Met. Thermo.

S.P. Butee
 Historical Perspective of
Thermodynamics
• 1824 – Carnot -steam engine -second law of
thermodynamics evolved
• 1884 - Joule - ‘Mechanical Equivalent of Heat’
• Clausius concluded that the two phenomena are not
contradictory but are two different laws
• 1906- Nernst - ‘Third Law of Thermodynamics’
• ‘Classical Thermodynamics’ – a science which has evolved
out of the study of heat and its capacity to do work –
thermo appl. to heat engines.
• Concepts were found to apply to chemical systems
(Chemical Thermodynamics) and high temperature
chemical reactions involving metals its oxides and other
compounds (Metallurgical Thermodynamics)
 •
Thermodynamics and
WHAT MAKES A REACTION FEASIBLE?
Feasibility
• For any process to occur spontaneously it must be accompanied by
a decrease in the system's energy content. The change in energy
during a reaction, i.e. energy of products - energy of reactants,
must be negative for a spontaneous reaction.
• Extent of heat liberation - relationship with the driving force behind
the reaction.
• For high intensities of reaction, it was more difficult to revert to the
reactants
• HEAT AND WORK – ARE THEY SYNONYMOUS? WHAT DOES
THERMODYNAMICS SAY?
• The science of thermodynamics deals with transformation of other
forms of energy to heat, and from heat to other forms
• Term ‘dynamics’ in thermodynamics refers to ‘transformation’ rather
than transfer
• Science of heat transfer is covered under the science of
Thermophysics

State.
 ENTROPY
Reversible Operation (where equilibrium conditions are always
maintained):
• With slower rates of operation of the heat engine, the efficiency of
conversion of heat into work increased, tending to a maximum
when the conversion is carried out at infinitesimally slow speed
• (In practice this is neither possible nor desirable)
• Under such a condition, the efficiency of conversion of heat into
work depended only on the temperatures of heat source and heat
sink
• “thermodynamically reversible processes” replicate the “real
processes” in an “ideal mode”
• The “Entropy” remains constant if the process is carried out in fully-
equilibrated condition.
• For any other condition (i.e., for real processes), the ‘Entropy” of
system and surroundings taken together always increases.
• Entropy, which is the mathematical ratio of energy per unit absolute
temperature, has been found to represent the extent of disorder
(randomness) and irreversibility.
 LINKAGE BETWEEN HEAT ENGINES &
CHEMICAL REACTIONS
• If the engine operates at near equilibrated
conditions, the entropy increase can be kept
to a minimum.
• The more the heat engine operates away from
the equilibrium conditions the efficiency of
conversion decreases and the entropy keeps
on increasing.
 TERMS USED IN THERMODYNAMICS
• Science of thermodynamics - mathematical treatment
of common observations related to heat and work
• “Internal Energy” - state of the molecules or atoms –
all the energy contained within them – including
kinetic energy (vibrations in case of solids and velocity
of movements in case of fluids)
• “Enthalpy” or “Heat Content” (H) - At constant
pressure conditions more relevant. It is the sum total of
the “Internal Energy” and the work it has already
performed on the surroundings.
• H can be measured relative to any reference level
which is usually done by defining H = 0 for a pure
element in its most stable state at 298 K (25°C).
• “Entropy” - quantity of bound energy in the system per
unit absolute temperature. This bound energy is not
normally available for reactions.
 FREE ENERGY – THE MEASURE OF FEASIBILITY
• “Free Energy” - a part of the energy, which can be easily released.
• If substantial “Free Energy” is available which can easily leave the
system, the transformation is easily feasible.
• If no such “Free Energy” were available (is zero), the system would
not materially change (i.e., it is in thermodynamic equilibrium).
• Its variants, “Gibbs Free Energy” and “Helmholtz Free Energy” also
called the “Work Function”
• Free Energy of a system is the sum of the entropies of the system
and surroundings multiplied by the absolute temperature (with a
negative sign). Thus, Free Energy is another way of expressing
Entropy.
• Measure of feasibility of reactions - the heat liberated goes towards
increasing the entropy of the surroundings.
• “Free Energy” = Total Energy represented by “Enthalpy” or “Heat
Content, H” minus “Bound Energy, T*S” (E = H –TS)
• ‘Entropy’ and ‘Free Energy’, determine ‘Randomness’ and
‘Feasibility’ respectively.
 Basic Concepts
• WHAT IS THERMODYNAMICS?
• Thermodynamics deals with transformation of heat into
other forms of energy and vice versa.
Definitions:
• Thermodynamics is a science dealing with changes in
energies of systems and transformations of energy within a
system.
• Thermodynamics is a science that deals with heat and
work and those properties of substances that bear a
relation to heat and work
• Thermodynamics concerns itself with the study of energy
and the transformations of that energy.
• Thermodynamics deals with the conversion of thermal
energy into work.
• Non-atomistic and non-microscopic
• Cannot predict structure, mechanism and rate of reaction.
 WHAT IS A ‘SYSTEM’?
• A ‘system’ is that part of physical world, which is under
consideration.
• The rest of the physical world is called ‘surroundings.’
• System and surroundings together make up the physical
world, which we often refer to as the universe.
• System is separated from surroundings by ‘system
boundaries’.
• These boundaries may either be movable or fixed.
• A system may be open, closed or isolated.
• An ‘open’ system is one, which can exchange energy and
matter with the surroundings.
• A ‘closed’ system cannot exchange matter with the
surroundings (exchange of energy may take place).
• An ‘isolated’ system has a definite amount of energy and
matter and it cannot exchange them with the surroundings.
 Homogeneity and Heterogeneity
• A homogeneous system is completely uniform
throughout.
• A system is heterogeneous when it is not uniform.
• Two types of heterogeneous:
• Concentration of species may vary from one point to
another;
• System may consist of two or more ‘phases,’
• A ‘phase’ is a chemically homogeneous part of a
system, separated by definite bounding surfaces from
other similar phases.
• Within a phase, concentration gradient i.e., variation of
concentration from point to point, may sometimes
exist, but it would always tend to homogenise itself.
 STATE AND THERMODYNAMIC PROPERTIES
• The variables whose values determine the thermodynamic state of a
system are called its thermodynamic coordinates or its state variables.
• The ‘state’ of a system is defined by the properties the system exhibits.
• When the thermodynamic coordinates of a system change, the system is
said to undergo a process (reversible and irreversible).
• In a reversible process, when a given process has been carried out and
then reversed, both the system and its surroundings come back exactly to
their original states and no net change occurs in any part of the system or
the surroundings.
• On the other hand, a process which involves the spontaneous transition
of a system from a nonequilibrium state to an equilibrium state is called
an irreversible process (also called spontaneous or a natural process).
• If these properties do not depend upon the path the system has taken to
reach that equilibrium state, then they are called ‘State Properties.’
• Mathematically, State Properties are ‘Exact Differentials.’
 Other processes
• Isobaric process : Changes implemented at
constant pressure.
• Isothermal process: Changes occurring at
constant temperature.
• Adiabatic process: When a process is carried out
under such conditions that heat can neither leave
the system nor enter it. A vacuum flask provides
an excellent example a practical adiabatic wall.
• Cyclic process: When a system, after going
through a number of changes, reverts to its initial
state.
STATE AND THERMODYNAMIC PROPERTIES
• The equilibrium state is essentially the result of a
spontaneous process from a certain nonequilibrium
state.
• The determination of the equilibrium state is of key
importance in thermodynamics, since a knowledge of
this state permits the determination of the direction in
which any spontaneous chemical reaction will proceed
from any given starting point.
• If these properties do not ‘tend’ to change with time,
the system is said to be in an ‘equilibrium state.
• In equilibrium state, the properties tend to be
interdependent.
• It is possible that only a limited number of properties
will completely define an equilibrium state of a system.
 State Properties
• If any thermodynamic property ‘G’ of a system is a single-
valued function of certain variables x, y, z, etc., which
again are the properties of the system; then G is called a
state property of that system.
• It means that G does not depend upon the path taken to
bring the system to that state or condition and depends
only on the properties of the system in that state.
• For example, the state of one mole of an ideal gas is
completely defined by defining pressure and
temperature, and under these defined conditions, it as a
definite specific volume.
• All the three i.e. pressure, temperature and specific
volume of an ideal gas are its state properties.
 Intensive and Extensive Properties

• Extensive property of a system is a thermodynamic property,

which is dependent upon the quantity of matter or size of the
system (e.g., volume, energy, mass, kinetic energy, heat capacity).
• Extensive properties are additive. Its value for the whole system is
the sum of the values of individual parts.
• An extensive property can be treated like an intensive property
by referring it as the unit amount of the substance concerned.
(e.g. mass and volume are extensive properties, but density,
which is mass per unit volume, and specific volume, which is
volume per unit mass are intensive prop.)
• Entropy is an extensive property (i.e. dependent on mass) the
total entropy, S, of systems S1 and S2 is given by S = S1 + S2, i.e.
they can be added
 Intensive and Extensive Properties
• Intensive property is a thermodynamic property, which
is independent of the mass (independent of system
size) of the system.
• These properties are not additive (e.g., temperature,
pressure, concentration, molar volume, specific heat).
• The value for the whole system is not the sum of the
values for different parts.
• The intensive properties are those which are
independent of the size of the system such as T and P,
whereas the extensive properties are directly
proportional to the quantity of material in the system,
e.g. V, E, H, S and G.
• Like internal energy, enthalpy and heat capacity are
also extensive properties.
 THERMODYNAMIC EQUILIBRIUM
• A system is said to be in Thermodynamic
Equilibrium State when its state properties
have defined values, which do not tend to
change with time.
• For example, molar volumes of all ideal gases
are same at a particular temperature and
pressure.
 WORK - DIFFERENT FORMS
• Mechanical work - ‘work is done’ when a body moves
under the influence of a force.
• When the point of application moves in the direction in
which the force acts, work is said to be done by the
force (or ‘the force has done the work’).
• If the point of application moves in the direction
opposite to that of the force, work is said to be done
against the force (or ‘work has been done on the
force’).
• Work is generally denoted by the symbol ‘W’. If a
system expands against the incumbent pressure of
the surroundings, the system is said to perform work
on the surroundings and W is assumed to be positive.
• If the system contracts under the influence of the
pressure of the surroundings then ‘W’ is assumed to be
negative.
 WORK - DIFFERENT FORMS
• Chemical Work - Chemical reaction, when a molecule
is broken, work is performed to break the bond, which
had been holding the atoms together in the molecule.
• On the other hand, work is done by the atoms, when
joining together to form new bonds and thereby a new
molecule is formed.
• Electrochemical Work -when the applied electrical
potential (e.m.f.), forces the ions to break the
electrovalent bond and then move them towards a
particular electrode.
• Electrical work - when electrons move in conductors,
overcoming its resistance and applied potential
BRANCHES OF THERMODYNAMICS
• Thermodynamics deals with the conversion of thermal
energy into work. The work may be mechanical, or of any
other type.
• ‘Mechanical Engineering Thermodynamics’ / ‘Engineering
Thermodynamics.’ - steam locomotives perform
mechanical work - manifests itself into displacement of a
body.
• ‘Chemical Thermodynamics. - Heat evolution or absorption
is also involved when substances react chemically to form
new molecules. In forming these new molecules, the atoms
in the old molecules have worked against the forces binding
it and in the process have used some energy available in
the vicinity – releasing some of it when it gets bound into
the new molecule. Chemical work is required to be
performed to make these new molecules revert back to the
reactants. Science of study of energy changes in such a
process is Chemical Thermo.
BRANCHES OF THERMODYNAMICS
• Science of study of a process where a chemical change generates
electricity or vice versa as in the charging of an electro-chemical
cell, when the imposed electro-motive force pushes the electrically-
charged ions to a higher energy state, is referred to as ‘Electro-
chemical Thermodynamics.’
• Similarly, Metallurgical Thermodynamics is that part of
thermodynamics, which deals with energy changes in reactions
involving metals and their compounds. Many look upon it as the
“High-Temperature Chemical Thermodynamics.”
• Thermodynamic properties based on the properties of micro
constituent (atoms and molecules) of the system. This branch is
called the “Statistical Thermodynamics.”
• “Nuclear Thermodynamics” - Where matter is treated as another
form of energy and role of atomic and subatomic particle forms are
studied.
• The science dealing with the basic concepts, the thermodynamic
laws and their understanding is termed as the “Classical
Thermodynamics.”
 BASIS OF THERMODYNAMICS
1ST AND 2ND LAW OF THERMODYNAMICS

0th LAW OF THERMODYNAMICS

(A, B and C are equally hot or at the same temp.)

Zeroeth Law of thermodynamics emphasizes the fluid nature of heat – a property also exhibited
by most of the other forms of energy (e.g., Electrical Potential in a conductor)
Usages and Limitations
• https://www.youtube.com/watch?v=nfMO7_hwYuE
• https://www.youtube.com/watch?v=EPTKg_gyCmE
• https://www.youtube.com/watch?v=XMknQYdAeLo
(ELECTROCHEMISTRY gate QUESTIONS)
• https://www.youtube.com/watch?v=Wo071BondS8
(SECOND AND 3RD LAW)
• https://www.youtube.com/watch?v=vDNlGG3O2Cg
(Ellingham Diagram)
• https://www.youtube.com/watch?v=0lcOTWrsAxI
Thank you!
• Two types of open systems exist: (1) steady-
state, and (2) unsteady state.
• If the properties of any part of the system are
constant, regardless of the duration of an
operation or a process, the so-called open
system is the steady-state flow system. When
the properties of any part of a system undergo
fluctuation and variation, the open system is
then termed as an unsteady state flow system.
 First Law
• Different statements:
(i) energy can neither be created nor destroyed though it may be converted
from one form to another;
(ii) whenever a quantity of one form of energy disappears, its equivalent in
another form makes its appearance;
(iii) for a system in contact with its surroundings the sum of the energies of
the system and its surroundings remains constant howsoever differently it
may be shared between the two; and
(iv) it is impossible to make a perpetual machine which would produce work
without consuming energy.
• It introduced the concept of conservation of energy
• The system and its surroundings together constitute an isolated system
and, according to the first law, the total energy of an isolated system is
constant.
• The total energy is also called the internal energy and it represents the
sum total of all types of energy contained within the system boundaries.
• It is not possible to assign an absolute value to the internal energy of a
system; however, changes in internal energy can be measured.
 Closed system undergoing a change of
state or a process
(Only energy transfer takes place and no mass transfer)

• If q is the amount of heat transferred to the

system and w is the amount of work transferred
from the system, then the change, ΔU, in the
internal energy, U, of the closed system can be
expressed as
• ΔU = q − w
• Here, q is considered to be the heat absorbed by
the system from the surroundings and w, the
work done by the system on the surroundings.
 First Law
• Internal energy U is a state property.
• The changes in it dU or ΔU, are said to be path independent.
• Heat and work changes between the two states depend on the
manner in which the process is carried out viz. depends on the path
that the system traverses in going from one state to the next.
• The quantities δq and δw are, therefore, path dependent.
• Changes in state functions such as U, V, T are indicated as dU, dV,
dT, similar changes in path-dependent quantities like heat and work
are represented as δq and δw.
• In mathematical parlance, dU is a perfect differential, while δq and
δw are not.
• When the path is specified, the changes in q and w become definite
and differential changes in these quantities can be represented as
dq and dw. The first law may then by expressed as
• dU = dq − dw
 First Law
• When a process is carried out at a constant pressure, P, the work
done by the system can be represented as:
dw = P dV
• and the first law expression is
dU = dq − P dV
• In chemical systems conservation of energy is usually handled in
terms of three quantities:
(i) Work done by the system on the surroundings which is taken as
plus (+) w or the work done by the surroundings on the system
which is taken as (−) w;
(ii) Heat gained by the system (+q) and heat lost by the system (−q);
and
(iii) The increase (+ΔU) or decrease (−ΔU) in the internal energy of the
system as a result of the process carried through.
 Thermochemistry
• The specific application of the first law of
thermodynamics to study chemical reactions is
referred to as thermochemistry.
• It deals with measurement or calculation of the
heat absorbed or given out in chemical reactions
• It is the part of thermodynamics dealing with
“enthalpy (i.e., heat content) changes”
accompanying chemical reactions.
• Heat capacity, C, of a system is defined as the
heat introduced or withdrawn to raise or lower
the temperature of the system by one degree
celsius.
• Thus,
 Thermochemistry
• The concept of heat capacity is used only when the
introduction of heat to, or the removal of heat from, the
system brings about a corresponding change in temperature.
• Not used in certain situations such as those involving phase
changes
• For e.g. at melting point as the definition goes, C would be
infinite.
• C is an indefinite quantity even when mass is specified, since
δq is so.
• At constant volume or constant pressure conditions, the heat
capacity becomes a definite quantity (Cv and Cp).
• For reactions or other processes carried out in containers that
are open to atmosphere we can assume the pressure on the
system is held constant.
Heat capacity (Cv and Cp)
Enthalpy
 Different types of reactions
• The heat absorbed in a process at constant pressure is equal
to ΔH, the increase in the enthalpy of the system.
• Heat of reaction, ΔH
ΔH = ∑H (products) - ∑H (reactants)
• Where all the enthalpy values refer to the specified
temperature and a pressure of one atmosphere.
• Exothermic reaction (ΔH is positive) Causes evolution of heat,
• Endothermic reaction (ΔH is negative) Causes absorption of
heat.
• Similarly, heat of formation of a compound, the heat of
combustion of a substance, the heat of transformation, and
the heat of solution for other reactions can be defined.
 Different types of reactions
• Heat of formation of a compound is the change in
enthalpy that results when one mole of the
compound is formed from its constituent
elements.
• Since the absolute value of the heat content of a
substance is not known, the convention in
thermochemistry is to take the heat contents of
elements in their standard states, i.e., in their
stable forms under one atmosphere pressure-to
be zero, at 25 °C (298 K).
 Different types of reactions
• The heat of formation of one mole of a compound at 25 °C,
as defined above, turns out to be the same as the heat
content of one mole of the compound at 25 °C.
• The heat of combustion of a substance is the enthalpy
change that occurs when one mole of the substance (an
element or a compound) is completely burnt in oxygen.
• The heat of transformation is defined as the change in
enthalpy that results when one mole of a substance
undergoes a specific change of state such as melting,
evaporation, or allotropic modification.
• The heat of solution is the enthalpy change that occurs
when one mole of the solute is added to form a solution of
a particular concentration.
 Hess’s Law
(first of two important relationships in the thermochemistry)
 Kirchoff’s Equation
(second of two important relationships in the thermochemistry)
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