Atmospheric reactions relative rates

Figure 5. Relative rate of the light-induced reductive dissolution of hematite in the presence of oxalate as a function of the wavelength. Experimental conditions 0,5 gL 1 hematite initial oxalate concentration 3.3 m mol L 1 pH = 3.0 nitrogen atmosphere. The relative rate is the rate of hematite dissolution at constant incident light intensity. Under the assumption that the light intensity, absorbed by the oscillator that enables the photoredox reaction, corresponds to the incident light intensity, IAX = Iox, the relative rate equals the quantum yield, of dissolved iron(II) formation. As...

The results of this study show (99) the involvement of fragments such as Cr(CO) , (3 < jc < 6) which react with CO molecules which come from any of several sources fragmentation of the original molecules, bulk radiolysis of the compound, application of an external atmosphere, or perhaps from intermolecular exchange. It was concluded from the data that diffusion processes are involved and that the relative rates of reaction and of diffusion away are important in determining the height of the annealing plateaus. 

If the primary loss mechanism of atmospheric reaction is accepted as having a 17h half-life, the D value is 1.6 x 109 mol/Pah. For any other process to compete with this would require a value of at least 108 mol/Pah. This is achieved by advection (4 x 10s), but the other processes range in D value from 19 (advection in bottom sediment) to 1.5 x 10s (reaction in water) and are thus a factor of over 100 or less. The implication is that the water reaction rate constant would have to be increased 100-fold to become significant. The soil rate constant would require an increase by 104 and the sediment by 10s. These are inconceivably large numbers corresponding to very short half-lives, thus the actual values of the rate constants in these media are relatively unimportant in this context. They need not be known accurately. The most sensitive quantity is clearly the atmospheric reaction rate. 

Harris, S.J., Kerr, J.A. (1988) Relative rate measurements of some reactions of hydroxyl radicals with alkanes studied under atmospheric conditions. Int. J. Chem. Kinet. 20, 939-955. 

Oxidation rate constant, k for gas-phase second order rate constants, kOH for reaction with OH radical, kNO, with N03 radical and k with 03 or as indicated, data at other temperatures see reference koH = (5.23 0.42) x 10 " cm3 molecule 1 s-1 with a calculated atmospheric lifetime of 5 h, and k0j < 4 x 10 19 cm3 molecule 1 s 1 at 295 1 K (relative rate, Atkinson Aschmann 1986) kN2o5 = (4.2 0.9) x 10 17 cm3 molecule 1 s 1 for reaction with N205 at 298 + 2 K (relative rate method, Atkinson Aschmann 1987)... 

Why temperatures and rainfall near Chesapeake Bay should be affected by variations of the tidal forces is not so clear. However the atmosphere and stratosphere are pulled away from the earth by tidal forces just as are the waters of the earth. These forces vary by as much as 10 percent during the tidal periods [67] resulting in density variations in the stratosphere with the same periods the consequent density variations may affect the relative rates of stratospheric chemical reactions, causing disturbances of temperature and rainfall on the ground with the tidal periodicities. 

Chemical/Physical. Atkinson et al. (2000) studied the kinetic and products of the gas-phase reaction of 2-heptanone with OH radicals in purified air at 25 °C and 740 mmHg. A relative rate constant of 1.17 x 10 " cmVmolecule Sec was calculated for this reaction. Reaction products identified by GO, FTIR, and atmospheric pressure ionization tandem mass spectroscopy were (with respective molar yields) formaldehyde, 0.38 acetaldehyde, L0.05 propanal, X0.05 butanal, 0.07 pentanal, 0.09 and molecular weight 175 organic nitrates. 

Tuazon et al. (1984a) investigated the atmospheric reactions of TV-nitrosodimethylamine and dimethylnitramine in an environmental chamber utilizing in situ long-path Fourier transform infared spectroscopy. They irradiated an ozone-rich atmosphere containing A-nitrosodimethyl-amine. Photolysis products identified include dimethylnitramine, nitromethane, formaldehyde, carbon monoxide, nitrogen dioxide, nitrogen pentoxide, and nitric acid. The rate constants for the reaction of fV-nitrosodimethylamine with OH radicals and ozone relative to methyl ether were 3.0 X 10 and <1 x 10 ° cmVmolecule-sec, respectively. The estimated atmospheric half-life of A-nitrosodimethylamine in the troposphere is approximately 5 min. 

In this section we discuss the major experimental methods used to determine absolute rate constants for gas-phase reactions relevant to atmospheric chemistry. These include fast-flow systems (FFS), flash photolysis (FP), static reaction systems, and pulse radiolysis. The determination of relative rate constants is discussed in Section C. 

Chemical kinetics is a subject of crucial environmental and economic importance. In the upper atmosphere, for example, maintenance or depletion of the ozone layer, which protects us from the sun s harmful ultraviolet radiation, depends on the relative rates of reactions that produce and destroy O3 molecules. In the chemical industry, the profitability of the process for the synthesis of ammonia, which is used as a fertilizer, depends on the rate at which gaseous N2 and H2 can be converted to NH3. 

In the presence of an atmosphere of air, reaction (1) has been studied by several groups using relative rate techniques under conditions of steady photolysis (18-21). and by Hynes et al. QJ) who employed the pulsed laser photolysis of H202 with LIF detection of OH. Inspection of Table I reveals that the direct time-resolved study (12) yielded a significantly lower result for k2. Hynes et al. (17) discuss the likelihood of there being a secondary reaction channel for DMS in the competitive kinetics experiments which leads to the high rate constants. Indeed, this discrepancy is repeated for the cases of OH + CH3SH and OH + CS2 (see Table II). For this reason the rate constants under atmospheric conditions obtained by the direct technique are recommended for all three of these reactions. 

In atmospheric chemistry, kinetic isotope effects have been measured for the reaction of hydroxyl radicals with acetone using the relative-rate method over a range of temperatures.334 Water vapour had relatively little effect on rates. Product studies have allowed partitioning of the reaction flux into routes that produce acetic acid directly, and secondary processes. 

Using a relative rate method, rate constants for the gas-phase reactions of O3 with 1- and 3-methylcyclopentene, 1-, 3- and 4-methylcyclohexene, 1-methylcycloheptene, cw-cyclooctene, 1- and 3-methylcyclooctene, cycloocta-1,3- and 1,5-diene, and cyclo-octa-l,3,5,7-tetraene have been measured at 296 2 K and atmospheric pressure. The rate constants obtained (in units of 10-18 cm3 molecule-1 s-1) are as follows 1-methylcyclopentene, 832 24 3-methylcyclopentene, 334 12 1-methylcyclohex-ene, 146 10 3-methylcyclohexene, 55.3 2.6 4-methylcyclohexene, 73.1 3.6 1-methylcycloheptene, 930 24 d.s-cyclooclcnc, 386 23 1-methylcyclooctene, 1420 100 3-methylcyclooctene, 139 9 d.v.d.v-cycloocta-1,3-diene, 20.0 1.4 cycloocta- 1,5-diene, 152 10 and cycloocta-l,3,5,7-tetraene, 2.60 0.19 the indicated errors are two least-squares standard deviations and do not include the uncertainties in the rate constants for the reference alkenes (propene, but-l-ene, d.s-but-2-ene, trans-but-2-ene, 2-methylbut-2-ene, and terpinolene). These rate data were compared with the few available literature data, and the effects of methyl substitution have been discussed.50... 

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