Chem 223: Experiment 3

Complexometric Determination of Nickel

(This experimental procedure of this experiment is mainly based on the lab. Volumetric
determination of Nickel”. Chem 223. UIUC)

References: 1. C. Chaps 7, 9 (223-235), 3 (pp. 79-86)

2. Harris, 7th ed. Chap. 12
3. S&W Chaps 6, 10, pp581-583
4. SWH, Chaps 4, 11, pp. 771-773

I. Purpose of the experiment

A volumetric titration is one in which the volume measurement capabilities of the burette are
exploited to determine a highly precise value of the mass of one reagent needed to react
stoichiometrically and completely with an unknown. The particular type of titration being
examined in this lab is a complexometric titration in which the titrant, EDTA, is a ligand that can
react completely with the analyte, Ni(II), with a well-defined stoichimetry. This lab also
introduces the concept of a secondary standard, since the EDTA is standardized against CaCO 3
to allow calculation of the amount of nickel in the solution

II. Introduction
The use of ethylenediaminetetraacetic acid (EDTA) as a titrant for the determination of metal ion
concentrations is a common analytical method.

HOOC - CH2 CH2 - COOH

>N - CH2 - CH2 - N<
HOOC - CH2 CH2 - COOH

EDTA

EDTA is a hexaprotic acid (pK1 = 0.0, pK2 =1.5, pK3 = 2.0, pK4 = 2.8, pK5 = 6.2, pK6 = 10.3),
since each of the carboxyl groups and H+ on the amines is ionizable. The completely
deprotonated (dissociated) EDTA molecule is capable of forming up to 6 separate coordination
bonds with a single metal ion; this is accomplished by donation of six separate lone pairs of
electrons on the dissociated EDTA molecule to empty orbitals existing on the metal ion.

The structure of EDTA and the magnesium-EDTA complex (without the hydrogen atoms) is
shown below:

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The resulting product of this reaction is a metal-chelate complex with one-to-one stoichiometry;
the reaction is described as:

Y4- + Mn+ ----> MYn-4

where Y represents the completely dissociated EDTA molecule and M represents the metal ion.
The reaction is usually rapid and, under the correct conditions, quantitative (conversion of 99.9%
of the metal ions into a metal-chelate complex is achieved at the equivalence point). The
condition of greatest concern is the pH of the solution containing the metal ion. Since EDTA is a
weak, polyprotic acid and can only react effectively with a metal ion when it is completely
dissociated, the pH of the metal ion solution directly affects whether the titration can be
performed quantitatively. This is reflected in the conditional formation constant for the
titration; a conditional formation constant for an EDTA titration is the product of the intrinsic
formation constant (the equilibrium constant for the condition where all EDTA is completely
dissociated) and the fraction of EDTA which is completely dissociated. This fraction is
determined by the pH of the solution containing the metal ion. (For a more detailed of conditional
formation constants see your text book.)

A note about indicators: Another complicating factor in this analysis is the choice of an
indicator; the indicators for EDTA titrations are chemically similar to EDTA itself. They are
polyprotic acids which can form complexes with the analyte and these complexes impart a color
to the solution.

HxInd + M M(Ind) + x H+
(Color #1)

Ideally, only a small fraction (> 0.1%) of the metal is complexed by the indicator, so that a
quantitative amount of the metal remains free to react with EDTA as it is added during the
progress of the titration; once sufficient EDTA has been added to reach the equivalence point, the
first excess drops of EDTA react with the metal-indicator complex to liberate the indicator and
produce a color change.

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 M(Ind) + Y + x H+  MY + HxInd
(Color #2)

To achieve this ideal behavior, the formation constant should be large enough to prevent reaction
between the EDTA and the metal-indicator complex before the equivalence point is reached, yet
significantly smaller than the formation constant for the metal-EDTA complex so that the EDTA
may displace the indicator from its complex with the metal after only adding a drop or two of
excess EDTA solution.

In this analysis, the standardization of the EDTA titrant solution against the Ca 2+ solution is
carried out at pH = 9.7 and uses the indicator Erichrome Black T, which is added as a solid
powder (1g Erichrome Black T in 100 g NaCl). The initial solution color is wine-red and the
endpoint is marked by a sharp color change to a deep blue.

The titration of the sample solution for Ni content is carried out at the same pH, but uses
Murexide as an indicator, since Ni forms complexes with Erichrome Black T which are too
stable to be decomposed by EDTA. Additionally, the pH 9.7 buffer (an NH3/NH4+ solution) must
be added carefully, so that excess NH3 does not interfere with the formation of the complexes
between Murexide and the analyte metals. The initial color is yellow to greenish-yellow and the
endpoint is marked by a change to a violet color. This change is slightly less sharp than the
Ca/EDTA titration using Erichrome Black T, with an orange color being seen just prior to the
endpoint. Once this orange color appears, the titration should be performed very slowly to avoid
overshooting the endpoint volume. Unfortunately, this lower pH reduces the stability constant for
the Ni-Murexide complex as well; as a result the titration does not produce a sharp endpoint, but
starts out as orangish-yellow and progresses gradually through a series of peachy-orange colors
until a reddish-violet color is reached at the endpoint. Since no sharp color change is observed,
the best strategy for obtaining a reproducible endpoint is to have a titration solution at the
endpoint color for comparison while carrying out each individual titration.

III. Reagents and materials

A. Reagents and Solutions available:

 Dry 1-2 g of CaCO3 for 90 min at 110°C in a weigh bottle. Cool to room temperature in
a desiccator before using.

 Concentrated HCl (12M)

 Eriochrome Black T (ground 1:10 with NaCl).

 Murexide indicator: Dissolve 150 mg dye in 100 g absolute ethylene glycol. Aqueous
solutions of the indicator are not stable for more than 1 day. Another way to prepare this
indicator is to grind 0.20 g of murexide to a fine powder with 20 g of potassium nitrate.

 unknown EDTA solution which was prepared from Na2H2Y.2H2O

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  a 0.8 g/L (~ 4 mM) solution of MgCl2·6H2O

 pH 10 buffer (2000 mL has been prepared by dissolving 140.0 g of NH4Cl in 650 mL of

deionized water, adding 1136 mL of conc. ammonia and diluting to 2000 mL.)

 Five 250 mL volumetric flasks and five 250 mL beakers for preparing Ca 2+ solution by
group of 4 students.

 Each 100.0 mL volumetric flask containing unknown sample of Nickel have been
prepared for each student. To save time, the sample has already been dissolved for
students.

B. Solutions to be prepared:
1. Preparation of Standard Solution of Ca2+.

 Weigh (to the nearest 0.1 mg on the analytical balance - an opportunity to weigh by
difference) about 0.15 - 0.25 g of primary standard calcium carbonate.
 Transfer the solid directly from your weigh bottle to a 250.0 mL volumetric flask, then
rinse the neck of the flask with about 20 mL of water.
 Calculate the amount of and add 6 M hydrochloric acid (dilute the 12 M HCl in the hood
to 6 M) dropwise until effervescence ceases and the solution is clear. Be careful to add
only enough acid to complete the evolution of CO2 . It may not dissolve the solid
completely, but it should dissolve most of the CaCO3. A large excess of acid may cause
pH problems in the titrations that use this solution.

Dilute with water to the mark, mix the solution thoroughly, and label. I.B.

2. Sample Unknown.
 When you get the unknown solution from TA, dilute the contents to the 100.0 mL line
with deionized water. When diluting to the mark on the neck of the flask, add the last
few drops carefully with a small pipette. If you go past the mark, you have ruined your
unknown, and you'll need to ask the TA for a new one.

IV. Experimental procedure

A. Standardization of EDTA Solution.

• Pipette a 10.00 mL aliquot of the standard calcium solution into a 250.0 mL Erlenmeyer
flask and add about 10 mL of an ammonia-ammonium chloride buffer solution pH9.7. Then
add a few crystals of the Eriochrome Black T indicator. The solution should look violet (or
pink-violet). If the solution, instead, appears to be a pale peach-pink, the problem is that the
pH is too low; add 5 mL more buffer.

• Next add a 5.00 mL aliquot (use a pipette) of a 0.8 g/L (~ 4 mM) solution of MgCl2. The
Mg2+ ion is needed to get a sharp color change in this titration.
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 • First, do a “dry-run titration” in which you deliberately over-titrate, i.e. blow past the
endpoint, so you can see the color changes associated with the endpoint. There is no need to
carefully record titrant volumes, since the purpose of this step is to calibrate yourself to the
color changes you want to observe.

• Now carefully titrate with the EDTA solution to the point where the color changes from pink
violet to blue.2. The endpoint is where the solution has just turned blue and no tinge of pink
remains.
• At the endpoint, you have added enough EDTA to complex not only the Ca2+ but also the
Mg2+. You need to do another titration to determine this indicator blank (the amount of
titrant added in excess of that needed to just titrate the Ca2+.) To determine this indicator
blank: place in a 250 mL Erlenmeyer flask ca. 10 mL water, 10 mL of ammonia-ammonium
chloride buffer solution pH 10, Eriochrome Black T indicator and 5.00 mL (use a pipette) of
the Mg2+ solution. Titrate to the same blue endpoint as before.
• Repeat both the Ca2+ titration and the indicator blank titration at least two additional times 3,4
to get good, average values and enough data so you can calculate precision. The average
volume used for the indicator blank titration needs to be subtracted from the volumes used in
the Ca2+ titration to determine the correct amount of EDTA required to react with the Ca 2+
standard solution.

B. Determination of the Nickel Unknown via Direct Titration

• Pipette a 10.00 mL aliquot of your unknown nickel solution into a 250 mL Erlenmeyer flask
and add about 10 mL of an ammonia-ammonium chloride buffer solution pH 10. Then add
Murexide indicator and about 20 mL of DI H2O. Do not add any MgCl2.

• Titrate carefully with the EDTA solution to the point where the color changes from yellow to
purple. The color will be yellow before the endpoint and change to purple at and beyond the
endpoint. Take as the endpoint the first definite purple color (no yellow remaining). For best
results, a titration should use more than 10 mL, but not so much that you have to use more
than one burette-full. Adjust the size of the aliquot on Ni2+ as necessary to stay within this
range.

• Repeat the titration with at least two additional aliquots of the nickel solution. Each time,
check that the pH is in the desired range.

C. Determination of the Nickel Unknown via Back Titration.

Please take care to add the reagents in the order specified here.

- Pipette a 10.00 mL aliquot of your unknown nickel solution into a 250 mL Erlenmeyer flask
and add about 10 mL of the ammonia ammonium chloride buffer solution, pH9.7.

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 - Add a volume of EDTA solution that is 5-6 mL greater than what you would expect to be
needed to exactly react with the nickel; record this volume added accurately (to 0.01 mL).
After the EDTA has been added, then add Eriochrome Black T indicator1. Do not add any
MgCl2.
- Prepare a total of four of these samples.3 Drain the EDTA solution from the burette and rinse
well with water; drain; rinse the burette with a small amount of standard calcium solution;
drain; fill the burette with the standard calcium solution.

- Titrate the excess EDTA in each of your samples by using the standard calcium solution
titrant. The endpoint will now be the color change from blue to violet. The color will be blue
before the endpoint and change to violet at and beyond the endpoint. Take as the endpoint the
first permanent appearance of violet.

NOTES

1. Add sufficient indicator (2-3 drops if using indicator solution or size as green bean seed if
using indicator solid ) to give a pale but distinct color to the solution. The solution should
not be so deeply colored that it is difficult to see through it.

2. Always titrate with a piece of plain, white paper beneath the flask so you can see color
changes more clearly.

3. It is advisable to titrate standards and unknowns during the same lab period because the
EDTA solution is somewhat unstable.

4. You need at least three assay values. To be safe, use one extra aliquot.

Graphical summary of the 4 types of titrations in this lab. Thin lines: concentration not known at the time
of titration. Thick lines: standard (primary is Ca 2+, secondary is EDTA).

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FOR YOUR REPORT

Calculate (1) molarity of your Ca2+ stock solution, (2) molarity of your EDTA solution (mean
value),(3) total mass (mean value) of the Ni(II) in your sample (100 mL) in milligrams. Report a
value for the direct titration, the back titration, and the average of the two.

Report the standard deviation of your measurements (both direct and back titration): (1) in
absolute terms (see Appendix I). (2) as a relative standard deviation in parts per thousand. (3)
calculate a 95% confidence interval for your results (use the t statistic; see Appendix I).

Test for a statistically significant different in precision (F-test; see Appendix I) between your
direct and back titration results at the 95% confidence level. Test for a statistically significant
difference between the mean values (t-test) for your direct titration and back titration results at
the 95% confidence level.

Estimate the uncertainty involved in each step of the direct titration (weight of standard, dilution
of standard, titration volume, etc.). Use propagation of error techniques (see Appendix (() to
arrive at the resultant uncertainty in your answers. How does the magnitude of this predicted
value compare to your observed standard deviation?

As an example of uncertainty estimation, you might feel very good about your ability to locate
the endpoint, so assign it a ± 0.02 mL uncertainty. Or, you might feel your technique is shaky, so
assign a ±0.05 mL uncertainty to it. Often, the volume uncertainty in a piece of glassware is
stated right on it. Analytical chemistry textbooks also list uncertainties for all types of glassware.

Draw the structure (indicate all atoms) of the disodium salt of EDTA (abbreviated Na 2H2Y where
EDTA is Y4-). When Na2H2Y is dissolved in water, what immediately happens to the two sodium
atoms?
What are four essential requirements for a volumetric analysis (also called a titrimetric
analysis)?

Why is MgCl2 added to the solution for standardization of EDTA?

Can you simultaneously determine Nickel and copper in a mixture using murexide indicator? If
you can, describe the procedure.

Why was the Ca2+ stock solution prepared from CaCO3 plus HCl instead of from solid CaCl2?

What is the purpose of the HCl? Why do you add HCl until effervescence ceases?

What compound is the primary standard for this determination?