Thermodynamic Cycles

NUCL 2010
Instructor: Dr. M.H. Kaye
Matthew.Kaye@ontariotechu.ca
Chapter 4 – Energy Analysis of Closed Systems
(January 17, 2024)
Chapter 4 – Energy Analysis of Closed Systems
• Recall that a closed system means
that there is not any mass flowing
across the boundary.
• But heat and work can…
Moving Boundary Work
• Consider the cylinder
piston set-up shown here.
• If the gas expands (or
contracts) then the
boundary has moved a
distance, ds.
• Force × distance = work

𝑤𝑤 = 𝐹𝐹𝐹𝐹𝐹𝐹 = 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 = 𝑃𝑃𝑃𝑃𝑃𝑃

Quasi-Equilibrium Process
• A process during which the system remains nearly in equilibrium at all
times;
• Also called a quasi-static process;
• Closely approximated by engines when the piston moves slowly (low
velocity);
Boundary Work
dV positive during expansion
dV negative during compression

𝜕𝜕𝑊𝑊𝑏𝑏 = 𝐹𝐹𝐹𝐹𝐹𝐹 = 𝑃𝑃𝑃𝑃𝑃𝑃𝑃𝑃 = 𝑃𝑃𝑃𝑃𝑃𝑃

2
𝑊𝑊𝑏𝑏 = � 𝑃𝑃𝑃𝑃𝑃𝑃
1

2 2
𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 = 𝐴𝐴 = � 𝑑𝑑𝑑𝑑 = � 𝑃𝑃𝑃𝑃𝑃𝑃
1 1
Boundary Work
• Since work is a path function, the area
under the curve changes depending on
the path.
• So, if we can make a cycle that goes
from 1 to 2 via path A, and returns via
path C, we have net work of 5 kJ.
• It is this net work that can be
transferred out of a closed system
(across the boundary).
Polytropic Process
During the expansion and compression cycles
the pressure and volume are
related by 𝑃𝑃𝑉𝑉 𝑛𝑛 = 𝐶𝐶, where
n and C are constants
 𝑛𝑛
Polytropic Process (𝑃𝑃𝑉𝑉 = 𝐶𝐶)
• To calculate the work done at the boundary:
2 2 −𝑛𝑛+1 −𝑛𝑛+1
−𝑛𝑛
𝑉𝑉2 − 𝑉𝑉
1 𝑃𝑃2 𝑉𝑉2 − 𝑃𝑃1 𝑉𝑉1
𝑊𝑊𝑏𝑏 = � 𝑃𝑃𝑃𝑃𝑃𝑃 = � 𝐶𝐶𝑉𝑉 𝑑𝑑𝑑𝑑 = 𝐶𝐶 =
1 1 −𝑛𝑛 + 1 1 − 𝑛𝑛
• For an ideal gas, 𝑃𝑃𝑃𝑃 = 𝑛𝑛𝑛𝑛𝑛𝑛, so (assuming n ≠ 1):
𝑚𝑚𝑚𝑚 𝑇𝑇2 − 𝑇𝑇1 Equivalent to
𝑊𝑊𝑏𝑏 = an isothermal
1 − 𝑛𝑛
process for an
• And if n = 1: 2 2
ideal gas
𝑉𝑉2
𝑊𝑊𝑏𝑏 = � 𝑃𝑃𝑃𝑃𝑃𝑃 = � 𝐶𝐶𝑉𝑉 −1 𝑑𝑑𝑑𝑑 = 𝑃𝑃𝑃𝑃 𝑙𝑙𝑙𝑙
1 1 𝑉𝑉1
Energy Balance for a Closed System
• From Chapter 2, we established that the energy balance for a system is:
𝐸𝐸𝐼𝐼𝐼𝐼 − 𝐸𝐸𝑂𝑂𝑂𝑂𝑂𝑂 = ∆𝐸𝐸𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
• Or expressed as a rate:
𝑑𝑑𝐸𝐸𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
𝐸𝐸̇ 𝐼𝐼𝐼𝐼 − 𝐸𝐸̇ 𝑂𝑂𝑂𝑂𝑂𝑂 =
𝑑𝑑𝑑𝑑
• For any system the energy in or out is: heat (q), work (w), and mass (m)
• For a closed system, energy in or out is: heat (q) and work (w), only
Energy Balance for a Closed System
• closed system, energy in or out is: heat (q) and work (w), only:
𝑑𝑑𝐸𝐸𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
𝐸𝐸̇ 𝐼𝐼𝐼𝐼 − 𝐸𝐸̇ 𝑂𝑂𝑂𝑂𝑂𝑂 =
𝑑𝑑𝑑𝑑
Rate of net Rate of change in
energy transfer internal, kinetic,
by heat and work potential, etc. energies
This is equivalent to:
𝜕𝜕𝐸𝐸̇ 𝐼𝐼𝐼𝐼 − 𝜕𝜕𝐸𝐸̇ 𝑂𝑂𝑂𝑂𝑂𝑂 = 𝑑𝑑𝐸𝐸𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
Energy Balance for a Closed Cycle
• Since the initial and final states are
identical in a cycle, ∆Esystem = 0
• Therefore, Ein – Eout = 0
• This is true for any cycle… but for a
closed system, only have heat and work,
so: 𝑊𝑊𝑛𝑛𝑛𝑛𝑛𝑛,𝑜𝑜𝑜𝑜𝑜𝑜 = 𝑄𝑄𝑛𝑛𝑛𝑛𝑛𝑛,𝑖𝑖𝑖𝑖
• and as a rate: 𝑊𝑊̇ 𝑛𝑛𝑛𝑛𝑛𝑛,𝑜𝑜𝑜𝑜𝑜𝑜 = 𝑄𝑄̇ 𝑛𝑛𝑛𝑛𝑛𝑛,𝑖𝑖𝑖𝑖
FOR A CYCLE
Caveat Emptor for solving problems
• When performing a general analytical study or solving an assignment
problem, it may not be obvious how the heat and work are interacting;
• Thus, an assumption of direction must be made. This is:
• Heat (Qin) transferred into system is positive
• Work (Wout) done by the system is positive
• Heat (Qout)transferred out is negative
• Work (Win)done on system is negative
• So: Qnet,in = Qin – Qout and Wnet,out = Wout – Win
• And when a calculated value is negative, it only means we assumed the
wrong direction. Direction should be reversed (but magnitude remains)
Restating the First Law
• The text points out that the First Law of
Thermodynamics has never been proven
mathematically… but more importantly, it
has never been shown not to be true.

For closed systems

Some Problems to Tackle for Understanding
• From the text, I suggest trying the following problems to test
understanding. Only two do not have answers (NA) given in text:
• 4-14; 4-17; 4-19; and 4-24
• 4-29 (NA); 4-31(NA); 4-35, and 4-38

• These are for practice, not assigned. But as the proverb states: “Practice
makes perfect.”
• Also, “Amateurs practice until they get it right; Professionals practice
until they can’t get it wrong!”
Specific Heats
• Specific heat is defined as the energy required to raise the temperature
of a unit mass of a substance by one degree.
• This quantity is dependent on how the process is performed, which leads
to two different specific heats:
• Specific heat at constant volume is cV
• Specific heat at constant pressure is cP
Examples of How this Works
• Consider Helium. In both situations 1 kg of Hegas

At a constant volume (on left) it

only takes 3.12 kJ to raise the
temperature of the gas by a
degree;
At a constant pressure (on right)
the volume expands, and it takes
more energy to raise the
temperature, specifically 5.19 kJ
Specific Heats
• Specific heats can be expressed in terms of other thermodynamic
properties.
• From the conservation of energy principle: ein – eout =∆esystem
• In differential form this is: 𝜕𝜕𝑒𝑒𝑖𝑖𝑖𝑖 − 𝜕𝜕𝑒𝑒𝑜𝑜𝑜𝑜𝑜𝑜 = 𝑑𝑑𝑑𝑑
• But the left hand side of this equation is the net amount of energy
transferred to the system.
• This is equal to: cVdT (at constant volume) or cPdT (at constant pressure)
• So… 𝑐𝑐 =
𝜕𝜕𝑢𝑢
and 𝑐𝑐 =
𝜕𝜕𝜕𝜕
𝑉𝑉 𝑑𝑑𝑑𝑑 𝑉𝑉 𝑃𝑃 𝑑𝑑𝑑𝑑 𝑃𝑃
Specific Heats – encore
• Since specific heats can be expressed in terms of other properties, they
are properties themselves.
• So, they depend on the state, which is specified by two independent
intensive properties.
• So specific heats are dependent on temperature.
Specific Heats – encore
• So cV is related to the changes in internal energy
• And cP is related to changes in the enthalpy
• In other words, cV is a measure of the variation of internal energy of a
substance with temperature;
• And, cP is a measure of the variation of enthalpy of a substance with
temperature;
• For both units are: kJ·kg-1·K-1 (also kJ·kg-1·ºC-1)
• Or as molar quantities: 𝑐𝑐𝑉𝑉̅ 𝑎𝑎𝑎𝑎𝑎𝑎 𝑐𝑐𝑃𝑃̅ , where the units are: kJ·mol-1·K-1
Internal Energy, Enthalpy, and Specific Heats
In 1843, Joule performed the following
experiment.
Two bulbs connected by a valve, one
has high pressure gas, other evacuated.
Submerged in water. Allow bulbs to
reach temperature of water.
Opens valve and allows gas to
equilibrate and measures T of water.
What do you think happened?
Internal Energy, Enthalpy, and Specific Heats
In 1843, Joule performed the following
experiment.
Two bulbs connected by a valve, one
has high pressure gas, other evacuated.
Submerged in water. Allow bulbs to
reach temperature of water.
Opens valve and allows gas to
equilibrate and measures T of water.
Temperature stays constant!
Conclusions by Joule
• Joule concluded for ideal gases:
• Joule assumed that no heat transferred to or from the air;
• No work done;
• Therefore, internal energy of air did not change, even though the volume and
pressure changed;
• Thus, internal energy is a function of temperature only.
• Internal energy is not a function of pressure or specific volume.
• Caveat: for gases that deviate significantly from ideal gas behaviour, the
internal energy is not a function of temperature alone.
Changes in Enthalpy and Internal Energy
• For an ideal gas during a process that goes from state 1 to state 2:
• Internal energy:
2
∆𝑢𝑢 = 𝑢𝑢2 − 𝑢𝑢1 = � 𝑐𝑐𝑉𝑉 𝑇𝑇 𝑑𝑑𝑑𝑑
1

• Enthalpy:
2
∆ℎ = ℎ2 − ℎ1 = � 𝑐𝑐𝑃𝑃 𝑇𝑇 𝑑𝑑𝑑𝑑
1
Specific Heat Relations for Ideal Gases
It can be show that for ideal gases (see assignment 1):
When dealing with mass amounts 𝑐𝑐𝑃𝑃 = 𝑐𝑐𝑉𝑉 + 𝑅𝑅 units are kJ·kg-1·K-1
In molar quantities: 𝑐𝑐𝑃𝑃̅ = 𝑐𝑐𝑉𝑉̅ + 𝑅𝑅𝑢𝑢 units are kJ·mol-1·K-1
The universal gas constant is Ru values given slide 32 of Lecture 3

𝑐𝑐𝑃𝑃
Specific heat ratio, k, given by: 𝑘𝑘 =
𝑐𝑐𝑉𝑉
For monatomic gases, k is essentially constant at 1.667
For many diatomic gases, including air, k ≈ 1.4 at room temperature
Solids and Liquids – what about them?
• An incompressible substance is one for whom the specific volume (or
density) is constant.
• Generally, liquids and solids can be approximated as incompressible
substances without sacrificing much accuracy.
• This assumption means that the energy change associated with a volume
is very small compared to other forms of energy.
• This means that for solids and liquids: 𝑐𝑐𝑃𝑃 = 𝑐𝑐𝑉𝑉 = 𝑐𝑐
Changes in Internal Energy for Solids/Liquids
• For a solid or liquid during a process that goes from state 1 to state 2:
• Internal energy:
2
∆𝑢𝑢 = 𝑢𝑢2 − 𝑢𝑢1 = � 𝑐𝑐 𝑇𝑇 𝑑𝑑𝑑𝑑
1

• Enthalpy is a bit more complicated:

Changes in Enthalpy for Solids
• For a solid during a process that goes from state 1 to state 2:
• Recall that h = u + PV 0
• Differentiating this gives: 𝑑𝑑𝑑 = 𝑑𝑑𝑑𝑑 + 𝑉𝑉𝑉𝑉𝑉𝑉 + 𝑃𝑃𝑃𝑃𝑃𝑃 = 𝑑𝑑𝑑𝑑 + 𝑉𝑉𝑉𝑉𝑉𝑉
• So: 𝑑𝑑𝑑 = 𝑑𝑑𝑑𝑑 + 𝑉𝑉𝑉𝑉𝑉𝑉, which upon integration gives:
0
∆ℎ = ∆𝑢𝑢 + 𝑉𝑉∆𝑃𝑃 ≅ 𝑐𝑐 𝑇𝑇 ∆𝑇𝑇 + 𝑉𝑉∆𝑃𝑃
2
• Enthalpy for solids: ∆ℎ = ℎ2 − ℎ1 = � 𝑐𝑐 𝑇𝑇 𝑑𝑑𝑑𝑑
1
Changes in Enthalpy for Liquids
• For a liquid during a process that goes from state 1 to state 2:
• Recall that h = u + PV 0
• Differentiating this gives: 𝑑𝑑𝑑 = 𝑑𝑑𝑑𝑑 + 𝑉𝑉𝑉𝑉𝑉𝑉 + 𝑃𝑃𝑃𝑃𝑃𝑃 = 𝑑𝑑𝑑𝑑 + 𝑉𝑉𝑉𝑉𝑉𝑉
• So: 𝑑𝑑𝑑 = 𝑑𝑑𝑑𝑑 + 𝑉𝑉𝑉𝑉𝑉𝑉, which upon integration gives:
∆ℎ = ∆𝑢𝑢 + 𝑉𝑉∆𝑃𝑃 ≅ 𝑐𝑐 𝑇𝑇 ∆𝑇𝑇 + 𝑉𝑉∆𝑃𝑃
• Two special cases commonly encountered:
• Constant pressure processes, as in a heater (∆P = 0), ∆ℎ = ∆𝑢𝑢 ≅ 𝑐𝑐 𝑇𝑇 ∆𝑇𝑇
• Constant temperature processes, as in pumps (∆T = 0), ∆ℎ = 𝑉𝑉∆𝑃𝑃
Some Problems to Tackle for Understanding
• From the text, I again suggest trying the following problems to test
understanding. Only two do not have answers (NA) given in text:
• 4-54; 4-66; 4-67; 4-71; 4-72; 4-80 (NA); and 4-85 (NA)

• These are for practice, not assigned.

Questions
• Ask now.
• Or, e-mail me at: Matthew.Kaye@ontariotechu.ca