CEE 680 12 December 2012

FINAL EXAM

Closed book, three pages of notes allowed.

Answer all Three Questions. Please state any additional assumptions you made, and show all work. If you
don’t have time to complete a section, please describe how you would solve the problem
(without using a computer program such as MINEQL).

Miscellaneous Information:
R = 1.987 cal/mole°K = 8.314 J/mole°K
Absolute zero = -273.15°C
1 joule = 0.239 calories

1. Buffers (25%)

You have prepared a 10 mM phosphate buffer designed to hold pH at 8.1 (25°C, assume I~0). The two
chemicals at your disposal are Na2HPO4 and KH2PO4.

A. How much of each compound (in mM concentration) would you add to create your buffer?
B. If you were to elevate the solution pH to 12.0, how much NaOH would you need to add (again in
mM)?

A. This is a good use for the empiricial Henderson Hasselbach Equation

CA
=
pH pK a + log
CHA
Where CA is the Na2HPO4 and CHA is the KH2PO4
CA pH − pK a 8.1− 7.2
= 10= =
10 7.943
CHA
And since CA + CHA = 10 mM,

CA
= 7.943
0.010 − C A
= C A 0.07943 − 7.943C A
8.943C A = 0.07943
= =
C A 0.00888 M Na2 HPO4
= =
CHA 0.00112 M KH 2 PO4

B. Now determine the new mixture at pH 12 and determine amount of protons that need to be
neutralized, but this time we’re closer to the third Ka, so CA is PO4-3 and CHA is HPO4-2
1
 CA pH − pK a 12.0 −12.3
= =
10 =
10 0.501
CHA
CA
= 0.501
0.010 − C A
= C A 0.00501 − 0.501C A
1.501C A = 0.00501
= =
C A 0.00334 M PO4−3
= =
CHA 0.00666 M HPO4−2

So the change in protons is:

∆H+ in Phosphates = 2*0.00122+0.00888-0.00666 = 0.00466M or 4.66mM

But you also have significant hydroxide in the amount of 10-2M or 10 mM. Therefore the overall hydroxide
addition must be equal to the sum or:

NaOH dose = 0.010+0.00466 = 0.01466M or 14.66mM

2. Redox (25%)

Sulfide and sulfate are two forms of sulfur that commonly exist in the aquatic environment. They
often are found in groundwaters with both reduced and oxidized iron.

A. Write a balanced equation for the oxidation of hydrogen sulfide (HS-) to sulfate by reaction
with amorphous ferric hydroxide, liberating free ferrous iron.
B. Determine the net cell potential (Eonet) and the equilibrium constant for this reaction and
comment on what thermodynamics tells you about whether this is a favorable reaction in a
typical groundwater and surface water systems.
C. At what pH does the eqilibrium rest half-way between the two sulfur species? Assume a free
ferrous iron concentration of 0.56 mg/L. Which species (sulfate or bisulfide) will predominate
at lower pHs?

So we use redox #1 and #14, but we need to reverse #14 and cut its stiochiometry by a factor of 2 so that
the electrons balance.
14 Fe(OH)3(am) + 3H+ + e- = Fe+2 + 3H2O +0.95
15 SO4-2 + 9H+ + 8e- = HS- + 4H2O +0.25

This requires that we reverse the sign on the ∆Eo, but since the potentals are expressed on a per-electron
basis, the change in stoichiometric factors doesn’t result in any additional change in ∆Eo.

Red 8Fe(OH)3(am) + 24H+ +8 e- =8 Fe+2 + 24H2O +0.95

Ox HS- + 4H2O = SO4-2 + 9 H+ + 8e- -0.25
Net 8Fe(OH)3(am) + 15H+ + HS- = 8 Fe+2 + SO4-2 + 20H2O +0.70
2
 n
log K = o
Enet
0.059
8
= (0.70)
0.059
= 94.9

+94.9 [ Fe +2 ]8 [ SO4−2 ]
10 =
[ H + ]15 [ HS − ]
Now substituing in for 10-5M Fe+2 (0.56 mg/L) we get:
+94.9 [10−5 ]8 [ SO4−2 ]
10 =
[ H + ]15 [ HS − ]
[ SO4−2 ]
−
= 10+134.9 [ H + ]15
[ HS ]
So when the quotient on the left is unity, the pH must be 134.9/15 or 9.0. Below this pH sulfate will
predominate and above it will be bisulfide.

3
3. Solubility (50%)

Ferrous Sulfide (Troilite, a form of Pyrrhotite) is a rather insoluble mineral with a Kso of about 10-18.1. One
would expect this to form in reduced groundwaters and sediments where ferrous iron and sulfide are major
forms of Fe and S. Fe(OH)2(s) would, of course form under the right conditions as well.

# Reaction pK
11 FeS(s) = Fe+2 + S-2 18.1
2 Fe(OH)2(s) + 2H+ = Fe+2 + 2H2O -12.9
3 FeOH+ + H+ = Fe+2 + H2O -9.5
4 Fe(OH)2o + 2H+ = Fe+2 +2H2O -20.6
5 Fe(OH)3- + 3H+ = Fe+2 + 3H2O -31.0

A. Prepare a combined Ferrous Hydroxide and Ferrous Sulfide solubility diagram assumng you have a
total sulfide concentration of 10-6M. The x-axis should be pH and the y-axixs should be log
concentration. Show lines for the four soluble iron species based on each precipitate. Identify the
key precipitation zones with FeT lines.
B. At what pH can both precipitates co-exist?
C. If the sulfide concentration was to increase, would the pH where the precipitates co-exist increase
or decrease?
D. Describe in qualitative terms how the presence of 10-3M total carbonate would affect the hydroxide
and sulfide precipitation zones.
E. Describe in qualitative terms how the presence of 10-6M mercury would affect the hydroxide and
sulfide precipitation zones

Development of hydroxide solubility diagram

a. Using the equilibria for ferric hydroxide from above:

[ Fe +2 ]
=K = + 2
10+12.9
[H ]
we get the following for the free aquo ion:
log[ Fe +2 ] =
+12.9 − 2 pH

From this we use the hydroxide equilibria to get hydroxide species concentrations:
and for the monohydroxide:

1 -
Because of uncertainty over K2 for the sulfide system, this equilibrium are often expressed in terms of HS rather than
-2
S . However, to be consistant, I have converted it to the more conventional Kso form in a way that is internally
-13.9
consistent with our value of 10 for the sulfide K2. These pK values were taken from Morel & Hering, 1993.

4
 [ Fe +2 ]
=K = + +
10+9.5
[ FeOH ][ H ]
+
log[ FeOH ] = −9.5 + log[ Fe +2 ] − log[ H + ]
log[ FeOH + ] = −9.5 + log[ Fe +2 ] + pH
log[ FeOH + ] = −9.5 + (12.9 − 2 pH ) + pH
log[ FeOH + ] = +3.4 − pH

now for the dihydroxide:

[ Fe +2 ]
=K = o + 2
10+20.6
[ Fe(OH ) 2 ][ H ]
−20.6 + log[ Fe +2 ] − 2 log[ H + ]
log[ Fe(OH )o2 ] =
log[ Fe(OH )o2 ] =
−20.6 + (12.9 − 2 pH ) + 2 pH
log[ Fe(OH )o2 ] = −7.7

now for the trihydroxide:

[ Fe +2 ]
=K = 10+31.0
[ Fe(OH )3−1 ][ H + ]3
log[ Fe(OH )3−1 ] =
−31.0 + log[ Fe +2 ] − 3log[ H + ]
log[ Fe(OH )3−1 ] =
−31.0 + (12.9 − 2 pH ) + 3 pH
log[ Fe(OH )3−1 ] =
−18.1 + pH

5
 0

-1 FeOH+ Fe+2
-2 H+
-3 FeTotal
-4

-5

-6
Log C

-7
Fe(OH)2 (aq)
-8

-9

-10
OH-
Fe(OH)3-
-11

-12

-13

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

pH

Development of Sulfide-based lines

b. Using the solubility product constant for ferrous sulfide from above:
+2
= =
K [ Fe ][ S −2 ] 10−18.1

b1. we get the following for the free aquo ion:

log[ Fe +2 ] =
−18.1 − log[ S −2 ]
−18.1 − log[ ST ] − log α 2
log[ Fe +2 ] =
And for 10-6 M total sulfides:
−18.1 − log[10−6 ] − log α 2
log[ Fe +2 ] =
−12.1 − log α 2
log[ Fe +2 ] =

6
 For Sulfide Calculations:
1
α2 =
[H ] [H + ]
+ 2
+ +1
K1K 2 K2
KK
For pH<7.02, α 2 ≈ 1 + 22 , or log α 2 ≈ −20.92 + 2 pH
[H ]
K2
For pH=7.02-13.9, α 2 ≈ , or log α 2 ≈ −13.9 + pH
[H + ]
For pH>13.9, α 2 ≈ 1 , or log α 2 ≈ 0

So for pH<7.02, we have:

log[ Fe +2 ] =−12.1 − (−20.92 + 2 pH )
+2
log[ Fe= ] 8.82 − 2 pH , @pH<7.02

And for pH=7.02-13.9, we have:

log[ Fe +2 ] =−12.1 − (−13.9 + pH )
log[ Fe +2 ] = +1.8 − pH , @pH=7.02-13.9

And for pH>13.9, we have:

log[ Fe +2 ] =−12.1 − (0)
log[ Fe +2 ] = −12.1 , @pH>13.9

b2. and for the monohydroxide:

from the Fe(OH)2(s) based calculations, we know that:
log[ FeOH + ] =
−9.5 + log[ Fe +2 ] + pH
And now substituting in the FeS(s)-based free iron equation for pH<7.02, we have:
log[ FeOH + ] =
−9.5 + (8.82 − 2 pH ) + pH
log[ FeOH + ] =
−0.68 − pH , @pH<7.02

And for pH=7.02-13.9, we have:

log[ FeOH + ] = −9.5 + (1.8 − pH ) + pH
+
log[ FeOH ] = −7.7 , @pH=7.02-13.9

And for pH>13.9, we have:

log[ FeOH + ] =−9.5 + (−12.1) + pH
log[ FeOH + ] =
−21.6 + pH , @pH>13.9

b3. now for the dihydroxide:

7
 from the Fe(OH)2(s)-based calculations, we know that:
−20.6 + log[ Fe +2 ] − 2 log[ H + ]
log[ Fe(OH )o2 ] =

And now substituting in the FeS(s)-based FeOH equation for pH<7.02, we have:
log[ Fe(OH )o2 ] =
−20.6 + (8.82 − 2 pH ) + 2 pH
log[ Fe(OH )o2 ] = −11.78 , @pH<7.02

And for pH=7.02-13.9, we have:

log[ Fe(OH )o2 ] =
−20.6 + (1.8 − pH ) + 2 pH
log[ Fe(OH )o2 ] =
−18.8 + pH , @pH=7.02-13.9

And for pH>13.9, we have:

log[ Fe(OH )o2 ] =−20.6 + (−12.1) + 2 pH
log[ Fe(OH )o2 ] =
−32.7 + 2 pH , @pH>13.9

B4. now for the trihydroxide:

from the Fe(OH)2(s)-based calculations, we know that:
log[ Fe(OH )3−1 ] =
−31.0 + log[ Fe +2 ] − 3log[ H + ]
log[ Fe(OH )3−1 ] =
−31.0 + log[ Fe +2 ] + 3 pH

And now substituting in the FeS(s) based Fe(OH)2 equation for pH<7.02, we have:
log[ Fe(OH )3−1 ] =
−31.0 + (8.82 − 2 pH ) + 3 pH
log[ Fe(OH )3−1 ] =
−22.18 + pH , @pH<7.02

And for pH=7.02-13.9, we have:

log[ Fe(OH )3−1 ] =
−31.0 + (1.8 − pH ) + 3 pH
log[ Fe(OH )3−1 ] =
−29.2 + 2 pH , @pH=7.02-13.9

And for pH>13.9, we have:

log[ Fe(OH )3−1 ] =−31.0 + (−12.1) + 3 pH
log[ Fe(OH )3−1 ] =
−43.1 + 3 pH , @pH>13.9

8
 FeTotal
FeTotal
FeOH+ Fe+2
0

-1
H+
-2

-3

-4

-5

-6
Log C

-7
Fe(OH)2o FeOH+
-8

-9
OH-
-10

-11 o
Fe(OH)2
-12 Fe+2
-
Fe(OH)3 - Fe(OH)3
-13

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

pH
Red lines are based on sulfide solubility and black are based on hydroxide

9
 Fe+2
0

-1
H+
-2
FeS Fe(OH)2
-3
-
-4 FeOH+ Fe(OH)3
-5

-6
Log C

-7
o
-8
Fe(OH)2

-9
-
OH
-10

-11 o
FeOH+
Fe(OH)2
-12 Fe+2
Fe(OH)3-
-13

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

pH
Now combining, we find that the hydroxide controls at pHs of 11.15 and above. Below this level,
the carbonate is less soluble.

A. (30 points) see above

B. (5 points) The co-exist at a pH of about 11.1

C. (5 points) pH increases; it forms over a wider pH range

D. (5 points) it forms a 3rd solid phase (FeCO3) which would infringe on the FeS(s) zone mostly

E. (5 points) it would precipiate HgS quite extensively, depressing the sulfide concentrations and thereby
diminish the FeS(s) zone, allowing Fe(OH)2(s) to expand into lower pHs.

10
4. Predominance (50%) Answer this or #3, your choice

Lead carbonate (PbCO3(s)) and red Lead Oxide (PbO (s)) are two important solid phases that may control lead
solubility in water 2. In the attached pages is a detailed solution leading to a zinc hydroxide solubility
diagram. Please use this to help solve the following problems.

A. Prepare a solubility diagram (log C vs pH) for a water that is potentially in equilibrium with lead
hydroxide and lead carbonate. Assume the water has 10-3 M total carbonates (i.e., 1 mM CT).
Show all soluble species along with the PbT line and indicate where precipitation will occur and
the type of precipitate. To help you, there is a full solubility diagram for lead hydroxide only
below. Feel free to work from this to prepare the combined carbonate-hydroxide diagram
B. Below is a partially completed predominance diagram for the lead oxide – lead carbonate
system. This was prepared for a total soluble lead concentration of 10-4 M (i.e., 0.1 mM PbT).
Please complete this diagram showing the line(s) separating the two precipitates (C lines) and
also determine and show the last remaining B line that separates the PbCO3 precipitation zone
from the Pb(OH)3- zone (no precipitate). Show your work.

Stumm & Morgan Present the following data in Table A6.1

OH- CO3-2
2+
Pb PbL 6.3
PbL2 10.9 PbL • s 13.1
PbL3 13.9
PbL2 • s 15.3

They note that the numerical values are Log formation contstants.

Using these data you can rearrange the equilibrium quotients to get the following

In equilibrium with PbO(s):

Log[Pb+2] = +12.7 -2pH
Log[PbOH+] = +5.0 –pH
Log[Pb(OH)2] = -4.4
Log [Pb(OH)3] = -15.4 +pH

2
Some mixed carbonate-hydroxide species may, in fact, be the most important, but they will not be considered here
for the purpose of simplicity.

11
 PbTotal
PbOH+ Pb+2
0

-1 H+ Pb(OH)3
-

-2

-3

o
-4 Pb(OH)2
-5

-6
Log C

-7

-8 -
OH
-9

-10

-11

-12

-13

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

pH

In equilibrium with PbCO3(s):

Log[Pb+2] = -13.1 –log[CO3-2]
Log[PbOH+] = -20.8 +pH –log[CO3-2]
Log[Pb(OH)2] = -30.2 +2pH –log[CO3-2]
Log [Pb(OH)3] = -41.2 +3pH –log[CO3-2]

12
 0

-1
#B3a
-2 PbCO3 (s)
-3

-4

-5
#B3b
Log CO3T

-6 #B4b

-7

-8 Pb(OH)3-

PbOH+
-9 Pb+2 PbO (s)
-10

-11 #B1 #B2

-12 #A1

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

pH

Answer to A.1.

13
 PbTotal PbTotal
PbOH+ Pb+2
0

-1 H+ Pb(OH)3-
-2

-3

-4 Pb(OH)2
o PbOH+

-5

-6
Log C

-7

-8 -
OH
-9

-10 o +2
Pb(OH)2 Pb
-11

-12 Pb(OH)3-
-13

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

pH

14
 +2
Pb
0

-1 H+ PbO Pb(OH)3-
-2
PbCO3
-3 PbOH+

-4
Pb(OH)2o
-5

-6
Log C

-7

-8
OH-
-9 PbOH+
-10 Pb(OH)2o
-11
Pb+2
-12 Pb(OH)3-
-13

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

pH

Answer to A.2.

Type A lines

First, lets consider the boundary between the aquo ion and the monohydroxide (line A1)

At this point the two are equal, so we can take both equations and set them equal:

15
 Log[Pb+2] = Log[PbOH+]

+12.7 -2pH = +5.0 –pH

pH = 12.7 – 5.0

pH = 7.7

following the same approach, we get the remaining A lines

A2:

Log[PbOH+] = Log[Pb(OH)2]

+5.0 –pH = -4.4

pH = 5.0 +4.4

pH = 9.4

A3:

Log[Pb(OH)2] = Log [Pb(OH)3]

-4.4 = -15.4 +pH

pH = -4.4 + 15.4

pH = 11.0

16
 0

-1

-2

-3 -
H2CO3 HCO3 CO3-2
-4

Pb(OH)2o
PbOH+
-5

-6
Log CT

-7
Pb+2 Pb(OH)3-
-8

-9

-10

-11

-12
#A1 #A2 #A3
-13 #L1 #L2

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

pH

Type B lines

First let’s examine the hydroxide equilibria. By looking at the PbO solubility graph, its appears that only free
lead (Pb+2) and the trihydroxide (Pb(OH)3-) are the dominant soluble species in equilibrium with the
hydroxide precipitate at a total soluble lead concentration of 10-4 M.

B1:

17
So, first let’s look at the Pb+2/PbOH+ precipitate boundary. From the solubility product equation:

Log[PbOH+] = +5.0 –pH

And presuming that this soluble species is the dominant one at the onset of precipitation, we set
the concentration equal to the MeT = 10-4M:

-4 = +5.0 –pH

pH = 9

this is in the range where the monohydroxide predominates, so our assumption is correct.

B2:

Now let’s look at the Pb(OH)3-/PbO precipitate boundary. From the given solubility calculations, we have:

Log [Pb(OH)3] = -15.4 +pH

And presuming that this soluble species is the dominant one at the onset of precipitation, we set
the concentration equal to the MeT = 10-4M:

-4 = -15.4 +pH

pH = 11.4

This falls beyond the A3 line, so we’re in the Pb(OH)3-1 zone, and the line is valid

18
 0

-1

-2

-3

-4

-5

-6
PbO (s)
Log CT

-7

Pb(OH)2o
Pb(OH)3-

PbOH+
-8

-9
Pb+2
-10
#B1 #B2
-11

-12 #A1 #A2 #A3

-13 -4 #L1 #L2
PbT = 10 M
-14
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

pH

Inspection of the carbonate/hydroxide solubility diagram leads one to conclude that free lead may be the
only soluble species that needs to be considered for the B lines defining carbonate solubility.

B3

So, lets look at the Pb+2/PbCO3 boundary: We may need to develop as many as three line segments due to
carbonate’s pH dependence.:

For Carbonate Calculations:

19
 1
α2 =
[H ] [H + ]
+ 2
+ +1
K1K 2 K2

K1 K 2
For pH<6.3, α 2 ≈ , or log α 2 ≈ −16.6 + 2 pH
[ H + ]2

K2
For pH=6.3-10.3, α 2 ≈ , or log α 2 ≈ −10.3 + pH
[H + ]

For pH>10.3, α 2 ≈ 1 , or log α 2 ≈ 0

Now looking at the given equilibrium expression:

Log[Pb+2] = -13.1 –log[CO3-2]

And presuming that this soluble species is the dominant one at the onset of precipitation, we set
the concentration equal to the MeT = 10-4M:

-4 = -13.1 –log[CO3-2]

-4 = -13.1 –log[CT] -logα

Log[CT] = -9.1 – logα

B3a:

Substituting in for the simplified logα at pH < 6.3

Log[CT] = -9.1 - (-16.6 + 2pH)

log[CT] = +7.5 - 2pH, @pH<6.3

B3b:

And for pH=6.3-10.3, we have:

20
 Log[CT] = -9.1 - (-10.3 + pH)

log[CT] = +1.2 - pH, @pH<6.3-7.7

Note that this is only valid up to pH 7.7, the limit of free lead’s predominance (A1 line)

Now we need to look at the PbOH+/PbCO3 boundary: From the solubility calculations we had developed
three line segments. We can conveniently take the equation for each, retaining the total carbonate term in
its general form:

B4

Now looking at the next given equilibrium expression:

Log[PbOH+] = -20.8 +pH –log[CO3-2]

And presuming that this soluble species is the dominant one at the onset of precipitation, we set
the concentration equal to the MeT = 10-4M:

-4 = -20.8 +pH –log[CO3-2]

-4 = -20.8 +pH –log[CT] -logα

Log[CT] = -16.8 + pH – logα

B4b:

And for pH=6.3-10.3, we have:

Log[CT] = -16.8 + pH - (-10.3 + pH)

21
 log[CT] = -6.5, @pH = 7.7-9.4

Note that this is only valid up to pH 9.4, the limit of lead monohydroxide’s predominance (A2 line)

At this point, we’re well into the PbO precipation zone, so let’s look at the other side where lead carbonate
may re-emerge at high pHs. This is beyond the A3 line, so we must consider the trihydroxide.

B5

Now looking at the final given equilibrium expression:

Log [Pb(OH)3] = -41.2 +3pH –log[CO3-2]

And presuming that this soluble species is the dominant one at the onset of precipitation, we set
the concentration equal to the MeT = 10-4M:

-4 = -41.2 +3pH –log[CO3-2]

-4 = -41.2 +3pH –log[CT] –logα

Log[CT] = -37.2 + 3pH – logα

B5c:

And for pH> 10.3, we have:

Log[CT] = -37.2 + 3pH -(0)

log[CT] = -37.2 + 3pH, @pH > 11.0

22
Note that this is only valid beyond pH 11, the lower limit of lead trihydroxide’s predominance (A3 line)

-1 #B5c
#B3a
-2 PbCO3 (s)
-3

-4

-5
#B3b
Log CO3T

-6 #B4b

-7 PbO (s)
-8
Pb(OH)2o Pb(OH)3-
PbOH+

-9 Pb+2
-10

-11 #B1 #B2

-12 #A1 #A2 #A3

-13 -4 #L1 #L2

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

pH

Type C lines

23
Finally, lets consider the boundary between the two solid phases. This line will start on the low pH side,
were the B lines intersect (pH=9). This is well within the zone where bicarbonate is the dominant carbonate
species.

To determine this, we can pick from any one of the matched equations. Each will give us the same answer,
so let’s just arbitrarily pick free lead. Now we set them equal to each other:

Log[Pb+2] = +12.7 -2pH = Log[Pb+2] = -13.1 –log[CO3-2]

+12.7 -2pH = -13.1 –log[CO3-2]

log[CO3-2] = -25.8 + 2pH

or:

log[CT] = -25.8 + 2pH -logα

C1b:

And for pH=6.3-10.3, we have:

Log[CT] = -25.8 + 2pH -(-10.3 + pH)

log[CT] = -15.5 + pH, @pH = 9.0-10.3

C1c:

And for the carbonate zone; pH>10.3, we determined:

Log[CT] = -25.8 + 2pH -(0)

Log[CT] = -25.8 + 2pH, @pH>10.3-11.4

Note that this is only valid beyond pH 11.4, the upper limit of lead oxide’s insolubility (B2 line)

24
The complete lines are as follows:

-1 #B5c
#B3a
-2 PbCO3 (s)
-3
#C1c
-4

-5 #C1b
#B3b
Log CO3T

-6 #B4b

-7 PbO (s)
-8 Pb(OH)3-

Pb(OH)2o
PbOH+

-9 Pb+2
-10

-11 #B1 #B2

-12 #A1 #A2 #A3

-13 -4 #L1 #L2

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

pH

And removing extra line segments and lead species that do not exist at 0.1 mM concentration (e.g., those
“under” the precipitates, we get the final diagram:

25
 0

-1 #B5c
#B3a
-2 PbCO3 (s)
-3
#C1c
-4

-5 #C1b
#B3b
Log CO3T

-6 #B4b

-7 PbO (s)
-8 Pb(OH)3-

Pb(OH)2o
PbOH+
-9 Pb+2
-10

-11 #B1 #B2

-12 #A1 #A2 #A3

-13 -4 #L1 #L2

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

pH

26
 0

-1 #B5c
#B3a
-2 PbCO3 (s)
-3
#C1c
-4

-5 #C1b
#B3b
Log CO3T

-6 #B4b

-7

-8 Pb(OH)3-

PbOH+
-9 Pb+2 PbO (s)
-10

-11 #B1 #B2

-12 #A1

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

pH

27
 0

-1

-2 PbCO3 (s)
-3

-4

-5
Log CO3T

-6

-7

-8 Pb(OH)3-

PbOH+
-9 Pb+2 PbO (s)
-10

-11

-12

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

pH

28
Some important equilibrium constants:
Equilibria Log K
Mg(OH)2 (s) = Mg+2 + 2OH- -11.6
Mg+2 + H2O = MgOH+ + H+ -11.44
MgCO3 (s) = Mg+2 + CO3-2 -7.5
CaCO3(s) = Ca+2 + CO3-2 -8.34
Ca(OH2)(s) = Ca+2 + 2OH- -5.19
CaSO4.2H2O(s) = Ca+2 + SO4-2 + 2H2O -4.62
CaOH+ = Ca+2 + OH- -1.15
FeCO3(s) = Fe+2 + CO3-2 -10.7
AlOH+2 = Al+3 + OH- -9.01
CdOH+ = Cd+2 + OH- -3.92
CoOH+ = Co+2 + OH- -4.80
CuOH+ = Cu+2 + OH- -6.00
HgOH+ = Hg+2 + OH- -10.60
NiOH+ = Ni+2 + OH- -4.14
PbOH+ = Pb+2 + OH- -6.29
ZnOH+ = Zn+2 + OH- -5.04
HgS(s) = Hg+2 + S-2 -42.7

Some important half-cell reactions

Equ# Half Cell Reaction ∆Eo (Volts)

1 O2(aq) + 4H+ + 4e- = 2H2O +1.23

+3 +2
2 Mn + e- = Mn +1.51
+3
3 Mn+4 + e- = Mn +1.65
+2
4 MnO4- + 8H+ + 5e- = Mn + 4H2O +1.49
+3 +2
5 Fe + e- = Fe +0.77
6 Cu+2 + e- = Cu+ +0.16
7 ½HOBr + ½H+ + e- = ½Br- + ½H2O +1.33
8 O3 (g) + 2H+ + 2 e- = O2 (g) + H2O +2.07
9 Al+3 + 3e- = Al(s) -1.68
10 ½HOCl + ½H+ + e- = ½Cl- + ½H2O +1.48
11 ½OCl- + H+ + e- = ½Cl- + ½H2O +1.64
12 BrO3- +5H+ +4e- = HOBr + 2H2O +1.45
13 ½NH2Cl + H+ +e- = ½Cl- + ½NH4+ +1.40
14 Fe(OH)3(am) + 3H+ + e- = Fe+2 + 3H2O +0.95
15 SO4-2 + 9H+ + 8e- = HS- + 4H2O +0.25
16 S(s) + 2H+ + 2e- = H2S (g) +0.17
+2
17 Zn + 2e- = Zn(s) -0.76
+2
18 Ni + 2e- = Ni(s) -0.24
+2
19 Pb + 2e- = Pb(s) -0.126
20 ClO2 + e- = ClO2- +0.95
21 PbO2(s) + 4H+ + 2e- = Pb+2 + 2H2O +1.451

29
 Properties of Selected Elements
Element Symbol Atomic # Atomic Wt. Valence Electronegativity
Aluminum Al 13 26.98 3 1.47
Bromine Br 35 79.904 1,3,5,7 2.74
Calcium Ca 20 40.08 2 1.04
Carbon C 6 12.01 2,4 2.50
Chlorine Cl 17 35.453 1,3,5,7 2.83
Copper Cu 29 63.54 1,2 1.75
Hydrogen H 1 1.01 1 2.20
Iron Fe 26 55.845 0,2,3 1.83
Magnesium Mg 12 24.31 2 1.23
Manganese Mn 25 54.94 2,3,4,6,7 1.60
Nitrogen N 7 14.0047 3,5 3.07
Oxygen O 8 16.00 2 3.50
Potassium K 19 39.10 1 0.91
Sodium Na 11 22.99 1 1.01
Strontium Sr 38 87.62 2 0.99
Sulfur S 16 32.06 2,4,6 2.44
Zinc Zn 30 65.39 2 1.65
Lead Pb 82 207.19 2,4

Selected Acidity Constants

(Aqueous Solution, 25°C, I = 0)
NAME FORMULA pKa
Perchloric acid HClO4 = H+ + ClO4- -7
Hydrochloric acid HCl = H+ + Cl- -3
Sulfuric acid H2SO4= H+ + HSO4- -3
Nitric acid HNO3 = H+ + NO3- 0
Bisulfate ion HSO4- = H+ + SO4-2 2
Phosphoric acid H3PO4 = H+ + H2PO4- 2.15
o-Phthalic acid C6H4(COOH)2 = H+ + C6H4(COOH)COO- 2.89
p-Hydroxybenzoic acid C6H4(OH)COOH = H+ + C6H4(OH)COO- 4.48
Nitrous acid HNO2 = H+ + NO2- 4.5
Acetic acid CH3COOH = H+ + CH3COO- 4.75
Aluminum ion Al(H2O)6+3 = H+ + Al(OH)(H2O)5+2 4.8
Carbonic acid H2CO3 = H+ + HCO3- 6.35
Hydrogen sulfide H2S = H+ + HS- 7.02
Dihydrogen phosphate H2PO4- = H+ + HPO4-2 7.2

30
 Hypochlorous acid HOCl = H+ + OCl- 7.5
Hypobromous acid HOBr = H+ + OBr- 8.71
Ammonium ion NH4+ = H+ + NH3 9.24
Bicarbonate ion HCO3- = H+ + CO3-2 10.33
Monohydrogen phosphate HPO4-2 = H+ + PO4-3 12.3
Sulfide HS- = H+ + S-2 13.9

Atmospheric Gases
Gas Atmospheric Abundance Henry’s Law Const 3
Nitrogen (N2) 780,840 ppmv (78.084%) 6.1 x 10-4
Oxygen (O2) 209,460 ppmv (20.946%) 1.3 x 10-3
Argon (Ar) 9,340 ppmv (0.9340%) 1.4 x 10-3
Carbon dioxide (CO2) 387 ppmv (0.0387%) 3.4 x 10-2
Neon (Ne) 18.18 ppmv (0.001818%) 4.5 x 10-4
Helium (He) 5.24 ppmv (0.000524%) 3.7 x 10-4
Methane (CH4) 1.79 ppmv (0.000179%)
Krypton (Kr) 1.14 ppmv (0.000114%)
Hydrogen (H2) 0.55 ppmv (0.000055%) 7.8 x 10-4
Nitrous oxide (N2O) 0.3 ppmv (0.00003%)
Xenon (Xe) 0.09 ppmv (9x10−6%)

α2 for a diprotic acid:

1
α2 =
[H ] [H + ]
+ 2
+ +1
K1K 2 K2

3
In: moles/L/atm

31
 0

-1

-2

-3

-4

-5

-6
Log CT

-7

-8

-9

-10

-11

-12

-13

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

pH

32