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    Print Version: Lecture #38 Metal Carbonates & Hydroxides

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    This document summarizes a lecture on the precipitation and dissolution of metal carbonates and hydroxides. It discusses solubility product constants (Ksp) for various metal hydroxides and carbonates. Graphs are presented showing speciation diagrams for calcium carbonate and zinc hydroxide systems under varying pH and carbonate concentrations. Equations are provided describing the solubility equilibrium and mass balance for these systems under closed and open conditions.

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    Print Version: Lecture #38 Metal Carbonates & Hydroxides

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    This document summarizes a lecture on the precipitation and dissolution of metal carbonates and hydroxides. It discusses solubility product constants (Ksp) for various metal hydroxides and carbonates. Graphs are presented showing speciation diagrams for calcium carbonate and zinc hydroxide systems under varying pH and carbonate concentrations. Equations are provided describing the solubility equilibrium and mass balance for these systems under closed and open conditions.

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    This document summarizes a lecture on the precipitation and dissolution of metal carbonates and hydroxides. It discusses solubility product constants (Ksp) for various metal hydroxides and carbonates. Graphs are presented showing speciation diagrams for calcium carbonate and zinc hydroxide systems under varying pH and carbonate concentrations. Equations are provided describing the solubility equilibrium and mass balance for these systems under closed and open conditions.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    29 views23 pages

    Print Version: Lecture #38 Metal Carbonates & Hydroxides

    Uploaded by

    wastequest
    This document summarizes a lecture on the precipitation and dissolution of metal carbonates and hydroxides. It discusses solubility product constants (Ksp) for various metal hydroxides and carbonates. Graphs are presented showing speciation diagrams for calcium carbonate and zinc hydroxide systems under varying pH and carbonate concentrations. Equations are provided describing the solubility equilibrium and mass balance for these systems under closed and open conditions.

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    © All Rights Reserved
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    of 23

    Updated: 13 April 2018 Print version

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

    David Reckhow CEE 680 #38 1


    Practice Session

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

    David Reckhow CEE 680 #38 2


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

    David Reckhow CEE 680 #38 3


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

    David Reckhow CEE 680 #38 4


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

    David Reckhow CEE 680 #38 5


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

    David Reckhow CEE 680 #38 6


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

    David Reckhow CEE 680 #38 7


    Chromium Hydroxide I
     Thermodynamic Data

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

    David Reckhow CEE 680 #36 8


    Chromium Hydroxide II
     Based on Constants
    in Stumm & Morgan

    Stumm &
    Morgan, 1996,
    Figure 7.4, pg.
    366
    David Reckhow CEE 680 #36 9
    ZnO solubility

    Stumm &
    Morgan, 1996,
    Figure 7.6a, pg.
    370
    David Reckhow CEE 680 #37 10
    Zinc with OH, CO3 and Cl
     Pg 636 in Benjamin

    David Reckhow CEE 680 #38 11


    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

    David Reckhow CEE 680 #38 12


    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

    David Reckhow CEE 680 #38 13


    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

    David Reckhow CEE 680 #38 pH 14


    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

    David Reckhow CEE 680 #38 pH 15


    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

    David Reckhow CEE 680 #38 pH 16


    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

    David Reckhow CEE 680 #38 17


    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
    David Reckhow CEE 680 #38 18
    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
    David Reckhow CEE 680 #38 19
    Open System
     Assuming
    equilibrium with
    a constant partial
    pressure of CO2
    (10-3.5 atm)

    Stumm &
    Morgan, 1996,
    Figure 7.10, pg.
    379
    David Reckhow CEE 680 #38 20
    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 ]

    David Reckhow CEE 680 #38 21


    Carbonate dissolution
     Pathways
     Not covered in class

    Stumm &
    Morgan, 1996,
    Figure 7.12, pg.
    385
    David Reckhow CEE 680 #38 22
     To next lecture

    David Reckhow CEE 680 #38 23

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