BE 8256 - Basic Mechanical Engineering

UNIT II HEATING AND EXPANSION OF GASES

Expressions for work done, Internal energy and heat transfer for Constant Pressure, Constant
Volume, Isothermal, Adiabatic and Poly-tropic processes-Derivations and problems; Free
expansion and Throttling process.

1. Elaborate heat and work?

Heat and work are both forms of energy. They are also related forms, in that one can be
transformed into the other. Heat energy (such as steam engines) can be used to do work (such as
pushing a train down the track). Work can be transformed into heat, such as might be experienced
by rubbing your hands together to warm them up.
Work and heat can both be described using the same unit of measure. Sometimes the calorie
is the unit of measure, and refers to the amount of heat required to raise one (1) gram of water one
(1) degree Celsius. Heat energy is measured in kilocalories, or 1000 calories. Typically, we use
the SI units of Joules (J) and kilojoules (kJ). One calorie of heat is equivalent to 4.187 J. You will
also encounter the term specific heat, the heat required to raise one (1) gram of a material one (1)
degree Celsius. Specific heat, normally referred at constant pressure, and represented by the
symbol "CP", is generally defined as:

𝑞
𝐶𝑃 =
𝑚∆𝑇

Where:
C P= specific heat in cal/g-°C
q = heat added in calories,
m = mass in grams
ΔT = rise in temperature of the material in °C.
The value of CP for water is 1 cal/g-°C.

2. Explain heat capacity.

The specific heat capacity of a solid or liquid is defined as the heat required raising unit
mass of substance by one degree of temperature. This can be stated by the following
equation:
∆𝑄 = 𝑚 𝐶 ∆𝑇
where, ∆Q= Heat supplied to substance, m= Mass of the substance, c= Specific heat
capacity, ∆T= Temperature rise.

There are two definitions for vapors and gases:

Cp = Specific heat capacity at constant pressure, i.e.

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 𝜕ℎ
𝐶𝑃 = ( )
𝜕𝑇 𝑃

Cv = Specific heat capacity at constant volume, i.e.

𝜕𝑢
𝐶𝑉 = ( )
𝜕𝑇 𝑉

It can be shown that for a an ideal or perfect gas, 𝐶𝑃 − 𝐶𝑉 = 𝑅, where R is the gas
constant.
𝐶
The ratio, 𝐶𝑃 , has been given symbol γ,
𝑉
𝐶𝑃
𝛾=
𝐶𝑉
and is always greater than unity. The approximate value of this ratio is 1.6 for monatomic gases
such as Ar and He. Diatomic gases (such as 𝐻2 , 𝑁2 , 𝑂2 , 𝐶𝑂) have a g ratio about 1.4 and triatomic
(such as𝑆𝑂2 , 𝐶𝑂3 ) 1.3

3. First law of thermodynamics.

The first law of thermodynamics may be stated in two forms
 As the law of conservation of energy: It states that energy can be transformed (changed
from one form to another), but cannot be created or destroyed
 In terms of increase in internal energy: The net energy change (ΔU) of a closed system is
equal to heat transferred to the system minus the work done by the system.
dU = dQ – dW which gives ΔU=Q-W

4. Enthalpy :
 The enthalpy which is defined to be the sum of the internal energy E plus the
product of the pressure p and volume V. Using the symbol H for the enthalpy.
 H = E + PV
 Where:
H=enthalpy
E= energy of the system
PV = pressure in atm times volume in liters
 Enthalpy is a state function.

5. Internal energy
 Internal energy is the total energy content of the system
 Internal energy (U) is the capacity to do work plus the capacity to release heat
 The internal energy of a thermodynamic system, or a body with well-defined
boundaries, denoted by U, or sometimes E, is the total of the kinetic energy due to

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 the motion of particles (translational, rotational, vibrational) and the potential energy
associated with the vibrational and electric energy of atoms within molecules or
crystals
 It is a state function of a system, and is an extensive quantity.

6. Heat capacity.
The heat capacity of a substance is the quantity of heat to be supplied to effect a
temperature rise of one degree, the units J/K (Joule per Kelvin)
C= dQ / dT

7. Write the first law thermodynamic equation for an open and a closed systems.
a. Open system
The general equation for energy and material balances are as follows:
𝐸𝑛𝑒𝑟𝑔𝑦 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
= 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡𝑝𝑢𝑡 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 + 𝐸𝑛𝑒𝑟𝑔𝑦 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
𝑀𝑎𝑠𝑠 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑀𝑎𝑠𝑠 𝑜𝑢𝑡𝑝𝑢𝑡 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 +
𝑀𝑎𝑠𝑠 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚
Under steady state condition energy and mass change in system are zero
b. Closed System
𝒎∆𝑬 = 𝑸 − 𝑾 𝑜𝑟 𝑖𝑛 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑡𝑖𝑎𝑙 𝑓𝑜𝑟𝑚 𝑎𝑠, 𝒎𝒅𝑬 = 𝒅𝑸 − 𝒅𝑾
Where, m is mass of the system, E is internal energy of the system, Q is heat added to the system
and W is the work done by the system.

8. 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.

9. First law for cyclic process.

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

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

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

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

11. 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

12. 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

13. 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
𝐶𝑃
And pressure and volume are related as, 𝑃𝑉 𝛾 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑎𝑛𝑑 𝛾 = 𝐶𝑉
Work done = 𝑊 = 𝐶𝑉 (𝑇1 − 𝑇2 )

14. 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.

15. “The enthalpy of an ideal gas depends only on the temperature” and “the internal is only a
function of temperature” – State your comment on the statement.
The internal energy of an ideal gas depends only on temperature. It is independent of
pressure and volume.

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 𝜕𝑈 𝜕𝑈
(
) =0= ( )
𝜕𝑉 𝑇 𝜕𝑃 𝑇
The increase in temperature of an ideal gas results in increased kinetic activity of molecules
which is noticed as increase in its internal energy. When a gas is compressed at constant
temperature, it will offer no resistance and consequently results in no change in its energy, as
there are no intermolecular forces to overcome. So it is clear that the change in internal energy
is a function of temperature.
As the enthalpy is the measure of change in internal energy of a system, enthalpy is also a
function depends only on temperature.

16. 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

17. 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.

18. 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

19. 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.

20. Define reduced pressure (PR), reduced temperature (TR) and reduced volume (VR).
𝑃 𝑇 𝑉
𝑃𝑅 = , 𝑇𝑅 = , 𝑎𝑛𝑑 𝑉𝑅 = , 𝑊ℎ𝑒𝑟𝑒 𝑃𝐶 , 𝑇𝐶 𝑎𝑛𝑑 𝑉𝐶 𝑎𝑟𝑒 critical pressure, critical
𝑃𝐶 𝑇𝐶 𝑉𝐶
temperature and critical volume.

𝑹
21. Show that 𝑪𝑽 = 𝜸−𝟏
𝐶𝑃
We know = 𝛾, also 𝐶𝑃 − 𝐶𝑉 = 𝑅
𝐶𝑉

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 𝑅
⟹ 𝐶𝑉 𝛾 − 𝐶𝑉 = 𝑅 ⟹ 𝐶𝑉 (𝛾 − 1) = 𝑅 𝐻𝑒𝑛𝑐𝑒 𝐶𝑉 = 𝛾−1

22. State the law of corresponding states.

The law states that all gases under the same reduced conditions of temperature and pressure
has the same compressibility factor. In other words all gases under identical reduced conditions
deviate from the ideal behavior by an equal quantity. Mathematically
𝑍 = 𝑓(𝑃𝑅 , 𝑇𝑅 )

23. What do you mean by a ‘Z’ chart?

‘Z’ charts are otherwise called as generalized compressibility charts, are the charts involve
plotting compressibility factor ‘Z’, reduced pressure (PR) and reduced temperature (TR), where
reduced pressure is in abscissa and compressibility factor in ordinate and reduced temperature
as parameter.
The generalized compressibility charts provide one of the best means of expressing the
deviation from ideal behavior. When the precise equation of state is not available, these charts
provide a convenient method for the evaluation of compressibility factor. The average
deviation of the values from the experimental value is within 5%.

24. State Dalton’s law and Amagat’s law.

Dalton’s law: It states that the total pressure exerted by a gaseous mixture is equal to the sum
of partial pressure of the constituting component gases.
𝑃 = 𝑝1 + 𝑝2 + 𝑝3 + ⋯ + 𝑝𝑖 , 𝑝1 = 𝑃𝑥1 and so on.
∑𝑛𝑖=1 𝑝𝑖 (OR) ∑𝑛𝑖=1 𝑃𝑥𝑖
Amagat’s law: It states the total volume occupied by a gaseous mixture is equal to the
sum of the partial volume
volume of the constituting component gas.
𝑉 = 𝑣1 + 𝑣2 + 𝑣3 + ⋯ + 𝑣𝑛 , 𝑣1 = 𝑉𝑥1
∑𝑛𝑖=1 𝑣𝑖 (OR) ∑𝑛𝑖=1 𝑉𝑥1

25. Explain Kay’s rule.

The compressibility factor Z M is evaluated at the molar average of the critical and
pressure of the mixtures,
𝑇𝐶𝑀 = 𝑇𝐶𝐴 𝑦𝐴 + 𝑇𝐶𝐵 𝑦𝐵
𝑃𝐶𝑀 = 𝑃𝐶𝐴 𝑦𝐴 + 𝑃𝐶𝐵 𝑦𝐵 , where 𝑦𝐴 𝑎𝑛𝑑 𝑦𝐵 are, mole fractions of A and B in the mixture.
The critical properties 𝑇𝐶𝑀 𝑎𝑛𝑑 𝑃𝐶𝑀 are called pseudo critical properties. If ZM is the
𝑃𝑉
compressibility factor of the mixture as evaluated from 𝑃𝐶𝑀 𝑎𝑛𝑑 𝑇𝐶𝑀 , then 𝑅𝑇 = 𝑍𝑀
In the intermediate range of 50 to 300 atm this rule is very reliable.

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26. 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

27. Explain concept of Enthalpy in detail.

Enthalpy is an interesting concept: it is defined by its change rather than a single entity. A
state property, the word enthalpy comes from the Greek "heat inside". If you have a chemical
system that undergoes some kind of change but has a fixed volume, the heat output is equal to the
change in internal energy (q = ΔU). We will define the enthalpy change, ΔH, of a system as being
equal to its heat output at constant pressure:
dH = q at constant pressure
Where,
ΔH = change in enthalpy
We define enthalpy itself as: H = U + PV
Where:
H = enthalpy
U = internal energy of the system
PV = pressure in atm times volume in liters
We will not able to calculate the enthalpy directly; we are only interested in the change in
enthalpy, or ΔH.
∆𝐻 = 𝐻𝐹𝑖𝑛𝑎𝑙 − 𝐻𝐼𝑛𝑖𝑡𝑖𝑎𝑙 Or ∆𝐻 = 𝐻𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐻𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
Usually tables of enthalpies are generally given as ΔH values.

We can also represent enthalpy change with the equation:

ΔH = ΔE + P ΔV
Where:
ΔV is the change in volume, in liters and P is the constant pressure

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 But work is defined as P ΔV, so enthalpy changes are simply a reflection of the amount of
energy change (energy going in or out, endothermic or exothermic), and the amount of
work being done by the reaction.
For example, if ΔE = -100 kJ in a certain combustion reaction, but 10 kJ of work needs to
be done for the products, the change in enthalpy is:
ΔH = -100 kJ + 10 kJ = -90 kJ
This is an exothermic reaction (which is expected with combustion), and 90 kJ of
energy is released to the environment. Basically, you get warmer. Notice the convention used
here a negative value represents energy coming out of the system.

28. Graphically represent various thermodynamic processes.

There are a number of different thermodynamic processes that can change the pressure and/or
the volume and/or the temperature of a system. To simplify matters, consider what happens when
something is kept constant. The different processes are then categorized as follows:
1. Isobaric - the pressure is kept constant. An example of an isobaric system is a
gas, being slowly heated or cooled, confined by a piston in a cylinder. The work
done by the system in an isobaric process is simply the pressure multiplied by the
change in volume, and the P-V graph looks like:

2. Isochoric - the volume is kept constant. An example of this system is a gas in a

box with fixed walls. The work done is zero in an isochoric process, and the P-V
graph looks like:

3. Isothermal - the temperature is kept constant. A gas confined by a piston in a

cylinder is again an example of this, only this time the gas is not heated or cooled,
but the piston is slowly moved so that the gas expands or is compressed. The
temperature is maintained at a constant value by putting the system in contact with
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 a constant-temperature reservoir (the thermodynamic definition of a reservoir is
something large enough that it can transfer heat into or out of a system without
changing temperature).
If the volume increases while the temperature is constant, the pressure must decrease,
and if the volume decreases the pressure must increase.
In an isothermal process, the temperature stays constant, so the pressure and volume
are inversely proportional to one another. The P-V graph for an isothermal process looks
like this:

The work done by the system is still the area under the P-V curve, but because this
is not a straight line the calculation is a little tricky, and really can only properly be done
using calculus.
The internal energy of an ideal gas is proportional to the temperature, so if the
temperature is kept fixed the internal energy does not change. The first law, which deals
with changes in the internal energy, thus becomes 0 = Q - W, so Q = W. If the system does
work, the energy comes from heat flowing into the system from the reservoir; if work is
done on the system, heat flows out of the system to the reservoir.

4. Adiabatic - in an adiabatic process, no heat is added or removed from the system.

In an adiabatic process, no heat is added or removed from a system. The first law
of thermodynamics is thus reduced to saying that the change in the internal energy
of a system undergoing an adiabatic change is equal to -W. Since the internal energy
is directly proportional to temperature, the work becomes:

Note: The suffix ‘i’ indicates the initial and ‘f’ indicates the final condition of a given
process

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 An example of an adiabatic process is a gas expanding so quickly that no heat can be
transferred. The expansion does work, and the temperature drops. This is exactly what happens
with a carbon dioxide fire extinguisher, with the gas coming out at high pressure and cooling as it
expands at atmospheric pressure.

29. Define a constant volume (isochoric) process in terms of thermodynamic equations.

An isochoric thermodynamic process is characterized by constant volume, i.e.,
. The process does no pressure-volume work, since such work is defined by
, where P is pressure. The sign convention is such that positive work is performed by
the system on the environment.
For a reversible process, the first law of thermodynamics gives the change in the system's
internal energy:

Replacing work with a change in volume gives

Since the process is isochoric, , the previous equation now gives

Using the definition of specific heat capacity at constant volume,

,

Integrating both sides yields

Where is, the specific heat capacity at constant volume, is initial temperature and is final
temperature. and conclude with:
(or)
∆𝑼 = 𝑼𝟐 − 𝑼𝟏 = ∫ 𝑪𝑽 𝒅𝑻

30. Define a constant pressure (isobaric) process in terms of thermodynamic equations.

An isobaric process is a thermodynamic process in which the pressure stays constant. The
term derives from the Greek isos, (equal), and barus, (heavy). The heat transferred to the
system does work but also changes the internal energy of the system:

According to the first law of thermodynamics, where W is work done by the system, U is
internal energy, and Q is heat. Pressure-volume work by the closed system is defined as:

where Δ means change over the whole process, whereas d denotes a differential. Since
pressure is constant, this means that
.
Applying the ideal gas law, this becomes

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 Assuming that the quantity of gas stays constant, e.g., there is no phase transition during a
chemical reaction. According to the equi-partition theorem, the change in internal energy
is related to the temperature of the system by
,
where is specific heat at a constant volume. Substituting the last two equations into the
first equation produces:

,where is specific heat at a constant pressure.(or)

∆𝑯 = 𝑯𝟐 − 𝑯𝟏 = ∫ 𝑪𝑷 𝒅𝑻

31. Define a constant temperature (isothermal) process in terms of thermodynamic equations.

For an isothermal, reversible process, this integral equals the area under the relevant
pressure-volume isotherm, and is indicated in blue in the figure (at the bottom right-hand of
the page) for an ideal gas. Again, p = nRT / V applies and with T being constant (as this is an
isothermal process), we have:

By convention, work is defined as the work the system does on its environment. If, for
example, the system expands by a piston moving in the direction of force applied by the
internal pressure of a gas, then the work is counted as positive, and as this work is done by
using internal energy of the system, the result is that the internal energy decreases.
Conversely, if the environment does work on the system so that its internal energy increases,
the work is counted as negative.
It is also worth noting that, for many systems, if the temperature is held constant, the
internal energy of the system also is constant, and so . From First Law of
Thermodynamics, , so it follows that for this same isothermal process.
When no heat flows into or out of the gas because the temperature is constant, then there is no
work done. Thus, work=0 which means external pressure is zero. This is called free expansion.

32. Define an adiabatic (no heat exchange within a system) process in terms of thermodynamic
equations.
An adiabatic process is a conversion that occurs without input or release of heat within a
system. Many rapid chemical and physical processes are described in this way. Such processes
are usually followed or preceded by events that do involve heat. Examples include electron-
transfer.
The mathematical equation for an ideal gas undergoing a reversible (i.e., no entropy
generation) adiabatic process is

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 where P is pressure, V is specific or molar volume, and

being the specific heat for constant pressure, being the specific heat for constant
volume, is the adiabatic index, and is the number of degrees of freedom (3 for
monatomic gas, 5 for diatomic gas).
For a monatomic ideal gas, , and for a diatomic gas (such as nitrogen and oxygen,
the main components of air) . Note that the above formula is only applicable to
classical ideal gases and not Bose–Einstein or Fermi gases.
For reversible adiabatic processes, it is also true that

, where T is an absolute temperature.

This can also be written as

33. Define a cyclic process.

Thermodynamic cycle consists of a series of thermodynamic processes transferring heat
and work, while varying pressure, temperature, and other state variables, eventually returning
a system to its initial state.[1] In the process of going through this cycle, the system may perform
work on its surroundings, thereby acting as a heat engine.
State quantities depend only on the thermodynamic state, and cumulative variation of such
properties adds up to zero during a cycle. Process quantities (or path quantities), such as heat
and work are process dependent, and cumulative heat and work are non-zero. The first law of
thermodynamics dictates that the net heat input is equal to the net work output over any cycle.
The repeating nature of the process path allows for continuous operation, making the cycle an
important concept in thermodynamics. Thermodynamic cycles often use quasistatic processes
to model the workings of actual devices.
Two primary classes of thermodynamic cycles are power cycles and heat pump cycles.
Power cycles are cycles which convert some heat input into a mechanical work output, while
heat pump cycles transfer heat from low to high temperatures using mechanical work input

Because the net variation in state properties during a thermodynamic cycle is zero, it
forms a closed loop on a PV diagram. A PV diagram's Y axis shows pressure (P) and X axis
shows volume (V). The area enclosed by the loop is the work (W) done by the process:

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 This work is equal to the balance of heat (Q) transferred into the system:

Equation (2) makes a cyclic process similar to an isothermal process: even though the
internal energy changes during the course of the cyclic process, when the cyclic process
finishes the system's energy is the same as the energy it had when the process began.
If the cyclic process moves clockwise around the loop, then W will be positive, and it
represents a heat engine. If it moves counterclockwise, then W will be negative, and it
represents a heat pump

34. What do you mean by adiabatic heating and cooling?

Adiabatic heating occurs when the pressure of a gas is increased from work done on it by
its surroundings, e.g. a piston. Diesel engines rely on adiabatic heating during their
compression stroke to elevate the temperature sufficiently to ignite the fuel.
Adiabatic cooling occurs when the pressure of a substance is decreased as it does work on
its surroundings. Adiabatic cooling occurs in the Earth's atmosphere with orographic
(Orographic lift occurs when an air mass is forced from a low elevation to a higher elevation
as it moves over rising terrain. As the air mass gains altitude it quickly cools down
adiabatically, which can raise the relative humidity to 100% and create clouds and, under the
right conditions, precipitation) lifting and lee waves, and this can form pileus or lenticular
clouds (Lenticular clouds (Altocumulus lenticularis) are stationary lens-shaped clouds that
form at high altitudes, normally aligned perpendicular to the wind direction) if the air is cooled
below the dew point. When the pressure applied on a parcel of air decreases, the air in the
parcel is allowed to expand; as the volume increases, the temperature falls and internal energy
decreases.

35. Define a polytropic process in terms of thermodynamic equations.

A polytropic process is a thermodynamic process that obeys the relation i.e pressure –
volume relation
where p is the pressure, V is volume, n, the polytropic index, is any real number, and C is a
constant. This equation can be used to accurately characterize processes of certain systems, notably
the compression or expansion of a gas and in some cases liquids and solids.
For certain values of the polytropic index, the process will be synonymous with other common
processes. Some examples of the effects of varying index values are given in the table.

Polytropic index 𝒏 Process Effect

𝑛 <0 unpredictab explosion occur
le

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 𝑛=0 isobaric constant pressure
𝑛=1 isothermal constant temperature
1 < 𝛾 <1 intermediat a quasi-adiabatic process such as in an internal combustion engine
e during expansion, or in vapor compression refrigeration during
compression
𝑛= 𝛾 adiabatic no heat transferred
𝑛= ∞ isochoric constant volume

When the index n is between any two of the former values (0, 1, gamma, or infinity), it means
that the polytrophic curve, will bounded by the curves of the two corresponding indices.

36. What are the limitations of first law of thermodynamics?

 The first law of thermodynamics have serious limitations by not specifying the
direction of flow of energy
 Not able to tell whether a process is feasible
 Does not speak about the spontaneous (i.e.,) natural process.

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

 All spontaneous processes are irreversible.
 All spontaneous processes proceed towards equilibrium.

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

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

39. Define spontaneous process.

 A process, which proceeds of its own under a given set of conditions, is called as
a spontaneous process.
 It occurs in one direction only and it is also known as natural process.
 It always proceeds is the direction which leads to the attainment of equilibrium.
The tendency of a process to occur spontaneously is called spontaneity.
Ex. Flow of water from hills, evaporation of water etc.

40. Non – spontaneous process; -

 A process, which cannot proceed by itself, is known as non-spontaneous process.
Ex. Electrolysis of water to produce hydrogen and oxygen takes place as long as the
electric current is passed, formation of ice in a refrigerator takes place as long as the
electric current is supplied to it etc.

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41. Write the two prepositions or two theorems of Carnot principles.
 No heat engine operating in a cycle between constant temperature reservoirs can
be more efficient than a reversible engine working between the same two
reservoirs.
𝜂𝐼𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 < 𝜂𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒
 All reversible engines say A,B working between two constant temperature
reservoirs have the same efficiency irrespective of the working substance and this
efficiency is depend only on the temperature levels,
𝜂𝐼𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒(𝐴) = 𝜂𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒(𝐵)

42. What is cannot efficiency?

Efficiency = Heat Energy converted into work
Heat energy supplied
𝑄1 − 𝑄2 𝑇2
𝜂= 𝑜𝑟 𝜂 = 1 −
𝑄1 𝑇1
From the above relation, we can say that
 Efficiency depends on the temperature of hot and cold bodies.
 It is independent of nature of working substance.
 It can be operated in a reverse process also
 Efficiency will never be 100% for any engine.

43. Define COP

 The work required would be minimum for an ideal Carnot machine acting as a
refrigerator. The relation gives the coefficient of performance (COP) of such a
machine.
𝑄2 𝑇2 𝑄2
𝐶𝑂𝑃 = = =
𝑊 𝑇1 − 𝑇2 𝑄1 − 𝑄2
 The efficiency or coefficient of performance (COP) of a refrigerator is defined as
the quantity of heat absorbed of the low temperature per unit work.

44. Define available energy.

When heat is supplied to the system some portion of this heat is used up in doing work. This
portion of heat is called workable or available energy.

45. Define unavailable energy.

The portion of energy not used for doing useful work called unavailable energy.

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  The second law of thermodynamics says that entropy is a measure of unavailable
energy. Hence, entropy can be defined as unavailable energy per unit temperature.
𝑈𝑛𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑒𝑛𝑒𝑟𝑔𝑦
 𝐸𝑛𝑡𝑟𝑜𝑝𝑦 = 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒

46. Distinguish between heat engine and heat pump.

S.No. Heat Engine Heat Pump

1 In a heat engine heat is absorbed from the In a heat pump the heat is absorbed
source and is given to the sink
2 The heat flows from a body of higher to The heat flows from a body of lower to
lower temperature higher temperature with the help of
external work
3 The work is done by the working material The work done on the work in material
and is always positive and is always negative

47. Third law of thermodynamics (or) absolute entropy:

At absolute zero temperature, the entropy tends to zero and the molecules of a system arranged in
a perfect order.
Ex: When ice is converted into water and then into steam, the entropy increases, when steam is
converted into water and then into ice, the entropy decreases

48. Write the combined statement of first and second law.

For a closed system by the first law: 𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 ⟹ 𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
By second law: 𝑑𝑄 = 𝑑𝑄𝑟𝑒𝑣 = 𝑇𝑑𝑆
For reversible process: 𝑑𝑊 = 𝑃𝑑𝑉 (for displacement work
Substituting for 𝑑𝑊 ∶ 𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉
Substituting for 𝑑𝑄: 𝑻𝒅𝑺 = 𝒅𝑼 + 𝑷𝒅𝑽
The enthalpy is given by: 𝐻 = 𝑈 + 𝑃𝑉 ⇒ 𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
Substituting for 𝑑𝑈 + 𝑃 𝑑𝑉 ⇒ 𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 ⟹ 𝑻𝒅𝑺 = 𝒅𝑯 − 𝑽𝒅𝑷
 The equations 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉 𝑎𝑛𝑑 𝑇𝑑𝑆 = 𝑑𝐻 − 𝑉𝑑𝑃 are known as fundamental
thermodynamic relations combining first and second laws into a single equation.
 Even though these equations derived for reversible process it is applicable for irreversible process
also, as it expresses relationship among the properties of the closed system which are independent
of path.

49. What is a free expansion process?

 Free expansion is an irreversible process in which a gas expands into an insulated evacuated
chamber. It is also called Joule expansion.
 The enclosure is insulated so there is no heat exchange. The first law tells us therefore that the
internal energy is constant. For an ideal gas, the internal energy is a function of temperature only
so that the temperature of the gas before the free expansion and after the expansion has been
completed is the same.

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  Unlike ideal gases, the temperature of a real gas will change during a Joule expansion. Empirically,
it is found that almost all gases cool during a Joule expansion at all temperatures investigated. Since
internal energy is constant, cooling must be due to the conversion of internal kinetic energy to
internal potential energy, with the opposite being the case for warming.
 For an ideal gas, no work done, i.e. a free expansion, there is no change in internal energy and the
process is isothermal.

50. What do you mean by inversion temperature of a gas?

 The inversion temperature in thermodynamics and cryogenics is the critical temperature below
which a non-ideal gas (all gases in reality i.e. real gases) that is expanding at constant enthalpy will
experience a temperature decrease, and above which will experience a temperature increase.
 This temperature change is known as the Joule-Thomson effect, and is exploited in the liquefaction
of gases. Inversion temperature depends on the nature of gas.

51. Why is work done in free expansion zero?

 From the first law for a closed system that the change in internal energy of the gas will be equal to
the heat transferred plus the amount of work the gas does.(or)
 the gas expands freely (the volume change of the system is zero), we know that no work will be
done, so W=0.

52. Write a note on throttling process.

 A throttling process, also called a Joule-Thomson process, is a type of isenthalpic process where a
liquid or gas is cooled as it passes from a higher pressure state to a lower pressure state. This process
is called a Joule –Thomson process.
 This process is especially very important in field of refrigeration where refrigerant passes from
higher pressure to lower pressure along with the corresponding decrease in temperature. The slope
of an isenthalpic curve is called the Joule Thomson coefficient

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  A throttling process is defined as a process in which there is no change in enthalpy from state one
to state two, h I = h 2: No work is done, W= 0 and the process is adiabatic Q = O.
 An example of throttling process is an ideal gas flowing through a valve in mid position.

53. What is throttling valve?

A throttle valve is nothing but a butterfly valve mounted with a spring: The principle involved
here are: Bernoulli's principle (velocity increases, pressure falls, vice-versa) Joule Thompson effect
(temperature decreases when fluid is forced through a valve) Venturi effect (pressure decreases
when flow is constricted).

54. How can you identify whether a process is feasible or not using entropy?

55. Define a nozzle and its types.

 Nozzle is a device to increase the kinetic energy of a flowing fluid by proper change in the
flow area.
 There are two types: a. Convergent nozzle , b. Convergent - Divergent nozzle
 In convergent the flow area continuously decreases
 In convergent – divergent the flow area decreases first as to attain a constant
value at the throat and the flow area increases

56. What is the significance of deriving thermodynamic relations?

 While designing the chemical process plants and equipment two types of thermodynamic
properties are needed.
 Directly measurable properties viz. pressure, temperature, volume etc.
 Properties that can’t be measured directly viz. enthalpy, entropy, free energy etc.
 Thermodynamic relations establish relation between above two properties.
 Thus these relations are useful to measure second category of properties.

57. What are the commonly used standard states?

 Pure liquid, gas or solid at 1 atm pressure
 Pure liquids and solids at its vapor pressure and defined temperature
 It is not necessary to specify the temperature for standard states, normally.

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 58. What is a throttling process?
 When a fluid flows through a partially opened valve or a porous media, the fluid suffers a
decrease in pressure due to friction.
 This expansion of the fluid due to decrease in pressure is called as throttling process.
 This is also called as Joule-Thompson expansion.
 Throttling is used for cooling, in liquefaction of gases and in refrigeration.
 Throttling has no moving parts and hence problems arising while lubricating at low
temperature is eliminated.
 Kinetic energy changes of the fluid during throttling can be made negligible by choosing
proper diameter of inlet and outlet pipes.
 The heat exchange with surrounding is neglected as the fluid flows quickly and hr won’t
be sufficient time for heat exchange.
 There is no work involved in the process.
 Potential energy change is also zero.
 ΔH = 0 H1 = H2, so throttling is constant enthalpy process.

59. Joule-Thompson Coefficient:

 It is defined as the change in temperature resulting from the expansion of a gas between
two constant pressure at adiabatic condition or after throttling process and indicated as ‘µ’
𝜕𝑇
 𝜇 = (𝜕𝑃) = 0
𝐻
 For ideal gas µ = 0 and no temperature takes place
 If µ = + ve then it indicates the gas cools on throttling process
 If µ = - ve then it indicates the gas heats on expansion

60. Write a short note on refrigeration.

 It is a process of producing and maintaining a temperature blow that of the surrounding
atmosphere.
 It finds wide application in domestic and industrial purposes, especially in food,
pharmaceutical, domestic refrigeration and petroleum refineries, textile, air conditioning
and host of other applications.
 The heat is removed from low temperature region and rejected in high temperature region.
 As it can’t happen as spontaneous process external work is required to achieve
refrigeration.
 Normal commercial method is, producing low temperature by evaporation (refrigerant) of
a liquid having a property such that, at pressure of evaporation the saturation temperature
is low. The evaporated liquid is subsequently condensed and returned back to its original
state.
 A typical refrigeration cycle includes evaporation of liquid refrigerants, compression of
refrigerant vapor, condensation of vapor into liquid and finally expansion of liquid.
 Common refrigerants are ammonia, propane, sulfur dioxide, carbon dioxide, Freon-12,
methyl chloride etc.
 The efficiency or coefficient of performance (COP) is defined as the quantity of heat
absorbed at the low temperature per unit of work.
𝑄2 𝑄2
𝐶𝑂𝑃 = 𝑊
= 𝑄1 − 𝑄2
COP is independent of refrigerant and is a function of temperature only.

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  The refrigerator capacity is the rate of heat removed so that to freeze 1 ton of water in 24
hrs. It is equivalent to a heat absorption rate of 12,000 BTU/h. (1 BTU = 1.055 kJ) i..e.
12660 kJ/H
 Various refrigeration cycles are used viz.
 Reversed Carnot Cycle
 Air Compression Cycle
 Vapor Compression Cycle
 Absorption refrigeration cycle.

61. What do you mean by a heat engine?

 In thermodynamics, a heat engine is a system that converts heat or thermal
energy—and chemical energy—to mechanical energy, which can then be used to
do mechanical work.
 In general an engine converts energy to mechanical work.
 Heat engines distinguish themselves from other types of engines by the fact that
their efficiency is fundamentally limited by Carnot's theorem.
 Although this efficiency limitation can be a drawback, an advantage of heat engines
is that most forms of energy can be easily converted to heat.
 As the heat source that supplies thermal energy to the engine can thus be powered
by any kind of energy, heat engines are very versatile and have a wide range of
applicability.

62. What do you mean by a heat pump?

 A heat pump is a device that transfers heat energy from a source of heat to a
destination called a "heat sink". Ex. Air conditioner
 Heat pumps are designed to move thermal energy in the opposite direction of
spontaneous heat transfer by absorbing heat from a cold space and releasing it to a
warmer one.
 A heat pump uses a small amount of external power to accomplish the work of
transferring energy from the heat source to the heat sink

63. How heat engines and heat pumps differs?

 In a heat engine, the energy is transferred from a higher temperature to a lower
temperature level called sink.
 During the process, we get the output as work.
 The higher temperature is known as source and the lower temperature is
known as sink. The Coefficient Of Performance (COP) value of a heat
engine will be always less than 1.
 Heat pumps are designed to move thermal energy in the opposite direction of
spontaneous heat transfer by absorbing heat from a cold space and releasing it to a
warmer one.
 Heat pump absorbs heat from cold body by gaining some work and takes the power
from source like electric motor and transfer heat from one place to other.

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  There is no difference between a heat pump and a refrigerator in the case of
its cycle of operation.
 The main purpose of the heat pump is to make its surrounding hot.
 The main difference between the heat pump and refrigerator is its operating
temperatures.
 The working temperatures of a refrigerator are cold temperature T1 and
atmospheric temperature Ta.
 Where as in the case of a heat pump, the working temperatures are
atmospheric temperature and hot body temperature T2.
 Here, T1 = Ta and COP always greater than 1.

64. What are the two main types of heat engines?

 There are two main types of heat engines: external combustion and internal
combustion:
 In an external combustion engine, the fuel burns outside and away from the
engine where the force and motion are produced for example by producing
steam. Ex: Steam engine
 In an internal combustion engine, the fuel burns inside the cylinder. Ex: Car

65. What are the different types of internal combustion engines?

 Types of Internal Combustion (IC) Engines and Compression ignition (CI)
 There are two main types of IC engines: spark ignition (SI) engines (petrol
or gasoline engine) and compression ignition (CI) or diesel engine.
 Both these engines are further classified as 2-stroke and 4-stroke engine.

66. Write a note on heat engine cycle.

 Heat Engine Cycle
 A heat engine typically uses energy provided in the form of heat to do work
and then exhausts the heat which cannot be used to do work.
 Thermodynamics is the study of the relationships between heat and work.

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 The first law and second law of thermodynamics constrain the operation
of a heat engine.
 The first law is the application of conservation of energy to the system,
and the second sets limits on the possible efficiency of the machine and
determines the direction of energy flow.
 Heat engines such as automobile engines operate in a cyclic manner, adding
energy in the form of heat in one part of the cycle and using that energy to do
useful work in another part of the cycle.

67. What do you mean by a refrigerator?
 A refrigerator (colloquially fridge or fridge freezer) is a popular household
appliance that consists of a thermally insulated compartment and a heat pump
(mechanical, electronic or chemical).
 This transfers heat from the inside of the fridge to its external environment
so that the inside of the fridge is cooled to a temperature below the ambient
temperature of the room.
 Refrigeration is an essential food storage technique in developed countries.
 The lower temperature lowers the reproduction rate of bacteria, so the
refrigerator reduces the rate of spoilage.
 A refrigerator maintains a temperature a few degrees above the freezing
point of water. Optimum temperature range for perishable food storage is
3 to 5 °C (37 to 41 °F).
 For an ideal heat pump cycle:
COP = TH/(TH-TL)

68. Write a note on heat pump cycle or refrigeration cycle.

 Thermodynamic heat pump cycles or refrigeration cycles are the conceptual and
mathematical models for heat pumps and refrigerators.
 A heat pump is a machine or device that moves heat from one location (the
"source") at a lower temperature to another location (the "sink" or "heat sink") at a
higher temperature using mechanical work or a high-temperature heat source
 According to the second law of thermodynamics heat cannot spontaneously flow
from a colder location to a hotter area; work is required to achieve this.
 An air conditioner requires work to cool a living space, moving heat from the cooler
interior (the heat source) to the warmer outdoors (the heat sink).
 Similarly, a refrigerator moves heat from inside the cold icebox (the heat source)
to the warmer room-temperature air of the kitchen (the heat sink).
 The operating principle of the refrigeration cycle was described mathematically by
Carnot in 1824 as a heat engine.
 A heat pump can be thought of as a heat engine which is operating in reverse.
 Heat pump and refrigeration cycles can be classified as vapor compression, vapor
absorption, gas cycle, or Stirling cycle types.
 Vapor compression cycle: (Applied in refrigerator)

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  Heat pump cycle:

In this cycle, a circulating refrigerant such as Freon enters the compressor
as a vapor.
 The vapor is compressed at constant entropy and exits the compressor
superheated.
 The superheated vapor travels through the condenser which first cools and
removes the superheat and then condenses the vapor into a liquid by
removing additional heat at constant pressure and temperature.
 The liquid refrigerant goes through the expansion valve (also called a
throttle valve) where its pressure abruptly decreases, causing flash
evaporation and auto-refrigeration of, typically, less than half of the liquid.
 That results in a mixture of liquid and vapor at a lower temperature and
pressure.
 The cold liquid-vapor mixture then travels through the evaporator coil or
tubes and is completely vaporized by cooling the warm air (from the space
being refrigerated) being blown by a fan across the evaporator coil or tubes.
 The resulting refrigerant vapor returns to the compressor inlet to complete
the thermodynamic cycle.
 Refrigeration Cycle (P-V diagram)

69. How COP is calculated for refrigeration and heat pump cycle for ideal and Carnot?

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  For ideal cycle:
 For an ideal refrigeration cycle:
COP = TL/ (TH-TL)
 For an ideal heat pump cycle:
COP = TH/ (TH-TL)
 For Carnot refrigerators and heat pumps cycle:
 For a Carnot refrigeration cycle:
COP-R (Carnot) = 1/ ((TH/TL) - 1)
 For a Carnot Heat Pump cycle:
COP-HP Carnot = 1/ (1 - (TL/TH))
 Where, TH is higher temperature
TL is lower temperature

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