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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
Fundamental Concepts
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.
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.
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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
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:
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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 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.
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 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 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
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
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.
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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
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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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.
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”.
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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.
There are different kinds of thermometer that can be used depending on their
thermometric property. They are as follows.
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I. Answer the following questions scientifically. Write your answer in red font.
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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1) 10o C ________
2) 30o C ________
3) 40o C ________
4) 37o C ________
5) 0o C ________
6) 32o F ________
7) 45o F ________
8) 70o F ________
9) 80o F ________
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12) 0o C ________
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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.
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SOLIDS
For many solids, expansion is directly proportional to temperature change.
∆ℓ = αℓ0∆T
∆A = 2αA0∆T
∆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
LIQUIDS
Liquids can only expand in volume.
∆V = βV0∆T
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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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?
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?
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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
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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.)
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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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
𝑛𝑇
𝑉
∝
𝑃
That is:
𝑛𝑇
𝑉=𝑅
𝑃
𝑃𝑉 = 𝑛𝑅𝑇
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Sample Problems:
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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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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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.
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. 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?
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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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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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.
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.
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Specific Heat - is the amount of energy necessary to raise the temperature of one
gram of substance by one degree Celsius.
𝐪
𝐂𝐩 =
𝐦𝚫𝐓
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Sample Problems:
Calorimetry
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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?
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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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.
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.
• Melting—Solid to liquid
• Vaporization—Liquid to gas (included boiling and evaporation)
• Sublimation—Solid to gas
• 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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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
Key Terms
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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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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?
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.
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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!
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
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E. Thermal conductivity
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
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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<
R = R1 + R2 + . . . + RN
where R1, . . . , are the R values of the individual slabs.
Example Problem:
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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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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.
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.
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Radiative Transfer
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Atmospheric Absorbers
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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.
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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.
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.
∆𝑈 = 𝑞 + 𝑤
𝑤 = −𝑃∆𝑉
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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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).
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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.
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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?
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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.
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Key Points
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)
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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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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
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.
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
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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.
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
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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.
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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
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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:
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:
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.
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.
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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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.
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
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
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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?
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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