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Lecture-2 Introduction-System of Variable Composition (Ideal Behaviour)

This document provides an overview of classical thermodynamics and phase equilibria. It discusses: 1) The definition of equilibrium as a state with no tendency to spontaneously change properties like temperature, pressure, or composition. 2) Classical problems in phase equilibrium consider internal equilibrium with respect to heat transfer, displacement of phase boundaries, and mass transfer across phases. 3) Fundamental thermodynamic property relations for homogeneous closed systems using the Born diagram and equations relating changes in internal energy, entropy, and volume. 4) Equilibrium conditions in heterogeneous closed systems consisting of multiple phases in internal equilibrium.

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Smruthi Suvarna
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501 views

Lecture-2 Introduction-System of Variable Composition (Ideal Behaviour)

This document provides an overview of classical thermodynamics and phase equilibria. It discusses: 1) The definition of equilibrium as a state with no tendency to spontaneously change properties like temperature, pressure, or composition. 2) Classical problems in phase equilibrium consider internal equilibrium with respect to heat transfer, displacement of phase boundaries, and mass transfer across phases. 3) Fundamental thermodynamic property relations for homogeneous closed systems using the Born diagram and equations relating changes in internal energy, entropy, and volume. 4) Equilibrium conditions in heterogeneous closed systems consisting of multiple phases in internal equilibrium.

Uploaded by

Smruthi Suvarna
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Lecture-2 Introduction

(Systems of Variable Composition


Ideal behavior)

Prof.Hitesh N. Panchal
Department of Chemical Engineering
FOT, D. D. University
Nadiad-387001
Equilibrium
 No tendency to depart spontaneously for certain changes or
processes, i.e., heat transfer, work of volume displacement and
mass transfer across the phase boundary.
 In other words at equilibrium
 properties are stable, i.e., not subjected to “catastrophic” changes on
slight variations of external condition
 properties are independent of time and of previous history of the
system
 One can distinguish an equilibrium state from a steady state,
insisting that in equilibrium state there are no net fluxes of the
kind under consideration (HT, etc.) across a plane surface placed
anywhere in the system i.e., say, in HT, (𝜕𝑇 𝜕𝑡)I =(𝜕𝑇 𝜕𝑡)II= 0
(at steady state) at equilibrium 𝑞(I) = 𝑞(II)
 A change in the equilibrium state of a system is called a process
Classical Thermodynamics of Phase Equilibria

 Classical problem of phase equilibrium considers internal


equilibrium w.r.t. three processes.
 Heat Transfer between any two phases within the heterogeneous
system (due to temperature), i.e., governing potential is
thermal potential.
 Displacement of a phase boundary (due to pressure), i.e.,
governing potential is mechanical potential.
 Mass Transfer of any component in the system across a phase
boundary, i.e., governing potential is chemical potential.
 A heterogeneous system that is in a state of internal
equilibrium is a system at equilibrium w.r.t. each of these
three processes.
Fundamental Property Relations (Born diagram)

 Thermodynamic square or Koenig-Born thermodynamic square


 Homogeneous Closed system, reversible system, Single phase
fluid, no chemical reaction.
 VAT UG SHiP
Homogeneous closed system-Born diagram

 So for finding out the change in Internal Energy(dU)


 Write natural variables in differential form
dU dS dV
 An arrow from S to T implies that TdS is a positive contribution
to dU, while arrow from P to V implies that PdV is a negative
contributoion.
 Read the coefficients for dS and dV together with signs from
“thermodynamic square”
dU = +TdS -PdV
Equilibrium in a Heterogeneous Closed System

 A heterogeneous closed system is made up of two or more


phases with each phase considered as an open system within
the overall closed system
 Consider a heterogeneous system is in a state of internal
equilibrium w.r.t. three processes of HT, boundary
displacement and mass transfer
 Criteria for equilibrium in a closed system
Homogeneous Closed Systems
 A homogeneous system is one with uniform properties throughout ; i.e., a
property such as density has the same value from point to pint in macroscopic
sense. In other words, a phase is a homogeneous system.
 A closed system: does not exchange matter with its surroundings although it
may exchange energy. In a closed system (in absence of chemical reaction), the
number of moles of each component is constant
𝑑𝑛𝑖 = 0 ; 𝑖 = 1, 2, 3, - - - - 𝑚
 For a homogeneous closed system taking into account interactions of the system
with its surrounding in the form of heat transfer and work of volumetric
displacement, a combined statement of 1st and 2nd laws of thermodynamics:
𝒅𝑼 ≤ 𝑻𝑩𝒅𝑺 − 𝑷𝑬𝒅𝑽
where ‘𝑇𝐵’ is surrounding temperature and ‘𝑃𝐸’ is surrounding pressure;
 𝑑𝑈,𝑑𝑆,𝑑𝑉 are small changes in energy, entropy and volume of system resulting
from interactions •
 Each of these properties (𝑈,𝑆,𝑉) is a state function whose value in prescribed
state is independent of previous history of the system
Important Aspects

 Chemical Engineering deals


 Species chemically react to form a desired product
 Product must be separated from other by-products and un-reacted
reactants
 Generally separation methods involve contact or formation of
different phases
 One species of a mixture preferentially segregates
 Industries have to follow pollution board regulations
 Cleaning contaminated environments also requires separation
methodology
 Important to estimate degree to which species transfer into a
different phase as function of processing conditions.

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Important Aspects

 Reliable design and simulation of separation processes


 In distillation, mixture of toluene and hexane, one shall want to know,
at certain 𝑇 & 𝑃 , how toluene (or hexane) is distributed between
liquid and gaseous phases.
 In extraction of acetic acid from an aqueous solution using benzene,
one should know how acetic acid distributes itself between two liquid
phases.
 It is necessary to have knowledge of Phase equilibrium behavior of
liquid and vapor phase
 Design and implementation of such processes for successful operation
depend entirely upon performance and results of VLE experiments
conducted on a bench-scale in thermodynamic labs around world.

9 06-Jul-21
Fundamental Property Relation (Homogeneous closed system )

 Other fundamental thermodynamic properties or grouping can be obtained by


using 𝑃,𝑉,𝑇,𝑆 as independent variables in the RHS of 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
 For example,
𝐻 = 𝑈 — (−𝑃𝑉) = 𝑈 + 𝑃𝑉
𝑑𝐻 = 𝑑𝑈 + 𝑉𝑑𝑃 + 𝑃𝑑𝑉
𝑑𝐻 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑉𝑑𝑃 + 𝑃𝑑𝑉 ⇒ 𝒅𝑯 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃
 Enthalpy change in the system 𝒅𝑯 = 𝑻𝒅𝑺 + 𝑽𝒅𝑷
 At constant 𝑆 and 𝑃, (𝒅𝑯)𝑺,𝑷 ≤ 𝟎
 Similarly, We have Helmholtz Energy,
𝐴 = 𝑈 − 𝑇𝑆
𝑑𝐴 = 𝑑𝑈 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
𝑑𝐴 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉
𝒅𝑨 = −𝑺𝒅𝑻 − 𝑷𝒅𝑽
 For constant 𝑇 and 𝑉 , (𝒅𝑨 )𝑻,𝑽 ≤ 𝟎
Fundamental Property Relation (Homogeneous closed system )

 We have Gibbs energy


𝑮 = 𝑼 − 𝑻𝑺 − (−𝑷𝑽) = 𝑯 − 𝑻𝑺 [ 𝐻 = 𝑈 + 𝑃𝑉 ]
By taking 𝑇 and 𝑃 as an independent variables,
𝑑𝐺 = 𝑑𝑈 − 𝑆𝑑𝑇 –𝑇𝑑𝑆 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
Since 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝒅𝑮 = −𝑺𝒅𝑻 + 𝑽𝒅𝑷
 At constant 𝑇 and 𝑃, (𝒅𝑮)T,P ≤ 𝟎
 𝐻,𝐴,𝐺 are treated as thermodynamic potentials
Thank you

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