Rate Laws and Stoichiometry

1.0 Rate Laws and Stoichiometry

Stoichiometry is a section of chemistry that involves using (studies the) relationships between reactants
and/or products in a chemical reaction to determine desired quantitative data. In Greek, stoikhein means
element and metron means measure, so stoichiometry literally translated means the measure of elements-
materials involved.

Lesson 5: Objectives
At the end of this chapter, you should be able to;
(a) Calculate the time dependent convers ions
(b) Prepare stoichiometric tables
(c) Explain the difference in the conversion between different reaction orders
(d) Use Design Equations for Flow Reactors to calculate the size of a reactor

There exists a relationship between the reaction rate and conversion from experimental observation.

From mass balance equation

N  N At
N A0  N At  rV  A0 V
r
XN A0
But N A0  N At  XN A0  V
r

Therefore design requires the use of an equation for the reaction rate in terms of concentrations at a
constant temperature to apply in the design equations, where each of the concentrations (and volumes or
volumetric flow rates) are expressed as a function of conversion.

This can be achieved by preparation of stoichiometric tables. While preparing the stoichiometric table, there
is need to understand how the rate of formation for any component is related to the rate of reaction taking
into consideration of the different rate laws and define the reaction order.

5.1 Stoichiometric tables for conversion

Consider the reaction:

aA+ bB  cC + dD
Taking the species A (limiting reactant) as the basis of calculation so divide through by the coefficient of A
b c d
A+ B C+ D
a a a
This implies that the concentration of all the species (A, B, C and D) are expressed in terms of the
concentration of the concentration of A. This makes every quantity is now ‘per mole of A’

This is as the case that` reaction rate is usually expressed in terms one of the components. In this case, the
rate of reaction is equal to the rate of formation of “A” in this case. Thus we need an expression for the rates

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 Rate Laws and Stoichiometry

of reaction for other components in terms of the rate of formation of “A”. For instance, every mole of “A”
c
consumed gives moles of C. Thus the rate of formation of
a
c c
C x Rate of dissapearance of A  C  rA   .
a a
From the equation aA+ bB  cC + dD the RELATIVE RATE expression can be written as
 rA  rB rC rD
   Thus rate is a function of concentration.
a b c d
rNO rO rNO
Another example ca be cited - For instance, 2NO + O2 → 2NO2, the rates are: -  2  2
2 1 2
If NO2 is being formed at a rate of4 mol dm-3 s-, then the rate of disappearance of NO is given by
- 2 rNO
4x 2
 4 mol dm- 3 s -1
2
- 1rO
Whereas the rate of disappearance of O2 is is given by 4 x 2
 2 mol dm- 3 s -1
2
b c d
Considering A + B  C + D :
a a a
We can express the number of remaining moles in a batch reaction vessel in terms of conversion X in a
stoichiometric table given below Table 2.
Table 1 A stoichiometric table.

Species Initial Change Remaining

A NA0 -(NA0X) =NA NA=NA0 - NA0X
b b
B NB0 -( )N A0 X NB=N BO -( N A0 X)
a a
c c
C NC0 ( ) N A0 X NC=N CO +( N A0X)
a a
d d
D ND0 ( ) N A0 X ND=N DO +( N A0 X)
a a
I(inerts) NI0 --- NI== NI0

TOTAL NT0 a

a a
 
NT  NT 0  d  c  b  1 N A0 X 
 d c b 
NTOTAL  NT 0  XN A0  (  )  (  1) 
 a a a 
d c b
The total from the Where, (  )  (  1) is the change of species Aor  A(dA)
a a a
ThusNTOTAL  NT 0  XNT 0 A
NTOTAL  (1  y A0 X ) NT 0

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 Rate Laws and Stoichiometry

Activity- Watch the video in the link below and discuss within the group

Watch video on the link provided below to help you develop a clear picture on the variation of the reactants to give a product
https://www.youtube.com/watch?v=80bc_bJM9lQ

A similar table can be constructed for the molar flow rates in terms of conversion for a PFR or CSTR where we
replace the Ni by ni. Note that the change in total number of moles (i.e. NT - NT0 or nT - nT0) can be calculated
c d  b
in terms of the conversion and is equal to X or dX , where X or d species     -  1   (see
a a  a
how it is worked at the table above showing the change in moles per mole of “A reacted”)

This quantity is especially important when working with gases in which case the change in total number of moles
leads to a change in pressure with time in a batch reactor or in a PFR to a change in volumetric flow rate along
the length of the reactor. The concentrations can be determined by dividing the items in the table by “V” for a
batch reaction or by v for the case of a flowing system.

The link provided below to help you develop a clear picture on how to develop stoichiometric tables
https://www.google.com/search?q=Stoichiometric+tables+for+conversion&source=lmns&bih=657&biw
=1366&safe=active&hl=en&ved=2ahUKEwiw24v3wNvqAhUF04UKHXNICm4Q_AUoAHoECAEQAA

5.2 Change in pressure for a gas phase reaction in a constant volume batch reactor

For a gas phase reaction, the gas law can be used to relate the pressure to the volume of the reaction at any
given instant in the batch reactor. It is worth to note that the vapour will take up the entire volume of the
reactor therefore the reaction volume is equal to the reactor volume, which is usually fixed. Under most
conditions of gas phase reactions, the ideal gas law provides a good approximation to the thermodynamic
behaviour of the gas.

PV  NTOTAL RT
where R is the ideal gas constant. A similar equation can written, which applies at the
start of the reaction as shown below

PV
0  N 0 RT0
Since it is a batch reactor the volume of the reactor is not changing so that no subscript on V used.

To get the value of P

NTOTAL T
P  P0 .
N0 T0
When NTOTAL is used as it is defined in the stoichiometric Table above gives

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 Rate Laws and Stoichiometry

NTOTAL  (1  y A0 X ) N A0
NTOTAL T (1  y A0 X ) N A0 T N T
P  P0 .  P0 .  P0 (1  y A0 X ) A0 .
N A0 T0 N A0 T0 N A0 T0
T
P  P0 (1  y A0 X ).
T0

The equation provides the desired relationship between pressure in the reactor and the conversion at a
constant temperature thus an isothermal reactor. However the Equation could also be used for calculating how
changes in temperature will alter the pressure in the reactor.

5.3. Change in volumetric flow rate in a PFR

For a flowing vapour, the ideal gas can also be used to relate the volumetric flow rate to the total molar flow
rate. In this case, we take the time derivative of the ideal gas law to give the relationship between the
volumetric and total molar flow rates at a given distance along the PFR in terms of the pressure and
temperature at the same location
Pv  nt RT
At the inlet to the PFR we have

P0 v  n t0 RT0
Taking the ratio
nt P0T
v  v0 .
n0 PT0
Referring to the definination in the stoichiometric Table 2. Gives

v  v0 1  yA0X .
P0T
PT0

The equation can be used for calculating the volumetric flow rate in terms of temperature and pressure.
However, an isothermal reactor is considered in most cases and the equation reduces to

v  v0 1  yA0X .  v0 1  X .
P0T
PT0

c d  b
where X  X or d species     -  1    yA0X
a a  a
As this is an isothermal reactor, concentrations of the components depend on the volumetric flow rate
according the general equation
nA
CA 
v
When the value of nA is extacted from the stoichiometric table and plugged into the equation above, we find
that

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 Rate Laws and Stoichiometry

nA nA0  nA0 X nA0 1  X   1  X  

CA     CA0  
v v0 1  X  v0 1  X   1  X  

Thus, the change in concentration of “A” with increasing conversion is not only due to losing moles to the
reaction, but also occurs due to changes in volumetric flow rate, which, in turn, are due to changes in the total
molar flow rate. This effect is emphasized by considering the concentration of an inert as a function of
conversion, which is given by
1
CI  CI 0
1  X

Thus the concentration of an inert material will be reduced with increasing conversion if the reaction
generates moles, and the concentration of the inert will increase if the reaction consumes moles. Similarly, you
should be able to generate a stoichiometric table for concentrations for a reactant B in terms of “A”.
  N B0 b  
  X 
  N A0 a  
CB  C A0 

1  X  
 
 
The equation above is a general equation for the rating species as they are in the stoichiometric table.

5.4 Reaction Rate Equation or Rate Law

The rate of reaction -rA depends on concentration and temperature as expressed as

rA  k (T ) xf (CA , CB ......)
Where k(T) is rate constant as a function of temperature. Considering an isothermal situation, the rate of
reaction can be written as

rA  k AC A CB
Where α is defined as the reaction order with respect to A and β the reaction order with respect to B. The
overall order of the reaction is given by the sum, n = α + β. For
instance, for the reaction of
2NO + O2 → 2NO2

the rate law can be expressed as rNO  k NOCNO

2
CO2

The overall order for the reaction is equal to 3, whereas the reaction is 2nd order with respect to NO and 1st
order with respect to O2. Note that the exponents α and β are not always equal to the stoichiometric
coefficients except for the case where the reaction is an elementary step as discussed below.

Rate Constant Units

The units of k depend on the form of the rate law. We know that the rate must have units of moles/(volume-time) so that k
has units of (concentration)1-n/time. Thus when n is equal to 1, k has units of s-1, for n equal to 2, k has units ofMol-1 dm3 s-1,
and when n is equal to 3, k has units of mol-2 dm6 s-1.
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 Rate Laws and Stoichiometry

This is the case for an elementary reaction is one that involves only a single step. For instance:
H + Br2 → HBr + Br
This occurs when one hydronium ion collides and reacts with one bromine molecule. In such a case, the rate of
reaction is given by
rHBr  k [H] [Br2 ].

Because the step involves the collision of the two molecules, the rate is then proportional to each of the
concentrations. A general rule is thus that for an elementary reaction, the reaction order follows from the
stoichiometric coefficients. However, many reactions are not elementary but instead have a complex, multistep
reaction mechanism. In this case the rate of reaction does not often follow from the stoichiometric
coefficients. For example, considering the rate of reaction for the reaction of
H2 + Br2 → 2 HBr
3
k1CH 2 CBr22
The rate law is rHBr  and must be determined experimentally.
CHBrk  k2CBr2
2

The common form of the rate law

This reaction occurs due to a free radical mechanism, which actually corresponds to a series of elementary
reaction steps as illustrated below.
Br2 → 2 Br*
Br*+H2 → HBr + H*
H*+Br2 → HBr + Br*
H*+HBr →H2 + Br*
2 Br→Br2

k
1 2 Br 
1. Br2 
k
2. Br  H 2 
 2 HBr  H  propagation

k
3. H  Br2  3  HBr  Br propagation

k4
4. H  HBr 
 H 2  Br inhibition
k5
5. 2 Br 
 Br termination
2

How this is achieved

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 Rate Laws and Stoichiometry

d[HBr]
I  k 2 [Br][H 2 ]  k 3 [H][Br2 ] – k 4 [H][HBr]
dt
d[Br]
II.  0  2 k 1 [Br2 ] – k 2 [Br][H 2 ]  k 3 [H][Br2 ]  k 4 [H][HBr] – 2 k 5 [Br] 2
dt
d[H]
III.  0  k 2 [Br][H 2 ] – k 3 [H][Br2 ] – k 4 [H][HBr]
dt
k1
IV . add II  III : 0  2 k 1 [Br2 ] – 2 k 5 [Br] 2  [Br]  [Br2 ]
k5

 k 
k 2  1 [Br2 ] [H 2 ]
k
  
k 2 [Br][H 2 ]
V. solve III for [H] : [H] 
5

k 3 [Br2 ]  k 4 [HBr] k 3 [Br2 ]  k 4 [HBr]

 k 2 [Br][H 2 ]  k 3 [H][Br2 ] – k 4 [H][HBr] - k 2 [Br][H 2 ] – k 3 [H][Br2 ] – k 4 [H][HBr]

d[HBr] d[H]
VI. subtract III from I : -
dt dt
Gives 2 k 3 [H][Br2 ]

d[HBr] 2 k 3 k 2 k 1 .k 5 [H 2 ] [Br2 ] [Br2 ] k [H 2 ] [Br2 ] . [Br2 ]

substituteV into VI :   rHB r 
dt k 3 [Br2 ]  k4[HBr] k 3 [Br2 ]  k4[HBr]

In this case, the rate law and reaction order must be determined experimentally. If a reaction has several
steps then the slowest elementary reaction step often is the rate-limiting (or rate determining) step. In some
cases, non-elementary reactions have stoichiometric coefficients are identical to the orders, for example for
the reaction of
2NO + O2 → 2NO2
the rate is equal to rNO  k NOC CO2 as indicated initially.
2
NO

SELF-TEST QUESTIONS

1. Given that for a reaction 2A+B→5C

a) If k = 5:7 x 10-4 mol-1 dm3 s-1 calculate the rate of reaction which is first order in both A
and B when [A] = 5:0 x 10-2 mol dm-3 and [B] = 2:0 x 10-2 mol dm-3.
b) What would the rate have been if [A] had been 5:0 x 10-4 mol dm-3.and [B] had been 2:0
x10-3 mol dm-3?
c) What conclusion can you draw from the results of your calculation?

2. Construct a stoichiometric table for the following batch reaction and derive expressions relating
the concentrations of the reactants to the conversion.
N2 + 3H2 ⇌ 2NH3

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