Formula

Collection
Thermodynamics
K4 Spring 2017
Chapter 3

Diagrams
A PVT diagram is very difficult to read, which is why we instead use PT and PV diagrams, as shown below.

PV diagram
Its important to note the difference
between the liquid phase and the fluid
phase. The fluid phase exists past the
critical point, which is the point where the
VLE line has disappeared and the liquid
and gas phases are not distinct from one
another.

PT diagram
Important distinction to know here is that
the critical point for temperature is
different for gas and vapor.

: < )

: > )

Degrees of freedom
When looking at the PT diagram, there are
some rules regarding degrees of freedom
which can be used to determine which
region or location a phase is in.

= 2 + ()

The triple point will have F = 0, since it is only a specific location in the diagram
The solid lines have F = 1, since a given temperature will always correspond to a certain pressure and vice
versa

The regions have F = 2, since both temperature and pressure can be changed and still remain within the
different regions

Equations of state

Ideal-gas EoS
The simplest equation of state is the ideal-gas equation of state

Which is used for low-pressure gas.

Volume expansivity
1

I

Isothermal compressibility
1

K

These can be combined to

=

If both beta and kappa are zero, the fluid is considered incompressible

When conditions are not close to the critical point, beta and kappa are weak functions of temperature and
pressure. Thus for small changes in T and P a little error is introduced if they are assumed constant. This then
yields:
O
ln = O P (O P )
P

Compressibility factor



In an ideal gas, Z = 1

Virial expansions
= 1 + S + S O +

=1+ + O +

Rules of thumb for applicability

Polytropic processes

Cubic equation of state
The most generic form of cubic equation of state is

=
( + )( + )

There are several different equations of state, as shown below, and they are all based on the same general
expression. However, a higher number of modifications of constants makes them more precise.

Acentric factor
Fluids can deviate due to their molecular structure. This can be described with the acentric factor.

For simple fluids, which have a Tr=0.7, the log Prsat is -1 and the deviance from this is the acentric factor

1.0 log ]^_` Ka bc.d


All fluids having the same value of omega, when compared at the same Tr and Pr, have about the same
value of Z, and all deviate from ideal-gas behavor to about the same degree.

Vapor correlations
= c + P

Liquid correlations
Estimation of molar volumes of saturated liquids:
g
^_` PfK h
= ) e a

Another option is two parameter correlation used for estimation of liquid volumes
)
] =
)

Chapter 6
Property relations:

Formulas

= l + 1

O
= l ln +
P

= (O O P P )

O
= O P (O P )
P

Maxwell Equation:
Change in enthalpy (dH):

Change in entropy (dS):

(Above equations show the application of Maxwell equation.)

Dimensionless form of Gibbs Energy:

Residual properties:

Gibbs Energy (equation remains the same for Gibbs Energy but the values of enthalpy and entropy change
for ideal gas or residual):

The residual volume and enthalpy as dimensionless values:

p
p
=

K

p
p
=

I

Pressure and compressibility factor in connection with CEoS:

The residual Gibbs energy, enthalpy and entropy dimensionless values in connection with CEoS:

With q parameter and I integral values being:

Expression of GR, HR and SR implied by the van der Waals equation of state

p
= 1 ln

p
=1

p
= ln

Two-phase systems

For a system of a pure species in two phases in equilibrium, the Gibbs energy is equal to each other:

t = u

Also, any change to the T or P in one of the phases, will result in similar change in the other phase:

t = u

The Clausius/Clapeyron equation (check assumptions below):

Assumptions of Clausius/Clapeyron equation:

- Vapor phase is an ideal gas

- Molar volume of the liquid is negligible compared to the molar volume of the vapor

Antoine Equation

^_` = exp
+

Chapter 10

1 - Mass fraction

The molar concentration is measure of concentration of a solute (A substance which dissolved in a

solvent) over a given volume.
C is the molar concentration (M) in mol/L.
Xi is the mass or weight of solute in grams (g).
V is volume of solution in liters (L)
ni is molar flowrate (mol)
q is volumetric flowrate (L)

2 - Molar fraction
The molar mass of a mixture of solution is, by definition, the mole-fracction-weighted sum of the
molar masses of all species present:

The molar mass of mixtures M can be calculated from the mole fractions Xi of the components and
their molar masses Mi.
3 - VLE calculation (Vapor/ Liquid equilibrium)
Under VLE calculations there are two law;

- Raoults law
- Henrys law

3.1 - Raoults law

Can only be used

- at low temperatures
- at low to moderate pressures
- If the species are chemical similar
Assume that:
 - Ideal vapor phase
- Ideal solution in liquid phase
{ = { { {^_` ( = 1,2, , )

The product ({ ) is know to as the partial pressure of species i

3.2 - Henrys law

Henrys law is used under 25 oC, and for species present as a very dilute solute in the liquid phase

{ = { {

{ S 10.1 357 25 1

4 - BUBL P
Calculate yi and P, at given xi and T

Example
P = 0,33
= 100

We use Antonie equation to find the saturation pressures:

ln ^_` = Antonie equation
+
Solving the saturation pressure, we get:

f
P^_` = K

g
g f
O^_` = Kg

We now determine the pressure (P)

= O^_` + P^_` O^_` P

After that we can determine yi

P P^_`
P =

5 - DEW P
Calculate xi and P, at given yi and T
Example
P = 0,33
O = 1 P
= 100

We use Antonie equation to find the saturation pressures:

ln ^_` = Antonie equation
+
Solving the saturation pressure, we get:

f
P^_` = K

g
g f
O^_` = Kg

We now determine the pressure (P)

1
=
P O
^_` + ^_`
P O

After that we can determine xi

P
P =
P^_`

6 - BUBL T
Calculate yi and T, at given xi and P

Example
1. Guess a value of T

2. Calculate at T

P^_`
=
O^_`

3. Calculate P2sat at given T

O^_` =
P + O

4. Calculate new T by Antoine for species 2

 O
= O
O O^_`

5. Determine new

6. Iterate from 2 to converge on a temperature

7. Calculate y

P P^_`
P =

7 - DEW T
Calculate xi and T, at given yi and P

1. Guess a value of T

2. Calculate at T

P^_` /O^_`

3. Calculate P1sat at given T

P^_` = (P O )

4. Calculate new T by Antoine for species 1

P
= P
P P^_`

5. Determine new

6. Iterate from 2 to converge on a temperature

7. Calculate x

P = P /P^_`

8 - Antoine equation
Is used to determine the saturated pressure at a given temperaturer

A, B and C are found in table B.2 (page 682)

ln ^_` =
+

Determine the saturation temperature

{
{^_` = {
{ ln ()

9 - VLE from K - Value correlations

{ = eq(10.10)
Ki = K -value

{ = for vapor
{ = for liquid

It is a measure of tendency of a given chemical species to partition itself preferentially between

liquid and vapor phases is the equilibrium ratio Ki. Serves as a measure of lightness of at
constituent species of its tendency to favor the vapor phase. When Ki is greater than unity,
species i exhibits a higher concentration in the liquid phase, and is considered a heavy constituent.

9.1 - K - Value for Raoults law:
I
{ =
I

9.2 - According to eq(10.10) Modificeret Raoults law is:
I
{ =
I

According to eq. 10.10, { = { { and summation with { { = 1

{ { = 1
{

For bubblepoint calculations, where the xi are known, the problem is to find set of K-values that satisfies
Eq(10.13). Alternatively Eq(10.10) can be written, { = { /{ .

{
= 1
{
{

Chapter 11

Partial properties
Total properties of solutions calculatede from partial properties (p. 385):

= {
{

M denotes V, U, H, S, G.

{ =

Chemical potential is the partial molar Gibbs energy and for equilibrium to exist the chemical potentials of a
species is the same across all phases at a given temperature and pressure (p. 381).
u
{t = { = = {

= 1, 2,

Fugacity (f)
Fugacity is a pressure measure.

PURE SPECIES:

For an ideal gas and a pure species (p. 395)

{
{ =

The residual Gibbs energy (p. 395)

{
{p = { { = ln {

Fugacity coefficient (p. 395)

{
{ =

For the CEoS (p. 396)

ln { = { 1 ln { { { {

is given by Eq. (3.50), q is given by Eq. (3.51) and I is given by Eq. (6.65b). All written for pure species i.

SPECIES IN SOLUTION:

For equilibrium the following have to be fulfilled:

t u
= = =

The partial residual Gibbs energy (p. 402):


p = = ( )

Fugacity coefficient of species I in solution (p. 402)

=
{

yi is used instead of xi when we are dealing with a gas.

Ideal solution
Ideal solution (p. 411)
{
{{ = = { , + ln ({ )

The ideal solution parameters relate to the pure species parameters in a fairly simple way (p. 411-412):
{
= {
{
= { ln {
{
= {

Relation to get the ideal properties (p. 412)

{
{ = {
{

A simple way to relate the fugacity to the ideal solution fugacity (Lewis/Randall rule) (p. 413).
{
= { {

Excess properties
The difference between the actual property value of a solution and the value it would have as an ideal
solution at the same temperature, pressure and composition (p. 413)

= {

M denotes V, U, H, S, G.

Excess Gibbs energy (p. 417):

{
= = ln {

Activity coefficient of species i in solution (p. 417)

{ =