Chapter 4

Nomenclature and Conformations

of Alkanes and Cycloalkanes
In this chapter we will consider:

How to name many simple organic molecules.

The flexible, three-dimensional nature of organic

molecules.

An organic reaction that can convert alkenes and

alkynes to alkanes.

4.0
The Four Classes of Hydrocarbons

Alkanes Alkenes Alkynes Arenes

Class
(Chapter 4) (Chapter 7/8) (Chapter 7/8) (Chapter 14)

Carbon-
carbon
bonding

Example

Ethene Ethyne
Name Ethane
(Ethylene) (Acetylene)

4.1
Introduction to Alkanes and Cycloalkanes
Alkanes (烷) are saturated hydrocarbons meaning they
have the maximum number of hydrogens for the
carbon number.

Alkanes have the general formula CnH2n+2.

Cycloalkanes are cyclic structures with the carbon

atoms in a ring.

Cycloalkanes have the general formula CnH2n.

4.1
Sources of Alkanes: Petroleum and Natural Gas

Petroleum is the source of alkanes. It is a complex

mixture of mostly alkanes and aromatic hydrocarbons
with smaller amounts of oxygen-, nitrogen-, and sulfur-
containing compounds.

Natural gas is a gaseous mixture of hydrocarbons

recovered from natural sources. It is mostly methane
(CH4, bp −162oC) with small amounts of ethane (C2H6,
bp −88oC) and propane (C3H8, bp −42oC).

4.1
Liquid petroleum and natural gas are usually separated
at the wellhead and shipped independently to processing
(refining) plants.

4.1
4.1
Cracking and Catalytic Reforming

800−900oC
CH3CH3 CH2=CH2 + H2
(thermal cracking)
Ethylene

catalyst
CH3CH2CH2CH2CH2CH3
− H2

catalyst

− 3H2

4.1
Octane Rating
Gasoline is a mixture of C6 to C12 hydrocarbons.

The octane rating of a particular gasoline is that

percentage of isooctane in a mixture of isooctane and
heptane that has antiknock properties equivalent to
those of the gasoline.

2,2,4-Trimethylpentane Heptane
(octane rating 100) (octane rating 0)

4.1
Shape of Alkanes
Tetrahedral about carbon.
All bond angles are approximately 109.5o.

4.2
Representing Alkanes
Name Pentane
Structural
CH3CH2CH2CH2CH3
Formula

Ball-and-Stick
Model

Bond-Line
(Line-Angle)
Formula

Wedge Dash
Dash-Wedge (3D)
C
4.2
Constitutional Isomerism in Alkanes
Constitutional isomers: compounds with the same molecular
formula but a different connectivity of their atoms. The
isomers have different chemical and physical properites.
From C4 and higher, alkanes exist as constitutional isomers.
There are two constitutional isomers with molecular formula
C4H10.

CH3
CH3 CH2 CH2 CH3
CH3 CH CH3
Butane (linear form)
2-Methylpropane (branched) 12
(bp -0.5oC) 4.2
(bp -11.6oC)
Branched-Chain Alkanes

4.2
The number of constitutional isomers goes up rapidly
with the carbon number.

4.2
Constitutional isomers are different compounds and
have different physical properties.

4.2
Classification of Carbons
Primary (1°): a C bonded to one other carbon.
Secondary (2°): a C bonded to two other carbons.
Tertiary (3°): a C bonded to three other carbons.
Quaternary (4°): a C bonded to four other carbons.

a 2o carbon
a 4o carbon
CH3 CH3 a 1o carbon

CH3 C CH2 CH CH3

a 1o carbon CH3
a 3o carbon

2,2,4-Trimethylpentane
4.3
Classification of Hydrogen Atoms

The hydrogen in an alkane is classified as primary (1o),

secondary (2o), or tertiary (3o) according to the type of
carbon it is attached to.

4.3
Naming Alkanes, Alkyl Halides, and Alcohols
The IUPAC System
IUPAC System (International Union of Pure and Applied
Chemistry) proposed the systematic nomenclature system.
Prefix-Infix-Suffix
Prefix tells the number of carbon atoms in the parent.
Infix tells the nature of the carbon-carbon bonds.
Suffix tells the class of compound.
Nature of Carbon-Carbon Suffix Class
Infix Bonds in the Parent Chain -e hydrocarbon
-an- all single bonds -ol alcohol
-en- one or more double bonds -al aldehyde
-yn- one or more triple bonds -amine amine
-one ketone
-oic acid carboxylic acid
Prefix Used in the IUPAC system

19
Nomenclature -- The IUPAC System
(International Union of Pure and Applied Chemistry)
Alkanes have the general formula CnH2n+2.
Molecular Molecular
N ame Formula N ame Formula
methane CH4 nonane C9 H2 0
ethan e C2 H6 decan e C1 0 H 2 2
propane C H dodecan e C1 2 H 2 6
3 8
bu tane C4 H1 0 tetrad ecane C1 4 H 3 0
pen tane C5 H1 2 hexadecane C1 6 H 3 4
hexan e C6 H1 4 octadecan e C1 8 H 3 8
hep tane C7 H1 6 eicosane C2 0 H 4 2
octane C8 H1 8 20
3.3
Propene = Prop-en-e Ethanol = Eth-an-ol

OH

2-Butanone = 2-But-an-one Butanal = But-an-al

O O
H

Pentanoic acid = Pent-an-oic acid Ethyne = Eth-yn-e

O
HC CH
OH 21
Substituents-Alkyl Groups
alkyl group: a substituent derived by removal of a
hydrogen from an alkane; given the symbol R-.
CH4 becomes CH3- (methyl).
CH3CH3 becomes CH3CH2- (ethyl).

Con dens ed Con dens ed

N ame Structu ral Formula N ame Structu ral Formula
methyl -CH3 isobu tyl -CH2 CHCH3
ethyl -CH2 CH3 CH3

propyl -CH2 CH2 CH3 sec-butyl -CHCH2 CH3

CH3 2o (secondary)
isopropyl -CHCH3
CH3 CH3
t ert-bu tyl -CCH3
bu tyl -CH2 CH2 CH2 CH3 CH3 3o (tertiary)
22
3.3
Nomenclature of Complicated Alkyl group
2 CH3 H2
H H
1 H3C CH2 1C H3C3 C2 C
H3C C H 3 2 1
CH3 CH3
isopropyl sec-butyl isobutyl
Or Or Or
1-methylethyl 1-methylpropyl 2-methylpropyl
3CH3

H3C 2C CH3
1CH2

Or
neopentyl 2,2-dimethylpropyl
23
Nomenclature of Alkanes with Substituents

Parent (root) name: the longest carbon chain.

Substituent: a group bonded to the parent chain.

substituent

1 3 5 7 parent chain
2 4 6 8

4-Methyloctane

Location + substituent + Parent (root) alkane name

24
4.3
Rules of Nomenclature (IUPAC)
Number the longest chain beginning with the end of the
chain nearer the substituent.

Designate the location of the substituent group.

4.3
When two or more substituents are present, give each substituent
a number corresponding to its location. The substituent groups
will be listed alphabetically.
2 4

CH3 6 4 2
7 2 5 4 3 6 1
CH3 CH2 CH CH2 CH CH2 CH3 1 3 5 7
CH2CH3
3-Ethyl-5-methylheptane

When two substituents are present on the same carbon, use

that number twice.

4.3
When two or more substituents are identical, indicate this by
the use of the prefixes di-, tri-, tetra-, and so on.
v.s. bis; tris; tetrakis

The prefixes di-, tri-, tetra-, etc. are not included in alphabetization.

6 4-Ethyl-2,2-dimethylhexane
1 2 3 4 5 1
5 3
3-Ethyl-5,5-dimethylhexane
6 4 2

4.3
When branching first occurs at an equal distance from either
end of the longest chain, choose the name that gives the lower
number at the first point of difference.

Where there are two or more parent chains of identical length,

choose the parent chain with the greater number of
substituents.

4.3
Nomenclature of Alkyl Halides
The halogen substituted alkanes are named as
haloalkanes in the IUPAC system.

4.3
Common names of alkyl halides are based on the alkyl
group name and the name of the halide.

4.3
Nomenclature of Alcohols
In the IUPAC naming system, there may be as many as
four features: locant, prefix, parent compound, and
suffix.
Locant: indicates the position of a substituent.
Prefix: names the substituent group.
Parent: is the parent alkane.
Suffix: names the key functional group.

4.3
Select the longest continuous chain containing the –OH
group as the parent.
Drop the “e” in the alkane name and add the suffix
“ol”.

Alkane Alkanol

Number the chain from the end that gives a lower

number to the position of the –OH group.

4.3
Common Names of Alcohols
Alkyl group names are approved by IUPAC for naming
alcohols.

R−OH: Alkyl alcohol

4.3
Glycols: alcohols containing two hydroxyl groups.

In the IUPAC substitutive system, they are named as

diols.

4.3
Cycloalkanes
Cycloalkanes have the general formula CnH2n.
Five- and six-membered rings are the most common.
Prefix the name of the corresponding open-chain alkane
with cyclo-, and name each substituent on the ring.
v. s. Cyclic
Cyclo Cyclo Cyclo Cyclo Cyclo Cycloal
Name
propane butane pentane hexane heptane kane
Molecular
C3H6 C4H8 C5H10 C6H12 C7H14 CnH2n
Formula

Structural (CH2)n
Formula

Line
Formula
35
3.5
Nomenclature of Cycloalkanes
Cyclic alkanes are names with the “cyclo” prefix
followed by the alkane name indicating the number of
the carbon atoms in the ring.

Cyclopropane

Cyclopentane
4.4
The name of a substituent is added as a prefix
to the cycloalkane name.

4.4
When there are two or more substituents, the
positions around the ring are numbered beginning
with the substituent first in the alphabet.

4.4
When a single ring system is attached to a single
chain with a greater number of carbon atoms, it
is appropriate to name the compounds as
cycloalkylalkanes.

1-Cyclobutylpentane 1,3-Dicyclohexylpropane

4.4
Hydrocarbons Having More than One Ring
-- Bicyclic (two rings),
-- Tricyclic (three rings),
-- In general, polycyclic compounds.
The molecular formulas of such compounds have H/C ratios that decrease
with the number of rings. In general, for a hydrocarbon composed of
n carbon atoms associated with m rings the formula is: CnH(2n+2 -2m).
Examples of Isomeric C8H14 Bicycloalkanes

Isolated Rings Spiro Rings Fused Rings Bridged Rings

No common
One common atom One common bond Two common atoms
atoms

40
Bicyclic Cycloalkanes-Bridged and Fused
The carbon atoms common to both rings are called
bridgeheads.
Bicyclic compounds are named by first counting the
total number of carbons in the bicyclic ring.
The base name is the alkane name for the total number
of carbons with the prefix “bicyclo”.

4.4
The number of carbons in each of the bridges is put in
brackets in decreasing order and then inserted between
the prefix and the alkane name.
The numbers are separated by periods.

Fused

Bicyclo[2.2.1]heptane Bicyclo[1.1.0]butane
(Norbonane)

4.4
Spiro Compounds

1 9 8
7
3
Spiro[2.6]nonane
2 4 6
5

1-bromo-3-chlorospiro[4.5]decan-7-ol
1-bromo-3-chlorospiro[3.6]decan-7-ol
Nomenclature of Alkenes and Cycloalkenes
Many older names for alkenes are still in common use.

4.5
Select the longest chain that contains the double bond.

Drop the “ane” in the alkane name and add “ene”.

Number the chain from the end to give lower numbers

to the alkene carbons. The location of the double bond
is given by the number of the first carbon of the alkene.

4.5
Indicate the locations of the substituent groups by the
number of the carbon atoms to which they are
attached.

4.5
Cycloalkenes
Number substituted cycloalkenes so that the alkene
carbons are positions 1 and 2 and in the direction that
gives the lower positional numbers to substituent.

4.5
Name compounds containing a double bond and an
alcohol group as alkenol and give the alcohol carbon
the lower number.

4.5
Order of Precedence
 For compounds that contain more than one functional group
indicated by a suffix.
Two frequently encountered alkenyl groups are the vinyl and
allyl group.

4.5
IUPAC Rules for Alkene and Cycloalkene Nomenclature

1. The ene suffix (ending) indicates an alkene or cycloalkene.

2. The longest chain chosen for the root name must include both carbon atoms
of the double bond.

3. The root chain must be numbered from the end nearest a double bond carbon atom.
If the double bond is in the center of the chain, the nearest substituent rule is used to
determine the end where numbering starts.

4. The smaller of the two numbers designating the carbon atoms of the double bond
is used as the double bond locator. If more than one double bond is present, the
compound is named as a diene, triene or equivalent prefix indicating the number
of double bonds, and each double bond is assigned a locator number.

5. In cycloalkenes the double bond carbons are assigned ring locations #1 and #2.
Which of the two is #1 may be determined by the nearest substituent rule.
2
1 CH3
6. Substituent groups containing double bonds are: 3
H2C=CH– Vinyl group
H2C=CH–CH2– Allyl group 4 6
5 CH3
1,6-dimethylcyclohex-(1)-ene
“Cis” and “trans” can be used to designate
isomers when there are two substituents on the
alkene.

4.5
Nomenclature of Alkynes
The name of the parent alkane is modified by dropping
the “ane” ending and adding “yne”.
The parent chain is numbered to give the carbons of the
alkyne lower numbers.
The location of the triple bond is given by the lower
positional number of the alkynyl carbons.

4.6
Positions of substituents are determined by the usual
rules.
In an alkynol, the alcohol has priority in numbering.

1-Alkynes are also called terminal alkynes.

4.6
IUPAC Rules for Alkyne Nomenclature
1. The yne suffix (ending) indicates an alkyne or cycloalkyne.
2. The longest chain chosen for the root name must include both carbon atoms of
the triple bond.
3. The root chain must be numbered from the end nearest a triple bond carbon atom.
If the triple bond is in the center of the chain, the nearest substituent rule is used to
determine the end where numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the triple bond is
used as the triple bond locator.
5. If several multiple bonds are present, each must be assigned a locator number.
Double bonds precede triple bonds in the IUPAC name, but the chain is numbered from
the end nearest a multiple bond, regardless of its nature.
6. Because the triple bond is linear, it can only be accommodated in rings larger than
ten carbons. In simple cycloalkynes the triple bond carbons are assigned ring locations #1
and #2. Which of the two is #1 may be determined by the nearest substituent rule.
7. Substituent groups containing triple bonds are:
HC≡C– Ethynyl group
HC≡CH–CH2– Propargyl group 55
Physical Properties of Alkanes and
Cycloalkanes
The unbranched alkanes form a regular series where
each member differs the next in order by one –CH2-
group. Such a regular series is called a homologous
series.
Alkanes are nonpolar compounds and have only weak
interactions between their molecules.
Alkanes are nonpolar compounds, they are insoluble in
water and dissolve well in other nonpolar or low
polarity organic solvents.
Good solvents for them are benzene, chloroform, and
carbon tetrachloride.
4.7
The boiling points of the unbranched alkanes increase
with increasing size reflecting the increasing van der
Waals attractions.

4.7
Boiling Point
Low-molecular-weight alkanes (1 to 4 carbons) are gases
at room temperature; e.g., methane, propane, butane.
Higher-molecular-weight alkanes (5 to 17 carbons) are
liquids at room temperature (e.g., hexane, decane,
gasoline, kerosene).
High-molecular-weight alkanes (18 or more carbons)
are white, waxy semisolids or solids at room
temperature; e.g., paraffin wax.
Chain-branching decreases the contact surface area
between molecules, lessening the dispersion forces
between them and leading to a lower boiling point.
Density
Average density is about 0.7 g/mL.
Liquid and solid alkanes float on water. 4.7
Pheromones
Pheromones: a secreted or excreted chemical factor that
triggers a social response in members of the same
species.
Pheromones are chemicals capable of acting outside the
body of the secreting individual to impact the behavior
of the receiving individual.

4.7
Sigma Bonds and Bond Rotation

Rotation is possible around single bonds (sigma bonds).

Conformation: any three-dimensional arrangement of
atoms in a molecule that results from rotation about a
single bond.
Each possible structure is called a conformer.
Different conformations may have different energies.
An analysis of the energy changes with rotation around
a bond is called conformational analysis.

4.8
Newman Projections
Newman Projection: a way to view a molecule by
looking along a carbon-carbon bond.

Front carbon and substituents

Back carbon and substituents
4.8
The Conformations of Ethane

An analysis of the rotation around the C-C bond in

ethane shows there are two extreme conformations.

4.8
Staggered conformation: a conformation about a
carbon-carbon single bond where the atoms on one
carbon are as far apart as possible from the atoms on
an adjacent carbon.

4.8
Eclipsed conformation: a conformation about a
carbon-carbon single bond in which the atoms on one
carbon are as close as possible to the atoms on an
adjacent carbon.

4.8
Conformational Analysis

4.8
Torsional Barrier

Torsional barrier: energy that arises when atoms

separated by 3 bonds are forced from a staggered
conformation to an eclipsed conformation.

The torsional barrier between staggered and eclipsed

ethane is approximately 3.0 kcal (12.6 kJ)/mol.

+3.0 kcal/mol

4.8
Conformational Analysis of Butane
Rotation around the internal bond in butane introduces
conformational features different from the CH3-CH3
systems.
Structures of the general type XCH2-CH2X, where X is
larger than H, have rotational barriers with significant
steric strain in the eclipsed conformation.

4.9
Conformational Analysis of Butane

4.9
4.9
The Relative Stability of Cycloalkanes: Ring Strain

Cycloalkanes do not all have the same stability.

Cyclohexane is the most stable cycloalkane and
cyclopropane and cyclobutane are much less stable.
The difference in relative stability is due to ring strain,
which comprises angle strain and torsional strain.
Angle strain: strain that arises when a bond angle is
either compressed or expanded compared with its
optimal value.
Torsional strain: the result of repulsive dispersion
forces that cannot be relieved due to restricted
conformational mobility.
4.10
Cyclopropane
Angle strain

Torsional strain

4.10
Cyclobutane

Cyclobutane also has both angle strain and torsional

strain.
The cyclobutane ring is not plannar.
By folding slightly the cyclobutane ring relieves more
of its torsional strain than it gains in the slight
increase in its angle strain.

4.10
Cyclopentane

In planar cyclopentane, all C-C-C bond angles are

108o, which differ only slightly from the tetrahedral
angle of 109.5o.
Consequently there is little angle strain.

4.10
In planar cyclopentane, there are 10 fully eclipsed C-H
bonds, which create torsional strain of approximately
10 kcal/mol.
Puckering to an “envelope” conformation relieves part
of this strain.
In an envelope conformation, eclipsed interactions are
reduced but angle strain is increased slightly (105o).

4.10
Conformations of Cyclohexane
The most stable conformation is a puckered chair
conformation.
Drawing Chair Form of Cyclohexane:

Two sets of axials Two sets of equatorial

In a chair conformation, all bond angles are approx.
109.5o, and all bonds on adjacent carbons are staggered.
Newman projection of the chair conformation of
cyclohexane:

4.11
Boat Conformation
A puckered conformation in which carbons 1 and 4 are
bent toward each other.

4.11
A boat conformation is less stable than a chair
conformation by 6.5 kcal (27 kJ)/mol.
Steric strain (nonbonded interaction strain) is created
by one set of flagpole interactions.

4.11
The boat conformation has torsional strain from
eclipsed H.
Newman projection of the boat conformation of
cyclohexane:

4.11
The twist boat conformation of cyclohexane has a
lower energy than the pure boat conformation.

4.11
More than 99% of the molecules are estimated to be in a
chair conformation at any given moment.

4.11
The Nobel Prize in Chemistry 1969:

Derek H. R. Barton Odd Hassel

(1918 - 1998) (1897 - 1981)

"for their contributions to the development of the concept

of conformation and its application in chemistry"
4.11
Substituted Cyclohexanes: Axial and
Equatorial H
The six-membered ring is the most common ring
found among nature’s organic molecules.
Six H are equatorial and six H are axial.

4.12
An axial bond extends from the ring parallel to the
imaginary axis of the ring.
Equatorial bonds are roughly perpendicular to the
imaginary axis of the ring.

4.12
Drawing Chair Conformational Structures

4.12
When a cyclohexane ring undergoes a ring flip, all of
the bonds that were axial become equatorial, and all
bonds that were equatorial become axial.

4.12
Conformational Analysis of Methylcyclohexane
The most stable conformation for a monosubstituted
cyclohexane ring is the conformation where the
substituent is equatorial.
As the size of the substituent increases, the
conformation with the group equatorial increases.

Diaxial interaction 7.28 kJ (1.74 kcal)

4.12
1,3-Diaxial Interaction
Interactions between groups in parallel axial positions
on the same side of a chair conformation of a
cyclohexane ring.

less stable more stable by 7.6 kJ/mol

ΔGo = -RT ln Keq

Keq = 18.9/1 4.12
ΔGo = -RT ln Keq Keq = 1/100
The origin of the steric strain are gauche interactions
as found in butane.

4.12
Conformational Analysis of Butane
The origin of the steric strain are gauche interactions
as found in butane.
Each gauche interaction introduces 3.8 kJ/mol of
steric strain. There is a total of 2 x 3.8 = 7.6 kJ/mol of
steric strain in the axial conformer.
Equatorial-methylcyclohexane has no steric strain
because the stereochemical relationships are anti.

4.12
In cyclohexane derivatives with larger alkyl substituents,
the strain caused by 1,3-diaxial interactions is even more
pronounced.

4.12
As the size of the substituent increases, the conformation
with the group equatorial increases. 95
Isomerism

96
Cis-Trans Isomerism in Cycloalkanes and Bicycloalkanes
Cis-trans isomers (stereoisomers) have
The same molecular formula.
The same connectivity of their atoms.
An arrangement of atoms in space that cannot be
interconverted by rotation about sigma bonds.

Configuration
v.s.
Conformation

97
Disubstituted Cyclohexanes: Cis-Trans
Isomerism
When there are two substituents in a cycloalkane at
different positions, cis and trans isomers are possible.
The cis and trans isomers are stereoisomers. They
differ in the arrangement of atoms in space but have
the same bond connectivities.

4.13
4.13
1,2-Disubstituted Cyclohexanes
Trans 1,2-Disubstituted Cyclohexanes

4.13
1,4-Disubstituted Cyclohexanes
The ring is commonly viewed through an edge or from above.
Cyclohexanes may be viewed as planar hexagons.

H3C CH3 H 3C CH3

CH3 cis or trans

H
or
H H3C
H CH3
CH3 H
In viewing chair conformations, remember that groups
equatorial in one chair are axial in the alternative chair.
For trans-1,4-dimethylcyclohexane, the diequatorial
chair is more stable than the diaxial chair.
More stable

For cis-1,4-dimethylcyclohexane, the alternative chairs

are of equal stability.

103
4.13
Trans 1,3-Disubstituted Cyclohexanes
The two chair conformers are of equal energy for trans-
1,3-dimethylcyclohexane.

There is more steric strain associated with the larger tert-

butyl group in the axial position.

4.13
Exercise

The structure of 2,3,4,6-tetrachloro-1-tert-butylcylcohexane is shown

below. How many chlorine atoms(s) is (are) at the axial position(s) ?

Cl
Cl
Cl Cl
Cl Cl
Cl Cl
105
Bicyclic and Polycyclic Alkanes
Polycyclic organic molecules are common in nature.
The steroid hormones are polycyclic alkane derivatives.

(pregnancy hormone) (male hormone)

4.14
Cis, Trans Isomerism in Bicycloalkanes

The A and B rings have stereochemical features of

bicyclo[4.4.0]decane, commonly called decalin.

107
The fusion of the A and B rings in decalin shows cis-
trans isomerism.

Equatorial to both rings

Axial to both rings
up
up
down
up down
down
up
down
109
Admantane contains a three-dimensional array of
cyclohexane rings, all of which are in the chair form.

4.14
Chemical Reactions of Alkanes
As nonpolar organic structures, alkanes have limited
chemical reactivity compared with other classes of
organic compounds.
Neither acids nor bases react readily with alkanes.
One important reaction of alkanes is combustion,
the combination with oxygen.
Oxidation is the basis for the use of alkanes as energy
sources for heat and power.

CH4 + 2O2 CO2 + 2H2O ΔHo = -212 kcal/mol

Methane

CH3CH2CH3 + 5O2 3CO2 + 4H2O ΔHo = -530 kcal/mol

Propane 4.15
The Relative Stability of Cycloalkanes: Ring Strain

Cycloalkanes do not all have the same stability.

Cyclohexane is the most stable cycloalkane and
cyclopropane and cyclobutane are much less stable.
The heat of combustion of a compound is the enthalpy
change for complete combustion of one mole of the
compound.

A bomb
calorimeter
The relative stability of isomeric hydrocarbons may
be determined by measuring their heats of
combustion under identical conditions.
Relative Stability and Heat of Combustion-C8H18

115
The cycloalkanes form a homologous series.
The general reaction for the combustion of a cycloalkane
is:

(CH2)n + 1.5n O2 nCO2 + nH2O + heat

In order to use the heats of combustion to

determine the relative stabilities of the
cycloalkane structures, the amount of heat
evolved must be adjusted for the number of
CH2 groups.
The greater amounts of heat evolved per CH2 group
can be attributed to ring strain.
The amount of heat evolved in the combustion of
cyclohexane is consistent with the value expected from
the combustion of unbranched alkanes.
Synthesis of Alkanes and Cycloalkanes
A chemical synthesis may require, at some point, the
conversion of a carbon-carbon double or triple bond to
a single bond.
This conversion is easily accomplished by
hydrogenation.

4.16
A standard way of preparing alkanes and cycloalkanes
is by the catalytic hydrogenation of the corresponding
alkenes and alkynes.
Metals such as Pt, Ni, and Pd provide active surfaces
for the reactants to rapidly interact.

4.16
Examples:

4.16
Hydrogenation allows us to distinguish between
rings and double or triple bonds.

4.17
Hydrogenation allows us to distinguish between
rings and double or triple bonds.

4.17
Structural Information from Molecular
Formulas
A compound’s molecular formula allows a chemist to
calculate the Index of Hydrogen Deficiency (IHD) of
that compound.
The IHD is calculated by converting the molecular
formula to a formula that contains carbons and
hydrogens only and then comparing it to the formula
for a saturated hydrocarbon (CnH2n+2).
The IHD increases by one for every missing two
hydrogens.
(Hreference − Hmolecule )
IHD =
2
4.17
If the molecular compound has the same number of
hydrogens as its saturated hydrocarbon counterpart
then it has an IHD = 0.
The IHD increases by one for every missing two
hydrogens.
Each IHD is equal to one ring or one multiple bond.
A double bond is equal to 1 IHD.
A triple bond is equal to 2 IHD.

4.17
Both 1-hexene and cyclohexane have an IHD equal to 1.

Saturated hydrocarbon C6H14

1-Hexene/Cyclohexane C6H12
Hydrogen missing 2 which means IHD = 1

4.17
Degree of Unsaturation as a Key to Structure CnH2n+2
Degree of
Formula Representative structures unsaturation
C6H14 0
C6H12
; 1

(one π bond) (one ring)

C6H10
; ; 2

(two π bonds) (one π bond (two rings)

+ one ring)
C6H8
; ; 3

(three π bonds) (two π bonds (one π bond

+ one ring) + two rings)
Compounds Containing X, O, and N
For compounds containing halogen atoms, each
halogen atom is equal to one hydrogen.
For compounds containing oxygen atoms, each oxygen
atom is equal to zero hydrogen atoms.
For compounds containing nitrogen atoms, each
nitrogen atom is equal to minus one hydrogen atoms.

Molecular Formula Converted to Compare to IHD

C6H10Cl2 C6H12 C6H14 1
C8H8Br4Cl2 C8H14 C8H18 2
C6H12O2 C6H12 C6H14 1
C7H12O3 C7H12 C7H16 2
C6H13N C6H12 C6H14 1
C10H26N4 C10H22 C10H22 0
Index of Hydrogen Deficiency
Problem: isopentyl acetate has a molecular formula of C7H14O2.
Calculate its IHD.
 reference hydrocarbon C7H16
 IHD = (16-14)/2 = 1

Problem: calculate the IHD for niacin, molecular formula

C6H6N2O.
 reference hydrocarbon C6H14
 IHD = 5
C4H8O (IHD = 1)

C4H9N (IHD = 1)