EXP072

==media type="custom" key="3635005"media type="custom" key="3556574"media type="custom" key="3556590"media type="custom" key="3556586"media type="custom" key="3556592"media type="custom" key="3678929"==

Researcher
David Bulger

Obejective
To determine the solubility of DL-mandelic acid, trans-cinnamic acid, 4-phenylbutyric acid, L-ascorbic acid, acetylsalicylic acid and 4,4-azoxydibenzoic acid in various solvents using 1H NMR.

Procedure
[|DL-mandelic acid], [|trans-cinnamic acid], [|4-phenylbutyric acid], [|L-ascorbic acid], [|acetylsalicylic acid], and [|4,4-azoxydibenzoic acid] were saturated in [|chloroform](except acetylsalicylic acid), [|tetrahydrofuran], [|methanol], [|hexanol], [|toluene], and [|diethyl ether] by adding excess solute to solvent and sonicating solution for 30 min. Samples were then left to equilibrate at room temperature (usually 23.0 degrees Celsius). Supernatant liquid pipetted into NMR tubes and 20 uL of CHCl3 added with a microsyringe if CHCl3 is not the solvent. NMR runs performed on 300 MHz JEOL Spectrometer with 16 384 x_points, 8 scans, 45 degree pulse, and 4 second relaxation delay. Molarity calculated using Semi-Automated Measurement of Solubility ([|SAMS]).

Results
The solubilities are calculated in [|ONSC-EXP072-sheet1], [|ONSC-EXP072sheet2], [|ONSC-EXP072sheet3], and [|ONSCEXP072sheet4].

Note: Solubility measurements will not be available until SAMS is adjusted to work with the .jdx format used in this experiment.
 * [Have you tried to resave the files according to AL's suggestion? To convert, open the spectrum file in JSpecView, then file -> export JCAMP-DX -> XY**
 * You can get the standalone** [|**JSpecView program from SourceForge**] **JCB]** Thank you for the suggestion. I converted it as you explained and adjusted the solute and solvent ranges accordingly. However, SAMS was still unable to read it. (See NMR20_ASA_detSAMS in [|ONSC-EXP072sheet3]) **[This resaved spectrum looks like the phasing is way off JCB]** You are right. When the file was converted, the phasing and shifts became distorted. The JSpecView program from SourceForge does not have phase correction. Besides, if the phasing were corrected, would SAMS be able to read it any better? **[AL is working on fixing this - it looks like just another little glitch to be fixed and you can generate results from this experiment - SAMS has worked fine in experiments done on our Varian instrument and it should work for you as well JCB]** AL explained that in order for the conversion to be right, the n=1 spectrum must be selected rather than the default of n=2. The n=2 spectra demonstrate the distorted phasing. SAMS is able to read the converted n=1 spectra. (See NMR23_DL-Ma_detS in [|ONSC-EXP072sheet3])
 * [OK it looks like you are getting your integrations now - but you need to fix several issues as you include all the rest:**
 * 1) You are significantly offscale - set the shift to the known value for the solvent - for example the** [|**triplet in diethyl ether is at 1.13 ppm**] **You can change this directly in the JCAMP file via the offset - see AL for help if needed.**
 * 2) Your spectrum is inverted - again there is a setting in the JCAMP file to switch this**
 * 3) You are counting 4H in some entries in the spreadsheet for diethylether, which is correct for the methylene groups next to O but your ranges are wrong.**
 * JCB]** AL showed me how to set the shift and reverse the spectra. The ranges change with the conversion of the spectra and have to be redone each time the spectrum changes.

(Photo linked) || Spectrum || Solute || Solvent || Solubility (M) ||
 * Sample Name
 * [|NMR1] ||  || Acetylsalicylic acid || THF || (Impure Solvent) ||
 * [|NMR2] || [|Spectrum_315] || Acetylsalicylic acid || Methanol || 1.32 ||
 * [|NMR3] ||  || 4,4-Azoxydibenzoic acid || THF || (Impure Solvent) ||
 * [|NMR4] ||  || L-Ascorbic acid || THF || (Impure Solvent) ||
 * [|NMR5] || [|Spectrum_353] || L-Ascorbic acid || CHCl3 || insoluble ||
 * [|NMR6] || [|Spectrum_361] || 4,4-Azoxydibenzoic acid || CHCl3 || insoluble ||
 * [|NMR7] ||  || 4,4-Azoxydibenzoic acid || Methanol || (Mislabeled) ||
 * [|NMR8] ||  || L-Ascorbic acid || Methanol || (Mislabeled) ||
 * [|NMR9] || [|Spectrum_355] || 4-Phenylbutyric acid || CHCl3 || 4.04 ||
 * [|NMR10] || [|Spectrum_330] || 4-Phenylbutyric acid || Methanol || 4.80 ||
 * [|NMR11] ||  || 4-Phenylbutyric acid || THF || (Impure Solvent) ||
 * [|NMR12] || [|Spectrum_334] || DL-Mandelic acid || Methanol || 3.62 ||
 * [|NMR13] ||  || DL-Mandelic acid || THF || (Impure Solvent) ||
 * [|NMR14] || [|Spectrum_359] || DL-Mandelic acid || CHCl3 || 0.10 ||
 * [|NMR15] || [|Spectrum_347] || trans-Cinnamic acid || Methanol || 1.32 ||
 * [|NMR16] ||  || trans-Cinnamic acid || THF || (Impure Solvent) ||
 * [|NMR17] || [|Spectrum_357] || trans-Cinnamic acid || CHCl3 || 0.83 ||

Photo || Spectrum || Solute || Solvent || Solubility (__M__) || [|EXP072_18_(ASAHexanol)] || [|NMR18_ASA_hex] || Acetylsalicylic acid || Hexanol || insoluble || [|EXP072_19_(ASAToluene)] || [|NMR19_ASA_tol] || Acetylsalicylic acid || Toluene || insoluble || [|EXP072_20_(ASADiethylether)] || [|NMR20_ASA_detS] || Acetylsalicylic acid || Diethyl Ether || 0.18 || [|EXP072_21_(LD-MaHexanol)] || [|NMR21_DL-Ma_hex] || DL-Mandelic acid || Hexanol || insoluble || [|EXP072_22_(DL-MaToluene)] || [|NMR22_DL-Ma_tol] || DL-Mandelic acid || Toluene || insoluble || [|EXP072_23_(DL-MaDiethylether)] || [|NMR23_DL-Ma_detS] || DL-Mandelic acid || Diethyl Ether || 0.98 || [|EXP072_24_(AscHexanol)] || [|NMR24_Asc_hex] || L-Ascorbic acid || Hexanol || insoluble || [|EXP072_25_(AscToluene)] || [|NMR25_Asc_tol] || L-Ascorbic acid || Toluene || insoluble || [|EXP072_26_(AscDiethylether)] || [|NMR26_Asc_det] || L-Ascorbic acid || Diethyl Ether || insoluble || [|EXP072_27_(44-AzHexanol)] || [|NMR27_44-az_hex] || 4,4-Azoxydibenzoic acid || Hexanol || insoluble || [|EXP072_28_(44-AzToluene)] || [|NMR28_44-az_tol] || 4,4-Azoxydibenzoic acid || Toluene || insoluble || [|EXP072_29_(44-AzDiethylether)] || [|NMR29_44-az_det] || 4,4-Azoxydibenzoic acid || Diethyl Ether || insoluble || [|EXP072_30_(4-PhbHexanol)] || [|NMR30_4-phb_hexS] || 4-Phenylbutyric acid || Hexanol || 0.50 || [|EXP072_31_(4-PhbToluene)] || [|NMR31_4-phb_tolS] || 4-Phenylbutyric acid || Toluene || 3.67 || [|EXP072_32_(4-PhbDiethylether)] || [|NMR32_4-phb_det] || 4-Phenylbutyric acid || Diethyl Ether || 4.13 || [|EXP072_33_(t-CinHexanol)] || [|NMR33_Cin_hex] || trans-Cinnamic acid || Hexanol || insoluble || [|EXP072_34_(t-CinToluene)] || [|NMR34_Cin_tol] || trans-Cinnamic acid || Toluene || 0.23 || [|EXP072_35_(t-CinDiethylether)] || [|NMR35_Cin_det] || trans-Cinnamic acid || Diethyl Ether || 0.54 || media type="googlespreadsheet" key="plwwufp30hfr0ns7tx_wXeQ" height="400" width="800" media type="googlespreadsheet" key="plY8_siwYHa3ZcpwPamVFNw" height="400" width="800" media type="googlespreadsheet" key="plY8_siwYHa13OUrFH0Nccw" height="400" width="800" media type="googlespreadsheet" key="plY8_siwYHa2--VqAqIA2Rg" height="400" width="800"
 * Sample Name
 * NMR18
 * NMR19
 * NMR20
 * NMR21
 * NMR22
 * NMR23
 * NMR24
 * NMR25
 * NMR26
 * NMR27
 * NMR28
 * NMR29
 * NMR30
 * NMR31
 * NMR32
 * NMR33
 * NMR34
 * NMR35

Discussion
Also, it appears that all the THF samples contain the same impurities. Therefore, the THF samples will not be included in the solubility measurements.
 * [NMR1 of ASA and THF has lots of impurities and is not zeroed properly - see EXP069 for the THF range - also the proton count is not right JCB]** You are right. I just recently figured out how to use the chloroform peak as a reference to get the spectra at the correct ppm. In future experiments, spectral shifts will be manually set using chloroform or the solvent **[You don't need to add chloroform to zero the peaks - just look up the shift of the solvent you happen to be using - for example** [|**methanol is 3.31 ppm**] **JCB]** Good point.

Conclusion
Acetylsalicylic acid was insoluble in hexanol and toluene and its solubility was measured to be 1.32 M in methanol and 0.18 M in diethyl ether. L-Ascorbic acid and 4,4-Azoxydibenzoic acid were measured to be insoluble in chloroform, hexanol, diethyl ether, and toluene. The solubility of 4-phenylbutryric acid was measured to be 4.04 M in chloroform, 4.08 M in methanol, 0.50 M in hexanol, 3.67 M in toluene, and 4.13 M in diethyl ether. DL-Mandelic acid was measured to be insoluble in hexanol and toluene, and soluble to 3.62 M in methanol, 0.10 M in chloroform, and 0.98 M in diethyl ether. Trans-Cinnamic acid was measured to be insoluble in hexanol, 1.32 M in methanol. 0.83 M in chloroform, 0.23 M in toluene, and 0.54 M in diethyl ether.

Log
03.27.09 CST

16.06 - Vials filled with solvent and excess solute.**[Define the names of the samples and how they correspond to each solute JCB]** Names and corresponding solutes and solvents are now under results. 18.08 - Began sonication (21 degrees Celsius) 18.36 - Removed from sonicator (30 degrees Celsius) 18.36 - Left to equilibrate for 72 h 44 min

03.30.09

19.20 - Photos of equilibrated samples **[give these a name - like ONSC072pic1 JCB]** Pictures have been uploaded. Future picture will be given names like ONSC072pic1 etc. **[ Did you notice the temp at this point? JCB]** No, I did not check the temperature in the water bath, but the lab temp is usually around 23 degrees Celsius. I will check the temperature when I redo the CHCl3 NMR runs. 19.33 - NMR1a (autogain = 3; spectrum 301; 10 uL CHCl3 added) **[Are you taking the NMR with the solid present or did you separate? Are you adding chloroform or CDCl3 JCB]** Supernatant liquid that was separated from solid during equilibration was used and CHCl3 was added. 19.41 - NMR1b (autogain = 3; spectrum 302; 20 uL CHCl3 added) 19.46 - NMR1c (autogain = 3; spectrum 304; 40 uL CHCl3 added) 19.59 - NMR1d (autogain = 3; spectrum 312; 100 uL CHCl3 added) 20.16 - NMR2 (autogain = 1; spectrum 315; 20 uL CHCl3 added) 20.29 - NMR3 (autogain = 1; spectrum 317; 20 uL CHCl3 added) **[If you added CHCl3 to a saturated CHCl3 solution you cant use the integrations to get the solubility. Adding CDCl3 would have been OK JCB JCB]** You are right. I will have to redo the CHCl3 NMR runs without adding CHCl3. I can use the left over equilibrated samples. 20.44 - NMR4 (autogain = 2; spectrum 319; 20 uL CHCl3 added) 20.55 - NMR5 (autogain = 9; spectrum 321; 20 uL CHCl3 added) 21.10 - NMR6 (autogain = 9; spectrum 322; 20 uL CHCl3 added) 21.14 - NMR7 (autogain = 1; spectrum 324; 20 uL CHCl3 added) 21.21 - NMR8 (autogain = 2; spectrum 326; 20 uL CHCl3 added) 21.29 - NMR9 (autogain = 5; spectrum 328; 20 uL CHCl3 added) 21.43 - NMR10 (autogain = 2; spectrum 330; 20 uL CHCl3 added) 21.47 - NMR11 (autogain = 4; spectrum 332; 20 uL CHCl3 added) 21.58 - NMR12 (autogain = 2; spectrum 334; 20 uL CHCl3 added) 22:04 - NMR13 (autogain = 5; spectrum 336; 20 uL CHCl3 added) 22.17 - NMR14 (autogain = 9; spectrum 345; 20 uL CHCl3 added) 22.23 - NMR15 (autogain = 1; spectrum 347; 20 uL CHCl3 added) 22.28 - NMR16 (autogain = 4; spectrum 349; 20 uL CHCl3 added) 22.34 - NMR17 (autogain = 8; spectrum 351; 20 uL CHCl3 added)
 * [You should only need one spectrum here per sample and use the solubility spreadsheet to calculate the solubilities directly JCB]**

03.31.09

17.51 - Room temperature checked (23.0 degrees Celsius) 18.00 - NMR5 (autogain = 9; spectrum 353; no CHCl3 added) 18.04 - NMR9 (autogain = 4; spectrum 355; no CHCl3 added) 18.16 - NMR17 (autogain = 8; spectrum 357; no CHCl3 added) 18.21 - NMR14 (autogain = 9; spectrum 359; no CHCl3 added) 18.26 - NMR6 (autogain = 9; spectrum 361; no CHCl3 added) 18.30 - Cleaned glassware 20.00 - Prepared samples 18-35 (solute and solvent added to vials) 21.30 - Began sonication (22.0 degrees Celsius) 22.00 - Removed from sonicator (31.2 degrees Celsius) 22.00 - Left to equilibrate

04.03.09

15.47 - Photos of Samples 18-35 16.58 - NMR18 (autogain = 1; NMR18_ASA_hex; 20 uL CHCl3 added) 17.10 - NMR19 (autogain = 2; NMR19_ASA_tol; 20 uL CHCl3 added) 17.18 - NMR20 (autogain = 2; NMR20_ASA_det; 20 uL CHCl3 added) 17.30 - NMR21 (autogain = 1; NMR21_LD-Ma_hex; 20 uL CHCl3 added) 17.38 - NMR22 (autogain = 2; NMR22_LD-Ma_tol; 20 uL CHCl3 added) 17.46 - NMR23 (autogain = 2; NMR23_LD-Ma_det; 20 uL CHCl3 added) 17.57 - NMR24 (autogain = 1; NMR24_Asc_hex; 20 uL CHCl3 added) 18.09 - NMR25 (autogain = 2; NMR25_Asc_tol; 20 uL CHCl3 added) 18.16 - Room temperature checked (23.0 degrees Celsius) 18.21 - NMR26 (autogain = 2; NMR26_Asc_det; 20 uL CHCl3 added) 18.28 - NMR27 (autogain = 1; NMR27_44-az_hex; 20 uL CHCl3 added) 18.38 - NMR28 (autogain = 2; NMR28_44-az_tol; 20 uL CHCl3 added) 18.44 - NMR29 (autogain = 2; NMR29_44-az_det; 20 uL CHCl3 added) 18.53 - NMR30 (autogain = 1; NMR30_4-phb_hex; 20 uL CHCl3 added) 19.01 - NMR31 (autogain = 2; NMR31_4-phb_tol; 20 uL CHCl3 added) 19.13 - NMR32 (autogain = 3; NMR32_4-phb_det; 20 uL CHCl3 added) 19.24 - NMR33 (autogain = 1; NMR33_Cin_hex; 20 uL CHCl3 added) 19.35 - NMR34 (autogain = 2; NMR34_Cin_tol; 20 uL CHCl3 added) 19.46 - NMR35 (autogain = 2; NMR35_Cin_det; 20 uL CHCl3 added) 19.54 - Room temperature checked (23.0 degrees Celsius)

Acknowledgements
The author wishes to thank Dr. Robert Stewart for his advice throughout the course of the experiment and for the use of the NMR lab, Dr. Jean-Claude Bradley for his helpful comments throughout the course of the experiment, Dr. Andrew Lang for his help with SAMS, and Dr. Hal Reed for the use of the department camera for the second series of measurements.

Tag loadtochemspider