Chemical Bonding IV:

Molecular Polarity
& Bond Energy
 Polar Molecules
• Dipole - A molecule such as HF which has
a positive and a negative end. This dipolar
character is often represented by an arrow
pointing towards the negative charge.
δ + δ -

H-F
• Dipole moments – the measure of the
net molecular polarity (overall pull of e-
towards one direction in a molecule)
– Measure of separation of charge in units of
Debyes (D) = Qr (charge x separation) (μ)
Dipole Moments and Polar Molecules

electron rich
electron poor
region
region

H F

δ + δ −

µ =Qxr
Q is the charge
r is the distance between charges
1 D = 3.36 x 10-30 C m 3
 Which Molecules Have a
Dipole Moment?
• Dipole moment forms when all dipoles do not cancel
each other completely
• Any two atom molecule with a polar bond
• With three or more atoms there are three considerations.
1) There must be at least one dipole (polar bond)
2) There are significant strength differences among the dipoles
3) There is molecular asymmetrical geometry
Non-polar Molecules w/
Polar Bonds

Cl Be Cl
Cl is more electronegative than Be
Polar covalent bonds  dipoles
Molecule is symmetrical  dipole forces cancel
Molecule has no dipole moment  nonpolar
 dipole moment

H Be F
F & H are more electronegative than Be
Polar covalent bonds  dipoles
F is more electronegative than H
 stronger dipole
Molecule is symmetrical but dipole
forces do not completely cancel
Molecule has a dipole moment  polar
 Ex: Is BF3 polar?
• Electronegativity of F > B
•
•
Dipoles (but of equal strength)
Trigonal planar is symmetrical
F
• All dipoles completely cancel
• No dipole moment
 not polar
B
F F
 Ex: Is CCl4 polar?
• Electronegativity of Cl > C
• Dipoles (but of equal strength)
Tetrahedron is symmetrical
Cl
•
• All dipoles completely cancel
• No dipole moment
 not polar
C
Cl
Cl
Cl
Ex: Is NH3 polar ?
• Electronegativity of H < N
• Dipoles
• Trigonal pyramidal
is asymmetrical
• All dipoles are additive δ -
• Dipole moment
N
 polar
Hδ +
δ + H
H δ +
Resultant dipole = 1.47 D
 Ex: Is NF3 polar?
• Electronegativity of F > N
• Dipoles
• Trigonal pyramidal
is asymmetrical
• All dipoles do not cancel δ +
• Dipole moment
N
 polar
Fδ -
δ - F
Fδ -
Resultant dipole = 0.24 D
 Ex: NH3 is more polar than NF3

δ - δ +

N N
Hδ + Fδ -
δ + H F
δ -

H F
δ + δ -

Resultant dipole = 1.46 D Resultant dipole = 0.24 D

Bond moments and resultant dipole moments in NH3 and NF3.

14
Water is even more polar
Lone e pairs
-

DO NOT
make a
molecule polar
 Ex: Is CBr3F polar?
δ -
• Electronegativity of F > Br > C
Dipoles (not of equal strength)
•
• Tetrahedron is symmetrical F
• But all dipoles do not completely cancel
• Dipole moment
 polar

C
Br
Br δ +

δ +

Br
δ +
Asymmetrical dipole
forces
make a
molecule polar
 Symmetrical Molecules

Trigonal Tetrahedral
planar
Linear

Trigonal Octahedral Square

bipyramidal planar
 Asymmetrical Molecules

Bent or V-shaped Trigonal

pyramidal

Seesaw T-shaped
Square pyramidal
Ex: Is CH3Cl polar?
 Bond Dissociation
Energy (Enthalpy)
• Bonded atoms are more stable (less PE)
than singular atoms
• Forming bonds  exothermic ∆ H < 0
• Breaking bonds  endothermic ∆ H > 0
• Bond Dissociation Energy: ∆ H required to
break a particular bond in 1 mole of gaseous
molecules
Interaction of Two H Atoms and the
Energy Profile
Bond length - the optimum
distance between nuclei in a
covalent bond.
next
Change in electron density as two hydrogen atoms
approach each other.
 H 2( g ) 
→ H( g ) + H( g )
−1
∆H = 436.4 kJmol

Cl2( g ) 
→ Cl( g ) + Cl( g )
−1
∆H = 242.7 kJmol

Bond Energy of H2 > Bond Energy of Cl2

H-H bond is more stable than Cl-Cl
Why?
Size

H H
Cl Cl

With smaller radius, bonding e- can be closer

and more attracted to the nucleus
• Bond energy is simplified, for example:
• It takes 1652 kJ to dissociate a mole of CH4
into its ions
• Each C-H bond has a different energy.
• CH4 → CH3 + H ∆ H = 435 kJ/mol
• CH3 → CH2 + H ∆ H = 453 kJ/mol
• CH2 → CH + H ∆ H = 425 kJ/mol
• CH→ C + H ∆ H = 339 kJ/mol
• Each bond is sensitive to its environment.
• Since each hydrogen is hooked to the carbon,
we get the average energy = 413 kJ/mol
More bondsshorter bond lengthmore B.E.
∆ Ho (kJmol-

C H )
1

413
C C 347
C C 620
C C 812
 Bond Energy Bond Length
(kJ/mol) (pm)
It is experimentally
found that there is
a direct correlation C-C 347 154
between the bond C=C 611 134
length and the bond C≡C 837 120
strength.
C-N 305 147
As the bond length C=N 615 128
decreases, the bond C≡N 891 116
strength increases.
N-N 163 145
N=N 418 123
N≡N 946 110

O-O 142 145

O=O 498 121
 Using Bond Energies
• We can estimate ∆ H for a reaction.
• ∆ H = total Einput – total Eoutput
• Energy and Enthalpy are state functions.

∆H o
rxn = ΣBE reactants − ΣBE products
or
∆H o
rxn = ΣBE broken − ΣBE formed
The enthalpy change required to break a particular bond in one mole of gaseous
molecules is the bond enthalpy.

Bond Enthalpy
H2( g) H (g) + H (g) ∆ H0 = 436.4 kJ

Cl2( g) Cl (g) + Cl (g) ∆ H0 = 242.7 kJ

HCl ( g) H (g) + Cl (g) ∆ H0 = 431.9 kJ

O2( g) O (g) + O (g) ∆ H0 = 498.7 kJ O O

N2( g) N (g) + N (g) ∆ H0 = 941.4 kJ N N

Bond Enthalpies
Single bond < Double bond < Triple bond

34
Bond Enthalpies (BE) and Enthalpy changes in reactions

Imagine reaction proceeding by breaking all bonds in the reactants and

then using the gaseous atoms to form all the bonds in the products.

∆ H0 = total energy input – total energy released

= Σ BE(reactants) – Σ BE(products)

exothermic
endothermic 35
H2 (g) + Cl2 (g) 2HCl (g) 2H2 (g) + O2 (g) 2H2O (g)

36
 Use bond enthalpies to calculate the enthalpy change for:
H2( g) + F2( g) 2HF (g)

∆ H0 = Σ BE(reactants) – Σ BE(products)

Type of Number of Bond enthalpy Enthalpy

bonds broken bonds broken (kJ/mol) change (kJ/mol)
H H 1 436.4 436.4

F F 1 156.9 156.9

Type of Number of Bond enthalpy Enthalpy change

bonds formed bonds formed (kJ/mol) (kJ/mol)
H F 2 568.2 1136.4

∆ H0 = 436.4 + 156.9 – 2 x 568.2 = -543.1 kJ/mol

37
Ex: Calculate the ∆ Horxn for the combustion of H2(g)
using the table below.
Bond ∆ HoBE
Rxn: 2 H2 + O2  2 H2O
H-H 436.4

2 (H-H) O=O 2 (H-O-H)

H-N 393
H-O 460
4 (H-O) O-O 142
∆H o
rxn = ΣBE broken − ΣBE formed
O=O 498.7

∆H o
rxn =  2 ( H-H ) + ( O=O )  − 4 ( H-O ) 
 Bond ∆ HoBE

∆H o
rxn =  2 ( 436.4 ) + ( 498.7 ) 
H-H 436.4
−  4 ( 460 ) 
H-N 393
−1 H-O 460
∆H o
rxn = −484 kJmol
O-O 142
O=O 498.7

∆H o
rxn =  2 ( H-H ) + ( O=O )  − 4 ( H-O ) 
BREAK

HW: p. 404 # 47 – 49
p. 405 # 50 – 54
p. 407 # 85 – 88
 The Covalent Bond
• The forces that causes a group of
atoms to behave as a unit.
• Why?
• Due to the tendency of atoms to
achieve the lowest energy state.
• The bond is a human invention.
• It is a method of explaining the
energy change associated with
forming molecules.
• Bonds don’t exist in nature, but are
useful.
• We have a model of a bond.
 What is a Model?
• Explains how nature operates.
• Derived from observations.
• It simplifies them and categorizes the
information.
• A model must be sensible, but it has
limitations.
 Properties of a Model
• A human invention, not a blown up
picture of nature.
• Models can be wrong, because they are
based on speculations and
oversimplification.
• Become more complicated with age.
• You must understand the assumptions
in the model, and look for weaknesses.
• We learn more when the model is
wrong than when it is right.
 Find the energy for this

+ +
2 CH = CHCH 2NH O
2 3 3 2
→ +
2 CH = CHC ≡ N 6H O
2 2

C-H 413 kJ/mol O-H 467 kJ/mol

C=C 614kJ/mol O=O 495 kJ/mol

N-H 391 kJ/mol C≡ N 891 kJ/mol

C-C 347 kJ/mol