11.

1: The Nature of Acids and Bases

There are three major classifications of substances known as acids or bases. The Arrhenius
definition states that an acid produces H + in solution and a base produces OH-. This theory was
developed by Svante Arrhenius in 1883. Later, two more sophisticated and general theories were
proposed. These are the Brønsted-Lowry and the Lewis definitions of acids and bases. The Lewis
theory is discussed elsewhere.

Introduction

Acids and bases are common solutions that exist everywhere. Almost every liquid that we
encounter in our daily lives consists of acidic and basic properties, with the exception of water.
They have completely different properties and are able to neutralize to form H 2O, which will be
discussed later in a subsection. The table below compares the different properties between them:

Table 1: Examples of Acids and Bases

ACIDS BASES

produce a piercing pain in a

give a slippery feel.
wound.

taste sour. taste bitter.

are colorless when placed in

are pink when placed in
phenolphthalein (an
phenolphthalein (an indicator).
indicator).

are red on blue litmus paper are blue on red litmus paper (a pH
(a pH indicator). indicator).

have a pH<7. have a pH>7.

produce hydrogen gas when

reacted with metals.
 produce carbon dioxide when
reacted with carbonates.

Common Examples: Soap,

Common examples: Lemons,
toothpaste, bleach, cleaning
oranges, vinegar, urine, agents, limewater, ammonia water,
sulfuric acid, hydrochloric acid sodium hydroxide.

The Arrhenius Theory of Acids and Bases

In 1884, the Swedish chemist Svante Arrhenius proposed two specific classifications of
compounds, termed acids and bases. When dissolved in an aqueous solution, certain ions were
released into the solution. An Arrhenius acid is a compound that increases the concentration
of H+ ions that are present when added to water. These H + ions form the hydronium ion (H3O+)
when they combine with water molecules. This process is represented in a chemical equation by
adding H2O to the reactants side.

HCl(aq)→H+(aq)+Cl−(aq)(11.1.1)(11.1.1)���(��)→�(��)++��(��)−
In this reaction, hydrochloric acid ( HCl���) dissociates completely into hydrogen (H +) and
chlorine (Cl-) ions when dissolved in water, thereby releasing H + ions into solution. Formation of
the hydronium ion equation:
HCl(aq)+H2O(l)→H3O+(aq)+Cl−(aq)(11.1.2)(11.1.2)���(��)
+�2�(�)→�3�(��)++��(��)−
The Arrhenius theory, which is the simplest and least general description of acids and bases,
includes acids such as HClO 4 and Hbr and bases such
as NaOH���� or Mg(OH)2��(��)2. For example the complete dissociation
of HBr��� gas into water results generates free H3O+�3�+ ions.
HBr(g)+H2O(l)→H3O+(aq)+Br−(aq)(11.1.3)(11.1.3)���(�)
+�2�(�)→�3�(��)++��(��)−
This theory successfully describes how acids and bases react with each other to make water and
salts. However, it does not explain why some substances that do not contain hydroxide ions, for
example F−�− and NO−2��2−, can make basic solutions in water. The Brønsted-Lowry
definition of acids and bases addresses this problem.

An Arrhenius base is a compound that increases the concentration of OH - ions that are present
when added to water. The dissociation is represented by the following equation:

NaOH(aq)→Na+(aq)+OH−(aq)(11.1.4)(11.1.4)����(��)→��+(��)
+��−(��)
In this reaction, sodium hydroxide (NaOH) disassociates into sodium (Na +) and hydroxide (OH-)
ions when dissolved in water, thereby releasing OH- ions into solution.

Note
 Arrhenius acids are substances which produce hydrogen ions in solution.
 Arrhenius bases are substances which produce hydroxide ions in solution.

Free Hydrogen Ions do not Exist in Water

Owing to the overwhelming excess of H2O�2� molecules in aqueous solutions, a bare
hydrogen ion has no chance of surviving in water. The hydrogen ion in aqueous solution is no
more than a proton, a bare nucleus. Although it carries only a single unit of positive charge, this
charge is concentrated into a volume of space that is only about a hundred-millionth as large as
the volume occupied by the smallest atom. (Think of a pebble sitting in the middle of a sports
stadium!) The resulting extraordinarily high charge density of the proton strongly attracts it to
any part of a nearby atom or molecule in which there is an excess of negative charge. In the case
of water, this will be the lone pair (unshared) electrons of the oxygen atom; the tiny proton will
be buried within the lone pair and will form a shared-electron (coordinate) bond with it, creating
a hydronium ion, H3O+�3�+. In a sense, H2O�2� is acting as a base here, and the
product H3O+�3�+ is the conjugate acid of water:

Although other kinds of dissolved ions have water molecules bound to them more or less tightly,
the interaction between H+ and H2O�2� is so strong that writing “H+(aq)” hardly does it
justice, although it is formally correct. The formula H3O+�3�+ more adequately conveys the
sense that it is both a molecule in its own right, and is also the conjugate acid of water.

The equation "HA → H+ + A–" is so much easier to write that chemists still use it to represent
acid-base reactions in contexts in which the proton donor-acceptor mechanism does not need to
be emphasized. Thus it is permissible to talk about “hydrogen ions” and use the formula H + in
writing chemical equations as long as you remember that they are not to be taken literally in the
context of aqueous solutions.

Limitations to the Arrhenius Theory

The Arrhenius theory has many more limitations than the other two theories. The theory suggests
that in order for a substance to release either H+ or OH- ions, it must contain that particular ion.
However, this does not explain the weak base ammonia (NH 3), which in the presence of water,
releases hydroxide ions into solution, but does not contain OH- itself.

Hydrochloric acid is neutralized by both sodium hydroxide solution and ammonia solution. In
both cases, you get a colourless solution which you can crystallise to get a white salt - either
sodium chloride or ammonium chloride. These are clearly very similar reactions. The full
equations are:
 NaOH(aq)+HCl(aq)→NaCl(aq)+H2O(l)(11.1.5)(11.1.5)����(��)
+���(��)→����(��)+�2�(�)
NH3(aq)+HCl(aq)→NH4Cl(aq)(11.1.6)(11.1.6)��3(��)
+���(��)→��4��(��)

In the sodium hydroxide case, hydrogen ions from the acid are reacting with hydroxide ions from
the sodium hydroxide - in line with the Arrhenius theory. However, in the ammonia case, there
are no hydroxide ions!

You can get around this by saying that the ammonia reacts with the water it is dissolved in to
produce ammonium ions and hydroxide ions:

NH3(aq)+H2O(l)⇌NH+4(aq)+OH−(aq)(11.1.7)(11.1.7)��3(��)
+�2�(�)⇌��4+(��)+��−(��)

This is a reversible reaction, and in a typical dilute ammonia solution, about 99% of the ammonia
remains as ammonia molecules. Nevertheless, there are hydroxide ions there, and we can
squeeze this into the Arrhenius theory. However, this same reaction also happens between
ammonia gas and hydrogen chloride gas.

NH3(g)+HCl(g)→NH4Cl(s)(11.1.8)(11.1.8)��3(�)+���(�)→��4��(�)

In this case, there are not any hydrogen ions or hydroxide ions in solution - because there isn't
any solution. The Arrhenius theory wouldn't count this as an acid-base reaction, despite the fact
that it is producing the same product as when the two substances were in solution. Because of
this short-coming, later theories sought to better explain the behavior of acids and bases in a new
manner.

The Brønsted-Lowry Theory of Acids and Bases

 A Brønsted-Lowry acid is a proton (hydrogen ion) donor.
 A Brønsted-Lowry base is a proton (hydrogen ion) acceptor.

In this theory an acid is a substance that can release a proton (like in the Arrhenius theory)
and a base is a substance that can accept a proton. A basic salt such as Na +F- generates
OH- ions in water by taking protons from water itself (to make HF):

F−(aq)+H2O(l)⇌HF(aq)+OH−(11.1.9)(11.1.9)�(��)−+�2�(�)⇌��(��)
+��−
When a Brønsted acid dissociates, it increases the concentration of hydrogen ions in the
solution, [H+][�+]; conversely, Brønsted bases dissociate by taking a proton from the solvent
(water) to generate [OH−][��−].
 Acid dissociation:
 HA(aq)⇌A−(aq)+H+(aq)(11.1.10)(11.1.10)��(��)⇌�(��)−+�(��)+
Ka=[A−][H+][HA](11.1.11)(11.1.11)��=[�−][�+][��]
 Base dissociation:
B(aq)+H2O(l)⇌HB+(aq)+OH−(aq)(11.1.12)(11.1.12)�(��)+�2�(�)⇌��(��)+
+��(��)−
Kb=[HB+][OH−][B](11.1.13)(11.1.13)��=[��+][��−][�]

Conjugate acids and bases

One important consequence of these equilibria is that every acid (HA��) has a conjugate
base (A−�−), and vice-versa. In the base dissociation equilibrium above the conjugate acid of
base B� is HB+��+. For a given acid or base, these equilibria are linked by the water
dissociation equilibrium:
H2O(l)⇌H+(aq)+OH−(aq)(11.1.14)(11.1.14)�2�(�)⇌�(��)++��(��)−

with

Kw=[H+][OH−](11.1.15)(11.1.15)��=[�+][��−]

for which the equilibrium constant K w is 1.00 x 10-14 at 25°C. It can be easily shown that the
product of the acid and base dissociation constants Ka and Kb is Kw.

Strong and Weak Acids and Bases

Strong acids are molecular compounds that essentially ionize to completion in aqueous solution,
disassociating into H+ ions and the additional anion; there are very few common strong acids. All
other acids are "weak acids" that incompletely ionized in aqueous solution. Acids and bases that
dissociate completely are said to be strong acids, e.g.:

 HClO4(aq)→H+(aq)+ClO−4(aq)����4(��)→�(��)++���4(��)−
 HBr(aq)→H+(aq)+Br−(aq)���(��)→�(��)++��(��)−
 CH3O−(aq)+H2O(l)→CH3OH(aq)+OH−(aq)��3�(��)−
+�2�(�)→��3��(��)+��(��)−
 NH−2(aq)+H2O(l)→NH3(aq)+OH−(aq)��2(��)−+�2�(�)→��3(��)
+��(��)−
Here the right-handed arrow (→→) implies that the reaction goes to completion. That is, a 1.0
M solution of HClO4 in water actually contains 1.0 M H +(aq) and 1.0 M ClO4-(aq), and no
undissociated HClO4.
Conversely, weak acids such as acetic acid (CH 3COOH) and weak bases such as ammonia (NH 3)
dissociate only slightly in water - typically a few percent, depending on their concentration and
exist mostly as the undissociated molecules.

 Strong Acids: HCl, HNO3, H2SO4, HBr, HI, HClO4

 Weak Acids: All other acids, such as HCN, HF, H2S, HCOOH
Strong acids such as HCl��� dissociate to produce spectator ions such as Cl−��− as
conjugate bases, whereas weak acids produce weak conjugate bases. This is illustrated below for
acetic acid and its conjugate base, the acetate anion. Acetic acid is a weak acid (K a = 1.8 x 10-5)
and acetate is a weak base (Kb = Kw/Ka = 5.6 x 10-10)

Like acids, strong and weak bases are classified by the extent of their ionization. Strong bases
disassociate almost or entirely to completion in aqueous solution. Similar to strong acids, there
are very few common strong bases. Weak bases are molecular compounds where the ionization
is not complete.

 STRONG BASES: The hydroxides of the Group I and Group II metals such as LiOH, NaOH, KOH,
RbOH, CsOH
 WEAK BASES: All other bases, such as NH3, CH3NH2, C5H5N
Note

The strength of a conjugate acid/base varies inversely with the strength or weakness of its parent
acid or base. Any acid or base is technically a conjugate acid or conjugate base also; these terms
are simply used to identify species in solution (i.e acetic acid is the conjugate acid of the acetate
anion, a base, while acetate is the conjugate base of acetic acid, an acid).

How does one define acids and bases? In chemistry, acids and bases have been defined
differently by three sets of theories. One is the Arrhenius definition, which revolves around the
idea that acids are substances that ionize (break off) in an aqueous solution to produce hydrogen
(H+) ions while bases produce hydroxide (OH -) ions in solution. On the other hand, the Brønsted-
Lowry definition defines acids as substances that donate protons (H +) whereas bases are
substances that accept protons. Also, the Lewis theory of acids and bases states that acids are
electron pair acceptors while bases are electron pair donors. Acids and bases can be defined by
their physical and chemical observations.

The Brønsted-Lowry Definition

In 1923, chemists Johannes Nicolaus Brønsted and Thomas Martin Lowry independently developed
definitions of acids and bases based on the compounds' abilties to either donate or accept protons
(H+ ions). In this theory, acids are defined as proton donors; whereas bases are defined as proton
acceptors. A compound that acts as both a Brønsted-Lowry acid and base together is
called amphoteric.This took the Arrhenius definition one step further, as a substance no longer needed
to be composed of hydrogen (H+) or hydroxide (OH-) ions in order to be classified as an acid or base.

Consider the following chemical equation:

HCl(aq)+NH3(aq)→NH+4(aq)+Cl−(aq)(11.1.16)(11.1.16)���(��)+��3(��)→��4+(��)
+��−(��)

Here, hydrochloric acid (HCl) "donates" a proton (H+) to ammonia (NH3) which "accepts" it ,
forming a positively charged ammonium ion (NH 4+) and a negatively charged chloride ion (Cl -).
Therefore, HCl is a Brønsted-Lowry acid (donates a proton) while the ammonia is a Bronsted-
Lowry base (accepts a proton). Also, Cl - is called the conjugate base of the acid HCl and NH4+ is
called the conjugate acid of the base NH3.

Neutralization

A special property of acids and bases is their ability to neutralize the other's properties. In an
acid-base (or neutralization) reaction, the H + ions from the acid and the OH - ions from the base
react to create water (H2O). Another product of a neutralization reaction is an ionic compound
called a salt. Therefore, the general form of an acid-base reaction is:

The following are examples of neutralization reactions:

1.

(NOTE: To see this reaction done experimentally, refer to the YouTube video link under the
section "References".)

2.

Sample Problems

1. Which of the following compounds is a strong acid?

1. CaSO4
2. NaCl
3. HNO3
4. NH3

Solution: There are 6 strong acids and all other acids are considered weak. HNO 3 is one of those
6 strong acids, while NH3 is actuallly a weak base.
The answer is (c) HNO3.

2. Which of the following compounds is a Bronsted-Lowry base?

1. HCl
2. HPO42-
3. H3PO4
4. NH4+
5. CH3NH3+

Solution: A Brønsted-Lowry Base is a proton acceptor, which means it will take in an H +. This
eliminates HCl, H3PO4 ,NH4+ and CH3NH3+ because they are Bronsted-Lowry acids. They all give
away protons. In the case of HPO42-, consider the following equation:

Here, it is clear that HPO42- is the acid since it donates a proton to water to make H 3O+ and PO43-.
Now consider the following equation:

In this case, HPO42- is the base since it accepts a proton from water to form H2PO4- and OH-. Thus,
HPO42- is an acid and base together, making it amphoteric.

Since HPO42- is the only compound from the options that can act as a base, the answer is (b)
HPO42-.

3. A 50 ml solution of 0.5 M NaOH is titrated until neutralized into a 25 ml sample of HCl.

What was the concentration of the HCl?

Solution: Since the number of moles of acid equals the number of moles of base at
neutralization, the following equation is used to solve for the molarity of HCl:

Now, plug into the equation all the information that is given:

MHCl(25 mL HCl) = (0.5 M NaOH)(50 mL NaOH)

MHCl = 1 M

The correct answer is 1 M HCl.

4. In the following acid-base neutralization, 2.79 g of the acid HBr (80.91g/mol) neutralized
22.72 mL of a basic aqueous solution by the reaction:

Calculate the molarity of the basic solution.

Solution:

First, the number of moles of the acid needs to be calculated. This is done by using the molar
mass of HBr to convert 2.79 g of HBr to moles.

(2.79 g HBr)/(80.91 g/mol HBr) = 0.0345 moles HBr

Since this is a neutralization reaction, the number of moles of the acid (HBr) equals the number
of moles of the base (NaOH) at neutralization:

moles of acid = moles of base

0.0345 moles HBr = 0.0345 moles NaOH

The molarity of NaOH can now be determined since the amount of moles are found and the
volume is given. Convert 22.72 mL to Liters first since molarity is in units of moles/L.

Molarity = (0.0345 moles NaOH)/(0.02272 L NaOH) = 1.52 M NaOH

The correct answer is 1.52 M NaOH.

5. Which of the following is a Brønsted-Lowry base but not an Arrhenius base?

1. NH3
2. NaOH
3. Ca(OH)2
4. KOH

Solution: The Brønsted-Lowry definition says that a base accepts protons (H + ions). NaOH,
Ca(OH)2, and KOH are all Arrhenius bases because they yield the hydroxide ion (OH -) when
they ionize. However, NH3 does not dissociate in water like the others. Instead, it takes a proton
from water and becomes NH4 while water becomes a hydroxide.

Therefore, the correct answer is (a) NH3.