EQ1021 Chemical Reaction Engineering

Lecture 3. Reaction Rate: Influence of Temperature and Conversion

1 Mathematical Equations for the Reaction Rate
2 The Homogeneous General Reaction
3 Constant-Rate Curves

1
Lecture 3. Reaction Rate: Influence of temperature and conversion

1. Mathematical Equations for the Reaction Rate

1.1 Reaction Rate
1.2 Rate Equation
1.3 Reaction Rate Referred to a Component and to the Chemical Equation
1.4 Elementary and non-elementary Reactions
1.5 Irreversible and Reversible Reactions
1.6 Autocatalytic and Non-Autocatalytic Reactions
1.7 Reaction rates in Single and Multiple Reaction Systems
1.8 Rate Constants
1.8.1 Influence of the Chemical Equations
1.8.2 Influence of Temperature
2 The Homogeneous General Reaction
2.1 The Kinetic Equation
2.2 Thermodynamic Consistency of Reactions
3 Constant-Rate Curves.
3.1 Constant Volume Systems.
a) First-order Irreversible Reaction
b) First-order Reversible Reaction
c) The Homogeneous General Reaction.
3.2. Variable Volume (Gas) Systems. Exothermic Reversible Reaction.
3.3 Optimum temperature progression

2
Lecture 3. Reaction Rate: Influence of temperature and conversion

The main objectives of this lecture are:

 Define the Rate Law and learn HOW TO EXPRESS IT in function of intensive variables such as cj,
pj, xj, and in terms of reaction progression (conversion, extent of reaction).

 Find expressions for the Reaction Rate for each species in single-reaction and in multiple-reaction
systems.

 Determine the influence of temperature and chemical equations onto the Rate Constants.

 Emphasize the need to obtain Rate Laws consistent with the thermochemical equilibrium
requirements.

 Learn HOW to obtain constant-rate curves and use them to determine the optimal temperature
conditions for our reaction.

3
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Reaction Rate

• The reaction rate is defined as the rate of disappearance of a reactant or

of formation of a product.
• Depending on the system :
 Homogeneous reactions:
• “moles of Aj species which are formed per unit time and per unit volume”.
 mol A j  mol A j formed
R j   =
 time ⋅ Volume
3
 m ·s

 Heterogeneous reactions:
• the reaction rate is not related to the volume of the system but to the reactants contact area
(specific surface area of the solid) or to the mass of catalyst.

 mol A j  mol A j formed

R'j   =
2
 m ·s  time ⋅ surface

 mol A j  mol A j formed

R"j   =
 s·kg  time ⋅ catalyst weight
4
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Equation... from the Material Balance?

• Batch Reactor (BR)

A → Pr oducts
cA = f ( t )
dc A
RA = Is RA equal to dcA/dt??
dt
A

• Continuous Stirred Tank Reactor (CSTR) .... Is NaOH reacting?

NaOH + CH3COOC2H5 CH3COONa + C2H5OH

NaOH AcOEt
c A = cte ≠ f ( t ) RA is equal to dcA/dt only in a
dc A batch system
=0
dt

Products RA = dcA/dt is NOT

the Rate Equation
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Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Equation

• The Rate Equation:

 p j  
 moles of A j 
   
R j   = f   x j  , rate constants, T  (*)
 m ⋅s
3
    
c
 j  
is an algebraic expression in terms of rate constants and composition (species that appear in the
reaction scheme and catalysts)

-RA in our
notation

• The units of the constants are adjusted so that the reaction rate is in (mol/m3·s)
• The form of the kinetic equation (*) and the parameters of this equation must be obtained
experimentally from experimental reactant systems.
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Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Equation

• Rate Equations ARE EXPERIMENTAL. They cannot be predicted; their expressions and the parameter
values are obtained from experiments.

• The material balances to the reactant systems are used to calculate the Rj values, with different
conditions of temperature and composition and thus obtain the Rate Equation (*) and its parameter
values.

• To measure the reaction rate it is necessary:

 a reactant system
 a means to monitor the reaction progress, which usually will be to continuously measure some
system property that varies with conversion.

7
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Reaction Rate Referred to a Component (Rj) and to the Chemical Equation (r)

• Let’s consider the reaction: N2 + 3H2 ↔ 2 NH3

• Rj: formation rate of Aj

• Rj values are not the same for all three chemical species:
1 1
RN2 = RH 2 = − RNH3
3 23
1 224
14 3
H 2 dissapears 3 times faster than N2 NH 3 forms twice as fast as N2

• Reaction rate can be referred to the reaction scheme, such as:

r = − R N 2 = − (1 3 )R H 2 = (1 2 )R NH 3

R1 R2 R3 R4
r = = = = R j = ν j r Eq. 3-1
ν1 ν2 ν3 ν4

 r is always positive

>0 for products

 Rj 8
<0 for reactants
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Expressions for the Rate Equation

• Algebraic expression, depending on the composition and temperature.

• It can take very different forms:
 in the synthesis of hydrogen bromide
1/ 2
k1cH2 cBr
Br2 + H 2 ↔ 2 HBr → RHBr = 2

k 2 + cHBr cBr2

 in enzymatic reactions:
− k cA
A + E → B + E → RA =
Km + cA

 Saponification of ethyl acetate, (AcOEt≡A1, NaOH≡A2, AcONa≡A3, and EtOH≡A4)

AcOEt + NaOH ↔ AcONa + EtOH → r = kc 1c 2 − k' c 3 c 4

• The expression may be more or less complex depending on the reaction mechanism
9
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Elementary and Non-Elementary Reactions.

• Consider a single reaction:

A + B → R
• If we postulate that the reaction involves the collision of a single molecule of A with a single molecule of B,
then the number of collisions of molecules A with B is proportional to the rate of reaction. But at a given
temperature the number of collisions is proportional to the concentration of reactants in the mixture; hence,
the rate of disappearance of A is given by

R A = − k c A cB
• Such reactions in which the stoichiometric equation corresponds to the mechanism are called elementary
reactions. There is a direct relationship between stoichiometry and rate.

• When there is no direct correspondence between stoichiometry and rate, then we have nonelementary
reactions. What we observe as a single reaction is in reality the overall effect of a sequence of elementary
reactions. The classical example of a nonelementary reaction is that between hydrogen and bromine,
1/ 2
k1 cH2 cBr
Br2 + H 2 → 2 HBr RHBr = 2

which has a rate k 2 + cHBr / cBr2

expression

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Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Elementary and Non-Elementary Reactions.

Molecularity:
The molecularity of an elementary reaction is the number of molecules involved in the reaction, and this has
been found to have the values of one, two, or occasionally three. Note that the molecularity refers only to an
elementary reaction, and must be an integer.

Order of Reaction:
Often we find that the rate of progress of a reaction, involving, say, materials A, B, . . . , D, can be
approximated by an expression of the following type:

R A = − k c Aβ A cBβB K cDβD

where βA, βB, . . . , βD are not necessarily related to the stoichiometric coefficients. We call the powers to
which the concentrations are raised the order of the reaction. Thus, the reaction is:
 βAth order with respect to A
 βBth order with respect to B where β = βA + βB + . . . + βD
 βth order overall

Since the order refers to the empirically found rate expression, it can have a fractional value and need not be an
integer. It can be negative. 11
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Reversible and Irreversible Reactions.

Reversible Reactions
• In some cases the extent of reaction is limited by the position of chemical equilibrium, and this extent (X∞) will
be less than 1. When the conversion at equilibrium differs measurably from 1, we will classify the reaction
involved as reversible. From a thermodynamic point of view, all reactions are reversible.
• For reversible reactions, the net reaction rate is the difference between the forward and the reverse reaction:

r = rf − ri = k ⋅ f 2 ( c j ) − k' ⋅ f 2′( c j )
Irreversible Reactions
However, in many cases X∞ is approximately equal to 1. In these cases the equilibrium for the reaction highly
favors formation of the products, and only an extremely small quantity of the limiting reagent remains in the
system at equilibrium. We will classify these reactions as irreversible.
r = rf = k f ⋅ f 2 ( c j )
What happens is that, at the temperature of operation, the reverse reaction rate constant k’ is very low and
negligible with respect to the forward reaction constant, k.

If the temperature of operation changes, the reaction can change

from apparently irreversible to reversible.
12
Hill
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Autocatalytic and Non-Autocatalytic Reactions.

• Autocatalytic reactions are chemical reactions in which at least one of the products is also a reactant.
• The simplest scheme is of the type:
A→B r = k c Ac B
 2 competing mechanisms:
• an elemental reaction:
A→B r = k cA very slow in the beginning, the reaction proceeds
(very slowly) through
• a mechanism in two steps: the elemental mechanism

A+B →E slow r1 = k1 c AcB

E → 2B fast r2 = k 2 cE when there is a small amount of B,
the reaction proceeds through
the second mechanisn

• One of the products (B) enhances the reaction rate (autocatalyst)

• It could also happen that one of the reactants decreases the reaction rate (inhibitor)

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Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Reaction rates in Single and Multiple Reaction Systems.

Single and Multiple Reactions

• series reactions,

• parallel reactions, which are of two types

• and more complicated schemes, an example of which is

• Here, reaction proceeds in parallel with respect to B, but in series with respect to A, R, and S. 14
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Reaction rates in Single and Multiple Reaction Systems.

• Single-Reaction Systems: Rj = ν j ⋅ r Eq. 3-1

R A = − 2 r = −2 k c A c B
2 A + B → 2C r = k c A cB RB = − r = − k c A c B
RC = 2 r = 2 k c A cB
R A = −2 r = −2 k c A cB + 2 k' cC2 / c A
2 A + B ↔ 2C r = k c A cB − k' cC2 / c A RB = − r = − k c A cB + k' cC2 / c A
RC = 2 r = 2 k c A cB − 2 k' cC2 / c A

• Multiple-Reaction Systems: R j =  ν ij ⋅ ri Eq. 3-4

i

R A = −2 r1 − r2 = −2 k1 c A2 − k 2 c AcB
2A → B + C r1 = k1 c A2 RB = r1 − r2 = k1 c A2 − k 2 c A cB
A+B →D r2 = k 2 c AcB RC = r1 = k1 c A2
RD = r2 = k 2 c A cB
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Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Reaction rates in Multiple Reaction Systems.

• Let’s suppose that the following reactions are happening c A0 = 2 mol / l

in the CSTR shown in the figure. QV 0

A →
k1
B →
k2
Cdesired cA
QV 0
↓ k3
↓ k4
cB
D+F E +F cC

V
= 0. 5 h
where reactions (1) and (2) could be isomerizations and QV 0
(3) and (4), decompositions. Some concentrations have
been measured at the reactor outlet:
c A = 0.6 mol / l cB = 0.2 mol / l cC = 0.7 mol / l cD = 0.3 mol / l

a) Would we need to measure the concentration of another chemical species in order to know ALL the
concentrations at the reactor outlet?
b) Which is the reaction rate of every chemical species in the system?
c) If all the reactions are first-order, could you estimate the value for the reaction constants?

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Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Influence of the Chemical Equation.

Rate Constants

Let’s consider the following reaction: A + 3B → 2 C ( ) %

That develops in an CSTR as shown in the picture.

We can determine the values of RA, RB, RC % & /
and the kinetic constant k. /
We can also calculate r (reaction rate referred to the QV 0
chemical equation), but the we have at least three logical forms
to express the reaction (three equivalent chemical equations)
cA
that are respectively obtained when 1 mole of A, B or C participates: QV 0
cB
/
3 +2 0
'
cC

1 2 !
+ 0 #$
3 3 "!
1 3
+ 0
2 2
1
1 1 1 1
That will give different values of r

1/3 3 2 3 2

1/2 And then, different

values of k 17
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Influence of the Chemical Equation.

Rate Constants

• In the literature, the rate constants can be:

 Referred to a given reaction scheme
• the reaction scheme used as reference has to be known, to select the value of
νj (or νk) that has to be used to calculate Rj (or Rk).

 Related to one of the reactants or products (Aℓ):

• the reaction scheme is modified to set the stoichiometric coefficient for Aℓ,
as 1 or -1, depending if the species is a product or a reactant, |νℓ | = 1.

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What if... ?
What is the Rate Law if stoichiometry changes?

A reaction with stoichiometric equation A + 2B ↔ 2R + S has the following

rate expression:

− R A = 2 c A0.5 cB

What is the value of RA for this reaction if the stoichiometric equation is written as
½ A + B ↔ R + ½ S?

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Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Influence of Temperature.

Rate Constants. Influence of Temperature

• Rate constants depend strongly on temperature.

This dependence usually follows the Arrhenius equation:

A : Preexponential or Frequency Factor

 E  E : Activation Energy, J/mol
k = A exp − 
 RT  R : Gas constant, 8.314 J/mol·K
T : Absolute Temperature, K

The Arrhenius equation was deduced for a reversible elementary reaction in liquid phase:

A↔B r = k c A − k' cB

k cBe k K
In equilibrium, r=0 = = Kc =
k' c Ae k' Kγ
{
Kc

d d d
Taking logarithms and differentiating: ln k − ln k' = ln KC ln k − ln k' = ln K c
dT dT dT 20
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Influence of Temperature.

Rate Constants. Influence of Temperature

• Equilibrium constant varies with temperature (Van't Hoff):

d ∆H 0
ln K =
dT RT 2

K Kγ varies little with T d ∆H 0

• In liquid systems: Kc = ln K c =
Kγ d
ln K γ ≅ 0 dT RT 2
dT

Arrhenius law
• Comparing with the previous expresion:

d ln k E  E 
= k = A exp  − 
d d ∆H 0 dT RT 2
 RT  A A' = K c*
ln k − ln k' =
dT dT RT 2 d ln k' E'  E'  ∆H 0 = E − E'
= k' = A' exp  −
 RT 
dT RT 2 21
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Influence of Temperature.

• Temperature Dependency from Arrhenius' Law

For many reactions, and particularly elementary reactions, the rate expression can be written as a
product of a temperature-dependent term and a composition-dependent term, or

r = f 1 ( temperature ) ⋅ f 2 ( composition ) = k ⋅ f 2 ( composition )

For such reactions the temperature-dependent term, the reaction rate constant, has been found in
practically all cases to be well represented by Arrhenius' law:

 E  Eq. 3-2
k = A exp  − 
 RT 

where A is called the frequency or pre-exponential factor and E is called the activation energy of the
reaction.

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Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Influence of Temperature.

• Temperature Dependency from Arrhenius' Law

What are the units of E? Joules per mole are clearly indicated in the equation.
What are the units of A? The same units as the constant.

At the same concentration, but at two different temperatures, Arrhenius' law indicates that

r2 k E1 1 
ln = ln 2 =  −  Eq. 3-3
r1 k1 R  T1 T2 

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Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Influence of Temperature.

Activation Energy and Temperature Dependency

•The temperature dependency of reactions is determined
by the activation energy and temperature level of the
reaction
•These findings are summarized as follows:
1. From Arrhenius' law a plot of In k vs 1/T gives a straight
line, with large slope for large E and small slope for
small E.
2. Reactions with high activation energies are very
temperature-sensitive; reactions with low activation
energies are relatively temperature-insensitive.

24
Example: Activation Energy

• Consider the following elementary reactions:

1) Which reaction has the highest activation energy?

2) Which reactions have the same activation energy?
3) Which reaction is virtually temperature insensitive?
4) Which reaction will dominate (i.e. take place the fastest) at high temperatures if all reactions were to
take place in the same reactor?
5) Which reaction will dominate (take place the fastest) at moderate temperatures?
25
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Influence of Temperature.

• Comparison of Theories with Arrhenius' Law

The expression
 E 
k = A T m exp  −  0 ≤ m ≤1
 R T 

summarizes the predictions of the simpler versions of the collision and transition state theories for the
temperature dependency of the rate constant.
For more complicated versions m can be as great as 3 or 4.

Now, because the exponential term is so much more temperature-sensitive than the pre-exponential
term, the variation of Tm with temperature is effectively masked, and we have in effect

 E 
k = A exp  − 
 RT 

26
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Reversible and Irreversible Reactions.

• Endothermic or Exothermic Reversible Reactions

r = rf − ri = k ⋅ f 2 ( c j ) − k' ⋅ f 2′( c j )

Endothermic, ∆H0>0, E>E’ Exothermic, ∆H0<0, E<E’

ln k ln k, pte:E/R ln k ln k’, pte:E’/R

ln k’, pte:E’/R ln k, pte:E/R

1 1
T T
at high T, at low T, at high T, at low T,
k > k’, forward k < k’, forward k < k’, forward k > k’, forward
reaction is favored reaction is disfavored reaction is disfavored reaction is favored

27
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Correct and Incorrect Rate Values.

• Example (Problem 3.19): Experimental studies of a specific decomposition of A in a batch reactor using
pressure units show exactly the same rate at two different temperatures:

  mol 
at 400 K: − R A = 2.3 pA2  − R A is in  3 
where  m ⋅ s 
at 500 K: − R A = 2.3 pA2  p A is [atm ]

Which is the activation energy, E?

28
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Correct and Incorrect Constant Values.

29
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Correct and Incorrect Constant Values.

30
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Rate Constants. Correct and Incorrect Constant Values.

1. Chemistry (collision theory or transition state theory) has developed the equations for reaction rates
and activation energies in terms of concentration.

2. Literature tabulations for E and -RA for homogeneous reactions are normally based on concentrations.
The clue to this is that the units for the rate constant are often s-1, liter/mol·s, etc., without pressure
appearing in the units.

3. It is a good idea when making runs at different temperatures first to change all pj values to cj values by
using the relationships
pj = cjRT for ideal gases
pj = z cjRT for nonideal gases, where z = compressibility factor
and then proceed to solve the problem. This will avoid confusion on units later on, especially if the
reaction is reversible or involves liquids and/or solids as well as gases.

31
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Arrhenius Law in Elementary and Non-Elementary Reactions.

Arrhenius Law in Elementary and Non-Elementary Reactions

• Elementary Reactions or Elementary Steps in a Reaction Mechanism.
 Almost always applicable. If not, the reliability of the Arrhenius fit is such that we will admit it is not a
elementary reaction, or even a system with a single reaction.
 For elementary reactions, always E > 0

• Nonelementary Reactions.
 Not necessarily applicable for the apparent rate constant, that can be a combination of the rate constants
of the mechanism steps.
 In some cases (involving NO), E < 0

32
Table from Davis
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Elementary and Non-Elementary Reactions. Reaction with E<0.

Example: oxidation of NO to NO2:

2 NO + O 2 → 2 NO 2

• It’s a third orden reaction: R NO 2 = k c NO

2
cO2 So, it is NOT elementary.
• Rate constant decreases when temp. increases (negative E) What happens?

33
Lecture 3. Reaction Rate: Influence of temperature and conversión
1. Mathematical Equations for the Reaction Rate
Elementary and Non-Elementary Reactions. Reaction with E<0.

• A mechanism in two steps:

c N 2 O2  ΔH 0 
a) fast equilibrium 2 NO ↔ N 2 O 2 Ka = Ka = Ka *
exp  − 

2
c NO  RT 

 Eb 
b) slow bimolecular step N 2 O 2 + O 2 → 2 NO 2 R NO 2 =k c N 2 O2 cO2 k b = Ab exp  − 

b
 RT 

The first reaction is ALWAYS in equilibrium, because it is very fast compared to the second.
The reaction rate comes from the second step.

 647 E 48 
 
R NO = k b cN O cO2  ∆ H a0 + E b 
2 2 2
k = k b K a = K a Ab exp  −
*

123
substituting c N 2 O 2 = K a c NO
2 RT
A  
 
R NO = k b K a c NO
2
cO 2 = k c NO
2
cO2 the apparent activation E is negative because
2
step a is exothermic
34
Lecture 3. Reaction Rate: Influence of temperature and conversión
2. The Homogeneous General Reaction.
Reminder: Molecularity and Order of Reaction.

Molecularity:
The molecularity of an elementary reaction is the number of molecules involved in the reaction, and this has
been found to have the values of one, two, or occasionally three. Note that the molecularity refers only to an
elementary reaction, and must be an integer.

Order of Reaction:
Often we find that the rate of progress of a reaction, involving, say, materials A, B, . . . , D, can be
approximated by an expression of the following type:

R A = − k c Aβ A cBβB K cDβD

where βA, βB, . . . , βD are not necessarily related to the stoichiometric coefficients. We call the powers to
which the concentrations are raised the order of the reaction. Thus, the reaction is:
 βAth order with respect to A
 βBth order with respect to B where β = βA + βB + . . . + βD
 βth order overall

Since the order refers to the empirically found rate expression, it can have a fractional value and need not be an
integer. It can be negative. 35
Lecture 3. Reaction Rate: Influence of temperature and conversión
2. The Homogeneous General Reaction
Expressions for the Rate Equation

• Algebraic expression, depending on the composition and temperature.

• It can take very different forms:
 in the synthesis of hydrogen bromide
1/ 2
k1cH2 cBr
Br2 + H 2 ↔ 2 HBr → RHBr = 2

k 2 + cHBr cBr2

 in enzymatic reactions:

− k cA
A + E → B + E → RA =
Km + cA

 Saponification of ethyl acetate, (AcOEt≡A1, NaOH≡A2, AcONa≡A3, and EtOH≡A4)

AcOEt + NaOH ↔ AcONa + EtOH → r = kc 1c 2 − k' c 3 c 4

The expression may be more or less complex depending on the reaction mechanism
36
Lecture 3. Reaction Rate: Influence of temperature and conversión
2. The Homogeneous General Reaction.
The Kinetic Equation.

S
• Let`s consider a certain reaction: Σν
j =1
j Aj =0

• For a reversible reaction, sometimes the forward and reverse reaction rates can both be expressed as a
potential function:
S
β β
rf = k c1 1 c2 2 KcSS = k
β
Πc
j =1
βj
j βj :order of Aj in the forward reaction
r = rf − ri S
γ γ
ri = k ′ c1 1 c2 2 KcSS = k ′
γ
Πc
j =1
γj
j γj :order of Aj in the reverse reaction

• Combining the expressions for the forward and reverse reactions in a single equation:
S S

r = k Πc
j =1
βj
j − k' Πc
j =1
γj
j

νj
• For a constant-volume system: c j = c j 0 − ck 0 X
νk

ν
βj γj β= Σβ
Πj =1  θ j − νν j X 
S S
 
Π
j
r [X ,T ] = k [T ] ck 0 − k' [T ] ck 0
β γ j
 θ j − j X  where
j =1
 νk   k  γ = Σγ j
37
j
Lecture 3. Reaction Rate: Influence of temperature and conversión
2. The Homogeneous General Reaction.
The Kinetic Equation.

βj γj
ν
Πj =1  θ j − νν j X 
S S
 
r [X ,T ] = k [T ] ck 0
β
Π
j =1
 θ j − j X 
νk 
− k' [T ] ckγ 0 Eq. 3-5
  k 

βj :order of Aj in the forward reaction

where
γj :order of Aj in the reverse reaction

• In normal reactions (Nonautocatalytic):

 reactants favor the forward reaction (βj>0) and hinder the reverse reaction (γj<0)
 products hinder the forward reaction (βj<0) and favor the reverse reaction (γj>0)

so, the following relationships are found: νj βj ≤ 0 and νj γj ≥ 0 Eqs. 3-6

38
Lecture 3. Reaction Rate: Influence of temperature and conversión
2. The Homogeneous General Reaction.
Thermodynamic Consistency of Reactions.

• This section is devoted to a discussion of the

limitations that thermodynamics places on reaction rate expressions.

For reversible reactions, the observed rate can usually be expressed as a difference of two terms, one
pertaining to the forward reaction and the other to the reverse reaction.

rneta = r f − rr

At equilibrium the net rate of reaction becomes zero.

• Consider an arbitrary reaction, which we may write in the form:

− ν A A − ν BB ↔ ν R R + ν SS

Suppose that evidence indicates that the initial reaction rate is of the form
S

rf = k c βA
A
βB
c c c
B
βR
R
βS
S == k Πc
j =1
βj
j

where the various orders may be positive, negative, or zero. 39

Lecture 3. Reaction Rate: Influence of temperature and conversión
2. The Homogeneous General Reaction.
Thermodynamic Consistency of Reactions.

Let's suppose that the form of the reverse reaction rate will also be a product of powers of concentrations, for
example,
S
γA
rr = k' c c c c
A
γB
B
γR
R
γS
S = k' Π
j =1
γ
cj j

• The net rate of reaction is given by

r = k c Aβ A cBβ B cRβ R cSβ S − k' c Aγ A cBγ B cRγ R cSγ S

= c Aγ Ae − β A cBγ Be − β B cRγ Re − β R cSγ Se − β S = Π c jej j

k γ −β
Hence, at equilibrium (r=0): Eq. 3-7
k' j =1

where the subscript e indicates any set of concentrations in equilibrium. The rate constants kf and kr and thus
their ratio are independent of the system composition and depend only on temperature.

• Eq 3-7 is an equilibrium expression reached using exclusively the principles of kinetics.

40
Lecture 3. Reaction Rate: Influence of temperature and conversión
2. The Homogeneous General Reaction.
Thermodynamic Consistency of Reactions.

• Taking the reaction scheme into account: * ↔ , + -.

equilibrium can be expressed from thermodynamics as:

2,47 2-48
5 5
56
/0 1 23 2,47 2-48 2 2*4:
5 5 59 5
2 2*4 :
4 4 ;59 ;5 Eq. 3-8
3 4

By combining Eq.3-7 and Eq. 3-8 (two expressions of equilibrium, from kinetics and from stoichiometry,
respectively), it is very tempting to conclude:
> ?
>* ?* *
2 49 9 2*4: : 2,47 7 2-48 8 2,47 2-48 2 49 2*4: >, ?,
< ;= < ;= < ;= < ;= 5 5 5 5
,
>- ?- -

But though there is ONLY ONE equilibrium expression from kinetics, you can obtain from stoichiometry
as many equilibrium laws as stoichiometric schemes can be set (infinite).
Which equilibrium equation is the consistent one?
41
Lecture 3. Reaction Rate: Influence of temperature and conversión
2. The Homogeneous General Reaction.
Thermodynamic Consistency of Reactions.

• Let’s see, we could express stoichiometry (and equilibrium) in different ways:

2,47 2-48
5 5
↔ + -. /0
2 2*4 :
Original scheme: * , ;59 ;5
4

/
2,47 2-48
5 5

↔ + . /0 /0
* , - /
2 2 2 2 2 2*4 :
Scheme a: @ ;59 ;5
4

2,47 2-48
5 5

2 2 ↔ 2 + 2 -. /0 /0
2 2*4 :
A ;59 ;5
* ,
Scheme b:
4

C
2,47 2-48
5 5

B B ↔ B + B -. /0 /0 C
2 2*4 :
C ;59 ;5
In general: * ,
4

• There is ONLY ONE of them which is consistent with the kinetic equilibrium, so that:
> ? B
>* ?* B *
C
2,47 2-48
5 5
2 2*4 2,4 2-4 /0 C
<9 ;=9 <: ;=: <7 ;=7 <8 ;=8
′ 4
2
;59
2*4 :
;5 >, ?, B ,
>- ?- B -
and
4

42
Lecture 3. Reaction Rate: Influence of temperature and conversión
2. The Homogeneous General Reaction.
Thermodynamic Consistency of Reactions.

• For a reversible reaction, the order of the reactants in the forward and the reverse directions are
bounded by stoichiometry:
γ j − β j = n ν j Eq. 3-9

• The relation between the rate constants and the equilibrium constant will be given by

k
= KCnstoich Eq. 3-10
k'

• In addition to its constraints on the concentration dependent portions of the rate expression,
thermodynamics requires that the activation energies of the forward and reverse reactions be related
to the enthalpy change accompanying reaction.

Ink - Ink' = n In KC E − E' = n ∆H 0 Eq. 3-11

43
Lecture 3. Reaction Rate: Influence of temperature and conversión
2. The Homogeneous General Reaction.
Thermodynamic Consistency of Reactions.

• We can change our chemical equation to a consistent one. The first step is to determine if our chemical
equation:
 ν′j A j = 0
is consistent or not.
• We take the values of νj, βj and γj, for one of the species and calculate n. This value of n converts our
non-consistent chemical equation to THE thermodynamically consistent one:

 n ν′ A
j j =0 it is to say ν j Aj = 0 where νj = n νj ‘

• For this equivalent, ν j Aj = 0 , consistent reaction scheme (and only for this one):

γ j −βj = νj

k
= KCstoich
k'

E − E ' = ∆H 0
44
Thermodynamic Consistency of Reactions.
Example

In a closed vessel of 1 liter 1 mole of iodine is reacted with 1 mole of hydrogen, at 823 K. At equilibrium,
the conversion reached is 0.5279.
The kinetic experiments have established that the reaction rate equation is:

r = k f c I2 cH 2 − k i cHI
2

and the rate constant of the forward reaction is 1.25·10-4 m3/kmol·s.

Use these data to determine the value of the rate constant for the reverse reaction.

45
Thermodynamic Consistency of Reactions.
Example 2. Phosgene synthesis.

CO + Cl 2 ↔ COCl 2
r f = k f c 2 c 33 / 2
− A2 − A3 + A1 = 0

• It IS NOT an elementary reaction ( r f ≠ k f c2 c3 )

• a chain reaction with 3 elemental steps :

initiation and termination Cl2 ↔ 2Cl· -A3+2A4 = 0 (i=1)

propagation Cl· +CO ↔ COCl· -A2-A4+A5 = 0 (i=2)
propagation COCl· +Cl2 ↔ COCl2+Cl· A1-A3+A4-A5 = 0 (i=3)

• Hypothesis: process controled by step i=3 (slow), steps 1 and 2 in equilibrium

⋅ /G ⋅ H/G I ⋅2 ⋅2 ⋅2 ⋅2
/ / /
E E E

• What is the reverse rate equation (independent of A2)?

⋅ H/G I ⋅2 ⋅2 ⋅2 ⋅2
• / / /
J J J J
Are there any autocatalytic effects?
46
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
Introduction.

Constant-Rate Curves

• To examine simultaneously the influence of the composition and temperature of the system on the
reaction rate, it is useful to graph the constant rate curves for the reaction.
• In these diagrams, curves for constant reaction rate are plotted as a function of system temperature
and the conversion of the reaction.

47
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems.

a) First-order Irreversible Reaction

A1 → A2

• For simplicity, let’s assume that c10 = 1 and c20 = 0, so that the concentrations of A1 and A2, at any
instant, will be:
c1 = c10 (1-X) = 1-X
c2 = c20 + c10X = X

• For a first-order reaction, the rate equation can be written as:

− E 
r [X ,T ] = A exp   (1 − X )
 RT 

• This equaRon can be solved, obtaining a series of values of X that correspond to the same value of r and
T. With these values,one can trace a set of curves for different values of r, in a representation of X = f
[T] which is known as conversion-temperature diagram.
48
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Irreversible Reaction (cont.)

• Solving for X, the following equation results: X

r=0
1
r exp [E RT ] Eq. 3-12
fix r
X = 1−
A give values to T and r increases
calculate X

 A growing function:
∂X r  E   E 
=− − exp  RT  > 0
With constant r, T
∂T r A  RT 2  X increases with T

r1 r2 r3 r4
T• =
E
 Intersection with abscissa (X=0):
R ln (A r )
T● increases as r increases, so r1 < r2 < r3 < r4
T1• T2• T3• T4• T
X
 Asyntotes: If T→∞ X∞ = 1 - r/A X∞,1 = 1 – r1/A
X∞,2 = 1 – r2/A
X∞ decreases as r increases
X∞,3 = 1 – r3/A
X∞,4 = 1 – r4/A 49
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Irreversible Reaction (cont.)

• In general, for irreversible reactions (non autocatalytic):

 When X increases at constant T,

X
reaction rate (r) decreases. r=0
1
 When T increases at constant X,
reaction rate (r) increases,
When T increases
independently of the reaction being at constant X, r
increases
exothermic or endothermic. r increases

 Some reaction rates cannot be

achieved for a certain conversion, When X increases in an T
isothermal path, r
even if T is raised (asyntotes). decreases

50
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Reversible Reaction (cont.)

b) First-order Reversible Reaction

Consider the elementary, reversible reaction:

A↔B

Suppose this reaction is occurring in a CSTR of fixed volume and throughput.It is desired to find the reaction
temperature that maximizes the yield of product B.

Endothermic: Ef > Er, when the global reaction is endothermic. Then the forward reaction is favored in respect
to the reverse reaction by increasing temperature. The equilibrium shifts in the desirable direction, and the
reaction rate increases.
The best temperature is the highest possible temperature and there is no interior optimum.

Exothermic: For Ef < Er, increasing the temperature shifts the equilibrium in the wrong direction, but the
forward reaction rate still increases with increasing temperature.
There is an optimum temperature for this case. A very low reaction temperature gives a low yield of B because
the forward rate is low. A very high reaction temperature also gives a low yield of B because the equilibrium is
shifted toward the left.

51
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Reversible Reaction (cont.)

Endothermic, ∆H0>0, E>E’ Exothermic, ∆H0<0, E<E’

ln k ln k, pte:E/R ln k ln k’, pte:E’/R

ln k’, pte:E’/R ln k, pte:E/R

1 1
T T
at high T, at low T, at high T, at low T,
k > k’, forward k < k’, forward k < k’, forward k > k’, forward
reaction is favored reaction is disfavored reaction is disfavored reaction is favored

X X=1
X X=1

Xe
Xe

52
T T
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Reversible Reaction (cont.)

b) First-order Reversible Reaction (cont.)

A1 ↔ A2
As in the First-Order Irreversible Reaction, we assume that c10 = 1 and c20 = 0, so that the concentrations
of A1 and A2, at any instant, are: c1 = 1-X and c2 = X. Reaction rate is then:

V V′
P, Q exp 1 P ′ exp P
E R
Q Q

exp V ⁄ Q
P
exp V ⁄ Q + ′ exp V′⁄ Q
Solving for X:

V
Q•
ln ⁄
Intersection with abscissa (X=0): (same expression as with irreversible reaction)
r increases, T● increases

Asyntotes: If T→∞ X∞ HA-rI/HA+A’I, so X∞ decreases as r increases

53
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Reversible Reaction (cont.)

First-order Reversible Reaction. Morphology of Constant Rate Curves.

We need to obtain the variation of X with T when r is kept constant.

exp V ⁄ Q
P
∂X > 0 ? increasing

exp V ⁄ Q + ′ exp V′ ⁄ Q
< 0 ? decreasing
∂T r = 0 ? maximun

But to differentiate that function is complicated, so a mathematical artifice is used. Let’s calculate:

V V′
P, Q exp 1 P ′ exp P
Q Q
It’s easier to differentiate
∂r
=0
∂T r It’s equal to zero because we are deriving r with respect to T when r is kept constant

[ V V [P V′ V′ [P
exp H1 PI + H 1I ′ exp P ′ 0
[Q \
Q Q [Q \
Q Q [Q \
] ]^

54
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Reversible Reaction (cont.)

[P V V′
Grouping terms:
+ ′ H1 PI `
′P
[Q \
Q Q \
\_ a

[P 1 1
V V′
[Q Q + ′ E R
and then: Eq. 3-13
\

∂X
(Er )
> 0 ? increasing > 0 ? increasing
Is < 0 ? decreasing It depends on the value of f − E' ri < 0 ? decreasing
∂T r = 0 ? maximun = 0 ? maximun

endothermic reaction, E > E’

and that depends on the relative value of E and E’
exothermic reaction, E < E’

 Endothermic reaction: as rf is always > ri then V E V′ R b 0 and an growing curve similar to that of
irreversible reactions results.
b 0
 Exothermic reaction: V E V′ R can be f 0
0 55
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Reversible Reaction (cont.)

Endothermic, ∆H0>0, E>E’ Exothermic, ∆H0<0, E<E’

ln k ln k, pte:E/R ln k ln k’, pte:E’/R

ln k’, pte:E’/R ln k, pte:E/R

1 1
T T
at high T, at low T, at high T, at low T,
k > k’, forward k < k’, forward k < k’, forward k > k’, forward
reaction is favored reaction is disfavored reaction is disfavored reaction is favored

X X=1
X X=1

Xe
Xe

56
T T
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Reversible Reaction (cont.)

Endothermic Reversible Reaction (E>E’):

V
• Intersection with abscises (X=0): Q • ln ⁄
(same expression as with irreversible first-order).

• Asyntotes: If T→∞ X∞ HA-rI/HA+A’I, so X∞ decreases as r increases.

[P
b0
[Q
• Growth: always, so X increases monotonically with temperature.
\

X equilibrium, X∞ = (A-r)/(A+A’)
r=0

r increases

57
T●
T
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Reversible Reaction (cont.)

• [P 1 1
V V′
Exothermic Reaction (E<E’), Growth:
[Q \
Q + ′ E R

lP
bb ij V V′ b0 kBl b0
g h g h
lQ
 at the beginning of the reaction
\
(low X, far from equilibrium):
lP
b≅ ij V V′ f0 kBl f0
lQ
 at the end of the reaction g h g h
(near equilibrium): \

lP
V V′ kBl 0
g h
lQ
 somewhere in the middle:
\

equilibrium
X conversion, Xe

dX
=0
dT r

dX
>0 Constant dX decreasing
dT r r curve < 0 curve
dT r controlled by the
X increases with decreasing Xe
temperature

T 58
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. First-Order Reversible Reaction (cont.)

• Exothermic Reversible Reaction.

V
Intersection with abscises (X=0): Q •
ln ⁄
• (same expression as with irreversible).

• Asyntotes: If T→∞ X∞ HA-rI/HA+A’I, so X∞ decreases as r increases.

∂X > 0 increasing
• Growth: = 0 maximum an initial increase, a maximum, then a decrease near equilibrium
∂T r < 0 decreasing

X
Tm[X]:
curve of maximum
rate for a given X

Curve Tm[X] is obtained from the condition:

lP
0 ij V V′
lQ \
g h

59
First-Order Exothermic Reversible Reaction
What happens with Reaction Rate when Increasing T (X=constant)?

• Curves of variation of r with T for a constant conversion:

[
[Q
We need to obtain and evaluate its value to know the morphology of the curve:
n

[ V V V′ V′
1 P exp ′P exp
[Q n
Q Q Q Q r 450000 X=0.40
3
mol/m ·h X=0.41

[ 1
400000

V V′
X=0.42

[Q Q g h X=0.43
n
350000
X=0.45
300000 X=0.5

250000
equilibrium
the same condition 200000 for every conversion, condition
found for there is a maximum
150000 rate at a certain T
∂X > 0 ? increasing
< 0 ? decreasing 100000
∂T r = 0 ? maximun
50000

[
As the condition is the same,
Tm[X] is the same tan that obtained from: [Q 0
n 400 600 800 1000 1200 1400
60
T (K)
First-Order Exothermic Reversible Reaction
Calculating Tm[X]

lP
0
lQ \
V V′
l g h
0
lQ n
Substituting rf and ri values:

V
exp H1 PI
g
Q
V^ V V^
^
exp P V exp H1 PI V^ ^ exp P
h
Q Qo Qo

pq r X
V V′
Qo
V′ ′ P
ln
V 1 P

61
 Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. The Homogeneous General Reaction

V = V′ <
exp Π23 6 P ′ exp Π23 6 P
Q 3 Q 3

• Results similar to that of the first-order reactions.

• For exothermic, reversible reactions, there is a curve Tm.
Deduction:
Let’s obtain the partial derivative of r with respect to T at constant X because, as we saw in the previous
section, the point of maximum r for a specific X COINCIDES with the point of maximum X for a specific r, and
gives E rf = E' ri .

[P [
0
[Q [Q
we calculate the both maxima

\ n
maximum by coincide
differentiating r

[ V = V′ <
Π23 6 P ′Π23 6 P 0
[Q Q Q X1 maximum r
n
\t \u for X1
maximum X

Δw x
for r =10
Qo P
V′ ′ < ;=
ln V Π23 6 6
3
Eq. 3-14 62
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. Autocatalytic Reactions.
c) Autocatalytic Reactions

→ 2 2
Let’s take the simplest case:

• Some addition of A2 in the initial reaction mixture is necessary. If NOT, r = 0.

• For an autocatalytic reaction in a batch reactor some product A2 must be present if the reaction is to proceed
at all (seed), so c20≠0.

2 2 x H1 PI
{ 2 1 P z +P
2 2 x + 2 xP 2 x z + P x Eq. 3-15

H1 z I | H1 z I 4H / 2 x z I
P
Eq. 3-16
2
Solving for X in Eq.3-15:

It is noted that, for each value of r and a given temperature, there are two solutions to Eq. 3-15: two
symmetrical values of X separated an equal distance a/2 from a central axis located at X = (1-θ2)/2:
H1 z Ik
P
2 2 ~ℎ€ € k H1 z I 4H / 2 z I
H1 z I k x
P +
2 2 a decreases as r increases, 63
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. Autocatalytic Reactions.

H1 z I | H1 z I 4H / 2 x z I H1 z I …
• lim P |
2 2 2
Asyntotes:
ƒ→„

b decreases as r
increases

[P b 0? increasing
[
complicated from Eq. 3-16, we
f 0? decreasing 0
• Growth:
[Q [Q
will obtain it from
\ 0? maximun \

[ V [P
2 x H1 PIHz + PI + 2 H1 PI Hz + PI
[Q Q x
[Q
Obtaining the partial derivative:
\ \

[P V H1 PIHz + PI f0
[P
‹ ∞
[Q [Q Q 1 z 2P
b0
and solving for : Eq. 3-17
\ \

Depending on the sign of (1-θ2-2X) 64

Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. Autocatalytic Reactions.

[P V H1 PIHz + PI
[Q Q 1 z 2P
Eq. 3-17
\

• [P
1 z 2P b 0 f0
At the beginning of the reaction,
[Q
X is very small (θ2 always is), then and the function is decreasing
\

1 z
P
2
• When the denominator is zero, so the slope of the curve is infinite

[P
1 z 2P f 0 b0
[Q
increasing
• Towards the end of the reaction, X is high, then and
\ function
X
∂X
>0
∂X ∂T
=∞
r

∂T r
1 − θ2
2

∂X
<0
∂T r
65
T
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.1 Constant-Volume Systems. Autocatalytic Reactions.

2 x 1 P z +P

This is the shape of the constant reaction rate

curves

increases

• The variation of reaction rate with X at a r

There’s a maximum !!!
constant temperature is as follows:

• And aplying the condition for the constant T

maximum, ∂r
=0
∂X T

[ 1 z
0 2 H1 PI Hz + PI P
[P x
2 1 z
ƒ P
2 X 66
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.2 Variable-Volume (Density) Systems. Exothermic Reversible Reaction.

Variable-Volume (density) Systems. Gas systems. Exothermic Reversible Reaction

z3 3⁄ ]P Ž•]x z3 3⁄ ]P
The problem now is that,
23 2]x
1 + •] P Q⁄Qx Qx Q⁄Qx 1 + •] P
for a gas in an open system
concentration depends on temperature

How do we calculate a Tm[X] in this case?

• Let’s simplify the system. A reaction: A1 ↔ A2, where parameters ∆ν, δ and εk, are zero, so that:
1 P Ž• x 1 P Ž• x
2 2 1 P
x
Q⁄Qx Qx Q⁄Qx Q V Ž• x V′ Ž• x
Ž• x exp 1 P ′ exp P
2 P Q Q Q Q
Q

• Differentiating r with respect to T, at constant X, and equating to zero:

[ V Ž• V 1 V′ Ž• V 1
exp 1 P ′ exp P 0
x x
[Q n
Q Q Q Q Q Q

P Δw• x V Qo
1 P ^ exp Qo V′ Qo
and operating: Eq. 3-18
67
Lecture 3. Reaction Rate: Influence of temperature and conversión
3. Constant-Rate Curves.
3.3 Optimum Temperature Progression.

• We define the optimum temperature progression to be that progression which minimizes V/Fk0, for a
given conversion of reactant.
• At any composition, it will always be at the temperature where the rate is a maximum.
• This optimum may be an isothermal or it may be a changing temperature:
 in time for a batch reactor,
 along the length of a plug flow reactor,
 or from stage to stage for a series of mixed flow reactors.

68
Summary

1. The rate of a chemical reaction depends on the temperature, pressure, and composition of the system
under investigation.

2. Certain species that DO NOT appear in the stoichiometric equation for the reaction under study can
markedly affect the reaction rate, even when they are present in only trace amounts. These materials are
known as catalysts or inhibitors, depending on whether they increase or decrease the reaction rate.

3. Reaction rate is expressed by a function of the type:

r = function( rate constants , c j )

where cj is the concentrations of the various species present in the system (reactants, products, catalysts, and
inhibitors). The form of the function(cj) may also depend on the temperature, as the rate of the steps that
conform the reaction mechanism change.
The reaction rate constants ki do not depend on the composition of the system and are consequently
independent of time in an isothermal system (but they depend on temperature).

4. Reaction rate expressions and constants ARE EXPERIMENTAL. They cannot be predicted and have to be
measured.

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Summary

5. Very often the function(cj), can be written as

=
functionH23 I 1 23 6
3

where the product Π is taken over all components of the system. The exponents βj are the orders of the
reaction with respect to each of the i species present in the system. The algebraic sum of the exponents is
called the total order or overall order of the reaction.

6. Orders of reaction higher than 3 or fractional imply that the reaction is not elementary.

7. In a system in which both forward and reverse reactions are important, the net rate of reaction can
generally be expressed as the difference between the rate in the forward direction rf and that in the opposite
direction ri.
g h

8. The mathematical expressions for the forward and reverse reactions have to be consistent with the
equilibrium expressions obtained from stoichiometry.

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Summary

9. The rate constant k generally varies with the absolute temperature T of the system according to the law

V
proposed by Arrhenius.
exp
Q
where
E is the apparent activation energy of the reaction R is the gas constant
A is the preexponential factor, sometimes called the frequency factor, which is assumed to be a temperature
independent quantity

10. The Activation Energy expresses HOW temperature influences the rate constant. The higher E, the higher
the influence of T on the constant value. So:
 Exothermic reactions: Er > Ef, the reverse reaction constant increases more with T. Equilibrium constant
decreases with temperature.
 Endothermic reactions: Ef > Er, the forward reaction constant increases more with T. Equilibrium constant
increases with temperature.

11. The Activation Energy should be calculated ONLY when the constant rate is in concentracion units.

12. The influence of temperature and composition on reaction rate is better represented in constant-rate
diagrams. They ilustrate the operation conditions that would increase reaction rate.
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 EQ1021 Chemical Reaction Engineering

Lecture 3. Reaction Rate: Influence of Temperature and Conversion

1 Mathematical Equations for the Reaction Rate
2 The Homogeneous General Reaction
3 Constant-Rate Curves

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