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LECTURE 2:
ENVIRONMENTAL
CHEMISTRY
Common Prefixes
Common Dimensions
Density,
Concentration,
(kg/m)
,
.
(kg/m, mg/L)
,
,
Retention time: time an average particle of the fluid spends in the container
through which the fluid flows.
2.3: Stoichiometry
A chemical equation provides both qualitative (which chemicals) and
quantitative (how much of each compound) information.
Stoichiometry balancing of chemical equations so that the same
number of each kind of atom appears on each side of the equation and
calculation to determine amounts of each compound involve.
1st step: Balance the equation
CH4 + O2 CO2 + H2O (combustion of methane)
CH4 + 2 O2 CO2 + 2 H2O
2nd step: Calculate the mass of each substance
Atomic weight mass of the atom measured in atomic mass units (amu)
Atomic number number of protons in the nucleus
Molecular weight sum of atomic weights of all the constituent atoms
Moles =
2 O2
CO2
2 H2O
16 g of methane
+ 64 g of oxygen
Conservation of mass:
2 mol of oxygen
2 mol of water
36g of water
10
= g
3. Specific gravity, S = /o = /o
the subscript zero denotes the density of water at 3.98C, 1,000 kg/m3, and the
specific weight of water, 9.81 kN/m.
The density of water at normal temperature is taken as 1,000 kg/m (1 kg/L) with
a specific gravity = 1.00.
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Chemical Units
Molarity is the number of moles in a liter of solution. A 1-molar (1 M)
solution has 1 mole of substance per liter of solution.
mg/L = Molarity Molecular weight 10
= (moles/L)(g/mole)(10mg/g)
Equivalent weight (EW) - molecular weight divided by the number (n) of
electrons transferred in redox reactions or the number of protons (H+)
transferred in acid/base reactions.
In a precipitation reaction, n is the valence of the element. For
compounds, n is equal to the number of hydrogen ions that would be
required to replace the cation.
Eg. 2 H+ are needed to replace the calcium in CaCO3, therefore, n = 2.
Normality (N) is the number of equivalent weights per liter of solution.
N = Mn
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Example 2.2
Commercial sulfuric acid, H2SO4, is often purchased as a 93 weight
percent solution. Find the mg/L of H2SO4 and the molarity and normality
of the solution. Sulfuric acid has a specific gravity of 1.839.
Solution. Since 1 L of water weighs 1,000 g, 1 L of 100% H2SO4 weighs
1,000(1.839) = 1,839 g
(0.93)(1,839 g) = 1,710 g of H2SO4 , or 1.7106 mg/L of H2SO4 in a 93%
solution.
The molecular weight of H2SO4 = 2 (1) + 32 + 4 (16) = 98 g/mole
mg/L = Molarity Molecular weight 10
Molarity = 1.7106 mg/L of H2SO4 / 98 g/mole 10 mg/g
= 17.45 mole/L or 17.45 M
H2SO4 can give up 2 H+ and therefore n = 2 equivalents/mole:
N = Mn
N = 17.45 mole/L (2 equiv/mole) = 34.9 equiv/L
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Chemical Reactions
There are four principal types of reactions of importance in environmental
engineering: precipitation, acid/base, ion-association, and
oxidation/reduction.
Most chemical reactions are to some extent reversible. They reach
equilibrium when the rates of reaction are the same for both directions
(products are being formed on the right at the same rate as they are
being formed on the left)
aA + bB cC + dD
a, b, c, d = number of molecules or ions in a balanced equation
At equilibrium,
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Precipitation Reactions
phase change reaction of dissolved ions to solid state
Ca2+
+ CO
precipitation
dissolution
CaCO3(s)
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Interestingly, the product of the activity of the ions is always a constant for
a given compound at a given temperature. That constant is called the
solubility constant, Ks.
solubility constant, Ks =
Ks values are often reported as pKs , where
pKs = -log Ks
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Example 2.3
How many mg/L of PO
AlPO4(s)?
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Acid/Base Reactions
Acids are defined as those compounds that release protons.
Bases are those compounds that accept protons.
HA H+ +AIn order for HA to release the proton (H+) , something must accept the
proton. Often that something is water, that is,
H+ + H2O H3O+
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Acids are classified as strong acids or weak acids. Strong acids have a
tendency to donate their protons to water. For example,
HCl H+ +Cl-
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Example 2.4
If 15 mg/L of HOCl is added to a potable water for disinfection and
the final measured pH is 7.0, what percent of the HOCl is not
dissociated? Assume the temperature is 25C.
Solution. The reaction is HOCl H++ OClpKa = 7.54
Ka = 10-7.54 = 2.55 10-8
Writing the equilibrium constant,
2.55 108
H+][OCl]
HOCl
107][OCl]
HOCl
[HOCl] = 3.47[OCl-]
Since the fraction of HOCl that has not dissociated plus the OCl- that
was formed by the dissociation must, by the law of conservation of mass,
equal 100 percent of the original HOCl added;
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[HOCl] + [OCl-] = 100% (of the total HOCl added to the solution)]
Then
3.47 [OCl-] + [OCl-] =100%
4.47 [OCl-] = 100%
[OCl-] = 100% /4.47 = 22.37%
and [HOCl] = 3.47 [OCl-] = 3.47 [22.37%] = 77.6%
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Buffer Solutions
A solution that resists large changes in pH when an acid or base is
added or when the solution is diluted is called a buffer solution.
The most important buffer system in environment and water and
wastewater treatment is the carbonate buffer system.
CO2(g) CO2 + H2O H2CO3 H+ + HCO 2H+ + CO
carbonic acid
bicarbonate ion
carbonate ion
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Alkalinity
Alkalinity is defined as the sum of all titratable bases down to about
pH 4.5. It is found by experimentally determining how much acid it takes
to lower the pH of water to 4.5.
Alkalinity (nature system)
= [HCO ] + 2 [CO ] + [OH-] [H+]
Alkalinity = HCO + CO + OH- - H+) mg/L as CaCO3
mg/L as CaCO3 = (mg/L as species)
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Example 2.5
A water contains 100.0 mg/L CO and 75.0 mg/L HCO at a pH of 10.
Calculate the alkalinity exactly at 25C. Approximate the alkalinity by
ignoring [OH- ] and [H+].
Solution. First, convert CO , HCO , OH-, and H+ to mg/L as CaCO3.
The equivalent weights are
CO : MW = 60, n = 2, EW = 30
HCO : MW = 61, n =1, EW = 61
H+ : MW = 1, n = 1, EW = 1
OH- : MW = 17, n = 1, EW = 17
and the concentration of H+ and OH- is calculated as follows: pH = 10;
therefore [H+] = 10-10M.
mg/L = (10-10 moles/L)(1 g/mole)(10 mg/g) = 10-7
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Kw = [H+][OH-] = 10-14
[OH-] = Kw / [H+] = 10-14 / 10-10 = 10-4 moles/L
mg/L = (10-4 moles/L)(17 g/mole)(10 mg/g) = 1.7
Now, find the mg/L as CaCO3 , taking the equivalent weight of CaCO3 to
be 50:
mg/L as CaCO3 = (mg/L as species)
CO
= 100.0
HCO = 75.0
H+ = 10-7
OH- = 1.7
=167
=61
=5 10-6
=5.0
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Reaction Kinetics
Many reactions in the environment do not reach equilibrium quickly.
(disinfection of water, gas transfer into and out of water, removal of
organic matter from water, and radioactive decay.)
Reaction kinetics - the study of how these reactions proceed
Rate of reaction, r - used to describe the rate of formation (+r) or
disappearance (-r) of a compound.
Homogeneous reactions -Reactions that take place in a single phase
(liquid, gas, or solid)
Moles or milligrams
r=
(Unit volume)(Unit time)
Heterogeneous reactions -Reactions that take place at surfaces between
phases
Moles or milligrams
r=
(Unit surface)(Unit time)
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