THERMODYNAMICS I

CHAPTER

Properties of
pure
substances
3 Properties of a pure substance
3-1 Pure substance
A substance that has a fixed chemical composition
through out. It may exist in more than one phases
e.g. H2O.
Some mixture of gases behave like pure substance
if no phase change occurs e.g. air.

3-2 Phases of a pure substance

A phase of a substance has a distinct molecular arrangement that is homogenous
throughout and can be separated from the others by identifiable phase boundaries
e.g. (ice, water and steam are three phases of H2O).
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Dr. S. Z. Shuja
3-3 Phase change processes of pure substance

T = 20oC T = 99.6oC T > 99.6oC

P = 100 kPa P = 100 kPa P = 100 kPa
change pressure to 101.325 kPa
T = 20oC T = 100oC T > 100oC
change pressure to 1000 kPa
T = 20oC T = 179.9oC T > 179.9oC
change pressure to 10 000 kPa
T = 20oC T = 311.1oC T > 311.1oC
decrease pressure to 3.17 kPa
T = 20oC T = 25oC T > 25oC
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Dr. S. Z. Shuja
3-3 Phase change processes of pure substance

Saturation temperature (Tsat):

Temp. at which vaporization (change of phase from liquid to vapor) takes place at a given pressure.
Corresponding pressure is called the Saturation pressure (Psat) at that temperature.
e.g. @ 100 kPa, Tsat = 99.6oC and @ 99.6oC, Psat = 100 kPa.

{
At Tsat and Psat the
substance can exist
as liquid or vapor
If it exist as all liquid at Tsat & Psat it is called Saturated liquid
If it exist as all vapor at Tsat & Psat it is called Saturated vapor
some part liquid
If it exist { some part vapor }at Tsat & Psat it is called Saturated mixture

At Psat { T < Tsat it is called Compressed liquid

T > Tsat it is called Superheated vapor
What we call Gases are
highly superheated vapor
(with negligible intermolecular PE) 4
Dr. S. Z. Shuja
3-3 Phase change processes of pure substance

For Saturated mixture we define the quality (x)

quality x  
mass of vapor
total mass

Quality is defined at Tsat and Psat only

It is not defined for Compressed liquid or Superheat vapor
 for Sat. liquid x0 no vapor
 for Sat. vapor x 1 all vapor

e.g .  for Sat. mixture 0  x  1 some liquid some vapor
for compressed liquid x not defined

for superheated vapor x not defined
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Liquid-Vapor saturation curve
For pure substance there exist a definite relation between Tsat and Psat.

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Liquid-Vapor saturation curve (Table A – 5)

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Liquid-Vapor saturation

Latent heat of vaporization

amount of energy absorbed during the vaporization process
e.g. for water at 101.325 kPa, latent heat of vap. = 2257 kJ/kg

Latent heat of fusion

amount of energy absorbed during the melting (change of phase from solid to
liquid) process

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3.4 Property diagrams for phase-change processes

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Dr. S. Z. Shuja
3.4 Property diagrams for phase-change processes
The T-v Diagram
Volume for Bf > Af because TB > TA
Volume for Bg < Ag because PB > PA
i.e. effect on
change of volume { inin liquid is dominated by temperature
vapor is dominated by pressure

As pressure is increased
Tsat also increases, and
the difference between
Bf Bg
saturated liquid (vf) and
saturated vapor (vg)
Af Ag
reduces
At P = 22.09 MPa the
constant temperature
vaporization process
reduces to a point . This
point with zero slope is
called the critical point.
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3.4 Property diagrams for phase-change processes
The T-v Diagram
Critical point
The point at which the
sat. liq. and sat. vap.
States are identical.
Tc  critical temperature
Pc  critical pressure
vc  critical sp. volume
 
Table A-1, Page 904, for various substances
e.g. for H 2 O, Pc  22.09 MPa ;Tc 374.14o C

For P > Pc e.g. 25 MPa

if we heat the 2 phases are
never present together.
Such pressures are called
Super-critical pressures
T  Tc Compressed liquid
T  Tc Superheated vapor
 

PP 11
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3.4 Property diagrams for phase-change processes
The Critical point (Table A – 1)

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3.4 Property diagrams for phase-change processes
The P-v Diagram

keep temperature constant

and decrease the pressure

T = 99.6oC T = 99.6oC T = 99.6oC

P = 40 MPa P = 100 kPa P < 100 kPa
Change temperature to 200oC
P = 40 MPa P = 1554 kPa P < 1554 kPa
Change temperature to 374.14oC
P = 40 MPa P = 22.09 MPa P < 22.09MPa
Change temperature to 400oC
P = 40 MPa no phase change process by decreasing P

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3.4 Property diagrams for phase-change processes
The P-v Diagram

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P-v diagram and Table A - 4 (and A – 5)
Tsat , Psat given
vf sp. volume for sat. liquid
vg sp. volume for sat. vapor
are also given.

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3.4 Property diagrams for phase-change processes
The P-T Diagram
Consider heat addition to 1 kg of ice at -20oC in a piston/cylinder at constant P

1 kg of ice
Isobaric process P = 100 kPa Process A
Ice saturated saturated compressed saturated saturated superheated
solid liquid liquid liquid vapor vapor
-20oC 0oC 0oC 0<T<99.6 99.6oC 99.6oC T>99.6
Isobaric process P = 0.26 kPa Process B
Ice saturated saturated superheated
At P = 0.260 kPa ,the solid directly
solid converts to vapor without going to vapor vapor
-20oC -10oC the liquid phase -10oC T>-10oC
Isobaric process P = 0.6113 kPa Process C
Ice saturated saturated superheated
At P = 0.6113 kPa, some solid
solid become vapor & some become liquid vapor vapor
-20oC o
0.01 C (Triple point) 0.01oC T>0.01oC
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3.4 Property diagrams for phase-change processes
The P-T Diagram

Same general behavior

for all pure substances,
but all have different
Triple points and
Critical points

Process A
Process C
Triple point: The state in which
Process B all 3 phases are in equilibrium
Sublimation line: Solid and vapor phases are in equilibrium
Melting line: Solid and liquid phases are in equilibrium
Vaporization line: liquid and vapor phases are in equilibrium

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3.4 Property diagrams for phase-change processes
Independent properties and the state postulate
Saturated
Superheated vapor
Saturated Saturated
Compressed liquid mixture vapor
liquid

P = 10 MPa P = 10 MPa P = 10 MPa

T = 20oC T = 40oC T = 200oC P = 10 MPa P = 10 MPa P = 10 MPa P = 10 MPa
P = 10 MPa T = 500oC
v = 0.0009972 m /kg
3 v = 0.001 m3/kg v = 0.001148 m3/kg T = 311.06oC T = 311.06oC T = 325oC
T = 311.06oC
v = 0.001452 m3/kg v = ?? m3/kg v = 0.019861 m /kg v = 0.03279 m3/kg
3
v = 0.018 m3/kg

  

if any 2 properties (T , P , or v ) are given, if T and P are given, v cannot be found if any 2 properties (T , P , or v )
the 3 rd can be found T and P are not independent in the are given, the 3 rd can be found
saturated region.
v or x must be known, apart from T or P

State postulate
Any 2 independent properties can In sat. state P and T cannot completely define
sat sat
completely define the state of a the state  they are not independent properties
simple compressible substance
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3.5 Property Tables (SI units)
given any 2 independent properties, all others can be found using tables

The substance can exist as

compressed liquid  different regions


saturated mixture  drawn on the
superheated vapor  Pv or Tv diagrams

The property tables provide the relation between P, T & v (and other properties e.g. u)
Each region has a corresponding table

e.g. for water H2O

}
Saturated liquid-vapor region Table A-4/A-5
Superheated region A-6
Compressed liquid region A-7 pages 910-919
Saturated solid-vapor A-8

Similarly for R-134a Tables A-11 --- A-13 pages 922-926

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Enthalpy and Entropy (2 other properties)
Enthalpy: a combination of properties
The combination U  PV  is needed for open systems (Control Volume)
 This is called enthalpy H 
and u  Pv 

thus H  U  PV   kJ
 units 
or, specific enthalpy h  u  Pv  kJ / kg
Another property Specific entropy (s) related to 2nd law of thermodynamics is also listed
in the tables.

Saturated liquid and Saturated vapor states (Table A-4, A-5)

Both are same table A-4 1st column is Temperature, A-5 1st column is Pressure
Subscript f used for Saturated liquid e.g. vf , uf , hf , sf
Subscript g used for Saturated vapor e.g. vg , ug , hg , sg
Subscript fg used for difference e.g. vfg = vg - vf , hfg = hg - hf

Thus e.g. vfg = difference in sp. volume between saturated vapor and saturated liquid
hfg is called the latent heat of vaporization or enthalpy of vaporization
= amount of energy needed to vaporize 1 kg of a substance at Psat & Tsat
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Saturated liquid-vapor mixture
mass of vapor m g mg
quality x    
total mass m m f  mg
for a saturated mixture of volume V, and mass m
V  V f  Vg m  m f  mg
mv  m f v f  m g v g m

mf

mg
m m m
mf mg mf
v vf  vg 1 m  x v  v f  x(v g  v f )  v f  xv fg
m m mf
 1 x
 m  u  u f  x(u g  u f )  u f  xu fg
v  (1 x)v f  xvg h  h f  x(hg  h f )  h f  xh fg
 v f  x (v g v f )
s  s f  x( s g  s f )  s f  xs fg
also for the mixture
U  U f  U g  mu  m f u f  m g u g For saturated mixture, v, u, h, and s
mf mg represent the average properties in
u uf  u g  (1  x)u f  xu g these regions.
m m
 u f  x(u g  u f )
Saturated solid-vapor mixture (Table A-8)
Similar to saturated liquid-vapor mixture, but all T < Ttriple point and P < Ptriple point
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Saturated liquid-vapor Tables A – 4 and A – 5

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Tables A – 4 and A – 5

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Saturated solid-vapor Table A – 8

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Superheated vapor (Table A-6)
P  Pc the region to the right of saturated vapor line
P  Pc the region to the right of T  Tc line

Compressed liquid (Table A-7)

from saturated tables Thus if compressed liquid table is
at T  180 o C , Psat  1002.1 kPa & v  0.0011270 kg / m 3 not given, we may assume
from compressed liquid tables vcompressed liquid = vf at the same temperature
at T  180 o C , Psat  10000 kPa & v  0.0011199 kg / m 3 similarly
i.e. increasing pressure 10 times decreases sp. volume by ucompressed liquid = uf at the same temperature
0.001127 - 0.0011199 hcompressed liquid = hf at the same temperature
 0.71% only scompressed liquid = sf at the same temperature
0.001127
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Superheated vapor Table A – 6

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Compressed liquid Table A – 7

If compressed liquid table is not given

we may assume
vcompressed liquid = vf at the same temperature

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Reference states and reference values
We need to fix the states and assign values to them so that all other values are
given with respect to (w.r.t) these states

e.g. KE of earth is taken as zero although it is moving around the sun.

Similarly we need reference states for u, h, s etc. thus

Reference state
Water Sat. liquid at 0.01o C u  0 & s  0
R - 134a Sat. liquid at -40o C h0 &s0

Because of reference states some properties may have –ve values e.g. all u’s and h’s
for sat. solid H2O are -ve
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3.6 The ideal gas equation of state
Experimental observation for gases show that at low densities the P - v - T behavior
can be approximated by the following equation of state.
v  molal specific volume

Pv  RT where  R  universal gas constant  8.3145 kJ / kmolK
T  temperature in Kelvins

divinding by molecular mass, M we have equation of state on unit mass basis
v  specific volume  m3 / kg 

Pv  RT where  R  R / M  gas constant (different for each gas) Table A1
 M  molecular mass Table A1

V
using v we may write PV  mRT
m
 gas at low density assumes 
Pv  RT is called the equation of state for ideal gases  
 no intermolecular forces 

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3.7 Compressibility Factor and the compressibility chart
Pv
Pv  RT is showing that the values of P, v, and T at a state are related such that 1
RT
but this is an approximation. Actually by experimental observation Pv / RT may not be 1
is defined to see how much the behavior of a Pv
Compressibility factor  z  z
gas is different from the ideal gas behavior RT
How to find z
Experimentally determine v
at a given temperature T for
various P, record in a table
Pexp vexp
Pexp vexp z
RTexp

repeat for various T

The deviation of z from 1 is a check of the deviation of the actual relation from the ideal gas eq. 30
Dr. S. Z. Shuja
3.7 Compressibility Factor and the compressibility chart
Pexp vexp
Plot of z  against P for different T is called the Compressibility chart.
RTexp
Observations from the Compressibility chart for Nitrogen
1) All temperatures as P  0 z  1 because at low pressures molecules are far away
2) T  300 K ~ 2Tc & P upto 10 MPa, z  1 at high temperature molecules are far away

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Dr. S. Z. Shuja
3.7 Generalized compressibility chart
T P
We define reduced temperature = Tr  reduced pressure = Pr 
Tc Pc
From table A1 find Tc and Pc and extend the table to include Tr and Pr
Texp
for various Tr  find
Tc
Pexp Pexp vexp
Pexp Pr  vexp z
Pc RTexp

Plot of z against Pr at various Tr is

very similar for most of the substances
and is known as
Generalized Compressibility Chart
It is given in Fig A-15 page 928
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Generalized compressibility chart (Figs A-15a, b)

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Dr. S. Z. Shuja
 Generalized compressibility chart (Figs A-15 a, b)
Observations from the Generalized Compressibility Chart
under these conditions
1) All temperatures and P  Pc z  1 
 we can assume
2) T  2Tc & P  5 Pc , z  1 
ideal gas behavior

Use of Generalized Compressibility Chart

To find the 3rd property e.g. given P & T
1) find Pc and Tc from table A1 for the substance
2) Calculate Pr  P / Pc and Tr  T / Tc
3) From the graph read z at the Pr & Tr
4) Determine vactual from the Pvactual  zRT

we can determine videal from Pvideal  RT

vactual
then z
videal
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Generalized compressibility chart (Fig A-15)

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Dr. S. Z. Shuja
3.8 Other equations of state
Ideal gas equation is simple to use but is correct for gases only.
Other equations can be developed
e.g. Benedict-Webb-Rubin equation of state (contains 8 constants)

such equations are more accurate but difficult to use.

Another equation is the
Van der Waals
with
equation of state
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Dr. S. Z. Shuja
4.3 Specific Heats (C)
Specific heat (C):
Energy required to raise the temperature of 1kg of a substance by one degree
It is defined when there is no phase change i.e. only solid, only liquid or only vapor
2 types
energy required to rasie the temp of 1kg of a
Specific heat at constant volume Cv
substance by one degree at constant volume
energy required to rasie the temp of 1kg of a
Specific heat at constant pressure Cp
substance by one degree at constant pressure
C p is always greater than Cv because
at constant volume substance
 change in internal energy/kg   u 
does not expand only U
  Cv      
internal  with change of temperature atvolume
constant  T v
internal energy increases energy
increases

at constant pressure
U  change in enthalpy/kg   h 
internal energy increase  Cp      
PV
  with change of temperature atpressure
constant  T  p
+ work done for expansion
 enthalpy
work done  F  x  P A x  PV increases

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 4.3 Specific Heats

 u 
Cv   
 T  v

 h 
Cp   
 T  p

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4.4 Internal energy, enthalpy, and specific heats of Ideal gases

 u  f (T ) only

for ideal gas i.e. u does not depend on 2 properties

 it depends only on T
Joules experiment
initially tank A  22 atm pressure
tank B  vaccum (evacuated)
Valve is opened
no change in temp of water is observed
 no heat transfer and no work done
 Internal energy of air did not change
but P and V have changed.
Conclusion
Internal energy does not change with
Change of pressure and volume

 u = f(T) only for ideal gas

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4.4 Internal energy, enthalpy, and specific heats of Ideal gases
for ideal gas
now h  u  Pv 
u  f (T ) only   h  u  RT  h  f (T ) only
but Pv  RT  both are f (T ) only

all gases approach ideal gas at very low pressure, then ideal gas specific heat are also called
zero pressure specific heat denoted by C p 0 and Cv 0

for ideal gas

 u  du
Cv    but for ideal gas u  f  T only   C 
 T v
v0
dT
2
or du  Cv 0 dT integrating u2  u1   Cv 0 dT
1

 h  dh
Cp    but for i deal gas h  f  T only   C 
 T  p
p0
dT
2
or dh  C p 0 dT integrating h2  h1   C p 0 dT
1

In general C p 0 and Cv 0 are f n T  as shown in Fig 4-24. i.e. at different temperature 1 kg of

an ideal gas needs different energy to increase its temperature by one degree.
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4.4 Internal energy, enthalpy, and specific heats of Ideal gases

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4.4 Internal energy, enthalpy, and specific heats of Ideal gases
To find  u2  u1  and  h2  h1  for ideal gas, we have 3 methods
method 1 Assume C p 0 and Cv 0 are constant (i.e. not f T  ) as C p 0,av and Cv 0,av

u2  u1   Cv 0 dT  Cv 0,av T2  T1 
2
then
1

similarly h2  h1   C p 0 dT  C p 0,av T2  T1 

2

this method is exact for Ar , He, Ne, Kr ,..... for which C p 0 and Cv 0 does not depend on T
but is less accurate for other gases. C p 0 and Cv 0 are given in Table A - 2a at T  300 K
and in Table A - 2b at different temperatures for various substances.
T
method 2 Intergals defined as hT   C p 0 dT are given in table A17 for air and A18 - A25
0K

for other gases

T2 T2 T1
then h2  h1   C p 0 dT   C p 0 dT   C p 0 dT = hT2  hT1
T1 0 0

hT hT  hT1
note: for other gases (A18 - A22) hT is given then hT  or h2  h1  2
M M
uT2  uT1 T
similarly u2  u1  uT2  uT1  where uT   Cv 0 dT are given in tables A17 - A25. 42
Dr. S. Z. Shuja
M 0K
4.4 Internal energy, enthalpy, and specific heats of Ideal gases
method 3 Analytical expressions of the form MC p 0  C p 0  a  bT  cT 2  dT 3 are
given in Table A - 2c.
 we intergrate 
  a  bT  cT  dT
T2 T2
then h2  h1   C p 0 dT  1
M
2
 dT 3
 
T1 T1
 and evaluate 
u2  u1   h2  h1   R T2  T1    C p 0 dT  R T2  T1 
T2
also du  dh  RdT 
T1

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4.4 Internal energy, enthalpy, and specific heats of Ideal gases
(method 1) (Table A – 2 a & b)

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Dr. S. Z. Shuja
4.4 Internal energy, enthalpy, and specific heats of Ideal gases
(method 2) Tables A-17 and A-18 to A-25

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4.4 Internal energy, enthalpy, and specific heats of Ideal gases
(method 3) (Table A – 2c)

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Dr. S. Z. Shuja
4.4 Internal energy, enthalpy, and specific heats of Ideal gases
Specific heat relations of ideal gas
h  u  Pv  u  RT (for ideal gas)
then dh  du  RdT but dh  C p 0 dT and du  Cv 0 dT
C p 0 dT  Cv 0 dT  RdT or C p 0  Cv 0  R or C p 0  Cv 0  R

C p0
we may also define specific heat ratio k
Cv 0
Common values for air at 300K
C p 0  1.005 kJ / kgK
Cv 0  0.718 kJ / kgK
R  0.287 kJ / kgK

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Dr. S. Z. Shuja
4.5 u, h, and C for solids and liquids
 u   h 
by defination Cv    and C   
 T v  T  p
p

for solids and liquids h  u  Pv or dh  du  Pdv  vdP

but for solids and liquids dv
  0 and   1/ v  large  v  0
incompressible

then dh  du  P dv  v dP  dh  du for solids and liquids

i.e. adding energy changes the internal energy only with no work done to change the volume
du dh
then Cv    C p i.e. Cv  C p  C for solids and liquids without phase change.
dT dT
Secific heats C for several liquids and solids is given in Table A  3

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Dr. S. Z. Shuja
4.5 u, h, and C for solids and liquids

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Dr. S. Z. Shuja