Chapter 3: An Introduction to Organic Reactions and  Lewis Acids - electron pair acceptors.

(electrophiles)
Their Mechanisms (Acids and Bases)  Lewis Bases - electron pair donors. (nucleophiles)
 Bases are much the same in the Lewis theory and in
 Reaction Mechanisms - a description of the events the Brønsted–Lowry theory,
that take place on a molecular level as reactants  Group IIIA atoms- common Lewis acids
become products. - have only a sextet of electrons in their outer
 Four Categories: shell.
A) Substitutions – characteristic reactions of  In Lewis Acid-Base Theory, the attraction of
saturated compounds (alkanes and alkyl halides) oppositely charged species is fundamental to
and of aromatic compounds (even though they reactivity
are unsaturated)  Carbon atoms that are electron poor because of
- One group replaces another bond polarity, but are not carbocations, can also be
B) Additions - Characteristic of compounds with electrophiles
multiple bonds  Lewis acid and Lewis base are terms that are used
- all parts of the adding reagent appear in the generally, but when one or the other reacts to form
product a bond to a carbon atom, we usually call it an
- two molecules become one electrophile or a nucleophile.
C) Eliminations – one molecule loses the elements
of another small molecule 4. Heterolysis & Homolysis of Covalent Bonds
- Method for preparing compounds with  Heterolysis- complete transfer of electron
double and triple bonds - results to carbocation and carbonion
D) Rearrangements- a molecule undergoes a - full arrow
reorganization of its constituents parts - Heterolysis doesn’t happen easily by itself. It
often needs help from another molecule (Y:),
1. Bronsted- Lowry Acids & Bases - involve the like a nucleophile that donates electrons.
transfer of protons. - For heterolysis to happen, the bond (A–B) must
 Brønsted–Lowry Acid- donate (or lose) a proton. already have uneven electron sharing — one
 Brønsted–Lowry Base- accept (or remove) a proton. atom (B) slightly negative (δ⁻) and the other (A)
 Conjugate Acid - when a base accepts proton slightly positive (δ⁺).
 Conjugate Base – when an acid loses its proton
 Common Strong Acids and Bases
Acids Bases
HCl LiOH
Hbr NaOH
HI KOH
HNO₃ RbOH  Homolysis – equal sharing of electrons
H₂SO₄ CsOH
HClO₄ Ca(OH)₂
- results to neutral radicals
HClO₃ Sr(OH)₂ - fish hook
Ba(OH)₂

 Acid strength- a measure of the percentage of

ionization and not of concentration.

⇌ = partial H⁺ transfer (weak acid)

→ = full H⁺ transfer (strong acid) 5. The Strength of Bronsted-Lowry Acids and Bases
A. Acidic Constant (Ka)- product/ reactant
 Spectator ions- play no part in the acid–base - Large Ka = Strong Acid =weaker conjugate base
reaction - Large pKa= weaker acid=stronger conjugate
base
2. Illustrating Reactions
 Curved arrows- from the source of electron pair to  The stronger the acid, the weaker will be its
the atom receiving (negative to positive) conjugate base.
 Never use curved arrows to show the movement of
atoms. Atoms are assumed to follow the flow of the 6. Predict the Outcome of Acid–Base Reactions
electrons.  The general principle to apply is this: acid–base
 Make sure that the movement of electrons shown reactions always favor the formation of the weaker
by the curved arrow does not violate the octet rule acid and the weaker base.
for elements in the second row of the periodic  Under equilibrium control
table.  Favor the formation of the most stable (lowest
potential energy)
 The weaker acid and weaker base are more stable
(lower in potential energy) than the stronger acid
and stronger base.

7. Water Solubility as the Result of Salt Formation

3. Lewis Acids and Bases
 Carboxylic acids of higher molecular weight are not  Kinetic Energy - the energy an object has because of
appreciably soluble in water. its motion.
 Because of their acidity, however, water-insoluble  Potential Energy - stored energy, exists only when
carboxylic acids dissolve in aqueous sodium an attractive or repulsive force exists between
hydroxide; they do so by reacting to form water- objects.
soluble sodium salts:  Chemical energy- a form of potential energy
 Increasing bond length generally means increasing  Chemical bond = lowering potential energy
acidity  The more potential energy an object has, the less
o A longer bond (like in HI) is weaker, so it stable it is.
breaks more easily, releasing H⁺ more  Enthalpy- heat content
readily → stronger acid. - negative, exothermic
o Which means “The Stronger the H-X bond, - positive, endothermic
the harder it is to let go of the H+, the
weaker the acid 11. The Relationship Between the Equilibrium constant
o Bond strength to the proton decreases as and the Standard Free-energy Change
we move down the column, increasing its
acidity.  This equation tells the ff:
o Acidity increases as we descend the vertical 1) For a reaction to favor the formation of
column of the Periodic Table products when equilibrium is reached it must
 The greater the electronegativity difference have a negative value for ∆G °. Free energy
between H and the atom it’s bonded to (X), must be lost as the reactants become products
o the more polarized the H–X bond becomes, 2) For reactions with a positive ∆G °, the
o making it easier for H⁺ to dissociate, formation of products at equilibrium is
o resulting in a stronger acid. unfavorable.
o Acidity increases from left to right
 The electronegativity of the atom in question affects  Negative value for ∆H °= negative ∆G °= favor
acidity in two related ways: formation of products
o (1) it affects the polarity of the bond to the  Positive value for ∆S ° = negative ∆G °= favor
proton and formation of products
o (2) it affects the relative stability of the
12. Acidity: Carboxylic Acids vs. Alcohols
anion (conjugate base) that forms when the
 Carboxylic Acid- weak acid
proton is lost.
- pKa = 3-5
 Less electronegative atom → less stable with
 Alcohols – very strong base
negative charge → stronger base.
- pKa = 15-18
 More stable conjugate base → stronger acid.
 the carboxylic acid is a stronger acid
8. The Effect of Hybridization
 The greater acidity of a carboxylic acid is
 Alkyne -sp (50% s char) = weakly acid.
predominantly due to the ability of its conjugate
 Alkene- sp2 (33% s char) = not acidic
base (a carboxylate ion) to stabilize a negative
 Alkane- sp3 (25% s char) = not acidic.
charge better than an alkoxide ion, the conjugate
 Having more s character = lower in energy = anion
base of an alcohol
will be more stable.
 The conjugate base of a carboxylic acid is a weaker
 Also, could mean that ethyne are more
base than the conjugate base of an alcohol.
electronegative. Having electrons closer to the
nucleus makes it more stable.
13. The Effect of Delocalization
 Charge delocalization is always a stabilizing factor
 Possible for a carboxylate, but not an alkoxide:
o No double bond nearby to share electrons
o No resonance structures possible
o charge stuck on one atom

9. Inductive Effects 14. Strength of Phenols as Acids

- are electronic effects transmitted through  Stronger acid than alcohol
bonds.  pKa 10, (alcohol pKa 18)
- The inductive effect of a group can be electron
donating or electron withdrawing. 15. The Effect of Solvent on Acidity
- Inductive effects weaken as the distance from  In the absence of a solvent (i.e., in the gas phase),
the group increases. most acids are far weaker than they are in solution.
 Protic solvent – has hydrogen atom
10. Energy Changes  Solvation of any species decreases the entropy of
 Energy- the capacity to do work the solvent because the solvent molecules become
much more ordered as they surround molecules of
the solute
 Proton transfer are often the first step in many
reactions

16. Acids and Bases in Nonaquaeuos Solutions