Chapter 20: The Second Law of Thermodynamics

20.20. (a) The equations under consideration are = H Eint + pV , =A Eint − TS and G = Eint + pV − TS. After
taking the differential of each equation, keeping in mind that no variable is always constant and using the
First Law of Thermodynamics, dE= int TdS − pdV , three equations arise.
(1) dH = dEint + pdV + Vdp = TdS + Vdp
(2) dA = dEint − TdS − SdT =− pdV − SdT
(3) dG = dEint + pdV + Vdp − TdS − SdT = Vdp − SdT
(b) From the three equations, it is clear that each energy ( H , A, G ) are actually functions of other variables
whereby H → H ( S, p ) , A → A (V , T ) , G → G ( p, T ) . This means a partial differential can be taken of each
variable so that ∂H /∂S = T , ∂H /∂p =V , ∂A/∂V =− p, ∂A/∂T =−S, ∂G /∂p =V and ∂G /∂T =−S. In
general, if the mixed second-order partial derivatives are continuous, then they are equal, i.e.
∂2 f ( x, y ) ∂2 f ( x, y ) ∂ 2 H ∂T ∂V
= . This yields three further Maxwell relations: = = ,
∂x∂y ∂y∂x ∂S∂p ∂p ∂S
∂2 A ∂p ∂S ∂ 2 G ∂V ∂S
=
− =− and = = − , where again each partial derivative is taken with its
∂V ∂T ∂T ∂V ∂p∂T ∂T ∂p
companion independent variable fixed.

20.21. In general, the Boltzmann definition of entropy is given as S = kB ln ( w ) . If there are two systems, A and B,
it can be seen that the system A has w A possible states and system B has w B possible states. Therefore, for
the given system A and B, the total number of possible states is = w w A ⋅ wB , so then the entropy is
separable by logarithm rules:
S =kB ln ( w ) =kB ln ( w A ⋅ wB ) =kB ln ( w A ) + kB ln ( wB ) =SA + SB .

20.22. The heat pump is doing work to move heat energy from the cold outside into the warm house. For each
6.28 kJ of electricity used by the heat pump, 21.98 kJ of heat is moved from the outside to the inside.
Adding the heat energy from the heat pump to the heat energy extracted from the cold reservoir gives the
total heat energy released to the hot reservoir.

20.23. The wind chill factor from Canada is given by Twc = 13.12 + 0.6215T − 11.37v 0.16 + 0.3965Tv 0.16 where T is
the surface temperature in °C and v is the wind speed in km/h at a point 10 m above the ground. Of
course, this formula for wind chill was never intended to be applied for the temperatures and wind speed
present in the clouds of Saturn. But supposing a temperature of 150 K (−123 °C), and a wind speed of
600. km/h, the wind chill is 42 K (−231 °C), which is still above absolute zero. The definition of absolute
zero is when a particle is completely without motion. As long as the particle is moving in the wind, it will
have some kinetic energy and thus the temperature is greater than absolute zero.
20.24. The process of turning water into steam is an irreversible process. The Second Law of Thermodynamics
states that entropy must increase in an irreversible process, so it would require energy to convert the steam
back into water to use over again, resulting in a net energy loss. Eventually, the engine will not have
enough energy to convert the steam back to water.
20.25. To increase the entropy, heat the water up. To decrease the entropy, cool the water down. As long as the
water is not a closed system, the entropy can decrease.

871