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Chelation and Binding of Metal Ions

in Complexation Titrations to
Determine Unknown Ion
Concentrations
William G. Anderson
Department of Chemistry
Georgia State University
11-20-2015

Introduction

In the following experiments, complexation reactions were performed


by automatic titration of nickel and magnesium solutions with
ethylenediaminetetraacetic acid (EDTA). This type of complexometric
titration, or chelatometry, is a well-established titration method (Irving &
Rossotti, 1954). In order to measure this type of titration, a spectrometric
probe may be used, whereas instead of measuring equivalency by pH
change, determination may be made based on feedback from the miniature
spectrometer, in order to measure complex concentration. This feedback is
generally provided in units of millivolts, providing a very precise scale of
measurement. As far as appropriate reagents, EDTA was used, as it contains
four carboxyl groups and two amine groups that can act as electron pair
donors, or Lewis bases. The ability of EDTA to potentially donate its six lone
pairs of electrons for the formation of coordinate covalent bonds to metal
cations makes EDTA a hexadentate ligand (Kluger et al., 1975). Additionally,
EDTA forms an octahedral complex with most 2+ metal cations, M2+, in
aqueous solution. The main reason that EDTA is used so extensively in the
standardization of metal cation solutions is that the formation constant for
most metal cation-EDTA complexes is very high, meaning that the
equilibrium for the reaction will lie far to the right, optimizing titration
measurements. In titration, a free indicator is necessary for use with EDTA,
to determine endpoint. Therefore, in this specific application of
chelatometry, endpoint is determined by indicator change rather than
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precipitate formation, necessitating the use of a spectrometer probe for


measurements. This type of titration has wide applications, from the
determination of water hardness to pollution analysis (Irving & Rossotti,
1954).
Materials & Methods
A standard solution of aqueous ethylenediaminetetraacetic acid (EDTA)
was prepared, using 18.6 g of EDTA disodium salt obtained from Fischer
Scientific with 99.8% purity, diluted to 1 L final mark with DI water and
gentle heat, hereafter referred to as solution A1. This was subsequently
diluted, taking 50 mL of the above solution and diluting to 100 mL final,
yielding a final solution of approximately 0.025 M, designated as solution A2.
To standardize this solution, it was titrated with a pH probe against
previously standardized NaOH solution of 0.1370 M. The concentration of
solution A1 was then back-calculated from this standardization, then used to
prepare solution A3, using 50 mL of solution A1 with 0.6 g of magnesium
sulfate heptahydrate (MgSO47H2O) obtained from EMD Scientific with 99.7 %
purity, diluted to 100 mL, to yield a final concentration of 0.025 M for both
EDTA and MgSO4. This was titrated against NaOH solution in triplicate, again
with pH probing, in order to examine the titration curve of EDTA in the
presence and absence of magnesium ions, and to exactly standardize the
concentration of solution A1. Subsequently, 250 mL of aqueous solution was
prepared, one of approximately 0.05 M Mg2+ ions, the other of approximately
0.05 M Ni2+ ions, prepared with 3.1 g of Ni(Ac)2 solid from Acros Scientific
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with 99.5 % purity, and the other prepared using 3.1 g of MgSO47H2O solid,
whose source is mentioned previously. These were each titrated against
EDTA solution A1 using spectrophotometric probing, once in acetate buffer
(pH=4.7, provided by GSU Department of Chemistry) and once in ammonium
buffer (pH=9.3, provided by GSU Department of Chemistry) with the addition
of murexide indicator from Acros Scientific, to determine appropriate buffers
for each metal ion. These solutions of Mg2+ and Ni2+ were then combined into
a mixture of 60 mL Ni2+ solution with 40 mL of Mg2+ solution to yield a
mixture with known ion ratio. This known mixture was titrated against EDTA
solution A1 in both ammonia and acetate buffers in triplicate to provide a
baseline for mixture titration. Subsequently, a mixture of unknown ratio was
titrated using the same method to determine the concentration. All titrations
were performed using a properly rinsed and calibrated TitroLine 7000 autotitrator from SI Analytics with constant stirring, running TitriSoft 3.1 analysis
software. Microsoft Excel 2013 was used for additional analysis and all
calculations.
Results
Table 1: Equivalency and concentration values for titration of solution A2
with NaOH
Trial #
1

Eq. Volume
(mL)
4.714

pH
8.55

Conc. EDTA Sol.


A2
0.02513 mol/L

Conc. EDTA
Sol. A1
0.05027 M

(These preliminary values for the molarity of EDTA in solution are consistent
with expected values of ~0.025 M and ~0.05 M for solutions A2 and A1,
respectively.)
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Table 2: Equivalency values for titration of solution A3 with NaOH


Trial #
1

Eq. Volume (mL)


9.303

pH
8.51

9.321

8.62

9.336

8.63

Avera

9.320

8.58

ges
(As shown by the values, when Mg2+ ions are present, titration requires
roughly twice as much base, due to the need of EDTA to lose 2 protons to
bind with Mg2+ ions, by the Mg2+ + EDTA4- [MgEDTA]2- reaction that takes
place, thus requiring twice as many OH- ions to be placed in solution for this
deprotonation to occur. Though not shown, concentration values from these
titrations agree almost exactly with the value from Table 1.)

Figure 1
14
12
10
8

pH

6
4
2
0

10

12

14

mL EDTA

Figure 1:
Titration curve of EDTA solution A2 with NaOH

Figure 2: Overlaid titration curves of EDTA solution A3 with NaOH


5

Figure 2
14
12
10
8

pH

6
4
2
0

10

12

14

mL EDTA
Trial 1

Trial 2

Trial 3

Table 3: Equivalency values for titration of Mg2+ ion solution with EDTA
Buffer

Eq. Volume (mL)

mV

Ammoni

10.104

762

Concentration
of Mg2+
0.05079 M

um
Acetate

N/A

N/A

N/A

(No measurable equivalence point was evident in the titration in acetate


buffer, leading to the assumption that in acidic buffer conditions, Mg2+ ions
will not react with EDTA.)
Table 4: Equivalency values for titration of Ni2+ ion solution with EDTA
Buffer
Ammoni

Eq. Volume (mL)

mV

10.420 (weak)

720 (weak)

um

Concentration of
Ni2+
0.05238 M

Acetate

10.531

315

0.05294 M

(Based on these results, titration data from the titration of Ni2+ ion solution
with EDTA in acetate buffer will yield satisfactory results. Therefore, titration
of the mixture in ammonium buffer will yield total ion concentration, and in
acetate buffer will yield Ni2+ ion concentration.)

Figure 3: Titration curves of titration of Mg2+ ion solution with EDTA

Figure 3
1400
1200
1000
800

mV

600
400
200
0

10

15

20

25

30

mL EDTA
Mg/Acetate

Mg/Ammonium

Figure 4: Titration curves of titration of Ni2+ ion solution with EDTA

Figure 4
1400
1200
1000
800

mV

600
400
200
0

10

12

14

mL EDTA
Ni/Ammonium

Ni/Acetate

Table 5: Equivalency values for titration of 60:40 Ni:Mg mixture with EDTA in
ammonium buffer
Trial #

Eq. Volume (mL)

mV

10.286

695

Total Ion Concentration


(M)
0.05171

10.307

690

0.05181

10.291

692

0.05173

Avera

10.295

692

0.05175

ges

Table 6: Equivalency values for titration of 60:40 Ni:Mg mixture with EDTA in
acetate buffer
mV

Ni2+ Ion

Exp. % of Ni2+

(mL)
6.082

722

Concentration (M)
0.03057

in mix
59.12%

6.213

737

0.03123

60.28%

6.149

725

0.03091

59.75%

Avera

6.148

728

0.03090

59.72%

Trial #

Eq. Volume

ges
(Experimental values for percent Ni2+ are consistent with expected. If % Ni2+
is 60, then percent Mg2+ must be 40, holding true to the prepared mixtures
ratio.)

Figure 5: Titration curves for titration of 60:40 Ni:Mg mixture with EDTA in
ammonium buffer

Figure 5
800

750

mV
700

650

10

mL EDTA
Trial 1

Trial 2

Trial 3

12

14

16

Figure 6: Titration curves for titration of 60:40 Ni:Mg mixture with EDTA in
acetate buffer

Figure 6
850
800

mV 750
700
650

10

12

14

16

mL EDTA
Trial 1

Trial 2

Trial 3

Table 7: Equivalency values for titration of unknown Ni:Mg mixture with EDTA
in ammonium buffer
Trial #

Eq. Volume (mL)

mV

13.224

550

Total Ion Concentration


(M)
0.06648

13.328

546

0.06699

13.257

552

0.06664

10

Avera

13.269

549

0.06670

ges

Table 8: Equivalency values for titration of unknown Ni:Mg mixture with EDTA
in acetate buffer

561

Ni2+ Ion
Concentration (M)
0.04235

Exp. % of Ni2+
in mix
63.70%

8.791

555

0.04419

65.97%

8.578

556

0.04312

64.71%

Avera

8.598

557

0.03090

64.79%

Trial #
1

Eq. Volume
(mL)
8.425

mV

ges
(Percent Mg2+ ion in solution will be calculated from a rounded value of 65%
Ni2+ ion concentration in solution.)

Figure 7: Titration curves of unknown Ni:Mg mixture with EDTA in ammonium


buffer

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Figure 7
1000
800
600

mV

400
200
0

10

15

20

25

mL EDTA
Trial 1

Trial 2

Trial 3

Figure 8: Titration curves of unknown Ni:Mg mixture with EDTA in acetate


buffer

Figure 8
1000
800
600

mV

400
200
0

10

15

mL EDTA
Trial 1

Trial 2

12

Trial 3

20

25

Discussion and Conclusions


Values obtained for the concentration of EDTA titrant solution A1 agree
with extremely small variance, leading to the use of 0.05027 M as the
standard molarity of EDTA titrant in all subsequent calculations. As shown
and mentioned in Table 2, the volume of NaOH required to titrate solution A3
was very close to twice the amount of NaOH needed to titrate solution A2.
This change of titration data experimentally demonstrates that in the
presence of Mg2+ ions, EDTA must lose two protons for chelation to occur.
EDTA contains multiple binding sites, which can form very stable
complexes with a variety of metal ions (Irving & Rossotti, 1954) as
mentioned in the introduction. In this experiment, clean equivalence points
were observed, as formation constants (Kf) were greater than 108. This
statement excludes the titration of Mg2+ ions in acetate buffer, as an acidic
pH is not appropriate for the EDTA ligand bonding in this particular case.
However, Ni2+ ions can properly chelate in an acetate buffer, due to their
significantly higher Kf value. The reason why the use of ammonium buffer
worked well for both metal ions is its contained auxiliary coupling agent, NH3,
which helps to ensure proper ligand bonding (Harris, 2010). Therefore, both
metal ions formed observable amounts of metal-ligand complexes under
basic conditions in ammonium buffer, but only Ni2+ ions complexed under
acidic conditions in acetate buffer. The calculated Kf value for [Mg(EDTA)]213

complex was 6.3x108, while [Ni(EDTA)]2- returned a Kf of 2.4x1018. Therefore,


since [Mg(EDTA)]2- only formed in ammonium buffer, any equivalence point
observed in titration of any mixture of Mg2+ and Ni2+ ions in acetate buffer
was confidently treated as only representative of [Ni(EDTA)]2- complexes.
Based on this assumption, in the analysis of both known and unknown
mixtures of Mg2+ and Ni2+ ions, concentration was calculated by taking the
values from acetate buffer titration as the Ni2+ ion concentration in solution.
Thus, the Mg2+ ion concentration was simply the difference between total ion
concentration (observed by ammonium buffer titration) and the previously
calculated Ni2+ ion concentration. This method proved quite accurate in
analysis of the known mixture of 60:40 Ni:Mg ions, only deviant by 0.28%.
Based on these results, experiments were confidently carried out on
the unknown Ni:Mg mixture (#50, #3) using the same method. Though
total ion concentration was slightly larger than the known mixture (exact
values in Tables 7&8), the ratio was close to the same, yielding a final value
of 65:35 Ni:Mg in unknown solution.

References
Harris, D. (2010). Quantitative chemical analysis (8th ed.). New York: W.H.
Freeman and Co.

Acid-base reaction. (2015). In Encyclopdia Britannica. Retrieved from


http://www.britannica.com/science/acid-base-reaction

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Johansson, A. (1970). Automatic titration by stepwise addition of equal


volumes of titrant. Part I. Basic principles. Analyst, 95(1131), 535-540.

Kluger, R., Wasserstein, P., Nakaoka, K. (1975). Factors Controlling


Association of Magnesium Ion and Acyl Phosphates. Journal of the American
Chemical Society 97(15), 4298-4301.

Irving, H., Rossotti, H. (1954). The calculation of formation curves of metal


complexes from pH titration curves in mixed solvents. Journal of the
Chemical Society, (0), 2904-2910. doi:10.1039/JR9540002904

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