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EDGEWOOD CHEMICAL BIOLOGICAL CENTER US ARMY RESFARCH, DEVELOPMENT AND ENGINFFRING COMMAND ECBC-TR-416 NMR METHOD FOR THE QUANTITATIVE ANALYSIS OF LIQUID SAMPLES H, Dupont Durst RESEARCH AND TECHNOLOGY DiRECTORATE David J. McGarvey Witliam R. Greasy ohn Pence Jennifer 1. Montgomery EA acccgercn —= == EAI CORPORATION ‘Abingdon, MD 21009 January 2008 ‘Approved fer public releaae; ‘itribution fo wot. 20050303 303 ABERDEEN PROVING GROUND, MD 21019-5424 Disclaimer The findings in this report are not to be construed as an official Department of the Army position unless so designated by other authorizing dacuments REPORT DOCUMENTATION PAGE ous Seine TREPORT OME REMY 2 REPORT TYPE BATES OOTERED Fam XXD1-2005 Final (et 2008 - Sep 2002 [NMR Medhad forthe Quumitative Analyris of Liquid Samples © ATOR, FROST Tae ‘O° Connar, Richard J; Brickhouse, Mark D.; Rice, eftey Su; Durst, H, 62399254200 Dupont (ECBO); MeGarvey, David J: Creasy. William R; Pence, John, [A TAB NUMEER sand Manigomery, Jeunifer L- (EAT Corperation) HORROR OEE RF ORTON@ ONGANEZATIONWAMEE| ANY ADDREESESTANG SDDRESIES) | 6 PERTGRTANE ORGANETION REPORT | DIR, ECRC, ATTN: AMSRD-ECH-RI-PDYAMSRD-ECB-RI-PC, APO, | Auer wn 21010-5424, TCBCARAIS EAI Corporation, 1308 Continental Drie, Suite J, Abingdon, MD 2100 [ EBPRNFORNE 7RONTORNE KERN naeisy Ai ADREBETEDT TO EPOREDRN TORS ACRONIS] Fi SPOMROOTERTTORT REPORT MOMBEREY Appioved for public relewse;diarbution is unlimited. ATOR ‘This prcedire is hased on previously published ERDEC-TR 449, Nuclear Magnet Resonance (NMR) Analysis of | ‘Chemicat Agents aud Resction Masses Produced hy heir Chemical Newtalizaton, and HCAC=IR-253, SMR ‘Method forthe Quantitative Puily Analyais of Feedstock Samples ‘Ihe procedure places the metal A ‘This prooodime uves an intemal stadard to establish an absolotc weight percent for the analyes in question ‘ening the suructuses of other couponcas inthe mixture is mot required lo determine the weleht percent of tie analyte, The weighr pereezcalculstions are nol negaively affected by the presence of undetectatle components (Gg. elemental sulfur, morgane als ee) in de sample, 1 SORRY TAR NMR i [Nuclear Magnotis Resonance Quuntiative 15 SEGURA CIASSERTN OF “F URRTRTTON GF [78 RRGER OF | Te WATE GF RESPONSTOCE PERSON — _ “aEaTRAST PACE ‘Sondra. Jolnsel TRERRE | EABARAGT Ye This ace [aE WELDON ER poe u v v wu. Alo) 4362914 cir Blank PREEACE This work desorihed ia this repon was authosizod under Project Nu 62262258200, The work ws started in Oxtober 2001 snd completed in September 2002, ‘The use of cithr trade or menulicturers” names in this report docs net constitute tn alficiat endorscmment of ary commercial produets,‘Lhis report may not he cited for purposes of advertisement, ‘This reporthas been apprewed lor public release, Registered users shan request Additional copies from the Defense Technical Information Center, unregistered users should cect such requests ia the National ‘Technica! information Service. Blank CONTENTS INTRODUCTION Purpose ‘Analyte Concenvration Range: Sample Matces aud Inecferouces.. ‘Throwshpun. RISK AND SAFETY ASSESSMENT SCIENTIFIC BASIS... TRAINING APPARATUS. Tnstrumentation Glassware, Miscellaneous Equipment, and Supplies. Chemicals PROCEDURE. Sample Preparation. ower ‘Obtaining NMR Spectr in Spectral Data Analysis CALCULATION, CATINRATION, AND DOCUMENTATION FIGURES P Spectrom of» Sample Containing HMPA Intemal Standard su al ‘I Spectrum of a Summple Containing HMEA intemal Standard, TABLES ACWA PHA Results for 50 perm TDG Standard in D0 on AC-300 Using Froton NMR Results for H20 Solvent Suppression, Standard in Dt Water, 8 Runs on Hach of Two Days i. . ACWA P&A Results foe 200 ppm TDG Standard in ACWA Sample ‘01 AC-300 Lising Froron NMR Results for ae HO Solver Suppression, & Rems (on Bach of Te ayer ' 2 NMR MITTIOD FOR THE QUANTITATIVE ANALYSIS OF LIQUID SAMPLES L INTRODUCTION Ma Purpose |, __ This procedure ia basa on the previously published HICDEC-1R-449" and KOBC- ‘TR-253* Tho procedure repluces the method ACI-021. ‘This procedure uses an internal standard to establish aa absolute weight percaut forthe aualytcs in question. Identifying Ihe euctures of other compouens inthe inistore is not required to determine the weight percent of the analyte, The woight percent ealculations are not negatively affected by the presence of undetocthle compunents (xy., eexnental sulfur, inoreanic sas, otc} in the sample 12 Analyte Concentration Range. Analytes ean be quantified at any concentration level fom the detection limit te ‘teat material, The following detection mit study (Tabley ¥ and 2) was performed using proton NMR ou the Bruker AC-300. Deteotion mite for other muclel and other instruments were costimatcd using the knowledge of Ure operator. Detection limits will depend on the matrix and interferemves. 1Tdeusetion limits ave sequired for a particular measurement, they should be ‘dzietqined for the pationlar matrix, analyte, and instrument and given inthe analysis report, 13 Sample Matrices and Interferences. This metho can be performed on tiguid mattices that solubilize the intemal standard. Generally, ether TEP (uiethylphosphatc) or HMPA (hexamethylphospheramide) have ‘been soluble in each AWCA matrix. Other internal stndards may be used as fong as they are stable andthe signs From the siandard do aot interfere with other peaks in the spectra, For Tposie malices, TEP isthe prefered internal standard, The internal standards must ato be commercially available with » high puny ‘Paramagnstic mctals such a ion and chrormium at funly low voncentralions will tvoaden the peaks and either inrzate the errr ofthe analysis, or invalidate it entirely. Ongoing research on the use of Tiron a8 an iron chelaror and spin-relasation agent may partially solve this ‘prem in the firs. Dike, MID Roos, MS; O'Conner, R1: Durst HD. Nuclear Segmetic Rexonmce (NBR) nals of Chemical Agere cet Reaction Masses Produced by Thr Cheol Nerang TROEC!TR-405 1.8. ety Jxjgesua ketearch, Developmanc and Frnceing Comer. Aberdcen Proving Ground, MID, 1297 _, UNCLASSIFIED Report (AD-A339 308, como, RI; Beckhams. MD; MoGarvey, D2: Dues ALD ; Cees. WI Kath 11. MH Mel fr te Quatre Party dns of Feastock Samples, HUBC-TK.253; DS, Aran Page Cheri Piaget Spee Abandon oring Crean MD, 2002, UNC. ASSTFIED Repo (AD-ASOS #13), Table 1. ACWA P&A Results for 50 ppm TDG Standard in RzO on AC-300 Using Proton ‘NMR Results for HO Solvent Suppression, Standard in DT Water. 8 Runs on Fach of Two Days Somple No. NB130022€ Integration from NUTS, 1S=HMPA, compound is TDG File Int 1S at omp. supa sample (ppm) AROOOE.105 1031536 t69.03 4507 ARO9IF 105, 1033091 146 45.39 AROSIP.1O5 1030570 164.89 44.01 AKOSSE105 1030391 14083 37.60 AROSME. 105 warns E39 39.77 ARO9SH 105 1027010 13838 36,26 AROSGE 105 1030428 17S91 46.96 AROS7E 105 1028647 159.97 QT AROSOR.107, 1089223, Yre8 46.27 AROOIEI7 1056418, 182.x4 4741 ARO92F.107 1057849 1843 4792 ARODST. 17 1039150 180.48 46.87 AROSAE.107 1037912 1799 46.78 AROOSE.I07 1058795, 199.81 49.31 ‘AROSGE_107 1056339, 156 40.62 AROO7E.107 1036515 134.06 4192 Average Concentration (ppm) 4aas Standard di 398 MDL (ppm) 1027 Sample concentration 45.81 Recavery % 97.02%