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By : Kishan

Inti International University

CONSERVATION OF MASS

Mass is neither created nor destroyed

9

3 5

Reactor

10

11

1

Distillation 4

2

12 13

6 Heat 8

Seperator

Exchanger

14

7

{Input} + {Genn} - {Consumption} – {Output} = {Accumulation}

2

SYSTEMS

Systems

OPEN or CLOSED

Any arbitrary portion of or a whole process that you

want to consider for analysis

Reactor, the cell, mitochondria, human body, section of a

pipe

Closed System

Material neither enters nor leaves the system

Changes can take place inside the system

Open System

Material can enter through the boundaries

3

STEADY-STATE Steady-State Nothing is changing with time @ steady-state accumulation = 0 500 kg 100 kg/min 100 kg/min H2O H2O H2O Rate of addition = Rate of removal Unsteady-State (transient system) {Input} ≠ {Output} 4 .

PROCESSES Batch Process Feed is fed at the beginning of the process Continuous Process The input and outputs flow continuously throughout the duration of proces Semibatch Process Any process neither batch nor continuous 5 .

BALANCES ON CONTINUOUS STEADY-STATE PROCESSES Input + Generation = Output + Consumption If the balance is on a nonreactive species. Thus. the generation and consumption will be 0. B: the mass flow rate of top stream=450 kg/h T: the mass flow rate of bottom stream=475 kg/h m1 kg Toluene/h 450 kg Benzene/h 1000 kg /h Benzene + Toluene Distillation %50 Benzene by mass 475 kg Toluene/h M2 kg Benzene/h 6 . Input = Output Example Input of 1000 kg/h of benzene+toluene containing 50% B by mass is separated by distillation column into two fractions.

BALANCES ON CONTINUOUS STEADY-STATE PROCESSES Solution of the example Input = Output Benzene balance . m2 = 50 kg/h Benzene Toluene balance 1000 kg/h · 0. m1 = 25 kg/h Toluene 7 . 1000 kg/h · 0.5 = 450 kg/h + m2 . .5 = 475 kg/h + m1 .

yF = D.BALANCES ON BATCH PROCESSES Initial Input + Generation = Final Output + Consumption Objective: generate as many independent equations as the number of unknowns in the problem D F=B+D F.xB (W+A) x: mole fraction of W B y: mole fraction of A 8 .xF = D.xB F F.xD + B.yD + B.

and the product stream contains 50 wt% cells. Assume that the feed has a density of 1 g/cm3.EXAMPLE (BATCH PROCESS) Centrifuges are used to seperate particles in the range of 0. Determine the amount of the cell-free discharge per hour if 1000 L/hr is fed to the centrifuge. Yeast cells are recovered from a broth ( a mix with cells) using tubular centrifuge.1 to 100 µm in diameter from a liquid using centrifugal force. the feed contains 500 mg cells/L. Feed (broth) 1000 L/hr Concantrated cells P(g/hr) Centrifuge 500 mg cells/L feed 50 % by weight cells ( d= 1 g/cm3) Cell-free discahrge D(g/hr) 9 .

. .5 g cells 1000 L feed . the feed contains 500 mg cells/L. Assume that the feed has a density of 1 g/cm3.5 = 500 g/h fluid Output 2: D(g/h) = (106 – 500)g/h – 500 g/h = (106 -103)g/h fluid 10 . Determine the amount of the cell-free discharge per hour if 1000 L/hr is fed to the centrifuge. 0.1 to 100 µm in diameter from a liquid using centrifugal force. EXAMPLE (Batch Process) Centrifuges are used to seperate particles in the range of 0. and the product stream contains 50 wt% cells. Feed (broth) 1000 L/hr Concantrated cells P(g/hr) Centrifuge 500 mg cells/L feed 50 % by weight cells (d= 1 g/cm3) Cell-free discharge D(g/hr) Cell balance 500 mg cells 1g 0. P[g/hr] 1 L feed 1000 mg 1gP P 1000 g/hr Fluid balance L 1g 10cm 3 1dm 3 6 g Input: (10 – 500) g/h fluid 6 1000 ( ) 10 h cm3 1dm L h Output 1: 1000g/h . Yeast cells are recovered from a broth ( a mix with cells) using tubular centrifuge.

Write the values and units of all known streams Assign algebraic symbols to unknown stream variables 100 mol C3H8 Combustion 50 mol C3H8 Condenser Chamber 750 mol O2 1000 mol O2 3760 mol N2 3760 mol N2 150 mol CO2 200 mol H2O 11 . FLOW CHARTS Boxes and other symbols are used to represent process units.

015 mol H2O/mol C y mol O2/mol (0.EXAMPLE (FLOW CHARTS) Humidification and Oxygenation Process in the Body: An exp. on the growth rate of certain organisms requires an environment of humid air enriched in oxygen.79 mol N2/mol . Three input streams are fed into an evaporator to produce an output stream with the desired composition. B: Air. A: liquid water. fed at a rate of 20 cm3/min.21 mol O2/mol 0.985 – y ) mol N2/mol .n2 mol H2O/min 20 cm3 H2O /min 12 .n1 mol air/min B A 0.n3 mol/min 0. .2 n1 mol O2/min 0. C: Pure oxygen (with a molar flow rate one-fifth of the molar flow rate of stream B) .

EXAMPLE (FLOW CHART) n2 = 20 cm3 H2O/min .8 mol/min N2 Balance n1 mol/min . 1 g H2O/cm3 . (0.79 mol N2/mol = n3 mol/min .1 mol/min Total Mole Balance 0.015 mol H2O/mol n3 = 74.02 g n2 = 1.985-y) mol N2/mol y = 0. 0. 0.337 mol O2/mol 13 .11 mol H2O/min H2O Balance n2 mol H2O/min = n3 mol/min . 1 mol/18.2 n1 + n1 + n2 = n3 n1 = 60.

FLOWCHART SCALING n1 n3 A n2 Scale factor: 100 100 n1 100 n3 A 100 n2 CHBI 201 14 .

Physical constraints 15 .DEGREE OF FREEDOM ANALYSIS (df) ndf = nunknowns – nindep. Physical props&laws. Energy balances. Process specificaitons.eqn’s If ndf = 0 Problem can be solved (determined) If ndf > 0 Unknowns > knowns (underspecified) If ndf < 0 overspecified (no solution) Material balances.

225 L/h 7 unknowns (n0 -> n6) 7 equations needed 3 independent material balance n3 = ρ. Example ρH20 is given Humid air Condenser Dry air (n4) O2 In the (n0) O2 (n5) N2 condenser. kg) Do not make mole balances in reactive processes. (n1) N2 95% of H2O (n6) H2O (n2) H2O in the inlet air is (n3) H2O condensed.V n0/n1 = 21/79 n3 = 0.95 n2 One more equation is needed Volume is not conserved! Use consistent units (mole. 16 .

Nsp = number of species System boundary Ns = number of streams Nu = total number of variables H2O NaOH M Product 17 .9. Determine the composition and flow rate of the product.EXAMPLE 2 A continuous mixer mixes NaOH with H2O to produce an aqueous solution of NaOH. if the flow rate of NaOH is 1000 kg/hr and the ratio of the flow rate of H2O to the product solution is 0.

etc. flow rate. T. P. V.continue Streams FEED WATER PRODUCT Species NaOH FNaOH WNaOH PNaOH Nu = 3(2+1) = 9 H2O FH2O WH2O PH2O Last row in the table Total F W P Specifications: ratio of two streams the % conversion in a reaction the value of each concentration.it is 0 18 . hence .EXAMPLE 2 . ρ. a variable is not present in a stream.

and N2 has to be prepared containing a CH4 to C2H6 mole ratio of 1.EXAMPLE 3 A cylinder containing CH4.5 to 1. C2H6. Avaliable to prepare the mixture are 1) a cylinder containing a mixture of 80% N2 and 20% CH4 2) a cylinder containing a mixture of 90% N2 and 10% C2H6 3) a cylinder containing a mixture of pure N2 What is the number of degrees of freedom? 19 .

8 N2 1 C2H6 xC2H6 F2 C2H6 0.EXAMPLE 3 .9 Unknowns: 3 xi and 4 Fi 20 .2 F3 N2 xN2 N2 0.continue F4 F1 CH4 xCH4 CH4 0.1 N2 0.

C2H6. N2) One specified ratio xCH4/xC2H6 = 1.continue Equations: Material balance (CH4.EXAMPLE 3 . CHBI 201 21 .5 One summation of mole fractions 5 independent equations x 1 for F i 4 Ndf = 7 – 5 = 2 If you pick a basis as F4=1. one other value has to be specified in order to solve the problem.

5 kg B/kg 30 kg/hr 4 0.9 kg A/kg 0.6 kg A/kg 0.7 kg B/kg 22 .5 kg A/kg 0. Balances on Multiple-unit Processes 40 kg/hr 30 kg/hr 0.4 kg B/kg Q1 Q2 1 3 x1 x2 Q3 100 kg/hr 2 x3 0.3 kg A/kg 0.1 kg B/kg 0.

(0.(0.(x1) x1 = 0.5) = 40.256 30 + Q3 = Q2 Q3 = 60 kg/hr x3 = 0.083 3 CHBI 201 23 . Balances on Multiple-unit Processes Q : mass flow rate You should treat any xA : mass fraction of A 1-xA : mass fraction of B junction as a process unit! Number of unknowns = 6 Number of equations = 2+2+2 = 6 Therefore.9) + 60.233 1 30 + Q1 = Q2 Q2 = 90 kg/hr 2 x2 = 0. solution exists 100 = 40 + Q1 Q1 = 60 kg/hr 100.

CHBI 201 24 .

Its efficiency is never 100. Feed Product Feed Process rxn Sep. this process is called bypass. If a fraction of the feed to a process unit is diverted around the unit and combined with the output stream. Some A in the product ! To find a way to send the “A” back to feed you need a seperation and recycle equipment. Unit Recycle Bypass stream 25 .RECYCLE & BYPASS STREAM It is rare that a chemical reaction A B proceeds to completion in a reactor. this would decrease the cost of purchasing more A.

7 mole% H2O. Take 100 mole of dehumidified air delivered to the room. In the air conditioner some of the water is removed as liquid. water condensed.EXAMPLE Feed: Fresh air with 4 mole% H2O(v) is “cooled” and “dehumidified” to a water content of 1. The blended stream entering unit contains 2. calculate moles of feed. dehumidified air recycled. Fresh air is combined with a recycle stream of dehumidified air. 26 .3 mole% H2O.

96 DA 0.continue n5 (mol) 0.977 DA 0.983 DA.983 DA 0.017 W(v) n3 mole W(ℓ) n2 (mol) 0. 0.023 W(v) 27 .04 W CONDITIONER 0.017 W 0.017 W n1 (mol) AIR n4 (mol) 100 mol 0. EXAMPLE .983 DA 0.

continue Overall system: 2 variables (n1. n5) Do not use SP in the solution 1 balance equation Degree of freedom = 1 28 . n3) 2 balance equations (two species) Degree of freedom = 0 (n1. n4) 2 balance equations (two species) Degree of freedom = 0 Splitting point: 2 variables (n4. n3) are determined!!! Mixing point: 2 variables (n2. EXAMPLE . n5) 2 balance equations (two species) Degree of freedom = 0 Cooler: 2 variables (n2.

EXAMPLE .continue Overall DA balance: 0.5 mol n5 = 290 mol recycled 29 .4 mol H2O condensed Mole balance on Mixing point: n1 + n5 = n2 Water blance on Mixing point: 0.983 (100) n1 = 102.96 n1 = 0.04n1 + 0.017n5 = 0.023n2 n2 = 392.4 mol fresh feed Overall mole balance: n1 = n3 + 100 n3 = 2.

1 and 2 are stoichiometric coefficients of a reaction 30 .CHEMICAL REACTION STOICHIOMETRY If there is a chemical reaction in a process More complications The stoichiometric ratios of the chemical reactions Constraints The stoichiometric equation 2SO2 + O2 2SO3 2 molecules of SO2 reacts with 1 molecule of O2 and yields 2 molecules of SO3 2.

(n ) ] Fractional excess of A A feed A stoich (n ) A stoich.LIMITING & EXCESS REACTANTS If the reactants are not in stoichiometric proportion one of them will be excess. the other will be limiting [ (n ) . moles reacted Fractional conversion of A moles fed n -n Extend of reaction () i i0 ν i 31 .

EXAMPLE C3H6 + NH3 + 3/2 O2 C3H3N + 3 H2O Feed: 10 mol % of C3H6. 12 mole % NH3 and 78 mole % air A fractional converison of limiting reactant = 30% Taking 100 mol of feed as a basis. and molar amounts of all product gas constituents for a 30% conversion of the limiting reactant. 100 mol nC3H6 0.79 mol N2/mol air nH2O 32 .12 mol NH3/mol 0.1 mol C3H6/mol nNH3 REACTOR nO2 0.21 mol O2/mol air nC3H3N 0.78 mol air/mol nN2 0. determine which reactant is limiting.

(ζ)= 11.5) (nNH3)stoich.EXAMPLE – continue Feed: nC3H6= 10 mole nNH3=12 mole nO2= 78.4 mole nNH3/nC3H6= 12/10 = 1.= 15 mole (% excess)NH3 = (12-10) /10 x 100 = 20% excess NH3 Moles reacted Moles fed (% excess)O2 = (16. 1.64 O2 is excess (stoich.4 – 1.(ζ) = 9 mole nN2= (nN2)0=61. ξ) nNH3 = 12.9 nC3H3N= ζ = 3 mole nH2O=3.(0.4-15) /15 x 100 = 9. 1) nO2/nC3H6= 16.3% excess O2 (nC3H6)out=0.6 mole 33 .4/10 = 1.1.21) =16.5.= 10 mole (nO2)stoich.7 x (nC3H6)0= 7 mole C3H6 (since the fractional conversion of C3H6 is 30%) Extent of reaction = ζ = 3 mole (since ni = ni0 + i ξ => 7= 10 .2 NH3 is excess (stoich.ζ =9 mole nO2=16.

CHEMICAL EQUILIBRIUM If you are given a set of reactive species and reaction conditions. a) What will be the final (equilibrium) composition of the reaction mixture? b) How long will the system take to reach a specified state short of equilibrium? Chemical equilibrium thermodynamics & Chemical Kinetics A reaction can be )Reversible )Irreversible CHBI 201 34 .

EXAMPLE CO (g) + H2O (g) CO2 (g) + H2 (g) Given @ T=1105 K. Equilibrium constant. K=1 nCO= 1 mol. nH2O= 2mol. K(T) = yCO2 y H 2 yCO y H 2O 35 . initially no CO2 and H2 Calculate the equilibrium composition and the fractional converison of the limiting reactant.

222 Limiting reactant is CO. nH2 = ζe yCO = (1-ζe)/3 yH2O = (2-ζe)/3 yCO2 = ζe /3 yH2 = ζe /3 K(T) = (ζe)2 / (1-ζe) (2-ζe) = 1 ζe = 0. nCO = 1-0.667 = 0. nCO2 = ζe .EXAMPLE – continue nCO = 1-ζe .667 mole yCO = 0.667 36 .333 Fractional conversion = (1-0.333) / 1 mol feed = 0.111 yH2O = 0.222 yH2 = 0.444 yCO2 = 0. nH2O = 2-ζe .

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