Lesson 1

Fundamentals of Material balances

 Introduction
• What do chemical and biological engineers do?

 its intriguing, challenging and flexible profession.

 work in wide variety of industries.
focus on design, control, operation, troubleshooting, research,
management, even political(environment and economics concerns).
Material balance, why?
• Material balance is simply an accounting of all materials flowing,
accumulated, or generated in a chemical and biological process.
• Material balances are nothing more than the application of the
conservation law for mass.
• Material balance calculations are almost invariably a prerequisite to
all calculations in the solution of both simple and complex chemical
and biological engineering problems.
Evaporation of Water from Salt Water
 System and control volume
• A system is any arbitrary portion of a process set out specifically for analysis.
• A control volume is any imaginary or tangible boundary which encloses the
system.
• A process is one or a series of actions or operations or treatments that result in
an end product.
• Process unit means the equipment assembled and connected by pipes and ducts
to process raw materials and to manufacture either a final or intermediate
product used in the onsite production of other products.
• Unit operations involve a physical change or chemical transformation such as
separation, crystallization, evaporation, filtration, polymerization, isomerization
etc.…
 Types of System
Closed System
• A system is closed if there is no mass passing through the control
volume during the period of analysis.
Open System
• A system is open if mass can pass through the control volume during
the period of analysis.
Types of balance
Differential balance: is a balance at one particular instant in time.
Integral balance: deals with the entire time of the process at once (so it
uses amounts rather than rates: e.g. mass not mass/time).
 The Steady-State Process
• In a steady-state process, the values of all variables in the process (such as
chemical composition, temperature, pressure, etc.) do not change with time.
Otherwise, it is an unsteady-state process.

For a steady-state process:

 

• Where xi = any process variable (T, p …) and θ = time

 The Mass Balance Equation

• Consider a control volume

Balancing B within the control volume,

• ∆mB = (mass increases) B - (mass decreases) B
• ∆mB = InputB +Generate dB – Consume dB – OutputB
 Possible scenarios for B,
 
If (input + generation)B > (output + consumption)B,

then the amount B within the control volume increases

(accumulation)
 
If (input + generation)B < (output + consumption)B,

then the amount B within the control volume decreases

(depletion/negative accumulation)
 
If (input + generation)B = (output + consumption)B,

then the amount B within the control volume will not change
(steady-state)
• The general mass balance equation can be written as
• Acc/Dep = Input + Generation – Output – Consumption
 
• For a steady-state process, there is no accumulation or depletion of materials:
 
• Input + Generation – Output – Consumption = 0 or
• Input + Generation = Output + Consumption
 
• If there is no chemical reaction, there is no means for a material to be
generated or consumed, then

Acc/Dep = Input – Output

• If there is no chemical reaction and steady-state condition exists, then:

• 0 = Input – Output OR
• Input = Output
 Degrees of Freedom (DF) Analysis

• The procedure of determining whether enough information is given to solve the

problem.
To determine the degrees of freedom (DF):
  DF = U – V
• where U = number of unknown variables to be solved.
• V = number of independent equations relating the unknown variables.

• What are independent equations?

• An equation is independent if it cannot be derived algebraically from the other
equations
 Degrees of Freedom (DF) Analysis

• Possible cases depending on the value of DF:

• DF = 0: there are equal number of unknowns and independent equations and

the problem, in principle, can be solved.

• DF > 0: there are more unknowns than independent equations and the problem
is underspecified and has infinitely many solutions.

• DF < 0: there are more independent equations than unknowns and the problem
is over specified and has no exact solution
Solving Material Balances Problems Involving Non-Reactive Processes
Component and Overall Material Balances
•  Consider a steady-state distillation process,
Component and Overall Material Balances

• Since the process is at steady-state condition and no chemical reaction is

involved, the material balance equation becomes
Input = Output
This balance equation can be applied to: 
 The total mass entering and leaving the process
 Mass of individual component entering and leaving the process.
Component and Overall Material Balances

• Total Mass (Overall Material Balance) 

m1 = m 2 + m 3
• Component A Balance
mA1 = mA2 + mA3
m1xA1 = m2xA2 + m3xA3
• Component B Balance 
mB1 = mB2 + mB3
m1xB1 = m2xB2 + m3xB3
Component and Overall Material Balances

• For the given process, 3 material balance equations can be written:

Total Balance: m1 = m2 + m3 (E1)

A-Balance: mA1 = mA2 + mA3 (E2)
B-Balance: mB1 = mB2 + mB3 (E3)
 
• Are these material balances independent equations?
 
• If (E1) and (E2) are added, what does the resulting equation represents?
Component and Overall Material Balances
• Consider the unsteady-state extraction process:

• Extraction is a physical process in which a component of a mixture is extracted

using an immiscible solvent.
Component and Overall Material Balances
• Writing the material balance equations:
 
Total Balance: (Acc)T = m1 + m2 - m3- m4
A-Balance: (Acc)A = mA1 – mA3
B-Balance: (Acc)B = mB1 – mB3 – mB4
C-Balance: (Acc)C = mC2 –mC4

• The total balance can also be obtained by adding the last 3 equations and is no
longer independent.
• Number of Independent Material Balance Equations in Process without Chemical
Reaction.
For processes with no chemical reaction;

Nm = Ni
• whereNm = number of independent material balance equations. 
Ni=total number of chemical species (or components) involved in the
process.
Mixing of Methanol-Water Mixtures
• Two methanol-water mixtures are contained in separate tanks.

• The first mixture contains 40.0 wt% methanol and the second contains 70.0 wt%
methanol.
 
• If 200 kg of the first mixture is combined with 150 kg of the second, what are the
mass and composition of the product?
• Step 1. Draw a flowchart to visually organize the data.
• Step 2. Determine the degrees of freedom (DF)
 
• Number of unknowns (U): 3 unknowns (m3, xM3, xW3)
• Number of independent equations (V):
  material balances: 2 equations
physical constraint: 1 equation (Sx = 1.00)
• total independent equations =3
• DF = U – V = 3 – 3 = 0, the problem is solvable
• Step 3. Write down the equations
 
• Material Balances (Steady-State, Non-Reactive Process):

• Total Balance: m1 + m2 = m3
• Methanol-Balance: m1xM1 + m2xM2 = m3xM3
• Water-Balance:m1xW1 + m2xW2 = m3xW3
• (choose only 2 equations since one of them is no longer independent)
 
• Physical Constraint (applied to mixture 3):

• xM3 + xW3 = 1.00

• Step 4. Solve the unknowns (m3, xM3, xW3)
• Always start with the equation with the least number of unknowns if possible
and minimize solving equations simultaneously.

Total Balance (m3)

Methanol Balance (xM3)

Physical Constraint (xW3)

• Step 4. Solve the unknowns (m3, xM3, xW3)
• Total balance:
m3 = (200 kg) + (150 kg)
m3 = 350 kg
• CH3OH balance:
(200 kg)(0.40) + (150 kg)(0.70) = (350 g)xM3
xM3 = 0.529
• Physical constraint:
xW3 = 1.00 – xM3 = 1 – 0.529
xW3 = 0.471
Solving Material Balances Problems Involving Reactive
Processes
• Material balances on processes involving chemical reactions may be solved by
applying:
• Molecular Species Balance – a material balance equation is applied to each
chemical compound appearing in the process.

• Atomic Species Balance – the balance is applied to each element appearing in

the process. 
• Extent of Reaction – expressions for each reactive species is written involving
the extent of reaction.
• Molecular and Elemental Balances
For steady-state reactive processes
Input + Generation = Output + Consumption
• The generation and consumption terms in the molecular balance equation is
usually obtained from chemical stoichiometry.
• But for an atomic balance, for all cases ;
Input = Output
 Example. Dehydrogenation of Ethane
• Consider the dehydrogenation of ethane in a steady-state continuous reactor,
 Dehydrogenation of Ethane

Total Balance:
Input = Output
Molecular Species Balance:
  C2H6: Input – Consumed = Output
C2H4: Generated = Output
H2: Generated = Output
 
Atomic (Elemental) Species Balance:
  C-Balance: Input = Output
  H-Balance: Input = Output
• Degrees of Freedom of Analysis for Reactive Processes
Molecular Species Balance;
+ No. identified/labeled unknowns
+ No. independent chemical reactions
- No. of independent molecular species
- No. other equations relating unknown variables
----------------------------------------------------------------------------------------------------
= No. degrees of freedom
• Degrees of Freedom of Analysis for Reactive Processes:
Atomic Species Balance
+ No. identified/labeled unknowns
-No. independent atomic species
-No. of independent nonreactive molecular species
-No. other equations relating unknown variables 
------------------------------------------------------------------------------------------------
= No. degrees of freedom
• Degrees of Freedom of Analysis for Reactive Processes;
Extent of Reaction
+ No. identified/labeled unknowns
+ No. independent chemical reactions
- No. of independent reactive molecular species
- No. of independent nonreactive molecular species
- No. other equations relating unknown variables
-------------------------------------------------------------------------------------------- 
= No. degrees of freedom
 Independent Chemical Reactions, Molecular and Atomic Species

• Chemical reaction: A chemical reaction is independent if it cannot be

obtained algebraically from other chemical reactions involved in the same
process. 
• Molecular Species: If two molecular species are in the same ratio to each
other wherever they appear in a process, then these molecular species are
not independent.

• Atomic Species: If two atomic species occur in the same ration wherever
they appear in a process, balances on those species will not be
independent equations.
 Independent Chemical Reactions, Molecular and Atomic Species
 
• Consider the following reactions:
A =======> 2B
B =======> C
A =======> 2C
Are these chemical reactions independent?
 Recycle, Bypass, & Purge Calculations
Recycle Stream 
• Recycle stream is a term denoting a process stream that returns material from
downstream of a process unit back to the process unit.
 Bypass Stream 
• Bypass stream is a stream that skips one or more stages of the process and goes
directly to another downstream stage.
 Purge Stream
• Purge stream is a stream bled off to remove an accumulation of inserts or
unwanted material that might otherwise build up in the recycle stream.
• Example. Distillation of Benzene and Toluene

• A distillation column separates 10,000 kg/hr of a mixture containing equal mass

of benzene and toluene. The product D recovered from the condenser at the top
of the column contains 95% benzene, and the bottom W from the column
contains 96% toluene.
• The vapor V entering the condenser from the top of the column is 8000 kg/hr. A
portion of the product from the condenser is returned to the column as reflux R,
and the rest is withdrawn as the final product D. Assume that V, R, and D are
identical in composition since V is condensed completely.
• Find the ratio of the amount refluxed R to the product withdrawn D.
• Overall Process
Total Balance: 10,000 = D + W
Benzene Balance: 10,000(0.50) = D(0.95) + W(0.04)

Solving simultaneously,
D = 5050 kg/hr. ; W = 4950 kg/hr.
Total balance around the separator: 
8000 = R + D
R = 2950 kg/hr.
Ratio (R/D) = (2950/5050) = 0.58