CHEMICAL THERMODYNAMICS: – TUTORIAL 3

THEORY QUESTIONS

1. State the third law of thermodynamics.

2. If the canonical variables of the Gibbs free energy are temperature and pressure, what
are the canonical variables of the Helmholtz free energy?
3. Is it possible to determine the residual temperature of a substance? Why/why not?
4. Is the fundamental property relation dH = TdS + VdP a general thermodynamic
relationship, or is it restricted to particular situations (e.g. isobaric, isothermal, etc)?
Explain.
5. Will air be ‘lighter’ or ‘heavier’ on a humid day? Explain.
6. Derive the Maxwell relation for the Gibbs free energy, using the first law of
thermodynamics as your starting point.

PROBLEMS

1. A hot brick at 200 oC is rested on top of another brick at 20 oC. Both bricks are placed
within a vacuum, so you may consider them isolated from any surroundings. If both
bricks have a mass of 1 kg each, calculate the total entropy change associated with
thermal equalization between the two bricks. The heat capacity of brick is 0.84 kJ.kg-
1
.K-1.
2. Estimate the molar volume of nitrogen gas at 273 K and 10 bar using the van der Waals
equation of state. Parameters a and b for nitrogen are 1.37 L2bar.mol-2 and 0.0387
L.mol-1, respectively. The universal gas constant is 8.314x10-2 L.bar.K-1.mol-1. The van
der Waals equation of state is:
P = RT/(V – b) – a/V2
3. Consider the reaction N2(g) + 2O2(g) ļ 2NO2(g). Initially, there are stoichiometric
amounts of nitrogen and oxygen in the reaction chamber which has a volume of 66 L.
'HWHUPLQHWKHH[WHQWRIWKHUHDFWLRQ ȟ XQGHUVWDQGDUGFRQGLWLRQVDWoC. The Gibbs
energy change of this reaction at 25 oC is -51.3 kJ.mol-1.
4. A particular power plant operates with heat source reservoir at 638 K and a heat sink
reservoir at 299 K. It has a thermal efficiency equal to 55 % of the Carnot engine
thermal efficiency for the same temperatures.
(a) What is the thermal efficiency of the plant?

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 (b) To what temperature must the heat source reservoir be raised to increase the thermal
efficiency of the plant to 33 %? Again the thermal efficiency of the plant is 55 % of the
Carnot engine value.
5. Determine the enthalpy change of water vapour at 4.42 MPa as it is heated from 647 K
to 776 K using the Pitzer generalized correlation. The acentric factor of water is 0.334,
and its critical point is at 647 K and 22.1 MPa. The mean heat capacity of water vapour
is 36.2 J.mol-1.K-1.
6. A Carnot engine receives 250 kJ/sec of heat from a heat source reservoir at 798 K and
rejects heat to a heat sink reservoir at 323 K. Calculate the power developed and the
heat rejected by the engine.
7. Large quantities of liquefied natural gas (LNG) are shipped by ocean tanker. At the
unloading port, provision is made for vapourization of the LNG so that it may be
delivered to pipelines as gas. The LNG arrives in the tanker at atmospheric pressure
and 113.7 K, and represents a possible heat sink for use as the cold reservoir of a heat
engine. Assume that LNG at 298 K and 1.0133 bar is an ideal gas with molar mass of
17. Also assume that the LNG vaporizes only, absorbing only its latent heat of 512
kJ/kg at 113.7 K. For unloading of LNG as a vapour at the rate of 9000 m3/s, as
measured at 298 K and 1.0133 bar and assuming the availability of an adequate heat
source at 303ºC,
(a) What is the maximum possible power obtainable?
(b) What is the rate of heat transfer from the heat source?
8. One mole of an ideal gas is compressed isothermally but irreversibly at 403 K from 2.5
bar to 6.5 bar in a piston/cylinder device. The work required is 30 % greater than the
work of a reversible isothermal compression. The heat transferred from the gas during
compression flows to a heat reservoir at 298K
(a) What is the entropy change of the gas?
(b) What is the entropy change of the heat reservoir?
(c) What is the total entropy change?
9. A 40 kg steel casting at temperature of 625 K is dropped into a well-insulated vessel
containing 160 kg of water at 276 K. Assume that the specific heat of iron is 0.45 kJ/
kg.K and that of water is 4.185 kJ/kg.K and if there are no heat losses, calculate
entropy change for:
(a) The casting?
(b) The oil?
(c) Both considered together?
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10. An inventor has developed a plastic heat engine that outputs 20 kW of power and
requires heat input of 30 kW. If it is rejecting heat to the atmosphere, discuss whether
this device is plausible.
11. A piston arrangement contains 1 mole of carbon dioxide gas at 373 K and 10 bar.
Estimate its molar volume using both the truncated virial equation of state and the ideal
gas equation. Comment on any differences or similarities between your two results. The
second virial coefficient of carbon dioxide (B) at 373 K is -0.0722 L.mol-1.
12. A steam engine requires 20 kW of heat to be added in the boiler, and generates 12 kW
of mechanical work as a result. Estimate the temperature of the boiler if the heat is
rejected to the atmosphere. You may assume that the steam engine operates with
optimal efficiency.

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USEFUL RELATIONSHIPS
Definitions Fundamental Property Relations
+Ł839 dU = TdS – PdV
$Ł8– TS dH = TdS + VdP
*Ł+– TS dA = – PdV – SdT
=Ł39 57 dG = VdP – SdT

Equations of State Pitzer Correlation

Virial: Z = 1 + B/V + C/V2 + … Z = Z0 Ȧ=1
Van der Waals: P = RT/(V – b) – a/V2 HR/RTC = (HR/RTC)0 +
Ȧ +R/RTC)1
Clausius-Clapeyron Equation Ȧ – 1.0 – log10(Prsat)|Tr=0.7
ln(P1/P2) = (-ǻ+5 72 - 1/T1) Equilibrium Constant
Carnot Engines ǻ*rxn = – RTlnKC
Ș – TC/TH Entropy
Thermodynamic Temperature dS = dQ/T
T (K) = 273.15 + T (oC)

DATA
Universal Gas Constant
R= 8.314 J.K-1.mol-1
8.206x10-2 L.atm.K-1.mol-1
8.314x10-2 L.bar.K-1.mol-1
8.314 Pa.m3.K-1.mol-1
1.987 cal.K-1.mol-1

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