Lecture Notes in Inorganic Chemistry 1

Acids and Bases

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 H2O.

Intended Learning Outcomes

At the end of the chapter, the student must be able to:

1. Described and discuss the different acid-base models; Arrhenius, Bronsted-Lowry and Lewis.
2. Identify hard and soft acids and bases and analyze the different applications of the hard-soft interaction
principles.

Acid and Base Definition

Arrhenius Definition- acids and bases are classified in terms of their formulas and their behavior in water.
Acid- substance that has an H in the formula and dissociates in water to yield H3O+.
Base- substance that has an OH in the formula and dissociates in water to yield OH-.
Bronsted-Lowry Definition

Figure 1. Acid or base in water as a Bronsted-Lowry acid-base reaction (Silberberg, 2017)

Acid- an acid is a proton donor, any species that donates an H+ ion. All Arrhenius acid is Bronsted-Lowry acid.
Base- a base is a proton acceptor, any species that accepts an H+ ion. Bronsted-Lowry bases are not Arrhenius
bases, but all Arrhenius bases contain the Bronsted-Lowry base OH-.
v From the Bronsted-Lowry perspective, the only requirement for an acid-base reaction is that one species
donate a proton and another species accepts it; an acid-base reaction is a proton-transfer process.
Lewis Definition
Acid is any species that accepts an electron pair.
Base is any species that donates an electron pair.

Conjugate acid-base pair

v Every acid has a conjugate base and every base has a conjugate acid.
How to identify Conjugate Pairs

1. HNO3 is an acid because it donates a proton to water and its conjugate base is NO3- .An easy way to
identify the conjugate base is that it differs from the acid by one proton.
2. H2O is a base because it accepts a proton from HNO3 and its conjugate acid is H3O+. Again to identify
the conjugate acid (or any conjugate pair) is that it differs from the base by one proton.
v In other words, the conjugate base has one fewer H and one more negative charge than the acid. The
conjugate acid has one more H and one fewer negative charge than the base.

The following table is an example of conjugate acid and base pairs in a given equation:
 Lecture Notes in Inorganic Chemistry 1
Acids and Bases

Practice Problem

I. Identify the acid, base, conjugate acid and conjugate base for each of the following.
a. HClO4(aq) + H2O(l) ⇄ H3O+(aq) + ClO4–(aq)
b. H2SO3(aq) + H2O(l) ⇄ H3O+(aq) + HSO3–(aq)
c. HC2H3O2(aq) + H2O(l) ⇄ H3O+(aq) + C2H3O2–(aq)
d. H2S(g) + H2O(l) ⇄ H3O+(aq) + HS–(aq)
e. HSO3–(aq) + H2O(l) ⇄ H3O+(aq) + SO32–(aq)
f. NH3(g) + H2O(l) ⇄ NH4+(aq) + OH–(aq)
g. HF (aq) + HSO3–(aq) ⇄ F–(aq) + H2SO3(aq)
h. HNO2 (aq) + HS–(aq) ⇄ NO2–(aq) + H2S(aq)

Acid Strength

The strength of an acid is defined by the equilibrium position of its dissociation (ionization reaction).

HA (aq) + H2O(l) ⇄ H3O+ (aq) + A- (aq)

A strong acid is one for which this equilibrium lies far to the right. This means that all the original HA is
ionized at equilibrium. A strong acid yields a weak conjugate base.

$%! &" '[)#]

𝑄!" $ [%)]
% (at equilibrium, Qc= Kc >> 1), because the reaction is essentially complete, we don’t
usually express it as an equilibrium process.

A weak acid is one for which the equilibrium lies far to the left. Most of the acid originally placed in the
solution is still present as HA at equilibrium. The weaker the acid, the stronger its conjugate base.

HCN(aq) + H2O(l) Û H3O+(aq) + CN-(aq)

$%! &" '[+,# ]

𝑄!" $ [%+,]
% at equilibrium, Qc = Kc <<1

The net direction of an acid-base reaction depends on relative acid and base strengths: A reaction proceeds to the
greater extent in the direction in which a stronger acid and stronger base form a weaker acid and weaker base.

In effect, the extent of acid (HA) dissociation in water can be viewed as the result of a competition for the proton
between the two bases, A− and H2O. Strong and weak acids give different results:
In strong acids, proton is completely transferred to the base, H2O, forming the conjugate base NO3-, and the conjugate
acid, H3O+.

In weak acids such as HF, the A- (or F- in this example), wins the competition for proton because it is a stronger base
than water and the net direction is to the left thus the net result only leaves small percentage of HF to be dissociated.

Table 1. Various ways to describe acid strength (Zumdahl, 2017)

 Lecture Notes in Inorganic Chemistry 1
Acids and Bases

Figure 2. Relative strength of conjugate pairs (Silberberg, 2017)

v The stronger the acid is, the weaker its conjugate base. The strongest
acid is at top left and the strongest base at bottom right. When an acid
reacts with a base farther down the list, the reaction proceeds to the
right (Kc > 1).

Water as an acid and a base

A substance is said to be amphoteric if it can behave either as an acid or as a base. Water is said to be
amphoteric because it can behave such. We can see this in the auto-ionization of water, which involves the transfer
of a proton from one water molecule to another to produce a hydroxide ion and a hydronium ion.

H2O(l) + H2O(l) ⇄ H3O+(aq) + OH-(aq) Kw= [H3O+] [OH-]= 1 x 10-14 @ 25°C

• [H3O+] = [OH-] = 1 x 10-7 M
The pH scale
Because the constant of water, Kw is always 1.0 x 10-14, the pKw is 14, the constant of water determines the
range of the pH scale. To understand what the pKw is, it is important to understand first what the "p" means in pOH,
and pH. The Danish Biochemist Soren Sorensen proposed the term pH to refer to the "potential of hydrogen ion." He
defined the "p" as the negative of the logarithm, -log, of [H+]. Therefore the pH is the negative logarithm of the
molarity of H. The pOH is the negative logarithm of the molarity of OH- and the pKw is the negative logarithm of the
constant of water. These definitions give the following equations:
pH= -log [H+]
pOH= -log [OH-]
pKw= -log [Kw]

Calculating the pH of weak acid/base solutions and % dissociation

1. Calculate the pH for a 15.0 M solution of NH3 (Kb= 1.8 x 10-5).

Ø Since NH3 is a weak base, as seen from its small Kb, most of the dissolved NH3 will remain as NH3. Thus, the
major species in solution are NH3 and H2O. Both of these substance can produce OH- according to the
reaction:

However, since Kb >>> Kw, the equilibrium for NH3 will dominate and the equilibrium expression will be

Substituting the equilibrium concentrations on the equilibrium expression, and making a particular assumption
 Lecture Notes in Inorganic Chemistry 1
Acids and Bases

Polyprotic acids are acids which contains more than one proton. It always dissociate in stepwise manner, one proton
at a time.
The diprotic carbonic acid is so important in maintaining a constant pH in human blood and it dissociates in
2-steps. The successive Ka values for the dissociation equilibria are designated Ka1 and Ka2. Note that the conjugate
base HCO3- of the first dissociation equilibrium becomes the acid in the second step.

Problem Solving. Calculate the pH of a 5.0-M H3PO4 solution and the equilibrium concentrations of the species
H3PO4, H2PO4-, HPO4-2, and PO43-.

Acid-Base Properties of Salts

Salt is simply another name for ionic compound. When a salt dissolves in water, we assume that it breaks
up into its ions, which move about independently, at least in dilute solutions. Under certain conditions, these ions
can behave as acids or bases.
Table 2. Acid-Base Properties of Various Types of Salt (Zumdahl, 2017)

Problem Solving. Salts as weak bases.

1. Calculate the pH of a 0.30-M NaF solution. The Ka value for HF is 7.2 x 10-4.

v Since HF is a weak acid, the F- ion must have a significant affinity for protons, and the dominant reaction
will be

[%&][(% - ]
which yields Kb expression 𝐾!" # [& - ]
$

The value of Kb can be obtained from Kw and Ka, wherein Kb is equal o 1.4 x 10-11.
 Lecture Notes in Inorganic Chemistry 1
Acids and Bases

Salts as weak acids.

2. Calculate the pH of a 0.010-M AlCl3 solution. The Ka value for Al(H2O)63+ is 1.4 x 10-5.

Practice exercise
1. Predict whether an aqueous solution of each of the following salts will be acidic, basic, or neutral.
a. NH4C2H3O2
b. NH4CN
c. Al2(SO4)3
d. KClO4
e. Cr(NO3)3
2. Dimethylamine, (CH3)2NH2, a key ingredient in detergent manufacture, has a Kb of 5.9 x 10-4. What is the pH
of 1.5M of its solution?
3. Sodium acetate (CH3COONa, NaAc) is used in textile dyeing. Wat is th pH of 0.25 NaAc at 25°C? the Ka of
acetic acid (HAc) is 1.8 x 10-5.

Equilibria of Acid-Base Buffers

Ø An acid-base buffer is a solution that lessens the impact on its pH of the addition of acid or base. Most often, the
components of a buffer are a conjugate acid-base pair (weak acid and conjugate base or weak base and conjugate
acid).
Ø Buffers work through the common-ion effect. A common-ion effect occurs when a given ion is added to an
equilibrium mixture that already contains that ion, and the position of the equilibrium shifts away from forming it.
v Case situation. When you dissolve acetic acid in water, the acid dissociates slightly:

Addition of water-soluble sodium acetate in the solution causes it to completely dissociate in water.
 Lecture Notes in Inorganic Chemistry 1
Acids and Bases

The Na+ does not interact with water and is a spectator ion. According to Le Châtelier’s principle, adding
CH3COO- ion will shift the equilibrium position to the left; thus, [H3O+] decreases, in effect lowering the
extent of acid dissociation:

Acetate ion is the common ion because it is “common” to both the acetic acid and sodium acetate solutions.

v A buffer works because a large amount of the acidic component (HA) of the buffer consumes small
amounts of the added OH- and a large amount of the basic component (A-) consumes small amounts of
added H3O+.

Figure 3. Summary of the effect of added acid or base on the concentrations of buffer
components. (Silberberg, 2017)

The Henderson-Hasselbalch Equation

For any weak acid, HA, the dissociation equation and Ka expression are

The key variable that determines [H3O+] is the concentration ratio of acid species to base species, so, as before,
rearranging to isolate [H3O+] gives

taking the negative common logarithm

of both sides gives

Generalizing the previous equation for any conjugate acid-base pair gives the Henderson-Hasselbalch equation:

Buffer Capacity and Buffer Range

Buffer capacity is a measure of the “strength” of the buffer , its ability to maintain the pH following addition of strong
acid or base. Capacity depends ultimately on component concentrations, both the absolute and relative concentrations:
a. In terms of absolute concentrations, the more concentrated the buffer components, the greater the capacity.
b. In terms of relative concentrations, the closer the component concentrations are each other, the greater the
capacity. A buffer has the highest capacity when the component concentrations are equal. When [A-]= [HA],
their ratio is 1, the log term is 0, so pH= pKa

v A buffer whose pH is equal to or near the pKa of its acid component has the highest capacity for a given
concentration.

Buffer range is the pH range over which the buffer is effective and is also related to the relative buffer-component
concentrations. The further the concentration ratio is from 1, the less effective the buffer (the lower the buffer capacity).
v Buffers have a usable range within ±1 pH unit of the pKa of the acid component: pH = pKa ± 1.

Preparing a buffer

Several steps are required to prepare a buffer:

1. Choose the conjugate acid-base pair. Suppose that you need a buffer whose pH is 3.90, therefore to
maximize the capacity, the pKa of the acid component should be close to 3.90 or Ka= 1 x 10-3.90.
2. Calculate the ratio of buffer component concentrations.
3. Determine the buffer concentration.
4. Mix the solution and correct the pH.
 Lecture Notes in Inorganic Chemistry 1
Acids and Bases

Preparing a Buffer.
1. An environmental chemist needs a carbonate buffer of pH 10.00 to study the effects of acid rain on limestone-
rich soils. How many grams of Na2CO3 must she add to 1.5 L of 0.20 M NaHCO3 to make the buffer (Ka of
HCO3− = 4.7×10−11)?
Solution:
The conjugate pair is HCO3− (acid) and CO32- (base)

Practice Exercise
1. A buffered solution contains 0.50 M acetic acid (CH3COOH, Ka= 1.8 x 10-5) and 0.5 M sodium acetate
(NaCH3COO). Calculate the pH of this solution.
2. Calculate the pH of a solution containing 0.75 M lactic acid (Ka= 1.4 x 10-4) and 0.25 M sodium lactate.
Lactic acid (HC3H5O3) is a common constituent of biologic systems. For example, it is found in milk and is
present in human muscle tissue during exertion.

Molecular Properties and Acid Strength

v The strength of an acid depends on its ability to donate a proton, which depends in turn on the strength of
the bond to the acidic proton.
Acid strength of nonmetal hydrides. Two factors determine how easily a proton is released from a nonmetal
hydride:
Ø The electronegativity of the central nonmetal (E). Across a period, acid strength increase. From left to right,
as E becomes more electro- negative, it withdraws electron density from H, and the E-H bond becomes more
polar. As a result, H+ is pulled away more easily by an O atom of a water molecule.
Ø The strength of the E-H bond. Down a group, acid strength increases. E-H bond strength determines this
vertical trend. As E becomes larger, the E-H bond becomes longer and weaker, so H+ comes off more easily.
Acid strength of oxoacids. All oxoacids have the acidic H atom bonded to an O atom, so bond length is not involved.
Ø For oxoacids with the same number of O atoms, acid strength increases with the electronegativity of E.
Ø For oxoacids with different numbers of O atoms, acid strength increases with the number of O atoms (or
with the O.N. of the central nonmetal). The electronegative O atoms pull electron density away from E, which
makes the O-H bond more polar. The more O atoms present, the greater the shift in electron density, and the
more easily the H+ ion comes off.

Figure 4. The relative strengths of oxoacids (Silberberg,

2017).
A. Cl withdraws electron density (thickness of green
arrow) from the O-H bond most effectively, making that
bond most polar (relative size of δ symbols).
B. Additional O atoms pull more electron density from
the O-H bond.
 Lecture Notes in Inorganic Chemistry 1
Acids and Bases

Acid strength of hydrated metal ions. The aqueous solutions of certain metal ions are acidic because the hydrated
metal ion transfers an H+ ion to water.

Consider a general metal nitrate, M(NO3)n, as it dissolves in water. The ions separate and the metal ion becomes
bonded to some number of H2O molecules. This equation shows the hydration of the cation (Mn+) using H2O molecules
and “(aq)”; hydration of the anion (NO3−) is indicated with just “(aq)”.
v If the metal ion, Mn+, is small and highly charged, its high charge density withdraws sufficient electron density
from the O-H bonds of the bound water molecules for an H+ to be released. Thus, the hydrated cation, M(H2O)xn+,
is a typical Brønsted-Lowry acid. The bound H2O that releases the H+ becomes a bound OH- ion:

v Salts of most M2+ and M3+ ions yield acidic aqueous solutions.
Figure 4. The acidic behavior of the hydrated Al3+
ion. (Silberberg, 2017).

The hydrated Al3+ ion is small and highly charged and

pulls electron density from the O-H bonds, so an H+
ion can be transferred to a nearby water molecule.

Electron Pair Donation and Lewis Acid-Base Definition

The final acid-base concept we consider was developed by Gilbert N. Lewis. the Lewis concept highlights the role of
the electron pair. The Lewis acid-base definition holds that
v A base is any species that donates an electron pair to form a bond.
v An acid is any species that accepts an electron pair to form a bond.
Ø The Lewis definition, like the Brønsted-Lowry definition, requires that a base have an electron pair to donate, so
it does not expand the classes of bases. However, it greatly expands the classes of acids. Many species, such as
CO2 and Cu2+, that do not contain H in their formula (and thus cannot be Brønsted-Lowry acids) are Lewis acids
because they accept an electron pair in reactions. In fact, the proton itself is a Lewis acid because it accepts the
electron pair donated by a base:

v Thus, all Brønsted-Lowry acids donate H+, a Lewis acid.

v The product of a Lewis acid-base reaction is an adduct, a single species that contains a new covalent bond:

Ø The Lewis concept broadens the concept of an acid-base reaction (it is the donation and acceptance of an
electron pair to form a covalent bond in an adduct).
Ø Thus, the following conditions must be present as per Lewis definition
§ A Lewis base must have a lone pair of electrons to donate.
§ A Lewis acid must have a vacant orbital (or have the ability to rearrange its bonds to form one) to
accept a lone electron pair and form a new bond.

Molecules as Lewis Acids

a. Lewis acids with electron-deficient atoms
b. Lewis acids with Polar Multiple Bonds
c. Metal cations as Lewis Acids
 Lecture Notes in Inorganic Chemistry 1
Acids and Bases

Ø A metal ion acts as a Lewis acid when it dissolves in water.

Ammonia is a stronger Lewis base than water, because when it is

added to the aqueous solution of the hydrated cation, it displaces H2O.

Practice Exercise.
1. Identify the Lewis acid and Lewis Base in the following reactions.

Hard and Soft acids and bases

Key Point: Hard and soft acids and bases are identified empirically by the trends in stabilities of the complexes that
they form: hard acids tend to bind to hard bases and soft acids tend to bind to soft bases.
Ø The classification of substances as ‘hard’ and ‘soft’ acids and bases was introduced by R.G. Pearson.
Ø Much of the hard-soft distinction depends on polarizability, the degree to which a molecule or ion is easily
distorted by interaction with other molecules or ions.
Ø Electrons in polarizable molecules can be attracted or repelled by charges on other molecules, forming slightly
polar species that can then interact with other molecules.
Ø Hard acids and bases are relatively small, compact and nonpolarizable. Hard acids are any cations with large
positive charge (3+ or larger) or those whose d electrons are relatively unavailable for p bonding (e.g. alkaline
earth ions, Al3+)
Ø Soft acids and bases are larger and more polarizable (therefore “softer”). Soft acids are those whose d electrons
are readily available for p bonding (+1 cations, heavier +2 cations).
Ø The larger and more massive the atom, the softer it is likely to be, because the large numbers of inner electrons
shield the outer ones and make the atom more polarizable.
Ø The trends in bases are easier to see with F- being hard and I- being soft. Again, more electrons and larger size
lead to softer behavior.
Table 3. The classification of Lewis acids and bases (Atkins et al., 2010)

Ø Metal-ligand interaction is an example of a Lewis acid-base interaction. Lewis bases can be divided into 2
categories such as hard bases which contain small, relatively nonpolarizable donor atoms (such as N, O, and F)
and soft bases which contain larger, relatively polarizable donor atoms (such as P, S, and Cl).
Ø Metal ions with highest affinities for hard bases are hard acids and vise versa. Hard acids are usually cations of
electropositive metals, relatively nonpolarizable and have higher charge-to-radius ratio. Whereas, soft acids tend
to be cations of less electropositive metals and have lower charge-to-radius ratio ad are more polarizable.
Ø The interaction between hard acids and bases is primarily electrostatic in nature, the stability of complexes
involving hard acids and bases increases as the positive charge on the metal ion increases and as its radius
decreases.
 Lecture Notes in Inorganic Chemistry 1
Acids and Bases

Ø The interaction between soft metals and soft bases is largely covalent in nature. Most soft-metal ions have a
filled or nearly filled d subshell, which suggests that metal-to-ligand π bonding is important. Complexes of soft
metals with soft bases are therefore much more stable than would be predicted based on electrostatic arguments.

References
Atkins, P., Overton, T., Rourke, J., Weller, M., Armstrong, F., & Hagerman, M. (2010). Shriver & Atkins Inorganic
Chemistry (5th edition), Oxford University Press, Great Britain
Meissler, G.L. & Tarr, D.A. (2008). Inorganic Chemistry (3rd Edition), Pearson Education South Asia Pte. Ltd.
Chang, Raymond, Kenneth A. Goldsby, (2017). Chemistry, (12th International Edition), New York: McGraw-Hill.
Silberberg, (2017). Chemistry: The Molecular Nature of Matter and Change. Advanced Topics (8th edition). New
York: McGraw-Hill.
Zumdahl, S.S., Zumdahl, S.A., & DeCoste, D.J. (2018). Chemistry (10th edition), Cengage Learning.

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