1462
J. Chem. Eng. Data 2010, 55, 1462–1465
Density Functional Theory Calculation on Polychlorinated Anthraquinones: Their Gas Phase Thermodynamic Function and Implication of the Cl Substituted Position. Chen Wang, Hong X. Liu, Zhe Y. Fang, and Zun Y. Wang,* J.
Chem. Eng. Data DOI: 10.021/je9003564. Because the molecular symmetry was missed in the calculation process, the values of je-2009-003564 have been corrected considering molecular symmetry. All molecules were calculated at the B3LYP/6-31G* level, and the vibrational scaling factor is 0.96. Eq 13 should be replaced by:
Sθ/J · mol-1 · K-1 ) 448.90 + 29.18N R2 ) 0.980 SE ) 6.40 F ) 3657.873 (13) Equations 14 and 15 should be replaced by:
∆fHθ/kJ · mol-1 ) -118.218 + 1.424NR - 26.971Nβ + 14.712No + 3.212Nm + 4.173Np R ) 0.988 2
SE ) 2.352
F ) 1139.471 (14)
∆fGθ/kJ · mol-1 ) -8.886 + 5.733NR - 21.994Nβ + 15.329No + 3.321Nm + 5.549Np R ) 0.990 2
SE ) 2.398
F ) 1352.333 (15)
JE100011N 10.1021/je100011n Published on Web 02/16/2010
Journal of Chemical & Engineering Data, Vol. 55, No. 3, 2010 1463 Table 5. Thermodynamic Parameters of PCAQNs Computed at B3LYP/6-31G* Level and NPCSa Sθ molecule
group
∆fHθ
∆fGθ
symmetry J · mol-1 · number K-1 kJ · mol-1 kJ · mol-1 kJ · mol-1 constant 10-3 T 105 T-1 107 T-2 4
430.53
-119.40
-6.26
mono-CAQN 1 C1 2 Cs
1 1
476.54 473.08
-117.93 -146.53
-4.31 -31.87
di-CAQN 1,2 1,3 1,4 1,5 1,6 1,7 1,8 2,3 2,6 2,7
C1 C1 Cs C2 C1 C1 Cs C2V C2h C2V
1 1 1 2 1 1 1 2 2 2
507.44 507.10 514.88 517.75 507.32 507.20 505.21 496.03 497.50 497.60
-129.25 -142.24 -108.29 -116.80 -144.56 -144.71 -114.53 -160.75 -173.07 -172.94
tri-CAQN 1,2,3 1,2,4 1,2,5 1,2,6 1,2,7 1,2,8 1,3,5 1,3,6 1,3,7 1,3,8 1,4,5 1,4,6 2,3,5 2,3,6
C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1 C1
1 1 1 1 1 1 1 1 1 1 1 1 1 1
537.04 540.64 541.94 537.84 538.48 533.09 544.98 537.80 537.76 535.83 535.25 546.90 536.06 532.59
TCAQN 1,2,3,4 1,2,3,5 1,2,3,6 1,2,3,7 1,2,3,8 1,2,4,5 1,2,4,6 1,2,4,7 1,2,4,8 1,2,5,6 1,2,5,7 1,2,5,8 1,2,6,7 1,2,6,8 1,2,7,8 1,3,5,7 1,3,5,8 1,3,6,7 1,3,6,8 1,4,5,8 1,4,6,7 2,3,6,7
Cs C1 C1 C1 C1 C1 C1 C1 C1 C2 C1 C1 C1 C1 Cs C2 C1 C1 Cs C2V Cs D2h
1 1 1 1 1 1 1 1 1 2 1 1 1 1 1 2 1 1 1 2 1 4
penta-CAQN 1,2,3,4,5 C1 1,2,3,4,6 C1 1,2,3,5,6 C1 1,2,3,5,7 C1 1,2,3,5,8 C1 1,2,3,6,7 C1 1,2,3,6,8 C1 1,2,3,7,8 C1 1,2,4,5,6 C1 1,2,4,5,7 C1 1,2,4,5,8 C1 1,2,4,6,7 C1 1,2,4,6,8 C1 1,2,4,7,8 C1 hexa-CAQN 1,2,3,4,5,6 C1 1,2,3,4,5,7 C1 1,2,3,4,5,8 Cs
AQN
D2h
Cp,m/J · mol-1 · K-1
∆fGθR
R2
SE
NR Nβ No Nm Np N1,8
565.63
43.76
-1.60
1.47
1.000 1.34
0
0
0
0
0
0
27.56 0.00
578.77 578.09
36.17 36.55
-1.57 -1.57
1.42 1.42
1.000 1.28 1.000 1.29
1 0
0 1
0 0
0 0
0 0
0 0
-10.63 -23.52 8.11 -1.26 -25.90 -26.02 4.75 -38.73 -51.49 -51.39
40.86 27.96 59.59 50.23 25.58 25.46 56.24 12.75 0.00 0.10
591.84 591.39 591.78 591.84 591.18 591.28 591.44 590.48 590.49 590.55
28.76 28.93 28.65 28.65 29.00 28.94 28.84 29.61 29.39 29.34
-1.54 -1.53 -1.53 -1.53 -1.53 -1.53 -1.53 -1.53 -1.53 -1.53
1.37 1.37 1.36 1.36 1.36 1.36 1.36 1.37 1.36 1.36
1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000
1.23 1.23 1.23 1.23 1.24 1.23 1.23 1.25 1.24 1.24
1 1 2 2 1 1 2 0 0 0
1 1 0 0 1 1 0 2 2 2
1 0 0 0 0 0 0 1 0 0
0 1 0 0 0 0 0 0 0 0
0 0 1 0 0 0 0 0 0 0
0 0 0 0 0 0 1 0 0 0
-140.20 -116.93 -128.05 -155.40 -155.42 -126.27 -140.87 -168.13 -168.42 -138.27 -109.56 -134.65 -158.39 -186.54
-16.20 5.99 -5.52 -31.64 -31.86 -1.09 -19.24 -44.36 -44.63 -13.92 14.97 -13.60 -34.10 -61.22
45.01 67.21 55.70 29.58 29.36 60.13 41.97 16.86 16.59 47.30 76.19 47.62 27.12 0.00
604.81 604.71 604.78 604.21 604.39 604.24 604.59 603.94 604.04 604.08 604.02 604.33 603.65 603.01
21.51 21.37 21.30 21.63 21.52 21.61 21.35 21.69 21.62 21.62 21.58 21.40 22.03 22.39
-1.51 -1.50 -1.50 -1.50 -1.50 -1.50 -1.50 -1.50 -1.50 -1.50 -1.49 -1.50 -1.50 -1.50
1.32 1.31 1.31 1.31 1.31 1.31 1.31 1.31 1.31 1.31 1.30 1.31 1.31 1.31
1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000
1.19 1.18 1.18 1.19 1.19 1.18 1.18 1.19 1.18 1.18 1.18 1.18 1.20 1.20
1 2 2 1 1 2 2 1 1 2 3 2 1 0
2 1 1 2 2 1 1 2 2 1 0 1 2 3
2 1 1 1 1 1 0 0 0 0 0 0 1 1
1 1 0 0 0 0 1 1 1 1 0 0 0 0
0 1 0 0 0 0 0 0 0 0 1 1 0 0
0 0 0 0 0 1 0 0 0 1 1 0 0 0
566.58 585.04 567.06 566.65 561.96 564.33 572.13 572.17 564.05 563.81 582.41 564.65 566.88 563.75 561.89 569.82 566.85 566.30 566.85 559.11 579.53 549.97
-110.07 -138.77 -165.80 -166.03 -136.74 -118.27 -142.72 -142.61 -118.85 -139.00 -151.51 -121.28 -168.81 -149.46 -137.65 -164.31 -132.45 -181.67 -161.16 -107.25 -148.09 -199.93
19.32 -14.88 -36.55 -36.66 -5.97 11.80 -14.98 -14.88 11.30 -8.78 -26.84 8.69 -39.50 -19.22 -6.86 -35.88 -3.14 -52.19 -31.84 24.38 -22.56 -65.58
84.91 50.71 29.04 28.93 59.62 77.38 50.60 50.70 76.88 56.80 38.74 74.27 26.08 46.36 58.72 29.70 62.45 13.39 33.74 89.96 43.03 0.00
618.85 617.96 617.37 617.33 617.23 616.97 617.38 617.33 616.94 617.62 617.61 616.67 616.84 617.02 617.10 617.24 616.64 616.35 616.70 616.07 616.78 615.50
13.53 13.97 14.27 14.29 14.36 14.32 14.08 14.10 14.35 14.07 13.99 14.46 14.56 14.29 14.34 14.12 14.37 14.76 14.40 14.66 14.46 15.40
-1.47 -1.47 -1.47 -1.47 -1.47 -1.46 -1.47 -1.46 -1.46 -1.47 -1.47 -1.46 -1.47 -1.46 -1.47 -1.47 -1.46 -1.46 -1.46 -1.45 -1.46 -1.47
1.27 1.27 1.27 1.27 1.26 1.26 1.26 1.26 1.26 1.26 1.26 1.25 1.26 1.26 1.26 1.26 1.25 1.26 1.26 1.25 1.26 1.26
1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000
1.13 1.14 1.15 1.14 1.14 1.13 1.13 1.13 1.13 1.13 1.13 1.13 1.15 1.14 1.14 1.13 1.13 1.15 1.14 1.13 1.14 1.16
2 2 1 1 2 3 2 2 3 2 2 3 1 2 2 2 3 1 2 4 2 0
2 2 3 3 2 1 2 2 1 2 2 1 3 2 2 2 1 3 2 0 2 4
3 2 2 2 2 1 1 1 1 2 1 1 2 1 2 0 0 1 0 0 1 2
2 1 1 1 1 1 1 1 1 0 1 0 0 1 0 2 1 1 2 0 0 0
1 0 0 0 0 1 1 1 1 0 0 1 0 0 0 0 1 0 0 2 1 0
0 0 0 0 1 1 0 0 1 0 0 1 0 1 1 0 1 0 1 2 0 0
1 1 1 1 1 1 1 1 1 1 1 1 1 1
591.92 597.28 601.51 608.75 592.81 595.68 592.97 590.29 593.86 595.15 593.45 601.87 594.94 592.84
-112.67 -135.49 -149.35 -161.89 -131.48 -179.06 -159.32 -147.84 -129.78 -140.92 -116.78 -155.72 -141.49 -130.54
23.38 -1.04 -16.17 -30.86 4.30 -44.14 -23.58 -11.31 5.68 -5.84 18.81 -22.64 -6.35 5.22
67.52 43.10 27.97 13.28 48.44 0.00 20.56 32.83 49.82 38.31 62.95 21.50 37.79 49.36
630.91 631.45 630.90 630.72 629.79 629.89 629.93 630.13 629.80 629.56 629.01 629.91 629.62 629.76
6.61 6.26 6.65 6.68 7.13 7.28 7.11 7.07 7.08 7.14 7.40 7.08 7.09 7.12
-1.44 -1.44 -1.44 -1.44 -1.43 -1.44 -1.43 -1.44 -1.43 -1.43 -1.42 -1.43 -1.43 -1.43
1.22 1.22 1.22 1.22 1.21 1.22 1.22 1.22 1.21 1.21 1.20 1.21 1.21 1.21
1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000
1.08 1.08 1.09 1.09 1.09 1.10 1.09 1.10 1.09 1.08 1.08 1.09 1.08 1.09
3 2 2 2 3 1 2 2 3 3 4 2 3 3
2 3 3 3 2 4 3 3 2 2 1 3 2 2
3 3 3 2 2 3 2 3 2 1 1 2 1 2
2 2 1 2 1 1 2 1 1 2 1 1 2 1
1 1 0 0 1 0 0 0 1 1 2 1 1 1
1 0 0 0 1 0 1 1 1 1 2 0 1 1
1 1 1
620.53 622.80 620.63
-124.24 -134.93 -111.57
17.49 6.11 30.12
36.37 24.99 49.00
643.74 643.63 642.87
-0.62 -0.66 -0.25
-1.40 -1.40 -1.40
1.17 1.17 1.16
1.000 1.04 1.000 1.03 1.000 1.04
3 3 4
3 3 2
4 3 3
2 3 2
1 1 2
1 1 2
1464
Journal of Chemical & Engineering Data, Vol. 55, No. 3, 2010
Table 5. Continued Sθ molecule 1,2,3,4,6,7 1,2,3,5,6,7 1,2,3,5,6,8 1,2,3,5,7,8 1,2,3,6,7,8 1,2,4,5,6,8 1,2,4,5,7,8
group
∆fHθ
∆fGθ
Cp,m/J · mol-1 · K-1
∆fGθR
symmetry J · mol-1 · number K-1 kJ · mol-1 kJ · mol-1 kJ · mol-1 constant 10-3 T 105 T-1 107 T-2
R2
SE NR Nβ No Nm Np N1,8
Cs C2 C1 C1 Cs C2 Cs
1 2 1 1 1 2 1
627.52 624.17 622.19 622.22 619.63 616.80 622.60
-148.21 -159.52 -139.63 -140.16 -157.45 -125.79 -125.79
-8.58 -18.88 1.60 1.06 -15.46 17.04 15.32
10.31 0.00 20.48 19.94 3.42 35.92 34.20
644.00 643.99 642.86 642.85 643.16 641.99 641.89
-0.74 -0.65 -0.21 -0.19 -0.20 0.13 0.20
-1.41 -1.41 -1.40 -1.40 -1.41 -1.39 -1.39
1.17 1.17 1.16 1.16 1.17 1.16 1.16
1.000 1.000 1.000 1.000 1.000 1.000 1.000
2 2 3 3 2 4 4
4 4 3 3 4 2 2
4 4 3 3 4 2 2
2 2 2 2 2 2 2
1 0 1 1 0 2 2
0 0 1 1 1 2 2
C1 C1
1 1
649.21 649.05
-133.77 -120.75
13.60 26.67
0.00 13.07
656.70 655.71
-7.84 -1.37 -7.43 -1.37
1.12 1.11
1.000 1.00 3 1.000 1.00 4
4 3
5 4
3 3
1 2
1 2
C2V
2
670.78
-115.44
39.71
669.53 -15.07 -1.34
1.07
1.000 0.95 4
4
6
4
2
2
1.04 1.05 1.04 1.05 1.05 1.04 1.04
hepta-CAQN 1,2,3,4,5,6,7 1,2,3,4,5,6,8 OCAQN 1,2,3,4,5,6,7,8 a
θ
θ
θ
Vm is the molecular volume. S is standard entropy. ∆fH is the standard enthalpy of formation of the compound. ∆fG is the standard Gibbs energy of formation of the compound. ∆fGθR is the relative magnitude of the standard Gibbs energy of formation. Cθp,m is the molar heat capacity at constant pressure. N is the number of Cl atom substitutions, and the subscript PCS indicates the positions.
Journal of Chemical & Engineering Data, Vol. 55, No. 3, 2010 1465
Figure 2. Plots of the values obtained from the correlations versus the corresponding DFT results.
