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Molecules
formula
shape
name
bonding
Atoms
3
Alkanes – Chapter 2
The electronic configuration of carbon (atomic number 6) is:
2p
2s
1s
4
C: 1s2 2s2 2px1 2py1
2p
2s
1s
5
Hybrid Orbitals
• The Problem:!
– We would expect two single bonds to carbon and bonding
by the 2p atomic orbitals would give a bond angle of
approximately 90°.!
– instead we observe bond angles of approximately 109.5°,
120°, and 180°.!
• The Solution:!
– hybridization of atomic orbitals.!
– 2nd row elements use sp3, sp2, and sp hybrid orbitals for
bonding.!
6
Hybrid Orbitals
• Hybridization of orbitals (L. Pauling).
– the combination of two or more atomic orbitals
forms a new set of atomic orbitals, called hybrid
orbitals.
• We deal with three types of hybrid orbitals.
sp3 (one s orbital + three p orbitals).
sp2 (one s orbital + two p orbitals).
sp (one s orbital + one p orbital).
• Overlap of hybrid orbitals can form two types of bonds.
depending on the geometry of overlap.
σ bonds are formed by “direct” overlap.
π bonds are formed by “parallel” overlap. 7
sp3 hybridization → example: CH4!
2p
2s
1s
8
Carbon bonding to hydrogen
According to this configuration, carbon has two unpaired
electrons, and should form two bonds with two hydrogen
atoms.
2p
2s
1s
2p
Hybridize sp3
2s
1s 1s
11
4 hybrid sp3 orbitals
12
hybrid sp3 orbitals
– the four sp3 hybrid orbitals are directed toward the corners
of a regular tetrahedron at angles of 109.5°
13
4 hybrid sp 3 orbitals
14
Methane (CH4): the C sp3 hybrid orbitals and the H 1s
orbitals overlap to form σ bonds - tetrahedron shape
The C-H bond energy is 104 kcal/mol - each σC-H lowers the
energy by 104 kcal/mol 15
Consider the molecule ammonia, NH3: 1s2 2s2 2p3
There are four hybrid orbitals and one of the orbitals is filled
with a pair of electrons.!
2p
Hybridize sp3
2s
1s 1s
HCl
+
17
Water H2O: 1s2 2s2 2p4
There are four hybrid orbitals and two of the orbitals are filled
with a pair of electrons.
2p
hybridize sp3
2s
1s 1s
19
sp2 Hybrid Orbitals!
One pure s orbital Two pure p orbitals
20
sp2 Hybrid Orbitals!
One pure s orbital Two pure p orbitals
21
3 hybrid sp 2 orbitals
2p 2p
Hybridize (sp2) sp2
2s
1s 1s
H H
B
23
Consider the methyl carbocation, CH3+:
2p
2s
1s
ground state of C+
24
The methyl carbocation, CH3+
To be as far apart from each other as possible, the three
sp2 orbitals are oriented at the corners of an equilateral
triangle.
2p 2pz
2s hybridize sp2
1s 1s
s + px + py
ground state of C+ sp2 hybridized carbocation
25
• Hydrocarbon: a compound composed only of
carbon and hydrogen.
26
Connectivity
The connectivity in a molecule describes which atoms are
attached to others.
One compound has one and only one connectivity (or structure).
Greek prefixes
After the first four members, the name is derived from
the Greek prefixes for the number of carbon atoms.
29
molecular condensed structural name
formula formula
CH4 CH4 METHANE
C 2H 6 CH3CH3 ETHANE
C 3H 8 CH3CH2CH3 PROPANE
C4H10 CH3CH2CH2CH3 BUTANE
C5H12 CH3(CH2)3CH3 PENTANE
C6H14 CH3(CH2)4CH3 HEXANE
C7H16 CH3(CH2)5CH3 HEPTANE
C8H18 CH3(CH2)6CH3 OCTANE
C9H20 CH3(CH2)7CH3 NONANE
C10H22 CH3(CH2)8CH3 DECANE
C11H24 CH3(CH2)9CH3 UNDECANE
30
Structure!
Carbon is tetravalent - it has four covalent bonds to other atoms.
Hydrogen is monovalent - it has one bond to another atom.
A hydrocarbon with n carbon atoms can hold a maximum of 2n+2
hydrogen atoms.
If a hydrocarbon has less than 2n+2 hydrogen atoms then there are
cyclic and/or atoms bonded to each other by more than one bond
(multiple bonds).
31
Alkanes
32
Representations of n-hexane
Condensed formula: C6H14
Lewis structure
Ball-and-stick representation
33
What is the correct condensed formula of the following
molecule?
A) CH3CH2CHBrCHO
B) CH3CH2BrCHCOOH
C) CH3CH2CHBrCO2H
D) CH3CH2CBrCO2H
35
Arrow pushing
H
H H
H H
The double bonds in benzene are not fixed in position and the
electrons of the double bonds are delocalized over the entire
ring → ʻresonanceʼ.! 36
Conformation
37
conformations of ethane
eclipsed conformation
39
conformations of ethane
40
conformations of ethane
41
conformations of ethane
42
conformations of ethane
staggered conformation
44
conformations of ethane
45
conformations of ethane
46
conformations of ethane
47
conformations of ethane
48
The relative positions of the hydrogen atoms on
the two carbon atoms are best represented with
a Newman Projection.
49
A Newman projection is a view of a molecule down the axis of a
carbon-carbon bond. The carbon in the front is represented by a dot,
and the carbon in the back is represented by a circle.
50
A Newman projection is a view of a molecule down the axis of a
carbon-carbon bond. The carbon in the front is represented by a
dot, and the carbon in the back is represented by a circle.
51
A Newman projection
52
53
54
A Newman projection is a view of a molecule down the axis of a
carbon-carbon bond. The carbon in the front is represented by a dot,
and the carbon in the back is represented by a circle.
55
A Newman projection is a view of a molecule down the axis of a
carbon-carbon bond. The carbon in the front is represented by a
dot, and the carbon in the back is represented by a circle.
56
A Newman projection
57
58
59
Staggered conformation
60
60° dihedral angle
0° dihedral angle
61
60° dihedral angle
0° dihedral angle
62
• Staggered conformation: a conformation of a
carbon-carbon single bond where the atoms
on one carbon are as far apart as possible
from the atoms on the adjacent carbon.
63
• Eclipsed conformation: a conformation of a
carbon-carbon single bond where the atoms
on one carbon are as close as possible to the
atoms on the adjacent carbon.
64
Energetics for ethane
65
Energetics for ethane
• Torsional strain: the force that opposes the rotation
of one part of a molecule about a bond while the
other part of the molecule is held fixed.
3.4 kcal/mol
66
Energetics for ethane
67
eclipsed
68
eclipsed
Ball-and-stick Space-filling
70
staggered
Ball-and-stick Space-filling
71
• At room temperature, molecules have
enough kinetic energy to get over barriers as
high as 20 kcal/mol.
72
consider butane
CH3CH2CH2CH3
74
Butane, CH3CH2CH2CH3
76
Forces involved in conformational preferences
• Weak attraction/repulsion that exists between nonpolar molecules
are known as van der Waals interactions.
• These forces are the result of the motion of electrons within bonds
and molecules.
• When molecules (or parts of the same molecule) are not too close,
attractive van der Waals interactions can occur.
• However, if the distance is too short (less than the van der Waals
radii of the interacting atoms, repulsive (unfavourable) van der
Waals interactions occur. 77
Butane
Eclipsed Eclipsed
78
Ethane
80
Butane conformations
energy diagram
81
Butane conformations
energy diagram
82
Butane conformations
energy diagram
83
Butane conformations
energy diagram
84
Butane conformations
energy diagram
85
Butane conformations
energy diagram
86
Butane conformations
energy diagram
87
Butane conformations
energy diagram
88
Butane conformations
energy diagram
eclipsed form 89
Butane conformations
energy diagram
90
Butane conformations
energy diagram
91
Butane conformations
energy diagram
92
Butane conformations
energy diagram
93
Butane conformations
energy diagram
94
Butane conformations
energy diagram
gauche form 95
Butane conformations
energy diagram
96
Butane conformations
energy diagram
97
Butane conformations
energy diagram
98
Butane conformations
energy diagram
99
Butane conformations
energy diagram
100
Butane conformations
energy diagram
101
Butane conformations
energy diagram
102
Butane conformations
energy diagram
5 kcal/mol
104
Butane conformations
105
Butane conformations
106
Butane conformations
107
Butane conformations
108
Butane conformations
110
Energetics for butane
[anti]/[gauche] = 4
111
Which Newman projection represents that of butane, viewed along the C2-C3
bond with a dihedral angle of 60º?
A) B)
C) D)
Hydrocarbons
space-filling models
Alkanes have the general formula CnH2n+2!
1 10
Compounds that differ from each other in their molecular formulas
by the unit -CH2- are members of a homologous series. 113
All alkanes have similar chemical properties, but their
physical properties vary with molecular weight and and the
shape of the molecule
The boiling points of linear alkanes increase steadily with
molecular weight.
straight-chain branched-chain
117
Constitutional Isomerism!
118
Nomenclature - IUPAC!
Suffix -ane specifies an alkane!
Prefix tells the number of carbon atoms!
119
methane, CH4
1,1-dichloroethane 1,2-dichloroethane
122
Propane, C3H8
124
Same classification for amines!
• Primary (1°) amine: nitrogen bonded to one carbon.
– R-NH2 e.g. CH3NH2 methylamine
125
Butane, C4H10
2-methyl-propane
127
CH3-H = methane
CH3- = methyl
CH3-CH3 = ethane
CH3-CH2- = ethyl
CH3-CH2-CH3 = propane
CH3-CH2-CH2- = propyl
CH3-CH2-CH2-CH3 = butane
CH3-CH2-CH2-CH2- = butyl
128
IUPAC
129
IUPAC SYSTEM OF NAMING COMPOUNDS
1. Select the longest continuous chain of carbon atoms for
the basic name.
2. Number the carbons in the chain from the end nearest the
first branch.
3. Identify substituents (e.g. methyl, ethyl, bromo, chloro). If
more than one substituent of the same kind is present, use
the prefixes “di,” “tri” or “tetra.”
4. Locate the substituents by the number of the carbon to
which they are attached.
5. Put substituents in alphabetical order (prefixes (di, tri,
tetra, n-, sec-, tert-, do not count).
6. Use commas to separate numbers and separate numbers
from letters by a dash and write the whole name as one word
with the basic name at the end. 130
6 4 2
5 3 1
3-methylhexane
131
1 2 3 4 5
pentane
2-methylpentane
132
CH3CH3 CH2CH3
CH3CHCHCH2CHCH2CH2CH3
1 2 3 4 5 6 7 8
5-ethyl-2,3-dimethyloctane
134
CH3CH3 CH2CH3
CH3CHCHCH2CHCH2CH2CH3
1 2 3 4 5 6 7 8
5-ethyl-2,3-dimethyloctane
135
CH3CH3 CH2CH3
CH3CHCHCH2CHCH2CH2CH3
1 2 3 4 5 6 7 8
5-ethyl-2,3-dimethyloctane
136
7 6
3 4 5
4 1
5 6
1 2
7 3 2
6
5
4 2
3
1
octane
3,5-dimethyloctane
4-ethyl-3,5-dimethyloctane 138
2
3 1
9 8 7 6 5 4
nonane
3-methyl nonane
3-methyl-4-propylnonane
139
line structure
6 5 4 3 2
1
hexane
tetramethylhexane
2,2,3,4-tetramethylhexane
140
• Number chain to make substituent locator numbers
as low as possible
141
What is the IUPAC name of the following compound?
A) 2,3-dimethyloctane
B) 2,3,6-trimethylheptane
C) 2,3,6-methylheptane
D) 2,5,6-trimethylheptane
E) both B and D
Provide an IUPAC name for the following:
A) 4-ethyl-4-methylhexane
B) 2,2-diethylpentane
C) 3-ethyl-3-methylhexane
D) 3-methyl-3-propylpentane
Cycloalkanes!
Cycloalkanes are cyclic hydrocarbons with the general formula CnH2n
145
Representations of cyclohexane!
146
Cycloalkanes
• General formula CnH2n.
– five- and six-membered rings are the most common.
methylcyclohexane
148
1-bromo-3-tert-butylcyclohexane
1-bromo-3-t-butylcyclohexane
149