Basic Concepts of Thermodynamics Study Notes for Mechanical Engineering

Thermodynamics is a science dealing with Energy and its transformation and its effect on the
physical properties of substances.

 It deals with equilibrium and feasibility of a process.

 Deals with the relationship between heat and work and the properties of systems in
equilibrium.

Thermodynamics System

 It is defined as the quantity of matter or a region in space chosen for study.

 The mass and region outside the system is called surrounding.
 Real or imaginary surface (mathematically thickness zero) that separates the system from
the surrounding is called the boundary.

Closed System (Control Mass):

 It consists of a fixed amount of mass and no mass can cross its boundary or leave or enter
a closed system.
 Energy in the form of heat or work can cross the boundary and the volume of closed
system does not have to be fixed
 Example: piston cylinder device.
Open System (Control Volume):

 It is a properly selected region in the space and both mass and energy region can cross the
boundary.
 The boundary of a control volume is called a control surface and they can be real or
imaginary.
 Example: Compressor, turbine, nozzle.

A control volume can be fixed, in size and shape as in case of nozzle or it may involve moving
boundaries as shown in Fig. (b).

Most control volume, however have fixed boundaries and thus do not involve any moving
boundaries.
Properties of a System: Any characteristic of a system is called a property. It can be
independent or dependent.

 Intensive properties: Which are independent of the size of system such as temperature,
pressure and density.
 Extensive properties: Whose values depend on the size or extent of the system such as
mass m, volume V and total energy E.

Divide the system into two equal parts with a partition to determine whether the property is
intensive or extensive.

Generally, upper case letters are used to denote extensive properties (exception m) and lower
case letters are used for intensive properties (exception P, T).

Extensive Property Intensive Property

Extensive properties are dependent on the mass of a Intensive properties are independent of the
system mass of a system
Extensive properties are additive Intensive properties are not additive
Its value for an overall system is the sum of its Its value remains the same whether one
values for the parts into which the system is divided considers the whole system or only a part of
 it.
Example:mass(m),volume(V),Energy(E),Enthalpy( Example:Pressure(P),Temperature(T),Densi
H) etc ty etc
Uppercase letters are used for extensive properties Lowercase letters are used for intensive
except mass properties except pressure(P) and temp.(T)

Specific Properties of a System: Extensive properties per unit mass are called specific
properties.

 Specific volume:

 Specific energy:

 Specific gravity (or relative density): It is used to define the density of a substance with
respect to density of some standard substance at a specified temperature. (Usually, water

at 4oC, = 1000 kg/m3)

Continuum:

 Continuum is defined as a continuous, homogeneous matter with no holes.

 The continuum idealization allows us to treat properties as point function.
 To assume properties to vary continually in space with no jump discontinuities.

State:

 State of system is described by its properties.

 At a given state, all the properties of a system have fixed values.
 However, there is no need to specify all the properties in order to fix a state.
 The number of properties required to fix the state of a system is given by the state
postulates.
 It property varies, other should be held constant.
 In other words, the condition of a system at any instant of time is called its state.
Equilibrium:

 The word equilibrium implies a state of balance.

 In an equilibrium state, there are no unbalanced potentials (or driving forces) within the
system.
 A system in equilibrium experience has no changes when it is isolated from its
surrounding.
 Thermodynamics deals with equilibrium states.
 A system is in thermal equilibrium if the temperature is same throughout the entire
system.
 In mechanical equilibrium, there is no change in pressure at any point of the system with
time.
 In chemical equilibrium, no chemical reactions occur.

Processes: Any change that a system goes from one equilibrium state to another equilibrium
state is called a process and series of states through which a system passes during a process is
called the path of the process.

Quasi-Equilibrium Process: When a process proceeds in such a manner that the system
remains infinitesimally close to an equilibrium state at all times, it is called a quasi-static or quasi
equilibrium process.
  Quasi equilibrium is an idealized process and is not a true representation of an actual
process.
 Quasi equilibrium processes are easy to analyze.
 Quasi equilibrium processes are work producing devices deliver the maximum work
when they operate on quasi equilibrium processes.
 Quasi equilibrium processes as standards to which actual processes can be compared.

Difference between Point Function Vs Path Function

Point Function Path Function

Any quantity, the value of which depends on
Any quantity whose change is independent of the
the path followed during a change of state is
path is known as point function
known as path function
The magnitude of such quantity in a process
The magnitude of such quantity in a process
is equal to the area under the curve on a
depends on the state.
property diagram
These are exact differential These are inexact differential. Inexact
 differential is denoted by δ
Properties are the examples of point function like
Ex: Heat and work
pressure(P), volume(V), Temp.(T),Energy etc.

Cycle: A system is said to have undergone a cycle if it returns to its initial state at the end of
process i.e., for a cycle the initial and final states are identical.

Steady Flow Process: Steady flow process is defined as a process during which a fluid flows
through a control volume steadily.

Temperature: The temperature is a measure (degree) of hotness or coldness. (freezing cold,

warm hot)

Temperature Scales:

 They are related to absolute temperature scales.

 The temperature scales used in the SI and English system are the celsius scale and the
Fahrenheit scale, respectively.
 A scale of temperature independent of the thermometric substance is called a
thermodynamic temperature scale.
 Kelvin scale is related to Celsius scale by

T(K) = T(C) + 273.16

 Rankine scale is related to Fahrenheit scale by

T(K) = T(C) + 459.67

 The temperature scales in the two unit systems are related by

Pressure

 Pressure is defined as the force exerted by a fluid per unit area.

 We speak of pressure only when we deal with gas or liquid.
 The counterpart of pressure is stress i.e., force per unit area.
o 1 pascal = 1N/m2
 o 1 bar = 105
o Pa = 0.1
o MPa = 100 kPa
o atm = 101325
o Pa = 101.325
o kPa = 1.01325 bar
o 1 kg f/cm2 = 9.807 N /cm2
o 1 kg f/cm2= 9.807 × 104 Pa
o 1 kg f/cm2= 0.9807 bar
o 1 kg f/cm2= 0.96788 atm

The actual pressure at a given position is called absolute pressure and it is measured relative to
absolute vacuum (i.e., absolute zero pressure)

 Pgauge = pabs – patm (for pressures above patm)

 pvac = patm - pabs (for pressures below patm)

where, Pgauge = gauge pressure, pabs = absolute pressure, and patm = atomic pressure

Thermodynamic Equilibrium

 A system is said to exist in a state of Thermodynamic Equilibrium when no changes in

macroscopic property is observed if the system is isolated from its surrounding.
 At the state of equilibrium, the properties of the system are uniform and only one value can be
assigned to it.
 A system will be in a state of thermodynamic equilibrium if the condition for following three
types of equilibrium are satisfied
 o Thermal Equilibrium (Equality of Temperature): A state of thermal equilibrium can be
described as one in which the temperature of the system is uniform.
o Mechanical Equilibrium(Equality of Pressure): In the absence of any unbalanced force
within the system itself and also between the system and the surroundings, the system
is said to be in a state of mechanical equilibrium.
 Mechanical equilibrium is related to pressure.
 A system is in mechanical equilibrium if there is no change in pressure at any
point of the system.
o Chemical Equilibrium(Equality of chemical potential): A system is in chemical
equilibrium when its chemical composition does not change with
time, that is no chemical reaction occurs .It is related to chemical potential

QUASI-STATIC PROCESS

 A quasi-static process is one in which the deviation from thermodynamic equilibrium is

infinitesimal.Characteristics:
 Infinite slowness is the characteristic feature of this process.
 A quasi-static process is thus a succession of equilibrium states.
 It can be represented as a continuous line on the property diagram.
 It is also known as a reversible process.

REVERSIBLE PROCESS

 A reversible process is one which is performed in such a way that at the end of the process both
the system and surrounding may be restored to their initial state without producing any changes
in rest of the Universe.
 A Reversible process is carried out infinitely slowly with an infinitesimal gradient so that every
state pass through by the system is in equilibrium.
 It is possible to execute the process in either of the direction.
 No dissipative effect such as friction, loss in a resistor, etc are present.
 Heat and work interactions of the system and the surroundings in the reverse process are equal
and opposite in direction to the same in the forward process.
 Eg of Reversible Process are
o Frictionless isothermal expansion or compression of a fluid.
o Frictionless adiabatic expansion or compression of a fluid.
o Elastic stretching of a solid.
o Electric current with zero resistance.
IRREVERSIBLE PROCESS

 An irreversible process is one that is carried out in such a way that the system and surrounding
can not be exactly restored to their respective initial state at the end of the reverse process, that
a net change occurs in the Universe.
 In an irreversible the surrounding would always be affected by loss of work and gain of low
temperature heat, which can be considered as waste heat for the surrounding.
 The irreversibility of a process may be due to either one or both of the following.
o Lack of Equilibrium: between the system and the surroundings or between the two
systems causes a spontaneous change which makes the process irreversible such as Free
expansion or Unrestrained expansion and Heat transfer through a finite temperature
difference
o Involvement of Dissipative effects: Dissipation results in the transformation of work into
molecular energy of the system such as Paddle wheel work transfer.

Heat & Work Transfer

 Thermodynamic Work: Work is said to be done by a system if the sole effect on things external
to the system can be reduced to the raising of a weight.

Displacement (or) pdV Work

Expression for pdV Work:
 Sign Convention for work transfer:Work done by the system is positive and Work done on the
system is negative
Work done during various Quasi-static Processes:
Constant Pressure Proces:
Constant Volume Process:
Constant Temperature Process:
eroth and First Laws of Thermodynamics
Study notes for Mechanical Engineering
 123 upvotes
 18 comments

Zeroth Law of thermodynamics

 When two bodies have equality of temperature with a third body, then they have equality of
temperature
 Definition of the zeroth law enables the use of a thermometer as a measurement device.
 A scale, however, needs to be defined. The old metric temperature scale, Celsius (◦C), was
defined so that 0◦C is the freezing point of water, and 100 ◦C is the boiling point of water
 These quantities varied with pressure, however, so that different values would be obtained on
top of a mountain versus down in the valley, and so this is not a good standard.
 The modern Celsius scale is defined to be nearly the same but has 0.01 ◦C as the so-called triple
point of water, and−273.15 ◦C as absolute zero in K.
 The triple point of water is defined at the state where three phase of water (solid, liquid, and
gas) are observed to co-exist.
 The transformation between the absolute Kelvin scale and the Celsius scale is given by

K =◦C + 273.15

 The English equivalents are degrees Fahrenheit (◦F) for relative temperature and degrees
Rankine (◦R) for absolute temperature. The conversions are
 T(◦R) = 1.8T(K),

T(◦F) = 1.8T(◦C) + 32, T(◦F) = T(◦R) − 459.67

Fixed Point Temp.(c)

Ice Point 0.01

Steam Point 100

Solidification of antimony 630.74

Solidification of Gold 1064.43

The First Law of Thermodynamics

 The first law of thermodynamics can be simply stated as follows: during an interaction between
a system and its surroundings, the amount of energy gained by the system must be exactly
equal to the amount of energy lost by the surroundings.
 A closed system can exchange energy with its surroundings through heat and work transfer. In
other words, work and heat are the forms that energy can be transferred across the system
boundary.
 Based on kinetic theory, heat is defined as the energy associated with the random motions of
atoms and molecules.
 Heat is a directional (or vector) quantity; thus, it has magnitude, direction and point of action.
o Q (kJ) amount of heat transfer
o Q° (kW) rate of heat transfer (power)
o q (kJ/kg) ‐ heat transfer per unit mass
o q° (kW/kg) ‐ power per unit mass
o Sign convention: Heat Transfer to a system is positive, and heat transfer from a system
is negative. It means any heat transfer that increases the energy of a system is positive,
and
heat transfer that decreases the energy of a system is negative
 Work is the energy interaction between a system and its surroundings. More specifically, work is
the energy transfer associated with a force acting through a distance.
o W (kJ) amount of work transfer
o W° (kW) power
o w (kJ/kg) ‐ work per unit mass
o w° (kW/kg) ‐ power per unit mass
o Sign convention: work done by a system is positive, and the work done on a system is
negative.
Similarities between work and heat transfer

 Both are recognized at the boundaries of the system as they cross them (boundary phenomena).
 Systems posses energy, but not heat or work (transfer phenomena).
 Both are associated with a process, not a state. Heat or work has no meaning at a state.
 Both are path functions, their magnitudes depend on the path followed during a process as well
as the end states

First Law of Thermodynamics

 First law, or the conservation of energy principle, states that energy can be neither created nor
destroyed; it can only change forms.
 The first law cannot be proved mathematically, it is based on experimental observations, i.e.,
there are no process in the nature that violates the first law.
 The first law for a closed system or a fixed mass may be expressed as:

net energy transfer to (or from) the system as heat and work= net increase (or decrease) in
the total energy of the system
 Q – W = ΔE (kJ)

where
Q = net heat transfer (=ΣQin – ΣQout)
W= net work done in all forms (=ΣWin – ΣWout)
ΔE= net change in total energy (= E2 – E1)

 The change in total energy of a system during a process can be expressed as the sum of the
changes in its internal, kinetic, and potential energies:

ΔE= ΔU + ΔKE + ΔPE (kJ)

ΔU= m(u2-u1)

ΔKE=1/2(mV22 - mV12)

ΔPE=mg(z2-z1)

Note: for stationary systems ΔPE=ΔKE=0, the first law reduces to

Q – W = ΔU

 The first law can be written on a unit‐mass basis:

q – w = Δe (kJ/kg)

or in differential form:

δQ – δW = dU (kJ)

 For a cyclic process, the initial and final states are identical, thus ΔE=0. The first law becomes:

Q – W = 0 (kJ)

 Note: from the first law point of view, there is no difference between heat transfer and work,
they are both energy interactions. But from the second law point of view, heat and work are
very different.

Specific Heats

 The specific heat is defined as the energy required to raise the temperature of a unit mass of a
substance by one degree. There are two kinds of specific heats:
o specific heat at constant volume, Cv (the energy required when the volume is
maintained constant)
o specific heat at constant pressure, Cp (the energy required when the pressure is
maintained constant)
 The specific heat at constant pressure Cp is always higher than Cv because at constant pressure
the system is allowed to expand and energy for this expansion must also be supplied to the
system.
 For a stationary closed system undergoing a constant‐volume process (wb = 0), Applying the first
law in the differential form:

δq – δw = du
at constant volume (no work) and by using the definition of Cv, one can write:

 Similarly, an expression for the specific heat at constant pressure Cp can be found. From the first
law, for a constant pressure process (wb + Δu = Δh). It yields:

 Specific heats (both Cv and Cp) are properties and therefore independent of the type of
processes.
 Cv is related to the changes in internal energy u, and Cp to the changes in enthalpy,h.
 It would be more appropriate to define:
o Cv is the change in specific internal energy per unit change in temperature at constant
volume.
o Cp is the change in specific enthalpy per unit change in temperature at constant
pressure.

Specific heats for ideal gases

 It has been shown mathematically and experimentally that the internal energy is a function of
temperature only

u=u(T)

 Using the definition of enthalpy (h = u + Pv) and the ideal gas equation of state (Pv = RT), we
have: h = u + RT
 Since R is a constant and u is a function of T only: h = h(T)
 Therefore, at a given temperature, u, h, Cv and Cp of an ideal gas will have fixed values
regardless of the specific volume or pressure.
 For an ideal gas, we have, du= Cv(T) dT and dh= Cp(T) dT
 For an ideal gas, we can write:

 The ratio of specific heats is called the specific heat ratio k = Cp/Cv
o varies with temperature, but this variation is very mild.
o for monatomic gases, its value is essentially constant at 1.67.
o Many diatomic gases, including air, have a specific heat ratio of about 1.4 at room
temperature.

Specific heats for solids and liquids

  A substance whose specific volume (or density) is constant is called incompressible substance.
 The specific volumes of solids and liquids (which can be assumed as incompressible substances)
essentially remain constant during a process.
 The constant volume assumption means that the volume work (boundary work) is negligible
compared with other forms of energy.
 As a result, it can be shown that the constant‐volume and constant‐pressure specific heats are
identical for incompressible substances:

Cp = Cv = C

 For small temperature intervals, a C at averaged temperature can be used and treated as a
constant, yielding:

ΔU≈ Cavg(T2-T1)

 The enthalpy change of incompressible substance can be determined from the definition of
enthalpy (h = u + Pv)

h2 – h1 = (u2 – u1) + v(P2 – P1)

Δh = Δu + vΔP (kJ/kg)

Calculation of Work and Heat in Various

Processes
 36 upvotes
 5 comments

Work Done in Moving the Boundaries of a Closed System

Suppose a gas contained in piston cylinder expands from position 1 to 2, then work done by the gas
 Constant Volume Process (Isochoric Process):
o In isochoric process, volume is constant during process.
o Work done: dW = pdV = 0
o Heat supplied to system: dQ = mCv dt
 o ΔQ = mCv(T2-T1) Where, Cv = Specific heat for constant volume process.

 Change in internal energy of system:

dU = mCv dt

ΔU = mCv(T2-T1)

Constant Pressure Process (Isobaric Process):

  In isobaric process, pressure is constant throughout process
 ΔW = p2V2 – p1V1 = mR (T2-T1)
 ΔQ = mCp(T2-T1)
 ΔU = mCv(T2-T1)

Constant Temperature (Isothermal Process):

 In isothermal process, temperature is constant during process.

 If an ideal gas follows a constant temperature process, then Boyle’s law is

pV = constant

or
Reversible Adiabatic Process:

In reversible adiabatic process there is no heat transfer between the system and the surrounding (Q = 0)

pVγ= constant,

Where, r = adiabatic index, and Cp = specific heat for constant pressure

ΔQ = 0 (No heat transfer from surrounding)

ΔU = -ΔW, (0 = ΔU + ΔW)

Reversible Polytrophic Process:

 In polytropic process, both heat and work transfers take place.

 The process equation is represented by p.Vn = C where n is called the index of process or
polytropic index.

where, n = polytropic index