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Vapor/liquid equilibrium :

Introduction

Preceding chapter have dealt largely with pure substances or with constant-composition

mixtures, e.g., air. However, composition changes are the desired outcome, not only of

chemical reactions, but of a number of industrially important mass-transfer operations.

Thus composition becomes a primary variable in the remaining chapters of this text.

Process such as distillation, absorption, and extraction bring phases of different

composition into contact, and when the phase are not equilibrium, mass transfer between

the phase alters their composition. Both the extent of change and the rate of transfer

depend on the departure of the system from equilibrium. Thus, for quantitative treatment

of mass transfer the equilibrium T, P, and phase compositions must be known.

The most commonly encountered coexisting phases practice are vapor and liquid,

although liquid/liquid, vapor/solid, and liquid/solid system are also found. In this chapter

we first discuss the nature of equilibrium, and the consider two rules that give the number

of independent variables required to determine equilibrium states. There follows in sec

10.3 a qualitative discussion of vapor/liquid phase behavior. In sec 10.4 we introduce

compositions for systems in vapor/ liquid equilibrium. The first, known as Roult’s law, is

valid only for systems at low to moderate pressures and in general only for sytems

comprised of chemically similar species. The second, known as Henry’s law, is valid for

any species present at low concentration, but as presented here is also limited to systems

at low to moderate pressures. A modification or Roult’s law that removes the restriction

so chemically similar spesies is treated in sec 10.5. Finally in sec 10.6 calculations based

on equilibrium ratios or k-values are considered. The treatment of vapor/liquid

equilibrium is developed further in chaps.12 and 14.

10.1 THE NATURE OF EQUILIBRIUM

Equilibrium is a static condition in which no changes occur in the macrocospic properties

of a system with time. This imlplies a balance of all potentials that may cause change. In

engineering practice, the assumption of equilibrium is justified it leads to results of

satisfactory accuracy. For example. In the reboilier for a distillation column, equilibrium

between vapor and liquid phases is commonly assumed. For finite vaporization rates this

is an an approximation, but it does not introduce significant error into engineering

calculations.

An isolated system consisting of liquid and vapor phases in intimate contact

eventually reaches a final state where in no tendency exists for change to accur within the

system. The temperature pressure and phase compositions reach final values which

thereafter remain fixed. The system is in equilibrium. Nevertheles, at the microscopic

level, condition are not static. The moleccules comprising a phase at a given instant are

not the same molecules that later occupy the same phase.Moleccules with sufficiently

high velocities near the interface overcame surface forces and phases into the other phase.

However, the average rate of passage of molecules is the same in both directions, and no

net interphase transfer of material occurs.

Measures of Composition

The three most common measures of composition are mass fraction, and molar

concentration. Mass or mole fraction is defined as the ratio of the mass or number of

moles of a particular chemical species in a mixture or solution to the total mass or

number of moles of the mixture or solution :

X1=mi/m=mi/m or xi=ni/n=ni/n

Molar concentration is defined as the ratio of the mole fraction of a perticular chemecal

species in a mixture or solution ti its molar volume :

Ci=xi/v

The quantity has units of moles of i per unit volume. For flow processes convenience

suggest its expression as ar ratio of rates. Multiplying and dividing by molar flow rate n

gives :

Ci=ni/q

Where ni. Is molar flow rate of species I, and q is volume flow rate.

The molar mass of a mixture or solution is, by definition , the mole fraction

weigted sum of the molar masses of all species present :

M=Σ XiMi

10.2 THE PHASE RULE. DUHEM’S THEOREM

The phase rule for nonreacting systems, presented without proof in sec 2.7, result

from application of a rule of algeora. Thus, the number of variables that may be

independently fixed in system at equilibrium is the difference between the total number

of variables that characteris the intensive state of the system and the nimber of

independent equations that can be written connecting the variables.

The intensive state of a PVT system containing N chemical species and π phases

in equilibrium is characterized by the intensive variables, temperature T, pressure P, and

N-1 mole fractions 1 for each phase. These are the phase ruke variables, because they

have no influence on the intensive state of the system.

As will become clear later in this chapter, an independent phase equilibrium

equation may be written connecting intensive variables for each of the N species for each

pair of phases present. Thus, the number of phase equilibrium equations is(π-1)(N). The

difference between the number of phase rule variables and the numberof independent

equilibriums connecting them is the number of variables that may be independently fixed.

Called the degrees of freedom of the system F, the number is

F=2+ (N-1)(π)-(π-1)(N)

Upon the reduction, this becomes the phse rule:

F=2-π+N

Duhem’s theorem is another rule, similar to the phase rule, but less celebrated. It

applies to closed systems at equilibrium for which the exrensive state as well as the

intensive state of the systems is fixed. The state of such a system is said to be completely

determined, and is characterized not only by the 2 =(N-1)π+π=2+ Nπ

If the system is closed and formed from specified amounts of the chemical species

present, then a material balance equation can be written for each of the N chemical

species. These in addition to the (π-1)N phase equilibrium equatins provide a total

number of independent equations equal to :

(π-1)N+N=Πn

The difference between the number of variables and the number of equations is therefore:

2+Nπ-Πn=2

On the basis of this results, Duhem’s theorem is stated as follows :

For any closed system formed initially from given masses of prescribed

chemical species, the equilibrium state is completely determined when any two

independent variables are fixed.

The two independent variables subject to specification may in general be either or

extensive. However, the number of independent intensive variables is given by the phase

rule. Thus when F=1, at least one of the variables muct be extensive, and when F=0, both

must be extensive.

WIDODO PRIHATIN

L0C0009008

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