Physical Chemistry I M - Z

The student must learn the quantitative notions and problem-solving of weak forces and interactions, conservation and energy transfers in the form of heat, entropy and thermal machines, chemical equilibrium, phase diagrams, and electrochemistry of reversible processes.

Specifically:

(a) knowledge and understanding skills. The knowledge objective will be achieved by rigorously explaining the basic concepts through the mathematics of differential calculus, integral and differential equations. The goal of understanding the topics covered will be pursued by using examples outside the topics of thermodynamics applied to chemistry, e.g., applications of the laws of thermodynamics to biology and materials in an interactive manner with students.

(b) ability to apply knowledge and understanding. These objectives will be achieved by performing numerical and theoretical classroom exercises of the topics covered.

(c) autonomy of judgment. The autonomy of the judgment test will have been achieved if and only if objectives (a) and (b) are met. If the test is negative, the teacher must take up the unclear topics with new examples and lectures to bridge the remaining lagoons.

(d) ability to communicate. The ability to communicate clearly and rigorously the topics covered will be addressed with lectures at the beginning of the science communication course and a final written test where students expound on a topic covered during the course.

(e) Ability to pursue study independently. This will be achieved and tested at the end of the course using scientific articles related to the program with classroom exposition by students.

The course includes 35 hours of theoretical lectures and 36 hours of classroom exercises.

Frontal lessons, numerical and theoretical exercises in the classroom.

Required knowledge of general chemistry, physics I, and mathematics I and II..

Minimum 80% of lessons.

Matter aggregation states. /2/

Macroscopic world, microscopic world and correlations properties - structure. Solid, liquid, gaseous and plasma state. Guiding forces in the assembly of condensed phases. Morse curve, interaction potentials and Madelung's problem.

Properties of the gases./4/

Perfect gas state equation; molar mass; perfect gas mixtures, ideality deviations and real gas state equations. The compressibility factor; actual gas mixtures.

The first principle of Thermodynamics./3/

Heat, work, and energy conservation. Expansion and compression work. Concept of reversibility and spontaneous phenomena. Route functions. Status and differential functions.

Thermology./3/

Specific heat and heat capacity. Internal energy and temperature; enthalpy and temperature: relations between specific heat. Isothermal and adiabatic processes - reversible or irreversible. The zero law of thermodynamics.

Thermochemistry./4/

Reaction enthalpy and Hess law; Standard enthalpy, relations between ΔH and ΔU; ΔH depending on temperature. Ion enthalpy in solution. Born-Haber cycle.

The second principle./10/

The second principle. The efficiency of thermal machines and Carnot cycle. The refrigerant of Carnot. Definition of entropy. Entropy and cyclic integral. The general test for the cyclic integral of entropy. The inequality of Clausius. Exact differential properties. Entropy in the operation of T,V and T,P. Changes in state and entropy.

The third law./3/

Entropy variations for the ideal gas. The standard status for the ideal gas. The third law and standard entropy. Entropy changes for a chemical reaction and temperature dependence.

Entropy and probability./5/

Entropy, probability and spontaneity. Probability, thermodynamic probability and entropy. General form for thermodynamic probability. Energy distribution. Third principle, entropy of mixing and point defects. Apparent exceptions - and not - to the third law.

Spontaneity and equilibrium./7/

The system's entropy, environmental entropy and conditions of spontaneity and equilibrium. The Helmholtz function and the Gibbs function. The fundamental equation of thermodynamics. Gibbs function and variations of T, P and composition. The chemical potential. The chemical potential of an ideal gas and real gases. The concept of formal uniqueness and fugacity.

Phase changes ./4/

Chemical potential and principle of phase stability. First-order phase transitions. Second-order phase transitions. Water status diagram. Surface, surface tension and capillarity.

Mixtures and activity./4/

Molar volume in the mixtures. The law of Gibbs-Duhem. Mixing and spontaneity processes. Solutions of non-volatile solutions; colligative properties: ebullioscopy, cryoscopy and osmosis. Mixtures of volatile liquids: the concept of activity. The limit laws of Raoult and Henry. The limit equations of Chemistry.

Chemical equilibrium./4/

The criterion of spontaneity and equilibrium for a chemical reaction. Equilibrium, the equilibrium constant and the influence of catalysts, inert substances, temperature and pressure.

Electrochemistry./8/

Ion activity in Debye-Huckel's solution and law. The concept of ionic strength and the influence on solubility. Form of the limit laws of dilute solution chemistry. Electrochemical potential. Most common electrodes and electrochemical cells. Standard electrochemical potentials and electrochemical series. The equation of Nernst. Batteries, accumulators and electrolysis.

Phase equilibrium./10/

Free mixing energy and phase diagrams. Phase rule, lever rule and phase diagrams. One component system. Two-component systems. Two-component systems with one or more products. Three-component systems. Influence of ionic strength.

Suggested books:

- G.W. Castellan : Physical Chemistry (Addison-Wesley Pu. Co.).

- S. Capasso : La Chimica Fisica attraverso esercizi (Loghia)

- G.K. Vemulapalli : Chimica Fisica (EDISES).

The learning verification will consist of a written test with numerical problem-solving on gases, thermodynamics, and electrochemistry. The date, time and classroom where the exams will be held will be available on the official calendar available on the following platforms: the department website and SMARTEDU.

For the conduct of the written test, the student must be equipped with a scientific calculator. Specific tables and numerical values of constants necessary for solving the assigned questions will be provided in the classroom by the professor.

Passing the written test is a "conditio sine qua non" for access to the oral test. This test will cover the topics covered in the course. The final exam grade will take into account both the written test and the oral test.

Other information posed by students will be given on the first day

Oral examination, sample questions:

Fundamental relations of thermodynamics.

Relationship between Gibbs free energy and equilibrium constant.

Entropy and thermal machines.

Phase transitions and phase diagrams.

Examples of numerical exercises from the written test:

(a) Plot the PV isotherm of a van der Waals gas for molecular chlorine at 350 3 450 K, with P between 0 and 100 bar and V between 0 and 3 cm3 mole-1 knowing that for Cl2 a= Pam6mole-2 and b= m3mole-1*10-3

(b) An average man weighs 70 kg and produces about 10460 kJ of heat per day. Considering that man is an open system and the main mechanism for maintaining constant temperature consists of water evaporation, calculate how much water must evaporate per day to maintain a constant temperature at 37°C, knowing that the change in enthalpy of evaporation at 37°C is worth 43.4 kJmole-1.

(c) Given a generic reaction in the gaseous state A<->C+D is endothermic and has an equilibrium constant of 1 bar at 25°C. Calculate;

1) the delta G° at 25°C.

2) the delta S° is positive or negative

3) at 40°C delta G° will be negative or positive.