SHR Chapter 2

Chemical Engineering
Thermodynamics
A Brief Review

1 Thermo.key - February 7, 2014

 “Rate” vs. “State”
Thermodynamics tells us how things “end up” (state) but not how (or how
fast) they “get there” (rate)

Limitations on getting to equilibrium:

• Transport (mixing): diffusion, convection

‣ example: why doesn’t more of the ocean evaporate to make higher humidity in the deserts? (heat transfer
alters dew point locally, atmospheric mixing limitations, etc.)

• Kinetics (reaction): the rate at which reactions occur are too slow to get to equilibrium

‣ example: chemical equilibrium says trees (and our bodies) should become CO2 and H2O (react with air)

‣ example: chemical equilibrium says diamonds should be graphite (or CO2 if in air)

Sometimes, mixing & reaction are sufficiently fast that equilibrium
assumptions are “good enough.”

• if we assume that we can use thermodynamics to obtain the state of the system, we avoid a lot
of complexity.

‣ do it if it is “good enough!”

• Most unit operations (e.g. distillation) assume phase equilibrium, ignoring transport limitations.

‣ good enough if things are mixed well and have reasonable residence/contact times.

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 Some Terminology...
◆ ✓
@N M ℳ      -
arbitrary thermodynamic
“Partial Molar” property M̄i ⌘ property (per mole)

C
X
@Ni T,P,Nj M= yi M̄i
change in ℳ due to adding a differential amount Ni
-
moles of species i
i=1
of species i. For ideal mixtures, M̄i = Mi yi
-
mole fraction of species i
(liquid or gas)
✓ ◆ ✓ ◆ C
X C
X
Gibbs-Duhem @M @M
dP + yi dM̄i = 0 Note at constant T and P, yi dM̄i = 0
Equation: @P T,y @T P,y i=1 i=1

C
X
“Residual” property M ⌘ M R
M ig
M ig
= yi Mig
i
how much ℳ deviates from i=1

the ideal gas (ℳig ) behavior.

C
X
“Excess” property M ⌘ M E
M ideal M ideal
= yi M i
i=1
how much ℳ deviates from
the ideal solution behavior.

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 SHR §2.2

Phase Equilibrium
C ✓
X ◆
Gibbs Energy Phase Equilibrium dG = S dT + V dP +
@G
dNi
(thermodynamic property) is achieved when i=1
@Ni P,T,Nj
G = G(T, P, N1 , N2 , . . . , NC ) G is minimized. ✓ ◆
Chemical Potential
@G
(thermodynamic property, µi ⌘
partial molar Gibbs energy) @Ni P,T,Nj
N
X
Gsystem = G(p) N
" C
#
For multiple In phase equilibrium,
X X
p=1 (p) (p)
phases in a T(1) = T(2) = ⋯ = T(N)
dGsystem = µi dNi
closed system, N
X
dGsystem = dG(p) P(1) = P(2) = ⋯ = P(N) p=1 i=1 T,P
p=1

" C #
For a nonreacting N
X N
X N
X X⇣ (p) (1)
⌘
(p)
(p) (1) (p)
system, moles dNi =0 dNi = dNi dGsystem = µi µi dNi
are conserved. p=1 p=2 p=2 i=1 T,P

To minimize G, dG=0. But each For phase equilibrium, the

(p) (1) (2) (N )
term in the summation for dG is µi = µi = µi = ··· = µi chemical potential of any
independent, so each must be zero. species is equal in all phases.

Problem: Solution: Partial Fugacity

⇣µ ⌘ For phase equilibrium, the fugacity
µi ! 1 ¯
fi = C exp
i of any species is equal in all phases.
as P ! 0 RT (p) (1) (2) (N )
C is a temperature- f¯i = f¯i = f¯i = · · · = f¯i
dependent constant.

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 SHR §2.2.1 & Table 2.2

Chemical Potential, Fugacity, Activity

Thermodynamic Quantity Definition Description Limiting case of ideal
gas and ideal solution
⇣ ⌘
∂G
Chemical potential µi ⌘ ∂Ni Partial molar free energy, gi µi = gi
T,P,Nj
Partial fugacity f i = C exp (µi/( RT )) Thermodynamic pressure f iV = yi P
Fugacity coefficient of a fi ⌘ f i/P Deviation of fugacity due to fiV = 1.0
pure species f¯i = fi for a pure species pressure fiL = Pis/P
Fugacity coefficient of a fiV ⌘ f iV/(yi P) Deviations to fugacity due fiV = 1.0
species in a mixture fiL ⌘ f iL/( xi P) to pressure and composition fiL = Pis/P
Activity ai ⌘ f i/ f io Relative thermodynamic aiV = yi
pressure aiL = xi
Activity coefficient giV ⌘ aiV/yi Deviation of fugacity due to giV = 1.0
giL ⌘ aiL/xi composition. giL = 1.0

Pis vapor pressure of species i.

For phase equilibrium, the chemical potential, fugacity,
activity (but not activity coefficient or fugacity yi vapor mole fraction of species i.
coefficient) of any species is equal in all phases.
xi liquid mole fraction of species i.

f¯iL = ¯iL xi P f¯iV = ¯iV yi P ¯ ¯ yi ¯iL we will use this on

o o
fiL = fiV ) = ¯ the next slide...
= iL xi fiL = iV yi fiV xi iV

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 SHR §2.2.2 & Table 2.3

Phase Equilibrium - K-Values

Note: liquid-liquid case equivalent
Phase equilibrium ratio:
yi Relative ↵ ⌘ Ki =
yi/xi
is the “relative selectivity” βij.
How much species i is Ki ⌘ volatility:
ij
Kj yj/xj K Di
enriched in the vapor xi ij ⌘
K Dj
Note: liquid-liquid
(1) αij = 0 αij = 1 αij = ∞
case equivalent is the KDi ⌘ xi /x(2)
“partition coefficient”
i
easy impossible easy
yi ¯iL
Solve for yi/xi from Ki ⌘ = ¯
xi Concept: determine Ki from
the previous slide: iV
o
iL fiL iL iL thermodynamic models.

= = This gives us yi/xi.
iV P iV

Equation Application

Mix & match for different

Rigorous forms

species in a mixture
Equation of state Ki = f̄iL/f̄iV Benedict-Webb-Rubin-Starling, SRK, PR
equations of state, Hydrocarbon and light gas
SHR Table 2.3

mixtures from cryogenic to critical

Activity coefficient Ki = giL fiL/f̄iV All mixtures from ambient to near critical.
Approximate forms
Raoult’s law (ideal) Ki = Pis/P Ideal solutions at low pressures
Modified Raoult’s law K = giL Pis
/P Nonideal liquid solutions near ambient pressure
⇣is⌘ ⇣ ⌘R
s Pi 1 P
Poynting correction Ki = giL fiV P exp RT Pis viL dP Nonideal liquid solutions at moderate pressures
and below Tc
Hi
Henry’s law Ki = P Low to moderate pressures for species above Tc

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 Example: Raoult’s Law (Ideal Mixtures)
Pis
Raoult’s law: Ki = Need: Pis - saturation pressure for each species
P B
Antoine equation: log10 Pis = A
C +T

Derivation of Raoult’s Law: SHR Figure 2.3: Pis for a few species
partial pressure is the
pi = xi Pis weighted saturation pressure
(ideal liquid mixture)
Dalton’s law

pi = y i P (ideal mixture of gases)
Atmospheric Pressure
combine yi Pis
to find = = Ki
xi P

Pis
Modified Raoult’s law: Ki = i
P For Raoult’s law, Ki is independent of composition,
but varies exponentially with temperature!

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 Liquid-Phase Activity Coefficients

Wilson 2-parameter
0 model1for mixtures: ⇤ij =
vjL
exp
( ij ii )
C C
! viL RT
X X xi ⇤ik
ln k =1 ln @ xj ⇤kj A PC ij = ji ⇤ij 6= ⇤ji
j=1 i=1 j=1 xj ⇤ij
ii = jj ⇤ii = 1
For a binary system: ✓ ◆
⇤12 ⇤21 • λij are functions of temperature
ln 1 = ln (x1 + x2 ⇤12 ) + x2 but not composition

x1 + x2 ⇤12 x2 + x1 ⇤21
✓ ◆ • Λij = Λij = 1 implies ideal
⇤12 ⇤21 solution (γi = γj = 1)
ln 2 = ln (x2 + x1 ⇤21 ) x1 +
x1 + x2 ⇤12 x2 + x1 ⇤21

Parameters λij or Λij are typically determined

from experimental data via regression.

Alternatively, if we can obtain γ at infinite dilution,

1
ln 1 =1 ln ⇤12 ⇤21 2 equations,
1 2 unknowns
ln 2 =1 ln ⇤21 ⇤12
Less accurate than regression.

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 SHR Figure 2.4

Example: Graphical Methods

NOTE: this can also be used to estimate
1. Locate appropriate species /mixture

the bubble point for a pure fluid. (how?)
2. Locate appropriate T and P.

3. Draw a straight line between the two
points to determine Ki.

Example: at T=60 F and P=1 atm,

• Kpropane = 7

• Kisopentane = 0.64

9 Thermo.key - February 7, 2014

 DePriester Chart

Empirical Correlation:
a1 a2 b2 b3
ln K = + + a 3 + b 1 ln p + +
T2 T p2 p
NOTE: T in °R and p in psia!
Compound a a a b b b
Methane -292,860 0 8.2445 -0.8951 59.8465 0
Ethylene -600,076.875 0 7.90595 -0.84677 42.94594 0
Ethane -687,248.25 0 7.90694 -0.886 49.02654 0
Propylene -923,484.6875 0 7.71725 -0.87871 47.67624 0
Propane -970,688.5625 0 7.15059 -0.76984 0 6.90224
Isobutane -1,166,846 0 7.72668 -0.92213 0 0
n-Butane -1,280,557 0 7.94986 -0.96455 0 0
Isopentane -1,481,583 0 7.58071 -0.93159 0 0
n-Pentane -1,524,891 0 7.33129 -0.89143 0 0
n-Hexane -1,778,901 0 6.96783 -0.84634 0 0
M. L. McWilliams, Chemical Engineering, 80(25), 1973 p. 138.

Chemical Engineering Progress

(AIChE),Vol. 74(4), pp. 85-86

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 SHR §2.5.2

Thermo from Equations of State

" Z P✓ ◆ #
fugacity V = exp
1
v
RT
dP For Redlich-Kwong (and S-R-K) EOS:
coefficient RT 0 P
 Z 1✓ ◆ Z3 Z2 + A B B2 Z AB = 0
1 RT
= exp P dv ln Z + Z 1 RT a aP bP
vapor
RT v v P = A= B=
v b v 2 + bv R2 T 2 RT
( Z "✓ ◆ # ) 2 3
1
partial fugacity ¯ = exp 1 @P RT
dV ln Z
C
X C
X p
C
X
coefficient
iV
RT @Ni V mixing rules: a= 4 y i yj a i a j 5 b = y i bi
V T,V,Nj
i=1 j=1 i=1
C
X  ✓ ◆
C
X 3A B
h= (yi hoi ) + RT Z 1 ln 1 +
V =v Ni volume i=1
2B Z
i=1  ✓ ◆
A B
= exp Z 1 ln (Z B) ln 1 +
B Z
" ! ◆#
yi ¯iL r ✓
¯i = exp (Z 1) Bi ln (Z B) A 2 Ai Bi B
Ki ⌘ = ¯ B B A B
ln 1 +
Z
xi iV
Note that these can be used in vapor or liquid phases, by
using appropriate values for Z, and using appropriate phase
mole fractions (yi for vapor, xi for liquid)

(because cubic EOS can approximate two-phase behavior.)

R-K: S-R-K (much better):

RTi,c RTi,c
bi = 0.08664 bi = 0.08664
Pi,c Pi,c
⇥ ⇤2
R2 Ti,c
2.5
R2 Ti,c
2
1 + f! 1 0.5
Ti,r
ai = 0.42748 ai = 0.42748
Pi,c T 0.5 Pi,c
f! = 0.48 + 1.574! 0.176! 2 ω - acentric factor

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 Example: K-Values from SRK
Given a mixture of propane
Z3 Z2 + A B B2 Z AB = 0
(x=0.0166, y=0.3656) and " r ! ✓ ◆#
benzene (x=0.9834, y=0.6344) ¯i = exp (Z Bi A Ai Bi B
1) ln (Z B) 2 ln 1 +
at 300 K & 1 atm, find the K- B B A B Z
yi ¯iL
value using SRK. Ki ⌘ = ¯
Redlich-Kwong (&SRK) parameters xi iV

Propane Benzene
T 369.8 562.2
P 4250 4890
1. Calculate ai, bi and then Ai, Bi (tedious, but not difficult).

ω 0.149 0.209
2. Calculate A and B using mixing rules.

3. Calculate Z in the vapor and liquid phases. This requires
Requires xi, yi.

us to solve the cubic equation and pick the appropriate
This is a problem since
roots.

we typically need Ki to
determine this ratio! 4. Calculate partial fugacity coefficient in vapor and liquid.

5. Calculate Ki.
This is typically used within
another solver to determine
xi, yi (more soon).

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 SHR §2.8

Heuristics for Property Model Selection

Aqueous
Solutions

Hydrocarbons
with or without Polar Compounds
electrolytes and no
light gases
polar compounds?

Yes No
Wide boiling with light gases?
range?
NRTL Special
Yes No Yes No

liquid phase
Corresponding separation?
SRK
States
(non cryogenic
T, all P) No Yes

BWRS PSRK UNIFAC

PR NRTL
(all T, sub- (see SHR Wilson
(all T, P) UNIQUAC
critical P) §2.7.1) NRTL

See also http://www.che.utah.edu/~sutherland/PropertySelection.pdf for a

much more extensive property selection flowchart from Professor Ring.
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