T – ds relations

Entropy change for a process can be evaluated by integrating δQ/T along

some imaginary internally reversible path between the actual end states

From energy equation for a closed stationary system (a reversible process)

δQint rev − δWint rev ,out = dU

δQint rev = TdS and δWint rev ,out = PdV

Thus
TdS = dU + PdV
Called Gibbs equation
Or per unit mass
Tds = du + Pdv
From the definition of enthalpy
h = u + Pv → dh = du + Pdv + vdP
Tds = ( dh − Pdv − vdP ) + Pdv
Thus Tds = dh − vdP
 Entropy change of liquids and solids
Entropy equation
(valid in both reversible and
irreversible processes)
Tds = du + Pdv

For ideal gas du = Cv dT and dh = C p dT

For incompressible substance dv ≅ 0

(specific volume remains constant)
C p = Cv = C
du CdT
ds = =
T T
2
Entropy change of dT T2
solid or liquid s2 − s1 = ∫ C (T ) ≅ Cav ln
1
T T1

where Cav = average specific heat of substance over the given temperature
 Entropy change of liquids and solids

For an isentropic process Δs = 0

T2
s2 − s1 = Cav ln = 0 T2 = T1
T1
This means that temperature is constant Isothermal process
 Example: effect of density of a liquid on entropy
Liquid methane is commonly used in various cryogenic applications. The
critical temperature of methane is 191 K (or 82°C), and thus methane must
be maintained below 191 K to keep it in liquid phase. The properties of
liquid methane at various temperatures and pressures are given in Table.
Determine the entropy change of liquid methane as it undergoes a process
from 110 K and 1 MPa to 120 K and 5 MPa
(a) using tabulated properties and
(b) approximating liquid methane as an incompressible substance. What is
the error involved in the latter case?
 Example: effect of density of a liquid on entropy
(a) Find entropy from actual data
‰ From following Table

State 1 P1 = 1 MPa ⎫ s1 = 4.875 kJ/kg.K

⎬
T1 = 110 K ⎭ C p ,1 = 3.471 kJ/kg.K
State 2 P2 = 5 MPa ⎫ s2 = 5.145 kJ/kg.K
⎬
T2 = 120 K ⎭ C p ,2 = 3.486 kJ/kg.K

Δs = s2 − s1 = 5.145 − 4.875 = 0.27 kJ/kg.K

 Example: effect of density of a liquid on entropy
(b) Find entropy from approximation assuming methane to be
incompressible
2
dT T2
s2 − s1 = ∫ C (T ) ≅ Cav ln
1
T T1

C p ,1 + C p ,2 3.471 + 3.486
C p ,ave = = = 3.7485 kJ/kg.K
2 2
Thus
120
Δs = ( 3.4785 ) ln = 0.303 kJ/kg.K
110

Δsactual − Δsideal 0.27 − 0.303

Error = = = 0.122 (12.2% )
Δsactual 0.27

Due to the change of density of liquid methane!

 Entropy change of ideal gas
Tds = du + Pdv
du Pdv dT dv
ds = + = Cv +R
T T T v
where for Ideal gas u = CvdT and Pv = RT

⎧2 dT ⎫ v2
Thus entropy change s2 − s1 = ⎨ ∫ Cv (T ) ⎬ + R ln
⎩1 T ⎭ v1
Tds = dh − vdP
dh vdP dT RdP
ds = − = Cp −
T T T P
where for Ideal gas h = CpdT and Pv = RT

⎧2 dT ⎫ P2
s2 − s1 = ⎨ ∫ C p (T )
Thus entropy change
⎬ − R ln
⎩1 T ⎭ P1
 Entropy change of ideal gas (cont.)
Entropy change

⎧2 dT ⎫ v2 ⎧2 dT ⎫ P2
s2 − s1 = ⎨ ∫ Cv (T ) ⎬ + R ln s2 − s1 = ⎨ ∫ C p (T ) ⎬ − R ln
⎩1 T ⎭ v1 ⎩1 T ⎭ P1

For constant specific heat, Cp,1-2 = Cp,av and Cv,1-2 = Cv,av

T2 v2 T2 P2
s2 − s1 = Cv ,av ln + R ln s2 − s1 = C p ,av ln − R ln
T1 v1 T1 P1

Acceptable when temperature change is small

 Isentropic process of ideal gas (cont.)
For constant specific heat
T2 v2
(a) s2 − s1 = 0 → Cv ,av ln = − R ln
R
T1 v1
k −1
T2 ⎛ v1 ⎞ Cv T2 ⎛ v1 ⎞ R = C p − Cv
ln = ln ⎜ ⎟ =⎜ ⎟
T1 ⎝ v2 ⎠ T1 ⎝ v2 ⎠ k = C p / Cv

T2 P2
(b) s2 − s1 = 0 → C p ,av ln = R ln
T1 P1
R k −1
T2 ⎛ P2 ⎞ Cp
T2 ⎛ P2 ⎞ k
ln = ln ⎜ ⎟ =⎜ ⎟
T1 ⎝ P1 ⎠ T1 ⎝ P1 ⎠
k
P2 ⎛ v1 ⎞
=⎜ ⎟
P1 ⎝ v2 ⎠
 Example: isentropic compression of an ideal gas
Helium gas is compressed by an adiabatic compressor from an initial state
of 14 psia and 50°F to a final temperature of 320°F in a reversible manner.
Determine the exit pressure of helium. Specific heat ratio k of helium is
1.667

T ( R ) = T ( O F ) + 459.67
 Example: isentropic compression of an ideal gas
Since helium is at high temperature relative to its critical point value of
-450OF, helium can be treated as an ideal gas

k −1
T2 ⎛ P2 ⎞ k
=⎜ ⎟
T1 ⎝ P1 ⎠
k 1.667
⎛P ⎞ k −1 ⎛ 780 R ⎞ 1.667 −1
P2 = P1 ⎜ 2 ⎟ = (14 psia ) ⎜ ⎟ = 40.5 psia
⎝ P1 ⎠ ⎝ 510 R ⎠
 Example
Air initially at 0.1 MPa, 27oC, is compressed reversibly to a final state.
(a) Find the entropy change of the air when the final state is 0.5 MPa, 227oC.
(b) Find the entropy change when the final state is 0.5 MPa, 180oC.
(c) Find the temperature at 0.5 MPa that makes the entropy change zero.
Assume air is an ideal gas with constant specific heats.
a.

b.
 Example
(c) Find the temperature at 0.5 MPa that makes the entropy change zero.

The T-s plot is

T
P2
2
a
c
b
P1

s
 Reversible Steady-Flow Work
Isentropic, Steady Flow through Turbines, Pumps, and Compressors
Consider a turbine, pump, compressor, or other steady-flow control
volume, work-producing device.

The general first law for the steady-flow control volume is

E in = E out
G2 G2
Vi Ve
Qnet + ∑ m i (hi +
 + gzi ) = Wnet + ∑ m e (he +
 + gze )
inlets 2 exits 2
For a one-entrance, one-exit device undergoing an internally reversible
process, this general equation of the conservation of energy reduces to, on a
unit of mass basis
δ wrev = δ qrev − dh − dke − dpe
where δ qrev = T ds
δ wrev = T ds − dh − dke − dp
 Reversible Steady-Flow Work
Using the Gibb’s second equation, this becomes

dh = T ds + v dP
δ wrev = −v dP − dke − dpe
Integrating over the process, this becomes

Neglecting changes in kinetic and potential energies, reversible work becomes

Based on the classical sign convention, this is the work done by the control
volume. When work is done on the control volume such as compressors or
pumps, the reversible work going into the control volume is

Reversible work input

 Reversible Steady-Flow Work

For the steady-flow of an incompressible fluid through a device that involves

no work interactions (such as nozzles or a pipe section), the work term
is zero, and the equation above can be expressed as the well-know
Bernoulli equation in fluid mechanics.

v ( P2 − P1 ) + Δke + Δpe = 0
 Example
Determine the compressor work input required to compress steam
isentropically from 100 kPa to 1 MPa, assuming that the steam exists as
(a) saturated liquid and (b) saturated vapor at the inlet state.

Assumptions
1. Steady operating condition
2. Neglect PE and KE
3. Isentropic process

(a) Steam is a saturated liquid initially v1 = v f @100 kPa = 0.001043 m3 /kg

2
wrev ,in = ∫ vdP ≅ v1 ( P2 − P1 )
1

= ( 0.001043 m /kg ) (1000 − 100 kPa )

1 kJ kJ
3
= 0.94
1 kPa.m3 kg
 Example
(b) From information pressure changes from 100 kPa to 1 MPa
Thus v varies with P

Tds = dh − vdP But for a isentropic process dh = vdP

2 2
Thus wrev ,in = ∫ vdP = ∫ dh = h2 − h1
1 1

State 1 P1 = 100 kPa ⎫ h1 = 2675.5 kJ/kg From table

⎬
( sat.vapor ) ⎭ s1 = 7.3594 kJ/kg.K
State 2 P2 = 1 MPa ⎫ From table
⎬ h2 = 3195.5 kJ/kg
s2 = s1 ⎭

wrev ,in = 3195.5 − 2675.5 = 520 kJ/kg

 Example
Saturated liquid water at 10 kPa leaves the condenser of a steam power
plant and is pumped to the boiler pressure of 5 MPa. Calculate the work for
an isentropic pumping process.

a. Work for the reversible process can be applied to the isentropic process

WC = mv
 1 ( P2 − P1 )

Here at 10 kPa, v1 = vf = 0.001010 m3/kg.

The work per unit mass flow is

WC
wC = = v1 ( P2 − P1 )
m
m3 kJ
= 0.001010 (5000 − 10)kPa 3
kg m kPa
kJ
= 5.04
kg
 Example

b. Using the steam table data for the isentropic process, we have

−Wnet = m (h2 − h1 )
−(0 − W ) = m (h − h )
C 2 1

From the saturation pressure table,

⎧ kJ
h = 191.81
P1 = 10 kPa ⎫ ⎪⎪
1
kg
⎬⎨
Sat. Liquid ⎭ ⎪ kJ
s1 = 0.6492
⎪⎩ kg ⋅ K
Since the process is isentropic, s2 = s1. Interpolation in the compressed
liquid tables gives
P2 = 5 MPa ⎫
⎪ kJ
kJ ⎬ 2 h = 197.42
s2 = s1 = 0.6492 ⎪ kg
kg ⋅ K ⎭
 Example

The work per unit mass flow is

WC
wC = = (h2 − h1 )
m
kJ
= (197.42 − 191.81)
kg
kJ
= 5.61
kg
 Isentropic or adiabatic efficiencies

Most steady-flow devices operate under adiabatic conditions, and the ideal
process for these devices is the isentropic process.

Isentropic device
- Turbine,
- Compressor or Pump
- Nozzle
 Turbine

The isentropic work is the maximum possible work output that the adiabatic
turbine can produce; therefore, the actual work is less than the isentropic
work. Since efficiencies are defined to be less than 1, the turbine isentropic
efficiency is defined as
Actual turbine work wa
ηT = =
Isentropic turbine work ws
h1 − h2 a
ηT ≅
h1 − h2 s
 Example
The isentropic work of the turbine in is 1152.2 kJ/kg. If the isentropic
efficiency of the turbine is 90 percent, calculate the actual work. Find the
actual turbine exit temperature or quality of the steam.
Steam enters the turbine at 1 MPa, 600oC, and expands to 0.01 MPa.

Actual turbine work w

ηT = = a
Isentropic turbine work ws
kJ kJ
wa = ηT ws = (0.9)(1153.0 ) = 1037.7
kg kg

h1 − h2 a
ηT ≅
h1 − h2 s
 Example
From the steam tables at state 1
⎧ kJ
⎪ h1 = 3698.6
P1 = 1 MPa ⎫ ⎪ kg
⎬⎨
T1 = 600 C ⎭ ⎪
o
kJ
s1 = 8.0311
⎩⎪ kg ⋅ K
At the end of the isentropic expansion process

P2 = 0.01 MPa ⎫⎧ kJ
⎪ ⎪ 2s
h = 2545.6
kJ ⎬ ⎨ kg
s2 s = s1 = 8.0311
kg ⋅ K ⎪⎭ ⎪⎩ x2 s = 0.984
The actual turbine work per unit mass flow is

wa = h1 − h2 a
h2 a = h1 − wa = (3698.6 − 1037.7)
kJ
= 2660.9
kJ
kg kg
 Example (cont.)
For the actual turbine exit state 2a, the computer software gives

A second method for finding the actual state 2 comes directly from the
expression for the turbine isentropic efficiency. Solve for h2a.

h2 a = h1 − ηT ( h1 − h2 s )
kJ kJ
= 3698.6 − (0.9)(3698.6 − 2545.6)
kg kg
kJ
= 2660.9
kg

Then P2 and h2a give T2a = 86.85oC.

 Compressor and Pump:
The isentropic work is the minimum possible work that the adiabatic
compressor requires; therefore, the actual work is greater than the isentropic
work. Since efficiencies are defined to be less than 1, the compressor
isentropic efficiency is defined as
Isentropic compressor work ws
ηC = =
Actual compressor work wa
h2 s − h1
ηC ≅
h2 a − h1
T1
P1
WC
Compressor
or pump
 Example
Air enters a compressor and is compressed adiabatically from 0.1 MPa,
27oC, to a final state of 0.5 MPa. Find the work done on the air for a
compressor isentropic efficiency of 80 percent.
2a
T 2s P2

P1
1

Ideal gas equations, assume constant properties.

Assume isentropic, steady-flow and then apply the compressor isentropic
efficiency to find the actual work.
 Example (cont.)
Conservation Principles:
For the isentropic case, Qnet = 0. Assuming steady-state, steady-flow, and
neglecting changes in kinetic and potential energies for one entrance, one
exit, the first law is  
Ein = E out
m 1h1 + WCs = m 2 h2 s
The conservation of mass gives
m 1 = m 2 = m
The conservation of energy reduces to
WCs = m (h2 s − h1 )
WCs
wCs = = (h2 s − h1 )
m
Using the ideal gas assumption with constant specific heats, the isentropic
work per unit mass flow is
wCs = C p ( T2 s − T1 )
 Example (cont.)
The isentropic temperature at state 2 is found from the isentropic relation
k −1
⎛ P2 ⎞ k
T2 s = T1 ⎜ ⎟
⎝ P1 ⎠
1.4-1
⎛ 0.5 MPa ⎞
= ( 27+273 K ) ⎜
1.4
⎟ = 475.4 K
⎝ 0.1 ⎠
The conservation of energy becomes

wCs = C p (T2 s − T1 )
kJ kJ
= 1.005 (475.4 − 300) K = 176.0
kg ⋅ K kg
The compressor isentropic efficiency is defined as
kJ
ws 176
ηC = wCa =
wcs
=
kg
= 220
kJ
wa ηC 0.8 kg
 Nozzle:
The isentropic kinetic energy at the nozzle exit is the maximum possible
kinetic energy at the nozzle exit; therefore, the actual kinetic energy at the
nozzle exit is less than the isentropic value. Since efficiencies are defined to
be less than 1, the nozzle isentropic efficiency is defined as
G2
Actual KE at nozzle exit V2 a / 2
ηN = = G2
Isentropic KE at nozzle exit V2 s / 2

T1
T2
P1
P2

Nozzle