Chapter three: - Thermodynamics

In this chapter, we introduce a physical quantity known as temperature, which is one of the seven SI
base quantities. Temperature is associated with our sense of hot and cold. Physicists and engineers
measure temperature more objectively using the Kelvin scale, which is independent of the properties of
any substance. We will study the effect of temperature on matter; solid, liquid, and gas.
3.1. Temperature and Zeroth law of thermodynamics
Explain the terms Thermal contact and Thermal equilibrium?
In describing the thermal phenomena, it is essential to have one quantity, which cannot be defined in
terms of the three basic quantities of mechanics: length, mass and time. This quantity is known as
temperature. However, the concept of temperature is related in qualitative ideas of "hotness" and
"coldness" of a body based on our sense of touch. A body that feels hot usually has a higher temperature
than a similar body that feels cold. This shows that temperature is a physical quantity, which is quite
different from the quantity of heat.

A body is said to be at a higher temperature than a cold one. Hence, temperature can be defined as the
degree of hotness or coldness of the body. Temperature is also related to the kinetic energies of the
molecules of a material. It is important to understand, however, that temperature and heat can be defined
independently of any detailed molecular picture. To understand the concept of temperature, it is useful to
define two often-used phrases: thermal contact and thermal equilibrium. To grasp the meaning of
thermal contact, imagine that two objects are placed in an insulated container such that they interact with
each other but not with the environment. If the objects are at different temperatures, energy is exchanged
between them, even if they are initially not in physical contact with each other. Therefore, the two objects
are said to be in thermal contact with each other if energy can be exchanged between them by these
processes due to a temperature difference.

Thermal equilibrium is a situation in which two objects would not exchange energy by heat or
electromagnetic radiation if they were placed in thermal contact.

On the other hand, if two bodies are brought in contact heat flows from a body at a higher temperature to
the other at a lower temperature until finally a stage is reached when there is no further flow of heat. In
this, state a thermal equilibrium is said to have reached and the two bodies are said to have the same
temperature. If two bodies are placed in contact, they will come to the same temperature. This is known
as the zeroth law of thermodynamics or if two systems are in thermal equilibrium with the third system
they must be in thermal equilibrium with each other.
This is the basis for making measuring device for temperature. Therefore, we can say that temperature is
the property that determines whether a body is in thermal equilibrium with the neigh boring system. If a
number of systems are in thermal equilibrium, this common property of the system must be represented
by a single numerical value called Temperature. This means that if two systems are not in thermal
equilibrium, they are at different temperature. Thus, the measurement of temperature and the measuring
device is very essential. Next, we will try to discuss the measurement and measuring devices of
temperature.

3.2Thermometers and Temperature Scale

Thermometers are devices used to measure the temperature of a system. All thermometers are based on
the principle that some physical property of a system changes as the system’s temperature changes. Some
physical properties that change with temperature are

(1) The volume of a liquid,

(2) The dimensions of a solid,

(3) The pressure of a gas at constant volume,

(4) The volume of a gas at constant pressure,

(5) The electric resistance of a conductor, and

(6) The color of an object.

A common thermometer in everyday use consists of a mass of liquid usually mercury or alcohol that
expands into a glass capillary tube when heated. In this case, the physical property that changes is the
volume of a liquid.

Any temperature change in the range of the thermometer can be defined as being proportional to the
change in length of the liquid column. The thermometer can be calibrated by placing it in thermal contact
with a natural system that remains at constant temperature. One such system is a mixture of water and ice
in thermal equilibrium at atmospheric pressure. On the Celsius temperature scale, this mixture is defined
to have a temperature of zero degrees Celsius, which is written as ; this temperature is called the ice
point of water. Another commonly used system is a mixture of water and steam in thermal equilibrium at
atmospheric pressure; its temperature is defined as 100 , which is the steam point of water.

The Kelvin scale

The limiting temperature of a body is taken as the zero of the Kelvin scale, and called the absolute zero.
To set up the Kelvin temperature scale, we select a standard fixed point and give it a standard fixed point
temperature. We select the triple point of water, where liquid water, solid ice, and water vapor can
coexist in thermal equilibrium at only specific values of pressure and temperature. By international
agreement, at water vapor pressure of 4.58mm Hg, the temperature of this mixture has been assigned a
value 273.16Kelvins, written as 273.16 K. That is:

Where the subscript 3 denotes the triple point. This agreement sets the size of the kelvin as 1/273.16 of
the difference between absolute zero and the triple-point temperature of water. This scale is used mostly
in basic scientific calculations and studies. On the Kelvin scale, measurements show that the lowest
reached temperature is K, and the freezing and boiling (at 1 atm. Pressure) temperature points
are:

The Celsius Scale

The symbol stands for degrees Celsius. The size of 1 on the Celsius scale is the same as the size of
1K on the Kelvin scale. However, the zero of the Celsius scale is shifted by 273.15 ◦ with respect to the
absolute zero of the Kelvin scale. On the Celsius scale, any temperature value is related to its Kelvin
equivalent T by:
( )
The Fahrenheit Scale
The symbol stands for degrees Fahrenheit. The Fahrenheit scale has a smaller degree size than the
Celsius and has a different zero (the freezing point of a certain concentration of salt water). The relation
between the Celsius and Fahrenheit scales is:

Table1. Some corresponding temperatures

Example 1
The normal boiling point of nitrogen is −195.75 . (a)What is this temperature in Kelvin and in
Fahrenheit? (b) If the temperature changes from −195.75 to −100 , find the change in the
temperature on the Fahrenheit scale.
Solution: (a) Substituting TC = −195.75 into Eq above we get:

Also we get

( )

Thus −195.75 , and are temperatures on different scales.

b) For a change [ ( )]

To find the change in temperature on the Fahrenheit scale as:

[ ( )]

Thus a change , where the notations and refer to temperature

difference, not to be confused with actual temperatures, which are written in terms of symbols and .
3.4Thermal Expansion of Solids and Liquids
Most bodies expand as their temperatures increase. This phenomenon plays an important role in
numerous engineering applications, such as the joints in buildings, highways, railroad tracks, bridges...
etc. Such thermal expansion is not always desirable. Microscopically, thermal expansion arises from the
change in the separation between the constituent atoms or molecules of the solid. To understand this, we
consider a crystalline solid of a regular array of atoms or molecules held together by electrical forces.
At an ordinary temperature, the average spacing between the atoms is of the order of , and they
vibrate about their equilibrium positions with an amplitude of about and a frequency of about
. As the temperature increases, the atoms vibrate with larger amplitudes and the average
separation between them increases.
Fig.3.1 A mechanical model representing the average spacing in a unit cell of crystalline solid at a given
instant. Neighboring atoms or molecules (red spheres) are imagined to be attached to each other by elastic
stiff springs, which represent the inter-atomic electric forces.

If the thermal expansion of an object is sufficiently small compared to its initial dimensions, then the
change in any dimension (length, width, or thickness) is, to a good approximation, a linear function of the
temperature.
Linear Expansion
If a rod of length and temperature experiences a small change in temperature , its length changes
by an amount , see Fig.3.2. We introduce a proportionally coefficient α for the solid and write:
⁄

For a sufficiently small change , experiments show that is proportional to both L and .

Where the proportionality constant is called the coefficient of linear expansion for a given material.
Note that Eq. 3.1 describes an expansion when is positive and a contraction when is negative. If we
set1 we see from Eq. 3.1 that represents the fractional change in length ( ) per one
degree change in temperature. Thus the unit of is( ).

Fig.3.2 The length of the rod will increase by when its temperature changes from to . The
expansion is exaggerated in the figure.
Example 3.2
A steel rod has a length and radius when the temperature is . Take
( ) and Young’s modulus of the rod to be (a) what is its length
on a hot day when the temperature is (b) If the rod’s ends were originally fixed, then find the
compression force on the rod?
Solution: (a) From Eq. 3.1, we can find the increase when the change in temperature is

as follows: [ ( ) ]( )( )
Therefore, the rod’s new length at . (b)
If the rod is not allowed to expand, we then calculate what force would be required to compress the rod
by the amount . From the definition of Young’s modulus ( ) ( )

( )( ) ( )( )( )

Volume Expansion
Not only does the length of an object increase with temperature, but its area and volume change as well.
The change in volume at a constant pressure is proportional to the original volume and to the
change in temperature according to the following relation:

Where the proportionality constant is called the coefficient of volume expansion for a given solid or
liquid. Setting in Eq. 3.2, we see that is numerically equal to the fractional change in
volume ( ) per one degree change in temperature. Thus, like , the unit of is ( )
An isotropic solid is a solid that has a coefficient of linear expansion that is equal in all directions.
Accordingly, for an isotropic solid, the coefficient of volume expansion is approximately three times the
linear expansion coefficient, i.e.
To find the relationship between and , assume the average coefficient of linear expansion of the solid
is the same in all directions; that is, assume the material is isotropic. Consider a solid box of
dimensions, , and Its volume at some temperature is . If the temperature changes to
, its volume changes to , where each dimension changes according to Equation 3.1.
Therefore,

( )( )( )
( )( )( )
( )
[ ( ) ( ) ]
Then dividing both sides by and isolating the term , we obtain the fractional change in volume:

( ) ( )

Because a for typical values of ( ), we can neglect the terms ( ) and ( ) .

Upon making this approximation, we see that
This implies that

Then comparing this expression to Equation 3.2 shows that

In a similar way, you can show that the change in area of a rectangular plate is given by .
Example 3
On a hot day, when the temperature was , an oil trucker fully loaded his truck from an oil
station with 10,000 gal of gasoline ( ). On his way to a delivery city, he encountered
cold weather, where the temperature went down to , see Fig. 3.3. The coefficients of volume
expansion of gasoline and steel are ( ) and ( ) , respectively.
How many gallons did the trucker deliver?

Solution: The change in temperature from the production city to the delivery city is

From Eq. 3.2, we can find the change in the gasoline volume as follows:
[ ( ) ]( )( )

Thus, the amount of gasoline delivered was:

The thermal expansion of the volume of the steel tank can also be calculated as follows:
[ ( ) ]( )( )
3.5Macroscopic Description of an Ideal Gas
The volume expansion equation is based on the assumption that the material has an initial
volume before the temperature change occurs. Such is the case for solids and liquids because they
have a fixed volume at a given temperature. The case for gases is completely different. The interatomic
forces within gases are very weak, and, in many cases, we can imagine these forces to be nonexistent and
still make very good approximations. Therefore, there is no equilibrium separation for the atoms and no
“standard” volume at a given temperature; the volume depends on the size of the container.
As a result, we cannot express changes in volume in a process on a gas with Equation 3.2 because we
have no defined volume at the beginning of the process. Equations involving gases contain the volume
, rather than a change in the volume from an initial value, as a variable.
For a gas, it is useful to know how the quantities volume , pressure , and temperature are related for
a sample of gas of mass In general, the equation that interrelates these quantities, called the equation
of state, is very complicated. If the gas is maintained at a very low pressure (or low density), however,
the equation of state is quite simple and can be determined from experimental results. Such a low-density
gas is commonly referred to as an ideal gas. We can use the ideal gas model to make predictions that are
adequate to describe the behavior of real gases at low pressures.
Equation of State of an Ideal Gas
One mole ( ) of a substance is the amount of substance that contains as many particles as in exactly
of the isotope carbon-12. Although the mole is one of the seven SI base units, it is convenient to
introduce the one kilo mole (1 k mole) of a substance as the amount of substance that contains as many
particles as in exactly 12 kilograms of the isotope carbon-12. Thus:
One kilo mole (1 k mole): One k mole is the number of atoms in a 12 kg sample of pure carbon-12.
This number is called Avogadro’s number, , after A. Avogadro, who suggested that all gases contain
the same number of particles (atoms or molecules) when they occupy the same volume under the same
conditions of pressure and temperature. Avogadro’s number is determined experimentally to be:

In addition, the molar mass of each chemical element is defined as:

Molar Mass (M): The molar mass M of a chemical element is its atomic mass expressed in g/mol or
equivalently in kg/k mol.
For example, the mass of one atom is (12 atomic mass units,); then the molar mass of is
and contains atoms. Now, for an ideal gas of mass (in ) confined to a container of
volume (in ) at a pressure (in ) and temperature (in ), it is convenient to express the amount
of the gas in terms of the number of kilomoles , see Fig. 3.4. This number is related to the gas mass
and its molar mass through the expression:

( )
Fig.3.5 An ideal gas defined by , and is contained in a cylinder with a movable piston to allow
the volume to be varied.
Moreover, we consider that the volume of the container can be varied, and hence the gas volume, by
means of the movable piston of Fig. 3.5. For this system, experiments show that at low densities, all
gases tend to obey the following equation of state (which is known as the ideal gas law):
( )
Where is the number of kilomoles of gas present and is the gas constant which is determined from
experiments to have the same value for all gases, namely:

3.6
Using this value of R and the equation of state, Eq. 3.5, we can find the volume occupied by 1 k mol (kilo
molar volume) of any ideal gas at the standard temperature and pressure (STP), which means temperature
of ( ) and atmospheric pressure ( ), as follows:
( )( )( )
( )

Where . Thus:
Volume of 1 kmol: One kmol of any ideal gas at atmospheric pressure and at occupies a space of

We can express the ideal gas law in terms of the total number of molecules by using the fact that
equals the product of the number of kmol and Avogadro’s number i.e. . Thus:

Or

Where is called Boltzmann’s constant, which has the value:

. Equation 3.7 indicates that the pressure of a fixed volume of gas depends only on the temperature and
the number of molecules in that volume.