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Units of Measurement - Liquids

Concentrations of substances dissolved in water expressed in terms of 1. mass or


number per unit volume of mixtureMass milligrams (mg), micrograms (g)Number
moles (mol)(one mole of any substance has Avogadros number of molecules in it
[6.02 1023 molecules/mol] and has a mass equal to its molecular weight)Volume
Litre (L) or cubic meter (m3)2. mass of substance per mass of mixture- parts per
million (ppm) [1 drop of ribena in 56.87L water]- parts per billion (ppb) [1 drop
of saliva in 70m3 swimming pool](practically 1L mixture has a mass of 1,000g)1 mg/L
= 1 g/m3 = 1ppm (by weight)1 g/L = 1 mg/m3 = 1 ppb (by weight)mg/L = ppm
specific gravity (in cases where conc. so high it affect SG)

2.2: Unifying Theories

Law of conservation of mass:When chemical reactions take place, matter is neither


created nor destroyed (except in nuclear reactions, mass can be converted to
energy)Law of conservation of energy: Energy cannot be created or destroyed(with
the birth of the nuclear age)Law of conservation of mass and energy : Total amount
of energy and matter is constant.Exchange between mass and energy is not an issues
in environmental application. Thus, there are generally two separate balances for
mass and energy.

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.

Atomic weight mass of the atom measured in atomic mass units (amu) Atomic

number number of protons in the nucleusMolecular weight sum of atomic weights


of all the constituent atoms

2.4: Water Chemistry

Water chemistry is important in the design of water and wastewater processes and in
the remediation of environmental pollution.Alkalinity chemistry natural
alkalinity in the environment maintains the waters of the world at a near neutral
pH. It prevents many contaminants from dissolving into the water. This balance
protect water sources, used in treatment of water to render it potable or more
aesthetically acceptable for consumption or to treat waste streams for discharge.
Water treatment - add chemicals to react with impurities to remove them
(precipitation) or render them harmless (oxidation, redox reaction). We must know
chemical doses, chemical type, reaction kinetics (rate of reaction [to determine
reactor size]), phase transfer from water to air (for volatile contaminants in
water)

Basic Water Properties and Units

Physical Properties of Water:

Density measure of the concentration of matter

1. Mass density, rho - mass per unit volume (kg/m3). Dissolved impurities change
the density in direct proportion to their concentration and their own density.
Common to ignore for low concentration impurities but not high concentration
(thickened sludge or commercial liquid chemicals)
2. Specific weight, Y - weight (force) per unit volume (kN/m3).

3. Specific gravity, S = rho/rho_o = Y/Yo

Viscosity - A measure of the friction


1. Dynamic viscosity, or absolute viscosity, , - mass per unit length per time,
(Pa.s). Represents a measure of a fluids internal resistance to flow. Important
for analysis of liquid flow, (designing pumps)2. Kinematic viscosity, v, = / rho
(m2/s). Used to evaluate the friction coefficient for flow in pipes.

States of Solution Impuritiessubstances can exist in water in three classifications


suspended, colloidal, or dissolved.

Dissolved substance - truly in the solution (there is only one phase),


homogeneously dispersed in the liquid. Involve change of phase to remove/separate
the substance (distillation, precipitation, adsorption, extraction, or passage
through ionic pore-sized membranes)

Suspended solids are large enough to settle out of solution or be removed by


filtration. There are two phases present (liquid and suspended-particle solid
phase). Removed from water by physical methods such as sedimentation, filtration,
and centrifugation.

Colloidal particles - size range between dissolved substances and suspended


particles. They are in a solid state and can be removed from the liquid by physical
means (very high-force centrifugation or filtration through membranes with very
small pore spaces).Tyndall effect - when light passes through a liquid containing
colloidal particles, the light is reflected by the particles.Degree to which a
colloidal suspension reflects light at a 90 degree angle to the entrance beam is
measured by turbidity.

Particle counting - counts the number of particles in a water sample and reports
the results by particle size, generally from 1 to 30mm. A technique used to
evaluate water quality.

Chemical UnitsMolarity 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 103 = (moles/L)(g/mole)(103mg/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

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

Precipitation Reactionsphase change reaction of dissolved ions to solid state

Ca2+ + CO <-> CaCO3(s)

Often, out of convenience, we talk about compounds when in reality a compound


(CaCO3) does not exist in water. In fact the water consists of the unassociated
ions: Ca2+ and CO32-.

All complexes are soluble in water to a certain extent. Likewise, all complexes are
limited by how much can be dissolved in water.

Solubility reaction: AaBb(s) <-> aAb+ + bBa-

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.

Ks values are often reported as pKs

Acid/Base ReactionsAcids are defined as those compounds that release protons. Bases
are those compounds that accept protons.

HA <-> H+ + A-

In order for HA to release the proton (H+) , something must accept theproton. Often
that something is water, that is,

H+ + H2O <-> H3O+

resulting in the net reaction

HA + H2O <-> H3O+ +A-

It is understood that water is generally present. Water acts as the base as it


accepts the proton. If a base is added to water, the water can act as an acid.

B- + H2O <-> HB + OH-

In the above reaction the base (B-) accepts a proton from water. If a compound is a
stronger acid than water, then water will act as a base. If a compound is a
stronger base than water, then water will act as an acid.

Acid/base chemistry centres on water and it is important to know how strong an acid
water is.
Water itself is ionized in water

H2O <-> H+ + OH-

The degree of ionization of water is very small and can be measured by what is
called the ion product of water, Kw It is found by

Kw = [H+][OH-] = 10-14 (at 25C)

A convenient expression for the hydrogen ion concentration is pH,


pH = -log[H+]

A solution is acidic if [H+] > [OH-], H+ > 10-7M, pH < 7

neutral if [H+] = [OH-] = 10-7M, pH = 7basic if [H+] < [OH-], H+ < 10-7M, pH > 7

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-

Weak acids are acids that do not completely dissociate in water. An equilibrium
exists between the dissociated ions and undissociated compound. The reaction of a
weak acid is

HW <-> H+ + W-

An equilibrium constant exists that relates the degree of dissociation:

Ka = [H+][W]/[HW]

As with other K values,

pKa = -log Ka

By knowing the pH of a solution (which can be easily found with a pH meter) it is


possible to get a rough idea of the degree of dissociation of the acid. If

x pH = pKa (that is [H+] = Ka), then [HW] = [W] and the acid is 50% dissociated.

x [H+] is 2 orders of magnitude (100 times) < Ka, then 100 [H+] = Ka (or pH >>
pK).100[H+]=[H+][W]/[HW] or 100 [HW] = [W]. All acid is dissociated (W >>HW).

x pH << pK then [HW] >> [W], none of the acid is dissociated.

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+ +HCO3- <->2H+ +CO32-

AlkalinityAlkalinity 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

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)

r = Moles or milligrams/[(Unit volume)(Unit time)]

Heterogeneous reactions -Reactions that take place at surfaces between phases

r = Moles or milligrams/[(Unit volume)(Unit time)]

Reaction rates are a function of temperature, pressure, and the concentration of


reactants. For a stoichiometric reaction of the form:aA + bB -> cC

the change in concentration of compound A is equal to the reaction rate equation


for compound A:

order of reaction - the sum of the exponents in the reaction rate equation. (my be
either integers or fractions)