INTRODUCING CARBOXYLIC ACIDS

Carboxylic acids are compounds which contain a -COOH group. Examples of carboxylic acids

The name counts the total number of carbon atoms in the longest chain - including the one in the -COOH group. If you have side groups attached to the chain, notice that you always count from the carbon atom in the -COOH group as being number 1. Salts of carboxylic acids Carboxylic acids are acidic because of the hydrogen in the -COOH group. When the acids form salts, this is lost and replaced by a metal. Sodium ethanoate, for example, has the structure:

Depending on whether or not you wanted to stress the ionic nature of the compound, this would be simplified to CH3COO- Na+ or just CH3COONa. Notice: The bond between the sodium and the ethanoate is ionic. Don't draw a line between the two (implying a covalent bond). That's absolutely wrong!

Physical properties of carboxylic acids
The physical properties (for example, boiling point and solubility) of the carboxylic acids are governed by their ability to form hydrogen bonds. Boiling points Before we look at carboxylic acids, a reminder about alcohols: The boiling points of alcohols are higher than those of alkanes of similar size because the alcohols can form hydrogen bonds with each other as well as van der Waals dispersion forces and dipole-dipole interactions.

The boiling points of carboxylic acids of similar size are higher still. For example: propan-1-ol ethanoic acid CH3CH2CH2OH CH3COOH 97.2°C 118°C

These are chosen for comparison because they have identical relative molecular masses and almost the same number of electrons (which affects van der Waals dispersion forces). The higher boiling points of the carboxylic acids are still caused by hydrogen bonding, but operating in a different way. In a pure carboxylic acid, hydrogen bonding can occur between two molecules of acid to produce a dimer.

This immediately doubles the size of the molecule and so increases the van der Waals dispersion forces between one of these dimers and its neighbours - resulting in a high boiling point. Solubility in water In the presence of water, the carboxylic acids don't dimerise. Instead, hydrogen bonds are formed between water molecules and individual molecules of acid. The carboxylic acids with up to four carbon atoms will mix with water in any proportion. When you mix the two together, the energy released when the new hydrogen bonds form is much the same as is needed to break the hydrogen bonds in the pure liquids. The solubility of the bigger acids decreases very rapidly with size. This is because the longer hydrocarbon "tails" of the molecules get between water molecules and break hydrogen bonds. In this case, these broken hydrogen bonds are only replaced by much weaker van der Waals dispersion forces.

Starting from the primary alcohol. Primary alcohols are oxidised to carboxylic acids in two stages . you are obviously just doing this second stage. in practice if it is a hydrogen. We often use simplified versions of these equations using "[O]" to represent oxygen from the oxidising agent.Making carboxylic acids by oxidising primary alcohols or aldehydes Chemistry of the reactions Primary alcohols and aldehydes are normally oxidised to carboxylic acids using potassium dichromate(VI) solution in the presence of dilute sulphuric acid. all the equations and colour changes would be identical. The formation of the aldehyde is shown by the simplified equation: "R" is a hydrogen atom or a hydrocarbon group such as an alkyl group. During the reaction. methanoic acid is very easily oxidised The aldehyde is then oxidised further to give the carboxylic acid: If you start with an aldehyde. the oxidation eventually goes all the way to carbon dioxide and water rather than stopping at methanoic acid. Because what matters is the dichromate(VI) ion. you could combine these into one single equation to give: . the potassium dichromate(VI) solution turns from orange to green. Note: Although "R" can in principle be a hydrogen atom.first to an aldehyde and then to the acid. Unlike most other carboxylic acids. The potassium dichromate(VI) can just as well be replaced with sodium dichromate(VI).

the simplified equation would be: It is possible that you might want to write proper equations for these reactions rather than these simplified ones. You can work these out from electron-half-equations. How you do this is described in detail elsewhere on the site. . The conversion of ethanol into ethanoic acid would be a typical example. When oxidation is complete. It isn't difficult to work out the aldehyde one using the same principles . You end up with an aqueous solution of the acid. If you choose to follow this link.For example. The alcohol is heated under reflux with an excess of a mixture of potassium dichromate(VI) solution and dilute sulphuric acid. Using an excess of oxidising agent is to be sure that there is enough oxidising agent present for the oxidation to go all the way to the carboxylic acid. or if you were starting from an aldehyde is: Note: The equation for the conversion of ethanol to ethanoic acid is worked out in detail on the page about electron-half-equations mentioned above. Doing the reactions It would actually be quite uncommon to make an acid starting from an aldehyde. .it would be a useful exercise to check that you understand what to do. but very common to start from a primary alcohol. use the BACK button on your browser to return to this page. if you were converting ethanol into ethanoic acid. Heating under reflux (heating in a flask with a condenser placed vertically in it) prevents any aldehyde formed escaping before it has time to be oxidised to the carboxylic acid. the mixture can be distilled. . The complete equation for the conversion of a primary alcohol to a carboxylic acid is: .

the -CN carbon counts as number 1. For example: . In particular. Some common examples include: The name is based on the total number of carbons in the longest chain . I have seen several cases of reaction mixtures which suddenly boiled and spurted out of the top of the condenser. .both of which result in an increase in the length of the carbon chain because of the extra carbon in the -CN group. the reagents have to be thoroughly mixed before you start heating.including the one in the -CN group. Where do nitriles come from? Nitriles are produced in two important reactions . . or during the reaction between aldehydes or ketones and hydrogen cyanide.Warning! The early stages of this reaction can be extremely vigorous if great care isn't taken in producing the original mixture in the flask. The second one is described on a page about addition reactions of aldehydes and ketones. the reaction between ethanal and hydrogen cyanide to make 2-hydroxypropanenitrile is: Note: The first reaction is described on the page about halogenoalkanes and cyanide ions. Making carboxylic acids by hydrolysing nitriles What are nitriles? Nitriles are compounds which contain -CN attached to a hydrocarbon group. They are formed in the reaction between halogenoalkanes (haloalkanes or alkyl halides) and cyanide ions. . For example. Where you have things substituted into the chain (as in the third example). Both of these pages include links to other pages dealing with the mechanisms of these reactions.

Acid hydrolysis The nitrile is heated under reflux with a dilute acid such as dilute hydrochloric acid. both of which involve reacting the carbon-nitrogen triple bond with water. This is described as hydrolysis. For example. This time you wouldn't. To liberate the weak acid. starting from ethanenitrile you would get ethanoic acid. Note: If you have a choice in an exam.any acid formed would react with the sodium hydroxide present to give a salt. because that's what we are trying to make. use the BACK button on your browser to return to this page. Alkaline hydrolysis The nitrile is heated under reflux with an alkali such as sodium hydroxide solution. ethanoic acid. you just have to supply hydrogen ions from a strong acid such as hydrochloric acid. it obviously makes a lot of sense to use acid hydrolysis rather than alkaline hydrolysis . Converting the nitrile into a carboxylic acid There are two ways of doing this. you would therefore get a solution containing ethanoate ions (for example. Now you can distill off the carboxylic acid. The two methods produce slightly different products . get a carboxylic acid produced . You also wouldn't get ammonium ions because they would react with sodium hydroxide to produce ammonia. A carboxylic acid is formed. Starting from ethanenitrile.If you choose to follow these links. You add enough hydrochloric acid to the mixture to make it acidic. of course.it saves a lot of bother! . You have to remember to convert the ions into the free carboxylic acid. sodium ethanoate if you used sodium hydroxide solution) and ammonia.you just have to be careful to get this right. The ethanoic acid could be distilled off the mixture.

This reaction is reversible and. you must include state symbols. The acidity of the carboxylic acids Why are carboxylic acids acidic? Using the definition of an acid as a "substance which donates protons (hydrogen ions) to other things". ammonia and amines. For example. Note: This page covers all the reactions likely to be asked by any of the UK syllabuses for 16 .CARBOXYLIC ACIDS AS ACIDS This page looks at the simple reactions of carboxylic acids as acids. you get an ethanoate ion formed together with a hydroxonium ion. with ethanoic acid. a hydrogen ion is transferred from the -COOH group to a water molecule. carbonates and hydrogencarbonates. Check your syllabus and past papers to find out what you need to know. no more than about 1% of the acid has reacted to form ions at any one time. . (This is a rough-and-ready figure and varies with the concentration of the solution. They imply that the hydrogen ion is actually attached to a water molecule. H 3O+. in the case of ethanoic acid. but no single syllabus is likely to want all of them. In solution in water.18 year olds. follow this link to find out how to get hold of them. the carboxylic acids are acidic because of the hydrogen in the -COOH group. metal hydroxides.) These are therefore weak acids. if you are going to use this second equation. If you are a studying a UKbased syllabus and haven't got these. including their reactions with metals. This equation is often simplified to: However.

Methanoic acid is rather stronger than the other simple acids.3 range. Warning! Students have a high tendency to get the formulae of salts like magnesium ethanoate wrong. you might be interested in my chemistry calculations book. If you choose to follow either of these links. Typical lab solutions have pH's in the 2 .5 pH units less than ethanoic acid of the same concentration. If you should know how to calculate the pH of weak acids like ethanoic acid. Ethanoic acid is typical of the acids where the -COOH group is attached to a simple alkyl group. Remember that these simple carboxylic acids form ions with a single negative charge. both are so fast that you probably wouldn't notice much difference. use the BACK button on your browser to return to this page. Reactions of the carboxylic acids With metals Carboxylic acids react with the more reactive metals to produce a salt and hydrogen.except that with these salts the metal is written at the end of the . If you use magnesium ribbon. In essence. and hydrogen is given off. depending on their concentrations.The pH of carboxylic acid solutions The pH depends on both the concentration of the acid and how easily it loses hydrogen ions from the COOH group. but with magnesium powder. and that the magnesium ion has two positive charges. Note: You will find factors affecting the acidity of organic acids discussed in detail if you follow this link. except they tend to be rather slower. For example. and solutions have pH's about 0. this is no different from writing the formula for magnesium chloride . the reaction is less vigorous than the same reaction with hydrochloric acid. The magnesium reacts to produce a colourless solution of magnesium ethanoate. but aren't happy about it. The reactions are just the same as with acids like hydrochloric acid. dilute ethanoic acid reacts with magnesium.

formula rather than at the beginning. for example. . the full equation for this particular reaction is: With carbonates and hydrogencarbonates In both of these cases. The only sign that a change has happened is that the temperature of the mixture will have increased. If you mix dilute ethanoic acid with sodium hydroxide solution. This change could well be represented by the ionic equation above. . however. but if you want it. They are most quickly and easily represented by the equation: Note: This assumes that the hydroxide is in solution. (It probably will be. Both are most easily represented by ionic equations. and for hydrogencarbonates: Note: This time. because almost the only reaction ever done of this type is with sodium hydroxide solution!) If you were using a solid hydroxide. you simply get a colourless solution containing sodium ethanoate. a salt is formed together with carbon dioxide and water. you would have to swap the hydroxide state symbol from "(aq)" to "(s)". this assumes that the carbonate or . With metal hydroxides These are simple neutralisation reactions and are just the same as any other reaction in which hydrogen ions from an acid react with hydroxide ions. For carbonates: .

say. However. there is an immediate fizzing as carbon dioxide is produced. you would notice the difference if you used a slower reaction . It transfers a hydrogen ion to the lone pair on the nitrogen of the ammonia and forms an ammonium ion. you would eventually produce a colourless solution of calcium ethanoate. You end up with a colourless solution of sodium ethanoate. With sodium carbonate. In this case. . If you used a solution of. With ethanoic acid. and for sodium hydrogencarbonate: There is very little obvious difference in the vigour of these reactions compared with the same reactions with dilute hydrochloric acid. sodium carbonate or hydrogencarbonate. With ammonia Ethanoic acid reacts with ammonia in exactly the same way as any other acid does. the marble chip would react noticeably more slowly with ethanoic acid than with hydrochloric acid.which it often is. you would have to remember to change the state symbol.hydrogencarbonate will be a solid .for example with calcium carbonate in the form of a marble chip. If you pour some dilute ethanoic acid onto some white sodium carbonate or sodium hydrogencarbonate crystals. . the full equation is: . .

However complicated the amine. Because all you have done to an ammonia molecule is swap a hydrogen for an alkyl group. Note: I have deliberately not tried to write this as a one line equation. Simple primary amines include: The small amines are very similar indeed to ammonia in many ways.If you mix together a solution of ethanoic acid and a solution of ammonia. because all of them have got a lone pair on the nitrogen atom. Don't be put off by the name of the product .methylammonium ethanoate. ethanoic acid reacts with methylamine to produce a colourless solution of the salt methylammonium ethanoate. "Methylammonium" just means an ammonium ion in which one of the hydrogens is replaced by a methyl group. For example. For simplicity. That means that they will react with acids (including carboxylic acids) in just the same way as ammonia does. and to remember it. you . These are called primary amines. With amines Amines are compounds in which one or more of the hydrogen atoms in an ammonia molecule have been replaced by a hydrocarbon group such as an alkyl group. we'll just look at compounds where only one of the hydrogen atoms has been replaced. the lone pair is still there on the nitrogen atom. For example. to write it. It is much easier to see what is happening. you will get a colourless solution of ammonium ethanoate. they smell very much like ammonia and are just as soluble in water. if you draw the structures.

the hydrogen in the -COOH group has been replaced by an ethyl group. Note: In my experience. ESTERIFICATION OF CARBOXYLIC ACIDS This page looks at esterification . In this case. The "ethyl" bit comes from the ethyl group on the end. What are esters? Esters have a hydrocarbon group of some sort replacing the hydrogen in the -COOH group of a carboxylic acid. students starting organic chemistry get more confused about writing names and formulae for esters than for almost anything else . We shall just be looking at cases where it is replaced by an alkyl group. A common ester .ethyl ethanoate The most commonly discussed ester is ethyl ethanoate.the reaction between alcohols and carboxylic acids to make esters. . The formula for ethyl ethanoate is: Notice that the ester is named the opposite way around from the way the formula is written. The "ethanoate" bit comes from ethanoic acid. Take time and care to make sure you understand! A few more esters In each case. Note: If you want to find out more about amines you could explore the amines menu by following this link. but it could equally well be an aryl group (one based on a benzene ring).would get the same sort of reaction.particularly when it comes to less frequently met esters like the ones coming up next. be sure that you can see how the names and formulae relate to each other.

and CH3CH2COO is the propanoate group. the equation would . The catalyst is usually concentrated sulphuric acid. Note: You can find more about naming acids and esters by following this link to a different part of this site. for example. Use the BACK button on your browser to return to this page. So. 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. Dry hydrogen chloride gas is used in some cases. but these tend to involve aromatic esters (ones containing a benzene ring).Remember that the acid is named by counting up the total number of carbon atoms in the chain including the one in the -COOH group. CH3CH2COOH is propanoic acid. If you are a UK A level student you won't have to worry about these. for example. if you were making ethyl ethanoate from ethanoic acid and ethanol. Making esters The chemistry of the reaction Esters are produced when carboxylic acids are heated with alcohols in the presence of an acid catalyst. The esterification reaction is both slow and reversible.

you don't get a lot of ester produced in this time. and distil off the ester as soon as it is formed. for example. It is not required for any UK A level chemistry syllabus. . Doing the reactions On a test tube scale Carboxylic acids and alcohols are often warmed together in the presence of a few drops of concentrated sulphuric acid in order to observe the smell of the esters formed. A simple way of detecting the smell of the ester is to pour the mixture into some water in a small beaker. the method used depends to some extent on the size of the ester. for example. and so it has the weakest intermolecular forces. This prevents the reverse reaction happening. The ester is the only thing in the mixture which doesn't form hydrogen bonds. The smell is often masked or distorted by the smell of the carboxylic acid. On a larger scale If you want to make a reasonably large sample of an ester. Because the reactions are slow and reversible. Excess acid and alcohol both dissolve and are tucked safely away under the ester layer. use the BACK button on your browser to return to this page. Small esters like ethyl ethanoate smell like typical organic solvents (ethyl ethanoate is a common solvent in.be: Note: The mechanism for the esterification reaction is covered in the catalysis section of this site. You would normally use small quantities of everything heated in a test tube stood in a hot water bath for a couple of minutes. you can gently heat a mixture of ethanoic acid and ethanol in the presence of concentrated sulphuric acid. the smells tend towards artificial fruit flavouring . To make a small ester like ethyl ethanoate. glues)."pear drops". It works well because the ester has the lowest boiling point of anything present. As the esters get bigger. Esters are virtually insoluble in water and tend to form a thin layer on the surface. Small esters are formed faster than bigger ones. If you follow this link.

water and sulphuric acid in the mixture by fractional distillation. Since aluminium only ever shows the +3 oxidation state in its compounds. The present page isn't done in the same sort of detail as that one. it may be necessary to heat the reaction mixture under reflux for some time to produce an equilibrium mixture. alcohol.Note: Follow this link if you aren't sure about hydrogen bonding. you should be looking at an organic practical book. you might find it useful to read a rather more detailed account of its use on the page about reduction of aldehydes and ketones. I shall leave it out for the rest of this page to make the name a bit shorter. Use the BACK button on your browser to return to this page. In these cases. If you need this sort of detail. REDUCTION OF CARBOXYLIC ACIDS This page looks at the reduction of carboxylic acids to primary alcohols using lithium tetrahydridoaluminate(III) (lithium aluminium hydride). The "(III)" is the oxidation state of the aluminium. LiAlH4. The ester can be separated from the carboxylic acid. Note: If you haven't come across this reducing agent before. Larger esters tend to form more slowly. the "(III)" is actually unnecessary. Use the BACK button on your browser to return to this page. The reaction The reducing agent Lithium tetrahydridoaluminate has the structure: . Note: Providing full details for organic preparations (including all the steps necessary in cleaning up the product) is beyond the scope of this site.

ethanoic acid will reduce to the primary alcohol. Because of the impossibility of stopping at the aldehyde. For example. there isn't much point in giving an equation for the two separate stages. one of the bonds is a co-ordinate covalent (dative covalent) bond using the lone pair on a hydride ion (H-) to form a bond with an empty orbital on the aluminium. Use the BACK button on your browser to return to this page. Use the BACK button on your browser to return to this page. Equations for these reactions are usually written in a simplified form for UK A level purposes. although it isn't important to understanding the rest of this page. Because lithium tetrahydridoaluminate reacts rapidly with aldehydes. ethanol. Note: If you aren't happy about co-ordinate covalent (dative covalent) bonding you could follow this link. The reduction of a carboxylic acid The reaction happens in two stages .first to form an aldehyde and then a primary alcohol. it is impossible to stop at the halfway stage.In the negative ion. Note: Follow this link if you aren't sure what a primary alcohol is. The overall reaction is: "R" is hydrogen or a hydrocarbon group. The "[H]" in the equations represents hydrogen from a reducing agent. Sodium tetrahydridoborate (sodium borohydride) won't work! .

If you are familiar with the reduction of aldehydes and ketones using lithium tetrahydridoaluminate. It CAN'T be used with carboxylic acids. RCOOH. you are probably aware that sodium tetrahydridoborate is often used as a safer alternative. The reaction happens at room temperature. It covers the use of phosphorus(V) chloride and phosphorus(III) chloride as well as sulphur dichloride oxide (thionyl chloride). Replacing -OH by -Cl Introduction We are going to be looking at converting a carboxylic acid. At the end of the reaction. RCOCl. . Acyl chlorides are also known as acid chlorides. the product is a complex aluminium salt. CONVERTING CARBOXYLIC ACIDS INTO ACYL CHLORIDES (ACID CHLORIDES) This page looks at ways of swapping the -OH group in the -COOH group of a carboxylic acid for a chlorine atom. The sodium tetrahydridoborate isn't reactive enough to reduce carboxylic acids. Reaction conditions Lithium tetrahydridoaluminate reacts violently with water and so the reactions are carried out in solution in dry ethoxyethane (diethyl ether or just "ether"). This is converted into the alcohol by treatment with dilute sulphuric acid. This produces useful compounds called acyl chlorides (acid chlorides). although you may need to know that you have to finish the reaction off using dilute sulphuric acid. into an acyl chloride. Note: You are unlikely to need this equation for UK A level purposes.

and can be used to make a wide range of other things. The acyl chloride can be separated by fractional distillation.POCl3. you can explore the acyl chlorides menu by following this link. PCl3 Phosphorus(III) chloride is a liquid at room temperature. Use the BACK button on your browser to return to this page. For example: Replacing the -OH group using phosphorus(III) chloride. Note: If you are want to find out more about acyl chlorides. PCl5 Phosphorus(V) chloride is a solid which reacts with carboxylic acids in the cold to give steamy acidic fumes of hydrogen chloride. It leaves a liquid mixture of the acyl chloride and a phosphorus compound. Acyl chlorides are very reactive. That's why they are important. Its reaction with a carboxylic acid is less . Replacing the -OH group using phosphorus(V) chloride.By far the most commonly used example of the conversion of a carboxylic acid into an acyl chloride is ethanoic acid to ethanoyl chloride. phosphorus trichloride oxide (phosphorus oxychloride) .

The hydrocarbon group could equally well be based on a benzene ring. Decarboxylation using soda lime What does "decarboxylation" mean? A carboxylic acid has the formula RCOOH where R can be hydrogen or a hydrocarbon group such as an alkyl group. The sodium salt of a carboxylic acid will have the formula RCOONa. Replacing the -OH group using sulphur dichloride oxide (thionyl chloride) Sulphur dichloride oxide (thionyl chloride) is a liquid at room temperature and has the formula SOCl2.dramatic than that of phosphorus(V) chloride because there is no hydrogen chloride produced. For example: Again. The sulphur dichloride oxide reacts with carboxylic acids to produce an acyl chloride. For example: The separation is simplified to an extent because the by-products are both gases. You would obviously still have to fractionally distil the mixture to separate the acyl chloride from any excess acid or sulphur dichloride oxide. and sulphur dioxide and hydrogen chloride gases are given off. . H3PO3. the ethanoyl chloride can be separated by fractional distillation. the formula is written as shown. You end up with a mixture of the acyl chloride and phosphoric(III) acid (old names: phosphorous acid or orthophosphorous acid). the -COOH or -COONa group is removed and replaced with a hydrogen atom. It does NOT cover the decarboxylation of some acids by simply heating them. despite the fact that the modern name writes the chlorine before the oxygen (alphabetical order). In decarboxylation. Traditionally. THE DECARBOXYLATION OF CARBOXYLIC ACIDS AND THEIR SALTS This page looks at the formation of hydrocarbons by the decarboxylation of the salts of carboxylic acids (and of certain acids themselves) by heating them with soda lime.

The mechanism Warning! This is a fairly complex mechanism. The reaction The solid sodium salt of a carboxylic acid is mixed with solid soda lime. It is an easier material to handle than solid sodium hydroxide. . it is almost always written as if it were simply sodium hydroxide. For example. In equations. THE MECHANISM FOR THE ESTERIFICATION REACTION This page looks in detail at the mechanism for the formation of esters from carboxylic acids and alcohols in the presence of concentrated sulphuric acid acting as the catalyst. ethyl ethanoate. if you heat sodium ethanoate with soda lime. benzene can be made by heating soda lime with solid benzoic acid (benzenecarboxylic acid). and then a decarboxylation as in the first example. You can think of this as first a reaction between the acid and the soda lime to make sodium benzoate. To reduce the chances of the reverse reaction happening. the ester is distilled off as soon as it is formed. It uses the formation of ethyl ethanoate from ethanoic acid and ethanol as a typical example. For example. The reaction is slow and reversible. Soda lime has much less tendency to absorb water. I have included it in case it is of use to my many non-UK visitors. you get methane gas formed: This reaction can be done with certain carboxylic acids themselves. C6H5COOH. calcium oxide and calcium hydroxide. The mechanism for the formation of ethyl ethanoate A reminder of the facts Ethanoic acid reacts with ethanol in the presence of concentrated sulphuric acid as a catalyst to produce the ester. It is essentially a mixture of sodium hydroxide. It comes as white granules.What is soda lime? Soda lime is manufactured by adding sodium hydroxide solution to solid calcium oxide (quicklime). Solid sodium hydroxide absorbs water from the atmosphere and you tend to end up with puddles of extremely concentrated (and corrosive) sodium hydroxide solution if you leave it exposed to the air. and the mixture is heated. and is definitley NOT required for any UK A level (or equivalent) syllabus.

The reverse reaction is actually done sufficiently differently that it affects the way the mechanism is written. you probably shouldn't be reading this page anyway . You will find a link to the hydrolysis of esters further down the page if you are interested. In other words. if you are that unsure about the conventions used in reaction mechanisms. Note: The explanation assumes that you know about the use of curly arrows in organic reaction mechanisms. The proton becomes attached to one of the lone pairs on the oxygen which is double-bonded to the carbon. Step 1 In the first step. If you aren't happy about these follow this link before you go any further. The positive charge is delocalised over the whole of the right-hand end of the ion. with a fair amount of positiveness on the carbon atom. The transfer of the proton to the oxygen gives it a positive charge. but it is actually misleading to draw the structure in this way (although nearly everybody does!).you will find it distinctly scary!) Use the BACK button on your browser to return to this page. the ethanoic acid takes a proton (a hydrogen ion) from the concentrated sulphuric acid. (To be honest.All the steps in the mechanism below are shown as one-way reactions because it makes the mechanism look less confusing. you can think of an electron pair shifting to give this structure: You could also imagine another electron pair shift producing a third structure: .

and also on the carbon atom. For the purposes of the rest of this discussion. Each of the bonds between the carbon and the two oxygens will be the same . that page looks at the structure of ions like the ethanoate ions which also have delocalised charges. The various structures are known as resonance structures or canonical forms. we are going to use the structure where the positive charge is on the carbon atom. They don't mean that the bonds are flipping back and forth between one structure and another. One way of writing the delocalised structure of the ion is like this: The double headed arrows are telling you that each of the individual structures makes a contribution to the real structure of the ion. Step 2 The positive charge on the carbon atom is attacked by one of the lone pairs on the oxygen of the ethanol molecule. Note: You will find a more pictorial look at a similar case to this in a page discussing the acidity of organic acids.somewhere between a single bond and a double bond. .So which of these is the correct structure of the ion formed? None of them! The truth lies somewhere in between all of them. Amongst other things. There will be some degree of positive charge on both of the oxygen atoms. Use the BACK button on your browser to return easily to this page.

it has too many bonds. and that particular oxygen doesn't look right . The net effect is: Step 4 Now a molecule of water is lost from the ion. by attaching to a lone pair on an unreacted ethanol molecule). you could realise that there has to be a positive charge somewhere (because you started with one). The positive charge is actually delocalised all over that end of the ion. On the other hand. The product ion has been drawn in a shape to reflect the product which we are finally getting quite close to! The structure for the latest ion is just like the one we discusssed at length back in step 1. and there will also be contributions from structures where the charge is on the either of the oxygens: . Put the charge on there! That's a quick rough-and-ready reasoning which works every time I use it! Step 3 What happens next is that a proton (a hydrogen ion) gets transferred from the bottom oxygen atom to one of the others. and then dumped back onto one of the oxygens more or less at random.Note: You could work out precisely why that particular oxygen carries the positive charge on the right-hand side. It gets picked off by one of the other substances in the mixture (for example.

It is easier to follow what is happening if we keep going with the structure with the charge on the carbon. Step 5 The hydrogen is removed from the oxygen by reaction with the hydrogensulphate ion which was formed way back in the first step. and the sulphuric acid catalyst has been regenerated. . And there we are! The ester has been formed.

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