Alkanes - Blog Posts

Alkanes: Crash Course Organic Chemistry #6:

Alkanes are kind of the wallflowers of organic chemistry, but they still have important functions in the world around us. In this episode of Crash Course Organic Chemistry we’re building our knowledge of organic molecules by learning all about these so called couch potatoes from how they are separated from crude oil to how to use Newman projections to predict torsional strain and steric hinderance. We’ll also learn the names of some common conformers and get an introduction to cycloalkanes. 

Structural Isomerism

In one boring history lesson, you and your friend (who both love chemistry) are doodling displayed formulas in the back of your textbook. You both decide to draw C5H12 - however, when you come to name what you’ve drawn, your friend has something completely different. You know what you’ve drawn is pentane and your friend knows what they’ve drawn is 2,3-dimethylpropane. So which one is C5H12?

The answer is both! What you and your friend have hypothetically drawn are structural isomers of C5H12 (another is 2-methylbutane). These are compounds which have the same molecular formula but different structural formulas.

Isomers are two or more compounds with the same formula but a different arrangement of atoms in the molecule and often different properties. 

There are several different kinds of structural isomers: chain, positional and functional group. 

Chain isomerism happens when there is more than one way of arranging carbon atoms in the longest chain. If we continue with the example C5H12, it exists as the three chain isomers shown above. Chain isomers have similar chemical properties but different physical properties because more branched isomers have weaker Van der Waals and therefore lower boiling points.

Positional isomers have the same carbon chain and the same functional group but it is attached at different points along the chain. 

This is a halogenoalkane. The locant “1″ describes where the chlorine is on the chain. For more on naming organic compounds, check out my nomenclature post.

The final type of isomer you need to know is a functional group isomer. This is a compound with the same molecular formula but a different functional group. For example, C2H6O could be ethanol or methoxymethane.

And surprisingly, that is all you need to know for the AS exam. There are also things called stereoisomers but those will be covered next year. Just make sure you know how to name and draw the three different kinds of structural isomers for the exam. Practice makes perfect!

SUMMARY

Structural isomers are compounds which have the same molecular formula but different structural formulas.

Isomers are two or more compounds with the same formula but a different arrangement of atoms in the molecule and often different properties.

There are several different kinds of structural isomers: chain, positional and functional group.

Chain isomerism happens when there is more than one way of arranging carbon atoms in the longest chain. Chain isomers have similar chemical properties but different physical properties because more branched isomers have weaker Van der Waals and therefore lower boiling points.

Positional isomers have the same carbon chain and the same functional group but it is attached at different points along the chain.

A functional group isomer is a compound with the same molecular formula but a different functional group.

Happy studying!

Combusting Alkanes

If you follow this blog, by now you must be thinking, when will we be done with the alkane chemistry? Well, the answer is never. There is still one more topic to touch on - burning alkanes and the environmental effects. Study up chums!

Alkanes are used as fuels due to how they can combust easily to release large amounts of heat energy. Combustion is essentially burning something in the presence of oxygen. There are two types of combustion: complete and incomplete. 

Complete combustion occurs when there is a plentiful supply of air. When an alkane is burned in sufficient oxygen, it produces carbon dioxide and water. How much depends on what is being burnt. For example:

butane + oxygen -> carbon dioxide + water

2C4H10 (g) + 13O2 (g) -> 8CO2 (g) + 10H2O (g)

Remember state symbols in combustion reactions. In addition, this reaction can be halved to balance for 1 mole of butane by using fractions when dealing with the numbers.

C4H10 (g) + 6 ½ O2 (g) -> 4CO2 (g) + 5H2O (g)

Incomplete combustion on the other hand occurs when there is a limited supply of air. There are two kinds of incomplete combustion. The first type produces water and carbon monoxide. 

butane + limited oxygen -> carbon monoxide + water

C4H10 (g) + 4 ½ O2 (g) -> 4CO (g) + 5H2O (g)

Carbon monoxide is dangerous because it is toxic and undetectable due to being smell-free and colourless. It reacts with haemoglobin in your blood to reduce their oxygen-carrying ability and can cause drowsiness, nausea, respiratory failure or death. Applicances therefore must be maintained to prevent the formation of the monoxide.

The other kind of incomplete combustion occurs in even less oxygen. It produces water and soot (carbon).

butane + very limited oxygen -> carbon + water

C4H10 (g) + 2 ½ O2 (g) -> 4C (g) + 5H2O (g)

Internal combustion engines work by changing chemical energy to kinetic energy, fuelled by the combustion of alkane fuels in oxygen. When this reaction is undergone, so do other unwanted side reactions due to the high pressure and temperature, e.g. the production of nitrogen oxides.

Nitrogen is regularly unreactive but when combined with oxygen, it produces NO and NO2 molecules:

nitrogen + oxygen -> nitrogen (II) oxide

N2 (g) + O2 (g) -> 2NO (g)

and

nitrogen + oxygen -> nitrogen (II) oxide

N2 (g) + 2O2 (g) -> 2NO2 (g)

Sulfur dioxide (SO2) is sometimes present in the exhaust mixture as impurities from crude oil. It is produced when sulfur reacts with oxygen. Nitrogen oxides, carbon dioxide, carbon monoxide, carbon particles, unburnt hydrocarbons, water vapour and sulfur dioxide are all produced in exhaust fumes and are also pollutants that cause problems you need to be aware of for the exam as well as how to get rid of them.

Greenhouse gases contribute to global warming, an important process where infrared radiation from the sun is prevented from escaping back into space by atmospheric gases. On the one hand, some greenhouse gases need to continue this so that the earth can sustain life as it traps heat, however, we do not want the earth’s temperature to increase that much. Global warming is the term given to the increasing average temperature of the earth, which has seen an increase in the last few years due to human activity - burning fossil fuels like alkanes has produced more gases which trap more heat. Examples of greenhouse gases include carbon dioxide, methane and water vapour.

Another pollution problem the earth faces is acid rain. Rain water is already slightly acidic due to the CO2 present in the atmosphere but acid rain is more acidic than this. Nitrogen oxides contribute to acid rain although sulfur dioxide is the main cause. The equation for sulfur dioxide reacting with water in the air to produce oxidised sulfurous acid and therefore sulphuric acid is:

SO2 (g) + H2O (g) + ½ O2 (g) -> H2SO4 (aq)

Acid rain is a problem because it destroys lakes, buildings and vegetation. It is also a global problem because it can fall far from the original source of the pollution.

Photochemical smog is formed from nitrogen oxides, sulfur dioxide and unburnt hydrocarbons that react with sunlight. It mostly forms in industralised cities and causes health problems such as emphysema.

So what can we do about the pollutants?

A good method of stopping pollution is preventing it in the first place, therefore cars have catalytic converters which reduce the amount of carbon monoxide, nitrogen oxides and unburnt hydrocarbons come into the atmosphere by converting them into less toxic gases. Shaped like a honeycomb for increased SA and therefore rate of conversion, platinum and rhodium coat ceramic and act as catalysts for the reactions that take place in an internal combustion engine.

As they pass over the catalyst, they react with each other to form less pollution:

octane + nitrogen (II) oxide -> carbon dioxide + nitrogen + water

C8H18 (g) + 25NO -> 8CO2 (g) + 12 ½ N2 (g) + 9H2O (g)

nitrogen (II) oxide + carbon monoxide  -> carbon dioxide + nitrogen

2NO (g) + 2CO (g) -> 2CO2 (g) + N2 (g)

Finally, sulfur dioxide must be dealt with. The first way it is dealt with is by removing it from petrol before it can be burnt, however, this is often not economically favourable for fuels used in power stations. A process called flue gas desulfurisation is used instead.

In this, gases are passed through a wet semi-solid called a slurry that contains calcium oxide or calcium carbonate. These neutralise the acid, due to being bases, to form calcium sulfate which has little commercial value but can be oxidised to produce a more valuable construction material.

calcium oxide + sulfur dioxide -> calcium sulfite

CaO (s) + SO2 (g) -> CaSO3 (s)

calcium carbonate + sulfur dioxide -> calcium sulfite + carbon dioxide

CaCO3 (s) + SO2 (g) -> CaSO3 (s) + CO2 (g)

calcium sulfite + oxygen -> calcium sulfate

CaSO3 (s) + O -> CaSO4 (s)

SUMMARY

Alkanes are used as fuels due to how they can combust easily to release large amounts of heat energy. Combustion is essentially burning something in the presence of oxygen.

Complete combustion occurs when there is a plentiful supply of air. When an alkane is burned in sufficient oxygen, it produces carbon dioxide and water

Remember state symbols in combustion reactions. In addition, reactions can be halved to balance for 1 mole of compounds by using fractions when dealing with the numbers.

Incomplete combustion occurs when there is a limited supply of air. There are two kinds of incomplete combustion. 

The first type produces water and carbon monoxide.

Carbon monoxide is dangerous because it is toxic and undetectable due to being smell-free and colourless. It reacts with haemoglobin in your blood to reduce their oxygen-carrying ability and can cause drowsiness, nausea, respiratory failure or death. 

The other kind of incomplete combustion occurs in even less oxygen. It produces water and soot (carbon).

Internal combustion engines work by changing chemical energy to kinetic energy, fuelled by the combustion of alkane fuels in oxygen. When this reaction is undergone, so do other unwanted side reactions due to the high pressure and temperature, e.g. the production of nitrogen oxides.

Nitrogen is regularly unreactive but when combined with oxygen, it produces NO and NO2 molecules:

Sulfur dioxide (SO2) is sometimes present in the exhaust mixture as impurities from crude oil. It is produced when sulfur reacts with oxygen.

Nitrogen oxides, carbon dioxide, carbon monoxide, carbon particles, unburnt hydrocarbons, water vapour and sulfur dioxide are all produced in exhaust fumes and are also pollutants that cause problems you need to be aware of for the exam as well as how to get rid of them.

Greenhouse gases contribute to global warming, an important process where infrared radiation from the sun is prevented from escaping back into space by atmospheric gases. Some greenhouse gases need to continue this so that the earth can sustain life as it traps heat, however, we do not want the earth’s temperature to increase that much. Global warming is the term given to the increasing average temperature of the earth, which has seen an increase in the last few years due to human activity - burning fossil fuels like alkanes has produced more gases which trap more heat. 

Another pollution problem the earth faces is acid rain. Nitrogen oxides contribute to acid rain although sulfur dioxide is the main cause. 

Acid rain is a problem because it destroys lakes, buildings and vegetation. It is also a global problem because it can fall far from the original source of the pollution.

Photochemical smog is formed from nitrogen oxides, sulfur dioxide and unburnt hydrocarbons that react with sunlight. It mostly forms in industralised cities and causes health problems such as emphysema.

A good method of stopping pollution is preventing it in the first place, therefore cars have catalytic converters which reduce the amount of carbon monoxide, nitrogen oxides and unburnt hydrocarbons come into the atmosphere by converting them into less toxic gases. Shaped like a honeycomb for increased SA and therefore rate of conversion, platinum and rhodium coat ceramic and act as catalysts for the reactions that take place in an internal combustion engine.

As they pass over the catalyst, they react with each other to form less pollution.

octane + nitrogen (II) oxide -> carbon dioxide + nitrogen + water

C8H18 (g) + 25NO -> 8CO2 (g) + 12 ½ N2 (g) + 9H2O (g)

nitrogen (II) oxide + carbon monoxide  -> carbon dioxide + nitrogen

2NO (g) + 2CO (g) -> 2CO2 (g) + N2 (g)

Finally, sulfur dioxide must be dealt with. The first way it is dealt with is by removing it from petrol before it can be burnt, however, this is often not economically favourable for fuels used in power stations. A process called flue gas desulfurisation is used instead.

In this, gases are passed through a wet semi-solid called a slurry that contains calcium oxide or calcium carbonate. Since they are bases, these neutralise the acid to form calcium sulfate which has little commercial value but can be oxidised to produce a more valuable construction material.

Happy studying!

Alkanes: Saturated Hydrocarbons

So you want to be an organic chemist? Well, learning about hydrocarbons such as alkanes is a good place to start…

Alkanes are a homologous series of hydrocarbons, meaning that each of the series differs by -CH2 and that the compounds contain carbon and hydrogen atoms only. Carbon atoms in alkanes have four bonds which is the maximum a carbon atom can have - this is why the molecule is described to be saturated. Saturated hydrocarbons have only single bonds between the carbon atoms.

The general formula of an alkane is CnH2n+2 where n is the number of carbons. For example, if n = 3, the hydrocarbon formula would be C3H8 or propane. Naming alkanes comes from the number of carbons in the chain structure.

Here are the first three alkanes. Each one differs by -CH2.

Shorter chain alkanes are gases at room temperature, medium ones are liquids and the longer chain alkanes are waxy solids.

Alkanes have these physical properties:

1. They are non-polar due to the tiny difference in electronegativity between the carbon and hydrogen atoms.

2. Only Van der Waals intermolecular forces exist between alkane molecules. The strength of these increase as relative molecular mass increases therefore so does the melting/boiling point.

3. Branched chain alkanes have lower melting and boiling points than straight chain isomers with the same number of carbons. Since atoms are further apart due to a smaller surface area in contact with each other, the strength of the VDWs is decreased.

4. Alkanes are insoluble in water but can dissolve in non-polar liquids like hexane and cyclopentane. Mixtures are separated by fractional distillation or a separating funnel.

The fractional distillation of crude oil, cracking and the combustion equations of the alkanes will be in the next post.

SUMMARY

Alkanes are a homologous series of hydrocarbons. Carbon atoms in alkanes have four bonds which is the maximum a carbon atom can have - this is why the molecule is described to be saturated. Saturated hydrocarbons have only single bonds between the carbon atoms.

The general formula of an alkane is CnH2n+2 where n is the number of carbons.

Shorter chain alkanes are gases at room temperature, medium ones are liquids and the longer chain alkanes are waxy solids.

They are non-polar.

Only Van der Waals intermolecular forces exist between alkane molecules. The strength of these increase as relative molecular mass increases therefore so does the melting/boiling point.

Branched chain alkanes have lower melting and boiling points than straight chain isomers with the same number of carbons.

Alkanes are insoluble in water but can dissolve in non-polar liquids like hexane. Mixtures are separated by fractional distillation or a separating funnel.

Haloalkanes and Their Angelic Reactions: Part One

Haloalkanes are more commonly referred to as halogenoalkanes. Obviously you’ve already read my post on halogenoalkanes and their properties so there’s no surprise that you’re itching to read what I’ve got to say about these beauties and their reactions! Should we delve in?

There are a few different kinds of reactions you must learn for the A Level exam that involve halogenoalkanes. 

The first is the synthesis of chloroalkanes via the photochemical chlorination of the alkanes. I know it looks scary, but don’t worry, it is simpler than it sounds. It essentially means “forming chloroalkanes through chlorinating an alkane in the presence of sunlight”.

Chlorine will react with methane when UV light is present and will form several kinds of chloroalkanes and fumes of hydrogen chloride gas. Chloromethane was once commonly used as a refridgerant. Depending on how many chlorine molecules there are, there will be different compounds formed:

methane + chlorine -> chloromethane + hydrogen chloride

CH4 + Cl2 -> CH3Cl + HCl

or

methane + chlorine -> trichloromethane + hydrogen chloride

CH4 + 3Cl2 -> CHCl3 + 3HCl

When undergone in real life, mixtures of halogenoalkanes are produced with some long chain alkanes which can be separated out with fractional distillation. 

To understand what happens in an overall chemical reaction, chemists use mechanisms. These basically show the step-by-step process that is usually shown by a simple symbol equation that summarises everything.

The chlorination of methane is something you must learn the mechanism for. It’s pretty easy but involves a lot of steps and must be revised periodically to remember them.

The actual reaction is a substitution reaction because one atom or group is replaced by another. Since the chlorine involved is a free radical, it can also be called a free-radical substitution reaction.

1. Initiation

UV light is essential for the first step in the mechanism. This breaks the Cl-Cl covalent bond so that each chlorine leaves with one electron from the shared pair. Chlorine free radicals, with one unpaired electron in the outer shell, are formed. Free radicals are only formed if a bond splits evenly - each atom getting one of the two electrons. The name given to this is homolytic fission.

2. Propagation

This has two sub-steps

(a) Chlorine free radicals (highly reactive) react with methane to form hydrogen chloride and leave a methyl free radical.

Cl• + CH4 -> HCl + •CH3

(b) This free radical then reacts with another chlorine to form chloromethane and another chlorine free radical. Producing free radicals is a chain reaction which is why it is such a problem in ozone depletion - a little amount can cause a lot of destruction.

•CH3 + Cl2 -> CH3Cl +  •Cl

3. Termination

This step stops the chain reaction. It only happens when two free radicals collide to form a molecule in several ways:

Cl• + Cl• -> Cl2

UV light would just break down the chlorine molecule again, so although this is technically a termination reaction it is not the most efficient.

Cl• +  •CH3 -> CH3Cl

Forming one molecule of methane uses one chlorine and one methyl free radical.

•CH3 +  •CH3 -> C2H6

Ethane can be formed from two methyl free radicals - this is why there are longer chain alkanes in the mixture. 

This whole process is how organic halogenoalkanes are the product of photochemical reactions of halogens with alkanes in UV light - made via free radical substitution mechanisms in chain reaction.

Another reaction you need to know is a nucleophilic substitution reactions. A nucleophile is an electron pair donor or proton acceptor - the name comes from Greek origins (”loves nucleus”) - such as hydroxide ions, cyanide ions or ammonia molecules. Hydroxide and cyanide ions are negative but ammonia is neutral.

Halogenoalkanes have a polar bond because of the difference between the highly electronegative halogen and the carbon atom. The 𝛿+ carbon can go under nucleophilic attack. The mechanism for negatively charged nucleophiles these in general is:

Nu represents the nucleophile. This example is with a bromoalkane. Make sure to include curly arrows that begin at a lone pair or the centre of a bond and end at an atom or centre of bond, and delta (slight) charges.

Lets look at a more specific example:

One nucleophile that can be used is a hydroxide ion, found in either water or sodium hydroxide. In this case, you need to know about aqueous sodium hydroxide or potassium hydroxide and a halogenoalkane. This takes place at room temperature but is slow so is often refluxed (continuously boiled and condensed back into the reaction flask). Reflux apparatus is shown below:

The halogenoalkane is dissolved into ethanol since it is insoluable in water and this solution along with the aqueous hydroxide can mix. The product produced is an alcohol, which is organic.

The general reaction is:

R-CH2X + NaOH -> CH3CH2OH + NaX

Where X represents a halogen.

You must learn the mechanism for this reaction. The lone pair on the hydroxide attacks the carbon atom attached to the halogen and this causes both carbon electrons to move to the halogen which becomes a halide ion.

The reaction of a hydroxide ion can also be classed as a hydrolysis reaction as it breaks down chemical bonds with water or hydroxide ions. The speed of reaction depends on the strength of the bond - a stronger carbon-halogen bond, a slower reaction.

C-I is the most reactive (reactivity increases down group 7) and C-F is therefore the least reactive and strongest.

Part two of this post will cover nucleophilic substitution of cyanide ions and ammonia molecules, as well as elimination reactions.

SUMMARY

You need to know about the synthesis of chloroalkanes via the photochemical chlorination of the alkanes. - “forming chloroalkanes through chlorinating an alkane in the presence of sunlight”.

Chlorine will react with methane when UV light is present and will form several kinds of chloroalkanes and fumes of hydrogen chloride gas. Depending on how many chlorine molecules there are, there will be different compounds formed.

When undergone in real life, mixtures of halogenoalkanes are produced with some long chain alkanes which can be separated out with fractional distillation. 

To understand what happens in an overall chemical reaction, chemists use mechanisms. These basically show the step-by-step process.

The chlorination of methane is something you must learn the mechanism for. The actual reaction is a substitution reaction because one atom or group is replaced by another. 

The first step is initiation - UV light is essential for the first step in the mechanism. This breaks the Cl-Cl covalent bond so that each chlorine leaves with one electron from the shared pair. Chlorine free radicals, with one unpaired electron in the outer shell, are formed. Free radicals are only formed if a bond splits evenly - each atom getting one of the two electrons.

Step two is propagation: (a) Chlorine free radicals (highly reactive) react with methane to form hydrogen chloride and leave a methyl free radical (b) this free radical then reacts with another chlorine to form chloromethane and another chlorine free radical. Producing free radicals is a chain reaction which is why it is such a problem in ozone depletion - a little amount can cause a lot of destruction.

To stop the chain reaction, the final step is termination. It only happens when two free radicals collide to form a molecule in several ways: two chlorine free radicals forming a chlorine molecule, two methyl FRs forming ethane or a chlorine FR and a methyl FR forming chloromethane.

Ethane contributes to the longer chain alkanes in the mixture. 

Another reaction you need to know is a nucleophilic substitution reactions. A nucleophile is an electron pair donor or proton acceptor, such as hydroxide ions, cyanide ions or ammonia molecules. Hydroxide and cyanide ions are negative but ammonia is neutral.

Halogenoalkanes have a polar bond because of the difference between the highly electronegative halogen and the carbon atom. The 𝛿+ carbon can go under nucleophilic attack. 

Nu represents the nucleophile. Make sure to include curly arrows that begin at a lone pair or the centre of a bond and end at an atom or centre of bond, and delta (slight) charges.

One nucleophile that can be used is a hydroxide ion, found in either water or sodium hydroxide. In this case, you need to know about aqueous sodium hydroxide or potassium hydroxide and a halogenoalkane. This takes place at room temperature but is slow so is often refluxed (continuously boiled and condensed back into the reaction flask). The halogenoalkane is dissolved into ethanol since it is insoluable in water and this solution along with the aqueous hydroxide can mix. The product produced is an alcohol, which is organic.

The general reaction is :R-CH2X + NaOH -> CH3CH2OH + NaX where X represents a halogen

The lone pair on the hydroxide attacks the carbon atom attached to the halogen and this causes both carbon electrons to move to the halogen which becomes a halide ion.

The reaction of a hydroxide ion can also be classed as a hydrolysis reaction as it breaks down chemical bonds with water or hydroxide ions. 

The speed of reaction depends on the strength of the bond - a stronger carbon-halogen bond, a slower reaction. C-I is the most reactive (reactivity increases down group 7) and C-F is therefore the least reactive and strongest.