MSE245

Organic Materials
Chemistry and Processing
Professor Naomi Matsuura
WB 138
naomi.matsuura@utoronto.ca

February 2, 2024

MSE 245 Course Outline

1. Review: bonding, Lewis structures, hybridization, acids base chemistry
2. Introduction to IUPAC nomenclature (handouts)
3. Alkanes and Cycloalkanes (Ch 3)
4. Alkenes and Alkynes (Ch 4)
5. Reactions of Alkenes/Alkynes (Ch 5)
6. Chirality and the Shape of Molecules (handouts)
7. Haloalkanes (Ch 7)
8. Alcohols, Ethers, and Thiols (Ch 8)
9. Benzene and its Derivatives (Ch 9)
10. Amines (Ch 10)
11. Aldehydes and Ketones (Ch13)
12. Carboxylic Acids and derivatives (Ch 14 &15)
13. Organic Polymer Chemistry and synthesis (Ch 16 + Brazel & Rosen Ch 1 & 2)
14. Polymer Physical properties (Brazel & Rosen Ch 3, 4, 5 and 6)
15. Polymer processing (Ch17 (Brazel & Rosen Ch-17)
16. Polymer recycling, degradation and environmental impact (handouts)
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 SHAPE OF MOLECULES
ISOMERS, STEREOCENTERS, CHIRALITY, SYMMETRY

Isomers are different compounds with

the same molecular formulas
• Isomers reflect the extraordinary versatility of carbon in forming
strong bonds to itself and to other elements
• All isomers are either constitutional isomers or stereoisomers
Constitutional isomers
Stereoisomers
(Structural isomers)
Isomers which have the same
Isomers which differ in "connectivity” connectivity (i.e., more subtle kind
(i.e., the difference is in the sequence of isomerism, the isomers differ
in which atoms are attached to one only in their spatial arrangement,
another). not in their connectivity).
e.g., C5H12

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 Constitutional isomers vs. Stereoisomers

Although constitutional isomers have the same molecular

formula, their physical and chemical properties may be
very different.

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 Geometrical Optical

ISOMERS
CONSTITUTIONAL (STRUCTURAL) ISOMERS

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 Constitutional (Structural) Isomers
• When the group of atoms that make up the molecules of
different isomers are bonded together in fundamentally different
ways, we refer to such compounds as constitutional isomers
(structural isomers).
• have the same molecular formula.
• have different bond connectivities.
• are different compounds.
• have unique names.
• have different physical properties.
• may or may not have similar chemical properties.
• There are 3 types of constitutional isomers:
• Chain (or nuclear) isomers
• Position isomers
• Functional group isomers

Chain (Nuclear) Isomers

• These isomers arise because of the possibility of
branching in carbon chains. For example, there are two
isomers of butane, C4H10. In one of them, the carbon
atoms lie in a "straight chain" whereas in the other the
chain is branched.

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 Position Isomers
• Position isomers have the same carbon skeleton and the same
substituent groups, but differ in the position of the substituent
group
• Position isomers occur among substituted alkanes and other
compounds. They have similar chemical properties since they
differ only in the location of the functional group
• This is an important group in cyclic compounds

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Functional Isomers
• They have the same molecular formula but differ in the nature
of the functional group.
• e.g: Dimethyl Ether: (CH3)2O and Ethanol: C2H5OH.
• Even though the atoms are the same, they are arranged differently. This
yields two different compounds with the same number of atoms. These
compounds have different functional groups. They are functional
isomers (belong to constitutional isomers).
• The first is a gas which will knock you out if inhaled. The other is
common alcohol drunk in spirits. The two molecules are shown below.

Dimethyl Ether Ethanol

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 Structural Formulas for C4H10O Isomers (total of 7 isomers)
Kekulé Formula Condensed Formula Line-angle Formula

Alcohols

Ethers

There are no double or triple bonds and no rings in any of these structures 13

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Which one is the same or different?

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 ISOMERS
STEREOISOMERS

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Stereoisomers

• There are two major types of stereoisomers:

1. Diastereomers (or Geometrical isomers) and
2. Enantiomers (or Optical isomers)
• Diastereoisomers: Stereoisomers which are not mirror images
• Cis- and trans-isomers are a type of diastereomers. They have
the same connectivity but are not mirror images of each other.
• Enantiomers: Stereoisomers which are mirror images
• The difference between diastereoisomers and enantiomers rests
upon the concept of mirror image isomerism.

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 Geometric (cis/trans) isomerism
(disasteromers)
• Geometric isomers have the same structural formulas but differ in the
arrangement of groups at a single atom, at double bonds, or in rings.

isomer melting point (°C) boiling point (°C)

cis -80 60
trans -50 48
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Properties of cis- vs. trans- Isomers

• cis-isomer has a higher boiling point
• trans-isomer has a higher melting point

Isomer Melting point (°C) Boiling point (°C)

cis-1,2-dichloroethene -80 60
trans-1,2-dichloroethene -50 48

Isomer Melting point (°C) Boiling point (°C)

cis-but-2-ene -139 4
trans-but-2-ene -106 1

Note: This Tb difference is distinct from what we saw in constitutional isomers in alkanes
(previous lecture) 18

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 Why is the boiling point of the cis-isomers
higher?
• There are stronger intermolecular forces between the molecules of
the cis-isomers than between trans-isomers in the liquid phase.
• Both isomers have exactly the same atoms joined up in exactly the same
order (i.e., the van der Waals dispersion forces between the molecules will be
the same).
• The difference is that the cis-isomer is a polar molecule whereas the trans-
isomer is non-polar.
• Both molecules contain polar chlorine-carbon bonds, but in the cis-isomer
they are both on the same side of the molecule. That means that one side of
the molecule will have a slight negative charge while the other is slightly
positive. The molecule is therefore polar.
• There will be dipole-dipole interactions as well as dispersion forces - needing
extra energy to break
e.g., 1,2-dichloroethene

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Why is the melting point of the trans-isomers

higher?
• In order for the intermolecular forces to work well in the
solid phase, the molecules must be able to pack together
efficiently in the solid.
• Trans-isomers pack better than cis-isomers. The "U" shape
of the cis-isomer doesn't pack as well as the straighter
shape of the trans-isomer.
• The poorer packing in the cis-isomers means that the
intermolecular forces aren't as effective as they should be
and so less energy is needed to melt the molecule - a lower
melting point.

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 Enantiomers (optical isomers) - Chirality
• A molecule or object which is not identical to (i.e., non-superimposable upon)
its mirror image molecule or object is said to be chiral. This means it resembles
a human hand in that the left and right hands are not superimposabile but can
be readily distinguished.
• To be isomers, molecules must not be identical. The test for "identicality" is
one of superimposability.
• Many molecules are chiral, especially complex molecules such as those found in
biological systems.

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Stereogenic (Chiral) Center

How can you anticipate if a molecule is chiral (has an enantiomer)
or is achiral (has no enantiomer)?
• One of the simple ways is to use the concept of a stereogenic
(chiral) center. If a molecule has a single stereogenic center it
will necessarily be chiral. The most common kind of stereogenic
center is a carbon (or other atom) which has four different
atoms or groups directly attached to it.

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 Chirality and Stereocenter
• The most common cause of chirality is the presence of a carbon atom bonded
to 4 different groups.
• Such carbon is referred as chirality center or stereocenter.
• Chirality is the property of the entire molecule, a stereocenter is the cause of
chirality.

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Tetrahedral carbon and their mirror images

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 Symmetry Elements
• If the molecule or object has either a plane of symmetry or a
center of symmetry it is achiral (non-chiral).
• It is especially useful when there is more than one
stereocenter.

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 Example
• Is 5-bromodecane chiral?
• If so, identify the stereocenter

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