Tutorial on Visual Minteq 2.30, adsorption.

One of the main purposes for Minteq type of programs is to perform adsorption
calculations, in addition to doing the straight forward acid-base-complexation-
precipitation calculations in the presence and absence of gas with and without redox
reactions. Often, the most important processes for trace elements are various adsorption
reactions and these reactions are rarely treated in courses or text books, probably because
they tend to be ill defined and there are not as many simplistic descriptions as with e.g.
solubility constants.

Solids in water generally form an oxide/hydroxide-water interface and are represented by
for example, ≡SOH and ≡SO
-
, where the “≡S” represents the solid-surface interface.
Adsorbed materials are written as complexes of these surface oxides, for example,
≡SOPb
+
, ≡SONa, or ≡SOAsO
3
-
, etc.

OH
-
Na
+
Cl
-
PbOH
+
H
HCO
3
-
+
OH
-
Cl
-
Pb
2+
OH ≡SOH
≡SO
-
≡SOPb
+
O
-
OPb
+
Solid Symbol Solution

Example Reactions:
≡SOH → ≡SO
-
+ H
+
≡SOH + Pb
2+
→ ≡SOPb
+
+ H
+


The units used in adsorption reactions have several peculiarities and conventions that are
not normal, but are in common use. At least four ideas need to be used to express
concentrations with reactive solids: 1. the amount of solid in solution, mg/l, g/l, kg/l,
etc.; 2. the concentration of reactive surface sites on the solid in solution, sites/m
2
,
sites/nm
2
, etc; 3. the specific surface area of the solid, m
2
/g; and 4. the concentration of
contaminant on the solid, mg/g, mg/kg, mol/kg. As will be seen these can be combined
to express the concentration of reactive sites per liter of solution. In addition, there is no
established set of symbols or conventions on how to represent these common concepts;
Visual Minteq uses “moles of adsorbents per liter of solution” as the working unit. This
simplifies the mathematics and allows all calculations to be performed in the exactly
same manner as acid/base or complexation reations.

1. Concentration units in common use:
Mason Tomson Visual Minteq Page 1 Adsorption 11/2/2004 1
a.






=
solid of kg
lead of moles
Conc.
“Total contaminant per gram” is what is measured, e.g., “mg of Pb/g of solid”
or “mole of Pb/g of solid.” This is what is measured in most laboratories by
filtering an amount of solid phase and acid digesting the lead from the solid
and measuring by ICP, AA, titrations…
b. ⎟














=






Solution of Liter
solid of kg
Solid of kg
Pb mol
solution of Liter
solid on lead of moles
Conc.
This concentration of contaminant on the solid phase is used in Visual Minteq
to do calculations wherein the concentration on the solid are in terms of M,
just like all other concentrations. For example, if Pb is 100 mg/kg (essentially
100 ppm), which is a common concentration of lead in soil, sediments, etc. If
the solid content is 10 mg/l, as with a slightly turbid lake, then the
concentration would be 10
-3
(mg of Pb)/(Liter of solution), which is of little
toxicity concern. On the other hand, if the same solids concentration is 1 kg/l,
as in sediment slurry, the total possible lead would be 100 mg/l –a deadly
poison.
c. Conc. in terms of Tot≡SOH
























⋅ ⎟





=






# s Av.'
mole 1
m
sites #
kg
m
Solution of Liter
Solid of kg
solution of liter
sites reactive of moles
2
2

This the form of the concentration that is used in Visual Minteq, represented
as, for example, Tot≡SOH (mol/l) component. Notice that this is combination
of solid concentration, surface area, site density on the surface, and
Avagadro’s number.
2. {≡SOPb
+
} = [≡SOPb
+
], i.e., the solid phase activity and concentration are taken to
be the same, the activity coefficients of the solid phase species are always taken to
be 1.00. This is a rather controversial assumption and many have challenged it,
but it is the assumption used in nearly all software programs. –Many books have
written on this topic, but for the sake of simplicity we will not cover all these
alternative arguments in this discussion.
3. Solid-solution equilibrium constants are typically written in terms solution phase
activities, {Pb
2+
} = [Pb
2+
]·γ
Pb2+
, of individual species. The activity coefficient in
solution is composed of two parts, the first related to normal ion-ion interactions
in solution from the other ions in solution (treated by the Davies or the Debye-
Huckel equation) and secondly a contribution from the charged solid-phase
surface, see next item.
4. As an ion approaches the solid surface, the electrostatic potential of the solid
surface can greatly affect the activity of the of the solution ion. This effect is
expressed as a Boltzmann factor, , where ψ
RT / F
o
e
ψ −
o
(V) is the potential of the
surface due to electrostatic potential from the charged solid surface.


Mason Tomson Visual Minteq Page 2 Adsorption 11/2/2004 2
Overall objective of adsorption speciation. Regardless of the specific mathematical
formulation of the adsorption, partitioning, complexing, etc., the overall objective in
terms of environmental fate and transport of contaminants in the environment is generally
to arrive at a single distribution coefficient, K
d
(L of solution/kg of solid) that describes
the amount of the contaminant on the solid phase versus the amount in the mobile
solution phase:

) solution of L / mol ( ] forms all in TotCont [
) solid of kg / mol ( ] forms all in on concentrai TotCont [
) kg / L ( K
solution aqueous in
solid on the
d
=

Often these measured K
d
values are used to report data. These K
d
values are tabulated for
specific solids and waters, e.g., sea water or lake water, etc., and as long as the overall
conditions of pH, redox, complexing agents, etc., are reasonably constant these K
d
values
can be used to calculate the overall concentration in solution from the solid phase value,
or vice versa, and thereby bio-availability to organisms:

TotCont
on solid
(mol/kg) = K
d
(L/kg)⋅TotCont
in solution
(mol/L)

These values of K
d
that are required to mathematically describe the transport of
contaminants of all kinds, regardless or the functional form used to arrive at the ratio of
adsorbed to aqueous concentrations. That is, the species that are in the aqueous phase are
assumed to be mobile and the species adsorbed to the solid are assumed to be immobile,
or not available. Minteq and Visual Minteq authors were sensitive to this end use when
they formulated the program for the EPA in the 1970’s and later. Notice that the output
screen always lists Total of Component in Solution and the Total of Component
Adsorbed, which is what is needed to know, the total that is available to organisms, etc.
After the various adsorption models are introduced, the K
d
values can be examined.

Solid metal oxides and other surfaces often are strong adsorbers of aqueous species, such
as Pb
2+
, PO
4
3-
, AsO
4
3-
, etc. There are many types of options for adsorption reactions.
Mostly, they divide into three groups.

1. Simple isotherms, illustrated for aqueous cadmium ion activity, {Cd
2+
}, adsorption
to a surface oxide site, ≡SOH, to for form ≡SOCd
+
+ {H
+
}:
a. Linear isotherm: [≡SOCd
+
]
adsorbed
= K
ads.
{Cd
2+
}
with K
ads
(L of solution/kg of solid). These K
ads.
constants are often supplied
by a local curve fitting of the adsorption of some metal onto the overall bulk
solid phase. Visual Minteq permits you to add any K
ads.
value you wish and it
will then incorporate that K
ads.
value into an overall speciation with redox,
precipitation, etc., scheme and model the amount of trace metal adsorbed.
This is a very practical and useful option for real site data to account for the
effect of e.g., added complexing agents or changes in pH in the site and still
use the measured K
ads.
Mason Tomson Visual Minteq Page 3 Adsorption 11/2/2004 3
b. Langmuir isotherm:
} Cd { K 1
} Cd { K ] SOCd [
] SOCd [
2
Lang
2
Lang
Maximum
adsorbed
adsorbed
+
+ +
+
+
⋅ ⋅ ≡
= ≡
with the constant, K
Lang.
(L/mol), note that when {Cd
2+
} is small the isotherm
is linear in {Cd
2+
} and when {Cd
2+
} is large the isotherm equals a constant,
. Numerous tables and books report these K
Maximum
adsorbed
] SOCd [
+

Lang
constants
(see below) and even values of for numerous different soils
or sediments. Also, you can make only one or two measurements to
determine K
Maximum
adsorbed
] SOCd [
+

Lang
and as constants for your soil or sediment
and then use Visual Minteq to calculate the effects of solution conditions on
the adsorption or fate of the trace heavy metal or contaminant.
Maximum
adsorbed
] SOCd [
+

c. Freundlich isotherm: [≡SOCd
+
]
adsorbed
= K
F
{Cd
2+
}
m

with m = constant and normally m ≈ 0.5 to 1.0. Again, values of K
F
and m are
often tabulated for different soils and sediments.
d. Various combination isotherms and numerous other isotherms are listed in
Visual Minteq.
Mason Tomson Visual Minteq Page 4 Adsorption 11/2/2004 4
For example, the following tables of data are taken from Bobek, et al., “Environmental
Inorganic Chemistry: Properties, Processes, and Estimation methods,” Pergamon Press,
1988. This text and numerous others like it list literally thousands of constants and sets
of constants for all kinds of isotherms and conditions. These tabulations are commonly
used to estimate the aqueous or solid concentrations by matching, as closely as possible,
one’s needs against what has already been measured. First, in the following table is
listed a few constants for Cadmium adsorption to a few materials:



Mason Tomson Visual Minteq Page 5 Adsorption 11/2/2004 5

Second for Arsenic(III), the much more toxic oxidation state of arsenic:


2. Ion exchange adsorption of ions, for example for Cd
2+
exchanging with Ca
2+
:
[≡SOCa
+
]
adsorbed
+ Cd
2+
[≡SOCd
+
]
adsorbed
+ Ca
2+
,
or:
} Cd { ] SOCa [
} Ca { ] SOCd [
K
2
adsorbed
2
adsorbed
exchange ion
+ +
+ +
⋅ ≡
⋅ ≡
= ,

with these dimensionless K
ion exchange
constants sometimes called “selectivity
coefficients.” The soil, sediment, clay, or organic matter are also characterized by
a total cation exchange capacity, CEC (mequivalents of exchangeable ions/g of
solid) There are literally thousands of such constants in texts, such as the one
referenced above and references therein.
Mason Tomson Visual Minteq Page 6 Adsorption 11/2/2004 6

Electrostatic double layer models (dlm), overview. These models will be the primary
focus of the remainder of this Visual Minteq Tutorial. Minteq can be used to describe
most heterogeneous reactions; the sample test problems that are listed in the File input
menu are excellent points of departure and can be used as “seed problems” that you can
modify for your particular needs. Adsorption data is not nearly as systematic and well
accepted as for acid/base and complexation. This is probably because not enough effort
has been spent to organize and establish the measurements in a manner that they can be
reliably used in all circumstances, i.e., this is still a developing field of science and
applied practice. Therefore, most of the adsorption data entries in Visual Minteq are such
that the values can be readily changed. Hohl and Westall in 1980 published a critical
paper (Adv. Coll. Interface Sci., 12,265) in which they compared five common
adsorption models and proved that you could not normally justify picking one as clearly
superior to the others. That is, it doesn’t matter too much which model you use as long as
the sorption constants have been curve fitted to that model. If you pick another model
and use the corresponding sorption constants, both will typically fit the experimental data
equally well. Therefore, it is probably only necessary to describe only one model and
that is what will be done herein. This discussion will focus on the model for which there
is the most data, the simple two pKa double layer model and will focus on adsorption to
what has been called “hydrous ferric oxide” which can be used as a model adsorbents for
a wide range of conditions and for which a Dzomback and Morel have published a large
amount of data.

The basic problem will be to describe the adsorption of arsenic, AsO
4
3-
, and cadmium,
Cd
2+
, to “hydrous ferric oxide, Fe(III)Oxide⋅H
2
O, versus pH and pe and in the presence
of various competing ions, etc., but first the acid/base chemistry of simple hydrous ferric
oxide. We will use 1 g/L at surface area of 100 m
2
/g and a site density of active ≡FeOH
sites of 1site/nm
2
–this is a reasonable, but low sorption condition that might correspond
to ferric oxide in sediment or in water treatment by adding ferric chloride to induce
“hydrous ferric oxide” precipitation and adsorption for arsenic removal. A graphic
representation is as follows from Stumm and Morgan, “Aquatic Chemistry 3
rd
ed.,”
Wiley, 1996:

Mason Tomson Visual Minteq Page 7 Adsorption 11/2/2004 7


Mason Tomson Visual Minteq Page 8 Adsorption 11/2/2004 8
The surfaces of most solids accumulate a net charge, σ
o
, and this charge is counter
balanced by an equal and opposite charge in the diffuse water layer around and near
the solid surface, σ
d
, i.e.:

σ
o
+ σ
d
= 0.00

Almost every text seems to use a different set of units to express surface charge and
related quantities, but Visual Minteq uses the following:

T
Surface charge
(mol/L) = N
s
(sites/m
2
)⋅S
A
(m
2
/g)⋅C
s
(g/L)/N
A
(#sites/mol)

The N
s
input is in units of (sites/nm
2
), which is commonly about 1 to 2 site/nm
2
, and
then the program converts to m
2
, internally. This expresses surface charge in moles
of surface charge per liter of solution –see example below.

Ordinarily, it would be expected to treat the charge on the surface just like is done
with activity coefficients and ionic strength and use some simple expression to correct
for the surface charge as is done using the Davies or the Debye-Huckel equations.
The problem with this reasonable approach is that practically solids accumulate so
much charge on the surface under some circumstances of pH and ionic strength the
impact on the adsorption or ions can be orders of magnitude in value, but at other
ionic strengths or pH’s it may not too important. All these circumstances are treated
with the electrostatic double layer models used in Visual Minteq (from the Minteq
tutorial on the EPA web site):

Mason Tomson Visual Minteq Page 9 Adsorption 11/2/2004 9


The iron, manganese, silica, etc., metal oxide surface accumulates charge similar to
the surface of the pH electrode, wherein the ≡SOH groups can either add a H
+
at
lower pHs values to form a net ≡SOH
2
+
or at higher pH values loss of a H
+
to form a
net negatively charged surface, ≡SO
-
:

≡SOH + H
+
≡SOH
2
+

and
≡SOH ≡SO
-
+ H
+

wherein the ≡SOH refers to the surface metal hydroxide, such as ≡FeOH with
hydrous ferric oxide or ≡SiOH with silica. The effect of the surface charge, ≡SO
-
or
≡SOH
2
+
, on adsorption is given by a Boltzmann-type factor for activities and in
Visual Minteq it is written as follows:

Mason Tomson Visual Minteq Page 10 Adsorption 11/2/2004 10
z ) T R /( F z z
s
] e [ } X { } X {
⋅ ⋅ ψ −
⋅ =

where z = charge on the ion including the sign, = activity of the ion
immediately next to the surface, = activity of the ion is solution far enough
away to not be influenced by the surface, = Boltzmann factor, (Volts)
surface potential relative to bulk solution and may be positive or negative, F =
Faraday constant = 96,500 C/mol, R = gas constant = 8.31 V⋅C/(mol⋅
} X {
z
s
} X {
z
) T R /( F
o
e
⋅ ⋅ ψ −
o
ψ
o
K) = 8.31
J/(mol⋅
o
K), and T =
o
K. Note for reference that the value of the exponential in the
Boltzmann factor, , is equal to 1.00 for the following common conditions
of 20
) T R /( F
o
e
⋅ ⋅ ψ −
o
C and a common surface potential of 25 mV (from Stumm and Morgan), -note
that this corresponds to about ½ pH unit:

37 . 0 e e e
1 ] K 293 ) K mol /( VC 31 . 8 [ ] mol / C 500 , 96 V 025 . 0 [ ) T R /( F
o o
o
= = =
− ⋅ ⋅ ⋅ − ⋅ ⋅ ψ −


As the surface becomes protonated, ionizes, or adsorbs charged ions, it obtains some
calculated surface charge, , as will be seen below. For a diffuse layer of ions next
to a solid the theoretical relationship between surface charge and surface potential is
given from electrostatic theory by:
o
T
σ

) T R 2 / Z sinh( I 1174 . 0 T
o
2 / 1
o
⋅ ⋅ ψ ⋅ ⋅ =
σ


at 25
o
C with I (M) ionic strength and Z = 1.00. The value of
o
ψ (V)can be either
plus or minus. The sinh(x) function looks like the following:

2 1 0 1 2
5
0
5
3.627
3.627 −
sinh x ( )
2 2 − x


At small values of “±x”, ≈ 2.3⋅I(M)
o
T
σ
1/2

o
ψ (V). For example, for an iron oxide
surface with no other adsorbing ions the surface charge is calculated from the surface
speciation:

o
T
σ
= [≡FeOH
2
+
] - [≡FeO
-
] Net surface charge.

The mass balance for all surface sites, Tot≡FeOH, would be:
Mason Tomson Visual Minteq Page 11 Adsorption 11/2/2004 11
Tot≡FeOH (M) = [≡FeOH
2
+
] + [≡FeOH] + [≡FeO
-
]

In Visual Minteq the reference component for surface sites is always the neutral
species, [≡FeOH], generally written as [≡SOH]. The equilibrium constant for the
formation of [≡FeOH
2
+
] and [≡FeO
-
] are as follows in Visual Minteq terminology in
terms of components, :
1 RT / F
] e [ and } H { and ] FeOH [
o
+ ψ − +


≡FeOH + H
+
≡FeOH
2
+


1
o
29 . 7
1 RT / F 29 . 7
s
29 . 7
2
] 1 Psi }[ H { ] FeOH [ 10
] e }[ H { ] FeOH [ 10 } H { ] FeOH [ 10 ] FeOH [
o
+ +
+ ψ − + + +
⋅ ≡ ⋅ =
⋅ ≡ ⋅ = ⋅ ≡ ⋅ = ≡


as seen in the following screen from Visual Minteq. It should be noted that the {H
+
}
term refers to the normal aqueous hydrogen ion activity which is the concentration
times the activity coefficient, {H
+
} = [H
+
]⋅ , which the program calculates. For
mathematical simplicity the Boltzmann factor term is treated as an explicit
component and given a name, Psi
+
γ
H
o
1, in Visual Minteq. This is illustrated in Visual
Minteq (details of how to open this screen will be listed below):




In summary, surface ionization and complexation is treated exactly like any other
acid/base or complex species in solution, except that the Boltzmann correction term
must be solved simultaneously with the sinh(…) term, similar to the activity
coefficient in solution and the Davies equation. Even though this complicates the
algebra, it adds nothing new to the formulation of a problem.

≡FeOH ≡FeO
-
+ H
+
, or
1
o
1 1 93 . 8
] 1 Psi [ } H { ] FeOH [ 10 ] FeO [
− − + + − −
⋅ ⋅ ≡ ⋅ = ≡

Mason Tomson Visual Minteq Page 12 Adsorption 11/2/2004 12


Expressed as the corresponding dibasic acid with two ionization constants, ≡FeOH
2
+
,
would have pK
1
= 7.29 for ≡FeOH
2
+
≡FeOH + H
+
and pK
2
= 8.93 for the reaction
≡FeOH ≡FeO
-
+ H
+
, in an exactly analogous manner to a dibasic acid, H
2
A.


Illustration of how to run Visual Minteq 2.30:

Adsorption 1 HFO.VDA Acid/base reactions of hydrous ferric oxide (HFA).
a. Open Visual Minteq
b. Ionic strength = 0.01 M
c. Select Adsorption and Surface complexation reactions



d. The screen will look like this:
Mason Tomson Visual Minteq Page 13 Adsorption 11/2/2004 13


e. Fill in the following, starting with “1” Specify number… box and then select the
drop-down button and select “2-pK DLM” option from the rather long list of
options. Fill in the numbers 1 g/l, 100 m
2
/g, and 1 site/nm
2
.












f. Click the X! button with the Site Conc. space empty and the program calculates
the Site conc. (low affinity; mmol of sites/l) = 0.166 mM low affinity sites. This
means that with this solid concentration the surface is the same as having
0.166x10
-3
M in solution for titration, etc. We normally just use the low affinity
sites, the high affinity sites are given used to model some systems and are
designated, ≡FehOH, etc. It is important to note that for the X! button to work,
the Site Conc. field must be blank!
Mason Tomson Visual Minteq Page 14 Adsorption 11/2/2004 14


g. Click on the “Go!” button and the “Read Reactions from…” button:



h. The following will appear and double click on the file, feo-dlm.mdb:



This tutorial will use this data base, feo-dlm.mdb, to illustrate the methods, but the reader
is encouraged to open and examine the various other data bases and examine the Minteq
tutorials for explanations of the various details and assumptions.

i. Click on Edit sorption … button and scroll down and click on ≡FeOCd
+
species
and the following will appear:
Mason Tomson Visual Minteq Page 15 Adsorption 11/2/2004 15


This illustrates what the values of the various constants are and it is not normally
necessary to do anything if you want to use the recommended constants, but you can
use this template to change log K values and to enter new constants for species not
listed. We will use these values in all calculations, so just click on Quit. This also
illustrates the way the component Psi
o
1 is defined; the equilibrium constant for Cd
2+

adsorption is:

≡FeOH + Cd
2+
≡FeOCd
+
+ H
+

1 1
o
1 2 1
eq
1
o
2 2
o
2
1
o
eq
} H { ] 1 Psi [ } Cd { ] FeOH [ K ] FeOCd [
or
] 1 Psi }[ Cd { ] FeOH [
} H { ] FeOCd [
] 1 Psi }[ Cd { ] FeOH [
] 1 Psi }[ H { ] FeOCd [
K
− + + + + + +
+
+ +
+
+ +
⋅ ≡ ⋅ = ≡
⋅ ≡
⋅ ≡
=
⋅ ≡
⋅ ≡
=


with K
eq
= 10
-2.9
this is the expression represented in the above screen image for the
species ≡FeOCd
+
.

Again, unless it is necessary to change these values or to add equilibrium values not
listed in the data base, it is not necessary to do anything; when you choose a
component from the list on the Main Menu or you add solid phase, etc., all
equilibrium related to that component and solids will be automatically included.
Click on Quit and then Save and Back to Main Menu and the adsorption data base
will be automatically included in all calculations.

Back at the Main Menu, click on “View/add edit” and the following will appear:

Mason Tomson Visual Minteq Page 16 Adsorption 11/2/2004 16


j. In the Main Menu, click on Run Minteq and then See calculated… and the
following will appear, click on See calculated adsorption parameters:



This Output screen says that 1 g/l of hydrous ferric oxide with 100 m
2
/g surface area
and 1 site/nm
2
on the surface when added to water with 0.01 M ionic strength will
have a pH = 8.015, a value of Psi
o
1 = 0.0048 and surface charge of 0.00111 C/m
2
.
Adsorption 2 HFO low ionic strength.VDA Alternatively, if you had selected the
Calculate Ionic Strength option on the Main Menu, the pH = 7.117, etc…
Mason Tomson Visual Minteq Page 17 Adsorption 11/2/2004 17



Adsorption 3 HFO vs pH 1 mM IS.VDA Log C vs. pH for hydrous ferric oxide with
10 g/l of HFO:

a. Open Visual Minteq, this will reset all parameters;
b. This time use 10 g/l and this will cause the total sites to be about 1.66 mM:


Click on Save and back to main menu.
Mason Tomson Visual Minteq Page 18 Adsorption 11/2/2004 18

c. Set up a pH titration and output and Click on Save and Back to Main Menu:


Notice that the species ≡FeOH(1) is represented as ≡SOH(1) in Visual Minteq.

d. Set ionic strength to 0.001 M and click on Run Minteq, selected sweep results on
the output menu, print to Excel and after a little plot formatting:


Notice that the point of zero
surface charge, where
[≡FeOH
2
+
] = [≡FeO
-
] is at
about 8.1 pH, as expected
from other sources such
zeta potential, and from
(pK
1
+pK
2
)/2 =
(7.29+8.93)/2 = 8.11. The
unusual thing to note about
this curve compared to the
corresponding log C vs. pH
curve for weak acids with the same pK-values is the exceptionally wide range over which
[≡FeOH], the neutral species, is the predominant species –from about 4 pH to 12 pH.
Since the corresponding dibasic acid would have had pK
1
= 7.29 and pK
2
= 8.93, the
middle species, [≡FeOH], would be predominant from pH = 7.29 to pH = 8.93. The
surface potential is the difference: at low pH values the positively charged surface repels
the solution H
+
causing the apparent ionization constant (i.e., where [≡FeOH
2
+
] =
[≡FeOH]) to be about pK
apparent,1
≈ 4.0 versus 7.29. At higher pH’s the opposite happens,
Log C vs. pH for 10 g FeOx/L at 100 m^2/g and 1 site/nm^2
1.E-06
1.E-05
1.E-04
1.E-03
1.E-02
0 1 2 3 4 5 6 7 8 9 1011 1213 14
pH
S
i
t
e

c
o
n
c
e
n
t
r
a
t
i
o
n
,

M
>FeOH2+(1) >SOH(1) >FeO- (1)
at 0.001 M Ionic strength
Mason Tomson Visual Minteq Page 19 Adsorption 11/2/2004 19
the negatively charged surface holds the H
+
on the surface making the pK
apparent,2
≈ 12,
where [≡FeOH] = [≡FeO
-
].


Adsorption 4 HFO vs pH at 100 mM IS.VDS Repeating the above calculations, but at
0.1 M ionic strength produces the following data. Notice that the range that [≡FeOH] is
the predominant species is now only from about 6 to10 pH vs. from 4 to 12 pH when I =
0.001 M. The ionic strength has altered the solid phase predominant species by two
orders of magnitude at the high and lower pH values. This can be shown to have an
enormous impact on anion and cation adsorptions.

Log C vs. pH for 10 g FeOx/L at 100 m^2/g and 1 sit e/nm^2 at
0.10 M ionic st renght .
1.E-06
1.E-05
1.E-04
1.E-03
1.E-02
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
S
i
t
e

c
o
n
c
e
n
t
r
a
t
i
o
n
,

M
>FeOH2+(1) >SOH(1) >FeO- (1)


Adsorption 5 Cd on HFO vs pH at 0.01 M IS.VDA Adsorption of Cadmium to
hydrous ferric oxide versus pH. Produce the following screen and select save and return
to main menu:



Mason Tomson Visual Minteq Page 20 Adsorption 11/2/2004 20
Set the Cd2+ to 1e-7 M, ionic strength to 0.01 M, and do a pH sweep from 0 to 14 pH
and plot the amount of TotCd(aqueous) vs. pH:

TotCd(aqueous), M
1.E-12
1.E-10
1.E-08
1.E-06
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14


Notice that the cadmium is adsorbed but only above about 7 to 8 pH. At higher pH
values, the hydrolysis of Cd
2+
to form hydroxide complexes increases the solubility.

Adsorption 6 Cd on HFO with CdCO3.VDA Impact of carbonate on adsorption. Set
TotCd = 1E-5 M, TotCO3 = 0.01 M and I = 0.01 M and permit Otivite (CdCO
3,ppt
):
Series 2 is without Otivite possible precipitation.

TotCd, aq, M; Series 2 is without CdCO3 ppt.
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
1.E-04
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Cd+2 Series2


Adsorption 7 As(III) As(V) on HFO vs pH.VDA Impact of adsorption on arsenic in
solution: Adsorption or arsenic (III) and (V) to 1 g/l FeOx, I = 0.01, TotAs = 1e-6, in
each case.

Mason Tomson Visual Minteq Page 21 Adsorption 11/2/2004 21
1.E-14
1.E-12
1.E-10
1.E-08
1.E-06
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
AsO4-3 H3AsO3


Adsorption 8 As(III) As(V) on HFO redox.VDA Same pH sweep as above, except
with redox set at pE = -3. Start from the problem above.

a. Set the pe value at –3.0 by selecting the Parameters then Specify pe and Eh:



b. Select Fixed pe and enter “–3” as follows and then Save and back to main menu:


c. Include the redox couple between AsO
4
3-
and H
3
AsO
3
by selecting Redox menu
and add the H3AsO3/AsO4 redox couple as follows and select Add and back to
main menu. Select Run Minteq.
Mason Tomson Visual Minteq Page 22 Adsorption 11/2/2004 22


Notice that nearly all of the arsenic remains in solution as the toxic form, As(III) till
about 8.5 pH, but at this pH, the surface is negatively charged and therefore the As(V) is
repelled from adsorption. This is apparently what happens as the system goes anaerobic
at pE = -3, a common value.

1.E-20
1.E-18
1.E-16
1.E-14
1.E-12
1.E-10
1.E-08
1.E-06
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
AsO4-3 H3AsO3


Adsorption 9 As(III) As(V) Fe(II) Fe(III) on HFO precipitation.VDA Same as above
but with AsO4-3 and H3AsO3 = 1e-6, Fe(II) and Fe(III) = 1E-4 M, pE = -3, also
permitting ferrihydrate (Fe(OH)3) and FeAsO
4
,

precipitation.

a. Set up the following input data:

Mason Tomson Visual Minteq Page 23 Adsorption 11/2/2004 23


b. Select the redox menu on the main menu and select both arsenic and iron redox.



c. Permit both ferrihydrate and FeAsO
4
solid formation as possible solids:



d. Select the pH sweep from 0 to 14 pH and the output of Total Dissolved for each
component in Excel will look something like this after some rearrangements.
First for specific pH = 9.0 and then for pH sweep.


Mason Tomson Visual Minteq Page 24 Adsorption 11/2/2004 24


1E-14
1E-12
1E-10
1E-08
1E-06
0.0001
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
TotAsO4-3 TotH3AsO3 TotFe+2 TotFe+3


Apparently, the minimum Total As conc. occurs at about 8.5 pH where from the above
plot output screen TotAs(III) ≈ TotAs(V) ≈ 3E-9 M ≈ 0.2 ppb TotAs dissolved in
solution. The present EPA standard is 50 ppb and that will be reduced to 10 ppb in 2006.
Alternatively, if the pH is 8.0 instead of 9.0, the TotAs conc. is about the same, but the
predominant form is As(III) which is by far the more toxic of the two forms.

The following is the Component outputs at 8 and then 9 pH.

At 8 pH:
Mason Tomson Visual Minteq Page 25 Adsorption 11/2/2004 25


At 9 pH. Notice the change in oxidation state of the predominant dissolved form or
arsenic, As(III) at 8 pH and As(V) at 9 pH.



Mason Tomson Visual Minteq Page 26 Adsorption 11/2/2004 26

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