First Law of Thermodynamics

Dvarkesh Mahera
First Law of Thermodynamics
The idea of designing an engine that would
produce mechanical work continuously without
drawing energy from external sources and without
undergoing a change.
The law of conservation of energy. The
fundamental implication of this law is that
“although energy may be converted from one form
to another, it cannot be created or destroyed”.
Whenever a quantity of one form of energy is
produced, an exactly equivalent amount of
another kind must be used-up.
First Law of Thermodynamics

When the law of conservation of energy was

proposed, heat was not considered to be a
form of energy.
It was a series of experiments conducted by
Joule between 1843 and 1847 that established
heat as a form of energy.
First Law of Thermodynamics
Joule Experiments.
A known quantity of water taken in an
insulated container was agitated by means of a
paddle wheel. The resulting temperature rise
was noted. It was found that an exact
proportionality existed between the amount of
work expended on the water and the rise in
temperature. The same proportionality was
obtained by the following different methods of
transforming work into heat.
First Law of Thermodynamics
Joule Experiments.
The mechanical work was converted to
electricity and the electric current was passed
through coils immersed in water.
A gas confined in a cylinder immersed in water
was compressed mechanically.
Two metal pieces immersed in water were
rubbed against each other by mechanical work.
First Law of Thermodynamics
Joule Experiments.
The use of a given amount of work on a quantity of
adiabatically enclosed water gave the same temperature
rise regardless of the way in which the process was
carried out.
Joule’s experiments established a quantitative
relationship between heat and work thus rejecting the
earlier theory that treated heat as a substance.
The recognition that heat and internal energy are forms
of energy led to their inclusion in the law of
conservation of energy along with work, potential
energy, and kinetic energy and the law came to be
known as first law of thermodynamics.
First Law of Thermodynamics
INTERNAL ENERGY
Heat and work represent energy in transit. Energy
exchange between the system and the surroundings
occurs either as heat or as work.
Heat and work are thus external effects of changes
occurring within the system or are external
manifestations of stored energy. What happens to the
state of the system after heat is supplied to it and before
work is extracted from it?
The energy stored in the system by virtue of the
configuration (Potential Energy) and motion (Kinetic
Energy) of the molecules constituting the system is
called its internal energy.
First Law of Thermodynamics
INTERNAL ENERGY
The molecules constituting the system possess
kinetic energy of translation, rotation, and
vibration. They also possess potential energy due
to the forces of attraction existing among them.
These molecular potential and kinetic energies
contribute to the internal energy of the system.
The addition of heat to the system results in the
increase of its molecular kinetic energy and thus
increases the internal energy of the system.
Internal energy is a state function.
First Law of Thermodynamics
FIRST LAW OF THERMODYNAMICS FOR NON-FLOW
PROCESS (CLOSED SYSTEM)
The first law of thermodynamics requires that the
change in the total energy of the system be
compensated by an equal but opposite change in the
total energy of the surroundings, so that, there is no net
change in the energy in any process.
The change in the total energy of the surroundings
occurs only through the exchange of heat or work with
the system. Then the change in the total energy of the
surroundings, must be equal to the energy transferred
to or from it as heat and work. Since Q is the heat
transferred to the system and W is the work extracted
from it during the process,
First Law of Thermodynamics
FIRST LAW OF THERMODYNAMICS FOR NON-
FLOW PROCESS (CLOSED SYSTEM)
(∆ E) sur = – Q + W,
(∆ E)sys = – (∆E) sur,
(∆ E) sys = Q – W.
For a closed system undergoing only changes in
the kinetic, potential, and internal energies, the
total energy change of the system (∆ E)sys is given
by
(∆ E)sys = ∆(KE) + ∆(PE) + ∆ U
Q – W = ∆(KE) + ∆(PE) + ∆ U
First Law of Thermodynamics
FIRST LAW OF THERMODYNAMICS FOR NON-FLOW
PROCESS (CLOSED SYSTEM)
In the above equations D(KE) and D(PE) denote changes
in kinetic energy and potential energy respectively.
Equation means that the total energy change in a closed
system is equal to the heat added to the system minus
the work done by the system.
For a steady-state non-flow process in which there are
no changes in the kinetic energy and potential energy,
the above equation simplifies to
∆U = Q – W
Differential form, dU = dQ - dW
First Law of Thermodynamics
ENTHALPY
For a system kept at constant volume in which no
work of expansion or any other kind of work is
done, the change in internal energy is equal to the
heat supplied to it.
When the system is free to change its volume
against a constant external pressure, the change in
internal energy is no longer equal to the energy
supplied as heat.
In effect, a part of the energy supplied is utilized by
the system for occupying a new volume;
First Law of Thermodynamics
ENTHALPY
The energy thus utilized is equal to the work
required to ‘push’ the surroundings against a
constant pressure.
Consequently, DU < Q. However, the heat supplied
at constant pressure can be measured as the
change in another thermodynamic property of the
system which we call the enthalpy.
Enthalpy is denoted by H and is perhaps the most
widely used of all thermodynamic functions. It is
defined as
H = U + PV
First Law of Thermodynamics
ENTHALPY
In differential form, can be written as
dH = dU + d(PV)
dH = dU + P dV + V dP
dH = dQ – dW + P dV + V dP
Noting that dW = P dV for a reversible non-flow
process and V dP = 0 for constant pressure
process, the above equation simplifies to
dH = dQ (for constant pressure process)………
First Law of Thermodynamics
HEAT CAPACITY
We remarked earlier that heat is often viewed
in relation to its effect on the object to which
or from which it is transferred.
This is the origin of the idea that a body has a
capacity for heat. The smaller the temperature
change in a body caused by the transfer of a
given quantity of heat, the greater its capacity.
Indeed, a heat capacity might be defined:
First Law of Thermodynamics
HEAT CAPACITY
The heat capacity of a substance is the quantity
of heat to be supplied to effect a temperature
rise of one degree.
dQ = C * dT
C=dQ/dT
where C is known as heat capacity of the
substance. Heat capacity of unit mass of a
substance is also known as specific heat of the
substance.
First Law of Thermodynamics
HEAT CAPACITY
The heat capacity depends on the way in which
heat is supplied. When heat is supplied to a system
at constant volume, the system is unable to do any
work and the quantity of heat required is given by
dQ = Cv * dT (constant volume)…
where CV is known as the heat capacity at
constant volume. Thus,
Cv = (dQ/dT)v
For constant volume Process, dQ=dU
Cv = (dU/dT)v
First Law of Thermodynamics
HEAT CAPACITY
If heat is supplied to a substance at constant pressure, it
is free to expand doing work against the constant
pressure.
A part of the heat supplied to the system is utilized for
the work of expansion and more heat will be required to
raise the temperature than that required in a constant
volume process for the same temperature change. The
amount of heat required is related to the temperature
rise as
dQ = Cp * dT (constant pressure)
where Cp is called the heat capacity at constant
pressure.
First Law of Thermodynamics
HEAT CAPACITY
Thus, dQ = Cp * dT (constant Pressure)…
Cp = (dQ/dT)p
For a constant pressure process, dQ=dH
Hence , Cp = (dH/dT)p