Topics Hydrolysis Aquo metal ion gives rise to hydroxo complexes - PDF document

CEE 680 Lecture #34 3/27/2020 Print version Updated: 27 March 2020 Lecture #34 Precipitation and Dissolution: Basics and metal solubility (Stumm & Morgan, Chapt.7) Benjamin; Chapter 8.7 ‐ 8.15 David Reckhow CEE 680 #34 1 Topics  Hydrolysis  Aquo metal ion gives rise to hydroxo complexes  Magnesium and Iron Hydroxide solubility David Reckhow CEE 680 #34 2 1

CEE 680 Lecture #34 3/27/2020 Precipitation and Dissolution  Environmental Significance  Engineered systems  coagulation, softening, removal of heavy metals  Natural systems  composition of natural waters  formation and composition of aquatic sediments  global cycling of elements  Composition of natural waters  S&M, 3rd ed., figure 15.1 (pg. 873)  Benjamin, 2 nd ed., figure 1.1 David Reckhow CEE 680 #34 3 Elemental Abundance in Crust  ad David Reckhow CEE 680 #34 4 2

CEE 680 Lecture #34 3/27/2020 IN EARTH’S CRUST Top 8  dfs From: USGS, 2005 David Reckhow CEE 680 #34 5 Abundance of inorganics in fresh water and in earth’s crust Terrestrial water From: Stumm & Morgan, 1996; Benjamin, 2002; fig 1.1 David Reckhow CEE 680 #35 6 3

CEE 680 Lecture #34 3/27/2020 Solubility Products  General Equilibrium  A m B n (s)  mA +n + nB ‐ m Cation Solid Anion  Solubility Product Equation  K so = [A +n ] m [B ‐ m ] n  also sometimes written: K sp  Example  Calcium Carbonate  sources: Smith & Martell; S&M, table 7.1 (pg.362 ‐ 364) David Reckhow CEE 680 #34 7 K so and Q  Reaction Quotient (Q)  computed value from actual measurements  may not be at thermodynamic equilibrium  comparison with K sp will tell you about tendency toward dissolution or precipitation  Q>K so , then water will precipitate solid phase  Q<K so , then water will dissolve solid phase  Example: Calcium Carbonate solubility  Ca +2 = 40 mg/L and CO 3 ‐ 2 = 100 mg/L as CaCO 3  what is Q?  if K so is 10 ‐ 8.34 , what does this tell us? David Reckhow CEE 680 #34 8 4

CEE 680 Lecture #34 3/27/2020 Solubility of some simple salts  Barium sulfate  BaSO 4 = Ba +2 + SO 4 ‐ 2  9 . 96  2 10 x  K so = 10 ‐ 9.96 = [Ba +2 ][SO 4 ‐ 2 ]   4 . 98 x 10  How much will dissolve, and what will the barium and sulfate concentrations be?    9 . 96   3  10 x 10 x  How much will dissolve in a   2  3 x 10 x 1mM solution of Na 2 SO 4 ?     3  6  9 . 96 10 10 4 x 10  x 2     1 . 097 x 10 7 10 6 . 96 David Reckhow CEE 680 #34 9 Solubility of “simple” salts Stumm & Morgan, 1996, Figure 7.1, pg. 354 David Reckhow CEE 680 #34 10 5

CEE 680 Lecture #34 3/27/2020 Solubility of oxides & hydroxides  Does not consider the hydroxometal complexes Stumm & Morgan, 1996, Figure 7.3, pg. 365 David Reckhow CEE 680 #34 11 Solubility of metal hydroxides  Adds complexity  hydroxide concentration is controlled by pH and therefore affected by buffering  many “hydrolyzing” metals have soluble hydroxide species too  Example: Magnesium Hydroxide  Weakly hydrolyzes  Only one soluble hydroxide species  Practical: we remove Mg by precipitative softening David Reckhow CEE 680 #34 12 6

CEE 680 Lecture #34 3/27/2020 -11.79 Benjamin -11.1 Morel -10.74 Butler -12.9 SM&P Magnesium Hydroxide -11.16 Brezonik -11.15 Smith  Thermodynamics  Mg(OH) 2 (s) = Mg +2 + 2OH ‐ K so = 10 ‐ 11.16  Mg +2 + OH ‐ = MgOH + K 1 = 10 2.6  Mass Balance  Mg T = [Mg +2 ] + [MgOH + ] 2.56 Stumm 2.12 Benjamin 2.6 Morel 2.58 Smith Total dissolved concentration: does not include precipitated Mg Mg(OH) 2 (s) is crystalline Brucite David Reckhow CEE 680 #34 13  Smith & Martell Mg(OH) 2 solid David Reckhow CEE 680 #34 14 7

CEE 680 Lecture #34 3/27/2020 Magnesium Hydroxide  Tableau  [Mg +2 ] = 10 16.84 [H + ] 2  same as:  [Mg +2 ] = 10 ‐ 11.16 /[OH + ] 2 Reactants Components MgOH2 (Brucite H+ Log K Mg+2 1 2 16.84 MgOH+ 1 1 5.42 H+ 0 1 0 David Reckhow CEE 680 #34 15 Magnesium Hydroxide II  Then use the K 1 to get an  From the K so and K w equation for the soluble develop an equation for the hydroxide species free metal in terms of H +  [ MgOH ]   2  2 K [ Mg ][ OH ]  K so 1   2 [ Mg ][ OH ] K  2  [ Mg ] so     2 [ MgOH ] K [ Mg ][ OH ]  2 [ OH ] 1   K [ Mg 2 ] K W K  1 [ H ]  2   2 [ Mg ] so [ H ]   K 2  2 . 6 16 . 84  2 10 10 [ H ]  14 10 W  [ H ]  2  16 . 84  2 [ Mg ] 10 [ H ]   5 . 44 10 [ H ]    Log [ Mg 2 ] 16 . 84 2 pH    Log [ MgOH ] 5 . 44 pH David Reckhow CEE 680 #34 16 8

CEE 680 Lecture #34 3/27/2020 Magnesium Hydroxide III  Total Magnesium  Applications  Mg T  Mg is a hardness cation = [Mg +2 ] + [MgOH + ]  Solubility is controlled  Follows upper line by hydroxide precipitate where lines are well  Easily removed by separated softening at high pH  Falls 0.3 log units above intersection of any two major species David Reckhow CEE 680 #34 17 0 -1 Mg +2 Mg Total -2 H + -3 Mg(OH) - -4 -5 -6 OH - Log C -7 -8 -9 -10 -11 -12 -13 -14 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 pH David Reckhow CEE 680 #34 18 9

CEE 680 Lecture #34 3/27/2020  To next lecture David Reckhow CEE 680 #34 19 Calcium Phosphate  Providence, RI example  See Edwards & Giammar manuscripts David Reckhow CEE 680 #34 20 10