Acids, Bases and Salts

Why everything tastes so differently? Why lemon is tangy and mango

is sweet? This is because of different percentage of acids, bases, and
salts in their chemical composition. Let’s learn how these can be
characterized, understanding the concepts by Arrhenius,
Bronsted-Lowry and Lewis etc.

Experimental Definitions

Earlier, acids, bases, and salts were characterized by the experimental

testing of their aqueous ​solutions​. An acid is defined as a substance
whose water solution tastes sour, turns blue litmus red and neutralizes
bases. A substance is called base if its aqueous solution tastes bitter,
turns red litmus blue or neutralizes acids.

Salt is a neutral substance whose aqueous solution does not affect

litmus. According to Faraday: acids, bases, and salts are termed as
electrolytes. Further, Liebig proposed that acids are compounds which
contain ​hydrogen​ that can be replaced by metals.

Acids

Acidity is a characteristic property of acids. Acidic substances are

usually very sour. Apart from hydrochloric acid, there are many other
types of acids around us. Citrus fruits like lemons and oranges contain
citric and ascorbic acids while tamarind paste contains tartaric acid.

In fact, the word ‘acid’ and ‘acidity’ are derived from the Latin word
‘acidus’ which means sour. If you dip a blue litmus paper into an acid,
it will turn red while a red litmus paper will not change colour. Acids
also liberate dihydrogen when they react with some ​metals​.

Bases

Bases turn red litmus paper blue while the blue litmus paper stays
blue. They taste bitter and also feel soapy. Some other common
examples of bases include sodium bicarbonate that is used in cooking
and household bleach.
 Image: Litmus paper test. [Source: Wikimedia Commons]

Salts

Apart from sodium chloride, other common salts are sodium nitrate,
barium sulfate etc. Sodium chloride or common salt is a product of the
reaction between the hydrochloric acid (acid) and sodium hydroxide
(base). Solid sodium chloride is made of a cluster of positively
charged sodium ions and negatively charged chloride ions held
together by electrostatic forces.

Electrostatic ​forces​ between opposite charges are inversely

proportional to the dielectric constant of the medium. In other words,
we can say that a compound that has acidity in its nature and a
compound that has basicity as its nature, may yield salts when
combined together.
The universal solvent, ​water​, has a dielectric constant of 80.
Therefore, when sodium chloride is dissolved in water, the dielectric
constant of water reduces the electrostatic force, allowing the ions to
move freely in the solution. They are also well-separated due to
hydration with water ​molecules​.

Image: Dissolution of sodium chloride in water [Source: Wikimedia Commons]

Ionization And Dissociation

Dissociation is the separation of ions from an ionic crystal when a

solid ionic compound dissolves in water. On the other hand, ionization
is the process where a neutral molecule breaks into charged ions when
dissolved in a solution. The extent of ionization depends on the
strength of the bonds between ions and the extent of solvation of ions.

The three most important modern concepts of acids and bases are:

Arrhenius Concept

According to Arrhenius concept, Substances which produce H​+​ ions

when dissolved in water are called acids while those which ionize in
water to produce OH​–​ ions are called bases.

HA → H​+​ + A​–​ (Acid)

BOH → B​+​ + OH​–​ (Base)

Arrhenius proposed that acid-base reactions are characterized by acids

if they dissociate in aqueous solution to form hydrogen ions (H​+​) and
bases if they form hydroxide (OH​–​) ions in aqueous solution.

Limitations of Arrhenius Concept

● The presence of water is absolutely necessary for acids and
bases. Dry HCl can’t act as an acid. HCl acts as an acid in
water only and not any other solvent.
 ● The concept does not explain the acidic and basic character of
substances in non-aqueous solvents.
● The neutralization process is only possible for reactions which
can occur in aqueous solutions, although reactions involving
salt formation can occur in the absence of a solvent.
● The acidic character of some salts such as AlCl​3​ in aqueous
solution can’t be explained.
● An extended as well as artificial explanation is needed to define
the basic nature of NH​3​.

Bronsted-Lowry Concept

Bronsted and Lowry in 1923 independently proposed a more general

definition of acids and bases. According to them, an acid is defined as
any hydrogen-containing material (molecule, anion or cation) which
can donate a proton to other substance and a Base is any
substance(molecule, cation or anion) that can accept a proton from any
other substance. Therefore, acids are proton donor whereas bases are
proton acceptor.
Conjugate Acid-Base Pairs

Consider a reaction

Acid​1​ + Base​2​ → Acid​2​ + Base​1

H​2​O + HCl ⇔ H​3​O​+ +

​ Cl​–

In this reaction, HCl donates a proton to H​2​O and is, therefore an acid.
Water, on the other hand, accepts a proton from HCl, and is, therefore,
a base. In the reverse reaction which at equilibrium proceeds at the
same rate as the forward reaction, the H​3​O​+​ ions donate a proton to
Cl– ion, hence H​3​O​+​, an ion is an acid. Cl​–​ ion, because it accepts a
proton fromH​3​O​+​ ion, is a base.
Acid-base pairs in which the members of reaction can be formed from
each other by the gain or loss of protons are called conjugate acid-base
pairs.

Limitations of Bronsted Lowry Concept

● Bronsted Lowry could not explain the reaction occurring in the
non-protonic solvent like COCl​3​, SO​2​, N​2​O​4​, etc.
● It cannot explain the reactions between acidic oxides like etc
and the basic oxides like etc which can easily take place in the
absence of solvent as well e.g. (No proton transfer)
● Substances like BF​3​, AlCl​3​ etc, do not contain hydrogen which
means they can’t donate a proton, still they behave as acids.

Lewis Concept

According to Lewis theory of acid-base reactions, bases donate pairs

of electrons and acids accept pairs of electrons. Thus, it can be said
that a Lewis acid is electron-pair acceptor.

The advantage of the Lewis theory is that complements the model of

oxidation-reduction reactions. Oxidation-reduction reactions take
place on a transfer of electrons from one atom to another, with a net
change in the oxidation number of one or more ​atoms​.

The Lewis theory further suggested that acids react with bases and
share a pair of electrons but there is no change in the oxidation
numbers of any atoms. Either an electron is transferred from one atom
to another, or the atoms come together to share a pair of electrons.

Al(OH)​3 ​+ 3H​+​ → Al​3+​ + 3H​2​O (Aluminium hydroxide is acting as a

base)

Al(OH)​3​ + OH​–​ → Al(OH)​4-​ (Aluminium hydroxide is acting as an

acid)

These reactions are showing clearly: When Aluminium hydroxide

accepts protons, it acts as a base. When it accepts electrons, it acts as
an acid. This Lewis acid-base theory also explains why non-metal
oxides such as ​carbon​ dioxide dissolve in H​2​O to form acids, such as
carbonic acid H​2​CO​3​.

CO​2​(​g​) + H​2​O(​l​) → H​2​CO​3​(​aq​)

Limitations of Lewis Concept

 ● Lewis concept gave a generalized idea including all
coordination reactions and compounds. This is not true always.
● An idea about the relative strength of acids and bases is not
provided by Lewis concept.
● Lewis concept is not in line with the acid-base reaction
concept.
● Lewis concept has not discussed the behaviour of protonic
acids like HCl.

Solved Example for You

Question: Whether the following ions or molecules can act as Lewis

acid or a Lewis base?

● Ag​+
● NH​3

Solution:

● A silver cation is Lewis acid

 ● Ammonia is Lewis base

Buffer Solutions

What do you think will happen if the pH of our blood changes

drastically from its normal pH of 7.35? Yes, the cells of our body will
not function properly and our body systems will fail! Human blood
contains a ‘buffer’ that allows it to maintain its pH at 7.35 to ensure
normal functioning of ​cells​. Buffer solutions are also important in
chemical and biochemical processes where the control of pH is very
important. Let’s understand buffer solutions in more detail.

Buffer Solutions

Buffers are solutions that resist a change in pH on dilution or on

addition of small amounts of ​acids​ or alkali.

A lot of biological and ​chemical reactions​ need a constant pH for the

reaction to proceed. Buffers are extremely useful in these systems to
maintain the pH at a constant value. This does not mean that the pH of
buffers does not change. It only means that the change in pH is not as
much as it would be with a solution that is not a buffer.

Browse more Topics under Equilibrium

● Acids, Bases and Salts
● Equilibrium in Chemical Processes
● Equilibrium in Physical Processes
● Factors Affecting Equilibria
● Ionization of Acids and Bases
● Law of Chemical Equilibrium and Equilibrium Constant
● Solubility Equilibria

Learn more about ​pH Scale​ here in more detail.

Types of Buffer Solutions

Buffers are broadly divided into two types – acidic and alkaline buffer
solutions. Acidic buffers are ​solutions​ that have a pH below 7 and
contain a weak acid and one of its salts. For example, a mixture of
acetic acid and sodium acetate acts as a buffer solution with a pH of
about 4.75.
Alkaline buffers, on the other hand, have a pH above 7 and contain a
weak base and one of its ​salts​. For example, a mixture of ammonium
chloride and ammonium hydroxide acts as a buffer solution with a pH
of about 9.25. Buffer solutions help maintain the pH of many different
things as shown in the image below.
Preparation of a Buffer Solution

If you know the pK​a​ (acid dissociation constant) of the acid and pK​b
(base dissociation constant) of the ​base​, then you can make a buffer of
known pH by controlling the ratio of salt and acid or salt and base.
Buffers can either be prepared by mixing a weak acid with its
conjugate base or a weak base with its conjugate acid.

For example, phosphate buffer, a commonly used buffer in research

labs, consists of a weak base (HPO​42-​) and its conjugate acid
(H​2​PO​4​–​). Its pH is usually maintained at 7.4.

Understand the ​Concept of Equilibrium in Chemical Process​ in detail

here.

Buffer Action

So, how does a buffer work? Let’s take the example of a ​mixture​ of
acetic acid (CH​3​COOH) and sodium acetate (CH​3​COONa). Here,
acetic acid is weakly ionized while sodium acetate is almost
completely ionized. The equations are given as follows:

CH​3​COOH H​+​ + CH​3​COO​–

CH​3​COONa Na​+​ + CH​3​COC​–

To this, if you add a drop of a strong acid like HCl, the H​+​ ions from
HCl combine with CH​3​COO​– ​to give feebly ionized CH​3​COOH.
Thus, there is a very slight change in the pH value. Now, if you add a
drop of NaOH, the OH​–​ ions react with the free acid to give
undissociated ​water​ ​molecules​.

CH​3​COOH + OH​–​ CH​3​COO​–​ + H​2​O

In this way, the OH​– ​ions​ of NaOH are removed and the pH is almost
unaltered.

Learn more about ​ionization of Acids and Bases​ here.

Solved Example for You

Question: Which of the following statement/s is false about buffer

solutions?

a. The pH of a buffer solution does not change on dilution.

b. Buffer solutions do not have a definite pH.
c. The pH of a buffer solution changes slightly on the addition of
a small amount of acid or base.
d. The pH of buffer solution does not change on standing for long.
Solution: The option ‘b’ is false. Buffer solutions have a definite pH.

Equilibrium in Physical Processes

Just the way ​chemical reactions​ attain a state of equilibrium, there

exists equilibrium in physical processes too. This refers to the
equilibrium that develops between different states or phases of a
substance such as solid, liquid and gas. Let’s try and understand
equilibrium in physical processes in more detail. Substances undergo
different phase transformation processes such as –

solid ​⇌ liquid

liquid ⇌ gas

solid ⇌ gas

Let’s understand how they attain equilibrium during each of these

transformations.

Solid-Liquid Equilibrium
What happens if you keep ice and water in a perfectly insulated
manner, such as in a thermos flask at a temperature of 273K and
atmospheric ​pressure​? We see that the mass of ice and water do not
change and that the temperature remains constant, indicating a state of
equilibrium.

However, the equilibrium is not static because there is intense activity

at the boundary between ice and water. Some ice molecules escape
into liquid water and some molecules of water collide with ice and
adhere to it. Despite this exchange, there is no change in mass of ice
and water. This is because the rates of transfer of ice molecules to
water and the reverse process are equal at 273K and atmospheric
pressure.

It is evident that ice and water are in equilibrium only at a particular

pressure and ​temperature​. Therefore, for any pure substance at
atmospheric pressure, the temperature at which the solid and liquid
phases are at equilibrium is called the normal melting point or normal
freezing point of the substance.
The system of ice and ​water​ is in dynamic equilibrium and we can
conclude the following –

● Both opposing processes occur at the same time.

● The two processes occur at the same rate such that the amount
of ice and water remain constant.

Browse more Topics under Equilibrium

● Acids, Bases and Salts
● Buffer Solutions
● Equilibrium in Chemical Processes
● Factors Affecting Equilibria
● Ionization of Acids and Bases
● Law of Chemical Equilibrium and Equilibrium Constant
● Solubility Equilibria

Liquid-vapour Equilibrium
Equilibrium Vapor Pressure

To understand this concept, let’s perform the following experiment.

Experiment:

● Place a drying agent like anhydrous calcium chloride for a few

hours in a transparent box with a U-tube containing mercury
i.e. manometer. This will soak up all the moisture in the box.
● Remove the drying ​agent​ by tilting the box to one side and
quickly place a petri dish containing water.

Observations:

● The mercury in the manometer rises slowly and then attains a

constant value. This is because the pressure inside the
manometer increases due to the addition of water ​molecules
into the gaseous phase.
● Initially, there is no water vapour in the box. As the water in
the petri dish evaporates, the volume of water in the petri dish
decreases and the pressure in the box increases.
● The rate of increase in pressure decreases with time because of
condensation of vapour into water.
 ● Finally, it reaches an equilibrium where there is no net
evaporation​ or condensation.

Conclusion: Equilibrium is reached when the

rate of evaporation = rate of condensation

H​2​O(l) ⇌ H​2​O (vap)

At equilibrium, the pressure that the water molecules exert at a given

temperature remains constant and is called the equilibrium ​vapour
pressure​ of water. The vapour pressure of water increases with
temperature.

Boiling Point

At the same temperature, different liquids have different equilibrium

vapour pressures. The liquid with a higher vapour pressure is more
volatile and has a lower boiling point. Let’s understand this concept
with the following experiment.

Experiment:
 ● Expose three Petri dishes containing 1ml each of acetone, water
and ethyl alcohol to the atmosphere.
● Repeat the experiment with different liquid volumes in a
warmer room.

Observations:

● In all cases, the liquid eventually disappears.

● The time taken for complete evaporation of each liquid differs.

Conclusions:

● The time taken for complete evaporation of the liquid depends

on – the nature of the liquid, the amount of liquid and the
temperature.
● In an open system i.e. when the petri dish is kept open, the rate
of evaporation remains constant but the molecules of the liquid
are dispersed into a larger volume of the room. Consequently,
the rate of evaporation is much higher than the rate of
 condensation from vapour to liquid. Therefore, open systems
do not reach an equilibrium.

On the other hand, in a closed vessel or system, water and water

vapour are in equilibrium at atmospheric pressure (1.013 bar) and
100°C.

For any pure liquid at one atmospheric pressure, the temperature at

which the liquid and vapour are at equilibrium is called the normal
boiling point of the liquid.

For water, the boiling point is 100°C at atmospheric pressure. The

boiling point of liquids depends on atmospheric pressure i.e. the
altitude of the place. Boiling point decreases at higher altitudes.

Solid-Vapor Equilibrium

Have you ever observed what happens to solid iodine placed in a

closed jar? The jar gets filled up with violet coloured vapour and the
colour intensity increases with time! The intensity of the colour
becomes constant after a certain time i.e. equilibrium is reached. In
this way, solid iodine sublimes to give iodine vapour while the vapour
condenses to form solid iodine. The equilibrium in this process is
given as –

I​2​(solid) ⇌ I​2​(vapour)

Sublimation of Iodine [Source: Wikimedia Commons]

Other substances that show this kind of equilibrium are –

Camphor (solid) ⇌ Camphor (vapour)

NH​4​Cl (solid) ⇌ NH​4​Cl (vapour)

Equilibrium Involving Dissolution of Solid or

Gases in Liquids
Solids In Liquids
What happens when you make a thick sugar solution by dissolving
sugar at high temperature, then allow it to cool at room temperature.
Yes, the sugar crystals separate out.

In this case, the thick sugar solution is a saturated solution because no

more solute i.e. sugar can be dissolved in it at a given temperature.
The concentration of solute in a saturated solution depends on the
temperature. A dynamic equilibrium exists between the solute
molecules in the solid state and in solution in a saturated solution.

Sugar (solution) ⇌ Sugar (solid)

Also, the rate of dissolution of sugar = rate of crystallization of sugar.

Let’s understand this further, using an example. What happens when
you add radioactive sugar to a saturated solution of non-radioactive
sugar? You will see radioactivity both in the solution and solid sugar
after some time. Initially, there are no radioactive sugar molecules in
the ​solution​.

But, due to the dynamic nature of equilibrium, there is an exchange

between the radioactive and non-radioactive sugar molecules from the
two phases. Thus, the ratio of radioactive to non-radioactive sugar
molecules in the solution increases till it reaches a constant value.

Gases In Liquids

Why do we see fizz and hear a sound when we open soda bottles?
This happens because some of the CO​2​ dissolved in it fizzes out
rapidly due to the difference in solubility of CO​2​ at different
pressures. The equilibrium between the CO​2​ molecules in the gaseous
state and those dissolved in liquid under pressure is given as –

CO​2​(gas) ⇌ CO​2​(in solution)

This equilibrium is governed by Henry’s law. It states that the mass of

a gas dissolved in a given mass of a solvent at any temperature is
proportional to the pressure of the gas above the solvent. This amount
decreases with increase in temperature.

The soda bottle is sealed under the pressure of the gas where its
solubility in water is high. When the bottle is opened, some of the CO​2
escapes trying to reach a new equilibrium or its partial pressure in the
atmosphere. This is why soda water turns flat when the bottle is left
open for too long.
 Fizz in soda water [Source: pxhere]

Features of Equilibrium in Physical Processes

Process Conclusion

Solid ⇌ Liquid
Melting point is fixed at constant pressure.
H​2​O(s) ⇌ H​2​O(l)

Liquid⇌ Vapour
pH​2​O constant at given temperature.
H​2​O(l)⇌ H​2​O(g)

Solute(s) ⇌ Solute (solution)

Concentration of solute in solution is constant at a given
temperature.
Sugar(s) ⇌ Sugar (solution)
 [gas(aq)]/[gas(g)] is constant at a given temperature.

Gas(g) ⇌ Gas (aq)

[CO​2​(aq)]/[CO​2​(g)] is constant at a given
CO​2​(g) ⇌ CO​2​(aq) temperature.

General Characteristics Of Equilibrium In Physical

Processes

The following characteristics are common to the state of equilibrium

in physical processes.

● At a given temperature, equilibrium in physical processes is

achieved only in a closed system.
● The opposing processes occur at the same rate and there exists
a dynamic but stable condition during equilibrium in physical
processes.
● All properties of the system that are measurable remain
constant.
● Equilibrium in physical processes is characterized by a constant
value of one of its parameters at a given temperature.
 ● The extent to which a physical process has progressed before
reaching equilibrium is indicated by the magnitude of the
abovementioned parameter at any stage.

Solved Example For You

Question: The fizz observed when you open a bottle of soda water is
governed by which of the following laws?

a. Murphy’s law
b. Henry’s law
c. Raoult’s law
d. Avogadro law

Solution: The answer is option ‘b’. Henry’s law explains the

phenomenon of fizz i.e. the escape of some CO​2​ molecules due to the
difference in solubility of CO​2​ at different pressures.

Factors Affecting Equilibria

Chemical equilibria in a chemical ​reaction​ define the state in which

there is no further change in the concentration of the reactants and
products. In numerous biological and environmental processes, these
chemical equilibria play an important role.

One example we can consider for chemical equilibria is that it

involves molecules of O2 and the protein haemoglobin play a crucial
role in the transportation and delivery of O2 from our lungs to our
muscles. Similarly, the equilibria that involve the CO molecules and
haemoglobin that accounts and leads to the toxicity of CO.

Factors Affecting Equilibria

According to the Le Chatelier’s Principle, states that if a system under

equilibrium is subjected to a change in pressure, temperature or
concentration, in this case, the equilibrium shifts further reducing as
well as to counteract the effect of the change. The factors that affect
equilibria are:

Effect of Pressure Change

There is no effect of pressure if the number of moles of gaseous
reactant and products is equalised. However, it is different for the total
number of moles of gaseous reactants and a total number of moles of
gaseous​ products. On increasing the ​pressure​, the total number of
moles per unit volume also increases leading to shifting in the
equilibrium direction wherein the number of moles per ​unit​ volume
will be less.

If the total number of ​moles​ of products are more than the total
number of moles of reactants, in this case, the low pressure will also
favour forward reaction. If the number of moles of reactants is more
than that of products, high pressure would be favourable to forward
reaction.

Effect of Change of Concentration

The equilibrium changes when the concentration of any reactants or

products in the reaction changes. It further leads to minimising its
effect.

Effect of Inert Gas Addition

After the addition of an inert ​gas​ and with the volume kept constant,
there is no effect on the equilibrium. This is because, at constant
volume, the addition of an inert gas does not change partial pressure or
molar ​concentration​.

Effect of Temperature Change

The equilibrium shifts in opposite direction when there is a change of

increase or decrease in the system of temperature. This takes effect in
order to neutralise the change in effect. In an exothermic reaction, the
low temperature favours forwards reaction –

For example. N2(g) + 3H2(G) ——— 2NH3 (g)

∆H = -92.38 kJ mol ​-1

Low temperature slows down the reaction for which we are using the
catalyst. In case of an endothermic reaction, the increase in
temperature will shift the equilibrium in direction of the endothermic
reaction.

Effect of a Catalyst

There is no effect on the equilibrium composition of a reaction

mixture. This is because catalyst increases the speed of both forward
and backward reactions to the same extent in a reversible reaction.
Solved Examples for You

Question: In the reaction A + B -> C + D, what will happen to the

equilibrium​ if the concentration of A is increased?

Solution: The reaction will increase in the forward direction.

Ionization of Acids and Bases

The process in which neutral molecules get splits up into charged ions
when exposed in a solution is referred to as the ionization of a
compound​. According to the Arrhenius theory, the acids are the
compounds that dissociate in the aqueous medium in order to generate
the hydrogen ions, H​+​ in the aqueous medium. Find interesting? Let’s
learn more about the ionization of acids and bases in this section.

Ionization of a Compound

While the bases are those compounds that furnish the hydroxyl ions,
OH​–​ in the aqueous medium. The degree of ionization of the acids and
bases helps determine its strength. On the basis of different acidic and
basic compounds, the degree of ionization may differ.

Browse more Topics Under Equilibrium

 ● Acids, Bases and Salts
● Buffer Solutions
● Equilibrium in Chemical Processes
● Equilibrium in Physical Processes
● Factors Affecting Equilibria
● Ionization of Acids and Bases
● Law of Chemical Equilibrium and Equilibrium Constant
● Solubility Equilibria

Ionization of Acids

The degree of Ionisation refers to the strength of an acid or a ​base​. A

strong acid is said to completely ionize in water whereas a weak ​acid
is said to only ionise partially. As there are different degrees of
ionization of acids, there are also different levels of weakness for
which there is a simple quantitative way to express.

Since the ionization of a weak acid is an ​equilibrium​, the ​chemical

equation​ and an equilibrium constant expression can be stated as :

HA ( aq ) + H​2​O ( l ) H​3​O​+​ ( aq ) + A​–

 K​a​ = [ H​3​O+ ] [A​–​] / [HA]

Equilibrium Constant for ionisation of an acid defines its Acid

Ionisation Constant (K​a​). However, the stronger the acid, the larger
will be the acid ionisation constant (K​a​). This means that a strong acid
is a better proton donor. As a result of the concentration of the product
in the numerator of the K​a​, the stronger the acid the larger is the acid
ionisation constant (K​a​).

Ionization of Bases

Some bases like lithium hydroxide or ​sodium​ hydroxide get

completely dissociated into their ​ions​ in an aqueous medium which is
referred to as strong bases. Therefore, the ionisation of these bases
yields hydrochloric ions, as (OH​–​). A similar expression for the bases
is:

A + H​2​O OH​–​ + HA​+

K​b​ = [ OH​–​ ] [ HA​+​ ] / [ A ]

The base ionisation constant i.e K​b​ refers to the equilibrium constant
for the ionisation of a base. Therefore, we can say that a strong base
implies a good proton acceptor while a strong acid implies a good
proton donor. The dissociation of weak acids or weak bases in ​water
is:

CH​3​COOH + H​2​O ⇔​ ​CH​3​COO‾ + H​3​O​+

NH​3​ + H​2​O ⇔​ ​NH​4+​ ( aq ) + OH‾( aq )

Solved Examples for You

Question: A 0.500 M solution of formic acid has a pH value of 2.04.

Determine the K​a​ for formic acid.
Solution. Initial [HCOOH] = 0.500 M and pH = 2.04. Unknown, K​a ​=
?

Concentrations [HCOOH] [H ​+ ​] [HCOO ​− ​]

Initial 0.500 0 0

Change -9.12 × 10 ​-3 +9.12 × 10 ​-3 +9.12 × 10 ​-3

Equilibrium 0.491 9.12 × 10 ​-3 9.12 × 10 ​-3

Now substituting into the K​a​ expression gives:

The value of K​a​ is consistent with that of a weak acid. Now, following
the same steps, we find the value of K​b o​ f the base. If 0.750 M
solution of the weak base ethylamine (C​2​H​5 ​NH​2​) has a pH of 12.31.
The pOH is 14 – 12.31 = 1.69. The [OH ​− ​] is found from 10 ​-1.69 ​ =
2.04 × 10 ​-2 ​ M. The ICE table shall be then as shown below.

Concentrations [C​2​H​5​NH​2​] [C​2​H​5​NH​3+​] [OH​−​]

Initial 0.750 0 0

Change -2.04 × 10 ​-2 +2.04 × 10 ​-2 +2.04 × 10 ​-2

Equilibrium 0.730 2.04 × 10 ​-2 2.04 × 10 ​-2

Substituting the value of K​b​ it yields the K​b​ for Ethylamine.

Law of Chemical Equilibrium and

Equilibrium Constant

Chemical equilibrium refers to the state wherein both the

reactants and the products present in the concentration have no
tendency to change with the period of time during a chemical
reaction. A ​chemical reaction​ achieves ​chemical equilibrium
when the rate of forward reaction and that of the reverse
reaction is same. Also, since the rates are equal and there is no
net change in the concentrations of the reactants and the
products – the state is referred to as a dynamic equilibrium and
the rate constant is known as equilibrium constant. Let’s find
out more.

Law of Chemical Equilibrium

Representation of the attainment of chemical equilibrium is –

The equilibrium constant is defined as the product of the molar

concentration​ of the products which is each raised to the power
equal to its ​stoichiometric coefficients​ divided by the product of
the molar concentrations of the reactants, each raised to the
power​ equal to its stoichiometric coefficients is constant at
constant temperature. T

his equilibrium constant can be simply expressed in terms of the

partial pressures of the reactants and the products. However, if
it is expressed in terms of the partial pressure, it is denoted by
K​p.

Browse more Topics under Equilibrium

● Acids, Bases and Salts
● Buffer Solutions
● Equilibrium in Chemical Processes
● Equilibrium in Physical Processes
● Factors Affecting Equilibria
● Ionization of Acids and Bases
● Solubility Equilibria

Equilibrium Constant
Equilibrium Constant Units and Formula

Law of ​mass​ action also forms the basis which states that the
rate of a chemical reaction is directly proportional to the
product of the concentrations of the reactants raised to their
respective stoichiometric coefficients. Therefore, given the
reaction –

aA(g) + bB(g) ⇔ cC(g) + dD(g)

By using the law of mass action here,

● The forward reaction rate would be k​+ ​[A]​a​[B]​b

● The backward reaction rate would be k​– ​[C]​c​[D]​d

where, [A], [B], [C] and [D] being the active masses and k​+​ and
k​−​ are rate constants of forward and backward reactions, also
the a, b, c, d are the stoichiometric coefficients related to A, B, C
and D respectively. However, at the equilibrium – the forward
and the backward rates are equal, stating –

Rate of forward reaction = Rate of backward reaction

or,

or,

where,

K​c ​is the equilibrium constant expressed in terms of the molar

concentrations. The equation K​c​ = [ C ]​c​·[ D ]​d​ / [ A ]​a​·[ B ]​b

or, K​c​ = K​f​ / K​b ​is the Law of Chemical Equilibrium. ​The
equilibrium constant is therefore related to the standard ​Gibbs​ free
energy change for the reaction which is stated by the equation –

§Gº= -RT ln K​eq

where T states the temperature, R is the universal ​gas​ constant and K​eq
is the equilibrium constant.
Solved Examples for You

Question: Write the equilibrium constant expression for the

reaction​ equation:

NH​3​ + HOAc = NH​4+​ + OAc​–

Solution:

[NH​4+​] [OAc​–​] ——————— = ​K​ (unitless constant) [NH​3​]

[HOAc]

Question: A closed container has N​2​O​4​ and NO​2​ gases in it. It

has been placed in the lab for many days. What would you
consider the container and the gases to be?

a. an open system
 b. a closed system
c. not a system

Solution: ​A closed system since it has been in the lab, the

temperature​ of the system is the same as its ​environment​.

Solubility Equilibria

The equilibrium constant that represents the maximum amount of

solid which can be dissolved in an aqueous solution is defined as the
solubility product. The Solubility Equilibria are based on the
assumption that the solids dissolve in water in order to give the basic
particles from which they are formed.

Solubility Equilibria

Each of the molecular solids dissolves to give an individual aqueous

molecule​ such as

H​2​O

C​12​H​22​O​11(S)​ —————> C​12​H​22​O​11​ ​(aq)

The ​ionic​ solids dissociate to give their respective positive and
negative ions :

H​2​O

NaCl ​(s)​ ————————-> Na + (aq) + Cl ​–​ (aq )

The ions formed from the dissociation of the ionic solids can also
carry an electrical current which makes the salt solutions good
conductors of electricity. However, ​molecular​ solids do not dissociate
in water to give ions so as no electrical current can be carried.

Browse more Topics under Equilibrium

● cids, Bases and Salts
● Buffer Solutions
● Equilibrium in Chemical Processes
● Equilibrium in Physical Processes
● Factors Affecting Equilibria
● Ionization of Acids and Bases
● Law of Chemical Equilibrium and Equilibrium Constant
Solubility

The ​ratio​ of the maximum amount of solute to the volume of the

solvent in which the solute can dissolve. This is generally expressed in
two ways i.e –

a. Grams of solute per 100 g of water

b. Moles of solute per litre of solution

A salt refers to be soluble if it dissolves in water to give a solution

along with the concentration of at least 0.1 m at the room temperature.
A salt is also considered to be insoluble if the concentration of an
aqueous solution is less than 0.0001 m at the room ​temperature​. Salts
are considered to be slightly soluble; those between 0.0001 m and 0.1
m.
According to the principles of solubility equilibria, the salts have low
solubilities in water. The reaction that can be considered for the
dissociation of the salt AgCl is –

AgCl​(s)​ ————— Ag​+(aq)​ + Cl​–​ ​(aq)

However, the reverse reaction for the dissolving of the salt would be
the precipitation of the ions to form a ​solid​ –

Ag​+(aq)​ + Cl​–​ ​(aq) ​—————– AgCl(s)

When the rate at which AgCl dissolves is equal to the rate at which
AgCl precipitates, the system has reached the solubility equilibria.

Solubility Product Equilibrium Constant (K​sp​)

The product of the equilibrium concentrations of the ions in a

saturated solution of a salt. Each concentration in this is raised to the
power of the respective coefficient of ​ion​ in the balanced equation.
For example, the solubility product equilibrium constant for the
dissociation of AgCl is:
Another example of a solubility product equilibrium constant where
we can consider the reaction for the dissociation of CaF​2​ in water is :

The solubility product equilibrium constant for this reaction would be

the product of the concentration of Ca​2+​ ion and the concentration of
the F​–​ ion raised to the second power (squared):

Solved Examples for You

Question: In the atmosphere, SO​2​ and NO are oxidised to SO​3​ and

NO​2​, respectively, which react with water to give H​2​SO​4​ and HNO​3​.
The resultant solution is called acid rain. SO​2​ dissolves in water to
form diprotic acid.

SO​2(g)​+H​2​O​(l)​⇔HSO​⊝3​+H​⊕​; K​a1​=10​−2
 HSO​⊝3​⇔SO​2−3​+H​⊕​; K​a2​=10​−7

and for equilibrium,

SO​2(aq)​+H​2​O​(l)​⇔SO​2−3(aq)​+2H​⊕(aq)

K​a​=K​a1​×K​a2​=10​-9​ at 300K.

A. H​2​SO​3​ is less acidic than H​2​SO​4

B. HNO​3 ​is less acidic than HNO​2
C. SO​2(g)​ is reduced in the atmosphere during a thunderstorm
D. CO​2​ gas develop more acidity in ​water​ than SO​2

Solution: Option A.​ ​Sulphurous acid H​2​SO​3​ is less acidic than

sulphuric acid H​2​SO​4​. When a proton is lost by sulphurous acid, the
negative charge is delocalized on 3 O atoms and when a proton is lost
by sulphuric acid, the negative charge is delocalized by 4 O ​atoms​.
Since the extent of delocalization in HSO​-1​ ion is less than the extent
of delocalization in HSO​-4​, the stability of anion and the acidity of the
acid in sulphurous acid is lower than in sulphuric ​acid​.