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Various Processes
(1) Constant Pressure ( isobaric / isopiestic Process)

(2) Constant Volume ( isochoric / isometric


process)

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(3) Constant Temperature ( isothermal process)


PV = constant

OR

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(4) Polytrophic Process (P Vn = c (constant )


or P = c V-n)
2 2 2
n V2 n 1 V1 n 1
1W2 W PdV cV dV c
1 1 1
n 1

P2V2 P1V1
2

PdV
1
1 n

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n = (constant V)

n=0 (constant P)

n=1 ( constant T)
n= 2,3,... ( polytrophic
Process)
n = ( Adiabatic
Process)

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Ideal-gas Equation
Of State

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Any equation that relates Pressure, Temperature


and Specific volume of a substance is called an
equation of state.

Property relations that involve other properties


of a substance at equilibrium states are also
referred to as equations of state.

The simplest and best- known equation of state


for substances in the gas phase is the ideal-gas
equation of state.
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In 1802, J. Charles and J. Gay-Lussac, experimentally


determined that at low pressures the volume of
the gas is proportional to its temperature.
That is

Or
ideal-gas
equation of state.

Where the constant of Proportionality R is called


the gas constant.
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And the gas which obeys this relation is called


ideal gas.
P = absolute pressure.
T = absolute Temperature.
v = specific volume.
The gas constant R is different for each gas and is
determined from:

Ru is universal gas constant and M is molar mass


of a gas. 17

The constant Ru is the same for all substances and its


values is :

Value units

8.31447 kJ/kmol .K
8.31447 kPa.m3/ kmol .K
Ru
0.0831447 bar. m3/ kmol .K
1.98588 Btu / lbmol. R
10.7316 psia.ft3 / lbmol. R

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Now, mass of a system is equal to the product of its


molar mass & mole number N.
m = M x N ( in kg)

Now ideal gas equation can be written in several


different forms.

where is molar specific volume (vol. per unit mole)


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James Prescott Joule (1840's)


Heat and mechanical Work are simply two
different forms of energy; & all the energy
that goes into a system comes out in some
other form; and energy does not vanish
and has the ability to be converted into any
of its other form.
This statement is an expression of what is
known as the First Law of
Thermodynamics.

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Joules Paddle Wheel Experiment


Using this apparatus, Joule confirmed the
equivalence between heat and mechanical work.
Consider a closed system with insulation on the
walls.
Water is filled with temp T1 as that of the
surroundings, which is measured with
thermometer.

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Thermometer Paddle wheel

Pulley

impellers weights

Water at
Temperature T1.

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Now work is done on the system by the paddle


wheel. This work can be measured by falling a
known quantity of weights from height z1 to
z2.
When the weights go down, the impellers in a
water tank rotate to stir the water. The
potential energy of the weights is converted
into the kinetic energy of the rotation of the
impeller, and the temperature of the water
rises to T2.
Therefore, work done on the system is
calculated as W12.

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Now, Remove the insulation.


System & surroundings will interact by heat
transfer till the system returns to the original
temperature T1.
Amount of heat transfer from the system is Q21.
Hence system executes a cycle, which consist of,
definite amount of work input (W12) to the
system followed by heat transfer from the system
(Q21). W 12
2

Q21
1

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Work was measured in mechanical units.


Heat was measured in thermal units.
For a wide variety of systems, and for
various amounts of work and heat,
measurements of heat and work were
done experimentally.
When the amounts of heat and work were
compared, it was found that they were
always proportional.

J as,
These results can be put Q W
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is the symbol for cyclic integral of heat
Q
transfer.

is the symbol for cyclic integral of work


W transfer.
J as a proportionality factor.
In S.I units, both heat and work are measured
in Joules and hence J = 1.

Q W
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Cyclic Process with Complex Path.


Algebraic sum of work transfer is = Algebraic
sum of heat transfer.

Q W

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The First Law of Thermodynamics


for a Change in State of a Closed
System.
Consider a system that undergoes a cycle in
which it changes from state 1 to state 2 by
process a and returns from state 2 to state
1 by process b.

From the first law, we have,

Q W 29

Breaking it into two separate processes we


have,
2 1 2 1

Q
1
a Qb Wa Wb
2 1 2
Now, consider another
cycle in which the closed
system changes from
state 1 to state 2 by
process c and then
returns to state 1 by
process b.

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For this cycle,


2 1 2 1

Q
1
c Qb Wc Wb
2 1 2

Subtracting this equation from the previous one, we


get 2 1 2 1

Q1
a Q
2
c W
1
a W
2
c

2 2

(Q W ) (Q W )
1
a
1
c

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From the above result, we conclude that,


The quantity (Q W ) is constant for all
processes between state 1 and state 2.

Which means that (Q W ) depends only on


initial and final states and NOT on the path followed
between the two states.

This means that, (Q W ) is a point function.


This property was termed as energy of closed
system, E.
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dE (Q W )
Integrating the above equation from state 1 to
state 2,
E2 E1 1Q2 1W2
Here, E1 and E2 are the initial and final values of
the energy of the closed system,
is the heat transferred to the closed system
Q
1 2 during the process, and

1W2 is the work done by the closed system


during the process.
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Property E represents all the energy of the


system in the given state.
In the study of thermodynamics, we consider
energy of a system as consisting of three
distinct components:
E = Internal energy + kinetic energy + potential
energy
E = U + KE + PE
The internal energy U includes all other forms
of energy of the closed system. It is
associated with the thermodynamic state of
the system.
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E = U + KE + PE
All the terms in above equation are point
functions, so
dE = dU + d(KE) + d(PE)
Now, we can write the first law of
thermodynamics for a change of state as,
dE = dU + d(KE) + d(PE) = Q W.
In the absence of motion & elevation
dE = dU = Q W

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As a closed system undergoes a


change of state, energy may cross
the boundary as either heat or
work. The net change in the energy
of the system will be exactly equal
to the net energy that crosses the
system boundary.

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Enthalpy
Consider a closed system undergoing a
quasi-equilibrium, constant-pressure
process. Assume that theres no
changes in kinetic & in potential
energy, and that the only work done
during the process is associated with
the boundary movement.

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Applying the first law,

1 Q2 U 2 U1 1W2
The work done can be given as 2
W2 PdV
1
1
Since the pressure is constant
2

1W2 P dV P(V2 V1 )
1

1 Q2 U 2 U1 P2V2 P1V1
1 Q2 (U 2 P2V2 ) (U1 P1V1 )

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1 Q2 (U 2 P2V2 ) (U1 P1V1 )


The heat transfer during the process is given
in terms of the change in the quantity (U + PV)
between the initial and final states. So, this
group (U + PV) represents some property of
the substance. We call this property as
Enthalpy, H.
H=U+PV
And h=u+Pv

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Thus, the heat transfer in a constant-


pressure, quasi-equilibrium process is
equal to the change in enthalpy.

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Specific Heat
Specific heat for any substance is
defined as the amount of heat required
per unit mass to raise the temperature
by one degree.
(1)Specific heat at constant volume.
(2) Specific heat at constant pressure.

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Specific Heat at constant Volume (Cv)

Cv =
By 1st law
dU = Q W

For isochoric process undergoing a change in


state from 1 to 2.
Then W = 0 and we have Q = dU.

Therefore (Q)v =
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Specific Heat at constant Pressure (CP)

Enthalpy by definition H=U+PV


Now dH = dU + d(PV) ; dH = dU +PdV +VdP
At constant Pressure , undergoing a change in
state from 1 to 2.
dH = dU +PdV . Comparing with dU = Q W
dH = Q.
On further integration
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So remember
Heat transfer in isochoric process is

(Q)v =

Heat transfer in isobaric process is

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Relationship b/w specific heat and


gas constant.
For ideal gas

Also

On differentiating w.r.t temperature

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where is adiabatic index or adiabatic


exponent.

and

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Free Expansion
Consider a thermally insulated rigid tank, which is
initially divided into two compartments by a
membrane.
One part contains an ideal gas and the other is
completely evacuated.

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Let the gas initially has Pressure P1 and volume V1 .


And after when the membrane is removed, gas will
completely fill the entire compartment and
hence ( we say ) let the Pressure P2 and volume
V2 .
So on PV diagram we have:-
P1,V1

P2,V2

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Now initially, when the gas was having P1 and V1 .


Then we slowly shift the membrane positions.

P1,V1
P1,V1
PA,VA
P
PB,VB
P
P2,V2 PCVC PD,VD
P2,V2
PE,VE
V
V
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So area under the curve will be the work done by


the system ?
Since there is no interaction between the system
and the surroundings or there is no boundary
movement b/w system and surroundings
when gas was expanding so there is NO
WORK.
And such kind of process is known as free
expansion.
Expansion of gas against vacuum is called as free
expansion.
So, in free expansion, No work is done on or by
the system.
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Salient aspects of free expansion.


No work is done on or by the system, as there is
no resistance to overcome.
Since system is insulated, therefore Q is also
zero.
From 1st law, Q = W + dU . Since both work &
heat interactions are zero, dU is also zero, i.e.
there is no change in internal energy of the gas.
for ideal gas, U =f(T)only and
Obviously there is no change in temperature of
the system, i.e. initial temperature is = final
temperature. 51

Further enthalpy, and since there is


no change in temperature, the enthalpy of the
system would also remain same.
Enthalpy is . Since U and H are constant
therefore the product must also remain
constant . As such the values of pressure and
volume change in such a manner that their
product remains constant.

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An ideal gas undergoes an


adiabatic process,
Calculate the amount of
work done by the system.

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By 1st law

Now, Gas equation Pv =RT


On differentiating

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Consider the system as shown in following fig.


Initially the gas is at 200 KPa & occupies a vol of 0.1
m3. Spring exerts a force which is directly
proportional to the displacement from its
equilibrium position. Patm of 100 KPa acts on the
other side of the piston. Gas is heated until the
volume gets doubled and final pressure of 500
Kpa. Calculate the work done by the gas.

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P1 = 200 KPa, V1 = 0.1 m3 ; P2 = 500 KPa, V1 = 0.2 m3


Given is force is directly proportional to
displacement from its equilibrium position.
A is the cross sectional area of the piston.
Apply force balance.

V0 is the volume of the gas when spring is in its natural


length.

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Or

From initial pressure condition


&
Adding equation (2+3) & divide by 2, we have

Now substitute in equation (1), we have


hence ans is 35KJ.
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Numerical
Problems

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Ques 1
It is desired to compress isothermally 1Kmol of NH3
from initial state of 30 m3/Kmol and 300K to the
final state of 5m3/Kmol and 300K. It is known
that NH3 obeys:
and
Where a = 422.55 Pa(m3/Kmol)2;
b = 0.037 m3/Kmol
Cv = 27.24 KJ/Kmol K and R = 8.314 KJ/Kmol K.
Calculate the heat and work interactions.
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Work Interaction W = PdV and


1

W = -4414.03 KJ/Kmol.
Now Heat interaction
Isothermally and integrate to U.
U = -70.425 KJ/Kmol.
By 1st law Q W = U ; Q = -4484.485 KJ/Kmol.
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Ques 2
Consider a gas enclosed in a piston cylinder
arrangement. Gas is initially at P = 500 KPa
and occupies V = 0.2 m3.Gas is taken to final
state of P = 100 KPa. Calculate the work done
by the gas by each case:-

(a) (b) PV1.4 = Constant

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(a) i.e. PV = constant process.

W = 160.94 KJ.

(b) PV1.4 = Constant i.e. any polytrophic process


P2V2 P1V1
2

PdV
1
1 n W = 92.15 KJ.

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Ques 3
A non-flow reversible process occurs for which
P and Volume are correlated as

Where P is in bar and V is in m3.


What is the amount of work done , where
volume changes from 4 m3 to 8 m3.

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Now

2
And W = PdV
1
and integrate

W = 153.5 x 102 KJ.

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Ques 4
1 mol of ideal gas at 0.5 MPa and T = 310 K is
heated at constant P till the volume is doubled
and then allowed to expand at constant
temperature till volume is doubled again.
Make calculations for total work done.
(Take R = 8.314 J/mol K)

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First draw PV diagram. 2


1
P
3

V
Process 1-2 ( constant Pressure)
W1-2 = P( V2-V1) and V2= 2V1 . So W1-2 = RT1.
Process 2-3 ( constant Temperature)
W2-3 =
W2-3 = 2RT1ln2.
Therefore total work = W1-2 + W2-3 = 6150.3 Joule.
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Ques 5
A piston cylinder m/c contains fluid , which passes
thru a complete cycle of 4 different processes.
During the cycle, sum of all heat transfer is -
200KJ. System completes 150 cycles/min.
complete the following table and compute net
rate of work output in KW.
Process Q ( KJ/min) W (KJ/min) E ( KJ/min)

1-2 0 2000 -------

2-3 22000 0 -------

3-4 -2100 ------- -36000

4-1 ------- ------- -------

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Process 1-2: Q = E + W ; E = -2000 KJ/min.


Process 2-3: Q = E + W ; E = 22000 KJ/min.
Process 3-4: Q = E + W ; W = 33900 KJ/min.

Q W
Process 4-1: Q=?; W =?
System completes 150 cycles/m.
Total heat transfer = -200KJ/cycle x 150 cycles/min
= -30,000 KJ/min. ( = total work Transfer)
Q12+Q23+Q34+Q41 = -30,000 KJ/min.
Q41= -49900 KJ/min.
Also in a cycle E = 0, Hence E12+ E23+ E34+ E41=0
E41 = 16000KJ/min. And W41 = -65900KJ/min.
Rate of work output is = -500KW.
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Ques 6
A gas undergoes a thermodynamic cycle consisting of
following processes:-
Process 1-2 :- Constt. P = 1.4 bar, V1= 0.028m3,
W12=10.5KJ.
Process2-3:- Compression with PV = Constt. , U3 = U2.
Process3-1:- Constt. V and U1-U3 = -26.4 KJ.
No significant change in KE and PE.
Sketch Cycle on PV diagram.
Calculate net work for the cycle (in KJ).
Calculate Q12.
Show Q W
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State 1: P1 =140 KPa, V1 = 0.028m3


W12 = 10.5 KJ.( = P1(V2-V1))
State 2: U = 0
State 3: U = -26.4 KJ, constant V
W31 =0 & Q31 = -26.4 KJ.
Also dE 0 (U)12+(U)23+(U)31 =0
(U)12 =26.4 KJ. Also Q12 =W12+ (U)12
Q12 = 36.9 KJ.
And finally W23 = -18.7KJ and Q23 = -18.7 KJ.
Hence Q12+Q23+Q31 = W12+W23+W31 . (=-8.2 KJ)
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