CVEN 3454 Water Chemistry Exam II Solution

1. (3 points) A soil pore water is in equilibrium with the soil atmosphere (PCO2 = 10-2.5 bar) and two
minerals, aragonite and siderite. What is the pH and alkalinity of the equilibrium solution?

Aragonite is another form of CaCO 3(s) that is slightly more soluble than calcite:

CaCO 3(s) = Ca2+ + CO 32- Ks0 = 10-8.36

Siderite is a ferrous carbonate (FeCO 3(s)):

FeCO 3(s) = Fe 2+ + CO 32- Ks0 = 10-10.55

Following the equilibrium of calcite with the atmosphere as in Lecture 22, we can make a tableau with CO 2(g)
and the two solids as components:

H+ CO 2(g) CaCO 3(s) FeCO 3(s)

H+ 1

OH- -1

H2CO 3* 1

HCO 3- -1 1

CO 32- -2 1

Ca2+ 2 -1 1

Fe 2+ 2 -1 1

CO 2(g) 1 ?

CaCO 3(s) 1 ?

FeCO 3(s) 1 ?

The TOTH equation is

[H +] - [OH-] - [HCO 3-] - 2[CO 32-] + 2[Ca2+] + 2[Fe 2+] = 0

With the addition of two carbonate minerals and an acid, the carbonic acid, at a higher than normal PCO2, we
can expect a near-neutral solution pH, so the proton, hydroxide, and carbonate concentrations should be
negligible:

[HCO 3-] = 2[Ca2+] + 2[Fe 2+]

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We can replace the calcium and ferrous iron concentrations with
+ 2
2+ K sarag K sarag K sarag
0 H CO2 [ H ]
[Ca ] = 0
= 0
=
[CO32 − ] K a1 Ka 2 PCO2 H CO−1
2
[ H + −2
] K a1 Ka 2 PCO2
+ 2
2+ K ssid0 K ssid0 K ssid
0 H CO2 [ H ]
[ Fe ] = = =
[CO32 − ] K a1 K a 2 PCO2 H CO −1
2
[ H + −2
] K a1 Ka 2 PCO2
We can replace the bicarbonate concentration as:

K a1 PCO2
[ HCO3− ] =
[ H + ] H CO2
The resulting simplified TOTH equation is
+ 2
K a1 PC O2 K sarag
0 H CO2 [ H ] K ssid0 H CO2 [ H + ]2
=2 +2
[ H + ] H CO2 K a1 Ka 2 PCO2 K a1 Ka 2 PCO2
Rearranging to solve for [H +],

K a1 PCO2  K sarag
0 H CO2 K ssid0 H CO2 
= [H ]  2
+ 2
+2 
[ H + ] H CO2  K a1 Ka 2 PCO K a1 Ka 2 PCO2
 2 
−1
Ka1PCO2  K sarag
0 H CO2 K ssid0 H CO2 
[H ] =
+ 3
2 +2 
H CO2  Ka1 Ka2 PCO2 Ka1 Ka2 PCO2 
−1
(10−6.35 )(10−2.5 ) 
+ 3 (10−8.36 )(28.8) (10−10.55 )(28.8) 
[H ] =  2 −6.35 −10.33
+ 2 
28.8  (10 )(10 )(10−2.5 ) (10−6.35 )(10−10.33 )(10−2.5 ) 
[ H +] 3 = 10−10.31 (1012.58 + 1010.39 ) = 10−10.31(10− 12.58 ) = 10−22.89
−1

[ H + ] = 10−7.63

So the pH of the solution is 7.63.

The alkalinity is

Alk = -[H +] + [OH-] + [HCO 3-] + 2[CO 32-]

At this pH, bicarbonate is the only important species in this equation, so

Alk = [HCO 3-] = Ka1PCO2 HCO2-1 [H +]-1 = (10-6.35)(10-2.5)(28.8)-1(10-7.63)-1

Alk = 10-2.68 M

The alkalinity for the solution is 10-2.68 M.

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2. (4 points) A stream water contaminated with nickel (TOTNi = 10-6 M) flows downstream from an
abandoned mine that used cyanide heap leaching. The pH of the stream gradually increases from
pH 4 near the mine to pH 8 about 5 km downstream. The water contains sulfate (TOTSO4 = 10-2 M),
chloride (TOTCl = 10-4 M), and cyanide (TOTCN = 10 -6 M) and is in equilibrium with the atmosphere
(PCO2 = 10-3.46 bar). At what pH will the concentration of free nickel ion, [Ni2+], drop below 10-7 M?

The expression to determine the concentration of nickel is

TOTNi =  Ni 2 +  +  NiOH +  +  N i(O H )02  +  Ni (OH ) −3  +  NiCO3−  +  Ni (C O3 ) 32−  +  NiHCO30 
+  NiSO4−  +  Ni ( SO4 ) 32−  +  NiCl +  +  NiCl20  +  N i(C N )20  +  N i(C N )3−  +  Ni ( HCN ) 23 + 
2 3
TOTNi =  Ni 2 +  + β1  Ni 2 +  OH −  + β2  Ni 2 +  OH −  + β3  Ni 2 +  OH − 
2
+ β1  Ni 2 +  CO32 − + β2  Ni 2 +  CO32 −  + β1  Ni 2 +  H +  CO32 − 
2 2
+ β1  Ni 2 +   SO42 −  + β2  Ni 2 +  SO42 −  + β1  Ni 2 +  Cl −  + β2  Ni 2 +  Cl − 
2 3 3 3
+ β2  Ni 2 +  CN −  + β3  Ni 2 +  CN −  + β1  Ni 2 +   H +  CN − 
 1 + β OH −  + β  OH −  2 + β OH − 3 + β CO2−  + β CO 2 − 2 + β  H +  CO2 −  
1  2   3   1  3  2  3  1   3 
TOTNi =  Ni   2+ 
 − 3 
 2−
  2− 2
  −
  − 2
  − 2
  − 3
  + 3
   
 +β1 SO4  + β 2 SO4  + β1 Cl  + β 2 Cl  + β2 CN  + β3 CN  + β1  H  CN  
TOTNi
 Ni 2 +  =
1 + β OH  + β OH  + β  OH  + β  CO 2−  + β CO 2 − 2 + β  H +  CO 2 − 
− − 2 − 3

1   2   3  1 3  2  3  1  3 
 
 2 2 2 3 3 3

+β  SO
 1 4 
2−
 + β 
2 
SO 2−
4 
 + β 
1 
Cl −

 + β 
2 
Cl −

 + β 2 
 CN −

 + β 
3 
CN −

 + β 
1 
H +

   CN −

 

Now, we will substitute [Ni2+] = 10-7 M and TOTNi = 10-6 M and insert values for the ligand concentrations that
are not pH-dependent (sulfate and chloride):
 1 + β  OH −  + β OH − 2 + β OH − 3 + β CO 2−  + β CO 2 − 2 + β  H +  CO 2 −  
1  2   3   1  3  2  3  1  3 
TOTNi
=  
 Ni 2 +   +β  SO 2 −  + β  SO 2−  2 + β Cl −  + β Cl −  2 + β  CN −  2 + β  CN −  3 + β  H +  3 CN −  3 
 1 4  2  4  1   2  2   3   1     
 − − 2 3 2
 OH −  + 106.87 CO32−  + 1010.11  CO32 −  + 1012.47  H +  CO32 −  
10−6  1 + 10  OH  + 10  OH  +10
4.14 9.00 12.00

= 
10−7  +10 2.29 (10−2 ) + 101.02 (10 −2 ) 2 + 100.4 (10− 4 ) + 100.96 (10−4 ) 2 + 1014.59  CN −  2 + 1022.64  CN −  3 +1043.95  H +  3  CN −  3 
         
 1 + 104.14  OH −  +109.00  OH −  2 + 1012.00  OH −  3 + 106.87 CO 2−  + 1010.11  CO 2 −  2 + 1012.47  H +  CO 2 −  
       3   3     3 
10 = 
 2 3 3 3 
− 2.98 − 3.6 − 7.04
 CN  + 10
−
 CN  + 10
−
 H  CN 
+ −
 +10 + 10 + 10 + 10 + 10
0.29 14.59 22.64 43.95
        
 100.47 + 104.14 OH −  + 109.00  OH −  2 + 1012.00 OH−  3 + 106.87  CO 2−  + 1010.11  CO 2−  2 + 1012.47  H +   CO 2 −  
       3   3    3 
10 = 
 − 2 − 3 + 3 − 3 
 CN  + 10  CN  + 10  H   CN 
 +10
14.59 22.64 43.95


Now we need some expressions for the pH-dependent ligands, hydroxide, carbonate, and cyanide.
Kw
[OH − ] = +
= 10−14.0 [ H + ]−1
[H ]
−6.35 −10.33 −3.46
2−
K a1 Ka 2 PCO2 (10 )(10 )(10 ) −21.6 + −2
[CO3 ] = + 2
= + 2
= 10 [H ]
[ H ] H CO2 [ H ] (28.8)
−9.24 −15.24
− Ka 10 −6 10
[CN ] = α1TOTCN = TOTCN = (10 ) =
K a + [H + ] 10−9.24 + [ H + ] 10−9.24 + [ H + ]

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These values can be inserted into the derived above.
−14.0 + −1 −14.0 + −1 2 −14.0 + −1 3
10 = 10 + 10 [ H ] ) + 10 [ H ] ) + 10
0.47 4.14 9.00 12.00
(10 (10 (10 [H ] )
−21.6 + −2 −21.6 + −2 2
+ 10
6.87
(10 [ H ] ) + 10
10.11
(10 [ H ] ) + 10
12.47
 H +  (10−21.6 [ H + ]−2 )
2 3 3
 10−15.24  22.64  10
−1 5.24
 + 3 10
− 15.24

+ 10
14.59
 −9.24 + 
+ 10  −9.24 + 
+ 10
43.95

 H 
  −9.24 + 
 10 + [H ]   10 + [H ]   10 + [H ] 
10 = 10 0.47 + 10 −9.86 [H + ]−1 + 10 −19.0 [H + ]−2 + 10 −30.0 [ H + ]−3
+ 10 −14.73[ H + ]−2 + 10−33.09 [ H + ]−4 + 10−9.13 [H + ]−1
3
10 −15.89 10−23.08 −1.77  [H + ] 
+ + + 10  −9.24 + 
(10 + [ H + ]) (10 + [H + ]) + [H ] 
2 3
−9.24 −9.24
 10
Rather than try to solve this equation for [H +], it can be entered into a spreadsheet and solved by iteration
(e.g., “Solver” in Microsoft Excel®). The interated solution for [H +] is 1.685x10- 8 M = 10-7.77 M ; therefore...

The pH at which [Ni2+] goes below 10-7 M is 7.77.

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3. (3 points) In the anoxic zone of the Everglades sediments, the concentration of Hg2+ is controlled
by equilibrium with a mineral phase. The water in the Everglades sediments is characterized by
pH 7.3, PH2S = 10-15.0 bar, PCO2 = 10-2.2 bar, and [Cl -] = 10-3.2 M. What mineral controls Hg2+ solubility
and what is [Hg2+] under these conditions?

Table 8.7 in Benjamin (2001) lists the following Hg2+ solid species:

Hg(OH)2(s) = Hg2+ + 2 OH- Ks0 = 10-25.40

HgO(s) + H2O = Hg2+ + 2 OH- Ks0 = 10-25.55
Hg(CN)2(s) = Hg2+ + 2 CN - Ks0 = 10-39.28
HgCO 3(s) = Hg2+ + CO 32- Ks0 = 10-22.52
HgS(s) = Hg2+ + S2- Ks0 = 10-52.01

The mineral that controls Hg2+ solubility is the mineral that results in the lowest [Hg 2 + ]. The minerals
Hg(OH)2(s), HgO(s), HgCO 3(s), and HgS(s) must be checked, but Hg(CN)2(s) does not need to be checked
because CN - was not listed as a constituent of the water. Notice also that none of the solids involves Cl- even
though the chloride concentration was provided.

To determine these concentrations of Hg2+, we must determine the concentrations of the ligands:

[OH-] = 10-6.7 M based on pH = 7.3

K a 1 K a 2 PCO2 (10 −6.35 )(10 −10.33 )10 −2.2

[CO32 − ] = + 2
= −7.3 2
= 10−5.74 M
[H ] H CO 2 (10 ) 28.8
2− K a1 K a 2 PH 2 S (10 −6.99 )(10 −12.92 )10 −15.0
[S ] = + 2
= −7.3 2
= 10 −21.30 M
[H ] HH 2S (10 ) 9.8

With these ligands, we can calculate the concentration of Hg2+:

K s0 10 −25.40
For Hg(OH)2(s): [ Hg 2 + ] = = = 10−12.0 M
[OH − ]2 (10 −6.7 )2
K s0 10−25.55
For HgO(s): [ Hg 2 + ] = − 2
= −6.7 2
= 10 −12.14 M
[OH ] (10 )
K s0 10−22.52
For HgCO 3(s): [ Hg 2 + ] = 2−
= −5.74
= 10−16.78 M
[CO3 ] 10
Ks0 10 −52.01
For HgS(s): [ Hg 2+ ] = = = 10 −30.71 M
[ S 2 −] 10−21.3

By a wide margin, HgS(s) (cinnabar) controls Hg2+ solubility.

The concentration of Hg2+ is 10-30.71 M.

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