CHEM

2211
Experiment Ten
Extraction of a Zinc Complex
Objective:
1. To measure the concentration of zinc in nonaqueous samples using the
spectrophotometer.
2. To evaluate the efficiency of extraction for zinc from aqueous into nonaqueous solutions
using dithizone as the chelating extractant.
Text Reference:
Harris Chapter 23
Introduction:
Partitioning of a mixture between two immiscible phases is a commonly used method for
isolating a component(s) of interest. This method is rapid and easily scaled to meet the needs of
the experimenter. Theory of partitioning is straightforward. The ratio of the concentration of
the species of interest, X, in each phase is defined as the partition coefficient, Kp.

Kp = [X]organic / [X]aqueous

When species X exists in more than one form in either phase, the term distribution ratio, D, is
used to quantify the total concentration of X in each phase.

D = Cxorganic / Cxaqueous

For example, if X is a weak acid, then it exists in the aqueous phase in both the associated and
dissociated forms HX and X-, respectively.

D = Cxorganic / Cxaqueous = [HX]organic / ([HX]aqueous + [X-]aqueous)

The distribution ratio is then dependent upon pH and the pKa of the weak acid.

D = Kp [H3O+] / (Ka + [H3O+])

In this experiment, dithizone (Dz) will be used as a chelating extractant for zinc ion. This
material is a diprotic acid, but its second ionization is so weak that it can be neglected.

H2Dz + H2O HDz- + H3O+

Ka1 = [H3O+][HDz-] / [H2Dz] = 1.5 x 10-5

The molar solubility of H2Dz in water is low (2 x 10-7) but HDz- dissolves in alkaline aqueous
solutions. The value of Kp for H2Dz is 108 (between chloroform and H2O).
The stoichiometry of the extraction of zinc using dithizone as a chelating extractant is:
Zn2+aqueous + 2H2Dzorg Zn(HDz)2 org + 2H3O+aqueous
The equilibrium constant for the above reaction is:
Keq = [Zn(HDz)2]org [H3O+]2aqueous / [Zn2+]aqueous [H2Dz]2org
The distribution ratio for zinc is:
DZn = CZn organic / CZn aqueous = [Zn(HDz)2]organic / ([Zn(HDz)2]aqueous + [Zn2+]aqueous)
Since the solubility of Zn(HDz)2 in the aqueous phase is very low, the distribution ratio reduces
to
DZn [Zn(HDz)2]organic / [Zn2+]aqueous
Substituting DZn into Keq (above) yields:
Keq = DZn [H3O+]2 / [H2Dz]2organic
Rearranging for DZn shows that DZn depends upon the pH of the aqueous solution.
DZn = Keq [H2Dz]2organic / [H3O+]2
Experimental:
Part I. Preparation
1. Obtain and clean the following items:
15 10-mL vials
1.0, 4.0, 5.0-mL volumetric pipettes
1 5.0-mL Mohr pipette
Several beakers for transporting stock solutions

2. Obtain the following materials and record their concentrations:

Zinc acetate reagent
Dithizone reagent
Buffer solutions
3. Open the Experiment 9 LoggerPro template from T-square and calibrate using the
Experiment 9 laboratory procedure.
Part II. Determining the Effect of pH on Extraction of Zinc from Aqueous Solution
Using the stock solutions acquired in Part I, prepare the following solutions by pipeting into
appropriately labeled vials the following volumes:
Soln. No.
1
2
3
4
5
6
7

Vol Zinc Stock Vol. H2Dz

Soln (mL)
Stock Soln.
(mL)
4.0
5.0
4.0
5.0
4.0
5.0
4.0
5.0
4.0
5.0
4.0
5.0
4.0
5.0

Buffer pH

Vol. of Buffer
(mL)

Purpose

1 (pH = 5.0)
2 (pH = 5.5)
3 (pH = 6.0)
4 (pH = 6.5)
5 (pH = 7.0)
6 (pH = 7.5)
7 (pH = 8.0)

1.0
1.0
1.0
1.0
1.0
1.0
1.0

pH study
pH study
pH study
pH study
pH study
pH study
pH study

Vigorously mix (shake) each solution for one minute and set aside for a couple of minutes to
allow complete extraction and layer separation. [See figure below for appearance of vials]
Carefully remove a portion of the organic phase and acquire its visible spectrum (from 350
to 750 nm) for each solution using pure organic solvent (CHCl3) in the reference cuvette. Be
sure to record the absorbance at all peak maxima in this spectral range.

Analyze the data and identify the peak maxima characteristic of dithizone and of the complex.
Select the buffer pH that provides the maximum amount of zinc extraction without partitioning
of dithizone into the aqueous phase. Use this buffer in preparing the solutions in Part III below.
3

Part III. Measuring Zinc Chelate Concentrations in the Organic Phase

Using the stock solutions acquired in Part I and the optimal buffer identified in Part II, prepare
the following solutions by pipeting into appropriately labeled vials the following volumes:
Soln. No.

Vol Zinc Stock Vol Water

Soln (mL)
Soln (mL)

8
9
10
11
12

0.0
1.0
2.0
3.0
4.0

4.0
3.0
2.0
1.0
0.0

Vol. H2Dz
Stock Soln.
(mL)
5.0
5.0
5.0
5.0
5.0

Vol. of Buffer
(mL)

Purpose

1.0
1.0
1.0
1.0
1.0

Blank
Conc. Study
Conc. Study
Conc. Study
Conc. Study

Vigorously mix (shake) each solution and set aside for a couple ofn minutes to allow complete
extraction and layer separation. Carefully remove a portion of the organic phase and measure
the absorbance at the peak maxima identified in Part II above.
Plot the measured absorbance vs. zinc complex concentration. Calculate the molar absorptivity
of the zinc-dithizone complex from the slope of the linear region of this plot. Use this value to
compute and plot the distribution ratio as a function of pH for the solutions prepared in Part II.
Part IV. Single vs. Multiple Extractions
Inspect the data acquired in Part II and select the buffer that gave partial extraction of zinc into
the organic phase. Use this buffer in preparing solution #13. After the extraction is complete,
remove the aqueous layer and transfer it to vial #14. Measure the absorbance of the organic
layer at the complex wavelength identified in Part II. Add a fresh 5.0 mL portion of H2Dz solution
to the aqueous phase (clear) in vial #14, mix, and remove the aqueous layer and transfer it to vial
#15. Again, measure the absorbance of the organic layer from the 2nd extraction at the complex
wavelength identified in Part II. Repeat the extraction a third time with fresh dithizone solution
and measure the absorbance of the organic layer at the complex wavelength identified in Part II.
Soln. No.
13
14


15

Vol Zinc Stock

Soln (mL)
4.0

Vol. H2Dz Stock

Soln. (mL)
5.0
5.0
5.0

Vol. of Buffer
(mL)
1.0

Purpose
1st extraction
2nd extraction
3rd extraction

Compute the concentration of zinc in the organic phase for each extraction. Sum these values
and compare the sum to the initial zinc concentration in the aqueous phase. How many
extractions are required for 99% removal of zinc from the aqueous phase at the pH used in this
part of the experiment (Question 4)?
4

Questions:
1. Is the plot of measured absorbance vs. zinc complex concentration linear? Why or why
not?
2. Using the appropriate mass balance equations for zinc and dithizone and your data,
calculate the equilibrium constant for the extraction. Hint: Given in protocol!
3. At what pH value will exactly one-half of the zinc present in the aqueous phase be
extracted into an equal volume of organic phase with the chelator and solvent used in
this experiment? Determine the pH from your plot of D vs. pH and compare it to the
calculated pH using the determined equilibrium constant.
4. How many extractions are required for 99% removal of zinc from the aqueous phase at
the pH used in part IV of this experiment?