Updated: 13 April 2018 Print version

Lecture #38
Precipitation and Dissolution: Metal
Carbonates & Hydroxides
(Stumm & Morgan, Chapt.7)
Benjamin; Chapter 8.7-8.15

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 Practice Session

 Al(OH)3 ppt
 Homework #8
 Cr(OH)3 ppt
 Zn(OH)2 ppt
 Cd(OH)2 ppt

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Metal Precipitates; Kso values (1/2)
 Table 11.1a in Benjamin (pg 581)

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Metal Precipitates; Kso values (2/2)
 Table 11.1b in Benjamin (pg 582)

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 Metal Hydrolysis
 Table 10.2 in
Benjamin
 Pg 858-859

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Cd(OH)2 example
 Cd species equations
 From Benjamin, pg 584

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Cd(OH)2 solubility diagram
 Pg 586 in Benjamin

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Chromium Hydroxide I
 Thermodynamic Data

Stumm &
 Although “metastable”, the Cr(OH)3 (s) is thought
Morgan, 1996,
to control solubility in wastewaters pg. 365

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Chromium Hydroxide II
 Based on Constants
in Stumm & Morgan

Stumm &
Morgan, 1996,
Figure 7.4, pg.
366
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ZnO solubility

Stumm &
Morgan, 1996,
Figure 7.6a, pg.
370
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Zinc with OH, CO3 and Cl
 Pg 636 in Benjamin

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Metal Carbonates
 Consider CaCO3 in a closed system
 Six species: Ca+2, H+, OH-
CO3-2, HCO3-, H2CO3*
 Need six equations
CO3-2
 K1, K2, Kw
Ca+2
 Kso
 ENE CaCO3
 MBE

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Calcium Carbonate
K so
 Kso [Ca + 2 ] =
[CO3− 2 ]
K so
=
α 2CT

 MBE [Ca +2 ] = CT = [ H 2CO3* ] + [ HCO3− ] + [CO3−2 ]

 combining [Ca + 2 ] =
K so
α 2 [Ca + 2 ]

K so
[Ca + 2 ] =
α2

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 0

-1

-2
Ca+2

-3 HCO3-
-4 +/-0.5 slope
+/-1 slope
-5

-6
Log C

-7 CO3-2
-8
H2CO3*
-9

-10

-11

-12
 Dissolution of CaCO3 in
pure water
-13

-14
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

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 0

-1 OH-
HCO3- Ca+2
-2

-3

-4
H+

-5

-6
Log C

-7
CO3-2
-8 H2CO3*
-9

-10

-11

-12

-13

-14
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

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 0

-1 OH-
HCO3- Ca+2
-2

 ENE
-3

-4
H+

-5
2[Ca +2 ] + [ H + ] = [ HCO-63− ] + 2[CO3−2 ] + [OH − ]
Log C

-7
CO3-2
-8 H2CO3*
-9

-10

-11

-12

-13

-14
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

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Analytical Solution
 Start with ENE and substitute
2[Ca +2 ] + [ H + ] = [ HCO3− ] + 2[CO3−2 ] + [OH − ]
K so Kw
2 + [ H + ] = α1CT + 2α 2CT +
α2 [H + ]
K so K so K so Kw
2 + [ H + ] = α1 + 2α 2 +
α2 α2 α2 [H + ]

[H + ] +
K so
(2 − α1 − 2α 2 ) − Kw
=0
α2 +
[H ]

 For CaCO3: pH=9.91 S&M, equation #30

Pg. 376

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With other acy/alk
 CaCO3 system with addition of:
 Strong acid (CA)
 Strong base (CB)

C B + 2[Ca +2 ] + [ H + ] = [ HCO3− ] + 2[CO3−2 ] + [OH − ] + C A

[H + ] +
K so
(2 − α1 − 2α 2 ) − Kw
= (C A − C B )
α2 +
[H ]

S&M, equation #31

Pg. 376
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 K so
[Ca + 2 ] =
[CO3− 2 ]
CaCO3 in open system =
K so
α 2CT
+2 K so  α 0 

 Applying the open system CT: [Ca ] =
α 2  K H pCO2 

 And substituting into the ENE:
2[Ca +2 ] + [ H + ] = [ HCO3− ] + 2[CO3−2 ] + [OH − ]

K soα 0 K H pCO2 K H pCO2 K

2 + [ H ] = α1
+
+ 2α 2 + w+
α 2 K H pCO2 α0 α0 [H ]

K soα 0 K H pCO2 K H pCO2 K

2 + [ H ] − α1
+
− 2α 2 − w+ = 0
α 2 K H pCO2 α0 α0 [H ]
 The pH is calculated to be:
 pH = 8.27
Quite similar to surface water processes
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 Open System
 Assuming
equilibrium with
a constant partial
pressure of CO2
(10-3.5 atm)

Stumm &
Morgan, 1996,
Figure 7.10, pg.
379
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 Open system with other acy/alk
 CaCO3 system with addition of:
 Strong acid (CA)
 Strong base (CB)

C B + 2[Ca +2 ] + [ H + ] = [ HCO3− ] + 2[CO3−2 ] + [OH − ] + C A

K soα 0 K H pCO2 K H pCO2

− + = (C A − C B )
Kw
2 + [ H ] − α1
+
− 2α 2
α 2 K H pCO2 α0 α0 [H ]

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Carbonate dissolution
 Pathways
 Not covered in class

Stumm &
Morgan, 1996,
Figure 7.12, pg.
385
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  To next lecture

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