Residual Functions

D.F. Mendoza

Universidad de Antioquia

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 Introduction

Residual function

A residual function, F R , is the difference between the property of interest

in its real state (at T , p, v) and in an ideal-gas state at the same
temperatute T and pressure p.

F R = F(T, p) − F ig (T, p)

where F corresponds to u, h, s, g, a and v. From this definition it is

possible to change from p to v as independent variable

F R = F(T, v) − F ig (T, v ig )

in this case both the volume of the real substance v and the ideal gas
volume v ig are calculated at T and p. i.e., v = v(T, p) and v ig = RT /p.

D.F. Mendoza (Universidad de Antioquia) Residual Functions 2 / 38

 Introduction

Residual functions using T and p as independent variables

A convenient way to calculate a residual function is
p ∂F ∂F ig
FR = ∫ [( ) −( ) ] dp
0 ∂p T ∂p T

this expression is valid since at p = 0 all substances behave as an ideal gas, thus,
F R = 0 at p = 0.
RT
v R = v(T, p) − v ig (T, p) = v(T, p) −
p
p ∂v
hR = h(T, p) − hig (T, p) = ∫ [v − T ( ) ] dp
0 ∂T p
∂v R p
sR = s(T, p) − sig (T, p) = − ∫ ) − ] dp [(
0 ∂T p p
p RT
g R = g(T, p) − g ig (T, p) = ∫ (v − ) dp
0 p

D.F. Mendoza (Universidad de Antioquia) Residual Functions 3 / 38

 Introduction

from these equations we can calculate, uR and aR as:

uR = hR − pv R
aR = g R − pv R

Note that...
Calculating departure functions using T and p as independent variables is
convenient if we use v explicit equations of state.

D.F. Mendoza (Universidad de Antioquia) Residual Functions 4 / 38

 Introduction

Residual functions using T and v as independent variables

A convenient way to calculate a residual function is

∂F ig
v v ig
∂F
F =∫
R
( ) dv − ∫ ( ) dv
∞ ∂v T ∞ ∂v T

Note that in general v(T, p) ≠ v ig (T, p).

We can rewrite F R as
∂F ig ∂F ig
v v ig
∂F
FR = ∫ [( ) −( ) ] dv − ∫ ( ) dv
∞ ∂v T ∂v T v ∂v T

this expression is more convenient from a mathematical point of view since

F R = 0 at v = ∞ .

D.F. Mendoza (Universidad de Antioquia) Residual Functions 5 / 38

 Introduction

The residual functions using T and v as independent variables are:

v
∂p
uR = u(T, v) − uig (T, v ig ) = ∫ ) − p] dv
[T (
∞ ∂T v
v ∂p R v ig
sR = s(T, v) − sig (T, v ig ) = ∫ [( ) − ] dv − R ln ( )
∞ ∂T v v v
v RT v ig
aR = a(T, v) − aig (T, v ig ) = − ∫ [p − ] dv + RT ln ( )
∞ v v

from these equations we obtain hR and hR as

hR = uR + pv R
g R = aR + pv R

Note that...
Calculating residual functions using T and v as independent variables is
convenient if we use p explicit equations of state.

D.F. Mendoza (Universidad de Antioquia) Residual Functions 6 / 38

 Generalized residual functions

Residual functions using compressibility factor

We can compute residual functions from using the compessibility factor:

pv = zRT

this equation allows us to use T and p as independent variables, because it

can be transformed into a v explicit equation
zRT
v=
p
∂v zR RT ∂z
( ) = + ( )
∂T p p p ∂T p
∂v zRT RT 2 ∂z
T( ) = + ( )
∂T p p p ∂T p

D.F. Mendoza (Universidad de Antioquia) Residual Functions 7 / 38

 Generalized residual functions

residual functions using compressibility factor are:

RT
vR = (z − 1)
p
p ∂z dp
hR = −RT 2 ∫ ( )
0 ∂T p p
p ∂z dp
sR = −R ∫ [(z − 1) + T ( ) ]
0 ∂T p p
p dp
g R = RT ∫ (z − 1)
0 p

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 Generalized residual functions

Residual functions from corresponding states principle

We can obtain generalized residual functions using reduced variables, to this end
we write T = Tc Tr and p = pc pr in the residual functions and form dimensionless
groups:

pc v R Tr
= (z − 1)
RTc pr
hR pr ∂z dpr
= −Tr2 ∫ ( )
RTc 0 ∂Tr pr pr
sR pr ∂z dpr
= −∫ [(z − 1) + Tr ( ) ]
R 0 ∂Tr pr pr
gR pr dpr
= Tr ∫ (z − 1)
RTc 0 pr
Corresponding states principle applied to residual functions: The
dimensionless residual functions (left-hand-side of the equations) are the same for
all substances at the same: Tr , pr and zc or ω.

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 Generalized residual functions

Lydersen’s approach (Tr , pr and zc )

Enthalpy departure (zc = 0.27). Hougen, Watson, Ragatz. Chemical process principles, part. II, Wiley, 1959.
D.F. Mendoza (Universidad de Antioquia) Residual Functions 10 / 38
 Generalized residual functions

Lydersen’s approach (Tr , pr and zc )

Entropy departure (zc = 0.27). Hougen, Watson, Ragatz. Chemical process principles, part. II, Wiley, 1959.
D.F. Mendoza (Universidad de Antioquia) Residual Functions 11 / 38
 Generalized residual functions

Lee-Kesler’s approach (Tr , pr and ω)

(0) (1)
h − hig h − hig h − hig
=( ) +ω( )
RTc RTc RTc
(0) (1)
s − sig s − sig s − sig
=( ) +ω( )
R R R

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 Generalized residual functions

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 Generalized residual functions

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 Generalized residual functions

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 Generalized residual functions

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 Generalized residual functions

Example
Use the generalized departure charts to estimate hR and sR
• Propane (Tc = 369.85 K, pc = 42.47 bar, zc = 0.276, ω = 0.153) at:
• 8.5 MPa and 296.0 K
• Ethylene (Tc = 282.4 K, pc = 51.2 bar, zc = 0.276, ω = 0.0866) at:
• 10.45 MPa and 313.0 K
• 1.135 MPa, x = 0.3

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 Generalized residual functions

Residual functions using Virial EoS

The virial EoS truntated in the second coefficient is:
Bp
z =1+
RT
where:
RTc 0 0.422 0.172
B= (B + ωB 1 ); B 0 = 0.083 − ; B 1 = 0.139 −
pc T r1.6 T r4.2
The derivative of the compressibility factor with respect to temperature.
keeping pressure constant is:
∂z p dB pB
( ) = ( )−
∂T p RT dT RT 2
where
dB R 0.6752 0.7224
= [ 2.6 + ω 5.2 ]
dT pc Tr Tr
D.F. Mendoza (Universidad de Antioquia) Residual Functions 18 / 38
 Generalized residual functions

Replacing z and its temperature derivative, given by the virial EoS, in the
residual property definition we get:
RT
vR = (z − 1) = B
p
p ∂z dp dB
hR = −RT 2 ∫ ( ) = [B − T ( )] p
0 ∂T p p dT
p ∂z dp dB
sR = −R ∫ [(z − 1) + T ( ) ] = −p ( )
0 ∂T p p dT
p dp
g R = RT ∫ (z − 1) = Bp
0 p

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 Generalized residual functions

Summary of residual functions using B-trunctated Virial EoS

vR = B
dB
hR = [B − T ( )] p
dT
dB
sR = −p ( )
dT
g R = Bp
uR = hR − pv R
aR = g R − T sR

Note that . . . Virial EoS describes gas phase only, thus these formulas
can be applied to gas phase exclusively.

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 Generalized residual functions

Example
Use B-truncated virial EoS to estimate: uR , hR , sR , aR , and g R for
propane at 8.5 MPa and 296.0 K. (Tc = 369.85 K, pc = 42.47 bar,
zc = 0.276, ω = 0.153)

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 Generalized residual functions

Residual properties using cubic EoS (gas and liquid)

The general form of a CEoS is:

RT a(T )
p= −
v − b (v + δ1 b)(v + δ2 b)

where:
R2 Tc2 RTc
a(T ) = a(Tc )f (T ); a(Tc ) = Ωa ( ); b = Ωb ( )
pc pc
√ 2
f (T ) = [1 + m(1 − Tr )]

EoS δ1 δ2 Ωa Ωb m
SRK 1√ 0√ 0.42748 0.08664 0.48 + 1.574 ω − 0.176ω 2
PR 1+ 2 1- 2 0.45724 0.0778 0.37464 + 1.54226 ω − 0.26992ω 2

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 Generalized residual functions

The derivatives of interest are:

∂p R a′ (T )
( ) = −
∂T v v−b (v + δ1 b)(v + δ2 b)
∂p RT 2v + (δ1 + δ2 )b
( ) =− + a(T )
∂v T (v − b)2 [(v + δ1 b)(v + δ2 b)]2
∂v (∂p/∂T )v
( ) =−
∂T p (∂p/∂v)T

where, √
T a′ (T ) = −m a(Tc )a(T )Tr

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 Generalized residual functions

Residual internal energy

The residual internal energy using T and v as independent variables is:
v ∂p
uR = u(T, v) − uig (T, v ig ) = ∫ [T ( ) − p] dv
∞ ∂T v
replacing the derivative given by the CEoS
v a(T ) − T a′ (T )
uR = u(T, v) − uig (T, v ig ) = ∫ dv
∞ (v + δ1 b)(v + δ2 b)

integrating
v
a(T ) − T a′ (T ) δ1 b + v
uR = ln ( )∣
(δ2 − δ1 )b δ2 b + v ∞
a(T ) − T a′ (T ) δ1 b + v
uR = ln ( )
(δ2 − δ1 )b δ2 b + v

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 Generalized residual functions

Residual entropy
The residual entropy using T and v as independent variables is:
v ∂p R v ig
sR = s(T, v) − sig (T, v ig ) = ∫ [( ) − ] dv − R ln ( )
∞ ∂T v v v

replacing the derivative given by the CEoS

v R a′ (T ) R v ig
sR = ∫ [ − − ] dv − R ln ( )
∞ v − b (v + δ1 b)(v + δ2 b) v v

integrating
v
v−b a′ (T ) δ1 b + v v ig
sR = R ln ( )− ln ( )∣ − R ln ( )
v (δ2 − δ1 )b δ2 b + v ∞ v
v−b a′ (T ) δ1 b + v
sR = R ln ( )− ln ( ) + R ln(z)
v (δ2 − δ1 )b δ2 b + v

where z = v/v ig = pv/RT .

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 Generalized residual functions

Residual Helmholtz energy

The residual Helmholtz energy using T and v as independent variables is:
v RT v ig
aR = a(T, v) − aig (T, v ig ) = − ∫ [p − ] dv + RT ln ( )
∞ v v

using p given by the CEoS

v RT a(T ) RT v ig
aR = − ∫ [ − − ] dv + RT ln ( )
∞ v − b (v + δ1 b)(v + δ2 b) v v

integrating
v
v a(T ) δ1 b + v v ig
aR = RT ln ( )+ ln ( )∣ + RT ln ( )
v−b (δ2 − δ1 )b δ2 b + v ∞ v
v a(T ) δ1 b + v
aR = RT ln ( )+ ln ( ) − RT ln(z)
v−b (δ2 − δ1 )b δ2 b + v

where z = v/v ig = pv/RT .

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 Generalized residual functions

from uR , sR and aR we calculate hR and g R as:

hR = uR + pv R
g R = aR + pv R

where v R is calculated using v(T, p) or z(T, p) obtained from the cubic

EoS
RT RT
vR = v − = (z − 1)
p p

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 Generalized residual functions

Summary of residual functions using CEoS

a(T ) − T a′ (T ) δ1 b + v
uR = ln ( )
(δ2 − δ1 )b δ2 b + v
v−b a′ (T ) δ1 b + v
sR = R ln ( )− ln ( ) + R ln(z)
v (δ2 − δ1 )b δ2 b + v
v a(T ) δ1 b + v
aR = RT ln ( )+ ln ( ) − RT ln(z)
v−b (δ2 − δ1 )b δ2 b + v
RT RT
vR = v − = (z − 1)
p p
hR = uR + pv R
g R = aR + pv R

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 Generalized residual functions

Example
Use SRK EoS to estimate: uR , hR , sR , aR , and g R of ethylene at 1.135
MPa and x =0.3. (Tc = 282.4 K, pc = 51.2 bar, zc = 0.276, ω = 0.0866)

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 Generalized residual functions

Change in thermodynamic functions using residual

functions

The value of a property F at T and p can be computed using the residual

function
F(T, p) = F ig (T, p) + F R (T, p)
The change in of a state property, using residual properties is

F(T2 , p2 ) − F(T1 , p1 ) =
F ig (T2 , p2 ) − F ig (T1 , p1 ) + F R (T2 , p2 ) − F R (T1 , p1 )

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 Generalized residual functions

Residual enthalpy

The enthalpy at T and p using residual property is

h(T, p) = hig (T, p) + hR (T, p)

The change in enthalpy is

h(T2 , p2 ) − h(T1 , p1 ) =
hig (T2 , p2 ) − hig (T1 , p1 ) + hR (T2 , p2 ) − hR (T1 , p1 )

in terms of heat capacity

T2
h(T2 , p2 ) − h(T1 , p1 ) = ∫ p dT + h (T2 , p2 ) − h (T1 , p1 )
cig R R
T1

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 Generalized residual functions

Residual entropy
The entropy at T and p using residual property is

s(T, p) = sig (T, p) + sR (T, p)

The change in entropy is

s(T2 , p2 ) − s(T1 , p1 ) =
sig (T2 , p2 ) − sig (T1 , p1 ) + sR (T2 , p2 ) − sR (T1 , p1 )

in terms of heat capacity and pressure

s(T2 , p2 ) − s(T1 , p1 ) =
T2 cig
p p2
∫ dT − R ln ( ) + sR (T2 , p2 ) − sR (T1 , p1 )
T1 T p1

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 Generalized residual functions

Example
Calculate the work and entropy change when 1 kmol/h of propane at 8.5
MPa and 296 K is expanded in a turbine to a discharge pressure of 2 MPa
and 222 K. Using residual properties obtained from
1 Generalized charts
2 Virial equation of state
3 SRK equation of state
Compare the outcome of each method with the solution obtained using
the propane tables.

D.F. Mendoza (Universidad de Antioquia) Residual Functions 33 / 38

 Generalized residual functions

Example
Calculate the vapor fraction obtained by the expansion of R134a from
313.15 K and 10 bar to 4 bar using:
1 Generalized charts
2 Virial EoS to describe the vapor phase and incompressible fluid model
to describe the liquid phase.
3 SRK EoS to describe vapor and liquid phases.
Compare the outcome of each method with the solution obtained using
tables.

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 Generalized residual functions

Thermodynamic tables using residual functions

Reference state
Ideal gas at T ref , pref . At this condition we set:
• href = hig, ref = 0
• sref = sig, ref = 0

From this reference we calculate each thermodynamic property F = u, h,

s, a, g, following the path:

F(T, p) = F ig, ref + [F ig (T, p) − F ig, ref ] + F R (T, p)

= F ig, ref + [F ig (T, p) − F ig, ref ] + F R (T, v(T, p))

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 Generalized residual functions

Thermodynamic functions using residual properties

T
h(T, p) = ∫ p dT + h (T, p)
cig R
T ref
T cig
p p
s(T, p) = ∫ dT − R ln ( ref ) + sR (T, p)
T ref T p
from these properties we calculate

g(T, p) = h(T, p) − T s(T, p)

u(T, p) = h(T, p) − pv(T, p)
a(T, p) = u(T, p) − T s(T, p)

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 Generalized residual functions

Example
Multistage compressor with intercooling
• Find the work and heat load of the following multistage compressor.
• Find the intermediate pressures that minimize the compression work.
Assume:
• Adiabatic efficency of 85% in each compressor.
• pvT behavior is well represented by a B-truncated virial EoS.
• Reference state: ideal gas, 25 °C, 1.01 bar.

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 Generalized residual functions

Example
Tank filling1 : A compressed nitrogen tank is to be pressurized from 1.01
bar and 25 °C to 50 bar by connecting it to a high pressure line containing
nitrogen at 70 bar and 25 °C. The pressurization of the tank occurs so
quickly that the process can be assumed adiabatic. Estimate the
temperature of the nitrogen in the tank when it reaches 50 bar. Assume
that pvT behavior can be described by the PR EoS.
Reference state: ideal gas, 25 °C, 1.01 bar.

1
See Illustration 2.5-2 of Sandler’s book. Sandler S. Chemical and engineering
thermodynamics, 1st ed.
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