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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. Calorimtrie (Bunzen ice-calorimeter, thermostat, thermocouple and Stefan law
of heat radiation)
14. Newton Cooling Law
15. Thermal expansion and determination of heat conductivity coefficient
A sketch that gives a rapid summary of the types of thermodynamic process
Meaning of the word and 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 (capacity
of a body to do work). Today, the scope includes energy and its relationship with
the MACROSCOPIC properties of matter. Engineers use the principles of
thermodynamics to conceive and analyze natural processes and 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 zero

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 designetc.).
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 deal only 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. Consequently, 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 close to)
equilibrium, assuming that the 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 is used in studying
equilibrium in the natural systems in geology, soils, water resources, and recently in
biology. Since equilibrium is not reached in most cases on the Earth crust (or
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 in terms of global
parameters; like mass, temperature, pressure, chemical potential, Gibbs 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 them 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
equilibrium may not actually be realized, and the natural processes are
irreversible and difficult to study. However, we assume equilibrium and any
irreversible process is composed of small reversible processes to be able to
solve it. This is admissible since the change in internal energy and
entropy are independent of pathway (since they are state functions)
whereas work and heat depend on the pathway (since they are non-state
functions) and the system does not contain work or heat, considering that the
thermodynamic process is an action leading to shift of the situation from
one equilibrium 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 may use thermodynamic predictions.
- It is 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 (for dealing with its temperature,
volume, temperature capacity, etc.) but we do not deal with the impact of these
characteristics on the internal structure and/or arrangement of atoms . In
addition, 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 behind the interest in thermodynamics and source of its authority. 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 enough relative to the
studied system. Thermodynamics is concerned only with the study of systems at
equilibrium, When some perturbation takes place, thermodynamics can predict
the new equilibrium (but cannot predict the pathway or the mechanism nor the
rate of reaction).
However, there is a field of non-equilibrium thermodynamics that will not be
dealt with here. In addition, some aspects that cannot be covered by
thermodynamics can be covered by kinetics. In fact, there is a close relationship
between kinetics and thermodynamics.
Energy - meaning and types
It is the capacity for doing work. Energy can exist in many forms:
1. Radiation, 2. Kinetic (vibration, oscillation, translocation) , 3. potential, 4.
chemical, 5. atomic (nuclear) energy, 6. electromagnetic, 7. electric and 8. heat
(thermal) energy .
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.
The thermodynamic variables are either intensive or extensive.
Intensive, i.e. it does not change with the number of moles of matter
- Density (kg/m
- Temperature (K)
- Pressure (N m
- Chemical potential, = = (J mol
Known also as the molar Gibbs free energy
Extensive, i.e. it changes with the number of moles of matter
- Gibbs free energy, G (J K
- Entropy, S (J K
- Enthalpy, H (= Work + Internal Energy) (J K
- Volume (m
- Mass (kg)
State Functions, and Non-State Functions
State Functions
(A function that does not depend on the pathway = trajectory the system will
follow to realize a change. A state function has exact differentials )
- 1- Volume, V
- 2- Internal energy, U
- 3- Entropy, S
- 4- Enthalpy (H = U + W)
- 5- Gibbs free energy, G
- 6- Equilibrium
Non-state Functions
(A function that depends on the pathway the system will follow to realize a change.
A non-state function has inexact differentials )
- 7- Work, W
- 8 Heat, Q
Thermodynamic Processes
When a macroscopic system shifts from an equilibrium to another, a process is
said to be taking place. There are two types:
- reversible (like thawing and freezing). In many processes the idea of
irreversible process is just an idealization. In fact, it may be approached, but not
perfectly achieved. However, its formula is very useful for solving problems when we
cannot directly use the formula of an irreversible process, in particular when the
studied variable is a state function (i.e. independent on pathway) since the irreversible
may be replaced by a series of imaginary reversible steps (that starts from the same
initial condition, and ends-up at the same final condition as the irreversible process),
hence an integration procedure leads to calculating the change that takes place
during the irreversible process of interest.
- irreversible (evaporation , dissolution , diffusion , gas seepage
through openings from a high pressure reservoir to a law pressure one, mixing of
solutions, gas mixing, weathering , rusting of iron, coagulation , aging (growing
older), heat flow from a hotter to a colder reservoir, also saline solutions (or ink and
water) do not separate by itself into salt (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 change . Heat and work have a common feature:
they both depend on the pathway , (i.e they are non-state functions) .
Laws of thermodynamics
These laws were discovered in the 19
century through painstaking
experimentation. They govern the thermodynamic processes and put limits on
The Zero

When two bodies (A) and (B), in thermal equilibrium, are in equilibrium
with a third body (C), the two bodies (A) and (B) will have the same
When each of two systems is in thermal equilibrium (no heat flow) with a third
one, the first two systems must be in equilibrium with each other.
Simple application : you may use a thermometer to measure temperature!
Note that for some unknown reason the Zero
Law came after the First Law.
The First law
This is a law that denies the possibility of creating or destroying energy (and
this is generally known as the energy conservation principle
The Second law
This is a law that denies the possibility of utilizing energy in a particular way
(work can be dissipated completely into heat whereas heat cannot be converted
100% into work.
This principle reflects the one-sidedness (one directional progress) of the
spontaneous - natural - processes.
Definition of Temperature
Difficult to define (since it is related to our sensation of hot and cold
bodies). Consequently, we better refer to the equity of temperatures . This
equity idea leads to the Zero
law of thermodynamics, and it is the basis of
temperature measurement.
For gases, temperature is a measure of the average kinetic energy of gas
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 (i.e. the absolute zero) at which the
volume of the ideal gas is zero (note that real gas should have a given volume at
the absolute zero.)
Temperature definition using the Zero
t h
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 zero
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 zero

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 environmentthat is, it reaches the same temperature as the
surroundings (we will soon study Newtons 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.
The 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 .
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,
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
Formulas of the First Law & Thermodynamic Processes
1. adiabatic process where there is no heat transfer (Q = 0) and net work
(done on or by the system) is the same as the change in internal energy.
- U
= U = -W
Enthalpy = (U
- U
) + W = 0
2. iso chor ic process, there is no way to carry out work (so, W = 0), and
U = Q
3. iso bar ic 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
Work can easily be calculated from the relationship:
W = P (V
- V
For gases W = P.V = C

4. isothermal process, the internal energy (and temperature) does not change,
(U = 0) and
Q = W
The work done by the system is positive, (so the internal energy decreases),
whereas the work done on the system is negative, (so the internal energy
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
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
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
A system that exchanges both matter and energy with its surroundings.
- Einstein's famous equation E = M C
(describing the relationship between energy and matter)
supports the credibility of the first law of thermodynamics.
- Historically, work units were erg and joule, whereas heat unit is calorie.
- One calorie is equivalent to 4.186 10
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. In addition, various familiar systems, such as automobile
engines, exhibit adiabatic phenomena.
How the 1
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 an 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 1
law of
thermodynamics) rules out = denies the possibility of this imaginary
perpetual machine ever being invented.
The Second Law of Thermodynamics
Heat can never pass spontaneously from a colder to a hotter body.
As a result the natural process that involves energy transfer must have one
direction and all the spontaneously natural processes are irreversible .
This law also predicts that the entropy of an isolated system left to
itself (without human intervention) will always increase with time ( if all
components are taken into account ).
This law can also be expressed in several ways as follows:
- If we let a natural system to its own, the only change will be towards the state
that has a maximum probability ( usual with much more disorder ) .
- It is impossible to introduce wastes through a discharge point, to produce
nutrients at an input point!
- It is impossible to build an engine capable of heat transfer in continuous circulation
from a reservoir at low temperature to another one at higher temperature
spontaneously (without work done by an external engine). It is impossible to cool-
down the air space inside a refrigerator, or a room, spontaneously and, on the
contrary, we need work to do that task .
- Heat can never be extracted, and completely transformed, into work (since there is
something, which we call the increase of entropy).
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
hot end of the system at high temperature , while keeping the 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 due to the progress of the natural
irreversible spontaneous processes.
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 (CO
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,
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 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 has been described the heat death of the universe .
- Entropy (J K
) - the meaning
It is a measure of disorder (randomness) of energy (and matter) in a
system. The change of entropy ( S) is defined by the integration of the
change in the transferred heat (d Q) divided by temperature (T):
For an infinitesimal change, we write
1. For an irreversible process, this relation is 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
When mixing equal masses of hot and cold water, 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 >
2. For non-cyclic single reaction, that is infinitesimal and reversible
process, under isothermal conditions

Q = T d

To calculate total entropy change under isothermal conditions (e.g.
ice melting):
3. When considering several reversible processes in a cycle process
(like Carnot cycle, and thawing-freezing), we get:
This means that the reversible cyclic process is a special case of the
irreversible process (with entropy increase in part of the system
balanced by entropy decrease in the other part .
This is the criterion for thermodynamic equilibrium.
In fact, here S = 0, since cycles (like Carnot cycle) have no
irreversible process.
Remember, entropy can never decrease in a 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 is known as an isentropic process.
But for an irreversible adiabatic process (like free 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 equations 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!).
Combining the 1
U = Q - W
in its isobaric infinitismal form (where V.dP = 0)
dU = d Q - d W
with the 2
law for a reversible reaction
dQ = T dS
we can write the following formula:
dU = T d S - d W
d U = T dS - P d V
The second law of thermodynamics gives a definition of a property called
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 that Nature seems to prefer disorder, or chaos .
It can be shown that the second law stipulates (= imposes a condition) that, in
the absence of a particular work (introduced through a given
human arrangement like in refrigerators and air-conditioning),
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.
The 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 on the vertical axis and temperature on the horizontal axis in an
isobaric process, the temperature of -273.16 Celsius is obtained at pressure zero). The
third law of thermodynamics states that:
The Absolute zero cannot be attained by any procedure in a finite
number of steps. The 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
Absolute Zero = 0 degrees Kelvin = -273.15 degrees Celsius.
For all materials, entropy is zero at 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 = m C dT i.e. C = d Q / m d T
In addition, for a reversible process , we already know that
dS That is to say dQ = T d S
By substitution: C = T d S / m d T
dS = m CdT
= m C
Consequently, the value of entropy, S, can be obtained by integration of
this equation (and the term under the integral in the right-hand side is normally
formulated as a polynomial, for which the solution is known.) The example of mixing
of mass, m, of hot water with a mass, m, of cold water is showing this integration for
any of the two bodies:
hot or cold
= = m . C . = m . C .
with m mass (of hot or cold water), kg.
C specific heat of water (4190, J/Kg . K)
assumed constant for the applied temperature range.
T temperature, in degrees Kelvin
S J / K
The absolute zero is the temperature at which Carnot ideal calculation of
efficiency (e
) leads to e
= one (i.e. 100%), for a vapor machine (blue
line in the following diagram) or an explosion motor (red line in the diagram);
something which is completely impossible.
Theoretically, at 20 C (= 20 + 273.15 = 293.16 K) the efficiency e
is 0.38 for the
vapor machine, and 0.77 for the explosion motor. However, the real efficiency is
much less for both for several industrial/technologic reasons.
Note that the x-axis on left-hand side diagram is on Celsius temperature scale,
the right-hand side diagram is on the Kelvin temperature scale.
Thermodynamic Cycles
All the 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
enginethat is, all the heat would be converted to mechanical work.
In the 19th-century the French scientist Nicolas Lonard 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
kind) 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 much 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
Lonard 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 .
Carnot showed that the efficiency of any engine depends on the
difference between the highest and lowest temperatures reached
during one cycle.
The greater the difference, the greater the efficiency.
An automobile engine, for example, would be more efficient if the fuel
burned hotter (T
), and the exhaust gas came out of the
cylinder at a lower temperature (T
). Note that (T
) and (T
must be in Kelvin.
The 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 sizethat is, ordinary on the human scalecontain
immense numbers (in the order of 10
) of molecules. Assuming spherical molecules,
each would need three variables to describe its position and three more to describe its
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 the macroscopic thermodynamic variables.
The statistical treatment of molecular mechanics is called statistical mechanics,
and it anchors thermodynamics to mechanics.
Viewed from the statistical perspective, temperature can be defined
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 because of
collisions. The transfer will continue until uniformity is achieved , in a
statistical sense, which corresponds to thermal equilibrium .
Heat can be defined as the kinetic energy of the molecules since it
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
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
classical physics.
In terms of quantum mechanics, residual molecular
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.
The Second Law and Equilibrium
For all materials, the entropy is zero at the absolute zero. At any
temperature (T), we can calculate the change of entropy for a material in a
reversible process from the relation defining the specific heat capacity:
d Q = m C dT i.e. C = d Q / m d T
In addition, for a reversible process , we already know that
dS That is to say dQ = T d S
By substitution: C = T d S / m d T
dS = m CdT
S = m C
Note: If we deal one mole of material we do not use the mass
Consequently, the value of entropy, S, can be obtained by integration of
this equation (and the term under the integral in the right-hand side is normally
formulated as a polynomial, for which the solution is known.) The example of mixing
of mass, m, of hot water with a mass, m, of cold water is showing this integration for
any of the two bodies:
hot or cold
= = m . C . = m . C .
with m mass (of hot or cold water), kg.
C specific heat of water (4190, J/Kg . K)
assumed constant for the applied temperature range.
T temperature, in degrees Kelvin
S J / K
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 that determines the free enthalpy
(the energy that is free for carrying out the reaction). i.e., a measure that determines
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 looking
for 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
G Gibbs free energy change, in J/kg, or, in kJ/mole.
H enthalpy (= U+ PV), in J/kg, or, in kJ/mole.
S entropy (disorder or randomness), in J/mole.K.
The term (H - T. S) means: the chemical work done in order to tackle 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 and lost fraction of energy is already consumed in
the increase of entropy. This is a natural role in the universe; it cannot be
Reactions will be initiated, and go on spontaneously, as long
as the Gibbs free energy difference (the change, G) between
two suggested reacting materials is a negative value (G < 0).
At G = zero, equilibrium is achieved.
If (S) and (H) are both positive, and T S > H , a melting reaction may
If (S) is positive, and (H) is negative, an ignition reaction can occur.
If (S) and (H) are both negative, and T S > H , a crystallization (or a
solidification) reaction can occur.
In any other case of sign, reaction cannot
occur (e.g. when both S and H are either positive or negative, and
T S < H) . In addition, when S is negative and H positive .
In fact, to know if a certain chemical reaction or a certain physical process
can or cannot occur, calculate G for the
reaction (by addition of the G of formation for the components phases -,
including the reactants and products and their stoichiometric coefficients). If the
obtained G is negative the reaction can occur.
If it is zero , the reaction is at equilibrium .
We usually use an equality that says that the (G
) of reaction is the sum
of (G
), at the standard state, and the term (RT ln K
= G
+ R T l n K
R T l n K
= G
- G

l n K
= (G
- G
)/R T





Now, as we know that at equilibrium, G
= zero, consequently,



Hence, we use this formula to calculate the equilibrium
constant K
using G
obtained from the thermodynamic tables (knowing
the G
of reactants and products). In addition, we can obtain a calculated K
value (the ionic activity product) and compare it with theoretical K
, in order
to know if a system is at equilibrium, K= K
), far behind (under-saturated, K
), or it has already by-passed the equilibrium status (over-saturated, K>K
In reactions that take place in aqueous solutions, we obtain the intensive
property known as the chemical potential by dividing G by the number
of moles. We write a relation (similar to what is given above) for the
chemical potential,
, of each aqueous species (ions and complexes):

+ R T l n a
R T l n a

l n a
= (
)/R T


the activity of the aqueous species (activity is the product of molality and
activity coefficient; and the later is the fraction of the total concentration that is
contributes in the reaction).
Thermodynamics and Chemical Reactions
In a chemical reaction like:
a A + b B = c C + d D
A, B, C, D concentrations (or activities or pressures) of reactants and product.
a, b, c, d their stoichiometric coefficients.

thermodynamics can be used to understand the equilibrium constant K (or the
solubility product, K
in the dissolution-precipitation reactions, or the standard half-
cell potential in the redox reactions) which describes the tendency of the
reactants to form products.
l n K = c ln [C] + d l n [D] - a l n [A] - b l n [B]
In a chemical reaction, a change in composition takes place since the
reactants are transformed into products. This is associated with certain change
in internal energy (U) that results in difference of the internal energy of
products and reactants that reflects the difference in mechanical stability of both
(since any amount of macroscopic chemical substance is an agglomeration of
numerous simple mechanical systems). U can be obtained 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
) which will
be equal to (U). From the first law, U = Q - W, and since W= 0, we get:
U = Q
2. Carrying out the reaction under constant pressure (isobaric conditions) - as
usual under atmospheric pressure - and measuring the emitted (or the
absorbed) heat (Q
) 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. Q
is greater
than Q
by the work done). Enthalpy is a state function that is defined (only
under isobaric conditions) as following:
H = U + W
H = U + P. V
H = Q
- W + P. V
H = Q
(In both methods, 1 and 2, when an exothermic reaction takes place, Q will be
negative, i.e. energy of products will be lower than energy of reactants, whereas
when an endothermic reaction takes place, Q will be positive, i.e. energy of
products 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

) for the reaction from formation enthalpy ( H

) of
reactants and products in their standard states (stoichiometric coefficients
are for sure included).

(when the range of temperatures under which the reaction takes place is small,
we suggest that enthalpy of reaction, H

, does not depend on temperature
since C
will be small to ignore the integral in the formula for one mole:
= H
under isochoric conditions: i.e. d U = C
. d T
and under isobaric conditions: i.e. d H = C
. d T
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 infinitesimally 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
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 dG was negative (dG<zero), the process should be
irreversible, whereas if dG= zero, the process is reversible. Using the entropy
change S, if S increases, the process can be defined as irreversible, if S=zero,
the process is reversible, if S decreases, the process is impossible to occur
Contrary to enthalpy, entropy is highly affected by temperature change :
under isochoric conditions: S =
that is to say: S =
under isobaric conditions: S =
For liquids: S =
S = m C
S = m C
For one mole, at any given temperature, T, starting from absolute zero:
S = S
- S
= C
But since entropy
(at absolute zero)
=zero (S
=0), we get S
(in J mol
= C
In fact, we are only interested in S

that is associated with the
chemical reaction. Its value can be calculated using the tabulated
values of S

(note: S

is the standard entropy of formation, at

C, in thermodynamic tables).

For liquids evaporation: S =
S =
And if evaporation is considered as a reversible process (instead of its
reality as irreversible process) taking place under isobaric conditions, the
amount of heat Q, added to the system, will be equal to enthalpy of
Q = H
Hence, S = =
For all liquids, S associated with evaporation = approximately 87.9 J K
When S

is a small positive value, the reaction is irreversible and
the structures of reactants and products are similar (like in evaporation), whereas
if S

was 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 a
simpler criteria, that depends only on system characteristics; this criteria
is known as Gibbs free energy G (it is a state function, just like volume,
internal energy, entropy and equilibrium, i.e. its change G, does not
depend on the pathway, but only on the initial and the final situations).
End of Optional Reading
7.1 temperature scales
7.1.1 Celsius (Swedish scientist)
Before 1954 two points were selected
- upper: water boiling assigned 100

C (temperature of water and vapor
mixture in equilibrium under 1 a tm).
- lower: ice point assigned 0

C (temperature of water and ice in
equilibrium with saturated air under 1 atm).
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
(and practically, water boiling point = 100
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)
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
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
= P h atm
0 0
+ = P h atm
100 100
+ = P h atm
t t

100 0
h h
h h

100 0
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
- thermocouple
- Platinum resistance thermometer
- a Wheat stone bridge is used to measure the electric resistance R.

100 0
End of Optional Reading
7.3 internal energy and thermal energy
7.3.1 Internal energy
- Internal energy =
Sum of
Kinetic + Potential + Pressure + 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 matters unit mass without
changing its temperature. (Melting, vaporization,
solidification). (Contrary to sensible heat that can be measured)
7.5.2 Heat of evaporation
- Amount of heat to transform liquids mass unit into vapor.
Heat of condensation
- Amount of heat to transform vapors mass unit into liquid.
7.6 specific heat measurement (calorimtrie )
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 * (

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:
Derivation of the Newtons Cooling Law
d T
d t

( )
d T
d t
k T C

( ) d T k d t T C .
Divide both sides by (T - C) and
multiply by (-1) to prepare for integration
( )

d T k d t .
By integration of (T-C) at time, t=0 zero t=t
( )
( )
( )

d T k d t
t t
. ( ) ( )
[ ]

ln ln T C T C k d t
( )
( )

k t
( )
( )

ln /
k time

( )
( )
k t

( ) T T C e
k t

h A
m S

k temperature decay constant, (in time
Room temperature (C) which is assumed constant and >T
thermal convection coefficient
A the cross-section area
m mass
specific heat
- Note that 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, Newtons law
can be used to know time, t
- knowing the values of k, S
, A and m, the last formula can be
used to determine the value of h
, but usually we get its value
by dimensional analysis or by experimental work.
Note that specific heat S
can also be obtained using equal
cooling rates of two different liquids knowing the specific
heat of one of them (e.g. water) when we heat both to same
temperature then we left them to cool-down in the same room.
Consequently, they cool down during different times, t
and t
but the two cooling rates (amount of heat divided by time for
each liquid) are equal (note that the masses of two calorimeters
are m
cal 1
and m
cal 2
and they are made-up of the same
material, so their specific heat, S

, is the same). Hence, we
can calculate the unknown specific heat of the liquid , S

( ) ( ) m S m S
m S m S
cal cal water water cal cal liquid liquid 1

Newton's Cooling Law
0 10 20 30 40 50
time, minute
T and T-C o
T model
room temp.
T-C model
always temperature differs
50 52 54 56 58 60
time, minute
room temp.
In the bottom diagram that we use ln of the inverse fraction, hence the
negative sign disappeared.
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.s
- 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 bodys specific heat can be determined.
- Preparation of the apparatus for experimental work (page 143).
- Mass of molten ice is calculated from the observation of the
recession of Mercury in capillary tube.
r l

10908 10001 . .
m * L = m * S *
(2 1)
2- Condensation method
- hot water vapor at 100
C is inflow is conducted into a
chamber where a body (of mass m
) is suspended at the plate of
a balance, body temperature increases from to 100
whereas a fraction of vapor condenses (its lost heat is controlled
by its latent heat, L, and the condensed mass, m).
m * L = m
* S * (100 )
7.7 thermal expansion
7.7.1 solid-phase expansion
- longitudinal expansion coefficient (

d L
d T L
(T = temperature)
- volume expansion coefficient (

d T V
Suppose the body is homogenous in three dimensions, so:
( )
dV L d l 3
divide by d T
( ) dV
d T
L d l

divide by V = L
( ) 1
d T
L d l
dT L

( )

d l
dT L
7.7.2 liquid-phase expansion
- liquid volume expansion coefficient (

real apparent container
7.7.3 gaseous-phase expansion
- previously dealt with under Charles law.
t o


7.8 heat transfer
7.8.1 by convection
- Heat flow mode with the movement of fluid particles due to
decrease of density with temperature increase (convection
- Water column stratification in deep lakes.
- Flow of air during air-conditioning.
- Flow of air from sea-side inland and vice versa during the day.
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 :

1 2

(d = distance)
- exposed cross-section area, A.
- duration, t.
Q t
Q A t R
Q k A t

1 2
Thermal conduction coefficient, k:
( )

1 2
Determination of heat
conductivity coefficient
- By Searles 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
( )
Q k A t
m S

1 2
4 3
( )
( )
m S d
A t

. .

4 3
1 2
- 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
Q k A t
m S

1 2
7.8.3 By radiation
- no need for any material medium for heat transfer by radiation.
- Stefan law:
( )
R e T T
e = constant.
= emission coefficient (fraction in the range from 0
= body temperature, k.
= surroundings temperature, k.
= net emission by radiation, watt/ m
i.e. Joul
- Heat radiation measurement
by a thermopile
- The thermopile is a set of thermocouples connected in series.
The extreme ends are connected to a galvanometer.
- The welded points are exposed to radiation increases, whereas
the non-exposed welded points are exposed.
- Temperature gradient generates an electric current that can
be read by the galvanometer.
7.9 other applications of heat theories
- Thermostats are used to control constant temperature in oven,
refrigerators and incubators.
7.9.1 Gas release regulator
- When temperature increases, mercury level rises and blocks gas
7.9.2 Heat electric-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
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
End of Optional Reading