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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
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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
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r nt n n t : If d n t h t pr nt th p , th n l t “ fr : f r t p t : l t p n th pr nt d l r n h n t n l br r h r v d f th p r n l nf r t n nd ll n t r fr th ppr v l p nd b r ph l t h f th nd d rt t n n rd r t pr t t th d nt t f I r d t nd f lt . A S AC
E MOC EMIS Y A O E E GIES O I O -A KA ES -A KE ES -CA O Y S A CO ES O I G I I ES
b S r Sn t r t
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n tr - l n - l n rb n l nd rr p nd n n tr t r pr nt n l r - l pr r nd r nd t rt r n tr p nd nd th r r d l r lt n fr th l
f l t l h dr n t G tr v br t n fr n nd th r h l
pr p rt Af ° 9 S °( nd C°p( (1 K 5 5 K r l l t d t th nd v d l
3 Y / -31G(d p 3 Y / -31+G( d p nd p t C S-Q 3 l v l t nt l
n r b rr r f r th nt rn l r t t n h v b n p t d t th 3 Y / -3lG(d p
l v l f th r nd th l r b rr r ntr b t n r n rp r t d nt ntr p nd h t
p t d t h t nd rd nth lp f f r t n t 9 K r v l t d n
d r t n h th v r l r r t n f r h p nd d
v l d r v d fr th t t bl nf r r f r p t v n tr - nd n tr t r
n l d -3 nd - l l f r n-pr p n - -33 9 nd -3 3 l l-¹ ¹ f r iso-
pr p n - - nd - 1 l l-¹ f r t rt-b t n -n tr p nd nd n tr t
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r d r d b 5 l l lph t th n tr r n tr t r p nd n r d b 5
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l f n r p r t n th j r nfl n n th C- b nd n r d l n rb n
dj nt t n tr t ( C O O r p d n t x t; th d t t th rr p nd n
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f th O— O b nd (- 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 Sn t r t
Degree: M t r f S n
Date: n r 9
Undergraduate and Graduate Education:
• M t r f S n n Env r n nt l S n r In t t t f hn l r 9
• h l r f S n n Ch tr Ch l l n rn Un v r t n h l nd 3
Major: Env r n nt l S n W r l d n t n d n v l v n v r b n h rt S n f n n n h r And d n l n n t h n Anonymous
It t t nt r t n v rn ht Eddie Cantor
h r r n r l f r h t t r f r tl n th l d G. K. Chesterton
Y b d pp nt d f f l b t r d d f d n t tr Beverly Sills ACK OW E GME
I ld l t r t f ll nd n r l th n r f ph W zz ll dv r f r h d n p t n nd t p rt ntl h fr ndl n d r n r d t t d
t I
Sp l th n r v n t ll th b r n r C p t t n l Ch tr
r h Gr p r b A tr n r n l Ol d nd Anj n G nt r ll f
h r thr b t fr nd nd ll h r n th t r bl h r nd h pp n b nd h ll n n l b r t r - r n nv r n nt
M n r ppr t n xt nd d t r f C r l A n nz ll r f
r M G nd f r rv n n tt h r nt pr v d d v l bl np t f r r r h
I r t f ll n l d pp rt fr th US Ar r h ff nd r
p rv n f r b rt Sh
h n f ln xpr d t th M t h ll f l f r r nt n n pp rt n t t l t A r n lt r nd b n f l n USA
t b t n t l t I ld l t xpr pr f nd r t t d t p r nt
bl n nd fr nd n tt b r h A nd h l nd f r n pl n n p t n p r nn l pp rt nd n r n r nt d r n t n USA
v A E O CO E S
Ch pt r 1 E MOC EMICA O E IES O O Y ISO- O Y A E - U Y I OA KA ES A A KY I I E 1 1 1 Obj t v 1 1 r nd Inf r t n 1 3 C p t t n l M th d 1 lt nd d n 5 1 1 C nf r t n f tr t 5 1 C nf r t n f tr Al n 1 3 Enth lp f r t n 1 nd t n En r 15 1 5 Int rn l t t n t nt l 1 1 Entr p nd t C p t t 3 1 7 Gr p Add t v t 1 5 C n l n 1 E MOC EMICA O E IES O A SE IES O I OCA O Y S I OO E I S 3 1 Ov rv 3 r nd Inf r t n 3 C p t t n l M th d 5 lt nd n 1 Enth lp f r t n 7 nd t n En r - 5 3 Int rn l t t n t nt l 5
v TABLE OF CONTENTS (continued)
Chapter Page
Entr p nd t C p t t 7
5 Gr p Add t v t 75
5 C n l n 7
A E I A COM A ISO E MOC EMIS Y A A 7
A E I I A IO EQUE CIES A O IMI E GEOME Y O I OA KA ES A KY I I E A EI A ICA S 79
A E I C I A IO EQUE CIES A O IMI E GEOME Y O I OCA O Y S I OO E I S CO ES O I G I I ES A EI A ICA S 97
E E E CES 113
viii LIST OF TABLES
Table Page
1 1 St nd rd Enth lp f r t n f f r n 1 C l l t d t n Enth lp t nd Ev l t d Enth lp f r t n f r t M l l 11 1 3 r t n Enth lp f r S r f tr nd tr t C p nd 13 1 t n Enth lp f r d l C l l t d Enth lp f r t n nd nd En r 17 1 5 S r f r t n Enth lp nd nd t n En r 1 Id l G -ph h r d n r p rt vs. p r t r 3 1 7 Gr p h r h l l 1 1 h St nd rd Enth lp f r t n f f r n Sp C l l t d t n Enth lp nd Ev l t d Enth lp f r t n f r t M l l 5 3 r t n Enth lp f r S r f tr rb n l tr l f n 5 t n Enth lp f r d l C l l t d Enth lp f r t n nd nd En r 55
5 S r f AfH298 nd nd En r l f r tr rb n l nd tr l f n nd th r C rb n d l 5 Id l G -ph h r d n r p rt vs p r t r 7 7 Gr p h r h l l 7 A1 l C p r th nth lp ntr p nd h t p t d t fr th t d th rr p nd n d t fr A h r ft nd Gr n 7
1 1 br t n r n 79
ix LIST OF TABLES (continued)
Table Page
1 G tr r t r f tr -n- r p n 1 1 3 G tr r t r f tr t n-pr p n 1 G tr r t r f tr - - r p n 3 1 5 G tr r t r f tr t - -pr p n B 1.6 G tr r t r f tr t rt r b t n 5 1 7 G tr r t r f tr t t rt r b t n 1 G tr r t r f C C C O 7 1 1 G tr r t r f C 3C C O
1 1 G tr r t r f C 3C C O 9 1 11 G tr r t r f C C C O O 9 B 1.12 G tr r t r f C 3C C O O 91
1 13 G tr r t r f C C ( O C 3 9
1 1 G tr r t r f C 3C( O C 3 93 1 15 G tr r t r f C C (O O C 3 9
1 1 G tr r t r f C C(C 3 ( O 95
1 17 G tr r t r f C C(C 3 (O O 9 C 1 br t n r n 97 C G tr r t r f tr t n 99 C 3 G tr r t r f r p n n n tr t 1 C G tr r t r f tr th l n 1 1 C 5 G tr r t r f n l n tr t 1 C G tr r t r f tr t t 1 3 LIST OF TABLES (continued)
Table Page
C 7 G tr r t r f A t l n tr t 1
C G tr r t r f C C(= C O 1 5 C 9 G tr r t r f C 3C(=O C O 1 C 1 G tr r t r f C C(=O C O O 1 7
C 11 G tr r t r f C =C O 1 C 1 G tr r t r f C =C O 1 9 C 13 G tr r t r f C =C O O 11 C 1 G tr r t r f C C(=O O 111 C 15 G tr r t r f C C(=O O O 11
xi LIST OF FIGURES
Figure Page
1 1 G tr f th l l nd rr p nd n bbr v t d n l t r 7 1 G tr f r d l nd n n l t r 1 l 3 1 t nt l En r r f l f r Int rn l t t n n tr -n-pr p n l 3 t nt l En r r f l f r Int rn l t t n n n-pr p l n tr t 1 3 3 t nt l En r r f l f r Int rn l t t n n tr - -pr p n 3 1 3 t nt l En r r f l f r Int rn l t t n n pr p l n tr t 3 l 3 5 t nt l En r r f l f r Int rn l t t n n tr -t rt-b t n l 3 t nt l En r r f l f r Int rn l t t n n t rt-b t l n tr t 1 3 7 t nt l En r r f l f r Int rn l t t n n C• C C O 5 l 3 t nt l En r r f l f r Int rn l t t n n C 3C• C O 1 3 9 t nt l n r pr f l f r nt rn l r t t n n C 3C C• O 7 1 3 1 t nt l En r r f l f r Int rn l t t n n C• C C O O 1 3 11 t nt l En r r f l f r Int rn l t t n n C 3C• C O O 9 l 3 1 t nt l En r r f l f r Int rn l t t n n C• C ( O C 3 3 1 3 13 t nt l En r r f l f r Int rn l t t n n C 3C• ( O C 3 31 l 3 1 t nt l En r r f l f r Int rn l t t n n C• C (O O C 3 3 1 3 15 t nt l En r r f l f r Int rn l t t n n C• C (C O 33 1 3 1 t nt l En r r f l f r Int rn l t t n n C• C (C 3 1 G tr f th t r t l l nd bbr v t d n n l t r 7 Str t r nd d n n l t r f r d l 5
3 l t nt l En r r f l f r Int rn l t t n n tr t n
x IS O IGU ES ( nt n d
r
3 t nt l En r r f l f r Int rn l t t n n pr p n n n tr t 3 3 t nt l En r r f l f r Int rn l t t n n tr th l n 1 3 t nt l En r r f l f r Int rn l t t n n n l n tr t 1 3 5 t nt l En r r f l f r Int rn l t t n n tr t t 3 t nt l En r r f l f r Int rn l t t n n A t l n tr t
3 7 t nt l En r r f l f r Int rn l t t n n j ( n 2 3
3 t nt l En r r f l f r Int rn l t t n n ( jn 2
3 9 t nt l n r pr f l f r nt rn l r t t n n j ( n 5
3 1 t nt l En r f r Int rn l t t n n j n 2
3 11 t nt l En r f r Int rn l t t n n jn 2 7
3 1 t nt l En r f r Int rn l t t n n j n
3 13 t nt l En r f r Int rn l t t n n j ( n 2 9
3 1 t nt l En r f r Int rn l t t n n j ( n 7 C A E 1
E MOC EMICA O E IES O - O Y ISO O Y A E - U Y I OA KA ES A A KY I I E
1 1 Obj t v
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.
Geometries, vibration frequencies and thermochemical properties, AfH°298, S °(T) and
C° p(T) (10K < T < 5000K) are calculated at the individual B3LYP/6-31G(d,p), B3LYP
/6-31+G(2d,2p) and composite CBS-QB3 levels. Potential energy barriers for the internal rotation have been computed at the B3LYP/6-31G(d,p) level of theory and the lower barrier contributions are incorporated into entropy and heat capacity data. The standard enthalpies of formation at 298 K are evaluated using isodesmic reaction schemes with several work reactions for each species. Recommended values derived from the most stable conformers of respective nitro- and nitrite isomers include: -30.57 and -28.44 kcal moi l for n-propane-, -33.89 and -32.32 kcal moi l for iso-propane-, -42.78 and -41.36 kcal moi l for tert-butane-nitro compounds and nitrites, respectively. Entropy and heat capacity values are also reported for the lower homologues: nitromethane, nitroethane and corresponding nitrites.
1 2
2 r nd Inf r t n
A r t f r t n nth lp Af ° 9 f r th pl t n tr nd n tr t l l r r r d n rd r t nd r t nd r t n p th nd t n th d v l p nt f d t l d
h l n t h n In t rn th h n n b ppl d t d l th f r t n nd d tr t n f n tr n p n v r t f nv r n nt p rt l rl f r t ph r nd b t n h tr S n l th n % f n n r n
p h v h d th r h t f f r t n r th ppl t n f d rn nt
h tr th d f r th d t f v l pr v d d th t r n bl r n b
bt n d h t bl h nt f th b v l ll l d n th d t r n t n f th th r h l pr p rt f h h r h l v f d r t n th
r p n rv t n ( t n r t n h t d nt n d v l p nt nd
v l t n f th r h l pr p rt n pl t n tr - nd n tr t p nd fr
r pr v n l 2 3
tr ( O nd n tr t ( O O d r v t v f h dr rb n nd r th r l d p t n t r l t v l l t p r t r nd h n h v p t nt l b th pr p ll nt nd n r t t r l th r t n b rr r f r b nd l v f - O
( l l n tr p nd nd O- O ( rr p nd n n tr t r . 1 nd l l -
1 r p t v l - h n tr l n nd l l l n tr t n r l O nd O nd h n
n rv t l t n x d t n f h dr rb n 9-11 In th r rd n tr p nd h v b n d l t d d b b th xp r nt l nd th r t l th d 4-8 1 -33 n v rth l th th r h l d t r rpr n l l t d
p t n f th pl t n tr l n pr t t p d l f r l r r
n pr p ll nt h b n th bj t f n r t d 1 - " 13-17 1- r n tr th n 3 th n rt d l n t n f O O via f v - nt r d nt r d t th l t n r d p t n h nn l rd n t th AC-M nd 3 Y / - 311+G(3df p
l l t n 1 E t t d b rr r f r n tr th n nd -n tr pr p n ( nd 39
l l r p t v l r p r bl t th xp r nt l t v t n n r d t f
n n nd - r r f 3 nd l l -¹²
C nf r t n l p t f l l n tr p nd n p rt l r syn-anti
l br h v b n t d d b v r l r r h r 1 ¹9 h r lt h th t -
l t l r p nl d t b l z t r ll f v r d syn nf r r h n t d f th t r f r h b n h n t rr l t th r l t v t b l t d t fr 1 M
n pr r l l n tr t r - l l n tr t th r v r rd r bt n d t
xp t d h r t l d l l nf r th t b l t f syn nf r r ¹ ¹9
In th pr nt r h v v l t d th f r t n nth lp f v r l n- l l n tr p nd b r n —O O (n tr t nd - O² (n tr - t n t p l pr r
nd r nd t rt r p t n b d n th r t t bl r t t n nf r r n
lt l v l nd nd v d l p t t n l h tr th d W d b th pl t b t nd G n p t l l t n th d h th d pl v r t
f d ff r nt tr fr n d t r n t n nd h h r rd r n r rr t n
(vide infra). h r f th th d h b n d n tr t d n r pr v
t d n O O r ² nd th l nd th l n tr nd n tr t p nd
A h r ft nd Gr n t l 9 h v r ntl r p rt d th r h l pr p rt nd
r p v l f r v r l n tr n- nt n n t bl l l n th t d th C S-
Q 3 b d t z t n th d th n l d d p n- rb t nd dd t v t rr t n
( AC p r l t d t th t d n l d tr -n-pr p n - 9 l l n- r p l 4 n tr t - 7 9 l l l tr - -pr p n -33 l l nd tr -t rt-b t n -
l l t l d 3 Y / -31G(d b d t z t n n r l l t n
nd t rr t n t pr d t nth lp f f r t n f v r l n r t t r l n-pr pl n tr t - 1 l l t rt-n tr b t n - 1 5 l l nd t rt-b t l n tr t
-3 7 l l r p t v l O nt t 1 5 p rf r d l r l l t n t
3 Y / -31G(d p l v l n n tr n-pr p n (-33 1 l l -¹ -n tr pr p n (-35 9
l 1 -¹ nd t rt-n tr b t n (- 3 l l -¹ r p t v l h h t f f r t n
f n-pr p l n tr t nd t rt-b t l n tr t bt n d fr d r t n t th
3 / -31G(d l v l b t l r - 59 l l nd -3 3 l l-¹ r p t v l In n r l AfH°298 v l r n d r nt th pr v v l t d l t r t r ( ISI d t th th x pt n f -n tr pr p n h h h v r l l
l-¹ d ff r n h r t th n l l t d v l
C p t t n l M th d
h r l t v t b l t f O O nd O r h l t b nd d t n n r
nd th h t f f r t n f r d l nd l l bt n d fr d r t n h v b n l l t d n 3 Y h br d d n t f n t n l th r th d n
nj n t n th th -31G(d p nd -31+G( d p b t ll th pl t b
t-Q 3 p t th d C S-Q 3 lt l v l d l h tr th t b n th r lt f v r l b n t nd nd v d l th d nd p r l t r t pr d t
l l r n r th h h r nd r l t v l l p t t n l t h r r d l tr n tr t r l l t n r tl n d f ll ( 3 Y / -
311G( d d p l v l tr nd fr n ; ( M / -311G(3df df p n r nd 5
C S xtr p l t n; ( M -(S Q / -31G(d(f p n r ; ( v CCS ( / -31+G(d
n r rr t n All nt h l l l t n h v b n p rf r d th n th
G n- 3 t f pr r 7
v l t h t f f r t n f th t tl d t d v r t f h d nd d r r t n h r th b nd n nv r n nt r l r
n pr d t nd r nt A h d r t n h p th t l r t n h r th n b r nd t p f b nd (h br d z t n f rr p nd n t r n rv d n b th
d f th r t n An d r t n n h r th n b r f b nd f h t p n rv d n h d f th r r t n
4 lt nd n
4 C nf r t n f tr t
h pt z d tr t th C S-Q 3 p t l v l f th r viz., 3 Y / -
311( d d p l l t n f r th t r t l l nd rr p nd n bbr v t d n n l t r r pr nt d n r 1 1
h t r n l p t nt l f r d l (vide infra) h th t rr p nd n cis nd
trans- r r p t v t th C-O- -O d h dr l n l h v l r n r n th
pr p ll rn-l n r nd -pr p l n tr t h t rt-b t l n tr t h n r 3 l
f r th trans nf r t n h cis p t n f n-pr p l n tr t h th t r n l x n
h h d t nt fr t h dr n t t 51 A h l th cis nf r r f
-pr p l n tr t h th t r n l x n t t A d t n fr h dr n h
cis nf r t n n n-pr pl n tr t 3 l l l r n n r th n
rr p nd n trans nf r t n r -pr p l n tr t nd t rt-b tl n tr t th trans
nf r t n r 3 nd 3 7 l l l r th n cis nf r t n r p t v l
1 C nf r t n f tr Al n
h x n t n th n tr pr p n r l t d t n r h p t n ( t 39 nd
91 A d t n r l t v t th t n th dj nt rb n t In -n tr pr p n
n x n l p d th th h dr n t n th ntr l rb n t In -n tr - -
th l pr p n n x n l p d th rb n t Str t r r ll tr t d n
r 1 1
1 3 Enth lp f r t n
Enth lp f f r t n (Δf ° 9 r v l t d n l l t d l tr n n r z r p nt v br t n n r rr t n ( E nd th r l ntr b t n (t 9 K f r h
f p n th r r t n 3 br t n fr n r l d b 9 f r C S-
Q 3 l v l l l t n
C l l t d r t n nth lp Arxn ° 9 r d t f nd Δf ° 9 f th t r t
l l
Δrxn ° 9 = E Hf (pr d t — E Hf (r t nt
Wh r th t pr d t nd n r t nt r th thr r f r n l l ;
th v l t d l t r t r th r d n pr p rt f r th thr r f r n p h
t nd rd nth lp f f r t n t 9 15 K f r th r f r n p d n th r t n r r z d n bl 1 1 C C 2C 2 O2 ( n 2 C C 2C 2O O ( n C C ( O2 C ( n 2 Nitro-n-propane n-Propyl nitrite Nitro-iso-propane
C C (O O C ( n C C(C 2 O2 ( ( 2 n 2 C C(C 2O O ( ( 2 n Iso-propyl nitrite Nitro-tert-butane Tert-butyl nitrite
Figure 1.1 Geometry of the lowest energy conformers of the titled molecules and corresponding abbreviated nomenclatures (see appendix A, Table A1.1, for more details). 8
bl St nd rd Enth lp f r t n t 9 15 K f f r n Sp d n r r t n f r nth lp f f r t n
A n x pl th f ll n t n d t t t Δf ° 9 f r C C C O
C C C O + C C + C C O
Δf ° 9 ( l l¹ - r t -20 04 -2 02 -2 06
S n nth lp f f r t n f th thr r f r n p nd (v l b v n b ld r ll t bl h d n th l t r t r h h t f r t n Δrxn ° 9 l l t d
nd th nth lp f f r t n f th t r t l l C C C O bt n d -
3 l- l-¹ fr l 9
h th d f d r h d r r t n r l n th l r t f b nd n nv r n nt n th r t nt nd pr d t th t l d t th n ll t n f
t t rr r n th b n t nd d n t f n t n l th r l l t n h z r p nt n r r l d b 9 f r 3 Y / -31G(d p l l t n r nd d b S tt t 14¹ h r t n nth lp nd th nth lp f f r t n f th l l n tr
nd n tr t bt n d fr th f th r t n h r h n n bl 1
In r pr v t d l l t d th th r h tr f th l nd th l n tr
nd n tr t p nd nd f nd th t n tr l n r r t bl th n th
rr p nd n n tr t r b l 1 f r O O v r O 3 l
l-¹ f r C O v r C O O nd 1 l l-¹ f r C C O v r
C C O O n th d ff r n n Δ (° 9 b t n O nd O O xp t d t b b t 1 7 l l W d n t b rv n f nt h n n th O vs O O f r pr r vs. nd r vs. t rt r b t t t d n tr r n tr t p nd h r th ht tr nd r d t d ff r n n l tr n pr p rt C p r n f th
l l t d nd v l t d xp r nt l d t h th t th v l p t d t C S-Q 3
p t l v l t xp t d r n f ntl l r t th xp r nt l d t ; th
r nt x ll nt h l p r n th IS d t b v l ( S h 1
S h 1 r t n nth lp ( l l f r r f tr nd tr t p nd l l t d t C S-Q 3 l v l f th r n p r n th rr p nd n IS d t
IS Sp h t d r f r n C C C O O - - C C (O O C -32.3 -31 9 C C(C O - - 3 C C(C O O - 1 - 1 1
W n t th t th r r n v r 3 l l-¹ d ff r n n 3 Y / -3 1G(d p r lt b t n Δf ° 9 v l v l t d n th t d v r th l l t d b O nt
t 1 5 r p n r j d d t r lt fr d ff r n n n d r t n
n l n r t d v r f th pt z d t f t z t n nv r n v l d r v d fr th l br t n n t v n l t d xO p nd n O nt t l
r 5 C rr p nd n d ff r n f r n-n tr pr p n -n tr pr p n nd tert- n tr b t n r 3 1 l l 3 3 l l-¹ nd l l-¹ r p t v l bl 2 Calculated Reaction Enthalpies at 298 K and Evaluated Enthalpies of Formation of Target Molecules'
( Reaction enthalpies include thermal correction and zero-point energy.) Table 1.2 (Continued) 13
Table 1.3 Formation Enthalpies for a Series of Nitro and Nitrite Compounds Calculated at Evaluated at Different Levels of Theory (Recommended Values are in Bold)
C 2C 2C 2 O2 ( j n 2 C C C 2 O2 ( j n 2 C C 2C O2 ( jn 2 C 2C 2C 2O O ( j n C C C 2O O ( j n C 2C ( O2 C ( j n 2
C C( O2 C ( jn 2 C C (O O CM ( j n C 2C(C 2 O2 ( j ( 2 n 2
C 2C(C 20 O ( j ( 2 n
r 1 Illustrations of the lowest energy conformers of radicals corresponding to the loss of a hydrogen atom from parent molecules (see Table B1.2-B1.17, appendix B, for details) and nomenclature.
4 4 nd t n En r
nd n r r d r v d fr Ar ° 9 f p r nt l l nd th r r d l
rr p nd n t th l f h dr n t r th t nd rd nth lp f h dr n t
t 9 15 K d 5 1 3 l 1 -1 h r lt d b nd d t n nth lp
p t d fr d nth lp f f r t n r v n n bl 1
W p r th b nd n r n t l r b nd n r n l n W h v
d f ll n v l pr r 1 1 1 l 1 -1 nd r 9 5 l l nd t rt r
9 5 l l-1 f r C— b nd n r n l n h C— b nd n th rb n n
lph p t n t th O /O O r p h th l r t d v t n (d r n b nd
n r f v r l l l h b nd n r f r jn 2 nd j(n 2 r d l t
r 9 l l nd 9 l l r p t v l h d t th r n n f th r d l nt r th th l tr n t v O r p K n tz t l 7 h v r p rt d tr n
rr l t n b t n nt rn l r t r b rr r nd r n n n C— t f r d W
l r rr l t n n C— b nd d t n tr - rb n r d l t
h j n nd j( n r d l d n t x t b th O— O b nd t 3
l l h r th n th rb n l -b nd (— l 1 f r d n pr p n l
C 3C C(=O nd th t n C 3C(=O C 3 l l th p t nt l pr d t f th b t n f rr p nd n CjO— O b nd In ff t th r d l f r d b l
f h dr n t n th C–O O b nd d rb n d t v b t n t
rb n l + O d t l p n r d l f r t n p t v C— b nd n r n
jn 2 (n-pr p l n tr t t t d t 95 l l fr l t r t r (tr n t n t t
l l t n 1
h d t n n r f r pr r th l rb n—h dr n b nd n n tr n pr p n nd n-pr p l n tr t r th th pr r C— b nd n r n
l n
h pr r rb n-h dr n b nd n r n n tr nd n tr t d r v t v f pr p n nd t rt-b t n r 1 l l h h 1 l 1 h h r th n th t n
l n h r d l nt r r l t d t b t p t n t th l tr n t v O„
r p p r t d b n p rb n b r n p rt l p t v h r W nt rpr t th
n r d b nd n r d t p l r z t n ff t C— b nd f nd r rb n
t n n tr -n-pr p n nd n-pr p l n tr t r – 5 l l tr n r th n r p t v b nd n l n (– 99 l l ; th l r lt thr h p l r z t n fr th
dj nt ( lph p t n rb n t b nd d t th O O r O r p bl 4 Reaction Enthalpies at 298 K for Radicals, Calculated Enthalpies of Formation and Bond Energya Table 1.4 (Continued) bl 4 (C nt n d
t n nth lp n l d th r l rr t n nd z r -p nt n r 20
bl S r f r t n Enth lp (Af 9 nd nd t n En r ( E f r tr l n nd Al l tr t M l l nd th r C rb n d l ( n l
d l r r pr nt d b bbr v t d f r l f r pl t ; j r pr nt r d l t 2
4 Int rn l t t n t nt l
En r pr f l f r nt rn l r t t n b t th C-C C- C- O C—O O nd - O b nd n th n tr l n nd l l n tr t r l l t d t d t r n n r f th r t t n l nf r r nd nt r nv r n b rr r b t n r r n l p t nt l
r th n d t v l t ntr b t n t th ntr p nd h t p t v l fr th l b rr r (b l 5 l 1 -1 r t r h t t l n r f n t n f th
rr p nd n d h dr l n l r p t d t th 3 Y / -31G(d p l v l f th r b nn n th t r n n l b t n ° nd 3 ° n t p f 15° h l ll r n n
rd n t r f ll pt z d All p t nt l r r - nn d h n l r n r
nf r r r l t v t th n t l l n r nf r r f nd h t t l n r f th
rr p nd n t t bl l l r nf r r rb tr r l t t z r nd th d
r f r n p nt t pl t th p t nt l b rr r h r lt n p t nt l n r b rr r f r nt rn l r t t n n th t bl n n-r d l nd r d l l l r h n n
1 3 1-1 3 1 h dr l n l bt n d f r th pt z d l t n r tr t r r
h n n p r nth
h l l t d r t t n l b rr r f th l r p n 1-n tr pr p n - n tr pr p n nd -n tr - - th l pr p n ( 1 3 1 1 3 3 nd 1 3 5 h th thr - f ld tr th th b rr r f 3 l 1 -1 h h l r t th th l r t r p t nt l n n-h dr rb n h C- O r t r n 1-n tr nd -n tr pr p n xh b t d l -f ld tr b rr r f 1 5 nd l 1 h ht r p t v l h l th p t nt l f r -n tr - - th l pr p n h d -f ld tr th b rr r f 3 l
O-- O nt rn l r t r ll h tr -f ld b rr r f 1 t 1 l l h ht 22
Hindered Rotation for cccno2
Figure 1.3.1 Potential Energy Profiles for Internal Rotations in Nitro-n-propane.
Figure 1.3.2 Potential Energy Profiles for Internal Rotations in n-propyl nitrite. 23
Hindered Rotation of cc(no2)c
Figure 1.3.3 Potential Energy Profiles for Internal Rotations in Nitro-iso-propane.
Figure 1.3.4 Potential Energy Profiles for Internal Rotations in iso-propyl nitrite
Hindered Rotation of cc(c2)no2
r 1 3 5 Potential Energy Profiles for Internal Rotations in Nitro-tert-butane
r 1 3 Potential Energy Profiles for Internal Rotations in tert-butyl nitrite 5
•1-1 C C O rb n r d l f n tr pr p n , cjccno2.
The rotation barrier of the methyl group j n 2 is reduced to 0.15 kcal moll , nearly a free rotor, where the corresponding potential is six-fold and similar to that in a normal hydrocarbon. Instead, the j n 2 rotor has a three-fold potential with one barrier located at 4.9 and two barriers at 2.6 kcal mol l . The j n 2 rotor is similar to the non- radical nitropropane (parent molecule) with two-fold barriers at 1.25 kcal moll.
r 1 3 7 Potential Energy Profiles for Internal Rotations in C•1 -12CH2CH2NO2 Radical ( j n 2 26
CH3C•HCH2NO2, /3-carbon radical of nitropropane, ccjcno2
There are significant differences in all three internal rotor potentials in the ccjcno2
(nitropropane -2y1) radical and the parent molecule. The c--cjcno2 methyl rotor is a three- fold one, but with extremely low barrier at 0.65 kcal moi l . For the ccj--cno2 rotor, there is a two-fold potential with barriers of 3.39 and 1.65 kcal mol l , respectively. The ccjc-- no2 rotor has a four-fold potential with alternating 0.6 and 0.2 kcal mol I barriers.
Figure 1.3.8 Potential Energy Profiles for Internal Rotations in CH3C•FICH2NO2 Radical (ccjcno2) 27
CH3CH2•HNO2, a-carbon radical of nitropropane, cccjno2
The methyl rotor c--ccjno2 is similar to a normal alkane as well as in the parent molecule.
The potential foldness in the ethyl rotor cc-cjno2 is similar to the parent molecule, but the barriers are reduced by near one half. The barrier for the -NO2 rotor between nitrogen atom and the radical carbon site in cccj--no2 is significantly high (9.5 kcal moi l ). The barrier increase (8.25 kcal mo1 -1 ) suggests a high degree of resonance between the carbon radical and the NO2 group; this was also observed by Kemnitz et 7 (see also bond energy discussion above).
Figure 1.3.9 Potential energy profiles for internal rotations in CH 3CH C•HNO Radical (cccjno2) 28
C• 2C 2C 2O O rb n r d l f pr p l n tr t , j n
The j n the internal rotors are similar to those in the parent propyl nitrite, with the exception of the methyl rotor j n , which has the barrier reduced from 3.0 to less than 0.5 kcal mol l . The 2-fold very high barrier (14.5 kcal mol -1 ) in the j n rotor is similar to that in the parent molecule.
r 0 Potential Energy Profiles for Internal Rotation in C•1 -12CH2CH2ONO Radical ( j n 9
C 3C•1C O O /3-carbon radical of propyl nitrite, ccjcono
rr r f r th th l nd th l r t r n ccjcono r d r d r l t v t b rr r n th p r nt l l nd th ccjc--ono b rr r l d r d fr 9 5 l l l n th p r nt t ca l l l n th r d l t h t -f ld ccjco--no r t r r t n th h h b rr r (1 5 l l l h h l r t th t n th p r nt l l h
C 3C •1-1 O r d l (cccjono) n t t bl ; t nd r r p d x th r d t n t pr p n l pl O p n f r t n f th rb n r d l b nd n t th
O O r p h lph rb n r d l d t l n t t f r t n f tr n n-b nd
( l ll n th rb n l nd l v n th ( 3 l l l — O b nd d d b v
r 1 3 11 t nt l En r r f l f r Int rn l t t n n C 3C• C O O d l (ccjcono) 3
C• C ( O C 3 primary carbon radical of nitro-iso-propane, j (n 2 .
The cjc(--no2)c rotor exhibits the same barriers as in the parent molecule with some distortion of the symmetric 2-fold potential of the parent, while the barrier of the methyl rotor is decreased from 3 to 1.4 kcal mola I
r 1 3 1 Potential Energy Profiles for Internal Rotation in C•1-12CH2(NO2)CH3 Radical (cjc(no2)c). 31
CH3C•(NO2)CH3 , t rt r rb n r d l f n tr pr p n , ccj(no2)c
The j(n 2 rotor is reduced to less than 0.1 kcal mol l , while the j( n 2 rotor is increased from 0.5 in 2 nitropropane to 11 kcal moi l in this radical, this is reflects in the
6 to 8 kcal moi l resonance, as determined from the decreased bond energy relative to a normal tertiary or secondary alkyl radical respectively, on this central carbon radical with the NO group.
Figure 1.3.13 Potential Energy Profiles for Internal Rotation in CH 3C•F1 (NO )CH3 Radical ( j(n 2 3
•1-1 C ( O C 3 pr r rb n r d l f pr p l n tr t , j ( n
There are significant differences in two internal rotor potentials between j ( n radicals (tr n configurations) and the parent (cis-configuration). The j ( n rotor has 3-folds with barrier of 9.1, 5.6 and 0.7 kcal mo1 -1 while the methyl radical rotor barrier is decreased from 3 to 1.4 kcal ma i and has a distorted two fold potential. The parent has a three fold potential. The j ( —n rotor is similar to that in the parent with a two fold potential and very high barrier (14 kcal mo1-1).
r 1 3 1 Potential Energy Profiles for Internal Rotation in C•112CH2(0NO)CH3 Radical (cjc(ono)c) 33
0 2C 2(C 2 2 O2 , pr r rb n r d l f n tr b t n , j ( 2 n 2
h O2 rotor in j ( 2 n 2 shows a six fold barrier, four barriers at 0.28 kcal mol l and two barriers at 0.12 kcal mol l . The CH2• has an internal rotor barrier that is approximately one half that of the methyl in 2-nitro-2-methyl propane and is now a distorted two fold potential compared to three fold for the parent. The two methyl (CH3-) rotor profiles are similar to that of the CH3 rotors on parent molecule and are not illustrated in Fig 1.3.15.
r 1 3 15 Potential Energy Profiles for Internal Rotation in C•H2CH2(CH2) 2NO2 Radical ( j ( 2 n 2 34
C•112CH2(CH2)20NO, primary carbon radical of iso-butyl nitrite, cjc(c2)no2
The methyl radical rotor has a two fold potential with barriers at 1.1 kcal mo1 -1 . The R--
ONO rotor, cjc(c2)--ono, and the RO—NO rotor, cj-- c(c2)o-no, are similar to the corresponding rotors in the closed-shell parents. The two methyl rotors are similar to those in the parent molecules and are not illustrated.
Hindered rotation of cjc(c2)ono
Figure 1.3.16 Potential Energy Profiles for Internal Rotation in C•H2CH2(CH2) 20N0 Radical (cjc(c2)ono)
1.4.6 Entropy and Heat Capacity Data
Entropy and heat capacity contributions as a function of temperature are determined from
the calculated structures, moments of inertia, vibration frequencies, symmetry, electron
degeneracy, number of optical isomers and the known mass of each molecule. The
calculations use standard formulas from statistical mechanics for the contributions of
translation, external rotation and vibrations using the "SMCPS" program. 42 This program
utilizes the rigid-rotor-harmonic oscillator approximation from the frequencies along with 35
nt f n rt fr th pt z d C S-Q 3 tr t r viz. 3 Y / -3 1 1 G( d d p l v l C ntr b t n fr nt rn l r t r (I n bl 1 n tz r-G nn f r l 5 r b t t t d f r ntr b t n fr nt rn l r t r t r n fr n
h r b rr r r d t r n d t b b l 5 l 1-1 h ntr p nd h t
p t d t r n d d t d t r n d p nd n f th nth lp ntr p G bb En r
nd l br n t nt th t p r t r Entr p nd h t p t l l t n r p rf r d n pl t b t -Q 3 d t r n d tr nd h r n fr n r z d n bl 1
h ntr p nd h t p t v l f th t d r p r d th th r ntl p bl h d d t f A h r ft nd Gr n 9 f r th t bl n tr l n l l nd th
ll tr t d n bl App nd x A1 1 h v l f ntr p nd h t p t r ll th n
n l th n l l K-1 th th x pt n f pr p n n tr t h h h v l
f h t p t v r n b p t l l K-1 nd n ntr p d ff r n rr p nd n t
ln(3 6
bl 6 Id l G -ph h r d n r p rt vs. p r t r
bl 6 (C nt n d 8
bl 6 (Continued)
bl 6 (C nt n d
h r d n pr p rt r r f rr d t t nd rd t t f n d l t 1 t S°( nd C°p( r n l l-1 K-1 b S tr n b r d f r l l t n f S°( r n p r nth
1 7 Gr p l f r n th Gr p Add t v t M th d f r E t t n f h r h l pr p rt
Gr p dd t v t 3 tr htf r rd nd r n bl r t l l t n th d t
t t th r d n pr p rt f h dr rb n nd x n t d h dr rb n ; t
p rt l rl f l f r ppl t n t l r r l l f r n d r d t b f r th t t n f th r h l pr p rt n r t n h n n r t n In th p p r t t x n tr l n l l n tr t nd th t n rr p nd n rb n
nt r d r d l r p b n th th r d n pr p rt d t d v l p d n th
t d pl th l l-h dr rb n r p n th l t r t r h xt n r p r l t d n th bl 1 7 l n th t nd rd h dr rb n r p d
C p r n f r p dd t v t d t f r thr r p — th th d t f A h r ft
nd Gr n 9 (t p r t r f 3 t 15 K r ll tr t d n bl App nd x A1 1 h
A h r ft nd Gr n d t r n t ntl f t nth f l 1 ICI h h r th n th d t n th t d ; f th pr b bl d t th r tr t nt f ll nt rn l r t r r t r h l tr t nl r t r th t h v b rr r b l 5 l l -1 4
bl Gr p h r h l l v l p d n th St d
tr n b r ( t n nt nt (S =S t - ln
C n l n
h r h l pr p rt nth lp f f r t n r b rv d t f ll th tr nd
f pr v v l f th l nd th l n tr t nd n tr p nd O r th r h tr
9 d t Af ° 9 S °( nd C°p( r n d r nt th d t fr Gr n t l
l l t d b C S-Q 3 th b nd rr t n h nth lp f f r t n f n tr l n r f nd t b l htl ( 1- l l r t bl (l r
nth lp th n th rr p nd n n tr t th th d ff r n n Af ° 9 b t n O
nd O O r n n n r n t nt t b t 1 7 l l l C rb n -- h dr n b nd
n r n th n tr - b t t t d rb n r b rv d t d r b 5 t l l -1 r l t v t C- b nd n rr p nd n l n In ntr t th rb n - h dr n b nd
n r r b rv d t n r b - 1 l 1 -1 f r rb n t l t d n b t p t n t th rb n b nd d t th l tr n t v n tr / n tr t r p C— b nd n
rb n t t th n tr r n tr t r p pp r d t b d nt l t th n
rr p nd n t n l n th n l l t n rr r b r v l f h dr n
t fr th rb n b nd d t th n tr t (O O r p r lt d n x th r r t n
th l ttl r n b rr r t f r rb n l pl O Enth lp f f r t n ntr p
S°( nd h t p t C° p( v l r r p rt d l n th b nd n r nd
rr p nd n th r h l pr p rt f r 1 nd n tr -pr p n nd -n tr - th l pr p n nd r d l rr p nd n t l f h dr n t fr th rb n t h
p t d nth lp f f r t n v d r r t n nd b nd d t n
n r f r n tr l n nd l l n tr t r n t f t r r nt th th l t d
xp r nt l d t v l bl Gr p f r n r p dd t v t r d v l p d C A E
E MOC EMICA O E IES O A SE IES O I OCA O Y S I OO E I S
1 Ov rv
Structures, enthalpy (AfH°298), entropy (S°298), and heat capacity (C p(T)) are determined for a series of nitrocarbonyls, nitroolefins, corresponding nitrites and their carbon centered radicals using the density functional B3LYP and composite CBS-QB3 calculations. Enthalpies of formation (AfH°298) are determined at the B3LYP/6-31G(d,p),
B3LYP /6-31+G(2d,2p) and composite CBS-QB3 levels using several work reactions for each species. Entropy (S) and heat capacity (Cp(7)) values from vibration, translational, and external rotational contributions are calculated using the rigid-rotor-harmonic- oscillator approximation based on the vibration frequencies and structures obtained from the density functional studies. Contribution to AfH (7), S, and C p(T) from analysis on the internal rotors is included. Recommended values for enthalpies of formation of the most stable conformers of nitroacetone, 2 propane nitrite, nitroacetate and acetyl nitrite are -
51.58 kcal mol -1 , -51.26 kcal moF 1 , -45.36 kcal ma i and -58.17 kcal moi l , respectively.
The calculated AfH°298for nitroethylene is 7.59 kcal ma i and for Vinyl nitrite is 7.23 kcal mo1-1 .
3 44
2 2 r nd Inf r t n
A r t f r t n nth lp Af ° 9 f r n tr nd n tr t l l r r r d n
rd r t nd r t nd r t n p th nd t n th d v l p nt f d t l d h l
n t h n h h n b ppl d t d l th f r t n nd d tr t n f n tr n p n v r t f nv r n nt p rt l rl f r t ph r nd
b t n h tr S n l th n % f n n r n p h v h d th r h t f f r t n r th ppl t n f nt h tr th d f r th d t
f v l pr v d d th t r n bl r n b bt n d h t bl h nt f th v l ll l d n th d t r n t n f th th r h l pr p rt f h h r h l via f d r t n th r p n rv t n ( t n r t n h t d nt n d v l p nt nd v l t n f th r h l pr p rt n pl t n tr - nd n tr t p nd fr r pr v n l 3
tr ( O nd n tr t ( O O d r v t v f h dr rb n nd r th r l d p t n t r l t v l l t p r t r nd h n h v p t nt l b th pr p ll nt nd n r t t r l th r t n b rr r f r b nd l v f - O
( l l n tr p nd nd O- O ( rr p nd n n tr t r ca. 1 nd l l -
1 r p t v l " h n tr l n nd l l l n tr t n r l O nd O nd h n
n rv t l t n x d t n f h dr rb n 9-11 In th r rd n tr p nd
- 1 -33 h v b n d l t d d b b th xp r nt l nd th r t l th d n v rth l th th r h l d t r rpr n l l t d
h tr t r h t f f r t n b nd d t n n r t f n tr nd n tr t l l h v b n th bj t f n xp r nt l nd th r t l
nv t t n Sh 5° d r p dd t v t t pr d t Af ° 9 n n tr th l n t 1 4
l l nd r7 pr f r d MI O/3 l l t n th 17 l 1 -1 x n 12 r p rt d h t f f r t n b CCS ( l l t n n n r t t r l th 9 5 l
ll f r n tr th l n h l n n 51 l t d 9 l l l Gr n t l 49 pr f r th r h l pr p rt nd r p v l f r n tr n- nt n n l l th C S-
Q 3 b d t z t n th d th p n- rb t nd dd t v t rr t n ( AC
Af ° 9 f v n l n tr t nd n tr th l n r 5 l l l nd 9 l l l r p t v l
In th pr nt r h v v l t d th f r t n nth lp f v r l n tr rb n l n tr l f n rr p nd n n tr t nd th r rb n nt r d r d l b d n th r t t bl r t t n nf r r n lt l v l nd nd v d l
p t t n l h tr th d W d b th pl t b t nd G n
p t l l t n th d h th d pl v r t f d ff r nt tr fr n d t r n t n nd h h r rd r n r rr t n (v d nfr . h r
f th th d h b n d n tr t d n r pr v t d n O G r nd
th l nd th l n tr nd n tr t p nd 3
2 C p t t n l M th d
h r l t v t b l t f O O nd O r h l t b nd d t n n r
nd th h t f f r t n f r d l nd l l bt n d fr d r t n h v b n p rf r d n 3 Y h br d d n t f n t n l th r th d n
nj n t n th th -3 1 G(d p nd -3 1+G( d p b t ll th pl t b
t - Q 3 p t th d C S-Q 3 lt l v l d l h tr th t b n th r lt f v r l b n t nd nd v d l th d nd p r l t r t pr d t 46
l l r n r th h h r nd r l t v l l p t t n l t h r r d l tr n tr t r l l t n r tl n d f ll ( 3 Y / -
311G( d d p l v l tr nd fr n ; ( M / -311G(3df df p n r nd
C S xtr p l t n; ( M -(S Q / -31G(d(f p n r ; ( v CCS ( / -31G n r
rr t n All nt h l l l t n h v b n p rf r d th n th
G n- 3 t f pr r 3
W d v r t f h d nd d r r t n h r th b nd n
nv r n nt r l r n pr d t nd r t nt A h d r t n h p th t l r t n h r th n b r nd t p f b nd ( rd n t th t t f h br d z t n r n rv d n b th d f th r t n An d r t n n
h r th n b r f b nd f h t p r n rv d n h d f th r r t n
2 4 lt nd n
h pt z d tr t th C S-Q 3 p t l v l f th r (viz., 3 Y / -
311( d d p l l t n f r th t r t l l nd rr p nd n bbr v t d n n l t r r pr nt d n r 1 h trans nf r t n r p t v t C-O- -O d h dr l n l n pr p n n tr t v n l n tr t nd t l n tr t r t bl th n
rr p nd n cis r b 1 l l 1 7 l l-1 nd 3 9 l 1 -1 r p t v l In n tr t n nd pr p n n tr t n tr nd n tr t r p r n trans
nf r t n t rb n l x n On x n n n tr th l n nd n tr n n v n l n tr t l p d th h dr n t n th f r t rb n h l n x n n n tr t t
nd n tr n n t l n tr t l p d th rb n l x n 7
C C( O C 2 O2 C C( O C 2O O C 2 C O2 ( ( n 2 ( ( n ( n 2 tr t n r p n n n tr t tr th l n
C =C O O C 3C(= O C 3C(= O ( n ( ( n 2 ( ( n n l n tr t tr t t A t l n tr t
r 1 G tr f th l t n r nf r r f th t r t l l nd bbr v t d n n l t r ( pp nd x C bl C -C 15 f r r d t l
1 Enth lp f r t n
En r fr th C S-Q 3 p t l v l r d th r f d
r t n h v n b nd n rv t n t t t th nth lp f f r t n (Af ° 9 f r
t r t l l h t t l n r r rr t d b z r --p nt v br t n n r
( E h h r l d b 97 r nd d b S tt nd d 1 h r l
rr t n - 9 15 K l l t d t t t Af ° 9 t 9 15 K W th
l l t d A x - ° 9 n th f r l t find AfH°298 f th t r t r t nt 48
ArxnH°2 8 E Hf pr d t — E Hf r t nt
Wh r th t pr d t nd n r t nt r th thr r f r n l l
th v l t d l t r t r th r d n pr p rt f r th thr r f r n p h
t nd rd nth lp f f r t n t 9 15 K f th r f r n p d n th r t n r r z d n bl 1
bl 2 h St nd rd Enth lp f r t n t 9 15 K f f r n Sp 4
A n x pl th f ll n t n d t t t Af ° 9 f r C =C O
(C =C O + (C 4 (CH2=CHCH ) + (CH NO2)
AfH°298 ( l l - : r t -20 04 4 88 - 6
S n nth lp f f r t n f th thr r f r n p nd ( n b ld b v
r ll t bl h d n th l t r t r th A „ ° 9 l l t d nd th nth lp f f r t n f th t r t l l C =C O bt n d fr l
h th d f d r t n t l z l r t n th b nd n
nv r n nt f r r t nt nd pr d t t n r r t n t ff t n ll t n f
t t rr r n th ab initio r d n t f n t n l l l t n h b r r nt
f n d r t n th t th n b r f h t p f b nd n rv d n th r t n h z r p nt n r r l d b 9 r nd d b S tt t 1 1 f r 3 Y / -31G(d p nd th r l rr t n t 9 15K C l l t n r p rf r d n
h p n thr r r t n f r h l l h r t n nth lp nd th
nth lp f f r t n f th t r t l l bt n d fr th f th r t n
h r h n n bl bl 2 2 Calculated Reaction Enthalpies at 298 K and Evaluated Enthalpies of Formation of Target Moleculesa bl 2 2 (continued) 52
Table 2.3 r t n Enth lp f r S r f tr rb n l tr l f n C p nd C l l t d t Ev l t d t ff r nt v l f h r ( nd d l r n ld
t n r nf r t n tr t r f th r d l r ll tr t d n r
2.4.2 Bond Dissociation Energies
nd n r r r p rt d fr th l l t d th Ar ° 9 f th p r nt l l nd t r d l rr p nd n t l f h dr n t h r th nth lp f p r nt l l
nd pr d t p r l l t d n th t d n nj n t n th th v l f 5 1
l l f r ; th d t rr p nd t th t nd rd t p r t r f 9 15 K h
nd v d l b nd d t n nth lp v l p t d fr d nth lp f f r t n r v n n bl
W p r th b nd n r n t l r b nd n r n t n ; nd f r p rp f p r n v l t nd th C-- b nd n r n t n 95
l l h b nd d t n n r f r --C C(=O C O nd H--
CH2C(=O)CH2ONO r th b nd n r n t n h b nd n r f r
( jn 2 r d l t r 95 l l ; —5 l l n r fr b nd n r
n nd r rb n n th l th l t n (MEK h d t r n n f th 53 r d l b t n th lph rb n nd th rb n l rb n K n tz t l 7 l f nd
rr l t n b t n th nt rn l r t r b rr r nd r n n n C-- t f r d
tr nd n tr t r p b t t t n f r h dr n t n th rb n l rb n n
t ld h d n r d b nd n r - 1 l l n --C C(=O O (95 9 l l
nd - l l f r -C C(= O (9 3 l Y 1 -l
h C-- b nd n r n n tr th l n -C =C O 115 l 1 -1
nd v n l n tr t --C =C O O 11 3 l l -1 h h - l 1 h h r th n th t n th l n h C-- b nd n r n C =C(-- O (11 5 l 1-1
n r d - l 1 p r d t th nd r b nd n r n pr p l n h r lt fr th O O O ( l tr n thdr n r p dr n n l tr n thr h th p b nd n th C rb n r l tr ph l ( rb n t r p t v nd
b ntl th C =C -- b nd tr n r
h ( j n nd j n l l d n t x t b th O— O b nd
t 3 l 1 h r th n th rb n l n b nd (- l l b n f r d
n C 3C(=O C (=O nd t n C =C= h l l th th r d l t
dj nt t th n r p d t t f r rb n l nd O r d l d t l
p n th r f r t n
5
C 2 C( O C 2 O2 CH3C(=O)CHNO2 C 2C( O C 2O O
( j ( n 2 ( ( jn 2 ( j ( n
CH=CHNO CH2=CNO2 C =C O O
(cj=cno2) ( jn 2 ( j n
C 2 C( 0 O 2 CH2C(=O)ONO
( j ( n 2 ( j ( n
r Structures and used nomenclature of th lowest energy conformers of radicals corresponding to the loss of a hydrogen atom from parent molecules (see Table C2.2-C2.15, appendix C, for details). bl 2 4 Reaction Enthalpies at 298 K for Radicals, Calculated Enthalpies of Formation and Bond Energy' bl 2 4 (Continued) bl 2 4 (C nt n d
t n nth lp n l d th r l rr t n nd z r -p nt n r 58
Table 2.5 S r f AfH298 nd nd En r l f r tr rb n l nd tr l f n nd th r C rb n d l a ( n l ld
a d l r r pr nt d b bbr v t d f r l f r pl t ; j r pr nt r d l t
2.4.3 Internal Rotation Potentials
t t n b t th C-C C- C- O C-O O nd - O b nd n th t r t l l
r t d d En r pr f l f r nt rn l r t t n r l l t d t d t r n n r f th r t t n l nf r r nd nt r nv r n b rr r l n th ntr b t n t th 59
ntr p nd h t p t f r th l b rr r (b l 5 l 1 r t r r n
l l t d b th G n d r x n d b v n th v br t n d v nt; th ntr b t n fr fr n rr p nd n t nt rn l r t t n r x l d d fr th ntr p nd h t p t nd r pl d th r r t t t f S nd Cp(T) fr th nt rn l r t r ntr b t n h t t l n r f n t n f th d h dr l
n l r p t d t th 3 Y / -31G(d p l v l f th r b nn n th t r n
n l b t n ° nd 3 ° n t p f 15° h l ll r n n rd n t r f ll
pt z d All p t nt l r r - nn d h n l r n r nf r r f nd r l t v t th n t l l n r nf r r h t t l n r rr p nd n t th t
t bl l l r nf r r rb tr r l t t z r nd th d r f r n p nt t pl t th p t nt l b rr r h r lt n p t nt l n r b rr r f r nt rn l r t t n
n th t bl n n-r d l nd r d l l l r h n n 3 1- 3 1 h dr l
n l d n pt z tr t r r h n n p r nth
h l l t d r t t n l b rr r f th l r p ll h th tr l thr -f ld tr th th b rr r b t n 1 nd 1 5 l 1 h h l ttl b t l r p r t t p l l l th l r t t n h h r n n b t n 7 nd 3 l
l h C- O r t r n n tr t n nd n tr t t xh b t d l -f ld tr b rr r f 1 nd l l h ht r p t v l h l th p t nt l f r n tr th l n h d -f ld tr th b rr r f 5 l l O-- O nt rn l r t r n pr p n n tr t nd v n l n tr t h tr -f ld h h b rr r f 13 l
l h l th p t nt l n t l n tr t h d -f ld b rr r f 3 nd 5 l l 60
Potential energy for nt rn l r t t n n Nitro ace tone
Figure 2.3.1 Potential Energy Profiles for Internal Rotations in Nitroacetone.
Figure 2.3.2 Potential Energy Profiles for Internal Rotations in 2 propanone nitrite. 1
r 3 3 Potential Energy Profiles for Internal Rotations in Nitroethylene.
r 3 Potential Energy Profiles for Internal Rotations in Vinyl nitrite. 62
Potential energy for internal rotation in Nitroacetate
Figure 2.3.5 Potential Energy Profiles for Internal Rotations in Nitroacetate.
Figure 2.3.6 Potential Energy Profiles for Internal Rotations in Acetyl nitrite. 3
•1 12C(.0)CH2NO2 cjc(=o)--cno2 rotor and --NO2 rotor barrier are similar to that in the parent cjc(=o)cno2.
The barrier for the cj--c(=o)cno2 rotor of the methyl radical site is significantly increased
(to 13 kcal mol ) and distorted two potential compared to a 3-fold barrier for the parent.
This barrier increase (11.6 kcal moi l ) suggests a high degree of resonance between the carbon radical and the carbonyl oxygen; this is interpreted as the difference between the barrier of the parent and was also abserved by Kemnitz et a1 7 .
r 3 7 Potential Energy Profiles for Internal Rotations in cjc(=o)cno2 64
C C(=0 • - O2
The --NO2 rotor in ( jn 2 is increased from 2.1 kcal mor l in nitroacetone to 8 kcal moi l in radical, this is reflected in the 6 kcal moi l resonance. The ( jn 2 rotor has a 2-fold potential with the barrier at 3.1 kcal moi l while the methyl rotor is similar to that in the parent.
t nt l n r f r nt rn l r t t n n ( jn 2
r 2 8 Potential Energy Profiles for Internal Rotations in ( jn 2 5
•1-1 C( C O O
h r r n f nt d ff r n n nt rn l r t r p t nt l b t n th j ( n r d l( nf r t n nd th p r nt (tr n nf r n h j ( n r t r h -f ld b rr r th th b rr r f 9 nd 3 l l l h l th j ( n r t r h
d t rt d n p t nt l t 3 5 l l l h p r nt h t f ld p t nt l h
j ( n r t r l r t th t n th p r nt th t f ld p t nt l nd v r h h b rr r (13 l l l h b rr r f r th j ( n r t r f th th l r d l t
n r d fr 1 5 l l l n th p r nt t 1 l l l n th r d l h r fl t d n th 1 5 l l l r n n
r 3 9 t nt l n r pr f l f r nt rn l r t t n n j ( n 66
C•FI=CHNO2
The --NO2 rotor in cj=cno2 has a 2-fold barrier with the barriers at 5 kcal ma compared to the parent with a 2-fold barrier at 6.5 kcal moll
Figure 2.3.10 Potential Energy for Internal Rotation in cj=cno2 67
CH2=C•NO2
The --NO2 rotor exhibits a 2-fold barrier with some distortion of the symmetric 2-fold potential of the parent and the barriers is decreased from 6.5 kcal mo1 -1 in the parent to
2.5 kcal mol 1 in this radical.
5
Figure 2.3.11 Potential Energy for Internal Rotation in c=cjno2
•1-1=C O O
All internal rotor in j n are similar to those in the parent vinyl nitrite. The j n rotor is similar to that in the parent with a two fold potential and very high barrier (13.5 kcal mol I ) while the j — n rotor has a three fold potential with one at barrier at 2 kcal moi l and two barriers at 4 kcal ma' .
r 3 1 Potential Energy for Internal Rotation in j n 9
C•11 C(= O
h b rr r f r th j ( n 2 r t r f th th l r d l t n f ntl n r d
(t 1 l l nd d t rt d t p t nt l p r d t th thr f ld f r th p r nt
h b rr r n r (11 l l t h h d r f r n n b t n th
rb n r d l nd th rb n l x n h j ( —n 2 r t r h -f ld b rr r th th b rr r f l l
r 3 13 t nt l En r f r Int rn l t t n n j ( n 2 0
C• 2C(=0 0 O
The barrier for the cj--c(=o)ono rotor of the methyl radical site is significantly increased
(to 9 kcal mol -1 ) and distorted two potential compared to three fold for the parent. This barrier increase (8.5 kcal ma i ) suggests a high degree of resonance between the carbon radical and the carbonyl oxygen. The cjc(=o)--ono and cjc(=o)o--no rotor barriers increase -1 kcal moi l with two fold compare to that in the parent.
r 2 4 Potential Energy for Internal Rotation in cjc(=o)ono
2 4 4 Entr p nd t C p t t
Entropy and heat capacity contributions as a function of temperature are determined from
the calculated structures, moments of inertia, vibration frequencies, symmetry, electron
degeneracy, number of optical isomers and the known mass of each molecule. The
calculations use standard formulas from statistical mechanics for the contributions of
translation, external rotation and vibrations using the "SMCPS" program. 42 This program
utilizes the rigid-rotor-harmonic oscillator approximation from the frequencies along with 71
nt f n rt fr th pt z d C S-Q 3 tr t r viz. 3 Y / -311G( d d p l v l C ntr b t n fr nt rn l r t r ( I n bl n th tz r-G nn f r l 5 46 r b t t t d f r ntr b t n fr nt rn l r t r t r n fr n
h r b rr r r d t r n d t b b l 5 l l h ntr p nd h t
p t d t r n d d t d t r n d p nd n f th nth lp ntr p G bb En r
nd l br n t nt th t p r t r Entr p nd h t p t l l t n r p rf r d n pl t b t -Q 3 d t r n d tr nd h r n fr n r z d n bl 7
bl Id l G -ph h r d n r p rt vs p r t r 73
bl (C nt n d 4
bl 2 6 (C nt n d
h r d n pr p rt r r f rr d t t nd rd t t f n d l t 1 t S°( nd C°p( r n l l 1C 1 b S tr n b r d f r l l t n f S°( r n p r nth
2 4 Gr p l f r n th Gr p Add t v t M th d f r E t t n f h r h l pr p rt
Gr p dd t v t 3 tr htf r rd nd r n bl r t l l t n th d t
t t th r d n pr p rt f h dr rb n nd x n t d h dr rb n "; t p rt l rl f l f r ppl t n t l r r l l nd f r n d r d t b f r th t t n f th r h l pr p rt n r t n h n n r t n In th p p r t t x n tr rb n l n tr l f n rr p nd n n tr t nd ht
rb n nt r d r d l r p b n th th r d n pr p rt d t d v l p d n th t d pl th l l-h dr rb n r p n th l t r t r h f rt n r p r l t d n th bl 7 l n th t nd rd h dr rb n r p d 6
bl 2 Gr p h r h l l
tr n b r ( t n nt nt (S =S nt - ln
2 C n l n
h r d n pr p rt (Af ° 9 S° 9 5 nd Cp(T), (5 T < 5 K f r n tr rb n l n tr l f n nd rr p nd n n tr t r r p rt d St nd rd nth lp
f f r t n Af ° 9 r l l t d n d n t f n t n l th r nd d r t n h nth lp f f r t n f t l n tr t r f nd t b -1 l l
r t bl (l r nth lp th n th rr p nd n n tr h l Af ° 9 f n tr t n
3 l l r t bl th n th rr p nd n n tr t h Af ° 9 f v n l n tr t
3 l l r t bl th n th rr p nd n n tr h tr n nf r t n r p t v t C- - - d h dr l n l n pr p n n tr t v n l n tr t nd t l n tr t
r r t bl th n rr p nd n r Enth lp f f r t n ntr p S°(
nd h t p t C° p( v l r r p rt d l n th b nd n r nd
rr p nd n th r h l pr p rt f r r d l rr p nd n t l f h dr n t fr th rb n t h b nd d t n n r n ll p r
b rv d t n r fr 5 t l l t t n l b rr r p t nt l r r p rt d f r nt rn l r t r nd h nd r d nt rn l r t r ntr b t n f r Af ° 9 9 S° 9 nd C p(
r l l t d Gr p f r n r p dd t v t r d v l p d A E I A
COM A ISO E MOC EMIS Y A A
bl A1 1 p r th nth lp ntr p nd h t p t d t fr th t d f r n tr pr p n n tr pr p n nd n tr th l pr p n th rr p nd n d t fr A h r ft nd Gr d°
I — h t d A-G A h r ft nd Gr n f r n 9
7 A E I
I A IO EQUE CIES A O IMI E GEOME Y O I OA KA ES A KY I I E A EI A ICA S
bl 1 1 C l l t d t C S-Q 3 p t viz. 3 Y / -311G( d d p v l br t n r n
79 80
bl (Continued) 1
bl 1 G tr r t r f tr -n- r p n C 3C C O (cccno2) Opt z d t C S-Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r cccno2: 77 7 9 nd 5 5
bl 1 3 G tr r t r f tr t n-pr p n C 3C C O O (cccono) Opt z d t C S-Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r cccono: 1 95 1115 5 nd 1 9 8
bl 4 G tr r t r f tr - - r p n C 3C ( O C 3 ( (n 2 Opt z d t C S-Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r (n 2 : 351 9 7 75 nd 71 9
bl 1 5 Geometry Parameters of Nitrite-iso-propane CH 3CH(ONO)CH 3 (cc(ono)c) Optimized at CBS-QB3 Composite, viz. B3LYP/6-311G(2d,d,p) Level
Moments of Inertia (amu unit) for cc(ono)c: 242.06, 861.77 and 1015.70 5
bl 1 G tr r t r f tr t rt r b t n C 3C(C 3 ( O ( ( n Opt z d t C S-Q 3 C p t v z. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r ( 2 n 2: 535 3 7 5 51 nd 59 1 86
Table B1.7 Geometry Parameters of Nitrite tertiary butane CH3C(CH3)2(ONO) (cc(c2)ono) Optimized at CBS-QB3 Composite, viz. B3LYP/6-311G(2d,d,p) Level
Moments of Inertia (amu unit) for cc(c2)ono: 412.35, 1052.39 and 1060.89 7
bl 1 G tr r t r f C C C O (cjccno2) Opt z d t C S-Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r cjccno2: 5 97 731 5 nd 7 9
bl 1 9 G tr r t r f C 3C C O ( j n 2 Opt z d t C S-Q 3 C p t v z. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r j n 2: 1 5 79 9 nd 919 7 8
bl 0 G tr r t r f C 3C C O ( jn 2 Opt z d t C S-Q 3 C p t v z. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r jn 2: 5 7 nd 9
bl 1 11 G tr r t r f C C C O O (cjccono) Opt z d t C S- Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r cjccono: 137 15 1 75 5 nd 11 9 91
bl 1 1 Geometry Parameters of CH3 CHCH2ONO (ccjcono) Optimized at CBS- QB3 Composite, v z. B3LYP/6-311G(2d,d,p) Level
Moments of Inertia (amu unit) for ccjcono: 155.99, 1030.21 and 1076.89 2
bl Geometry Parameters of CH2CH (NO2)CH3 (cjc(no2)c) Optimized at CBS- QB3 Composite, viz. B3LYP/6-311G(2d,d,p) Level
Moments of Inertia (amu unit) for cjc(no2)c: 341.80, 579.54 and 701.28 93
bl 1 1 G tr r t r f C 3C( O C 3 (ccj(no2)c) Opt z d t C S- Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r ccj(no2)c: 3 7 3 nd 1 5 9
bl 1 15 G tr r t r f C C (O O C 3 (cjc(ono)c) Opt z d t C S- Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r cjc(ono)c: 1 nd 95
bl 1 1 G tr r t r f C C(C 3 ( O ( j ( 2 n 2 Opt z d t C S-Q 3 C p t v z. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r j ( 2 n 2: 5 7 1 nd 5 9
bl 1 17 G tr r t r f C C(C 3 (O O (cjc(c2)ono) Opt z d t C S-Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r cjc(c2)ono: 399 7 1 9 nd 1 7 A E I C
I A IO EQUE CIES A O IMI E GEOME Y O I OCA O Y S I OO E I S CO ES O I G I I ES A EI CA O CE E E A ICA S
bl C 1 C l l t d t C S-Q 3 p t viz. 3 Y / -311G( d d p v l br t n r n
97 8
bl C2 (continued) 99
bl C G tr r t r f tr t n C 3C(=O C O ( ( n 2 Opt z d t C S-Q 3 C p t v z. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r ( n 2: 35 1 1 1 9 nd 1 9 100
Table C 3 Geometry Parameters of 2 Propanone nitrite CH 3C(=O)CH ONO (cc(=o)ono) Optimized at CBS-QB3 Composite, viz. B3LYP/6-311G(2d,d,p) Level
Moments of Inertia (amu unit) for cc(=o)ono: 254.56, 1311.02 and 1483.46 1 1
bl C G tr r t r f tr th l n C =C O (c=cno2) Opt z d t C S-Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r c=cno2: 15 31 3 3 nd 53 3 1
bl C 5 G tr r t r f n l n tr t C =C O O ( n Opt z d t C S-Q 3 C p t v z. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r n : 5 93 9 nd 73 15 1 3
bl C Geometry Parameters of Nitroacetate CH3C(=0)NO2 ( ( n 2 Optimized at CBS-QB3 Composite, viz. B3LYP/6-311G(2d,d,p) Level
Moments of Inertia (amu unit) for ( n 2: 313.64, 488.55 and 791.17 1
bl C 7 Geometry Parameters of Acetyl nitrite CH3C(=0)NO2 ( ( n Optimized at CBS-QB3 Composite, v z. B3LYP/6-311G(2d,d,p) Level
Moments of Inertia (amu unit) for ( n : 183.21, 809.92 and 981.98 1 5
bl C G tr r t r f C C(=O C O ( j ( n 2 Opt z d t C S-Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r j ( n 2: 3 1 1 9 31 nd 11 5 1 1
bl C 9 G tr r t r f C 3C(=O C O (cc(=o)cjno2) Opt z d t C S-Q 3 C p t v z. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r cjc(=o)cno2: 3 91 97 55 nd 1 39 95 1 7
bl C 1 G tr r t r f C C(=O C O O ( j ( n Opt z d t C S-Q 3 C p t v z. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r j ( n : 3 5 1 35 9 nd 1 1
bl C 11 G tr r t r f C =C O ( j n 2 Opt z d t C S-Q 3 C p t v z. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r j n 2: 1 7 373 7 nd 5 1 9
bl C 1 Geometry Parameters of CH2=CNO2 ( jn 2 Optimized at CBS-QB3 Composite, v z. B3LYP/6-311G(2d,d,p) Level
Moments of Inertia (amu unit) for jn 2: 140.09, 394.99 and 535.09 11
bl C 13 G tr r t r f C =C O O ( j n Opt z d t C S-Q 3 C p t v z. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r j n : 3 19 71 5 nd 7 7 77 111
bl C 1 Geometry Parameters of CH2C(=O)NO2 ( j ( n 2 Optimized at CBS- QB3 Composite, v z. B3LYP/6-311G(2d,d,p) Level
Moments of Inertia (amu unit) for j ( n 2: 296.03, 469.70 and 765.73 11
bl C 15 G tr r t r f C C(=O O O (cjc(=o)ono) Opt z d t C S- Q 3 C p t viz. 3 Y / -311G( d d p v l
M nt f In rt ( n t f r cjc(=o)ono: 17 7 5 nd 9 9 E E E CES
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35 A O nt C t r I Gö lp Y n Ab n t nt h l pr d t n f nth lp f f r t n h t p t nd ntr p f -ph n r t p nd Combustion and Flame 7 151 - 73 3 - - h n - Y n n t f n t n l t d f th h t f f r t n f v r l n tr t r p nd Journal of Molecular Structure: THEOCHEM 7 15 151-15 37 G n 3 v n 1 r h M ; r G W ; S hl l ; S r G E ; bb M A ; Ch n ; M nt r A r ; r v n ; K d n K ; r nt C ; M ll M ; I n r S S ; ; r n ; M nn ; C M ; S l n G ; t r n G A ; t j ; d M ; Eh r M ; t K ; d ; ; I h d M ; j ; nd Y ; K t O ; ; Kl n M ; ; Kn x E ; r t h n ; Cr ; Ad C ; r ll ; G p rt ; Str t nn E ; Y z v O ; A t n A ; C ; ll C ; O ht r W ; A l Y ; M r K ; th G A ; S lv d r ; nn nb r ; rz G ; ppr h S ; n l A ; Str n M C ; r O ; M l K ; b A ; h v h r K ; r n ; Ort z ; C Q ; b l A G ; Cl ff rd S ; C l ; St f n v ; G ; h n A ; rz ; K r I ; M rt n ; x ; K th ; Al- h M A ; n C Y ; n r A ; Ch ll b M ; G ll M W ; hn n ; Ch n W ; W n M W ; G nz l z C ; pl A G n In tt b r h A 3 3 W hr d S hl r nd A pl Ab In t M l l r Orb t l h r ( hn W l S n Y r 19 39 IS Ch tr W bb http://webbook.nist.gov/chemistry/ A M El- h W zz ll M S M v rr G l nd C rr n J. Phys. Chem. A 11 13 1 -13 3 1 A S tt nd d Phys. Chem. 199 1 1 5 Sh n C h rt t n p rt nt f Ch l En n r n r In t t t f hn l 3 S W n n Thermochemical Kinetics; W l -Int r n Y r 197 l nd n J. Am. Chem. Soc. 19 1 5 ( tz r K S Chem. Phys. 1937 5, 9 (b Ibid. 19 14, 39 tz r K S.; G nn W J. Chem. Phys. 19 10, 7 K n tz C ; n M J. Am. Chem. Soc. 7 129(9), 5 1- 5 h ; zz ll W ; K rd M J. Phys. Chem. A., 7; 111(28); 3 1- 377 6
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