CHEM 214

ORGANIC CHEMISTRY

UNIT 1: (Part 4)
Basic Knowledge of Acids and
Bases
CHAPTER 02 POLAR COVALENT BONDS; ACIDS AND BASES, MC MURRY
1

2.1 Polar Covalent Bonds:

Electronegativity
Chemical bonds
• Ionic bonds
• Ionsheld together by electrostatic attractions between
unlike charges
• Bond in sodium chloride
-
• Sodium transfers an electron to chlorine to give Na+ and Cl •
 Nonpolar Covalent bonds
• Twoelectrons are shared equally by the two bonding
atoms • Carbon-carbon bond in ethane
• Symmetrical electron distribution in the bond

Most bonds are neither fully ionic or covalent

Polar Covalent Bonds: Electronegativity

• Polar covalent bonds

• A covalent bond in which the electron distribution between
atoms is unsymmetrical
 •
Bond polarity is due to difference in electronegativity (EN)

Polar Covalent Bonds: Electronegativity

Electronegativity (EN)
• The ability of an atom to attract shared electrons in a
covalent bond
• Generally increases across the periodic table from left to
right and from bottom to top
 Polar Covalent Bonds: Electronegativity
• Bonds between atoms whose electronegativities differ by
less than 0.5 are nonpolar covalent
• Bonds between atoms whose electronegativities differ by
0.5 to 2.0 are polar covalent
• Bonds between atoms whose electronegativities differ by
more than 2.0 are largely ionic

Carbon hydrogen bonds are nonpolar. Bonds between carbon

(EN = 2.5) and more electronegative elements, such as
oxygen (EN = 3.5) and nitrogen (EN = 3.0) are polar
covalent bonds with the bonding electrons drawn towards
the more electronegative atoms

Electrostatic potential maps

Polar Covalent Bonds: Electronegativity
Inductive effect
• The electron-attracting or electron
withdrawing effect transmitted through σ
bonds. Electronegative elements have an
electron-withdrawing inductive effect
• Metals inductively donate electrons •
Reactive nonmetals inductively withdraw
electrons
• Inductive effects play a major role in
 understanding chemical reactivity

2.2 Polar Covalent Bonds: Dipole Moments

Molecules as a whole are often polar •

Molecular polarity results from the vector
summation of all individual bond polarities and lone

pair contributions in the molecule • Strongly polar

substances are soluble in polar solvents like water
Polar Covalent Bonds: Dipole Moments
Polar Covalent Bonds: Dipole Moments
Factors Affecting Dipole
Moments
• Lone-pair electrons on
oxygen and nitrogen
project
out into space away
from
positively charged
nuclei
giving rise to a considerable
charge separation and
contributing to the dipole
moment
• Symmetrical structures of
molecules cause the
individual bond polarities
and
lone-pair contributions to
exactly cancel
Worked

Example 2.1 Predicting the Direction of a

Dipole Moment
Make a three-dimensional drawing of methylamine,
CH3NH2, and show the direction of its dipole
moment (μ = 1.31)
Worked Example 2.1 Predicting the
Direction of a Dipole Moment
Strategy
• Look for any lone-pair electrons
• Identify any atom with an electronegativity
substantially different from that of carbon (usually O,
N, F, Cl, or Br)
• Electron density will be displaced in the general
direction of the electronegative atoms and the lone
pairs
Worked Example 2.1 Predicting the
Direction of a Dipole Moment
Solution
• Methylamine has an
electronegative nitrogen
atom and a lone pair of
electrons. The dipole
moment thus points
generally from –CH3toward
the nitrogen
Dipole Moments of Molecules
LEARNING OBJECTIVES 1. explained in
detail the concepts of acids and bases and their reactions.

Chapter 2
Acids and Bases – Reactions in
Equilibrium
Two acid base theories will be explored in this
chapter:
• Bronsted Lowry acid base theory: loss
and gain of a proton
• Lewis acid base theory: donation or
acceptance of a pair of electrons
BRONSTED LOWRY ACID
BASE THEORY
Acids and Bases: The Brønsted-Lowry
Definition
In a general sense

An Acid Loses a Proton

A Base Gains a Proton
An Acid and its Conjugate Base
A Base and its Conjugate Acid

When an acid loses a proton, it forms its conjugate base.

When a base gains a proton, it forms its conjugate acid.
The stronger the acid, the weaker its conjugate base.
Acids and Bases:
The Brønsted-Lowry Definition
Water can act either as an acid or as a base
2.8 Acid and Base Strength Acids differ in
their ability to donate H+
• The exact strength of a given acid, HA, in water
solution is described using the equilibrium constant
Keq (Ka) for the acid-dissociation equilibrium
 HA + H O A + H O
⎯⎯→
←⎯⎯ - +
23

HOA
⎡⎤⎡⎤
⎣⎦⎣⎦
+-

=
HA H O
3
K
eq
[ ][ ] 2
 Acid and Base Strength
The concentration of water, [H2O], remains nearly constant at
55.5 M at 25 °C
• Can rewrite equilibrium expression using new quantity called
the acidity constant Ka
Acidity constant Ka
• A measure of acid strength in water
• For any weak acid HA, the acidity constant is given by the
expression Ka
HA + H O A + H O
⎯⎯→
←⎯⎯ -+
 ⎡⎤⎡⎤
⎣⎦⎣⎦
+-
KK
23H O A

=HO= []
HA [ ]
a eq 2 3

Acid and Base Strength ←⎯⎯⎯⎯→ HA + H

-+

O A + H O 23
• Equilibria for stronger acids favor the products (to the right)
and thus have larger acidity constants
• Equilibria for weaker acids favor the reactants (to the left)
 and thus have smaller acidity constants

Acid strengths are normally expressed using pKa values

pKa
• The negative common logarithm of the Ka
pKa = -log Ka
• Stronger acids (larger Ka) have smaller pKa
• Weaker acids (smaller Ka) have larger pKa

Acids Have Different Strengths

Acid Strength
 The
stronger the acid, the larger the Ka.
The stronger the acid, the smaller the pKa.

Acid and Base Strength

Acid and Base Strength • Strong acid
(BrØnsted-Lowry)
• One that loses H+ easily
• Conjugate base holds on to the H+ weakly (weak
base)
• Strong acid has weak conjugate base

• Weak acid (BrØnsted-Lowry)

• One that loses H+ with difficulty
• Conjugate base holds on to the H+ strongly (strong
base)
• Weak acid has strong conjugate base
PREDICTING ACIDS AND
BASE REACTION
2.9 Predicting Acid-Base Reactions from
pKa Values
• An acid will donate a proton to the conjugate base
of a weaker acid
• The conjugate base of a weaker acid will remove
the proton from a stronger acid
Acid and Base Strength
Predicting Acid-Base Reactions from
pKa Values
• Product of conjugate acid must be weaker and less
reactive than the starting acid
• Product of conjugate base must be weaker and less
reactive than the starting base
 ORGANIC ACIDS AND BASES
2.10 Organic Acids and Organic Bases
Most biological reactions involve organic acids and
organic bases
Organic acid
• Positively polarized hydrogen atom
• Two main kinds of organic acids
1. Contains a hydrogen atom bonded to an
oxygen atom (O-H)
2. Contains a hydrogen atom bonded to a carbon
atom next to a C=O double bond (O=C-C-H)
Organic Acids and Organic Bases
Conjugate base
• Anion stabilized by having its negative charge on a highly
electronegative atom
• Anion stabilized by resonance

Methanol

Acetic Acid

Acetone
Organic Acids and Organic Bases
 • Conjugate bases from methanol, acetic acid,
and acetone • The electronegative oxygen atoms
stabilize the negative charge in all three
Organic Acids and Organic Bases
Carboxylic acids
• Contain the –CO2H grouping
• Occur abundantly in all living organisms
• Involved in almost all metabolic pathways
• At cellular pH of 7.3 carboxylic acids are usually dissociated
and exist as their carboxylate anions, –CO2-

Organic Acids and Organic Bases

Organic bases
• Characterized by the presence of an atom
with a lone pair of electrons that can bond to
+
H

Organic Acids and Organic Bases

 ACIDS AND BASES:
THE LEWIS DEFINITION

2.11 Acids and Bases: The Lewis Definition

The Lewis definition is broader than the Brønsted-Lowry definition Lewis
acid – an electrophile
• A substance with a vacant low energy orbital that can accept an electron
pair from a base
• All electrophiles are Lewis acids
Lewis base – a nucleophile
• A substance that donates an electron lone pair to an acid •
All nucleophiles are Lewis bases
Acids and Bases: The Lewis

Definition
Lewis Acids and the Curved Arrow Formalism •
To accept an electron pair a Lewis acid must have
either: • A vacant, low-energy orbital
• A polar bond to hydrogen so that it can donate H +

• Various metal cations, such as Mg2+, are Lewis acids

because they accept a pair of electrons when they
form a bond to a base
Acids and Bases: The Lewis Definition
Curved arrow formalism
• Indicates the direction of
electron flow from the base
to
the acid
• Always means that a pair of
 electrons moves from the atom
at the tail of the arrow to the
atom at the head of the arrow
• For the reaction of boron
trifluoride, a Lewis acid, with
dimethyl ether, a Lewis base.
All movement of electrons from
the Lewis base to the Lewis
acid is indicated by a curved
arrow

Acids and Bases: The Lewis Definition

Acids and Bases: The Lewis

Definition
Further examples of Lewis acids
A MECHANISM FOR THE
REACTION
Acids and Bases: The Lewis

Definition
Lewis bases
• A compound with a pair of nonbonding electrons that
it can use in bonding to a Lewis acid
• Definition of Lewis base similar to Brønsted-Lowry
definition • H2O acts as a Lewis base
• Has two nonbonding electrons on oxygen
Acids and Bases: The Lewis

Definition
• Most oxygen- and nitrogen- containing organic
compounds are Lewis bases
• They have lone pair electrons

Acids and Bases: The Lewis

Definition • Some compounds can act as
both acids and bases • Some compounds have more
than one atom with a lone pair of electrons
• Reactionnormally occurs only once in such instances •
The more stable of the two possible protonation products is
formed
• Occurs with carboxylic acids, esters, and amides
Curved arrows show the direction of electron flow in a reaction
mechanism.
1. Draw the curved arrow so that it points from the source of an
electron pair to the atom receiving the pair.
2. Always show the flow of electrons from a site of higher
electron density to a site of lower electron density. 3. Never
use curved arrows to show the movement of atoms. Atoms
are assumed to follow the flow of the electrons. 4. Make sure
that the movement of electrons shown by the curved arrow
does not violate the octet rule for elements in the second row
of the periodic table.

Worked Example 2.6 Using Curves

Arrows to Show Electron Flow
Using curved arrows, show how acetaldehyde,
CH3CHO, can act as a Lewis base.
Worked Example 2.6 Using Curves
Arrows to Show Electron FlowStrategy
• A Lewis base donates an electron pair to a Lewis
acid
• Locatethe electron lone pairs on acetaldehyde • Use
a curved arrow to show the movement of a pair
toward the H atom of the acid

Worked Example 2.6

Using Curves Arrows to Show Electron
FlowSolution

SEATWORK Using curved arrows, show how

the species in part (a) can act as Lewis bases in their
reactions with HCl, and show how the species in part
(b) can act as Lewis acids in their reaction with
OH. (a) CH3CH2OH HN(CH3) 2 P(CH3) 3

(b) H3C, B(CH3) 3 MgBr2

NON COVALENT
INTERACTION
2.12 Noncovalent Interactions
between Molecules
Noncovalent Interactions
• Also called intermolecular forces or van der Waals
forces • Types of noncovalent interactions include:
• Dipole-Dipole forces
• Occur between polar molecules as a result of electrostatic

interactions among dipoles

• Forces are either attractive or repulsive
Attractive Repulsive
• Attractive geometry is lower in energy and therefore predominates

Noncovalent Interactions between Molecules

• Dispersion forces
• Attractive dispersion forces in nonpolar molecules are caused by
 temporary dipoles
• One side of the molecule may have a slight excess of electrons
relative to the opposite side, giving the molecule a temporary
dipole
• Temporary dipole in one molecule causes a nearby molecule to
adopt a temporarily opposite dipole resulting in a small attraction
between the two molecules
• Arise because the electron distribution within molecules is
constantly changing
LONDON DISPERSION FORCES
Noncovalent Interactions between
Molecules • Hydrogen Bonds
• A weak attraction between a hydrogen atom bonded to an

electronegative O or N and an electron lone pair on another O

or N atom
• Strong dipole-dipole interaction involving polarized O-H and

N-H bonds
• Important noncovalent interaction in biological molecules
Hydrogen Bonding
• The dipole–dipole
interactions experienced
when H is bonded to N, O,
or F are unusually strong.
• We call these interactions
hydrogen bonds.
Noncovalent Interactions between

Molecules • Effects of Hydrogen Bonding

• Causes water to be a liquid rather than a gas at room
temperature
• Holds enzymes in the shapes necessary for catalyzing

biological reactions
• Causes strands of deoxyribonucleic acid (DNA) to pair up and
 coil into a double helix

Summarizing Intermolecular Forces

Identifying Substances That Can
Form Hydrogen Bonds

• In which of these substances is hydrogen

bonding likely to play an important role in
determining physical properties:
•
methane (CH4), hydrazine (H2NNH2), methyl
fluoride (CH3F), hydrogen sulfide (H2S)?
Noncovalent Interactions between Molecules
Hydrophilic (water-loving)
• Dissolves in water
• Table sugar
 • Has ionic charges, polar –OH groups, in its structure

Hydrophobic (water-fearing)
• Does not dissolve in water
• Vegetable oil
• Does not have groups that form hydrogen bonds

Of the two vitamins A and C, one is hydrophilic

and water-soluble while the other is hydrophobic
and fat-soluble. Which do you think is which?