Jaycee Angeline C.

Lorenzo IV-Fermi
Aromatic compounds These are compounds based on benzene rings. What are arenes? Arenes are aromatic hydrocarbons. The term "aromatic" originally referred to their pleasant smells, but now implies a particular sort of delocalised bonding (see below). The arenes you are likely to meet at this level are based on benzene rings. The simplest of them is benzene itself, C6H6. The next simplest is methylbenzene (old name: toluene) which has one of the hydrogen atoms attached to the ring replaced by a methyl group C6H5CH3. The structure of benzene The structure of benzene is covered in detail in two pages in the organic bonding section of this site. It is important to understand these thoroughly to make sense of benzene and methylbenzene chemistry. Unless you have read these pages recently, you should spend some time on them now before you go any further on this page. What you need to understand about benzene is: Benzene, C6H6, is a planar molecule containing a ring of six carbon atoms each with a hydrogen atom attached. The six carbon atoms form a perfectly regular hexagon. All the carbon-carbon bonds have exactly the same lengths - somewhere between single and double bonds. There are delocalised electrons above and below the plane of the ring. The presence of the delocalised electrons makes benzene particularly stable. Benzene resists addition reactions because that would involve breaking the delocalisation and losing that stability. Benzene is represented by this symbol, where the circle represents the delocalised electrons, and each corner of the hexagon has a carbon atom with a hydrogen attached. Methylbenzene just has a methyl group attached to the benzene ring - replacing one of the hydrogen atoms. Attached groups are often drawn at the top of the ring, but you may occasionally find them drawn in other places with the ring rotated. Physical properties Boiling points In benzene, the only attractions between neighbouring molecules are van der Waals dispersion forces. There is no permanent dipole on the molecule. Benzene boils at 80C - rather higher than other hydrocarbons of similar molecular size (pentane and hexane, for example). This is presumably due to the ease with which temporary dipoles can be set up involving the delocalised electrons. Methylbenzene boils at 111C. It is a bigger molecule and so the van der Waals dispersion forces will be bigger.

Methylbenzene also has a small permanent dipole, so there will be dipole-dipole attractions as well as dispersion forces. The dipole is due to the CH3 group's tendency to "push" electrons away from itself. This also affects the reactivity of methylbenzene (see below). Melting points You might have expected that methylbenzene's melting point would be higher than benzene's as well, but it isn't - it is much lower! Benzene melts at 5.5C; methylbenzene at -95C. Molecules must pack efficiently in the solid if they are to make best use of their intermolecular forces. Benzene is a tidy, symmetrical molecule and packs very efficiently. The methyl group sticking out in methylbenzene tends to disrupt the closeness of the packing. If the molecules aren't as closely packed, the intermolecular forces don't work as well and so the melting point falls. Solubility in water The arenes are insoluble in water. Benzene is quite large compared with a water molecule. In order for benzene to dissolve it would have to break lots of existing hydrogen bonds between water molecules. You also have to break the quite strong van der Waals dispersion forces between benzene molecules. Both of these cost energy. The only new forces between the benzene and the water would be van der Waals dispersion forces. These aren't as strong as hydrogen bonds (or the original dispersion forces in the benzene), and so you wouldn't get much energy released when they form. It simply isn't energetically profitable for benzene to dissolve in water. It would, of course, be even worse for larger arene molecules. Reactivity Benzene It has already been pointed out above that benzene is resistant to addition reactions. Adding something new to the ring would need you to use some of the delocalised electrons to form bonds with whatever you are adding. That results in a major loss of stability as the delocalisation is broken. Instead, benzene mainly undergoes substitution reactions - replacing one or more of the hydrogen atoms by something new. That leaves the delocalised electrons as they were. Methylbenzene You have to consider the reactivity of something like methylbenzene in two distinct bits: The tendency of the CH3 group to "push" electrons away from itself also has an effect on the ring, making methylbenzene react more quickly than benzene itself. You will find this explored in other pages in this section as well. The structure of chlorobenzene There is an interaction between the delocalised electrons in the benzene ring and one of the lone pairs on the chlorine atom. This delocalisation is by no means complete, but it does have a significant effect on the properties of both the carbon-chlorine bond and the polarity of the molecule.

The delocalisation introduces some extra bonding between the carbon and the chlorine, making the bond stronger. This has a major effect on the reactions of compounds like chlorobenzene. There is also some movement of electrons away from the chlorine towards the ring. Chlorine is quite electronegative and usually draws electrons in the carbonchlorine bond towards itself. In this case, this is offset to some extent by the movement of electrons back towards the ring in the delocalisation. The molecule is less polar than you would otherwise have expected. Physical properties Boiling points Chlorobenzene, bromobenzene and iodobenzene are all oily liquids. The boiling points increase as the halogen atom gets bigger. boiling point (C) C6H5Cl 132 C6H5Br 156 C6H5I 189 The main attractions between the molecules will be van der Waals dispersion forces. These increase as the number of electrons in the molecule increases. This is the reason that the boiling points increase as the halogen atom gets bigger. There will also be permanent dipole-dipole attractions involved in the chlorobenzene and bromobenzene, but very little in the iodobenzene. Iodine has much the same electronegativity as carbon. These dipole-dipole attractions must be very unimportant relative to the dispersion forces because the most polar molecule (the chlorobenzene) has the lowest boiling point of the three. Solubility in water The aryl halides are insoluble in water. They are denser than water and form a separate lower layer. The molecules are quite large compared with a water molecule. In order for chlorobenzene to dissolve it would have to break lots of existing hydrogen bonds between water molecules. You also have to break the quite strong van der Waals dispersion forces between chlorobenzene molecules. Both of these cost energy. The only new forces between the chlorobenzene and the water would be van der Waals dispersion forces. These aren't as strong as hydrogen bonds (or the original dispersion forces in the chlorobenzene), and so you wouldn't get much energy released when they form. It simply isn't energetically profitable for chlorobenzene (and the others) to dissolve in water. Aromatic hydrocarbons are one of the three classes of compounds found in petroleum. They are less abundant than the alkanes and cycloalkanes, amounting to only a few percent of the total, but they are quite important commercially. All aromatic hydrocarbons contain a benzene ring. You will recall from the discussion onresonance that benzene, C6H6 contains a flat ring of six carbon atoms joined by bonds which are intermediate in character between single and double bonds. The benzene ring is usually indicated by

In the latter structure the lines represent CC bonds, but carbon and hydrogen atoms, as well as CH bonds, have been omitted. The benzene ring is very stable, surviving unchanged in most chemical reactions. It is very different in reactivity and shape from the puckered six-membered rings found in cycloalkanes. Below are 3D Jmol models of both cyclohexane and benzene. Examples of aromatic hydrocarbons found in crude oil are

Note that the three xylenes are also isomers. Compounds containing two benzene rings joined together, such as naphthalene, are also found in crude oil, though they are much rarer than benzene-related compounds.

Aromatic hydrocarbons are much more common in coal than in petroleum, though in the United States they are mostly manufactured from the latter. In addition to their use in motor fuel, they may be made into dyes, plastics, explosives, detergents, insecticides, medicines, and many 12 other products. In 2000, a total of 6.74 10 liters of benzene were produced in the US, after compensation for [1] exportation and importation . Some aromatic compounds, benzene among them, are toxic. The compound 1,2-benzopyrene was the cause of the first demonstrated case of occupational disease.

During the eighteenth century chimney sweeps in London were found to have extremely high rates of skin cancer relative to the average person. This was eventually traced to the carcinogenic (cancer-causing) properties of 1,2benzopyrene in the soot which coated the insides of the chimneys they cleaned. Small quantities of the compound were produced by inefficient combustion of coal in the fireplaces used to heat London houses.