Chapter 3
Acids & Bases
Intro to Organic Reactions & Their Mechanisms
Mechanism
• A reaction mechanism is a detailed description
of the bonding changes as a reaction proceeds
• A plausible mechanism must be consistent
with the principles of organic chemistry
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Types of Reactions
• Addition reactions – usually found in compounds with
multiple bonds
– The component of the multiple bond is lost as the new bonds are
formed
• Elimination reactions – atoms are lost resulting in a multiple
bond
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Types of Reactions
• Substitution reactions – replaces one atom or part of a
molecule with another
• Rearrangements – same number of atoms present in reactant
& product; the bonds have a different arrangement
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Mechanisms
• A mechanism describes what takes place at each
stage of a chemical reaction
• It shows how electrons move as well as how bonds
break and form
• There are two types of bond breaking
– Homolytic (symmetrical) – forms radicals
– Heterolytic (unsymmetrical) – forms ions
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Mechanisms
• Half curved arrow ( ) shows the movement of one
electron
• Whole curved arrow ( ) shows the movement of two
electrons
• There are two types of bond forming
– Homolytic (symmetrical) – one electron from two different atoms pair
up to form a bond
– Heterolytic (unsymmetrical) – two electrons from one atom form a
bond with a second atom
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Mechanisms
• Heterolytic bond breaking and forming are the
most common; usually happens with polar
covalent bonds
– They are sometimes called polar reactions
because they usually have one species more
negative than the other
• Terminology
– Electrophile – more positive, electron poor species
– Nucleophile – more negative, electron rich species
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Mechanisms
• When drawing curved arrows, the nucleophile
(negative) always points toward the electrophile
(positive)
• Nucleophiles can be neutral or negatively charged
– Examples
– Almost anything that has a lone pair can be a
nucleophile
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Mechanisms
• Electrophiles can be neutral or positively
charged
– Examples
• Some compounds can act as either a
nucleophile or an electrophile depending on
what it is reacting with
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Acids and Bases
• Bronsted-Lowry acid – substance that donates a
proton (H+)
• Bronsted-Lowry base – substance that accepts a
proton (H+)
• Example
– HCl is a B-L acid; H2O is a B-L base
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Acids and Bases
• Acid strength is a measure of the % ionization
• Strong acids completely dissociate (ionize) in
water
– Ex: HCl, HI, HBr, H2SO4, HNO3
• Weak acids partially dissociate (ionize) in
water; doesn’t give up a proton easily
– Ex: CH3COOH, HCN, H3PO4
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Acids and Bases in Water
• H3O+ (hydronium) – strongest acid in water
• OH– (hydroxide) – strongest base in water
• When a strong acid or base is added to water
the form hydronium or hydroxide
• Example
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Acids and Bases in Water
• When ionic compounds dissolve in water the
ions are solvated
• Mix HCl(aq) & NaOH(aq)
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Lewis Acids and Bases
• Not all compounds contain hydrogen so the B-L definition
doesn’t always apply
• Lewis acid – substance that can accept a pair of electrons
• Lewis base – substance that can donate a pair of electrons
• Curved arrow indicates e- movement
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Organic Reactions
• The attraction of oppositely charged species is
fundamental to reactivity
• The negative area of one species is attracted
to the positive area of another species
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Carbocations & Carboanions
• Heterolysis of a carbon bond can produce
either a carbocation or carbanion
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Carbocations & Carboanions
• Carbocations are Lewis acids and are
electrophiles (electron seeking)
• All Lewis acids are electrophiles
• Carboanions are Lewis bases & are
nucleophiles
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How to use Curved Arrows
• Curved arrows denote electron flow from a
site of higher electron density to a site with
lower electron density
• Arrows are in the direction from the
nucleophile to the electrophile
• Example
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Acids and Bases
• Organic acids are weak acids
• Many biological reactions involve organic
acids and bases
• Major types:
– Compounds that have H attached to an
electronegative atom
– Compounds that have H attached to a carbon next
to a C=O
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Acids and Bases
• The strength of an acid can be expressed by the
acidity constant (Ka)
𝐴− [𝐻3 𝑂+ ]
𝐾𝑎 =
[𝐻𝐴]
• Strong acids have larger Ka values; weaker acids
have smaller Ka values
• Ka values range from 1015 to 10-60
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Acids and Bases
• Its easier to express acidity in terms of pKa
pKa = -log(Ka)
• Strong acids: small pKa (large Ka)
• Weak acids: large pKa (small Ka)
Check out
Table 3.1 in
the book on
page 115
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Acids & Bases
• Predicting base strength
– The stronger the acid, the weaker its conjugate
base
– The larger the pKa value of the conjugate acid, the
stronger the base
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Acids and Bases
• Predicting acid-base reactions
– Acid-base reactions always favor the formation of
the weaker acid and weaker base
– Example 1:
– Example 2:
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Acids and Bases
• Carboxylic acids – contain a COOH group; a
type of organic acid
– Example: acetic acid (CH3COOH)
• Organic bases – usually contain an atom that
has a lone pair of electrons (like amines)
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Water Solubility
• Most medicines are organic compounds – they are turned into salts that
the body can absorb
• Several carboxylic acids that contain less than 5 carbons are water soluble
• Most organic compounds that have more than 5 carbons are not water
soluble
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Bond Strength & Acidity
• The stronger the bond, the weaker the acid
• A strong acid has a weak bond – easy to lose a
proton (H+)
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Electronegativity & Acidity
• Acidity increases as electronegativity increases
• Fluorine is the most electronegative & holds
electrons close to itself but farther away from
the other atom
• A strong acid has a weak conjugate base
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Hybridization & Acidity
• The more S character, the more acidic
• Having more S character means that the
electrons on the anion will be lower in energy
& the anion will be more stable
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Inductive Effects
• Electronic effects transmitted through bonds
• The effects weaken as the distance from the
group increases
• Fluorine is electron withdrawing
• C1 is more positive than C2
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Energy Changes
• The stability of a system is inversely related to
its potential energy
• Chemical energy (energy of molecules) is a
form of potential energy
• “The more energy an object has, the less
stable it is”
• Chemists use the word stability to describe
systems – the most stable system has the
lowest energy
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Thermodynamics Review
• ΔH = enthalpy (heat)
– Positive value = endothermic reaction
– Negative value = exothermic reaction
• ΔG = Gibbs free energy
– Positive value = reactant favored
– Negative value = product favored
• ΔS = entropy (disorder)
– Positive value = more disorder
– Negative value = more order
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Carboxylic Acids
• If you compare a carboxylic acid to an alcohol,
why is the carboxylic acid more acidic?
• Resonance of the conjugate base – can
stabilize the negative charge by delocalizing it
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Carboxylic Acids
• Carboxylic acids also have more inductive
effects than alcohols
• Carboxylic acids do not have as much electron
density holding onto the hydrogen
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Substituent Effects
• Electron withdrawing groups near the
carboxylic acid can increase its acidity
• Any factor that stabilizes the conjugate base of
an acid increases the acid strength
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Solvent Effects on Acidity
• Protic solvent – has a hydrogen attached to a strong
electronegative atom
– Example: H2O, CH3OH, NH3, etc.
• Water causes acetic acid to be more acidic when
dissolved
• Water solvates the ions & stabilizes them
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Organic Bases
• Compounds with lone pairs have the potential
to be bases
• Proton transfer is the very first step in many
reactions
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Organic Reaction Mechanisms
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Acids & Bases in Non-Aqueous Solutions
• Water donates a proton to any base stronger
than hydroxide
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Acids & Bases in Non-Aqueous Solutions
• Alcohols are good solvents because they are
less polar than water & dissolve less polar
compounds
• Bases much stronger than hydroxide:
– BuLi, EtLi, LDA (lithium diisopropylamide), NaNH2,
NaH, acetylides, & more
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Practice Problems
• Chapter 3 (12th Ed.): 1-19, 20, 22-28, 30, 34,
35, 38, and 44
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