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Advanced Thermodynamics Guide

This document provides an overview of key concepts in advanced thermodynamics and separation processes including: Vapour-liquid equilibrium, the phase rule, PTxy and Txy phase diagrams, azeotropes, Raoult's law for ideal gases, dewpoint and bubblepoint calculations, Henry's law, and using K-values from correlations to model vapour-liquid equilibrium. Key concepts covered include vapor pressure, the relationship between intensive variables and phases, representation of saturated and two-phase regions on phase diagrams, characterization of azeotropes, using mole fractions to calculate partial pressures and equilibrium, and models for solubility and volatility.

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173 views3 pages

Advanced Thermodynamics Guide

This document provides an overview of key concepts in advanced thermodynamics and separation processes including: Vapour-liquid equilibrium, the phase rule, PTxy and Txy phase diagrams, azeotropes, Raoult's law for ideal gases, dewpoint and bubblepoint calculations, Henry's law, and using K-values from correlations to model vapour-liquid equilibrium. Key concepts covered include vapor pressure, the relationship between intensive variables and phases, representation of saturated and two-phase regions on phase diagrams, characterization of azeotropes, using mole fractions to calculate partial pressures and equilibrium, and models for solubility and volatility.

Uploaded by

Zooy2012
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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CEIC3001 Advanced

Thermodynamics and Separation

Vapour Liquid Equilibrium


Vapour pressure: the pressure exerted by a vapour at equilibrium with a solid or
liquid phase

The Phase Rule


F = 2 N
where F = number of independent intensive variables (or degrees of freedom)
= number of phases in equilibrium
N = number of components

PTxy Phase Diagrams

The under surface contains the saturated vapour states: PTy data
The upper surface contains the saturated liquid states : PTx data
Superheated- vapour lies below the PTy ; subcooled-liquid lies above the
PTx
Interior space between the two surfaces represents the coexistence of
both the saturated phases 2-phase mixture

Txy diagram

P constants
BUBBLEPOINT (saturated liquid) curve - LOWER curve represents Tx data
DEWPOINT (saturated vapour )curve - UPPER curve represents Ty data
Equilibrium between vapour and liquid phases is represented by horizontal tie
lines
A pure liquid boils at a single T for a given P, as indicated by the end-points of
the Txy diagram

Pxy diagram

BUBBLEPOINT curve UPPER curve Px


DEWPOINT curve LOWER curve Py

PT diagram

PT diagram represents data for saturated vapour and liquid at constant


composition

Azeotropes

azeotrope is a point where the bubblepoint and dewpoint curves intersect in a


Txy or Pxy diagram
vapour and liquid = same composition ; liquid does not change composition
when evaporated
mixtures cannot be separated by distillation

Raoults Law Ideal gas

pi = yiP = x1Pisat
pi = partial pressure of component i
yi = mole fraction of component i in the vapour phase
P = total pressure
xi = mole fraction of component i in the liquid phase
Pisat= vapour pressure of component i at the system T

for an ideal gas the total pressure equals the sum of the partial pressures

Dewpoint and bubblepoint calculation with raoults law


BUBL P: Calculate {yi} and P, given {xi} and T
DEW P: Calculate {xi} and P, given {yi} and T
BUBL T: Calculate {yi} and T, given {xi} and P
DEW T: Calculate {xi} and T, given {yi} and P

Henrys Law
Estimating the solubility soluble gases in liquids
Pi = yip = xiHi

VLE from k-value correlations


Ki = yi/ xi

K value is a measure of the volatility of a component

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