Section A – Structure and bonding

3
A3 SP HYBRIDIZATION

Key Notes
3
Definition In sp hybridization, the s and the p orbitals of the second shell are ‘mixed’
3
to form four hybridized sp orbitals of equal energy.

Electronic Each hybridized orbital contains a single unpaired electron and so four
configuration bonds are possible.

3
Geometry Each sp orbital is shaped like a deformed dumbbell with one lobe much
larger than the other. The hybridized orbitals arrange themselves as far
apart from each other as possible such that the major lobes point to the cor-
3
ners of a tetrahedron. sp Hybridization explains the tetrahedral carbon in
saturated hydrocarbon structures.

3
Sigma bonds Sigma (σ) bonds are strong bonds formed between two sp hybridized car-
3
bons or between an sp hybridized carbon and a hydrogen atom. A σ bond
3
formed between two sp hybridized carbon atoms involves the overlap of
3
half filled sp hybridized orbitals from each carbon atom. A σ bond formed
3
between an sp hybridized carbon and a hydrogen atom involves a half-
3
filled sp orbital from carbon and a half-filled 1s orbital from hydrogen.

3
Nitrogen, oxygen Nitrogen, oxygen, and chlorine atoms can also be sp hybridized in organic
3
and chlorine molecules. This means that nitrogen has three half-filled sp orbitals and can
form three bonds which are pyramidal in shape. Oxygen has two half-filled
3
sp orbitals and can form two bonds which are angled with respect to each
3
other. Chlorine has a single half-filled sp orbital and can only form a single
bond. All the bonds which are formed are σ bonds.

Related topics Covalent bonding and Bonds and hybridized centers (A6)
hybridization (A2)

3
Definition In sp hybridization, the 2s orbital is mixed with all three of the 2p orbitals to give a
3
set of four sp hybrid orbitals. (The number of hybrid orbitals must equal the
number of original atomic orbitals used for mixing.) The hybrid orbitals will
each have the same energy but will be different in energy from the original
atomic orbitals. That energy difference will reflect the mixing of the respect-
ive atomic orbitals. The energy of each hybrid orbital is greater than the original s
orbital but less than the original p orbitals (Fig. 1).

3
Electronic The valence electrons for carbon can now be fitted into the sp hybridized orbitals
configuration (Fig. 1). There was a total of four electrons in the original 2s and 2p orbitals. The s
orbital was filled and two of the p orbitals were half filled. After hybridization,
3
there is a total of four hybridized sp orbitals all of equal energy. By Hund’s rule,
6 Section A – Structure and bonding

they are all half filled with electrons which means that there are four unpaired
electrons. Four bonds are now possible.

Energy

2px 2py 2pz

2s

Original atomic orbitals sp3 hybridized orbitals

3
Fig. 1. sp Hybridization.

3
Geometry Each of the sp hybridized orbitals has the same shape – a rather deformed looking
dumbbell (Fig. 2). This deformed dumbbell looks more like a p orbital than an s
orbital since more p orbitals were involved in the mixing process.

Minor lobe Major lobe

3
Fig. 2. sp Hybridized orbital.

3
Each sp orbital will occupy a space as far apart from each other as possible by
pointing to the corners of a tetrahedron (Fig. 3). Here, only the major lobe of each
hybridized orbital has been shown and the angle between each of these lobes is
109.5. This is what is meant by the expression tetrahedral carbon. The three-
dimensional shape of the tetrahedral carbon can be represented by drawing a nor-
mal line for bonds in the plane of the page. Bonds going behind the page are
represented by a hatched wedge, and bonds coming out the page are represented
by a solid wedge.

H Bond in the plane

109 .5 o of the page
C Bond going behind
C
H the page
H H
Bond coming out
Tetrahedral shape of the page

3
Fig. 3. Tetrahedral shape of an sp hybridized carbon

3
Sigma bonds A half-filled sp hybridized orbital from one carbon atom can be used to form a
3
bond with a half-filled sp hybridized orbital from another carbon atom. In Fig. 4a,
3
the major lobes of the two sp orbitals overlap directly leading to a strong σ bond.
It is the ability of hybridized orbitals to form strong σ bonds that explains why
hybridization takes place in the first place. The deformed dumbbell shapes allow
a much better orbital overlap than would be obtained from a pure s orbital or a
3
pure p orbital. A σ bond between an sp hybridized carbon atom and a hydrogen
3
atom involves the carbon atom using one of its half-filled sp orbitals and the
hydrogen atom using its half-filled 1s orbital (Fig. 4b).
 3
A3 – sp Hybridization 7

a)
C C C C
+

sp3 sp3 sigma bond

b) H H
C C
+

sp3 1s sigma bond

Fig. 4. (a) σ Bond between two sp hybridized carbons; (b) σ bond between an sp
3 3

hybridized carbon and hydrogen

3
Nitrogen, oxygen, Nitrogen, oxygen and chlorine atoms can also be sp hybridized in organic
and chlorine structures. Nitrogen has five valence electrons in its second shell. After
3
hybridization, it will have three half-filled sp orbitals and can form three
bonds. Oxygen has six valence electrons. After hybridization, it will have two
3
half-filled sp orbitals and will form two bonds. Chlorine has seven valence
3
electrons. After hybridization, it will have one half-filled sp orbital and will
form one bond.
3
The four sp orbitals for these three atoms form a tetrahedral arrangement with
one or more of the orbitals occupied by a lone pair of electrons. Considering the
atoms alone, nitrogen forms a pyramidal shape where the bond angles are slightly
less than 109.5 (c. 107) (Fig. 5a). This compression of the bond angles is due to the
orbital containing the lone pair of electrons, which demands a slightly greater
amount of space than a bond. Oxygen forms an angled or bent shape where two
lone pairs of electrons compress the bond angle from 109.5 to c. 104 (Fig. 5b).
Alcohols, amines, alkyl halides, and ethers all contain sigma bonds involving
nitrogen, oxygen, or chlorine. Bonds between these atoms and carbon are formed
3
by the overlap of half-filled sp hybridized orbitals from each atom. Bonds involv-
ing hydrogen atoms (e.g. O–H and N–H) are formed by the overlap of the half-
3
filled 1s orbital from hydrogen and a half-filled sp orbital from oxygen or
nitrogen.

a)

N = N
H H
CH3 CH3
H H

Pyramidal
107o
b)

O
O = H CH3
H
H3C 104o
Angled molecule

3 3
Fig. 5. (a) Geometry of sp hybridized nitrogen; (b) geometry of sp hybridized oxygen.
Section A – Structure and bonding

2
A4 SP HYBRIDIZATION
Key Notes
2
Definition In sp hybridization, a 2s orbital is ‘mixed’ with two of the 2p orbitals to
2
form three hybridized sp orbitals of equal energy. A single 2p orbital is left
over which has a slightly higher energy than the hybridized orbitals.

2
Electronic For carbon, each sp hybridized orbital contains a single unpaired electron.
configuration There is also a half-filled 2p orbital. Therefore, four bonds are possible.

2
Geometry Each sp orbital is shaped like a deformed dumbbell with one lobe much
larger than the other. The remaining 2p orbital is a symmetrical dumbbell.
2
The major lobes of the three sp hybridized orbitals point to the corners of
a triangle, with the 2p orbital perpendicular to the plane.

2 2
Alkenes Each sp hybridized carbon forms three σ bonds using three sp hybridized
orbitals. The remaining 2p orbital overlaps ‘side on’ with a neighboring 2p
orbital to form a pi (π) bond. The π bond is weaker than the σ bond, but is
strong enough to prevent rotation of the CC bond. Therefore, alkenes are
planar, with each carbon being trigonal planar.

2
Carbonyl groups The oxygen and carbon atoms are both sp hybridized. The carbon has three
2
sp hybridized orbitals and can form three σ bonds, one of which is to the
2
oxygen. The oxygen has one sp orbital which is used in the σ bond with
carbon. The p orbitals on carbon and oxygen are used to form a π bond.

2
Aromatic rings Aromatic rings are made up of six sp hybridized carbons. Each carbon
forms three σ bonds which results in a planar ring. The remaining 2p orbital
on each carbon is perpendicular to the plane and can overlap with a neigh-
boring 2p orbital on either side. This means that a molecular orbital is
formed round the whole ring such that the six π electrons are delocalized
around the ring. This results in increased stability such that aromatic rings
are less reactive than alkenes.

Conjugated systems Conjugated systems such as conjugated alkenes and α,β-unsaturated

carbonyl compounds involve alternating single and double bonds. In such
systems, the p lobes of one π bond are able to overlap with the p lobes of a
neighboring π bond, and thus give a small level of double bond character to
the connecting bond. This partial delocalization gives increased stability to
the conjugated system.

Related topics Properties of alkenes and alkynes Properties (J2)

(H2) α,β-Unsaturated aldehydes and
Conjugated dienes (H11) ketones (J11)
Aromaticity (I1) Structure and properties (K1)
 2
A4 – sp Hybridization 9

2
Definition In sp hybridization, the s orbital is mixed with two of the 2p orbitals (e.g. 2px and
2
2pz) to give three sp hybridized orbitals of equal energy. The remaining 2py orbital
is unaffected. The energy of each hybridized orbital is greater than the original s
orbital but less than the original p orbitals. The remaining 2p orbital (in this case
the 2py orbital) remains at its original energy level (Fig. 1).

Energy

2px 2py 2pz 2py

sp2
2s

Original atomic orbitals sp2 hybridized orbitals

2
Fig. 1. sp Hybridization.

2
Electronic For carbon, there are four valence electrons to fit into the three hybridized sp
configuration orbitals and the remaining 2p orbital. The first three electrons are fitted into each
of the hybridized orbitals according to Hund’s rule such that they are all half-
filled. This leaves one electron still to place. There is a choice between pairing it
2
up in a half-filled sp orbital or placing it into the vacant 2py orbital. The usual prin-
ciple is to fill up orbitals of equal energy before moving to an orbital of higher
energy. However, if the energy difference between orbitals is small (as here) it is
easier for the electron to fit into the higher energy 2py orbital resulting in three
2
half-filled sp orbitals and one half-filled p orbital (Fig. 1). Four bonds are possible.
2
Geometry The 2py orbital has the usual dumbbell shape. Each of the sp hybridized orbitals
3
has a deformed dumbbell shape similar to an sp hybridized orbital. However,
2
the difference between the sizes of the major and minor lobes is larger for the sp
hybridized orbital.
The hybridized orbitals and the 2py orbital occupy spaces as far apart from each
other as possible. The lobes of the 2py orbital occupy the space above and below
2
the plane of the x and z axes (Fig. 2a). The three sp orbitals (major lobes shown
only) will then occupy the remaining space such that they are as far apart from the
2py orbital and from each other as possible. As a result, they are all placed in the
x–z plane pointing toward the corner of a triangle (trigonal planar shape; Fig. 2b).
The angle between each of these lobes is 120. We are now ready to look at the
2
bonding of an sp hybridized carbon.

y y
a) b)

120o

x x

z z

2
Fig. 2. (a) Geometry of the 2py orbital; (b) geometry of the 2 py orbital and the sp
hybridized orbitals.
10 Section A – Structure and bonding

2 2
Alkenes sp Hybridization results in three half-filled sp hybridized orbitals which form a
trigonal planar shape. The use of these three orbitals in bonding explains the
shape of an alkene, for example ethene (H2CCH2). As far as the C–H bonds are
concerned, the hydrogen atom uses a half-filled 1s orbital to form a strong σ bond
2
with a half filled sp orbital from carbon (Fig. 3a). A strong σ bond is also possible
2
between the two carbon atoms of ethene due to the overlap of sp hybridized
orbitals from each carbon (Fig. 3b).

H H
C C
+
2
sp 1s
C C C C
+

sp2 sp2

Fig. 3. (a) Formation of a C–H σ bond; (b) formation of a C–C σ bond.

The full σ bonding diagram for ethene is shown in Fig. 4a and can be simplified as
shown in Fig. 4b. Ethene is a flat, rigid molecule where each carbon is trigonal pla-
2
nar. We have seen how sp hybridization explains the trigonal planar carbons but
we have not explained why the molecule is rigid and planar. If the σ bonds were
the only bonds present in ethene, the molecule would not remain planar since
rotation could occur round the C–C σ bond (Fig. 5). Therefore, there must be fur-
ther bonding which ‘locks’ the alkene into this planar shape. This bond involves

H H
H H
C C C
C H
H
H H

Fig. 4. (a) σ Bonding diagram for ethene; (b) simple representation of σ bonds for ethene.

H
H H H
C C C C
H H Bond H
rotation H

Fig. 5. Bond rotation around a σ bond.

the remaining half-filled 2py orbitals on each carbon which overlap side-on to pro-
duce a pi (p) bond), with one lobe above and one lobe below the plane of the mol-
ecule (Fig. 6). This π bond prevents rotation round the C–C bond since the π bond
would have to be broken to allow rotation. A π bond is weaker than a σ bond since
the 2py orbitals overlap side-on, resulting in a weaker overlap. The presence of a π
bond also explains why alkenes are more reactive than alkanes, since a π bond is
more easily broken and is more likely to take part in reactions.
 2
A4 – sp Hybridization 11

2py 2py

H H
C O H
H H
H

π Bond

Fig. 6. Formation of a π bond.

Carbonyl groups The same theory explains the bonding within a carbonyl group (CO) where
2
both the carbon and oxygen atoms are sp hybridized. The following energy level
2
diagram (Fig. 7) shows how the valence electrons of oxygen are arranged after sp
2
hybridization. Two of the sp hybridized orbitals are filled with lone pairs of
2
electrons, which leaves two half-filled orbitals available for bonding. The sp
orbital can be used to form a strong σ bond, while the 2py orbital can be used for
the weaker π bond. Figure 8 shows how the σ and π bonds are formed in the
carbonyl group and explains why carbonyl groups are planar with the carbon
atom having a trigonal planar shape. It also explains the reactivity of carbonyl
groups since the π bond is weaker than the σ bond and is more likely to be
involved in reactions.

Energy

2px 2py 2pz 2py

sp2
2s

Original atomic orbitals sp2 hybridized orbitals

2
Fig. 7. Energy level diagram for sp hybridized oxygen.

a)

H H
C O C O
H H
sp2 2
sp sigma bond

2py 2py

b)

H
C O
H

Fig. 8. (a) Formation of the carbonyl σ bond; (b) formation of the carbonyl π bond.
12 Section A – Structure and bonding

2
Aromatic rings All the carbons in an aromatic ring are sp hybridized which means that each
carbon can form three σ bonds and one π bond. In Fig. 9a, all the single bonds are
σ while each double bond consists of one σ bond and one π bond. However, this
is an oversimplification of the aromatic ring. For example, double bonds are
shorter than single bonds and if benzene had this exact structure, the ring would
be deformed with longer single bonds than double bonds (Fig. 9b).

a) H
b)
H H

=
H H

Fig. 9. (a) Representation of the aromatic ring; (b) ‘deformed’ structure resulting from fixed
bonds.

In fact, the C–C bonds in benzene are all the same length. In order to understand
this, we need to look more closely at the bonding which takes place. Figure 10a
shows benzene with all its σ bonds and is drawn such that we are looking into the
2
plane of the benzene ring. Since all the carbons are sp hybridized, there is a 2py
orbital left over on each carbon which can overlap with a 2py orbital on either side
of it (Fig. 10b). From this, it is clear that each 2py orbital can overlap with its neigh-
bors right round the ring. This leads to a molecular orbital which involves all the 2py
orbitals where the upper and lower lobes merge to give two doughnut-like lobes
above and below the plane of the ring (Fig. 11a). The molecular orbital is symmetri-
cal and the six π electrons are said to be delocalized around the aromatic ring since
they are not localized between any two particular carbon atoms. The aromatic ring
is often represented as shown in Fig. 11b to represent this delocalization of the π

a) b)

H H
H H

H H

Fig. 10. (a) σ Bonding diagram for benzene, (b) π Bonding diagram for benzene.

a)
a) H b)
b)
H

C C
H H
= C C =

H H C C

Fig. 11. Bonding molecular orbital for benzene; (b) representation of benzene to illustrate
delocalization.
 2
A4 – sp Hybridization 13

electrons. Delocalization increases the stability of aromatic rings such that they are
less reactive than alkenes (i.e. it requires more energy to disrupt the delocalized π
system of an aromatic ring than it does to break the isolated π bond of an alkene).

Conjugated Aromatic rings are not the only structures where delocalization of π electrons can
systems take place. Delocalization occurs in conjugated systems where there are alternat-
ing single and double bonds (e.g. 1,3-butadiene). All four carbons in 1,3-butadiene
2
are sp hybridized and so each of these carbons has a half-filled p orbital which can
interact to give two π bonds (Fig. 12a). However, a certain amount of overlap is
also possible between the p orbitals of the middle two carbon atoms and so the
bond connecting the two alkenes has some double bond character (Fig. 12b) –
borne out by the observation that this bond is shorter in length than a typical
single bond. This delocalization also results in increased stability. However, it is
important to realize that the conjugation in a conjugated alkene is not as great
as in the aromatic system. In the latter system, the π electrons are completely
delocalized round the ring and all the bonds are equal in length. In 1,3-butadiene,
the π electrons are not fully delocalized and are more likely to be found in the ter-
minal C–C bonds. Although there is a certain amount of π character in the middle
bond, the latter is more like a single bond than a double bond.
Other examples of conjugated systems include α,β-unsaturated ketones and α,β-
unsaturated esters (Fig. 13). These too have increased stability due to conjugation.

a) 2py 2py
2py 2py

H C C H
H C C H
H C C H H C C H
H H H H

1,3-Butadiene

b) 2py 2py
2py 2py

H C C H
H C C H
H H

Fig. 12. (a) π Bonding in 1,3-butadiene; (b) delocalization in 1,3-butadiene.

a) H3C H b) H3C H

C C C C

H C CH3 H C OCH3

O O

Fig. 13. (a) α,β-Unsaturated ketone; (b) α,β-unsaturated ester.

Section A – Structure and bonding

A5 SP HYBRIDIZATION

Key Notes

Definition In sp hybridization, the 2s orbital and one of the three 2p orbitals are ‘mixed’
to form two hybridized sp orbitals of equal energy. Two 2p orbitals are left
over and have slightly higher energy than the unhybridized orbitals.

Electronic For carbon, each sp hybridized orbital contains a single unpaired electron.
configuration There are also two half-filled 2p orbitals. Therefore, four bonds are possible.

Geometry Each sp orbital is shaped like a deformed dumbbell with one lobe much
larger than the other. The remaining 2p orbitals are symmetrical dumbbells.
If we define the 2p orbitals as being aligned along the y and the z axes, the
two sp hybridized orbitals point in opposite directions along the x axis.

Alkynes Each sp hybridized carbon of an alkyne can form two σ bonds using sp
hybridized orbitals. The remaining 2p orbitals can overlap ‘side-on’ to form
two π bonds. Alkynes are linear molecules and are reactive due to the π
bonds.

Nitrile groups The nitrogen and carbon atoms of a nitrile group (C
N) are both sp
hybridized. The carbon has two sp hybridized orbitals and can form two σ
bonds, one of which is to nitrogen. The nitrogen has one sp orbital which is
used in the σ bond with carbon. Both the carbon and the nitrogen have two
2p orbitals which can be used to form two π bonds.

Related topics Properties of alkenes and Chemistry of nitriles (O4)

alkynes (H2)

Definition In sp hybridization, the 2s orbital is mixed with one of the 2p orbitals (e.g. 2px) to
give two sp hybrid orbitals of equal energy. This leaves two 2p orbitals unaffected
(2py and 2pz) with slightly higher energy than the hybridized orbitals (Fig. 1).

Energy

2px 2py 2pz 2py 2pz

sp

2s

Original atomic orbitals sp hybridized orbitals

Fig. 1. sp Hybridization of carbon.

A5 – sp Hybridization 15

Electronic For carbon, the first two electrons fit into each sp orbital according to Hund’s rule
configuration such that each orbital has a single unpaired electron. This leaves two electrons
which can be paired up in the half-filled sp orbitals or placed in the vacant 2py and
2pz orbitals. The energy difference between the orbitals is small and so it is easier
for the electrons to fit into the higher energy orbitals than to pair up. This leads to
two half-filled sp orbitals and two half-filled 2p orbitals (Fig. 1), and so four bonds
are possible.

Geometry The 2p orbitals are dumbbell in shape while the sp hybridized orbitals are
deformed dumbbells with one lobe much larger than the other. The 2py and 2pz
orbitals are at right angles to each other (Fig. 2a). The sp hybridized orbitals
occupy the space left over and are in the x axis pointing in opposite directions
(only the major lobe of the sp orbitals are shown in black; Fig. 2b).

a) y b) y

2py sp 2py

2p z 2p z

z x z sp x

Fig. 2. (a) 2py and 2pz orbitals of an sp hybridized carbon; (b) 2py, 2pz and sp hybridized
orbitals of an sp hybridized carbon.

A molecule using the two sp orbitals for bonding will be linear in shape. There
are two common functional groups where such bonding takes place – alkynes and
nitriles.

Alkynes Let us consider the bonding in ethyne (Fig. 3) where each carbon is sp hybridized.
The C–H bonds are strong σ bonds where each hydrogen atom uses its half-filled

H C C H

Fig. 3. Ethyne.

1s orbital to bond with a half-filled sp orbital on carbon. The remaining sp orbital

on each carbon is used to form a strong σ carbon–carbon bond. The full σ bonding
diagram for ethyne is linear (Fig. 4a) and can be simplified as shown (Fig. 4b).

a) b)
H C C H H C C H

Fig. 4. (a) σ Bonding for ethyne; (b) representation of σ bonding.

Further bonding is possible since each carbon has half-filled p orbitals. Thus, the
2py and 2pz orbitals of each carbon atom can overlap side-on to form two π bonds
(Fig. 5). The π bond formed by the overlap of the 2py orbitals is represented in dark
16 Section A – Structure and bonding

gray. The π bond resulting from the overlap of the 2pz orbitals is represented in
light gray. Alkynes are linear molecules and are reactive due to the relatively weak
π bonds.

Nitrile groups Exactly the same theory can be used to explain the bonding within a nitrile group
(C
N) where both the carbon and the nitrogen are sp hybridized. The energy
level diagram in Fig. 6 shows how the valence electrons of nitrogen are arranged
after sp hybridization. A lone pair of electrons occupies one of the sp orbitals, but
the other sp orbital can be used for a strong σ bond. The 2py and 2pz orbitals can be
used for two π bonds. Figure 7 represents the σ bonds of HCN as lines and how
the remaining 2p orbitals are used to form two π bonds.

2py
2py

H
2pz C C C
C
2pz
H

Pi Bond (π)

Fig. 5. π-Bonding in ethyne.

Energy

2px 2py 2pz 2py 2pz

sp

2s

Original atomic orbitals sp hybridized orbitals

Fig. 6. sp Hybridization of nitrogen.

2py
2py

H
C C N
2pz
N
N
2pz

Pi Bond (π)

Fig. 7. π-Bonding in HCN.

Section A – Structure and bonding

A6 BONDS AND HYBRIDIZED CENTERS

Key Notes
σ and π bonds Every bond in an organic structure is a σ bond or a π bond. Every atom in
a structure is linked to another by a single σ bond. If there is more than one
bond between any two atoms, the remaining bonds are π bonds.

2 3
Hybridized centers All atoms in an organic structure (except hydrogen) are either sp, sp or sp
3
hybridized. Atoms linked by single bonds are sp hybridized, atoms linked
2
by double bonds are sp hybridized* and atoms linked by triple bonds are
sp hybridized.*

3 2
Shape sp Hybridized centers are tetrahedral, sp hybridized centers are trigonal
planar and sp centers are linear. This determines the shape of functional
2
groups. Functional groups containing sp hybridized centers are planar
while functional groups containing sp hybridized centers are linear.

Reactivity Functional groups containing π bonds tend to be reactive since the π bond
is weaker than a σ bond and is more easily broken.

3 sp Hybridization (A5)
Related topics sp Hybridization (A3)
2
sp Hybridization (A4)

(* with the exception of allenes R2CCCR2)

σ and π bonds Identifying σ and π bonds in a molecule (Fig. 1) is quite easy as long as you
remember the following rules:
● all bonds in organic structures are either sigma (σ) or pi (π) bonds;
● all single bonds are σ bonds;
● all double bonds are made up of one σ bond and one π bond;
● all triple bonds are made up of one σ bond and two π bonds.

π O H
Cl π H
π π O
CH3 C CH3 C CH3 C
CH
H3C CH2 H3C CH2 H3C C C C π
H3C O
H

Fig. 1. Examples – all the bonds shown are σ bonds except those labelled as .

2 3
Hybridized centers All the atoms in an organic structure (except hydrogen) are either sp, sp or sp
hybridized (Fig. 2).
18 Section A – Structure and bonding

3 O sp2
Cl sp H

CH CH3 C CH3 C CH3

H3C sp2 CH2 sp3 3
H3C sp3 CH2 sp3 H3C sp 2 C 2 sp
sp3 sp3 sp
sp3 sp3 sp3
H
sp2 O H
C
C C sp
H3C sp2 O sp
sp3 sp3

2 3
Fig. 2. Examples of sp, sp and sp hybridized centers.

2 3
The identification of sp, sp and sp centers is simple if you remember the following
rules:
3
● all atoms linked by a single bond are sp hybridized (except hydrogen).
2
● both carbon atoms involved in the double bond of an alkene (CC) must be sp
hybridized.*
2
● both the carbon and the oxygen of a carbonyl group (CO) must be sp
hybridized.
2
● all aromatic carbons must be sp hybridized.
● both atoms involved in a triple bond must be sp hybridized.
● hydrogen uses a 1s orbital for bonding and is not hybridized.
Hydrogen atoms cannot be hybridized. They can only bond by using an s orbital
since there are no p orbitals in the first electron shell. It is therefore impossible for
a hydrogen to take part in π bonding. Oxygen, nitrogen and halogens on the other
hand can form hybridized orbitals which are either involved in bonding or in
holding lone pairs of electrons.

Shape The shape of organic molecules and the functional groups within them is
determined by the hybridization of the atoms present. For example, functional
2
groups containing trigonal planar sp centers are planar while functional groups
containing sp centers are linear:
● planar functional groups – aldehyde, ketone, alkene, carboxylic acid, acid
chloride, acid anhydride, ester, amide, aromatic.
● linear functional groups – alkyne, nitrile.
● functional groups with tetrahedral carbons – alcohol, ether, alkyl halide.

Reactivity Functional groups which contain π bonds are reactive since the π bond is weaker
than a σ bond and can be broken more easily. Common functional groups which
contain π bonds are aromatic rings, alkenes, alkynes, aldehydes, ketones,
carboxylic acids, esters, amides, acid chlorides, acid anhydrides, and nitriles.

* Functional groups known as allenes (R2CCCR2) have an sp hybridized carbon located

at the center of two double bonds, but these functional groups are beyond the scope of this
text.