John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 1
Structure and Bonding

Credits to Paul D. Adams • University of Arkansas

 General Chemistry 2 (MF010)

What is Organic Chemistry?

 Living things are
made of organic
chemicals
 Proteins that
make up hair
 DNA, controls
genetic make-up
 Foods,
medicines
 Examine
structures to the
right
 General Chemistry 2 (MF010)

Origins of Organic Chemistry

 Foundations of organic chemistry from mid-1700’s.

 Compounds obtained from plants, animals hard to

isolate, and purify.

 Compounds also decomposed more easily.

 Torben Bergman (1770) first to make distinction between

organic and inorganic chemistry.

 It was thought that organic compounds must contain

some “vital force” because they were from living sources.
 General Chemistry 2 (MF010)

Origins of Organic Chemistry

 Because of “vital force”, it was thought that organic
compounds could not be synthesized in laboratory unlike
inorganic compounds.

 1816, Chevreul showed that not to be the case, he could

prepare soap from animal fat and an alkali and glycerol is
a product

 1828, Woehler showed that it was possible to convert

inorganic salt ammonium cyanate into organic substance
“urea”
 General Chemistry 2 (MF010)

Origins of Organic Chemistry

 Organic chemistry is study of carbon compounds.
 Why is it so special?
 90% of more than 30 million chemical compounds contain carbon.
 Examination of carbon in periodic chart answers some of these questions.
 Carbon is group 4A element, it can share 4 valence electrons and form 4
covalent bonds.
 General Chemistry 2 (MF010)

Why This Chapter?

 Review ideas from general chemistry: atoms, bonds,

molecular geometry and…….

….most importantly…….

……to familiarize you with important things you need to

know before studying organic chemistry!
 General Chemistry 2 (MF010)

1.1 Atomic Structure

 Structure of an atom
 Positively charged nucleus (very dense, protons and neutrons) and small (10 -15
m)

 Negatively charged electrons are in a cloud (10 -10 m) around nucleus

 Diameter is about 2  10-10 m (200 picometers (pm)) [the unit ångström (Å) is
10-10 m = 100 pm]
Atomic Number
General Chemistry 2 (MF010)

and Atomic Mass

 The atomic number (Z) is the number of protons in the
atom's nucleus

 The mass number (A) is the number of protons plus

neutrons

 All the atoms of a given element have the same atomic

number

 Isotopes are atoms of the same element that have different

numbers of neutrons and therefore different mass numbers

 The atomic mass (atomic weight) of an element is the

weighted average mass in atomic mass units (amu) of an
element’s naturally occurring isotopes
1.2 Atomic Structure:
General Chemistry 2 (MF010)

Orbitals
What exactly is an “orbital”?

A good way of viewing an “orbital” (a.k.a. atomic orbital) is to

think of it as a mathematical expression whose square of wave
function or orbital (denoted as Ψ2) predicts the volume of
space around a nucleus where an electron can be found.

In other words, although we don’t know the exact position of an

electron at any given time, but the orbital reveals to us where
the electron is most likely to be found.

Another way of putting it: an orbital represents the space where

an electron spends most (90% to 95%) of its time.
 General Chemistry 2 (MF010)

Shapes of Atomic Orbitals

 Four different kinds of orbitals for electrons based on
those derived for a hydrogen atom
 Denoted s, p, d, and f
 s and p orbitals most important in organic and biological
chemistry
 s orbitals: spherical, nucleus at center
 p orbitals: dumbbell-shaped, nucleus at middle
 d orbitals: elongated dumbbell-shaped, nucleus at
center
Orbitals and Shells
General Chemistry 2 (MF010)

(Continued)
 Orbitals are grouped in shells (or layers) of increasing
size and energy
 Different shells contain different numbers and kinds of
orbitals
 Each orbital can be occupied by two electrons
Orbitals and Shells
General Chemistry 2 (MF010)

(Continued)
 First shell contains one s orbital, denoted 1s, holds only
two electrons
 Second shell contains one s orbital (2s) and three p
orbitals (2p), eight electrons
 Third shell contains an s orbital (3s), three p orbitals
(3p), and five d orbitals (3d), 18 electrons
 General Chemistry 2 (MF010)

p-Orbitals
 In each shell there are three perpendicular p orbitals,
px, py, and pz, of equal energy

 Lobes of a p orbital are separated by region of zero

electron density, a node
 General Chemistry 2 (MF010)

1.3 Atomic Structure: Electron

Configuration
Rules for Orbital Occupancies in Ground-state
Electron Configuration of an Atom
1. Lowest-energy orbitals fill first: 1s  2s  2p  3s 
3p  4s  3d (Aufbau (“build-up”) principle).

2. Electron spin can have only two orientations, up  and

down . Only two electrons can occupy an orbital, and
they must be of opposite spin (Pauli’s exclusion
principle) to have unique wave equations.

3. If two or more empty orbitals of equal energy are

available, electrons occupy each orbital with parallel
spins until all orbitals have one electron (Hund's rule).
 General Chemistry 2 (MF010)

1.4 Development of Chemical

Bonding Theory
 Kekulé and Couper independently observed that
carbon always has four bonds
 van't Hoff and Le Bel proposed that the four bonds of
carbon have specific spatial directions
 Atoms surround carbon as corners of a tetrahedron
 General Chemistry 2 (MF010)

Development of Chemical
Bonding Theory

 Atoms form bonds because the compound that results

is more stable than the separate atoms

 Ionic bonds in salts form as a result of electron

transfers

 Organic compounds have covalent bonds from sharing

electrons (G. N. Lewis, 1916)
 General Chemistry 2 (MF010)

Development of Chemical
Bonding Theory
 Lewis structures
(electron dot) show
valence electrons of an
atom as dots
 Hydrogen has one
dot, representing its
1s electron
 Carbon has four dots
(2s2 2p2)

 Kekulé structures (line-

bond structures) have a
line drawn between two
atoms indicating a 2
electron covalent bond.

 Stable molecule results

at completed shell, octet
(eight dots) for main-
group atoms (two for
hydrogen)
 General Chemistry 2 (MF010)

Development of Chemical
Bonding Theory
 Atoms with four or more valence electrons form as
many bonds as they need electrons to fill the s and p
levels of their valence shells to reach a stable octet.

 Carbon has four valence electrons (2s2 2p2), forming

four bonds (CH4).

 Nitrogen has five valence electrons (2s2 2p3) but forms

only three bonds (NH3).

 Oxygen has six valence electrons (2s2 2p4) but forms

two bonds (H2O)
 General Chemistry 2 (MF010)

Development of Chemical
Bonding Theory
 General Chemistry 2 (MF010)

Non-Bonding Electrons
 Valence electrons not used in bonding are called nonbonding
electrons, or lone-pair electrons
 E.g. Nitrogen atom in ammonia (NH3)
 Shares six valence electrons in three covalent bonds
and remaining two valence electrons are nonbonding
lone pair
 General Chemistry 2 (MF010)

1.5 Describing Chemical Bonds:

Valence Bond Theory
 Covalent bond forms when two atoms approach each other closely
so that a singly occupied orbital on one atom overlaps a singly
occupied orbital on the other atom
 Two models to describe covalent bonding: Valence Bond Theory,
and Molecular Orbital Theory

Valence Bond Theory:

 Electrons are paired in the overlapping orbitals and are attracted to
nuclei of both atoms
 H–H bond results from the overlap of two singly occupied
hydrogen 1s orbitals
 H-H bond is cylindrically symmetrical, the bond is called sigma
() bond
Bond Energy (a.k.a. Bond
General Chemistry 2 (MF010)

Strength)
 Reaction 2 H·  H2 releases 436 kJ/mol
 Product has 436 kJ/mol less energy than two atoms:
H–H has bond strength of 436 kJ/mol. (1 kJ = 0.2390
kcal; 1 kcal = 4.184 kJ)
Bond Energy (a.k.a. Bond
General Chemistry 2 (MF010)

Strength)
Covalent bond formation in H2

Atoms are far apart

Attraction between an atom’s

nucleus and another atom’s
electrons draws the atoms
closer. So potential energy of
system lowers.
Any shorter distance
will increase
repulsions and cause
rise in potential At some internuclear distance, attraction is
energy. maximum, so potential energy of system is at its
lowest.
 General Chemistry 2 (MF010)

1.6 sp3 Orbitals and the

Structure of Methane
 Carbon has 4 valence electrons (2s2 2p2)
 In CH4, all C–H bonds are identical (tetrahedral)
 sp3 hybrid orbitals: s orbital and three p orbitals
combine to form four hybrid orbitals (sppp = sp3).
These four sp3 orbitals are oriented tetrahedrally.
 General Chemistry 2 (MF010)

The Structure of Methane

 sp3 orbitals on C overlap with 1s orbitals on 4 H atoms to
form four identical C-H bonds
 Each C–H bond has a strength of 439 kJ/mol and length of
109 pm
 Bond angle: each H–C–H is 109.5°, the tetrahedral angle.
 General Chemistry 2 (MF010)

1.7 sp3 Orbitals and the

Structure of Ethane
 The two carbon atoms bond to each other by  overlap of an sp3
orbital.
 The three remaining sp3 orbitals on each C overlap with H 1s
orbital to form C–H bonds (6 C-H bonds altogether).
 All bond angles of ethane are tetrahedral, i.e. approx. 109.5°.
 General Chemistry 2 (MF010)

1.8 sp2 Orbitals and the

Structure of Ethylene
 sp2 hybrid orbitals: 2s
orbital combines with
two 2p orbitals, giving 3
hybrid orbitals (spp =
sp2).

 sp2 orbitals are in a

plane with 120° bond
angles and trigonal
planar orientation.

 Remaining p orbital is
perpendicular to the
plane
Bonds From sp2 Hybrid
General Chemistry 2 (MF010)

Orbitals
 Two sp2-hybridized orbitals (i.e., one sp2 hybrid orbital
from each C) overlap to form a  bond.
 The remaining p non-hybrid orbitals overlap side-by-
side to formation a pi () bond
 One sp2–sp2  bond and one 2p–2p  bond result in the
sharing of four electrons, thus the formation of C-C
double bond.
 H atoms form  bonds with four sp2 orbitals (i.e., two
sp2 orbitals from each C atom).
 General Chemistry 2 (MF010)

Structure of Ethylene
 H–C–H and H–C–C bond angles of about 120°.

 C=C double bond in ethylene is shorter and stronger

than single bond in ethane

 Ethylene C=C bond length 134 pm (whereas C–C bond

length is 154 pm)
 General Chemistry 2 (MF010)

1.9 sp Orbitals and the

Structure of Acetylene
 C-C a triple bond sharing six electrons
 Carbon 2s orbital hybridizes with a single p orbital giving
two sp hybrids
 Thus, the two remaining p non-hybrid orbitals remain
unchanged.
 sp orbitals are linear, 180° apart on x-axis.
 The two non-hybrid p orbitals are perpendicular on the y-
axis and z-axis.
 General Chemistry 2 (MF010)

Orbitals of Acetylene
 Two sp hybrid orbitals from each C form sp–sp  bond.
 pz non-hybrid orbitals from each C form a pz–pz  bond by
sideways overlap and py non-hybrid orbitals also overlap
similarly.
 Thus, one  bond and two  bonds altogether result in
carbon-carbon triple bond.
 General Chemistry 2 (MF010)

Bonding in Acetylene
 Sharing of six electrons forms C C

 The remaining two sp orbitals (i.e., one sp orbital

from each C atom) form  bonds with hydrogens
Comparison of C–C and C–H Bonds in General Chemistry 2 (MF010)

Methane, Ethane, Ethylene, and

Acetylene

Trend to note: From carbon-carbon single bond to triple

bond, bond strength increases but bond length
decreases.
 General Chemistry 2 (MF010)

1.10 Hybridization of Nitrogen

and Oxygen
 Elements other than C can have hybridized orbitals.
 H–N–H bond angle in ammonia (NH3) 107.3°
 C-N-H bond angle is 110.3 °
 N’s orbitals (sppp) hybridize to form four sp3 orbitals
 One sp3 orbital is occupied by two nonbonding
electrons (i.e., lone-pair electrons), and three sp3
orbitals have one electron each, thus forming bonds to
H, H and CH3.
 General Chemistry 2 (MF010)

1.11 Describing Chemical Bonds:

Molecular Orbital Theory
 A molecular orbital (MO): where electrons are most likely to
be found in a molecule .
 Additive combination (bonding) MO is lower in energy
 Subtractive combination (antibonding) MO is higher energy
Molecular Orbitals in
General Chemistry 2 (MF010)

Ethylene
 The  bonding MO is from combining p orbital lobes with the
same algebraic sign
 The  antibonding MO is from combining lobes with opposite
signs
 Only bonding MO is occupied
 General Chemistry 2 (MF010)

1.12 Drawing Structures

 Drawing every bond in organic molecule can be very
tedious.
 Several shorthand methods have been developed to draw
structures.
 Condensed structures don’t have C-H or C-C single
bonds shown. They are merely understood.
e.g.
Drawing Structures
General Chemistry 2 (MF010)

(Continued)
3 general rules for drawing organic structures:

1) Carbon atoms aren’t usually shown. Instead a carbon

atom is assumed to be at each bend of a line and at the
end of each line.

2) Hydrogen atoms bonded to carbon aren’t shown.

3) Atoms other than carbon and hydrogen are shown.

 General Chemistry 2 (MF010)

Summary
 Organic chemistry – chemistry of carbon compounds
 Atom: charged nucleus containing positively charged protons and
netrually charged neutrons surrounded by negatively charged
electrons
 Electronic structure of an atom described by wave equation
 Electrons occupy orbitals around the nucleus.
 Different orbitals have different energy levels and
different shapes
 s orbitals are spherical, p orbitals are dumbbell-shaped

 Covalent bonds - electron pair is shared between atoms

 Valence bond theory - electron sharing occurs by overlap of two
atomic orbitals
 Molecular orbital (MO) theory - bonds result from combination of
atomic orbitals to give molecular orbitals, which belong to the
entire molecule
 General Chemistry 2 (MF010)

Summary (Continued)
 Sigma () bonds - Circular cross-section and are formed by head-
on interaction
 Pi (π) bonds - “dumbbell” shape from sideways interaction of p
orbitals
 Carbon uses hybrid orbitals to form bonds in organic molecules:
 In single bonds with tetrahedral geometry, a carbon has four sp3
hybrid orbitals.
 In double bonds with trigonal planar geometry, a carbon has
three equivalent sp2 hybrid orbitals, but uses only one sp2
hybrid orbital and one unhybridized p orbital to form double bond.
 In triple bonds with linear geometry, a carbon has two equivalent
sp hybrid orbitals, but uses only one sp hybrid orbital and two
unhybridized p orbitals to form triple bond.
 Atoms such as nitrogen and oxygen hybridize to form strong,
oriented bonds
 The nitrogen atom in ammonia and the oxygen atom in water are
sp3-hybridized
 General Chemistry 2 (MF010)

Let’s Work a Problem

Draw an electron-dot structure for acetonitrile, C2H3N, which

contains a carbon-nitrogen triple bond. How many electrons
does the nitrogen atom have in its outer shell ? How many of
the electrons are bonding, and how many are non-bonding?
 General Chemistry 2 (MF010)

Answer

To address this question, we must realize that the nitrogen

will contain 8 electrons in its outer shell. Six electrons will be
used in the C-N triple bond (shaded box), and two electrons
are non-bonding.
 General Chemistry 2 (MF010)

Additional Reference

 Silberberg, M. S. 2006. CHEMISTRY: THE

MOLECULAR NATURE OF MATTER AND
CHANGE, 4th ed. McGraw Hill.
 General Chemistry 2 (MF010)

Self-test Problems
1. Draw all the bonds in propene, CH3CH=CH2.
Indicate the hybridization of each carbon in
propene, and predict the value of each bond
angle.
2. Draw a line-bond structure for propyne,
CH3C≡CH. Indicate the hybridization of each
carbon in propyne, and predict the value of each
bond angle.
3. Draw line-bond structure for formaldimine,
CH2NH. How many electrons are shared In the C-
N bond? What is the hybridization of the N atom?