Carbonaceous molecules

Propylene cokage experiments followed by gravimetry have shown that higher is the 5A zeolite calcium content, higher are the cokage kinetics and carbon content inside the pores (Fig. 1). The total carbon contents retained in the porosity after desorption at 350°C of physisorbed propylene are 14.5% and 11% for 5A 86 and 5A 67 samples respectively. These carbon contents are relatively important and probably come from the formation of heavy carbonaceous molecules (coke) as it has been observed by several authors [1-2], The coke formation requires acid protonic sites which seems to be present in both samples but in more important quantity for the highly Ca-exchanged one (5A 86). 

The chemistry of carbon, and radiocarbon, in the atmosphere represents one of the most important areas of environmental research today. The primary practical reason for this is the increasing attention which must be paid to the critical balance between energy and the environment, especially from the viewpoint of man s perturbations of natural processes and his need to maintain control. Probably more than other species, carbonaceous molecules play a central role in this balance. Some of the deleterious effects of carbonaceous gases and particles in the atmosphere are set down in Table 3. The potential effects of increased local or global concentrations of these species on health and climate have led to renewed interest in the carbon cycle and the "C02 Problem". It should be evident from the table, however, that carbon dioxide is not the only problem. In fact, the so-called "trace gases and particles" in the atmosphere present an important challenge to our interpretation of the climatic effects of carbon dioxide, itself [20]. 

No other allotropic forms of carbon were known until ten years ago then arising from studies of interstellar carbonaceous molecules, a new form of carbon, namely fullerene or buckyballs , was discovered (Kroto et al 1985), for which the authors received the 1996 Nobel Prize for Chemistry. Its structure is basically a ball or spherically shaped cage consisting of pure carbon. The most stable... 

Polyynes and other novel carbonaceous molecules are worthy of thorough studies from the viewpoint of both pure and applied sciences. Thus, they are investigated in various fields such as molecular spectroscopy, combustion chemistry, material sciences, and interstellar chemistry. They are produced under various conditions as described in other chapters of this book. In this chapter we will present the results of our study by time-of-flight mass spectroscopy of the title molecules to obtain insights into some aspects of their formation and stability in the gas phase. 

In this paper, the phenomena occuring in catalysts used to hydrocrack petroleum residua are discussed. Reaction sites are provided by the catalyst sulphide phase (Mo is the majority cation) and by the catalyst oxide phase (A1 is the majority cation). The influence of the promoter cations (typically Co or Ni) is also described. The catalyst is deactivated by coke and by metals. Furthermore, the reaction rate is often controlled by the rate of diffusion of the large carbonaceous molecules in the residua. All of these factors have been considered in mathematical simulations of the phenomena occuring in the catalyst. 

Several types of reactions occur on residual oil hydrocracking catalysts(1], molecular weight reduction (hydrogenation and bond cleavage), hydrodemetallization (Ni and V), and heteroatom removal (S, N, and 0). These DESIRABLE REACTIONS can all be generalized as a reaction between a carbonaceous molecule, CM, and hydrogen, as follows ... 

The carbonaceous molecule in Equation 1 is chemisorbed by electron acceptor states (represented as I" ) in the catalyst. Examples of electron acceptor states include anion vacancies in molybdenum sulphides and Lewis acid sites in alumina. Heckelsberg and Banks [7] have explained catalytic cracking in terms of electron transfer which occurs via electron acceptor states. 

The carbonaceous molecule will be adsorbed at anion vacancies [8-10] which in this case are sulphur vacancies in MoS. As an example, a carbonaceous molecule in a residual oil would probably be a polycyclic aromatic containing a thiophenic ring, CM-S... 

The sulphur containing carbonaceous molecule could be chemisorbed by an electron acceptor state, which is a sulphur vacancy in MoS, as indicated in Equation 4. The chemisorbed species can react with hydrogen as shown in Equation 5. 

The hydrogen which reacts is also chemisorbed on the catalyst in a manner to be described below. The reaction products are MoS and a hydrogenated carbonaceous molecule. The MoS can also be considered to be MoS containing non-stoichiometric sulphur. The non-stoichiometric MoS , containing excess sulphur anions, must also contain electron holes in order to preserve electron neutrality, as shown in Equation 6... 

Equations 10-13 are based on the carbonaceous molecules being chemisorbed by electron acceptor states and on hydrogen being chemisorbed by electron holes. 

The work function O is the energy required to remove an electron from a metal. It is an intrinsic property of the metal, which is measured under conditions of ultrahigh vacuum, on surfaces that have been meticulously cleaned. Even a small amount of impurity adsorbed on the surface (e.g. oxygen or an oxide, water, or carbonaceous molecule), could give rise to significant errors in the measured value of the work function. Moreover, the value measured on a polycrystalline metal surface is a weighted average of the contribution of the work function for different crystal faces. Thus, each metal has in fact several work function values, each characteristic of a different crystal face. The relevant scientific literature is replete with data with values of for different metals and many of the common crystal faces for each metal. 

At pressures of 13 GPa many carbonaceous materials decompose when heated and the carbon eventually turns into diamond. The molecular stmcture of the starting material strongly affects this process. Thus condensed aromatic molecules, such as naphthalene or anthracene, first form graphite even though diamond is the stable form. On the other hand, aUphatic substances such as camphor, paraffin wax, or polyethylene lose hydrogen and condense to diamond via soft, white, soHd intermediates with a rudimentary diamond stmcture (29). 

This is not the case in most fires where some oi the intermediate produces, formed when large, complex molecules are broken up, persist. Examples are hydrogen cyanide from wool and silk, acrolein from vegetable oils, acetic acid from timber or paper, and carbon or carbon monoxide from the incomplete combustion of carbonaceous materials. As the fire develops and becomes hotter, many of these intermediates, which are often toxic, are destroyed—for example, hydrogen cyanide is decomposed at about 538°C (1000°F). 

Apart from reactions with the electrolyte at the carbon surface, the irreversible specific charge is furthermore strongly affected by the possible co-intercalation of polar solvent molecules between the graphene layers of highly graphitic matrices [139]. This so-called "solvated intercalation reaction" depends (i) on the crystallinity and the morphology of the parent carbonaceous material, which will be discussed in Sec. 

Methylcyclopentane is a powerful probe molecule for the study of metal surfaces. The product distribution on platinum depends on the following factors particle size 491 reaction conditions 492-494 carbonaceous residues,492,493,495 and the extent of the interface between the metal and the support.492,493,495 The hydrogenolysis rate of methylcyclopentane depends on the hydrogen pressure.496,497 The rate exhibits a maximal value as a function of hydrogen pressure on EuroPt catalysts.498 The hydrogenolysis of methylcyclopentane has also been studied over Pt-Ru bimetallic catalysts.499... 

The darkness associated with dense interstellar clouds is caused by dust particles of size =0.1 microns, which are a common ingredient in interstellar and circum-stellar space, taking up perhaps 1% of the mass of interstellar clouds with a fractional number density of 10-12. These particles both scatter and absorb external visible and ultraviolet radiation from stars, protecting molecules in dense clouds from direct photodissociation via external starlight. They are rather less protective in the infrared, and are quite transparent in the microwave.6 The chemical nature of the dust particles is not easy to ascertain compared with the chemical nature of the interstellar gas broad spectral features in the infrared have been interpreted in terms of core-mantle particles, with the cores consisting of two populations, one of silicates and one of carbonaceous, possibly graphitic material. The mantles, which appear to be restricted to dense clouds, are probably a mixture of ices such as water, carbon monoxide, and methanol.7... 

On adding one drop of nitrobenzene to an equimolar, ten millimolar, mixture of the other two solids a violent reaction produced gas and carbonaceous material. This was initially attributed to the oxidative powers of the nitrobenzene [1], However, diphenylacetylene is a high energy molecule, AH°f +315 kJ/mole. At least 98% of the potential chemical energy present will have been the diphenylacetylene. It is probable that the nitrobenzene merely provided a liquid phase in which the aluminium chloride could interact with the acetylene, catalysing reaction beyond the intended azulene dimerisation product[2]. 

The authors chose pyruvic acid as their model compound this C3 molecule plays a central role in the metabolism of living cells. It was recently synthesized for the first time under hydrothermal conditions (Cody et al., 2000). Hazen and Deamer carried out their experiments at pressures and temperatures similar to those in hydrothermal systems (but not chosen to simulate such systems). The non-enzymatic reactions, which took place in relatively concentrated aqueous solutions, were intended to identify the subsequent self-selection and self-organisation potential of prebiotic molecular species. A considerable series of complex organic molecules was tentatively identified, such as methoxy- or methyl-substituted methyl benzoates or 2, 3, 4-trimethyl-2-cyclopenten-l-one, to name only a few. In particular, polymerisation products of pyruvic acid, and products of consecutive reactions such as decarboxylation and cycloaddition, were observed the expected tar fraction was not found, but water-soluble components were found as well as a chloroform-soluble fraction. The latter showed similarities to chloroform-soluble compounds from the Murchison carbonaceous chondrite (Hazen and Deamer, 2007). 

UV radiation hypothetical, but so is the transport of molecules from outer space to Earth. Recent analyses of the Murchison meteorite by two scientists from the University of Arizona, Tucson (Cronin and Pizzarello, 1997 Cronin, 1998) have shown it to contain the four stereoisomeric amino acids DL-a-methylisoleucine and DL-a-methylalloisoleucine. In both cases, the L-enantiomer is present in a clear excess (7.0 and 9.1%). Similar results were obtained for two other a-methyl amino acids, isovaline and a-methylvaline. Contamination by terrestrial proteins can be ruled out, since these amino acids are either not found in nature or are present in only very small amounts. Since the carbonaceous chondrites are thought to have been formed around 4.5 billion years ago (see Sect. 3.3.2), the amino acids referred to above must have been subject to one or more asymmetric effects prior to biogenesis. 

The acidic character of 5A zeolite as a function of the calcium content has been explored by different techniques propylene adsorption experiments, ammonia thermodesorption followed by microgravimetry and FTIR spectroscopy. Propylene is chemisorbed and slowly transformed in carbonaceous compounds (coke) which remain trapped inside the zeolite pores. The coke quantities increase with the Ca2+ content. Olefin transformation results from an oligomerization catalytic process involving acidic adsorption sites. Ammonia thermodesorption studies as well as FTIR experiments have revealed the presence of acidic sites able to protonate NH3 molecules. This site number is also correlated to the Ca2+ ion content. As it has been observed for FAU zeolite exchanged with di- or trivalent metal cations, these sites are probably CaOH+ species whose vas(OH) mode have a spectral signature around 3567 cm"1. 

The formation of heavy carbonaceous compounds in 5A calcium exchanged zeolites depends on the calcium content. These zeolites are able to protonated ammonia molecules in ammonium ions. This Bronsted acidity results from the presence of CaOH+ species which are formed by water dissociation on Ca2+ ions and have an IR signature at 3515 cm"1. 

Microprobe laser desorption laser ionisation mass spectrometry (/xL2MS) is used to provide spatial resolution and identification of organic molecules across a meteorite sample. Tracking the chemical composition across the surface of the meteorite requires a full mass spectrum to be measured every 10 p,m across the surface. The molecules must be desorbed from the surface with minimal disruption to their chemical structure to prevent fragmentation so that the mass spectrum consists principally of parent ions. Ideally, the conventional electron bombardment ionisation technique can be replaced with an ionisation that is selective to the carbonaceous species of interest to simplify the mass spectrum. Most information will be obtained if small samples are used so that sensitivity levels should be lower than attomolar (10—18 M) fewer than 1000 molecules can be detected and above all it must be certain that the molecules came from the sample and are not introduced by the instrument itself. 

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