 Kirchhoff’s Law of Thermal Radiation

 In general, both the emissivity, ε, and

the absorptivity, α, of a surface depend on
the temperature and the wavelength of the
radiation.
 Kirchhoff’s law of thermal radiation,
postulated by a German physicist Gustav
Robert Kirchhoff, states that the emissivity
and the absorptivity of a surface at a given
temperature and wavelength are equal.
 Kirchhoff’s Law of thermal radiation:
 For an arbitrary body emitting and absorbing
thermal radiation in thermodynamic
equilibrium, the emissivity is equal to the
absorptivity.
 emissivity ε = absorptivity α
 This law must be also valid in order to satisfy
the Second Law of Thermodynamics. As was
written, all bodies above absolute zero
temperature radiate some heat.
 Two objects radiate heat toward each other. But
what if a colder object with high emissivity
radiates toward a hotter object with very low
emissivity? This seems to violate the Second Law
of Thermodynamics, which states that heat
cannot spontaneously flow from cold system to
hot system without external work being
performed on the system.
 . The paradox is resolved by the fact that each
body must be in direct line of sight of the other
to receive radiation from it.
 Therefore, whenever the cool body is radiating
heat to the hot body, the hot body must also be
radiating heat to the cool body. Moreover, the
hot body will radiate more energy than cold
body.
 The case of different emissivities is solved by the
Kirchhoff’s Law of thermal radiation, which states
that object with low emissivity have also low
absorptivity. As a result, heat cannot
spontaneously flow from cold system to hot
system and the second law is still satisfied
 The emissivity, ε, of the surface of a material
is its effectiveness in emitting energy
as thermal radiation and varies between 0.0
and 1.0.By definition, a blackbody in thermal
equilibrium has an emissivity of ε = 1.0. Real
objects do not radiate as much heat as a
perfect black body. They radiate less heat
than a black body and therefore are called
gray bodies
 Another important radiation property of a
surface is its absorptivity, α, which is the
fraction of the radiation energy incident on a
surface that is absorbed by the surface. Like
emissivity, value of absorptivity is in the
range 0 < α < 1.From its definition,
a blackbody, which is an idealized physical
body, absorbs all incident electromagnetic
radiation, regardless of frequency or angle of
incidence.
 In general, the absorptivity and
the emissivity are interconnected by
the Kirchhoff’s Law of thermal radiation,
which states:
 For an arbitrary body emitting and absorbing
thermal radiation in thermodynamic
equilibrium, the emissivity is equal to the
absorptivity.
 emissivity ε = absorptivity α
 The Grotthuss–Draper law (also called
the Principle of Photochemical Activation) states
that only that light which is absorbed by a system
can bring about a photochemical change.
Materials such as dyes and phosphors must be
able to absorb "light" at optical frequencies. This
law provides a basis
for fluorescence and phosphorescence. The law
was first proposed in 1817 by Theodor
Grotthuss and in 1842, independently, by John
William Draper.[5]
 This is considered to be one of the two basic
laws of photochemistry.
 Grotthus-Draper Law (or) The Principle of
Photochemical Activation: Grotthus-Draper
law states that only the light which is
absorbed by a substance can bring about a
photochemical change. However, the
absorbed radiation does not necessarily
cause a chemical reaction. When the
conditions are not favourable for the
molecules to react, the light energy may be
reemitted as heat or light or it remains
unused.
 First law of thermodynamics: When energy
passes, as work, as heat, or with matter, into or
out of a system, the system's internal
energy changes in accord with the law
of conservation of energy

 Second law of thermodynamics: In a

natural thermodynamic process, the sum of
the entropies of the interacting thermodynamic
systems increases.
 Third law of thermodynamics: The entropy of a
system approaches a constant value as the
temperature approaches absolute zero.
 absolute zeroThe lowest temperature that is
theoretically possible.
 entropyA thermodynamic property that is the
measure of a system’s thermal energy per
unit of temperature that is unavailable for
doing useful work.
 The first law, also known as Law of
Conservation of Energy, states that energy
cannot be created or destroyed in an isolated
system.
 The second law of thermodynamics states
that the entropy of any isolated system
always increases.
 The third law of thermodynamics states that
the entropy of a system approaches a
constant value as the temperature
approaches absolute zero.
 First law
 This law says that there are two kinds of processes,
heat and work, that can lead to a change in the
internal energy of a system. Since both heat and work
can be measured and quantified, this is the same as
saying that any change in the energy of a system
must result in a corresponding change in the energy
of the surroundings outside the system. In other
words, energy cannot be created or destroyed. If heat
flows into a system or the surroundings do work on
it, the internal energy increases and the sign of q and
w are positive. Conversely, heat flow out of the
system or work done by the system (on the
surroundings) will be at the expense of the internal
energy, and q and w will therefore be negative.
 Second law
 A simple way to think of the second law of
thermodynamics is that a room, if not
cleaned and tidied, will invariably become
more messy and disorderly with time –
regardless of how careful one is to keep it
clean. When the room is cleaned, its entropy
decreases, but the effort to clean it has
resulted in an increase in entropy outside the
room that exceeds the entropy lost.
 The zeroth law of thermodynamics states that
if two thermodynamic systems are each in
thermal equilibrium with a third one, then
they are in thermal equilibrium with each
other. Accordingly, thermal equilibrium
between systems is a transitive relation.