Constant Volume (Isochoric) Process
◼ This process is also termed as isovolumetric
process during which volume of the system
remains constant. The term ‘isochoric’ has been
derived from Greek word in which ‘iso’ means
equal and ‘chor’ means place. If there is no
change in volume of the system, then the
change in other thermodynamic parameters can
be calculated with the help of first law of
thermodynamics.
◼ For example, a gas is heated in a rigid vessel.
Then pressure and temperature of the gas will
increase, but there will be no change in
volume.
Continued…
◼ From first law of thermodynamics, we have
◼ dQ = dU + dW = dU + PdV -------------(1)
◼ At constant volume i.e., volume (V) = const
◼ dV = 0
◼ Putting the condition in equation (1), we have
◼ dQ = dU
◼ For ‘n’ mole of gas, dQ = ndU
◼ Hence, the heat absorbed by the system at
constant volume goes completely to increase
the internal energy of the system.
Constant Pressure (Isobaric) Process
It is thermodynamic process in which the pressure of
the gas remains constant i.e., P = constant or dP = 0.
Now, in this process, the change in enthalpy
can be calculated by the following way.
Considering the system under two different
states,
◼ At the initial state, H1 = U1 + PV1 1
◼ At the final state, H 2 = U 2 + PV
2 2
Continued…
◼ Hence, change in enthalpy
◼ H = H2 − H1 = (U 2 + PV
2 2 ) − (U1 + PV
1 1)
= (U 2 − U1 ) − ( PV 1 1)
2 2 − PV
◼ = U + PV ------------(A)
◼ Since, the term enthalpy is conveniently used to
express the process under constant pressure, then the
above equation can be written as
◼ H = U + PV
= U + W = Q
◼ Hence, the enthalpy-change of a system is equal to
change in heat absorbed at constant pressure
Constant-Temperature (Isothermal) Process
In the constant temperature or isothermal process
the temperature of the system remains constant i.e.,
a temperature constancy is maintained
throughout the operation.
If the gas is allowed to expand at constant
temperature, the pressure will decrease during
expansion. Hence, if an ideal gas undergoes an
expansion at constant temperature, the expansion
process is termed as isothermal expansion, and it
will be accompanied by no change in internal
energy.
Continued….
◼ Work done, internal energy, heat interaction can be
calculated from the knowledge of first law of
thermodynamics.
◼ From the first law of thermodynamics, we have
◼ dQ = dU + dW
dQ = CV dT + PdV
◼ At constant temperature i.e., temperature (T) = const
◼ dT = 0
◼ Then, on substituting the condition, we get
dQ = dW = PdV
Continued……
Therefore, 2 2
dv v2
Q = W = Pdv = RT = RT ln
1 1
v v1
For ‘n’ moles of an ideal gas,
v2 p1
Q = W = nRT ln = nRT ln
v1 p2
Hence, the character of an isothermal process for an
ideal gas can be summarized as follows-
◼ Change in internal energy, ∆U = 0
◼ Change in enthalpy, ∆H = 0 and
◼ v2 p1
Q = W = nRT ln = nRT ln
v1 p2
Assignment:
◼ 1 kg of air at 50 0C expands reversibly and
adiabatically to 5 times its original volume. Initial
pressure of the air mass was 8 atms. Determine
the final pressure, temperature, work done when
the expansion is
i) adiabatic and
ii) isothermal.
Given the heat capacity ratio = γ = 1.4
PROBLEM
◼ 5 kg of air is heated from an initial state of 370C
and 101.33 kPa until its temperature reaches 237
C. Calculate ∆U, Q, W, and ∆H for the
following processes-
◼ i) isochoric process
◼ ii) isobaric process
◼ Air is assumed to be an ideal gas. Given, CP
= 29.10 J/mole-K and CV = 20.78 J/mole-K
◼ Molecular weight of air = 29
solution
◼ Since air is assumed to behave ideally, then it
obeys the ideal gas law PV = nRT and number of
moles of air can be calculated by this relation
m
◼ PV= nRT = RT
M
◼ Where, m = mass of the gas and
◼ M = Molecular weight
m 5
◼ Number of moles = n = = = 0.1724 kmol
M 29
nR1T1 0.1724 x8.314 x310
◼ Volume of air at initial state, V1 = =
P1 101.33
◼ = 4.385 m3
8/12/2024 Dr. G. N. Halder- NIT Durgapur 10
Continued…
◼ a) Isochoric Process:
◼ The process is an isochoric one i.e., volume,
V = constant
◼ V1 = V2 = 4.385 m3 and
◼ T2 = 237 C = 510 K
◼ i) ∆U, Change in internal energy
◼ ∆U = nCV (T2 − T1 )
◼ = 0.1724 x 20.785 x (510-310)
◼ = 716.66 kJ
Continued…
◼ ii) Q, Heat Supplied
◼ Q = U + W = U + PdV
◼ Since, V = constant then
◼ Q = U = 716.66 kJ
◼ iii) W, Work-done
◼ W = Q − U = 0
◼ iv) ∆H, Change in enthalpy
◼
H = U + ( PV ) = U + V P = U + V ( P2 − P1 )
◼
◼ = 1003.36 kJ [Find P2 ]
Continued….
◼ b) Isobaric Process:
◼ The process is a constant pressure
process, so P = Constant
◼ P1 = P2 = 101.33 kPa, T2 = 510 K
◼ i) ∆H, Change in enthalpy
◼ = nCP ( − T1 )
◼ = 0.1724 x 29.10 x (510-310)
=1003.36 kJ
◼ ii) Q, Heat Supplied at constant P
◼ QP = H P = 1003.36 kJ
Continued……..
◼ iii) ∆U, Change in internal energy
◼ U = H − PV = H − nR
= 1003.36 - 0.1724 x 8.314 (510-310)
◼ = 716.69 kJ
◼ iv) W, Work-done
◼ W = Q − U
◼ = 1003.36 - 716.69 = 286.67 kJ
Assignment:
◼ One mole of an ideal gas is used as a working
substance in a Carnot cycle operates initially at
610 K and 106 N/m2 in compression stage. The gas
then expands isothermally to a pressure of 105
N/m2 and adiabatically at 310 K. Determine, ∆E,
Q and W for each step and net work done and
efficiency of the cycle.
◼ Given, Heat capacity of gas at constant volume,
CV = 20.78 J/mol-K
PROBLEM:
◼ In a frictionless, piston-cylinder arrangement, an
ideal gas undergoes a compression process from
an initial state of 1 bar at 298.15 K to 5 bar at
298.15 K. The entire process comprises of the
following two mechanically reversible processes:
◼ a) cooling at constant pressure followed by
heating at constant volume
◼ b) heating at constant volume followed by
cooling at constant pressure.
◼ Calculate Q, W, ∆U and ∆H for the two
processes. Given, CP = 29.10 J/mol-K , CV = 20.78
J/mol-K and volume of the gas at initial state
0.02479 m3/mol.
Temperature Variation in the
Entire Process:
First Process: ◼ Second Process:
Cooling at const P Heating at constant V
followed by heating at followed by Cooling at
constant V const P
First step: First step:
T1= 298.15K T2= 59.63K T1= 298.15K T2= 1490.75K
Second step: Second step:
T1= 59.63K T2= 298.15K T1= 1490.75K T2= 298.15K
Solution:
◼ Basis: 1 mol of ideal gas
Initial state: P1 = 1 bar, T1 = 298.15K, V1 =
0.02479 m3/mol
◼ Final state: P2 = 5 bar, T2 = 298.15 K, V2 = ?
◼ The final volume of the gas can be calculated
as
PV 1 0.02479
V2 = 1 1
= = 0.004958m3
P2 5
◼ a) In the first step of the first process, the
cooling of gas takes place at constant pressure
process in which the volume is reduced
appreciably and consequently the temperature
decreases as, say T′.
Continued….
TV 298.15 0.004958
T = 1 2
= = 59.63K
V1 0.02479
◼ i) QP, Heat requirement:
Since, the process is a constant pressure process,
then
QP = H P = CP T = CP (T2 − T1 )
= 29.10 (59.63-298.15) = -6941 J
ii) ∆UP, change in internal energy:
U = H − ( PV ) = H − PV = H − P (V2 − V1 )
= -6941-(1x105)(0.004958-0.02479) = -4958 J
Continued..
◼ In the second step, the gas is heated at
constant volume i.e., V = constant
dV = 0
◼ Then from first law of thermodynamics, we
have
◼
dQ = dU
◼ i) QV, Heat requirement:
◼ = 20.78 (298.15-59.63) = 4958 J
◼ ii) ∆UV, change in internal energy:
◼ ∆UV = 4958 J
Continued..
◼ Since the process comprises two steps,
therefore actual Q and ∆H can be
obtained by summing up of respective
values for 2 different steps.
Q = QP + QV = -6941+4958 = -1983 J
∆U = -4958 J + 4958 J = 0
∆W, Work done:
From first law, W = Q - ∆U = -1983 - 0
W = -1983 J
Continued….
◼ b) In the first step of 2nd process, gas is
heated at constant volume i.e., V = const or
dV = 0
◼ The temperature of the air, say T′, at the
end of the first step can be calculated as
◼ T1 P2 298.15 5
T = = = 1490.75 K
P1 1
◼ i) QV, Heat requirement:
◼ = 20.78 (1490.75-298.15) = 24,788 J
Continued…….
◼ ii) ∆UV, change in internal energy:
◼ ∆UV = 24,788 J
◼ In the 2nd step, gas is cooled at constant
pressure of 10 bars.
◼ i) QP, Heat requirement:
QP = H P = CP T = CP (T2 − T1 )
◼ = 29.10 (298.15-1490.75) = -34703 J
◼ ii) ∆UP, change in internal energy
U = H − ( PV ) = H − PV = H − P (V2 − V1 )
= -34703 – 5x105 (0.004958-0.02479) = -24788 J
Continued…….
◼ For the two steps, the above quantities are
to be summed-up
◼ Q = QP + QV
◼ = 24788-34703= -9915J
◼ ∆U = 24788 -24788 = 0 J
◼ ∆W, Work-done:
◼ Work done = Q – ∆U
◼ = (-9915) – 0 = -9915 J
Problem:
A spherical balloon of 1m diameter contains
a gas at 120 kPa. The gas inside the balloon is
heated until the pressure reaches 360 kPa.
During heating the pressure of the gas inside
the balloon is proportional to the cube of the
diameter of the balloon. Determine the work
done by the gas inside the balloon.
Solution
◼ The pressure (P) of the gas inside the balloon
is proportional to the cube of the diameter of
the balloon, i.e., P = kD3
Where, k = proportionality constant
◼ Now, work-done by the gas inside the
balloon can be estimated as
3 4 3
W = PdV = kD .d r
3
3 4 D3
= kD .d
3 8
Continued……
◼ Then k
D2
=
2
D1
D 5 dD
k
= D2 − D1
6 6
12
◼ Given,
P1 = kD1
3
P1 120 103
◼ or, k= 3 = = 120 103
D1 1
◼ Now, we can calculate the final pressure
◼ P2 = kD23
3
◼ or, 360 x 103 = 120 x 103 D
x 2
Solution:
◼ D2 = 1.442 m
◼ = Diameter of the balloon at the final
pressure
◼ Hence, work-done by the gas would be
◼ 120 10 3
W= 1.442 − 1
6
6 2
◼ = 251013.25J = 251.01 kJ
Do it now:
A spherical balloon having a diameter of
0.25 m and containing CO2 at a pressure
of 150 kPa is heated so that its diameter
becomes 0.4 m. During the process the
pressure is proportional to diameter.
Calculate the work done by carbon
dioxide during the process.
Ans: 5.111kJ
Mass Balance for Open System:
In order to prepare a mass balance for an open
system, the region in the figure is identified for
the analysis of mass interaction only. The first
law of thermodynamics can be applied to
establish a mathematical expression on mass
balance.
Continued…
◼ It is very much clear from the figure that the two
fluid input streams m1 and m2 enter the control
volume and one fluid output stream m3 leaves the
control volume.
◼ The mass balance equation can be represented as
Rate of input- Rate of output = Rate of accumulation
◼ It can be mathematically expressed as
dmCV
m 1 + m 2 − m3 =
dt
dmCV
+ m3 − m 1 − m 2 = 0
dt
Continued…
◼ Then
dmCV
+ m 3 − m1 + m 2 = 0
dt
dmCV
+ m out − min = 0
dt
◼ In case of consideration of number of inlets and
outlets, summation signs are used.
◼ Then above equation can be expressed as
dmCV
+ m out − m in = 0
dt
Energy Balance for Open System
Consider the fluid stream is flowing into and out
of the control volume shown in the figure. The
total energy associated with transferring of fluid
mass, comprises of internal energy (U), kinetic energy
and potential energy.
◼ Hence, the total energy transported by each stream
= U + 1 u 2 + Zg
2
◼ Where, U = internal energy,
◼ u = average velocity of the stream
◼ Z = elevation of the flowing masses
◼ g = acceleration due to gravity
Energy Balance of Open System
Continued….
So, the rate of energy transport
= m U + 1 u 2 + Zg
2
It is necessary to consider the flow energy (PV) of
the fluid entering or leaving a control volume. This
additional form of energy is required to push the
fluid mass into or out of the control volume.
◼ This flow energy comes from the work done to
flow the fluid. This work is known as ‘Flow work’.
◼ It is clear from the figure that amount of heat is
transferred
Q to the control volume and the work done
by the fluid is W.
Continued…
◼ So the energy stored within the control
volume is given by
dECV 1 2
+ U + u + Zg m = Q − W
dt 2
The flow work done by the control volume
= ( PV )out . m out
The flow work done on the control volume
= ( PV )in . min
Net flow work done by the control volume
= ( PV ) . mout − ( PV ) . min = ( PV ) m
out in
Continued…..
The net work done by the control volume,
W = Shaft work + Flow work
= WS + ( PV ) m
Applying the first law of thermodynamics,
we have
dECV 1 2
+ U + u + Zg m + ( PV ) m = Q− WS
dt 2
dECV 1 2
+ H + u + Zg m = Q− WS
dt 2
Continued………..
◼ In most of the cases, the kinetic and potential
energy are negligible, then the equation becomes
dECV
+ ( H ) m = Q − WS
dt
dECV
◼ At steady state condition, = 0 , then the
dt
◼ above expression becomes
◼ Q WS
H = −
m m
H = Q − WS
