CYL 110 Tutorial 1 SS
CYL 110: 2012-2013
Thermodynamics Tutorial 1
1. � − b)exp(a/RV
Dieterici's equation of state for a gas is P(V � T) = RT, where a, b, and R are constants. (a) Determine
∂V ∂T ∂P
(∂V/ ∂T), (∂T/ ∂P), and (∂P/ ∂V) and verify that � � � � � � = 1.(b) Show that the Dieterici critical constants are
∂T ∂P ∂V
𝑎𝑎 𝑎𝑎
𝑝𝑝𝑐𝑐 = 2 𝑒𝑒 −2 , 𝑉𝑉𝑐𝑐 = 2𝑏𝑏, 𝑇𝑇𝑐𝑐 =
4𝑏𝑏 4𝑅𝑅𝑅𝑅
𝑇𝑇 𝜕𝜕𝜕𝜕 𝑃𝑃 𝜕𝜕𝜕𝜕 𝑃𝑃 2 𝜕𝜕𝜕𝜕
2. Deviation coefficients for real gases are defined as � � , � � , � � . Calculate these values for an ideal gas,
𝑃𝑃 𝜕𝜕𝜕𝜕 𝑉𝑉 𝑅𝑅 𝜕𝜕𝜕𝜕 𝑃𝑃 𝑅𝑅 𝜕𝜕𝜕𝜕 𝑇𝑇
a van der Waals gas, and a Dieterici gas.
1 1 2
3. (a) Express the van der Waals equation of state in virial form PV� = RT + B � � + C � � + ⋯ and determine B and C
�
V �
V
in terms of a and b. (b) Use the virial form of the van der Waals equation to determine the Boyle temperature.
4. The critical pressure and temperature for hydrogen are 1.30 MPa and 33.2 K. Calculate the a and b parameters of the
𝑎𝑎
Redlich-Kwong equation �𝑃𝑃 + 1/2 � � � (𝑉𝑉� − 𝑏𝑏) = 𝑅𝑅𝑅𝑅.
𝑇𝑇 𝑉𝑉 (𝑉𝑉 +𝑏𝑏)
6 -5 3 7
5. Assume that oxygen (Tc = 154.6K, Pc = 5.046 x 10 Pa, Vc = 7.32 x 10 m /mol) and water (Tc = 647.3K, Pc = 2.205 x 10
-5 3
Pa, Vc = 5.6 x 10 m /mol) can be considered as van der Waals fluids. a) Find the value of the reduced volume both
fluids would have at Tr = 3/2 and Pr = 3. b) Find the T, P, and V of each gas at Tr = 3/2 and Pr = 3. c) If oxygen and water
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are both at 200 °C and 2.5 x 10 Pa, find their specific volumes.
6. A quantity of 0.850 mol of an ideal gas initially at a pressure of 15 atm and 300 K is allowed to expand isothermally
until its final pressure is 1 atm. Calculate the work done if the expansion is carried out (a) against a vacuum, (b) against
a constant external pressure of 1 atm, and (c) reversibly. (d) Calculate also the work done if the same process is
carried out adiabatically and reversibly and comment on the difference.
7. Show that for an ideal gas 𝑑𝑑𝑑𝑑 = 𝐶𝐶𝑉𝑉 𝑑𝑑𝑑𝑑 + 𝑅𝑅𝑅𝑅𝑅𝑅 ln 𝑉𝑉 is not an exact differential, but 𝑑𝑑𝑑𝑑 = 𝐶𝐶𝑉𝑉 𝑑𝑑 ln 𝑇𝑇 + 𝑅𝑅𝑅𝑅 ln 𝑉𝑉 is an
exact differential.
8. A kettle containing 1 kg of boiling water is heated until evaporation is complete. Calculate w, q, ΔU for this process.
Assume water vapour behaves ideally.
9. (a) Write the expression for dV given that V is a function of p and T. deduce an expression for d(lnV) in terms of the
expansion coefficient α and the isothermal compressibility 𝜅𝜅 𝑇𝑇 .
(b) Show that (𝜕𝜕𝜕𝜕/𝜕𝜕𝜕𝜕)𝑉𝑉 = 𝛼𝛼/𝜅𝜅 𝑇𝑇 .
(c) Evaluate the ratio for a perfect gas.
(d) For a van der Waals gas, show that 𝜅𝜅 𝑇𝑇 𝑅𝑅 = 𝛼𝛼(𝑉𝑉� − 𝑏𝑏).
10. When a fluorocarbon gas was allowed to expand reversibly and adiabatically to twice it volume the temperature fell
from 298.15 to 248.44 K and its pressure fell from 1522.2 Torr to 613.85 Torr. Evaluate Cv and Cp. You may assume
that the gas behaves perfectly.
11. Over narrow range of temperature and pressure, the differential expression for the volume of a fluid as a function of
temperature and pressure can be integrated to obtain 𝑉𝑉 = 𝐾𝐾 𝑒𝑒 −𝛼𝛼𝛼𝛼 𝑒𝑒 −𝜅𝜅𝜅𝜅 . Show that V is a state function.
3 3
12. One mole of chlorine undergoes adiabatic expansion from 1 dm to a 10 dm against an external pressure of 0.1013
6 -2 3 -1 -1 -2
Mpa. What is the final temperature of gas? a = 665 dm Kpa mol , b = 0.055 dm mol and CV,m = 33.91 JK mol
13. A constant-volume perfect gas thermometer indicates a pressure of 6.69 kPa at the triple point temperature of water
(273.16 K). (a) What change of pressure indicates a change of 1.00 K at this temperature? (b) What pressure indicates
a temperature of 100.00°C? (c) What change of pressure indicates a change of 1.00 K at the latter temperature?
1
CYL 110 Tutorial 1 SS
14. Derive a general relation between CP and CV to get the general result
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕
𝐶𝐶𝑝𝑝 − 𝐶𝐶𝑉𝑉 = �𝑃𝑃 + � � � � �
𝜕𝜕𝜕𝜕 𝑇𝑇 𝜕𝜕𝜕𝜕 𝑃𝑃
15. Show for a van der Waals gas 𝐶𝐶𝑝𝑝 − 𝐶𝐶𝑉𝑉 = 𝛼𝛼 2 𝑇𝑇𝑇𝑇/𝜅𝜅 𝑇𝑇 . You will need to use an identity (to be derived later in this course)
𝜕𝜕𝜕𝜕
𝜋𝜋 𝑇𝑇 = 𝑇𝑇 � � − 𝑃𝑃
𝜕𝜕𝜕𝜕 𝑉𝑉
16. A mole of ideal gas is compressed adiabatically to one-half of its original volume when the temperature of the gas is
increased from 273 K to 433 K. Assuming ���
𝐶𝐶𝑉𝑉 is independent of the temperature, calculate the value of ���
𝐶𝐶𝑉𝑉 for this gas.
17. Show that the work involved in a reversible, adiabatic pressure change of one mole of an ideal gas is given by
𝑃𝑃2 𝑅𝑅/𝐶𝐶𝑃𝑃
𝑤𝑤 = 𝑐𝑐𝑉𝑉 𝑇𝑇1 [� � − 1]
𝑃𝑃1
where T1 is the initial temperature and P1 and P2 are the initial and final pressures, respectively.
7
18. A sample of 1.00 mol perfect gas molecules with Cp,m = /2R is put through the following cycle: (a) Constant volume
heating to twice its initial volume, (b) Reversible, adiabatic expansion back to its initial temperature, (c) reversible
isothermal compression back to 1.00 atm. Calculate q, w, ΔU, and ΔH for each step and overall.
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19. Take nitrogen to be a van der Waals gas with a = 1.390 dm atm mol and b = 0.03913 dm mol , and calculate ΔHm
when the pressure on the gas is decreased from 500 atm to 1.00 atm at 300 K. For a van der Waals gas, μJT = {(2a/RT)
7
– b}/Cp,m. Assume Cp,m = /2R.
2 2 2 2
20. (a) What is the total differential of z = x + 2y – 2xy + 2x – 4y – 8? (b) Show that ∂ z/∂y∂x = ∂ z/∂x∂y for this function.
(c) Let z = xy – y + ln x + 2. Find dz and show that it is exact.
21. Calculate the work done during the isothermal reversible expansion of a gas that satisfies the virial equation of state,
2
� = RT + B � 1 � + C � 1 � + ⋯. Evaluate (a) the work for 1.0 mol Ar at 273 K (B = -21.7 cm3 mol-1) and (b) the same
PV �
V �
V
3 3
amount of a perfect gas. Let the expansion be from 500 cm to 1000 cm in each case.
2
22. A gas obeys the equation of state Vm = RT/p + aT and its constant-pressure heat capacity is given by Cp,m = A + BT +
Cp, where a, A, B, and C are constants independent of T and p. Obtain expressions for (a) the Joule–Thomson
coefficient and its constant-volume heat capacity.
23. Calculate the heat needed to raise the temperature of air in a house from 20 to 25 °C. Assume that the house contains
3 -3
600 m of air, which should be taken to be a perfect diatomic gas. The density of air is 1.21 kg m at 20 °C Calculate
ΔU and ΔH for the heating of the air.
𝑥𝑥
24. Find the maximum inversion temperature of the gas whose equation of state is �𝑃𝑃 + � (𝑉𝑉 − 𝑦𝑦) = 𝑅𝑅𝑅𝑅 where x and
𝑇𝑇𝑉𝑉 2
y are constants.
25. When a fluorocarbon gas was allowed to expand reversibly and adiabatically to twice it volume the temperature fell
from 298.15 to 248.44 K and its pressure fell from 1522.2 Torr to 613.85 Torr. Evaluate Cv and Cp. You may assume
that the gas behaves perfectly.
26. Verify that the enthalpy of a perfect gas is independent of its pressure while it is dependent upon pressure for a van
der Waals gas. [Use the approximate form of van der Waals equation PV = nRT + nP(b - a/RT)].
27. An important application of adiabatic cooling/heating is in atmospheric physics. Pressure varies with altitude as
𝑑𝑑𝑑𝑑/𝑑𝑑ℎ = −𝑔𝑔𝑔𝑔, where ρ is the density. Calculate the change in temperature at the top of a mountain 2 km above the
valley floor assuming the process is adiabatic and air behaves ideally.
28. Which of these cyclic integrals must vanish for a closed system with P-V work only? (a) ∮ 𝑃𝑃𝑃𝑃𝑃𝑃, (b) ∮(𝑃𝑃𝑃𝑃𝑃𝑃 + 𝑉𝑉𝑉𝑉𝑉𝑉), (c)
∮ 𝑑𝑑𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟 , (d) ∮ 𝑑𝑑𝑞𝑞𝑟𝑟𝑟𝑟𝑟𝑟 / 𝑇𝑇.