LJ

CHP 9 SLIDES

Acids and Bases, pH, and

Buffers

Chapter 9

Guinn, Essentials of General, Organic, and Biochemistry, 3e,

©2019 W. H. Freeman and Company

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 1Outline

9.1 Acids and Bases

9.2 pH

9.3 Acid-Base Neutralization

Reactions

9.4 Buffers

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 2Concepts in Context:

Metabolic Acidosis and Blood pH

A marathon runner stumbles into an aid station breathing

heavily and acting confused.

Nurse measures arterial blood pH and finds it below normal.

• Treatment – IV of saline plus oral sodium bicarbonate

• Result – runner recovers fairly quickly

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 3Importance of Maintaining

Blood pH

Proper organ function

requires blood pH to be

between 7.35 and 7.45, acid-

base homeostasis.

• acidosis = pH < 7.35

• alkalosis = pH > 7.45

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 4Cellular Metabolism and Metabolic Acidosis

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 5Acid-Base Homeostasis in the Blood

Cellular metabolism produces substances that affect blood pH

such as CO2 and H+ ions.

Blood pH maintained by

-increasing respiration to exhale more CO2, or

-shifting buffer equilibria to consume more H+

.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 69.1 Acids and Bases

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 7Core Concept – Acids and Bases

Acids and bases are found in many household

products and in various foods.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 8In Aqueous Solution, Acids Produce Hydronium Ions

Acids produce hydronium ions, H3O+

.

H3O+ = polyatomic ion – water molecule, H2O, + proton, H+

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 9In Aqueous Solution, Bases Produce Hydroxide Ions

Bases produce hydroxide ions, OH–

.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 10Core Concept – Arrhenius Definition

According to the Arrhenius definition, an acid is a substance

that produces hydronium ions, H3O+, and a base is a substance

that produces hydroxide ions, OH–, in aqueous solution.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 11Ionic Compounds Containing Hydroxide Ions

Are Bases

Group 1A hydroxide salts:

NaOH, KOH

soluble in water

strong electrolytes

dissolve entirely to

produce ions in water

Group 2A hydroxide salts:

Ca(OH)2, Mg(OH)2

slightly soluble in water

weak electrolytes

dissolve slightly to produce

few ions in water

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 12Core Concept – Soluble Hydroxide Ion Salts

Soluble hydroxide ion salts (group 1A salts) are strong

electrolytes, and slightly soluble hydroxide ion salts (group 2A

salts) are weak electrolytes.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 13Core Concept – Ionic Compounds Composed

of Hydroxide Ions

Ionic compounds composed of hydroxide ion (OH–) are bases

because they produce solvated hydroxide ions in solution.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 14PE 9-2 HF, HCl, HBr, and HI are acids. What

common product do they all produce in water?

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 15PE 9-2 HF, HCl, HBr, and HI are acids. What

common product do they all produce in water?

(Answer)

hydronium ion, H3O+

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 16PE 9-4 Which of the following ionic

compounds is a base ? Explain.

a. Ba(OH)2

b. NaBr

c. LiOH

d. CaBr2

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 17PE 9-4 Which of the following ionic

compounds is a base ? Explain. (Answer)

Ionic compounds that are bases contain hydroxide ion, OH–

.

a. Ba(OH)2

b. NaBr

c. LiOH

d. CaBr2

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 18Brønsted–Lowry Theory of Acids and Bases

Acid: a proton (H+) donor Base: a proton (H+) acceptor

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 19Acids, According to Brønsted–Lowry Theory

Hydrochloric acid, HCl, donates a proton to a water molecule,

which acts as a base by accepting the proton.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 20Brønsted–Lowry Theory Terminology

Neutral acid loses proton to form conjugate base.

A conjugate base has one fewer H+ and, thus, a –1 charge

(compared to formula of acid).

HCl → Cl–

Water acts as a base, accepting proton to form conjugate acid.

A conjugate acid has one more H+ and, thus, a +1 charge

(compared to formula of base).

H2O → H3O+

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 21Core Concept - Brønsted-Lowry Defintions

According to the Brønsted-Lowry theory, when an acid is

added to water, the acid donates a proton to water to form

the conjugate base; and water accepts a proton to form

hydronium ion (H3O+), the conjugate acid of water.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 22Bases, According to Brønsted–Lowry Theory

Ammonia, NH3, acts as a base by accepting a proton from a

water molecule, which now acts as an acid.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 23Brønsted–Lowry Theory Terminology

(continued)

Neutral base accepts a proton to form the conjugate acid.

A conjugate acid has one more H+ and, thus, a +1 charge.

NH3 ⇄ NH4

+

Neutral water donates a proton to form conjugate base.

A conjugate base has one fewer H+ and, thus, a –1 charge.

H2O ⇄ OH–

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 24Core Concept - Brønsted-Lowry Theory

According to the Brønsted-Lowry theory, a base accepts a

proton from water to produce the conjugate acid, and water

donates a proton to the base to form hydroxide ion (OH–).

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 25Water

According to the Brønsted-Lowry theory, water can accept or

donate a proton.

Water can act as an acid or a base.

Any substance that can act as an acid or a base is an

amphoteric compound.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 26Core Concept – Amphoteric Compounds

Amphoteric compounds can act as either an acid or a base.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 27Conjugate Acid-Base Pairs

An acid and its conjugate base or a base and its conjugate acid

are called a conjugate acid-base pair.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 28Core Concept – Acid-Base Conjugate Pairs

An acid and its conjugate base are a conjugate acid-base pair.

A base and its conjugate acid are a conjugate acid-base pair.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 29Which H+ Can Be Donated?

Only certain H atoms can be donated, and these are usually

indicated at the beginning of a formula.

HCl hydrochloric acid Cl– chloride ion

HC2H3O2 acetic acid C2H3O2

– acetate ion

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 30Predicting Formula of Conjugate Base

Start with

formula and

charge of the

acid.

Decrease

number of H

atoms by 1.

Decrease

charge by 1.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 31Predicting Formula of Conjugate Acid

Start with

formula and

charge of base.

Add an H to the

formula.

Add +1 charge.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 32Core Concept – Acid to Conjugate Base and

Base to Conjugate Acid

The conjugate base of an acid has one fewer hydrogen and a

charge one unit more negative than the acid. The conjugate

acid of a base has one more hydrogen and a charge one unit

more positive than the base.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 33PE 9-6 Label the conjugate acid-base pairs.

a. H2SO4 + H2O → H3O+ + HSO4

b. HCO3

– + H2O ⇄ OH– + H2CO3

c. HI + H2O → I– + H3O+

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 34PE 9-6 Label the conjugate acid-base pairs.

(Answer a)

a. H2SO4 + H2O → H3O+ + HSO4

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 35PE 9-6 Label the conjugate acid-base pairs.

(Answer b)

a. H2SO4 + H2O → H3O+ + HSO4

b. HCO3

– + H2O ⇄ OH– + H2CO3

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 36PE 9-6 Label the conjugate acid-base pairs.

(Answer c)

a. H2SO4 + H2O → H3O+ + HSO4

b. HCO3

– + H2O ⇄ OH– + H2CO3

c. HI + H2O → I– + H3O+

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 37PE 9-9 Hydrogen phosphate, HPO4

2–, is an amphoteric ion.

What is its conjugate acid? What is its conjugate base?

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 38PE 9-9 Hydrogen phosphate, HPO4

2–, is an amphoteric ion.

What is its conjugate acid? What is its conjugate base?

(Answer part 1)

The conjugate acid has one more H+ and +1 charge compared

to HPO4

2–

:

H2PO4

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 39PE 9-9 Hydrogen phosphate, HPO4

2–, is an amphoteric ion.

What is its conjugate acid? What is its conjugate base?

(Answer part 2)

The conjugate acid has one more H+ and +1 charge compared

to HPO4

2–

:

H2PO4

The conjugate base has one less H+ and –1 charge compared

to HPO4

2–

:

PO4

3–

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 40Strengths of Acids and Bases

Strength of an acid depends on the extent to which the

acid donates a proton to water.

Strength of a base depends on the extent to which the

base accepts a proton from water.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 41Strong Acids

Strong acids dissociate in water

completely to form a conjugate

base and hydronium ions.

HCl is the only strong acid

produced in human body.

Strong acids are highly corrosive

when concentrated, but are

safe to handle as dilute

solutions.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 42Six Common Strong Acids

Acid Name Conjugate Base Name of Ion

HNO3 Nitric acid NO3

Nitrate ion

H2SO4 Sulfuric acid HSO4

Hydrogen sulfate ion

HClO4 Perchloric acid ClO4

Perchlorate ion

HCl Hydrochloric acid Cl−

Chloride ion

HBr Hydrobromic acid Br−

Bromide ion

HI Hydroiodic acid I−

Iodide ion

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 43Core Concept – Strong Acids

In solution, a strong acid contains mostly H3O+ and

the conjugate base, and very little of the acid. Strong

acids are strong electrolytes because they produce

many ions in solution.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 44Strong Bases

(Groups 1A and 2A Metal Ions with Hydroxide Ions)

Completely dissociate in aqueous solution, producing hydroxide

ions and cations (conjugate acids).

Strong electrolytes if soluble

Strong bases are highly corrosive when concentrated; can be

handled safely as dilute solutions.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 45Common Strong Bases

Formula Unit Name

Ba(OH)2 Barium hydroxide

Ca(OH)2 Calcium hydroxide

LiOH Lithium hydroxide

KOH Potassium hydroxide

NaOH Sodium hydroxide

Sr(OH)2 Strontium hydroxide

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 46Core Concept – Strong Bases

Strong bases include ionic compounds composed of hydroxide

ions and group 1A or 2A metal ions. Strong bases of soluble

ionic compounds are strong electrolytes.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 47PE 9-11 Which of the following compounds is

a strong acid?

a. H2SO4

b. H2O

c. H2CO3

d. HF

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 48PE 9-11 Which of the following compounds is

a strong acid? (Answer)

a. H2SO4

b. H2O

c. H2CO3

d. HF

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 49PE 9-12 Identify any strong bases.

a. Ca(OH)2

b. NH3

c. NaOH

d. methylamine, CH3NH2

e. Ba(OH)2

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 50PE 9-12 Identify any strong bases. (Answer)

a. Ca(OH)2

b. NH3

c. NaOH

d. methylamine, CH3NH2

e. Ba(OH)2

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 51Weak Acids and Weak Bases

Characterized by little dissociation in water; produce few ions

in aqueous solution; are weak electrolytes.

Reaction with water is reversible. At equilibrium,

reactants > products.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 52Acetic Acid Is a Weak Acid and a Weak Electrolyte

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 53Examples of Weak Acids

Organic acids: acetic acid (HC2H3O2) and citric acid (H3C6H5O7)

Inorganic acids: carbonic acid (H2CO3), phosphoric acid

(H3PO4), and hydrofluoric acid (HF)

Any acid NOT listed in the Six Common Strong Acids

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 54Ammonia, NH3, Is a Weak Base

Nonbonding pair of electrons on N forms bond with H+ to form

conjugate acid.

Common organic weak bases include N with nonbonding electron

pair and N—C bonds.

Common inorganic weak bases: hydrogen carbonate ion (HCO3

–)

and carbonate ion (CO3

2–)

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 55PE 9-14 Strong or weak acid?

a. acetic acid, HC2H3O2

b. nitric acid, HNO3

c. hydrochloric acid, HCl

d. hydrofluoric acid, HF

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 56PE 9-14 Strong or weak acid? (Answer)

a. acetic acid, HC2H3O2 weak

b. nitric acid, HNO3 strong

c. hydrochloric acid, HCl strong

d. hydrofluoric acid, HF weak

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 57Le Châtelier’s Principle

Reaction shifts in direction that counteracts a disturbance.

• Forward reaction enhanced (a shift to the right) until a new

equilibrium is attained.

• Reverse reaction enhanced (a shift to the left) until a new

equilibrium is attained.

Very important in weak-acid and weak-base reactions.

Biochemical pathways – reactions are approaching equilibrium.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 58Carbonic Acid in Aqueous Solution

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 59PE 9-17 Ammonia, NH3, is a weak base.

a. b. c. Write the equilibrium reaction for ammonia, NH3, in

aqueous solution.

If additional hydroxide ions, OH–, are added, will the

reaction shift to the left or to the right? Explain.

If some ammonia molecules are removed from solution,

will the reaction shift to the left or to the right? Explain.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 60PE 9-17 Ammonia, NH3, is a weak base.

(Answer part a)

a. Write the equilibrium reaction for ammonia, NH3, in

aqueous solution.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 61PE 9-17 Ammonia, NH3, is a weak base.

(Answer part b)

b. If additional hydroxide ions, OH–, are added, will the

reaction shift to the left or to the right? Explain.

Adding hydroxide will enhance the reverse reaction and cause

a shift to the left.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 62PE 9-17 Ammonia, NH3, is a weak base.

(Answer part c)

c. If some ammonia molecules are removed from solution,

will the reaction shift to the left or to the right? Explain.

Removing ammonia molecules will decrease the rate of the

forward reaction and, thus, enhance the reverse reaction,

causing a shift to the left.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 639.2 pH

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 64pH

pH measures concentration of hydronium ions (H3O+) in

aqueous solution.

[H3O+] = molar concentration (mole/L) of H3O+

[OH–] = molar concentration of OH–

pH < 7 is acidic, [H3O+] > [OH–]

pH > 7 is basic (alkaline), [H3O+] < [OH–]

pH = 7 is neutral, [H3O+] = [OH–]

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 65Physiologic pH

Blood pH: 7.35–7.45

• Lower = acidosis; higher = alkalosis

• Can be life-threatening

Other body fluids also have specific normal pH values.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 66pH of Some Body Fluids

Body Fluid Normal pH range

Gastric fluid 0.5–2

Urine 5–8

Saliva 6.5–7.5

Muscle cells 6.7–6.8

Arterial blood 7.35–7.45

Interstitial fluid 7.35

Intracellular fluid ≤7.0

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 67Core Concept – Physiological pH

Physiological pH is between 7.35 and 7.45. Acidosis occurs

when blood plasma pH is lower than 7.35, and alkalosis occurs

when the pH is above 7.45.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 68Kw and the Autoionization of Water

Autoionization of water occurs when very few water

molecules react with other water molecules to produce

hydronium ions and hydroxide ions.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 69Kw and the Autoionization of Water

(continued)

In pure water at 25 °C,

[H3O+] = 1.0 × 10–7 M

[OH–] = 1.0 × 10–7 M

𝐾! = H"O# × OH$

𝐾! = 1×10$% × 1×10$% = 1×10$&'

𝐾! = 10$&'

Kw

= ion-product constant for water

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 70Core Concept – Ion Product Constant, Kw

In pure water, the concentration of hydroxide and hydronium

ions is 1 × 10–7 M. The product of these two concentrations is

equal to the ion product constant, Kw. At room temperature,

Kw = 1 × 10–14. Thus, [H3O+] × [OH–] = 1 × 10–14

.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 71Calculating Hydroxide and Hydronium Ion

Concentrations Using the Ion-Product Constant

(part 1)

When acid or base is added to water, autoionization of water

shifts, but Kw is constant. Kw = 10–14

.

When hydronium ion increases, hydroxide must decrease.

[H3O+] /[OH-]

[H3O+] /[OH-]

and vice versa.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 72Calculating Hydroxide and Hydronium Ion

Concentrations Using the Ion-Product Constant

(part 2)

Add acid to water: H!O" increases from 1×10#$ 𝑀 to

1×10#% 𝑀.

H!O" × OH#

= 1×10#&'

1×10#% × 1×10#( = 1×10#&'

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 73Calculating Hydroxide and Hydronium Ion

Concentrations Using the Ion-Product Constant

(part 3)

H!O" × OH#

= 1×10#&'

1×10#&'

H!O" =

OH#

1×10#&'

OH#

=

H!O"

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 74Core Concept – The Ion Product Constant

The ion product constant is H3O+ × 𝑂𝐻#

= 1×10#&' at 25

℃. Using this equation, [H3O+] can be calculated from [OH–],

or [OH–] can be calculated from [H3O+].

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 75Table 9.4

The Relationship

between pH and

the

Concentration of

H3O+ and OH−

in

Solution

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 76PE 9-19 What is the hydroxide ion concentration for an

aqueous solution with a hydronium ion concentration

of 1 × 10–3 M?

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 77PE 9-19 What is the hydroxide ion concentration for an

aqueous solution with a hydronium ion concentration

of 1 × 10–3 M? (Answer)

H!O" × OH#

1×10!"#

= 1×10#&'

1×10!"#

OH!

=

=

= 𝟏×𝟏𝟎!𝟏𝟏 𝑴

H$O%

1×10–3

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 78PE 9-20 What is the hydronium ion concentration for an

aqueous solution with a hydroxide ion concentration of

1 × 10–10 M?

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 79PE 9-20 What is the hydronium ion concentration for an

aqueous solution with a hydroxide ion concentration of

1 × 10–10 M? (Answer)

H!O" × OH#

1×10!"#

= 1 × 10#&'

1×10!"#

H$O% =

OH!

=

= 𝟏×𝟏𝟎!𝟒 𝑴

1×10–10

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 80Calculating pH from the Hydronium Ion

Concentration

pH of an aqueous solution = the logarithm of the hydronium

ion concentration multiplied by –1.

pH = −log"#[H$O%]

For pure water,

pH = −log"( 1×10!) = 7.0

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 81pH Scale

pH decreases as hydronium ion increases.

[H3O+] = 1 × 10–6 has a pH = 6

[H3O+] = 1 × 10–4 has a pH = 4

Differ by 2 pH units, but

100 times different in

concentration!

pH scale is logarithmic; each unit is a 10-fold change in

hydronium and hydroxide ion concentrations

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 82Core Concept - pH

pH = –log[H3O+]. As the hydronium ion concentration increases

and the hydroxide ion concentration decreases, pH decreases.

The pH scale is a logarithmic scale.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 83PE 9-23. What is the pH of a solution with a hydronium

ion concentration of 1 × 10–9 M? Is this solution acidic,

neutral, or basic?

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 84PE 9-23. What is the pH of a solution with a hydronium

ion concentration of 1 × 10–9 M? Is this solution acidic,

neutral, or basic? (Answer)

pH = – log[H3O+]

pH = – log 1×10!* = 𝟗. 𝟎

The solution is basic.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 85PE 9-29 What is the hydronium ion concentration

of a sample of stomach acid with a pH = 2?

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 86PE 9-29 What is the hydronium ion concentration

of a sample of stomach acid with a pH = 2?

(Answer)

pH = – log 𝑥 rearranges to – pH = log 𝑥

10#)* = 𝑥

𝑥 = 10#)* = 10#+

H3O +

= 𝟏×𝟏𝟎!𝟐 𝑴

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 879.3 Acid-Base Neutralization Reactions

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 88Acid-Base Neutralization Reactions

When an acid is combined with a base, a neutral product is

formed and a neutralization reaction has occurred.

Neutralization reactions are double replacement reactions.

Antacids react with stomach acid (HCl) and neutralize the acid.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 89Common Bases Used in Neutralization Reactions

Ionic compounds containing:

• hydroxide ion, OH–

• hydrogen carbonate ion, HCO3

• carbonate ion, CO3

2–

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 90Core Concept – Neutralization Reaction

The reaction between an acid and a base to form a neutral

product is known as a neutralization reaction.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 91Neutralization Reactions with Bases

Containing Hydroxide Ions

If an equal numbers of moles of NaOH and HCl are combined,

the result is a neutral solution.

Sodium and chloride ions are unchanged during the reaction;

they remain in solution as spectator ions.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 92Net Reaction for Reaction of Any Acid and

Hydroxide Ions

OH&(aq) + H%(aq) → H'O(l)

hydroxide ion hydrogen ion water

(base) (acid) (neutral)

H+ from any acid combines with OH– from any base

to form neutral water.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 93Core Concept – A Neutralization Reaction

Produces Water and a Salt

The reaction of an acid with a hydroxide ion-containing

base produces water and a dissolved salt. The net reaction

is H+ + OH– ® H2O. The solution is neutral when an equal

number of moles of hydroxide ions, OH–, and protons, H+

,

are combined.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 94Neutralization Reactions with Polyprotic Acids

Acids with more than one acidic proton are known as

polyprotic acids.

• sulfuric acid, H2SO4

• phosphoric acid, H3PO4

• citric acid, H3C6H5O7

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 95Neutralization Reactions with Polyprotic Acids

(continued)

All acidic protons can be donated in a neutralization reaction.

One hydroxide ion is needed to neutralize each acidic proton.

Combine the spectator ions in a ratio that forms a neutral salt

for the ionic compound.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 96Core Concept – Polyprotic Acid

A polyprotic acid is an acid with two or more acidic

protons, H+. In a neutralization reaction, a polyprotic acid

donates all of its acidic protons to hydroxide ions to form

water molecules and a salt.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 97PE 9-30 Answer the questions below for the neutralization

reaction between aqueous hydrobromic acid, HBr, and

aqueous potassium hydroxide, KOH.

a. b. c. d. e. Which solution is acidic? What ions are dissolved in the acidic

solution?

Which solution is basic? What ions are dissolved in the basic solution?

Write the complete balanced equation for the neutralization reaction.

Remember to first determine the correct formula unit for the ionic

compound formed.

What is the net reaction?

What is a spectator ion? What are the spectator ions in this

neutralization reaction?

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 98PE 9-30 Answer the questions below for the neutralization

reaction between aqueous hydrobromic acid, HBr, and

aqueous potassium hydroxide, KOH. (Answer a)

a. Which solution is acidic? HBr solution

What ions are dissolved in the acidic solution? H+ and Br–

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 99PE 9-30 Answer the questions below for the neutralization

reaction between aqueous hydrobromic acid, HBr, and

aqueous potassium hydroxide, KOH. (Answer b)

b. Which solution is basic?

KOH solution

What ions are dissolved in the basic solution?

K+ and OH–

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 100PE 9-30 Answer the questions below for the neutralization

reaction between aqueous hydrobromic acid, HBr, and

aqueous potassium hydroxide, KOH. (Answer c)

c. Write the complete balanced equation for the

neutralization reaction.

HBr (aq) + KOH (aq) → H2O (l) + KBr (aq)

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 101PE 9-30 Answer the questions below for the neutralization

reaction between aqueous hydrobromic acid, HBr, and

aqueous potassium hydroxide, KOH. (Answer d)

d. What is the net reaction?

OH– (aq) + H+ (aq) ® H2O (l)

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 102PE 9-30 Answer the questions below for the neutralization

reaction between aqueous hydrobromic acid, HBr, and

aqueous potassium hydroxide, KOH. (Answer e)

e. What is a spectator ion?

Spectator ions are ions that are unchanged during

the reaction.

What are the spectator ions in this neutralization

reaction? K+ and Br–

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 103PE 9-31b Complete and balance the

neutralization reaction of HF and Al(OH)3.

HF (aq) + Al(OH)3 (s) →

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 104PE 9-31b Complete and balance the neutralization

reaction of HF and Al(OH)3. (Answer)

3 HF (aq) + Al(OH)3 (s) → 3 H2O (l) + AlF3

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 105Hydrogen Carbonate and Carbonate

Ion-Containing Bases

Ionic compounds containing hydrogen carbonate, HCO3

–, and

carbonate ion, CO3

:

• are weak bases,

• are frequently used in neutralization reactions, and

• can react with acids to produce water, an ionic

compound and CO2 gas.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 106Reaction of Baking Soda and Vinegar

HC2H3O2(aq) + NaHCO3 (aq) → H2O(l) + NaC2H3O2(aq) + CO2(g)

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 107Core Concept – Gas Producing Neutralization

Reaction

The products of the reaction between an acid and a hydrogen

carbonate (HCO3

–) or carbonate ion (CO3

2–) containing base

are water, an ionic compound, and carbon dioxide gas.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 108Net Reactions

Between hydrogen carbonate ion and acids:

H+ (aq) + HCO3- (aq) ® H2O (l) + CO2 (g)

Between carbonate ion and acids:

2H+ (aq) + CO3

2- (aq) ® H2O (l) + CO2 (g)

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 109Core Concept – Net Reaction of a Gas

Producing Neutralization Reaction

The net reaction in a neutralization reaction involving

hydrogen carbonate ion (HCO3

–) is H+ + HCO3

® H2O + CO2,

and for carbonate ion (CO3

2–) it is 2 H+ + CO3

2– ® H2O + CO2.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 110PE 9-33 Write the complete balanced equation for the

reaction between hydroiodic acid, HI, and potassium hydrogen

carbonate, KHCO3. What are the spectator ions? What is the

net reaction?

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 111PE 9-33 Write the complete balanced equation for the

reaction between hydroiodic acid, HI, and potassium hydrogen

carbonate, KHCO3. What are the spectator ions? What is the

net reaction? (Answer part 1)

Balanced equation:

HI (aq) + KHCO3 (aq) → H2O (l) + CO2 (g) + KI (aq)

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 112PE 9-33 Write the complete balanced equation for the

reaction between hydroiodic acid, HI, and potassium hydrogen

carbonate, KHCO3. What are the spectator ions? What is the

net reaction? (Answer part 2)

Balanced equation:

HI (aq) + KHCO3 (aq) → H2O (l) + CO2 (g) + KI (aq)

Spectator ions: I– and K+

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 113PE 9-33 Write the complete balanced equation for the

reaction between hydroiodic acid, HI, and potassium hydrogen

carbonate, KHCO3. What are the spectator ions? What is the

net reaction? (Answer part 3)

Balanced equation:

HI (aq) + KHCO3 (aq) → H2O (l) + CO2 (g) + KI (aq)

Spectator ions: I– and K+

Net reaction:

H+ (aq) + HCO3

– (aq) → H2O (l) + CO2 (g)

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 1149.4 Buffers

Buffer = solution that resists changes in pH when small

amounts of acid or base are added.

How acid-base homeostasis works to prevent acidosis and

alkalosis.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 115Buffer Components

Weak acid + its conjugate base in similar concentrations.

pH range maintained by buffer depends on identity of the

weak acid.

Buffer capacity depends on the concentration of the buffer

components.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 116Table 9-5 Common Buffers

Buffer Weak Acid Conjugate

Base

Function

Acetic acid/acetate

buffer

CH3COOH CH3COO−

Common laboratory

buffer

Carbonic

acid/hydrogen

carbonate buffer

H2CO3 HCO3

Extracellular buffer

Dihydrogen

phosphate/hydrogen

phosphate buffer

H2PO4

HPO4

2−

Intracellular buffer and

common laboratory

buffer

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 117Core Concept - Buffers

A buffer contains approximately equal concentrations of a

weak acid and its conjugate base, therefore resisting changes

in pH when a small amount of acid or base is added.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 118The Buffer Equilibrium

Adding H3O+ increases the rate of the reverse reaction,

producing more HA and H2O, a shift to the left.

[H3O+] changes only a very little, resulting in a relatively

constant pH. pH = –log [H3O+]

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 119The Buffer Equilibrium (continued)

Adding OH– decreases [H3O+], slowing the rate of reverse

reaction, producing more H3O+ and A –, a shift to the right.

Again, [H3O+] changes only a very little, resulting in a relatively

constant pH. pH = –log [H3O+]

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 120Core Concept – How a Buffer Works

A buffer resists changes in pH because the equilibrium shifts in

response to the addition or removal of H3O+, maintaining the

concentration of H3O+. The addition of hydroxide ion is

equivalent to the removal of hydronium ion, H3O+:

[H3O+] /[OH-]

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 121Example: Acetic Acid/Acetate Ion Buffer

Buffer range = pH 3.8 – pH 5.8

Acetic acid (HC2H3O) and sodium acetate (NaC2H3O2)

combined in equal numbers of moles

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 122Adding Acid to Acetic Acid/Acetate Ion Buffer

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 123Adding Base to Acetic Acid/Acetate Ion Buffer

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 124The Carbonic Acid/Hydrogen Carbonate

Buffer in the Blood

Primary blood buffer = combination of carbonic acid (H2CO3) +

hydrogen carbonate (HCO3

–)

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 125Carbonic Acid Forms from CO2 and Water

Combination reaction; reversible

Equilibrium

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 126Central Role of H2CO3

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 127Adding H3O+ [H3O+] /[OH-]

Adding H3O+ causes a shift to the left in H2CO3/HCO3

– equilibrium.

[H2CO3] increases, causing a shift to the left in the CO2/H2CO3

equilibrium.

[CO2] increases, causing lungs to exhale more CO2.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 128[H3O+] /[OH-]

Adding OH–

Adding OH– decreases H3O+ and causes a shift to the right in H2CO3/HCO3

equilibrium.

[H2CO3] decreases, causing a shift to the right in the CO2/H2CO3 equilibrium.

[CO2] decreases, causing lungs to exhale less CO2.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 129PE 9-35 A buffer can be made from a weak base and its

conjugate acid. For example, approximately equal amounts of

ammonia, NH3, and ammonium chloride, NH4

+, in solution

form a buffer.

a. b. c. d. e. Show the reversible equilibrium reaction by treating NH4

+ as

the acid. Label the buffer components.

How would this equilibrium shift if hydronium ions were

added?

How would this equilibrium shift if hydroxide ions were added?

Why does the pH not change significantly when hydronium or

hydroxide ions are added to the buffer?

If a large excess of hydronium ions or hydroxide ions were

added, exceeding the buffer capacity, would the pH change?

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 130PE 9-35 A buffer can be made from a weak base and its

conjugate acid. For example, approximately equal amounts of

ammonia, NH3, and ammonium chloride, NH4

+, in solution

form a buffer. (Answer part a)

a. Show the reversible equilibrium reaction by treating NH4

+

as the acid. Label the buffer components.

NH4

+ (aq) + H2O (l) ⇄ NH3 (aq) + H3O+ (aq)

acid conjugate base

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 131PE 9-35 A buffer can be made from a weak base and its

conjugate acid. For example, approximately equal amounts of

ammonia, NH3, and ammonium chloride, NH4

+, in solution

form a buffer. (Answer part b)

NH4

+ (aq) + H2O (l) ⇄ NH3 (aq) + H3O+ (aq)

acid conjugate base

b. How would this equilibrium shift if hydronium ions were

added?

Shift to the left

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 132PE 9-35 A buffer can be made from a weak base and its

conjugate acid. For example, approximately equal amounts of

ammonia, NH3, and ammonium chloride, NH4

+, in solution

form a buffer. (Answer part c)

NH4

+ (aq) + H2O (l) ⇄ NH3 (aq) + H3O+ (aq)

acid conjugate base

c. How would this equilibrium shift if hydroxide ions were

added?

Shift to the right

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 133PE 9-35 A buffer can be made from a weak base and its

conjugate acid. For example, approximately equal amounts of

ammonia, NH3, and ammonium chloride, NH4

+, in solution

form a buffer. (Answer part d)

NH4

+ (aq) + H2O (l) ⇄ NH3 (aq) + H3O+ (aq)

acid conjugate base

d. Why does the pH not change significantly when hydronium

or hydroxide ions are added to the buffer?

The addition of hydronium or hydroxide ions shifts the

equilibrium to a new position, causing only a small change in

the hydronium ion concentration and a small change in pH.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 134PE 9-35 A buffer can be made from a weak base and its

conjugate acid. For example, approximately equal amounts of

ammonia, NH3, and ammonium chloride, NH4

+, in solution

form a buffer. (Answer part e)

NH4

+ (aq) + H2O (l) ⇄ NH3 (aq) + H3O+ (aq)

acid conjugate base

e. If a large excess of hydronium ions or hydroxide ions were

added, exceeding the buffer capacity, would the pH change?

Yes, pH would decrease if excess hydronium ions or increase if

excess hydroxide ions were added.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 135Chemistry in Medicine: Acid-Base

Homeostasis, Acidosis, and Alkalosis

Acid-Base homeostasis is maintained in the blood by:

• buffers

• regulation of breathing (lung ventilation)

• absorption and release of HCO3

– by kidneys

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 136Breathing Rate Affects CO2 Levels in Blood

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 137Breathing Rate Affects CO2 Levels in Blood

(continued)

During exercise, [H3O+] increases, causing a shift to the left,

producing more H2CO3, shifting left again to produce more

CO2, which is exhaled by increasing ventilation.

Kidneys can support the shift to the left by releasing

additional HCO3

– into the blood.

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 138Acid-Base Homeostasis

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 139Acidosis – Blood pH < 7.35

Respiratory acidosis –

breathing weak and shallow so

CO2 is not exhaled

Causes a shift to the right,

increasing [H3O+] and

decreasing pH

Caused by head injuries,

emphysema, asthma, narcotic

use

Metabolic acidosis—kidneys do

not release sufficient HCO3

– to

support normal shift to the left

Leads to increasing [H3O+] and

decreasing pH

Caused by kidney failure,

uncontrolled diabetes,

starvation

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 140Alkalosis – Blood pH > 7.45

Respiratory alkalosis occurs

when rapid breathing removes

too much CO2.

Causes a shift to the left,

decreasing [H3O+] and

increasing pH

Hyperventilation caused by

anxiety, altitude sickness,

intense exercise

Metabolic acidosis—kidneys do

not remove enough HCO3

– from

blood

Causes a shift to the left,

decreasing [H3O+] and

increasing pH

Caused by excessive vomiting,

excess usage of antacids, and

adrenal gland diseases

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 141Treatment

Respiratory or metabolic

acidosis: IV infusion of HCO3

causing a shift to left.

Respiratory alkalosis: breathing

into paper bag to increase

blood CO2 and shift

equilibrium to right

Metabolic alkalosis: IV infusion

of dilute HCl causing a shift to

right

Guinn, Essentials of General, Organic, and Biochemistry, 3e, ©2019 W. H. Freeman and Company 142