A laboratory study of heterogeneous reactions relevant to the atmospheric boundary layer

The present work deals with two subjects. The interaction of NO2 and HONO with different types of soot are examined in the first part whereas in the second part an experimental set-up is presented which has been built in order to measure the kinetics of the degradation of organic compounds by OH radicals. Both soot particles as well as NO2 are mainly produced by fossil fuel and biomass burning. The two species are therefore ubiquitous in the atmospheric boundary layer where they may react with each other. It has been shown that one possible product of this heterogeneous interaction is nitrous acid (HONO). HONO is an important trace gas in atmospheric chemistry because it is easily photolysed resulting in OH radical and NO. Thus, the photolysis of HONO significantly enhances photooxidation processes early in the morning. In the present study two different types of decane soot have been produced. It has been shown that the air/fuel ratio of the diffusion flame is a key parameter influencing the reactivity of soot towards NO2. Whereas soot from a rich flame ("grey" decane soot) leads to HONO with yields up to 100% upon interaction with NO2, only small amounts of HONO, but significant amounts of NO are formed in the presence of soot originating from a lean flame ("black" decane soot). A reaction mechanism has been developed showing that NO2 is initially converted to HONO by a redox reaction. HONO produced in this way is subsequently either quantitatively desorbed into the gas phase on "grey" decane soot or it decomposes to a large extent in a disproportionation reaction on "black" decane soot. The products of disproportionation are NO, which is instantaneously desorbed into the gas phase and NO2, which undergoes secondary reactions. In addition to the HONO producing pathway there is a reaction channel that leads to adsorption of NO2 for both types of soot which is irreversible on the time scale of our standard experiments. Saturation effects that are occurring on the time scale of our experiments are primarily caused by saturation of adsorption sites and not by the depletion of the reducing agent. It seems that the fraction of NO2 that is irreversibly adsorbed is blocking part of the surface sites where NO2 is initially adsorbed. Uptake coefficients γ take initial values of up to 0.1 for both types of soot. However, with increasing uptake of NO2 γ is decreasing. After a NO2 consumption of approximately 8×1013 molecule cm-2, which corresponds to 13% of a formal monolayer, γ drops to values of 3×10-7 for "grey" decane soot and 6×10-7 for "black" decane soot, respectively. Furthermore, our results show that the rate of initial uptake is the rate limiting step of the NO2/soot interaction mechanism. Experiments where "black" decane soot has been exposed to a flow of HONO revealed that it readily decomposes into NO and NO2. For HONO concentrations above 3.3×1011 molecule cm-3 a total product yield of 50%, whereof 40% NO and 10% NO2, has been observed. The initial uptake coefficient ( γ0) for HONO on "black" decane soot did not show clear saturation effects but varied randomly in the concentration range from 1.2×1012 to 5.9×1012 molecule cm-3. The average value measured at these concentrations was equal to 0.027. The strong interaction of HONO with "black" decane soot shows that soot is not only a potential source, but also a potential sink of HONO. On the other hand, no significant uptake could be observed when "grey" decane soot was exposed to HONO. This is consistent with the observation that NO2 is converted to HONO at yields of up to 100%. Acetylene soot is an additional type of soot that has been examined. The results for the initial uptake coefficients were basically the same as for "grey" and "black" decane soot, that is maximum values of γ0 of 0.1 for NO2 uptake decreasing with increasing concentrations of NO2. This similarity holds only for the first few seconds of interaction because acetylene soot saturates much faster than "grey" and "black" decane soot with continuous exposure. The acetylene samples are generally almost completely saturated after only three minutes of exposure to NO2. Soxhlet extractions of "grey" decane soot which have been performed using tetrahydrofuran as a solvent also produced HONO upon interaction with NO2. This shows that the active reactants are not part of the graphitic soot backbone but are extractable, rather polar compounds of the organic fraction of soot. This assumption is supported by the observation that the corresponding benzene extraction is not reactive in relation to NO2 uptake and HONO formation. In the second part of the present work an experimental set-up is described which has been built in order to measure the rate constants of the reaction of organic compounds with the OH radical in the gas phase using a relative rate technique at atmospheric pressure. The system may be called a "mini smog chamber" as the reaction cell has a volume of only 480 cm3. The system was validated by measuring the relative rate constants of the reactant pair cyclohexane/toluene. These measurements have been performed for temperatures ranging from 300 to 360 K and led to results which are in excellent agreement with literature data. However, the experimental set-up also had some important limitations. Biphenyl which has a boiling point of 529 K was the compound with the lowest volatility that could be examined in our reaction cell. Compounds with lower vapor pressures or compounds with polar groups adsorbed to a large extent onto the glass walls of the reaction cell even at temperatures of up to 373 K. Additional problems occurred in the closed ion source of the mass spectrometer leading to non linear and/or unstable MS signals. These phenomena were most probably caused by secondary ion-molecule reactions in the closed ion source.

Heterogeneous kinetics of some atmospherically relevant reactions

A low pressure reactor (Knudsen cell) coupled to molecular beam modulated mass spectrometry was used to study the heterogeneous kinetics of the following three systems: (1) NO2 on amorphous carbon, (2) H2O vapor on ice and (3) gaseous HCl on ice. The first system was investigated at ambient temperature while the two last ones were investigated at temperatures typical of the stratosphere, that is roughly between 160 and 220K. The solid phase samples correspond to model surfaces whose physicochemical properties come very close to the ones of atmospheric particulates. Firstly, we studied the interaction of gaseous NO2 with three different commercial samples of amorphous carbon having widely differing physicochemical properties. Using in situ laser-induced fluorescence, the only major product was unambiguously determined to be NO with the oxidation product of carbon apparently remaining on the surface. Probing the gas phase with mass spectrometry (MS), both pulsed valve dosing and steady state experiments were performed and revealed a complex reaction mechanism for both the uptake as well as product formation. The initial uptake coefficient γo for NO2 was (6.4±2.0)·10-2 and proved to be identical within experimental uncertainty for all three types of amorphous carbon. The initial NO2 uptake rate was independent of the mass of the carbon sample and scaled with its external geometrical surface. Applying a simple chemical kinetic model to both pulsed dosing and steady state experiments resulted in an effective surface for uptake on amorphous carbon ranging between a factor of 2.8 to 8.4 larger than the geometrical surface area, but inversely proportional to the measured BET surface area of the three types of amorphous carbon. This means that the amorphous carbon with the highest BET surface (FW2) had the lowest external surface for NO2 adsorption. The chemical kinetic model included competing processes between Langmuir-type adsorption and inhibition controlling the adsorption kinetics of NO2 and revealed that the NO generation rate differed greatly between the three carbon samples examined. All samples showed saturation effects of differing degree that were partially reversible through prolonged pumping at 10-4 Torr and/or heating. Virgin amorphous carbon samples did not take up H2O vapor at 20 mTorr, and no HONO and/or HNO3 was detected in simultaneous NO2/H2O exposure experiments. CO and CO2 were detected when a sample previously exposed to NO2 was heated by an incandescent lamp. Moreover, upon heating such a sample, a MS signal m/e 62 originating from NO3 and/or N2O5 was detected. In addition to the experiments conducted on the three commercial carbon samples, we carried out uptake experiments of NO2 on acetylene soot. Originating from the flame of an acetylene burner, this soot was freshly deposited on glass dishes before each experiment. The initial uptake coefficient γo for NO2 was measured to be (3.0±1.1)·10-2 is smaller by a factor of two compared to γo observed in the uptake on commercial samples whose mass was a factor of 10 higher. In addition to NO, a net formation of HONO (m/e 47) was observed. This HONO formation is strongly dependent on the instantaneous water desorption from the sample as well as on the NO2 partial pressure in the reactor. On the other hand, it is not enhanced by an external water flow which did not show any interaction with the carbon sample. Upon heating the sample using an incandescent lamp, significant amounts of water desorbed, suggesting that the water vapor had condensed into the micropores of the soot during combustion. No quantitative results are presented yet. However, as no correlation between HONO formation and NO partial pressure has been observed so far, we suggest a reaction mechanism that only involves NO2 and H2O but no NO: 2 NO2 (g) + H2O HONO + HNO3 In a second study, the kinetics of condensation and evaporation of water on ice was determined in the temperature range of 170 to 220K. The rate of evaporation Fev corresponds to the evaporation of 70±10 monolayers of H2O per second at 200K. The condensation rate constant kc has a negative activation energy of -3.l±1.5kcal/mol which is significantly larger than the one recently measured by Haynes et al. We report the first real time kinetic measurements of water condensation on ice at stratospherically relevant temperatures. At temperatures above 160K, pulsed dosing experiments show a dose dependence of the condensation rate coefficient. For example, the condensation rate coefficient increases by a factor of five with a 1000 fold increase of the H2O dose from 1·1015 to 1·1018 molecules per pulse at 180K. This pressure dependence of the condensation rate constant may be explained by an autocatalytic mechanism involving the competition of two condensation channels. These two channels feed two different surface species, one of which leads to autocatalytic condensation. This mechanism gives insight into the manner in which a gas phase molecule is stepwise incorporated into tetrahedrally coordinated bulk ice. In a third and ongoing study, the uptake kinetics of HCl on ice has been investigated by pulsed valve experiments in the temperature range of 180 to 210K and are discussed as a function of the state of the surface. In fact, some of the pulsed valve experiments present a relaxation to a steady state level. It is shown that this level originates from the evaporation of a liquid solution corresponding to a temperature specific HCl concentration. The threshold of the injected dose leading to this solution layer is estimated to be 8·1014 molecules. This threshold corresponding to a fraction of a monolayer may be explained by the formation of small domains along grain boundaries or other lattice imperfections. Within detection limit, no difference in keff has been observed for pulses on the solution or on a previously exposed sample without formation of the solution. In the case of pulses forming a solution layer, a fraction of 20±20% of the injected molecules remains permanently adsorbed on the surface. In the temperature range from 210 to 180K, the pulsed valve experiments yield values of keff roughly between 5 and 25s-1 and an activation energy of -1.6±0.7kcal/mol which are consistent with the values observed by Flueckiger in steady state experiments using the 15mm escape aperture (kuni varying from 12 to 23s-1 and an activation energy of -1.9±0.25 kcal/mol).

EPFL1996

The heterogeneous interaction of trace gases on mineral dust and soot

Federico Karagulian

The present thesis work deals with the investigation of the heterogeneous reactions involving nitrate radical (NO3), dinitrogen pentoxide (N2O5) and ozone (O3) on surrogates of atmospheric mineral dust particles characteristic of the troposphere. An additional investigation of heterogeneous reaction of NO3 on flame soot was carried out. The goal is to characterize the kinetics (the uptake coefficient γ) as well as the reaction products. The obtained results are intended to provide reliable data for numerical modelling studies. The experiments were performed in a very low pressure flow reactor (Knudsen cell reactor), coupled to mass spectrometry (MS) and optical probing (Resonance Enhanced Multiphoton Ionization (REMPI)). The used mineral dust powder samples were: Kaolinite, CaCO3, natural limestone, Saharan Dust and Arizona Test Dust. Two different types of soot were produced: soot originating from a rich decane flame at a high fuel/oxygen ratio ("grey" soot) and soot generated from a lean flame at a low fuel/oxygen ratio ("black" soot). Uptake experiments of NO3 on mineral dust were carried out under continuous molecular flow conditions (steady state) at 298 ± 2 K using the thermal decomposition of N2O5 as a NO3 source. In situ laser detection (REMPI) was employed in addition to beam-sampling electron-impact mass spectrometry in order to specifically detect NO2 and NO in the presence of N2O5, NO3 and HNO3. We found a steady state uptake coefficient γss ranging from (3.4 ± 1.6) × 10-2 for natural limestone to 0.12 ± 0.08 for Saharan Dust with γss decreasing as [NO3] increased. NO3 adsorbed on mineral dust led to uptake of NO2 in an Eley-Rideal mechanism where usually no uptake is observed in the absence of NO3. The disappearance of NO3 was in part accompanied by the formation of N2O5 and HNO3 in the presence of NO2. NO3 uptake performed on small amounts of Kaolinite and CaCO3 led to formation of some N2O5 according to NO3(ads) + NO2(g) –> N2O5(ads) –> N2O5(g). Slow formation of gas phase HNO3 on Kaolinite, CaCO3, Arizona Test Dust and natural limestone has also been observed and is clearly related to the presence of adsorbed water involved in the heterogeneous hydrolysis of N2O5(ads). Uptake of N2O5 on mineral dust samples led to γss values ranging from (3.5 ± 1.1) × 10-2 for CaCO3 to 0.20 ± 0.05 for Saharan Dust with γss decreasing as [N2O5]0 increased. We have observed delayed production of HNO3 upon uptake of N2O5 for every investigated sample owing to hydrolysis of N2O5 with surface-adsorbed H2O. At high and low [N2O5] Arizona Test Dust and Kaolinite turned out to be the samples to produce the largest amount of gas phase HNO3 with respect to N2O5 taken up. In contrast, the yield of HNO3 for Saharan Dust and CaCO3 is lower. On CaCO3 the disappearance of N2O5 was also accompanied by the formation of CO2. For CaCO3 sample masses ranging from 0.33 to 2.0 g, the yield of CO2 was approximately 42 – 50% with respect to the total number of N2O5 molecules taken up. The reaction of N2O5 with mineral dust and the subsequent production of gas phase HNO3 leads to a decrease in [NOx] which may have a significant effect on global ozone decrease. The rate of uptake of ozone on various mineral dust substrates was very similar for all the examined substrates. Both initial and steady state uptake coefficients γ0 and γss were found to be similar for all examined substrates. Uptake experiments on cut marble samples have shown that γ0 and γss based on the geometric and total internal (BET) surface area may be over and underestimated between a factor of 50 to 100, respectively. Based on these considerations we proposed initial and steady state uptake coefficients of the order of 10-4 and 10-5, respectively. For all uptake experiments on mineral dust surrogates, the disappearance of O3 was accompanied by formation of O2. The different mineral dust surrogates may be more accurately distinguished by their time-dependent relative O2 yield rather than the magnitude of γ. The heterogeneous reaction of O3 on mineral dust has been found to be non-catalytic and of limited importance in the atmosphere. Uptake experiments of NO3 on decane flame soot led to a large steady state uptake coefficient γss of 0.2 ± 0.02 for grey and black soot with γss decreasing as [NO3] increased. Adsorbed NO3 led to an uptake of NO2 admitted from the hot NO3 source. On large quantities of grey soot we observed production of HONO (nitrous acid) corresponding to almost 100% of NO2 taken up, whereas no HONO was formed on black soot. The disappearance of NO3 was in part accompanied by the formation of N2O5 according to reaction: NO3(ads) + NO2(ads) –> N2O5(ads) –> N2O5(g) probably due to the presence of adsorbed NO3 on the substrate. Subsequently, hydrolysis of N2O5(ads) with adsorbed H2O led to production of gas phase HNO3. For both grey and black soot we observed production of NO which did not depend of the amount of soot and [NO3]. Decomposition of NO3 and HONO on the soot substrates has been proposed to be responsible of gas phase NO formation.

EPFL2006

Study of N2O decomposition over Fe-ZSM-5 with transient methods

Petra Prechtl

Nitrous oxide is the third most important gas contributing to global warming and its concentration in the atmosphere is still on the rise. Nitric acid production represents the largest source of N2O in the chemical industry, with a total annual emission of about 400 kt N2O. An efficient way to reduce the N2O is the catalytic decomposition into N2 and O2. ZSM-5 zeolites containing iron are known to be effective in this reaction involving Fe(II)-extraframework species as active sites. But the nature of these sites and the reaction network is still under debate. Often the N2O is in the exhaust together with other gases like NOx, COx, oxygen, and water vapor, which may influence the catalyst efficiency towards N2O decomposition. The effect of these gases on the reaction mechanism is still not understood yet. The aim of this work is to study the decomposition mechanism of N2O over isomorphously substituted Fe-ZSM-5 (0.02-0.55% Fe) using transient response methods. Kinetic studies under steady-state conditions give overall information about the reaction, whereas transient experiments lead to information on the individual steps and the possibility to suggest a reaction model. Transient response methods are applied in vacuum using a Temporal Analysis of Products (TAP) setup and at ambient pressure using a Micromeritics AutoChem 2910 analyzer. The influence of different gases such as NO, H2O and NO2 on the decomposition of N2O over Fe-ZSM-5 is investigated to gain insight into their effect on this reaction. The TAP multifunctional reactor system is used to perform transient pulse experiments for micro-kinetic analysis of complex heterogeneous catalytic reactions. This setup allows to dose precisely reactants and to monitor product formation with submillisecond time resolution implying the absence of external mass or heat transfer. A reproducible low hydroxylation level of the catalyst can be attained in vacuum. The results from the transient responses with the Micromeritics analyzer are obtained under conditions more relevant to "operando". The mechanism of N2O decomposition over Fe containing ZSM-5 was studied by transient response methods at ambient pressure with the Micromeritics analyzer and under vacuum with the TAP setup. Both approaches showed that the mechanism strongly depends on the reaction temperature, but in all cases involves atomic oxygen loading from N2O with N2 evolution as the first reaction step. The surface oxygen, (O)Fe, formed from N2O possesses very high reactivity and oxidizes CO to CO2 already at 373 K. A complete saturation of the active sites can be reached by the catalyst exposure to N2O at low temperatures (T < 600 K in vacuum, T < 523 K at ambient pressure). Under these conditions oxygen is stored and does not desorb. On that basis, the concentration of sites active for the surface atomic oxygen loading from N2O is determined by pulse experiments using the TAP setup. The concentration of active sites is found to be the same as in a flow experiment with the Micromeritics analyzer. The mechanism of surface atomic oxygen recombination and desorption as O2 depends on the temperature. At temperatures higher than 773 K, the mechanism probably involves direct (O)Fe recombination. The investigation of the response profiles upon N2O pulses at 803 K evidences the O2 formation is the rate-determining step since the oxygen desorption is found to be slow compared to N2O and N2. Furthermore, a fit of the oxygen desorption curve corresponded to a first order dependence on the oxygen surface coverage. In the range of 523 to 773 K, the O2 formation is facilitated by NO, which is formed on the catalyst surface from N2O. The addition of NO to the gas phase confirmed the accelerating effect of NO on the oxygen desorption. NO and (O)Fe are adsorbed on adjacent, but different sites and are not competing for the same ones. Adsorbed NO accommodates oxygen from N2O forming higher oxidized nitrogen oxide species NO2/NO3 which decompose back to NOads and molecular oxygen. Thus, the recombination of surface oxygen loaded from N2O is accelerated by a NO/NOx redox cycle whereas adsorbed NOx acts as co-catalyst. Adsorbed NO is oxidized by N2O easily as shown also by temperature-programmed desorption (TPD) experiments. Therefore, the interaction of gaseous NO2 with Fe-ZSM-5 at 523 K in vacuum and at ambient pressure is investigated and demonstrates the formation of two different NOx surface species accompanied by the evolution of gaseous NO. These surface species block the sites for oxygen loading from N2O whereas the amount of reversible adsorbed N2O stays constant compared to the standard pre-treated catalyst. The formation of reactive surface oxygen from NO2 could neither be evidenced in TPD nor with CO oxidation experiments. Adsorbed water strongly influences the N2O decomposition inhibiting it completely, at least at temperatures ≤ 673 K. Water pulses at 523 and 593 K result in partial desorption of the loaded atomic surface oxygen as O2, indicating the competition of water for the same adsorption sites. The residual adsorbed oxygen desorbs during TPD experiments at 849 K instead of 715 K for the dry catalyst and it can not oxidize CO to CO2. It means that the active sites are transformed into an inactive form in the presence of water. The oxygen which stays on the catalyst seems to participate in the Fe(II) oxidation to the hydroxylated Fe(III) species. These Fe(III) species are inactive in N2O decomposition and could be activated again by high temperature treatment in He or in vacuum. During TAP experiments only small amounts of water are dosed and the water desorption is facilitated due to vacuum. Therefore, the effect of water could be shown to be reversible at temperatures > 700 K. At 803 K oxygen desorbs significantly faster with increasing water amount suggesting a water assisted O2 desorption. Simultaneously, the catalyst activity decreases to about a half of the initial activity of the dry zeolite. To conclude, from the TAP reactor data obtained under vacuum conditions and the results from the transient flow experiments at ambient pressure it follows that the mechanism of the N2O decomposition over Fe-containing ZSM-5 depends strongly on the reaction temperature and on the presence of NO, H2O and NO2. In general, below 523 K only surface atomic oxygen loading from N2O takes place with simultaneous evolution of N2 in the gas phase. The O2 formation proceeds via direct (O)Fe recombination at temperatures above 773 K. In the range of 523 to 773 K, the recombination of the atomic oxygen involves NOx adsorbed on the catalyst surface.

EPFL2007