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SYNTHESIS AND SPECTROPHOTOMETRIC DETERMINATION THE ACID DISOCCIATION CONSTANT OF DIAZO DYES
SHARA MAY TANIA A. SALVACION 1 INSTITUTE OF CHEMISTRY, UNIVERSITY OF
PHILIPPINES, QUEZON CITY, PHILIPPINES 1600 from protonation. The acetamido group, although much less activating than a free amino group, is ABSTRACT nevertheless an activating, ortho, para-directing group in aromatic The aim of this experiment is to substitution. Following nitration of explore the synthesis of organic azo acetanilide, the acetyl group is dyes, specifically Alizarin Yellow R, removed to give p-nitroaniline. This and to spectrophotometrically will serve as the diazonium component determine the acid dissociation of the Alizarin Yellow R. constant of the diazo dye and acidAfter the first synthesis (the base indicator, Methyl Red. The Beer’s synthesis of p-nitroaniline), law and the Henderson-Hasselbach diazotization would occur once the equation were used in the second part coupling agent is added. The reaction of the experiment dealing with is called azo coupling. In this reaction, spectrophotometry. Because of the low the diazonium compound, the ppercent yield of Alizarin Yellow R, the nitroaniline, is an electrophile and the first part was considered a failure. The salicylic acid is the nucleophile in an second part, however, resulted to only electrophilic aromatic substitution. In 0.6% deviation from the literature pKa azo coupling, the end product would value of Methyl Red and was most likely be used as dyes and pH considered a successful experiment. indicators such as methyl red, pigment red 170, and alizarin yellow R.1 In the second experiment, the INTRODUCTION spectrophotometric determination of pKa of methyl red uses the concept of Azo dyes are important in our daily absorbances according to Bouguerlives. As a result of n-delocalization, Lambert-Beer law and the concept of azo dyes or aryl azo compounds have the relationship between pKa and pH vivid colors, especially reds, yellows, according to the Hendersonand oranges. Some azo compounds, Hasselbach equation. The Bouguerlike methyl orange, is used as acidLambert-Beer law forms the base indicators due to the different mathematical-physical basis of lightcolors of their acid and salt forms. absorption measurements on gases Most discs use blue azo dyes as and solutions in the UV-VIS and IRrecording layer. The synthesis of azo region: dyes plays a very important role in the chemical industry. The total synthesis of Alizarin Yellow R involves two syntheses: where nitration and diazotization. Pyridine must be added to aniline first. An is the absorbance, amide group is much less basic than in % is the an amino group. Hence, acylation of transmttance, the amino group of aniline with acetyl chloride to give N-phenylacetamide εν is the molar absorptivity (acetanilide will protect the nitrogen coefficient.
In order to eliminate this sources of error. and added with concentrated NH3 until no more solids had formed. was dissolved in minimal amount of hydrochloric acid and the solution is chilled in an ice bath.0 mL water for 30 minutes. the protecting group of the para-nitroacetanilide was removed and para-nitroaniline had been successfully synthesized in the solution. placed in an ice bath after. acetanilide was first used to synthesize the diazonium component of the dye. 1. Acetanilide. The total synthesis of Alizarin Yellow R was finished after the slow mixing of the diazonium solution and the salicylic acid solution in a very low temperature environment (below 0oC) and allowed to stand for 10 minutes after the complete reaction of the diazonium component and the coupling agent. Meanwhile. the Henderson-Hasselbach equation must be used since pH and the molarities of the substances in the solution had already been determined.0 g salicyclic acid was also dissolved by the other members of the group in minimal volume of 100% NaOH and cooled in an ice bath. After the formation of paranitroacetanilide. which was in solid form.60 g of NaNO3 crystals was added to the cold para-nitroaniline solution. The solution was filtered and the solids was allowed to reflux wih 15. . This is to prepare it for the slow and gradual addition of aqua regia (1. This is the diazonium solution.I0 is the intensity of the monochromatic light entering the sample and I is the intensity of the light emerging from the sample.0 mL HCl in the fume hood and chilled in an ice bath. The recrystalized para-nitroaniline was dissolved in 20. part of the light is lost through reflection at the cuvette surfaces. However. METHODOLOGY I.2 The absorbances of substances at the same wavelength is additive. c is the concentration of the lightabsorbing substance and d is the pathlength of the sample in cm.00 mL of HNO3 and 1. The Bouguer-Lambert-Beer law presupposes a measurement of the relationship between the light intensities I and I0. Since most UV-VIS spectroscopy is carried out with solutions. Therefore: To compute for the pKa of methyl red. the standard cuvette contains the pure solvent. the yellow product was filtered out after the cooling of the solution so that the product could go through recrystallization. cold distilled water was added until no more solid was produced.50 mL. when measuring in quartz cuvettes (UV-VIS region) or cuvettes made of special optical glass (VIS region). The solution was then coold in an ice bath for 10 minutes and to room temperature with occasional stirring. The rusty colored product was collected and recrystallize using acetone. To make sure that the percent yield of the para-nitroaniline is high. This was cooled to room temperature. TOTAL SYNTHESIS OF ALIZARIN YELLOW R In the total synthesis of Alizarin Yellow R. a reference measurement is made in a cuvette with the same pathlength but not containing the substance to be measured. the para-nitroaniline.20 mL of H2SO4) in increments of 0. Through this process. 3. It was then filtered out again. The residue was washed with water and was added to 1:2 mixtures of toluene and absolute ethanol. which ideally should not absorb in the spectral region under consideration. This reaction will form para- nitroacetanilide.0 mL HCl and 20.
Instead.6 g. the pH of the sample solutions 7-10 were measured. the solution. The experiment almost failed in the recrystallization of Alizarin Yellow R.0 nm (λHMR) were measured . standard methyl red. Spectrophotometric Determination of the Acid Dissociation Constant of Methyl Red The solutions were prepared first and foremost.0 g original weight (3. The spectra of the basic and acidic methyl red solutions between 350 to 600 nm was obtained using distilled water in reference cell of the UV-VIS Spectrophotometer.040 M NaOAc were the actual sample to measure the concentrations of the acidic and basic methyl red. The round bottom flask containing the dissolved acetanilide was not chilled in an ice bath before the addition of aqua regia. para-nitroaniline.0200 M HOAc. 0.0 g salicylic acid). During the synthesis of Alizarin Yellow R. The solids had been refluxed to form the diazonium component. It was then recrystallized for a higher percent yield. Although a source of error had already been found.0200 M HOAc. Meanwhile. The 0.010 M HCl and the acidic methyl red solutions were used in samples 1-3 with different volumes.0g acetanilide and 3. 0. The salicylic acid and the paranitroaniline had been mixed and allowed to stand for 10 minutes in a very low temperature. acidic methyl red. The data of the absorbance was then read out and plotted in the computer. From the 6. Because of this.010 M HCl. SPECTROPHOTOMETRIC DETERMINATION OF ACID DISSOCIATION CONSTANT OF METHYL RED THE The following solutions were prepared from the stock solutions: 0. became yellowcolored already.040 M NaOAc. 0. the standard methyl red. All absorbances in the wavelengths 428. the experiment still continued.010 M NaOAc. These solutions were prepared for calibration.5 nm (λMR-) and 520. which contains the para-nitroacetanilide. II. The 0.RESULTS AND DISCUSSION OF OF RESULTS I. The product did not recrystallize using acetone. which forms the end product. and basic methyl red solutions. the percent yield was 27% only. Alizarin Yellow R. This is the coupling reaction. The weight of the paranitroaniline was not measured as advised by the instructor due to lack of time. The molarities of the solutions were also calculated from the molarity of the methyl red stock solution. distilled water was used for the process. and 0. Total Synthesis of Alizarin Yellow R II. Using a pH meter. SPECTROPHOTOMETRIC DETERMINATION OF ACID DISSOCIATION CONSTANT OF METHYL RED THE Figure 2. an error occurred just after dissolving the acetanilide using minimal amount of concentrated H2SO4.010 M NaOAc and basic methyl red solutions were used in samples 4-6 with different volumes also. TOTAL SYNTHESIS ALIZARIN YELLOW R Figure 1. 0. The mass of the dry product was found to be 1. and the molarity of the standard solution.
-51 L mol-1 cm-1.4 0.02 3 5 0.00001 1.598 x 10-5 3. Data for Sample Solutions 710 Although the pKa of Methyl Red could be calculated from the data using the Henderson-Hasselbach equation.80 5.68 0 0.2 0.2E-05 1. Determination of εHMR.4E-05 1.3 0. D eterm ination of εHMR.15 4 7 0.λHMR .λHMR.λHMR .λMR0.6E-05 - Concentration of MR Solution Figure 5.40 3 λHMR 0.082 L mol -1 cm-1.05 0. Furthermore.90 1 1.17 3 5. The εHMR. Table 1.46 6 9 0.5 Absorbance at λHMR 0. the pH. b.00001 1.20 4. in sample solutions 1-3.025 0.56 4 0. and εMR-.035 0.266 10-5 2.4E-05 1.1 0 0 2E-06 4E-06 6E-06 8E-06 0.2E-05 1. Determination of εHMR. The y-intercept.60 5.05 0.04 0. On the other hand.70 2 0.283 x 10-6 6.03 0.54 4 0. it was assumed that [HMR] is approximately zero.6E-05 - 6.02 0.40 3 0.189 x 10-6 1.947 10-5 x x x x MR4. and the log ([MR-]/[HMR]).18 0.01 0 0 2E-06 4E-06 6E-06 8E-06 0.016 10-5 1.4E-05 1. 398. Determination of εMR-.15 0. for sample solutions 4-6.02 5 4 Molarity of Solution (M) 1.λMRwas found to be 4. which are used for the determination of the molar absorptivity coefficients.λHMR 0. 5 and 6 serve as the molar absorptivity coefficients.393 x 10-5 Determ ination of εMR-.283 x 10 -6 Concentration of MR Solution Figure 6.00001 1. are tabulated below.14 0. From the molar absorptivity coefficients. and assuming that.03 0.λMRD eterm ination of εHMR.6E-05 Concentration of HMR Solution Absorbance at λMR- Figure 3.015 0.04 0. the least squares method could also be used still obtaining the same pKa. Solutio n 7 8 Absorbance pH λMR0.can be computed also using the Beer’s law and is tabulated on a table below including the absorbances.2 Absorbance at λMR0.λMR0.λHMR 0. the molarity of HMR and MR.06 0.λMR-.89 Concentration of Methyl Red (M) HMR 1.4E-05 1.573 L mol-1 cm-1.01 0. is the pKa.03 1 5 0. Figure 4.189 x 10-6 Absorbance at λHMR 9. 4.393 x 10-5 9.31 0 1 0.07 0. εHMR.2E-05 1. εMR-. The data of the absorbances and the molarities of sample solutions 1-6.05 0 0 2E-06 4E-06 6E-06 8E-06 0. Determination of εMR-.866 x 10-5 4.372 10-5 2.00001 1. there is no concentration of MRpresent in the solutions.02 0. the pH’s was plotted against log ([MR-]/[HMR])’s to obtain the equation of the line.06 0.07 0.6E-05 Concentration of HMR Solution 9 10 Table 2.through the UV-VIS spectrophotometer.474 x 10-5 2.083 x 10-5 The molar absorptivity coefficients were determined by using Beer’s law.λMR- D eterm ination of εMR-.03 0.334 L mol-1 cm-1.005 0 0 2E-06 4E-06 6E-06 8E-06 0.2E-05 1. 13.1 0. Data for Sample Solutions 16 Solutio n 1 2 3 4 5 6 Absorbance λMRλHMR 0.λHMR The slope of the lines of figures 3.
careful measuring of the amount of basic methyl red and NaOAc is advised. This is 0. H. Figure 6 showed this error. The figure showed a curve which is supposedly a straight line. 5. Inc.4 0.Concentrations Sample Solution 7 0.6% deviating from the literature value.8 -0.6 5. The experimental pKa was only 0.004551)[HMR] + (13572. This may be because the solution might not be prepared according to the manual. if the end product did not recrystallize in future experiments. Plot of pH against log ([MR-]/ [HMR]) The pKa obtained is 5. In the spectrophotometric determination of the acid dissociation constant of methyl red. Organic Chemistry 3rd Edition.403 = (39833. = 26.05 L) (M methyl red stock) M methyl red stock = 3. SAMPLE CALCULATIONS Percent Yield Alizarin Yellow R Figure 7. or maybe because of the error of the spectrophotometer.02526355) [MR-] [HMR] = 1. The experiment had a known source error from the start which may be the cause of the Alizarin Yellow R not recrystallizing. M.6 0. we recommend that distilled water should be used in the recrystallization.305 x 10-3 M) (0. However.8 5. This might lessen the yield of the pure product but it is still a good substitute for the acetone. they were positive.00. Pages 3-4. Benjamin/Cummings Publishing Company. page 138  Perkampus. the experiment was successfully conducted. there was still a source of error.03. MR 6 log ([MR]/[HMR]) 5.72209)[HMR] + (-51.035 L) = (0. UV-VIS Spectroscopy and Its Applications.305 x 10-3 M (5.6% higher then the literature value of the pKa of Methyl Red. Nevertheless.865993696 x 10-5 pKa Determination Henderson-Hasselbach (Solution 7) pKa = 5. this may be another source of error that’s why we obtained a really small yield of the end product.67% Molar Concentrations of Solutions Methyl red stock solution = 5.2 5 4.2 0 0. Springer-Verlag Berlin Heidelberg 1992. The slope is negative while on the other graphs. CONCLUSIONS AND - RECOMMENDATIONS The first part.8 -  Loudon G.702 = (4082. H.4 5. Since the error of the instrument cannot be controlled. the total synthesis of Alizarin Yellow R was deemed to be a failure.12 Least Squares solutions) Method (For all Equation .713 x 10-3 M HMR and MR.REFERENCES pHvs log([MR ]/[H ]) . Chapter 23. 1988.017938623 x 10-5 [MR] = 4.2 pH 0.71999) [MR-] 0. But then again.
121 – 5.106 Mean RSD (in ppt) = 9.Xlowest = 5.03 Relative Error Calculation = 0.6% Range Range = Xhighest .046 Confidence Limits = 5.015 = 0.0458 =0.063 .Standard Deviation = 5.
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