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Acids

and
Bases

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Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
9.1 Introduction to Acids and Bases
The earliest definition was given by Arrhenius:

•An acid contains a hydrogen atom and dissolves


in water to form a hydrogen ion, H+.

HCl(g) H+(aq) + Cl−(aq)


acid

•A base contains hydroxide and dissolves in water


to form OH−.

NaOH(s) Na+(aq) + OH− (aq)


base
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9.1 Introduction to Acids and Bases

•The Arrhenius definition correctly predicts the


behavior of many acids and bases.

•However, this definition is limited and sometimes


inaccurate.

•For example, H+ does not exist in water. Instead, it


reacts with water to form the hydronium ion, H3O+.

H+(aq) + H2O(l) H3O+(aq)


hydrogen ion: hydronium ion:
does not really exist actually present in
in solution aqueous solution
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9.1 Introduction to Acids and Bases
The Brønsted–Lowry definition is more widely used:

•A Brønsted–Lowry acid is a proton (H+) donor.

•A Brønsted–Lowry base is a proton (H+) acceptor.

This proton is donated.


HCl(g) + H2O(l) H3O+(aq) + Cl−(aq)

•HCl is a Brønsted–Lowry acid because it donates


a proton to the solvent water.
•H2O is a Brønsted–Lowry base because it accepts
a proton from HCl.
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9.1 Introduction to Acids and Bases
A. Brønsted–Lowry Acids

•A Brønsted–Lowry acid must contain a hydrogen atom.

•Common Brønsted–Lowry acids (HA):

HCl H2SO4
hydrochloric acid sulfuric acid
H
HBr O acidic H
hydrobromic acid H C C atom

H O H
HNO3
nitric acid acetic acid
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9.1 Introduction to Acids and Bases
A. Brønsted–Lowry Acids
•A monoprotic acid contains one acidic proton.
HCl

•A diprotic acid contains two acidic protons.


H2SO4

•A triprotic acid contains three acidic protons.


H3PO4
•A Brønsted–Lowry acid may be neutral or it may
carry a net positive or negative charge.
HCl, H3O+, HSO4−
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9.1 Introduction to Acids and Bases
B. Brønsted–Lowry Bases

•A Brønsted–Lowry base is a proton acceptor,


so it must be able to form a bond to a proton.
•A base must contain a lone pair of electrons that
can be used to form a new bond to the proton.

This e− pair forms a new


bond to a H from H2O. H +

H N H + H2O(l) H N H + OH− (aq)


H H
Brønsted–Lowry
base 7
9.1 Introduction to Acids and Bases
B. Brønsted–Lowry Bases
•Common Brønsted–Lowry Bases (B ):
Lone pairs make these The OH− is the base in
neutral compounds bases. each metal salt.

NH3 NaOH
sodium hydroxide
ammonia
KOH
H2O potassium hydroxide
water Mg(OH)2
magnesium hydroxide
Ca(OH)2
calcium hydroxide
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9.2 The Reaction of a Brønsted–Lowry
Acid with a Brønsted–Lowry Base
This e− pair forms
This e− pair a new bond to H+.
stays on A. gain of H+

H A + B A − + H B+
acid base

loss of H+

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9.2 The Reaction of a Brønsted–Lowry
Acid with a Brønsted–Lowry Base

gain of H+

H A + B A − + H B+
acid base conjugate conjugate
base acid

loss of H+

•The product formed by loss of a proton from an


acid is called its conjugate base.
•The product formed by gain of a proton by a base
is called its conjugate acid.
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9.2 The Reaction of a Brønsted–Lowry
Acid with a Brønsted–Lowry Base

gain of H+

H Br + H2O Br− + H3O+


acid base conjugate conjugate
base acid

loss of H+

•HBr and Br− are a conjugate acid–base pair.


•H2O and H3O+ are a conjugate acid–base pair.
•The net charge must be the same on both sides
of the equation. 11
9.2 The Reaction of a Brønsted–Lowry
Acid with a Brønsted–Lowry Base

•When a species gains a proton (H+), it gains a +1


charge.
add H +
H2O H3O+
base
zero charge +1 charge

•When a species loses a proton (H+), it effectively


gains a −1 charge.

HBr lose H+
Br−
acid
zero charge −1 charge 12
9.2 The Reaction of a Brønsted–Lowry
Acid with a Brønsted–Lowry Base
Amphoteric compound: A compound that contains
both a hydrogen atom and a lone pair of e−; it can
be either an acid or a base.
H +
add H+
H O H H O H
H2O as a base conjugate acid


remove H+
H O H H O
H2O as an acid conjugate base
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9.3 Acid and Base Strength
A. Relating Acid and Base Strength

•When a covalent acid dissolves in water, the proton


transfer that forms H3O+ is called dissociation.
•When a strong acid dissolves in water, 100% of
the acid dissociates into ions.

HCl(g) + H2O(l) H3O+(aq) + Cl−(aq)

•A single reaction arrow is used, because the


product is greatly favored at equilibrium.

•Common strong acids are HI, HBr, HCl, H2SO4,


and HNO3.
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9.3 Acid and Base Strength
A. Relating Acid and Base Strength

•When a weak acid dissolves in water, only a


small fraction of the acid dissociates into ions.

•Unequal reaction arrows are used, because the


reactants are usually favored at equilibrium.

CH3COOH(l) + H2O(l) H3O+(aq) + CH3COO−(aq)

•Common weak acids are H3PO4, HF, H2CO3, and


HCN.

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9.3 Acid and Base Strength
A. Relating Acid and Base Strength

A strong acid, HCl, is A weak acid, CH3COOH,


completely dissociated contains mostly
into H3O+(aq) and Cl−(aq). undissociated acid.

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9.3 Acid and Base Strength
A. Relating Acid and Base Strength

•When a strong base dissolves in water, 100% of


the base dissociates into ions.

NaOH(s) + H2O(l) Na+(aq) + −OH(aq)

•Common strong bases are NaOH and KOH.

•When a weak base dissolves in water, only a


small fraction of the base dissociates into ions.

NH3(g) + H2O(l) NH4+(aq) + −OH(aq)

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9.3 Acid and Base Strength
A. Relating Acid and Base Strength

A strong base, NaOH, is A weak base contains


completely dissociated mostly undissociated
into Na+(aq) and −OH(aq). base, NH3.
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9.3 Acid and Base Strength
A. Relating Acid and Base Strength

•A strong acid readily donates a proton, forming


a weak conjugate base.
HCl Cl−
strong acid weak conjugate base

•A strong base readily accepts a proton, forming


a weak conjugate acid.

OH− H2O
strong base weak conjugate acid

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9.3 Acid and Base Strength
A. Relating Acid and Base Strength

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9.3 Acid and Base Strength
B. Using Acid Strength to Predict the Direction
of Equilibrium
•A Brønsted–Lowry acid–base reaction represents
an equilibrium.

H A + B A − + H B+
acid base conjugate conjugate
base acid

•The position of the equilibrium depends upon the


strengths of the acids and bases.

•The stronger acid reacts with the stronger base


to form the weaker acid and the weaker base.
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9.3 Acid and Base Strength
B. Using Acid Strength to Predict the Direction
of Equilibrium
•When the stronger acid and base are the reactants
on the left side, the reaction readily occurs and
the reaction proceeds to the right.

H A + B A − + H B+
stronger stronger weaker weaker
acid base base acid

•A larger forward arrow means that products are


favored.

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9.3 Acid and Base Strength
B. Using Acid Strength to Predict the Direction
of Equilibrium
•If an acid–base reaction would form the stronger
acid and base, equilibrium favors the reactants
and little product forms.

H A + B A − + H B+
weaker weaker stronger stronger
acid base base acid

•A larger reverse arrow means that reactants are


favored.

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9.3 Acid and Base Strength
HOW TO Predict the Direction of Equilibrium in an
Acid–Base Reaction
Are the reactants or products favored in
Example
the following acid–base reaction?
gain of H+

HCN(g) −OH(aq) −CN(aq)


+ + H2O(l)
acid base conjugate conjugate
base acid

loss of H+

Step [1] Identify the acid in the reactants and the


conjugate acid in the products.
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9.3 Acid and Base Strength
HOW TO Predict the Direction of Equilibrium in an
Acid–Base Reaction

Step [2] Determine the relative strength of the acid


and the conjugate acid.
•From Table 9.1, HCN is a stronger acid than H2O.
Equilibrium favors the formation of the
Step [3]
weaker acid.
HCN(g) −OH(aq) −CN(aq)
+ + H2O(l)
stronger weaker
acid acid
Products are favored.
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9.4 Equilibrium and Acid Dissociation
Constants
For the reaction where an acid (HA) dissolves in
water,

HA(g) + H2O(l) H3O+(aq) + A − (aq)

the following equilibrium constant can be written:

[H3O+][ A −]
K =
[HA][H2O]

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9.4 Equilibrium and Acid Dissociation
Constants
•Multiplying both sides by [H2O] forms a new constant,
called the acid dissociation constant, Ka.

[H3O+][ A −]
Ka = K[H2O] =
[HA]
acid dissociation
constant

•The stronger the acid, the larger the Ka value.

•Equilibrium favors formation of the weaker acid,


the acid with the smaller Ka value.
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9.4 Equilibrium and Acid Dissociation
Constants

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9.5 Dissociation of Water

Water can behave as both a Brønsted–Lowry acid


and a Brønsted–Lowry base. Thus, two water
molecules can react together in an acid–base reaction:

loss of H+ +
H

H O H + H O H O H + H O H
acid base conjugate conjugate
base acid

gain of H+

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9.5 Dissociation of Water
•From the reaction of two water molecules, the
following equilibrium constant expression can be
written:
[H3O+][OH−]
K =
[H2O]2

•Multiplying both sides by [H2O]2 yields Kw, the


ion-product constant for water.

Kw = [H3O+][OH−]
ion-product
constant
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9.5 Dissociation of Water

•Experimentally it can be shown that:

[H3O+] = [OH−] = 1.0 x 10−7 M at 25 oC

Kw = [H3O+] [OH−]

Kw = (1.0 x 10−7) x (1.0 x 10−7)


Kw = 1.0 x 10−14

•Kw is a constant, 1.0 x 10−14, for all aqueous


solutions at 25 oC.

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9.5 Dissociation of Water

To calculate [OH−] when To calculate [H3O+] when


[H3O+] is known: [OH−] is known:

Kw = [H3O+][OH−] Kw = [H3O+][OH−]

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9.5 Dissociation of Water
If the [H3O+] in a cup of coffee is 1.0 x 10−5 M, then
the [OH−] can be calculated as follows:

Kw 1.0 x 10−14
[OH−] = = −5
= 1.0 x 10−9 M
[H3O+] 1.0 x 10

In this cup of coffee, therefore, [H3O+] > [OH–], and


the solution is acidic overall.

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9.5 Dissociation of Water

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9.6 The pH Scale
A. Calculating pH

The lower the pH, the higher the concentration of


H3O+:
•Acidic solution: pH < 7 → [H3O+] > 1 x 10−7

•Neutral solution: pH = 7 → [H3O+] = 1 x 10−7

•Basic solution: pH > 7 → [H3O+] < 1 x 10−7

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9.6 The pH Scale
A. Calculating pH

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9.6 The pH Scale
B. Calculating pH Using a Calculator

•A logarithm has the same number of places after


the decimal as there are digits in the original number.
•Example:
If [H3O+] = 1.2 x 10–5 M for a solution, what is its pH?
pH = –log [H3O+]

pH = –log (1.2 x 10–5) 2 digits


pH = –(–4.92) 2 decimal places

pH = 4.92

The solution is acidic because the pH < 7. 37


9.6 The pH Scale
B. Calculating pH Using a Calculator

If the pH of a solution is 8.50, what is the [H3O+]?


pH = −log [H3O+]

8.50 = −log [H3O+]

−8.50 = log [H3O+]

antilog (−8.50 ) = [H3O+] 2 decimal places

[H3O+] = 3.2 x 10−9 M 2 digits

The solution is basic because [H3O+] > 1 x 10–7 M.


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9.6 The pH Scale

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9.7 Common Acid–Base Reactions
A. Reaction of Acids with Hydroxide Bases

Neutralization reaction: An acid-base reaction that


produces a salt and water as products.

HA(aq) + MOH(aq) H OH(l) + MA(aq)


acid base water salt

•The acid HA donates a proton (H+) to the OH− base


to form H2O.
•The anion A− from the acid combines with the
cation M+ from the base to form the salt MA.

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9.7 Common Acid–Base Reactions
HOW TO Draw a Balanced Equation for a Neutralization
Reaction Between HA and MOH

Example Write a balanced equation for the reaction


of Mg(OH)2 with HCl.

Step [1] Identify the acid and base in the reactants


and draw H2O as one product.

HCl(aq) + Mg(OH)2(aq) H2O(l) + salt


acid base water

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9.7 Common Acid–Base Reactions
HOW TO Draw a Balanced Equation for a Neutralization
Reaction between HA and MOH

Step [2] Determine the structure of the salt.


•The salt is formed from the parts of the acid and
base that are not used to form H2O.
HCl Mg(OH)2

H+ Cl− Mg2+ 2 OH−


reacts to used to used to react to
form H2O form salt form salt form water

Mg2+ and Cl− combine to form MgCl2.


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9.7 Common Acid–Base Reactions
HOW TO Draw a Balanced Equation for a Neutralization
Reaction between HA and MOH

Step [3] Balance the equation.


Place a 2 to
balance O and H.

2 HCl(aq) + Mg(OH)2(aq) 2 H2O(l) + MgCl2


acid base water salt
Place a 2 to
balance Cl.

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9.9 Titration
•To determine the concentration of an acid or base
in a solution, we carry out a titration.

•If we want to know the concentration of an acid


solution, a base of known concentration is
added slowly until the acid is neutralized.

•When the acid is neutralized:

# of moles of acid = # of moles of base

•This is called the end point of the titration.

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9.9 Titration

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9.10 Buffers
A buffer is a solution whose pH changes very little
when acid or base is added.

Most buffers are solutions composed of roughly


equal amounts of:
•A weak acid
•The salt of its conjugate base

The buffer resists change in pH because


•Added base, OH−, reacts with the weak acid
•Added acid, H3O+, reacts with the conjugate base
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9.10 Buffers
A. General Characteristics of a Buffer
If an acid is added to the following buffer equilibrium,
then the excess acid reacts with the conjugate base,
so the overall pH does not change much.

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9.10 Buffers
A. General Characteristics of a Buffer
If a base is added to the following buffer equilibrium,
then the excess base reacts with the conjugate acid,
so the overall pH does not change much.

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9.10 Buffers

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9.10 Buffers
B. Calculating the pH of a Buffer
•The effective pH range of a buffer depends on its Ka.
HA(aq) + H2O(l) H3O+(aq) + A −(aq)

[H3O+][ A −]
Ka =
[HA]

•Rearranging this expression to solve for [H3O+]:

[HA]
[H3 O+] = Ka x
[ A −]

determines the
buffer pH 50
9.11 Focus on the Human Body
Buffers in the Blood

•Normal blood pH is between 7.35 and 7.45.


•The principle buffer in the blood is carbonic acid/
bicarbonate (H2CO3/HCO3−).
H2O
CO2(g) + H2O(l) H2CO3(aq)

H3O+(aq) + HCO3−(aq)

•CO2 is constantly produced by metabolic


processes in the body.
•The amount of CO2 is related to the pH of the blood.
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9.11 Focus on the Human Body
Buffers in the Blood
Respiratory acidosis results when the body fails to
eliminate enough CO2, due to lung disease or failure.

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9.11 Focus on the Human Body
Buffers in the Blood
Respiratory alkalosis is caused by hyperventilating;
very little CO2 is produced by the body.

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