Chemical Engineering Fundamentals 2A

CEFCHA2

Lecture 4: Atomic & Molecular Specie Balances

V Naidoo
JOB 4134
vizellen@uj.ac.za

1
Objectives

 Understand the difference between dependent and independent species,

equations and reactions

 Understand the methods used for the molecular species and atomic specie

balances

 Be able to solve problems using all 3 methods

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 Molecular and Atomic Specie Balances
Molecular Specie Balance
Balance on the system using the molecular species present within the process
eg. , ,

At steady state: Input + Generation = Output + Consumption

Atomic Specie Balance

Balance on the system using the atoms of the species present within the process
Break the molecules into their atomic/elemental forms

Atoms cannot be
eg. C, H, N, O
created nor At steady state: Input = Output
destroyed

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Independent Equations
Reactions are independent if they cannot be related by a factor
If reactions can be related by a factor, they are dependent

}
X+Y=2 (1)

are dependent equations

2X + 2Y = 4 (2)

3X + 4Y = 7 (3)

are independent equations and therefore not related

X + 2Y = 4 (1)

Related by a factor of 3:
3X + 6Y = 12 (2)
dependent equations

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 Independent Species
In terms of chemical species present in the chemical reaction:
If information is given relating the two (or more) species to one another, they are dependent species
If species are not related, they are independent

Air
n3 mol/s O 2
n1 mol/s O 2 Mixe 3.76 n3 mol/s N 2
3.76 n1 mol/s N 2 r n4 mol/s CH 4

Methane
n2 mol/s CH 4 CH 4 is a molecule that is made
Nitrogen & Oxygen are related by the up of one carbon atom & 4
3.76 ratio and are dependent species hydrogen atoms

Only 2 independent equations can be written:

CH4 & O2 or CH4 & N2
C or H and O or N

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Independent Reactions
Chemical reactions are independent if the stoichiometric equation of any one of them cannot be
obtained by adding or subtracting multiples of the stoichiometric equations of the others

}
A B (1)

are dependent equations: (2) is a multiple of (1)

2A 2B (2)

are independent equations

A 2B (1) A 2B
+ 2(B C)
B C (2)
A 2C
A 2C (3)

(1) And (2) are independent, (3) is dependent on (1) and (2)

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Independent equations, species & reactions
A mixture of ethylene and nitrogen is fed to a reactor in which the ethylene is dimerized to butene

100 mol/s n1 mol C2 H4 /s

0.6 mol C2 H4 /mol 2C 2 H 4 C4 H8 n2 mol
0.4 mol N2 /mol C4 H8 /s n3
mol N2/s

a) How many independent molecular species are involved in the process? Show your analysis and list
down all molecular species balances.
3 independent molecular species balances (C H , C H and N )
2 4 4 8 2

b) How many independent atomic species are involved in the process? Show your analysis and list down
all atomic species balances. 2 independent atomic species balances (C or H and N )

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 Degrees of Freedom Analysis on Reactive Systems

Molecular species balances

@steady state: Input + generation = output + consumption

All unknowns in problem

No. unknown labeled variables
+ No. independent chemical reactions # of reactions occurring
- No. independent molecular species balances
- No. other equations relating unknown
variables

= Degree of freedom 8
 Degrees of Freedom Analysis on Reactive Systems
Atomic species balances

@steady state: Input = output

No. unknown labeled variables

- No. independent atomic specie balances Inerts
- No. independent molecular species balances on non-
reactive species
- No. other equations relating unknown variables
Extra information relating the
= Degree of freedom variables in the process

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 Degrees of Freedom Analysis on Reactive Systems

Extent of Reaction

@steady state: = +

One ξ per reaction

No. unknown labeled variables
+ No. independent chemical reactions
- No. independent reactive species balances
One reaction for every species
- No. independent non-reactive species in respect to ξ
- No. other equations relating unknown variables

= Degree of freedom

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Example

A + 2B C

10 mol A
30 mol B

𝑓 𝐴 =0.9

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Example 1: Extent of Reaction Method

Write in terms of the extent of reaction:

𝑛𝐴 =10−ξ
A: B:
𝑛𝐶 =0+ξ
C:

=9
12
1 mol A =
1 = 10
=9

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 Example 1: Molecular Species Balance @SS: A = 0

Input + generation = output + consumption

B: Output = Input – Consumption

A:B = 1:2
𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = (9 mol A reacted)(
f =
𝑚𝑜𝑙 𝑓𝑒𝑑 = 18 mol consumed
𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
0 .9 =
10
= 9 mol A reacted
C: Input + Generation = Output + Consumption
1 mol A = A:C = 1:1
0 + Generation = Output + 0
= (9 mol A reacted)(
= 9 mol generated

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Example 1: Atomic Specie Balance
A + 2B C
@SS: Input = output
C2H2 + 2H2 C2H6

Write balances on every specie in the system:

Carbon Balance: (10 mol C2H2)( = + )
1 mol A =
20 = 2(1) +
= 9 mol

Hydrogen Balance: (10 mol C2H2)()= + ) + )

)
= 12 mol

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 Method Comparison

Molecular Species Balance

 Use the general balance & determine
which terms are left for each
respective reactant & products
 Need to use stoichiometric ratio to
determine the generation &
consumption terms
Molecular species balances require
more complex calculations than either of the
other two approaches and should be used
only for systems involving one reaction
Atomic Specie Balance
 Input = Output
 Construct balances for each element
present the system
 Represent: flowrate(amount of atom
in the molecule per molecule)
Atomic species balances generally lead
to the most straight forward solution
procedure, especially when more than one
reaction is involved
Extent of Reaction Method
 Write each specie in terms of
the extent of reaction
 Solve for the extent of reaction
 Solve remaining unknowns
Extents of reaction are
convenient for chemical equilibrium
problems
ξ

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Example 2:
Dehydrogenation of ethane

C2 H6 C2 H4 + H2
n1 mol C2 H6 /s
100 mol/s C 2 H 6 n2 mol
C2 H4 /s 40
mol/s H 2

Mass balance analysis

1. Extent of reaction
ξ= ?
2. Atomic species balances
INPUT = OUTPUT
3. Molecular species balances
INPUT + GENERATION = OUTPUT + CONSUMPTION

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Example 2: Extent of Reaction Method
C2H6:
= 100 -

= 60 mol
C2H4:
= 0+ = 40 mol

H2:
40 = 0 –
= 40

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Example 2: Atomic Specie Balance Method
C: (100 mol C2H6)(
200 = 2 + 2 ------ (1)

H: (100 mol C2H6)( +

600 = 6 + 4 + 2(40)
520 = 6 + 4 ------(2)

= 100 - ---- substitute (1) in (2): = 40 mol; = 60 mol

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Example 2: Molecular Specie Balance
H2: Input + Generation = Output
0 + G = 0utput
40 mol = Output C2H4: Input + Generation = Output
C2H4:H2
1:1
0 + 40 = Output
C2H6: Input – Consumption = Output
40 mol = Output
C2H6:H2
1:1
100 – 40 = 60 Mol

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Product Separation & Recycle

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 Product Separation & Recycle

Normally, reactions are not complete, thus requiring product separation and subsequently recycle of unconverted reactants to further
improve the percentage yieldand conversion

Reactants Product Products

Reactor Separation
Unit

Recycle

Examples of product separation unit :

condenser, absorber, distillation column, flash
vessel

Compositions of product and recycle streams are not identical when they
emanate from a separation unit

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Overall Conversion
Boundary system

Product
Fresh Separation
Reactor s
reactant Unit +
s unconverte
d reactants

Overall Conversion

(reactant input to process) - (reactant output from process)

(reactant input to process)
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 Single-Pass
Conversion Boundary system

Fresh reactants unconverte Product Products

Reactor
R e a ctorr
Reactant t d reactants Separation
s Unit +
unconverted
reactants
Recycle

Single pass Conversion

reactant input to reactor - reactant output from reactor

reactant input to reactor
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 EXAMPLE

Methanol (CH 3 OH) is produced by reacting carbon monoxide (CO) and hydrogen (H2). A fresh feed stream containing C O and H 2
joins a recycle stream and the combined stream is fed to a reactor. The reactor outlet stream flows at a rate of 350 mol/min and contains
10.6 wt % H2, 64 wt % C O and 25.4 wt % C H 3 O H (Note : wt % is weight or mass % N O T mole %). This stream enters a
cooler in which most of the methanol is condensed. The liquid methanol condensate is withdrawn as a product and the gas stream leaving
the condenser which contains CO, H 2 and 0.4 mole % uncondensed C H 3 O H vapor is then recycled and combines with the fresh feed.
Calculate

a) The production of liquid CH 3 OH.

b) The molar flow rates of C O and H 2 in the fresh feed.
c) The molar flow rates of CO, H 2 and C H 3 O H to the reactor
d) The percentage single pass and overall conversion of H 2 and CO.

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Unit conversion of the compositions of the reactor outlet stream containing 10.6 wt % H2, 64 wt % C O

and 25.4 wt % C H 3 O H (from wt % to mol %)

C O + 2H 2 CH3 OH

n1 mol/min C O F F1 F 350 mol/min

Reactor Condenser P
n2 mol/min H 2 n3mol/min C O 0.273 mol CO/mol
2 0.632 mol H /mol P mol/min
n4 mol/min H 2 2
CH 3 OH
0.095 mol CH3OH/mol
n5 mol/min CH 3 OH

Mixing point R n6 mol CO/min

n7 mol H2/min
n8 mol
CH3OH/min
(0.004 mol
CH3OH/mol) 25
Solution: Molecular Specie Balance
GeneralBalance: Input + generation = output + consumption

Start solving the unknown of any stream with the most available information and possibly without any reaction and perform the degree of freedom analysis

350 mol/min
0.273 mol CO/mol
Condenser
P mol CH3 O H /min
0.632 mol H2/mol
Mass balance 0.095 mol
CH3OH/mol
around the condenser
n6 mol CO/min
n7 mol H2/min
n8 mol
CH3OH/min
(0.004 mol
CH3OH/mol) 26
Degree of Freedom Analysis:

3 No. unknown labeled variables (P, n6 , n7 , )

+1 No. independent chemical reactions
-3 No. independent molecular species balances (CH3 OH, CO,
-
H2 )
2 No. other equations relating unknown variables
(0.004 = n8 / (n6 +n7 + n8 ) )

0 degree of freedom
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 Answers

(A) R = 317.90 mol/min & P = 32.11 mol/min OH

(B) n1 = 32 mol/min CO ; n2 = 64 mol/min H2

(C) n3 = 128 mol/min CO; n4 = 285 mol/min H2; n5 = 1.27 mol/min CH3CHO

(D) SPC CO = 25%; SPC H2 = 22.4%

OC CO = 100% ; OC H2 = 100%

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