouped together into macrostates. Using the calculated hopping rates between macrostates, kinetic Monte Carlo was then used to obtain the diffusivity of methane with a coadsorbate benzene loading such that all channel intersections are filled by benzene - conditions where molecular dynamics simulations fail. Passage of methane across cyclohexane molecules involved pushing the cyclohexane molecules into the channels from their preferred channel intersection positions.     

The initial stage of uranium oxidation: mechanism of UO(2) scale formation in the presence of a native lateral stress field

In this work, an oxidation model for alpha-uranium is presented. It describes the internally lateral stress field built in the oxide scale during the reaction. The thickness of the elastic, stress-preserving oxide (UO(2+x)) scale is less than 0.5 microm. A lateral, 6.5 GPa stress field has been calculated from strains derived from line shifts (delta(2theta)) as measured by the X-ray diffraction of UO(2). It is shown that in the elastic growth domain, (110) is the main UO(2) growth plane for gas-solid oxidation. The diffusion-limited oxidation mechanism discussed here is based on the known "2:2:2" cluster theory which describes the mechanism of fluorite-based hyperstoichiometric oxides. In this study, it is adapted to describe oxygen-anion hopping. Anion hopping toward the oxide-metal interface proceeds at high rates in the [110] direction, hence making this pipeline route the principal growth direction in UO(2) formation. It is further argued that growth in the pure elastic domain of the oxide scale should be attributed entirely to anion hopping in 110. Anions, diffusing isotropically via grain boundaries and cracks, are shown to have a significant impact on the overall oxidation rate in relatively thick (>0.35 microm) oxide scales if followed by an avalanche break off in the postelastic regime. Stress affects oxidation in the elastic domain by controlling the hopping rate directly. In the postelastic regime, stress weakens hopping, indirectly, by enhancing isotropic diffusion. Surface roughness presents an additional hindering factor for the anion hopping. In comparison to anisotropic hopping, diffusion of isotropic hopping has a lower activation energy barrier. Therefore, a relatively stronger impact at lower temperatures due to isotropic diffusion is displayed.     

OH-stretch vibrational relaxation of HOD in liquid to supercritical D2O

The population relaxation of the OH-stretching vibration of HOD diluted in D2O is studied by time-resolved infrared (IR) pump-probe spectroscopy for temperatures of up to 700 K in the density range 12 1 OH stretching transition with a 200 fs laser pulse centered at approximately 3500 cm(-1). Above 400 K these spectra show no indication of spectral diffusion after pump-probe delays of 0.3 ps. Over nearly the entire density range and for sufficiently high temperatures (T > 360 K), the vibrational relaxation rate constant, kr, is strictly proportional to the dielectric constant, epsilon, of water. Together with existing molecular dynamics simulations, this result suggests a simple linear dependence of kr on the number of hydrogen-bonded D2O molecules. It is shown that, for a given temperature, an isolated binary collision model is able to adequately describe the density dependence of vibrational energy relaxation even in hydrogen-bonded fluids. However, dynamic hydrogen bond breakage and formation is a source of spectral diffusion and affects the nature of the measured kr. For sufficiently high temperatures when spectral diffusion is much faster than energy transfer, the experimentally observed decays correspond to ensemble averaged population relaxation rates. In contrast, when spectral diffusion and vibrational relaxation occur on similar time scales, as is the case for ambient conditions, deviations from the linear kr(epsilon) relation occur because the long time decay of the v = 1 population is biased to slower relaxing HOD molecules that are only weakly connected to the hydrogen bond network.     

Atomic motions in the alphabeta-merging region of 1,4-polybutadiene: a molecular dynamics simulation study

We present fully atomistic molecular dynamics simulations on 1,4-polybutadiene in a wide temperature range from 200 to 280 K, i.e., in the region where the alpha- and beta-relaxations merge and above. A big computational effort has been performed-especially for the lowest temperatures investigated-to extend the simulation runs to very long times (up to 1 mus for 200 K). The simulated sample has been carefully validated by using previous neutron scattering data on the real sample with similar microstructure. Inspecting the trajectories of the different hydrogens in real space, we have observed a heterogeneous dynamical behavior (each kind of hydrogen moves in a different way) with signatures of combined hopping and diffusive motions in the whole range investigated. The application of a previously proposed model [Colmenero et al., Europhys. Lett. 71, 262 (2005)] is successful and a characterization of the local motions and diffusion is possible. The comparison of our results to those reported in the literature provides a consistent scenario for polybutadiene dynamics and puts into a context the different experimental observations. We also discuss the impact of the hopping processes on the observation and interpretation of experimentally accessible magnitudes and the origin of the deviations from Gaussian behavior in this system.     

Electric mass transport of sodium chloride through cation-exchange membrane MK-40 in dilute sodium chloride solutions: A rotating membrane disk study

The polarization properties of an electromembrane system consisting of an MK-40 membrane and a dilute sodium chloride solution are investigated with an experimental apparatus, which includes a rotating membrane disk with a horizontally positioned membrane. For the electrochemical systems of MK-40/0.01 M NaCl and MK-40/0.001 M NaCl, effective ion transport numbers and partial current-voltage curves are determined for sodium and hydrogen ions, and limiting-current densities and the diffusion-layer thickness are calculated as functions of the rotation rate of the membrane disk. The space-charge distribution in the diffusion layer and in the membrane is calculated for various current densities and rotation rates of the membrane. It is shown that when electric-current densities are greater than the limiting value, ion fluxes of the salt increase as a result of a decrease in the effective thickness of the diffusion layer. This decrease is caused by the development of space charge, electroconvection, water dissociation, and the exaltation effect in the region near the membrane. It has been established that in dilute solutions the limiting current is not purely electrodiffusive in nature.     

Pulsed EPR characterization of encapsulated atomic hydrogen in octasilsesquioxane cages

Hydrogen atoms encapsulated in molecular cages are potential candidates for quantum computing applications. They provide the simplest two-spin system where the 1s electron spin, S = 1/2, is hyperfine-coupled to the proton nuclear spin, I = 1/2, with a large isotropic hyperfine coupling (A = 1420.40575 MHz for a free atom). While hydrogen atoms can be trapped in many matrices at cryogenic temperatures, it has been found that they are exceptionally stable in octasilsesquioxane cages even at room temperature [Sasamori et al., Science, 1994, 256, 1691]. Here we present a detailed spin-lattice and spin-spin relaxation study of atomic hydrogen encapsulated in Si(8)O(12)(OSiMe(2)H)(8) using X-band pulsed EPR spectroscopy. The spin-lattice relaxation times T(1) range between 1.2 s at 20 K and 41.8 μs at room temperature. The temperature dependence of the relaxation rate shows that for T < 60 K the spin-lattice relaxation is best described by a Raman process with a Debye temperature of θ(D) = 135 K, whereas for T > 100 K a thermally activated process with activation energy E(a) = 753 K (523 cm(-1)) prevails. The phase memory time T(M) = 13.9 μs remains practically constant between 200 and 300 K and is determined by nuclear spin diffusion. At lower temperatures T(M) decreases by an order of magnitude and exhibits two minima at T = 140 K and T = 60 K. The temperature dependence of T(M) between 20 and 200 K is attributed to dynamic processes that average inequivalent hyperfine couplings, e.g. rotation of the methyl groups of the cage organic substituents. The hyperfine couplings of the encapsulated proton and the cage (29)Si nuclei are obtained through numerical simulations of field-swept FID-detected EPR spectra and HYSCORE experiments, respectively. The results are discussed in terms of existing phenomenological models based on the spherical harmonic oscillator and compared to those of endohedral fullerenes.     

An extremely stable host-guest complex that functions as a fluorescence probe for calcium ions

Herein, we report a crown ether based molecular cage that forms extremely stable supramolecular complexes with dimethyldiazapyrenium (DMDAP) ions in CD(3)CN through the collaboration of multiple weak C-HO hydrogen bonds. The very strong binding affinity in this host-guest system allows the molecular cage to bleach the fluorescence signal of DMDAP substantially in equimolar solutions at concentrations as low as 1 x 10(-5) M. Remarkably, a 1x10(-5) M equimolar solution of the molecular cage and DMDAP is highly selective toward Ca(2+) ions-relative to other biologically important Li(+), Na(+), K(+), and Mg(2+) ions-and causes a substantial increase in the fluorescence intensity of the solution. As a result, this molecular cage/DMDAP complex behaves as a supramolecular fluorescence probe for the detection of Ca(2+) ions in solution.     

Separation performance of foils from Pd—In(6%)—Ru(0.5%), Pd—Ru(6%), and Pd—Ru(10%) alloys and influence of CO<Subscript>2</Subscript>, CH<Subscript>4</Subscript>, and water vapor on the H<Subscript>2</Subscript> flow rate through the test membranes

The H₂ flow rate through the 30-μm thick foil from Pd—Ru(6%) and Pd—Ru(10%) alloys at 673 and 773 K was found to be controlled by the diffusion of H atoms in the foil bulk. The interrelation between hydrogen permeability through the Pd—In(6%)—Ru(0.5%), Pd—Ru(10%), Pd—Ru(6%), and Pd—Ag(23%) membranes and the permeability pre-exponential factors in the Sieverts equation in the 573—773 K temperature interval indicated that the hydrogen permeability depended on the structural characteristics of palladium alloys. The influence of the CO₂, CH₄, and water vapor impurities on the H₂ flow rate through the studied membranes depended on the driving force nature (the sweep gas or transmembrane pressure) used for the development of the partial hydrogen pressure difference across the membrane. The negative influence of CH₄ and CO₂ was observed only when using a transmembrane pressure and at the impurity content of 20% or more. This effect increased with increasing temperature in the 573—773 K range, with the influence of CO₂ being more pronounced due to its reaction with hydrogen leading to the formation of CO. The influence of water vapor was studied at its 11—23% content in hydrogen and at 573 and 773 K of temperature. The negative influence of water vapor was found to subside as its content in the hydrogen mixture decreased and the temperature increased. It was shown that water vapor can be used as a sweep gas and at T = 773 K its influence on the H₂ flow rate through the membrane was almost the same as that of N₂.