Assignment 1, 2021 PHYS2020 Thermodynamics and Cond. Mat.

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Question 3
(7 marks)
A jet engine is fuelled by liquid octane (C8 H18 ) via the combustion reaction
C8 H18 (l) + 12.5 O2 (g) → 8 CO2 (g) + 9 H2 O(g).
The combustion chamber is maintained at atmospheric pressure throughout the reaction,
with air entering at 500 K and exiting as exhaust at 1,000 K. The excess energy from the
reaction is used to accelerate the exhaust and thereby propel the aircraft.
(a) The enthalpy of formation of octane is ∆f H(C8 H18 ) = −250 kJ/mol at the temperature
it enters the combustion chamber and atmospheric pressure, and the mass of exhaust
gas generated by the reaction of one mole of octane is 1.8 kg. Using the table of
thermodynamic properties given at the back of the exam paper, determine the excess
energy per mole of octane burnt and, assuming this energy is fully converted into
exhaust kinetic energy, the velocity of the exhaust gas.

∆Hreactants = ∆f H(C8 H18 ) + 12.5 × ∆H(O2 ) (1)

= −250kJ/mol + 12.5 × (∆f H(02 ) + CP ∆T ) (2)
= −250kJ/mol + 0 + 12.5 × 29.38 × (500 − 298)/1000 (3)
= −175kJ/mol (4)

∆Hproducts = 8∆H(CO2 ) + 9∆H(H2 O) (5)

= −8 × (−394kJ/mol + 37.11 × (1000 − 298)/1000) +
9 × (−242kJ/mol + 33.58 × (1000 − 298)/1000) (6)
= −4, 910kJ/mol (7)

∆H = ∆Hproducts − ∆Hreactants = −4, 735kJ/mol (8)

r
−2∆H
v= = 2.3km/s (9)
M

(b) Discuss some of the implicit approximations made in the above calculation.
Assumptions:
• Assume that CP is constant at the room temperature and atmospheric pressure value,
but temperature gets up to 1,000 K. At these sort of temperatures the vibrational
energy levels of molecules begin to be activated, modifying the heat capacity. Expect
this to be a relatively minor effect both because it’s only increasing the degrees of
freedom by a few, and because the square-root in the velocity decreases the relative
error.

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Assignment 1, 2021 PHYS2020 Thermodynamics and Cond. Mat.

• Assume that all of the octane is burnt, and that the reaction only proceeds as indicated
(e.g. no carbon monoxide generated).
• Neglect heating of the background air (primarily nitrogen). This heating can be calcu-
lated relatively straightforwardly and shown to introduce a relatively minor correction.

Question 4
(7 marks)

(a) Give a statement of the second law of thermodynamics. Describe in words how this
law arises from the microscopic statistics of large systems.
Second Law statements:
• Heat can never pass from a colder to a warmer body without some other change,
connected therewith, occurring at the same time.
• It is impossible to construct an engine which will work in a complete cycle, and
produce no effect except the raising of a weight and cooling of a heat reservoir.
• Entropy tends to increase.
• All irreversible heat engines between two heat reservoirs are less efficient than a
Carnot engine operating between the same reservoirs.
• The total entropy of an isolated system can never decrease over time.
• In all processes that occur, including spontaneous processes, the total entropy of
the system and its surroundings increases.
• ...
The second law is intrinsically probabilistic. Entropy is the logarithm (times a constant)
of the multiplicity, which defines the number of possible microscopic configurations of
a system in a specific macrostate. Statistically, it is more likely to find a system in the
macrostate with largest multiplicity. If a system is prepared in an initial low entropy
(low multiplicity) macrostate, as it randomly explores the possible microstates of the
system it will probabilistically move towards higher entropy (multiplicity) – i.e. entropy
tends to increase. As systems become larger, the likelihood of finding them far from
the most likely macrostate decreases. Since thermodynamic systems generally deal with
very large numbers of particles (e.g. 1023 ), when in equilibrium with their environment
the chances of finding them far away from the most likely state is generally vanishingly
small.
(b) Consider a two-state paramagnet which consists of a total of four magnetic dipoles.
What is the most likely macrostate of the paramagnet? Calculate the entropy of this
state.
The most likely macrostate is the one with two magnetic dipoles pointing up and two
pointing down. This is because there are a total of six microscope ways this can occur,
compared with four ways to have a total of one dipole up, four ways to have a total of
one dipole down, one way to have all dipoles up, and one way to have all dipoles down.
The multiplicity of this state is exactly the number of possible microstates, so six. This
gives an entropy of S = k ln 6 = 2.4 × 10−23 J/K.

END OF ASSIGNMENT

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Assignment 1, 2021 PHYS2020 Thermodynamics and Cond. Mat.

PHYS2020 Formula Sheet

Units and constants: Equipartition theorem:

1 atm = 101.3 kPa = 1.013 bar f f

U (T ) = U (0) + nRT = U (0) + N kT
= 1.013 ×105 N/m2 2 2
0 ◦C = 273.15 K Entropy:
1 cal = 4.186 J S = k ln Ω
NA = 6.022 ×1023
Qrev
R = 8.315 J/(mol·K) dS =
kB = R/NA = 1.381 × 10−23 J/K T
e = 1.602 ×10−19 C ∆trs H
∆trs S =
F = NA e = 96485 J/V·mol Ttrs
Z Tf
CP dT
Ideal gas equation of state: S(Tf ) = S(Ti ) +
Ti T
P V = nRT = N kT Clausius-Clapeyron equation:
Van der Waals equation of state: dP ∆S L
= =
nRT  n 2 dT ∆V T ∆V
P = −a
V − nb V Clausius inequality:
Virial equation of state: I
dQ
≤0
P Vm = RT (1 + BP + CP 2 + . . . ) Tenv
 
B C Entropy of mixing:
P Vm = RT 1 + + + ...
Vm Vm2
∆Smixing = −nR [x ln x + (1 − x) ln(1 − x)]
Compression factor:
Efficiency of a heat engine:
Z = P V /N kT
work performed W
Work and heat: ≡ =
heat absorbed Qh
∆U = Q + W
Z Carnot efficiency:
W = − P dV Tc
C = 1 −
Z Th
Q = T dS
Coefficient of performance:
Heat capacities: energy transferred as heat Qc
COP ≡ =
work performed W
Cm = C/n , c = C/m

∂U
 
∂H
 Carnot refrigerator:
CV = , CP =
∂T V ∂T P 1
COPC =
f f Th /Tc − 1
CV = N k = nR (ideal gas)
2 2
Thermodynamic potentials:
CP − CV = nR (ideal gas)
Adiabatic expansion of an ideal gas: H = U + PV
f +2 F = U − TS
P V γ = const; T V γ−1 = const; γ = G = H − TS
f

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Assignment 1, 2021 PHYS2020 Thermodynamics and Cond. Mat.

Thermodynamic identity: Gibbs-Helmholtz equations:

dU = T dS − P dV + µdN 
∂ G

H
dG = −SdT + V dP + µdN = − 2
∂T T P T
 
∂ F U
Maxwell relations: = − 2
    ∂T T V T
∂T ∂V
=
∂P S ∂S P Partial derivatives:
   
∂T ∂P
= −      
∂x ∂y ∂z
∂V S ∂S V = −1

∂V
 
∂S
 ∂y z ∂z x ∂x y
= −
∂T P ∂P T
        −1
∂P ∂S ∂x ∂y
= =
∂T V ∂V T ∂y z ∂x z

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