Chemisorption and surface reactivity of nitric oxide on clean and sodium-dosed Ag(110)

The chemisorption of NO on clean and Na-dosed Ag(110) has been studied by LEED, Auger spectroscopy, and thermal desorption. On the clean surface, non-dissociative adsorption into the α-state occurs at 300 K with an initial sticking probability of ～0.1, and the surface is saturated at a coverage of about $\text{1}\text{25}$. Desorption occurs without decomposition, and is characterised by an enthalpy of E_d ～104 kJ mol^?1 — comparable with that for NO desorption from transition metals. Surface defects do not seem to play a significant role in the chemistry of NO on clean Ag, and the presence of surface Na inhibits the adsorption of αNO. However, in the presence of both surface and subsurface Na, both the strength and the extent of NO adsorption are markedly increased and a new state (β₁NO) with E_d ～121 kJ mol^?1 appears. Adsorption into this state occurs with destruction of the Ag(110)-(1 × 2)Na ordered phase. Desorption of β₁NO occurs with significant decomposition, N₂ and N₂O are observed as geseous products, and the system's behaviour towards NO resembles that of a transition metal. Incorporation of subsurface oxygen in addition to subsurface Na increases the desorption enthalpy (β₂NO), maximum coverage, and surface reactivity of NO still further: only about half the adsorbed layer desorbs without decomposition. The bonding of NO to Ag is discussed, and comparisons are made with the properties of α and βNO on Pt(110).     

Adsorption and surface structural chemistry of Na and Na + O2 on Ag(110)

The adsorption of Na and the coadsorption of Na and O₂ on Ag(110) have been studied by LEED, thermal desorption, and Auger spectroscopy. For Na coverages in the regime 0 < θ_Na < 2 the Na desorption spectra show a single peak (β) corresponding to a desorption energy of ～195 kJ mol^?1, and at θ_Na ～ 2 a (1 × 2) LEED pattern appears. At still higher coverages (2 < θ_Na < 5), a (1 × 3) surface phase is formed, and a new peak (α) appears in the desorption spectra; this is identified with Na desorption from an essentially Na surface. The desorption energy of αNa (～174 kJ mol^?1) indicates that Na adatoms beyond the first chemisorbed layer are significantly influenced by the presence of the Ag substrate. The initial sticking probability of O₂ on Na-dosed Ag(110) is enormously enhanced over the clean surface value, being of the order of unity, and O₂ chemisorption ultimately leads to a (4 × 1) surface structure. The presence either subsurface Na alone, or of both Na and O below the surface, causes substantial changes in surface behaviour. In the former case, submonolayer doses of Na lead to the appearance of a (1 × 2) structure; and in the latter case, Na + O₂ coadsorption results in a c(4 × 2) structure. Auger spectroscopy indicates that the Ag(110)-c(4 × 2)$\text{Na}\text{O}$ phase forms with a constant stoichiometry which is independent of the initial Na dose. The Na:O ratio in this adlayer is believed to be of the order of unity. The structures of the various ordered phases, the nature of the AgNa bonding, and the interatomic spacing between the alkali adatoms on Ag(110) are discussed.     

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.     

Oxygen chemisorption and the carbon monoxide-oxygen interaction on Ru(101)

The adsorption of oxygen and the interaction of carbon monoxide with oxygen on Ru(101) have been studied by LEED, Auger spectroscopy and thermal desorption. Oxygen chemisorbs at 300 K via a precursor state and with an initial sticking probability of ~0.004, the enthalpy of adsorption being ~300 kJ mol^?1. As coverage increases a well ordered ¦11,30¦ phase is formed which at higher coverages undergoes compression along [010] to form a ¦21,50¦ structure, and the surface eventually saturates at 0 ~ $\text{8}\text{9}$. Incorporation of oxygen into the subsurface region of the crystal leads to drastic changes in the surface chemistry of CO. A new high; temperature peak (γ CO, E_d ~ 800 kJ mol^?1) appears in the desorption spectra, in addition to the α and β CO peaks which are characteristic of the clean surface. Coadsorption experiments using ¹⁸O₂ indicate that γ CO is not dissociatively adsorbed, and this species is also shown to be in competition with β CO for a common adsorption site. The unusual temperature dependence of the LEED intensities of the ¦11,30¦-O phase and the nature of α, β, and β CO are discussed. Oxygen does not displace adsorbed CO at 300 K and the converse is also true, neither do any Eley-Rideal or Langmuir-Hinshelwood reactions occur under these conditions. Such processes do occur at higher temperatures, and in particular the reaction CO(g) + O(a) → CO₂(g) appears to occur with much greater collisional efficiency than on Ru(001). The oxidation of CO has been examined under steady state conditions, and the reaction was found to proceed with an apparent activation energy of 39 kJ mol^?. This result rules out the commonly accepted explanation that CO desorption is rate determining, and is compared with the findings of other authors.     

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.     

Chemical shifts in auger electron spectra from silicon in silicon nitride

The chemisorption of nitric oxide on (110) nickel has been investigated by Auger electron spectroscopy, LEED and thermal desorption. The NO adsorbed irreversibly at 300 K and a faint (2 × 3) structure was observed. At 500 K this pattern intensified, the nitrogen Auger signal increased and the oxygen signal decreased. This is interpreted as the dissociation of NO which had been bound via nitrogen to the surface. By measuring the rate of the decomposition as a function of temperature the dissociation energy is calculated at 125 kJ mol^?1. At ～860 K nitrogen desorbs. The rate of this desorption has been measured by AES and by quantitative thermal desorption. It is shown that the desorption of N₂ is first order and that the binding energy is 213 kJ mol^?1. The small increase in desorption temperature with increasing coverage is interpreted as due to an attractive interaction between adsorbed molecules of ～14 kJ mol^?1 for a monolayer. The (2 × 3) LEED pattern which persists from 500–800 K is shown to be associated with nitrogen only. The same pattern is obtained on a carbon contaminated crystal from which oxygen has desorbed as CO and CO₂. The (2 × 3) pattern has spots split along the (0.1) direction as $\text{(m,}\text{n}\text{3}\text{)}$ and $\text{(}\text{m}\text{2, n}\text{)}$. This is interpreted as domains of (2 × 3) structures separated by boundaries which give phase differences of $\text{2π}\text{3}$ and π. The split spots coalesce as the nitrogen starts to desorb. A (2 × 1) pattern due to adsorbed oxygen was then observed to 1100 K when the oxygen dissolved in the crystal leaving the nickel (110) pattern.     

Cyanide chemistry of rubidium-dosed silver and the use of cyanogen as a titrant for surface alkali

The presence of adsorbed rubidium induces dissociation of cyanogen during chemisorption and leads to a mixed adiayer containing two kinds of cyanide surface species. One of these is weakly bound in an undissociated state and desorbs as (CN)₂ (E_d ? 100 k J mole^?1). A second species is the result of dissociation to CN_adsand appears to be closely associated with the Rb adatoms. This species desorbs exclusively as RbCN (E_d ~ 165 kJ mole^?1) with a kinetic order of between zero and unity depending on the surface coverage. This behaviour, together with the electron impact properties of the Rb + CN overlayer suggest that nucleation and island growth of RbCN occurs above a certain critical coverage. This model can account for the way in which the initially large ESD cross-section for CN loss (~3.5 × 10^?18 cm²) rapidly decreases towards zero with decreasing coverage. It is demonstrated that the special properties of the Ag-(CN)₂-Rb system permit (CN)₂ to be used as a specific titrant for surface alkali, and the technique is used to obtain a value for the activation energy (30 kJ mole^?1) for surface → bulk diffusion of Rb in Ag, as well as the above cross-section to ESD.     

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.     

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(101&#x0304;1).     

Absolute coverage and isostemc heat of adsorption of deuterium on Pt(111) studied by nuclear microanalysis

The absolute coverage (θ) of deuterium adsorbed on Pt(111) in the ranges 180< T<440 K and 5 × 10^?6 < P < 5 × 10^?2 Pa D₂ has been determined by nuclear microanalysis using the D(³He, p)⁴He reaction. From these data, the isosteric heat of adsorption (E_a) has been determined to be 67 ± 7 kJ mol^?1 at θ ? 0.3. This heat of adsorption yields values of the pre-exponential for desorption (10^?5 to 10^?2 cm² atom^?1 s^?1) that lie much closer to the normal range for a second order process than those determined from previous isosteric heat measurements. The E_a versus θ relationship indicates that the adsorbed D atoms are mobile and that there is a repulsive interaction of 6–8 kJ mol^?1 at nearest neighbour distances. At 300 K the coverage decreases to ? 0.05 monolayer (? 8 × 10¹³ D atoms cm^?2) as P→ 0, apparently invalidating a recent model of site exchange in the adsorbed layer.     

Molecular beam reactive scattering of Br2 from Pd(111) using an electrochemical effusive source

A computer-controlled modulated molecular beam source is used to investigate the kinetics of the surface reactions which occur when bromine is reactively scattered by Pd(111). The reaction products are atomic bromine and molecular bromine: the latter species arises from an adatom recombination process and gives rise to a product vector modulated at twice the frequency of the incident beam (2ω.) By making suitable measurements of the temperature dependence of the product vector phase shifts at ω and 2ω, the four kinetic parameters which characterise the first-order and second-order rate processes are obtained. These are: A₁ = 2.5×10⁹ s^?1, E₁ = 177 kJ mol^?1, A₂ = 3.6×10^?10 m² s^?1, E₂ = 131 kJ mol^?1. The significance of these values is discussed in terms of the properties of the transition state to desorption.     

Formic acid desorption from graphitized Ni(110)

The adsorption/desorption behavior of formic acid from a monolayer of graphite carbon on Ni(110) was studied using AES, LEED and flash desorption spectroscopy. Formic acid adsorbed at 165 K did not form multilayers of adsorbate. Instead, due to strong hydrogen-bonding interactions the formic acid formed a two-dimensional condensed phase on the surface and exhibited zero-order desorption kinetics initially for a 30-fold change in initial coverage. The zero-order desorption rate constant was k_d = 10¹⁸ exp[?68.2 kJ mol^?1/RT]s^?1, suggesting a desorption transition state with nearly full translational and rotational freedom on the surface. The desorption kinetics and the coverage limit were consistent with the formation of a surface polymer-monomer equilibrium.     

Thermochemistry of azide salts and the azide ion using direct minimisation equations to obtain the lattice energy of the univalent azide salts

The opportunity to test a new equation for the computation of the lattice energy and at the same time examine a disparity in the literature data for the enthalpy of formation of the azide ion, $\text{ΔH}{}^{\mathrm{\theta }}{}_{\mathrm{?}}\text{(}\text{N}{}_3{}^{\mathrm{?}}\text{) (}\text{g}\text{)}$ was the motivation for this study. The results confirm our earlier calculation and show the new equation to be reliable. Thermodynamic data produced in the study take values: $\text{ΔH}{}^{\mathrm{\theta }}{}_{\mathrm{?}}\text{(}\text{N}{}_3{}^{\mathrm{?}}\text{)(}\text{g}\text{) = 144}\text{kJ mor}{}^{\mathrm{?1}}$ΔH^θ_hyd(N₃^?) = ?315 KJ mol^?1 or ΔH^θ_hyd(N₃^?) = ?295 KJ mol^?1U_POT(NaN₃) = 732 kJ mol^?1U_POT(KN₃) = 659 kJ mol^?1U_POT(RbN₃) = 637 kJ mol^?1U_POT(CsN₃) = 612 kJ mol^?1U_POT(TIN₃) = 689 kJ mol^?1. The lattice energies of azides whose enthalpies of formation are documented have been calculated as well as the enthalpy of formation of the azide radical.     

Carbon monoxide and carbon dioxide interaction with tantalum

The adsorption of carbon monoxide and carbon dioxide on tantalum and the dissolution of these gases in the adsorbent at T ? 300 K have been studied. The flash-filament method (FFM) in a monopole mass-spectrometer and a field emission microscopy was used in the same apparatus. Carbon monoxide and carbon dioxide dissociate on the tantalum surface, carbon monoxide being desorbed in both cases during the flash. The desorption curves of CO reveal three different binding states: two of them (α and $\text{}\text{?}$gb₁) for the adsorbed particles whereas the high temperature desorption state relates to the adsorbate dissolved in the metal, For the $\text{}\text{?}$gb₁ state of CO the activation energy, the pre-exponential factor and the kinetic order in the kinetic equation of desorption have been estimated. They turned out to be E = 110 kcal/mol, C = 3 × 10¹²sec^?1, and ν = 1. The activation energy of diffusion for CO in tantalum and the energy of outgassing for the metal were found to be 9.4 and 49 kcal/mole, respectively.     

A molecular beam study on the interaction of NO with a Pt(111) surface

NO adsorbs on Pt(111) with a (temperature independent) initial sticking coefficient S₀=0.88. The fraction of molecules not being chemisorbed is directly inelastically scattered back due to failure of translational energy accommodation. The nonlinear variation of s with coverage can well be described by a precursor-state model, the precursor state being formed by NO molecules translationally and rotationally accommodated in a physisorbed second layer. Dissociation is essentially restricted to defect sites and is negligible on perfect (111) planes. These defect sites (present in small concentration) are first populated and are also sampled by the modulated beam technique yielding an activation energy for desorption E_d = 33.1 kcal/mole and preexponential factor v_d = 10^15.5s^?1. Isothermal desorption measurements yielded E_d and v_d as a function of coverage: E_d rapidly drops from its initial value (at defect sites) to about 27 kcal/mole — which value is considered as representing the adsorption energy on a perfect (111) plane — and then decreases continuously due to effective repulsive interactions. Simultaneously v_d is decreasing to about 10¹² s^?1 at θ = 0.25 which marks the equilibrium coverage to be reached at 300 K. If the surface is precovered with oxygen atoms the NO sticking coefficient is reduced to 0.6, and the desorption parameters are lowered to E_d = 17.1 kcal/mole and v_d= 10^12.6s^?1 (at zero NO coverage).     

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.     

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.     

The growth and chemisorptive propertles of Ag and Au monolayers on platinum single crystal surfaces: An AES,TDS and LEED study

The growth and chemisorptive properties of monolayer films of Ag and Au deposited on both the Pt(111) and the stepped Pt(553) surfaces were studied using Auger electron spectroscopy (AES), thermal desorption spectroscopy (TDS), and low energy electron diffraction (LEED). AES studies indicate that the growth of Au on Pt(111) and Pt(553) and Ag on Pt(111) proceeds via a Stranski-Krastanov mechanism, whereas the growth of Ag on the Pt(553) surface follows a Volmer-Weber mechanism. Au dissolves into the Pt crystal bulk at temperatures > 800 K, whereas Ag desorbs at temperatures > 900 K. TDS studies of Ag-covered Pt surfaces indicate that the AgPt bond (283 kJ mol^?1) is ～25 kJ mol^?1 stronger than the AgAg bond (254 kJ mol^?1). On the Pt(553) surface the Au atoms are uniformly distributed between terrace and step sites, but Ag preferentially segregates to the terraces. The decrease in CO adsorption on the Pt crystal surfaces is in direct proportion to the Ag or Au coverage. No CO adsorption could be detected for Ag or Au coverages above one monolayer at 300 K and 10^?8 Torr. The heat of adsorption of CO on Pt is unaltered by the presence of Ag or Au.     

Adsorption and reaction of nitric oxide and oxygen on Rh(111)

Adsorption of NO and O₂ on Rh(111) has been studied by TPD and XPS. Both gases adsorb molecularly at 120 K. At low coverages (θ_NO < 0.3) NO dissociates completely upon heating to form N₂ and O₂ which have peak desorption temperatures at 710 and 1310 K., respectively. At higher NO coverages NO desorbs at 455 K and a new N₂ state obeying first order kinetics appears at 470 K. At saturation, 55% of the adsorbed NO decomposes. Preadsorbed oxygen inhibits NO decomposition and produces new N₂ and NO desorption states, both at 400 K. The saturation coverage of NO on Rh(111) is approximately 0.67 of the surface atom density. Oxygen on Rh(111) has two strongly bound states with peak temperatures of 840 and 1125 K with a saturation coverage ratio of 1:2. Desorption parameters for the 1125 peak vary strongly with coverage and, assuming second-order kinetics, yield an activation energy of $\text{85 ± 5}\text{kcal}\text{mol}$ and a pre-exponential factor of 2.0 cm² s^?1 in the limit of zero coverage. A molecular state desorbing at 150 K and the 840 K state fill concurrently. The saturation coverage of atomic oxygen on Rh(111) is approximately 0.83 times the surface atom density. The behavior of NO on Rh and Pt low index planes is compared.     

Density functional study of the reaction of O2 with a single site on the zigzag edge of graphene

The reaction between molecular oxygen and an isolated zigzag graphene edge has been studied using density functional theory at the B3LYP/6-31G(d) level of theory. The initial reaction forms a peroxide, ΔH = −135 kJ mol⁻¹. If the graphene edge is pre-oxidised, the dangling peroxy atom can (E_a = 91 kJ mol⁻¹) migrate across contiguous ketone groups until finding another vacant site and stabilizing as a ketone. However, if no further vacant sites are available, the peroxy oxygen has a number of other possibilities open to it, including desorption of an oxygen atom (E_a = 140 kJ mol⁻¹), migration via the basal plane to form a lactone (E_a = 147 kJ mol⁻¹), and direct interaction with an adjacent oxide to form the lactone or a carbonate (E_a = 146 kJ mol⁻¹). The combination of thermal energy and the heat released in the initial formation of the peroxy adduct is likely to be sufficient to overcome these secondary barriers at modest temperatures.Transfer of the dangling peroxy O to the basal plane produces an epoxide that is mobile on the basal surface (E_a = 40–80 kJ mol⁻¹) but that is transferred back to the edge upon coming into proximity of either a vacant edge site or ketone. The instability of the edge epoxide structure implies that it cannot play a significant role in carbon gasification through promoting the reactivity of ketones, contrary to earlier suggestions.The desorption of an oxygen atom creates a very active species capable of reacting with basal or edge sites as well as with oxygen complexes. The reaction of ketone + O has been reported to yield a five-membered ring + CO₂, leading to an overall stoichiometry which is consistent with the observed oxyreactivity of carbon surface oxides identified in isotopic labelling studies in which one O atom is gasified and the other forms a new surface oxide.