1

Atomic numbers and atomic weights

(Mines & Lackey, sections 3.2.1 & 3.2.2)
Common examples in environmental engineering:
Hydrogen H 1
Carbon C 12 (14 is for radioactive form of C !)
Nitrogen N 14
Oxygen O 16
Sodium Na 23
Phosphorus P 31
Sulfur S 32
Chlorine Cl 35.45
Calcium Ca 40
For other elements, see the Periodic Table of Elements (Mines & Lackey, page 33)
Molecule = combination of atoms
Atom = nucleus + orbiting electrons
Electrons have a negative charge and are virtually weightless.
Nucleus = protons + neutrons
Protons have a positive charge; neutrons have no charge
Atomic number = number of protons in nucleus = number of orbiting electrons
Atomic weight = sum of masses of protons and neutrons in nucleus
atomic number.
Radicals
(Mines & Lackey, pages 34-35)
Oftentimes, species and products of reactions dissolved in water are incomplete
molecules. These possess a non-zero electric charge and are called radicals.
Examples:
H
+
simple proton
OH

hydroxyl or hydroxide ion

HCO
3

bicarbonate
CO
3
2
carbonate
NH
4
+
ammonium
NO
2

nitrite
NO
3

nitrate
PO
4
3
(ortho)phosphate
SO
4
2
sulfate
Note that some have positive charges and some negative charges; some have single
charges, others double charges. Triple charge is possible but rare.
Definition: z = number of charges (absolute) or valence.
2
Types of chemical reactions
(Mines & Lackey, section 3.3)
1. Synthesis
2. Decomposition
3. Single-replacement reaction
4. Double-replacement reaction
5. Combustion / Thermal oxidation
Generic: A + B AB
Examples: CaO + H
2
O Ca(OH)
2
CO
2
+ H
2
OH
2
CO
3
Generic: A + BC AC + B
Example: (cant find one in environmental context)
Generic: AB A + B
Example: H
2
CO
3
H
+
+ HCO
3

Generic: AB + CD AD + CB
Example: HCl + NaOH H
2
O + NaCl
Generic: C
m
H
n
+ O
2
n CO
2
+ (n/2)H
2
O
Example: CH
4
+ 2 O
2
CO
2
+ 2 H
2
O
Stoichiometry
(Mines & Lackey, section 3.3.1 + more here)
Stoichiometry is the application of mass balance to chemical transformation.
In short, atoms are conserved, and when combinations of atoms disintegrate,
new combinations form with the same atoms. In other words molecules exchange
among themselves bits and pieces, without any net loss or gain.
Example: Oxidation of glucose
C
6
H
12
O
6
+ (???) O
2
(???) CO
2
+ (???) H
2
O
First, equilibrate the Cs and Hs before and after:
C
6
H
12
O
6
+ (???) O
2
6 CO
2
+ 6 H
2
O
Thus, we need 6x2 + 6x1 = 18 Os on the right; already 6 on left, need 12 more:
C
6
H
12
O
6
+ 6 O
2
6 CO
2
+ 6 H
2
O
3
Use of stoichiometry to make material budgets
Take oxidation of glucose again:
C
6
H
12
O
6
+ 6 O
2
6 CO
2
+ 6 H
2
O
From this, we note that it takes
6 molecules of oxygen (O
2
) to oxidize 1 molecule of glucose (C
6
H
12
O
6
).
Thus, 6 moles of oxygen are needed to oxidize 1 mole of glucose.
MWof oxygen = 2x16 = 32 g/mol
MWof glucose = 6x12 + 12x1 + 6x16 = 72 + 12 + 96 = 180 g/mol
So, it takes 6x32 = 192 grams of oxygen to oxidize 180 grams of glucose.
Check values on the right:
Production is 6 moles of carbon dioxide (CO
2
) 6x(12+32) = 6x44 = 264 grams
6 moles of water (H
2
O) 6x(2+16) = 6x18 = 108 grams
Total on right = 264 + 108 = 372 grams
while total on left is = 180 + 192 = 372 grams.
In-class problems
Combustion of butane: C
4
H
10
Formation of ambient ozone (O
3
), by three successive reactions:
NO
2
splits into NO and atomic O
O combines with oxygen to make ozone
Ozone reacts with NO to produce O
2
and NO
2
Answers:
C
4
H
10
+ 6.5 O
2
4 CO
2
+ 5 H
2
O (208 grams of oxygen needed
to burn 58 grams of butane)
NO
2
NO + O
O + O
2
O
3
(46 grams of nitrogen dioxide produces 48 grams of ozone)
O
3
+ NO O
2
+ NO
2
4
pH
(Mines & Lackey, section 3.4.1)
The concentration [H
+
] of protons is of utmost importance because it affects
most ambient chemical processes.
A typical value of [H
+
] is small and expressed as xx.x 10
-n
moles/liter (mol/L or M).
This can be rewritten as [H
+
] = 10
-y.yy
mol/L with y.yy =n log
10
(xx.x) .
Note: value 1.0
in front
y.yy is called the pH.
In other words, the pH is none other than the negative power of 10 in the value of [H
+
] .
It is only defined as shorthand for convenience and by tradition.
Natural dissociation of water
(Mines & Lackey, page 44)
Liquid water always dissociates a little bit on its own, with the following equilibrium
being reached almost instantaneously and in all circumstances (= even if other
substances are present!):
H
2
O H
+
+ OH

with [H
+
] [OH

] = 10
-14
.
If water is pure, there are no other sources of H
+
and OH

ions, and the two ions can

only result form water dissociation, thus being equal to each other in amount.
It follows that in pure water:
[H
+
] = [OH

] = 10
-7
with the attending result: pH = 7. This is the neutral state.

5
(Source: Mines & Lackey, Figure 3.2, page 43)
Example of pH values
Acids and Bases
(Mines & Lackey, section 3.4.2
An acid is a substance which, when dissolved in water, splits by forming the H
+
ion.
The added H
+
ions lower the pH.
Generically: HA H
+
+ A

Examples: H
2
CO
3
H
+
+ HCO
3

HNO
3
H
+
+ NO
3

In contrast, a base is a substance which, when dissolved in water, splits by forming

the OH

ion, which in turns drives the water dissociation equilibrium toward fewer H
+
ions, with the result of increasing the pH.
Generically: BOH B
+
+ OH

Example: NH
3
+ H
2
O NH
4
+
+ OH

Oftentimes, however, in the environment, a substance acts as a base more directly,

by absorbing H
+
ions rather than by producing OH

ions.

6
Example of a substance acting as a base in the environment:
CaCO
3
Ca
2+
+ CO
3
2
CO
3
2
+ H
+
HCO
3

HCO
3

+ H
+
H
2
CO
3
H
2
CO
3
H
2
O + CO
2
Note how this series of reactions take away 2 H
+
ions for each CaCO
3
that is dissolved.
Terminology: Calcium carbonate (CaCO
3
) is said to buffer the solution.
It has buffering capacity.
Chemical kinetics
(Mines & Lackey, Section 6.2.1; Mihelcic & Zimmerman, Section 3.11)
This is the answer to what happens when chemical equilibrium is not reached.
For example, take the two-way reaction
A + B C + D
As A and B come into contact with each other, they start to react one with the other, and
the reaction rate can be expressed as
R
forward
=k
f
[A] [B].
This expression reflects the fact that the more A and B there is, the more encounters
take place, and the faster the rate of reaction.
This rate depletes the amounts of both A and B, and adds to the amounts of C and D:
[A][B]
[D] [C]
[A][B]
[B] [A]
f forward
f forward
k R
dt
d
dt
d
k R
dt
d
dt
d
+ = + = =
= = =
7
But, at the same time, C and Dcome in contact, too, and carry their own (reverse) reaction,
at a rate proportional to their amounts
R
reverse
=k
r
[C] [D]
This rate depletes the amounts of both C and D, and adds to the amounts of A and B:
[C][D]
[D] [C]
[C][D]
[B] [A]
r reverse
r reverse
k R
dt
d
dt
d
k R
dt
d
dt
d
= = =
+ = + = =
Putting the two reactions together, we have:
[C][D] [A][B]
[D] [C]
[C][D] [A][B]
[B] [A]
r f reverse forward
r f reverse forward
k k R R
dt
d
dt
d
k k R R
dt
d
dt
d
+ = + = =
+ = + = =
At equilibrium, the two rates equate each other and the amounts of A, B, C and D
no longer change in time (zero time derivatives).
The condition for equilibrium is thus:
,
[A][B]
[C][D]
[C][D] [A][B]
r f reverse forward
K
k
k
k k R R
r
f
= =
= =
a constant (which depends on temperature).
8
Reaction order
(Mines & Lackey page 122; Mihelcic & Zimmerman, Section 3.11)
The previous example assumed that it takes two chemicals for each reaction. This is
not always the case. For example, when a substance dissolves in water
H
2
CO
3
H
+
+ HCO
3

The forward reaction needs only one concentration

R
forward
=k
f
[H
2
CO
3
]
Nomenclature:
Second-order reaction:
First-order reaction:
Zeroth-order reaction:
k
dt
d
k
dt
d
k
dt
d
=
=
=
] A [
] A [
] A [
] B ][ A [
] A [
Note: the units of the k coefficients vary!
Equilibrium & Kinetics of Phase Change
(Mihelcic & Zimmerman, Sections 3.5 3.6)
Consider a closed vessel half filled with water
and topped with air. As we can expect, some of
the water evaporates into the air, and some of the
water vapor in the air will condense back into
liquid water. The two processes of evaporation
and condensation will eventually come to
equilibrium and set a certain level of moisture in
the air above the water.
layer air the of height the is
air
where
c e
c e
conden evap air
(moisture) air in the water of ion concentrat where
c conden
: on Condensati
contact of surface where
e evap
: n Evaporatio




S
V
H C
H
k
H
k
dt
dC
SC k S k
R R
dt
dC
V
C SC k R
S S k R
= =
=
=
= =
= =
9

c e
C
H
k
H
k
dt
dC
=
If (initially dry air), then the evolution of the water vapor in the air
over time is
0 ) 0 ( = = t C
(

|
.
|

\
|
= t
H
k
k
k
t C
c
c
e
exp 1 ) (
Eventually, equilibrium is reached
in which
c
e
k
k
C =
Concentration of water vapor in the air can be transformed into partial pressure
of water vapor.
Water weighs 18 grams per mole. Thus, the number of moles of water vapor
per volume of air is
grams/mole 18
me grams/volu
air
water
C
V
n
=
and the partial pressure of water is (assuming that it behaves as an ideal gas):
RT
C
RT
V
n
P
18
air
water
water
= =