Researcher

Matthew McBride

Objective

To determine the solubility of trans-dibenzalacetone (Product 284A in UCEXP284) in water and 1-octanol at 25°C using the temperature controlled Shake Flask Method and UV/Vis Spectroscopy.

Procedure

Add solute and solvent to a vial and allow the vial to mix on the shake flask apparatus at 25°C and then measure the solubility using UV/Vis Spectroscopy.

Results

Vial A (water): After 30 minutes of shaking
UV/Vis Spectrum of Vial A_50 dilution
λ max: 326 nm
Absorption units at λ max (A): 0.702311
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 0.001058 M

Vial A (water): After 1 day of shaking
UV/Vis Spectrum of Vial A_100dilution
λ max: 326 nm
Absorption units at λ max (A): 0.202799
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 6.1102e-4 M

Vial A (water): After 2 days of shaking
UV/Vis Spectrum of Vial A_100dilution
λ max: 327 nm
Absorption units at λ max (A): 0.430041
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 0.001296 M

Vial A (water): After 9 days of shaking
Lambda 2 Spectrometer
Spreadsheet with results of Vial A_100dilution
λ max: 327 nm
Absorption units at λ max (A): 0.873
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 0.00263 M

Lambda 35 Spectrometer
UV/Vis Spectrum of Vial A_9days100dilution
UV/Vis Spectrum of Sample cuvette (ethanol) vs Control cuvette (ethanol)
λ max: 328 nm
Absorption units at λ max (A): 0.821373
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 0.002475 M

Vial A (water): After 15 days of shaking and filtering the supernatant
Lambda 2 Spectrometer
Spreadsheet with results for Solution A_15days100dilution
Spreadsheet with results for Solution A_15days5dilution



Vial B (1-octanol): After 30 minutes of shaking
UV/Vis Spectrum of Vial B_500dilution
λ max: 326 nm
Absorption units at λ max (A): 0.560293
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 0.008441 M
HNMR Spectrum of the supernatant Vial B (1-octanol)

Vial B (1-octanol): After 1 day of shaking
UV/Vis Spectrum of Vial B_1,000dilution
λ max: 326 nm
Absorption units at λ max (A): 2.057319
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 0.06199 M

UV/Vis Spectrum of Vial B_10,000dilution
λ max: 327 nm
Absorption units at λ max (A): 0.171625
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 0.05171 M

Vial B (1-octanol): After 2 days of shaking
UV/Vis Spectrum of Vial B_10,000dilution
λ max: 329 nm
Absorption units at λ max (A): 0.471385
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 0.142 M
SAMS Sheet 1
Solubility determined from NMR: 0.092M

Vial B (1-octanol): After 9 days of shaking
Lambda 2 Spectrometer
Spreadsheet with results of Vial B_10000dilution
λ max: 328 nm
Absorption units at λ max (A): 0.350
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 0.105 M

UV/Vis Spectrum of Vial B_10000dilution
λ max: 329 nm
Absorption units at λ max (A): 0.338397
Pathlength (L): 1 cm
Extinction coefficient (ε) of trans-dibenzalacetone in ethanol: 33190 l·mol-1cm-1
Calculated concentration (c) using Beer's Law (A=εLc): 0.10196 M

Discussion

It was determined the solutions of water contained small bits of the product and was entering the ethanol dilutions and falsely increasing the number. The water supernatant must be filtered prior to being diluted.

Conclusion

The solubility of trans-dibenzalacetone in 1-octanol was measured to be about 0.1M, but the solubility in water could not be determined.

Log

2012-07-30

12:26 Added 0.1215 g of trans-dibenzalacetone (Product 284A in UCEXP284) to a 20 mL screw cap test tube (Vial A).
12:28 Added 0.1239 g of trans-dibenzalacetone to a 20 mL screw cap test tube (Vial B).
12:39 Added 5 mL of distilled water to Vial A. Crystals were still visible.
12:41 Added 5 mL of 1-octanol to Vial B. Crystals were still visible.
13:07 Attached the vials to the vortex genie and placed in the 25°C water bath. The vortex genie was turned on and was set to a shake level of 3.
13:40 The vials were removed from the water bath and the vortex genie.
13:48 Some of the crystals in Vial A were below the supernatant, but most of the crystals were floating above. 1 mL of the supernatant from Vial A (measured using a 1 mL volumetric flask) was added to a 5 mL volumetric flask. Ethanol was used to transfer the solution and to fill the 5 mL flask to create a 5 fold dilution.
13:52 All of the crystals in Vial B were below the supernatant. 1 mL of the supernatant from Vial B (measured using a 1 mL volumetric flask) was added to a 5 mL volumetric flask. Ethanol was used to transfer the solution and to fill the 5 mL flask to create a 5 fold dilution.
13:56 A few drops of the supernatant from Vial B was added to the inner coaxial NMR Tube 1.
13:59 The vials were reattached to the vortex genie and placed back in the water bath. The vortex genie was turned on.
14:19 A cuvette with a 1cm path length was filled with the VialA_5dilution solution. A cuvette with a 1cm path length was filled with the VialB_5fold solution. The solutions were analyzed using UV/Vis spectroscopy and ethanol as the control. The absorption units were well above 1 for both.
15:22 1 mL of the VialA_5dilution solution was added to a 10 mL volumetric flask. Ethanol was used to make the transfer and was used to fill the 10 mL volumetric flask to create a VialA_50dilution solution. This solution was added to a 1cm path length cuvette and analyzed by UV/Vis Spectroscopy. The file of the spectrum was saved as ONSEXP328VialA_30minutes50dilution.
16:00 1 mL of the VialB_5dilution solution was added to a 10 mL volumetric flask. Ethanol was used to make the transfer and was used to fill the 10 mL volumetric flask to create a VialB_50dilution solution. This solution was added to a 1cm path length cuvette and analyzed by UV/Vis Spectroscopy. The absorption units were around 11.
16:19 1 mL of the VialB_50dilution solution was added to a 10 mL volumetric flask. Ethanol was used to make the transfer and was used to fill the 10 mL volumetric flask to create a VialB_500dilution solution. This solution was added to a 1cm path length cuvette and analyzed by UV/Vis Spectroscopy. The file of the spectrum was saved as ONSEXP328VialB_30minutes500dilution.
16:30 Placed NMR Tube 1 (containing supernatant from Vial B) in a thin-walled NMR tube containing D2O and analyzed by 500MHz HNMR. The small peak at around 4.6ppm was referenced to 4.8ppm. The file of the spectrum was saved as ONSEXP328VialB_30minutes.

2012-07-31

11:04 Removed the vials from the 25°C water bath. Crystals were visible in both solutions. Vial A (water) had a clear supernatant and Vial B (1-octanol) had a light yellow supernatant. The crystals in both vials was below the supernatant.
13:30 Add 50 µL of the Vial A supernatant into a 5 mL volumetric flask and filled with ethanol. This was a Vial A_100dilution.
13:41 3 mL of the Vial A_100dilution was added to a cuvette and analyzed by UV/Vis spectroscopy. The file of the spectrum was saved as ONSEXP328VialA_1day100dilution.
14:16 Added 50 µL of the Vial B supernatant into a 5 mL volumetric flask and filled with ethanol. This was a VialB_100dilution. Added 1 mL of the VialB_100dilution solution to a 10 mL volumetric flask and filled with ethanol to make a VialB_1,000dilution.
14:39 Added 3 mL of the VialB_1,000dilution solution to a cuvette and analyzed by UV/Vis spectroscopy. The absorption units were at 2.5.
14:45 Added 1 mL of the VialB_1,000dilution to a 10 mL volumetric flask and filled with ethanol to create VialB_10,000dilution.
15:39 Added 3 mL of the VialB_10,000dilution to the cuvette with 1 cm pathlength and analyzed by UV/Vis spectroscopy. The spectrum of the file was saved as ONSEXP328A_1day10,000dilution.
16:13 The vials were placed back on the vortex genie in the 25°C water bath.

2012-08-01

16:48 Removed the vials from the vortex genie and the 25°C water bath. Yellow crystals were visible in both solutions.
16:56 Added 50 µL from the supernatant of Vial A (water) to a 5 mL volumetric flask and filled with ethanol. This was Solution A_2days100dilution. The flask was inverted several times to mix. 3 mL of the solution was added to a cuvette with a 1 cm pathlength and analyzed by UV/Vis spectroscopy. The file of the spectrum was saved as ONSEXP328VialA_2days100dilution.
17:14 A few drops of the supernatant from Vial B (1-octanol) was added to the inner coaxial NMR Tube 2.
17:25 Added 50 µL of the supernatant of Vial B to a 5 mL flask and filled with ethanol. This was Solution B_2days100dilution. The flask was inverted several times to mix. 50 µL of the Solution B_2days100dilution was added to a 5 mL flask and filled with ethanol. This was Solution B_2days10,000dilution. The flask was inverted to mix. 3 mL of the Solution B_2days10,000dilution was added to a cuvette with a 1 cm pathlength and analyzed by UV/Vis spectroscopy. The file of the spectrum was saved as ONSEXP328VialB_2days10,000dilution.
17:50 The NMR Tube 2 was placed in a thin-walled NMR tube holding D2O and analyzed by 500MHz HNMR. The spectrum was referenced by moving the peak near 4.6ppm to 4.8ppm. The file of the spectrum was saved as ONSEXP328VialB_2daysNMR.

2012-08-08

9:35 Removed Vials A and B from the 25°C water bath and the vortex genie that makes up the shake flask apparatus. Crystals were visible at the bottom of each solution and the supernatant for Vial A (water) was clear (little to no yellow color), while the supernatant for Vial B (1-octanol) was a yellow color. Took Picture #1.
9:41 50 µL (0.0495 g) of the supernatant from Vial A was transferred to a 5 mL volumetric flask. The flask was filled with ethanol and inverted to create Solution A_9days100dilution.
10:01 The sample cuvette and the control cuvette (both have a pathlength of 1 cm) were placed in the Lambda 2 Spectrometer and the absorption results were manually recorded at different wavelengths. The sample cuvette and the control cuvette were both filled with ethanol and the absorption results were manually recorded. Solution A_9days100dilution was placed in the sample cuvette and ethanol was in the control cuvette and the sample was analyzed. The sample was also analyzed using the Lambda 35 Spectrometer and the file of the spectrum was saved as ONSEXP328A_9days100dilution.
11:07 50 µL (0.0411 g) of the supernatant from Vial B was transferred to a 5 mL volumetric flask. The flask was filled with ethanol and inverted to create Solution B_9days100dilution.
11:11 50 µL (0.0372 g) of Solution B_9days100dilution was transferred to a 5 mL volumetric flask. The flask was filled with ethanol and inverted to create Solution B_9days10000dilution.
11:15 Solution B_9days10000dilution was placed in a cuvette and analyzed by the Lambda 2 Spectrometer. The absorbances were manually recorded at individual wavelengths. Ethanol was in the control cuvette. The sample was also analyzed by the Lambda 35 Spectrometer and the file of the spectrum was saved as ONSEXP328B_9days10000dilution. Vials A and B were placed back on the shake flask apparatus.

2012-08-13

16:17 Filtered a small amount of the supernatant from Vial A (water) through a pasteur pipette filter into a small vial. Transferred 50 µL (0.0491 g) of the filtered supernatant to a 5 mL volumetric flask and filled with ethanol. Inverted to mix the solution and transferred the solution to a cuvette with a pathlength of 1 cm. This sample was analyzed by the Lambda 2 Spectrometer with ethanol in the control cuvette. This sample was Solution A_15days100dilution.
16:35 1 mL of the filtered supernatant from Vial A (water) was added to a 5 mL volumetric flask and filled with ethanol. The flask was inverted to mix and transferred to a 1 cm pathlength cuvette. The sample was analyzed by Lambda 2 Spectrometer using ethanol in the control cuvette. The sample was also analyzed with a 4:1 ethanol/water mixture in the control cuvette. This sample was Solution A_15days5dilution.