INTRODUCING ALCOHOLS

This page explains what alcohols are, and what the difference is between primary, secondary and tertiary alcohols. It looks in some detail at their simple physical properties such as solubility and boiling points. Details of the chemical reactions of alcohols are described on separate pages.

What are alcohols?

Examples Alcohols are compounds in which one or more hydrogen atoms in an alkane have been replaced by an -OH group. For the purposes of UK A level, we will only look at compounds containing one -OH group. For example:

Note: If you aren't confident about naming organic compounds, then you really ought to follow this link before you go on. Use the BACK button on your browser to return to this page.

The different kinds of alcohols Alcohols fall into different classes depending on how the -OH group is positioned on the chain of carbon atoms. There are some chemical differences between the various types. Primary alcohols In a primary (1) alcohol, the carbon which carries the -OH group is only attached to one alkyl group.
Note: An alkyl group is a group such as methyl, CH 3, or ethyl, CH3CH2. These are groups containing chains of carbon atoms which may be branched. Alkyl

groups are given the general symbol R.

Some examples of primary alcohols include:

Notice that it doesn't matter how complicated the attached alkyl group is. In each case there is only one linkage to an alkyl group from the CH2 group holding the -OH group. There is an exception to this. Methanol, CH3OH, is counted as a primary alcohol even though there are no alkyl groups attached to the carbon with the -OH group on it. Secondary alcohols In a secondary (2) alcohol, the carbon with the -OH group attached is joined directly to two alkyl groups, which may be the same or different. Examples:

Tertiary alcohols In a tertiary (3) alcohol, the carbon atom holding the -OH group is attached directly to three alkyl groups, which may be any combination of same or different. Examples:

Physical properties of alcohols

Boiling Points The chart shows the boiling points of some simple primary alcohols with up to 4 carbon atoms. They are:

They are compared with the equivalent alkane (methane to butane) with the same number of carbon atoms.

Notice that:

The boiling point of an alcohol is always much higher than that of the alkane with the same number of carbon atoms. The boiling points of the alcohols increase as the number of carbon atoms increases.

The patterns in boiling point reflect the patterns in intermolecular attractions.

Note: If you aren't happy about intermolecular forces(including van der Waals dispersion forces and hydrogen bonds) then you really ought to follow this link

before you go on. The next bit won't make much sense to you if you aren't familiar with the various sorts of intermolecular forces. Use the BACK button on your browser to return to this page.

Hydrogen bonding Hydrogen bonding occurs between molecules where you have a hydrogen atom attached to one of the very electronegative elements - fluorine, oxygen or nitrogen. In the case of alcohols, there are hydrogen bonds set up between the slightly positive hydrogen atoms and lone pairs on oxygens in other molecules.

The hydrogen atoms are slightly positive because the bonding electrons are pulled away from them towards the very electronegative oxygen atoms.
Note: If you want to be fussy, the diagram is slightly misleading in that it suggests that all of the lone pairs on the oxygen atoms are forming hydrogen bonds. In an alcohol that can't happen. Taking the alcohol as a whole, there are only half as many slightly positive hydrogen atoms as there are lone pairs. At any one time, half of the lone pairs in the total liquid alcohol won't have hydrogen bonds from them because there aren't enough slightly positive hydrogens to go around. In the diagram, to show the 3-dimensional arrangement, the wedge-shaped lines show bonds coming out of the screen or paper towards you. The dotted bonds (other than the hydrogen bonds) show bonds going back into the screen or paper away from you.

In alkanes, the only intermolecular forces are van der Waals dispersion forces. Hydrogen bonds are much stronger than these and therefore it takes more energy to separate alcohol molecules than it does to separate alkane molecules.

That's the main reason that the boiling points are higher.

The effect of van der Waals forces . . . . . . on the boiling points of the alcohols: Hydrogen bonding isn't the only intermolecular force in alcohols. There are also van der Waals dispersion forces and dipole-dipole interactions. The hydrogen bonding and the dipole-dipole interactions will be much the same for all the alcohols, but the dispersion forces will increase as the alcohols get bigger. These attractions get stronger as the molecules get longer and have more electrons. That increases the sizes of the temporary dipoles that are set up. This is why the boiling points increase as the number of carbon atoms in the chains increases. It takes more energy to overcome the dispersion forces, and so the boiling points rise. . . . on the comparison between alkanes and alcohols: Even if there wasn't any hydrogen bonding or dipole-dipole interactions, the boiling point of the alcohol would be higher than the corresponding alkane with the same number of carbon atoms. Compare ethane and ethanol:

Ethanol is a longer molecule, and the oxygen brings with it an extra 8 electrons. Both of these will increase the size of the van der Waals dispersion forces and so the boiling point. If you were doing a really fair comparison to show the effect of the hydrogen bonding on boiling point it would be better to compare ethanol with propane rather than ethane. The length would then be much the same, and the number of electrons is exactly the same.

Solubility of alcohols in water The small alcohols are completely soluble in water. Whatever proportions you mix them in, you will get a single solution.

However, solubility falls as the length of the hydrocarbon chain in the alcohol increases. Once you get to four carbons and beyond, the fall in solubility is noticeable, and you may well end up with two layers in your test tube. The solubility of the small alcohols in water Consider ethanol as a typical small alcohol. In both pure water and pure ethanol the main intermolecular attractions are hydrogen bonds.

In order to mix the two, you would have to break the hydrogen bonds between the water molecules and the hydrogen bonds between the ethanol molecules. It needs energy to do both of these things. However, when the molecules are mixed, new hydrogen bonds are made between water molecules and ethanol molecules.

The energy released when these new hydrogen bonds are made more or less compensates for that needed to break the original ones. In addition, there is an increase in the disorder of the system - an increase in entropy. That is another factor in deciding whether things happen or not.
Note: If you haven't come across entropy before, don't worry about it. I mention it because the energy released when the new bonds are made isn't quite enough to compensate for breaking the old ones, meaning that the mixing process is endothermic. If it weren't for the increase in entropy, the solution wouldn't be

formed. To really understand this, you need to have studied entropy and free energy. If you should know about this, but aren't happy about the calculations involved, you might like to have a look at chapter 11 of my chemistry calculations book.

The lower solubility of bigger alcohols Imagine what happens when you have got, say, 5 carbon atoms in each alcohol molecule.

The hydrocarbon chains are forcing their way between water molecules and so breaking hydrogen bonds between those water molecules. The -OH end of the alcohol molecules can form new hydrogen bonds with water molecules, but the hydrocarbon "tail" doesn't form hydrogen bonds That means that quite a lot of the original hydrogen bonds being broken aren't replaced by new ones. All you get in place of those original hydrogen bonds are van der Waals dispersion forces between the water and the hydrocarbon "tails". These attractions are much weaker. That means that you don't get enough energy back to compensate for the hydrogen bonds being broken. Even allowing for the increase in disorder, the process becomes less feasible. As the length of the alcohol increases, this situation just gets worse, and so the solubility falls.

THE MANUFACTURE OF ALCOHOLS

This page looks at the manufacture of alcohols by the direct hydration of alkenes, concentrating mainly on the hydration of ethene to make ethanol. It then compares that method with making ethanol by fermentation.

Manufacturing alcohols from alkenes

The manufacture of ethanol from ethene Ethanol is manufactured by reacting ethene with steam. The catalyst used is solid silicon dioxide coated with phosphoric(V) acid. The reaction is reversible.

Only 5% of the ethene is converted into ethanol at each pass through the reactor. By removing the ethanol from the equilibrium mixture and recycling the ethene, it is possible to achieve an overall 95% conversion. A flow scheme for the reaction looks like this:

Note: This is a bit of a simplification! When the gases from the reactor are cooled, then excess steam will condense as well as the ethanol. The ethanol will have to be separated from the water by fractional distillation. All the sources I have looked at gloss over this, so I don't have any details. I assume it is a normal fractional distillation of an ethanol-water mixture. If you are interested in the reasons for the conditions used in this reaction, you will find them in the equilibrium section of this site by following this link. If you are interested in the mechanism for the hydration of ethene, follow this link to the catalysis section. Because these pages are (somewhat illogically!) in different parts of the site, use the BACK button (or HISTORY file or GO menu) on your browser to return to this page later.

The manufacture of other alcohols from alkenes Some - but not all - other alcohols can be made by similar reactions. The catalyst used and the reaction conditions will vary from alcohol to alcohol. The only set of conditions you are going to need for UK A level purposes are those given above for manufacturing ethanol. The reason that there is a problem with some alcohols is well illustrated with trying to make an alcohol from propene, CH3CH=CH2. In principle, there are two different alcohols which might be formed:

You might expect to get either propan-1-ol or propan-2-ol depending on which way around the water adds to the double bond. In practice what you get is propan-2-ol. If you add a molecule H-X across a carbon-carbon double bond, the hydrogen nearly always gets attached to the carbon with the most hydrogens on it already - in this case the CH2 rather than the CH.

Note: The reason for this is dealt with in detail in the mechanism section of this site on a page about addition to unsymmetrical alkenes. If you choose to follow this link, use the BACK button on your browser to return to this page.

The effect of this is that there are bound to be some alcohols which it is impossible to make by reacting alkenes with steam because the addition would be the wrong way around.

Making ethanol by fermentation

This method only applies to ethanol. You can't make any other alcohol this way. The process The starting material for the process varies widely, but will normally be some form of starchy plant material such as maize (US: corn), wheat, barley or potatoes. Starch is a complex carbohydrate, and other carbohydrates can also be used - for example, in the lab sucrose (sugar) is normally used to produce ethanol. Industrially, this wouldn't make sense. It would be silly to refine sugar if all you were going to use it for was fermentation. There is no reason why you shouldn't start from the original sugar cane, though. The first step is to break complex carbohydrates into simpler ones. For example, if you were starting from starch in grains like wheat or barley, the grain is heated with hot water to extract the starch and then warmed with malt. Malt is germinated barley which contains enzymes which break the starch into a simpler carbohydrate called maltose, C12H22O11. Maltose has the same molecular formula as sucrose but contains two glucose units joined together, whereas sucrose contains one glucose and one fructose unit. Yeast is then added and the mixture is kept warm (say 35C) for perhaps several days until fermentation is complete. Air is kept out of the mixture to prevent oxidation of the ethanol produced to ethanoic acid (vinegar). Enzymes in the yeast first convert carbohydrates like maltose or sucrose

into even simpler ones like glucose and fructose, both C6H12O6, and then convert these in turn into ethanol and carbon dioxide. You can show these changes as simple chemical equations, but the biochemistry of the reactions is much, much more complicated than this suggests.

Yeast is killed by ethanol concentrations in excess of about 15%, and that limits the purity of the ethanol that can be produced. The ethanol is separated from the mixture by fractional distillation to give 96% pure ethanol. For theoretical reasons, it is impossible to remove the last 4% of water by fractional distillation.
Note: If you are interested in this, you will have to read about it in a physical chemistry textbook under "azeotropic mixtures". Currently I haven't dealt with these on this site, and am unlikely to do so until at least 2005. I will add a link if or when I get around to it!

A comparison of fermentation with the direct hydration of ethene Fermentation Type of process A batch process. Everything is put into a container and then left until fermentation is complete. That batch is then cleared out and a new reaction set up. This is inefficient. Very slow. Produces very impure ethanol which needs further processing Uses gentle temperatures and atmospheric pressure. Hydration of ethene A continuous flow process. A stream of reactants is passed continuously over a catalyst. This is a more efficient way of doing things. Very rapid. Produces much purer ethanol. Uses high temperatures and pressures, needing lots of energy input.

Rate of reaction Quality of product Reaction conditions

Use of resources

Uses renewable resources based on plant material.

Uses finite resources based on crude oil.

THE DEHYDRATION OF ALCOHOLS

This page (a simple duplicate of a page in the section on alkenes!) looks at the dehydration of alcohols in the lab to make alkenes - for example, dehydrating ethanol to make ethene.

Dehydration of alcohols using aluminium oxide as catalyst The dehydration of ethanol to give ethene This is a simple way of making gaseous alkenes like ethene. If ethanol vapour is passed over heated aluminium oxide powder, the ethanol is essentially cracked to give ethene and water vapour.

To make a few test tubes of ethene, you can use this apparatus:

It wouldn't be too difficult to imagine scaling this up by boiling some ethanol in a flask and passing the vapour over aluminium oxide heated in a long tube.

Dehydration of alcohols using an acid catalyst The acid catalysts normally used are either concentrated sulphuric acid or concentrated phosphoric(V) acid, H3PO4. Concentrated sulphuric acid produces messy results. Not only is it an acid, but it is also a strong oxidising agent. It oxidises some of the alcohol to carbon dioxide and at the same time is reduced itself to sulphur dioxide. Both of these gases have to be removed from the alkene. It also reacts with the alcohol to produce a mass of carbon. There are other side reactions as well, but these aren't required by any current UK A level (or equivalent) syllabus.

The dehydration of ethanol to give ethene Ethanol is heated with an excess of concentrated sulphuric acid at a temperature of 170C. The gases produced are passed through sodium hydroxide solution to remove the carbon dioxide and sulphur dioxide produced from side reactions. The ethene is collected over water.
WARNING! This is potentially an extremely dangerous preparation because of the close proximity of the very hot concentrated sulphuric acid and the sodium hydroxide solution. I knew of one chemistry teacher who put several students into hospital by getting it wrong! That was many years ago before safety was taken quite so seriously as it is now.

The concentrated sulphuric acid is a catalyst. Write it over the arrow rather than in the equation.