Physical chemistry

TRN MAI PHNG tmphuong@yahoo.com tmphuong@hcmut.edu.vn http://www2.hcmut.edu.vn/~tmphuong

Content
Thermodynamics Thermochemistry Chemical equilibrium Phase equilibrium

Thermodynamics & Thermochemistry

Thermochemistry how we observe, measure and predict energy changes for

physical

Thermodynamics how to predict if a chemical reaction will occur or not.

changes chemical reactions

Thermodynamics & Thermochemistry

Chemical Equilibrium

Phase Equilibrium

Concepts

The Nature of Energy

Energy is the capacity to do work or to transfer heat. Heat is the energy transferred from one object to another because of a difference in temperature.

The Nature of Energy

Kinetic Energy and Potential Energy Kinetic energy is the energy of motion:

KE = mv2

Potential

energy is the energy an object possesses by virtue of its position.

Represents the capacity to do work.

Energy Units
Joule Calorie

calorie is the heat required to raise the temperature of 1.00 g of H2O by 1C.

1 cal = 4.184 J

Work & Heat

Work (A): product of force applied to an object over a distance. Heat (Q): transfer of energy between two objects

Thermodynamic system
Thermodynamic system is a quantity of matter of fixed identity, around which we can draw a boundary . Everything outside the boundary is the surroundings

The Universe = The System + The Surroundings

The System and Surroundings

The environment of a chemical reaction is separated into two parts, the system and the surroundings. The system is the part of the environment we single out for study. The system generally is comprised only of the participants (reactants, products, solvents, etc..) in the reaction.
we divide the universe into a system and its surroundings. The boundary between the system and its surroundings can be as real as the walls of a beaker that separates a solution from the rest of the universe

Thermodynamic Systems - Definitions

Open System: Free exchange across system boundaries. Closed System: Energy can be exchanged but matter cannot.

Isolated System: No matter or energy cross system boundaries. No work can be done on the system. Adiabatic System: Special case where no heat can be exchanged but work can be done on the system (e.g. PV work).

States of Matter

Solid

Liquid

Gas

Plasma

The thermodynamic state

The thermodynamic state of a system is defined by specifying values of a set of measurable properties sufficient to determine all other properties . A thermodynamic state is the macroscopic condition of a thermodynamic system as described by its particular thermodynamic parameters. The state of any thermodynamic system can be described by a set of thermodynamic parameters, such as temperature, pressure, density, composition, independently of its surroundings or history.

Thermodynamic State Properties/Parameters

Extensive properties: These variables or properties depend on the amount of material present (e.g. mass or volume).
Intensive properties: These variables or properties DO NOT depend on the amount of material (e.g. density, pressure, and temperature).

Process

If the state of a system changes, then it is undergoing a process. The succession of states through which the system passes defines the path of the process. a cyclic process or a cycle: If, at the end of the process, the properties have returned to their original values (but the state of the surroundings may have changed)
Isochoric process : Isobaric process : Isotherma process l: Adiabatic process : V = const P = const T = const Q=0

Exothermic process & Endothermic process

Exothermic: energy released by system to surrounding. Endothermic: energy absorbed by system from surrounding.

Spontaneous process:

All exothermic reactions are spontaneous. However, some endothermic reactions are also spontaneous.

State function

A state function (a function of state) is a property of a system that depends only on the current state of the system, not on the way in which the system got to that state. A state function describes the equilibrium state of a system. Common state function: internal energy, enthalpy and entropy. They describe quantitatively an equilibrium state of thermodynamic systems. State functions are functions that are independent of the pathway by which a process occurs.
DX = Xfinal - Xinitial

Process functions

mechanical work and heat are process quantities because they describe quantitatively the transition between equilibrium states of thermodynamic systems. State function: depends only on the initial and final states of system, not on how the internal energy is used.

Internal Energy (U)

The internal energy (U) of a system consists of the kinetic energy of all the particles plus the potential energy of interaction between the particles and within the particles.

U = kinetic + potential

Internal Energy (U)

Internal Energy (U)

Cannot measure absolute internal energy. Can only measure the change in energy of the system

Internal Energy

The internal energy is a state function it depends only on the state of a system, the method of preparation of this state (path) is irrelevant (other state functions T, P, V, etc.).
In equilibrium:

U = U (V, T)

Internal Energy depends on the kinetic energy of particles in a system and their density ) Internal Energy of a chemical system depends on number of particles type of particles temperature