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Chapter#2
Zeroth law,
FirstLawofThermodynamics,
A li ti i l t Applicationinclosesystem
Zeroth lawofthermodynamics
If each of two given systems 1 and 2 are in thermal equilibrium
with a third system 3, then the two systems 1 and 2 are in
thermal equilibrium with each other. q
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Joulespaddlewheelexperiments
Workdoneonsystem(water)byloweringthemass
Temperatureincreaseofwaterafterperformingwork
(Heattransfer?)
Systemrestoredtotheinitialstatewithanotherwaterbath.
Heattransfertowaterbath?
Joule performed many experiments. In some experiments, the
paddle wheel was replaced by an electrical resistor, supplied
with an electric current by using a reversible cell.
Joule found, during a cycle change net work done on the
system was always proportional to net energy removed from system was always proportional to net energy removed from
the system as heat irrespective of the type of work
interaction.
Mathematically,inSIunits, or
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Firstlawofthermodynamics
Whenever the system undergoes a cyclic change, however
complex the cycle may be, the algebraic sum of work transfers is
equal to the algebraic sum of energy transfers as heat.
Consider a reversible cycle,
Applying first law to the cycle,
Subtractingequation(2)fromequation(1),
dQ anddW pathdependent,(dQdW)pathindependent
Define(dQdW)=Energychangeofsystem=dE
Where,E=K.E.+P.E.+U=propertyofsystem
dE =d(K.E.+P.E.+U)=dQ dW
or,dU =dQ dW
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Example:
A fluid system undergoes a non-flow frictionless process
following the pressure-volume relation as p = 5/V + 1.5 where p
is in bar and V is in m
3
. During the process the volume changes
from 0.15 m
3
to 0.05 m
3
and the system rejects 45 kJ of heat.
D t i Ch i i t l Determine : Change in internal energy.
Solution:
Given, V
1
= 0.15 m
3
, V
2
= 0.05 m
3
,Heat rejected Q = 45 kJ
Now work done = PdV = [ (5/V + 1 5)dV ] 10
5
N-m Now, work done = PdV = [ (5/V + 1.5)dV ] 10 N-m
= - 5.64 10
5
N-m = - 564 kJ
Applying the first law energy equation, U = Q W = 519 kJ
Perpetual motion machine of first kind (PMMI)
A cyclically operating device which would produce work
continuously without absorbing energy from surrounding
(Impossible) (Impossible)
From first law for cyclic process,
If then W = 0
Think: Expansion of a high pressure gas in a piston cylinder
assembly to a certain extent, without absorbing any heat
(PMMI?)
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Firstlawanalysisforfewelementaryprocesses
Isochoricprocess
Isobaricprocess p
Isothermalprocess
Adiabaticprocess
Polytropic process
Constantinternalenergyprocess
ConstantVolumeProcess(Isochoric)
ConsideragasconfinedinrigidvesselofvolumeVasthesystem.
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Applying the first law, dU = dQ dW
Here, dW = 0
So dU = dQ or Q = U U So, dU = dQ, or Q = U
2
U
1
heat interaction of system =
Change in the internal energy of the system
Specific heat at constant volume, Specific heat at constant volume,
C
V
= (dq/dT)
V
= (u/T)
V
IfC
V
isconstantthen,
Also,ifC
V
isvarieswithtemperaturethen,
Where,meanspecificheat=
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Example:
An insulated rigid tank initially contains 0.7 kg of
helium at 30C and 364 kPa. A paddle wheel with a
power rating of 0.02 hp is operated within the tank for
30 min Determine: 30 min. Determine:
(a) the final temperature
(b) the final pressure of the helium gas
(Given, C
V
= 3.1156 kJ/kg.C)
Solution:
Consider He gas in tank as closed system
Given, m = 0.7 kg, T
1
= 30C, P
1
= 364 kPa
Here, no work done by system but, work is done onto
system by paddle wheel action.
So, work done in process (amount of paddle wheel
work done on the system) work done on the system),
W = - (power)(time) = - (0.02)(3060) = - 26.9 kJ
System is adiabatic, heat transfer Q = 0
Applying first law,
U = Q W,
U = W
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mC
V
(T
2
T
1
) = W
Put values,
(0.7)(3.1156)( T
2
300) = - (- 26.9)
T
2
= 39.3C Ans T
2
39.3 C Ans
Also, for He (ideal gas), at constant volume,
P
1
/ T
1
= P
2
/T
2
Put values, 364/300 = P
2
/312.3,
P
2
= 378.9 kPa Ans
ConstantPressureProcess(Isobaric)
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Consider heating of a gas at constant pressure and
reversibly.
Work done by system from state 1 to state 2,
2
Applying first law of thermodynamics,
dU = dQ dW
= dQ PdV
2 1
1
( ) W P d V P V V = =

Q
= dQ d(PV)
Or, dQ = dU + d(PV)
dQ = d(U + PV)
Put U + PV = H, So, dQ = dH, Q = H
2
H
1
Heat transfer at constant P = Total enthalpy change
Here, H = enthalpy of system
Property of system, point function
Measured in KJ
Specific enthalpy = h = H/m = u + Pv
Molar enthalpy = = H/n Molar enthalpy H/n
Specific heat at constant pressure (C
P
):
C
P
= (dq/dT)
P
= (h/T)
P
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Total heat interaction
If C
p
is constant,
Q = mC
P
T = mC
P
(T
2
T
1
)
2
1
T
P
T
Q m C d T =

Q mC
P
T mC
P
(T
2
T
1
)
If C
p
is not constant,
2 1
( )
p
Q mC T T =
2 T
P
C d T

Where, mean specific heat =

1
2 1
T
P
C
T T
=

Example:
1 kg of gaseous CO
2
contained in a closed system
undergoes a reversible process at constant pressure.
During this process 42 kJ of internal energy is
decreased Determine the work done during the process decreased. Determine the work done during the process.
(Take C
P
= 840 J/kgC and C
V
= 600 J/kgC)
Solution:
Given, m = 1 kg, U = 42 kJ = 42 10
3
J
Now, U = mC
V
(T
2
T
1
)
Put values, 42 10
3
= 1600(T
2
T
1
)
So, T
2
T
1
= 70C
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Now, Heat transfer in isobaric process,
Q = mC
P
(T
2
T
1
)
Put values, Q = 1840( 70)
Q = 58800 J or 58.8 kJ
Applying first law, Q = U + W
Put values 58.8 = 42 + W
W = 16.8 kJ
Work done on the system during process = 16 8 kJ Work done on the system during process 16.8 kJ
(Ans)
ConstantTemperatureProcess(Isothermal)
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System is allowed to undergo reversible expansion.
The process path can be drawn on PV diagram.
A l i fi t l f th Applying first law of thermo.,
dU = dQ dW= dQ PdV
Assume gas as ideal one, U = U(T),
So, dU = C
V
dT = 0 at constant temp.
So, We have, dQ = dW,
Heat transfer = Work transfer
dQ = PdV
Integrate, Q = W =
Put P = nRT/V for ideal gas,
2
1
V
V
P d V

2
2
ln
V
nRT V
Q W dV nRT

= = =

PV = constant (process equation)

1 1
ln
V
Q W dV nRT
V V

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ReversibleAdiabaticProcess(Isentropic)
Gas is allowed to expand reversibly and adiabatically (dQ
= 0), Isentropic process
Applying first law of thermo.,
dU = 0 dW,
W = U
W = nC
V
(T)
= nC
V
(T
2
T
1
)
= nR(T
2
T
1
)/( 1)
= (P
1
V
1
P
2
V
2
)/( 1)
Again, dU = - dW
nC
V
dT = - PdV
nC
V
dT = - nRTdV/V (For ideal gas P = nRT/V)
nRdT/( 1) = - nRTdV/V (For C
V
= R/( 1))
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Rearranging,
dT/T = - ( 1) dV/V
Integrate,
ln(T
2
/T
1
) = - ( 1) ln(V
2
/V
1
)
(T
2
/T
1
) = (V
1
/V
2
)
( 1)
T
1
V
1
( 1)
= T
2
V
2
( 1)
TV
( 1)
= Constant
Using PV = nRT We can also have Using PV nRT, We can also have,
PV

= constant, T

P
(1-)
= constant
PolytropicProcess
When a process undergoes a reversible process in
which heat is transferred and
Frequently, a plot of lnP versus lnV yields a straight
line. (Polytropic process)
For such a process, PV
n
= constant
Where n = index of expansion Where, n = index of expansion
We know for any reversible process,
Work done = W = PdV
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Putp=C/V
n
PutCasP
1
V
1
n
andP
2
V
2
n
,
2 1 1
1 2
1
( )
1
V n n
n
V
CdV V V
W C
V n
+ +

= = =

1 1 2 2
1 1
1 1 1 2 2 2
1 1 2 2
( . . )
( 1)
( )
( 1)
n n n n
PV V PV V
W
n
PV PV
W
+ +

=
N:Numberofmoles
1 2
( 1)
( )
( 1)
n
R T T
W N
n

Heat transfer during polytropic process:

Q = U + W
= NC
V
(T
2
T
1
) + NR(T
1
T
2
)/(n1)
Put value of C
V
,
= NR(T
2
T
1
)/(1) + NR(T
1
T
2
)/(n1)
= NR(T
1
T
2
)[ n+1 + 1]/(1) (n1)
= NR[(T
1
T
2
)( n)/(1) (n1)
Q = ( n)/(1) . W
Index n depends on work and heat interactions of
process.
Some processes are special cases of polytropic.
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n = 0; PV
0
= constant; P = constant; isobaric process
1 PV
1
I h l n = 1; PV
1
= constant; Isothermal process
n = ; PV

= constant; Adiabatic process

n = ; PV

= constant; V = constant; Isochoric process

Example: Equation u = 3.64 pv + 90 gives the internal energy
of a certain substance where u is in kJ/kg, p is in kPa and v is
in m
3
/kg. A system composed of 3.5 kg of this substance
expands from an initial pressure of 500 kPa and a volume of
0.25 m
3
to a final pressure 100 kPa in a process in which
pressure and volume are related by pv
1 25
= constant pressure and volume are related by pv
1.25
= constant.
(i) If the expansion is quasi-static, find Q, U and W for the
process.
(ii) In another process, the same system expands according to
the same pressure-volume relationship as in part (i) and from the same pressure volume relationship as in part (i), and from
the same initial state to the same final state as in part (i), but
the heat transfer in this case is 32 kJ. Find the work transfer for
this process.
(iii) Explain the difference in work transfer in parts (i) and (ii).
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Solution:
Given, Internal energy equation : u = 3.64 pv + 90, V
1
= 0.25 m
3
, p
1
= 500 kPa, p
2
= 100 kPa, pv
1.25
= const.
u = u
2
u
1
= 3.64 (p
2
v
2
p
1
v
1
) ... per kg
2 1
(p
2 2
p
1 1
) p g
U = 3.64 (p
2
V
2
p
1
V
1
) ...for 3.5 kg
Using, p
1
V
1
1.25
= p
2
V
2
1.25
V
2
= 0.906 m
3
and U = 125 2 kJ (Ans) and U 125.2 kJ (Ans)
For a quasi-static polytropic process,
W = (p
1
V
1
p
2
V
2
)/(n 1)
= 137.6 KJ (Ans)
Applying first law,
Q = U + W
= 12.4 kJ (Ans)
In second case U would remain as 125 2 kJ and Q In second case, U would remain as 125.2 kJ and Q
= 32 KJ (given)
Applying first law again,
W = Q U
= 32 ( 125 2) 32 ( 125.2)
= 157.2 kJ (Ans.)
In second case, process is not quasi static and work is
not pdV