Physical Chemistry (CBE) Reviewer Laws of Thermodynamics

Jerome Sadudaquil Date Transcribed: November 4, 2011

Transcribed by: Aaron Abad, Io Angeles, Dana Arellano, Kayemar Aseron, Aaron Ayro

References: Atkins, P., de Paula, J. Physical Chemistry 8 Edition; Mortimer, R. Physical Chemistry

th

Law of Thermodynam ics Zeroth (Law of Thermal Equilibrium) First (Energy)

Mp

Statement

Definition of Terms

Notes/ Implications
Coined by Ralph H. Fowler Gives operational definition of temperature and suggests a method for measuring the temperature in any system.

If two objects, A and B, are at thermal equilibrium with each other and if B is at thermal equilibrium with a third object C, then A is also at thermal equilibrium with C.

Mathematical Statement: The first law of thermodynamics asserts that the internal energy U is a state function if

Internal Energy: the total potential and kinetic energy of the molecules in the system Energy: capacity of a system to do work. There are two equivalent ways of changing a systems internal energy. Work: energy transfer making use of the organized motion of atoms in the surroundings Heat: energy transfer making use of thermal motion in the surroundings

Provides means to calculate amounts of work and heat transferred in various processes, including adiabatic processes. Acquisitive convention: w>0, q>0: energy is transferred to (done on) the system as work or heat w<0, q<0: energy is lost (done by) from the system as work or heat Most general statement of the Law of Conservation of Energy

U = q + w
Where q is the amount of heat transferred to the system and w is the amount of work done on the system. Alternative Statements: The internal energy of an isolated system is constant. If a system is subjected to any cyclic transformation, the work produced in the surroundings is equal to the heat withdrawn from the surroundings. Mathematical Statement:

Second (Entropy)

Entropy: randomness in a spatial or energy distribution of the constituent particles.

The mathematical statement provides a means of calculating the entropy change of any process that begins and ends at equilibrium states. Implies that no macroscopic process can decrease the entropy of the universe. Implies that no heat engine can have an efficiency as great as unity. Implies that all reversible engines operating between the same two temperature reservoirs have the same efficiency.

Kelvin Statement: It is impossible for a system to undergo a cyclic process where sole effects are the flow of an amount of heat from the surroundings to the system and the performance of an equal amount of work on the surroundings. (It is impossible for a system to undergo a cyclic process that turns heat completely into work done on the surroundings.) Clausius Statement: It is impossible for a process to occur that has the sole effect of removing a quantity of heat from an object at a lower temperature and transferring this quantity of heat to an object at a higher temperature. (Heat cannot flow spontaneously from a cooler to a hotter object if nothing else happens.)

Page 1 of 2

Third

The third law of thermodynamics allows the entropy of any pure perfect crystalline substance consistently to be set equal to zero at absolute zero of temperature.

First statement of the third law was made by Nernst in 1906, the Nernst

heat theorem.

Permits the calculation of equilibrium constants from calorimetric data (thermal data) exclusively.

Trivia: What is the order of announcement of the laws? 2, 1, 3, 0

Page 2 of 2