NAME: AGBOOLA FAWZIYYAH AYOMIDE

MATRIC NO: CHE/2017/021

COURSE CODE: CHE 301
THE SECOND LAW OF THERMODYNAMICS: SUMMARY
 The first law of thermodynamics reflects the observation that energy is
conserved, but it imposes no restriction on the process direction. Yet, all
experience indicates the existence of such a restriction, the concise statement of
which constitutes the second law.
 Work is readily transformed into other forms of energy: for example, into
potential energy by elevation of a weight, into kinetic energy by acceleration of a
mass, into electrical energy by operation of a generator and readily transformed
completely into heat.
 The statements of the second law are;
i. No apparatus can operate in such a way that its only effect (in system and
surroundings) is to convert heat absorbed by a system completely into work done
by the system. It is impossible for a cyclic process to convert the heat absorbed by
a system completely into work done by the system.
ii. No process is possible which consists solely in the transfer of heat from one
temperature level to a higher one.
 Heat reservoirs are bodies imagined capable of absorbing or rejecting an infinite
quantity of heat without temperature change.
 In operation, the working fluid of a heat engine absorbs heat |Q H| from a hot
reservoir, produces a net amount of work|W |, discards heat |QC|to a cold reservoir,
and returns to its initial state. The first law therefore reduces to:
|W |=|Q H|−|Q C|
 The thermal efficiency of the engine is defined as:
net work output
η≡
heat absorbed

|W | |Q H|−|QC|
η≡ =
|Q H| |Q H|
 |QC|
η=1−
|QH|
 A Carnot engine operates between two heat reservoirs in such a way that all heat
absorbed is absorbed at the constant temperature of the hot reservoir and all heat
rejected is rejected at the constant temperature of the cold reservoir.
 Carnot’s theorem states that for two given heat reservoirs, no engine can have a
thermal efficiency higher than that of a Carnot engine. All Carnot engines
operating between heat reservoirs at the same two temperatures have the same
thermal efficiency. Therefore, the thermal efficiency of a Carnot engine depends
only on the temperature levels and not upon the working substance of the engine.
 Consider two Carnot engines, one operating between a hot reservoir at
temperature θ H and a cold reservoir at temperature, θC , and a second operating
between the reservoir at θC and a still colder reservoir at θ F. The heat rejected by
the first engine |QC| is absorbed by the second; therefore the two engines working
together constitute a third Carnot engine absorbing heat IQHI from the reservoir at |
QH| and rejecting heat |QF| to the reservoir at |θF|. The thermal efficiency of the first
engine is a function of θ H ∧θC :
|QC|
η=1− =ϕ (θ H , θC )
|QH|

|Q H| 1
= =f (θ H , θC )
|QC| 1−ϕ (θ H ,θ C)

|QC| ( θ C ,θ F ) ∧|Q H|
For the second and third engines, =f =f (θH , θ F )
|Q F| |Q F|

|Q H| ψ ( T H )
=
|QC| ψ ( T C )

 We conclude that the kelvin temperature scale, based on the properties of ideal
gases, is in fact a thermodynamic scale, independent of the characteristics of any
particular substance. Therefore ψ ( T )=T and the Carnot’s equations are:
|Q H| T H
=
|QC| T C
 |W | TC
η= =1−
|Q H| TH
 Actual heat engines are irreversible, and their thermal efficiencies rarely exceed
0.35.
 If the heat quantities refer to the engine (rather than to the heat reservoirs), the
numerical value of QH is positive and that of QC is negative.
QH −Q C
=
TH TC
QH QC
+ =0
T H TC

 When the adiabatic curves are so closely spaced that the isothermal steps are
infinitesimal, the heat quantities become dQH and dQC :
d Q H d QC
= =0
TH Tc
 Summation of all quantities dQ/T for the Carnot engines leads to the integral:
d Q rev
∮ T
=0

The property is called entropy and its differential changes are:

t d Q rev
dS =
T
 There exists a property called entropy S, which is an intrinsic property of a
system, functionally related to the measureable coordinates which characterize the
system.
 The entropy change of a heat reservoir, however, is always given by Q/T, where
Q is the quantity of heat transferred to or from the reservoir at temperature T,
whether the transfer is reversible or irreversible. The reason is that the effect of
heat transfer on a heat reservoir is the same regardless of the temperature of the
source or sink of the heat.
 If a process is reversible and adiabatic, dQrev=0. Therefore, the entropy of a
system is constant during a reversible adiabatic process, and the process is said to
be isentropic.
 For one mole or a unit mass of fluid undergoing a mechanically reversible
process in a closed system, the first law becomes:
dU =d Q rev−PdV
 A general equation for calculating entropy changes in an ideal gas is given as:
T ig
∆S C P dT P
=∫ −ln
R T R T 0
P0

 Integrating the first term on the right gives:

[ ( )( )]
T
CigP dT
∫ R T =A ln τ + B T 0+ C T 20 + τ 2DT 2 τ +1
2
( τ−1 )
T 0 0

T
where τ =
T0
 For computational purposes:
T
CigP dT
∫ R T =ICPS ( T 0 , T ; A , B , C , D )
T 0

Mean heat capacity:

T

∫ Cigp dT /T
⟨ C igP ⟩S= T 0

T
ln ( )
T0
Entropy change equation:
∆ S ⟨ C P ⟩S T
ig
P
= ln −ln
R R T0 P0
 The entropy changes of two heat reservoirs, one at temperature TH and a second
at the lower temperature TC are:
−|Q| |Q|
∆ StH = ∧∆ S tC =
TH TC
t
∆ Stotal =∆ S H + ∆ S C =
t −|Q| |Q|
+ =|Q|
TH TC
T H −T C
T H TC ( )
 For the process of irreversible heat transfer, ∆ Stotal is always positive, approaching
zero as the process becomes reversible.
 If the initial process results in an entropy change of the fluid, then there must be
heat transfer during the reversible, constant-P second step such that:
A
d Q rev
∆ S =S −S =∫
t t t
A B
B T
 This mathematical statement of the second law affirms that every process
proceeds in such a direction that the total entropy change associated with it is
positive, the limiting value of zero being attained only by a reversible process. No
process is possible for which the total entropy decreases.
|W |=−T C ∆ S total +|Q H| 1− ( TC
TH )
The maximum work is obtained when the engine is reversible, in which case
∆ Stotal =0.
 The equation of entropy balance is:
f
d ( mS )cv d S surr
∆ ( S ṁ )fs + + = ṠG ≥ 0
dt dt
d ( mS )cv Q̇ j
 ∆ ( S ṁ )fs + dt −∑ T = ṠG ≥ 0
j σ ,j

 In the limiting case where ṠG =0, the process must be completely reversible,
implying:

i. The process is internally reversible within the control volume.

ii. Heat transfer between the control volume and its surroundings is reversible.
 For steady state flow process, the mass and entropy of the fluid in the control
d ( mS )cv
volume are constant and is zero . ∆ ( S ṁ )fs −∑ ṠG ≥ 0
dt j

 If there is but one entrance and one exit, with m the same for both streams:
Q̇ j
∆ S−∑ =S G ≥0
j Tσ , j
 The ideal work is
W ideal =∆ ( H ṁ )fs −T σ ∆ ( S ṁ )fs
 For a single stream flowing through the control volume:
W ideal =ṁ(∆ H −T σ AS)
 The only connection between the hypothetical reversible process and an actual
process is that it brings about the same change of state as the actual process.
 When Wideal is positive, it is the minimum work required to bring about a given
change in the properties of the flowing streams, and the thermodynamic efficiency
is defined as the ratio of the ideal work to the actual work:
W ideal
ηr =
Ẇ s
 When Wideal is negative, it is the maximum work obtainable from a given change
in the properties of the flowing streams, and the thermodynamic efficiency is
defined as the ratio of the actual work to the ideal work:
Ẇ s
ηf=
W ideal

 Lost work is work that is wasted as a result of irreversibilities. It is the difference

between the actual work of a process and the ideal work for the process.
W lost =T σ ∆˙ ( S ṁ )fs −Q̇
Ẇ lost =T σ ṠG
 The engineering significance of this result is clear: The greater the irreversibility
of a process, the greater the rate of entropy production and the greater the amount
of energy that becomes unavailable for work. Thus, every irreversibility carries
with it a price.
 The absolute entropy is zero for all perfect crystalline substances at absolute zero
temperature. The absolute entropy of a gas at temperature T based on calorimetric
T T
f
(C P)s ∆ Hfs
( C P )l ∆ Hv
T
(C )
data is: ∫
S= dT + +∫ dT + +∫ P g dT
0
T Tf Tf
T Tv Tv
T
 For an adiabatic expansion that accomplishes no work from the microscopic
viewpoint: ∆ U =C v ∆T =0
 The means for expressing disorder in a quantitative way was developed by L.
Boltzmann and J. W. Gibbs through a quantity Ω , defined as the number of
different ways that microscopic particles can be distributed among the "states"
accessible to them. It is given by the general formula :
n!
Ω=
( n1 ! )( n2 ! ) ( n3 ! ) …
Where n is the total number of particles, and n1, n2, n3 , etc. represent the numbers of
particles in “states” 1,2,3, etc.
 The total number of particles is NA molecules, and initially they are all in a single
"state." Thus:
N A!
Ω 1= =1
( N A !)(0 !)
NA
n1 =n2=
2
 NA!
Ω 2=

[( ) ]
2
NA
!
2
 The connection established by Boltzmann between entropy S and Ω is given by
the equation:
S=k ln Ω

[
S2−S 1=k N A ln N A −N A −2 ( NA NA NA
2
ln
2
−
2 )]
= k N A ln
NA
N A /2
=k N A ln 2=R ln 2

NAME: AGBOOLA FAWZIYYAH AYOMIDE

MATRIC NO: CHE/2017/021
COURSE CODE: CHE 301
VAPOR/LIQUID EQUILIBRIUM: INTRODUCTION:
SUMMARY
 The most commonly encountered coexisting phases in industrial practice are
vapor and liquid, although liquid/liquid, vapor/solid, and liquid/solid systems are
also found.
 Equilibrium is a static condition in which no changes occur in the macroscopic
properties of a system with time. This implies a balance of all potentials that may
cause change.
 Mass or mole fraction is defined as the ratio of the mass or number of moles of a
particular chemical species in a mixture or solution to the total mass or number of
moles of the mixture or solution:
mi ṁi ni ṅ i
xi≡ = ∨x i ≡ =
m ṁ n ṅ
 Molar concentration is defined as the ratio of the mole fraction of a particular
chemical species in a mixture or solution to its molar volume:
xi ṅ
C i= Ci = i
V q
Where ṅi is the molar flow rate of species i, and q is the volumetric flow rate.

 The molar mass of a mixture or solution is, by definition, the mole-fraction-

weighted sum of the molar masses of all species present:
M ≡ ∑ xi M i
i

 The difference between the number of phase-rule variables and the number of
independent equations connecting them is the number of variables that may be
independently fixed. Called the degrees of freedom of the system F, the number is:
F=2+ ( N−1 ) ( π )−( π−1 ) ( N )
F=2−π + N
 Duhem’s theorem applies to closed systems at equilibrium for which the
extensive state as well as the intensive state of the system is fixed. The state of
such a system is said to be completely determined.
2+ Nπ−πN=2
 Duhem’s theorem states that for any closed system formed initially from given
masses of prescribed chemical species, the equilibrium state is completely
determined when any two independent variables are fixed.
 When F = 1, at least one of the two variables must be extensive, and when F = 0,
both must be extensive.
 Vapor/liquid equilibrium (VLE) is the state of coexistence of liquid and vapor
phases.
 All equilibrium states of the system can therefore be represented in three-
dimensional P-T-composition space.
 The critical locus is defined by the points at which vapor and liquid phases in
equilibrium become identical. It is the envelope curve.
 At points where saturated-liquid and saturated-vapor lines intersect, a saturated
liquid of one composition and a saturated vapor of another composition have the
same T and P, and the two phases are therefore in equilibrium.
 The tie lines connecting the coinciding points are perpendicular to the P-T plane.
 The critical point of a binary mixture occurs where the nose of a loop is tangent
to the envelope curve.
 For a pure species the critical point is the highest temperature and highest
pressure at which vapor and liquid phases can coexist, but for a mixture it is in
general neither.
 Therefore under certain conditions a condensation process occurs as the result of
a reduction in pressure.
 If the original condition corresponds to a point of a state of saturated vapor,
liquefaction occurs upon reduction of the pressure and reaches a maximum at a
point, after which vaporization takes place until the dewpoint is reached. This
phenomenon is called retrograde condensation.
 Although VLE in the critical region is of considerable importance in the
petroleum and natural-gas industries, most chemical processing is accomplished at
much lower pressures.
 Azeotrope is used to describe the state of a constant-boiling solution that does not
change in composition as it evaporates.
 The two major assumptions required to reduce VLE calculations to Raoult's law
are:
i. The vapor phase is an ideal gas (applies only for low moderate pressures).
ii. The liquid phase is an ideal solution (it can have approximate validity only when
the species that comprise the system are chemically similar).
 Examples of compounds that conform to ideal-solution are: a mixture of isomers,
such as ortho-, meta-, and para-xylene, adjacent members of a homologous series,
such as n-hexane/n-heptane, ethanol/propanol, and benzene/toluene. Other
examples are acetone/acetonitrile and acetonitrile/nitromethane.
 The mathematical expression which reflects the two listed assumptions and
which therefore gives quantitative expression to Raoult's law is:
sat
y i P=x i Pi (i=1,2, … .. , N )
Where xi is a liquid-phase mole fraction, yi is a vapor-phase mole fraction and Pisat is
the vapor pressure of pure species I at the temperature of the system. The product
yiP on the left side of the equation is known as the partial pressure of species i.
 A limitation of Raoult's law is that it can be applied only to species for which a
vapor pressure is known, and this requires that the species be "subcritical," i.e., that
the temperature of application be below the critical temperature of the species.
 An important and useful feature of Raoult's law is that it is valid for any species
present at a mole fraction approaching unity, provided only that the vapor phase is
an ideal gas. Chemical similarity of the constituent species is not a requirement.
 There are four classes of dewpoint and bubblepoint calculations:
BUBL P: Calculate {yi) and P, given {xi} and T
DEW P: Calculate {xi} and P, given {yi} and T
BUBL T: Calculate {yi} and T, given {xi} and P
DEW T: Calculate {xi} and T, given {yi} and P
summed
 Because ∑ yi =1 , Raoul t s law s expression may be all species ¿ ¿ yield:
' '

P=∑ xi Psat
i
i

 For a binary operation with x 2=1−x 1 :

P=P2 + ( P1 −P 2 ) x 1
sat sat sat

A plot of P vs x1 at constant temperature is a straight line connecting P2sat at x1 =0

with P1sat at x1 =1.
 Solving for xi and summing over all species, with ∑
i
x i=1 yields:

1
P=
∑ y i / Psati
i
An equation applied in dewpoint calculations, where liquid-phase compositions are
not known.
 For a species present as a very dilute solute in the liquid phase, Henry's law then
states that the partial pressure of the species in the vapor phase is directly
proportional to its liquid-phase mole fraction. Thus:
y i P=x i H i
Hi is Henry’s constant, the values of Hi come from experiment.
 For low to moderate pressures:
y i P=x i γ i P sat
i (i=1,2 , … , N )

γ i is an activity coefficient (functions of temperature and liquid-phase composition,

based on experiment).
 Because ∑ yi =1, summing over all species yields: P= x γ P
∑ i i i sat
i

1
 Solving for xi and summing over all species yields: P=
∑ y i /γ i Pisat
 A measure of the tendency of a given chemical species to partition itself
preferentially between liquid and vapor phases is the equilibrium ratio Ki defined
yi
as: K i ≡ x
i

 It serves as a measure of the “lightness” of a constituent species i.e., of its

tendency to favor the vapor phase.
 When
K i >1 , species i exhibits a higher concentration∈the vapor phase . When K i <1 , a higher concentration∈the liquid p
 The K-value for Raoult’s law is:
Psat
i
K i=
P
 The K-value for modified Raoult’s law is given as:
sat
γi P i
K i=
P
 y i=K i x i ; because ∑
i
y i=1 , t hen :

∑ K i x i=1
i

yi
 Alternatively, x i= K ;because ∑ xi =1, then:
i i

y
∑ Ki =1
i i
 For flash calculations, only the P, T-flash are considered. This refers to any
calculation of the quantities and compositions of the vapor and liquid phases
making up a two-phase system in equilibrium at known T, P, and overall
composition.
 Consider a system containing one mole of non-reacting chemical species with an
overall composition represented by the set of mole fractions {zi}. Let L be the
moles of liquid, with mole fractions {xi}, and let V be the moles of vapor, with
mole fractions {yi}. The material-balance equations are:
z i=x i ( 1−V ) + y i V (i =1,2, … , N )
zi K i
y i= (i=1,2 , … , N )
1+V ( K i−1)
z K
∑ 1+V (i K i−1) =1 V =1 is always a trivial solution.
i i