Hydroxyl radicals, reaction with methane

The hydroxyl radical, in turn, is integral to many atmospheric reactions including those that activate the various lower hydrocarbons to more reactive radical groups. For example, the hydroxyl radical combines with methane to produce the methyl radical (CH3), as shown in Equation (16.63) ... 

By combining these reactions, hydroxyl radicals, generated with the photocatalyst and the electron transfer reagent, should react with methane to produce m yl radicals. In our... 

Hydrocarbon reactivity is best based upon the interaction of hydrocarbons with hydroxyl radical. Methane, the least-reactive common gas-phase hydrocarbon with an atmospheric half-life exceeding 10 days, is assigned a reactivity of 1.0. (Despite its low reactivity, methane is so abundant in the atmosphere that it accounts for a significant fraction of total hydroxyl radical reactions.) In contrast, P-pinene produced by conifer trees and other vegetation, is almost 9000 times as reactive as methane, and i7-limonene, (from orange rind) is almost 19000 times as reactive. 

Of course, all the appropriate higher-temperature reaction paths for H2 and CO discussed in the previous sections must be included. Again, note that when X is an H atom or OH radical, molecular hydrogen (H2) or water forms from reaction (3.84). As previously stated, the system is not complete because sufficient ethane forms so that its oxidation path must be a consideration. For example, in atmospheric-pressure methane-air flames, Wamatz [24, 25] has estimated that for lean stoichiometric systems about 30% of methyl radicals recombine to form ethane, and for fuel-rich systems the percentage can rise as high as 80%. Essentially, then, there are two parallel oxidation paths in the methane system one via the oxidation of methyl radicals and the other via the oxidation of ethane. Again, it is worthy of note that reaction (3.84) with hydroxyl is faster than reaction (3.44), so that early in the methane system CO accumulates later, when the CO concentration rises, it effectively competes with methane for hydroxyl radicals and the fuel consumption rate is slowed. 

Hsu, K. J., and W. B. DeMore, Rate Constants and Temperature Dependences for the Reactions of Hydroxyl Radical with Several Halogenated Methanes, Ethanes, and Propanes by Relative Rate Measurements, J. Phys. Chem., 99, 1235-1244 (1995). 

Gas-phase oxidation of methane could be enhanced by the addition of a small amount of NO or N02 in the feed gas.1077 Addition of methanol to the CH4-02-N02 mixture results in a further increase in methane reactivity.1078 Photocatalytic conversion of methane to methanol is accomplished in the presence of water and a semiconductor photocatalyst (doped W03) at 94°C and atmospheric pressure.1079 The yield of methanol significantly increased by the addition of H202 consistent with the postulated mechanism that invokes hydroxyl radical as an intermediate in the reaction. 

Whereas several transient species have been observed for dioxygen activation by MMOH, no intermediates were found by rapid-mixing spectroscopic methods for the actual methane hydroxylation step. Mechanistic probes, i.e. certain non-natural substrates that are transformed into rearranged products only if the reaction proceeds via a specific intermediate such as a radical or a cation, give ambivalent results Some studies show that products according to a pathway via cationic intermediates are obtained in sMMO hydroxylations and at least one study suggests the presence of a radical intermediate [40]. Computational analyses of the reaction of MMOHq with methane suggest a so-called radical recoil/rebound mechanism in which MMOHq... 

Reactions may exhibit kinetic isotope effects as a result of the lighter isotope reacting faster. To illustrate this type of isotope effect, consider the oxidation of methane in the atmosphere (22). The oxidation is initiated by a reaction with the hydroxyl free radical (OH) in which OH irreversibly abstracts a hydrogen atom from the carbon. Methane molecules containing the lighter carbon isotope react faster, and as a consequence, the 613C value of the product is lower. 

Mueller, C.R., Ignatowski, J. (1960) Kinetics of the reaction of hydroxyl radical with methane and nine chloride- and fluorine-substituted methanes. I. Experimental results, comparisons, and application. J. Chem. Phys. 32, 1430-1434. 

The atmospheric fate of a halocarbon molecule depends upon whether or not it contains a hydrogen atom. Hydrohalomethanes are oxidized by a series of reactions with radicals prominant in the troposphere, predominantly hydroxyl OH. Fully halogenated methanes are unreactive towards these radicals and consequently are transported up through the troposphere into the stratosphere, where their oxidation is initiated by UV photolysis of a carbon-halogen bond. 

The oxidation scheme for halomethanes not containing a hydrogen atom is similar to that for those which do, except that it is not initiated by tropospheric reaction with hydroxyl radicals, since the fully halogenated methanes are unreactive. Consequently, substantial amounts of CFCs and halons are transported intact up into the stratosphere, where they absorb UV radiation of short wavelength and undergo photodissociation (equation 36) to a halogen atom and a trihalomethyl radical. The halogen atom Y may enter into catalytic cycles for ozone destruction, as discussed in the introduction. 

The OH/OOH pathway. First a bit of terminology OH is called the hydroxyl radical and OOH is called the hydroperoxyl radical. There are several ways to form OH in the atmosphere. One such reaction is the reaction of methane with excited atomic oxygen ... 

Hydroxyl radical, OH, is the principal atmospheric oxidant for a vast array of organic and inorganic compounds in the atmosphere. In addition to being the primary oxidant of non-methane hydrocarbons (representative examples of these secondary reactions are given in Table 6), OH radical controls the rate of CO and CH4 oxidation. Furthermore, the OH reaction with ozone also limits the destruction of O3 in the troposphere, it also determines the lifetime of CH3CI, CHsBr, and a wide range of HCFC s, and it controls the rate of NO to HNO3 conversion. Concentration profiles for hydroxyl radical in the atmosphere are shown in Fig. 2. 

Thus the lifetime of a constituent with a first order removal process is equal to the inverse of the first order rate constant for its removal. Taking an example from atmospheric chemistry, the major removal mechanism for many trace gases is reaction with hydroxyl radical, OH. Considering two substances with very different rate constants for this reaction, methane and nitrogen dioxide... 

Reaction of CO with hydroxyl radicals (OH ) is the major method of removing CO from the atmosphere (IPCS, 1999). The cycle of hydroxyl radicals is coupled to cycles of CO, methane, water, and ozone they are produced by the photolysis of ozone followed by the reaction of the excited oxygen atoms with water vapor to produce two hydroxyl radicals (0( D) + H2O —> OH + OH ). A small proportion of atmospheric CO is removed by the sod. 

It is estimated that about 500 million tons of methane are being added to the air each year (Craig and Chou, 1982), largely by anaerobic production in rice paddies and wetlands as well as from the metabolism of ruminant domestic animals and, possibly, African termites (Rasmussen and Khalil, 1981 Zimmerman et d., 1982). This gas is slowly oxidized by reactions with Hydroxyl free radical. Its atmospheric content is around 5 gigatons, indicating that the residence time in the atmosphere is about 10 years. As Figure 12 shows, since 1965 the atmospheric concentration of methane has increased by about 3096. If this rate continues, the methane concentration will have doubled early in the 21st century. 

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