Summary for ch 1,2,3,4,5,6,7 (Here some molar properties without underline)

(1) The three laws of Thermodynamics

－1st law: Total energy of system (SYS) plus surrounding (SUR) is conserved.
－2nd law: Total change of entropy of the universe (SYS+SUR) is positive.
－3nd law: The entropy of a perfect crystal is zero.
(2) Math preliminaries
∂2M ∂2M
(i) Exact differentials = M: any molar property
∂x∂y ∂y∂x
m
(ii) Legendre transforms dU T = TdS − PdV + ∑ μi dni
i =1

m m
(iii) Euler's and G-D Theorem M = ∑ xi M i (T , P, x) ; ∑ x d M (T , P, x)
i i T ,P =0
i =1 i =1

nM= MT = any total property in system; n: total number of moles

(3) Fundamental property relations for a closed system derived from the 1st,
2nd and 3rd laws
m
dn r U = Tdn r S − Pdn r V + ∑ μir dnir γ : any arbitrary phase
r r r
(i)
i =1

γ ⎛ ∂U T ⎞ ⎛ ∂H T ⎞ ⎛ ∂AT ⎞ ⎛ ∂G T ⎞ ⎛ ∂GT ⎞
(ii) μi = Gi = ⎜ ⎟ =⎜ ⎟ =⎜ ⎟ =⎜ ⎟ ; only ⎜ ⎟ = Gi
⎝ ∂ni ⎠V , S ⎝ ∂ni ⎠ S , P ⎝ ∂ni ⎠V ,T ⎝ ∂ni ⎠T , P ⎝ ∂ni ⎠T , P

(iii) Relationship of molar U to molar G, H, A by using Legendre transformations.

Employing the graphic plot:

- - Obtaining U and G based on H below arrow line:

V A T
(U = H − PV )
U G (G = H − T S )
H Obtaining U and G based on A above arrow line:
S P
(U = A + T S )
(G = A + PV )

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(4) Maxwell relations and more thermodynamic properties
(4-basic relations – 8-differentiations – 4-Maxwell equations)

(5) Energy and entropy balances, heat engines and heat pumps

(6) Practical thermodynamic property relations (most useful)

(i) T, P dependence of μi (chemical potential of the i component)

(ii) U, S, H in terms of (T, P, V) and in terms of (Cp, Cv).

(iii) (Cp, Cv) in terms of T, P, V dependence.

(iv) General strategy for reducing difficult derivatives (i.e. containing S) to T, P, V

(or Cp and Cv) that are measurable state variables by using Jacob procedure.

∂M ∂M ∂M
i.e. Using the form of , , M: molar property
∂T ∂P ∂V
⎛ ∂M ⎞
and ⎜ ⎟ = CP
⎝ ∂T ⎠ P
⎛ ∂M ⎞
and ⎜ ⎟ = CV
⎝ ∂T ⎠V

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Jacob procedure:
Step 1: If difficult derivatives contain G, H, U, A (say molar property, M), always
bring M in the numerator.
⎛ ∂x ⎞ 1
(A) If M in the denominator, using ⎜ ⎟ =
⎝ ∂M ⎠ y ⎛ ∂M ⎞
⎜ ⎟
⎝ ∂x ⎠ y
⎛ ∂M ⎞
−⎜ ⎟
⎛ ∂x ⎞ ⎝ ∂y ⎠x
(B) If M is the constrain, using ⎜ ⎟ =
⎝ ∂y ⎠ m ⎛ ∂M ⎞
⎜ ⎟
⎝ ∂x ⎠ y
⎛ ∂H ⎞ ⎛ ∂V ⎞
−⎜ ⎟ T ⎜ ⎟ −V
∂T ⎞ ∂ ⎝ ∂ ⎠P, x
μ = ⎛⎜ = ⎝ ⎠T =
P T
Ex: ⎟
⎝ ∂P ⎠ H , x ⎛ ∂H ⎞ Cp
⎜ ⎟
⎝ ∂T ⎠ P

Step 2: Using fundamental property relations, which contain only P, V, T, and S as

state variables (canonical variables), for those M in the numerator. e.g.:
⎡ ⎛ ∂P ⎞ ⎤
dU = TdS − PdV = Cv dT + ⎢T ⎜ ⎟ − P ⎥ dV
⎣ ⎝ ∂T ⎠V , x ⎦
⎡ ⎛ ∂V ⎞ ⎤
dH = TdS + VdP = CP dT + ⎢V − T ⎜ ⎟ ⎥ dP
⎣ ⎝ ∂T ⎠ p , x ⎦
⎛ G ⎞ 1 1 −H
d⎜ ⎟= [(− S )dT + VdP ] = ⎢⎡ dT + VdP ⎥⎤
⎝ RT ⎠ RT RT ⎣ T ⎦
⎛ A ⎞ 1
[ − SdT − PdV ] = ⎢⎡− dT + PdV ⎥⎤
1 U
d⎜ ⎟=
⎝ RT ⎠ RT RT ⎣ T ⎦

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 ⎛ ∂H ⎞ ⎡ ⎛ ∂V ⎞ ⎤
−⎜ ⎟ − ⎢V − T ⎜ ⎟ ⎥
⎛ ∂T ⎞ ⎝ ∂P ⎠T ⎣ ⎝ ∂T ⎠ P , x ⎦
Example: μ =⎜ ⎟ = =
⎝ ∂P ⎠ H , x ⎛ ∂H ⎞ CP
⎜ ⎟
⎝ ∂T ⎠ P

∂S
Step 3: Eliminate derivative of S ( , or dS) by Maxwell relation and by relation
∂
of S with Cp, Cv

(a) If S derivative with respect to (wrt) pressure and volume

⎛ ∂S ⎞ ⎛ ∂P ⎞ ⎛ ∂S ⎞ ⎛ ∂V ⎞
⎜ ⎟ =⎜ ⎟ or ⎜ ⎟ = −⎜ ⎟
⎝ ∂V ⎠T , X ⎝ ∂T ⎠V , X ⎝ ∂P ⎠T , X ⎝ ∂T ⎠ P , X

(b) If S derivative wrt temperature

⎛ ∂S ⎞ ⎛ ∂S ⎞
T⎜ ⎟ = Cp or T ⎜ ⎟ = CV
⎝ ∂T ⎠ P , X ⎝ ∂T ⎠V , X

Step 4: If any S constrains ( S ) are left from application of Maxwell relation, further

eliminate S constrains by using the triple product rule and repeat step 3.

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(7) Thermodynamic property relations for ideal gases
(i) Ideal gas volumetric properties (no molecular volume, etcetera)
(ii) U(T), H(T), Cp(T), Cv(T), is a function of temperature only
(iii) S (a function of T, P), or S (a function of T, V), or S (a function of V, P)

(8) Auxiliary functions

1 ∂V
(i) α = ⎛⎜ ⎞⎟ Expansibility (expansion coefficient) of any substance
V ⎝ ∂T ⎠ P , x

1 ∂V
(ii) KT = − ⎛⎜ ⎞⎟ Isothermal compressibility of any substance
V ⎝ ∂P ⎠T , x

(9) Residual properties (i.e. departure function of ideal gas from real gas mixture)
(i) ΔM R = M IG − M e.g.: ΔH R ; ΔS R
Aside: PΔV R = RT (1 − Z ) (residual volume is equal to B(T) at zero pressure).

(ii) The property difference (ΔH, ΔS) calculations using ideal gas relationship and
residual properties.

(10) Partial molar property of the component i ( M i )

∂ (nM )
(i) Mi = M: molar property in system
∂ni T , P ,n
j ≠i

m
(ii) M T = nM = ∑ ni M i (T , P, n) or M = Σxi M i (T , P, x)
i =1

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(11) Gibbs-Duhem Equation
⎛ ∂M ⎞ ⎛ ∂M ⎞ m
(i) 0=⎜ ⎟ dT + ⎜ ⎟ dP − ∑ xi dM i (T , P, xi ) M: molar property
⎝ ∂T ⎠ P , x ⎝ ∂P ⎠T , x i =1

⎛ ∂nM ⎞ ⎛ ∂nM ⎞ m
or 0=⎜ ⎟ dT + ⎜ ⎟ dP − ∑ ni dM i (T , P, n) nM: total property
⎝ ∂T ⎠ P ,n ⎝ ∂P ⎠T ,n i =1

(12) Relations using Gibbs energy (G)

⎛ ⎛ G ⎞⎞
⎜ ∂⎜ ⎟⎟
(i) Gibb's - Helmholtz equation ⎜ ⎝ RT ⎠⎟ = − H
⎜ ∂T ⎟ RT 2
⎜ ⎟
⎝ ⎠ P,x

⎛ G ⎞ −H ⎛ V ⎞
(ii) G in terms of H and V (or T, P) d⎜ ⎟ = dT + ⎜ ⎟dP
⎝ RT ⎠ x RT ⎝ RT ⎠
2

(13) Partial molar analogies of those fundamental property relations

e.g. dU i = TdSi − PdVi ; dGi = −S i dT + Vi dP

(14) Fugacity and fugacity coefficient definition and calculation

(i) Definitions
f
dG T , x = RTd lnf =φ for a whole system
P
f i , pure
dGi , pure T = RTd lnf i , pure = φi , pure for a pure substance
P
fi
dGi T = RTd lnf i = φi for a real mixture
xi P

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(ii) Relations for φ (whole system), φi , pure (pure substance), φi (real mixture) and
f i = xi Pφi . Fugacity is a new defined function in terms of T, P, x:

⎛ V − Vi ' ⎞ ⎛ V V ⎞ ⎛ Vi 1⎞
d ln(φi )T , x = ⎜ i ⎟ dP = ⎜ i − ⎟ dP = ⎜ RT − P ⎟ dP
⎝ RT ⎠ ⎝ RT RT ⎠ ⎝ ⎠

NOTE:
fi
EOS Calculation of = φi is easy in terms of ∫ dV . However, Experimental
xi P
measurement is easy in terms of ∫ dP .
By looking up the following equations in the 2nd Ed. Prausnitz book (3.4.-14)
⎡⎛ ∂P ⎞ RT ⎤
RTln(φi )T , x = ∫ ⎢⎜⎜
∞
⎟⎟ − ⎥ dV − RTlnZ for real mixture
⎢⎣⎝ ∂ni ⎠T ,V ,n
V
V ⎥
j ⎦
1 ∞⎡ ∂P RT ⎤
ln( φ )T , x = ∫V ⎢ − ⎥ dV − lnZ for whole system
RT ⎣ ∂n V ⎦
1 ∞ ⎛ ∂P ⎞
dln( φi )T , x = ∫ ⎜⎜ − Pi ⎟⎟dV − lnZ for pure substance
RT V ⎝ ∂ni ⎠

It means that the φi values in terms of T, V, x could be calculated using EOS more

easily than those of (T, P, x). Remember only here the volume (V) is total
volume.

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(15) Phase equilibrium with fugacity
α
(i) f i , pure = f i , pureβ = for a pure substance
α β
(ii) fi = fi = for the component i in a real mixture

(16) Behavior of pure fluids

(i) Clausius-Clapeyron Equation to calculate the heat of phase transition
(ii) Corresponding state theorem (plots) for calculation of Z, H, S, f of fluids
(iii) Critical fluids- A scaling law (e.g. ZC= 3/8 for all fluids obeying vdW EOS

(17) Behavior of real gaseous mixtures

(i) CS theorem for mixtures (one-fluid theory)
(ii) Cubic in volume (or in compressibility factor) EOS models (vdW, PR, SRK)
(iii) Adopting Mixing rules for the mixture calculation

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(18) Additional for Critical fluids, EOS, and Phase equilibrium
Figure 1: An ideal fluid isochore (equal density curves)
P
V2
V1

C.P.
V3

Ideal fluid behaves like figure 1

T

Figure 2: A real fluid isochore (equal density curves)

ρ 4 ρ3
P
ρ5
Real fluid behaves like figure 2

ρ2
ρ1
T
⎛ ∂2P ⎞ ⎛ ∂Cv ⎞
At the isochore inflection locus: ⎜ 2⎟ =0 ⇒ ⎜ ⎟ =0
⎝ ∂T ⎠ ρ , x ⎝ ∂V ⎠T , x
Figure 3: There are minimum points occurred at curves of Cv vs ρ.

Cv
T = constant

shown one of the isochore

inflection locus points

Figure 3
ρ

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(19) Representation of the P-V-T curve by a cubic volume EOS model

P C.P.

Psat b Vapor phase T=Tc

a
T<Tc

SL Sy SV V
V V V

At the critical point (C.P.) of any fluid:

⎛ ∂n P ⎞
⎜ n⎟ =0 (n= 1, 2, 3, 4)
⎝ ∂V ⎠T c

mi: moles of the phase i;

VSj: molar volume of the phase j at saturated pressure (Psat). y: a mixed phase.
mV
q: quality of vapor moles =
mt
mt: mV + mL

V SV mV + V SL mL = V t = V sy mt
⇒
V sy − V SL a
V sy
=V SV
(q ) + V (1 − q )
SL
where q = SV =
V − V SL b

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At phase equilibrium:

⎛ ∂P ⎞
○
1 Mechanical Stability ⎜ ⎟<0
⎝ ∂V ⎠

○
2 Chemical Stability must be fitted by Maxwell equal area rule

For any mixture:

∂μ I ⎛ ∂μ II ⎞
= μi = μi = ⎜⎜ ⎟⎟ ⇒ Gi = Gi
I II I II

∂ni ⎝ ∂ni ⎠T , p

For a pure component:

μ SV = μ SL ⇒ G SV = G SL

Integration of dA T = − PdV T It gives ASV − ASL = − ∫ SLSV PdV

then ASV + Pσ V SV = ASL + Pσ V SL

⇒ ASV − ASV = Pσ (V SV − V SL )

⇒ ∫ SL
SV
PdV − pσ (V SV − V SL ) = 0 It is the Maxwell equal area rule

What is the physical meaning of the Maxwell equal area rule?

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Any cubic EOS adopted for the phase equilibrium calculation must follow the
Maxwell equal area rule. i.e.:
The area of (Psat) (VSV-VSL), i.e. two domes, given by the EOS curve must be equal
to the area of (Psat)(VSV-VSL), i.e. cross rectangle, represented by the experimental
PV curve (bold line). Then, finding a suitable vapor pressure (Psat) is possible
to get vapor phase volume (VSV) and liquid phase volume (VSL).

P
C.P.

V
L
cubic EOS curve

Psat
T<Tc

SL Sy SV V
V V V

V
P-V curve
at T=constant
V SV
A2

A1 cubic EOS curve

SL
V
P
Pσ

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For example:

Supposed that VDW cubic EOS is good to represent the PVT data
RT a
P= − 2
V −b V
Integrate the above equation from VSV to VSL at a certain Pσ, then:

Maxwell equal area relation for Chemical Stability in phase equilibrium:

RT a
∫
SV
dV − ∫ 2 dV − P σ (V SV − V SL ) = 0
V −b
SL
V

V SV − b ⎛ 1 1 ⎞
⇒ RTln SL + a⎜ SV − SL ⎟ − P σ (V SV − V SL ) = 0 EQ(1)
V −b ⎝V V ⎠

RT a
Pσ = − EQ(2)
V SL − b ( V SL )2

RT a
Pσ = − EQ(3)
V SV − b ( V SV )2

EQ(1), EQ(2), EQ(3) for relations of Pσ ,V SV ,V SL indeed existed at

σ
T < Tc . In other words, it is possible to find a suitable pressure ( P ) in

fulfillment of the Maxwell equal area relation, then, two roots of vapor
phase volume (VSV) and liquid phase volume (VSL) could be solved by
using EQ(1), EQ(2), EQ(3), simultaneously.

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Discussion:

Even if the experimental P-T-x-y data could be fitted by the EOS, such as the
van der Waals (vdW) EOS as follows, but the accuracy can not be always
satisfied:
RT a
P= − 2
V −b V
PV V a
Z= = −
RT V − b RTV

At critical point, it is easy to find the a and b values from the values of Tc and Pc.
Then, substitute them into the Z equation of the vdW EOS.
PcVc 3
⇒ Zc = = = 0.375
RTc 8

According to the corresponding state theory, however, for most real fluids the
experimental Zc data ranged from 0.31 to 0.27. Again, the following good EOS
models did not give a correct answer for the ZC value of the polar water

compound:

For instance, experimental data of Zc : Z c water = 0.22 + 0.02

But:
Peng-Robinson EOS: Z c water = 1 / 3 = 0.333

SRK EOS: Z c water = 1 / 3 = 0.337

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(20) Introduction of a digitalized computer project
Suppose there is a 3-phase equilibrium problem containing V−LI, V−LII, and LI−LII

Method 1: Prausnitz approach (φ - φ method)

(Vapor phase: φi V ; Liquid phase: φi L )
At phase equilibrium of binary system, four phase equations (n(π-1)=4) could be
formulated as follows:
yiφi
V V
fi
= =1 for (V−LI) and (V−LII)
xiφi
I or II I or II
L L
fi
xiI φi
LI LI
fi
= =1 for (LI−LII) which may be not accurate as vapor phase.
x φi
LII II LII
fi i

γ
Method 2: approach (γ - φ method)
φ
A few models, NRTL, Wilson, Unifac, Uniquac, etc.
i.e. vapor phase using φi V ; liquid phase (I, II) using γ i I , II :
yiφi yiφi
V V V
fi
= = =1
fi
L
xi
fi
f i , pure xiγ i (T , P, x; xi = 1) f i , pure
xi f i , pure

xiI γ iI (T , P, x ; xi = 1) f i , pure (T , P) xiI γ iII

L I
T
fi
= II II = II II = 1
xi γ i (T , P, x ; xi =1 ) f i , pure (T , P ) xi γ i
II
L II
fi

15
(A)Calculation procedure of the computer language programming
(Please refer to Sandler’s book, MATHCAD, MATHLAB, VBASIC programs)

FORTRAN main program (bubble point-pressure calculation by giving T, xi)

Common T, etc.
aP bP
Common ai, bi, a, b, A, B A= , B =
R 2T 2 RT

Input (Tc, Pc, ω); critical property and accentric factor

Input (T, kij, δij ); bubble point temperature and binary interactional parameters
Input (xi); bubble point liquid-phase composition of the i component (0.0 to 1.0)

Check point: Σyi = S = Σki xi = k1( x1 ) + k2 ( 1 − x1 )

If S→1
ki xi
Then yi = = ki xi (↑ )
Σki xi

Then, increasing the tried bubble point pressure (P) by using a try and error
method.

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(B) Flow Chart

main program
Guess initial P, Bubble point pressure
change P, calculation
and input data
P, x, y
K1,K2
KVAL subroutine
P, x
φ φ
L L
subroutines
K1 = 1 V K 2 = 2 V
φ2 φ2
print interactive values
φ1L , φ L2
P, y
φ1V ,φV2
Fugacity L subroutine
Fugacity V subroutine
Common
Common
ai, bi, a, b, δ, A, B
ai, bi, a, b, δ, A, B
pick ZL
pick ZV
cale φL
cale φV

P, x
P, y
Z1 , Z 2 , Z3
Z1 , Z2 , Z3

Cubic (at P, T, x, y known)

Common T
Common ai, bi, a, b, δ, A, B
Calc , a & b, calc, A and B

solve for Z1, Z2, Z3 (each time)

large for vapor
small for liquid, separately

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