- 1 -

Chapter 1

Review of Concepts

Thermodynamics is used to describe processes that involve changes in temperature,
transformation of energy, and the relationships between heat and work. The engineer has
to deal with problems that require calculation of heat and work requirements for physical
and chemical processes, determination of equilibrium conditions for chemical reactions
and for the transfer of chemical species between phases. For various unit operations,
Thermodynamics provides the equilibrium data and enthalpy data for design of
distillation columns, absorption columns, evaporators, condensers and other units where
heat exchange is involved. For unit processes, where chemical reactions are involved,
thermodynamics provide information regarding heat effects, maximum conversion, and
other parameters.

Thermodynamics: the study of interrelation of various physical properties ( such as
temperature, pressure, volume and entropy) and their relation to process properties ( sucj
as heat and work)

Chemical Engineering Thermodynamics: studies in particular the evaluation/
estimation of physical properties ( i.e energy, entropy) for a given setoff conditions
(usually temperature, pressure, composition) and their use in process calculations
(material & energy balances)

Fundamental concepts and notation

1. Mass & Moles :
mass = molecular weight x Moles
2. Temperature:
Fahrenheit T > -459.67,
Celsius T > -273.15 ToC = 5/9*(ToF-32)
Kelvin T>0 T9K) = ToC+273.15
Rankine T>0 T9oR) = 1.8 T(k) = T(of)+459.67
Note: Always we use absolute Temperature in thermodynamics.
3. Pressure
Simple definition is Force/area
P has various units : 1Pa = 1N/m2; 1kPa = 1000N/m2
1 bar = 100 kPa = 105N/m2
1 atm = 1.01325 bar
1 atm = 14.696 psia

4. Volume and Density
Actual volume is called the extensive or total volume V
t

Most thermodynamic equations use the molar volume V
V = V
t
/n ; V
t
= nV
Related quantity is Specific volume V = V
t
/m
Process Engineering Thermodynamics lecture notes winter 2011-12
- Only for slow performing students



- 2 -
Molar density is reciprocal of molar volume, and mass density is reciprocal of
specific volume. = 1/V

5. Energy

Matter can posses 3 basic forms of energy:
a) Kinetic energy calculated by motion of mass relative to reference frame, E =
mV
2
.
b) Potential energy Calculated by position of center of mass relative to reference
frame. E = mgh
c) Internal energy - Energy within the system, energies of the molecules in the
system relative to center of mass

There fore Total energy of the system

TE = (KE + PE)
macroscopic
+ IE
(due to translation, rotational and vibration of molecules)



6. Processes
Real processes occur due to imbalances in force ( driving force)

Driving/ Imbalanced physical forces Motion ( Momentum transfer)
Driving/ Imbalanced chemical forces Diffusion ( Mass transfer)
Driving/ Imbalanced thermal forces heat flow ( heat transfer)

Balanced forces no transfer (ie.) equilibrium
Infinitesimal forces infinitely slow transfer ( also called quasi- static)
Dissipative forces always work to retard process ( eg. friction)

Reversible process if quasi-static and no dissipative forces. Represent an
idealization that may/may not be approached.


7. Work
a. Resulting from a change in system

From Physics work = force x distance
dW = Force x dL
but pressure P = Force/Area
Force = Pressure x Area
There fore dW = Press x Area x dL
But Volume = area x Length ( note V
t
= nV)
dV
t
= area x dL
dW = Press x d(nV)

b. Work not associated with change in system Then it is refered as shaft work.



- 3 -

There fore Total work W = Ws + System- Change-work

Sign convention : Work done by the system means Positive
Work done on to the system means negative
If First law notation U = Q- W

8. Heat
The energy transfer that occurs when two objects at different temperatures come
in contact.
All energy exchanges between objects can be classified as either Heat or Work
dQ = T d(nS)


1.1 System
In order to deal with the subject in a rigorous manner, some of the basic concepts have to
be reviewed.

A thermodynamic system is any definite quantity of matter we are interested or
prescribed region of space enclosed by a boundary (fig 1.1) to which thermodynamic
analyses can be applied. The boundaries may be fixed or moveable. Work or heat can be
transferred across the system boundary.


Figure 1.1. Piston (boundary) and gas (system)

In a closed system, matter cannot cross the boundary. Hence the principle of the
conservation of mass is automatically satisfied whenever we employ a closed system
analysis.

When working with devices such as engines it is often useful to define the system to be
an identifiable volume with flow in and out. This is termed a control volume.



- 4 -

Fig 1.1a Sample control volume

1.2 Surroundings

Beyond the system, another part of the universe is the surroundings. Everything outside
the boundary is the surroundings. The surroundings contain all the ways by which one
can observe the system and make manipulations.

1.3 Boundary

The system and the surrounding may be separated by a boundary, which may be real like
a wall of a holding tank or imaginary like that we draw on paper (fig 1.1).
Different boundaries have different characteristics and it may influence the manipulations
and observations that can be made on the system.

1.4 Interactions between system and surroundings
To manipulate the system there has to be interactions between system and surrounding
through the boundary. These interactions cause change in matter or energy. Change in
amount of matter can be caused by bulk mode of transfer and diffusion mode of transfer.
Change in energy can be caused by thermal mode and work mode of interaction.

1.5 The Concept of a ``State''
The thermodynamic state of a system is defined by specifying values of a set of
measurable properties sufficient to determine all other properties. For fluid systems,
typical properties are pressure, volume and temperature. More complex systems may
require the specification of more unusual properties. As an example, the state of an
electric battery requires the specification of the amount of electric charge it contains.


1.5 Equilibrium state of a system
The condition of the system at a particular time is called state, such that if we change the
temperature, we change the state of the system. This also includes phase changes e.g.
changing liquid water at 100 deg C to steam at 100 deg C .In Thermodynamics focus is
mainly on equilibrium states.



- 5 -
Equilibrium means the state of a system in which properties have definite, unchanged
values as long as external conditions are unchanged is called an equilibrium state.
[Mechanical Equilibrium]

[Thermal Equilibrium]
A system in thermodynamic equilibrium satisfies:
1. mechanical equilibrium (no unbalanced forces)
2. thermal equilibrium (no temperature differences)
3. chemical equilibrium.
1) mechanical equilibrium : there is absence of any net driving force for bulk mass
transfer of for change in system volume this means here (ie.) balance of system pressure
P with surrounding pressure or P
ext

P = P
ext

2) Thermal equilibrium: That means there is no driving force for causing thermal
interaction. The system temperature will be same as surrounding temperature.
3) Diffusional equilibrium:
This means absence of net driving forces for causing diffusional mass transfer.

1.6 Intensive and extensive properties
The thermodynamic state of a system is defined by specifying values of a set of
measurable properties. For fluid systems, typical properties are pressure, volume and
temperature. Properties may be extensive or intensive. Extensive properties depend on
the quantity of matter in the system. Thus, if the system is divided into a number of sub-
systems, the value of the property for the whole system is equal to the sum of the values
for the parts, e.g. volume. Intensive properties do not depend on the quantity of matter
present, e.g. temperature and pressure. Specific properties are extensive properties per
unit mass, e.g. specific enthalpy, molar volume. Specific properties are intensive because
they do not depend on the mass of the system. Properties describe states only when the
system is in equilibrium. Changes in property values depend only on the initial and final



- 6 -
value of the state and not on the path taken. Hence properties are also called state
functions.

1.7 Process
The state of a system can be changed from the initial state to the final state by applying a
process through the available interactions fig (1.2).

Fig 1.2
Just as a system has a set of quantities for identifying its state, so does a process have a
set of variables called process variables for monitoring the progress and characterizing
its behavior, e.g. P
ext
, work, Heat. They are not state functions. The nature of the systems
boundary can limit the kind of processes that we can apply.
Boundary Process
Open
Insulated
Rigid
Closed
Isolated
Any mass transfer or energy transfer possible
Adiabatic(no thermal interaction)
Isometric( no volume change)
No bulk or diffusional mass transfer
No mass or energy interaction


The succession of states through which the system passes defines the path of the process.
If, at the end of the process, the properties have returned to their original values, the
system has undergone a cyclic process or a cycle. If a system and surroundings can be
returned to its original state, then the process is a reversible process. If the state of the
surroundings has changed then the process is an irreversible process. All real life
processes are irreversible.

1.8 Changing the state through heat, work
The state of a closed system can be changed by interaction with the surrounding through
heat and work which are two different ways of energy transfer. Heat (denoted by Q)
is energy transferred because of differences in temperature. Heat is identified as it comes
across system boundaries.
Any other means for changing the energy of a system is called work (denoted by W).
There are push-pull work (e.g. in a piston-cylinder, lifting a weight), electric and
magnetic work (e.g. an electric motor), chemical work, surface tension work, elastic
work, etc. In defining sign convention for heat and work, we focus on the effects that the
surroundings has on the system. Thus we define heat (Q) and work (W) as being positive
when transferred to the system.



- 7 -

1.9 State functions and path functions
Consider at system at an initial state 1 undergoes a process & goes to a final state 2.(Fig
1.2) Since T, P are properties, changes will be the difference between the initial and final
values.
T = T
2
T
1
P = P
2 -
P
1

If the process proceeds by a sequence of differential steps, then we can write
T dT
T
T
=

2
1

Differentials following this are called exact differentials. Their integrals give changes,
whose values depend only on the initial and final values and are independent of the
integration path. dT refers to differential change in T. All properties are exact
differentials. And hence they are also called state functions. A state function is one
whose change on going from initial to final is independent of the route taken. In a cyclic
process the change in the state function will be zero.
In contrast process variables like work W do not form exact differentials. For a process
variable dW represents a small amount of work, not change, because work is not a
property of the system.,
If dW is integrated over the entire process, we get the total amount of work involved in
the process.
W dW =

2
1

If the change in a function is dependent on the route taken, then the function is known as
a path function. Some familiar path functions are work, heat.

1.10 The phase rule
For multi phase systems at equilibrium, the number of independent variables that must be
specified to establish its intensive state is given by Gibbs phase rule.

N F + = 2

Is the number of phases (a phase is a homogeneous region of matter e.g. gas, mixture
of gases, liquid, crystalline solid etc), N is the number of chemical species and F is the
degrees of freedom of the system. For a pure homogeneous fluid=1, =1, therefore F=2.
The state of the pure homogeneous fluid is fixed whenever two intensive thermodynamic
properties are set.

1.11 Internal energy
Internal energy (denoted by U
t
) refers to the kinetic and potential energy changes
associated with molecules and intermolecular forces. Because of their ceaseless motion,
all molecules possess kinetic energy of rotation, vibration, potential energy resulting from
intermolecular forces, bond energy, etc. This form of energy is named internal energy to
distinguish it from the kinetic and potential energy of the system resulting from its



- 8 -
macroscopic position or motion. Absolute values of internal energy cannot be measured,
only changes from one state to another. Addition of heat or work to a substance increases
the molecular activity, which in turn increases the internal energy. Specific internal
energy, represented as
m
U
or
n
U
U
t t
= where n and m are the number of moles or mass of
the system is an intensive property.

1.12 The first law of thermodynamics ( Conservation of Energy)
One formal statement of the first law of thermodynamics is that although energy assumes
many forms, the total quantity of energy is constant, and when energy disappears in one
form, it appears simultaneously in other forms.
(energy of system) + (energy of surrounding) =0
( Note: Energy (like mass) can be neither created nor destroyed)

For a closed system, the total energy change equals the net energy transferred into it as
heat and work from the surrounding.
(nU) = n(U)=Q + W
U is the change in the internal energy per unit mass or mole of the system. The quantity
Q is defined as the heat absorbed by the system from the surroundings. The quantity W is
defined as the amount of work done on the system by the surroundings.

Ex 1.1
When a system is taken from state a to state b (ref fig) along path acb, 120 J of heat flows
into the system and the system does 50 J of work.

(a) How much heat flows into the system along path aeb if the work done by the
system is 30J?
(b) The system returns from b to a along path bda.If the work done on the system is
40 J, does the system absorb or liberate heat? How much?




Sol :




- 9 -
Assume that the system changes only in the internal energy.
(a) Applying 1
st
law,
acb acb
t
ab
W Q U + = = 120-50=70J
Since U is a state function
t
adb
t
aeb
t
acb
U U U = =

aeb aeb
t
aeb
W Q U + =
30 70 = + =
aeb aeb aeb
Q W Q
J Q
aeb
100 =
(b) For path bda,
40 70 + = + = = =
bda bda bda
t
bda
t
adb
Q W Q U U
J Q
bda
110 40 70 = =
Heat is therefore transferred to the surroundings from the system.

1.13 Enthalpy
Enthalpy is equivalent to the sum of the internal energy of the system plus the product of
its volume multiplied by the pressure exerted on it by its surroundings. So, enthalpy H =
U + PV. Its value is determined by the temperature, pressure, and composition of the
system at any given time.

1.14 Specific heat

The specific heat of a substance is the amount of energy required to raise the temperature
of 1 kg of the substance by 1 C. For gases and vapors, which expand when heated, the
specific heat depends on how the substance is heated.

The specific heat or molar heat capacity at constant volume C
v
is found by keeping the
volume of the system constant during heating.

V
v
T
U
C

= depending on whether U is the molar or specific internal energy.

For the constant volume process, the above can be written as dU = C
v
dT
Integrating,

=
2
1
T
T
v
dT C U

Applying the first law for a mechanically reversible constant volume process in a closed
system,
dT C n U n Q
T
T
v

= =
2
1






- 10 -
The specific heat or molar heat capacity at constant pressure C
p
is found by keeping the
pressure of the system constant during heating.

P
P
T
H
C

=
For the constant pressure process, the above can be written as dH = C
P
dT
Integrating,

=
2
1
T
T
P
dT C H
Applying the first law for a mechanically reversible constant pressure process
In a closed system
dT C n H n Q
T
T
P

= =
2
1


Ex 1.2
Liquid water at 180 C and 1002.7 kPa has an internal energy of 762 kJ/kg and a specific
volume of 1.128 cm3/gm.
What is its enthalpy?
The water is brought to the vapor state at 300 C and 1500 kPa where its internal energy
is 2784.4kJ/kg and its specific volume is 169.7 cm
3
/gm. Calculate U and H for the
process.

Sol :
(a) U
1
=762 kJ/kg, P
1
=1002.7kPa, v
1
=1.128 cm3/g
1 cm3 = 10
-6
m3 , 1 g = 10
-3
kg
v
1
= 1.128 (10
-6
)/10
-3
m3)/kg = 1.128(10
-3
)m3
H
1
= U
1
+ P
1
v
1
= 762 +(1002.7) (1.128x10-3)
= 763.13kJ/kg

(b) U
2
=2784.4 kJ/kg, P
2
=1500kPa, v
2
=169.7 cm3/g
v
2
= 169.7 (10-6)/10-3m3)/kg = 169.7(10-3)m3
H
2
= U
2
+ P
2
v
2
= 2784.4 +(1500)(169.7x10-3)
= 3037.5 kJ/kg

U = U
2
-U
1
= 2784.4 - 762 = 2022.4 kJ/kg
H = H
2
-H
1
= 3037.5 - 763.13 = 2274.37 kJ/kg

Tutorial 1

1) Define a thermodynamic system?
2) What is a process?
3) Classify the following properties as intensive and extensive: volume, pressure,
temperature, specific volume, internal energy, and molar mass, mass.
4) How many degrees of freedom have each of the following systems?
a) Liquid water in equilibrium with its vapor



- 11 -
b) Liquid water in equilibrium with a mixture of water vapor and nitrogen
c) A liquid solution of alcohol in water in equilibrium with its vapor
d) A system comprising of chloroform, 1,4-dioxane and ethanol in a two phase
system .
5) One mole of gas in a closed system undergoes a four step thermodynamic cycle. Use
the data given in the following table to determine numerical values for the missing
quantities.










6) In the following take C
v
= 20.8 and C
p

= 29.1 Jmol
-1
C
-1
for nitrogen gas:
a) Three moles of nitrogen at 30 C ,
contained in a rigid vessel, is heated to 250
C. How much heat is required if the vessel
has a negligible heat capacity? If the vessel weighs 100 kg and has a heat capacity of
0.5kJkg
-1
C
-1
, how much heat is required?
b) Four moles of nitrogen at 200 C is contains in a piston/cylinder arrangement. How
much heat much be extracted from this system, which is kept at constant pressure to cool
it to 40 C if the heat capacity of the piston and cylinder is neglected?
Step U
t
(J) Q(J) W(J)
1-2
2-3
3-4
4-1
-200
?
?
4700
?
-3800
-800
?
-6000
?
300
?
1-2-3-4-1 ? ? -1400



- 15 -
Chapter 2

PVT behavior of pure substances

The heat and work flows on to a system depend on the thermodynamic properties such as
enthalpy and internal energy. For example, the heat required to change the temperature
of 1 kg water by 10 degrees will be different from that needed to change the temperature
of one kg of air by 10 degrees. For fluids these properties are evaluated from
measurements of molar volume as a function of temperature and pressure. The
relationship between pressure (P), molar volume (V) and temperature (T) may be
expressed mathematically as equations of state. E.g. PV=RT gives a simple realistic
model of fluid behaviour. Equations of state are useful in metering of fluids, sizing of
vessels and pipelines. The behaviour of a pure substance can be expressed in terms of
PVT diagrams. Understanding of phase diagrams is essential to thermodynamics because
there will be many occasions in which reference to a phase diagram (or a tabular
representation of one) is essential in order to obtain needed property information.


2.1 Schematic representation of P T relation for a pure fluid
PT diagram is actually the projection of the 3 d PVT diagram shown in the below
figure.



Fig 2.1
On the PVT diagrams, one phase situations, solid (s), liquid (L), vapour (Va) appear as
areas. Applying Gibbs phase rule, two variables (P, V) or (T, V,) or (P, T) will be
required to identify the state. In addition to solid, liquid and vapour phase, the graph also
depicts fluid and gas which are liquid and vapour states extended to high temperatures.



- 16 -
The two phase lines for solid - liquid, solid vapour and liquid- vapour appear in pairs as
shown in the figure. The lines for solid liquid equilibrium are the melting curves and are
separated by the region marked S +L. The two melting curves are parallel and never
intersect. The lines for solid vapour equilibrium are the sublimation curves and are
separated by the region marked S + Va . The lines for vapour liquid equilibrium are
branches of the vapour pressure curve and are separated by the region marked L + Va.


All three of the two-phase regions collapse to single lines or curves in the PT diagram
(fig 2.2). This is because coexisting phases always exist at the same temperature and
pressure. So, on a PT diagram the infinite number of mixtures of liquid and vapour that
could coexist at a particular pressure and temperature will all collapse onto a single PT
point along a curve.

Fig 2.2
Measurements of the vapour pressure of a pure substance both as a solid and liquid lead
to pressure versus temperature curves shown by lines 1-2 and 2-C in the figure 2.2. The
third line 2-3 gives the solid/liquid equilibrium relationship.Line1-2 the sublimation
curve separates the solid and gas regions. Line 2-3 the fusion curve separates the solid
and gas regions. Line 2-C, the vaporisation curve separates the liquid and gas regions.
All three lines meet at the triple point where the three phases coexist in equilibrium .The
vaporization curve 2-C terminates at point C ,the critical point, the coordinates being
critical pressure P
c
and the critical temperature, T
c
the highest pressure and temperature at
which a pure species can exist in vapour/liquid equilibrium. The vaporisation curve does
not give any information about where inside the two phase region this state lies - it could
be saturated liquid, saturated vapour or any one of the infinite number of mixtures of
liquid and vapour between the two. Changes of state may be represented by lines on the
PT diagram: an isothermal change by a vertical line; an isobaric change by a horizontal
line.

2.2 PV diagram



- 17 -
If a projection is made from the 3D surface onto a plot of pressure versus volume, a PV
diagram is obtained (fig 2.3). One phase states occupies areas, two phase estates occupy
lines and the solid - liquid - vapour equilibrium point projects as three points.


Fig 2.3
On the P V diagram, the two phase lines appear in pairs for although, the phases are in
equilibrium at the same T and P, the two phases have different molar volumes. These two
molar volumes can be connected by tie lines. Every tie line is at one particular
temperature and pressure. An infinite number of tie lines exist. Each melting line extends
without limit to high pressures. The two branches of the vapour pressure curve coincide
at a maximum pressure which identifies the critical point.
Three isotherms are also shown in the graph: a supercritical isotherm (T>T
c
), critical
isotherm (T=T
c
), sub critical isotherm (T<T
c
). The critical point passes through a point of
inflection at the critical point, thus defining the critical point as
0 =

=
c
T T
v
P
, 0
2
2
=

=
c
T T
v
P


2.3 Mathematical representation of PVT behaviour
The most convenient method of representing the PVT behaviour of a substance as a
single phase, is through the mathematical expression called PVT equation of state.
0 ) , , ( = T V P f .
An equation of state may be solved for any one of the three quantities P, V or T as a
function of the other two.
If V is considered as a function of T and P, That is, ) , ( P T V V = ,



- 18 -
dP
P
V
dT
T
V
dV
T P

=
The above partial derivatives have definite physical meanings and are related to two
properties commonly tabulated for liquids and defined as follows.
Volume expansivity,
P
T
V
V

=
1

Isothermal compressibility,
T
P
V
V

=
1

As seen from fig 2.3, the isotherms for the liquid phase are very steep and closely spaced.
Thus both and are very small. For idealized case of incompressible fluid, and are
zero. Hence no equation of state can be written for an incompressible fluid as V is
independent of T and P.
Hence, dP dT
V
dV
=
For small changes in T and P, and may be taken constant.
Hence, ) ( ) ( ln
1 2 1 2
1
2
P P T T
V
V
=

Ex 2.1

For acetone at 20
0
C and 1 bar,
=1.487x10
-3
C
-1
,=62x10
-6
cm
3
g
-1
,V=1.287cm
3
g
-1 .
Find
a) The pressure generated when acetone is heated at constant volume from 20
0
C and 1 bar
to 30
0
C.
b) The volume change when acetone is changed from 20
0
C and 1 bar to 0
0
C and 10 bars.



Solution:

a).
) ( ) ( ln
1 2 1 2
1
2
P P T T
V
V
=
0= ( ) ( ) ) tan (
1 2 1 2
V t cons P P T T
( ) ( )
bar P P
bar
x
x
T T P P
241 240 1 240
240 ) 10 )( 24 ( ) 20 30 (
10 2 . 6
10 487 . 1
1 2
5
3
1 2 1 2
= + = + =
= =

b).




- 19 -
0303 . 0 ) 9 )( 10 62 ( ) 20 )( 10 487 . 1 ( ln
6 3
1
2
= =

x x
V
V

g cm V V V
g cm V
V
V
/ 038 . 0 287 . 1 249 . 1
/ 249 . 1 ) 287 . 1 )( 9702 . 0 (
. 9702 . 0
3
1 2
3
2
1
2
= = =
= =
=




2.4 Virial equations of state
Isotherms for gases and vapors lying on the right of fig 2.3 are simple curves for which
V increases as P decreases. The product PV can be expressed as a power series in P:
......
2
+ + + = cP bP a PV
If
' '
, aC c aB b = = ,
......) 1 (
3 ' 2 ' '
+ + + + = P D P C P B a PV
where etc C B a , , ,
' '
are constants for a given temperature and chemical species.

It has been shown experimentally that a is the same function of temperature for all
species and an be taken as a=RT
The above equation can be written as
......) 1 (
3 ' 2 ' '
+ + + + = P D P C P B RT PV

Define
RT
PV
Z = called compressibility factor. With this definition and with a=RT, the
above equation reduces to
........ 1
2 ' '
+ + + = P C P B Z
An alternate expression for Z is also in common use:
...... 1
2
+ + + =
V
C
V
B
Z
Both the above equations are known as virial expansions and the parameters B,C,D and
B,C,D are called virial coefficients.
It can be shown that
( )
2
2
' , '
RT
B C
C
RT
B
B

= =

The accuracy required determines the number of terms that are kept -- more terms makes
the equation more accurate, but also more complicated to work with. Virial coefficients
are different for each gas, but other than that are functions of temperature only.
Coefficients are normally obtained by making measurements of P, V, and T, and fitting
the equation.

2.5 The ideal gas



- 20 -
The internal energy of a real gas is a function of pressure and temperature(phase rule).
This pressure dependency arises as a result of forces between the molecules. If such
forces do not exist, no energy would be required to alter the average intermolecular
distance, and therefore no energy would be required to bring about volume and pressure
changes in a gas at constant temperature. In the absence of molecular interactions, the
internal energy of a gas depends on temperature only. These considerations of the
behaviour of an ideal gas in which no intermolecular forces exist and of a real gas in the
limit as pressure approaches zero lead to the definition of an ideal gas.

Because the terms B/V, C/V
2
, etc of the virial expansion arise on account of molecular
interactions, the virial coefficients B,C etc would be zero if there were no such
interactions and the virial expansion would reduce to that for an ideal gas.
Z=1 or PV =RT

The ideal gas is only a model fluid that is useful because it is described by simple
equations applicable as good approximation for actual gases. In engineering calculations,
gases at very low pressures up to a few bars may be considered ideal.

2.6 Implied property relations for an ideal gas:
The definition of heat capacity at constant volume leads for an ideal gas to the conclusion
that C
v
is a function of temperature only.
C
v

=
dT
dU
T
U
v

=C
v
(T)
The defining equation for enthalpy, applied to an ideal gas leads to the conclusion that
enthalpy H also is a function of temperature only.
H= U+PV
= U(T)+RT= H(T)
The heat capacity at constant pressure C
p
is a function of temperature only:
C
p
( )
dT
T dH
T
H
p
=

=
= C
p
(T)
A useful relation between C
p
and C
v
for an ideal gas is obtained from above.
C
p R
dT
dU
dT
dH
+ = =
= C
v
+ R
The above relation shows that C
p
and C
v
vary with temperature for an ideal gas in such a
way that their difference is equal to R.

For any change of state for an ideal gas, the above equations lead to
U=C
v
dT
H=C
p
dT



2.7 Equations for process calculations for ideal gases
The processes considered are mechanically reversible closed system processes.
a) The constant-volume process (isometric process)



- 21 -
Change in internal energy between two states is given by:
dT C U
V

= , dT C H
P

= = 0 PdV W
By 1
st
law , dT C U Q
v

= =
Q is the quantity of heat added to the system.
b) The constant-pressure process (isobaric process)
dT C U
V

= dT C Q H
P

= =
dT C Q
p

= ) (
1 2
T T R W =
By 1st law, dT C H Q
p

= =
c) The constant-temperature (isothermal process)
The internal energy of an ideal gas does not change in an isothermal process.
0 = = H U

=
1
2
1
2
ln ln
V
V
RT
P
P
RT Q

=
1
2
1
2
ln ln
P
P
RT
V
V
RT W

d) The adiabatic process:
1
1
]
1

|
|

\
|

=
1
1
]
1

|
|

\
|

=
|
|

\
|
=
|
|

\
|
=
= =
=

1
1
2 1
1
1
2 1 1
1
1
2
1
2
1
1
2
2 2 1 1
1
1
1
1
,
tan
tan
P
P RT
P
P V P
W
by given is process adiabatic an of Work
P
P
V
V
T
T
Hence
t cons V P V P
t cons PV


e) The irreversible process
The above equations which give property changes U, H are valid for ideal gases
whether the process is reversible or irreversible., in both closed and open systems as the
change in properties depend only on the initial and final states of the system. On the other
hand, Q and W depend on the process.
The work of an irreversible process is calculated by a two step procedure:
i) W is determined for a mechanically reversible process that accomplishes the
same change of state as the actual irreversible process.
ii) The above result is multiplied or divided by the efficiency.





- 22 -
Ex 2.2
Air is compressed from an initial condition of 1 bar and 25
0
C to a final state of 5 bar and
25
0
C by three different mechanically reversible processes.
(a)Heating at constant volume followed by cooling at constant pressure;
(b)Isothermal compression;
(c)Adiabatic compression followed by cooling at constant volume.

At these conditions, air may be considered an ideal gas with the constant heat capacities
C
V
=20.785
K mol
J
.
=(5/2) R C
P
=29.099
K mol
J
.
= (7/2) R.=8.314J/mol K
Calculate the work required, heat transferred, and the changes in internal energy and the
enthalpy of air for each process.
Solution:
Basis : 1 mol of air
Applying ideal gas law,
3
5
1
1
1
02479 . 0
10 1
15 . 298 314 . 8
m
x
x
P
RT
V = = =
Similarly, we get,
3
2
004958 . 0 m V =
As T is the same in the initial and final state.
0 = = H U in all the three cases
(a) For constant volume process,
2
2
1
1
T
P
T
P
=
K
P
T P
T 75 . 1490 ) 15 . 298 )( 5 (
1
1 2
2
= = =
For constant volume process, ) 0 , (sin = = = W ce T nC U n Q
V

=(20.785)(1490.75-298.15)= 24788 J.
J T C H
P
34703 ) 15 . 298 75 . 1490 )( 099 . 29 ( = = = /mole
W=0
For the second step at constant pressure,

J Q U W
mole J T C U
J T C H Q
V
P
9915 ) 34703 ( 24788
/ 24788 ) 75 . 1490 15 . 298 )( 785 . 20 (
34703 ) 75 . 1490 15 . 298 )( 099 . 29 (
= = =
= = =
= = = =

Hence for the entire process,
J W
J Q
H
U
9915 9915 0
9915 34703 24788
0 34703 34703
0 24788 24788
= + =
= =
= =
= =

(b) for the isothermal compression of an ideal gas,



- 23 -
( ) J
P
P
nRT W Q Hence
H U
3990
1
5
ln ) 15 . 298 )( 314 . 8 ( ln ,
0
1
2
= =
|
|

\
|
= =
= =

(c) Adiabatic compression:

The initial step of adiabatic compression takes the air to its final volume of
0.004958 m
3
. The temperature T at this point is:

J W
mole J T C H
mole J T C U
U W
Hence
Q step this For
K
V
V
T T
P
V
5600
/ 7840 ) 15 . 298 57 . 567 )( 099 . 29 (
/ 5600 ) 15 . 298 57 . 567 )( 785 . 20 (
,
. 0 ,
57 . 567
004958 . 0
02479 . 0
) 15 . 298 (
4 . 0
1
2
1
1
'
=
= = =
= = =
=
=
=

=



For the second step,

W=0 (constant volume).

mole J T C H
J T C U Q
P
V
/ 7840 ) 57 . 567 15 . 298 )( 099 . 29 (
5600 ) 57 . 567 15 . 298 )( 785 . 20 (
= = =
= = = =


Hence for the entire process,

J W
J Q H U
5600 0 5600
5600 5600 0 0 7840 7840 0 5600 5600
= + =
= = = = = =


The following figure shows these processes sketched on a PV diagram.



- 24 -



Ex 2.3
An ideal gas undergoes the following sequence of mechanically reversible processes in a
closed system:
(a)From an initial state of 70 C and 1 bar, it is compressed adiabatically to 150 C.
(b)It is then cooled from 150 to 70 C at constant pressure.
(c)Finally it is expanded isothermally to the original state.
Calculate W, Q, U and H for each of the three processes and for the entire cycle.
Take R C R C
p v
2
5
,
2
3
= = . If the processes are carried out irreversibly, but so as to
accomplish exactly the same changes of state the same changes of state in P, T, U and
H, then different values of Q and W result. Calculate Q and W if each step is carried out
with an efficiency of 80 %. R=8.314 J mol
-1
K
-1

Sol:
Basis: 1 mol of gas
The cycle is shown on a PV diagram below

(a) For the adiabatic compression process, Q = 0;

( )( )
( )( ) mole J T C H
mole J T C U
p
v
/ 1663 70 150 785 . 20
/ 998 70 150 471 . 12
= = =
= = =




- 25 -
Applying 1
st
law, W= U=998 J
Pressure P
2
is found
1
1
2
1 2

T
T
P P =( )
5 . 2
273 70
273 150
1

+
+
=1.689 bar

(b) For the constant pressure process,
( )( )
( )( ) mole J T C H
mole J T C U
p
v
/ 1663 150 70 785 . 20
/ 998 150 70 471 . 12
= = =
= = =

Q= H= -1663 J
W=U-Q = -998 (- 1663) = 665 J
(c) For ideal gases undergoing an isothermal process, U and H are zero;

= =
1
2
1
2
ln ln
P
P
RT
P
P
RT W Q = ( )( ) J 1495
1
689 . 1
ln 15 . 343 314 . 8 =

For the entire cycle,

Q= 0-1663+1495=-168 J
W=998+665-1495=165 J
U=998-998 +0=0
H=1663-1663 +0 =0


a) If the property changes above are carried out irreversibly, for mechanically reversible
adiabatic compression=998 J. If the process is 80 % efficient= 998/0.8=1248 J. This step
cannot be adiabatic
By the 1
st
law, Q= U-W= 998-1248 = -250J
b) The work for the mechanically reversible cooling process is 665 J. For the reversible
process, W=665/0.8=831 J
Q= U-W = -998 - 831= -1839 J
c) As work is done by the system in this step, the irreversible work in absolute value will
be less than the reversible work of -1495 J
W= (0.8)(-1495)= -1196 J
Q= U-W = 0 + 1196 = 1196 J

For the entire cycle U and H are zero with Q = -250 -1829+1196=-883 J
W = 1248 +831 -1196 = 883 J


2.8 Applications of the virial equations
At temperatures below critical temperatures and low to moderate pressures, the ideal gas
equation ceases to apply. Under these conditions, you must deal with "real" gases.
Real gases require more complex equations of state than do ideal gases , one of some of
them being virial equations of state .
The two forms of the virial equations are infinite series. Reasonably close values



- 26 -
are realized when two or three terms are used for gases and vapours at low to moderate
pressures. As with the ideal gas equation, the temperatures and pressures used must be
absolute.


Ex 2.4
Reported values for the virial coefficients of methyl chloride at 125 C are B = - 207.5
cm
3
mol
-1
and C = 18200 cm
6
mol
-2
.Calculate V and Z for methyl chloride at 125C and
10 bar by
a) The ideal gas equation
b) Virial equation
RT
BP
1
RT
PV
Z + = =
c) virial equation
2
V
C
V
B
1
RT
PV
Z + + = =
The absolute temperature is T = 398K and the appropriate value of the gas constant is R
= 83.14 cm
3
bar

mol
-1
K
-1
Sol :
a) By Ideal gas equation,
V
( )( )
10
398 14 . 83
P
RT
= = = 3308.972 cm
3
.mol
-1
Z=1

(b) Z
RT
BP
1
RT
PV
+ = =

V

+ =
RT
BP
1
P
RT
= B
P
RT
+ = 3308.972 207.5= 3101 cm
3
mol
-1


( )( )
( )( ) 398 14 . 83
3101 10
RT
PV
Z = = =0.937

c) To facilitate iteration, write equation
2
V
C
V
B
1
RT
PV
Z + + = = as

+ + =
+
2
i i
1 i
V
C
V
B
1
P
RT
V

For the first iteration, i=0,

+ + =
2
0 0
1
V
C
V
B
1
P
RT
V , take 3309.97 V
0
= cm
3
mol
-1

V
1
( )( )
( )

+ =
2
97 . 3308
18200
97 . 3308
5 . 207
1
10
398 14 . 83


= 3106.97 cm
3
mol
-1




- 27 -

V
2

+ + =
2
1 1
V
C
V
B
1
P
RT



( )( )
( )

+ =
2
97 . 3106
18200
97 . 3106
5 . 207
1
10
398 14 . 83


= 3094.22 cm
3
mol
-1

Iteration continues until the difference V
i+1
-V
i
is insignificant

+ + =
2
2 2
3
V
C
V
B
1
P
RT
V

( )( )
( )

+ =
2
22 . 3094
18200
22 . 3094
5 . 207
1
10
398 14 . 83

= 3093.36 cm
3
mol
-1

+ + =
2
3 3
4
V
C
V
B
1
P
RT
V

( )( )
( )

+ =
2
36 . 3093
18200
36 . 3093
5 . 207
1
10
398 14 . 83

= 3093.30 cm
3
mol
-1


V = 3093.30 cm
3
mol
-1
from which Z = 0.934


2.9 Cubic equations of State
Virial equations cannot represent thermodynamic systems where both liquid and vapor
are present. A "cubic" equation of state is needed to do this. One such is the Vander
Waals equation and the Redlich Kwong equation.

Van der Waals equation

In real gases, the molecules occupy some space and so the actual volume available for the
movement of the molecules is (V-b) where b is the correction for the volume occupied by
the molecules. Similarly the velocity of a molecule about to strike the wall of the
container is reduced due to attractive forces of the neighboring molecules. Since pressure
is a direct consequence of the velocity with molecules strike the container walls,
attractive forces decreases pressure.

This reduction in pressure is equal to
2
v
a
.




- 28 -
( ) b V
V
a
P

+
2
=RT

Imposing mathematical conditions at the critical point, parameters a and b can be
determined.

P
c
=

c
c
V
RT
8
3


a
c
2
c
2
64P
T 27R
=

b =
c
c
8P
RT



c
c c
c
RT
V P
Z =

Redlich/Kwong equation :
Another two parameter real gas equation is the Redlich-Kwong equation. It is almost
always more accurate than the van der Waals equation and often more accurate than some
equations with more than two parameters. The Redlich-Kwong equation is
P
( )
( )( )( ) b V V T
a
b V
RT
+

=


( )
c
c
P
T R
a
2 2
42748 . 0
=



( )
c
c
P
RT
b
08664 . 0
=





2.10 Theorem of Corresponding States : Acentric Factor

Experimental observation shows that compressibility factors Z for different fluids exhibit
similar behavior when correlated as a function of reduced temperature T
r
and reduced
pressure P
r
;

By definition
c
r
T
T
T = and
c
r
P
P
P =



- 29 -

These dimensionless thermodynamic co-ordinates provide the basis for the simplest form
of the theorem of corresponding states:

All fluids, when compared at the same reduced temperature and the reduced
pressure, have approximately the same compressibility factor (Z) , and all
deviate from ideal gas behavior to about the same degree.

Corresponding-states correlations of Z based on this theorem are called two-parameter
correlations, because they require use of the two reducing parameters T
c
and P
c
. Although
these correlations are very nearly exact for the simple fluids (argon, krypton and xenon)
systematic deviations are observed for more complex fluids. Appreciable improvement
results from introduction of a third corresponding states parameter (in addition to T
c
and
P
c),
characteristic of molecular structure;

the most popular such parameter is the acentric
factor , introduced by K.S.Pitzer and coworkers.

The basic premise of the three parameter theorem of corresponding states can be
written as

All fluids, having the same value of , when compared at the same reduced
temperature and the reduced pressure, have approximately the same
compressibility factor (Z) , and all deviate from ideal gas behavior to about the
same degree.




2.11 Generalised correlation for gases:
Equations of state that express Z in terms of T
r
and P
r
are said to be generalised because
of their general applicability to all gases and liquids. Generalised correlations find
widespread use. Most popular are the correlations developed by Pitzer and co-workers for
the compressibility factor Z and for the second and third virial coefficients B, C.
Pitzer correlation for the compressibility factor Z:
Z = Z
0
+ Z
1


Z
0
and Z
1
are functions of both T
r
and P
r.
When

=0, as is the case for simple fluids,
the second term disappears, and Z
0
becomes identical with Z. Because the second term of
above equation is relatively a small correction to this correlation, its omission does not
introduce large errors, and a correlation for Z
0
may be used alone for quick but less
accurate estimates of Z than are obtained from a three-parameter correlation.

The above is a simple linear relation between Z and for given values of T
r
and P
r.
Lee
and Kesler have developed tables, which present values of Z
0
and Z
1
as functions of T
r
and P
r

Pitzer correlation for the second virial coefficient:



- 30 -
Analytical expressions were given to Z
0
and Z
1
using the simplest form of the virial
equation.

r
r
T
P
B
RT
BP
Z
^
1 1 + = + = where
^
B is a reduced second virial
coefficient given by :

c
c
RT
BP
B =
^


Pitzer and coworkers proposed the correlation.


1 0
^
B B B + =

Therefore
r
r
r
r
T
P
B
T
P
B Z
1 0
1 + + =


r
r
T
P
B Z
0 0
1+ =

r
r
T
P
B Z
1 1
=


0
B and
1
B are functions of reduced temperature only represented by the following
equations:


6 . 1
0
422 . 0
083 . 0
r
T
B =


2 . 4
1
172 . 0
139 . 0
r
T
B =

Ex 2.5
Determine the molar volume of n-butane at 510 K and 25 bar by each of the following :
(a) The ideal gas equation
(b) The generalized compressibility factor equation
(c) Equation
r
r
T
P
B
RT
BP
Z
^
1 1 + = + = with the generalized correlation for
^
B


(a) By the ideal gas equation
V
( )( )
25
510 14 . 83
= =
P
RT
= 1696.1cm
3
mol
-1
(b) T
c
= 425.2K P
c
= 38 bar = 0.200



- 31 -

2 . 1
1 . 425
510
= =
r
T 659 . 0
38
25
= =
r
P

From graphs or Lee Kesler tables ,
Z
0
=0.865, Z
1
=0.038
Z= 0.865 + (0.200)(0.038)=0.873

V
( )( )( )
25
510 14 . 83 873 . 0
P
ZRT
= = = 1480.7 cm
3
mol
-1
(c)
6 . 1
0
422 . 0
083 . 0
r
T
B =
6 . 1
2 . 1
422 . 0
083 . 0 = = -0.232

2 . 4
1
172 . 0
139 . 0
r
T
B =
2 . 4
2 . 1
172 . 0
139 . 0 = = 0.059

1 0
^
B B B + = = -0.232+ (0.2)(0.059)=-0.220

r
r
T
P
B
RT
BP
Z
^
1 1 + = + = = ( ) 879 . 0
2 . 1
659 . 0
220 . 0 1 = + ,
V=
( )( )( )
25
510 14 . 83 879 . 0
=
P
ZRT
= 1489.1 cm
3
mol
-1


Ex 2.6

A mass of 500 g of gaseous ammonia is contained in a 30000 cm3 vessel immersed in a
constant temperature bath at 65 C. Calculate the pressure of the gas by:
(a) The ideal gas equation
(b) A generalized correlation

Sol :

The molar volume of ammonia in the vessel is

02 . 17 500
30000
= = =
M m
V
n
V
V
t t
= 1021.2cm
3
mol
-1


(a) By the ideal gas equation,


( )( )
2 . 1021
15 . 273 65 14 . 83 +
= =
V
RT
P = 27.53 bar


(b) For ammonia , 253 . 0 , 8 . 112 , 7 . 405 = = = bar P K T
c c
,



- 32 -
because the reduced pressure is low,( 244 . 0 8 . 112 53 . 27 =
r
P ), the generalized virial
coefficient should suffice.
834 . 0
7 . 405
15 . 338
= =
r
T

6 . 1
0
422 . 0
083 . 0
r
T
B =
6 . 1
834 . 0
422 . 0
083 . 0 = = -0.481
2 . 4
1
172 . 0
139 . 0
r
T
B =
2 . 4
834 . 0
172 . 0
139 . 0 = = -0.229

1 0
^
B B B + = = -0.481 + (0.253)(-0.229) = - 0.539

( )( )( )
17 . 161
8 . 112
7 . 405 14 . 83 539 . 0
=

= =

c
c
P
RT B
B cm
3
mol
-1


RT
BP
RT
PV
Z + = = 1

( )
( )
( )( )
( )
bar
B V
RT
P
RT B V P
B V
RT
P
RT
BP
RT
PV
77 . 23
17 . 161 2 . 1021
15 . 338 14 . 83
1
1
=

=

=
=
=
=



















- 33 -

Tutorial 2

1. For water at 50
0
C and 1 bar, . 10 418 . 4
1 5
= bar x To what pressure must water be
compressed at 50
0
C to change its density by 1 %? Assume that is independent of P.


2. Five kilograms of liquid carbon tetrachloride undergoes a mechanically reversible,
isobaric change of state at 1 bar during which the temperature changes from 273 K to 293
K . Determine V
t
,W,Q, H
t
,U
t .
The properties for liquid carbon tetra chloride at 1 bar
and 273 K may be assumed independent of temperature: = 1.2 x 10
-3
K
-1
, Cp =
0.84kJkg
-1
K
-1
and = 1590 kgm
-3
.


3. One mole of an ideal gas C
P
=(7/2) R and C
V
=(5/2) R, expands from P
1
=10 bar and
T
1
=600k to P
2
=1 bar by each of the following paths:

a. Constant volume;
b. Constant temperature;
c. Adiabatically.

Assuming mechanical reversibility, calculate W, Q, H and U for each process.
Sketch each path on a single PV diagram.


4. One mole of an ideal gas initially at 30 C and 1 bar is changed to 130 C and 10 bar
by three different mechanically reversible processes:

a) The gas is first heated at constant volume until its temperature is 130 C: then it is
compressed isothermally until its pressure is 10 bar.
b) The gas is first heated at constant pressure until its temperature is 130 C; then it
is compressed isothermally to 10 bar.
c) The gas is first compressed isothermally to 10 bar; then it is heated at constant
pressure to 130 C
Calculate Q, W, H and U in each case. Take R C
p
2
7
= and R C
v
2
5
=

5. Estimate the following:
a) The volume occupied by 18 kg of ethylene at 55 C and 35 bar
b) The mass of ethylene contained in a 0.25 m3 cylinder at 50 C and 115 bar



- 44 -
CHAPTER 3

THERMOCHEMISTRY

Thermo chemistry is the study of heat produced or consumed in a chemical reaction

3.1 Heat capacity (specific heat)

It is the quantity of heat required in J to raise the temperature of 1 kg mass of a substance
by 1 K.

Heat capacity of water is 4186
K kg
J

.

3.2 Sensible heat

It is the quantity of heat effect (enthalpy change) associated with temperature change but
no phase change when a known quantity of substance is heated or cooled.

T mC at Sensiblehe
P
=
Where, m is the mass of substance in kg, C
P
is the heat capacity of substance in
K kg
J

and T is the temperature change.

3.3 Enthalpy of vaporization or Latent heat

It is the quantity of heat effect (enthalpy change) associated with phase change but no
temperature change when a known quantity of substance is heated or cooled.

Estimates of the latent heat of vaporization of a pure liquid at any temperature from the
known value at a single temperature may be based on the empirical equation given by
Watson :


38 . 0
1
2
1
2
1
1

=
r
r
T
T

where
2 1
, are the latent heats of vaporization at
temperatures T
1
,T
2
in Jg
-1





3.4 Temperature Dependence of Heat Capacity

Temperature dependence of the heat capacity for a substance in the ideal gas state is
given by the empirical equation:




- 45 -
2 2
+ + + = DT CT BT A
R
C
ig
P


A, B, C and D are constants characteristic of the particular substance.


= = =
1
0
1
0
T
T
T
T
p
p
dT
R
C
R dT C H Q for a mechanically reversible constant pressure closed
system process

Evaluation of the integral is accomplished by substitution of C
p
as a function of T

( )
) ]( ) 1 (
3
) 1 (
2
[
1 ] ) 1 (
3
) 1 (
2
[
)
1
( ) 1 (
3
) 1 (
2
) 1 (
0
2
0
2 2
0 0
0
2 3
0
2
0 0
0
0
3 3
0
2 2
0 0
0
0
0
T T
T
D
T
C
T
B
A dT
R
C
T
D
T
C
T
B
AT dT
R
C
T
T
where
T
D
T
C
T
B
AT dT
R
C
T
T
P
T
T
P
T
T
P
+ + + + + + =
+ + + + + + =
=

+ + + =

Ex 3.1

Calculate the heat required to raise the temperature of 1 mol of methane from 533.15 to
873.15 K in a steady-flow process at a pressure sufficiently low that methane may be
considered an ideal gas.

Data:

A=1.702 B=9.081x10
-3
C=-2.164x10
-6





Solution:




- 46 -
J T
x
T
x
T
dT
R
C
R H Q
K T
K T
ig
P
19778 )] 1 (
3
10 164 . 2
) 1 (
2
10 081 . 9
) 1 ( 702 . 1 [ 314 . 8
6377 . 1
15 . 533
15 . 873
15 . 873
15 . 533
3 3
0
6
2 2
0
3
0
15 . 873
15 . 533
0
=
+ =
= =
= =
=
=

Ex 3.2:

Given that the latent heat of vaporization of water at 100 C is 2257Jg-1, estimate the
latent heat at 300 C.

Let
1
= latent heat at 100 C = 2257 J g
-1
and
2
= latent heat at 300 C
577 . 0
1 . 647
373
1
= =
r
T 886 . 0
1 . 647
573
2
= =
r
T

( ) 1371
577 . 0 1
886 . 0 1
2257
38 . 0
2
=

= J g
-1
















Tutorial 3






- 47 -
1. For steady flow in a heat exchanger at atmospheric pressure, calculate the heat
transferred:
(a) When 10 mol of SO2 is heated from 200 to 1100 C
(b) When 12 mol of propane is heated from 250 to 1200 C




2. How much heat is required when 10,000 kg of CaCO3 is heated at atmospheric
pressure from 50 C to 880 C.?


3 Handbook values for the latent heats of vaporization in Jg
-1
is given in the table
below for the following pure liquids at 0 C. Calculate the latent heat of
vaporization at the normal boiling point (Appendix 1)























CHAPTER 4


THERMOCHEMISTRY (CONTINUATION)


4.1 Standard Enthalpy of Reaction

H at 0 C
Chloroform
Methanol
Tetrachloromethane
270.9
1189.5
217.8



- 48 -
mM lL bB aA + +

The standard enthalpy of reaction is defined as the enthalpy change when a moles of A
and b moles of B in their standard states at temperature T react to form l moles of L and
m moles of M in their standard states at the same temperature T.

4.2 Standard Conditions

Gas: The standard state is in the ideal gas state at 1 bar
Liquid/solid: The standard state is the real pure liquid or solid at 1 bar

4.3 Standard Enthalpy of Formation

Standard enthalpy of formation is defined as the heat change when 1 mole of compound
is formed from its constituent elements at standard conditions of temperature and
pressure.The usual temperature is 298.15K or 25 C
The standard heat of formation of a compound at this temperature is represented by
0
298 f
H


Ex 4.1

Calculate the standard heat at 298.15 K for the following reaction:

) ( 2 2 ) ( ) ( 4
2 2 2
g Cl O H g O g HCl + +


Data: Standard enthalpy of formation HCl(g)= 92307
0
298
=
f
H Jmole
-1

Standard enthalpy of formation of H
2
O(g)= 241818
0
298
=
f
H jmole
-1



Writing the formation equations so that their sum yields the desired reaction equations so
that , the he following combination gives the desired result :


4HCl(g) 2H
2
(g) + 2Cl
2
(g) ( )( ) 307 , 92 4
0
298
= H
2H
2
(g) + O
2
(g) 2H
2
O(g) ( )( ) 818 , 241 2
0
298
= H
______________________________

)
sin (
) Re ( 2
2
1
:
4 2
4 2 3 2
3 2 2
elements its from formed not is SO H
ce reaction formation a not SO H SO O H
action Formation OH CH H O C Example
+
+ +



- 49 -
4HCl(g) + O
2
(g) 2H
2
O(g) + 2Cl
2
(g) 408 , 114
0
298
= H J

4.4 Standard enthalpy of Combustion

It is the Quantity of heat released when 1 mole of compound reacts with oxygen under
standard conditions of temperature and pressure.

4.5 Temperature dependence of
0
H

The general chemical reaction may be written as:

.
..... ......
4 1 3 1 2 1 1 1
formula chemical the is A t coefficien tric stoichiome the is where
A A A A
i i

+ + +


The species on the left hand side are reactants and the sign convention is negative and on
the right hand side are products for which the sign convention is positive.

H H
i
f
i
i

=
0 0


Ex. :

3 , 2 , 1 ,
2 3
2 3 2
3 2 2
= + = =
+
H NH N
then
NH H N



For standard reactions, products and reactants are always at the standard-state pressure of
1 bar. Standard state enthalpies are therefore functions of temperature only.







The fundamental equation relating heats of reaction to temperature is as follows

dT
R
R
T
T
0
P
0
298
0
0
C
H H
+ =

H H
and

0
298
0
are heats of reaction at temperature T and at reference temperature
298 K respectively.




- 50 -
D C B for s definition ous ana with
A A
T
D
T
C
T
B
T A dT
R
i
i
i
T
T
P C

=

+

+ =

, , log
)
1
( ) 1 (
3
) 1 (
2
) 1 ( ) (
0
3 3
0
2 2
0 0
0
0

Ex 4.2

Calculate the standard heat of the methanol-synthesis reaction at 1073.15 K

) ( ) ( 2 ) (
3 2
g OH CH g H g CO +

Data:

mol kJ
H
/ 135 . 90 ) 525 . 110 ( 66 . 200
0
15 . 298
= =

i
i
A 10
3
B 10
6
C 10
-5
D
CH
3
OH 1 2.211 12.216 -3.450 0.000
CO -1 3.376 0.557 0.000 -0.031
H
2
-2 3.249 0.422 0.000 0.083

A = (1)(2.211) + (-1)(3.376) + (-2)(3.249) = -7.663
B = (1)(12.216x10
-3
) + (-1) (0.557x 10
-3
) + (-2)(0.422 x 10
-3
)= 10.809x10
-3
C = (1)(-3.45x10
-6
) + (-1)(0) + (-2)(0) = -3.45x10
-6

D = (1)(0) + (-1)(-0.031x10
5
) + (-2)(0.083 x 10
5
) = -0.135 x 10
5


Substituting in the above equation,

( )( )
( )( )
2
15 . 298 15 . 1073 10 809 . 10
15 . 298 15 . 1073 663 . 7
2 2 3 15 . 1073
15 . 298
0

+ =

R
C
P


( )( )
( )

15 . 298
1
15 . 1073
1
10 135 . 0
3
15 . 298 15 . 1073 10 45 . 3
5
3 3 6


= -1618.653



- 51 -
dT
R
R
T
T
P C
H H

+ =
0
0
0
298
0

( )( ) 653 . 1618 314 . 8 90135
0
15 . 1073
+ = H = -103593 J


























Tutorial 4



1) If the enthalpy of combustion of urea, ) ( ) (
2 2
s CO NH , at 29.15 K is 631660 J/mol
when the products are CO
2
(g), H
2
O(l) and N
2
(g), what is
0
298 , f
H for urea at 298.15 K?

Data:

Standard enthalpy of formation of CO
2
(g) = -393509
mol
J

Standard enthalpy of formation of H
2
O(l) = --285830
mol
J






- 52 -


2) Calculate the standard enthalpy of the following reaction (oxidation of ethylene to
ethylene oxide) at 873.15 K by choosing 1 mol of ethylene as basis.

( ) ) ( ) (
2
1
) (
2 2 2 4 2
g O CH g O g H C +

I
i
A 10
3
B 10
6
C 10
-5
D
CH
3
OH 1 2.211 12.216 -3.450 0.000
CO -1 3.376 0.557 0.000 -0.031
H
2
-2 3.249 0.422 0.000 0.083


3) Determine the standard heat of each of the following reactions at 25 C:

(a) ( ) ( ) g NH g H g N
3 2 2
2 ) ( 3 +
(b) ( ) ( ) ( ) ( ) g O H g NO g O g NH
2 2 3
6 4 5 4 + +
(c) ( ) ( ) ( ) ( ) g NO l HNO l O H g NO + +
3 2 2
2 3
(d) ( ) ( ) ( ) ( ) s CaO g H C l O H s CaC + +
2 2 2 2








CHAPTER 5

Thermodynamic properties of fluids

Numerical values for thermodynamic properties are essential to the calculation of heat
and work quantities for industrial processes. Fundamental property relations can be
developed using the first and second law of thermodynamics. The only requirement being
that the system be closed and that the changes occur between equilibrium states.

5.1 Internal energy:

Internal energy is defined as the energy associated with the random, disordered motion of
molecules. It is separated in scale from the macroscopic ordered energy associated with
moving objects; it refers to the invisible microscopic energy on the atomic and molecular
scale.

The first law of thermodynamics is the application of conservation of energy principle.




- 53 -
The change in internal energy of a system is equal to the heat added to the system minus
the work done by the system

U=Q-W

5.2 Enthalpy

H=U+PV

P and V are the pressure and volume and U is the internal energy. Enthalpy (H) is
exactly measurable state variable since it is defined in terms of three other precisely
defined state variables. It is parallel to first law of thermodynamics for a constant
pressure system.

Q=U=PV, in this case, Q=H.
Enthalpy is a useful quantity for tracking chemical reactions. If as a result of an
exothermic reaction, some energy is released to a system, it has to show up in some
measurable form in terms of the state variables. An increase in enthalpy H=U+PV might
be associated with an increase in internal energy which could be measured by calorimetry
or with work done by the system or a combination of two.

The internal energy U might be thought of as the energy required to create a system in the
absence of changes in temperature or volume. But if the process changes with volume, as
in a chemical reaction, which produces a gaseous product, then work must be done to
produce the change in volume. For a constant pressure process, the work you must do to
produce a volume change V is PV. Then PV term can be interpreted as the work you
must do to create room for the system if you presume it started at zero volume.

5.3 Helmholtz free energy:

F=U-TS

If the system is created in an environment of temperature T, then some of the energy can
be obtained by spontaneous heat transfer from the environment to the system. The
amount of this spontaneous energy transfer is TS where S is the final entropy of the
system.


5.4 Gibbs free energy:

Gibbs free energy, G=U-TS+PV = H-TS

The internal energy might be thought of as the energy required to create a system in the
absence of changes in temperature or volume. But as discussed in defining enthalpy, an
additional amount of work PV must be done if the system is created from a very small
volume in order to create room for the system. As discussed in defining Helmholtz free



- 54 -
energy, an environment at constant temperature T will contribute an amount TS to the
system, reducing the overall investment necessary for creating the system. This net
energy contribution for a system created in environment temperature from a negligible
initial volume is the Gibbs free energy.

Relation between the properties can be shown graphically below:







These fundamental property relations are general equations for a homogeneous fluid of
constant composition.

5.5 Thermodynamics relations:
H = ENTHALPY
TS
G = FREE ENERGY
TS PV
A=TOTAL
USEFUL WORK
PV
U= INTERNAL ENERGY
UNAVAIL-
ABLE
ENERGY
EXTERNAL
WORK



- 55 -

In the design of chemical plants and equipments, two types of thermodynamic properties
are needed.

a. Directly measurable properties like pressure, temperature, volume etc.


b. Properties which can not be measured directly. Examples are enthalpy, entropy,
free energy etc.

The thermodynamic relations establish a relationship between directly measurable
properties and properties which are not directly measurable. Thus the properties under
the second category may be evaluated from their relation with directly measurable
properties or from thermodynamic relations.

5.6 Theorem of exact differential:

y x
F
x
N
and
x y
F
y
M
obtain we ation differenti further By
y
F
N
x
F
M
Ndy Mdx dF or
dy
y
F
dx
x
F
dF
F of al differenti total the then
y x F F If
y
x
x
y
x
y

=
+ =

=
=
2 2
, ,
) , (


Since the order of differentiation in mixed second derivatives is immaterial, these
equations gives,

x
y
M

=
y
x
N

When F is a function of x and y, Mdx+Ndy is an exact differential expression.

The functions, dU, dH, dA and dG are exact differential expressions.









- 56 -
5.7 Maxwell relations:

We can write the following relations, called Maxwell relations using the criterion of
theorem of exactness.

T P
T V
P
S
V S
P
S
T
V
V
S
T
P
S
V
P
T
S
P
V
T

Tutorial 5


1. Show that:

dP
T
V
T
dT
C dS
P
P

=


2. Show that:




- 57 -
dV
T
P
T
dT
C dS
V
V

+ =


3. Prove that,
V
V
C
V
U
=

4. Prove that,
P
P
C
T
H
=

5. Show that for an ideal gas,

0 .
0 .
=

T
T
P
H
b
V
U
a



6. Show that for a PVT system,

dV
V
dT dP

1
=


7. Prove that,

2
2
TV
V
P
T
V
T C C
T
P
V P
=

=






- 59 -


CHAPTER 6


CHEMICAL REACTION EQUILIBRIA


The rate of a chemical reaction and the maximum possible (or equilibrium) conversion of
a chemical reaction are of primary concern and depend on the temperature, pressure and
composition of the reactants.

Ex: Consider the reaction, oxidation of SO
2
to SO
3
.

A catalyst is required if a reasonable reaction rate is to be attained. With V
2
O
5
catalyst,
the rate becomes appreciable at about 573.15 K and continues to increase at higher
temperatures. On the basis of rate alone, one would operate the reactor at the highest
practical temperature. However, the equilibrium conversion to SO
3
falls as temperature
rises decreasing from about 90 % at 793.15 K to 50 % at about 953.15 K. These values
represent maximum possible conversion regardless of catalyst or reaction rate. Hence
both equilibrium and rate has to be considered in the process design .Equilibrium
conversions can be obtained by thermodynamic calculations.


6.1 Reaction coordinate:

The general chemical reaction can be written as:

...... ........
4 4 3 3 2 2 1 1
+ + + + A A A A

where
i
is the stoichiometric coefficient and A
i
stands for chemical formula.
i
s are
called as stoichiometric numbers (positive for products and negative for reactants).

Ex:

2 2 4
3H CO O H CH + +

3
1
1
1
2
2
4
=
=
=
=
H
CO
O H
CH

Stoichiometric number of an inert species is zero.





- 60 -

The changes in the numbers of moles of the species are in direct proportion to the
stoichiometric numbers. If 0.5 mol of CH
4
disappears by reaction, 0.5 mol of H
2
O must
also disappear. Simultaneously 0.5 mol of CO and 1.5 mol of H
2
are formed.

) ,.... 2 , 1 ( , .
....
3
3
2
2
1
1
1
1
3
3
1
1
2
2
N i d dn e i
d
dn dn dn
dn dn
dn dn
i i
= =
= = = =
=
=


is called reaction coordinate which characterizes the extent or degree to which a reaction
has taken place.

+
+
= =
+ =
+ = =
= + =
=


0
0
0
0
0
0
,
) ,.... 3 , 2 , 1 (
0
n
n
n
n
y
is i species of fraction mole
n n
n n n
N i n n
d dn
i i i
i
i
i
i
i
i
i
i i i
i
n
n
i
i
i



Ex. 1:

For a system in which the following reaction occurs

2 2 4
3H CO O H CH + +
Assume that there are initially 2 mol CH
4
, 1 mol H
2
O, 1 mole CO and 4 mol H
2
.
Determine the mole fractions y
i
as functions of .



sol:
For the given reaction, 2 3 1 1 1 = + + = =
i

For the given numbers of moles of species initially present,



- 61 -

8 4 1 1 2 = + + + = =
io o
n n

2 8
2
4
+

=
CH
y

2 8
1
2
+

=
O H
y

2 8
1
+
+
=
CO
y

2 8
3 4
2
+
+
=
H
y



6.2 Multi reaction stoichiometry:

When two or more independent
reactions proceed simultaneously, the
stoichiometric numbers are doubly
spaced to identify their association with
both species and the reaction. Thus
i,j

refers to stoichiometric number of
species i in reaction j.




Ex. 3:

Consider a system in which the following reactions occur:

) 2 .......( 4 2
) 1 .......( 3
2 2 2 4
2 2 4
H CO O H CH
H CO O H CH
+ +
+ +


Where (1) and (2) represent the values of j, the reaction index. If there are initially 2 mol
CH
4
and 3 mol H
2
O, determine expressions for y
i
as functions of
1
and
2
.
Sol : The stochiometric numbers
j i,
can be arrayed as follows

__________________________________________________
j CH
4
H
2
O CO CO
2
H
2

j
__________________________________________________

+
+
=
+ =
=
=
+ = + =
= + =
= =
j
j j
j
j
j i i
i
j
j
j
i
j i j
i
i
j i
j j i j
i j
j i
i
i
j
j
j i i i
j
j
j i i
n
n
y
n n
n n n
N i n n
N i d dn








0
, 0
0
,
, 0 , 0
, 0
,
) (
) ,..... 2 , 1 (
) ,..... 2 , 1 (



- 62 -

1 -1 -1 1 0 3 2
2 -1 -2 0 1 4 2
__________________________________________________


2 1
2 1
4
2 2 5
2


+ +

=
CH
y
2 1
2 1
2
2 2 5
2 3


+ +

=
O H
y
2 1
1
2 2 5

+ +
=
CO
y
2 1
2
2
2 2 5

+ +
=
CO
y

2 2
2 1
2
2 2 5
4 3


+ +
+
=
H
y

























Tutorial 6


1. Develop expressions for the mole fractions of reacting species as functions of the
reaction co-ordinate for:



- 63 -
(a). A system initially containing 2 mol NH
3
and 5 mol O
2
and
undergoing the reaction:

) ( 6 ) ( 4 ) ( 5 ) ( 4
2 2 3
g O H g NO g O g NH + +

(b). A system initially containing 3 mol H
2
S and 5 mol O
2
and
undergoing the reaction:

) ( 2 ) ( 2 ) ( 3 ) ( 2
2 2 2 2
g SO g O H g O g S H + +

(c). A system initially containing 3 mol NO
2
, 4 mol NH
3
and 1 mol N
2

and undergoing the reaction:
) ( 12 ) ( 7 ) ( 8 ) ( 6
2 2 3 2
g O H g N g NH g NO + +
Consider a vessel which initially contains only n
0
moles of H
2
O vapor. If decomposition
occurs according to the reaction,

2 2 2
2
1
O H O H +
Find expressions which relate the number of moles and the mole fraction of each
chemical species to the reaction coordinate .

2. A system initially containing 2 mol C
2
H
4
and 3 mol O
2
undergoes the reactions:


) ( 2 ) ( 2 ) ( 3 ) (
) ( ) ( ) (
2
1
) (
2 2 2 4 2
2 2 2 4 2
g O H g CO g O g H C
g O CH g O g H C
+ +
+


Develop expressions for the mole fractions of the reacting species
as functions of the reaction coordinates for the two reactions.

3. A system formed initially of 2 mol CO
2
, 5 mol H
2
and 1 mol CO undergoes the
reactions:


) ( ) ( ) ( ) (
) ( ) ( ) ( 3 ) (
2 2 2
2 3 2 2
g O H g CO g H g CO
g O H g OH CH g H g CO
+ +
+ +


Develop expressions for the mole fractions of the reacting species
as functions of the reaction coordinates for the two reactions.

CHAPTER 7


CHEMICAL REACTION EQUILIBRIA (CONTINUATION)




- 64 -

7.1 Equilibrium criteria to chemical reactions:

The total Gibbs energy, G
t
of a closed system at constant T and P must decrease during
an irreversible process and that the condition of equilibrium is reached when G
t
attains a
minimum value.

At equilibrium state, . 0 ) (
,
=
P T
t
dG

When G
t
is plotted against , the reaction coordinate, the reaction coordinate has the
minimum value
e
at the minimum of the curve.

7.2 Relationship between Standard Gibbs energy change and the equilibrium
constant:

=
RT
G
K
0
exp
Kelvin in e temperatur the is T
t cons gas universal
K kmol
J
R
change energy Gibbs dard s the is G
t cons m equilibriu the is K
tan
.
8314
tan
tan
0
= =

Effect of temperature on the equilibrium constant:

We know that the differential change in Gibbs energy,

SdT VdP dG = ------(1)

G=H-TS---------------- (2)

where G is Gibbs energy, S is the entropy and V is the volume.

G=G(T,P), that is Gibbs energy is a function of temperature and pressure.

= =

= =

) tan ( 0
, , var tan
) (
) (
1 1
2 2
t cons P dP
then e temperatur only with y reaction of changes property dard s Since
dT
RT
TS H
SdT VdP
RT
dT
RT
G
dG
RT RT
G
d





- 65 -
( )
1
]
1

+ |

\
|
|

\
|
+ |

\
|
+ |

\
|
+ =
+

+ +

+ + =

+ =
+

=

=

I
T
D
T
C
T
B
T A RT J G
I
T
D
T
C
T
B
T A
RT
J
K
result following the gives A equation in C equation of on Substituti
C
T
D
T
C
T
B
T A
R
J
R
H
egration of t cons another is J where
B dT C J H
reaction of change enthalpy dard S that know We
egration of t cons the is I where
A I dT
RT
H
K
RT
H
dT
K d
RT
H
dT
RT
G
d
P
2
2 0
2
2
3 2
0
0 0
2
0
2
0
2
0
0
1
2 6 2
ln ) (
2 6 2
ln ) ( ln
: ) ( ) (
) (
3 2
) (
. int tan
) (
, tan
. int tan
) ( ln
ln

Standard Gibbs energy change
0
G and standard enthalpy change
0
H values can be
found from literature and these values when substituted in the above equations give the
integration constants I and J.

Then, the values of I and J can be substituted in the equation for ln K. This gives the
relationship between equilibrium constant K and temperature T.


Ex 7.1:

Calculate the equilibrium constant for the vapor phase hydration of ethylene at 145 and
320
0
C. The pertinent chemical reaction can be represented by the following equation:

) ( ) ( ) (
5 2 2 4 2
g OH H C g O H g H C +

Solution:

5 5
6 6
3 3
10 121 . 0 10 ) 121 . 0 0 0 (
10 61 . 1 10 ) 0 392 . 4 002 . 6 (
10 157 . 4 10 ) 45 . 1 394 . 14 001 . 20 (
376 . 1 47 . 3 424 . 1 518 . 3
x x D
x x C
x x B
A
= =
= + =
= =
= =






- 66 -

Standard enthalpy change of reaction at 298 K is calculated as follows:

7 . 5308
15 . 298
12100
) 15 . 298 )( 10 5367 . 0 ( ) 15 . 298 )( 10 0785 . 2 ( ) 15 . 298 )( 376 . 1 (
314 . 8
45792
3677 . 3
) 15 . 298 )( 314 . 8 (
8348
ln
8348 ) 228572 ( 68430 168490
45792 ) 241818 ( 52510 235100
3 6 2 3
0
0
298
0
298
=
+ + =

= =

=
= =
= =

R
J
x x
R
J
RT
G
K
mol
J
G
mol
J
H

125 . 7
) 15 . 298 )( 2 (
12100
) 15 . 298 )( 10 2683 . 0 ( ) 15 . 298 )( 10 0785 . 2 ( ) 15 . 298 ln( 376 . 1
15 . 298
7 . 5308
3677 . 3
2
2 6 3
=
+
+ =

I
I
x x

The general expression for K ln is as follows:

3 0 0
2 0 0
2
2 6 3
10 91 . 2 , 15 . 593 320
10 26 . 14 , 15 . 418 145
125 . 7
2
12100
10 2683 . 0 10 0785 . 2 ln 376 . 1
7 . 5308
ln

= = =
= = =
+ =
x K K C T when
x K K C T when
T
T x T x T
T
K










Tutorial 7


1) Calculate the equilibrium constant for the following reaction at 150
0
C:

) ( ) ( 2 ) (
3 2
g OH CH g H g CO +




- 67 -

2) For the ammonia synthesis reaction written:

) ( ) (
2
3
) (
2
1
3 2 2
g NH g H g N +

with 0.5 mol N
2
and 1.5 mol H
2
as the initial amounts of reactants and with the
assumption that the equilibrium mixture is an ideal gas, show that:

( )
5 . 0
299 . 1 1 1

+ = KP
e



3) Three members A, B and C are asked to find the equilibrium composition at a
particular T and P and for given initial amounts of reactants for the following gas phase
reaction:

2 2 3
2
5
3 3 2 N O H NO NH + + -------------(1)
Each solves the problem correctly in a different way. A bases her solution on reaction (1)
as written. B, who prefers whole numbers, multiples reaction (1) by 2:

2 2 3
5 6 6 4 N O H NO NH + + -------------(2)
C, who usually does things backward, deals with the reaction:

NO NH N O H 3 2
2
5
3
3 2 2
+ + ------------(3)

Write the chemical equilibrium equations for the three reactions, indicate how the
equilibrium constants are related, and show why A,B and C all obtain the same result.





4) The following reaction reaches equilibrium at 773.15 K and 2 bar:

) ( 2 ) ( 2 ) ( ) ( 4
2 2 2
g Cl g O H g O g HCl + +

If the system initially contains 5 mol HCl for each mole of oxygen, find the composition
of the system at equilibrium. Assume ideal gases.


5) The following reaction reaches equilibrium at 923.15 K and atmospheric pressure:

) ( 2 ) ( ) (
2 2 2
g HCN g H C g N +



- 68 -

If the system initially is an equimolar mixture of nitrogen and acetylene, find the
composition of the system at equilibrium. What would be the effect of doubling the
pressure? Assume ideal gases.


6) The following reaction reaches equilibrium at 623.15 K and 3 bar:

) ( ) ( ) (
5 2 2 3
g OH H C g H g CHO CH +

If the system initially contains 1.5 mol H
2
for each mole of acetaldehyde, find the
composition of the system at equilibrium. What would be the effect in reducing the
pressure to 1 bar? Assume ideal gases.















- 59 -
CHAPTER 8

FUNDAMENTALS IN SOLUTION THERMODYNAMICS AND FLUID PHASE
EQUILIBRIA


8.1 Definitions


Residual Property


The residual property is the difference between the fluid property and ideal gas property.

Excess Property

The excess property is the difference between the solution property and ideal solution
property.

Equilibrium

Equilibrium is a static condition in which no changes occur in the properties of a system
with time.


Chemical Potential

The term chemical potential is equivalent to free energy for one mole.


Raoults Law

The partial vapor pressure of a component in a mixture is equal to the vapor pressure of
the pure component multiplied by its mole fraction in the mixture.
Partial Pressure = Vapor pressure Mole fraction (
Py P x
i i
sat
i
=
)




Partial Pressure
In any mixture of gases, each gas exerts its own pressure known as partial pressure. This
partial pressure is independent of the other gas present in the mixture.

Ideal Mixture
An ideal mixture is the one which obeys Raoults law.
Example: Hexane and Heptane



- 60 -
Benzene and Methylbenzene

Azeotrope
Azeotrope is defined as a mixture of liquids that has a constant boiling point because the
vapor has the same composition as the liquid mixture.
For azeotropic mixture Mole fraction in Vapor phase = Mole fraction in Liquid phase



8.2 General Phase Equilibrium Relations

Phase equilibrium variables: T, P, moles of each component n

Consider a closed system with no chemical reactions. The fundamental property relation
with T and P as independent variables involved the Gibbs free energy:


( ) ( ) ( )
( )
( )
P
T
T
nG
nS
P
nG
nV
dT nS dP nV nG d

=
=

The 1st and 2nd laws and definition of G (G=H-TS) are involved in deriving this property
relation. If the system can exchange mass with its surroundings (another phase), then it
becomes an open system, and the fundamental property relationship must be modified:


( ) ( ) ( )
( )
i
s n P T
i
i
i
N
i
i
G
n
nG
dn dT nS dP nV nG d
j
=

=
+ =

=
' , ,
1

This new defined property i is called the chemical potential for component i in a
mixture.

At equilibrium, the temperature and pressure must be the same in all phases, for
thermal and mechanical equilibrium considerations (i.e., no driving forces to cause fluxes
of heat or fluid movement).

Considering a system considering two phases at temperature T and pressure P
In the vapor() and liquid phase() we can write the following fundamental property
relations



- 61 -


( ) ( ) ( )
( ) ( ) ( )

i i
i i
dn dT nS dP nV nG d
dn dT nS dP nV nG d

+ =
+ =

The total change in Gibbs free energy for the entire system is the sum of the above
equations


( ) ( ) ( )

+ + =


i i i i
dn dn dT nS dP nV nG d


But, since this is a closed system, the last two terms must sum to zero. Also, any mass
leaving one phase must enter the other.


( ) 0
0
=
=
= +

i i i
i i
i i i i
dn
dn dn
dn dn


Since the dn's are arbitrary independent variables, we conclude that


N i
i i
,...., 3 , 2 , 1 = =




This can be expanded to any number of phases.

Thus, in addition to thermal and mechanical equilibrium, the chemical potential for any
given component must be the same in all phases at equilibrium.

This is phase equilibrium (i.e., no driving forces for diffusion).

At equilibrium in a system of phases and N components,




i i i
i N = = = = .... , , .... , 1 2






8.3 Calculations Using Raoult's Law

Bubble-point pressure problem -- T,x given -- P,y unknown.



- 62 -
P
x P
y
x P P Py
i
sat
i
i
sat
i i
=
= =




For a binary system,

sat sat
P x P x P
2 2 1 1
+ =

( )( )
P
P x
y
sat
1 1
1
=


Bubble point temperature problem -- P,x given -- T,y unknown.

A trial and error procedure must be followed, where T is assumed, the vapor pressures
calculated, and then see if the correct total pressure is obtained (or the vapor mole
fractions sum to unity).


= =
P
x P
y
i
sat
i
i
1

Dew-point pressure problem -- T,y given -- P,x unknown.

No trial and error is needed, as P can be directly calculated.

=
=
=
sat
i
i
i
sat
i
i
i
P
y
P
x
P
Py
x
1
1





- 63 -


Dew-point temperature problem -- P,y given -- T,x unknown.

Guess a T, find the vapor pressures, and see if the liquid mole fractions sum to unity.

= =
sat
i
i
i
P
Py
x 1


Ex 8.1

The binary system acetonitrile(1),nitromethane(2) confirms closely to Raoults law.
Vapor pressures for the pure species are given by the following Antoine equations:



( )
( ) 209
644 . 2972
2043 . 14 ln
224
47 . 2945
2724 . 14 ln
2
1
+
=
+
=
t
P
t
P
sat
sat
. P in kPa, T in C
a) Generate data for P versus x1 and P versus y1 for a temperature of 75C and prepare
graph.

b) Generate data for t versus x1 and t versus y1 for a pressure of 70 kPa and prepare
graph.



Sol : At 75 C vapor pressures calculated are
21 . 83
1
=
sat
P
kPa,
98 . 41
2
=
sat
P
kPa

a)
Writing Raoults law for each species,

sat
sat
P x P y
P x P y
2 2 2
1 1 1
=
=


Since
1
2 1
= + y y
, adding the above gives

sat sat
P x P x P
2 2 1 1
+ =


putting
1 2
1 x x =
,the above equation reduces to


( )
1 2 1 2
x P P P P
sat sat sat
+ =





- 64 -

For
0
1
= x
to
1
1
= x
, calculate P , and
( )( )
P
P x
y
sat
1 1
1
=




1
x

1
y

P
0.0
0.2
0.4
0.6
0.8
1.0

0.0
0.33
0.57
0.75
0.89
1.0
41.98
50.23
58.47
66.72
74.96
83.21


b) For a given pressure, the temperature range is bounded by the saturation temperatures
sat
t
1
and
sat
t
2


At
kPa P P
sat
i
70 = =


58 . 89
84 . 69
2
1
=
=
sat
sat
t
t
in C

When x1 is known along with P

+ = + =
2
2
1
1 2 2 2 1 1
x
P
P
x P P x P x P
sat
sat
sat sat sat


or
|
|

\
|
+
=
2
2
1
1
2
x
P
P
x
P
P
sat
sat
sat
(1)

209
64 . 2972
224
47 . 2945
0681 . 0 . ln
2
1
+
+
+
=

t t P
P
sat
sat
(2)



a) choose a value of
sat
sat
P
P
2
1
calculated at some intermediate temperature
b) calculate
sat
P
2
from (1)




- 65 -
c) calculate t from the Antoine equation for species 2 :
209
ln 2043 . 14
64 . 2972
2

=
sat
P
t
d) determine a new value of
sat
sat
P
P
2
1
by equation (2) and a new value of
sat
P
2
by equation
(1)

e) return to step (c) and continue iteration till convergence

When
1
y is known along with P, use
sat sat
sat
sat sat
P P y y
P
P y P y
P
2 1 2 1
1
2 2 1 1
1
+
=
+
=

( )
sat sat sat
P P y y P P
2 1 2 1 1
+ =


224
ln 2724 . 14
47 . 2945
1

=
sat
P
t



For purpose of generating data to prepare txy diagram, select values of t between

sat
t
1
and
sat
t
2
,calculate
sat
P
1
and
sat
P
2
and evaluate x
1
by
sat sat
sat
P P
P P
x
2 1
2
1

=

for example at 86 C, 118
1
=
sat
P and 03 . 62
2
=
sat
P kPa

142 . 0
03 . 62 118
03 . 62 70
1
=

= x

( )( )
24 . 0
70
118 142 . 0
1 1
1
= = =
P
P x
y
sat



values generated as shown below

1
x
1
y
t C
0.0
0.1424
0.3184
0.5156
0.7378
0.0
0.2401
0.4742
0.6759
0.8484
89.58
86
82
78
74



- 66 -
1.0 1.0 69.84





8.4 Fugacity

The chemical potential can also be defined as

( ) T f RT
i i i
+ =

ln

Where
i
is the chemical potential of species i

i
f

is the fugacity of species i in solution

i
is a function of temperature.


.

In terms of fugacities, the phase equilibrium relations do not change:


$ $
......
$
, , .... , f f f i N
i i i

= = = = 1 2





Fugacity is equal to the pressure when the pressure approaches zero (Ideal gas condition).

Fugacity Coefficient :

The fugacity coefficient is defined as the ratio of the fugacity to pressure.



essure
Fugacity
t Coefficien Fugacity
Pr
=

The fugacity coefficient takes into account the departure of gas phase from ideal gas
behavior.

If the value of > 1 then it shows the deviation from ideal gas behavior.


Fugacities in Mixtures - Ideal Behavior



- 67 -

Gas Phase -- Ideal Gases


$
f Py
i
V
i
=


Liquid Phase -- Ideal Solutions


$
f f x
i
L
i
L
i
=


The coefficient on the RHS is the fugacity of the pure liquid at the same
T,P as the actual liquid mixture.

This relation is called the Lewis-Randall rule.

Note: Ideal solutions exhibit no volume change on mixing
and no heat of mixing.



8.5 Activity and activity coefficient
The activity of any component is defined as ratio of partial fugacity of the component to
fugacity of pure component.
( )
0

f ponent f pure com Fugacity o

f ent the compon gacity of Partial Fu
Activity a

=

Activity Coefficient :

The activity coefficient is defined as the ratio of the activity to the mole fraction.


ion Mole fract
Activity
t Coefficien Activity =

The activity coefficient takes into account the departure of liquid phase from ideal
solution behavior.

If the value of > 1 then it shows the deviation from ideal solution behavior.




Ex 8.2



- 68 -

A mixture of ethylene and oxygen (67%C
2
H
4
and 33%O
2
) exists at 25 atm and 0C at
which partial fugacities of components are reported to be
Partial fugacity of C
2
H
4
4 2

H C
f = 14.38 atm
Partial fugacity of O
2
2

O
f = 8.12 atm

The pure component fugacities are given by

Pure component fugacity of C
2
H
4
atm 6 . 20
0
4 2
=
H C
f

Pure component fugacity of O
2
atm 5 . 24
0
2
=
O
f

Calculate
1. Activity of C
2
H
4
and O
2


2. Activity Coefficient of C
2
H
4
and O
2






Solution
( )
0

f ponent f pure com Fugacity o

f ent the compon gacity of Partial Fu
a) Activity (

=

Activity of C
2
H
4
is given by


69 . 0
6 . 20
28 . 14

0
4 2
4 2
4 2
= = =
H C
H C
H C
f
f
a

Activity of O
2
is given by


33 . 0
5 . 24
12 . 8

0
2
2
2
= = =
O
O
f
O f
a




- 69 -
( )
ion Mole fract
Activity
t Coefficien Activity =




Activity Coefficient of C
2
H
4
is given by


03 . 1
67 . 0
69 . 0
4 2
4 2
4 2
= = =
H ion of C mole fract
a
H C
H C

Activity of Coefficient O
2
is given by


00 . 1
33 . 0
33 . 0
2
2
2
= = =
ion of O mole fract
a
O
O

8.6 Lewis Randall Rule

Lewis Randall rule states that

Partial Fugacity of any component = Pure component Fugacity Mole fraction
i i i
x f f =
0

Ex 8.3

A mixture of ethylene and oxygen (67%C
2
H
4
and 33%O
2
) exists at 25 atm and 0C.

The pure component fugacities are given by

Pure component fugacity of C
2
H
4
atm 6 . 20
0
4 2
=
H C
f
Pure component fugacity of O
2
atm 5 . 24
0
2
=
O
f

Calculate

1. Partial Fugacity of C
2
H
4
and O
2
using Lewis Randall Rule



- 70 -

2. Activity of C
2
H
4
and O
2


3. Activity Coefficient of C
2
H
4
and O
2



Solution

Partial Fugacity of any component = Pure component Fugacity Mole fraction

Partial Fugacity of C
2
H
4 on molefracti H ity of C nent fugac Pure compo f
H C
=
4 2
4 2

atm 8 . 13 67 . 0 6 . 20

4 2
= =
H C
f

Partial Fugacity of O
2 on molefracti ity of O nent fugac Pure compo f
O
=
2
2

atm 08 . 8 33 . 0 5 . 24

2
= =
O
f

Activity of C
2
H
4
is given by

67 . 0 6699 . 0
6 . 20
8 . 13

0
4 2
4 2
4 2
= = = =
H C
H C
H C
f
f
a
Activity of O
2
is given by

33 . 0 3298 . 0
5 . 24
08 . 8

0
2
2
2
= = = =
O
o
o
f
f
a

Activity Coefficient of C
2
H
4
is given by


9998 . 0
67 . 0
6699 . 0
4 2
4 2
4 2
= = =
H ion of C mole fract
a
H C
H C

Activity of Coefficient O
2
is given by


9993 . 0
33 . 0
3298 . 0
2
2
2
= = =
ion of O mole fract
a
O
O

- 71 -


8.7 Models for Excess Gibbs Energy
The excess property is the difference between the solution property and ideal solution
property.

id E
M M M =

The excess Gibbs Energy is given by

id E
G G G =

Activity Coefficients have traditionally been calculated from correlating equations for
RT G
E
equations, hence the models of excess Gibbs energy is important in chemical
engineering thermodynamics

The excess Gibbs energy is a function of temperature, pressure and compositions, but for
liquids at low to moderate pressures it is a weak function of pressure. Hence the pressure
dependence of activity coefficient is usually neglected, thus

Excess Gibbs energy is a function of composition at constant temperature.
( )
N
E
x x x g
RT
G
,......, ,
2 1
= (Const T)

Redlich Kister Equation

The excess Gibbs energy is given by

( ) ( )
2
2 1 2 1
2 1
x x C x x B A
RT x x
G
E
+ + =

Margules Equation

If B=C=0, then
A
RT x x
G
E
=
2 1
or
2 1
x Ax
RT
G
E
=

The activity coefficients are calculated by
2
2 1
ln Ax =
2
1 2
ln Ax =



- 72 -

This is the simplest expression for the excess Gibbs energy.


Van Laar Equation
The excess Gibbs energy is given by

2 1 2 1
Bx Ax
AB
RT x x
G
E
+
=

The activity coefficient are calculated by
2
2
1
1
1
ln

+
=
Bx
Ax
A


2
1
2
2
1
ln

+
=
Ax
Bx
B



8.8 Deviation from Ideal Behavior

If the excess Gibbs free energy
RT
G
E
is positive, then
1
ln and
2
ln are positive, ten
these systems are said to exhibit positive deviation from Ideality.

Example: Furan and Carbon tetrachloride at 30C
If the excess Gibbs free energy
RT
G
E
is negative, then
1
ln and
2
ln are negative, ten
these systems are said to exhibit negative deviation from Ideality.

Example: Tetrahydrofuran and Carbon tetrachloride at 30C

8.9 Vapor- Liquid Equilibrium in mixtures non ideal behaviour

Let us consider a closed system considsting of coexisting vapor and liquid phases. The
system is maintained at constant temperature (T) and Pressure (P).


The condition of equilibrium between the two phases is given by

Chemical potential of one phase = Chemical Potential of another phase



- 73 -

Chemical potential of Vapor phase = Chemical Potential of Liquid phase (1)

We know that the chemical potential is defined as
+ = f RT ln
(2)
Hence the condition for equilibrium is given by
Fugacity of Vapor phase

v
i
f
__
= Fugacity of Liquid phase

l
i
f
__
(3)

Where v represent vapor phase and l represent liquid phase.

Fugacity in Vapor phase P y f
i i
v
i
=

__

(4)
Where y represent vapor phase composition
is the fugacity coefficient in vapor phase
P represent the pressure
Fugacity in Liquid phase
sat
i i
o
i i
l
i
P x f x f = =

__

(5)
Where x represent liquid phase composition
is the activity coefficient
sat
P represents the saturation pressure

Substituting equation (4) and (5) in equation (3) we get
sat
i i i i
P x P y =
(6)

At low pressure (upto atleast 1 bar), the vapor phase can be assumed to behave like an
ideal gas and hence 1 =
i
, hence the equation (6) reduces to
sat
i i i
P x P y =
(7)
This equation is the modified Raoults law.
If the vapor is in equilibrium with the ideal solution, 1 =
i
, then equation (6) reduces to
sat
i i
P x P y =
(8)
This reduces to the Raoults law.



- 74 -


8.10 Relative Volatility and Margules Constant

For a binary system the excess Gibbs energy of the liquid phase is given by
2 1
x Bx RT G
E
= Where B is a weak function of temperature only. Making usual
assumptions for low pressure vapor liquid equilibrium, show that relative volatility of
species 1 to species 2 at infinite dilutions of species 1 is given by
( ) ( ) B
P
P
x
sat
Sat
exp 0
2
1
1 12
= = .

Proof

Relative Volatility of species 1 to 2 is given by

2 2
1 1
12
x y
x y
=
(1)
For azeotrope mixture 0 . 1
12
=

We know from the modified Raoults law
sat
i i i i
P x P y = (i=1,2,.., N)
(2)

P
P
x
y
sat
i i
i
i

=
(3)

For Component 1
P
P
x
y
sat
1
1
1 1

=
(4)

For component 2

P
P
x
y
sat
2
2
2
2

=
(5)

Substituting Equations (4) and (5) in equation (1), we get



- 75 -

sat
sat
sat
sat
P
P
P
P
P
P
2
2
1
1
2
2
1
12
1

= =

(6)
If
2 1
x Bx RT G
E
= Margules Equation

Then
2
2 1
ln Bx = and
2
1 2
ln Bx =

At infinite dilutions of species 1 x
1
=0 and x
2
=1.0, B = =

2 1
ln ln and 1
2
=
Then equation 6 becomes
sat
sat
P
P
2
1
1
12

=


(7)

Sub. B = =

2 1
ln ln in the equation 7 we get

) exp(
2
1
12
B
P
P
sat
sat
=
(8)

Hence it is proved that relative volatility of species 1 to species 2 at infinite dilutions of
species 1 is given by ( ) ( ) B
P
P
x
sat
Sat
exp 0
2
1
1 12
= = .

8.11 Azeotropic Composition and Azeotropic Pressure

The excess Gibbs energy for a particular system is
2 1
x Bx RT G
E
= , where B is a
function of temperature only. Assuming the validity of modified Rauolts law show that
at every temperature for which an azeotrope exists. The azeotropic composition
az
x and
azeotropic pressure
az
p are related by
( )
( )
2 / 1
2
1
1
ln
ln
1
1

+ =
sat az
sat az
az
P P
P P
x

Proof:




- 76 -
Let us consider a azeotropic system with the azeotropic composition
az
x and azeotropic
pressure
az
p
The excess Gibbs energy of the system is represented by
2 1
x Bx RT G
E
=

Then
2
2 1
ln Bx = and
2
1 2
ln Bx =

For azeotropic system the modified Rauolts law is assumed to be valid

We know from the modified Rauolts law for the azeotropic system
sat
i i i
az
i
P x P y = (i=1,2,.., N)
(1)
At azeotropic point
i i
x y =
Therefore sub. This in equation we get
sat
P
P
1
1
=
(2)
sat
P
P
2
2
=
(3)
sat
az
P
P
1
1
ln ln =
(4)

sat
az
P
P
2
2
ln ln =
(5)
Divide equation (4) by equation (5)
( )
( )

=
sat az
sat az
P P
P P
2
1
2
1
ln
ln
ln
ln

(6)
( )
( )

=
sat az
sat az
P P
P P
Bx
Bx
2
1
2
1
2
2
ln
ln

(7)
Replacing
1 2
1 x x = in equation (7) and taking square root on both sides and replacing
the composition as aezotropic composition
az
x x =




- 77 -
( )
( )
2 / 1
2
1
1
ln
ln
1
1

sat az
sat az
az
az
P P
P P
x
x

(8)

( )
( )
2 / 1
2
1
1
ln
ln
1
1

=
sat az
sat az
az
P P
P P
x

(9)

( )
( )
2 / 1
2
1
1
ln
ln
1
1

+ =
sat az
sat az
az
P P
P P
x

(10)

Hence it is proved that At every temperature for which an azeotrope exists. The
azeotropic composition
az
x and azeotropic pressure
az
p are related by

( )
( )
2 / 1
2
1
1
ln
ln
1
1

+ =
sat az
sat az
az
P P
P P
x








Ex 8.4


For the system methanol (1) / methyl acetate(2) , the following equations provide a
reasonable correlation for the activity coefficients:


2
2 1
ln Ax =
2
1 2
ln Ax = where A = 2.771 0.00523T

Using Antoinnes equations and assuming validity of Modified Raoults law, calculate P
and {y
i
} for T = 318.15K and x
1
=0.25 .

Sol :




- 78 -

( )
( ) 424 . 53
54 . 2665
25326 . 14 ln
424 . 33
31 . 3643
59158 . 16 ln
2
1

=
T
P
T
P
sat
sat





kPa P
kPa P
sat
sat
64 . 65
51 . 44
2
1
=
=



A = 2.771-(0.00523)(318)=1.107

( )( )
2
1
75 . 0 107 . 1 exp = = 1.864

( )( )
2
2
25 . 0 107 . 1 exp = = 1.072


P = (0.25)(1.864)(44.51) +(0.75)(1.072)(65.64) = 73.50 kPa


718 . 0
282 . 0
2
1 1 1
1
=
= =
y
P
P x
y
sat

Tutorial 8




1) Assuming Raoults law to be valid for the system
Benzene(1)/ethylbenzene (2),



- 79 -
a)Prepare a Pxy diagram for a temperature of 100 C
b) prepare a txy diagram for a pressure of 101.33 kPa

Vapor pressures of the pure species are given by the following Antoines
equations

20 . 213
47 . 3279
0045 . 14 ln
79 . 220
51 . 2788
8858 . 13 ln
2
1
+
=
+
=
t
P
t
P
sat
sat
where t is in C and vapor pressure in kPa


2) The system acetone (1)/acetonitrile(2),the vapor pressures of the pure
species are given by,

224
47 . 2945
2724 . 14 ln
22 . 237
46 . 2940
5463 . 14 ln
2
1
+
=
+
=
t
P
t
P
sat
sat
where t is in C and vapor pressure in kPa
Assuming Raoults law to describe the vapor liquid equilibrium states of
the system,determine,
a) x
1
and y
1
for the equilibrium phases at 54 C and 65 kPa
b) t and y
1
for for P = 65 kPa and x
1
= 0.4
c) P and y
1
for t= 54 C and x
1
= 0.4
d) t and x
1
for P= 65 kPa and y
1
= 0.4
e) P and x
1
for t= 54C and y
1
=0.4