CHE 1502 – General Chemistry

1B

Prof. Adewale O. Adeloye

Lecturer In-Charge

University of South Africa.

Lecture 03

20th April, 2024

 3rd Week Lecture Outlines

 Lewis structures;
 Structural representation of organic molecules;
Formal charges
 Concept of constitutional / structural isomerism/
The position of carbon in the periodic table. Other
elements commonly found in organic compounds are
shown in the colors typically used to represent them
 The Atomic Structure: Electron Configurations
 The lowest-energy arrangement, or ground-state electron
configuration, of an atom is a listing of the orbitals that the atom’s
electrons occupy. The three important rules to remember when
predicting this arrangement are listed below:

RULE 1: The orbitals of lowest energy are filled first, according to

the order 1s 2s 2p 3s 3p 4s 3d.

RULE 2: Only two electrons can occupy an orbital, and they must
be of opposite spin. (Electrons act in some ways as if they were
spinning on an axis, somewhat as the earth spins. This spin can
have two orientations, denoted as up and down )

RULE 3: If two or more empty orbitals of equal energy are

available, one electron occupies each with the spins parallel.
 Hydrogen, for instance, has only one electron, which must
occupy the lowest-energy orbital. Thus, hydrogen has a 1s1
ground-state electron configuration. Carbon has six electrons and
the ground-state electron configuration 1s2 2s2 2p2.

**Note that a superscript is used to represent the number of

electrons in a particular orbital.
 Lewis structures and formal charges
 Lewis structures are a fundamental tool in organic chemistry
for representing the bonding between atoms and the arrangement
of electrons around them. They provide a simplified picture that
helps us understand various aspects of organic molecules,
including:
Structure:
 Lewis structures show how atoms are connected by single,
double, or triple bonds using lines or dots.
 They also depict lone pairs (unbonded electrons) around atoms.

Bonding:
 The number of lines connecting two atoms represents the bond
order (single, double, or triple). This indicates the number of
shared electron pairs between the atoms.
 Lone pairs contribute to bonding by participating in the octet
rule, where most elements in organic chemistry aim to have eight
electrons in their valence shell.

Valence Electrons:
 Lewis structures are constructed by considering the valence
electrons of each atom involved in the molecule.
By summing the valence electrons of all atoms and subtracting
the number of electrons used in forming bonds, we can determine
the number of lone pairs around each atom.

Drawing Lewis Structures:

1. Skeletal Structure: Start by drawing the basic framework of
the molecule, showing how the atoms are connected.
2. Valence Electrons: Count the total valence electrons from all
atoms in the molecule.
3. Octet Rule: Place two electrons (a single bond) between each
connected pair of atoms. Then, distribute remaining electrons
as lone pairs around each atom to satisfy the octet rule (except
for hydrogen, which needs two electrons).
4. Formal Charge Check: Sometimes, achieving the octet rule
might require forming double or triple bonds between certain
atoms. In these cases, verify that the formal charges (the
difference between an atom's valence electrons and the
number of electrons assigned to it in the Lewis structure) are
minimized.

Limitations of Lewis Structures:

 While helpful for most organic molecules, Lewis structures do
not perfectly depict resonance structures or situations involving
significant delocalization of electrons.

 They primarily focus on valence electrons and do not account

for all the complexities of electron interactions in molecules.
 Importance of Lewis Structures in Organic Chemistry:
Understanding Lewis structures allows you to:

1. Predict the geometry of molecules based on VSEPR theory

(Valence Shell Electron Pair Repulsion theory).
2. Determine the formal charges of atoms, which can be helpful
in understanding reactivity.
3. Identify functional groups in organic molecules, which play a
vital role in their properties and reactions.
4. Draw resonance structures for conjugated systems, where
electrons are delocalized
Structure Representations in Organic Molecules: Dot structures:
Single bonds
 This is the maximum electrons that can be found in the energy
level where carbon, nitrogen and oxygen occur in the periodic
table is 8 Electrons.
H
H C O H
(i) CH3OH
H
*** Note that 2 Valence Electrons
= 1 Single Covalent bond
H

C
(ii) CH3NH2 N H
H
H
H
Whereas, if you look at hydrogen, it’s one level above the energy
level to the carbon. This level can only have a maximum of 2
Electrons.
(i) Shows complete Dot structure for methanol, while in (ii) the
Dot structures for methylamine were combined to make a single
bond leaving (Nitrogen) atom with a lone pair electron
uncombined.

 What observation can you draw on the carbon, nitrogen,

oxygen and hydrogen atoms: (i) Carbon, nitrogen, oxygen and
hydrogen are surrounded by 8, 8, 8 and 2 electrons respectively.

 Because the electrons forming the bonding pairs are shared, the
compounds are said to be have covalent bonding and they are
stable.

Each of the atoms in the compounds obey the

octet rule:
 The octet rule is a chemical rule of thumb that reflects the
theory that main-group elements tend to bond in such a way that
each atom has eight electrons in its valence shell, giving it the
same electronic configuration as a noble gas.

 The rule is especially applicable to carbon, nitrogen, oxygen,

and the halogens; although more generally the rule is applicable
for the s-block and p-block of the periodic table

 By mastering Lewis structures, you gain a solid foundation for

understanding organic chemistry concepts like molecular
structure, bonding, and reactivity. This knowledge is essential for
further exploration of organic reactions, mechanisms, and
functional group chemistry.
Let us draw dot structure of a compound – Propane, and check if
it obeys octet rule:
H H H
Alkane = CnH2n+2
H C C C H
for n = 3; H H H
H H H
C3H(2x3)+2 = C3H6+2
H C C C H
Propane = C3H8 H H H
Propane has 3 Carbon atoms, each carbon atom has a valence of 4, so you have
3 x 4 electrons, which gives you Total of 12.
Now, you have 8 hydrogen atoms, each atom only contains 1 electron.
Therefore, you have a total of (1x8) hydrogen electrons.

When you add the total number of electrons together: 12 + 8 = 20.

To know if you’re correct, count the total number of dots in Propane.

 Dot structures: Multiple bonds
Acetone = 2-Propanone
H O H H O H H O H
H C C C H H C C C H H C C C H
H H H H H H

Propene = Propan-1-ene
H H H H H H H
H C C C H H C C C H H C C C H
H H H H H

Propyne = Propan-1-yne
H H H
H C C C H H C C C H H C C C H
H H H
 Lewis structures, or electron-dot structures, in which the
valence shell electrons of an atom are represented as dots.
Thus, hydrogen has one dot representing its 1s electron,
carbon has four dots (2s2 2p2), oxygen has six dots (2s2 2p4),
and so on.

A stable molecule results whenever a noble-gas

configuration is achieved for all the atoms—eight dots (an
octet) for main-group atoms or two dots for hydrogen.

 Another Simpler way is the use of Kekulé structures, or

line-bond structures, in which a two-electron covalent bond
is indicated as a line drawn between atoms.
 The number of covalent bonds an atom forms
depends on how many additional valence electrons it
needs to reach a noble-gas configuration.
Hydrogen has one valence electron (1s) and needs one more to
reach the helium configuration (1s2), so it forms one bond.

Carbon has four valence electrons (2s2 2p2) and needs four more
to reach the neon configuration (2s2 2p6), so it forms four bonds.

Nitrogen has five valence electrons (2s2 2p3), needs three more,
and forms three bonds;

Oxygen has six valence electrons (2s2 2p4), needs two more, and
forms two bonds;

Halogens have seven valence electrons (2s2 2p5), need one more,
and form one bond.
 Valence electrons that are not used for bonding are called
lone-pair electrons, or nonbonding electrons.

 The nitrogen atom in ammonia (NH3), for instance, shares

six valence electrons in three covalent bonds and has its
remaining two valence electrons in a nonbonding lone pair.

 Despite the lone-pair electrons not written in equations,

you must keep them in mind since they are often crucial in
certain chemical reactions.
 Formal Charges
 Formal charge is a bookkeeping tool in Lewis
structures that helps us represent the distribution of
electrons around atoms. It is calculated as:
 Formal charge (FC) = Valence electrons (VE) - Number
of lone pair electrons (LPE) - (1/2) Number of bonding
electrons (BE)
 To determine the formal charge for a specific case, you
will need the Lewis structure of the molecule containing
the atom in question. Here is how to proceed:
Interpretation:
 FC = 0: The atom has its ideal electron configuration
and shares electrons fairly in the molecule.
 FC ≠ 0: The atom may have gained or lost electrons
relative to its neutral state, indicating a more polar
distribution. However, formal charge does not directly
translate to actual charge separation.
 Draw the Lewis structure: Identify the central atom (often
the least electronegative element) and arrange the surrounding
atoms to minimize formal charges. Connect atoms with single
or double bonds as needed to satisfy their octet rule. Place lone
pairs around terminal atoms to complete their octets.
 Count electrons: Determine the valence electrons for each
atom and add them up for the entire molecule.
 Assign electrons: Assign two electrons to each bond (one
from each bonded atom).
 Calculate formal charges: Use the formula above for each
atom in the Lewis structure.
Limitations:
 Formal charge does not account for electronegativity
differences. A more electronegative atom will tend to attract
the shared electrons more, resulting in a slight negative
formal charge even when FC = 0.
 It is a bookkeeping tool, not a measure of actual charge. Do
not assume a formal charge of +1 directly translates to a
positive point charge on the atom.

Uses:
 Helps evaluate the most reasonable Lewis structure for a
molecule by considering electron distribution and
minimizing formal charges.
 Provides a starting point for understanding electron flow
and reactivity in molecules (although electronegativity plays
a more significant role).
Additional Tips:
 When drawing Lewis structures, prioritize placing formal
charges on less electronegative atoms like carbon or
hydrogen.
 Molecules with zero formal charge on all atoms are
generally more stable than those with significant formal
charges.

Further Information on Formal Charge:

For a deeper understanding, you can explore concepts like:
Resonance structures: In some cases, a molecule can have
multiple valid Lewis structures, each contributing to the
overall electronic structure.
Electronegativity: This property determines how strongly
an atom attracts electrons in a bond, influencing the
distribution of formal charges.
 By understanding formal charges and their limitations,
you will gain a valuable tool for analyzing Lewis structures
and visualizing electron distribution in molecules.

Example:
Let us calculate the formal charge of the carbon atom in the
molecule CH₃OH (methanol):
Valence electrons (VE): Carbon has 4 valence electrons.
Lone pair electrons (LPE): Carbon has 0 lone pairs in this
structure.
Bonding electrons (BE): Carbon forms 4 single bonds (8
bonding electrons).
Formal charge (FC): FC = 4 (VE) - 0 (LPE) - (1/2) * 8 (BE) =
4 - 4 = 0.
Example:
Consider the ammonium ion (NH₄⁺).

Lewis structure: H-N-H (with H atoms surrounding the

central N) and a positive charge on the upper right corner.

Electron count: N (5 valence electrons) + 4 H (1 each, total 4) +

1 (positive charge removes one electron) = 10 electrons.

Assigned electrons: 4 bonds (2 electrons each) = 8 electrons.

Formal charge of N: 5 - 0 - (1/2)(8) = +1 (as expected for four

bonds and no lone pairs).
 However, it should be noted that the formal charge of a
nitrogen atom can vary depending on its bonding
environment:

Take note that:

• Three bonds and one lone pair: In this common scenario,

the nitrogen atom has a formal charge of zero. This is
because the electrons are distributed evenly between bonds
and lone pairs.
• Four bonds and no lone pairs: This is less frequent, but the
nitrogen atom would have a formal charge of +1. Here, there
are more bonding electrons than lone pair electrons.
 Generally, to determine the formal charge for a specific
case, you will need the Lewis structure of the molecule
containing the specific atom.
 Another method used in the determination or calculation
of the formal charge for a specific case involved the use of
the Lewis structure of the molecule containing the atom.
Example 1: Calculate the Formal charges O, N, Br and C of
the following molecules:

Use this formula:

Formal charge (FC) = V– (b + d);

where V = valence electrons

b = number of bonding
d = number of dots
 CH3O Valence electrons for O = 6
(i) Number of bonding = 1
Number of Dot = 6

Formal Charges = Valence electron - (b + d)

= 6 - (1 +6)

= 6 - 7 = -1

CH3O

(ii) Valence electrons for N = 5

N(CH3)4
Number of bonding = 4
Number of Dot = 0

Formal Charges = Valence electron - (b + d)

= 5 - (4 +0)

= 5 - 4 = +1

N(CH3)4
 H2C=Br Valence electrons for Br = 7
(iii) Number of bonding = 2
Number of Dot = 4

Formal Charges = Valence electron - (b + d)

= 7 - (2 + 4)

= 7 - 6 = +1

H2C=Br

(iv) R3C Valence electrons for C = 4

Number of bonding = 3
Number of Dot = 0

Formal Charges = Valence electron - (b + d)

= 4 - (3 + 0)

= 4 - 3 = +1

R3C (A carbocation)
 Understanding the concept of constitutional / structural
isomerism
 Structural isomerism and constitutional isomerism are both
types of isomerism, but they differ in the following ways.
Constitutional isomers usually have different connectivity, and
stereoisomers have the same connectivity, but differ in spatial
arrangements.

Structural isomers have the same molecular formula, but a

different binding arrangement among atoms.

Isomers always have the same chemical formula. When the

chemical formulae are different, then the compounds are
completely different.

Important information can be gained from the chemical

formulas when comparing compounds.
 Example:
 Consider the molecules butane (C₄H₁₀) and methylpropane
(C₄H₁₀).
Both have the same molecular formula.
Butane has a straight chain of four carbon atoms (CH₃-CH₂-
CH₂-CH₃).
Methylpropane has a branched chain with three carbon atoms
in a row and a methyl group (CH₃) attached to the second
carbon (CH₃-CH(CH₃)-CH₂).
 These different arrangements make them structural
isomers, even though they have the same number of carbon
and hydrogen atoms.
END OF LECTURE 03

QUESTIONS?????