Grade 12 Unit One

Thermodynamics
 A branch of physics that studies the relationship between energy and the
work of a system is called Thermodynamics. It shows how heat energy can
be converted into other forms of energy while affecting the matter as well.
 Thermodynamics is the study of energy relationships that involve heat,
mechanical work, and other aspects of energy and heat transfer.
Heat and Temperature
Energy can be transferred to a system by heat and by work done on the
system. Heat is a flow of energy from hotter regions to colder ones.
When we heat up a substance,
o The particles of the substance gain kinetic energy and so move
more rapidly.
o and/or The bonds between the particles in the substance are
broken and the potential energy of the particles increases. When
this happens, the substance changes state.
The concept of temperature has evolved from the common concepts
(sense) of hot and cold. The scientific definition of temperature is
proportional to the average kinetic energy of translation. Heat transfer is
the movement of energy from one place or material to another as a result
of a difference in temperature.
 Temperature is the average kinetic energy of particles in a body,
and used to determine in which direction there will be a net heat
energy flow when the two bodies are in-contact (or closed) each
other.
Thermal energy is the energy contained in a system. Heat is the flow of thermal
energy. Temperature is the average kinetic energy of the molecules. The concept
of temperature requires to understanding easily what is thermal contact thermal
expansion and thermal equilibrium.
 Two objects are in thermal contact *(it may not necessary to be in
body contact) if energy can be exchanged between them. Heat
energy flows from a hotter body to a colder body.
 Thermal expansion is the change of size of the material (object) due
to heating, linear area and volume expansion of materials.
 Two objects are in thermal equilibrium if they are in thermal contact
and there is no net exchange of energy.
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  OR Two objects are in thermal equilibrium if they are in close
contact that allows either to gain energy from the other, but
nevertheless, no net energy is transferred between them.
Temperature scales and thermometer
Two objects in thermal equilibrium with each other are at the same temperature.
 Three types of thermometers are alcohol, liquid crystal, and infrared
radiation (pyrometer).

 The main temperature scales are Celsius,

Fahrenheit, Rankine and Kelvin. Temperatures
can be converted from one scale to other using
temperature conversion equations.

 absolute zero the temperature at which a

substance has no thermal energy

Zeroth Law of Thermodynamics

The zeroth law of thermodynamics states that when two systems, A and B, are in
thermal equilibrium with each other, and B is in thermal equilibrium with a third
system C, then A is also in thermal equilibrium with C.
 The expansion of substances on heating is called thermal expansion.
 The exchange of energy between two objects because of differences in their
temperatures is called heat and the process called heating.
 The Zeroth law of thermodynamics states that if two bodies are individually
in equilibrium with a separate third body, then the first two bodies are also
in thermal equilibrium with each other.
 The zeroth law of thermodynamics enables us to use thermometers to
compare the temperature of any two objects that we like.

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 System
A thermodynamic system is a specific portion of matter with a definite
boundary on which our attention is focused. The system boundary may be real
or imaginary, fixed or deformable.
There are three types of systems:
 Isolated System – An isolated system cannot exchange energy and mass
with its surroundings. The universe is considered an isolated system.
 Closed System – Across the boundary of the
closed system, the transfer of energy takes place
but the transfer of mass doesn’t take place.
Refrigerator, compression of gas in the piston-
cylinder assembly are examples of closed systems.
 Open System – In an open system, the mass and
energy both may be transferred between the
system and surroundings. A steam turbine is an example of an open system.
Surrounding
Everything outside the system that has a direct influence on the behaviour of the
system is known as a surrounding.

Phases of matter
A phase of matter is when all the physical
properties within a material are uniform.
At a given phase of matter a material will
have the same density and refractive
index.
 The three phases of water (ice,
liquid water, and water vapor) can
coexist at a single pressure and
temperature known as the triple
point
The phase of a given substance depends
on the pressure and temperature. Thus, plots of pressure versus temperature
showing the phase in each region provide considerable insight into thermal
properties of substances. Such a pT graph is called a phase diagram.

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The boiling point curve ends at a certain point called the critical point—that is, a
critical temperature and critical pressure, above which the liquid and gas phases
cannot be distinguished.
Triple point is pressure and temperature at which a substance exists in equilibrium
as a solid, liquid, and gas.
Thermodynamic Process
A system undergoes a thermodynamic process when there is some energetic change
within the system that is associated with changes in pressure, volume and internal
energy.
There are four types of thermodynamic processes that have their unique properties,
and they are:
 Adiabatic Process – A process where no heat transfers into or out of the
system occurs.
 Isochoric Process – A process where no change in volume occurs and the
system does no work.
 Isobaric Process – A process in which no change in pressure occurs.
 Isothermal Process – A process in which no change in temperature occurs.
Laws of Thermodynamics
Thermodynamics laws define the fundamental physical quantities like energy,
temperature and entropy that characterize thermodynamic systems at thermal
equilibrium. These thermodynamics laws represent how these quantities behave
under various circumstances.
There are four laws of thermodynamics and are given below:
 Zeroth law of thermodynamics  Second law of thermodynamics
 First law of thermodynamics  Third law of thermodynamics
First Law of Thermodynamics
First law of thermodynamics, also known as the law of conservation of energy,
states that energy can neither be created nor destroyed, but it can be changed from
one form to another
∆U = Q - W
A thermodynamic system, its boundary, and its surroundings must be defined with
all the roles of the components fully explained before we can analyze a situation.
Thermal equilibrium is reached with two objects if a third object is in thermal
equilibrium with the other two separately.

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A general equation of state for a closed system has the form f (p, V, T) = 0, with an
ideal gas as an
Work, Heat, and Internal Energy
 Positive (negative) work is done by a thermodynamic system when it
expands (contracts) under an external pressure.
 Heat is the energy transferred between two objects (or two parts of a
system) because of a temperature difference.
 The internal energy U in a of a thermodynamic system is, by definition, the
sum of the mechanical energies of all the molecules or entities in the
system, then Internal energy of a thermodynamic system is its total
mechanical energy.
First Law of Thermodynamics
 The internal energy of a thermodynamic system is a function of state and
thus is unique for every equilibrium state of the system.
 The increase in the internal energy of the thermodynamic system is
given by the heat added to the system less the work done by the system
in any thermodynamics process.
 Thermodynamic Processes; the thermal behavior of a system is
described in terms of thermodynamic variables. For an ideal gas, these
variables are pressure, volume, temperature, and number of molecules
or moles of the gas.
 The first law states that the change in internal energy of that system is
given by Q−W. Since added heat increases the internal energy of a
system, Q is positive when it is added to the system and negative when
it is removed from the system.
or
 ∆U=Q + W where Q is the energy exchanged between the system and
the environment, and W is the work done on the system
 Both ∆U=Q + W and ∆U=Q – W have the same interpretation, since if work is
done by the system it is negative and if work is done by the system its is
positive.
For systems in thermodynamic equilibrium, the thermodynamic variables are
related by an equation of state.

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A heat reservoir is so large that when it exchanges heat with other systems, its
temperature does not change.
A reversible process is one that can be made to retrace its path and both the
temperature and pressure are uniform throughout the system.
 A thermodynamic process is defined as a change from one equilibrium
macro-state to another macro-state. The initial and final states are the
defining elements of the process.
Insulated systems allow no transfer of energy by heating. Isolated systems do not interact
with their surroundings so their internal energy remains constant.

Some list of thermodynamic processes, including

 isothermal, where the system’s temperature is constant; ΔU = 0 ,Q=W;
 slow process
 perfectly conducting wall
 An isothermal process is a thermodynamic process, in which the
temperature of the system remains constant (T = const). The heat
transfer into or out of the system typically must happen at such a slow
rate in order to continually adjust to the temperature of the reservoir
through heat exchange. In each of these states the thermal equilibrium
is maintained.
 no change in the internal energy
 The heat transfer into or out of the system typically must happen
at such a slow rate to continually adjust to the temperature of the
reservoir through heat exchange.
 The wall is perfectly conducting wall
 In the isothermal process and the ideal gas, all heat added to the
system will be used to do work:

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 First law thermodynamics Q=W since ∆U=0
Ideal gas relation PV= constant
P1V1=P2V2
Heat and work done Q=W= nRT ln

Q=W=P1V1 ln
Q=W=P1V1 ln
Adiabatic Process
An adiabatic process is a thermodynamic process in which there is no heat
transfer into or out of the system (Q = 0).
 adiabatic, where no heat is exchanged by the system; : Q= 0 , ΔU= −W;
 very fast process
 insulating wall
In isobaric process the pressure remains constant as the gas expands or is
compressed. The work done by the gas on its environment must come at
the expense of the change in its internal energy, ∆U. Because the change in
the internal energy of an ideal gas is given by ∆U=nCv∆T, the temperature of
an expanding gas must decrease as the internal energy decreases.
The system can be considered to be perfectly insulated.
In an adiabatic process, energy is transferred only as work.
The assumption of no heat transfer is very important since we can use the
adiabatic approximation only in very rapid processes.
In real devices (such as turbines, pumps, and compressors), heat losses and
losses in the combustion process occur. Still, these losses are usually low
compared to overall energy flow, and we can approximate some
thermodynamic processes by the adiabatic process.
First law thermodynamics ∆U =W since Q =0
PVꝩ= constant
Ideal gas relation
P1Vꝩ1=P2Vꝩ2
Heat and work done ∆U =W= nCV∆T

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Isobaric Process
An isobaric process is a thermodynamic process in which the pressure of the
system remains constant (p = const). The heat transfer into or out of the
system does work but also changes the internal energy of the system.
Any work done by the system will result in an increase in volume.
First law thermodynamics ∆U = Q - W
Ideal gas relation PV= constant
P1V1=P2V2
work done W=P∆V
Heat Q= nCP∆T
Isochoric Process
An isochoric process is a thermodynamic process in which the volume of the
closed system remains constant (V = const). It describes the behavior of gas
inside the container that cannot be deformed. Since the volume remains
constant, the heat transfer into or out of the system does not the p∆V
work but only changes the system’s internal energy (the temperature).
 isobaric, where the system’s pressure is constant; and ΔU=Q−W;
 isochoric, where the system’s volume is constant. : W= 0 , ΔU=Q
First law thermodynamics ∆U = Q since W=0
PV= constant
Ideal gas relation
P1V1=P2V2
work done W=0
Heat ∆U = Q= nCV∆T

PVΎ= constant PV=nRT V= P=

Ύ-1
TV = constent Ύ= 1 + 2/f
where f is degree of freedom 356=12poly
 Dalton's law of partial pressures states that the total pressure of a mixture
of gases is equal to the sum of the partial pressures of the component
gases:
PTotal=Pgas1 + Pgas2 + Pgas 3...
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 If the molecule’s velocity changes in the x -direction, its momentum changes from
mvx to +mvx . Thus, its change in momentum is Δmv = +mvx–(–mvx) = 2mvx . The
force exerted on the molecule is given by
F= F=2mvx/t
PV= NmV2
3PV/2N = 1/2mv2

K.Eavg= =

Graham's law states that the rate of diffusion or of effusion of a gas is inversely
proportional to the square root of its molecular weight.

The Second Law of Thermodynamics

Second law of thermodynamics states that the entropy in an isolated system always
increases. Any isolated system spontaneously evolves towards thermal
equilibrium—the state of maximum entropy of the system

 No heat engine operating in a cycle can absorb energy from a reservoir and
use it entirely for the performance of an equal amount of work.
 means that the efficiency e of engines must always be less than 1.
 If two systems are in thermal contact, net thermal energy transfers
spontaneously by heat from the hotter system to the colder system.
Reversible and Irreversible Processes
 In a reversible process, every state along the path is an equilibrium state, so
the system can return to its initial conditions by going along the same path
in the reverse direction. A process that doesn’t satisfy this requirement is
irreversible.

Entropy(S)
Then the change in entropy during any constant temperature process connecting
the two equilibrium states is defined as the amount of heat absorbed during a
reversible divided to constant temperature.

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The entropy of the Universe always increases in all natural processes, the entropy of
a system can decrease.
Entropy and Second law thermodynamics
The First Law of Thermodynamics is a statement of the principle of
conservation of energy. The Second Law of Thermodynamics is
concerned with the maximum fraction of a quantity of heat that can
be converted into work.
Second Law of Thermodynamics is:: The Heat Flow Statement
 Heat flows spontaneously from a substance at a higher
temperature to a substance at a lower temperature and
does not flow spontaneously in the reverse direction.
 “only by transferring heat from a warmer to a colder body can
heat can be converted into work in a cyclic process.”
 Heat can be converted into work in a cyclic process only by
transferring heat from a warmer to a colder body.
Or
 Heat cannot of itself pass from a colder to a warmer body in a
cyclic process.
A cyclic process is a series of operations by which the state of a
substance changes but finally returns to its original state.
If the volume of the working substance changes, the substance may
do external work, or work may be done on the working substance,
during a cyclic process.
Since the initial and final states of the working substance are the
same in a cyclic process, and internal energy is a function of state, the
internal energy of the working substance is unchanged in a cyclic
process.
Therefore, the net heat absorbed by the working substance is equal
to the external work that it does in the cycle.

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 Entropy is a function of the state of a system and not the path by
which the system is brought to that state. It does not depend on the
process, only depends on the initial and final states
Entropy is a measure of the disorder (or randomness) of a system.
The Second Law implies that the disorder of the universe is inexorably
increasing.
 A reversible process is one in which both the system and
its environment can be returned to exactly the states
they were in before the process occurred.
 An irreversible process is one that cannot be reversed by
means of small changes in the environment.
 a spontaneous process is a process which occurs without any
external input to the system.
 all spontaneous processes are irreversible, such as the
explosion of an unstable chemical or the bursting of a
bubble.
Entropy increases. If an irreversible process occurs in a closed system,
the entropy S of the system always increases, it never decreases
For the free expansion, we have ΔS > 0. It is an irreversible process in
a closed system.
For the reversible isothermal process, for the gas ΔS > 0 for expansion
and ΔS < 0 for compression. However, the gas itself is not a closed
system. It is only a closed system if we include both the gas and the
reservoir.
during expansion: So: ΔStotal = 0
If a process occurs in a closed system, the entropy of the system
increases for irreversible processes and remains constant for
reversible processes. It never decreases.
A reversible process is one that can be reversed by means of small
changes in the environment. In this case, ∆S = 0. e.g. An isothermal
expansion/compression of an ideal gas.

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 ΔS = 0 reversible process; ΔS > 0 irreversible process
Entropy is different: No conservation law – the entropy change ΔS
associated with an irreversible process in a closed system is always
greater than or equal to zero.
 The two laws of thermodynamics may be summarized as
follows:
o The energy of the universe is constant
o The entropy of the universe tends to a maximum.
THE SECOND LAW OF THERMODYNAMICS can be stated in three equivalent
ways:
 Heat flows spontaneously from a hotter to a colder ob ect, but not
vice versa.
 No heat engine that cycles continuously can change all its heat-in to
useful work-out.
 If a system undergoes spontaneous change, it will change in such a
way that its entropy will increase or, at best, remain constant.
The Second Law tells us the manner in which a spontaneous change
will occur, while the First Law tells us whether or not the change is
possible. The First Law deals with the conservation of energy; the
Second Law deals with the dispersal of energy.

ENTROPY …S† is a state variable for a system in equilibrium. By this is

meant that S is always the same for the system when it is in a given
equilibrium state. Like P, V, and U, the entropy is a characteristic of
the system at equilibrium.
When heat Q enters a system at an absolute temperature T, the
resulting change in entropy of the system is
S=Q/T
provided the system changes in a reversible way. The SI unit for
entropy is J/K.
A reversible change (or process) is one in which the values of
P, V, T, and U are well-defined during the change. If the process is
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 reversed, then P, V, T, and U will take on their original values when
the system is returned to where it started. To be reversible, a process
must usually be slow, and the system must be close to equilibrium
during the entire change.
Another, fully equivalent, definition of entropy can be given
from a detailed molecular analysis of the system. If a system can
achieve a particular state (i.e., particular values of P, V, T, and U) in
(omega) different ways (different arrangements of the molecules, for
example), then the entropy of the state is
S=kb lnΩ
where ln is the logarithm to base e, and kB is Boltzmann's
constant, 1.38x10 -23J/K.
ENTROPY IS A MEASURE OF DISORDER: A state that can occur
in only one way (one arrangement of its molecules, for example) is a
state of high order.

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