Termodinamika Larutan: Teori

(Solution Thermodynamics: Theory)

Lecturer: Bregas S T Sembodo

 Pendahuluan
• Sistem nyata biasanya berupa campuran fluida
• Komposisi sering menjadi peubah (variabel) utama
• Dikembangkan teori dasar aplikasi termodinamika
untuk campuran gas dan larutan
• Akan diperkenalkan:
– Potensial kimia (chemical potential)
– Sifat parsial (partial properties)
– Fugasitas (fugacity)
– Sifat ekses (excess properties)
– Larutan ideal (ideal solution)
Hubungan sifat-sifat fundamental
• Hubungan antara Energi Gibbs dengan suhu dan
tekanan pada sistem tertutup:
 ∂ ( nG )   ∂ ( nG ) 
d ( nG ) =   dP +   dT = ( nV ) dP − ( nS ) dT
 ∂P  T ,n  ∂T  P , n
– Diterapkan untuk fluida fase tunggal dalam sistem
tertutup dimana tidak terjadi reaksi kimia.
• Untuk fase tunggal, sistem terbuka (a single-phase,
open system):
 ∂ ( nG )   ∂ ( nG )   ∂ ( nG ) 
d ( nG ) =   dP +   dT + ∑   dni
 ∂P  T , n  ∂T  P , n i  ∂ni  P ,T , n
j
  ∂ ( nG ) 
Definisi potensial kimia: µi ≡  
 ∂ ni  P ,T , n j

Hubungan sifat fundamental untuk sistem fluida fase tunggal dengan komposisi
konstan maupun sebagai variabel:
d ( nG ) = ( nV ) dP − ( nS ) dT + ∑ µ i dni
i

Jika n = 1, dG = VdP − SdT + ∑ µ i dxi G = G ( P, T , x1 , x2 ,..., xi ,...)

i

 ∂G   ∂G 
V =  S = − 
 ∂P T , x  ∂T P,x
Sifat larutan, M
Energi Gibbs dinyatakan sbg fungsi
Sifat parsial, M i dari variabel-variabel kanonis

Sifat spesies murni, Mi

 Potensial kimia dan kesetimbangan fase
• Untuk sistem tertutup terdiri dari 2 fase dalam
kesetimbangan:
d ( nG )α = ( nV )α dP − ( nS )α dT + ∑ µ iα dniα d ( nG ) β = ( nV ) β dP − ( nS ) β dT + ∑ µ iβ dniβ
i i

nM = ( nM )α + (nM ) β

d ( nG ) = ( nV ) dP − ( nS ) dT + ∑ µ iα dniα + ∑ µ iβ dniβ
i i

Neraca massa:
Multi fase pada T dan P yg sama adalah dniα = − dniβ
dalam kesetimbangan jika potensial
kimia setiap spesies pada semua fase
sama.
µ iα = µ iβ
 Sifat Parsial (Partial properties)
• Definisi sifat molar parsial (partial molar property)
spesies i :
 ∂ ( nM ) 
Mi ≡  
 ∂ni  P ,T ,n j
arti : perubahan besaran M terhadap perubahan ni (jml mol i) jika
P, T dan nj (jml mol spesies lain) tetap
– Potensial kimia adalah Energi Gibbs molar parsial: µ ≡ G
i i
– Untuk sifat termodinamika M:
nM = M ( P, T , n1 , n2 ,..., ni ,...)

 ∂M   ∂M 
d ( nM ) = n   dP + n   dT + ∑ M i dni
 ∂P  T , n  ∂T  P , n i
  ∂M   ∂M 
d ( nM ) = n   dP + n   dT + ∑ M i dni
 ∂P  T , n  ∂T  P ,n i

 ∂M   ∂M 
ndM + Mdn = n   dP + n   dT + ∑ M i ( xi dn + ndxi )
 ∂P  T , n  ∂T  P , n i

  ∂M   ∂M    


dM −  
 ∂P T ,n
dP −  
 ∂T  P , n
dT − ∑
i
M i dx i

n + 

M − ∑
i
xi M i  dn = 0


 ∂M   ∂M  M − ∑ xi M i = 0
dM −   dP −   dT − ∑ M i dxi = 0 dan
 ∂P T ,n  ∂T  P ,n i
i

dM = ∑ xi dM i + ∑ M i dxi
i i
nM − ∑ ni M i = 0
i

 ∂M   ∂M 
 dT − ∑ xi dM i = 0
Perhitungan sifat-sifat
  dP + 
 ∂P T ,n  ∂T  P ,n i
campuran dari sifat-
sifat parsialnya
Persamaan Gibbs/Duhem
 Sifat Parsial pada Larutan Biner
• Untuk sistem biner
M = x1M 1 + x2 M 2

dM = x1dM 1 + M 1dx1 + x2 dM 2 + M 2 dx2

P and T tetap, menggunakan pers. Gibbs/Duhem
dM = M 1dx1 + M 2 dx2
x1 + x2 = 1
dM dM dM
= M1 − M 2 M 1 = M + x2 M 2 = M − x1
dx1 dx1 dx1
Constant T, P
Constant T, P
Pada suatu Lab dibutuhkan 2000 cm3 antifreeze solution (larutan antibeku)
mengandung 30 mol-% metanol dalam air. Berapa volume metanol murni dan air
murni pada 25°C harus dicampur untuk memperoleh 2000 cm3 antifreeze pada 25°C?
Volume molar parsial dan volume murni masing-masing spesies diketahui.

V = x1V1 + x2V2 V = (0.3)(38.632) + (0.7)(17.765) = 24.025 cm 3 / mol

Vt 2000 n1 = (0.3)(83.246) = 24.974 mol

n= = = 83.246 mol
V 24.025 n2 = (0.7)(83.246) = 58.272 mol

V1t = n1V1 = ( 24.974)( 40.727) = 1017 cm 3 V2t = n2V2 = (58.272)(18.068) = 1053 cm 3

Entalpi sistem cairan biner dari spesies 1 dan 2 pada T dan P tertentu adalah:
H = 400 x1 + 600 x2 + x1 x2 ( 40 x1 + 20 x2 )
Tentukan H 1 dan H 2 sbg fungsi x1, nilai numerik entalpi spesies murni H1 and H2,
∞ ∞
nilai numerik entalpi parsial pada pengenceran tak berhingga H 1 dan H 2

H = 400 x1 + 600 x2 + x1 x2 ( 40 x1 + 20 x2 )
x1 + x2 = 1
x1 + x2 = 1
H = 600 − 180 x1 − 20 x 3
1 H 1 = 420 − 60 x12 + 40 x13 H 2 = 600 + 40 x13
dH
H 1 = H + x2
dx1

x1 = 0 x1 = 1

∞ J ∞ J
H 1 = 420 H 2 = 640
mol mol
 Hubungan antar Sifat Parsial
d ( nG ) = ( nV ) dP − ( nS ) dT + ∑ Gi dni
i

• Relasi Maxwell :
 ∂V   ∂S   ∂Gi   ∂ ( nS )   ∂Gi   ∂ ( nV ) 
  = −    = −     = −  
 ∂T  P ,n  ∂P  T , n  ∂T P ,n  ∂ ni  P ,T , n j  ∂P T ,n  ∂ ni  P ,T , n j

 ∂Gi   ∂Gi 
  = − S i   = −Vi
 ∂T  P ,x  ∂P T ,x

dGi = Vi dP − S i dT

H = U + PV H i = U i + PVi
 Campuran Gas Ideal
• Teorema Gibbs’s
– Sifat molar parsial spesies (kecuali volume) dalam
camp. gas ideal SAMA DENGAN sifat molarnya sbg
gas ideal murni pada suhu campuran tetapi pada
tekanan yg sama dengan tekanan parsialnya dalam
campuran.

M iig ≠ Vi ig M (T , P ) = M (T , pi )
i
ig
i
ig
Untuk yg tidak tergantung tekanan, mis.
H (T , P ) = H (T , pi ) = H (T , P )
ig ig ig H ig = ∑ yi H iig U ig = ∑ yiU iig
i i i i i

Untuk yg tergantung tekanan, mis. dS iig = − Rd ln P const .T

P P
S iig (T , P ) − S iig (T , pi ) = − R ln = − R ln = R ln yi
pi yi P
M iig (T , P ) = M iig (T , pi )

S iig (T , P ) − S iig (T , P ) = R ln yi S ig = ∑ yi S iig − R ∑ yi ln yi

i i

H iig (T , P ) = H iig (T , P )
Gi ig = H iig − TS iig Gi ig = H iig − TS iig + RT ln yi
S iig (T , P ) − S iig (T , P ) = R ln yi
µ iig ≡ Gi ig = Giig + RT ln yi
or
G = ∑ yi Γi (T ) + RT ∑ yi ln yi P
ig
µ iig = Γi (T ) + RT ln yi P Giig = Γi (T ) + RT ln P
i i
 S ig = ∑ yi S iig − R ∑ yi ln yi
i i

1
S − ∑ yi S = − R ∑ yi ln yi = R ∑ yi ln = ∆S
ig
i
ig
>0
i i i yi

Perubahan entropi pencampuran gas ideal selalu positif ATAU

entropi campuran gas ideal lebih besar dari pada entropi spesies
murni konstituennya
 Fugasitas dan Koefisien Fugasitas
 ∂ ( nG ) 
• Potensial kimia: µi ≡  
 ∂ni  P ,T , n j

– Menyediakan kriteria dasar kesetimbangan fase

– Namun, Energi Gibbs juga µi didefinisikan
berhubungan dengan energi dalam dan entropi
(nilai absolut tidak diketahui, sulit ditentukan
nilainya dari T dan P).
• Fugasitas: Gi ≡ Γi (T ) + RT ln f i
– Suatu kunatitas yg menggantikan µi
Dengan satuan tekanan
Gi ≡ Γi (T ) + RT ln f i
Giig = Γi (T ) + RT ln P
fi
Gi − Gi = RT ln
ig fi
GiR = RT ln φi
φi =
P
P
Residual Gibbs energy Fugacity coefficient

P dP
ln φi = ∫ ( Z i − 1) (const . T )
0 P
 Kesetimbangan Uap-Cair (VLE)
untuk Spesies Murni
• Uap Jenuh: Giv = Γi (T ) + RT ln f i v

• Cairan Jenuh: Gil = Γi (T ) + RT ln f i l

fi v
G − G = RT ln l
i
v
i
l

fi
VLE
fiv
G − G = RT ln l = 0
i
v
i
l

fi

φiv = φil = φisat f i v = f i l = f i sat

For a pure species coexisting liquid and vapor phases are in equilibrium when they
have the same temperature, pressure, fugacity and fugacity coefficient.
 Fugasitas Cairan Murni
• Fugasitas spesies murni i sebagai cairan tertekan
(compressed liquid):
fi
Gi − G i
sat
= RT ln Gi − G sat
P
= ∫ sat Vi dP (isothermal process )
f i sat i
Pi

fi 1 P
ln
fi sat
=
RT ∫ Pi sat
Vi dP

Karena Vi sedikit dipengaruhi P (weak function)

fi Vi l ( P − Pi sat ) Vi l ( P − Pi sat )
ln = f i = φ Pi
sat sat
exp
f i sat RT fi sat
= φ Pi sat sat
i
RT
i
For H2O at a temperature of 300°C and for pressures up to 10,000 kPa (100 bar)
calculate values of fi and φi from data in the steam tables and plot them vs. P.

For a state at P: Gi = Γi (T ) + RT ln f i
For a low pressure reference state: Gi* = Γi (T ) + RT ln f i *

fi 1  H i − H i* * 
fi
=
1
− *
ln * =  − ( Si − Si ) ln *
(Gi Gi )
fi RT
fi R T  Gi = H i − TS i

The low pressure (say 1 kPa) at 300°C: f i * = P * = 1 kPa S * = 10.3450 J

i gK
H i* = 3076.8 J
g
For different values of P up to the saturated pressure at 300°C, one obtains the
values of fi ,and hence φi . Note, values of fi and φi at 8592.7 kPa are obtained
Vi l ( P − Pi sat )
Values of fi andφi at higher pressure: fi = φ P
i
sat sat
i exp
RT

Fig 11.3
 Fugasitas dan Koefisien Fugasitas:
spesies dalam larutan
• Untuk spesies i dalam campuran gas nyata atau dalam
larutan cair:
µ i ≡ Γi (T ) + RT ln fˆi

Fugasitas spesies i dalam larutan

(mengganti tekanan parsial yiP)
• Multi fase pada T dan P yg sama adalah dalam
kesetimbangan jika fugasitas masing-masing spesies
konstituen sama pada semua fase:
α β π
fˆi = fˆi = ... = fˆi
Sifat Residual: M R = M − M ig

Sifat residual parsial M iR = M i − M iig

Gi R = Gi − Gi ig
µ i ≡ Γi (T ) + RT ln fˆi
µ iig = Γi (T ) + RT ln yi P
fˆi
µi − µ = RT ln
ig
i
yi P

 ∂ (nG ) 
µi ≡   = Gi
 ∂ni  P ,T ,nj
Untuk gas ideal,
Gi R = 0 Gi R = RT ln φˆi ˆ fˆi
φi ≡
ˆ yi P
f
φˆi = i = 1 fˆi = yi P Koefisen fugasitas spesies i
yi P
dalam larutan
 Fundamental residual-property relation
 nG  1 nG
d  = d ( nG ) − 2
dT
 RT  RT RT
d ( nG ) = ( nV ) dP − ( nS ) dT + ∑ µ i dni
i

G = H − TS

 nG  nV nH Gi nG
d =
 RT  RT
dP −
RT 2
dT + ∑
i RT
dni
RT
= f ( P, T , ni )

G/RT as a function of its canonical variables allows evaluation of all other

thermodynamic properties, and implicitly contains complete property information.
The residual properties:

 nG R  nV R nH R Gi
R
 nG R  nV R nH R
d   = dP − 2
dT + ∑ dni or d   = dP − 2
dT + ∑ ln φˆi dni
 RT  RT RT i RT  RT  RT RT i
  nG R  nV R nH R Gi
R
 nG R  nV R nH R
d   = dP − 2
dT + ∑ dni d   = dP − 2
dT + ∑ ln φˆi dni
 RT  RT RT i RT  RT  RT RT i

Fix T and composition: V R  ∂ (G R / RT ) 

=  
RT  ∂P T , x

Fix P and composition: HR  ∂ (G R / RT ) 

= −T  
RT  ∂T  P,x

Fix T and P:  ∂ ( nG R / RT ) 
ln φi = 
ˆ 
 ∂ni  P ,T ,n j
Develop a general equation for calculation of ln φˆi values form compressibility-
factor data.

 ∂ ( nG R / RT ) 
ln φi = 
ˆ 
 ∂ni  P ,T ,n j

nG R P dP
= ∫ ( nZ − n)
RT 0 P

P  ∂ ( nZ − n )  dP
ln φi = ∫ 
ˆ

0
 ∂ni  P ,T , n j P

∂n ∂ ( nZ )
=1 = Zi
∂ni ∂ni
P dP
ln φi = ∫ ( Z i − 1)
ˆ
0 P Integration at constant temperature and composition
 Fugacity coefficient from the virial
E.O.S
• The virial equation: BP
Z = 1+
RT
B = ∑∑ yi y j Bij
– the mixture second virial coefficient B: i j

– for a binary mixture: B = y1 y1 B11 + y1 y2 B12 + y2 y1 B21 + y2 y2 B22

• n mol of gas mixture: nBP
nZ = n +
RT
 ∂ ( nZ )  P  ∂ ( nB ) 
Z1 =   = 1+  
 ∂ n1  P ,T , n2 RT  ∂ n1  T , n2

1 P  ∂ ( nB )  P  ∂ ( nB ) 
ln φˆ1 = ∫   dP =  
RT 0
 ∂ n1  T , n2 RT  ∂ n1  T , n2
 1 P  ∂ ( nB )  P  ∂ ( nB ) 
ln φˆ1 = ∫   dP =  
RT 0
 ∂ n1  T , n2 RT  ∂ n1  T , n2

B = y1 y1 B11 + y1 y 2 B12 + y2 y1 B21 + y 2 y2 B22

δ 12 ≡ 2 B12 − B11 − B22 yi = ni / n

ln φˆ1 =
P
RT
(
B11 + y22δ12 ) Similarly: ln φˆ
2 =
P
RT
B22 + y(
1 δ 12
2
)
For multicomponent gas mixture, the general form:
P  1 
ln φk =
ˆ 
 Bkk + ∑∑ yi y j ( 2δ ik − δ ij ) 
RT  2 i j 

where δ ≡ 2 B − B − B
ik ik ii kk
Determine the fugacity coefficients for nitrogen and methane in N2(1)/CH4(2) mixture
at 200K and 30 bar if the mixture contains 40 mol-% N2.

3
δ12 ≡ 2 B12 − B11 − B22 = 2( −59.8) + 35.2 + 105.0 = 20.6 cm mol

ln φˆ1 =
P
RT
( )
B11 + y 22δ12 =
30
(83.14)(200)
[ ]
− 35.2 + (0.6) 2 ( 20.6) = −0.0501

φˆ1 = 0.9511

ln φˆ2 =
P
RT
( )
B22 + y12δ12 =
30
(83.14)(200)
[ ]
− 105.0 + (0.4) 2 (20.6) = −0.1835

φˆ2 = 0.8324
 Generalized correlations for the
fugacity coefficient
Pr 0
Z −1 = ( B + ωB 1 )
Pr dPr Tr Pr 0
ln φi = ∫ ( Z i − 1) (const . Tr ) ln φ = ( B + ωB1 )
0 Pr Tr

Z = Z 0 + ωZ 1
Pr dP Pr dP
φ = PHIB (TR , PR , OMEGA )
ln φ = ∫ ( Z 0 − 1) r + ω ∫ Z 1 r (const . Tr ) For pure gas
0 Pr 0 Pr
or
ln φ = ln φ 0 + ω ln φ 1 with
Pr dPr Pr dP
ln φ ≡ ∫
0
( Z − 1)
0
ln φ ≡ ∫ Z 1 r For pure gas
1
0 Pr 0 Pr

Table E1:E4 or Table E13:E16

Estimate a value for the fugacity of 1-butene vapor at 200°C and 70 bar.

Tr = 1.127

Pr = 1.731 φ 0 = 0.627 and φ 1 = 1.096

ω = 0.191 Table E15 and E16

ln φ = ln φ 0 + ω ln φ 1 φ = 0.638 f = φP = (0.638)(70) = 44.7 bar

For gas mixture:

P  1 
ln φk =
ˆ 
 Bkk + ∑∑ yi y j ( 2δ ik − δ ij ) 
RT  2 i j 
Empirical interaction parameter
RTcij ωi + ω j
Bij = ( B 0 + ωij B1 ) ωij =
Pcij 2 Tcij = (TciTcj ) (1 − kij )
Z cij RTcij Z ci + Z cj  Vci1/ 3 + Vcj1/ 3 
3
Prausnitz et al. 1986 Pcij = Z cij = Vcij =  
Vcij 2  2 
 
Estimate φˆ1 and φˆ2 for an equimolar mixture of methyl ethyl ketone (1) /
toluene (2) at 50°C and 25 kPa. Set all kij = 0.

ωi + ω j Z ci + Z cj Z cij RTcij  1/ 3
+
3
1/ 3

ωij = Z cij = Pcij = Vcij = 
Vci Vcj

2 2 Vcij  2 
 
RTcij Tcij = (TciTcj ) (1 − kij ) δ 12 ≡ 2 B12 − B11 − B22
Bij = ( B 0 + ωij B1 )
Pcij

ln φˆ1 =
P
RT
( )
B11 + y 22δ12 = −0.0128 φˆ1 = 0.987

ln φˆ2 =
P
RT
(
B22 + y12δ12 = −0.0172) φˆ2 = 0.983
 The ideal solution
• Serves as a standard to be compared:
M id = ∑ xi M iid
Gi = Gi + RT ln xi
id
i
G id = ∑ xi Gi + RT ∑ xi ln xi
i i

cf. Gi = Gi + RT ln yi
ig ig

 ∂Gi id   ∂G  id
= ∑ xi S i − R ∑ xi ln xi
S id
= −  = − i  − R ln xi S id
= S i − R ln xi S
 ∂T  ∂T
i i
 P,x P i i

 ∂Gi id   ∂G  id
= ∑ xiVi
Vi id = −  = − i  Vi id
= Vi V
 ∂P T , x  ∂P T i

H id
= Gi + TS
id id
= Gi + RT ln xi + TS i − RT ln xi H id
= Hi H id
= ∑ xi H i
i i i
i
 The Lewis/Randall Rule
• For a special case of species i in an ideal solution:
µ i ≡ Γi (T ) + RT ln fˆi µ iid = Gi id = Γi (T ) + RT ln fˆi id

Gi id = Gi + RT ln xi
Gi ≡ Γi (T ) + RT ln f i

The Lewis/Randall rule fˆi id = xi f i

φˆiid = φi
The fugacity coefficient of species i in an ideal solution is
equal to the fugacity coefficient of pure species i in the same
physical state as the solution and at the same T and P.
 Excess properties
• The mathematical formalism of excess properties
is analogous to that of the residual properties:
M E ≡ M − M id
– where M represents the molar (or unit-mass) value of
any extensive thermodynamic property (e.g., V, U, H, S,
G, etc.)
– Similarly, we have:
 nG E  nV E nH E Gi
E
d   = dP − 2
dT + ∑ dni
 RT  RT RT i RT

The fundamental excess-property relation

(1) If CEP is a constant, independent of T, find expression for GE, SE, and HE as
functions of T. (2) From the equations developed in part (1), fine values for GE , SE,
and HE for an equilmolar solution of benzene(1) / n-hexane(2) at 323.15K, given the
following excess-property values for equilmolar solution at 298.15K:
CEP =-2.86 J/mol-K, HE = 897.9 J/mol, and GE = 384.5 J/mol
 ∂ 2G E   ∂ 2G E  a
From Table 11.1: C = −T E
   = −
∂ ∂
P 2 2
 T  P , x C PE = a = const .  T  P,x T
integration
 ∂G E   ∂G E 
From Table 11.1: S = − E
   = − a ln T + b
 ∂T  P,x  ∂T  P,x
integration integration
S E = a ln T − b G E = − a (T ln T − T ) + bT + c

H E = G E + TS E = aT + c

C PE = a = −2.86 We have values of a, b, c

897.9 = a ( 298.15) + c and hence the excess-
384.5 = − a (( 298.15) ln( 298.15) − ( 298.15) + b(198.15) + c properties at 323.15K
The excess Gibbs energy and the
activity coefficient
• The excess Gibbs energy is of particular interest:
G E ≡ G − G id
Gi = Γi (T ) + RT ln fˆi
Gi id = Γi (T ) + RT ln xi f i

fˆi
Gi = RT ln
E

xi f i
fˆi The activity coefficient of species i in solution.
γi ≡ A factor introduced into Raoult’s law to
xi f i
account for liquid-phase non-idealities.
Gi E = RT ln γ i For ideal solution, G E = 0, γ = 1
i i

c.f. Gi R = RT ln φˆi
  nG E  nV E nH E Gi
E
d   = dP − 2
dT + ∑ dni
 RT  RT RT i RT

 nG E  nV E nH E
d   = dP − 2
dT + ∑ ln γ i dni
 RT  RT RT i

V E  ∂ (G E / RT ) 
=  
RT  ∂P T , x
Experimental accessible values:
H E
 ∂ (G / RT ) 
E
= −T   activity coefficients from VLE data,
RT  ∂T  P, x VE and HE values come from mixing experiments.
 ∂ ( nG E / RT ) 
ln γ i =  
 ∂ni  P ,T ,n j

GE
= ∑ xi ln γ i
RT i Important application in phase-equilibrium
∑ x d ln γ
i
i i = 0 (const . T , P ) thermodynamics.
 The nature of excess properties
• GE: through reduction of VLE data
• HE: from mixing experiment
• SE = (HE - GE) / T

• Fig 11.4

– excess properties become zero as either species ~ 1.

– GE is approximately parabolic in shape; HE and TSE exhibit
individual composition dependence.
– The extreme value of ME often occurs near the equilmolar
composition.