Chapter 1

By,
Prashant Kumar
 Enthalpy
• When a process takes place at constant pressure, the heat absorbed or released is
equal to the Enthalpy change.
• Enthalpy is sometimes known as “heat content”, but “enthalpy” is an interesting
and unusual word, so most people like to use it.
• Enthalpy(H) is nothing but the sum of the internal energy(U) and the product of
pressure(P) and volume(V).
• Enthalpy H can be written as,
• H = U + pV
• Where, H = Enthalpy of the system
• U = Internal energy of the system
• p = Pressure of the system
• V = Volume of the system
 The Steady State Steady Flow
Process
•  A steady state is a situation in which all state variables are constant in spite
of ongoing processes that strive to change them.
• For an entire system to be at steady state, i.e. For all state variables of a
system to be constant, there must be a flow through the system
(compare mass balance).
• One of the simplest examples of such a system is the case of a bathtub with
the tap open but without the bottom plug: after a certain time the water flows
in and out at the same rate, so the water level (the state variable being
volume) stabilizes and the system is at steady state.
• Of course the volume stabilizing inside the tub depends on the size of the
tub, the diameter of the exit hole and the flowrate of water in.
• Since the tub can overflow, eventually a steady state can be reached where
the water flowing in equals the overflow plus the water out through the
drain.
• A steady state flow process requires conditions at all points in an
apparatus remain constant as time changes.
• There must be no accumulation of mass or energy over the time period of
interest.
• The same mass flow rate will remain constant in the flow path through
each element of the system.
• Thermodynamic properties may vary from point to point, but will remain
unchanged at any given point
 Phase Rule
• The Phase Rule describes the possible number of degrees of freedom in
a (closed) system at equilibrium, in terms of the number of separate
phases and the number of chemical constituents in the system.
• It was deduced from thermodynamic principles by J. W. Gibbs in the
1870s.
• The Degrees of Freedom [F] is the number of independent intensive
variables (i.e. those that are independent of the quantity of material
present) that need to be specified in value to fully determine the state
of the system.
• Typical such variables might be temperature, pressure, or
concentration.
• A Phase is a component part of the system that is immiscible with the
other parts (e.g. solid, liquid, or gas).
• A phase may of course contain several chemical constituents, which
may or may not be shared with other phases. The number of phases
is represented in the relation by P.
• The Chemical Constituents are simply the distinct compounds (or
elements) involved in the equations of the system. (If some of the
system constituents remain in equilibrium with each other whatever
the state of the system, they should be counted as a single
constituent.) The number of these is represented as C.
 Reversible Process
• When the system undergoes a change from its initial state to the final
state, the system is said to have undergone a process.
• During the thermodynamic process, one or more of the properties of
the system like temperature, pressure, volume, enthalpy or heat,
entropy, etc. changes.
• The second law of thermodynamics enables us to classify all the
processes under two main categories: reversible or ideal processes
and irreversible or natural processes.
• The process in which the system and surroundings can be restored to
the initial state from the final state without producing any changes in
the thermodynamics properties of the universe is called a reversible
process.
• In the figure below, let us suppose that the system has undergone a
change from state A to state B. If the system can be restored from
state B to state A, and there is no change in the universe, then the
process is said to be a reversible process.
• The reversible process can be reversed completely and there is no
trace left to show that the system had undergone thermodynamic
change.
• For the system to undergo reversible change, it should occur infinitely
slowly due to infinitesimal gradient.
• During reversible process all the changes in state that occur in the
system are in thermodynamic equilibrium with each other.
• Thus there are two important conditions for the reversible process to
occur.
• Firstly, the process should occur in infinitesimally small time and
secondly all of the initial and final state of the system should be in
equilibrium with each other.
• If during the reversible process the heat
content of the system remains constant,
i.e. it is adiabatic process, then the
process is also isentropic process, i.e.
the entropy of the system remains
constant.
• The phenomenon of undergoing
reversible change is also called
reversibility. In actual practice the
reversible process never occurs, thus it
is an ideal or hypothetical process.
 Irreversible Process
• The irreversible process is also called the natural process because all
the processes occurring in nature are irreversible processes.
• The natural process occurs due to the finite gradient between the
two states of the system.
• For instance, heat flow between two bodies occurs due to the
temperature gradient between the two bodies; this is in fact the
natural flow of heat.
• Similarly, water flows from high level to low level, current moves
from high potential to low potential, etc.
• 1) In the irreversible process the initial state of the system and
surroundings cannot be restored from the final state.
• 2) During the irreversible process the various states of the system on
the path of change from initial state to final state are not in
equilibrium with each other.
• 3) During the irreversible process the entropy of the system increases
decisively and it cannot be reduced back to its initial value.
• 4) The phenomenon of a system undergoing irreversible process is
called as irreversibility.
 Limitations of First Law of Thermodynamics

• The limitation of the first law of thermodynamics is that it does not

say anything about the direction of flow of heat.
• It does not say anything whether the process is a spontaneous
process or not.
• The reverse process is not possible. In actual practice, the heat
doesn’t convert completely into work.If it would have been possible
to convert the whole heat into work, then we could drive ships across
the ocean by extracting heat from the water of the ocean.
 Second Law of Thermodynamics

• If you ever drop a glass and watch it shatter, you know there is no way
of going back in time and getting back the unbroken glass.
• This is irreversibility. 
• The second law of thermodynamics states that the heat energy
cannot transfer from a body at a lower temperature to a body at a
higher temperature without the addition of energy. 
• This is why running an air conditioner for a long period of time, costs
you money.
 Kelvin-Planck statement
• It is impossible to convert all the heat extracted from a hot body into
work.
• In the heat engine, the working substance takes heat from the hot
body, converts a part of it into work and gives the rest to the cold
body.
• There is no engine that can convert all the heat taken from the source
into work, without giving any heat into the sink.
• This means that for obtaining continuous work, a sink is necessary.
 Clausius statement

• It is not at all possible to transfer heat from a cold body to a hot body
without the expenditure of work by an external energy source.
Clausius Inequality

Clausius' theorem is another way of stating the Second Law. Thus:

∫dQ/T < 0  (Integral around one complete cycle)

• The integral represents the net change in the entropy of the working fluid during one
complete heat cycle when in the working fluid in the heat engine returns to its initial state.
• At first glance it would appear that this would violate the second law since it shows that the
entropy change will always be zero or negative and we know that entropy can only increase or
stay the same.
 Entropy
• Let us see what is entropy, and its relation to the second law of
thermodynamics.
• The entropy of the system is measured in terms of the changes the
system has undergone from the previous state to the final state.
• Thus the entropy is always measured as the change in entropy of the
system denoted by ∆S.
• If at all it is necessary to measure the value of the entropy at a
particular state of the system, then zero value of entropy is assigned
to the previously chosen state of the system.
• The process during which the entropy of the system remains constant
is an isentropic process.
• During the isentropic process, the value of entropy of the system at
initial and final state remains constant.
• Thus during the isentropic process the value of ∆S=0.
• The reversible isentropic process never really occurs, it is only an
ideal process.
• In actual practice whenever there is a change in the state of the
system the entropy of the system increases.
 Heat Engine

• A heat engine involves a thermodynamic process that converts the

heat supply in it into mechanical work. Let’s look at the types of heat
engines.
• Steam engine
• Internal combustion engine
• Gas turbine
• There are three main parts in an engine. A hot body called source,
a working substance, and a body called sink.
• Source : There must be the source of heat of infinite thermal capacity, and
that should be at a constant high temperature so that if any amount of heat
is withdrawn from it or given to it, that does not affect its temperature.
• Working Substance : It must be some substance through which the heat is
absorbed or rejected into the sink. This is the working substance.
• Sink : There must be a sink of finite thermal capacity, and that should be at a
constant high temperature so that if any amount of heat is withdrawn from
it or given to it, that does not affect its temperature.
The efficiency of Heat Engine
• so here efficiency will be 100%
but in actual, this is not possible
because there will be some loss
of energy in the system.
• Hence for every engine, there is a
limit for its efficiency.
• Gasoline and diesel engines, jet
engines, and steam turbines that
generate electricity are all
examples of heat engines.
 Heat pump

• A heat pump is a device that pulls the energy out of air for the purpose of
either heating or cooling a space.
• This process is known as space conditioning.
• Heat pumps operate as a heat engine in reverse, as they do work from an
input of electricity to push heat from a cold place to a warm place.
• This would seemingly violate the Second law of thermodynamics, but the
key reason it doesn't is because this heat transfer is not spontaneous; it
requires an input of energy to do so.
• For home heating, a heat pump extracts heat from outside air, heats the
warm air up even more, and transfers it indoors.
• For home cooling, a heat pump reverses this process and heat is extracted
from the indoor air and expelled to the outside, just like a refrigerator or air
conditioner, thereby making the inside air cooler
 Third Law of Thermodynamics
• The Third Law of Thermodynamics is concerned with the limiting
behavior of systems as the temperature approaches absolute zero.
• Most thermodynamics calculations use only entropy differences, so
the zero point of the entropy scale is often not important.
• However, we discuss the Third Law for purposes of completeness
because it describes the condition of zero entropy. 
• The Third Law states, “The entropy of a perfect crystal is zero when
the temperature of the crystal is equal to absolute zero (0 K)