Email: jrobichaud@champlaincollege.qc.

ca
Office: f-228
Phone: x311
CHAMPLAIN COLLEGE
SAINT-LAMBERT
GENERAL CHEMISTRY
202-NYA-205
Winter 2012
Joel Robichaud
Course Outline
nomenclature
empirical & molecular
formulas
stoichiometry
gas laws
molarity
UNIT 1:
Basics
UNIT 2:
Atomic Theory
history of atomic theory
the Bohr atom
the modern approach
(quantum theory)
quantum numbers
electron configurations
electron affinity
UNIT 3:
Periodicity &
Chemical Reactions
electron configuration & chemical
properties of elements
ionization energy
atomic and ionic size
electronegativity & electron affinity
reactions of the main group elements
writing molecular & net ionic equations
UNIT 4:
Chemical Bonding
analysis of ionic & covalent bonding
writing Lewis structures, resonance
structures formal charges
shapes of molecules bond angles
bond polarity
dipole moments
hybridization theory orbital diagrams
UNIT 5:
Intermolecular Forces
intermolecular forces intramolecular
bonds
dispersion forces, dipole-dipole forces
hydrogen bonding
relationship of melting & boiling point
& solubility to intermolecular forces
classification of substances
UNIT 6:
Liquids & Solutions
properties of solids
phase changes & phase
diagrams
physical properties of
solutions
concentration units
colligative properties
describe the formation of a covalent bond between two atoms using the total interactive energy of the system. (9.4)
interpret the information given in a potential energy vs. internuclear distance diagram (10.3)
use Lewis symbols of the elements to explain formation of ionic compounds. (9.2)
apply the octet rule and know its limitations. (9.6 & 9.9)
define and understand the concept of covalent bonding. (9.4)
compare and contrast covalent and ionic bonding. (9.2 & 9.4)
define electronegativity and explain trends within the representative elements of the periodic table. (9.5)
recognize polar and non-polar covalent bonds. (9.5)
draw Lewis structures for covalent compounds and polyatomic ions. (9.6 & 9.7)
define terms and recognize examples of structural and geometric isomers. (22.4 & Molecular Geometry experiment)
draw resonance structures with arrow pushing. (9.8)
determine formal charge. (9.7)
explain how the concept of resonance can be used to explain bond energies, bond lengths, and stabilities of some
molecules & ions. (9.8)
learn the basic geometric shapes and the angles associated with them. (10.1)
use the valence shell electron pair repulsion theory (VSEPR) for predicting molecular geometries. (10.1)
predict the molecular geometry and bond angles for species with lone pairs on the central atom. (10.1)
predict the polarity of molecules based on the overall geometry and bond polarities. (10.2)
use the valence bond theory to explain covalent bonding. (10.3)
apply hybridization theory to show how atoms maximize their bonding possibilities. (10.4)
use orbital (box) diagrams to show how atoms form a particular set of hybrid orbitals. (10.4 & Molecular Geometry
experiment)
determine the geometry & bond angles of any species using the concept of hybridization of the central atom. (10.4)
predict the hybridization of carbon in its compounds, indicating those containing multiple bonds. (10.4)
draw an orbital overlap diagram for the following molecules: CH
4
, C
2
H
4
, C
2
H
2
, H
2
, X
2
, N
2
, O
2
& CO
2
(10.4)
Unit IV: Chemical Bonding (Chang, Ch. 9, 10 & 22)
Objectives:
Unit IV: Chemical Bonding (Chang, Ch. 9, 10 & 22)
4.1 Lewis Structures
(Chang, 9.1, Textbook Problems, )
Lewis Dot symbol: Consists of the symbol of an element and one dot for each valence
electron in an atom of the element.
Br

Lewis Structures: Shows the bonding arrangement of covalent compounds &
polyatomic ions in a 2-dimensional picture (based on the concept
that atoms search to complete their octet).
Br

Br

Ex.
Bonded electrons (a covalent bond) are represented by a dash.
A pair of electron (belonging only to one atom) are represented by a lone pair.
Ex.
Typically:
Atom Lewis
Structure
Bonding
Arrangement
Valence Example
C 4 bonds
0 lone pair
Tetravalent
N 3 bonds
1 lone pair
Trivalent
O 2 bonds
2 lone pairs
Divalent
Halogen
(X= F, Cl, Br or I)
1 bond
3 lone pairs
Monovalent
H 1 bond
0 lone pair
Monovalent
C C
H
H
H H
N N
H
H H
O
O H H
X
X H
H X H
Continuation...
In a molecule with a formula Ax
n
:
A is usually the central atomto which X are attached.
A is usually the one which can make the most bonds or the least electronegative.
When drawing a Lewis structure:
Draw a diagram connecting all the atoms with a SINGLE bond.
Add the # of valence electrons to find the total # of valence electrons.
Note: each covalent bond requires 2 electrons (subtract the electrons needed for covalent bonds).
The other electrons complete the octet (each atom wants to see 8 electrons, Hydrogen 2).
4.1.1 Exercises:
1. Complete the Lewis Diagram for the following molecules:
a) CH
4
b) H
2
O c) NH
3
Exceptions to the Octet Rule
Compounds with Beryllium & Boron are content to not complete the octet:
Be is content to see 4 electrons
B is content to see 6 electrons
If there are insufficient electrons to complete all octets, then you must
complete the octet of the most electronegative atoms first.
4.1.2 Exercises:
1. Complete the Lewis Diagram for the following molecules:
a) BeCl
2
b) BeH
2
c) BF
3
d) BH
3
Charged Molecules
For every negative charge, one electron must be added to the total electron count.
For every positive charge, one electron must be subtracted to the total electron count.
4.1.3 Exercises:
1. Complete the Lewis Diagram for the following molecules:
a) H
3
O
+
b) NH
4
+
c) BCl
4
-
d) NH
2
-
Atoms from the 3
rd
or Later Periods
If the central atom is from the 3
rd
period or later, it is allowed to go above the octet
(atoms in the 2
nd
period NEVER go above the octet).
Complete the octet of outer atoms and if theres any extra [expanded octet]
they are added to the central atom(only if it is from the 3
rd
period or more).
4.1.4 Exercises:
1. Complete the Lewis Diagram for the following molecules:
a) SCl
4
b) ClF
3
c) XeF
2
d) BrF
4
+
e) SbCl
5
Double & Triple Bonds
Double bonds are created when atoms dont complete their octet
(most likely N, O, C & S).
Lone pairs are converted into a covalent bond.
4.1.5 Exercises:
1. Complete the Lewis Diagram for the following molecules:
a) O
2
b) C
2
H
4
c) H
2
CO d) N
2
e) CO f ) CN
-
4.2 Formal Charges
Formal charge: charge given to a particular atomin a Lewis diagram.
Neutral Removed 1 electron Added 1 electron
Formal charge = 0 Formal charge = +1 Formal charge = -1
Carbon 4 bonds
0 lone pair
3 bonds
0 lone pair
3 bonds
1 lone pair
Nitrogen 3 bonds
1 lone pair
4 bonds
0 lone pair
2 bonds
2 lone pairs
Oxygen 2 bonds
2 lone pairs
3 bonds
1 lone pair
1 bonds
3 lone pairs
C
C
C
N
N
N
O O O
Established by comparing the # of electrons before & after bonding
(the sum of the formal charges must equal the charge of the compound).
Continuation...
You can also use the formula:
Formal charge = Group # of Atom - # of unshared e
-
- # of covalent bond
Formal charge = Group # of Atom ( (# of shared electrons) + # of unshared e
-
)
or
4.2.1 Exercises:
1. Complete the Lewis Diagram for the following molecules and assign formal charges:
a) H
2
O b) H
3
O
+
c) NH
3
d) SbCl
5
2-
Continuation...
When there is a choice:
The Lewis structure which creates the least # of formal charge is preferred.
The Lewis structure where the negative charge is on the most electronegative atom
is preferred (or positive on the least electronegative).
4.2.2 Exercises:
1. Complete the Lewis Diagram for the following molecules and assign formal charges:
a) CO
2
b) SCN
-
4.2.2 Exercises:
2. Complete the Lewis Diagram for the following molecules and assign formal charges:
a) H
2
S b) AsF
5
-
c) BeF
2
d) C
2
H
2
e) TeF
4
f ) CS
2
g) BrF
3
h) ICl
4
-
i) N
2
H
4
j) HCN
k) BrF
5
l) XeF
3
+
m) XeF
4
n) C
2
Cl
4
o) BCl
3
p) C
2
F
2
q) N
2
H
2
4.3 Isomers
Isomers: compounds with the same molecular formula but different structures
(atoms are connected differently, bonds have to be broken to get from
one to another).
Note: While single bonds can rotate, double bonds cannot.
4.3.1 Exercises:
1. Draw different isomers for the following molecules:
a) C
2
H
2
Cl
2
b) C
2
H
4
O
c) C
2
H
4
ClBr d) C
3
H
5
F
4.4 Resonance
Resonance: when it is possible to shift electrons around (i.e. delocalization) using
lone pairs & double bonds (both Lewis structures are equally plausible).
Note: The actual molecule is a hybrid of the resonance structures.
Resonance adds a lot of stability to the molecule.
4.4.1 Exercises:
1. Draw the Lewis diagram (if not given) and resonance structures for the following:
a) b) NO
2
-
c) d) SO
2
e) SO
3
f ) CO
3
2-
C
C
C
C
C
C
H
H
H
H
H
H
N
O
O O
O O O
4.5 Bond Length
Length of bonds is affected by the # of bonds between two atoms.
Bonds between 2 carbon atoms:
C
2
H
6
= 0.154 nm
C
2
H
4
= 0.134 nm
C
6
H
6
= 0.139 nm
C
2
H
2
= 0.120 nm
The more bonds between 2 atoms, the shorter the length of that bond.
Ex.
4.5.1 Exercises:
1. Arrange the following in order of increasing bond length
a) The N-N bond in N
2
, N
2
H
4
, N
2
H
2
b) The C-O bond in CH
3
OH, HCO
2
-
, CO
3
2-
, H
2
CO, CO
c) The N-O bond in NO
+
, NO
2
-
, NO
3
-
4.5 Molecular Geometry, VSEPR Theory
Valence Shell Electron Pair Repulsion Theory (VSEPR Theory):
A molecule will adopt a 3-dimensional shape where bonds & lone pairs,
are as far away as possible from one another to minimize repulsion between them.
The next table describes the shape of molecules with a repulsion # from 2-6:
A represents the central atom
B represents bonds
E represents a lone pair of electrons
Note: Single, double or triple bonds all count as one
(they all occupy the same region in space).
The electronic repulsion between lone pairs (LP) & bond pairs (BP) is:
LPLP > LPBP > BPBP
The repulsion number (also known as the #of electron clouds)
includes: Lone Pairs (LP) & Bond Pairs (BP).
Linear
Trigonal
bipyramidal
Octahedral
Trigonal
planar
Tetrahedral
Linear
Trigonal
bipyramidal
Octahedral
Trigonal
planar
Tetrahedral
Molecular Geometry: No Lone Pair (LP)
Linear (rep. # = 2)
Octahedral (rep. # = 6)
AB
6
AB
5
AB
4
AB
3
AB
2
Trigonal planar (rep. # = 3)
Trigonal bipyramidal (rep. # = 5)
Tetrahedral (rep. # = 4)
Molecular Geometry: No Lone Pair (LP)
When a lone pair is added, it requires a bit more roomthan a covalent bond
therefore all bond angles will become smaller.
H
C
H
H
H
H
N
H
H
H
N
H
H
H
H
O
H
109.5 109.5 107.3 104.7
Ex.
Molecular Geometry: Introduction of Lone Pairs (LP)
Note 2: while the angles for a tetrahedral geometry without LP must be known (i.e. 109.5
o
),
simply write < 109.5
o
for the angles of a tetrahedral geometry where a LP is present.
Note 1: angle values are only given for two adjacent atoms connected through a central
atom (i.e. never give angle values between a LP and another atom).
Trigonal bipyramidal
Tetrahedral
Trigonal
pyramidal
Seesaw
Bent
Trigonal planar
Bent
Tetrahedral
Molecular Geometry: With Lone Pair(s) (LP)
Octahedral
Trigonal bipyramidal
Trigonal bipyramidal
Octahedral
Square
planar
Square
pyramidal
Linear
T-shaped
AB
2
E
(rep. # 2)
AB
3
E
(rep. # 4)
AB
2
E
2
(rep. # 4)
AB
4
E
(rep. # 5)
Molecular Geometry: With Lone Pair(s) (LP)
Tetrahedral
Bent
Trigonal
bipyramidal
Trigonal
planar
Tetrahedral
Trigonal
pyramidal
Bent
Seesaw
AB
3
E
2
AB
2
E
3
AB
5
E
AB
4
E
2
Molecular Geometry: With Lone Pair(s) (LP)
Trigonal
bipyramidal
Linear
Octahedral
Octahedral
Trigonal
bipyramidal
Square
planar
Square
pyramidal
T-shaped
4.6 Polarity of Molecules
A molecule is considered to be polar if it has a net dipole.
Steps to follow:
4.6.1 Exercise:
1. Determine if the following molecules are polar or non-polar, if they are polar then determine the
direction of the resultant.
a) H
2
O b) PF
3
c) BF
3
d) HF
e) CO
2
f ) ClF
3
g) CH
4
A vector is drawn for all bonds which have dipole, the arrow going towards the most
electronegative atom(if the electronegativity difference is larger, the vector is also larger).
If after the addition of the bond dipole vectors, there is a net vector then the molecule is
polar, otherwise the molecule is non-polar.
Note: a molecule may be non-polar even though it has polar bonds.
First draw the Lewis diagramof the molecule,
Then do the VSEPR sketch,
Then find all vectors,
Then find the resultant.
4.6.1 Exercises:
2. For the following determine or draw: Lewis Structure
Repulsion number
Name of geometry without lone pairs
VSEPR sketch
Name of actual geometry
Bond angles
If the molecule is polar or non-polar
a) OF
2
b) CH
4
c) BeCl
2
d) CH
2
F
2
e) BF
3
f ) NH
3
g) PCl
5
h) ClF
3
i) SF
6
j) IF
5
k) BrF
4
-
l) XeF
2
m) XeF
4
n) ClF
4
+
o) SO
2
p) H
2
CO
q) HCN r) N
2
H
4
s) CO
2
t) NH
2
-
u) I
3
-
4.7 Hybridization
Only electrons that are alone in an orbital can bind, all others form lone pairs.
How to explain the following molecule: CH
4
?
Hybridization splits electron pairs to other orbitals close
in energy in order to have the desired # of single electrons.

2p
2

2s
2

C :
C* :
C* :
2p

2s


sp
3
Excited state: promotion of an electron from s to p.
[He]
[He]
[He]
Hybridization: the half-filled orbitals are blended to obtain
degenerate orbitals (i.e. all of the same energy).
Result: formation of 4 equivalent orbitals.
Problem: as written, only 2 bonds can be made.
Problem: different orbitals different types of bonds.

2p
3

2s
2

N : [He]
N* : [He]
In this case the electron pair does not need to be split.
sp
3
Molecular
Geometry
(excludes LP):
Electron pair
Arrangement
(includes LP):
Many molecules however, possess not only bond pairs (BP), but also lone-pair s(LP).
Ex. NH
3
Question: Is hybridization is still required?
< 109.5
o
Note: a lone pair is represented by 2 electrons in an orbital.
4.7 Hybridization
Solution: hybridization affords 4 equivalent sp
3
orbitals
and explains the tetrahedral geometry.
Note: one of the sp
3
hybridized orbitals contains a Lone Pair (LP).
4.7.1 Exercises:
1. Determine the hybridization of the orbitals in the following central atom in order to
obtain the molecules below.
For each, give: # of covalent bonds
# of electron pairs
Orbital box diagram:
Excited State:
Hybridized State:
a) BeH
2
b) BH
3
c) CH
4
d) PCl
5
e) SF
4
f ) SF
6
g) XeF
2
h) XeF
4
i) KrF
4
j) ClF
3
4.8 Valence Theory of Bonding
A bond is not actually a line, it is an overlap between 2 electron clouds.
An overlap between orbital can lead to various types of bond:
bond & bond (others are possible but will not be discussed)
The Bond:
a stronger bond is obtained when there is a greater overlap between electron clouds.
the atoms cant get too close because at a certain point repulsion between nuclei occurs.
A s bond can result from the overlap of:
2 s orbitals, s & p orbital,
2 p orbital (head-to-head), 2 hybrid orbitals,
s & hybrid orbital, p & hybrid orbital.
The 1
st
bond between 2 atoms is always a s bond.
The s bond allows free rotation between the atoms.
4.8 Valence Theory of Bonding
All other bonds between atoms (for this course).
The Bond:
The p bond is rigid & no rotation is possible.
Is the result from 2 p orbitals side by side.
Hybridization hints:
Repulsion Number Hybridization
2 sp
3 sp
2
4 sp
3
5 sp
3
d
6 sp
3
d
2
4.9 Hybridization for More Complex Molecules
If the central atomhas a formal charge, the # of electrons must reflect the charge.
4.9.1 Exercises:
1. Determine the hybridization of the orbitals in the following central atom in order to obtain the
following molecules:
a) NH
4
+
# of bonds
# of electron pairs
# of bonds
Orbital box diagram:
Excited State:
Hybridized State:
b) AsF
5
2-
# of bonds
# of electron pairs
# of bonds
Orbital box diagram:
Excited State:
Hybridized State:
If the charge is positive: there are less electrons than a typical neutral atom.
If the charge is negative: there are more electrons than a typical neutral atom.
A bond is higher in energy than a bond: meaning that
electrons which form a bond should not be hybridized.
1. Determine the hybridization of the orbitals in the following central atom in order to obtain the
following molecules:
a) C
2
H
4
# of bonds
# of electron pairs
# of bonds
Orbital box diagram:
Excited State:
Hybridized State:
b) C
2
H
2
# of bonds
# of electron pairs
# of bonds
Orbital box diagram:
Excited State:
Hybridized State:
4.9 Hybridization for More Complex Molecules
4.9.2 Exercises:
4.10 Orbital Overlap Diagram
The Orbital Overlap Diagram represents molecules as electron clouds
(closer to reality, rather than representing bonds with straight lines).
First find the VSEPR sketch,
Then the hybridization of each atom,
Then bonds are replaced by electron clouds,
Indicate the type of bond ( or ),
Electron clouds must be labelled according to their name/hybridization.
H
2
Lewis Diagram
Orbital Box Diagram:
VSEPR Sketch Orbital Overlap Diagram
Steps to follow:
Continuation...
CH
4
Lewis Diagram
Repulsion Number (C) : Hybridization (C) :
VSEPR sketch Orbital Overlap Diagram
Br
2
Lewis Diagram
Repulsion Number (Br
1
) : Hybridization (Br
1
) :
Repulsion Number (Br
2
) : Hybridization (Br
2
) :
VSEPR sketch Orbital Overlap Diagram
O
2
Lewis Diagram
Repulsion Number (O
1
) : Hybridization (O
1
) :
Repulsion Number (O
2
) : Hybridization (O
2
) :
VSEPR sketch Orbital Overlap Diagram
C
2
H
4
Lewis Diagram
Repulsion Number (C
1
) : Hybridization (C
1
) :
Repulsion Number (C
2
) : Hybridization (C
2
) :
VSEPR sketch Orbital Overlap Diagram
Continuation...
Continuation...
N
2
Lewis Diagram
Repulsion Number (N
1
) : Hybridization (N
1
) :
Repulsion Number (N
2
) : Hybridization (N
2
) :
VSEPR sketch Orbital Overlap Diagram
C
2
H
2
Lewis Diagram
Repulsion Number (C
1
) : Hybridization (C
1
) :
Repulsion Number (C
2
) : Hybridization (C
2
) :
VSEPR sketch Orbital Overlap Diagram
Continuation...
CO
2
Lewis Diagram
Repulsion Number (C) : Hybridization (C) :
Repulsion Number (O) : Hybridization (O) :
VSEPR sketch Orbital Overlap Diagram
End of unit exercises:
1. For the following molecules give: Box diagram of the central atom
Box diagram of the excited central atom
Box diagram of the hybridized atom
VSEPR sketch
Bond Angles
Name of geometry
a) BeH
2
b) BH
3
c) CH
4
d) NH
3
e) H
2
O f ) HF
g) PCl
5
h) SF
4
i) ClF
3
j) XeF
2
k) KrF
4
l) SiF
4
2-
m) ClF
4
+
n) AsF
5
-2
o) BrF
4
-
p) IF
6
+
q) XeF
3
+
r) CN
-
s) CH
2
O t) CO
2