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NTRODUCING ALKANES AND CYCLOALKANES

This is an introductory page about alkanes such as methane, ethane, propane, butane and the rest. It deals with their formulae and isomerism, their physical properties, and an introduction to their chemical reactivity.

What are alkanes and cycloalkanes?


Alkanes Formulae Alkanes are the simplest family of hydrocarbons - compounds containing carbon and hydrogen only. They only contain carbon-hydrogen bonds and carbon-carbon single bonds. The first six are: methane ethane propane butane pentane hexane CH4 C2H6 C3H8 C4H10 C5H12 C6H14

You can work out the formula of any of them using: CnH2n+2 Isomerism All the alkanes with 4 or more carbon atoms in them show structural isomerism. This means that there are two or more different structural formulae that you can draw for each molecular formula. For example, C4H10 could be either of these two different molecules:

These are called respectively butane and 2-methylpropane.


Note: If you aren't confident about naming organic compounds, the various ways of drawing organic compounds, or structural isomerism, then you really ought to follow these links before you go on. You should read the whole of the page about drawing organic molecules, but there is no need to read the other two beyond where they talk about alkanes. Use the BACK button on your browser to return to this page.

Cycloalkanes Cycloalkanes again only contain carbon-hydrogen bonds and carbon-carbon single bonds, but this time the carbon atoms are joined up in a ring. The smallest cycloalkane is cyclopropane.

If you count the carbons and hydrogens, you will see that they no longer fit the general formula CnH2n+2. By joining the carbon atoms in a ring, you have had to lose two hydrogen atoms.

You are unlikely to ever need it, but the general formula for a cycloalkane is C nH2n. Don't imagine that these are all flat molecules. All the cycloalkanes from cyclopentane upwards exist as "puckered rings". Cyclohexane, for example, has a ring structure which looks like this:

This is known as the "chair" form of cyclohexane - from its shape which vaguely resembles a chair.

Note: This molecule is constantly changing, with the atom on the left which is currently pointing down flipping up, and the one on the right flipping down. During the process, another (slightly less stable) form of cyclohexane is formed known as the "boat" form. In this arrangement, both of these atoms are either pointing up or down at the same time.

Physical Properties
Boiling Points The facts

The boiling points shown are all for the "straight chain" isomers where there are more than one.

Notice that the first four alkanes are gases at room temperature. Solids don't start to appear until about C17H36. You can't be more precise than that because each isomer has a different melting and boiling point. By the time you get 17 carbons into an alkane, there are unbelievable numbers of isomers! Cycloalkanes have boiling points which are about 10 - 20 K higher than the corresponding straight chain alkane. Explanations There isn't much electronegativity difference between carbon and hydrogen, so there is hardly any bond polarity. The molecules themselves also have very little polarity. A totally symmetrical molecule like methane is completely non-polar.
Note: If you aren't sure about electronegativity and polarity, then you really ought to follow this link before you go on. Use the BACK button on your browser to return to this page.

This means that the only attractions between one molecule and its neighbours will be Van der Waals dispersion forces. These will be very small for a molecule like methane, but will increase as the molecules get bigger. That's why the boiling points of the alkanes increase with molecular size.
Note: If you aren't sure about Van der Waals forces, then you should follow this link before you go on. Use the BACK button on your browser to return to this page.

Where you have isomers, the more branched the chain, the lower the boiling point tends to be. Van der Waals dispersion forces are smaller for shorter molecules, and only operate over very short distances between one molecule and its neighbours. It is more difficult for short fat molecules (with lots of branching) to lie as close together as long thin ones. For example, the boiling points of the three isomers of C5H12 are:

boiling point (K) pentane 2-methylbutane 2,2-dimethylpropane 309.2 301.0 282.6

The slightly higher boiling points for the cycloalkanes are presumably because the molecules can get closer together because the ring structure makes them tidier and less "wriggly"!

Solubility The facts What follows applies equally to alkanes and cycloalkanes. Alkanes are virtually insoluble in water, but dissolve in organic solvents. The liquid alkanes are good solvents for many other covalent compounds. Explanations Solubility in water When a molecular substance dissolves in water, you have to

break the intermolecular forces within the substance. In the case of the alkanes, these are Van der Waals dispersion forces. break the intermolecular forces in the water so that the substance can fit between the water molecules. In water the main intermolecular attractions are hydrogen bonds.

Note: If you aren't sure about hydrogen bonds, then you should follow this link before you go on. Use the BACK button on your browser to return to this page.

Breaking either of these attractions costs energy, although the amount of energy to break the Van der Waals dispersion forces in something like methane is pretty negligible. That isn't true of the hydrogen bonds in water, though.

As something of a simplification, a substance will dissolve if there is enough energy released when new bonds are made between the substance and the water to make up for what is used in breaking the original attractions. The only new attractions between the alkane and water molecules are Van der Waals. These don't release anything like enough energy to compensate for what you need to break the hydrogen bonds in water. The alkane doesn't dissolve.
Note: The reason that this is a simplification is that you also have to consider entropy changes when things dissolve. If you don't yet know about entropy, don't worry about it!

Solubility in organic solvents In most organic solvents, the main forces of attraction between the solvent molecules are Van der Waals - either dispersion forces or dipole-dipole attractions. That means that when an alkane dissolves in an organic solvent, you are breaking Van der Waals forces and replacing them by new Van der Waals forces. The two processes more or less cancel each other out energetically - so there isn't any barrier to solubility.

Chemical Reactivity
Alkanes Alkanes contain strong carbon-carbon single bonds and strong carbon-hydrogen bonds. The carbon-hydrogen bonds are only very slightly polar and so there aren't any bits of the molecules which carry any significant amount of positive or negative charge which other things might be attracted to. For example, you will find (or perhaps already know) that many organic reactions start because an ion or a polar molecule is attracted to a part of an organic molecule which carries some positive or negative charge. This doesn't happen with alkanes, because alkane molecules don't have this separation of charge. The net effect is that alkanes have a fairly restricted set of reactions. You can

burn them - destroying the whole molecule; react them with some of the halogens, breaking carbon-hydrogen bonds; crack them, breaking carbon-carbon bonds.

These reactions are all covered on separate pages if you go to the alkanes menu (see below). Cycloalkanes Cycloalkanes are very similar to the alkanes in reactivity, except for the very small ones - especially cyclopropane. Cyclopropane is much more reactive than you would expect. The reason has to do with the bond angles in the ring. Normally, when carbon forms four single bonds, the bond angles are about 109.5. In cyclopropane, they are 60.

With the electron pairs this close together, there is a lot of repulsion between the bonding pairs joining the carbon atoms. That makes the bonds easier to break. The effect of this is explored on the page about reactions of these compounds with halogens which you can access from the alkanes menu below.

THE COMBUSTION OF ALKANES AND CYCLOALKANES


This page deals briefly with the combustion of alkanes and cycloalkanes. In fact, there is very little difference between the two.

Complete combustion
Complete combustion (given sufficient oxygen) of any hydrocarbon produces carbon dioxide and water.

Equations It is quite important that you can write properly balanced equations for these reactions, because they often come up as a part of thermochemistry calculations. Don't try to learn the equations - there are far too many possibilities. Work them out as you need them. Some are easier than others. For example, with alkanes, the ones with an even number of carbon atoms are marginally harder than those with an odd number! For example, with propane (C3H8), you can balance the carbons and hydrogens as you write the equation down. Your first draft would be:

Counting the oxygens leads directly to the final version:

With butane (C4H10), you can again balance the carbons and hydrogens as you write the equation down.

Counting the oxygens leads to a slight problem - with 13 on the right-hand side. The simple trick is to allow yourself to have "six-and-a-half" O2 molecules on the left.

If that offends you, double everything:

Note: You might well come across either version of these equations. The ones with the halves left in are often used in calculation work. Forgive me if you find this last bit on equations unbearably trivial - not everybody does! Just be grateful that you have been well taught.

Trends The hydrocarbons become harder to ignite as the molecules get bigger. This is because the bigger molecules don't vaporise so easily - the reaction is much better if the oxygen

and the hydrocarbon are well mixed as gases. If the liquid isn't very volatile, only those molecules on the surface can react with the oxygen. Bigger molecules have greater Van der Waals attractions which makes it more difficult for them to break away from their neighbours and turn to a gas.
Note: If you aren't sure about Van der Waals forces, then you should follow this link before you go on. Use the BACK button on your browser to return to this page.

Provided the combustion is complete, all the hydrocarbons will burn with a blue flame. However, combustion tends to be less complete as the number of carbon atoms in the molecules rises. That means that the bigger the hydrocarbon, the more likely you are to get a yellow, smoky flame.

Incomplete combustion
Incomplete combustion (where there isn't enough oxygen present) can lead to the formation of carbon or carbon monoxide. As a simple way of thinking about it, the hydrogen in the hydrocarbon gets the first chance at the oxygen, and the carbon gets whatever is left over! The presence of glowing carbon particles in a flame turns it yellow, and black carbon is often visible in the smoke. Carbon monoxide is produced as a colourless poisonous gas. Why carbon monoxide is poisonous Oxygen is carried around the blood by haemoglobin (US: hemoglobin). Unfortunately carbon monoxide binds to exactly the same site on the haemoglobin that oxygen does. The difference is that carbon monoxide binds irreversibly - making that particular molecule of haemoglobin useless for carrying oxygen. If you breath in enough carbon monoxide you will die from a sort of internal suffocation.

Note: There is more about haemoglobin towards the bottom of the page about complex ions. If you want some description of catalytic converters which help to remove carbon monoxide and some other pollutants, see the introductory page on catalysis.

If you want full details about any of the environmental problems associated with burning hydrocarbons, you can't do better than explore the excellent US Environmental Protection Agency site. If you want details about the role of hydrocarbons in the formation of photochemical smog, a Google search on photochemical smog will quickly lead you to some detailed chemistry. There is a Google search box on the Main Menu (link below). Don't forget that you want to search the whole web - not chemguide. Use the BACK button (or the HISTORY or GO menus) on your browser if you want to return to this page later.

THE HALOGENATION OF ALKANES AND CYCLOALKANES


This page describes the reactions between alkanes and cycloalkanes with the halogens fluorine, chlorine, bromine and iodine - mainly concentrating on chlorine and bromine.

Alkanes
The reaction between alkanes and fluorine This reaction is explosive even in the cold and dark, and you tend to get carbon and hydrogen fluoride produced. It is of no particular interest. For example:

The reaction between alkanes and iodine Iodine doesn't react with the alkanes to any extent - at least, under normal lab conditions. The reactions between alkanes and chlorine or bromine There is no reaction in the dark. In the presence of a flame, the reactions are rather like the fluorine one - producing a mixture of carbon and the hydrogen halide. The violence of the reaction drops considerably as you go from fluorine to chlorine to bromine. The interesting reactions happen in the presence of ultra-violet light (sunlight will do). These are photochemical reactions, and happen at room temperature.

We'll look at the reactions with chlorine. The reactions with bromine are similar, but rather slower. Methane and chlorine Substitution reactions happen in which hydrogen atoms in the methane are replaced one at a time by chlorine atoms. You end up with a mixture of chloromethane, dichloromethane, trichloromethane and tetrachloromethane.

Note: Follow this link if you aren't happy about naming organic compounds. Use the BACK button on your browser to return to this page.

The original mixture of a colourless and a green gas would produce steamy fumes of hydrogen chloride and a mist of organic liquids. All of the organic products are liquid at room temperature with the exception of the chloromethane which is a gas. If you were using bromine, you could either mix methane with bromine vapour, or bubble the methane through liquid bromine - in either case, exposed to UV light. The original mixture of gases would, of course, be red-brown rather than green. You wouldn't choose to use these reactions as a means of preparing these organic compounds in the lab because the mixture of products would be too tedious to separate. The mechanisms for the reactions are explained on separate pages.
Note: If you want the methane-chlorine mechanism, follow this link. If you want the methane-bromine mechanism, follow this one.

Use the BACK button on your browser to return to this page.

Larger alkanes and chlorine You would again get a mixture of substitution products, but it is worth just looking briefly at what happens if only one of the hydrogen atoms gets substituted (monosubstitution) just to show that things aren't always as straightforward as they seem! For example, with propane, you could get one of two isomers:

Note: If you aren't sure about isomerism, you might like to follow this link. Use the BACK button on your browser to return to this page.

If chance was the only factor, you would expect to get 3 times as much of the isomer with the chlorine on the end. There are 6 hydrogens that could get replaced on the end carbon atoms compared with only 2 in the middle. In fact, you get about the same amount of each of the two isomers. If you use bromine instead of chlorine, the great majority of the product is where the bromine is attached to the centre carbon atom. The reasons for this are beyond UK A level chemistry.

Cycloalkanes
The reactions of the cycloalkanes are generally just the same as the alkanes, with the exception of the very small ones - particularly cyclopropane.

The extra reactivity of cyclopropane In the presence of UV light, cyclopropane will undergo substitution reactions with chlorine or bromine just like a non-cyclic alkane. However, it also has the ability to react in the dark. In the absence of UV light, cyclopropane can undergo addition reactions in which the ring is broken. For example, with bromine, cyclopropane gives 1,3-dibromopropane.

This can still happen in the presence of light - but you will get substitution reactions as well. The ring is broken because cyclopropane suffers badly from ring strain. The bond angles in the ring are 60 rather than the normal value of about 109.5 when the carbon makes four single bonds. The overlap between the atomic orbitals in forming the carbon-carbon bonds is less good than it is normally, and there is considerable repulsion between the bonding pairs. The system becomes more stable if the ring is broken.

CRACKING ALKANES
This page describes what cracking is, and the differences between catalytic cracking and thermal cracking used in the petrochemical industry.

Cracking
What is cracking? Cracking is the name given to breaking up large hydrocarbon molecules into smaller and more useful bits. This is achieved by using high pressures and temperatures without a catalyst, or lower temperatures and pressures in the presence of a catalyst. The source of the large hydrocarbon molecules is often the naphtha fraction or the gas oil fraction from the fractional distillation of crude oil (petroleum). These fractions are obtained from the distillation process as liquids, but are re-vaporised before cracking.

There isn't any single unique reaction happening in the cracker. The hydrocarbon molecules are broken up in a fairly random way to produce mixtures of smaller hydrocarbons, some of which have carbon-carbon double bonds. One possible reaction involving the hydrocarbon C15H32 might be:

Or, showing more clearly what happens to the various atoms and bonds:

This is only one way in which this particular molecule might break up. The ethene and propene are important materials for making plastics or producing other organic chemicals. The octane is one of the molecules found in petrol (gasoline).

Catalytic cracking Modern cracking uses zeolites as the catalyst. These are complex aluminosilicates, and are large lattices of aluminium, silicon and oxygen atoms carrying a negative charge. They are, of course, associated with positive ions such as sodium ions. You may have come across a zeolite if you know about ion exchange resins used in water softeners. The alkane is brought into contact with the catalyst at a temperature of about 500C and moderately low pressures. The zeolites used in catalytic cracking are chosen to give high percentages of hydrocarbons with between 5 and 10 carbon atoms - particularly useful for petrol (gasoline). It also produces high proportions of branched alkanes and aromatic hydrocarbons like benzene.

For UK A level (and equivalent) purposes, you aren't expected to know how the catalyst works, but you may be expected to know that it involves an ionic intermediate.

Note: You should check your syllabus to find out exactly what you need to know. If you are studying a UK-based syllabus and haven't got one, follow this link. Use the BACK button on your browser to return quickly to this page.

The zeolite catalyst has sites which can remove a hydrogen from an alkane together with the two electrons which bound it to the carbon. That leaves the carbon atom with a positive charge. Ions like this are called carbonium ions (or carbocations). Reorganisation of these leads to the various products of the reaction.

Note: If you are interested in other examples of catalysis in the petrochemical industry, you should follow this link. It will lead you to information on reforming and isomerisation (as well as a repeat of what you have just read about catalytic cracking). Use the BACK button on your browser if you want to return quickly to this page.

Thermal cracking In thermal cracking, high temperatures (typically in the range of 450C to 750C) and pressures (up to about 70 atmospheres) are used to break the large hydrocarbons into smaller ones. Thermal cracking gives mixtures of products containing high proportions of hydrocarbons with double bonds - alkenes.

Warning! This is a gross oversimplification, and is written to satisfy the needs of one of the UK A level Exam Boards (AQA). In fact, there are several versions of thermal cracking designed to produce different mixtures of products. These use completely different sets of conditions. If you need to know about thermal cracking in detail, a Google search on thermal cracking will throw up lots of useful leads. Be careful to go to industry (or similarly reliable) sources. You will find a Google search box at the bottom of the Main Menu (link below). Remember to search the whole web rather than Chemguide otherwise you will just end up back here again!

Thermal cracking doesn't go via ionic intermediates like catalytic cracking. Instead, carbon-carbon bonds are broken so that each carbon atom ends up with a single electron. In other words, free radicals are formed.

Reactions of the free radicals lead to the various products.