Representative Carbon Compounds:

Functional Groups, Intermolecular

Forces
 Carbon-carbon Covalent Bonds
 Carbon forms strong covalent bonds to other carbons
and to other elements such as hydrogen, oxygen,
nitrogen and sulfur
This accounts for the vast variety of organic compounds possible
 Organic compounds are grouped into functional group
families
A functional group is a specific grouping of atoms (e.g. carbon-
carbon double bonds are in the family of alkenes)
An instrumental technique called infrared (IR) spectroscopy is
used to determine the presence of specific functional groups

Chapter 1 2
 Hydrocarbons: Representative Alkanes, Alkenes
Alkynes, and Aromatic Compounds
Hydrocarbons contain only carbon and hydrogen atoms
Subgroups of Hydrocarbons:
 Alkanes contain only carbon-carbon single bonds
 Alkenes contain one or more carbon-carbon double bonds
 Alkynes contain one or more carbon-carbon triple bonds
 Aromatic hydrocarbons contain benzene-like stable structures (discussed later)
Saturated hydrocarbons: contain only carbon-carbon single
bonds e.g. alkanes
Unsaturated hydrocarbons: contain double or triple carbon-
carbon bonds e.g. alkene, alkynes, aromatics
 Contain fewer than maximum number of hydrogens per carbon
 Capable of reacting with H2 to become saturated

Chapter 1 3
 Representative Hydrocarbons
 Alkanes
Principle sources of alkanes are natural gas and petroleum
 Smaller alkanes (C1 to C4) are gases at room temperature
Methane is
 A component of the atmosphere of many planets
 Major component of natural gas
 Produced by primitive organisms called methanogens found in mud, sewage and
cows’ stomachs

Chapter 1 4
 Alkenes
Ethene (ethylene) is a major industrial feedstock
 Used in the production of ethanol, ethylene oxide and the polymer polyethylene

Propene (propylene) is also very important in industry

 Molecular formula C3H6
 Used to make the polymer polypropylene and is the starting material for acetone
Many alkenes occur naturally

Chapter 1 5
 Alkynes
Ethyne (acetylene) is used in welding torches because it burns at
high temperature

Many alkynes are of biological interest

 Capillin is an antifungal agent found naturally
 Dactylyne is a marine natural product
 Ethinyl estradiol is a synthetic estrogen used in oral contraceptives

Chapter 1 6
 Benzene: A Representative Hydrocarbon
Benzene is the prototypical aromatic compound
 The Kekulé structure (named after August Kekulé who formulated it) is a six-
membered ring with alternating double and single bonds

Benzene does not actually have discreet single and double

carbon-carbon bonds
 All carbon-carbon bonds are exactly equal in length (1.38 Å)
 This is between the length of a carbon-carbon single bond and a carbon-carbon
double bond
Resonance theory explains this by suggesting there are two
resonance hybrids that contribute equally to the real structure
 The real structure is often depicted as a hexagon with a circle in the middle

Chapter 1 7
 Molecular orbital theory explains the equal bond lengths
of benzene by suggesting there in a continuous overlap
of p orbitals over the entire ring
All carbons in benzene are sp2 hybridized
 Each carbon also has a p orbital
Each p orbital does not just overlap with one adjacent p but
overlaps with p orbitals on either side to give a continuous
bonding molecular orbital that encompasses all 6 carbons
All 6 p electrons are therefore delocalized over the entire ring and
this results in the equivalence of all of the carbon-carbon bonds

Chapter 1 8
 Polar Covalent Bonds
 Polar covalent bonds occur when a covalent bond is
formed between two atoms of differing
electronegativities
The more electronegative atom draws electron density closer to
itself
The more electronegative atom develops a partial negative charge
(d-) and the less electronegative atom develops a partial positive
charge (d+)
A bond which is polarized is a dipole and has a dipole moment
The direction of the dipole can be indicated by a dipole arrow
 The arrow head is the negative end of a dipole, the crossed end is the positive end

Chapter 1 9
 Example: the molecule HCl
The more electronegative chlorine draws electron density away
from the hydrogen
 Chlorine develops a partial negative charge

 The dipole moment of a molecule can be measured

experimentally
It is the product of the magnitude of the charges (in
electrostatic units: esu) and the distance between the charges
(in cm)
The actual unit of measurement is a Debye (D) which is
equivalent to 1 x 10-18 esu cm

Chapter 1 10
 A map of electrostatic potential (MEP) is a way to
visualize distribution of charge in a molecule
Parts of the molecule which are red have relatively more electron
density or are negative
 These region would tend to attract positively charged species
Parts of the molecule which are blue have relatively less electron
density or are positive
 These region would tend to attract negatively charged species
The MEP is plotted at the van Der Waals surface of a molecule
 This is the farthest extent of a molecule’s electron cloud and therefore indicates
the shape of the molecule
The MEP of hydrogen chlorine clearly indicates that the negative
charge is concentrated near chlorine
 The overall shape of the molecule is also represented

Chapter 1 11
 Molecular Dipole
In diatomic molecules a dipole exists if the two atoms are of
different electronegativity
In more complicated molecules the molecular dipole is the sum of
the bond dipoles
Some molecules with very polar bonds will have no net molecular
dipole because the bond dipoles cancel out
 The center of positive charge and negative charge coincide in these molecules

Chapter 1 12
 Examples
In carbon tetrachloride the bond dipoles cancel and the overall
molecular dipole is 0 Debye

In chloromethane the C-H bonds have only small dipoles but the
C-Cl bond has a large dipole and the molecule is quite polar

An unshared pair of electrons on atoms such as oxygen and

nitrogen contribute a great deal to a dipole
 Water and ammonia have very large net dipoles

Chapter 1 13
 Some cis-trans isomers differ markedly in their dipole
moment
In trans 1,2-dichloroethene the two carbon-chlorine dipoles cancel
out and the molecular dipole is 0 Debye
In the cis isomer the carbon-chlorine dipoles reinforce and there
is a large molecular dipole

Chapter 1 14
 Functional Groups
Functional group families are characterized by the presence of a
certain arrangement of atoms called a functional group
A functional group is the site of most chemical reactivity of a
molecule
 The functional group is responsible for many of the physical properties of a
molecule
Alkanes do not have a functional groups
 Carbon-carbon single bonds and carbon-hydrogen bonds are generally very
unreactive

Chapter 1 15
 Alkyl Groups and the Symbol R
 Alkyl groups are obtained by removing a hydrogen from an alkane
 Often more than one alkyl group can be obtained from an alkane by removal
of different kinds of hydrogens

 R is the symbol to represent a generic alkyl groups

 The general formula for an alkane can be abbreviated R-H

Chapter 1 16
A benzene ring with a hydrogen removed is called a phenyl and
can be represented in various ways

Toluene (methylbenzene) with its methyl hydrogen removed is

called a benzyl group

Chapter 1 17
 Alkyl Halides
In alkyl halides, halogen (F, Cl, Br, I) replaces the hydrogen of an
alkane
They are classified based on the carbon the halogen is attached to
 If the carbon is attached to one other carbon that carbon is primary (1o) and the
alkyl halide is also 1o
 If the carbon is attached to two other carbons, that carbon is secondary (2o) and
the alkyl halide is 2o
 If the carbon is attached to three other carbons, the carbon is tertiary (3o) and the
alkyl halide is 3o

Chapter 1 18
 Alcohols
In alcohols the hydrogen of the alkane is replaced by the hydroxyl
(-OH) group
 An alcohol can be viewed as either a hydroxyl derivative of an alkane or an alkyl
derivative of water

Alcohols are also classified according to the carbon the hydroxyl

is directly attached to

Chapter 1 19
 Ethers
Ethers have the general formula R-O-R or R-O-R’ where R’ is
different from R
 These can be considered organic derivatives of water in which both hydrogens
are replaced by organic groups
 The bond angle at oxygen is close to the tetrahedral angle

 Amines
Amines are organic derivatives of ammonia
 They are classified according to how many alkyl groups replace the hydrogens of
ammonia
 This is a different classification scheme than that used in alcohols

Chapter 1 20
 Aldehydes and Ketones
 Both contain the carbonyl group

 Aldehydes have at least one carbon attached to the carbonyl group

 Ketones have two organic groups attached to the carbonyl group

 The carbonyl carbon is sp2 hybridized

 It is trigonal planar and has bond angle about 120o

Chapter 1 21
 Carboxylic Acids, Esters and Amides
All these groups contain a carbonyl group bonded to an oxygen or
nitrogen
Carboxylic Acids
 Contain the carboxyl (carbonyl + hydroxyl) group

Esters
 A carbonyl group is bonded to an alkoxyl (OR’) group

Chapter 1 22
Amide
 A carbonyl group is bonded to a nitrogen derived from ammonia or an amine

Chapter 1 23
Summary of Important Families of Organic
Compounds

Chapter 1 24
 Summary (cont.)

Chapter 1 25
 Physical Properties and Molecular Structure
The strength of intermolecular forces (forces between molecules)
determines the physical properties (i.e. melting point, boiling
point and solubility) of a compound
Stronger intermolecular forces result in high melting points and
boiling points
 More energy must be expended to overcome very strong forces between
molecules
The type of intermolecular forces important for a molecule are
determined by its structure

Chapter 1 26
 Dipole-Dipole Forces
Dipole-dipole forces are between molecules with permanent
dipoles
 There is an interaction between d+ and d- areas in each molecule; these are
much weaker than ion-ion forces
 Molecules align to maximize attraction of d+ and d- parts of molecules
 Example: acetone

Chapter 1 27
 Hydrogen Bonds
Hydrogen bonds result from very strong dipole-dipole forces
There is an interaction between hydrogens bonded to strongly
electronegative atoms (O, N or F) and nonbonding electron pairs
on other strongly electronegative atoms (O, N or F)

Chapter 1 28
 Example
Ethanol (CH3CH2OH) has a boiling point of +78.5oC; its isomer
methyl ether (CH3OCH3) has a boiling point of -24.9oC
 Ethanol molecules are held together by hydrogen bonds whereas methyl ether
molecules are held together only by weaker dipole-dipole interactions

A factor in melting points is that symmetrical molecules tend to

pack better in the crystalline lattice and have higher melting
points

Chapter 1 29
 van der Waals Forces (London or Dispersion Forces)
Van der Waals forces result when a temporary dipole in a
molecule caused by a momentary shifting of electrons induces an
opposite and also temporary dipole in an adjacent molecule
 These temporary opposite dipoles cause a weak attraction between the two
molecules
 Molecules which rely only on van der Waals forces generally have low melting
points and boiling points

Chapter 1 30
 Solubilities
Water dissolves ionic solids by forming strong dipole-ion
interactions
 These dipole-ion interactions are powerful enough to overcome lattice energy and
interionic interactions in the solid

Chapter 1 31
Generally like dissolves like
 Polar solvents tend to dissolve polar solids or polar liquids
 Methanol (a water-like molecule) dissolves in water in all proportions and interacts
using hydrogen-bonding to the water

A large alkyl group can overwhelm the ability of the polar group to
solubilize a molecule in water
 Decyl alcohol is only slightly soluble in water
 The large alkyl portion is hydrophobic (“water hating”) and overwhelms the
capacity of the hydrophilic (“water loving”) hydroxyl

Chapter 1 32
 Summary of Attractive Electric Forces

Chapter 1 33