LESSON I

1.Introduction to Environmental Engineering

Environmental Engineering - is the application of science and engineering principles, to improve
Natural environments( air, water and for land resources) to provide healthy water, air, and land or
Human habitation ( house or Home ) and for other organisms, and remediate polluted sites.

2. Environmental Engineering is concentrated in the following aspects:

a. Waste water management
b. Air pollution control
c. recycling
d. waste disposal
e. radiation protection
f. Industrial Hygiene
g. Environmental Sustainability
h. public Health
3. Environmental Science
a. Units of Measurements
Quantity

SI Units

SI symbol

Conversion factor

= USCS units

Length

meter

3.28

ft

Mass

Kilogram

Kg

2.2

lb

Temperature

Celcius

Deg C

1.8 deg C + 32

Deg F

Area

Square metre

m2

10.76

ft2

Volume

Cubic meter

m3

35.31

ft3

Energy

Kilo joule

kJ

0.95

Btu

Power

Watt

3.41

Btu/hr

Velocity

meter/sec

m/s

2.23

mi/hr

Flow rate

m3/sec

m3/s

35.31

ft3/s

Density

Kilogram/m3

Kg/m3

0.0624

lb/ft3

2. Liquids
Concentration of substances dissolved in water are usually expressed in terms of the weight
of the substance per unit volume.
1 mg/L = 1 g/m3 = 1 ppm by weight
1 g/ L = 1 mg/m3 = 1 ppb by weight
If concentration of liquids wastes is high:

= ppm x SG

Where SG = Specific gravity

3. Gases
1
106

22.4

= 1 ppm ( by volume)
x

273
()

Where T in deg K = T in deg C + 273

()
1

Example 1.
The quality air standard for carbon monoxide ( CO) based on an 8 hr measurement is 9 ppm.
Express this in mg/m3 at 1 atm and at 25 deg C. also express as a percentage volume.
Solution:
mol. weight of CO = 12 + 16 = 28 g/mole

9 28
22.4

273

x 298 x 1 = 10.3 3

Percentage by volume =

9
106

x 100% = 0.0009%

Material Balance:
A Substance that enters a region has three possible fates. Some of it may leave the region
unchanged; some of it may accumulate along the boundary; and some of it may be converted along the
boundary( e.g. CO entering may be converted to CO2)
Material Balance Equation:
Input rate = Output rate + Decay rate + Accumulation rate
Inputs

Boundary
Acc
Decay

Outputs
Material Balance Diagram

Three cases for the material balance equation:

1. Steady state or Equilibrium Conditions
Equilibrium simply means that nothing is change with time; the system has had its inputs
Held constant for a long time that any transients have had a chance to die out.
Pollutant concentration is set equal to zero.

2. Conservative System
The substance is conserved within the region in question, meaning there is no radioactive
decay, bacterial decomposition or chemical reaction occurring. In the material balance equation,
decay rate = 0
Example: dissolved solids in water or CO2 in air.
3. Non Conservative System
These would include radioactive radon gas in a home or decomposing organic wastes in lake.

I. STEADY STATE CONSERVATIVE SYSTEM

Accumulation Rate = 0 and Decay Rate = 0
Material balance equation:
INPUT RATE = OUTPUT RATE
Let one input be a stream of water or air with a flow rate Qs ( Vol/time) and pollutant
concentration Cs(mass/volume). Let the other input be a waste stream with flow rate Qw and pollutant
And pollutant concentration Cw. Let the output is a volume Qm and pollutant concentration Cm.
If the pollutant ids conservative:
CsQs + CwQw = CmQm

Example 2.
A stream flowing at 10m3/s has tributary feeding into it with flow of 5 m3/s.
The stream concentration of chlorides upstream of the junction is 20 mg/L and the
Tributary chloride concentration is 40 mg/L. Treating chloride as a conservative substance,
And assume complete mixing of the two streams, find the downstream chloride concentration.

Cs = 20 mg/L

Cm = ?

Qs = 10 m3/s

Qm = ?

Cw = 40 mg/L
Qw = 5 m3/s

Solution:
CsQs + CwQw = input rate
( Qs + Qw)Cm = output rate
Input Rate = 10 m3/s x 20 mg/L + 5 m3/s x 40 mg/L = 400

Output Rate = Cm(15

3
)

Input Rate = Output Rate

400 = 15Cm
Cm =

= 26.67

II. STEADY STATE SYSTEM WITH NON CONSERVATIVE SYSTEM

Material Balance Equation:
Input rate = Output rate + Decay Rate
The Decay of non conservative substance is usually modelled as first order reaction:
The rate of loss of a substance is proportional to the amount of substance that is present:

= -KC

Solving the DE:

Then, C = Coe-Kt
Where Co is the initial concentration
Example 3. A radium decomposes at the rate proportional to the amount present. It is found that
0.2% of disappears in 10 yrs.. What percentage will disappear in 1000 yrs.
Solution:
Co - initial concentration of radium
t = 0 , C = Co

Co = Coeo , Co = Co
From C = Coe-Kt
t = 10 yrs , 0.2% disappears ( 99.8% remains)
t = 10 yrs

C = 0.998Co
0.998Co = Coe-K(10)
0.998 = e-10K
K=

ln 0.998
10

= 2.002 x 10-4

C = Coe-2.002x10-4t

When t = 1000 yrs

C = Coe -2.002 x 10-4(1000)

C = 0.8185Co
Then the amount waste lost is
1 81.85% = 18.15%

Eq 1 indicates the rate of change of concentration of the substance.

If we assume that the substance is uniformly distributed throughout a volume V, then the total
Amount of the substance is CV . The total rate of decay of the amount of the non conservative
Is:
The material balance equation is given by:
Input rate = Output rate + KCV

Example 4.
Consider a lake with a volume 0f 107 cubic meter that is fed by a stream with a flow rate
Of 5 cu. m/s and a pollution concentration equal to 10 mg/L. There is also sewage outfall that discharges
0.5 cu.m/s of the same pollutant in the lake. The sewage has concentration of 100 mg/L and a reaction
rate coefficient of 0.2/day. Assuming that the pollution is completely mixed in the lake, and assuming
No evaporation or other losses or gains, find the steady state concentration.

outfall

Qw = 0.5 m3/s
Cw = 100 mg/L

Lake
Incoming stream

Outgoing
V = 10 x 106 m3
K = 0.2/day
C=?

Qs = 5 m3/s
Cs = 10 mg/L

Cm = ?
Qm =?

Solution:
Let C = the steady state concentration in mg/L
3

Input rate = 5

= 105

x 10

1000
3

+ 0.5

x 100

1000
3

Output rate = ( 5 + 0.5)

Decay rate = KCV =

0.2

xC

1
24 3600

= 23,148 C

x 1000 3 = 5,500 C
xC

Input rate = Output rate + Decay rate

C = 3.5

x 107 m3 x 1000 3

105 = 5,500 C + 23,148 C

Example 5.
A bar with volume 500 m3 has 50 smokers in it, each smoking two cigarettes per hour. An
Individual cigarettes emits, among other things, about 1.40 mg of formaldehyde(HCHO). Formaldehyde
Converts to carbon dioxide with reaction rate coefficient K = 0.4/hr. Fresh air enters the bar at the rate
of 1000 m3/hr. and stale air leaves at the same rate. Estimate the steady state concentration of
formaldehyde in the air, assuming complete mixing. At 25 deg C and 1 atm of pressure, how does the
result compare with the threshold for eye irritation of about 0.05 ppm?

1000 m3/hr

Indoor concentration C
V = 500 m3

1000 m3/hr

140 mg/hr
Fresh air

K = 0.40/hr

Solution:
Input rate = 50 smokers x 2 cig/hr x 1.4 mg = 140 mg/hr
Since there is complete mixing : concentration of formaldehyde C in the bar is the same
as the concentration that is leaving:
Output rate = 1000 m3/hr x C mg/m3 = 1000 C mg/hr
Decay rate = KCV = 0.4/hr x C mg/m3 x 500 m3 = 200 C mg/hr
Input rate = Output rate + Decay rate
140
= 1000 C + 200 C
C = 0.117 mg/m3
To convert to ppm:

22.4

273
()

()
1

mol wt. of HCHO = 1 + 12 + 1 + 16 = 30

0.117 =

30
22.4

273
25+273

1
1

ppm = 0.95 ppm > 0.05 ppm

thus, more than enough to cause eye irritation.

Exercise 1. Conversion

1. The air quality standard for ozone is O3 is 0.08 ppm. Express that standard in 3 at
1 atm pressure and 20 deg C. Ans.

159. 73

2. The exhaust gas from an automobile contains 1 % by volume of carbon monoxide.

Express this concentration in 3 at 25 deg C and 1 atm. Ans. 114.51 mg/m3

3. Suppose the average concentration of SO2 is measured to be 400 3 at 25 deg C and 1 atm.
Does this exceed the 24 hr air quality standard of 0.04 ppm? Ans. 0.15 ppm > 0.04 it exceeds
the 24 hr. air quality standard

STEADY STATE CONSERVATIVE SYSTEM

4. Five million gallons per days (MGD) of a conservative substance with concentration 10 mg/L,
is released into a stream having upstream flow of 10 MGD and substance concentration of 3 mg/L.
Assume complete mixing.
a) What is the concentration in ppm just downstream? Ans. C = 5.33 mg/L
b) What is the mass rate of the substance in lb/day passing just downstream of the junction
Note: 1.0 cu. m = 264 gal. Ans. mass rate = 15 MGD/264 gal. = 56.818 m3/day = 12,500 lbs./day

STEP FUNCTION RESPONSE: input rate = output rate + decay rate + accumulation rate
A case wherein there is a sudden change in the amount of pollution entering the
system.
In the box fig. below, the environmental system that is to be modelled has been drawn
as if it were a box of volume V that has equal flows Q into and out of the box. Let assume that the
contents of the box are at all times completely mixed so that the pollutant concentration C in the box
Is the same as the concentration leaving in the box
Total mass of the pollutant in the box = VC
Rate of increase of pollutant = V dC/dt
Let S = total at which pollutant enters the box ( unit: mass/time)
Input rate = Output rate + Decay rate + Accumulation rate
Accumulation rate = Input rate - Output rate - decay rate

V = S - QC - KCV
Incoming

vol V
C

Flow rate, Q
Rate pollutant input, S

outgoing
Flow rate, Q

Pollutant reaction rate, K

Concentration in the box and leaving, C

Where
V = volume of the box
C = concentration in the box and the exiting waste
S = total rate at pollutant enters a box
Q = the total flow rate into and out of the box
K = reaction rate
To find the Steady State solution that is after time t = , set dC/dt =0
C() =

Concentration before it reaches the steady state ( Ct )

C(t) =[ Co - C()]e-(K + )t + C()

2
Where Co = initial concentration in the box at time t = 0
Example 6.
The bar of example 5 Had a volume of 500 m3, withfresh air entering at the rate of 1000 m3/hr.
Suppose the air in the bar is clean when it opens at 5 pm, If formaldehyde with reaction rate k = 0.4/hr
Is emitted from the cigarette smoke at the constant rate of 140 mg/hr starting at 5 pm, what would be
the concentration at 6 pm?
Solution
Q =1000 m3/hr

V = 500 m3

S = 140 mg/hr

Steady State Concentration C() ;

C() = 0.117 3

To determine the concentration at any time after 5 pm ( t = 0)

C(t) = 0.117 - 0.117e-2.4t
At 6 pm ( t = 1 hr)

C (1) = 0.106 3

k = 0.4/hr

Exercise 2.
5. A steady state conservative system
A river with 400 ppm of salts ( conservative substance) and an upstream flow of 25 m3/s
receives an agricultural discharges of 5 m3/s carrying 2000 mg/L of salts. The salts quickly become
uniformly distributed in the in the river. A municipality just downstream withdraws water and mixes it
with enough pure water ( no salt) from another source to deliver water having no more than 500 ppm
salts to its customers. What should be the mixture ratio F of pure water to river water?
500 ppm
FQ m3/s
25 m3/s
0 ppm
400 ppm
Q m3/s

5 m3/s
2000 mg/L
6. Non conservative system : Input rate = output rate + decay rate
A lake with constant volume 10 x 106 m is fed by a pollution free stream with flow rate 50 m3/s
A factory dumps 5 m3/s of a non conservative waste with concentration 100 mg/L into the lake. The
Pollution has reaction rate coefficient K = 0.25/day. Assume the pollution is well mixed in the lake. Find
the steady state concentration of pollution in the lake.
7. Step function response: Input rate = output rate + decay rate + accumulation rate
A lagoon with volume 1200 m3 has been receiving a steady flow of a non conservative waste
At the rate of 100 m3/day for a long enough time to assume that steady state conditions apply. The
waste entering the lagoon has a concentration of 10 mg/L. Assuming complete mix conditions, a) what
would be the concentration of pollutant in the effluent leaving the lagoon? If the input waste
concentration suddenly increases to 100 mg/L, b) What would the concentration in the effluent be 7
days later? K = 0.2/day

2-1

ENVIROMENTAL CHEMISTRY

Stoichiometry- Balancing of equation so that the same number of each kind of

atom appears on each side of the equation and the subsequent calculations which
can be used to determine amounts of each compound involved.
Atomic weight of an atom- is the mass of the atom measured in atomic mass units
(a mu). 1 a mu = 1/12 of the atom mass of the carbon atom having 6 protons and
6 neutrons in its molecules.
Isotopes- atoms having the same number of protons but differing number of
neutrons.
Atomic number is the number protons in the nucleus.
Molecular weight of the molecule is the sum of the atomic weights of all the
constituent atoms.
1 mole = mass of the substance divided by its molecular weight
Moles =

1 g/ mole = 6.022 x 1023 molecules

Examples 1
For the reaction:
CH4 + 202 CO2 + 2H2 O
CH4 = 12 + 4 x 1 = 16 g/ mole
O2 = 2 x 16
= 32 g/ mole
H2O = 2 x 1 + 16 = 18 g/mole
The given reaction means:
CH4 + 202 CO2 + 2H2O
1 mole of methane + 2 moles of oxygen = 1 mole of carbon dioxide + 2 moles of
water

Mole Context of Expressing Concentration:

1.Molality (m) mole/kg = moles of solution

1 kg of solution
2.Molarity (M) mole/L=

- amount of substance

concentration
3. Normality (N) =

Where equivalent weight in g/eq =

()
()

Where n is change the number of protons denoted by in an acid base

reaction or is the total Change in valence in an oxidation reduction
reaction. If two different solutions have the
Same normality, they will react in equal proportion:
VANA =VBNB
Where VA,VB are the volumes of solutions A and B and NA, NB are
the Respective normalities.

4.Mole fraction X==

= XB =

Example 2
A solution is 3% by weight of CaS04 in water. Express the
concentration in
a.molality
b.molarity
c.mole fraction
Solution:
Mol weight of CaS04 is 20+32+16x4=136 g/mole
3% by weight= 0.03 g/ kg =30 g/kg
Mol wt. water = 1x2 +16 = 18 g/mole

a.molality m =

b.molarity (M)

= 0.22

= 0.22 mole/L =0.22M

2-4

c. Mole fraction of CaSO4

Total volume of solution = 1 liter=1000 ml
Solute: 30 ml Solvent (water): 970 ml
XCaSO4=

30/136

=0.0041

30/136+970/18

XH20 =

970/18
30
136+970/18

= 0.9959

Mass Concentration of CaCO3:

A very common system for expressing hardness
(calcium and magnesium) and alkalinity (HCO3-, CO32-, OH) concentration in water chemistry is the calcium
carbonate system. This system of units can be thought of
normalizing concentration to CaCO3, a substance
commonly used in water chemistry. In this system, the
concentration of a substance as mg/L is determined by the
equation:
Number of equivalents of substance per liter
x

50 103 3

For example for Hardness:

CaCO3
Ca2+ +
CO321 mole
1 mole
1 mole

2 equivalents 2 equivalents
For Ca2+ in a precipitation or dissolution reactions,
100 /

Equivalent weight of CaCO3=

2 /

= 50 /

Example 3
Given the concentration of Ca2+ as 92 mg/L in a solution,
express the concentration in eq/L and also in mg/L of CaCO3.

Solution:
The equivalent weight of Ca2+ in mg/meq=molecular
weight/charge
=40/2 =20 mg/meq
/

The normality in eq/L =

/
/

= . /

But the equivalent weight of Ca as CaCO3 = 50 g/eq = 50

mg/meq
Concentration of Ca in mg/L as CaCO3
=50 mg/meq x 4.6 meq/L = 230 mg/L

Stochiometric Examples:
Example 4
What mass of carbon dioxide would be given if 100 g of butane C4H10
is completely oxidized to carbon dioxide and water?
Solution:
Reaction: C4H10+ O2 CO2+H2O
Balance the equation: 2C4H10 +1302 8CO2+10H2O
Mol. Weight of C4H10 = 4x12+10x1=58 g/mole
Mol. wt of O2=32 g/mole
Mol. wt CO2=12+2x16=44 g/mole
Mol. wt of H2O=2x1+16=18 g/mole

In the equation:
2 moles of C4H10 + 13mole of O2 yields 8 CO2+ 10 moles H2O
2x58 g of C4H10 + 13x32 g of O2 yields 8x44g of CO2 + 10x18g of H2O
Ratio:
116:416------352:180 ;
dividing 116 by 100 make 1.16
100:358.62-----303.45:155.17
Answer: 303.44 g of CO2 are produced:

The proportion:

X = 303.44 g of CO2 are produced

Exercise 1. Consider the following equation representing the combustion of

propane:
C3H8 + O2 = CO2 + H2O
a) Give the balance equation
b)How many moles of oxygen are required to burn one mole of propane?
c) How many grams of oxygen are required to burn 100 g propane?
d) At standard temperature and pressure, what volume of oxygen would be
required to burn 100 g of propane? If the oxygen is 21 % of air, what volume of
air at STP would be required?
2. Balance the following reactions:
a) C + O2 = CO
b) H2 + Br2 = HBr
c)O3 = O2
d) k + H2O =KOH + H2
e) Cl2+ Nal = NaCl + I2

2-6

CHEMICAL EQUILIBRIA
In the reaction considered in the previous discussion, the assumption has been

that they proceed in one direction only. Most chemical reaction are, to some extent,
reversible, proceeding in both directions at once. When the rates of reaction are the
same, I.e. product are being formed on the right at the same rate as they are being
formed on the left, the reaction is said to have reached equilibrium.

Generalized Reversible Reaction:

aA+bB

cC+dD

a, b, c, and d are coefficients corresponding to the number of molecules or ions of

the respective substances that result in a balanced equation.
A,B,C and D are chemical species.
Double arrow ( ) indicates that the reaction proceeds in both directions at the same time.

In equilibrium: [C]c [D]d

[A]a[B]b

= K

(1)

Where [ ] designation represents concentration of the substances in equilibrium,

Expressed in moles per liter.
K= equilibrium constant
Many molecules, when dissolved in water, separate into positively charged ions called
cations and negatively charged ions called anions.
Equation 1 can be applied to the dissociation of these molecules, in which K is known
As the ionization constant.
ACID BASE REACTIONS
Water dissociates slightly into hydrogen ions(proton, H+) and hydroxide ions (OH+)
H20 H+ + OHThe corresponding equilibrium concentration for this reaction is:

[ + ][]
[2 0]

= K

The molar concentration of water in its pure state is 1000 g/L divided by 18 g/ mole=
55. 56 mole/L . Since water dissociates only slightly, the molar concentration after
Ionization is not changed enough to be of significance, so {H2O} is essentially a constant that
can be include in the equilibrium constant.

2-7

The result [H+][OH-] = KW = 10-14 AT 25 DEG C.

To express hydrogen ion concentration, we use the pH scale:

pH = -log[H+] or [H+] = 10-pH
A neutral solution correspond to the case where the concentration of hydrogen ion =
Concentration of hydroxide ion.
[H+][OH-] = [H+][H+] = [H+]2 = 10-14
Thus: [H+] = 10-7 or pH = 7
Acidic solution is one which [H+] is greater than [OH-]: pH < 7
Basic solution : [OH-] is greater than [H+] : pH >7

The pH scale
Acid base reaction are among the most important in the environmental engineering. Often, to
protect the local ecosystem, wastes will require neutralization before being released into the
environment. Most aquatic forms of life, for example are very sensitive to the pH scale of their habitat,
in other circumstances by forcing the pH toward one end of the spectrum or the other, chemical
equilibrium equations can be shifted toward the left or the right, possibly resulting in unwanted
substances being given out of solutions as precipitate or gases.
As an example of the value of being able to control pH consider the problem of removing
Nitrogen from municipal wastewater. One reason we might want to remove nitrogen is to keep it from
Stimulating the growth of algae in the receiving body of water. Another reason might be to prevent
Excessive nitrate [NO3 -] levels in drinking from causing a potential lethal condition in babies
Known as methemoglobinemia.

2--6

Example 6

Find the hydrogen ion concentration and hydroxide ion

concentration in tomato Juice having a pH of 4. 1.
Solution:
[H+] = 10-pH = 10-4.1 = 7.94 X 10-5 mol/L
[H+][0H-] =10-14

[0H-] =

= 1.26 x 10-10 =1.26 x 10-10 mole/L

Solubility Product
All solids are to some degree soluble, some much more so than the others.
Generalized equation describing equilibrium condition

( solid dissociating into its ionic components- dissolution)

( ionic components are recombining into the solid form precipitation)
Dissolution is occurring at the same rate as precipitation
Solid aA + bB
A and B are ionic components that make up the solid:
[][]

[]

=K

As long as there is still solid present in equilibrium:

[A]a[B]b = K sp K sp is called the solubility product

TYPICAL SOLUBILITY-PRODUCT CONSTANT AT 25c

Significance in
Equilibrium equation
K sp
environmental engineering
2+
9
CaCO3 Ca + CO
4.7 x 10
Hardness removal, scaling
2
+
2/4
5
CaSO4 Ca + SO
2.4 x 10
Fuel gas desulfurization
Cu(OH)2 Cu2+ +20H
1.6 x 10- 19
Heavy metal removal
Al(OH)3 Al3+ + 30H
5 x 10- 33
Coagulation acidification
23/4
-32
Ca3(PO4)2 3Ca +2PO
1.3 x 10
Phosphate removal
CaF2 Ca2+ + 2F
3.9 x 10 -11
Fluoridation

Example 7

Find the equilibrium concentration of fluoride ions in pure water caused by

the dissociation of CaF2 . Express the answer both units of mol/L and mg/L.
From the table:
CaF2 Ca 2+ + 2F-

K sp = 3.9 x 10-11

Mass action equation:

[Ca2+ ] [F- ]2 = 3.9 x 10-11
(1)
2+
Let s = solubility of Ca in mole/L
Then 2s = solubility of F- : ( 2 moles of F- is produced for every mole of Ca2+ )
Equation 1 becomes:

( s )(2s)2 = 3.9 x 10 -11

4s3 = 3.9 x 10-11

S = [ Ca2+] = 2.1 X 10-4
2s = [F-] = 4.2 x10-4

Concentration of fluoride ions in mg/L =

4.2 x 10-4

x 19 x

1000

= 8

This fluoride concentration is far above recommended drinking water levels at 1.8
mg/L. fluoride concentrations of approximately 1 mg/L in drinking water help prevent
dental cavities in children, but discoloration of teeth, called mottling is relatively
common when concentrations exceed 2 mg/L.
Example 7. Solid aluminium Phosphate AlPO4 is in equilibrium with its ions in solution:
AlPO4 Al3+ + PO43Ksp = 10-22
Find the Equilibrium concentration of Phosphate ions in mg/L.
Exercise 8. What is the pH of a solution containing 3 x 10-4 mg/L of OH- (25 deg. C)

Solubility of gases in water :

When air comes in contact with water, some of it dissolves in water. Different
constituents of air dissolve to different degrees and in amounts that vary with
temperature and water purity. The behavior of gases in contact with water was
reported by W. Henry:
Henrys Law:
X = KH Pg
X = mole fraction of gas dissolved in liquid
KH = Henrys Law constant
Pg = partial pressure of the gas in air ( atm )
1 atm = 760 mm Hg = 101. 325 kPa