Lecture 5

Entropy changes in selected physical/chemical

processes
 S(Br2 liq) < S(Br2 gas) S(H2O, ice) < S(H2O liq)

Q: A range of liquids show molar entropy of vaporization to be almost constant

Around 85 J K-1 mol-1. For Br2 and H2O, H0 vap is 40.7 and 29.5 kJ mol-1
respectively. Comment on the observation. Liquid Br2 boils at 59.20C.
 So (J/Kmol)
MgO 26.9
NaF 51.5

Entropies of ionic solids depend on coulombic attractions.

Increase in
molecular
complexity
generally
leads to
increase in S.
 A solid has Cp 0.43 JK-1 at 4.2K (liquid He
temperature). Calculate its molar entropy.

At very low temperatures, you can assume Cp varies

with temperature as aT3.

dS=qrev/T. Integrating S=Sm(T)-Sm(0)=1/3 aT3

Sm(T) = Sm(0) + 1/3 Cp = Sm(0) + 0.14

Third law of thermodynamics states that as T0,

entropy of a perfect crystalline substance S 0 as the matter is devoid of
All thermal motion. There is only one way of arranging molecules.
Calculate the standard reaction entropy for the combustion
of hydrogen and methane at 25oC. What does the negative
sign suggest about the process?
A tank contains 20 L of compressed nitrogen at 10 atm and 25C.
Calculate the work when the gas is allowed to expand reversibly and
adiabatically to 1 atm pressure. Assume that the gas behaves ideally.

Estimate the final temperature of one mole of gas at 200.0 atm and 19.0C
as it is forced through a porous plug to a final pressure of 0.95 atm. The
Joule-Thomson coefficient of the gas is 0.150 K/atm.
What is the change in the boiling point of H2O at 1000 C per mm change in
the atmospheric pressure? The heat of vaporization is 539.7 cal g-1. The
molar volume of H2O (l) is 18.78 ml and that of H2O (g) is 30.199 lit. (at
1000C and 1 atm )

Calculate the change in entropy of a mole of aluminium (at.wt .27) which

is heated from 600 to 7000 C. The m. p. of Al is 660 0C, the heat of fusion
is 393 Jg-1 and the heat capacities of the solid and liquid may be taken as
31.8 and 34.3 JK-1 mo-1 respectively.

Calculate entropy change when 0.5 L ideal gas, CV = 12.6 JK-1mol-1, at

300 K and 1 atm was allowed to expand to double its volume while
heated simultaneously to 373 K.

In an open beaker held at 27 oC and 1 at pressure containing dilute

sulphuric acid, 100 g zinc were added. Calculate the work done by the
liberated gas.
1 mole of ideal gas initially at 10 atm and 300 K was expanded
adiabatically against a constant pressure of 4 atm so as to reach
equilibrium. Cp = 28.48 + 1.76 x 10-2 T Jmol-1. Calculate U, H and
S.

Calculate the change in the entropies of the system and the surroundings,
and the total change in entropy, when the volume of a sample of argon
gas of mass 21 g at 298 K and 1.50 bar increases from 1.20 dm3 to 4.60
dm3 in (a) an isothermal reversible expansion, (b) an isothermal
irreversible expansion against pex = 0, and (c) an adiabatic reversible
expansion.

The entropy change of argon is given to a good approximation by the

expression, S JK-1 mol-1 = 36.36 + 20.79 ln T. Calculate change in Gibbs
free energy of one mole of argon gas if it is heated at constant pressure
from 25 oC to 50 oC.