Module in SEd 212

Thermodynamics

Topic 1
Temperature and Zeroth Law of Thermodynamics

Introduction
This section introduces the fundamental concepts in thermodynamics like
thermal energy, heat, temperature and temperature scales. It discusses the Zeroth
Law of Thermodynamics and provides examples of its application

Intended Learning Outcomes

At the end of this section, the students are expected to:
1.   Apply temperature conversion formulas
2.   Understand how to relate different temperature scales
3.   Explain how the thermometer works
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Fundamental Concepts

Thermodynamics is the science of the relationship

between heat, work, temperature, and energy. In broad terms, thermodynamics
deals with the transfer of energy from one place to another and from one form to
another. The key concept is that heat is a form of energy corresponding to a definite
amount of mechanical work.

Thermal energy is the energy a substance or system has due to its

temperature, i.e., the energy of moving or vibrating molecules, according to
the Energy Education website of the Texas Education Agency. Thermodynamics
involves measuring this energy, which can be "exceedingly complicated," according
to David McKee, a professor of physics at Missouri Southern State University.

"The systems that we study in thermodynamics … consist of very large

numbers of atoms or molecules interacting in complicated ways. But, if these
systems meet the right criteria, which we call equilibrium, they can be described
with a very small number of measurements or numbers. Often this is idealized as
the mass of the system, the pressure of the system, and the volume of the system, or
some other equivalent set of numbers."

Heat
Thermodynamics, then, is concerned with several properties of matter;
foremost among these is heat. Heat is energy transferred between substances or systems
due to a temperature difference between them. As a form of energy, heat is conserved,
i.e., it cannot be created or destroyed. It can, however, be transferred from one place

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to another. Heat can also be converted to and from other forms of energy. For
example, a steam turbine can convert heat to kinetic energy to run a generator that
converts kinetic energy to electrical energy. A light bulb can convert this electrical
energy to electromagnetic radiation (light), which, when absorbed by a surface, is
converted back into heat.

The Nature of Energy and Types of Energy

Energy is usually defined as the capacity to do work. We define work as the

“force x distance” but we will soon see that there are other kinds of work.

o   Radiant Energy – or solar energy, comes from the sun and is the
Earth’s primary source of energy.
o   Thermal Energy – is the energy associated with the random motion
of atoms and molecules. In general, thermal energy can be calculated
from temperature measurements. The more vigorous the motion of
atoms and molecules in a sample of matter, the hotter the sample is
and the greater its thermal energy.
o   Chemical Energy – is stored within the structural units of chemical
substances; its quantity is determined by the type and arrangement
of constituent atoms. When substances participate in chemical
reactions, chemical energy is released, stored or converted to other
forms of energy.
o   Potential Energy – is the energy available by virtue of an object’s
position. Chemical energy can be considered a form of potential
energy because it is associated with the relative positions and
arrangements of atoms within a given substance.
o   Kinetic Energy – is the energy by virtue of an object’s motion. It is
one form of energy that is of particular interest to the chemist.

Temperature
The amount of heat transferred by a substance depends on the speed and
number of atoms or molecules in motion. The faster the atoms or molecules move,
the higher the temperature, and the more atoms or molecules that are in motion, the
greater the quantity of heat they transfer.

Temperature is "a measure of the average kinetic energy of the particles in a

sample of matter, expressed in terms of units or degrees designated on a standard
scale. The most commonly used temperature scale is Celsius, which is based on the
freezing and boiling points of water, assigning respective values of 0 degrees C and
100 degrees C. The Fahrenheit scale is also based on the freezing and boiling points
of water which have assigned values of 32 F and 212 F, respectively.

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Scientists worldwide, however, use the Kelvin (K with no degree sign) scale,
named after William Thomson, 1st Baron Kelvin, because it works in calculations.
This scale uses the same increment as the Celsius scale, i.e., a temperature change of
1 C is equal to 1 K. However, the Kelvin scale starts at absolute zero, the temperature
at which there is a total absence of heat energy and all molecular motion stops. A
temperature of 0 K is equal to minus 459.67 F or minus 273.15 C.

Celsius Scale

Celsius, or centigrade, is a scale and unit of measurement for temperature. It

is one of the most commonly used temperature units.

Celsius, also known as centigrade, is a scale to measure temperature. The unit

of measurement is the degree Celsius (°C). It is one of the most commonly used
temperature units in the world. The unit system is named after the Swedish
astronomer Anders Celsius (1701-1744), who developed a similar temperature scale.

From 1743 until 1954, 0°C was defined as the freezing point of water, and
100°C was defined as the boiling point of water, both at a pressure of one standard
atmosphere, with mercury as the working material. Although these defining
correlations are commonly taught in schools today, by international agreement the
unit “degree Celsius” and the Celsius scale are currently defined by two different
temperatures: absolute zero and the triple point of Vienna Standard Mean Ocean
Water (VSMOW; specially purified water). This definition also precisely relates the
Celsius scale to the Kelvin scale, which defines the SI base unit of thermodynamic
temperature and which uses the symbol K. Absolute zero, the lowest temperature
possible (the temperature at which matter reaches minimum entropy), is defined as
being precisely 0K and -273.15°C. The temperature of the triple point of water is
defined as precisely 273.16K and 0.01°C. Based on this, the relationship between
degree Celsius and Kelvin is as follows:

TCelsius = TKelvin − 273.15TCelsius

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Fahrenheit Scale

In the Fahrenheit scale, the freezing of water is defined at 32 degrees, while the
boiling point of water is defined to be 212 degrees.

The Fahrenheit system puts the boiling and freezing points of water exactly 180
degrees apart. Therefore, a degree on the Fahrenheit scale is 1/180 of the interval
between the freezing point and the boiling point. On the Celsius scale, the freezing
and boiling points of water are 100 degrees apart. A temperature interval of 1 °F is
equal to an interval of 5/9 degrees Celsius (°C). To convert °F to °C, you can use the
following formula:

Absolute Zero

Absolute zero is the coldest possible temperature; formally, it is the

temperature at which entropy reaches its minimum value.

•   Absolute zero is universal in the sense that all matter is in ground state at this
temperature. Therefore, it is a natural choice as the null point for a temperature
unit system.
•   K system at absolute zero still possesses quantum mechanical zero-point
energy, the energy of its ground state. However, in the interpretation of
classical thermodynamics, kinetic energy can be zero, and the thermal energy
of matter vanishes.

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•   The lowest temperature that has been achieved in the laboratory is in the 100
pK range, where pK (pico- Kelvin ) is equivalent to 10-12 K. The lowest natural
temperature ever recorded is approximately 1K, observed in the rapid
expansion of gases leaving the Boomerang Nebula.

Absolute zero is the coldest possible temperature. Formally, it is the

temperature at which entropy reaches its minimum value. More simply put,
absolute zero refers to a state in which all the energy of a system is extracted (by
definition, the lowest energy state the system can have). Absolute zero is universal
in the sense that all matteris in ground state at this temperature. Therefore, it is a
natural choice as the null point for a temperature unit system.

Kelvin Scale

The kelvin is a unit of measurement for temperature; the null point of the
Kelvin scale is absolute zero, the lowest possible temperature.

The Kelvin is a unit of measurement for temperature. It is one of the seven

base units in the International System of Units (SI) and is assigned the unit symbol
K. The Kelvin scale is an absolute, thermodynamic temperature scale using absolute
zero as its null point. In the classical description of thermodynamics, absolute zero
is the temperature at which all thermal motion ceases.

The choice of absolute zero as null point for the Kelvin scale is logical.
Different types of matter boil or freeze at different temperatures, but at 0K (absolute
zero), all thermal motions of any matter are maximally suppressed. The Kelvin scale
is used extensively in scientific work because a number of physical quantities, such
as the volume of an ideal gas, are directly related to absolute temperature.

The Kelvin scale is named after Glasgow University engineer and physicist
William Thomson, 1st Baron Kelvin (1824-1907), who wrote of the need for an
“absolute thermometric scale. ” Unlike the degree Fahrenheit and the degree
Celsius, the kelvin is not referred to or typeset as a degree. The kelvin is the primary
unit of measurement in the physical sciences, but it is often used in conjunction with
the degree Celsius, which has the same magnitude. The kelvin is defined as the
fraction 1/273.16 of the thermodynamic temperature of the triple point of water
(exactly 0.01°C, or 32.018°F). To convert kelvin to degrees Celsius, we use the
following formula:

TCelsius=TKelvin − 273.15

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Sample Temperature Conversions:

Sample Problems:

The boiling temperature of liquid oxygen at normal pressure at -182.96 °C. What
is the value in Kelvin Scale ?

Solution
K = ºC + 273.15

ºC= -182.96

Put the value of ºC in the formula : K = -182.96 + 273.15

Value in Kelvin Scale : K = 90.19 K

The temperature at which liquid oxygen boils under normal pressure is 90.19 K .

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Practice Problem:

A general rule of thumb used by pilots is for every 1,000 feet of altitude, the
temperature falls 3.5 F. If the temperature at sea level is 78 F, what would you
expect the temperature to be at 10,000 feet in Celsius (to the 10th)? Ans. 6.1OC or
43 F

Thermodynamic states

System – specific part of the universe chosen for study.

Surrounding – part of the universe immediately outside the system in
which matter and energy interactions can be detected.

The application of thermodynamic principles begins by defining a system

that is in some sense distinct from its surroundings. For example, the system could
be a sample of gas inside a cylinder with a movable piston, an entire steam engine,
a marathon runner, the planet Earth, a neutron star, a black hole, or even the
entire universe. In general, systems are free to exchange heat, work, and other forms
of energy with their surroundings.

A system’s condition at any given time is called its thermodynamic state. For
a gas in a cylinder with a movable piston, the state of the system is identified by
the temperature, pressure, and volume of the gas. These properties are characteristic
parameters that have definite values at each state and are independent of the way
in which the system arrived at that state. In other words, any change in value of a
property depends only on the initial and final states of the system, not on the path
followed by the system from one state to another. Such properties are called state
functions. In contrast, the work done as the piston moves and the gas expands and
the heat the gas absorbs from its surroundings depend on the detailed way in which
the expansion occurs.

The behaviour of a complex thermodynamic system, such as Earth’s

atmosphere, can be understood by first applying the principles of states and
properties to its component parts—in this case, water, water vapour, and the various
gases making up the atmosphere. By isolating samples of material whose states and
properties can be controlled and manipulated, properties and their interrelations
can be studied as the system changes from state to state.

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Types of System
Open System – can exchange mass and energy usually in the form of heat with its
surroundings
Closed system – allows transfer of energy but not mass between system and
surrounding
Isolated system – does not allow the transfer of either mass or energy

Closed system (m = constant):

When there is an exchange of energy (work and heat) but not matter between the
system and surrounding the system is known as control mass or closed system. For
Example, a greenhouse is a closed system that exchanges heat but not work with its
surroundings. Depending on the properties of its boundary a system exchanges
work, heat, or both. An Adiabatic boundary does not allow the exchange of heat
from the system to surroundings and a rigid body does not allow the exchange of
work between system and surroundings.

Isolated systems:
An isolated system does not allow the exchange of heat, work, or matter between
the system & surroundings. For example, an insulated container, such as an
insulated gas cylinder.
i.e min=mout=Ein=Eout=0

Open system:
In an open or control volume system, there is an exchange of energy i.e. heat, work,
and matter between the system & surroundings. A boundary that allows the
exchange of matter is known as the permeable boundary. For example, the ocean,
turbine, water heater, car radiator, nozzle, etc. To analyze an open system, the
energy of the system is always taken equal to the energy leaving the system.

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Other Type of Systems:

Rigid system: It is a type of closed system in which the system interacts with the
surroundings by exchanging heat only.
Adiabatic system: It is a closed or open system in which energy is transferred to its
surroundings only as work (without transfer of heat or matter).

Properties of a System:
Intensive properties: Intensive properties are independent of the size of a system,
for example, Density, Molar volume, Surface tension, Refractive index, Viscosity,
Specific heat, temperature, Free energy per mole, pressure, etc. They are not additive
in nature.
Extensive properties: These are properties that are dependent on the size of the
system, for example, number of moles, volume, mass, entropy, free energy,
enthalpy, heat capacity, internal energy, etc. They are additive in nature. The specific
properties are per unit mass extensive properties, for example, specific mass,
specific energy, specific volume, etc.

Thermodynamic Process:
The Thermodynamic process deals with the change of a system’s state from one
state to another. The different types of thermodynamic process are isothermal,
adiabatic, isobaric and isochoric.
In an Isothermal process, the temperature of the system remains constant [dE and
dT = 0] during the state change. This process is carried out in a thermostat and the
energy exchange takes place without any change in temperature. In an Adiabatic
process, the exchange of energy between the system and surroundings does not
occur [dQ = 0]. It is carried out in a perfectly insulated container. The temperature
of the system might change during an adiabatic process. In an Isobaric process, the
pressure of the system remains constant [dP = 0]. In an Isochoric process, the
volume of the system remains constant [dV = 0].
Cyclic Thermodynamic
1. In a cyclic process, a system returns to its initial state after undergoing a number
of different thermodynamic processes.
2. A process that is carried out on its own without any external help, is known as
Spontaneous Process.
3. In the Quasi-Static or reversible process, the system and its surroundings can be
returned from its final state to its initial state without any changes in the
thermodynamic properties of the universe. The irreversible processes are also

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known as the natural processes because all the processes that occur in nature are
irreversible processes. It occurs due to the finite gradient between the two states of
the system.

Zeroth Law of Thermodynamics

Zeroth law of thermodynamics is one of the four laws of thermodynamics.

The credit for formulating the law goes to Ralph H. Fowler. Interestingly, the zeroth
law of thermodynamics was actually developed much later than the original three
laws. However, there were few confusions regarding the nomenclature whether it
should be named the fourth law or some other name. The complication arose
because the new law gave a much clearer definition of the temperature and basically
replaced what the other three laws had to state. Fowler finally came up with the
name to end this conflict.

The zeroth law of thermodynamics frames an idea of temperature as an

indicator of thermal equilibrium.

What is Zeroth Law of Thermodynamics?

When a body ‘A’ is in thermal equilibrium with another body ‘b’, and also
separately in thermal equilibrium with a body ‘C’, then body ‘B’ and ‘C’ will also be
in thermal equilibrium with each other. This statement defines the zeroth law of
thermodynamics. The law is based on temperature measurement.

There are also various ways to state the zeroth law of thermodynamics.
However, in simple terms, it can be said, “Systems that are in thermal equilibrium
exist at the same temperature”.

Zeroth law of thermodynamics takes into account that temperature is

something worth measuring because it predicts whether the heat will transfer
between objects or not. This is true regardless of how the objects interact. Even if
two objects are not in physical contact, heat still can flow between them, by means

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of radiation mode of heat transfer. Whereas, zeroth law of thermodynamics states

that, if the systems are in thermal equilibrium, no heat flow will take place.

Thermal Equilibrium
Temperature is a property that distinguishes thermodynamics from other
sciences. This property can distinguish between hot and cold. When two or more
bodies at different temperatures are brought into contact then after some time they
attain a common temperature and they are said to exist in thermal equilibrium.

Systems are said to be in thermal equilibrium if there is no heat transfer, even

if they are in a position to transfer heat, based on other factors. For Example, If we
put food in the refrigerator overnight then that food is in thermal equilibrium with
the air of that refrigerator. Heat no longer flows from food to the air or from the air
to the food this state is known as thermal equilibrium.

Zeroth Law of Thermodynamics Example and Applications

The law is important for the mathematical formulation of thermodynamics

or more precisely for stating the mathematical definition of temperature. This law is
mostly used to compare temperatures of different objects.

If we want to measure the accurate temperature, a reference body is required

and a certain characteristic of that body which changes with temperature. The
change in that characteristic may be taken as an indication of a change of
temperature. That selected characteristic is known as thermodynamic property.

Nonetheless, the most common application of the zeroth law of

thermodynamics can be seen in thermometers. We can observe the zeroth law in
action by taking a very common thermometer having mercury in a tube. As the
temperature is increased this mercury expands since the area of the tube is constant.
Due to this expansion, the height is increased. Now, the increase in the height of the
mercury label shows the changes in temperature and basically helps us to measure
it.

There are different kinds of thermometer that can be used depending on their
thermometric property. They are as follows.

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Thermometer Thermometric Property

Constant volume gas thermometer Pressure

Constant pressure gas thermometer Volume

Electrical resistance thermometer Resistant

Thermocouple Thermal e.m.f

Mercury -in -glass thermometer Length

Similarly, another example of the zeroth law of thermodynamics is when you
have two glasses of water. One glass will have hot water and the other will contain
cold water. Now if we leave them in the table for a few hours they will attain thermal
equilibrium with the temperature of the room.

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Name: __________________________________ Rating: _____________

Section: _________________________________ Date: ______________

Problem Set No. 1

Temperature and Zeroth Law of Thermodynamics

I.   Answer the following questions scientifically. Write your answer in red font.

1.   What is the difference between heat, thermal energy and temperature?

2.   In terms of thermal energy, why does a bottle of soda left in the sun have a
higher temperature than one left in an ice chest?

3.   Which has more thermal energy, a 5-kg bowling all that has been resting on a
hot driveway for 4 hours on a 350C day, or the same bowling ball rolling down
a lane in an air-conditioned bowling alley? Explain.

4.   Why does your hand feel cool if you spill some alcohol on it?

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5.   Explain why poor conductors of heat are good insulators of heat.

II.   Temperature Conversion

Convert the following temperatures to the required unit. Show your
solution by either typing the solution or taking a picture of the solution and
pasting the picture in this document.

Convert the following to Fahrenheit

1) 10o C ________

2) 30o C ________

3) 40o C ________

4) 37o C ________

5) 0o C ________

Convert the following to Celsius

6) 32o F ________

7) 45o F ________

8) 70o F ________

9) 80o F ________

10) 90o F ________

11) 212o F ________

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Convert the following to Kelvin

12) 0o C ________

13) -50o C ________

14) 90o C ________

15) -20o C ________

Convert the following to Celsius

16) 100o K ________

17) 200o K ________

18) 273o K ________

19) 350o K ________

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Topic 2
Thermal Expansion

Introduction
This section discusses the thermal expansion property of matter and
demonstrates the calculation of thermal expansion based on the thermal expansion
coefficient and change in temperature.

Intended Learning Outcomes

At the end of this section, the students are expected to:
4.   Apply the concept of linear expansion and relate it to stress;
5.   Apply the volume expansion in global warming and coastal flooding
6.   Determine experimentally the coefficient of linear expansion of metal
samples
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Thermal Expansion

Thermal expansion, the general increase in the volume of a material as

its temperature is increased. It is usually expressed as a fractional change in length
or volume per unit temperature change; a linear expansion coefficient is usually
employed in describing the expansion of a solid, while a volume expansion
coefficient is more useful for a liquid or a gas. If a crystalline solid is isometric (has
the same structural configuration throughout), the expansion will be uniform in all
dimensions of the crystal. If it is not isometric, there may be different expansion
coefficients for different crystallographic directions, and the crystal will change
shape as the temperature changes.

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In a solid or liquid, there is a dynamic balance between the cohesive forces

holding the atoms or molecules together and the conditions created by temperature;
higher temperatures imply greater distance between atoms. Different materials
have different bonding forces and therefore different expansion coefficients.

SOLIDS
For many solids, expansion is directly proportional to temperature change.

∆ℓ = αℓ0∆T

Areas expand twice as much as lengths do.

∆A = 2αA0∆T

Volumes expand three times as much as lengths do.

∆V = 3αV0∆T
Applications
•   buckling
•   expansion gap/joint
•   anti-scalding valve
•   bimetallic strip, thermostat
•   expansion of holes (mounting train tires)
•   "What's more, the aircraft expands by 15-25 centimeters during flight because
of the scorching heat created by friction with air. Designers used rollers to
isolate the cabin from the body, so that stretching doesn't rip the plane apart."
Helen Pearson "Concorde wings its way into retirement." Nature Physics
Portal. October 2003.
•   "Concorde measures 204ft in length - stretching between six and ten inches in-
flight due to heating of the airframe. She is painted in a specially developed
white paint to accommodate these changes and to dissipate the heat generated
by supersonic flight." source
•   Thermal expansion is a small, but not always insignificant effect. Typical
coefficients are measured in parts per million per kelvin (10−6/K). That means
your typical classroom meter stick never varies in length by more than a
100 µm in its entire lifetime — probably never more than 10 µm while students
are using it.

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measurement techniques
•   length comparator
•   push rod dilatometer (gives relative expansion, since the device itself expands)
•   interferometer (highest precision method)
•   x-ray diffactometer
•   capacitance dilatometer
•   strain gauge
•   optical dilatometer (basically a digital camera)

anisotropic expansion

•   Some materials expand differently in different directions, notably graphite and

wood (lumber).

LIQUIDS
Liquids can only expand in volume.

∆V = βV0∆T

Liquids have higher expansivities than solids.

β ~ 10−3/K, 3α ~ 10−5/K

applications
•   Liquid in glass thermometer. The alcohol is colored red to look like wine.
ethyl alcohol 1120 × 10−6/K
mercury 181 × 10−6/K
glass 3(8.5 × 10−6/K) = 25.5 × 10−6/K

Sample Problems

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Name: __________________________________ Rating: _____________

Section: _________________________________ Date: ______________

Problem Set No. 2

Thermal Expansion

Directions: Solve the following problems correctly. Show you systematic solution
on the space provided after each item. Apply the proper number of significant
figures in expressing your final answer. Box your final answer.

1.   Most bridges contain interlocking steel grates (α steel = 1.2 x 10 - 5 ºC -1) that
allow the bridge to expand and contract with the changes in temperature. The
Golden Gate Bridge in San Francisco is about 1350 meters long.

a.   The seasonal temperature variation in San Francisco ranges from about 0ºC
to 30ºC. How much will the bridge expand between these two extremes?

b.   What percent of the length of a subcompact automobile, 2.5 meters, does

this gap represent?

2.   Selena has a fire in her fireplace to warm her 20ºC apartment. She realizes that
she has accidentally left the iron poker (α iron = 1.2 x 10- 5 ºC-1) in the fire. How
hot is the fire if the 0.60-meter poker lengthens 0.30 cm?

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3.   Just before midnight, when the air temperature is 10.0ºC, Karl stops and fills the
0.0600 m3 gas tank in his car. At noon the next day, when the temperature has
risen to 32ºC, Karl finds a puddle of gasoline (βgas = 3 x 10-4 ºC-1) beneath his car.
How much gasoline spilled out of Karl's car? (assume that there was virtually
no change in the volume of his tank).

4.   As he rides the train to work on a -4ºC winter day, Mr. Trump notices that he
can hear the click of the train going over the spaces between the rails. Six
months later, on a 30ºC summer day, the rails are pushed together and he hears
no clicks. If the rails are 5 meters long when the temperature is 30ºC, how large
a gap is left between the steel rails (α steel = 1.2 x 10 - 5 ºC -1) on the cold winter
day?

5.   A popular winter activity of many college students is "traying," or sliding down

a snow-covered hill on a tray borrowed from the dining hall. If Joanne removes
a 0.35 m x 0.65 m aluminum tray (α aluminum = 2.4 x 10-5 ºC-1) from the 20ºC
dining hall to go traying outside in the brisk -8ºC winter air, how much will the
tray shrink when it is taken outside?

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Topic 3
IDEAL GASES AND THE KINETIC MOLECULAR THEORY OF GASES

Introduction
This section discusses the different gas laws and the kinetic molecular theory
of gases and

Intended Learning Outcomes

At the end of this section, the students are expected to:
1.   Use the ideal gas law to analyze a system of gas;
2.   Understand the assumptions of the kinetic theory of gases model;
3.   Explain the molecular interpretation of temperature;
4.   Calculate the root-mean-square speed of a gas to its molar mass
5.   Determine the internal energy of monoatomic gases
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Macroscopic Description of an Ideal Gas

An ideal gas is a theoretical gas composed of many randomly moving point

particles that are not subject to interparticle interactions. The ideal gas concept is
useful because it obeys the ideal gas law, a simplified equation of state, and is
amenable to analysis under statistical mechanics.
In most usual conditions (for instance at standard temperature and pressure),
most real gases behave qualitatively like an ideal gas. Many gases such
as nitrogen, oxygen, hydrogen, noble gases, and some heavier gases like carbon
dioxide can be treated like ideal gases within reasonable tolerances.[2] Generally, a
gas behaves more like an ideal gas at higher temperature and lower pressure,[2] as
the potential energy due to intermolecular forces becomes less significant compared
with the particles' kinetic energy, and the size of the molecules becomes less
significant compared to the empty space between them. One mole of an ideal gas
has a capacity of 22.710947(13) litres[3] at standard temperature and pressure
(a temperature of 273.15 K and an absolute pressure of exactly 105 Pa) as defined
by IUPAC since 1982.
The ideal gas model tends to fail at lower temperatures or higher pressures,
when intermolecular forces and molecular size becomes important. It also fails for
most heavy gases, such as many refrigerants, and for gases with strong
intermolecular forces, notably water vapor. At high pressures, the volume of a real
gas is often considerably larger than that of an ideal gas. At low temperatures, the
pressure of a real gas is often considerably less than that of an ideal gas. At some
point of low temperature and high pressure, real gases undergo a phase transition,

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such as to a liquid or a solid. The model of an ideal gas, however, does not describe
or allow phase transitions. These must be modeled by more complex equations of
state. The deviation from the ideal gas behavior can be described by a dimensionless
quantity, the compressibility factor, Z.
The ideal gas model has been explored in both the Newtonian dynamics (as
in "kinetic theory") and in quantum mechanics (as a "gas in a box"). The ideal gas
model has also been used to model the behavior of electrons in a metal (in the Drude
model and the free electron model), and it is one of the most important models in
statistical mechanics.
If the pressure of an ideal gas is reduced in a throttling process the
temperature of the gas does not change. (If the pressure of a real gas is reduced in a
throttling process, its temperature either falls or rises, depending on whether
its Joule–Thomson coefficient is positive or negative.)

There are three basic classes of ideal gas:

(a)  the classical or Maxwell–Boltzmann ideal gas,
(b)  the ideal quantum Bose gas, composed of bosons, and
(c)   the ideal quantum Fermi gas, composed of fermions.

The classical ideal gas can be separated into two types: The classical
thermodynamic ideal gas and the ideal quantum Boltzmann gas. Both are
essentially the same, except that the classical thermodynamic ideal gas is based on
classical statistical mechanics, and certain thermodynamic parameters such as
the entropy are only specified to within an undetermined additive constant. The
ideal quantum Boltzmann gas overcomes this limitation by taking the limit of the
quantum Bose gas and quantum Fermi gas in the limit of high temperature to
specify these additive constants. The behavior of a quantum Boltzmann gas is the
same as that of a classical ideal gas except for the specification of these constants.
The results of the quantum Boltzmann gas are used in a number of cases including
the Sackur–Tetrode equation for the entropy of an ideal gas and the Saha ionization
equation for a weakly ionized plasma.

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Classical thermodynamic ideal gas

The classical thermodynamic properties of an ideal gas can be described by
two equations of state:

Ideal gas law

The ideal gas law is the equation of state for an ideal gas, given by:

PV = nRT
The ideal gas law is an extension of experimentally discovered gas laws. It
can also be derived from microscopic considerations.
Real fluids at low density and high temperature approximate the behavior of
a classical ideal gas. However, at lower temperatures or a higher density, a real fluid
deviates strongly from the behavior of an ideal gas, particularly as it condenses from
a gas into a liquid or as it deposits from a gas into a solid. This deviation is expressed
as a compressibility factor.
This equation is derived from

$
Boyle’s Law: 𝑉   ∝  
%

Charles’s Law : 𝑉   ∝ 𝑇

Avogadro’s Law: 𝑉   ∝ 𝑛

After combining three laws we get

𝑛𝑇
𝑉   ∝  
𝑃
That is:
𝑛𝑇
𝑉=𝑅
𝑃
𝑃𝑉 = 𝑛𝑅𝑇

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Sample Problems:

The Kinetic Theory of Gases

The kinetic molecular theory of gases is a model that helps us understand the
physical properties of gases at the molecular level. It is based on the following
concepts:
1.   Gases consist of particles (molecules or atoms) that are in constant random
motion.
2.   Gas particles are constantly colliding with each other and the walls of their
container. These collisions are elastic; that is, there is no net loss of energy
from the collisions.
3.   Gas particles are small and the total volume occupied by gas molecules is
negligible relative to the total volume of their container.
4.   There are no interactive forces (i.e., attraction or repulsion) between the
particles of a gas.
5.   The average kinetic energy of gas particles is proportional to the absolute
temperature of the gas, and all gases at the same temperature have the same
average kinetic energy.

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Avogadro’s Number (NA) is the number of particles of (molecules or atoms) in 1

kmol of substance. For all substances,

NA = 6.022 x 1026 particles/mol

As examples, M = 2 kg/kmol for H2 and M = 32 kg/kmol for O2. Therefore, 2 kg

of H2 and 32 kg of O2 contain 6.02 x 1026 molecules.

The Mass of a Molecule (or atom) can be found from the molecular mass M of the
substance and Avogadro’s number NA. Since M kg of substance contains NA
particles, the mass mo of one particle is given by:

𝑀
𝑚, =  
𝑁/

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Sample Problems

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Name: __________________________________ Rating: _____________

Section: _________________________________ Date: ______________

Problem Set No. 3

Gas Laws and the Kinetic Theory of Gases

Directions: Solve the following problems correctly. Show you systematic solution
on the space provided after each item. Apply the proper number of significant
figures in expressing your final answer. Box your final answer.

1.   Identify each statement as True or False.

According to the basic assumption of kinetic molecular theory gas particles:

____________a.   are far apart
____________b.   have a significant volume with respect to the volume of
the container they occupy
____________c.   move rapidly in a constant random motion
____________d.   lose kinetic energy when colliding

2.   Give one reason why industrial companies prefer to store a condensed fuel
as a liquid rather than a gas.

3.   Using the kinetic molecular theory, explain why a gas can be easily
compressed, while a liquid and a solid cannot?

4.   Describe the cause of pressure inside of any container filled with a gas.

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5.   List three common units of pressure and their value at atmospheric

pressure.

6.   How does temperature relate to kinetic energy?

7.   Using the terms particles, collisions, pressure, volume, and temperature

answer the following questions.

a.   Describe the effect of adding a gas to a container that cannot expand.

b.   Describe the effect of making the container size smaller.

c.   Describe the effect of cooling a gas in a container.

Boyle’s Law, Charles’s Law, and Gay-Lussac’s Law

1.   A child brings an inflatable ball on a small plane. Before take-off, the 2.00 L
ball has a pressure of 101.3 kPa. The pilot flies the plane at an altitude where
the air pressure is 75.0 kPa. What is the volume of the ball at this altitude if
the temperature in the plane remains constant?

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2.   At a depth of 30 meters, the combined pressure of air and water on a diver

is about four times the normal atmospheric pressure (400. kPa rather than
100. kPa). Suppose a diver exhales into the water, and one of the air bubbles
has a volume of 10.0 mL. What will be the volume of this bubble when it
reaches the surface of the water, assuming that it does not break apart and
that its temperature does not change?

3.   A 2.0 L helium balloon at a pressure of 1.00 atm on the Earth's surface

ascends 10 km into the atmosphere, where the pressure is 0.27 atm. What is
the volume of the balloon at that altitude (assuming the temperature stays
the same)?

4.   A child receives a balloon filled with 2.30 L of helium from a vendor at an

amusement park. The temperature outside is 31°C. What will be the volume
of the balloon when the child brings it home to an air-conditioned house at
22°C?

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5.   A 1.5 L pocket of air with a temperature of 295 K rises in the air. If pressure
is not changed, what will be the temperature of the air pocket when the
volume decreases to 0.90 L?

Combined Gas Law and Ideal Gas Law

1.   The air in a balloon has a volume of 3.00 L and exerts a pressure of 101.3
kPa at 27°C. What pressure does the air in the balloon exert if the
temperature is increased to 400.0 K and the air is allowed to expand to 15.0
L?

2.   A sample of carbon dioxide occupies 4.50 L at 750 K and 500.0 kPa. What is
the volume of this gas at STP?

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3.   A sample of methane that initially occupies 850.0 ml at 500.0 kPa and

227.0°C is compressed to a volume of 700.0 ml. To what temperature will
the gas need to be cooled to lower the pressure of the gas to 200.0 kPa?

4.   A helium balloon has a volume of 500.0 ml at STP. What will be its new
volume if the temperature is increased to 152°C and its pressure is increased
to 125 kPa?

5.   An 8.00 L sample of neon gas at 25°C exerts a pressure of 900. kPa. If the gas
is compressed to 2.00 L and the temperature is raised to 225°C, what will
the new pressure be?

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Dalton’s Law and Graham’s Law

1.   Hydrogen gas is collected by water displacement at a total pressure of 111.0

kPa. The temperature is 50.0°C, and therefore the partial pressure of water
vapor is 12.34 kPa. What is the pressure exerted by the 'dry' gas?

2.   A mixture of gases of 3 moles of oxygen, 1 moles of carbon dioxide, and 8

moles of nitrogen. Calculate the mole fraction and partial pressure of each gas
in the mixture if the total pressure on the system is 0.65 atm.

3.   A mixture of 28.0 g of ammonia and 16.0 g of hydrogen has a total pressure of

1.3 atm. What is the partial pressure of each gas?

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4.   A container contains 20.0 g of oxygen and 80.0 grams of nitrogen gas. a.

Calculate the mole fraction of each gas in the mixture. b. Determine the partial
pressure of each gas if the mixture of gases has a total pressure of 99.3 kPa.

5.   Nitrogen gas effuses through an opening at a rate 2.39 times faster than an
unknown gas. What is the molecular mass of the unknown gas?

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Topic 4
Internal Energy, Heat and Specific Heat

Introduction
This section discusses interrelationship of heat and internal. It also presents
the concepts of specific heat and calorimetry.

Intended Learning Outcomes

At the end of this section, the students are expected to:
1.   Explain the difference between heat and internal energy;
2.   Identify the different units of heat
3.   Relate caloric energy to mechanical energy using mechanical
equivalent of hear
4.   Define specific heat capacity of a substance.
5.   Compare the specific heats of some materials at atmospheric pressure
6.   Determine experimentally the specific heat of a sample metal
7.   Use the energy transfer equation in the context of linear expansion and
compressional stress
8.   Solve a calorimetric problem involving three substances at three different
temperatures
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Heat and Internal Energy

A thermal system has internal energy (also called thermal energy), which is the
sum of the mechanical energies of its molecules. The internal energy of a system is
identified with the random, disordered motion of molecules; the total (internal)
energy in a system includes potential and kinetic energy. The symbol for internal
energy is U.

A system’s internal energy is proportional to its temperature. As we saw earlier in

this chapter, if two objects at different temperatures are brought into contact with
each other, energy is transferred from the hotter to the colder object until the bodies
reach thermal equilibrium (that is, they are at the same temperature). No work is
done by either object because no force acts through a distance. These observations
reveal that heat is energy transferred spontaneously due to a temperature
difference.

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Energy on a smaller scale

•   Internal energy includes energy on a microscopic scale

•   It is the sum of all the microscopic energies such as:
1.   translational kinetic energy
2.   vibrational and rotational kinetic energy
3.   potential energy from intermolecular forces

Mechanical Equivalent of Heat

It is also possible to change the temperature of a substance by doing work, which

transfers energy into or out of a system. This realization helped establish that heat
is a form of energy. James Prescott Joule (1818–1889) performed many experiments
to establish the mechanical equivalent of heat—the work needed to produce the
same effects as heat transfer. In the units used for these two quantities, the value for
this equivalence is

1.000 kcal = 4186 J

1 cal = 4.186 J

Specific Heat - is the amount of energy necessary to raise the temperature of one
gram of substance by one degree Celsius.

𝐪
𝐂𝐩 =  
𝐦𝚫𝐓

Where Cp = specific heat

q = heat energy
m = mass
ΔT = change in temperature

Heat Capacity – is the amount of energy necessary to raise a given amount of

substance by one degree Celsius. The relationship between specific
heat and heat capacity of a given substance is given by:
C = mc C = heat capacity
m = mass
c = specific heat

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Sample Problems:

Calorimetry

•   Calorimetry – deals with the measurement of heat and energy changes in

chemical and physical processes and depends on an understanding of specific heat
and heat capacity.

•   Calorimeter - a device which contains water and/or another substance with a

known capacity for absorbing energy (heat). Calorimeters are adiabatic systems
(thermally insulated from the rest of the universe).

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Name: __________________________________ Rating: _____________

Section: _________________________________ Date: ______________

Problem Set No. 4

Internal Energy, Heat and Specific Heat

1.   How much heat is required to raise the temperature of 67.0g of water from
25.7°C to 66.0°C? The specific heat of H2O is 4.184J/g°C)

2.   What is the mass of a sample of metal that is heated from 58.8°C to 88.9°C with
a specific heat of 0.4494J/g°C, if Q = 4500.0J?

3.   How much heat is required to raise the temperature of a 10.35g sample of

carbon tetrachloride from 32.1°C to 56.4°C? The specific heat of carbon
tetrachloride is 0.85651J/g°C.

4.   Calculate the heat given off when 177 g of copper cools from 155.0°C to 23.0°C.
The specific heat of copper is 0.385 J/g°C.

5.   How much heat is released as 5.00 g of Pb cool from 75.0oC to 25.0oC? The
specific heat of Pb is 0.128 J/g°C.

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6.   73.5 g of aluminum is heated in boiling water to a temperature of 98.7°C. the

Aluminum is then placed in a calorimeter containing 1500.0 g of water at a
temperature of 25.40°C. The temperature of the water in the calorimeter
increase to a final temperature of 28.20°C. What is the specific heat of the
Aluminum?

7.   A piece of metal with a specific heat capacity of 0.460 J/g°C at a temperature

of 100.0°C is dropped into an insulated container of water. The mass of water
is 140.0 g and its temperature before adding the metal is 16.0°C. The final
temperature of the water is 17.6°C. What is the mass of the metal?

8.   A 5.00 g piece of metal is heated to 100.0oC, then placed in a beaker containing

20.0 g of water at 10.0oC. The temperature of the water rises to 15.0oC.
Calculate the specific heat of the metal.

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9.   A sample of cobalt (specific heat of Co = 0..418 J/g˚C) at 200.0˚C is dropped

into a calorimeter containing 50.0 mL of water at 21.1˚C. The final temperature
of the water/cobalt mixture was 67.1˚C. What was the mass of the sample of
cobalt?
(Hint: 1 mL of water has a mass of 1 gram)

10.  Hot lead with a mass of 200.0 g of (Specific heat of Pb = 0.129 J/g˚C) at 176.4˚C
was dropped into a calorimeter containing an unknown volume of water. The
temperature of the water increased from 21.7˚C to 56.4˚C. What volume of
water is in the calorimeter?

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Topic 5
Latent Heat and Phase Change

Introduction
This section discusses the mechanism behind phase changes and calculating
the amount of heat absorbed or released in such changes.

Intended Learning Outcomes

At the end of this section, the students are expected to:
1.   Compare and contrast the three common phases of matter.
2.   Define latent heats of substances.
3.   Solve problems involving phase changes.
4.   Determine experimentally the latent heat of fusion of ice.
--------------------------------------------------------------------------------------------------------------

During a phase change, matter changes from one phase to another, either
through the addition of energy by heat and the transition to a more energetic state,
or from the removal of energy by heat and the transition to a less energetic state.

The latent heat is the energy associated with a phase change of a substance.

Phase changes to a more energetic state include the following:

•   Melting—Solid to liquid
•   Vaporization—Liquid to gas (included boiling and evaporation)
•   Sublimation—Solid to gas

Phase changes to a less energetic state are as follows:

•   Condensation—Gas to liquid
•   Freezing—Liquid to solid

Energy is required to melt a solid because the bonds between the particles in the
solid must be broken. Since the energy involved in a phase changes is used to break
bonds, there is no increase in the kinetic energies of the particles, and therefore no
rise in temperature. Similarly, energy is needed to vaporize a liquid to overcome the
attractive forces between particles in the liquid. There is no temperature change
until a phase change is completed. The temperature of a cup of soda and ice that is
initially at 0 0C stays at 0 0C until all of the ice has melted. In the reverse of these
processes—freezing and condensation—energy is released from the latent heat

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The heat, Q, required to change the phase of a sample of mass m is

Q = mLf (for melting/freezing)

Q = mLv (for vaporization/condensation)

where Lf and Lv are latent heat of fusion and latent heat of vaporization. The latent
heat of fusion is the amount of heat needed to cause a phase change between solid
and liquid. The latent heat of vaporization is the amount of heat needed to cause a
phase change between liquid and gas. Lf and Lv are coefficients that vary from
substance to substance, depending on the strength of intermolecular forces, and
both have standard units of J/kg.

Key Points

•   Energy is required to change the phase of a substance, such as the energy to

break the bonds between molecules in a block of ice so it may melt.
•   During a phase change energy my be added or subtracted from a system, but
the temperature will not change. The temperature will change only when the
phase change has completed.
•   The heat Q required to change the phase of a sample of mass m is given
by Q=mLfQ=mLf (melting or freezing) and Q=mLvQ=mLv (evaporating or
condensing), where Lf and Lv are the latent heat of fusion and the latent heat
of vaporization, respectively.

Key Terms

•   latent heat of fusion: the energy required to transition one unit of a

substance from solid to liquid; equivalently, the energy liberated when one
unit of a substance transitions from liquid to solid.
•   latent heat of vaporization: the energy required to transition one unit of a
substance from liquid to vapor; equivalently, the energy liberated when one
unit of a substance transitions from vapor to liquid.
•   sublimation: the transition of a substance from the solid phase directly to the
vapor state such that it does not pass through the intermediate, liquid phase

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Let’s consider the example of adding heat to ice to examine its transitions
through all three phases—solid to liquid to gas. A phase diagram indicating the
temperature changes of water as energy is added is shown in Figure. The ice starts
out at −20°C, and its temperature rises linearly, absorbing heat at a constant rate
until it reaches 0°. Once at this temperature, the ice gradually melts, absorbing 334
kJ/kg. The temperature remains constant at 0°C during this phase change. Once all
the ice has melted, the temperature of the liquid water rises, absorbing heat at a new
constant rate. At 100°C, the water begins to boil and the temperature again remains
constant while the water absorbs 2256 kJ/kg during this phase change. When all the
liquid has become steam, the temperature rises again at a constant rate.

Figure 1 A graph of temperature versus added energy. The system is constructed so that no vapor forms while ice warms
to become liquid water, and so when vaporization occurs, the vapor remains in the system. The long stretches of constant
temperature values at 0

We have seen that vaporization requires heat transfer to a substance from its
surroundings. Condensation is the reverse process, where heat in transferred away
from a substance to its surroundings. This release of latent heat increases the
temperature of the surroundings. Energy must be removed from the condensing
particles to make a vapor condense. This is why condensation occurs on cold
surfaces: the heat transfers energy away from the warm vapor to the cold surface.
The energy is exactly the same as that required to cause the phase change in the
other direction, from liquid to vapor, and so it can be calculated from Q=mLv. Latent
heat is also released into the environment when a liquid freezes, and can be
calculated from Q=mLf.

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Sample Problems

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Name: __________________________________ Rating: _____________

Section: _________________________________ Date: ______________

Problem Set No. 5

Latent Heat and Phase Change

1.   Calculate the energy transfered when 36.8g of water forms an ice cube in a
freezer at 0.0°C. Is energy absorbed or released?

2.   Mercury is a neurotoxin that when inhaled can be highly dangerous.

Calculate the amount of energy required to change 14g of liquid mercury into
a gas at 357°C? See the values in the table at the end of this worksheet to solve
this problem. Is energy absorbed or released?

3.   Calculate the energy needed to evaporate 340.0g water from an ocean to form
water vapor. Is energy absorbed or released?

4.   Ethanol is used as a fuel and is the main ingredient of alcohol. Calculate the
amount of energy required to evaporate 2.5g of ethanol. See the values in the
table at the end of this worksheet to solve this problem. Is energy absorbed
or released?

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5.   How much energy in joules is required to heat 25g of ice from -10.0°C to 0.0°C
and change it to water? Was energy absorbed or released? The specific heat
of ice is 2.09J/g°C.

6.   Calculate the energy transfered in joules when 29.5g of liquid water decreases
from 14°C to 0.0°C and then freezes at 0.0°C. Was energy absorbed or
released?

7.   Calculate the energy transfered in joules when 12g of liquid water raises from
22°C to 100.0°C and then boil? Was energy absorbed or released?

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8.   How much energy in joules does it take to raise 50.0g of ice at 0.0°C to 100.0°C
and then boil?

9.   How much energy in joules does it take to raise 50.0g of liquid ethanol at
25.0°C to 78.0°C and then evaporate? The specific heat of liquid ethanol is
2.44 J/g°C.

10.  How much energy in joules does 28.5g of liquid sulfur lose when it lowers
from 120°C to 115°C, then change into a solid? The specific heat of liquid
sulfur is 0.71 J/g°C.

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Topic 6
Heat Transfer

Introduction
This section discusses the mechanism behind the three methods of heat
transfer, explains the difference between natural and forced convections and
demonstrates application of the principles in solving different scientific problems.

Intended Learning Outcomes

At the end of this section, the students are expected to:
1.   describe the three methods of heat transfer
2.   explain the home insulation system
3.   calculate the R-value of several layers of insulating material and its
effect on thermal energy transfer
4.   explain the difference between natural and forced convections
5.   apply Stefan’s Law to describe how the energy transfer through
radiation
6.   Explain how a Thermos bottle works

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Heat transfer occupies a field which comprises a wide range of functions,

from the simple processes of objects heating and cooling to advanced
thermodynamic concepts in thermal physics. In order to understand how a drink
cools in the summer or how heat travels from the sun to the Earth, you must grasp
these basic principles of heat transfer on a fundamental level.

A.   Heat Transfer by Conduction

When particles of matter are in direct contact, heat transfers by means of

conduction. The adjacent atoms of higher energy vibrate against one another, which
transfers the higher energy to the lower energy, or higher temperature to lower
temperature. That is, atoms of higher intensity and higher heat will vibrate, thereby
moving the electrons to areas of lower intensity and lower heat. Fluids and gases
are less conductive than solids (metals are the best conductors) due to the fact that
they are less dense, meaning that there is a larger distance between atoms.

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B.   Convection Heat Transfer

Convection describes heat transfer between a surface and a liquid or gas in
motion. As the fluid or gas travels faster, the convective heat transfer increases. Two
types of convection are natural convection and forced convection. In natural
convection, fluid motion results from the hot atoms in the fluid, where the hot atoms
move upwards toward the cooler atoms in the air--the fluid moves under the
influence of gravity. Examples of this include the rising clouds of cigarette smoke,
or heat from the hood of a car that rises upwards. In forced convection, the fluid is
forced to travel over the surface by a fan or pump or some other external source.

Natural vs. Forced

The processes we've talked about so far are called natural convection. Natural
convection is where processes just happen on their own whenever there's a
temperature difference between two places. But there's another kind of convection
called forced convection.
Forced convection occurs when you try to speed up the process of convection, by
pushing the fluid along a bit. For example, you might push the air around with a
fan. This is how fan ovens work.

Examples
There are many, many examples of convection in everyday life. But let's start with
a nice one: relaxing on a lovely, warm beach. When you're lying on the beach, you
get hot pretty fast. So you're always thankful to feel a nice, cool breeze. But have
you ever noticed where those sea breezes come from? More often than not, they
came from the sea, towards the land. But why is that?
Well, that's also because of convection. In the summertime, the air above land
tends to be hotter than the air above the sea. The sea air is just harder to heat up.
As the land air heats up, it rises like we've talked about, but this time it isn't the
cooler air above that fills the gap. Instead, the cooler air out at sea gets sucked into
the space the hot air left behind - sucked towards land. That's your nice, cool
breeze.
We've talked about the sea air, but let's go deeper. Much deeper! Not under the
sea, though they do say it's better down where it's wetter. Deeper than that. Let's
go all the way down into the belly of the Earth itself. Deep below the surface, miles
and miles below: in the outer core!
Convection happens here too. It's hotter the closer you get to the center of the
Earth, and cooler further out... though, to be fair, it's insanely hot everywhere!
Nevertheless, this temperature difference is enough for convection currents of
liquid metals to flow even here. And thank goodness they do!

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These liquid metals contain charged particles, and the movement of those charged
particles gives the Earth its magnetic field. Without it, the Earth wouldn't be able
to push dangerous radiation from the Sun out of the way. Without it, we humans
wouldn't survive long at all. Not to mention Captain Cook would have had real
trouble exploring the Pacific -- it's hard to navigate if your compass no longer
works!

C.   Heat Transfer and Radiation

Radiation (not to be confused with thermal radiation) refers to the transfer of
heat through empty space. This form of heat transfer occurs without an intervening
medium; radiation works even in and through a perfect vacuum. For instance,
energy from the sun travels through the vacuum of space before the transfer of heat
warms the Earth.
Heat transfer forms an integral part of education in relevant subjects, such as
in the curriculum of chemical or mechanical engineering. Manufacturing and
HVAC (heating, ventilating and air cooling) are examples of industries that rely
heavily on thermodynamics and principles of heat transfer. Thermal science and
thermal physics are higher fields of education that deal with heat transfer.

In a fireplace, heat transfer occurs by all three methods: conduction, convection, and
radiation. Radiation is responsible for most of the heat transferred into the room. Heat
transfer also occurs through conduction into the room, but at a much slower rate. Heat
transfer by convection also occurs through cold air entering the room around windows and
hot air leaving the room by rising up the chimney.

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D.   Thermal Insulation

The thermal properties of insulating materials are known or can be accurately

measured. The amount of heat transmission (flow) through any combination of
materials can be calculated. However, it is necessary to know and understand
certain technical terms to be able to calculate heat losses and understand the factors
that are involved.

How Does Insulation Work?

Heat flows naturally from warmer areas to cooler ones. During the winter,
heat moves directly from warm spaces (such as your home!) to outdoors and
unheated spaces. During the summer months, heat moves from the warm outdoors
to the cooler interior of your home.
Insulation works by slowing the movement of heat from a hot space to a
cooler space. Insulation helps increase the energy efficiency of your home by
reducing the amount of heat that escapes from it in the winter (containing the heat
and keeping the house warm) and keeping it from getting too warm in the summer
months (retaining the cold air and keeping the interior comfortable).
When installed properly, insulation can increase the comfort levels of your home by
maintaining a consistent, uniform temperature from room to room. Insulation will
also increase your home’s energy efficiency, significantly lowering heating and
cooling bills.

What Are the Different Types of Insulation?

There are several types of thermal insulation to choose from, including:
•   Fiberglass insulation: Fiberglass insulation is one of the most widely used types
of insulation, and it can be installed as a blanket system of rolls and batts.
•   Cellulose insulation: One of the most environmentally friendly types of
insulation available, cellulose is made of up to 80 percent recycled material. It is
also one of the best types of insulation for soundproofing.
•   Spray foam insulation: Spray foam is ideal for all the small cracks, gaps and
crevices behind your walls and can help eliminate air leaks which can cause your
energy bills to skyrocket!
•   Radiant barrier insulation: Here at MIG, we don’t offer radiant barrier
insulation. However, this type of insulation is ideal for warm climates. It is
installed in the attic, right under the roof, to help your home reflect, rather than
absorb, heat from the sun.

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•   Rigid foam insulation: Rigid foam, or rigid board, insulation is available as a

foam panel that can be cut. It’s mainly used for new construction insulation
projects.
•   Rockwool insulation: Made of rocks and minerals spun into small, high
temperature-resistant fibers, rockwool (or mineral wool) insulation is used for a
variety of applications.
•   Icynene insulation: A spray foam insulation often installed between floor joists,
and around wiring, piping and ductwork. It’s great for maximizing energy
efficiency!
Many types of insulation—fiberglass, cellulose and foam board—absorb heat. They
stop heat flow known as conduction. Radiant barrier, on the other hand, reflects heat
from the sun and is installed in attics to keep homes cool and comfortable (and much
more energy-efficient). As its name suggests, radiant barrier insulation stops radiant
heat transfer.

E.   Thermal conductivity

In simple terms this is a measure of the capacity of a material to conduct heat

through its mass. Different insulating materials and other types of material have
specific thermal conductivity values that can be used to measure their insulating
effectiveness. It can be defined as the amount of heat/energy (expressed in kcal, Btu
or J) that can be conducted in unit time through unit area of unit thickness of
material, when there is a unit temperature difference. Thermal conductivity can be
expressed in kcal m-1 °C-1, Btu ft-1 °F-1 and in the SI system in watt (W) m-1 °C-1.
Thermal conductivity is also known as the k-value.

Coefficient of thermal conductance “ l” (kcal m-2 h-1 °C-1)

This is designated as l (the Greek letter lambda) and defined as the amount of heat
(in kcal) conducted in one hour through 1 m2 of material, with a thickness of 1 m,
when the temperature drop through the material under conditions of steady heat
flow is 1 °C. The thermal conductance is established by tests and is the basic rating
for any material. l can also be expressed in Btu ft-2 h-1 °F-1 (British thermal unit per
square foot, hour, and degree Fahrenheit) or in SI units in W m-2 Kelvin (K)-1.

Thermal resistivity

The thermal resistivity is the reciprocal of the k-value (1/k).

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F.   Thermal resistance (R-value)

The thermal resistance (R-value) is the reciprocal of l (1/l) and is used for calculating
the thermal resistance of any material or composite material. The R-value can be
defined in simple terms as the resistance that any specific material offers to the heat
flow. A good insulation material will have a high R-value. For thicknesses other than
1 m, the R-value increases in direct proportion to the increase in thickness of the
insulation material. This is x/l, where x stands for the thickness of the material in
metres.

The thermal resistance (or R value) of a slab is defined by the heat-flow equation in
the form

∆𝑄 𝐴∆𝑇
=  
∆𝑡 𝑅

where
𝐿
𝑅 =  
𝑘<

Its SI unit is m2žK/W. Its customary unit is ft2žhžoF/Btu, where 1 ft2žhžoF/Btu =

0.176 m2žK/W. (It is unlikely that you will have occasion to confuse this symbol R
with the symbol for the constant.)
For several slabs of the same surface area in series, the combined R value is

R = R1 + R2 + . . . + RN
where R1, . . . , are the R values of the individual slabs.

Example Problem:

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Name: __________________________________ Rating: _____________

Section: _________________________________ Date: ______________

Problem Set No. 6

Heat Transfer

I.   Identify the method of heat transfer that takes place in each illustration. Some
illustration may show more than one form of heat transfer.

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II.   Problem Solving:

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Topic 7
Global Warming and Greenhouse Gases

Introduction
This section discusses the scientific explanation and thermodynamics behind
the current dilemma of global warming and greenhouse gases.

Intended Learning Outcomes

At the end of this section, the students are expected to:
1.   Determine how the principles of energy transfer explain global
warming and greenhouse gases operation
--------------------------------------------------------------------------------------------------------------

Key Points

•   The atmosphere can both absorb and reflect radiation, either increasing or
decreasing the Earth’s average temperature.
•   All bodies naturally emit radiation; warmer bodies emit more photons, with
higher average energies.
•   In absorbing sunlight and emitting infrared radiation, the Earth produces
entropy.

Key Terms

•   selective absorber: An object that will absorb radiation over a particular set
of wavelengths but will not (is transparent) at other wavelengths.
•   greenhouse effect: The process by which a planet is warmed by its
atmosphere.
•   greenhouse gas: Any gas, such as carbon dioxide or CFCs, that contributes to
the greenhouse effect when released into the atmosphere.
•   radiative transfer: The transfer of radiation (energy) leaving one object and
being absorbed by another.
•   blackbody: An object that is a perfect absorber and emitter of radiation.

Radiation is a natural process of heat transfer; everything is constantly

radiating heat. When a system is at equilibrium, we do not notice this exchange of
energy because every object absorbs and emits precisely the amount of energy it
receives, but this equilibrium is dynamic–the exchange is always taking place. In
general, as the temperature of an object increases, it emits energy more rapidly by

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emitting photons at a faster rate, and by emitting photons of a greater average

energy.

If we approximate the Earth as a perfect absorber and emitter of the radiation

received from the sun (called a blackbody), we would expect the Earth to be at an
average temperature of 5°C, rather than the 14°C which we observe. The extra
temperature comes from the Earth and it’s atmosphere selectively absorbing certain
wavelengths of radiation while reflecting other wavelengths. The 9°C discrepancy
is due to the greenhouse effect. The gases of the atmosphere are “selective
absorbers”; energy in the visible part of the electromagnetic spectrum passes
through the atmosphere directly to the Earth’s surface (with some reflection
occurring as well). The Earth absorbs this energy and then re-emits radiation in the
infrared portion of the spectrum. The gases in the atmosphere, primarily CO2 and
water vapor are highly absorbent in the infrared part of the spectrum. The
atmosphere absorbs the infrared radiation from the Earth, preventing it from
escaping to space. Because all objects are continually emitting radiation, the
atmosphere (having absorbed the Earth’s radiation) then emits radiation, some of
which is then reabsorbed by the Earth’s surface. Thus the greenhouse effect is a
continuous cycle of absorption and emission of energy between the Earth and
atmosphere. This causes the Earth’s atmosphere and surface to be warmer than
otherwise expected.

Radiative Transfer

The greenhouse effect is a phenomenon of radiative transfer, the process by which

the energy of light waves is exchanged in matter. Radiative transfer dictates what
energy is reflected, absorbed, and emitted.

The greenhouse effect: A summary of heat transfer in the Earth’s atmosphere.

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Atmospheric Absorbers

The radiative transfer properties of atmospheric chemicals depend on the energy of

the radiation (both for absorption and emission), and those properties are unique to
each chemical. In the context of global warming, we find that it is important to
consider both how chemicals and particles reflect sunlight and how they absorb
energy radiated from the Earth. Atmospheric reflecters, notably sulfates and
nitrates, reflect and scatter light before it ever hits the surface of the Earth, effectively
reducing the power that the Earth receives. On the other hand, greenhouse gases
such as carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) are
characteristically strong absorbers of the energy radiated by the Earth’s surface.
They absorb so strongly because they typically exhibit resonant absorption behavior
in the same energy range as the radiation emitted by the earth. These trap heat
before it leaves the Earth, insulating the Earth and increasing the Earth’s equilibrium
temperature.

Entropy and Solar Radiation

The Second Law of Thermodynamics implies that in order to produce energy

sources, entropy must be produced. On a planetary scale, this production of entropy
is primarily accounted for by the absorption and re-emisson of radiation. In general,
the earth radiates the same energy that it receives. (If greenhouse gases increase,
then temperature increases, and higher temperatures cause the Earth to radiate
more, compensating for the greater energy absorbed in the atmosphere. ) With light
radiation, we find the entropy carried by the photons decreases as temperature
increases, S∝1TS∝1T. Since the Earth is cooler than the Sun, as the Earth absorbs
radiation from the Sun and re-emits radiation from the Earth’s surface, there is a net
production of entropy. This net production of entropy allows energy to be stored
and reused, particularly in the form of chemical energy stored by cells through
photosynthesis.

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Name: __________________________________ Rating: _____________

Section: _________________________________ Date: ______________

Learning Activity No. 7

Global Warming and Greenhouse Gases

Directions:
Create a physical or virtual model that simulates global warming. Show and
explain your work through a video recording that will be uploaded in Google
classroom. The following rubric will be used in grading your output.

Global Warming Model

Below Approaching Meets Exceeds

Total
Criteria Expectation Expectation Expectation Expectation
pts
1 pts 2 pts 3 pts 4 pts

Explanation Below Approaching Meets Exceeds

of Concepts Expectation Expectation Expectation Expectation

Explanation is Explanation Explanation Explanation is

unclear; it lacks shows shows a clear and
accuracy and evidence of complete shows
understanding understanding understanding complete
of concepts. , but facts and of concepts. understanding
(9-0 points) concepts are There are some . Concepts and
not accurate. facts and facts are
(11 points) concepts that accurate.
are not (15 points)
accurate.
(13 points)

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Research Below Approaching Meets Exceeds

Expectation Expectation Expectation Expectation

Model shows no Model shows Model is Model is

research in evidence of accompanied accompanied
planning. research in by a by a
(4-0 points) planning but bibliography bibliography
does not cite a but cites only citing at least
bibliography. one research two research
(6 points) reference used references
in planning the used in
model. planning the
(8 points) model.
(10 points)

Model Below Approaching Meets Exceeds

related to Expectation Expectation Expectation Expectation
Science
Concepts Model does not Scientific Model Model clearly
relate to a concepts and represents represents
scientific connections to scientific scientific
concept nor real world concepts with concepts and is
make applications minor errors scientifically
connections to are unclear in and shares correct, having
real world the model. connections for connections to
applications. (11 points) real world real world
(9-0 points) applications. applications.
(13 points) (15 points)

Construction Below Approaching Meets Exceeds

, creativity, Expectation Expectation Expectation Expectation
neatness
The model is The model is The model is The model is
poorly constructed carefully carefully
constructed. It with little constructed, constructed
lacks in neatness neatness and but does not with materials
in creativity. creativity. showcase that showcase
(2-0 points) (3 points) student's student's
creativity. creativity and
(4 points) are
appropriate.
(5 points)

Presentation Below Approaching Meets Exceeds

Expectation Expectation Expectation Expectation

Does not speak Eye contact, Speaks clearly, Anticipates

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clearly, make clear speech, makes eye questions and

eye contact, or is or preparation contact, and takes
unprepared to to present presents model ownership of
present model. model is well. the model.
(2-0 points) minimal. (4 points) (5 points)
(3 points)

Total/50

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Topic 8
The First Law of Thermodynamics

Introduction
This section discusses the First Law of Thermodynamics and its various
applications in solving various problems that involve the interrelationship between
heat, work and internal energy.

Intended Learning Outcomes

At the end of this section, the students are expected to:
1.   Use the first law of thermodynamics in explaining the relationships among
internal energy, work and heat.
2.   Calculate the change in internal energy of the gas.
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A hot gas, when confined in a chamber, exerts pressure on a piston, causing it to move downward. The movement can be
harnessed to do work equal to the total force applied to the top of the piston times the distance that the piston moves.

The First Law of Thermodynamics states that heat is a form of energy, and
thermodynamic processes are therefore subject to the principle of conservation of
energy. This means that heat energy cannot be created or destroyed. It can, however,
be transferred from one location to another and converted to and from other forms
of energy.

The First Law says that the internal energy of a system has to be equal to the
work that is being done on the system, plus or minus the heat that flows in or out of
the system and any other work that is done on the system.
 

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The change in internal energy of a system is the sum of all the energy inputs
and outputs to and from the system similarly to how all the deposits and
withdrawals you make determine the changes in your bank balance.

Mathematically, this is represented as

∆𝑈 = 𝑞 + 𝑤

with ∆𝑈= total change in internal energy of the system

q = heat exchange between a system and its
surroundings
w = work done on or by the system

Work is also equal to the negative external pressure on the system

multiplied by the change in volume:

𝑤 =   −𝑃∆𝑉

with 𝑃  = external pressure on the system

∆𝑉 = change in volume

The internal energy of a system would decrease if the system gives off heat
or does work. Therefore, internal energy of a system increases when the heat
increases (this would be done by adding heat into a system). The internal energy
would also increase if work were done onto a system. Any work or heat that goes
into or out of a system changes the internal energy. However, since energy is never
created nor destroyed (thus, the first law of thermodynamics), the change in internal
energy always equals zero. If energy is lost by the system, then it is absorbed by the
surroundings. If energy is absorbed into a system, then that energy was released by
the surroundings:

∆𝑈BCBDEF =   −∆𝑈BGHH,GIJKILB

where ΔUsystem is the total internal energy in a system, and ΔUsurroundings is the
total energy of the surroundings.

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Name: __________________________________ Rating: _____________

Section: _________________________________ Date: ______________

Problem Set No. 8

First Law of Thermodynamics

Directions: Solve the following problems correctly.

1.   Calculate ∆U for each of the following cases:

a.   Q = + 51 kJ, W = - 15 kJ
b.   Q = + 100. kJ, W = - 65 kJ
c.   Q = - 65 kJ, W = - 20 kJ
d.   In which of these cases does the system do work on the surroundings?

2.   A system releases 125 kJ of heat while 104 kJ of work is done on the system.
Calculate
the change in internal energy (in kJ).

3.   A system undergoes a process consisting of the following two steps:

Step 1: The system absorbs 73 J of heat while 35 J of work is done on it.
Step 2: The system absorbs 35 J of heat while performing 72 J of work.
Calculate the change in internal energy for the overall process (in J).

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4.   In the figure below, two cylinders are filled with the same ideal gas. A
piston is fit so that no gas escapes; friction is negligible between the piston
and the cylinder walls. The block is removed from each piston, the piston
moves upward.

In each case, does the gas do work or is work done on the gas? Explain your
reasoning in a few sentences.

5.   In a certain process, 678 J of heat is absorbed by a system while 294 J of

work is done on the system. What is the change in internal energy for the
process?

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6.   If 1500 cal of heat is added to a system while the system does work
equivalent to 2500 cal by expanding against the surrounding atmosphere,
what is the value of the internal energy in kilojoules?

7.   A sample of 0.20 mol of a gas at 440C and 1.5 atm pressure is cooled to 270C
and compressed to 3.0 atm. Calculate the change in volume. Suppose the
original sample of gas were heated at constant volume until its pressure
was 3,0 atm and then cooled at constant pressure to 270C. What would have
been the change in volume?

8.   If 1.000 kcal of heat is added to 1.200 L of oxygen in a cylinder at constant

pressure of 1.00 atm, the volume increases to 1.500 L. Calculate the change
in internal energy for the process.

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9.   A balloon is inflated to its full extent by heating the air inside it, using 6.3 x
108 J of heat. The initial volume is 2.5 x 103 L. Assume that the balloon
expands against a constant pressure of 1.0 atm. The change in internal energy
is 5.8 x 108 J. What is the final volume of the balloon? (101.3 J = 1 L atm)

10.  Two liters of an ideal gas is expanded into a vacuum and the new volume is
4 L. If 500 J of heat flow out of the container, what is the change in the internal
energy of the system?

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Topic 9
Heat Engines and the Second Law of Thermodynamics

Introduction
This section discusses the Second Law of Thermodynamics and its various
applications like the operation of heat engines. It tackles the principle behind the
Carnot Cycle and explains how the Carnot Engine works.

Intended Learning Outcomes

At the end of this section, the students are expected to:
1.   Define heat engine.
2.   Apply the efficiency formula to heat engines.
3.   Analyze an engine cycle
4.   Compare and contrast the operation of heat engines and refrigerators and
heat pumps.
5.   State the Second Law of Thermodynamics in different ways.
6.   Explain the difference between reversible and irreversible processes.
7.   Explain how the Carnot Engine works.

--------------------------------------------------------------------------------------------------------------

Key Points

•   The second law of thermodynamics indicates that a Carnot engine operating

between two given temperatures has the greatest possible efficiency of any
heat engine operating between these two temperatures.
•   Irreversible processes involve dissipative factors, which reduces the efficiency
of the engine. Obviously, reversible processes are superior from the efficiency
perspective.
•   Carnot efficiency, the maximum achievable heat engine efficiency, is given
as Effc=1−TcThEffc=1−TcTh.

Key Terms

•   The Second Law of Thermodynamics: A law stating that states that the
entropy of an isolated system never decreases, because isolated systems
spontaneously evolve toward thermodynamic equilibrium—the state of
maximum entropy. Equivalently, perpetual motion machines of the second
kind are impossible.
•   heat engine: Any device which converts heat energy into mechanical work.

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These ice floes melt during the Arctic summer. Some of them refreeze in the winter, but the second law of
thermodynamics predicts that it would be extremely unlikely for the water molecules contained in these particular floes to
reform the distinctive alligator-like shape they formed when the picture was taken in the summer of 2009. (credit: Patrick
Kelley, U.S. Coast Guard, U.S. Geological Survey)

The second law of thermodynamics deals with the direction taken by

spontaneous processes. Many processes occur spontaneously in one direction
only—that is, they are irreversible, under a given set of conditions. Although
irreversibility is seen in day-to-day life—a broken glass does not resume its original
state, for instance—complete irreversibility is a statistical statement that cannot be
seen during the lifetime of the universe. More precisely, an irreversible process is
one that depends on path. If the process can go in only one direction, then the
reverse path differs fundamentally and the process cannot be reversible. For
example, as noted in the previous section, heat involves the transfer of energy from
higher to lower temperature. A cold object in contact with a hot one never gets
colder, transferring heat to the hot object and making it hotter. Furthermore,
mechanical energy, such as kinetic energy, can be completely converted to thermal
energy by friction, but the reverse is impossible. A hot stationary object never
spontaneously cools off and starts moving. Yet another example is the expansion of
a puff of gas introduced into one corner of a vacuum chamber. The gas expands to
fill the chamber, but it never regroups in the corner. The random motion of the gas

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molecules could take them all back to the corner, but this is never observed to
happen.

Examples of one-way processes in nature. (a) Heat transfer occurs spontaneously from hot to cold and not from cold to
hot. (b) The brakes of this car convert its kinetic energy to heat transfer to the environment. The reverse process is
impossible. (c) The burst of gas let into this vacuum chamber quickly expands to uniformly fill every part of the chamber.
The random motions of the gas molecules will never return them to the corner.

Heat Engines

Now let us consider a device that uses heat transfer to do work. As noted in
the previous section, such a device is called a heat engine, and one is shown
schematically in the figure below. Gasoline and diesel engines, jet engines, and
steam turbines are all heat engines that do work by using part of the heat transfer
from some source. Heat transfer from the hot object (or hot reservoir) is denoted as
𝑄h, while heat transfer into the cold object (or cold reservoir) is 𝑄c, and the work
done by the engine is 𝑊. The temperatures of the hot and cold reservoirs are 𝑇h and
𝑇c, respectively.

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(a)Heat transfer occurs spontaneously from a hot object to a cold one,

consistent with the second law of thermodynamics. (b) A heat engine,
represented here by a circle, uses part of the heat transfer to do work. The
hot and cold objects are called the hot and cold reservoirs. 𝑄h is the heat
transfer out of the hot reservoir, 𝑊 is the work output, and 𝑄c is the heat
transfer into the cold reservoir.

Because the hot reservoir is heated externally, which is energy intensive, it is

important that the work is done as efficiently as possible. In fact, we would like 𝑊
to equal 𝑄h, and for there to be no heat transfer to the environment (𝑄c=0).
Unfortunately, this is impossible. The second law of thermodynamics also states,
with regard to using heat transfer to do work (the second expression of the second
law):

Carnot's principle

How can an engine achieve its maximum efficiency? It must operate using
reversible processes: a reversible process is one in which the system and the
surroundings can be returned to state they were in before the process began. If
energy is lost to friction during a process, the process is irreversible; if energy is lost
as heat flows from a hot region to a cooler region, the process is irreversible. The
efficiency of an engine using irreversible processes can not be greater than the
efficiency of an engine using reversible processes that is working between the same
temperatures. This is known as Carnot's principle, named after Sadi Carnot, a
French engineer.

A cyclical process brings a system, such as the gas in a cylinder, back to its
original state at the end of every cycle. Most heat engines, such as reciprocating
piston engines and rotating turbines, use cyclical processes. The second law, just
stated in its second form, clearly states that such engines cannot have perfect
conversion of heat transfer into work done. Before going into the underlying reasons
for the limits on converting heat transfer into work, we need to explore the
relationships among 𝑊, 𝑄h, and 𝑄c, and to define the efficiency of a cyclical heat
engine. As noted, a cyclical process brings the system back to its original condition

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at the end of every cycle. Such a system’s internal energy 𝑈 is the same at the
beginning and end of every cycle—that is, Δ𝑈=0. The first law of thermodynamics
states that

Δ𝑈=𝑄−𝑊

where 𝑄 is the net heat transfer during the cycle (𝑄=𝑄h−𝑄c) and 𝑊 is the net work
done by the system. Since Δ𝑈=0 for a complete cycle, we have

0=𝑄−𝑊
so that

𝑊=𝑄  

Thus the net work done by the system equals the net heat transfer into the system,
or

𝑊=𝑄h−𝑄c(cyclical process)

just as shown schematically in Figure 15.17(b). The problem is that in all processes,
there is some heat transfer 𝑄c to the environment—and usually a very significant
amount at that.

In the conversion of energy to work, we are always faced with the problem of getting
less out than we put in. We define conversion efficiency 𝐸𝑓𝑓 to be the ratio of useful
work output to the energy input (or, in other words, the ratio of what we get to what
we spend). In that spirit, we define the efficiency of a heat engine to be its net work
output 𝑊 divided by heat transfer to the engine 𝑄h; that is,

𝑊
𝐸PP =  
𝑄Q

Since 𝑊=𝑄h−𝑄c in a cyclical process, we can also express this as

RQ-­‐‑RT RW
𝐸PP =   = 1 −    
(cyclical process)
RU RU
 
𝐸𝑓𝑓=  𝑄ℎ-­‐‑𝑄𝑐𝑄ℎ=1−    𝑄𝑐𝑄ℎ (cyclical process)
making it clear that an efficiency of 1, or 100%, is possible only if there is no heat
transfer to the environment (𝑄c=0). Note that all 𝑄s are positive. The direction of
heat transfer is indicated by a plus or minus sign. For example, 𝑄c is out of the
system and so is preceded by a minus sign.

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Example

Daily Work Done By A Coal-Fired Power Station, Its Efficiency And Carbon Dioxide
Emissions

1.   A coal-fired power station is a huge heat engine. It uses heat transfer from
burning coal to do work to turn turbines, which are used to generate
electricity. In a single day, a large coal power station has 2.50×1014 J of heat
transfer from coal and 1.48×1014 J of heat transfer into the environment.

(a)  What is the work done by the power station?

(b)  What is the efficiency of the power station?
(c)   In the combustion process, the following chemical reaction occurs:
C+O2→CO2. This implies that every 12 kg of coal puts 12 kg + 16 kg + 16
kg = 44 kg of carbon dioxide into the atmosphere. Assuming that 1 kg of
coal can provide 2.5×106 J of heat transfer upon combustion, how much
CO2 is emitted per day by this power plant?

Solution for (a)

Work output is given by: W =𝑄h−𝑄c.

Substituting the given values:

𝑊  = 2.50 × 1014J – 1.48 × 1014 J

= 1.02×1014J.

Strategy for (b)

The efficiency can be calculated with

𝐸𝑓𝑓=𝑊/𝑄h
since 𝑄h is given and work 𝑊 was found in the first part of this example.

Solution for (b)

Efficiency is given by: 𝐸𝑓𝑓=𝑊/𝑄h. The work 𝑊 was just found to be 1.02 × 1014J, and
𝑄h is given, so the efficiency is

1.02  𝑥  10$_  𝐽
𝐸PP =   = 0.408, 𝑜𝑟  40.8%
2.50  𝑥  10$_  𝐽

Strategy for (c)

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The daily consumption of coal is calculated using the information that each day
there is 2.50 × 1014 J of heat transfer from coal. In the combustion process, we have
C+O2→CO2. So every 12 kg of coal puts 12 kg + 16 kg + 16 kg = 44 kg of CO2 into
the atmosphere.

Solution for (c)

The daily coal consumption is

2.50  𝑥  10$_  𝐽
h
= 1.0  𝑥  10j  𝑘𝑔
2.50  𝑥  10  𝐽/𝑘𝑔    

Assuming that the coal is pure and that all the coal goes toward producing carbon
dioxide, the carbon dioxide produced per day is

44  𝑘𝑔  𝐶 𝑂o
1.0  𝑥  10j  𝑘𝑔  𝑐𝑜𝑎𝑙  𝑥   = 3.7  𝑥  10j  𝑘𝑔  𝐶 𝑂o
12  𝑘𝑔  𝑐𝑜𝑎𝑙

This is 370,000 metric tons of CO2 produced every day.

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Name: __________________________________ Rating: _____________

Section: _________________________________ Date: ______________

Problem Set No. 9

Heat Engines and the Second Law of Thermodynamics

1.   A certain heat engine does 10.0 kJ of work and 8.50 kJ of heat transfer occurs
to the environment in a cyclical process.
(a)  What was the heat transfer into this engine?
(b)  What was the engine’s efficiency? 18.5 kJ, 54.1%

2.   With 2.56 × 106 J of heat transfer into this engine, a given cyclical heat engine
can do only 1.50 × 105 J of work.
(a)  What is the engine’s efficiency?
(b)  How much heat transfer to the environment takes place? 5.86%, 𝟐. 𝟒𝟏 ×
𝟏𝟎 𝟔 J

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3.   (a) What is the work output of a cyclical heat engine having a 22.0% efficiency
and 6.00 × 109 J of heat transfer into the engine?
(b) How much heat transfer occurs to the environment? 𝟏. 𝟑𝟐 × 𝟏𝟎𝟗 J, 𝟒. 𝟔𝟖
× 𝟏𝟎𝟗 J

4.   (a) What is the efficiency of a cyclical heat engine in which 75.0 kJ of heat
transfer occurs to the environment for every 95.0 kJ of heat transfer into the
engine?
(c)   How much work does it produce for 100 kJ of heat transfer into the
engine? (OpenStax 15.23) 21.1%, 21.1 kJ

5.   The engine of a large ship does 2.00 × 108 J of work with an efficiency of
5.00%.
(a) How much heat transfer occurs to the environment?
(b) How many barrels of fuel are consumed, if each barrel produces 6.00 ×
109 J of heat transfer when burned? 𝟑. 𝟖𝟎 × 𝟏𝟎𝟗 J, 0.667 barrels

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Topic 10
Entropy and the Second Law of Thermodynamics

Introduction
This section discusses the application of the second law of thermodynamics
in the context of the property of entropy.

Intended Learning Outcomes

At the end of this section, the students are expected to:
1.   Define entropy of a system.
2.   Calculate the change in entropy for a system and its environment.

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There is yet another way of expressing the second law of thermodynamics.

This version relates to a concept called entropy. By examining it, we shall see that the
directions associated with the second law—heat transfer from hot to cold, for
example—are related to the tendency in nature for systems to become disordered
and for less energy to be available for use as work. The entropy of a system can in
fact be shown to be a measure of its disorder and of the unavailability of energy to
do work.

Recall that the simple definition of energy is the ability to do work. Entropy
is a measure of how much energy is not available to do work. Although all forms of
energy are interconvertible, and all can be used to do work, it is not always possible,
even in principle, to convert the entire available energy into work. That unavailable
energy is of interest in thermodynamics, because the field of thermodynamics arose
from efforts to convert heat to work.

We can see how entropy is defined by recalling our discussion of the Carnot
engine. We noted that for a Carnot cycle, and hence for any reversible processes,

𝑄T 𝑇T
=  
𝑄Q 𝑇Q

Rearranging terms yields

𝑄T 𝑄Q
=  
𝑇T 𝑇Q

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For any reversible process. Qc and Qh are absolute values of the heat transfer at
temperatures Tc and Th, respectively. This ratio of

𝑄
=  𝑐ℎ𝑎𝑛𝑔𝑒  𝑖𝑛  𝑒𝑛𝑡𝑟𝑜𝑝𝑦  ∆𝑆  𝑓𝑜𝑟  𝑎  𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒  𝑝𝑟𝑜𝑐𝑒𝑠𝑠
𝑇

𝑄
                                                           ∆𝑆 =  
𝑇 HE‚

where Q is the heat transfer, which is positive for heat transfer into and negative for
heat transfer out of, and T is the absolute temperature at which the reversible
process takes place. The SI unit for entropy is joules per kelvin (J/K). If temperature
changes during the process, then it is usually a good approximation (for small
changes in temperature) to take T to be the average temperature, avoiding the need
to use integral calculus to find ΔS.

The definition of ΔS is strictly valid only for reversible processes, such as used in a
Carnot engine. However, we can find ΔS precisely even for real, irreversible
processes. The reason is that the entropy S of a system, like internal energy U,
depends only on the state of the system and not how it reached that condition.
Entropy is a property of state. Thus the change in entropy ΔS of a system between
state 1 and state 2 is the same no matter how the change occurs. We just need to find
or imagine a reversible process that takes us from state 1 to state 2 and calculate ΔS
for that process. That will be the change in entropy for any process going from state
1 to state 2. (See Figure 2.)

Figure 2. When a system goes from state 1 to state 2, its entropy changes by the same amount ΔS,
whether a hypothetical reversible path is followed or a real irreversible path is taken.

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Now let us take a look at the change in entropy of a Carnot engine and its heat
reservoirs for one full cycle. The hot reservoir has a loss of entropy
−𝑄Q
∆𝑆Q =    
𝑇Q

because heat transfer occurs out of it (remember that when heat transfers out,
then Q has a negative sign). The cold reservoir has a gain of entropy
−𝑄T
∆𝑆T =  
𝑇T

because heat transfer occurs into it. (We assume the reservoirs are sufficiently large
that their temperatures are constant.) So the total change in entropy is:

ΔStot = ΔSh + ΔSc

Thus, since we know that

𝑄T 𝑄Q
=  
𝑇T 𝑇Q

for a Carnot engine,

𝑄T 𝑄Q
∆𝑆D,D =   =   =0
𝑇T 𝑇Q

This result, which has general validity, means that the total change in entropy
for a system in any reversible process is zero.

The entropy of various parts of the system may change, but the total change
is zero. Furthermore, the system does not affect the entropy of its surroundings,
since heat transfer between them does not occur. Thus the reversible process
changes neither the total entropy of the system nor the entropy of its surroundings.
Sometimes this is stated as follows: Reversible processes do not affect the total
entropy of the universe. Real processes are not reversible, though, and they do
change total entropy. We can, however, use hypothetical reversible processes to
determine the value of entropy in real, irreversible processes. Example 1 illustrates
this point.

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Strategy

How can we calculate the change in entropy for an irreversible process when ΔStot =
ΔSh + ΔSc is valid only for reversible processes? Remember that the total change in
entropy of the hot and cold reservoirs will be the same whether a reversible or
irreversible process is involved in heat transfer from hot to cold. So we can calculate
the change in entropy of the hot reservoir for a hypothetical reversible process in
which 4000 J of heat transfer occurs from it; then we do the same for a hypothetical
reversible process in which 4000 J of heat transfer occurs to the cold reservoir. This
produces the same changes in the hot and cold reservoirs that would occur if the
heat transfer were allowed to occur irreversibly between them, and so it also
produces the same changes in entropy.

Reference: https://courses.lumenlearning.com/physics/chapter/15-6-entropy-
and-the-second-law-of-thermodynamics-disorder-and-the-unavailability-of-
energy/

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Discussion

There is an increase in entropy for the system of two heat reservoirs undergoing
this irreversible heat transfer. We will see that this means there is a loss of ability
to do work with this transferred energy. Entropy has increased, and energy has
become unavailable to do work.

It is reasonable that entropy increases for heat transfer from hot to cold. Since the
change in entropy is Q/T, there is a larger change at lower temperatures. The
decrease in entropy of the hot object is therefore less than the increase in entropy
of the cold object, producing an overall increase, just as in the previous example.
This result is very general:

There is an increase in entropy for any system undergoing an irreversible process.

With respect to entropy, there are only two possibilities: entropy is constant for a
reversible process, and it increases for an irreversible process. There is a fourth
version of the second law of thermodynamics stated in terms of entropy:

The total entropy of a system either increases or remains constant in any process; it never
decreases.

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For example, heat transfer cannot occur spontaneously from cold to hot, because
entropy would decrease.

Entropy is very different from energy. Entropy is not conserved but increases in all
real processes. Reversible processes (such as in Carnot engines) are the processes
in which the most heat transfer to work takes place and are also the ones that keep
entropy constant. Thus we are led to make a connection between entropy and the
availability of energy to do work.

Entropy and the Unavailability of Energy to Do Work

What does a change in entropy mean, and why should we be interested in it? One
reason is that entropy is directly related to the fact that not all heat transfer can be
converted into work. Example 2 gives some indication of how an increase in
entropy results in less heat transfer into work.

1.   Calculate the work output of a Carnot engine operating between temperatures

of 600 K and 100 K for 4000 J of heat transfer to the engine.
2.   Now suppose that the 4000 J of heat transfer occurs first from the 600 K
reservoir to a 250 K reservoir (without doing any work, and this produces the
increase in entropy calculated above) before transferring into a Carnot engine
operating between 250 K and 100 K. What work output is produced? (See
Figure 4.)

Figure 4. (a) A Carnot engine working at between 600 K and 100 K has 4000 J of heat transfer and performs 3333 J of work.
(b) The 4000 J of heat transfer occurs first irreversibly to a 250 K reservoir and then goes into a Carnot engine. The increase
in entropy caused by the heat transfer to a colder reservoir results in a smaller work output of 2400 J. There is a permanent
loss of 933 J of energy for the purpose of doing work.

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Discussion

There is 933 J less work from the same heat transfer in the second process. This
result is important. The same heat transfer into two perfect engines produces
different work outputs, because the entropy change differs in the two cases. In the
second case, entropy is greater and less work is produced. Entropy is associated
with the unavailability of energy to do work.

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Section: _________________________________ Date: ______________

Problem Set No. 10

Entropy and the Second Law of Thermodynamics

Solve the following problems correctly.

1.   Twenty grams of ice at precisely 0 oC melts to water with no change in

temperature. By how much does the entropy of the 20-g mass change in this
process?

2.   As shown in the figure, an ideal gas is confined to a cylinder by a piston. The

piston is pushed down slowly so that the gas temperature remains at 20oC.
During the compression, 730 J of work is done on the gas. Find the entropy
change of the gas.

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3.   As shown in figure 21-2, a container is separated into two equal-volume

compartments. The two compartments contain equal masses of the same gas,
0.740 g in each, and cv for the gas is 745 j/kg-K. At the start, the hot gas is
67.0oC, while the cold gas is at 200C. No heat can leave or enter the
compartments except slowly through the partition AB. Find the entropy
change of each compartment as the hot gas cools from 67.0 OC to 65 oC.

4.   The ideal gas in the cylinder in Figure 21-1 is initially at conditions P1, V1, T1.
It is slowly expanded at constant temperature by allowing the piston to rise.
Its final conditions are P2, V2, T1, where V2 = 3V1. Find the change in entropy
of the gas during this expansion. The mass of gas is 1.5 g and M = 28 kg/kmol
for it.

5.   Two vats of water, one at 87 oC and the other at 14oC, are separated by a metal
plate. If heat flows through the plate at 35 cal/s, what is the change in entropy
of the gas during this expansion. The mass of gas is 1.5 g and M = 28 kg/kmol
for it.

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Topic 11
Third Law of Thermodynamics

Introduction
This section discusses the principles of the Third Law of Thermodynamics
and its relation to absolute zero.

Intended Learning Outcomes

At the end of this section, the students are expected to:
1.   State the third law of thermodynamics and relate it to absolute zero
temperature.
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Key Points

•   Entropy is related to the number of possible microstates, and with only one
microstate available at zero kelvin, the entropy is exactly zero.
•   The third law of thermodynamics provides an absolute reference point for
the determination of entropy. The entropy determined relative to this point is
the absolute entropy.
•   Absolute entropy can be written as S=kBlogWS=kBlogW, where W is the
number of available microstates.

Key Terms

•   microstate: The specific detailed microscopic configuration of a system.

•   absolute zero: The coldest possible temperature: zero on the Kelvin scale and
approximately -273.15°C and -459.67°F. The total absence of heat; the
temperature at which motion of all molecules would cease.
•   degeneracy: Two or more different quantum states are said to be degenerate
if they are all at the same energy level.

The third law of thermodynamics is sometimes stated as follows: The entropy of a

perfect crystal at absolute zero is exactly equal to zero.

At zero kelvin the system must be in a state with the minimum possible energy, thus
this statement of the third law holds true if the perfect crystal has only one minimum
energy state. Entropy is related to the number of possible microstates, and with only
one microstate available at zero kelvin the entropy is exactly zero.

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The third law was developed by the chemist Walther Nernst during the years 1906-
1912. It is often referred to as Nernst’s theorem or Nernst’s postulate. Nernst
proposed that the entropy of a system at absolute zero would be a well-defined
constant. Instead of being 0, entropy at absolute zero could be a nonzero constant,
due to the fact that a system may have degeneracy (having several ground states at
the same energy).

In simple terms, the third law states that the entropy of a perfect crystal approaches
zero as the absolute temperature approaches zero. This law provides an absolute
reference point for the determination of entropy. (diagrams the temperature entropy
of nitrogen. ) The entropy (S) determined relative to this point is the absolute
entropy represented as follows:

S=kBlogW

where kB is the Bolzmann constant and W is the number of microstates. Provided

that the ground state is unique (or W=1), the entropy of a perfect crystal lattice as
defined by Nernst’s theorem is zero provided that its ground state is unique,
because log(1) = 0.

The Kelvin temperature scale

The person most associated with the concept of absolute zero is William Thomson,
1st Baron Kelvin. The temperature unit bearing his name, the kelvin (K), is the one
most commonly used by scientists worldwide. Temperature increments in the
Kelvin scale are the same size as in the Celsius scale, but because it starts at absolute
zero, rather than the freezing point of water, it can be used directly in mathematical
calculations, particularly in multiplication and division. For example, 100 K actually
is twice as hot as 50 K. A sample of confined gas at 100 K also contains twice as much
thermal energy, and it has twice the pressure as it would have at 50 K. Such
calculations cannot be done using the Celsius or Fahrenheit scales, i.e., 100 C
is not twice as hot as 50 C, nor is 100 F twice as hot as 50 F.

Implications of the Third Law

Because a temperature of absolute zero is physically unattainable, the Third Law
may be restated to apply to the real world as: the entropy of a perfect crystal
approaches zero as its temperature approaches absolute zero. We can extrapolate
from experimental data that the entropy of a perfect crystal reaches zero at absolute
zero, but we can never demonstrate this empirically.

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Name: __________________________________ Rating: _____________

Section: _________________________________ Date: ______________

Problem Set No. 11

Third Law of Thermodynamics

1.   What exactly is thermodynamics?

a.   The study of the movement of heat
b.   The study of thermal energy.
c.   The study of engines.
d.   The study of entropy changes.

2.   What is the temperature of absolute zero in Celsius and kelvin?

a.   0 K, 273C
b.   0K, 0C
c.   0 K, -273C
d.   -273 K, 0 C

3.   What is the entropy of an ideal crystal at absolute zero, according to the 3rd
law of thermodynamics?

a.   There is no way to know.

b.   Infinity.
c.   1
d.   0

4.   Which of the following correctly classifies entropy?

a.   It is an intensive property, in that it depends on the identity of the
substance
b.   It is an extensive property, in that it depends on the number of moles
c.   It is neither extensive nor intensive
d.   It is an extensive property, in that it depends on the identity of the
substance

5.   Which of the following represents the value for the entropy of the perfect
crystal at 0K?
a.   Positive
b.   Negative
c.   0
d.   1

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