CHAPTERTHREE:THERMODYNAMICS

 Thermodynamics is a science of the relationship

between heat, work, temperature, and energy.
 In broad terms, thermodynamics deals with the
transfer of energy from one system to another and
from one form to another.
 In thermodynamics, one usually considers both
thermodynamic systems and their environments.
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 A typical thermodynamic system is a definite quantity
of gas enclosed in a cylinder with a sliding piston that
allows the volume of gas to vary.
 But in general a thermodynamic system is a quantity
of matter of fixed identity that is the subject of study
and it may be solid, liquid or gas.
 The surrounding is the environment that is around a
system and in thermal contact with it.
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 In general, a thermodynamic system is defined by its
temperature, volume, pressure, and chemical
composition.
 A system is in equilibrium when each of these variables
has the same value at all points
3.1. Temperature and the Zeroth Law of Thermodynamics

 Heat is defined as the flow of energy from one object

to another.
 This flow of energy is caused by a difference in
temperature.
 Heat can flow between objects if they are in thermal
contact.
 An important concept related to temperature is
thermal equilibrium.
 Temperature – Definition
 Temperature can be thought of as the property that
determines whether an object is in thermal equilibrium
with other objects.
 Two objects in thermal equilibrium with each other are at
the same temperature.
If two objects have different temperatures, they are not
in thermal equilibrium with each other.
 Temperature is something that determines whether or not
energy will transfer between two objects in thermal
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 Two objects are in thermal equilibrium if they are in close

contact that allows either to gain energy from the other, but
nevertheless, no net energy is transferred between them.

 Even when not in contact, they are in thermal

equilibrium if, when they are placed in contact, no net
energy is transferred between them.
 If two objects remain in contact for a long time, they
typically come to equilibrium.
 In other words, two objects in thermal equilibrium do not
exchange energy.
 Cont..
 Experimentally, if object A is in thermal equilibrium
with object B, and object B is in thermal equilibrium
with object C, then object A is in thermal equilibrium
with object C.
 That statement of transitivity is called the Zeroth law of
thermodynamics.
 Understanding the concept of temperature requires
understanding thermal contact and thermal equilibrium.
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 Two objects are in thermal contact if energy can be
exchanged between them.
 Two objects are in thermal equilibrium if they are in
thermal contact and there is no net exchange of energy.
 The exchange of energy between two objects because of
differences in their temperatures is called heat.
 Zeroth Law of Thermodynamics, Example

 Object C (thermometer) is placed in contact with A until

they achieve thermal equilibrium.
The reading on C is recorded.
 Object C is then placed in contact with object B until
they achieve thermal equilibrium.
The reading on C is recorded again.
 If the two readings are the same, we can conclude that A
and B are in thermal equilibrium with each other.
3.2 Thermometers and Temperature Scale
 A thermometer is a device that is used to measure the temperature

of a system.

 Thermometers are based on the principle that some physical

property of a system changes as the system’s temperature changes.

 These properties include:

 The volume of a liquid

 The dimensions of a solid

 The pressure of a gas at a constant volume

 The volume of a gas at a constant pressure

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The electric resistance of a conductor

The color of an object

 A temperature scale can be established on the basis of any

of these physical properties.

 One common thermometer in everyday use consists of a
mass of liquid-usually mercury or alcohol.
 Other properties used to measure temperature include
electrical resistance, color and the emission of infrared
radiation.
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 Thermometers measure temperature according to well-
defined scales of measurement.
 The three most common temperature scales are
Fahrenheit, Celsius, and Kelvin.
 Temperature scales are created by identifying two
reproducible temperatures.
 The freezing and boiling temperatures of water at
standard atmospheric pressure are commonly used.
 Cont.….
 On the Celsius scale, the freezing point of water is

0 oC and the boiling point is 100 oC .

 The unit of temperature on this scale is the degree
Celsius (oC ).
 The Fahrenheit scale has the freezing point of water
at 32 oF and the boiling point at 212 oF . Its unit is the
degree Fahrenheit (oF).
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Relationships between the Fahrenheit, Celsius, and Kelvin

temperature scales are shown.
 Conversions from one temperature scale to the other are
possible using the following relations:
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Example: The temperature gradient between the skin and the air is
regulated by cutaneous (skin) blood flow. If the cutaneous blood
vessels are constricted, the skin temperature and the temperature of the
environment will be about the same. When the vessels are dilated more
blood is brought to the surface. Suppose during dilation the skin warms
from 72.0°F to 84.0°F. (a) Convert these temperatures to Celsius and
find the difference. (b) Convert the temperatures to Kelvin, again
finding the difference.
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• (a) Convert these temperatures to Celsius and find
the difference.
• Lower= °C (72.0°F)
• Upper= °C (84.0°F.)
• Difference= °C
• The relationship between the temperature in
Fahrenheit and the temperature in Kelvin is given as
follows.
5 5
𝑇 𝐶=
9
( 𝑇 𝐹 − 32 )=
9
( 72− 32 )= 22℃

• Convert the upper temperature:

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 Find the difference of the two temperatures

∆ 𝑇 𝐶 = 29℃ − 22 ℃ =7 ℃
(b) Convert the temperatures from Fahrenheit to Kelvin
and find their difference. Convert the lower temperature,
using the answers for Celsius found in part (a):
 3.3 Thermal Expansion of Solids and Liquids

 As temperature of the substance increases its volume

increases.
 This phenomenon, known as thermal expansion, plays
an important role in numerous applications.
 Thermal expansion joints, for example must be
included in buildings, concrete highways, and bridges
to compensate for changes in dimensions with

variations in temperature.
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 The overall thermal expansion of an object is a
consequence of the change in the average separation
between its constituent atoms or molecules.
 To understand this idea, consider how the atoms in a
solid substance behave.
 These atoms are located at fixed equilibrium positions;
if an atom is pulled away from its position, are storing

force pulls it back.

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 If an atom is pulled away from its equilibrium position,
the distortion of the springs provides a restoring force.
 At ordinary temperatures, the atoms vibrate around their
equilibrium positions with an amplitude (maximum
distance from the center of vibration) of about with an
average spacing between the atoms of about
 As the temperature of the solid increases, the atoms
vibrate with greater amplitudes and the average separation
between them increases.
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 As the temperature of the solid increases, the
atoms vibrate with greater amplitudes and the
average separation between them increases.
 Suppose an object has an initial length along some
direction at some temperature .
 Then the length increases by for a change in
temperature
 So for small changes in temperature
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 Where L is the object‘s final length, T is its final

temperature, and the proportionality constant a is
called the coefficient of linear expansion for a given

material and has units of .

 Thermal Expansion
Gases expand
more when
Liquids heated than
expand more liquids
when heated (depending
than solids. upon P, V and
T)
Material Coefficient of expansion

When heated, solids (and liquids and gases) Glass 8.5x

gain thermal energy. The particles start to Concrete 12x
move about more – their vibrations take up
more space, so there is expansion in all 19x
Brass
directions. The opposite is true when the
temperature falls – the material will get 11x
smaller (contract). Steel

Aluminium 23x
Example: A steel railroad track has a length of 30.000 m
when the temperature is 0°C. What is its length on a hot
day when the temperature is 40.0°C? solution
Linear Expansion due to rise in temperature in given by:
ΔL = LαΔT
Here ΔL is the increase in length due to change in
temperature ΔT.
α = coefficient of linear expansion
Given that, α = 11x , L =30 m, and ΔT = 40°C
so, ΔL = 30 × 11x × 40
ΔL = 0.013 m is the increase in length.
Add the change to the original length to find the final
length:
 3.3.1. Volume and Area Expansions

 Increasing temperature usually causes increases in

volume for both solid and liquid materials, Just as with
linear expansion, experiments show that if the
temperature change is not too great (less than or so), the
increase in volume is approximately proportional to
both the temperature change and the initial volume .

 The constant characterizes the volume expansion

properties of a particular material; it is called the
For area expansion,
The quantity (Greek letter gamma) is called the coefficient
of area expansion.
Example: A200- glass flask is filled to the brim with
mercury at 20°C. How much mercury overflows when the
temperature of the system is raised to .The coefficient of
linear expansion of the glass is
γglass=1.2× ,γmercury=1.8× ) solution:
Due to increase in the temperature, both the mercury and
the glass vessel will expand
Increase in the volume of mercury
=VγmercuryΔT=(200)×1.8××(100−20) =2.88 𝑐𝑚^3

Increase in the volume of

glass=VγglassΔT=(200)×1.2××(100−20)

=0.192𝑐𝑚^3.

So, the amount as mercury that will overflow

=(2.880−0.192)=2.688=2.69 𝑐𝑚^3.
 3.4 .Macroscopic Description of an Ideal Gas
Describing a sample of a gas
 4 variables are needed to completely describe a sample of a gas:

 Temperature

 Pressure

 Volume

 Amount (number of moles) of gas

 An equation relating the macroscopic variables that describe

some type of matter.

 The ideal gas law is an equation of state for gases.

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 Macroscopic Description of an Ideal Gas Avogadro‘s number is

NA particles/mol. A mole of anything, by definition, consists of

an Avogadro‘s number of particles.

 Avogadro‘s number and the definition of a mole are fundamental

to chemistry and related branches of physics. The number of

moles of a substance is related to its mass m by the expression.

 ..............3.5

 Where the molar mass of the substance is defined as the mass of

one mole of that substance, usually expressed in grams per mole.

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 the atomic mass of an atom expressed in atomic mass

units is numerically the same as the mass of an
Avogadro‘s number of that kind of atom expressed in
grams.
 Because there are particles in one mole of any
element the mass per atom for a given element is
………3.6
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Boyle’s Law Charles’ Law Avogadro’s

Law
V  1/P V  T (Kelvin) Vn

Constant T, n Constant P, n Constant T, P

So V  1/P X n X T
 Cont….
 To turn a proportionality into an equation, insert a
constant: V = RnT/P
 Or multiply both sides by P:
 PV = nRT where R is the ideal gas law constant.
 If three of the variables are known, the 4 th can be
determined.
 The units of R depend on the units used for P, T, and V.
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 In this equation R is a constant for a specific gas that must be
determined from experiments, whereas T is the temperature in
kelvins.
 Each point on a P versus V diagram would represent a different
state of the system.
 Experiments on several gases show that, as the pressure
approaches zero, the quantity PV/nT approaches the same value of
R for all gases.
 For this reason, R is called the universal gas constant.
 In SI units, where pressure is expressed in Pascal and volume in
cubic meters . R=8.31J/mol.K
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• Example: An ideal gas at 20.0°C and a pressure ofPa is
in a container having a volume of 1.00 L. (a) Determine
the number of moles of gas in the container. (b) The gas
pushes against a piston, expanding to twice its original
volume, while the pressure falls to atmospheric pressure.
Find the final temperature. Solution: (a) Find the number
of moles of gas. Convert the temperature to kelvins:
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 b) Find the temperature after the gas expands to 2.00
L. Divide the ideal gas law for the final state by the
ideal gas law for the initial state:

Thank You