CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

The Language of Organic Chemistry

How to Draw and Interpret Organic Structures:
Structural diagrams need to include all the necessary information.
Also need to reduce superfluous information for ease of viewing structures.
Drawing Hydrocarbon Frameworks:
The hydrocarbon framework is made up of hydrogen and carbon atoms ONLY it can be in a
straight or branched chain, or in a ring.
Carbon can form four covalent bonds to other atoms.
Hydrogen can form one covalent bond to other atoms.
Steps for drawing hydrocarbon frameworks (using a five carbon chain as an example):
o Notice the three dimensional shape of the molecule (which we will ignore for now).
H H H H H
H C C C C C H
H H H H H

1. Draw chains of atoms as zig-zags (to imitate the three dimensional shape).
H H H H
H
H
C
C
C
C
H C
H H H
H H

2. To make the diagram above less "busy" miss out the Hs attached to carbon atoms, along with
C-H bonds. Occasionally the Hs are included, especially is they take place in a reaction or are
part of a functional group (see below).
C

3. Now remove capital "Cs" representing carbon atoms and draw a zig-zag chain. This is
typically how an organic chemist draws the structure of pentane.

Q1: Draw three different hydrocarbons that contain two carbon atoms. Write out both the
empirical formula and molecular formula for each example.
Hint: Carbon can form single, double and triple bonds with itself add the appropriate number of
hydrogen atoms to complete the carbon frameworks.

Used with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

Q2: Work out the molecular formula of the hydrocarbon molecule shown below, and calculate its
molecular weight.

Q3: Draw stick diagrams of hydrocarbon molecules with five carbon atoms (containing only
single bonds) that have a:
1. Single chain
2. Branched chain
3. Ring

Q4: Re-draw (and therefore tidy up) the following as stick representations.
H2
C H2
C
H3C CH

H2C CH3 CH3

H
C
C
H2
CH3

H2C

CH2

Wedge and hash bonds can be used to represent molecule in three dimensional space:
The three dimensional structure of methane (CH4) can be represented as:
Straight line is in the
plane of the paper

Hashed line points behind the

plane of the paper
Wedged line points forw ard

Used with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

Heteroatoms:
This is an atom that is neither carbon nor hydrogen.
For organic chemistry this is most commonly O, N, F, Cl, Br, I, S, P, Si.
These atoms are ALWAYS included in the structural drawing.
Heteroatoms are generally the "reactive" portion of organic molecules.
Q5: How many covalent bonds can be made by the following atoms:
O=

S=

N=

F=

Cl =

Br =

I=

Functional Groups:
Functional groups are the key to the chemistry of molecules.
Diagrams must emphasize the functional groups, and let the hydrocarbon framework fade
into the background.
Q6: Circle & name the functional groups in the molecule below:
The following structure represents NutraSweet, an artificial sweetener that is 200 times sweeter
than sugar (i.e. sucrose).

CO2H

H
N

H 2N

O
O

Q7: What is the molecular formula of this molecule ?

Used with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

Q8: Circle & name the functional groups in the molecule below:
The structure shown below represents Astra-Zenecas drug Tenormin, a cardiovascular -blocker
for the treatment and prevention of heart disease.

OH

H
N

Q9: What is the molecular weight of Tenormin ?

Q10: Name the functional groups in the molecules shown below:

Me

NO2

CN
Me

H3C

H
CH3

Q11: Write out the molecular formula under each structure shown above.
Functional Groups of Hydrocarbons:
Carbon-carbon double and triple bonds are considered to be functional groups.
Q12: Name the following functional groups:

Used with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer
Interpreting Lewis Structures
The Structure of a Molecule ultimately Determines Its Bulk Properties:
A molecule is a group of atoms held together by electrons to give a definite three dimensional
shape.
The structure and properties of the molecule are determined not only by its constituent
atoms, but also by how they are arranged the shape of the molecule.
An understanding of the fundamental principles related to the structure and bonding of
atoms is essential for understanding the diverse architecture and properties of molecules.
Atoms, Electrons, and Orbitals:
Each element in the periodic table is characterized by a unique atomic number (Z) which is
equal to the number of protons in its nucleus.
99% of naturally occurring carbon atoms are carbon-12, 1% of carbon is the isotope carbon-13.
For each isotope below:

12

C
6

13
6

Q13: What is the atomic number ?

Q14: What is signified by the mass number ?

Q15: How many protons, neutrons and electrons does each isotope have ?

Q16: How many protons, neutrons and electrons does the following ion have ?
13

C
6

Used with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

Organic chemists are primarily concerned only with the electrons in atoms, and
more importantly with the electrons in molecules.

Q16: Write out the electronic configurations of:

Hydrogen:

Carbon:

Oxygen:

Q17: How many valence electrons do the following atoms have:

Hydrogen:

Lithium:

Carbon:

Nitrogen:

Oxygen:

Chlorine:

The Lewis Model of Chemical Bonding:

In 1916 G. N. Lewis proposed that atoms combine in order to achieve a more stable electron
configuration.
Maximum stability results when an atom is isoelectronic with a noble gas.
An ionic bond is the force of electrostatic attraction between oppositely charged ions.
An electron pair that is shared between two atoms constitutes a covalent bond.
Structural formulae in which electrons are shown as dots are called Lewis Structures.
e.g. H for a hydrogen atom.

Sharing electrons allows atoms to become isoelectronic to a noble gas.

e.g. Two atoms of H become H:H filling their 1s shell.

A shared electron (covalent) bond is represented by a dash

i.e. H:H becomes H-H

Used with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

Q18: Draw Lewis structures for the following (show all valence electrons):
F2

HCN

H2O

Li+Cl (ionic bond)

Q19: Why is the following structure not possible ?

H H
H

Q20: Draw stick diagrams for the following (include all lone pairs of electrons):

OH
H3C

C
H

CH3

H2C
H2C

C
C
H2

CH2Cl
CH2
CH2

CH3
H3C

CH3

H3C

CH3

Used with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer
The Shapes of Some Simple Molecules:
So far, covalent bonding has only been considered in two dimensions, specifically:
o How many covalent bonds an atom can form (and why).
o Drawing simple molecules using Lewis structures.
What three dimensional shapes do organic molecules take, and why do they assume these
shapes?
Types of three dimensional representations you may encounter:
Stick Model
(Ethanol)

Ball-and-Stick Model
(Acetone)

Space Filling Model

(Hexane)

Application of the Valence Shell Electron Pair Repulsion (VSEPR) theory where the most stable
arrangement of groups attached to a central atom is the one that has the maximum
separation of electron pairs (bonded or non-bonded).

Q21: What are the shapes of the following simple molecules:

H
H C H

..
H O
.. H

: O:

Used with permission from Dr. A. Causton, UC Chem

H
N
H .. H

..
..
O C O
..
..

CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer
Ionic Bonding:
An ionic bond is the force of electrostatic attraction between oppositely charged ions.
Ionic bonds are common in inorganic chemistry but rare in organic chemistry.
o e.g. NaCl
_
_
+
Na+Cl
Na + Cl
Na + Cl

The charge on an atom changes upon loss or gain of an electron

..

O:
Formal Charge for Organic Structures:
..
To demonstrate how to calculate formal charges for individual atoms H O
.. N
in organic molecules (with covalent bonds), consider the Lewis formula
:O
.. :
of nitric acid (HNO3) shown on the left without any charges assigned.
In order to calculate the formal charge on each atom it is necessary to know how many
electrons the neutral atom has in its valence shell (H = 1, C = 4, N = 5, O = 6, F = 7 etc.).
Count up the number of electrons that belong to each atom:
o Each line in the Lewis structure represents a covalent bond a shared pair of
electrons where one electron belongs to each atom on either side of the bond.
o Add to this the number of lone pairs of electrons on each atom.

6 electrons

6 electrons

(4 from "lone Pairs" plus 2 from covalent bonds)

(4 from "lone Pairs" plus 2 from covalent bonds)

O
H O N
1 electron

(from covalent bond)

4 electrons
(4 from covalent bonds)

7 electrons
(6 from "lone Pairs" plus 1 from covalent bonds)

For the atoms in nitric acid to be considered neutral, H, O, and N must have 1, 6 and 5
electron(s) belonging to their valence shell
o The H atom has one electron therefore is neutral
o Two of the O atoms have six electrons - therefore are neutral
o One O atom has seven electrons associate with it that is one extra negatively
charged electron - therefore this atom is assigned a negative charge
o The N atom has four electrons associated with it that is one less negatively charged
electron - therefore this atom is assigned a positive charge
Thus the formal charges on the Lewis diagram of nitric acid are:

or

NOTE: You should be able to look at the formal charges on an atom in an organic structure
(i.e. the bottom left representations) and work "backwards" to figure out how many electrons
(and lone pairs) are associated with each atom.

Used with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

Q22: Calculate the formal charges (if any) associated with the following structures:
:
:

..

..
..

..
:
..

Q23: Add the appropriate number of electrons to the following:

O

_
H O N O
+

H
H C

Q24: Draw a Lewis representation (and include any formal charges) of ozone, O3:

Q25: From you drawing, comment on the expected bond lengths between each of the oxygen
atoms.

VERY IMPORTANT CONCEPT: Resonance:

Sometimes more than one Lewis structures may be written for a compounds (or ion) these
are known as resonance hybrids (or contributing structures).
o Consider ozone (O3) the O-O-O bonds are all equal in length therefore the two
possible Lewis structures must represent an averaged structure.
o Notice the double-headed arrow that designates resonance structures.
Used with permission from Dr. A. Causton, UC Chem

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CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

Q26: Draw resonance structures of ozone, O3:

Q27: What assumption(s) are made when reading a resonance structure ?

Q28: How is the concept of resonance important to interpreting the structure of benzene ?

NOTE: By definition, resonance structures differ only in the distribution of electrons in the
Lewis structure - the connectivity of the individual atoms must be the same in all resonance
hybrids.

Q29: Draw resonance structures for the following NO3 ion:

_

Equavlent
Resonance
Structure to
the one shown.

Impossible
Resonance
Structure.

Different
Resonance
Structure to
the one shown.

Not a resonance
Structure.

Used with permission from Dr. A. Causton, UC Chem

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CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer
Curved Arrows:
Curved arrows are used to track the flow of electrons.
o Full arrows are used to show the movement of a pair of electrons.
+

o Half arrows show the movement of one electron

Cl

Cl

Cl

Cl

Q30: Draw the curved arrows to show the electron shift between resonance structures in the
amide functional group:

"Bad" Resonance Structure

...but not impossible...

Q31: Draw an impossible resonance structure for the amide functional group:

Q32: Complete the following arrow pushing reaction schemes:

Br

Used with permission from Dr. A. Causton, UC Chem

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CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

Polar Covalent Bonds and Electronegativity:

Electronegativity is a measure of the ability of an element to attract electrons toward itself
(when bonded to another element) - electronegative elements attract electrons
Electronegativity increases from left to right in the periodic table
Electronegativity decreases going down a group in the periodic table
The greater the difference in electronegativity between two bonded atoms - the more polar
the bond
A bond can be classed as polar or non-polar - the symbols + and - are used to signify the
distribution of the electron density in a polar bond.
+
Non-Polar Bond

Polar Bond

Q33: Draw a circle around the most polar molecule in the following series:

H Cl

H F

H Br

Q34: Draw a circle around the polar molecule(s) in the following series:
H2O

CH4

CO2

NH3

BF3

Q35: Draw a circle around the polar molecule(s) in the following series:
CH4

CH3Cl

CH2Cl2

CHCl3

CCl4

Electronegativity and Resonance Structures:

Among Lewis structural formulae that satisfy the octet rule and in which one or more atoms
bears a formal chargethe major contributor is the one in which the negative charge resides
on the most electronegative atom.

Major

Minor

Oxygen is more electronegative

than nitrogen.

Q36: Rank the relative importance of the following resonance contributors to ethanamide:
O
H2N

O
CH3

H2N

+
_
CH3

Used with permission from Dr. A. Causton, UC Chem

_
O
+ C
H2N
CH3

H2N

_
O
+
C

CH3

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CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

Q37: Rank the relative importance of the following resonance contributors to the nitro functional
group:

N
R + O

N
R + O

N
R 2+ O

O
R

Rules for Ranking Resonance Structures:

MOST STABLE
1. All atoms neutral with full octet
2. All atoms with formal charges have full octet
2a. More electronegative atom bears negative charge
3. Atoms present without full octet
3a. More electronegative atom bears negative charge
4. Too many electrons in valence electron shell
LEAST STABLE
The concept of electronegativity can help explain why/how reactions proceed:
e.g. SN2, nucleophilic substitution reactions a one-step reaction mechanism in which the
negatively charged species attacks the carbon centre that has low electron density (i.e. is
electropositive), with the bond to the leaving group being broken at the same time.

H O

H
Br

HO

CH3

Br

H CH3

Q38: In the above example, why is the carbon electropositive ?

Q39: Define:
Electrophilic:

Nucleophilic:

Used with permission from Dr. A. Causton, UC Chem

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CHEM 357 Winter 2016-Workbook#01

L02 - A. Musgrove Richer

Q40: Shown below is an alternate two-step mechanismthat can be proposed to the SN2,
nucleophilic substitution reactions shown on the previous page. Why is this "proposed"
mechanism seriously flawed ?

_
Br

Question to think about:

Q41: When looking at the reaction at the top of the page do you think the reverse reaction is
possible ? i.e. products reactants
H
H O-

H
Br

CH3

Used with permission from Dr. A. Causton, UC Chem

Br

HO
H CH3

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