Chemical and Phase Equilibrium: Çengel Boles

Çengel
Boles
CHAPTER
15
Chemical
Thermodynamics
and Phase
Equilibrium
Third Edition
WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

15-1
Equilibrium Criteria for a Chemical
Reaction That Takes Place Adiabatically
(fig. 15-2)
Çengel
Boles
Thermodynamics
Third Edition
WCB/McGraw-Hill © The
© The
McGraw-Hill
McGraw-Hill
Companies,
Companies,Inc.,1998
Inc.,1998
15-2
Criteria for Chemical Equilibrium at
a Specified Temperature and Pressure
(Fig. 15-4)
Çengel
Boles
Thermodynamics
Third Edition

15-3
Three Equivalent KP Reactions
for Reacting ideal-gas mixtures
Çengel
Boles
Thermodynamics
Third Edition

15-4
The Larger the KP Reaction,
the More Complete the Reaction
(Fig. 15-9)
Çengel
Boles
Thermodynamics
Third Edition

15-5
Exothermic Reactions are Less
Complete at Higher Temperatures
(Fig. 15-16)
Çengel
Boles
Thermodynamics
Third Edition

15-6
Phase Equilibrium
The multicomponent multiphase system is in phase equilibrium when the
specific Gibbs function of each component is the same in all phases
Çengel
Boles
Thermodynamics
Third Edition

15-7
Equilibrium Diagram for a Two-Phase
Mixture of Oxygen and Nitrogen at 0.1 MPa
Çengel
Boles
Thermodynamics
Third Edition

15-8
Mole Fraction of Species on the
Two Sides of a liquid-Gas Interface
Unlike temperature, the mole fraction of species on the two sides of a
liquid-gas (or solid-gas or solid-liquid) interface are usually not the same
(Fig. 15-22)
Çengel
Boles
Thermodynamics
Third Edition

15-9
Dissolved Gases in a Liquid can be
Driven Off by Heating the Liquid
(Fig. 15-23)
Çengel
Boles Gas: A
Liquid: B
Thermodynamics
Third Edition

15-10
Chapter Summary
• An isolated system is said to be in chemical
equilibrium if no changes occur in the chemical
composition of the system. The criterion for
chemical equilibrium is based on the second law
Çengel
Boles
of thermodynamics, and for a system at a
specified temperature and pressure it can be
Thermodynamics
expressed as
For the reaction
where the v's are the stoichiometric coefficients.

Third Edition

15-11
Chapter Summary
Çengel • The equilibrium criterion can be expressed in

Boles
terms of the Gibbs functions as
Thermodynamics
which is valid for any chemical reaction

regardless of the phases involved.
Third Edition

15-12
Chapter Summary
• For reacting systems that consist of ideal gases
only, the equilibrium constant KP can be
expressed as
Çengel
Boles
Thermodynamics
where the standard-state Gibbs function

change G*(T) and the equilibrium constant KP
are defined as
and
Third Edition Here, Pi's are the partial pressures of the

components.
15-13
Chapter Summary
• The KP of ideal-gas mixtures can also be
expressed in terms of the mole numbers of the
components as
Çengel
Boles
Thermodynamics
where v = vC + vD - vA - vB, P is the total pressure,

and Ntotal is the total number of moles present in
the reaction chamber, including any inert gases.
The equation above is written for a reaction
involving two reactants and two products, but it
can be extended to reactions involving any
Third Edition number of reactants and products.
15-14
Chapter Summary
• The equilibrium constant KP of ideal-gas mixtures

depends on temperature only. It is independent of
Çengel
Boles
the pressure of the equilibrium mixture, and it is
not affected by the presence of inert gases. The
Thermodynamics
larger the KP, the more complete the reaction. Very

small values of KP indicate that a reaction will not
proceed to any appreciable degree. A reaction
with KP > 1000 is usually assumed to proceed to
completion, and a reaction with
KP < 0.001 is assumed not to occur at all. The
mixture pressure affects the equilibrium
composition, although it does not affect the
Third Edition
equilibrium constant KP.
15-15
Chapter Summary
• The variation of KP with temperature is expressed

Çengel
Boles in terms of other thermochemical properties
through the van't Hoff equation
Thermodynamics
where hR(T) is the enthalpy of reaction at

temperature T.
Third Edition

15-16
Chapter Summary
• For small temperature intervals, the van't Hoff

Çengel equation can be integrated to yield
Boles
Thermodynamics
This equation shows that combustion processes

will be less complete at higher temperatures since
KP decreases with temperature for exothermic
reactions.
Third Edition

15-17
Chapter Summary
Çengel • Two phases are said to be in phase equilibrium

Boles
when there is no transfor-mation from one phase
Thermodynamics
to the other. Two phases of a pure substance are

in equilibrium when each phase has the same
value of specific Gibbs function. That is,
gf = gg
Third Edition

15-18
Chapter Summary
• In general, the number of independent variables

Çengel associated with a multi-component, multiphase
Boles system is given by the Gibbs phase rule,
Thermodynamics
expressed as
IV = C - PH + 2
where IV = the number of independent variables, C

= the number of components, and PH = the
number of phases present in equilibrium
Third Edition

15-19
Chapter Summary
Çengel
Boles
• A multicomponent, multiphase system at a
Thermodynamics
specified temperature and pressure will be in

phase equilibrium when the specific Gibbs
function of each component is the same in all
phases.
Third Edition

15-20
Chapter Summary
• For a gas i that is weakly soluble in a liquid (such

Çengel as air in water), the mole fraction of the gas in the
Boles liquid yi liquid side is related to the partial pressure of
Thermodynamics
the gas Pi, gas side by Henry's Law expressed as
where H is Henry's constant.
Third Edition

15-21
Chapter Summary
• When a gas is highly soluble in a liquid (such as

ammonia in water), the mole fractions of the
Çengel species of a two-phase mixture in the liquid and
Boles gas phases are given approximately by Raoult's
Thermodynamics
law expressed as
where Ptotal is the total pressure of the mixture,

Pi,sat(T) is the saturation pressure of species i at the
mixture temperature, and yi, liquid side and
yi, gas side are the mole fractions of species i in the
Third Edition liquid and vapor phases, respectively

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Çengel

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

For the reaction

where the v's are the stoichiometric coefficients.

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

Çengel • The equilibrium criterion can be expressed in

which is valid for any chemical reaction

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

where the standard-state Gibbs function

Third Edition Here, Pi's are the partial pressures of the

where v = vC + vD - vA - vB, P is the total pressure,

• The equilibrium constant KP of ideal-gas mixtures

larger the KP, the more complete the reaction. Very

• The variation of KP with temperature is expressed

where hR(T) is the enthalpy of reaction at

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

• For small temperature intervals, the van't Hoff

This equation shows that combustion processes

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

Çengel • Two phases are said to be in phase equilibrium

to the other. Two phases of a pure substance are

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

• In general, the number of independent variables

where IV = the number of independent variables, C

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

specified temperature and pressure will be in

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

• For a gas i that is weakly soluble in a liquid (such

the gas Pi, gas side by Henry's Law expressed as

where H is Henry's constant.

WCB/McGraw-Hill © The McGraw-Hill Companies, Inc.,1998

• When a gas is highly soluble in a liquid (such as

where Ptotal is the total pressure of the mixture,

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