Atmospheric gases transfer models

When we talk about tracers, we generally mean conservative tracers with no sources or sinks. This is opposed to gas tracers, with gas transfer to the atmosphere, and reactive tracers, with a reaction occurring. Tracer studies typically use a conservative tracer, input to the system in a highly unsteady manner, such as a pulse or a front. The pulse and front are typically a more stringent test of the model than a steady-state process with any variety of reactions. Thus, a model that properly simulates the output concentration curve of a pulse or front is assumed to be sufficient for most real conditions with reactions. 

As shown in Figure 23.7, the continuous lake model nicely describes the concentration maximum, which slowly moved to greater depth due to the deepening of the surface mixed layer. From the model calculation we can conclude that the processes involved in producing this maximum were the combination of riverine PCE input into the surface mixed layer and loss to the atmosphere by gas transfer. The extra input of PCE into the lake between May 6 and July 1, 1985 had to be about 360 moles. The model calculations suggest that the input had dropped to virtually zero after July 1. Part of the compound was quickly and continuously lost to the atmosphere so that the PCE content of the lake never increased much beyond 200 moles. 

A critical parameter in all models of DMS chemistry in the marine atmosphere is tne sea-to-air flux. Although the sea surface concentrations of DMS nave been measured in a wide variety of environments (14). the flux has never been measured directly. Instead, it has been calculated using observed concentrations and various models of gas transfer across the air sea interface. All of the models parameterize die transfer as a first order loss, as follows... 

Transfer of DMS Across the Sea-Air Interface into the Atmosphere. At this time there is no empirical evidence for isotope discrimination during the sea-air transfer of DMS. Theoretically, the transfer of DMS is estimated from gas exchange models (Equation 3)... 

Despite the central role that air-sea gas exchange plays in studies of marine productivity, biogeochemical cycles, atmospheric chemistry, and climate, it has proved extremely difficult to measure air-sea gas fluxes in situ. Only in 2001 were believable direct measurements of oceanic CO2 fluxes reported in the literature (McGillis et al., 2001a). In this section we examine the various models that have been proposed to understand the basic processes that control gas exchange mechanisms, describe results from laboratory experiments, and discuss the various techniques that have been developed to try to measure gas transfer rates in situ. Finally, we describe the development of wind speed (U) based para-metrizations and assess their impact on computation of air-sea gas fluxes. 

A schematic representation of the surface renewal model of air-water gas transfer. Water parcels arrive at the interface from the water interior, where they remain for some time period, 0. The fugacity and concentration at the air-wvater interface are at equilibrium and atmospheric gas diffuses into or out of the liquid as though it were an infinitely deep layer. 

Sportisse, B. 2010. Fundamentals in Air Pollution From Processes to Modelling. Dordrecht, The Netherlands Springer. Includes chapters on atmospheric radiative transfer atmospheric boundary layer, gas-phase atmospheric chemistry aerosols, clouds, and rain and numerical simulations. 

Fig. 2.1. Schematic diagram of a reaction model. The heart of the model is the equilibrium system, which contains an aqueous fluid and, optionally, one or more minerals. The system s constituents remain in chemical equilibrium throughout the calculation. Transfer of mass into or out of the system and variation in temperature drive the system to a series of new equilibria over the course of the reaction path. The system s composition may be buffered by equilibrium with an external gas reservoir, such as the atmosphere.

At later times, solar heat fluxes and convective heat transfer from the atmosphere become important. For a spill onto an insulated dike floor these fluxes may be the only energy contributions. This approach seems to work adequately for liquefied natural gas (LNG) and perhaps for ethane and ethylene. The higher hydrocarbons (C3 and above) require a more detailed heat transfer mechanism. This model also neglects possible water freezing effects in the ground, which can significantly alter the heat transfer behavior. More details on boiling pools is provided elsewhere.19... 

The reaction of ammonia and hydrogen chloride in the gas phase has been the subject of several studies in the last 30 years [56-65], The interest in this system is mainly that it represents a simple model for proton transfer reactions, which are important for many chemical and biological processes. Moreover, in the field of atmospheric sciences, this reaction has been considered as a prototype system for investigation of particle formation from volatile species [66,67], Finally, it is the reaction chosen as a benchmark on the ability, of quantum chemical computer simulations, to realistically simulate a chemical process, its reaction path and, eventually, its kinetics. 

The following, well-acceptable assumptions are applied in the presented models of automobile exhaust gas converters Ideal gas behavior and constant pressure are considered (system open to ambient atmosphere, very low pressure drop). Relatively low concentration of key reactants enables to approximate diffusion processes by the Fick s law and to assume negligible change in the number of moles caused by the reactions. Axial dispersion and heat conduction effects in the flowing gas can be neglected due to short residence times ( 0.1 s). The description of heat and mass transfer between bulk of flowing gas and catalytic washcoat is approximated by distributed transfer coefficients, calculated from suitable correlations (cf. Section III.C). All physical properties of gas (cp, p, p, X, Z>k) and solid phase heat capacity are evaluated in dependence on temperature. Effective heat conductivity, density and heat capacity are used for the entire solid phase, which consists of catalytic washcoat layer and monolith substrate (wall). 

In the emulsion phase/packet model, it is perceived that the resistance to heat transfer lies in a relatively thick emulsion layer adjacent to the heating surface. This approach employs an analogy between a fluidized bed and a liquid medium, which considers the emulsion phase/packets to be the continuous phase. Differences in the various emulsion phase models primarily depend on the way the packet is defined. The presence of the maxima in the h-U curve is attributed to the simultaneous effect of an increase in the frequency of packet replacement and an increase in the fraction of time for which the heat transfer surface is covered by bubbles/voids. This unsteady-state model reaches its limit when the particle thermal time constant is smaller than the particle contact time determined by the replacement rate for small particles. In this case, the heat transfer process can be approximated by a steady-state process. Mickley and Fairbanks (1955) treated the packet as a continuum phase and first recognized the significant role of particle heat transfer since the volumetric heat capacity of the particle is 1,000-fold that of the gas at atmospheric conditions. The transient heat conduction equations are solved for a packet of emulsion swept up to the wall by bubble-induced circulation. The model of Mickley and Fairbanks (1955) is introduced in the following discussion. 

Cyclohexene hydrogenation is a well-studied process that serves as model reaction to evaluate performance of gas-liquid reactors because it is a fast process causing mass transfer limitations for many reactors [277,278]. Processing at room temperature and atmospheric pressure reduces the technical expenditure for experiments so that the cyclohexene hydrogenation is accepted as a simple and general method for mass transfer evaluation. Flow-pattern maps and kinetics were determined for conventional fixed-bed reactors as well as overall mass transfer coefficients and energy dissipation. In this way, mass transfer can be analyzed quantitatively for new reactor concepts and processing conditions. Besides mass transfer, heat transfer is an issue, as the reaction is exothermic. Hot spot formation should be suppressed as these would decrease selectivity and catalytic activity [277]. 

In the development of these processes and their transference into an industrial-scale, dimensional analysis and scale-up based on it play only a subordinate role. This is reasonable, because one is often forced to perform experiments in a demonstration plant which copes in its scope with a small produdion plant ( mock-up plant, ca. 1/10-th of the industrial scale). Experiments in such plants are costly and often time-consuming, but they are often indispensable for the lay-out of a technical plant. This is because the experiments performed in them deliver a valuable information about the scale-dependent hydrodynamic behavior (arculation of liquids and of dispersed solids, residence time distributions). As model substances hydrocarbons as the liquid phase and nitrogen or air as the gas phase are used. The operation conditions are ambient temperature and atmospheric pressure ( cold-flow model ). As a rule, the experiments are evaluated according to dimensional analysis. 

Interfacial mass transfer is an important consideration in many dynamic processes involving the transport of a gaseous species across a gas-liquid interface. In particular the rate of trace gas incorporation into aqueous drops in the atmosphere has recently received much attention because of its relevance to acid precipitation (1,2). In the present paper, mass accommodation coefficient measurements are reported for O3 and SO2 on water surfaces, using an UV absorption-stop flow technique. The results are incorporated into a simple model considering the coupled interfacial mass transfer and aqueous chemistry in aqueous drops. Some implications of the measured accommodation coefficients on the oxidation of SO2 by O3 in cloud water are discussed. 

It would, therefore, be interesting to examine how important the newly measured accommodation coefficients would be in the conversion of S(IV) to S(VI) in a water droplet. A simple model is set up, which considers only aqueous chemistry and gas-phase mass transfer of O3 and SO2 to a cloud droplet. At t = 0, the droplet is exposed to an atmosphere containing constant concentrations of SO2 and O3. The aqueous concentrations of S(IV) and S(Vl) are then calculated as a function of time. 

The cloud chemistry simulation chamber (5,6) provides a controlled environment to simulate the ascent of a humid parcel of polluted air in the atmosphere. The cloud forms as the pressure and temperature of the moist air decreases. By controlling the physical conditions influencing cloud growth (i.e. initial temperature, relative humidity, cooling rate), and the size, composition, and concentration of suspended particles, chemical transformation rates of gases and particles to dissolved ions in the cloud water can be measured. These rates can be compared with those derived from physical/chemical models (7,9) which involve variables such as liquid water content, solute concentration, the gas/liquid interface, mass transfer, chemical equilibrium, temperature, and pressure. 

Gas-liquid interfacial areas, a, and volumetric liquid-side mass transfer coefficients, kLa, are measured in a high pressure trickle-bed reactor. Increase of a and kLa with pressure is explained by the formation of tiny bubbles in the trickling liquid film. By applying Taylor s theory, a model relating the increase in a with the increase in gas hold-up, is developed. The model accounts satisfactorily for the available experimental data. To estimate kLa, contribution due to bubbles in the liquid film has to be added to the corresponding value measured at atmospheric pressure. The mass transfer coefficient from the bubbles to the liquid is calculated as if the bubbles were in a stagnant medium. 

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