Determination of Zinc and Nickel Concentration by: Ion Exchange Chromatography,

Chelometric Titration, and Atomic Adsorption

Chem 2272L-002
Oct-24-2007

I. Introduction

Ion-exchange chromatography is method used to separate ions; where a

mobile phase interacts with a fixed phase and the ions of interest are separated due
to their properties of interaction with the fixed phase. In this experiment the fixed
phase is an ion-exchange resin and the mobile phase is a solution containing zinc
and nickel ions. Anion exchange resins, like the one in this experiment, are high

molecular weight polymers with amine functional groups such as

. In

the presence of hydrochloric acid, zinc ions form chlorozincate anions which replace
the chlorine on the resin; nickel ions pass through the column unaffected and can
be collected. When water is passed through the column hydroxide ions replace the
chlorozincates bonded with the resin, which then decompose into zinc and chloride
ions which can be collected. In this experiment only one ion-exchange column was
utilized for separation. Had more columns been used there would have been an
increase in the experiment time; an increase in precision and accuracy would also
have occurred in correlation with the increased number of samples.
Once the metal ions are separated they can be titrated using
ethylenediamine tetraacetic acid (EDTA). One mole of EDTA can chelate one mole
of metal ions, if the molarity of EDTA is known the amount of EDTA used in titration
can be used to determine the concentration of metal ions in the sample.
An alternate method for determining the concentration of metal ions in a
sample is Atomic Adsorption Spectroscopy (AAS). In this method a solution,
containing ions, is passed through a flame and atomized. The adsorption of certain

wavelengths of light by the sample is recorded, and the amount of adsorption

determines the amount of the analyte being analyzed.

II. Procedure
1. Column Preparation
A small amount of glass wool was placed at the end of one buret and packed.
Resin, mixed with 6M ammonia, was added to test if the glass wool prevented the
resin from passing through the stopcock. About 33 mL of resin was added slowly to
the column with care taken to avoid the formation of gaps and bubbles in the resin
column. Excess ammonia was drained from the column so that the fluid level did
not fall below the surface of the resin. 100 mL of 6M ammonia was then passed
through the column at a rate of 5.01 mL/min, followed by 200 mL of deionized
water, and 150 mL of 2M hydrochloric acid.
The unknown sample was prepared by adding 75 mL of unknown solution,
containing zinc and nickel ions, with 16 mL of concentrated HCl, and then diluting to
100 mL. The sample was then slowly passed through the column, and nickel ions
were collected in a flask at the bottom of the column. 125 mL of 6M HCl was
passed through the column to finish eluting the Ni. Zinc ions were collected by
passing 150 mL of water through the column, the resulting solution was collected in
a flask.
2. Titration of Nickel
The collected nickel containing solution was evaporated on a hotplate till dry
to eliminated excess HCl. The resulting residue was dissolved in 100 mL of water

and 16 mL of pH 10 buffer was added to the solution. 30 mL aliquots were taken

from the parent solution and a small amount of murexide was added as an indicator.
The solution was then titrated with EDTA.
3. Titration of Zinc
The collected zinc containing solution was diluted to 250 mL, and tested
using 30 mL aliquots. Sodium bicarbonate and excess pH 10 buffer was added to
each sample in order to reach the required pH 10 for titration. Small amounts of
Eriochrome Black T were added to each sample as an indicator, and the solution
was titrated with EDTA.
4. Atomic Absorption Spectroscopy
Several standards were prepared for both nickel and zinc solutions; 5 ppm,
10 ppm, and 15 ppm were prepared for both zinc and nickel, and extra solution of
30 ppm was prepared for nickel. Two solutions were made for each zinc and nickel
containing 10 mL in 100 mL, and 15 mL in 100 mL.
Each sample was then run through the AAS using an air acetylene flame, with
wavelengths of 341.5 nm for nickel and 213.9 nm for zinc; slit widths of 0.5 were
used for both nickel and zinc.

III. Data and Observations

1. Data
Table 1 contains data for nickel titration, all samples were 30 mL aliquots and
were titrated with 0.001M EDTA.

Table 1: Amount of EDTA Added During Nickel Titration

Titration One
Titration Two
Titration Three
Mean EDTA Added

mL EDTA Added
16.48
15.65
16.38
16.17

Table 2 contains data on zinc titration, all titrations were 30 mL aliquots

titrated with 0.001M EDTA.
Table 2: Amount of EDTA Added During Zinc Titration
mL EDTA
Added
Titration One

2.71

Titration Two

2.70

Titration Three

2.40

Titration Four

2.68

Titration Five

3.12

Titration Six

2.90

Mean EDTA Added

2.75

Table 3 contains data on nickel AAS runs, with concentrations and

absorptions. Unknown sample 1 is 10 mL unknown in 100 mL water, and unknown
sample 2 is 15 mL in 100 mL water.
Table 3: Atomic Absorption Spectroscopy Data (Nickel)

Standard Runs
#1
#2
#3
#4

Concentration
Absorpti
(ppm)
on
15.0
0.084
20.0
0.103
25.0
0.135
30.0
0.165

Unknown Sample 1
Runs
#1
#2
#3
Mean

Concentration
Absorpti
(ppm)
on
18.6001
0.100
17.9092
0.097
18.3260
0.099
18.2784
0.099

Unknown Sample 2
Runs
#1
#2
#3
Mean

Concentration
Absorpti
(ppm)
on
26.7621
0.145
27.2662
0.148
28.6202
0.155
27.5495
0.149

Chart 1 plots concentration of nickel as a function of absorbance for the

standard runs as well as the mean for unknown samples one and two.
Chart 1: AAS Nickel Concentration as a Function of Absorbance

2. Observations:
During ion-exchange chromatography the resin in the column was not
uniformly mixed. Several gaps were present, although they were not numerous.
After the addition of HCl the resin changed color from orange to bright yellow.
Prior to addition of the unknown solution to the column it was allowed to set
for two days, the column was saturated with HCl solution, and did not dry out during
this period.
The column was not completely drained of final addition of deionized, it is
possible that some of the zinc solution remained in the column. Given the large
quantities of water that already passed through the column, the majority of the zinc,
if not all of it, was already collected.
During the evaporation of nickel a small portion of the collected nickel turned
brown while the remainder stayed green. The brown nickel may have represented
the formation of NiO.

IV. Calculations and Results

1. Calculations
Mean and Standard Deviation of EDTA Added for Nickel and Zinc
Titrations:
x

x
n

(x

x)2

n 1

0.241mL(Zinc)

Mean and Standard Deviation of Concentrations for Nickel and Zinc

Determined by AAS.

Determination of Unknown Nickel and Zinc Concentrations by

Chelometric Titration:

Determination of Unknown sample 1 Nickel Concentration by AAS:

Determination of Unknown sample 2 Nickel Concentration by AAS:

2. Results
According to AAS the nickel concentration of the original unknown sample
was 0.0031292M, while chelometric titration yielded 0.002396M. There is a 30.60%
error between these two methods of determination. AAS found nickel
concentrations to be nearly the same when the sample consisted of 10 mL or 15 mL
of unknown in 100 mL of water.
Chelometric titration of zinc yielded a concentration for the unknown of
0.00102M.

V. Comments and Conclusion

Both chelometric titration and AAS would be invaluable tools for determining
the concentration of various ions in water samples in order to determine whether
quantities meet standards set by the various governmental organizations.
Chelometric titration is a much more time consuming process when
compared to AAS, with a more complicated procedure allowing for more personal
error; while AAS is a quicker method that does not require the separation of metal
ions from solution. In the hands of a skilled individual both procedures seem to be
more than sufficient in terms of accuracy and precision.

Sources of error in this experiment could have included the presence of very
few air pockets in the resin while it was in the column. The column was not
completely drained of HCl prior to addition of water resulting in some HCl existing in
the zinc eluent. Also, the column was not completely drained of water creating the
possibility that some zinc ions were retained in the resin. Upon complete
evaporation of the nickel solution some of the nickel turned brown as opposed to
remaining green, this indicated the possibility of some NiO formation, which could
not be titrated with EDTA. The zinc solution was extremely acidic do to the
presence of HCl in the solution, and required the addition of sodium bicarbonate and
excess buffer to reach a pH of 10.