Two adiabatic processes 2 to 3 &4 to1 PVk=constant
COP of carnot refrigeration cycle
Statements of second law of thermodynamics
Clausius Statement:Heat cannot be caused to flow from a cooler body to hotter body without producing
some other effect.
Kelvin and Planck Statement:It is impossible to build an engine which operating in a cycle that can
convert all the heat it absorbs into work.
The second law of thermodynamics for closed and open systems
General ΔS(universe)>=0
For irreversible process ΔS(universe)>0
For reversible process ΔS (universe)=0
Calculation for entropy change for closed system
The change in entropy of the surroundings is identical for reversible heat transfer and for
irreversible heat transfer ,as long as the magnitude of Q is same .If the surroundings are at constant
temperature
(if heat flows from surroundings to the system)
Calculation of entropy change for open system
At steady state (ds/dt) system is zero
At constant temperature ,the rate of entropy change with respect to surroundings
Steady state
For one stream in and one stream out
Inlet and out let molar flows are equal then
For unsteady state problem
# problem
Consider an isolated system containing two blocks of copper with equal
mass. One block is initially at 0ºC while the other is at 100ºC. They are
brought into contact with each other and allowed to thermally equilibrate.
What is the entropy change for the system during this process?
Take the heat capacity for copper to be: cP = 24.5 J/ mol K
Calculation of ΔS for ideal gas
Step I Isothermal expansion
For reversible process du=δq rev+δw rev=0
δq rev=- δw rev=P dv
❑ ❑ ❑
δ q rev P R
ΔS 1=∫ =∫ dv =∫ dv
❑ T ❑ T ❑ v
[ ]
RT 1
RT 1/ P 2
R P2 P1 P2 ΔS 1
∫ v
dv =Rln
v1
=R ln
P2
=−Rln
P1
=¿ ¿
v1
Step 2:Reversible Isobaric heatingType equation here .
du=δq rev+δw rev= δq rev-P dv
δq rev=du+P du+vdP=d(u+Pv)=dh (dP=0)
The change in entropy
❑ ❑ T2
δ q rev dh C p dT
ΔS2=∫ =∫ =∫
❑ T ❑ T T1 T
T2
P2 C p dT
ΔS=−Rln +∫
P 1 T1 T
T2 P2
ΔS=C p ln −Rln
T1 P1
T2 v2
ΔS=C v ln + Rln where Cv is constant.
T1 v1
The entropy changes for process equipment
Mechanical Energy and Bernouli Equation
For steady state and reversible
0=n ¿˙ ¿;MW-Molecular weight
δq ( surr )
˙ +
The second law is nds =0
T
δq(surr)=-δq(sys)
0=−n˙ ¿ ¿
δW (s )
=¿]
n
du=δqrev+δwrev=Tds-Pdv
dh=d(u+Pv)=Tds+vdP
δW (s )
=¿]
n
On integration
2 2 2
W (s) v2 −v 1
=∫ vdP+ MW ( )+ MWg(z 2−z 1)
n 1 2
No kinetic and potential Energy
2
W (s)
=∫ vdP (for pumps∧turbines)
n 1
No work: Nozzles and Diffusers
2 2 2
v 2 −v 1
0=∫ vdP+ MW ( )+ MWg ( z 2−z 1) (for nozzles∧diffusers)
1 2
Calculate entropy changes when 1 mole of air is heated and expanded from 25
deg C and 1 bar to 100 deg C and 0.5 bar
T2 P2
ΔS=C p ln −Rln
T1 P1
❑
Cp P2
ΔS=∫ dT −Rln
❑ T P1
A=3.355
B=0.000575
D= -0.0000105
Entropy change for process equipments
An ideal gas enters a turbine with a flow rate of 250 mol/s at a pressure of 125
bar and specific volume of 500 cm 3/mol. The gas exit pressure is 8 [Link]
process is reversible and polytropic Pv1.5=constant. Find the power generated by
turbine.
2
W (s)
=∫ vdP (for pumps∧turbines)
n 1
Write v interms of P,Pv1.5=constant=P1(v1)1.5
v=[P1(v1)1.5/P]2/3
2
W (s)
=∫ vdP (for pumps∧turbines)
n 1
2 2
∗1.5
P2 ❑
W (s ) P v 1.5 P2
p3 v 3
=∫ [ 1 1 ]dP=∫ 1 12 dP
n P1 P P1
P❑3
W (s ) j
=−11,250
n mol
W(s)=-11,250 (j/mol)*250 (mol/s)=-282786.17 (j/s)=-2851 KW
The ideal cycle for vapor power cycles: RANKINE CYCLE
Many of three impracticalities associated with carnot cycle can be
eliminated by superheating the steam in the boiler and condensing it
completely in the condenser
The ideal Rankine cycle does not involve any internal irreversibilities
1-2: Isentropic compression in a pump
2-3: Constant pressure heat addition in a boiler
3-4: Isentropic expansion in a turbine
4-1:Constant pressure heat rejection in a condenser
Compressed Superheated vapor
liquid
Saturated
liquid
Energy analysis of ideal Rankine cycle
Pumps,boiler,compressor,condenser are steady flow devices
Steady flow energy equation per unit mass of steam
(Qin-Q out)+(win-W out)=he-hi -----(1)
No work for boiler and condenser, pump and the turbine assumed to
be isentropic.
Pump: w pump,in=h2-h1-----(2)
W pump,in=v(P2-P1) ;h1=hf@P1&v=v1=vf@P1
Bolier (w=0) Qin=h3-h2
Turbine (q=0) W turb,out=h3-h4
Condenser (w=0) Q out=h4-h1
Thermal efficiency of the Rankine cycle= W net/Qin
=1-(Q out/Q in)
Where W net=Qin-Q out=W turb,out-W turb,in
Vapor compression Refrigeration cycle
Ideal vapor compression cycle
Deviations of Actual Vapor power cycles
Fluid friction associated with process components
Heat loss
Efficiency of the pump
Ƞ=(h2s-h1)/(h2a-h1)
Efficiency of the turbine
Ƞ=(h3-h4a)/(h3-h4s)
Problem
A steam power plant operates on rankine [Link] the isentropic
efficiency of the turbine is 87% and the isentropic efficiency of the
pump is 85%.Determine the thermal efficiency of the cycle & the net
power output of the palnt for the mass flow rate of 15 kg/s.
Pump work input
Ƞ= Ws pump in/ w pump in
W pump,in = v (P2-P1)/0.85
W pump ,in= [0.001009 m3/kg (16000-9)kPa]/0.85
= 18.99 kW
Boiler heat input
The inlet temperature to the boiler is 35 deg C
The outlet temperature to the boiler is 625 deg C
Q in= h outlet-h inlet
=3647.6 kJ/kg- 160.1 kJ/kg
=3487.5 kJ/kg
Turbine workoutput (Steam enters at 15 Mpa and 600 deg C&outlet of
turbine the pressure is 10 kPa)
W turb,out=ƞ*Ws turb
=0.87*(3583.1-2115.3) kJ/kg
=1276 kJ/kg
Network W net=1276-18.99 kJ/kg
=1257.01 kJ/kg
Efficiency= 1257.01/3487.5
= 36%
The power produced by plant
=( 15 kg/s)*(1257 kJ/kg)
=18,855 kW
Irreversibilites Elimination
⮚ Lowering the condenser pressure
⮚ Superheating the steam to higher temperature
⮚ Increasing the boiler pressure
The ideal Reheat Rankine cycle
The ideal Regenerative Rankine cycle
JET Propulsion cycles
Slight acclereation-Propeller driven
Higher Acceleration- Turbo propeller/jet engines
W (turboprop engine)= F*V (aircraft) =m*(V exit-V inlet)*V aircraft
Propulsive Effciency= Propulsive powera rate/Energy input rate= W/Q
Turbo fan Engines
Ram jet Engine
Scram jet (Mach 5 or 6)
Generalizations of fluid
Derivative Relationship from fundamental Relationship
Fundamental Relationship: connection between energy balance and
entropy balance. It relates state functions to one another such that no
specific physical situation is necessary when considering how the
energy and entropy change.
One variable changes with respect to some other variable changes
Objectives
To transform the variables dU into dH,dA,dG,dS,dP,dV, and dT given dU
and the definitions of H,A,and G
To describe the “measurable properties and its applications
To apply chain rule and other aspects of multivariable calculus to
transform one derivative to another
Use Maxwell relations to interchange derivatives
Manipulate partial derivatives using two to three steps of
manipulations to put in terms of measurable properties
Substitute Cp and Cv for the appropriate temperature derivatives of
entropy
Recognize common characters of derivative properties like isothermal
compressibility and the joule Thompson coefficient and express tehm in
measurable properties
Devise stepwise paths to compute dU (T,V) and dS(T,P) and ds(T,V)
from ideal gas and density dependent terms
The fundmental property relation for dU in simple systems
The energy balance for simple closed systems
d (U+Ek+Ep)=dQ+dWs+dW Ec
The simple system has no gradients or shaft work
dU=dQ-PdV
dU (rev)=dQ(rev)-(PdV)(rev)
dS=dQ(rev)/T (sys)
T(sys) dS=dQ (rev) (Tsys-system temperature where Q transferred)
On a molar basis
dU=T-Pdv
Auxillary relations for convenience properties
dU is most simply written function of S and V and its termed as natural
function of S and V.
H=U+PV
dH=dU+Pdv+VdP=Tds-Pdv+Pdv+VdP
dH=Tds+VdP
Helmholtz energy (contraction/expansion work for an isothermal
system)
A=U-TS
dA=dU-Tds-SdT=Tds-PdV-Tds-SdT
dA=-SdT-PdV A is a function of T and V
Gibbs Free energy (Phase equilibria problems when temperature and
pressure are controlled)
G=U-TS+PV=A+PV=H-TS
dG=dH-Tds-SdT=Tds+VdP-Tds-sdT
dG=-sdT+vdP
dG=0 when T and P are constant (dT=0 and dP=0)
A=U-TS
G=U-TS+PV
Derivative Relations
Measurable properties (P,V,T and derivatives only involving P-V-T)
Cp and Cv which are known functions of temperature at low pressure
S is accepatable if it is not a derivative consdtraint or with in derivative
term.S can be calculated once the state is specified
dU=f(P,V,T,Cp ,Cv)dV+g(P,V,T,Cp,Cv)dT
set of variables:[T,S,P,V,U,H,A,G]
T,S,P,V
U,H,A,G
∂u δu
dU=( ∂ x dx+ δy dy)
Basic Identities
δx 1
(z )=
δy δy
(z)
δx
∂x
( constant x )=0
∂y
∂x
( constant y )=∞
∂y
Triple Product rule
F=F(x,y)
δF ∂F
dF= δx dy+
∂y dy
δx ∂y ∂F
( const F ) ( constant x ) ( constant y )=1
δy ∂F ∂x
Exact Differentials
Any state property in terms of any other two state [Link] a
function which is only dependent on two variables, We can obtain the
following differential relation, called Exact Differential.
∂U ∂U
U=U(S,V)=dU= ∂ S ¿ dS + ∂V S dV
dU=Tds-PdV
T=¿)_
∂U
-P= ∂ V S
∂H ∂H
H=H(S,P)=dH= ∂ S ❑P dS+ ∂ PS dP
dH=Tds+VdP
∂H
T= ∂ S ❑P
∂H
V= ∂ P S
For an exact differential M,differentiating with respect to x we can
define some function M
∂F
M= ∂ x ( const y ) =M (x , y )
❑ ❑
∂F
N= ∂ y ( const x ) =N (x , y )
❑ ❑
2
∂ F ( x , y) ∂ ∂ F ( x , y ) ❑ ∂
= {( ) } y= {¿ ¿
∂x∂ y ∂x ∂y x ∂y
∂N ∂M
( const y )= (const x )
∂x ∂y
∂H ∂H
dH= ∂ S ❑P dS+ ∂ PS dP
dH=Tds+VdP
considering second derivatives
2 2
∂ H ∂ H ∂ ∂H ∂ ∂H
= =[ ( ) ] =[ ( ) ]
∂S ∂P ∂ P∂S ∂S ∂ P S P ∂ P ∂ S P S
∂V ∂T
[ ] =[ ]
∂S ❑ P ∂P S
MAXWELL’S RELATIONS
dH =TdS+VdP=
[ ] [ ]
∂V
=
∂T
∂S ❑ P ∂ P S
dU =TdS−PdV =− [ ] [ ]
∂P
=
∂T
∂S ❑ V ∂V S
dA=−SdT −PdV =−
[ ] [ ]
∂P
=
∂S
∂T V ∂V T
dG=−SdT +VdP=−
[ ] [ ]
∂v
=
∂S
∂T P ∂ P T
∂H
Derive the relation for ( ∂ P )T and evaluate derivative for a) water at 20
−4 3 −5 3
∂V 2.07∗10 c m ∂V −4.9∗10 c m
deg C where ( ∂T ) =
g. K
,( )=
∂P T g . ¯¿ ¿
,density=0.998
P
g/cm^3
b) for an ideal gas
consider the relationship dH=TdS+VdP apply the expansion rule
∂H ∂S ∂P ∂S ∂V
=T +V =T +V =−T +V
∂ PT ∂ PT ∂ PT ∂ PT ∂T P
∂V R −T∗R
For ideal gas V=RT/P= ∂T P= P =( P
)+V=-V+V=0
Thermodynamic Web
The importance of derivative manipulations
Converting derivatives involving unmeasurable properties into
derivatives involving measurable properties.
Important derivatives measurable
● if we have a pressure explicit equation of state, P=f(T,v), we can analytically assess the
partial derivative ( ∂∂ TP )
v
● A volume explicit equation of state, v=f(T,P) allow us to obtain ( ∂∂TV ) P
−1 ∂ V
Isothermal compressibility κ= V ( )
∂P T
Isobaric coefficient of thermal expansion β= V ( ) = −1ρ ∂∂ Tρ
−1 ∂ V
∂T P P
∂P
(β/ κ)=( ∂ T )v
Joule Thompson Coeffcient µ=¿
Thermal expansion coeffi cient
( ∂∂TV ) =β V
P
Entropy change for a simple non ideal gas
A gas is compressed from ambient conditions to a high [Link]
a model equation for computing ΔS(T,P) with the equation of state
V=RT/P+(a+bT) where a and b are constants
∂V R
V=RT/P= ∂T P= P + b
Entropy changes of any fluid with respect to temperature and pressure
in terms of Cp
∂V
dS(T,P)=Cp/T dT- ∂T P dP
R R
dS(T,P)=Cp/T dT-( P + b ¿ dP=Cp/T dT- P dP−bdP
=CpdlnT-RlnP-bdP
ΔS=Cp ln(T2/T1)-Rln(P2/P1)-b ΔP
∂U
Derive an expression for ∂ V T in terms of measurable properties
(a)Evaluate for the ideal gas
(b)Evaluate for the VanderWaals EoS,P=RT/(V-b)-a/V^2
dU=TdS-PdV
apply the expansion rule
∂U ∂S ∂V
=T −P
∂V T ∂V T ∂V T
∂U ∂P
=T ( ) −PT
∂V T ∂T V
For ideal gas P=RT/V
∂P
( ) =R /V
∂T V
∂ U (ig) T∗R
= −P
∂V T V
For VanderWaals Equation
∂P R
( ) =
∂ T V V −b
∂U T∗R
= −¿)=a/v^2
∂ V T V −b
Examples
One mole of propane gas is to be expanded from 0.001 m 3 to 0.040 m3 while in
contact with a heating bath that keeps the temperature constant at 100ºC. The
expansion is not reversible. The heat extracted from the bath is 10.4 KJ. Using the
van der Waals equation of state, determine the work for the expansion.
Consider for example the flow of gas through a pipeline. If the states and
thermodynamic properties of the gas entering and leaving the pipeline are known,
then application of the first law establishes the magnitude of the energy exchange
with the surroundings of the pipeline.
If one has only incomplete knowledge of the initial or final state of the gas, then
more detailed information about the process is needed before any calculations are
made.
For example, the exit pressure of the gas may not be specified. In this case, one
must apply the momentum principle of fluid mechanics, and this requires an
empirical or theoretical expression for the shear stress at the pipe wall.
● Flow processes inevitably result from pressure gradients within the fluid.
● Temperature, velocity, and even concentration gradients may exist within the
flowing fluid. This contrasts with the uniform conditions that prevail at
equilibrium in closed systems.
● The distribution of conditions in flow systems requires that properties be attributed
to point masses of fluid. Thus we assume that intensive properties, such as density,
specific enthalpy, specific entropy, etc., at a point are determined solely by the
temperature, pressure, and composition at the point, uninfluenced by gradients that
may exist at the point.
● Moreover, we assume that the fluid exhibits the same set of intensive properties at
the point as though it existed at equilibrium at the same temperature, pressure, and
composition.
● The implication is that an equation of state applies locally and instantaneously at
any point in a fluid system, and that one may invoke a concept of local state,
independent of the concept of equilibrium
DUCT FLOW OF COMPRESSIBLE FLUIDS
Thermodynamics does provide equations that interrelate the changes occurring in
pressure, velocity, cross-sectional area, enthalpy, entropy, and specific volume of a
flowing stream.
We consider here the adiabatic, steady-state, one-dimensional flow of a compressible
fluid in the absence of shaft work and of changes in potential energy.
The pertinent thermodynamic equations are first derived; they are then applied to flow in
pipes and nozzles.
● Thus the pressure decreases and the velocity increases in the direction of flow.
● For subsonic flow, the maximum fluid velocity obtainable in a pipe of constant
cross section is the speed of sound, and this value is reached at the exit of the pipe.
● At this point dS/dx reaches its limiting value of zero. the mass rate of flow
decreases
● The equations for pipe flow indicate that when flow is supersonic the pressure
increases and the velocity decreases in the direction of flow.
● However, such a flow regime is unstable, and when a supersonic stream enters a
pipe of constant cross section, a compression shock occurs, the result of which is
an abrupt and finite increase in pressure and decrease in velocity to a subsonic
value.