Stoichiometry

CHEMICAL REACTION ENGINEERING 1

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Chemical Reaction Engineering
Chemical reaction engineering (CRE) is the field that studies
the rates and mechanisms of chemical reactions and the
design of the reactor in which they take place.

 rA  kCA 𝐶𝐴 = 𝑓 𝑋

STOICHIOMETRIC TABLE
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Lecture 4.1
Building Block 1 - Mole Balance
Building Block 2 - Rate Laws
Building Block 3
Stoichiometry

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 Chapter 3

Algorithm
How to find −𝑟𝐴 = 𝑓 𝑋

Step 1: Rate Law −𝑟𝐴 = 𝑔 𝐶𝑖

Step 2: Stoichiometry 𝐶𝑖 = ℎ 𝑋

Step 3: Combine to get −𝑟𝐴 = 𝑓 𝑋

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Stoichiometry
For the general reaction
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
Relative rates of reaction
−𝑟𝐴 −𝑟𝐵 𝑟𝐶 𝑟𝐷
= = =
𝑎 𝑏 𝑐 𝑑
Taking species A as basis for calculation
𝑏 𝑐 𝑑
𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
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 𝑏 𝑐 𝑑
𝐴+ 𝐵 → 𝐶+ 𝐷
Batch Systems 𝑎 𝑎 𝑎
In a batch reactor, a number of moles of species A, B, C, D,
and inerts 𝑰 will be placed at 𝒕 = 𝟎.
Species A will be the basis for calculation, 𝑵𝑨𝟎 moles of A
will initially be present in the reactor. After a time 𝒕, 𝑵𝑨𝟎 𝑿
moles of A will be consumed in the system as a result of the
chemical reaction, leaving 𝑵𝑨𝟎 − 𝑵𝑨𝟎 𝑿 moles of A in the
system. The number of moles of A remaining in the reactor
after a conversion 𝑿 is achieved will be 𝑵𝑨 = 𝑵𝑨𝟎 − 𝑵𝑨𝟎 𝑿.

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 Stoichiometric Table for Batch𝑏 𝑐 𝑑
System 𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
Species Initial (mol) Change (mol) Remaining (mol) Conc
A 𝑵𝑨𝟎 −𝑵𝑨𝟎 𝑿 𝑵𝑨 = 𝑵𝑨𝟎 − 𝑵𝑨𝟎 𝑿
𝒃
B 𝑵𝑩𝟎 − 𝒃/𝒂 𝑵𝑨𝟎 𝑿 𝑵𝑩 = 𝑵𝑩𝟎 − 𝑵𝑨𝟎 𝑿
𝒂
𝒄
C 𝑵𝑪𝟎 𝒄/𝒂 𝑵𝑨𝟎 𝑿 𝑵𝑪 = 𝑵𝑪𝟎 + 𝑵𝑨𝟎 𝑿
𝒂
D 𝑵𝑫𝟎 𝒅/𝒂 𝑵𝑨𝟎 𝑿 𝒅
𝑵𝑫 = 𝑵𝑫𝟎 + 𝑵𝑨𝟎 𝑿
𝒂
I 𝑵𝑰𝟎 - 𝑵𝑰 = 𝑵𝑰𝟎
𝒅 𝒄 𝒃
Total 𝑵𝑻𝟎 𝑵𝑻 = 𝑵𝑻𝟎 + + − − 𝟏 𝑵𝑨𝟎 𝑿
𝒂 𝒂 𝒂
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Looking at the totals for remaining number of moles
𝒅 𝒄 𝒃
𝑵𝑻 = 𝑵𝑻𝟎 + + − − 𝟏 𝑵𝑨𝟎 𝑿
𝒂 𝒂 𝒂
𝒅 𝒄 𝒃
The stoichiometric coefficients in the parentheses, − −𝟏 , +
𝒂 𝒂 𝒂
represent the change in the number of moles per mole of A
reacted.
𝒅 𝒄 𝒃
𝜹= + − −𝟏
𝒂 𝒂 𝒂
𝜹 gives the change in the total number of moles per mole of A
reacted.

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The total number of moles can now be calculated from
𝑵𝑻 = 𝑵𝑻𝟎 + 𝜹𝑵𝑨𝟎 𝑿

The reaction rate, −𝒓𝑨 , usually depends on the concentration

of the reacting species raised to some power.
Since there is a need to determine the reaction rate as a
function of conversion, 𝑿, there is a need to know the
concentrations of the reacting species as a function of
conversion, 𝑿.

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Stoichiometric Table for Batch𝑏 𝑐 𝑑
System 𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
Remaining (mol) Concentration
𝑵𝑨 𝑵𝑨𝟎 − 𝑵𝑨𝟎 𝑿
𝑵𝑨 = 𝑵𝑨𝟎 − 𝑵𝑨𝟎 𝑿 𝑪𝑨 = =
𝑽 𝑽
𝒃
𝒃 𝑵𝑩 𝑵𝑩𝟎 − 𝑵𝑨𝟎 𝑿
𝒂
𝑵𝑩 = 𝑵𝑩𝟎 − 𝑵𝑨𝟎 𝑿 𝑪𝑩 = =
𝒂 𝑽 𝑽
𝒄 𝑵𝑪 𝒄
𝑵𝑪𝟎 + 𝑵𝑨𝟎 𝑿
𝑵𝑪 = 𝑵𝑪𝟎 + 𝑵𝑨𝟎 𝑿 𝑪𝑪 = = 𝒂
𝒂 𝑽 𝑽
𝑵𝑫 𝒅
𝒅 𝑵𝑫𝟎 + 𝑵𝑨𝟎 𝑿
𝑵𝑫 = 𝑵𝑫𝟎 + 𝑵𝑨𝟎 𝑿 𝑪𝑫 = = 𝒂
𝒂 𝑽 𝑽
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 𝑽 = 𝑽𝟎
Stoichiometric Table for Batch 𝝂 = 𝝂𝟎
𝑏 𝑐 𝑑
System 𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
Remaining (mol) Concentration
𝑵𝑨 𝑵𝑨𝟎 − 𝑵𝑨𝟎 𝑿 𝑵𝑨𝟎 𝟏 − 𝑿
𝑵𝑨 = 𝑵𝑨𝟎 − 𝑵𝑨𝟎 𝑿 𝑪𝑨 = = = = 𝑪𝑨𝟎 𝟏 − 𝑿
𝑽 𝑽 𝑽
𝒃 𝒃
𝒃 𝑵𝑩 𝑵𝑩𝟎 − 𝒂 𝑵𝑨𝟎 𝑿
𝑵𝑩 = 𝑵𝑩𝟎 − 𝑵𝑨𝟎 𝑿 𝑪𝑩 = = = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝑿
𝒂 𝑽 𝑽 𝒂
𝒄 𝑵𝑪 𝑵𝑪𝟎 + 𝑵𝑨𝟎 𝑿𝒄 𝒄
𝑵𝑪 = 𝑵𝑪𝟎 + 𝑵𝑨𝟎 𝑿 𝑪𝑪 = = 𝒂 = 𝑪𝑪𝟎 + 𝑪𝑨𝟎 𝑿
𝒂 𝑽 𝑽 𝒂
𝑵 𝒅 𝒅
𝒅 𝑫 𝑵𝑫𝟎 + 𝑵𝑨𝟎 𝑿
𝑵𝑫 = 𝑵𝑫𝟎 + 𝑵𝑨𝟎 𝑿 𝑪𝑫 = = 𝒂 = 𝑪 + 𝑪 𝑿
𝒂 𝑫𝟎 𝑨𝟎
𝑽 𝑽 𝒂
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In a batch system, for the reaction
𝑏 𝑐 𝑑
𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
the rate law can be written as
−𝒓𝑨 = 𝒌𝑨 𝑪𝑨 𝑪𝑩
to obtain −𝒓𝑨 = 𝒇 𝑿
𝑏
−𝒓𝑨 = 𝒌𝑨 𝑪𝑨 𝑪𝑩 = 𝑘𝐴 𝐶𝐴0 1 − 𝑋 𝐶𝐵0 − 𝐶𝐴0 𝑋
𝑎
𝑏
−𝑟𝐴 = 𝑘𝐴 𝐶𝐴0 1 − 𝑋 𝐶𝐵0 − 𝐶𝐴0 𝑋
𝑎

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 SUMMARY: Stoichiometric Table
𝑏 𝑐
for 𝑑
Batch System 𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
Species Initial (mol) Change (mol) Remaining (mol) Concentration

A 𝑵𝑨𝟎 −𝑵𝑨𝟎 𝑿 𝑵𝑨 = 𝑵𝑨𝟎 − 𝑵𝑨𝟎 𝑿 𝑪𝑨 = 𝑪𝑨𝟎 𝟏−𝑿

𝒃
B 𝑵𝑩𝟎 − 𝒃/𝒂 𝑵𝑨𝟎 𝑿 𝑵𝑩 = 𝑵𝑩𝟎 − 𝑵𝑨𝟎 𝑿 𝑪𝑩 = 𝑪𝑩𝟎 − 𝒃/𝒂 𝑪𝑨𝟎 𝑿
𝒂
𝒄
𝒄/𝒂 𝑵𝑨𝟎 𝑿 𝑵 = 𝑵 + 𝑵 𝑿 𝑪𝑪 = 𝑪𝑪𝟎 +
C 𝑵𝑪𝟎 𝑪 𝑪𝟎
𝒄/𝒂 𝑪𝑨𝟎 𝑿
𝒂 𝑨𝟎
D 𝑵𝑫𝟎 𝒅/𝒂 𝑵𝑨𝟎 𝑿 𝑵 = 𝑵 + 𝒅 𝑵 𝑿 𝑪𝑫 = 𝑪𝑫𝟎 + 𝒅/𝒂 𝑪𝑨𝟎 𝑿
𝑫 𝑫𝟎
𝒂 𝑨𝟎
I 𝑵𝑰𝟎 - 𝑵𝑰 = 𝑵𝑰𝟎
Total 𝑵𝑻𝟎 𝑵𝑻 = 𝑵𝑻𝟎 + 𝜹𝑵𝑨𝟎 𝑿

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Stoichiometric Table for Flow
Systems
The form of the stoichiometric table for a continuous-flow
system is essentially the same as that for a batch system,
except that molar flow rate terms are used.
Beginning with
𝑏 𝑐 𝑑
𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎

the stoichiometric table is established

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 Stoichiometric Table for Flow
𝑏 𝑐 𝑑
Systems 𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
Species Feed rate to Change within Effluent rate from reactor, mol/time Conc
reactor, mol/time reactor, mol/time
A 𝑭𝑨𝟎 −𝑭𝑨𝟎 𝑿 𝑭𝑨 = 𝑭𝑨𝟎 − 𝑭𝑨𝟎 𝑿
𝒃
B 𝑭𝑩𝟎 − 𝒃/𝒂 𝑭𝑨𝟎 𝑿 𝑭𝑩 = 𝑭𝑩𝟎 − 𝑭𝑨𝟎 𝑿
𝒂
𝒄
C 𝑭𝑪𝟎 𝒄/𝒂 𝑭𝑨𝟎 𝑿 𝑭𝑪 = 𝑭𝑪𝟎 + 𝑭𝑨𝟎 𝑿
𝒂
D 𝒅
𝑭𝑫𝟎 𝒅/𝒂 𝑭𝑨𝟎 𝑿 𝑭𝑫 = 𝑭𝑫𝟎 + 𝑭𝑨𝟎 𝑿
𝒂
I 𝑭𝑰𝟎 - 𝑭𝑰 = 𝑭𝑰𝟎
𝒅 𝒄 𝒃
Total 𝑭𝑻𝟎 𝑭𝑻 = 𝑭𝑻𝟎 + + − − 𝟏 𝑭𝑨𝟎 𝑿
𝒂 𝒂 𝒂
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Looking at the totals for remaining molar flow rate
𝒅 𝒄 𝒃
𝑭𝑻 = 𝑭𝑻𝟎 + + − − 𝟏 𝑭𝑨𝟎 𝑿
𝒂 𝒂 𝒂
Where 𝒅 𝒄 𝒃
𝜹= + − −𝟏
𝒂 𝒂 𝒂

𝑭𝑻 = 𝑭𝑻𝟎 + 𝜹𝑭𝑨𝟎 𝑿

For concentration in terms of molar flow rate,

𝑭𝑨
𝑪𝑨 =
𝝂
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 Stoichiometric Table for Flow 𝑏 𝑐 𝑑
System 𝐴+ 𝐵→ 𝐶+ 𝐷
𝑎 𝑎 𝑎
Effluent rate from reactor, mol/time Concentration
𝑭𝑨 𝑭𝑨𝟎 − 𝑭𝑨𝟎 𝑿
𝑭𝑨 = 𝑭𝑨𝟎 − 𝑭𝑨𝟎 𝑿 𝑪𝑨 = =
𝝂 𝝂
𝒃
𝒃 𝑭𝑩 𝑭𝑩𝟎 − 𝑭𝑨𝟎 𝑿
𝒂
𝑭𝑩 = 𝑭𝑩𝟎 − 𝑭𝑨𝟎 𝑿 𝑪𝑩 = =
𝒂 𝝂 𝝂
𝑭𝑪 𝒄
𝒄 𝑭𝑪𝟎 + 𝑭𝑨𝟎 𝑿
𝑭𝑪 = 𝑭𝑪𝟎 + 𝑭𝑨𝟎 𝑿 𝑪𝑪 = = 𝒂
𝒂 𝝂 𝝂
𝒅 𝑭𝑫 𝒅
𝑭𝑫𝟎 + 𝑭𝑨𝟎 𝑿
𝑭𝑫 = 𝑭𝑫𝟎 + 𝑭𝑨𝟎 𝑿 𝑪𝑫 = = 𝒂
𝒂 𝝂 𝝂
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Concentration in Flow Systems
𝑭𝑨
𝑪𝑨 =
𝝂
For cases when volume and volumetric flow rate are
constant
𝑽 = 𝑽𝟎
𝝂 = 𝝂𝟎

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 𝑽 = 𝑽𝟎
Stoichiometric Table for Flow 𝑏 𝑐 𝑑 𝝂 = 𝝂𝟎
System 𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
Effluent rate from reactor,
mol/time
Concentration
𝑭𝑨 𝑭𝑨𝟎 − 𝑭𝑨𝟎 𝑿 𝑭𝑨𝟎 𝟏 − 𝑿
𝑭𝑨 = 𝑭𝑨𝟎 − 𝑭𝑨𝟎 𝑿 𝑪𝑨 = = = = 𝑪𝑨𝟎 𝟏 − 𝑿
𝝂 𝝂 𝝂
𝒃 𝒃
𝒃 𝑭𝑩 𝑭𝑩𝟎 − 𝒂 𝑭𝑨𝟎 𝑿
𝑭𝑩 = 𝑭𝑩𝟎 − 𝑭𝑨𝟎 𝑿 𝑪𝑩 = = = 𝑪𝑩𝟎 − 𝑪𝑨𝟎 𝑿
𝒂 𝝂 𝝂𝒄 𝒂
𝒄 𝑭𝑪 𝑭𝑪𝟎 + 𝒂 𝑭𝑨𝟎 𝑿 𝒄
𝑭𝑪 = 𝑭𝑪𝟎 + 𝑭𝑨𝟎 𝑿 𝑪𝑪 = = = 𝑪𝑪𝟎 + 𝑪𝑨𝟎 𝑿
𝒂 𝝂 𝝂 𝒂
𝒅 𝑭𝑫 𝑭𝑫𝟎 + 𝒅 𝑭𝑨𝟎 𝑿 𝒅
𝑭𝑫 = 𝑭𝑫𝟎 + 𝑭𝑨𝟎 𝑿 𝑪𝑫 = = 𝒂 = 𝑪𝑫𝟎 + 𝑪𝑨𝟎 𝑿
𝒂 𝝂 𝝂 𝒂
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Concentration in Flow Systems
𝑭𝑨
𝑪𝑨 =
𝝂
For cases when volume and volumetric flow rate are not
constant (gas-phase reactions)
𝑽 ≠ 𝑽𝟎
𝝂 ≠ 𝝂𝟎
𝑽 = 𝑽𝟎 𝟏 + 𝜺𝑿
𝝂 = 𝝂𝟎 𝟏 + 𝜺𝑿
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Fractional change in volume
What is 𝜺?
change in total number of moles for complete conversion
𝜺=
total moles fed
𝜺 = 𝒚𝑨 𝜹 Holds for both gas-phase
flow and batch system
𝒚𝑨 – mole fraction of A in the feed
𝑽 = 𝑽𝟎 𝟏 + 𝜺𝑿
𝝂 = 𝝂𝟎 𝟏 + 𝜺𝑿
𝜺 and 𝜹 – may be negative, zero, or positive values

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Stoichiometric 𝑏Table𝑐 for𝑑 Flow
𝑽 = 𝑽𝟎 𝟏 + 𝜺𝑿
System 𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎 𝝂 = 𝝂𝟎 𝟏 + 𝜺𝑿
Concentration
𝑭𝑨 𝑭𝑨𝟎 − 𝑭𝑨𝟎 𝑿 𝑭𝑨𝟎 𝟏 − 𝑿 𝟏−𝑿
𝑪𝑨 = = = = 𝑪𝑨𝟎
𝝂 𝝂 𝝂𝟎 𝟏 + 𝜺𝑿 𝟏 + 𝜺𝑿
𝒃
𝑭𝑩 𝑭𝑩𝟎 − 𝒂 𝑭𝑨𝟎 𝑿 𝑪𝑩𝟎 − 𝒃/𝒂 𝑪𝑨𝟎 𝑿
𝑪𝑩 = = =
𝝂 𝒄𝝂 𝟏 + 𝜺𝑿
𝑭𝑪 𝑭𝑪𝟎 + 𝒂 𝑭𝑨𝟎 𝑿 𝑪𝑪𝟎 + 𝒄/𝒂 𝑪𝑨𝟎 𝑿
𝑪𝑪 = = =
𝝂 𝝂 𝟏 + 𝜺𝑿
𝑭𝑫 𝑭𝑫𝟎 + 𝒅 𝑭𝑨𝟎 𝑿 𝑪𝑫𝟎 + 𝒅/𝒂 𝑪𝑨𝟎 𝑿
𝑪𝑫 = = 𝒂 =
𝝂 𝝂 𝟏 + 𝜺𝑿
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 SUMMARY: Stoichiometric Table
𝑏
for
𝑐 𝑑
Flow System (𝝂 = 𝝂𝟎 ) 𝐴 + 𝑎 𝐵 → 𝑎 𝐶 + 𝑎 𝐷
Feed rate to Change within reactor, Effluent rate from reactor, mol/time
Species reactor, mol/time mol/time
Concentration

A 𝑭𝑨𝟎 −𝑭𝑨𝟎 𝑿 𝑭𝑨 = 𝑭𝑨𝟎 − 𝑭𝑨𝟎 𝑿 𝑪𝑨 = 𝑪𝑨𝟎 𝟏−𝑿

𝒃
B 𝑭𝑩𝟎 − 𝒃/𝒂 𝑭𝑨𝟎 𝑿 𝑭𝑩 = 𝑭𝑩𝟎 − 𝑭𝑨𝟎 𝑿 𝑪𝑩 = 𝑪𝑩𝟎 − 𝒃/𝒂 𝑪𝑨𝟎 𝑿
𝒂
𝒄
𝒄/𝒂 𝑭𝑨𝟎 𝑿 𝑭 = 𝑭 + 𝑭 𝑿 𝑪𝑪 = 𝑪𝑪𝟎 +
C 𝑭𝑪𝟎 𝑪 𝑪𝟎
𝒄/𝒂 𝑪𝑨𝟎 𝑿
𝒂 𝑨𝟎
D 𝑭𝑫𝟎 𝒅/𝒂 𝑭𝑨𝟎 𝑿 𝑭 = 𝑭 + 𝒅 𝑭 𝑿 𝑪𝑫 = 𝑪𝑫𝟎 + 𝒅/𝒂 𝑪𝑨𝟎 𝑿
𝑫 𝑫𝟎
𝒂 𝑨𝟎
I 𝑭𝑰𝟎 - 𝑭𝑰 = 𝑭𝑰𝟎
Total 𝑭𝑻𝟎 𝑭𝑻 = 𝑭𝑻𝟎 + 𝜹𝑭𝑨𝟎 𝑿

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 SUMMARY: Stoichiometric Table 𝑏
for𝑐 𝑑
Flow System 𝝂 = 𝝂𝟎 𝟏 + 𝜺𝑿 𝐴 + 𝑎 𝐵 → 𝑎 𝐶 + 𝑎 𝐷
Feed rate to Change within reactor, Effluent rate from reactor, mol/time
Species reactor, mol/time mol/time
Concentration
𝑭𝑨 = 𝑭𝑨𝟎 − 𝑭𝑨𝟎 𝑿 𝟏−𝑿
A 𝑭𝑨𝟎 −𝑭𝑨𝟎 𝑿 𝑪𝑨 = 𝑪𝑨𝟎
𝒃 𝟏 + 𝜺𝑿
B 𝑭𝑩𝟎 − 𝒃/𝒂 𝑭𝑨𝟎 𝑿 𝑭𝑩 = 𝑭𝑩𝟎 − 𝑭𝑨𝟎 𝑿 𝑪𝑩𝟎 − 𝒃/𝒂 𝑪𝑨𝟎 𝑿
𝒂 𝑪𝑩 =
𝒄/𝒂 𝑭𝑨𝟎 𝑿 𝑭 = 𝑭 + 𝑭 𝑿
𝒄 𝟏 + 𝜺𝑿
C 𝑭𝑪𝟎 𝑪 𝑪𝟎
𝒂 𝑨𝟎
𝑪𝑪𝟎 + 𝒄/𝒂 𝑪𝑨𝟎 𝑿
D 𝑭𝑫𝟎 𝒅/𝒂 𝑭𝑨𝟎 𝑿 𝑭 = 𝑭 + 𝒅 𝑭 𝑿 𝑪𝑪 =
𝑫 𝑫𝟎
𝒂 𝑨𝟎 𝟏 + 𝜺𝑿
I 𝑭𝑰𝟎 - 𝑭𝑰 = 𝑭𝑰𝟎 𝑪𝑫𝟎 + 𝒅/𝒂 𝑪𝑨𝟎 𝑿
𝑪𝑫 =
Total 𝑭𝑻𝟎 𝑭𝑻 = 𝑭𝑻𝟎 + 𝜹𝑭𝑨𝟎 𝑿 𝟏 + 𝜺𝑿

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KEEPING UP
The tower of CRE, is it stable?

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 Algorithm

Full CRE Algorithm

Stoichiometry

Rate Laws

Mole Balance
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 Algorithm

CRE building blocks

Mole Balance Rate Laws

Be careful not to cut corners on any of the

CRE building blocks while learning this material!

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 Algorithm

CRE building blocks

Heat Effects
Isothermal Design

Stoichiometry
Rate Laws

Mole Balance
Otherwise, your algorithm becomes unstable.
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End of Lecture 4.1

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