LEARNING UNIT 4

Fundamental Principles of Environmental Engineering

Mothusi Motjale
MEng, PMP®, MCIPS, C.E.M.

Date : August 2023

 Presentation Outline

4.1 INTRODUCTION 4.7 Introduction to Reactors and Reactor

4.2 Units of Expression for Chemical Analysis
Concentrations 4.7.1 Types of Reactors
4.3 Chemical Equilibrium 4.7.2 BATCH REACTORS
4.3.1 Reaction Stoichiometry 4.7.3 CONTINUOUS-FLOW REACTORS
4.3.2 Concentration and Activity 4.7.4 CONTINUOUSLY MIXED FLOW
4.4 Chemical Kinetics REACTORS
4.5 Reactions Used in Water Treatment 4.7.5 PLUG FLOW REACTORS
4.5.1 Acid–base reactions 4.7.6 Time Dependence
4.5.2 Precipitation–Dissolution Reactions 4.7.7 Reaction Characteristics
4.5.3 Oxidation–Reduction Reactions 4.7.8 Input Characteristics for Flow Reactors
4.6 Mass Balance Analysis 4.8 Reactions in Batch Reactors
4.6.1 Fundamental Mass Balance Equation 4.9 Hydraulic Characteristics of Ideal Flow
4.6.2 Accumulation Term Reactors
4.6.3 Input and Output Terms 4.9.1 Completely Mixed Flow Reactor
4.6.4 Reaction Term 4.9.2 Plug Flow Reactor
4.10 REVIEW QUESTIONS
 LEARNING OUTCOMES

On completion of this unit, you should be able to

➢ Explain the importance of the mass balance to environmental engineering;
➢ Compute species concentrations using equilibrium constants;
➢ Value the significance of mass transfer in physical-chemical treatment processes
➢ Identify and define the symbols used in chemical reaction in relation to
environmental engineering;
➢ Evaluate the characteristics of a Batch Reactor, a Plug Flow Reactor (PFR) and a
Continuously Mixed Flow Reactor (CMFR);
➢ Evaluate the significance of mass transfer in physical-chemical treatment
processes
 REVIEW QUESTIONS
1. Convert concentrations into different units,
2. Calculate species concentrations using equilibrium constants.
3. Describe the importance of the mass balance to environmental engineering.
4. Good control volume for mass balances and a steady-state system.
5. Solve the mass balance analysis equations,
6. Calculate the change in concentration in a batch reactor over time due to chemical
reactions and demonstrate how this data can be used to determine reaction
kinetics.
7. Describe the characteristics of a batch reactor, a PFR, and a CMFR.
8. Develop an equation for and calculate the influent or effluent concentrations,
9. Explain why a PFR will have a lower effluent concentration than a CMFR if both
are the same size and treating the same contaminant at the same flow rate.
OVERVIEW FUNDAMENTAL PRINCIPLES OF
ENVIRONMENTAL ENGINEERING
• Principles include
– equilibrium and kinetics of chemical reactions,
– mass balance analysis,
– reactor analysis, and
– mass transfer
 UNITS OF EXPRESSION FOR CHEMICAL
CONCENTRATIONS
• Mass concentration - component per volume of solution mg/L
• Molar concentration or molarity - (mol/L or M)
– [A](MW) = CA (Units of Expression for Chemical Concentrations e.g. Concentration of A is (CA))

– [A] = molar concentration of component A, mol/L

– MW = molecular weight of component A, g/mol
– CA = mass concentration of component A, g/L

• Mole fraction or mass fraction

X = mole fraction n = amounts of mol – C = mass fraction of component

n = amount of component, mol – m = mass in kg
N = number of components
• Mass concentration (mg/L)
– NH3, NH4+, NO3−, or NO2
– Change in mass concentration of nitrogen species even though the total
amount of nitrogen in the water has not changed (?!?!)
• Normality (N) or equivalents/volume (eq/L) - concentration in specific cases
related to ionic species in water
 CHEMICAL EQUILIBRIUM
• Chemical Equilibrium
A + B → C + D and C + D → A + B becomes
• Reaction Stoichiometry

– a, b, c, d = stoichiometric coefficients of species A, B, C, D, respectively, unitless

– One method for removing Fe2+ from water is to oxidize it with oxygen to produce insoluble ferric
hydroxide [Fe(OH)3] according to the following reaction:

– Water contains 2.6 mg/L of Fe2+. Calculate O2 required to oxidize it and the
amount of Fe(OH)3
– Q1 - Determine the molecular weight of each species involved
– Q2 - Calculate the concentration of oxygen required to oxidize the iron.
• Convert mass concentration to mol concentration (mg/L to mol/L)
• Use stoichiometry to relate mmol (Fe) to mmol O 2 [A](MW) = CA
• Convert mol concentration to mass Concentration

– Q3 - Calculate the concentration Fe(OH)3 that will be produced

• Convert mass concentration to mol concentration (mg/L to mol/L)
• Use stoichiometry to relate mmol (Fe) to mmol Fe(OH)3 or mmol O2
• Convert mol concentration to mass Concentration
• Q1. Molecular weight of each species
MW of Fe2+ = 55.8 g/mol or 55.8mg/mmol
MW of Fe(OH)3 = 55.8 + (3)(16.0) + (3)(1.0) = 106.8 g/mol or mg/mmol
• Q2. Oxygen Required
• S1 Convert mass concentration to mol concentration (mg/L to mol/L)
2,6𝑚𝑔
𝐹𝑒 ∗ 1/𝐹𝑒 𝑀𝑊 {[A](MW) = CA}
𝐿
𝑚𝑔 𝑚𝑚𝑜𝑙 𝑚𝑚𝑜𝑙
– 2,6 ∗ = 0.0465 Fe
𝐿 55.8𝑚𝑔 𝐿

• S2 Use stoichiometry to relate mmol (Fe) to mmol O2

𝑚𝑚𝑜𝑙 1𝑚𝑚𝑜𝑙𝑂𝑥𝑦 𝑚𝑚𝑜𝑙𝑂𝑥𝑦
– 0.0465 𝐹𝑒 ∗ = 0.0116
𝐿 4𝑚𝑚𝑜𝑙𝐹𝑒 𝐿

• S3 Convert mol concentration to mass Concentration

– MW of O2 is 16mg/mmol*2 = 32 mg/mmol
𝑚𝑚𝑜𝑙 𝑚𝑔 mg
– 0.0116 ∗ 32 = 0.37
𝐿 𝑚𝑚𝑜𝑙 l

Step 1 Step 2 Step 3

• Q3 Fe(OH)3 produced
• S1 Convert mass concentration to mol concentration (mg/L to mol/L)
2,6𝑚𝑔
– 𝐹𝑒 ∗ 1/𝐹𝑒 𝑀𝑊
𝐿
𝑚𝑔 𝑚𝑚𝑜𝑙 𝑚𝑚𝑜𝑙
– 2,6 ∗ = 0.0465 Fe
𝐿 55.8𝑚𝑔 𝐿

• S2 Use stoichiometry to relate mmol (Fe) to mmol Fe(OH)3

𝑚𝑚𝑜𝑙 1𝑚𝑚𝑜𝑙𝐹𝑒(𝑂𝐻)3 0.465𝑚𝑚𝑜𝑙𝐹𝑒 𝑂𝐻 3
– 0.0465 𝐹𝑒 ∗ =
𝐿 1𝑚𝑚𝑜𝑙𝐹𝑒 𝐿

• S3 Convert mol concentration to mass Concentration

𝑚𝑚𝑜𝑙 𝑚𝑔 mg F𝑒 𝑂𝐻 3
– 0.0465 ∗ 106.8 = 4.98 Step 1 Step 2 Step 3
𝐿 𝑚𝑚𝑜𝑙 L

Note that the amount of each element (Fe, H, and O) is conserved in the chemical reaction on a molar basis,
but that the mass of O2 consumed and Fe(OH)3 produced depends on the stoichiometry of the reaction and
the molecular weights of the species. On a mass basis, more Fe(OH)3 is produced than Fe2+ is consumed.
The amount of residuals produced is an important consideration during water treatment.
 CHEMICAL KINETICS
• Chemical Kinetics
• Chemical kinetics is the study of the rate at which chemical reactions take place

• the amount of reactants consumed or products generated by the

reaction per unit of volume and per unit time
– rA = reaction rate, mol/L·s
– n = amount of reactant consumed or product generated, mol
– V = volume of reactor, L
– t = time, s

• The rate of a reaction is equal to the change in concentration over time, that is,
rA = dC/dt.
 Reactions Used in Water Treatment

• (1) acid-base reactions, e.g.

– HA = acid species, H+ = hydrogen ion (hydrated proton, i.e., H3O+)
– A− = conjugate base species

Acid–base reactions involve the transfer of a hydrogen ion, or proton, between two species.

• (2) precipitation–dissolution reactions, dissolved contaminants can be removed by

causing them to precipitate and the removing the solids from water

– The precipitation–dissolution reaction for gypsum is

• (3) oxidation–reduction reactions. involve the transfer of electrons between two

chemical species. Half reaction
– OxA = oxidized species A , n = number of electrons transferred, e− = electron,
– RedA = reduced species A
– overall oxidation–reduction
 Mass Balance Analysis
• The basic steps for performing a mass balance analysis are as follows:

– 1. Draw a picture of the system.

– 2. Identify the control volume, for example, the boundaries of the system of interest.

– 3. Identify all inflows, outflows, or transformations to the components in the system.

– 4. Write the mass balance equation and identify simplifying assumptions, such as whether the
system is at steady state or whether any reactions are occurring. Clearly identify the answer you are
looking for, whether the solution should be dependent on time, and the like.

– 5. Solve the equations.

– 6. Do a ‘‘reality check,’’ verifying items such as

– (a) are the units correct?,

– (b) is the time dependence of the final equation correct?,

– (c) are the assumptions valid?, and

– (d) is the magnitude of the answers reasonable?

Mass Balance Example
Introduction to Reactors and Reactor
Analysis
 Introduction to Reactors and Reactor
Analysis

batch reactor, continuously mixed flow reactor, plug flow reactor,

 Reactions in Batch Reactors
• Reactions in Batch Reactors

• The change in mass due to chemical reactions can be determined simply by

multiplying the reaction rate by the volume of the control volume

• which implies
• r =−kC for first-order reaction Substituting r into the above equation rearrange
and intergrade both side of the equation

• Take the natural logarithm of both sides of the equation yield

• As proven First-order decay • Similarly Second-order decay reaction
• (r =−kC) results in • ( r = −kC2) results in

• Linearized form of concentration of (b)

• Linearized form of concentration of (a) second-order reactions in a batch
first-order reactions in a batch reactor reactor.
Completely Mixed Flow Reactor (CMFR)
• Pulse input

• At t= 0

• Rearange equation

• Intergrade both sides

Completely Mixed Flow Reactor (CMFR)
• Mass balance for CMFR with Step input nonreactive Chemicals

• hydraulic residence time

• After rearranging, integrating, and substituting τ

 Completely Mixed Flow Reactor
• Pulse input with nonreactive chemicals • Step input nonreactive Chemicals
 Plug Flow Reactor
Plug Flow Reactor (tracer curves for Pulse input and step input))
 Example 5

Determining the reaction order and rate constant for decomposition of ozone
 The end
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