[DOCUMENT TITLE]

(For B.Tech. (Chemical Engineering)

 BE 8256 - BASIC MECHANICAL ENGINEERING

UNIT I LAWS OF THERMODYNAMICS

Basic concepts and hints; Zeroth law; First Law of Thermodynamics - Statement and application;
Steady flow energy equation-problems- Second law of Thermodynamics – Kelvin - Plank statement
and Clausius statement- problems; Limitations; Heat Engine, Refrigerator and Heat Pump,
Available energy, Third law of Thermodynamics - Statement.

1. Define Thermodynamics.
 The science of thermodynamics deals with energy and its transformation.
 Also it the study of relationships between different forms of energy
.
2. Write the limitations of thermodynamics.
 Thermodynamics does not give information about the rate of any process.
 Thermodynamics is concerned only with final conditions and not the mechanism
by which final conditions are attained.

3. Define System and surrounding?

System is a region of space, under consideration for the analysis. Ex: A reaction vessel, a
heat engine, a distillation column.

4. Define Surroundings?
Anything outside the thermodynamic system is called the surroundings.

5. Define a boundary?
The system is separated from the surroundings by the boundary.

6. Define a process.
The change taking place within a system is a process.

7. How systems are classified?

 Open systems: Exchange of energy and matter takes place between system and
surrounding. (Ex: A continuous reactor)

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 An Open System (energy and mass in and out)

 Closed systems : Exchange energy alone takes place between system and surrounding.
Ex: A Batch reactor

A Closed System (No mass entry or out)

 Isolated systems: No exchange of energy and matter takes place between system and
surrounding. No system is completely isolated.

An Isolated system (Fixed mass i.e. no mass / energy in or out)

 Homogeneous systems: A system having single phase is a homogeneous system.
(system with uniform physical property and chemical composition) Ex: Sugar
solution.)
 Heterogeneous System: A system having more than one phase is a heterogeneous
system. (Ex: Solution of water and oil)

8. State property:
The conditions of a system are described using some measurable properties. They are
called as state properties. Ex: temperature, pressure, and volume.

9. State function or point functions.

State properties describe system’s present state and do not give the previous history. So
state properties are state functions and fixed for a particular state of a system. Ex: temperature,
pressure, and volume.

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10. Path functions:
The functions or properties, depends on the path, followed by a system to attain the present
state. (Ex: Heat, Work)

11. Extensive properties:

Properties depend upon the quantity/size of matter contained in the system.
Ex. mass, volume, heat capacity, internal energy, enthalpy, entropy

12. Intensive properties:

Properties not depend upon the quantity/size of matter contained in the system.
Ex: temperature, density, specific heat, and boiling point.

13. Thermodynamic process:

A thermodynamic process has occurred when the system changes from one state (initial)
to another state (final). The operation by which this change of state occurs is called a process.

14. Types of thermodynamic processes:

Isothermal process: The temperature of the system is kept constant during a process.
Adiabatic process: No heat can flow from the system to the surroundings or vice versa.
Isochoric process: The volume of the system is kept constant during a process.
Isobaric process: The pressure of the system is kept constant during a process.
Isentropic process: The entropy of the system is kept constant during a process.

15. What is quasi static process?

The infinitesimal or quasi-static process is the one which ensures that the system is always
in equilibrium so that the properties of the system are same throughout and change very slowly.

16. Force
𝐹 = 𝑚𝑎 = 𝑚𝑎𝑠𝑠 × 𝑎𝑐𝑐𝑒𝑙𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑢𝑒 𝑡𝑜 𝑔𝑟𝑎𝑣𝑖𝑡𝑦
𝑚
= 𝑘𝑔. 𝑠2 = 𝑁

17. Energy
 Energy is defined as capacity to do work.
 Energy is exchanged in form of Heat and work.
 Heat and work are called energy in transit, because they cannot be stored within the
system.

18. Heat
 The heat is the energy that flows from a body at higher temperature to one at lower
temperature due to the temperature difference.

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  It is a path function.
 Unit of heat is expressed in Joules (J) or calories.

19. Pressure
Force F
P= =
Area A

𝑵
= = Pa (Pascal)
𝒎𝟐

20. Work / Work done

 Work is said to be done when a force applied against a load over a distance.
 𝑊𝑜𝑟𝑘𝑑𝑜𝑛𝑒 = 𝑑𝑊 = 𝐹𝑜𝑟𝑐𝑒 × 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑚𝑜𝑣𝑒𝑑 = 𝐹𝑑𝑍
= 𝑁. 𝑚 (𝑁𝑤𝑒𝑡𝑜𝑛 𝑚𝑒𝑡𝑟𝑒) = 𝐽 (𝑗𝑜𝑢𝑙𝑒)
 It is a path function.
𝑑𝑉
 If work done is expressed in terms of P and V, 𝐹 = 𝑃𝐴 𝑎𝑛𝑑 𝑑𝑧 = 𝐴
𝑑𝑉 𝑉2
𝑡ℎ𝑒𝑛 𝑑𝑊 = 𝑃𝐴. = 𝑃. 𝑑𝑉, 𝑠𝑜 𝑊 = ∫𝑉 𝑃. 𝑑𝑉
𝐴 1
𝑁
= . 𝑚3 = 𝑁. 𝑚 = 𝐽
𝑚2

21. Power
𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑊 𝐽
Work done per unit time is power, i.e. = = = 𝑊𝑎𝑡𝑡, 𝑊
𝑇𝑖𝑚𝑒 𝑡 𝑠
Power is sometimes expressed in horse power, 1 hp = 746 W

22. What are the general sign conventions used for heat and work?
Process Sign
Heat added to the System + 𝑣𝑒
Heat rejected by the system − 𝑣𝑒
Work done by the system + 𝑣𝑒
Work done on the system − 𝑣𝑒

23. Heat capacity and Specific heat capacity

 The ratio between the heat added (or removed), and the corresponding rise (or
decrease) in the temperature of the material.
 The heat capacity, or 'thermal mass' of an object, is defined as the Energy in Joules
required to raise the temperature of a given object by 1º C.

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  This is the 'specific heat' of the object (a defined physical/chemical property)
multiplied by its mass and the change in temperature.

24. What is temperature?

 Temperature is measure of heat. It measures Hotness or coldness of a body.” A
 Temperature is the measure of the average kinetic energy of the particles in a
substance, which is related to how hot or cold that substance is.

25. Zeroth Law of Thermodynamics

The Zeroth law of thermodynamics is a definition of thermodynamic equilibrium.
It states that if two systems, A and B are in thermal equilibrium and a third system C is in
thermal equilibrium with system A then systems B and C will also be in thermal equilibrium.
𝐼𝑓 𝐴 = 𝐵 𝑎𝑛𝑑 𝑖𝑓 𝐶 = 𝐴, 𝑡ℎ𝑒𝑛 𝐶 = 𝐵 𝑎𝑙𝑠𝑜.

26. Define equilibrium.

𝐷𝑟𝑖𝑣𝑖𝑛𝑔 𝑓𝑜𝑟𝑐𝑒
The rate of a process = 𝑅𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒
Equilibrium may be defined as a state wherein the net rate of the process is zero.

27. Internal energy and enthalpy.

 Internal energy of a substance is the energy possessed by the molecules present in the
substance.
 Heat change occurring in a system is called as enthalpy. (The heat supplied to a system
at constant pressure can be measured as the change in another thermodynamic property
and is known as enthalpy).

28. Thermodynamic equilibrium

In thermodynamics, a thermodynamic system is said to be in thermodynamic equilibrium
when it is in thermal equilibrium, mechanical equilibrium, and chemical equilibrium.
 Two systems are in thermal equilibrium when their temperatures are the same.
 Two systems are in mechanical equilibrium when their pressures are the same.
 Two systems are in diffusive equilibrium when their chemical potentials are the same

29. What do you understand by the term “Thermodynamics”?

Thermodynamics is the science of energy transfer and its effect on the physical properties
of the substances. This word consists of two words, “Thermo” meaning heat and “dynamics”
means motion, which is most descriptive of the early efforts to convert heat into power. But
today the same name is broadly interpreted and also includes all aspects of,
Energy and energy transformations
Relationships among the properties of ideal and non-ideal systems
Phase and chemical equilibria in single and multiphase systems.

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30. Define the terms Systems, Process and Surroundings.
Systems: In thermodynamics a substance or group of substances in which we have special
interest or under consideration is called as a system. It is that part of the universe which is set
apart for our special consideration. It may be a reaction vessel, a distillation column, or a heat
engine etc.
Process: The change taking place within the system is referred to as a process. So in
combustion of hydrocarbon fuel, the fuel and oxygen in a combustion chamber constitute the
system and the combustion of fuel to form water and carbon dioxide constitute a process.
Surroundings: The part of the universe outside the system and separated from the system by
boundaries is called surroundings. The boundaries may be either physical or imaginary; they
may be rigid or movable.
Note: But for practical reasons, the surroundings are usually restricted to that portion of the
universe which is in the immediate vicinity of the system and are affected by the changes
occurring in the system. For example, when the steam condensing in a shell and tube heat
exchanger is treated as the system, the cooling water to which the latent heat of vaporization
is transferred may be treated as the surroundings.

31. What are state functions and path functions?

State functions Or Point functions: Properties of a substance describes its present state
and do not give a record of its previous history. They are independent of the path through which
the current or he state under consideration and do not in any way depend upon the past history
or the path through which the state was arrived. When a system is considered in two different
states, the difference in property between two states depends only upon the states itself and not
upon the manner in which the system changes from one state to other. Ex: Internal energy,
enthalpy, entropy, free energy etc.
Path functions: These functions depend upon the path for a variation from an initial to final
state. The values of heat and work accompanying a given change in state vary with the path
from the initial to the final state. For example consider combustion of a mass of an hydrocarbon
may be completely burnt in presence of air in a combustion chamber. The following are the
possibilities. All the energy lost by the system appears as heat.
Otherwise a large part of the energy is converted to mechanical work and only the remainder
into heat in an internal combustion engine. That is the heat and work involved in a given change
of state are not solely determined by the initial and final state, but also depends on the manner
in which the change is carried out. Heat and work are not thermodynamic properties of the
system, but are the properties of the process and are called path functions.

32. How state functions are represented mathematically? (What are exact and inexact
differentials?)
Mathematically a state function is an exact differential and path function is an inexact

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 differential, i.e. 𝐼𝑓 𝑍 =
𝑓(𝑥, 𝑦)𝑎𝑛𝑑 𝑍 𝑡𝑜 𝑏𝑒 𝑎𝑛 𝑒𝑥𝑎𝑐𝑡 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑡𝑖𝑎𝑙, 𝑡ℎ𝑒 𝑓𝑜𝑙𝑙𝑜𝑤𝑖𝑛𝑔 𝑐𝑟𝑖𝑡𝑒𝑟𝑖𝑎
𝑎𝑟𝑒 𝑡𝑜 𝑏𝑒 𝑠𝑎𝑡𝑖𝑠𝑓𝑖𝑒𝑑.
𝜕𝑍 𝜕𝑍
(𝑖) 𝑑𝑍 = ( ) 𝑑𝑥 + ( ) 𝑑𝑦
𝜕𝑥 𝜕𝑦
𝑦 𝑥
𝜕𝑍 𝜕𝑍
= 𝑀 𝑑𝑥 + 𝑁 𝑑𝑦 ; 𝑤ℎ𝑒𝑟𝑒 𝑀 = (𝜕𝑥 ) 𝑎𝑛𝑑 𝑁 = (𝜕𝑦) and
𝑦 𝑥
𝜕𝑀 𝜕𝑁
(𝑖𝑖) ( ) = ( )
𝜕𝑦 𝑥𝜕𝑥 𝑦

33. State some general properties of state and path functions.

 State functions can be expressed as difference between two states while path functions are
absolute quantities. (Density or viscosity changes but not work or heat, a definite quantity
of hat is added or removed.
 State functions are represented by a point on a graph so the name as point function while
path function is represented by an area.
 For a cyclic process the change in state function are zero while it is no so for path function.

34. Define and classify energy?

Energy could be classified as, (i) Accumulated energy and (ii) Transitory energy
Accumulated energy: This could be classified into two Microscopic energy or internal
energy and macroscopic energy or external energy.
The internal energy: In which a system possess by virtue of the molecular configuration
and motion of molecules is a thermodynamic property of a system. Ex: Transitional,
rotational, vibrational energies, nuclear energy etc.
The external energy: are not the thermodynamic properties of the system, they do not
change with the change in pressure or temperature. Ex: Potential energy (energy possessed
by the system due o its position above some arbitrary reference, energy possessed by the
water stored in a overhead tank), Kinetic energy (energy possessed by the body by virtue
of the motion, energy possessed by a moving vehicle)
Transitory energy or energy in transit: The energy stored in a system could be exchanged
between the system and surroundings. The exchange of energy occurs either as heat or
work and called as energy in transit, they cannot be stored within the system.

35. Define work and enumerate the types of work.

Energy is expended in the form of work when a force acts through a distance.
𝑑𝑊 = 𝐹 𝑑𝑍, that is where ‘W’ is the work done, F is the force acting and Z is the
displacement. The unit of work is N m or joules.
Mechanical work: Consider a gas confined in a piston and cylinder arrangement. The work
due to the Movement of the piston is termed as mechanical work

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 Elastic work: A stretched spring carrying a load of 50 kg, is contracted if some load say 5
kg is removed and contraction for a definite distance and the work is done by the system
and his work is called as elastic work.
Chemical work: This is the work that comes due to the vaporization of a liquid or due to a
chemical reaction.

36. Temperature Scales

 In SI units the reference temperature is triple point of water, i.e. the temperature at
which the solid, liquid and vapor phase of water coexist in equilibrium. The value is
273 K (actually 273.16 K), where K is Kelvin.
 0°C = 273 K
 The Fahrenheit scale is widely used. On this scale the freezing point of water
corresponds to 32 °F and the boiling point to 212 °F.
 The following conversion formulas may be used to convert between Fahrenheit (F)
and Celsius (C) temperature values:
5 9
° 𝐶 = (°𝐹 − 32) 𝑎𝑛𝑑 °𝐹 = °𝐶 + 32
9 5
 °R (Rankin) = °F + 459.69
 The relation between various scales as follows;
0° 𝐶 = 273.16 𝐾 = 32 °𝐹 = 491.67 𝑅

37. Define true equilibrium.

The rate can be zero due to driving force being zero. This is called true equilibrium. They
are of three types.
Mechanical equilibrium: If there is no imbalance of forces in a system when it is isolated and
said to be in mechanical equilibrium.
Thermal equilibrium: When there is no change in the thermal condition of a system when it
is isolated, it is said to be in a state of thermal equilibrium.
Chemical equilibrium: If there is no change in the composition of a system due to the mass
transfer or chemical reaction when the system is isolated, then it is said to be in a stat of
chemical equilibrium.
A system which is simultaneously in a state of thermal, mechanical and chemical equilibrium
is said to be a state of thermodynamic equilibrium.

38. What do you understand by the term “false equilibrium”?

𝐷𝑟𝑖𝑣𝑖𝑛𝑔 𝑓𝑜𝑟𝑐𝑒
The rate of a process= , and the rate could be zero due to the resistance
𝑅𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒
being infinitely large. This is called false equilibrium.
Under ordinary conditions hydrogen and oxygen do not combine to give water even
though the chemical potentials (It is thermodynamic property widely used, I is used as an
index of chemical equilibrium in a similar manner as pressure and temperature are used as

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 indices of mechanical and thermal equilibrium. It is seen as contribution of the component
to Gibbs free energy, which is widely used in chemical reaction equilibria) of hydrogen
and oxygen are greater than that of water. This is because of an extremely large resistance,
so hydrogen and oxygen are under false equilibrium at ordinary conditions.

39. Write a note on Reversible and Irreversible processes:

A thermodynamic process occurs when there is a driving force for a change exists. This
driving force may be within a system or between and its surrounding.
 If this driving force infinitesimal (very very small) then it is a reversible process.
 If the driving force is finite then it is an irreversible process.
Properties of reversible process:
 This process is carried out infinitesimally and slowly, so that all changes occurring
can be exactly reversed.
 It can be reversed by any of the thermodynamic variables.
 The system remains almost in a state of equilibrium with the surroundings at every
stage of the process.
 Reversible processes are necessarily frictionless process
 It is a slow process.
 The work obtained is more.
 It is an unreal process.
Properties of Irreversible process:
 These processes are also called as natural process because all the processes
occurring in the nature are irreversible processes.
 The natural process occurs due to finite driving force between the two states of the
system. Ex: heat flow between two bodies if there is a temperature difference
between the two bodies.
 In these processes the initial state of the system and surroundings cannot be restored
from the final state.
 During the process the various stages of the system on the path of change are not
in equilibrium with its surrounding.

40. Some examples of nature of some common systems we encounter:

S System Nature S System Nature

No No
1 Bike engine Open 9 Mix of air and water vapor Homogeneous
2 Liq. cooling system in a plant Closed 10 Sol. Of NH3 in water Homogeneous
3 Boiler in a power plant Open 11 Octane plus Heptane Homogeneous
4 Electric fan Open 12 Water + Steam Heterogeneous
5 Car battery Closed 13 Ice + Water Heterogeneous

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6 Air compressor Open 14 Water + Oil Heterogeneous
7 Water pump Open 15 Water + Nitric acid Homogeneous
8 Pressure Cooker Closed 16 Thermometer surrounded Closed
by High temperature
medium

41. Define energy.

Accord the first to the law of thermodynamics: energy cannot be created or destroyed.
Energy can only change form. Chemically, that usually means energy is converted to work, energy
in the form of heat moves from one place to another, or energy is stored up in the constituent
chemicals. You have seen how to calculate work. Heat is defined as that energy that is transferred
as a result of a temperature difference between a system and its surroundings. Mathematically, we
can look at the change in energy of a system as being a function of both heat and work:
ΔE = q - w
Where:
ΔE is the change in internal energy of a system
q is the heat flowing into the system
w is the work being done by the system
If q is positive, we say that the reaction is endothermic, that is, heat flows into the reaction
from the outside surroundings. If q is negative, then the reaction is exothermic, that is, heat is
given off to the external surroundings.

42. Write a note on some types of energy.

Look around you. Is anything moving? Can you hear, see or feel anything? Sure... this is
because something is making something happen, and most probably, there is some power at
work. This power or ability to make things happen is what we can call energy. It makes things
happen. It makes change possible.
Energy moves cars along the roads and makes airplanes fly. It plays our music on the radio
and lights our homes. Energy is needed for our bodies, together with plants to grow and move
about. So energy is capacity or ability to do work. Energy can be (is) stored or transferred from
place to place, or object to object in different ways. There are various types of energy.

Kinetic Energy : All moving things have kinetic energy. It is energy possessed by an object
due to its motion or movement. These include very large things, like planets, and very small

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 ones, like atoms. The heavier a thing is and the faster it moves the more kinetic energy it
has. Now let's see this illustration below. Let There is a small and large ball resting on a
table. Let’s say both balls will fall into the bucket of water. Let's see what is going to
happen.
Both balls had potential energy as they rested on the table. By resting up on a high
table, they also had gravitational energy. By moving and falling off the table (movement),
potential and gravitational energy hanged to Kinetic Energy. Let's see another classic
example. If you are in a hot room and you turn on the fan, what do you begin to feel? Air
(wind). The speedy movement of the fan's blades has kinetic energy, which is then
transferred into air (wind) that you now feel. Other examples of Kinetic Energy include a
moving car, moving water, moving wheel, and a moving arrow.

b. Sound energy
Sound is the movement of energy through substances in longitudinal (compression
/rarefaction) waves.
Sound is produced when a force causes an object or substance to vibrate — the energy
is transferred through the substance in a wave. Typically, the energy in sound is far less
than other forms of energy.
A vibrating drum in a disco transfers energy to the room as sound. Kinetic energy
from the moving air molecules transfers the sound energy to your dancers eardrums. Notice
that Kinetic (movement) energy in the sticks is being transferred into sound energy. Sound
vibrations create sound waves which move through mediums such as
air and water before reaching our ears.

c. Heat (Thermal energy)

Thermal energy is what we call energy that comes from heat. A cup of hot tea has

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 thermal energy in the form of kinetic energy from its particles. Some of this energy is
transferred to the particles in cold milk, which you pour in to make the tea cooler.

d. Chemical energy
Chemical Energy is energy stored in the bonds of atoms and molecules. Batteries,
biomass, petroleum, natural gas, and coal are examples of stored chemical energy. For
example, when an explosive goes off, chemical energy stored in it is transferred to the
surroundings as thermal energy, sound energy and kinetic energy. Let's see one good
example in the illustration below. The dry wood is a store of chemical energy. As it burns
in the fireplace, chemical energy is released and converted to thermal energy (heat) and
light energy. Food is also a good example of stored chemical energy. This energy is
released during digestion, and the energy keeps us warm, maintains and repair bodies, and
makes us able to move about. Different foods store different amounts of energy. Energy in
food is measured in kilocalories (or Calories).

e. Electrical energy
A battery transfers stored chemical energy as charged particles called electrons, typically
moving through a wire. For example, electrical energy is transferred to the surroundings by the
lamp as light energy and thermal (heat) energy. Lightning is one good example of electrical
energy in nature, so powerful that it is not confined to a wire. Thunderclouds build up large
amounts of electrical energy. This is called static electricity. They are released during lightning
when the clouds strike against each other.

f. Gravitational Energy, Potential Energy

A rock on a mountain has stored energy because of its position above the ground and the
pull of gravity. It is energy stored in an object's height. This is the energy it would release if it fell.
As the rock falls to the ground, the gravitational potential energy is transferred as kinetic energy.
See the diagram. It is important to know the difference between potential energy and gravitational
energy. Every object may have Potential energy but Gravitational energy is only stored in the
height of the object. It is important to note that the heavier the object, the more its potential energy.

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Note: Remember the terms kinetic energy and potential energy. Kinetic energy is the energy of
motion -- the amount of energy in an object that is moving. Potential energy is stationary, stored
energy. If you think of a ball sitting on the edge of a table, it has potential energy in the energy
possible if it falls off the table. Potential energy can be transformed into kinetic energy if and when
the ball actually rolls off the table and is in motion. The total energy of the system is defined as
the sum of kinetic and potential energies

43. What is the difference between temperature and heat?

There is a fundamental difference between temperature and heat. Heat is the amount of
energy in a system. The SI units for heat are Joules. A Joule is a Newton times a meter.
A Newton is a kilogram-meter per second squared. Heat is transferred through radiation,
conduction and convection. The amount that molecules are vibrating, rotating or moving is a direct
function of the heat content.
Energy is transported by conduction as molecules vibrate, rotate and/or collide into each
other. Heat is moved along similar to dominos knocking down their neighbors in a chain reaction.
An increase of electromagnetic radiation into a system causes the molecules to vibrate,
rotate and/or move faster. With convection, higher energy molecules are mixed with lower energy
molecules. When higher energy molecules are mixed with lower energy molecules the molecular
motion will come into equilibrium over time.
The faster moving molecules will slow down and the low moving molecules will speed up.
Temperature is the MEASURE of the AVERAGE molecular motions in a system and simply has
units of (degrees F, degrees C, or K).
Notice that one primary difference between heat and temperature is that heat has units of Joules
and temperature has units of (degrees F, degrees C, or K). Another primary difference is that
energy can be transported without the temperature of a substance changing (e.g. latent heat, ice
water remains at the freezing point even as energy is brought into the ice water to melt more ice).
But, as a general statement (ignoring latent heat), as heat energy increases, the temperature
will increase. If molecules increase in vibration, rotation or forward motion and pass that energy
to neighboring molecules, the measured temperature of the system will increase.

44. What is the difference between thermal energy and heat energy?
Thermal energy is the energy a substance or system has related to its temperature, i.e., the
energy of moving or vibrating molecules. Atoms and molecules, the smallest particles of any
substance, are always in motion. The motion of thermal energy is usually not visible, but we can
feel or see its effects. We use thermal energy to cook our food and heat our homes, and we use it
to generate electricity.
Thermal energy is not the same as heat. Heat is energy transferred between substances or
systems due to a temperature difference between them. So it is correct to say that a system contains
thermal energy, but not that it "contains" heat, since heat means energy that is transferred from one
thing to another.

13 | BE 8256 Basic Mechanical Engineering / U – I / Compiled by R.Arul Kamalakumar

 The amount of heat transferred by a substance depends on the speed and number of atoms or
molecules in motion. The faster the atoms or molecules move, the higher the temperature, and the
more atoms or molecules that are in motion, the greater the quantity of heat they transfer.
This could be explained by the following example. Consider a candle where the energy is
stored as light, thermal energy. When the candle is lit the stored thermal energy is converted to
heat energy, which could be felt when we move our finger near to it. Once we felt it is absorbed
by our body and converted to thermal energy.

45. Application of, “heat and thermodynamics”.

46. Write down the first law equation for a steady stat and unsteady state open systems.
a. Steady state open system:
𝑚(∆𝐻 + ∆𝐾𝐸 + ∆𝑃𝐸) = 𝑄 − 𝑊𝑆
b. Unsteady state open system:
∆(𝑚𝐻) = 𝑄 − 𝑊𝑆 − ∆(𝑚𝐸) , 𝑊ℎ𝑒𝑟𝑒 ∆(𝑚𝐻) = 𝑚2 𝐻2 − 𝑚1 𝐻1
𝑎𝑛𝑑 ∆(𝑚𝐸) = 𝑚𝑓 𝐸𝑓 − 𝑚𝑖 𝐸𝑖
Where ‘m’ is mass; ‘H’ is enthalpy; ‘KE’ is kinetic energy; ‘PE’ is potential energy; ‘Q’
is heat added, ‘WS’ is shaft work; ‘E’ is internal energy; i and f indicates initial and final conditions,
of the system.

47. First law for cyclic process.

The first law of thermodynamics dictates that the net heat input is equal to the network output over
any cycle. The area enclosed by the loop is the work (W) done by the process:

Equation (1) shows the work is equal to the balance of heat (Q) transferred into the system.
Equation (2) makes a cyclic process.

48. First law equation for constant volume (Iso-choric) process.

14 | BE 8256 Basic Mechanical Engineering / U – I / Compiled by R.Arul Kamalakumar

 When a gas is undergoing a constant volume process between state 1 and 2, the change in internal
energy is given by
∆𝑈 = 𝑈2 − 𝑈1 = ∫ 𝐶𝑉 𝑑𝑇
49. First law equation for constant pressure (Iso-baric) process.
When a gas is undergoing a constant pressure process between state 1 and 2, the change in internal
energy is given by
∆𝐻 = 𝐻2 − 𝐻1 = ∫ 𝐶𝑃 𝑑𝑇
50. First law equation for constant Temperature (Iso-thermal) process.
For isothermal process involving an ideal gas the internal change occurs only when temperature
changes. So internal energy (U) and enthalpy (H) is zero. So, dW = dQ. If initial and final volume in
an isothermal process is 𝑉1 𝑎𝑛𝑑 𝑉2 and corresponding initial and final pressure be 𝑃1 𝑎𝑛𝑑 𝑃2 , then
𝑉2 𝑃1
𝑄 = 𝑊 = 𝑅𝑇 𝑙𝑛 = 𝑅𝑇 ln
𝑉1 𝑃2
51. First law equation for adiabatic process.
In an adiabatic process there is no heat interaction between system and the surrounding, so dQ is
zero.
𝑑𝑈 = −𝑑𝑊 = −𝑃𝑑𝑉 𝑓𝑜𝑟 𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
𝐶
And pressure and volume are related as, 𝑃𝑉 𝛾 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑎𝑛𝑑 𝛾 = 𝐶𝑃
𝑉
Work done = 𝑊 = 𝐶𝑉 (𝑇1 − 𝑇2 )

52. Define a polytrophic process.

In a polytrophic process the relationship between pressure and volume is assumed to be
𝑃𝑉 𝑛 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑤ℎ𝑒𝑟𝑒 𝑛 𝑖𝑠 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡.

53. First law for closed system.

We balance the changes in the internal energy of the gas with the amount of heat transferred to/from
the gas and work done by/on the gas. This energy balance is called the first law for a closed system.
It is written in differential form dU = dQ - dW ,integrated form

54. Limitations of first law of thermodynamics.

 It puts no restriction on the direction of flow of heat.
 It is unable to explain why it is not possible to convert heat energy completely into an equivalent
amount of work.

55. Show that 𝑪𝑷 − 𝑪𝑽 = 𝑹 for ideal gas.

Enthalpy is given by 𝐻 = 𝑈 + 𝑃𝑉,
𝑖. 𝑒. 𝑑𝐻 = 𝑑𝑈 + 𝑑(𝑃𝑉)……….1
For ideal gas 𝑃𝑉 = 𝑅𝑇 𝑎𝑛𝑑 ℎ𝑒𝑛𝑐𝑒, 𝑑𝐻 = 𝑑𝑈 + 𝑅𝑑𝑇, But 𝑑𝑈 = 𝐶𝑉 𝑑𝑇 𝑎𝑛𝑑 𝑑𝐻 = 𝐶𝑃 𝑑𝑇
Substituting in Eq.1 we get, 𝐶𝑃 𝑑𝑇 = 𝐶𝑉 𝑑𝑇 + 𝑅𝑑𝑇 , Rearranging results 𝐶𝑃 − 𝐶𝑉 = 𝑅

56. At what conditions the ideal gas law is obeyed more closely by a real gas?
The ideal gas law is applicable only at very low pressures and temperatures far away from the
critical temperatures. The most engineering applications the normal pressure range is between 10 and
20 atm. Also if the absolute temperature involved is at least twice the critical temperature the ideal
gas relations do not introduce serious error.

57. What are the two forms of second law of thermodynamics?

 All spontaneous processes are irreversible.

15 | BE 8256 Basic Mechanical Engineering / U – I / Compiled by R.Arul Kamalakumar

  All spontaneous processes proceed towards equilibrium.

58. Write down the statements of second law of thermodynamics?

 Kelvin Plank’s Statement: “No engine operating in a cycle can convert all heat it takes into
work”
 Clausius Statement: “Heat cannot flow from the cooler to a hotter body without producing
some other effects.”

59. What is third law of thermodynamics?

 The third law of thermodynamics implies that the entropy of any solid compound or for crystalline
substance is zero at absolute zero temperature.
 Entropy has a positive value at temperatures greater than absolute zero, which is useful to
measure the absolute entropy of a given substance.

 In the eighteenth century, the properties of matter at extremely low temperatures were being
investigated.
 The total entropy of the cold crystalline material was measured experimentally and that
began approaching zero.
 Since the entropy is an obvious function of T for all substances, the above equation became
obvious:

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16 | BE 8256 Basic Mechanical Engineering / U – I / Compiled by R.Arul Kamalakumar