Thermodynamic Equilibrium

Thermodynamic Equilibrium
• Generally, a system is said to be in equilibrium
when its properties do not change appreciably with
time.
• A system is said to be in thermodynamic
equilibrium with its surrounding or with another
system if and only if the system is in thermal
equilibrium, in chemical equilibrium and in
mechanical equilibrium with the surrounding or
with another system.
• If any one of the above conditions is not fulfilled,
the system is not in thermodynamic equilibrium.
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Thermal equilibrium: For a system to be in
thermal equilibrium, there should be no temperature
difference between the parts of the system or between
the system and the surroundings i.e. the temperature is
the same throughout the entire system

A closed system reaching thermal equilibrium.

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Mechanical Equilibrium: is related to pressure,
and a system is in mechanical equilibrium if there is no
change in pressure at any point of the system with time.
A system attains mechanical equilibrium with its
surrounding when there is no unbalance or net force in
the interior of the system and also none between the
system and its surroundings.
Chemical Equilibrium: A system attains
chemical equilibrium when the chemical composition
of a system does not change with time i.e. no chemical
reactions going on within the system or there is no
transfer of matter from one part of the system to other
due to diffusion.
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 The State Postulate
• The number of properties
required to fix the state of a
system is given by the state
postulate:
❖The state of a simple
compressible system is
completely specified by two
independent, intensive
properties.
• Simple compressible system: If
a system involves no electrical, The state of nitrogen is
fixed by two independent,
magnetic, gravitational, motion, intensive properties.
and surface tension effects.
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Checkpoint:
1) A can of soft drink at room temperature is put into
the refrigerator so that it will cool. Would you model
the can of soft drink as a closed system or as an open
system? Explain.
A can of soft drink should be analyzed as a closed
system since no mass is crossing the boundaries of the
system.
2) Is the state of the air in an isolated room completely
specified by the temperature and the pressure? Explain.
Yes, because temperature and pressure are two
independent properties and the air in an isolated room
is a simple compressible system.
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Process: Any change that a system undergoes from
one equilibrium state to another is called process.
A system undergoes a thermodynamic process when
there is some sort of energy changes within the system,
generally associated with changes in pressure, volume,
internal energy, temperature, or any sort of heat
transfer.
Path: The series of states through which a system
passes during a process is called the path of the
process.

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Quasi-static or quasi-equilibrium process: When a
process proceeds in such a manner that the system
remains infinitesimally close to an equilibrium state at
all times.

A quasi-equilibrium process
can be viewed as a
sufficiently slow process that
allows the system to adjust
itself internally so that
properties in one part of the
system do not change any
faster than those at other
parts.
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In most of the processes that we will study, one
thermodynamic property is held constant.
The prefix iso- is often used to designate a process for
which a particular property remains constant.
Some of these processes are
Adiabatic process: This is a thermodynamic process in
which there is no heat transfer into or out of the system. For
this process, change in quantity of heat is zero (i.e. DQ = 0
during this process)
Isochoric process: This is a thermodynamic process that
occurs at constant volume (i.e. DV = 0 during this process).
This implies that during this process no work is done on or
by the system.
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Isobaric process: This is a thermodynamic process
that occurs at constant pressure (i.e. Dp=0 during this
process).
Isothermal process: This is a thermodynamic process
that takes place at constant temperature (i.e. DT = 0
during this process).
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P Process B
Cycle: A system is said to
have undergone a cycle if it
returns to its initial state at the Process A
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end of the process i.e. for a
cycle, the initial and final
states are identical. V
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Temperature:
• Temperature (T) is defines as the degree of hotness or
coldness of a body.
• Temperature is one of the seven SI base quantities and it
is measured in Kelvin (K).
• Temperature of a body has no upper limit but it has
lower limit (absolute zero or zero Kelvin).
Heat: Heat is defined as energy in transit.
• Heat (Q) is a form of energy that is transferred from one
body to another by virtue of a difference in temperature.
• Temperature gradient gives the direction of heat flow
(i.e. from a body of higher temperature to a body of
lower temperature).
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 Heat:
• The process of heat flow is called heat exchange.
• For two bodies in thermal contact, this process of
heat exchange will continue until the two bodies
attained thermal equilibrium (i.e. equal temperature).
• Sign of heat (Q)
• Q is positive when there is a flow of heat into the
system.
• Q is negative when there is a flow of heat out of the
system.

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 Units for Heat
• SI unit for heat is the joule, J.
• Calorie is another unit for heat. The calorie (cal) was
defined as the amount of heat that would raise the
temperature of 1g of water from 14.5°C to 15.5°C.
• The calorie is now defined to be 4.1868 J.
• In the British system, the corresponding unit of heat
was the British thermal unit (Btu), defined as the
amount of heat that would raise the temperature of 1lb
of water from 63°F to 64°F.

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The zeroth law of thermodynamics: If systems A and B
are each in thermal equilibrium with a third system C,
then A and B are in thermal equilibrium with each other.
By replacing the third system C with a thermometer, the
zeroth law can be restated as
Two bodies are in thermal equilibrium if both have the
same temperature reading even if they are not in contact.
The zeroth law was first formulated and labeled by R. H.
Fowler in 1931.
As the name suggests, its value as a fundamental physical
principle was recognized more than half a century after the
formulation of the first and the second laws of
thermodynamics.
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A statement of the zeroth law in terms of temperature is
the following:
There exists a scalar quantity called temperature, which
is a property of all thermodynamic systems in
equilibrium.
Two systems are in thermal equilibrium if and only if
their temperatures are equal.

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