Organic I (Basics)

Formulae
Molecular formula This is a list of each type of atom in a molecule, and the number of atoms present. For example, the formula C4H10 indicates that there are four carbon atoms and ten hydrogen atoms. Structural formula This indicates which atoms are bonded to which other atoms. For example, both CH3CH2CH2CH3 and CH3CH(CH3)CH3 have the molecular formula C4H10, but they are clearly different compounds, butane and methyl propane respectively. Structural formula can be abbreviated as above, or shown with all bonds, which is called the full structural formula or displayed structural formula. Draw full structural formulae for CH3CH2CH2CH3 and CH3CH(CH3)CH3.

These molecules have the same molecular formula (atoms) but different structural formulae (bonds). They are structural isomers. Molecules can have the same structural formula and still be different. The structural formula only tells us about the connections between atoms, not about the spatial arrangement of the atoms. A good analogy for this idea is that the connections between bones in right and left hands are identical, but right and left hands are not interchangeable and have a different shape (as is obvious if you try to put a right hand into a left glove). Similarly, the structural formula CH3CH=CHCH3 denotes but-2-ene, but does not specify how the H and CH3 groups are distributed across the rigid C=C bond, which is rigid and flat. Draw the different arrangement of CH3 and H groups in but-2-ene molecules.

So, these isomers have the same molecular formula (atoms) and the same structural formula (bonds) but differ by the spatial arrangement of their atoms. They are stereoisomers. Page 1 of 9 thisisrevision.com

Organic I (Basics) Homologous series and general formulae A homologous series is a series of compounds that have a general formula and whose molecular formulae differ by a CH2 unit. Alkanes Compound CH4 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 Name methane ethane propane butane Molecular formula

The general formula of alkanes is CnH2n+2. Alkenes Compound CH2CH2 CH3CH=CH2 CH3CH2CH=CH2 CH3CH2CH2CH=CH2 Name ethene propene but-1-ene pent-1-ene Molecular formula

The general formula of alkanes is CnH2n. Halogenoalkanes Compound CH3Br CH3CH2Br CH3CH2CH2Br CH3CH2CH2CH2Br Name bromomethane bromoethane 1-bromo propane 1-bromo butane Molecular formula

The general formula of halogenoalkanes is CnH2n+1X. Alcohols Compound CH3OH CH3CH2OH CH3CH2CH2OH CH3CH2CH2CH2OH Name methanol ethanol propan-1-ol butan-1-ol Molecular formula

The general formula of alcohols is CnH2n+1OH or CnH2nO [NB The range of compounds used here to illustrate isomerism is wider than that covered by the unit, and also discussion of the impact of isomerism on physical properties is made to link the topic to structure and bonding]

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Organic I (Basics)

Isomerism
Isomerism is about how different molecules can be made from the same set of atoms. The set of atoms is called the molecular formula. For example, C4H8 means that there are 4 carbon atoms and 8 Hydrogen atoms. C atoms have four bonds H atoms have one bond N atoms have three bonds O atoms have two bonds Halogen atoms have one bond (in organic chemistry)

Broadly speaking, there are two ways in which molecules can be different yet have the same molecular formula: 1. The atoms can be joined up in a different order, for example but-1-ene and but-2-ene have the same molecular formula C4H8 but their structural formulae are different.

This type of isomerism is structural isomerism. 2. Alternatively, the structural formula can be kept the same but the shape of the molecule can be varied. For example, but-2-ene can exist as two different molecules, cis-but-2-ene and trans-but-2-ene.

This type of isomerism is an example of stereoisomerism, called geometrical isomerism.

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Organic I (Basics)

Structural Isomerism
There are three types of structural isomerism, Chain (or Branch), Positional and Functional Group. Chain Isomerism

Draw all the molecules that have the molecular formula C5H12.

Simple chain isomers have very similar chemical properties has they are governed by the chemistry of C-H and C-C bonds. However, you need to understand how the boiling point of the above molecules is affected by branching. When the above substances boil, the intermolecular forces are broken by the heat energy being supplied. The C-C and C-H bonds do not break at all. The intermolecular force in operation between these molecules is the induced dipole force, which is studied in more detail in Structure and Bonding. Usually we think about the size of the electron cloud with this type of force, but since the molecules are isomers they will have the same size electron cloud because they have exactly the same atoms. Instead, we look to for branching in the molecule because branching lowers the surface area, which in turn lowers the points of contact between the molecules. Show how pentane molecules have more points of contact than dimethylpropane molecules.

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Organic I (Basics) Positional Isomerism

In positional isomerism, the position of an atom or group of atoms moves along a carbon chain that otherwise stays the same. Draw butan-1-ol and butan-2-ol.

Draw 1-bromo butane and 2-bromo butane.

Compounds that are met later in different Units can also undergo positional isomerism. Draw positional isomers of dichlorobenzene

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Organic I (Basics) The chemical properties of positional isomers are broadly similar because they will contain the same functional group, but there will be some variation because the reactions of a functional group do depend on its environment. The physical properties such as boiling point depend on the intermolecular forces. Discuss the order of boiling points between 1- and 2-bromo butanes (Hint, they depend upon the exposure of the C-Br dipole and surface area).

1-bromobutane has the higher boiling point because it has the larger surface area as it is not branched, so there are more points of contact between the molecules as they pass by each other, which enables the induced dipole forces of attraction to interact more. Also, the polar C-Br bond at the end of the molecule can interact more freely with other polar C-Br bonds than when it is in the body of the molecule, with bulky CH3 groups on either side sterically hindering (getting in the way of) its interactions.

Discuss the order of boiling points between butan-1 and 2-ols (Hint, they depend upon the exposure of the OH group and surface area).

Butan-1-ol has the higher boiling point because it has the larger surface area etc its OH groups are exposed and can H-bond more effectively to OH groups in another molecule.

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Organic I (Basics) Functional Group Isomerism

In functional group isomerism, a structural change completely alters the functional group of the molecule. Consequently, both chemical and physical properties change significantly. Draw all the isomers of C2H6O, using what you know about how many bonds each atom may have.

Draw all the isomers of C3H6O that are aldehydes or ketones.

Explain why CH3CH2OH is a liquid whereas CH3OCH3 is a gas (Hint, it is something to do with intermolecular forces!)

Molecules of ethanol have OH groups, so they have H-bonding between them. Molecules of ethoxyethane do not, they have a mixture of induced and permanent dipoles. The intermolecular forces in ethanol are stronger due to the presence of H-bonding, which explains why it is a liquid at room temperature, yet ethoxy ethane is a gas.

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Organic I (Basics)

Stereoisomerism
There are two types of stereoisomersim, geometrical and optical (Optical isomerism is covered in a later unit). In both types, the structural formula stays the same. The molecules differ because of the spatial arrangement of the atoms. Geometrical

A restriction of rotation (such as C=C) allows the groups around it to be arranged in two different ways. Often the words cis and trans can be used to identify the isomers. Draw out the geometrical isomers of CH3CH=CHCH3

Draw out the geometrical isomers of CH3CH=CHC2H5

Draw out the geometrical isomers of CH3CH=C(OH)Br

The further condition is that there cannot be two identical groups on either C in the double bond. To illustrate this, try drawing CH2=CHCH3 as geometrical isomers.

It doesnt work!

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Organic I (Basics) In addition, you need to understand why there is no free rotation about a double bond. Draw out the p orbitals that make the pi bond in a C=C, and show that there is no free rotation due to sideways overlap of p orbitals.

NB there are plenty of examples of geometrical isomers that do not have a C=C, and equally they might not even be organic molecules. Cyclic isomers of C3H4Cl2

Isomers of CH3CH=NC6H5

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