Oxidation Reaction Enthalpy

In recent years, aqueous solutions of Xe03 have been used to oxidize a species in solution, from which A[H°m can be calculated when AH for the oxidation reaction is combined with AH for other reactions. The noble gas oxide Xe03 is used as an oxidant because of its stability and the fact that the final reaction product is Xe(g), which has a zero enthalpy of formation and is easily removed from the reaction mixture. As an example, O Hare4 has reported AfHcm for UCI4. We will not go through the details of his procedure, but the critical step involved measuring A TH for the reaction... 

STRATEGY We expect a strongly negative value because all combustions are exothermic and this oxidation is like an incomplete combustion. First, add up the individual standard enthalpies of formation of the products, multiplying each value by the appropriate number of moles from the balanced equation. Remember that the standard enthalpy of formation of an element in its most stable form is zero. Then, calculate the total standard enthalpy of formation of the reactants in the same way and use Eq. 20 to calculate the standard reaction enthalpy. 

Two successive stages in the industrial manufacture of sulfuric acid are the combustion of sulfur and the oxidation of sulfur dioxide to sulfur trioxide. From the standard reaction enthalpies... 

In the manufacture of nitric acid by the oxidation of ammonia, the first product is nitric oxide, which is then oxidized to nitrogen dioxide. From the standard reaction enthalpies... 

C06-0135. The five stable oxides of nitrogen are NO, NOg, Ng O, Ng O4, and N2 O5. Balance each of the following oxidation reactions, and then use standard formation enthalpies to calculate the heats of reaction per mole of atomic nitrogen for each reaction ... 

These data appeared to be very useful for the estimation of the relative O H bond dissociation energies in hydroperoxides formed from peroxyl radicals of oxidized ethers. All reactions of the type R02 + RH (RH is hydrocarbon) are reactions of the same class (see Chapter 6). All these reactions are divided into three groups RO + R (alkane, parameter bre = 13.62 (kJ moC1)172, R02 + R2H (olefin, bre = 15.21 (kJ mob1)1 2, and R02 + R3H (akylaromatic hydrocarbon), hrc 14.32 (kJ mol )12 [71], Only one factor, namely reaction enthalpy, determines the activation energy of the reaction inside one group of reactions. Also,... 

The important role of reaction enthalpy in the free radical abstraction reactions is well known and was discussed in Chapters 6 and 7. The BDE of the O—H bonds of alkyl hydroperoxides depends slightly on the structure of the alkyl radical D0 H = 365.5 kJ mol 1 for all primary and secondary hydroperoxides and P0—h = 358.6 kJ mol 1 for tertiary hydroperoxides (see Chapter 2). Therefore, the enthalpy of the reaction RjOO + RjH depends on the BDE of the attacked C—H bond of the hydrocarbon. But a different situation is encountered during oxidation and co-oxidation of aldehydes. As proved earlier, the BDE of peracids formed from acylperoxyl radicals is much higher than the BDE of the O—H bond of alkyl hydroperoxides and depends on the structure of the acyl substituent. Therefore, the BDEs of both the attacked C—H and O—H of the formed peracid are important factors that influence the chain propagation reaction. This is demonstrated in Table 8.9 where the calculated values of the enthalpy of the reaction RjCV + RjH for different RjHs including aldehydes and different peroxyl radicals are presented. One can see that the value A//( R02 + RH) is much lower in the reactions of the same compound with acylperoxyl radicals. 

We see, at first, that the reaction enthalpy for quinone abstraction reactions with the C—H bond of alkylperoxyl radicals is higher than with the O—H bond of the hydroperoxyl radical. The second important factor is different triplet repulsions in these two types of abstraction reactions. Indeed, the reaction with R02 proceeds via TS of the C H O type. Such reaction is characterized by the high thermally neutral activation energies Eeo = 62.9 kJ mol-1. The value of Ee0 for the reaction involving the O H O TS reaction center is much lower (27.3 kJ mol-1). With the rate constants have a very low value, the reaction Q + R02 cannot influence the oxidative chain termination in comparison with the interaction of two R02 radicals. Indeed, the rate constant for the latter is 105—107 L mol-1 s-1 and, in these cases, the inequality (2k6v )1/2 2k[Q] always holds. The reason for such high Ee0 values and, hence,... 

In accord with calculations performed by Cavell et al. [110], the oxidative addition of C2-X functionalized azolium cations (X = halogen) to metal centers proceeds faster and with a more favorable reaction enthalpy than the oxidative addition of the C2-H substimted imidazolium cations [118, 119]. The former reaction was applied successfully for the preparation of nickel and palladium complexes bearing a variety of different ylidene ligands [119]. 

These values of A Hr are standard state enthalpies of reaction (aU gases in ideal-gas states) evaluated at 1 atm and 298 K. 7VU values of A are in kilojoules per mole of the first species in the equation. When A Hr is negative, the reaction hberates heat, and we say it is exothermic, while, when A Hr is positive, the reaction absorbs heat, and we say it is endothermic. Tks Table 2-2 indicates, some reactions such as isomerizations do not absorb or liberate much heat, while dehydrogenation reactions are fairly endothermic and oxidation reactions are fairly exothermic. Note, for example, that combustion or total oxidation of ethane is highly exothermic, while partial oxidation of methane to synthesis gas (CO + H2) or ethylene (C2H4) are only slightly exothermic. 

An indication of the degree of exothermicity of sulphide oxidation reactions can be gained by comparing the enthalpy of formation (A//f), that is, a measure of the energy locked up in each chemical species, relative to native elements. The difference in enthalpies of formation of all reactants and all products defines the enthalpy (heat released or absorbed) of the reaction. Thermodynamic data on sulphide minerals, such as pyrite, are notoriously varied and disputed, and the values in Table 4 must be treated with caution. Nevertheless, depending on whether one defines the reaction as ending in an aqueous solution (equation 5), an intermediate secondary sulphate (e.g., melanterite - equation 6) or in complete oxidation to an oxyhydroxide (equation 7), the calculated reaction enthalpy (AH°) released is of the order of at least 1000 kJ/mol. 

The enthalpy of reaction, AHr (or reaction enthalpy ), is closely related to the quantity AH that appears in a thermochemical equation, but its units are kilojoules per mole (kj-mol-1) rather than kilojoules. We interpret the per mole to mean per number of moles of each substance as indicated by its stoichiometric coefficient in the chemical equation. For example, the oxidation of methane described by reaction A signifies that 890 kj of heat is released per mole of CFI4 molecules consumed or per... 

Calculate the reaction enthalpy for the oxidation of sulfur dioxide to sulfur trioxide in the reaction 2 S02(g) + 02(g) -2S03(g). 

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