What is Chemical Energetic?

Chemical energetic is the study of chemical

changes caused by energy. Chemical energetic
discusses both thermodynamics and kinetics
of 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).
Chemical Kinetics deals with the rate of
reactions.
 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.
 (a) 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 open systems, closed
systems and isolated systems. An open system is
one in which matter and energy can be exchanged
with the surroundings. A closed System is a system
that can exchange energy but not matter with their
surroundings. While an isolated system is one in
which neither energy nor matter can be exchanged
with the surroundings.
 (b) 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.
 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; 1J = 1Nm.
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 to 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.
For example, the simplest form of mechanical work arises
when an object moves a certain distance against an opposing
force.
Electrical work is done when a body having a certain charge
moves through a potential difference.
Gravitational work is said to be done when a body is raised
through a certain height against the gravitational field,
formulae: mgh.
 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 contd.
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
Fig. 1 shows a quantity of gas confined in a cylinder
by means of a moveable piston. Weights placed on
x
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 quantity of work,
fx 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
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. Since
pressure is force per unit area and the product of
the length A and the area has the dimensions of
volume we obtain: 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.
 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
Where ∆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
EA..It absorbs from the surroundings a certain amount
of heat Q and undergoes a change in its state to B
where it’s energy is EB.
The increase in energy of the system ∆E is given by
∆E = EB - 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 i.e., ∆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.
APPLICATIONS OF THE FIRST LAW OF THERMODYNAMICS
 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
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)
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)
We can also represent enthalpy change with the equation:
ΔH = ΔE + P ΔV ……(1)
Where, ΔV is the change in volume, in liters and P is the constant pressure
If ΔH be the difference of enthalpy of a system in the final state (H2) and that in the
initial state (H1),
ΔH = H2 - H1 ...(2)
Substituting the values of H2 and H1,as from (1) and( 2) , we have
ΔH = (E2 +P2V2) – (E1 +P1V1)
= (E2 -E1) + (P2V2 – P1V1 )
= ΔE + ΔPV
If P is constant while the gas is expanding, we can write
ΔH = ΔE +P ΔV
or ΔH = ΔE +w (w = work) ……………..(3)
According to the First Law, ΔE = q – w ……………..(4)
where q = heat transferred
From equation (3) and (4)
ΔH = q when change in state occurs at constant pressure. This relationship is usually
written as : ΔH = qp
where subscript p means constant pressure.
Thus ΔH can be measured by measuring the heat of a process occurring at constant
pressure.
 Relationship Between ΔH and ΔE
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 =ΔE
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 = ΔH
At constant pressure while the gas is expanding we
have
ΔH = E + PΔV …………… (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 n2 moles of gases after it. Assuming ideal gas
behavior, we have
P V2 = n2 RT and P V1 = n1RT
Therefore P (V2 –V1) = (n2- n1) RT
Or P ΔV = Δn RT
Substituting in equation (1) we have,
ΔH =ΔE + ΔnRT