Water Stabilization

Department of Civil, Water Resource and Environmental

Engineering

King Fahd University

 Water Stabilization
As in water softening, when the concentrations of
CaCO3 and Mg(OH)2 exceed their solubilities, the
solids may continue to precipitate.

This condition can cause scale to form, a solid that

deposits due to precipitation of ions in solution.

To prevent scale formation, the water must be

stabilized.
 If the pH is high, stabilization may be accomplished
using one of several acids or using CO2, a process called
recarbonation.
If the pH is low, stabilization may be accomplished using
lime or some other bases.
Because of the universal presence of
carbon dioxide, any water body is affected
by the reaction products of carbon dioxide
and water.

The species produced from this reaction CO2

H2O
form the carbonate system equilibria. As
discussed later, the stability or instability
of water can be gaged using these
equilibria.
1. Carbonate Equilibria
The carbonate equilibria is a function of :
the ionic strength of water,
activity coefficient,
and the effective concentrations of the ionic
species.
Carbonate Equilibria:
• Calcium is one of the major cations that can form
scales as a result of the instability of water.
• Calcium plays an important role in the carbonate
equilibria.
• We will therefore express the carbonate
equilibria in terms of the interaction of the
calcium ion and the carbonate species which are
the reaction products of carbon dioxide and
water.
Carbonate Equilibria:
• Since the equilibria occur in water, the
dissociation of the water molecule must also
be involved.

• Using calcium as the cation, the equilibrium

equations of the equilibria along with the
respective equilibrium constants at 25 ºC are
as follows (Rich, 1963):
Carbonate Equilibria:
K w  10 14  {H  }{OH  }
{H  }{HCO3 }
K l  10 6.35 
H 2CO3*
{H  }{CO32 }
K 2  10 10.33 
HCO3

K sp ,CaCO3  4.8(10 9 )  {Ca 2 }{CO32  }

Carbonate Equilibria:
• The Ks are the values of the respective
equilibrium constants.

• Ksp.CaC03 is the equilibrium constant for the

solubility of CaC03.

• The pair of braces, { }, are read as "the activity

of,"
Carbonate Equilibria:
• the equilibrium constants are calculated using
the activity.

• Activity: is a measure of the effectiveness of a

given species in its participation in a reaction.

• It is an effective or active concentration and

has units of concentrations.
Carbonate Equilibria:
{sp} = γ [sp]
• Where sp represents any species involved in
the equilibria.

• The pair of brackets, [], is read as "the

concentration of,“.

• γ is the activity coefficient.

:Carbonate Equilibria.1
1.1 Ionic Strength:
• As the particle ionizes, the number of particles
increases.
• the activity coefficient is a function of the
number of particles in solution.
• The number of particles is characterized by
the ionic strength μ.
1
   [ spi ]z i
2

2
1.1 Ionic Strength:
• i is the index for the particular species and z
is its charge.
• The concentrations are in gmmols/L In terms
of the ionic strength.
• the activity coefficient is given by the DeBye-
Huckellaw as follows (Snoeyink and Jenkins,
1980; Rich, 1963):
1.1 Ionic Strength:
0.5 z i2 (  )
 log  
1  1.14(  )
0.5 zi2 (  )

11.14 (  )
  10
Langelier estimated  as
(TDS  2.5  10-5)
Russell estimated  as
) specific conductance  1.6  10-5 (
Example 1
• The pH of a solution is 7. Calculate the
hydrogen ion concentration?
Solution:
pH = -log10{H+}
7 = -log10{H+}
{H+} = 10-7 gmmols/L Ans.
Example 2
• The concentration of carbonic acid was
analyzed to be 0.2 gmmols/L. If the pH of the
solution is 7, what is the concentration of the
bicarbonate ion if the temperature is 25°C?
• Solution:
  7 
 6.35 { H }{ HCO } 10 { HCO 3}
K l  10  *
3

{H 2 CO3 } 0.2 / 1000

{HCO3 }  8.93(10  4 ) gmol / L  [ HCO3 ] Ans.

Example 3
• A sample of water has the following
composition: CO2 = 22.0 mg/L, Ca2+ = 80
mg/L, Mg2+ = I2.0 mg/L, Na+ = 46.0 mg/L,
HCO3- = 152.5 mg/L, and SO42- = 216 mg/L.
What is the ionic strength of the sample?
• Solution:

1
   [ sp i ]z i
2

2
 Ion Mg/L Mol. Mass gmmols/L
Ca2+ 80 40.1 0.001995
Mg2+ 12.0 24.3 0.0004938
Na+ 46.0 23 0.002
HCO3- 152.5 61 0.0025
SO42- 216 96.1 0.0022

μ = 1/2[0.001995(22) + 0.0004938(22) + 0.002(1) +

0.0025(1) + 0.0022(22)]
= 0.023 Ans.
Example 4
 • In Example 3, calculate the activity coefficient
and the activity in mg/L of the bicarbonate
ion.
• Solution: 2
0.5 zi (  )

11.14 (  )

  10
0.5 (1)( 0.023 )

  10 11.14 ( 0.023)
 0.86
γ [sp]} = sp{
.0.86(0.0025) = 0.00215 mg/L Ans} = -HCO3{
1.2. Equilibrium Constant As a Function Of
Temperature:
• The equilibrium constants given previously
were at 25°C.
• To find the values of the equilibrium constants
at other temperatures, the Van't Hoff equation
is needed;

d ln K 
 2
dt RT
• Where:
• T: is the absolute temperature.
• ΔHº: is the standard enthalpy change, where the
standard enthalpy change has been adopted as the
change at 25°C at one atmosphere of pressure.
• R: is the universal gas constant.

• The value of R depends upon the unit used for the

other variables. Table 11.1 gives its various
values and units
• Table 11.2 shows values of interest in water
stabilization. It is normally reported as enthalpy
changes.
• The enthalpy change is practically constant
with temperature; thus ΔHº may be replaced
by ΔHº298 Doing this and integrating the Van't
Hoff equation from KT1 to KT2 for the
equilibrium constant K and from T1 to T2 for
the temperature,


KT 2  K T 1 exp[ (T2  T1 )]
298
RT1T2
“This equation expresses the equilibrium constant
as a function of temperature”.
1.3. ΔH298o, For Pertinent Chemical
Reactions Of the Carbonate Eq.:
According to Hess's low, if the chemical reaction
can be written in steps, the enthalpy changes can
be obtained as the sum of the steps;
• The values of the ΔH298o’s are obtained from
the previous Table 11.2.
• The values in the table indicate ΔH298o of
formation having negative values.
• If the reaction is not a formation but a breakup
such as;
1 ,
HOH (l )  H 2  O2 The sign is positive.
2
Example 5
 Hand-off

• Any questions?
2. Criteria For Water Stability at
Normal Conditions:
• In the preceding discussions, a criterion for
stability was established using the equilibrium
constant Ksp.
• At normal conditions, as especially in the
water works industry, specialized forms of
water stability criteria have been developed.
• These are saturation pH, Langelier index, and
the precipitation potential of a given water.
 2.1. Saturation pH and Langelier
Index:
• Because pH is easily determined the determination of
saturation pH is convenient method of determining the
stability of water.
• If the condition is at equilibrium no precipitate or scale
will form.
• If the pH of the sample is determined , this can be
compared with the equilibrium pH to see if the water
stable or not.
• Therefore, we now proceed to derive the equilibrium
pH. “Equilibrium pH is also called saturation pH”.
• In natural systems, the value of the pH is
strongly influenced by the carbonate equilibria
reactions.
• The CO32- species of these reactions well pair
with a cation, thus the equilibrium reactions
into a dead end by forming a precipitate.
• For example, the complete carbonate equilibria
reactions as follows:
 
HOH  H  OH Kw
 
H 2CO  H  HCO
*
3 3 K1
 HCO3( aq )  H ( aq )  CO32 K2
c 2
Cation 2 (CO3 ) c ( s )  2Cation  cCO
3 K sp

• c is the charge of the cation that pairs with

CO32- forming the precipitate Cation2(CO3)c(s).
• We call the formation of this precipitate as the
dead end of the carbonate equilibria, since the
carbonate species in solution are removed by
the precipitation.
• In order to find the dead end cation , several
cations can possibly pair with the carbonate.
• The pairing will be governed by the value of Ksp.
• The cation with smallest Ksp value is the one that
can form a dead end for the carbonate equilibria
reactions.
• however, of all the possible cations, Ca2+ is the
one that is found in great abundance in the nature
compared to the rest.
• Thus, although all the other cations have much
more smaller Ksp’s than the calcium, they are of
no use as dead ends if they do not exist (see Table
11.3).
• As will be shown later, the saturation pH may
conveniently be expressed in terms of total
alkalinity.
• The species which are the components of the
carbonate equilibria , they also represent as
components of the total alkalinity of the
carbonate system equilibria.
• They may be added together to produce the
value of the total alkalinity.
• A convenient common unit is the gram
equivalent. Letting [A]geq represent the total
alkalinity;
[ A] geq  [OH  ] geq  [ HCO3 ] geq  [CO32 ]  [ H  ]
• Equations to calculate the carbonate
equilibria species:

{OH } Kw
[OH  ] geq 
 [OH ]  
 OH  OH {H  }

 

{H }{CO } 2
{H  }K sp ,CaCO3
[ HCO ]3 geq  [ HCO ] 
3
3

 HCO3 K 2  HCO3 K 2 {Ca 2 }

[CO32 ] K sp ,CaCO3
[CO32 ] geq  
2 2 CO3 {Ca 2 }

 { H }
[H ] 
H
 • Then the total alkalinity equation becomes;
Kw {H  }K sp,CaCO3
K sp ,CaCO3 {H  }
[ A] geq    
 OH {H }  HCO3 K 2 {Ca } 2 CO3 {Ca }  H
 2 2

Let
A  [ A] geq , B  Kw K sp ,CaCO3 1
,C  ,
 OH  HCO3 K 2 {Ca }  H
2

K sp ,CaCO3
and D
2 CO3 {Ca 2 }
Solving for {H+},
  ( D  A)  ( D  A) 2
 4CB
{H }   {H s }
2C
thus, the saturation pH, pHs is


pH s   log10 {H } s

• The Langlier Index (or Saturation Index) (LI)

is the difference between the actual pH and
the saturation pH of the a solution, thus;

LI  pH  pH s
Example 6
Example 7
2.2. Determination of {Ca2+}:
• The activity of the calcium ion is affected by
its complexation with anions.
• Ca2+ forms complexes with the carbonate
species, OH- and SO42-.
• The complexation reactions are as follows:
CaCO3  Ca 2  CO32
CaHCO3  Ca 2  HCO3
CaOH   Ca 2  OH 
CaSO4  Ca 2  SO42 

Ca anion = anion complex of calcium ion

. represent complex of calcium ion =
• Let the total concentration of the calcium
species as determined by titration be [CaT].
• Thus, the concentration of the calcium ion
[Ca2+(aq)] is
    
[Ca(2aq ) ]  [Ca T ]  ([CaCO3 ]  [CaHCO3 ]  [CaOH ]  [CaSO4 ])

• Table 11.4 shows the equilibrium constants of

the previous complexes at 25 oC.
• By applying Hess’s law and using solubility
product relations the above equation becomes:

 
2 [Ca ]  [CaCO ]  [CaHCO 3 ]
[Ca ]  T 3

 Ca K w  Ca  SO4 [ SO42 ]
1 
 CaOHc K CaOHc  H [ H ]

K CaSO4c
Example 8
2.3. Total Alkalinity As Calcium
Carbonate:
• The unit of concentration that we used for alkalinity
is equivalent per unit volume.
• But alkalinity also can be expressed in terms of
CaCO3.
• Expressing the alkalinity in terms of CaCO3 is a sort
of equivalence.
• depending upon the chemical reaction it is involved
with, CaCO3 can have more than one value for its
equivalent mass.
• If the reaction is
 2
CaCO3  2 H  H 2 CO3  Ca
CaCO3 has an equivalent mass of CaCO3/2, because
the number of reference species is 2.
• To illustrate the use of this concept, assume 10 -3
gmmol/L of the hydroxide ion and express this
concentration in terms of CaCO3.
the pertinent reaction is OH   H   HOH .
[OH-] = 10-3 gmmol/L = 10-3 geq/L
= 10-3(CaCO3/2) g/L as CaCO3
= 0.05 g/L as CaCO3 = 50 mg/L as CaCO3.
 2.4. Precipitation Potential:
Precipitation potential is another
criterion for water stability, and
application of this concept can help
prevent situations like the one
shown in this figure.

All solutions are electrically neutral and negative

charges must balance the positive charges. Thus, the
balance of charges, where concentration must be
expressed in terms of equivalents, is
[CO32 ]eq  [ HCO3 ]eq  [OH ]eq  [ H  ]eq  [Ca 2 ]eq
• Expressing in terms of moles,

2[CO32 ]  [ HCO3 ]  [OH ]  [ H  ]  2[Ca 2 ]

• the amount of calcium carbonate that precipitates

is simply the equivalent of the calcium ion that
precipitates, Cappt.
• Because the number of moles of Cappt is equal to
the number of moles of the carbonate solid
CaCO3ppt that precipitates,
[CaCO3ppt] = [Cappt]
• [CaCO3ppt] is the precipitation potential of calcium
carbonate, Cappt, in turn, can be obtained from the
original calcium, Ca2+before, minus the calcium at
equilibrium, Ca2+after.
[Cappt] = [Ca2+before] - [Ca2+after]

• To use the above equation [Ca 2+before] must first be known.

• To determine [Ca2+after], the charge balance equation

derived previously will be used. [Ca 2+after] is the [Ca2+] in
the charge balance equation, thus
 2[CO32 ]  [ HCO3 ]  [OH ]  [ H  ]  2[Caafter
2
]

By substituting the carbonate system equilibria equations

in the above equation and solving for , [Ca2+after], produces
2
[Caafter ]

2
 Kw    2 Kw   K [ H  2
] K sp ,CaCO3 
  [ H  ]2     [ H ]    8[ H  ]  2 sp , CaCO 3 
[H ]  
  OH  H    OH  H      HCO3  H K 2 Ca 
 CO3 Ca 
4[ H  ]

• The [H+] in the previous equation is the saturation pH.

• Finally, the precipitation potential [CaCO3ppt] is:

]Ca2+after] - [Ca2+before] = [Cappt] = [CaCO3ppt[

 2.5. Determination of Percent Blocking
Potential of Pipes:
• Let Volpipe be the volume of the pipe segment upon
which the percent blocking potential is to be
determined.
• The amount of volume precipitation potential in this
volume after a time t is:
100([Ca 2
before
2
]  [Ca after 
])Vol pipe t /  CaCO3 t d

•  CaCO3 = the mass density of the carbonate precipitate.

• t d = the detention time of the pipe segment.
 td = Volpipe/Qpipe

• Qpipe = the rate of flow through the pipe.

• by substituting this expression for td, the
percent blocking potential P block after time t is:

2 2
100([Cabefore ]  [Ca after ])Q pipe t
Pblock  (100)
 CaCO3 Vol pipe
• = 2600 g/L.
• Note
CaCO3 that since the concentrations are expressed in

gram moles per liter, volumes and rates should be

expressed in liters and liters per unit time, respectively.
Example 9
Example 10
• Assume that the pH of the treated water in Example 11.9
was raised to cause the precipitation of the carbonate
solid. The water is distributed through a distribution
main at a rate of 0.22 m3/s. Determine the length of time
it takes clog a section of the distribution main 1 km in
length, if the diameter is 0.42 m.
Solution:
 Hand-off

• Any questions?
3. Recarbonation of Softened Water
• After the softening process, the pH is so high
that reduction is necessary to prevent
deposition of scales in distribution pipes.
• This can be accomplished inexpensively using
carbon dioxide.
• We will therefore develop the method for
determining the carbonic acid necessary to set
the water to the equilibrium pH.
• In recarbonation, the available calcium ion in
solution is prevented from precipitation.
• Therefore, it remains to determine at what pH
will the equilibrium condition be, given this
calcium concentration.
• This determination is, in fact, the basis of the
Langelier saturation pH.
• Adding carbonic acid will increase the acidity
of the solution after it has neutralized any
existing alkalinity.
• Let the current pH be pHcur and the pH to
which it is to be adjusted (the destination pH)
be pHto.
• The hydrogen ion concentration corresponding
to pHcur is 10-pHcur gram moles per liter and that
corresponding to pHto is 10-pHto gram moles per
liter.
• Assuming no alkalinity present, the total acid to
be added is 10-pHto - 10-pHcur gram moles per liter.
Alkalinity is always present, however, so more
acid must be added to counteract the natural
alkalinity, [Acur]geq. Thus, the total acidity to be
added, [Acadd]geq, is:
  pH to  pH cur
10  10
[ Acadd ] geq  [ Acur ] geq 
a
• Where Фa is the fractional dissociation of the
hydrogen ion from the acid supplied.
• For strong acids, Фa is unity; for weak acids, it
may be calculated from equilibrium constants
(Table 11.5).
Th anks
 Q&A
• Any questions?
Thanks