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Complex Reactions Write the net rate laws
𝑟𝐴 = 𝑟1𝐴 + 𝑟2𝐴
Identify every reaction
You must know the
𝒌𝟏𝑨
𝑟𝐵 = 𝑟1𝐵 + 𝑟2𝐵
individual rate laws
(1) 𝐀 + 𝐁 𝟑𝐂 + 𝐃
𝑟1𝐴 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 𝑟𝐶 = 𝑟1𝐶 + 𝑟2𝐶
𝒌𝟐𝑨
(2) 𝑨 + 𝟐𝑪 𝟑𝑬 𝑟2𝐴 = −𝑘2𝐴 𝐶𝐴 𝐶𝐶2 𝑟𝐷 = 𝑟1𝐷 + 𝑟2𝐷
𝑟𝐸 = 𝑟1𝐸 + 𝑟2𝐸
Write the net rate laws in terms of
concentration

𝒓𝟏𝑨 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 Relate the individual rate

laws
𝑟1𝐵 = 𝒓𝟏𝑨 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵
𝑟1𝐶 = 3 −𝒓𝟏𝑨 = 3𝑘1𝐴 𝐶𝐴 𝐶𝐵 𝒓𝟏𝑨 𝑟1𝐵 𝑟1𝐶 𝑟1𝐷
= = =
𝑟1𝐷 = −𝒓𝟏𝑨 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 −1 −1 3 1
𝒓𝟐𝑨 = −𝑘2𝐴 𝐶𝐴 𝐶𝐶2 𝒓𝟐𝑨 𝑟2𝐶 𝑟2𝐸
= =
𝑟2𝐶 = 2𝒓𝟐𝑨 = −2𝑘2𝐴 𝐶𝐴 𝐶𝐶2 −1 −2 3
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𝑟2𝐸 = −3𝒓𝟐𝑨 = 3𝑘2𝐴 𝐶𝐴 𝐶𝐶2
Complex Reactions
Mole balance
𝑉
𝑑𝑁𝐴
= 𝐹𝐴0 − 𝐹𝐴 + න 𝑟𝐴 𝑑𝑉
𝑑𝑡

Molar quantities Concentration

(Gas or Liquid) (Liquid)

Batch 𝑑𝑁𝐴 𝑑𝐶𝐴
= 𝑟𝐴 𝑉 = 𝑟𝐴
𝑑𝑡 𝑑𝑡
𝑑𝑁𝐵 𝑑𝐶𝐵
= 𝑟𝐵 𝑉 = 𝑟𝐵
𝑑𝑡 𝑑𝑡
PFR/PBR 𝑑𝐹𝐴 𝑑𝐶𝐴 𝑟𝐴
= 𝑟𝐴 =
𝑑𝑉 𝑑𝑉 𝑣0
𝑑𝐹𝐵 𝑑𝐶𝐵 𝑟𝐵
= 𝑟𝐵 =
𝑑𝑉 𝑑𝑉 𝑣0
CSTR 𝐹𝐴0 − 𝐹𝐴 𝑣0 𝐶𝐴0 − 𝐶𝐴
𝑉= 𝑉=
−𝑟𝐴 −𝑟𝐴
𝐹𝐵0 − 𝐹𝐵 𝑣0 𝐶𝐵0 − 𝐶𝐵
𝑉= 𝑉=
−𝑟𝐵 −𝑟𝐵
Semibatch B added to A 𝑑𝑁𝐴 𝑑𝐶𝐴 𝑣0 𝐶𝐴
= 𝑟𝐴 𝑉 = 𝑟𝐴 −
𝑑𝑡 𝑑𝑡 𝑉
𝑑𝑁𝐵 𝑑𝐶𝐵 𝑣0 𝐶𝐵0 − 𝐶𝐵
= 𝐹𝐵0 + 𝑟𝐵 𝑉 = 𝑟𝐵 −
𝑑𝑡 𝑑𝑡 𝑉
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Algorithm to Multiple Reactions

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Net Rates of Reaction
• If q reactions are taking place
𝑘1𝐴 Net rate of reaction
Reaction 1 A+B 3C + D
𝑘2𝐴
Reaction 2 𝐴 + 2𝐶 3E 𝑞
𝑘3𝐵 𝑟𝑗 = ෍ 𝑟𝑖𝑗
Reaction 3 2B + 3E 4F
𝑖=1
…
𝑘𝑞𝐸
Reaction q E + 2F G

The net rates of formation fo A and B are found by summing up the rates of formation of A and B for every
reaction in which species A and B occur
𝑞 𝑞

𝑟𝐴 = 𝑟1𝐴 + 𝑟2𝐴 + 𝑟3𝐴 + ⋯ + 𝑟𝑞𝐴 = ෍ 𝑟𝑖𝐴 𝑟𝐵 = 𝑟1𝐵 + 𝑟2𝐵 + 𝑟3𝐵 + ⋯ + 𝑟𝑞𝐵 = ෍ 𝑟𝑖𝐵
𝑖=1 𝑖=1

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Rate Laws
• The rate laws for each of the individual reactions are expressed in terms of concentrations,
𝐶𝑗 , of the reacting species.
• A rate law is needed for one species in each reaction.

𝑟𝑖𝑗 = 𝑘𝑖𝑗 𝑓𝑖 𝐶𝐴 , 𝐶𝐵 … 𝐶𝑗 … 𝐶𝑛
• If Reaction (1)
𝒌𝟏𝑨
𝐀+𝐁 𝟑𝐂 + 𝐃
Followed an elementary rate law, then the rate of disapperance of A in Reaction A would be
−𝑟1𝐴 = 𝑘1𝐴 𝐶𝐴 𝐶𝐵
and in Reaction 2
𝒌𝟐𝑨
𝑨 + 𝟐𝑪 𝟑𝑬
−𝑟2𝐴 = 𝑘2𝐴 𝐶𝐴 𝐶𝐶2
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Rate Laws
• The net rate of formation of A for these two reactions is

𝑟𝐴 = 𝑟1𝐴 + 𝑟2𝐴 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 − 𝑘2𝐴 𝐶𝐴 𝐶𝐶2

Net Rate Laws
𝑟1𝐴 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 𝑟𝐴 = 𝑟1𝐴 + 𝑟2𝐴
𝑟2𝐴 = −𝑘2𝐴 𝐶𝐴 𝐶𝐶2 𝑟𝐵 = 𝑟1𝐵 + 𝑟2𝐵
Reactions
Rate of formation of A in reaction 𝑖 𝑟𝐶 = 𝑟1𝐶 + 𝑟2𝐶
𝒌𝟏𝑨
(1) 𝐀 + 𝐁 𝟑𝐂 + 𝐃 𝑟𝐷 = 𝑟1𝐷 + 𝑟2𝐷
𝒌𝟐𝑨
(2) 𝑨 + 𝟐𝑪 𝟑𝑬 𝑟𝐸 = 𝑟1𝐸 + 𝑟2𝐸

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Stoichiometry: Relative Rates of Reaction
• The next step is to relate the rate law for a particular reaction and species to other species
participating in that reaction.

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

Relate the rates of appearance of A and B to the rates of formation of C and D

−𝑟𝐴 −𝑟𝐵 𝑟𝐶 𝑟𝐷
= = =
𝑎 𝑏 𝑐 𝑑

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Stoichiometry: Relative Rates of Reaction
Reactions Rate of formation of A in reaction 𝑖
• In working with multiple reactions,
𝒌𝟏𝑨 𝑟1𝐴 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵
−𝑟𝑖𝐴 −𝑟𝑖𝐵 𝑟𝑖𝐶 𝑟𝑖𝐷 (1) 𝐀 + 𝐁 𝟑𝐂 + 𝐃 𝑟2𝐴 = −𝑘2𝐴 𝐶𝐴 𝐶𝐶2
= = = 𝒌𝟐𝑨
𝑎𝑖 𝑏𝑖 𝑐𝑖 𝑑𝑖 (2) 𝑨 + 𝟐𝑪 𝟑𝑬

From Reaction (1) From Reaction (2)

𝒓𝟐𝑨 𝑟2𝐶 𝑟2𝐸

𝒓𝟏𝑨 𝑟1𝐵 𝑟1𝐶 𝑟1𝐷 = =
= = = −1 −2 3
−1 −1 3 1 −1 1
−1 1 1 𝑟1𝐷 𝒓𝟏𝑨 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 𝒓𝟐𝑨 = 𝑟2𝐶 = − 𝑟2𝐸
𝒓𝟏𝑨 = 𝑟 = − 𝑟1𝐶 = − −2 3
−1 1𝐵 3 1 1 𝑟1𝐵 = 𝒓𝟏𝑨 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵
𝒓𝟐𝑨 = −𝑘2𝐴 𝐶𝐴 𝐶𝐶2
𝑟1𝐶 = 3 −𝒓𝟏𝑨 = 3𝑘1𝐴 𝐶𝐴 𝐶𝐵
𝑟2𝐶 = 2𝒓𝟐𝑨 = −2𝑘2𝐴 𝐶𝐴 𝐶𝐶2
𝑟1𝐷 = −𝒓𝟏𝑨 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 𝑟2𝐸 = −3𝒓𝟐𝑨 = 3𝑘2𝐴 𝐶𝐴 𝐶𝐶2
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Combine Individual Rate Laws to Find the Net Rate
Reactions
𝒌𝟏𝑨 Individual rate laws
(1) 𝐀 + 𝐁 𝟑𝐂 + 𝐃
𝒌𝟐𝑨 𝒓𝟏𝑨 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 Net rate laws
(2) 𝑨 + 𝟐𝑪 𝟑𝑬
𝑟1𝐵 = 𝒓𝟏𝑨 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 𝑟𝐴 = 𝑟1𝐴 + 𝑟2𝐴 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 −𝑘2𝐴 𝐶𝐴 𝐶𝐶2
𝑟1𝐶 = 3 −𝒓𝟏𝑨 = 3𝑘1𝐴 𝐶𝐴 𝐶𝐵 𝑟𝐵 = 𝑟1𝐵 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵
Net Rate Laws
𝑟1𝐷 = −𝒓𝟏𝑨 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵 𝑟𝐶 = 𝑟1𝐶 + 𝑟2𝐶 = 3𝑘1𝐴 𝐶𝐴 𝐶𝐵 − 2𝑘2𝐴 𝐶𝐴 𝐶𝐶2
𝑟𝐴 = 𝑟1𝐴 + 𝑟2𝐴 𝑟𝐷 = 𝑟1𝐷 = −𝑘1𝐴 𝐶𝐴 𝐶𝐵
𝒓𝟐𝑨 = −𝑘2𝐴 𝐶𝐴 𝐶𝐶2 𝑟𝐸 = 𝑟2𝐸 = 3𝑘2𝐴 𝐶𝐴 𝐶𝐶2
𝑟𝐵 = 𝑟1𝐵 + 𝑟2𝐵
𝑟2𝐶 = 2𝒓𝟐𝑨 = −2𝑘2𝐴 𝐶𝐴 𝐶𝐶2
𝑟𝐶 = 𝑟1𝐶 + 𝑟2𝐶 𝑟2𝐸 = −3𝒓𝟐𝑨 = 3𝑘2𝐴 𝐶𝐴 𝐶𝐶2
𝑟𝐷 = 𝑟1𝐷 + 𝑟2𝐷
𝑟𝐸 = 𝑟1𝐸 + 𝑟2𝐸

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Stoichiometry and rate laws for multiple reactions
Considering the following set of reactions:
Rate Laws
Reaction 1: 4𝑁𝐻3 + 6𝑁𝑂 → 5𝑁2 + 6𝐻2 𝑂 1.5 (1)
−𝑟1𝑁𝑂 = 𝑘1𝑁𝑂 𝐶𝑁𝐻3 𝐶𝑁𝑂
Reaction 2: 2𝑁𝑂 → 𝑁2 + 𝑂2 2 (2)
𝑟2𝑁2 = 𝑘2𝑁2 𝐶𝑁𝑂
Reaction 3: 𝑁2 + 2𝑂2 → 2𝑁𝑂2 −𝑟3𝑂2 = 𝑘3𝑂2 𝐶𝑁2 𝐶𝑂22 (3)

Write the rate law for each species in each reaction and then write the net rates of formation of NO, O2,
and N2.

Work with your team on this activity. It must be uploaded individually by the end of this lecture.

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Contact Information
Orlando Castilleja-Escobedo, M.Sc.
• orlandocastilleja@tec.mx

Updated: August 17nd, 2022

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