Bonding in Carbon and
Orbital Hybridization
Structure
Structureof
ofMethane
Methane
tetrahedral
bond angles = 109.5°
bond distances = 110 pm
but structure seems inconsistent with
electron configuration of carbon
Electron
Electronconfiguration
configurationof
ofcarbon
carbon
only two unpaired
2p
electrons
should form
bonds to only two
hydrogen atoms
bonds should be
2s at right angles to
one another
sp
sp3Orbital
3
OrbitalHybridization
Hybridization
2p
Promote an electron from the 2s
to the 2p orbital
2s
sp
sp3Orbital
3
OrbitalHybridization
Hybridization
2p 2p
2s 2s
sp
sp3Orbital
3
OrbitalHybridization
Hybridization
2p
Mix together (hybridize) the 2s
orbital and the three 2p orbitals
2s
sp
sp3Orbital
3
OrbitalHybridization
Hybridization
2p
2 sp3
4 equivalent half-filled
orbitals are consistent
with four bonds and
tetrahedral geometry 2s
Shapes
Shapesof
oforbitals
orbitals
s
Nodal
Nodalproperties
propertiesof
oforbitals
orbitals
p + –
s +
Shape
Shape of sp3hybrid
of sp 3
hybridorbitals
orbitals
p + –
take the s orbital and place it on
top of the p orbital
s +
Shape
Shape of sp3hybrid
of sp 3
hybridorbitals
orbitals
s+p + + –
reinforcement of electron wave in
regions where sign is the same
destructive interference in regions of
opposite sign
Shape
Shape of sp3hybrid
of sp 3
hybridorbitals
orbitals
sp hybrid + –
orbital shown is sp hybrid
analogous procedure using three s orbitals
and one p orbital gives sp3 hybrid
shape of sp3 hybrid is similar
Shape
Shape of sp3hybrid
of sp 3
hybridorbitals
orbitals
sp hybrid + –
hybrid orbital is not symmetrical
higher probability of finding an electron on
one side of the nucleus than the other
leads to stronger bonds
The C—HBond
TheC—H BondininMethane
Methane
In-phase overlap of a half-filled 1 s orbital of
hydrogen with a half-filled sp3 hybrid orbital of
carbon:
+
s H + C– sp3
gives a bond.
+
H—C H C–
Justification
Justificationfor
forOrbital
OrbitalHybridization
Hybridization
consistent with structure of methane
allows for formation of 4 bonds rather than 2
bonds involving sp3 hybrid orbitals are stronger
than those involving s-s overlap or p-p overlap
1.16
sp3 Hybridization
and Bonding in Ethane
Structure
Structureof
ofEthane
Ethane
C2H6
CH3CH3
tetrahedral geometry at each carbon
C—H bond distance = 110 pm
C—C bond distance = 153 pm
The C—CBond
TheC—C BondininEthane
Ethane
σ bonds are covalent bonds formed between atoms
when end-on overlap of orbitals occurs.
In-phase overlap of half-filled sp3 hybrid
orbital of one carbon with half-filled sp3
hybrid orbital of another.
Overlap is along internuclear axis to give a bond.
The C—CBond
TheC—C BondininEthane
Ethane
In-phase overlap of half-filled sp3 hybrid
orbital of one carbon with half-filled sp3
hybrid orbital of another.
Overlap is along internuclear axis to give a bond.
sp + sp + sp + sp
3 3 3 3
Because we combined the s orbital and all three p orbitals, we call these
new orbitals “sp3 orbitals”. There are four of them, each pointing
towards a corner of a tetrahedron, exactly where we want them.
Copyright © 2003 Charles B. Abrams
=Csp + Hs 3
Each of the C-H bonds in ethane, CH3CH3, can be described as the
combination of a carbon sp3 and a hydrogen 1s orbital. These are
cylindrically symmetrical, and are called sigma bonds ()
Copyright © 2003 Charles B. Abrams
C sp + C sp
1 3 2 3
The bond between the two carbon atoms can be described as the
combination of an sp3 orbital on one carbon with an sp3 orbital on
the other carbon.
Copyright © 2003 Charles B. Abrams
=C sp + C sp 1 3 2 3
The resulting combination is cylindrically symmetrical, and is therefore
called a sigma () bond. Because it is cylindrically symmetrical, this bond
can rotate without changing the overlap between the two sp3 orbitals
Copyright © 2003 Charles B. Abrams
The next few slides show that rotating around the C-C bond in ethane
does not change the overlap of the two C sp3 orbitals, and therefore does
not change the bond in any way.
Copyright © 2003 Charles B. Abrams
(Rotated 30 degrees)
Copyright © 2003 Charles B. Abrams
(Rotated 60 degrees)
Copyright © 2003 Charles B. Abrams
(Rotated 90 degrees)
Copyright © 2003 Charles B. Abrams
(Rotated 120 degrees). This completes the discussion of bonding in
ethane.
Copyright © 2003 Charles B. Abrams
sp2 Hybridization
and Bonding in Ethylene
Structure
Structureof
ofEthylene
Ethylene
C2H4
H2C=CH2
planar
bond angles: close to 120°
bond distances: C—H = 110 pm
C=C = 134 pm
sp
sp2Orbital
2
OrbitalHybridization
Hybridization
2p
Promote an electron from the 2s
to the 2p orbital
2s
sp
sp2Orbital
2
OrbitalHybridization
Hybridization
2p 2p
2s 2s
sp
sp2Orbital
2
OrbitalHybridization
Hybridization
2p
Mix together (hybridize) the 2s
orbital and two of the three 2p
orbitals
2s
sp
sp2Orbital
2
OrbitalHybridization
Hybridization
2p
2 sp2
3 equivalent half-filled
sp2 hybrid orbitals plus
1 p orbital left
unhybridized 2s
sp
sp2Orbital
2
OrbitalHybridization
Hybridization
p
2 of the 3 sp2 orbitals
2 sp2 are involved in bonds
to hydrogens; the other
is involved in a bond
to carbon
sp
sp2Orbital
2
OrbitalHybridization
Hybridization
p
2 sp2
Bonding
BondingininEthylene
Ethylene
the unhybridized p orbital of
p carbon is involved in bonding
to the other carbon
2 sp2
Bonding
BondingininEthylene
Ethylene
2 sp2
each carbon has an unhybridized 2p orbital
axis of orbital is perpendicular to the plane of the bonds
Bonding
BondingininEthylene
Ethylene
A π bond is a covalent bond formed by the
sideways overlap of two parallel atomic orbitals.
2 sp2
side-by-side overlap of half-filled
p orbitals gives a bond
double bond in ethylene has a
component and a component
sp + sp + sp + pz
2 2 2
These hybrid orbitals are called sp2 orbitals. The complete set of orbitals
available for bonding now includes three sp2 orbitals and the p orbital
which was not involved in the hybridization.
Copyright © 2003 Charles B. Abrams
=Csp + Hs 2
Each of the C-H bonds ethene, CH2=CH2, can be described as the
combination of a carbon sp2 and a hydrogen 1s orbital. These are
cylindrically symmetrical sigma bonds ()
Copyright © 2003 Charles B. Abrams
C sp + C sp
1 2 2 2
There are two bonds between the carbon atoms. One of these can
be described as the combination of an sp2 orbital on one carbon
with an sp2 orbital on the other carbon.
Copyright © 2003 Charles B. Abrams
=C sp + C sp 1 2 2 2
The resulting combination is cylindrically symmetrical, and is therefore
called a sigma () bond. Before we can decide if this bond can rotate, we
must consider the other bond in ethene.
Copyright © 2003 Charles B. Abrams
C pz + C pz
1 2
The second bond between the carbon atoms can be described as the
combination of the p orbital on one carbon with the p orbital on the other
carbon. These two p orbitals are parallel and therefore have good overlap.
Copyright © 2003 Charles B. Abrams
=C pz + C pz 1 2
The resulting combination is not cylindrically symmetrical; instead it has
a plane of symmetry. It is called a pi () bond. The p orbitals can only
overlap if they are parallel. This bond can not rotate.
Copyright © 2003 Charles B. Abrams
However, what if carbon 2 was rotated …. (step through the next three slides to
see the rotation)
Copyright © 2003 Charles B. Abrams
(rotated 45 degrees)
Copyright © 2003 Charles B. Abrams
C pz + C py
1 2
(Rotated 90 degrees.) The p orbital on carbon 2 now does not overlap with the
p orbital on carbon 1. Because the p orbital now points in a different direction,
it is labeled with a different Cartesian coordinate. No pi bond can form.
Copyright © 2003 Charles B. Abrams
Let’s rotate the carbon atom back to where it was, so that the p orbitals can
overlap… (rotated 45 degrees)
Copyright © 2003 Charles B. Abrams
(Rotated 0 degrees.) Again the p orbitals can overlap, and a pi bond can form.
Copyright © 2003 Charles B. Abrams
The carbon-carbon double bond in ethene can be described as one sigma
and one pi bond. The pi bond prevents the double bond from rotating. All
of the atoms (H and C) are in one plane, so this is a planar molecule.
Copyright © 2003 Charles B. Abrams
The plastics shown here were
manufactured with ethylene.
Source: Comstock - Mountainside, NJ
Copyright © Houghton Mifflin Company. All rights reserved.
sp Hybridization
and Bonding in Acetylene
Structure
Structureof
ofAcetylene
Acetylene
C2H2
HC CH
linear
bond angles: 180°
bond distances: C—H = 106 pm
CC = 120 pm
sp
spOrbital
OrbitalHybridization
Hybridization
2p
Promote an electron from the 2s
to the 2p orbital
2s
sp
spOrbital
OrbitalHybridization
Hybridization
2p 2p
2s 2s
sp
spOrbital
OrbitalHybridization
Hybridization
2p
Mix together (hybridize) the 2s
orbital and one of the three 2p
orbitals
2s
sp
spOrbital
OrbitalHybridization
Hybridization
2p 2p
2 sp2
2 equivalent half-filled
sp hybrid orbitals plus
2 p orbitals left 2s
unhybridized
sp
spOrbital
OrbitalHybridization
Hybridization
2p
1 of the 2 sp orbitals
is involved in a bond
2 sp2
to hydrogen; the other
is involved in a bond
to carbon
sp
spOrbital
OrbitalHybridization
Hybridization
2p
2 sp2
Bonding
BondingininAcetylene
Acetylene
the unhybridized p orbitals of
2p carbon are involved in separate
bonds to the other carbon
2 sp2
Bonding
BondingininAcetylene
Acetylene
2p
2 sp2
one bond involves one of the p orbitals on each carbon
there is a second bond perpendicular to this one
Bonding
BondingininAcetylene
Acetylene
2p
2 sp2
Bonding
BondingininAcetylene
Acetylene
2p
2 sp2
sp + sp + py + pz
These hybrid orbitals are called sp orbitals. The complete set of orbitals
available for bonding now includes these two sp orbitals and the two p
orbital which were not involved in the hybridization.
Copyright © 2003 Charles B. Abrams
C sp + C sp
1 2
One bond between the carbons is described as the combination of the
carbon 1 sp orbital plus the carbon 2 sp orbital.
Copyright © 2003 Charles B. Abrams
= C sp + C sp 1 2
This is called a sigma bond, as in the previous examples.
Copyright © 2003 Charles B. Abrams
C py + C py
1 2
There are now two sets of p orbitals which can be combined. The p y
orbitals on each carbon can combine to form one pi bond…
Copyright © 2003 Charles B. Abrams
=C py + C py 1 2
This is one of the pi bonds in ethyne.
Copyright © 2003 Charles B. Abrams
C pz + C pz
1 2
The other set of p orbitals can also combine to form a second pi bond.
Copyright © 2003 Charles B. Abrams
=C pz + C pz 1 2
Here is another pi bond in ethyne.
Copyright © 2003 Charles B. Abrams
The triple bond in ethyne (acetylene) is described as one sigma bond and
two pi bonds.
Copyright © 2003 Charles B. Abrams
What is the hybridization in each carbon atom?
4
2 5
6
3
7
1
sp3 – 2, 5 sp2 – 1, 3, 4 sp – 6, 7
tetrahedral trigonal planar linear
Allene, H2C=C=CH2
What is the hybridization?
The clouds of the two double bonds are oriented
perpendicular to each other. Hence the
hydrogens are turned 90o. The is due to the
original orientation of the p orbitals on the center
carbon atom. Spartan 02
= C py + C py 2 3
This model shows the two pi bonds in allene, and makes it clear that
allene is not planar; not all of the atoms of allene are in the same plane.
Instead, allene is twisted.
Copyright © 2003 Charles B. Abrams
1.19
Which Theory of
Chemical Bonding is Best?
POLAR COVALENT BONDS
AND ELECTRONEGATIVITY
Electrons in covalent bonds are not necessarily
shared equally by the two atoms that they connect.
greater tendency to attract electrons toward itself
than the other, we say the electron distribution is
polarized, and the bond is referred to as a polar
covalent bond.
Hydrogen fluoride has a polar covalent bond.
Because fluorine attracts electrons more strongly
than hydrogen
the electrons in the H±F bond are pulled toward
fluorine, giving it a partial negative
δ– charge, and
away from hydrogen giving it a partial positive
charge. δ+ F
H
Copyright © 2003 Charles B. Abrams
POLAR COVALENT BONDS
.
AND ELECTRONEGATIVITY
The tendency of an atom to draw the electrons in a
covalent bond toward itself is referred to as its
electronegativity.
An electronegative element attracts electrons; an
electropositive one donates them.
Electronegativity increases across a row in the
periodic table.
The most electronegative of the second-row
elements is fluorine; the most electropositive is
lithium.
Copyright © 2003 Charles B. Abrams
Dipole and dipole moment
Centers of positive and negative charge that are separated from each other
constitute a dipole. The dipole moment of a molecule is equal to the
charge µ (either the positive or the negative charge, since they must be
equal) multiplied by the distance between the centers of charge:
µ=e xd
Polar and Non-polar Compounds
Polar Compounds : H2O, HCl, CH3Cl Non-Polar Compounds: CH4, C2H6
Shared electrons unevenly Shared electrons evenly
Have partial positive end and partial Have no Charges
negative end
Electronegativity must be 0.4 and above Electronegativity must be 0 or less than
0.4
Have stronger intermolecuar forces .i.e Have weaker intermolecuar forces .i.e
higher melting and boiling points lower melting and boiling points
Soluble in polar solvents Soluble in non-polar solvents
