Thermal Physics

Instructor-
Golam Dastegir Al-Quaderi
Professor
Department of Physics, DU

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 Generalized Force and Generalized
Work
• In the previous lectures we have studied five
types of simple thermodynamics systems:
• A. Real Gas
• B. Stretched Wire
• C. Thin Surfaces
• D. Dielectric Slab in a Capacitor
• E. Paramagnetic Rod inside a Magnetic Field

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 Generalized Force and Generalized
Work
• The work done on these systems are given in
the table below:

Thermodynamic Intensive Extensive Coordinate

Work Done 𝒅𝑾
Systems Coordinate
Hydrostatic System Pressure 𝑃 Volume 𝑉 −𝑃𝑑𝑉
Stretched Wire Tension 𝐹 Length 𝐿 𝐹𝑑𝐿
Thin Surface Surface tension 𝛾 Area 𝐴 𝛾𝑑𝐴
Dielectric Slab Electric Field 𝐸 Total Polarization Π 𝐸 𝑑Π
Paramagnetic Rod Magnetic Field 𝐻 Total Magnetization 𝑋 𝜇0 𝐻 𝑑𝑋

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 Generalized Force and Generalized
Work
• Note that, each expression of the work done is a
product of an intensive coordinate and an
infinitesimal change of extensive coordinate.
• Hence, the work done is an extensive coordinate.
• A work diagram is obtained if anyone of the
intensive coordinates is plotted against its
corresponding extensive coordinate.
• There are, therefore, as many work diagrams as
there are systems.
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 Generalized Force and Generalized
Work
• Generalized Displacement: The extensive
thermodynamic variable, whose change
multiplied by the appropriate generalized
conjugate variable, gives the work done on a
system is called the generalized displacement.
• In our systems these are: volume 𝑉, length 𝐿,
area 𝐴 , total polarization Π and the total
magnetization 𝑋.
• All these relate to the total size of the system and
are extensive.
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 Generalized Force and Generalized
Work
• Generalized Force: The intensive thermodynamic
coordinates which multiplied with the
generalized displacements of the thermodynamic
systems, give the work done on the system are
called the generalized forces.
• For example, in our systems these are: pressure
𝑃, tension 𝐹, surface tension 𝛾, electric field 𝐸
and the magnetic intensity times permeability
𝜇0 𝐻.
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 Generalized Force and Generalized
Work
• In terms of the generalized variables, we may
represent the work done by any simple system
on a generalized work diagram by plotting the
generalized force Y against the generalized
displacement X.
• Conclusions based on such a diagram will hold
for any simple system.

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 Work and Heat
• A system could be transferred from an initial to a
final state by means of a quasi-static process.
• We have seen the expressions for the work done
on a system.
• There are, however, other means of changing the
state of a system that do not necessarily involve
the performance of work.
• Consider the following four processes which
involve closed systems (no matter or energy
passes between the system and its environment).
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 Work and Heat
• System-A: The system consists of water and a paddle
wheel, which is caused to rotate and churn the water
by means of a falling weight.
• As a result, the temperature of the water rises from the
room temperature to a slightly higher temperature.
• System-B: In the second system the water and the
resistor constitute the system.
• The electric current in the resistor is being maintained
by a generator turned by means of a falling weight.
• Again, the temperature of the water rises.

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 Work and Heat
• In both cases, the state of the system is
caused to change; and since the agency for
changing the state of the system is a falling
weight, both processes involve the
performance of work.

Change of state by work 10

 Work and Heat
• In the other two situations, the system is water in a
diathermic container.
• System-C: In the third case system (water) is in contact
with the burning gases at a high temperature,
everything being contained in a adiabatic wall.
• System-D: In the fourth case, the system (water) is near
but not in contact with a lamp whose temperature is
much higher than that of the water.
• In both cases, the system is caused to change, but in
neither case can the agency of change be described by
mechanical means.

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 Work and Heat
• In the last two cases, the state of the system
changes by means of flow of heat from one
part to the other.

Change of state by heat transfer

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 Work and Heat
• We define heat as:
• Definition: Heat is that which is transferred
between a system and its surroundings by virtue
of a temperature difference only.
• We know that heat is a form of energy.
• We also define:
• Adiabatic Wall or heat insulator: A wall which is
impervious to heat transfer.
• Diathermic wall or heat conductor: A wall that
transmits heat.

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 Work and Heat
• Adiabatic Work: When a closed system is
completely surrounded by an adiabatic boundary,
the system may still be coupled to the
surroundings so that work may be done.
• Work done in an adiabatic container is called an
adiabatic work.
• The state of a system may be caused to change
from a given initial state to the same final state by
the performance of adiabatic work only.
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 Work and Heat
• We have different examples of adiabatic work.
• In all three cases, the system is surrounded by
adiabatic wall.

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 Work and Heat
• We may change the state of a system by different
adiabatic paths.
• There are an infinite
number of paths
by which a system
may be transferred
from an initial state
to a final state by
the performance of
adiabatic work only.
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 Work and Heat
• Experiment proved that the adiabatic work is the
same along all such paths.
• The generalization of the statement that the
adiabatic work is path independent is a restricted
statement of the first law of thermodynamics:

lf a closed system is caused to change from an

initial state to a final state by adiabatic means
only, then the work done on the system is the
same for all adiabatic paths connecting the two
states.
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 Work and Heat
• Whenever a quantity is known to depend only on the
initial and final states, and not on the path connecting
them, an important conclusion can be drawn.
• Therefore, it follows from the restricted statement of
the first law of thermodynamics that:

There exists a function of the coordinates of a

thermodynamic system whose value at the final state
minus its value at the initial state is equal to the
adiabatic work done in going from one state to the
other.
• This function is known as the internal-energy function.

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 Work and Heat
• Hence, we have
𝐸𝑖𝑛𝑡 = 𝑈
𝑊𝑖→𝑓 adiabatic = 𝑈𝑓 − 𝑈𝑖
where,𝑊𝑖→𝑓 adiabatic denotes adiabatic work done on
the system.
• Thus, thermodynamic work, which is generally path-
dependent, becomes path-independent for an adiabatic
process.
• The equation above states that:
There exists an energy function, whose difference between
two values, is the energy change of the system and is equal
to the adiabatic work done on the system.

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 Work and Heat
• Internal Energy Function: For a hydrostatic
system, if 𝑈 is regarded as a function of 𝑇 and 𝑉:
𝑈 = 𝑈 𝑇, 𝑉 and
𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑈 𝑇, 𝑉 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
• Again, internal energy may be thought of a
function of 𝑇 and 𝑃 only: 𝑈 = 𝑈(𝑇, 𝑃)
𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑈 𝑇, 𝑃 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇

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 Work and Heat
• Mathematical Formulation of the First Law:
• The process of adiabatic work is not the only
process the state of a system may be changed.
• We may have processes involving diathermic wall
in which heat is exchanged between the
surroundings and the system as well as work
done.
• In the first case, the gas is in contact with a flame
whose temperature is higher than that of the gas.
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 Work and Heat
• At the same time, the gas is forced to contract, so
diathermic work is performed on the system.
• In the second case,
the total magnetization
of a paramagnetic solid
is increased while it
is in contact with liquid
helium.

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 Work and Heat
• The temperature of liquid helium is lower than
that of the solid.
• Hence, some of the helium boils away during the
magnetization.
• We may have work done on/by a system while
heat passing to/from the system.
• Consider two cases of same change of a closed
system:
• A. In the first system, only adiabatic work is done
to change the state of the system from 𝑖 to 𝑓 in
order to obtain 𝑈𝑓 − 𝑈𝑖 .
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 Work and Heat
• B. In the second case, we cause the system to
undergo the same change of state, so we have
the same 𝑈𝑓 − 𝑈𝑖 , but the process is diathermic.
• We measure the diathermic work 𝑊 done.
• The result of all such experiments is that the
nonadiabatic work 𝑊 is not equal to 𝑈𝑓 − 𝑈𝑖 .
• In order that this result shall be consistent with
the law of the conservation of energy, we are
forced to conclude that energy has been
transferred by means other than the
performance of work.
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 Work and Heat
• This energy, whose transfer between the system and its
surroundings is required by the law of the conservation
of energy and which has taken place only by virtue of
the temperature difference between the system and its
surroundings, is called heat.
When a system whose surroundings are at a different
temperatures and on which diathermic work may be done
undergoes a process, then the energy transferred by non-
mechanical means, equal to the difference between the
change of internal energy and the diathermic work, is
called heat.

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 Work and Heat
• Mathematically, we define heat transferred as:
𝑄 = 𝑊(adiabatic) − 𝑊(diathermic)
⇒ 𝑄 = 𝑈𝑓 − 𝑈𝑖 − 𝑊(diathermic)
Or, 𝑈𝑓 − 𝑈𝑖 = 𝑄 + 𝑊
• Here, 𝑄 is the heat entering the system and 𝑊 is
the diathermic work done on the system.
• This is called the mathematical formulation of the
first law of thermodynamics. Recall our previous
notation:
Δ𝐸𝑖𝑛𝑡 = 𝑄𝑖𝑛 + 𝑊𝑜𝑛
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 Work and Heat
• Concepts from the First Law of
Thermodynamics:
• The mathematical formulation of the first law
contains three related ideas:
• (1) the existence of an internal-energy
function;
• (2) the principle of the conservation of energy;
• (3) the definition of heat as energy in transit
by virtue of a temperature difference.
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 Work and Heat
• Amount of Heat Transferred:
• Heating is a process by which there is an exchange of
energy between a system and its surroundings because
of a difference in temperature.
• But what is the amount of heat energy that is
exchanged?
• The question cannot be answered until the conditions
for the process of heating are determined.
• Consider a hydrostatic system and the following two
cases:

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 Work and Heat
• Case-A: The diathermic boundary of a hydrostatic
system is held rigid, then the volume of the
system does not change.
• Then the isochoric heat transferred is simply the
internal energy (work done is zero).
• Case-B: If the diathermic boundary of a
hydrostatic system is movable (a piston), and the
pressure of the system does not change.
• The isobaric heat transferred is known as the
enthalpy, which is another type of energy.
Prove that the isobaric heat transfer is equal to change of enthalpy H where H=U+PV.
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Sol: In isobaric case: dP=0, dH=dU+PdV+VdP=dU+PdV=(dQ-PdV)+PdV=dQ in isobaric case.
 Work and Heat
• Concept of Heat: Heat is either internal energy or
enthalpy in transit, depending on the
experimental conditions.
• During the process of heating, energy flows from
one part of a system to another, or from one
system to another, by virtue of only a
temperature difference.
• When the flow has ceased, there is no longer any
occasion to use the word heat or the symbol 𝑄,
because the process has completed/ended.
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 Work and Heat
• All that remains after heating has been
completed is a different state of the system, that
is, a new value for the internal energy or
enthalpy.
• Consequently, it is incorrect to refer to the "heat
in a body," just as it is incorrect to speak of the
"work in a body."
• The processes of working and heating are
transient activities that lead to a change of the
energy found in a system.
• All that endures is the new value of the energy.
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 Work and Heat
• The energy of a system cannot be separated into
a mechanical part and a thermal part.
• This is analogous to water in a lake as originating
from a river, and other water from rain. The river
and the rain lose their relevance/meanings, but
the new water level endures.
• The work done on or by a system is not a function
of the coordinates of the system, so the
calculation of the work depends on the path of
integration by which the system is brought from
the initial to the final state.

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 Work and Heat
• The same situation applies to the heat
transferred in or out of a system.
• Heat 𝑄 is not a function of the thermodynamic
coordinates, that is, not a state function.
• So the calculation of the heat depends on the
path of integration.
• An infinitesimal amount of heat 𝑑𝑄, therefore, is
an inexact differential and not the differential of
an actual function of the thermodynamic
coordinates.
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 Work and Heat
• Equations of a Hydrostatic System:
• From the infinitesimal form of the first law:
𝑑𝑈 = 𝑑𝑄𝑖𝑛 + 𝑑𝑊𝑜𝑛 = 𝑑𝑄 + 𝑑𝑊
⇒ 𝑑𝑄 = 𝑑𝑈 − 𝑑𝑊 = 𝑑𝑈 + 𝑃𝑑𝑉
• Here, 𝑈 is a function of any two of 𝑃, 𝑉 and 𝑇.
• Using 𝑈 = 𝑈(𝑇, 𝑉) we get
𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑈 𝑇, 𝑉 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
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 Work and Heat
• Thus from the first law:
𝜕𝑈 𝜕𝑈
𝑑𝑄 = 𝑑𝑇 + + 𝑃 𝑑𝑉
𝜕𝑇 𝑉 𝜕𝑉 𝑇
• Dividing by 𝑑𝑇, we get
𝑑𝑄 𝜕𝑈 𝜕𝑈 𝑑𝑉
= + +𝑃
𝑑𝑇 𝜕𝑇 𝑉 𝜕𝑉 𝑇 𝑑𝑇
• This equation is true for any process involving any
temperature change 𝑑𝑇 and any volume change
𝑑𝑉.
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 Work and Heat
• Case-A: If 𝑉 is constant, then 𝑑𝑉 = 0, then
𝑑𝑄 𝜕𝑈
= = 𝐶𝑉
𝑑𝑇 𝑉 𝜕𝑇 𝑉
where 𝐶𝑉 is the heat capacity at constant volume.
• Case-B: If 𝑃 is constant, then
𝑑𝑄 𝜕𝑈 𝜕𝑈 𝜕𝑉
= + +𝑃
𝑑𝑇 𝑃 𝜕𝑇 𝑉 𝜕𝑉 𝑇 𝜕𝑇 𝑃

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 Work and Heat
• But from definition, 𝐶𝑃 = 𝑑𝑄/𝑑𝑇 𝑃 and we
1 𝜕𝑉
got 𝜕𝑉/𝜕𝑇 𝑃 = 𝑉𝛽, where 𝛽 = .
𝑉 𝜕𝑇 𝑃
𝜕𝑈
𝐶𝑃 = 𝐶𝑉 + + 𝑃 𝛽𝑉
𝜕𝑉 𝑇
𝜕𝑈 𝐶𝑃 −𝐶𝑉
Or, = −𝑃
𝜕𝑉 𝑇 𝑉𝛽

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