Cyclohexanol analysis

Corrective Action Application Case 1 - Groundwater at the MEMOREX Computer Tape Plant (Santa Clara, California) was contaminated by a leaking underground solvent storage tank (Skladany et al., 1987). Chemical analysis of the groundwater identified the presence of methyl ethyl ketone (MEK) up to 500 ppm xylenes together with ethyl benzene up to 40 ppm cyclohexanone up to 30 ppm cyclohexanol up to 10 ppm acetone up to 10 ppm and toluene, tetrahydrofuran, 2-butanol, and methyl propyl ketone each less than 1 ppm. A biological... 

Figure 12.14 Chromatographic analysis of aniline (a) Precolumn chromatogram (the compound represented by the shaded peak is solvent flushed) (b) main column chromatogram without cryotrapping (c) main column chromatogram with ciyottapping. Conditions DCS, two columns and two ovens, with and without ciyottapping facilities columns OV-17 (25 m X 0.32 mm i.d., 1.0 p.m d.f.) and HP-1 (50 m X 0.32 mm, 1.05 p.m df). Peak identification is as follows 1, benzene 2, cyclohexane 3, cyclohexylamine 4, cyclohexanol 5, phenol 6, aniline 7, toluidine 8, nittobenzene 9, dicyclohexylamine. Reprinted with permission from Ref. (20).

The reaction product was filtered to remove catalyst and analyzed in GC equipped with an HP5 (30 m X 0.32 mm X 0.25 pm) column. The temperature program used for analysis (31 °C - 35 min - 1 °C/min - 40 °C - 10 °C/min -120 °C) ensured complete separation of the cyclohexanol, cyclohexanone, and phenol peaks. The conversion and selectivity were calculated directly from the area of each peak. 

General Methods. Methanol used in kinetic runs was distilled from sodium methoxide or calcium hydride in a nitrogen atmosphere before use. Freshly distilled cyclohexanol was added to the methanol in the ratio 6.0 ml cyclohexanol/200 ml MeOH and was used as an internal standard for gas chromatographic (GC) analysis. Benzaldehyde was distilled under vacuum and stored under nitrogen at 5°. Other aldehydes (purchased from Aldrich) were also distilled before use. The corresponding alcohols (purchased from Aldrich) were distilled and used to prepare GC standards. All metal carbonyl cluster complexes were purchased from Strem Chemical Company and used as received. Tetrahydrofuran (THF) was distilled from sodium benzophenone under nitrogen before use. 

Gas chromatographic analysis shows that the ethereal extract contains solely cyclohexanol (>98%). 

Gas chromatographic analysis of the product shows that the product is at least 99.2% pure and is contaminated only with trace amounts of cyclohexanol. The submitter reported a 62-69% yield (15.7-17.5 g.) using the indicated scale. 

The conclusion of this short analysis is that particular attention should be paid to the selection and design of the evaporator, in order to reduce the amount of phenol in the residual waste. In general, this process should not raise critical environmental and health problems. The amount of waste to environment may be reduced even more. Thus, by evaporation/distillation, about 40 kg/h phenol and 50kg/h cyclohexanol can be recovered from waste. In this way the overall material yield can be increased to 99.35%. Additionally, cyclohexene can be reconverted in cyclohexanol and recycled into the process. In this way the amount of waste may be decreases to below 0.5%, consistent with the initial target. 

The above points are explained by discussing retrosynthetic analysis of cyclohexanol ... 

Hexadecafluorophthalocyanine (FiePc) complexes of Ru(II) which were prepared by the reaction of tetrafluorophthalonitrile and Ru3(CO)i2, have been encapsulated in the supercages of zeolites NaX. The X type zeolites were synthesized around the RuFiePc complexes. The zeolites modified with the metal complexes were characterized by XRD, FT-IR and UV-Vis spectroscopy as well as elemental analysis. The oxidation of cyclohexane using t-butylhydroperoxide was catalyzed by the intrazeolite RuFiePc complexes. Complete conversion to cyclohexanone and cyclohexanol was achieved with nearly 3000 turnovers per day. These ship-in-a-bottle RuFisPc complexes show no signs of deactivation in contrast to the iron analogs, regardless of how the peroxide is administered during the reaction. 

SCHEME 18. Stereoselective formation of calix[4]cyclohexanone 63 and caUx[4]cyclohexanol 64. (a) RhCl3-3H20/AIiquat336/H20/CH2Cl2, 200 psi H2, 90°C. (b) NaOEt/HOEt (c) NaBa,. The indicated configuration of 64 was confirmed by X-ray analysis... 

For cyclohexanol adsorption on the three faces of lowest indices of zinc (in 100 mM KCl + 0.1 mM H2SO4), C(E) curves are given in Fig. 50. Obviously, only one of the adsorption-desorption peaks is observable in the dl region. These results were shown to fit the two-parallel-capacitors model (dashed lines). For a given concentration of adsorbate, the potentials of the peak and of the maximum of adsorption shift in the same order as the pzc s in base electrolyte. From the complete analysis of the curves, all adsorption parameters were found to be co dependent.f... 

Materials. Samples of NaY zeolite with Si/Al ratio of 2.47 determined by ICP and of 3.80 by XPS analysis are obtained liom Zeocat 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminocyclohexene, 1,2-diaminobenzene with 99 % purity were from ALDRICH dichloromethane, cyclohexene, cyclohexanol with 99 % purity, H2O2 (30 % soln. in water) and /er/-butylhydroperoxide (tBHP) (70 % soln. in di-/er/-butylperoxide) were from ACROS. 

Oxidation of cyclohexanol was carried out at 328 K in a three necked round bottomed flask under reflux conditions using 30 wt.% H2O2 as oxidant and acetone as solvent. The temperature was maintained by thermostated oil bath. For oxidation of cyclohexane, reaction was performed in a PARR (4842) autoclave at 423 K for 3h. Quantitative analysis of the products were done using Nucon G.C. fitted with a FID. 

The reactions were monitored by recording the hydrogen uptake to allow calculation of the reaction rate as mol/hr/gm cat. The hydrogen uptake was then cotr ared to the theoretical amount of hydrogen (0.448 litres) required to convert the phenol to the cyclohexanol. The selectivity was determined by GC analysis of the reaction products after filtering off the catalyst. 

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