Numerical Study on the Impacts of Heterogeneous Reactions on Ozone Formation in the Beijing Urban Area

The air quality model CMAQ-MADRID （Community Multiscale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization and Dissolution） was employed to simulate summer O3 formation in Beijing China, in order to explore the impacts of four heterogeneous reactions on O3 formation in an urban area. The results showed that the impacts were obvious and exhibited the characteristics of a typical response of a VOC-limited regime in the urban area. For the four heterogeneous reactions considered, the NO2 and HO2 heterogeneous reactions have the most severe impacts on O3 formation. During the O3 formation period, the NO2 heterogeneous reaction increased new radical creation by 30%, raising the atmospheric activity as more NO→NO2 conversion occurred, thus causing the O3 to rise. The increase of O3 peak concentration reached a maximum value of 67 ppb in the urban area. In the morning hours, high NO titration reduced the effect of the photolysis of HONO, which was produced heterogeneously at night in the surface layer. The NO2 heterogeneous reaction in the daytime is likely one of the major reasons causing the O3 increase in the Beijing urban area. The HO2 heterogeneous reaction accelerated radical termination, resulting in a decrease of the radical concentration by 44% at the most. O3 peak concentration decreased by a maximum amount of 24 ppb in the urban area. The simulation results were improved when the heterogeneous reactions were included, with the O3 and HONO model results close to the observations.

Melting heat transfer with radiative effects and homogeneous–heterogeneous reaction in thermally stratified stagnation flow embedded in porous medium

The present article deals with thermally stratified stagnation-point flow saturated in porous medium on surface of variable thickness along with more convincing and reliable surface condition termed as melting heat transfer.Homogeneous–heterogeneous reaction and radiative effects have been further taken into account to reconnoiterproperties of heat transfer.Melting heat transfer and phenomenon of homogeneous–heterogeneous reaction have engrossed widespread utilization in purification of metals,welding process,electroslag melting,biochemical systems,catalysis and several industrial developments.Suitable transformations are utilized to attain a scheme of ordinary differential equations possessing exceedingly nonlinear nature.Homotopic process is employed to develop convergent solutions of the resulting problem.Discussion regarding velocity,thermal field and concentration distribution for several involved parameters is pivotal part.Graphical behaviors of skin friction coefficient and Nusselt number are also portrayed.Concentration of the reactants is found to depreciate as a result of strength of both heterogeneous and homogeneous reaction parameters.With existence of melting phenomenon,declining attitude of fluid temperature is observed for higher radiation parameter.

A modified model for isothermal homogeneous and heterogeneous reactions in the boundary-layer flow of a nanofluid

The homogeneous and heterogeneous reactions in the boundary-layer of a flat surface are considered. The autocatalysts are assumed to be of regular sizes, while the solution is a dilute nanofluid. The heat release due to the chemical reactions is taken into account. The Buongiorno’s model is used to describe the behaviors of this reaction system. This configuration makes the current model be different from all previous publications. Multiple solutions are given numerically to the rescaled nonlinear system, whose stability is verified. The results show that the strength coefficients of the homogeneous and heterogeneous reactions are key factors to cause the appearance of the multiple solutions in the distribution of the chemical reactions. Nanofluids enhance the diffusion of heat and help maintain the stability of chemical reactions.

Laboratory simulation of SO_2 heterogeneous reactions on hematite surface under different SO_2 concentrations

The variations of sulfate formation and optical coefficients during SO2 heterogeneous reactions on hematite surface under different SO2 concentrations were examined using in situ diffuse reflectance infrared Fourier transform spectroscopy （DRIFTS） and ion chromatograph （IC）. Laboratory experiments revealed that within ambient SO2 of 0.51-18.6 ppmv, sulfate product, producing velocity, absorption and backward scattering coefficients showed an increasing trend with SO2 concentration. Under given SO2 concentration, the velocity of sulfate producing performed an evolution of initial increasing, midterm decreasing and final stabilizing. The reactive uptake and Brunaner-Emmett-Teller （BET） uptake coefficients of heterogeneous reactions rose with SOz and exhibited high reactivities. Considering global warming, this result is important for the knowledge of heterogeneous reactions of SO2 on mineral particle surface in the atmosphere and the assessment of their impacts on radiative forcing.

Modeling Study of the Impact of Heterogeneous Reactions on Dust Surfaces on Aerosol Optical Depth and Direct Radiative Forcing over East Asia in Springtime

The spatial distributions and interannual variations of aerosol concentrations, aerosol optical depth （AOD）, aerosol direct radiative forcings, and their responses to heterogeneous reactions on dust surfaces over East Asia in March 2006-10 were investigated by utilizing a regional coupled climate-chemistry/aerosol model. Anthropogenic aerosol concentrations （inorganic ＋ carbonaceous） were higher in March 2006 and 2008, whereas soil dust reached its highest levels in March 2006 and 2010, resulting in stronger aerosol radiative forcings in these periods. The domain and five-year （2006-10） monthly mean concentrations of anthropogenic and dust aerosols, AOD, and radiative forcings at the surface （SURF） and at the top of the atmosphere （TOA） in March were 2.4 μg m 3 13.1 lag m^-3, 0.18, -19.0 W m^-2, and -7.4 W m^-2, respectively. Heterogeneous reactions led to an increase of total inorganic aerosol concentration; however, the ambient inorganic aerosol concentration decreased, resulting in a smaller AOD and weaker aerosol radiative forcings. In March 2006 and 2010, the changes in ambient inorganic aerosols, AOD, and aerosol radiative forcings were more evident. In terms of the domain and five-year averages, the total inorganic aerosol concentrations increased by 13.7% （0.17 μg m^-3） due to heterogeneous reactions, but the ambient inorganic aerosol concentrations were reduced by 10.5% （0.13 lag m-3）. As a result, the changes in AOD, SURF and TOA radiative forcings were estimated to be -3.9% （-0.007）, -1.7% （0.34 W m^-2）, and -4.3% （0.34 W m^-2）, respectively, in March over East Asia.

Heterogeneous Reactions between Starch and AKD under Solvent-free Conditions

Oxidized starch powder and cationic starch solution were reacted with alkyl ketene dimer(AKD) under heterogeneous conditions at 70℃ for 12 h.The AKD molecules reacted with starch hydroxyl groups to form β-keto ester linkages under the above conditions.The reaction products were separated into CHCl_3-soluble and CHCl_3-insoluble fractions.FT-IR spectroscopy,SEM,Xray diffraction,and TG-DTA analyses of the CHCl_3-insoluble fraction indicated that β-keto ester substituents were introduced to hydroxyl groups on the starch surfaces.The results indicated that hydrogen bonds between the starch molecules were disrupted under heterogeneous conditions upon heating.The activity and accessibility of hydroxyl groups were enhanced,as a result of which β-keto ester bonds were produced between AKD and starch.Based on these results,we speculate that the β-keto esters which existed in the sheets sized by AKD emulsions were generated by the reaction between AKD and starch.

Reinterpret the heterogeneous reaction of α-Fe_(2)O_(3) and NO_(2) with 2D-COS:The role of SDS,UV and SO_(2)

Heterogeneous reaction of mineral aerosols and atmospheric polluting gases play an important role in atmospheric chemistry.In this study,the reactions of NO_(2) with or without SO_(2) mixture gas on the surface of α-Fe_(2)O_(3) particles under dry conditions were studied.The effects of sodium dodecyl sulfate(SDS)and the heterogeneous reaction under both dark and UV irradiation conditions were investigated.The infrared spectrum analyzed by the two-dimensional correlation spectroscopy(2D-COS)was used to obtain the products formation sequences.The results showed that UV irradiation can promote the production of nitrate.The 2D-COS analysis indicated SDS changed the sequence order of nitrate and nitrite species during reactions.In oxidation conditions,the final product of heterogeneous reaction of NO_(2) and α-Fe_(2)O_(3) was monodentate nitrate.Only the heterogenous reaction of NO_(2) and α-Fe_(2)O_(3) containing SDS(FOS)without UV light,the final product was bidentate nitrate.SDS was the catalysis agent supply and photoresist to the system.With surface active compounds,the environmental lifetime of heterogeneous reactions between trace gases and aerosols extends.Surfactants,ultraviolet light,and the types of gases involved in the reaction all have complex effects on the aerosol aging process.This study provided a reference for subsequent heterogeneous reaction studies and the formation of aerosols.

Heterogeneous reaction of NO_(2) on the surface of NaCl particles

The heterogeneous reaction of NO_(2)on NaCl particles has been investigated with the new sample preparation and the mode of gas-solid free diffusion.Diffuse Reflectance Infrared Fourier Transform Spectroscopy(DRIFTS)is used to characterize the adsorbed products in situ,combined with Ion Chromatographic(IC),X-ray Photoelectron Spectroscopy(XPS)and Scan Electron Micros-copy(SEM).Our results indicate that the reaction is not limited to the surface of the NaCl particles,but penetrated into the upper layers.Surface reactive sites determine the reaction.Kinetic measurements show that nitrate formation on sodium chloride is second order in NO_(2)concentration and reactive uptake coefficient is(1.54±0.70)×10^(-5).

Raman micro-spectrometry as a technique for investigating heterogeneous reactions on individual atmospheric particles

Investigating the heterogeneous reaction on individual atmospheric particles is important because it approximates actual atmospheric conditions and can aid in reducing artifacts in elucidating real mechanisms and processes,and determining real kinetic parameters of the atmosphere relevance.This study developed a Raman microspectrometry method to investigate heterogeneous reactions on individual particles.The method was applied to the reaction of NO2 with individual CaCO3 particles.It was demonstrated that Raman microspectrometry can obtain information on both chemical composition and microscopic morphology at the same time,as well as information on chemical characteristics,such as the phase,which is useful for studying reaction processes.Raman spectra of individual particles deposited on a substrate showed no interference by morphological resonance,which is helpful for obtaining high-quality spectra.Moreover,Raman microspectrometry was compared with other methods for investigating heterogeneous reactions on individual particles and was found to have several advantageous characteristics.

Heterogeneous reaction of NO_2 on the surface of montmorillonite particles

The studies on heterogeneous reactions over montmorillonite, which is a typical 2：1 layered aluminosilicate, will benefit to the Understanding of heterogeneous reactions on clay minerals. Montmorillonite can be classified as sodium montmorillonite or calcium montmorillonite depending on the cation presented between the different layers. Using diffuse reflectance infrared Fourier transform spectroscopy （DRIFTS）, the heterogeneous reaction mechanism of NO2 on the surface of montmorillonite was firstly investigated. Results showed that the reaction of NO2 on the surface of sodium and calcium montmorillonite fit a first-order kinetics, and the reaction duration of calcium montmorillonite was longer than that of sodium montmorillonite under the dry condition. For either sodium or calcium montmorillonite, the uptake coefficient decreased as humidity increased.

Using X-ray computed tomography and micro-Raman spectrometry to measure individual particle surface area, volume, and morphology towards investigating atmospheric heterogeneous reactions

Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogeneous reactions usually have large variations and may not be relevant to real atmospheric conditions. One of the major reasons for this is the use of bulk samples in laboratory experiments, while particles in the atmosphere are suspended individually. A number of technologies have been developed recently to study heterogeneous reactions on the surfaces of individual particles. Precise measurements on the reactive surface area, volume, and morphology of individual particles are necessary for calculating the uptake coefficient, quantifying reactants and products, and understanding the reaction mechanism better. In this study, for the first time we used synchrotron radiation X-ray computed tomography（XCT） and micro-Raman spectrometry to measure individual CaCO_3 particle morphology, with sizes ranging from 3.5–6.5 μm. Particle surface area and volume were calculated using a reconstruction method based on software threedimensional（3-D） rendering. The XCT was first validated with high-resolution fieldemission scanning electron microscopy（FE-SEM） to acquire accurate CaCO_3 particle surface area and volume estimates. Our results showed an average difference of only 6.1% in surface area and 3.2% in volume measured either by micro-Raman spectrometry or X-ray tomography. X-ray tomography and FE-SEM can provide more morphological details of individual Ca CO3 particles than micro-Raman spectrometry. This study demonstrated that X-ray computed tomography and micro-Raman spectrometry can precisely measure the surface area, volume, and morphology of an individual particle.

Heterogeneous reaction mechanism of gaseous HNO3 with solid NaCI： a density functional theory study

Sea salt particles containing NaCl are among the most abundant particulate masses in coastal atmosphere. Reactions involving sea salt particles potentially generate Cl radicals, which are released into coastal atmosphere. Cl radicals play an important role in the nitrogen and O3 cycles, sulfitr chemistry and particle formation in the troposphere of the polluted coastal regions. This paper aimed at .the heterogeneous reaction between gaseous HNO3 .and solid NaCl. The mech.anis.m was in.vestigatedby density functional theory （DFT）. The results imply that water molecules induce the surface reconstruction, which is essential for the heterogeneous reaction. The surface reconstruction on the defective （710） surface has a barrier of 10.24 kcal.mol-1 and is endothermic by 9.69 kcal.mol-1, whereas the reconstruction on the clean （100） surface has a barrier of 18.46 kcal.mol-1 and isendothermic by 12.96 kcal.mol-1. The surface reconstruction involved in water-adsorbed （710） surface is more energetically favorable. In comparison, water molecules adsorbed on NaCl （100） surface likely undergo water diffusion or desorption. Further, it reveals that the coordination number of the Cl-out is reduced after the surface reconstruction, which assists Clout to accept the proton from HNO3. HCl is released from heterogeneous reactions between gaseous HNO3 and solid NaCl and can react with OH free radicals to produce atomic Cl radicals. The results will offer further insights into the impact of gaseous HNO3 on the air quality of the coastal areas.

Heterogeneous reaction of SO_(2) on CaCO_(3) particles:Different impacts of NO_(2) and acetic acid on the sulfite and sulfate formation

Despite the heterogeneous reaction of sulfur dioxide(SO_(2))on mineral dust particles significantly affects the atmospheric environment,the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear.In this work,using the in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)technique,we employed a mineral dust particle model(CaCO_(3))combined with NO_(2)and acetic acid to investigate their effects on the heterogeneous reaction of SO_(2)on CaCO_(3)particles.Itwas found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate.The addition of NO_(2)or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly.There was a synergistic effect between NO_(2)and SO_(2)that promoted the oxidation of sulfite to sulfate,and a competitive effect between acetic acid and SO_(2)that inhibited the formation of sulfite.Moreover,light and water vapor can also affect the heterogeneous reaction of SO_(2)with the coexistence ofmultiple gases.These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.

Atmospheric heterogeneous reactions on soot:A review

Soot particles,composed of elemental carbon and organic compounds,have attracted widespread attention in recent years due to their significant impacts on climate,the environment and human health.Soot has been found to be chemically and physically active in atmospheric aging processes,which leads to alterations in its composition,morphology,hygroscopicity and optical properties and thus changes its environmental and health effects.The heterogeneous reactions on soot also have a significant impact on the transformation of gaseous pollutants into secondary aerosols.Therefore,the interactions between soot and atmospheric substances have been widely investigated to better understand the environmental behaviors of soot.In this review,we systematically summarize the progress and developments in the heterogeneous chemistry on soot over the past_(3)0 years.Atmospheric trace constituents such as NO_(2),O_(3),SO_(2),N_(2)O_(5),HNO_(3),H_(2)SO_(4),OH radical,HO_(2)radical,peroxyacetyl nitrate etc.,are presented in detail from the aspect of their heterogeneous reactions on soot.The possible mechanisms and the effects of environmental conditions on these heterogeneous reactions are also addressed.Further,the impacts of the heterogeneous reactions of soot on the atmospheric environment are discussed,and some aspects of soot-related research which require further investigation are proposed as well.

Heterogeneous reaction of NO_(2) with feldspar, three clay minerals and Arizona Test Dust

Heterogeneous reaction of NO_(2) with mineral dust aerosol may play important roles in troposphere chemistry,and has been investigated by a number of laboratory studies.However,the influence of mineralogy on this reaction has not been well understood,and its impact on aerosol hygroscopicity is not yet clear.This work investigated heterogeneous reactions of NO_(2)(∼10 ppmv)with K-feldspar,illite,kaolinite,montmorillonite and Arizona Test Dust(ATD)at room temperature as a function of relative humidity(<1%to 80%)and reaction time(up to 24 hr).Heterogeneous reactivity towards NO_(2) was low for illite,kaolinite,montmorillonite and ATD,and uptake coefficients of NO_(2),γ(NO_(2)),were determined to be around or smaller than 1×10^(−8);K-feldspar exhibited higher reactivity towards NO_(2),and CaCO_(3) is most reactive among the nine mineral dust samples considered in this and previous work.After heterogeneous reaction with NO_(2) for 24 hr,increase in hygroscopicity was nearly insignificant for illite,kaolinite and montmorillonite,and small but significant for K-feldspar;in addition,large increase in hygroscopicity was observed for ATD,although the increase in hygroscopicity was still smaller than CaCO_(3).

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol （SOA） formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer （SMPS） during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer （VUV-ATOFMS）. Gas chromatograph/mass spectrometer （GC/MS） analyses of oxidation products of anthracene were carried out for assigning the time-of-flight （TOF） mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.

Effects of heterogeneous reaction with NO_(2) on ice nucleation activities of feldspar and Arizona Test Dust

Mineral dust is an important type of ice nucleating particles in the troposphere;however,the effects of heterogeneous reactions on ice nucleation(IN)activities of mineral dust remain to be elucidated.A droplet-freezing apparatus(Guangzhou Institute of Geochemistry Ice Nucleation Apparatus,GIGINA)was developed in thiswork to measure IN activities of atmospheric particles in the immersion freezingmode,and its performancewas validated by a series of experimental characterizations.This apparatus was then employed to measure IN activities of feldspar and Arizona Test Dust(ATD)particles before and after heterogeneous reaction with NO_(2)(10±0.5 ppmv)at 40%relative humidity.The surface coverage of nitrate,θ(NO_(3)^(−)),increased to 3.1±0.2 for feldspar after reaction with NO_(2) for 6 hr,and meanwhile the active site density per unit surface area(ns)at-20℃ was reduced from 92±5 to<1.0 cm^(−2) by about two orders of magnitude;however,no changes in nitrate content or IN activities were observed for further increase in reaction time(up to 24 hr).Both nitrate content and IN activities changed continuously with reaction time(up to 24 hr)for ATD particles;after reaction with NO_(2) for 24 hr,θ(NO_(3)^(−))increased to 1.4±0.1 and ns at-20℃ was reduced from 20±4 to 9.7±1.9 cm^(−2) by a factor of∼2.Our work suggests that heterogeneous reaction with NO_(2),an abundant reactive nitrogen species in the troposphere,may significantly reduce IN activities of mineral dust in the immersion freezing mode.

MHD Stagnation Point Flow of Williamson Fluid over a Stretching Cylinder with Variable Thermal Conductivity and Homogeneous/Heterogeneous Reaction

The present study reveals the effect of homogeneous/hetereogeneous reaction on stagnation point flow of Williamson fluid in the presence of magnetohydrodynamics and heat generation/absorption coefficient over a stretching cylinder. Further the effects of variable thermal conductivity and thermal stratification are also considered. The governing partial differential equations are converted to ordinary differential equations with the help of similarity transformation.The system of coupled non-linear ordinary differential equations is then solved by shooting technique. MATLAB shooting code is validated by comparison with the previously published work in limiting case. Results are further strengthened when the present results are compared with MATLAB built-in function bvp4c. Effects of prominent parameters are deliberated graphically for the velocity, temperature and concentration profiles. Skin-friction coefficient and Nusselt number for the different parameters are investigated with the help of tables.

Impact of greenhouse gas CO_(2) on the heterogeneous reaction of SO_(2) on alpha-Al_(2)O_(3)

The heterogeneous reaction of SO_(2) on mineral dust surfaces is generally considered as an important chemical pathway for secondary sulfate formation in the troposphere.To this day,there are no reported studies that assess the impact of atmospheric CO_(2) in sulfate production on mineral dust surfaces.In this work,we investigate the impact of CO_(2) on SO_(2) uptake on dust proxy aluminum oxide particles using a diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).CO_(2) is demonstrated to suppress the heterogeneous oxidation of SO_(2) on alpha-Al2 O_(3).Compared to that measured in the CO_(2)-free case,the uptake coefficient is decreased by nearly 57%when Al_(2)O_(3) particles are exposed to the gas flow with atmospheric CO_(2) at a relative humidity(RH)of 25%.It is also found that there is a balance between the yield of active moiety-OH provided by AI(OH)3(CO)(OH)2 clusters and the loss of basic hydroxyl group on aluminum oxide surfaces blocked by CO_(2)-derived(bi)carbonate species.This work,for the first time,reveals a negative effect of atmospheric CO_(2) on the sulfate formation,which potentially decreases solarradiation scattering and further exacerbates global warming.

Reaction Kinetics for Heterogeneous Oxidation of Mn(III) ～Toluene

The reaction kinetics of the heterogeneous oxidation of toluene with Mn 3+ was studied by considering the effects of disproportionation of Mn 3+ in reaction system, a 'parallel' modulus was set up. And then the concentration of Mn 3+ in disproportionation and the concentration of benzaldehyde in oxidation were respectively determined in turn, the rate constant, order and pseudo activation energy of the heterogeneous oxidation were obtained by mathematical deduction and the kinetic equation was concluded. In addition, the reaction mechanism was analyzed. It shows that the results are completely consistent with modulus.