Roberto Holub Thermodynamics 6°TEC

UNIT 0 - HEAT AND CALORIMETRY - review

When two objects with different temperatures are placed in thermal contact, the temperature of the warmer object
decreases while the temperature of the cooler object increases. With time, they reach a common equilibrium
temperature somewhere in between their initial temperatures.
During this process, we say that energy is transferred from the warmer object to the cooler one. Until about 1850,
the subjects of thermodynamics and mechanics were considered two distinct branches of science, and the principle
of conservation of energy seemed to describe only certain kinds of mechanical systems. Experiments performed by
the English physicist James Joule (1818–1889) and others showed that the decrease in mechanical energy (kinetic
plus potential) of an isolated system was equal to the increase in the internal energy of the system. Today, the
internal energy is treated as a form of energy that can be transformed into mechanical energy and vice versa. Once
the concept of energy was broadened to include internal energy, the law of conservation of energy emerged as a
universal law of nature.

HEAT AND INTERNAL ENERGY

A major distinction must be made between internal energy and heat. These terms are not interchangeable—heat
involves a transfer of internal energy from one location to another. The following formal definitions will make the
distinction precise.

Internal energy U is the energy associated with the microscopic components of a system—the atoms and molecules
of the system. The internal energy includes kinetic and potential energy associated with the random translational,
rotational, and vibrational motion of the particles that make up the system, and any potential energy bonding the
particles together.

Heat is the transfer of energy between a system and its environment due to a temperature difference between
them.

The symbol is used to represent the amount of energy transferred by heat between a system and its environment.

Units of Heat

Early in the development of thermodynamics, before scientists realized the connection between thermodynamics
and mechanics, heat was defined in terms of the temperature changes it produced in an object, and a separate unit
of energy, the calorie, was used for heat. The calorie (cal) is defined as the energy necessary to raise the
temperature of 1 g of water from 14.5° to 15.5°C. (The “Calorie,” with a capital “C,” used in describing the energy
content of foods, is actually a kilocalorie.)

In 1948, scientists agreed that because heat (like work) is a measure of the transfer of energy, its SI unit should be
the joule. The calorie is now defined to be exactly:

1 = 4,186

This definition is known as the mechanical equivalent of heat.

Roberto Holub Thermodynamics 6°TEC

SPECIFIC HEAT
On a hot day, the water in a swimming pool may be cool, even if the air around it
is hot. This may seem odd because both the air and water receive energy from
sunlight. One reason that the water may be cooler than the air is evaporation,
which is a cooling process.
However, evaporation is not the only reason for the difference. Experiments have
shown that the change in temperature due to adding or removing a given amount
of energy depends on the particular substance. In other words, the same change
in energy will cause a different temperature change in equal masses of different
substances. This fact is due to differences in the motion of atoms and molecules
at the microscopic level.

The historical definition of the calorie is the amount of energy necessary to raise the temperature of one gram of a
specific substance—water—by one degree. That amount is 4,186 . Raising the temperature of one kilogram of
water by 1℃ requires 4,186 of energy. The amount of energy
required to raise the temperature of one kilogram of an arbitrary
substance by 1℃ varies with the substance.
Every substance requires a unique amount of energy per unit mass to
change the temperature of that substance by 1℃.

If a quantity of energy is transferred to a substance of mass ,

changing its temperature by ∆ = − , the specific heat c of the
substance is defined by:
=
∆

The table to the right lists specific heats for several substances. From the definition of the calorie, the specific heat
of water is 4,186 / ° . From the definition of specific heat, we can express the energy needed to raise the
temperature of a system of mass by ∆ as:
= ∆

The equation applies to both substances that absorb energy from their surroundings and those that transfer energy
to their surroundings. Note that when the temperature increases, ∆ and are positive, corresponding to energy
flowing into the system. When the temperature decreases, ∆ and are negative, and energy flows out of the
system.
The table shows that water has the highest specific heat relative to most other common substances. This high
specific heat is responsible for the moderate temperatures found in regions near large bodies of water. As the
temperature of a body of water decreases during winter, the water transfers energy to the air, which carries the
energy landward when prevailing winds are toward the land.
The fact that the specific heat of water is higher than the specific heat of sand
is responsible for the pattern of airflow at a beach. During the day, the Sun
adds roughly equal amounts of energy to the beach and the water, but the
lower specific heat of sand causes the beach to reach a higher temperature
than the water. As a result, the air above the land reaches a higher
temperature than the air above the water. The denser cold air pushes the less
dense hot air upward, resulting in a breeze from the ocean to land during the
day. Because the hot air gradually cools as it rises, it subsequently sinks, setting
up the circulation pattern shown in the figure.
Roberto Holub Thermodynamics 6°TEC

LATENT HEAT AND PHASE CHANGE

A substance usually undergoes a change in temperature when energy is transferred between the substance and its
environment. In some cases, however, the transfer of energy doesn’t result in a change in temperature. This can
occur when the physical characteristics of the substance change from one form to another, commonly referred to
as a phase change. Some common phase changes are solid to liquid (melting), liquid to gas (boiling), and a change
in the crystalline structure of a solid. Any such phase change involves a change in the internal energy, but no change
in the temperature.
The energy needed to change the phase of a given pure substance is:
=±
where , called the latent heat of the substance, depends on the nature of the phase change as well as on the
substance.
The word latent means “lying hidden within a person or thing.” The positive sign in the previous equation is chosen
when energy is absorbed by a substance, as when ice is melting. The negative sign is chosen when energy is removed
from a substance, as when steam condenses to water. The latent heat of fusion is used when a phase change
occurs during melting or freezing, while the latent heat of vaporization is used when a phase change occurs
during boiling or condensing.
Another process, sublimation, is the passage from the solid to the gaseous phase without going through a liquid
phase. The fuming of dry ice (frozen carbon dioxide) illustrates this process, which has its own latent heat associated
with it—the heat of sublimation.
Phase changes can be described in terms of rearrangements of
molecules when energy is added to or removed from a
substance. Consider first the liquid-to-gas phase change. The
molecules in a liquid are close together, and the forces between
them are stronger than the forces between the more widely
separated molecules of a gas. Work must, therefore, be done on
the liquid against these attractive molecular forces in order to
separate the molecules. The latent heat of vaporization is the
amount of energy that must be added to the one kilogram of
liquid to accomplish this separation.
Similarly, at the melting point of a solid, the amplitude of
vibration of the atoms about their equilibrium positions becomes
great enough to allow the atoms to pass the barriers of adjacent
atoms and move to their new positions. On average, these new
positions are less symmetrical than the old ones and therefore have higher energy. The latent heat of fusion is equal
to the work required at the molecular level to transform the mass from the ordered solid phase to the disordered
liquid phase.
Roberto Holub Thermodynamics 6°TEC

The average distance between atoms is much greater in the gas phase than in either the liquid or the solid phase.
Each atom or molecule is removed from its neighbors, overcoming the attractive forces of nearby neighbors.
Therefore, more work is required at the molecular level to vaporize a given mass of a substance than to melt it, so
in general, the latent heat of vaporization is much greater than the latent heat of fusion.

Suppose you place an ice cube with a temperature of −25°C in a glass, and then you place the glass in a room. The
ice cube slowly warms, and the temperature of the ice will increase until the ice begins to melt at 0°C. The graph
below and data in the table show how the temperature of 10.0 g of ice changes as energy is added.
You can see that temperature steadily increases from −25°C to 0°C (segment A of the graph). You could use the
mass and the specific heat capacity of ice to calculate how much energy is added to the ice during this segment. At
0°C, the temperature stops increasing. Instead, the ice begins to melt and to change into water (segment B). The
ice-and-water mixture remains at this temperature until all of the ice melts. Suppose that you now heat the water
in a pan on a stovetop. From 0°C to 100°C, the water’s temperature steadily increases (segment C). At 100°C,
however, the temperature stops rising, and the water turns into steam (segment D). Once the water has completely
vaporized, the temperature of the steam increases (segment E).
Roberto Holub Thermodynamics 6°TEC

Saving Energy

Suppose you are cooking spaghetti, and the instructions say “boil the pasta in water for ten minutes.” To cook
spaghetti in an open pot using the least amount of energy, should you (a) turn up the burner to its fullest so the
water vigorously boils or (b) turn down the burner so the water barely boils?

Reasoning The spaghetti needs to cook at the temperature of boiling water for ten minutes. In an open pot, the
pressure is atmospheric pressure, and water boils at 100 ℃, regardless of whether it is vigorously boiling or just
barely boiling. To convert water into steam requires energy in the form of heat from the burner, and the greater
the amount of water converted, the greater the amount of energy needed.
Answer (a) is incorrect. Causing the water to boil vigorously just wastes energy unnecessarily. All it accomplishes is
to convert more water into steam.
Answer (b) is correct. Keeping the water just barely boiling uses the least amount of energy to keep the spaghetti
at 100 ℃, because it minimizes the amount of water converted into steam.

The physics of steam burns

In comparison to the latent heat of fusion, the latent heat of vaporization for water has a much larger value. When
water boils at 100 ℃, 540 of heat must be supplied for each gram of liquid turned into steam. And when steam
condenses at 100 ℃, this amount of heat is released from each gram of steam that changes back into a liquid.
Liquid water at 100 ℃ is hot enough by itself to cause a bad burn, and the additional effect of the large latent heat
can cause severe tissue damage if condensation occurs on the skin.

The physics of high-tech clothing

By taking advantage of the latent heat of fusion, designers can now engineer clothing that can absorb or release
heat to help maintain a comfortable and approximately constant temperature close to your body. As the
photograph below shows, the fabric in this type of clothing is coated with microscopic balls of heat-resistant plastic
that contain a substance known as a “phase-change material” (PCM).
When you are enjoying your favorite winter sport, for example, it is easy to become overheated. The PCM prevents
this by melting, absorbing excess body heat in the process. When you are taking a break and cooling down, however,
the PCM freezes and releases heat to keep you warm. The temperature range over which the PCM can maintain a
comfort zone is related to its melting/freezing temperature, which is determined by its chemical composition.
Roberto Holub Thermodynamics 6°TEC

Gobal Warming
Scientists typically devise solutions to problems and then test the solution to determine if it indeed solves the
problem. But sometimes the problem is only suggested by the evidence, and there are no chances to test the
solutions. A current example of such a problem is climatic warming.
Data recorded from various locations around the world over the past century indicate that the average atmospheric
temperature is 0.6°C higher now than it was 100 years ago. Although this sounds like a small amount, such an
increase can have pronounced effects. Increased temperatures may eventually cause the ice in polar regions to
melt, causing ocean levels to increase, which in turn may flood some coastal areas.
But such disasters depend on whether global temperatures continue to increase. Historical studies indicate that
some short-term fluctuations in climate are natural, like the “little ice age” of the seventeenth century. If the current
warming trend is part of a natural cycle, the dire predictions may be overstated or wrong.
Even if warming is continuous, climatic systems are very complex and involve many unexpected factors. For
example, if polar ice melts, a sudden increase in humidity may result in snow in polar areas. This could counter the
melting, thus causing ocean levels to remain stable.

Greenhouse Gases
Most of the current attention and concern about climatic
warming has been focused on the increase in the amount of
“greenhouse gases,” primarily carbon dioxide and methane, in
the atmosphere. Molecules of these gases absorb energy that is
radiated from the Earth’s surface, causing their temperature to
rise. These molecules then release energy as heat, causing the
atmosphere to be warmer than it would be without these gases.
While carbon dioxide and methane are natural components of
the air, their levels have increased rapidly during the last hundred years. This has been determined by analyzing air
trapped in the ice layers of Greenland. Deeper sections of the ice contain air from earlier times. During the last ice
age, there was about 185 ppm of carbon dioxide, CO2, in the air, but the concentration from 130 years ago was
slightly below 300 ppm. Today, the levels are 370 ppm, an increase that can be accounted for by the increase in
combustion reactions, primarily from coal and petroleum burning, and by the decrease in CO2- consuming trees
through deforestation.
But does the well-documented increase in greenhouse gas concentrations enable detailed predictions?
atmospheric physicists have greatly improved their models in recent years, and they are able to correctly predict
past ice ages and account for the energy-absorbing qualities of oceans. But such models remain oversimplified,
partly because of a lack of detailed long-term data. In addition, the impact of many variables, such as fluctuations
in solar energy output and volcanic processes, are poorly understood and cannot be factored into predictions. To
take all factors into account would require more-complex models and more-sophisticated supercomputers than
are currently available. As a result, many questions whether meaningful decisions and planning can occur.

Risk of Action and Inaction

The evidence for climatic warming is suggestive but not conclusive. What should be done? Basically, there are two
choices: either do something or do nothing.
The risks of doing nothing are that the situation may worsen. But it is also possible that waiting for better evidence
will allow for a greater consensus among the world’s nations about how to solve the problem efficiently. Convincing
the world’s population that action taken now will have the desired benefit decades from now will not be easy.
Acting now also involves risks. Gas and coal could be rationed or taxed to limit consumption. The development of
existing energy-efficient technologies, such as low-power electric lights and more efficient motors and engines,
could cut the use of coal and gasoline in half. However, the economic effects could be as severe as those resulting
from climatic warming.
But none of these options can guarantee results. Even if the trend toward climatic warming stops, it will be hard to
prove whether this was due to human reduction in greenhouse gases, to natural cyclic patterns, or to other causes.
Roberto Holub Thermodynamics 6°TEC

CALORIMETRY – Solved Problems

1) An electric heater consumes 2000 of electric power. We use this heater to raise the temperature of 250
of water inside a 120 ceramic cup initially at 20℃. How much time is needed to raise the temperature of the
water to 80℃?
Data:

%
Mass of water ! = " ∙ $ = 1 &'( 250 = 250 Mass of the cup & = 120

Initial temperature of the water )! = 20℃ (liquid) Initial temperature of the cup )& = 20℃ (solid)

Final temperature of the water )! = 80℃ (liquid) Final temperature of the cup )& = 80℃ (solid)

Solution:
Both the cup and the water will absorb energy in the form of heat from the electric heater.
For the system heater-cup-water the energy balance is then:

* =0= +,-.,/ + &12 + !-.,/

0= +,-.,/ + & ∙ & ∙∆ & + ! ∙ ! ∙∆ !

0= +,-.,/ + & ∙ & ∙ 3)& − )& 4 + ! ∙ ! ∙ 3)! − )! 4

0= +,-.,/ + 120 ∙ 0,19 ∙ 680 − 207 + 250 ∙ 1 ∙ 680 − 207

0= +,-.,/ + 120 ∙ 0,19 ∙ 680 − 207 + 250 ∙ 1 ∙ 680 − 207

0= +,-.,/ + 16368

+,-.,/ = −16368

The minus sign has to do with the fact that this energy is flowing from the heater to the water+cup.
By definition, power is energy (heat or work) transferred per unit time. In this case, the energy is in the form
of heat:
9=
)
In SI units,
6;<= >7
1 6: ))7 = 1
? 6?> <@A7

The amount of heat, in joules, is:

4,186
= 16368 ∙ = 68516,5

From 9 = /) we get:
68516,5
)= =
9 2000 /?

) = 34,3?
Roberto Holub THERMODYNAMICS 6ºTEC

2) For the following mixture, determine the final temperature and composition
200 of ice at −20℃ ; 150 of water at 35℃ ; 5 of vapor at 115℃
Temperature scale and initial conditions:

Possible outcomes: 1,2,3,4,5,6,7,8,9

In this case, we have a lot of ice and it’s logical to assume that the final state of the system will be between zones
1 and 4.
Solution:
Energy needed to heat up the ice from −20℃ to 0℃ → +,-. &, = C ∙ C ∙ D0 − 6−207E
= 200 ∙ 0,52 ∙ 20
= 2080 (2)
Energy needed to melt the ice → ',F. &, = C ∙ = 200 ∙ 80 = 16000
Therefore, we need 62080 + 160007 = 18080 to heat up the ice and turn it to liquid water at 0℃ (4)

Energy released when cooling the vapor from 115℃ to 100℃ → &GGF -2G/ = ∙ ∙ 6100 − 1157
= −5 ∙ 0,48 ∙ 15
= −36
Energy released when condensing the vapor → &GHI -2G/ = ∙ = −30 ∙ 540 = −2700
Energy released when cooling the water (ex-vapor) from 100℃ to 0℃ → = !6 7 ∙
&GGF !6 7 ! ∙ 60 − 1007
= −5 ∙ 1 ∙ 100
= −500
So, the vapor can provide (36 + 2700 + 5007 = 3236 by cooling, then condensing, and cooling again as
liquid water, starting at 115℃ and ending at 0℃ (4)

Energy released when cooling the water from 35℃ to 0℃ → &GGF !-.,/ = ! ∙ ! ∙ 60 − 357
= −150 ∙ 1 ∙ 35
= −5250 (4)

Conclusion: the combined energies of vapor and water add up to 63236 + 52507 = 8486 which is smaller
than 18080 but larger than 2080 . Therefore, the system will end at zone (3). It cannot reach point (4).

Now we can conclude that the final temperature of the system is = 0℃ and we have to calculate the amount of
ice that melts.
The available energy for the melting process is = 8486 − 2080 = 6406 , so:
6406
',F.,I = = = 80
80
And this mass is smaller than the initial mass of ice, so the result makes sense.
The final composition is then: Ice → &, = 200 − 80 = 120 (solid)
Water → !-.,/ = 150 + 5 = 155 (liquid)
Vapor → -2G/ = 5 − 5 = 0