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Unit 5 B.L. Acid–Base Reactions in Equilibrium

Acids and Bases – Reactions in Equilibrium

Two acid base theories will be explored in this Equilibrium arrows indicate the if the products or
chapter: reactants are favored
• Bronsted Lowery acid base theory: loss and
gain of a proton
• Lewis acid base theory: donation or
acceptance of a pair of electrons

An Acid Loses a Proton An Acid and its Conjugate Base

A Base Gains a Proton A Base and its Conjugate Acid

When an acid loses a proton, it forms its conjugate base.

When a base gains a proton, it forms its conjugate acid.

An Acid and its Conjugate Base

A Base and its Conjugate Acid Acids Have Different Strengths

When an acid loses a proton, it forms its conjugate base.

When a base gains a proton, it forms its conjugate acid.

The stronger the acid, the weaker its conjugate base.

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Acid Strength

See “Simple pKa Chart” on course

web for a complete list. You must
The stronger the acid, the larger the Ka. know pKa values for exams.

The stronger the acid, the smaller the pKa.

Water & Alcohols Can Act as

Make notecard for pKa/functional groups Either Acid or Base
For example, benzoic acid is a carboxylic acid and all
carboxylic acids can be approximated to a pKa of 5.
Your note card would look like:

An Amine Can Behave An Amine Can Behave

as an Acid and as a Base as an Acid and as a Base

A curved arrow points from the electron donor to the electron acceptor.

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Other Amine Acid/Base Chemistry The Position of Equilibrium

The equilibrium favors formation of the weaker acid.

Determine Position of Equilibrium Determine Position of Equilibrium

acid acid

First Label the acids First Label the acids

Second, approximate the pKas

Determine Position of Equilibrium Determine Position of Equilibrium

Acid Acid Acid Acid

35 15 35 15

First Label the acids First Label the acids

Second, approximate the pKas Second, approximate the pKa value

Equilibrium always favors the weaker

acid(higher pKa value)

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The Stronger the Acid,

Electronegativity Affects pKa Values the Weaker Its Conjugate Base

When atoms are the same size, the strongest acid has
its hydrogen attached to the most electronegative atom. stable bases are weak bases

Why Are Protonated Alcohols Stronger Acids

Why are Alcohols Stronger Acids Than Amines?
Than Protonated Amines?

Oxygen is more electronegative than nitrogen. Oxygen is more electronegative than nitrogen.

Substituents Affect the

Hybridization Affects Electronegativity
Strength of the Acid

inductive electron withdrawal

The weakest acid has the

strongest conjugate base.

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The Length and Strength of a

HX vs Substituted Acetic Acid Trends
Hydrogen Halide Bond
Comparing acids such as HCl to HI, you can think
about the bond strength. The weaker the bond, the
easier to break.
Acid Base
strength Base strength
pKa form

3.14 F-

-7 Cl-

-8 Br-

-9 I-

HX vs Substituted Acetic Acid Trends HX vs Substituted Acetic Acid Trends

For acids such as substituted carboxylic acids, consider the conjugate
base forms. The area circled in red has a lot of excess electron density.
Group near this electron density can help stabilize it if they are
electronegative. Since Cl is more electronegative than Br, the conjugate
base form of 2-chloroacetic acid is more stable - therefore the acid is
stronger
Another way to think about it is bond dipoles. Because the singly bonded
oxygen of the carboxylate is negatively charged, that forces the carbon
next to it to be positively charged, which in turn forces the next carbon to
be negatively charged. The more electronegative atom will stabilize
carbon #2 better

O O O O
base O

OH O Cl Br
F3C OH
δ+ O δ+ O
δ- δ-
O base O
pKa 2.81 pKa 2.86 pKa ~0
Cl Cl
OH O

O base O
Br Br
OH O

A Substituent’s Effect on pKa Why is a Carboxylic Acid a Stronger Acid

Depends on Distance Than an Alcohol?

delocalized electrons (resonance)

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Is a Compound Charged or Neutral? Most Amine-based Drugs are Salts

A carboxylic acid is neutral in its acidic form and charged in its basic form. A carboxylic acid is neutral in its acidic form and charged in its basic form.

An amine is charged in its acidic form and neutral in its basic form. An amine is charged in its acidic form and neutral in its basic form.

Lewis Acids and Bases Lewis Acids and Bases

Lewis definitions:
acid: a species that accepts a share in an electron pair
base: a species that donates a share in an electron pair

All Brønsted acids are Lewis acids.

All Brønsted bases are Lewis bases.

Self-Ionization of Water (1 of 3) Self-Ionization of Water (2 of 3)

Pure water contains a very small number of H3O+ ions and – In pure water, H3O+ and OH– are formed in equal
OH– ions formed by proton transfer from one water molecule
(the proton donor) to another (the proton acceptor). amounts (remember the balanced equation for
the self-ionization of water).
– This means that in pure water:

– The equilibrium constant for the ionization of water, Kw, is

called the ion product of water.

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or posted to a publicly accessible website, in whole or in part. or posted to a publicly accessible website, in whole or in part.

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Self-Ionization of Water (3 of 3) pH and pOH (1 of 3)

– The equation for the ionization of water applies – Because hydronium ion concentrations for most
not only to pure water but also to any aqueous solutions are numbers with negative exponents,
solution. we commonly express these concentrations as pH,
– The product of [H3O+] and [OH–] in any aqueous where:
solution is equal to 1.0 x 10–14. pH = –log [H3O+]
– For example, if we add 0.010 mol of HCl to 1.00 – We can now state the definitions of acidic and
liter of pure water, it reacts completely with basic solutions in terms of pH:
water to give 0.010 mole of H3O+. – Acidic solution: One whose pH is less than 7.0.
– In this solution, [H3O+] is 0.010 or 1.0 x 10–2. – Basic solution: One whose pH is greater than 7.0.
– This means that the concentration of hydroxide – Neutral solution: One whose pH is equal to 7.0.
ion is 1.0 x 10–12.
© 2020 Cengage. All Rights Reserved. May not be scanned, copied or duplicated, © 2020 Cengage. All Rights Reserved. May not be scanned, copied or duplicated,
or posted to a publicly accessible website, in whole or in part. or posted to a publicly accessible website, in whole or in part.

pH and pOH (2 of 3) pH and pOH (3 of 3)

– Just as pH is a convenient way to designate the Table 8.5 pH Values of Some Common Materials/Substances
concentration of H3O+, pOH is a convenient way to Material/Substance pH Material/Substance pH
designate the concentration of OH–. Battery acid 0.5 Saliva 6.5–7.5
pOH = –log[OH–] Gastric juice 1.0–3.0 Pure water 7.0

– The ion product of water, Kw, is 1.0 x 10–14 Lemon juice 2.2–2.4 Blood 7.35–7.45
Vinegar 2.4–3.4 Bile 6.8–7.0
Tomato juice 4.0–4.4 Pancreatic fluid 7.8–8.0
Carbonated 4.0–5.0 Seawater 8.0–9.0
– Taking the logarithm of this equation gives: beverages

pH + pOH = 14 Black coffee 5.0–5.1 Soap 8.0–10.0

Urine 5.5–7.5 Milk of magnesia 10.5
– Thus, if we know the pH of an aqueous solution, we can
Rain (unpolluted) 6.2 Household ammonia 11.7
easily calculate its pOH.
Milk 6.3–6.6 Lye (1.0 M NaOH) 14.0
© 2020 Cengage. All Rights Reserved. May not be scanned, copied or duplicated, © 2020 Cengage. All Rights Reserved. May not be scanned, copied or duplicated,
or posted to a publicly accessible website, in whole or in part. or posted to a publicly accessible website, in whole or in part.