Material and Energy Balances

Chapter 3

Material Balance-Part 2
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Material Balance Problems With Chemical Reactions

Stoichiometry
Stoichiometry theory of proportions in which chemical species combine with one another. Stoichiometric equation of chemical reaction statement of the relative number of molecules or moles of reactants and products that participate in the reaction.

2 SO2 + O2 ---> 2 SO3

 Stoichiometric ratio ratio of species stoichiometry coefficients in the balanced reaction equation can be used as a conversion factor to calculate the amount of particular reactant (or product) that was consumed (produced). 2 mol SO3 generated 2 mol SO2 consumed 2 mol SO2 consumed 1 mol O2 consumed

C4H8 + 6 O2 --------> 4 CO2 + 4 H2O

1. Is the stochiometric equation balance? Yes 2. What is stochiometric coefficient for CO2 4 3. What is stochiometric ratio of H2O to O2 including it unit 4 mol H2O generated/ 6 mol O2 consumed 4. How many lb-moles of O2 reacted to form 400lb-moles CO2 600 lb-moles O2 reacted 5. 100 mol/min C4H8 fed into reactor and 50% is reacted. At what rate water is formed? 200 mol/min water generated
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Limiting Reactant & Excess Reactant

The reactant that would run out if a reaction proceeded to completion is called the limiting reactant, and the other reactants are termed excess reactants. A reactant is limiting if it is present in less than its stoichiometric proportion relative to every other reactant. If all reactants are present in stoichiometric proportion, then no reactant is limiting.
Fractional Excess n
feed

-n

stoich

n n

stoich

Percentage Excess

feed

-n

stoich

100%
5

stoich

C2H2 + 2H2 ------> C2H6 Inlet condition: 20 kmol/h C2H2 and 50 kmol/h H2 What is limiting reactant and fractional excess? (H2:C2H2) feed = 2.5 : 1 (H2:C2H2) stoich = 2 : 1 H2 is excess reactant and C2H2 is limiting reactant Fractional excess of H2 n - n stoich Fractional Excess feed n stoich n (stoich)= 40 n (feed)= 50 = (50-40)/40 =0.25

Fractional Conversion
Chemical reactions do not take place instantaneously. In normal operation, there always will be the unconverted reactant. To calculate the conversion of a chemical reaction;

moles reacted Fractional Conversion, f mole fed moles reacted Percentage Conversion, f 100% mole fed
The fraction unreacted is 1-f.
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Extent of Reaction
Extent of Reaction,

ni nio v i or i n io v i n

ni nio vi

= extent of reaction (amount of species react) = moles of species i present in the system after the reaction occurred = initial moles of species i in system when the reaction starts = stoichiometric coefficient for species i in the particular chemical reaction equation. (-ve for reactants, +ve for products. 8

Considering C2H2 + 2H2 ------> C2H6 , suppose 20 kmol of C2H2, 50 kmol H2 and 50 kmol C2H6 are charged to the batch reactor to form C2H6. After sometimes 30 kmol of H2 has reacted. How much of each species will be present in the reactor at this moment? H2 left = 50 - 30 kmol= 20 kmol H2
30 kmol H2 react => 15 kmol C2H2 C2H2 left= 20 15 kmol = 5 kmol C2H2 30 kmol H2 react from 15 kmol C2H6 C2H6 in the reactor = 15 + 50 kmol = 65 kmol C2H6
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N2 + 3H2 ------------> 2NH3 Reactor inlet: 100 mol N2/s; 300 mol H2/s; 1 mol Ar/s. If fractional conversion of H2 is 0.6, calculate extent of reaction and the outlet composition.

n H 2 300 3 n N 2 100 n Ar 1 n NH 3 2
From fractional conversion, moles of species H2 present in the system after the reaction occurred nH2 = (1-0.6) 300 = 120 mol H2/s Extent of reaction = (300-120)/3= 60 mol/s nN2 = 100- 60= 40 mol/s nNH3 = 2(60)= 120 mol/s
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Try This
2 C2H4 + O2 ------->2 C2H4O The feed to a reactors contains 100kmol C2H4 and 100kmol O2. a) Which is limiting reactant? C2H4 b) Percentage of excess? [(100-50)/50 ]x100%=100% c) O2 out? C2H4 formed? Extent of reaction? 50kmol, 100kmol C2H4, 50kmol
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d) If fractional conversion for limiting reactant is 50%, what is outlet composition and extent of reaction? 50kmol C2H4, 75 kmol O2, 50 kmol C2H4O extent of reaction = 25 kmol e) If reaction proceed to a point where 60kmol O2 left, what is fractional conversion for C2H4, fractional conversion of O2 and extent of reaction? fC2H4=0.8, fO2=0.4, extent of reaction=40 kmol

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Try This
Acrylnitrile is produced in the reaction of production of propylene, ammonia and oxygen: C3H6 + NH3 + 3/2O2 -> C3H3N + 3H2O The feed contains 10.0 mole% propylene, 12.0mole% ammonia and 78 mole% air. A fractional conversion of 30.0% of the limiting reactant is achieved. Taking 100 mol of feed as a basis, determine which reactant is limiting, the percentage by which each of the other reactant is excess, and the molar amounts of all product gas constituents for 30% conversion of the limiting reactant.
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Extent of Reaction for Multiple Reaction

Concept of extent of reaction can also be applied for multiple reaction. Only now each independent reaction has its own extent.

ni nio vi j
j ij

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CLASS DISCUSSION for Example 4.6-3

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Chemical Equilibrium
2 fundamental questions might be ask for a give set reactive species and reaction condition, : 1.What will be the final (equilibrium) composition of the reaction mixture? chemical engineering thermodynamics 2.How long will the system take to reach a specified state short of equilibrium? chemical kinetics

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 Irreversible reaction reaction proceeds only in a single direction (from reactants to products) the concentration of the limiting reactant eventually approaches zero. Reversible reaction reactants form products for forward reaction and products undergo the reverse reactions to reform the reactants. Equilibrium point is a rate of forward reaction and reverse reaction are equal
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CLASS DISCUSSION for Example 4.6-2

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 Some of the chemical reaction has a side reaction which is formed undesired product- multiple reaction occurred. Effects of this side reaction might be: 1. Economic loss 2. Less of desired product is obtained for a given quantity of raw materials 3. Greater quantity of raw materials must be fed to the reactor to obtain a specified product yield.
selectivity =
moles of desired product moles of undesired product
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Multiples Reaction, Yield & Selectivity

Yield
3 definitions of yield with different definitions:
Moles of desired product formed Yield = Moles that would have been formed if there were no side reaction and the limiting reactant had reacted completely

Yield

Moles of desired product formed

Moles of reactant fed

Yield

Moles of desired product formed Moles of reactant consumed

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Balance of Reactive Processes

Balance on reactive process can be solved based on 3 methods: 1. Atomic Species Balance 2. Extent of Reaction 3. Molecular Species Balance

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Atomic Species Balance

No. of unknowns variables - No. of independent atomic species balance - No. of molecular balance on indep. nonreactive species - No. of other equation relating the variable ============================= No. of degree of freedom =============================

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Extent of Reaction
No. of unknowns variables + No. of independent chemical reaction - No. of independent reactive species - No. of independent nonreactive species - No. of other equation relating the variable ============================= No. of degree of freedom =============================

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Molecular Species Balance

No. of unknowns variables + No. of independent chemical reaction - No. of independent molecular species balance - No. of other equation relating the variable ============================= No. of degree of freedom =============================

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Degree-of-Freedom Analysis

Independent Equation Independent Species Independent Reaction

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Independent Equation
Algebraic equation are independent if we cannot obtain any one of them by adding and subtracting multiples of any of the others x + 2y = 4 [1] 3x + 6y = 12 [2] Only one independent equation because [2]= 3 x [1] x + 2y = 4 [1] 2x z= 2 [2] 4y + z= 6 [3] Although 3 equations, but only two independent equation exist because [3]=2x[1] [2]

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Independent Species
If two MOLECULAR species are in the SAME RATIO to each other wherever they appear in a process, balance on those species will not be independent (i.e. only one independent equation is obtained)

Similarly
If two ATOMIC species are in the SAME RATIO to each other wherever they appear in a process, balance on those species will not be independent (i.e. only one independent equation is get)

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Independent Molecular Speciescont.

If two MOLECULAR species are in the SAME RATIO to each other wherever they appear in a process, balance on those species will not be independent (i.e. only one independent equation is obtained)
n3 mol O2 n1 mol O2 3.76 n1 mol N2 3.76 n3 mol N2 n4 mol CCl4(v)

n2 mol CCl4(l)

Process Unit

n5 mol CCl4(l)

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Independent Molecular Species-cont.

Since N2 and O2 have a same ratio wherever they appear on the flowchart (3.76 mol N2 / mol O2), only ONE independent balance can obtain. Let make a molecular balance on both species to prove it Balance on O2 : n1=n3 [1] Balance on N2 : 3.76 n1=3.76n3 n1=n3 [2] Eq. [1] and [2] are SAME. Only ONE INDEPENDENT EQUATION OBTAINED although two species involved.

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Independent Atomic Species

If two ATOMIC species are in the SAME RATIO to each other wherever they appear in a process, balance on those species will not be independent (i.e. only one independent equation is get)

n3 mol O2 n1 mol O2 3.76 n1 mol N2 n2 mol CCl4(l)

3.76 n3 mol N2
n4 mol CCl4(v)

Process Unit

n5 mol CCl4(l)

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Independent Atomic Species-cont.

Atomic N and O are always in same proportion to each other in the process (3.76:1), similar for atom C and Cl which always same ratio too (1:4). Although FOUR atomic species exist, only TWO independent equation can obtain for this cases.

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 Prove: Balance on atomic O: Balance on atomic N: Balance on atomic C:

2n1=2n3 n1=n3 [1] 2(3.76)n1=2(3.76)n3 n1=n3 [2] n2=n4+n5 [3]

Balance on atomic Cl: 4n2=4n4 +4n5 n2=n4+n5 [4] Eq. [1]=[2] and [3]=[4], only TWO independent equation obtained

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Independent Reaction
Used when we using either molecular species balance or extent of reaction method to analyze a balance on reactive process Chemical reaction are independent if the stoichiometric equation of any one of them cannot be obtained by adding and subtracting multiples of the stoichiometric equations of the others A ------> 2B [1] B ------> C [2] A ------> 2C [3] Only TWO independent eqn. can obtained although three equation exist since [3]=[1] + 2[2].

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Balance of Reactive Processes

Balance on reactive process can be solved based on 3 methods:

1.Atomic Species Balance 2.Extent of Reaction 3.Molecular Species Balance [arrange according to the easiest method(1) to more difficult method(2), but not always true]

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Atomic Species Balance

No. of unknowns variables No. of independent atomic species balance No. of molecular balance on indep. nonreactive species No. of other equation relating the variable ============================= No. of degree of freedom =============================

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Extent of Reaction
No. of unknowns variables

+ -

No. of independent chemical reaction No. of independent reactive species No. of independent nonreactive species No. of other equation relating the variable ============================= No. of degree of freedom =============================

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Molecular Species Balance

No. of unknowns variables

+ -

No. of independent chemical reaction No. of independent molecular species balance No. of other equation relating the variable ============================= No. of degree of freedom =============================

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Application of Method
C2H6 -------> C2H4 + H2

100 kmol C2H6/min

Reactor

40 kmol H2/min n1 kmol C2H6/min n2 kmol C2H4/min

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Method 1: Atomic Species Balance

All atomic balance is INPUT=OUTPUT Degree-of-freedom analysis 2 unknowns variables (n1, n2) - 2 independent atomic species balance (C, H) - 0 molecular balance on indep. nonreactive species - 0 other equation relating the variable ============================= 0 No. of degree of freedom =============================

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Method 1: Atomic Species Balance

Balance on atomic C (input= output)
100 kmol C2H6 2 knol C 1 kmol C2H6 = n1 kmol C2H6 2 kmol C 1 kmol C2H6 + n2(2 )

200=2n1 + 2n2 100=n1 + n2

Balance on atomic H (input = output) 100(6)=40(2) + 6n1+4n2 520 = 6n1 + 4n2 [2]

[1]

Solve simultaneous equation,

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Method 2: Extent of Reaction

Degree-of-freedom analysis 2 unknowns variables (n1,n2) + 1 independent chemical reaction 3 independent reactive species (C2H6, C2H4, H2) 0 independent nonreactive species 0 other equation relating the variable ============================ = 0 No. of degree of freedom 41 ============================

Method 2: Extent of Reaction

Write extent of reaction for each species C2H6 : C2H4 : H2 n1 = 100- n2= 40=

Solve for n1 and n2 ( =40) n1= 60 kmol C2H6/min; n2= 40 kmol C2H4/min
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Method 3: Molecular Species Balance

Degree-of-freedom analysis
2 unknowns variables (n1, n2) +1 independent chemical reaction - 3 independent molecular species balance (C2H6, C2H4, H2) - 0 other equation relating the variable ============================= 0 No. of degree of freedom =============================

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Method 3: Molecular Species Balance

H2 balance (Gen=Output): H2 Gen= 40 kmol H2/min C2H6 Balance (input=output + cons.): 100 kmol C2H6/min = n1 kmol C2H6/min + 40 kmol H2 gen X (1 kmol C2H4 gen/1 kmol H2 gen) n1= 60 kmol C2H6/min

C2H4 balance (Gen.=Ouput): 40 kmol H2 gen x (1 kmol C2H4 gen./ 1 kmol H2 gen) = n2 n2= 40 kmol C2H4/min

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CLASS DISCUSSION EXAMPLE 4.7-1

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Product Separation & Recycle

75 mol A/min 100 mol A/min

Reactor

25 mol A/min 75 mol B/min

Product Separation Unit

75 mol B/min

Overall Conversion 25 mol A/min Reactant input to Process reactant output from Process Reactant input to Process Single Pass Conversion Reactant input to Reactor reactant output from Reactor Reactant input to Reactor

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Purging
To prevent any inert or insoluble substance build up and accumulate in the system Purge stream and recycle stream before and after the purge have a same composition.
Fresh Feed

Reactor

Product Separation Unit

Product

Recycle

Purge

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CLASS DISCUSSION EXAMPLE 4.7-2

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CLASS DISCUSSION EXAMPLE 4.7-3

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COMBUSTION REACTIONS
Combustion Rapid reaction of a fuel with oxygen. This reaction releases tremendous quantities of energy that can be manipulated to boil water to produce steam. Combustion releases products such as CO, CO2 and SO2 and as chemical engineers, we are tasked to monitor and analyze the production of these noxious gases. Combustion fuels could be coal (carbon, some hydrogen, and sulfur and various noncombustible materials), fuel oil (mostly high molecular weight hydrocarbons, some sulfur), gaseous fuel (such as natural gas, which is primarily methane) or it 50 could be liquefied petroleum gas, which is usually

Combustion Chemistry
From Fuel Perspective Fuel contains carbonaceous material that will form either CO2 or CO, Hydrogen forming H2O and Sulfur forming SO2. From O2 Source Perspective For economic reason, AIR is the source of oxygen in N2 78.03% most combustion reactions. Dry air has the following O2 20.99% Average Molecular average molar composition: 0.94% Ar Weight = 29.0
CO2 H2, He, Ne, Kr, Xe 0.03% 0.01%

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 However, in most combustion calculations, it is acceptable to simplify this composition to 79% N2, 21% O2 For combustion reaction, generally we have TWO type of expressions to express the mole composition of a gas, that is Composition On A Wet Basis and Composition On A Dry Basis. Composition On A Wet Basis is commonly used to denote mole fractions of a gas that contains water. Composition On A Dry Basis can also be used to denote mole fractions of the same gas that contains water but by excluding the presence of water in the calculation. Example: A gas contains 33.3 mole% CO2, 33.3% N2 and 52 33.3% H2O on wet basis is deemed to have a

 The MAIN REASON is whenever flow rate of a product gas leaving the stack (stack gas or flue gas refers to product gas that leaves a combustion furnace) is measured, the measurement is for the total flow rate that also involved the product H2O, while on the other hand, common techniques for analyzing stack gases provide compositions on a dry basis. The procedure to convert Dry Basis to Wet Basis or vice versa follows exactly the same procedure outlined earlier on for converting Mass Compositions to Mole Compositions or vice versa in previous chapter.
EXAMPLE 4.8-1: A stack gas contains 60.0 mole% N2, 15.0% CO2,53 10.0% O2 and the balance O2. Calculate the

SOLUTION Basis: 100 mol Wet Gas

60.0/85.0 = 0.706 mol N2/mol DG 15.0/85.0 = 0.176 mol CO2/mol DG 10.0/85.0 = 0.118 mol O2/mol DG

60.0 mol N2 15.0 mol CO2 10.0 mol O2 85.0 mol dry gas (DG)

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Theoretical and Excess Air

Theoretical Oxygen: The moles (batch process) or molar flow rate (continuous process) of O2 needed for complete combustion of all the fuel fed to the reactor, assuming that all the carbon in the fuel is oxidized to CO2 and all the hydrogen is oxidized to H2O. Theoretical Air: The quantity of air that contains the theoretical oxygen. Excess Air: The amount by which the air fed to the reactor exceeds the theoretical air. moles air fed moles air theoretical Percent Excess Air:

moles air

100%

theoretical

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TEST YOURSELF PAGE 146

56

Material Balances on Combustion Process

The procedure for writing and solving material balances for a combustion reactor is the same as that for any other reactive system. However, be extra cautious with these: When you draw and label flow chart, be sure that Unreacted fuel unless N2 if the fuel burned Unreacted O 2 the outlet stream (the stack gas) includes: you are told otherwise With AIR and Not PURE
O2 H2O and CO2, also CO if the problem statement says so
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 To calculate the O2 feed rate from a specified percent oxygen excess, first is to calculate the theoretical O2 from the fuel feed rate and the reaction stoichiometry for COMPLETE COMBUSTION, then calculate the oxygen feed rate by multiplying the theoretical O2 by (1+fractional excess of O2). Atomic balances are usually most convenient for use in the calculation.

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EXAMPLE 4.8-3

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