CHE3161 Week8Notes

CHE3161 Chemistry & Chemical Thermodynamics
CHE4162 Particle Technology
Lecture 11 :
Lecture 18: The Framework of Solution Thermodynamics -
Part IV Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
Lecture 11 :
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
This equality holds true for any system

Excess properties need to be introduced in order
in vapour/liquid equilibrium
to calculate fugacity for liquid mixtures
Generalized Correlations for Fugacity Coefficient
The generalized compressibility correlation can be applied
directly to obtain the fugacity coefficients of pure species
Since P = PCPr, and dP = PCdPr , the integral for the pure
component fugacity coefficient can be written as,
Lecture
P
lnΦi = ∫ 0 (Z i −1)
dP 11
P
:
= ∫ 0 (Z i −1)
dPr
r
P Pr
Dilute
Substituting the Lee/Kessler Phase
correlation, Zi = Zi0 + ωZi1, into this
expression,
Pneumatic
dPr 1 dPr
P P
lnΦi = ∫ 0 (Z i −1) + ω ∫0 Zi
0 r r
€
Rhodes: Chapter 8
transport
Pr Pr
or lnΦi = lnΦ0i + ω lnΦ1i (*)
Pr dPr Pr dPr
where lnΦ =0
i ∫ 0
(Z −1)
i
1
lnΦ =
i ∫ Z1
i
€ 0 Pr 0 Pr
€
The two integrals can be evaluated graphically or numerically
from tables of Z0 and Z1
Equation (*) can also be written as,
ω
ΦLecture
i = (Φ )(Φ )11
0
i
1
i :
Values of Φ 0 and Φ1 from the Lee/Kessler compressibility
correlation are tabulatedDilute Phase
i i
in SVA, and can be used in the the same
way as other generalized correlations
€ Pneumatic
When the simplest form of the virial expansion is valid one can
use
€ the two transport
€ term virial expansion
Rhodes: Chapter 8
formulation of the Lee/Kessler
correlation Pr
0 1 Pr
Z = 1+ B + ωB
Tr Tr
0 0.422 1 0.172
B = 0.083 − 1.6 B = 0.139 − 4.2
Tr Tr
€
Substituting this into,
Pr dPr
lnΦi = ∫ 0
(Z i −1)
Pr
Leads to, Pr 0
lnΦi = ( B + ωB1 )
Lecture
Tr 11 :
or, € Dilute
$ Pr 0 Phase '
Φi = exp & ( B + ωB ) )
1
% Tr (
€ Pneumatic
This expression gives the fugacity coefficients only of pure
species. To find
Rhodes: the fugacity
Chapter 8
transport
coefficients of species in mixture,
mixing €
rules are required
We have derived the expression for evaluating the fugacity
coefficients of species in mixtures from second coefficient data
earlier,
P $ 1 '
ln Φ̂ k = & Bkk + ∑∑ yi y j (2δik − δij ))
RT &%Lecture
2 i j 11 : )(
Values of the virial coefficients Bij can be obtained from mixing
rule, Dilute Phase
RT
Bij = (
Cij
Pneumatic
PCij
)
B 0 + ω ij B1
ωi +ω j
TCitransport
ZCij RTCij
ω ij =Rhodes: Chapter
TCij 8= TCj (1 − K ij ) PCij =
2 TCij
€ ZCi + ZCj " VCi1/ 3 + VCj1/ 3 % 3
ZCij = VCij =$ '
2 # 2 &
€ €
€
The quantity Kij is an empirical interaction parameter specific to
an i-j molecular pair. When i=j and for chemically similar species, kij
= 0. It is often set equal to zero when it is unknown. When
possible, it is evaluated from PVT data, and is generally a small
positive number
Lecture 11 :
Dilutereduce
When i = j, all the expressions Phase
to the pure component
expressions
Pneumatic
The advantage of the generalized correlation for second virial
coefficients
Rhodes: isChapter
transport
their simplicity
8 – they have no physical significance.
More complex correlations appear in literature.
The Ideal Solution
The ideal solution is used as a reference state for liquid mixtures,
similar to the use of the ideal gas a reference state for real gases.
Just as residual properties represent the departure of a real gas
from the ideal gas state, excess properties will be introduced
shortly as the departure of a real liquid mixture from an ideal
solution Lecture 11 :
Dilute
The ideal solution is defined Phasethat the chemical
by assuming
potential of a species in the solution depends on composition in
Pneumatic
the same way as for a species in an ideal gas mixture. Recall that
for an ideal gas mixture,
Rhodes: Chapter 8
transport
µiig ≡ Giig = Giig + RT ln y i
€
The Ideal Solution
The chemical potential for a species in an ideal solution is
defined by, id id
µi ≡ Gi = Gi + RT ln x i
Where, Gi is the Gibbs energy of the pure species at the mixture T

Lecture
and P, and in the same physical 11liquid
state (gas, : or solid) as the
mixture.€The mole fraction is represented by xi to reflect the fact
Dilute
that application is most often Phase
to liquids.
Pneumatic
Note that the pure species are REAL and NOT ideal
transport
AllRhodes: Chapter
other partial 8 properties follow from the definition of
molar
the chemical potential
Since,
In order to apply the basic form
$ ∂G id ' ! ∂ G id $
of FRP for Gibbs energy, the
Siid = −& i ) Vi id = # i & mixture as a system must be
x1 x2 ... xN are all % ∂T ( P ,x " ∂ P %T ,x closed with fixed compositions
held constant for all species
Lecture
It is straightforward to show 11 :
that,
€ Dilute
S id Phase
i = S i − Rln x i
VPneumatic
i
id
= Vi
H iid = H i
The summability
Rhodes: € relation
Chapter
transport
8 applied to ideal solution is written as,
€ M id = ∑ x i M iid
i
€
As a result,
G id = ∑ x iGi + RT ∑ x i ln x i
i i
S id = ∑ xLecture
i S i − R∑ x i 11
: ln x i
i i
Dilute Phase
€ V = ∑ x iVi
id
Pneumatic
i
€ H id = ∑ x i H i
Rhodes: Chapter 8
transport
i
Note that€the enthalpy of mixing and the volume change of

mixing of an ideal solution is zero
€
All summations highlighted by red squares are ideal solution properties before mixing
The Lewis/Randall Rule
The fugacities of the components of an ideal solution can be
computed in a straightforward manner
Recall the definition fugacity of a species in a mixture,

µi Lecture ln fî :
= Γi (T) + RT11
For an ideal solution,
Dilute Phase
µ = Γi (T) + RT ln fî id
id
i
€
For a pure species, Pneumatic
Gi = Γtransport
i (T) + RT ln f i
Rhodes: Chapter 8
€ these equations into the expression just defined,
Substituting
µiid = Gi + RT ln x i
€
The Lewis/Randall Rule
Comparison of the two expressions for μiid leads to,
f̂ i id = x i f i
This expression is known as the Lewis/Randall Rule – the
fugacity of each species in an ideal solution is proportional to its
Lecture 11 :
mole fraction, and the proportionality constant is the pure species
€
Dilute
fugacity at the same physical Phase
state and T and P of the solution
In terms of the fugacity coefficients,
Pneumatic
ˆ id = fˆ id / x P
Φ i i i
ˆ id transport
Rhodes:∴Chapter 8 Φ = f /P = Φ
i i i
This is the alternative form of Lewis/Randall rule – the fugacity
coefficient of each species
€ in an ideal solution is equal to the pure species
fugacity coefficient at the same physical state and T and P of the solution
€ €
Note that although partial fugacity coefficient in an ideal solution is the same as the fugacity coefficient of the
corresponding pure species, the relationship between partial fugacity coefficient and partial fugacity still holds true
(Eq. 121 in Formula Sheet)
Excess Properties
Liquid solutions are more easily dealt with through properties
that measure their departure form ideal solution behavior rather
than ideal gas behavior
Excess properties are defined as the difference between the

Lecture
properties of a real solution 11 :
and the corresponding ideal solution
at the same temperature, pressure and composition,
Dilute Phase
M = M − M id
E
Pneumatic
The partial molar excess property of a species in the solution is
related real and8idealtransport
to theChapter
Rhodes: partial molar properties through the
relation, €
M iE = M i − M iid
A fundamental excess property relation can be derived
analogous to the fundamental residual property relation derived
earlier,
! nG E $ nV E nH E GiE
d# &= Lecture
dP − 2
11+ ∑
dT : dni
" RT % RT RT i RT
Dilute Phase
Relations between excess Pneumatic
properties can be derived (see the
table in the next page). Note that excess properties have no
meaning
Rhodes:for pure species,
Chapter
transport
8 whereas residual properties exist for
pure species as well as mixtures
This is because excess properties use ideal solution (mixture) as the reference state
whereas residual properties use ideal gas as the reference state.
Pure species can be compared with ideal gas but not ideal solution.
Lecture 11 :
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
Excess Gibbs Energy and the Activity Coefficient
The partial molar excess Gibbs energy is particularly interesting,
and can be derived from the two relations we had obtained earlier,
Gi = Γi (T) + RT ln fî
Giid = Γi (T) + RT ln x i f i
Lecture 11 :
ˆ
GiDilute Phase
€ f
− Giid = RT ln i
xi fi
€
The ratio appearing in the Pneumatic
rhs of the expression is defined as the
activity coefficient of species i in the mixture
Rhodes: Chapter 8
transport
ˆ
€ fi
γi =
xi fi
Activity coefficient is a measure of the deviation of the fugacity of a pure species in a real solution
from the fugacity of a pure species in an ideal solution under the same T and P
€
In terms of the activity coefficient, the excess Gibbs energy is
consequently,
GiE = RT ln γ i
The activity coefficient isLecture 11partial

related to the : molar excess
Gibbs energy in exactly the same way as the fugacity coefficient is
€ molar
related to the partial Dilute
residualPhase
Gibbs energy
For an ideal solution Pneumatic

G E
i =80
Rhodes: Chapter
transport
γi = 1
€ €
The set of equations for chemical potential in solution
Ideal Gas Mixture µiig = Giig + RT ln yi

Lecture 11 :
id
Ideal Solution µ = Gi + RT ln xi
i
Dilute Phase
Real Solution µi = Gi Pneumatic
+ RT ln γ i xi
Rhodes: Chapter 8
transport
The fundamental excess property relation can be written in
terms of the activity coefficient,
! nG E $ nV E nH E
d# &= dP − 2
dT + ∑ ln γ i dni
" RT % RT RT i
Knowledge of the excess Gibbs energy as a function of T, P and
composition is sufficient to obtain the excess volume, excess
enthalpy and activity coefficients from equations analogous to the
ones derived earlier from the fundamental residual property relation,
V E Lecture
# ∂ (G E /RT)11
: &
=% (
RT $ ∂P
Dilute Phase 'T ,x
HE $∂ (G E /RT) '
RT
Pneumatic
= −T &
∂T
)
% ( P,x
€ transport
Rhodes: Chapter 8 $ ∂ (nG E /RT) '
ln γ i = & )
% ∂n i ( P ,T ,n j
€
This partial derivative expresses the activity coefficient
of a pure species in a solution mixture as the partial, γi is a partial property
dimensionless Gibbs energy
€
We shall see shortly that VE, HE and ϒi are all experimentally
accessible
The last equation in the set above indicates that lnϒI is a partial
molar property with respect to (nG E /RT)
Lecture 11 :
The activity coefficient consequently obeys the summability
relation, the Gibbs-Duhem Dilute
relation,Phase
and all other relationships
derived earlier for partial
€ molar properties
Pneumatic
Applying the summability relation,
Rhodes: Chapter 8 E
transport
G
= ∑ x i ln γ i
RT i
€
The Gibbs-Duhem relation at constant T and P leads to,
∑ x d lnγ
i i =0 (constant T, P)
i
The Gibbs-Duhem relation restricts the way in which activity
coefficients can vary Lecture 11 :
The effect of pressure and temperature on the activity coefficients
can be obtained from theDilute
relations,Phase
€
$ ∂ ln γ i ' Vi E
& Pneumatic) =
% ∂P (T ,x RT
$
Rhodes: Chapter &8∂ ln γ transport
i
' H E
) = i2
% ∂T ( P ,x RT
The qualitative features of the dependence of the excess
€
properties of a binary solution on composition are discussed in SVA.
€
Brief Summary of Solution Thermodynamics - Theory
Pure Species Properties VS Partial Properties VS Solution Properties
µiα = µi β = ... = µiπ Equilibrium criterion for

multiphase system
(i = 1,2,3,...,N)
Lecture 11 :
ig
µ i = Γi (T) + RT ln y i P
€ Dilute Phase
€
Gi = Γi (T) + RT ln f iPneumaticµ = Γ (T ) + RT ln fˆ
R i i i
G = RT lnΦ
i i
Rhodes:
lnΦ =
€
i
P
∫ Chapter
( ) 8
Z −1 dP /P
i
transport
(Constant T) G = RT ln ˆ
Φ
R
i i
0
$ V l ( P − P sat ) ' ˆ = P Z i −1
€€ f i = Φsat
i Pi
sat
exp&
&
i
RT
i
)
)
ln Φ i ∫ 0 P
dP
% (
€ €
€
fîα = fî β = ... = fîπ
€
µiig ≡ Giig = Giig + RT ln y i Gi ≡ µi = Γ i (T ) + RT ln fî
µiid ≡ Giid = Gi + RT ln x i Giid ≡ µiid = Γ i (T ) + RT ln fî id
€
id
Lecture 11 : fˆ
€ f̂ i = x i f i E id
Gi = Gi − Gi = RT ln i = RT ln γ i
Dilute Phase xi fi
M E = M − M id
Pneumatic µi = Gi + RT ln γ i xi
€ ig
µ = G + RT ln yig
M E
Rhodes:
i = M − M id
i Chapter
i
transport
i
i
id
8 µ = G + RT ln x
i
i
VS
ln γ = &
i
i
$ ∂ (nG /RT) '
) i
E
% ∂n i ( P ,T ,n j
! nG E $ nV E nH E GE
€ d# &= dP − dT + ∑ ln γ i dni = ∑ x i ln γ i
" RT % RT RT 2
i RT i
€ ∑ x d lnγi i =0
i
€
Lecture
Lecture 11 :#2
19: Review
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
1
Lecture 11
Chapter 4: Heat Effects
:
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
3
Latent Heats of Pure Substances
When one mole of a pure substance undergoes a change of
phase (solid to liquid, liquid to vapor), it is accompanied by the
transfer of a finite amount of heat, called the latent heat of
fusion and the latent heat of vaporization
Lecture 11 :
According to the phaseDilute
rule, onlyPhase
one intensive variable is
required to fix the state of the system. Thus, the latent heat is a
Pneumatic
function of temperature only, which is described by the
Clapeyron equation.
Rhodes: Chapter 8 ΔH = TΔV
transportdP sat Saturation pressure
dT
Latent Heat
Volume change with phase transition
€ 4
Temperature Dependence of Heat Capacity
A common representation is in the form of an
expansion in powers of temperature
CP
= A + BT + CT 2 + DT −2
R
Lecture
Where A, B, C, D are constants 11 : of the
of characteristic
particular substance and their values are given in Table
Dilute Phase
C.1. Note that CP/R is dimensionless.
€ an ideal gas mixture the molecules have no influence on
In
another and each gas existsPneumatic
independent of the others. Hence,
the ideal-gas heat capacity of a mixture is the mole-fraction-
weighted
Rhodes:sumChapter
of the heat
transport
8 capacities of individual gases.
CPig mixture = y A CPig A + y B CPig B + yC CPig C
Where, CPig A , CPig B ,CPig are the molar heat capacities of pure
C
A, B, C in ideal gas state, and yA, yB and yc are the mole fractions.
€
Lecture 11 :
Chapter 5: Second Law of Thermodynamics
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
6
Statements of the Second Law
Statement 1: No apparatus can operate in such a way that its
only effect is to convert heat absorbed by a system completely
into work done by the system
Statement 2: No process is possible which consists solely in the

transfer of heat from oneLecture 11
temperature : to a higher
level
Dilute Phase
Modified form of the first statement in terms of cyclic processes:
Pneumatic
Statement 1a: It is impossible by a cyclic process to convert the
heat absorbed by a systemtransport
completely into work done by the
Rhodes: Chapter 8
system
Heat Engine
In operation, the working fluid of a heat engine absorb heat QH
from a hot reservoir, produces a net amount of work W , discard
heat Qc to a cold reservoir, and return to its original state.
Since the process is cyclic, the internal energy doesn’t

€ change,
therefore, Lecture 11 €:
W = QH − QC
€ Dilute Phase
The thermal efficiency of the engine is defined as,
Pneumatic
€
Rhodes: Chapter 8
transport
100% efficiency can be achieved only if Qc =0.

Carnot’s Theorem and Equations
For two given heat reservoirs no engine can have a
thermal efficiency higher than that of a Carnot engine.
The thermal efficiency of a Carnot engine depends on the
temperature levels and not upon the working substance of
the engine Lecture 11 :
W TC
η ≡Dilute = 1 −Phase
QH TH
A Carnot engine can have 100% efficiency only if TH ∞ or
Pneumatic
TC  0. Neither conditions exist on earth.
TheRhodes: €Chapter on
cold reservoirs
transport
8 earth are the atmosphere, lakes and
rivers, and the oceans, for which TC is about 300K. The hot
reservoirs are furnaces, which usually operate at about 600K.
With these values, 300
η ≡1− = 0.5
600
Entropy
axiom: There exists a property called entropy S, which is an
intrinsic property of a system, functionally related to
the measurable coordinates which characterize the
system. For a reversible process, changes in this
property are give by: dQrev
LecturedS11= : t
T
Dilute Phase
Entropy is a State Property.
Since entropy is a state property, its change on going from
state A to state B is always, Pneumatic
SBt − SAt even for an irreversible
process €
However,
Rhodes: forChapter 8
transport
an irreversible process, SB − SA ≠ ∫ A → B
t t dQ
T
The entropy change € of a heat reservoir 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.
€
Entropy Changes for Ideal Gases
Lecture 11 :
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
The Mathematical Statement of 2nd Law
In the case of direct heat transfer and for an adiabatic process,
we have seen that,
ΔStotal ≥ 0
Where the equality appliesLecture 11processes.
to reversible : This can be
shown to be true for all processes
€ Dilute Phase
Pneumatic
No process is possible for which
the total entropy decreases
Rhodes: Chapter 8
transport
Work done by a heat engine
Consider a cyclic heat engine that absorbs heat QH from a
reservoir at TH and reject heat QC into another reservoir at
lower temperature TC, and produces work W
ΔStotal = ΔS Ht + ΔSCt + ΔS HE
t
€
− QH QC €
− QH QC
Lecture 11 :
= + +0 = + TC
TH Dilute Phase
€
TH TC TC W = −TC ΔStotal + QH (1 − )
TH
W = QH − QC
Pneumatic
work output
TheRhodes: Chapter
transport
is zero8 when the heat engine is completely
€
inefficient  irreversible heat transfer between two heat reservoirs
€ The work output is maximum when the engine reversible 
Carnot engine
Lost Work
Lecture 11 :
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
The engineering significance of this result is clear: The greater the
irreversibility of a process, the greater the rate of entropy production
and greater the amount of energy that becomes unavailable for work
Lecture 11 :
Chapter 6: Thermodynamic Properties of Fluids
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
15
The General Big Picture
dH = CP dT + V (1− β T )dP
1st 2nd Property Maxwell’s dT
Law Law relations Equations dS = CP
T
− βVdP
Volumetric
Lecture
Two integrals 11 : Gibbs Energy as a
properties of Residual generating
pure fluids 5 methods
Dilute
propertiesPhase function
Pneumatic
Rhodes: Chapter 8
transport
Ideal-gas
Process
Calculation
Real-gas
Process Non-reacting
Calculation mixtures 16
Fundamental Relations and Maxwell’s Equation
# ∂M & # ∂ N &
dF = Mdx + Ndy % ( =% (
$ ∂y ' x $ ∂ x ' y
# ∂T & # ∂P &
€ dU = TdS − PdV
Lecture %11 (: = −% (
$ ∂V ' S $ ∂S 'V
€
Dilute Phase
# ∂T & # ∂ V &
dH = TdS + VdP % ( =% (
€
Pneumatic
€
$ ∂P ' S $ ∂ S ' P
# ∂P & # ∂ S &
€ dA = −PdV
Rhodes: − SdT8
Chapter
transport
% ( =% (
$ ∂T ' $ ∂ V '
V T
€
# ∂V & # ∂S &
dG = VdP − SdT % ( = −% (
€ $ ∂T ' P $ ∂P 'T
€
17
Enthalpy and Entropy as functions of T and P
$ ∂V ' dT $ ∂V '
dH = CP dT + (V − T& ) )dP dS = CP − & ) dP
% ∂T ( P T % ∂T ( P
Lecture 11 :
Internal Energy and Entropy as functions of T and V
€
Dilute Phase
# ∂P & € dT # ∂P &
dU = CV dT + (T% ( Pneumatic
− P)dV dS = CV + % ( dV
$ ∂T 'V T $ ∂T 'V
Rhodes: Chapter 8
transport
For ideal gas, it reduces to,
€ ig ig €ig ig dT dP
dH = C dT P
dS = CP −R
T P
18
Alternative Forms for Liquid
The enthalpy and entropy changes of liquids are usually
represented in terms of isothermal compressibility κ, and volume
expansivity β.
Substituting these into the expressions for enthalpy and entropy

change, Lecture 11 :
Dilute
dH = C Phase
P dT +V (1− β T )dP
dS = CPPneumatic
dT
− βVdP
T
From pressure
Rhodes: dependence
Chapter 8
transport
of internal energy
# ∂U & # ∂V & # ∂V &
% ( = −T% ( − P% ( = (κP − βT)V
$ ∂P 'T $ ∂T ' P $ ∂P 'T
19
T
− βVdP
Volumetric
Lecture
pure fluids 5 cases
Dilute
Pneumatic
Rhodes: Chapter 8
transport
Ideal-gas
Process
Calculation
Real-gas
Gibbs Energy as a Generating Function
V # ∂ (G /RT) & H $ ∂ (G /RT) '
=% = −T &
RT $ ∂P ('T RT % ∂T )( P
Lecture 11 :
S H G U H PV
€
=
R RT RT
− Dilute
€
Phase=
RT RT RT
−
Pneumatic
The Gibbs energy when given as a function of T and P serves as a
Rhodes:function
€ generating Chapterfor € transport
8 the other thermodynamic properties, and
implicitly represents complete property information
21
Residual Gibbs Energy as a Generating Function
Definition of a generic residual property as,
M R ≡ M − M ig
where, M is the molar value of any extensive thermodynamic
property, such as, V, G, H, U, or S
€
Lecture 11 :
∂ (G /RT)Dilute Phase $ /RT) '
R R
V R # R & H ∂ (G
=% ( = −T & )
RT $ ∂P 'T RT % ∂T (P
Pneumatic
R R R
R R R U H PV
S
=
H
−
G
Rhodes: Chapter 8
transport
RT RT
= −
RT
R RT RT
€ €
The residual Gibbs energy therefore serves as a generating
functions for other residual properties
€ €
22
Linking Residual Gibbs Energy with Volumeric Properties of Fluids
GR P dP HR P $ ∂Z ' dP
RT
= ∫ 0
(Z −1)
P RT
= −T ∫ 0 & )
% ∂T ( P P
S R
P $ ∂Z ' dPLecture P 11dP: (constant T)
= −T ∫ 0 & ) − ∫ 0 (Z −1)
€ R % ∂T ( P Dilute
P Phase P
€
Pneumatic
€ P # ∂Z & dP
Rhodes: Chapter 8
transport
P dP
∫ 0 %$ ∂T (' P ∫ 0 (Z −1) P
P
€ € 23
Residual Properties by Equations of States
This requires an equation which can be directly solved for Z (or
V) as a function of P at constant T – so called volume explicit EOS;
Reformulation is required to use pressure explicit EOS
Lecture 11 :
Case 1: When the compressibility factor is given by the two term
virial equation, Dilute Phase
G R BP H R ! PPneumatic
$! B dB $ SR PdB
= = # &# − & =−
RT RT RT " R %" T dT % R RdT
Rhodes: Chapter 8
transport
24
Case 2: The simplest pressure-explicit EOS is the three-term three
term virial equation, which can be written in terms of ρ as,
Z −1 = Bρ + Cρ 2
G R Lecture
3 2
11 :
= 2Bρ + Cρ − ln Z
RT 2Dilute Phase
€
HR Pneumatic
*# B dB & # C 1 dC & 2 -
= T ,% − (ρ + % − (ρ /
RT +$ T dT ' $ T 2 dT ' .
€
Rhodes: Chapter 8
transport
SR *# B dB & 1 # C dC & 2 -
= ln Z − T ,% + ( ρ + % + (ρ /
R +$ T dT ' 2 $ T dT ' .
€
25
€
Case 3: Cubic EOS
GR α (Tr )R 2TC2
= (Z −1) − ln(Z − β ) − qI a(T) = Ψ
RT PC
HR " d ln α (Tr ) %
= Z −1+ $ −1' qI RTC
RT b=Ω
# d lnTr & PC
SR d ln α (Tr )Lecture 11 : bP a(T)
= ln(Z − β ) + qI € β≡ q≡
R d lnTr bRT
Dilute Phase RT
d( ρ b) Z −β
I=∫
ρ
Pneumatic
Z = 1+ β − qβ
(Z + εβ)(Z + σβ)
0
(1+ ερ b)(1+ σρ b) €
Rhodes: Chapter 8
transport
When ε ≠ σ When ε = σ
1 " Z +σ b % €
I= ln $ ' I=b/Z
σ − ε # Z + εb &
26
Calculation Steps with Cubic EOS
Calculate the parameters in the EOS: a, b, q, β, etc. using the
critical properties of the fluid, and the definitions of these
quantities for the particular choice of EOS
α (Tr )R 2TC2 RTC a(T) bP
a(T) = Ψ b=Ω q= β≡
PC
PC Lecture11 :bRT RT
Solve the EOS for the volume root of interest (vapor-like or
Dilute Phase
liquid-like), and the compressibility Z, using an iterative procedure
on the appropriate form of the EOS
€ € Z − β Pneumatic € €
Z = 1+ β − qβ
(Z + εβ)(Z + σβ)
Solving I
Rhodes: Chapter 8
transport
For the given EOS, evaluate dlnα(Tr)/dln(Tr) at the temperature of
interest
€
from the plot or analytically.
Substitute all these values into the equations for GR/RT, HR/RT
and SR/RT
Case 4: Table-based Generalised Correlations
0 1
H R
=
(H) R
+ω
) (H R
S R
( S )R
0
( S ) R
1
RTC RTC RTC = +ω

R R R
Lecture 11 :
Steps for using these expressions to evaluate residual properties
€
Dilute
 Find the critical properties
€
and Phase
accentric factor for the gas
 Compute the reduced temperature and pressure
 Look up the values of (H Pneumatic
R)0/RT , (HR)1/RT , (SR)0/R, (SR)1/R, at
C C
the desired conditions, using interpolation if necessary
SubstituteChapter
 Rhodes: these values
8
transport
in the expressions for the residual
enthalpy and entropy
28
ØCase 5: Analytical Correlations of Residual Properties at low pressures
HR * dB 0 $ dB1 '-
= Pr ,B 0 − Tr + ω & B1 − Tr )/
RTC + dTr % dTr (.
SR $ dB 0 dB1 '
= −Pr & Lecture
+ω ) 11 :
R % dTr dTr (
€ Dilute Phase
0
B = 0.083 − 1.6Pneumatic
0.422 1 0.172
B = 0.139 − 4.2
€ Tr Tr
dB 0
0.675
Rhodes: Chapter 8
transport
dB 1
0.722
= 2.6 =
dTr T
r dTr Tr5.2
€ €
€ € 29
T
− βVdP
Volumetric
Lecture
pure fluids 5 cases
Dilute
Pneumatic
Rhodes: Chapter 8
transport
Ideal-gas
Process
Calculation
Real-gas
The three Step Calculation Procedure
Step 1: transform the real gas from (T1, P1) to a hypothetical ideal
gas at (T1, P1). The entropy change and enthalpy change for this
process are by definition,
H1ig − H1 = −H1R
S1ig − S1 = −S1R Lecture 11 :
Step 2: transform the
hypothetical ideal gas at Dilute
(T1, P1) to Phase
€
a hypothetical ideal gas at (T2, P2).
€ Pneumatic
This change can be computed from
ideal gas heat capacity,
Rhodes: Chapter T8
transport
ΔH ig = H 2ig − H1ig = ∫T CPig dT
2
ig dT P2
T
ΔS = S2 − S1 = ∫T CP
ig ig ig 2
− Rln
1 T 1 P
31
With the heat capacity given by an expression of the form
CPig /R = A + BT + CT 2 + DT −2
these expressions can be easily evaluated,
$ B 2 C 3 1 1 '
ΔH = R & A(T2 − T1 ) + Lecture
ig
(T2 − T1 ) +11(T:2 − T1 ) − D( − ) )
2 3
€ % 2 3 T2 T1 (
ig
$ T2
Dilute C Phase
2 2 D 1 1 ' P2
ΔS = R & Aln + B(T2 − T1 ) + (T2 − T1 ) − ( 2 − 2 ) ) − Rln
€
% T1 Pneumatic
2 2 T2 T1 ( P1
Step 3: transform the hypothetical ideal gas at (T2, P2) back to a
real gas at (T2, Chapter
Rhodes: P2). The 8 transport
entropy change and enthalpy change for this
process are by definition,
H 2 − H 2ig = H 2R
S2 − S2ig = S2R
32
The original equations have therefore been rearranged to
develop a 3 step calculational path:
Lecture T
11 :
ΔH = −H1R + ∫T CPig dT + H 2 R
2
Dilute Phase
1
R T P2
∫T CP dT − Rln P + S2R
2
ig
ΔS = −S1 + Pneumatic
1
1
€
Rhodes: Chapter 8
transport
€
33
Extension to Gas Mixtures
Approximate results for mixtures can be obtained by extending the
generalized correlations for pure gases to mixtures with the help of
simple linear mixing rules to define pseudocritical parameters:
ω = ∑ y iω i TPC = ∑ y iTCi PPC = ∑ y i PCi

i iLecture 11 : i
Where the subscript pc stands for pseudocritical
Dilute Phase
Pseudocritical reduced temperature and pressure can then be
defined via
€ € T Pneumatic
€ P
Tpr = Ppr =
Tpc Ppc
parameters
TheRhodes:
transport
ω, T , 8and P for a gas mixture obtained in this way,
Chapter pr pr
can then be used in place of pure gas parameters ω, Tr, and Pr in tables
(such as those in Appendix E of SVA), to evaluate residual properties.
€ €
34
T
− βVdP
Volumetric
Lecture
pure fluids 5 cases
Dilute
Pneumatic
Rhodes: Chapter 8
transport
Ideal-gas
Process
Calculation
Real-gas
Enthalpy Change for Liquid-Vapor Phase changes
dP sat Saturation pressure
ΔH = TΔV
dT
Latent Heat
Volume change with phase transition
Lecture 11 :
The most commonly used is the Antoine equation,
€
Dilute
sat Phase
B
ln P = A −
T +C
Pneumatic
Antoine coefficients, A, B and C are available for many
Rhodes: Chapter 8
transport
compounds. Each set of constants is valid only for a
specified temperature range. Values are given in Table b.2
€
of App. B.
36
Lecture 11 :
Chapter 10: Theoretical Framework of Solution
Thermodynamics
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
37
Brief Summary of Solution Thermodynamics Framework
µiα = µi β = ... = µiπ

(i = 1,2,3,...,N)
Lecture 11 :
ig
€ Dilute Phase
€
R i i i
G = RT lnΦ
i i
Rhodes:
lnΦ =
€
i
P
∫ Chapter
( ) 8
Z −1 dP /P
i
transport
Φ
R
i i
0
$ V l ( P − P sat ) ' ˆ = P Z i −1
€€ f i = Φsat
i Pi
sat
exp&
&
i
RT
i
)
)
ln Φ i ∫ 0 P
dP
% (
€ €
€
€
€
id
Lecture 11 : fˆ
Dilute Phase xi fi
M E = M − M id
€ ig ig
µ = G + RT ln y
M E
Rhodes:
i = M − M id
i Chapter
i
transport
i
i
id
8 µ = G + RT ln x
i
i
VS
ln γ = &
i
i
$ ∂ (nG /RT) '
) i
E
% ∂n i ( P ,T ,n j
€ d# &= dP − dPdT + ∑ ln γ i dni = ∑ x i ln γ i
" RT % RT RT 2
i RT i
i
€
Partial Properties
CHE4162 Particle
Definition of partial properties,
Technology
$∂ (nM) '
Mi ≡ & )
% ∂n i (T ,P,n j
Lecture
The three kinds of properties used in 11 : thermodynamics
solution
are distinguished by the following symbolism:
€
Dilute Phase
Solution properties For example: V U H S G
MPneumatic
Partial properties For example:
M i transport V i U i H i Si Gi
Rhodes: Chapter 8
Pure-species€ For example:
€ € € Vi€U€
Mi i H i S i Gi
properties
€ € € € € €
€ € € € € €
Rules of Partial Properties
Summability Relations - they allow for a calculation of molar
properties from partial properties
M = ∑ xi Mi nM = ∑ n i M i
Lecture 11 :
i i
Gibbs/Duhem Theorem:
at constant T and P, Dilute Phase
€ € ∑ xid M i = 0
Pneumatic
i
This relation
Rhodes: between
Chapter
transport
8 all the partial molar properties
implies that they cannot all change independently at
constant T and€ P.
Partial Properties in Binary Solutions
Partial molar properties of a binary solution can be obtained
directly from a measurement of total solution properties as
functions of composition
dM dM
M1 = M + x 2 M 2 = M + x1
dx1 Lecture 11 : dx1
Dilute Phase
€ Pneumatic
€
Rhodes: Chapter 8
transport
Relations Among Partial Properties
Partial properties are related to each other, and a simple rule can
be applied to find these relationships:
Every equation that provides a linear relation among
thermodynamic properties of a constant composition
Lecture
solution, has its counterpart 11 : connecting the
an equation
corresponding partial properties of each species in solution
Dilute
Many equations that relate partialPhase
properties can simply be
written by analogy
Pneumatic
dGi = Vi dP − Si dT H i = U i + PVi
Rhodes: Chapter 8
transport
# ∂G & " ∂G %
Si = − % i ( Vi = $ i '
$ ∂T 'P,x # ∂P &T ,x
€ €
Chemical Potential
Definition of chemical potential
$∂ (nG) '
µi ≡ & )
Lecture 11j
% ∂n i (T ,P,n :
Dilute
µiα = µi β = ... = µiπ Phase
(i = 1,2,3,...,N)
Multiple phases at the same
€ Pneumatic
T and P are in equilibrium when
the chemical potential of each species is the same in all phases
This result Chapter
€Rhodes: € transport
forms the8basis for the description of phase and
reaction equilibria
Partial Properties for Ideal Gas Mixtures
CHE4162
Gibbs theorem
Particle Technology
ig ig
M (T, P) = M (T, Pi )
i i (M ig
i ≠V
ig
i )
Enthalpy: Since the enthalpy of an ideal gas is independent on pressure,
ig
H =H
i
ig
i
H ig
= ∑ i i 11 :
Lecture y H ig
H ig
− ∑ y ig
i i =0
H
€ i i
Entropy: the entroy of an ideal gas is dependent on pressure,
ig
Dilute Phase 1
ig
S i (T,P) = Si (T,P) − Rln y i S − ∑ yi Si = R∑ yi ln
ig ig
€
Gibbs Energy: € Pneumatic
€ i i yi
Rhodes:
ig ig
Chapter
ig 8
transport
µi = G i = Gi + RT ln y i
€ G ig = ∑ y iΓi (T) + RT ∑ y i ln Pi
µiig = Γi (T) + RT ln y i P i i
€
€ €

(i = 1,2,3,...,N)
Lecture 11 :
ig
€ Dilute Phase
€
R i i i
G = RT lnΦ
i i
Rhodes:
lnΦ =
€
i
P
∫ Chapter
( ) 8
Z −1 dP /P
i
transport
Φ
R
i i
0
$ V l ( P − P sat ) ' ˆ = P Z i −1
€€ f i = Φsat
i Pi
sat
exp&
&
i
RT
i
)
)
ln Φ i ∫ 0 P
dP
% (
€ €
€
€
Calculation of Fugacity for Pure Gas Species
 Volume-explicit EOS:
P
lnΦi = ∫ (Z −1)dP /P
0
Lecture 11 :
i
Dilute Phase
Cubic
€ EOS, Pneumatic
Rhodes:lnΦ i = Z
Chapter i 8
−1 − transport
ln(Z i − βi ) − qi Ii
€
Calculating Fugacity Coefficient of Pure Species From
Generalized Correlations
The generalized compressibility correlation can be applied
directly to obtain the fugacity coefficients of pure species
ω
Φi = (Φ 0
i )(Φ )
1
i
Values of Φ 0 and Φ1 from the Lee/Kessler compressibility

correlation are tabulated Lecture 11be: used in the the same
i i
in SVA, and can
way as other generalized correlations
€ Dilute Phase
When the simplest form of the virial expansion is valid one can
use
€ the two Pneumatic
€ term virial expansion formulation of the Lee/Kessler
correlation $ Pr 0 '
& ( B + ωB ) )
transport
1
Φi = exp
Rhodes: Chapter 8 % Tr (
0.422 0.172
where, B = 0.083 − 1.6
0 1
B = 0.139 − 4.2
Tr Tr
€
Vapor/Liquid Equilibrium for Pure Species
The Gibbs energy for pure vapor and liquid phases can be written
in terms of fugacity as,
Giv = Γi (T) + RT ln f iv
Gil = Γi (T) + RT ln f il
Lecture
If two pure species are in 11
equilibrium, :
then
€
Dilute
f i v = f i l =Phase
f i sat
Where, fisat€
indicates the value for either saturated vapor or liquid
Pneumatic
In terms of fugacity coefficients,
Rhodes:
v sat l sat
φi Pi Chapter
= φi Pi 8
€ transport φ i
v
= φ i
l
= φ i
sat
For a pure species, coexisting liquid and vapor phases are

in equilibrium when they have the same temperature,
pressure and fugacity (or fugacity coefficient)
Calculation of Fugacity for a Pure Liquid
The fugacity of a pure species i as a compressed liquid is
calculate in two steps:
1. The fugacity coefficient of saturated vapor is determined from,

Pisat dP
ln φ i
sat
=Lecture
∫ 0 ( Zi −1)11
:P
The fugacity of the saturated
Dilutevapor (and the saturated liquid) is
Phase
then, fisat = ΦisatPisat
Pneumatic
2. The fugacity change due to the pressure increase from the
saturation pressure to the actual pressure of the liquid is then
transport
Rhodes:
calculated Chapter 8
as the second step
" V l ( P − P sat ) %
i i
sat sat
fi = φi Pi exp $ '
$ RT '
# &

(i = 1,2,3,...,N)
Lecture 11 :
ig
€ Dilute Phase
€
R i i i
G = RT lnΦ
i i
Rhodes:
lnΦ =
€
i
P
∫ Chapter
( ) 8
Z −1 dP /P
i
transport
Φ
R
i i
0
$ V l ( P − P sat ) ' ˆ = P Z i −1
€€ f i = Φsat
i Pi
sat
exp&
&
i
RT
i
)
)
ln Φ i ∫ 0 P
dP
% (
€ €
€
€
Calculating Fugacity Coefficients for Mixture From the Virial EOS
The fugacity coefficient of each species in solution can be found
from an equation of state that gives the compressibility as a
function of the pressure, temperature and composition
The simplest example is the virial EOS for a mixture, which has
Lecture
the same form as the virial 11
equation for : species,
a pure
BP
Dilute
Z = 1+Phase
RT
In this case however, the Pneumatic
virial coefficient B is a function of both
temperature and composition
The composition
Rhodes: Chapter 8
transport
€dependence is B = ∑∑ y y B i j ij (*)
i j
Where yi and yj are mole fractions, and the sums are over all the
mole fractions in the mixture
€
Calculating Fugacity Coefficients for Mixture From the Virial EOS
For a Binary System,
ˆ P ˆ P
ln Φ1 = (B11 + y 22δ12 ) ln Φ2 = (B22 + y12δ12 )
RT RT
Where, δ12 = 2B12 − B11 − B22
Lecture 11 :
The binary case can be extended to multicomponent gas
€ €Dilute
mixtures; the general equation is, Phase
P # 1 &
€ ln φˆ =
k %BPneumatic
kk + ∑ ∑ yi y j (2δik − δij )(
RT %$ 2 i j ('
Where the dummy
Rhodes: indices
Chapter 8
transport
i and j run over all species, and,
δ ik ≡ 2Bik − Bii − Bkk and δ ij ≡ 2Bij − Bii − B jj
with δ ii = 0; δ kk = 0, and δ ik = δ ki
€ €
Values of the virial coefficients Bij can be obtained from mixing
rule,
RTCij
Bij =
PCij
( B 0 + ω ij B1 )
ωi +ω j
Lecture 11 :
ZCij RTCij
ω ij = TCij = Dilute
TCiTCj (1 −Phase
K ij ) PCij =
2 VCij
1/ 3 % 3
Z Ci Pneumatic
+ Z " 1/ 3
€ Cj VCi + VCj
ZCij = VCij = $ '
2 2
€ €
Rhodes: Chapter 8
transport # &
€
€
The quantity Kij is an empirical interaction parameter specific to
an i-j molecular pair. When i=j and for chemically similar species, kij
= 0. It is often set equal to zero when it is unknown. When
possible, it is evaluated from PVT data, and is generally a small
positive number
Lecture 11 :
Dilutereduce
When i = j, all the expressions Phase
to the pure component
expressions
Pneumatic
The advantage of the generalized correlation for second virial
coefficients
Rhodes: isChapter
transport
their simplicity
8 – they have no physical significance.
More complex correlations appear in literature.

(i = 1,2,3,...,N)
Lecture 11 :
ig
€ Dilute Phase
€
R i i i
G = RT lnΦ
i i
Rhodes:
lnΦ =
€
i
P
∫ Chapter
( ) 8
Z −1 dP /P
i
transport
Φ
R
i i
0
$ V l ( P − P sat ) ' ˆ = P Z i −1
€€ f i = Φsat
i Pi
sat
exp&
&
i
RT
i
)
)
ln Φ i ∫ 0 P
dP
% (
€ €
€
€
€
id
Lecture 11 : fˆ
Dilute Phase xi fi
M E = M − M id
€ ig
µ = G + RT ln yig
M E
Rhodes:
i = M − M id
i Chapter
i
transport
i
i
id
8 µ = G + RT ln x
i
i
VS
ln γ = &
i
i
$ ∂ (nG /RT) '
) i
E
% ∂n i ( P ,T ,n j
€ d# &= dP − dT + ∑ ln γ i dni = ∑ x i ln γ i
" RT % RT RT 2
i RT i
i
€
Lecture 11 :
Lecture 20: Mixing Processes and Heat of Reaction
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
Property Changes of Mixing
Residual properties can be evaluated from experimental PVT-
data and equations of state. Excess property values can be found
from mixing experiments
These ideal solution properties are derived from partial
property equations of a pure species in an ideal solution
For an ideal solution,
Lecture 11 :
G id = ∑ x iGi + RT ∑ x i ln x i
Dilute
i Phase
i
S id = ∑Pneumatic
x i Si − R∑ x i ln x i
i i
idtransport
€
Rhodes: Chapter 8 V = ∑ x iVi
i
€ H id = ∑ x i H i
i
€
The corresponding excess properties are, by definition, the
difference between the actual properties of the (non-ideal)
mixture and ideal solution properties
Lecture 11 :
G E = G − G id = G − ∑ x iGi − RT ∑ x i ln x i
Dilutei Phase i
S − ∑ x i Si + R∑ x i ln x i
S E = S − S id =Pneumatic
i i
€ V E
Rhodes: Chapter 8
= V −transport
V id
= V − ∑ x iVi
i
€ H E = H − H id = H − ∑ x i H i
i
€
The first two terms on the right side of each equation express a
difference of the form,
M − ∑ xi Mi
i
Lecture 11 :
These quantities are property changes of mixing, denoted by the
symbol ΔM, Dilute Phase
€ ΔM ≡ M − ∑ x i M i
Pneumatic
i
Where, M is a molar solution property, and Mi is a molar pure-

species property,
Rhodes:
transport
all at8 the same T and P
Chapter
€
The excess property equation can now be written as,
G E = ΔG − RT ∑ x i ln x i
i
S E =Lecture : 11x i
ΔS + R∑ x i ln
EDilute
V = ΔV
i
Phase
€
H E =Pneumatic
ΔH
€
Rhodes:€Chapter 8
transport
Where, ΔG, ΔS, ΔV, and ΔH, are the Gibbs energy, entropy, volume
and enthalpy
€ changes of mixing, respectively
ΔV = 0 only for ideal mixing
Lecture 11 :
Dilute Phase
Pneumatic Total volume of a real solution is not
simply a weighted sum of the molar
Rhodes: Chapter 8
transport volume of its constituent species
Instead, it is a weighted sum of the

partial molar volume of its
constituent species
This implies one could always expect

a volume change of mixing which is
equal to the excess volume when a
solution is formed from mixing
Heat of Reactions
Lecture 11 :
Dilute Phase
Pneumatic Important assumption for calculation
of heat of reaction
Rhodes: Chapter 8
transport
Such constant temperature assumption allows the heat involved in the reaction
process to be calculated as the enthalpy change
Heat of Reactions
Consider the generic balanced chemical reaction,
aA + bB →lL + mM
The standard heat of reaction is defined as the enthalpy change
when a mole of A, and b moles of B, in their standard states at
temperature€ T, react to Lecture
form l moles 11
of L, :
and m moles of M, in
their standard states at the same temperature T
Dilute Phase
A standard state is a particular state of a species at temperature T
and at specified conditions Pneumatic
of pressure, composition, and physical
condition as, e.g., gas, liquid, or solid
Rhodes: Chapter 8
transport
Standard states for computing heats of reactions are:
Gases: the pure substance in the ideal gas state at 1 bar;
Liquids and solids: the real pure liquid or solid at 1 bar.
Property values in their ideal standard state are denoted by the
degree symbol. For example, Cpo is the standard state heat capacity.
Since the standard state for gases is the ideal gas state, Cpo=Cpig
Note that standard state properties are functions of temperature
Lecture
only, since all other conditions are fixed11 :
When a heat of reaction is given for a particular reaction, it
Dilute
applies for the stoichiometric Phase
coefficients as written. If each
stoichimetric coefficient is doubled, the heat of reaction is doubled
Pneumatic
as well. For example, the ammonia synthesis reaction may be
written 1 3 transport o
N
Rhodes: Chapter2 + H
8 2 →NH 3 ΔH 298 = −46,110J
2 2
o
N 2 + 3H 2 →2NH 3 ΔH 298 = −92,220J
The symbol, ΔH o indicates that the heat of reaction is the
298
standard value for a temperature
€ of 298.15K
€
€
Standard Heat of Formation
It is impractical to tabulate the heats of reaction for all possible
reactions of interest – fortunately, the standard heat of any
reaction can be calculated if the standard heats of formation of the
compounds taking part in the reaction are known
A formation of reaction Lecture

is defined as 11 : which forms a
a reaction
single compound from its constituent elements – the heat of
Dilute Phase
reaction is based on 1 mole of compound formed
Pneumatic
The reaction C + 1/2O2 +2H2  CH3OH is the formation reaction
for methanol. The reaction
Rhodes: Chapter
transport
8 H2O +SO3  H2SO4 is not a formation
reaction
Standard Heat of Combustion
Many standard heats of formation come from standard heats of
combustion – a combustion reaction is defined as a reaction
between an element or compound and oxygen to form specified
combustion products
Data are always based on 1 mol of substance burned
Lecture 11 :
A reaction such as the formation of n-butane:
4C(s) + 5HDilute
Lecture 24 Phase
2 (g) →C 4 H10 (g) 9
cannot carried out in practice. However, this equation results from

the combustion of the
• However, Pneumatic
thefollowing
this equation results from the combination of
combustion
following combustion reactions:
reactions:
transport
◦
Combustion equation is written 4 C(s) + 4 O (g) → 4 CO (g) ; ∆H = (4)(−393, 509) J
2 2 298
in the normal €Rhodes:

order for both Chapter 58 2
1
2 2
◦
H (g) + 2 O (g) → 5 H O(l) ; ∆H = (5)(−285, 830) J
298
reactants (substance + oxygen to 2
1
produce combustion products) 4 CO2 (g) + 5 H2O(l) → C4 H10(g) + 6 O2(g) ; ◦
∆H298 = 2, 877, 396 J
2
Combustion equation is written in
the reversed order for the product
◦
(combustion products react to 4 C(s) + 5 H2 (g) → C4 H10(g) ; ∆H298 = −125, 790 J
produce substance + oxygen)
Combustion products are always CO2 and/or H2O ◦
The Temperature Dependence of ∆H
Lecture 11 :
Dilute Phase
Pneumatic
Rhodes: Chapter 8
transport
give the standard heat of the resulting reaction — such
equations often include an indication of the physical
state of each reactant and product, i.e., the letter g, l,
or s
• The water-gas-shift reaction, CO2(g)+H2(g) → CO(g)+
H2O(g) is commonly encountered in chemical industry
— usually at temperatures well above 25◦ C. The
initial step is to evaluate the standard heat of reaction
at 25◦ C Lecture 11 :
• The pertinent formation reactions are:
Dilute Phase◦
CO2(g) : C(s) + O2(g) → CO2(g) ; ∆Hf 298 = −393, 509 J
Pneumatic
H2(g) : Since hydrogen is an element ; ∆Hf◦298 = 0
CO(g) : C(s) +
1
Rhodes: Chapter 82 O 2 transport
(g) → CO(g) ; ∆H ◦
f 298 = −110, 525 J
1
H2O(g) : H2(g) + O2(g) → H2O(g) ; ∆Hf◦298 = −241, 818 J
2
Lecture 24 8
• The formation reaction for CO needs to be written in
 The formation reaction for CO2 needs
2 to be written in
reverse
reverse in order
in order to sum
to sum the the formation
formation reactions
reactions to the
to yield yield
the water-gas-shift reaction
water-gas-shift reaction
◦
CO2 (g) → C(s) + O2 (g) ; ∆H298 = 393, 509 J
1
Lecture 11 :
C(s) + O2 (g) → CO(g) ; ∆H298
2
◦
= −110, 525 J
1
+
◦
2 Dilute Phase
H2 (g) + O2 (g) → H2 O(g) ; ∆H298 = −241, 818 J
Pneumatic ◦
CO (g) + H (g) → CO(g) + H O(g) ; ∆H = 41, 166 J
2 2 2 298
 The enthalpy of 1 mol CO

Rhodes: Chapter 8
transport
of plus 1 mol of H2O is greater
• The
than theenthalpy
enthalpy of
of 11mol
molofCO of plus
H2 plus 1 mol1ofmol
CO2 of H2O isJ
by 41,166
greater
when each than theand
product enthalpy
reactantofis 1taken
molasofthe
H2pure
plusgas
1 at
mol
25◦C
of in
COthe ideal
2 by gas state
41,166 at 1 each
J when bar product and reactant is
taken as the pure gas at 25◦C in the ideal gas state at
1 bar
The standard heats of reaction at other temperatures can be
calculated from a knowledge of the value at the reference
temperature
The general chemical reaction can be written,
ν1 A1 + ν 2 ALecture
2 + ... → ν A11
3 3 + ν:4 A4 + ...
Dilute
Where, ΙνiΙ is a stochiometric Phase
coefficient, and Ai stands for a
chemical formula – the species on the left are reactants, and those
on the
€ right are products.
Pneumatic
The sign convention
Rhodes: Chapter for
transport
8 νi is as follows:
Positive (+) for products
Negative (-) for reactants
The νi with their accompanying signs are called stoichiometric
numbers. For example, when the ammonia synthesis reaction is
written,
N 2 + 3H 2 →2NH 3
Then, Lecture 11 :
ν N = −1 ν H = −3 ν NH = 2
Dilute Phase
2 2 3
The sign €convention allows the definition of a standard heat of

Pneumatic
reaction to be expressed mathematically by equation:
€ € ΔH o =€∑i i
ν H o
Rhodes: Chapter 8
transport
i
Summation over all The enthalpy of species i

products and reactants in its standard state
Following the sign convention for heat of reaction, Δ = Product - Reactant

€
the standard state enthalpy of a chemical compound is equal to
its heat of formation, when the convention that the standard state
enthalpy of element is zero is used, i.e.,
H io = ΔH ofi
Thus, Lecture o11 :
ΔH = ∑ν i ΔH fi
o
Dilute i
Phase
Since standard
€ state enthalpies are functions of temperature only,
dHPneumatic
i
o
= C o
p dT
i
Rhodes: Chapter 8
transport
Where the subscript i identifies a particular product or reactant
Multiplying by νi and summing over all products and reactants
gives, €
∑ i i ∑ i p i dT
ν dH o
= ν C o
i i
Since νi is a constant, it can be placed inside the differential,
∑ d(ν H ) = d∑ (ν H ) = ∑ (ν C
i
o
i i
o
i i
o
pi )dT
i i i
Lecture 11ofStandard
Standard heat of
reaction ΔHo
:reactionheat capacity change
ΔC ≡ ∑ν C o
p i
o
pi
€ preceding equationDilute
The Phase
then becomes,
i
Pneumatic
dΔH o
= ΔC o
p dT €
Rhodes: Chapter 8
transport
This is the fundamental equation relating heats of reaction to
temperature
T ΔC po
gives,
Integration € ΔH = ΔH + R ∫T
o o
0 dT
0 R
Heat of reaction at T
Heat of reaction at reference T0
If the individual heat capacities of the species are written in the
usual polynomial form,
C po i
= Ai + BiT + CiT 2 + DiT −2
Lecture 11 :
R
Then we can write,
Dilute Phase
ΔC p = ∑ν iC p = R∑ν i ( Ai + BiT + CiT 2 + DiT −2 )
o o
Pneumatic
i
€ i i
If we define,
∑ν i Ai 8 transport
ΔA =Chapter
Rhodes: ΔB = ∑ν i Bi
i i
€
ΔC = ∑ν iCi ΔD = ∑ν i Di
i i
€ €
T
ΔH = ΔH + R ∫T ( ΔA + ΔBT + ΔCT 2 + ΔDT −2 ) dT
o o
0
0
* ΔB ΔC $ 1 1 ' -
ΔH o = ΔH 0o + R , ΔA(T − T0 ) +Lecture
( T 2
− T011
2
) + : (T 3
− T0 ) + ΔD&
3
− )/
€ + 2 3 % T T0 (.
Dilute Phase
As we have seen, the reference temperature T0 is usually 298.15K
Pneumatic
The heat effects of mixing transport
are similar in many aspects to heats of
Rhodes:
reaction Chapter
– section 12.4 8is to be covered by you as a home reading
assignment – problems on this section will be given in the problem
set, and can appear in the exam
Summary
CHE4162
Mixing processes
Particle Technology
G E = ΔG − RT ∑ x i ln x i V E = ΔV
i
S = ΔS + R∑ x i ln x i
E H E = ΔH
i Lecture
Heat of reactions at standard state
€ 11 :
ΔH o = ∑ν i ΔH ofi Dilute Phase
€
i
€
€
o
Pneumatic
Heat of reactions at arbitrary temperature
ΔC
dT transport
T p
o
ΔH 0 + R ∫Chapter
o
ΔH = Rhodes: 8
T 0 R
* ΔB 2 ΔC 3 $ 1 1 '-
ΔH = ΔH + R , ΔA(T − T0 ) +
o o
0
2
( T − T0 ) +
2
3
(T − T0 ) + ΔD& − )/
3
% T T0 (.
+

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CHE3161 Chemistry & Chemical Thermodynamics

CHE4162 Particle Technology

This equality holds true for any system

Where, Gi is the Gibbs energy of the pure species at the mixture T

Note that€the enthalpy of mixing and the volume change of

Recall the definition fugacity of a species in a mixture,

Excess properties are defined as the difference between the

The activity coefficient isLecture 11partial

For an ideal solution Pneumatic

Ideal Gas Mixture µiig = Giig + RT ln yi

µiα = µi β = ... = µiπ Equilibrium criterion for

Statement 2: No process is possible which consists solely in the

Since the process is cyclic, the internal energy doesn’t

100% efficiency can be achieved only if Qc =0.

Substituting these into the expressions for enthalpy and entropy

RTC RTC RTC = +ω

ω = ∑ y iω i TPC = ∑ y iTCi PPC = ∑ y i PCi

µiα = µi β = ... = µiπ

µiα = µi β = ... = µiπ

Values of Φ 0 and Φ1 from the Lee/Kessler compressibility

For a pure species, coexisting liquid and vapor phases are

1. The fugacity coefficient of saturated vapor is determined from,

µiα = µi β = ... = µiπ

µiα = µi β = ... = µiπ

Where, M is a molar solution property, and Mi is a molar pure-

Instead, it is a weighted sum of the

This implies one could always expect

A formation of reaction Lecture

cannot carried out in practice. However, this equation results from

in the normal €Rhodes:

 The enthalpy of 1 mol CO

The sign €convention allows the definition of a standard heat of

Summation over all The enthalpy of species i

Following the sign convention for heat of reaction, Δ = Product - Reactant

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