Product distribution analysis

By studying the scattering pattern (the velocity and angular distribution) of the products formed in a crossed molecular beam experiment, much can be deduced about mechanistic details of an elementary reaction. The effect of varying impact parameter, collision geometry, and internal states of the reactants can all be investigated. 

We shall consider three systems which exemplify distinct types of collision dynamics. Two are direct reactions collision, reaction, and separation take place in a time comparable to molecular vibration periods, about 10 sec. The reaction 

Molecular beam experiments are performed in a laboratory frame of reference but the chemically interesting events take place with respect to the center of mass of the colliding species. In order to interpret the data, differential cross sections measured in the laboratory (LAB) coordinate system must be transformed to reflect events which took place in the center-of-mass (CM) coordinate system. To effect this transformation the invariant motion of the center of mass must be subtracted from the scattering data obtained in the LAB system. A simple example which illustrates the difference between LAB and CM kinematics is shown, for an elastic collision, in Fig. 8.6. In CM the particles always move directly toward one another before interaction and directly apart afterwards. This condition is a consequence of momentum conservation in a system with a stationary center of mass. The interaction causes each particle to be deflected through 

This problem is analyzed by R. D. Levine and R. B. Bernstein, Molecular Reaction Dynamics (Oxford Clarendon Press, 1974), pp. 60-63, 192-196. 

The LAB angular distribution of ArD+ at the lowest collision energy is shown in Fig. 8.7. All the ArD+ is scattered at angles close to the direction of the incident Ar+ beam, which is expected since the center-of-mass momentum does not differ greatly from the momentum of the heavy incident (Ar+) or scattered (ArD+) particles. By transforming these data to CM a portrait of the reaction dynamics can be constructed. 

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From product distribution analysis it could be concluded that larger particles present higher selectivity to glycerate due to the reduction of consecutive reaction, i.e. oxidation of glycerate to tartronate, remaining glycolate amount being almost stable. 

Analogously, by assuming first order kinetics with respect to the other organic components, a product distribution analysis can be performed. The reaction rates of steps (l)-(5) in scheme (Figure 12.2) are expressed as... 

What is the influence of the structural and electronic properties of the precursor adducts on the product distribution Analysis of various experimental and calculated [6,6] monoadduct structures shows that the bond length alternation between [5,6]-and [6,6]-bonds is preserved [1]. Significantly, independently of the nature of the... 

Product distribution analysis, and kinetics determined by classical and advanced NMR techniques the transition-metal-catalysed metathesis of alkenes... 

Product distribution analysis confirms the earlier proposed mechanism of cationic olefin polymerizations using alkylaluminum-alkyl halide systems. 

In general, product distribution analysis is only used to provide qualitative evidence for template effects. In the next section, we will discuss the parameters which are important in the quantification of template effects and show how choice of concentration regime can be used to optimize the effectiveness of a template. 

Cobalt. Solvent effects on hydroformylation of propene and of pent-l-ene catalysed by CoH(CO)4 have been investigated by product distribution analysis. Effects of temperature and pressures of hydrogen and carbon monoxide on the mechanism of hydroformylation of propene in the presence of Co2(CO)8(PBu8)a have similarly been probed by product analysis. The reaction of (36) with methanol or ethanol (R OH) produces CHR(COaRi)2. ... 

Lloyd-Jones GC. Product distribution analysis, and kinetics determined by classical and advanced NMR techniques the transition-metal-catalysed metathesis of alkenes. In MaskiU H, ed. The Investigation of Organic Reactions and Their Mechanisms. Oxford Wiley Blackwell 2006 343-352. 

Garcia E, Corchado JC, Espinosa-Garcia J (2012) A detailed product distribution analysis of some potential energy surfaces describing the OH + CO —> H + CO2 reaction. Comput Theor Chem 990 47... 

Interest in the mechanism and product distribution of thermal and photochemical transformations of aryl azides led to the isolation of some nitrogen-containing derivatives of heptafulvalene. Based on elemental analysis and spectroscopic data it has been suggested tentatively that the compound isolated following vapor-phase pyrolysis of azidopentafluoro-... 

In 1971, a short communication was published [54] by Kumada and co-workers reporting the formation of di- and polysilanes from dihydrosilanes by the action of a platinum complex. Also the Wilkinson catalyst (Ph3P)3RhCl promotes hydrosilation. If no alkenes are present, formation of chain silanes occurs. A thorough analysis of the product distribution shows a high preference for polymers (without a catalyst, disproportionation reactions of the silanes prevail). Cross experiments indicate the formation of a silylene complex as intermediate and in solution, free silylenes could also be trapped by Et3SiH [55, 56],... 

Thermal properties of several chlorinated phenols and derivatives were studied by differential thermal analysis and mass spectrometry and in bulk reactions. Conditions which might facilitate the formation of stable dioxins were emphasized. No two chlorinated phenols behaved alike. For a given compound the decomposition temperature and rate as well as the product distribution varied considerably with reaction conditions. The phenols themselves seem to pyro-lyze under equilibrium conditions slowly above 250°C. For their alkali salts the onset of decomposition is sharp and around 350°C. The reaction itself is exothermic. Preliminary results indicate that heavy ions such as cupric ion may decrease the decomposition temperature. 

The catalytic reaction was carried out at 270°C and 101.3 kPa in a stainless steel tubular fixed-bed reactor. The premixed reaction solution, with a molar ratio catechol. methanol water of 1 1 6, was fed into the reactor using a micro-feed pump. To change the residence time in the reactor, the catechol molar inlet flow (Fio) and the catalyst mass (met) were varied in the range 10 < Fio <10 mol-h and 2-10 < met < 310 kg. The products were condensed at the reactor outlet and collected for analysis. The products distribution was determined quantitatively by HPLC (column Nucleosil 5Ci8, flow rate, 1 ml-min, operating pressure, 18 MPa, mobile phase, CH3CN H2O =1 9 molar ratio). 

In summary, the H + HD reaction shows little sign of resonance scattering in the ICS. Furthermore, the product distributions without angle resolution show no unusual behavior as functions of energy that might indicate resonance behavior. On the other hand, the forward peaking in the angular product distribution does appear to reveal resonance structure. Since time-delay analysis is at present not possible in a molecular beam experiment, it is the combination of a sharp forward peak with the unusual... 

An extensive review of the literature reveals that the only studies of vibrational effects in insertion chemistry have focused on reactions of 0(1D)175-177 and C(1D)177,178 with H2. Since there is no potential energy barrier to insertion in these systems, reaction proceeds readily even for unexcited reactants.179 Since the efficiency of vibrational excitation was 20% in both studies, due to the large cross-sections for ground state reactions, only small changes were observed in the experimental signal. From an analysis of the product distributions, it was concluded that while H2(v = 0) primarily reacted via an insertion mechanism, direct abstraction seemed to become important for = 1). For 0(1D), this is similar to behavior at elevated collision energies.180... 

The first point to be established in any experimental study is that one is dealing with parallel reactions and not with reactions between the products and the original reactants or with one another. One then uses data on the product distribution to determine relative values of the rate constants, employing the relations developed in Section 5.2.1. For simple parallel reactions one then uses either the differential or integral methods developed in Section 3.3 in analysis of the data. 

The volumetric expansion parameter S may thus be taken as 0.9675. The product distribution will vary somewhat with temperature, but the stoichiometry indicated above is sufficient for preliminary design purposes. (We should also indicate that if one s primary goal is the production of ethylene, the obvious thing to do is to recycle the propylene and ethane and any unreacted propane after separation from the lighter components. In such cases the reactor feed would consist of a mixture of propane, propylene, and ethane, and the design analysis that we will present would have to be modified. For our purposes, however, the use of a mixed feed would involve significantly more computation without serving sufficient educational purpose.)... 

Referring first of all to the reactions over 0.2% platinum/alumina (Table V) the major features of the product distributions may be explained by a simple reaction via an adsorbed C5 cyclic intermediate. For instance, if reaction had proceeded entirely by this path, 2-methylpentane-2-13C would have yielded 3-methylpentane labeled 100% in the 3-position (instead of 73.4%) and would have yielded n-hexane labeled 100% in the 2-position (instead of 90.2%). Similarly, 3-methylpentane-2-I3C would have yielded a 2-methylpentane labeled 50% in the methyl substituent (instead of 42.6%), and would have yielded n-hexane labeled 50% in the 1- and 3-positions (instead of 43.8 and 49% respectively). The other expectations are very easily assessed in a similar manner. On the whole, the data of Table V lead to the conclusion that some 80% or so of the reacting hydrocarbon reacts via a simple one step process via an adsorbed C5 cyclic intermediate. The departures from the distribution expected for this simple process are accounted for by the occurrence of bond shift processes. It is necessary to propose that more than one process (adsorbed C6 cyclic intermediate or bond shift) may occur within a single overall residence period on the catalyst Gault s analysis leads to the need for a maximum of three. The number of possible combinations is large, but limitations are imposed by the nature of the observed product distributions. If we designate a bond shift process by B, and passage via an adsorbed Cs cyclic intermediate by C, the required reaction paths are... 

A more detailed analysis of the results obtained over 10% platinum/ alumina (115) leads to an extended array of parallel, multistep reaction paths, and it was concluded (for 273°C) that an adsorbed species had a chance of reacting via an adsorbed C5 cyclic intermediate of about 0.3, of reacting via a bond shift of about 0.2, and a chance of desorption of about 0.5. One would expect these probabilities to be temperature dependent, but to different extents, so that the nature of the product distributions should also be temperature dependent. 

More than just a few parameters have to be considered when modelling chemical reactivity in a broader perspective than for the well-defined but restricted reaction sets of the preceding section. Here, however, not enough statistically well-balanced, quantitative, experimental data are available to allow multilinear regression analysis (MLRA). An additional complicating factor derives from comparison of various reactions, where data of quite different types are encountered. For example, how can product distributions for electrophilic aromatic substitutions be compared with acidity constants of aliphatic carboxylic acids And on the side of the parameters how can the influence on chemical reactivity of both bond dissociation energies and bond polarities be simultaneously handled when only limited data are available ... 

The chromatograms of the liquid phase show the presence of smaller and larger hydrocarbons than the parent one. Nevertheless, the main products are n-alkanes and 1-alkenes with a carbon number between 3 to 9 and an equimolar distribution is obtained. The product distribution can be explained by the F-S-S mechanism. Between the peaks of these hydrocarbons, it is possible to observe numerous smaller peaks. They have been identified by mass spectrometry as X-alkenes, dienes and also cyclic compounds (saturated, partially saturated and aromatic). These secondary products start to appear at 400 °C. Of course, their quantities increase at 425 °C. As these hydrocarbons are not seen for the lower temperature, it is possible to imagine that they are secondary reaction products. The analysis of the gaseous phase shows the presence of hydrogen, light alkanes and 1-alkenes. 

One way to get a representative product distribution for a specific period is to remove all FT products in the reactor system and replace them with a substance that will not influence selectivity determination. The FT reaction is then run for a specific period, after which a full analysis can be done that will represent only the products produced during that specific period. In Figure 13.8, data are presented for a run started with the catalyst suspended in a highly paraffinic wax (FT HI wax, C30-C90). After a certain time of synthesis, the FT run was stopped and the catalyst placed under inert conditions (argon). The reactor content was then displaced with degassed and dried polyalphaolefin oil (Durasyn). After restarting the FT synthesis, the total product spectrum was determined (HI run after displacement). It was found that the value of a2 was much lower than before the displacement of the HI wax. In fact, the a2 values were quite comparable to those measured when the FT synthesis was started up with Durasyn (compare with Durasyn runs 1, 2, and 3). This clearly illustrates the impact that the reactor medium used to start the FT reaction can have on the determination of the a-value. The results further show that there was no change in the value of a2 of the iron catalyst up to 500 h on-line. 

Donnelly, T.J., Yates, I.C., Satterfield, C.N. 1988. Analysis and prediction of product distributions of the Fischer-Tropsch synthesis. Energy Fuels 2 734. 

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