Chapter 3 Rate Laws and Stoichiometry

Chapter 3
Rate Laws and Stoichiometry
Prepared by Dr Lee Kiat Moon

Relative rates of reaction
• Consider
aA  bB  cC  dD a, b, c, d = stoichiometric coefficients
A, B, C, D = chemical species
• Taking reactant A (limiting reactant) as basis of calculation:

b c d
A B  C D
a a a
c
Rate of formation of C = Rate of disapperance of A
a
rA rB rC rD
  
a b c d
Example:
2NO + O2 ↔ 2NO2
• If NO2 is being formed at a rate of 4 mol/m3.s, i.e.,

rNO2 = 4 mol/m3.s
• What is the rate of formation of NO and rate of disappearance of

oxygen, O2?
rNO rO2 rNO2
 
 2 1 2
rNO 

 2 4mol / m 3 s  4mol / m 3 s
2
 rO2 

 1 4mol / m 3 s 
 2mol / m 3 .s
2
The reaction order and rate law
• The algebraic equation that relates –rA to the species concentrations
is called the kinetic expression or rate law.
-rA = [kA(T)][fn (CA, CB, …)]

• The specific rate of reaction (rate constant), kA, always refers to a
particular species in the reaction and strongly dependent on
temperature. kA could be determined by Arrhenius equation.
A = preexponential factor / frequency factor

𝒌𝐀 𝑻 = 𝑨𝒆−𝑬Τ𝑹𝑻 E = activation energy, J/mol or cal/mol
R = gas constant = 8.314 J/mol.K = 1.987 cal/mol.K
T = absolute temerpature, K
𝛼 𝛽
−𝑟A = 𝑘A 𝐶A 𝐶B
• The order of a reaction refers to the powers to which the
concentrations are raised in the kinetic rate law.
• In the above equation, the reaction is α and β order with respect to
reactant A and B, respectively.
• Unit of –rA = mol/dm3.s and kA varies with the order of the reaction
Reaction Order Rate Law k unit
Zero -rA=kA mol/dm3.s
One -rA=kACA s-1
Two -rA=kACA2 dm3/mol.s
Three -rA=kACA3 (dm3/mol)2.s-1

• An elementary reaction is one that involves a single step. The
stoichiometric coefficients in this reaction are identical to the powers in the
rate law.
aA  bB  cC  dD
 rA  k AC C a
A
b
B
• Many reactions involving multiple steps and pathways. The stoichiometric
coefficients in these reactions may not be identical to the powers in the
rate law.
• It is important to remember that the rate laws are determined by
experimental observation!
Stoichiometry
• Rate law is expressed as a function of concentration (conversion) and it

depends on more than one species
• Relate the concentrations of the different species to each other 
Stoichiometric Table!
• Stoichiometric table presents the stoichiometric relationship between
reacting molecules for a single reaction.
• Take species A as the basis of calculation (i.e. limiting reactant)  per
mole of A
b c d
A B  C D
a a a
• Let NAo – initial number of moles of A
NAoX – moles of A consumed in the system
NA – number of moles of A in the system
Hence, NA = NAo – NAoX = NAo(1-X)
• For every moles of A that reacts, B/A moles of B must react

moles B reacted
moles B reacted   moles A reacted
moles A reacted
b
 ( N Ao X )
a
• In stoichiometric table,
Column 1: particular species
Column 2: the number of moles of each species initially present
Column 3: the change in the number of moles brought about by reaction
Column 4: the number of moles remaining in the system at time t
• δ - Change in the total number of moles per mole of A reacted
d c b
   1
a a a
• i – to factor NAo in each expressions for concentration
N io Fio Cio yio

i    
N Ao FAo C Ao y Ao
Change in total number of moles to attain completeconversion of A

• . 
Total number of moles of all species fed to the reactor
N AO
   y A0  
NTO
Stoichiometric table (batch system)
b c d
A B  C D
a a a
Constant volume batch system
• For constant volume systems:
NA
• Hence, we can express concentration (for species A) as: C A 
V
Concentration of Reactant A Concentration of Product C

N A N A0 (1  X)  c 
CA    C A0 (1  X) CC  C A0  ΘC  X 
V V0  a 
Concentration of Reactant B Concentration of Product D

N B N A0  b   b   d 
CB    B
Θ  X   C A0  B
Θ  X CD  CA0  Θ D  X 
V V0  a   a   a 
Example:
• The saponification for the formation of soap from aqueous caustic
soda and glyceryl stearate is
3NaOH  (C17 H35COO)3 C3H5  3C17 H35COONa  C3H5 (OH)3
• Letting X represent the conversion of sodium hydroxide (the moles of

sodium hydroxide reacted per mole of sodium hydroxide initially
present), set up a stoichiometric table expressing the concentration
of each species in terms of its initial concentration and the conversion
X.
• If the initial mixture consists of NaOH at a concentration of 10
mol/dm3 and of C17H35COO)3C3H5 at a concentration of 2 mol/dm3,
what is the concentration of glycerine (C3H5(OH)3) when the
conversion of NaOH is (a) 20% and (b) 90%?
Stoichiometric table (flow system) Constant volume
(Liquid, no phase change)
b c d
A B  C D
a a a
Variable volume
• Equation of state: 𝑃𝑉 = 𝑍𝑁𝑇 𝑅𝑇
• Dividing with equation of state at t = 0 (𝑃𝑜 𝑉𝑜 = 𝑍𝑜 𝑁𝑇𝑜 𝑅𝑇𝑜 ), resulting
𝑃𝑜 𝑇 𝑍 𝑁𝑇 𝑃𝑜 𝑇 𝑍
𝑉 = 𝑉𝑜 = 𝑉𝑜 1 + 𝜀𝑋
𝑃 𝑇𝑜 𝑍𝑜 𝑁𝑇𝑜 𝑃 𝑇𝑜 𝑍𝑜
• However, the compressibility factor (Z) will not change significantly

for the gas-phase system studied, hence
Batch system Flow system
 Po  T   Po  T 
V  Vo (1  X )   v  vo (1  X )  
P  To  P  To 
Stoichiometric table (variable volume)
Example:

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Chapter 3

Rate Laws and Stoichiometry

Prepared by Dr Lee Kiat Moon

• Taking reactant A (limiting reactant) as basis of calculation:

• If NO2 is being formed at a rate of 4 mol/m3.s, i.e.,

• What is the rate of formation of NO and rate of disappearance of

-rA = [kA(T)][fn (CA, CB, …)]

A = preexponential factor / frequency factor

Zero -rA=kA mol/dm3.s

One -rA=kACA s-1

Two -rA=kACA2 dm3/mol.s

Three -rA=kACA3 (dm3/mol)2.s-1

• Rate law is expressed as a function of concentration (conversion) and it

• For every moles of A that reacts, B/A moles of B must react

N io Fio Cio yio

Change in total number of moles to attain completeconversion of A

Concentration of Reactant A Concentration of Product C

Concentration of Reactant B Concentration of Product D

• Letting X represent the conversion of sodium hydroxide (the moles of

• However, the compressibility factor (Z) will not change significantly

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