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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
22.4
= 1 ppm ( by volume)
x
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
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.
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
3
)
= 26.67
= -KC
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
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
0.2
xC
1
24 3600
= 23,148 C
x 1000 3 = 5,500 C
xC
C = 3.5
x 107 m3 x 1000 3
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
30
22.4
273
25+273
1
1
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
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
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
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() =
V = 500 m3
S = 140 mg/hr
C() = 0.117 3
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
- amount of substance
concentration
3. Normality (N) =
()
()
= 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
2-4
30/136
=0.0041
30/136+970/18
XH20 =
970/18
30
136+970/18
= 0.9959
50 103 3
2 equivalents 2 equivalents
For Ca2+ in a precipitation or dissolution reactions,
100 /
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
/
/
/
= . /
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:
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.
aA+bB
cC+dD
[A]a[B]b
= K
(1)
[ + ][]
[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 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
[0H-] =
Solubility Product
All solids are to some degree soluble, some much more so than the others.
Generalized equation describing equilibrium condition
[]
=K
Example 7
K sp = 3.9 x 10-11
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)