Tutorial 4
(1) 3 moles of N2 originally at 1 atm is mixed with 5 moles of H2 at 1 atm isothermally to
yield a mixture whose pressure is also 1 atm. Calculate ∆Smix .
(2) U is a function of only the temperature for a gas that obeys the equation of state
RT
P =
V̄ − b
where b is a constant that reflects the size of the molecules. Calculate ∆S̄ when one mole
of such a gas at T and V̄1 is allowed to expand into a vacuum to a total volume of V̄2
(3) The constant-pressure molar heat capacity of O2 (g) from 300K to 1200K is given by
C̄p (T )[JK −1 mol−1 ] = 25.72 + (12.98 × 10−3 K −1 )T − (38.62 × 10−7 K −2 )T 2
where T is in kelvins. Calculate the value of ∆S̄ when one mole of O2 (g) is heated at
constant pressure from 300K to 1200K.
(4) Consider the expansion of an isolated ideal gas initially at 298K into a volume that is
twice as large as its initial volume. Calculate ∆S̄ for the gas. Is this expansion
spontaneous?
(5) Half a mole of an ideal gas expands isothermally and reversibly at 298.15K from a
volume of 10L to 20L.
(a) What is the change in the entropy of the gas?
(b) How much work is done on the gas?
(c) What is qsurr ?
(d) What is the change in the entropy of the surroundings?
(e) What is the change in the entropy of the system plus surroundings?
(6) Now consider that the expansion in the preceding question (5) occurs irreversibly by
simply opening a stopcock and allowing the gas to rush into an evacuated bulb from an
initial volume of 10L to 20L.
(a) What is the change in the entropy of the gas?
(b) How much work is done on the gas?
(c) What is qsurr ?
(d) What is the change in the entropy of the surroundings?
(e) What is the change in the entropy of the system plus surroundings?
(7) Calculate the change in entropy of an ideal monoatomic gas B in changing from P1 , T1
to P2 , T2 .
1
(8) What is the change in molar entropy of helium in the following process?
1He(298K, 1bar) → 1He(100K, 10bar)
(9) Calculate the change in entropy when two moles of water vaporize at 100oC. The value
of ∆H̄vap = 40.65KJmol−1 . Comment on the sign of ∆Svap .
(10) An ideal gas at 27oC expands isothermally and reversibly from 10 to 1 bar against a
pressure that is gradually reduced. Calculate q, w and each of the thermodynamic
quantities ∆U, ∆H, ∆G, ∆A and ∆S for one mole of this gas.
(11) Naphthalene melts at 80.2o C. If the vapor pressure of the liquid is 10 Torr at 85.8o C
and 40 Torr at 119.3o C, use the Clausius-Clapeyron equation to calculate the enthalpy of
vaporization, the normal boiling point and the entropy of vaporization at the boiling point.
(12) The temperature dependence of the vapour pressure of solid sulfur dioxide can be
approximately represented by the relation log(p/T orr) = 10.5916 − 1871.2K/T and that of
liquid SO2 by log(p/T orr) = 8.3186 − 1425.7K/T . Estimate the temperature and pressure
at the triple point of SO2 .
(13) Calculate the change in pressure required to change the freezing point of water by
1o C. At 0o C the heat of fusion of ice is 333.5 J g−1 , the density of water is 0.9998 g cm−3
and the density of ice is is 0.9168 g cm−3 .
(14) the vapor pressure of benzene can be expressed by the empirical formula
3884K
ln(P/torr) = − + 17.63
T
Use this formula to show that benzene boils at 670 C when the atmospheric pressure is 500
torr.
(15) Determine the value of dT /dP for ice at its normal melting point. The molar enthalpy
of fusion for ice 273.15K and 1 atm is 6010 J mol−1 and ∆V̄f us under the same condition is
−1.63 cm3 mol−1 . Estimate the melting point of ice at 1000 atm.
(16) The vapor pressure of benzene is found to obey the empirical formula
3229.86K 118345K 2
ln(P/torr) = 16.725 − −
T T2
from 298.2K to its normal boiling point 353.24K. Given that the molar enthalpy of
vaporization at 353.24K is 30.8 KJ mol−1 molar volume of liquid benzene at 353.24K is
96.0 cm3 mol−1 , use the above equation to determine the molar volume of the vapor at its
equilibrium pressure at 353.24K and compare this value with the ideal gas value.