ACIDS

ARRHENIUS DEFINITION OF ACIDS:

An acid is a substance which gives hydrogen ions (H+) when dissolved in water.

For example, in its aqueous solution hydrochloric HCl (aq) dissociates as:

HCl (aq) ⎯⎯→ H+(aq) + Cl–(aq)

HNO3(aq) ⎯⎯→ H+(aq) + NO3–(aq)

BRONSTED LOWRY DEFINITION OF ACIDS:

Acids are Proton donors. An acid must have an acidic proton that can be donated. An acid
molecule can be monoprotic, diprotic, or triprotic (based on number of acidic protons). E.g HCl,
HNO3 H2SO4, H3PO4.

Water can act as an acid, donating a proton to a base and form hydroxide ion OH-

HCl (aq) ⎯⎯→ H+(aq) + Cl–(aq)

An acid and base must always work together to transfer a proton. In aqueous solutions of acids
or bases, water acts as the base or acid “partner”:

LEWIS THEORY

Acid are electron-pair acceptor. It does not necessarily have to supply (H+) or be a proton donor

Some examples of acids are:

(i) Hydrochloric acid (HCl) in gastric juice

(ii) Carbonic acid (H2CO3) in soft drinks

(iii) Ascorbic acid (vitamin C) in lemon and many fruits

(iv) Citric acid in oranges and lemons

(v) Acetic acid in vinegar

(vi) Tannic acid in tea

(vii) Nitric acid (HNO3) used in laboratories

(viii) Sulphuric acid (H2SO4) used in laboratories

Characteristics/reactions of acids

Acids have long been recognized as a distinctive class of compounds whose aqueous solutions
exhibit the following properties:

• A characteristic sour taste;

• Ability to change the color of litmus from blue to red
● It is corrosive
• React with certain metals to produce gaseous H2

Acid + Metal ⎯→ Salt + Hydrogen gas

Zn + H2SO4 ⎯→ ZnSO4 + H2 ↑

• React with bases to form a salt and water. This process is called Neutralization reaction.

HCl(aq) + NaOH(aq) ⎯→ NaCl(aq) + H2O(l)

H2SO4(aq) + 2KOH(aq) ⎯→ K2SO4(aq) + 2H2O(l)

• Reaction of Acids with metal oxides to form salt and water

Metal oxide + Acid ⎯→ Salt + Water

CaO(s) + 2HCl(aq) ⎯→ CaCl2(aq) + H2O(l)

TYPES OF ACIDS

There are 2 types of acids:

STRONG acids- are strong electrolytes because they donate H+ so easily that their dissociation
in water is essentially complete. For example, when HCl, a strong acid, dissociates in water, H+
is transferred to H2O; the resulting solution contains essentially only the ions H3O+ and Cl-. E.g
HI, HCl, HBr, H2SO4, HNO3, H30+

Weak acids are weak electrolytes because they dissociate slightly in water, forming only a small
amount of H3O+ ions. A weak acid has a strong conjugate base, which is why the reverse
reaction is more prevalent. Even at high concentrations, weak acids produce low concentrations
of H3O+ ions. Many of the products you use at home contain weak acids. Citric acid is a weak
acid found in fruits and fruit juices such as lemons, oranges, and grapefruit. The vinegar used in
salad dressings is typically a 5% (m/v) acetic acid (HC2H3O2 ) solution. In water, a few
HC2H3O2 molecules donate H+ to H2O to form H3O+ ions and acetate ions (C2H3O2 -). The
reverse reaction also takes place, which converts the H3O+ ions and acetate ions (C2H3O2 -)
back to reactants. The formation of hydronium ions from vinegar is the reason we notice the sour
taste of vinegar.
BASES

They are ionic compounds that dissociate into cations and hydroxide ions (OH-) when they
dissolve in water. They are another example of strong electrolytes. For example, sodium
hydroxide is an Arrhenius base that dissociates completely in water to give sodium ions (Na+)
and hydroxide ions (OH-).

Most Arrhenius bases are formed from Groups 1A (1) and 2A (2) metals, such as NaOH, KOH,
LiOH, and Ca(OH)2. The hydroxide ions (OH-) give Arrhenius bases common characteristics,
such as a bitter taste and a slippery feel. A base turns litmus indicator blue and phenolphthalein
indicator pink.

A Brønsted–Lowry base is a substance that accepts H+.

Strong and Weak Bases:

As strong electrolytes, strong bases dissociate completely in water. Because these strong bases
are ionic compounds, they dissociate in water to give an aqueous solution of metal ions and
hydroxide ions. The Group 1A (1) hydroxides are very soluble in water, which can give high
concentrations of OH- ions. A few strong bases are less soluble in water, but what does dissolve
dissociates completely as ions. For example, when KOH forms a KOH solution, it contains only
the ions K+ and OH-.

KOH(s) K+(aq) + OH-(aq)

Strong Bases

Lithium hydroxide (LiOH), Sodium hydroxide (NaOH), Potassium hydroxide (KOH), Rubidium
hydroxide (RbOH), Cesium hydroxide (CsOH), Calcium hydroxide (Ca(OH)2),

Weak bases are weak electrolytes that are poor acceptors of hydrogen ions and produce very
few ions in solution. A typical weak base, ammonia (NH3) is found in window cleaners. In an
aqueous solution, only a few ammonia molecules accept hydrogen ions to form NH4 + and OH-.

NH3(g) + H2O(l) NH4 + (aq) + OH-(aq)

CHARACTERISTICS/REACTIONS OF BASES

• Feel slippery or soapy

• Tastes bitter
• Change red litmus blue
• become less basic on mixing with with bases acids
• Reaction of bases with metals: Like acids, bases also react with active metals liberating
hydrogen gas. For example, sodium hydroxide reacts with zinc as shown below:
 Zn(s) + 2NaOH(aq) ⎯→ Na2ZnO2(aq) + H2(g) ↑

• Reaction of Bases with non-metal oxides Bases react with oxides of non-metals like CO2,
SO2, SO3, P2O5 etc. to form salt and water

Ca(OH)2(aq) + CO2(g) ⎯→ CaCO3(s) + H2O(l)

• Reaction of bases with acids: Such reactions are called neutralization reactions and result
in the formation of salt and water. E.g

HCl(aq) + KOH(aq) ⎯→ KCl(aq) + H2O(l)

H2SO4(aq) + 2NaOH(aq) ⎯→ Na2SO4(aq) + 2H2O(l)

SALTS

Salts are ionic compounds made of a cation other than H+ ion and an anion other than OH– ion.

Formation of salts

Salts are formed in many reactions involving acids and bases.

• By Neutralization of acids and bases: Salts are the product (besides water) of a
neutralization reaction. For example
NaOH + HCl ⎯→ NaCl + H2O
KOH + HNO3 ⎯→ KNO3 + H2O
• By action of acids on metals: In a reaction between an acid and a metal, salt is produced
along with hydrogen, Metal, Acid Salt, Hydrogen

Zn + H2SO4 ⎯→ ZnSO4 + H2

• By action of acids on metal carbonates and hydrogen carbonates: Salts are produced
in reactions between acids and metal carbonates and hydrogen carbonates (bicarbonates)
along with water and carbon dioxide

CaCO3 + 2HCl ⎯→ CaCl2 + H2O + CO2

NaHCO3 + HCl ⎯→ NaCl + H2O + CO2

CONJUGATE ACID BASE PAIR

There is a relationship between the components in each conjugate acid–base pair. Strong acids
have weak conjugate bases that do not readily accept H+. As the strength of the acid decreases,
the strength of its conjugate base increases. In any acid–base reaction, there are two acids and
two bases. However, one acid is stronger than the other acid, and one base is stronger than the
other base. By comparing their relative strengths, we can determine the direction of the reaction.
For example, the strong acid H2SO4 readily gives up H+ to water. The hydronium ion H3O+
produced is a weaker acid than H2SO4, and the conjugate base HSO4 - is a weaker base than
water.

H2SO4(aq) + H2O(l) H3O+(aq) + HSO-4 (aq)

S.acid s.base w.acid w.base

We can rank the strengths of acids by the extent to which they ionize in aqueous solution. The
reaction of an acid with water is given by the general expression:

HA(aq)+H2O(l)⇌H3O+(aq)+A−(aq)

Water is the base that reacts with the acid HA, A − is the conjugate base of the acid HA, and the
hydronium ion is the conjugate acid of water. A strong acid yields 100% (or very nearly so)
of H3O+H3O+ and A− when the acid ionizes in water.

we write the equation for the ionization constant as:

Ka=[H3O+] / [A−][HA]
where the concentrations are those at equilibrium. Although water is a reactant in the reaction, it
is the solvent as well, so we do not include [H 2O] in the equation. The larger the Ka of an acid,
the larger the concentration of H3O+ and A− relative to the concentration of the non ionized acid,
HA. Thus a stronger acid has a larger ionization constant than does a weaker acid. The ionization
constants increase as the strengths of the acids increase.

We can rank the strengths of bases by their tendency to form hydroxide ions in aqueous solution.
The reaction of a Brønsted-Lowry base with water is given by:

B(aq)+H2O(l)⇌HB+(aq)+OH−(aq)

Water is the acid that reacts with the base, HB + is the conjugate acid of the base B, and the
hydroxide ion is the conjugate base of water. A strong base yields 100% (or very nearly so) of
OH− and HB+ when it reacts with water.

A weak base yields a small proportion of hydroxide ions. Soluble ionic hydroxides such as
NaOH are considered strong bases because they dissociate completely when dissolved in water.

Calculate the relative strengths of bases by measuring their base-ionization constant (Kb) in
aqueous solutions. In solutions of the same concentration, stronger bases ionize to a greater
extent, and so yield higher hydroxide ion concentrations than do weaker bases. A stronger base
has a larger ionization constant than does a weaker base. For the reaction of a base, B:

B(aq)+H2O(l)⇌HB+(aq)+OH−(aq)

we write the equation for the ionization constant as:

Kb= [HB+]/[OH−][B]

Where the concentrations are those at equilibrium. Again, we do not include [H 2O] in the
equation because water is the solvent.

Self dissociation of water

Water plays an important role in acid base chemistry. We have seen that it helps in the
dissociation of acids and bases resulting in the formation of H+(aq) and OH– (aq) ions
respectively. Water itself undergoes dissociation process which is called ‘self-dissociation of
water’.

Water dissociates into H+(aq) and OH–(aq) ions as:

H2O(l) H+(aq) + OH–(aq)

 The dissociation of water is extremely small and only about two out of every billion, water
molecules are dissociated at 25°C. As a result, the concentrations of H+(aq) and OH–(aq) ions
formed is also extremely low.

At 25°C, [H+] = [OH–] = 1.0 × 10–7 mol L–1 Here, square brackets denote the molar
concentration of the species enclosed within. Thus, [H+] denotes the concentration of H+(aq)
ions in moles per litre and [OH–] the concentration of OH–(aq) ions in moles per litre. It must be
noted here that in pure water and in all aqueous neutral solutions, [H+] = [OH–] Also, in pure
water as well as in all aqueous solutions at a given temperature, product of concentrations of H+
(aq) and OH–(aq) always remains constant. This product is called ‘ionic product of water’ and is
given the symbol Kw. It is also called ionic product constant of water.

Thus, Kw = [H+] [OH–] At 25°C (298 K), in pure water,

Kw can be calculated as:

Kw = (1.0 × 10–7) × (1.0 × 10–7) = 1.0 × 10–14

Neutral, acidic and basic solutions

We have seen that in pure water H+(aq) and OH–(aq) ions are produced in equal numbers as a
result of dissociation of water and therefore, their concentrations are also equal i.e. [H+] = [OH–]
(i) Neutral solutions: In all neutral aqueous solutions, the concentrations of H+(aq) and OH–
(aq) ions remains equal i.e. [H+] = [OH–] In other words the neutral solution is the one in which
the concentrations of H+ and OH– ions are equal.

(ii) Acidic solutions: Acids furnish H+(aq) ions in their solutions resulting in increase in their
concentration. Thus, in acidic solution.

[H+] > [OH–] and [H+] > 1.0 × 10–7 mol L–1

In other words the acidic solution is the one in which the concentration of H+(aq) is greater than
that of OH–(aq) ions.

(iii) Basic solutions: Bases furnish OH–(aq) ions in their solutions. This results in an increase in
their concentration. Therefore, in basic solution [OH–] > [H+] and [OH–] > 1.0 × 10–7 mol L–1
In other words, the basic solution is the one in which the concentration of H+(aq) ions is smaller
than that of OH–1(aq) ions. Here also, because of constancy of ionic product of water Kw, the
concentration of H+(aq) decreases. Thus and [H+] < 1.0 × 10–7 mol L–1
PH

pH is a unit of measure which describes the degree of acidity or alkalinity of a solution. It is

measured on a scale of 0 to 14. The formal definition of pH is: the negative logarithm of
Hydrogen ion activity.

pH = -log[H+]

pH provides needed quantitative information by expressing the degree of activity of an acid or

base in terms of its hydrogen ion activity. The pH value of a substance is directly related to the
ratio of hydrogen ion [H+] and hydroxyl ion [OH-] concentrations. If the H+ concentration is
greater than the OH-, the material is acidic; i.e., the pH value is less than 7. If the OH
concentration is greater than its H+, the material is basic, with a pH value greater than 7. If equal
numbers of H+ and OH ions are present, the material is neutral, with a pH of 7.

The pH is the logarithm of the reciprocal of the hydrogen ion concentration. It is written as:

pH = + 1 log ⎡ ⎤ H ⎣ ⎦

Alternately, the pH is the negative logarithm of the hydrogen ion concentration i.e

pH = –log [H+].

Because of the negative sign in the expression, if [H+] increases, pH would decrease and if it
decreases, pH would increase.

In pure water at 25° (298 K)

[H+] = 1.0 × 10–7 mol L–1

log[H+] = log(10–7) = –7

and pH = –log[H+] = –(–7)

pH = 7

Since in pure water at 25°C (298 K)

[OH–] = 1.0 × 10–7 mol L–1

Also, pOH = 7 Since,

Kw = 1.0 × 10–14 pKw = 14

The relationship between pKw, pH and pOH is

pKw = pH + pOH at 25°C (298 K)

14 = pH + pOH

at 25°C (298 K)

14 = pH + pOH

EXAMPLE

Calculate the pH of 0.001 molar solution of HCl.

Solution: HCl is a strong acid and is completely dissociated in its solutions according to the
process:

HCl(aq) ⎯→ H+(aq) + Cl–(aq)

From this process it is clear that one mole of HCl would give one mole of H+ ions. Therefore,
the concentration of H+ ions would be equal to that of HCl i.e.

0.001 molar or 1.0 × 10–3 mol L–1.

Thus, [H+] = 1 × 10–3 mol L–1

pH = –log[H+] = –(log 10–3) = –(–3 × log10) = –(3 × 1) = 3 Thus, pH = 3

2. Calculate the pH of a solution in which the concentration of hydrogen ions is

1.0 × 10–8 mol L–1.

pH = –log[H+]

given [H+] = 1.0 × 10–8 mol L–1

∴ pH = –log10–8 = –(–8 × log10)

= –(–8 × 1) = 8
pH SCALE

Determination of pH

pH of a solution can be determined by using proper indicator or with the help of a pH meter. The
latter is a device which gives accurate value of pH.

Universal Indicator/pH paper: It is a mixture of a number of indicators. It shows a specific

colour at a given pH. A colour guides is provided with the bottle of the indicator or the strips of
paper impregnated with it which are called pH paper strips. The test solution is tested with a drop
of the universal indicator, or a drop of the test solution is put on pH paper. The colour of the
solution on the pH paper is compared with the colour chart/guard and pH is read from it. The pH
values thus obtained are only approximate values.
BUFFERS

A buffer is a solution containing either a weak acid and its salt or a weak base and its salt, which
is resistant to changes in pH. In other words, a buffer is an aqueous solution of either a weak acid
and its conjugate base or a weak base and its conjugate acid. A buffer may also be called a pH
buffer, hydrogen ion buffer, or buffer solution.

Buffers are used to maintain a stable pH in a solution, as they can neutralize small quantities of
additional acid of base. For a given buffer solution, there is a working pH range and a set amount
of acid or base that can be neutralized before the pH will change. The amount of acid or base that
can be added to a buffer before changing its pH is called its buffer capacity.

The Henderson-Hasselbalch equation may be used to gauge the approximate pH of a buffer. In

order to use the equation, the initial concentration or stoichiometric concentration is entered
instead of the equilibrium concentration.

The general form of a buffer chemical reaction is:

HA ⇌ H+ + A−

Examples of Buffers

blood - contains a bicarbonate buffer system

TRIS buffer

phosphate buffer

As stated, buffers are useful over specific pH ranges. For example, here is the pH range of
common buffering agents:
Buffer pKa pH range

citric acid 3.13., 4.76, 6.40 2.1 to 7.4

acetic acid 4.8 3.8 to 5.8

KH2PO4 7.2 6.2 to 8.24

Borate 9.24 8.25 to 10.25

CHES 9.3 8.3 to 10.3

When a buffer solution is prepared, the pH of the solution is adjusted to get it within the correct
effective range. Typically a strong acid, such as hydrochloric acid (HCl) is added to lower the pH
of acidic buffers. A strong base, such as sodium hydroxide solution (NaOH), is added to raise the
pH of alkaline buffers.

How Buffers Work

In order to understand how a buffer works, consider the example of a buffer solution made by
dissolving sodium acetate into acetic acid. Acetic acid is (as you can tell from the name) an acid:
CH3COOH, while the sodium acetate dissociates in solution to yield the conjugate base, acetate
ions of CH3COO-. The equation for the reaction is:

CH3COOH(aq) + OH-(aq) ⇆ CH3COO-(aq) + H2O(aq)

If a strong acid is added to this solution, the acetate ion neutralizes it:

CH3COO-(aq) + H+(aq) ⇆ CH3COOH(aq)

This shifts the equilibrium of the initial buffer reaction, keeping the pH stable. A strong base, on
the other hand, would react with the acetic acid.

Universal Buffers

Most buffers work over a relative narrow pH range. An exception is citric acid because it has
three pKa values. When a compound has multiple pKa values, a larger pH range becomes
available for a buffer. It's also possible to combine buffers, providing their pKa values are close
(differing by 2 or less), and adjusting the pH with strong base or acid to reach the required range.
For example, McIvaine's buffer is prepared by combining mixtures of Na 2PO4 and citric acid.
Depending on the ratio between the compounds, the buffer may be effective from pH 3.0 to 8.0.
A mixture of citric acid, boric acid, mono potassium phosphate, and diethyl barbituic acid can
cover the pH range from 2.6 to 12!