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Unit 5

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25 views10 pages

Unit 5

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padminisuthakar
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© © All Rights Reserved
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REACTION EQUILIBRIA 9 Criteria of chemical reaction

equilibrium in thermodynamic systems, Homogeneous gas and


liquid phase reactions, heterogeneous reactions – phase and
chemical equilibrium , Introduction to molecular
thermodynamics, Intermolecular forces, Potential function
Introduction
• the “activities” (partial pressures for ideal gases) of products divided by reactants can be related to a
quantity, Ka, that does not depend on pressure or composition, and despite its dependence on
temperature, it is called the equilibrium constant
• Developing the relationship between activities utilizes the concept of minimizing Gibbs energy and
rearranging the basic relation. By study of the derivation we learn how to generalize reaction equilibrium
analysis to multiple reactions and simultaneous reaction and phase equilibria.
• the
yiP relation between
is the partial equilibrium
pressure constraint
(always expressed and
in bar) of partial pressure isand
the ith component, written
vi is the stoichiometric coefficient

• The major steps to solving an equilibrium problem are as follows.


• 1. Ascertain how many phases are present and the method to be used for the equilibrium calculations.
• 2. Use standard state properties to obtain the value of the equilibrium constant at the reaction temperature, or for the Gibbs
minimization method find the Gibbs energies of the species. Usually this consists of two substeps:
• a. Perform a calculation using the standard state Gibbs energies at a reference temperature and pressure.
• b. Correct the temperature (and pressure for Gibbs method) to the reaction conditions.
• 3. Perform a material balance on the reactant and product species and relate the composition to the equilibrium constant or
standard state properties from steps (1) and (2).
• 4. Solve for the equilibrium compositions.
Reaction Equilibrium Constraint
• At reaction equilibria, the total Gibbs energy is minimized. If the composition of a system is changing, the change in the
Gibbs energy is given by:

• The fact that species are being created or consumed by a reaction does not alter this equation. At constant temperature
and pressure, the first two terms on the right-hand side drop out

Because G is minimized at equilibrium at fixed T and P, the derivative with respect to reaction coordinate is zero:

• rewrite above eqns in terms of fugacities fugacity dG = RT dln f

where Gio is the standard state Gibbs energy of species i and fio is the standard state fugacity
• The Equilibrium Constant
• The ratio appearing in the logarithm is known as the activity
• We define the product term at equilibrium as the equilibrium constant Ka
with the a subscript to denote that activity is used:

• Combining all the equations


• The Equilibrium Constant for Ideal Gases
• For ideal gases, the numerator of the activity is
• For gaseous reacting species, the convention is to use a standard state of
the pure gas at P° = 1 bar. For an ideal gas, fio = Po
• Thus, fio = 1 bar. The fugacity ratio (activity) is dimensionless provided that
we always express the partial pressure in bar.
The Standard State Gibbs Energy of Reaction
• is called the standard state Gibbs energy of reaction at the
temperature of the reaction, which we will denote
• The standard state Gibbs energy for reaction can be calculated using Gibbs
energies of formation.

• Relation between Gibbs energy of reaction and the equilibrium constant.


Effects of Pressure, Inerts, and Feed Ratios
• At a given temperature, equilibrium values of the reaction coordinate are affected by pressure, inerts, and
feed ratios. The principle that changing the quantities affect
• Pressure Effects
• Pressure has little effect on the activities of condensed species (e.g., the Poynting correction is typically small)
and thus it has a primary significance only for reactions with gas phase components.
• Pressure has important effects when both 1) gas species are involved in reactions and 2) the stoichiometric
numbers of gas species are different for reactants and products.
• When the stoichiometric moles of gas species are the same for reactants and products, P has no effect by the
ideal gas approximation, and for nonideal gases only indirect effects due to fugacity coefficients.s equilibrium
conversions is known as Le Châtelier’s principle
• The equilibrium constants for ideal gases can be written
• When the stoichiometric number of gas moles is the same for products and reactants, Σvi = 0 and the
pressure effect drops out.
• When the stoichiometric numbers of vapor reactant moles is greater than the stoichiometric numbers of
product vapor moles, an increase in pressure will drive the reaction to higher conversions,. Σvi < 0.
• qualitatively the pressure “squeezes” the reaction towards the side with fewer gas moles
• Inerts
• A component that does not participate in a reaction is called inert. Inert gas
components often have an indirect, but important effect on the equilibrium reaction
coordinate when gas phase species are present.
• Inerts change the overall mole fractions and thus mitigate the pressure effects.
• When Σvi > 0, adding an inert will increase conversion at a fixed total pressure.
• However, when Σvi < 0, the mitigation of the pressure effect is undesirable and inerts
should be avoided.
• Qualitatively, the presence of an inert decreases the “squeezing” effect
• Nonstoichiometric Feed
• Conversions of specific reactants are influenced using nonstoichiometric feed.
Determining the Spontaneity of Reactions

• For no product in the reactant and assumption of ideal condition

• For actual condition, weighting with the stoichiometric numbers


• Gibbs energy of reaction

• A reaction with is called exergonic and results in Ka > 1


• reaction with is called endergonic, resulting in Ka < 1
• The propensity for the reaction to go forward or backward depends instead on the Gibbs
energy of reaction ΔGT at the concentrations represented by the fugacity ratios.
• If the conditions provide ΔGT< 0, then the Gibbs energy is lowered when the reaction
proceeds in the forward direction. If we evaluate conditions and ΔGT > 0, then the reaction
goes in the reverse direction
Temperature Dependence of Ka

• temperature effects by applying classical thermodynamics to the change in


Gibbs energy with respect to temperature using theGibbs-Helmholtz relation

• which results in the van’t Hoff equation

• Substituting into the van’t Hoff equation and integrating again,

• all values at TR can be lumped together in a constant, I.

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