SPECTROPHOTOMETRIC DETERMINATION OF IRON IN AQUEOUS SOLUTIONS AS A COMPLEX OF 1,10PHENANTHROLINE

SALVADOR MARROD M. CRUZ DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES

RESULTS AND DISCUSSION

Light is formed due to the presence of an electric field and a magnetic field perpendicular to each other and the wave travels perpendicular to both of these fields. This light carries energy due to the movement of the particle which can interact with different chemical solutions. These interactions between radiation and matter are the subject of the science called spectroscopy [1]. In spectrophotometry, the concentration of an unknown species is determined by using the ability of the species to absorb light of a specific wavelength. In the experiment, the concentration of iron (II) in a colored solution of iron phenanthroline complex was determined by relating the absorbance recorded using the UV-vis spectrophotometer and the concentration of the solution using beers law. A spectrophotometer is a device capable of determining the absorbance of the solution. The spectrophotometer is composed of five crucial parts with specific functions. The first part of the spectrophotometer is called the light source which provides light with a certain range of wavelength, the light from the light source then hits the monochromator which is the part of the spectrophotometer which filters out the light of a specific wavelength desired. The monochromatic light then passes through the sample holder where the sample being determined is placed in a cuvette, the light coming out from the sample holder then enters the detector or transducer and finally, the absorbance of the solution will then be displayed. Transmittance (T) = (1) the transmittance of a solution is sometimes so small, the term absorbance was then coined in order to stand up for a much larger value which is obtained by getting the negative logarithm of the transmittance (2). Absorbance is also more commonly used because it forms a linear relationship with the concentration of the solution of the species being determined which is given by the beers law. Transmittance is seldom used because it forms a more complicated logarithmic function with the concentration of the species. ( ) A= absorbance a= specific absorptivity coefficient b=path length (b= 1cm in experiment) c=concentration =molar absorptivity coefficient. As said earlier, the absorbance of a colored solution is related to its concentration under certain conditions given by the beers law. The beers law states that the absorbance of a colored solution is directly proportional to its concentration and to the path length of the cuvette used. A cuvette is an object made from quartz or plastic depending on the classification of the electromagnetic wave used in the spectrophotometer because certain materials cannot be used under a certain range of wavelength. Absorbance is just directly proportional to the product of the path length and concentration, with the aid of a constant called the molar absorptivity coefficient ( ) or specific absorptivity constant (a), the concentration in molarity of the former and any concentration for the latter, the absorbance can then be equated to the product of the constant, path length, and the concentration of the colored species (3). The equation given by the beers law is limited to dilute solutions less than 0.01M because at concentrations higher than 0.01 M, the graph fails to achieve a linear relationship due to the electrostatic interactions between the molecules in a solution. Beers law is also limited to the presence of a monochromatic light because at the presence of stray

Absorbance (A) = -log(T) (2) The transmittance of a solution is defined as the ratio of the amount of light that passed through a solution (Io or Iinitial) and the amount of light that entered the solution (I or Iafter)(1). Due to the fact that

lights, the absorbance of the solution changes due to absorption at different wavelengths. Beers law is limited to solutions in which the chemical species being analysed must be stable in the solution because changes in the solution contributes to changes in absorbance and hence cannot give an accurate concentration of the solution. It is also a must that the solution being analysed must be able to absorbs light at the range of wavelengths available and it must have a high constant of formation in order to prevent the reverse reaction from occurring and to create a stable analyte that can be detected by the machine used. 4Fe3++2NH2OH HCl Fe2+ + 3C12H8N2 4Fe2+ + N2O+ 4H+ +H2O (4)

Absorbance vs. Concentration

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 0.5 1 1.5 2 2.5 3

y = 0.2502x - 0.0023 Concentration (ppm Fe(II)) R = 0.9992

Figure.1 Calibration Curve The solutions prepared were then analysed using the double beam spectrophotometer. Two cuvettes with water were first placed on the two sample holders in the spectrophotometer and the baseline was declared in order to autozero the range of the spectral scanning. The solution of maximum concentration was then placed on the sample cell and water was placed in the reference cell in order to determine the analytical wavelength of the solution by the means of spectral scanning because the solution absorbs color at most at the analytical wavelength. It is a must that the solution must be analysed at the analytical wavelength in order to yield accurate and precise results. The experiment was able to obtain a wavelength of 509.0 as the wavelength at which the most concentrated solution absorbs the most. After determining the analytical wavelength, the machine was then autozeroed in order to remove the absorbance contributed by the blank solution, the solution containing all the components of the solution except for the analyte, and in order to present only the absorbance due to the analyte. The solutions were then placed in a cuvette one by one by first washing the cuvette with distilled water followed by washing with the solution three times and the absorbance obtained were recorded. The recorded absorbance for each trial is placed in table 1. Upon determining the absorbance of all solutions, the calibration curve was then obtained by getting the best fit curve for the data. The best fit curve was obtained by using Microsoft excel in order to yield the equation of the line, and the equation of the best fit curve obtained in the experiment was A=0.2502c 0.0023 with a linearity coefficient of 0.9992. An alternative way for obtaining the equation of the best fit curve was done by using the least squares method (6) and (7) in order to obtain the value for the slope and the yintercept. The equation of the best fit curve was able to yield a specific absorptivity coefficient of 0.2502, the slope of the line is the specific absorptivity coefficient directly because the path length of the cuvette used was 1cm. The calibration curve obtained is of special importance because it is the primary equation to be used in order to determine the concentration of the iron (II) species present in the unknown samples.

Fe(C12H8N2)32+ (5)

In the experiment, the solutions of known concentration of iron (II) in 6 different trials were first prepared by adding iron (II) solutions of varying concentration in a volumetric flask with one solution having all the components except for the species desired in the experiment. 10% hydroxylamine hydrochloride solution was then added to the solution in the volumetric flask in order to convert iron (III) in the solution to iron (II) given by reaction (4) because it is the desired species in the experiment performed. An excess of phenanthroline was then added to the solution in order to form a colored complex of iron (II) on which the absorbance can be detected by the spectrophotometer since the spectrophotometer can measure the absorbance of a certain species under the visible range of light and it was added in excess in order to make sure that all of the iron (II) was able to complexate with the phenanthroline solution so that the concentration of the colored species, the one used in the beers law, can be determined easily (5). And lastly, a buffer with an acidic pH was added in order to prevent the hydrolysis of iron forming pentaaquahydroxoiron (III) (Fe(H2O)5OH2+) which can decrease the resulting absorbance of the solution because the complex formed does not absorb at the analytical wavelength of the spectrophotometer. The procedure of adding the reagents were strictly followed in order to prevent the appearance of Fe 3+ in the solution and to prevent the hydrolysis of iron since Fe2+ is the species analysed in the experiment.

Absorbance

Table.2 Data of unknown species. Unk Absor Conce Concentration now bance ntratio in stock (Stock n n = 100mL (ppm) solution)(ppm) 1 0.523 2.10 10.5 2 0.538 2.16 10.8 3 0.532 2.14 10.7 Ave 10.7 rage

Molarity in Stock 1.88x10-4 1.93x10-4 1.91x10-4 1.91x10-4

be performed using other complexing species as long as it could form a stable species with a large constant of formation and a colored species that absorbs purely in the visible light range which was the range used in the experiment. The data obtained was quite precise because they lie close to each other and is also accurate because the concentration of the solution in the 100mL sample solution was 12.5 ppm which is quite close to 10.7 with about 14.7% error which is caused by different errors present in the experiment. One possible source of error is the presence of bubbles in the cuvette in the region where light passes because the path length decreases and hence the absorbance of the solution also decreases. The formation of other complexes also may have caused a decrease in the absorbance because other complex with a different color does not absorb at the analytical wavelength because certain colors absorb certain wavelength of light. Performing the solution not at the analytical wavelength can also contribute to the inaccuracy of the experiment because of smaller absorbance recorded for each trial and an absorbance that does not differentiate much from each other which could possibly yield a curve that will give an inaccurate concentration of the unknown solution. The improper sequence of reagent addition in the solution preparation could have also been a reason because of the decrease in the amount of iron (II) ions present and the formation of iron complexes which could have caused a decrease in the absorbance recorded. And other possible errors are errors due to the instrument which cannot be known easily and other random errors which could have affected the precision of the experiment. Overall, the experiment yielded a confidence limit of 0.000191 0.000007 M for the concentration of iron (II) in the 100mL sample solution.

For the unknown solutions, the same procedures were followed as before in preparing the solution and in determining the absorbance of the solution. By substituting the recorded absorbance in the calibration curve obtained, the concentration of the solution in the diluted sample was obtained and placed in table.2. With the aid of stoichiometry, the amount of iron (II) in the stock solution was obtained by simply adding a dilution factor of 5 in order to determine the concentration of the 10.00mL of aliquot that served as a representative of the whole 100mL solution of the unknown sample. Also with the aid of stoichiometry, the concentration of the samples in molarity were determined and listed in table 2. The results of the experiment was quite valid because of the fact that the molarity of the solution must be small enough in order for the law to hold, because there are points called the minimum and maximum sensing in the experiment performed such that the linear behaviour cannot be followed beyond the given range. In the experiment, the concentration of iron(II) was determined easily because the colored compound called the iron phenanthroline complex is formed by reacting one mole of iron (II) and three moles of phenanthroline hence the concentration of the colored complex, the concentration obtained from the calibration curve, is also the concentration of the iron (II) present in the solution. The calibration curve was obtained using the solutions of known concentration of iron (II) with excess phenanthroline in order to form a complete reaction in order to assume that the concentration of the complex is equal to the concentration of the iron (II) in the solution. The experiment was performed at the analytical wavelength determined during the spectral scanning in order to yield an accurate and precise result because a solution analysed not at the analytical wavelength will yield concentration that are not that accurate or precise due to the fact that the absorbance not at the analytical wavelength is smaller than that at the analytical wavelength. Due to the smaller absorbance obtained in the wavelength not at the analytical wavelength, there could be a possibility of overlapping absorbance of two different concentration which are very small which is prevented here in the experiment. The experiment can

REFERENCES

[1]Harris, D. C. Quantitative chemical analysis. (8th ed.)(2010). [2] Skoog, D., West, D., Holler, F., & Crouch, S. (2010).. InFundamentals of Analytical Chemistry (8th ed.). Cengage Learning Asia Pte Ltd. [3] Harvey, D. (2000). In Modern Analytical Chemistry. The Mc-Graw hill companies, Inc.

APPENDIX

Table.1 Calibration curve data. Concentration Fe(II) ppm 0.50 1.00 1.50 2.00 2.50

Absorbance 0.121 0.251 0.368 0.506 0.619

Extra calculations: The equation of the best fit curve was obtained using Matlab 2012b given by the code: function [m,b] = linreg(x,y) m=(length(x)*sum(x.*y)(sum(x)*sum(y)))/(length(x)*sum(x.^2)-(sum(x))^2); b=(sum(y)-m*sum(x))/length(y); end The code given above yielded a value of 0.2502 for the slope of the line and a value of -0.0023 for the yintercept. The code used was from the formula using the least squares method given by the formula:
( )

(6)

(7)