Professional Documents
Culture Documents
Chapter 13 EDTA Titrations: 12-1 Metal Chelate Complexes
Chapter 13 EDTA Titrations: 12-1 Metal Chelate Complexes
What does the equation for complex formation look like? Its really quite simple
M + nL 6MLN
We measure this equilibrium using a Formation Constant Kf
Kf = [MLn]/[M][L]n
Now if we are dealing with a complex ion system that has several different states
lie ML1 and ML2 and ML3...ML6 you have lots of equilibria that are all linked together
and things get relatively ugly pretty quickly.
However for a multidentate like EDTA that forms a 1:1 complex it is quite simple
M + EDTA WM@EDTA
Kf = [M@EDTA]/[M][EDTA]
2
3
A second reason would be cooperativity. Once the EDTA is bound at one site,
the metal and the EDTA are now physically tied together so the second site is
physically close and can bind almost instantly.
A third, more subtle argument effect is based on the entropy of the reaction.
Entropy is a measure of randomness, and thing that more ordered are generally less
favored than thing that are more random. If we have a complex between 1 metal and 6
monodentate ligands, you enforce order on 7 different compounds. If you have a
complex between a metal and a single 6-dentate ligand, you only enforce order on two
molecules, so this is much more favored.
13-2 EDTA
While there are a host of biologically relevant complexes we might study, we will
focus on complexes between EDTA and metals because the turn out to be excellent
complexes for quantifying metals in solutions.
Here is the Structure of EDTA Figure 13-1
Notice that EDTA has 4 COOH functionalities and 2 NH2 functionalities. Each of
these groups can complex with a metal, so this one molecule usually acts as a
multidentate molecules to form a 1:1 complex with metal thus our Formation Constant
Kf usually looks very simple.
Kf = [MEDTA]/[M][EDTA]
The Kf for most multivalent metals and EDTA is VERY large. 1010-1030 (See
table 13-1)
4
5
However you should appreciate the fact that each of the functional groups is and
acid or a base. You can see that this compound is going to have some interesting
Acids-base properties , and you might wonder which of the acid/base forms of EDTA
the [EDTA] in the above equation refers to.
Now you might expect that dealing with 1 Kf and 6 Ka’s might make thing pretty
complicated, but we can simplify the math very easily, so we don’t have to deal with
these complications. (Will look at in more details in section 13-5)
There are actually two different pH effects you have to worry about. AS you will
see, the binding constants are determined for the EDTA-4 form, because this is the form
that binds metals the best. This form only occurs when the pH of the solution is 11 or
so. As the pH gets lower, the % of EDTA in this form gets lower, so the binding of
metal and EDTA also gets lower
In the other direction you should remember from Gen Chen, that metal hydroxide
complexs are only slightly soluble, so they tend to precipitate out of solution. As the pH
of a solution goes up, the [OH] goes up, and this tends to make many metals ppt out
has hydroxides. Once the metal has ppt’s out, it is not in solution, so it cannot react,
and no chemistry can occur.
The effect of hydroxides can be ameliorated through the use of auxiliary
complexing agents. These are others anions that form metal complexes, like
ammonia, tartarate, citrate, or ethanolamine, however thee complexes are soluble, so
the metal stays in solution and can continue to react.
The use of auxiliary complexing agents is a little trick, because you have a
competition between the metal-complexing agent and Metal-EDTA complex. The Kf for
the metal-EDTA complex must be many orders of magnitude larger than the Kf for the
metal-auxiliary complex agent so that the EDTA can remove the metal from the
complexing agent.
6
Direct Titrations
In direct titrations you simply add an indicator to a solution of the metal ion and
titrate with EDTA. Before you start the titration yo need to check that the pH of the
solution gives a good Kf’ and that the pH is consistent with you indicator color change
as well. auxiliary complexing agents like ammonia, tartarate, or citrate may be added
to block formation of insoluble OH complexes
metal does not displace the analyte ion from its complex with EDTA.
Back titration are used when the metal ion blocks the indicator (see above),
when the metal-EDTA complex forms too slowly, or when the metal precipitates in the
absence of EDTA.
Masking
I mentioned earlier that you can add auxiliary complexing agents to keep metal
ions in solution. You can also add masking agent that will bind so tightly to a metal
ion that it will not titrate with EDTA. These can be used to prevent other ions from
interfering in a given titration. For instance CN- (cyanide) will form strong complexs
with Zn2+, Hg2+ Co2+,Cu+, Ag+, Ni2+ Pd2+ Pt2+ Fe2+ and Fe3+, but not Mg2+,Ca2+, Mn2+ or
Pb2+ so you can titrate any into in the second set in the presence of an ion from the first
set by adding CN- to the solution (Note CN- is extremely toxic -don’t do this at home)
CN- is especially nice because you can demask it with formaldehyde
F- is an example of another masking agent, if you read some of the warnings in
the text you find that it too, is fairly nasty stuff, so we won’t use masking agents, per se
in the lab.
In the lab that you so, however, we do something like making. We will titration a
mixture that contains both Mg2+ and Ca2+. In our first titration the indicator won’t
change color until both metals are bound by the EDTA, so what we wil determine is the
total metal in the sample. In the second titration we will add more OH-. This additional
OH- makes the Mg2+ precipitate out of the solution as Mg(OH)2 so only Ca2+ remains in
solution to be titrated.
8
If you think back to the previous chapter you should remember that the " value
for a particular ionization state is a function of the K’s and the [H+] of the solution for "-4
the equation is:
Don’t worry about memorizing this equation or making calculations on it. To save
people math errors and memorization, the values for "-4 have already been calculated
and tabulated in table 13-3 of your text. (Overhead)
Why are we worried about the "-4 value?? Because, as shown table 13-1, the K
of complex formation between metals and EDTA are usually given in terms of the
complex of the metal and the Y-4 form of EDTA. Yet, if you look at table 13-1, at any pH
less that 13, less than 100% of the EDTA in solution is in the Y-4 form.
This allows us to calculate the CONDITIONAL FORMATION Constant (Kf’) at any pH.
Let’s try an example. Say we wish to titrate Ca+2 with EDTA at pH 10, what is our
Conditional Formation Constant?
One general trend you should see is that as pH gets lower so does the Kf. At what point
does it get so low that we can no longer do the titration?? As a general rule of thumb
we use 108 as a cutoff. Thus Kf’ must be >=108 for an EDTA titration to work.
Let’s try another one. What is the lowest pH at which you can successfully titrate
+2
Fe ?
pMetal vs ml of titrant
The curve has three region to worry about, before the EP, at the equiv. point and
after the EP.
Let’s carry on with the problem we started above, a titration of Ca with EDTA at pH 10,
since we have already calculated that Kf’= 1.7610 +10
Lets define the rest of the parameters, we are titrating a 50 ml solution of
0.01M Ca with 0.01 EDTA. Since EDTA and Ca react to form a 1:1 complex, you
11
2. Another point This is easy let's pick the initial point and, say 30 mls
At 30 mls
What are the moles of EDTA and metal at this point?
Mole Ca 2+ = 50 ml x .01M = .5 mmoles
Mole EDTA = 30 mls x .01M = .3 mmoles
Reaction table:
Ca 2+ + EDTA 6 Ca@EDTA
Before reaction .5 .3 0
Reaction -.3 -.3 +.3
After reaction .2 0 .3
2. Equivalence point
At the equivalence point we have
moles Ca 2+ = 50 ml x .01 M = .5 mmole
moles EDTA = 50 ml x .01 M = .5 mmole
Ca 2+ + EDTA 6 Ca@EDTA
Before reaction .5 .5 0
Reaction -.5 -.5 +.5
After reaction 0 0 .5
It is our task then, to use the K at this point to figure out how much free Ca 2+
is left in the solution from the back reaction.
Let’s look at the equilibrium calculation:
12
[Ca]=[EDTA]=X;
Taking into account the back reaction
[CaEDTA]=.005-X
So K eff=.005-X/X 2
Now, you could multiply through by X 2 and use the quadratic equation to
solve the above equation, but it is a waste of your time. With K so large, X is
going to be small compared to .005, so the -X term can be neglected. Thus:
K f’=.005/x 2; X 2=.005/K f’; X=sqrt(.005/1.76x10 +10)=sqrt(2.84x10 -13);
X=5.33x10 -7 ;pCa=6.27
Ca 2+ + EDTA 6 Ca@EDTA
Before reaction .5 .6 0
Reaction -.5 -.5 +.5
After reaction 0 .1 .5
[Ca@EDTA] = 4.55x10 -3 M - x
14
BEWARE
In the above treatment I have totally ignored any other equilibrium like Metal-OH
or Metal-Complexing agent. To calculate a true titration curve under these conditions
takes a bit more work and a few more pieces of scratch paper. We will have to skip
over this for this class.