Engineering Science Department Pakistan Navy Engineering College National University of Sciences & Technology

Lesson # 10 - 12 : Laws of Thermodynamics
Thermodynamics I (ME 130)

Objective of lesson
1. State and discuss

a. Zeroth Law of Thermodynamics
b. Law of Conservation of Mass
c. First Law of Thermodynamics and its consequences.
2. Learn to apply mass balance and energy balance

equations for solution of numerical problems.
Engineering Science Department
Khurram Jamal Hashmi Pakistan Navy Engineering College 1 of 17
National University of Sciences & Technology
Laws of Thermodynamics
Laws of thermodynamics (like Newton’s laws of motion and other laws of nature) are generalized statement
deduced from the observation of the universe and for which no exception is observed. The validity of the law lies
in the fact that it is not violated within its framework, even by a single event occurring anywhere in the universe.
There are four laws of thermodynamics: zeroth, first, second and third law. Law of conservation of mass is also
required for thermodynamic analysis.
There are different statements of the same law. One statement has to be accepted as the universal truth, the
other statements can be proved equivalent to this one.
Various important consequences can be derived from a law. These consequences define new concepts which
are building blocks of science of thermodynamics.
For our scope of study: only statements of zeroth and third law are required; first law, second law and principle
of conservation of mass are to be utilized in thermodynamic analysis.

Zeroth Law of Thermodynamics
Statement: When two systems, isolated from other environment are in

thermal equilibrium with a third system, the two are in thermal equilibrium
with each other. [Thermodynamics by V M Faires 5th edition]
The law can simply be understood as: if temperature of system A equals

temperature of system B, and temperature of system B equals
temperature of system C, then system A and system C are at equal
temperatures.
The law has applications in area of temperature measurement.

Law of Conservation of Mass
Statement: Mass is neither created nor destroyed.
Mathematically: Σmin - Σmout = Δmsystem [Mass Balance Equation]

i.e. the difference of total mass that enters a system and that leaves the system equals change in
mass of the system itself.
Law is valid for total mass of the system, as well as individual chemical constituent of the system. For
our scope, later is not required. Thus, mass balance relation (as given above) is not required for
closed systems.
For steady-state steady-flow process mass balance is written in rate form and there is no change
within the system (by definition). Mathematically,
Σmin - Σmout = 0
First Law of Thermodynamics
Statement: Energy is neither created nor destroyed (energy

conservation principle)
Mathematically: ΣEin - ΣEout = ΔEsystem [Energy Balance Equation]

i.e. the difference of total energy that enters a system and that
leaves the system equals change in energy of the system itself.
The right hand side of the equation is the change within the system
and left hand side represent changes at the boundary of the system
Change in energy of the system ΔEsystem is sum of change in internal energy ΔU, change in kinetic energy ΔKE,
change in gravitational potential energy ΔPE, change in electromagnetic potential energy and others. Change in
internal energy comprises of change in nuclear bond energy, change in chemical bond energy and change in
thermal energy. Mathematically,
ΔEsystem = ΔUnuclear + ΔUchemical + ΔUthermal + ΔKE + ΔPE + others
For thermo-mechanical systems (our scope of study) changes in nuclear bond energy, chemical bond energy and
other forms energies are negligible as compared changes in thermal energy, kinetic energy , gravitational
potential energy.
ΔEsystem = ΔU + ΔKE + ΔPE
For thermo-mechanical stationary systems
ΔEsystem = ΔU
There are three modes of energy transfer: heat Q, work W and mass m. Each element of mass m
crosses a boundary with specific energy e; which is sum of energies as discussed in last slide i.e. e =
u + ke +pe for thermo-mechanical systems. Mathematically,
ΣEin = ΣQin + ΣWin + Σminein = ΣQin + ΣWin + Σmin (uin + kein + pein)
In most commonly used form of the equation work W includes all form of work except flow work. Flow
work adds to internal energy to give enthalpy (Enthalpy = Internal Energy + Flow Work)
ΣEin = ΣQin + ΣWin + Σmin (hin + kein + pein)
Similarly,
ΣEout = ΣQout + ΣWout + Σmout (hout + keout + peout)

The final form of energy balance equation for thermo-mechanical systems is:
[ΣQin+ΣWin+Σmin (hin+kein+pein)] – [ΣQout+ΣWout+Σmout (hout+keout+peout)] = ΔU+ΔKE+ΔPE
For closed thermo-mechanical systems:

[ΣQin + ΣWin] – [ΣQout + ΣWout] = ΔU + ΔKE + ΔPE
For stationary closed thermo-mechanical system:

[ΣQin + ΣWin] – [ΣQout + ΣWout] = ΔU
For steady-state steady-flow process rate form of equation is used:

[ΣQin+ΣWin+Σmin (hin + kein + pein)] – [ΣQout+ΣWout+Σmout (hout + keout + peout)] = 0
First Law of Thermodynamics – Numerical Problem
Problem # 1:
A system undergoes a process in which the heat transfer to the system is 40 kJ and the
work done by the system is 45 000 N m. Evaluate the increase in the energy of the
system.
Solution:
Energy balance for closed system:

[ΣQin + ΣWin] - [ΣQout + ΣWout] = ΔE
[40000 + 0] - [0 + 450000] = ΔE
ΔE = 40000 - 45000
ΔE = -5000 J
Problem # 2:
A 100 mm-diameter vertical cylinder, closed by a piston, contains a combustible

mixture at a temperature of 15oC. The piston is free to move and its mass is such
that mixture pressure is 240 kPa; the upper surface of the piston exposed to
atmosphere. The mixture is ignited. As the reaction proceeds, the piston moves
slowly upwards and heat transfer to the surroundings takes place. When the
reaction is complete and the temperature of contents has been reduced to initial
value, 15oC, it is found that the piston has moved upwards a net distance of 85
mm and that the magnitude of the heat transfer to the surroundings is 4 kJ.
Evaluate the increase in the energy of the contents of cylinder.
Solution: [Note: Complete solution is shown below. The application of the laws start from next slide]
System: Mass contained within cylinder piston arrangement. Initially the system contains
combustible mixture and finally mixture of combustion products.
Known: diameter of cylinder, initial and final temperatures, constant pressure maintained in cylinder,
heat transfer to surrounding atmosphere, net distance the piston has moved.

Find: increase in energy of the contents of cylinder

Assumptions:
The system is leak-proof (closed system).
The process is isobaric.

Analysis:

Mass balance: Not required for closed system

Energy balance for closed system:
[ΣQin + ΣWin] - [ΣQout + ΣWout] = ΔE
[0+0] - [Qout +∫PdV] = ΔE [as Wout = Wboundary = ∫PdV]
ΔE = - [4000 + (240 x 103) [(0.25) (π) (0.1)2 (0.085)]
ΔE = -4160 J
Problem # 3:
A gasoline engine develops a brake power of 50 kW. The mass flow

rate of fuel into the engine is 15 kg/h and that of air is 215 kg/h; the
temperature of the fuel-air stream entering the engine is 15oC and the
temperature of the gas leaving the engine is 900oC. The heat transfer
rate to the jacket cooling water is 42 kJ/s and that to surrounding
atmosphere is 15 kJ/s. Evaluate the increase in specific enthalpy of
the mixture stream as it flows through the engine, assuming the
kinetic and potential energies to be negligible.
Solution: [Note: Complete solution is shown below. The application of the laws start from next slide]
System: Control volume including cylinder-piston arrangements, crankshaft and all mechanical linkages, exhaust
manifold, intake manifold up till the fuel inlet and air inlets. Control volume may be depicted as mixing chamber with
air and fuel entering and exhaust gases leaving.

Known: Inlet flow rates, heat transfer to cooling water and surrounding atmosphere, power output (brake power),
intake mixture temperature and exhaust temperature.

Find: increase in specific enthalpy of mixture stream

Assumptions:
Steady-state steady flow process with uniform properties at inlets and outlets. Although engine operation is
intermittent, but owing to continuous operation with high rpm this assumption is valid.
Changes in kinetic, potential, electrical, electromagnetic and other form of energies (except internal energies) are
negligible.

Analysis:

Mass balance for steady-state steady-flow: Σmin - Σmout = 0
For the given system: m1 + m2 = m3

Energy balance: For steady-state steady flow:

[Σmin(h + pe + ke + ……..) +ΣQin + ΣẂin] - [Σmout(h + pe + ke + ……..) +ΣQout + ΣẂout] = 0

The changes in streams’ potential, kinetic and other form of energies (except internal energy) are negligible. The equation for given
system reduce to:

[m1h1 + m2h2] - [m3h3 + Qjacket water + Qsurrounding + Wbrake] = 0
[h3 – (m2h2 + m1h1)/m3] = -[Qjacket water + Qsurrounding + Wbrake] / m3
= -[42 + 15 + 50] / [(15 + 215) / 3600)]
= -1674 kJ/kg mixture
First Law of Thermodynamics – Consequences
1. When any closed system is taken through a cycle, the net work delivered to
the surrounding is proportional to net heat taken from the surroundings.
∫cycleδQ α ∫cycleδW
J∫cycleδQ = ∫cycleδW
The ‘J’ is constant proportionality known as Joule equivalent or mechanical
equivalent of heat. It has value of 1 in SI units and 778 ft-lbf/BTU in US
customary system of units.
2. A perpetual motion machine of first kind (PMM I) is impossible. A perpetual

motion machine of first kind is a type of machine that provides a continuous
supply of work without absorbing energy from the surroundings.
Outcome of Lesson
At the end of the lesson the student should be able to:
1. State and explain zeroth and first law of thermodynamics.
2. Write down mass balance and energy balance equation in their

general form and apply them for closed and steady-state systems.
3. Can define and describe perpetual machine of first kind and

mechanical equivalent of heat.

Engineering Science Department Pakistan Navy Engineering College National University of Sciences & Technology

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Lesson # 10 - 12 : Laws of Thermodynamics

Thermodynamics I (ME 130)

1. State and discuss

2. Learn to apply mass balance and energy balance

Engineering Science Department

Statement: When two systems, isolated from other environment are in

The law can simply be understood as: if temperature of system A equals

The law has applications in area of temperature measurement.

Statement: Mass is neither created nor destroyed.

Mathematically: Σmin - Σmout = Δmsystem [Mass Balance Equation]

Statement: Energy is neither created nor destroyed (energy

Mathematically: ΣEin - ΣEout = ΔEsystem [Energy Balance Equation]

ΔEsystem = ΔUnuclear + ΔUchemical + ΔUthermal + ΔKE + ΔPE + others

ΔEsystem = ΔU + ΔKE + ΔPE

For thermo-mechanical stationary systems

ΣEin = ΣQin + ΣWin + Σmin (hin + kein + pein)

ΣEout = ΣQout + ΣWout + Σmout (hout + keout + peout)

For closed thermo-mechanical systems:

For stationary closed thermo-mechanical system:

For steady-state steady-flow process rate form of equation is used:

Energy balance for closed system:

A 100 mm-diameter vertical cylinder, closed by a piston, contains a combustible

A gasoline engine develops a brake power of 50 kW. The mass flow

For the given system: m1 + m2 = m3

2. A perpetual motion machine of first kind (PMM I) is impossible. A perpetual

At the end of the lesson the student should be able to:

1. State and explain zeroth and first law of thermodynamics.

2. Write down mass balance and energy balance equation in their

3. Can define and describe perpetual machine of first kind and

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