Ethylene 2 molecules

The barriers in Fig, 4-10 are high because it is difficult to twist ethylene out of its normal planar conformation. The energy is the same at the midpoint and the end points in Fig, 4-10 because, on twisting an ethylene molecule 180" out of its normal conformation, one obtains a molecule that is indistinguishable from the original. The molecule has 2-foid torsional syinnteiry. 

It is a property of linear, homogeneous differential equations, of which the Schroedinger equation is one. that a solution multiplied by a constant is a solution and a solution added to or subtracted from a solution is also a solution. If the solutions Pi and p2 in Eq. set (6-13) were exact molecular orbitals, id v would also be exact. Orbitals p[ and p2 are not exact molecular orbitals they are exact atomic orbitals therefore. j is not exact for the ethylene molecule. 

Contrast the Diels-Alder reaction with a cycloaddition reaction that looks superfl cially similar the combination of two ethylene molecules to give cyclobutane... 

Figure 10 12 shows the interaction between the HOMO of one ethylene molecule and the LUMO of another In particular notice that two of the carbons that are to become ct bonded to each other m the product experience an antibondmg interaction during the cycloaddition process This raises the activation energy for cycloaddition and leads the reaction to be classified as a symmetry forbidden reaction Reaction were it to occur would take place slowly and by a mechanism m which the two new ct bonds are formed m separate steps rather than by way of a concerted process involving a sm gle transition state... 

Polyethylene (PE) is a genetic name for a large family of semicrystalline polymers used mostiy as commodity plastics. PE resins are linear polymers with ethylene molecules as the main building block they are produced either in radical polymerization reactions at high pressures or in catalytic polymerization reactions. Most PE molecules contain branches in thek chains. In very general terms, PE stmcture can be represented by the following formula ... 

Fig. 22.1. (a) The ethylene molecule or monomer (b) the monomer in the activated state, ready to polymerise with others (<)-(f) the ethylene polymer ("polyethylene") the chain length is limited by the addition of terminators like —OH. The DP is the number of monomer units in the chain. 

Polyethylene, a linear polymer, is made by an addition reaction. It is started with an initiator, such as FIjOj, which gives free, and very reactive —OFI radicals. One of these breaks the double-bond of an ethylene molecule, C2FI4, when it is heated under pressure, to give... 

The left-hand end of the activated monomer is sealed off by the OH terminator, but the right-hand end (with the star) is aggressively reactive and now attacks another ethylene molecule, as we illustrated earlier in Fig. 22.1. The process continues, forming a longer and longer molecule by a sort of chain reaction. The —OH used to start a chain will, of course, terminate one just as effectively, so excess initiator leads to short chains. As the monomer is exhausted the reaction slows down and finally stops. The DP depends not only on the amount of initiator, but on the pressure and temperature as well. 

The remaining AOs are the four H 1, two C 1, and four C 2p orbitals. All lie in the molecular plane. Only two combinations of the C 2s and H U orbitals meet the molecular symmetry requirements. One of these, nearest-neighbor atoms. No other combination corresponds to the symmetry of the ethylene molecule. 

Frontier orbital theory also provides the basic framework for analysis of the effect that the symmetiy of orbitals has upon reactivity. One of the basic tenets of MO theory is that the symmetries of two orbitals must match to permit a strong interaction between them. This symmetry requirement, when used in the context of frontier orbital theory, can be a very powerful tool for predicting reactivity. As an example, let us examine the approach of an allyl cation and an ethylene molecule and ask whether the following reaction is likely to occur. 

The complementary relationship between thermal and photochemical reactions can be illustrated by considering some of the same reaction types discussed in Chapter 11 and applying orbital symmetry considerations to the photochemical mode of reaction. The case of [2ti + 2ti] cycloaddition of two alkenes can serve as an example. This reaction was classified as a forbidden thermal reaction (Section 11.3) The correlation diagram for cycloaddition of two ethylene molecules (Fig. 13.2) shows that the ground-state molecules would lead to an excited state of cyclobutane and that the cycloaddition would therefore involve a prohibitive thermal activation energy. 

HOMO of one ethylene molecule and the LUMO of another do not have the proper symmetry to permit two CT bonds to be formed in the same transition state for concerted cycloaddition. 

In order to understand the physical properties and reactivity patterns of S-N compounds it is particularly instructive to compare their electronic structures with those of the analogous organic systems.On a qualitative level, the simplest comparison is that between the hypothetical HSNH radical and the ethylene molecule each of these units can be considered as the building blocks from which conjugated -S=N- or -CH=CH-systems can be constructed. To a first approximation the (j-framework of... 

The result of this cts-insertion is that a vacant site is left behind, and this can be occupied by another ethylene molecule and steps (a) and (b) repeated indefinitely. 

Ethylene is sometimes known as the king of petrochemicals hecause more commercial chemicals are produced from ethylene than from any other intermediate. This unique position of ethylene among other hydrocarbon intermediates is due to some favorable properties inherent in the ethylene molecule as well as to technical and economical factors. These could be summarized in the following ... 

I Propagation Polymerization occurs when the carbon radical formed in the initiation step adds to another ethylene molecule to yield another radical. 

The shape of the ethylene molecule has been learned by a variety of types of experiments. Ethylene is a planar molecule—the four hydrogen and the two carbon atoms all lie in one plane. The implication of this experimental fact is that there is a rigidity of the double bond which prevents a twisting movement of one of the CHj groups relative to the other. Rotation of one CHt group relative to the other—with the C—C bond as an axis—must be energetically restricted or the molecule would not retain this flat form. 

Let us now apply these results to the ethylene molecule (Fig. 14), for which we attempt to build the bonding molecular orbitals. Clearly there are three symmetry planes. Two of these are of special interest... 

Ethylene molecules can join together into immensely long chains, converting the double bond into a single bond as they join to become polyethylene. 

Unsaturated organic molecules, such as ethylene, can be chemisorbed on transition metal surfaces in two ways, namely in -coordination or di-o coordination. As shown in Fig. 2.24, the n type of bonding of ethylene involves donation of electron density from the doubly occupied n orbital (which is o-symmetric with respect to the normal to the surface) to the metal ds-hybrid orbitals. Electron density is also backdonated from the px and dM metal orbitals into the lowest unoccupied molecular orbital (LUMO) of the ethylene molecule, which is the empty asymmetric 71 orbital. The corresponding overall interaction is relatively weak, thus the sp2 hybridization of the carbon atoms involved in the ethylene double bond is retained. 

In the first investigation 20), ethylene in the collision chamber was bombarded with positive ions, and the intensities of the fragment ions, obtained after the charge exchange, were recorded. The mass spectra were thus not normalized. At low pressure only primary ions were observed that were formed from ethylene in the charge exchange, but at higher pressures also secondary and tertiary ions were obtained as a result of ion-molecule reactions between the primary ions and the ethylene molecules in the collision chamber. 

An estimate for the G value for ethylene removal by ionic reactions can be made from the ion intensities of the 5-torr spectrum. First, the total intensity of accounted ions is set equal to unity. Then we multiply the intensities of the given ions by the number of ethylene molecules used up in their formation. Some of the weighing factors used were ... 

Proceeding in this manner one finds that some 4.5 ethylene molecules are used up per ion formed. Using the established value of 3.88 ion pairs per 100 e.v. we find a G value for ethylene used up by ionic reactions at 5 torr pressure G( — AC2H4) 17. This shows that ionic mechanisms account for the major part of the ethylene consumed in gas phase radiolysis. 

Radiolytic ethylene destruction occurs with a yield of ca. 20 molecules consumed/100 e.v. (36, 48). Products containing up to six carbons account for ca. 60% of that amount, and can be ascribed to free radical reactions, molecular detachments, and low order ion-molecule reactions (32). This leaves only eight molecules/100 e.v. which may have formed ethylene polymer, corresponding to a chain length of only 2.1 molecules/ ion. Even if we assumed that ethylene destruction were entirely the result of ionic polymerization, only about five ethylene molecules would be involved per ion pair. The absence of ionic polymerization can also be demonstrated by the results of the gamma ray initiated polymerization of ethylene, whose kinetics can be completely explained on the basis of conventional free radical reactions and known rate constants for these processes (32). An increase above the expected rates occurs only at pressures in excess of ca. 20 atmospheres (10). The virtual absence of ionic polymerization can be regarded as one of the most surprising aspects of the radiation chemistry of ethylene. 

Neither methyl nor ethyl fluoride gave the corresponding cations when treated with SbFs. At low temperatures, methyl fluoride gave chiefly the methylated sulfur dioxide salt, (CH3OSO) ShF while ethyl fluoride rapidly formed the rert-butyl and ferf-hexyl cations by addition of the initially formed ethyl cation to ethylene molecules also formed ° At room temperature, methyl fluoride also gave the tert-butyl cation. In accord with the stability order, hydride ion is abstracted from alkanes by super acid most readily from tertiary and least readily from primary positions. 

The accuracy of LDF calculations in the prediction of surface geometries not only holds for clean metal surfaces such as the W(001) surface discussed above, but is also found for adsorbates such as H (27), O (28), and S (29) on Ni(OOl) surfaces. Rather than going into detail on clean and adsorbate covered surfaces, we will now focus on the description of the C-C bond by LDF theory. To this end, we first discuss a layer of condensed benzene rings, i.e. a graphite monolayer, and then focus our attention on the ethylene molecule. 

Rotational Barrier in Ethylene. It is well known that the rotational barrier of the ethylene molecule cannot be adequately described by a single reference Hartree-Fock calculation SCF calculations on this level resulted in values of 126 kcal/mole (30) and 129 kcal/mole (31) whereas the experimental value is 65 kcal/mole (32). Open-shell ab initio calculations of double zeta+polarization quality give the more acceptable value of 48 kcal/mole (33). Inclusion of correlation such as in CEPA calculations yield theoretical results within the experimental error bar (34), albeit at a considerable computational cost. 

Using local spin density functional (LSDF) theory, we obtain 70 kcal/mole for the rotational barrier of the ethylene molecule (35). In these calculations, we use the equivalent of a double-zeta+polarization basis set, i.e. for C two 2s functions. 

Table I. Bond lengths (in A) and bond angles (in degrees) for the ethylene molecule...

Triethyiaiuminum, Al (CH2 CH3)3, has long been used in the chemical indushy in the production of alkenes— hydrocarbons that have CDC double bonds. In the presence of triethyiaiuminum, two or more ethylene molecules... 

The simplest of all polymers is polyethylene, formed by bonding many ethylene molecules together in long chains containing 500 or more repeating CH2 groups. 

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