Physical Chemistry

Code:

Q223

Acronym:

Q223

Keywords
Classification	Keyword
OFICIAL	Chemistry

Instance: 2010/2011 - 1S

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

Cycles of Study/Courses

Acronym	No. of Students	Study Plan	Curricular Years	Credits UCN	Credits ECTS	Contact hours	Total Time
L:Q	112	Plano de estudos Oficial	2	-	7,5	-

Teaching language

Portuguese

Objectives

The aim of this course is to teach some fundamental topics of Physical Chemistry, following the basic knowledge that the student should have acquired during the past academic year in the course of Fundamentos de Química. The actual syllabus adopted for the Licentiate Chemistry Degree has only a compulsory semester of Physical Chemistry, which is clearly very short as so compels the choice of only some fundamental topics of this branch of Chemistry, even so with a quite superficial treatment, with the loss of other fundamental topics that have no time to be introduced. So, the following topics have been selected for the contents of the Physical Chemistry course: Chemical Thermodynamics (in view of its fundamental character and applicability on the study of many other topics), Chemical Kinetics (due to its importance on the understanding of the mechanisms of the chemical processes) and an Introduction to the Chemistry of Surfaces.

Program

1 – FUNDAMENTAL CONCEPTS
Thermodynamics: Nature and Applicability. Macroscopic variables: Independent variables and dependent variables. Condition to choose de variables of a system.

2 – THE ZEROTH LAW
Empirical concept of Thermal State. Thermal permeable walls and thermal impermeable walls Statement of the Zeroth Law of Thermodynamics. Definition of the temperature concept. Definition of the International System unit of temperature: Kelvin. Scales of temperature. The temperature fixed points.

3 - THE FIRST LAW OF THERMODYNAMICS: PRINCIPLE OF CONSERVATION OF ENERGY
Statement of the First Law of Thermodynamics. Energy, heat and work.
The Enthalpy Function.
Heat of reaction and thermal coefficients in the variables temperature, volume and composition: heat capacity at constant pressure and composition; heat capacity at constant volume and composition; heat of expansion at constant temperature and composition; heat of reaction at constant temperature and volume.
Heat of reaction and thermal coefficients in the variables temperature, pressure and composition: heat capacity at constant pressure and composition; heat of compression at constant temperature and composition; heat of reaction at constant temperature and pressure.
Relations between thermal coefficients. Clausius and Kirchhoff relations.
Thermochemistry and its Laws. Combustion and Reaction- solution calorimetry.

4 - THE SECOND LAW OF THERMODYNAMICS: PRINCIPLE OF THE CREATION OF ENTROPY
Equilibrium and Potential. Reversible and irreversible phenomena: reversibility conditions.
Statement of the Second Law of Thermodynamics. Thermodynamic potentials. Equilibrium conditions. Affinity of reaction.

5 – APPLICATIONS OF THE SECOND LAW OF THERMODYNAMICS
Affinity and Thermodynamic Potentials. Gibbs-Helmholtz equations.
The Maxwell relations. De Donder relations.
Thermodynamic potentials and chemical potentials.
Physical significance of chemical potential: pure substance, component of a mixture. Gibbs-Duhem equation.
Chemical potential and phases equilibrium. Phase diagrams. The Clausius-Clapeyron Equation.
The Gibbs-Helmholtz Equation.

6 – CHEMICAL TRANSFORMATIONS: SOME APPLICATIONS OF THE CHEMICAL POTENTIAL TO CHEMICAL REACTIONS
Applications of chemical potentials to chemical reactions: The Law of Mass Action. The ideal gases: equilibrium constant in terms of its equilibrium partial pressure and of equilibrium molar fractions. Le Chatelier-Van't Hoff' Principle. The real gases: equilibrium constant in terms of fugacity. Ideal solutions and non-ideal solutions. Heterogeneous reactions.

7 – THE THIRD LAW OF THERMODYNAMICS AND THE ABSOLUTE ENTROPY
Statement and interpretation of the Law; absolute entropies and entropies change
The calculation of entropy changes.
Calculation of absolute entropies.

8 – CHEMICAL KINETICS
Revision of the basic concepts.
Experimental methods in chemical kinetics studies and treatment of data.
Determination of the rate constants.
Complex kinetic systems. Classification of Complex Kinetic Systems.
Reverse Reactions. Consecutive reactions.
The Steady-state approximation. Chain reactions: formulation of the approximation; working procedure. Catalysis. Industrial importance of the catalysers. Homogeneous, heterogeneous and enzimatic catalysis.

9- PHYSICAL CHEMISTRY OF SURFACES
Surface tension. Pressure difference through the surface of a liquid drop: Laplace equation
Capillary rising up and capillary depression: establishment of the relevant equations.
Vapour pressure inside small liquid bubbles. Influence of the temperature on the surface tension.
Thermodynamic of Adsorption: fundaments. Adsorption on solid surfaces. Physical adsorption and chemical adsorption: mechanisms, characteristics and properties. Gibbs and Langmuir adsorption isothermals.

Mandatory literature

P. Atkins; Physical Chemistry, Oxford University Press, 2003
I. N. Levine; Physical Chemistry, McGraw Hill, , 2002
A. A. Frost and R. G. Pearson; Kinetics and Mechanisms, Wiley International Edition, , 1961
D. J. Shaw; Introduction to Colloid and Surface Chemistry, Butterwords, 1986

Evaluation Type

Assessment Components

Description	Type	Time (hours)	Weight (%)	End date
Attendance (estimated)	Participação presencial	70,00
	Total:	-	0,00

Eligibility for exams

The attendance of the problem-solving (PS) classes is compulsory.
The maximum number of absences from TP classes is 1/4 of the foreseen TP classes

Calculation formula of final grade

A- Continuous assessment
i) There will be two tests (T1, T2) during the semester that will take place within the classes, which will give the student the right of excuse of the final examination if the average of both tests will be positive (at least 10 in the score of 0 to 20).

ii) Assessment of the participation of the student in the lectures and problem-solving classes (attendance and participation during the classes, PIA)

Final mark of the continuous assessment: 0,45 T1 + 0,45 T2 + 0,10 PIA

or

B- Final examination



Final marks higher than 18 (scale of 0 to 20) may require a complementary oral test

Examinations or Special Assignments

Two tests (T1, T2) during the semester.

Special assessment (TE, DA, ...)

Os estudantes trabalhadores, ou outros que estejam legalmente dispensados de frequentar as aulas, poderão também optar entre a avaliação contínua e o exame.

Classification improvement

Os estudantes dispensados de exame poderão, se assim o desejarem, submeter-se a exame final, sendo classificados com a melhor das notas entre a da avaliação contínua e a do exame.