Maximum Possible Conversion.

Stoichiometric Table

Lecture 2_00 REA401T

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What highest conversion is possible in a chemical
reactor?

• After infinite time t chemically reacting mixture will

reach equilibrium (thermal and chemical).
• The chemical composition at equilibrium will
determine the maximum possible, or equilibrium
conversion X

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 Topic: EQUILIBRIUM CONVERSION (revision)

The key to understanding reaction equilibrium is the Gibbs free energy, or

free energy, G defined as

G = H − TS (6.3)

where G = free energy (kJ)

H = enthalpy (kJ)
T = absolute temperature (K)
S = entropy (kJ·K−1)

Like enthalpy H, the absolute value of G for a substance cannot be measured,

and only changes in G are meaningful.

For a process occurring at constant temperature, the change in free energy

from Equation 6.3 is:
ΔG = ΔH −T ΔS (6.4)

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A negative value of G implies a spontaneous reaction of reactants to products
(forward reaction). A positive value of G implies the reverse reaction is
spontaneous.

A system is in equilibrium when:

ΔG = 0 (6.5)

An example of a reversible reaction

is:

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The free energy can also be expressed in differential form:

dG = −SdT + VdP (6.6)

where V is the system volume.

At constant temperature, dT = 0 and Equation 6.6 becomes:

dG = VdP (6.7)

For N moles of an ideal gas PV = NRT, where R is the universal gas

constant.

Substituting this in Equation 6.7 gives:

dG = NRT x (dP/P) (6.8)

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More on the change in Gibb’s free energy

For a change in pressure from P1 to P2 Equation 6.8 can be integrated to give:

Values for free energy are usually referred to the standard free energy G0.
The standard state is arbitrary. A gas is considered to be at a standard state
if it is at a pressure of 1 bar for the designated temperature of an isothermal
process.

Thus, integrating Equation 6.9 from standard pressure P0 to pressure P

gives:

G = G0 + NRT ln(P/P0) (6.10)

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For a real system, rather than an ideal gas, Equation 6.10 is written as:

G = G0 + NRT ln(f/f0) = G0 + NRT ln(a) (6.11)

where f = fugacity, (N·m2 or bar)

f0 = fugacity at standard conditions, (N·m2 or bar)
a = f/f0 activity, (dimensionless)

The concepts of fugacity and activity have no strict physical significance but are
introduced to transform equations for ideal systems to real systems. However, it
does help to relate them to something that does have physical significance.
Fugacity can be regarded as an “effective pressure”, and activity can be
regarded as an “effective concentration” relative to a standard state.

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Free energy change for the general reaction
bB + cC + . . . . ←→ sS + tT + . . . . (6.12)
The free energy change for the reaction is given by:

where
_ ΔG = free energy change of reaction (kJ)
Gi = partial molar free energy of component i (kJ·kmol−1)

Note that the partial molar free energy is used to

designate the molar free energy of the individual component
as it exists in the mixture. This is necessary because,
except in ideal systems, the properties of a mixture
are not additive properties of the pure components. As
a result, for a mixture.

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The free energy change for reactants and products at standard conditions is given by:

where ΔG0 = free energy change of reaction when all of the reactants and
products are at their respective standard conditions, (kJ). It also called
standard Gibbs free energy of formation. It can be found experimentally (and
is reported in thermodynamics reference books!)

= partial molar free energy of component i at standard conditions,

(kJ·kmol−1)

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 ΔG continued
Combining Equations 6.13 and 6.14:

Writing Equation 6.11 for the partial molar free energy of component i in a
mixture:

where ai refers to the activity of Component i in the mixture.

Substituting Equation 6.16 in Equation 6.15 gives:

Since s ln aS = ln as S , t ln aT = ln at T . . ., Equation 6.17 can be arranged to

give:

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 At equilibrium ΔG=0!

Ka is known as the equilibrium constant. Why do we need it?

Activities ai of each component i can be expressed through partial

pressures Pi, molar fractions yi or concentrations Ci.

Conversion X (by its definition) can be expressed through Pi, yi or Ci.

Therefore we can obtain equation relating equilibrium constant Ka to

conversion X and calculate equilibrium conversion Xe and chemical
composition in a reactor at equilibrium
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Equation relating equilibrium constant Ka to conversion
X
Homogeneous gaseous reactions.
Substituting for the fugacity in Equation 6.20 gives:

For homogeneous gaseous reactions, the standard state fugacities can be

considered to be unity, that is, f0i= 1.
Fugacity is expressed as the product of partial pressure and fugacity
coefficient:
where fi = fugacity of component i
φi = fugacity coefficient of component i
Pi = partial pressure of component i
Substituting Equation 6.22 into Equation 6.21, assuming f 0i= 1:

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Also, by definition partial pressure pi is
related to total pressure P and molar fraction
yi:

Substituting Equation 6.24 into Equation 6.23 gives:

Where ΔN = s + t + . . . − b − c − . . .

For an ideal gas the fugacity coefficient of component i φi = 1, thus:

Got it: equlibrium constant Ka=f(partial pressure pi) – see eq. 6.26
and Ka=f(molar fraction yi) – see eq. 6.27!!!

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 Equation: equilibrium constant Ka=f(conversion X) – last step
To relate Ka and X, we need to know stoichiometry of our chemical reaction!

Example:

For P=1 bar:

See also example C-1, page 1024,

Fogler 4th ed.
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Stoichiometric Tables

We shall set up Stoichiometric Table using limiting reactant A as our basis of

calculation in the following reaction. We will use the stoichiometric tables to
express the concentration Ci of each reactant I as a function of conversion X.
Then we will combine Ci = f(X) with the appropriate rate law to obtain -rA = f(X).

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Batch System Stoichiometric Table (p. 85 3rd, p.101 4th )
N C y d c b
Parameter i  i 0  i 0  i 0     1
N A0 C A0 y A0 a a a

Species Symbol Initial Change Remaining

A A

B B

C C

D D

Inert I

Increase in total number of moles per mole A reacted is δ

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Concentration -- Batch System:

Constant Volume Batch:

Note: if the reaction occurs in the liquid phase or if a gas phase reaction
occurs in a rigid (e.g., steel) batch reactor
Then

etc.

if

and we have -rA=f(x)

then

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Flow System Stoichiometric Table (p. 85 3rd ed., p. 107 4th ed. ):

Where:

Species Symbol Reactor Feed Change Reactor Effluent

A A

B B

C C

D D

Inert I

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Liquid Phase Flow System:
Concentration -- Flow System:

If the rate of reaction were

This gives us -rA = f(X). Consequently, we can use the methods

discussed in Chapter 2 to size a large number of reactors, either
alone or in series.

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Gas Phase Flow System: need to account for possible volume change ε
changein total number of moles for complete conversion

total number of moles fed to reactor

etc. Again, these equations give us information about -rA = f(X), which we can use to size
reactors. For example if the gas phase reaction has the rate law

then with

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 Algorithm for Isothermal Reactor Design (Chapter 4, p. 147, 4th ed)

The Evaluate (volume V or conversion X) step can be carried out

A. Graphically (Chapter 2 plots)
B. Numerical (Quadrature Formulas Chapter 2 and Appendices)
C. Analytical (Integral Tables in Appendix)
D. Software Packages ( Polymath, SCILAB)

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Example: The elementary gas phase reaction
takes place in a CSTR at constant temperature (500 K) and constant pressure (16.4 atm).
The feed is equal molar in A and B. Find the volume of reactor V, if required conversion
X=0.9

Mole Balance

Rate Law

Stoichiometry gas phase, isothermal (T = T0), no pressure drop (P = P0)

[Why do you suppose CB is a constant, when B is being consumed?]

Combine

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Evaluate

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