Activation energy of methanation

The data presented in Table 1.3 illustrate the dependence of the activation energy of methane on the edge or corner (kink) atom position of some transition-metal surfaces. 

If methane is considered for reaction (3.13), a first order reaction rate is usually assumed, i.e. the coefficient n of expression (3.22) is equal to 1. According to Achenbach [22], the activation energy of methane steam reforming is 82 kJ mol-1 and the pre-exponential factor is 4274 mol m-2 bar-1 s-1. More recent experimental studies report an activation energy of 112 15 kJ mol-1 [23],... 

Thus, what we still need for description of heterogeneous rate constants is a method for evaluation of activation energies. One important observation helped to solve this problem. While studying kinetics and thermochemistry of redox processes over typical OCM catalysts, it was found (Bychkov et al., 1989 Sinev et al., 1990) that the activation energy of methane interaction with [0]s sites can be sufficiently well described in terms of the well-known Polanyi-Semenov correlation (see Fig. 7)... 

Table 6.60 Activation energy of methanation and rate of eunmonia synthesis...

Table 22.2 Comparison of apparent activation energy of methane and carbon dioxide over La2Ni04 and LaSrNi04.

Decomposition. Acetaldehyde decomposes at temperatures above 400°C, forming principally methane and carbon monoxide [630-08-0]. The activation energy of the pyrolysis reaction is 97.7 kj/mol (408.8 kcal/mol) (27). There have been many investigations of the photolytic and radical-induced decomposition of acetaldehyde and deuterated acetaldehyde (28—30). 

Methane reacts with sulfur (an active nonmetal element of group 6A) at high temperatures to produce carbon disulfide. The reaction is endothermic, and an activation energy of approximately 160 KJ is required. Activated alumina or clay is used as the catalyst at approximately 675°C and 2 atmospheres. The process starts by vaporizing pure sulfur, mixing it with methane, and passing the mixture over the alumina catalyst. The reaction could be represented as ... 

This linear variation in catalytic activation energy with potential and work function is quite noteworthy and, as we will see in the next sections and in Chapters 5 and 6, is intimately linked to the corresponding linear variation of heats of chemisorption with potential and work function. More specifically we will see that the linear decrease in the activation energies of ethylene and methane oxidation is due to the concomitant linear decrease in the heat of chemisorption of oxygen with increasing catalyst potential and work function. 

Thus, the elementary cellular structure could be regarded as an intrinsic characteristic of fhe detonation in a mixture at given initial composition, temperature, and pressure. The dimension of X is of fhe order of magnitude of millimeters or less for gaseous mixfures with oxygen, but several centimeters for less sensitive mixtures (even larger, for methane/air af afmospheric pressure). It decreases when the initial pressure increases. Its variation with the initial temperature is more complicated and depends on the value of fhe reduced activation energy of fhe chemical reactions. The value of... 

Then the activation energy for methane production from Cads is the overall activation energy for the hydrogenation of Cads to CH4, and Eq. (1.5) gives the rate of methane production ... 

Tec and rn decrease when the carbon adsorption energy increases. Volcano-type behavior of the selectivity to coke formation is found when the activation energy of C-C bond formation decreases faster with increasing metal-carbon bond energy than with the rate of methane formation. Equation (1.16b) indicates that the rate of the nonselective C-C bond forming reaction is slow when Oc is high and when the metal-carbon bond is so strong that methane formation exceeds the carbon-carbon bond formation. The other extreme is the case of very slow CO dissociation, where 0c is so small that the rate of C-C bond formation is minimized. 

The trend is illustrated for ammonia activation in Figure 1.17 [19]. In this figure, the activation energies of ammonia activation are compared for stepped and nonstepped surfaces of Pt. Similarly as also found for H2O activation [20], the dissociation barrier is found to be invariant to surface structural changes. This is very different compared to the earlier discussed activation of methane that shows a very strong structural dependence. 

A slow oxidation of acetic acid by Mn(III) acetate occurs at 100 °C to give mainly acetoxyacetic acid and CO2 with an activation energy of 28 kcal.mole F In the presence of excess Mn(Il) a first-order disappearance of oxidant is found . The low yield of methane is incompatible with an initial homolysis of the type... 

A different picture is observed when a polar radical reacts with a C—H bond of a polar molecule. For example, the reaction of an oxygen atom with the methane C—H bond is characterized by the activation energy of thermoneutral reaction /ic0 54.6 kJ mol-1 and parameter bre= 13.11 (kJ mol-1)172 while the reaction with the methanol C—H bond is characterized by Ed) 50 kJ mol-1 and parameter brc 12.55 (kJ mol-1)172 [30]. For these values of bre, the difference between the activation energies is 4.6 kJ mol-1. The decrease in the activation energy can be explained by the fact that the polar O—H group in the O H C—OH transition state interacts with the O H C polar reaction center. 

The induction time data and density profiles pf detonations in oxy-hydrogen and oxy-methane mixtures were analyzed on the basis of the kinetic data obtained by the reflected-wave technique and similar methods. A plot of the ignition delay vs 1/T in oxy-ammonia mixtures gave a straight line with a slope corresponding to an activation energy of 42.5 kcal/mole. In these mixtures the induction zone is not uniform, but the shock front is flat and end of the reaction zone is clearly discernible. Onedimensional detonation waves of low Mach number but relatively stable were obtained in a gas preheated to 600-1800°K ahead of the shock front... 

The arguments behind the d band model are quite general and should apply to the interactions in the transition state as well as in the initial and final (adsorbed) states of the process. We therefore expect correlations between the d band center and transition state energies to be the same as for chemisorption energies. This is illustrated in the bottom panel of Figure 4.10. Figure 4.16 shows in detail how the activation energy for methane on different Ni surfaces scales with the center of the d bands projected onto the appropriate metal states to which the transition state couples. 

Figure 4.16. Calculated variations in the activation energy for methane dissociation over a number of different surfaces. The results are shown as a function of the energy of the d states coupling to the transition state methane molecule. Adapted from Ref. [57].

Kassel67 proposed an activation energy of 44 kcal. for the reaction on the basis of an uncertain mechanism for CH4 pyrolysis, and Bawn3 reported that ethane was not formed when methylene was (presumably) produced in the presence of methane at 300°C. by reaction of Na vapor with CH2Br2. 

The activation energy of free radical recombination approached zero. As a result of these investigations, the conditions for selective conjugated oxidation of methane to formaldehyde with hydrogen peroxide were determined and the process mechanism was suggested. The example is notable, because two types of free radicals (CH and H02) are reactive particles in it. 

The glow electrolysis technique (electrolysis with an anode immersed in the solution and the cathode above the surface) at 600-800 V dc and 300-500 mA converts a solution of starch into ethylene, methane, hydrogen, and both carbon mono- and dioxides.323 Electrochemical methods for converting polysaccharides and other biomass-derived materials have been reviewed briefly by Baizer.324 These methods are mainly oxidations along a potential gradient, which decreases the activation energy of the reactants. Starch in 5 M NaOH solution is oxidized on platinum electrodes to carboxylic acids with an activation energy of about 10 kcal/mol. In acidic media oxidation takes place at C-l followed by decarboxylation and oxidation at the C-2 and C-6 atoms.325... 

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