DIPOLES IN CHEMICAL COMPOUNDS

Chapter 2 Ionic bonding between different elements and covalent

bonding between atoms of the same element can be
“Polar Covalent Bonds; Acids thought of as limits of electron distribution in compounds,
and Bases” either uniformly shared or completely transferred.

But most covalent bonds occur between different

elements, and in these bonds, electron distribution is not
necessarily uniform. That is they do not share the
electron pair equally.
+ –

Cl Cl Na Cl
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DIPOLES IN CHEMICAL COMPOUNDS DIPOLES IN CHEMICAL COMPOUNDS

Consider molecular hydrogen (H2) and hydrogen fluoride

(HF). Both of these are molecular compounds which can For molecular hydrogen,
be represented by the molecular models shown above. the electrostatic potential
map is uniform, showing
equal distribution of
electron density around
both hydrogen atoms.

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DIPOLES IN CHEMICAL COMPOUNDS DIPOLES IN CHEMICAL COMPOUNDS

Molecular compounds in which electron distribution is

unsymmetrical are called polar compounds and the
direction of the polarization is often shown using an
The blue color is associated arrow with a positive charge on one end.
with positive charge.

For hydrogen fluoride,

however, the electrostatic
potential map shows a This unsymmetrical charge
significant polarization of the distribution is also called a
electron density, with the dipole moment.
greatest charge associated with
the fluorine atom.

The red color is associated with

a negative charge.
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DIPOLE MOMENTS AND ELECTRONEGATIVITY DIPOLES IN CHEMICAL COMPOUNDS
The formation of dipole moments in molecules is a In the Lewis structure for water, there is a single
result of differences in electronegativity between the bond to each hydrogen and there are two unshared
elements in a covalent bond. pairs of electrons on the oxygen. Because there are
These elements four “things” surrounding the oxygen, the
have the highest molecular geometry of water is bent.
electronegativities.
Valence shell electron pair
repulsion theory predicts
that the molecular geometry
of water will be bent.
O H
H
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DIPOLES IN CHEMICAL COMPOUNDS DIPOLES IN CHEMICAL COMPOUNDS

For the O–H bonds in water, the electronegativity of The predicted molecular dipole of water is
oxygen is 3.5 and the electronegativity of hydrogen confirmed by the electrostatic potential map, which
is 2.1. The prediction is that the O–H bond in water shows the oxygen being electron-rich and the
should therefore be polar. hydrogens being electron-poor.

Because the molecular

geometry of water is bent,
the combination of the two
3.5 local dipoles will generate 3.5
a molecular dipole with
enhanced negative charge
2.1
towards the oxygen and 2.1
2.1 enhanced positive charge 2.1
towards the hydrogen.

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DIPOLES IN CHEMICAL COMPOUNDS FORMAL CHARGES

Alcohols, such as methanol (CH3OH) are also polar The concept of a formal charge in a molecular
compounds and we will see that many of the compound can be rationalized as follows:
reactions of alcohols are a simple result of this One of these bonding electrons came from
polarity. carbon, but now it’s gone! That means
carbon must now have a positive charge!

3.5 –
+

2.5

Likewise, oxygen now has one extra

electron. That means carbon must
now have a negative charge!
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FORMAL CHARGES IN-CLASS PROBLEM

In a molecular compound, each atom can be Calculate the formal charges of the nitrogen and
assigned a formal charge that can be calculated as oxygen atoms in trimethylamine-N-oxide.
follows:

First, take the Group number for the atom in the H 3C

periodic table. Subtract 1/2 of the number of ••
bonding electrons. Then, subtract the number of
H 3C N O
•
•
non-bonding (lone pair) valence electrons. ••

Group 1 - (1/2 x 2) - 0 = 0

Group 4 - (1/2 x 6) - 0 = +1
H H 3C
C H
FC = Group- (1/2 bonding)
- unshared H
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IN-CLASS PROBLEM IN-CLASS PROBLEM

Calculate the formal charges of each of the atoms in Azide anion can also be drawn in the Lewis structure
the azide anion (N3-). shown below. Determine the formal charges on each
atom.

•• ••

N N N N N N
• • • •
• • • •
•• ••

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FORMAL CHARGES IN-CLASS PROBLEM

First, take the Group number for the atom in the Draw the Lewis structure for nitrate anion (NO3-).
periodic table. Subtract
A carbonAwith
carbon
1/ of the number of
A three2 bonds
carbon
withwith
three
three
and
bonds
two
bonds
andand
oneno non-
bonding electrons. Then,
non-bonding subtract
non-bonding
electrons
bonding theis
electrons anumber
is electrons
called called a of
is called a Draw the atoms and their
non-bonding (lonewith
carbanion pair)
radical valence
carbocation
a formal electrons.
with acharge
formal
with aof
charge
formal
–1. ofcharge
0. of +1. associated electrons.

I VIII
1 II III IV V VI VII

6
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IN-CLASS PROBLEM IN-CLASS PROBLEM

O N O O N O O N O O N O
O O O O
The hybrid looks something
These structures are
like this.
called resonance forms
and because they differ
only in the arbitrary O N O O N O O N O
placement of electrons,
they are all equivalent.
O O O
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IN-CLASS PROBLEM RULES FOR DRAWING RESONANCE FORMS

O N O In the hybrid, each

oxygen is linked by “1⅓
• Move only electrons, not atoms.
• All resonance structures must be legal Lewis
bonds” and each oxygen structures.
O has
• Electrons can move only between adjacent sp
⅓ negative charge.
and sp2 centers, and between heteroatoms
attached to these centers.

The electron and charge distribution • Always remember that resonance forms are
in the hybrid is actually best electronic limits; and just like a mathematical
described as a “cloud”, with the limit, you never get there! The actual molecule
entire group having one net is the hybrid, it never looks like any of the limits,
negative charge. but is always something in between.

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BENZENE – THE ULTIMATE IN RESONANCE BENZENE – THE ULTIMATE IN RESONANCE

Benzene is an organic molecule with the molecular Benzene is an organic molecule with the molecular
formula C6H6. The structure of benzene is best described formula C6H6. The structure of benzene is best described
as a ring of carbons, each with one hydrogen, linked by as a ring of carbons, each with one hydrogen, linked by
alternating double and single bonds. alternating double and single bonds.

H
H C H
C C
C C
H C H
H
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BENZENE – THE ULTIMATE IN RESONANCE BENZENE – THE ULTIMATE IN RESONANCE
The resonance in benzene can be described as a cloud The resonance in benzene can be described as a cloud
formed from the overlap of the adjacent electron orbitals. formed from the overlap of the adjacent electron orbitals.
This electron-rich region is referred to as a π-cloud. This electron-rich region is referred to as a π-cloud.

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THE CARBOXYLATE ANION IN-CLASS PROBLEM

Another simple example of a resonance-stabilized Draw the major (cationic) resonance forms of the
system is the carboxylate anion. tropylium cation...

O O H
H H
O O
The resonance hybrid.
H H
O
equal bond lengths H H
O
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IN-CLASS PROBLEM IN-CLASS PROBLEM

In the tropylium cation, the positive charge is evenly Acetone (2-propanone) and 2,4-pentanedione undergo
distributed over all seven ring carbons... ionization to give the anions shown below. Draw
resonance structures for these anions.
H
H δ δ H
δ
δ
H H
δ δ
δ
H H

Tropylium cation, showing the uniform

distribution of the positive charge.
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DIPOLES IN CHEMICAL COMPOUNDS DIPOLES IN CHEMICAL COMPOUNDS
Draw the Lewis structure for water… In the Lewis structure for water, there is a single
bond to each hydrogen and there are two unshared
pairs of electrons on the oxygen. Because there are
four “things” surrounding the oxygen, the
molecular geometry of water is bent.

Valence shell electron pair

repulsion theory predicts
that the molecular geometry
of water will be bent.

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DIPOLES IN CHEMICAL COMPOUNDS DIPOLES IN CHEMICAL COMPOUNDS

For the O–H bonds in water, the electronegativity of The predicted molecular dipole of water is
oxygen is 3.5 and the electronegativity of hydrogen confirmed by the electrostatic potential map, which
is 2.1. The prediction is that the O–H bond in water shows the oxygen being electron-rich and the
should therefore be polar. hydrogens being electron-poor.

Because the molecular

geometry of water is bent,
the combination of the two
3.5 local dipoles will generate 3.5

2.1 a molecular dipole with 2.1

enhanced negative charge
towards the oxygen and
enhanced positive charge
2.1 towards the hydrogen. 2.1

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HYDROGEN BONDING HYDROGEN BONDING IN NUCLEIC ACIDS

Space-filling models showing extended hydrogen- Hydrogen-bonding is a very important force in aqueous
bonded complexes in liquid water are shown below. solution and hydrogen bonds such as these are well
known to stabilize biological molecules such as
proteins and nucleic acids. Base-pairing in DNA is
shown in the model given below.

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HYDROGEN BONDING IN NUCLEIC ACIDS HYDROGEN BONDING IN NUCLEIC ACIDS

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AUTOPROTOLYSIS OF WATER AUTOPROTOLYSIS OF WATER

As described previously, liquid As described previously, liquid
water consists of a dynamic water consists of a dynamic
complex of hydrogen-bonded complex of hydrogen-bonded
water molecules. If this polar water molecules. If this polar
attraction is sufficiently strong, a attraction is sufficiently strong, a
water molecule can transfer a water molecule can transfer a
proton along a hydrogen bond to proton along a hydrogen bond to
an adjacent water molecule, an adjacent water molecule,
forming a pair of ions. forming a pair of ions.

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AUTOPROTOLYSIS OF WATER IONIZATION OF WATER

As described previously, liquid The hydronium and hydroxide
water consists of a dynamic ions, H3O+ and HO- are very polar
+
complex of hydrogen-bonded molecules with a high
water molecules. If this polar concentration of positive charge
attraction is sufficiently strong, a associated with the hydrogens
water molecule can transfer a of H3O+ and a negative charge
proton along a hydrogen bond to associated with the oxygen of
an adjacent water molecule, HO-, as shown in the
forming a pair of ions. – electrostatic potential maps
shown here.

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IONIZATION OF WATER IONIZATION OF WATER
The hydronium ion, H3O+, itself is a very polar The stabilizing effect of this hydrogen bonding is
molecule with a high concentration of positive clearly shown by the electrostatic potential map for
charge associated with the hydrogens and a negative this complex, which is given below.
charge associated with the oxygen, as shown in the
electrostatic potential map given below.

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IONIZATION OF WATER IONIZATION OF MOLECULAR COMPOUNDS

This type of stabilization can extend over many Just like water can promote the dissociation of the
layers of adjacent water molecules, although a fairly O–H bond in water, polar molecular compounds can
stable structure is actually formed which involves also undergo ionization in the presence of a polar
hydrogen-bonding interactions between the solvent.
hydronium ion and eight adjacent water molecules.
Consider hydrogen
fluoride; this highly
polar molecule readily
ionizes in water to form
hydronium ion and
fluoride anion. Electrostatic potential
map of HF.

H–F + H2O H3O+ + F–

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IONIZATION OF MOLECULAR COMPOUNDS IONIZATION OF MOLECULAR COMPOUNDS

In Brønsted acid-base theory, a
The products of the ionization of HF are hydronium The reaction shown belowBrønsted
would therefore be donor
acid is a proton
ion and fluoride anion. As we have seen, it is also described as an equilibrium
anddissociation
a Brønsted baseofisHF to
a proton
reasonable to suggest that hydronium ion can form hydronium ion and fluoride anion.
acceptor.
associate with the fluoride anion and donate the
proton back, to reform molecular HF.
H–F + H2O H3O+ + F–
H–F + H2O H3O+ + F–
Compounds which ionize in the presence of water to
H–F + H2O H3O+ + F– form equilibrium concentrations of hydronium ion
are termed acids. The distinction between strong
Reactions which proceed in both directions are termed and weak acids is simply in the relative amounts of
equilibria and are written using a double arrow. hydronium ion which are present in the equilibrium
mixture.
H–F + H2O H3O+ + F–
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COMMON STRONG ACIDS LAW OF MASS ACTION K=
(P ) (P )
C
c
D
d

(P ) (P )
A
a
B
b

Hydrochloric acid The law of mass action can be summarized as:

H–Cl + H2O H3O+ + Cl– • Equilibrium expressions may contain gasses
Nitric acid as partial pressures, or solutes, expressed in
molar concentrations.
HNO3 + H2O H3O+ + NO3–
• Solids and liquids do not appear in
Perchloric acid equilibrium expressions.

HClO4 + H2O H3O+ + ClO4– • The equilibrium constant, K, is given by the

ratio of the product of the pressures (or
Sulfuric acid concentrations ) of the products of a
reaction, divided by the product of the
H2SO4 + H2O H3O+ + HSO4– pressures (or concentrations ) of the
HSO4– + H2O H3O+ + SO42– reactants, each raised to the powers of their
stoichiometric exponents.
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THE EQUILIBRIUM CONSTANT, K W IONIZATION OF MOLECULAR COMPOUNDS

Given the fact that, in pure water at 25˚C, the Strong acids, such as HCl, HNO3 and H2SO4
concentration of H3O+ and HO– are both 1.0 x 10-7 M, dissociate completely (or nearly so) into ions.
write the equilibrium constant for the autoionization
of water:
H–Cl + H2O H3O+ + Cl–
2 H2O H3O+ + HO–
⎡H3O+ ⎤⎦ ⎡⎣Cl− ⎤⎦
K w = ⎡⎣H3O+ ⎤⎦ ⎡⎣HO- ⎤⎦ Kc = ⎣ and Kc >> 1
[HCl]
and, at 25˚C, Kw = 1.0 x 10-14
For strong acids, such as HCl, HNO3 and H2SO4, the
acid dissociation constant, Kc, is large.
Liquid water does not appear in
the equilibrium expression.

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IONIZATION OF MOLECULAR COMPOUNDS IONIZATION OF MOLECULAR COMPOUNDS

Weak acids, such as HF and Weak acids, such as HF and
acetic acid (the acidic component acetic acid (the acidic component
of vinegar) dissociate into ions to of vinegar) dissociate into ions to
a very small extent. a very small The
extent.
smaller the value of Ka the
stronger the acid.

CH3COOH + H2O H3 O+ + CH3 COO– CH3COOH + H2O H3O+ + CH3COO–

⎡H3O+ ⎤⎦ ⎡⎣CH3COO− ⎤⎦ ⎡H3O+ ⎤⎦ ⎡⎣CH3COO− ⎤⎦

Ka = ⎣ = 1.8 x 10-5 Ka = ⎣ = 1.8 x 10-5
[CH3COOH] [CH3COOH]
-(log 1.8 x 10-5) = 4.74 = pKa -(log 1.8 x 10-5) = 4.74 = pKa

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PKA VALUES FOR SOME COMMON ACIDS SOME COMMON ORGANIC ACIDS
Methanol: pKa = 15.54

Acetic acid: pKa = 4.74

Acetone: pKa = 19.3

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LEWIS ACIDS AND BASES LEWIS ACIDS AND BASES

Lewis acids are electron pair acceptors; Lewis Lewis acids are electron pair acceptors; Lewis
bases are electron pair donors. bases are electron pair donors.

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HYDROGEN BONDING HYDROGEN BONDING IN POLAR LIQUIDS

Of all of the intermolecular forces we will encounter in Hydrogen bonding readily occurs between water and
Organic Chemistry, hydrogen-bonding is the strongest polar solutes such as alcohols and ammonia, and
force. When the hydrogen is attached to nitrogen, indeed, hydrogen bonding is important in the structure
oxygen or fluorine, hydrogen bonding will be the most and properties of other polar liquids.
important.

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HYDROGEN BONDING IN POLAR LIQUIDS HYDROGEN BONDING AND BOILING POINT
Hydrogen bonding readily occurs between water and The more polar and the more efficient the hydrogen-
polar solutes such as alcohols and ammonia, and bonding in a molecule the higher the boiling point will
indeed, hydrogen bonding is important in the structure be.
and properties of other polar liquids.
100

Boiling Point, oC
0

-200
H-Bond Efficiency

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OTHER TYPES OF INTERMOLECULAR INTERACTIONS INDUCED DIPOLES

Induced dipole attractions. Polar molecules and Although simple gasses such as oxygen and nitrogen
ions can induce a re-distribution of the electron are very non-polar, they readily dissolve in water.
cloud surrounding a non-polar molecule, resulting This is a result of the ability of water to induce a
in a net (weak) attraction. dipole in the non-polar molecules by deforming the
electron cloud surrounding the molecule.

δ- δ+
δ+ δ+

δ- δ- δ+ δ-

δ+ δ-
δ+ δ+

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INDUCED DIPOLES DISPERSION FORCES

Consider the high molecular weight, non-polar Dispersion forces. In non-polar molecules such
molecule I2 dissolving in the polar solvent ethanol as iodine, a temporary fluctuation of the electron
(CH3CH2OH). As the I2 interacts with the ethanol, a distribution in one atom can induce a transient
dipole is induced, increasing the solubility. dipole in a neighboring molecule, resulting in a
net (very weak) attraction.

δ- δ+ δ- δ+

Intermolecular forces arising between non-polar

molecules are generally referred to as van der Waals
forces.

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VAN DER WAALS FORCES AND BOILING POINTS MOLECULAR SHAPE AND BOILING POINT
n-Pentane and neopentane (2,2-dimethylpropane) are
In non-polar hydrocarbons, the boiling points
two isomers of the hydrocarbon, C5H12. The boiling
increase regularly with increasing molar mass due to
points the two are 36.1 oC, and 9.5 oC, respectively.
increased intermolecular forces.
This difference can be attributed to the enhanced
surface in n-pentane allowing more van der Waals
interactions.
Pentane, bp = 36.1 C
o

Neopentane,
bp = 9.5 oC

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VAN DER WAALS FORCES AND BOILING POINTS IN-CLASS PROBLEM

In non-polar hydrocarbons, the boiling points Any species that can accept electrons.
increase regularly with increasing molar mass due to A bond between two atoms differing in electronegativity
increased intermolecular forces. by 0.5 - 2.
A term used to describe a "water loving" species.
0

A compound that can donate a proton.

The ability of an atom to attract the shared electrons in a
Boiling Point, oC

covalent bond.
A term used to describe a "water fearing" species.

Any species that can donate electrons.

-200
Molar Mass
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A compound that can accept a proton. © ChemistryOnline, 2009-2015

IN-CLASS PROBLEM IN-CLASS PROBLEM

Assign any formal charges to atoms in the Use the δ⊕ - δ⊝ convention and the crossed arrow to
representation of phenylalanine… show the direction of the expected polarity of the C–F
and C–O bonds in the following compounds.
The oxygen atom labeled A. has ______ non-bonding
electrons.

The oxygen atom labeled B. has _____ bonding

electrons.

The C-Si bond in tetramethylsilane CH3

⊝
Si
⊕ H 3C
CH3

CH3
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IN-CLASS PROBLEM IN-CLASS PROBLEM
Refer to the following… Identify the acids and bases in the compounds shown
below:

The strongest Brønsted-Lowry acid in the equation is

______.

The strongest Brønsted-Lowry base in the equation is

______.
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IN-CLASS PROBLEM IN-CLASS PROBLEM

Draw two resonance forms of the ion shown below: Draw two resonance forms of the ion shown below:

CH3
O CH2

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