Chapter 14

Chemical Reaction Engineering

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 What Actually Drives Reactions?

Is it Energy?

Can We Just Calculate or Measure the Energy

Difference of Reactants and Products and Know
Which Way the Reaction Will Go?

Why do chemical reactions occur??????

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 Some Basic Definitions

Le Chatelier's Principle
"If a change is made to a system, the system will respond so as
to absorb the force causing the change.“

Equilibrium
At equilibrium none of the properties of a system change with
time. A system at equilibrium returns to equilibrium if disturbed.

"Stable" describes a system or phase in its lowest energy state.

"Metastable" describes a system or phase in any other energy

state.

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Chemical Engineering Thermodynamics
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 Gibbs Free Energy of a Phase

The Gibbs free energy G is the thermodynamic potential that

tells us which way a reaction goes at a given set of physical
conditions--neither the enthalpy change nor the entropy change
for a reaction alone can provide us with this information.

The two measures of energy (enthalpy H and entropic energy

TS) are brought together in the Gibbs free energy equation: (the
chemical potential is the equivalent for a component)

G = U + PV – TS (14.1)

which says that the Gibbs free energy G is the internal energy
U plus the energy gains by virtue of not being allowed to expand
minus the entropic energy TS.

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G is the difference between the heat energy and the entropic
energy.

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 How does Gibbs Law relate to the First Law of
Thermodynamics?

H = U + PV
and

dH = dU + PdV + VdP

substitution of dU gives:

dH = T dS + V dP

substituting the above equation into the defined equation for

Gibbs free energy:
dG = V dP – S dT (14.2)

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These relations indicate that:

the change in Gibbs free energy with respect to pressure is the

molar volume V;

the change in Gibbs free energy with respect to temperature is

minus the entropy S

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Methods of Determining Free Energy from Formation
Data
The defining equation for Gibbs free energy

G = H - TS
can be written as

ΔG = ΔH - TΔS
such that the Gibbs free energy of formation ΔGf° is

ΔGf° = ΔHf° - T ΔSf° (14.3)

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Example 14.1:
Determine the Gibbs free energy of formation of anhydrite
(Calcium Sulphate)

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Methods of Determining Free Energy from Reaction
Data
Gibbs free energy of reaction can be written as the enthalpy
change of reaction minus the entropic energy change of
reaction

ΔGRxn = ΔHRxn – TΔSRxn (14.4)

If the heat energy equals the entropic energy

ΔHRxn = TΔSRxn
then

ΔGRxn = 0
and there is no reaction.

We can now determine whether a given reaction will occur if we

know H and S, and both of these are measurable or can be
calculated.
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If ΔGRxn < 0; Gibbs free energy of the products is lower than the
Gibbs free energy of the reactants, and the reaction moves to
produce more products.

If ΔGRxn > 0; Gibbs free energy of the products is greater than

the Gibbs free energy of the reactants, and the reaction moves
to produce more reactants.

Example 14.2:
Determine the Gibbs free energy for the following reaction at
STP.

Chemical Engineering Thermodynamics

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