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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.

1

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.

2

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)

3

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 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.

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

4

Where,

T2

(12)

T1

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

T3

Now, substituting

T1

x 1 x

N s ln (16)

1 x

N s N s x,

Rate of exergy lost due to mixing is,

Wlost To S gen (17)

x 1 x

Wlost T0 mC p ln (18)

1 x

heat loss at two different temperatures, exergy loss is more with higher temperature and

the more temperature, the more is the quality of energy.

5

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)

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

6

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.

7

References

p_mahanta_adv_engg_thermo/Chapter-3.pdf

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

01-03.pdf

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

mixing

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