03 Fundamentals

Ali Kh. Al-matar

(aalmatar@kfupm.edu.sa)
Chemical Engineering Department
King Fahd University of Petroleum and
Minerals
Dhahran, Saudi Arabia
(aalmatar@ju.edu.jo)
Chemical Engineering Department
University of Jordan
Amman, Jordan
Outline
• Importance of phase equilibria.
• Essence of the problem.
• Two phase equilibria.
• The phase rule.
• Equilibrium mechanisms.
• Combined first and second laws.
• Fundamental groupings.
• Legendre transform.
• Fundamental relations.
• Maxwell relations.

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Importance of Phase Equilibria
• The world we live in is composed of mixtures:
– The air we breathe.
– The food we eat.
– The cars we drive, and their fuel etc.
• Consequently, it is of a paramount importance to
understand the way these mixtures behave and
interact.

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Essence of the Problem
• Relate quantitatively the variables that describe
the state of equilibrium of two or more
homogeneous phases that are free to
interchange energy and matter.
• Phase equilibria refers to the existence of two or
more phase in contact:
– Two phases may be VLE, LLE, SLE, SVE,
– Three phase equilibria VLLE, and
– Four phase equilibria VL3E.
– Higher number of phases.
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Two Phases Equilibria
T1
Oil and water at the interface
P1 Phase I

xi1,i=1,…,N

P2

Phase II

xi2,i=1,…,N
T2
Given xi1, i=1,…,N and T (or Given xi2, i=1,…,N and T (or
P) P)
Find xi2, i=1,…,N and P (or T) Find xi1, i=1,…,N and P (or T)

Adv. Thermo -Lecture 02: Phase equilibria 5

The Phase Rule I
• The number of intensive independent variables
that must be arbitrarily fixed to establish the
state of any system (degrees of freedom F) is
given by the Gibbs phase rule

F  2  N P  NC  N r

• Where
– NC : number of chemical species
– Nr : number of independent chemical reactions
– NP : number of phases

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Phase Rule II
• This is subject to the absence of special forces
e.g., due to gravitational, electric, or magnetic
fields, and surface forces.
• When you have special constraints such as
membranes you must take them into
consideration, since they place constraints on the
equilibrium state of the system.

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Equilibrium Mechanisms
• Within a heterogeneous system, internal
equilibrium must be considered for three types
of processes:
– Mechanical contact. Displacement of a phase
boundary. (Pressure)
– Thermal contact. Heat transfer between any two
phases within the heterogeneous system.
(Temperature)
– Material/Chemical contact. Mass transfer of any
component in the system across a phase boundary.
(Chemical potential)
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Equilibrium for a Heterogeneous System

• The governing potentials for the thermal and

mechanical equilibrium are temperature and
pressure respectively.
• A heterogeneous system that is in a state of
internal equilibrium is a system at equilibrium
with respect to each of the three processes of
contact.

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The Closed System
• A closed system is a system that does not
exchange matter with the surroundings,
although it may exchange energy.
• In the absence of any chemical reactions,
the number of moles of each component is
constant.
dni  0, i  1, ,m

• Where
• ni is the number of moles of the ith component,
• m is the number of components.

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Combined First and Second Laws
• For a closed and homogeneous system, the combined first
and second law are given as:
dU  TB d S  PE dV
• The operator d indicate small changes resulting from
interaction with the surroundings.
• The surroundings are considered to be two distinct
bodies:
– A constant volume heat bath, at a constant uniform
temperature TB in thermal contact only with the system,
and
– An external body at a constant uniform pressure PE, in
volumetric contact only with the system through a movable,
thermally insulated piston.

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Closed System Interactions
constant volume heat bath at TB

System
TB
Wj

System
Q1 PE PE
PE
W1
Ql

System

PE
Movable, thermally insulated piston

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Reversible Interactions
• If interactions occur reversibly, then the equality sign
applies and TB =T, and PE =P
dU  Td S  PdV
• This equation signifies that:
– The first term on the right is the heat absorbed by the
system (TdS=dQrev).
– The second term is the work done by the system
(PdV=dWrev).
• The same equation (equality) applies for irreversible
processes. However, the two terms can no longer be
identified with heat transfer and work.

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Finite Changes of State Properties
• Because U is a state function, we can integrate it
along a reversible path between the initial and
final states to obtain:
S2 V2

U  U 2  U1   TdS   PdV
S1 V1

• Due to the property being a state function, this

result applies whether we are talking about a
reversible or an irreversible process.

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Fundamental Grouping I
• Represents the fundamental thermodynamic
relation

dU  Td S  PdV

• If U is considered to be a function of S and V,

and if this function is known, then all other
thermodynamic properties can be obtained by
purely mathematical operations on the function.

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Fundamental Grouping II
• The temperature and pressure are defined as
 U   U 
T   P   
 S V  V S
• While another pair of independent variables
could be used to determine U, no other pair has
this simple physical significance.
• Therefore, we call the group of variables (U,S,V)
a fundamental grouping.

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Fundamental Grouping III
• Depending on the property of interest, we can
define four main fundamental groups

S S T T

U H A G

V P V P

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18
Criterion for Equilibrium
• The fundamental equation represents a potential
function.
• If the variation dU is constrained to occur at
constant S and V, then
dU S ,V  0

• At constant S and V, U tends towards a minimum

in an actual or irreversible process in a closed
system and remains a constant in a reversible
process.
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Legendre Transforms I
• Other fundamental groupings can be found using
partial Legendre transforms.
• The Legendre transforms enable us to
interchange the rules of certain variables to
other variables (conjugate).
• Examples are interchanging P and V, T and S.

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Legendre Transforms II
• To transform the fundamental relationship into a
different set of variables:
– Obtain the product of the two variables to be
interchanged.
– Make sure to take due regard for the sign of the term
in the original equation.
– Define a new function, which is the original function
minus the product of the two variables.
– Take a differential change on the new function to
obtain its differential form.

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Interchange P and V: Enthalpy
• The product of the two variables is PV
• There is a minus sign before the PdV term.
• →define transformed potential function as
the original equation minus -PV.
H  U  ( PV )
• H is the enthalpy of the system which is a
state function because it is defined in terms
of state functions.
dH  TdS  VdP
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• The independent variables now are S and P.
• The role of enthalpy as a potential for a closed
system at a constant S and P means that

dH S , P  0

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Interchange T and S: Helmholtz Energy

• The product of the two variables is TS

• There is a positive sign before the TdS term.
• → define transformed potential function as the
original equation minus TS.
A  U  (TS )

• A is the Helmholtz energy of the system which

is a state function because it is defined in terms
of state functions.
dA  SdT  PdV
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• The independent variables now are T and V.
• The role of Helmholtz energy as a potential for a
closed system at a constant T and V means that

dAT ,V  0

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Interchange T,S and P,V: Gibbs Energy

• The product of the two variables is TS and PV

• There is a positive sign before the TdS term
and a negative sign before the PdV term.
• → define transformed potential function as
the original equation minus TS-(-PV).
G  U  (TS )  (PV )  H  TS
• G is the Gibbs energy of the system which is a
state function because it is defined in terms of
state functions.
dG  SdT  VdP
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• The independent variables now are T and P.
• The role of Gibbs energy as a potential for a
closed system at a constant T and P means that

dGT , P  0

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Maxwell Relations
• The Maxwell relations may be obtained from the
fundamental equations by the application of the
Euler’s reciprocity theorem.
• Euler’s reciprocity theorem makes use of the fact
that the order of differentiation in forming
second partial derivatives is immaterial for
continuous functions and their derivatives.
  U    U 
   
x  y  y  x 

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Example
• Determine if the following function is an exact
function

Answer: It is an exact function 29

• Is the following differential exact?

Answer: It is not an exact differential

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• For an exact differential, d, expressed as

• The following relationship holds for all state

functions i.e. U, H, S, etc.

Fundamental equations
dU  TdS  PdV
dH  TdS  VdP
dA   SdT  PdV
dG   SdT  VdP 31
Fundamental Definitions and Equations

Definitions Fundamental equations

U (intrinisc) dU  TdS  PdV
H  U  PV dH  TdS  VdP
A  U  TS dA   SdT  PdV
G  H  TS  A  PV dG   SdT  VdP

Maxwell relations
 T   P   2U  S   P  2 A
      ,     
 V  S  S V S V  V T  T V T V
 T   V   2
H  S   V   2
G
     ,      
 P  S  S  P S P  P T  T  P T P
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Identities from Fundamental Equations
Identities
 U   P   H   V 
  T   P    V T  
 V T  T V  P T  T  P
 U   H   H   G 
  T     V   
 S V  S  P  P  S  P T
 U   A   A   G 
   P       S   
 V  S  V T  T V  T  P
Heat Capacities
 U   S  CV
   CV   
 T V  T V T
 H   S  CP
   CP   
 T P  T  P T 34
Journals
• J. Chem. Thermodynamics
• J. Fluid Phase Equilibria
• J. Chem. Eng. Data

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