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com

38 Refrigeration and Air Conditioning

Ê p Tˆ
ÁË s v ˜¯

One has to take the negative sign while taking derivatives along columns, that is,

Ê ∂T ˆ Ê ∂v ˆ
ÁË ˜¯ and ÁË ˜¯

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∂v s ∂T p

2.11 THIRD LAW OF THERMODYNAMICS

This law gives the definition of absolute value of entropy and also states that absolute zero cannot

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be achieved. Another version of this law is:
The entropy of perfect crystals is zero at absolute zero.

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This statement is attributed to Planck. This is in line with the concept that entropy is a measure
of disorder of the system. If W is the probability of achieving a particular state out of a large
number of states, then entropy of the system is equal to ln (W). The transitional movement of

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molecules ceases at absolute zero and the position of atoms can be uniquely specified. In addition,
if we have a perfect crystal, then all of its atoms are alike and their positions can be inter-
changed without changing the state. The probability of this state is unity, that is W = 1 and
ln (W) = ln (1) = 0.
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For imperfect crystals, however, there is some entropy associated with configuration of
molecules and atoms even when all motions cease, hence the entropy in this case does not tend to
zero as T Æ 0, but it tends to a constant called the entropy of configuration.
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The third law allows absolute entropy to be determined with zero entropy at absolute zero as
the reference state. In refrigeration systems we deal with entropy changes only, the absolute entropy
is not of much use. Therefore entropy may be taken to be zero or a constant at any suitably chosen
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state, which serves as a reference. Evaluation of entropy requires correlations for specific heats
and latent heats as function of temperature.
Another consequence of third law is that absolute zero cannot be achieved. One tries to approach
absolute zero by magnetization to align the molecules. This is followed by cooling and then
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demagnetization, which extracts energy from the substance and reduces its temperature. It can be
shown that this process will require infinite number of cycles to achieve absolute zero. In a later
chapter it will be shown that infinitely large amount of work is required to maintain absolute zero
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if at all it can be achieved. For many interesting problems related to these laws the reader is
referred to Thermodynamics by J.E. Lay (1963).
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2.12 PERFECT GAS

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The molecular forces of attraction between gas molecules are small compared to those in liquids.
In the limit when these forces are zero, a gas is called a perfect gas. In addition, the volume of the
molecules should be negligible compared to total volume for a perfect gas. An equation expressing
a relation between pressure, temperature and volume of a substance is called Equation of State. A
large number of such equations have been proposed for fluids based upon validation by experimental
data. In case of perfect gas, this relation has the simplest form, namely
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Thermal Principles—A Review of Fundamentals 39

pv = RT (2.32a)
pV = mRT (2.32b)
pV = nRT (2.32c)
pv = RT (2.32d)

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where, p is the absolute pressure inkPa, v is the specific volume in m3/kg,V is volume in m3 andv
is molal volume in m3 per kgmole. T is the temperature in kelvin. R is universal gas constant in kJ/
kgmole-K and R is gas constant for a particular gas in kJ/kg-K.
R = 8.314 kJ/kgmole-K (2.33)

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and R = R /M, M being the molecular weight of gas in kg/kgmole
Equation (2.32) is a good approximation for gas at temperatures well above the critical
temperature and at low pressures, where the intermolecular forces are negligibly small.

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According to another definition of perfect gas, it is a gas, for which the internal energy is a
function of temperature only, that is,
u = u(T)
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h = u + pv = u(T) + RT = h(T)
Hence, the enthalpy of perfect gas is a function of temperature only.
(2.34)
(2.35)
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A large number of useful relations for various properties can be derived using the perfect gas
relations and specific heats, for example, change in internal energy and enthalpy between states 1
and 2 is given by
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u2 – u1 = cv (t2 – t1) (2.36)

h2 – h1 = cp (t2 – t1) (2.37)
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Integrating Eqs. (2.24) and (2.25) between states 1 and 2, we get

s2 – s1 = cv ln (T2/T1) + R ln (v2/v1) (2.38)
s2 – s1 = cp ln (T2/T1) + R ln (p2/p1) (2.39)
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In a constant volume heat transfer process, the work done w12 = 0. Hence from first law,
q12 = u2 – u1 = cv (t2 – t1)
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Similarly for a constant pressure process, by definition

q12 = h2 – h1 = cp (t2 – t1)
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2.13 MIXTURE OF IDEAL GASES

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While dealing with moist air and mixture of refrigerants, one has to consider mixture of gases.
Here, we consider a mixture of ideal gases, say A and B. The molecular forces of attraction between
the molecules of each constituent gas, that is, A–A and B–B molecules are zero if these are ideal
gases. For the mixture to be treated as a perfect gas, the molecular forces between molecules of
different gases, that is, A–B should also be zero.
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40 Refrigeration and Air Conditioning

We first consider a given volume V of the mixture of gases A and B at pressure p and temperature
T. Each of the gases is assumed to follow the ideal gas relation, i.e. Eq. (2.32). If mA and mB are the
masses of constituent gases and m is the mass of the mixture, then mass conservation yields
m = mA + mB (2.40)
The partial pressure pA of species A is defined as the pressure that species A would exert if it

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alone occupied the whole volume V. Since there are no forces of interaction between two gases,
the sum of partial pressures of the two gases is equal to the total pressure, p. This is known as
Dalton’s law of partial pressures and is expressed as
p = pA + pB (2.41)
From Eq. (2.32), we have

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pAV = mARAT, pBV = mBRBT and pV = mRT (2.42)
where R is the gas constant for the mixture and is given by

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R = (mARA + mBRB)/m (2.43)
If the gases are mixed adiabatically without any change in kinetic and potential energy, and without

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any work output, then according to first law of thermodynamics, in steady state the initial and final
enthalpies are the same, therefore the mixture enthalpy is given by
h = (mA hA + mB hB)/m (2.44)
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or in differential form,
mdh = mA dhA+ mB dhB
For a perfect gas dh = cp dt, therefore the specific heat of the mixture is given by
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cp = (mA cpA + mB cpB)/m (2.45)

Similarly, the internal energy of the mixture is given by
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u = (mA uA + mB uB)/m (2.46)

and cv = (mA cvA + mB cvB)/m (2.47)
The entropy of a mixture is not equal to the sum of entropies of individual components; the entropy
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of mixing (which is an irreversible process) has to be included.

2.14 REAL GAS AND VAPOURS

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The relation between various thermodynamic properties is called the equation of state since these
properties help in uniquely fixing the thermodynamic state of a system in equilibrium. Various
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equations of state have been proposed to model the real gas and the vapours in which the forces of
attraction between molecules are not negligible. One of the earliest attempts to improve upon the
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ideal gas equation was the van der Wall’s equation.

2.14.1 van der Wall’s Equation

Ê aˆ
ÁË p + 2 ˜¯ (v - b) = RT (2.48)
v
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Thermal Principles—A Review of Fundamentals 41

In this equation, a / v 2 accounts for the forces of attraction between molecules and b accounts
for the finite volume of the molecules. The constants a and b are found by looking at the isotherm
passing through the critical point which is supposed to have a point of inflection there. Here,
a = (27/64) R 2Tc2 / pc and b = R Tc /(8pc) where Tc and pc are the critical temperature and pressure
respectively. Four more equations are as follows:

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2.14.2 Dieterici Equation
p (v - b) exp (a / v RT ) = RT (2.49)
where, a = 4 RTc2 /(e2 pc ) and b = RTc /(e2 pc ) and e = 2.718

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2.14.3 Beattie Bridgman Equation

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p = RT (1 - e )(v + B) / v 2 - A / v2 (2.50a)
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where, B = B0 (1 - b / v ), e = c / v T and A = A0 (1 - a / v )
or

2.14.4 Benedict–Webb–Rubin (BWR) Equation

an
pv 2 = RT [v + B0 {1 - b / v }] [1 - c /(v T 3 )] - A0 (1 - a / v ) (2.50b)
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RT B0 RT - A0 - C / T 2 RT (b - a) aa C Ê g ˆ 2
p= - + + 6 + 2 3 ÁË1 + 2 ˜¯ exp ( -g / v ) (2.51)
v v2 v3 v T v v
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where A0, B0, C0, a, b, c, a and g are constants for a gas. This equation is good for predicting the
properties of light hydrocarbons.
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2.14.5 Redlich–Kwong Equation

This equation has only two constants. The BWR equation has eight constants, hence extensive
experimental data points are required to determine these constants. In case of the gases for which
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experimental values are available at only a few points, the RK equation gives a better approximation
than that given by van-der Wall’s equation.
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RT a
p= - where a = Wa R 2Tc2.5 /pc and b = Wb RTc / pc (2.52)
v -b T v (v + b)
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Here Wa and Wb are determined from the values at two points where the experimental data is
available. When no p,v,T experimental data is available, then these constants may be chosen as,
Wb = 0.0867 and Wa = 0.4278. This equation does not give so good an accuracy.
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2.14.6 Peng–Robinson Equation

RT a
p= - 2 (2.53)
v - b v + 2bv - v 2
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42 Refrigeration and Air Conditioning

where
0.45724 RTc2
a= [1 + f (w ) (1 - (T / Tc )]2 and b = 0.0778 RTc /pc
pc
Another popular equation is Martin–Hu equation of state, which is as follows:

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2.14.7 Martin–Hu (MH) Equation

5
RT Ai + Bi + Ci exp ( - kT / Tc )
p= + Â
v - b i=2 (v - b)i
(2.54)

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The constant k ª 4.2 for most gases and is an adjustable constant.
This equation has been used in Du Pont tabulated properties of refrigerants.

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The values of constants Ai, Bi, Ci and b are available for various refrigerants.
Another equation of state is virial equation of state, which has been used to predict the properties
of moist air. This equation is described below.

2.14.8 Virial Equation of State

pv
an
= 1 + A2 (T ) p + A3 (T ) p 2 + A4 (T ) p 3 + " (2.55)
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RT
Another form of this equation is
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pv
= 1 + C2 (T ) r + C3 (T ) r 2 + C4 (T ) r 3 + " (2.56)
RT
where, density is used on the right hand side for convenience. NEL tables for refrigerant R12 are
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based upon this equation with up to 15 terms. The virial equation requires more terms than than
those in BWR or MH equation, but power series is easier to evaluate than the terms in BWR and
MH equations.
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2.15 DRY AIR

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In air conditioning we consider moist air to be a mixture of dry air and water vapour, since the
control of latter is one of the aims of air conditioning. On volume basis, standard air is considered
to consist of 78.08% N2, 20.95% O2 and traces of about fifteen other gases. The molecular weight
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and gas constant of dry air are

M = 28.966 kg/kgmole (2.57)
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R = 0.2871 kJ/kg-K
Precise measurements indicate that perfect gas approximation is correct at sufficiently low pressures
and temperatures well above the critical temperature. For other cases, a reliable equation of state
may be derived from statistical mechanics. This equation is called virial equation of state and is
given by a power series in pressure. One may take as many terms as possible depending upon the
degree of accuracy desired. This equation is as follows:
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Thermal Principles—A Review of Fundamentals 43

pv
= 1 + A2 (T ) p + A3 (T ) p 2 + A4 (T ) p 3 + " = Z (2.58)
RT
where, A2, A3, etc are called virial coefficients. These are functions of temperature and are determined
experimentally. Z is called the compressibility factor. The variation of Z with temperature and
pressure is available in standard textbooks on thermodynamics. At atmospheric pressure, Z is

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essentially unity between –75°C and 100oC, hence in this range it behaves like a perfect gas. The
specific heat of dry air varies between 1.0048 and 1.013 between –75°C and 100oC.
In the air conditioning range of temperatures from 0 to 50oC, the following values are used:
cp = 1.005 kJ/kg-K, cv = 0.7179 kJ/kg-K

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2.16 Properties of Pure Substance
A pure substance is one whose chemical composition does not change during thermodynamic

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processes. Water and refrigerants are pure substances. Nowadays, emphasis is on the use of mixture
of refrigerants. The understanding of properties of mixtures also requires a sound knowledge of
the properties of pure substances.

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Water is a substance of prime importance in refrigeration and air conditioning. It exists in
three states, namely, ice, water and water vapour and undergoes transformation from one state to
another. Steam and hot water are used for heating of buildings while chilled water is used for
cooling of buildings. Hence, an understanding of its properties is essential for air conditioning
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calculations. Substances which absorb heat from other substances or space, are called refrigerants.
These substances also exist in three states. These also undergo transformations usually from liquid
to vapour and vice-versa during heat absorption and rejection respectively. Hence, it is important
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to understand their properties as well.

If a liquid (pure substance) is heated at constant pressure, the temperature at which it boils is
called saturation temperature. This temperature will remain constant during heating until all the
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liquid boils off. At this temperature, the liquid and the associated vapour at the same temperature
are in equilibrium and are called saturated liquid and saturated vapour respectively. The saturation
temperature is a function of pressure only. At atmospheric pressure, the saturation temperature is
called normal boiling point. Similarly, if the vapour of a pure substance is cooled at constant
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pressure, the temperature at which the condensation starts, is called the dew point temperature.
For a pure substance, the dew point and the boiling point are same at a given pressure.
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Similarly, when a solid is heated at constant pressure, it melts at a definite temperature called
melting point. Similarly, cooling of a liquid causes freezing at the freezing point. The melting
point and freezing point are same at same pressure for a pure substance and the solid and liquid are
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in equilibrium at this temperature.

For all pure substances there is a temperature at which all the three phases exist in equilibrium.
This is called the triple point.
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The liquid–vapour phase diagram of a pure substance is conveniently shown in temperature–

entropy diagram or pressure–enthalpy diagram or p–v diagram. Sometimes, three-dimensional
p-v-t diagrams are also drawn to show the phase transformation. In most of the refrigeration
applications except dry ice manufacture, we encounter liquid and vapour phases only.