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Chemical Equilibrium

A condition in which the system is at its minimum attainable


chemical energy level and hence has no tendency to undergo
chemical change.

Analogous Physical Equilibria:

r1
r2

h2 r1
r1 gh1  r2 gh2 K 
h1 r 2
The Equilibrium Constant, Keq

For any reaction with stoichiometry:

aA + bB  cC + dD

 C  D
c d

K eq 
 A   B
a b

where (i) is a normalized (non-dimensional) concentration


of chemical i, and the values are all measured in a system
at equilibrium
The Equilibrium Constant, Keq
 C  D
c d

aA + bB  cC + dD K eq 
 A   B
a b

Analogous to defining an
equilibrium constant relating
liquids 1 and 2 as the ratio of
the liquid column heights
(h2/h1) for a system that has
reached static equilibrium.
h1 r1 Note that one need not know
r2 h2 the densities of the fluids (or
understand how they relate to
to the heights) if the “K” value
is given. Also, h2/h1 K if the
system is not at equilibrium.
The Equilibrium Constant, Keq

• If the actual ratio of normalized concentrations (Q) equals Keq,


the reaction is at equilibrium
• If Q does not equal Keq, the reaction will proceed in the
direction that causes Q to approach Keq
• Evaluation/use of Keq requires knowledge of:
– the chemical reaction (stoichiometry)
– conventions for quantifying and normalizing the
concentrations of the reactants and products
The Equilibrium Constant, Keq
• Concentration Conventions
– For dilute dissolved species (e.g., Na+, Cl- in water),
concentrations are expressed in mol/L, and the
normalizing concentration is 1.0 mol/L
– For the main constituents of a condensed phase (e.g.,
water, or a pure solid), concentrations are expressed as
the mole fraction of that phase that the species
represents (moles of i/total moles in phase). This fraction
is typically so close to 1.0 that we can approximate the
normalized concentration as exactly 1.0.
– For gases, concentrations are expressed as the pressure
that the species exerts (the partial pressure), in
atmospheres, and the normalizing concentration is
1.0 atm.
The Equilibrium Constant for Water
Dissociation, Kw

H2O  H+ + OH-

K eq 
  
H +
OH -


  
H +
OH -

 10-14.0  K w
 H 2O  1.0

pH = -log10(H+)
Some Important Equilibria in Water
Treatment Involving Solids
• CaCO3(s)  Ca2+ + CO32- Hardness
• Mg(OH)2(s)  Mg2+ + 2 OH- Hardness
• PbCO3(s)  Pb2+ + CO32- Lead & Copper Rule (LCR)
• Cu(OH)2(s)  Cu2+ + 2 OH- LCR
• Cu2(OH)2CO3(s)  2Cu2+ + 2 OH- + CO32- LCR
• Fe(OH)3(s)  Fe3+ + 3 OH- Coagulation
• Al(OH)3(s)  Al3+ + 3 OH- Coagulation
• SiO2(s) + 2 H2O  H4SiO4 Membrane fouling,
Arsenic treatment
Equilibrium Constants Involving
Solids

XY2Z(s)  X + 2 Y + Z

 X  Y   Z   X  Y   Z 
2 2

Keq    K sp or K so
 XY2 Z  s   1.0

• “Solubility product” (Ksp or Kso) is Keq for dissolution of


the solid into its constituents
• The solid (and sometimes H2O) are the only chemicals
on the left side
Some Solids are Very Soluble or Very
Insoluble
• Some solids (e.g., NaCl, CaCl2, Na2SO4) are so soluble
under normal water treatment conditions that we never
consider the possibility that the solid will be present in an
equilibrium solution.
• Other solids (e.g., Fe(OH)3, MnO2) are so insoluble under
normal water treatment conditions that we assume 100% of
the limiting species (e.g., Fe, Mn) precipitates.
• Some solids (CaCO3) are “slightly soluble” under normal
water treatment conditions, so neither assumption applies.
Others (PbCO3, AlPO4) are very insoluble, but the trace
amount that dissolves is still of concern.
Issues that Arise Regarding Slightly
Soluble Solids in Water Treatment
• Is Qso greater than, less than, or equal to Kso initially?
• How much does the concentration of some constituent have
to change to cause Qso to equal or exceed Kso (i.e., for
precipitation to begin)?
• How much of some chemical must be added to cause Qso to
equal or exceed Kso?
• Will a solid precipitate if a specified amount of some chemical
is added? If so, how much?
• If a solution with known composition comes into contact with a
solid, how much solid will dissolve?
Example: Dissolution of
Gypsum (CaSO4(s))

• Kso for gypsum is 10-4.6


• 1.0 g of gypsum is dispersed in 1.0 L of water containing no
Ca2+ or SO42-. How much solid (if any) remains after the
system reaches equilibrium?
• Repeat the analysis if the solution initially contains 200 mg/L
SO42-.
Dissolution of CaSO4(s) if
(Ca2+)init = (SO42-)init = 0

K sp  10-4.6 
  4 
Ca 2
SO 2-


  4 
Ca 2
SO 2-

  Ca 2 SO24- 
 CaSO  s 
4 1.0

   4 
Ca 2
 SO 2-

10 -4.6
  Ca 
2 2

 Ca 2
  10 
-4.6 0.5
 10-2.3  5.0x10-3  SO42- 
Dissolution of CaSO4(s) if
(Ca2+)init = (SO42-)init = 0
 -2.3 mol  g 
 Ca   10 L 
2
40
 mol 
  0.20
g
L

SO 
4
2-  -2.3 mol  
 10

  96
g 
L   mol 
  0.48
g
L

CaSO4(s) dissolved = 0.68 g/L


CaSO4(s) remaining undissolved = 0.32 g/L (32%)
Dissolution of CaSO4(s)
with (SO42-init >0

mg   1 mol 
SO 
4
2-
init

  200

   2.08x10
L   96, 000 mg 
-3 mol

Ksp  10-4.6   Ca 2   4 
SO 2-
  x   2.08x10-3  x 
final final

x  4.08x10-3
Dissolution of CaSO4(s)
with (SO42-init >0
mol  mg 
 Ca  2
final
 x  4.08x10-3

L 
 40, 000   163
mol 
mg
L

mol  mol  mg 
SO42-  final
  x  2.08x10-3 
L
  6.16x10-3


L 
96, 000 
mol 
 591
mg
L

CaSO4(s) dissolved = 163 mg/L + (591 - 200)mg/L = 554 mg/L


CaSO4(s) remaining undissolved = 446 mg/L (44.6%)
The Carbonate Chemical
Group in Water
• Dissolved Carbonate-containing species
– Carbonic Acid: H2CO3. Can form by combination of a
carbon dioxide molecule and water:

CO2 + H2O  H2CO3 Keq 


 H2CO3 
 CO2  g   H2O
– Bicarbonate Ion: HCO3-. Can form by “dissociation”
of carbonic acid:

H2CO3  HCO3- + H+ K eq 
 HCO  H 
3
- +

K
 H 2CO3  a1
The Carbonate Chemical Group
• Dissolved Carbonate-containing species
– Carbonate Ion: CO32-. Can form by dissociation of
bicarbonate ion:

HCO3-  CO32- + H+ K eq 
 3  
CO 2-
H +

 Ka 2
 HCO 
3
-

• Other Commonly Defined Quantities


– Total Dissolved Carbonate: TOTCO3
TOTCO3 = (H2CO3) + (HCO3- + (CO32-) + [others?]

– Alkalinity: ALK
ALK = (HCO3- + 2(CO32-) + (OH- - (H+)
Units for Expressing Alkalinity
• Equivalents: One equivalent (equiv) of alkalinity refers
to one mole of "H+ binding capacity."
– one mole of HCO3- has the capacity to combine with
one mole of H+, so one mole of HCO3- is one
equivalent of alkalinity
– one mole of CO32- has the capacity to combine with
two moles of H+, so one mole of CO32- is two
equivalents of alkalinity
Units for Expressing Alkalinity
• mg/L as CaCO3: The number of mg/L of CaCO3 that
would have to be dissolved into pure water for that
water to have the same alkalinity as the water of
interest
– one mole of CaCO3 can combine with two moles of H+,
so one mole of CaCO3 is two equivalents of alkalinity
– the MW of CaCO3 is 100, so 50 g of CaCO3 is one
equivalent. An alkalinity of “75 mg/L as CaCO3” is
therefore 1.5 meq/L
Equilibrium Among Dissolved
Carbonate Species
H2CO3/TOT CO3 - 2-
HCO3 /TOTCO3 CO3 /TOTCO3
1.0
0.9
0.8
Conc'n / TOT CO3

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
2 3 4 5 6 7 8 9 10 11 12
pH
Other Types of Precipitation &
Dissolution Problems
• In preceding example (precipitation of CaSO4(s)), TOTCa
& TOTSO4 varied due to solid precipitation, but under all
conditions, TOTCa=(Ca2+) and TOTSO4=(SO42-).

• In other commonly encountered systems, the


concentration of one or both precipitating ions depends
not only on the amount of solid formed, but also other
variables (especially pH).
Example: Precipitation & Dissolution
of a Phosphate Solid
• Drinking water at pH 8.0 contains 3.22x10-6 mol/L TOTPO4
(0.1 mg/L TOTPO4-P); Corrosion of galvanized pipe releases
Zn2+

• TOTPO4 distributed among four HxPO4x-3 species:


 H3PO4  H2PO4- + H+ Ka1=10-2.2
 H2PO4-  HPO42- + H+ Ka2=10-7.2
 HPO42-  PO43- + H+ Ka3=10-12.4

• Question: What is the maximum concentration of Zn2+ that


can be dissolved in the solution, considering possible
precipitation of Zn3(PO4)2(s) (Ks0=10-36.7)
K a1 
 H PO  H 
2
 10
4
- 
-2.2

 H3PO4 
 HPO   10  PO  H 
4
2- 12.4
4
3- 

 HPO  H  2- 
-7.2
 10  PO  4.4 3-

  10
4 4
Ka 2
 H PO 2 4
-


 PO  H 
4
3-

 10

-12.4
Ka3
 HPO  4
2-  H PO   10  PO  H 
2 4
- 19.6
4
3-  2

 10  PO 3.6
4
3-

 PO43-  H 
2

Ka 2 Ka3   10-19.6
 H PO  2 4
-

 PO  H  3-  3
-21.8
 H3PO4   10 21.8
 PO  H 
4
3-  3

  10
4

 PO 
K a1 K a 2 K a 3
 H3PO4   10-2.2 4
3-
TOTPO4   H3PO4    H 2 PO4 -    HPO4 2-    PO43- 
 10-2.2  PO43-   103.6  PO43-   104.4  PO43-    PO 43- 
 2.91x104  PO43- 

-6

 PO43-   2.91x104  1.11x10-10


3.22x10

1/ 3 1/ 3
   -36.7 
    s30- 2 
Zn 2 K

10   2.56x10-6
  PO 4  
 1.11x10-10  
2

 
Example: Water Softening
• Drinking water at pH 7.0 contains 3x10-3 mol/L Ca2+
(120 mg/L), and 1.0x10-3 Alk; Ks0 for CaCO3(s) is 10-8.3
– Is the solution supersaturated, undersaturated, or at equilibrium with
respect to CaCO3(s)?
– What is the stoichiometric dose of lime (Ca(OH)2) required to convert
H2CO3 and HCO3- to CO32-?
– If TOTCO3 is essentially all converted to CO32-, will CaCO3(s)
precipitate? If so, how much, and what will the final concentration of
Ca2+ be?
Determine TOTCO3 and Distribution of
Carbonate Species
  
ALK  HCO3-  2 CO32-  OH - - H      
 HCO  K -

1.0x10-3  HCO3-  2 H 3 a2



Kw
 
- H
  
H 

 HCO 10 - -10.3


10-14.0
1.0x10 -3

 HCO3 -
 2
3

10-7.0
 -7.0 - 10-7.0
10

1.0x10-3  1.001 HCO3-  


1.0x10-3
 HCO  3
-

1.001
 1.0x10-3
Determine TOTCO3 and Distribution of
Carbonate Species
 HCO  K - -3.0 -10.3
 
CO  -

10 10
3 a2
 10-6.3
3
H  10  -7.0

 H CO  
 HCO  H  10 10

3
-  -3.0 -7.0
 10-3.7  2x10-4
10-6.3
2 3
Ka1

TOTCO3   H2CO3   HCO3-  CO32-    


 2.0x10-4  1.0x10-3  5x10-7  1.2x10-3

 Ca  CO   3x10 10   10
2+
3
2- -3 -6.3 -8.8
 Ks0

Thus, CaCO3(s) is undersaturated in the initial solution


Estimate Stoichiometric Dose of Lime
OH- will be used to (1) convert HCO3- and H2CO3 to CO32-, and (2)
decrease free H+ and increase free OH- . Assume required pH is ~10.8.

HCO3-  OH-  CO32-  H2O H2CO3  2OH-  CO32-  2H2O

 Moles of OH - required to 

 
 cause CO32-  TOTCO3 
     
  2  H 2CO3   HCO3-   OH - -  H 
 

      
 2 2.0x10-4  1.0x10-3  10-3.2 - 10-7.0 - 10-7.0 - 10-10.8 
 2.03x10-3
Estimate Stoichiometric Dose of Lime

 Moles of lime required to  1  Moles of OH - required to 


   
  2-
   
 cause CO3  TOTCO3  2  cause CO3  TOTCO3 
2 -
 


1
 2.03x10-3
2

 1.02x10-3
After Dosing with Lime, the Solution is
Supersaturated

TOTCO3  1.2x10-3  CO32-  


 Ca    Ca 
2 2
init

 Ca 2 
lime
 3.0x10-3  1.0x10-3  4.0x10-3

     
Ca 2 CO32-  4.0x10-3 1.2x10-3  4.8x10-6  10-5.32 > K s 0
How Much Solid Will Precipitate?
If x is the amount (mol/L) of CaCO3(s) that precipitates, the
concentrations of TOTCa and TOTCO3 in solution will each
decrease by x. If (CO32-)  TOTCO3 after precipitation (i.e., if the
pH is >10.8), then x is also the decrease in (CO32-). In such a
case, we can write:


Ks 0  Ca 2  CO 
equil
3
2-
equil 
  Ca 2 
init

- x   CO32-
 
init
- x

 
10-8.3  4.0x10-3 - x 1.2x10-3 - x 
x  1.198x10-3
TOTCO3, final  2x10-6 TOTCa final  2.8x10-3

Precipitation removes 99.8% of TOTCO3 but lowers


TOTCa by only 7% compared to initial value
(2.8x10-3 vs 3.0x10-3).
Determine How Much Soda Ash to Add
To remove more Ca2+, we must add more TOTCO3. A frequently
cited, but somewhat outdated rule of thumb is to add Na2CO3 to
make TOTCa=TOTCO3. If that is done:

 Na 2CO3 dose  TOTCa - TOTCO3,init 


 4.0x10-3 - 1.2x10-3  2.8x10-3

Then, when the solution equilibrates with the solid:

 Ca  CO    Ca 
2
3
2- 2 2
 10-8.3

Ca  
2
10-8.3  10-4.15  7.1x10-5  2.8 mg/L

This Ca2+ concentration is very low. Since Na2CO3 is expensive, the actual
dose is usually less than the dose based on the rule of thumb.