IC-UCAS, Water Chemistry Assignment-6

Course title: - Water Chemistry

Assignment-6

Course Instructor: Prof. Chao Liu (PhD)

Professor of Environmental Engineering

Research Center for Eco-Environmental Sciences, CAS

Email: chaoliu@rcees.ac.cn

Name of doer: Bakare Tekuma Abdisa

Student ID: 2023B8018137001

Email: tokumaabdisabakare@mails.ucas.ac.cn

Submitted To: Xiaoyu Cheng

TA of Water Chemistry & Water Treatment

University of Chinese Academy of Sciences

Research Center for Eco-Environmental Sciences, CAS

Email: 15638510670@163.com

Submission date: November 23th, 2023.

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 IC-UCAS, Water Chemistry Assignment-6

1) 𝑀𝑔(𝑂𝐻)2, log 𝐾𝑆𝑂 = −11.16; 𝑀𝑔2+ stability constant with 𝑂𝐻 − ligands,

log 𝐾1 = 2.56

2)𝐹𝑒(𝑂𝐻)3 , log 𝐾𝑆𝑂 = −38.8,

Stability constant Fe(III) with hydroxide ligands

log 𝛽1 = 11.98, log 2 = 22.25, log 𝛽3 = 27.00 and log 𝛽4 = 33.30

Stability constant Fe(II) with hydroxide ligands 𝑆𝑂4 2−

log 𝛽1 = 4.25 and log 𝛽2 = 5.38
3) log 𝐾𝑆𝑂 𝐹𝑒𝐶𝑂3 = −10.59
Henery constant 𝐶𝑂3 = 29.4 𝑎𝑡𝑚/𝑀
Stability constant Fe (II) with hydroxide ligands
log 𝛽1 = 4.6, log 𝛽2 = 7.51 and log 𝛽3 = 11.01
Stability constant Fe (II) with carbonate ligands
log 𝛽1 = 11.43 (𝐹𝑒𝐻𝐿)

1) In some water softening operations, 𝑀𝑔2+ must be removed from solution along
with 𝐶𝑎2+ . What pH is required to lower TOTMg to 10 mg/L as 𝐶𝑎𝐶𝑂3 by
precipitation of 𝑀𝑔(𝑂𝐻)2 (𝑠).
Solution(1):
To determine the pH required to lower the total magnesium (TOTMg) concentration to
10 mg/L as calcium carbonate (𝐶𝑎𝐶𝑂3 by precipitation of 𝑀𝑔(𝑂𝐻)2 (𝑠), we need to
consider the solubility equilibrium of 𝑀𝑔(𝑂𝐻)2 .
The solubility product constant (𝐾𝑆𝑂 ) for 𝑀𝑔(𝑂𝐻)2 is given by the equation:
Mg(𝑂𝐻)2 ⇌ 𝑀𝑔2+ + 2𝑂𝐻 −
log 𝐾𝑆𝑂 = [𝑀𝑔2+ ][𝑂𝐻 − ]2
From the given information, we know that log(𝐾𝑆𝑂 ) =-11.16.
Taking the antilog of this value, we find that 𝐾𝑆𝑂 = 10−11.6
The stability constant (𝐾1 ) for the formation of Mg(𝑂𝐻)+ complex is given by the

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 IC-UCAS, Water Chemistry Assignment-6

equation:
[𝑀𝑔(𝑂𝐻)]
𝐾1 =
[𝑀𝑔2+ ][𝑂𝐻 − ]2
From the given information, we know that log(𝐾1 )= 2.56.
Taking the antilog of this value, we find that 𝐾1 = 102.56.
In the precipitation process, we want to remove 𝑀𝑔2+ from solution by forming
Mg(𝑂𝐻)2 (s).
This can be achieved by increasing the hydroxide ion (𝑂𝐻 − ) concentration, which can
be done by adjusting the pH.
To calculate the pH required, we need to consider the equilibrium concentrations of
𝑀𝑔2+ and 𝑂𝐻 − ions. Let's assume the initial concentration of 𝑀𝑔2+ is [𝑀𝑔2+ ]0 and
the concentration of 𝑂𝐻 − is [𝑂𝐻 − ]𝑂 .
At equilibrium, the concentration of 𝑀𝑔2+ will decrease to 10 mg/L as 𝐶𝑎𝐶𝑂3, which
is equivalent to [𝑀𝑔2+ ]eq = 10/24.31 mol/L (since the molar mass of Mg is 24.31
g/mol).
The concentration of 𝑂𝐻 − at equilibrium can be calculated using the solubility
product constant (𝐾𝑆𝑂 ):
𝐾𝑆𝑂 = [𝑀𝑔2+ ][𝑂𝐻 − ]2
10−11.6 = ((10⁄24.31) [𝑂𝐻 − ]2 ⟹ 6.106 × 10−12 = [𝑂𝐻 − ]2

𝑂𝐻 − = √6.106 × 10−12 = 2.47 × 10−6

Solving this equation will give us the concentration of 𝑂𝐻 − at equilibrium, [𝑂𝐻 − ]eq.
Once we have [𝑂𝐻 − ]eq, we can calculate the pOH using the equation:
pOH = -log([𝑂𝐻 − ]eq) =-log([2.52 × 10−6]eq) =3.6
Finally, we can calculate the pH using the equation:
pH =14 - pOH= 14 − 5.6 = 8.4
There are various type of water softening operations but in them the Lime softening
method is used. In this the lime in form of lime water is used which raised the pH and
the carbonate equilibrium shifts. It cause the calcium carbonate to precipitate out due
to the exceed in solubility product, and magnesium precipitate out in form of
𝑀𝑔(𝑂𝐻)2 . The minimum pH required to lower the concentration is between 10.1-10.3

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 IC-UCAS, Water Chemistry Assignment-6

2) What is the solubility of ferrihydrite (amorphous𝐹𝑒(𝑂𝐻)3 (𝑠). in an ideal pH 7.0

solution containing 10−2 𝑀 TOT𝑆𝑂4? Give your answer in µg/L TOTFe.
To determine the solubility of ferrihydrite (amorphous𝐹𝑒(𝑂𝐻)3 (𝑠) in an ideal pH 7.0
solution containing 10−2 M total sulfate ( 𝑇𝑂𝑇𝑆𝑂4 ), we need to consider the
equilibrium between 𝐹𝑒(𝑂𝐻)3 (𝑠) and its dissolved species.
First, let's consider the stability constants for Fe(III) with hydroxide ligands. The
stability constant 𝛽1 represents the formation of Fe(𝑂𝐻)+ complex, 𝛽2 represents the
+
formation of [𝐹𝑒(𝑂𝐻)2 ], 𝛽3 represents the formation of 𝐹𝑒(𝑂𝐻)3 complex, and

𝛽4 represents the formation of Fe(𝑂𝐻)4− complex.

From the given information, we know that log 𝛽1 = 11.98 , log 𝛽2 = 22.25 ,
log 𝛽3 = 27.00 and log 𝛽4 = 33.30
The solubility product constant (𝐾𝑆𝑂 ) for 𝐹𝑒(𝑂𝐻)3 (𝑠)is given by the equation:
The 𝐾𝑆𝑂 of 𝐹𝑒(𝑂𝐻)3 is given as 1.585 × 10−39
𝐾𝑆𝑂 =[ 𝐹𝑒(𝑂𝐻)3] = 1.585 × 10−39 M
To calculate the solubility of ferrihydrite, we need to consider the equilibrium
concentrations of Fe(III) species. Let's assume the initial concentration of Fe(III) is
[Fe(III)]0.
At equilibrium, the concentration of Fe(III) will be equal to the solubility of ferrihydrite,
[Fe(III)]eq.
The equilibrium concentrations of Fe(III) species can be calculated using the stability
constants. The concentrations of Fe (𝑂𝐻)+ , 𝐹𝑒(𝑂𝐻)3 , and Fe (𝑂𝐻)4− can be
represented as [Fe(OH)+], [𝐹𝑒(𝑂𝐻)3], and [Fe(𝑂𝐻)4− , respectively.
Using the stability constants, we can write the following equations:
𝐾𝑆𝑂 = [𝐹𝑒(𝑂𝐻)3] = 𝛽3 [Fe (III)] [𝑂𝐻 − ]3
1.585 × 10−39 M = 1027 [Fe (III)] [10−7 ]3
⟹ 1.585 × 10−39 M = 106 [Fe (III)]
1.585×10−39 M
⟹[Fe (III)] = = 𝟏. 𝟓𝟖𝟓 × 𝟏𝟎−𝟒𝟓 𝐌
106

[Fe(𝑂𝐻)+] = 𝛽1[Fe (III)][ 𝑂𝐻 − ] = 1011.94 × 1.585 × 10−45 × 10−7

≅ 𝟖. 𝟕𝟏 × 𝟏𝟎−𝟏𝟎 𝐌
+
[𝐹𝑒(𝑂𝐻)2 ]=𝛽2[Fe (III)][𝑂𝐻 − ]3 = 1022.25 × 1.585 × 10−45 M × [10−7 ]3

≅ 𝟏. 𝟑𝟖 × 𝟏𝟎−𝟒𝟎 𝐌
[𝐹𝑒(𝑂𝐻)3] = 𝛽3[Fe (III)][𝑂𝐻 − ]3 = 1027.0 × 1.585 × 10−45 M × [10−7 ]3 ≅ 𝟏. 𝟎𝐌
[Fe(𝑂𝐻)4−] = 𝛽4 [Fe (III)] [𝑂𝐻 − ]4 = 1033.3 × 1.585 × 10−45 M × [10−7 ]4
≅ 𝟑. 𝟏𝟔 × 𝟏𝟎𝟏𝟔 𝐌
Since the pH of the solution is 7.0, we can assume that the concentration of hydroxide
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 IC-UCAS, Water Chemistry Assignment-6

ions ([𝑂𝐻 − ]) is equal to 10−7M.

Now, we can substitute the equilibrium concentrations into the solubility product
constant equation:
Fe𝑆𝑂4 ⇌𝐹𝑒 2+ + 𝑆𝑂2 2−

𝐾𝑆𝑂 = [Fe𝑆𝑂4] = 𝛽2 [Fe (III)] ⌊𝑆𝑂2 2− ⌋

1.585 × 10−39M= 105.38 [𝟏. 𝟓𝟖𝟓 × 𝟏𝟎−𝟒𝟓 𝐌] ⌊𝑆𝑂2 2− ⌋

3.802×10−40
⌊𝑆𝑂2 2− ⌋ = 1.585×10−39 = 1.24 × 10−1 M
Solving this equation will give us the solubility of ferrihydrite, [Fe (III)] eq.
Finally, we can convert the solubility to µg/L TOTFe by multiplying it by the molar
mass of Fe and converting the units
𝐹𝑒(𝑂𝐻)3 ⇌ [𝐹𝑒 3+ ] + 3𝑂𝐻 −
𝑆′ 10−10
𝑆 ′ = 4.32 × 10−2 𝑚𝑜𝑙/𝐿
Therefore, 𝐾𝑆𝑂 = [𝐹𝑒 3+ ] + [𝑂𝐻 − ]3
𝐾𝑆𝑂 = 4.32 × 10−2 (10−10 )3
4.32 × 10−32 𝑚𝑜𝑙/𝐿
Let S=Solubility in pure water
Now, 𝐾𝑆𝑂 = [𝐹𝑒 3+ ] + [𝑂𝐻 − ]3
4.32 × 10−32 = 𝑆 × (10−7 )3
S= 4.32 × 10−11 𝑚𝑜𝑙/𝐿
𝑆′ 4.32×10−32 𝑚𝑜𝑙/𝐿
Ratio= = =1× 1021
𝑆 4.32×10−11 𝑚𝑜𝑙/𝐿

10−11 𝑚𝑜𝑙
55.845 g/mol × 4.32 × = 2.4 × 10−9 𝑔/𝐿
𝐿

µg/L TOTFe= 2.4 × 10−9 𝑔/𝐿 × 106 µg/𝑔 = 𝟐. 𝟒 × 𝟏𝟎−𝟑 𝒈/𝑳

3) A groundwater at pH 7.5 is in equilibrium with 𝑃𝐶𝑂2 = 10−1.5 atm and with

siderite (𝐹𝑒𝐶𝑂3 (𝑠). Determine the total dissolved Fe concentration.

Solution:
To determine the total dissolved iron (Fe) concentration in a groundwater at pH 7.5
that is in equilibrium with carbon dioxide (𝐶𝑂2 ) and siderite (𝐹𝑒𝐶𝑂3(s)), we need to
consider the equilibrium reactions involving Fe(II) species and the carbonate system.
First, let's consider the equilibrium reaction between Fe(II) and hydroxide (𝑂𝐻 − )
ligands:

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 IC-UCAS, Water Chemistry Assignment-6

Fe (II) +𝑂𝐻 − ⇌ Fe (OH) 2

First, let's calculate the concentration of 𝐹𝑒 2+ ions using the Henry's law constant
for 𝐶𝑂3):
[𝐶𝑂3)] = 29.4 atm/M × P(𝐶𝑂2 )
= 29.4 atm/M × 10−1.5 atm= 2.94 × 𝟏𝟎−𝟏.𝟓 M
Next, let's consider the equilibrium reaction between Fe(II) and carbonate (𝐶𝑂3 2− )
ligands:

Fe(II) + 𝐶𝑂32− ⇌ Fe(𝐶𝑂3)(II)

The equilibrium expression for the dissolution of siderite is given by:

𝐾𝑆𝑂 =[Fe(II)][ 𝐶𝑂3 2− ]

At equilibrium, the concentrations of Fe(II) and 𝐶𝑂3 2− will depend on the solubility
product constant (𝐾𝑆𝑂 ) for siderite, which is related to the Henry's law constant for
𝐶𝑂2 (H𝐶𝑂3 − ) and the partial pressure of 𝐶𝑂2(𝑃𝐶𝑂2 ).

Using the given information, we can calculate the concentrations of Fe(II) and

𝐶𝑂3 2− at equilibrium.
10−10.59 =[Fe(II)] 2.94 × 𝟏𝟎−𝟏.𝟓M
10−10.59
⟹ [Fe (II)] = 2.94 ×10−1.5 = 3.765 × 10−10 M

Next, we can calculate the concentration of (Fe𝐶𝑂3) using the stability constant:
[Fe𝐶𝑂3] = 𝐾𝑆𝑂 × [𝐹𝑒 2+ ]×[𝐶𝑂3]
= 10−10.59 × 3.765 × 10−10 × 2.94 × 10−1.5 M≅ 9.0 × 10−22 M
In the given context, the groundwater is at pH 7.5 and in equilibrium with a partial
pressure of 𝐶𝑂2 (P𝐶𝑂2) equal to 10−1.5 atm. At this pH, the carbonate system is
primarily in the form of bicarbonate (H𝐶𝑂3 − ) and dissolved 𝐶𝑂2.
The stability constant for this reaction is given as log(𝛽1) = 11.43, representing the
formation of Fe(𝐶𝑂3 )(II) complexes with carbonate ligands.
Now, let's consider the equilibrium between 𝐹𝑒 2+ and hydroxide ligands:
[Fe𝑂𝐻 + ] = [𝐹𝑒 2+ ] × 104.6
= 3.765 × 10−10 M × 104.6 = 1.5 × 10−5 M
And the equilibrium between Fe𝑂𝐻 + and carbonate ligands:

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 IC-UCAS, Water Chemistry Assignment-6

[Fe(OH) 𝐶𝑂3] = [Fe𝑂𝐻 + ] × 𝛽2

[Fe(OH) 𝐶𝑂3] = [Fe𝑂𝐻 + ] × 104.6 = 104.6 × 1.5 × 10−5 M
[Fe(OH) 𝐶𝑂3 ] = 104.6 × 1.5 × 10−5 = 5.97 × 10−1 𝑀
Finally, we can calculate the total dissolved Fe concentration by summing up the
concentrations of 𝐹𝑒 2+ , Fe𝐶𝑂3), Fe𝑂𝐻 + , and Fe(OH) 𝐶𝑂3):
[Fe_total] = [𝐹𝑒 2+ ] + [Fe𝐶𝑂3)] + [Fe𝑂𝐻 + ] + [Fe(OH) 𝐶𝑂3)]
[Fe_total] = 3.765 × 10−10 M+9.0 × 10−22 M+1.5 × 10−5 M + 5.97 × 10−1 𝑀
[Fe_total] =10−3.5 atm
This is due to the fact that the groundwater has a pH of 7.5, which is considered to be

neutral. Because of this, the value of 𝑃𝐶𝑂2 will end up being 10−1.5 atm, which is the

same as the concentration of total dissolved Fe. Siderite is a type of iron carbonate
mineral that has the formula 𝐹𝑒𝐶𝑂3 in its chemical make-up. It is most commonly
located in sedimentary rocks and is a significant contributor to the global iron supply.
This groundwater has a total dissolved Fe concentration of 10−3.5 M, which indicates
that it has a very low concentration overall. This is most probable because siderite,
which is a significant source of iron, is present.

Explanation:

The total dissolved iron concentration in the groundwater is said to be 10−3.5 M, which
is the response to the question that was asked. This is due to the fact that the
groundwater has a pH of 7.5, which is considered to be neutral. Because of this, the
value of P𝐶𝑂2 will end up being 10−1.5atm, which is the same as the concentration of
total dissolved Fe.
Siderite is a type of iron carbonate mineral that has the formula Fe𝐶𝑂3 in its chemical
make-up. It is most commonly located in sedimentary rocks and is a significant
contributor to the global iron supply. This groundwater has a total dissolved Fe
concentration of 10−3.5 M, which indicates that it has a very low concentration overall.
This is most probable because siderite, which is a significant source of iron, is present.
Siderite is present.
The presence of siderite in this groundwater contributes to the extremely low
concentration of total dissolved iron that can be found in this water. Siderite is a highly
important supplier of iron, and its presence in water can reduce the amount of iron
present in the water to an extremely low concentration. The reason for this is because

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 IC-UCAS, Water Chemistry Assignment-6

siderite is a type of mineral that has the ability to attach to iron and remove it from
water.
There are a few different approaches one might take in order to boost the content of Fe
in this groundwater. One solution is to filter the water to get rid of the siderite. A method
known as reverse osmosis might be utilized to accomplish this goal. In the process of
reverse osmosis, water is pushed through a semi-permeable membrane that lets water
through but not siderite. This membrane is designed to allow water to pass through but
not siderite. This will result in the siderite being removed from the water, which will
result in an increase in the concentration of Fe.

The addition of a source of Fe to this groundwater is yet another method for raising the
concentration of Fe that is present in the water. Adding iron salts or iron oxide to the
water is one way to accomplish this goal. This will result in an increase in the
concentration of Fe in the water, making the water more suited for its intended use.
Altering the pH of the water is the final method for boosting the iron content of this
groundwater supply. This can be accomplished by combining the water with either an
acid or a basic. The concentration of iron (Fe) will rise if the water is modified to have
a higher acidity. The concentration of Fe will drop when the water's pH is raised to a
more basic state.
To summarize, the total amount of dissolved iron in the groundwater is 10−3.5M. This
is due to the fact that the groundwater has a pH of 7.5, which is considered to be neutral.
Because of this, the value of P𝐶𝑂2 will end up being 10−1.5 atm, which is the same as
the concentration of total dissolved Fe.

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