What is Chemical Energetic?

Chemical energetic is the study of chemical changes caused by energy.

Chemical energetic discusses both thermodynamics and kinetics or
reactions. Thermodynamics is the branch of physical science that deals with
the relations between heat and other forms of energy (such as mechanical,
electrical, or chemical energy). It is also defined as the study of energy
transfer and the effects of energy changes. In the study of energy transfer, it
is useful to divide the universe into manageable pieces.

DEFINITION OF SOME THERMODYNAMIC TERMS

1. SYSTEMS AND SURROUNDINGS

There are a number of terms that are commonly used in the discussions of
these changes in energy during chemical reactions. Thermodynamics
considers everything globally as the universe and defines a system as that
particular part of the universe that we are interested in and wish to study.
The remaining part of the universe apart from that we are interested in is
called the surrounding. The separation between the system and the
surrounding is the boundary.

We shall illustrate these definitions by considering water in a flask whose

temperature changes we wish to study. The water constitutes the system,
flask and every other thing outside the water constitutes the surrounding and
the contact between the water and flask is the boundary.

2. TYPES OF SYSTEMS

In thermodynamics, we deal mainly with three different types of systems

depending on the interactions between the system and the surroundings.
These are( a) open systems , (b) closed systems and (c ) isolated systems.

(a) Open systems: A systems which can exchange both matter and energy
with the surroundings is known as an open system. Hot water contained
in a beaker placed on laboratory table is an open system. The water
vapour (matter) and also heat (energy) is transferred to the surroundings
through the imaginary boundary.
(b)Closed systems: A close system is one which cannot transfer matter but
can transfer energy in the form of heat, work and radiation to and from its
surroundings. A specific quantity of hot water contained in a sealed tube,
is an example of a closed system. As the piston is raised, the gas expands
and transfers heat (energy) in the form of work to the surroundings.
(c) Isolated systems: Systems that can exchange neither matter nor energy
with the surroundings are called isolated system. A substance, say
boiling water, contained in a thermos flask is an example of an isolated
system.
3. PROPERTIES OF A SYSTEM

The macroscopic or bulk properties of a system (volume, pressure, mass,

etc.) can be divided into two classes :

(a) Intensive properties

(b) Extensive properties

Intensive Properties

A property that dose not depend on the quantity of matter present in the
system, is known as Intensive Property.

Some examples of intensive properties are pressure, temperature, density,

boiling and freezing points, surface tension, refractive index, viscosity,
and concentration. If the concentration of salt, NaCl, in the glass of water
is 0.1 mole/litre, then any drop of water from the glass also has a Small
concentration of 0.1 mole/litre.

Extensive Properties

A property that does depend on the quantity of matter present in the

system, is called an

Extensive Property.

Some examples of extensive properties are volume, number of moles,

enthalpy, entropy, and Gibbs’ free energy.
 By definition, the extensive properties are additive while intensive
properties are not. Let us consider the system ‘a glass of water’. If we
double the mass of water, the volume is doubled and so is the moles and the
internal energy of the system.

4 STATE OF A SYSTEM

A thermodynamic system is said to be in a definite state when the

properties have definite values. Various measurable properties of a system
which completely define the state of a system are pressure, volume,
temperature and concentration. Since a change in the magnitude of such
properties alters the state of the system, these are referred to as State
variables or State functions or Thermodynamic parameters. Any change in
the property due to a change in the state of the system depends only on the
initial and the final states of the system. These variables are directly
measureable from experiments and do not require any assumption regarding
the structure of matter and related to one another by an equation called the
equation of state. For an ideal gas, the equation of state for one moles of a
pure gas is:

PV = RT

Where R is a gas constant. If of the three state variables(P,V,T), P and T are

specified, the valve of third (V) is fixed automatically and can be calculated
from the equation of state. The variables (P and T) which must be
necessarily specified to define a state of a system, are designated as
Independent state variables. The remaining state variable (V) which
depends on the valve of P and T, is called Dependent state variable.

5 THERMODYNAMIC EQUILIBRIUM

A system is said to be in a state of thermodynamic equilibrium if none

of the observable properties of the system appears to change with time.
There are three types of equilibria in the system namely:
(i) Thermal equilibrium : A system is said to be in thermal equilibrium if
the temperature remains the same in all parts of the system.
(ii) Mechanical equilibrium: It implies the uniformity of pressure
throughout the whole system.
(iii) Chemical equilibrium : If the composition of the system remains
constant and uniform throughout, the system is said to be in chemical
equilibrium.

6 THERMODYNAMIC PROCESSES

When a thermodynamic system changes from one state to another,

the operation is called a process. These processes involve the change of
conditions (temperature, pressure and volume). The various types of
thermodynamic processes are:

(i) Isothermal Processes

Those processes, in which the temperature remains fixed, are termed
isothermal processes. It is often achieved by placing the system in a
thermostat (a constant temperature bath)
For an isothermal process dT = 0
(ii) Adiabatic Processes

Those processes in which no heat can flow into or out of the system
are called adiabatic processes. These conditions can be approached by
carrying the process in an insulated container such as ‘thermos’ bottle.

For an adiabatic process dq = 0

(iii) Isobaric Processes

Those processes which take place at constant pressure are called
isobaric processes. For example, heating of water to its boiling point
and its vapourization take place at the same atmospheric pressure.
For an isobaric process dp = 0
 (iv)Isochoric Processes

Those processes in which the volume remains constant are known as

isochoric processes. For example the heating of a substance in a non–
expanding chamber.

For isochoric processes dV =0

(iv) Cyclic Process

When a system in a given state goes through a number of different

processes and finally returns to its initial state, the overall process is
called a cyclic or cyclic process.

For a cyclic process dE =0, dH= 0.

(v) Reversible Process

A thermodynamic reverse process is one that takes place

infinitesimally slowly and its direction at any point can be reversed by
an infinitesimal change in the state of the system.

(vi) Irreversible Process

When a process goes from the initial to the final state in a single step
and cannot be carried in the reverse order, it is said to be an
irreversible process.

HEAT AND WORK

When a change in the state of a system occurs, energy is transferred to or from the
surroundings. This energy may be transferred as heat or mechanical work.

Work in thermodynamics is defined as any quantity of energy that ‘flows’ across

the boundary between the systems and surroundings that can be used to change the
height of a mass in the surroundings.

In SI system of units, work is expressed in Joule or kilo joule; 1 J = 1 Nm.

When work is done on a system by the surroundings and the energy of the system
is thus increased, it is taken to be positive, +w. If work is done by the system on
the surroundings and energy of the system is decreased, it is taken to be negative, -
w. Work, like energy, can take various forms: mechanical, electrical, gravitational,
etc. All have in common the fact that they are the product of two factors, an
intensity term and a capacity term. For example, the simplest form of mechanical
work arises when an object moves a certain distance against an opposing force,
formulae: F ∆ X .
Electrical work is done when a body having a certain charge moves through a
potential difference, formulae: Q ∆ E. Gravitational work is said to be done when
a body is raised through a certain height against the gravitational field, formulae:
mg h.

HEAT
Heat is a form of energy and can be produced from work or can be partly
converted into work. It appears only during a change in the state and flows from a
region of higher temperature to a region of lower temperature. The flow ceases
when the thermal equilibrium is attained. Heat is different from other forms of
energy. All other forms of energy can be quantitatively converted into work but
heat cannot be completely converted into work without producing permanent
changes either in the system or in the surroundings.

Heat is an algebraic quantity and is denoted by q. If the heat flows from the
surroundings into the system to raise the energy of the system, it is taken to be
positive,+q. If heat flows from the system into the surroundings, lowering the
energy of the system, it is taken to be negative, -q.

Pressure-volume work

The kind of work most frequently associated with chemical change occurs when
the volume of the system changes owing to the disappearance or formation of
gaseous substances. This is sometimes called expansion or PV work-work, and it
can most easily be understood by reference to the simplest form of matter we can
deal with, the ideal gas.
 Fig. 1: Expansion of a gas subjected to a constant external pressure

The figure shows a quantity of gas confined in a cylinder by means of a moveable

piston. Weights placed on top of the piston exert a force f over the cross-section
area A, producing a pressure P = f / A which is exactly countered by the pressure of
the gas, so that the piston remains stationary. Now suppose that we heat the gas
slightly; according to Charles’ law, this will cause the gas to expand, so the piston
will be forced upward by a distance x. Since this motion is opposed by the force A,
a quantity of work f ∆ x will be done by the gas on the piston. By convention,
work done by the system (in this case, the gas) on the surroundings is negative, so
the work is given by
w= – f ∆ x
When dealing with a gas, it is convenient to think in terms of the more relevant
quantities pressure and volume rather than force and distance. We can accomplish
this by multiplying the second term by A/A which
of course leaves it unchanged:
By grouping the terms differently, but still not changing anything, we obtain
Since pressure is force per unit area and the product of the length A and the area
has the dimensions of volume,
this expression becomes
w = –P ∆ V (2)
This equation is a good illustration of how a non-state function like the work
depends on the path by which
a given change is carried out. In this case the path is governed by the external
pressure P.

Problem Example 1
Find the amount of work done on the surroundings when 1 liter of an ideal gas,
initially at a pressure of 10 atm,
is allowed to expand at constant temperature to 10 liters by a) reducing the external
pressure to 1 atm in a single
step, b) reducing P first to 5 atm, and then to 1 atm, c) allowing the gas to expand
into an evacuated space so its
total volume is 10 liters.
Solution. First, note that DV, which is a state function, is the same for each path:
V2 = (10/1) ´ (1 L) = 10 L, so DV = 9 L.
For path (a), w = –(1 atm) ´ (9 L) = –9 L-atm.
For path (b), the work is calculated for each stage separately:
w = –(5 atm) ´ (2–1 L) – (1 atm) ´ (10–2 L) = –13 L-atm
For path (c) the process would be carried out by removing all weights from the
piston in Fig. 1 so that the gas expands to 10 L against zero external pressure. In
this case w = (0 atm) ´ 9 L = 0; that is, no work is done because there is no force to
oppose the expansion.

Internal energy

Internal energy is simply the totality of all forms of kinetic and potential energy
of the system.
The internal energy of a system, like temperature, pressure, volume, etc., is
determined by the state of a system and is independent of the path by which it is
obtained. Hence internal energy of a system is a state function. The internal energy
of a system is represented by the symbol E or U. In thermodynamics we are
concerned only with the energy changes when a system changes from one state to
another. If E be the difference of energy of the initial state ( Ein ) and the final
state (Ef ), we can write

∆E =Ef –Ein
∆E is +ve if Ef is greater than Ein and –ve if Ef is less than Ein .
The SI unit for internal energy of a system is the joule (J).Another unit of energy
which is not an SI unit is the calorie, 1 cal = 4.184 J.

FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics is the law of conservation of energy, it states that
energy can not be created or destroyed; it can only be redistributed or changed
from one form to another. In other words, whenever energy of a particular form
disappears an exactly equivalent amount of another form must be produced.
Consider a system in a state A with internal energy E A..It absorbs from the
surroundings a certain amount of heat Q and undergoes a change in its state to B
where it energy is EB. The increase in energy of the system ∆ E is given by

∆E = E B - EA

This energy change is brought about by the evolution or absorption of heat and /or
by work being done by the system. Because the total energy of the system must
remain constant, we can write the mathematical statement of the First Law as
∆E=q-w ………(1)

Where q = the amount of heat supplied to the system and w = work done by the system

Thus First Law may also be stated as : the change in internal energy of a system
is equal to the heat added to the system minus the work done by the system.

A way of expressing this law that is generally more useful in Chemistry

is the sum

∆ E= q + w
It is the same law, of course - the thermodynamic expression of the conservation of
energy principle. It is just that W is defined as the work done on the system instead
of work done by the system.

SOME SPECIAL FORMS OF FIRST LAW OF THERMODYNAMICS

Mathematical statement of the First law of Thermodynamics is

E=q-w
Case 1 : For a cyclic process involving isothermal expansion of an ideal gas

E=0
therefore q=w
 Case 2 : For an isochoric process ( no change in volume) there is no work
of expansion i.e w = 0. Hence
 E = qv

Case 3 : For an adiabatic process there is no change in heat gained or lost i.e
q=0. Hence

E=-w
In other words, the decrease in internal energy is exactly equal to the work
done the system by surroundings.

Case 4 : For an isobaric process there is no change in pressure, i.e. P

remains constant. Hence

E = q-w

Or  E = q – P V

ENTHALPY (H)
The sum of the internal energy of the system plus the product of the pressure of
the gas in the system and its volume:

HSYS = ESYS + PV …………..(1)

where P and V are the pressure and volume, and E is internal energy. Enthalpy is
then a precisely measurable state variable, since it is defined in terms of three other
precisely definable state variables.

Change in Enthalpy
We will define Enthalpy change, ΔH, of a system as being equal to its heat output
at constant pressure:

ΔH = q at constant pressure
 Where: ΔH = change in enthalpy

You will not need to be able to calculate the enthalpy directly; in chemistry, we are
only interested in the change in enthalpy, ΔH, because it is a state function. It is
expressed in Kcal/mol.

ΔH = Hfinal - Hinitial or ΔH = H(products) - H(reactants)

Tables of enthalpies are generally given as ΔH values.

Example Problem: Calculate the ΔH value of the reaction:

HCl + NH3 → NH4Cl

(ΔH values for HCl is -92.30 Kcal/mol; NH3 is -80.29 Kcal/mol; NH4Cl is -
314.4 Kcal/mol)

Answer:

ΔH = ΔHproducts - ΔHreactants
ΔHproducts = -314.4
ΔHreactants = -92.30 + (-80.29) = -172.59
ΔH = -314.4 – (-172.59) = -141.8

We can also represent enthalpy change with the

equation:

ΔH = ΔE + P ΔV

Where:

ΔV is the change in volume, in liters

P is the constant pressure

as follows :
f be the difference of enthalpy of a system in the final state (H 2) and that in
the initial state (H1),


Substituting the values of H2 and H1,as from (1) and( 2) , we have

P2V2) – (E1 +P1V1)

 P2V2 – P1V1 )

= E +PV
If P is constant while the gas is expanding, we can write

H = E +P V

or H = E +w (w =work) ……………..

(3)

According to the First Law,

E = q – w ……………..(4)

where q = heat transferred

From equation (3) and (4)

 H = q when change in state occurs at constant pressure

This relationship is usually written as

 H = qp
where subscript p means constant pressure.

Thus H can be measured by measuring the heat of a process occurring at constant

pressure.
Sign Conventions of Enthalpy
Since

 H = H2 – H1
H is positive if H2 > H1 and the process or reaction will be endothermic, i.e. a
reaction in which a system absorbs heat from its surroundings. H is negative if H 1
> H2 and the reaction will be exothermic, i.e. a reaction in which a system releases
heat to its surroundings.

Let's distinguish various phase changes of water as either endothermic or

exothermic.

1) The above reaction is EXOTHERMIC because heat is released when liquid

water freezes to form ice.

2) The above reaction is ENDOTHERMIC because there must be an input of

energy in order for water molecules in the liquid phase to have enough energy to
escape into the gas phase.

3) The above reaction is ENDOTHERMIC because there must be an input of

energy to break the bonds holding water molecules together as ice.

Relationship Between H and E

If we consider a system at constant volume, the heat is equal to change in Internal
energy, E.
We can measure heat at constant volume in a Bomb calorimeter. Calorific values
of many gaseous fuels are determined in constant volume calorimeters. These
values are, therefore, given by the expression

qv =E
When any fuel is burnt in the open atmosphere, additional energy of expansion,
positive or negative, against the atmosphere is also involved. The value of q thus
actually realized, i.e.,

qp = H
At constant pressure while the gas is expanding we have

 H=E+PV …………… (1)

If gases are involved in a reaction, they account for most of the volume changes as
the volumes of solids and liquids are negligibly small in comparison.

Suppose we have n1 moles of gases before reaction, and n 2 moles of gases after it.
Assuming ideal gas behavior, we have

P V2 = n2 RT

P V1 = n1RT

Therefore P (V2 –V1) = (n2- n1) RT

Or P V = n RT
Substituting in equation (1) we have,

H =E +  n RT
SOLVED PROBLEM. For the reaction

2O3 (g) → 3O2(g) 25°C, 1 atm

ΔE = - 287.9KJ
Calculate ΔH for the reaction .
SOLUTION

ΔH for a constant-pressure change is given by

ΔH = ΔU + P ΔV

Since ΔU is known from the question, we need only calculate P ΔV. The initial
volume of the system V1 is that of 2 mol O3 at 25°C.

Similarly, the final volume is that of 3 mol O2 at 25°C:

Thus

and

= 2479J = 2.479KJ

Thus ΔH = ΔU + P ΔV = − 287.9 kJ + 2.5 kJ = − 285.5 kJ

State Functions

Both enthalpy and the internal energy are often described as state functions. This
means that they depend only on the state of the system, i.e., on its pressure,
temperature, composition, and amount of substance, but not on its previous history.
Thus any solution of NaCl at 25°C and 101.3 kPa (1.000 atm) which contains a
mixture of 1 mol NaCl and 50 mol H 2O has the same internal energy and the same
enthalpy as any other solution with the same specifications. It does not matter
whether the solution was prepared by simply dissolving NaCl(s) in H2O, by
reacting NaOH(aq) with HCl(aq), or by some more exotic method.