Lecture 08

Reaction Engineering

Huynh Kim Lam

www.lamhuynh.net

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Scenario A: The HCl assignment
The memo from your supervisor
You are a chemical engineer for the
ABC Chemical Company, which
makes a valuable product but also
makes hydrochloric acid (HCl) as a
waste byproduct.
This hypothetical problem is a
useful prototype
⇒ to perform some relevant
chemical engineering
calculations, design some
equipment,
⇒ justify the proposal to the
“company” through an economic
analysis, all of which are typical
tasks and approaches for a
chemical engineer, regardless of
the specific application
From: Barbara Magelby, Supervisor, Chemical Process Group
To: Lam K. Huynh
We’ve just received information indicating that the company
that has been disposing of our HCl byproduct is not doing
well. We anticipate that they will be going out of business in
6-12 months. This puts us in a very dangerous situation,
since we can’t operate very long without disposing of that
waste. Our marketing people have tried to find a potential
buyer for the acid, but the byproduct is apparently not at an
appropriate concentration or purity to be valuable to
anyone in our local area.
One possibility to consider is treatment of the waste in
order to be able to dispose of it in the lake next to our
company site. However, at this point, no engineering
analysis has been conducted on this or any other strategy.
Your assignment is to propose a strategy and design (with a
cost analysis) for safely and legally disposing of the acid
waste.
Please keep me informed of your progress.
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Scenario A: The HCl assignment

@ Neutralization reactor: HCl(aq) + NaOH(aq) → NaCl(s) + H2O

• How much time should the reactants spend in the reactor so that the
reaction proceeds to the extent desired?

• Which factors affect the reaction?

Reaction Rates
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Reaction Rates
∆ 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = −
∆𝑡𝑡
∆[𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃]
=+
∆𝑡𝑡

∆𝑡𝑡 → 0: Instantaneous rate

∆𝑡𝑡 ≫ 0: average rate over ∆𝑡𝑡

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Reaction Rates
𝐶𝐶𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
r1× 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 1 + . . + 𝑟𝑟𝑟𝑟 × (𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 2) p1 ×(Product 1) + ... + pn × (Product n)

A rate law is an equation that relates the rate of a reaction to the

concentrations of reactants (and catalyst) raised to various powers

Rateforward = 𝑘𝑘(𝑇𝑇, 𝑃𝑃) × Reactant 1 𝑚𝑚 × Reactant 2 𝑛𝑛 × [Catalyst]p

• [X] denotes concentrations of species X

• The exponents m, n and p must be determined experimentally
• k(T, P) (called rate constant or rate coefficient) is a proportionality
constant in the relationship between rate and concentrations

Ratereverse =?

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Reaction Rates

An elementary reaction is a single molecular event, such as a

collision of molecules, resulting in a reaction.

The set of elementary reactions whose overall effect is given

by the net chemical reaction/equation

A reaction intermediate is a species produced during a

reaction that does not appear in the net equation because it
reacts in a subsequent step in the mechanism

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Reaction Rates
Net chemical reaction
H2 + 1/2O2 = H2O

Elementary reactions A n Ea
H+H+M=H2+M 7.000E+17 -1.0 0.0
O+O+M=O2+M 1.000E+17 -1.0 0.0
O+H+M=OH+M 6.750E+18 -1.0 0.0
H2O+M=H+OH+M 6.06E+27 -3.3 120770.
H2O+H2O=H+OH+H2O 1.E+26 -2.4 120160.
H+O2 (+M) =HO2 (+M) 4.660E+12 0.44 0.0
H+O2(+AR)=HO2(+AR) 4.660E+12 0.44 0.0
H+O2(+O2)=HO2(+O2) 4.660E+12
H+O2(+H2O)=HO2(+H2O) 9.060E+12 0.2
0.44
0.0
0.0
The rate-determining step is
OH+OH(+M)=H2O2(+M)
OH+OH(+H2O)=H2O2(+H2O)
1E+14
1E+14
-0.37
-0.37
0.0
0.0 the slowest step
in the reaction mechanism
O+H2=OH+H 5.060E+04 2.67 6290.0
H+O2=OH+O 2.06E+14 -0.097 15022.
H2+OH=H2O+H 2.140E+08 1.52 3450.0
OH+OH=H2O+O 3.34E+04 2.42 -1930.
HO2+O=OH+O2 1.630E+13 0.0 -445.0
H+HO2=OH+OH 1.900E+14 0.0 875.0
H+HO2=H2O+O 1.45E+12 0. 0. 0.0
H+HO2=H2+O2 1.05E+14 0.0 2047.
H2+O2=OH+OH 2.040E+12 0.44 69155.0
HO2+HO2+M=H2O2+O2+M 6.84E+14 0.0 -1950.
H2O2+H=HO2+H2 1.700E+12 0.0 3755.0
H2O2+H=H2O+OH 1.000E+13 0.0 3575.0
H2O2+O=HO2+OH 9.55E+6 2.0 3970
H2O2+OH=HO2+H2O 2.000E+12 0.0 427.0

Intermediate
O, H, HO2, ....

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Reaction Rates
For an elementary reaction

The rate is proportional to the product of the concentration of

each reactant molecule

Unimolecular
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = 𝑘𝑘 × [𝐴𝐴]

Bimolecular
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = 𝑘𝑘 × 𝐴𝐴 × [𝐵𝐵]

Termolecular
𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 = 𝑘𝑘 × [𝐴𝐴] × [𝐵𝐵] × [𝐶𝐶]

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Reaction Rates
For an elementary reaction
Collision theory of reaction rates: for reaction to occur, reactant molecules must collide with
an energy greater than some minimum value and with the proper orientation

 No collision → No reaction

 The minimum energy of collision required for two molecules to react is called the
activation energy, Ea, which depends on the particular reaction

 Proper orientation Improper orientation

Copyright @ Houghton Mifflin Company. All rights reserved

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Reaction Rates
For an elementary reaction
𝒌𝒌 𝑻𝑻 = 𝒑𝒑 × 𝒁𝒁 × 𝒆𝒆−𝑬𝑬𝑬𝑬/𝑹𝑹𝑹𝑹
 Z : the frequency of molecular collision (≡number of collisions per unit of time)

 p : the fraction of collisions that occur with the reactant molecules properly oriented

 𝒆𝒆−𝑬𝑬𝑬𝑬/𝑹𝑹𝑹𝑹 : the fraction of collisions having energy greater than the activation energy

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Reaction Rates
A catalyst is a substance that increase the rate of a reaction
but is not consumed by it

A catalyst has no effect on the equilibrium composition of a

reaction mixture. A catalyst merely speeds up the attainment
of equilibrium

A catalyst provides an
alternative route for the
reaction. That alternative route
has a lower activation energy.

From unknown source

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Designing the reactor

Idealized types of reactors

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Designing the reactor

𝑟𝑟𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐,𝐴𝐴 = 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟,𝐴𝐴 × 𝑉𝑉

𝑟𝑟𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐,𝐴𝐴 : [moles/time]
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟,𝐴𝐴 : [moles/time/volume]

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Assignments

Questions 1, 3 & 7

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