Modeling Free Copper Concentrations Using MINTEQ

Introduction
As mentioned in the Introduction to the previous laboratory, complexation is an important
factor in describing the behavior of metal-containing chemical species in aquatic environments. Many molecules and ions are capable of forming complexes with metal ions,
which are generally less toxic than the free (uncomplexed) metal ions.
In this experiment, we will use the computer model named MINTEQ to simulate complexation of metals in aquatic systems. After an introduction to the model, we will compare the measured free Cu concentrations measured in the previous experiment with the
free Cu concentrations predicted by the model. We will then use the model to investigate other factors that can influence complexation and free metal ion concentrations.
As you saw in the experiment last week, free copper concentrations can vary over a
wide range. The calibration standards for the copper probe varied by a factor of 1000
(10-3 to 10-6 M), and the measured free copper concentrations probably varied even
more than this. Because there is such a wide range of possible concentrations (and other
factors), if the results from the copper probe and the model differ by a factor of 10 or
less, the agreement is considered to be acceptable. It is unlikely that the model will
predict the exact concentration measured by the copper probe, but if the relevant parameters were measured accurately last week and if the model was constructed with the appropriate information, the results should be reasonably close. In any case, the trends predicted by the model should match those observed in the laboratory.

Procedure
Part 1. Starting and Getting Familiar with the Model
1. From the Windows Start menu, select Programs, then VISUAL Minteq, then
Visual Minteq to start the program.
2. The screen that appears should be entitled Visual Minteq. This is the Main Menu.
At the bottom left of the screen, you will see an Add Components section where you
will select molecules and/or ions from a drop-down menu and specify their
concentrations for each run.
3. For this demonstration, select Fixed at from the drop-down menu to the right of
pH. A small box with 7.00 will appear to the right of the drop-down menu. This is the
correct pH for the demonstration.
4. Select Parameters which is located at the top left of the screen, to the right of the
File tab. Select Specify Alkalinity. When asked Would you like to specify
dissolved inorganic carbon in this problem? select Yes. A Reminder box will appear

and click OK. Select mg/l CaCO3 as the concentration unit. Type in 150 for the
alkalinity, then click OK.
5. Now you will select the molecules and/or ions from the components drop-down menu
that will be modeled in this run. Select Cu2+. (Be sure that you do not select Cu+; both
ions are on the list.) For this demonstration, a Cu2+ concentration of 1 x 10-4 M will be
used. This can be entered as 0.0001 or 1e-4. Click Add to List. The Cu2+
concentration specified will now be included in the run.
6. To view the list of components that will be included in the run, select View / edit
list. This screen will show you all of the components and their corresponding
concentrations. If you need to delete a component, you can do so by selecting Delete
this component. Select Back to Main Menu.
7. To run this model, select Run MINTEQ. A box will appear in the top left of the
screen telling you that the program is running. In a few seconds, the output screen will
appear.
8. The output screen that is now displayed shows all of the possible aqueous complexes
of Cu that can form under the conditions you specified. With each complex is its
concentration. To view the solids that may form, select Display saturation indices. A
small window will open to show a table with any solids that could form and their
saturation index. Take note of the colors in the saturation index column. The color code
is located at the bottom left of the window. As you can see, five out of six of these solids
that could form are oversaturated. Select Back to main output menu.
9. Also note that this program is not capable of showing the chemical formulas with
proper sub- and superscripts. You are responsible for showing the chemical formulas
correctly in your notebook and report.
10. Record the concentration of free copper (Cu2+). Record the chemical formula and
concentration of the dissolved complex with the highest concentration. (Dont forget that
a larger negative exponent corresponds to a smaller number!) Dissolved complexes
correspond to the table of aqueous inorganic species. All concentrations are reported as
molarity (M). If two or more complexes have comparable concentrations (i.e., within one
or two orders of magnitude of the highest concentration), then record the formulas and
concentrations of them all. [For this demonstration, you can ignore the concentrations of
the carbonate ions (CO32-, HCO3-, and H2CO3) because the alkalinity was fixed.]
11. To start another simulation, select Back to input menu then select Reset. This
will take you to a new Main Menu.

Part 2. Comparison of Free Cu Concentrations From Copper Probe and Model

You should have a table of concentration values for the different constituents (Cu 2+, NH3,
etc.) measured in last weeks laboratory. In this part of the experiment, you will
model those conditions to see how well the model agrees with the free copper
concentrations measured by the copper ion-selective electrode. Only select the
components that are present in the individual water types. Use the values measured
last week for your input for this weeks calculations. You are only required to
model the initial solution prepared (90 mL of river water + 10 mL of 10 -3 M Cu) for
each of the three sites. (You may, of course, choose to do more than this if you
desire.)
Record the concentration of free copper (Cu2+). Record the formula and concentration of
the dissolved complex with the highest concentration. (As in step 14 above, you may
wish to record the formula and concentration of more than one complex if they are
comparable in concentration.)
For the Pee Dee water, the complexing substance in solution was the dissolved organic
matter (DOM). In nature, DOM is a very heterogeneous material composed of many different molecules. Because of this, it is difficult to model the effect of this type of ma terial on complexation. For the Pee Dee water samples, select only Cu 2+ (in addition to
H2O and H+) and enter the measured pH for the samples. This will show the amount of
free Cu that is present due to pH alone. You can then determine the extent of complexation by the DOM by comparing the modeled free Cu concentration due to pH and the
measured free Cu concentration that was due to both pH and DOM.

Part 3. Effect of pH on Free Cu Concentrations

This part of the experiment does not use any lab data from last week.
The pH of the water used in Part 2 varied depending on the source. In this part of the
experiment, you will determine the effect of pH alone (without any complexing
substances in the water) on free copper concentrations.
Selecting only Cu2+ as a component, specify a total copper concentration of 1.0 x 10 -4 M
and pH = 3.0 and determine the amount of free copper under these conditions. Also
record the formula and concentration of the two dissolved complexes with the highest
concentrations. Repeat for pH 5, 7, 9, and 11.
Part 4. Effect of Complexing Substances on Various Metals
This part of the experiment does not use any lab data from last week.
Thus far, all of the simulations have dealt with copper as the metal being complexed. In
this part of the experiment, you will determine how other metals behave in comparison to
copper. Use the following conditions for the metals listed below. Acetate (C 2H3O2-) is a
small organic species (it is the anion of acetic acid, the material which gives vinegar its
characteristic smell and taste) that is sometimes present in small amounts in natural
waters.
Run the model for each of the five metal ions Cu 2+, Pb2+, Cd2+, Ca2+, and Mg2+ at a total
metal ion concentration of 0.0001 M with a pH of 6.0 and an acetate concentration of
0.01 M. (This means to run the model five times, once for each metal ion.) In each case,
record the concentrations of the free metal ion and the formula(s) and concentration(s)
of one or more complexes present at relatively high concentration.
When you have completed all your calculations, close the program by clicking the X in
the upper right corner of the screen, then clicking on OK when asked whether you want
to close the program.

In Your Report
Organize your data and results for Part 2 into a table. Use the table of results from last
week (that you made for the beginning of this lab) and add columns for the additional information you gathered today.
Prepare two separate tables summarizing the conditions and results from Parts 3 and 4.
Answer the questions listed below.

Questions
1. How well did the modeled free Cu results agree with the free Cu measured for the
three sources of water last week? Describe the correspondence between the model and
copper probe in terms of the factor of 10 principle described in the Introduction.
2. The Pee Dee water was modeled using only the total Cu concentration and the pH.
How well does the modeled free Cu concentration agree with the measured free Cu
concentration from the lab last week? What does this indicate about the effect of DOM
on Cu complexation?
3. In Part 3, what was the relationship between the concentration of free copper and
the pH? As the pH increased, which complexes increased in concentration and which decreased? Are these trends and relationships reasonable? (Dont forget the relationship
between pH, the concentration of H+, and the concentration of OH-.)
4. In Part 4, which of the modeled metals had the highest level of complexation when
acetate was added? (I.e., which had the lowest level of free metal ion?) Which had the
lowest level of complexation? If you had to generalize based on these results, which
types of metals form complexes to a greater extent, transition and post-transition metals
or alkaline earth metals?