PIERO M.

ARMENANTE
NJIT
Neutralization
of Acid and Alkaline
Wastewaters
PIERO M. ARMENANTE
NJIT
Molarity and Normality
A (gram)mole is the quantity of a chemical species
that has a weight (in grams) numerically equal to its
molecular weight.
Molarity is the number of moles of a substance
present in solution (measured in moles/L [M]).
An equivalent is the quantity of a chemical species
whose weight (in grams) is numerically equal to the
amount of that substance that can react or combine
(directly or indirectly) with a mole of H or H
+
.
Normality is the number of equivalents of a
substance present in solution (measured in
equivalents/L [N]).
PIERO M. ARMENANTE
NJIT
Equivalence Point
The equivalence point in a titration is the point at
which an exact stoichiometric amount of the
titrant has been added so that all the acid (or
base) molecules in the solution have reacted with
the titrant.
At the equivalence point the number of
equivalents of the titrant that have been added to
the solution is equal to the number of equivalents
of the acid (or base) initially present in the
solution, (i.e., the added base (or acid) has
stoichiometrically reacted with all the acid (or
base) initially present in the solution).
PIERO M. ARMENANTE
NJIT
Equivalence Point: Nomenclature
N
ac
= normality of the acid solution
(equivalents/liter)
N
b
= normality of the basic solution
(equivalents/liter)
V
ac
= volume of the acid solution (liters)
V
b
= volume of the basic solution (liters)
PIERO M. ARMENANTE
NJIT
Equivalence Point
At the equivalence point it must be that:
N
ac
V
ac
= N
b
V
b
(or N
b
V
b
= N
ac
V
ac
)
Remark: At the equivalence point the pH is equal
to 7 only if a strong acid is used to titrate a strong
base (or vice versa).
If a strong acid is used to titrate a weak base the
equivalence point will be reached at a pH lower
than 7 because of hydrolisis. Vice versa, for the
case of a strong base titrating a weak acid the pH
at equivalence point will be higher than 7.
PIERO M. ARMENANTE
NJIT
Equivalence Point
Example: the equivalence point of a 150 mL
solution containing 5 g of H
2
SO
4
(i.e., having a
molarity of 0.34 moles/L, a normality of 0.68 eq/L
and containing 0.051 moles of H
2
SO
4
) titrated with
a 0.1 M NaOH solution is reached when 1020 mL
of this solution are added (i.e., when 0.102 moles
of NaOH are added, corresponding to 0.102
equivalents).
Reaction:
H
2
SO
4
+ 2 NaOH Na
2
SO
4
+ 2 H
2
O
PIERO M. ARMENANTE
NJIT
pH Requirements for Wastewaters
Many industrial wastewaters have a pH which
is too high or too low for discharge or for
further wastewater processing;
Typically, the pH must be adjusted before
discharging to a POTW or into a receiving
body of water (pH =6-9);
Wastewaters entering a biological treatment
process must have a pH typically within the
range 6-8.5.
PIERO M. ARMENANTE
NJIT
Neutralization of Wastewaters
If the pH of a wastewater is too acid (the most
common occurrence) or too alkaline it must be
adjusted. Different approaches exist:
Mixing the wastewater with another
wastewater of different pH to (partially)
adjust the pH of the combined
wastewaters;
Adding a base (e.g., sodium hydroxide) if
the wastewater is acid;
Adding an acid (e.g., sulfuric acid) if the
wastewater is alkaline;
PIERO M. ARMENANTE
NJIT
Neutralization of Wastewaters
(continued)
Adding a salt from a weak acid and a
strong base, such as sodium carbonate
(resulting in hydrolysis when added to
water), if the wastewater is acid;
In principle, adding a salt from a weak base
and a strong acid (resulting in hydrolysis
when added to water), if the wastewater is
basic. This case is not typically used in
wastewater neutralization.
PIERO M. ARMENANTE
NJIT
Neutralization Reactions
Neutralization reactions involve the reaction of
an acid with a base (hydroxide) to form a salt
and water;
Acids and bases are typically classified as
strong or weak (and everything in between)
depending on whether they are, respectively,
completely dissociated or only partially
dissociated, when present in aqueous solutions;
Whenever partially dissociated acids or bases
are involved in neutralization the corresponding
dissociation reaction must be included in the
equilibrium calculations.
PIERO M. ARMENANTE
NJIT
Acid-Base Neutralization Reactions
In general, there are four possible types of acid-
base reactions:
1. Strong Acid + Strong Base Salt + Water
2. Strong Acid + Weak Base
Salt (subject to acidic hydrolysis) + Water
3. Weak Acid + Strong Base
Salt (subject to basic hydrolysis) + Water
4. Weak Acid + Weak Base
Salt (subject to hydrolysis) + Water
Reaction #4 is not commonly used in neutralization
reactions.
PIERO M. ARMENANTE
NJIT
Neutralization Reaction Involving a
Strong Acid and a Strong Base
Neutralization reaction:
Strong Acid + Strong Base Salt + Water
Examples:
HCl + NaOH NaCl + H
2
O
H
2
SO
4
+ 2 NaOH Na
2
SO
4
+ 2 H
2
O
PIERO M. ARMENANTE
NJIT
Titration of a Strong Acid with a
Strong Base
0 5 10 15 20
mL of 10
-2

N NaOH solution added
0
2
4
6
8
10
12
14
p
HEquivalence
Point
V
ac
N
ac
= V
b
N
b
Titration of 1000 mL HCl solution (10
-4
N) with 10
-2
N NaOH
PIERO M. ARMENANTE
NJIT
Partial Dissociation of Weak Acids
and Bases
Unlike strong acids and bases that, when in
solution, are practically all dissociated in ions
weak acids and bases are only partially
dissociated. Example:
NH H O NH OH
3 2 4
+
+
[ ][ ]
[ ]
K
NH OH
NH H O

4
3 2
5
18 10 .
pK K log .
10
4 74
PIERO M. ARMENANTE
NJIT
Dissociation Constant of Acids and Bases
Substance Equilibrium equation K pK Significance
Acetic acid CH
3
COOH=
H
+
+CH
3
COO
-
1.8x10
-5
4.7 Organic wastes,
anaerobic digestion
Ammonia NH
3
+H
2
O=NH
4
+
+OH
-
1.8x10
-5
4.7 Disinfection
Boric acid H
3
BO
3
=H
+
+H
2
BO
3
-
5.8x10
-10
9.2 Nitrogen analysis
Butyric acid C
3
H
7
COOH=
H
+
+C
3
H
7
COO
-
1.5x10
-5
4.8 Anaerobic digestion
Carbonic acid H
2
CO
3
*=H
+
+HCO
3
-
HCO
3
-=H
+
+CO
3
=
4.3x10
-7
4.7x10
-11
6.4
10.3
Numerous applications
Hydrochloric acid HCI=H
+
+Cl
-
Strong 3 Analyses
Hydrocyanic acid HCN=H
+
+CN
-
7.2x10
-10
9.1 Toxicity
Hydrofluoric acid HF=H
+
+F
-
6.75x10
-4
3.2 Fluoridation
Hydrosulfuric acid
(hydrogen sulfide)
H
2
S=H
+
+HS
-
HS
-
=H
+
+S
=
9.1x10
-8
1.3x10
-13
7.0
12.9
Odor, corrosion,
anaerobic digestion,
toxicity
Hypochlorous acid HOCI=H
+
+OCl
-
2.9x10
-8
7.5 Disinfection
Nitric acid HNO
3
=H
+
+NO
3
-
0.10 -1.0 Nitrification, analyses
Nitrous acid HNO
2
=H
+
+NO
2
-
5.1x10
-4
3.29 Nitrification
After Droste, Theory and Practice of Water and Wastewater Treatment, 1997, pp. 59.
PIERO M. ARMENANTE
NJIT
Dissociation Constant of Acids and Bases
Substance Equilibrium equation K pK Significance
Perchloric Acid HCIO
4
=H
+
+CIO
4
-
Strong 7 Analyses
Phenol C
6
H
5
OH=H
+
+C
6
H
5
O
-
1.2x10
-10
9.9 Tastes, odors
Phosphoric acid H
3
PO
4
=H
+
+H
2
PO
4
-
H
2
PO
4
-
=H
+
+HPO
4
=
HPO
4
=
=H
+
+PO
4
-3
7.5x10
-3
6.2x10
-8
4.8x10
-13
2.1
7.2
12.3
Buffer, nutrient
Potassium hydroxide KOH=K
+
+OH
-
Strong
(base)
Analyses
Propionic acid C
2
H
5
COOH=
H
+
+C
2
H
5
COO
-
1.3x10
-5
4.9 Anaerobic digestion
Sodium hydroxide NaOH=Na
+
+OH
-
Strong
(base)
Analyses,
neutralization
Sulfuric acid H
2
SO
4
=H
+
+HSO
4
-
HSO
4
=H
+
+SO
4
=
Strong
1.2x10
-2
-3
1.9
Coagulation, pH
control, analyses
Sulfurous acid H
2
SO
3
=H
+
+HSO
3
-
HSO
3
-
=H
+
+SO
3
=
1.7x10
-2
6.3x10
-8
1.8
7.2
Dechlorination
After Droste, Theory and Practice of Water and Wastewater Treatment, 1997, pp. 59.
PIERO M. ARMENANTE
NJIT
Water Dissociation and pH
The dissociation of water can be written as:
H O H OH
2
+
+
[ ] [ ]
[ ]
[ ] [ ] [ ]
K
H OH
H O
H OH K H O K
w

+
+
2
2
The definitions of pH and pOH are then:
[ ] [ ]
pH and pOH
+
log log
10 10
H OH
PIERO M. ARMENANTE
NJIT
Water Dissociation and pH
At 25
o
C it has been found experimentally that:
K
w


10
14
Hence, in any aqueous solutions it must be that:
pH pOH pK
w
+ 14
Note that for the case of pure water at 25
o
C (i.e.,
when no other chemical species are present) it is:
[ ] [ ] [ ]
H OH H K
w
+ +

2
14
10
i.e.:
[ ] [ ]
H OH K
w
+
10 7
7
pH
PIERO M. ARMENANTE
NJIT
Hydrolysis
When a salt from a weak base and a strong acid
[or a weak acid and a strong base] dissolves in
water it reacts with water, partially reforming the
undissociated base [or acid] plus H
+
[or OH
-
].
This shifts the pH in the direction of the strong
acid [or strong base].
Example: Hydrolysis of NH
4
Cl
NH
4
Cl = NH
4
+
+ Cl
-
NH
4
+
+ H
2
O = NH
3
+ H
+
In this case hydrolysis occurs because the weak
base (NH
3
) is not completely dissociated.
PIERO M. ARMENANTE
NJIT
Hydrolysis (continued)
The hydrolysis constant, K
h
, is:
K
NH H
NH
NH
NH
K
OH
K
K
h
w w
weak base

+

3
4
3
4
If the salt is the only solute in the solution one
can reasonably assume that:
NH H
3

+
and
C NH
t

+
4
The pH of the solution containing a single salt
undergoing hydrolysis is then:
H K C
h t
+

pH K C
h t
log
PIERO M. ARMENANTE
NJIT
Neutralization Involving a Strong
Base and a Weak Acid
An aqueous solution of a weak acid (e.g.,
HClO) contains H
+
ions, the acid anion (e.g.,
ClO
-
), and the undissociated acid (e.g., HClO);
In this case the concentration of OH
-
ions from
water dissociation is typically exceedingly
small and can be calculated from the water
dissociation reaction;
If a small amount of strong (dissociated) base
is added the OH
-
ions react with the H
+
ions in
the solution forming water;
PIERO M. ARMENANTE
NJIT
Neutralization Involving a Strong
Base and a Weak Acid (cont.d)
The disappearance of H
+
ions shifts the
dissociation equilibrium of the weak acid,
which dissociates more releasing H
+
ions, until
the neutralization of added OH
-
ions is
complete;
Further additions of the base produce the
same effect until all the weak acid has
dissociated and reacted;
Past this point further caustic additions
produce sharp pH increases;
PIERO M. ARMENANTE
NJIT
Neutralization Involving a Strong
Base and a Weak Acid (cont.d)
During the period in which the weak
(undissociated) acid is in the presence of the
salt formed from the caustic addition the pH
changes slowly if more base is added. This
can be calculated from the equilibrium
reactions. In such a case the solution
constitutes a buffer solution;
A similar but reverse process occurs when a
strong acid is added to a weak base (in which
case the added H
+
ions react with the OH
-
ions
is solution.
PIERO M. ARMENANTE
NJIT
Neutralization Reactions Involving a
Strong Base and a Weak Acid
Neutralization reactions:
Weak Acid + Strong Base Salt + Water
Weak Acid Dissociated Weak Acid
Water Dissociated Water
Example:
HClO + NaOH Na
+
+ ClO
-
+ H
2
O
HClO H
+
+ ClO
-
(K=3.7 10
-8
)
H
2
O H
+
+ OH
-
(K=10
-14
)
PIERO M. ARMENANTE
NJIT
Titration of a Weak Acid with a
Strong Base
0 10 20 30 40 50
mL of 10
-2
N NaOH solution added
0
2
4
6
8
10
12
14
p
H
Equivalence
Point
ac b
b ac
V N =V N
Titration of 1000 mL HClO solution (10
-4
N) with 10
-2
N NaOH
PIERO M. ARMENANTE
NJIT
Neutralization Involving a Strong
Acid and a Salt from a Weak Acid
Acid wastewaters can be neutralized adding a
salt such as calcium carbonate (CaCO
3
) or
sodium carbonate (Na
2
CO
3
) derived from a
strong base and a weak acid such as carbonic
acid
When one of these salts is dissolved in water it
undergoes hydrolysis, partially re-forming the
undissociated weak acid (H
2
CO
3
), generating
an excess OH
-
ions, and increasing the pH.
H
2
CO
3
then generates CO
2
(which volatilizes)
plus water
PIERO M. ARMENANTE
NJIT
Neutralization Involving a Strong
Acid and a Salt from a Weak Acid
(cont.d)
If a small amount of this solution is added to a
strong acid the OH
-
ions react with the H
+
ions
in the solution forming water. This shifts the
equilibrium resulting in further hydrolysis of
the salt, neutralization of the strong acid, and
CO
2
evolution
Further additions of the salt solution produce
the same effect until all the acid has been
neutralized
PIERO M. ARMENANTE
NJIT
Buffer Solutions
Buffer solutions are chemical solutions having
the characteristic of maintaining their pH
relatively constant even when an acid or a
base is added (within limits of course);
Buffer solutions are typically made by adding,
in roughly equal molar proportions, a solution
of a weak acid to a solution of a salt coming
from the same weak acid and a strong base
(or, vice versa, by adding a weak base and a
salt of the same weak base and a strong acid);
PIERO M. ARMENANTE
NJIT
Buffer Solutions (continued)
The buffering capacity of such a buffer
solution is strongest at a pH equal to the pK of
dissociation of the weak acid (or weak base);
Typically, buffer solutions maintain their pH
practically unchanged for additions of acids or
bases up to 1/50 of the amount of the chemical
species initially present in the buffer solution.
PIERO M. ARMENANTE
NJIT
Example of a Buffer Solution
Example: acetic acid/sodium acetate buffer.
When acetic acid and sodium acetate are added
to water the following reactions take place:
CH COOH H O CH COO H
CH COO H O CH COOH OH
H O H OH
3 2 3
3 2 3
2
+ +
+ +
+
+

+
PIERO M. ARMENANTE
NJIT
Example of a Buffer Solution
The following equilibria must be satisfied:
[ ] [ ]
[ ]
[ ] [ ]
[ ]
[ ] [ ]
K
CH COO H
CH COOH
K
CH COOH OH
CH COO
K H OH
weak acid
h
w

+
3
3
3
3
PIERO M. ARMENANTE
NJIT
Example of a Buffer Solution
After solving for [H
+
] it is:
[ ]
[ ]
[ ]
H K
CH COOH
CH COO
weak acid
+

3
3
i.e.:
[ ]
[ ]
pH pK
CH COO
CH COOH
weak acid
+

_
,

log
10
3
3
Note that:
[ ] [ ]
[ ] [ ]
CH COOH CH COOH
CH COO CH COO
initial
initial
3 3
3 3

PIERO M. ARMENANTE
NJIT
Wastewater Alkalinity
The pH of a wastewater indicates the
concentration of H
+
ions present in solution.
In general, the pH alone is useless to
understand how much acid or base must be
added to neutralize the wastewater.
This is especially true for wastewaters having
some buffering capacity due to the presence of
weak acids and their salts.
Alkalinity (or acid-neutralizing capacity) is the
capacity of a solution to neutralize an acid
down to a reference pH (i.e., 7).
PIERO M. ARMENANTE
NJIT
Wastewater Alkalinity (continued)
Alkalinity is determined by titrating an alkaline
wastewater (pH>7) with a strong acid,
determining the amount of acid equivalents
required to do so, and reporting this
measurement as the corresponding alkaline
equivalents of a standard alkaline substance.
Typically, the reference pH for alkalinity
determination is 4.3, i.e., the pH at which
methyl orange indicator changes color (from
yellow above pH=4.4 to red below pH=3.1).
PIERO M. ARMENANTE
NJIT
Wastewater Alkalinity (continued)
Since carbonates often contribute to water and
wastewater alkalinity, alkalinity is often
reported as mg CaCO
3
/L (obtained by
multiplying the alkalinity obtained from the
titration in meq/L by 50 mg/meq CaCO
3
).
PIERO M. ARMENANTE
NJIT
Wastewater Acidity
Acidity (or base-neutralizing capacity) is the
capacity of a solution to neutralize a base up
to a reference pH (i.e., 7).
Acidity is determined by titrating an acid
wastewater (pH<7) with a strong base,
determining the amount of base equivalents
required to do so, and reporting this
measurement as the corresponding acid
equivalents of a standard acid substance.
Acidity is often reported as meq H
+
/L.
PIERO M. ARMENANTE
NJIT
Wastewater Acidity (continued)
Typically, the reference pH for acidity
determination is 8.3, i.e., the pH at which
phenolphtalein indicator changes color (from
colorless below 8.2 to purple above 9.8).
PIERO M. ARMENANTE
NJIT
Neutralization of Wastewaters Having
Some Buffering Capacity
If the wastewater does not have any buffering
capacity the pH will change very rapidly once
the strong acid (or base) it contains has been
neutralized
If the wastewater has some buffering capacity
the pH will change gradually in
correspondence of the pK value(s) (i.e., the
water has a reserve of [H
+
] stored as
undissociated acid, which dissociates as more
base is added; the opposite is true for basic
wastewaters).
PIERO M. ARMENANTE
NJIT
Typical Titration Curves for Wastewaters
Acid Added (meq)
0
2
4
6
8
10
12
p
H
Acid Added (meq)
0
2
4
6
8
10
12
p
H
Little or no buffering capacity Some buffering capacity
PIERO M. ARMENANTE
NJIT
Steps Involved in the Design of
Neutralization Systems
Experimentally obtain a titration curve for the
wastewater to be treated using as titrant the
neutralizing agent to be used in the plant
Determine the kinetics of the dissolution-
reaction process
Determine the agitation intensity required to
achieve solid suspension (if slurries are used)
Decide number of stages involved in
neutralization process
Size neutralization system
PIERO M. ARMENANTE
NJIT
Titration Curve for a Strong Acid
Using Lime as a Titrant
0 500 1000 1500 2000 2500 3000
Lime Addition (mg lime/L of wastewater)
0
2
4
6
8
10
12
14
p
H
Titration
Curve
Second Stage (pH=7)
First Stage (pH=3.5)
After Eckenfelder, Industrial Water Pollution Control, 1989, p. 51
PIERO M. ARMENANTE
NJIT
Neutralization by Mixing Together
Acid and Alkaline Wastewaters
Occasionally, different acid and alkaline
wastewaters can be mixed together to
(partially) neutralize each other.
This approach can be quite inexpensive.
However, large equalization basins may be
necessary.
Depending on the wastewaters, sludges can
be formed, including sludges containing heavy
metals (if heavy metals are present and the
wastewater is alkaline).
PIERO M. ARMENANTE
NJIT
Neutralization by Mixing Together
Acid and Alkaline Wastewaters
Additional neutralization equipment and
supplies must be available to accommodate
changes in wastewater flows and
compositions that could reduce the
effectiveness of the neutralization process and
require neutralization via acid/base addition.
Some wastewaters (e.g., wastewaters
containing cyanides) cannot be neutralized
because of the potential to generate toxic
fumes (e.g., hydrogen cyanide).
PIERO M. ARMENANTE
NJIT
Neutralization of Acid Wastewaters
Acid wastewaters can be neutralized by adding:
Sodium hydroxide (caustic soda, NaOH)
Lime (a term applied to several combinations
of calcium and oxygen). Typically, lime and
slaked lime refer to Ca(OH)
2
, and quicklime
and slaked quicklime to CaO. Lime or
quicklime slurries are often used
Limestone (CaCO
3
) beds or limestone slurries
Sodium carbonate (soda ash, or Na
2
CO
3
)
Ammonia (NH
3
), or ammonium hydroxide
solutions (NH
4
OH)
PIERO M. ARMENANTE
NJIT
Caustic Soda in Acid Wastewater
Neutralization
Caustic soda (NaOH) and high-calcium lime
are typically used for high acidity wastewaters
Caustic soda is more expensive than other
caustic material but it is easy to store and
deliver (as a solution), thus reducing capital
costs.
Neutralization times with NaOH are short (3-15
minutes).
PIERO M. ARMENANTE
NJIT
Caustic Soda in Acid Wastewater
Neutralization (continued)
No sludge is typically produced during
neutralization with NaOH.
Since NaOH is a strong base and does not
have any buffering capacity, fine pH control
is difficult to achieve and overneutralization
to pH 13 is possible.
NaOH solutions (50%) freeze at 50 C.
PIERO M. ARMENANTE
NJIT
Lime and Quicklime in Acid
Wastewater Neutralization
Lime is inexpensive and very widely used.
Neutralization to pH values in the range 6-12.4
can be obtained.
Slaked lime slurries are obtained by reacting
CaO (quicklime) with water producing Ca(OH)
2
slurries (solid concentration: 10-35%).
Lime can be slow to react and can form
insoluble precipitates (e.g., CaSO
4
) that
coat the lime particles and the equipment.
PIERO M. ARMENANTE
NJIT
Multistage Neutralization Process
Acid
Waste
Alkaline
Waste
Slaked Lime
Lime Slurry
Discharge to
Treatment Plant
By-pass
Tank # 1 Tank # 2
Tank #3
Pre-
Neutralization
Tank
PIERO M. ARMENANTE
NJIT
Practical Design Aspects of Lime
Slurry Neutralization Processes
A residence time of at least 10 minutes is
typically allowed to complete the mass
transfer-reaction process.
The agitation intensity required to suspend the
particles, promote mass transfer, and blend
the reagents is typically in the range 0.04- 0.1
kW/m
3.
The pH needs to be carefully controlled in the
neighborhood of the equalization point to
prevent overshooting.
PIERO M. ARMENANTE
NJIT
Acid Wastewater Neutralization with
Slurries
The following steps occur during neutralization of
a wastewater with a slurry (e.g., lime):
lime particles are suspended in slurry
solids partially dissolve in the slurry (mass
transfer dominated process)
dissolved lime partially dissociates into ions
(fast reaction)
ions react with acid in wastewater (fast
reaction)
PIERO M. ARMENANTE
NJIT
Limestone in Acid Wastewater
Neutralization
Limestone (CaCO
3
) is widely used. Limestone
reactivity is low, resulting in longer
neutralization time (>45 minutes).
pH above neutrality cannot be achieved with
limestone.
Typical designs of limestone neutralization
equipment include a limestone bed, 3-8 ft
deep, through which the wastewater can pass
and be neutralized.
Downflow and upflow systems are used
PIERO M. ARMENANTE
NJIT
Limestone in Acid Wastewater
Neutralization (continued)
Maximum specific flow rate in downflow
systems 0.04 m
3
/m
2
min
Coating of bed with insoluble precipitates
can occur. The maximum concentration of
sulfuric acid in wastewater to prevent coating
of limestone particles with CaSO
4
(downflow
systems) is 0.6%
Sludge production can be significant
especially if sulfates are present
PIERO M. ARMENANTE
NJIT
Typical Apparatus for Neutralization
with a Limestone Bed
Acid
Wastewater
Recycle Recycle
Pump
Effluent
Conveyor
3 ft of Limestone
Presedimentation
Limestone Bed
Grit Removal
Final Sedimentation
After Eckenfelder, Industrial Water Pollution Control, 1989, p. 50
PIERO M. ARMENANTE
NJIT
Sodium Carbonate in Acid
Wastewater Neutralization
Sodium carbonate (soda ash) is used in the
form of a slurry.
It is less reactive and more expensive than
other treatments. However, it provides some
buffering action.
Carbon dioxide evolution can create some
foaming problem.
PIERO M. ARMENANTE
NJIT
Ammonia in Acid Wastewater
Neutralization
Ammonia and ammonium hydroxide solutions
are highly reactive, thus reducing residence
time requirements.
However, nitrogen is introduced in the water,
and this could be objectionable.
PIERO M. ARMENANTE
NJIT
Neutralization of Alkaline
Wastewaters
Alkaline wastewaters are typically neutralized by
adding:
Sulfuric acid (H
2
SO
4
)
Hydrochloric acid (HCl)
Carbon dioxide (CO
2
)
PIERO M. ARMENANTE
NJIT
Sulfuric Acid in Alkaline Wastewater
Neutralization
Neutralization with sulfuric acid (H
2
SO
4
) is
typically the cheapest alternative.
Reaction times of 15-30 minutes are needed.
The formation of calcium sulfate sludges is
possible when calcium-containing
wastewaters are neutralized.
PIERO M. ARMENANTE
NJIT
Hydrochloric Acid in Alkaline
Wastewater Neutralization
Hydrochloric acid (HCl) is more expensive than
sulfuric acid.
Reaction times of 5-20 minutes are needed.
No sludges are typically formed.
However, the acid forms a very corrosive mist
during the reaction.
PIERO M. ARMENANTE
NJIT
Carbon Dioxide in Alkaline
Wastewater Neutralization
Carbon dioxide (CO
2
) additions are made by
injecting flue gases from combustion
processes (flue gases typically contain 14%
CO
2
) resulting in the addition of carbonic acid
to the wastewater.
Reaction time is typically short (1.5-2 minutes).
This approach is typically costly unless flue
gases are readily available.
PIERO M. ARMENANTE
NJIT
Carbon Dioxide in Alkaline
Wastewater Neutralization
(continued)
Calcium carbonate precipitates can be formed
when calcium-containing wastewaters are
neutralized.
Neutralization by carbon dioxide is more easily
controlled than when other acids are used.
PIERO M. ARMENANTE
NJIT
Chemical Equilibria
PIERO M. ARMENANTE
NJIT
Free Energy of Reaction
Generalized reaction:
bB + cC rR + sS
At constant temperature and pressure the change in
free energy associated with this reaction is:
G rG sG bG cG
R S B C
+
where:
G G RT a
i i i
+
0
ln
and: G
i
0
= free energy per mole of component i in
a selected standard state
a
i
= activity of component i in the mixture
PIERO M. ARMENANTE
NJIT
Free Energy of Reaction (continued)
A substitution yields:
( ) ( )
( ) ( )
G r G RT a s G RT a
b G RT a c G RT a
R R S S
B B C C
+ + +
+ +
0 0
0 0
ln ln
ln ln
The free energy change at the standard state is
defined as:
G rG sG bG cG
R S B C
0 0 0 0 0
+
Hence:
G G RT
a a
a a
R
r
S
s
B
b
C
c
+
0
ln
PIERO M. ARMENANTE
NJIT
Free Energy of Reaction (continued)
At constant pressure and temperature chemical
equilibrium is associated with:
G 0
i.e.:
G RT
a a
a a
R
r
S
s
B
b
C
c
0
ln
or:
G RT K
0
ln
where:
K
a a
a a
R
r
S
s
B
b
C
c

PIERO M. ARMENANTE
NJIT
Activity Coefficients
Definition of activity coefficient '
i
:
a X
i i i
'
Alternative definition of activity coefficient
i
:
a C
i i i

i.e.:
( ) ( )
( ) ( )
K
C C
C C
R
r
R
r
S
s
S
s
B
b
B
b
C
c
C
c

PIERO M. ARMENANTE
NJIT
Application of Equilibrium to
Electrolyte Solutions
Electrolyte dissociation:
A B A B
Z Z


+ + +
+

+
where:

+
and - are the numbers of positive and
negative ions produced during dissociation
and:
Z
+
and Z
-
are the charges of the positive and
negative ions
PIERO M. ARMENANTE
NJIT
Activities in Electrolyte Solutions
a C
+ + +

a C


Mean ion activity coefficients


t +
+

where:
+
+
The ionic strength is defined as:
I m Z
i i
i

1
2
2
PIERO M. ARMENANTE
NJIT
Debye-Hckel Theory
For ionic strengths below 0.005 (molality) it is:
( )
log
10
2

+ +
AZ I
( ) log
10
2

AZ I
( ) log
10

t +
AZ Z I
The value of A depends on the solvent and its
temperature. For water it is:
A = 0.492 at T = 0 C
A = 0.509 at T = 25 C
A = 0.596 at T = 100 C
PIERO M. ARMENANTE
NJIT
Davies Theory
For ionic strengths below 0.5 (molality) it is:
( )
log .
10
2
1
0 2
+ +

+

_
,
AZ
I
I
I
( )
log .
10
2
1
0 2


+

_
,
AZ
I
I
I
( )
log .
10
1
0 2
t +

+

_
,
AZ Z
I
I
I
PIERO M. ARMENANTE
NJIT
CO
2
-Bicarbonate-Carbonate Systems
CO
2
(aq) = CO
2
(g)
K
p
CO
H
co
aq

2
2
CO
2
(aq) + H
2
O = H
2
CO
3
K
H CO
CO
aq

2 3
2
H
2
CO
3
= H
+
+ HCO
3
-
K
H HCO
H CO
1
3
2 3
'

+
HCO
3
-
= H
+
+ CO
3
=
K
H CO
HCO
2
3
3

PIERO M. ARMENANTE
NJIT
CO
2
-Bicarbonate-Carbonate Systems
Since it is difficult to distinguish between CO
2
(aq)
and H
2
CO
3
it is common practice to combine the
two equilibrium equations together to yield:
K
H HCO
H CO CO
K K
K
aq
1
3
2 3 2
1
1

+

+
+
'
and to define:
[H
2
CO
3
*] = [H
2
CO
3
] + [CO
2
]
aq
i.e.:
K
H HCO
H CO
1
3
2 3

+
*
PIERO M. ARMENANTE
NJIT
Values of K
1
and K
2
pK
1
= 6.35
pK
2
= 10.30
PIERO M. ARMENANTE
NJIT
Carbonate Solutions Closed to the
Atmosphere
Consider a carbonate solution (H
2
CO
3
, HCO
3
-
,
CO
3
=
) not in contact with CO
2
or solid calcium
carbonate. The equilibria are:
[ ] [ ]
[ ]
( ) ( )
( )
K
H HCO
H CO
H HCO
H CO
H HCO
H CO
1
3
2 3
3
2 3
3
2 3

+ +
+
* *
*

[ ] [ ]
[ ]
( ) ( )
( )
K
H CO
HCO
H CO
HCO
H CO
HCO
2
3
3
3
3
3
3

PIERO M. ARMENANTE
NJIT
Carbonate Solutions Closed to the
Atmosphere
In addition it is:
( ) ( ) ( ) C H CO HCO CO
t
+ +

2 3 3 3
*
and, from electroneutrality (charge balance):
( ) ( ) ( ) ( ) H OH HCO CO
+
+ +
3 3
2
PIERO M. ARMENANTE
NJIT
Carbonate Solutions Closed to the
Atmosphere - Known pH
If the pH of a carbonate solution is known the
relative composition of all the species is:
( )
[ ]
[ ]
H CO C
K
H
K K
H
C
t
c c c
H CO t 2 3
1 1 2
2
1
1
2 3
+ +

1
]
1
1

+
+

( )
[ ]
[ ]
HCO C
H
K
K
H
C
t
c
c
HCO
t 3
1
2
1
1
3

+
+

+ +

1
]
1
1

PIERO M. ARMENANTE
NJIT
Carbonate Solutions Closed to the
Atmosphere - Known pH (continued)
( )
[ ] [ ]
CO C
H
K
H
K K
C
t
c c c
CO
t 3
2
2
1 2
1
1
3

+ +

+ +

1
]
1
1

where:
[ ] ( )
( )
K
H HCO
H CO
c
1
3
2 3

+
*
[ ] ( )
( )
K
H CO
HCO
c
2
3
3

and:

H CO
HCO CO 2 3
3 3
1 + +

PIERO M. ARMENANTE
NJIT
Carbonate Solutions Closed to the
Atmosphere - Known pH (continued)
3 5 7 9 11 13
pH
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
M
o
l
a
r

F
r
a
c
t
i
o
n
CO
3
=
HCO
3
-
H
2
CO
3
*
PIERO M. ARMENANTE
NJIT
Carbonate Solutions in Contact with CO
2
CO
2
(aq) = CO
2
(g)
[ ] ( )
K
p
CO
p
H CO
H
co
aq
co

2 2
2 2 3
*
If the pH is known then:
( )
H CO
K
p
H
CO 2 3
1
2
*

( )
[ ]
HCO
K
K
p
H
c
H
CO
3
1 2
+

( )
[ ]
CO
K K
K
p
H
c c
H
CO
3
1 2
2
2
+

and:
( ) ( ) ( ) ( ) H OH HCO CO
+
+ +
3 3
2
PIERO M. ARMENANTE
NJIT
Carbonate Solutions in Contact with
Solid CaCO
3
Equilibrium:
[ ][ ] ( )( )
K Ca CO Ca CO
s
Ca CO

++ ++
++
3 3
3

Electroneutrality (charge balance):
( ) ( ) ( ) ( ) ( )
2 2
3 3
Ca H HCO CO OH
++ +
+ + +
Mass Balance (assuming all ions come from the
solid):
( )
( )
( ) ( ) ( )
C Ca H CO HCO CO OH
t
+ + +
++
2 3 3 3
*
PIERO M. ARMENANTE
NJIT
Equivalence Points for Carbonate
Systems
The first and second equivalence points are
reached when enough acid is added to alkaline
carbonate-bicarbonate solutions to complete the
following reactions, respectively:
CO HCl Cl HCO
3 3

+ +
(first equivalence point)
and
CO HCl Cl H CO
3 2 3
2 2

+ +
HCO HCl Cl H CO
3 2 3

+ +
(second equivalence point)
PIERO M. ARMENANTE
NJIT
Carbonate Alkalinity
In correspondence of the carbonate equivalent
points one can determine the alkalinities of the
carbonate system.
Carbonate alkalinity:
( ) ( ) ( ) ( ) CO OH H CO H
3 2 3
+
+ *
Total alkalinity:
( ) ( ) ( ) ( ) HCO CO OH H
3 3
2
+
+ +
PIERO M. ARMENANTE
NJIT
Alkalinity Titration Curves
Acid Added (meq)
0
2
4
6
8
10
12
p
H
Total Alkalinity
Carbonate Alkalinity
PIERO M. ARMENANTE
NJIT
Equations Typically Required in
Equilibrium Calculations
Typically, the solution of chemical equilibrium problems
involves the use of some or all the following equations:
Equilibrium equations (including equilibrium constant)
for all species involved
Dissociation equations
Electroneutrality equation (charge balance) stating that
the total number of all positive charges must be equal to
the number of all negative charges
Mass balances of species
Activity coefficient equations
PIERO M. ARMENANTE
NJIT
Additional Information and Examples
Neutralization and Chemical Equilibrium
Additional information and examples can be found in the
following references:
Corbitt, R. A. 1990, The Standard Handbook of
Environmental Engineering, McGraw-Hill, New York, pp.
6.154-6.160.
Droste, R. L., 1997, Theory and Practice of Water and
Wastewater Treatment, John Wiley & Sons, New York, pp.
57-66.
Eckenfelder, W. W., Jr., 1989, Industrial Water Pollution
Control, McGraw-Hill, New York, pp. 48-53.
Haas, C. N. and Vamos, R. J., 1995, Hazardous and
Industrial Waste Treatment, Prentice Hall, Englewood Cliffs,
NJ, pp. 118-131.
PIERO M. ARMENANTE
NJIT
Additional Information and Examples
Neutralization and Chemical Equilibrium
Metcalf & Eddy, 1991, Wastewater Engineering: Treatment,
Disposal, and Reuse, McGraw-Hill, New York, pp. 303-305.
Smith, J. M. and Van Ness, H. C., Introduction to Chemical
Engineering Thermodynamics, 3rd Edition, McGraw-Hill,
New York, pp. 496-547.
Sundstrom, D. W. and Klei, H. E., 1979, Wastewater
Treatment, Prentice Hall, Englewood Cliffs, NJ, pp. 301-334.
Weber, W. J., Jr., 1972, Physicochemical Process for Water
Quality Control, Wiley-Interscience, John Wiley & Sons,
New York, pp. 7-15.
Wentz, C. W., 1995, Hazardous Waste Management, Second
Edition, McGraw-Hill, New York, pp. 154-156.
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Creation Date: 02/20/97 7:31 PM
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