Albert A. Viggiano

How the Shape of an H-Bonded Network Controls Proton-Coupled Water Activation in HONO Formation

Its the Network Numerous reactions of small molecules and ions in the atmosphere take place in the confines of watery aerosols. Relph et al. (p. 308; see the Perspective by Siefermann and Abel) explored the specific influence of a water clusters geometry on the transformation of solvated nitrosonium (NO+) to nitrous acid (HONO). The reaction involves (O)N–O(H) bond formation with one water molecule, concomitant with proton transfer to additional, surrounding water molecules. Vibrational spectroscopy and theoretical simulations suggest that certain arrangements of the surrounding water network are much more effective than others in accommodating this charge transfer, and thus facilitating the reaction. Vibrational spectroscopy uncovers the role of a surrounding water network in the mediating reaction of a solvated ion. Many chemical reactions in atmospheric aerosols and bulk aqueous environments are influenced by the surrounding solvation shell, but the precise molecular interactions underlying such effects have rarely been elucidated. We exploited recent advances in isomer-specific cluster vibrational spectroscopy to explore the fundamental relation between the hydrogen (H)–bonding arrangement of a set of ion-solvating water molecules and the chemical activity of this ensemble. We find that the extent to which the nitrosonium ion (NO+)and water form nitrous acid (HONO) and a hydrated proton cluster in the critical trihydrate depends sensitively on the geometrical arrangement of the water molecules in the network. Theoretical analysis of these data details the role of the water network in promoting charge delocalization.

The February–March 2000 Eruption of Hekla, Iceland from a Satellite Perspective

An 80,000 km 2 stratospheric volcanic cloud formed from the 26 February 2000 eruption of Hekla (63.98° N, 19.70° W). POAM-III profiles showed the cloud was 9-12 km asl. During 3 days this cloud drifted north. Three remote sensing algorithms (TOMS SO 2 , MODIS & TOVS 7.3 μm IR and MODIS 8.6 μm IR) estimated ∼0.2 Tg SO 2 . Sulfate aerosol in the cloud was 0.003-0.008 Tg, from MODIS IR data. MODIS and AVHRR show that cloud particles were ice. The ice mass peaked at ∼1 Tg ∼10 hours after eruption onset. A ∼0.1 Tg mass of ash was detected in the early plume. Repetitive TOVS data showed a decrease of SO 2 in the cloud from 0.2 Tg to below TOVS detection (i.e.<0.01 Tg) in ∼3.5 days. The stratospheric height of the cloud may result from a large release of magmatic water vapor early (1819 UT on 26 February) leading to the ice-rich volcanic cloud. The optical depth of the cloud peaked early on 27 February and faded with time, apparently as ice fell out. A research aircraft encounter with the top of the cloud at 0514 UT on 28 February, 35 hours after eruption onset, provided validation of algorithms. The aircrafts instruments measured ∼0.5-1 ppmv SO 2 and ∼35-70 ppb sulfate aerosol in the cloud, 10-30% lower than concentrations from retrievals a few hours later. Different SO 2 algorithms illuminate environmental variables which affect the quality of results. Overall this is the most robust data set ever analyzed from the first few days of stratospheric residence of a volcanic cloud.

Reactive nitrogen budget during the NASA SONEX Mission

The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the North Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of reactive nitrogen in the upper troposphere (8–12 km altitude). The median measured total reactive nitrogen (NOy) mixing ratio was 425 parts per trillion by volume (pptv). A data set merged to the HNO3 measurement time resolution was used to calculate NOy (NOy sum) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing it to measured NOy (NOy meas.). Comparisons were done for tropospheric air (O3 100 ppbv) with both showing good agreement between NOy sum and NOy meas. (slope >0.9 and r² ≈ 0.9). The total reactive nitrogen budget in the upper troposphere over the North Atlantic appears to be dominated by a mixture of NOx (NO + NO2), HNO3, and PAN. In tropospheric air median values of NOx/NOy were ≈ 0.25, HNO3/NOy ≈ 0.35 and PAN/NOy ≈ 0.17. Particulate NO3− and alkyl nitrates together composed <10% of NOy, while model estimated HNO4 averaged 12%. For the air parcels sampled during SONEX, there does not appear to be a large reservoir of unidentified NOy compounds.

Conversion of Methane to Methanol: Nickel, Palladium, and Platinum (d9) Cations as Catalysts for the Oxidation of Methane by Ozone at Room Temperature

The room-temperature chemical kinetics has been measured for the catalytic activity of Group 10 atomic cations in the oxidation of methane to methanol by ozone. Ni(+) is observed to be the most efficient catalyst. The complete catalytic cycle with Ni(+) is interpreted with a computed potential energy landscape and, in principle, has an infinite turnover number for the oxidation of methane, without poisoning side reactions. The somewhat lower catalytic activity of Pd(+) is reported for the first time and also explored with DFT calculations. Pt(+) is seen to be ineffective as a catalyst because of the observed failure of PtO(+) to convert methane to methanol.

SOx oxidation and volatile aerosol in aircraft exhaust plumes depend on fuel sulfur content

Volatile and nonvolatile aerosols were measured in the wake of a B757 airliner in flight, in concert with measurements of gaseous SO x and CO 2 emissions, while the airplane was burning fuel with a sulfur content of either 72 parts per million by mass (ppmm) or 676 ppmm. The volatile aerosol number density exceeded that of the nonvolatile for both fuels and, while the nonvolatile (soot) component was largely insensitive to the fuel sulfur content, the volatile component depleted the gas-phase sulfur species with a condensed fraction that increased from 6% (low S) to 31% (high S). The large proportion of SO, in the aerosol phase and its nonlinear dependence on fuel sulfur content cannot be explained by known combustion mechanisms and has the potential for significant environmental effects.

Low-energy electron attachment to SF6. I. Kinetic modeling of nondissociative attachment

Low-energy electron-molecule collisions are analyzed by kinetic modeling within the framework of statistical unimolecular rate theory. Nondissociative electron attachment to SF(6) is used to illustrate the approach. An internally consistent representation is provided for attachment cross sections and rate coefficients in relation to detachment lifetimes, and both thermal and specific rate coefficients for detachment. By inspecting experimental data, the contributions of intramolecular vibrational redistribution and vibrationally inelastic collisions can be characterized quantitatively. This allows for a prediction of attachment rate coefficients as a function of electron and gas temperature as well as gas pressure over wide ranges of conditions. The importance of carefully controlling all experimental parameters, including the carrier gas pressure, is illustrated. The kinetic modeling in Part II of this series is extended to dissociative electron attachment to SF(6).

Dissociative attachment reactions of electrons with strong acid molecules

Using the flowing afterglow/Langmuir probe (FALP) technique, we have determined (at variously 300 and 570 K) the dissociative attachment coefficients β for the reactions of electrons with the common acids HNO3 (producing NO−2) and H2SO4 (HSO−4), the superacids FSO3H (FSO−3), CF3SO3H (CF3SO−3), ClSO3H (ClSO−3,Cl−), the acid anhydride (CF3SO2)2O (CF3SO−3), and the halogen halides HBr (Br−) and HI (I−). The anions formed in the reactions are those given in the parentheses. The reactions with HF and HCl were investigated, but did not occur at a measurable rate since they are very endothermic. Dissociative attachment is rapid for the common acids, the superacids, and the anhydride, the measured β being appreciable fractions of the theoretical maximum β for such reactions, βmax. The HI reaction is very fast ( β∼βmax) but the HBr reaction occurs much more slowly because it is significantly endothermic. The data indicate that the extreme acidity of the (Bronsted‐type) superacids has its equivalence in the very ef...

Reactions of mass-selected cluster ions in a thermal bath gas

Technologicaldevelopments of fast-flow tubes that led to major advances in the study of cluster ion reactions are reviewed, including the coupling of high-pressure cluster ion sources to flowing-afterglow and selected-ion flow tube (SIFT) instruments. Several areas of cluster ion chemistry that have been studied recently in our laboratory, using a SIFT instrument with a supersonic expansion ion source, are reviewed. Firstly the thermal destruction of cluster ions is highlighted by a discussion of the competition between electron detachment and thermal dissociationin hydrated electron clusters (H O) . Rates and activationenergies for the n thermal destruction (dissociation plus detachment) of these clusters are discussed. The reactivity of hydrated electron clusters with several neutral electron scavengers is also reviewed. Secondly cluster ion chemistry related to trace neutral detection of atmospheric species using chemical ionization mass spectrometry is discussed. Recent rate measurements needed for ch...

Low-energy electron attachment to SF6. II. Temperature and pressure dependences of dissociative attachment

Low-energy electron-molecule collisions, leading to dissociative attachment through metastable anionic states, are kinetically modeled within the framework of statistical unimolecular rate theory. The reaction e(-)+SF(6)-->SF(5)(-)+F is used as an illustrative example. The modeling is applied to new measurements of branching fractions for SF(5)(-) formation in the bath gas He between 360 and 670 K at 1 and 2 Torr, and between 490 and 620 K over the range of 0.3-9 Torr. The analysis of the data follows the previous kinetic modeling of the nondissociative electron attachment, e(-)+SF(6)-->SF(6)(-), from Part I of this series. Experimental results from the present work and the literature on branching fractions and total cross sections for anion formation as functions of electron energies, bath gas temperatures and pressures, as well as observation times are analyzed. The assumption of a participation of the electronic ground state of SF(6)(-) alone suffices to model the available experimental data. A value of the dissociation energy of SF(6)(-) into SF(5)(-)+F of E(0,dis)=1.61(+/-0.05) eV is determined, which may be compared to the electron affinity of SF(6), EA=1.20(+/-0.05) eV, such as derived in Part III of this series.

Low-energy electron attachment to SF6. III. From thermal detachment to the electron affinity of SF6

The thermal attachment of electrons to SF(6) is measured in a flowing-afterglow Langmuir-probe apparatus monitoring electron concentrations versus axial position in the flow tube. Temperatures between 300 and 670 K and pressures of the bath gas He in the range of 0.3-9 Torr are employed. Monitoring the concentrations of SF(6)(-) and SF(5)(-), the latter of which does not detach electrons under the applied conditions, an onset of thermal detachment and dissociation of SF(6) at temperatures above about 530 K is observed. Analysis of the mechanism allows one to deduce thermal detachment rate coefficients. Thermal dissociation rate coefficients for the reaction SF(6)(-)-->SF(5)(-)+F can only be estimated by unimolecular rate theory based on the results from Part I and II of this series. Under the applied conditions they are found to be smaller than detachment rate coefficients. Combining thermal attachment and detachment rates in a third-law analysis, employing calculated vibrational frequencies of SF(6) and SF(6)(-), leads to the electron affinity (EA) of SF(6)(-). The new value of EA=1.20(+/-0.05) eV is significantly higher than previous recommendations which were based on less direct methods.