4.

6 Chemical Reaction Stoichiometry

 Chemical reaction in a process
 Reaction imposes constraints on the relative amount of reactants and
products in the streams
 Material balance : add generation/consumption term

 Stoichiometry
 The theory of the proportions in which chemical species combine
with one another
(Example) 2SO2 + O2  2SO3

2 SO2 + 1 O2  2 SO3

Stoichiometric coefficients of the reaction

1
 4.6a Stoichiometry

 Stoichiometric ratio
 Ratio of stoichiometric coefficients
 Used as a conversion factor to calculate the amount of particular
reactant (or product) that was consumed (produced)
(Example) 2SO2 + O2  2SO3

2 mol SO 3 generated (produced) 2 lb - mols SO 2 consumed

1 mol O 2 consumed(reacted) 2 lb - mol SO 3 generated
stoichiometric
ratio used as a
The required amount of O2 to produce 1600 kg/hr SO3 ? conversion factor
conversion factor
1600 kg SO3 produced 1kg - mole SO 3 1 kg - mol O 2 reacted
10 kg - mol O2/hr
hr 80 kg 2 kg - mol SO 3 produced

kg-mol O2 32kg O2
10 = 320 kg O2/h
h 1 kg-mol O2
2
 4.6b Terminology

 Limiting reactants
 Exists less than ideal stoichiometric proportion
 Excess reactants
 Exists more than ideal stoichiometric proportion

(Example) 2SO2 + O2  2SO3

(30 mol) (10 mol)

(SO2/O2)stoi = 2.0
SO2 is an excess reactant
(SO2/O2)0 = 3.0
(O2/SO2)stoi = 0.5
O2 is a limiting reactant
(O2/SO2)0 = 0.333

3
 4.6b Terminology

 Fractional excess n  ns
 fraction of excess reactants ns
 ns : the amount needed to react completely with the limiting
reactant ( 양론비에 해당하는 몰수 )

 Percent excess n  ns
100
 percent of excess reactants ns

 Example
 H2 + Br2  2HBr
 H2 : 25 mol /hr
 Br2 : 20 mol /hr
 Fractional Excess H2 = (25 – 20) /20 = 0.25
4
 4.6b Terminology
 Fractional conversion
 Chemical reaction is not always complete

f = (moles reacted) / (moles fed)

 Extent of conversion : xi)

n i n i 0  i  N 2  3H 2  2 NH 3
where N 2 : 100 mol , H 2 : 300 mol
i  i (products) nN 2 100 mol  
i   i (reactants) nH 2 300 mol  3
 : extent of reaction nNH 3 2

5
 Example 4.6-1

 Acrylonitrile is produced by the reaction of propylene, ammonia

and oxygen.
C3H6 + NH3 + 3/2 O2  C3H3N + 3H2O

 The feed contains 10 mol % propylene, 12 % ammonia and 78

% air. A fractional conversion of 30 % of the limiting reactant is
achieved. Determine which reactant is limiting, the percentage
by which each of the reactants is in excess, and the molar flow
rates of all product gas constituents for a 30 % conversion of the
limiting reactants, taking 100 mol of feed as a basis.

6
 Solution
 Basis: 100 mol feed
C3H6 + NH3 + 3/2 O2  C3H3N + 3H2O

100 mol
Reactor
0.100 mol C3H6 /mol nC3H6 mol C3H6
0.120 mol NH3/mol n NH3 mol NH3
0.780 air /mol n O2 mol O2
0.21 mol O2 /mol n N2 mol N2
0.79 mol N2 /mol n C3H3N mol C3H3N
n H2O mol H2O
Composition of the feed
(C3 H 6 ) 0 100 0.10 10.0mol
( NH 3 ) 0 100 0.12 12.0mol
(O2 ) 0 100 0.78 0.21 16.4mol
Ratios of Reactants
( NH 3 / C3 H 6 ) 0 (12.0 / 10.0) 1.20 NH3 is in excess
( NH 3 / C3 H 6 ) STOI (1 / 1) 1.0
(O2 / C3 H 6 ) 0 (16.4 / 10.0) 1.64 O2 is in excess C3H6 is limiting
(O2 / C3 H 6 ) STOI 1.5 / 1 1.5
7
 Solution - Continued
C3H6 + NH3 + 3/2 O2  C3H3N + 3H2O
Percent Exess
( NH 3 ) STOICH 10.0mol
(O2 ) STOICH 15.0mol
% Excess NH 3 (12  10) / 10 100 20%
% Excess O 2 (16.4  15) / 15 100 9.3%
Fractional conversion 30 %
 10mol 0.3 3mol
nC H 10mol   7.0mol
3 6

nNH 3 12mol   9.0mol

nO2 16.4mol  1.5 11 .9mol
nN 2 (nN 2 ) 0 61.6mol (78 mol x 0.79 = 61.6
mol)
nC3 H 3 N  3mol

8
 4.6c Chemical Equilibrium

 Reaction type : A  B (irreversible)

A ↔ B (reversible)
 What is final composition ?
 Chemical equilibrium  Thermodynamics
D+E+F A+B+C
yA·yB·yC (K: equilibrium constant)
K=
yD·yE·yF (y: mole fraction of reactive species)

 How long it will take to reach equilibrium ?

 Chemical kinetics  Reaction Engineering

9
 Example 4.6-2

 Shift reaction
CO (g) + H2O(g) ↔ CO2 (g) + H2 (g)

yCO2 y H 2
Equilibrium constant K (y: mole fraction)
yCO y H 2O

at 1105 K, K = 1.00
feed : 1.0 mol CO + 2.0 mol H2O

Calculate the fractional conversion of limiting reactants

10
 Solution

 Strategy CO (g) + H2O(g) ↔ CO2 (g) + H2 (g)

 Use the extent of reaction
 Total moles  mole fraction  K value equation

nCO 1.00   yCO (1.00   ) / 3.0 yCO2 y H 2

nH 2O 2.00   y H 2O (2.00   ) / 3.0 K
yCO y H 2O
nCO2  yCO2  / 3.0 2
nH 2   1.0
y H 2  / 3.0 (1   )(2   )
ntotal 3.00

 0.667 f CO 0.667 / 1.0 0.667

(f: fractional conversion)

11
 4.6d Multiple Reaction, Yield, Selectivity

 Multiple reaction : one or more reaction

 Side Reaction : undesired reaction

 Example ) Production of ethylene

C 2H 6  C2H 4 + H 2

(Side Reactions)
C2H6 + H2  2CH4
C2H4 + C2H6  C3H6 + CH4

 Design Objective
 Maximize desired products (C2H4)
 Minimize undesired products (CH4, C3H6)

12
 4.6d Multiple Reaction, Yield, Selectivity

 Yield ( 수율 )
 Could be defined in a slightly different way
(check the definition every time)

(moles of desired product formed)

Moles of reactant fed
(moles of desired products, theoretical) or moles of reactant consumed
in the reactor

 Selectivity ( 선택도 )
(moles of desired product formed)
(moles of undesired product formed)

13
 4.6d Multiple Reaction, Yield, Selectivity

 Extent of reaction for multiple reactions

n i n i 0    ij j
j

 ij  0(if i is a product in reaction j)

 ij  0(if i is a reactant in reaction j)

14
 Example 4.6-3

 The reaction

C 2H 6  C 2H 4 + H 2

C2H6 + H2  2CH4

take place in a continuous reactor at steady state. The feed contain 85

mole % ethane and 15 % inert. The fractional conversion of ethane is
0.501 and yield of ethylene is 0.471. Calculate the composition of
products and selectivity of ethylene to methane production.

15
Basis : 100 mol feed
nC2 H 6 85.0  1   2 42.4
nC2 H 6 85.0  1   2
nC2 H 4 1 40.0
nC2 H 4 1
nH 2 1   2 37.4
nH 2 1   2
nCH 4 2 2 5.2
nCH 4 2 2
nI 15.0
nI 15.0

Fractional conversion of ethane = 0.501

yC2 H 6 0.303
85.0 (1  0.501) 85.0  1   2
yC2 H 4 0.286
Yield of ethylene = 0.471
y H 2 0.267
85.0 0.471 1 40.0
yCH 4 0.037
 2 2.6
y I 0.107

Selectivity = (40)/(5.2)=7.7 mol C2H4/mol CH4

16
 Example 4.7-1
 Methane is burned with oxygen to yield carbon dioxide
and water. The feed stream consisting of 20% CH4, 60 %
O2 and 20 % CO2 are fed into a reactor, in which
conversion of 90 % of the limiting reactant is obtained.
Calculate the molar composition of the product stream.

17
Basis : 100 mol
Reactor
0.200 CH4 nCH4
0.600 O2 nO2
0.200 CO2 nCO2
CH4 + 2O2  CO2 + 2H2O nH2O

Limiting reactant : CH4

Conversion of 90 % of limiting reactants

 nCH4= 100×0.2×0.1 = 2.0 mol CH4

There are three methods to solve the same problem

1. Molecular balance
2. Atomic balance
3. Extent of reaction

18
 Using Molecular Balance
Basis : 100 mol
Reactor
0.200 CH4 nCH4 = 2.0 mol
0.600 O2 nO2
0.200 CO2 nCO2
CH4 + 2O2  CO2 + 2H2O nH2O
Input + Generation = Output + Consumption

90 % conversion
= 18 mol CH4 reacted = 36 mol O2 reacted
= 18 mol CO2 produced = 36 mol H2O produced

CH4 Balance 100×0.2 + 0 = nCH4 + 18 nCH4 `= 2

O2 Balance 100×0.6 + 0 = nO2 + 36 nO2 =24

CO2 Balance 100×0.2 + 18 = nCO2 + 0 nCO2 =38

nH2O =36
H2O Balance 0 + 36 = nH2O + 0

19
 Using Atomic Balance
Basis : 100 mol
Reactor
0.200 CH4 nCH4 = 2.0 mol
0.600 O2 nO2
0.200 CO2 nCO2
CH4 + 2O2  CO2 + 2H2O nH2O

Input = Output

C Balance 100×0.2 +100×0.2 = nCH4 + nCO2

H Balance 100×0.2×4 = nCH4×4 + nH2O×2

O Balance 100×0.6×2 + 100×0.2×2= nO2×2+nCO2×2+nH2O×1

nCH4 = 2 nO2 =24 nCO2 =38 nH2O =36

20
 Using Extent of Reaction
Basis : 100 mol
Reactor
0.200 CH4 nCH4 = 2.0 mol
0.600 O2 nO2
0.200 CO2 nCO2
CH4 + 2O2  CO2 + 2H2O nH2O

nCH 4 20  1 2.0 1 18

nO2 60  21 24.0

nCO2 20  1 38.0

nH 2O 21 36.0

21
 4.7f Product separation and recycle

 Normally, reactions are not complete

 Separation and recycle
 Improved yield, conversion ,…

Reactants Product Products

Reactor Separation
Unit

Recycle

22
 Single Pass Conversion & Overall Conversion
reactantinputto process - reactantoutputfromprocess
 Overall conversion : reactantinputto process

 Single-pass conversion : reactant input to reactor - reactant output from reactor

reactant input to reactor

Product 75 mol B/min

75 mol A/min 100 mol A/min 25 mol A/min
Reactor Separation
75 mol B/min
Unit
Reaction AB
Single-pass
25 mol A/min conversion Conversion
= (input-output)/input

Overall
75 - 0
conversion Overall Conversion of A  100 % 100 %
75
100 - 25
Single Pass Conversion of A  100 % 75 %
100
23
 4.7g Purging

 Getting rid of undesired materials in recycle stream.

Reactants Product Products

Reactor Separation
Unit
Recycle
Purging

24
 Example 4.7-2
 Propane is dehydrogenated to form propylene in a catalytic reactor :

C3H8  C3H6 + H2

 The process is to be designed for a 95 % overall conversion of propane.

 The reaction products are separated into two streams :
 the first ,which contains H2, C3H6 and 0.555 % of the propane that leaves the
reactor, is taken off as product,
 and the second stream, which contains the balance of unreacted propane and 5
% of propylene in the product stream is recycled to the reactor.
 Calculate the composition of the product, the ratio (moles recycled)/(moles
fresh feed), and the single pass conversion.

25
1. A flow chart, and labeling.
2. Choose as a basis of calculation
3. Unify all units (mass and molar flow rates to mass or molar
flow rates)
4. Write material balance equations.
5. Solve equations.

100 mol C3H8 Separation

Reactor
FC3H8 P1,C3H8 Unit P2,C3H8
FC3H6 P1,C3H6 P2,C3H6
P1,H2 P2,H2

RC3H8
RC3H6

Basis 100 mol feed (propane)

26
100 mol C3H8 Separation
Reactor
FC3H8 P1,C3H8 Unit P2,C3H8
FC3H6 P1,C3H6 P2,C3H6
P1,H2 P2,H2

RC3H8
RC3H6

Degree of freedom analysis first, consider overall process

No. of Unknown = 3 (P2) + 1 ()

one more information required !
No. of eqn = 3 (No. of Comp.s)

Translate given information

95 % overall conversion of propane = 95

Material Balance
P2,C 3 H 8 100   5 mol
P2,C 3 H 6  95 mol
P2, H 2  95 mol 27
100 mol C3H8 Separation
Reactor
FC3H8 P1,C3H8 Unit 5 mol C3H8 (P2,C3H8)
FC3H6 P1,C3H6 95 mol C3H6 (P2,C3H6)
P1,H2 95 mol H2 (P2,H2)

RC3H8
RC3H6

Degree of freedom analysis first, consider overall process

No. of Unknown = 5 (P1,R)

two more information required !
No. of eqn = 3 (No. of Comp.s)

Translate given information

P2 contains 0.555 % propane in P1 P2,C3H8 = 0.00555 P1,C3H8

R contains 5 % propylene in P2 RC3H6 = 0.05 P2,C3H6

P1,C3H8 =P2,C3H8 / 0.00555 = 5/0.00555 = 900.9 mol

RC3H6 = 0.05 P2,C3H6=0.05×95=4.75 mol

From Material Balance , RC3H8 = 895 mol, P1,H2 = 95 mol 28

100 mol C3H8 Separation
Reactor
FC3H8 P1,C3H8 Unit 5 mol C3H8
FC3H6 P1,C3H6 95 mol C3H6
P1,H2 95 mol H2

RC3H8= 895 mol

RC3H6= 4.75 mol

Material Balance

FC3H8 = 100 + RC3H8 = 995 mol

FC3H6 = RC3H6 = 4.75 mol

Recycle Ratio = (895 + 4.75)/(100) = 9.0

Single Pass Conversion = (995-900.9)/995 = 9.55 %

29
 4.8 Combustion Reactions
 Combustion
 the rapid reaction of a fuel with oxygen

 products are worthless (CO2, H2O, CO, SO2,…)

 significance
 heat release  steam  power production

 power generation : mechanical engineers

 but… chemical engineers are heavily involved in the analysis of chemical

reactions, reactors and environmental consideration

 The method determining the heat will be treated in energy balance

(Ch. 7 – 9)

30
 4.8a Combustion Chemistry
 Fuels
 Coal ( C, H, S and various materials)
 Fuel oil (heavy hydrocarbons, some sulfur)
 Gaseous fuel
 liquefied natural gas (LNG)
 liquefied petroleum gas (LPG)

 Combustion
 partial combustion ( 부분연소 )
 complete combustion ( 완전연소 )

Example )
C + O2  CO2 (Complete combustion of carbon)

C3H8 + 5O2  3 CO2 + 4 H2O (Complete combustion of propane)

C3H8 + 7/2 O2  3 CO + 4 H2O (Incomplete combustion of propane)

CS2 + 3O2  CO2 + 2 SO2 (Complete combustion of carbon disulfide)

31
 4.8a Combustion Chemistry

 For obvious economic reasons, air is the source of oxygen in most

reactors
Components Mole Percent Average M.W
N2 78.03 29.0
O2 20.99
Ar 0.94
CO2 0.03
He, He, Ne, Kr, Xe 0.01
100

 In most combustion calculations,

 79 % N2 and 21 % O2  3.76 mole N2 / mole O2

32
 4.8a Combustion Chemistry

 Methods to express the composition of a gas mixture

 Wet basis
 component mole fraction / percent that contains water
 Dry basis
 component mole fraction / percent without water

Wet Basis
33.3 mole % CO2
33.3 mole % N2
33.3 mole CO2 33.3 mole % H2O
33.3 mole N2
33.3 mole H2O Dry Basis
50 mole % CO2
50 mole % N2

33
 4.8a Combustion Chemistry
 Stack gas or flue gas
 The product gas that leaves a combustion chamber

 Flow rate of a stack gas is normally measured with water

 The analysis of stack gas is performed without water

 Wet basis  dry basis conversion is important

 assume a certain amount (e.g. 100 mol) and calculate the composition

34
 Example 4.8-1

 A stack gas contains 60 mole % N2, 15 mole % CO2, 10

% O2 and the balance H2O. Calculate the molar
composition of the gas on a dry basis.

Basis : 100 mol stack gas

60 mol N2 60 mol N2 60/85=0.706 N2

15 mol CO2 15 mol CO2 15/85=0.176 CO2
10 mol O2 10 mol O2 10/85=0.118 O2
15 mol H2O

35
 4.8b Theoretical and Excess Air

A+BC

Expensive Cheap
(e.g. fuel ) (e.g. air)

 It is advantageous to provide excess amount of cheap reactant

 air : cheap reactant, free
 Terminology
 Theoretical oxygen
 Amount of oxygen needed for complete combustion
 Theoretical air
 The quantity of air that contains theoretical oxygen ( = × 100/21)
 Excess air
 The amount by which the air fed to reactor exceeds the theoretical air
 Percent excess air

(moles air)fed  (moles air) theroretical

100%
moles air theoretical
36
 Example 4.8-2

 100 mol/hr of butane (C4H10) and 5000 mol/hr of air are fed into a

combustion reactor. Calculate the percent excess air.

C4H10 +(13/2) O2  4CO2 + 5 H2O

100 mol C 4 H10 6.5 mol O 2

(O 2 ) theoretical  650 mol O 2 /hr
hr 1 mol C 4 H10

650 mol O 2 100 mol Air

(Air) theoretical  3094 mol Air/hr
hr 21 mol O 2

5000 - 3094
(% excess air )  100 61.6%
3094
37
 Two points of confusion
on theoretical and excess air

 The theoretical air required to burn a given quantity of fuel does not

depend on how much is actually burned.

 Always assume complete combustion!

 The value of the percent excess air depends only on the theoretical

air and the feed rate, and not on how much O2 is consumed in the

reactor or whether combustion is complete or partial.

38
 4.8c Material balance on Combustion Reactor

 Solving the material balance for combustion

reactions is essentially the same as for other
systems.
 Important Points
 remember to include N2 at both inlet and outlet

 remember to include unreacted fuel, O2 and

combustion products (CO2, H2O, CO)

39
 Example 4.8-3: Combustion of Ethane

 Ethane C2H6 is burned with 50 % excess air.

 The percent conversion of the ethane is 90 %; of the
ethane burned., 25 % reacts to form CO and the
balance reacts to form CO2.

 Calculate the composition of the flue gas on a dry

basis and the ratio of water to dry flue gas.

40
 100 mol C2H6
n1 mol C2H6
n2 mol O2
Q mol O2 n3 mol N2
3.76 Q mol N2
n4 mol CO
C2H6 + (7/2) O2  2CO2 + 3H2O n5 mol CO2
C2H6 + (5/2) O2  2CO + 3 H2O n6 mol H2O

Basis 100 mol ethane

Theoretical O2 = 100 * (7/2) = 350 mol

O2 fed = 350 * 1.5 = 525 mol O2

N2 fed = 525*(79/21) = 1974 mol N2

41
 100 mol C2H6
n1 mol C2H6
n2 mol O2
525 mol O2 n3 mol N2
1974 mol N2
n4 mol CO
C2H6 + (7/2) O2  2CO2 + 3H2O n5 mol CO2
C2H6 + (5/2) O2  2CO + 3 H2O n6 mol H2O
1   2 90 1 67.5
 2 0.25 (1   2 )  2 22.5

n1 n i , 0    i j j 100  1   2 10
n 2 n i , 0    i j j 525  (7 / 2)1  (5 / 2) 2 232.5
n 3 1974
n 4 n i , 0    i j j 0  2 2 45 now, you can calculate
the composition and the ratio
n 5 n i , 0    i j j 0  21 135
n 6 n i , 0    i j j 0  31  3 2 270.0

Total moles (n1+n2+--+n6) = 2666 mol

42
Total moles (n1+n2+--+n6) = 2666 mole

Dry gas = 2666 mole – 270 mole H2O = 2396 mol dry
gas
10 mol C2H6
y1 =
2396 mol dry gas
232 mol O2
y2 =
2396 mol dry gas
1974 mol N2
y3 =
2396 mol dry gas

45 mol CO
y4 =
2396 mol dry gas

135 mol CO2

y5 =
2396 mol dry gas

43