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