Degree: Habilitation

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Affiliation(s):

FCUP

Bio

Maria D. M. C. Ribeiro da Silva. Completed the Habilitation in Chemistry in 2001, from the University of Porto (Faculty of Sciences), the PhD in Chemistry in 1985, from the University of Porto (Faculty of Sciences), the Degree in Chemistry in 1976, from the University of Porto (Faculty of Sciences ) and a Bachelor's degree in Chemistry in 1974, from the University of Porto (Faculty of Sciences).

Associate Professor (1993-2023) in the Department of Chemistry and Biochemistry, Faculty of Science, University of Porto (FCUP). Invited Associate Professor (2024-)

Vice-President of Department of Chemistry, FCUP (2002-2003). Head of the Committees for M.Sc. Degrees in Chemistry and in Chemical Education (1997 – 2005) and Director of the 2nd Cycle of Studies in Chem. (Bologne System) since 2007 until January 2018. Since 2009 until September/2017, she has been the Coordinator of Erasmus Mundus SERP Chem in UP. She was nominated as the Portuguese Chemistry Mentor for EU Science Olympiads (2009-2017) and President of the XXIV Ibero-American Chemistry Olympiad in Portugal (2019). She was member of the Coordinator Council of Junior University ( UP; 2008-2023.). She was Member of the Representatives Council in FCUP (2018-2023). Conference Chair and Organizer of MEDICTA 2023 (16th Mediterranean Conference on Calorimetry and Thermal Analysis, Porto, Portugal, 2023) and 11ENQF (11º National Physical Chemistry Meeting, Porto, Portugal, 2011). Organizer of Porto Summer School on Calorimetry and Thermal Analysis (Porto, Portugal, 2023).

She develops her work in the area of Exact Sciences, with an emphasis on the area of Physical Chemistry (Thermochemistry and Molecular Energetics).

Author of ~210 publications in international journals, 3 book chapters,  and co-author in several manuals for laboratorial activities. Supervisor or co-Supervisor of 11 Ph.D. theses (10 completed), 21 M.Sc theses. and 51 B.Sc. theses in Chemistry. Supervisor of 10 Pos-Doctoral Projects. Member of the scientific team of several research projects awarded by national or international funding agencies (coordinator of two projects).

Scientific Interests: Molecular energetics of oxygen/nitrogen/sulphur heteropolycyclic compounds; Energetics of N-oxide nitrogen heterocyclic derivatives; Energetics of organic compounds (basic structures for larger molecules); Energetics of the metal-ligand bonds in organometallic compounds.

Techniques expertise: Combustion Calorimetry/ DSC/ Calvet Microcalorimetry/ Reaction-Solution/Calorimetry/Knudsen-effusion techniques.

Publications
Showing 5 latest publications. Total publications: 212
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1. Thermochemistry of amino-1,2,4-triazole derivatives, Amaral, LMPF; Carvalho, TMT; da Silva, MDMCR in JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, 2024, ISSN: 1388-6150, 
Article in Press,  Indexed in: crossref, scopus, wos  DOI: 10.1007/s10973-024-13161-0 P-010-C6E
Abstract The present work is focused on determining the enthalpy of formation of several derivatives of amino-1,2,4-triazoles. Experimentally, the enthalpies of formation of the crystalline phase and the enthalpies of sublimation of 3-amino- and 3,5-diamino-1H-1,2,4-triazole were derived, respectively, from static-bomb combustion calorimetry and Calvet microcalorimetry or Knudsen effusion measurements. For 4-amino-4H-1,2,4-triazole, only the enthalpy of sublimation was measured. Gas-phase standard molar enthalpies of formation were also estimated using theoretical calculations performed with the G3(MP2) composite approach. The very good agreement of these estimates with the experimental results, support the extension of this study to the estimate of this property for the remaining compounds not studied experimentally. The results obtained are interpreted in terms of structural contributions.
2. Phase transition study of bathophenanthroline and bathocuproine: A multitechnique approach, Ferraz, JMS; Romagnoli, L; Brunetti, B; Ciccioli, A; Ciprioti, SV; Freitas, VLS; da Silva, MDMCR in JOURNAL OF CHEMICAL THERMODYNAMICS, 2024, ISSN: 0021-9614,  Volume: 198, 
Article,  Indexed in: crossref, scopus, wos  DOI: 10.1016/j.jct.2024.107346 P-010-QH9
Abstract The thermal behaviour of bathophenanthroline and bathocuproine has been studied using several techniques, namely, differential scanning calorimetry and thermogravimetry. To determine their respective enthalpies of sublimation, vapor pressure measurements were carried out using different methods, such as Knudsen effusion mass loss/mass spectrometry, isothermal thermogravimetry, and a quartz crystal microbalance technique. Furthermore, the enthalpies of sublimation were determined by measuring the heat change of the sublimation process using high-temperature Calvet microcalorimetry. The results obtained in this work allowed the determination of the standard molar enthalpies of sublimation at 298.15 K, for bathophenanthroline and bathocuproine. The values obtained were (183.8 +/- 2.2) kJ & sdot;mol- 1 and (206.2 +/- 2.8) kJ & sdot;mol- 1, respectively. Additionally, the standard molar enthalpies of fusion were determined to be (30.4 +/- 0.4) kJ & sdot;mol- 1 and (26.5 +/- 1.6) kJ & sdot;mol- 1 for bathophenanthroline and bathocuproine, respectively. The analysis of the results allows a deeper understanding of the phase transition behavior for these compounds from the condensed to the gaseous phases, elucidating molecular decomposition and the inherent intermolecular forces governing the species.
3. Thermodynamic Properties of Two Cinnamate Derivatives with Flavor and Fragrance Features, Freitas, VL; Silva, CAO; Ribeiro da Silva, MD 2024,
Unpublished,  Indexed in: crossref  DOI: 10.20944/preprints202409.1831.v1 P-017-1SC
Abstract <jats:p>The standard molar enthalpies of formation in the liquid phase for ethyl (E)-cinnamate and ethyl hydrocinnamate, two cinnamate derivatives with notable flavor and fragrance characteristics, were determined experimentally using combustion calorimetry in an oxygen atmosphere. To derive the gas-phase enthalpies of formation for these derivatives, their enthalpies of vaporization were measured using a high-temperature Calvet microcalorimeter and the vacuum drop micro-calorimetric technique. Additionally, a computational analysis employing the G3(MP2)//B3LYP composite method was conducted to calculate the gas-phase standard enthalpies of formation at T = 298.15 K for both compounds. These findings enabled a detailed assessment and analysis of the structural and energetic effects of the vinyl and ethane moieties between the phenyl and carboxylic groups in the studied com-pounds. Considering the structural features of ethyl (E)-cinnamate and ethyl hydrocinnamate, a gas-phase enthalpy of hydrogenation analysis was conducted to explore their energetic profiles more thoroughly.</jats:p>
4. Thermodynamic study of tin tetraiodide (SnI4) 4 ) sublimation by effusion techniques, Romagnoli, L; Almeida, ARRP; Ferraz, JMS; Latini, A; Freitas, VLS; da Silva, MDMCR Schiavi, PG; Ciprioti, SV; Ciccioli, A in JOURNAL OF CHEMICAL THERMODYNAMICS, 2024, ISSN: 0021-9614,  Volume: 199, 
Article,  Indexed in: crossref, scopus, wos  DOI: 10.1016/j.jct.2024.107348 P-011-0HK
Abstract This study presents the first investigation of the sublimation behavior of tin tetraiodide, SnI4, 4 , using effusion- based techniques, within a low temperature range (313-340) K. The temperature range covered in the experiments was lower than in previously reported studies based on static methods. Knudsen Effusion Mass Loss (KEML) measurements were performed in the range of (317.1-339.6) K using effusion cells with different orifice sizes. The vapor pressures were measured in the range (0.13-1.13) Pa and were found to be independent of the orifice size. The standard molar enthalpy and Gibbs energy of sublimation at 298.15 K obtained by the Clarke and Glew fit of experimental data are (88.1 +/- 0.9) kJ & sdot;mol-1 & sdot; mol- 1 and (38.96 +/- 0.08) kJ & sdot;mol-1, & sdot; mol- 1 , respectively. Knudsen Effusion Mass Spectrometry (KEMS) experiments were also performed in the range (313.3-331.7) K, resulting in a sublimation enthalpy value in good agreement with the KEML values and not negligibly higher vapor pressure values. KEMS vapor pressure data were also analyzed by the third-law method. A comparison of our experimental results with the literature data available for both sublimation and evaporation properties of SnI4 4 is reported. Additionally, ancillary DFT and ab initio calculations were performed to estimate the molecular properties of SnI4(g) 4 (g) and the extent of the gas-phase dissociation to SnI2 2 and I2. 2 .
5. Determination and Analysis of Thermodynamic Properties of Methyl Methylanthranilate Isomers, Silva, CAO; Freitas, VLS; da Silva, MDMCR in MOLECULES, 2023, ISSN: 1420-3049,  Volume: 28, 
Article,  Indexed in: crossref, scopus, wos  DOI: 10.3390/molecules28186686 P-00Z-21V
Abstract The enthalpies of formation in the gaseous phase of methyl 3-methylanthranilate and methyl 5-methylanthranilate were determined from experimental measurements of the corresponding standard energies of combustion, obtained from combustion calorimetry, and the standard enthalpies of vaporization and sublimation, obtained from Calvet microcalorimetry and Knudsen mass-loss effusion. A computational study, using the G3(MP2)//B3LYP composite method, has also been performed for the calculation of the gas-phase standard enthalpies of formation of those two molecules at T = 298.15 K, as well as for the remaining isomers, methyl 4-methylanthranilate and methyl 6-methylanthranilate. The results have been used to evaluate and analyze the energetic effect of the methyl substituent in different positions of the ring.