BASIC PHYSICAL CHEMISTRY CHM 131

Thermochemistry
Thermochemistry is the study of the heat released or absorbed as a result of chemical reactions.
Chemical reactions involve the conversion of a set of substances collectively referred to as "reactants"
to a set of substances collectively referred to as "products. Reactions that liberate heat are termed
exothermic reactions, and reactions that absorb heat are termed endothermic reactions. The heat
associated with a chemical reaction depends on the pressure and temperature at which the reaction is
carried out. The quantity of heat released in a reaction depends on the amount of material undergoing
reaction. Thermochemistry also depends on the physical state of the reactants and products.

First Law of Thermodynamics

Thermochemical changes are often discussed in terms of the "system" and the "surroundings." The
system is regarded as the reaction products and reactants, whereas the surroundings consist of everything
else in the universe. A boundary separates the system from the surroundings. The first law of
thermodynamics relates the energy change belonging to a system to the amount of work and heat
crossing the boundary. A statement of the first law applied to chemical reactions in which only heat and
work cross the boundary is given by the expression:
The First Law of Thermodynamics states that energy can be converted from one form to another with
the interaction of heat, work and internal energy, but it cannot be created nor destroyed, under any
circumstances. Mathematically, this is represented as

Here U products represents the energy of the products and U reactants represents the energy of the
reactants. The heat associated with the reaction is given as q, and w represents work done during the
transformation of reactants to products.
Work is also equal to the negative external pressure on the system multiplied by the change in volume:

where P is the external pressure on the system, and ΔV is the change in volume. This is specifically
called "pressure-volume" work.

The internal energy of a system would decrease if the system gives off heat or does work. Therefore,
internal energy of a system increases when the heat increases (this would be done by adding heat into a

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system). The internal energy would also increase if work were done onto a system. Any work or heat
that goes into or out of a system changes the internal energy. However, since energy is never created
nor destroyed (thus, the first law of thermodynamics), the change in internal energy always equals zero.
If energy is lost by the system, then it is absorbed by the surroundings. If energy is absorbed into a
system, then that energy was released by the surroundings.

A reversible chemical reaction is one in which the products, as soon as they are formed, react to produce
the original reactants. At equilibrium, the two opposing reactions go on at equal rates. for the reversible
reaction
A ⇋ B + C,
the velocity of the reaction to the right, r1, is given by the mathematical expression (based on the law of
mass action) r1 = k1(A), where k1 is the reaction-rate constant and the symbol in parentheses represents
the concentration of A. The velocity of the reaction to the left, r 2, is r2 = k2(B)(C). At equilibrium, r1 =
r2

Enthalpy
Enthalpy is a central factor in thermodynamics. It is the heat content of a system. The heat that passes
into or out of the system during a reaction is the enthalpy change. Whether the enthalpy of the system
increases (i.e. when energy is added) or decreases (because energy is given off) is a crucial factor that
determines whether a reaction can happen.

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Entropy
Entropy refers to the measure of the level of disorder in a thermodynamic system. It is measured as
joules per kelvin (J/K) and denoted by the symbol 'S'. For any spontaneous process, the entropy of the
system should increase. Entropy is calculated in terms of change as well and defined with the following
formula:
∆S = ∆Q / T
where ΔS = change of entropy, ΔQ= change of heat content of the system and T = temperature of the
system. This equation is for a thermodynamically reversible process.

Free Energy
Free energy is energy that is available to do work. Spontaneous reactions release free energy as they
proceed. In order to define the relationship that exists between entropy and enthalpy, a new concept
known as the Gibbs free energy is introduced. Gibbs Free Energy is used to measure the amount of
available energy that a chemical reaction provides. As reactions are usually temperature dependent, and
sometimes work significantly better at some temperatures than other.

Similar to the equations for ΔH and ΔS for a system, ΔG is defined as the difference between the sum
of the free energy of formation values of the products and reactants. If a reaction is not spontaneous, its
ΔG will be positive. If a reaction is spontaneous, its ΔG will be negative. For all temperatures, including
25°C, the following equation can be used to determine spontaneity of a chemical reaction:
ΔG = ΔH – TΔS
The symbol for free energy is G, ΔH is in kJ/mol, while ΔS is in J/K • mol. It is necessary to change the
units for Delta S to kJ/K • mol, so that the calculation of Delta G is in kJ/mol.

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In thermodynamics, a spontaneous process is a process which occurs without any external input to the
system. For a process that occurs at constant temperature and pressure, spontaneity can be determined
using the change in Gibbs free energy, which is given by:

{\displaystyle \Delta G=\Delta H-T\Delta S\,}\Delta G=\Delta H-T\Delta S\,,

where the sign of ΔG depends on the signs of the changes in enthalpy (ΔH) and entropy (ΔS). The sign
of ΔG will change from positive to negative (or vice versa) where T = ΔH/ΔS.

In cases where ΔG is: negative, the process is spontaneous and may proceed in the forward direction as
written. positive, the process is non-spontaneous as written, but it may proceed spontaneously in the
reverse direction. zero, the process is at equilibrium, with no net change taking place over time.

Chemical equilibrium
Chemical equilibrium is a state in which the rate of the forward reaction equals the rate of the backward
reaction for a reversible reaction. In other words, there is no net change in concentrations of reactants
and products. This kind of equilibrium is also called dynamic equilibrium due to the fact there is
continuous interchanging of molecules.

A graph with the concentration on the y-axis and time on the x-axis can be plotted. Once the
concentration of both the reactants and the products stops showing change, chemical equilibrium is
achieved.

Types of Chemical Equilibrium

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There are two types of chemical equilibrium: Homogeneous Equilibrium and Heterogeneous
Equilibrium. Homogenous chemical equilibrium is the one in which the reactants and the products are
all in the same phase. For example,

Heterogeneous chemical equilibrium is the one, the reactants and the products of chemical equilibrium
are present in different phases. A few examples of heterogeneous equilibrium are listed below.

Factors Affecting Chemical Equilibrium

According to Le-Chatelier’s principle, if there is any change in the factors affecting the equilibrium
conditions, the system will counteract or reduce the effect of the overall transformation. This principle
applies to both chemical and physical equilibrium. There are several factors like temperature, pressure
and concentration of the system which affect equilibrium. Some important factors affecting chemical
equilibrium are discussed below.

If the concentration of a substance is changed, the equilibrium will shift to minimize the effect of that
change. If the concentration of a reactant is increased the equilibrium will shift in the direction of the
reaction that uses the reactants, so that the reactant concentration decreases.

When there is an increase in pressure, the equilibrium will shift towards the side of the reaction with
fewer moles of gas. When there is a decrease in pressure, the equilibrium will shift towards the side of
the reaction with more moles of gas.

If the temperature is increased, the position of equilibrium moves in the direction of the endothermic
reaction. If the temperature is reduced, the position of equilibrium moves in the direction of the
exothermic reaction.

In the presence of a catalyst, both the forward and reverse reaction rates will speed up equally, thereby
allowing the system to reach equilibrium faster. However, it is very important to keep in mind that the
addition of a catalyst has no effect whatsoever on the final equilibrium position of the reaction.

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Importance of Chemical Equilibrium
It is useful in many industrial processes like, preparation of ammonia by Haber’s process: In this nitrogen
combines with hydrogen to form ammonia, the yield of ammonia is more at low temperature, high
pressure and in the presence of iron as catalyst. preparation of sulphuric acid by contacts process: In this
process, the fundamental reaction is the oxidation of sulphur (IV) oxide into sulphur (VI) oxide.

General Concepts of Acids and Bases

There is no general definition of acids and bases. There are three different concepts of acids and bases
as proposed by Arrhenius, Brønsted and Lowry and Lewis respectively.

Arrhenius Concept
This concept was developed by Svante Arrhenius in 1884. According to this concept an acid is a
substance that is capable of producing hydrogen ion (H+) by dissociating in aqueous solution. The
reaction can be represented as

Where HA represents the acid and A refers to the acid molecule without the hydrogen ion. Hydrochloric
acid, HCl is an example of an Arrhenius acid whose ionization can be represented as

The proton or hydrogen ion binds itself to a water molecule and form H3O + ion which is called
hydronium ion.

The hydronium ion is also known as oxonium ion or the hydroxonium ion.
A base on the other hand is defined as a substance capable of providing a hydroxyl ion (HO -) on
dissociation in aqueous solutions.

Where M+ refers to the base molecule without the hydroxyl ion. Sodium hydroxide is an example of an
Arrhenius base, dissociating as,

Brønsted and Lowry Concept

In 1923, Brønsted and Lowry defined an acid as a proton (H+) donor, and a base is defined as a proton
acceptor. The definition is sufficiently broad and removes the first limitation of Arrhenius concept. Any

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hydrogen-containing molecule or ion capable of donating or transferring a proton is an acid, while any
molecule or ion that can accept a proton is a base.
For example, in a reaction between ammonia (NH3 and hydrogen fluoride (HF); ammonia acts as a base
(accepts a proton) while HF behaves as an acid (donates a proton).

In any acid-base equilibrium both forward and reverse reactions involve proton transfers. Let us consider
the reaction of NH3 with H2O.

In the forward reaction, NH3 accepts a proton from H2O. Thus, NH3 is a base and H2O is an acid. In the
reverse reaction, NH4+ donates a proton to –OH. Thus NH4+ ion acts as an acid and –OH as a base. Here
you find that NH3 and NH4+ differ by a proton. That is, NH3 becomes NH4+ ion by gaining a proton,
whereas NH4+ ion becomes NH3 molecule by losing a proton. The species NH4+ and NH3 are called
conjugate acid-base pair.

Some species can act both as an acid and as a base. Such species are called amphiprotic species. In the
above reactions HCO3– (aq) acts as a base in presence of HF but an acid in presence of CN. Similarly,
H2O behaves as an acid and a base.
Lewis Concept
Lewis proposed (1923) a yet another concept of acids and bases that includes such substance also.
According to him, an acid may be defined as, ‘any atom, molecule or ion that can accept an electron pair
from any other atom, molecule or ion, a Lewis base on the other hand can be defined as, ‘ any atom ,
molecule or ion that can donate a pair of electrons, for an example

In the above example AlCl3 is an electron deficient species. It accepts an electron pair from a molecule
of NH3 which has a lone pair of electrons on N atom. Thus, AlCl 3 is a Lewis acid and NH3 is a Lewis
base.

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pH Scale
In aqueous solutions of acids and bases the concentration of H 3O+ and OH ions may vary from about
10 M to 1014 M. It is quite inconvenient to express these concentrations by using powers of 10. in
1909 a Danish botanist S.P.L. Sorensen proposed a logarithmic scale (called pH scale) for expressing
the concentrations of H+ ions. He defined pH as the negative logarithm of the molar concentration of
hydrogen ions. That is, a strongly acidic solution can have a pH of less than zero (i.e., negative) and a
strongly alkaline solution can have a pH value greater than 14. However, the pH ranges normally
observed is between 0 to 14.

Indicators
Indicators are substances whose solutions change color due to changes in pH. These are called acid-base
indicators. They are usually weak acids or bases, but their conjugate base or acid forms have different
colors due to differences in their absorption spectra. Indicators are organic weak acids or bases with
complicated structures. For simplicity, we represent a general indicator by the formula HIn, and its
ionization in a solution by the equilibrium,

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and define the equilibrium constant as Kai

which can be rearranged to give

When [H+] is greater than 10 Kai, In− color dominates, whereas color due to HIn dominates if [H +] <
Kai 10. The above equation indicates that the color change is the most sensitive when [H +] = Kai in
numerical value. We define pKai = - log (Kai), and the pKai value is also the pH value at which the color
of the indicator is most sensitive to pH changes. Taking the negative log of K ai gives,

Buffer and Buffer Action

Buffer solutions are the ones that resist a change in its pH on adding a small amount of an acid or a base.
There are two kinds of commonly used buffer-solutions
i. A weak acid and a soluble ionic salt of the weak acid e.g. acetic acid and sodium acetate;
CH 3COOH + CH3COONa
ii. A weak base and a soluble ionic salt of the weak base e.g. ammonium hydroxide and ammonium
chloride NH4OH + NH4Cl
The buffers with pH less than 7 are called acidic buffers and those with pH above 7 are called basic
buffers. Acetic acid - sodium acetate buffer is an example of acidic buffer while Ammonium hydroxide
- ammonium chloride is a basic buffer.

A buffer system contains a conjugate acid- base pair and the concentrations of these two are quite high
as compared to that of the hydronium ions. These are called as the acid reserve and the base reserve

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respectively. The added acid or base reacts with these reserves and gets consumed without significantly
altering the hydronium ion concentration and therefore the pH does not change significantly. Let us
consider a buffer solution containing acetic acid, CH 3COOH and sodium acetate CH3COONa to
understand the buffer action.

In acetic acid - sodium acetate buffer CH3COOH is the acid reserve while CH3COONa (or CH3COO-
ions) is the base reserve. In the solution mixture the added components dissociate as follows. The weak
acid dissociates partially while the salt undergoes complete dissociation.

If we add a strong acid such as HCI to this solution, it produces H3O+. These added H3O+ (acid) react
with an equivalent amount of the base reserve [CH3COO-] to generate undissociated acetic acid. The
reaction being

The net effect of this reaction is that there is a slight increase in the concentration of the acid reserve and
an equivalent decrease in the concentration of the base reserve. The effective reaction being

Similarly, when small amounts of a strong base like NaOH is added, it generates OH - ions. These
additional OH- neutralize some of the H3O+ ions present in the solution,

Chemical Kinetics
Chemical kinetics is an area of chemistry dealing with speeds/rates of reactions. chemical kinetics, also
known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the
rates of chemical reactions. The rate of reaction or reaction rate is the speed at which reactants are
converted into products. Rates of reactions affected by four factors
i. concentrations of reactants: Increasing the concentration of one or more reactants will often
increase the rate of reaction. This occurs because a higher concentration of a reactant will
lead to more collisions of that reactant in a specific time period.
ii. temperature at which reaction occurs: An increase in temperature typically increases the rate
of reaction. An increase in temperature will raise the average kinetic energy of the reactant

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molecules. Therefore, a greater proportion of molecules will have the minimum energy
necessary for an effective collision.
iii. presence of a catalyst: A catalyst is a substance that accelerates a reaction by participating in
it without being consumed. Catalysts provide an alternate reaction pathway to obtain
products.
iv. surface area of reactants: If reactant molecules exist in different phases, as in a heterogeneous
mixture, the rate of reaction will be limited by the surface area of the phases that are in
contact. For example, if a solid metal reactant and gas reactant are mixed, only the molecules
present on the surface of the metal are able to collide with the gas molecules. Therefore,
increasing the surface area of the metal by pounding it flat or cutting it into many pieces will
increase its reaction rate.
Rate Law
The rate law (also known as the rate equation) for a chemical reaction is an expression that provides a
relationship between the rate of the reaction and the concentrations of the reactants participating in it.
Expression
For a reaction given by: aA + bB → cC + dD
Where a, b, c, and d, are the stoichiometric coefficients of the reactants or products, the rate equation
for the reaction is given by: Rate ∝ [A]a [B]b ⇒ Rate = k[A]a[B]b
Where, [A] and [B] denote the concentrations of the reactants A and B, a and b denote the partial reaction
orders for reactants A and B (which may or may not be equal to their stoichiometric coefficients a and
b).
The proportionality constant ‘k’ is the rate constant of the reaction. It is important to note that the
expression of the rate law for a specific reaction can only be determined experimentally. The rate law
expression cannot be obtained from the balanced chemical equation (since the partial orders of the
reactants are not necessarily equal to the stoichiometric coefficients).

Reaction Orders and Molecularity

The sum of the partial orders of the reactants in the rate law expression gives the overall order of the
reaction. If Rate = k[A]a[B]b; overall order of the reaction (n) = a + b. The order of a reaction provides
insight into the change in the rate of the reaction that can be expected by increasing the concentration of
the reactants. For example: If the reaction is a zero-order reaction, doubling the reactant concentration
will have no effect on the reaction rate. If the reaction is of the first order, doubling the reactant

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concentration will double the reaction rate. In second-order reactions, doubling the concentration of the
reactants will quadruple the overall reaction rate. For third-order reactions, the overall rate increases by
eight times when the reactant concentration is doubled.

Rate Constants: Rearranging the rate equation, the value of the rate constant ‘k’ is given by:
k = Rate/[A]x[B]y
Therefore, the units of k (assuming that concentration is represented in molL-1 or M and time is
represented in seconds) can be calculated via the following equation.
k = (M.s-1) *(M-n) = M(1-n). s-1
The number of ions or molecules that take part in the rate-determining step is known as molecularity.
The sum of powers to which the reactant concentrations are raised in the rate law equation is known as
the order of the reaction.

Molecularity: If a chemical reaction proceeds by more than one step or stage, its overall velocity or rate
is limited by the slowest step, the rate-determining step. This "bottleneck concept" has analogies in
everyday life. For example, if a crowd is leaving a theater through a single exit door, the time it takes to
empty the building is a function of the number of people who can move through the door per second.
Once a group gathers at the door, the speed at which other people leave their seats and move along the
aisles has no influence on the overall exit rate. When we describe the mechanism of a chemical reaction,
it is important to identify the rate-determining step and to determine its "molecularity". The molecularity
of a reaction is defined as the number of molecules or ions that participate in the rate determining step.
A mechanism in which two reacting species combine in the transition state of the rate-determining step
is called bimolecular. If a single species makes up the transition state, the reaction would be called
unimolecular. The relatively improbable case of three independent species coming together in the
transition state would be called termolecular.

Zero Order Reaction: Zero-order reaction is a chemical reaction wherein the rate does not vary with
the increase or decrease in the concentration of the reactants. Therefore, the rate of these reactions is
always equal to the rate constant of the specific reactions (since the rate of these reactions is proportional
to the zeroth power of reactants concentration). The reverse Haber process is an example of a zero-order
reaction because its rate is independent of the concentration of ammonia.

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Rate = = [ ] =k[A]0 = k

Where ‘Rate’ refers to the rate of the reaction and ‘k’ is the rate constant of the reaction. This differential
form can be rearranged and integrated on both sides to get the required Integral form as shown below.

First-Order Reaction: A first-order reaction can be defined as a chemical reaction in which the reaction
rate is linearly dependent on the concentration of only one reactant. In other words, a first-order reaction
is a chemical reaction in which the rate varies based on the changes in the concentration of only one of
the reactants. Thus, the order of these reactions is equal to 1.
Examples of First-Order Reactions
SO2Cl2 → Cl2 + SO2
2N2O5 → O2 + 4NO2
2H2O2 → 2H2O + O2
The differential rate expression for a first-order reaction can be written as:
Rate = -d[A]/dt = k[A]1 = k[A]
Where,
‘k’ is the rate constant of the first-order reaction, whose units are s-1.
‘[A]’ denotes the concentration of the first-order reactant ‘A’.
d[A]/dt denotes the change in the concentration of the first-order reactant ‘A’ in the time interval ‘dt’.

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Arrhenius Equation: The Arrhenius equation is an expression that provides a relationship between the
rate constant (of a chemical reaction), the absolute temperature, and the A factor (also known as the pre-
exponential factor; can be visualized as the frequency of correctly oriented collisions between reactant
particles). It provides insight into the dependence of reaction rates on the absolute temperature. The
expression of the Arrhenius equation is:

Where, k denotes the rate constant of the reaction, A denotes the pre-exponential factor which, in terms
of the collision theory, is the frequency of correctly oriented collisions between the reacting species, e
is the base of the natural logarithm (Euler’s number), Ea denotes the activation energy of the chemical
reaction (in terms of energy per mole), R denotes the universal gas constant and T denotes the absolute
temperature associated with the reaction (in Kelvin).
Considering a chemical reaction at two different temperatures T 1 and T2, whose corresponding rate
constants are k1 and k2 respectively, the logarithmic form of the Arrhenius equation is:

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