Week 4-5b

Physical Properties
of
Alkanes, Alkyl
Halides, Alcohols,
Ethers and Amines

Dr. C. V. Raidron

Sources:
© Pearson 2014; www.libtretext.com; www.leah4sci.com
 Physical properties
Learning Objectives:
• Explain and predict the physical properties incl. relative bp and solubility in a
mixture.
• Predict relative boiling points and solubility of alkyl halides.
• Explain why the boiling points of alcohols and phenols are much higher than
those of alkanes, ethers, etc., of similar molecular mass.
• Discuss the factors that are believed to determine the acidity of alcohols and
phenols.
• Explain why the boiling points of primary and secondary amines are higher than
those of alkanes or ethers of similar molar mass but are lower than those of
alcohols.
• Compare the boiling points of tertiary amines with alcohols, alkanes, and ethers
of similar molar mass.
• Compare the solubilities in water of amines of five or fewer carbon atoms with
the solubilities of comparable alkanes and alcohols in water.
• Explain why the boiling point of an ether is generally higher than that of an
alkane of similar molecular mass.
 Physical properties - Alkanes
General Properties:
• Alkanes are not very reactive.
• They are colourless, and odour-less and non-polar.
• Due to weak London dispersion forces,
• the short carbon chains are gaseous substances,
• moderate chains are volatile liquids,
• long chains are solids.
• Alkanes are less dense than water (and will float on the surface).

These differences occur because there is a direct relationship

between size and shape of molecules and the strength of the
intermolecular forces.
Physical properties - Alkanes
 Boiling Points
• bp of a compound is the temperature at which the
liquid form becomes a gas (vaporizes).
• The forces that hold the individual molecules close
to each other in the liquid must be overcome.
The greater the attractive forces between
molecules, the higher the boiling point.
attractive forces
van der Waals forces
dipole–dipole interactions
hydrogen bonds
© 2014 Pearson Education, Inc.
 Boiling Points
• Methane –167.7 °C
• Ethane –88.6 °C
• Propane –42.1 °C
• Butane –0.5 °C
• Pentane 36.1 °C
• Hexane 68.7 °C induced dipole-induced
dipole interactions
• Heptane 98.4 °C
• Octane 125.7 °C van der Waals forces
The greater the surface area of the molecule,
the higher the bp.
© 2014 Pearson Education, Inc.
 Branching Lowers the Boiling
Point
• by reducing the surface area of contact,
• weakens the intermolecular forces.

“cigar”
“tennis ball”

Cycloalkanes have boiling points that are approximately 20º higher than the
corresponding straight chain alkane.
© 2014 Pearson Education, Inc.
 Melting Points:
• The mp is influenced by the packing of the molecules in
the crystal lattice.
• alkanes with an odd number of carbons pack less tightly
 The Structure of an Alkyl Halide
• Have the same geometry as alkanes.
• C−X bond is formed by overlap of sp3 orbital of
carbon with an sp3 orbital of halogen.

The C—X bond of an alkyl halide becomes

longer and weaker as the size of the halogen
increases.

© 2014 Pearson Education, Inc.

 The Structure of an Alkyl Halide
• Halogens are more electronegative than carbons.
• i.e. Carbon-halogen bond is polarized.

Down a group:
• molecular size increases,
• bond length increases,
• bond strength decreases. Higher bp for haloalkanes
compared to alkanes.
© 2014 Pearson Education, Inc.
 The Structure of an Alcohol
Resembles the Structure of Water

An alcohol is structurally like water with

one H replaced by an R.
© 2014 Pearson Education, Inc.
 The Structure of an Ether
Resembles the Structure of Water

An ether is structurally like water with

both Hs replaced by Rs.
© 2014 Pearson Education, Inc.
 Structures of Amines

© 2014 Pearson Education, Inc.

 Dipole–Dipole Interactions

Dipole–dipole interactions
are stronger than van der
Waals forces.

Van der Waals Van der Waals

© 2014 Pearson Education, Inc. dipole–dipole
 Comparative Boiling Points
The larger the atom, the more loosely it holds the electrons in its
outermost shell, and the more they can be distorted.

Polarizability indicates how readily an electron cloud can be

distorted to create a strong induced dipole.
The larger the halogen, the more polarizable it is.
© 2014 Pearson Education, Inc.
 Hydrogen Bonds in H2O and NH3

ºC

CH4 –167.7 ºC H2O 100 ºC

no hydrogen bonds hydrogen bonds
Hydrogen bonds are stronger than other dipole–dipole interactions.
© 2014 Pearson Education, Inc.
 Hydrogen Bonds in Water

© 2014 Pearson Education, Inc.

 Hydrogen Bonds in Amines

Hydrogen bonds are stronger in primary amines than

in secondary amines because primary amines have
stronger dipole–dipole interactions.
Tertiary amines cannot form hydrogen bonds with
each other. Do you know why not?
© 2014 Pearson Education, Inc.
 Comparative Boiling Points

A hydrogen bond is a special kind of dipole-dipole

interaction that occurs between a hydrogen that is
attached to an oxygen, nitrogen, or fluorine and a
lone pair of an oxygen, nitrogen, or fluorine in
another molecule.
© 2014 Pearson Education, Inc.
 Hydrogen Bonds in Proteins
They play a crucial role in biology,
• including holding protein chains
in the correct 3-D shape.

© 2014 Pearson Education, Inc.

 Hydrogen Bonds in DNA
They play a crucial role in biology,
• making it possible for DNA to
copy all its hereditary
information.

© 2014 Pearson Education, Inc.

 Compounds with Similar Shapes and Properties
Often Have Similar Physiological Activities

Drugs bind to their receptors by van der Waals interactions,

dipole-dipole interactions, and hydrogen bonding.
© 2014 Pearson Education, Inc.
 Solubility

like dissolves like

Polar compounds dissolve in polar solvents (H2O).

Nonpolar compounds dissolve in nonpolar solvents

(hexane).

Both alkanes and cycloalkanes are virtually

insoluble in water.
© 2014 Pearson Education, Inc.
 Solvation

Solvation is the interaction between solute molecules

and solvent molecules.
© 2014 Pearson Education, Inc.
 An Oxygen Can Drag
Three Carbons Into Water

© 2014 Pearson Education, Inc.

“Like Dissolves Like” is Important in
Drug Action
• Crossing the blood–brain barrier requires a fat-soluble drug.
• THC and barbiturates have a hydrocarbon tail to facilitate
crossing the barrier.

© 2014 Pearson Education, Inc.

 Solubilities of Alkyl Halides

Only alkyl fluorides have an atom that can form a

hydrogen bond with water.

© 2014 Pearson Education, Inc.

 Rotation Occurs About C—C
Single Bonds (σ)

© 2014 Pearson Education, Inc.

Staggered and Eclipsed Conformers
(conformational isomers) of Ethane

Newman
Projections

© 2014 Pearson Education, Inc.

 Newman Projection:
Video 1
Introduction

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.
© 2014 Pearson Education, Inc.
© 2014 Pearson Education, Inc.
© 2014 Pearson Education, Inc.
© 2014 Pearson Education, Inc.
 Eclipsed conformers

Staggered conformers
© 2014 Pearson Education, Inc.
 A Staggered Conformer is More
Stable Than an Eclipsed Conformer
Empty antibonding
Filled bonding
orbital
orbital

Delocalization of electrons by the overlap

of a σ orbital with an empty orbital is
hyperconjugation – a stabilizing interaction.
Only in the staggered conformation are
the two orbitals parallel.
© 2014 Pearson Education, Inc.
 Newman Projection:
Video 2
Butane

© 2014 Pearson Education, Inc.

 Rotation Can Occur About the
Three Carbon—Carbon Bonds in Butane

© 2014 Pearson Education, Inc.

 Rotation About C-2—C-3 in
Butane

Steric strain is the repulsion between the electron clouds of

atoms or groups.

© 2014 Pearson Education, Inc.

 Rotation About C-2—C-3 in
Butane

• Of the three staggered conformers, D has the two methyl groups

as far apart as possible.
• D is more stable than the other two staggered conformers (B & F).
• D is called the anti conformer (Anti is Greek for “opposite”)
• B & F are called gauche conformers (gauche is French for “left”).
• The anti and gauche conformers have different energies because
of steric strain.
• In general, steric strain in molecules increases as the size of the
interacting atoms or groups increases.
© 2014 Pearson Education, Inc.
 Bond Angles in Planar Cyclic Alkanes
Von Baeyer believed that all cyclic compounds were planar.
Deviating from the ideal angle (109.5°) causes angle strain
which decreases the stability.

© 2014 Pearson Education, Inc.

 Angle Strain

tetrahedral bond angle = bond angle <

109.5° 109.5°
Angle strain results from poor orbital–orbital overlap
because bonds have to deviate from the ideal (109.5°)
bond angle.
© 2014 Pearson Education, Inc.
 Cyclopropane

© 2014 Pearson Education, Inc.

 Cyclobutane

Molecules twist out of a planar arrangement

to minimize angle strain and the number of eclipsed hydrogens.

© 2014 Pearson Education, Inc.

 Cyclopentane

Molecules twist out of a planar arrangement to

minimize angle strain and the number of eclipsed hydrogens.

© 2014 Pearson Education, Inc.

 Newman Projection:
Video 3
Chair conformers

© 2014 Pearson Education, Inc.

 Chair Conformer of Cyclohexane

The chair conformer of cyclohexane is completely

free of strain.
All bond angles are 111° and all adjacent bonds
are staggered.
© 2014 Pearson Education, Inc.
 • ─4.92 kcal/mol for each “strainless” CH2 group. Can calculate the heat of formation
of the other “strainless" cycloalkane.
• You should be able to verify the strain energy given for any cycloalkane.
© 2014 Pearson Education, Inc.
 Drawing the Chair Conformer

Notice that each equatorial bond is parallel to two ring bonds.

© 2014 Pearson Education, Inc.
 Axial and Equatorial Bonds

© 2014 Pearson Education, Inc.

 Newman Projection:
Video 4
Ring flip to boat conformer

© 2014 Pearson Education, Inc.

 Ring Flip

Cyclohexane interconverts between two

stable chair conformers.

© 2014 Pearson Education, Inc.

 The Boat Conformer of Cyclohexane

The boat conformer:

• is free of angle strain.
• is not as stable as the chair conformer, because some of the
C―H bonds are eclipsed.
• The “flagpole hydrogens” cause steric strain, causing further
destabilization.

© 2014 Pearson Education, Inc.

© 2014 Pearson Education, Inc.
 Build a model of cyclohexane. Convert it from one
chair conformer to the other by pulling the topmost
carbon down and pushing the bottommost carbon up.

© 2014 Pearson Education, Inc.

 Conformers of Cyclohexane

© 2014 Pearson Education, Inc.

 Conformers of Monosubstituted
Cyclohexanes

• The two chair conformers of a monosubstituted cyclohexane

are not equivalent.
• The substituent is in an equatorial position (more stable)
in one conformer and in axial position (less stable) in the other.
• In equatorial position the substituent has more room and fewer
steric interactions.
© 2014 Pearson Education, Inc.
 A Substituent is More Stable in
an Equatorial Position

© 2014 Pearson Education, Inc.

 1,3-Diaxial Interactions

1 5
6

2 3
4

© 2014 Pearson Education, Inc.

 Comparing Conformers

Gauche is 0.87 kcal/mole Axial is 1.74 (2 × 0.87) kcal/mol

less stable than anti. less stable than equatorial.

© 2014 Pearson Education, Inc.

 The larger the
substituent,
the more the
equatorial-substituted
conformer will be
favored.

© 2014 Pearson Education, Inc.

 The Only Difference Between Starch and Cotton
is an Equatorial Bond Versus an Axial Bond

© 2014 Pearson Education, Inc.

 Conformers of Disubstituted Cyclohexanes
Cis and Trans Isomers
Example: 1,4-dimethylcyclohexane
• cis-trans isomers are geometric isomers.
• Same atoms and atoms are linked in the same order
but have different spatial arrangements.
• Are different compounds with different mp’s and bp’s.
• Can be separated.

© 2014 Pearson Education, Inc.

 Each Isomer Has
Two Chair Conformers

© 2014 Pearson Education, Inc.

 This Chair Conformer
Has Four Diaxial Interactions

© 2014 Pearson Education, Inc.

 cis-1-tert-butyl-3-methylcyclohexane

• Both substituents of the cis isomer are in equatorial positions

(more stable) in one chair conformer and both are in axial positions
in the other.

© 2014 Pearson Education, Inc.

 trans-1-tert-butyl-3-methylcyclohexane

• Both conformers of the trans isomer have one substituent in an

equatorial position and the other in an axial position.
• tert-butyl group is bigger than methyl group, the 1,3-diaxial
interactions are stronger with it in axial position.
• With tert-butyl group in equatorial position, the conformer is more
stable.
© 2014 Pearson Education, Inc.
 Rings Can Be
Trans Fused or Cis Fused

© 2014 Pearson Education, Inc.

 Newman Projection:
Video 4
Chair conformations to Newman projections

© 2014 Pearson Education, Inc.

 The Steroid Ring System

© 2014 Pearson Education, Inc.

 Tetrahydrofuran (THF, bp 66 °C) has a higher
bp than cyclopentane (bp 49 °C) primarily due
to
A. increased van der Waals
forces.
B. hydrogen bonding.
O
C. increased mass. THF cyclopentane
D. increased Baeyer bp 66 °C bp 49 °C
interactions.
E. increased dipole–dipole
interactions.

© 2014 Pearson Education, Inc.

 Tetrahydrofuran (THF, bp 66 °C) has a higher
bp than cyclopentane (bp 49 °C) primarily due
to
A. increased van der Waals
forces.
B. hydrogen bonding.
O
C. increased mass. THF cyclopentane
D. increased Baeyer bp 66 °C bp 49 °C
interactions.
E. increased dipole–dipole A permanent dipole exists
interactions. between C and O.

© 2014 Pearson Education, Inc.

 The most stable conformation of trans-1,4-
dimethylcyclohexane is the ________
conformation.
A. chair
B. half chair
C. twist chair
D. twist boat
E. boat

© 2014 Pearson Education, Inc.

 The most stable conformation of trans-1,4-
dimethylcyclohexane is the ________
conformation.
A. chair CH3
B. half chair H3C
C. twist chair
D. twist boat
In most cases the chair conformation is
E. boat the most stable. In this isomer both
methyl groups are in equatorial
positions.

© 2014 Pearson Education, Inc.

 Rank the alcohols, all of similar molecular
mass, in order of decreasing boiling point.

A. 1>2>3>4
1 CH3CH2CH2CH2OH
B. 4>3>2>1
2 CH3CH2(CH3)CHOH
C. 3>2>1>4
3 (CH3)COH
D. 4>1>2>3
4 HOCH2CH2CH2OH
E. 1>2>4>3

© 2014 Pearson Education, Inc.

 Rank the alcohols, all of similar molecular
mass, in order of decreasing boiling point.

A. 1>2>3>4
1 CH3CH2CH2CH2OH
B. 4>3>2>1
2 CH3CH2(CH3)CHOH
C. 3>2>1>4
3 (CH3)COH
D. 4>1>2>3
4 HOCH2CH2CH2OH
E. 1>2>4>3
Increased hydrogen bonding
increases the boiling point.

© 2014 Pearson Education, Inc.