SKF 1113 - Material Balances

Balances on Reactive Process (Part A)

Azeman Mustafa, PhD Kamarul Asri Ibrahim, PhD

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Material Balance

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Chemical Reaction Stoichiometry

Stoichiometry The theory of proportions in which chemical species combine with one another. Stoichiometric equation
SO2 O2 SO3

input output 2SO2 + 1O2 2 SO3

Stoichiometric coefficients, (vi)
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Instructor: Dr. Azeman Mustafa

SKF 1113 - Material Balances

Chemical Reaction Stoichiometry

Write the stoichiometric reaction of gaseous methane with pure oxygen to produce carbon dioxide and water vapour

Stoichiometric Ratio : Ratio of stoichiometric coefficients can be used as a conversion factor. It can be used to calculate the amount or reactant (or product) that was consumed (or produced) given another quantity of another reactant or product that participated in reaction.
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Chemical Reaction Stoichiometry

Stoichiometry equation : Stoichiometry ratio ; 2SO2 + O2 -----> 2SO3 (A) (B) (C) 2 mol (or kg-mole, Ib-mole) SO3 produced 1 mol (or kg-mole, Ib-mole) O2 reacted 2 mol (or kg-mole, Ib-mole) SO2 reacted 2 mol (or kg-mole, Ib-mole) SO3 produced Two reactants, A and B are in Stoichiometry proportion when: mole A present mole B present
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= Stoichiometry proportion ratio obtained from the the balanced equation

Material Balance Page 4-4

Instructor: Dr. Azeman Mustafa

SKF 1113 - Material Balances

Chemical Reaction Stoichiometry

For the production of 1600 kg/hour of SO3, calculate the rate of oxygen needed: Recall stoichiometric equation : 2SO2 + O2 2SO3

1600 kg SO3 produced hour = 10 kmol O2/hour

1 kmol SO3 80 kg SO3

1 kmol O2 reacted 2 kmol SO3 produced

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Working Session I
Consider the reaction C4H8 + 1. 2. 3. 4. 5. 6. O2 CO2 + H2O

Write the stoichiometric equation of the above reaction? What is the stoichiometric coefficient of CO2? What is the stoichiometric ratio of H2O to O2? (Include units) Does the total moles of the reactants equal that of the products? Does the total mass of the reactants equal that of the products? How many lb-moles of O2 react to form 400 lb-moles of CO2 (Use a dimensional equation.) 7. One hundred g-moles of C4H8 are fed into a reactor, and 50% reacts. At what rate is water formed?
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Instructor: Dr. Azeman Mustafa

SKF 1113 - Material Balances

Limiting and Excess Reactants

Limiting reactant

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

Excess reactants

Reactant that if its is more than its stoichiometric proportion relative to every other reactant Reactant that would have some unconsumed / unreacted after the reaction is complete = n - nstoic

Fractional Excess

nstoic

% Excess =

100 x n - nstoic

nstoic

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Limiting and Excess Reactants Example

. disappear first for a complete reaction Limiting reactant will

ni nf ni nf

2SO2 = 200 mol = 0 mol = 180 mol = 0 =

O2 100 mol 0 mol 100 mol 10 mol

2 SO3 0 mol 200 mol 0 mol 180 mol

Limiting reactant

SO2

excess reactant % Excess of O2 = 10%

= O2

Fractional excess of O2 = 0.1

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?
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Instructor: Dr. Azeman Mustafa

SKF 1113 - Material Balances

Fractional Conversion
Fractional Conversion, f = Percentage Conversion = mol reacted moles feed mol reacted x 100% moles feed

Example : Calculate the percentage conversion of SO2 and O2 for the following reaction. 2SO2 + O2 100 mol ? mol ? mol -----> 2SO3

ninitial nreacted nfinal

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= 200 mol = ? mol = ? mol

150 mol
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Material Balance

Extent of Reaction
Suppose we start with 100 mol of H2 , 50 mol of Br2 and 30 mol of HBr. 30 mol of H2 reacts with Br2 to form HBr. a) Which reactant is limiting? b) What is the percentage excess of other reactant? c) If 30 mol of H2 reacts with Br2 to form HBr, calculate the molar compositions of the product? H2
100 mol H2 50 mol Br2 30 mol HBr
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Br2

2HBr
? mol H2 ? mol Br2 ? mol HBr
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Instructor: Dr. Azeman Mustafa

SKF 1113 - Material Balances

Extent of Reaction
If 30 mol of H2 reacts with Br2 to form HBr, calculate the molar compositions of the product? H2 + Br2 2HBr ninitial = 100 mol 50 mol 30 mol nreacted = 30 mol 30 mol 60 mol nfinal = 70 mol 20 mol 90 mol

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Extent of Reaction

(n HBr ) final = (nHBr )initial + 2

Recall stoichiometric coefficient (vi) :-

(nH ) final = (nH )initial (nBr ) final = (nBr )initial

2 2 2 2

is the extent of reaction (30 mol of H2 reacted)

n i = n i0 + i where i = + i i = i i = 0 (products) (reactants) (inert)

vi = negative for reactant vi = positive for products

Example 1H2 + 1Br2 2HBr vH2 = -1 vBr2 = -1 vHBr = +2
Material Balance

: extent of reaction
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Instructor: Dr. Azeman Mustafa

SKF 1113 - Material Balances

Working Session II
The oxidation of ethylene to produce ethylene oxide proceeds according to the equation: 2C2H4 + O2 -----> 2C2H4O ethylene oxygen ethylene oxide

The feed to the reactor contains 100 kmol C2H4 and 100 kmol O2.

(1) Which reactant is limiting? (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; how much C2H4O will be formed; and what is the extent of reaction? (4) If the reaction proceeds to a point where the fractional conversion of the limiting reactant is 50%, how much of each reactant and product is present at the end, and what is the extent of reaction? (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?
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Balances on Reactive Systems

Example 4.6-1

Acetonitrile is produced by the reaction of propylene, ammonia and oxygen. C3H6 + NH3 + 3/2 O2 ----> C3H3N + 3H2O The feed contains 10 mole% 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 basis.

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Instructor: Dr. Azeman Mustafa

SKF 1113 - Material Balances

Balances on Reactive Systems

Example 4.6-1

100 mol 0.100 mol C3H6/mol 0.120 mol NH3/mol 0.780 mol air/mol (0.21 mol O2/mol 0.79 mol N2/mol)

Reactor

NC3H6 mol C3H6 NNH3 mol NH3 NO2 mol O2 NN2 mol N2 NC3H3N mol C3H3N NH2O mol H2O

The feed to the reactor contains: (C3H6)feed = 10.0 mol (NH3)feed = 12.0 mol (O2)feed = 78.0 mol air
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(NH3/C3H6)feed = 1.2, NH3 is in excess (O2/C3H6)feed = 1.64, O2 is in excess 0.210 mol O2 mol air
Material Balance

= 16.4 mol
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Balances on Reactive Systems

Example 4.6-1
x 100%

(% excess) NH3 = (NH3)feed - (NH3)stoich

(NH3)stoich

= (12 - 10)/10 x 100 = 20% excess NH3 (% excess) O2 = (O2)feed - (O2)stoich

(O2)stoich

x 100

= (16.4 - 15.0)/15.0 x 100 = 9.3% excess O2 If the fractional conversion of C3H6 is 30%, then (C3H6)out = 0.700(C3H6)feed = 7.0 mol C3H6 Extent of reaction, = 3.0 NO2 = 16.4 - 1.5 = 11.9 mol O2 NN2 = (N2)o = 61.6 mol N2
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NC3H6 = 12.0 - = 9.0 mol NH3; NC3H3N = = 3.00 mol C3H3 ; NH2O = 3 = 9.0 mol H2O
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Material Balance

Instructor: Dr. Azeman Mustafa

SKF 1113 - Material Balances

Working Session III

In the Deacon process for the manufacture of chlorine (Cl2), hydrochloride acid (HCl) and oxygen (O2) react to form Cl2 and water (H2O). Sufficient air (21 mole % O2, 79% N2) is fed to provide 35% excess oxygen and the fractional conversion of HCl is 85%. Calculate the mole fractions of the product stream components using the extent of reaction.

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Solution to Working Session III

i) Draw a process flow chart 2HCl + 0.5O2 Cl2 + H2O 100 mol HCl nair mol Air 0.21 mol O2/mol 0.79 mol N2/mol (35% excess O2) np mol n1 mol Cl2 n2 mol H2O n3 mol HCl n4 mol O2 n5 mol N2 y1 mol Cl2/mol y2 mol H2O/mol y3 mol HCl/mol y4 mol O2/mol y5mol N2/mol

f = (100 - n3)/100 = 0.85

ii) Basis : 100 mol HCl (WHY???)

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Instructor: Dr. Azeman Mustafa

SKF 1113 - Material Balances

Solution to Working Session III

IV. Total moles of air required with 35% excess O2

nair = 100 mol HCl x = 160.2 mol

0 .5 mol O 2 1.35 mol O 2 mol air x x 2 mol HCl mol O 2 0 .21 mol O 2

V. Moles of HCl reacted (% conversion = 85%)

0 .85 mol HCl r eacted 100 mol HCl f ed x = 85 mo l mol HCl fe d

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Material Balance

Solution to Working Session III

II. Extent of Reaction

ni = ni ,o + v i HCl bal . n3 = 100 2

= 42.5 mol

Cl 2 bal . n1 = 0 + = 42.5 mol O 2 bal . n4 = 0.21(nair ) 0.5 = 12.5 mol N 2 bal . n5 = 0.79 (nair ) = 120 mol H 2O bal . n2 = 0 + = 42.5 mol

n p = 239.5 mol y1 = y4 = n1 = 0.177 , np y2 = n n2 = 0.177 , y 3 = 3 = 0.0626 np np

n n4 = 0.0522 , y 5 = 5 = 0.5312 np np

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SKF 1113 - Material Balances

Chemical Equilibrium
Chemical Reaction Engineering Chemical Equilibrium Thermodynamics Chemical Reaction Kinetics How long the system take to reach a specified state of equilibrium

Final equilibrium composition

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Chemical Equilibrium
Reversible reaction CO(g) + H2O(g) <===> CO2(g) + H2(g) The rates of forward and reverse reactions are identical when the equilibrium is reached. The compositions of product and reactant do no change when the reaction mixture is in chemical equilibrium.

y co y H 2 2 = K (T ) yco y H 2 O
Irreversible reaction: 2C2H4 + O2 ===> 2C2H4O

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.
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Instructor: Dr. Azeman Mustafa

SKF 1113 - Material Balances

Equilibrium Composition Example 4.6-2

If the water-gas shift reaction CO(g) + H2O(g) <===> CO2(g) + H2(g) Proceeds to equilibrium at a temperature T(K), the mole fractions of the four reactive species satisfy the relation
y co y H 2
2

yco y H 2 O

= K (T )

where K (T) is the reaction equilibrium constant. At T = 1105 K, K = 1.0 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. Calculate the equilibrium composition and the fractional conversion of the limiting reactant.
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Equilibrium Composition Example 4.6-2

T = 1105 K 1.00 mol CO 2.00 mol H2O

CO H2O CO2 H2

Strategy:

y co y H 2 2 = K ( T ) = 1.0 yco y H 2 O

1. Express all mole fraction in terms of a single variable e (extent of reaction) 2. Substitute e in the equilibrium relation and solve for e. 3. Use e to calculate mole fractions and any other desired quantity.
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SKF 1113 - Material Balances

Equilibrium Composition Example 4.6-2

1. Express all moles and mole fractions in terms e nCO = 1.00 - e yCO = (1.00 - e)/3.00 nH2O = 2.00 - e =====> yH2O = (2.00 - e)/3.00 nCO2 = e yCO2 = e /3.00 nH2 = e _____________ yH2 = e /3.00 ntotal = 3.00 2. Substitute mole fractions from (1) in the equilibrium reaction = 1.00; e = 0.667 (1.00 - e)(2.00 - e) = 0.111; yH2O = 0.444; yCO2 = 0.222; yH2 = 0.222

====> (1)

e2

3. yCO

(a) limiting reactant CO; (b) At equilibrium, nCO = 1.00 - 0.667 = 0.333 Fractional conversion at equilibrium
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= f co =

(1.00 - 0.333) mol reacted 1.00 mol fed

Material Balance

= 0.667
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Multiple Reaction, Yield, Selectivity

Multiple reaction : one or more reaction

Side Reaction : undesired reaction Example :- Production of ethylene (dehydrogenation of ethane) Main reaction C2H6 C2H4 + H2 Side Reactions C2H6 + H2 2CH4 C2H4 + C2H6 C3H6 + CH4 Design Objective Maximize desired products (C2H4) Minimize undesired products (CH4, C3H6)
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SKF 1113 - Material Balances

Multiple Reaction, Yield, Selectivity

Yield (moles of desired product formed) (moles of product formed, assuming no side reactions and the limiting reactant is completely reacted) Selectivity (moles of desired product formed) (moles of undesired product formed)
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Multiple Reaction, Yield, Selectivity

Calculation of molar flow rates for multiple reactions

ni = ni0 +

v
ij j

+ ij if i is a product in reaction j ij if i is a reactant in reaction j v ij = 0 if i does not appear in reaction j

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SKF 1113 - Material Balances

Multiple Reaction, Yield, Selectivity

Test Your Self pg. 125

Consider the following pair of reactions A 2B (desired) A C (undesired) Suppose 100 mol of A is fed to a batch reactor and the final product contains 10 mol of A, 160 mol of B and 10 mol of C. Calculate a) b) c) d) The fractional conversion of A. (f=0.9) The percentage yield of B. ( Y = 80%) The selectivity of B relative to C. (S = 16 mol B/mol C) The extents of the first and second reactions. (80, 10)

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Working Session IV
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 (CO2) and water (H2O) : CH4 + O2 HCHO + H2O CH4 + 2O2 CO2 + 2H2O 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 of formaldehyde is 0.855. Calculate the molar composition of the reactor output stream and the selectivity of formaldehyde production relative to carbon dioxide production.

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SKF 1113 - Material Balances

Solution to Working Session IV

i) Draw a process flow chart
Overall process :- CH4 + 1.5O2 0.5HCHO + 0.5CO2 + 1.5H2O Fractional conversion of methane = 0.9 Fractional yield of formaldehyde = 0.855

100 mol /s 0.5 mol CH4/mol 0.5 mol O2/mol

n1 mol/s CH4 n2 mol/s HCHO n3 mol/s H2O n4 mol/s CO2 n5 mol/s O2

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Solution to Working Session IV

II. Mass balance analysis using the extents of reactions

ni = ni,o + CH 4 bal. H 2 O bal. CO 2 bal. O 2 bal.

v
ij j

n1 = 50 i j n3 = 0 + i + 2 j n4 = 0 + j n5 = 50 i 2 j

.. ( 1 ) .. ( 2 ) .. ( 3 ) .. ( 4 ) ..( 5 )
Material Balance Page 4-32

HCHO bal. n2 = 0 + i

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SKF 1113 - Material Balances

Solution to Working Session IV

Given : CH 4 conversion = 0 .9 , i j = 0 .9( 50 ) = 45

Given : HCHO yield = 0 .855 Moles of HCHO formed if the lim iting reac tan t is reacted complet ely = 50 mol Thus, 0 .855 = i 50 ..... i = 42 .75 mol and j = 2 .25 mol

From eq. 1 , n1 = 50 0 .9( 50 ) = 5 mol/s CH 4 From eq. 2 , n2 = 42 .75 mol/s HC HO From eq. 3 , n3 = 42 .75 + 2( 2 .25 ) = 47 .25 mol/s H 2 O From eq. 4 , n4 = 2 .25 mol/s CO 2 From eq. 5 , n5 = 50 42 .75 2( 2 .25 ) = 2 .75 mol/s O 2
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Solution to Working Session IV

Molar com position of the product stream Total mola r flowrate of product stream = 100 mol/s (WHY same as that of the feed? ) (In a reactive system, must th e molar fl owrate of the input stream equal to that of the output st ream?) y 1 = 0 .05 mol/s CH 4 /mol y 3 = 0 .4725 mol/s H 2 O/mol y 5 = 0 .0275 mol/s O 2 /mol Selectivity of HCHO production relative to CO 2 production => n2 mol HCHO = 19 .0 n4 mol CO 2
Material Balance Page 4-34

y 2 = 0 .4275 mol/s HC HO/mol y 4 = 0 .0225 mol/s CO 2 /mol

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SKF 1113 - Material Balances

Working Session V
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 (CO2) and water (H2O) : CH4 + O2 HCHO + H2O CH4 + 2O2 CO2 + 2H2O Suppose 50 mol/s of methane and 240 mol/s of air (21 mole % O2, 79% N2) are fed to a continuous reactor. The fractional conversion of methane is 0.9 and the fractional yield of formaldehyde is 0.855. Calculate the molar composition of the reactor output stream and the selectivity of formaldehyde production relative to carbon dioxide production.

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