Exp102

Researcher
David Bulger

Objective
Verify the SAMS method using varying known concentrations of [|2-phenylbutyric acid] in DMSO against an internal standard of 1,2-dichloroethane.

Procedure
Calibrate pipets, make very dilute solution in 5-mL volumetric flask, make more concentrated solutions in 1-mL volumetric flask, prepare three solutions per concentration with CDCl3 and 1,2-dichloroethane for NMR, run NMR, and measure concentration using SAMS and internal standard.

NMR
[|ONSC102-1A] (0.024 M) [|ONSC102-1B] (0.024 M) [|ONSC102-1C] (0.024 M) [|ONSC102-2A] (0.25 M) [|ONSC102-2B] (0.25 M) [|ONSC102-2C] (0.25 M) [|ONSC102-3A] (0.5 M) [|ONSC102-3B] (0.5 M) [|ONSC102-3C] (0.5 M) [|ONSC102-4A] (1 M) [|ONSC102-4B] (1 M) [|ONSC102-4C] (1 M) [|ONSC102-5A] (2 M) [|ONSC102-5B] (2 M) [|ONSC102-5C] (2 M) [|ONSC102-6A] (3 M) [|ONSC102-6B] (3 M) [|ONSC102-6C] (3 M) [|Raw JCAMP-DX file for ONSC102-1A] [|Raw JCAMP-DX file for ONSC102-1B] [|Raw JCAMP-DX file for ONSC102-1C] [|Raw JCAMP-DX file for ONSC102-2A] [|Raw JCAMP-DX file for ONSC102-2B] [|Raw JCAMP-DX file for ONSC102-2C] [|Raw JCAMP-DX file for ONSC102-3A] [|Raw JCAMP-DX file for ONSC102-3B] [|Raw JCAMP-DX file for ONSC102-3C] [|Raw JCAMP-DX file for ONSC102-4A] [|Raw JCAMP-DX file for ONSC102-4B] [|Raw JCAMP-DX file for ONSC102-4C] [|Raw JCAMP-DX file for ONSC102-5A] [|Raw JCAMP-DX file for ONSC102-5B] [|Raw JCAMP-DX file for ONSC102-5C] [|Raw JCAMP-DX file for ONSC102-6A] [|Raw JCAMP-DX file for ONSC102-6B] [|Raw JCAMP-DX file for ONSC102-6C]

Pictures
[|ONSC102-1] [|ONSC102-2] [|ONSC102-3] [|ONSC102-4] [|ONSC102-5] [|ONSC102-6] [|ONSC102-7] [|ONSC102-8]

Spreadsheets
[|ONSCExp102-1] This spreadsheet contains general calculations. [|ONSC102-1] This spreadsheet contains SAMS for a variety of protons. [|ONSC102-2] This spreadsheet contains internal standard calculations for a variety of protons. [|ONSC102-3] This spreadsheet contains more SAMS for a variety of protons. [|ONSC102-4] This spreadsheet contains more internal standard calculations for a variety of protons. [|ONSC102-5] This spreadsheet contains summaries of data analysis. ONSC-EXP102Hsheet The spreadsheet compares the error between the methyl and the methine protons media type="googlespreadsheet" key="r2RAdVGfcLjYN4NMGFHbsaw" height="400" width="900"
 * [This is too confusing - just have one SAMS sheet and one sheet for the internal standard calculations JCB]** Googledocs only allows 50 import functions per sheet. For SAMS alone, I can only fit a little over half of the calculations before it gives me an error message informing me that I am trying to import more than 50 functions.**[Right - forgot about that limitation. I'll wait till you are done and comment later JCB]**

Discussion
[|ONSC102ExcelGraphs.xls] Screenshots of Graphs are Below: The average error for the SAMS method was found to average at approximately 20% error. The graphs for SAMS show a decreasing percent error as the concentration increases. This could be attributed to the NMR's ability to process both the large solvent peak and the small solute peak better when they have closer heights. Towards the higher concentrations, the graphs for SAMS show a slight increase in percent error. This could be attributed to the error in the density assumptions for the solute increasing in significance as the solute concentration increases. Although the Internal Standard method seems to average at approximately 45% error, the peak used in all the graphs was quite distorted with unclear beginning and ending. Therefore, the results for the Internal Standard error calculations are deemed unreliable.
 * [An [|analysis of error vs. concentration for each hydrogen] selected for integration shows that the methyl group on 2-phenylbutanoic acid generated an average error of 8.4%, while the methine hydrogen generated an average error of 26%. There is no strong correlation of concentration with error, showing that errors related to volume expansion or contraction or estimate of solute density are not dominant. The difference in error between the methyl and methine hydrogens is likely related to relaxation time differences. JCB]**

Conclusion
For 2-phenylbutyric acid in DMSO, the average percent error is approximately 20%.
 * [Actually the story gets more interesting if you plot the CH3 and CH measurements separately JCB]**

Log
2009-05-28 11:40 Weighed three 1-dram vials: 11:45 Pipetted 1 000 uL CDCl3 to 102A700, 100 uL DMSO to 102B100, and 10 uL 1,2-dichloroethane to 102C10 11:50 Weighed vials: 12:00 Weighed vials: 12:02 Pipetted 700 uL CDCl3 to 102A700-2, 100 uL DMSO to 102B100, and 10 uL 1,2-dichloroethane to 102C10 12:07 Weighed vials: 12:11 Pipetted 100 uL DMSO to 102B100 and 10 uL 1,2-dichloroethane to 102C10 12:14 Weighed vials: 12:23 Weighed 102B100 (5.618 4 g) 12:28 Added 100 uL DMSO to 102B100 12:29 Weighed 102B100 (5.777 6 g) 12:30 Added 100 uL DMSO to 102B100 12:31 Weighed 102B100 (5.936 9 g) 12:32 Reweighed 102B100 (5.937 3 g) and reweighed 102B100 again (5.936 1 g) 12:33 Added 100 uL DMSO to 102B100 12:34 Weighed 102B100 (6.096 1 g) using 10uL-100uL pipet 12:35 Added 100 uL DMSO to 102B100 12:36 Weighed 102B100 (6.207 2 g) 12:37 Reweighed 102B100 (6.199 3 g) 12:38 Added 100 uL DMSO to 102B100 and weighed (6.310 1 g) 12:39 Added 100 uL DMSO to 102B100 and weighed (6.419 3 g) 13:15 Weighed 5-mL volumetric flask (8.646 3 g) 13:32 Reweighed 5-mL volumetric flask (8.646 7 g) 13:35 Added 0.020 0 g 2-phenylbutyric acid to 5-mL volumetric flask 13:39 Weighed volumetric flask (8.666 7 g) 13:40 Added DMSO to just under 5-mL mark (solution 102-1) 13:45 Parafilmed and vortexed for 30 sec 13:47 Photo ([|ONSC102-1]) 13:48 Room temperature is 21 degrees Celsius 13:49 Weighed 1-mL volumetric flask (15.605 1 g) 13:52 Began sonication (31 degrees Celsius) with copper wire support for 45 min 13:53 Added 0.041 1 g 2-phenylbutyric acid to 1-mL volumetric flask 13:58 Weighed 1-mL volumetric flask (15.646 2 g) 13:59 Added DMSO to just under 1-mL volumetric flask (solution 102-2) 14:01 Parafilmed and vortexed for 30 sec 14:03 Photo ([|ONSC102-2]) 14:04 Began sonication for 30 min 15:21 Temperature in sonicator was 35 degrees Celsius 15:22 Photo ([|ONSC102-3]) 15:23 Cleaned, dried, and labeled six NMR tubes (102-1A, 102-1B, 102-1C, 102-2A, 102-2B, 102-2C) 15:44 Labeled six 1-dram vials (102-1AP, 102-1BP, 102-1CP, 102-2AP, 102-2BP, 102-2CP) 15:47 Weighed vials: 15:52 Added 700 uL CDCl3 to each vial and weighed: 16:03 Added 10 uL 1,2-dichloroethane and weighed: 16:12 Added 100 uL of solutions 102-1 and 102-2 to corresponding vials as follows: pipetting into the solution followed by parafilming and vortexing for 30 sec 16:28 Transferred preparatory solutions to NMR tubes, capped amd parafilmed 16:40 Collected NMR's ([|ONSC102-1A], [|ONSC102-1B], [|ONSC102-1C], [|ONSC102-2A], [|ONSC102-2B], [|ONSC102-2C]) 18:39 Cleaned 12 NMR tubes and 1-mL volumetric flask 19:12 Weighed 1-mL volumetric flask (15.630 7 g) 19:13 Added 0.082 1 g, 0.164 2 g, 0.328 4 g, and 0.492 6 g of 2-phenylbutyric acid onto four weighing sheets 19:27 Added 0.082 1 g to volumetric flask and weighed (15.712 2 g) 19:31 Added DMSO to just below 1-mL mark 19:35 Vortexed for 30 sec 19:35 Photo ([|ONSC102-4]) - competely dissolved 19:36 Transferred to 1-dram vial (102-3) and parafilmed 19:38 Clean 1-mL volumetric flask with DMSO 19:39 Weighed 1-mL volumetric flask (15.603 3 g) 19:40 Added 0.164 2 g 2-phenylbutyric acid to 10mL volumetric flask and weighed (15.766 9 g) 19:47 Added DMSO to just below mark 19:50 Vortexed for 30 sec 19:51 Added DMSO to 1-mL mark and vortexed for 10 sec 19:52 Photo ([|ONSC102-5]) - completely dissolved 19:53 Transferred solution to 1-dram vial (102-4) and parafimed 19:54 Cleaned 1-mL volumetric flask with DMSO 19:57 Weighed 1-mL volumetric flask (15.599 2 g) 20:01 Added 0.328 4 g 2-phenylbutryic acid to volumetric flask 20:02 Weighed volumetric flask (15.927 1 g) 20:03 Added DMSO to just below 1-mL mark 20:06 Vortexed for 1-min - completely dissolved 20:08 Added DMSO up to 1-mL mark 20:09 Weighed volumetric flask (16.658 1 g) 20:09 Photo ([|ONSC102-6]) 20:10 Transferred solution to 1-dram vial (102-5) and parafilmed 20:13 Cleaned volumetric flask with DMSO 20:15 Weighed volumetric flask (15.594 2 g) 20:17 Added 0.492 6 g to volumetric flask and weighed (16.086 0 g) 20:25 Added DMSO to just below 1-mL mark 20:29 Vortexed for 1-min - completely dissolved and expanded to 1-mL mark 20:31 Photo ([|ONSC102-7]) 20:32 Weighed volumetric flask (16.679 5 g) 20:33 Transferred solution to 1-dram vial (102-6) and parafilmed 20:35 Photo ([|ONSC102-8]) 20:35 Weighed vials: 20:46 Added 700 uL CDCl3 to each vial and weighed: 20:58 Added 10 uL of 1,2-dichloroethane to each vial and weighed: 21.13 Added 100 uL of solutions (102-3 through 102-6) to corresponding preparatory vials 21:29 Tricherated solutions, transferred solutions to corresponding NMR tubes, and parafilmed 21:53 Vortexed NMR tubes for 10 sec 21:55 Collected NMR's ([|ONSC102-3A], [|ONSC102-3B], [|ONSC102-3C], [|ONSC102-4A], [|ONSC102-4B], [|ONSC102-4C], [|ONSC102-5A], [|ONSC102-5B], [|ONSC102-5C], [|ONSC102-6A], [|ONSC102-6B], [|ONSC102-6C])
 * Vial || Mass (g) ||
 * 102A700-1 || 5.135 9 ||
 * 102B100 || 5.148 7 ||
 * 102C10 || 5.097 0 ||
 * Vials || Mass (g) ||
 * 102A700-1 || 6.820 9 ||
 * 102B100 || 5.303 6 ||
 * 102C10 || 5.111 8 ||
 * Vials || Mass (g) ||
 * 102A700-2 || 5.118 6 ||
 * 102B100 || 5.303 6 ||
 * 102C10 || 5.111 1 ||
 * Vials || Mass (g) ||
 * 102A700-2 || 6.268 6 ||
 * 102B100 || 5.466 8 ||
 * 102C10 || 5.124 2 ||
 * Vials || Mass (g) ||
 * 102B100 || 5.617 8 ||
 * 102C10 || 5.137 8 ||
 * Vial || Mass (g) ||
 * 102-1AP || 5.131 1 ||
 * 102-1BP || 5.072 5 ||
 * 102-1CP || 5.131 9 ||
 * 102-2AP || 5.123 0 ||
 * 102-2BP || 5.110 7 ||
 * 102-2CP || 5.120 4 ||
 * Vial || Mass (g) ||
 * 102-1AP || 6.233 9 ||
 * 102-1BP || 6.194 8 ||
 * 102-1CP || 6.260 9 ||
 * 102-2AP || 6.260 9 ||
 * 102-2BP || 6.268 1 ||
 * 102-2CP || 6.250 4 ||
 * Vial || Mass (g) ||
 * 102-1AP || 6.243 7 ||
 * 102-1BP || 6.204 9 ||
 * 102-1CP || 6.270 3 ||
 * 102-2AP || 6.270 4 ||
 * 102-2BP || 6.260 3 ||
 * 102-2CP || 6.278 7 ||
 * Vial || Solution ||
 * 102-1AP || 102-1 ||
 * 102-1BP || 102-1 ||
 * 102-1CP || 102-1 ||
 * 102-2AP || 102-2 ||
 * 102-2BP || 102-2 ||
 * 102-2CP || 102-2 ||
 * Vials || Mass (g) ||
 * 102-3AP || 5.098 6 ||
 * 102-3BP || 5.124 5 ||
 * 102-3CP || 5.070 2 ||
 * 102-4AP || 5.104 4 ||
 * 102-4BP || 5.105 4 ||
 * 102-4CP || 5.089 2 ||
 * 102-5AP || 5.113 0 ||
 * 102-5BP || 5.123 5 ||
 * 102-5CP || 5.101 0 ||
 * 102-6AP || 5.079 1 ||
 * 102-6BP || 5.082 8 ||
 * 102-6CP || 5.098 9 ||
 * Vials || Mass (g) ||
 * 102-3AP || 6.203 6 ||
 * 102-3BP || 6.254 9 ||
 * 102-3CP || 6.326 8 ||
 * 102-4AP || 6.231 1 ||
 * 102-4BP || 6.239 0 ||
 * 102-4CP || 6.210 2 ||
 * 102-5AP || 6.246 5 ||
 * 102-5BP || 6.258 0 ||
 * 102-5CP || 6.224 4 ||
 * 102-6AP || 6.228 4 ||
 * 102-6BP || 6.222 8 ||
 * 102-6CP || 6.217 5 ||
 * Vials || Mass (g) ||
 * 102-3AP || 6.216 3 ||
 * 102-3BP || 6.265 2 ||
 * 102-3CP || 6.229 5 ||
 * 102-4AP || 6.242 0 ||
 * 102-4BP || 6.251 2 ||
 * 102-4CP || 6.221 7 ||
 * 102-5AP || 6.259 3 ||
 * 102-5BP || 6.269 0 ||
 * 102-5CP || 6.234 4 ||
 * 102-6AP || 6.239 0 ||
 * 102-6BP || 6.235 5 ||
 * 102-6CP || 6.228 3 ||