CHAPTER 2

Structure and Reactivity:

Acids and Bases, Polar and

Nonpolar Molecules
2-1 Kinetics and Thermodynamics of Simple Chemical
Processes
Chemical thermodynamics: Is concerned with the extent that a
reaction goes to completion.
Chemical kinetics: Is concerned with the speed that a reaction
goes to completion.
Thermodynamic Control: The most stable products are formed.
Kinetic Control: The fastest product is formed.
Equilibria are governed by the thermodynamics
of chemical change.
When the concentrations of reactants and products no longer
change, the system is said to be at equilibrium.
A system at equilibrium is described mathematically:

[B ]
A  B, K =
[A ]
or
[C ][D ]
A + B  C + D, K =
[A ][B ]

A large value of K indicates that the reaction goes to

completion.
The equilibrium constant can be related to the
thermodynamic function Go:
 G   RT ln K
o

When Go is negative, the equilibrium constant is greater

than 1 and the products of the reaction are favored over the
reactants.
When Go is positive, the equilibrium constant is less that 1
and the reactants of the reactions are favored over the
products.
The free energy change is related to changes in
bond strengths and the degree of order in the
system.
The Gibbs free energy change for a reaction is related to the
enthalpy change and the entropy change for the reaction:

G  H  T S
o o o

The enthalpy change, Ho, can be estimated:

H    B ond E nergies     B ond E nergies 

o

R eactants Products

The entropy change, So, is related to the amount of disorder in

the system. The entropy of a substance phase is much larger in
the gas than in the liquid phase.
In a chemical reaction where all substances are in the same
phase, the entropy will increase if there are more product
molecules than reactant molecules.
The rate of a chemical reaction depends on the
activation energy.
The potential energy of the system as a chemical change occurs
can be plotted vs. time:

The higher the activation energy, Ea, the slower the reaction.
Collisions supply the energy to get past the
activation-energy barrier.
The average kinetic energy of molecules at room temperature is
about 0.6 kcal mol-1. The kinetic energies of individual molecules
can be plotted as a Boltzmann distribution curve:

As can be seen from the curves, there are more molecules having large
kinetic energies at high temperature than at low temperature.
Since the energy required to reach the transition state in a chemical
reaction comes from molecular collisions, the rate of chemical reactions
always increases with rising temperatures.
The concentration of reactants can affect reaction
rates.
The rate of a chemical reaction can be expressed as a rate law.
The rate law must be experimentally determined; it cannot be
derived directly from the balanced chemical equation.

F irst O rd er R eactio n :
A  B , R ate = k [A ]
S eco n d O rd er R eactio n :
A + B  C + D , R ate = k [A ][B ]
The Arrhenius equation describes how temperature
affects reaction rates.
The rate constant, k, depends upon temperature according to the
Arrhenius equation:
 E a / RT
k  Ae

In general, raising the reaction temperature by 10 oC will increase

the rate constant by a factor of 2 or 3.
2-2 Acids and Bases; Electrophiles and Nucleophiles
Acid and base strengths are measured by
equilibrium constants.
Brønsted-Lowry acid: a proton donor.
Brønsted-Lowry base: a proton acceptor.
In water:
Water itself is both an acid and a base:
+ 
H 2O + H 2O  H 3O + O H
+   14 o
K W = [H 3 O ][O H ] = 1.0 x 10 at 25 C

The pH of a solution is defined:

pH =  log[H 3 O ]
+

In pure water, the pH is 7. In acidic solutions the pH is less than 7

and in basic solutions the pH is above 7.

The behavior of a general acid, HA, in water can be described:

+ 
H A + H 2O  H 3O + O H
+ 
[H 3 O ][A ]
KA= , pK A =  log(K A )
[H A ]

The pKA is the pH at which the acid is 50% dissociated. If the pKA
is less than 1, the acid is termed strong; if greater than 4, weak.
We can estimate relative acid and base strengths.
The relative strength of a weak acid, HA, increases with:
•Increasing electronegativity of A (CH4 < NH3 < H2O < HF)
•Increasing size of A (HF < HCl < HBr < HI)
•Resonance in A-

The same molecule can act as both an acid and as a base:

 +
HNO3 + H 2 0  N O 3 + H 2O
 +
H 2 SO 4 + H N O 3  H SO 4 + H 2 N O 3
Lewis acids and bases interact by sharing an
electron pair.
Lewis Acid: A species containing an atom that is at least two
electrons short of a closed outer shell.

Lewis Base: A species containing at least one lone pair of

electrons.
A Lewis base shares its lone pair with a Lewis acid
to form a new covalent bond:

+   H  H  O
H + O
   H
 
The dissociation of a Brønsted acid is the reverse of the
association of a Lewis acid and a Lewis base:

Note that the curved arrow points to the departing anion.

Electrophiles and nucleophiles also interact through
movement of an electron pair.
Many processes in organic chemistry exhibit characteristics of
acid-base reactions.

C H 3C l + N aO H    C H 3 O H + N a C l
2H O ,Δ

The carbon atom in chloromethane is termed electrophillic. The

oxygen in the hydroxide is termed nucleophillic.
The reaction of chloromethane and hydroxide ion is an example of
a nucleophillic substitution reaction.
The terms Lewis acid and nucleophile are synonymous.
Nucleophilic substitution is a general reaction of the class of
compounds called haloalkanes. Additional examples include:

The C-X bond in these examples constitutes the functional group,

or center of chemical reactivity for the haloalkane class of organic
compounds.
2-3 Functional Groups: Centers of Reactivity
Functional groups are groups of atoms at sites of comparatively
high chemical reactivity. They control the reactivity of the
molecule as a whole.

Hydrocarbons are molecules that contain only

hydrogen and carbon.
Alkanes are compounds of hydrogen and carbon which contain
only single bonds.
When the carbon atoms form a ring, the compounds are called
cycloalkanes.
Alkenes are hydrocarbons containing one or more C-C double
bonds while alkynes contain one or more C-C triple bonds:

Benzene, C6H6, and its derivatives are examples of the class of

organic compounds called aromatic:
Many functional groups contain polar bonds
Haloalkanes have already been introduced. Alcohols (C-O-H) and
ethers (C-O-C) can be converted into a large variety of other
functionalities:

The carbonyl functionality, C=O, is found in aldehydes, ketones,

and carboxylic acids:
Alkyl nitrogen and sulfur compounds are named amines and
thiols:
R represents a part of an alkane molecule in the
following common functional groups:
2-4 Straight-Chain and Branched Alkanes
Alkanes can be classified into three general classes: straight-chain
alkanes, branched alkanes, and cycloalkanes:
Straight-chain alkanes form a homologous series.
The general formula of a straight chain alkane is CnH2n+2. Each
member of the series differs from the previous one by the
addition of a –CH2-, or methylene, group.
Molecules related in this manner are called homologs of each
other and the series is called a homologous series.
Branched alkanes are constitutional isomers of
straight-chain alkanes.
Branched chain alkanes have the same molecular formula as
straight chain alkanes, CnH2n+2, but differ in connectivity. A
branched and straight chain alkane are constitutional isomers of
each other.
There are three isomeric pentanes:

The number of isomeric

alkanes increases
dramatically with the
number of carbon atoms:
2-5 Naming the Alkanes

Many common or trivial names are still used widely used to name
certain alkanes.
Systematic IUPAC names are more precise. The first 20 straight
chain alkanes are:
An alkyl group is formed by removing a hydrogen from an alkane.
It is named by removing the –ane suffix and replacing it by –yl.
CH3- methyl; CH3CH2- ethyl; CH3CH2CH2- propyl
Additional prefixes are also used: sec- (or s-) for secondary, and
tert- (or t-) for tertiary. A secondary carbon is directly attached to
two other carbons. A tertiary carbon is directly attached to three
other carbons.
Some common branched alkyl groups are:
For systematically naming branched alkanes, four IUPAC rules are
used:
IUPAC RULE 1: Find the longest chain (stem) in the molecule and
name it. Groups other than hydrogen attached to this chain are
called substituents. If the molecule has two or more stems of
equal length, the one with the most substituents is the base stem
chain.
IUPAC RULE 2: Name all groups attached to the longest chain as
alkyl substituents. If a substituents chain is branched, find the
longest chain in the substituents and then name all of its
substituents.
IUPAC RULE 3: Number the carbons of the longest chain
beginning with the end closest to a substituents.

If there are two substituents at equal distance from the ends of

the chain, assign the lower number to the substituents coming
first in alphabetical order.
If there are three or more substituents, the chain is numbered to
give the lower number at the first difference between the two
possible numbering schemes (first point of difference principle).

Substituents are numbered outward from the main chain. C1 will

be the carbon attached to the main stem.
IUPAC RULE 4: Write the name of the alkane by first arranging all
the substituents in alphabetical order. Precede each with the
carbon number to which it is attached (to the stem) and a
hyphen.
When a molecule contains more than one instance of a particular
substituents, precede the name by the attachment positions
separated by commas and a prefix: di, tri, tetra, etc. In general,
the Greek prefixes, sec- and tert- are not considered in the
alphabetical ordering process.
If a particular complex substituents is present more than once,
the prefixes bis, trix, tetrakis, pentakis, etc. are used. Remember
the substituents carbon number 1 is the one attached to the stem
chain.
Haloalkanes are named treating the halogen as a substituents to
the longest stem, as for other substituents:
2-6 Structural and Physical Properties of Alkanes
Alkanes exhibit regular molecular structures and
properties.
Alkane structures are regular. The carbon atoms are tetrahedral
(bond angles close to 109o), C-C bond lengths all ~1.54 Å, and C-
H bond lengths all ~ 1.10 Å.
The 3-D structures are depicted by the dashed/wedged link
notation.
The physical constants of alkanes follow predictable trends:
Attractive forces between molecules govern the
physical properties of alkanes.
The physical forces between alkane molecules are due to London
forces. These forces arise from the correlation of electron motion
on neighboring molecules.
London forces are very weak and fall off with the 6th power of the
distance between molecules (Coulomb forces fall off with the 2nd
power).
With alkanes, London forces and therefore melting points increase
with increasing molecular size (increased surface area contacts).
Branched alkanes have smaller surface areas than their linear
isomers and also cannot pack together as efficiently. Their melting
points are usually lower than the corresponding linear isomers.
Highly compact branched molecules (symmetrical) are
exceptions.
In addition there is a slight difference between odd and even
numbered alkane chains. The odd numbered chains cannot pack
as well in the solid, and therefore have slightly lower melting
points than otherwise expected.
2-7 Rotation about Single Bonds: Conformations
Rotation interconverts the conformations of ethane.
The barrier to rotation of the two methyl groups in ethane is
approximately 2.9 kcal/mol. Since this amount of energy is
readily available at room temperature from molecular collisions,
the methyl groups are said to have free rotation.
The rotation motions within ethane can be represented by the
dashed/wedged notation:

During the rotation, the conformation moves from the staggered

to the eclipsed, and to a second staggered conformation.
Newman projections depict the conformations of
ethane.
The Newman projection is an alternative to using the
dashed/wedged notation:
The rotamers of ethane have different potential
energies.
The point of lowest potential during the C-C bond rotation in
ethane is at the staggered conformation, the highest potential
energy is at the eclipsed conformation (about 2.9 kcal/mole
higher).
The lifetime of the eclipsed conformation is extremely short and
this conformation represents a transition state connecting two
staggered conformations.
2-8 Rotation in Substituted Ethanes
Steric hindrance raises the energy barrier to
rotation.
The potential energy diagram for C-C bond rotation in
propane shows steric hindrance. The energy of the eclipsed
conformation is 3.2 kcal/mole above that of the staggered
conformation.
There can be more than one staggered and one
eclipsed conformation: conformational analysis of
butane.
There are two different types of staggered arrangements in
butane. One in which the two terminal methyl groups are 180o
apart (Anti), and two in which they are 30o apart (Gauche).
These are connected by two types of eclipsed conformations, one
in which the two methyl groups pass each other, and two in which
the methyl groups pass by hydrogen atoms:
The transition state (eclipsed conformation) energies are 3.6
kcal/mol and 4.0 kcal/mol in butane:

The most stable anti conformation represents about 72% of the

confomers present at 25% while the less stable gauche
conformation represents about 28% of the confomers present.
2 Important Concepts

1. Chemical Reaction – An equilibrium controlled by

thermodynamic and kinetic parameters.
The Gibbs Free Energy: Go = -RT ln(K) = Ho - TSo.
Ho: Related to bond energies of products and reactants.
Exothermic: Ho < 0. (BE products < BE reactants)
Endothermic: Ho > 0. (BE products > BE reactants)
So: Related to change in disorder.

2. Reaction Rate – Depends upon concentration of

reactants, activation energy, and temperature.
k = A exp(-Ea/RT)
3. Reaction Order – Cannot determine from
balanced chemical equation.
1st: Order: rate depends upon one reactant concentration.
2nd Order: rate depends upon two reactant concentrations.
2 Important Concepts

4. BrØnsted and Lewis Acids and Bases -

BrØnsted acids and bases are proton donors and
acceptors. Lewis acids and bases are electron pair
acceptors and donors.
Ka measures acid strength. pKa = - log(Ka).
5. Organic Molecule – A carbon skeleton with
attached functional groups.
6. Hydrocarbons – Composed of carbon and
hydrogen only. Alkanes possess only single bonds and
do not contain functional groups. Alkanes may be
straight chain, branched, or cyclic. Straight chain and
branched alkanes have the formula: CnH2n+2.
7. Homologs – Differ only in the number of methylene
groups in the chain.
2 Important Concepts

8. Primary Carbon – Attached to only one other

carbon.
Secondary Carbon – Attached to two other carbons.
Tertiary Carbon – Attached to three other carbons.
9. IUPAC Rules – Naming saturated hydrocarbons:
1. Name the longest continuous chain in the molecule.
2. Name all attached groups as substituents.
3. Number the carbon atoms of the longest chain.
4. Name the alkane, citing all substituents as prefixes arranged in
alphabetical order and preceded by numbers designating their
positions.
10. Alkane Attractions – Weak London forces. Polar
molecules through stronger dipole-dipole interactions,
and salts through very strong ionic interactions.
2 Important Concepts

8. Conformations – Rotation about C-C single bonds.

• Substituents on adjacent carbons can be staggered
or eclipsed. The eclipsed conformer is the transition
state between two staggered conformations.
• The activation energy for rotation is the energy
difference between the staggered and eclipsed
states.
• If both carbons bear alkyl or other groups, additional
conformers may be possible.
• Those in close proximity (60o) are gauche.
• Those directly opposite (180o) are anti.
• Molecules adopt conformations of minimum steric
hindrance.