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.

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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