THERMODYNAMICS

Study of the transformation of

energy
FACTORS affecting The STATE of
a thermodynamic system

• Absolute Pressure (P) in Pascal

• Temperature (T) in Kelvin
• Volume (V) in cubic meters
• Number of moles (n) of working gas
FORMS OF ENERGY
• WORK
• Force is moved through a distance
• W = force x distance (expressed as Joule)
• HEAT
• A form of energy that flows from a
warmer object to a cooler object.
• Expressed as Calorie
• CONDUCTION - The "diffusion" of thermal
energy (heat) through a substance.
• CONVECTION - The transfer of heat
energy by the movement of a substance.
• RADIATION – It refers just to light
continuously emit, or radiate
electromagnetic waves (that is, light
waves) into their surroundings. It takes
place even in a vacuum.
 Thermodynamic process
• Isobaric process (dP) = occur at constant
pressure
P=0
• Isometric/ isochoric = occurs at constant Volume
dV = 0
• Isothermic process (dT) = occur at constant
temperature
T = 0; U = 0
• Adiabatic process (q) = occur without heat
exchange with the surroundings
q=0
 TYPES OF SYSTEM
• System:
• The part of universe of
interest

• Surrounding:
• everything else; relevant
to the system.

• Universe:
• System + Surroundings
 TYPES OF SYSTEM
• Closed system - exchange heat and work but
not matter with its surroundings
• Ex. stoppered flask
• Open system - involves a transfer of matter in
addition to the exchange of heat and work
• Ex. flask that is not stoppered and to which various
substances can be added
• Isolated system - a system that can
exchange neither matter nor energy with its
surroundings
• Ex. sealed flask that is thermally, mechanically,
and electrically insulated from its surroundings
THERMODYNAMIC SYSTEMS
INTERNAL ENERGY
• Function of the chemical nature of the substance, its
temperature and at times the pressure and volume of the
system.
• Determined by the kinetic, rotational and vibrational
motion of the molecules
• ΔE = E2 + E1
ENTHALPY (H)
• Heat transfer between the system and its
surroundings under constant pressure.
• the sum of the internal energy and the product of
the pressure and volume of a thermodynamic
system
• H = E + PV
• value is determined entirely by the temperature,
pressure, and composition of the system and not
by its history
• Enthalpy is a guide to whether a reaction is likely
to proceed.
First law of
thermodynamics
Second law of
thermodynamics
Third law of
thermodynamics
ZEROTH LAW OF
THERMODYNAMICS
 ZEROTH LAW OF THERMODYNAMICS

• Thermal Contact
• Thermal Equilibrium
• If two objects are in thermal equilibrium
with a third, then they are in thermal
equilibrium each other.
• Two objects are defined to have the
same temperature if they are in thermal
equilibrium with each other
FIRST LAW OF
THERMODYNAMICS
• Energy cannot be created nor destroyed.
• Total energy in a given system remains
constant
• Energy can, however, be converted from
one form to another or transferred from a
system to the surroundings or vice versa.
FIRST LAW OF THERMODYNAMICS
ΔE = q – w
Where:
ΔE = internal energy
w = work done
q = heat change
Example : In the figure, the gas absorbs 400 J
of heat and at the same time does 120 J of
work on the piston. What is the change in
internal energy of the system?
Wout =120 J

Qin
400
J
DQ is positive: +400 J (Heat IN)
DW is positive: +120 J (Work OUT) Wout =120 J
DU = DQ - DW
Qin
DE = DQ - DW 400
= (+400 J) - (+120 J) J
= +280 J
SECOND LAW OF
THERMODYNAMICS
• All forms of energy can be converted into heat but
heat cannot be completely transformed into other
forms of energy
• The entropy of the universe increases (real,
spontaneous processes).But, entropy can
decrease for individual systems.
 SECOND LAW OF THERMODYNAMICS

The entropy of the universe does not change for

reversible processes and increases for
spontaneous processes.

Reversible (ideal):

Irreversible (real, spontaneous):

ENTROPY (S)
• term coined by Rudolph Clausius in the
19th century.
• can be thought of as a measure of the
randomness of a system.
• It is related to the various modes of
motion in molecules.
ENTROPY
• A measure of randomness or disorder
• S = entropy in J/K·mole
• Increasing disorder or increasing
randomness is increasing entropy.
ENTROPY

• Like total energy, E, and enthalpy, H,

entropy is a state function.
• Therefore,
DS = Sfinal - Sinitial
THIRD LAW OF
THERMODYNAMICS
THIRD LAW OF THERMODYNAMICS
The entropy of a pure crystalline
substance at absolute zero is 0.
THIRD LAW OF THERMODYNAMICS
ž The entropy of a system at absolute zero is
typically zero, and in all cases is determined
only by the number of different ground
states it has. Specifically, the entropy of a pure
crystalline substance at absolute
zero temperature is zero.
ž As the temperature approaches zero, the
entropy of a system approaches a constant
value which is called the Residual Entropy.
THIRD LAW OF THERMODYNAMICS
ž Third Law of Thermodynamics relates the entropy
(randomness) of matter to its absolute
temperature.
ž The Third Law of Thermodynamics refers to a
state known as Absolute Zero. At zero
temperature the system must be in a state with the
minimum thermal energy. This statement holds
true if the perfect crystal has only one state with
minimum energy.
 Standard Entropies

Larger and more complex molecules have

greater entropies.
 Gibbs Free Energy
• Josiah Willard Gibbs
• • Gibbs free energy, originally called
available energy, Gibbs defined: “ The
greatest amount of mechanical work
which can be obtained from a given quantity
of a certain substance in a given initial state,
without increasing its total volume or
allowing heat to pass to or from external
bodies, except such as at the close of the
processes are left in their initial condition.”
 Gibbs free energy
1. If ΔG is negative, the forward reaction
is spontaneous.
2. If ΔG is 0, the system is at
equilibrium.
3. If ΔG is positive, the reaction is
spontaneous in the reverse direction.
Thank
You!