Anlise do Petrleo

Anlise de Dados em PetrolemicaGssica VasconcelosOrientador: Boniek G. Vaz

PetrolemicaPetroleomics is the principle that from sufficiently complete characterization of the organic composition of petroleum and its relatives and products, it should be possible to correlate (an ultimately predict) their properties and behavior

Petrolemica a caraterizao do petrleo a nvel molecular.Composio do Petrleo

VAZ, Boniek Gontijo. Petrolemica por FT-ICR MS: desvendando a composio de polares do petrleo e derivados. Tese de Doutorado. Curso de Ps-graduao em Qumica, Instituto de Qumica, Unicamp, Campinas, 5p, 2011.Composio Elementar do Petrleo

THOMAS, J. E. Fundamentos de Engenharia do Petrleo. Editora Intercincia. Rio de Janeiro, 2001.

Fontes de Ionizao

Espectro de Massas do Petrleo

Because the organic composition ofpetroleum is so complex, its characterization was until recentlylimited to bulk properties (e.g., density, viscosity, osmotic pressure,light scattering, UV-visible and infrared spectroscopy,NMR, x-ray scattering, and absorption-edge spectroscopy)

Figura 1: Espectro de Massas de um leo cru europeu obtido por ESI (+) 9,4 T FT-ICR MS.Marshall, A. G.; Rodgers, R. P. Petroleomics: Chemistry of the underworld. PNAS, 2008. v. 105, pp. 18090-18095.

8000 picos resolvedFalar de EIFalar de FT ICR MS Como era feita a caracterizacoPq se usar FT MSFourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) offers the highest available broadband massresolution, mass resolving power, and mass accuracy

6Sries Homlogas-CH2, -COOH, -CH2O, -NH2

Fortunately, petroleum and its derivatives typically consist primarily of homologous series. Each homologous series is categorized by heteroatom class (NnOoSs), double bond equivalents (DBE) (see Eq. 1), and carbon numberThus, compoundswhose compositions differ by masses associated with astructural unit 7Sries Homlogas

Distribuio de ClassesC42H53NC36H74NC59 H67NFigura 2: Grfico de distribuio de classes de compostos com mesmo (NnSsOo)

Marshall, A. G.; Rodgers, R. P. Petroleomics: Chemistry of the underworld. PNAS, 2008. v. 105, pp. 18090-18095.

Double Bound Equivalent (DBE)C42H59N1C42H53N1DBE=14DBE=17

Figura 3: Representao da distrubio de DBE para a classe.Marshall, A. G.; Rodgers, R. P. Petroleomics: Chemistry of the underworld. PNAS, 2008. v. 105, pp. 18090-18095.

DBE vs. Nmero de Carbono

Marshall, A. G.; Rodgers, R. P. Petroleomics: Chemistry of the Underworld. PNAS, 2008. v. 105, pp. 18090-18095.

Figura 4: Representao grfica do DBE vs. nmero de Carbono para a frao 375-400C do betume de Athabasca usando ESI (-) 9.4 T FT-ICR MS Exemplo

McKenna, A. M.; Blakney, G. T.; Xian, F.; Glaser, P. B.; Rodgers, R. P.; Marshall, A. G. Heavy Petroleum Composition. 2. Progression of the Boduszynski Model to the Limit of Distillation by Ultrahigh-Resolution FT-ICR Mass Spectrometry. Energy Fuels, 2010. v. 24, pp. 29392946.

ExemploFigura 5: Representao grfica do DBE vs. Nmero de Carbono para a classe S1de uma frao pesada do leo cru Oriente MdioMcKenna, A. M.; Blakney, G. T.; Xian, F.; Glaser, P. B.; Rodgers, R. P.; Marshall, A. G. Heavy Petroleum Composition. 2. Progression of the Boduszynski Model to the Limit of Distillation by Ultrahigh-Resolution FT-ICR Mass Spectrometry. Energy Fuels, 2010. v. 24, pp. 29392946.Defeito de Massahomologous series of molecules of the sameheteroatom class and DBE, but a varying degree of alkylationMembers of that series will vary in composition by multiples of-CH2, corresponding to multiples in mass of 14.0565 Da. A particularlyuseful way to identify such a series is to convert the Syste`meinternational dunites (SI) mass to Kendrick mass (20):Kendrick mass SI mass (14.00000/14.0565).

Kendrick mass defect = nominal Kendrick mass - Kendrick mass

SubstnciaMassa monoisotpica (uma)CH3CH2CH2CH358.078250

CH3CH2CH2CH2CH372.093899CH3CH2CH2CH2CH2CH386.109550CH3CH2CH2CH2CH2CH2CH3100.125199

tomoMassa monoisotpica1H1.00782512C12.0000014N14.00307416O15.99491531P30.97376332S31.972072Marshall, A. G.; Rodgers, R. P. Petroleomics: Chemistry of the underworld. PNAS, 2008. v. 105, pp. 18090-18095.

Figura 6: Representao grfica do defeito de massa para alguns istopos da tabela peridica.Atomic mass defects for selected isotopes of some common chemicalelements. Because no two have the same mass defect, it is possible to determinea unique elemental composition for any molecule from a sufficientlyaccurate mass measurement.

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Defeito de Massa

Marshall, A. G.; Rodgers, R. P. Petroleomics: The Next Grand Challenge for Chemical Analysis. Acc. Chem. Res., 2004. v. 37, pp. 53-59.Figura 7: Amplificao de um espectro de massas demonstrando a variao de massa de um leo cru da Amrica do Sul. Kendrick Mass-CH2 = 14.00000

Kendrick Mass Defect (KMD) = Nominal Kendrick Mass - Kendrick Exact MassonIUPAC MassExact Kendrick mass[C23H43O2]-

351.32685350.93456onMassa NominalKMD[C23H43O2]-

3510.6544KMD = 351 - 350.93456 = 0,6544-CH2 = 14.01565

Kendrick Mass Plot

Figura 8: Representao grfica do Kendrick Mass Defect vs. valor nominal Kendrick Mass.

Wu, Z.; JernstrOm, S.; Hughey, C.A.; Rodgers, R. P.; Marshall*, A.G. Resolution of 10 000 Compositionally Distinct Components in Polar Coal Extracts by Negative-Ion Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Energy & Fuels, 2003. v. 17, pp. 946-953.van Krevelen Plot

Marshall, A. G.; Rodgers, R. P. Petroleomics: Chemistry of the underworld. PNAS, 2008. v. 105, pp. 18090-18095.

18Obrigada!