Chemical Engineering Fundamentals 2A

CEFCHA2
Lecture 3: Chemical Equilibrium, Multiple Reactions, Selectivity &
Yield

V Naidoo
JOB 4134
vizellen@uj.ac.za
 Objectives

 Understand how to relate chemical equilibrium to extent of reaction

 Understand the concept of multiple reactions, yield and selectivity

 Be able to use manipulate equations using extent of reaction

 Be able to do yield and selectivity calculations

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 Chemical Equilibrium
Chemical Equilibrium a state achieved in a reversible chemical reaction when the concentrations of the reactants
and products remain constant.

aA bB
Rate of forward reaction (A B)
equals the rate of the reverse
reaction (B A)

K=

3
 Chemical Equilibrium Composition

• “K” – the equilibrium constant represents the CO(g) + H2O(g) CO2(g) + H2(g)
ratio of product to reactant concentrations for a
Equilibrium constant
chemical reaction.

• “K” therefore, can predict/ indicate the extent of K (T) =

reaction in terms of how far the reaction has
progressed.
To indicate this relation holds
for a certain temperature Molar fractions

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 Equilibrium Composition

CO(g) + H2O(g) CO2(g) + H2(g)

Write the molar composition in terms of the

T = 1105 K CO extent of reaction:
1.00 mol C O H 2O
 =
2.00 mol H 2 O CO 2
H2
∴=  +
yco yH
2
2 = K(T)
y= ycoyH 2O =1.0

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 Equilibrium Composition

𝑛𝐶𝑂 =1 𝑚𝑜𝑙 𝐶𝑂 − 𝜉 𝑒
)/3
𝑛 𝐻 2 𝑂 =2 𝑚𝑜𝑙 𝐻 2 𝑂 − 𝜉 𝑒
)/3
𝑛𝐶𝑂 2=𝜉 𝑒
)/3
𝑛 𝐻 2=𝜉 𝑒
)/3
𝑛𝑡𝑜𝑡𝑎𝑙 =3 𝑚𝑜𝑙

𝑦 𝐶𝑂 2 𝑦 𝐻 2 (𝜉 ¿¿ 𝑒)
2
= =1 ¿
𝑦 𝐶𝑂 𝑦 𝐻 2 𝑂 (1 − 𝜉 𝑒 )(2 − 𝜉 𝑒 )
= 0.667

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Multiple
Reactions,
A+B C+D
Selectivity A+C E
B+D C
&
Yield
 Multiple Reactions

Multiple reaction : one or more reactions occurring simultaneously

Side Reaction : undesired reaction

Production of ethylene (dehydrogenation of ethane)

Design Objective
Main reaction Maximize desired products (C2H4)
C2 H6 C2 H4 + H2 Minimize undesired products (CH4, C3 H6 )

Side Reactions
C2 H6 + H2 2CH 4

C2 H4 + C2 H6 C3 H6 + C H 4
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 Yield & Selectivity

where the limiting reactant would be consumed

Yield:

0 < Yield < 1

Positive
The higher the selectivity, the more of the desired product formed

Selectivity:

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 Extent of Reaction & Multiple Reactions

desired A:

𝜉1 B:
A+B C+D
A+C E 𝜉2
C:
undesired
D:

∴=  + E:

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 Example 1

C2 H6 C2 H4 + H2 rxn 1
C2 H6 + H2 rxn 2
2CH 4

The feed contains 85.0 mole% ethane (C2H6) and the balance inerts (I).The fractional conversion of ethane is

0.501, and the fractional yield of ethylene is 0.471.

If reaction 1 is desired, calculate the percent molar composition of the product gas & selectivity of C 2 H 4 to CH4.

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 Example 1

Fractional yield of C 2 H 4 =0.471

fC2H6 = 0.501

n1 mol C 2 H 6
F (mol) n2 mol C 2 H 4
Process
n3 mol H 2
0.85 mol C2H6/mol
n4 mol CH 4
0.15 mol I/mol
n5 mol I

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 Example 1

C2 H6 :
C2 H6 :
C2 H6 C2 H4 + H2 𝝃𝟏
C2 H6 + H2 𝝃𝟐 C2 H4 :
2CH 4
C2 H4 :

∴=  + H2 :
H2 :

CH 4 :
CH 4 :

I: 13
 Example 1

𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 Assume basis: 100 mol

𝑓 𝐶 2 𝐻 6=
𝑚𝑜𝑙 𝑓𝑒𝑑
0.501
𝑚𝑜𝑙 𝐶 2 𝐻 4 𝑓𝑜𝑟𝑚𝑒𝑑
𝑓𝑦𝑖𝑒𝑙𝑑𝐶 2 𝐻 4 =
42.585𝑚𝑜𝑙=𝑚𝑜𝑙 𝐶2 𝐻 6𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑚𝑜𝑙 𝐶 2 𝐻 4 𝑓𝑜𝑟𝑚𝑒𝑑 𝑤𝑖𝑡h𝑜𝑢𝑡 𝑠𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
= 42.415 mol 𝑚𝑜𝑙 𝐶 2 𝐻 4 𝑓𝑜𝑟𝑚𝑒𝑑
0.471=
85

40.035 𝑚𝑜𝑙=𝑚𝑜𝑙 𝐶2 𝐻 4 𝑓𝑜𝑟𝑚𝑒𝑑

= 40.035 mol =

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Example 1

C2 H6 :

C 2 H 6 : 42.415 % molar compositions:

= 2.55
C 2 H 6¿ 30.29 %
C 2 H 4 ¿ 28.59 %
H2
¿ 26.77 %
¿ 3.64 %
CH 4
¿ 10.71 %
I

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 Example 1

Selectivity of C 2 H 4 to CH 4 = moles of desired product formed

moles of undesired product formed
= (40.035 mol C 2H 4) / (5.1 mol C H 4

= 7.85

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