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I.

INTRODUCTION
Mixing is the dispersing of components, one throughout the other. It occurs in
innumerable instances in the food industry and is probably the most commonly
encountered of all process operations. Understanding the thermodynamic behavior of
mixtures is integral to the study of any system involving either ideal or non-ideal solutions
because it provides valuable information on the molecular properties of the system.
Moreover, when solids, liquids or gases are combined, the thermodynamic quantities of
the system experience a change as a result of the mixing. Most substances found in nature
are mixtures of pure chemical elements or compounds: air, natural gas, seawater (but also
tap water), coffee, wine, gasoline, antifreeze, body fluids, etc. The reason for this
widespread occurrence is that there is a natural tendency for entropy to increase in the
mixing (although energy minimization might work against, as in liquid vapor equilibrium
under gravity). Thus, some exergy has to be applied to a mixture to separate its
components. Furthermore, some exergy is also applied in many practical cases to
accelerate the natural mixing process, notably by mechanical stirrers, vibrations and
ultrasounds, or electromagnetic forcing; in flow systems, nozzles, swirls, colliding jets, or
pulsating injectors are commonly used for the same purpose. The mixing time may be
short in gases (we soon detect the smell of an open perfume flask), long in liquids (who
waits for sugar to dissolve in a coffee cup), or extremely long in solids.
Mixtures usually form multiphasic systems except when the components are perfectly
miscible, or when, having some miscibility gap, the mixture is unsaturated. In
thermodynamics, a saturated state is a multiphasic equilibrium state. When phase changes
in pure substances were studied, saturated vapour, saturated liquid and saturated solid,
were considered. For mixtures, saturation (with respect to one of its components) is the
point at which the mixture can dissolve no more of that substance. For example water
saturated with sugar is the sugar/water solution in equilibrium with sugar, air saturated
with water vapour is the water/air mixture in equilibrium with liquid water, and so on.

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II. DISCUSSION
Energy conversion processes are governed by the laws of conservation of mass and
energy. However, entropy is generated and exergy is destroyed by irreversibilities within
a thermal system. Furthermore, exergy is lost, in general, when the exergy associated with
a material or energy stream is rejected to the surroundings. Thermodynamic properties of
a mixture depend on temperature, pressure, and composition.

Entropy of Mixing
In thermodynamics the entropy of mixing is the increase in the total entropy when
several initially separate systems of different composition, each in a thermodynamic state
of internal equilibrium, are mixed without chemical reaction by the thermodynamic
operation of removal of impermeable partition(s) between them, followed by a time for
establishment of a new thermodynamic state of internal equilibrium in the new
unpartitioned closed system.
Visualize that we have a container divided into two compartments. In one compartment
we have n1 moles of an ideal gas, gas 1, at pressure, p and temperature, T. In the other
compartment we have n2 moles of another ideal gas, gas 2, at the same p and T.

If we remove the partition the gases will begin to diffuse into each other and the system
will eventually reach the state where both gases are uniformly distributed throughout the
container. This is clearly an irreversibly process so that we would expect that the entropy
would increase.
To calculate the entropy change we must find a reversible path to carry out the process,
even if the path is fictitious. Imagine that we can devise a process that will expand one gas
reversibly and isothermally, but leave the other gas undisturbed.

Recall that dU 0 for the isothermal expansion of an ideal gas. Then,

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dU TdS PdV 0 . So,
TdS PdV
P nR
dS dV dV , for an ideal gas.
T V
For gas number 1 in isothermal expansion we have,
V1 V2
S1 n1 R ln , and for gas number 2,
V1

V1 V2
S 2 n2 R ln
V2

The total entropy change is the sum of these two individual entropy changes,
V1 V2 V V2
S mix S1 S 2 n1 R ln n2 R ln 1 (1)
V1 V2

Equation 1 could be used for calculations, but it is not in the foSrm that we will see in
other contexts. To obtain the usual form factor the R out of Equation 1 and invert the
argument of the logarithms,
V1 V2
S mix R n1 ln n2 ln (2)
V1 V2 V1 V2
Since we are doing a calculation for ideal gases, notice that the argument of the first
logarithm in Equation 2 can be written,
n1 RT
V1 P n1
X1 , (3)
V1 V2 n1 RT n2 RT n1 n 2

P P
where X1 is the mole fraction of component 1. There is an equivalent expression for the
argument of the second logarithm. The entropy of mixing becomes,
S mix Rn1 ln X 1 n2 ln X 2 (4)
Equation 4 is also suitable for calculations, but it is not yet in the standard form. To obtain
the standard form write the total number of moles n1 + n2 as n and multiply and divide
equation 4 by n. The result is
S mix nR X 1 ln X 1 X 2 ln X 2

S mix R xi ln xi (5)

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Thus, mixing gases always results in the increase of entropy. Therefore, mixing is
spontaneous, which in general, true to any material (solid or liquid).

Demonstration of Quality of Energy Based on Exergy


Exergy is the tool, which indicates how far the system departs from equilibrium state.
It is a low grade energy available for conversion termed as available energy, availability
or exergy. Exergy is defined as the maximum work obtainable while the system contacts
with environment reversibly.

Consider Figure 2, where two fluid streams 1 and 2 of an incompressible fluid or ideal
gas mixing adiabatically at constant pressure is shown.

Figure 2: Mixing of two Fluid Streams


Mass Balance:
m1 m2 m3 m (6)
Let,
m1
x (7)
m1 m2
By first law of thermodynamics,
m1h1 m2 h2 m1 m2 h3 (8)
or,
xh1 1 x h2 h3 (9)

Since, h hT
xT1 1 x T2 T3 (10)
T3
x 1 x 2 x 1 x
T
(11)
T1 T1

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Where,
T2
(12)
T1

By second law of thermodynamics,


S gen m3 s3 m2 s 2 m1 s1 ms3 xms1 1 x s 2 (13)

S gen T3
s3 s2 xs 2 s1 C p ln
T
xC p ln 2 (14)
m T1 T1

or,
x
S gen T T
ln 3 2 (15)
mC p T1 T1
S gen
Let, N s = Entropy generation number =
mC p

x 1 x equation 15, we get


T3
Now, substituting
T1

x 1 x
N s ln (16)
1 x
N s N s x,

For, 1, N s 0 , m2 0 , the system is with single stream.

For, 1, N s 0 , temperature of both the streams are the same.


Rate of exergy lost due to mixing is,
Wlost To S gen (17)

x 1 x
Wlost T0 mC p ln (18)
1 x

The interpretations are that, for the same


heat loss at two different temperatures, exergy loss is more with higher temperature and
the more temperature, the more is the quality of energy.

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Energy and Exergy of Ideal Mixtures
Energy, for an ideal two-phase mixture, is just the simple addition of the energies of
every component in every phase; by unit of total amount of substance:
hT , P, xij xV 0 xV 1 hV 1 xV 2 hV 2 x L 0 x L1 hL1 x L 2 hL 2 (19)

whereas the entropy is,


S T , P, xij xV 0 xV 1 SV 1 xV 2 SV 2 x L 0 x L1 S L1 x L 2 S L 2 (20)

Equation 19 shows that the energy needed to perform a complete phase change at
constant pressure, from a saturated liquid mixture at the boiling temperature Tb, to a
saturated vapour mixture at the condensation temperature Tc (with the same composition)
is:

hLV xV 1 hV 1 xV 2 hV 2 x L1 hL1 x L 2 hL 2 xi c Li Tbi Tb hLVbi C pVi Tc Tbi

and also teaches that the isobaric thermal capacity during the phase change (that for pure
substances was infinite), for a two-phase binary mixture is:

C pmix T , P, xij
dh
dT

The result is that the isobaric thermal capacity during two-phase boiling is very high
(inversely proportional to the temperature span for complete boiling), but finite.

III. SUMARRY
Mixing is the dispersing of components, one throughout the other. Mixtures usually
form multiphasic systems except when the components are perfectly miscible, or when,
having some miscibility gap, the mixture is unsaturated. In thermodynamics, a saturated
state is a multiphasic equilibrium state.
Energy conversion processes are governed by the laws of conservation of mass and
energy. However, entropy is generated and exergy is destroyed by irreversibilities within
a thermal system. Furthermore, exergy is lost, in general, when the exergy associated with
a material or energy stream is rejected to the surroundings.
In thermodynamics the entropy of mixing is the increase in the total entropy when
several initially separate systems of different composition, each in a thermodynamic state
of internal equilibrium, are mixed without chemical reaction by the thermodynamic
operation of removal of impermeable partition(s) between them, followed by a time for
establishment of a new thermodynamic state of internal equilibrium in the new

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unpartitioned closed system. Thus, mixing gases always results in the increase of entropy.
Therefore, mixing is spontaneous, which in general, true to any material (solid or liquid).

Exergy is a low grade energy available for conversion termed as available energy,
availability or exergy. It is defined as the maximum work obtainable while the system
contacts with environment reversibly. For the same heat loss at two different temperatures,
exergy loss is more with higher temperature and the more temperature, the more is the
quality of energy.

Energy is needed in mixing, and as time passes by, the degree of disorder or entropy
also increases, which causes the exergy to decrease. The lost work dW, increase in entropy
of the heat dS and lowest available temperature T0 are related by dW=T0 dS. If the heat
source for an ideal heat engine consists of two vessels each containing a different perfect
gas, no loss of thermal efficiency occurs when the gases mix, but there is an increase in
entropy of the heat source. It is shown, however, that the relationship between entropy and
available work still holds.

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References

Exergy Analysis. http://www.iitg.ernet.in/scifac/qip/public_html/cd_cell/chapters/


p_mahanta_adv_engg_thermo/Chapter-3.pdf

Mixtures. http://webserver.dmt.upm.es/~isidoro/bk3/c07/Mixtures.pdf

Exergy analysis of simple processes. http://www.eolss.net/sample-chapters/c08/e3- 19-


01-03.pdf

Lost work and the entropy of mixing.


https://www.researchgate.net/publication/231151698_Lost_work_and_the_entropy_of_
mixing

Thermodynamics of Mixing, (November 29, 2016).