SUPPLEMENTARY INFORMATION
THERMOCHEMICAL PROPERTIES OF
4-N,N-DIALKYLAMINO-7-NITROBENZOFURAZAN DERIVATIVES
(ALKYL = METHYL, ETHYL)
Ana Filipa L. O. M. Santos,  Ana L. R. Silva,  Otília D. F. Santiago,  Jorge M. Gonçalves, **
Siddharth Pandey,* W. E Acree Jr., Maria D. M. C. Ribeiro da Silva
Centro
de Investigação em Química, Department of Chemistry and Biochemistry,
Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007, Portugal
Department
of Chemistry, University of North Texas, Denton, Texas 76203 (USA)
*Present address
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, 110016
(India)
** Corresponding author:
e-mail address: jmgoncalves@fc.up.pt;
fax: +351 220 402 659; phone: + 351 220 402 534
This supplementary information includes the data and the details of all the combustion calorimetry
experiments for the 4-N,N-dimethylamino-7-nitrobenzofurazan and 4-N,N-diethylamino-7-nitrobenzofurazan, the
computed G3(MP2)//B3LYP enthalpies for the compounds studied, auxiliary molecules used in the
working reactions, as well as the literature values of  f H mo (g) for the auxiliary molecules, and a
scheme for the estimation of the gas-phase enthalpy of formation, at T = 298.15 K, for the N,Ndiethyl-4-nitrobenzenamine.
TABLE S1
Standard (pº = 0.1 MPa) mass energy of combustion of 4-N,N-dimethylamino-7-nitrobenzofurazan, at T = 298.15 K.
m (CO2, total) /g
1
1.74819
2
1.63039
3
1.61561
4
1.26931
5
1.61235
6
1.58986
7
1.65685
8
1.56299
9
---
10
1.51307
m (cpd) /g
0.63972
0.57978
0.58546
0.36548
0.39306
0.39691
0.40105
0.35046
0.40517
0.18827
m (fuse) /g
0.00428
0.00436
0.00430
0.00453
0.00458
0.00457
0.00458
0.00431
0.00438
0.00455
m (n-hex.) /g
0.21203
0.20671
0.19890
0.20706
0.30234
0.29302
0.31231
0.30978
0.29714
0.38181
ΔTad /K
1.53495
1.43465
1.41938
1.13917
1.46692
1.44328
1.50796
1.43027
1.47255
1.42690
f /(J·K ─1)
16.14
16.60
16.56
16.25
16.79
16.60
16.71
16.54
16.68
16.88
m (H2O) /g
0.0
-0.5
-1.4
-1.7
-1.2
-0.6
-1.4
-0.1
-13.0
-9.7
U (IBP) /J
23881.78
22318.87
22075.84
17715.68
22816.85
22452.48
23453.85
22252.98
22831.57
22143.73
U (HNO3) /J
75.84
41.51
42.25
28.68
33.13
47.84
48.52
41.74
42.06
22.31
U (ign.) /J
1.19
1.14
1.20
1.19
1.19
1.19
1.20
1.19
1.19
1.18
UΣ /J
15.46
14.53
14.54
9.81
11.73
11.51
11.93
10.73
11.66
8.29
ΔU (n-hex.) /J
69.51
70.81
69.83
73.57
74.38
74.22
74.38
69.99
71.13
73.89
ΔU (fuse) /J
10000.37
9749.14
9380.81
9765.67
14259.86
13820.22
14729.73
14610.73
14014.31
18007.94
−Δcuº /(J·g─1)
21447.82
21461.38
21467.58
21445.63
21466.82
21412.13
21417.01
21456.91
21453.74
21412.33
< Δcuº (compound) > = − (21444.14 ± 7.00) J·g─1
m(CO2, total) is the total mass of CO2 recovered in the experiment; m(cpd) is the mass of compound burnt in each experiment; m(fuse) is the mass of fuse (cotton) used in each experiment; m(n-hex.) is the mass of nhexadecane burnt in the experiment; ∆Tad is the corrected temperature rise; f is the energy equivalent of contents in the final state; ∆m(H2O) is the deviation of the mass of water added to the calorimeter from 2900.0 g;
∆U(IBP) is the energy change for the isothermal combustion reaction under actual bomb conditions and includes ∆U(ign); ∆U(HNO3) is the energy correction for the nitric acid formation; ∆U(ign) is the electrical
energy for ignition; ∆U is the standard state correction; ∆U(n-hex.) is the energy of combustion of n-hexadecane; ∆U(fuse) is the energy of combustion of the fuse (cotton); ∆cuº is the standard massic energy of
combustion.
TABLE S2
Standard (pº = 0.1 MPa) mass energy of combustion of 4-N,N-diethylamino-7-nitrobenzofurazan, at T = 298.15 K.
1
2
3
4
5
6
7
m (CO2, total) /g
1.69248
1.69271
1.67678
1.75108
1.63728
1.67225
1.66772
m (cpd) /g
0.39012
0.38936
0.39527
0.39300
0.44253
0.39890
0.39985
m (fuse) /g
0.00460
0.00453
0.00433
0.00440
0.00454
0.00483
0.00479
m (n-hex.) /g
0.30815
0.30872
0.30016
0.32537
0.25903
0.29627
0.29426
ΔTad /K
1.55618
1.55712
1.54025
1.61366
1.49094
1.53573
1.53316
16.83
16.86
16.88
16.95
16.73
16.48
16.47
m (H2O) /g
-1.6
0.0
-3.7
-0.8
-3.2
-2.5
-5.7
U (IBP) /J
24203.94
24229.03
23942.72
25103.55
23179.10
23879.56
23819.05
U (HNO3) /J
45.33
42.08
36.54
43.20
41.43
47.07
47.41
U (ign.) /J
1.19
1.18
1.18
1.19
1.16
1.17
1.19
UΣ /J
11.21
11.21
11.26
11.56
11.62
11.13
11.12
ΔU (fuse) /J
74.70
73.57
70.32
71.46
73.73
78.44
77.79
14533.76
14560.67
14156.92
15345.99
12217.01
13973.22
13878.78
24448.25
24502.57
24455.44
24504.20
24482.29
24488.67
24516.09
f /(J·K ─1)
ΔU (n-hex.) /J
─1
−Δcuº /(J·g )
─1
< Δcuº (compound) > = − ( 24485.36 ± 9.62) J·g
m(CO2, total) is the total mass of CO2 recovered in the experiment; m(cpd) is the mass of compound burnt in each experiment; m(fuse) is the mass of fuse
(cotton) used in each experiment; m(n-hex.) is the mass of n-hexadecane burnt in the experiment; ∆Tad is the corrected temperature rise; f is the energy
equivalent of contents in the final state; ∆m(H2O) is the deviation of the mass of water added to the calorimeter from 2900.0 g; ∆U(IBP) is the energy change for
the isothermal combustion reaction under actual bomb conditions and includes ∆U(ign); ∆U(HNO3) is the energy correction for the nitric acid formation;
∆U(ign) is the electrical energy for ignition; ∆U is the standard state correction; ∆U(n-hex.) is the energy of combustion of n-hexadecane; ∆U(fuse) is the
energy of combustion of the fuse (cotton); ∆cuº is the standard massic energy of combustion.
TABLE S3
G3(MP2)//B3LYP computed enthalpies for the 4-N,N-dimethylamino-7-nitrobenzofurazan, 4-N,Ndiethylamino-7-nitrobenzofurazan and for the auxiliary molecules used in the gas-phase working
reactions and standard molar enthalpies of formation, at T = 298.15 K, taken from the literature.
computed G3(MP2)//B3LYP
enthalpies a
4-N,N-dimethylamino-7-nitrobenzofurazan
−753.108828
4-N,N-diethylamino-7-nitrobenzofurazan
−831.582486
N,N-dimethyl-4-nitrobenzenamine
−569.872078
N,N-diethyl-4-nitrobenzenamine
−648.346939
N,N-dimethylbenzenamine
−365.569406
N,N-diethylbenzenamine
−444.043302
benzofurazan
a
−415.078855
4-nitrobenzofurazan
−619.366283
2,1,3-benzothiadiazole
−737.775889
4-nitro-2,1,3-benzothiadiazole
−942.063789
naphthalene
−385.223727
nitronaphthalene
−589.516753
quinoline
−401.263696
8-nitroquinoline
−605.552321
benzene
−231.835149
 f H mo g 
kJ  mol 1
----62.8 ± 2.6 b
24.4 ± 8.7 c
100.5 ± 3.4 d
62.1 ± 7.6 e
300.2 ± 2.2 f
306.6 ± 6.2 g
276.6 ± 2.5 h
283.7 ± 4.9 i
150.3 ± 1.4 j
145.0 ± 1.9 k
200.5 ± 0.9 l
206.9 ± 2.6 m
82.6 ± 0.7 j
All energies are in Hartrees. (1 Hartree = 2625.5 kJ·mol -1)
W.E. Acree, S.A. Tucker, G. Pilcher, G. Toole, J. Chem. Thermodyn. 26 (1994) 85-90;
c
Estimated through the scheme presented in figure S1, in the supporting information;
d
J. Furukawa, M. Sakiyama, S. Seki, Y. Saito, K. Kusano, Bull. Chem. Soc. Jpn. 55 (1982) 3329-3330, in
NIST Chemistry Webbook, NIST Standard Reference Database Number 69; P.J. Linstrom, W.G. Mallard,
Eds.; National Institute of Standards and Technology: Gaithersburg MD, 20899,
(http://webbook.nist.gov);
e
M.A.V. Ribeiro da Silva, M.D.M.C. Ribeiro da Silva, M.F.B.M. Monteiro, M.L.A.C.N. Gomes, J.S.
Chickos, A.P. Smith, J.F. Liebman, Struct. Chem. 7 (1996) 367-373;
f
M.L.P. Leitão, G. Pilcher, W.E. Acree Jr., A.I. Zvaigzne, S.A Tucker, M.D.M.C. Ribeiro da Silva, J.
Chem. Thermodyn. 22 (1990) 923-928;
g
W.E. Acree Jr., S.G. Bott, S.A Tucker, M.D.M.C. Ribeiro da Silva, M.A.R. Matos, G. Pilcher, J. Chem.
Thermodyn. 28 (1996) 673-683;
h
M.S. Miranda, M.A.R. Matos, V.M.F. Morais, J.F. Liebman, J. Chem. Thermodyn. 50 (2012) 30-36;
i
M.D.M.C. Ribeiro da Silva, V.L.S. Freitas, M.A.A. Vieira, M.J. Sottomayor, W.E. Acree Jr., J. Chem.
Thermodyn. 49 (2012) 146-153;
j
J.B. Pedley, Thermochemical Data and Structures of Organic Compounds, vol. 1, TRC Data Series:
College Station, TX, 1994;
k
M.A.V. Ribeiro da Silva, L.M.P.F. Amaral, A.F.L.O.M. Santos, J.R.B. Gomes, J. Chem. Thermodyn. 38
(2006) 748-755;
l
W.V. Steele, D.G. Archer, R.D. Chirico, W.B. Collier, I.A. Hossenlopp, A. Nguyen, N.K. Smith, B.E.
Gammon, J. Chem. Thermodyn. 20 (1988) 1233-1264;
m
M.A.V. Ribeiro da Silva, M.A.R. Matos, L.M.P.F. Amaral, J. Chem. Thermodyn. 29 (1997) 295-303.
b
O2N
O2N
+
=
C2H5
H3C
62.8 ± 2.6
N
N
N
N
C2H5
-
CH3
C2H5
62.1 ± 7.6
C2H5
H3C
CH3
100.5 ± 3.4
FIGURE S1
Scheme for the estimation of the gas-phase enthalpy of formation, at T = 298.15 K, of N,Ndiethyl-4-nitrobenzenamine. All values are in kJmol-1.