Chem 223 : Experiment 7

Ion – exchange and Titration Method for the Determination of

Cobalt and Nickel

References:

1. C, Chaps. 13 (pp. 371-376), 16 (pp. 451-455).

2. H7, Chaps. 19, 23, and 25
3. S & W, Chaps. 15 (especially pp. 443-49), 17 (pp. 487-89).
4. SWH, Chaps. 18, 20 (pp. 505-518), 25 (pp. 652-653), 29 (pp. 715-716).
5. J. S. Fritz & G. H. Schenk, Jr., Quanta. Analyt. Chem., 4th ed., (pp. 582 & 621).
6. J. A. Dalziel and A. K. Slawinski, Talanta 15, 367-372 (1968).
7. Bjerrum, A. S. Halonin, and L. H. Skibsted, Acta Chem. Scand. 29A, 326-332
(1975).
8. Chem 222. Truman State University
The procedure of separation of Co2+ and Ni2+ in this experiment is mainly based on the lab.
“Spectrophotometric determination of cobalt and nickel” Chem. 223. UIUC

I. Purpose of the experiment

Determination of multiple components in a single unknown is frequently required. An analyst

has a choice of attempting a simultaneous determination or performing a preliminary
separation. Each approach has its advantages and drawbacks. Because few techniques are
truly specific, any simultaneous determination usually suffers from some mutual interference
between the combined components, with resulting loss of accuracy and/or precision.
Frequently, however, the resulting uncertainties are less than those introduced by the extra
sample handling required for preliminary separation. Furthermore, simultaneous
determinations are often faster, and therefore more efficient, than those relying on separations.
Generally, the choice of a preferred method must be based on the analyst's assessment of the
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balance among these factors.

In this experiment, the amounts of Co(II) and Ni(II) in a mixture will be determined by two
different approaches. First of all, the Co(II) and Ni(II) will be isolated by ion exchange and
the separated components assayed. After that Co2+ will be complexometrically titrated using
replacement method and Ni2+ will be determined by gravimetric analysis.

II. Introduction

Ion Exchange Chromatography relies on charge-charge interactions between the solutes in

your sample and the charges immobilized on the resin of your choice. Ion exchange
chromatography can be subdivided into cation exchange chromatography, in which positively
charged ions bind to a negatively charged resin; and anion exchange chromatography, in
which the binding ions are negative, and the immobilized functional group is positive. Once
the solutes are bound, the column is washed to equilibrate it in your starting buffer, which
should be of low ionic strength, then the bound molecules are eluted off using a gradient of a
second buffer which steadily increases the ionic strength of the eluent solution. Alternatively,
the pH of the eluent can be modified as to give your solues or the matrix a charge at which
they will not interact and your molecule of interest elutes from the resin. If you know the pH
you want to run at and need to decide what type of ion exchange. If it is negatively charged at
the pH you wish, use an anion exchanger; if it is positive, use a cation exchanger. In many
 cases it may be more advantageous to actually select conditions at which your solutes will
flow through while the contaminants will bind. This mode of binding is often referred to as
"flow through mode". This is a particularly good mode to use in the case of anion exchange.
In this experiment, the separation employs an ion exchange column, and depends on the
selective formation of an anionic complex of cobalt(II). In 9 M HCl the principal equilibrium
forms of the two metal ions are CoCl42- and Ni2+ (or NiCl+).

The Co(II) ions are exchanged onto the resin:

2 Res-NR3 +Cl- + CoCl42- (Res-NR3+)2 CoCl42- + 2Cl-

And the Ni(II) passes through the resin. The R group is often -CH3. In 4 M HCl the CoCl42-
ion breaks down into cationic forms of cobalt(II) and all the cobalt(II) passes through the
resin.

Determinations of the separated components (and of the ions in the mixture) will employ
volumetric and gvarimetric method. For the determination of Cobalt or Nickel, the EDTA
with substitution titration (PAN as an indicator) will be applied and dimethylglyoxime uses as
precipitant for the determination of nickel.

Nickel(II) forms a precipitate with the organic compound dimethylglyoxime, C4H6(NOH)2.

The formation of the red chelate occurs quantitatively in a solution in which the pH is
buffered in the range of 5 to 9. The chelation reaction that occurs is illustrated below.
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Adding tartarate or citrate ions before the precipitation of the red nickel complex prevents
interference from Cr, Fe and other metals. These anions selectively form tightly bound soluble
complexes with the metals and prevent the formation of insoluble metal hydroxides in the
buffered solution.
An alcoholic solution of dimethyglyoxime (DMG) is used as the precipitating reagent during
the experiment because DMG is only slightly soluble in water (0.063 g in 100 mL at 25°C). It
is therefore crucial to avoid the addition of too large an excess of the reagent because it may
crystallize out with the chelate. It is also important to know that the complex itself is slightly
soluble
III. to some extent in alcoholic solutions. By keeping the volume added of the chelating
Reagents
reagent small, the errors from these sources are minimized. The amount of the reagent added
Provided:
is also governed by

Prepare an ion exchange
the presence column
of other metals as demonstrated
such by the
as cobalt, which formteaching
solublestaff. Use
a glass wool
complexes plugreagent.
with the in the bottom then
If a high add a of
quantity slurry ofions
these resinis(Dowex-1X8, 20-50
present, a greater mesh),ofuntil
amount
DMG themust
height
beof the resin column is 15 cm. Never allow the liquid to drop below the resin
added.
level.
 Next, add another glass wool plug to the top of the level of glass wool column. Keep
about 5 cm of liquid above the resin column initially, and keep the liquid just above the
glass wool at all other times. Don't let any air into the resin.

Sample Unknown.

• Obtain an unknown from the TA in a clean 100.0 mL volumetric flask. Add 75 mL of

12 M HCl, then dilute to volume with deionized water and mix thoroughly.

WARNING - Glassware used for this experiment must be scrupulously clean! The various
dilutions are tricky to keep track of, and are a common cause of error.

IV. Experimental Procedure

A. Ion- exchange Separation

After the column is made up, it should be "charged" by passing 9 M HCl through the
column. See the following figure for details, and follow the directions there very carefully.

With a pipette, add 5.00
mL of the unknown onto
the column.1Allow the level
of the liquid to fall to just
the top of the glass wool
before adding the HCl
eluent.

Elute the nickel from the

column with 9 M HCl using
the portions and flow rates
specified below. During
elution of the nickel, the
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cobalt complex will appear

as a green or blue stationary
band on the column. Collect
the NiCl+ complex in a 250
mL beaker.

Transfer the collected

nickel solution
quantitatively to a 100 mL
volumetric flask and dilute
to volume with deionized
water. (A solution).

After all the nickel is

seen to be eluted,2 stop the
flow of eluent, and replace
the collection beaker with
another 250 mL beaker.
 Figure 1. Details of the anion exchange process.

• Elute the cobalt with 4 M HCl using the portions and flow rates as indicated in the figure. As
the HCl is diluted on the column, the blue CoCl42- complex will break down to form a pink
color as Cl- is replaced by water in the complex.

• After all the cobalt is eluted,3 stop the flow and transfer the collected solution to a 100 mL
volumetric flask. Dilute to volume with deionized water (sample B).

• Rinse the column with 75 mL of DI H2O in 15 mL portions. Remove the glass wool, and
dump the resin in the container provided.

The following dilutions should be made during this lab period in preparation for the second
week of this experiment. (Use pipettes and volumetric flasks for all dilutions.)
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 B.Volumetric determination of Cobalt[AS1]

Method A: Direct titration

1. Add 10 mL of 4 M sodium acetate to each 10.00 mL of unknown Co2+ solution (B

solution) and using a pH meter, adjust the pH to 5.8 with 3 M sodium hydroxide.

2. Heat the solution to approximately 950 C using the hot plate/stirrer (DO NOT BOIL!).

3. Add 5 drops of xylenol orange indicator (0.2 g/100 mL, 50% alcohol) and a stirring bar
to the solution, and titrate immediately with EDTA solution. Maintain the solution
temperature in the range of 85-950 C. The endpoint is a sudden color change from violet
to yellow-pink.

Method B: Replacement Titration

1. Add 10 mL of sodium acetate- acetic acid buffer pH=5 to each 10.00 mL of unknown
Co2+ solution (B solution)

2. Heat solution to the boiling using the hot plate/stirrer (DO NOT BOIL!) Add 3 dropps
of copper sulfate-EDTA solution and 8 drops of PAN indicator solution. Titrate to a
green-yellow color with standard solution.

C. Gravimetric determination of Nickel[AS2]

Pipetting 10.00 mL of (A) sample to 250 mL beaker. Add 10 ml. 20% ammonium
chloride solution, add 20 ml. 10% tartaric acid, dilute to 200 ml., heat to nearly boiling,
cautiously add ammonium hydroxide (1:1) from a buret until the solution is slightly
alkaline. Take back to feebly acid by addition of a few ml. HCl. The reason the
precipitation is from acid solution is that a more easily filterable precipitate will result.
The changes in color will indicate the acidity to alkalinity of the solution, but this should
be checked against a sensitive indicator paper (not litmus). If iron hydroxide appears when
the solution is made alkaline, insufficient tartaric acid is present.
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Add 15 ml. of 1% solution (alcoholic) of dimethylglyoxime drop-wise. (A buret is an easy

way to do this.) Add 1:1 ammonium hydroxide until the solution is just alkaline (do NOT
use litmus) then add 2 or 3 drops in excess. (A buret is a convenient method for the
addition of ammonium hydroxide.) A dense red ppt. should form. Stir vigorously. Place
on a hot plate for 15-20 minutes, stir occasionally, finally check alkalinity and filter
through a constant weight sintered glass crucible. Wash well with hot water containing 2
or 3 drops of ammonium hydroxide. Dry at 110o - 120o C for 2 hours. Weigh as
C8H14H4O4Ni containing 20.32% Ni.

TO GET AN ITEM TO CONSTANT WEIGHT: Constant weight is defined as that state

when a substance will not change its weight on heating. This is achieved by heating the
object. Weighing the cooled object and then heating again, cooling again, and weighing a
second time. If the two weights agree within 0.5 mg, the object is said to be at constant
weight. If not then the heating, cooling and weighing process is continued until two
successive weighings do agree within 0.5 mg. Use the final weight in the calculations.

NOTES:

1. Once you load the sample on the resin, the elution must be completed within the same lab
period.
 2. Use dimethylglyoxime test solution with l drop of eluent to test for completion of Ni2+
elution. Add a couple of drops of NH4OH to the test solution. Look for red Ni(DMG)2. In a
separate test, you may also use a drop of the yellow ligand solution (which you will use more
of in week 2). Ni2+ is indicated by a color change from yellow, to pink or red.

3. Use thiocyanate test solution with 10 drops of ethanol and l drop of eluent to test for
completion of Co2+ elution. A blue color signifies Co2+ is present. In a separate test, you may
also use a drop of the yellow ligand solution (which you will use more of in week 2). Co2+ is
indicated by a color change from yellow, to pink or red.

4. Use a burette to deliver the buffer solution, a volumetric pipette to deliver the complexing
agent, and the graduated (Mohr) pipette for the metals and unknown (columns 2, 3, and 4, of
all three tables).

FOR YOUR REPORT

Calculate the Ni(II) and Co(II) concentrations in unknown sample giving by TA .

What are some of the advantages of method A and B used in this experiment? Which would
you expect to be more precise?

Could KCl be used instead of HCl (as a source of chloride ion) for elution? How about LiCl?
Explain.

Why is solution # used as a blank instead of deionized water?

What is the difference between ion- exchange chromatography and ion chromatography? Try
to figure out the principle of ion chromatography for determination of Cobalt and nickel in a
mixture.

What are the advantage(s) and limitation(s) of using gravimetric analysis?

What are gravimetric interferences in determining Nickel by dimethylglyoxime.

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Suggest alternative methods for the determination of nickel in steel. Explain in detail the
principle of ONE alternative method.