Acids and Bases

Three acid-base systems:

Arrhenius acids and bases: An Arhennius acid yields a proton in solution. An Arhennius base yields a hydroxide ion in solution. Bronstead-Lowry acids and bases: A Brnsted-Lowry acid is a proton donor. A Brnsted-Lowry base is a proton acceptor. Lewis acids and bases: A Lewis acid is an electron pair acceptor. A Lewis base is an electron pair donor.

KIM3200 Acids & Bases

Brnsted-Lowry Acids and Bases:

Proton donors and acceptors. H+ or H3O+ = a proton
Figure 2.1 Examples of Brnsted - Lowry acids and bases

Reactions of Brnsted-Lowry Acids and Bases:

A Brnsted-Lowry acid base reaction results in the transfer of a proton from an acid to a base. In an acid-base reaction, one bond is broken, and another one is formed. The electron pair of the base B: forms a new bond to the proton of the acid. The acid HA loses a proton, leaving the electron pair in the HA bond on A: . These forms represent conjugate acid/conjugate base pairs. Note the equilibrium arrows.

Acid Strength and pKa:

Acid strength is the tendency of an acid to donate a proton. The more readily a compound donates a proton, the stronger is its acidity. The equilibrium constant is a measure of acidity. When a Brnsted-Lowry acid HA is dissolved in water, an acid-base reaction occurs, and an equilibrium constant can be written for the reaction.

Acids and Bases

Acid Strength and pKa :
Because the concentration of the solvent H2O is essentially constant, the equation can be rearranged and a new equilibrium constant, called the acidity constant, Ka, can be defined.

It is generally more convenient when describing acid strength to use pKa values than Ka values.

Acids and Bases

Acid Strength and pKa :

Acids and Bases

Factors that Determine Acid Strength:
Anything that stabilizes a conjugate base A: makes the starting acid HA more acidic. Four factors affect the acidity of HA. These are: Element effects (trends in periodic table) Inductive effects (electronegativity) Resonance effects (multiple resonance structures) Hybridization effects (sp, sp2, sp3)

Acids and Bases

Factors that Determine Acid Strength:
No matter which of these factors is discussed, to compare the acidity of any two acids: o Always look at the conjugate bases. o Determine which conjugate base is more stable. o The more stable the conjugate base, the more acidic the acid. The strengths of a conjugate acid and its conjugate base are inversely related. A strong conjugate base has a weak conjugate acid. A weak conjugate base has a strong conjugate acid.
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Acids and Bases

Factors that Determine Acid Strength: Element EffectsTrends in the Periodic Table.
Across a row of the periodic table, the acidity of HA increases as the electronegativity of A increases.

Positive or negative charge is stabilized when it is spread over a larger volume.

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Acids and Bases

Factors that Determine Acid Strength: Element EffectsTrends in the Periodic Table.
Down a column of the periodic table, the acidity of H A increases as the size of A increases.

Acids and Bases

Factors that Determine Acid Strength: Inductive Effects
An inductive effect is the pull of electron density through bonds caused by electronegativity differences between atoms. In the example below, when we compare the acidities of ethanol and 2,2,2-trifluoroethanol, we note that the latter is more acidic than the former.

Size, and not electronegativity, determines acidity down a column. The acidity of HA increases both left-to-right across a row and down a column of the periodic table. Although four factors determine the overall acidity of a particular hydrogen atom, element effectsthe identity of Ais the single most important factor in determining the 11 acidity of the HA bond.

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Acids and Bases

Factors that Determine Acid Strength: Inductive Effects
The reason for the increased acidity of 2,2,2trifluoroethanol is that the three electronegative fluorine atoms stabilize the negatively charged conjugate base. This effect is limited to a three bond distance.

Acids and Bases

Factors that Determine Acid Strength: Resonance Effects Resonance is a third factor that influences acidity. In the example below, when we compare the acidities of ethanol and acetic acid, we note that the latter is more acidic than the former.

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Acids and Bases

Factors that Determine Acid Strength: Resonance Effects When the conjugate bases of the two species are compared, it is evident that the conjugate base of acetic acid enjoys resonance stabilization, whereas that of ethanol does not.

Acids and Bases

Factors that Determine Acid Strength: Resonance Effects Resonance delocalization makes CH3COO more stable than CH3CH2O, so CH3COOH is a stronger acid than CH3CH2OH.

The acidity of HA increases when the conjugate base A: is resonance stabilized.

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Acids and Bases

Factors that Determine Acid Strength: Hybridization Effects The final factor affecting the acidity of HA is the hybridization. Let us consider the relative acidities of three different compounds containing CH bonds.

Acids and Bases

Factors that Determine Acid Strength: Hybridization Effects

Figure 2.4 Electrostatic Potential plots

The higher the percent of s-character of the hybrid orbital, the closer the lone pair is held to the nucleus, and the more stable the conjugate base.
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Acids and Bases

Factors that Determine Acid Strength: Summary of Effects
Figure 2.5 Summary of the factors that determine acidity

Acids and Bases

Commonly Used Acids in Organic Chemistry:
In addition to the familiar acids HCl, H2SO4 and HNO3, a number of other acids are often used in organic reactions. Two examples are acetic acid and p-toluene-sulfonic acid (TsOH).

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Acids and Bases

Commonly Used Bases in Organic Chemistry:
Common strong bases used in organic reactions are more varied in structure.
Figure 2.6 Common negatively charged bases

Acids and Bases

Commonly Used Bases in Organic Chemistry:
It should be noted that:
Strong bases have weak conjugate acids with high p Ka values, usually > 12. Strong bases have a net negative charge, but not all negatively charged species are strong bases. For example, none of the halides F, Cl, Br, or I, is a strong base. Carbanions, negatively charged carbon atoms, are especially strong bases. A common example is butyllithium. Two other weaker organic bases are triethylamine and pyridine.

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Acids and Bases

Lewis Acids and Bases:
The Lewis definition of acids and bases is more general than the Brnsted-Lowry definition. A Lewis acid is an electron pair acceptor. A Lewis base is an electron pair donor. Lewis bases are structurally the same as Br nstedLowry bases. Both have an available electron pair a lone pair or an electron pair in a bond. All Brnsted-Lowry acids are also Lewis acids, but the reverse is not necessarily true.

Acids and Bases

Lewis Bases:
A Brnsted-Lowry base always donates this electron pair to a proton, but a Lewis base donates this electron pair to anything that is electron deficient. Common examples of Lewis bases (which are also Brnsted-Lowry bases)

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Acids and Bases

Lewis Acids:
A Lewis acid must be able to accept an electron pair and can be any species that is electron deficient and capable of accepting an electron pair. Common examples of Lewis acids (which are not Brnsted-Lowry acids) include BF3 and AlCl3.

Acids and Bases

Electrophiles and Nucleophiles:
A Lewis acid is also called an electrophile. When a Lewis base reacts with an electrophile other than a proton, the Lewis base is also called a nucleophile. In this example, BF3 is the electrophile and H2O is the nucleophile. A Lewis Acid-Base Reaction:

Electrophile
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Nucleophile
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Acids and Bases

Lewis Acid-Base Reactions: Two other examples are shown below. Note that in each reaction, the electron pair is not removed from the Lewis base. Instead, it is donated to an atom of the Lewis acid and a new covalent bond is formed.

Acids and Bases

Lewis Acids and Bases:
Consider the Lewis acid-base reaction between cyclohexene and HCl. The Brnsted-Lowry acid HCl is also a Lewis acid, and cyclohexene, having a bond, is the Lewis base.

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Acids and Bases

Lewis Acids and Bases:
To draw the product of this reaction, the electron pair in the bond of the Lewis base forms a new bond to the proton of the Lewis acid, generating a carbocation. The HCl bond must break, giving its two electrons to Cl, forming Cl. Because two electron pairs are involved, two curved arrows are needed.

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