The adsorption of chlorine and chloridation of Ag(111)

The adsorption of chlorine on the Ag(111) surface has been studied using LEED, Auger and temperature programmed desorption. Chlorine adsorbs dissociately with an initial sticking probability of ~ 0.4, and a precursor state is implicated in the chemisorption process. The chlorine appears to form a close-packed monolayer with the same packing density as in AgCl(111), and is epitaxially related to the substrate mesh. Chlorine continues to adsorb above a monolayer in coverage, though the sticking probability drops precipitately, being ~ 0.01 after the adsorption of 5 monolayers at 300 K. There is little increase in the chlorine Auger signal above one monolayer coverage at 300 K, but when adsorption is carried out at 240 K the chlorine signal is more than doubled. This is interpreted as being due to the formation of a layer structure of alternate Cl and Ag layers at the lower temperature, while adsorption at 300 K results in dissolution of subsurface Cl into the bulk of the crystal. Upon heating, the low temperature layer structure is destroyed, the chlorine signal diminishes to a limiting value at 450 K equivalent to the value for one adsorbed monolayer — apparently due to the dissolution of the near surface Cl layers into the bulk. However, the chlorine re-emerges at the surface at ~ 600 K, probably due to an exothermic heat of solution of Cl in the silver lattice. Desorption from the multilayers peaks at 670 K and both AgCl and Ag are desorbed coincidently with kinetics identical to those for the sublimation of bulk AgCl (ΔH = 235 kJ mol^?1, ΔS = 90 JK^?1 mol^?1). After the multilayers have desorbed, the final Cl layer desorbs in a higher temperature peak ( ~ 760 K) as AgCl (no silver desorption) which shows complex desorption kinetics indicative of the strong influence of a precursor state in the desorption process.     

Chemisorption of nitrogen on platinum {111}: Reflection-absorption infrared spectroscopy

Reflection-absorption infrared spectroscopy has been combined with thermal desorption and surface coverage measurements to study nitrogen adsorption on a {111}-oriented platinum ribbon under ultrahigh vacuum conditions. Desorption spectra show a single peak (at 180 K) after adsorption at 120 K, giving a coverage-independent activation energy for desorption'of ～40 kJmol^?1. The initial sticking probability at this temperature is 0.15, and the maximum uptake was ～1.1 × 10¹⁴ molecule cm^?2. The adsorbed nitrogen was readily displaced by CO, h₂ and O₂. An infrared absorption band was observed with a peak located at 2238 ± 1 cm^?1, and a halfwidth of 9 cm^?1, with a molecular intensity comparable to that reported for CO on Pt{111}. The results are compared with data for chemisorption on other group VIII metals. An earlier assignment of infrared active nitrogen to B₅ sites on these metals is brought into question by the present results.     

Mechanism of catalytic reduction of NO by H2 or CO on a Pd foil; Role of chemisorbed nitrogen on Pd

The adsorption of NO and its reaction with H₂ over polycrystalline Pd were investigated using flash desorption technique and ultraviolet photoelectron spectroscopy under 10^?5 Pa pressure range of reactants and surface temperatures between 300 and 900 K. NO was adsorbed dissociatively onto the Pd surface above 500 K, and the heat of dissociative adsorption was ca. 126 kJ/mol. Atomic nitrogen was observed to accumulate on the Pd surface during the NO-H₂ reaction, whose desorption rate exhibited second order kinetics and is expressed as follows: V_d = 10^{?9.8 ± 0.3}exp(?67(kJ/mol)/RT) (cm²/atom·s). Hydrogenation of the adsorbed nitrogen proceeded rapidly at 485 K. It was confirmed from these results that formation of N₂ and NH₃ in the NO-H₂ reaction proceeds through this atomically adsorbed nitrogen. Pd-N bond energy and enthalpies of some intermediate states of the NO-H₂ reaction were estimated.     

Chemisorption,surface structural chemistry,and electron impact properties of carbon monoxide on rhodium (110)

The adsorption, desorption, surface structural chemistry, and electron impact properties of CO on Rh(110) have been studied by LEED, Auger spectroscopy, thermal desorption, and surface potential measurements. At 300 K, CO adsorbs into a single chemisorbed state whose desorption energy (E_d) is ~130kJmol^-1. The initial sticking probability is unity, and at saturation coverage a (2 × 1)plgl ordered phase reaches its maximum degree of perfection, thus demonstrating that this CO structure is common to the (110) faces of all the cubic platinum group metals. The saturated adlayer corresponds to θ = 1 and shows a surface potential of Δ? = +0.97 V. Under electron impact, desorption and dissociation of CO occur with about equal probability, the relevant cross sections being ~10^-22 m² in each case. Slow thermal dissociation of CO occurs at high temperature and pressure, leaving a deposit of C and O atoms on the surface. The thermal, electron impact, and Δ? properties of Rh(110)CO resemble those of Ni(110)CO rather closely, and are very different from those of Pt(110)CO. Surface carbon is shown to inhibit CO chemisorption, whereas surface oxygen appears to lead to the formation of a new more tightly bound form of CO with a considerably enhanced desorption energy (E_d ~ 183 kJmol^-1). Similar oxygen-induced high temperature CO states have been reported recently on Co(0001) and Ru(101̄1).     

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.     

Thermodynamic properties of Rb2ZnCl4 associated with three phase transitions

Transitions were observed by heat capacity measurements at 74.6 K, 195.2 K, and 303 K. They are a soft mode transition (ΔH_t = 30 J mol^?1, ΔS_t = 0.42 J K^?1 mol^?1), a first-order commensurate-incommensurate transition (ΔH_t = 6.2 J mol^?1ΔS_t = 0.032 J K^?1 mol^?1), and a second-order incommensurate-normal transition, respectively.     

A single crystal study of the initial stages of silver sulphidation: The chemisorption and reactivity of molecular sulphur (S2) on Ag(111)

Molecular sulphur undergoes rapid dissociative chemisorption on Ag(111) with an essentially constant sticking probability of unity up to the completion of the first layer of S atoms. At this stage a $\text{(√39 R 16.1° × √39}\text{R}\text{?}\text{16.1°)}$ structure is formed in which the S atom arrangement and spacing is similar to that in the (100) plane of γ-Ag₂S (the high temperature form of silver sulphide). Further dosing with S₂ leads to continued rapid uptake of sulphur and the appearance of a (√7 × √7) R 10.9° structure, the Auger, Δφ and thermal desorption data all indicate that fast formation of Ag₂S now occurs. Very well-ordered growth of γ-Ag₂S(111) is now observed, and low-temperature S₂ desorption spectra appear which show that the activation energy for S₂ desorption is ~175 kJ mol^?1 ; this value is in excellent agreement with that observed for the enthalpy of decomposition of bulk Ag₂S (2 Ag₂S(s) → 4 Ag(s) + S₂(g), ΔH = +179 kJmol^?1). All the properties of the Ag(111)-S system imply that the material characterised by the √39 structure (i.e. the first adsorbed layer of S) is very different from bulk Ag₂S. This is discussed and compared with the results of other studies on metal-sulphur systems.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

The methanation activity of W(110)

The methanation activity of W(110) was measured over a range of reactant partial pressures and temperatures (P_H2 = 1–1000 Torr, P_CO = 0.1–10 Torr, T = 475–820 K). Plotting the results in an Arrhenius fashion yielded a lower apparent activation energy (E_a = 56 kJmol^?1) than previously determined for Ni(100) (E_a = 103 kJmol^?1) with an activity surpassing that of Ni at lower temperatures. The H₂ pressure dependence of the methanation activity was found to be much stronger for W(110) than for Ni(100), the surface becoming increasingly inactive at the lowest H₂ pressures investigated. Auger electron spectroscopy revealed the active catalytic surface to be carbidic in nature.     

Adsorption,coadsorption, and reactivity of sodium and nitric oxide on Ag(111)

The adsorption, desorption, and surface structural properties of Na and NO on Ag(111), together with their coadsorption and surface reactivity, have been studied by LEED, Auger spectroscopy, and thermal desorption. On the clean surface, non-dissociative adsorption of NO into the a-state occurs at 300 K with an initial sticking probability of ~0.1, saturation occurring at a coverage of $\text{~}\text{1}\text{20}$. Desorption occurs reversibly without decomposition and is characterised by a desorption energy of E_d ~ 103 kJ mol^?1. In the coverage regime 0 < θ_Na < 1, sodium adsorbs in registry with the Ag surface mesh and the desorption spectra show a single peak corresponding to E_d ~ 228 kJ mol^?1. For multilayer coverages (1 < θ _Na < 5) a new low temperature peak appears in the desorption spectra with E_d ~ 187 kJ mol^?1. This is identified with Na desorption from an essentially Na surface, and the desorption energy indicates that Na atoms beyond the first chemisorbed layer are significantly influenced by the presence of the Ag substrate. The LEED results show that Na multilayers grow as a (√7 × √7) R19.2° overlayer, and are interpreted in a way which is consistent with the above conclusion. Coadsorption of Na and NO leads to the appearance of a more strongly bound and reactive chemisorbed state of NO (β-NO) with E_d ~ 121 kJ mol^?1. β-NO appears to undego surface dissociation to yield adsorbed O and N atoms whose subsequent reactions lead to the formation of N₂, N₂O, and O₂ as gaseous products. The reactive behaviour of the system is complicated by the effects of Na and O diffusion into the bulk of the specimen, but certain invariant features permit us to postulate an overall reaction mechanism, and the results obtained here are compared with other relevant work.     

The adsorption and desorption of oxygen on the Pt(110) surface; A thermal desorption and LEED/AES study

The interaction of oxygen with a Pt(110) crystal surface has been investigated by thermal desorption mass spectroscopy, LEED and AES. Adsorption at room temperature produces a β-state which desorbs at ~800 K. Complete isotopic mixing occurs in desorption from this state and it populates with a sticking probability which varies as (1 ? θ)², both observations consistent with dissociative adsorption. The desorption is second order at low coverage but becomes first order at high coverage. The saturationcoverage is 3.5 × 10¹⁴ mol cm^?2. The spectra have been computer analysed to determine the fraction desorbing by first (β₁) and second (β₂) order kinetics as a function of total fractional coverage θ using this fraction as the only adjustable parameter. The β₁ desorption commences at θ ～ 0.25 and β₁ and β₂ contribute equally to the desorption at saturation. The kinetic parameters for β₁ desorption were calculated from the variation of peak temperature with heating rate as ν₁ = 1.7 × 10⁹ s^?1 and E^≠₁ = 32 kcal mole^?1 whereas two different methods of analysis gave consistent parameters ν₂ = 6.5 × 10^?7 cm² mol^?1 s^?1 and E^≠₂ = 29 and 30 kcal mole^?1 for β₂ desorption. The kinetics of desorptior are discussed in terms of the statistics for occupation of near neighbour sites. While many fea tures of the results are consistent with this picture, it is concluded that simple models considering either completely mobile or immobile adlayers with either strong or zero adatom repulsion are not completely satisfactory. The thermal desorption surface coverage has been correlated with the AES measurements and it has been possible to use the AES data for PtO as an internal standard for calibration of the AES oxygen coverage determination. At low temperature (170 K) oxygen populates an additional molecular α-state. Adsorption into the α- and β-states is competitive for the same sites and pre-saturation of the β-state at 300 K excludes the α-state. This, together with the AES observation that the adsorption is enhanced and faster at 450 than 325 K suggests a low activation energy for adsorption into the β-state.     

Thermal evidences for successive CDW phase transitions in 1T-TaS2

The heat capacity of 1T-TaS₂ has been measured over the temperature range including the successive phase transitions (140 K–370 K) by an adiabatic calorimeter. There are three transitions in the measured temperature range, two first-order transitions (at about 226 K (T₁) and about 353.5 K (T₃)) and one small anomaly at about 283 K (T₂) with a broad peak. The transition enthalpies are as follows; ΔH₁=52±5 cal·mol^-1, ΔH₂=7.5±2 cal· mol^-1 and ΔH₃=122±8cal·mol^-1.     

Adsorption-desorption properties,coadsorption, and surface structural chemistry of chlorine and oxygen on Ag(331)

At 300 K oxygen chemisorbs on Ag(331) with a low sticking probability, and the surface eventually facets to form a (110)?(2 × 1) O structure with ΔΦ = +0.7 eV. This facetting is completely reversible upon O₂ desorption at ~570 K. The electron impact properties of the adlayer, together with the LEED and desorption data, suggest that the transition from the (110) facetted surface to the (331) surface occurs at an oxygen coverage of about two-thirds the saturation value. Chemisorbed oxygen reacts rapidly with gaseous CO at 300 K, the reaction probability per impinging CO molecule being ~0.1. At 300 K chlorine adsorbs via a mobile precursor state and with a sticking probability of unity. The surface saturates to form a (6 × 1) structure with ΔΦ = +1.6 eV. This is interpreted in terms of a buckled close-packed layer of Cl atoms whose interatomic spacing is similar to those for Cl overlayers on Ag(111) and Ag(100). Desorption occurs exclusively as Cl atoms with E_d ~ 213 kJ mol^?1; a comparison of the Auger, ΔΦ, and desorption data suggests that the Cl adlayer undergoes significant depolarisation at high coverages. The interaction of chlorine with the oxygen predosed surface, and the converse oxygen-chlorine reaction are examined.     

Adsorption behavior of H2O on clean and oxygen precovered Ni(s)(111)

Photoelectron spectroscopy (UPS), thermal desorption spectroscopy (TDS), isotope exchange experiments, work function change (δφ) and LEED were used to study the adsorption and dissociation behavior of H₂O on a clean and oxygen precovered stepped Ni(s)[12(111) × (111)] surface. On the clean Ni(111) terraces fractional monolayers of H₂O are adsorbed weakly in a single adsorption state with a desorption peak temperature of 180 K, just above that of the ice multilayer desorption peak (T_m = 155 K). In the angular resolved UPS spectra three H₂O induced emission maxima at 6.2, 8.5 and 12.3 eV below E_F were found for θ ≈ 0.5. Angular and polarization dependent UPS measurements show that the C_2v symmetry of the H₂O gas-phase molecule is not conserved for H₂O(ad) on Ni(s)(111). Although the Δφ suggest a bonding of H₂O to Ni via the negative end of the H₂O dipole, the O atom, no hints for a preferred orientation of the H₂O molecular axes were found in the UPS, neither for the existence of water dimers nor for a long range ordered H₂O bilayer. These results give evidence that the molecular H₂O axis is more or less inclined with respect to the surface normal with an azimuthally random distribution. H₂O adsorption at step sites of the Ni(s)(111) surface leads in TDS to a desorption maximum at T_m = 225 K; the binding energy of H₂O to Ni is enhanced by about 30% compared to H₂O adsorbed on the terraces. Oxygen precoverage causes a significant increase of the H₂O desorption energy from the Ni(111) terraces by about 50%, suggesting a strong interaction between H₂O and O(ad). Work function measurements for H₂O+O demonstrate an increase of the effective H₂O dipole moment which suggests a reorientation of the H₂O dipole in the presence of O(ad), from inclined to a more perpendicular position. Although TDS and Δφ suggest a significant lateral interaction between H₂O+O(ad), no changes in the molecular binding energies in UPS and no “isotope exchange” between ¹⁸O(ad) and H₂¹⁶O(ad) could be observed. Also, dissociation of H₂O could neither be detected on the oxygen precovered Ni(s)(111) nor on the clean terraces.     

On the phase transition in α-NH4HgCl3, a two-dimensional version of ammonium chloride

Heat capacity of α-NH₄HgCl₃ crystal has been measured with an adiabatic calorimeter from 11 to 300 K. A sharply peaked anomaly due to an order-disorder change of the ammonium ions was found at 54.97 ± 0.04 K. The entropy and enthalpy changes were estimated to be ΔS = 5.2 ± 1.0JK^?1 mol^?1 and ΔH = 342 ± 65 J mol^?1. In accordance withthe structural two-dimensionality of α-NH₄HgCl₃ crystal, Onsager's solution of the two-dimensional Ising model was used in calculation of the transition temperature. On the assumption that the octopole-octopole interaction is responsible for the ordering of the ammonium ions in the present crystal and in ammonium chloride, the calculation gives 74.44 K for the transition temperature. Several possibilities were discussed for explaining the remaining discrepancy between the observed and calculated transition temperatures.     

Surface chemistry of the metal-halogen interface: Bromine chemisorption and dibromide formation on palladium (111)

At 300 K and in the coverage regime ($\text{0<θ<}\text{1}\text{3}$) bromine chemisorbs rapidly on Pd(111); the sticking probability and dipole moment per adatom remain constant at 0.8 ± 0.2 and 1.2 D, respectively. This stage is marked by the appearance of a √3 structure: desorption occurs exclusively as atomic Br. At higher coverages, desorption of molecular Br₂ begins (desorption energy ～130 kJ mol^?1) as does the nucleation and growth of PdBr₂ on the surface. This latter stage is signalled by the appearance of a √2 LEED pattern and the observation of PdBr₂ as a desorption product (desorption energy ～37 kJ mol^?1). Some PdBr₂ is also lost by surface decomposition and subsequent evaporation of atomic Br. The data indicate that the transition state to Br adatom desorption is localised and that PdBr₂(a) ? Br(a) interconversion occurs; these surface species do not appear to be in thermodynamic equilibrium during the desorption process.     

The low temperature water formation reaction on Pt(111): A static SIMS and TDS study

The formation of water by the reaction of preadsorbed oxygen with hydrogen on a Pt(111) surface has been characterized, using secondary ion mass spectroscopy, below the desorption temperature of H₂O (180 K). The concentration of chemisorbed water was monitored during the reaction by following the SIMS H₃O⁺ signal. Reaction profiles were measured over a temperature range of 120 to 153 K, and an H₂ pressure range of 10^-9 to 10^-6 Torr. Under all conditions the reaction profiles were characterized by an induction time, a region of rapid reaction, and finally a steady decline in the rate. In the rapid region, an overall activation energy of 2.9 ± 0.3 kcalmol^-1 and a half-order H₂ pressure dependence were observed. At low initial oxygen concentrations the induction time increased and the maximum rate decreased. The reaction was slow in the absence of gas phase hydrogen, even when the surface coverage of hydrogen was relatively high. Water and hydrogen thermal desorption spectra, measured after stopping the reaction by removal of gas phase hydrogen, were complex functions of the H₂ exposure, exhibiting several peaks between 170 and 400 K. However, after an exposure large enough to drive the reaction to completion, only one H₂O peak at 173 K and one H₂ peak at 350 K were observed. The results indicate that only a fraction of the total H(a) on the surface was readily available for reaction during H₂ exposure at T ? 153 K. the remainder either recombined to form H₂ or reacted with O(a) during the thermal desorption ramp. There is good evidence for a surface rearrangement during the induction period. A model is proposed which involves the formation of water clusters that accelerate the rate.     

Adsorption and decomposition of formic acid on the NiO(111)-p(2 × 2) surface: TPD and steady state kinetics studies

The adsorption and decomposition of formic acid on NiO(111)-p(2 × 2) films grown on Ni(111) single crystal surface were studied by temperature-programmed desorption (TPD) spectroscopy. Exposure of formic acid at 163 K resulted in both molecular adsorption and dissociation to formate. The adsorbed formate underwent further dissociation to H₂, CO₂ and CO. H₂ and CO₂ desorbed at the same temperatures of 340, 390 and 520 K, while CO desorbed at 415 and 520 K. The desorption features varied with the formic acid exposure. Two reaction channels were identified for the decomposition of formate under equilibrium with gas-phase formic acid with a pressure of 2.5 × 10⁻⁴Pa, one preferentially producing H₂ and CO₂ with an activation energy of 22 ± 2 kJ mol⁻¹ and the other preferentially producing CO and H₂O with an activation energy of 16 ± 2 kJ mol⁻¹. The order of both reaction paths was 0.5 with respect to the pressure of formic acid.     

Hydrogen-induced low temperature CO displacement from the Pt(111) surface

A new low temperature displacement mechanism for CO on the Pt(111) surface has been observed in the presence of high pressures of hydrogen (0.001 to 0.1 Torr H₂). Temperature-programmed fluorescence yield near-edge spectroscopy (TP FYNES) was used to continuously monitor the CO coverage as a function of temperature both with and without hydrogen. For hydrogen pressures above 0.01 Torr, removal of CO begins at 130 K (E_d = 10.6 kcal/mol) instead of near the desorption temperature of 400 K (E_d = 26 kcal/mol). The large decrease in CO desorption energy appears to be caused by substantial repulsive interactions in the compressed monolayer induced by coadsorbed hydrogen. The new low temperature CO desorption channel appears to be caused by displacement of the compressed CO adlayer by coadsorbed hydrogen. In addition, the desorption activation energy for the main desorption channel of CO near 400 K is lowered by ~ 1 kcal/mol for hydrogen pressures in the 0.001 to 0.1 Torr range. These new results clearly emphasize the importance of in-situ methods capable of performing kinetic experiments at high pressures on well characterized adsorbed monolayers on single crystal surfaces. High coverages of coadsorbed hydrogen resulting from substantial overpressures may substantially modify desorption activation energies and thus coverages and kinetic pathways available even for strongly chemisorbed species. These phenomena may play an important role in surface reactions which occur at high pressure.     

Studies on kinetics and thermodynamics of ion adsorption reactions by applications of short-lived radioactive tracer isotopes

The short-lived radiotracer isotopes were applied to study the kinetics and thermodynamic feasibility of iodide as well as bromide ion adsorption reactions using industrial-grade resin materials. Free energy of activation (ΔG ^?) and energy of activation (E _a) were calculated by using Arrhenius equation, enthalpy of activation (ΔH ^?), and entropy of activation (ΔS ^?) calculated by using the Eyring-Polanyi equation. These parameters were used to predict the thermodynamic feasibility of the two ion adsorption reactions performed by using Dowex SBR LC and Indion-810 resins. It was observed that during iodide ion adsorption reactions, the values of energy of activation (?18.79 kJ mol^?1), enthalpy of activation (?21.37 kJ mol^?1), free energy of activation (58.13 kJ mol^?1), and entropy of activation (?0.26 kJ K^?1 mol^?1) calculated for Indion-810 resins were lower than the respective values of ?4.28 kJ mol^?1, ?6.87 kJ mol^?1, 64.97 kJ mol^?1, and ?0.23 kJ K^?1 mol^?1 calculated for Dowex SBR LC under similar experimental conditions. Identical trends were observed for the two resins during bromide ion adsorption reactions. The low values of different thermodynamic parameters obtained for Indion-810 resins during both the ion adsorption reactions indicate that the reactions are thermodynamically more feasible using Indion-810 resins as compared to Dowex SBR LC resins. It is expected here that the present nondestructive technique can be extended further for different ions in the solution in order to predict the thermodynamic feasibility of different ion adsorption reactions for the range of resins which are widely used for treatment of industrial waste water effluent.