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GMR Institute of Technology

Rajam, Andhra Pradesh


(An Autonomous Institution Affiliated to JNTUK, AP)

Department of Chemical Engineering


rd
Class 3 Sem. - B. Tech. (Chemical Engineering)
Course Chemical Process Calculations Course Code CHEM-2403
Prepared by Mr. P. Satya Sagar, Sr. Assistant Professor
Lecture Topic Antoine equation
Course Outcome CCHEM203.2 Program Outcome PO1,PO13
Duration 50 min Lecture 6 of 45 Unit I
REMEMBER UNDERSTAND APPLY ANALYSE EVALUATE CREATE
Learning Level
(Tick whichever is applicable)

1. Objectives
a. Enable impart knowledge on Antoine equation
b. Learnt the calculation of vapor pressure of components from Antoine equation
2. Topic Learning Outcomes
After the completion of the class the students will able to:
a. be able to identify the various parts of a three dimension Pressure-Volume-
Temperature (PvT) phase diagram including those regions where a single phase
exists and those where two phases coexist.
b. Explain phase diagram and its components Vapor pressure, triple point, equilibrium,
Dew point, bubble point
c. Calculate vapor pressure of a substance from a vapor pressure equation
d. Calculate temperature of substance from vapor pressure
3. Teaching Methodology
a. Chalk & Talk /PPT Mode
4. Applications
a. Evaporation
b. Drying
c. Distillation
d. Humidification and dehumidification
e. Cooling towers

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5. Evocation

6. Discussion

Vapor pressure or equilibrium vapor pressure is defined as the pressure exerted by a vapor in
thermodynamic equilibrium with its condensed phases (solid or liquid) at a given temperature in
a closed system. The equilibrium vapor pressure is an indication of a liquid's evaporation rate. It
relates to the tendency of particles to escape from the liquid (or a solid). A substance with a high
vapor pressure at normal temperatures is often referred to as volatile. The pressure exhibited by
vapor present above a liquid surface is known as vapor pressure. As the temperature of a liquid
increases, the kinetic energy of its molecules also increases. As the kinetic energy of the
molecules increases, the number of molecules transitioning into a vapor also increases, thereby
increasing the vapor pressure.
Main points on the phase diagram:

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Normal boiling point temperature is the point at which liquids start to boil at one
atmospheric pressure.
Triple point is the point at which the three phases, i.e. solid, liquid and vapor coexist in
equilibrium.
Critical temperature is the temperature at which a substances cant coexist in two phases
whatever pressure is applied.
Vapor pressure is the equilibrium pressure of the vapor above its liquid.
It indicates the tendency of a species to transfer from one phase to another.
Volatility of a species is the degree to which the species tends to transfer from liquid (or solid) to
state to the vapor state.
Four methods can be used to estimate the component vapor pressures:
1.Vapor pressure tables in references
2.Clapeyron equation.
3.Cox chart.
4.Antoine equation.
Clapeyron equation: Effect of Temperature on Vapour Pressure :

The forces causing the vaporization of a liquid are derived from the kinetic energy of
translation of its molecules. An increase in kinetic energy of molecular translation should
increase the rate of vaporization and therefore the vapour pressure. It was pointed out that the
kinetic energy of translation is directly proportional to the absolute temperature. On the basis of
this theory, an increase in temperature should cause an increased rate of vaporization and a
higher equilibrium vapour pressure. This is found to be universally the case. It must be
remembered that it is the temperature of the liquid surface that is effective in determining the rate
of vaporization and the vapour pressure.
An exact thermodynamic relationship between vapour pressure and temperature is
developed as
dp
dT T (VG VL )
(1)
Where p = vapour pressure
T = absolute temperature
= heat of vaporization at temperature T

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VG = volume of gas
VL = volume of liquid
The above relationship is the Clapeyron equation. It is rigorous and is applied to any
vaporization equilibrium. Its use in this form is, however, greatly restricted because it
presupposes knowledge of , VG and VL and their variation with temperature.
If the volume of the liquid is neglected and the applicability of the ideal-gas law
assumed, the above relation reduces to the Clausius-Clapeyron equation

dp dT d 1
d ln p
p RT 2 or R T (14)

Where R = gas-law constant


= molal heat of vaporization
The Clausius-Clapeyron equation in the form written above is accurate only when the
vapour pressure is relatively low, where it may be assumed that the vapour obeys the ideal-gas
law and that the volume in the liquid state is negligible compared with that of the vapour state.
Where the temperature does not vary over wide limits, it may be assumed that the molal
latent heat of vaporization is constant and equation 14 may be integrated between the limits po,
To and p, T; to give
p 1 1
ln
po R T0 T
(15)
p 1 1
log
po 2.303R T0 T
or (16)
Equation 16 permits calculation of the vapour pressure of a substance at temperature To
be known, together with the latent heat of vaporization . The results are accurate only over
limited ranges of temperature in which it may be assumed that the latent heat of vaporization is
constant, and at such conditions that the ideal-gas law is obeyed.
The Antoine equation is a vapor pressure equation and describes the relation between vapor
pressure and temperature for pure components. The Antoine equation is derived from the
ClausiusClapeyron relation.
{\displaystyle \log _{10}p=A-{\frac {B}{T}}}

where:

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A, B, C are constant picked up from references
The simplified form with C set to zero:
{\displaystyle \log _{10}p=A-{\frac {B}{T}}}

is named the August equation, after the German physicist Ernst Ferdinand August (17951870).
The August equation describes a linear relation between the logarithm of the pressure and the
reciprocal temperature. This assumes a temperature-independent heat of vaporization. The
Antoine equation allows an improved, but still inexact description of the change of the heat of
vaporization with the temperature.
The Antoine equation can also be transformed in a temperature-explicit form with simple
algebraic manipulations:

T{\displaystyle T={\frac {B}{A-\log _{10}\,p}}-C}T

7. Mind Map

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8. Readings:

1. Hougen, Olaf A., and Kenneth M. Watson. "Chemical Process Principles-Part 1: Material
and Energy Blances." (1948).
2. Himmelblau, David Mautner, and James B. Riggs. Basic principles and calculations in
chemical engineering. FT Press, 2012.
3. Bhatt, B. I., and S. M. Vora. Stoichiometry:(si units). Tata McGraw-Hill Pub. Co., 1996.
4. https://en.wikipedia.org/wiki/Antoine_equation
5. nptel.ac.in/courses/103103035/module5/lec1.pdf
6. https://www.youtube.com/watch?v=YxplklxQDmI
9. Questions:
Remember:
1. Dene i. Vapour pressure. ii. Normal boiling point
2. Write Antoines Equation, explain its significance.
3. What is Bubble point and Dew point?
Understand:
1. What is the main principle involved to derive Clausius Clapeyron equation and what
are the assumptions made.
Apply:
1. A liquid mixture containing equimolar amounts of benzene, toluene and ethylebenzene
is flashed to conditions of T= 110oC, P= 90 KPa, determine the equilibrium
molefraction{xi} and {yi} of the liquid and vapour phase formed and the molar fraction
of V of the vapour formed. Assume that raoults law applies

{\displaystyle \log _{10}p=A-{\frac {B}{T}}}


A B C

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Benzene 13.8594 2773.78 -53.08
Ethyl benzene 14.0045 3279.47 -59.95
Toluene 14.0098 31.03.01 -53.36

10. Key Words:


Clausius Clapeyron Equation,
Antoines Equation,
Vapour Liquid Equilibrium
11. Scope for Mini Project
a. Try to solve the above problems in Aspen one
b. Prepare an excel sheet to easy converting obtaining of remaining parameters when two
parameters

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