Part 3 Env Chemistry

Part 3: Environmental Chemistry
Objective: to be able to understand water quality, pollution, and chemical

treatment processes, knowledge of basic chemistry is essential
Every pollution problem we face has a chemical basis. Examples include

green house effect, acid rain, and ozone depletion. So, need to know the
chemical principles
SI Units:
● Mass ……Kg, g, mg, μg…
● Amount of substance ….Mole

N = 6.02 1023
Avogadro’s number (N) of molecules of substance
Mwt (gr/mole)
● Volume…..m3, L, ml, μl
● Concentration units
o Molarity (M): # of moles of solute liter of substance (mol/L)
o Molality (M) …………(mol/kg)
o Normality (N)………...(g-eq/L)
meq/L = mg/l (valence/ atomic weight) = (mg/l) / (equivalent

weight)
Example: what is the molecular and equivalent weight of ferric sulfate

(Fe2(SO4)3)
Solution:
Types of reactions
1) Acid – Base reaction

● Change of protons (H+)
● Acid…..gives off protons
● Base…..Accept protons
H2O can be acid or Base
Example:
HNO3 +H2O……H3O+ + NO3
Acid Base Acid Base
NH3 (aq) + H2O …….NH4+ + OH-

Base Acid Acid Base
pH = - Log [H ]
+
pOH = - Log [OH-]
2) Precipitation
● Solubility of substance varies
● Supersaturated, Saturated, and under saturated

3) Oxidation reduction (redox)
● Involve transfer of e- (change of oxidation status)
● Gain e-………..Reduced
● Lose e-……….Oxidized
Balance Chemical Reaction (Stoichiometry)

o MB: atoms are not created or destroyed in chemical rxn
o Charge balance: Net charge in the reactants equals the net
charge in the products
Example 1: What mass of CO2 would be produced if 100 gr of butane
(C4H10) is completely oxidized to CO2 and water
Solution:
Example 2: Theoritical O2 demand

Consider 1.67 10-3 M glucose solution (C6H12O6) that is completely oxidized
to CO2 and H2O. Find the amount of O2 required to complete the reaction
Solution:
Chemical Equilibrium
● Rate of forward reaction equals rate of backward reaction
● Equilibrium constant depends on how the equation is written
aA + bB cC + dD
cC + dD aA + bB
[H2O] =1 [Solid] = 1
H2O H+ + OH-
S S
S2 = 10-14 ……..S = 10-7

pH = -Log[H] =7
Example: Find [H+] and [OH-] in tomato juice having pH = 4.1

Solution:
Example: Ammonia stripping

N in wastewater treatment plant is in the form of ammonia and ammonium
ion. Find the fraction of N that is in the ammonia form as a function of pH
and draw a graph. The equilibrium constant (Keq = 1.82 10-5).
Solution:
The results of this example suggest that to drive a reaction significantly
toward the ammonia side, the pH should exceed 10.
NOTE: the pH of wastewater is usually < 7.0. Therefore, to remove the

ammonia from wastewater in waste water treatment plants some chemicals
should be added such as lime (CaO) to raise the pH sufficiently.
Solubility Product:
Solid aA + bB
Where, [solid] = 1
Ksp = [A]a + [B]b

Ksp: solubility product
NOTE: Refer to text book (table 2.3) to see the tabulated values of Ksp for
several reactions.
Example: Fluoride Solubility
Find the equilibrium concentration of fluoride ions in pure water caused by

dissociation of CaF2
CaF2 Ca +2 + 2F- Ksp = 3 x 10-11

[Ca] [F]2 = 3 x 10-11
Solubility of gases in water:

Henry’s law ……
[gas] = KH Pg
[gas]: concentration of dissolved gas (mol/L)
KH : Henry’s law constant
Pg: partial pressure of the gas in air (mol/L.atm)
Or H = Ca/Cw
NOTE1: 1 atm = 101325 pascals (Pa)
1 Pa = 1 Newton/m2
NOTE2: O2 make up 21% of atmosphere
So, at 1 atm ρg = 0.21 x 1 atm = 1 atm.
NOTE3: Each gas-liquid system has its own value for Henry’s coefficient
and the coefficient varies with temperature …..(Solubility decreases as t
increases)
NOTE4: Since atmosphere pressure changes with altitude, ρg will change as

well
Ρ = P0 -1.15 10-4 H
P: atmosphere pressure at altitude H (atm)
P0: atmospheric pressure at see level (atm)
H: altitude (m)
Example: Solubility of O2 in water

Find the equilibrium concentration of O2 in water at 25oc and 1 atm of
pressure
Solution:
⮚ Chemical Kinetics......define the rate of reaction
● Fast reaction (immediately reach equilibrium = always assume

equilibrium)
● Slow reaction (Need long time to reach equilibrium = described
by kinetics
Zero-order reactions proceed at a rate independent of the concentration of

any reactant or product.
First-order reactions …most commonly define reactions that occur in the
chemical and biological processing of water and wastewater are first order.
Reactions proceed at a rate directly proportional to the concentration of

one reactant
Second-order reactions
Proceed at a rate proportional to the second power
of a single reactant being converted to a single product.
Effect of temperature on reaction rate

k2=k1θT2-T1
θ: temp coefficient (dimensionless)
k: reaction rate constant at respective temp.
T: temp. in Co
Example: if 3 gr of substance A in each L decomposes for 36 min and the
mass of A remaining uncreated is 0.375 gr. What is the half life of this
reaction if it follows (a) zero order (b) 1st order (c) 2nd order reaction rate
Solution:
Soil Chemistry:
Typical soil contains about 95% minerals and 5% organic matter, but exact
composition varies considerably.
●Ion Exchange:
Movement of ionic nutrients are governed by ionic exchange reaction
2(Na+-soil) + Ca+2 ……..Ca+2 – (soil)2 + 2 Na+
Exchange capacity: extent to which a unit mass of soil exchange a mass of

certain ion of interests.
It is important for its application as water treatment, and soil amendment

Ex: Zeolite can remove ammonia and odor problems…( cationic exchange)
● Adsorption:
Kd = Cs / Cw
Kd: Partitioning coefficient (L/Kg)
Cs: concentration in solid phase (mg/kg)
Cw: concentration in water (mg/L)
⮚ Linear adsorption isotherm
Cs = Kd Cw
⮚ Non linear adsorption isotherm

o Freundlich isotherm
Cs = Kf C1/n
Kf : freundlich isotherm
1/n: impirical constant
To linearize Log Cs = Log Kf + (1/n) Log C
o Langmair isotherm
Cs = Cmax Kd Cw / (1 + Kd Cw)
And can be linearized by rearranging equation
(Cw /Cs) = (1/k Cmax) + ( Cw / Cmax)
⮚ Effect of soil organic matter on adsorption
Adsorption of organic chemicals is strongly influenced by the organic

content of the solid
If foc > 0.001 ………Kd = Koc foc
foc : fraction of organic content and can be measured in lab
Koc : is tabulated or predicted from solubility or Kow using empirical equations
Kow : octanol water partitioning coefficient which is a measure of hydrophobicity
………………………..See provided table
Example:
What is the sorbed concentration of toluene in soil matrix having 4% organic
matter if the equilibrium concentration in water is 100 mg/L …assuming the
adsorption is linear.
Solution:
⮚ Sorption onto unsaturated soil
At equilibrium, the insaturated soil must have the same concentration as the saturated
soil.
H = (Ca / Cw) Kd = (Cs / Cw)
Kdu = Cs / Ca = Kd Cw / H Cw = Kd / H
And we have also, H = Poc / Xoc

For previous example, soil is under unsaturated condition when
P/ Po = 100/515 and Cs = 564 mg/Kg
BUT P for toluene = 0.0374 atm
0
SO,
NOTE:
● Use the molarity of air to convert to mole fraction
Molarity of air = 4.15 10-2 mol air/ L air
● Use molarity of water to concert to mole fraction
Molarity of water = 55.5 mol/L
Basic knowledge of Atmosphere:

Composition
● Non variable
o N 78%
o O2 21%
o Argon 0.93%
o Neon 0.02%
● Variable
o CO2 0.035%
o CH4, H2O, O3, NOx, SOx……
o
NOTE: CO2, CH4, H2O, NOx, SOx are called green house gases
Fundamentals gas law
● Ideal Gas Law ……relates gas pressure, temperature, and volume

PV = nRT
P: absolute pressure (Pa)
V: volume of gas (m3)
n: number of moles n = M/Mwt ( M is mass of gas (gr) and Mwt is
molecular weight (gr/mole)
R: Universal ideal gas constant = 8.314 J/K. mole
T: temperature in Kelvin
PV = n RT
P = (n/v) RT = (m/V) (R/ Mwt) T
But m/V = ρ gas density (g/m3)
Thus
P = ρ RT/Mwt = ρ R*T
Where, R* = R/Mwt
NOTE: 1 mole of an ideal gas at 1 atm and 25oc occupies a volume of 24.465 L
(24.465*10-3 m3)

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Part 3: Environmental Chemistry

Objective: to be able to understand water quality, pollution, and chemical

Every pollution problem we face has a chemical basis. Examples include

● Amount of substance ….Mole

meq/L = mg/l (valence/ atomic weight) = (mg/l) / (equivalent

Example: what is the molecular and equivalent weight of ferric sulfate

1) Acid – Base reaction

● Acid…..gives off protons

NH3 (aq) + H2O …….NH4+ + OH-

pOH = - Log [OH-]

● Supersaturated, Saturated, and under saturated

Balance Chemical Reaction (Stoichiometry)

Example 2: Theoritical O2 demand

● Equilibrium constant depends on how the equation is written

S2 = 10-14 ……..S = 10-7

Example: Find [H+] and [OH-] in tomato juice having pH = 4.1

Example: Ammonia stripping

NOTE: the pH of wastewater is usually < 7.0. Therefore, to remove the

Ksp = [A]a + [B]b

Example: Fluoride Solubility

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

CaF2 Ca +2 + 2F- Ksp = 3 x 10-11

Solubility of gases in water:

NOTE4: Since atmosphere pressure changes with altitude, ρg will change as

Example: Solubility of O2 in water

● Fast reaction (immediately reach equilibrium = always assume

Zero-order reactions proceed at a rate independent of the concentration of

Reactions proceed at a rate directly proportional to the concentration of

Effect of temperature on reaction rate

2(Na+-soil) + Ca+2 ……..Ca+2 – (soil)2 + 2 Na+

Exchange capacity: extent to which a unit mass of soil exchange a mass of

It is important for its application as water treatment, and soil amendment

⮚ Linear adsorption isotherm

⮚ Non linear adsorption isotherm

To linearize Log Cs = Log Kf + (1/n) Log C

(Cw /Cs) = (1/k Cmax) + ( Cw / Cmax)

⮚ Effect of soil organic matter on adsorption

Adsorption of organic chemicals is strongly influenced by the organic

And we have also, H = Poc / Xoc

Basic knowledge of Atmosphere:

Fundamentals gas law

● Ideal Gas Law ……relates gas pressure, temperature, and volume

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