POLYTECHNIC UNIVERSITY OF THE PHILIPPINES

THERMODYNAMICS
BACHELOR OF SCIENCE
IN
ELECTRONICS AND COMMUNICATION ENGINEERING

SUBMITTED TO:

ENGR. ARMINGOL MORALES

SUBMITTED BY:

MARQUEZ, JESSIE NIÑO C.

Thermodynamics
Science of the relationship between heat, work, temperature, and energy. In broad terms,
thermodynamics deals with the transfer of energy from one place to another and from one form to
another. The key concept is that heat is a form of energy corresponding to a definite amount of
mechanical work.
The most important laws of thermodynamics are:
The zeroth law of thermodynamics
When two systems are each in thermal equilibrium with a third system, the first two
systems are in thermal equilibrium with each other. This property makes it meaningful to
use thermometers as the “third system” and to define a temperature scale.
The first law of thermodynamics, or the law of conservation of
energy.
The change in a system’s internal energy is equal to the difference between heat added
to the system from its surroundings and work done by the system on its surroundings.
The second law of thermodynamics.
Heat does not flow spontaneously from a colder region to a hotter region, or,
equivalently, heat at a given temperature cannot be converted entirely into work. Consequently,
the entropy of a closed system, or heat energy per unit temperature, increases over time toward
some maximum value. Thus, all closed systems tend toward an equilibrium state in
which entropy is at a maximum and no energy is available to do useful work. This asymmetry
between forward and backward processes gives rise to what is known as the “arrow of time.”
The third law of thermodynamics.
The entropy of a perfect crystal of an element in its most stable form tends to zero as
the temperature approaches absolute zero. This allows an absolute scale for entropy to be
established that, from a statistical point of view, determines the degree of randomness or
disorder in a system.
Although thermodynamics developed rapidly during the 19th century in response to the
need to optimize the performance of steam engines, the sweeping generality of the laws of
thermodynamics makes them applicable to all physical and biological systems. In particular, the
laws of thermodynamics give a complete description of all changes in the energy state of any
system and its ability to perform useful work on its surroundings.
This article covers classical thermodynamics, which does not involve the consideration of
individual atoms or molecules. Such concerns are the focus of the branch of thermodynamics
known as statistical thermodynamics, or statistical mechanics, which expresses macroscopic
thermodynamic properties in terms of the behaviour of individual particles and their interactions.
It has its roots in the latter part of the 19th century, when atomic and molecular theories of matter
began to be generally accepted.
 THERMODYNAMIC STATE

The application of thermodynamic principles begins by defining a system that is in some

sense distinct from its surroundings. For example, the system could be a sample of gas inside a
cylinder with a movable piston, an entire steam engine, a marathon runner, the planet Earth,
a neutron star, a black hole, or even the entire universe. In general, systems are free to
exchange heat, work, and other forms of energy with their surroundings.

Thermodynamic equilibrium
A particularly important concept is thermodynamic equilibrium, in which there is no
tendency for the state of a system to change spontaneously. For example, the gas in a cylinder with
a movable piston will be at equilibrium if the temperature and pressure inside are uniform and if
the restraining force on the piston is just sufficient to keep it from moving. The system can then
be made to change to a new state only by an externally imposed change in one of the state
functions, such as the temperature by adding heat or the volume by moving the piston. A sequence
of one or more such steps connecting different states of the system is called a process. In general,
a system is not in equilibrium as it adjusts to an abrupt change in its environment. For example,
when a balloon bursts, the compressed gas inside is suddenly far from equilibrium, and it rapidly
expands until it reaches a new equilibrium state. However, the same final state could be achieved
by placing the same compressed gas in a cylinder with a movable piston and applying a sequence
of many small increments in volume (and temperature), with the system being given time to come
to equilibrium after each small increment. Such a process is said to be reversible because the
system is at (or near) equilibrium at each step along its path, and the direction of change could be
reversed at any point. This example illustrates how two different paths can connect the same initial
and final states. The first is irreversible (the balloon bursts), and the second is reversible. The
concept of reversible processes is something like motion without friction in mechanics. It
represents an idealized limiting case that is very useful in discussing the properties of real systems.
Many of the results of thermodynamics are derived from the properties of reversible processes.

Temperature
The concept of temperature is fundamental to any discussion of thermodynamics, but its
precise definition is not a simple matter. For example, a steel rod feels colder than a wooden rod
at room temperature simply because steel is better at conducting heat away from the skin. It is
therefore necessary to have an objective way of measuring temperature. In general, when two
objects are brought into thermal contact, heat will flow between them until they come into
equilibrium with each other. When the flow of heat stops, they are said to be at the same
temperature. The zeroth law of thermodynamics formalizes this by asserting that if an object A is
in simultaneous thermal equilibrium with two other objects B and C, then B and C will be in
thermal equilibrium with each other if brought into thermal contact. Object A can then play the
role of a thermometer through some change in its physical properties with temperature, such as its
volume or its electrical resistance.
Total internal energy
Although classical thermodynamics deals exclusively with the macroscopic properties of
materials—such as temperature, pressure, and volume—thermal energy from the addition of heat
can be understood at the microscopic level as an increase in the kinetic energy of motion of
the molecules making up a substance. For example, gas molecules have translational kinetic
energy that is proportional to the temperature of the gas: the molecules can rotate about their centre
of mass, and the constituent atoms can vibrate with respect to each other (like masses connected
by springs). Additionally, chemical energy is stored in the bonds holding the molecules together,
and weaker long-range interactions between the molecules involve yet more energy. The sum total
of all these forms of energy constitutes the total internal energy of the substance in a given
thermodynamic state. The total energy of a system includes its internal energy plus any other forms
of energy, such as kinetic energy due to motion of the system as a whole (e.g., water flowing
through a pipe) and gravitational potential energy due to its elevation.

THE FIRST LAW OF THERMODYNAMICS

HEAT ENGINES
The classic example of a heat engine is a steam engine, although all modern engines follow
the same principles. Steam engines operate in a cyclic fashion, with the piston moving up and
down once for each cycle. Hot high-pressure steam is admitted to the cylinder in the first half of
each cycle, and then it is allowed to escape again in the second half. The overall effect is to take
heat Q1 generated by burning a fuel to make steam, convert part of it to do work, and exhaust the
remaining heat Q2 to the environment at a lower temperature.

ISOTHERMAL AND ADIABATIC PROCESSES

Isothermal expansion, involves keeping the gas at a constant temperature. As the gas does
work against the restraining force of the piston, it must absorb heat in order to conserve energy.
Otherwise, it would cool as it expands (or conversely heat as it is compressed). This is an example
of a process in which the heat absorbed is converted entirely into work with 100 percent efficiency.
The process does not violate fundamental limitations on efficiency, however, because a single
expansion by itself is not a cyclic process.
The second condition, known as an adiabatic expansion (from the Greek adiabatos,
meaning “impassable”), is one in which the cylinder is assumed to be perfectly insulated so that
no heat can flow into or out of the cylinder. In this case the gas cools as it expands, because, by
the first law, the work done against the restraining force on the piston can only come from
the internal energy of the gas. Thus, the change in the internal energy of the gas must be ΔU = −W,
as manifested by a decrease in its temperature. The gas cools, even though there is no heat flow,
because it is doing work at the expense of its own internal energy. The exact amount of cooling
can be calculated from the heat capacity of the gas.
2ND LAW OF THERMODYNAMICS
ENTROPY
The concept of entropy was first introduced in 1850 by Clausius as a precise mathematical
way of testing whether the second law of thermodynamics is violated by a particular process
ENTROPY AND EFFICIENCY LIMITS
The test begins with the definition that if an amount of heat Q flows into a heat reservoir
at constant temperature T, then its entropy S increases by ΔS = Q/T. The condition ΔS ≥ 0
determines the maximum possible efficiency of heat engines.
ENTROPY AND HEAT DEATH
The example of a heat engine illustrates one of the many ways in which the second law of
thermodynamics can be applied. One way to generalize the example is to consider the heat engine
and its heat reservoir as parts of an isolated (or closed) system—i.e., one that does not exchange
heat or work with its surroundings.
ENTROPY AND THE ARROW OF TIME
The inevitable increase of entropy with time for isolated systems plays a fundamental role
in determining the direction of the “arrow of time.” Everyday life presents no difficulty in
distinguishing the forward flow of time from its reverse.

OPEN SYSTEMS
THERMODYNAMIC POTENTIALS
Most real thermodynamic systems are open systems that exchange heat and work with
their environment, rather than the closed systems described thus far.
GIBBS FREE ENERGY AND CHEMICAL REACTIONS
The Gibbs energy (also referred to as) is also the thermodynamic potential that is
minimized when a system reaches chemical equilibrium at constant pressure and temperature. Its
derivative with respect to the reaction coordinate of the system vanishes at the equilibrium point.
The change in the Gibbs free energy of the system that occurs during a reaction is therefore
equal to the change in the enthalpy of the system minus the change in the product of the
temperature times the entropy of the system. If the reaction is run at constant temperature,
this equation can be written as follows.
ENTHALPY AND THE HEAT OF REACTION
The free energy change Wmax = −ΔG corresponds to the maximum possible useful work
that can be extracted from a reaction, such as in an electrochemical battery. This represents one
extreme limit of a continuous range of possibilities.
THERMODYNAMIC PROPERTIES AND RELATIONS
In order to carry through a program of finding the changes in the various thermodynamic
functions that accompany reactions—such as entropy, enthalpy, and free energy—it is often useful
to know these quantities separately for each of the materials entering into the reaction.
WORK OF EXPANSION AND CONTRACTION
The first task in carrying out the above program is to calculate the amount of work done
by a single pure substance when it expands at constant temperature. Unlike the case of a chemical
reaction, where the volume can change at constant temperature and pressure because of the
liberation of gas, the volume of a single pure substance placed in a cylinder cannot change unless
either the pressure or the temperature changes. To calculate the work, suppose that a piston moves
by an infinitesimal amount dx. Because pressure is force per unit area, the total restraining force
exerted by the piston on the gas is PA, where A is the cross-sectional area of the piston. Thus,
the incremental amount of work done is d′W = PA dx.
EQUATIONS OF STATE
The equation of state for a substance provides the additional information required to
calculate the amount of work that the substance does in making a transition from
one equilibrium state to another along some specified path.
HEAT CAPACITY AND SPECIFIC HEAT
There is an equivalence between heat (measured in calories) and mechanical work
(measured in joules) with a definite conversion factor between the two. The conversion factor,
known as the mechanical equivalent of heat, is 1 calorie = 4.184 joules. (There are several slightly
different definitions in use for the calorie. The calorie used by nutritionists is actually a
kilocalorie.) In order to have a consistent set of units, both heat and work will be expressed in the
same units of joules.
HEAT CAPACITY AND INTERNAL ENERGY
The goal in defining heat capacity is to relate changes in the internal energy to measured
changes in the variables that characterize the states of the system. For a system consisting of a
single pure substance, the only kind of work it can do is atmospheric work, and so the first law
reduces todU = d′Q − P dV.
ENTROPY AS AN EXACT DIFFERENTIAL
Because the quantity dS = d′Qmax/T is an exact differential, many other important
relationships connecting the thermodynamic properties of substances can be derived. For example,
with the substitutions d′Q = T dS and d′W = P dV, the differential form (dU = d′Q − d′W) of
the first law of thermodynamics becomes (for a single pure substance)dU = T dS − P dV. (39)
The advantage gained by the above formula is that dU is now expressed entirely in terms
of state functions in place of the path-dependent quantities d′Q and d′W. This change has the very
important mathematical implication that the appropriate independent variables are S and V in
place of T and V, respectively, for internal energy.
THE CLAUSIUS-CLAPEYRON EQUATION
Phase changes, such as the conversion of liquid water to steam, provide an important
example of a system in which there is a large change in internal energy with volume at
constant temperature. Suppose that the cylinder contains both water and steam in equilibrium with
each other at pressure P, and the cylinder is held at constant temperature T, as shown in the figure.
The pressure remains equal to the vapour pressure Pvap as the piston moves up, as long as both
phases remain present. All that happens is that more water turns to steam, and the heat reservoir
must supply the latent heat of vaporization, λ = 40.65 kilojoules per mole, in order to keep the
temperature constant.

 Chemical energy - is related to the relationships between molecules in chemical

compounds. When chemicals react with each other, they may give off heat (exothermic
reaction) or require heat (endothermic reaction)
 Electric energy - is related to electrons moving through a conductor
 Energy - can be reduced to the concepts of heat and work and can be found in various
forms: potential energy, kinetic energy, thermal or internal energy, chemical energy, and
nuclear energy
 Enthalpy - is a term with energy units that combines internal energy with a
pressure/volume or flow work term
 Entropy - is a property of matter that measures the degree of randomization or disorder.
The natural state is for entropy to be produced by all processes
 Heat - is energy in motion from one region to an other as a result of temperature difference
 Internal energy - has to do with activity within the molecular structure and is typically
observed with temperature measurement
 Kinetic energy - is the energy of motion and is proportional to the square of the velocity
as well to the mass of the moving body
 Nuclear energy - is related to the energy of atomic relationships between the fundamental
particles. Nuclear fission and fusion are reactions which release nuclear energy
 Potential energy - is the energy of location or position of a mass in a force field
 Property - is a measurable characteristic of a system or substance. Temperature, density,
pressure etc
 Specific Heat - The specific heat is the amount of heat required to change a unit mass (or
unit quantity, such as mole) of a substance by one degree in temperature
 Temperature - is a term used to quantify the difference between warm and cold level of
internal energy of a substance
 Work - is an energy form which can be equated to the rising of a weight as moving a mass
in a force field or moving a liquid against a resisting force
 Thermodynamics - Effects of work, heat and energy on systems
 1st Law of Thermodynamics - The First Law of Thermodynamics simply states that
energy can be neither created nor destroyed (conservation of energy). Thus power
generation processes and energy sources actually involve conversion of energy from one
form to another, rather than creation of energy from nothing
 2nd Law of Thermodynamics - Entropy and disorder
 Air - Thermophysical Properties - Thermal properties of air - density, viscosity, critical
temperature and pressure, triple point, enthalpi and entropi, thermal conductivity and
diffusicity, and more
 Dimensionless numbers - Definitions and symbols for physical and chemical
dimensionless quantities, with areas of application of the different numbers. Reynolds,
Euler, Nusselt, Prandtl..... and many more
 Heat Capacity - The heat capacity of a substance is the amount of heat required to change
its temperature by one degree, and has units of energy per degree
 Heat of combustion - Tabulated values of heat of combustion (= energy content) of
common substances, together with examples showing how to calculate the heat of
combustion
 Melting and Boiling Points, Densities and Solubility for Inorganic Compounds in
Water - Physical constants for more than 280 common inorganic compounds. Density is
given for the actual state at 25°C and for liquid phase at melting point temperature.
 Properties and State - Concept of properties and state
 Symbols Used to Denote a Chemical Reaction, Process or Condition - Explanation of
symbols used as subscripts or superscripts to tell more about the type of chemical reaction,
process or condition
 Third Law of Thermodynamics - The entropy of a substance is zero if the absolute
temperature is zero
 Universal and Individual Gas Constants - The Universal and Individual Gas Constants
in fluid mechanics and thermodynamics. Individual gas constant is given for the most
common gases.
 WABT - weighted average bed temperature - Definition and examples of calculation of
weighted average bed temperature in adiabatic reactors
 Water - Thermophysical Properties - Thermal properties of water - density, freezing
temperature, boiling temperature, latent heat of melting, latent heat of evaporation, critical
temperature and more
  Term Function

Activity coefficient γi = fi/(xifiθ)

Chemical potential μi = (∂G/∂ni)T,p,nj≠i

Energy U

Enthalpy H = U + pV

Entropy S

Fugasity fi = (xi)exp{(μi - μiÞg)/RT}

Gibbs (free) energy G = U + pV - TS

Gibbs-Duhem relation 0 = SdT - Vdp + Σinidμi

Gibbs-Helmholtz equation H = G - T(∂G/∂T)p

Helmholtz energy A = U - TS

Isentropic (constant heat and mass)

= - (∂V/∂p)S/V
compressibility

Isothermal (constant temperature)

= - (∂V/∂p)T/V
compressibility

 = T V2V/Cp

Isobaric (constant pressure) expansivity V= (∂V/∂T)p/V

Isobaric heat capacity Cp = (∂H/∂T)p

Isochoric (constant volume) heat capacity CV = (∂U/∂T)v

Cp - CV = T2V/
  Term Function

Joule-Thompson expansion μJT = (∂T/∂p)H = - {V - (∂V/∂T)p}/Cp

ΦJT = (∂H/∂p)T = V - T(∂V/∂T)p

Maxwell relations (∂S/∂p)T = - (∂V/∂p)p

(∂S/∂V)T = - (∂p/∂T)V

Partial molar quantity Xi = (∂X/∂ni)T,p,nj≠i

Perfect (ideal) gas [symbol Þg] pV = (Σini)RT

μiÞg = μiθ + RTln(xip/pθ)

Where

p = pressure
V = Volume
T = temperature
ni = amount of substance i
xi = ni/Σjnj = mole fraction of substance i
R = gas constant