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Organic Chemistry, 8th Edition L. G. Wade, Jr.

Chapter 1 Lecture
Introduction and Review

Rizalia Klausmeyer Baylor University Waco, TX


2013 Pearson Education, Inc. 2013 Pearson Education, Inc.

Organic Chemistry
O
H H CH3CH2CH CHCH2CONH O N S CH3 CH3 COONa

O O H5C6 N H C6H5 O O OH H5 C6 O
O H NCH3 HO

O OH

HO O O O CH3

2-Pentenylpenicillin

CH3O

Taxol

Codeine

Organic chemistry is the chemistry of carbon compounds.


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Chapter 1

Electronic Structure of the Atom


An atom has a dense, positively charged nucleus surrounded by a cloud of electrons. The electron density is highest at the nucleus and drops off exponentially with increasing distance from the nucleus in any direction.

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Chapter 1

The 2p Orbitals
There are three 2p orbitals, oriented at right angles to each other. Each p orbital consists of two lobes. Each is labeled according to its orientation along the x, y, or z axis.
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Isotopes
12 6

14 6

Isotopes are atoms with the same number of protons but different number of neutrons. Mass number is the sum of the protons and neutrons in an atom.
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Chapter 1

Electronic Configurations of Atoms


Valence electrons are electrons on the outermost shell of the atom.

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Chapter 1

Electronic Configurations
The aufbau principle states to fill the lowest energy orbitals first. Hunds rule states that when there are two or more orbitals of the same energy (degenerate), electrons will go into different orbitals rather than pairing up in the same orbital.

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Ionic Bonding
To obtain a noble gas configuration (a full valence shell), atoms may transfer electrons from one atom to another. The atoms, now bearing opposite charges, attract each other, forming an ionic bond.

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Covalent Bonding
Electrons are shared between the atoms to complete the octet. When the electrons are shared evenly, the bond is said to be nonpolar covalent, or pure covalent. When electrons are not shared evenly between the atoms, the resulting bond will be polar covalent.

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Chapter 1

Lewis Structures
CH4
H
Carbon: 4 e 4 H@1 e ea: 4 e 8e

NH3
H C H H
Nitrogen: 5 e 3 H@1 e ea: 3 e 8e

H N H H

H2O
Oxygen: 6 e 2 H@1 e ea: 2 e 8e
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Cl2
H O H
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2 Cl @7 e ea: 14 e

Cl Cl
10

Bonding Patterns
Valence electrons # Bonds # Lone Pair Electrons 0 1 2 3
11

C N

4 5 6 7
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4 3 2 1

O
Halides
(F, Cl, Br, I)
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Nonbonding Electrons

Also called lone pairs. Nonbonding electrons are valence shell electrons that are not shared between atoms.

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Multiple Bonding

Sharing two pairs of electrons is called a double bond. Sharing three pairs of electrons is called a triple bond.
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Lewis structures are the way we write organic chemistry. Learning now to draw them quickly and correctly will help you throughout this course.

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Dipole Moment

Dipole moment is defined to be the amount of charge separation (d) multiplied by the bond length (m). Charge separation is shown by an electrostatic potential map (EPM), where red indicates a partially negative region and blue indicates a partially positive region.
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Pauling Electronegativities
Electronegativities can be used to predict whether a bond will be polar and the direction of its dipole moment. Since the electronegativities of carbon and hydrogen are similar, CH bonds are considered to be nonpolar.

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Formal Charges
Formal charge = [group number ] [nonbonding electrons ] [shared electrons]

H3O+
6 2 (6) = +1

NO+
6 2 (6) = +1

H O H H
5 2 (6) = 0

N O

Formal charges are a way of keeping track of electrons. They may or may not correspond to actual charges in the molecule.

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Solved Problem 1
Compute the formal charge (FC) on each atom in H3N BH3.

Solution

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Common Bonding Patterns

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Work enough problems to become familiar with these bonding patterns so you can recognize other patterns as being either unusual or wrong.

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Resonance Forms
The structures of some compounds are not adequately represented by a single Lewis structure. Resonance forms are Lewis structures that can be interconverted by moving electrons only. The true structure will be a hybrid between the contributing resonance forms.

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Resonance Forms
Resonance forms can be compared using the following criteria, beginning with the most important:
1. Has as many octets as possible. 2. Has as many bonds as possible. 3. Has the negative charge on the most electronegative atom. 4. Has as little charge separation as possible.

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Major and Minor Contributors


The major contributor is the one in which all the atoms have a complete octet of electrons.

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Major and Minor Contributors (Continued)


When both resonance forms obey the octet rule, the major contributor is the one with the negative charge on the most electronegative atom.

N C O
MAJOR

N C O
MINOR

The oxygen is more electronegative, so it should have the negative charge.


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Non-Equivalent Resonance
Opposite charges should be on adjacent atoms.
CH3 O N O
MAJOR

CH3 O N O
MINOR

The most stable one is the one with the smallest separation of oppositely charged atoms.

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Solved Problem 2
Draw the important resonance forms for [CH3OCH2]+. Indicate which structure is the major and minor contributor or whether they would have the same energy.

Solution

The first (minor) structure has a carbon atom with only six electrons around it. The second (major) structure has octets on all atoms and an additional bond.

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Solved Problem 3
Draw the resonance structures of the compound below. Indicate which structure is the major and minor contributor or whether they would have the same energy.

Solution

Both of these structures have octets on oxygen and both carbon atoms, and they have the same number of bonds. The first structure has the negative charge on carbon, the second on oxygen. Oxygen is the more electronegative element, so the second structure is the major contributor.

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Resonance Forms for the Acetate Ion

When acetic acid loses a proton, the resulting acetate ion has a negative charge delocalized over both oxygen atoms. Each oxygen atom bears half of the negative charge, and this delocalization stabilizes the ion. Each of the carbonoxygen bonds is halfway between a single bond and a double bond and is said to have a bond order of 1.
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Condensed Structural Formulas


Lewis Condensed

H H H C
1 2

C H

CH3CH3

H H
Condensed forms are written without showing all the individual bonds. Atoms bonded to the central atom are listed after the central atom (CH3CH3, not H3CCH3). If there are two or more identical groups, parentheses and a subscript may be used to represent them.
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Condensed Structural Formulas


Lewis
H H H C
1 2

Condensed
Br CH3CH2CHCH3

Br H
3 4

C C C H

H H H H H H O H H C
1 2

O HOCH2CH2CCH3

C C C H H
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OH H
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Condensed Structural Formulas (Continued)

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Condensed Structural Formulas (Continued)

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Condensed Structural Formulas (Continued)

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Line-Angle Drawings
H H H H H C C C C H H H H H
Sometimes called skeletal structure or stick figure. Bonds are represented by lines, and carbons are present where a line begins or ends and where two lines meet. Hydrogens attached to carbon are not shown. Nitrogen, oxygen, and halides must be shown.
1 2 3 4

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Line-Angle Drawings
H H H H H
1 2 3 4 5 6

O H

H C C C C C C H H H H H

Atoms other than carbon must be shown. Double and triple bonds must also be shown.

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Line-Angle Formulas (Continued)

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Calculating Empirical Formulas


The following are items that need to be considered when calculating empirical formulas:
Given % composition for each element, assume 100 g. Convert the grams of each element to moles. Divide by the smallest number of moles to get ratio. Molecular formula may be a multiple of the empirical formula.
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If an elemental analysis does not add up to 100%, the missing percentage is assumed to be oxygen.

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Arrhenius Acids
Arrhenius acids are substances that dissociate in water to give H3O+ ions.

Stronger acids dissociate to a greater degree than weaker acids.


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Arrhenius Bases
Arrhenius bases are substances that dissociate in water to give hydroxide ions.

Stronger bases (NaOH) dissociate more than weaker bases (Mg(OH)2).


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Brnsted-Lowry Acids and Bases


Brnsted-Lowry acids are any species that donate a proton. Brnsted-Lowry bases are any species that can accept a proton.

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Conjugate Acids and Bases

Conjugate acid: when a base accepts a proton, it becomes an acid capable of returning that proton. Conjugate base: when an acid donates its proton, it becomes capable of accepting that proton back.
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Effect of Electronegativity on pKa


As the bond to H becomes more polarized, H becomes more positive and the bond is easier to break.

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Effect of Size on pKa

As size increases, the H is more loosely held and the bond is easier to break. A larger size also stabilizes the anion.
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Effect of Resonance on pKa

If the negative charge on an atom can be delocalized over two or more atoms, the acidity of that compound will be greater than when the negative charge cannot be delocalized. The ethoxide anion is less acidic than the acetate ion simply because the acetate ion can delocalize the negative charge. Methanesulfonic acid can delocalize the charge in three different resonance forms, making it more acidic than the acetate ion.
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Lewis Acids and Lewis Bases


Lewis bases are species with available electrons than can be donated to form a new bond. Lewis acids are species that can accept these electrons to form new bonds. Since a Lewis acid accepts a pair of electrons, it is called an electrophile.

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Nucleophiles and Electrophiles


Nucleophile: Donates electrons to a nucleus with an empty orbital. Electrophile: Accepts a pair of electrons. When forming a bond, the nucleophile attacks the electrophile, so the arrow goes from negative to positive. When breaking a bond, the more electronegative atom receives the electrons.
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Nucleophiles and Electrophiles

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