Chemical Engineering

Thermodynamics
CHME322

Introduction
Classical Thermodynamics is divided into:

1. Engineering Thermodynamics: studied last year

covers machines (turbines, compressors, etc)
2. Chemical
Thermodynamics:
deals
with
equilibrium, both in chemical reactions, and
between phases

Why we need to study it?

Chemical Engineers are concerned with changes
of systems not in equilibrium.
Example: chemical reactions, the transfer of
components from liquid to vapour in distillation
and so on.
The rate of such processes depends on a driving
force
Driving force is a function of how far the system
is from equilibrium
Hence, equilibrium data are needed
Thermodynamics helps deals with classification,
correlation and prediction of chemical and phase
equilibrium data.

System
A region of the universe separated from the rest by real
or imaginary boundaries.

isolated

adiabatic closed
transfer of work only

closed
transfer of heat
and work

open

Types of systems
Isolated system: neither energy nor matter is
transferred across the boundary.
Closed system: energy, but not matter may be
transferred across the boundary. If work but not
heat may be transferred, the system is called
adiabatic.
Open system is one in which both matter and
energy may be transferred.

State
Is specified by a number of properties such as
Temperature, Pressure, Volume, etc.
These properties are state variables
A system is at equilibrium when none of them
change with time.

Types of properties
State variables can be either intensive
(independent of the quantity of material present)
- eg. P, T, etc - or extensive (proportional to the
quantity of material) - eg. V, H, etc.
When extensive variable is divided by the mass
or moles, it becomes a specific variable.
Thus, specific volume,v = V/n (molar density-1)
Unless otherwise stated, the specific variables
will be molar

 Most single component, single phase systems can be

completely specified by two state variables (i.e., two
degrees of freedom), and all the other variables
expressed as functions of these two, thus:
u = u(P,v) = u(P,T) = u(T,v) etc.
The value of any state variable depends only on the
state of the system (independent of the path
followed by the system between the two states)

Reversible process
Happens so slowly that the system may be regarded
as being in equilibrium at all times.
The state variables have values only infinitesimally
different from their equilibrium values, so that an
infinitesimal change is enough to cause the process to
go in the opposite direction, hence the name
"reversible

 To calculate the change Dh, Du, etc between any two

given states, we devise a reversible path between
them for which information is available to calculate
the change.

The change along any other path, including nonreversible path will be the same as that calculated
(properties are state functions).

Equations of State
Represents the relationship between state variables
(usually PvT)
P = f(v,T) or f(P,v,T) = 0
The simplest equation of state is the ideal gas
equation: Pv = RT
It represents the limiting behaviour of real gases at
low pressures.
More complex equations, such as van der Waals,
Redlich-Kwong, Benedict-Webb-Rubin (BWR) etc
have been devised, which contain additional,
adjustable constants.

Compressibility factor
Law of Corresponding States: there exists a unique
relation between the three reduced variables, the same
for all substances.
This unique relation need not be expressible by any
analytical equation
A convenient way of representing this empirical
relation is through the compressibility factor, z

Pv
PV
z =
=
RT
nRT

Van der Waals EOS

RT a
P=
- 2
v-b v
a and b are characteristic constants for each gaseous
species
b: Correction for molecular size (i.e., volume occupies
by molecules themselves)
a/v2: Correction for attractive forces between
molecules. (decrease the effective pressure)

Reduced Variables
For equations which have only two additional constants
(van der Waals, Redlich Kwong), the constants can be
eliminated by working with the reduced variables
Pr = P/Pc, Tr = T/Tc and vr = v/vc, where the suffix c
indicates the critical value
This is because, at the critical conditions there are two
extra equations that can be written:
2

P
P

= 2
=0

v T,crit v T,crit

 Applying this to the van der Waals equation:

RT a
P=
- 2
v-b v
leads to:
and
then

b =

vc
3

9 R T c vc
a = 3Pv =
8
2
c c

8 Tr
3
- 2
Pr =
3 vr - 1 vr
PcVc 3
zc
0.375
RTc 8

(1)
(2)
(3)

 It is possible to construct a unique graph of z as a

function of Pr and Tr, valid for all substances:
z = f(Tr,Pr) (therorem of corresponding state)
This is only applied when zc is the same for all gases.
In practice, this is not the case, thus, z = f(Tr, Pr, zc).
The critical compressibility factor lies in the range
0.23 < zc < 0.31
Majority of not-too-polar organics having a value
close to 0.27.
Alternatively, acentric factor w is used instead of zc

Class Problem 1
a) Derive that b = vc/3 and a= 9/8 RTcvc in the van der Waals equation
from the critical point conditions.
b) Calculate the numerical value of zc for a gas obeying van der Waals
equation. How does it compare with the range of 0.23 to 0.31 for real
gases?
c) Substitute for b in Eq.1 and a in Eq.2 to demonstrate that this leads to
the reduced form of Eq.3

d) Using the generalised compressibility factor chart:

(i) Locate the critical point and read off the value of zc.
(ii) Water has Pc = 221.2 bar, Tc = 374.2oC. What is the maximum
pressure at which saturated steam can be treated as an ideal gas
with an error of not more than 10%?
(iii) After estimating Tr, the ideal and (estimated) real densities of
saturated steam in these conditions?

Acentric factor
Symmetrical molecules or simple fluids (eg, inert gases: Ar, Kr)
conform very closely with the corresponding state principle
It is observed that for simple fluids, all vapour pressures lie on the
same line when plotting log Prsat vs 1/Tr
The line passes by log Prsat = -1.0 at 1/Tr = 1.43 (i.e., Prsat = 0.1 at
Tr = 0.7)
Normal fluids have Prsat < 0.1 at Tr = 0.7 (Prsat at Tr = 0.7
decreases with increasing asymmetry)
Acentric factor w is defined as:

w = log10 Prsat SF T 0.7 log10 Prsat T 0.7

r

w -1.0 log10 Prsat T 0.7

r

w = 0 for the inert gases.

 Compressibility factor, is given as linear functions of w:

z = z0 + wz1
Charts are given for z0 and z1 as complex functions of
Pr and Tr.
More recent cubic EOS (Redlich-Kwong-Soave, 1972,
Peng-Robinson, 1976) include a function of w as a
multiplying constant, thus enabling them to give a
closer fit to a wide range of real gases.
They are well suited to computer implementation, and
the EXCEL spreadsheet can solve them.
Because w is based on saturated vapour pressure data,
these equations are better suited to predict vapour-liquid
equilibrium than the simpler Redlich-Kwong equation.

Note that all equation of state are semi-empirical in

nature as opposed to the virial equation, which has
a strong theoretical basis in statistical mechanics.

The Fundamental Equation

The 1st and 2nd laws of thermodynamics combined to
give:
(4)
dU = T dS - P dV
Where, U (internal energy) and S (entropy).
For reversible changes only, TdS is equal to the heat
supplied to the system, while PdV is the work done
by the system
For irreversible changes the equation still applies,
but the heat supplied and work done are both less
than in the reversible case.

Flow system
Gas enters at state 1 (P1,T1)
and leaves at state 2.
The specific energy content
of the gas entering and
leaving are u1 and u2,
respectively.

P2 T2
v2 u 2
P1 T1
v1 u 1

Work P1v1 is done to force one mole of it into the system, and
P2v2 is done against the environment as it leaves.
If there is no other energy input to the system, an energy balance
gives:

u1 + P1 v1 = u2 + P2 v2
h (enthalpy)

Enthalpy:
H = U + PV
DH (the net energy input in all cases)

(5)

Helmholtz Free Energy:

Gibbs Free Energy

(6)
(7)

A = U - TS
G = H - TS

Differentiating equations (5), (6) and (7), and

substituting from (4) gives the fundamental equation:
dH = TdS + VdP
dA = -SdT - PdV
dG = -SdT + VdP

Net Work and Spontaneous Change

For any change that takes place in a closed system at
constant temperature T, the 2nd law gives:
T DS Q
(8)
where Q is the heat supplied to the system from a
reservoir at temperature T. Here, > sign applies to
irreversible processes and the = to reversible
1st Law: DU = Q - W
Then,
(9)
T DS DU - A W

 The work done by the system, W:

1. PV work against the environment
(at constant pressure = PDV)
2. Net work (e.g. mechanical, electrical, etc).
T DS DU + P DV - DG W net
In any spontaneous change at constant temperature
and pressure which produces no net work other than
PV work against the environment, the Gibbs Free
Energy must decrease, i.e. DG < 0.
Hence, any process where DG > 0 will not occur
spontaneously, but will need an input of net work

 At Equilibrium no further change occurs, so

G has reached a minimum
for any process at constant temperature and
pressure, DG = 0 at equilibrium
This equation forms the basis of much of the
study of Chemical Engineering
Thermodynamics