This document discusses a study of reaction pathways in the oxidation of acrolein. It identifies intermediates, transition states, and products in the pathway using computational chemistry methods. Heat of formation energies were calculated for each species using different functionals and basis sets. An energy diagram is presented showing the energies of species in the pathway. Several reaction enthalpies are also presented in tables comparing results from different computational methods. References are provided for thermochemical data of species used in the calculations.

1. The Study of One of the Important Pathway on
the Acrolein Oxidation
Chemistry and Environmental Science Department, New Jersey Institute of Technology
Jinhong Tan
Advisor: Joseph W. Bozzelli
6/18/2015

2. Abstract:
In thisreportwe studied areactionpathwayfromradical qjcdccdo to intermediates,transitionstates
and final products.Firstlywe identifiedthe intermediatesandproductsinthe reactionpathway.Then
we use work reactionstocalculate the heatof formationenergyof eachof the speciesinthe pathway
by usingM062x/6-31+G(d,p) and B3LYP/6-31+G(d,p) methodsandbasisset. Lastlywe estimatedthe
transitionstate structure andbuildthe Gaussianinputfile tocalculate the transitionstate energy.
Introduction:
Thispathwaywe studiedisanimportantpathwayon the researchof molecule 2-Propenal oxidation.2-
Propenal oracroleinisthe simplestunsaturatedaldehyde.It’susuallycreatedbyglycerol whenburning
fat or cigarette smoke.Acroleinistoxicandisa strongirritantfor the skin,eyesandnasal passages,it’s
alsothe risk of cancer specie.We studiedone of the importantpathwayof the acroleinoxidation.
We usedbothM062x and B3lYP methodstocalculate eachof the moleculesorradicalsinthe work
reaction,apply 6-31+G(d,p) basissetfor bothmethods. ForeachGaussianinputfile created,we firstly
use Chem95 programsto buildthe molecule structure,thenuse Mopacprogram to calculate (use pm3
precise aigoutcommend) togetthe Gaussianinputfile.Foreachof the Gaussiancalculationof the
species,we calculate all of the rotational energy inthe molecule togetthe most optimizedstructure.
Thenwe use it to calcualte the heatof formationenergy.
The transitionstate structure wasestimatedunderthe guidance of professorBozzelli.We use M062x/6-
31+G(d,p) opt=(calcfc,ts,oeigen)freqscf=qcasthe commend line tocalculate the transitionstate
energy.
Afteridentifythe heatof formationenergyof all the specie (transitionstate use relative energymethod
to identify) inthe pathway,we createdthe energydiagramof thispathway.

3. Result andDiscussion:
Figure 1 showsthe energydiagramof thispathwaycalculatedbyM062x method. Table 1 showsthe
reference dataof speciesinthe workreactions.Table 2is the workreactionscalculated. The mostof the
heatof formationenergycalculatedbytwomethodsinthe workreactionmatcheswell.Thismaydue to
the careful buildingof the inputfileandrotational energy calculationof eachmolecule togetthe most
optimizedstructure. While thereare some datacalculatedbytwomethodstill have bigdifference.For
example the radical ojycoccdo(Table 2) twocalculatedaverage energyare -74.4kcal/mol and -
68.35kcal/mol byB3LYP and M062x respectively.We have checkedthe outputstructure calculatedby
bothmethods.We foundthatthe outputstructure byB3LYP was similarwiththe inputstructure,while
for M062x Outputstructure it has a bigdifference withthe inputstructure.We cannot figure outthe
reason.
Additionally,some of the workreactions we chosen canbe betterto contribute tothe more accurate
result. the furtherstudymaybe the more accurate work reactionchose andhigherlevel method
calculation.
Figure 1. Energy Diagram of this studied pathway.

4. Species ΔfH298
kcal/mol
Reference
c ch4 -17.83 1
cc ch3ch3 -20.04 1
ccdo Ch3ch2cho -39.72 4
cccdo ch3ch2ch=o -45.09 2
ccccdo ch3ch2ch2ch=o -49.27 9
cdc ch2=ch2 12.54 1
cjdc ●ch=ch2 71.2 4
cdcc ch2=chch3 4.89 1
cjdcc ●ch=chch3 63.66 3
ycoc Ych2och2 -12.57 14
ycoo Ych2o2 1.2 10
coh ch3oh -48.04 5
ccoh Ch3ch2oh -56.12 6
odcoc o=choch3 -85 7
odcocc O=choch2ch3 -92.83 8
cjcdo ●ch2ch=o 4.4 4
ccjcdo ch3c●hch=o -5.7 4
hocdc ch2=choh -30.59 11
odc ch2=o -27.7 12
odcdc o=c=ch2 -20.89 13
Table 1. Heat of formation energy of reference species used in the work reactions.
Reaction Enthalpies ΔfH298 kcal/mol
Work reaction B3LYP M062X B3LYP M062X
1 ycooccdo+ c = ycoo + cccdo 7.18 7.64 -33.34 -33.77
2 ycooccdo+ cc = ycoo + ccccdo 5.57 5.13 -33.60 -33.16
Average -33.47 -33.47
3 ycoocjcdo+cdc=ycooccdo+cjdc 22.48 19.84 2.71 5.35
4 ycoocjcdo+cdcc=ycooccdo+cjdcc 23.16 20.65 2.14 4.65
Average 2.43 5
5 oycoccdo+c=oycoc+ccdo 3.29 3.55 -82.70 -82.96
6 oycoccdo+cc=oycoc+cccdo 2.21 1.89 -84.87 -84.55
Average -83.79 -83.76
7 ojycoccdo+cdc=oycoccdo+cjdc 49.03 42.9 -74.12 -67.99

5. 8 ojycoccdo+cdcc=oycoccdo+cjdcc 49.70 43.72 -74.68 -68.70
Average -74.4 -68.35
9 odcoccdo+c=ccdo+odcoc 0.08 0.77 -106.97 -107.66
10 odcoccdo+cc=ccdo+odcocc -5.27 -5.2 -107.24 -107.32
Average -107.11 -107.49
11 odcocjcdo+cdc=odcoccdo+cjdc 26.35 24.20 -75.18 -73.03
12 odcocjcdo+cdcc=odcoccdo+cjdcc 27.03 25.02 -75.75 -73.74
Average -75.47 -73.39
13 qcdccdo+cc=qcdc+cccdo 7.64 6.18 -43.00 -41.54
14 qcdccdo+c=qcdc+ccdo 8.72 7.84 -40.83 -39.95
Average -41.92 -40.75
15 qjcdccdo+cdc=qcdccdo+cjdc 24.59 24.01 -6.68 -6.10
16 qjcdccdo+cdcc=qcdccdo+cjdcc 25.26 24.83 -7.24 -6.81
Average -6.96 -6.46
17 ocdccdo+cc=hocdc+cccdo 8.42 6.80 -64.15 -62.53
18 ocdccdo+c=hocdc+ccdo 9.50 8.45 -61.98 -60.93
Average -63.07 -61.73
19 ojcdccdo+cdc=ocdccdo+cjdc 26.29 25.06 -29.36 -28.13
20 ojcdccdo+cdcc=ocdccdo+cjdcc 26.96 25.88 -29.92 -28.84
Average -29.64 -28.49
21 cdccdo + c = cdc + ccdo 7.03 6.47 -16.26 -15.7
22 cdccdo + cc = cdcc + ccdo 1.71 0.96 -16.38 -15.63
Average -16.32 -15.67
23 odcj+cdc=cjdc+odc 21.71 21.36 9.25 9.6
24 odcj+cdcc=cjdcc+odc 22.38 22.17 8.69 8.90
Average 8.97 9.25
25 qcdccjdo+ cdc = qcdccdo + cjdc 21.03 20.35 -3.12 -2.43
26 qcdccjdo+ cdcc = qcdccdo + cjdcc 21.71 21.16 -3.69 -3.14
Average -3.41 -2.79
27 odcocdcdo+c = odcoc + odcdc -13.28 -14.24 -80.40 -79.44
28 odcocdcdo+cc = odcocc + odcdc -7.94 -8.27 -80.12 -79.79
Average -80.26 -79.62
Work ReactionM062x Reaction Enthalpies ΔfH298 kcal/mol
1 oycoc + c = ycoc + coh 14.68 -57.46
2 oycoc + cc = ycoc + ccho 8.92 -57.57
Average -57.52
Table 2. Work reactions for different molecules and radicals.

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