Faculty of

Faculty of Petroleum Faculty of

FACULTY OF PETROLEUM & RENEWABLE ENERGY ENGINEERING
& RenewablePetroleum
Energy &
Engineering Renewable Energy
Topic Learning Outcomes Petroleum &
Renewable Energy
www.utm.my/petroleumwww.utm.my/petroleum Engineering www.utm.my/petroleum Engineering

CHAPTER 4.1 - 4.3 At the end of this course students will be able to

Write and balance chemical reaction equations

Balances on
Define excess reactant, limiting reactants, fractional or percentage
Reactive Process conversion, selectivity and yield in a reaction

Perform material balance calculations for a reactive system using
an extent of reaction method

Sem 2 (2014/15) Sem 2 (2014/15) 2

Faculty of Faculty of
Balance on Continuous Steady-State Petroleum & Balance on Continuous Steady-State Petroleum &
Renewable Energy Renewable Energy
Reactive Process www.utm.my/petroleum Engineering Reactive Process www.utm.my/petroleum Engineering

 General material balance

Input - Output = Generation - Consumption
Input - Output + Generation - Consumption = Accumulation

 For steady state, accumulation = 0

 Then,

Input - Output = Consumption - Generation

3H2 + N2 2NH3

PROCESS

Sem 2 (2014/15) 3 Sem 2 (2014/15) 4

 Faculty of Faculty of
Chemical Reaction Stoichiometry Petroleum &
Renewable Energy Chemical Reaction Stoichiometry Petroleum &
Renewable Energy
www.utm.my/petroleum Engineering www.utm.my/petroleum Engineering

 Stoichiometry  Write the stoichiometric reaction of gaseous methane with pure

 The theory of proportions in which chemical species combine oxygen to produce carbon dioxide and water vapour
with one another.
 Stoichiometric equation CH4 + 2 O2 → CO2 + 2 H2O
SO2
SO3  Stoichiometric Ratio :
O2
 Ratio of stoichiometric coefficients can be used as a conversion
input  output factor.
2SO2 + 1O2  2 SO3  It can be used to calculate the amount or reactant (or product)
that was consumed (or produced) given another quantity of
Stoichiometric coefficients, (vi)
another reactant or product that participated in reaction.

Sem 2 (2014/15) 5 Sem 2 (2014/15) 6

Faculty of Faculty of
Chemical Reaction Stoichiometry Petroleum &
Renewable Energy Chemical Reaction Stoichiometry Petroleum &
Renewable Energy
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Stoichiometry equation : 2SO2 + O2 ----->

-----> 2SO3 For the production of 1600 kg/hour of SO3, calculate the mole and mass flowrate of
(A) (B) (C) oxygen needed :

Stoichiometry ratio ; 2 mol (or kmol, Ib-mole) SO3 produced Recall stoichiometric equation : 2SO2 + O2  2SO3
1 mol (or kmol, Ib-mole) O2 reacted
1600 kg SO3 produced 1 kmol SO3 1 kmol O2 reacted
2 mol (or kmol, Ib-mole) SO2 reacted
hour 80 kg SO3 2 kmol SO3 produced
2 mol (or kmol, Ib-mole) SO3 produced
produced=generated ; reacted=consumed = 10 kmol O2/hour
Two reactants, A and B are in Stoichiometry proportion when:
⇒10 kmol O2 32 kg O2 = 320 kg O2
mole A present = Stoichiometry proportion ratio obtained from the h 1 kmol O2 h
mole B present balanced equation

Sem 2 (2014/15) 7 Sem 2 (2014/15) 8

 Faculty of Faculty of

Working Session IV – Q#1 Petroleum &

Renewable Energy Limiting and Excess Reactants Petroleum &
Renewable Energy
www.utm.my/petroleum Engineering www.utm.my/petroleum Engineering

Consider the reaction  Limiting reactants

 Reactant that its present is less than its stoichiometric proportion relative to every
C4H8 + O2  CO2 + H2O other reactant
 Reactant that would be first fully consumed / reacted

1) Write the stoichiometric equation of the above reaction?

2) What is the stoichiometric coefficient of CO2?  Excess reactants
3) What is the stoichiometric ratio of H2O to O2? (Include units)  Reactant that if it is more than its stoichiometric proportion relative to every other
reactant
4) How many lb-moles of O2 react to form 400 lb-moles of CO2? (Use a
 Reactant that would have some unconsumed / unreacted after the reaction is
dimensional equation) complete
5) One hundred g-moles of C4H8 are fed into a reactor, and 50% reacts. At what
rate is water formed? Fractional Excess = n – nstoic % Excess = 100 X (n – nstoic)

nstoic nstoic
Sem 2 (2014/15) 9 Sem 2 (2014/15) 10

Faculty of Faculty of
Limiting and Excess Reactants – Petroleum &
Fractional Conversion Petroleum &
Renewable Energy Renewable Energy
Example www.utm.my/petroleum Engineering www.utm.my/petroleum Engineering

. disappear first for a complete reaction

Limiting reactant will
Fractional Conversion, f = mol reacted
moles feed
2SO2 + O2  2 SO3
Percentage Conversion = mol reacted x 100%
ni = 200 mol 100 mol 0 mol moles feed
nf = 0 mol 0 mol 200 mol
Example : Calculate the percentage conversion of SO2 and O2 for the following
ni = 180 mol 100 mol 0 mol reaction.
nf = 0 10 mol 180 mol 2SO2 + O2 ----->
-----> 2SO3

Limiting reactant = SO2 excess reactant = O2 ninitial = 200 mol 100 mol
nreacted = ? mol ? mol
Fractional excess of O2 = 0.1 % Excess of O2 = 10%
nfinal = ? mol ? mol 150 mol
From the stoichiometric equation
- What can you say about the total moles of input and output?
- What can you say about the total mass of input and output?

Sem 2 (2014/15) 11 Sem 2 (2014/15) 12

 Faculty of Faculty of
Extent of Reaction Petroleum &
Renewable Energy Extent of Reaction – Ex part (c) Petroleum &
Renewable Energy
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Suppose we start with 100 mol of H2 , 50 mol of Br2 and 30 mol of HBr. If 30 mol of H2 reacts with Br2 to form HBr, calculate the molar compositions of the
product?
a) Which reactant is limiting? H2 + Br2  2HBr
ninitial = 100 mol 50 mol 30 mol  2 mol HBr produced 
b) What is the percentage excess of other reactant?  
 1 mol H 2 reacted 
c) If 30 mol of H2 reacts with Br2 to form HBr, calculate the molar nreacted = 30 mol 30 mol 60 mol  
 x 30 mol H 2 reacted 
compositions of the product? nfinal = 70 mol 20 mol 90 mol

H2 + Br2  2HBr
 30 mol HBr fed 
100 mol H2 ? mol H2  50 mol Br 2 fed   
   2 mol HBr produced 
50 mol Br2 ? mol Br2  1 mol Br 2 reacted  + 1 mol H 2 reacted
x 30 mol H 2 reacted 
 − 1 mol H reacted x 30 mol H 2 reacted   
30 mol HBr ? mol HBr  2 

Sem 2 (2014/15) 13 Sem 2 (2014/15) 14

Faculty of Faculty of
Extent of Reaction Petroleum &
Renewable Energy Extent of Reaction Petroleum &
Renewable Energy
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(nH ) final = (nH )initial − ξ

2 2
Output = Input + Generation - Consumption
(nBr ) final = (nBr )initial − ξ ξ is the extent of reaction
2 2

(n HBr ) final = (n HBr )initial + 2ξ

(30 mol of H2 reacted) (n )
H2 final
( )
= nH 2 initial
−ξ

n i = n i0 + β i ξ
(n )
Br 2 final
= (n )
Br 2 initial −ξ
Recall stoichiometric coefficient (vi) (n HBr ) final = (n HBr )initial + 2ξ
:- where
ξ = 30 mol H 2 reacted
vi = negative for reactant
vi = positive for products
βi = + νi (products)
Example βi = − νi (reactants) (n )
H2 final
= 100 − 30 = 70 mol H 2
1H2 + 1Br2  2HBr βi = 0 (inert) (n )
Br 2 final
= 50 − 30 = 20 mol Br 2
vH2 = -1 vBr2 = -1 vHBr = +2
ξ : extent of reaction (n HBr )final = 30 + 2(30) = 90 mol HBr

Sem 2 (2014/15) 15 Sem 2 (2014/15) 16

 Faculty of Faculty of

Working Session IV – Q#2 Petroleum &

Renewable Energy
Petroleum &
Renewable Energy
www.utm.my/petroleum Engineering www.utm.my/petroleum Engineering

The oxidation of ethylene to produce ethylene oxide proceeds according to the The oxidation of ethylene to produce ethylene oxide proceeds according to the
equation: 2C H + O ----->
-----> 2C H O equation: 2C H + O ----->
-----> 2C H O
2 4 2 2 4 2 4 2 2 4
ethylene oxygen ethylene oxide ethylene oxygen ethylene oxide
The feed to the reactor contains 100 kmol C2H4 and 100 kmol O2.
The feed to the reactor contains 100 kmol C2H4 and 100 kmol O2.
(1) Which reactant is limiting? C2H4
(1) Which reactant is limiting? (2) What is the percentage excess of the excess reactant? 100%100%
(2) What is the percentage excess of the excess reactant? (3) If the reaction proceeds to completion, how much of the excess reactant will be left;
(3) If the reaction proceeds to completion, how much of the excess reactant will be left; how much C2H4O will be formed; and what is the extent of reaction? 50 mol O2, 100
how much C2H4O will be formed; and what is the extent of reaction? mol C2H4O, ξ = 50 mol.mol
(4) If the reaction proceeds to a point where the fractional conversion of the limiting (4) If the reaction proceeds to a point where the fractional conversion of the limiting reactant
reactant is 50%, how much of each reactant and product is present at the end, and is 50%, how much of each reactant and product is present at the end, and what is the
what is the extent of reaction? extent of reaction? 50 mol C2H4 , 75 mol O2, 50 mol C2H4O, ξ = 25 mol
(5) If the reaction proceeds to a point where 60 mol O2 are left, what is the fractional
(5) If the reaction proceeds to a point where 60 mol O2 are left, what is the fractional
conversion of C2H4? The fractional conversion of O2? The extent of reaction?
conversion of C2H4? The fractional conversion of O2? The extent of reaction?
f C2H4 = 0.8 , fO2 = 0.4 , ξ = 40 mol

Sem 2 (2014/15) 17 Sem 2 (2014/15) 18

Faculty of Faculty of

Working Session IV – Q#3 Petroleum &

Renewable Energy
Petroleum &
Renewable Energy
www.utm.my/petroleum Engineering www.utm.my/petroleum Engineering

In the Deacon process for the manufacture of chlorine i) Draw a process flow chart

2HCl + 0.5O2  Cl2 + H2O

(Cl2), hydrochloride acid (HCl) and oxygen (O2) react to
100 mol HCl np mol
form Cl2 and water (H2O). Sufficient air (21 mole % O2,
n1 mol Cl2 y1 mol Cl2/mol
nair mol Air
79% N2) is fed to provide 35% excess oxygen and the n2 mol H2O y2 mol H2O/mol
y3 mol HCl/mol
n3 mol HCl
0.21 mol O2/mol y4 mol O2/mol
fractional conversion of HCl is 85%. Calculate the mole 0.79 mol N2/mol
n4 mol O2
y5mol N2/mol
n5 mol N2
(35% excess O2)
fractions of the product stream components using the f = (100 - n3)/100 = 0.85

extent of reaction. ii) Basis : 100 mol HCl (WHY???)

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 Faculty of Faculty of
Petroleum & Petroleum &
Renewable Energy Renewable Energy
www.utm.my/petroleum Engineering www.utm.my/petroleum Engineering

2HCl + 0.5O2  Cl2 + H2O 2HCl + 0.5O2  Cl2 + H2O

III. Total moles of air required with 35% excess O2 or

(n ) − (n
O 2 act. )
O 2 stoic. 0.5 mol O2 1.35 mol O2 mol air
% Excess O 2 = x 100% nair = 100 mol HCl x x x
(n ) O 2 stoic.
2 mol HCl mol O2 0.21 mol O2
HINT : Excess reactant (i.e. O2) is calculated assuming the limiting reactant (LR)
undergoes complete reaction (not actual amount (i.e % conversion ) of LR
= 160.7 mol
reacted!!)

0.5 mol O 2
(n ) O 2 stoic. = 100 mol HCl x
2 mol HCl
= 25 mol IV. Percentage conversion of HCl = 85%)
(n ) O 2 act. ( )
= 0.35 n O 2 stoic.
( )
+ n O 2 stoic. = (0.35)(25 ) + 25 = 33.75 mol
 1 mol air  100 - n3
( )
n air = n O 2 x
act. 
 = 160.7 mol f = = 0 .85 ... n3 = 15 mol HCl
 0.21 mol O 2  100

Sem 2 (2014/15) 21 Sem 2 (2014/15) 22

Faculty of Faculty of
Petroleum &
Renewable Energy Working Session IV – Q#4 Petroleum &
Renewable Energy
www.utm.my/petroleum Engineering www.utm.my/petroleum Engineering

2HCl + 0.5O2  Cl2 + H2O

V. Extent of Reaction Ammonia is occasionally oxidized to produce nitric oxide which is can be
subsequently used along with more ammonia in the production of ammonium
ni = ni ,o + viξ Cl 2 bal . n1 = 0 + ξ = 42.5 mol nitrate (a fertilizer). When ammonia is oxidized at relatively low
H 2 O bal . n2 = 0 + ξ = 42.5 mol temperatures (about 400°C), the oxidation occurs by the following reaction:
HCl bal. n3 = 100 − 2ξ O 2 bal . n4 = 0.21(nair ) − 0.5ξ = 12.5 mol
ξ = 42.5 mol N 2 bal . n5 = 0.79(nair ) = 120 mol 4NH3 + 5O2  4NO + 6H2O

n p = 239.5 mol The feed stream contains 1000 kmol/h ammonia and 1750 kmol/h
oxygen. 70% of the ammonia fed to the reactor is converted:
n1 n2 n
y1 = = 0.177 , y2 = = 0.177 , y 3 = 3 = 0.0626
np np np
a.What is the limiting reactant? What is the excess reactant?
n4 n
y4 = = 0.0522 , y5 = 5 = 0.5312 b.What percentage is the excess reactant in excess?
np np
c.Calculate the flow rate (kmol/h) and mole fraction compositions of the
product stream using the extent of reaction

Sem 2 (2014/15) 23 Sem 2 (2014/15) 24

 Faculty of Faculty of
Chemical Equilibrium Petroleum &
Renewable Energy Chemical Equilibrium Petroleum &
Renewable Energy
www.utm.my/petroleum Engineering www.utm.my/petroleum Engineering

Reversible reaction CO(g) + H2O(g) <===> CO2(g) + H2(g)

Chemical Reaction  The rates of forward and reverse reactions are identical when the
equilibrium is reached.
Engineering
 The compositions of product and reactant do no change when the reaction
mixture is in chemical equilibrium.
Chemical Equilibrium Chemical Reaction
y co y H 2
Thermodynamics Kinetics 2
= K (T )
yco y H 2 O

Final equilibrium How long the system take Irreversible reaction: 2C2H4 + O2 ===> 2C2H4O
composition to reach a specified
state of equilibrium  The reaction proceeds only in a single direction (reactants  products)
 The reaction ceases and hence equilibrium composition is attained when the
limiting reactant is fully consumed.

Sem 2 (2014/15) 25 Sem 2 (2014/15) 26

Faculty of Faculty of
Mass Balance involving Process in Petroleum & Mass Balance involving Process in Petroleum &
Renewable Energy Renewable Energy
Chemical Equilibrium State www.utm.my/petroleum Engineering Chemical Equilibrium State www.utm.my/petroleum Engineering

aA + bB <===> cC + dD aA + bB <===> cC + dD

OUTPUT (out) Extent of Reaction, ξ …… n out, i = n in, i ± v i ξ

INPUT (in)
A
A, B, C, D  n out, C  n out, D 
B
   
 nT  n T 
= 
yCy D
K(T) =
y AyB  n out, A  n out, B 
yC yD    
K(T) =  n T  n T 
yA yB
 (n in, C + cξ )  (n in, D + dξ )  
n out, C n out, D n out, A n out, B    
yc = , yc = , yc = , yc =
=  nT  nT 
=
(n in, C + cξ )(n in, D + dξ )
nT nT nT nT
 (n in, A − aξ )  (n in, B − bξ )   (n − aξ )(n in, B − bξ )
    in, A
nT = nA + nB + nC + nD
 nT  nT 

Sem 2 (2014/15) 27 Sem 2 (2014/15) 28

 Faculty of Faculty of
Working Session IV – Q#5 Petroleum &
Renewable Energy
Petroleum &
Renewable Energy
Example 4.6-2 www.utm.my/petroleum Engineering www.utm.my/petroleum Engineering

If the water-gas shift reaction T = 1105 K CO

1.00 mol CO H2O
CO(g) + H2O(g) <===> CO2(g) + H2(g) CO2
2.00 mol H2O
H2
Proceeds to equilibrium at a temperature T(K), the mole fractions of the y co y H 2
2
four reactive species satisfy the relation = K (T ) = 1.0
yco y H 2 O
y co 2 y H 2
= K (T )
y co y H 2 O
where K (T) is the reaction equilibrium constant. At T = 1105 K, K = 1.0. Strategy:
Suppose the feed to a reactor contains 1 mol of CO, 2 mol of H2O and no
CO2 or H2, and the reaction mixture comes to equilibrium at 1105 K. 1. Express all mole fraction in terms of a single variable xe (extent of
Calculate the equilibrium composition and the fractional conversion of the reaction)
limiting reactant. 2. Substitute xe in the equilibrium relation and solve for xe.
3. Use xe to calculate mole fractions and any other desired quantity.
Sem 2 (2014/15) 29 Sem 2 (2014/15) 30

Faculty of
Petroleum & Multiple Reaction, Yield, Faculty of
Petroleum &
Renewable Energy Renewable Energy
www.utm.my/petroleum Engineering Selectivity www.utm.my/petroleum Engineering

1. Express all moles and mole fractions in terms ξe  Multiple reaction : one or more reaction
nCO = 1.00 - ξe
nH2O = 2.00 - ξe yCO = (1.00 - ξe)/3.00
 Main Reaction
nCO2 = ξe =====> yH2O = (2.00 - ξe)/3.00 ====> (1)
yCO2 = ξe /3.00  Side Reaction : undesired reaction
nH2 = ξe
_____________ yH2 = ξe /3.00
ntotal = 3.00  Example :- Production of ethylene (dehydrogenation of ethane)
2. Substitute mole fractions from (1) in the equilibrium reaction Main reaction
How do you control
C2H6  C2H4 + H2
ξe2 the reaction, i.e.
= 1.00; ξe = 0.667 Side Reactions minimize the side
(1.00 - ξe)(2.00 - ξe) C2H6 + H2  2CH4 reaction?
C2H4 + C2H6  C3H6 + CH4
3. yCO = 0.111; yH2O = 0.444; yCO2 = 0.222; yH2 = 0.222
(a) limiting reactant  CO;  Design Objective Learn more in
(b) At equilibrium, nCO = 1.00 - 0.667 = 0.333  Maximize desired products (C2H4)
chemical reaction
engineering course
Fractional conversion= f co = (1.00 - 0.333) mol reacted  Minimize undesired products (CH4, C3H6)
= 0.667
at equilibrium 1.00 mol fed

Sem 2 (2014/15) 31 Sem 2 (2014/15) 32

 Multiple Reaction, Yield, Faculty of
Petroleum & Multiple Reaction, Yield, Faculty of
Petroleum &
Renewable Energy Renewable Energy
Selectivity www.utm.my/petroleum Engineering Selectivity www.utm.my/petroleum Engineering

 Yield
(moles of desired product formed at given fractional  Calculation of molar flow rates for multiple reactions
conversion of limiting reactant)
(moles of desired product formed, assuming no side
reactions and the limiting reactant is completely reacted)
ni = ni0 +
∑v ξ j
ij j

+ ν ij if i is a product in reaction j
 Selectivity
(moles of desired product formed) − ν ij if i is a reactant in reaction j
(moles of undesired product formed) v ij = 0 if i does not appear in reaction j

Sem 2 (2014/15) 33 Sem 2 (2014/15) 34

Faculty of Faculty of

Working Session IV – Q#6 Petroleum &

Renewable Energy
Engineering
Petroleum &
Renewable Energy
Engineering
www.utm.my/petroleum www.utm.my/petroleum

Consider the following pair of reactions a) The fractional conversion of A.

A bal. Output = input – consumption

A  2B (desired) 10 = 100 – consumption …. consumption = 90 mol
A  C (undesired)
fractional conversion of A = moles A reacted / moles A fed = 90/100 = 0.9

Suppose 100 mol of A is fed to a batch reactor and the final product
b) The percentage yield of B
contains 10 mol of A, 160 mol of B and 10 mol of C. Calculate
% yield of B = (moles B generated/ moles B generated if limiting reactant is
a) The fractional conversion of A. completely consumed) x 100%
b) The percentage yield of B. = (160/200) x 100%
= 80%
c) The selectivity of B relative to C.
d) The extents of the first and second reactions.

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 Faculty of Faculty of
Petroleum &
Renewable Energy
Engineering
Working Session IV – Q#7 Petroleum &
Renewable Energy
Engineering
www.utm.my/petroleum www.utm.my/petroleum

Consider the following pair of reactions

c) The selectivity of B relative to C.

Selectivity = (moles of desired product formed / (moles of undesired product formed) 4A + 5B  4C + 6D (desired)
= 160 mol B/10 mol C = 16 mol B/mol C 4A+ 6C  5E + 6D (undesired)

d) The extents of the first and second reactions.

Component A undergoes complete reaction, however, 70% takes in the desired reaction and the balance
A  2B (desired) …………rxn 1 is the undesired reaction. Based on a feed stream containing 1000 kmol/h A and 1750 kmol/h B .
A  C (undesired) …………rxn 2
a. What is the limiting reactant? What is the excess reactant?
B bal. Output = input + (2)ξ1 b. What percentage is the excess reactant in excess?
160 = 0 + 2(1) ξ1 ……………. ξ1 = 80 mol
c. Write down the mass balance of each component using the extent of reaction
C bal. Output = input - (1)ξ2 d. Calculate the molar flow rate of each component in the product stream
10 = 0 - (1) ξ2 ……………. ξ2 = 10 mol e. Calculate the percentage yield of C
f. Calculate the selectivity of C relative to E
Check!!! A bal. Output = input – (1) ξ2 - (1) ξ2
10 = 100 – (1) ξ1 – (1) ξ2 ……………. ξ1 + ξ2 = 90 mol g. What percentage of the C component produced by the desired reaction is consumed by the
undesired reaction?

SOLVE AT YOUR OWN TIME

Sem 2 (2014/15) 37 Sem 2 (2014/15) 38

Faculty of Faculty of
Petroleum &
Renewable Energy
Engineering
Working Session IV – Q#8 Petroleum &
Renewable Energy
Engineering
www.utm.my/petroleum www.utm.my/petroleum

Consider the following pair of reactions What is the limiting reactant (LR) ? Methane (CH4) and oxygen (O2) react in the presence of a catalyst to form
formaldehyde (HCHO). In a parallel reaction methane is oxidized to carbon dioxide
4A + 5B  4C + 6D (desired) ………(1) HINT !! LR is determined using the (CO2) and water (H2O) :
4A+ 6C  5E + 6D (undesired) ………….(2) main (i.e. desired) reaction

CH4 + O2  HCHO + H2O

A feed stream contains 1000 mol/h A and 1750 mol/h B.
Write down the mass balance of each component using the extent of reaction.
CH4 + 2O2  CO2 + 2H2O

A bal. n1 = 1000 − 4ξ1 − 4ξ 2 .. ( 1 )

nout ,i = nin ,i + ∑v ξ
j =1, 2
ij j B bal. n2 = 1750 − 5ξ1 .. ( 2 )
Suppose 100 mol/s of equimolar amount of methane and oxygen is fed to a
continuous reactor. The fractional conversion of methane is 0.9 and the fractional yield
C bal. n3 = 0 + 4ξ1 − 6ξ 2 .. ( 3 ) of formaldehyde is 0.855. Calculate the molar composition of the reactor output stream
Calculate the extents of the D bal. n4 = 0 + 6ξ1 + 6ξ 2 .. ( 4 ) and the selectivity of formaldehyde production relative to carbon dioxide production.
first and second reactions
(ξ1 & ξ2 ?) E bal. n5 = 0 + 5ξ 2 ..( 5 )

SOLVE AT YOUR OWN TIME

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