CEE 680 Spring 2016

Water Chemistry

Homework Set #9

Work in groups of 3-4 for this homework

Aluminum Solubility Continued

Below are the relevant chemical equilibria for amorphous aluminum hydroxide and
aluminum phosphate. These will be used in the problems below.

Equilibria Log K
AlOH3(s) (amorphous) + = 3H+ Al+3
+ 3 H 2O 10.8
Al+3 + H2O = AlOH+2 + H+ -4.97
Al+3 + 2H2O = Al(OH)2+ + 2H+ -9.3
Al+3 + 3H2O = Al(OH)3(aq) + 3H+ -15.0
Al+3 + 4H2O = Al(OH) - + 4H+
4
-23.0
AlPO4•2H2O(s) (variscite) = Al+3 + PO4-3 + 2H2O -21
H PO = H+ + H PO -
3 4 2 4
-2.15
H2PO4- = H+ + HPO4-2 -7.2
HPO -2 = H+ + PO -3
4 4
-12.3

9.1 Solubility and Mixed Solids (4 points)

Prepare a solubility diagram for Aluminum in water. Assume that the hydroxide phase
that forms is amorphous. Also assume that 0.5 mM total phosphate is present in the
system. Present the diagram in the usual form (log C vs pH). Outline the zones of
precipitation and mark the identity of the precipitates.

Solution

Determine lines for all soluble Al species for amorphous aluminum hydroxide as with
previous problems of this type. Do the same for equations based on Aluminum
phosphate. This requires that one assume a total phosphate concentration of 0.5 mM, and
consider the α3, value. Line segments are determined between the pKa’s of the phosphate
system, and smooth curved portions are drawn between them.

1
 Summary for Al(OH)3-based lines on Log C vs pH diagram
Species Intercept Slope
+3
Al 10.8 -3
AlOH+2 5.8 -2
Al(OH)2+ 1.5 -1
Al(OH)3o -4.2 0
Al(OH)4- -12.2 +1

Summary for AlPO4–based lines on Log C vs pH diagram

Species pH < 2.15 pH =2.15-7.2 pH = 7.2-12.3 pH > 12.3
Intercept Slope Intercept Slope Intercept Slope Intercept Slope
Al+3 3.95 -3 1.8 -2 -5.4 -1 -17.7 0
AlOH+2 -1.02 -2 -3.17 -1 -10.37 0 -22.7 +1
Al(OH)2+ -5.35 -1 -7.50 0 -14.70 +1 -27.0 +2
Al(OH)3(aq) -11.05 0 -13.20 +1 -20.4 +2 -32.7 +3
Al(OH) -
4 -19.05 +1 -21.2 +2 -28.4 +3 -40.7 +4

For more on how the AlPO4-based lines are determined see the ferrous carbonate example done in class (lecture #42). The methods
are analogous.

2
Many of you did this using a spreadsheet without determining the individual line
segements, which is OK.

0.0001 M total phosphate with amorphous Al(OH)3

0
H+
-1 AlTotal
-2 +3 AlTotal
Al
-3 -
Al(OH)4
-4 Al(OH)3
AlOH+2
-5

-6
Log C

-7 Al(OH)2+ Al(OH)2
+

-8

-9

-10 Al(OH)3
+2
-11 +3 AlOH
Al
-12 -
OH
-
-13 Al(OH)4
-14
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

pH

From the above graph it can be seen that the total Al concentrations based on the two
solid phases intersect at about pH 8.1. At this same pH all lines representing the same
specific Al species should also intesect. Draw a vertical line from the intersecion of the
total Al lines. Decide which solid phase controls on each side of that line (i.e., which one
is least soluble), and erase those portions of each line that do not give the minimum
solubility (i.e., that represent the non-controlling solid).

3
 0.0005 M total phosphate with amorphous Al(OH)3
0
H+
-1

-2

-3 -
Al(OH)4
-4 Al(OH)3
+2
AlOH
-5

-6
Log C

-7 Al(OH)2+
+
-8
Al(OH)2

-9

-10
Al(OH)3
-11 AlOH+2
-12 -
OH Al+3
-
-13 Al(OH)4 +3
Al
-14
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

pH

Finally, mark off and label the precipitation regions accordingly.

4
9.2. Predominance Diagram (4 points)

Prepare a predominance diagram based on the Aluminum Hydroxide / Aluminum

Phosphate equilibria in the table above. Use a soluble aluminum concentration (AlT of 1
mM). Again, you should outline the zones of precipitation and mark the identity of the
precipitates. Outside of these zones, you should indicated the principal soluble species.

Solution

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The predominance diagram must have pH on the x-axis and log PT (log total phosphate)
on the y-axis.

Type A lines

Line Species pH Notes

A1 Al+3/AlOH+2 4.97 Later found to be under Al(OH)3 precipitate

A2 AlOH+2/Al(OH)2+2 4.33 Doesn’t appear as dihydroxide never predominates

A3 Al(OH)2+/Al(OH)3o 5.7 Later found to be under Al(OH)3 precipitate

A4 Al(OH)3o/Al(OH)4- 8.0 Later found to be under Al(OH)3 precipitate

Type B lines for hydroxide precipitate

B1: Determine the equations defining the lower and upper pH boundary on aluminum
hydroxide precipitation
Equilibrium between Al(OH)3 and Al+3 is:
pH =4.65

assumption is OK as this is below the A1 line. Now we turn to the other side of the
hydroxide precipitation zone.

B4: Equilibrium between Al(OH)3 and Al(OH)4- is:

pH = 9.2

This is also OK as it is at a pH above that of the A4 line where the tetra hydroxide
predominates.

Type B lines for the phosphate precipitate

pH for L <2.15 2.15-7.2 7.2-12.3 >12.3

pH for M >4.97 4.97-5.7 5.7-8.0 >8.0
Dominant Al+3 Al+3 Al(OH)2+ Al(OH)3o Al(OH)3o Al(OH)4- Al(OH)4-
-
Species H3PO4 H2PO4 H2PO4- H2PO4- HPO4-2 HPO4-2 PO4-3
pH range <2.15 2.15-4.97 4.97-5.7 5.7-7.2 7.2-8.0 8.0-12.3 >12.3
Equ # B5a B5b B7b B8b B8c B9c B9d

Next, determine boundary between AlPO4 and Al+3. This requires separate equations
below and above pH 2.15.

First the B5a line:

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 Log PT = 3.65 - 3pH

Next the B5b line:

Log PT = 1.5 - 2pH

And finally, we need to know the boundary between AlPO4 and Al(OH)4-, all of which
falls between the second and third pKa where HPO4-2 is the dominant phosphate
species:

So the B9c line is:

Log PT = -28.7 + 3pH

Type C lines:

Next determine boundary between Al(OH)3 and AlPO4. This must be evaluated from pH
4.65 to 7.2, and then from 7.2 to 9.2

The C1b line is:

Log PT = -12.3 + pH

The C1c line is:

Log PT = -19.5 + 2pH

This gives us the following predominance diagram.

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 Total Al = 1mM; amorphous Al(OH)3
0
#B9c
-1
#B5a
-2

-3 AlPO4 (s)
#C1c
-4
#B5b
-5

-6
#C1b
Log C

-7

-8
-
+3 Al(OH)4
-9 Al Al(OH)3 (s)
-10

-11

-12 #B1 #B4

-13

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

pH