* heat of formation of the varius benson group * -------------------------------------------- * * this file is read up to the keyword END. * Comment line (* as first character) can be placed * everywhere in the file. * * Format of the file is fixed : a21,1x,f10.3 * Benson group [21] + 1X [1] + value [10] * * data have 3 origins : * - the original data from Benson * - additional data given in the SAPRC99 documentation * - some crude estimates performed to complete the database. * These last data need to be revisited and additional work is * required. * * data from benson * ---------------- C*_(C) 39.10 C*_(C)(C) 40.95 C*_(C)(C)(C) 42.60 C*_(C)(O) 35.10 C*_(CO) 37.90 C_(CO*) -5.40 C_(CO*)(C) -0.30 C_(CO*)(C)(C) 2.60 C_(C) -10.20 C_(C)(C) -4.93 C_(C)(C)(C) -1.90 C_(C)(C)(C)(C) 0.50 C_(C)(C)(C)(Cd) 1.68 C_(C)(C)(C)(CO) 1.40 C_(C)(C)(C)(NO2) -11.70 C_(C)(C)(C)(O) -6.60 C_(C)(C)(C)(O*) 8.60 C_(C)(C)(Cd) -1.48 C_(C)(C)(CO) -1.70 C_(C)(C)(NO2) -13.60 C_(C)(C)(O) -7.20 C_(C)(C)(O)(O) -18.60 C_(C)(C)(O*) 7.80 C_(C)(C*) -4.95 C_(C)(Cd) -4.76 C_(C)(Cd)(O) -6.50 C_(C)(CO) -5.20 C_(C)(NO2) -14.40 C_(C)(O) -8.10 C_(C)(O)(O) -16.30 C_(C)(O)(O)(O) -29.60 C_(C)(O*) 6.10 C_(C*) -10.08 C_(Cd) -10.20 C_(Cd)(Cd) -4.29 C_(Cd)(CO) -3.80 C_(CO) -10.20 C_(CO)(CO) -7.20 C_(O) -10.20 C_(O)(O) -16.20 Cd_(C)(C)(Cd) 10.34 Cd_(C)(Cd) 8.59 Cd_(C)(Cd)(Cd) 8.88 Cd_(C)(Cd)(CO) 7.50 Cd_(C)(Cd)(O) 10.30 Cd_(Cd) 6.26 Cd_(Cd)(Cd) 6.78 Cd_(Cd)(Cd)(Cd) 4.60 Cd_(Cd)(Cd)(O) 8.90 Cd_(Cd)(CO) 5.00 Cd_(Cd)(CO)(O) 11.60 Cd_(Cd)(O) 8.60 CO_(C) -29.10 CO_(C)(C) -31.40 CO_(C)(C*) -31.40 CO_(C)(CO) -29.20 CO_(C)(O) -35.10 CO_(Cd) -29.10 CO_(CO) -25.30 CO_(CO)(O) -29.30 CO_(O) -32.10 CO_(O)(O) -29.70 O_(C) -37.10 O_(C)(C) -23.20 O_(C)(C*) -23.20 O_(C)(Cd) -30.50 O_(C)(CO) -43.10 O_(C)(NO2) -19.40 O_(C)(O) -4.50 O_(C*) -37.90 O_(Cd)(Cd) -33.00 O_(Cd)(CO) -45.20 O_(CO) -58.10 O_(CO)(CO) -46.50 O_(CO)(O) -19.00 O_(NO2)(O) 4.00 O_(O) -16.30 O_(O)(O) 14.70 CO*_(C) 0.00 NO2_(C) 0.00 NO2_(O) 0.00 ONO2_(C) 0.00 * data taken from the SAPRC99 documentation * --------------------------------------- CO*_(O) -4.20 CO*_(ONO2) -19.40 C*_(C)(C)(CO) 42.25 C*_(C)(C)(O) 31.50 C*_(C)(C)(ONO2) 12.10 C*_(C)(CO) 38.58 C*_(C)(CO)(O) 32.46 C*_(C)(O)(O) 24.50 C*_(C)(ONO2) 15.70 C*_(CO)(O) 34.95 C*_(CO)(ONO2) 15.55 C*_(O) 35.75 C*_(O)(O) 29.93 C*_(ONO2) 16.35 C_(CO*)(C)(C)(C) 5.70 C_(CO*)(C)(ONO2) -20.53 C_(CO*)(CO) -2.41 C_(CO*)(O) -1.76 C_(CO*)(ONO2) -21.71 C_(C)(C)(C)(C*) -1.20 C_(C)(C)(C)(ONO2) -26.00 C_(C)(C)(C)(OO*) 5.50 C_(C)(C)(C*) -3.60 C_(C)(C)(C*)(O) -8.90 C_(C)(C)(C*)(ONO2) -28.30 C_(C)(C)(CO)(CO) -1.47 C_(C)(C)(CO)(O) -5.70 C_(C)(C)(CO)(O*) 9.50 C_(C)(C)(CO)(ONO2) -25.10 C_(C)(C)(O)(O*) -3.40 C_(C)(C)(O)(ONO2) -38.00 C_(C)(C)(O)(OO*) -6.50 C_(C)(C)(O*)(ONO2) -23.80 C_(C)(C)(ONO2) -26.60 C_(C)(C)(OO*) 4.90 C_(C)(C*)(CO) -3.40 C_(C)(C*)(CO)(O) -8.00 C_(C)(C*)(CO)(ONO2) -27.40 C_(C)(C*)(O) -9.50 C_(C)(C*)(ONO2) -28.90 C_(C)(Cd)(ONO2) -25.90 C_(C)(CO)(CO) -4.57 C_(C)(CO)(CO)(O) -8.57 C_(C)(CO)(O) -6.32 C_(C)(CO)(O)(O) -17.70 C_(C)(CO)(O)(O*) -2.50 C_(C)(CO)(O*) 7.87 C_(C)(CO)(ONO2) -25.72 C_(C)(NO2)(NO2) -9.90 C_(C)(O)(O)(ONO2) -49.00 C_(C)(O)(O*) -2.10 C_(C)(O)(ONO2) -35.70 C_(C)(O)(OO*) -4.20 C_(C)(O*)(ONO2) -21.50 C_(C)(ONO2) -27.50 C_(C)(OO*) 3.34 C_(C*)(CO) -6.90 C_(C*)(CO)(O) -8.02 C_(C*)(CO)(ONO2) -27.42 C_(C*)(O) -9.73 C_(C*)(O)(O) -18.60 C_(C*)(ONO2) -29.13 C_(Cd)(O) -8.05 C_(Cd)(O*) 5.25 C_(Cd)(OO*) 3.39 C_(CO)(CO)(O) -9.19 C_(CO)(CO)(O)(ONO2) -30.58 C_(CO)(CO)(O*) 5.81 C_(CO)(CO)(ONO2) -28.59 C_(CO)(O) -6.95 C_(CO)(O)(O) -15.42 C_(CO)(O)(O*) -1.22 C_(CO)(O*) 7.24 C_(CO)(ONO2) -26.36 C_(CO)(OO*) 6.05 C_(O)(O)(O) -26.92 C_(O)(O)(O)(O) -40.25 C_(O)(O)(O*) -12.72 C_(O)(O)(O)(O*) -25.05 C_(O)(O*) -1.90 C_(O)(ONO2) -35.50 C_(O)(OO*) -4.00 C_(O*)(ONO2) -21.30 C_(ONO2) -29.60 C_(OO*) 2.49 CO_(C)(Cd) -34.09 CO_(C)(O*) -39.36 CO_(C)(OO*) -30.91 CO_(C*) -29.10 CO_(C*)(CO) -31.10 CO_(C*)(O) -34.10 CO_(CO)(CO) -26.89 CO_(O)(O*) -34.10 CO_(O)(OO*) -25.51 CO_(O*) -36.84 O_(CO*) -42.64 O_(CO*)(C) -27.30 O_(C*)(CO) -40.65 O_(C*)(NO2) -12.45 O_(C*)(O) -4.50 O_(Cd) -44.86 O_(O)(O*) 17.50 O_(O*)(ONO2) 14.00 ONO2_(C*) 6.95 * crude estimation for the following group (see below the doc) * ---------------------------------------- O_(CO*)(O) -3.40 O_(CO)(ONO2) -15.00 ONO2_(O) 0.00 O_(CO*)(ONO2) 0.60 CO_(CO*) -16.90 CO*_(CO) 0.00 CO_(CO*)(C) -20.65 CO_(CO*)(O) -20.75 C_(C)(CO)(CO)(ONO2) -27.97 C*_(C)(CO)(ONO2) 20.01 C_(C)(CO)(CO)(O*) 5.62 C_(CO)(CO)(CO)(O) -5.50 C*_(CO)(CO)(O) 30.96 C_(CO)(CO)(CO) -5.00 C*_(CO)(CO) 37.10 C_(CO)(CO)(CO)(O*) 8.69 C_(CO*)(C)(O) -1.30 CO_(CO*)(CO) -18.50 C_(CO*)(CO)(O) -0.80 C_(Cd)(CO)(O*) 6.98 CO_(Cd)(CO) -29.20 C_(C)(Cd)(O*) 6.95 C_(Cd)(CO)(O) -4.92 C_(C*)(Cd) -4.78 Cd_(C*)(Cd) 4.85 C*_(Cd) 35.84 CO_(Cd)(O) -35.10 C_(CO*)(CO)(ONO2) -18.64 C_(C)(C*)(Cd) -3.43 Cd_(C*)(Cd)(CO) 3.76 Cd_(Cd)(CO)(CO) 3.91 C_(C)(C)(Cd)(O*) 7.75 C_(C)(Cd)(CO) -0.30 C*_(C)(Cd) 37.89 CO_(C*)(Cd) -31.40 C_(CO*)(C)(C)(ONO2) -19.35 C_(CO*)(C)(C)(O) 1.8 C_(CO*)(C)(CO)(O) -0.84 C_(CO*)(C)(CO)(ONO2) -15.54 C_(CO*)(CO)(CO)(O) 0.16 C_(CO)(CO)(CO)(ONO2) -30.82 C*_(CO)(CO)(ONO2) 17.03 C_(CO*)(C)(CO) 2.69 C_(C)(C)(C*)(CO) 0.10 C_(CO*)(C)(C)(CO) 5.89 CO_(CO)(O*) -36.94 C_(CO)(O)(ONO2) -22.47 C*_(O)(ONO2) 12.35 O_(CO*)(CO) -48.64 C_(O*) 4.40 C_(C)(CO)(CO)(CO) -2.37 C*_(C)(CO)(CO) 40.75 C_(CO)(CO)(CO)(CO) -2.8 C*_(CO)(CO)(CO) 36.3 C_(C*)(CO)(CO) -3.72 C_(CO*)(CO)(CO) -0.58 C_(C)(C*)(CO)(CO) -0.22 C_(CO*)(C)(CO)(CO) 5.68 ONO2_(CO) 0. CO_(C)(ONO2) -27.5 CO_(ONO2) -29.6 CO_(CO)(ONO2) -26.36 C_(C)(CO)(O)(ONO2) -17.7 C*_(C)(O)(ONO2) 24.50 C_(C*)(O)(ONO2) -33.68 C_(CO*)(O)(ONO2) -21.99 C_(CO*)(O)(O) 1.88 C_(CO)(O*)(ONO2) -20.36 C_(CO*)(Cd) 0.88 C_(C*)(CO)(CO)(O) -6.31 C_(CO*)(Cd)(O) -0.12 C*_(Cd)(O) 31.84 C_(Cd)(CO)(ONO2) -24.32 C_(C*)(Cd)(O) -9.33 C_(C*)(CO)(CO)(ONO2) -25.71 C_(Cd)(ONO2) -27.45 C_(C)(Cd)(CO)(O*) 8.68 C_(CO*)(CO)(CO)(ONO2) -14.97 C_(CO*)(Cd)(ONO2) -19.35 C_(C*)(Cd)(ONO2) -28.05 C_(CO*)(CO)(CO)(CO) 1.25 CO_(CO*)(Cd) -20.65 C_(C*)(CO)(CO)(CO) 1.52 C_(Cd)(CO)(CO)(O*) 6.51 C_(C)(C)(Cd)(O) -4.95 C_(C)(C)(Cd)(CO) 3.00 C*_(C)(C)(Cd) 39.94 C_(C)(Cd)(CO)(O) -4.30 C_(C)(C)(Cd)(ONO2) -25.30 C_(C)(C*)(Cd)(ONO2) -26.70 C_(Cd)(CO)(CO)(O) -7.17 C_(C)(Cd)(CO)(ONO2) -23.70 C_(Cd)(CO)(CO)(ONO2) -26.57 C_(Cd)(CO)(CO) 0.88 C*_(Cd)(CO) 36.00 Cd_(C)(C*)(Cd) 7.18 C*_(CO)(O)(ONO2) 11.55 C_(CO)(CO)(O)(O*) -2.85 C_(CO)(CO)(O)(O) -17.66 C*_(CO)(O)(O) 26.48 **estimates by Lee-Taylor, July 2006** *------------------------------------- C_(C)(C*)(Cd)(O) -7.3 C_(C)(CO)(OO*) 5.6 C_(C)(CO)(O*)(ONO2) -3.3 C_(C*)(Cd)(CO)(O) -6.6 C_(C*)(Cd)(CO)(ONO2) -25.6 C_(C*)(CO)(O)(ONO2) -17.5 C_(CO)(CO)(OO*) 3.5 C_(CO)(CO)(O*)(ONO2) -16.2 C_(CO*)(CO)(O)(O) -0.06 C_(CO*)(CO)(O)(ONO2) -18.1 C_(CO*)(C)(Cd) 4.3 CO_(CO)(OO*) -27.8 ONO2_(CO*) 0.0 **Ric, May 2008** *------------------------------------- C*_(C)(Cd)(CO) 38.86 C*_(Cd)(CO)(CO) 37.79 C_(C)(Cd)(CO)(CO) -0.59 C_(Cd)(CO)(CO)(CO) -0.6 C_(CO*)(Cd)(CO)(O) 3.03 C_(CO*)(Cd)(CO)(ONO2) -20.07 **Ric, Nov 2008 *------------------------------------- C_(C*)(Cd)(CO) -3.45 Cd_(Cd)(Cd)(CO) 8.88 Cd_(C*)(Cd)(Cd) 9.0 C_(CO*)(C)(Cd)(ONO2) -18.3 C_(CO*)(Cd)(CO) 1.04 C_(CO*)(C)(Cd)(O) 2.58 **Ludo, July 2009** *------------------------------------- Cd_(Cd)(O*) 22.8 CO_(CO*)(ONO2) -15.3 C_(C)(C*)(O)(O) -14.2 C_(C)(C*)(O)(ONO2) -40.3 C_(CO*)(C)(O)(O) -13.4 C_(CO*)(C)(O)(ONO2) -33.11 C_(C*)(CO)(O)(O) -12.72 Cd_(C)(Cd)(O*) 25.3 Cd_(C*)(Cd)(O) 10.42 CO_(C*)(ONO2) -27.5 Cd_(Cd)(CO)(O*) 26.6 C_(C)(Cd)(O)(O*) -8.2 C_(Cd)(CO)(O)(O*) -2.27 C_(C)(Cd)(O)(O) -11.2 C_(C)(Cd)(O)(ONO2) -30.6 C_(C*)(Cd)(O)(ONO2) -30.48 CO_(Cd)(ONO2) -27.5 C_(Cd)(O)(O*) 4.68 C_(C)(Cd)(O*)(ONO2) -23.63 C_(Cd)(Cd)(O*) 8.44 C_(Cd)(CO)(O)(ONO2) -36.87 C_(CO*)(Cd)(O)(ONO2) -25.68 CO_(Cd)(Cd) -34.09 C_(C*)(Cd)(O)(O) -8.05 C_(Cd)(CO)(O)(O) -17.47 C_(Cd)(CO)(O*)(ONO2) -22.67 C_(CO*)(Cd)(O)(O) -3.6 C_(Cd)(O)(O) -10.32 C_(Cd)(O)(ONO2) -29.72 C_(Cd)(O*)(ONO2) -16.42 Cd_(Cd)(Cd)(O*) 23.9 C_(Cd)(Cd)(ONO2) -25.96 C_(Cd)(Cd)(O) -6.56 C_(Cd)(Cd)(O)(O*) -2.76 C_(Cd)(Cd)(O)(O) -17.96 C_(Cd)(Cd)(O)(ONO2) -37.36 CO_(Cd)(O*) -39.36 C*_(C)(Cd)(O) 32.41 ** Ric 2015 CO_(OO*) 2.39 C_(C)(OO*)(ONO2) -20.4 C_(C)(C)(OO*)(ONO2) -17.32 C_(C)(CO)(O)(OO*) -6.50 C_(C)(CO)(OO*)(ONO2) -17.78 C_(C)(ONO2)(ONO2) -46. C*_(ONO2)(ONO2) 12.47 C_(CO)(ONO2)(ONO2) -48.33 C_(C)(C)(CO)(OO*) 5.5 C_(C*)(ONO2)(ONO2) -50.8 C_(CO)(OO*)(ONO2) -16.53 C_(CO)(O)(OO*) -4.20 C_(CO)(CO)(OO*)(ONO2) -21.19 C_(C)(C)ONO2)(ONO2) -42.4 C_(C)(CO)(ONO2)(ONO2) -45.12 END *********************************** Following groups were found in Carter's Table (Table 37) in SAPRC99 documentation. These groups are ordered in the wrong way. In addition the groups were found in Table 38 (ordered in the correct way) but with different values. Selected values are taken from table 38. C_(C)(C*)(C) -1.90 C_(C)(C*)(C)(C) 1.50 Some additional group estimations : ---------------------------------- O_(CO*)(O) estimated as -3.40 from O_(CO)(O) and using the differences found between O_(CO) and O_(CO*) and O_(CO)(C) and O_(CO*)(C). Of course, highly uncertain O_(CO)(ONO2) = O_(CO)(O) + O_(NO2)(O) = -15.00 and setting group for ONO2_(O) to 0. O_(CO*)(ONO2) = O_(CO*)(O) + O_(NO2)(O) = 0.60 CO_(CO*) and CO*_(CO) : I did not find any useful data to estimate those groups. I used the minimum of bond dissociation energy linked to H-COR (i.e. 360 kJ) that I found in the Handbook (see ref). Then using -211.9 kJ for the formation heat of glyoxal gives -69.9 kJ for the heat of formation of HCO-CO. Finally, setting CO*_(CO) to 0 gives a group contribution of -16.9 kcal for CO_(CO*). CO_(CO*)(C) : same approach as for CO_(CO*) above. Using methyl glyoxal (instead of glyoxal) leads to CO_(CO*)(C)=-20.65 kcal CO_(CO*)(O) : use value given for above for CO_(CO*)(C), increased by 0.1 which corresponds to the difference between CO_(CO)(C) and CO_(CO)(O) C_(C)(CO)(CO)(ONO2) = C_(C)(CO)(CO)(O) + O_(C)(NO2) = -27.97 C*_(C)(CO)(ONO2) = C*_(C)(CO)(O) + O_(C*)(NO2) = 20.01 C_(C)(CO)(CO)(O*) = C_(C)(CO)(CO)(O) +14.19=5.62 14.19 is the difference between C_(C)(O*) and C_(C)(O) C_(C)(CO)(O*)and C_(C)(CO)(O) C_(CO)(O*) and C_(CO)(O) C_(CO)(CO)(CO)(O) : estimated to be around -5.50, based on the following data available for C_{(C)or(CO)}(O) : C_(C)(O) : -8.10 C_(C)(C)(O) : -7.20 C_(CO)(O) : -6.95 C_(C)(C)(C)(O) : -6.60 C_(C)(CO)(O) : -6.32 C_(C)(C)(CO)(O) : -5.70 Note that the data given for C_(C)(CO)(CO)(O) : -8.57 seems too high C*_(CO)(CO)(O) : set equal to C*_(C)(CO)(O) (32.46) decreased by 1.5 due to the substitution of (C) to (CO) => 30.96 C_(CO)(CO)(CO) estimated to be -5.00 based on : C_(C)(C) : -4.93 ; C_(C)(CO) : -5.20 ; C_(CO)(CO) : -7.60 C_(C)(C)(C) : -1.90 ; C_(C)(C)(CO) : -1.70 ; C_(C)(CO)(CO) : -4.57 C*_(CO)(CO) : set equal to C*_(C)(CO) (38.58) decreased by 1.5 due to the substitution of (C) to (CO) => 37.1 C_(CO)(CO)(CO)(O*) = C_(CO)(CO)(CO)(O) + 14.19 (see above) C_(CO*)(C)(O) = C_(CO)(C)(O) -5.00 = -1.30 ; based on the decrease between C_(CO*) and C_(CO) C_(CO*)(O) and C_(CO*)(C) CO_(CO*)(CO) = CO_(CO)(CO) + 8.4 = -18.5 based on the differences between CO_(CO) and CO_(CO*) CO_(CO)(C) and CO_(CO*)(C) C_(CO*)(CO)(O) = C_(CO)(CO)(O) +8.4= -0.80 /// C_(Cd)(CO)(O*) = 6.98 based on C_(C)(CO)(O*) - difference between C_(C)(O*) and C_(Cd)(O*) coherent with the value for C_(CO)(O*) : 7.24 CO_(Cd)(CO) estimated to be -29.20 based on : no difference between CO_(C) and CO_(Cd) so there is difference between CO_(Cd)(CO) and CO_(C)(CO) C_(Cd)(C)(O*) = 6.95 based on C_(C)(C)(O*) - difference between C_(C)(O*) and C_(Cd)(O*) C_(Cd)(CO)(O) = -4.92 based on C_(C)(CO)(O) - difference between C_(C)(CO) and C_(Cd)(CO) C_(Cd)(C*) = -4.78 based on C_(C)(C*) + difference between C(Cd)(C) and C(C)(C) Cd_(C*)(Cd) 4.85 C*_(Cd) 35.84 are calculated to imply a k decomposition for Cd=Cd-CH2-CH2O. equal to (k reaction with O2 * [o2]) Actually, Cd_(C*)(Cd) + C*_(Cd) = 37.65 , so the two thermochemical groups are adjusted with the mean values of the Cd_ groups and the C*_ groups. CO_(Cd)(O) -35.10 the same as CO_(C)(O) because there is no difference between CO_(C) and CO_(Cd) C_(CO*)(CO)(ONO2) -18.64 based on C_(CO*)(CO) + the mean value of [C_(CO)(ONO2) - C_(CO)] and [C_(CO*)(ONO2) - C_(CO*)] C_(C)(C*)(Cd) -3.43 based on C_(C)(C)(C*) + difference between C(Cd)(C) and C(C)(C) Cd_(C*)(Cd)(CO) 3.76 based on Cd_(C*)(Cd) + difference between Cd_(C)(Cd) and Cd_(Cd)(C)(CO) Cd_(Cd)(CO)(CO) 3.91 based on Cd_(Cd)(CO) + difference between Cd_(C)(Cd) and Cd_(Cd)(C)(CO) C_(C)(C)(Cd)(O*) 7.75 based on C_(C)(C)(C)(O*) + difference between C_(C)(O*) and C_(Cd)(O*) C_(C)(Cd)(CO) -0.30 based on C_(C)(C)(CO) + difference between C_(C)(CO) and C_(Cd)(CO) C*_(C)(Cd) 37.89 based on C*_(Cd) + difference between C*_(C) and C*_(C)(C) CO_(C*)(Cd) -31.40 same value as CO_(C)(C*) because there is no difference between CO_(C) and CO_Cd C_(CO*)(C)(C)(ONO2) -19.35 based on C_(CO*)(C)(ONO2) + difference between C_(CO*)(ONO2) and C_(CO*)(C)(ONO2) C_(CO*)(C)(C)(O) 1.8 based on C_(CO*)(C)(C)(C) + difference between C_(CO*)(C)(C) and C_(CO*)(C)(O) C_(CO*)(C)(CO)(O) -0.84 based on C_(CO*)(CO)(O) + difference between C_(CO*)(O) and C_(CO*)(O)(C) C_(CO*)(C)(O) C_(CO*)(C)(CO)(ONO2) -15.54 based on C_(CO*)(CO)(ONO2) + difference between C_(CO*)(C)(C)(C) and C_(CO*)(C)(C) C_(CO*)(CO)(CO)(O) 0.16 based on C_(CO*)(CO)(O) + difference between C_(CO*)(O) and C_(CO*)(CO)(O) C_(CO)(CO)(CO)(ONO2) -30.82 based on C_(CO)(CO)(ONO2) + difference between C_(CO)(ONO2) and C_(CO)(CO)(ONO2) C*_(CO)(CO)(ONO2) 17.03 mean value between [C*_(CO)(CO)(O) + O_(C*)(NO2)] and [C*_(CO)(CO) + difference between C*_(CO) and C*_(CO)(ONO2)] C_(CO*)(C)(CO) 2.69 = C_(CO*)(C) + [C_(CO*)(CO) - C_(CO*)] C_(C)(C)(C*)(CO) 0.10 = C_(C)(C*)(CO) + [C_(C)(C)(CO) - C_(C)(CO)] = C_(C)(C*)(CO) + [C_(C)(C)(C*) - C_(C)(C*)] C_(CO*)(C)(C)(CO) 5.89 = C_(CO*)(C)(C)(CO) + [C_(CO*)(C)(C)(CO) - C_(CO*)(C)(C)(CO)] CO_(CO)(O*) -36.94 = CO_(O*) + [ CO_(C)(CO) - CO_(C) ] C_(CO)(O)(ONO2) -22.47 = C_(CO)(O) + [ C_(CO)(ONO2) - C_(CO)] C*_(O)(ONO2) 12.35 = C*_(O) + [C*_(C)(ONO2) - C*_(C) ] O_(CO*)(CO) -48.64 = O_(CO*) + [O_(C)(CO) - O_(C) ] coherent with O_(CO) + [O_(C)(CO*) - O_(C) ] = -48.3 C_(O*) 4.40 = C_(C)(O*) - (C_(C)(C)(O*) - C_(C)(O*)] C_(C)(CO)(CO)(CO) -2.37 =C_(CO)(CO)(CO) + [C_(CO)(CO)(C) - C_(CO)(CO)] C*_(C)(CO)(CO) : set equal to C*_(C)(C)(CO) (42.25) decreased by 1.5 due to the substitution of (C) to (CO) => 40.75 C_(CO)(CO)(CO)(CO) -2.8 C_(CO)(CO)(CO) + [C_(CO)(CO)(CO) - C_(CO)(CO)] C*_(CO)(CO)(CO) 36.3 =C*_(CO)(CO) + [C*_(CO)(CO) - C*_(CO)] C_(C*)(CO)(CO) -3.72 = C_(C*)(CO) + [C_(C*)(CO) - C_(C*)] C_(CO*)(CO)(CO) -0.58 =C_(CO*)(CO) + [ C_(CO*)(CO) - C_(CO*)] C_(C)(C*)(CO)(CO) -0.22 = C_(C*)(CO)(CO) + [C_(C)(C*)(CO) - C_(C*)(CO)] C_(CO*)(C)(CO)(CO) 5.68 = C_(CO*)(C)(CO) +[C_(CO*)(C)(CO) - C_(CO*)(C)] ONO2_(CO) 0. These values are those for the same CO_(C)(ONO2) -27.5 groups but with a C instead of a CO, thus CO_(ONO2) -29.6 the estimations are very crude. CO_(CO)(ONO2) -27.5 C_(C)(CO)(O)(ONO2) -21.81 = C_(CO)(O)(ONO2) + [ C_(C)(CO)(ONO2) - C_(CO)(ONO2)] C*_(C)(O)(ONO2) 6.25 = C*_(C)(C)(ONO2) + [C*_(C)(O) - C*_(C)(C)] C_(C*)(O)(ONO2) - 33.68 = C_(C*)(ONO2) + [C_(C)(C*)(O) - C_(C)(C*)] C_(CO*)(O)(ONO2) -21.99 = C_(CO*)(C)(ONO2) + [C_(CO*)(O) - C_(CO*)(C)] C_(CO*)(O)(O) 1.88 = C_(CO*)(O) + [C_(CO*)(O) - C_(CO*)] C_(CO)(O*)(ONO2) -20.36 = C_(C)(O*)(ONO2) + [C_(CO)(O*) - C_(C)(O*)] C_(CO*)(Cd) 0.88 = C_(CO*)(C) + [C_(C)(C)(C)(Cd) - (C_(C)(C)(C)(C)] C_(C*)(CO)(CO)(O) -6.31 = C_(C*)(CO)(O) + [ C_(C*)(CO)(O) - C_(C*)(O) ] C_(CO*)(Cd)(O) -0.12 = C_(CO*)(C)(O) + [C_(C)(C)(C)(Cd) - C_(C)(C)(C)(C)] C*_(Cd)(O) 31.84 = C*_(C)(O) + [C*_(C)(O) - C*_(C)] C_(Cd)(CO)(ONO2) -24.32 = C_(Cd)(CO) + [C_(C)(CO)(ONO2) C_(C)(CO)] C_(C*)(Cd)(O) -9.33 = C_(C*)(Cd) + [C_(C*)(C)(O) - C_(C*)(C)] C_(C*)(CO)(CO)(ONO2) -25.71 = C_(C*)(CO)(ONO2) + [C_(C*)(CO)(ONO2) - C_(C*)(ONO2)] C_(Cd)(ONO2) -27.45 = C_(C)(ONO2) + [C_(Cd)(O) - C_(C)(O)] C_(C)(Cd)(CO)(O*) 8.68 = C_(Cd)(CO)(O*) + [C_(C)(Cd)(O*) - C_(Cd)(O*)] C_(CO*)(CO)(CO)(ONO2) -14.97 C_(CO*)(CO)(ONO2) + [C_(CO*)(CO)(ONO2) - C_(CO*)(ONO2) ] C_(CO*)(Cd)(ONO2) -19.35 = C_(CO*)(C)(ONO2) + [(C_(CO*)(Cd) - C_(CO*)(C)] C_(C*)(Cd)(ONO2) -28.05 mean value between = C_(C*)(C)(ONO2) + [C_(C*)(Cd)(O) - C_(C*)(C)(O)] and = C_(C*)(Cd) + [C_(C*)(C)(ONO2)-C_(C*)(C)] C_(CO*)(CO)(CO)(CO) 1.25 = C_(CO*)(CO)(CO) + [C_(CO*)(CO)(CO) - C_(CO*)(CO)] CO_(CO*)(Cd) -20.65 = CO_(Cd) + [CO_(CO*)(C) - CO_(C)] C_(C*)(CO)(CO)(CO) 1.52 = C_(C)(CO)(CO)(CO) + [C_(C)(CO)(CO) - C_(C*)(CO)(CO)] C_(Cd)(CO)(CO)(O*) 6.51 = C_(C)(CO)(CO)(O*) + [C_(Cd)(CO)(O*) - C_(C)(CO)(O*)] C_(C)(C)(Cd)(O) -4.95 = C_(C)(Cd)(O) + [C_(C)(Cd)(O) - C_(Cd)(O) ] C_(C)(C)(Cd)(CO) 3.00 mean values between : C_(C)(Cd)(CO) + [C_(C)(Cd)(CO) - C_(Cd)(CO)] => +3.2 C_(C)(C)(C)(CO) + [C_(C)(Cd)(CO) - C_(C)(C)(CO)] => +2.8 C*_(C)(C)(Cd) 39.94 = C*_(C)(Cd) + [C*_(C)(Cd) - C*_(Cd)] C_(C)(Cd)(CO)(O) -4.30 = C_(C)(C)(CO)(O) + [C_(Cd)(CO)(O)- C_(C)(CO)(O)] C_(C)(C)(Cd)(ONO2) -25.30 = C_(C)(C)(C)(ONO2) + [C_(C)(Cd)(ONO2) - C_(C)(C)(ONO2)] C_(C)(C*)(Cd)(ONO2) -26.70 = C_(C*)(Cd)(ONO2) + [C_(C)(C*)(Cd) - C_(C*)(Cd)] C_(Cd)(CO)(CO)(O) - 7.17 = C_(C)(CO)(CO)(O) + [C_(Cd)(CO)(O) - C_(C)(CO)(O)] C_(Cd)(CO)(CO)(ONO2) -26.57 = C_(C)(CO)(CO)(ONO2) + [C_(Cd)(CO)(ONO2) - C_(C)(CO)(ONO2)] C_(C)(Cd)(CO)(ONO2) -23.70 = C_(C)(C)(CO)(ONO2) + [C_(Cd)(CO)(ONO2)- C_(C)(CO)(ONO2)] C_(Cd)(CO)(CO) 0.88 = C_(C)(Cd)(CO) + [C_(C)(Cd)(CO) - C_(C)(C)(Cd)] C*_(Cd)(CO) 36.00 mean value between : C*_(CO) + [C*_(C)(Cd) - C*_(C)] => 36.69 C*_(Cd) + [C*_(C)(CO) - C*_(C)] => 35.32 Cd_(C)(C*)(Cd) 7.18 = Cd_(C*)(Cd) + [Cd_(C)(Cd) - Cd_(Cd)] C_(CO)(CO)(O)(ONO2) -30.58 = C_(CO)(CO)(ONO2) + [C_(CO)(CO)(O) - C_(CO)(CO)] C*_(CO)(O)(ONO2) 11.55 = C*_(O)(ONO2) + [C*_(CO)(ONO2) - C*_(ONO2)] C_(CO)(CO)(O)(O*) -2.85 = C_(CO)(O)(O*) + [C_(CO)(O*) - C_(CO)(CO)(O*)] C_(CO)(CO)(O)(O) -17.66 = C_(CO)(CO)(O) + [C_(CO)(O) - C_(CO)(O)(O)] C*_(CO)(O)(O) 26.48 = C*_(CO)(O) + [C_(CO)(O) - C_(CO)(O)(O)] Julia Lee-Taylor, NCAR, July 2006 --------------------------------- B = Benson; S = SAPRC; A = Aumont estimate CO_(CO)(OO*) -27.8 = mean of: CO_(C)(OO*) + CO_(CO) - CO_(C) = -30.91(S) + -25.3(B) - -29.1(B) CO_(C)(OO*) + CO_(CO)(O*) - CO_(C)(O*) = -30.91(S) + -36.94(A) - -39.36(S) C_(CO)(CO)(OO*) 3.5 = mean of: C_(CO)(CO)(O*) + C_(CO)(OO*) - C_(CO)(O*) = 5.81(S) + 6.05(S) - 7.24(S) C_(CO)(CO)(O*) + C_(C)(OO*) - C_(C)(O*) = 5.81(S) + 3.32(S) - 6.1(S) C_(CO)(CO)(O*) + C_(C)(C)(OO*) - C_(C)(C)(O*) = 5.81(S) + 4.9(S) - 7.8(S) C_(C)(CO)(OO*) 5.6 = mean of: C_(C)(CO)(O*) + C_(CO)(OO*) - C_(CO)(O*) = 7.87(S) + 6.05(S) - 7.24(S) C_(C)(CO)(O*) + C_(C)(OO*) - C_(C)(O*) = 7.87(S) + 3.32(S) - 6.1(S) C_(C)(CO)(O*) + C_(C)(C)(OO*) - C_(C)(C)(O*) = 7.87(S) + 4.9(S) - 7.8(S) C_(CO*)(CO)(O)(O) -0.06 = C_(CO*)(CO)(CO)(O) + C_(CO*)(CO)(O) - C_(CO*)(CO)(CO) = 0.16(A) + -0.8(A) - -0.58(A) C_(CO*)(CO)(O)(ONO2) -18.1 = mean of: C_(CO*)(CO)(CO)(ONO2) + C_(CO*)(CO)(O) - C_(CO*)(CO)(CO) = -14.97(A) + -0.8(A) - -0.58(A) = -15.19 C_(CO*)(CO)(CO)(O) + C_(CO*)(CO)(ONO2) - C_(CO*)(CO)(CO) = 0.16(A) + -18.64(A) - -0.58(A) = -17.9 C_(CO*)(CO)(CO)(ONO2) + C_(CO*)(O)(ONO2) - C_(CO*)(O)(ONO2) = -14.97(A) + -21.99(A) - -18.64(A) = -18.32 C_(CO*)(CO)(CO)(O) + C_(CO*)(O)(ONO2) - C_(CO*)(CO)(O) = 0.16(A) + -21.99(A) - -0.8(A) = -21.03 ONO2_(CO*) 0.00 estimated equivalent to ONO2_(CO) C_(C)(CO)(O*)(ONO2) -3.3 = C_(C)(CO)(O)(ONO2) -17.7(A) + mean of: C_(C)(CO)(O*) - C_(C)(CO)(O) = 7.87(S) - -6.32(S) = 14.2 C_(C)(CO)(CO)(O*) - C_(C)(CO)(CO)(O) = 5.62(A) - -8.57(S) = 14.2 C_(C)(CO)(O)(O*) - C_(C)(CO)(O)(O) = 2.5(S) - -17.7(S) = 15.2 C_(C)(O*)(ONO2) - C_(C)(O)(ONO2) = -21.5(S) - -37.5(S) = 14.2 C_(O*)(ONO2) - C_(O)(ONO2) = -21.3(S) - -35.5(S) = 14.2 i.e. radicalisation of the (O) group raises DHf by 14.4 C_(CO)(CO)(O*)(ONO2) -16.2 = C_(CO)(CO)(O)(ONO2) -30.58(S) + 14.4 (see above) (radicalisation of the (O) group raises DHf by 14.4) C_(CO*)(C)(Cd) 4.3 = C_(C)(Cd)(Cd) -0.3(A) + mean of: C_(CO*)(C) - C_(C)(CO) = -0.3(B) - -5.2(B) = 4.9 C_(CO*)(C)(C) - C_(C)(C)(CO) = 2.6(B) - 1.7(B) = 4.3 C_(CO*)(Cd) - C_(Cd)(CO) = 0.88(A) - 3.8(B) = 4.7 i.e. radicalisation of the (CO) group raises DHf by -4.6 C_(C)(C*)(Cd)(O) -7.3 = C_(C)(C)(Cd)(O) -4.95(A) + mean of: C_(C)(C*)(O) - C_(C)(C)(O) = -9.5(S) - -7.2(B) = -2.3 C_(C)(C*)(Cd) - C_(C)(C)(Cd) = -3.43(A) - -1.48(B) = -1.95 C_(C)(Cd)(O) - C_(C*)(Cd)(O) = -9.33(A) - -6.5(B) = -2.83 C_(C)(C)(C*)(O) - C_(C)(C)(C)(O) = -8.9(S) - -6.6(B) = -2.3 i.e. radicalisation of a (C) group lowers DHf by 2.3 C_(C*)(Cd)(CO)(O) -6.6 = C_(C)(Cd)(CO)(O) -4.3(A) + mean of: C_(C*)(CO)(O) - C_(C)(CO)(O) = -8.02(S) - -6.32(S) = -1.7 C_(C*)(Cd)(O) - C_(C)(Cd)(O) = -9.33(A) - -6.5(B) = -2.8 i.e. radicalisation of a (C) group lowers DHf by 2.3 (as above) C_(C*)(Cd)(CO)(ONO2) -25.6 = C_(C)(Cd)(CO)(ONO2) -23.7(A) + mean of: C_(C*)(Cd)(ONO2) - C_(C)(Cd)(ONO2) = -28.05(A) - -25.9(S) = -2.15 C_(C*)(CO)(ONO2) - C_(C)(CO)(ONO2) = -27.42(S) - -25.72(S) = -1.7 i.e. radicalisation of the (C) group lowers DHf by 1.9 C_(C*)(CO)(O)(ONO2) -17.5 = C_(C)(CO)(O)(ONO2) -17.7(A) + mean of: C_(C*)(CO)(ONO2) - C_(C)(CO)(ONO2) = -27.42(S) - -25.72(S) = -1.7 C_(C*)(O)(ONO2) - C_(C)(O)(ONO2) = -33.7(A) - -35.7(S) = 2.0 i.e. radicalisation of the (C) group raises DHf by 0.2 ------------------ Ric, May 2008 ------------------ C*_(C)(Cd)(CO) 38.86 mean value between : = C*_(C)(C)(CO) + [C*_(Cd) - C*_(C)] = C*_(C)(C)(Cd) + [C*_(CO) - C*_(C)] C*_(Cd)(CO)(CO) 37.79 = C*_(C)(C)(CO) + [C*_(Cd) - C*_(C)] + [C*_(CO) - C*_(C)] C_(C)(Cd)(CO)(CO) -0.59 = C_(C)(C)(C)(Cd) + [C_(CO)(CO) - C_(C)(C)] C_(Cd)(CO)(CO)(CO) -0.6 mean value between : = C_(C)(C)(C)(CO) + [C_(CO)(CO) - C_(C)(C)] + [C_(Cd) - C_(C)] = -0.87 = C_(C)(C)(C)(Cd) + [C_(CO)(CO) - C_(C)(C)] + [C_(CO) - C_(C)] = -0.59 = C_(C)(C)(CO)(CO) + [C_(Cd)(CO) - C_(C)(C)] = -0.34 C_(CO*)(Cd)(CO)(O) 3.03 mean value between : = C_(C)(C)(C)(O) + [C_(Cd)(CO) - C_(C)(C)] + [C_(CO*) - C_(C)] = -0.67 = C_(CO*)(C)(C)(C) + [C_(Cd)(CO) - C_(C)(C)] + [C_(O) - C_(C)] = 6.83 = C_(CO*)(C)(C)(O) + [C_(Cd)(CO) - C_(C)(C)] = 2.93 C_(CO*)(Cd)(CO)(ONO2) -20.07 = C_(C)(C)(C)(ONO2) + [C_(Cd)(CO) - C_(C)(C)] + [C_(CO*) - C_(C)] ------------------ Ric, Nov 2008 ------------------ C_(C*)(Cd)(CO) -3.45 = C_(C)(C)(Cd) + [C_(C*)(CO) - C_(C)(C)] Cd_(Cd)(Cd)(CO) 8.88 = Cd_(C)(Cd)(Cd) + [C_(CO) - C_(C)] Cd_(C*)(Cd)(Cd) 9.0 = Cd_(C)(Cd)(Cd) + [C_(C*) - C_(C)] C_(CO*)(C)(Cd)(ONO2) -18.3 = C_(CO*)(C)(C)(C) + [C_(C)(Cd)(ONO2) - C_(C)(C)(C)] C_(CO*)(Cd)(CO) 1.04 = C_(C)(C)(Cd) + [C_(CO*)(CO) - C_(C)(C)] C_(CO*)(C)(Cd)(O) 2.58 = C_(CO*)(C)(C)(C) + [C_(Cd)(O) - C_(C)(C)] ------------------ Ludo, July 2009 ------------------ Cd_(Cd)(O*) 22.8 = Cd_(Cd)(O) + C_(C)(O*) - C_(C)(O) CO_(CO*)(ONO2) -15.3 = CO_(CO*) - CO_(C) + CO_(C)(ONO2) C_(C)(C*)(O)(O) -14.2 = C_(C)(C)(C)(O) + [C_(C)(C*)(O) - C_(C)(C)(O)] + [C_(C)(C)(O) - C_(C)(C)(C)] C_(C)(C*)(O)(ONO2) -40.3 = C_(C)(C)(O)(ONO2) + [C_(C)(C*)(O) - C_(C)(C)(O)] C_(CO*)(C)(O)(O) -13.4 = C_(C)(C)(O)(O) + C_(CO*)(C)(C)(C) - C_(C)(C)(C)(C) C_(CO*)(C)(O)(ONO2) -33.11 = C_(C)(C)(O)(ONO2) + C_(CO*)(ONO2) - C_(C)(ONO2) C_(C*)(CO)(O)(O) -12.72 = C_(C*)(CO)(O) + C_(C)(C)(C)(O) - C_(C)(C)(C) Cd_(C)(Cd)(O*) 25.3 = Cd_(C)(Cd)(O) + C_(C)(C)(O*) - C_(C)(C)(O) Cd_(C*)(Cd)(O) 10.42 = Cd_(C)(Cd)(O) + C_(C*) - C_(C) CO_(C*)(ONO2) -27.5 = CO_(C*) - CO_(C) + CO_(C)(ONO2) Cd_(Cd)(CO)(O*) 26.6 = Cd_(Cd)(CO)(O) + C_(C)(C)(O*) - C_(C)(C)(O) C_(C)(Cd)(O)(O*) -8.2 = C_(C)(Cd)(O) + C_(C)(C)(O)(O*) - C_(C)(C)(O) C_(Cd)(CO)(O)(O*) -2.27 = C_(Cd)(CO) + C_(C)(C)(O)(O) - C_(C)(C) + C_(C)(C)(C)(O*) - C_(C)(C)(C)(O) C_(C)(Cd)(O)(O) -11.2 = C_(C)(Cd)(O) + C_(C)(C)(C)(O) - C_(C)(C)(C) C_(C)(Cd)(O)(ONO2) -30.6 = C_(C)(Cd)(O) + C_(C)(C)(C)(ONO2) - C_(C)(C)(C) C_(C*)(Cd)(O)(ONO2) -30.48 = C_(C)(Cd)(O) + C_(C)(C)(C)(ONO2) - C_(C)(C)(C) + C_(C*) - C_(C) CO_(Cd)(ONO2) -27.5 = CO_(Cd) - CO_(C) + CO_(C)(ONO2) C_(Cd)(O)(O*) 4.68 = C_(Cd)(O) + C_(C)(C)(O*) - C_(C)(C) C_(C)(Cd)(O*)(ONO2) -23.63 = C_(C)(Cd) + C_(C)(C)(O*)(ONO2) - C_(C)(C) C_(Cd)(Cd)(O*) 8.44 = C_(Cd)(Cd) + C_(C)(C)(O*) - C_(C)(C) C_(Cd)(CO)(O)(ONO2) -36.87 = C_(Cd)(CO) + C_(C)(C)(O)(ONO2) - C_(C)(C) C_(CO*)(Cd)(O)(ONO2) -25.68 = C_(C)(Cd)(O)(ONO2) + C_(CO*) - C_(C) C_(C*)(Cd)(O)(O) -8.05 = C_(C*) + C_(C)(Cd)(O) + C_(C)(C)(C)(O) - C_(C) - (C)_(C)(C) C_(Cd)(CO)(O)(O) -17.47 = C_(Cd)(CO) + C_(C)(C)(O*)(O) - C_(C)(C) C_(Cd)(CO)(O*)(ONO2) -22.67 = C_(Cd)(CO) + C_(C)(C)(O*)(ONO2) - C_(C)(C) C_(CO*)(Cd)(O)(O) -3.6 = C_(CO*)(C)(C)(C) + C_(C)(Cd)(O)(O) - C_(C)(C)(C)(C) C_(Cd)(O)(O) -10.32 = C_(Cd)(O) + C_(C)(C)(O) - C_(C)(C) C_(Cd)(O)(ONO2) -29.72 = C_(Cd)(O) + C_(C)(C)(ONO2) - C_(C)(C) C_(Cd)(O*)(ONO2) -16.42 = C_(Cd)(O*) + C_(C)(C)(ONO2) - C_(C)(C) Cd_(Cd)(Cd)(O*) 23.9 = Cd_(Cd)(Cd)(O) - C_(C)(C)(O) + C_(C)(C)(O*) C_(Cd)(Cd)(ONO2) -25.96 = C_(Cd)(Cd) + C_(C)(C)(ONO2) - C_(C)(C) C_(Cd)(Cd)(O) -6.56 = C_(Cd)(Cd) + C_(C)(C)(O) - C_(C)(C) C_(Cd)(Cd)(O)(O*) -2.76 = C_(C)(C)(O)(O*) + C_(Cd)(Cd) - C_(C)(C) C_(Cd)(Cd)(O)(O) -17.96 = C_(C)(C)(O)(O) + C_(Cd)(Cd) - C_(C)(C) C_(Cd)(Cd)(O)(ONO2) -37.36 = C_(C)(C)(O)(ONO2) + C_(Cd)(Cd) - C_(C)(C) CO_(Cd)(O*) -39.36 = CO_(Cd) - CO_(C) + CO_(C)(O*) C*_(C)(Cd)(O) 32.41 mean value between : = C*_(C)(C)(O) + [C*_(O) - C*_(C)] = C*_(C)(C)(Cd) + [C*_(Cd) - C*_(C)]