Вы находитесь на странице: 1из 48

OXIDATION

a method by which wastewater is treated by using


oxidizing agents.
Generally, two forms viz.
Chemical oxidation and
UV assisted oxidation using chlorine, hydrogen
peroxide, fentons reagent, ozone, or potassium
permanganate are used for treating the effluents,
especially those obtained from primary treatment
(sedimentation)
CHEMICAL OXIDATION
(Oxidants)
Rapid and efficient process
High energy cost, chemicals required

REDOX
Oxidation and reduction in terms of oxygen transfer

Definitions
Oxidation is gain of oxygen.
Reduction is loss of oxygen.

Fe2O3 + 3CO 2Fe + 3CO2


Another definition

Oxidation and reduction in terms of hydrogen transfer


These are old definitions which aren't used very
much nowadays. The most likely place you will
come across them is in organic chemistry.
Definitions
Oxidation is loss of hydrogen.
Reduction is gain of hydrogen.

CH3CH2OH CH3CHO
Oxidation by loses of hydrogen
Another definition
Oxidation and reduction in terms of electron
transfer
This is easily the most important use of the
terms oxidation and reduction at A' level.
Definitions
Oxidation is loss of electrons.
Reduction is gain of electrons.
OIL RIG oxidation is loss, reduction is gain
CuO + Mg Cu + MgO
Cu2+ + Mg Cu + Mg2+
OXIDATION STATES (OXIDATION
NUMBERS)

Oxidation state shows the total number of


electrons which have been removed from an
element (a positive oxidation state) or added
to an element (a negative oxidation state) to
get to its present state.
Oxidation involves an increase in
oxidation state
Reduction involves a decrease in
oxidation state
Some elements almost always have the
same oxidation states in their compounds:

Group 1 metals : always +1


Group 2 metals : always +2
Oxygen : usually -2 except in peroxides and
F2 O
Hydrogen : usually +1 except in metal
hydrides where it is -1
Fluorine : always -1
Chlorine : usually -1 except in compounds
with O or F
Example 1:

This is the reaction between magnesium and


hydrochloric acid or hydrogen chloride gas:
Mg + 2HCl MgCl2 + H2
0 +1 -1 +2 -1 0
The magnesium's oxidation state has increased - it
has been oxidised. The hydrogen's oxidation state has
fallen - it has been reduced. The chlorine is in the
same oxidation state on both sides of the equation - it
hasn't been oxidised or reduced.
Example 2:

The reaction between sodium hydroxide and


hydrochloric acid is:
NaOH + HCl NaCl + H2O
+1 -2 +1 +1 -1 +1 -1 +1 -2

Nothing has changed. This isn't a redox


reaction.
Example 3:

The reaction between chlorine and cold dilute


sodium hydroxide solution is:
2NaOH + Cl2 NaCl + NaClO + H2O
+1 -2 +1 0 +1 -1 +1 +1 -2 +1 -2

One atom has been reduced because its


oxidation state has fallen. The other has been
oxidised.
Symbols

European Union chemical hazard symbol for


oxidizing agents

Dangerous goods label for oxidizing agents


Common oxidizing agents

Hydrogen peroxide and other inorganic peroxides


Nitric acid and Nitrates
Chlorites, chlorate, perchlorate, and other analogous
halogen compounds
Hypochlorite and other hypohalite compounds such
as bleach
Fluorine and other halogens
Ozone
Nitrous oxide(N2O)
Silver oxide
Permanganate salts
Hydrogen peroxide

In acidic solutions H2O2 is one of the most powerful


oxidizers knownstronger than chlorine, chlorine
dioxide, and potassium permanganate.
Also, through catalysis, H2O2 can be converted into
hydroxyl radicals (.OH), which are highly reactive.
H2 + O2 H2O2
It is used as a disinfectant, antiseptic, oxidizer,
propellant in rocket. Hydrogen peroxide is naturally
produced in organisms as a by-product of oxidative
metabolism. Nearly all living things (specifically, all
obligate and facultative aerobes) possess enzymes
known as peroxidase.
Nitric acid

Nitric acid is made by reacting nitrogen dioxide


(NO2) with water.
3 NO2 + H2O 2 HNO3 + NO
Nitric acid reacts with most metals.
3 Cu + 8 HNO2 3 Cu2+ + 2 NO + 4 H2O + 6 NO3-
Cu + 4 H+ + 2 NO3- Cu2+ + 2 NO2 + 2 H2O
For example, if copper and hydrogen half-cells are joined
together we find that the copper half-cell will gain electrons
from the hydrogen half-cell. Thus the copper half-cell is
given a positive voltage and given a relative value of +0.34
V:
Cu2+(aq) + 2e- Cu(s) E = 0.34 V
Since both half-reactions cannot undergo reduction, we
must reverse the equation of the reaction that will undergo
oxidation. This will give us an electrochemical cell voltage
of 0.34 V:
E
Cu2+(aq) + 2e- Cu(s) 0.34 V
H2 (g) 2H+(aq) + 2e- 0.00 V
Cu2+(aq) + H2 (g) 2H+(aq) + Cu(s) 0.34 V
We see in the Table of Standard Reduction Potentials that
zinc has a negative E indicating that it is not as good at
competing for electrons as hydrogen.
Zn2+(aq) + 2e- Zn(s) E = -0.76 V
Therefore if zinc and hydrogen are paired together in an
electrochemical cell, the hydrogen would be reduced (gain
the electrons) and zinc would be oxidized (losing electrons).
To determine the net redox reaction as well as the voltage of
the electrochemical cell we reverse the zinc equation, and
also reverse it's sign before adding the equations and E
together:
E
Zn(s) Znu2+(aq) + 2e- 0.76 V
2H+(aq) + 2e- H2 (g) 0.00 V
Zn(s)+ 2H+(aq) Zn2+(aq) + H2 (g) 0.76 V
CHEMICAL PRECIPITATION
CHEMICAL PRECIPITATION
Some things (chemists use term compounds)
dissolve in water these are said to be soluble.

Some things (compounds) dont dissolve in water these


are said to be insoluble.
CHEMICAL PRECIPITATION
Definition:
Removal of metal ions
from solution by changing
the solution composition,
thus causing the metal ions
to form insoluble metal
complexes.
chemical
solution with reaction insoluble + clean
soluble ions complexes Water
A precipitation reaction is a reaction
in which soluble ions in separate
solutions are mixed together to form
an insoluble compound that settles
out of solution as a solid. That
insoluble compound is called a
precipitate.
Precipitate Formation

soluble insoluble
Natural methods of precipitation include settling or
sedimentation, where a solid forms over a period of time due to
ambient forces like gravity or centrifugation
CHEMICAL PRECIPITATION
(Applications)
Removal of metals from waste stream
e.g. plating and polishing operations, mining, steel
manufacturing, electronics manufacturing
include arsenic, barium, chromium, cadmium, lead,
mercury, silver
Treatment of hard water removal of
Mg2+ and Ca2+
Phosphorus removal
Removing salts from water in water
treatment
CHEMICAL PRECIPITATION
(Theoretical Background)
Solubility equilibria
A chemical reaction is said to have reached
equilibrium when the rate of forward reaction is
equal to the rate of the reverse reaction

ABs A+ + B-

where ABs : solid; A+, B- - ionic species


CHEMICAL PRECIPITATION
(Theoretical Background)
Due to dilute concentration,
-
(A )(B )
K eq Ksp = [A+] [B-]
(ABs ) = solubility product constant

where [ ] refer to molar concentration

Eg.

A + + B- Solubility
Compound (mg/L) Ksp
CaCO3 18 5 x 10-9

ABs CaCl 745000 159 x 106


CaCO3(s) Ca2+ + CO3-
Ksp = [Ca2+ ][CO3-]/[CaCO3(s) ] = [Ca2+ ][CO3-]

=1
Ksp = equilibrium solubility product constant

Ksp > ion concentration product


Ksp< hasil perkalian konsentrasi

Undersaturated condition, Supersaturated, condition,


no precipitation precipitation
After the Ksp = [A][B]

26 TL-
61
CHEMICAL PRECIPITATION
(Basic Principles)

A. Add chemical
precipitants to
waste stream
B. Mix thoroughly
C. Allow solid
precipitates to
form floc by
slow mixing
D. Allow floc to
settle in clarifier
CHEMICAL PRECIPITATION
(Types of Precipitation)

Heavy metals removal


Hydroxide precipitation (OH-)
Sulphide precipitation (S2-)
Carbonate precipitation (CO32-)

Phosphorus removal
Phosphate precipitation (PO42-)
CHEMICAL PRECIPITATION
Reaction rate

Reaction rate is a measure of how fast a reaction


occurs, or how something changes during a given
time period.
Consider the oxidation of glucose, C6H12O6 :
C6H12O6(s) + 6 O2(g) 6 CO2(g) + 6 H2O(g)
One of the things that happens during this reaction
is simply that glucose gets used up as it reacts with
oxygen in the air, and carbon dioxide and water
start to form.
A common measure of reaction rate is to express how
the concentration of a reaction participant changes
over time. It could be how the concentration of a
reactant decreases, or how the concentration of a
product increases. This is the standard method we will
be using.
Now that we have something that changes to measure,
we must consider the second key aspect of
determining rate - time. Rate is a measure of how
something changes over time.

Change in concentration
Change in time
Chemistry Notation

In chemistry, we typically represent concentration by using


square brackets around the chemical formula of the
substance. For example to indicate the concentration of
SO2(g) in the following reaction we would write it as [SO2].
Also, the delta symbol, is used to indicate a change. T, for
example, means "the change in temperature."
Therefore, if we wanted to express the rate of the following
reaction:
SO2(g) + NO2(g) SO3(g) + NO(g)
Let's try an example of calculating a reaction rate.
Consider the following reaction:
AB
The following data were obtained for how the
concentration of these substances changed during the
experiment.

Time A B
(min) mol/L mol/L
0.0 1.000 0.000
3.0 0.400 0.600
6.0 0.250 0.750
We could measure the rate of the reaction either by measuring how
the concentration of reactant A changes or how the concentration of
product B changes. Let's measure A's average rate of change first:

Compare this rate to the rate of just the first three minutes of the
reaction:

If we calculate the average rate based on the production of


product B:
Factors that Affect the Chemical Reaction
Rate
Concentration of Reactants
A higher concentration of reactants leads to more effective
collisions per unit time, which leads to an increasing
reaction rate (except for zero order reactions).
Temperature
Usually, an increase in temperature is accompanied by an
increase in the reaction rate. Temperature is a measure of
the kinetic energy of a system, so higher temperature
implies higher average kinetic energy of molecules and
more collisions per unit time.
Factors that Affect the Chemical Reaction
Rate
Medium
The rate of a chemical reaction depends on the medium in
which the reaction occurs. It may make a difference
whether a medium is aqueous or organic; polar or
nonpolar; or liquid, solid, or gaseous.
Presence of Catalysts and Competitors
Catalysts (e.g., enzymes) lower the activation energy of a
chemical reaction and increase the rate of a chemical
reaction without being consumed in the process. Catalysts
work by increasing the frequency of collisions between
reactants, altering the orientation of reactants so that more
collisions are effective, reducing intramolecular bonding
within reactant molecules, or donating electron density to
the reactants.
CHEMICAL PRECIPITATION
(Sulphide Precipitation)

Use of sulphide in the form of FeS, Na2S or NaHS


Better metal removal as sulphide salt has low
solubility limit
Cu2+ + FeS CuS + Fe2+
Limitation: can produce H2S (g) at low pH
2H+ + FeS H2S + Fe2+
At low pH, reaction will proceed to the right.
Thus, require pH > 8 for safe sulphide
precipitation.
Distribusi spesi sulfur dalam air akibat
perubahan pH air
Hydroxide Precipitation

Most Soluble Heavy Metals Will Precipitate


When pH is Raised to a Given Point

pH is Raised by Addition of Hydroxide

Cu(NO3)2(aq) + 2 NaOH(aq) Cu(OH)2(s)


+ 2 NaNO3(aq)
CHEMICAL PRECIPITATION
(Hydroxide Precipitation)
Add lime (CaO) or sodium hydroxide (NaOH) to
waste stream to precipitate heavy metals in the
form of metal hydroxides.

Cd2+ + Ca(OH)2 Cd (OH)2 + Ca2+

CaO in the form of slurry (Ca(OH)2) while NaOH


in the form of solution.
NaOH is easier to handle but is very corrosive.
Will form floc and settle in clarifier
Hydroxide Precipitation
Sodium Hydroxide,
NaOH
Caustic Soda

Calcium Hydroxide,
Ca(OH)2
Hydrated Lime
Sodium Hydroxide
Caustic Soda, Soda Lye
Available in Liquid or Dry Form
Liquid:
Commercial Strength
50 % , 73 % NaOH
Often Stored at 20 %
50 % Crystallizes at 53 Deg. F
Dry:
99.9 % NaOH
Safety Bag, Drum, or Bulk
Caustic Poison
Dangerous to Handle, Corrosive
Prevent All Body Contact
Protect Eyes
Calcium Hydroxide
Ca(OH)2
Hydrated Lime, Slaked Lime
Available in Dry or Liquid Form

Dry Form Available in Bags or Bulk


Commercial Strength 82 - 95 %
Safety
Caustic, Irritant, Dusty
Avoid Contact with Eyes, Nose,
Respiratory System
Hydroxide Precipitation
Sodium Hydroxide

VS
Hydrated Lime
Less Expensive
Solids Settle Faster
Higher Sludge Solids Conc
Sludge Easier to Dewater
Takes Longer to Neutralize
More Complicated Feed System
A Lot More Sludge
CARBONATE PRECIPITATION
PHOSPORUS REMOVAL

pH : 5.5-7.0 requires
water alkalinity
Chemical
Process Water Treatment

..

Equalization Tank Treatment Tank

Treated Water Clarifier

Back To
Filter Press
Equalization Tank

Sludge Tank
Sludge Bin