Thermodynamics

Introduction, 1st Law & Thermodynamic & properties

Module 1
Prof. Anand Veeraragavan
[email protected]
Co-Director, Centre for Hypersonics
School of Mechanical and Mining Engineering

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 MECH3400 Thermodynamics and Heat Transfer

Where we are up to
Course outline – we talked about what thermodynamics can tell us. (and what Heat Transfer can extend
that to).
We will go through a quick revision of some of the fundamentals of thermodynamics.
This will all be familiar to you from ENGG1500. It is very important that you become proficient. Falling
behind at the start, where you should already be capable will not bode well for the rest of the course.

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MECH3400 vs ENGG1500
ENGG1500 Exam Formulae (2013) MECH3400 Exam Formulae (2014)

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Useful tips
Write notes if it helps you learn, all lecture materials are posted on Blackboard.
Practice, practice, and practice!
Reference book that we recommend “Thermodynamics: An Engineering
Approach” by Yunus Cengel, Michael Boles and Mehmet Kanoglu
Online resources from McGraw-Hill Education
http://connect.mheducation.com
Contact me via: email

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Structure of the “Thermodynamics” Lectures

We will cover the following modules throughout the

“thermodynamics” part in the following weeks

1. Introduction, 1st Law & Thermodynamic properties

2. Entropy
3. Performance of thermodynamic processes
4. Refrigeration and heat pumps
5. Psychrometry
6. Thermodynamic cycles
7. Thermodynamics of Combustion

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Content outline in Module 1

Thermodynamics introduction
••• Chapter 1
Systems
Energy
1st Law of Thermodynamics ••• Chapter 2
▪ 1st Law for closed system ••• Chapter 4
▪ 1st Law for control volume ••• Chapter 5
Properties for pure substance ••• Chapter 3

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Thermodynamics is everywhere!

https://www.thoughtco.com/laws-
of-thermodynamics-373307

SCRAMSPACE-1 test vehicle (UQ)

https://en.wikipedia.org/wiki/Black_hole_thermodynamics

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What is Thermodynamics? Also referred to as

Classical thermodynamics
❑ Thermodynamics deals with macroscopic properties of substance
Explains how they are related and how they change with time;
No need to know the exact behaviour of individual particles;
Related to but different from kinetic theory and statistical mechanics, which deal with discrete micro-
properties (at molecular or atomic level).
❑ Deals with substances at an equilibrium state, or near-equilibrium.
❑ Involves 0th, 1st, 2nd, and 3rd laws of thermodynamics.
❑ For our purposes, we are most interested in classical thermodynamics: the relation between heat,
energy, and work.

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What thermodynamics can and cannot

Thermodynamics can Thermodynamics cannot

• tell what is possible and what is × determine how long things take to
impossible happen
• determine the properties of matter - Thermodynamics fundamentally deals
• determine energy flows (changes in with equilibrium, and cannot tell use
relations between time and other scales
energy) (such as length, temperature, pressure,
- Changes between energy forms etc).
- Transfer from one place to -Heat Transfer component will deal with
another transient time-dependent processes
• help to avoid experiments related to heat
× tell us about micro-scale behaviour

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Some basic concepts

Definitions of system (a quantity of matter or a region in space chosen for
study), surroundings and boundary.
Closed system: a fixed quantity of mass.
Open system: a properly selected region, i.e. control volume. Its boundaries
are called control surface.

System

Boundary Closed system Control volumes

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Some basic concepts Specific heat capacity, specific gravity…

Properties: any characteristics of a system, i.e. physical quantities.
-Intensive properties: independent of mass or size, like T, P, and ρ.
-Extensive properties: dependent on mass or size, like E, U, M, H, entropy…
Specific properties: extensive properties per unit mass, e.g.
𝒱 1
Specific volume: 𝓋= = Intensive property now
𝑚 𝜌

State: a “moment” when the system is considered not changing; a state is described by a set of
properties.

• State postulate: the minimum set of properties required to fix the

state of a system. For simple compressible system, two independent
intensive properties are usually required.

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Some basic concepts (continued)

Equilibrium: a system in state of balance–no driving force within the system.
Thermal equilibrium, mechanical equilibrium, phase equilibrium, chemical
equilibrium
Process: any change that a system undergoes from one equilibrium state to another.
Path: the “trajectory in property diagram” (series of states) a system passes through
during a process.
A closed-loop
process is
State postulate for
called a
a simple
cycle.
compressible
system is two
independent
properties. A compression process
from equilibrium state 1 to
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Some basic concepts (continued)

Special processes in practice:
Quasi-equilibrium process: a process when the system remains infinitesimally close to an
equilibrium state at all times. Usually it is a sufficiently slow-changing process.
Isothermal (constant T), isobaric (constant P), isochoric/isometric process (constant V or v).
Steady-flow process: a process during which a fluid flows through a control volume steadily.

𝜕𝑇 𝜕𝑃
=0 =0 Note the difference
𝜕𝑡 𝜕𝑡
between “steady” and
𝑚𝐶𝑉 = 𝑐𝑜𝑛𝑠𝑡 𝐸𝐶𝑉 = 𝑐𝑜𝑛𝑠𝑡 “uniform”!

Steady-flow process
S1 S2
𝜕𝑇 𝜕𝑇 𝜕𝑇
however ≠0 ≠0 ≠0
𝜕𝑥 𝜕𝑦 𝜕𝑧
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Energy
What is energy? The “ability” to do work. SI unit Joule. Other units calorie, kW⋅h, BTU, eV…
Energy exists in different forms, sum of which in a system contributes total energy E.
In Thermodynamics, we consider E is composed of three components:

𝐸 = 𝑈 + 𝐸𝑘 + 𝐸𝑝 (J) 𝑒 = 𝑢 + 𝑒𝑘 + 𝑒𝑝 (J/kg)
Energy forms Total mass form Unit-mass form Most closed systems are
Internal Energy 𝑈 = 𝑚𝑢 𝑢 actually stationary
Kinetic Energy 1 1 𝑉2 𝑅 2 𝜔2 systems which means
𝐸𝑘 = 𝑚𝑉 2 𝑜𝑟 𝐼𝜔2 𝑒𝑘 = 𝑜𝑟 there is no change in Ek
2 2 2 2
Potential Energy 𝐸𝑝 = 𝑚𝑔𝑧 𝑒𝑝 = 𝑔𝑧 and Ep during a
-gravitational field thermodynamic process

• Consequently we can have 𝑬 = 𝒎𝒆 or 𝑬 = 𝒎 𝒖 + 𝒆𝒌 + 𝒆𝒑

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In-depth: what is “internal energy”?

Internal energy U , or specific internal energy 𝑢 (mass) or 𝑢ത (molar), is the sum of
molecular kinetic energy and molecular potential energy of a system.
Molecular kinetic energy is associated with molecular motions (translation, rotation,
vibration, spin, etc.);
- also referred to as sensible energy/heat;
- ability for internal molecular bonds to move (“inertia”) is the cause of different heat
capacities of different substances
Molecular potential energy is a combination of various binding forces at microscopic
level:
- inter-molecular binding—related to phase-changing, called latent energy/heat.
- intramolecular atomic bonds—chemical energy (e.g. between oxygen atoms in O2).
- strong bonds within nucleus—nuclear energy.

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Energy — basic principles

I. Energy can be stored in a system—energy stays with mass.
II. Energy can change between different forms within a system, e.g. 𝐸𝑘 → 𝑈 or 𝐸𝑝 → 𝐸𝑘 .
III. Total energy change of a system occurs when system state changes, and equals to the
difference between energies at two states, i.e.:
Subscripts:
∆𝑬𝒔𝒚𝒔 = 𝑬𝒇𝒊𝒏𝒂𝒍 − 𝑬𝒊𝒏𝒊𝒕𝒊𝒂𝒍 = 𝑬𝟐 − 𝑬𝟏 “1” denotes “initial”
“2” denotes “final”
∆𝑬𝒔𝒚𝒔 = (𝑈 + 𝐸𝑘 + 𝐸𝑝 )𝒇𝒊𝒏𝒂𝒍 −(𝑈 + 𝐸𝑘 + 𝐸𝑝 )𝒊𝒏𝒊𝒕𝒊𝒂𝒍 = ∆𝑼 + ∆𝑬𝒌 + ∆𝑬𝒑

IV. Energy can be transported into and out of a system thru the system boundary.

The forms of energy transportation of a system are: We decide boundaries of

• Heat transfer driven by temperature difference system to simplify analysis
• Work associated with forces acting thru distances of energy flows for a given
problem
• Mass flow only available for control volume
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Energy transportation
Heat transfer
Heat (as a form of energy) transfers from higher temperature to the lower until a thermal equilibrium is reached.
Three mechanisms of heat transfer: conduction, convection, radiation.
“heat transferred” 𝑄 (J), “heat transfer rate” 𝑄ሶ (J/s or W), “unit-mass form” 𝑞 (J/kg) 𝑄𝑖𝑛
Adiabatic process: a process without heat transfer. 𝑄𝑜𝑢𝑡
𝑊𝑖𝑛
Work
Energy transferred other than heat. 𝑊𝑜𝑢𝑡
• Work is denoted by 𝑊 (J). The rate of work is 𝑊ሶ (J/s or W);
• Mechanical work: 𝑊 = 𝐹𝑠 = 𝑃∆𝒱 , 𝑊ሶ = 𝐹𝑣 = 𝑃𝒱ሶ (𝒱 is volume, 𝑣 is velocity)
Mass flow
Mass flow in or out of a system carries energy with it: 𝐸 = 𝑚𝑒

The total transfer of ∆𝑬 = 𝑸𝒊𝒏 − 𝑸𝒐𝒖𝒕 + 𝑾𝒊𝒏 − 𝑾𝒐𝒖𝒕 + (𝑬𝒎𝒂𝒔𝒔,𝒊𝒏 − 𝑬𝒎𝒂𝒔𝒔,𝒐𝒖𝒕 )

energy quantity is
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The 1st Law of Thermodynamics

Basic statement: energy can be neither created nor destroyed, it can only change forms. Also known
as “conservation of energy”.
For a system, the Law essentially states an Energy Balance —
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦
∆𝑬𝒔𝒚𝒔 = 𝑬𝒊𝒏 − 𝑬𝒐𝒖𝒕 = −
𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑙𝑒𝑎𝑣𝑖𝑛𝑔 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚

• As we know ∆𝐸𝑠𝑦𝑠 = 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙 , then we can have the equation

𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡 = 𝑬𝒊𝒏 − 𝑬𝒐𝒖𝒕 = ∆𝑼 + ∆𝑬𝒌 + ∆𝑬𝒑 including
• Heat transfer, Q
• In the rate forms, Energy balance states 𝑑𝐸𝑠𝑦𝑠 /𝑑𝑡 = 𝐸ሶ 𝑖𝑛 − 𝐸ሶ 𝑜𝑢𝑡 • Work transfer, W
• Mass flow, me
or 𝑑𝑒𝑠𝑦𝑠 /𝑑𝑡 = 𝑒ሶ𝑖𝑛 − 𝑒ሶ𝑜𝑢𝑡

We will examine generalised forms for both closed systems and control volumes.
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1st Law for closed systems

Generalised form 1st law of thermodynamics for a closed system:
Sign convention: any
energy added to the
∆𝐸𝑠𝑦𝑠 = 𝑸 − 𝑾 = ∆𝑼 + ∆𝑬𝒌 + ∆𝑬𝒑 system is positive.
Any energy from or
done by the system
• Q: heat supplied into the system (IN) is negative.
• W: work done by the system (OUT)
• No mass transfer — but system boundary can move (boundary work)
Note: ∆𝑬𝒔𝒚𝒔 can be zero, or can be non-zero!
‘Δ’ specifies an exact difference
between two states
Differential form: 𝑑𝐸 = 𝛿𝑄 − 𝛿𝑊
Other forms

‘d’ specifies the differential as the

Rate of change form: 𝐸ሶ = 𝑄ሶ − 𝑊ሶ = 𝑈ሶ + 𝐸ሶ 𝑘 + 𝐸ሶ 𝑝 derivative at a given state
‘𝛿’ specifies an infinitesimally small
Per unit-mass form: ∆𝑒 = 𝑞 − 𝑤 = 𝑢 + 𝑒𝑘 + 𝑒𝑝 difference
Over-dot specifies a rate of change,
or ∆𝑬 = 𝑸 − 𝑾 = 𝒎(𝒖 + 𝒆𝒌 + 𝒆𝒑 ) e.g. 𝐸ሶ ≡ 𝑑𝐸/𝑑𝑡
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Example 1.1
A flowerpot of mass 1 kg falls at terminal velocity of 100 km/h and hits the ground, at which point all its
kinetic energy is converted to heat. How much heat is generated by the impact?

Closed
system

100 km/h

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1st Law for closed systems—boundary work

Boundary work is the work caused by a change in the volume of the system,
usually through compression and expansion
2 ∆𝐸𝑠𝑦𝑠 = 𝑄 − 𝑊 = ∆𝑈 + ∆𝐸𝑘 + ∆𝐸𝑝
𝛿𝑊𝑏 = 𝑃𝑑𝒱
𝑊𝑏 = න 𝑃𝑑𝒱
𝑊𝑏 = 𝑃 𝒱2 − 𝒱1 1
= 𝑃∆𝒱 𝑊 = 𝑃𝑑𝒱 + 𝑊𝑜𝑡ℎ , i.e.
• ∆𝐸 = 𝑄 − 𝑃∆𝒱 − 𝑊𝑜𝑡ℎ
𝐴 ∙ 𝑑𝑠
• 𝑑𝐸 = 𝛿𝑄 − 𝑃𝑑𝒱 − 𝛿𝑊𝑜𝑡ℎ
• 𝐸ሶ = 𝑄ሶ − 𝑃𝒱ሶ − 𝑊ሶ 𝑜𝑡ℎ
• −𝑃𝑑𝒱 represents expansion
• 𝑃𝑑𝒱 represents compression
When P is constant When P is a function of V
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1st Law for closed systems—boundary work*

Polytropic process*
Expansion or compression process of gas during which 𝑃𝒱 𝑛 = 𝐶, where n and
C are constants.
Work done during a polytropic
process:
2 2
𝑃2 𝒱2 − 𝑃1 𝒱1
𝑊𝑏 = න 𝑃𝑑𝒱 = න 𝐶𝒱 −𝑛 𝑑𝒱 = (𝑛 ≠ 1)
1 1 1−𝑛

2 2
−1
𝒱2
𝑊𝑏 = න 𝑃𝑑𝒱 = න 𝐶𝒱 𝑑𝒱 = 𝑃𝒱 ln (𝑛 = 1)
1 1 𝒱1

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Example 1.2 – Piston System

A frictionless piston-cylinder contains 5 kg of steam at 400 kPa and 200°C, the
specific volume of steam at this state is 0.53434 m3/kg. Heat is now transferred to
the steam until the temperature reaches 250°C, specific volume is 0.59520 m3/kg.
If the piston is freely moving and its mass is constant, determine the work done by
the steam during the process.
S1 S2

Heat

𝑚 = 5𝑘𝑔 𝑃2 = 400 𝑘𝑃𝑎

𝑃1 = 400 𝑘𝑃𝑎 𝓋2 = 0.5920 𝑚3/𝑘𝑔
𝓋1 = 0.5343 𝑚3/𝑘𝑔
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Example 1.3 – Piston System

Air is contained at 2 bar inside a frictionless piston-cylinder. It is heated to expand
freely to twice its initial volume. Given an initial specific volume of 0.393 m3/kg,
and a heat input of 100 kJ/kg, what is the change in internal energy?

S1 S2

2 bar 2 bar

𝑞 = 100 𝑘𝐽/𝑘𝑔

𝓋 = 0.393 𝑚3/𝑘𝑔

2 𝑏𝑎𝑟 = 200 𝑘𝑃𝑎

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1st Law for control volumes

Conservation of mass principle

𝒎𝒊𝒏 − 𝒎𝒐𝒖𝒕 = ∆𝒎𝑪𝑽 𝒌𝒈 or 𝑑𝑚𝐶𝑉 Τ𝑑𝑡 = 𝑚ሶ 𝑖𝑛 − 𝑚ሶ 𝑜𝑢𝑡 𝑘𝑔/𝑠

• For steady-flow process, ∆𝑚𝐶𝑉 ≡ 0

⇒ 𝚺𝒎𝒊𝒏 = 𝚺𝒎𝒐𝒖𝒕
• For incompressible steady-flow process

⇒ 𝚺𝓥ሶ 𝒊𝒏 = 𝚺𝓥ሶ 𝒐𝒖𝒕

Note that compressible processes do not
necessarily have this volume rate equality.
• For unsteady-flow process, ∆𝑚𝐶𝑉 ≠ 0 A
compressible
⇒ 𝚺𝒎𝒊𝒏 − 𝚺𝒎𝒐𝒖𝒕 = ∆𝒎𝒔𝒚𝒔 process
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1st Law for control volumes

In a closed system, the total energy of per unit mass in the system is described by 𝑒 = 𝑢 + 𝑒𝑘 + 𝑒𝑝 .
However, the unit-mass energy in a control volume is not.
𝑃𝒱 is flow work (flow energy) — the work required to push the mass into or out of the control
volume expressed as 𝑾𝒇𝒍𝒐𝒘 = 𝑷𝓥 (𝐽) , or 𝒘𝒇𝒍𝒐𝒘 = 𝑷𝓿 (𝐽/𝑘𝑔) on unit-mass basis.

Add not only e,

𝑢, 𝑒𝑘 , 𝑒𝑝
but also 𝑃𝒱.

• Total energy of a flowing fluid per unit mass is not described by e, but 𝜽, i.e.

𝜃 = 𝑃𝓋 + 𝑒 = 𝑃𝓋 + 𝑢 + 𝑒𝑘 + 𝑒𝑝 (𝐽/𝑘𝑔)
Here 𝑷𝓿 + 𝒖 is defined as enthalpy h.
Unit-mass energy of 𝑽𝟐
flowing fluid 𝜽 = 𝒉 + 𝒆𝒌 + 𝒆𝒑 = 𝒉 + + 𝒈𝒛
𝟐
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1st Law for control volumes

Energy transport by mass flow

Amount of energy transport: 𝐸𝑓𝑙𝑜𝑤𝑚𝑎𝑠𝑠 = 𝑚𝜃 𝑬𝒇𝒍𝒐𝒘𝒎𝒂𝒔𝒔 = 𝒎(𝒉 + 𝒆𝒌 + 𝒆𝒑 )
Rate of energy transport: ሶ
𝐸𝑓𝑙𝑜𝑤𝑚𝑎𝑠𝑠 = 𝑚𝜃
ሶ 𝑬ሶ 𝒇𝒍𝒐𝒘𝒎𝒂𝒔𝒔 = 𝒎(𝒉
ሶ + 𝒆𝒌 + 𝒆𝒑 )

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Example 1.4 – Energy transport by mass

Air flows steadily in a pipe at 300 kPa, 77°C, and 25 m/s at a rate of 18 kg/min.
Determine the specific flow work and the energy rate transported by flow mass. If
the specific volume and specific internal energy of air under this condition is known
as 0.3346 m3/kg and 252.33 kJ/kg.

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1st Law for control volumes

Based on the generic form of 1st Law: 𝑬𝒊𝒏 − 𝑬𝒐𝒖𝒕 = ∆𝑼 + ∆𝑬𝒌 + ∆𝑬𝒑 , we can derive

∆𝐸 = 𝑄 − 𝑊 + 𝑚𝑖𝑛 ℎ + 𝑒𝑘 + 𝑒𝑝 𝑖𝑛
− 𝑚𝑜𝑢𝑡 ℎ + 𝑒𝑘 + 𝑒𝑝 𝑜𝑢𝑡
Total energy change (J)
𝑑𝐸
= 𝑄ሶ − 𝑊ሶ + 𝑚ሶ 𝑖𝑛 ℎ + 𝑒𝑘 + 𝑒𝑝 − 𝑚ሶ 𝑜𝑢𝑡 ℎ + 𝑒𝑘 + 𝑒𝑝 Rate of energy (J/kg)
𝑑𝑡 𝑖𝑛 𝑜𝑢𝑡

Energy transport by mass Energy transport by mass

• Left-side represents change in
total system energy, i.e.
∆𝑼 + ∆𝐸𝑘 + ∆𝐸𝑝 ;
• Right-side represents total
energy in and out 𝑬𝒊𝒏 − 𝑬𝒐𝒖𝒕 .

Total Q and W
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1st Law for control volumes—steady flow

“Steady flow” condition implies (1) Δ𝒱 = 0, (2) Δ𝑚 = 0, (3) Δ𝐸 = 𝐸𝑓𝑖𝑛 − 𝐸𝑖𝑛𝑖 = 0
such as flow problems in turbines, compressors, nozzles

• The total “in” and “out” energies are balanced 𝑑𝐸 Τ𝑑𝑡 = 𝐸ሶ 𝑖𝑛 − 𝐸ሶ 𝑜𝑢𝑡 = 0 ⇒ 𝑬ሶ 𝒊𝒏 = 𝑬ሶ 𝒐𝒖𝒕
0 = 𝑄ሶ − 𝑊ሶ + 𝑚ሶ 𝑖𝑛 ℎ + 𝑒𝑘 + 𝑒𝑝 𝑖𝑛
− 𝑚ሶ 𝑜𝑢𝑡 ℎ + 𝑒𝑘 + 𝑒𝑝 𝑜𝑢𝑡

For single-stream problem, by re-arranging the above equation and applying the
sign convention, it comes to
2 2
𝑉𝑜𝑢𝑡 − 𝑉𝑖𝑛
𝑄ሶ − 𝑊ሶ = 𝑚ሶ ℎ𝑜𝑢𝑡 − ℎ𝑖𝑛 + + 𝑔 𝑧𝑜𝑢𝑡 − 𝑧𝑖𝑛
2

Rate of heat transfer Power Enthalpy change Kinetic energy potential energy
between CV and its between out and in Δℎ change Δ𝑒𝑘 change Δ𝑒𝑝
surroundings
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Example 1.5 – Flow work

A water pump increases the pressure from 101 kPa to 1000 kPa. Determine the
rate of flow work. If the density of water is 1000 kg/m3.

CV 𝑃𝑜𝑢𝑡 = 1000 𝑘𝑃𝑎

𝑃𝑖𝑛 = 101 𝑘𝑃𝑎

work

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1st Law for control volumes—nozzles

• Convert pressure to velocity
– Cannot assume that kinetic energy is negligible!
• Important in equipment where high velocities are desired (e.g. propulsion applications, spraying
equipment)
• Also important in machinery involving flows to prevent backflow

• General assumptions: 𝒒 = 𝟎, 𝒘 = 𝟎, 𝜟𝒆𝒑 = 𝟎, 𝒎ሶ = 𝒄𝒐𝒏𝒔𝒕., 𝒖 = 𝒄𝒐𝒏𝒔𝒕. (for incompressible case)

• ∴ 0 = 𝑚ሶ ℎ𝑜𝑢𝑡 − ℎ𝑖𝑛 + 𝛥𝑒𝑘 (𝑓𝑜𝑟 𝑏𝑜𝑡ℎ 𝑖𝑛𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑙𝑒/𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑙𝑒)
2 2
𝑉𝑜𝑢𝑡 − 𝑉𝑖𝑛
∴ 𝑢𝑖𝑛 + 𝑃𝑖𝑛 𝓋 − 𝑢𝑜𝑢𝑡 + 𝑃𝑜𝑢𝑡 𝓋 = (𝑓𝑜𝑟 𝑖𝑛𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑙𝑒 𝑓𝑙𝑢𝑖𝑑𝑠)
2
2 2
∴ 2𝓋 𝑃𝑖𝑛 − 𝑃𝑜𝑢𝑡 + 𝑉𝑖𝑛 = 𝑉𝑜𝑢𝑡 ⇒ 𝑽𝒊𝒏 ≪ 𝑽𝒐𝒖𝒕 (Also used u = const assumption which is problem dependent)
• Solve for unknown properties through calculation of Δh and one other known thermodynamic
property.
• Non-ideal systems may have heat flows
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1st Law for control volumes — diffusers

Reverse of nozzles: convert velocity to pressure
Again, cannot assume that kinetic energy is negligible
Important in compressor design, found at entrance to jet engines (where it is not
incompressible flow!)
Same analysis approach as for nozzles
∴ 0 = 𝑚ሶ ℎ𝑖𝑛 − ℎ𝑜𝑢𝑡 − 𝛥𝑒𝑘 (𝑓𝑜𝑟 𝑏𝑜𝑡ℎ 𝑖𝑛𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑙𝑒/𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑙𝑒)
2 2
𝑉𝑜𝑢𝑡 − 𝑉𝑖𝑛
∴ 𝑢𝑖𝑛 + 𝑃𝑖𝑛 𝓋 − 𝑢𝑜𝑢𝑡 + 𝑃𝑜𝑢𝑡 𝓋 = (𝑓𝑜𝑟 𝑖𝑛𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑙𝑒 𝑓𝑙𝑢𝑖𝑑𝑠)
2
2 2
𝑉𝑖𝑛 = 𝑉𝑜𝑢𝑡 + 2𝓋 𝑃𝑜𝑢𝑡 − 𝑃𝑖𝑛 ⇒ 𝑽𝒊𝒏 ≫ 𝑽𝒐𝒖𝒕 (assuming u = const. If not, best
to use the enthalpy expression and proceed)

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1st Law for control volumes—throttling valves

Impingement on flow causes drop in pressure (can be a variety of physical forms)
No significant change in potential or kinetic energy, no heat, or work
ℎ𝑖𝑛 = ℎ𝑜𝑢𝑡
Energy transferred between flow energy and internal energy
(𝑢 + 𝑃𝒱)𝑖𝑛 = (𝑢 + 𝑃𝒱)𝑜𝑢𝑡
For ideal gases, no change in temperature as h = h(T) only;
For real gases generally there is a temperature drop due to transfer from internal
energy to flow energy.
Solve for unknown properties from enthalpy and one other known thermodynamic
property.

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1st Law for control volumes — turbines

Turbines are designed to extract work (important in all engines and
other power cycles)
Generally assume no change in potential or kinetic energy, often Q is
lost from system, if non-negligible

If the system is sufficiently specified we can determine unknown

quantities from property tables or equations of state.
If the system is not sufficiently specified we must know some other
piece of information about the internal path of the process.
You will be familiar with isentropic efficiency or adiabatic efficiency
from ENGG1500. We will revisit that concept after we discuss entropy.

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1st Law for control volumes — compressors

Compressors do opposite job to turbines. Compressors
include pumps and fans too.
Energy balance is identical to turbines.
𝑊ሶ 𝑖𝑛 = 𝑄ሶ 𝑜𝑢𝑡 + 𝑚(ℎ
ሶ 𝑜𝑢𝑡 − ℎ𝑖𝑛 )
If not fully specified, behaviour depends on the path. We will
review calculation of both turbines and compressors for ideal
gases after a discussion of entropy.
Note that for incompressible fluids (i.e. in pumps), specific
volume v is constant, and therefore a change in flow work
can be calculated explicitly:
𝑊ሶ 𝑖𝑛 = 𝑄ሶ 𝑜𝑢𝑡 + 𝑚(𝑢
ሶ 𝑜𝑢𝑡 − 𝑢𝑖𝑛 + 𝓋[𝑃𝑜𝑢𝑡 − 𝑃𝑖𝑛 ])
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Example 1.6 – Pump

The pump for a fountain needs to be designed: it will take 2 L/s water from a
lake, and eject it out of a 20 m vertical pipe at 50 m/s. How much power will this
require?
𝑚ሶ 𝑜𝑢𝑡 𝑣𝑜𝑢𝑡
50 m/s 𝑧𝑜𝑢𝑡 𝑢𝑜𝑢𝑡 𝑃𝑜𝑢𝑡

20 m
𝑊ሶ

𝑚ሶ 𝑖𝑛 𝑣𝑖𝑛 𝑃𝑖𝑛
2 L/s = 2 kg/s
𝑧𝑖𝑛 𝑢𝑖𝑛
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Example 1.6 – Pump (method 2)

The pump for a fountain needs to be designed: it will take 2 L/s water from a
lake, and eject it out of a 20 m vertical pipe at 50 m/s. How much power will this
require?

50 m/s 𝑚ሶ 𝑧2 𝑉2 𝑢2

20 m
𝑊ሶ

𝑧1 𝑉1 𝑢1
2 L/s = 2 kg/s
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1st Law for control volumes — heat exchanger

Transfer heat from one fluid to another. You will be familiar with these from
the heat transfer component
Generally assumed to be steady-state, and have no work, and negligible
changes in kinetic and potential energy:
0 = 𝑄ሶ 𝑖𝑛 + 𝑚ሶ ℎ𝑖𝑛 − ℎ𝑜𝑢𝑡
For incompressible fluids, 0 = 𝑄ሶ 𝑖𝑛 + 𝑚ሶ 𝑢𝑖𝑛 − 𝑢𝑜𝑢𝑡
Generally isobaric.
Where the system boundary is drawn is very important. E.g. a boundary
around the entire system calculates heat losses only.
Thermodynamic analysis where input and output states are specified is
trivial. Where they are not specified, analysis by heat transfer is necessary.

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1st Law for control volumes — Unsteady Flow

What about cases where an assumption of steady state doesn’t apply, but where system is open?
E.g. filling or emptying gas cylinders
Unlike steady-state flow, system energy of unsteady flow changes with time, namely 𝑑𝐸𝑠𝑦𝑠 /𝑑𝑡 =
𝐸ሶ 𝑖𝑛 − 𝐸ሶ 𝑜𝑢𝑡 ≠ 0, therefore we have:

𝑑𝐸 𝑑
= 𝑄ሶ − 𝑊ሶ + 𝑚ሶ 𝑖𝑛 ℎ + 𝑒𝑘 + 𝑒𝑝 − 𝑚ሶ 𝑜𝑢𝑡 ℎ + 𝑒𝑘 + 𝑒𝑝 = 𝑚(𝒖 + 𝑒𝑘 + 𝑒𝑝 )
𝑑𝑡 𝑖𝑛 𝑜𝑢𝑡 𝑑𝑡
• Most unsteady-flow problems are uniform-flow process, so we consider system energy
difference between final and initial states

𝒅 Subscripts:
𝑄ሶ − 𝑊ሶ + 𝑚ሶ 𝑖𝑛 ℎ + 𝑒𝑘 + 𝑒𝑝 − 𝑚ሶ 𝑜𝑢𝑡 ℎ + 𝑒𝑘 + 𝑒𝑝 = (𝒎𝟐 𝒆𝟐 − 𝒎𝟏 𝒆𝟏 )𝒔𝒚𝒔 “1” denotes “initial”
𝑖𝑛 𝑜𝑢𝑡 𝒅𝒕 “2” denotes “final”
To compare, we rewrite the energy conservation equation for steady-state flow:
𝑄ሶ − 𝑊ሶ + 𝑚ሶ 𝑖𝑛 ℎ + 𝑒𝑘 + 𝑒𝑝 𝑖𝑛
− 𝑚ሶ 𝑜𝑢𝑡 ℎ + 𝑒𝑘 + 𝑒𝑝 𝑜𝑢𝑡
=𝟎

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Example 1.7 – Filling steam into tank

A rigid, insulated tank is initially evacuated and connected to a steam line (at 1 MPa
and 300°C, specific enthalpy is 3051.6 kJ/kg). Steam is allowed to flow into the tank
slowly until the tank reaches 1 MPa. Determine the specific internal energy of steam
in the tank at this moment.

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Thermodynamic Properties
Pure substance
Phase changes
Property diagrams & tables
Equations of State
Ideal Gas
Real Gas
Specific Heat Capacities

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Properties of Pure Substances Intro

We have talked in general terms about solving 1st Law problems
Solving specific problems requires us to determine thermodynamic properties, and how to calculate
changes in properties
We will deal predominantly with pure substances, but it is important you are aware of the behaviour of
mixtures.

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Pure substances
A pure substance is one with fixed chemical composition throughout the system
-About homogeneousness of chemical compositions, does NOT have to be single chemical
compound;
-Oxygen (O2), water, and air are all pure systems;
-A mixture of two phases of a pure substance is still a pure substance, e.g. a mixture of ice and
water;
-However, a mixture of liquid air and gaseous air isn’t;
(as the composition of liquid air is different from
that of the gaseous air. This is due to different
compositions in air condensing at different
temperatures at a specified pressure.)

This is a somewhat clunky definition, but it is used as the properties of pure substances can be
defined explicitly.

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Phase Change
“phase” is the identification of a distinct molecular
arrangement of substance.
Three principle phases, several sub-phases
Heat addition or removal from a substance can result in
phase change.
Generally quantified by a change in enthalpy (this takes
into account the substantial changes in volume that can be
associated with the phase change)

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Phase Change
Consider a heating process of liquid water contained in a cylinder with a very light lid.

Compressed Saturated Saturated liquid- Saturated Superheated

liquid liquid vapor mixture vapor vapor
- liquid not about to - liquid about to - two phases coexist - vapor about - vapor not about
vaporize vaporize in equilibrium to condense to condense
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Saturated
Phase Change l-v mixture
Superheated
Saturated vapor
liquid All the states
the heating
Saturation temperature 𝑻𝒔𝒂𝒕
process goes
- a temperature at which the
through can
phase starts to change
be illustrated
by a path in a
diagram.
Compressed Reversed
liquid process will
retrace the
Saturated same path.
vapor

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Thermodynamic properties to describe states

In many analyses we know some properties but must determine others.
For a pure substance system, at the equilibrium state, we can generally determine all thermodynamic
properties if we know any two independent intensive properties(e.g. T, P, v, ρ, u, h, s, etc.).
-For each additional component present we must know an additional property (often composition).

There are broadly two ways to determine these properties:

- 1. Thermodynamic property tables or diagrams.
- 2. Equations of state (there are a variety of these).
We will use one (the ideal gas law) frequently.

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Property diagrams
The phase-change process is usually characterised by two intensive properties
in T, P, and V. Consequently, we can obtain three diagrams T-v diagram, P-v
diagram and P-T diagram.
Fixed T does
NOT mean NO
heat transfer!

Saturation
pressures

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Property diagrams
Saturation liquid line and saturation vapor line meets at the critical point. All compressed
liquid states are located to the left of saturation liquid line, while all superheated vapor states are
to the right of saturation vapor line. Saturated liquid-vapor states are located under
the dome. Saturation temperature has a definite relation with
saturation pressure, i.e. 𝑇𝑠𝑎𝑡 = 𝑓 𝑃𝑠𝑎𝑡

Table A-1
is used
for
different
substance
.
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Supercritical state
In states beyond the critical point, i.e. supercritical states, there is not a distinct
phase change happening. It exhibits a single phase neither liquid nor vapor. Instead,
the supercritical phases “look” similar to superheated vapor (if you can see them!).

CO2

Saturated liquid-vapor mixture state Supercritical state

Thermodynamics: Introduction, First Law and Properties 51
Property Tables

Property tables are used for most substances depending on regions of interest (states).

Saturated liquid and/or saturated vapor states (A & E) — Tables A-4 & A-5
• T and P are dependent to each other. Properties are acquired directedly in the
Tables based on T or P.
Saturated liquid-vapor mixture (D) — Tables A-4 & A-5
• Properties are the averaged values between sat. liquid and sat. vapor from
Table A-4 and A-5., calculated using quality.

𝑚 𝑣𝑎𝑝𝑜𝑟
• Quality (of saturated mixture): 𝑥 = , then 𝓋𝑎𝑣𝑔 = 𝓋𝑓 + 𝑥𝓋𝑓𝑔 , where 𝓋𝑓𝑔 = 𝓋𝑔 − 𝓋𝑓
𝑚𝑡𝑜𝑡𝑎𝑙
• u, h, and s also have: 𝑦𝑎𝑣𝑔 = 𝑦𝑓 + 𝑥𝑦𝑓𝑔
Critical point (F) — Tables A-1
• T, P and 𝓋 are fixed for one substance.

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Property Tables
Superheated vapor (B) — Table A-6
Properties can be looked up in Table A-6, but confirm the state first!
Rules for determining a superheated state
▪ 𝑃 < 𝑃𝑠𝑎𝑡 at a given temperature
▪ 𝑇 > 𝑇𝑠𝑎𝑡 at a given pressure
▪ 𝓋 > 𝓋𝑔 , 𝑢 > 𝑢𝑔 or ℎ > ℎ𝑔 at a given P or T

Compressed liquid (C) — Table A-7

similar to superheated vapour. Determine rule:
u
▪ 𝑃 > 𝑃𝑠𝑎𝑡 at a given temperature
▪ 𝑇 < 𝑇𝑠𝑎𝑡 at a given pressure
▪ 𝓋 < 𝓋𝑓 , 𝑢 < 𝑢𝑓 or ℎ < ℎ𝑓 at a given P or T
Most problems in this Course rely on determination of thermodynamic properties which you will need to be
proficient at.
Often, states are not explicitly given. You will need to determine the state using properties.

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Example 1.8 – Applications of Property tables

1. A rigid tank contains 50 kg of saturated liquid water at 90°C,
determine the pressure in the tank and the tank volume.

2. Piston-cylinder device contains 0.06 m3 of saturated water vapor at

350 kPa pressure, determine the temperature and mass of vapor in
the cylinder.

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Example 1.8 – Applications of Property tables

3. An 80 L vessel contains 4 kg of R-134a at a pressure of 160 kPa, determine the
temperature, the quality, the enthalpy, and the volume occupied by the vapor phase.

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Example 1.8 – Applications of Property tables

4. Water inside a container is at a pressure of 0.5 MPa and an enthalpy of 2890 kJ/kg.
Determine the temperature of water.

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Equations of State
Any equation that relates the pressure, temperature and specific volume of a
substance (i.e. P-v-T behaviour) is called an Equation of State.
A variety of more precise equations of state are used for different purposes.
These vary from empirical fits of data to theory-based equations.
In all instances, they provide an explicit link between T, P, and v (or ρ).
-This in fact provides a jumping-off point for determining the other
thermodynamic properties.
We are most interested in the ideal-gas equation of state in this course.

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Ideal Gases
Ideal gas can be imagined as a number of randomly moving particles which have only elastic
(and rare) collisions.
Ideal gas is approached for dilute systems (it is approximately true for many real gases at room
temperature and pressure.
Ideal-gas equation of state (ideal gas law) — 𝑃𝒱 = 𝑁𝑅𝑢 𝑇 where P is absolute
pressure (Pa), V is total
More common forms volume (m3), N is number of
moles (J), Ru is the
𝑹𝒖
unit-mass: 𝑷𝓿 = 𝑹𝑻 = 𝑻 unit-mole: 𝑃𝓋 ഥ = 𝑅𝑢 𝑇 universal gas constant
𝑴
(8.314 J/mol/K) and T is
total-mass: 𝑃𝒱 = 𝑚𝑅𝑇 ❖ R is gas constant; absolute temperature (K)
Two different states: ❖ M is molecular mass for
𝑷𝟏 𝓥𝟏 𝑷𝟐 𝓥𝟐 a substance, in g/mol;
= ❖ m is mass, in kg; Be careful with units
𝑻𝟏 𝑻𝟐 𝑅
Must be fixed mass!
❖ 𝑅 = 𝑢 , 𝑚 = 𝑁𝑀
𝑀
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Example 1.9 – Temperature rise in tires

A car tyre is measured to have gage pressures of 210 kPa before a trip and 220 kPa
after the trip at a location where the atmospheric pressure is 95 kPa. Assume the
volume of the tyre remains nearly constant and the air temperature before the trip is
25°C, determine the air temperature in the tire after the trip.

210 kPa
25°C
S1

220 kPa
S2 ? °C

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Limits on Accuracy of Ideal Gas Law

At low pressure and high temperature, real gases
behave as ideal gases.
In practice, many common gases can be treated as
ideal gas.
At other conditions, potential for deviation
Water vapor is ideal gas at pressure lower than 10 kPa,
see figure.

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Real Gases

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Real Gases
In pure real gases, state is characterised by any 2 intensive thermodynamic
properties. For example, T & P, P & v, T & v, T & ρ, etc, i.e. u = u(T,P), h =
h(T,P), v = v(T,P)
Most common equation of state for real gases is:

where 𝑃𝒱 = 𝑍𝑅𝑇
𝒱𝑎𝑐𝑡𝑢𝑎𝑙
▪ Z is a compressibility factor, defined by 𝑍 =
𝒱𝑖𝑑𝑒𝑎𝑙
▪ Z is generally identified through a ‘compressibility chart’

• This model provides a good estimate of gas behaviour for many gases.
You should be familiar with this as professional engineers.

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Compressibility Charts
The compressibility factor, Z, is
function of reduced pressure.
𝑃
Reduced pressure: 𝑃𝑅 =
𝑃𝑐𝑟
𝑇
Reduced temperature: 𝑇𝑅 =
𝑇𝑐𝑟
Z for all gases is quite same at
same 𝑃𝑅 and 𝑇𝑅 .
At 𝑃𝑅 ≪ 1 and 𝑇𝑅 > 2, gases
behave like an ideal gas.
Deviation from ideal gas
behaviour is greatest in the
vicinity of the critical point.

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Specific heat capacities

Specific heat (capacity): the heat required to raise the temperate of a unit
mass of a substance by one degree.
Provide a link between changes in temperature and internal energy or
enthalpy.
Constant volume: 𝑑𝑢 = 𝛿𝑞 = 𝑐𝑣 𝛿𝑇 ⇒ 𝑐𝑣 𝛿𝑇 = 𝑑𝑢
𝝏𝒖 ഥ
𝜕𝑢
𝒄𝒗 = ( )𝒗 , per mole 𝑐ഥ𝑣 = ( )𝑣
𝝏𝑻 𝜕𝑇
Constant pressure: 𝑑𝑢 = 𝛿𝑞 − 𝑃𝑑𝓋 = 𝐶𝑃 𝛿𝑇 − 𝑃𝑑𝓋
⇒ 𝑑𝑢 + 𝑃𝑑𝓋 = 𝐶𝑃 𝛿𝑇 = 𝑑ℎ
𝝏𝒉 ഥ
𝜕ℎ
𝒄𝒑 = ( )𝒑 , per mole 𝑐𝑝 = ( )𝑝
𝝏𝑻 𝜕𝑇
Enthalpy: ℎ = 𝑢 + 𝑃𝓋 or 𝐻 = 𝑈 + 𝑃𝒱
Enthalpy commonly used in gas and liquid, seldom in solids.

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Specific heat capacities

Specific heat is not constant for most substances:
they vary with temperature
Specific heat is a function of temperature
𝑐ഥ𝑝 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 + 𝑑𝑇 3
T in K, 𝑐ഥ𝑝 in kJ/kmol K
𝑐𝑝
Specific heat ratio: 𝑘 =
𝑐𝑣

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Properties for ideal gases & incompressible substances

Ideal gas Incompressible substances
𝐶𝑝 = 𝐶𝑣 + 𝑅 𝐶𝑝 = 𝐶𝑣 = 𝐶
Specific heat ratio 𝑘 = 𝐶𝑝 /𝐶𝑣
𝑢 = 𝑢(𝑇) 𝑑𝑢 = 𝑐 𝑇 𝑑𝑇
𝑑𝑢 = 𝑐𝑣 𝑇 𝑑𝑇 ∆𝒖 ≅ 𝒄𝒂𝒗𝒈 (𝑻𝟐 − 𝑻𝟏 )
𝑇2
∆𝑢 = 𝑢2 − 𝑢1 = න 𝐶𝑣 𝑑𝑇
𝑇1
∆𝒖 ≅ 𝒄𝒗,𝒂𝒗𝒈 (𝑻𝟐 − 𝑻𝟏 )
ℎ = ℎ(𝑇) ∆𝒉 = ∆𝒖 + 𝓿∆𝑷
𝑑ℎ = 𝑐𝑃 𝑇 𝑑𝑇 ≅ 𝒄𝒂𝒗𝒈 ∆𝑻 + 𝓿∆𝑷
𝑇2
∆ℎ = ℎ2 − ℎ1 = න 𝐶𝑃 𝑑𝑇
𝑇1
∆𝒉 ≅ 𝒄𝑷,𝒂𝒗𝒈 (𝑻𝟐 − 𝑻𝟏 )

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Temperature (Zeroth Law)

What is temperature anyway?
Not easy to define precisely, but related to the heat content of matter
It allows us to indicate thermal equilibrium

Planck’s statement of the zeroth law of thermodynamics:

If a body A, be in thermal equilibrium with two other bodies, B and C, then B and C are in thermal
equilibrium with one another

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Example 1.10 – Heating of air in a cylinder

An air-fuel mixture in a car cylinder is ignited and, at constant pressure, increases in
temperature from 30°C to 900°C. Determine the heat input based on mean heat
capacity and property tables, treating the mixture as consisting of only air.

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Example 1.11 – Air compressor

Air is compressed from 100 kPa and 30°C to 400 kPa and 150°C. The flow-rate
of air in is 5 litres per second, and there is a heat flow of 430 J/s out of the walls
of the compressor. Determine the work input.
𝑤𝑜𝑟𝑘 =?

100 kPa 400 kPa

30°C 150°C

𝑄ሶ = 430 𝐽/𝑠
0.005
𝑣ሶ = 5 𝐿Τ𝑠 ∴ 𝑚ሶ = = 0.004 𝑘𝑔/𝑠
1.225
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Next up
entropy

Thermodynamics: Introduction, First Law and Properties 70