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Hydrogen cyanide (HCN) is the primary cyanide species in combustion processes and plays a key role in the formation of NO

Bromoacetaldehyde (BrCH2CHO) is a major stable brominated organic intermediate of the bromine-ethylene addition reaction during the arctic bromine explosion events. Similar to acetaldehyde, which has been recently identified as a source of organic acids in the troposphere, it may be subjected to photo-tautomerization initially forming brominated vinyl compounds. In this study, we investigate the unimolecular reactions of BrCH2CHO under both photolytic and thermal conditions using high-level quantum chemical calculations and Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation analysis. The unimolecular decomposition of BrCH2CHO takes place through 14 dissociation and isomerization channels along a potential energy surface involving eight wells. Under the assumption of singlet ground-state potential energy surface-dominated photodynamics, the primary photodissociation yields of BrCH2CHO are investigated under both collision-free and collision energy transfer conditions. At atmospheric pressure and under tropospheric actinic flux conditions at ground level, depending on the assumed collisional energy transfer parameter, 150 cm-1 < ⟨ΔEdown⟩ < 450 cm-1, 78-33% of BrCH2CHO undergoes direct photodissociation instead of collisional deactivation at an excitation wavelength of 320 nm. This is significantly higher than the 14% reported for acetaldehyde, hence indicating a strong effect of bromine substitution on the product photolysis yield that is related to additional favorable Br and HBr forming dissociation channels. In contrast to the overall photodissociation quantum yield, the relative branching fractions of the photodissociation products are less dependent on the collisional energy transfer parameter. For a representative value of ⟨ΔEdown⟩ = 300 cm-1 and an excitation wavelength of 320 nm, with 27% for C-C bond fission, 11% for C-Br bond fission, 7% for HBr elimination, and only below 2% each for a consecutive O-Br fission reaction and the photo-tautomerization channel yielding brominated vinyl alcohol, the photodissociation is markedly different from the acetaldehyde case. Finally, as brominated halogenated compounds are of interest for flame inhibition purposes, thermal multichannel unimolecular rate constants were calculated for temperatures in the range from 500 to 2000 K. At a temperature of 2000 K and ambient pressure, the two main reaction channels are the C-Br and C-C bond fissions, contributing 35 and 43% to the total reaction flux, respectively.

The reaction kinetics of the isomers of the methylallyl radical with molecular oxygen has been studied in a flow tube reactor at the vacuum ultraviolet (VUV) beamline of the Swiss Light Source storage ring. The radicals were generated by direct photodissociation of bromides or iodides at 213 nm. Experiments were conducted at room temperature and low pressures between 1 and 3 mbar using He as the buffer gas. Oxygen was employed in excess to maintain near pseudo-first-order reaction conditions. Concentration–time profiles of the radical were monitored by photoionisation. For the oxidation of 2-methylallyl (2-MA) and with k(2-MA + O2) = (5.1 ± 1.0) × 1011 cm3 mol−1 s−1, the rate constant was found to be in the high-pressure limit already at 1 mbar. In contrast, 1-methylallyl exists in two isomers, E- and Z-1-methylallyl. We selectively detected the E-conformer as well as a mixture of both isomers and observed almost identical rate constants within the uncertainty of the experiment. A small pressure dependence is observed with the rate constant increasing from k(1-MA + O2) = (3.5 ± 0.7) × 1011 cm3 mol−1 s−1 at 1 mbar to k(1-MA + O2) = (4.6 ± 0.9) × 1011 cm3 mol−1 s−1 at 3 mbar. While for 2-methylallyl + O2 no previous experimental data are available, the rate constants for 1-methylallyl are in agreement with previous work. A comparison is drawn for the trends of the high-pressure limiting rate constants and pressure dependences observed for the O2 recombination of allylic radicals with the corresponding reactions of alkyl radicals.

Self-assembled monolayers (SAMs) of azobenzene (AB) functionalized alkyl thiols on gold diluted with simple alkyl thiols provide a straightforward way to photochromic surfaces with high and tunable photoswitching efficiency. Trans-cis isomerization of the AB molecule changes the physical properties of the surface, including the nonlinear optical (NLO) response. Vibrational sum-frequency generation (VSFG) spectroscopy as a nonlinear type of laser spectroscopy offers surface- and orientation-sensitive insight into the molecular structure of mixed SAMs. In this study, VSFG as well as ultraviolet-visible (UV/Vis) spectroscopy has been employed to investigate the morphology, molecular structure, and NLO response of mixed SAMs with systematically varied surface composition. Methylazobenzene (MeAB) has been used as the molecular switch with the methyl substituent serving as orientational VSFG marker. Both short-chain and long-chain alkyl thiol co-ligands have been used to gain insight into the interplay between SAM structure and sterical constraints that are known to limit the free switching volume. Underlining the dominating role of sterical effects for controlling photochromic properties, a strong inhibition of the photoswitching efficiency and NLO response has been observed for the SAMs with an alkyl thiol co-ligand long enough to spatially extend into the layer of the MeAB chromophore. Overall, with

The NCN radical plays a key role for modelling prompt-NO formation in hydrocarbon flames. Recently, in a combined shock tube and flame modeling study the so far neglected reaction NCN + H2 and the ...

We have developed a 3 μm mid-IR continuous wave OPO-based two-tone frequency modulation laser absorption technique. The optical spectrometer was characterized and deployed for investigating C2H2 concentration dynamics in a particle forming dusty plasma environment.

The reaction kinetics of the isomers of the methylallyl radical with molecular oxygen has been studied in a flow tube reactor at the vacuum ultraviolet (VUV) beamline of the Swiss Light Source storage ring. The radicals were generated by direct photodissociation of bromides or iodides at 213 nm. Experiments were conducted at room temperature and low pressures between 1 and 3 mbar using He as the buffer gas. Oxygen was employed in excess to maintain near pseudo-first-order reaction conditions. Concentration-time profiles of the radical were monitored by photoionisation. For the oxidation of 2-methylallyl (2-MA) and with k(2-MA + O2) = (5.1 ± 1.0) × 1011 cm3 mol-1 s-1, the rate constant was found to be in the high-pressure limit already at 1 mbar. In contrast, 1-methylallyl exists in two isomers, E- and Z-1-methylallyl. We selectively detected the E-conformer as well as a mixture of both isomers and observed almost identical rate constants within the uncertainty of the experiment. A small pressure dependence is observed with the rate constant increasing from k(1-MA + O2) = (3.5 ± 0.7) × 1011 cm3 mol-1 s-1 at 1 mbar to k(1-MA + O2) = (4.6 ± 0.9) × 1011 cm3 mol-1 s-1 at 3 mbar. While for 2-methylallyl + O2 no previous experimental data are available, the rate constants for 1-methylallyl are in agreement with previous work. A comparison is drawn for the trends of the high-pressure limiting rate constants and pressure dependences observed for the O2 recombination of allylic radicals with the corresponding reactions of alkyl radicals.

International audience; The cyanonitrene radical, NCN, has been shown in the last two decades to play a crucial role in the formation of prompt-NO in combustion. This has stimulated a large number of experimental and theoretical studies on fundamental physico-chemical properties of NCN as well as on mechanistic and kinetic aspects of NCN reactions under combustion conditions. In this review, spectroscopic, thermodynamic, and kinetic data of NCN are collected and discussed. Methodic approaches for the detection of NCN in flames and in kinetic experiments are elucidated, and the suitability of cyanogen azide, NCN3, as a precursor for NCN in kinetic experiments is examined. Kinetic and mechanistic aspects of a number of NCN elementary chemical steps are extensively reviewed. Regarding prompt-NO formation, the role of the reaction network initialized by the reaction CH + N2 ⇌ NCN + H is examined by modeling measured flame profiles of NCN, HCN, and NO. In these simulations, the critical role of the product channel-branching of the NCN + H reaction, termed the prompt-NO switch, is confirmed. A particularly sensitive balance is observed between the product channels leading back to CH + N2 or forward to HCN + N. The roles of spin conservation and intersystem crossing processes under flame conditions and in kinetic experiments with NCN3 as NCN precursor are highlighted. A number of critical points and remaining open problems in NCN chemistry and prompt-NO formation are indicated.

Methyl iodide is a toxic halocarbon with diverse industrial and agricultural applications, and it is an important ocean-derived trace gas that contributes to the iodine burden of the atmosphere. Quantitative analysis of CH3I is mostly based on gas chromatography coupled with mass spectrometry or electron capture detection (GC–MS/ECD) as of yet, which often limits the ability to conduct in situ high-frequency monitoring studies. This work presents an alternative detection scheme based on mid-infrared continuous wave cavity ringdown spectroscopy (mid-IR cw-CRDS). CH3I was detected at the RR2(15) rovibrational absorption transition at ṽ = 3090.4289 cm–1; part of the corresponding v4 vibration band has been measured with Doppler-limited resolution for the first time. A line strength of S(T = 295 K) = (545 ± 20) cm/mol, corresponding to a line center absorption cross-section σc(p = 0 bar) = (1.60 ± 0.06) × 105 cm2/mol, and pressure-broadening coefficients γp(Ar) = (0.094 ± 0.002) cm–1/bar and γp(N2) = (0.112 ±...

The Doppler limited non-saturated rotationally resolved infrared spectra of the symmetric and asymmetric CH-stretch bands of CH2Br2 have been measured. A continuous wave cavity ringdown setup with a widely tunable Mid-IR-OPO laser light source yielded a single-shot minimum absorption of 4.9 × 10 −8 cm −1. In contrast to the heavily congested ν1 band, the ν6 band showed partially resolved rotational features that may serve as suitable absorption targets in future environmental detection schemes for CH2Br2. A straightforward, VPT2 (second-order vibrational perturbation theory) assisted quantum-chemical approach for assigning the rotational structure has been tested using different model chemistries. The molecular structures, anharmonic frequencies and the structural changes upon vibrational excitation of CH2Br2 have been investigated. The predicted changes of the anharmonic rotational constants have been used together with available spectroscopic ground state constants to simulate the rovibrational structures of the ν1 and ν6 bands of CH2Br2. A refined analysis of the ν6 band is presented yielding accurate values for the band origin and the rotational constants. A fit of the line positions of 312 prominent transitions of the three isotopologues revealed a low standard error of 0.00056 cm −1, hence within the absolute 0.0009 cm −1 wavelength accuracy of the used spectrometer setup. A combined analysis of the predicted line strengths and positions of the strong Q sub-branches of the ν6 band has been performed to test the ability of the different density functionals for VPT2 prediction of anharmonic molecular constants. The M06/6-311++G(d,p) model chemistry turned out to yield reliable state-dependent rotational constants that are accurate enough to reproduce the overall rotational structure even without fitting.

Six different chiral and achiral alkane dicarboxylic C4-acids, i.e. succinic acid (H2SUC), dl-2-methylsuccinic acid (H2MS), 2,3-dimethylsuccinic acid (H2DMS) and aspartic acid (d-, l- and dl-H2ASP), were used to obtain Ce(iv)-MOFs via microwave assisted reactions. In water-based syntheses, MOFs with three different topologies, denoted as UiO-66 (fcu), CAU-41 (bcu) and CAU-44 (bct), were obtained within 30 min under mild reaction conditions. The MOFs were fully characterized and their structures were refined from PXRD data. The chirality of the incorporated linker molecules was confirmed by circular dichroism spectroscopy. The optical activities were also investigated by second-harmonic generation (SHG) measurements. The use of H2MS, H2DMS and H2ASP leads to the formation of a UiO-66-type structure, and a hydrated form of the common hexanuclear cluster, i.e. [Ce6(μ3-O)4(μ3-OH)4(H2O)6]12+ was observed. Rietveld refinement of the PXRD data showed an ordered arrangement of the d- and l-enantiomers in Ce-UiO-66-dl-ASP. By employing H2SUC as the linker, the other two title compounds are obtained. CAU-41, [Ce6(μ3-O)4(μ3-OH)4(SUC)4(OH)4(H2O)4], exhibits the well-known eight-fold connectivity of the hexanuclear cluster, whereas in CAU-44, [Ce6(μ3-O)4(μ3-OH)4(SUC)4(NO3)2(OH)2(H2O)2], the connection of the clusters is also achieved by nitrate ions resulting in a framework with bct topology. ispartof: DALTON TRANSACTIONS vol:48 issue:23 pages:8433-8441 ispartof: location:England status: published

Six different chiral and achiral alkane dicarboxylic C

Knowledge about the high temperature kinetics of HNO, which represents a key species in NOx flame chemistry, is scarce. Using the very sensitive absorption based frequency modulation (FM) spectroscopy, HNO has been measured behind shock waves for the first time. The UV photolysis of glyoxal/NO mixtures at λ = 193 nm served as an HNO source with stable HNO concentration plateaus generated via the fast initial formation of HCO radicals followed by the reaction HCO + NO → CO + HNO. FM line shapes of three selected transitions of the A ˜ 1 A ′ ′ ( 100 ) − X ˜ 1 A ′ (000) band of HNO have been recorded and their pressure broadening coefficient has been determined. By analyzing HNO and HCO concentration-time profiles measured under very similar reaction conditions it was possible to confirm an HCO/HNO formation mechanism and to determine the HNO absorption cross section. The expression log [ σ c ( HNO , p = 0 bar , 295 K T 1800 K ) / cm 2 mol − 1 ] = 5.86 – 1.62 × 10 − 3 × T / K + 2.74 × 10 − 7 × T 2 / K 2 with an uncertainty of ± 40% in σc is recommended for the RR3(4) rotational line at ν ˜ = 16173.86 cm − 1 (618.2816 nm). The capability to perform quantitative HNO measurements behind shock wave make possible direct rate constant studies of bimolecular HNO reactions in future experiments.

Pre-service teachers for secondary schools do not often perceive the academic content knowledge from their university teaching programme to be relevant for their future teaching profession. Hence, they lack motivation to learn those contents, which may have effect on their achievement. The aim of the study was, to develop a specific learning programme to enhance the perceived relevance of academic content knowledge. The learning programme was applied as an obligatory course for pre-service chemistry teachers with three 90-minute sessions and aimed to connect the academic content knowledge with the school-related content knowledge by structured content knowledge. The intervention study with a control group and a pre-post-test design to evaluated this approach involved N = 55 pre-service chemistry teachers (nintervention group = 23, ncontrol group = 32) and analysed the effects of this intervention on the perceived relevance of academic content knowledge. The results showed that pre-service chemistry teachers evaluate the academic course more likely to be relevant for their future profession already before the intervention took place. Nevertheless, compared to the control, the intervention showed a positive effect on the perceived relevance of academic content knowledge and the overall assessment of this academic course. Examining the explanations for the pre-service teachers’ perceived relevance revealed that they reasoned mainly from a school associated perspective, though their explanations remained at a rather low level.

Unravelling elementary steps, reaction pathways, and kinetic mechanisms is key to understanding the behaviour of many real-world chemical systems that span from the troposphere or even interstellar media to engines and process reactors. Recent work in chemical kinetics provides detailed information on the reactive changes occurring in chemical systems, often on the atomic or molecular scale. The optimisation of practical processes, for instance in combustion, catalysis, battery technology, polymerisation, and nanoparticle production, can profit from a sound knowledge of the underlying fundamental chemical kinetics. Reaction mechanisms can combine information gained from theory and experiments to enable the predictive simulation and optimisation of the crucial process variables and influences on the system's behaviour that may be exploited for both monitoring and control. Chemical kinetics, as one of the pillars of Physical Chemistry, thus contributes importantly to understanding and describing natural environments and technical processes and is becoming increasingly relevant for interactions in and with the real world.

The rate constant of the comparably slow bimolecular NCN radical reaction NCN + O-2 has been measured for the first time under combustion relevant conditions using the shock tube method. The thermal decomposition of cyanogen azide (NCN3) served as a clean high-temperature source of NCN radicals. NCN concentration-time profiles have been detected by narrow-bandwidth laser absorption at 30383.11 cm(-1). The experiments behind incident shock waves have been performed with up to 17% O-2 in the reaction gas mixture. At such high O-2 mole fractions, it was necessary to take O-2 relaxation into account that caused a gradual decrease of the temperature during the experiment. Moreover, following fast decomposition of NCN3 and collision-induced intersystem crossing of the initially formed singlet NCN to its triplet ground state, an unexpected and slow additional formation of triplet NCN has been observed on a 100-s timescale. This delayed NCN formation was attributed to a fast recombination of (NCN)-N-1 with O-2 forming a (NCNOO)-N-3 adduct acting as a reservoir species for NCN. Rate constant data for the reaction NCN + O-2 have been measured at temperatures between 1674 and 2308 K. They are best represented by the Arrhenius expression . No pressure dependence has been observed at pressures between 216 and 706 mbar.

The coordination network consisting of trivalent bismuth ions and pyromellitic acid (H4Pyr), [Bi(HPyr)], was successfully applied as a host matrix for in situ incorporation of trivalent rare earth (RE3+) ions Sm3+, Eu3+, Tb3+ and Dy3+. High-throughput methods for hydrothermal synthesis allowed us to prepare and study the phase purity and crystallinity of the sample series, accelerating and facilitating the comparison between the synthesis parameters. Infrared absorption spectroscopy, elemental and thermogravimetric analysis, scanning electron microscopy and energy-dispersive X-ray spectroscopy, as well as powder X-ray diffraction and refinement of the unit cell parameters of the compounds, indicated that doping did not affect the structure, crystallinity, morphology and thermal stability of the matrix. The study of the spectroscopic luminescence properties of the nondoped and doped [Bi(HPyr)] allowed investigation of the sensitization processes of dopant RE3+ ions. The characteristic spectroscopic properties of the Eu3+ ion were used to study the incorporation site and coordination environment of the dopant by calculation of the experimental intensity parameters Ωλ (λ: 2 and 4) and intrinsic quantum yield of the Eu3+ single-doped [Bi(HPyr)]. Straightforward emission color tuning by changing the relative concentrations of the dopant ions is possible and has been studied for the four systems double-doped with Tb3+:Eu3+, Tb3+:Sm3+, Dy3+:Eu3+ and Dy3+:Sm3+ ions. The Dy-containing systems show different shades of white emission and a wide range of correlated color temperatures (CCT), ranging from 2500 to 7500 K, hence being a promising candidate for the development of single-phase white light emitting devices.

A detailed mechanism for the thermal decomposition and oxidation of the flame intermediate glyoxal (OCHCHO) has been assembled from available theoretical and experimental literature data. The modeling capabilities of this extensive mechanism have been tested by simulating experimental HCO profiles measured at intermediate and high temperatures in previous glyoxal photolysis and pyrolysis studies. Additionally, new experiments on glyoxal pyrolysis and oxidation have been performed with glyoxal and glyoxal/oxygen mixtures in Ar behind shock waves at temperatures of 1285-1760 K at two different total density ranges. HCO concentration-time profiles have been detected by frequency modulation spectroscopy at a wavelength of λ = 614.752 nm. The temperature range of available direct rate constant data of the high-temperature key reaction HCO + O2 → CO + HO2 has been extended up to 1705 K and confirms a temperature dependence consistent with a dominating direct abstraction channel. Taking into account available literature data obtained at lower temperatures, the following rate constant expression is recommended over the temperature range 295 K < T < 1705 K: k1/(cm(3) mol(-1) s(-1)) = 6.92 × 10(6) × T(1.90) × exp(+5.73 kJ/mol/RT). At intermediate temperatures, the reaction OCHCHO + HO2 becomes more important. A detailed reanalysis of previous experimental data as well as more recent theoretical predictions favor the formation of a recombination product in contrast to the formerly assumed dominating and fast OH-forming channel. Modeling results of the present study support the formation of HOCH(OO)CHO and provide a 2 orders of magnitude lower rate constant estimate for the OH channel. Hence, low-temperature generation of chain carriers has to be attributed to secondary reactions of HOCH(OO)CHO.

Bimolecular reactions of the NCN radical play a key role in modeling prompt-NO formation in hydrocarbon flames. The rate constant of the so-far neglected reaction NCN + H2 has been experimentally determined behind shock waves under pseudo-first order conditions with H2 as the excess component. NCN3 thermal decomposition has been used as a quantitative high temperature source of NCN radicals, which have been sensitively detected by difference UV laser absorption spectroscopy at [small nu, Greek, tilde] = 30383.11 cm(-1). The experiments were performed at two different total densities of ρ≈ 4.1 × 10(-6) mol cm(-3) and ρ≈ 7.4 × 10(-6) mol cm(-3) (corresponding to pressures between p = 324 mbar and p = 1665 mbar) and revealed a pressure independent reaction. In the temperature range 1057 KT2475 K, the overall rate constant can be represented by the Arrhenius expression k/(cm(3) mol(-1) s(-1)) = 4.1 × 10(13) exp(-101 kJ mol(-1)/RT) (Δlog k = ±0.11). The pressure independent reaction as well as the measured activation energy is consistent with a dominating H abstracting reaction channel yielding the products HNCN + H. The reaction NCN + H2 has been implemented together with a set of reactions for subsequent HNCN and HNC chemistry into the detailed GDFkin3.0_NCN mechanism for NOx flame modeling. Two fuel-rich low-pressure CH4/O2/N2-flames served as examples to quantify the impact of the additional chemical pathways. Although the overall NCN consumption by H2 remains small, significant differences have been observed for NO yields with the updated mechanism. A detailed flux analysis revealed that HNC, mainly arising from HCN/HNC isomerization, plays a decisive role and enhances NO formation through a new HNC → HNCO → NH2→ NH → NO pathway.

Analyzing the dynamics of biofilm formation helps to deepen our understanding of surface colonization in natural environments. While methods for screening biofilm formation in the laboratory are well established, studies in marine environments have so far been based upon destructive analysis of individual samples and provide only discontinuous snapshots of biofilm establishment. In order to explore the development of biofilm over time and under various biotic and abiotic conditions, we applied a recently developed optical biofilm sensor to quasicontinuously analyze marine biofilm dynamics in situ . Using this technique in combination with microscope-assisted imaging, we investigated biofilm formation from its beginning to mature multispecies biofilms. In contrast to laboratory studies on biofilm formation, a smooth transition from initial attachment to colony formation and exponential growth could not be observed in the marine environment. Instead, initial attachment was followed by an adaptation phase of low growth and homogeneously distributed solitary bacterial cells. Moreover, we observed a diurnal variation of biofilm signal intensity, suggesting a transient state of biofilm formation of bacteria. Overall, the biofilm formation dynamics could be modeled by three consecutive development stages attributed to initial bacterial attachment, bacterial growth, and attachment and growth of unicellular eukaryotic microorganisms. Additional experiments showed that the presence of seaweed considerably shortened the adaptation phase in comparison with that on control surfaces but yielded similar growth rates. The outlined examples highlight the advantages of a quasicontinuous in situ detection that enabled, for the first time, the exploration of the initial attachment phase and the diurnal variation during biofilm formation in natural ecosystems.

A single-tone mid-infrared frequency modulation (MIR-FM) spectrometer consisting of a cw-OPO-based laser system, a 500 MHz LiTaO 3 electro-optical modulator (EOM), and a high-bandwidth GaAs mid-infrared detector has been developed. In order to assess the instrument’s sensitivity and time resolution, FM spectra of selected CH 4 transitions around 3070 cm −1 were measured and the reaction Cl + CH 4 following the 193 nm excimer laser photolysis of oxalyl chloride was investigated by recording concentration-time profiles of HCl at 2925.90 cm −1 in a low-pressure slow-flow reactor. Furthermore, OH radicals were generated by UV photolysis of H 2O 2 and its transients were recorded at 3447.27 cm −1. The minimal detectable absorption of the spectrometer was determined to be A min=4⋅10−4 (Δ f BW=1 MHz, ν~=3447 cm −1) by using the Allan approach. Mainly due to thermal noise contributions of the easy-to-saturate photodetector, the detection limit is about a factor of 4 above the shot-noise limit. To the best of our knowledge, this work reports the first implementation of a single-tone MIR-FM spectrometer based on an external EOM modulation scheme and its use for the detection of transient molecular species.

The very thin sea surface nanolayer on top of the sea surface microlayer, sometimes just one monomolecular layer thick, forms the interface between ocean and atmosphere. Due to the small dimension and tiny amount of substance, knowledge about the development of the layer in the course of the year is scarce. In this work, the sea surface nanolayer at Boknis Eck Time Series Station (BE), southwestern Baltic Sea, has been investigated over a period of three and a half years. Surface water samples were taken monthly by screen sampling and were analyzed in terms of organic content and composition by sum frequency generation spectroscopy, which is specifically sensitive to interfacial layers. A yearly periodicity has been observed with a pronounced abundance of sea surface nanolayer material (such as carbohydrate-rich material) during the summer months. On the basis of our results we conclude that the abundance of organic material in the nanolayer at Boknis Eck is not directly related to phytoplankton abundance alone. We speculate that indeed sloppy feeding of zooplankton together with photochemical and/or microbial processing of organic precursor compounds is responsible for the pronounced seasonality.

The Doppler limited non-saturated rotationally resolved infrared spectra of the symmetric and asymmetric CH-stretch bands of CH

Cavity ringdown spectroscopy (CRDS) in the linear absorption regime is a well-established method for sensitive trace gas detection, but only a few studies have addressed quantitative measurements in the presence of a saturated sample. In fact, saturation is usually avoided in order to escape from the required complex modeling of the saturation process that depends on the characteristics of the absorbing species, its interaction with the surrounding gas as well as on the temporal and spectral characteristics of the cavity excitation. Conversely, the novel saturated-absorption cavity ringdown spectroscopy approach (SCAR/Sat-CRDS) takes advantage of sample saturation in order to allow one to extract both the gas absorption and the empty cavity loss rates from a single ringdown event. Using a new continuous-wave infrared CRD spectrometer equipped with a tunable narrow-bandwidth high-power OPO laser system and a 18 bit digitizer, the transient dynamics of absorption saturation and the working limits of the Sat-CRDS approach in terms of its ability to extract reliable trace gas concentrations have been experimentally studied in this work. Using a strong methane transition as a test case, the excitation power P0 and saturation power PS have been systematically varied to explore a wide range of saturation regimes. At pressures 5 μbarp2 mbar, the saturation intensity revealed a nearly linear pressure dependence showing that non-collisional processes contribute to the overall relaxation. A ratio of P0/PS ≈ 15 turned out to be optimal with working limits of 5P0/PS300. Moreover, the ratio of the absorption and empty cavity loss rates, γg/γc, has been varied to test the dynamic range of the method. At γgγc, a pronounced coupling between the two parameters has been observed. Finally, a standard error analysis was performed revealing that the Sat-CRDS approach holds its advantages over conventional CRDS implementations in particular when the attainable ultimate detection sensitivity is limited by uncertainties in the empty cavity ringdown constant.

The role of the global surface ocean as a source and sink for atmospheric carbon dioxide and the flux strengths between the ocean and the atmosphere can be quantified by measuring the fugacity of CO2 (ƒCO2) as well as the dissolved inorganic carbon (DIC) concentration and its isotopic composition in surface seawater. In this work, the potential of continuous wave cavity ringdown spectroscopy (cw-CRDS) for autonomous underway measurements of ƒCO2 and the stable carbon isotope ratio of DIC [δ13C(DIC)] is explored. For the first time, by using a conventional air-sea equilibrator setup, both quantities were continuously and simultaneously recorded during a field deployment on two research cruises following meridional transects across the Atlantic Ocean (Bremerhaven, Germany–Punta Arenas, Chile). Data are compared against reference measurements by an established underway CO2 monitoring system and isotope ratio mass spectrometric analysis of individual water samples. Agreement within ΔƒCO2 = 0.35 μatm for atmospheric and ΔƒCO2 = 2.5 μatm and Δδ13C(DIC) =0.33‰ for seawater measurements have been achieved. Whereas “calibration-free” ƒCO2 monitoring is feasible, the measurement of accurate isotope ratios relies on running reference standards on a daily basis. Overall, the installed CRDS/equilibrator system was shown to be capable of reliable online monitoring of ƒCO2, equilibrium δ13C(CO2), δ13C(DIC), and pO2 aboard moving research vessels, thus making possible corresponding measurements with high spatial and temporal resolution.

The thermal decomposition of cyanogen azide (NCN3) and the subsequent collision-induced intersystem crossing (CIISC) process of cyanonitrene (NCN) have been investigated by monitoring excited electronic state 1NCN and ground state 3NCN radicals. NCN was generated by the pyrolysis of NCN3 behind shock waves and by the photolysis of NCN3 at room temperature. Falloff rate constants of the thermal unimolecular decomposition of NCN3 in argon have been extracted from 1NCN concentration–time profiles in the temperature range 617 K

The rate constant of the reaction NCN + O has been directly measured for the first time. According to the revised Fenimore mechanism, which is initiated by the NCN forming reaction CH + N(2)→ NCN + H, this reaction plays a key role for prompt NO(x) formation in flames. NCN radicals and O atoms have been quantitatively generated by the pyrolysis of NCN(3) and N(2)O, respectively. NCN concentration-time profiles have been monitored behind shock waves using narrow-bandwidth laser absorption at a wavelength of λ = 329.1302 nm. Whereas no pressure dependence was discernible at pressures between 709 mbarp1861 mbar, a barely significant temperature dependence corresponding to an activation energy of 5.8 ± 6.0 kJ mol(-1) was found. Overall, at temperatures of 1826 KT2783 K, the rate constant can be expressed as k(NCN + O) = 9.6 × 10(13)× exp(-5.8 kJ mol(-1)/RT) cm(3) mol(-1) s(-1) (±40%). As a requirement for accurate high temperature rate constant measurements, a consistent NCN background mechanism has been derived from pyrolysis experiments of pure NCN(3)/Ar gas mixtures, beforehand. Presumably, the bimolecular secondary reaction NCN + NCN yields CN radicals hence triggering a chain reaction cycle that efficiently removes NCN. A temperature independent value of k(NCN + NCN) = (3.7 ± 1.5) × 10(12) cm(3) mol(-1) s(-1) has been determined from measurements at pressures ranging from 143 mbar to 1884 mbar and temperatures ranging from 966 K to 1900 K. At higher temperatures, the unimolecular decomposition of NCN, NCN + M → C + N(2) + M, prevails. Measurements at temperatures of 2012 KT3248 K and at total pressures of 703 mbarp2204 mbar reveal a unimolecular decomposition close to its low pressure limit. The corresponding rate constants can be expressed as k(NCN + M) = 8.9 × 10(14)× exp(-260 kJ mol(-1)/RT) cm(3) mol(-1) s(-1)(±20%).

The high-temperature rate constants of the reactions NCN + NO and NCN + NO(2) have been directly measured behind shock waves under pseudo-first-order conditions. NCN has been generated by the pyrolysis of cyanogen azide (NCN(3)) and quantitatively detected by sensitive difference amplification laser absorption spectroscopy at a wavelength of 329.1302 nm. The NCN(3) decomposition initially yields electronically excited (1)NCN radicals, which are subsequently transformed to the triplet ground state by collision-induced intersystem crossing (CIISC). CIISC efficiencies were found to increase in the order of Ar < NO(2) < NO as the collision gases. The rate constants of the NCN + NO/NO(2) reactions can be expressed as k(NCN+NO)/(cm(3) mol(-1)s(-1)) = 1.9 × 10(12) exp[-26.3 (kJ/mol)/RT] (±7%,ΔE(a) = ± 1.6 kJ/mol, 764 K < T < 1944 K) and k(NCN+NO(2))/(cm(3) mol(-1)s(-1)) = 4.7 × 10(12) exp[-38.0(kJ/mol)/RT] (±19%,ΔE(a) = ± 3.8 kJ/mol, 704 K < T < 1659 K). In striking contrast to reported low-temperature measurements, which are dominated by recombination processes, both reaction rates show a positive temperature dependence and are independent of the total density (1.7 × 10(-6) mol/cm(3) < ρ < 7.6 × 10(-6) mol/cm(3)). For both reactions, the minima of the total rate constants occur at temperatures below 700 K, showing that, at combustion-relevant temperatures, the overall reactions are dominated by direct or indirect abstraction pathways according to NCN + NO → CN + N(2)O and NCN + NO(2) → NCNO + NO.

The recent unraveling of the rather complex acid-base equilibrium of nitroxyl (HNO) has stimulated a renewed interest in the significance of HNO for biology and pharmacy. HNO plays an important role in enzymatic mechanisms and is discussed as a potential therapeutic agent against heart failure. A cumbersome property for studying HNO reactions, its fast dimerization leading to the rapid formation of N(2)O, is surprisingly far from being well understood. It prevents isolation and limits intermediate concentrations of nitroxyl in solution. In this study, a new mechanism for the HNO dimerization reaction in aqueous solution has been theoretically derived on the basis of DFT calculations. Detailed analysis of the initial reaction step suggests a reversal of the cis-trans isomer preference in solution compared to the corresponding gas phase reaction. In contrast to a gas phase derived model based on intramolecular rearrangement steps, an acid-base equilibrium model is in agreement with previous experimental findings and, moreover, explains the fundamental differences between the well studied gas phase reaction and the solvent reaction in terms of polarity, cis-trans isomerizations, and acidities of the intermediates. In the case of cis-hyponitrous acid, the calculated pK(a) values of the acid-base equilibria were found to be significantly different from the corresponding experimental value of the stable trans isomer. Under physiological conditions, N(2)O formation is dominated by the decomposition of the unstable monoanion cis-N(2)O(2)H(-) rather than that of the commonly stated cis-HONNOH.

The potential of a continuous wave cavity ringdown spectrometer for monitoring the isotope ratio 13CO2/12CO2 and the partial pressure pCO2 of CO2 dissolved in water was thoroughly analyzed by quantitative measurements. Running calibration gas standards under typical operation conditions, a relative accuracy of D(d13C[CO2]) = ±0.1‰ with 120 min averaging time has been demonstrated. Absolute uncertainties were determined to be D(d13C[CO2]) = ±0.2‰ and D(xCO2) = ±0.5 ppmv. No principle problems were encountered when using the instrument in combination with a water-air equilibration setup. By contrast, when performing measurements of CO2 in gas matrices with a composition different from that of ambient air, pressure broadening linewidth effects induced significant errors in both d13C(CO2) and xCO2 values. These effects, which compromise the accessible accuracy in environmental studies, can be quantitatively taken into account by using a spectroscopically based correction procedure. Relying on linewidth analysis, the instrument was shown to be capable of continuous and simultaneous measurement of d13C(CO2), pCO2, as well as water content and O2 supersaturation, and thus holds the potential for online monitoring of these quantities aboard research vessels.

Vibrational Sum Frequency Generation (VSFG) is a surface sensitive nonlinear laser spectroscopic technique, which has been widely used in physics and physical chemistry to investigate interface processes and heterogeneous chemistry. As the technique advances from basic to applied research, we have assessed its suitability for investigations of natural air-water interfaces, which are typically covered with an organic nanolayer. Vibrational spectra of natural sea surface nanolayer samples are presented. Strong signals attributable to the alkyl chains of lipids and indications for more or less soluble carbohydrate material have been found. Furthermore, the use of VSFG spectroscopy as a time-resolved detection tool for monitoring surface layer formation and its reactive decay is demonstrated. Ozone-induced film oxidation served as an example. We successfully applied VSFG to characterize the efficiency of a surface water screen sampler as well. Overall, VSFG spectroscopy turns out to be a versatile tool that can provide valuable information about composition, structure, chemical reactivity, and film formation dynamics of the sea surface nanolayer.

The reaction of pyridine with ditechnetium decacarbonyl [Tc2(CO)10] (1) leads to a novel ortho-pyridyl-ditechnetium hydrido complex, [Tc2(mu-H)(mu-NC5H4)(NC5H5)2(CO)6] (2) and its precursor [Tc2(mu-CO)2(NC5H5)2(CO)6] (3). At ambient temperature 1 was found to react slowly with pyridine to afford the substitution product 3 after 120 h. However, heating the reaction mixture to reflux exclusively leads to the pyridine-ortho-metalated complex 2 in only 30 min. Similarly, complex 3 can be converted completely into 2 upon heating in pyridine for 30 min. Both compounds 2 and 3 were characterized by NMR spectroscopy and X-ray analysis. Both compounds 2 and 3 show a complex dynamic behavior in solution that was investigated by one-dimensional and two-dimensional NMR spectroscopy. Both compounds 2 and 3 show isomerization in solution according to the relative position of the non-bridging pyridine ligands. For 2 the existence of three isomers was shown at equilibrium conditions, 2a (56%) with trans-diaxial, 2b (38%) with cis-diaxial, and 2c (6%) with axial-equatorial arrangement of the non-bridging pyridines. For 3 an equilibrium was detected between two isomers, 3a (67%) with a cis-diaxial and 3b (33%) with a trans-diaxial arrangement of the pyridines.

Room-temperature rate constants for the pressure-dependent reactions SiH2 + ethene, propene, and t-butene have been determined at total pressures of 3.3 mbar < or = p < or = 300 mbar with Ar as buffer gas. SiH2 was detected by means of time-resolved cavity ringdown spectroscopy (CRDS), and the deconvolution of ringdown, kinetics, and laser bandwidth effect was accomplished with the extended simultaneous kinetics and ringdown model (eSKaR). In this way, pseudofirst-order rate constants could be extracted from nonexponential ringdown profiles. The recombination reactions, including the reaction SiH2 + i-butene, have been modeled based on the simplified statistical adiabatic channel model (SACM) and weak collision energy-grained master equation (ME) simulations. The influence of an interfering fast isomerization channel was investigated based on the Rice, Ramsperger, Kassel, Marcus theory (RRKM) and was found to be only important for the C2H4 reaction. Using ab initio energies (G3) and structures (MP2/6-311G(d,p)) as input parameters for the kinetic models, a consistent description of the pressure and temperature dependences of all four reactions was possible. In the temperature range 295 K < or = T < or = 600 K, the extrapolated limiting high-pressure rate constants, k(infinity)(C2H4)/(cm(3) x mol(-1) x s(-1)) = 1.9 x 10(14) (T/K)(-0.065), k(infinity)(C3H6)/(cm(3) x mol(-1) x s(-1)) = 1.3 x 10(14) (T/K)(0.075), k(infinity)(i-C4H8) = 1.8 x 10(14) cm(3) x mol(-1) x s(-1), and k(infinity)(t-C4H8)/(cm(3) x mol(-1) x s(-1)) = 4.6 x 10(13) (T/K)(0.21), are close to the collision number and are more or less temperature independent. In the case of ethene, probably due to the approximate treatment of rotational effects and/or the interfering isomerization process, the applied model slightly underestimates the falloff and thus yields too high extrapolated rate constants at p < 10 mbar.

Cavity ringdown spectroscopy (CRDS) and frequency modulation spectroscopy (FMS) are sensitive absorption based detection methods that have found widespread applications in gas phase reaction kinetics. In part 2 of this review, the theoretical foundations of CRDS are addressed with a special emphasis on quantitative time-resolved measurements of concentration profiles. A complementary review of FMS can be found in part 1 (Z. Phys. Chem. 222 (2008) 1–30). Practical aspects, possible pitfalls, attainable sensitivities, and modern trends are discussed. Recent kinetic studies based on CRDS measurements as a time-resolved detection tool are briefly reviewed and a bibliography with 136 entries is included to facilitate the access to the large body of original literature.

Frequency modulation spectroscopy (FMS) and cavity ringdown spectroscopy (CRDS) are sensitive absorption based detection methods that have found widespread applications in gas phase reaction kinetics. In part 1 of this review, the theoretical foundations of FMS are addressed with a special emphasis on time-resolved quantitative measurements of concentration profiles. A complementary review of CRDS can be found in part 2 (Z. Phys. Chem. 222 (2008) 31–61). Practical aspects, possible pitfalls, attainable sensitivities, and modern trends are discussed. Kinetic studies based on FMS measurements as a time-resolved detection tool are briefly reviewed and a bibliography with more than a hundred entries is included to facilitate the access to the large body of original literature.

International Workshop: Applications and Perspectives of Cavity Enhanced Optical Detection Techniques in Ocean Sciences; Kiel, Germany, 20–21 April 2015

The rate of the reaction 1, HCO+O2--HO2+CO, has been determined (i) at room temperature using a slow flow reactor setup (20 mbarp500 mbar) and (ii) in the temperature range 739 KT1108 K behind reflected shock waves (0.82 barp1.84 bar) employing a perturbation approach. Following the 193 nm excimer laser photolysis of mixtures of glyoxal in Ar, concentration-time profiles were measured using frequency modulation (FM) detection of HCO at a wavelength of lambda=614.752 nm. Observed differences between HCO concentration-time profiles measured with and without O2 added to the reaction mixtures could be almost exclusively attributed to reaction 1. The determined rate constants, k1(295 K)=(3.55+/-0.05)x10(12) cm3 mol-1 s-1, k1(739-1108 K)=3.7x10(13) exp(-13 kJ mol-1/RT) cm3 mol-1 s-1 (Delta log k1=+/-0.16), reveal a slightly positive temperature dependence of reaction 1 at high temperatures. Furthermore, the 193 nm photolysis of glyoxal, (CHO)2, has been proven to be an efficient HCO source. Besides HCO, photolysis of the precursor also produces H atoms. The ratio of initially generated H atoms and HCO radicals, f=[H]0/[HCO]0total, was found to depend on the total density rho. At room temperature, it varies from f=1.6 at rho=8x10(-7) mol cm-3 to f=3.0 at rho=2x10(-5) mol cm-3. H atoms are transformed via reaction 4, H+(CHO)2--H2+HCO+CO, into additional HCO radicals. The rate constants of reaction 4 were determined from unperturbed photolysis experiments to be k4(295 K)=(3.6+/-0.3)x10(10) cm3 mol-1 s-1 and k4(769-1107 K)=5.4x10(13)exp(-18 kJ mol-1/RT) cm3 mol-1 s-1(Delta log k4=+/-0.12).

The determination of rate constants for fast chemical reactions from nonexponential cavity ringdown profiles requires a consideration of the interfering laser bandwidth effect that arises if the line width of the ringdown probe laser exceeds the absorption line width of the detected species. The deconvolution of the kinetics and the bandwidth effect can be accomplished with the extended simultaneous kinetics and ringdown (eSKaR) model presented by Guo et al. (Guo, et al. Phys. Chem. Chem. Phys. 2003, 5, 4622). We present a detailed validation of this eSKaR model by a corresponding investigation of the well-known rate constant for the reaction NH2 + NO. Line profiles of the pulsed ringdown probe laser and the NH2 absorption line were determined from forward modeling of experimental ringdown profiles and verified by narrow-bandwidth laser absorption measurements. In addition, the rate constant for the title reaction was evaluated using the eSKaR model and also by means of a conventional pump-probe approach with variable time delays between the photolysis (pump) and ringdown (probe) laser pulses. The resulting room temperature rate constant for the NH2 + NO reaction, k1= (8.5 +/- 1.0) x 10(12) cm(3) mol(-1) s(-1), and the room temperature pressure broadening coefficient of NH2, = 2.27 GHz/bar, measured on the A2A1

The acetylene reduction assay is a common method for assessing nitrogen fixation in a variety of marine and freshwater systems. The method measures ethylene, the product of the conversion of the gas acetylene to its reduced form by nitrogenase. Knowledge of the solubility of ethylene in aqueous solution is crucial to the calculation of nitrogen fixation rates and depends on the temperature and salinity of the assay conditions. Despite the increasing interest in marine nitrogen fixation, no gas solubility (Bunsen) coefficients for ethylene in seawater are published to date. Here, we provide a set of equations and present semiempirically derived Bunsen coefficients for ethylene in water (ranging from 0.069 to 0.226) for a range of temperatures and salinities that are relevant for aquatic nitrogen fixation. We apply these data to nitrogen fixation scenarios at different temperatures and salinities and stress the importance of using accurate Bunsen coefficients in nitrogen fixation assays.

The thermal decomposition of formaldehyde was investigated behind shock waves at temperatures between 1675 and 2080 K. Quantitative concentration time profiles of formaldehyde and formyl radicals were measured by means ofsensitive 174 nm VUV absorption (CH 2 O) and 614 nm FM spectroscopy (HCO), respectively. The rate constant of the radical forming channel (1a), CH 2 O + M → HCO + H + M, of the unimolecular decomposition of formaldehyde in argon was measured at temperatures from 1675 to 2080 K at an average total pressure of 1 2 bar, k 1 a = 5.0 x 10 1 5 exp(-308 k] mol - 1 /RT) cm 3 mol - 1 s - 1 . The pressure dependence, the rate of the competing molecular channel (1b), CH2O + M → H 2 + CO + M, and the branching fraction β = k 1 a /(k 1 a + k 1 b ) was characterized by a two-channel RRKM/master equation analysis. With channel (1b) being the main channel at low pressures, the branching fraction was found to switch from channel (1b) to channel (1a) at moderate pressures of 1-50 bar. Taking advantage of the results of two preceding publications, a decomposition mechanism with six reactions is recommended. which was validated by measured formyl radical profiles and numerous literature experimental observations. The mechanism is capable of a reliable prediction of almost all formaldehyde pyrolysis literature data, including CH 2 O, CO, and H atom measurements at temperatures of 1200-3200 K, with mixtures of 7 ppm to 5% formaldehyde. and pressures up to 15 bar. Some evidence was found for a self-reaction of two CH 2 O molecules. At high initial CH 2 O mole fractions the reverse of reaction (6), CH 2 OH + HCO ⇄ CH 2 O + CH 2 O becomes noticeable The rate of the forward reaction was roughly measured to be k 6 = 1.5 x 10 1 3 cm 3 mol - 1 s - 1 .

Recently, Brown et al. (S. S. Brown, A. R. Ravishankara and H. Stark, J. Phys. Chem. A, 2000, 104, 7044) demonstrated the potential of cavity ringdown spectroscopy (CRDS) for investigating the kinetics of fast chemical reactions occurring on the same time scale as the ringdown. Based on an approach referred to as the simultaneous kinetics and ringdown (SKaR) model, they were able to determine reaction rate constants from the non-exponential ringdown profiles that arise from the convolution of the concentration change and the ringdown. However, non-exponential ringdown curves are also observed without any reactions when radicals are detected with absorption linewidths comparable to or narrower than the bandwidth of the probe laser. We present an extended SKaR model (eSKaR) that takes this bandwidth effect into account and allows us to extract rate constants from non-exponential ringdown profiles originating from a convolution of the bandwidth effect and the kinetics. The investigation of the rate constant for the fast reaction SiH2 + O2 → products (R1), which has been measured at total pressures in the range 2.5 mbar ≤p ≤ 350 mbar with argon as inert buffer gas, serves as an example for its application. A pressure independent rate constant of k1(295 K) = (9.9 ± 1.9) × 1012 cm3 mol−1 s−1 was obtained.

Using FM spectroscopy formyl radicals were detected for the first time behind shock waves. HCO radicals have been generated by 308 nm photolysis of mixtures of formaldehyde in argon. The HCO spectrum of the (A2A″ ← 2A′) (0900 ← 0010) transition was measured at room temperature with high resolution and the predissociative linewidths Γ of the individual rotational lines were fitted to Γ = X + ZN′2(N′ + 1)2, where X = 0.22 cm−1 and Z = 1.0 × 10−5 cm−1. Since FM spectroscopy is very sensitive to small line shape variations the spin splitting in the Q-branch could be resolved. Time resolved measurements of HCO profiles at temperatures below 820 K provided the temperature independent rates of reaction (4), H + HCO → H2 + CO, and reaction (5), HCO + HCO → CH2O + CO, k4 = 1.1 × 1014 cm3 mol−1 s−1k5 = 2.7 × 1013 cm3 mol−1 s−1and the low pressure room temperature absorption cross section of the Q(9)P(2) line at 614.872 nm, αc = (1.5 ± 0.4) × 106 cm2 mol−1 (base e). Measurements of the unimolecular decomposition of HCO, reaction (3) HCO + M → H + CO + M, were performed at temperatures from 835 to 1230 K and at total densities from 3.3 × 10−6 to 2.5 × 10−5 mol cm−3. They can be represented by the following Arrhenius expression. k3 = 4.0 × 1013·exp(−65 kJ mol−1/RT) cm3 mol−1 s−1 (Δ log k3 = ±0.23)The corresponding RRKM fit, 4.8 × 1017·(T/K)−1.2·exp(−74.2 kJ mol−1/RT) cm3 mol−1 s−1 (600