UNIT 1: STRUCTURE AND BONDING

Objectives:
When the students have completed this lesson, the students should be able to:

Overview of Organic Chemistry

 Know what is organic chemistry
 Know the importance of organic chemistry
 Define organic chemistry and know its importance to our everyday life
 Be familiarize with organic products commonly used
 Have the background information on the chemistry of carbon
 Learn and understand how structures of organic molecules are drawn and written
Structure and Bonding
 Recognize the bonding characteristics of covalent compounds
 Draw Lewis structures for covalent compounds
 Draw resonance structures for some ions and molecules
 Determine the molecular shape
 Draw organic structures
 Draw the Lewis structures
 Understand the concept of hybridization
 Study ethane, ethylene, and acetylene
 Study bond length and bond strength
 Use electronegativity to determine whether a bond is polar or nonpolar
 Determine whether a molecules is polar or nonpolar

1 Arranged by: Janet A. Dungog

What is Organic Chemistry?

Organic chemistry is a chemistry subdiscipline involving the scientific study of the structure,
properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms
that contain carbon atoms.

 It is one branch in the entire field of chemistry, which encompasses many classical subdisciplines including
inorganic, physical, and analytical chemistry, and newer fields such as bioinorganic chemistry, physical
biochemistry, polymer chemistry, and materials science.

 It is the study of the compounds that contain carbon, many of which are found in living organisms.

Some examples of organic compounds:

Organic Compounds

Biomolecules Synthetic
cotton medicines soap
wool foods shampoo
silk nylon contact lens

Importance of Organic Chemistry

1. By studying the principles and concepts of organic chemistry, you can learn more about compounds and how
they affect the world around you.
2. Organic chemistry provides both comforts and necessities that were previously nonexistent, or reserved for
only the wealthy.
3. Organic chemistry has found a way to increase in life span, from 47 years in 1900 to over 70 years today.
4. Organic chemistry allowed us to control insect populations that spread diseases.
4. Organic chemistry helps increase food production.

Products of Organic Chemistry

Some common products of organic chemistry used in medicine:

Organic chemistry has given us contraceptives, plastics, antibiotics, synthetic heart valves, and a myriad of other materials.
Our lives would be vastly different today without these products of organic chemistry.

2 Arranged by: Janet A. Dungog

The 3 Major Structural Units of Carbon

H H
C H H
3 2
sp hybrid = tetrahedral sp = trigonal planar sp = linear
0 0 0
bond angle = 109 bond angle = 120 bond angle = 180

Properties of Carbon

1. As a group 4A nonmetal, carbon atoms have the unique ability to form four strong covalent bonds.

2. Carbon forms strong π-bonds.

3. Carbon atoms can bond together, forming long chains and rings.

cellulose fructose (honey) polyvinyl chloride (PVC)

3 Arranged by: Janet A. Dungog

Some Representative Organic Molecules

Formula Structure Name / Uses

H methane
CH4 H C H gas used for cooking
H

C2H2 H C C H acetylene
gas used for welding

H H ethanol
C2H5OH H C C O H the alcohol found in beer, wine
H H and other alcoholic beverages

Complicated organic compounds contain many carbon atoms that organic chemists have devised a shorthand notation to draw
them. Keep in mind the following when examining these structures:
H H

H H H C H
C C
a two-electron bond
C C
H H H C H

H H

a carbon is located at each corner

• Each solid line represents a two-electron covalent bond.

• When no atom is drawn at the corner of a ring, an organic chemist assumes it to be carbon.

Exercise
1. Determine the number of carbon and hydrogen atoms in the following organic compounds.

___ Cs ___ Hs ___ Cs ___ Hs ___ Cs ___ Hs

2. How many different kinds of atoms can you see in the following organic compounds?

Br NH O
Br

Examples of complex organic molecules that are important medications are amoxicillin and fluoxetine.

H H H H
H H
O H
H H CF3 O C CH2CH2 N
HO C C S CH3
H CH3
N CH3 H
NH2
H H
H H H N O
O C
H H H
OH
H
Amoxicillin Fluoxetine
 most widely used antibiotics in the penicillin family  generic name for the antidepressant Prozac
 treats ear infection

4 Arranged by: Janet A. Dungog

Drawing Organic Structures
Molecules are actual, three-dimensional entities. Their structure is a major factor that determines their physical properties and
the way one molecule interacts with another molecule. Because molecules are normally too small to see, chemists have
devised ways to visually represent molecules, the structural formulas.

The structural formula of a chemical compound is a graphical representation of the molecular structure, showing
how the atoms are arranged.

There are several common representations used.

1. Two-Dimensional Structural Formula
H H H H H H H

H C C C C C C C H

H H H H H H H

heptane

Hydrocarbons provide the backbone of all organic compounds. Each carbon atom in a hydrocarbon forms a total of FOUR
BONDS. These bonds are combinations of single bonds with hydrogen atoms and single or multiple bonds with other carbon
atoms.

2. Condensed Structural Formula

For molecules that contain a large number of atoms or complex structures, drawing every bond and every atom is time and
space consuming. A common notation developed to abbreviate the drawing without sacrificing the clarity of the structure is the
condensed structural formula.

Condensed formulas show ALL THE ATOMS

CH4 CH3CH3
explicitly and the bonds between them are
inferred.
Condensed formulas for linear structures are
CH3CH2CH2CH2CH3 CH3(CH2)2CH3
straightforward.

How to Draw the Condensed Structural Formula

CH3 CH2 CH2 CH2 CH2 CH2 CH3

CH3CH2CH2CH2CH2CH2CH3

CH3(CH2)5CH3

Condensed formulas for branched molecules are done by enclosing branching group(s) in parentheses.
Example: isobutene (2-methylpropane)

H H H
H C C C H CH3CH(CH3)CH3
H CH3 H
structural formula condensed formula

5 Arranged by: Janet A. Dungog

Exercise
Write the condensed formula for each of the following structures.

OH

Br

O
NH2
O OH

3. Bond-Line Structural Formula

Not all hydrocarbons are straight chains; many are rings. Chemists use the same
structural formulas for them.
Because the illustration of the two-dimensional structural formula of
methylcyclopentane is so cluttered, it does not clearly show the ring.

The condensed structural formula is clearer. CH2 CH3

CH2 CH

CH2 CH2

methylcyclopentane

The bond-line structural formula is even clearer. Thus, chemists use it most
frequently.
Both the ends and the angles of the structure represent the carbon atoms. C—H
bonds are not shown, but you should assume that the appropriate number of methylcyclopentane
hydrogen atoms is present to complete the four bonds required by carbon to have
its octet of electrons.

Often, chemists combine the bond-line and condensed notations to clarify a CH3

structure or emphasize specific features. This formula also represents

methylcyclopentane. methylcyclopentane

Rules for Drawing Bond Line Structures

1. Each carbon is represented by the end of a line segment or the junction between a two line segments.
2. All hydrogens attached to carbons are NOT drawn.
3. All other atoms (heteroatoms and hydrogens attached to heteroatoms) are SHOWN explicitly.

Look at a few more examples, in order to become familiar with bond line structures:

ethane ethene butane 2-methylpropane

O O

NH2
OH
OH
ethanol cyclobutanone propanoic acid butylamine

6 Arranged by: Janet A. Dungog

Heteroatoms
Hydrogen atoms attached to
heteroatoms are SHOWN
explicitly.
Heteroatoms are atoms other
than carbon and hydrogen.
Hydrogen atoms bonded to
carbons must be inferred.

Exercise
1. Redraw each of the following condensed structural formulas using the bond-line notation.

CH3CH2CH2CH2CH2CH3 (CH3)2CH(CH2)4CH3 CH3

CH3 CH CH2 CH CH3

CH3

CH3 H2C CH2 CH2 CH3 CH( CH2) 4CH3

CH2 CH C CH CH3 CH
H2C CH H2 C
CH3 CH2 CH2
H2C CH CH3
H2 C CH2
CH2

2. Redraw each of the following bond-line structural formulas as condensed structures.

OH O

OH

7 Arranged by: Janet A. Dungog

Molecular Formula
Very rarely used in organic
chemistry, because they don't give
any useful information about the
A molecular formula simply counts the numbers of bonding in the molecule.
each sort of atom present in the molecule, but tells
you nothing about the way they are joined
together.

Exercise
Ten hydrocarbon structural formulas are drawn below (A to J). All these hydrocarbons answer the following questions. Enter
A to J, corresponding to your selections.

1. Which compounds have the molecular formula C8H14?

2. Which compounds have the molecular formula C8H12?

3. Which compounds have the molecular formula C8H10?

4. Which compounds have the molecular formula C8H8?

5. Which compound(s) have the greatest unsaturation?

In this introduction, we have seen a variety of molecules that have diverse structures. They represent only a fraction of the
organic compounds currently known and the many thousands that are newly discovered or synthesized each year. The
principles you learn in organic chemistry will apply to all of these molecules, from simple ones like methane and ethanol, to
complex ones like capsaicin. It is these beautiful molecules, their properties, and their reactions that we will study in organic
chemistry.

WELCOME TO THE WORLD OF ORGANIC CHEMISTRY!

8 Arranged by: Janet A. Dungog

Covalent Compounds
Most compounds that we come in contact with in our daily lives are covalent compounds, formed by sharing electrons
between atoms. The air we breathe is composed largely of the gases nitrogen and oxygen, two covalent molecules. The body is
mostly water, which contains two covalent hydrogen–oxygen bonds. Most of the drugs routinely used—aspirin,
acetaminophen, ibuprofen, and all antibiotics—are covalent compounds. Virtually all products of the chemical industry—
polyethylene, nylon, synthetic dyes, gasoline, and pesticides, to name a few—are covalent compounds.

Covalent bond is a bond in which one or more pairs of electrons are shared by two atoms.

Single bonds Double bonds

Triple bonds

Covalent Bonds of Atoms

-
Valence e s No. of Covalent Bonds
2 2
3 3
-
4 or more 8 – no. of valence e s
(follow the octet rule)

Covalent Bonding and the Periodic Table

Two atoms form covalent bonds when:

 two nonmetals combine

 metalloid and a nonmetal combine

Covalent bonding is preferred with elements in the middle of the periodic table that would otherwise have
to gain or lose several electrons to form an ion with a complete outer shell of electrons.

9 Arranged by: Janet A. Dungog

Bonding Patterns for Common Main Group Elements

Exercise

1. How many covalent bonds are predicted for each atom?

F Si Br O P S

2. Fill in the lone pairs on each atom to give every main group element except hydrogen an octet.

H H H

H C Cl H N O H H C O H Br C Br
H H
H H

Lewis Structures

A Lewis structure is a diagram representing the covalent bonding of a molecule or ion.

Examples:

Rules for Drawing Lewis Structures

There are three general rules for drawing Lewis structures.

1. Draw only the valence electrons.

2. Give every second-row element no more than eight electrons.
3. Give each hydrogen two electrons.

To draw a Lewis structure for a diatomic molecule like HF, recall that hydrogen has one valence electron and fluorine has seven.
H and F each donate one electron to form a two-electron bond. The resulting molecule gives both H and F a filled valence shell.

In a Lewis structure, a solid line indicates a two-electron covalent bond.

10 Arranged by: Janet A. Dungog

How to Draw Lewis Structures

Step [1] Arrange atoms next to each other that you think are bonded together.
 Always place hydrogen atoms and halogen atoms on the periphery because H and X (X = F, Cl, Br, and I) form
only one bond each.

 As a first approximation, place no more atoms around an atom than the number of bonds it usually forms.

 In truth, the proper arrangement of atoms may not be obvious, or more than one arrangement may be possible.
Even in many simple molecules, the connectivity between atoms must be determined experimentally.

Step [2] Count the electrons.

• Count the number of valence electrons from all atoms.
• Add one electron for each negative charge.
• Subtract one electron for each positive charge.
• This sum gives the total number of electrons that must be used in drawing the Lewis structure.

Step [3] Arrange the electrons around the atoms.

• Place a bond between every two atoms, giving two electrons to each H and no more than eight to any second-
row atom.
• Use all remaining electrons to fill octets with lone pairs.
• If all valence electrons are used and an atom does not have an octet, form multiple bonds.

Step [4] Assign formal charges to all atoms.

Sample Problem 1 Draw a Lewis structure for methane, CH4.

Step [1] Arrange the atoms

Step [2] Count the electrons

Step [3] Add the bonds and lone pairs

Adding four two-electron bonds around carbon uses all eight valence electrons, and so there are no lone pairs. To check
whether a Lewis structure is valid, we must answer YES to three questions:
• Have all the electrons been used?
• Is each H surrounded by two electrons?
• Is each second-row element surrounded by no more than eight electrons?
The answer to all three questions is YES, so the Lewis structure drawn for CH4 is valid.

11 Arranged by: Janet A. Dungog

Sample Problem 2 Draw a Lewis structure for methanol, a compound with molecular formula CH 4O.

Step [1] Step [2] Step [3] Add

Arrange the atoms Count the electrons the bonds and lone pairs

• four atoms around C

• two atoms around O

In Step [3], placing bonds between all atoms uses only 10 electrons, and the O atom does not yet have a
complete octet. To complete the structure, give the O atom two nonbonded electron pairs. This uses all
14 electrons, giving every H two electrons and every second-row element eight. We have now drawn a
valid Lewis structure.

Exercise
Draw a valid Lewis structure for each species.

Step [1] Step [2] Step [3]

a. CH3CH3

b. CH5N

–
c. CH3

d. CH3Cl

12 Arranged by: Janet A. Dungog

Two examples below illustrates when multiple bonds are needed in Lewis structures.

Sample Problem 3 Draw a Lewis structure for each compound. Assume the atoms are arranged as follows:

a. ethylene, C2H4 b. acetylene, C2H2

a. Ethylene, C2H4: Follow Steps [1] to [3] to draw a Lewis structure. After placing five bonds between the atoms and
adding the two remaining electrons as a lone pair, one C still has no octet.

To give both C's an octet, change one lone pair into one bonding pair of electrons between the two C's, forming a
double bond.

This uses all 12 electrons, each C has an octet, and each H has two electrons. The Lewis structure is valid. Ethylene
contains a carbon–carbon double bond.

b. Acetylene, C2H2: A similar phenomenon occurs with acetylene. Placing the 10 valence electrons gives a Lewis
structure in which one or both of the C's lack an octet.

In this case, change two lone pairs into two bonding pairs of electrons, forming a triple bond.

This uses all 10 electrons, each C has an octet, and each H has two electrons. The Lewis structure is valid. Acetylene
contains a carbon–carbon triple bond.
After placing all electrons in bonds and lone pairs, use a lone pair to form a multiple bond if an atom does not
have an octet. You must change one lone pair into one new bond for each two electrons needed to complete an
octet. In acetylene, for example, four electrons were needed to complete an octet, so two lone pairs were used to
form two new bonds, forming a triple bond.

13 Arranged by: Janet A. Dungog

Sample Problem 2 Draw an acceptable Lewis structure for each compound, assuming the atoms are connected as arranged.
Hydrogen cyanide (HCN) is a poison, formaldehyde (H2CO) is a preservative, and glycolic acid (HOCH2CO2H) is used to make
dissolving structures.

Exercise
Draw a valid Lewis structure for each species.

Step [1] Step [2] Step [3]

a.

b.

c.

d.

Formal Charge
To manage electron bookkeeping in a Lewis structure, organic chemists use formal charge.

Formal charge is the charge assigned to individual atoms in a Lewis structure.

By calculating formal charge, we determine how the number of electrons around a particular atom compares to its number of
valence electrons. Formal charge is calculated as follows:

The number of electrons “owned” by an atom is determined by its number of bonds and lone pairs.

An atom “owns” all of its unshared electrons and half of its shared electrons.

14 Arranged by: Janet A. Dungog

The number of electrons “owned” by different carbon atoms is indicated in the following examples:

+
Sample Problem 1 Determine the formal charge on each atom in the ion H3O .

Solution
For each atom, two steps are needed:
Step [1] Determine the number of electrons an atom “owns.”
Step [2] Subtract this sum from its number of valence electrons.

The formal charge on each H is 0. The formal charge on oxygen is +1. The overall charge on the ion is the sum of all
of the formal charges; 0 + 0 + 0 + 1 = +1.

Exercise
1. Calculate the formal charge on each second-row atom.

2. Draw a Lewis structure for each ion.

15 Arranged by: Janet A. Dungog

Formal Charge Observed with Common Bonding Patterns for C, N, and O

Isomers
In drawing a Lewis structure for a molecule with several atoms, sometimes more than one arrangement of atoms is possible for
a given molecular formula. For example, there are two acceptable arrangements of atoms for the molecular formula C2H6O.

Both are valid Lewis structures, and both molecules exist. One is called ethanol, and the other, dimethyl ether. These two
compounds are called isomers.

Isomers are different molecules having the same molecular formula.

Ethanol and dimethyl ether are constitutional isomers because they have the same molecular formula, but the connectivity of
their atoms is different.

Exercise
Draw Lewis structures for each molecular formula.

Octet Rule
The octet rule is a chemical rule of thumb that states that atoms of low (<20) atomic number tend to combine in such a way
that they each have eight electrons in their valence shells, giving them the same electronic configuration as a noble gas.

When atoms have less than eight

The octet rule is the tendency of atoms to have eight electrons, they tend to react and
electrons in their valence shell. form more stable compounds.

16 Arranged by: Janet A. Dungog

Octet Rule/Duet Rule/Exceptions

The atoms that commonly follow the octet rule C N O F Cl Br I

The atoms that do not regularly follow the octet rule: H He P S

(2 e-s) (2 e-s) (10 e-s) (12 e-s)

Exercise
Fill in the missing lone pairs. Assign formal charges to ALL atoms in the Lewis structures.

a. O H e.
N C
O As O H

b. f. C N
O
N
O

c. g. H3P C CH3

OH H
S
O O

d. H3C N N N h. H2C N N

Exercise
Questions 1 to 8 refer to the group shown below. Enter appropriate letters from A through K in each answer box. If no structure
fits the property enter the letter X.
Which structures satisfy the following conditions?

1. No formally charged atoms are present in the structure

2. At least one nitrogen has a (+) formal charge

3. At least one nitrogen has a () formal charge

4. At least one oxygen has a (+) formal charge

5. At least one oxygen has a () formal charge

6. At least one carbon has a (+) formal charge

7. At least one carbon has a () formal charge

8. At least one sulfur has a (+) formal charge

17 Arranged by: Janet A. Dungog

Resonance
Some molecules can’t be adequately represented by a single Lewis structure.
–
Example: Two valid Lewis structures can be drawn for the anion (HCONH) .

A structure that has a (-) charged N atom A structure that has a (-) charged O atom
and a C – O double bond (1) and a C – N double bond (2)
(1) (2)
O O
H C N H H C N H

These structures are called resonance structures or resonance forms. A doubleheaded

arrow is used to separate two resonance structures.

Resonance structures are two Lewis structures having the same placement of atoms but a different arrangement of
electrons.

–
Which resonance structure is an accurate representation for (HCONH) ?

Answer: neither of them

The true structure is a composite of both resonance forms, and is called a resonance hybrid. The hybrid
shows characteristics of both resonance structures.

Resonance allows certain electron pairs to be delocalized over two or more atoms, and this delocalization of electron density
adds stability. A molecule with two or more resonance structures is said to be resonance stabilized.

Resonance Theory
Keep in mind the following basic principles of resonance theory.

 Resonance structures are not real. An individual resonance structure does not accurately represent the structure of a
molecule or ion. Only the hybrid does.

 Resonance structures are not in equilibrium with each other. There is no movement of electrons from one form to
another.

 Resonance structures are not isomers. Two isomers differ in the arrangement of both atoms and electrons, whereas
resonance structures differ only in the arrangement of electrons.

Examples:

Ions A and B are resonance structures because the Compounds C and D are isomers since the atom placement is
atom position is the same in both compounds, but the different; C has an O – H bond, and D has an additional C– H
location of an electron pair is different. bond.
Isomers
Resonance Structures
an O-H

one electron pair in a different location

O H O

CH2 C CH3 and CH3 C CH3

CH3 C O and CH3 C O

one more C-H bond

18 Arranged by: Janet A. Dungog

Exercise
1. Classify each pair of compounds as isomers or resonance structures.

O O
a. N C O and C N O
b. HO C O and HO C O

2. Considering structures A–D, classify each pair of compounds as isomers, resonance structures, or neither: (a) A and B; (b) A
and C; (c) A and D; (d) B and D.

O O O O
(a) A and B __________ (c) A and D __________
CH3 C OH CH3 C OH CH3 C OH H C CH2OH
(b) A and C __________ (d) B and D __________
A B C D

Drawing Resonance Structures

To draw resonance structures, use the three rules that follow:

Rule [1] Two resonance structures differ in the position of multiple bonds and nonbonded electrons. The placement of
atoms and single bonds always stays the same.

Rule [2] Two resonance structures must have the same number of unpaired electrons.

Rule [3] Resonance structures must be valid Lewis structures. Hydrogen must have two electrons and no second-row
element can have more than eight electrons.

19 Arranged by: Janet A. Dungog

Curved Arrow Notation
Curved arrow notation is a convention that shows how electron position differs between the two resonance forms.

Curved arrow notation shows the movement of an electron pair. The tail of the arrow always begins at an
electron pair, either in a bond or lone pair. The head points to where the electron pair “moves.”

Move an electron pair to O.

O O
H C N H H C N H

A B

Use this electron pair to form a double bond

A curved arrow always begins at an electron pair. It ends at an atom or a bond.

Notes:
1. Resonance structures A and B differ in the location of two electron pairs, so two curved arrows are needed.
2. To convert A to B, take the lone pair on N and form a double bond between C and N. Then, move an
electron pair in the C – O double bond to form a lone pair on O.
3. Curved arrows thus show how to reposition the electrons in converting one resonance form to another.
4.The electrons themselves do not actually move.

Example: Follow the curved arrows to draw a second resonance structure for each ion.

a. CH2 C CH2

Solution
a. The curved arrow tells us to move one electron pair in the double bond to the adjacent C – C bond. Then
determine the formal charge on any atom whose bonding is different.

Move one electron pair ...

a. CH2 C CH2 CH2 C CH2

H H

... then assign formal charge ( 1 )

Positively charged carbon atoms are called carbocations. Carbocations are unstable intermediates because
they contain a carbon atom that is lacking an octet of electrons.

20 Arranged by: Janet A. Dungog

 O

b. H C C CH3

Solution
b. Two curved arrows tell us to move two electron pairs. The second resonance structure has a formal charge
of (–1) on O.
Move two electron pairs ...

O O
H C C CH3 H C C CH3
H H

... then calculate formal charges.

This type of resonance-stabilized anion is called an enolate anion. Enolates are important intermediates in
many organic reactions.

The ability to draw and manipulate resonance structures is an important skill that will be needed throughout your study of
organic chemistry. With practice, you will begin to recognize certain common bonding patterns for which more than one Lewis
structure can be drawn.
For now, notice that two different resonance structures can be drawn in the following situations:

• When a lone pair is located on an atom directly bonded to a multiple bond.

lone pair adjacent to C=C

CH2 C CH2 CH2 C CH2

H H

O O

H C C CH3 H C C CH3

H H
lone pair adjacent to C=O

• When an atom bearing a (+) charge is bonded to either a multiple bond or an atom with a lone pair.

( +) charge adjacent to a CH2 C CH2 CH2 C CH2

double bond
H H

( +) charge adjacent to CH3 O CH2

CH3 O CH2
an atom with a lone pair

21 Arranged by: Janet A. Dungog

Exercise

1. Follow the curved arrows to draw a second resonance structure for each species.

a. H C O b. CH3 C C CH2
H H H

2. Use curved arrow notation to show how the first resonance structure can be converted to the second resonance structure.

a. CH2 C C CH3 CH2 C C CH3 b. O C O O C O

H H H H O O

3. Draw a second resonance structure for each ion.

O
O OH
CH2 NH2
CH3 C O H C H

4. Draw all possible resonance forms for each structure below. Use curved arrows. Note that some structures only show
charge, and not implied protons or lone pairs!

a. b. c.

5. For each molecule, determine the formal charge of the indicated atom.

H H e.
a. O C N g.
H c. C

N O
d.
b. f. h. H Cl Cl
N

22 Arranged by: Janet A. Dungog

6. For each molecule below, draw in all implied lone pairs and/or protons (hydrogens) based on the formal charge shown.

H
O Cl
O

N Cl C

7. Draw all possible resonance forms for each structure below. Use curved arrows. Note that some structures only show
charge, and not implied protons or lone pairs!

O O

a. C C
H3C O H3C O

O O

b. C C
H3C NH2 H3C NH2

O O O O
c. O Cl O O Cl O O Cl O O Cl O
O O O O

8. Draw all possible resonance forms for each structure below. Use curved arrows. Note that some structures only show
charge, and not implied protons or lone pairs!

O O O O O O
a. b. C.

23 Arranged by: Janet A. Dungog

The Resonance Hybrid
The resonance hybrid is the composite of all possible resonance structures. In the resonance hybrid, the electron pairs drawn in
different locations in individual resonance structures are delocalized.

The resonance hybrid is more stable than any resonance structure

because it delocalizes electron density over a larger volume.

Characteristic Features of a Resonance Hybrid

1. When all resonance forms are identical, each resonance form contributes equally to the hybrid.
Move one electron pair ...

a. CH2 C CH2 CH2 C CH2

H H

... then assign formal charge ( 1 )

2. When two resonance structures are different, the hybrid looks more like the “better” resonance structure. The
“better” resonance structure is called the major contributor to the hybrid, and all others are minor contributors. The
hybrid is the weighted average of the contributing resonance structures.

What makes one resonance structure “better” than another?

A “better” resonance structure is one that has more bonds and fewer charges.

Exercise
1. Label the resonance structures in each pair as major, minor, or equal contributors to the hybrid.

2. Draw a second resonance structure for nitrous acid. Label each resonance structure as a major, minor, or equal contributor
to the hybrid.

24 Arranged by: Janet A. Dungog

Determining Molecular Shape
We can now use Lewis structures to determine the shape around a particular atom in a molecule. Consider the H 2O molecule.
The Lewis structure tells us only which atoms are connected to each other, but it implies nothing about the geometry. What
does the overall molecule look like? Is H2O a bent or linear molecule? Two variables define a molecule’s structure: bond length
and bond angle.

Bond Length

Bond length is the average distance between the centers of two bonded nuclei. Bond lengths
are typically reported in picometers (pm), where 1 pm = 10–12 m.

General Trends:

1. Bond length decreases across a row of the periodic table as the size of the atom decreases.

C H N H O H

2. Bond length increases down a column of the periodic table as the size of the atom increases.
H F H Cl H Br

Average Bond Lengths for Common Bonds

Bond Length (pm) Bond Length (pm) Bond Length (pm)

H-H 74 H-F 92 C-F 133

C-H 109 H-Cl 127 C-Cl 177
N-H 101 H-Br 141 C-Br 194
O-H 96 H-I 161 C-I 213

Bond Angle
Bond angle determines the shape around any atom bonded to two other atoms. To determine the bond angle and shape
around a given atom, we must first determine how many groups surround the atom. A group is either an atom or a lone pair of
electrons. Then we use the valence shell electron pair repulsion (VSEPR) theory to determine the shape.
VSEPR (Valence- Shell Electron-Pair Repulsion) Theory
The shapes of molecules can be predicted from their Lewis structures with a model known as the valence-shell electron-pair
repulsion (VSEPR) theory.

Valence-shell electron-pair repulsion (VSEPR) is a model used to describe molecular

geometry that can be summed up as electrons repel each other.

25 Arranged by: Janet A. Dungog

Molecular Shapes

Molecule Bond Angle

0
180
Linear

0
120

Trigonal planar Bent

0
109.5

Tetrahedral Trigonal pyramidal Bent

0 0
90 , 120

Trigonal bipyramidal Seesaw T-shaped Linear

0
90

Octahedral Square pyramidal Square planar T-shaped Linear

VSEPR Geometries

26 Arranged by: Janet A. Dungog

Assumptions of the VSEPR theory:

1. Each atom in a molecule will achieve a geometry that

minimizes the repulsion between electrons in the valence shell
of that atom. These will result in
geometry with the
lowest possible
2. Electron pairs, whether involved in bonds or as non-bonding energy.
pairs, will adopt a geometry in which they maximize the
distance from one another.

Some of the following terms are defined here.

1. An 'electron cloud' may be a single, double or

3. 'Electron clouds' are negatively charged since the
triple bond, or a lone pair of electrons.
electrons are negatively charged, so electron clouds repel
one another and try to get as far away from each other as
2. A lone pair of electrons is a non-bonding pair possible.
of electrons.

Trend in Repulsion:

LP - LP repulsion > LP - BP repulsion > BP - BP repulsion

How to Work Out the Number of Electron Pairs

Step 1 Work out how many electrons there are around the central atom.

1. Write down the number of 2. Add one electron for each bond 3. Allow for any ion charge. For
electrons in the outer level of the being formed. example, if the ion has a 1- charge,
central atom. add one more electron. For a 1+
charge, deduct an electron.

Step 2 Work out how many bonding pairs and lone pairs of electrons there are.

1. Divide by 2 to find the total number of electron pairs 2. Work out how many bonding pairs and lone pairs.
around the central atom.

Step 3 Use this information to work out the shape.

Arrange these electron pairs in space to minimize repulsions.

27 Arranged by: Janet A. Dungog

Case A Two electron pairs around the central atom
Geometry: linear
Example: BeCl2
Can form
2 bonds 0
Bond angle: 180
 Be 
2 electron pairs

Bonding and molecular shape of BeCl2:

Case B Three electron pairs around the central atom

Example: BF3 or BCl3 Geometry:

trigonal planar
Can form
3 bonds
B Bond angle: 120
0

 3 electron pairs

The other electrons on the

fluorine atoms have been
Bonding and molecular shape of BeCl2: left out because they are
irrelevant.

Case C Four electron pairs around the central atom

Example 1: CH4 Geometry:

tetrahedral
Can form
4 bonds 0
Bond angle: 109.5

C 4 electron pairs


Bonding and molecular shape of BeCl2:

28 Arranged by: Janet A. Dungog

Other examples with four electron pairs around the central atom

Example 2: NH3

Geometry:
trigonal pyramidal

Can form
3 bonds
 Bond angle: 107
0

N 6 electron pairs;

 1 LP

Bonding and molecular shape of BeCl2:

Why the bond angle in NH3 is shorter?

That forces the bonding
Because LP-BP repulsion pairs together slightly -
> BP–BP repulsion. reducing the bond angle
from 109.5° to 107°.
Lone pairs are in orbitals that
are shorter and rounder than
the orbitals that the bonding
pairs occupy.

Example 3: H2O 0
Bond angle: 104

Can form
2 bonds Geometry:
 bent/V-shaped

O 2 electron pairs;

 2 LPs

Bonding and molecular shape of BeCl2:

29 Arranged by: Janet A. Dungog

Case D Five electron pairs around the central atom
Geometry:
Example 3: phosphorus (V) fluoride, PF5 trigonal
bipyramidal
Can form
5 bonds
Bond angles:
 90, 120
0

P 10 electron pairs



Bonding and molecular shape of BeCl2:

Case E Six electron pairs around the central atom

Geometry:
Example 3: SF6
octahedral
Can form
12 bonds

0
Bond angle: 90

S
6 electron pairs


Bonding and molecular shape of BeCl2:

Bond Length and Bond Strength

A Comparison of Carbon-Carbon Double Bonds
As the number of electrons between two nuclei increases, bonds become shorter and stronger.

Thus, triple bonds are shorter and stronger than double bonds, which are shorter and stronger than single bonds.

30 Arranged by: Janet A. Dungog

Values for bond lengths and bond strengths for CH3CH3, CH2–– CH2 and HCCH are shown below. Be careful not to confuse two
related but different principles regarding multiple bonds such as C – C double bonds.

Double bonds, consisting of both  and  bond are strong. The  component of the double bond, however, is usually
much weaker than the  component. This is a particularly important consideration when studying alkenes.

Bond Lengths and Bond Strengths for Ethane, Ethylene, and Acetylene

A Comparison of Carbon-Hydrogen Bonds

The length and strength of a C – H bond vary slightly depending on the hybridization of the carbon atom.

As the percent s-character increases, a hybrid orbital holds its electrons closer to the nucleus, and the bond becomes shorter
and stronger.
sp hybrid one 2s orbital
------------------------ = 50% s-character
two hybrid orbitals

2
sp hybrid one 2s orbital
------------------------- = 33% s-character
three hybrid orbitals

3
sp hybrid one 2s orbital
------------------------- = 25% s-character
four hybrid orbitals

General Trends:

Increased % s-character Increased bond strength Decreased bond length

31 Arranged by: Janet A. Dungog

Exercise
1. Determine the shape around each indicated atom.

H NF 3 H

H C O H H C S H

H H

2. Add lone pairs to the N and O atoms to give octets and then determine the shape around each indicated atom.

H H O

H N O H H C C OH

H
H
H N N H H C O O H
H H

3. Rank the following bonds in order of increasing bond length.

H H
C C H C C H C CH3 H C C CH2 C C C H
H H H
b H H H
1 2 3 c
a

4. Answer the following questions about compound A. Use letters a – e.

a. Label the shortest C-C single bond.

b. Label the longest C-C single bond. ( 1)

c. Considering all the bonds, label the shortest C-C single bond.
( 2)
d. Label the weakest C-C single bond.
A
e. Label the strongest C-C single bond.

f. Explain why bond (1) and bond (2) are different in length, even though they are both C-C single bonds.

32 Arranged by: Janet A. Dungog

5. Indicate the longer labeled bond in each compound.

NH2 Cl
HO Br
N NH2

6. What bond angles do you expect for each of the following, and what kind of hybridization do you expect for the central
atom in each?

O H N H OH O
C C
CH3 CH C OH
H2N CH2 C OH C C
H C H lactic acid
glycine
H ( in sour milk)
( an amino acid)
pyridine

7. Predict the bond angles around the indicated atoms in each compound.

H C F H C C O

H
H

H H H

H C C Cl H C C C N H

H H H H

8. Rank the indicated bonds in each compound in order of (a) increasing bond strength and (b) increasing bond length.

bond 1 bond 1
bond 2
H
N bond 3
b. CH3 N
bond 3
a. C C
C N

bond 2

9. Which of the indicated bonds in each pair of compounds is shorter?

CH3 H H
c. CH2 N H or CH3 N H
a. CH3 C C H or C CH2 C O or H C OH H
b.
H H H
A B
A B A B

33 Arranged by: Janet A. Dungog

Electronegativity and Bond Polarity
Electronegativity is a measure of an atom’s attraction for electrons in a bond. Thus, electronegativity indicates how much a
particular atom “wants” electrons.
Trends in electronegativity are observed in the periodic table:

Electronegativity values are used as a guideline to indicate whether the electrons in a bond are equally shared or unequally
shared between two atoms.

 Whenever two identical atoms are bonded

together, each atom attracts the electrons in the
 Whenever two different atoms having similar
bond to the same extent.
electronegativity values are bonded together, each
 The electrons are equally shared, and the bond is
atom attracts the electrons in the bond to the same
nonpolar.
extent.
 Thus, a carbon–carbon bond is nonpolar.
 C – H bonds are considered to be nonpolar, because
the electronegativity difference between C (2.5) and
H (2.2) is small.

Bonding between atoms of different electronegativity values results in the unequal sharing of electrons.

In this C – O bond, the electrons are pulled away from C (2.5) toward
O (3.4), the element of higher electronegativity. The bond is polar, or polar covalent. The bond is said to have
a dipole; that is, a separation of charge.

34 Arranged by: Janet A. Dungog

Using EN to Identify Ionic, Covalent, and Polar Covalent Compounds

EN is the ability of an atom to attract electrons in a covalent bond.

These are the rules:

1. If the electronegativity difference (usually called EN) is less than 0.5, then the bond is nonpolar covalent bond.

2. If the EN is between 0.5 and 1.6, the bond is considered polar covalent bond.

3. If the EN is greater than 2.0, then the bond is ionic bond.
4. If the EN is between 1.6 and 2.0 and if a metal is involved, then the bond is considered ionic bond. If only
nonmetals are involved, the bond is considered polar covalent bond.

Examples:

Sodium bromide EN = 1.9 Hydrogen fluoride EN = 1.9

(formula = NaBr; ENNa = 0.9, ENBr = 2.8) (formula = HF; ENH = 2.1, ENF = 4.0)

We use rule #4 to decide that NaBr has ionic bonds and that HF has a polar covalent bond in each HF molecule.

Exercise

Determine the type of bonding between two atoms. Show proof of your answer.

Pair of Atoms EN Type of Bond

1. Sn – Cl ____________________ ____________________

2. Ga – As ____________________ ____________________

3. N – O ____________________ ____________________

4. Se - S ____________________ ____________________

35 Arranged by: Janet A. Dungog

5. Na – Br ____________________ ____________________

6. Mg – O ____________________ ____________________

7. Cu – N ____________________ ____________________

8. Al – P ____________________ ____________________

9. Be - Cl ____________________ ____________________

10. Mg – B ____________________ ____________________

11. Ag – Hg ____________________ ____________________

13. Si – Si ____________________ ____________________

14. C – C ____________________ ____________________

15. U – F ____________________ ____________________

16. Co – P ____________________ ____________________

17. C – H ____________________ ____________________

18. Cd – I ____________________ ____________________

19. Rb – Sn ____________________ ____________________

20. Ti – O ____________________ ____________________

21. Sr – Cl ____________________ ____________________

22. Ni – Cl ____________________ ____________________

23. Sr – Cl ____________________ ____________________

24. Mn – O ____________________ ____________________

36 Arranged by: Janet A. Dungog

The Direction of Polarity

 The head of the arrow is pointing toward the more electronegative element.
 The tail of the arrow, with a perpendicular line drawn through it, is positioned at the less electronegative element.
+ –
 Alternatively, the symbols δ and δ indicate this unequal sharing of electron density.
+
•  means an atom is electron deficient (has a partial positive charge).
–
•  means the atom is electron rich (has a partial negative charge).

Exercise
+ –
Use the symbols δ and δ to indicate the polarity of the labeled bonds.

Br Cl NH2 OH CH3 NH2

Li

Polarity of Molecules
Thus far, we have been concerned with the polarity of one bond. To determine whether a molecule has a net dipole, use the
following two-step procedure:

1. Use electronegativity differences to identify all of the polar bonds and the directions of the bond dipoles.
2. Determine the geometry around individual atoms by counting groups, and decide if individual dipoles cancel
or reinforce each other in space.

no net dipole
The net dipole bisects the H-O-H bond angle.
The two dipoles cancel
The two individual dipoles reinforce.

37 Arranged by: Janet A. Dungog

Exercise
1. Indicate which of the following molecules is polar because it possesses a net dipole. Show the direction of the net dipole if
one exists.

a. CH3Br Cl Cl
d. C C
H H

b. CH2Br2 Cl H
e. C C
H Cl

c. CF4

2. Label the polar bonds in each molecule. Indicate the direction of the net dipole (if there is one).

CH3 Br Cl
O C
CH3 Cl
Br

3. The principles of this unit can be applied to organic molecules of any size. Answer the following questions about
amoxicillin, an antibiotic from the penicillin family.

a. Predict the hybridization and geometry around each indicated atom. H H

H O
H H
b. Label five polar bonds using the symbols δ+ and δ–. HO C C S CH3
N CH3
NH2
c. Label five polar bonds using the symbols δ+ and δ–. Label them. H H H N O
O C
H
d. Draw a skeletal structure. OH
amoxicillin

4. Stalevo is the trade name for a medication used for Parkinson’s disease, which contains both L-dopa and entacapone.

HO CON( CH2CH3) 2

CN
HO

NO2

Entacapone

a. Draw a Lewis structure for b. Which C–C bond in c. Which C–C single bond is d. Which C–N bond is the
entacapone. entacapone is the longest? the shortest? longest?

38 Arranged by: Janet A. Dungog