DEFINITIONS

MECH103P Thermodynamics
2015

Course Structure

Lectures
Tutorial sessions
Laboratory exercises (3)
Evaluation:
Final Exam (1)

Resources

Moodle.ucl.ac.uk
UCLWiki Thermodynamics page
Handouts
Online Discussion Forums
Surgery Hours

Introduction
Thermodynamics is the science of the relations between heat,
work and the properties of systems.
It is the science of energy transfer and its effects on the physical
properties of substances
It is primarily based upon the observations of common experience
formulated into laws, which govern energy conversion.

The applications of the thermodynamic laws and principles are

found in

Internal combustion engines

Gas turbines
Steam and nuclear power plants
Air conditioning and refrigeration
Gas dynamics
Jet propulsion
Chemical processing plants
Any direct energy conversion devices

Thermodynamic System
In the study of any special branch of physics we usually start with a
separation of a restricted region of space or a finite portion of matter
from its surroundings. The portion that is set aside and on which
attention is focused is called the system.
System is a fixed and identifiable collection of matter enclosed by a
real or imaginary surface which is impermeable to matter but which
may change its shape or volume. The surface is called the
boundary.
Surroundings or environment: Everything outside the system
which has a direct bearing on the system's behaviour.

Classes of Systems
boundary
of ??

(1)

(2)

gas in cylinder

Closed system:
Fixed mass. No mass transfer across the system boundary;
energy transfer into or out of the system may occur

Open system:
Matter crosses the boundary of the system; energy transfer
may also exist

Isolated system:
There is no interaction between the system and the
surrounding

Find out about: Control volume, Control surface

Macroscopic Vs Microscopic
When a system has been chosen, the next step is to describe it in
terms of quantities related to the behaviour of the system or its
interactions with the surrounding or both. Two points of view may
be adopted: macroscopic or microscopic
Microscopic approach considers the behaviour of every molecule
by using statistical methods. The study based on this approach is
generally called Molecular thermodynamics
In Macroscopic approach we are concerned with the gross or
average effects of many molecules' interactions. These effects,
such as pressure and temperature, can be perceived by our senses
and can be measured with instruments. This approach greatly
reduces the complexity of the problem and we use this approach in
this course. This is known as "Classical Thermodynamics".

Property
The conditions of the system, and the substance within it, is defined
by the properties of a system.
A Property is any observable characteristic of a system.
Properties can be defined only when they are uniform throughout a
system eg impossible to define the pressure of an exploding system
(??).
Examples:

Length,
volume,
pressure,
density,
refractive index, etc.

Property: Pressure
A property which is quite important in thermodynamics is the
pressure.
A fluid exerts forces on its boundaries, due to the change in
momentum of molecules when they collide with the boundary.
These forces are not concentrated at one particular point, due to
random motion of molecules, but are distributed. Therefore, we can
define pressure as the normal force exerted on a surface, divided by
the area of the surface.
The unit of pressure is the force 1 Newton acting on a square metre
area, which is called a Pascal.
1 Pa = 1 N/m2 and 1 bar = 105 Pa

Property: Pressure

In most thermodynamics investigations we are concerned with the

absolute pressure. However, most pressure gauges measure the
difference between the absolute pressure and the atmospheric
pressure which is known as gauge pressure.

gauge pressure
measured by pressure
gauge

absolute
pressure

atmospheric
pressure
0 pressure

Extensive & Intensive Properties

In general one can make distinction between two types of
properties.
(i) Extensive:
Extensive properties are those whose value is the sum of the
values for each subdivision of the system, eg mass, volume.
(ii) Intensive
Properties are those which have a finite value as the size of the
system approaches zero, eg pressure, temperature, etc.
Extensive properties may be made intensive by dividing them by
the system mass. For example:
system volume = 12 m3, mass = 4 kg
system specific volume = 12/4 = m3/kg

State
The state of a system is fixed by defining all its properties or
sufficient properties so that all others may be described. The state
of a system changes if any property changes. In most of the simple
systems that we shall consider a small number of properties will be
enough to completely define the state of a system.
Equilibrium

A system is in thermodynamic equilibrium if no tendency towards

spontaneous change exists within the system. Energy transfers across
the system disturb the equilibrium state of the system but may not shift
the system significantly from its equilibrium state if carried out at low
rates of change.
Note: to define the properties of a system, they have to be uniform
throughout the system. Therefore to define the state of a system, the
system must be in equilibrium. (Inequilibrium of course implies nonuniformity of one or more properties).

Process (1/2)
A process is the description of what happens when a system
changes its state by going through a succession of equilibrium
states.
Property Diagram and Path
Consider a system which we are monitoring and assume that properties X
(pressure) and Y (eg. volume), which are being measured, are enough to define
the state of the system. Then if we plot X versus Y, we get a Property diagram.

2
1

Process (2/2)

A point, such as 1, on the diagram represents the properties of the system at a particular instant and is known as
a state point. Three different hypothetical processes have been drawn:

Process 1 - 2:

Process 3 - 4

In this case the properties have been measured at points a, b, c, d, ..., etc, and so we can draw a dotted line
through the points.

Process 5 - 6:

is relatively undefined. We cannot guess what happens between the two equilibrium states 1 and 2.

In this case the properties have been measured continuously and we have obtained an infinity of equilibrium
states between 5 and 6. We are now justified in drawing a full line. This line is called the path of the
process. Note: to fully define the process we need to monitor the system - surrounding interactions as well.

Cyclic Process
A cyclic process is one for which the initial and final states of the system are
identical.

4
Y

2
6

5
x

Interactions Between Systems (Work &

Heat)

What happens when we bring two systems into contact?

The configuration or states of (A) and (B) may be altered until after a certain time
when the systems reach equilibrium, and there is no change. Systems (A) and
(B) can interact even at a distance, eg. earth and moon (tide). But in
Thermodynamics, we are concerned with only two kinds of interactions, work and
heat.
Thermodynamic Definition of Heat and Work
In mechanics work is defined as a force acting through a displacement x, the
displacement being in the direction of the force. That is:
W=Fxx
or in the case in which F is varying

Unit of work - 1 Nm = 1 Joule

But this definition of work is very restrictive and not adequate in
Thermodynamics. (Example a system consisting of a battery!)

Work - Interactions Between Systems I

"Positive work is done by a system,
during a process, when the ONLY
effect external to the system could
be reduced to the rise of a weight".
Definition seems arbitrary! But partly
is forced on us since we have to
make distinctions between work and
heat as a result of the Second Law
of Thermodynamics.
A simple way to visualise this:
The system boundary moves in such a way as
to push the lever system to a new dotted
position. The work done as in mechanics is
(WxL) Nm.

Work - Interactions Between Systems I

This does not show the width of the application of Thermodynamic
definition. So consider a battery which we take as our system. The
battery terminals are connected to a resistor through a switch:

When the switch is shut for a time, current flows through the resistor
and it becomes "Warmer". Is this a work interaction? Of course from
mechanics we would say NO! (since no force has moved its point of
application).

Work - Interactions Between Systems I

But now let us image that:

That is we have imagined a practical arrangement which includes a

pulley and an electric motor.
If we again close the switch, the electric current will drive the electric
motor which winds up a string attached to a weight. That is the sole
effect external to the system could be the rise of a weight. This
interaction is work!

Some Notes:
(i) The "ONLY effect", is necessary since, an interaction
in the form of heat transfer could result in the rise of a
weight as a part of its effect.
(ii) External to the system - Work is defined with respect
to a system boundary. If you choose a different system
and hence boundary, then work may be changed.
(iii) "Could be reduced to" - This means that a weight does
not actually have to be raised, but we must be able to
visualise a real physical method of raising the weight by
hypothetical changes in the surroundings!
(iv) "Positive Work"; also implies negative work!

Negative Work

"If a system does positive work, then obviously the surrounding do an equal amount of
negative work and vice versa. In symbols:
W system+ Wsurroundings = 0

Sign Convention

Work is done by the system

Work is done on the system

Important to know:
Work is a Transient. It is present during the interaction but does not exist either before or
after the interaction. It is something which happens to a system but it is not a
characteristic of a system ie not a property!

Further-study
Homogenous Heterogeneous systems
Types of pressure gauges
On Equilibrium State
Chemical
Mechanical
Thermal

Quasi-static process
Prepare a chart on Units and Dimensions

Interactions Between Systems:

Heat and Work

Displacement work

Consider a system consisting of a cylinder and a piston:

Assume that the system is in equilibrium, i.e. PA = Force

due to weight.
Now if we remove the small weight, the finite unbalanced
force will cause the system to pass through non-equilibrium
states. This is not desired: Thermodynamic state cannot be
defined?!
So we assume that process is "quasi-static", that is, the
force is infinitesimal and so the state is infinitesimally near a
thermodynamic equilibrium. This is called fully resisted
expansion.

But AdL = dV, change in volume of the gas, so:

The total work done at the moving boundary can be

performed by integrating this equation, i.e;

Interactions Between Systems:

Heat and Work
A number of points should be made here:
i) P is the pressure at the systems'
boundary and not necessarily the system
pressure!
ii) dV is the differential of the volume
swept out by the system boundary and
not in general the differential of the
system volume
e.g.
iii) The total work done by a system is not
equal to integral of pdV since other forms
of work such as electrical, magnetic etc
might be present!

The relationship between P&V

At the start of the process, the piston is at position 1, the

pressure being relatively low. At the end of the process the
piston is at 2. Assume the process is quasi-static so that we
know the state of the system from 1-2 and so can draw a full
line. The work done on the air during the compression
process =
= Area under the curve 1-2, or (1-2-b-a)

Possible to go from 1 to 2 along many different quasi-static

paths, such as B & C. Since the work done is equal to the
area underneath the curve, we can see that the amount of
involved in each case is a fraction not only of the end-states
of the process, but in addition is dependant on the path that
is followed in going from 1-2. For this reason work is called
a path function, as opposed to thermodynamics properties
which are point functions.

Special cases of P&V

relationships
1.The constant volume process
(isochoric)

Area underneath curve = 0

Special cases of P&V

relationships
2. Constant pressure process
(isobaric)

Special cases of P&V

relationships
3. PV= constant process
This simple algebraic formula is in fact satisfied by
many substances when expanding in fully resisted
expansion at constant temperature, so called
isothermal process.

Special cases of P&V

relationships
4. PVn= k (constant)
Also known as the polytropic process. This represents
a family of processes which are very useful
approximations to real processes.

Un-resisted expansion
Consider a rigid vessel divided by a light diaphragm:
When diaphragm gives way under pressure the gas expands to fill the whole vessel. If we consider system S1

dv=0
The pressure on the moving boundary, i.e. The face of the boundary exposed to vacuum is always zero while that part
of the boundary is in motion.
Consider S
2: Initial 0, finally volume is the same, so W = 0

S1

P=1atm

diaphragm

S2

P=0

Shear work
Consider a block being pushed along a rough horizontal surface by an agent which
applies a force F.

Assume that we want to calculate the work done on the lower part of the block by the
system consisting of the agent and the upper part of the block. A shear exists along the
part of S in the block tending to make the upper half of the block slide relative to the
lower half. If this shear stress has uniform value and acts over area A, then from static:

Thus

or in general:

I.e. when sigma is a function of (L), we consider each element of area dA separately and
multiply by the value of sigma prevailing there at the moment in question and by the
elementary distance dL.

Shaft work

A very important form of shear work which we are concerned with is shaft work.
This comes across in actions such as power transmission in cars and steam turbines,
gas turbines etc.
Consider a shaft penetrating a system boundary:
Where the shaft crosses the boundary S, for each element of cross-section area dA
there is a shear stress sigma in the tangential direction, tending to cause the relative
rotation of the two parts of the shaft on either side of S i.e. the torque dT on the
element =

dT = dAr

T = rdA
Suppose that shaft turns through a small angle
and as a result each element (both sides of S) moves a distance
in the direction
of the stress. The shear work done by the element dA on its surroundings during the
elementary rotation is given by:

dWs = (dA)(rd )

Thus the shear work done by the system on the surroundings is given by:
or
For steady condition T is constant and independent of

, then:

Dividing both sides by dT (time increment), we obtain the shaft power,

Where

Electrical work
In an electric field, electrons in a wire move under the effect of
electromotive forces, doing work. When N electrons move through
a potential difference V, the electrical work done is:
We = VN(kJ)
Which can be expressed in the rate form as:

Where

Interaction Between Systems II - Heat

The thermodynamic definition of heat is:
"Heat transfer is the interaction between systems which occurs by virtue of their
temperature difference when they communicate".

But what is temperature?

Temperature is the thermodynamics property that we are most familiar with and yet
it is amongst the most difficult properties to define!
On the microscopic level temperature is related to the kinetic energy of the
molecules. But in thermodynamics we are interested in temperature because it
enables us to know whether or not two system are in thermal equilibrium.
So we define temperature as:"The temperature of a system is a property that
determines whether or not a system is in thermal equilibrium with other systems".

Interaction Between Systems II - Heat

The concept of thermal equilibrium is very familiar to us:
Cold bottle of milk from fridge and cup of hot water, if left in a room for few hours
will reach the same temperature as that of the room..
That is they both reach thermal equilibrium with the room.
Thus we say:
"Two systems are equal in temperature if no change in any property occurs when
they are bought into communication".
We can also conclude that:
"Two systems which are equal in temperature to a third system are equal in
temperature to each other".
This is the Zeroth Law of Thermodynamics and provides the basis for temperature
measurements.

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Temperature inequality & thermometers

Consider an experiment involving three systems S1, S-2 and
S3. Suppose we bring S3 into contact with S1 until they reach
thermal equilibrium.

No work interactions assumed!

Now if we bring S3 into contact with S2 and as a result
observable changes occur in S3 then we can conclude that
the temperatures of S1 and S2 are unequal. To measure this
inequality we use a thermometer.

Thermometers
For thermometer, we can use any property that changes with temperature.
For example, if we chose a glass tube containing mercury as system S3, then we
would have a mercury in glass thermometer. The mercury in glass thermometer is
usually calibrated between two fixed points- one at the melting point of ice and the
other at the boiling point of water- both at the pressure of one atmosphere.
Temperature scales are then defined by assigning numbers to the ice point and
steam point and to the equally-spaced points between them.
Celsius or centigrade:
Ice point: 0 deg C. Steam point: 100 deg C, with 100 equal subdivisions.
Farenheit:
Ice point: 32 deg F. Steam point: 212 deg F, with 180 equal subdivisions.
Other thermometers:
1. Constant volume thermometer, gives a very close result to the thermodynamic
temperature scale which is not based on a particular thermometric substance.
2. Platinum resistance thermometer

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Sign Conventions for Heat transfer

Heat transfer is +ve when the surroundings have a higher temperature i.e. heat is
transferred to the system
Heat transfer is -ve when the system has a higher temperature, i.e. heat is
transferred from the system
Heat like work is transitory, i.e. not an observable characteristic of the system. Of
course it is a path function.

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Some Notes on Definition of Heat

1. Heat is not "that which inevitably causes a temperature rise".
For example if a system comprising of ice and water is heated, no temperature
rise occurs at least until the ice has melted.
2. Heat is not "that which is always present when a temperature rise happens". E.g.
from below, water can be heated by work only.

How heat transfer occurs

Conduction:
Conduction is a mode of heat transfer involving solid media due to the impact of
adjacent molecules vibrating about mean position.
Some solids such as metal rods, copper and silver are very good conductors, while
others like wood, cork are very poor conductors and are used as insulators.
Convection:
This is a mode of heat transfer in a fluid media in motion, e.g. hot wall heats a mass
of air which moves to heat a cold wall
Radiation:
Thermal communication which involves no matter of media, e.g. sun radiates heat to
warm the earth. The rate of radiative heat transfer increases rapidly with
temperature but is negligible at room temperature.
Adiabatic processes:
If all the above three modes of heat transfer are absent then Q=0, and we have an
adiabatic process.

Thermometers
For thermometer, we can use any property that changes with temperature.
For example, if we chose a glass tube containing mercury as system S3, then we
would have a mercury in glass thermometer. The mercury in glass thermometer is
usually calibrated between two fixed points- one at the melting point of ice and the
other at the boiling point of water- both at the pressure of one atmosphere.
Temperature scales are then defined by assigning numbers to the ice point and
steam point and to the equally-spaced points between them.
Celsius or centigrade:
Ice point: 0 deg C. Steam point: 100 deg C, with 100 equal subdivisions.
Farenheit:
Ice point: 32 deg F. Steam point: 212 deg F, with 180 equal subdivisions.
Other thermometers:
1. Constant volume thermometer, gives a very close result to the thermodynamic
temperature scale which is not based on a particular thermometric substance.
2. Platinum resistance thermometer

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First law of thermodynamics

One important concept in thermodynamics is the relationship
between heat and work.
However, there is no logical relationship between heat and
work and so it had to be found experimentally. The
experiments were carried out by J P Joule between 1840 to
1849. The important experiment involved a system consisting
of a well-lagged cylinder containing water going through a
cycle composed of two processes.
In the first process, shear work was done on the system when
a paddle turned as a weight was lowered, as shown here.
As a result of this process the water temperature was found to
rise steadily. When the temperature reached a certain value,
the paddle wheel was stopped and the work done noted
(historically in foot pounds-force).
In the second process the system was brought into contact
with a cold body so that heat was transferred from the system,
as shown here.

First law of thermodynamics

This process was then cut-off when the system reached its original state and again
the amount of heat transfer was noted down (in British Thermal units or calorie).
After making the measurements for a variety of systems and for various amounts of
work and heat, it was found that the amounts of work and heat were always
proportional.
These observations were then formalised into the First Law of Thermodynamics
which is stated as:
"If any system is carried through a cycle (the end state being precisely the
same as the initial state) then the net work is proportional to the net heat
transfer".

dw =J dQ

or

dw = dQ In SI units
Where J is a constant known as the Mechanical Equivalent of
Heat. In British units J is 778 ft lbf per Btu and in SI units its 1.
Nm per Joules

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First law for non-cyclic process

We defined first law for cyclic processes, but what
happens when we have a change of state.
For this purpose consider a system that undergoes a
cycle changing from state 1 to 2 by process A and
returning from state 2 to 1 by process B, as shown in
the image:
Now consider another cycle, the system changing from State 1 to 2 by process A and returning to state 1 by
process C, so that

Subtracting the equations we get:

or on rearranging:

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Energy..
Since B & C represent arbitrary processes between states 1 and 2, we can conclude that the quantity (dQ -dW)
is the same for all processes between states 1 and 2. Therefore, (dQ -dW) depends only on the initial and final
states and not on the path followed between the two states. That is this quantity is a point function, which
means that it is a property of the system, called the energy of the system and is given smybol E-

When we integrate this equation we get:

where:
1Q2 is the heat transferred to the system during process 1 - 2
E2 and E1 are the energy at the initial and final states
1W2 is the work done during process 1 - 2
E represents all the energy in the system i.e. E = P. E + K.E. + energy associated with position and
motion of molecules + chemical energy (e.g. storage battery), etc.
In thermodynamics it is convenient to consider the bulk K. E. and P.E. separately and then to consider
all the other energy of the system in a single property that we call internal energy, U.

So: E = U + KE + PE
dQ = dU + d (KE) + d(PE) + dW

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Expression for KE
Consider a system initially at rest acted on by a horizontal force F that
moves the system a distance dx in the direction of the force.
dW = - Fdx = - d KE

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Expression for PE
Consider a system initially at rest. Let this system be acted on by a vertical force F that is of
such magnitude that it raises (in elevation) the system with constant velocity an amount dz. If
acceleration due to gravity is g
dW = - F d Z = - dPE
But:
F = Ma = mg
Then:
dPE = FdZ = mgdZ

Thus we can write:

Observations..

We can make three observations about this equation.

(i ) We can write the first law of Thermodynamics for a system which changes its state during a non-cyclic
process, when we employ the property of system E energy.
(ii) The net change of the energy of the system is always equal to the net transfer of energy across the
system boundary as heat and work. This is somewhat similar to a husband and wife having a joint bank
account. There are two ways in which deposits and withdrawals can be made, either by husband or wife,
and the balance will always reflect the net amount of the transaction - Similarly there are two ways in which
energy can cross the boundary of a system, either as heat or work, and the energy of the system will change
by the exact amount of net energy crossing the system boundary. This leads to the law of conservation of
energy: "The energy of a system remains unchanged if the system is isolated from its environment as
regards to work and heat regardless of the nature of changes within the system".
(iii) Equations (1) can give only changes in, internal energy, PE and KE. We can learn nothing about
absolute values of these quantities. Therefore, we must assign reference states to these quantities. Easy to
assign reference states for PE, e.g. zero elevation on surface earth and KE, zero KE when velocity is zero
relative to earth but more difficult for U.
(iv) This equation also implies that "a perpetual motion machine of a first kind is impossible" This device is
a system which will continuously deliver work without a supply of heat i.e. Q = 0, W =+ ve, dU ve. Thus
work is obtained at the expense of internal energy which will eventually run out.
(v) Internal energy is an extensive property. But of course u=U/m, is an intensive property.
(vi) dU is an exact differential?

to continue