3.

RATE LAWS AND STOICHIOMETRY

Rational For Chapter 3
In chapter 2 we saw that if we had –rA as a function of X, [–rA= f(X)] we could size
many reactors and reactor sequences and systems.

How do we obtain –rA = f(X)?

We do this in two steps
1. Part 1 Rate Law – Find the rate as a function of concentration,
–rA = k fn (CA, CB …)
2. Part 2 Stoichiometry – Find the concentration as a function of
conversion
CA = g(X)
Part 1: Rate Laws
1. Relative Rates of Reaction
2. Power Law Model
3. Rate Constant, k
4. Elementary Reactions
5. Non-Elementary Rate Laws
6. Reversible Reactions
Part 2: Stoichiometry
1. Batch System Stoichiometric Table
2. Flow System Stoichiometric Table
Part 1: Rate Law
A rate law describes the behavior of a reaction. The rate of a reaction is a function of temperature (through the rate
constant) and concentration. A homogeneous reaction is one that involves only one phase. A heterogeneous
reaction involves more than one phase, and the reaction usually occurs at the interface between the phases .An
irreversible reaction is one that proceeds in only one direction and continues in that direction until the reactants are
exhausted. A reversible reaction can proceed in either direction, depending on the concentrations of reactants and
products relative to the corresponding equilibrium concentrations.

1. Relative Rates of Reaction

The relative rates of reaction of the various species involved in a reaction can be obtained from
the ratio of stoichiometric coefficients.
aA  bB  cC  dD b c d
A B C D
For reaction or a a a
for every mole of A that is consumed, c/a moles of C appear.
c
C
Rate of formation of a (rate of disappearance of A)
c c
rC  (rA )   rA
a a
c
rC  rD
The relationship betweenthe rates of formation of C and D is d
The relationship can be expressed directly from the stoichiometry of the reaction:
rA r r r
 B  C  D
a b c d

2. Power Law Model

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The dependence of the reaction rate (-rA) on the concentrations of the species present,f(C), is almost without
exception determined by experimental observation. One, of the most common general forms of this dependence is
the product of concentrations of the individual reacting species, each of which is raised to a power.
 rA  kC A C B the exponents of the concentrations in this equation lead to the concept of reaction order.
The order of a reaction refers to the powers to which the concentrations are raised in the kinetic rate law.
  order in respect to reactant A
  order in respect to reactant B
    n - overall order of reaction
The units of  rA are always in terms of concentration per unit time, while the units of specific rate constant, k A ,
will vary with the order of the reaction.
For the reaction A  P with a reaction order n, the units of the specific reaction rate constant are:

k
concentration 1n
time
Rate law corresponding to a zero-, first, second, and third-order reaction, together with typical units for the
corresponding rate constants are:

Zero-order (n=0) :  rA  k A k   mol / dm 3 s

First-order (n=1) :  rA  k A C A k   s 1
Second-order (n=2):  rA  k A C A2 k   dm 3 / mol  s
Third-order (n=3) :
 rA  k A C A3 k   dm 3 / mol 2  s 1

3. Rate Constant, k
The reaction rate constant k, is not truly a constant, it is merely independent of the concentrations of the species
 E / RT
involved in the reaction) and is given by the Arrhenius Equation: k A (T )  Ae . It is almost strongly
dependent on temperature. It depends on whether or not a catalyst is present, and in gas-phase reactions it may be
a function of total pressure. In liquid systems it can be function of other parameters, such as ionic strength and
choice of solvent.

T  k  A

Where T  0 k  0

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 E –activation energy (cal/mol) or (J/mol).
R = gas constant =8.314 J/mol K=1.987cal/mol K
T = absolute temperature (K)
A = frequency factor (units of A, and k, depend on overall reaction order)
The activation energy is determined experimentally by caring out the reaction at
 E / RT
several different T. After taking the natural Logarithm(ln) of k  Ae
E1  E  1 1 
ln k  ln A    k T2   k T1  exp    
R T 
 R  T1 T2 
It can be seen that a plot of (lnk) versus (1/T) should be straight line whose slope is proportional to the
activation energy.

More on Activation Energy

The activation energy can be thought of as a barrier to the reaction. One way to view the barrier to a reaction is
through the reaction coordinates. These coordinates denote the energy of the system as a function of progress
along the reaction path. For the reaction

the reaction coordinate is

progress along reaction path

Figure above shows the potential energy of the three atoms (or molecules) system A, B, and C, as well as the reaction
progress as we go from reactant species A and BC to products AB and C. Initially A and BC are far apart and the
system energy it just the bond energy BC. At the end of the reaction, the products AB and C are far apart, and the
system energy is the bond energy AB. As we move along reaction coordinates (x-axis) to the right, the reactants A and
BC approach each other, the BC bond begins to break, and the energy of the reaction pair increases until the top of the
barrier is reached. At the top, the transition state is reached where the intermolecular distances between AB and
between BC are equal. (e.g. A-B-C), as a result, the potential energy of the initial three atoms (molecules) is high. As
a reaction proceeds further, the distance between AB and C increases and the energy of the reacting pair decreases to
that of the AB bond energy.
We see that for the reaction to occur, the reactants must overcome an energy barrier or activation energy EA.
Why is there an Activation Energy?
1. the molecules need energy to distort or stretch their bonds in order to break them and to
thus form new bonds

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 2. as the reacting molecules come close together they must overcome both steric and electron
repulsion forces in order to react

In our development of collision theory we assumed all molecules had the same average energy. However, all the
molecules don’t have the same energy, rather there is distribution of energies where some molecules have more energy
than others. The distraction function f(E,T) describes this distribution of the energies of the molecules. The distribution
function is read in conjunction with dE

f(E, T) dE = fraction of molecules with energies between E and

E + dE

One such distribution of energies is in the following figure.

Increase Temperature

By increasing the temperature we increase the kinetic energy of the reactant molecules which can in turn be transferred
to internal energy to increase the stretching and bending of the bonds causing them to be in an activated state,
vulnerable to bond breaking and reaction. We see that as the temperature is increased we have greater number of
molecules have energies E A or greater and hence the reaction rate will be greater.

You can tell the overall reaction order by the units of k

Reaction
CA -rA Rate Law k
Order
(mol/dm3) (mol/dm3*s) Zero -rA = k (mol/dm3*s)

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 (mol/dm3) (mol/dm3*s) 1st -rA = kCA s-1
(mol/dm3) (mol/dm3*s) 2nd -rA = kCA2 (dm3/mol*s)

4. Elementary Rate Law

A reaction follows an elementary rate law if and only if the stoichiometric coefficients are the same
as the individual reaction order of each species. For the reaction in the previous example (
), the rate law would be:  rA  kC AC B

if 2NO+O2 2NO2 then -rNO = kNO (CNO)2 CO2 it is elementary!

5. Non-Elementary Rate Laws
A large number of both homogeneous and heterogeneous reactions do not follow simple rate laws.
Homogeneous Reactions. The overall order of a reaction does not have to be an integer, nor does the
order have to be an integer with respect to any individual component.

Example: If the rate law for the non-elementary reaction A  B  C  D

is found to be  rA  kC A C B
2

then the reaction is said to be 2nd order in A, 1st order in B, and 3rd order overall.

Heterogeneous Reactions. In many gas-solid catalyzed reactions, it historically has been the practice to write the
rate law in terms of partial pressures rather than concentrations. Pi  C i RT
6. Reversible Reactions
All rate laws for reactions must reduce to the thermodynamic relationship relating the
reacting species concentration at equilibrium. At equilibrium, the rate of reaction is
identically zero for all species (i.e, rA  0)
For general reaction: aA  bB  cC  dD the concentrations at equilibrium are related by
the thermodynamic relationship for thye equilibrium constant K C :
c
C Ce d
C De KC
KC  a b
C Ae C Be The units of the thermodynamic equilibrium constant, , are
mol / dm  3 d  c b  a

The net rate of formation of any species is equal to its rate of formation in the forward reaction plus its
rate of formation in the reverse reaction:

ratenet = rateforward + ratereverse

Part 2: Stoichiometry
We shall set up Stoichiometric Tables using A as our basis of calculation in the following reaction.
aA  bB  cC  dD We will use the stoichiometric tables to express the concentration as a
function of conversion. We will combine Ci = f(X) with the appropriate rate law to obtain -rA = f(X).

b c d
A B C D
a a a

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 1. Batch System Stoichiometric Table
Species Symbol Initial Change Remaining
A A

B B

C C

D D
Inert I -------
________ ____________

Where: NA0, NB0 – number of moles initially present

-NA0X – number of moles are consumed in the system as a result of chemical reaction

NA – number of moles remaining in then system after conmversion X has been achieved.

 - the stoichiometric coefficient in parentheses( d / a  c / a  b / a  1 ) represent the increase in the total

number of moles per mole of A reacted.
The parameter  i allows us to factor NA0 in each of the expressions for concentration.
N i0 C y d c b
i   i0  i0     1
N A0 C A0 y A0 and a a a

NA
CA 
V - batch system concentration of A is a number of moles of A per unit volume
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

V  V0
N A N A0 (1  X )
CA    C A0 (1  X )
V V0
N B N A0  b   b 
CB     B  X   C A0   B  X 
Then V V0  a   a 
 c   d 
C C  C A0   C  X  C D  C A0   D  X 
 a   a 
 rA  k A C A C B
2
 b 
 rA  C A3 0 (1  X ) 2   B  X 
If , then  a  - constant volume batch
and we have  rA  F ( X )

2. FLOW SYSTEM STOICHIOMETRIC TABLE

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 The form of Stoichiometric tables for a continuous-flow system
virtually identical to that for a batch system except that we replace number of moles by molar
flow rate. Taking A as a basis, divide eqn. aA  bB  cC  dD through by the stoichiometric
b c d
A B C D
coefficient of A to obtain a a a

Species Symbol Reactor Feed Change Reactor Effluent

A A

B B

C C

D D

Inert I -------
________ ____________

Fi 0 C  C y d c b
i   i0 0  i0  i0     1
Where: FA0 C A0 0 C A0 y A0 and a a a

Concentration -- Flow System:

FA
CA 


Liquid Phase Flow System:

0  
FA FA0 (1  X )
CA    C A0 (1  X )
 0
F B FA0  b   b 
CB     B  X   C A0   B  X 
0 0  a   a 

If the rate of reaction were -rA = kCACB then we would have

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  b 
 rA  kC A2 0 (1  X )  B  X 
 a 
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.

Flow Reactors with Variable Volumetric Flow Rate. To derive the concentrations of each species in terms of
conversion for a gas phase flow system, we shall use the relationships for the total concentration. The total
concentration, CT, at any point in the reactor is the total molar flow rate, FT divided by volumetric flow rate ʋ .In the
P
CT 
gas phase, the total concentration is also found from the gas law, zRT Equating these two relationships gives
FT P
CT  
 zRT ( 3.1 )

FT 0 P0
CT 0  
At the entrance to the reactor, 0 z 0 RT0 ( 3.2 )

Taking the ratio of Equation( 3.1 ) to Equation (3.2) and assuming negligible changes in the compressibility factor, Z,
during the course of the reaction we have upon rearrangement
 F P T 
   0  T  0  
 FT 0  P  T0 
(3.3)
We can now express the concentration of species j for a flow system in terms of its flow rate, Fj, the temperature, T,
and total pressure, P.
Fj Fj FT 0  Fj  P  T0   Fj  P  T0 
Cj        C j  CT 0    
 FT  P0  T 0  FT  P0  T   FT  P0  T 
0  
FT 0  P  T0 ( 3.4)

The total molar flow rate is just the sum of the molar flow rates of each of the species in the system;
n
FT  FA  FB  FC  ...   FJ
j 1 ( 3.5 )

The molar flow rates, Fi, are found by solving the mole balance equations. The concentration given by Equation ( 3.4)
will be used for measures other than conversion when we discuss membrane reactors multiple gas-phase reactions .
Now let's express the concentration in terms of conversion for gas flow systems. The total molar flow rate can be
written in terms of conversion and is species in the system and is FT  FT 0  FA0X (3.6) we divide this equation
FT F
 1  A0 X  1  y A0X  1  X
by FT0: FT 0 FT 0
d c b  F F  FT 0
      1 A0  y A0   Tf
a a a  FT 0 where FT 0 when X =1 and FT = FTf
substituting for FT/FT0 for the volumetric flow rate we have:

T P0
   0 (1  X )
T0 P - volumetric flow rate for gas-phase flow systems

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 change in total number of moles when reaction is completed

total number of moles fed in to reactor
d c b  N NT N  XN A0
      1 A 0  y A 0   T0  1  X
 a a a  NT 0 NT 0 NT 0

For the gas-phase flow system concentration of A:

FA FA0 (1  X ) T0 P (1  X ) T0 P
CA    C A0
  0 (1  X ) T P0 (1  X ) T P0

b b
FA0 (  B  X) ( B  X )
F a T P a T0 P
CB  B  0
 C A0
  0 (1  X ) T P0 (1  X ) T P0

c c
FA0 ( C  X) ( C  X )
FC a T0 P a T0 P
CC    C A0
  0 (1  X ) T P0 (1  X ) T P0

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 :  rA  k A C A C B
2

 b 
C A3 0 (1  X ) 2   B  X 
 a 
 rA 
then (1  X ) 3

PA0 y B 0 C B 0 FB 0
C A0  B   
with RT y A 0 C A 0 FA 0