Property

Relationships
Chapter 6

1
:The T-ds relations
Apply the differential form of the first law for a closed
stationary system for an internally reversible
process

Qint rev  Wint rev dU

Qint rev TdS Wint rev PdV

TdS  PdV dU 2

Divide by the
mass, you get Tds du  Pdv
This equation is known as:
First Gibbs equation or First Tds
relationship
Divide by T, .. du Pdv
ds  
T T
Although we get this form for internally reversible
process, we still can compute s for an irreversible
process. This is because S is a point function.

3
Second T-ds (Gibbs) relationship
Recall that… h u  Pv
Take the differential for both sides

dh du  Pdv  vdP

Rearrange
to find du du dh  Pdv  vdP
Substitute in
the First Tds
relationship Tds du  Pdv
Tds dh  vdP
Second Tds relationship, or Gibbs equation
4
 dh vdP
Divide by T, .. ds  
T T
Thus We have two equations for ds
du Pdv dh vdP
ds   ds  
T T T T
To find s, we have to integrate these equations.
Thus we need a relation between du and T (or dh
and T).
Now we can find entropy change (the LHS of the
entropy balance) for liquids and solids

5
Entropy Change of Liquids -2
and Solids
Solids and liquids do not change specific volume
appreciably with pressure. That means that dv=0, so
the first equation is the easiest to use.
0
du Pdv Thus For du
ds   solids and ds 
T T liquids
T
,Recall also that For solids and liquids du CdT
du CdT
 ds  
T T 6
Integrate  T2  Only true
to give… s C ln  for solids
 T1  and
liquids!!
What if the process  T2 
s 0,  C ln  0
?is isentropic
 T1 
The only way this
expression can equal 0 is T1 T2
if,
Hence, for solids and liquids,
isentropic processes are also 7

isothermal.
Example(6-7): 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 -82oC), 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
next page.
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 actual data for methane and
(b) approximating liquid methane as an incompressible
substance. What is the error involved in the later case?

8
 s s 2  s 2 5.145  4.875 0.270kj / kgK

 T2   T2   120 
s C ln  Cavg ln  3.4785 ln  0.303kj / kgK
 T1   T1   110  9
Example (6-19): Entropy generated when a hot
block is dropped in a lake

A 50-kg block of iron casting at 500 K is dropped in a large

lake that is at 285 K. The block reaches thermal equilibruim
with lake water.
Assuming an average specific heat of 0.45 kJ/kg.K for the
iron, determine:
(a) The entropy change of the iron block,
(b) The entropy change of the water lake,
(c) the entropy generated during this process.

10
(a) The entropy change of the iron block,

 T2   285 
Siron  
mC ln  50 0.45 ln   12.65 kj / K
 T1   500 
we need also to find Q coming out of the system.

Q  W U Q  0 mC (T2  T1 )

Q 50 0.45(285  500)  4838 kJ
Tsurr= 285 K
(b) The entropy change of the water lake,
T=500K
Q 4838
Slake   16.97 kJ / K
Tlake 285

11
 (c) the entropy generated during this process.

Choose the iron block and the lake as the system

and treat it is an isolated system.

Tsurr= 285 K
Thus Sg = Stot = Ssys + Slake
T=500K

Sg = Stot = -12.6 + 16.97

= 4.32 System
boundary

12
The Entropy Change of Ideal -3
Gases, first relation
First relation
The entropy change of an ideal gas can be obtained by
substituting du = CvdT and P /T= R/ into Tds relations:

Tds du  pd  du Pd  dT d
ds   ds C v R
T T T 

integrating 2
dT 2
 s2  s1  Cv T  R ln

1
T 1
13
Second relation
A second relation for the entropy change of an ideal gas
for a process can be obtained by substituting dh = CpdT
and /T= R/P into Tds relations:
dh vdp dT dp
Tds dh  vdp ds   ds C p R
T T T p

integrating
2
dT P2
s2  s1  C p T   R ln

1
T P1
14
 2
dT 2
s2  s1 Cv T  R ln
1
T 1
2
dT P2
s2  s1  C p T   R ln

1
T P1

 The integration of the first term on the RHS can be done via
two methods:

1. Assume constant Cp and constant Cv (Approximate Analysis)

2. Evaluate these integrals exactly and tabulate the data (Exact

Analysis)
15
Method 1: Constant specific
heats (Approximate Analysis)
First relation
2
dT 2  T2   v2 
s2  s1 Cv T  R ln  s Cv ln   R ln 
1
T 1  T1   v1 
Only true for ideal gases, assuming constant heat
capacities
Second relation
2
dT P2  T2   P2 
s2  s1 C p T   R ln  s C p ln   R ln 
1
T P1  T1   P1 
Only true for ideal gases, assuming constant heat
capacities
16
Sometimes it is more convenient to calculate the
change in entropy per mole, instead of per unit mass

 T2   v2 
s s2  s1 Cv ln   Ru ln  kJ/kmol. K
 T1   v1 
 T2   P2 
s s2  s1 C p ln   Ru ln  kJ/kmol. K
 T1   P1 

Ru is the universal gas constant

17
Method 2: Variable specific
heats (Exact Analysis)
C p dT
2
P2
We use the
second relation
s 
1 T
 R ln
P1
 Wecould substitute in the equations for Cv
and Cp, and perform the integrations
 Cp = a + bT + cT2 + dT3
 But this is time consuming.
 Someone already did the integrations and
tabulated them for us (table A-17)
 They assume absolute 0 as the starting point
18
The integral is expressed as:
T2 dT T2 dT T1 dT
T1 C p (T ) T  0 C p (T ) T  0 C p (T ) T
T2
dT

0 0
Cp( T ) s2  s1
T1 T
T
dT

s  Cp( T )
0
Where 0 T
is tabulated in Table A-17

Therefore
P2
s s  s  R ln
0
2
0
1
unit : kJ / kg .K P1 19
Is s = f (T) only? like u for an
.ideal gas Let us see
Temperature dependence
Pressure

P2 dependence

s s  s  R ln
0
2
0
1
P1
 From this equation, It can be seen that the
entropy of an ideal gas is not a function only of
the temperature ( as was the internal energy) but
also of the pressure or the specific volume.
 The function s° represents only the temperature-
dependent part of entropy
20
How about the other relation
2
dT v2
1
s  Cv
T
 R ln
v1
 We can develop another relation for the
entropy changed based on the above relation
 but this will require the definition of another

function and tabulating it which is not

practical. T
dT

?  Cv ( T )
0 T
21
6-4 Isentropic Processes
 The entropy of a fixed mass can be
changed by
1. Heat transfer,

2. Irreversibilities
 It follows that the entropy of a system

will not change if we have

1. Adiabatic process,

2. Internally reversible process.

 Therefore, we define the following:
22
Isentropic Processes of Ideal
Gases
 Many real processes can be modeled as
isentropic

 Isentropic
processes are the standard against
which we should measure efficiency

 We need to develop isentropic relationships

for ideal gases, just like we developed for
solids and liquids
23
Constant specific heats (1st relation)
Recall  T2   v2 
s Cv ln   R ln 
 T1   v1 
For the isentropic case, S=0. Thus
R
 T2   v2   T2  R  v2   v1  Cv
Cv ln   R ln  ln   ln  ln 
 T1   v1   T1  Cv  v1   v2 
Recall also from ch 2, the following relations..…

R C p  Cv  R / Cv C p / Cv  1 k  1
k1 Only applies
 T2   v1 
     to ideal
gases, with
 T1   v2  constant 24

specific heats
 Constant specific heats (2nd
relation)  T2   P2 
s C p ln   R ln  0
 T1   P1 
R
 T2  R  P2   P2  Cp
ln   ln  ln 
 T1  C p  P1   P1 
k 1
Recall..… R / Cv k  1 or R /C p 
k
k1
Only applies
 T2   P2  k
to ideal
     gases, with
 T1   P1  constant
specific heats 25
…Since
k1 k1
 T2   v1   T2   P2  k
    and    
 T1   v2   T1   P1 
k1
k1
HENCE  v1   P2  k
   
 v2   P1 

k
Which can be  v1   P2  Third
simplified to…     isentropic
 v2   P1  relationship
26
 Full form of Isentropic relations of Ideal
Gases
k1 k1 k
 T2   v1   T2   P2  k  v1   P2 
           
 T1   v2   T1   P1   v2   P1 
Compact form
1 k

Tv k1
constant TP k
constant Pv k constant
 Valid for only for
 1- Ideal gas

 2- Isentropic process

 3- Constant specific heats

27
That works if the specific heat constants can
be approximated as constant, but what if
?that’s not a good assumption

We need to use the

exact treatment 0  P2 
s s  s  R ln 
0
2
0
1
 P1 
This equation is a
good way to  P2 
evaluate property s s  R ln 
0
2
0
1
changes, but it can
be tedious if you  P1 
know the volume
ratio instead of the 28
pressure ratio
  P2 
s s  R ln 
0
2
0
1
s20 is a function
 P1  only of
temperature!!!
0
s  s 0
 P2  Rename the exponential
2
ln 
1
term as Pr , (relative
R  P1  pressure) which is only a
function of temperature,
P2  s20  s10  and is tabulated on the
exp 
P1 ideal gas tables
 R 
 s 20   s 20 
exp   exp   P
P2  R   R   r2 P2 Pr 2
 
P1  s10   s10  Pr 1 P1 Pr 1
exp   exp  
R  R 
  29
You can use either of the following 2 equations
P2 Pr 2  P2 
 s s  R ln 
0
2
0
1
P1 Pr1  P1 
This is good if you know the pressure ratio but
how about if you know only the volume ratio
In this case, we use the ideal gas law
P1v1 P2 v2 v2 T2 P1 T2 Pr1 T2 Pr1 vr 2
     
T1 T2 v1 T1 P2 T1 Pr 2 Pr 2 T1 vr 1
v2 vr 2
wher vr T / P r  
e v1 vr1
Remember, these relationships only hold for ideal
gases and isentropic processes 30
Example (6-10):
Isentropic Compression of Air in a Car Engine
Air is compressed in a car engine from 22oC and 95
kPa in a reversible and adiabatic manner. If the
compression ratio V1/V2 of this piston-cylinder device
is 8, determine the final temperature of the air.
<Answer: 662.7 K>
Sol:

31