Rate law

Biological Rate Processes

Instructor: Vignesh Muthuvijayan

Rate law
• An algebraic equation
• Solely a function of
• the reacting materials
• reaction conditions
• species concentration
• temperature
• pressure
• type of catalyst
• Independent of the type of reactor (batch or continuous flow)
• As properties and reaction conditions may vary with position in
a reactor, 𝑟𝑗 can be a function of position

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 Rate law

Equation from Octave Levenspiel, Chemical Reaction Engineering,

3rd Edition, 2006, Wiley

Rate law
• Algebraic form of the rate law for −𝑟𝐴 for the rxn

A → products

can be the following linear function of concentration

−𝑟𝐴 = 𝑘𝐶𝐴
• Other forms such as the following are also possible
𝑘 𝐶𝐴
−𝑟𝐴 = 𝑘𝐶𝐴𝑛 (or) −𝑟𝐴 = 1+𝑘1
2 𝐶𝐴
• Concentration dependence of the rate law is established
through experiments

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 Temperature-dependent term
• Consider the k’s in the rate expressions
• Called as rate coefficients or rate constants
• Not a true constant
• Independent of concentrations
• Strong functions of temperature
• Depends on whether a catalyst is present or not
• May be a function of pressure in gas-phase reactions
• May depend on ionic strength and choice of solvent
• Here, k is treated as a function of temperature only

Arrhenius equation
• Temperature dependence of the rate coefficient is
given by the Arrhenius equation
𝑘 𝑇 = 𝐴𝑒 −𝐸/𝑅𝑇
• A = preexponential factor or frequency factor
• E = activation energy, J/mol
• R = universal gas constant = 8.314 J/mol.K
• T = absolute temperature, K
• Verified empirically

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 Arrhenius equation
• ln k vs T is a straight line with large slope
for high E, and small slope for small E
• Reactions with high E are more
temperature-sensitive
• Reactions are more temperature-sensitive
at lower temperatures compared to

ln k
higher temperatures
• Value of frequency factor does not affect
the temperature-sensitivity

Image from Octave Levenspiel, Chemical Reaction Engineering,

3rd Edition, 2006, Wiley

Arrhenius equation
• Temperature rise needed to double the reaction
rate for given activation energies and average
temperatures

Table from Octave Levenspiel, Chemical Reaction Engineering, 3rd

Edition, 2006, Wiley

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 Example #1
• Milk is pasteurized if it is heated to 63 °C for 30 min, but if it is heated
to 74 °C it only needs 15 s for the same result. Find the activation
energy of this sterilization process.

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 Concentration-dependent term
• Form of the concentration term depends on the
type of reaction
• Form and number of kinetic equations used to
describe the reaction
• For this analysis, temperature is held a constant →
Rate constant doesn’t change

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Single and multiple reactions

• Single reaction: one stoichiometric equation and
one rate equation
• Multiple reactions: more than one stoichiometric
equation needing more than one kinetic expression
• Series
A→R→S
• Parallel: two types

Equation from Octave Levenspiel, Chemical Reaction Engineering,

3rd Edition, 2006, Wiley

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 Single and multiple reactions
• More complex reaction schemes are also possible
A+B→R
R+B→S
• Reaction is in parallel for B and in series for R

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Elementary and nonelementary reactions

• Elementary reaction: a reaction in which the
molecules react exactly as written in the
stoichiometric equation
• Nonelementary reaction: reactions in which
formation of products from the reactants occurs
through a series of steps
• observed as a single reaction because the intermediates
formed are negligibly small and can’t be detected

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 Power law model
• Theory can postulate the relation between rate of
reaction and concentration
• Experiments are required to confirm the form
• Most common form is the power law model
• Rate of reaction is proportional to the product of
concentrations of the reactants raised to a power
𝛽
−𝑟𝐴 = 𝑘𝐶𝐴𝛼 𝐶𝐵
𝑛 =𝛼+𝛽

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Order of reaction
• Powers to which the concentrations are raised in
the kinetic rate law
• Reaction is 𝜶 order w.r.t. A, 𝜷 order w.r.t. B
• Overall order of the reaction is 𝒏
• As orders are found empirically, these values can be
fractional
Concentration 1−𝑛
• Units for the rate constant are
Time

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 Rate laws
A → Products
• Zero-order: −𝑟𝐴 = 𝑘; 𝑘 = mol. dm−3 . s −1
• First-order: −𝑟𝐴 = 𝑘𝐶𝐴 ; 𝑘 = s −1
• Second-order: −𝑟𝐴 = 𝑘𝐶𝐴2 ; 𝑘 = dm3 . mol−1 . s −1
2
• Third-order: −𝑟𝐴 = 𝑘𝐶𝐴3 ; 𝑘 = dm3 . mol−1 . s −1

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Elementary reactions
• Stoichiometric coefficients are identical to the powers in the
rate law
• Consider the following reaction
A+B→R
• If the rate controlling step is the collision of molecule A with
molecule B, then the rate of the reaction is proportional to
the number of collisions
• At a given temperature, number of collisions is proportional
to the concentrations of A and B
⟹ −𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵

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 Molecularity
• Number of atoms, ions, or molecules involved in a
reaction step
• Unimolecular, bimolecular, and occasionally
termolecular
• Termolecular reactions
• are almost nonexistent
• usually follow a series of bimolecular reactions
• Molecularity must be an integer as it refers to the
reaction mechanisms

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Nonelementary reactions
• Possible for nonelementary reactions to have identical
reaction orders and stoichiometric coefficients
• Happens due to pathways involving active intermediates
and series reactions
• For many reactions involving multiple steps and pathways,
the powers of rate law surprisingly agree with the
stoichiometric coefficients
• These reactions are said to follow an elementary rate law
• 2NO + O2 → 2NO2 is a nonelementary reaction
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• But, −𝑟𝑁𝑂 = 𝑘𝐶𝑁𝑂 𝐶𝑂2

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 Reversible reactions
• A reversible reaction can be written as two
simultaneous reactions
aA + bB ⇄ cC →𝑟
• can be considered as
aA + bB → cC → 𝑟𝑓
cC → aA + bB → 𝑟𝑏
• Rate expression is simply a combination of the two
reactions
𝑟 = 𝑟𝑓 − 𝑟𝑏

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Examples of reaction rate laws

Table from Scott H. Fogler, Elements of Chemical Reaction

Engineering, 4th Edition, 2015, Pearson

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 Nonelementary rate laws
• Stoichiometry does not match with the kinetics
• Reaction between hydrogen and bromine
H2 + Br2 → 2HBr
• which has a rate expression
𝑘1 𝐻2 𝐵𝑟2 1/2
𝑟𝐻𝐵𝑟 =
𝑘2 + 𝐻𝐵𝑟 /[𝐵𝑟2 ]
• Need to develop a multistep reaction model to
explain the kinetics

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Kinetic models for nonelementary reactions

• Assumptions
• A sequence of elementary reactions are occurring
• Intermediates can’t be measured or observed as they are in negligible
quantities
• We only observe the initial reactants and the final products, which appears
to be in a single reaction
• The following nonelementary reaction,
A2 + B2 → 2AB
• can be broken down to the following elementary reactions
A2 ⇄ 2A*
A* + B2 ⇄ AB + B*
A* + B* ⇄ AB

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 Kinetic models for nonelementary reactions
• To confirm the mechanism, the predicted kinetic
expression for the postulated mechanism has to be
compared against the empirical rate equation
• Types of intermediates postulated is based on the
chemistry of the materials
• Free radicals
• Ions and polar substances
• Molecules
• Transition complexes

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Kinetic models for nonelementary reactions

• Free radicals
• Free atoms or larger fragments of stable molecules that
contain one or more unpaired electrons
• Unstable and highly reactive
• E.g. – CH3·, I·, H·, CCl3·
• Ions and polar substances
• Electrically charged atoms, molecules, or fragments of
molecules
• E.g. – N3–, Na+, OH–, H3O+

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 Kinetic models for nonelementary reactions
• Molecules
• In a series reaction A → R → S, if R is highly reactive, its
concentration in the reaction mixture is too small to
measure
• R is a reactive intermediate
• Transition complexes
• Collision of reactant molecules can result in unstable
forms
• Strained bonds, unstable forms of molecules, or
unstable association of molecules can then decompose
to form products or return to molecules in normal state

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Kinetic models for nonelementary reactions

• Reaction schemes involving these four kinds of
intermediates can be of two types
• Nonchain reactions

• Chain reactions

Equations from Octave Levenspiel, Chemical Reaction

Engineering, 3rd Edition, 2006, Wiley

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 Free radicals, chain reaction

Equations from Octave Levenspiel, Chemical Reaction

Engineering, 3rd Edition, 2006, Wiley

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Molecular intermediates, nonchain

Equations from Octave Levenspiel, Chemical Reaction

Engineering, 3rd Edition, 2006, Wiley

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 Transition complex, nonchain
• Spontaneous decomposition of azomethane

Equations from Octave Levenspiel, Chemical Reaction

Engineering, 3rd Edition, 2006, Wiley

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Testing kinetic models

• Problems with identifying the correct model
• Reaction may proceed by more than one mechanism
with relative rates that change with conditions
• More than one model can be consistent with the
experimental data
• Resolving these problems require an extensive
knowledge on the chemistry of the materials

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 Examples of reaction rate laws

Table from Scott H. Fogler, Elements of Chemical Reaction

Engineering, 4th Edition, 2015, Pearson

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Points to remember
• Rate laws are determined by experimental observation
• Reaction orders can’t be determined by using
stoichiometry
• Many reactions are elementary, but at least an equal
number are not
• Process engineers use rate equations that give an
accurate enough description of the problem
• Make whatever approximations are reasonable to find
answers at the level of sophistication required

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