CHEMISTRY24 WhathaveyouheardaboutOCHEM?

Difficulty Level?
Organic Chemistry Lecture I Study Time?
Fall 2015 How to Study? Memorization?
Tips for Success
Dr. John D. Spence
Office Hours M and W 2:00-3:30 SQU 528 WhyareyoutakingOCHEM?
jspence@csus.edu Chemistry Major?

http://www.csus.edu/indiv/s/spencej/ Biology Major?

Pre-med? Pre-Dental? Pre-Pharm?

HowdoyousucceedinOCHEM?
attend class
work as many problems as possible
learn good study habits (everyday, learn foundation, limit memorization)

SyllabusandSacCT
1 2

WhatisOrganicChemistry? OriginsofLife
1780s
Chemistry of compounds from living organisms
Vitalism: 1750-1850 (Berzilius)
Stanley Miller 1950
Inorganic compounds from non-living source
Organic compounds only from a living source
Friedrich Wohler 1800-1882 (Berzilius's student)
1828 converts ammonium cyanate into organic compound urea
Justis von Liebig 1803-1873
Creator of modern lab instruction
August Kekule 1829-1896
1861 Organic chemistry a study of the compounds of carbon
1858 Tetravalent Carbon and C-C bond, 1865 Structure of Benzene
Jacobus van't Hoff 1852-1911
1874 Tetrahedral Carbon, First Chemistry Nobel Prize 1901
Synthesis of amino acids, formaldehyde, purines and pyrimidines
1890's Bayer synthesis of acetylsalicyclic acid (aspirin)
from earths primordial atmosphere (H2, H2O, O2, NH3, CO2, CH4)
Linus Pauling 1901-1994 and static discharge
Resonance, hybridization, molecular orbital theory
TODAY - over 18 million organic compounds synthesized (more than all other atoms
combined!) 3 4

AtomicStructure
1 Organic Chemists View of 6
H the Periodic Table of C
1.007 12.01
94
Elements 1

3 6 5 6 7 8 9 6 Structure of an atom
Li C B C N O F C
6.941 12.01
1
10.81
1
12.01
1
14.00
67
15.99
94
18.99
840
12.01
1
Positively charged nucleus (very dense, protons
11 12 13 14 15 16 17 6
N M Al
26.98
Si
28.08
P
30.97
S
32.06
Cl
35.45
C
12.01
and neutrons) and small (10-15 m)
a g 154 55 376 6 27 1
22.98 24.30
977 5

19 20 6 22 6 24 25 26 6 6 29 30 6 6 6 6 35 6
K
39.09
83
Ca
40.07
8
C
12.01
1
Ti
47.88
C
12.01
1
Cr
51.996
1
Mn
54.938
0
Fe
55.847
C
12.01
1
C
12.01
1
Cu
63.546
Zn
65.39
C
12.01
1
C
12.01
1
C
12.01
1
C
12.01
1
Br
79.90
4
C
12.01
1
Negatively charged electrons are in a cloud (10-10
6 6 6 6 6 6 6 6 6 46 6 6 6 6 6 6 53 6 m) around nucleus (orbitals)
C C C C C C C C C Pd C C C C C C I C
12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 106.42 12.01 12.01 12.01 12.01 12.01 12.01 126.9 12.01
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 045 1

6 6 6 6 6 6 6 76 6 6 6 80 6 6 6 6 6 6
C
12.01
1
C
12.01
1
C
12.01
1
C
12.01
1
C
12.01
1
C
12.01
1
C
12.01
1
Os
190.2
C
12.01
1
C
12.01
1
C
12.01
1
Hg
200.59
C
12.01
1
C
12.01
1
C
12.01
1
C
12.01
1
C
12.01
1
C
12.01
1
Diameter is about 2 10-10 m (200 picometers (pm))
C
6
C
6 6
C C
6
C
6 6
C
6
C
6
C C
6 110
(269)
111
(272)
112
(277)
114
(285)
116
(289)
118
(293)
[the unit angstrom () is 10-10 m = 100 pm]
12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01
1 1 1 1 1 1 1 1 1

*Lanthanide Series 6 6 6 6 6 6 6 6 6 6 6 6 6 6
C C C C C C C C C C C C C C
12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01
1 1 1 1 1 1 1 1 1 1 1 1 1 1

Actinide Series 6 6 6 6 6 6 6 6 6 6 6 6 6 6
C C C C C C C C C C C C C C
12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01 12.01
1 1 1 1 1 1 1 1 1 1 1 1 1 1

5 6

1
 6

AtomicNumberandAtomicMass C AtomicStructure:Orbitals
12.011

The atomic number (Z) is the number of protons in Quantum mechanics: describes electron energies
the atom's nucleus (neutral atom then has same and locations by a wave equation
number of electrons) Wave function solution of wave equation
Each wave function is an orbital,
The mass number (A) is the number of protons plus
neutrons
A plot of 2 describes where electron most likely to
All the atoms of a given element have the same be
atomic number
Isotopes are atoms of the same element that have Electron cloud has no specific boundary so we show
different numbers of neutrons and therefore different most probable area
mass numbers (13C, 2H or D)
The atomic mass (atomic weight) of an element is
the weighted average mass in atomic mass units
(amu) of an elements naturally occurring isotopes
(there is no bromine on the planet that weighs 79.9 g/mol)
7 8

ShapesofAtomicOrbitals
Four different kinds of orbitals for electrons based on
those derived for a hydrogen atom
Denoted s, p, d, and f
s and p orbitals most important in organic chemistry
s orbitals: spherical, nucleus at center
p orbitals: dumbbell-shaped, nucleus at middle
pOrbitals
In each shell there are three perpendicular p
orbitals, px, py, and pz, of equal energy
Lobes of a p orbital are separated by region of
zero electron density, a node

9 10

Orbitals andShells AtomicStructure:ElectronConfiguration

Orbitals are grouped in shells of increasing size and energy Ground-state electron configuration of an atom
Different shells contain different numbers and kinds of orbitals
Each orbital can be occupied by two electrons
lists orbitals occupied by its electrons. Rules:
First shell contains one s orbital, denoted 1s, holds only two
electrons 1. Lowest-energy orbitals fill first: 1s 2s 2p 3s
Second shell contains one s orbital (2s) and three p orbitals 3p 4s 3d (Aufbau (build-up) principle)
(2p), eight electrons
Third shell contains an s orbital (3s), three p orbitals (3p), and 2. Electron spin can have only two orientations, up
five d orbitals (3d), 18 electrons
and down . Only two electrons can occupy an
orbital, and they must be of opposite spin (Pauli
valence
shell exclusion principle) to have unique wave equations

3. If two or more empty orbitals of equal energy are

octet for
second row available, electrons occupy each with spins parallel
until all orbitals have one electron (Hund's rule).

11 12

2
ElectronConfigurationandBonding
Z=6 Z=7
How do atoms fill octet? BONDING
Ionic = bonds from exchanging electrons
Covalent = bonds from sharing electrons
Valency = number of covalent bonds needed to fill valence octet
C = tetravalent N = trivalent O = divalent F = monovalent
BondingModel#1:ValenceBondTheory
Singly occupied orbital on one atom
overlaps a singly occupied orbital on
the other atom
Electrons are paired and localized in
the overlapping orbitals and are
attracted to nuclei of both atoms
HH bond results from the overlap
Z=8 Z=9
of two singly occupied hydrogen 1s
orbitals
Certain optimal distance
Smaller, more directional orbitals
make stronger bonds due to
better orbital overlap
(best from smallest, similar size orbitals)
pingpong ball - pingpong ball
pingpong ball - basketball
(H = monovalent also) pingpong ball - watermelon

13 14

HybridizationfortheCarbonAtom sp3 Orbitals

sp3 hybrid orbitals: s orbital and three p orbitals

combine to form four equivalent, unsymmetrical,
tetrahedral orbitals (s+p+p+p = sp3) - note the total
number of orbitals is conserved

smaller back
Why Hybridize? lobes not drawn
1. can now form 4 bonds instead of two to fill octet
2. more directional orbital (increased s-character)
gives stronger bond from better overlap of orbital
3. maximize separation of electrons (VSEPR); 109.5
bond angles instead of 90
more directional orbital
(one side bigger than other)
Again, why can't we use ground state?
15 16

TheStructureofMethane Hybridization:sp3 Orbitals andtheStructure

ofEthane
sp3 orbitals on C overlap with 1s orbitals of 4 H atoms
to form four identical C-H bonds Two Cs bond to each other by overlap of an sp3
Each CH bond has a strength of ~100 kcal/mol orbital from each
Bond angle: each HCH is 109.5, the tetrahedral Three sp3 orbitals on each C overlap with H 1s
orbitals to form six CH bonds
angle
CC bond strength is ~85 kcal/mol
All bond angles of ethane are ~tetrahedral

one Csp3-Csp3 bond

6 Csp3-H1s bonds

17 18

3
sp2 Orbitals
sp2 hybrid orbitals: 2s orbital combines with two 2p
orbitals, giving 3 orbitals (s+p+p = sp2). This results in
a double bond
sp2 orbitals are in a plane with120 angles
Remaining p orbital is perpendicular to the plane
DoubleBondsFromsp2 HybridOrbitals
Two sp2-hybridized orbitals overlap to form a bond
p orbitals overlap side-to-side to form a pi () bond
sp2sp2 bond and 2p2p bond result in sharing
four electrons and formation of C-C double bond
Electrons in the bond are centered between nuclei

Electrons in the bond occupy regions of space

above and below plane of sigma bond
As a result of weaker orbital overlap, bonds are
weaker than sigma bonds (~50 kcal/mol versus ~100
kcal/mol for bond)

19 20

TheStructureofEthylene
H atoms form bonds with four sp2 orbitals
HCH and HCC bond angles of ~120
CC double bond in ethylene shorter and stronger
(~150 kcal/mol) than single bond in ethane
(not twice as strong!)
spOrbitals
sp hybrid orbitals: 2s orbital combines with one 2p
orbital, giving 2 orbitals (s+p = sp). This results in a
triple bond
sp orbitals are linear with 180 angles
Remaining p orbitals are perpendicular to the plane
along the y-axis and z-axis

one Csp2-Csp2 bond

one Cp-Cp bond
4 Csp2-H1s bonds

21 22

TheStructureofAcetylene HybridizationofNitrogenandOxygen
HCC bond angles of ~180 sp3 orbital
Elements other than C can
CC triple bond in acetylene shorter and stronger have hybridized orbitals
(~200 kcal/mol) than double/single bonds
(not two/three times as strong!) HNH bond angle in
ammonia (NH3) 107.3

Ns orbitals (sppp) hybridize to

form four sp3 orbitals
one Csp-Csp bond
One sp3 orbital is occupied by sp3 orbitals
two Cp-Cp bonds
2 Csp-H1s bonds two nonbonding electrons, and
three sp3 orbitals have one
electron each, forming bonds
to H

23 24

4
 SummaryforHybridizationofCarbon BondingModel#2:MolecularOrbitalTheory
(remember,neutralcarbonalwayshasfourbonds)
A molecular orbital (MO): where electrons are most
4 electron groups = sp3 Tetrahedral likely to be found in a molecule (delocalized over the
(four bonds) 109.5 entire molecule not just between atoms like valence
bond)
3 electron groups = sp2 Trigonal Combine n atomic orbitals to give n molecular orbitals
(three bonds) planar Additive combination (bonding) MO is lower in energy
(one bond) 120
Subtractive combination (antibonding) forms MO that
is higher in energy
2 electron groups = sp
(two bonds) Linear
(two bonds) 180

What do you predict for C-H bond ~ 100 kcal/mol

CH3+, CH3-, :CH2 C-C bond ~ 85 kcal/mol
C-C bond ~ 50 kcal/mol

25 26

used for -bonds only

MolecularOrbitals inEthylene DrawingChemicalStructures
The bonding MO is from combining p orbital lobes Chemists use shorthand ways for writing structures
with the same algebraic sign Condensed structures: C-H and C-C single bonds aren't
shown but understood
The antibonding MO is from combining lobes with If C has 3 Hs bonded to it, write CH3
opposite signs
If C has 2 Hs bonded to it, write CH2; and so on. The
Only bonding MO is occupied compound called 2-methylbutane, for example, is written as
follows:
Horizontal bonds between carbons aren't shown in condensed
structuresthe CH3, CH2, and CH units are simply written next
to each other but vertical bonds are added for clarity

27 28

SkeletalStructures ExamplesofSkeletalStructures
Lewis Structure Skeletal Structure
Minimum amount of information but unambiguous
Cs not shown, assumed to be at each intersection of
Pay attention to atom valency and
two lines (bonds) and at end of each line any potential lone pairs.
Hs bonded to Cs aren't shown whatever number is
For neutral atoms:
needed will be there (each neutral carbon will have
four total bonds). H's on non-carbon atoms are C = four bonds, no lone pairs
shown
N = three bonds, one lone pair
All atoms other than C and H are shown
O = two bonds, two lone pairs
Non-bonding electrons not typically shown (assumed
enough to satisfy charge)
Charges (if any) must be explicitly shown

29 30

5
ClassProblems
1. Explain why the hydrogens atoms in the following compound are
not all in the same plane!
2. Predict the hybridization for each of the following central atoms.
ClassProblems
For the following compound provide the following:
hybridization of atoms
bond angles (assume ideal values)
geometry around atom (electronic, atomic)
describe bond overlap, orbital location of lone pairs
provide number of pi-bonds, sigma bonds
provide missing hydrogens (later in 3-D), lone pairs

Will not be asked specific bond length, strength values but you
should be able to qualitatively compare bond lengths and
strengths (predict which is stronger, shorter, etc and explain)
For example, what is the weakest bond to carbon in this
compound? Explain. Which is strongest C-H bond? Explain.

May be asked to draw and label orbitals involved in bonding

For example, what orbitals overlap to form the carbon-oxygen
double bond?
31 32