# Patent

## Title
Method for quantifying permanganate-reducing compounds

## Abstract

A method for quantifying the permanganate-reducing compounds (PRCs) in an acetic acid sample is disclosed. The method comprises establishing a correlation between permanganate absorbances of standard samples and their PRC contents and determining the PRC content of the acetic acid sample by measuring its permanganate absorbance of a reaction mixture containing a standard permanganate solution and the acetic acid sample. The permanganate absorbance is obtained by subtracting the manganese dioxide absorbance from the absorbance of the mixture.

## Background
FIELD OF THE INVENTION
The invention relates to quantifying the permanganate-reducing compound content of an acetic acid sample.
BACKGROUND OF THE INVENTION
Acetic acid produced by the methanol carbonylation process contains oxidizable impurities such as aldehydes (see, e.g., U.S. Pat. No. 7,208,625). A qualitative test, called the Permanganate Time (PT), is used to determine the product quality. The PT test has a Pass or Fail designation. To perform the PT test, a known amount of KMnO4 is added to a known amount of acetic acid. To pass the test, the initial pink color of KMnO4 must not have completely dissipated after two hours. KMnO4, a strong oxidizing agent, can oxidize aldehydes and other oxidizable compounds (also called “permanganate-reducing compound” or PRC). In doing so, MnO4− is reduced to colorless Mn2+ according to the following reaction:

MnO4−+8H+→Mn2++4H2O

As PT is a visual test, there is considerable operator subjectivity involved in determining the point at which the pink color has disappeared. This visual test is further complicated and compromised by the fact that Mn2+ is relatively unstable and is prone to oxidation by MnO4− to form manganese dioxide (MnO2), a brownish/yellowish species, through the following reaction:

2MnO4−+3Mn2++2H2O→5MnO2+4H+

MnO2 in the reaction mixture interferes with the observation of the pink color. To overcome this difficulty, a recent report discloses a spectrophotometric method for correlating an objective colorimetric measurement with a subjective visual measurement and determining PT based on instrumental analysis (“A New System For Automatic Measurement of Permanganate Time,” Laboratory Automation and Information. Management, 34, 1999, 57-67). However, the report does not teach quantitatively determining the PRC content (or concentration) of an acetic acid sample.
SUMMARY OF THE INVENTION
The invention is a method for quantifying the permanganate-reducing compounds (PRCs) in an acetic acid sample. The method comprises establishing a correlation between the permanganate absorbances of standard samples and their PRC contents by (i) preparing two or more standard samples with known PRC contents; (ii) adding a known amount of a standard permanganate solution to each standard sample to form a mixture; (iii) for each standard sample, measuring the absorbance of the mixture at a selected wavelength in the range of 460 to 580 nm at a set reaction time; (iv) for each standard sample, determining the permanganate absorbance by the difference between the absorbance of the mixture and the manganese dioxide absorbance; and (v) establishing a correlation between the permanganate absorbances of the standard samples and their PRC contents. The PRC content of the acetic acid sample is determined from the correlation and its permanganate absorbance that can be determined by repeating steps (ii) to (iv) above.



BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a typical UV-Vis absorption spectrum of an aqueous KMnO4 solution.
FIG. 2 shows UV-Vis absorption spectra of a mixture of an acetic acid sample (containing 15.2 ppm equivalent crotonaldehyde, 2 mL), distilled water (10 mL), and a standard KMnO4 solution (0.02 N, 0.5 mL) recorded after (a) 15 min; (b) 30 min; and (c) 120 min.
FIG. 3 is a UV-Vis spectrum of a mixture of an aqueous KMnO4 solution (0.02 N, 0.5 mL), distilled water (10 mL), and an acetic acid sample (containing 20.4 ppm equivalent crotonaldehyde, 2 mL) recorded 15 min after they are mixed.
FIG. 4 shows permanganate absorbances of mixtures of standard samples as a function of the reaction time. The crotonaldehyde contents are: (a) 3.8 ppm; (b) 7.9 ppm; (c) 10.6 ppm; (d) 13.0 ppm; (e) 15.2 ppm; (f) 20.4 ppm; and (g) 25.2 ppm.
FIG. 5 is a crotonaldehyde content v. permanganate absorbance calibration curve.
FIG. 6 is a UV-Vis spectrum of a mixture of an aqueous KMnO4 solution (0.02 N, 0.5 mL), distilled water (10 mL), and an unknown acetic acid sample (2 mL) recorded 15 min after they are mixed.



DETAILED DESCRIPTION OF THE INVENTION
The invention is a method for quantifying the permanganate-reducing compounds (PRCs) in an acetic acid sample. Acetic acid produced by the methanol carbonylation process often contains aldehydes, including acetaldehyde, propionaldehyde, butyraldehydes, crotonaldehyde, their derivatives such as 2-ethyl crotonaldehyde, 2-ethyl butyraldehyde, and the like. In addition to aldehydes, an acetic acid sample may contain other compounds that can be oxidized by permanganate (see, e.g., U.S. Pat. No. 7,208,625).
The method uses a standard permanganate solution, preferably an aqueous solution. More preferably, the standard permanganate solution is an aqueous solution of potassium, sodium, ammonium, or alkylammonium permanganate salt. An aqueous potassium permanganate solution is most preferred.
The method comprises preparing two or more standard samples with known PRC contents. A standard sample may be prepared by mixing a solvent with a known amount of PRC. Examples of suitable solvents include water, alcohols, carboxylic acids, amides, nitriles, and the like. Preferably the solvent contains negligible amount of PRC, for example, less than 0.5 ppm equivalent crotonaldehyde, more preferably, less than 0.1 ppm equivalent crotonaldehyde. One preferred solvent is water. Conveniently, an aldehyde may be spiked in the solvent to prepare the standard samples.
A known amount of the standard permanganate solution is added to each standard sample to form a reaction mixture (“mixture”). Depending on the PRC content of the standard sample, additional solvent may be used to prepare the reaction mixture. The amount of solvent used depends on the PRC content of the acetic acid sample to be analyzed.
For each standard sample, the absorbance of the mixture (also called “mixture absorbance” or Amix) at a selected wavelength in the range of 460 to 580 nm is measured at a set reaction time. Generally, a peak absorbance at about 506, 525, or 544 nm is measured. The reaction time between the standard permanganate solution and the standard sample is conveniently 10 to 30 min. The reaction is preferably carried out at room temperature.
Generally, an ultraviolet-visible (UV-Vis) spectrophotometer is used to measure the absorbance of the mixture. A plot of the absorbance versus wavelength is called an absorption spectrum. FIG. 1 shows a typical UV-Vis spectrum of an aqueous KMnO4 solution recorded at room temperature. The solution is prepared by mixing distilled water (12 mL) and a standard KMnO4 solution (0.02 N, 0.5 mL).
In a quantitative analysis, the absorbance A at a given wavelength is related to the analyte content c by Beer's law: A=a×b×c, where a is absorptivity of the analyte and b is the sample pathlength. The absorbance of a species depends on not only its concentration, but also the pathlength of the cuvette used.
When a standard permanganate solution is added to a standard sample containing PRCs, the reaction between them gives colorless Mn2+. However, Mn2+ can react with MnO4− to form yellowish/brownish manganese dioxide (MnO2). FIGS. 2(a), 2(b), and 2(c) are spectra of a mixture of a standard sample containing 15.2 ppm equivalent crotonaldehyde (2 mL), water (10 mL), and an aqueous KMnO4 solution (0.02 N, 0.5 mL) recorded after they react for 15, 30, and 120 min, respectively. The initial permanganate concentrations in the mixtures of FIG. 1 and FIG. 2 are the same, because there is not reaction in either mixture when they are just formed. FIG. 2(a) shows a large decrease in permanganate absorbance at around 525 nm as compared to FIG. 1. However, the amount of MnO2 present in the solution is not significant as indicated by the small increase of absorption at around 425 nm. This indicates that the permanganate is predominantly reduced by PRCs during the first 15 min. Spectras (b) and (c), on the other hand, show the formation of significant amounts of MnO2, indicating that significant amount of permanganate is reacted with Mn2+ to form MnO2. Since the absorption of light by the MnO2 and permanganate in the mixture is additive, the absorbance of the mixture, Amix, is the sum of the permanganate absorbance (Aperm) and the absorbance due to MnO2 present in the mixture (AMnO2), i.e., Amix=Aperm+AMnO2.
AMnO2 can be determined by many techniques. See K. A. Rubinson, “Chapter 7. Introduction to Spectroscopy,” Chemical Analysis (1986) pp. 615-661). In one technique, AMnO2 is determined by drawing a baseline across the base of a permanganate absorption band. Such a baseline correction technique was used to analyze samples containing rock dust and coal by infrared spectrometry (R. A. Friedel, J. A., Queiser, “Inorganic and Organic Analysis by Infrared Spectrometry in Coal Problems,” ACS Preprints—Fuel Chemistry Division Symposium, 10(3), 1966, pp. 1-6, available at http://www.anl.gov/PCS/acsfuel/preprint %20archive/Files/10—3_NEW %20YORK—0966—0120.pdf). The non-specific absorption due to the coal is corrected out by drawing a baseline across the base of the absorption band of the rock dust.
FIG. 3 is a UV-Vis spectrum of a reaction mixture recorded 15 min after the addition of a standard KMnO4 solution (0.02 N, 0.5 mL) and distilled water (10 mL) in a standard sample containing 20.4 ppm equivalent crotonaldehyde (2 mL). A baseline is drawn across the base of the permanganate absorption band from 460 nm to 580 nm. The segment M′N′ approximates the absorbance of MnO2 between 460 nm and 580 nm. The absorbance due to MnO2 in the mixture at 525 nm is represented by segment Q′R′.
A correlation is established between the PRC contents and permanganate absorbances of the standard samples. The correlation may be a graph, a table, a mathematical equation, or the like. Preferably, a calibration curve is constructed by plotting PRC contents against their permanganate absorbances. FIG. 4 is a calibration curve constructed from the permanganate absorbances of the standard samples and their equivalent crotonaldehyde contents.
To determine the PRC content of an unknown acetic acid sample, the same amount of the standard permanganate solution, and the same amount of solvent if used, is added to the unknown acetic acid sample to form a mixture. The absorbance of the mixture (Amix) is measured at the selected wavelength at the set reaction time. The permanganate absorbance is determined by subtracting from Amix the MnO2 absorbance. The PRC content of the unknown sample is determined from the permanganate absorbance and the correlation obtained from the standard samples.
Since identities of aldehydes or other PRCs present in an acetic acid sample is often not known, The PRC content may be expressed in any convenient manner, e.g., in terms of —CHO content. Conveniently, the PRC content is expressed in term of an equivalent aldehyde concentration, e.g., ppm equivalent acetaldehyde, crotonaldehyde, or the like.
EXAMPLE
A Shimadzu 1700 Pharma spectrophotometer is used. All UV-Vis measurements are performed at room temperature. A standard KMnO4 solution (0.02 N) is prepared by dissolving 0.63 g KMnO4 (0.63 g) in distilled water (1 L).
The standard KMnO4 solution (0.5 mL) is mixed with distilled water (12 mL). A portion of the mixture (3 mL) is transferred to a disposable, 1-cm pathlength polystyrene cuvette. A UV-Vis spectrum is recorded immediately, as shown in FIG. 1. Further spectra recorded over a period of one hour show no change in absorption, indicating that there is no decomposition of KMnO4 in the mixture.
An acetic acid sample (Aldrich, >99.99%) is determined to have a PRC content of 3.8 ppm equivalent crotonaldehyde (see co-pending U.S. patent application Ser. No. 12/589,931, filed Oct. 30, 2009. A standard acetic acid sample (containing 20.4 ppm equivalent crotonaldehyde) is prepared by spiking crotonaldehyde in the Aldrich acetic acid. The standard sample (2 mL) is mixed with distilled water (10 mL) and the standard KMnO4 solution (0.5 mL). A portion of the mixture (3 mL) is transferred to a disposable, 1-cm pathlength polystyrene cuvette. A UV-Vis spectrum is recorded after 15 min, as shown in FIG. 3. A baseline is drawn across the base of the absorption band of permanganate. The segment M′N′ approximates the absorbance of MnO2 between 440 nm and 600 nm. The absorbance due to MnO2 in the mixture at 525 nm is represented by segment Q′R′. Thus the absorbance of the permanganate in the mixture at 525 nm after the MnO2 absorption correction is represented by segment P′Q′, which is 0.101.
Additional standard samples are prepared by adding known amounts of crotonaldehyde to the Aldrich acetic acid. Their equivalent crotonaldehyde contents are shown in Table 1. The permanganate absorbances of mixtures are determined by the method described as above and plotted as a function of time as shown in FIG. 4. FIG. 4 shows that most of the permanganate reaction takes place during the first 15 min.










TABLE 1








Equivalent Crotonaldehyde



Standard Sample
(ppm)



















a
3.8



b
7.9



c
10.6



d
13.0



e
15.2



f
20.4



g
25.2










Permanganate absorbances of mixtures of the standard samples at 15 min are plotted against their crotonaldehyde contents, as shown in FIG. 5. A good linear fit provides a correlation equation of the form: PRC content=−126.7×Aperm+32.6. The PRC content is expressed in equivalent crotonaldehyde (ppm).
The PRC content of an unknown acetic acid sample can be determined from the calibration curve in FIG. 5 by measuring its permanganate absorbance. One can also calculate the PRC content using the above equation.
An acetic acid sample of unknown PRC content (2 mL) is mixed with distilled water (10 mL) and the standard KMnO4 solution (0.5 mL). A portion of the mixture (3 mL) is transferred to a 1-cm pathlength polystyrene cuvette. A UV-Vis spectrum is recorded 15 min after the mixture is made, as shown in FIG. 6. The unknown acetic acid sample has an Aperm value of 0.188. Its PRC content is calculated to be 8.8 ppm equivalent crotonaldehyde.

## Claims

1. A method for quantifying a permanganate-reducing compound (PRC) content of an acetic acid sample, comprising:
(a) measuring a permanganate absorbance of a reaction mixture comprising a known amount of a standard permanganate solution and the acetic acid sample at a selected wavelength from 460 nm to 580 nm at a set reaction time wherein the permanganate absorbance is determined by determining manganese dioxide absorbance and subtracting the determined manganese dioxide absorbance from the absorbance of the mixture;
(b) adding a known concentration of PRC to the acetic acid sample to produce a spiked sample;
(c) repeating step (a) with the spiked sample to measure the absorbance of the reaction mixture of the spiked sample (Asp);
(d) measuring the permanganate absorbance of a blank sample (ABL) and
(e) determining the PRC content of the acetic acid sample by:


[PRC]AA=(ABL−AAA)×[PRC]sp/(AAA−Asp),

wherein
[PRC]AA is the PRC content of the acetic acid sample,
[PRC]sp is the spiked PRC concentration,
Asp is the absorbance of the reaction mixture of the spiked sample and the standard permanganate solution,
AAA is the permanganate absorbance of the reaction mixture of the acetic acid sample and the standard permanganate solution, and
ABL is the permanganate absorbance of the mixture of the blank sample and the standard permanganate solution.

2. The method of claim 1 wherein the manganese dioxide absorbance is determined by a baseline drawn across the base of a permanganate absorption band.

3. The method of claim 1 wherein the standard permanganate solution is a potassium permanganate solution.

4. The method of claim 1 wherein the set reaction time is from 10 to 30 min.

5. The method of claim 1 wherein the blank sample is selected from the group consisting of water, alcohols, carboxylic acids, amides, nitriles, and mixtures thereof.

6. The method of claim 5 wherein the blank sample is water.

7. The method of claim 1 wherein a solvent is used to form the mixture.

8. The method of claim 7 wherein the solvent is selected from the group consisting of water, alcohols, carboxylic acids, amides, nitriles, and mixtures thereof.

9. The method of claim 8 wherein the solvent is water.