Carbon

Chemistry
Structure an
d Formulae
Science Yea

r2

1.1 Explain the occurrence of carbon

compounds with straight chains, branched
chains and rings

Revision
0What are atomic orbitals?
0What atomic orbitals are present in carbon?
0What are the shapes of these orbitals?

Atomic Orbitals
0A region of space around the nucleus within which the

probability of finding an electron is high (~95%)

0This region can be calculated using advanced

mathematical procedures (Schredinger)

There is no way of determining the exact location of an

electron within an atom

There is a definite 3 dimensional area around the nucleus
within which an electron is most likely to be found

Atomic Orbitals in Carbon

0s orbitals are spherical
1s and 2s orbitals are similar in shape however

electron density is closer to the nucleus for the 1s

orbital

0p orbitals are dumbbell shaped

There are three p orbitals - 2px, 2py and 2pz

Shapes of Orbitals

The Carbon Atom

http://chemwiki.ucdavis.edu/Organic_Chemistry/Organic_Chemistry_With_a_Biological_Emphasis/Chapter__1%3A_Chapter_1%3A_Introduction_to_organic_structure_and_bonding_
I/Section_1.5%3A_Valence_bond_theory%3A_sp,_sp2,_and_sp3_hybrid_orbitals

Organic Compounds
Carbon forms a vast number of compounds because
of:
1. Tetravalency each carbon atom forms four
bonds
2. Catenation - carbon has the ability to form
strong covalent bond with other carbon atoms
3. Hybridisation -2s and 2p orbitals mix and
rearrange to form hybrid orbitals; can form
multiple bonds [single (sp3), double (sp2), triple
bonds (sp)]

Catenation
0The ability for carbon to bond to itself, gives rise to:
Straight chains

Branched chains

Rings

0You can also get a combination of rings and chains

Catenation and Tetravalency

0 Carbon can also form single, double or triple bonds with itself

0 Different atoms or groups of atoms can be attached to the carbon atom

The basic atom is HYDROGEN but groups containing OXYGEN,

NITROGEN, HALOGENS and SULPHUR may be attached to the

carbon atom or chain
This group attached to the carbon chain, called the functional group, may
determine the chemistry of an organic compound

Why does carbon form four bonds?

0 Carbon forms four

bonds (instead of two)

2s 2 electrons

1s 2 electrons

0 Simple model of

carbon does not help

in explaining the
phenomenon

2p 2 electrons

0 Explanation found

using actual
illustration of atomic
orbitals

Simplistic Carbon atom

1s2, 2s2, 2p2

Bonding
The ground state configuration
of carbon is unsuitable for
bonding
In the ground state carbon can
only form bonds of unequal
length and strength
For correct bonding to occur
some changes have to be made
in the orbitals

2px

2py

2pz

Energy
2s

1s
Ground State of Carbon

Hybridisation
0 2s electrons spontaneously

promoted to empty 2p orbital

0 s orbital and the THREE

p orbitals mix to form

FOUR hybrid orbitals (sp3)

0 number of orbitals is

conserved during
hybridisation

The Excited Carbon Atom

Four identical sp3 orbitals formed

All the same shape, size and energy

sp hybridized orbitals
3

s and p orbitals

sp3 orbitals
Arranged in a tetrahedral
conformation
Gives minimum repulsion
between orbitals
Angle of 109 from each
other
Can form bonds by
overlapping with orbitals of

Bonding in Methane (CH4)

0 Overlap of s and sp3 orbitals

form sigma () bond

0 Carbon atom is sp3

hybridized

0 Bonds are formed by

overlapping of the 1s
orbitals of four hydrogen
atoms with the sp3 orbitals
of the carbon atom

Methane has 4 bonds

Note that each bond contains 2 electrons:

1 from s orbital of hydrogen
1 from sp3 orbital of carbon

Bonding in Ethene (C2H4)

0 Ethene contains a double bond

0 In carbon of double bond there are three sp2 hybrid orbitals and one

unused p orbital
0 Each carbon in the double bond is sp2 hybridised
0 Unused p orbital overlaps above and below the plane to form a pi ()
bond

http://www.citycollegiate.com/hybridization2.htm

Bonding in Ethyne (C2H2)

0 Ethyne contains a triple bond

0 In carbon of triple bond there are two sp hybrid orbitals and two

unused p orbital
0 Each carbon in the triple bond is sp hybridised
0 The two unused p orbitals overlap above and below the plane to form
two pi () bonds

 The triple bond consists of one sigma bond and

two pi bonds
The geometry around each carbon is linear with a
bond angle of 180o
http://pages.towson.edu/ladon/carbon.html

Some carbon compounds can display Resonance

Some molecules cannot be adequately represented by a single Lewis
structure

For example, two valid Lewis structures can be drawn for the anion
(HCONH)

These structures are called resonance structures or resonance forms

A double headed arrow is used to separate the two resonance structures
22

1.2 Explain the meaning of the

term homologous series

Homologous Series
A series of compounds of similar structure in which each member
differs from the next by a common repeating unit, CH2
All members share the same general formula
Molecular formula of each member differs from its neighbour by CH2

(e.g. CH4, C2H6, ...)

Each member contains the same functional group
Each member has similar chemical properties
Each member shows a gradual change in physical properties as molar
mass increases
Each member of the series can usually be prepared by similar methods
eg. First three members of the ALCOHOLs homologous series

CH3OH
METHANOL

C2H5OH
ETHANOL

C3H7OH
PROPAN-1-OL

Functional Groups
0 Large number of organic compounds, so it is easier to split them into small

sections for study

0 This is done by studying compounds which behave in a similar way because
they have a particular atom, or group of atoms, Functional Group, in their
structure
Functional groups can consist of one atom, a group of atoms or multiple
bonds between carbon atoms
0 Each functional group has its own distinctive properties which means that the

properties of a compound are governed by the functional group(s) in it

H H H H H

H H H H H
H C C C C C

NH2

OH

H H H H H

H H H H H
Carbon
skeleton

H C C C C C

Functional
Group = AMINE

Carbon
Functional
skeleton
Group = ALCOHOL

COMMON FUNCTIONAL
GROUPS
Group

Suffix

General
Formula

Example
(name)

Example
(molecular
formula)

Alkane

- ane

CnH2n+2

Ethane

C2H6

Alkene

- ene

CnH2n

Ethene

C2H4

Alkyne

- yne

CnHn

Ethyne

C2H2

Alcohol

- ol

CnH2n+1OH

Ethanol

C2H5OH

Halogenoalkane
Aldehyde
Ketone
Carboxylic Acid

COMMON FUNCTIONAL
GROUPS
Group

Amine
Amide
Ester
Nitrile
Ether
Acyl chloride

Suffix

General
Formula

Example
(name)

Example
(molecular
formula)

1.3 Distinguish between

empirical, molecular and
structural formulae

Depiction of Organic Molecules

Empirical formula is the simplest whole number ratio of atoms
in a compound e.g. CH2
Molecular formula is the actual number of atoms in a
compound e.g. C2H6 for ethene
Structural formula is the diagrammatic representation of an
organic molecule showing the arrangement of atoms

Structural Formulae
May be represented as:
Displayed formula
Condensed formula
Skeletal formula carbon atoms and hydrogens are not shown;

An open end represents a CH3 group while a bend represents

a CH2 group

http://www.ivy-rose.co.uk/Chemistry/Organic/How-to-draw-skeletal-formulae-of-organic-molecules.php

Depiction of Organic Molecules eg. Butane

MOLECULAR FORMULA
The exact number of atoms of each
element present in the molecule

C4H10

EMPIRICAL FORMULA
The simplest whole number ratio
of atoms in the molecule

C2H5

STRUCTURAL FORMULA
The minimal detail using conventional
groups, for an unambiguous structure
DISPLAYED FORMULA
Shows both the relative placing of atoms
and the number of bonds between them

CH3CH2CH2CH3 CH3CH(CH3)CH3
***there are two possible structures

H
H
H C H
H

1.4 Determine formulae from

experimental data

Determining Empirical Formulae

1. What is the empirical formula for a compound

containing 38.8% carbon, 16.2% hydrogen and 45.1%

nitrogen?
Ans: CH5N

2. Find the empirical formula of a compound containing

4g of hydrogen and 32g of oxygen

Ans: H2O

3. When 3.79 grams of an organic compound is burned,

6.61 grams of CO2 and 3.59 grams of H2O are

produced. What is the empirical formula of this
Ans: C3H8O2
compound?
http://thechemguys.blogspot.com/2010/12/calculating-emperical-formula-of.html

Determining Molecular Formulae

The empirical formula of hexane is C3H7. Its molecular weight is 86.2
amu. What is the molecular formula of hexane?
Calculate the formula weight of C3H7

Calculate the ratio between the molecular weight and the empirical

weight:

The molecular formula must be twice the empirical formula:

(C3H7)2 or C6H14

Determining Molecular Formulae

1. The compound ethylene glycol is often used as an

antifreeze. It contains 38.7% carbon, 9.75% hydrogen, and

the rest oxygen. The molecular weight of ethylene glycol is
62.07 g. What is the molecular formula of ethylene glycol?
2. The compound dioxane contains only carbon, hydrogen,

and oxygen. When 0.956 g dioxane is burned, 1.91 g

carbon dioxide and 0.782 g water are formed. In another
experiment, it was determined that 6.04x10 -3 mol dioxane
weighs 0.532 g. What is the molecular formula of dioxane?

1.5 Write structural formulae

Structural Formulae
May be represented as:
Displayed formula
Condensed formula
Skeletal formula carbon atoms and hydrogens are not shown;

An open end represents a CH3 group while a bend represents

a CH2 group

http://www.ivy-rose.co.uk/Chemistry/Organic/How-to-draw-skeletal-formulae-of-organic-molecules.php

Structural Formula
Examples of structural formulae for ring compounds:

Homework
Write the following using the (a) displayed formula and (ii)
skeletal formula:
a. CH3CH2CH(OH)CH2CH2CH3
b. CH3CH2CH(OH)CH2CH(CH3)2
c. CH3CH2CH(OH)CHBrCH3
d. C6H6
e. C6H5Br

1.6 Apply the IUPAC rules to

named organic compounds

Nomenclature

Two ways to name organic compounds:

Systematic based on IUPAC rules for naming organic
compounds eg. Ethanoic acid
Trivial based on some characteristic of compound or
historical aspect eg. Acetic acid (from acetum; latin for vinegar)

IUPAC Nomenclature
A systematic way of naming organic compounds. The name
consists of two parts:
Stem - based on the carbon skeleton (backbone)
Suffix based on the functional group present (homologous group)

Nomenclature
1. STEM
Based on the carbon skeleton
Carbon skeleton is named using the number of

carbon atoms in longest chain bearing the

functional group + a prefix showing the
position and identity of any side-chain
substituents/groups
Apart from the first four the number of

carbons atoms is indicated by a prefix derived

from the Greek numbering system
Working out which is the longest chain can

pose a problem with larger molecules

Prefix
methethpropbutpenthexheptoctnondec-

C atoms
1
2
3
4
5
6
7
8
9
10

Nomenclature
2. SUFFIX
The last part of the name tells you

which functional group is present

The relevant suffix is added to the
end of the basic stem
In many cases the position of the
functional group must be given to
avoid any ambiguity
Substituents
- Many compounds have substituents
(additional atoms, or groups)
attached to the main chain
- Their position is numbered

Functional group
ALKANE
ALKENE
ALKYNE
ALCOHOL
ALDEHYDE
KETONE
ACID

1-CHLOROBUTANE

Suffix

- ANE
- ENE
- YNE
- OL
- AL
- ONE
- OIC ACID

2-CHLOROBUTANE

Nomenclature - Alkanes
0 Identify the main carbon chain/skeleton - the

carbon chain containing the most carbon

atoms
0 Remember:
It is too complicated to draw molecules with

the correct bond angles

Single covalent bonds are free to rotate

0 A simple way to check the length of carbon

chain is to run a pencil along the chain and

see how many carbon atoms can be covered
without reversing direction or taking the
pencil off the page
0 For eg. in all the compounds below, there are
five carbon atoms in the main chain
0 All the structures are of the same molecule Pentane C5H12

CH3 CH2 CH2 CH2 CH3

CH3
CH2 CH2 CH2 CH3
CH3
CH2 CH2 CH2
CH3
CH3 CH2 CH3
CH2 CH2

Nomenclature - Alkanes
How long is the longest chain?
Look at the structures and work out how many carbon atoms are in the
longest chain.
CH3
CH2
CH3

CH

CH2

LONGEST CHAIN = 5

CH3
CH3

CH3

CH2

CH2

CH2

CH

CH3

LONGEST CHAIN = 6

CH3
CH3 CH2
CH3

CH2

CH

CH

CH3

LONGEST CHAIN = 6

Nomenclature - Alkanes

What if the stem (or carbon backbone) has a side group or substituent on it?

SIDE-CHAIN - carbon based substituents are placed before the chain name they have the
prefix -yl added to the basic stem (e.g. CH 3 is methyl)

Alkyl radicals

methyl CH3 -

CH3

ethyl
CH3- CH2C2H5
propyl CH3- CH2- CH2C3H7
1. Number the principal chain from one end to give the lowest numbers.
2. Side-chain names appear in alphabetical order - butyl, ethyl, methyl, propyl
3. Each side-chain is given its own number
4. If identical side-chains appear more than once, prefix with e.g. di, tri, tetra, penta
5. Numbers are separated from names by a HYPHEN e.g.

2-methylheptane

6. Numbers are separated from numbers by a COMMA e.g. 2,3-dimethylbutane

Examples of Substituents
chloro

Cl

bromo

Br

iodo

nitro

NO2

methoxy

OCH3

amino

NH2

Nomenclature

Example: longest chain 8 (it is an octane)

3,4,5 are the numbers NOT 4,5,6
order is ethyl, methyl, propyl
3-ethyl-5-methyl-4-propyloctane
CH3 CH3
CH3

CH2

CH2

CH

CH2

CH3

CH2

CH2

CH

CH

CH2

CH3

I.U.P.A.C. Nomenclature
Longest chain = 5 ; so it is a pentane

CH3

A CH3, methyl, group is attached to the

third carbon from one end...

CH2
CH3 CH CH2 CH3

3-methylpentane

CH3
CH3 CH2 CH2 CH2 CH CH3

Longest chain = 6;so it is a hexane

A CH3, methyl, group is attached to the
second carbon from one end...
2-methylhexane

CH3
CH3 CH2
CH3 CH2 CH CH CH3

Longest chain = 6
hexane

so it is a

CH3, methyl, groups are attached to

the third and fourth carbon atoms
(whichever end you count from).
3,4-dimethylhexane

1.7 Define, with examples,

structural isomerism

Structural Isomerism
Structural isomerism (or constitutional isomerism), is a
form of isomerism in which molecules have the same
molecular formula but different bonding arrangement

Chain isomerism eg. C4H10

***isomers have
different
arrangements of
the carbon chain

Structural Isomerism
Positional isomerism eg. C4H9OH
P.I contain same
carbon skeleton but
the functional
group is in different
positions on the
carbon chain

Structural Isomerism
Functional group isomerism eg. C3H6O
F.G. isomers
contain
different
functional
groups

Classwork
1. Draw and name all the possible isomers for
a. C5H12
b. C8H18
2. Draw two positional isomers with the molecular

formula C3H7Br
3. Draw two functional group isomers with the

molecular formula C3H6O

1.8 Explain stereoisomerism

Stereoisomerism
Stereoisomerism occurs when isomers have identical

molecular formulae and the atoms are linked together in the

same order, but have different relative positions in space
Stereoisomers may be classified as geometric isomers or optical

isomers

Geometric (or cis-trans) isomerism eg. alkenes

bond restricts rotation around a bond eg. double bond
cis isomer identical groups are on the same side of the double

bond
trans isomer - identical groups are on opposite sides of the
double bond

Geometric Isomerism
Geometric (or cis-trans) isomerism eg. butene
cis isomer vs. trans isomer

The identical groups in question MUST be on two different

carbons in order to display cis-trans isomerism

Geometric Isomerism
There are two requirements for cis-trans isomerism:
Rotation must be restricted in the molecule
There must be two non-identical groups on each doubly bonded

carbon atom
Cis-trans isomerism also occurs in cyclic compounds (ring structures)
since groups are unable to rotate about any of the ring carboncarbon
bonds.
In cyclic compounds, groups can be either on the same side of the
ring (cis) or on opposite sides of the ring (trans).

Geometric Isomerism
Alkenes with a C=CH2 unit do not exist as cis-trans isomers.

Alkenes with a C=CR2 unit, where the two R groups are the same, do

not exist as cis-trans isomers.

Alkenes of the type RCH=CHR can exist as cis and trans isomers;

cis if the two R groups are on the same side of the carbon-to-carbon
double bond, and trans if the two R groups are on opposite sides of
the carbon-to-carbon double bond.

Stereoisomerism
Optical isomerism
exists for compounds which are

mirror images of each other; nonsuperimposable on each other

Molecules possess a CHIRAL

centre
Optical isomers show similar

physical and chemical properties

How can we distinguish

between two optical isomers?
http://astrobiology.berkeley.edu/Mars101/definitions.htm

Optical isomers
Differ in the direction in which

they rotate plane polarized light

D-isomer (dextrorotary) rotates

light in clockwise (+) direction

L-isomer (laevorotary) rotates

light in anticlockwise (-) direction

The isomers are called

enantiomers
Racemic mixture optically

inactive; contains equal amounts

(50:50) of each enantiomer
http://www.chem.yale.edu/~chem125/125/thalidomide/thalidomide.html

1.9 determine the possible

isomers from given molecular
formulae

Classwork
1. Draw and name all the possible isomers for the following

molecular formula:
a.

C5H11Br

b.

C6H14

c.

C4H8

d.

C6H12

2. For the molecular formulae above, state the type of isomerism

which may exist