Thermochemistry and Molecular Energetics

Code:

Q4017

Acronym:

Q4017

Level:

400

Keywords
Classification	Keyword
OFICIAL	Chemistry

Instance: 2017/2018 - 2S

Active?	Yes
Responsible unit:	Department of Chemistry and Biochemistry
Course/CS Responsible:	Master in Chemistry

Cycles of Study/Courses

Acronym	No. of Students	Study Plan	Curricular Years	Credits UCN	Credits ECTS	Contact hours	Total Time
M:Q	10	Official study plan until 2022/2023	1	-	6	56	162

Teaching language

Português

Objectives

This course deals with the application of Thermochemistry to the study of molecular energetics and the thermodynamic stability of the molecules. This implies the study of the techniques and methods used in Thermochemistry and Thermophysics as well as the consideration of the applications of the experimental results to chemical problems, mainly to the relations of the energetics of the chemical bonds with the structural and reactivity properties of chemical compounds. The impact and relevance of these aspects and their applications in Chemistry, Chemical Industry, Life Sciences and Environmental Chemistry, etc., are presented and discussed.

Learning outcomes and competences

At the end of this course the students should:

-Recognize the importance of the energetic characterization of molecules in chemistry in general, from the academic and applied points of view. 

- Select "key" compounds for the establishment of energetic-structural correlations.

- Know how to discuss the impact that this Physical Chemistry area has in terms of the information available for the definition of strategies in studies of reactivity.

To recognize the fundamental role of calorimetry in the characterization of proteins, membranes, surfactant aggregation, thermodynamic characterization of complexation reactions

Working method

Presencial

Pre-requirements (prior knowledge) and co-requirements (common knowledge)

Basic background on Chemical Thermodynamics.

Program

Theoretical classes

CHAPTER 1 – THERMODYNAMIC BACKGROUND General considerations about the principles of thermodynamics. Reaction and phase transition enthalpies. Standard and reference states. Dependence of enthalpy with temperature. Standard training enthalpies. Gibbs energy and equilibrium constant. Calorimetric and non-calorimetric methods for enthalpy determination. Conventions for the presentation of uncertainties in Chemical Thermodynamics.

CHAPTER 2: FUNDAMENTALS OF CALORIMETRY Calorimetry: General. Measurement of temperature gradient and heat transfer.Calorimetric techniques: fundaments and applications. More recent developments in methodologies related to calorimetry

CHAPTER 3: EXPERIMENTAL ASPECTS OF THE MEASURING OF ENTHALPIES OF REACTIONExperimental techniques and methods for the determination of enthalpies of reaction. Combustion calorimetry, isoperibol reaction-solution calorimetry, heat flow calorimetry, photocalorimetry, titration calorimetry, photoacoustic calorimetry. Considerations regarding the choice of the experimental methodology.

CHAPTER 4: ENTHALPIES OF PHASE-TRANSITION: FUSION, VAPORIZATION AND SUBLIMATION Importance of the knowledge of enthalpies of fusion, vaporization and sublimation. Theoretical aspects of the determination of enthalpies of vaporization of organic liquids. Direct and indirect methods. Methods of estimation of enthalpies of sublimation of organic solids.

CHAPTER 5: MOLECULAR THERMOCHEMISTRY Thermochemistry of organic, inorganic and organometallic compounds. Thermodynamic data as a framework to discuss molecular stability. Correlations between the energy of chemical bonds and the structural and reactivity properties of the molecules.

CHAPTER 6: PREDICTING ENTHALPIES OF FORMATION OF ORGANIC COMPOUNDS The practical application of thermochemical data in Science and Technology. Methods of estimation of enthalpies of reaction. Bond energy terms. Modern bond energy schemes. Estimation of energetic properties using thermochemical group increments models or molecular mechanics calculations. Use and relevance of computational chemistry on thermochemical studies.

CHAPTER 7. Isothermal titration calorimetry. Titration curves and (i) thermodynamic parameters of complexation reactions derived from them; (ii) Characterization of surfactant aggregation; (iii) partition of solutes for membranes.

CHAPTER 8. Differential Scanning Calorimetry. Analysis of thermal behavior of materials: phase transitions, heat capacities, thermal stability. (i) fusion; (ii) crystallization; (iii) glass transition; (iv) protein denaturation; (V) phase characterization of lipid systems.

 

 

Practical classes

 Resolution/discussion of some questions related to the theoretical contents. Oral presentations. Whenever possible, practical laboratory works will be done or presented.

Mandatory literature

José A. Martinho Simões, Manuel E. Minas da Piedade; Molecular Energetics. Condensed-Phase Thermochemical Techniques, Oxford University Press (2008)
J. D. Cox, G. Pilcher, Thermochemistry of Organic and Organometallic Compounds, Academic Press, London (1970)
W. Hemminger, G. Hohne, Calorimetry, Fundamentals and Practice, Verlag Chemie, Weinheim (1984)
M. Bastos (ed); Biocalorimetry: Foundations and Contemporary Approaches, CRC Press, Taylor & Francis Group, Boca Raton, 2016. ISBN: 978-1-4822-4665-0.

Teaching methods and learning activities

In the theoretical lectures the contents of the curricular unit are presented, encouraging theactive participation ofstudents. Digital educational resourceswill be usedwhere appropriateto a better understandingof the studied topics. Inpractical classes, the students should/can/must use the theoretical fundamentalsto solve practical problems, as well as performing laboratory work involving specific techniquesto thisfield.Theclassesalso includethe developmentof acurrent topic, which will be presentedorally.

keywords

Physical sciences

Evaluation Type

Distributed evaluation with final exam

Assessment Components

designation	Weight (%)
Exame	40,00
Trabalho laboratorial	60,00
Total:	100,00

Eligibility for exams

The attendance of the practical classes (P), including laboratories and problem-solving, is compulsory.

The maximum number of absences from P classes is 1/4 of the foreseen P classes.

Calculation formula of final grade

Evaluation: Distributed evaluation with final exam.