Tittrations Based On Complex Formation
Tittrations Based On Complex Formation
Tittrations Based On Complex Formation
Purpose:
The aim is to titrate the cations and determine their amounts in a solution by complexation
reactions.
Theory:
A ligand is an ion that forms covalent bonds by donating its a pair of electrons with a cation or a
neutral atom. A ligand should have at least one pair of unshared electrons. Iodide, bromide etc.
are examples for ligands.
Chelate is the ligand that can form multiple bonds. When a metal ion coordinates with a ligand,
forming metal complex is chelate. Metal-EDTA chelate is an example.
Coordination number is the number of ligand bonds formed around the coordination center. A
cation tends to form a number of covalent bonds with electron donors is its coordination number.
2, 4, 6 are typical values for coordination numbers.
In the titration of ions such as magnesium, calcium etc. , the solution was titrated with EDTA
which has the structure and the bonding sides ( the dark ones) :
EDTA
Eriochrome Black T is a typical metal ion indicator for metal ions in EDTA titrations. Its
behaviour in weak acid by the quation:
The titration methods that are employiong EDTA are direct titration, back titration methods and
dispalcement methods. Direct titration procedures with a metal ion indicator are the the easiest
and most convenient for use. Methods based on indicators for an added metal ion also widely
used. Back titration is used when there is no suitable indicator avaliable, when the reaction
between analyte and EDTA is slow and when the analyte forms precipitates at the pH required
for its titration. In the titration, a measured excess amount of EDTA is put into analyte solution
and after reaction is complete the excess EDTA is back titrated with standard magnesium(or a
zinc) soplution to an Eriochrome black T end point. Displacement titrations are used when any
indicator for an analyte is not available. In displacement titrations, into the analyte solution, an
unmeasured excess of solution which contains magnesium complex of EDTA is put. If the
analyte forms more stable complex than magnesium that rection occurs:
Then liberated Mg(2+) is titrated with EDTA solution. In the determination in water hardness
also EDTA titration is used. After the sample has been buffered to pH 10, the sample is titrated
with EDTA for the determination of water hardness. Eriochrome Black t can be used as an
indicator.
Water “hardness” is defined as the capacity of cations in water to replace sodium or potassium
ions in soap.Hard water contains calcium, magnesium, and heavy metal ions and it forms
precipitate with soap but not with detergents.
Using EDTA as a complexing agent has many advantages that is because it has widespread use.
EDTA is a reagent that forms chelates with all cations except alkali metals and also most of these
chelates are sufficiently stable for titrations. This great stability results from the several
complexing sites within the molecule that give rise to a cage like a structure cation is surrounded
effectively by and isolated from solvent molecules. Another thing is the reagent combines with
metal ions in 1:1 ratio that gives sharpness in titration curves.
Multidentate ligands have advantages when compared with unidentate counterparts. Multidentate
ligands that have more donor groups than unidentates(4 or 6), can react much more completely
with cations that will make sharp end points than unidentates and they form more stable ions.
Another thing is that they react with meatl ions in a singke step but unidentate ligands usually
react two or more intermediate steps.
Discussion:
pH control in complexometric titrations is important. Because when the acid is dissociated, it is
important to realize that electron pairs of carboxylic groups of EDTA are only available for metal
ions. In low pH, EDTA will be in acid form and it will not be an effective complexing reagent.
Another thing is that metal ions form complexes with hydroxide ions, and hydroxide ions
compete with chelating agent for coordination sites in the metal ion. Therefore, effectiveness of
complexing agent will be reduced at high pH. Therefore it should be considered that for every
chealiting agent and metal ion, there is an optimum pH for the titration.
In back titration, excess EDTA is titrated with magnesium or zinc ion solution. For this procedure
to be successful, magnesium and zinc ions form an EDTA complex that is less stable than the
corresponding analyte complex. Therefore, if our analyte becomes magnesium, another reagent
instead of EDTA or\ and cation solution instead of magnesium or zinc ion solution that will form
less stable complex with EDTA than the analyte (magnesium) complex should be used (it should
be considered that in normal conditions magnesium is used for the formation of less stable
complex than analyte but this time it will form strong complex). In displacement titration,
opposite event occurs. This time there should be used an ion solution which our
analyte(magnesium) will make more stable complexes than them. Therefore, if these situations
can be done magnesium ion can get with displacement and back titrations.
Displacement titration is used when there is no available indicator of the analyte therefore, in
order to understand, in order to determine that how much EDTA should be used in the titration,
unmeasured amount Mg/EDTA is used. The aim is to use the Mg ion that forms when the analyte
forms more stable complex than magnesium, as an indicator. Therefore, it is not required to know
its amount because we need to know the amount of EDTA that will determine the end point, we
need to know color change. The reaction is:
In back titration, the opposite case occurs. The logic is to find the concentration of a reactant of
unknown concentration by reacting it with an excess volume of another reactant of known
concentration which is EDTA. Example for this type of reaction (for determination of calcium by
bac titration):
The resulting mixture is then titrated back, consediring the molarity of the excess(EDTA) which
was added. This forms a complex with the excess EDTA molecules until the end-point, when all
the excess EDTA has been complexed.
Water hardness can be defined as the measure of the capacity of the water to precipitate soap. In
other words, hard water is not a health hazard. In daily life, instead of taking calcium
supplements, consuming extremely hard water could be a major contributor of calcium and
magnesium. In some cases such as bathing, washing dishes and clothes and many other uses of
water, soft water is more convenient and efficient than hard water. Also hard water can cause
lemiscales in kettles and washing machines.
The satisfactory titrations of Ca(2+) and Mg(2+), pH should be 12. During experiment, while
adding EDTA pH will decrease that will cause the color change in indicator and that can cause to
not see end point color change therefore pH should stay at 12.
When color change of the indicator is very slow the absence of magnesium is indicated.
Therefore, before the end point color is red because of excess metal ion (at endpoint turns blue)
for water hardness.
In part A, relative error is -6.995% means that the experimental result is less than calculated
result and also this error can be acceptable. For RSD% value which is %1.505, precision is good
means this value is also acceptable.
In part B, standard deviation and %RSD values became zero. Because in both measurements
same results found therefore, good precision occurs. However, because experimental result is
again less than calculated, relative error had a minus sign with a value, which is better than part A
and is good, %0.4822.
In part D, relative error is % -11.02 which is again a minus value and % RSD is %3.646 which is
an acceptable precision, value.
In the three of these parts, all relative errors have minus sign. Therefore, it is obvius that when the
color change occurred, it was not waited enough to see whether color disseappears or not.
Therefore, in all experiments substances were not titrated enough.
In part E, it is seen that all Qcalc. values are nearly same (sometimes by roundation). Tha is
because in all questionable values, the difference between questionable and nearest values nearly
equal to 10 (and of course same widespread). Besides this it is seen that any of the experimental
results cannot be rejected according to Q test.
Conclusion:
Our aim was to titrate the cations and determine their amounts in a solution by complexation
reactions. We used direct titration, displacement titration and back titration for determining
amounts of cations in the solution.
Referances:
1-) http://en.wikipedia.org/wiki/Hard_water
2-) http://infohost.nmt.edu/~jaltig/EDTATitration.pdf
3-)A.Skoog, M.West, R.Crouch, Fundamentals of Analytical Chemistry, Chap.17, pp. 450-482,
Thomson Brooks/Cole, 2004.