CHAPTER II

PROPERTIES OF PURE
SUBSTANCES
KKKR1243 CHEMICAL ENGINEERING THERMODYNAMICS I
(PROF. IR. DR. SITI ROZAIMAH SHEIKH ABDULLAH &
PROF. MADYA DR. IR. MASTURAH MARKOM @ JKKP, FKAB, UKM)
 Pure substances ?

How to illustrate
H? phase changes on
property figures of P-v
U?
and T-v?
LEARNING
OUTCOMES OF
CHAPTER II

Ideal gas? Compressibility How to get data

factor? from property
tables?
PURE SUBSTANCES
Has a fixed chemical composition throughout and can exist in
What?
more than one phase.

Examples - water (solid, liquid and gas), Nitrogen, Carbon

Examples
Dioxide, Helium, etc.

A mixture of various chemical elements or compounds also

Mixture of
qualifies as a pure substance as long as the mixture is
elements
homogeneous, such air ( 79% N2 and+ 21% O2).

A mixture of two or more phases of a pure substance is still a

Mixture of
pure substance as long as the chemical composition of all
phases
phases is the same such as a mixture of ice and liquid water.
 PHASES OF PURE SUBSTANCES
• Distinct molecular arrangement - homogeneous throughout and separated from
the others by identifiable boundary surfaces.
Phases? • A substance may have several phases within a principal phase, each with a
different molecular structure such as water (ice, water, steam).

Principal • Solid
• Liguid
phases • Gas / Vapour

• Compressed Liquid / Subcooled Liquid

Subsidiary • Saturated liquid
• Saturated vapour
phases • Saturated Mixture/ Sat. liquid-Sat. vapour Mixture
• Superheated Vapour

Molecular • Solid (closest  strongest) > Liquid > Gas (very far separated  weakest)
bond
 PHASE-CHANGE PROCESSES OF PURE SUBSTANCES

Pure substances PVT EOS

Pure substances such Relationship between

as water, refrigerant- P, V and T is very Those properties
134a and ammonia, complex and normally are visualized by a
are readily changing those thermodynamic function of
phases from SL and properties are in (P,v.T)=0, 
then to G and tables  Property Equation of state
generally do not Tables and visualized (EOS).
behave ideally. as Property Figures.

(b) P-v-T surface of a

(a) P-v-T surface of a substance that expands
substance that contracts on freezing (eg. Water)
on freezing
 EXAMPLE OF ASUMMARY
PHASE CHANGE FOR WATER
OF PROCESS 1-2-3-4-5

At saturated
temperature (Tsat),
State 4
water starts to State 2
Saturated
vaporize Saturated
vapour
(vaporization liquid
occurs).
State 5
Superheated
Tsat
vapour

State 1
Compressed Both liquid and vapour are in
State 2-4
liquid equilibrium @ the same T
Saturated and P
mixture

v2=vf v4=vg
 Heating process at constant P is
repeated at other constant P

Both lines meet at critical point and form

“steam dome”

Saturated liquid points

joined together 
Saturated liquid line
Saturated vapour points
joint together 
Saturated vapour line
CRITICAL POINT Above Tcr and Pcr  no significant
process of phase change occurs. V and
only one phase that similar to vapour
phase exists.

At critical points (Tcr, Pcr), sat. L

conditions are similar to those of sat. V
(Table A-1 lists critical data)
Along constant P lines T v Along constant T lines P v

T-v diagram of a pure substance P-v diagram for a pure substance

SIMILARITIES and DIFFERENCES ???

Which data easier to be generated?
P-V DIAGRAM THAT COMBINES ALL THE THREE PHASES (S,L,V)

(a) For a substance that contracts on (b) For a substance that expands on
freezing freezing
P-T OF PURE SUBSTANCE  PHASE DIAGRAM

𝑀𝑒𝑙𝑡𝑖𝑛𝑔/𝐹𝑢𝑠𝑖𝑜𝑛
𝑆 𝐿

Separates L 𝐹𝑟𝑒𝑒𝑧𝑖𝑛𝑔

and V
𝑉𝑎𝑝𝑜𝑟𝑖𝑠𝑎𝑡𝑖𝑜𝑛
Separates L 𝐿 𝑉
and V
𝐶𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑖𝑜𝑛

𝑆𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛
𝑉 𝑆

Separates S All the three phases are in equilibrium. For H2O:

and V 0.01oC and 0.6113 kPa
 PROPERTY TABLES
• Compiles complex data of thermodynamic properties for substances.
Property
Tables? • Tables A-4 until A-8 list T, P, v (specific volume), h (specific enthalpy), u (specific internal
energy), s (specific entropy)

Steam Tables • Property Tables for water

• ‘E’ refers to data of substances in ES unit.

Data in SI
and ES units • Eg. Tables A-6 and A-6E, respectively list properties of superheated vapour in SI and ES
units.

• Combination of internal energy, U, P and V: H = U + PV (kJ)

Enthalpy (H) • Enthalpy per unit mass  specific enthalpy: h = u + Pv (kJ/kg)
• Used to determine energy in and out of a control volume and in energy balance of a piston-
cylinder system that undergoes an isobaric process

• Thermodynamic property that relates to 2nd Law of Thermodynamics

Entropy (S) • Equals to heat transfer to a system divided by the temperature
• Entropy unit  kJ/K.
 PROPERTY
TABLES

SATURATED SUPERHEATED
ICE-WATER COMPRESSED SATURATED
LIQUID TABLE TABLE
VAPOUR TABLE TABLE
(Table A-8) (Table A-7) (Table A-6)

Temperature-
Pressure-based
based
( Table A-5)
(Table A-4)
 2 types of saturated tables (both give similar data but arranged
differently):
* Saturated Table based on T (Table A-4)
* Saturated Table based on P (Table A-5)

Subscripts used:
f = property for saturated liquid,
SATURATED g = property for saturated vapour, and
TABLES fg =the difference of similar property between sat. liquid and
sat. vapour (ufg =difference between ug and uf =ug-uf.

*hfg = enthalpy or latent heat of vaporization

= total energy required to vaporize a unit mass of saturated
liquid at a given T or P.
*hfg as T or P and hfg=0 @ critical point.
EXAMPLE OF SATURATED TABLES – TEMPERATURE BASED

First
column is T

Sat. pressure (Psat)

– pressure at
which liquid and sfg =sg-sf
vapour phases are
in equilibrium at ufg =ug-uf
given T

Enthalpy or latent heat of

vaporization hfg=hg-hf
 EXAMPLE OF SATURATED TABLES – PRESSURE BASED

First
column is P

Saturated
temperature (Tsat)
– temperature at
which liquid and
vapour phases are
in equilibrium at a
given P
Example of saturated tables – different data representation

Saturated
liquid
vf x 103
 QUALITY AND SATURATED REGION
Vaporization
• 2 phases exist in equilibrium, consisting a mixture of saturated liquid and saturated vapour.
• Ratio of saturated liquid and saturated vapour in the mixture  Quality
 0  x 1
 x  0  Saturated liquid

x  
mvapour mvapour mg
mliquid  mvapour m f  mg 
 x  1  Saturated vapour
mtotal

0  x  1  Saturated mixture

Quality
• Quality has significance for saturated mixtures only. No meaning in compressed liquid or superheated
vapor regions.
• Other terms to denote quality  dryness.
• Wetness / moisture content / humidity are opposite terms for quality.
• Properties of the saturated liquid are the same whether it exists alone or in a mixture with saturated vapor.
During the vaporization process, only the amount of sat. L or sat. V changes, not its properties.
 Average properties of mixtures
are always between the values of
the saturated liquid and the
saturated vapor properties:
yf y  yg

• To determine extensive property per unit mass within saturated region (Y = extensive property and y=Y/m = intensive
property):
yfg = yg - yf = difference of
y  y f  xy fg property y between saturated
vapour and saturated liquid

y can be represented
by v, u, h or s y  yf
Quality of x
saturated mixture y fg
SUPERHEATED VAPOUR TABLE

SUPERHEATED VAPOUR
Region to the right of the saturated vapor line and at
temperatures above the critical point temperature

TABLE

Table A-6 lists down the properties for superheated

vapour for water in which T and P are independent

Characterized by:
(1) Lower pressure (P < Psat at given T), or
(2) Higher temperature (T > Tsat at given P), or
(3) Higher values of other properties (y>yg at given P or T,
with y=v, h, u, s)
 EXAMPLE OF SUPERHEATED VAPOUR TABLE

Data in first row

represents the Tsat @ P
saturated
vapour
properties at
given P
 COMPRESSED LIQUID TABLE OF WATER
Table A–7  the only
Substance with its pressure > compressed liquid table for
Psat at a given temperature water. Not a common table for
 Compressed Liquid other substances

Data in Table A-7 starts at 5 MPa. For water,

data at P<5 MPa: Characterized by:
*For v, u and s : y  y f @ T (1) Higher pressure (P > Psat at given T), or
*Enthalpy of compressed liquid is highly (2) Lower temperature (T < Tsat at given P), or
dependent on P: (3) Lower values of other properties (y<yf at
h  h f @T  v f @T P  Psat@T  given P or T, with y=v, h, u, s)
 EXAMPLE OF COMPRESSED LIQUID TABLE

Tsat @ P
Format of Table A–
7 is similar to the
superheated vapor
tables, except the
saturated data
represent the
saturated liquid
properties
 ICE-SATURATED VAPOUR TABLE
T < triple point Properties of mixture

Saturated solid and saturated vapour Specific properties of V, U, H and S for a

are in equilibrium (Table A-8). mixture of sat. solid (ice) and sat. vapour:

yig  y g  yi

y  yi  xyig

0  x  1

x  mi gmg
m
Quality is defined (i=ice/sat.solid)   x  0  Saturated solid (ice)
 x  1  Saturated vapour

EXAMPLE OF ICE-SATURATED VAPOUR TABLE

Difference between
saturated vapour and
saturated solid (ice):
yig=yg-yi
 • TTsat or
COMPRESSED
LIQUID
• PPsat or
• yyf

• T=Tsat or
PHASE • P=Psat or
CONDITIONS SATURATED
MIXTURE
• y=yf, or
• y=yg, or
• yfyyg

• TTsat or
SUPEHEATED
VAPOUR
• PPsat or
• yyg
GUIDELINES FOR DATA
ACQUISATION FROM
PROPERTY TABLES
 DATA INTERPOLATION /
EXTRAPOLATION

INTERPOLATION EXTRAPOLATION

Performed when the

SINGLE
TRIPLE INTERPOLATION required data is beyond
INTERPOLATION
the listed data

Performed when the Performed when the required

required data is within data are between the four-
the two-listed data listed data

HORIZONTAL VERTICAL
INTERPOLATION INTERPOLATION
 SINGLE INTERPOLATION c

P or T a b c b
y d e f a

d e f
Values of a, c, d, e and f are
obtained from Property
Tables and value of b can b  a   e  d  c  a 
be determined from:   f  d 
 

Values of a, b, c, d and f are

found from Property Tables
and value of e can be
determined from:
 b  a 
ed   f d

 ca  
 TRIPLE INTERPOLATION
P P1 P P2
T
T1 a e b
T f y=?? g
T2 c h d

Horizontal interpolation
• f and g are firstly determined before calculating y.

 T  T1    T  T1    P  P1  
f a c  a ; g b d  b ; y  f  g  f 
 T2  T1   T2  T1   P2  P1 

Vertical interpolation
• e and h are firstly determined before calculating y.

 P  P1    P  P1    T  T1  
ea b  a ; hc d  c ; y  e h  e
 P2  P1   P2  P1   T2  T1 

Both ways should end up with the same value for y.

DATA EXTRAPOLATION
c
P or T a b c b
y d e f
a

d e f
If c to be determined:

 c  b    b  a   c  b    b  a   f  e
  
 f  e e  d    e  d  
 IDEAL-GAS EQUATION OF STATE
• Any equation that relates P, T and v of a substance.
Equation of State (EOS)
• Simplest EOS  ideal-gas equation

• The vapor phase of a substance  a gas when it is above the critical

Gas and vapour temperature.
• Vapor usually implies a gas that is not far from a state of condensation.

T 
P  R  or Pv  RT
Ideal Gas Equation v
• with, R = gas constant, P = absolute P, T = absolute T, and v = specific volume.

• 1) Forces between gas molecule are very weak

Assumptions
• 2) The volume of gas molecules are very small
GAS CONSTANT (R) VS UNIVERSAL GAS CONSTANT (RU)

Ru R value is different for each

R
Ru is similar for all gas
gas (Physical Constant
M (Table A-1) Table)

Pv  RT PV  NRuT
IDEAL GAS V
EQUATION P  RT P VN  RuT
m
PV  mRT Pv  RuT

P = absolute pressure (MPa or kPa) m = mass of gas (kg)

N = mole of gas (mol)
SYMBOLS v = molar specific volume (m /kmol)
3

M = molar mass or
T = absolute temperature (K)
molecular weight
Ru = 8.314 kJ/(kmol K) (kg/kmol)
COMPRESSIBILITY FACTOR
Gases deviate from ideal-gas behavior
significantly at states near the
saturation region and the critical point

Compressibility factor (Z) = deviation

from ideal-gas behavior at a given T
and P:
Pv
Z or Pv  ZRuT
RuT

Z=1  ideal gas

Z>1 or Z<1  real gases

Further away Z from unity  the more

deviation from ideal-gas behavior
 HOW TO OBTAIN Z FROM COMPESSIBILITY CHART?
Compressibility factor

• A function of reduced pressure, PR and reduced temperature TR:

T P Critical P (Table
Critical T (Table TR  and PR  A-1)
A-1) Tcr Pcr

• When P and v, or T and v, are given instead of P and T, Z can still be determined through pseudo-reduced specific
volume vR:
vactual
vR 
R Tcr Pcr

How to get Z data ?

• From the generalized compressibility charts in Figures A-15(a-b).
 OTHER EQUATIONS OF STATE

Van der  a 27 R 2Tcr2

Waals  P  2 
v  b  RT with a and b 
RTcr
 v  64 Pcr 8Pcr

RuT  c 
P  1  v  B  
A
Beattie- v2  vT 3  v2
Bridgeman  a  b
with A  Ao 1   and B  Bo 1  
 v  v

RuT  C  1 bR T  a a c   
Benedict- P   Bo RuT  Ao  o2  2  u 3  6  3 2 1  2 e  v2

Webb-Rubin v  T v v v vT  v 
SPECIFIC HEATS (CP, CV), INTERNAL ENERGY (U) AND ENTHALPY (H)

1st Law U H Specific heats

• Internal • For pure • Enthalpy (H or • The energy
energy, U substance such h) = the sum of required to
internal energy raise the
• Enthalpy, H as water, U
u, and temperature
from the
multiplication of a unit mass
property.
of pressure- of a substance
• For ideal gases, volume Pv by one
U can be degree.
determined H  U  PV
from the specific
heats. or
h  u  Pv
 TYPES OF SPECIFIC HEATS

Specific heat at constant V (Cv) Specific heat at constant P (Cp)

= energy required to raise the = energy required to raise the
temperature of the unit mass of a temperature of the unit mass of a
substance by one degree as the volume is substance by one degree as the pressure
maintained constant is maintained constant

Change in the internal energy of Change in the enthalpy of a

a substance per unit change in substance per unit change in
temperature at constant V: temperature at constant P:
 u   h 
Cv    CP   
 T  v  T  P

Units  kJ/(kg.K) = kJ/(kg.oC) (???)

Molar basis unit (ĈV and ĈP)  kJ/(kmoloC)= kJ/(kmol.K)
 ENTHALPY AND INTERNAL ENERGY OF IDEAL GASES

U for ideal gas Function of T only u  uT 

h  u  Pv 
Definition of enthalpy and
ideal gas Pv  RT 
 h  u  RT

The enthalpy of an ideal

Since R is constant and
u=u(T)
gas is also a function of h  hT 
T only

At given T  u, h, Cv and Cp
For an ideal gas, u and h Specific heats Cv and Cp
of an ideal gas have fixed
depend only on T also depend on T only
values regardless of v or P
 HOW TO DETERMINE U AND H FOR IDEAL GASES?
kJ kg 
2
du  CV (T ) dT   u  u2  u1   CV (T ) dT
integration
1

kJ kg 
2
dh  CP (T ) dT   h  h2  h1   CP (T ) dT
integration
1

An ideal gas undergoes 3 different

processes in the same temperature range: P
2a
• Process 1-2a: Constant volume
• Process 1-2b: P=a+bV, a linear relationship 2b
• Process 1-2c: Constant pressure
1 2c
All the 3 processes gone through by ideal T2
gases have same value of U and H:
T1
ua  ub  uc  1 CV (T )dT
2

V
ha  hb  hc  1 CP (T )dT
2
 HOW TO DETERMINE CP AND CV OF IDEAL GASES?
2 2

CV ,ave 

1
CV (T )dT
and CP ,ave 

1
CP (T )dT

Best average (T2  T1 ) (T2  T1 )

• Table A-2(c)  CP (kJ/kmol.K) as function of T (K) in the form of: CP = a + bT + cT2 + dT3

CV T1   CV T2  C T   CP T2 

CV ,ave  and CP ,ave  P 1 , or
Good average 2 2
T T
(CV,ave, CP,ave or CV or C P @ Tave  1 2
2
CV, CP at Tave )
• Table A–2(b) Cp and Cv (kJ/kg.K) for some common gases as function of T (K)

Cv ,ave  CV (300K ) and CP,ave  CP (300K)

Acceptable
average @ 300 K
• Table A-2(a)  Cp and Cv (kJ/kg.K) for common gases at 300 K
SPECIFIC HEAT RELATIONS OF IDEAL GASES
Replaced by ideal
Definition of
h  u  Pv
gas equation
enthalpy
DIFFERENTIATION

dh  du  d RT 
Replaced by
definition of Cp R, CP and CV have
and Cv units of kJ/kg.K
or on molar
basis: kJ/kmol.K.
CP dT  CV dT  RdT The specific heat
ratio k:

CP  CV  R or CP  CV  Ru CP
k
CV
Important relationship for ideal gases - enables
to determine
CV from CP and the gas constant R
 METHODS TO DETERMINE U AND H FOR ANY SUBSTANCE
(1) DATA FROM PROPERTY TABLES – EASIEST AND MOST ACCURATE

u  u2  u1 h  h2  h1

(2) USE CP AND CV RELATIONS AS A FUNCTION OF TEMPERATURE (CP=A+BT+CT2+DT3) AND (CP=CV+R)

T2 T2
h   CP (T )dT   (a  bT  cT 2  dT 3 )dT
T2 T2
u   CV (T )dT   (a  bT  cT 2  dT 3  R )dT T1 T1
T1 T1

(3) USE AVERAGE SPECIFIC HEATS

u   CV T dT  CV , aveT h   CP T dT  CP , ave T
T2 T2

T1 T1

CV T1   CV T2  C T   C P T2  T T

CV ,ave  and C P ,ave  P 1 OR CV ,ave and C P ,ave @ Tave  1 2
2 2 2
OR
CV ,ave  CV 300 K  or CV ,ave  C P 300 K 
INTERNAL ENERGY, ENTHALPY AND SPECIFIC HEATS OF SOLIDS AND LIQUIDS
Specific volumes of
Incompressible The constant-volume and
solids and liquids
substance = substance constant-pressure specific
essentially remain
whose specific volume heats are identical for
constant during a
(or density) is constant incompressible substances
process.

Specific heats of Specific heat values for

incompressible several common liquids
CV  CP  C
substances depend on T
only.
and solids are given in
Table A–3.
kJ kg.K 

du  CdT INTEGRATIO
 N
 u  Cave T2  T1 
HOW TO DETERMINE U AND H FOR LIQUIDS AND SOLIDS?

DIFFERENTIATION
h  u  Pv Definition of
enthalpy

dh  du  vdP  Pdv
dv=0 for
dh  du  vdP incompressible
substances
INTEGRATION

h  u  vP

SOLIDS (v0) LIQUIDS

h  u  Cave T2  T1  At const. P (P=0)

such as in heaters
At const. T (T=0)
such as in pumps

h  u  Cave T2  T1  h  vP

GUIDELINES FOR DATA
ACQUISATION OF A
SUBSTANCE
 Pure substances ?

H?
LEARNING How to illustrate phase
U? changes on property
OUTCOMES OF figures of P-v and T-v?
CHAPTER II

Ideal gas? Compressibility How to get data

factor? from property
tables?