New Jersey Institute of Technology Digital Commons @ NJIT Theses Electronic Theses and Dissertations Fall 1-31-2009 Thermochemistry and bond energies of nitro -alkanes, -alkenes, -carbonyls and corresponding nitrites Surawee Snitsiriwat New Jersey Institute of Technology Follow this and additional works at: https://digitalcommons.njit.edu/theses Part of the Environmental Sciences Commons Recommended Citation Snitsiriwat, Surawee, "Thermochemistry and bond energies of nitro -alkanes, -alkenes, -carbonyls and corresponding nitrites" (2009). Theses. 305. https://digitalcommons.njit.edu/theses/305 This Thesis is brought to you for free and open access by the Electronic Theses and Dissertations at Digital Commons @ NJIT. It has been accepted for inclusion in Theses by an authorized administrator of Digital Commons @ NJIT. For more information, please contact [email protected]. Cprht Wrnn & trtn h prht l f th Untd Stt (tl , Untd Stt Cd vrn th n f phtp r thr rprdtn f prhtd trl. 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ASAC EMOCEMISY A O EEGIES O IO -AKAES -AKEES -CAOYS A COESOIG IIES b Sr Sntrt nt fntnl nd b nt thr bd lltn r prfrd n r f ntr -ln -ln rbnl nd rrpndn ntrt rprntn lr-l prr ndr nd trtr ntr pnd nd thr rdl rltn fr th l f ltl hdrn t Gtr vbrtn frn nd thrhl prprt Af°9 S °( nd C°p( (1K 5 5K r lltd t th ndvdl 3Y/-31G(dp 3Y /-31+G(dp nd pt CS-Q3 lvl tntl nr brrr fr th ntrnl rttn hv bn ptd t th 3Y/-3lG(dp lvl f thr nd th lr brrr ntrbtn r nrprtd nt ntrp nd ht pt dt h tndrd nthlp f frtn t 9 K r vltd n d rtn h th vrl r rtn fr h p ndd vl drvd fr th t tbl nfrr f rptv ntr- nd ntrt r nld -3 nd - l l fr n-prpn- -339 nd -33 l l-¹ ¹ fr iso- prpn- - nd -1 l l-¹ fr trt-btn-ntr pnd nd ntrt rptvl Entrp nd ht pt vl r l rprtd fr th lr hl ntrthn ntrthn nd rrpndn ntrt C— bnd nr r drd b 5 l l lph t th ntr r ntrt rp nd nrd b 5 l l bt t th ntr nd ntrt rp ndd vl fr nthlp f frtn f th t tbl nfrr f ntrtn tntrt ntrtt nd tl ntrt r -51 l l -¹ -51 l l-¹¹ -5 l l nd -5 l l rptvl h lltd Af°9 fr ntrthln 7 l l -¹ nd fr vnl ntrt 7 l l h rbnl nd lfn rp rtn th jr nfln n th C- bnd nr dl n rbn djnt t ntrt (COO rp d nt xt; th dt t th rrpndn rbnl (C=O + O th 3 l l xthr nd n pprnt brrr h rlt fr frtn f th trn rbnl (t bnd l l th dtn f th O—O bnd (-3 l l THERMOCHEMISTRY AND BOND ENERGIES OF NITRO -ALKANES, -ALKENES, -CARBONYLS AND CORRESPONDING NITRITES by Suarwee Snitsiriwat A Thesis Submitted to the Faculty of New Jersey Institute of Technology in Partial Fulfillment of the Requirements for the Degree of Master of Science in Environmental Science New Jersey Institute of Technology and Rutgers, The State University of New Jersey — Newark January 2009 APPROVAL PAGE THERMOCHEMISTRY AND BOND ENERGIES OF NITRO -ALKANES, -ALKENES, -CARBONYLS AND CORRESPONDING NITRITES Suarwee Snitsiriwat r. Jos; ph W. Bozzelli, Thesis Advisor Date istinguished Professor of Chemistry and Environmental Science, NJIT Dr. Carol A. Venanzi, Committee Member Date Distinguished Professor of Chemistry and Environmental Science, NJIT Dr. Tamara M. Gund, Committee Member Date Professor of Chemistry and Environmental Science, NJIT BIOGRAPHICAL SKETCH Author: Suarwee Sntrt Degree: Mtr f Sn Date: nr 9 Undergraduate and Graduate Education: • Mtr f Sn n Envrnntl Sn r Inttt f hnl r 9 • hlr f Sn n Chtr Chllnrn Unvrt n hlnd 3 Major: Envrnntl Sn Wr l dnt nd n v l v nvr bn hrt Sn f n n n hr And dn l n n thn Anonymous It t tnt r t n vrnht Eddie Cantor hr r n rl f rhttr fr tl n th ld G. K. Chesterton Y b dppntd f fl bt r dd f dnt tr Beverly Sills ACKOWEGME I ld l t rtfll nd nrl thn rf ph W zzll dvr fr h dn ptn nd t prtntl h frndln drn rdt td t I Spl thn r vn t ll th br n r Cpttnl Chtr rh Grp r b Atrn r nl Old nd Anjn Gntr ll f h r thr bt frnd nd ll hrn th t rbl hr nd hppn bnd hllnn lbrtr-rn nvrnnt M nr pprtn xtndd t rf Crl A nnz ll rf r M Gnd fr rvn n tt hr nt prvdd vlbl npt fr rrh I rtfll nld pprt fr th US Ar rh ff ndr prvn f r brt Sh hnfln xprd t th Mthll fl fr rntn n pprtnt t lt Arn ltr nd bn fl n USA t bt nt lt I ld l t xpr prfnd rttd t prnt bln nd frnd n ttbrh A nd hlnd fr nplnn ptn prnnl pprt nd nr nrnt drn t n USA v AE O COES Chptr Page 1 EMOCEMICA OEIES O OY ISO-OY A E-UY IOAKAES A AKY IIE 1 11 Objtv 1 1 rnd Infrtn 2 13 Cpttnl Mthd 4 1 lt nd dn ... 5 11 Cnfrtn f trt 5 1 Cnfrtn f tr Aln 6 13 Enthlp f rtn 6 1 nd tn Enr 15 15 Intrnl ttn tntl 1 1 Entrp nd t Cpt t 3 17 Grp Addtvt 40 15 Cnln 1 EMOCEMICA OEIES O A SEIES O IOCAOYS IOOEIS 3 1 Ovrv 3 rnd Infrtn 44 3 Cpttnl Mthd 5 lt nd n 46 1 Enthlp f rtn 7 nd tn Enr - 5 3 Intrnl ttn tntl 5 v TABLE OF CONTENTS (continued) Chapter Page Entrp nd t Cpt t 7 5 Grp Addtvt 75 5 Cnln 7 AEI A COMAISO EMOCEMISY AA 7 AEI IAIO EQUECIES A OIMIE GEOMEY O IOAKAES AKY IIE A EI AICAS 79 AEI C IAIO EQUECIES A OIMIE GEOMEY O IOCAOYS IOOEIS COESOIG IIES A EI AICAS 97 EEECES 113 viii LIST OF TABLES Table Page 11 Stndrd Enthlp f rtn f frn 8 1 Clltd tn Enthlp t nd Evltd Enthlp f rtn f rt Mll 11 13 rtn Enthlp fr Sr f tr nd trt Cpnd 13 1 tn Enthlp fr dl Clltd Enthlp f rtn nd nd Enr 17 15 Sr f rtn Enthlp nd nd tn Enr 20 1 Idl G-ph hrdn rprt vs. prtr 3 17 Grp hrhl l 1 1 h Stndrd Enthlp f rtn f frn Sp 48 2.2 Clltd tn Enthlp nd Evltd Enthlp f rtn f rt Mll 5 3 rtn Enthlp fr Sr f trrbnl trlfn 5 2.4 tn Enthlp fr dl Clltd Enthlp f rtn nd nd Enr 55 5 Sr f AfH298 nd nd Enr l fr trrbnl nd trlfn nd thr Crbn dl 5 2.6 Idl G-ph hrdn rprt vs prtr 7 7 Grp hrhl l 7 A1l Cpr th nthlp ntrp nd ht pt dt fr th td th rrpndn dt fr Ahrft nd Grn 7 11 brtn rn 79 ix LIST OF TABLES (continued) Table Page 1 Gtr rtr f tr-n-rpn 1 13 Gtr rtr f trt n-prpn 82 1 Gtr rtr f tr--rpn 3 15 Gtr rtr f trt--prpn 84 B 1.6 Gtr rtr f tr trtr btn 5 17 Gtr rtr f trt trtr btn 86 1 Gtr rtr f CCCO 7 11 Gtr rtr f C3CCO 88 11 Gtr rtr f C3CCO 9 111 Gtr rtr f CCCOO 9 B 1.12 Gtr rtr f C3CCOO 91 113 Gtr rtr f CC (O2C3 9 11 Gtr rtr f C3C(O2C3 93 115 Gtr rtr f CC(OOC3 9 11 Gtr rtr f CC(C3(O 95 117 Gtr rtr f C 2C(C3(OO 9 C1 brtn rn 97 C Gtr rtr f trtn 99 C3 Gtr rtr f rpnn ntrt 1 C Gtr rtr f trthln 11 C5 Gtr rtr f nl ntrt 1 C Gtr rtr f trtt 13 LIST OF TABLES (continued) Table Page C7 Gtr rtr f Atl ntrt 1 C Gtr rtr f CC(=CO 15 C9 Gtr rtr f C3C(=OCO 1 C1 Gtr rtr f CC(=OCOO 17 C11 Gtr rtr f C=CO 1 C1 Gtr rtr f C=CO 19 C13 Gtr rtr f C=COO 11 C1 Gtr rtr f CC(=OO 111 C15 Gtr rtr f CC(=OOO 11 xi LIST OF FIGURES Figure Page 11 Gtr f th ll nd rrpndn bbrvtd nltr 7 1 Gtr f rdl nd nnltr 1 l31 tntl Enr rfl fr Intrnl ttn n tr-n-prpn 22 l3 tntl Enr rfl fr Intrnl ttn n n-prpl ntrt 22 133 tntl Enr rfl fr Intrnl ttn n tr--prpn 3 13 tntl Enr rfl fr Intrnl ttn n prpl ntrt 3 l35 tntl Enr rfl fr Intrnl ttn n tr-trt-btn 24 l3 tntl Enr rfl fr Intrnl ttn n trt-btl ntrt 24 137 tntl Enr rfl fr Intrnl ttn n C•CCO 5 l3 tntl Enr rfl fr Intrnl ttn n C3C•CO 26 139 tntl nr prfl fr ntrnl rttn n C3CC•O 7 131 tntl Enr rfl fr Intrnl ttn n C•CCOO 28 1311 tntl Enr rfl fr Intrnl ttn n C3C•COO 9 l31 tntl Enr rfl fr Intrnl ttn n C•C(OC3 3 1313 tntl Enr rfl fr Intrnl ttn n C3C• (OC3 31 l31 tntl Enr rfl fr Intrnl ttn n C•C(OOC3 3 1315 tntl Enr rfl fr Intrnl ttn n C•C(CO 33 131 tntl Enr rfl fr Intrnl ttn n C•C(C 3 1 Gtr f th trt ll nd bbrvtd nnltr 7 2.2 Strtr nd d nnltr f rdl 5 3l tntl Enr rfl fr Intrnl ttn n trtn 60 x IS O IGUES (ntnd r Page 3 tntl Enr rfl fr Intrnl ttn n prpnn ntrt 60 33 tntl Enr rfl fr Intrnl ttn n trthln 1 3 tntl Enr rfl fr Intrnl ttn n nl ntrt 1 35 tntl Enr rfl fr Intrnl ttn n trtt 62 3 tntl Enr rfl fr Intrnl ttn n Atl ntrt 62 37 tntl Enr rfl fr Intrnl ttn n j(n2 3 3 tntl Enr rfl fr Intrnl ttn n (jn2 64 39 tntl nr prfl fr ntrnl rttn n j(n 5 31 tntl Enr fr Intrnl ttn n jn2 66 311 tntl Enr fr Intrnl ttn n jn2 7 31 tntl Enr fr Intrnl ttn n jn 68 313 tntl Enr fr Intrnl ttn n j(n2 9 31 tntl Enr fr Intrnl ttn n j(n 7 CAE 1 EMOCEMICA OEIES O -OY ISOOY A E-UY IOAKAES A AKY IIE 11 Objtv Density functional theory based calculations are performed on a series of alkyl nitrites and nitroalkanes representing large-scale primary, secondary and tertiary nitro compounds and their radicals resulting from the loss of skeletal hydrogen atoms.