The Second Law

 Kelvin statement of the Second law of thermodynamics states that no process is

possible in which the sole result is the absorption of heat from a reservoir and its
complete conversion into work.
 The entropy of an isolated system increases in the course of a spontaneous change.
∆Stot > 0.
 The thermodynamic definition of entropy is dS=¿ dqrev/T.
 The statistical definition of entropy is given by the Boltzmann formula S=k lnW .
 A Carnot cycle is a cycle composed of a sequence of isothermal and adiabatic
reversible expansions and compressions.
Tc
 The efficiency of a heat engine is ε =1−
Th .
 The Kelvin scale is a themodynamic temperature scale in which the Triple Point of
water defines the point 273.16 K .
dq
 The Clausius Inequality is dS ≥ T
 The normal transition temperature, Ttrs, is the temperature at which two phases are in
equilibrium at 1 atm. The entropy of transition at the transition temperature, ∆ trsS = ∆trsH/Ttrs.
 Trouton’s rule states that many normal liquids have approximately the same standard
entropy of vapourisation (about 85 J K -1 mol-1)
Tf
 The variation of entopy with temperature is given by S(Tf) = S(Ti) + ∫ (Cp /T ) dT .
Ti
 The entropy of a substance is measured from its area under a graph of C p/T against T, using
the Debye extrapolation at low temperatures, Cp =aT3 as T → 0.
 The Nernst Heat Theorem states that the entropy change accompanying any physical or
chemical transformation approaches zero as the temperature approaches zero, ∆S→0 as
T→0, provided all the substances involved are perfectly ordered.
 The Third law of Thermodynamics goes like this: The entropy of all perfectly crystalline
substances is zero at T=0.
 The Helmholtz energy is A = U –TS. The Gibbs energy is G = H – TS.