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September 5, 2011

SYNTHESIS AND SPECTROPHOTOMETRIC DETERMINATION THE ACID DISOCCIATION CONSTANT OF DIAZO DYES
SHARA MAY TANIA A. SALVACION 1 INSTITUTE OF CHEMISTRY, UNIVERSITY OF
THE

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 Beers 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 is the molar absorptivity (acetanilide will protect the nitrogen coefficient.

I0 is the intensity of the monochromatic light entering the sample and I is the intensity of the light emerging from the sample; c is the concentration of the lightabsorbing substance and d is the pathlength of the sample in cm. The Bouguer-Lambert-Beer law presupposes a measurement of the relationship between the light intensities I and I0. However, when measuring in quartz cuvettes (UV-VIS region) or cuvettes made of special optical glass (VIS region), part of the light is lost through reflection at the cuvette surfaces. In order to eliminate this sources of error, a reference measurement is made in a cuvette with the same pathlength but not containing the substance to be measured. Since most UV-VIS spectroscopy is carried out with solutions, the standard cuvette contains the pure solvent, which ideally should not absorb in the spectral region under consideration.2 The absorbances of substances at the same wavelength is additive. Therefore:

To compute for the pKa of methyl red, the Henderson-Hasselbach equation must be used since pH and the molarities of the substances in the solution had already been determined.

METHODOLOGY I. TOTAL SYNTHESIS


OF

ALIZARIN YELLOW R

In the total synthesis of Alizarin Yellow R, acetanilide was first used to synthesize the diazonium component of the dye, the para-nitroaniline. Acetanilide, which was in solid form, was dissolved in minimal amount of hydrochloric acid and the solution is chilled in an ice bath. This is to prepare it for the slow and gradual addition of aqua regia (1.00 mL of HNO3 and 1.20 mL of H2SO4) in increments of 0.50 mL. This reaction will form para-

nitroacetanilide. The solution was then coold in an ice bath for 10 minutes and to room temperature with occasional stirring. After the formation of paranitroacetanilide, cold distilled water was added until no more solid was produced. The solution was filtered and the solids was allowed to reflux wih 15.0 mL HCl and 20.0 mL water for 30 minutes. This was cooled to room temperature, placed in an ice bath after, and added with concentrated NH3 until no more solids had formed. Through this process, the protecting group of the para-nitroacetanilide was removed and para-nitroaniline had been successfully synthesized in the solution. To make sure that the percent yield of the para-nitroaniline is high, the yellow product was filtered out after the cooling of the solution so that the product could go through recrystallization. The residue was washed with water and was added to 1:2 mixtures of toluene and absolute ethanol. It was then filtered out again. The recrystalized para-nitroaniline was dissolved in 20.0 mL HCl in the fume hood and chilled in an ice bath. 1.60 g of NaNO3 crystals was added to the cold para-nitroaniline solution. This is the diazonium solution. Meanwhile, 3.0 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. 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. The rusty colored product was collected and recrystallize using acetone.

RESULTS

AND

DISCUSSION
OF

OF

RESULTS

I. TOTAL SYNTHESIS

ALIZARIN YELLOW R

Figure 1. Total Synthesis of Alizarin Yellow R II. SPECTROPHOTOMETRIC DETERMINATION OF ACID DISSOCIATION CONSTANT OF METHYL RED
THE

The following solutions were prepared from the stock solutions: 0.010 M HCl, 0.010 M NaOAc, 0.0200 M HOAc, 0.040 M NaOAc, standard methyl red, acidic methyl red, and basic methyl red solutions. The 0.010 M HCl and the acidic methyl red solutions were used in samples 1-3 with different volumes. The 0.010 M NaOAc and basic methyl red solutions were used in samples 4-6 with different volumes also. These solutions were prepared for calibration. Meanwhile, the standard methyl red, 0.0200 M HOAc, and 0.040 M NaOAc were the actual sample to measure the concentrations of the acidic and basic methyl red. Using a pH meter, the pH of the sample solutions 7-10 were measured. 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. The data of the absorbance was then read out and plotted in the computer.

During the synthesis of Alizarin Yellow R, an error occurred just after dissolving the acetanilide using minimal amount of concentrated H2SO4. The round bottom flask containing the dissolved acetanilide was not chilled in an ice bath before the addition of aqua regia. Because of this, the solution, which contains the para-nitroacetanilide, became yellowcolored already. Although a source of error had already been found, the experiment still continued. The solids had been refluxed to form the diazonium component, para-nitroaniline. It was then recrystallized for a higher percent yield. The weight of the paranitroaniline was not measured as advised by the instructor due to lack of time. The salicylic acid and the paranitroaniline had been mixed and allowed to stand for 10 minutes in a very low temperature. This is the coupling reaction, which forms the end product, Alizarin Yellow R. The experiment almost failed in the recrystallization of Alizarin Yellow R. The product did not recrystallize using acetone. Instead, distilled water was used for the process. The mass of the dry product was found to be 1.6 g. From the 6.0 g original weight (3.0g acetanilide and 3.0 g salicylic acid), the percent yield was 27% only. II. SPECTROPHOTOMETRIC DETERMINATION OF ACID DISSOCIATION CONSTANT OF METHYL RED

THE

Figure 2. Spectrophotometric Determination of the Acid Dissociation Constant of Methyl Red

The solutions were prepared first and foremost. The molarities of the solutions were also calculated from the molarity of the methyl red stock solution, and the molarity of the standard solution. All absorbances in the wavelengths 428.5 nm (MR-) and 520.0 nm (HMR) were measured

through the UV-VIS spectrophotometer. The data of the absorbances and the molarities of sample solutions 1-6, which are used for the determination of the molar absorptivity coefficients, are tabulated below. Table 1. Data for Sample Solutions 16
Solutio n 1 2 3 4 5 6 Absorbance MRHMR 0.06 0.46 6 9 0.05 0.31 0 1 0.03 0.15 4 7 0.18 0.02 3 5 0.14 0.03 1 5 0.07 0.02 5 4 Molarity of Solution (M) 1.393 x 10-5

Determ ination of MR-,MR0.2 Absorbance at MR0.15 0.1 0.05 0 0 2E-06 4E-06 6E-06 8E-06 0.00001 1.2E-05 1.4E-05 1.6E-05
-

Concentration of MR Solution

Figure 5. Determination of MR-,MR-

D eterm ination of MR-,HMR


0.04 0.035 0.03 0.025 0.02 0.015 0.01 0.005 0 0 2E-06 4E-06 6E-06 8E-06 0.00001 1.2E-05 1.4E-05 1.6E-05
-

6.189 x 10-6 1.393 x 10-5 9.283 x 10-6 6.189 x 10-6

Absorbance at HMR

9.283 x 10

-6

Concentration of MR Solution

Figure 6. Determination of MR-,HMR The slope of the lines of figures 3, 4, 5 and 6 serve as the molar absorptivity coefficients. The HMR,MRwas found to be 4,082 L mol -1 cm-1; HMR,HMR , 398,334 L mol-1 cm-1; MR-,MR-, 13,573 L mol-1 cm-1; and MR-,HMR, -51 L mol-1 cm-1. From the molar absorptivity coefficients, the molarity of HMR and MR- can be computed also using the Beers law and is tabulated on a table below including the absorbances, the pH, and the log ([MR-]/[HMR]).
Solutio n 7 8 Absorbance pH MR0.70 2 0.68 0 0.56 4 0.40 3 HMR 0.40 3 0.54 4 0.90 1 1.17 3 5.80 5.60 5.20 4.89 Concentration of Methyl Red (M) HMR 1.016 10-5 1.372 10-5 2.266 10-5 2.947 10-5 x x x x MR4.866 x 10-5 4.598 x 10-5 3.474 x 10-5 2.083 x 10-5

The molar absorptivity coefficients were determined by using Beers law, and assuming that, in sample solutions 1-3, there is no concentration of MRpresent in the solutions. On the other hand, for sample solutions 4-6, it was assumed that [HMR] is approximately zero.
D eterm ination of HMR,MR0.07 0.06 0.05 0.04 0.03 0.02 0.01 0 0 2E-06 4E-06 6E-06 8E-06 0.00001 1.2E-05 1.4E-05 1.6E-05 Concentration of HMR Solution Absorbance at MR-

Figure 3. Determination of HMR,MRD eterm ination of HMR,HMR


0.5 Absorbance at HMR 0.4 0.3 0.2 0.1 0 0 2E-06 4E-06 6E-06 8E-06 0.00001 1.2E-05 1.4E-05 1.6E-05 Concentration of HMR Solution

9 10

Table 2. Data for Sample Solutions 710 Although the pKa of Methyl Red could be calculated from the data using the Henderson-Hasselbach equation, the pHs was plotted against log ([MR-]/[HMR])s to obtain the equation of the line. The y-intercept, b, is the pKa. Furthermore, the least squares method could also be used still obtaining the same pKa.

Figure 4. Determination of HMR,HMR

REFERENCES
pHvs log([MR ]/[H ]) . MR
6 log ([MR]/[HMR]) 5.8 5.6 5.4 5.2 5 4.8 -0.2 0 0.2 pH 0.4 0.6 0.8
-

[1] Loudon G. M. Organic Chemistry 3rd Edition. Benjamin/Cummings Publishing Company, Inc. 1988. Chapter 23, page 138 [2] Perkampus, H. H. UV-VIS Spectroscopy and Its Applications. Springer-Verlag Berlin Heidelberg 1992. Pages 3-4. SAMPLE CALCULATIONS Percent Yield Alizarin Yellow R

Figure 7. Plot of pH against log ([MR-]/ [HMR]) The pKa obtained is 5.03. This is 0.6% deviating from the literature value, 5.00. CONCLUSIONS
AND

RECOMMENDATIONS

The first part, the total synthesis of Alizarin Yellow R was deemed to be a failure. The experiment had a known source error from the start which may be the cause of the Alizarin Yellow R not recrystallizing. But then again, this may be another source of error thats why we obtained a really small yield of the end product. However, if the end product did not recrystallize in future experiments, we recommend that distilled water should be used in the recrystallization. This might lessen the yield of the pure product but it is still a good substitute for the acetone. In the spectrophotometric determination of the acid dissociation constant of methyl red, the experiment was successfully conducted. The experimental pKa was only 0.6% higher then the literature value of the pKa of Methyl Red. Nevertheless, there was still a source of error. Figure 6 showed this error. The figure showed a curve which is supposedly a straight line. The slope is negative while on the other graphs, they were positive. This may be because the solution might not be prepared according to the manual, or maybe because of the error of the spectrophotometer. Since the error of the instrument cannot be controlled, careful measuring of the amount of basic methyl red and NaOAc is advised.

= 26.67% Molar Concentrations of Solutions Methyl red stock solution

= 5.305 x 10-3 M (5.305 x 10-3 M) (0.035 L) = (0.05 L) (M methyl red stock) M methyl red stock = 3.713 x 10-3 M HMR and MR- Concentrations Sample Solution 7
0.702 = (4082.004551)[HMR] + (13572.71999) [MR-] 0.403 = (39833.72209)[HMR] + (-51.02526355) [MR-]

[HMR] = 1.017938623 x 10-5 [MR] = 4.865993696 x 10-5 pKa Determination Henderson-Hasselbach (Solution 7) pKa = 5.12 Least Squares solutions) Method (For all Equation

Standard Deviation = 5.03 Relative Error Calculation = 0.0458 =0.6% Range Range = Xhighest - Xlowest = 5.121 5.015 = 0.106 Mean RSD (in ppt)

= 9.046 Confidence Limits

= 5.063

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