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r1
r2
h2 r1
r1 gh1 r2 gh2 K
h1 r 2
The Equilibrium Constant, Keq
aA + bB cC + dD
C D
c d
K eq
A B
a b
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
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
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
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
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
-
– 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-).
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
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 -
10-7.0
-7.0 - 10-7.0
10
H CO
HCO H 10 10
3
- -3.0 -7.0
10-3.7 2x10-4
10-6.3
2 3
Ka1
Ca CO 3x10 10 10
2+
3
2- -3 -6.3 -8.8
Ks0
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
1
2.03x10-3
2
1.02x10-3
After Dosing with Lime, the Solution is
Supersaturated
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
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.