THERMODYNAMICAL SYSTEM Internal energy of a real gas is sum of internal

Thermodynamical system is an assembly of an kinetic energy and internal potential energy of the
extremely large number of particles (atoms or molecules of the gas. Hence it depends on the
molecules). The thermodynamical system may exist temperature as well as volume of the gas.
in the form of a solid, a liquid or a gas or a Important points regarding internal energy
combination of two or more states. (a)The internal energy of a thermodynamic system
THERMAL EQUILIBRIUM AND (such as a gas) depends on its state described by the
TEMPERATURE: ZEROTH LAW OF specified values of pressure, volume and
THERMODYNAMICS: temperature.
Zeroth law: According to it, If systems A and B (b) The change in the internal energy for two given
are each in thermal equilibrium with a third system states of a system depends only upon those states; it
C, then A and B are in thermal equilibrium with does not depend upon the path adopted by the
each other. system between the two states.
It defines temperature as the property of the system (c)The internal energy of a thermodynamic system
which equals that of another system when the two is a characteristic property of the state of the
systems are in thermal equilibrium, e.g., if two system; it does not matter how that state has been
gases in different containers at different obtained. Hence the internal energy is a unique
pressures, temperature and volumes are put in function.
thermal contact for sufficient time to reach thermal (d) The state of pressure, temperature, volume and
equilibrium, their pressures will in general not be hence the internal energy of a thermodynamic
equal, nor will their volumes; their temperatures, system can be changed by mechanical work, by
however, will always be equal in thermal heat-transfer, or by both.
equilibrium. THERMODYNAMIC STATE VARIABLES:
Obviously, if two systems are in thermal Thermodynamic state variables of a system are the
equilibrium, their temperature must be same, and if parameters which describe equilibrium states of the
they are not in thermal equilibrium, their system. For example, pressure, volume,
temperatures must be different. temperature, mass and composition.
TEMPERATURE: Temperature is a physical Internal energy of a system is also a state variable.
quantity, equality of which is the only condition for THE EQUATION OF STATE: The equation of state
represents the connection between the state
thermal equilibrium of two systems or bodies in
variables of a system.
contact.
WORK: Work can be defined as the energy that is
HEAT: It is the energy that is transferred between a transferred from one body to other owing to a
system and its environment because of temperature force that acts between them.
difference between them. Figure shows a gas confined to a cylinder that has a
Heat energy flows from higher temperature to movable piston at one end. If the gas expands
lower temperature. against the piston, it exerts a force through a
SI unit of heat is Joule and CGS is calorie distance 𝑑𝑥 and does the work on the piston. If
[1 calorie = 4.186J = 4.2 J] the piston compresses the gas as it is moved
INTERNAL ENERGY: Internal energy of a system inward, work is also done- in this case on the gas.
is the energy possessed by the system due to The work associated with such volume changes can
molecular motion and molecular configuration. It is be determined as follows.
represented by ‘U’
𝑈 = 𝑈𝑘 + 𝑈𝑝
The energy due to molecular motion is called
internal kinetic energy (𝑈𝑘 ), the motion includes
translational, rotational and vibrational motion. Let the gas pressure on the piston is ‘P’. Then the
The energy due to molecular configuration is called force on the piston due to gas is ‘PA’, where
internal potential energy (𝑈𝑝 ). ‘A’ is the area of the face.
When the piston is pushed outward an infinitesimal
Internal energy of an ideal gas (or perfect gas)
distance 𝑑𝑥, the word done by the gas is
consists only of internal kinetic energy which
⃗⃗⃗⃗⃗ = 𝐹(𝑑𝑥) = 𝑃𝐴𝑑𝑥
𝑑𝑊 = 𝐹⃗ . 𝑑𝑥
depends only on temperature of the gas.
which, since the change in volume of the gas is
𝑑𝑉 = 𝐴𝑑𝑥, becomes 𝑑𝑊 = 𝑃𝑑𝑉
For a finite change in volume from 𝑉1 to 𝑉2, this 𝑑𝑈 = −𝑑𝑊
equation is then integrated between 𝑉1 to 𝑉2 to That is, the internal energy of the system decreases.
find the net work (IV) ISOCHORIC OR ISOVOLUMIC PROCESS:
𝑉2 If a process takes place in a system at a constant
𝑊 = ∫ 𝑑𝑊 = ∫ 𝑃𝑑𝑉 volume(dV=0), then the process is called isochoric
𝑉1
process.
FIRST LAW OF THERMODYNAMICS: dW = PdV = 0
If an amount of heat energy (dQ) is given to a From the first law of thermodynamics
system, a part of it will be used in increasing the 𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
internal energy (dU) of the system and the rest in 𝑑𝑄 = 𝑑𝑈
doing work (dW) by the system on the surrounding Hence, entire heat given to the system is used in
(or environment) increasing the internal energy of the system.
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 (V) ISOBARIC PROCESS: A process taking
The first law of thermodynamics is a form of the place
law of conservation law of energy. At a constant pressure is called an ‘isobaric’
APPLICATIONS OF THE FIRST LAW OF process. For example, when a liquid boils, its
THERMODYNAMICS: pressure and temperature remain constant till whole
(I) CYCLIC PROCESS: When a system after of the liquid is converted in to vapours.
passing through different states returns to its Let V1 = initial volume of the liquid
original state, then it is called a ‘cyclic process’ that V2 = final volume of the vapours
is , in such a process, the system returns to its initial P = constant pressure at which liquid converts in to
state after any number of changes. vapours, then
In cyclic process dU=0, Work done dW = P(dV) = P (V2-V1)
From the first law of thermodynamics If m = mass of the liquid and
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 L = latent heat of vaporisation of liquid then,
𝑑𝑄 = 𝑑𝑊 Heat supplied for converting entire liquid in to
Therefore, net work done during a cyclic process vapours, dQ=mL
exactly equals the amount of heat energy From the first law of thermodynamics
transferred. 𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
(II)ISOTHERMAL PROCESS: In an isothermal 𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊
process, temperature remains constant. If the 𝑑𝑈 = 𝑚𝐿 − 𝑃(𝑉2 − 𝑉1 )
system is an ideal gas, there will be no change in its This is the change in internal energy of the liquid
internal energy, dU=0 on vaporisation.
From the first law of thermodynamics (VI) BOILING PROCESS: In boiling, a liquid is
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 changed into vapours at constant temperature and
𝑑𝑄 = 𝑑𝑊 pressure.
Hence for an isothermal process in an ideal gas, the Let m =mass of the liquid at its boiling point,
heat absorbed by the gas is entirely used in the V1 = initial volume of the liquid,
work done by the gas against the external P = constant pressure at which boiling process
surrounding. occurs,
(III) ADIABATIC PROCESS: The process during V2 = final volume of the same liquid in the vapour
which no heat exchange(dQ=0) between the system form under the same constant pressure,
and the surrounding for the entire process is called L = latent heat of vaporisation of the liquid
adiabatic process. Therefore work done in expansion
From the first law of thermodynamics dW = P(dV) = P (V2-V1)
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 Heat absorbed by the liquid in the boiling process is
0 = 𝑑𝑈 + 𝑑𝑊 dQ=mL
𝑑𝑈 = −𝑑𝑊 From the first law of thermodynamics
Hence, if work is done on the system 𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
𝑑𝑈 = −(−𝑑𝑊) 𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊
𝑑𝑈 = 𝑑𝑊 𝑑𝑈 = 𝑚𝐿 − 𝑃(𝑉2 − 𝑉1 )
That is, the internal energy of the system increases. (VII) MELTING PROCESS: The melting process
If work is done by the system, then of a solid occurs at constant temperature.
𝑑𝑈 = −(+𝑑𝑊) Let m =mass of the liquid;
L = latent heat of the solid
Heat absorbed by the solid during the melting (As the rise in temperature in both the cases is
process is same)
dQ=mL Therefore, Cp dT = CV dT + PdV
In melting process the change in the volume (dV) is
∴ (Cp - Cv) dT = PdV ..............(2)
very small and can be neglected dV≈ 0
Therefore, dW = P(dV) = P× 0 = 0 (vi) For one mole of gas,
From the first law of thermodynamics
PV = RT
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
𝑚𝐿 = 𝑑𝑈 + 0 ∴ P dV = R dT, (since pressure is constant.)
𝑑𝑈 = 𝑚𝐿
Substituting in the equation (2),
Hence, the internal energy during the melting
process increases by mL. (Cp - Cv) dT = R dT
(VIII) RELATION BETWEEN TWO PRINCIPAL
∴ Cp - Cv = R Mayer’s Formula
SPECIFIC HEATS OF A GAS (MAYER’S
WORK DONE IN AN ISOTHERMAL
FORMULA ): (i) Consider one mole of an ideal
EXPANSION: Let us consider 1 mole of gas is
gas that is enclosed in a cylinder by a light,
enclosed in an isothermal container. Let P1, V1 and
frictionless airtight piston.
T be the initial pressure, initial volume, and
(ii) Let P, V, and T be the pressure, volume, and
temperature. As work is done, let the gas expand
temperature respectively of the gas.
to P2, V2 where P2 is the reduced pressure and V2 is
(iii) If the gas is heated so that its temperature rises
the expanded volume. Since the process is an
by dT, but the volume remains constant, then the
Isothermal Process, the temperature remains
amount of heat supplied to the gas (dQ) is used to
constant. We know that work done is given by,
increase the internal energy of the gas (dU).
dW = PdV
Since the volume of the gas is constant, no work is
Total work done by the gas in expansion from
done in moving the piston.
initial volume V1 to final volume V2 is
∴ dQ = dU = CV dT ..............(1) 𝑉2

where CV is the molar specific heat of the gas at 𝑊 = ∫ 𝑃𝑑𝑉

𝑉1
constant volume. From perfect gas equation for one mole
(iv) If the gas is heated to the same temperature PV = RT or P = RT/V
(dT), at constant pressure, the volume of the gas 𝑉2
𝑅𝑇
increases by an amount say dV. 𝑊=∫ 𝑑𝑉
𝑉1 𝑉
The amount of heat supplied to the gas is used to 𝑉2
1
increase the internal energy of the gas as well as to 𝑊 = 𝑅𝑇 ∫ 𝑑𝑉
𝑉1 𝑉
move the piston to allow expansion of gas. The 𝑉
𝑊 = 𝑅𝑇[log 𝑒 𝑉]𝑉21
work is done to move the piston
𝑊 = 𝑅𝑇[log 𝑒 𝑉2 − log 𝑒 𝑉1 ]
dW = PdV.
𝑉2
∴ dQ′ = dU′ + dW′ 𝑊 = 𝑅𝑇 [log 𝑒 ]
𝑉1
Cp dT = dU′ + PdV 𝑉
𝑊 = 2.3026𝑅𝑇 [log10 𝑉2 ]------------(1)
Where CP is the molar specific heat of the gas at 1

𝑉2 𝑃1
constant pressure. 𝑃1 𝑉1 = 𝑃2 𝑉2 ⇒ =
𝑉1 𝑃2
dU′ = 𝑑𝑈 = CV dT
 𝑃1 1
𝑊 = 2.3026𝑅𝑇 [log10 ] − − − − − (2) 𝑊= [𝑃 𝑉 − 𝑃1 𝑉1 ]
𝑃2 (1 − 𝛾) 2 2
WORK DONE IN AN ADIABATIC EXPANSION: From the perfect gas equation
Let us consider 1 mole of gas is enclosed in an 𝑃1 𝑉1 = 𝑅𝑇1 and 𝑃2 𝑉2 = 𝑅𝑇2
adiabatic (that is a cylinder with perfectly non 1
𝑊= [𝑅𝑇2 − 𝑅𝑇1 ]
conducting walls) container. Let P1, V1 and T1 be (1 − 𝛾)

the initial pressure, volume, and temperature of the 𝑅(𝑇2 − 𝑇1 )

𝑊=
(1 − 𝛾)
gas and as work is done, let the gas expand to V2 at
SECOND LAW OF THERMODYNAMICS:
pressure P2 and temperature T2 be the final volume,
KELVIN-PLANCK STATEMENT: It is impossible
pressure, and temperature respectively. We know
to convert ‘all’ the heat extracted from a hot body in
that work done is given by,
to work.
dW = PdV
CLAUSIUS STATEMENT: It is impossible to
Total work done by the gas in expansion from
transfer heat from a cold body to a hot body
initial volume V1 to final volume V2 is
𝑉2
without expenditure of work by an external energy
𝑊 = ∫ 𝑃𝑑𝑉 source.
𝑉1
REVERSIBLE PROCESS: A reversible process is
The equation of adiabatic process is given by,
one which can be reversed in such a way that all
𝑃𝑉 𝛾 = 𝐾
𝐶𝑝
changes taking place in the direct process are
Where, 𝛾 = 𝐶𝑣 exactly repeated in the inverse order and opposite
𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑎 𝑔𝑎𝑠 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 sense, and no changes are left in the system taking
=
𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑎 𝑔𝑎𝑠 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
part in the process or in the universe.
𝐾
𝑃 = 𝛾 = 𝐾𝑉 −𝛾 A process is said to be reversible, if, it is:
𝑉
𝑉2 (i) quasi-static
𝐾
𝑊=∫ 𝛾
𝑑𝑉 (ii) Non-dissipative
𝑉1 𝑉
𝑉2 (i) Quasi static:
−𝛾
𝑊 = ∫ 𝐾𝑉 𝑑𝑉 (i) If the process is carried out very slowly then
𝑉1
𝑉2 system will be in almost thermodynamic
𝑉 (1−𝛾)
𝑊 = 𝐾[ ] equilibrium and this process is called quasi-static
1−𝛾 𝑉
1
process.
𝐾 1−𝛾 1−𝛾
𝑊= [𝑉2 − 𝑉1 ] (ii) Non-dissipative: If no heat dissipation takes
1−𝛾
1 place during the process then it is called non-
1−𝛾 1−𝛾
𝑊= [𝐾𝑉2 − 𝐾𝑉1 ]
1−𝛾 dissipative.
From the equation of adiabatic process These conditions are never realised in practice.
𝛾 𝛾
𝑃2 𝑉2 = 𝑃1 𝑉1 = 𝐾 Hence, a reversible process is only an ideal
1 𝛾 1−𝛾 𝛾 1−𝛾 conception and no process in nature is truly
𝑊= [𝑃2 𝑉2 𝑉2 − 𝑃1 𝑉1 𝑉1 ]
1−𝛾 reversible. For example, slow expansion and
For example, INDICATOR DIAGRAM OR P-V DIAGRAM:
(i)slow expansion and compression of an ideal gas This diagram represents the variation of volume V
in a cylinder fitted with frictionless piston, of a system with the pressure P of the system.
(ii) slow expansion and compression of a spring, Usually, volume V is plotted on the X- axis and
(iii) electrolysis if the resistance offered by the pressure along the Y- axis.
electrolyte is zero.
IRREVERSIBLE PROCESS: A process, which
does not satisfy even one of the conditions for
reversible process is called an irreversible process.
All natural processes are irreversible processes, for
example, heat conduction, ordinary expansion of a
gas, diffusion of gases, radiation, radioactive decay,
stopping of a moving body through friction etc.
Thus, irreversibility is a rule.
LIMITATIONS OF THE FIRST LAW OF
THERMODYNAMICS:
(i) The first law does not indicate the direction in
which the change can occur.
(ii) The first law gives no idea about the extent of
change.
(iii) The first law gives no information about the
source of heat that is whether it is a hot or a cold
body.
SIGN CONVENTIONS:
(i) When heat is supplied to a system, dQ is taken
as positive.
(ii) When heat is drawn from the system, dQ is
taken as negative.
(iii)When a gas expands, work is done by the gas,
dW is taken as positive.
(iv) When a gas compressed, work is done on the
gas, dW is taken as negative.
(v) When temperature of a gas increases, its internal
energy increases, dU is taken as positive.
(vi) When temperature of a gas decreases, its
internal energy decreases, dU is taken as negative.
Work done in each case = area under the P-V curve