Organic Chemistry 4th Edition

Paula Yurkanis Bruice

Chapter 1
Electronic Structure and Bonding Acids and Bases

Irene Lee Case Western Reserve University Cleveland, OH 2004, Prentice Hall

Organic Chemistry
Organic compounds are compounds containing carbon Carbon neither readily gives up nor readily accepts electrons

Carbon shares electrons with other carbon atoms as well as with several different kinds of atoms

The Structure of an Atom

An atom consists of electrons, positively charged protons, and neutral neutrons Electrons form chemical bonds Atomic number: numbers of protons in its nucleus

Mass number: the sum of the protons and neutrons of an atom

Isotopes have the same atomic number but different mass numbers The atomic weight: the average weighted mass of its atoms Molecular weight: the sum of the atomic weights of all the atoms in the molecule

The Distribution of Electrons in an Atom

Quantum mechanics uses the mathematical equation of wave motions to characterize the motion of an electron around a nucleus Wave functions or orbitals tell us the energy of the electron and the volume of space around the nucleus where an electron is most likely to be found

The atomic orbital closer to the nucleus has the lowest energy
Degenerate orbitals have the same energy

Table 1.1

 The Aufbau principle: electrons occupy the orbitals with the lowest energy first

The Pauli exclusion principle: only two electrons can occupy one atomic orbital and the two electrons have opposite spin

Hunds rule: electrons will occupy empty degenerated orbitals before pairing up in the same orbital

 Ionic compounds are formed when an electropositive element transfers electron(s) to an electronegative element

Covalent Compounds
Equal sharing of electrons: nonpolar covalent bond (e.g., H2) Sharing of electrons between atoms of different electronegativities: polar covalent bond (e.g., HF)

Electrostatic Potential Maps

A Dipole
A polar bond has a negative end and a positive end

dipole moment (D) = m = e x d

(e) : magnitude of the charge on the atom

(d) : distance between the two charges

Lewis Structure

Formal charge = number of valence electrons (number of lone pair electrons +1/2 number of bonding electrons)

Important Bond Numbers

one bond
H F Cl Br I

two bonds

three bonds

four bonds

The s Orbitals

The p Orbitals

Molecular Orbitals

Molecular orbitals belong to the whole molecule

s bond: formed by overlapping of two s orbitals

Bond strength/bond dissociation: energy required to break a bond or energy released to form a bond

In-phase overlap forms a bonding MO; out-of-phase overlap forms an antibonding MO

Sigma bond (s) is formed by end-on overlap of two p orbitals

A s bond is stronger than a p bond

Pi bond (p) is formed by sideways overlap of two parallel p orbitals

Bonding in Methane and Ethane: Single Bonds

Hybridization of orbitals:

The orbitals used in bond formation determine the bond angles

Tetrahedral bond angle: 109.5

Electron pairs spread themselves into space as far from each other as possible

Hybrid Orbitals of Ethane

Bonding in Ethene: A Double Bond

An sp-Hybridized Carbon

The bond angle in the sp2 carbon is 120

The sp2 carbon is the trigonal planar carbon

Bonding in Ethyne: A Triple Bond

A triple bond consists of one s bond and two p bonds

Bond angle of the sp carbon: 180

Bonding in the Methyl Cation

Bonding in the Methyl Radical

Bonding in the Methyl Anion

Bonding in Water

Bonding in Ammonia and in the Ammonium Ion

Bonding in Hydrogen Halides

Summary
A p bond is weaker than a s bond The greater the electron density in the region of orbital overlap, the stronger is the bond The more s character, the shorter and stronger is the bond The more s character, the larger is the bond angle

Molecular Dipole Moment

The vector sum of the magnitude and the direction of the individual bond dipole determines the overall dipole moment of a molecule

BrnstedLowry Acids and Bases

Acid donates a proton Base accepts a proton

Strong reacts to give weak The weaker the base, the stronger is its conjugate acid

Stable bases are weak bases

An Acid/Base Equilibrium
H2O + HA H3O+ + A-

[H3O+][A-] Ka = [H2O][HA] pKa = -log Ka

Ka: The acid dissociation constant

The HendersonHasselbalch Equation

The pH indicates the concentration of hydrogen ions (H+)

pK a

HA pH log

A compound will exist primarily in its acidic form at a pH < its pKa

A compound will exist primarily in its basic form at a pH > its pKa
A buffer solution maintains a nearly constant pH upon addition of small amount of acid or base

 When atoms are very different in size, the stronger acid will have its proton attached to the largest atom

 When atoms are similar in size, the stronger acid will have its proton attached to the more electronegative atom

Inductive electron withdrawal increases the acidity of a conjugate acid

Acetic acid is more acidic than ethanol O

CH3COH pKa = 4.76 acetic acid CH3CH2OH pKa = 15.9 ethanol

The delocalized electrons in acetic acid are shared by more than two atoms, thereby stabilizing the conjugated base

O CH3CO-

O CH3CO-

Lewis Acids and Bases

Lewis acid: non-proton-donating acid; will accept two electrons

Lewis base: electron pair donors