2 - Law of Thermodynamics

17 December 2020 09:35

▪ Facts About Entropy :

Entropy, the measure of a system’s thermal energy per unit temperature that is
unavailable for doing useful work. Because work is obtained from
ordered molecular motion, the amount of entropy is also a measure of the molecular
disorder, or randomness, of a system

▪ It is impossible to take heat from a hotter reservoir and completely convert into work by a
cyclic process without transferring a part of heat to a cooler reservoir [Kelvin Statement]

▪ It is impossible for a cyclic process to transfer heat from a body at lower temperature to one at
a higher temperature without converting some work to heat [Classius Statement]

▪ The entropy of universe increases in a spontaneous process.

▪ Entropy is an extensive property.

▪ Entropy for a system is state function but not for surrounding.

▪ Entropy is a measure of the degree of spreading and sharing of thermal energy among the
microstates possible in a system.

▪ Total change in entropy of system and surrounding is zero in a reversible process.

▪ Absolute entropy of a system is proportional to temperature but change in entropy is inversely

proportional to temperature at which the process occurs.

▪ Entropy of a perfectly ordered solid at 0K is zero [but not at 0ºC]. Third law of
thermodynamics is Nernst law of thermodynamics.

▪ Thermodynamic expression for change in entropy is given by qrev./T.

▪ Unit of molar entropy is JK–1 mol–1.

▪ Entropy of solid < liquid < gas of a substance.

▪ An ideal gas occupying a larger volume has higher entropy than gas occupying small volume
under given conditions.

▪ Molar entropy of a dilute solution is greater than that of concentrated solution.

▪ Molecules with more number of bonds and atoms have higher entropy.

▪ Precipitation of Ionic solid has –ve entropy change.

▪ Dissolution of Ionic solid have +ve entropy change.

▪ Entropy is a measure of driving force behind chemical reactions.

▪ Entropy can be created or destroyed.

▪ Entropy is a measure of number of ways energy can be distributed among the motions of
particles.
▪ FREE ENERGY

▪ Gibbs free energy dG is equal to –TdStotal at constant temperature and pressure.

▪ Gibbs free energy is equal to maximum useful work other than PV work.

▪ Hemholtz free energy is equal to –TdStotal at constant temperature and volume.

▪ Hemholz free energy is maximum work.

▪ Gibbs energy is state function

▪ Gibbs energy is extensive property.

▪ Molar Gibbs free energy is intensive property.

▪ Gibbs free energy is not conserved.

▪ In G = H – TS

▪ TdSsystem represents heat that is wasted in the form of PV work and is not available to do
useful work.