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ISSN 0012-5008, Doklady Chemistry, 2008, Vol. 420, Part 2, pp. 150155. Pleiades Publishing, Ltd., 2008.

. Original Russian Text A.L. Lapidus, V.M. Bavykin, E.A. Smolenskii, I.V. Chuvaeva, 2008, published in Doklady Akademii Nauk, 2008, Vol. 420, No. 6, pp. 771776.

CHEMISTRY

Cetane Numbers of Hydrocarbons as a Function of Their Molecular Structure


Corresponding Member of the RAS A.
a

L. Lapidusa, V. M. Bavykinb, E. A. Smolenskii , and I. V. Chuvaevaa


Received November 28, 2007

DOI: 10.1134/S0012500808060074

Previously, we suggested a radically new mathematical approach to the solution of the structureproperty relationship problem, referred to as the inverse function method, which was applied to the calculation of the octane numbers of alkanes and cycloalkanes [1]. The idea of such an approach is that, for each physicochemical property, some formally new properties can be constructed that, rst, are related in a one-to-one way to the initial properties and, second, linearly depend for nalkanes on the number of carbon atoms in a molecule. This considerably simplies the solution of the initial problem since these formally new properties are additive. An advantage of this simplication is that approximating functions can be found for the formally new properties and then the initial properties can be calculated since there is a one-to-one correspondence between them. In particular, the inverse function method allowed us to considerably improve the accuracy of calculations of the octane numbers (ONs) of hydrocarbons [1] as compared to the results obtained by known methods [25] and to develop a mathematical model with the following statistical characteristics: for the training set, comprising 41 hydrocarbons, R2 = 0.9989, s = 0.8289, and |max| = 3.0; for the test set, comprising 30 hydrocarbons, R2 = 0.9901, s = 2.6204, and |max| = 5.6. With the use of this model, the ONs were calculated for 231 hydrocarbons containing up to ten carbon atoms inclusive (94 alkanes, 98 cyclopentanes, and 39 cyclohexanes), both as yet unsynthesized and with unknown ONs [6]. One of the few properties for which no structure property relationship model has been developed is the cetane number (CN), a practically important characteristic of diesel oils.

In this study, we used the inverse function method [1] for constructing a similar model suitable for prediction and calculation of CNs of saturated hydrocarbons, as well as cyclopentanes and cyclohexanes. In general, a new property takes the form P 1 = ( P ) = a f ( P exp ) + b, (1) where P is some property, Pexp is the experimental value of the property P, and P1 is the new property derived from the initial one. After some algebra described in detail in [1, 6], we obtain the value of the new property derived from the initial property, i.e., the CN, which is described by the formula
1

n P, exp ( g i ) = bP exp ( bP exp + d ) 4a ( cP exp + eP exp + f ),


2 2

(2)

where n is the number of carbon atoms in a molecule and nP, exp(gi) is the value of the new property P1.
P 140 120 100 80 60 40 20 0 20 40 5 10 15 20 Number of CC bonds 1 2

Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Leninskii pr. 47, Moscow, 119991 Russia b Gubkin Russian State University of Oil and Gas, Leninskii pr. 65, Moscow, 119991 Russia 150

Fig. 1. Modeling of the CNs of n-alkanes: (1) experimental and (2) calculated data.

CETANE NUMBERS OF HYDROCARBONS Table 1. Modeling of the initial property P (cetane number) and the new function P1 for n-alkanes n 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 R2 s |max| a b n0 K0 Pexp 20.0 22.0 30.0 44.8 56.3 63.8 73.0 76.9 81.1 87.6 90.0 96.1 98.0 100.0 105.0 108.3 110.0 112.0 Pcalc |Pexp Pcalc | P1, exp P1, calc 0.2621 0.2693 0.2766 0.2839 0.2911 0.2984 0.3056 0.3129 0.3202 0.3274 0.3347 0.3420 0.3492 0.3565 0.3637 0.3710 0.3783 0.3855 0.9979 0.0017 0.0031 15.8665 54.1370 1.5401 101.5311 0.2851

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|P1, exp P1, calc | 0.0011 0.0027 0.0012 0.0007 0.0000 0.0007 0.0019 0.0004 0.0018 0.0013 0.0017 0.0029 0.0002 0.0031 0.0014 0.0026 0.0000 0.0018

18.8 1.2 0.2610 15.9 6.1 0.2721 35.0 5.0 0.2754 47.7 2.9 0.2831 57.1 0.8 0.2911 64.5 0.7 0.2976 70.8 2.2 0.3075 76.3 0.6 0.3125 81.2 0.1 0.3184 85.6 2.0 0.3287 89.8 0.2 0.3330 93.7 2.4 0.3449 97.4 0.6 0.3489 101.0 1.0 0.3534 104.5 0.5 0.3652 107.8 0.5 0.3737 111.1 1.1 0.3782 114.3 2.3 0.3837 Statistical characteristics of the model 0.9956 2.3164 6.1 8.9451 47.8033 0.1277 76.1549 0.1850

Note: Pcalc stands for the calculated properties P, and K0 , a, b, n0 , and are the parameters of the hyperbola branches.

Of special note is the fact that a new property P1 can be designed for any physicochemical property P if the value of the latter and n are in a one-to-one correspondence, i.e., if the function P(n) is monotonic and has no extreme points. Figures 1 and 2 show the plots of the initial property P (CN) and the new property P1 versus the number of carbon atoms in a molecule. It is seen that, as distinct from the initial property P (Fig. 1), the plot of the new property P1 versus the number of carbon atoms is linear. The initial and new values of the property for n-alkanes are summarized in Table 1, which also presents the computation results and parameters used for constructing the models. Then, we performed calculations by the scheme for nding optimal topological indices suggested in [7, 8]. All the available experimental data on cetane numbers were separated into a training set (27 compounds) and a test set (44 compounds) in order to additionally conrm the reliability and predictive power of the resulting models. Table 2 shows the fragments used for constructing an extrapolation model and their contributions
DOKLADY CHEMISTRY Vol. 420 Part 2 2008

to the overall property P1 according to the solution of the matrix equation for the structureproperty relationship [7]. This procedure was described in detail in [8].
P1 0.39 0.37 0.35 0.33 0.31 0.29 0.27 0.25 0 5 10 15 20 Number of CC bonds

Fig. 2. New function P1 vs. the number of CC bonds in a hydrocarbon molecule.

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Table 2. Extrapolation model of cetane numbers of hydrocarbons Hydrocarbon Pexp Training set n-Octane n-Decane n-Pentadecane n-Heptadecane n-Nonadecane 2-Methylpentane 5-Butylnonane 5-Butyldodecane 8-Propylpentadecane 7-Hexylpentadecane 2,2-Dimethyloctane 2,5-Dimethylundecane 5,6-Dibutyldecane 4,5-Diethyloctane 9,10-Dipropyloctadecane 1-Ethyl-3-methylcyclopentane 1,1-Dimethylcyclopentane 1,1,3-Trimethylcyclopentane iso-Butylcyclopentane Methylcyclohexane Ethylcyclohexane 1,2,3-Trimethylcyclohexane tert-Butylcyclohexane n-Butylcyclohexane 1-Methyl-2-propylcyclohexane iso-Butylcyclohexane sec-Butylcyclohexane R s |max| Test set n-Pentane n-Hexane n-Heptane n-Nonane n-Undecane n-Dodecane n-Tridecane n-Tetradecane 30.0 44.8 56.3 73.0 81.1 87.6 90.0 96.1 32.2 45.5 55.7 70.9 82.0 86.6 90.8 94.6 2.2 0.7 0.6 2.1 0.9 1.0 0.8 1.5 R2 s |max|
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Pcalc

|Pexp Pcalc | 0.2 0.0 0.1 0.5 0.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

Hydrocarbon Test set

Pexp

Pcalc

|Pexp Pcalc | 1.4 0.9 0.9 1.0 4.8 1.4 0.6 0.6 0.1 2.5 5.7 6.3 2.1 5.6 2.1 0.8 2.7 4.9 0.0 2.0 1.0 3.5 0.0 4.2 2.0 0.7 1.9 2.1 2.1 2.4 2.3 2.2 1.2 1.5 0.7 0.7 0.9926 2.4948 6.3
2008

63.8 76.9 98.0 105.0 110.0 34.0 53.0 45.0 48.0 83.0 59.0 58.0 29.8 20.0 47.3 21.9 15.0 16.0 47.8 20.0 45.0 29.8 29.9 46.5 58.0 40.0 35.1

64.0 76.9 98.1 104.5 110.2 34.0 53.0 45.0 48.0 83.0 59.0 58.0 29.8 20.0 47.3 21.9 15.0 16.0 47.8 20.0 45.0 29.8 29.9 46.5 58.0 40.0 35.1

n-Hexadecane (cetane) n-Octadecane n-Eicosane 3-Methylpentane 3-Ethyldecane 4-Propyldecane 7-Butyltridecane 9-Methylheptadecane 8-Hexylpentadecane 9-Heptylheptadecane 2,2-Dimethylbutane 2,3-Dimethylbutane 2,4-Dimethylbutane 9,10-Dimethyloctadecane 7,8-Dimethyltetradecane 7,8-Diethyltetradecane 10,13-Dimethyldocosane Cyclopentane Ethylcyclopentane 1,3-Dimethylcyclopentane n-Propylcyclopentane iso-Propylcyclopentane Methylcyclopentane 1,2,4-Trimethylcyclopentane 1,1,2,4-Tetramethylcyclopentane Cyclohexane 1,1-Dimethylcyclohexane 1,2-Dimethylcyclohexane

100.0 108.3 112.0 30.0 47.0 39.5 70.0 66.0 83.0 88.0 24.4 21.0 29.0 59.5 40.5 67.0 56.0 7.0 21.0 16.0 37.0 25.3 13.0 19.0 34.2 15.0 21.0 23.0 23.0 22.7 52.0 41.1 29.0 29.3 30.5 30.5

101.4 107.4 112.9 29.0 42.2 38.1 70.6 65.4 83.1 90.5 30.1 14.7 26.9 53.9 38.4 67.8 58.7 11.9 21.0 14.0 36.0 28.8 13.0 23.2 32.2 14.3 22.9 25.1 25.1 25.1 54.2 38.9 27.8 27.8 29.8 29.8

Statistical characteristics of the model

0.9999 1,3-Dimethylcyclohexane 0.1168 1,4-Dimethylcyclohexane 0.5 n-Propylcyclohexane iso-Propylcyclohexane 1,1,2-Trimethylcyclohexane 1,1,3-Trimethylcyclohexane 1,3,5-Trimethylcyclohexane 1,2,4-Trimethylcyclohexane

Statistical characteristics of the model

Table 3. Prediction of cetane numbers of hydrocarbons with unknown cetane numbers CN Hydrocarbon CN Hydrocarbon CN

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2-Methylhexane 3-Methylhexane Ethylpentane 2,2-Dimethylpentane 3,3-Dimethylpentane 2-Methylheptane 3-Methylheptane 4-Methylheptane Ethylhexane 2,2-Dimethylhexane 2,3-Dimethylhexane 2,4-Dimethylhexane 2,5-Dimethylhexane 3,3-Dimethylhexane 3,4-Dimethylhexane 2-Methyl-3-ethylpentane 3-Methyl-3-ethylpentane 2-Methyloctane 3-Methyloctane 4-Methyloctane 2-Ethylheptane 3-Ethylheptane 2,2-Dimethylheptane 2,3-Dimethylheptane 2,4-Dimethylheptane 1,3-Diethylcyclopentane 1-Methyl-1-isopropylcyclopentane 1-Methyl-2-isopropylcyclopentane 1-Methyl-3-isopropylcyclopentane 1,1,2,2-Tetramethylcyclopentane

35.1 16.7 32.7 35.1 10.3 42.4 26.9 26.9 12.7 42.4 31.1 26.9 42.4 4.9 25.1 12.9 213.3 48.7 35.4 35.4 2.9 2.9 37.2 34.6 30.6 26.8 41.1 38.5 28.1 45.6

2,5-Dimethylheptane 2,6-Dimethylheptane 3,3-Dimethylheptane 3,4-Dimethylheptane 3,5-Dimethylheptane 4,4-Dimethylheptane 2-Methyl-3-ethylhexane 2-Methyl-4-ethylhexane 3-Methyl-3-ethylhexane 3-Methyl-4-ethylhexane 2-Methylnonane 3-Methylnonane 4-Methylnonane 5-Methylnonane 2-Ethyloctane 3-Ethyloctane n-Propylheptane 2,2-Dimethyloctane 2,3-Dimethyloctane 2,4-Dimethyloctane 2,5-Dimethyloctane 2,6-Dimethyloctane 3,3-Dimethyloctane 3,4-Dimethyloctane 3,5-Dimethyloctane 1-Methyl-2-sec-butylcyclopentane 1-Methyl-1-isobutylcyclopentane 1-Methyl-1-sec-butylcyclopentane Neopentylcyclopentane (1,1-Dimethylpropyl)cyclopentane

30.6 32.6 17.1 33.9 17.1 17.1 23.7 2.9 146.1 16.8 54.2 42.6 42.6 42.6 15.5 15.5 15.5 37.8 38.6 38.6 23.9 47.8 8.4 37.2 21.6 53.7 49.4 46.5 58.9 54.9

3,6-Dimethyloctane 4,4-Dimethyloctane 4,5-Dimethyloctane 2-Methyl-3-ethylheptane 3-Methyl-3-ethylheptane 2-Methyl-4-ethylheptane 3-Methyl-4-ethylheptane 2-Methyl-5-ethylheptane 3-Methyl-5-ethylheptane 4-Methyl-5-ethylheptane 4-Methyl-4-ethylheptane 4-Isopropylheptane 3,4-Diethylpentane 1,2-Dimethylcyclopentane 1-Methyl-1-ethylcyclopentane 1-Methyl-2-ethylcyclopentane 1,1,2-Trimethylcyclopentane 1,2,3-Trimethylcyclopentane n-Butylcyclopentane sec-Butylcyclopentane tert-Butylcyclopentane 1-Methyl-1-propylcyclopentane 1-Methyl-2-propylcyclopentane 1,1-Diethylcyclopentane 1,2-Diethylcyclopentane 1,3,4-Trimethyl-4-ethylcyclopentane 1,2,3-Trimethyl-2-ethylcyclopentane 1,2,4-Trimethyl-4-ethylcyclopentane 1,2,2-Trimethyl-3-ethylcyclopentane 1,3,3-Trimethyl-4-ethylcyclopentane

15.4 27.2 41.3 27.7 97.0 8.6 26.9 0.7 12.2 26.9 97.0 32.7 7.0 21.3 28.8 30.0 31.4 31.9 35.6 45.6 34.8 42.9 43.8 43.4 37.3 46.3 60.1 37.1 53.9 41.6

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Table 3. (Contd.) CN Hydrocarbon CN Hydrocarbon CN

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Hydrocarbon

LAPIDUS et al.

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1,1,3,3-Tetramethylcyclopentane 1,1,2,3-Tetramethylcyclopentane 1,2,2,3-Tetramethylcyclopentane 1,1,3,4-Tetramethylcyclopentane 1,2,3,4-Tetramethylcyclopentane Pentylcyclopentane 1-Methyl-1-butylcyclopentane 1-Methyl-2-butylcyclopentane 1-Methyl-3-butylcyclopentane (3-Methylbutyl)cyclopentane (2-Methylbutyl)cyclopentane (1-Methylbutyl)cyclopentane 1-Ethyl-1-propylcyclopentane 1-Ethyl-2-propylcyclopentane 1-Ethyl-3-propylcyclopentane (1-Ethylpropyl)cyclopentane 1,1-Dimethyl-2-propylcyclopentane 1,1-Dimethyl-3-propylcyclopentane 1,3-Dimethyl-1-propylcyclopentane 1,2-Dimethyl-1-propylcyclopentane 1-Methyl-2-isobutylcyclopentane 1-Methyl-3-isobutylcyclopentane 1-Methyl-3-sec-butylcyclopentane 1,4-Dimethyl-4-ethylcyclohexane 1,2-Dimethyl-3-ethylcyclohexane 1,3-Dimethyl-4-ethylcyclohexane 1,3-Dimethyl-2-ethylcyclohexane 1,4-Dimethyl-2-ethylcyclohexane 1,1,3,4-Tetramethylcyclohexane 1,1,3,5-Tetramethylcyclohexane

20.2 42.2 47.2 25.7 40.6 35.6 42.9 43.8 36.8 36.2 50.6 45.6 54.1 49.4 41.4 60.2 51.9 39.0 55.7 43.9 54.8 49.4 46.5 49.7 44.7 44.7 50.8 57.6 32.3 32.3

(1,2-Dimethylpropyl)cyclopentane 1,2-Dimethyl-3-propylcyclopentane 1,3-Dimethyl-4-propylcyclopentane 1,3-Dimethyl-2-propylcyclopentane 1,2-Dimethyl-4-propylcyclopentane 1-Methyl-2,2-diethylcyclopentane 1-Methyl-3,3-diethylcyclopentane 1-Methyl-1,2-diethylcyclopentane 1-Methyl-1,3-diethylcyclopentane 1-Methyl-2,3-diethylcyclopentane 1-Methyl-2,4-diethylcyclopentane 1-Methyl-2,5-diethylcyclopentane 1-Methyl-3,4-diethylcyclopentane 1-Methyl-1-tert-butylcyclopentane 1-Methyl-2-tert-butylcyclopentane 1-Methyl-3-tert-butylcyclopentane 1,2-Dimethyl-1-isopropylcyclopentane 1,3-Dimethyl-1-isopropylcyclopentane 1,1-Dimethyl-2-isopropylcyclopentane 1,1-Dimethyl-3-isopropylcyclopentane 1,2-Dimethyl-3-isopropylcyclopentane 1,3-Dimethyl-4-isopropylcyclopentane 1,3-Dimethyl-2-isopropylcyclopentane 1,2-Dimethyl-4-isopropylcyclopentane 1,1,2-Trimethyl-2-ethylcyclopentane 1,1,3-Trimethyl-3-ethylcyclopentane 1,2,3-Trimethyl-3-ethylcyclopentane 1,3-Dimethyl-5-ethylcyclohexane 1,2,3,4-Tetramethylcyclohexane 1,2,3,5-Tetramethylcyclohexane

59.6 50.7 44.7 52.2 42.9 58.7 44.4 52.3 35.3 47.0 36.4 45.2 38.5 52.1 46.6 35.9 57.1 42.2 49.2 30.8 46.2 39.5 49.5 35.3 58.9 32.7 53.5 63.5 34.0 14.1

1,1,3-Trimethyl-2-ethylcyclopentane 1,1,2-Trimethyl-3-ethylcyclopentane 1,1,2-Trimethyl-4-ethylcyclopentane 1,1,3-Trimethyl-4-ethylcyclopentane 1,2,3-Trimethyl-4-ethylcyclopentane 1,2,4-Trimethyl-3-ethylcyclopentane 1-Methyl-1-ethylcyclohexane 1-Methyl-2-ethylcyclohexane 1-Methyl-3-ethylcyclohexane 1-Methyl-4-ethylcyclohexane 1,1,4-Trimethylcyclohexane 1-Methyl-1-propylcyclohexane 1-Methyl-3-propylcyclohexane 1-Methyl-4-propylcyclohexane 1,1-Diethylcyclohexane 1,2-Diethylcyclohexane 1,3-Diethylcyclohexane 1,4-Diethylcyclohexane 1,1-Dimethyl-2-ethylcyclohexane 1,1-Dimethyl-3-ethylcyclohexane 1,1-Dimethyl-4-ethylcyclohexane 1,2-Dimethyl-2-ethylcyclohexane 1,3-Dimethyl-3-ethylcyclohexane 1,2-Dimethyl-4-ethylcyclohexane 1,1,2,2-Tetramethylcyclohexane 1,1,2,3-Tetramethylcyclohexane 1,2,2,4-Tetramethylcyclohexane 1,2,2,3-Tetramethylcyclohexane 1,2,4,5-Tetramethylcyclohexane

51.2 48.0 37.6 33.7 46.6 48.3 46.5 47.8 47.8 47.8 27.7 66.8 56.2 67.6 62.2 63.1 63.1 63.1 49.7 49.7 49.7 43.3 49.7 50.8 30.5 32.3 32.3 32.3 34.0

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CETANE NUMBERS OF HYDROCARBONS CN(exp) 120 110 100 90 80 70 60 50 40 30 20 10 0 10 20 30 40 50 60 70 80 90 100 110 120 CN(calc) 1 2

155

las derived in this work can be used for predicting the CN values for unstudied and as yet unsynthesized compounds. Thus, we can conclude that we solved the practical structureproperty relationship problem for one of the most important characteristics of diesel oils. ACKNOWLEDGMENTS This work was supported by the Council for Grants of the President of the Russian Federation for Support of Leading Scientic Schools (grant no. NSh 9071.2006.3). REFERENCES
1. Smolenskii, E.A., Ryzhov, A.N., Bavykin, V.M., Chuvaeva, I.V., and Lapidus, A.L., Dokl. Chem., 2007, vol. 417, part 1, pp. 267272 [Dokl. Akad. Nauk, 2007, vol. 417, no. 3, pp. 347352]. 2. Randic, M., J. Chem. Inf. Comput. Sci., 1997, vol. 37, no. 4, pp. 672685. 3. Sidorova, A.V., Baskin, I.I., Petelin, D.E., Palyulin, V.A., and Zerov, N.S., Dokl. Chem., 1996, vol. 350, nos. 46, pp. 254258 [Dokl. Akad. Nauk, 1996, vol. 350, no. 5, pp. 642646]. 4. Smolenskii, E.A., Vlasova, G.V., and Lapidus, A.L., Dokl. Phys. Chem., 2004, vol. 397, part 1, pp. 145149 [Dokl. Akad. Nauk, 2004, vol. 397, no. 2, pp. 219223]. 5. Balaban, A.T., J. Chem. Inf. Comput. Sci., 1985, vol. 25, no. 3, pp. 334343. 6. Smolenskii, E.A., Ryzhov, A.N., Bavykin, V.M., et al., Izv. Akad. Nauk, Ser. Khim., 2007, no. 9, pp. 16191631. 7. Smolenskii, E.A., Izv. Akad. Nauk, Ser. Khim., 2006, no. 9, pp. 14481453. 8. Smolenskii, E.A., Vlasova, G.V., Platunov, D.Yu., and Ryzhov, A.N., Izv. Akad. Nauk, Ser. Khim., 2006, no. 9, pp. 14541461.

Fig. 3. Extrapolation model of the cetane numbers of saturated hydrocarbons: (1) training and (2) test sets.

Table 2 also presents the results of interpolation by this model for the training set and those of extrapolation for the test set. The results of our calculations are shown graphically in Fig. 3. With the use of this model, we calculated the CN values for 180 hydrocarbons with n 10 that have not been synthesized thus far or for which CNs are unknown. The calculation results are summarized in Table 3. Although the results for the training set R2 = 0.9999 (Table 2) surpass those for the test set R2 = 0.9926 in accuracy, the difference is small; therefore, the formu-

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