Alcohols Lab
Alcohols Lab
Alcohols Lab
Alcohols are compounds in which one or more hydrogen atoms in an alkane have
been replaced by an -OH group.
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 alcohol, the carbon which carries the -OH group is only attached to
one alkyl group.
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 alcohol, the carbon with the -OH group attached is joined directly to two alkyl
groups, which may be the same or different.
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.
Boiling Points
The chart shows the boiling points of some simple primary alcohols with up to 4
carbon atoms.
They are:
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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.
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 oxygen’s in other molecules.
The hydrogen atoms are slightly positive because the bonding electrons are
pulled away from them towards the very electronegative oxygen atoms.
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.
Consider ethanol as a typical small alcohol. In both pure water and pure ethanol
the main intermolecular attractions are hydrogen bonds.
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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.
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.
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.
Sodium ethoxide is just like sodium hydroxide, except that the hydrogen has
been replaced by an ethyl group. Sodium hydroxide contains OH- ions; sodium
ethoxide contains CH3CH2O- ions.
Rather than using hydrobromic acid, you usually treat the alcohol with a mixture
of sodium or potassium bromide and concentrated sulphuric acid. This produces
hydrogen bromide which reacts with the alcohol. The mixture is warmed to distil
off the bromoalkane.
In this case the alcohol is reacted with a mixture of sodium or potassium iodide
and concentrated phosphoric(V) acid, H3PO4, and the iodoalkane is distilled off.
The mixture of the iodide and phosphoric(V) acid produces hydrogen iodide
which reacts with the alcohol.
A similar thing happens to some extent with bromide ions in the preparation of
bromoalkanes, but not enough to get in the way of the main reaction. There is no
reason why you couldn't use phosphoric(V) acid in the bromide case instead of
sulphuric acid if you wanted to.
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Reacting alcohols with phosphorus halides
OXIDATION OF ALCOHOLS
Primary alcohols
You get an aldehyde if you use an excess of the alcohol, and distil off the
aldehyde as soon as it forms.
The excess of the alcohol means that there isn't enough oxidising agent present
to carry out the second stage. Removing the aldehyde as soon as it is formed
means that it doesn't hang around waiting to be oxidised anyway!
If you used ethanol as a typical primary alcohol, you would produce the aldehyde
ethanal, CH3CHO.
The full equation for this reaction is fairly complicated, and you need to
understand about electron-half-equations in order to work it out.
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In organic chemistry, simplified versions are often used which concentrate on
what is happening to the organic substances. To do that, oxygen from an
oxidising agent is represented as [O]. That would produce the much simpler
equation:
You need to use an excess of the oxidising agent and make sure that the
aldehyde formed as the half-way product stays in the mixture.
The alcohol is heated under reflux with an excess of the oxidising agent. When
the reaction is complete, the carboxylic acid is distilled off.
The full equation for the oxidation of ethanol to ethanoic acid is:
Alternatively, you could write separate equations for the two stages of the
reaction - the formation of ethanal and then its subsequent oxidation.
Secondary alcohols
Secondary alcohols are oxidised to ketones - and that's it. For example, if you
heat the secondary alcohol propan-2-ol with sodium or potassium dichromate(VI)
solution acidified with dilute sulphuric acid, you get propanone formed.
Tertiary alcohols
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Tertiary alcohols aren't oxidised by acidified sodium or potassium
dichromate(VI) solution. There is no reaction whatsoever.
If you look at what is happening with primary and secondary alcohols, you will
see that the oxidising agent is removing the hydrogen from the -OH group, and a
hydrogen from the carbon atom attached to the -OH. Tertiary alcohols don't have
a hydrogen atom attached to that carbon.
ESTERIFICATION
Esters are derived from carboxylic acids. A carboxylic acid contains the -COOH
group, and in an ester the hydrogen in this group is replaced by a hydrocarbon
group of some kind. We shall just be looking at cases where it is replaced by an
alkyl group, but it could equally well be an aryl group (one based on a benzene
ring).
Esters are produced when carboxylic acids are heated with alcohols in the
presence of an acid catalyst. The catalyst is usually concentrated sulphuric
acid. Dry hydrogen chloride gas is used in some cases, but these tend to involve
aromatic esters (ones containing a benzene ring). If you are a UK A level student
you won't have to worry about these.
The esterification reaction is both slow and reversible. The equation for the
reaction between an acid RCOOH and an alcohol R'OH (where R and R' can be
the same or different) is:
So, for example, if you were making ethyl ethanoate from ethanoic acid and
ethanol, the equation would be: