Lect- 1

CH-104: CHEMISTRY
Dr. Uzma Habib
Associate Professor
SINES
Where to contact: [Link]@[Link]
Where to find: Ground Flr, A-Wing-SINES, NUST
 Myself
Ø M-phil in Inorganic/Analytical Chemistry
Quaid-e-Azam University, Islamabad

Ø PhD in Computational Chemistry

Heidelberg University, Germany
 Computational Chemistry

Theory Experiment
Solution

Computation
4
 Lecture / Week Topic
1st Structure & Bonding
2nd Acid and base
3rd Organic Molecules and Functional Groups
4th Alkanes
5th Stereochemistry
6th Alkenes and Alkynes
Understanding Chemical Reactions- Nucleophilic
7th
Substitution Reactions
8th Revision
WEEK-WISE
Mid Term Exam
PLAN
Alkyl halides and elimination reactions
10th

11th Alcohol, Ethers, and Epoxides

Oxidation reduction reactions
12th
Benzene and aromatic compounds
13th Polymer Chemistry
14th Carbohydrates
15th Amino Acids and Proteins
16th Lipids 5
17th Revision
SUCCESS RULES
7
 The Periodic Table

§ The nucleus contains positively charged protons and

uncharged neutrons.
§ The electron cloud is composed of negatively charged
electrons.
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 s orbital, p orbital
• An s orbital has a sphere of electron density and is lower in
energy than the other orbitals of the same shell.
• A p orbital has a dumbbell shape and contains a node of
electron density at the nucleus. It is higher in energy than an s
orbital.

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 s orbital, p orbital
Since there is only one orbital in the first shell, and each shell can hold a
maximum of two electrons, there are two elements in the first row, H and
He.

Each element in the second row of the periodic table has four orbitals
available to accept additional electrons: one 2s orbital, and three 2p
orbitals.

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 Second Row Elements

• The second row of the periodic chart consists of eight

elements, obtained by adding electrons to the 2s and three
2p orbitals.

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 Review of Bonding

• Bonding is the joining of two atoms in a stable

arrangement.
• Through bonding, atoms attain a complete outer shell of
valence electrons and attain a stable noble gas
configuration.
• Ionic bonds result from the transfer of electrons from one
element to another.
• Covalent bonds result from the sharing of electrons
between two nuclei.

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 Bonding in Molecular Hydrogen (H2)

• Hydrogen forms one covalent bond.

• When two hydrogen atoms are joined in a bond, each has a
filled valence shell of two electrons.

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 Second row elements
• Second row elements can have no more than eight
electrons around them. For neutral molecules, this has two
consequences:
v Atoms with one, two, or three valence electrons form one, two,
or three bonds, respectively, in neutral molecules.
v Atoms with four or more valence electrons form enough bonds
to give an octet. This results in the following equation:

v When second-row elements form fewer than four bonds their

octets consist of both bonding (shared) and nonbonding
(unshared) electrons. Unshared electrons are also called lone
pairs.

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Figure 1.3 Summary: The usual number of bonds
of common neutral atoms

15
 Review of Lewis Structures
Lewis structures are electron dot representations for
molecules. There are three general rules for drawing Lewis
structures:
1. Draw only the valence electrons.
2. Give every second-row element an octet of electrons, if
possible.
3. Give each hydrogen two electrons.

In a Lewis structure, a solid

line indicates a two-electron
covalent bond. 14 16
 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.
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 Formal Charge
The number of electrons “owned” by different atoms is
indicated in the following examples:
Example 1

Example 3

Example 2

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Formal Charge

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 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.
Example:

Both are valid Lewis structures and both molecules exist.

These two compounds are called isomers.
Isomers are different molecules having the same molecular
formula.
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 Exceptions to the Octet Rule
Elements in Groups 2A and 3A

Elements in the Third Row

19 21
 Resonance structures
Some molecules cannot be adequately represented by a single
Lewis structure. For example, two valid Lewis structures can be
drawn for the anion (HCONH)¯.

These structures are called resonance structures or resonance

forms. A double headed arrow is used to separate the two
resonance structures.

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 Introduction to Resonance Theory

• Neither resonance structure is an accurate representation for

(HCONH)¯. The true structure is a composite of both resonance forms
and is called a resonance hybrid.

• The hybrid shows characteristics of both structures.

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

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

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 Introduction to Resonance Theory

The following basic principles of resonance theory should be

kept in mind:

1. Resonance structures are not real. An individual resonance

structure does not accurately represent the structure of a
molecule or ion. Only the hybrid does.

2. Resonance structures are not in equilibrium with each other.

There is no movement of electrons from one form to another.

3. 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.

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 Drawing Resonance Structures
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.

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 Drawing Resonance Structures

Rule [3]: Resonance structures must be valid Lewis structures.

Hydrogen must have two electrons and no second-row
element can have more than eight.

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 Drawing Resonance Structures
• Curved arrow notation is a convention that is used to show 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 the electron pair, either in a
bond or lone pair. The head points to where the electron pair “moves.”

Example 1:

Example 2:

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 Determining Molecular Shape
Two variables define a molecule’s structure: bond length and
bond angle.
• Bond length decreases across a row of the periodic
table as the size of the atom decreases.

• Bond length increases down a column of the periodic

table as the size of an atom increases.

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 Determining Molecular Shape—Bond Angle

Bond angle determines the shape around any atom bonded

to two other atoms.
• The number of groups surrounding a particular atom
determines its geometry. A group is either an atom or a lone
pair of electrons.
• The most stable arrangement keeps these groups as far
away from each other as possible. This is exemplified by
Valence Shell Electron Pair Repulsion (VSEPR) theory.

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 Determining Molecular Shape—Bond Angle

Two groups around an atom—

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 Drawing Three Dimensional Structures
• A solid line is used for a bond in the plane.
• A wedge is used for a bond in front of the plane.
• A dashed line is used for a bond behind the plane.

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A Nonbonded Pair of Electrons is Counted as a “Group”

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40
 Drawing Organic Molecules—Condensed Structures

• All atoms are drawn in, but the two-electron bond lines are generally
omitted.
• Atoms are usually drawn next to the atoms to which they are bonded.
• Parentheses are used around similar groups bonded to the same atom.
• Lone pairs are omitted.

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Examples of Condensed Structures (from Figure 1.5)

45

35
 Skeletal Structures
• Assume there is a carbon atom at the junction of any two lines or
at the end of any line.
• Assume there are enough hydrogens around each carbon to make
it tetravalent.
• Draw in all heteroatoms and hydrogens directly bonded to them.

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47
Examples of Skeletal Structures (from Figure 1.7)

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 Words of Caution Regarding Interpretation of Skeletal Structures

• A charge on a carbon atom takes the place of one hydrogen atom.

• The charge determines the number of lone pairs. Negatively
charged carbon atoms have one lone pair and positively charged
carbon atoms have none.

49 38
 Orbitals and Bonding: Hydrogen

Carbon has two core electrons, plus four valence electrons. To fill
atomic orbitals in the most stable arrangement, electrons are
placed in the orbitals of lowest energy.

Note: The lowest energy arrangement of electrons for an atom is called its ground state. 39
 Orbitals and Bonding: Methane

•Carbon has only two unpaired valence electrons, therefore

CH2 should be a stable molecule.

• However, CH 2 is a very unstable species that cannot be

isolated under typical laboratory conditions.
•Also, CH2, carbon would not have an octet of electrons.
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 Orbitals and Bonding: Methane
Another Option
Promotion of an electron from a 2s to a vacant 2p orbital would
form four unpaired electrons for bonding
This process requires energy because it moves an electron to a higher
energy orbital Electronically excited state

Carbon would form two different types of bonds: three with 2p

orbitals and one with a 2s orbital.
However, experimental evidence points to carbon forming four
identical bonds in methane.
Hybridization 41
 Orbitals and Bonding: Methane
Hybridization is the combination of two or more atomic orbitals to
form the same number of hybrid orbitals, each having the same
shape and energy.

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 Bonding Using sp3 Hybrid Orbitals

Figure 1.9 Bonding in CH4 using sp3 hybrid orbitals

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 Other Hybridization Patterns
• One 2s orbital and three 2p orbitals form four sp3 hybrid orbitals.
• One 2s orbital and two 2p orbitals form three sp2 hybrid orbitals.
• One 2s orbital and one 2p orbital form two sp hybrid orbitals.

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 Other Hybridization Patterns

• To determine the hybridization of an atom in a molecule, we

count the number of groups around the atom.
• The number of groups (atoms and nonbonded electron pairs)
corresponds to the number of atomic orbitals that must be
hybridized to form the hybrid orbitals.

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Hybridization Examples

Figure 1.12
Hybrid orbitals of NH3
and H2O

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 Bond Length and Bond Strength
• 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.

• The length and strength of C—H bonds vary depending on the

hybridization of the carbon atom.

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 Bond Length and Bond Strength

Increased percent s-character  increased bond strength

 decreased bond length

As the percent s-character increases, a hybrid orbital holds its

electrons closer to the nucleus, and the bond becomes shorter and
stronger.
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 Electronegativity and Bond Polarity

Electronegativity is a measure of an atom’s attraction for electrons

in a bond.

Electronegativity values for some common elements:

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 Electronegativity and Bond Polarity
Electronegativity values are used as a guideline to indicate whether the
electrons in a bond are equally shared or unequally shared between two
atoms.
When electrons are equally shared, the bond is nonpolar.
When differences in electronegativity result in unequal sharing of electrons,
the bond is polar, and is said to have a “separation of charge” or a “dipole”.

C (2.5) O (3.4)

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 Polarity of Molecules

Use the following two-step procedure to determine if a

molecule has a net dipole:
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.
Electrostatic potential plot of CH3Cl

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 Polarity of Molecules
A polar molecule has either one polar bond, or two or more bond dipoles that
reinforce each other

A nonpolar molecule has either no polar bonds, or two or more bond dipoles that
cancel

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 L-Dopa—A Representative Organic Molecule
The principles learned in this chapter apply to all organic molecules regardless of
size or complexity. For example, we now know a great deal about the structure of
ʟ-dopa, a drug used to treat Parkinson’s disease

For example, you should be able to do all of the following:

ü Convert this skeletal structure of l-dopa to a Lewis structure.
ü Determine the hybridization and geometry around every atom.
ü Label all polar and nonpolar bonds.
ü Compare bond length and bond strength for certain bonds.
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