INTRODUCTION TO CHEMICAL ENGINEERING

MODULE 2 : ENERGY AND MATERIAL BALANCE CALCULATIONS

This module covers :

 Basic Chemical Principles

 Calculations on solid mixture

 Material Balance and its step-by-procedure

 Material Balance for simple systems

 Material Balance for simple system involving reaction

 Energy Balance on simple systems

INTRODUCTION

WHAT IS MATERIAL BALANCE:

Material balance is an exact accounting of all the materials that enters, leaves, accumulates
or is depleted in an industrial process or a particular process equipment in a given time of
interval.

Principle followed by Material Balance:

All material balance calculations are based on the principle of conservation of mass, which
states that matter can neither be created nor be destroyed, but it can undergo physical and
chemical changes.

As an equation it can be given as,

Rate at which quantity enters + rate of quantity generation = rate at which quantity leaves +
rate of quantity accumulation

WHAT IS ENERGY BALANCE:

An energy balance provides insight of the energy requirements of a system undergoing a

change. Since moving or stored mass contains energy, the energy balance equation adds the
energy terms to the total mass balance. Additionally, energy can be transported independent
of mass such as in the form of heat or work.
Principle followed by Energy balance:

The fundamental principle that is followed in energy balance states that energy can neither
be created nor be destroyed, it can only be transferred or transformed. This principle
ensures that when a system is experiencing a change, the total energy input, output and
accumulation must be accounted in order to maintain an equilibrium. (OUTPUT – INPUT +
ACCUMULATION = 0)

Process:

A process is defined as a series of interconnected operations or steps designed to convert

raw materials into desired products through physical, chemical, or biological
transformations.

Key Aspects of a Chemical Engineering Process:

1. Input & Output – Raw materials (inputs) are transformed into products (outputs).

2. Unit Operations – Individual steps like mixing, heating, cooling, separation, and chemical
reactions.

3. Mass & Energy Balance – Conservation principles applied to ensure efficiency.

4. Control & Optimization – Monitoring variables such as temperature, pressure, and flow
rates to maintain process stability

System:
A system is defined as a specific portion of matter or a region in space chosen for analysis,
where mass and energy interactions occur. It is used to study processes and apply
principles like mass and energy balances. (or) A system is defined as the part of physical
universe , which is under consideration.

Types of Systems in Chemical Engineering

1. Open System – Exchanges both mass and energy with its surroundings.

Example: A distillation column where feed enters, and products leave

2. Closed System – Exchanges energy but not mass with its surroundings.

Example: A sealed reactor with heat transfer but no mass flow.

3. Isolated System – No exchange of mass or energy with surroundings (ideal case).

Example: A perfectly insulated batch reactor (theoretical concept).

Flow:
Flow refers to the movement of fluids (liquids or gases) through a system, typically driven by
pressure, gravity, or other forces. Flow is a fundamental aspect of chemical processes,
affecting mass transfer, heat transfer, and reaction rates.

Types of Flow in Chemical Engineering:

1. Laminar Flow – Smooth, orderly fluid motion with parallel layers; occurs at low velocities.

Example: Blood flow in small capillaries.

2. Turbulent Flow – Chaotic, irregular fluid motion with mixing; occurs at high velocities.

Example: Flow in industrial pipelines.

3. Single-phase vs. Multiphase Flow – Involves one phase (e.g., water flow) or multiple
phases (e.g., gas-liquid flow in distillation).

4. Steady vs. Unsteady Flow – Steady flow has constant properties over time, while unsteady
flow changes with time.

Flow sheeting:
Flow sheeting is the process of creating a flowsheet, which is a graphical representation of a
chemical process, showing the sequence of unit operations, streams, and flow of materials
and energy. It is used for designing, analyzing, and optimizing chemical processes.

Types of Flowsheets:

1. Block Flow Diagram (BFD) – A high-level diagram showing major process units and flow
directions.

2. Process Flow Diagram (PFD) – A detailed representation including equipment, major

pipelines, and operating conditions.

3. Piping and Instrumentation Diagram (P&ID) – A highly detailed diagram that includes all
control instruments, valves, and piping details.

Importance of Flow sheeting:

Helps in process design and simulation.

Assists in troubleshooting and optimization.

Provides a blueprint for plant operation and safety analysis.

Block Diagram:
A block diagram (or Block Flow Diagram, BFD) is a simplified graphical representation of a
chemical process, showing the major process units (blocks) and the flow of materials
between them. It provides a high-level overview without detailed equipment specifications or
process conditions.

Key Features of a Block Diagram:

Blocks represent process units (e.g., reactors, separators, heat exchangers).

Arrows indicate flow direction of raw materials, intermediates, and products.

Minimal details (no instrumentation, piping, or operating conditions).

Importance of Block Diagrams:

Provides a quick overview of the process.

Helps in conceptual process design and communication.

Used as a first step before detailed process flow diagrams (PFDs).

Difference:
Aspects Block Diagram Flow sheeting
Level of details Minimal details High details
Complexity Less complex More complex
Usage in analysis Serves as a preliminary tool Provides the necessary
to understand the major details for advanced
mass and energy flow in the process simulations and
process . control strategy
development .

Tie Substance:
A tie substance is a component in a process that is neither consumed nor generated in any
chemical reaction but is used as a reference to track mass balances across unit operations.
It helps simplify material balance calculations by providing a conserved quantity.

Example:

In a distillation process, if a mixture of ethanol and water is separated, water can be chosen
as a tie substance to track mass balances since it does not react chemically during
separation.

Flow Process:
A flow process is one where material, energy, or both move continuously through the system.
These processes are characterized by a constant input and output of materials, allowing the
process to operate in a steady state over extended periods

Non-Flow Process:
A non-flow process typically refers to processes where there is no continuous movement of
material through the system. Instead, the process is conducted in discrete batches or
remains static over a period of time.

How to find the key substance?

1. Examine the Process Flowsheet:

Look at the diagram of the process to see where materials are added, transformed, or
removed. This helps you identify the major steps and streams in the process.

2. Identify Main Reactants and Products:

Focus on the chemicals that enter the process (reactants) and those that are produced
(products). These are usually the most important substances in any reaction.

3. Select a Tie Substance:

Choose a substance that is present in several streams and does not change during the
process (i.e., it is not consumed or created). This substance helps track overall mass
balance and flow.

4. Consider Measurement Ease:

Pick substances that can be easily and accurately measured. This helps in monitoring the
process and verifying that mass and energy are conserved.

5. Review Stoichiometry:

Check the reaction equations. The substances that appear directly in the balanced chemical
equations are typically the key ones because they directly influence how much product is
made.

Exothermic Reaction:
Definition: Releases heat; products have lower energy than reactants.

Rate of Reaction: Measured by the speed of conversion and the rate of heat release; may
accelerate with increasing temperature but requires cooling control.

Endothermic Reaction:
Definition: Absorbs heat; products have higher energy than reactants.

Rate of Reaction: Measured by the speed of conversion and the rate of heat absorption;
requires external heating to maintain an adequate reaction rate.

Variable:
Variables change during the process and are the primary focus of dynamic analysis. (or)
changes with time and position.

Constant:
Constants are fixed values that do not vary throughout the problem or experiment. (or) does
not changes with time and position.

Parameter:
Parameters are values that define the behavior or characteristics of a system; they are held
fixed during a given analysis but can be varied in different design or simulation scenarios. (or)
for a particular period and position, it may be variable or constant.

Difference:
Aspect Variable Constant Parameter
Definition Changes with time Does not change For a particular
and position with time and period or position, it
position may be variable or
constant

Example Concentration in a The universal gas Reaction rate

reactor, temperature constant (R), constant ,heat
in a heat exchanger standard transfer coefficients
etc.. atmospheric etc…
pressure

How to fix the basis?

Fixing the basis in chemical engineering is a method used to simplify material balance
calculations. It involves selecting a convenient reference amount of material (like 100 kg or
100 kmol) and using that fixed amount to perform all your calculations.

1. Choose a Reference Quantity:

Pick a fixed amount of a key component or the feed stream. For example, assume you have
100 kmol of a reactant

2. Perform Calculations Using This Fixed Amount:

Use the stoichiometry of your reaction and the process flows to calculate the amounts of
products, by-products, or leftover reactants. All the values in your calculations will be
expressed relative to your chosen basis (e.g., 100 kmol).

3. Scale as Needed:

Once you have calculated all the stream compositions and flows based on the fixed basis,
you can easily scale the results up or down to match the actual production rate. For instance,
if the actual process uses 500 kmol, simply multiply the calculated amounts by 5.

By fixing the basis, you ensure that your mass and energy balance calculations are
consistent and easier to handle, especially when dealing with percentages or ratios. This
approach is very useful during the design and analysis stages of a chemical process.

MOLES, MOLECULAR MASS AND ATOMIC MASS:

GRAM ATOM:

A gram atom is the amount of an element whose mass in grams is numerically equal to its
atomic weight or one mole of atoms of that element. It is expressed in grams (g).

Gram atom = (Mass in gram of element) / (Atomic weight)

GRAM MOLE:

A gram mole for a compound is defined as the amount of a substance that contains the
same number of molecules. This is known as Avagadro’s number (6.022×10²³). It is
expressed in moles (mol) .

Gram mole = (Mass in gram of compound) / (Molecular weight)

GRAM EQUIVALENT :

A gram equivalent or equivalent weight is the mass of a substance in grams that reacts with
one mole of hydrogen ions. It is expressed in g / eq.

Gram equivalent = (Mass in gram of element or compound) / ( Equivalent weight)

NORMALITY (N) :

Normality is a measure of solution concentration of the number of gram equivalents of a

solute per litre of solution .

Normality = (Number of gram equivalents of solute) / (Volume of solution in litres)

MOLARITY (M) :

Molarity is defined as the number of moles of solute present in one litre of the solution.

Molarity = (Number of moles of solute) / (Volume of solution in litre)

MOLALITY (m) :

Molality is the amount of a substance dissolved in a certain mass of solvent. It is defined as

the moles of solute per kilograms of a solvent.

Molality = (Number of moles of solute) / (Mass of solvent in kg)

MOLE FRACTION (x) :

Mole fraction of a component is the ratio of number of moles of a specific component in a

mixture to the total number of moles of all components in that mixture.

X(solute) = (Mass of solute) / (Total moles of solution )

X(solvent) = (Mass of solvent) / (Total moles of solution)

X(solute) + X(solvent) = 1

MOLAR RATIO:

Molar ratio is defined as the relationship between the number of moles of one substance to
the number of moles of another substance in a balanced chemical equation.
Molar ratio = (Number of moles of solute) / (Number of moles of solvent)

MASS PERCENTAGE (% w/w) :

Mass percentage is the percentage of the total mass of the solution or a mixture that is
contributed by a specific component.

Mass % = (Mass of solute or component in g / Total mass of mixture or solution in g) * 100%

VOLUME PERCENTAGE (% v/v) :

Volume percentage is the percentage of the total volume of a solution or a mixture that is
contributed by a specific component .

Volume % = (Volume of solute in mL / Volume of solution in mL )* 100%

Calculation on solid mixtures and solutions

=> Select a suitable basis for calculation for a batch process the quantity of a substance
present in the system may be taken as a basis for a flow system unit time may be taken as a
basis.

1. How many grams of carbon or present in 264 grams of carbon

dioxide(CO2)? Soln:

44 gram of (CO2) contain 12 gram of

carbon C = 12

O2 = 2 ( 16 )= 32

CO2 = 32+12 = 44
1 gram of (CO2) contain 12/44 gram of carbon

264 gram of carbon dioxide contain 12 /44 ×

264 => 72 grams of carbon.

2. How many moles of potassium carbonate( K2CO3) will contain 234 Kg of K ?

Soln:

K2 = 39×2 = 78

C = 12

O3 = 3×16 = 48

:. K2CO3 = 138
Mass fraction of potassium(K) in K2CO3 = 78/ 138

Convert 234 kilogram into grams :

234kg = 234000g
Moles of K2CO3 = Mass of K2CO3 / Mass of K in K2CO3

= 234000 / 78

= 3000 moles

3. What is the weight percentage of CaO in calcium hydroxide Ca(OH)2 ?

Molar mass of Ca(OH)2 = 40 + 2 × 16 + 2× 1

= 74 g / mol

Molar mass of CaO = 40 + 60

= 56 g / mol

[ Calcium hydroxide Ca(OH)2 is made from CaO and H2O

CaO + H2O —---> Ca(OH)2

⇒ Mass of CaO in Ca(OH)2 = 56g

⇒ Total mass of Ca(OH)2 = 74g

Weight percentage = Mass of CaO / Mass of Ca(OH) of Cao

= 56 / 74 × 100 = 75.68%

MATERIAL BALANCE:

STEP BY STEP PROCEDURE FOR MATERIAL BALANCE

CALCULATION

(i) Draw a flow sheet of the entire process each of the complex processes, such as those
taking place within a reactor, drier, rectification column, evaporator, etc. being represented by
a single block.

(ii) Write down the available quantitative information. The available information may
include the flow rates of incoming and outgoing streams and their compositions.

(iii) Try to identify a substance which enters a process equipment through only one incoming
stream and leaves through one outgoing stream. Such a substance is known as tie
substance and knowledge of its percentage in the two streams establishes the ratio of the
weights of the streams. Existence of a tie substance or key component is not essential. In
complex problems, there may be more than one tie substance.

(iv) Select a suitable basis for calculation. For a batch process, the quantity of a substance
present in the system may be taken as a basis. For a flow system, unit time may be taken as
a basis.

(v) If no chemical reaction takes place, material balance is computed on the basis of
chemical compounds. Mass units are used.

(vi) If chemical reactions occur, material balance is computed with reference to chemical
elements or radicals. Molar units are normally used.

(vii) Write the overall mass balance equations and the mass balance equations for
each of the components in the entire process and around each piece of equipment.

(viii) The number of unknown quantities to be calculated cannot exceed the number of
independent material balance equations, otherwise, the problem is indeterminate.

(ix) If the number of independent material balance equations exceeds the number of
unknown quantities, one has to select certain equations. Usually, equations based on
components forming a higher percentage of the total mass are selected.

(x) For processes involving phase changes, phase equilibrium relations become important.

ENERGY BALANCE:

In the context of energy balance,there are three forms of energy that we will consider
(expressed per mass of material): internal energy, kinetic energy and potential energy

Internal energy: Internal energy (U) represents the total energy within a system, including
kinetic and potential energies of its molecules, and its change (ΔU) reflects the net energy
input minus the net energy output.

Kinetic energy: kinetic energy represents the energy associated with the movement of the
system or its components. It’s one of the forms of energy that can be exchanged or
transformed within a system.

Potential energy: potential energy (PE) represents stored energy due to an object’s position
or configuration, like gravitational PE or elastic PE, and is a key component of the total
energy of a system

Reacting systems:

All chemical reactions are accompanied by either an absorption or an evolution of

energy as a consequence of the forces involved in chemical bonding .When heat is evolved
in a reaction,the reaction is [Link] heat is absorbed, the reaction is said to be
[Link] is calculated using enthalpy (CpΔT)
Heat of reaction:

The Heat of Reaction (also known and Enthalpy of Reaction) is the change in the enthalpy of
a chemical reaction that occurs at a constant pressure

Standard heat of reaction:

The standard heat of reaction is the change in enthalpy of a system as a result of

the chemical reaction taking place under a pressure of 1 atm (101.3kpa) starting and ending
with all the components at a constant temperature of 25°C.

Effect of pressure on heat of reaction:

In case of a reaction involving solid or liquid reactants and products,pressure has

little effect on heat of [Link] gaseous reactants and products may be assumed to
behave ideally,the change in enthalpy is independent of pressure.

If the pressure differences are high, the assumption of ideal behaviour is no longer justified
and the change in enthalpy becomes dependent on the change in [Link] the effect of
pressure on the heat of a reaction is relatively negligible compared to the magnitude of the
heat of reaction and is generally ignored.

Effect of temperature on heat of reaction :

Temperature affects the heat of reaction through the enthalpies of the reactants and
products. The enthalpy of a substance increases with temperature.

The effect of temperature on the heat of reaction is described by Kirchhoff’s equation.

The enthalpy of the reaction changes if the increase in enthalpy of the products and
reactants is different.

The rate of a chemical reaction increases as the temperature increases.

This is because the reactant particles move faster and collide more often and with more
force.

This increases the likelihood of the reaction to cause collisions between the particles, which
speeds up the reaction.
Steps to Follow in Energy Balance Calculations Across a Piece of Equipment

1. Prepare a block diagram for the unit.

2. Write down the available information such as the flow rates of the incoming and outgoing
streams, their enthalpies, heat and work input, heat losses, etc.

3. Try to identify a tie substance.

4. Select a suitable basis for calculation.

5. If no chemical reaction takes place within the system, consider whether there is a phase
change such as vaporization and condensation, fusion and solidification, sublimation,
transition from one crystal structure to another, crystallization, etc. Consider enthalpy
changes accompanying such a change, if any.

6. If chemical reactions occur, consider enthalpy changes accompanying the reactions.

7. Tabulate all energy input items in one column and all output items in another. For
convenience, all entries in each column are arranged to be of positive sign. Work done on the
system will appear as an input item while work done by the system will appear as an output
item. Heat absorbed is an input item, and heat evolved and/or losses are output items. The
enthalpies of all entering streams are entered as input items, and those of the outgoing
streams as output items. Heats of reaction, if negative, are input items, while they are
considered to be output items if positive.

Selection Basis for Material and Energy Balance

1. Introduction

Material and energy balance calculations are fundamental in chemical engineering to

analyze chemical processes. To perform these calculations, we must first define a
selection basis , which is a reference quantity chosen to simplify and standardize the
calculations.

Why is Selection Basis Important?

 Helps in simplifying complex process calculations.

 Provides a consistent approach to solving material and energy balance

problems.

 Facilitates comparison between different cases and scaling of processes.

 Ensures clarity in mass and energy flow calculations.

2. Common Selection Bases

1. Mass Basis

 Involves selecting a fixed mass of a substance as the basis for calculations.

 Commonly used in solid and liquid processes.

 Helps in tracking mass changes in unit operations like mixing, distillation, and
crystallization.

Example:

 Taking 100 kg of a reactant as the basis.

 If the reaction consumes 20% of the reactant, the remaining reactant = 80 kg.

2. Molar Basis

 Used in processes where chemical reactions are involved.

 More convenient for dealing with gases and molecular-level interactions.

 Expresses quantities in moles (kmol or mol) rather than mass.

Example:
For the reaction N₂ + 3H₂ → 2NH₃, if we choose 1 kmol of N₂ as the basis:

 Hydrogen required = 3 kmol

 Ammonia produced = 2 kmol

3. Time Basis
  Used in continuous processes where flow rates are involved.

 Expresses material and energy quantities per unit time (e.g., per hour, per
second).

Example:
A distillation column produces 500 kg of ethanol /hr . If we analyze for 1 hour, the
total output is 500 kg.

4. Per Unit Product Basis

 Helps in normalizing calculations for production efficiency.

 Used to determine resource consumption and waste generation per unit of

product.

Example:

 A factory produces 1 ton of sulfuric acid using 2 tons of raw materials.

 If we take 1 ton of sulfuric acid as the basis, then the raw material
requirement is 2 tons/ton of product.

5. Per Unit Feed Basis

 Used to analyze the amount of product formed per unit of raw material input.

Example:

 A process uses 100 kg of limestone and produces 56 kg of CaO.

 If we take 100 kg of limestone as the basis, the conversion efficiency is 56%.

6. Stoichiometric Basis

 Used when solving reaction-based problems.

 The limiting reactant is taken as the basis for all calculations.

Example:
For the combustion reaction CH₄ + 2O₂ → CO₂ + 2H₂O, choosing 1 kmol of CH₄ as
the basis:

 Oxygen needed = 2 kmol

  Carbon dioxide produced = 1 kmol

 Water produced = 2 kmol

3. How to Choose the Selection Basis?

Factors to Consider:

1. Type of Process – Batch or continuous process.

2. Given Data – Mass flow rate, molar flow rate, or time constraints.

3. Reaction Stoichiometry – Choosing the limiting reactant in reaction-based

calculations.

4. Ease of Calculation – Selecting a basis that simplifies unit conversions.

5. Practicality – Using common industry standards like "per ton of product" or

"per hour of operation."

PROBLEM:

A reaction produces ammonia (NH₃) from nitrogen (N₂) and hydrogen (H₂) using the
equation:

N2+3H2→2NH3

If 56 kmol of Nitrogen are fed into the reactor, calculate:

1. The amount of hydrogen required.

2. The amount of ammonia produced.

Solution:

Step 1: Choose a Selection Basis

Let’s take 56 kmol of N₂ as the basis.

Step 2: Use Stoichiometric Ratios

From the reaction equation:

 1 kmol of N₂ reacts with 3 kmol of H₂

 1 kmol of N₂ produces 2 kmol of NH₃

For 56 kmol of N₂:

  Hydrogen required = 56×3=168 kmol

 Ammonia produced = 56×2= 112 kmol

Final Answer:

 168 kmol of H₂ is required.

 112 kmol of NH₃ is produced.