ANTIOQUIA UNIVERSITY

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Homework 1
The Stoichiometry of Reactions
Francisco Danilo Londono Garcia *, Daniel Moreno Cañaveral *, Lic Amiris Perea
Cuesta*
*Student, Antioquia University, Engineering Faculty, Chemical Engineering Department,
Medellin, Antioquia, Colombia.

Exercise 2.5 Independent reactions for methane oxidation

Consider a mixture of CO, H2 and CH4 that is fed into a furnace with O2 and produces CO,
CO, and HO. The following chemical reactions have been suggested to account or the
products that form.
1
CO + O2 ↔ CO2 (1.1)
2
1
H2 + O2 ↔ H2O (1.2)
2

CH4 + 2O2 ↔ CO2 + 2 H2O (1.3)

3
CH4 + O2 ↔ CO + 2 H2O (1.4)
2

(a) Are these reactions linearly independent? How many reactions comprise a linearly
independent set?
Not, the reactions are not linearly independent, because as you can see in the next
procedure, the reaction 1.3 minus the reaction 1.4 is equal to reaction 1.1.

CH4 + 2O2 ↔ CO2 + 2 H2O

3 3 1
-(CH4 + O2 ↔ CO + 2 H2O) (where, 2O2 - O2 = O2 )
2 2 2
1
CO + O2 ↔ CO2
2

To know how many reactions comprise a linearly independent set, we calculate the
rank of the stoichiometric matrix.

So, first we take the next order in the species:

A1=CO, A2=H2, A3=CH4, A4=O2, A5=CO2, A6= HO2
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Assigning the A vector as:

A = [CO, H2, CH4 , O2, CO2, HO2]
Then, the stoichiometric matrix is:

A1
−𝟏 𝟎 𝟎 −𝟎. 𝟓 𝟏 𝟎 A2
V= [ 𝟎 −𝟏 𝟎 −𝟎. 𝟓 𝟎 𝟏] A3
𝟎 𝟎 −𝟏 −𝟐 𝟏 𝟐 A4
𝟏 𝟎 −𝟏 −𝟏. 𝟓 𝟎 𝟐 A5
[A6 ]
Finding the rank of the matrix, using PYTHON (see attachment 2.5py)
we have:

Then the rank is 3, as the rank of a matrix is a way to define the number of linearly
independent reactions in a network, in consequence in this set of reactions, the number
of reactions that comprise a linearly independent reactions set is 3, this could be seen
in the procedure done at the beginning.

(b) List all sets of linearly independent reactions. Which reaction is included in all of the
linearly independent sets of reactions? Why?

To list all the sets of linearly independent reactions we follow the next procedure:
- First, we write the reactions of formation of the species from the elements, trying to use
species that are in the species list, following the order in which the species appear in the
list.
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In this case we use H2 and O2 because O and H don’t are in the original species list.

C + O2 ↔ CO2
2C + O2 ↔2 CO
2H2 + O2 ↔ 2H2O
C +2H2 ↔ CH4

- With this new set of reactions, we form a new vector of species extended with the species
that do not appear in the original list and with this we organize a stoichiometric matrix.

Assigning the A’ vector as:

A’ = [CO, H2, CH4 , O2, CO2, HO2, C]T
Then, the stoichiometric matrix is summarized as: VA = 0

−𝟏 𝟏 𝟎 𝟎 𝟎 𝟎 −𝟏 (1.5)
V= [ −𝟏 𝟎 𝟐 𝟎 𝟎 𝟎 −𝟐] (1.6)
−𝟏 𝟎 𝟎 𝟐 −𝟐 𝟎 𝟎 (1.7)
𝟎 𝟎 𝟎 𝟎 −𝟐 𝟏 −𝟏 (1.8)
- If we add a species that is not in the original list, this must be eliminated later making it
zero by procedures between the reactions.

As you can see, in this case we add C so we wish to eliminate C by combinations between
the four reactions.
For example, if we:
 Replace the reaction 1.5 by the subtraction between reaction 1.5 and reaction 1.8 (row 1-
row 4)
 Then replace reaction 1.6 by the subtraction between reaction 1.6 and 2* reaction 1.8 (row
2- row 4*2)
 Write the row 1.7 as the same because already is zero (write row 1.7 as the same)
 And finally eliminate the row 1.8 because there are no more rows below to eliminate C
(eliminate row 4)

After this procedure, we have the next matrix:

−𝟏 𝟏 𝟎 𝟎 𝟐 −𝟏 0
v’ = [ −𝟏 𝟎 𝟐 𝟎 𝟒 −𝟏] [0]
−𝟏 𝟎 𝟎 𝟐 −𝟐 𝟎 0

Therefore, the maximal linearly independent set for the original species contains three
reactions, which are written below.
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CH4 + O2 ↔ CO2 + 2H2

2CH4 + O2 ↔2CO + 4H2
2H2 + O2 ↔ 2H2O

To determine the reactions that is found in all sets of linearly independent reactions, we
analyze different sets of three reactions from the original reactions of the system, this to
determine if there is any linear combination between them.

By analyzing the set of reactions 1.1, 1.2 and 1.3, it is found that all three reactions are
linearly independent, because there is no way to produce CH4 only by linear combination of
reactions 1.1 and 1.2, CO only by combination of reactions 1.2 and 1.3 and H2 only by
combining reactions 1.1 and 1.3.

If we take the set of reactions 1.2, 1.3 and 1.4, we see that the three reactions are linearly
independent, because there is no way to produce CO only by linear combination of reactions
1.2 and 1.3, H2 only by combination of reactions 1.3 and 1.4, and CO2 by combining only
reactions 1.2 and 1.4.

If we take the set of reactions 1.1, 1.2 and 1.4, we see that the three reactions are linearly
independent, because there is no way to produce CH4 only by linear combination of reactions
1.1 and 1.2, CO2 only by combination of reactions 1.2 and 1.4 and H2 by combining only
reactions 1.1 and 1.4.

If we take the set of reactions 1.1, 1.3 and 1.4, we see that the three reactions are not linearly
independent, because reaction 1.1 is the subtraction between the reaction 1.3 and 1.4.

Analyzing this set of linearly independent reactions, the reaction that is included in all of the
linearly independent sets reactions is the reaction 1.2 (2H2 + O2 ↔ 2H2O). This could be
because this reaction is the formation reaction of the water, which is part of the two of the
reactions that are part of the non-independent set of reactions.
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Exercise 2.7: Production rates from reaction rates

(a) Consider the following set of chemical reactions,

2N2O5 ↔2N2O4 + O2 (2.1)

N2O5 ↔NO2 + NO3 (2.2)
NO2 + NO3 ↔ N2O5 (2.3)
NO2 + NO3 ↔NO2 + O2 + NO (2.4)
NO + N2O5 ↔3NO2 (2.5)
NO2 + NO2 ↔N2O4 (2.6)

Determine the rates of production of each component in terms of the rates of each reaction.
Using the symbol Aj to represent jth species taking part in the reaction, and ordering the
species as:
A1=N2O5, A2=N2O4, A3=O2, A4=NO2, A5=NO3, A6=NO
Assigning the A vector as:
A = [N2O5, N2O4, O2, NO2 , NO3, NO]
Using the Aj notation
A1 ↔ A2 + A3
A1 ↔ A4 + A5
A4 + A5 ↔A1
A4 + A5 ↔ A4 + A3 + A6 A5 ↔ A3 + A6
A1 + A6 ↔ 3A4
A1 + A1 ↔A2 2A1 ↔A2

Moving all of the variables to the right-hand side of the chemical reaction symbol and
replacing it with an equality sign we have:
- A1 + A2 + A3 = 0
- A1 + A4 + A5 = 0
A1 - A4 - A5 = 0
- A4 - A5 + A3 + A6 = 0
- A1 - A6+ 3A4 = 0
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- 2A1 + A2 = 0

Using the rule from [1], for the stoichiometric matrix ν and the column vector A,

νA =0
−𝟏 𝟏 𝟏 𝟎 𝟎 𝟎 A1
−𝟏 𝟎 𝟎 𝟏 𝟏 𝟎 A2
νA = 𝟏 𝟎 𝟎 −𝟏 −𝟏 𝟎 A3
𝟎 𝟎 𝟏 𝟎 −𝟏 𝟏 A4
−𝟏 𝟎 𝟎 𝟑 𝟎 −𝟏 A5
[ −𝟐 𝟏 𝟎 𝟎 𝟎 𝟎 ] [A6 ]
From [1] the production rate in terms of reaction rate could be express as:

R = νT r R: production rate; v: transpose of stoichiometric matrix; r: reaction

rate
The matrix of the rates of production of each component in terms of the rates of each reaction
are:
R N2O5 −𝟏 𝟏 𝟏 𝟎 𝟎 𝟎 r1
R N2O4 −𝟏 𝟎 𝟎 𝟏 𝟏 𝟎 r2
R O2 𝟏 𝟎 𝟎 −𝟏 −𝟏 𝟎 r3
=
R NO2 𝟎 𝟎 𝟏 𝟎 −𝟏 𝟏 r4
R NO3 −𝟏 𝟎 𝟎 𝟑 𝟎 −𝟏 r5
R NO [ −𝟐 𝟏 𝟎 𝟎 𝟎 𝟎 ] [r6 ]
Solving the problem in PYTHON following the steps in the next image (see attachment
[Link]):
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Then the rates of production of each component in terms of the rates of each reaction
are:
R N2O5 −17 r1
R N2O4 7 r2
R O2 5 r3
=
R NO2 14 r4
R NO3 −5 r5
R NO [ −1 ] [r6 ]

(b) Butene isomerization reactions are shown below.

𝑘1
←
1 - butene cis - 2 - butene (3.1)
→
𝑘−1
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𝑘2
←
1 - butene trans - 2 - butene (3.2)
→
𝑘−2
𝑘3
←
1 - butene isobutene (3.3)
→
𝑘−3

𝑘4
←
cis - 2 - butene trans - 2 – butane (3.4)
→
𝑘−4
𝑘5
←
cis - 2 - butene isobutene (3.5)
→
𝑘−5

Determine the rates of production of each component in terms of the rates of each reaction.

Renaming the species as:

A= 1 – butane, B= cis - 2 – butane, C= trans - 2 – butane, D= isobutene
We have:
𝑘1
←
A B (3.1)’
→
𝑘−1
𝑘2
←
A C (3.2)’
→
𝑘−2
𝑘3
←
A D (3.3)’
→
𝑘−3

𝑘4
←
B C (3.4)’
→
𝑘−4
𝑘5
←
B D (3.5)’
→
𝑘−5

The production rate of jth species (Rj) is directly related with de reaction rate (rj) as:
Rj = - rj = -KCj
Using this for each species of reaction system (3-1 -3.5) then, the reactions rates are:
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r1=K1CA –K-1CB (3.6)

r2= K2CA –K-2Cc (3.7)
r3= K3CA –K-3CD (3.8)
r4= K4CB –K-4CC (3.9)
r5= K5CB –K-5CD (3.10)
And the production rate for the species, in terms of the reaction rate are:
RA= -r1 –r2 -r3 (3.11)
RB= r1 –r4 -r5 (3.12)
RC= r2 +r4 (3.13)
RD= r3 +r5 (3.14)

Replacing equations 3.11-3.14 in 3.6-3.10,

RA= -( K1CA –K-1CB) –(K2CA –K-2Cc) -( K3CA –K-3CD)
RB= K1CA –K-1CB –(K4CB –K-4CC) –( K5CB –K-5CD)
RC= K2CA –K-2Cc + K4CB –K-4CC
RD= K3CA –K-3CD + K5CB –K-5CD
Operating,
RA= -K1CA +K-1CB – K2CA +K-2Cc -K3CA +K-3CD (3.15)
RB= K1CA –K-1CB –K4CB +K-4CC –K5CB +K-5CD (3.16)
RC= K2CA –K-2Cc + K4CB –K-4CC (3.17)

Replacing the original species:

• R1 - butene = –K1C1 - butene +K-1C cis - 2 – butane – K2C1 - butene +K-2Cc –K3C1 - butene +K-3C
isobutene
• R cis - 2 – butane = K1C1 - butene –K-1C cis - 2 – butane –K4C cis - 2 – butane +K-4CC –K5C cis - 2 – butane
+K-5C isobutene
• R trans - 2 – butane = K2C1 - butene –K-2C trans - 2 – butane + K4C cis - 2 – butane –K-4C trans - 2 – butane
• R isobutene = K3C1 - butene –K-3C isobutene + K5C cis - 2 – butane –K-5C isobutene
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Exercise 3.3: More than one reaction

Consider the following two gas-phase reactions:
𝐴+𝐵 ⇌𝐶 (𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 1)
2𝐶 ⇌ 𝐷 (𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 2)
(a) What are the two equilibrium equations relating the two unknown extents of reaction
and the initial gas-phase compositions? You can assume the pressure is low enough
that the gases are ideal.

By the definition of the equilibrium constant derived form the assumption that at equilibrium
state, the Gibbs energy is at the minimum with respect to the temperature, pressure and
number of moles:
𝜕𝐺
( ) = ∑ 𝜈𝑗 𝜇𝑗 = 0 (𝐸𝑞𝑛. 3.1)
𝜕𝑛
𝑗

𝜈
⟹ K = e−ΔG°⁄𝑅𝑇 = ∏ 𝑎𝑗 𝑗 (𝐸𝑞𝑛 3.2)
𝑗

Where:
𝜈𝑗 : Stoichiometric coefficient of each species
𝜇𝑗 : Chemical potential of the species.
𝑎𝑗 : Activity coefficient of the species.

Considering that the ideal gas phase is valid in this case, the fugacity of each species is equal
to its partial pressure. Therefore, it is possible to express the activity coefficient as follows:
𝑃𝑖
𝑓𝑖 = 𝑃𝑖 ⟹ 𝑎𝑖 = (𝐸𝑞𝑛. 3.3)
1𝑎𝑡𝑚
If the constant is expressed in atm, equation 3.3 allows the simplification of the expression
for the equilibrium:
𝜈 𝜈𝑗
𝐾 = ∏ 𝑎𝑗 𝑗 = ∏ 𝑃𝑗 (𝐸𝑞𝑛 3.4)
𝑗 𝑗

For the chemical reactions presented in this exercise, the equilibrium constants are expressed
as:
𝑃𝐶 𝑦𝐶 𝑃𝐷 𝑦𝐷
𝐾1 = = (𝐸𝑞𝑛 3.5) 𝐾1 = 2 = 2 (𝐸𝑞𝑛 3.6)
𝑃𝐴 𝑃𝐵 𝑦𝐴 𝑦𝐵 𝑃 𝑃𝐶 𝑦𝐶 𝑃
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Now, to find the mole fractions as a function of the reaction extents, the mole balance of each
species is presented:

𝑛𝐴 = 𝑛𝐴0 − 𝜉1 (𝐸𝑞𝑛 3.7)

𝑛𝐵 = 𝑛𝐵0 − 𝜉1 (𝐸𝑞𝑛 3.8)
𝑛𝐶 = 𝑛𝐶0 + 𝜉1 − 2𝜉2 (𝐸𝑞𝑛 3.9)
𝑛𝐷 = 𝑛𝐷0 + 𝜉2 (𝐸𝑞𝑛 3.10)
𝑛𝑇 = 𝑛 𝑇0 − 𝜉1 − 𝜉2 (𝐸𝑞𝑛 3.11)

Considering the mole fractions as 𝑦𝑗 = 𝑛𝑗 /𝑛𝑇 :

𝑛𝐴0 − 𝜉1 𝑦𝐴0 − 𝜉1′

𝑦𝐴 = = (𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 3.12)
𝑛 𝑇0 − 𝜉1 − 𝜉2 1 − 𝜉1′ − 𝜉2′
𝑛𝐵0 − 𝜉1 𝑦𝐵0 − 𝜉1′
𝑦𝐵 = = (𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 3.13)
𝑛 𝑇0 − 𝜉1 − 𝜉2 1 − 𝜉1′ − 𝜉2′
𝑛𝐶0 + 𝜉1 − 2𝜉2 𝑦𝐶0 + 𝜉1′ − 2𝜉2′
𝑦𝐶 = = (𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 3.14)
𝑛 𝑇0 − 𝜉1 − 𝜉2 1 − 𝜉1′ − 𝜉2′
𝑛𝐷0 + 𝜉2 𝑦𝐷0 2𝜉2′
𝑦𝐷 = = (𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 3.15)
𝑛𝑇0 − 𝜉1 − 𝜉2 1 − 𝜉1′ − 𝜉2′
Where:
𝜉1 𝜉2
𝜉1′ = (𝐸𝑞𝑛 3.16) 𝜉2′ = (𝐸𝑞𝑛 3.17)
𝑛𝑇0 𝑛 𝑇0

Finally, the two equations that set the reaction extents at the equilibrium state are:
• Reaction 1:

𝑦𝐶 (𝑦𝐶0 + 𝜉1′ − 2𝜉2′ )(1 − 𝜉1′ − 𝜉2′ )

𝐾1 = = (𝐸𝑞𝑢𝑖𝑎𝑡𝑖𝑜𝑛 3.5.2)
𝑦𝐴 𝑦𝐵 𝑃 (𝑦𝐴0 − 𝜉1′ )(𝑦𝐵0 − 𝜉1′ ) ∙ 𝑃

• Reaction 2:

𝑦𝐷 (𝑦𝐷0 + 𝜉2′ )(1 − 𝜉1′ − 𝜉2′ )

𝐾2 = = 2
(𝐸𝑞𝑢𝑖𝑎𝑡𝑖𝑜𝑛 3.6.2)
𝑦𝐶2 𝑃 (𝑦𝐶 + 𝜉 ′ − 2𝜉 ′ ) 𝑃
0 1 2
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(b) What is the equilibrium gas-phase composition at 2.0 atm total pressure given initial
gas-phase composition 𝒚𝑨 = 𝒚𝑩 = 𝟎. 𝟓 , 𝒚𝑪 = 𝒚𝑫 = 𝟎, and 𝑲𝟏 = 𝟏, 𝑲𝟐 = 𝟐. 𝟓? Solve
the two nonlinear equations numerically. If a computer is not available, you can use
trial and error (partial answer: y = 0.31).

To find the compositions at equilibrium, it is necessary to solve the nonlinear equations

system of 3.5.2 and 3.6.2. Using a computational tool (Python) the reaction extents calculated
are:
𝜉1′ = 0.312 𝜉2′ = 0.096

Figure 1 Script for solving exercise 3.3.b

The compositions at equilibrium are calculated using equations 3.12 to 3.16 and are reported
in the following table.
Table 1 Mole fractions distribution at equilibrium

𝒚𝑨𝒔 𝒚𝑩𝒔 𝒚𝑪 𝒔 𝒚𝑫𝑺

0.318 0.318 0.202 0.163
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(c) What is the equilibrium gas-phase composition at 2.0 atm total pressure given initial
gas-phase composition yA = yc = 0.5, yg = yD = 0 (partial answer: yA = 0.62)?

Using the same conditions as before, equations 3.5.2 and 3.6.2 are solved with the same
numeric solution but in this case, the initial conditions are changed to: 𝑦0 = [0.5, 0, 0.5, 0]
where the compositions of the vector correspond respectively to A, B, C and D.
The solution in this case is

𝜉1′ = −0.132 𝜉2′ = 0.1026

The reason why the first advance of the reaction is negative is because that reaction in moved
towards the reagents, this is duw to the absence of the reagent B and the presence of C in the
system.

Figure 2. Script for solving the nonlinear equation system in 3..3.c

The corresponding mole compositions are:

Table 2 Mole compositions at equilibrium

𝒚𝑨𝒔 𝒚𝑩𝒔 𝒚𝑪 𝒔 𝒚𝑫𝑺

0.614 0.128 0.158 0.010
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Exercise 3.7: Creating a second phase with reaction

Consider the gas-phase reaction:
𝐴+𝐵 ⇌𝐶
Product C has a fairly low vapor pressure, so we are concerned about the formation of a liquid
phase in the reactor. The Clausius-Clapeyron equation well represents the vapor pressure of
component C as a function of temperature:
∆𝐻𝑣𝑎𝑝
ln 𝑃𝐶° = 𝑐 −
𝑅𝑇
The reactor is initially filled with an equimolar mixture of A and B. The equilibrium constant
at T = 298 K. is K = 8, the reaction is exothermic with ΔH° = -10 kcal/mol, and the system
pressure is P = 1.0 atm. Components A and B are not very soluble in liquid C. 3The heat of
vaporization of component C is ΔHvap = 5 kcal/mol, and value of the Clausius-Clapeyron
constant is c = 7.53.
(a) Over what temperature range does the reactor contain a liquid phase?

To observe condensation inside the reactor, it is necessary to reach a point where the advance
of reaction produces enough moles of C that its partial pressure gets equal or higher than its
vapor pressure, at this point there will be a thermodynamical equilibrium between the liquid
and gaseous phases of C where the Clausius-Clapeyron equation is valid. Additionally, the
final partial pressure of C in this system is determined by the chemical equilibrium that’s
modeled with the definition of the equilibrium constant. The criteria to find the ranges where
there is condensation is:
If (𝑃𝐶𝑠 ≥ 𝑃𝐶 °) Then there is condensation

• Develop of the equilibrium pressures:

Considering the definition the equilibrium constant and assuming ideal gas model:
𝜈𝑗 𝑃𝐶 𝑦𝐶
𝐾 = ∏ 𝑃𝑗 = = (𝐸𝑞𝑛. 4.1)
𝑃𝐴 𝑃𝐵 𝑦𝐴 𝑦𝐵 𝑃
𝑗

The development to obtain the mole fractions in terms of the reaction extent starts with the
mole balances of each species:

𝑛𝐴 = 𝑛𝐴0 − 𝜉 (𝐸𝑞𝑛 4.2)

𝑛𝐵 = 𝑛𝐵0 − 𝜉 (𝐸𝑞𝑛 4.3)
𝑛𝐶 = 𝑛𝐶0 + 𝜉 (𝐸𝑞𝑛 4.4)
𝑛𝑇 = 𝑛 𝑇0 − 𝜉 (𝐸𝑞𝑛 4.5)
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Dividing by the total moles: 𝑦𝑗 = 𝑛𝑗 ⁄𝑛𝑇 :

𝑦𝐴 𝑜 − 𝜉 ′
𝑦𝐴 = (𝐸𝑞𝑛 4.6)
1 − 𝜉′
𝑦𝐵 𝑜 − 𝜉 ′
𝑦𝐵 = (𝐸𝑞𝑛 4.7)
1 − 𝜉′
𝑦𝐶0 + 𝜉 ′
𝑦𝐶 = (𝐸𝑞𝑛 4.8)
1 − 𝜉′
Where 𝜉 ′ = 𝜉 ⁄𝑛 𝑇0

Compiling the mole fractions in the expression for chemical equilibrium:

(𝑦𝐶0 + 𝜉 ′ )(1 − 𝜉 ′ )
𝐾= (𝐸𝑞𝑛 4.9)
(𝑦𝐴0 − 𝜉 ′ )(𝑦𝐵0 − 𝜉 ′ )𝑃

At this point, it is necessary to find an expression for the equilibrium constant at any
temperature since it is only known at 298K. Using the Van’t Hoff equation as it is reported in
equation 3.52 of Rawlings &Ekerdt (2002):
𝐾2 Δ𝐻° 1 1
ln ( ) = − [ − ] (𝐸𝑞 4.10)
𝐾1 𝑅 𝑇2 𝑇1
Defining 𝐾1 as the equilibrium constant at 298K, its value at any temperature T is:
𝛥𝐻° 1 1
𝐾(𝑇) = 𝐾1 exp (− [ − ]) (𝐸𝑞. 4.11)
𝑅 𝑇 𝑇1
Defining a temperature range to evaluate the possibility of condensation, it is possible to find
the partial pressure of C at equilibrium as a function of the temperature solving equations 3.11
and 4.9 for 𝜉 ′ and replacing it in 𝑦𝐶 (Equation 4.8).

• Calculation of the saturation pressure:

Simplifiyng the partial pressure of C at the vapor pressure:

𝛥𝐻𝑣𝑎𝑝
𝑃𝐶 ° = exp (𝑐 − ) (𝐸𝑞. 4.12)
𝑅𝑇
The expression of equation 4.12 can also be calculated for a temperature range. In this case,
we select the range from -50° to 50°C (223K – 323K) to calculate and compare the vapor
pressure of C and the partial pressure of C at the chemical equilibrium. This comparison is
presented below:
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Figure 3 Comparison PCe vs PCsat

From figure 3 it is possible to observe that the chemical equilibrium favors the reagents when
temperature increases, this is because the reaction is exothermic. Therefore, the higher the
temperature, the lower conversion of reagents. For this reason, the partial pressure of C is only
higher than its vaporization temperature at low temperatures. In this case, the condensation of
C will be observed at temperatures lower than 21°C. To lower limit in which the condition is
valid depends on at which point the ideal gas phase is no more valid or the condensation of
the rest of the species in the system.
Evidence of the calculations:

Figure 4 Evidences of exercise 3.7

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(b) If the reaction is endothermic with Δ𝐻° = 10 𝑘𝑐𝑎𝑙/𝑚𝑜𝑙, over what temperature range
does the reactor contain a liquid phase?

For this case, the reaction presented for the exercise is endothermic, this means that it will be
favored at higher temperatures. The considerations of ideal gas phase and the validity of the
Clausius – Clapeyron equation are maintained to use equation 4.12 to find the saturation
pressures and and equations 4.11 and 4.9 to solve to find the reaction extent at equilibrium
which will be used for the calculation for the partial pressure of C at the equilibrium with
equation 4.8.
The pressures profiles are:

Figure 5 Comparison of PCe vs PCsat for the endothermic reaction.

We observe that having an endothermic reaction, now the behavior pf the partial pressure of
the product 𝑃𝐶 in now inverse, the extent of the reaction is higher at higher temperatures
because it is favored by the temperature. Additionally, we observe a short span of
temperatures where 𝑃𝐶 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 is slightly higher than 𝑃𝐶 °. Only at this short section of
temperatures we will observe condensation at the reactor. To observe the plot more closely,
figure 6 present a zoom to the ranges at which the condensation occurs.
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Figure 6 Comparison of PCe vs PCsat for the endothermic reaction.

The numerical data obtained from the solution and that’s presented in figures 5 and 6
indicates that the condensation occurs when the reaction is perfomed between −11.4°𝐶 and
11.2°𝐶.
Evidence:

Bibliography
Rawlings, James B. and Ekerdt, John G. Chemical Reactor Analysis and Design
Fundamentals. Nob Hill Publishing (2002)