Chapter 2.

2 Mass Balance on Reactive Processes System

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CONTENT

Stoichiometry Limiting and Excess Reactant, Fractional Conversion and Extent of Reaction Chemical Equilibrium Multiple Reaction, Yield and Selectivity Balance on Reactive System
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I. 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
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C4H8 + 6 O2 --------> 4 CO2 + 4 H2O

1. 2. 3.

Test Yourself

1.

1.

Is the stochiometric equation balance? Yes What is stochiometric coefficient for CO2 ; 4 What is stochiometric ratio of H2O to O2 including it unit 4 mol H2O generated/ 6 mol O2 consumed How many lb-moles of O2 reacted to form 400lbmoles CO2 ; 600 lb-moles O2 reacted 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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II. 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. n -n
Fractional Excess feed stoich = n stoich n -n feed stoich11 Percentage Excess = 1% n stoich

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Example
C2H2 + 2H2 ------> C2H6 Inlet condition: 20 kmol/h C2H2 and 50 kmol/h H2 What is limiting reactant and fractional excess? (H2:C2H2) o = 2.5 : 1 (H2:C2H2) stoich = 2 : 1 H2 is excess reactant and C2H2 is66

II. FRACTIONAL CONVERSION

Fractional Conversion (f)

moles reacted Fractional Conversion , f = mole fed moles reacted Percentage Conversion , f = 11 1% mole fed

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II. EXTENT OF REACTION

Extent of Reaction,
ni = nio + vi or ni = nio + vi

ni nio vi

= extent of reaction = moles of species i present in the system after the reaction occurred = moles of species i in the system when the reaction starts. = stoichiometry coefficient for species i in the particular chemical reaction equation #
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Example
N2 + 3H2 ------------> 2NH3 Reactor inlet: 100 mol N2/s; 300 mol H2/s; 1 mol Ar/s If fractional conversion of H2 0.6, calculate extent of reaction and the outlet n = 11 1 1 composition. n = 11 1
H1 N1

n Ar = 1 n NH 1 = 1

Unreacted H2 or H2 outlet= (1-0.6) 300 = # 99 120 mol H2/s

Test Yourself Page 119

2 C2H4 + O2 ------->2 C2H4O The feed to a reactors contains 100kmol C2H4 and 100 kmol O2. a) which is limiting reactant? C2H4 b) Percentage of excess? { (100-50)/50} x 100% = 100% c) O2 out? C2H4 formed? Extent of reaction? 50kmol 100kmol C2H4 50kmol d) if fractional conversion for limiting reactant is 50%, what is outlet # 1010 composition and extent of reaction?

Test Yourself Page 119

2 C2H4 + O2 ------->2 C2H4O The feed to a reactors contains 100kmol C2H4 and 100kmol O2. 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 kmol extent of rxn=40
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Class Discussion Example 4.6-1

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III. CHEMICAL EQUILIBRIUM

For a given set reactive species and reaction condition, two fundamental question might be ask:
1.

2.

What will be the final (equilibrium) composition of the reaction mixture? chemical engineering thermodynamics How long will the system take to reach a specified state short of equilibrium? chemical kinetics reaction proceeds only in a single direction (from reactants to products) #
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Irreversible reaction
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Chemical Equilibrium

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

However the discussion to get the chemical equilibrium point is not covered in this text- learn in chemical engineering thermodynamic
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Class Discussion Example 4.6-2 CO + H2O <----> CO2 + H2 nco = 1- nH2O = 2- n CO2 = nH2 = ntotal = 3 K=yCO2 yH2 / y CO y H2O=1 yY CO2 = /3 yH2 = /3 y CO = (1- )/3 y H2O = (2- )/3

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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. 2.

MULTIPLES REACTION, YIELD & SELECTIVITY

3.

Economic loss Less of desired product is obtained for a given quantity of raw materials 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 1616 #

YIELD

3 definition of yield with different working definition

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 1717 #

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 Example 4.6-3

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BALANCE OF REACTIVE PROCESSES

Balance on reactive process can be solved based on three method:

1.

Atomic Species Balance Extent of Reaction Molecular Species Balance

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1.

1.

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 # 2121 =============================

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
Reactor 100 kmol C2H6/min 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
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Method 1: Atomic Species Balance

100 kmol C2H6

Balanceknol C atomic C (input= output) on 2 n1 kmol C2H6 2 kmol C

1 kmol C2H6 = 1 kmol C2H6 + n2(2)

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

[1]

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

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

=============================
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Method 2: Extent of Reaction

Write extent of reaction for each species

C2H6 : n1 = 100- C2H4 : n2= H2 : 40= Solve for n1 and n2 ( =40)

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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 ============================= 2929 #

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

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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

25 mol A/min

Overall Conversion Reactant input to Process reactant output from Process # 3232 Reactant input to Process

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 Product Reactor Fresh Feed Product Separation composition. Unit

Recycle Purge

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CLASS DISCUSSION EXAMPLE 4.7-2 & 4.7-3

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Balance on Reactive Processes System: COMBUSTION REACTIONS

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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.
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COMBUSTION REACTIONS

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 could be liquefied petroleum gas, which is usually propane or butane.

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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 most combustion reactions. Dry air has the following average molar N2 78.03% Average composition: O2 20.99%
Ar 0.94% CO2 0.03% H2, He, Ne, Kr, Xe 0.01% Molecular Weight = 29.0

COMBUSTION CHEMISTRY

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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 # 3939 same gas that contains water but by

Example: A gas contains 33.3 mole% CO2, 33.3% N2 and 33.3% H2O on wet basis is deemed to have a composition of 50.0 mol% CO2 and 50.0 mol% H2O on dry basis.

It is important to have a grasp of knowledge on the correct technique to calculate these two type of compositions or to convert from dry basis to wet basis or vice versa.
4040 #

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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

EXAMPLE 4.8-1: A stack gas contains 60.0 mole% N2, 15.0% CO2, 10.0% O2 and the balance O2. Calculate the molar composition of the gas on a dry basis.
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

SOLUTION Basis: 100 mol Wet Gas 15.0 mol CO2 4242 10.0 mol O2

60.0 mol N2
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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.
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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 the outlet stream (the if the fuel burned stack gas) Unreacted fuel N2 unless With AIR and Not includes: Unreacted
you are told O2 otherwise H2O and CO2, also CO if the problem statement says so PURE O2

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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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