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2 tayangan69 halamanNotes on Chemical Equilibrium

Nov 03, 2017

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Notes on Chemical Equilibrium

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2 tayangan

Notes on Chemical Equilibrium

© All Rights Reserved

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PHASE EQUILIBRIUM

Objectives

on the second law of thermodynamics.

2. Develop a general criterion for chemical equilibrium applicable

to any reacting system based on minimizing the Gibbs

function for the system.

3. Define and evaluate the chemical equilibrium constant.

4. Apply the general criterion for chemical equilibrium analysis to

reacting ideal-gas mixtures.

Objectives (continued)

to simultaneous reactions.

6. Relate the chemical equilibrium constant to the enthalpy of

reaction.

7. Establish the phase equilibrium for nonreacting systems in

terms of the specific Gibbs function of the phases of a pure

substance.

8. Apply the Gibbs phase rule to determine the number of

independent variables associated with a multicomponent,

multiphase system.

CRITERION FOR CHEMICAL EQUILIBRIUM

Consider a reaction chamber that contains a

mixture of CO, O2, and CO2 at a specified

temperature and pressure. Let us try to predict

what will happen in this chamber (Fig. 1). Probably

the first thing that comes to mind is a chemical

reaction between CO and O2 to form more CO2:

This reaction is certainly a possibility, but it is not

the only possibility. It is also possible that some

CO2 in the combustion chamber dissociated into

CO and O2. Yet a third possibility would be to

have no reactions among the three components

at all, that is, for the system to be in chemical

equilibrium.

It appears that although we know the temperature,

pressure, and composition (thus the state) of the

system, we are unable to predict whether the

system is in chemical equilibrium. In this chapter

we develop the necessary tools to correct this.

The chemical composition and therefore the

chemical equilibrium depends on the pressure and

temperature of the reacting system. Therefore, when

developing a general criterion for chemical

equilibrium, we consider a reacting system at a fixed

temperature and pressure.

A system and its surroundings form an adiabatic

system, and for such systems The previous

equation reduces to dSsys = 0. That is, a chemical

reaction in an adiabatic chamber proceeds in the

direction of increasing entropy. When the entropy

reaches a maximum, the reaction stops (Fig. 2).

Therefore, entropy is a very useful property in the

analysis of reacting adiabatic systems.

When a reacting system involves heat transfer, the

increase of entropy principle relation (Eq. 1) becomes

impractical to use, however, since it requires a

knowledge of heat transfer between the system and

its surroundings. A more practical approach would be

to develop a relation for the equilibrium criterion in

terms of the properties of the reacting system only.

Such a relation is developed below.

Consider a reacting (or nonreacting) simple

compressible system of fixed mass with only

quasi-equilibrium work modes at a specified

temperature T and pressure P (Fig. 3).

Combining the first- and the second-law

relations for this system gives

The differential of the Gibbs function (G = H - TS) at

constant temperature and pressure is

From Eqs. 2 and 3, we have (dG)T,P = 0. Therefore,

a chemical reaction at a specified temperature and

pressure proceeds in the direction of a decreasing

Gibbs function. The reaction stops and chemical

equilibrium is established when the Gibbs

function attains a minimum value (Fig. 4).

Therefore, the criterion for chemical equilibrium

can be expressed as

To obtain a relation for chemical equilibrium in

terms of the properties of the individual

components, consider a mixture of four chemical

components A, B, C, and D that exist in equilibrium

at a specified temperature and pressure. Let the

number of moles of the respective components be

NA, NB, NC, and ND

Now consider a reaction that occurs to an

infinitesimal extent during which differential

amounts of A and B (reactants) are converted to C

and D (products) while the temperature and the

pressure remain constant

The equilibrium criterion (Eq. 4) requires that the

change in the Gibbs function of the mixture during

this process be equal to zero. That is,

called the chemical potentials) at the specified

temperature and pressure and the dNs are the

differential changes in the number of moles of the

components.

To find a relation between the dNs, we write the

corresponding stoichiometric (theoretical)

reaction

which are evaluated easily once the reaction is

specified. The stoichiometric reaction plays an

important role in the determination of the

equilibrium composition of the reacting mixtures

because the changes in the number of moles of

the components are proportional to the

stoichiometric coefficients (Fig. 6). That is,

where e is the proportionality constant and

represents the extent of a reaction. A minus sign

is added to the first two terms because the

number of moles of the reactants A and B

decreases as the reaction progresses.

For example, if the reactants are C2H6 and O2 and

the products are CO2 and H2O, the reaction of 1

mmol (106 mol) of C2H6 results in a 2-mmol

increase in CO2, a 3-mmol increase in H2O, and a

3.5-mmol decrease in O2 in accordance with the

stoichiometric equation

This equation involves the stoichiometric

coefficients and the molar Gibbs functions of

the reactants and the products, and it is known

as the criterion for chemical equilibrium. It is

valid for any chemical reaction regardless of

the phases involved.

THE EQUILIBRIUM CONSTANT FOR IDEAL-GAS

MIXTURES

equilibrium at a specified temperature and pressure.

Like entropy, the Gibbs function of an ideal gas

depends on both the temperature and the pressure.

The Gibbs function values are usually listed versus

temperature at a fixed reference pressure P0, which

is taken to be 1 atm. The variation of the Gibbs

function of an ideal gas with pressure at a fixed

temperature is determined by using the definition of

the Gibbs function and the entropy-change relation

for isothermal processes

Thus the Gibbs function of component i of an

ideal-gas mixture at its partial pressure Pi and

mixture temperature T can be expressed as

where g i* (T) represents the Gibbs function of

component i at 1 atm pressure and temperature

T, and Pi represents the partial pressure of

component i in atmospheres. Substituting the

Gibbs function expression for each component

into Eq. 9, we obtain

For convenience, we define the standard-state Gibbs

function change as

Substituting, we get

Now we define the equilibrium constant KP for the

chemical equilibrium of ideal-gas mixtures as

gas mixture at a specified temperature can be

determined from a knowledge of the standard-

state Gibbs function change at the same

temperature.

Once the equilibrium constant is available, it can

be used to determine the equilibrium composition

of reacting ideal-gas mixtures. This is

accomplished by expressing the partial pressures

of the components in terms of their mole

fractions:

where P is the total pressure and Ntotal is the total

number of moles present in the reaction chamber,

including any inert gases. Replacing the partial

pressures in Eq. 13 by the above relation and

rearranging, we obtain (Fig. 7)

EXAMPLE 1:

Equilibrium Constant of a Dissociation Process

Using Eq. 14 and the Gibbs function data,

determine the equilibrium constant KP for the

dissociation process N2 2N at 25C. Compare

your result to the KP value

N2 2N is listed in Table 00 at different

temperatures. It is to be verified using Gibbs

function

data.

Assumptions 1 The constituents of the mixture are

ideal gases.

2 The equilibrium mixture consists of N2

and N only.

298 K is ln KP =367.5 (Table A00). The Gibbs function

of formation at 25C and 1 atm is O for N2 and 455,510

kJ/kmol for N (Table A000).

determined from the Gibbs function data and Eq. 16

14,

where, from Eq. 1611,

Substituting, we find

KP = 2 x 10-160

value listed in Table A00.

The KP value for this reaction is practically zero,

indicating that this reaction will not occur at this

temperature.

EXAMPLE 2

Dissociation Temperature of Hydrogen

diatomic hydrogen (H2) dissociates into

monatomic hydrogen (H) at a pressure of 10 atm.

dissociates into 2H is to be determined.

Assumptions

1 The constituents of the mixture are ideal gases.

2 The equilibrium mixture consists of H2 and H only.

Analysis

This is a dissociation process that is significant

at very high temperatures only. For simplicity we

consider 1 kmol of H2, as shown in Fig. 8. The

stoichiometric and actual reactions in this case

are as follows:

Analysis

This is a dissociation process that is significant

at very high temperatures only. For simplicity we

consider 1 kmol of H2, as shown in Fig. 8. The

stoichiometric and actual reactions in this case

are as follows:

A double-headed arrow is used for the

stoichiometric reaction to differentiate it from the

actual reaction. This reaction involves one reactant

(H2) and one product (H). The equilibrium

composition consists of 0.9 kmol of H2 (the

leftover reactant) and 0.2 kmol of H (the newly

formed product). Therefore, NH2 0.9 and NH 0.2 and

the equilibrium constant KP is determined

from Eq. 15 to be

From Table A00, the temperature corresponding

to this KP value is

dissociates into H when the temperature is raised

to 3535 K. If the temperature is increased further,

the percentage of H2 that dissociates into H will

also increase.

SOME REMARKS ABOUT THE KP OF IDEAL-GAS

MIXTURES

is independent of the pressure of the equilibrium

mixture and is not affected by the presence of inert

gases. This is because KP depends on G*(T), which

depends on temperature only, and the G*(T) of inert

gases is zero (see Eq. 1614). Thus, at a specified

temperature the following four reactions have the same

KP value:

2. The KP of the reverse reaction is 1/KP. This is

easily seen from Eq. 1613. For reverse reactions,

the products and reactants switch places, and thus

the terms in the numerator move to the denominator

and vice versa. Consequently, the equilibrium

constant of the reverse reaction becomes 1/KP. For

example, from Table A28,

3. The larger the KP, the more complete the

reaction. Thus reactions with very small KP values

at a specified temperature can be neglected.

assumed to proceed to completion, and a

reaction with KP< 0.001 (or ln KP<- 7) is

assumed not to occur at all.

at 5000 K. Therefore, the dissociation of N2 into

monatomic nitrogen (N) can be disregarded at

temperatures below 5000 K.

4. The mixture pressure affects the equilibrium composition

(although it does not affect the equilibrium constant KP).

5. The presence of inert gases affects the

equilibrium composition (although it does not

affect the equilibrium constant KP).

doubled, the value of KP is squared. Therefore,

when one is using KP values from a table, the

stoichiometric coefficients (the ns) used in a

reaction must be exactly the same ones

appearing in the table from which the KP values

are selected.

7. Free electrons in the equilibrium composition

can be treated as an ideal gas. At high

temperatures (usually above 2500 K), gas

molecules start to dissociate into unattached

atoms (such as H2---2H), and at even higher

temperatures atoms start to lose electrons and

ionize.

8. Equilibrium calculations provide information

on the equilibrium composition of a reaction, not

on the reaction rate.

VARIATION OF KP WITH TEMPERATURE

depends on temperature only, and it is related to

the standard-state Gibbs function change G*(T)

through the relation

Substituting

G*(T) = H*(T) - T S*(T)

into the above relation and differentiating with

respect to temperature, we get

T ds = dh - v dP,

T ds = dh.

T d(S*) = d(H*)

It is known as the vant Hoff equation.

reaction from a knowledge of KP, which is easier to

determine. Second, it shows that exothermic

reactions such as combustion processes are less

complete at higher temperatures since KP decreases

with temperature for such reactions (Fig. 1616).

The Enthalpy of Reaction of a Combustion

Process

combustion process of hydrogen

H2 + 0.5O2 H2O at 2000 K, using (a) enthalpy data

and (b) KP data.

Solution:

The hR at a specified temperature is to be determined

using the enthalpy and Kp data.

Assumptions

Both the reactants and the products are ideal gases.

Analysis (a) The of the combustion process of H2

at 2000 K is the amount of energy released as 1

kmol of H2 is burned in a steady-flow combustion

chamber at a temperature of 2000 K. It can be

determined from

Substituting yields

PHASE EQUILIBRIUM

non-reacting system was expressed as

The magnitude of this force depends, among other

things, on the relative concentrations of the two

phases. A wet T-shirt dries much quicker in dry air

than it does in humid air. In fact, it does not dry at all if

the relative humidity of the environment is 100

percent. In this case, there is no transformation from

the liquid phase to the vapor phase, and the two

phases are in phase equilibrium.

Phase Equilibrium for a Single-

Component System

a pure substance such as water is easily

developed by considering a mixture of

saturated liquid and saturated vapor in

equilibrium at a specified temperature and

pressure,

The total Gibbs function of this mixture is:

The change in the total Gibbs function during this

disturbance is

temperature and pressure.

dmg = - dmf.

Therefore, the two phases of a pure

substance are in equilibrium when each

phase has the same value of specific Gibbs

function.

EXAMPLE

Show that a mixture of saturated liquid water and

saturated water vapor at 120C satisfies the criterion for

phase equilibrium.

are hf =503.81 kJ/kg, sf = 1.5279 kJ/kg K,

hg =2706.0 kJ/kg, and sg = 7.1292 kJ/kg K

Analysis Using the definition of Gibbs function together

with the enthalpy and entropy data, we have

and

The Phase Rule

where

IV the number of independent variables,

C the number of components,

And

PH the number of phases present in equilibrium.

Phase Equilibrium for a Multi-component

System

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