Material and Energy Balances

Chapter 3

Material Balance-Part 1

This chapter will present the methods for organizing known information about process variables, setting up a material balance equations for individual process units and multiple-unit processes and solving the equations for unknown variables.

What are in this chapter?

Material Balance Process classification Material Balances Problems with Chemical reaction Balances on Multiple-Unit Process Recycle and Bypass

Balances
Material balance calculations Material Balance Problems without Chemical reaction

Topic Outcomes
At the end of Chapter 3, you should:
Briefly and clearly describe batch process, semibatch, continuous, transient. Briefly and cearly describe recycle, purge, degree-of-freedom, fractional conversion of a limiting reactant, percentage excess of reactant, yield and selectivitiy, dry and wet basis compositions, theoretical air and also percent excess air in a combustion reaction.

Topic Outcomes-cont.
At the end of Chapter 3, you should:
Draw and fully label a flowchart representing a chemical process (single unit or multiple unit), choose a convenient basis, perform a degree-offreedom analysis, write in order the equations to be used to calculate specified process variables and subsequently solving for material balances. Calculate the feed rate of air from a given percent excess of air given a combustion reactor and information about the fuel composition.

Topic Outcomes-cont.
At the end of Chapter 3, you should:
Calculate the flow rate and composition of the poduct gas given information about the conversion of the fuel and the absence or presence of CO in the product gas.

Process Classification
3 type of chemical processes; 1. Batch process Feed is charge to the process and product is removed when the process is completed No mass is fed or removed from the process during the operation Used for small scale production Operate in unsteady state

2. Continuous process Input and output is continuously red and remove from the process Operate in steady state Used for large scale production 3. Semibatch process Neither batch nor continuous During the process a part of reactant can be fed or a part of product can be removed.

2 type of process operations; 1. Steady state All the variables (i.e. temperatures, pressure, volume, flow rate, etc) do not change with time Minor fluctuation can be acceptable 2. Unsteady state or transient Process variable change with time

Try This
Define type and operation of processes given: A balloon is filled with air at steady rate of 2 g/min Semibatch and unsteady state A bottle of milk is taken from the refrigerator and left on the kitchen Batch and unsteady state Water is boiled in open flask Semibatch and unsteady state

Balances
General Balance Equation
A balance on a conserved quantity (total mass, mass of a particular species, energy, momentum) in a system ( a single process unit, a collection of units, or an entire process) may be written as: INPUT + GENERATION OUTPUT CONSUMPTION = ACCUMULATION

IN GROUP DISCUSSION
Eq. (4.2-1) from pg 85 [INPUT + GENERATION OUTPUT CONSUMPTION = ACCUMULATION] See Example 4.2-1

Differential vs. Integral Balances

2 types of balances: 1. Differential balances balances that indicate what is happening in a system at an instant time. balance equation is a rate (rate of input, rate of generation, etc.) and has units of the balanced quantity unit divided by a time unit (people/yr, g SO2/s). usually applied to a continuous process.

2. Integral balances Balances that describe what happens between two instants of time. balance equation is an amount of the balanced quantity and has the corresponding unit (people, g SO2). usually applied to a batch process, with the two instants of time being the moment after the input takes place and the moment before the product is withdrawn.

Simplified Rules for Material Balance Equation:

If the balanced quantity is TOTAL MASS, set generation = 0 and consumption = 0. Mass can neither be created nor destroy. If the balanced substances is a NONREACTIVE SPECIES (neither a reactant nor a product), set generation = 0 and consumption = 0. If a system is at STEADY STATE, set accumulation = 0, regardless of what is being balanced.

Balances on Continuous Steady-State Process

Steady state; accumulation = 0 INPUT + GENERATION = OUTPUT + CONSUMPTION

If balance on nonreactive species or on total mass; generation = 0, accumulation = 0

INPUT = OUTPUT

Balances on Batch Process

Ammonia is produced from nitrogen and hydrogen in a batch reactor. At time t = 0 there are n0 mol of NH3 in the reactor, and at a later time tf the reaction terminates and the contents of the reactor, which include nf ammonia, are withdrawn. Between t0 and tf no ammonia enters or leaves through the reactor boundaries. From GBE; input=0 and output=0 GENERATION CONSUMPTION = ACCUMULATION For batch reactor: ACCUMULATION= INITIAL INPUT FINAL OUTPUT

Final General Balance Equation for batch processes: INITIAL INPUT + GENERATION = FINAL OUTPUT CONSUMPTION

Material Balance Calculation

In material balances problems, equations involving input and output stream variables are derived. Solving the equations is simple, but deriving them from a description of process is considered tricky. Hence, procedure to derive a set of equations that can be solved for unknown variables will be outlined.

Flowcharts
When you are given process information and asked to determine something about the process, it is essential to organize the information in a way that is convenient for subsequent calculations. The best way to do this is to draw a flowchart using boxes or other symbols to represent process units (reactors, mixers, separation units, etc.) lines with arrows to represent inputs and outputs.

Flowcharts-continue
The flowchart of a process can help get material balance calculations started and keep them moving. Flowchart must be fully labeled when it is first drawn, with values of known process variables and symbols for unknown variables being written for each input and output stream. Flowchart will functions as a scoreboard for the problem solution: as each unknown variable is determined its value is filled in, so that the flowchart provides a continuous record of where the solution stands and what must still be done.

Labeling a flowchart
2 suggestions for labeling flowchart: 1. Write the values and units of all known stream variables at the locations of the streams on the flowchart. For example, a stream containing 21 mole% O2 and 79% N2 at 320C and 1.4 atm flowing at a rate of 400 mol/h might be labeled as:
400 mol/h 0.21 mol O2/mol 0.79 mol N2/mol T = 320C, P = 1.4 atm

Labeling a flowchart-continue
Process stream can be given in two ways: a) As the total amount or flow rate of the stream and the fractions of each component b) Or directly as the amount or flow rate of each component.
10 lbm 3.0 lbm CH4 4.0 lbm C2H4 3.0 lbm C2H6 0.3 lbm CH4/lbm 0.4 lbm C2H4/lbm 0.3 lbm C2H6/lbm

100 kmol/min
60 kmol N2/min 40 kmol O2/min 0.6 kmol N2/kmol 0.4 kmol O2/kmol

Labeling a flowchart-continue
2. Assign algebraic symbols to unknown stream variables [such as m (kg solution/min), x (lbm N2/lbm), and n (kmol C3H8)] and write these variable names and their units on the flowchart.
mol/h n
0.21 mol O2/mol 0.79 mol N2/mol T = 320C, P = 1.4 atm 400 mol/h y mol O2/mol (1-y) mol N2/mol T = 320C, P = 1.4 atm

Labeling a flowchart-continue
If that the mass of stream 1 is half that of stream 2, label the masses of these streams as m and 2m rather than m1 and m2. If you know that mass fraction of nitrogen is 3 times than oxygen, label mass fractions as y g O2/g and 3y g N2/g rather than y1 and y2. When labeling component mass fraction or mole fraction, the last one must be 1 minus the sum of the others. If volumetric flow rate of a stream is given, it is generally useful to label the mass or molar flow rate of this stream or to calculate it directly, since balance are not written on volumetric qualities.

Consistent on Notation
m mass mass flow rate m n moles molar flow rate n V volume volume flow rate V x component fraction (mass or moles) in liquid y moles fraction in gas

Try This..
Two methanol-water mixture are contained in separate flask. The first mixture contains 40wt% methanol and the second flask contains 70wt% methanol. If 200g of the first mixture are going to be mixed with 150g of the second in a mixing unit, what are the mass and composition of the product of the mixing unit?

Drawing the flowchart

200 g
0.40 g MeOH/kg 0.60 g H2O/kg 150 g 0.70 g MeOH/kg 0.30 g H2O/kg mg Mixing

x g MeOH/kg (1-x) g H2O/kg

Solution
Batch process- unit in amount

Balance Equation for batch processes: INITIAL INPUT + GENERATION = FINAL OUTPUT CONSUMPTION
But NONREACTICE process; generation=0, consumption=0

INPUT=OUTPUT

Solution-continue
Balance on TOTAL MASS (Input=Output)

200 g + 150 g = m m = 350 g Balance on MeOH (Input=Output)

200 g 0.40 g MeOH g + 150 g 0.70 g MeOH g = 350 g x g MeOH g

x= 0.529 g MeOH/g (1-0.529) g H2O/g = 0.471 g H2O/g

Try This..
An experiment on the growth rate of certain organism requires an environment of humid air enriched in oxygen. Three input streams are fed into an evaporation chamber to produce an output stream with the desired composition. A: Liquid water fed at rate of 20 cm3/min B: Air (21% O2 and 79% N2) C: Pure O2 with a molar flow rate one-fifth of the molar flow rate of stream B The output gas is analyzed and is found to contain 1.5 mole% water. Draw and label the flowchart of the process, and calculate all unknown stream variables.

Solution

CLASS DISCUSSION

Solution

1 mol O2/min 0.200 n 1 mol air/min n

0.21 mol O2 /mol 0.79 mol N2 /mol

3 mol/min n
Evaporation
0.015 mol H2O /mol y mol O2 /mol (0.985-y) mol N2/mol

20 cm3 H2O (l)/min

2 mol H2O/min n

TEST YOURSELF Page 93

Flowchart Scaling & Basis of Calculation

Flowchart scaling procedure of changing the values of all stream amounts or flow rates by a proportional amount while leaving the stream compositions unchanged. The process would still be balance. Scaling-up if final stream quantities are larger than the original quantities.

Scaling down if final stream quantities are smaller than the original quantities.

Flowchart Scaling & Basis of Calculation

1 kg C6H6 2 kg 0.5 kg C6H6/kg 0.5 kg C7H8/kg x 300 300 kg C6H6 600 kg 0.5 kg C6H6/kg 0.5 kg C7H8/kg kg kg/h Replace kg with lbm 600 lbm/h 0.5 lbm C6H6/lbm 0.5 lbm C7H8/lbm

1 kg C7H8

300 kg C7H8

300 lbm/h

300 lbm/h

Flowchart Scaling & Basis of Calculation

Suppose you have balanced a process and the amount or flow rate of one of the process streams is n1.You can scale the flow chart to make the amount or flow rate of this stream n2 by multiplying all stream amounts or flow rate by the ratio n2/n1. You cannot, however, scale masses or mass flow rates to molar quantities or vice versa by simple multiplication; conversions of this type must be carried out using the methods as discussed in mass fraction and mol fraction section.

Basis of Calculation
A basis of calculation is an amount (mass or moles) of flow rate (mass or molar) of one stream or stream component in a process. All unknown variables are determined to be consistent with the basis. If a stream amount or flow rate is given in problem, choose this quantity as a basis If no stream amount or flow rate are known, assume one stream with known composition. If mass fraction is known, choose total mass or mass flow rate as basis. If mole fraction is known, choose a total moles or molar flow rate as basis.

CLASS DISCUSSION Example 4.3-2

Balancing a Process
3.0 kg/min of benzene and 1.0 kg/min of toluene are mixed
3 kg C6H6/min m (kg/min) x (kg C6H6/kg) (1-x) (kg C7H8/kg)

1 kg C7H8/min

Two unknown quantities m and x, associated with process, so two equations are needed to calculate them. For NONREACTIVE process, so input = output. 3 possible balance can be written Balance on total mass, benzene, and toluene any two of which provide the equations needed to determine m and x.

Balancing a Process-continue
2 rules for balancing nonreactive processes: 1. The maximum number of independent equations that can be derived by writing balances on a nonreactive system equals the number of chemical species in the input and output streams. (balances for substance and total mass) 2. Write balances first that involve the fewest unknown variables.

Solution
Total Mass Balance: 3.0 kg/min + 1.0 kg/min = m kg/min = 4.0 kg/min Benzene Balance: 3.0 kg C6H6/min = 4.0 kg/min (x kg C6H6/kg) x = 0.75 kg C6H6/kg

TEST YOURSELF Page 98

Degree-of-Freedom Analysis
Before do any material balance calculation, use a properly drawn and labeled flowchart to determine whether there is enough information to solve a given problem. The procedure for doing so is referred to as degree-of-freedom analysis.

Degree-of-Freedom Analysis-continue
4 steps to perform a degree-of-freedom analysis: 1. Draw and completely label a flowchart 2. Count the unknown variables on the chart (n unknowns) 1. Count the independent equations (n indep. eq.) 2. Find number of degree-of-freedom (ndf)

ndf= n

unknowns

-n

indep. eq.

3 possibilities from degree-of-freedom analysis: 1. If ndf = 0 the problem can in principle be solved. 2. If ndf > 0 there are more unknowns than independent equations relating to them at least ndf additional variable values must be specified before remaining variable values can be determined. Either relations have been overlooked or the problem is underspecified.

3. If ndf < 0 there are more independent equations than unknowns. Either the flowchart is incompletely labeled or the problem is overspecified with redundant and possibly inconsistent relations. There is little point wasting time trying to solve material balance for n df > 0 or n df <0.

Sources of equations of unknown process variables: Material balances. An energy balance. Process specifications 4. Physical properties and laws 5. Physical constraints 6. Stoichiometric relations

General Procedure for Single Unit Process Material Balance Calculation

9 steps for single unit material balance calculation: 1. Choose as basis of calculation an amount or flow rate of one of the process streams. 2. Draw a flowchart and fill in all unknown variables values, including the basis of calculation. Then label unknown stream variables on the chart. 3. Express what the problem statement asks you to determine in terms of the labeled variables.

General Procedure for Single Unit Process Material Balance Calculation-continue

4. If you are given mixed mass and mole units for a stream (such as a total mass flow rate and component mole fractions or vice versa), convert all quantities to one basis. 5. Do the degree-of-freedom analysis. 6. If the number of unknowns equals the number of equations relating them (i.e., if the system has zero degree of freedom), write the equations in an efficient order (minimizing simultaneous equations) and circle the variables for which you will solve.

General Procedure for Single Unit Process Material Balance Calculation-continue

7. Solve the equations. 8. Calculate the quantities requested in the problem statement if they have not already been calculated. 9. If a stream quantity or flow rate ng was given in the problem statement and another value nc was either chosen as a basis or calculated for this stream, scale the balanced process by the ratio ng/nc to obtain the final result.

Material Balance Problems Without Chemical Reactions

Material Balance on a Mixing Unit
An aqueous solution of sodium hydroxide contains 20.0% NaOH by mass. It is desired to produce and 8.0% NaOH solution by diluting a stream of the 20% solution with a stream of pure water. Calculate the ratios (liters H2O/kg feed solution) and (kg product solution/kg feed solution).

9 steps for single unit material balance calculation 1. Choose as basis of calculation an amount or flow rate of one of the process streams. 2. Draw and label the flowchart Choose a basis of 100kg of the 20% feed solution.
100 kg 0.20 kg NaOH/kg 0.80 kg H2O/kg Mixing

m2 kg 0.080 kg NaOH/kg 0.920 kg H2O/kg

m1 (kg H2O) V1 (liters H2O)

3. Express what the problem statement asks you to determine in terms of the labeled variables. The desired quantities are V1/100 (liters H2O/kg feed solution) and m2/100 (kg product/kg feed solution). Our task is therefore to calculate the variables V1 and m2. 4. Convert unit into one basis, 5. Do degree-offreedom analysis. count unknown variables and equations relating them. 6. Write the balances equations in an efficient order. Unknowns: 3 unknowns- m1, m2 and V1. Equations: nonreactive process, as there are 2 species, can write 2 balances. As 3 balances are needed, another solution for V1 will be taken from the information of density of water.

7. Outline the solution and 8. Calculate the properties of unknown variables. Balances for the system: INPUT=OUTPUT NaOH Balance: (0.2 kgNaOH/kg)(100kg)=(0.008 kg NaOH/kg)m2 m2= 250 kg NaOH Total Mass Balance: 100kg+m1=m2 (m2=250 kg NaOH) m1=150 kg NaOH

7. Outline the solution and 8. Calculate the properties of unknown variables.

Calculate the volume of water V1=

150 kg V1 = = 150 L 1L kg

Ratios V1/100 kg= 1.5 L H2O/ kg feed solution m2/100 kg= 2.5 kg product /kg feed solution

Material Balance on a Condenser

CLASS DISCUSSION Example 4.3-4

Material Balance on a Distillation Column

CLASS DISCUSSION Example 4.3-5