Organic Chemistry

 The study of the compounds of carbon

 Over 10 million compounds have been
identified
 C is a small atom
◦ it forms single, double, and triple bonds
◦ it is intermediate in electronegativity (2.5)
◦ it forms strong bonds with C, H, O, N, and some
metals
 Schematic View of an Atom
◦ a small dense nucleus,
diameter 10-14 - 10-15 m,
which contains positively
charged protons and most
of the mass of the atom
◦ an extranuclear space,
diameter 10-10 m, which
contains negatively
charged electrons
Electron Configuration of Atoms
 Electrons are confined to regions of space
called principle energy levels (shells)
◦ each shell can hold 2n2 electrons (n =
1,2,3,4......)

N u mb er of Relative En ergies
Electrons S hell of Electrons
S hell Can Hold in Thes e Shells
4 32 h igh er
3 18
2 8
1 2
low er
Electron Configuration of Atoms
 Aufbau Principle:
◦ orbitals fill in order of increasing energy from
lowest energy to highest energy
 Pauli Exclusion Principle:
◦ only two electrons can occupy an orbital and
their spins must be paired
 Hund’s Rule:
◦ when orbitals of equal energy are available but
there are not enough electrons to fill all of them,
one electron is added to each orbital before a
second electron is added to any one of them
Electron Configuration of Atoms
Drawing electron
Lewis Dot Structures
 Gilbert N. Lewis
 Valence shell:
◦ the outermost occupied electron shell of an atom
 Valence electrons:
◦ electrons in the valence shell of an atom; these
electrons are used to form chemical bonds and in
chemical reactions
 Lewis dot structure:
◦ the symbol of an element represents the nucleus
and all inner shell electrons
◦ dots represent valence electrons
 Struktur Lewis Dot
 Struktur Dot Lewis untuk unsur 1-18
1A 2A 3A 4A 5A 6A 7A 8A
H. He :
. . . . .

:
Li . Be : B: C : . N : : O. : :F : :N e :

:
. . . . .

: :
N a. M g : A l : Si : . P : :S :
.
:Cl : :A r :

:
Lewis Model of Bonding
 Atoms bond together so that each atom acquires
an electron configuration the same as that of the
noble gas nearest it in atomic number
◦ an atom that gains electrons becomes an anion
◦ an atom that loses electrons becomes a cation
◦ the attraction of anions and cations leads to the
formation of ionic solids
◦ an atom may share electrons with one or more
atoms to complete its valence shell; a chemical bond
formed by sharing electrons is called a covalent bond
◦ bonds may be partially ionic or partially covalent;
these bonds are called polar covalent bonds
In chemistry, a bond is typically classified as one of two types:

covalent
Purely covalent (non-polar): The bonding electrons are shared
equally between the two bonding atoms.
Polar covalent: The electrons are shared between the two
bonding atoms, but unequally, with the electrons spending
more time around the more electronegative atom.

Ionic
Ionic: The electrons aren’t shared. Instead, the more
electronegative atom of the two bonding atoms selfishly grabs
the two electrons for itself, giving this more electronegative atom
a formally negative charge and leaving the other atom with a
formal positive charge. The bond in an ionic bond is an
attraction of opposite charges.
Electronegativity
 Electronegativity:
◦ a measure of an atom’s attraction for the
electrons it shares with another atom in a
chemical bond
 Pauling scale
◦ generally increases left to right in a row
◦ generally increases bottom to top in a column
Electronegativity:

 The ability of atoms in a molecule to attract electrons to itself.

 On the periodic chart, electronegativity increases as you go…
◦ …from left to right across a row.
◦ …from the bottom to the top of a column.
 Formation of Ions
 A rough guideline:
◦ ions will form if the difference in electronegativity
between interacting atoms is 1.9 or greater
◦ example: sodium (EN 0.9) and fluorine (EN 4.0)
◦ we use a single-headed (barbed) curved arrow to
show the transfer of one electron from Na to F
•• ••
+ -
•
•

•
•
•
•
Na + F
••
Na F
••

◦ in forming Na+F-, the single 3s electron from Na

is transferred to the partially filled valence shell
of F
Na(1s22s 22p 63s1 ) + F(1s 22s2 2p5 ) Na+(1s2 2s22p 6) + F-(1s2 2s2 2p6 )
Covalent Bonds
 The simplest covalent bond is that in H2
◦ the single electrons from each atom combine to
form an electron pair
H• + •H H-H H 0 = -435 kJ (-104 kcal)/mol
◦ the shared pair functions in two ways
simultaneously; it is shared by the two atoms and
fills the valence shell of each atom
 The number of shared pairs
◦ one shared pair forms a single bond
◦ two shared pairs form a double bond
◦ three shared pairs form a triple bond
Polar and Non-polar Covalent Bonds
 Although all covalent bonds involve
sharing of electrons, they differ widely in
the degree of sharing
 We divide covalent bonds into
◦ Non-polar covalent bonds
◦ polar covalent bonds
D i fference in
El ectron eg ati vity
Betw een Bo nded Ato ms Typ e of Bond
Less than 0.5 N on pol ar cov alent
0.5 to 1.9 Pol ar co valent
Greater than 1.9 Io ns f orm
Polar and Non-polar Covalent Bonds
◦ an example of a polar covalent bond is that of
H-Cl
◦ the difference in electronegativity between Cl
and H is 3.0 - 2.1 = 0.9
◦ we show polarity by using the symbols d+ and
d-, or by using an arrow with the arrowhead
pointing toward the negative end and a plus
sign on the tail of the arrow at the positive
end
d+ d-
H Cl H Cl
 Polar Covalent Bonds
 Bond dipole moment (m):
◦ a measure of the polarity of a covalent bond
◦ the product of the charge on either atom of a
polar bond times the distance between the nuclei
◦ Table below shows average bond dipole moments
of selected covalent bonds
Bond Bond Bond
Dipole Dipole D ipole
Bond (D ) Bond (D ) Bond (D)

H-C 0.3 C-F 1.4 C-O 0.7

H-N 1.3 C-Cl 1.5 C=O 2.3
H-O 1.5 C-Br 1.4 C-N 0.2
H-S 0.7 C-I 1.2 --
C=N 3.5
Lewis Structures
 To write a Lewis structure
◦ determine the number of valence electrons
◦ determine the arrangement of atoms
◦ connect the atoms by single bonds
◦ arrange the remaining electrons so that each
atom has a complete valence shell
◦ show a bonding pair of electrons as a single line
◦ show a nonbonding pair of electrons as a pair of
dots
◦ in a single bond atoms share one pair of
electrons, in a double bond they share two pairs
of electrons, and in a triple bond they share three
pairs of electrons
 Lewis Structures
H
H-O-H H-N-H H-C-H H-Cl
H H
H 2 O (8) N H 3 (8) CH 4 (8) HCl (8)
Water Ammonia Meth ane Hyd rogen ch loride
H H H O
C C H-C C-H C O H C H
O O
H H H
C2 H 4 (12) C2H 2 (10) CH 2O (12) H 2CO 3 (24)
Ethylene Acetylen e Formald ehyde Carbonic acid

 In neutral molecules
◦ hydrogen has one bond
◦ carbon has 4 bonds and no lone pairs
◦ nitrogen has 3 bonds and 1 lone pair
◦ oxygen has 2 bonds and 2 lone pairs
◦ halogens have 1 bond and 3 lone pairs
Formal Charge
 Formal charge: the charge on an atom in a molecule or a
polyatomic ion
 To derive formal charge
1. write a correct Lewis structure for the molecule or ion
2. assign each atom all its unshared (nonbonding)
electrons and one-half its shared (bonding) electrons
3. compare this number with the number of valence
electrons in the neutral, unbonded atom

N umber of
Formal All One h alf of
= valence electrons un shared + all sh ared
charge in th e neutral,
un bonded atom electrons electrons
Structure and Bonding
 Formal Charge
 Draw Lewis structures, and show which atom in each
bears the formal charge

C3H4 ClO2- CH3COO-

HCOO- BH4- CH3NH2

 Exceptions to the Octet Rule
 Molecules containing atoms of Group 3A
elements, particularly boron and aluminum
6 electrons in the
:

:
: F: valence shells of boron : Cl :
and aluminum
: :

: :
:F B : Cl Al
:F: : Cl :
:

:
Boron trifluoride Aluminum chloride
 Exceptions to the Octet Rule
 Atoms of third-period elements have 3d
orbitals and may expand their valence
shells to contain more than 8 electrons
◦ phosphorus may have up to 10

:
: Cl : :O:
: : : :

: : : :
: Cl Cl :
:

: :

:
CH3 -P- CH3 P H- O-P- O-H

:
CH3 : Cl Cl : O-H

:
Trimethyl- Phosphorus Phosphoric
phosphine pentachloride acid
Exceptions to the Octet Rule
◦ sulfur, another third-period element, forms
compounds in which its valence shell contains
8, 10, or 12 electrons
: O: : O:
:

:
H-S- H CH 3 -S-CH 3 H-O- S-O-H
:

:
:
:O :

Hydrogen Di methyl Sulfuric

sul fi de sul foxi de aci d
 VSEPR
 Based on the twin concepts that
◦ atoms are surrounded by regions of electron density
◦ regions of electron density repel each other

H
4 region s of e - d ensity

:
C N O
(tetrahed ral, 109.5°) H H H
H H H H H

3 region s of e - d ensity H H H H H

: :
(trigon al planar, 120°) C C C O C N

:
H H H H

2 region s of e - d ensity
: :

: :

O C O H C C H H C N
(lin ear, 180°)
 VSEPR Model
 Example: predict all bond angles for these molecules and
ions

( a) NH4 + ( b ) CH3 NH 2 ( d ) CH3 OH

( e) CH 3 CH= CH 2 ( f ) H 2 CO 3 ( g ) HCO 3 -
( h) CH3 CHO ( i) CH 3 COOH ( j ) BF4 -
Polar and Nonpolar Molecules
 To determine if a molecule is polar, we
need to determine
◦ if the molecule has polar bonds
◦ the arrangement of these bonds in space
 Molecular dipole moment (m): the vector
sum of the individual bond dipole
moments in a molecule
◦ reported in debyes (D)
Polar and Nonpolar Molecules
 these molecules have polar bonds, but
each has a zero dipole moment

F Cl

O C O B F C
F Cl Cl
Cl
Carbon dioxide Boron trifluoride Carbon tetrachloride
m=0D m=0D m=0D
Polar and Nonpolar Molecules
 these molecules have polar bonds and are polar
molecules
direction O N direction
of dipole of dip ole
H H H H moment
moment H
Water Ammonia
m = 1.85D m = 1.47D
 Polar and Nonpolar Molecules
◦ formaldehyde has polar bonds and is a polar
molecule

direction O
of dip ole C
moment H H
Formaldehyde
m = 2.33 D