Thermodynamics

Content of Lecture
1. Scope and use of thermodynamics macroscopic system
2. Energy, thermodynamic variables, state and non-state functions
3. Reversible and irreversible processes
4. Heat, temperature and the zero t h law of thermodynamics
5. The first law of thermodynamics
6. Adiabatic process and the closed System versus open system
7. The second law of thermodynamics and the entropy
8. The third law of thermodynamics
9. Thermodynamic cycles and Carnot engine
10. The microscopic basis of thermodynamics
11. The second law and equilibrium, temperature scales and thermometers
12. Latent heat and heat transfer
13. Calorimétrie (Bunzen ice calorimeter, thermostat, thermocouple and Stefan law
of heat radiation)
14. Newton cooling law
15. Thermal expansion and determination of heat conductivity coefficient

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Meaning of the word and the scope of the field
The word thermodynamics comes from the Greek words “therme” (heat)
and “dynamis” (force). The formal study of thermodynamics began in the early
nineteenth century through consideration of the motive power of work (the
capacity of bodies to produce work). Today, the scope includes energy and it's
relationship with the MACROSCOPIC properties of matter. Engineers use the
principles of thermodynamics to conceive and analyze natural processes as well
as for designing devices and equipment to meet human needs. Studying
thermodynamics is studying energy and its transformations. More appropriately
stated: “thermodynamics governs what's possible and what's not”. In fact,
thermodynamics is the field of physics that describes and correlates the physical
properties of macroscopic systems of matter and energy. The principles of
thermodynamics are of fundamental importance to all branches of science and
engineering since they are expressions of global roles governing the behavior of
natural systems. If any of the laws of thermodynamics is violated, you can rest
assured the inventor (either knowingly or unknowingly) is misrepresenting his
discovery. The laws of thermodynamics are descriptions of some of the fundamental
phenomena of nature as observed and concluded by scientists. Three laws (first,
second and third), have been formulated, and there is a statement that is sometimes
referred to as the zeroth law of thermodynamics.
Thermodynamic provides a link between several sciences and engineering
disciplines (physics, biophysics, chemistry, geochemistry, astronomy, physical
chemistry, oceanography, soil science, hydrology, engine design…etc.). It is may be
studied in standalone courses that are normally written to tackle the major
requirements and interests of each of those fields. We will only deal with the broad
concepts considered as the main introductory common parts on any account on
thermodynamics in general. Phase change of matter and the chemical and physical
reactions (processes) involve exchange of energy. So we apply thermodynamics to
know, follow and predict the output of processes and the state of matter.
Thermodynamics may be used to predict the temperature at which certain process
may occur, to understand the sequence of reaction progress and to follow the nature
of the reactants and products. In particular, thermodynamics deals with studying
systems at (or near) equilibrium assuming that process is reversible.
Thermodynamics neither deal with the pathways the system follows to carry out
the change nor with the mechanism of reaction. Despite this limitation,
thermodynamics are used in studying equilibrium in the natural systems in geology,
soils, water resources and recently biology. Since equilibrium is not reached in
most cases on the Earth crust (or only reached very slowly), this could seem
contradictory. However, kinetics help to understand how equilibrium is reached
(or why it is not reached!), i.e. there is close connection between thermodynamic
and kinetics.

Purposes and use of thermodynamics

1. following up and understanding the processes that include energy transfer.
2. predicting what should result from the change of state of matter in terms of
global parameters; like mass, temperature, pressure, chemical potential, Gibbs
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 free energy, entropy, and enthalpy (which refers to the sum of work & internal
energy change), i.e. predicting system behavior.
3. carrying out virtual experiments when it is difficult to carry it in reality.
4. generalization of conclusions that we may arrive at from experimental work.
5. through thermodynamics we can study the natural systems. We know that in
these system equilibrium is not actually realized and the natural processes are
irreversible and difficult to study. However, in thermodynamics we assume
equilibrium and assume that an irreversible process is constituted of many
small reversible processes to be able to solve it. This is possible since the
change in “internal energy” and the “entropy” are independent of the
pathway (i.e. they are “state functions”) whereas “work” and “heat” do
depend on the pathway (i.e. non-state functions) and the system does not
contain work or heat, considering that thermodynamic process is that the
action which leads to the change of the state of the system from a given
equilibrium situation to another.
In brief, the Uses of Thermodynamics are:
- it has a general applicability in the prediction of the behavior of systems under
different temperatures, pressures and chemical compositions.
- if we cannot carry out certain experiments (due to very slow rate of reaction,
high costs…), we use thermodynamic predictions.
- it used for the generalization of the output of experimental work.

The macroscopic system

The macroscopic nature of thermodynamics means that we are dealing with
the characteristics of the system as a whole (from the point of view of its
temperature, volume, temperature capacity, etc.) but we do not deal with the impact
of these characteristics on the internal structure and arrangement of atoms.
Also, in thermodynamics and we do not deal with the rate of reaction or its
mechanism. The macroscopic system is a central concept of thermodynamics. It is
the reason of our interest in thermodynamics and the source of its power. The
macroscopic system is a “geometrically isolated” system within an “infinite,
unperturbed environment”. The so-called “infinite environment” is a mathematical
abstraction of what we can also call “a thermal reservoir”. In reality the
environment need only be large relative to the system being studied.
Thermodynamics is concerned only with the study of systems at equilibrium,
When perturbation takes place, thermodynamics can predict the new
equilibrium (but cannot predict the pathway or the mechanism nor the speed of
reaction). However, there is a field of non-equilibrium thermodynamics. Also, the
aspects that cannot be covered by thermodynamics can be covered by kinetics. In
fact, there is a close relationship between kinetics and thermodynamics.
Energy - its meaning and types
It is the capacity for doing work. Energy can exist in many forms:
1. radiation, 2. kinetic energy, 3. potential energy, 4. chemical energy,
5. atomic (nuclear) energy, 6. electromagnetic energy, 7. electrical energy and
8. heat (thermal) energy.

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Thermodynamic properties and variables
At equilibrium, the state of a macroscopic system can be described in
terms of some measurable properties (temperature – pressure – volume) known as
thermodynamic variables. Meanwhile, other variables (such as density -
specific heat - compressibility - coefficient of thermal expansion) can also be
identified and correlated to produce complete description of a system, and its
relationship to its surroundings.
Thermodynamic variables are either intensive or extensive.
Intensive = variable that does not change with the number of moles, like:
- density (kg/m3)
- temperature (K)
- pressure (N m-2)
- chemical potential (= Gibbs free energy/ number of moles) (J kg-1)
extensive variable that changes with the number of moles, like:
- Gibbs free energy, G (J K-1)
- entropy, S (J K-1)
- enthalpy (H = work + internal energy) (J K-1)
- volume (m3)
- mass (kg)

State Functions, and Non-State Functions

State Functions
(functions that do not depend on the pathway the system follows to realize a change
and have exact differentials)
- volume
- internal energy
- entropy
- entalpy
- Gibbs free energy
- equilibrium
Non-state Functions
(functions that depend on the pathway the system follows to realize a change and
have inexact differentials)
- work
- heat
This means that heat and work have inexact differentials since they depend on the
pathway the process follows during the change of the state of the system.
Thermodynamic Processes
When a macroscopic system moves from a state of equilibrium to another, a
thermodynamic process is said to be taking place.
Some thermodynamic processes are
- reversible this is just an idealization, in fact it may be approximated but not
perfectly achieved. However, its formula is useful for solving problems when we
cannot directly use the formula of the irreversible process, in particular when the
studied variable is a state function (independent of pathway) and can be replaced by a
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series of imaginary reversible steps (that starts from the same initial state and ends-
up by the same final state as the irreversible process), hence an integration leads to
calculating the change that takes place during the irreversible process of interest.

Other thermodynamic processes are

- irreversible (evaporation, dissolution, diffusion, gas seepage through
openings from a high pressure reservoir to a law pressure one, gas mixing, mixing of
solutions, weathering, rusting of iron, coagulation, aging (growing older), heat flow
from a hotter to a colder reservoir, also water salt solutions (or ink and water) do not
separate by itself to salt (or ink) and water. These one-directional processes can be
studied by the second law of thermodynamics.

Definition of Heat
Heat is defined through thermal energy transfer (for example, from a hot
solid-phase body to a cold liquid; in this case, heat is the energy transferred from
the first body to the second). That is to say, heat can only be determined when it
flows across the boundaries of the hot to the cold body (heat transfer starts only
upon the “contact” of the two bodies, whereas we consider that neither of these two
bodies contain heat before this start). So, heat definition is:
“energy that flows across system boundaries due to their different
temperatures” i.e. heat - just like work - is a “transient” phenomena, i.e. it can
only be observed during system state change,
and both heat and work have a feature in common: both depend on the pathway of
the change, i.e these are non-state functions.

Laws of thermodynamics
The laws of thermodynamics, discovered in the 19th century through
painstaking experimentation, govern the nature of all thermodynamic processes and
place limits on them.
First law denies the possibility of creating or destroying energy
(conservation)
Second law denies the possibility of utilizing energy in a particular way (work
can be dissipated completely into heat, whereas heat cannot be completely
converted into work; reflecting one-sidedness of spontaneous – natural – processes).

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Zeroth Law of Thermodynamics
When two bodies (A) and (B), in thermal equilibrium, are in equilibrium with a
third body (C), then the two bodies (A) and (B) have the same temperature.
Or when each of two systems is in thermal equilibrium (no heat flow) with a
third, the first two systems must be in equilibrium with each other.
(the simple interpretation is: You can use a thermometer to measure
temperature!) (note that for some unknown reason the Zeroth Law came after
the First Law.)

Definition of Temperature
Difficult to define (since it is related to our “sensation” of hot and cold
bodies). So, we better refer to the “equity” of temperatures. This “equity idea”
leads to the Zeroth law of thermodynamics and it is the basis of temperature
measurement. For gases, temperature is a measure of the average kinetic energy
of gas molecules. In fact, the law of ideal gas can be used to design a
thermometer. Also, there is an implicit idea in this law saying that there is a
definite minimum value of the absolute temperature (absolute zero) at which the
volume of the ideal gas is zero (note that real gas should have a given volume
even at the absolute zero.)

Temperature definition using the Zero t h Law

The vocabulary of empirical (experimental) sciences is often borrowed from
daily language. Thus, although the term “temperature” appeals to common sense, its
meaning suffers from this imprecise “non-mathematical” language. A precise,
though empirical, definition of temperature is provided by the zeroth law of
thermodynamics. From what we previously stated about this law, it is understood that
when two systems are in thermal equilibrium, they share a certain property. This
property can be measured, and a definite numerical value ascribed to it. In other
words the zeroth law is a consequence of the statement:
temperature is the “shared property” of systems in “thermal equilibrium”.
If any system is placed in contact with an “infinite environment or reservoir”
that exists at some lower temperature, the system will eventually come into
equilibrium with that environment—that is, it reaches the same temperature as the
surroundings (we will soon study Newton’s Cooling Law that mathematically
describes this phenomenon using the first-order kinetic law). Temperatures are
measured with devices called thermometers (some types of thermometers are
described later in an optional part, where we present the basic ideas behind major
types of thermometer designs). A thermometer contains a substance with
conveniently “identifiable” and “reproducible” states, (such as the normal
“boiling” and “freezing” points of pure water). If a graduated scale is marked
between two such states, the temperature of any system can be determined by
bringing that system into thermal contact with the thermometer provided that the
system is large enough relative to the thermometer.

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First Law of Thermodynamics
Energy can be transferred from one "system" to another in many forms.
However, it cannot be created nor destroyed. Thus, the total amount of energy
available in the universe is constant. This is an expression of the principle of
“Conservation of Energy”, i.e. the first law states that the change of the
internal energy, ∆ U, is equal to the algebraic sum of the transferred
heat, Q and the work done, W:
∆ U=Q-W
This is equivalent to saying that the “supplied heat Q is contributing to both the
increase of the internal energy by ∆ U and the work done W”, i.e.
Q = ∆U + W
Special formulae of the 1st Law in four thermodynamic processes:
1. in the special case of an adiabatic process between two states, since
there is no heat transfer (Q = 0), the net work done (on or by the system) is
the same as the change in the internal energy
(The simple interpretation is: You don't get something for nothing!)
U2 - U1 = ∆ U = -W and in this case
enthalpy = (U2 - U1 ) + W = 0
2. in the particular case of an isochoric process, there is no way to carry
out work (so, W = 0), and
∆U = Q
3. in the special case of an isobaric process, the change of internal energy,
heat transferred and work done could not be zero, so the general formula of
the first law is directly applicable (like under the atmospheric conditions),
∆U = Q - W
and work can easily be calculated from the relationship:
W = P (V2 - V1)
where (for gases) W = P.∆V = CV ∆θ
4. in the special case of an isothermal process, the internal energy (and
temperature) does not change, (so, ∆U = 0) and
Q=W
Note:
the work done by the system is positive, (so internal energy decreases).
whereas the work done on the system is negative, (so internal energy increases),
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Adiabatic process - the meaning
A process in which heat does not enter or leave a system. In the atmospheric
sciences, adiabatic processes are often used to model internal energy changes in
rising and descending parcels of air. When a parcel of air rises in expands (because
of a reduction in pressure). If no other non-adiabatic processes occur (like
condensation, evaporation and radiation), expansion causes the parcel of air to cool
at a rate of 0.98 degrees per 100 meters. The opposite occurs when a parcel of air
descends in the atmosphere. The air in a descending parcel becomes compressed.
Compression causes the temperature within the parcel to increase at a rate of 0.98
degrees per 100 meters.
The adiabatic system can exchange energy with the surroundings in the form of
work but it does not exchange thermal energy nor matter with them since its
boundary are thermally isolated.

Adiabatic System
It is a system that exchanges energy with its surroundings in the form of work,
but not in the form of heat or matter transfer, that is to say its boundaries are
considered thermally isolated (no heat flow). This is a thermodynamic imaginary
concept, but it has many important applications since many of the natural system
could be considered as having good thermal isolation to the extent that it could
be considered as adiabatic systems.

Closed System
It is a system that does not exchange matter with its surroundings, but can
exchange energy with these surroundings (in the form of heat and work).
Open System
It is a system that exchanges both matter and energy with its surroundings.

Notes
- Einstein's famous equation E =MC2
(describing the relationship between energy and matter)
supports the credibility of the first law of thermodynamics.
- Originally, work units are erg and joule whereas heat unit is calorie.
- One calorie is equivalent to 4.186 × 107 ergs, or 4.186 joules.
- We can also, say that
the first law of thermodynamics presents a definition of heat.

A common example of an adiabatic process is the drop in temperature of an

aerosol can, when some of the can's contents are released. Energy was used-up as the
gases expanded too quickly for significant heat transfer to occur, hence the drop
in temperature.
A reverse effect of temperature rise is seen when a gas is compressed
quickly.

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 Also, various familiar systems, such as automobile engines, exhibit adiabatic
phenomena.

How 1st law has enhanced the conservation of energy principle?

1. It has extended the scope of the conservation of energy principle to cover
mechanical work and heat transfer.
2. It has introduced the concept of internal energy and reveals the distribution of
heat between work and internal energy.
3. It provides a practical measurement of the change of internal energy (so, the
internal energy may be indirectly measured knowing its reference level for the
standard state). So, we avoid the details internal energy related to microscopic
structure of matter.
4. It assures that there is only one value for the internal energy for any system in a
given case.
5. It indicates that the total changes that may take place in internal energy in a
cycle made-up of several thermodynamic processes is zero (∆ U = 0). Also, the
internal energy of an isolated system will stay constant (∆U = 0) (provided that
that it does not do work).
6. It indicates that the internal energy of the ideal gas depends only on its
temperature (but for other systems it also depends on pressure).
7. this law is open to include other types of energy and its transfer methods.
8. it prevents the invention of the illusionary perpetual machine of the first kind
which is a machine that does not need heat to do mechanical work.
A perpetual machine “of the first kind” is a machine that does
not need heat to perform work. The law of energy conservation (the 1st law of
thermodunamics) “rules out” the possibility of this imaginary perpetual
machine ever being invented.

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Second Law of Thermodynamics
Heat can never pass “spontaneously” from a colder to a hotter body.
As a result of this phenomenon, natural processes that involve energy transfer
must have one direction, and all natural processes are irreversible.

This law also predicts that the “entropy” of an isolated system left
to itself (without human intervention) always increases with time (if all
compnent processes are taken into account). This law can also be stated as follows:
- If we let a natural system to its own, the only change will be towards the state
that has the maximum probability.
- it is impossible to introduce wastes through the discharge point, to produce
nutrients at the input point !
- It is impossible to build an engine capable of heat transfer in continuous circulation
from a reservoir at low temperature to another at high temperature spontaneously
(without work done by an external engine). (we know effectively that it is
impossible to cool-down the air space inside a refrigerator or a room
spontaneously, on the contrary we need work to do that).
- heat can never be extracted and completely transformed into work (since there is
something which we call “entropy increase”). This means that engine efficiency
can never by 100%. (however, the best method - as stated by Carnot cycle - to
improve engine efficiency is to keep the high temperature end of the system at
high temperature while keeping its cool end at low temperature; that is why car
engine is cooled down by a water circuit and a fan, while fuel ignition is carried
out at high temperature).
- entropy is ever increasing in the universe.

In fact, the second law summarizes some of our familiar daily observations like:
- we cannot use the cow to produce Alfalfa (if we can feed it with its excretions),
only the inverse is possible.
- you can never introduce waste gases (CO2 and water) into an engine to get a
new non-ignited fuel while pushing the car backward on the road. Only the
inverse is possible - that is to say fuel ignition is an irreversible process.
- if you open a wall that separates two gas chambers each containing different
gas, the two gases mix and you never get the two gases spontaneously
separated again, by their own, and return back to their respective original
reservoirs, if you insert again the wall to its original position.
- water mixes with salt in a closed vessel (dissolving it), but the mixture never
returns back to its original state (pure water and salt apart from each other).
- people get older but never the inverse.
- heating a broken egg, you get an omelet, but you can never use an omelet to
get an egg.

In fact, examples of the natural (irreversible) processes are end-less. All

these observations (feeding cows with Alfalfa and getting excretions, fuel ignition
in an engine and getting wastes, mixing of gases, salt dissolution into water,

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people get older, getting an omelet from eggs) are so familiar that their inverse is
just a completely funny idea that can never be realized.
In reality there is nothing in the fist law of thermodynamics which stands
against realizing this inverse processes (the only condition that is imposed by the
fist law is that the number of joules on both sides is similar), However, the
second law presents an additional condition on the natural process; this is the
condition of the direction of the process: natural process has a direction that can
never be inverted; this is the unidirectional character of nature, and it is the
reason behind the ever increase of entropy in nature.
With the progress of these processes, energy becomes more and more
unavailable. Energy is not lost in these processes, but the opportunity is lost (the
opportunity to covert a portion of the heat flowing out of hot water, for example,
to mechanical work); we say the universe is run-down to that extent, and this is
the true significance of the term ”irreversible”. The tendency of all natural
processes is to bring about a uniformity of temperature, pressure, composition,
etc., at all points. One may visualize a distant future in which as a consequence
of these processes, the entire universe has attained a state of absolute uniformity
throughout. When and if such a state is reached, although there would be no
change in the energy of the Universe, all physical, chemical, and presumably
biological processes would have to cease. This goal toward which we appear
headed gas been described the “heat death” of the universe.

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- Entropy (J K-1) - the meaning
is a measure of the disorder (randomness) of energy (and matter) in a
system. The change of entropy (∆ S) is defined by the integral of the
change in transferred heat (d Q) divided by temperature (T):
or for an infinitesimal change

1. For an “irreversible” process, these two relations are not directly

applicable (but only applicable using a trick , which is replacing the
irreversible process by a series of isothermal reversible processes.
This is acceptable since entropy depends only on the initial and final
states), for the “irreversible” process, entropy is ever increasing:
∆ S>0
In the mixing equal masses of hot and cold water, the entropy increase
of cold water is greater than the entropy decrease of hot water), so the
overall irreversible process leads to a net increase of entropy (∆ S >
0).
2. For a “non-cyclic single reaction that is infinitismal and reversible
process that undergoes under isothermal conditions”, we have:
i.e. dQ = T . dS
To calculate total entropy change under isothermal conditions (e.g.
for ice melting):

3. However, when we consider several “reversible processes in a cycle”

process (like Carnot cycle), we get:

this means that the reversible cyclic process is a special case of the
irreversible process with the increase in entropy “in a part” of the
system is balanced by the decrease in entropy of “the other part”
of the system. This is the criterion for thermodynamic
equilibrium. In fact, hear ∆ S = 0, since the cycle (like Carnot cycle)
has no irreversible process. Remember, entropy can never
decrease in whole system undergoing a natural irreversible
process.
4. For an adiabatic reversible process (reversible adiabatic expansion or
adiabatic compression), there is no heat transfer (d Q = 0) so, there is
no change in entropy (dS = 0). (this in known an isentropic
process). But for an irreversible adiabatic process (like free
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 expansion of a gas without doing work on a piston), there should be a
given amount of entropy change that can only be calculated using a
trick (replacing the irreversible adiabatic process by a series of
isothermal reversible expansion - for the case of free expansion - for
example, that can be solved using the relations applicable to the
reversible process). For the natural irreversible process which takes
place when thermal imbalance exists between two systems (like heat
flow from a hot body to a cold on in contact or by mixing), before
doing the process there existed an opportunity for developing
mechanical work. This opportunity becomes irrevocably (=
irreversibly or irretrievably) lost if the systems were allowed to
come into thermal equilibrium in an uncontrolled way. (the
simple interpretation is: Even if you do get something, you won't get as much
as you thought you might!).
Note that: combining the 1st law of thermodynamics
∆ U=Q-W
in its isobaric infinitismal form (where V.dP = 0)
dU = dQ - dW
and the 2nd law of thermodynamics for a reversible reaction
dQ = T. dS
we can write the following formula:
dU = T . dS - dW or dU = T . dS - P . dV

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Notes
We can say that the second law of thermodynamics gives a precise definition
of a property called entropy.
Entropy can be thought of as a measure of how close a
system is to equilibrium (it is at maximum at equilibrium,
whereas internal energy is at minimum); Entropy can also be thought
of as a measure of the “disorder” in the system.
The second law states that the entropy of an isolated system
can never decrease.
Thus, when an isolated system achieves a configuration of maximum
entropy, it can no longer undergo change: It has reached equilibrium
(e.g. thermal equilibrium to which hot and cold water reach
when they are put into contact or mixed).
We can say the Nature, then, seems to “prefer” disorder or chaos.
in
It can be shown that the second law stipulates (= imposes a condition) that,
the absence of work, heat cannot be transferred from a region
at a lower temperature to one at a higher temperature.
It is not enough to conserve energy (according to the first law) , but a direction
of the natural process must be also respected.
An imaginary machine that would deliver work while violating the second
law (by continually draw energy from a cold environment to do work in a hot
environment at no cost) is called a “perpetual-motion” machine of the
“second kind,” The second law says that this machine can never be invented.

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Third Law of Thermodynamics
The second law suggests the existence of an absolute temperature scale that
includes an absolute zero of temperature (on a plot of the relationship between
pressure - the vertical axis - and temperature - the horizontal axis - in an isobaric
process, temperature of -273.16 is obtained at pressure zero). The third law of
thermodynamics states that:
“absolute zero cannot be attained by any procedure in a finite
number of steps. Absolute zero can be approached arbitrarily closely,
but it can never be reached”.
If all the thermal motion of molecules (kinetic energy) could be removed, a
state called “absolute zero” would result and all energy would be randomly
distributed.

Absolute Zero = 0 degrees Kelvin = -273.15 degrees Celsius.

For all materials, the entropy is zero at the absolute

zero. At any other temperature (T), we can calculate the value of entropy for
the material in an reversible reaction from the relation defining the heat
capacity:

d Q = C * dT or heat capacity (C) is C = d Q / dT

but we know already, for a reversible reaction that
that is to say d Q = T . dS
and by substitution: C = T d S / dT
i.e. d S = (C/T) dT
S = C * [(1/T) d T]

Entropy (S) value can be obtained from the integration of this equation
(the equation under the integral in the right-hand side is normally formulated as a
polynomial, for which the solution is known).

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 OPTIONAL READING
Thermodynamic Cycles

All important thermodynamic relations used in engineering are derived from

the first and second laws of thermodynamics. One useful way of discussing
thermodynamic processes is in terms of cycles (processes that return a system to its
original state after a number of stages, thus restoring the original values for all the
relevant thermodynamic variables).

In a complete cycle the internal energy of a system depends solely on these

variables and cannot change. Thus, the total net “heat transferred” to the system
must “equal” the “total net work” delivered from the system (i.e. respecting the
first law of thermodynamics).

An imaginary ideal cycle would be performed by a perfectly efficient heat

engine—that is, all the heat would be converted to mechanical work. The 19th-
century French scientist Nicolas Léonard Sadi Carnot, who conceived a
thermodynamic cycle that is the basic cycle of all efficient heat engines, showed that
such an imaginary engine (perpetual machine of the second order)
cannot exist. Any heat engine must expend some fraction of its
heat input as exhaust (due to the increase of entropy).
The second law of thermodynamics places an upper limit on the efficiency
of engines; that upper limit is less than 100 percent.

The limiting case is now known as a Carnot cycle.

Carnot Engine
The idealized Carnot engine was envisioned by the French physicist Nicolas
Léonard Sadi Carnot, who lived during the early 19th century. The Carnot engine is
theoretically perfect, that is, it converts the maximum amount of
energy into mechanical work.
efficiency of any engine depends on the
Carnot showed that the
difference between the highest and lowest temperatures reached
during one cycle.

The greater the difference, the greater the efficiency.

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 more efficient if the fuel
An automobile engine, for example, would be
burned hotter and the exhaust gas came out of the cylinder at
a lower temperature.
Microscopic Basis of Thermodynamics

The recognition that all matter is made up of molecules provided a microscopic

foundation for thermodynamics. A thermodynamic system consisting of a pure
substance can be described as a collection of like molecules, each with its individual
motion describable in terms of such mechanical variables as velocity and momentum.

At least in principle, it should therefore be possible to

derive the collective properties of the system by solving
equations of motion for the molecules. In this sense,
thermodynamics could be regarded as a mere application of
the laws of mechanics to the microscopic system.
Objects of ordinary size—that is, ordinary on the human scale—contain
immense numbers (on the order of 1024) of molecules. Assuming the molecules to be
spherical, each would need three variables to describe its position and three more to
describe its velocity.

Describing a macroscopic system in this way would be a

task that even the largest modern computer could not manage.
A complete solution of these equations, furthermore,
would tell us where each molecule is and what it is doing at
every moment. Such a vast quantity of information would be
too detailed to be useful and too transient to be important.
Statistical methods were devised therefore to obtain averages of the mechanical
variables of the molecules in a system and to provide the gross features of the system.

These gross features turn out to be, precisely, the macroscopic thermodynamic
variables.

The statistical treatment of molecular mechanics is called statistical mechanics,

and it anchors thermodynamics to mechanics.

59
 temperature can be defined
Viewed from the statistical perspective,
as a measure of the average kinetic energy of the molecules of
a system.
Increases in temperature reflect increases in the vigor of molecular motion.
When two systems are in contact, energy is transferred between molecules as a result
of collisions. The transfer will continue until uniformity is achieved, in a
statistical sense, which corresponds to thermal equilibrium.

kinetic energy of the molecules since it

Heat can be defined as the
corresponds to heat and (together with the potential energy
arising from interaction between molecules) makes-up the
internal energy of a system.
The conservation of energy, a well-known law of mechanics, translates
readily to the first law of thermodynamics,

The concept of entropy translates into the extent of disorder on the

molecular scale. By assuming that all combinations of molecular motion are
equally likely, thermodynamics shows that the more disordered the state
of an isolated system, the more combinations can be found
that could give rise to that state, and hence the more
frequently it will occur. The probability of the more
disordered state occurring overwhelms the probability of the
occurrence of all other states. This probability provides a
statistical basis for definitions of both equilibrium state and
entropy.
Finally, temperature can be reduced by taking energy out of a system, that is,
by reducing the vigor of molecular motion. Absolute zero corresponds to the state of
a system in which all its constituents are at rest. This is, however, a notion from
residual molecular
classical physics. In terms of quantum mechanics,
motion will exist even at absolute zero. An analysis of
the statistical basis of the third law goes beyond the scope of the present discussion.

End of Optional Reading

60
The Second Law and Equilibrium
For all materials, the entropy is zero at the absolute
zero. At any other temperature (T), we can calculate the value of entropy for
the material in an reversible reaction from the relation defining the heat
capacity:

d Q = C * dT or heat capacity (C) is C = d Q / dT

but, for a reversible reaction, we know already that
that is to say dQ = T. dS
and by substitution: C = T . d S / dT
i.e. d S = (C/T) dT
S = C * [(1/T) d T]

Entropy (S) value can be obtained from the integration of this equation
(the equation under the integral in the right-hand side is normally formulated as a
polynomial, for which the solution is known).

In the chemical application of thermodynamics, we are interested in a state

function known as Gibbs free energy (G) and its change (d G). In fact, Gibbs
free energy is a measure to determine the free enthalpy (the energy which is free
for carrying out the reaction). i.e. it is a measure to determine the chemical work (a
type of work that differs from the usual gas work that depends on the change of
volume and pressure).

In fact, we are always interested in knowing the change of Gibbs free

energy (∆ G) to compare the free energy of materials i.e. to know the amount
of heat available between two materials to carry out a reaction (instead of
knowing the absolute value of Gibbs free energy). In other words, (∆G) is the
motive force that drive the reaction.

G = H - T.S
∆G = ∆H - T . ∆S
where
H enthalpy (= U+ PV), J/kg (or kJ/mole).
S entropy (disorder or randomness, units J/mole.K).

the term (∆H - T . ∆S) means:

61
a chemical work is done in order to face the natural tendency of disorder
(entropy) increase.

This means also that:

a fraction of the energy in any system can NEVER appear in the form of work.
The reason: this “hidden” fraction is already consumed in the increase of
entropy. This is a natural role of the universe that cannot be avoided.

Reactions will be initiated, and go on, as long as the Gibbs free

energy difference (∆G) between two suggested reacting
materials is a negative value (∆G < 0).
When difference is zero (∆G = 0), equilibrium is reached.
If (∆S) and (∆H) are both positive and T ∆S is greater than ∆H, a melting
reaction can occur.
If (∆S) is positive and (∆H) is negative,
a ignition reaction can occur.
If (∆S) and (∆H) are both negative and T ∆S is greater than ∆H,
a crystallization (or solidification) reaction can occur.

In any other case of sign reaction cannot occur

(like when ∆S and ∆H are both positive or both negative, with T ∆S is smaller
than ∆H, or when ∆S is negative and ∆H positive).

can or cannot
In fact, to know if a certain chemical reaction
occur, we calculate the value of (∆ G) for the
reaction (by addition of the ∆ G values of formation for the components or
phases, including the reactants and the suggested products, and their stoichiometric
If the obtained value is negative the
coefficients).
reaction can occur. If it is zero, the reaction is
at equilibrium.

62
 In addition, we usually use a relation that states that the (∆G) of reaction
is the sum of (∆G°) for the reaction for the standard state and the term
(RT l n Keq):
∆Gr = ∆Gr° + RT ln Keq
But we know that at equilibrium, ∆G r = 0, so
- RT ln Keq = ∆Gr°
- l n Keq = ∆Gr° / RT
l n Keq = - ∆Gr° / RT

Keq = e-∆ Gr°/RT

so, we can use this formula to calculate the equilibrium constant
K e q of the reaction using the ∆G r° value that can be obtained from the
thermodynamic tables (knowing the ∆G f° of reactants and products). Also, we
can obtain a calculated K (the activity product) for a give solution and compare
it with theoretical K e q, in order to know if the reaction is at equilibrium, or if it
is still far behind it, or if it has already by-passed the equilibrium status.

In reactions that take place in aqueous solutions, we obtain the chemical

potential by dividing Gibbs free energy by the
63
number of moles to get the intensive property
(potential) corresponding to it. We write a relation (similar to what is given
above for Gibss free energy), for the chemical potential of each
aqueous species:
µ i = µ i° + RT ln ai
where for dissolved solids
a i activity of the aqueous species (activity is the product of molality and
activity coefficient), Activity is the fraction of the total concentration which
is contributing in the reaction.

Third Law of Thermodynamics

The second law suggests the existence of an absolute temperature scale that
includes an absolute zero of temperature (on a plot of the relationship between
pressure - the vertical axis - and temperature - the horizontal axis - in an isobaric
process, temperature of -273.16 is obtained at pressure zero). The third law of
thermodynamics states that:
“absolute zero cannot be attained by any procedure in a finite
number of steps. Absolute zero can be approached arbitrarily closely,
but it can never be reached”.
If all the thermal motion of molecules (kinetic energy) could be removed, a
state called “absolute zero” would result and all energy would be randomly
distributed.

Absolute Zero = 0 degrees Kelvin = -273.15 degrees Celsius.

OPTIONAL READING
Thermodynamics and Chemical Reactions

In a chemical reaction like:

a A + bB = c C + d D
where
A, B, C, D concentrations (or activities or pressures) of reactants and product.
a, b, c, d their stoachiometric coefficients.

64
thermodynamics can be used to understand the relationship of the equilibrium
constant K (or the solubility product, K s p in dissolution-precipitation reactions, or
the standard half-cell potential ∆ ε ° in redox reactions) - which describes the
tendency of the reactants to form products - through the characteristics of the
reactants and products.

ln K = c ln [C] + d ln [D] - a ln [A] - b ln [B]

In the chemical reaction, a change in system composition takes place since
reactants are transformed into products. This change is associated with a certain
change in internal energy (∆ U) that results in the fact that the internal energy
of products differ from that of reactants, reflecting the difference of the
“mechanical stability” of both (since any amount of macroscopic chemical
substance is an agglomeration of numerous simple mechanical systems).
∆U can be obtain be four methods:

1. carrying out the reaction in a constant volume (i.e. under isochoric

conditions) and measuring the emitted (or the absorbed) heat (Q v) which will
be equal to (∆U). From the first law, ∆U = Q - W, and since W= 0, we get:
∆ U= Qv
2. carrying out the reaction under constant pressure (isobaric conditions) - as
usual under atmospheric pressure - and measuring the emitted (or the
absorbed) heat (Q p) which will be equal to the change in enthalpy (∆H).
Enthalpy (which is U under isobaric conditions, is greater under isobaric
conditions than U under isochoric conditions by the work done, i.e. Qp is greater
than Qv by the work done). Enthalpy is a state function which is defined (only
under isobaric conditions) as:
H = U + W
∆H = ∆U + P ∆V
∆H = Qp - W + P ∆V
∆H = Qp
(in both method, 1 and 2, when an exothermic reaction takes place, Q will be
negative, i.e. energy of reactants will be lower than energy of reactants, whereas
when an endothermic reaction takes place, Q will be positive, i.e. energy of
reactant will be greater than energy of reactants).
3. when ∆H cannot be measured, Hess Law for constant heat sum is used to
calculate ∆H, but this could be as difficult as the above-mentioned methods.
° °
4. calculating (∆H R ) for the reaction from formation enthalpy (∆H f ) of
reactants and products in their standard states (stoichiometric coefficients
are for sure included).
∆H°R =

65
 (when the range of temperatures under which the reaction takes place is small,
°
we suggest that enthalpy of reaction, ∆H R, does not depend on temperature
since ∆ Cp will be small to ignore the integral in the formula for one mole:
∆H2 = ∆H1 +
under isochoric conditions: i.e. dU = Cv . dT
and under isobaric conditions: i.e. dH = Cp . dT
From the second law of thermodynamics, chemically we can predict the
extent to which the spontaneous reaction can develop. Also, the second law gives
an interpretation for the direction of the spontaneous reaction (for example, a gas
flows out from a hole - not for decreasing its energy as can be suggested from the
first law - note that this interpretation based on the first law is not right since gas
energy does not depend on its volume but on its temperature - ; the right
interpretation is given by the second law: during a spontaneous reaction a material
has a natural tendency to arrive to a higher disorder - and entropy increase - by
the irreversible reaction which results in producing products which accommodate
with the higher probability of the microscopic states associated with one macroscopic
state, and since the microscopic states can never by described by equations due to
their extremely huge number, the only way we have is to express the macroscopic
state in terms of its entropy).
In the irreversible reaction, the process takes place at a given rate (which
is usually slow; like dissolution, evaporation and solution mixing). If this reaction
involved a change in temperature or pressure, there should be a substantial
difference between temperature and pressure of the system and its
surroundings, so this reaction cannot be stopped or reversed in direction by
making a very small change in the external conditions of the surroundings since
this small change will not be able to supersede the great difference in
temperature and pressure (or other thermodynamic functions) between the system
and its surroundings (difference which is originally behind the occurrence of the
irreversible reaction).
Also, in the irreversible reaction, the work done by the system is smaller
(than if the reaction were reversible), and the amount of heat needed by the
irreversible reaction is smaller (than that needed if the reaction were reversible).
An irreversible reaction is conveniently replaced by a series of reversible
reactions in order to apply the quantitative estimate of entropy valid only for the
reversible reactions.
Contrary to the irreversible process, the reversible process (which is a
conceptual simplification that has no real existence) is a process that takes place
such that state functions does infinitismally change (so it is sometimes called the
semi-static process) also the state functions of the system are very slightly
different from the surroundings. The reversible process (for example, equilibrium,
and to some extent precipitation of solid-phases and condensation of water from
vapor) is very fast, and we can control its direction by doing a very small change
in surroundings conditions.
Also, in the reversible reaction, the work done by the system is greater
(than if the reaction were irreversible), and the amount of heat needed by the
66
irreversible reaction is greater (than that needed if the reaction were irreversible).
We previously said that in a reversible process, entropy is constant (entropy
change for the system and its surroundings together is zero; ∆S = 0).
For the reversible process, Gibbs free energy (more precisely Gibbs free
enthalpy for reactions done under constant pressure) is zero (dG = 0).

If the calculated d G is negative, d G < 0, the process is irreversible,

whereas if d G= 0, the process is reversible. Using entropy change ∆S, if ∆S
increases, the process can be defined as irreversible, if ∆S = 0, the process is
reversible, if ∆S decreases, the process is impossible to occur spontaneously.

Contrary to enthalpy, entropy is highly affected by temperature change:

under isochoric conditions: ∆S =

under isochoric conditions: ∆S =
under isobaric conditions: ∆S =
for liquids: ∆S =
∆S = m C
∆S = m C
for one mole at any given temperature starting from absolute zero:
∆S = ST - S0 = C
but since entropy at absolute zero = zero (S0 = 0), we get ST in J mol-1 K-1:
ST=C
°
in fact, we are only interested in ∆S R associated with the chemical
reaction that can be calculated using tabulated values of ∆S °f
(note that ∆S °f is the standard entropy of formation at 25 °C, it is
tabulated in thermodynamic tables).

∆S°R =
For liquids evaporation: ∆S =
∆S =
and if evaporation is considered as a reversible process (instead of its reality
an an irreversible process) taking place under isobaric conditions, the
amount of heat Q added to the system will be equal to enthalpy of
formation:
Q = ∆Hf
hence, ∆S = =
For all liquids, ∆S associated with evaporation = approximately 87.9 J K-1.

When ∆S °R is a small positive value, the reaction is irreversible and

the structures of reactants and products are similar, whereas if ∆S ° R was
67
a great positive value, the reaction is irreversible with the atomic structure
of the products and reactants being greatly different.

Note that using ∆S for judging if the process is reversible or

irreversible requires the recognition of the characteristics of the system
and the surroundings (not only the system), so we need an easier way, or
criteria, that depends only on system characteristics; this criteria is known
as Gibbs free energy G (it is a state function).

End of Optional Reading

68
7.1 temperature scales

7.1.1 Celsius (Swedish scientist)

Before 1954 two points were selected
- upper: water boiling assigned 100 o C (temperature of water and vapor
mixture in equilibrium under 1 a tm).
- lower: ice point assigned 0 o C (temperature of water and ice in
equilibrium with saturated air under 1 a tm).
After 1954 one point was selected on the ideal gas temperature scale
this point is the tertiary (triple) water point (ice-water-vapor in
equilibrium), it is 0.01 oC
(and practically, water boiling point = 100 oC).
i.e. there is agreement before and after 1954.

The Absolute Temperature Scale:

results from the second law of thermodynamics. Its advantage: on this
scale, temperature does not depend on any thermometry material.
Disadvantage: its use is very complicated. So, practically we use the:

Practical International Scale:

based on assignment of different temperatures to some points which can
be easily repeated.

The link between the Absolute Temperature Scale and the Celsius Scale
is the Kalvin Scale.

7.1.2 Fahrenheit
7.1.3 Reaumr
7.1.4 Kelvin (Lord William Thomson)

OPTIONAL READING
69
7.2 thermometers

7.2.1 based on solid-phase expansion

(bi-metallic thermometer)
- two metal bands that obviously differ in their thermal expansion
coefficients. The deviation of their free ends are used to move a
pointer (or producing the closure of an electric circuit).

7.2.2 based on the expansion of a liquid

- well known! Mercury and colored alcohol filled capillary
connected to a liquid reservoir.

7.2.3 based on the expansion of gas

- constant volume gas bulb reservoir (kept constant by a
connected U-shape Mercury manometer and to read gas
pressure deviation “h” from atmospheric).
- fitness to ice point
- fitness to water boiling point
- fitness to temperature “t” to be measured
P0 = h 0 + atm P100 = h100 + atm Pt = h t + atm

Pt − P0 t ht − h0 t
= =
P100 − P0 100 h100 − h0 100

7.2.4 based on temperature-induced

electromotive force (e. m. f.)
- temperature difference between the ends of two welded metal
wires produces an “e.m.f.”
- fitness to ice, boiling water and temperature “t” to be measured
70
 - thermocouple
- Platinum resistance thermometer
- a Wheatstone bridge is used to measure the electric resistance R.

Rt − R0 t
=
R100 − R0 100

End of Optional Reading

7.3 internal energy and thermal energy
7.3.1 internal energy
- internal energy =
sum of kinetic + potential + chemical + electric + nuclear
(where kinetic = transitional + rotational + vibrational)
7.3.2 thermal energy
- defined as energy flow upon contact of two bodies having
different temperatures as said before.

7.4 heat capacity and specific heat capacity

- amount of heat to change temperature of a body by 1 degree.
- amount of heat to change temperature of mass unit by 1 degree.

7.5 latent heat

7.5.1 latent heat
- amount of heat to change state of matter’s unit mass without
changing its temperature. (melting, evaporization,
solidification). (contrary to sensible heat that can be measured)
7.5.2 heat of evaporation
- amount of heat to transform liquid’s mass unit into vapor.
and condensation
- amount of heat to transform vapor’s mass unit into liquid.
71
7.6 specific heat measurement (calorimétrie)
7.6.1 based on temperature differences
1- mixing method
amount of gained heat = amount of lost heat

amount of heat = mass * specific heat * temperature difference

= m* S * (θ 1 − θ 2)

72
 2- Newton cooling law
It is an excellent example on a first order law of kinetics related to heat
dissipation from a higher to a lower temperature body (one directional process
according to the second law of thermodynamics) accompanied by a certain
unavailability of energy through entropy increase, but it is also related to the
zeroth law (due to the approach to equality of temperatures of two systems with a
third) as long as we are measuring temperatures using a thermometer during th
cooling-down process.

From a kinetic point of view, while temperature of the cooling-down body is

always decaying, the rate of cooling (dT/dt) is ever decreasing with the decrease
of the temperature difference (T-C) between the body temperature (T) and room
temperature (C). This law can be derived as follows:

73
 Derivation of Newton’s Cooling Law
dT dT
∝ T−C =−k ( T−C) d T =−k ( T −C) . d t
dt dt
1
− d T =k . d t
( T −C )
( T −C ) t t t

−
∫)
1
(T −C ) ∫ [
d T = k . d t − ln (T −C )t −ln (T −C )0 =k ] ∫d t
( T −C 0
0 0

( T −C ) t  ( T −C) 
t 
− ln =k t − ln / k = time
( T −C) 0 
 ( T − C ) 0

( T − C) t −k t
=e
( T − C) 0

hc . A
Tt =(T −C )0 . e
−k t
+C
with k =
m .Sp

- k decay constant in units of (time-1).

- room temperature (C) is assumed constant.
- the “type” of this law is frequently used in other applications
such as radio-active decay, and Beer-Lambert Law in optics.
- if we know the value of the decay constant, k, Newton’s law
can be used to know time, t, elapsed since the start of
cooling.
- knowing the variables: the decay constant, k, specific heat S p,
cross-section area A, and mass m, the formula:
hc A
k=
m Sp

can be used to determine thermal convection coefficient h c

but usually we get it by dimensional analysis or
experimentation.
Note that specific heat S p can be obtained using equal cooling
rates of two different liquids knowing the specific heat of one
74
of them (e.g. water) when we heat both to same temperature
then left them to cool-down in same room temperature. So, they
cool-down during different times, t1 and t2, but the two cooling
rates (amount of heat divided by time for each liquid) are
equal (note that the masses of two calorimeters are mcal 1 and
mcal 2 and they are made-up of the same material, so their
specific heat, S p cal, is the same). Hence, we can calculate the
unknown specific heat of the liquid, S p liquid :
(m cal 1 S cal +m water S water ) =
(m cal 2 S cal +m liquid S liquid )
t 1 t 2

75
T and T-C o Newton's Cooling Law
C
100

80 T model
60 data
room temp.
40 T-C model
20 data

0
0 10 20 30 40 50
time, minute

o
T, C always temperature differs
28.9

28.7

28.5 model
28.3 room temp.

28.1

27.9
50 52 54 56 58 60
time, minute

76
 OPTIONAL READING
7.6.2 Specific heat measurement
based on latent heat

1- Bunzen ice calorimeter

- mixing a known heated mass of the body with an ice mass, a
fraction of ice melts.

- using the mass of the melted ice and the latent melting heat (L),
the amount of heat gained by ice is defined, it is equal to heat
lost by the body, so body’s specific heat can be determined.

- look preparation of the apparatus for experimental work in book

(page 143).

- mass of molten ice is calculated from the observation of the

recession of Mercury in capillary tube.
V πr 2 l
m = =
∆V 10908
. −1.0001

m * L = m * S *
(θ2 − θ1)

2- condensation method
- hot water vapor at 100oC is inflow is conducted into a
chamber where a body (of mass m1) is suspended at the plate of
a balance, body temperature increases from θ to 100 o C,
whereas a fraction of vapor condenses (its lost heat is controlled
by its latent heat, L, and the condensed mass, m).

77
m * L = m1 * S * (100 − θ)

78
7.7 thermal expansion
7.7.1 solid-phase expansion
- longitudinal expansion coefficient (oC-1).
α=
∆L / L
∆T
or
dL 1
dT L (T = temperature)
- volume expansion coefficient (oC-1).
∆V / V dV 1
γ = or
∆T dT V
Suppose the body is homogenous in three dimensions, so:

dV (
=3 L2 d l )

divide by dT
dV
=
(
3 L2 d l )
dT dT

divide by V = L3
1 dV
=
3 L2 d l ( ) 1
V dT dT L3
3 ( d l) 1
γ=
dT L

γ =3 α

7.7.2 liquid-phase expansion

- liquid volume expansion coefficient (oC-1).

γ real =γ apparent +γ container

7.7.3 gaseous-phase expansion

- previously dealt with under Charles law.
 t 
Vt =Vo 1 + 
 273 

7.8 heat transfer

79
 7.8.1 by convection
- heat flow mode with the movement of fluid particles due to
decrease of density with temperature increase (convection
currents).
- stratification of deep lakes.
- flow of air during air-conditioning.
- flow of air from sea-side inland and vice versa during the day.

 application:
domestic water heating
- hot-water flows upward in the heated reservoir, whereas colder
water sinks down (higher density).
7.8.2 by conduction
- heat Q flow mode (without translocation of particles) due to
heat gradient effect on increasing kinetic energy.

- it depends on heat gradient R, area A and time t :

R=
θ1 −θ2
Q ∝R (d = distance)
d

- exposed cross-section area, A. Q ∝A

- duration, t. Q ∝t

Q ∝ AtR
θ1 −θ2
Q =k At
d

thermal conduction coefficient, k:

80
 Qd
k =
(θ1 −θ2 ) At

81
 Determination of heat
conductivity coefficient

- by Searle’s cylinder method

- steady state flow of heat is accomplished in the apparatus
(shown in the book page 150), this state is verified by constant
reading of four thermometers during enough long time (two in
the metal cylinder and two others in cooling water-tube coil).
- the gradient is created by fixation of one end of the metal
cylinder in a vapor chamber.
- heat transferred by conduction = heat gained by flowing water
θ 1 −θ 2
Q=kAt = m . S ( θ 4 −θ 3 )
d
m . S . d (θ4 −θ3 )
k=
A t (θ1 −θ2 )

- by Lees disk method

- the “unknown” metal disk is inserted between two brass disks.
- heating the upper surface of the “unknown” disk by boiling
water vapor, for long time to accomplish steady state, this state
is verified by constant temperature readings of two
thermometers inserted in the upper and lower brass disks.
- heat transferred by conduction = heat lost by radiation to air

θ 1 −θ 2
Q=kAt = m . S ∆θ
d

7.8.3 by radiation
- no need for any material medium for heat transfer by radiation.

- Stefan law:

(
Rnet = e .σ T14 −T24 )
82
e = constant.

σ = emission coefficient (fraction range from 0 to 1).

T1 = body temperature, k.

T2 = surroundings temperature, k.

Rnet = net emission by radiation, watt/ m-2 i.e. Joul-1.s-1.m-2.

- heat radiation measurement

by the thermopile
- the thermopile is a set of thermocouples connected in series,
the extreme ends are connected to a galvanometer.

- temperature of the welded points exposed to radiation increases,

whereas temperature of the non-exposed welded points does not
increase.

- Temperature gradient generates an electric current that can

be read by the galvanometer.
7.9 other applications of heat theories

(thermostats)

- thermostats are used to control constant temperature in oven,

refrigerators and incubators.

7.9.1 gas release regulator

83
- when temperature increases, mercury level rises and blocks gas
release.

7.9.2 heat electrical regulator

- when temperature increases, mercury rises and contact is

ensured with a wire closing an electric circuit, this activates a
magnet, which in turn isolates another electric circuit (including
resistance) that controls temperature in the device to be heated
(an oven, for example). This situation is activated as long as
temperature is in the defined range.

- when temperature drops, mercury surface drops, the wire

becomes isolated, the magnet is inactivated, and the heating
resistance circuit is closed to re-start heating the concerned
device.

7.9.3 thermocouple regulator

- two ends of a thermocouple are welded and connected to the
heating circuit inserted into the device to be heated (an oven, for
example), whereas the other ends of the thermocouple are
connected to a galvanometer.
- when temperature increases to the required level, an electric
current is generated in the thermocouple and the galvanometer
puts off the heating circuit.
- when temperature drops, no electric current is produced in the
thermocouple, so the galvanometers returns back to a position
that connects the heating circuit, and oven heating restarts
again.

84
End of Optional Reading

85