ACEE 219

E i
Environmental
t l Chemistry
Ch i t

Week
W k 10
May 4, 2010
Innovation Hall 127
ACEE 219 Spring 2010 HDP 1
 Dissolution

http://www.uwec.edu/boulteje/Boulter103Notes/30October_files/image034.jpg

Dissolution is the process by which a solid forms a homogeneous mixture with

a solvent (solution)
(solution).

ACEE 219 Spring 2010 HDP 2

 Precipitation

http://www.uwec.edu/boulteje/Boulter103Notes/30October.htm

Precipitation is the formation of a solid in a solution during association of

reactive components (i(i.e.,
e ions)
ions).

ACEE 219 Spring 2010 HDP 3

Rock weathering
th i is
Weathering
W i th
the alteration
lt ti off rocks
k to
t more
stable material from their exposure to the agents
of air, water, and organic fluids.

Mechanical weathering includes processes that

fragment and disintegrate rocks into smaller pieces
without changing the rock's mineral composition.

Chemical weathering is the alteration of the rock into

new minerals. Both pathways constitute weathering,
but one p
process mayy dominate over the other.

http://www.waterencyclopedia.com/Tw-Z/Weathering-of-Rocks.html

ACEE 219 Spring 2010 HDP 4

 Lime Softening

Ca2+ + CO32- ↔ CaCO3(s)

Mg2+ + 2OH- ↔ Mg(OH)2(s)

http://www.lakelandgov.net/water/images/A5A8FEF5821E478080CB8A36B334F2DC.jpg

Hardness is defined as the sum of all polyvalent cations although calcium

and magnesium ions are predominant.

Softening is the process to remove hardness in water. Generally this process

involve the addition of lime (Ca(OH)2 or CaO) and/or soda (Na2CO3)

ACEE 219 Spring 2010 HDP 5

 Characteristics
1 Some heterogeneous equilibria are slowly established
1. established.

2. The thermodynamically predicted stable solid phase for a given set of

conditions may not indeed be the phase that is formed.

3. Solubility depends on the degree of crystallinity and the particle size of the s
olids ((which mayy varyy from case to case).
)

4. Supersaturation may exist; solution concentrations in excess of those

predicted by equilibrium calculations may prevail.

5. The ions produced by the dissolution of solids may undergo further reaction
in solution.

Heterogeneous equilibria may only provide us with the boundary

conditions of the system rather than the situation that truly exists.

ACEE 219 Spring 2010 HDP 6

 Snoeyink & Jenkins Fig. 6-1

ACEE 219 Spring 2010 HDP 7

 Solubility Product
Solubilityypproduct is equilibrium
q constant that describes the reaction by
y which
a precipitate dissolves in pure water to its constituent ions.

Ca(OH)2(s) ↔ Ca2+ + 2OH- AzBy(s) ↔ zAy+ + yBz-

{Ca 2+ }{OH − }2
K so = = [Ca 2+ ][OH − ]2 K so = [ A y + ]z [ B z − ] y
{Ca (OH ) 2 ( s )}

I.A.P. > Kso : Precipitation will occur

I A P = Kso : Equilibrium (i
I.A.P. (i.e.,
e saturation) has been achieved
I.A.P. < Kso : Undersaturated

ACEE 219 Spring 2010 HDP 8

 Solubility
y is the amount of a substance in moles/liter or mg/liter
Solubility g that can
dissolve in a solution under a given set of condition.

Example 6-1. Calculate the solubility in mg/liter of CaF2 in pure water @ 25oC.
Solubility product of CaF2 is 5 x 10-11.

CaF2 (s) ↔ Ca2+ + 2F-

Kso = 5 x 10-11 =[Ca2+ ][F-]2

Set the saturation molar concentration of Ca2+ as S (i.e., [Ca2+ ]=S),

then the saturation molar concentration of F- will be 2S (i
(i.e.,
e [F- ]]=2S)
2S)

5 x 10-11 = S(2S)2 S = 2.32 x 10-4 moles/liter

8,000 mg/mole
= 78,000 g/ o e x 2.323 x 10
0-4 moles/liter
o es/ te = 18.1
8 mg/liter
g/ te
M.W. of CaF2 = 78
Snoeyink & Jenkins Example 6-1
ACEE 219 Spring 2010 HDP 9
 Temperature Effect
• Temperature affects both the equilibrium position of the
precipitation reaction and the reaction rate

• Generally, solubility increases with increasing temperature.

• Solubility decreases with increasing temperature for CaCO3,

Ca3(PO4)2, CaSO4, and FePO4.

http://comps.fotosearch.com/comp/FDC/FDC003/sprinkling-salt-glass_~943107.jpg
http://prhslibrary com/pictures/Bunsen-Burner jpg
http://prhslibrary.com/pictures/Bunsen-Burner.jpg

ACEE 219 Spring 2010 HDP 10

 Example 6
6--2
• Find
Fi d Kso for
f FePO
F PO4 att 50oC given
i th
the ffollowing
ll i iinformation
f ti att 25oC.
C

FePO4(s) ↔ Fe3+ + PO43-

∆Ho = -18.7
18 7 kcal/mole Exothermic reaction
∆Go = 24.4 kcal/mole

⎡ − ΔG 0 ⎤ −18
K so, 25o C = exp ⎢ ⎥ = 1.19 ×10
⎣ RT ⎦

K so, 50o C ΔH o 1 1
ln = ( − ) = -2.444
K so,, 25o C R T2 T1

K so, 50o C = 1.03 ×10 −19

Snoeyink & Jenkins Example 6-2

ACEE 219 Spring 2010 HDP 11

 Common Ion Effect
Common ion effect refer to a modification of solubilityy when a solution
contains an ion that is same as one of the ions which result from the
dissociation of the solid.

Generally, the solubility of the solid will be less than that when the solid
dissolves in pure water.

Example 6-4. Calculate the solubility in mole/liter of SnF2 in a 10-4 mole/liter

NaF solution. (Kso of SnF2 = 3.5 x 10-9)

Let [ Sn 2+ ] = S '
[ F − ] = 10 − 4 + 2S '
K so = [ Sn 2+ ][ F − ]2 = ( S ' )(10 − 4 + 2S ' ) 2 = 3.5 ×10 −9
3.5 ×10 −9
S'≈ = 0.35 ∴ Solubility of SnF2 = 0.35 mole/liter
(10 − 4 ) 2

Snoeyink & Jenkins Example 6-4

ACEE 219 Spring 2010 HDP 12
 pH Effect
C (OH)2(s)
Ca(OH) ( )↔C
Ca2+ + 2OH- ; Kso = 10-5.3
53

Mg(OH)2(s) ↔ Mg2+ + 2OH- ; Kso = 10-10.74

pH
0 2 4 6 8 10 12 14
0

2
oncentraation, pC
C

6 [Ca2+]
[C
8
‐log Co

10
[OH-]
[Mg2+]
12
[H+]
14

ACEE 219 Spring 2010 HDP 13

 pH Effect
Examplep 6-7. 10-4M Mgg2+ and 10-3M Ca2+ g groundwater
At what pH will Mg(OH)2 begin to precipitate? At what pH will [Mg2+] be reduced
to 10-6M?
pH 10.65 11.65
0 2 4 6 8 10 12 14
0

2
oncentraation, pC
C

6 [Ca2+]
[C
8
‐log Co

10
[OH-]
[Mg2+]
12
[H+]
14
Snoeyink & Jenkins Example 6-7
ACEE 219 Spring 2010 HDP 14
 Complexation Effect
When anyy of the constituent ions of a solid pparticipate
p in complex
p formation
following dissolution, there will be an increase in the solubility of the solid.

Fe3+ + H2O ↔ Fe(OH)2+ + H+; logK = -2.16

Fe3+ + 2H2O ↔ Fe(OH)

( )2+ + 2H+; logK
g = -6.74

Fe(OH)3(s) ↔ Fe3+ + 3OH-; logKso = -38

Fe3+ + 4H2O ↔ Fe(OH)4- + 4H+; logK = -23

2Fe3+ + 2H2O ↔ Fe2(OH)24+ + H+; logK = -2.85

ACEE 219 Spring 2010 HDP 15

Complexation Effect
pH
0 2 4 6 8 10 12 14
0

oncentrattion, pC
4 Fe(OH)3(s)

6
CT,Fe(III)

8
‐log Co

10

12

14

Fe2(OH)24+ Fe 3+ FeOH2+ Fe(OH)2+

Fe(OH)4-

ACEE 219 Spring 2010 HDP 16

 Competitive Effects
Where there are a wide varietyy of ligands
g that can influence both the
solubility of a solids.

Fe(OH)2(s) ↔ Fe2+ + 2OH-; logKso = -14.5

Fe(OH)
( )2((s)) ↔ FeOH+ + OH-; logK
g = -9.4

Fe(OH)2(s) + OH- ↔ Fe(OH)3- ; logK = -5.1

FeCO3(s) ↔ Fe2+ + CO32-; logKso = -10.7

FeCO3(s) + OH- ↔ FeOH+ + CO32-; logK = -5.6

FeCO3(s) + 3OH- ↔ Fe(OH)3- + CO32-; logK = -1.3

ACEE 219 Spring 2010 HDP 17

Competitive Effects

FeCO3(s)
Fe(OH)2(s)
Fe2+
CO32-

FeOH+
( ) 3-
Fe(OH) Fe(OH)3-
Fe2+
FeOH+

Snoeyink & Jenkins Figs. 6-9 and 6-10

ACEE 219 Spring 2010 HDP 18

Competitive Effects

Snoeyink & Jenkins Fig. 6-11

ACEE 219 Spring 2010 HDP 19

Competitive Effects

Snoeyink & Jenkins Fig. 6-12

ACEE 219 Spring 2010 HDP 20