PENG-ROBINSON

EQUATION

OF

STATE:

Z FACTOR

Purpose
This workbook provides a working example of the z factor, enthalpy and entropy calculations for
using the Peng-Robinson Equation of State (EOS). This is the same calculation written into the zf
provided in this format to help users who are less familiar with code to understand the calculatio

Liability
No warrantees are made with respect to the accuracy or applicability of the calculations in this sp
the user to verify that any results obtained are correct and appropriate for the work being carryin

Copyright
This spreadsheet is the intellectual property of the author, Andrew Hooks. You are free to use it a
you may not make it available for download from any website without prior written consent and y
obscure any notices regarding authorship.
Contact
Email:
For other tools, visit: www.firstprincipleseng.wordpress.com

ACTOR

d entropy calculations for a multi-component fluid

ulation written into the zfactor Excel add-in but
understand the calculation approach.

f the calculations in this spreadsheet. The onous is on

for the work being carrying out.

ks. You are free to use it and distribute it however,

prior written consent and you must not remove or

PENG-ROBINSON
Stream conditions
Temperature
Pressure
z factor
Enthalpy
Entropy

EQUATION

310.92 K
689.47 kPaA
0.9910 -79923 kJ/kgmol
171 kJ/(kgmol.K)

OF

STATE:

Constants
R

Z FACTOR

8.31451 kPa.m3/(kmol.K)

Constants and derived properties

Composition
ID
0 Nitrogen
1 CO2
2 Methane
3 Ethane
4 Propane
5 i-Butane
6 n-Butane
7 i-Pentane
8 n-Pentane

MolFrn
mol/mol
0.000
0.000
0.800
0.100
0.050
0.000
0.030
0.010
0.010
1 OK

Component constants
MolWeight
CritTemp CritPres
kg/kgmol
K
kPa
28.013
126.2
3394
44.010
304.1
7370
16.043
190.7
4641
30.070
305.4
4884
44.097
369.9
4257
58.124
408.1
3648
58.124
425.2
3797
72.151
460.4
3334
72.151
469.6
3375

Mixture parameters
am
0.173
bm
3.209E-005
A
0.018
B
0.009
z factor
Solve cubic
b
c
d
p
q
r
r>0
r=0
r<0

-0.991
0.00052606
-7.900E-005
-0.3271263
-0.0720937
2.843E-006

z -(1-B).z + (A.B - B - B).z - (A.B - B - B) = 0

b = -(1 - B)
c = (A - 2.B - 3.B)
d = - (A.B - B - B)
p = (1/3)(3b - a)
q = (1/27)(27c - 9a.b + 2a)
r = (p/3) + (q/2)

0.9910 **
-

If there are multiple roots we use fugacity (related

stable root). For a single component fluid the tran
fluid the phase transition occurs over a range of P
phase transition boundary (a dew/bubble point ca
multi-component fluid the z values in the region e
z factor can only meaningfully be calculated for a

Determine stable root

z(vap)
0.9910
z(liq)
0.9910
Fugacity(vap)
0.9909
Fugacity(liq)
0.9909
z
z(add-in)

of the separate liquid and vapour phases and z ca

In addition note that even though there may be 2

0.9910 UNAVAIL.

Ethalpy
Ethalpy and entropy are state properties which means that their value at a given T, P is indep
We define a reference enthalpy at a given P, T then calculate the change in enthalpy to the re
Different literature/software uses different reference values which isn't really important since w
HYSYS and UNISIM use the Heat of formation at 25C as the reference enthalpy and this is als
Reference enthalpy
Reference T
298.15 K
Reference P
101.325 kPaA
H reference
-80385 kJ/kgmol

Arbitary reference value (since

dH ideal (T.ref --> T)

dH ideal

Change in enthalpy from referen

dH (ideal) = SUM[xi.dHideal]

556 kJ/kgmol

H departure (P=1bara --> P)

Kappa
0.431 Tc
224 K
alpha
0.852 H departure
-95 kJ/kgmol
"Real" enthalpy
Hreal
-79923 kJ/kgmol
Hreal (add-in)
UNAVAIL.
kJ/kgmol

H(ref) = SUM[xi.dH(formation)]

Change in enthalpy from (T requ

Hd = (z - 1 - LN((z + (1 + Sqr(2)) * B

Enthalpy = Href + dHideal + Hd

Entropy
S reference
dS ideal
dS mixing
S departure
S depart. (ref.)
S real
S real (add-in)

z factor add-in

179 kJ/(kgmol.K)
1.83 kJ/(kgmol.K)
6.28 kJ/(kgmol.K)
-0.23 kJ/(kgmol.K)
0.00 kJ/(kgmol.K)
171 kJ/(kgmol.K)
UNAVAIL.
kJ/(kgmol.K)

S(ref) = SUM[xi.dS(formation)]
dS (ideal) = SUM[xi.dSideal]
Enthalpy of mixing is zero for an ide
Sd = GAS_CONST * LN(z - B) - LN((z
Sd(ref) is ignored since it requires re
Entropy = Sref + dSideal + dSmix -

The zfactor add-in expands on the above calculations - adding Cp-real and Cv-real, Isenthalpic
us to model real world processes (e.g. compression or expansion across a valve or turbo-expa
These calculations are the same as those carried out above but need to be solved multiple tim
* Cp-real = dH/dT as dT approaches 0 requires two enthalpy calculations
* Isenthalpic temperature rise (compression) requies an iteration to find the temperature (at t

ACTOR

Pa.m3/(kmol.K)

Binary interaction parameters (from Unisim Design)

AccFactor Nitrogen
CO2
Methane Ethane
Propane
i-Butane
0.0400
-0.02000
0.03600
0.05000
0.08000
0.09500
0.2389 -0.02000
0.10000
0.12980
0.13500
0.12980
0.0115
0.03600
0.10000
0.00224
0.00683
0.01311
0.0986
0.05000
0.12980
0.00224
0.00126
0.00457
0.1524
0.08000
0.13500
0.00683
0.00126
0.00104
0.1848
0.09500
0.12980
0.01311
0.00457
0.00104
0.2010
0.09000
0.12980
0.01230
0.00410
0.00082
0.00001
0.2222
0.09500
0.12500
0.01763
0.00741
0.00258
0.00035
0.2539
0.10000
0.12500
0.01793
0.00761
0.00270
0.00039

z - (A.B - B - B) = 0

we use fugacity (related to Gibbs Free Energy) to determine which is the stable root (the root with the lowest
omponent fluid the transition between z(v) and z(l) denotes the vapour-liquid phase change. However, for a
ccurs over a range of P,T (lighter components vapourising first etc) and the change from z(v) to z(l) does not
a dew/bubble point calculation is required for this which considers the fugacities of the individual componen
values in the region either side of the phase transition will be "suspect" as we are likely to be in the two pha
ully be calculated for a single phase fluid. If two phases exist then a flash calc must be performed to determi

apour phases and z calculated for each of them.

hough there may be 2 or 3 roots this does not imply that we are in the two phase region - this may or may n

at a given T, P is independent of the path taken to get there

e in enthalpy to the requested P, T in two steps - first an ideal step (no change in P), then a departure functio
eally important since we are normally interested in the change in enthalpy
nthalpy and this is also adopted here to make it easy for users to carry out their own validation if desired

erence value (since practical calculations are interested in change in enthalpy)

[xi.dH(formation)]

nthalpy from reference T to requested T (at P=1 bara therefore "ideal" change in enthalpy)
SUM[xi.dHideal]

nthalpy from (T requested, P=1bara) to (T requested, P=P requested). "Departure function"

N((z + (1 + Sqr(2)) * B) / (z + (1 - Sqr(2)) * B)) * A / (B * Sqr(8)) * (1 + K * Sqr(Tr) / Sqr(alpha))) * GAS_CONST

ref + dHideal + Hd

xi.dS(formation)]
UM[xi.dSideal]
mixing is zero for an ideal fluid but entropy of mixing is not, dS(mix) = -R*SUM[xi.LN(xi)]
NST * LN(z - B) - LN((z + (1 + Sqr(2)) * B) / (z + (1 - Sqr(2)) * B)) * A * GAS_CONST / (B * Sqr(8)) * (K * Sqr(Tr)
ored since it requires recalculation of z at reference P,T and is generally very small. It is calculated in the zfac
ef + dSideal + dSmix - GAS_CONST * LN(Pres / Pref) + Sd - Sd_ref

nd Cv-real, Isenthalpic and Isentropic temperature/pressure change etc. which allow

a valve or turbo-expander)
be solved multiple times, or as an iteration, and are therefore well suited for code, e.g.
the temperature (at the target pressure) that corresponds to dS=0

n-Butane i-Pentane n-Pentane

0.09000
0.09500
0.10000
0.12980
0.12500
0.12500
0.01230
0.01763
0.01793
0.00410
0.00741
0.00761
0.00082
0.00258
0.00270
0.00001
0.00035
0.00039
0.00050
0.00055
0.00050
1.23E-06
0.00055 1.23E-06

t (the root with the lowest fugacity is the

se change. However, for a multi-component
e from z(v) to z(l) does not correspond to the
of the individual components). In fact for a
e likely to be in the two phase region.
st be performed to determine the composition

Component derived properties

kappa
alpha(T)
a(Tc)
0.436
0.565
0.148
0.728
0.984
0.397
0.392
0.795
0.248
0.524
0.991
0.604
0.603
1.103
1.016
0.650
1.172
1.443
0.674
1.205
1.505
0.704
1.267
2.010
0.749
1.298
2.065

region - this may or may not be the case.

P), then a departure function to account for non-ideality at high pressure

own validation if desired

hange in enthalpy)

Departure function"

/ Sqr(alpha))) * GAS_CONST * Temp

T / (B * Sqr(8)) * (K * Sqr(Tr) / Sqr(alpha))

. It is calculated in the zfactor add-in

operties
a
-

b
0.084
0.390
0.197
0.598
1.121
1.692
1.813
2.546
2.682

(xi.ai^0.5)*SUM[xj.aj^0.5 * (1-BIP(i,j))]
2.40E-05
0.0000
2.67E-05
0.0000
2.66E-05
0.0715
4.05E-05
0.0371
5.62E-05
0.0266
7.24E-05
0.0000
7.24E-05
0.0207
8.93E-05
0.0085
9.00E-05
0.0088

Ideal gas heat capacities

A
27.529681
27.204112
37.934881
34.366889
17.418315
8.9104093
0.4964127
-9.509358
-0.844289

Used for Enthalpy/Entropy calculation only

eal gas heat capacities

dH(ideal)
dS(ideal)
B
C
D
E
kJ/kgmol
kJ/(kgmol.K)
0.0054425 -3.5E-008 -4.1E-010 5.67E-014
373
1.223
0.0426441 -2.0E-005 4.03E-009 -3.0E-013
491
1.613
-0.068422 0.0002725 -2.4E-007 6.91E-011
462
1.519
-0.019461 0.0003828 -4.1E-007 1.33E-010
684
2.246
0.1864501 5.25E-005 -1.2E-007 3.70E-011
971
3.189
0.3062891 1.27E-005 -1.7E-007 6.88E-011
1266
4.159
0.3809435 -0.000193 4.11E-008 -1.9E-012
1273
4.181
0.5109734 -0.000289 7.26E-008 -4.7E-012
1550
5.088
0.4785632 -0.000253 5.76E-008 -3.1E-012
1571
5.158

Reference H, S
Hfo

Sfo

kJ/kgmol

kJ/(kgmol.K)

0 148.06301205
-393790 172.38727811
-74900 183.47583308
-84738 195.21914485
-103890 161.65472113
-134590 160.65022232
-126190 127.49554566
-154590 36.940704156
-146490 75.009591303

PENG-ROBINSON

EQUATION

OF

STATE:

Z FACTOR

Table created using the 'Scenario Tool' Add-in - available from

Re-run scenarios to update results for a change in composition
Pressure
Temperature
z
kPaA
K
INP: '[zfactor-spreadsheetversion.xlsx]zFactor'!$C$5

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INP: '[zfactor-spreadsheetversion.xlsx]zFactor'!$C$4

248.15

CHART

https://firstprinciplese

1.2

OUT: $zFactor.$C$6

0.995
0.991
0.986
0.981
0.977
0.972
0.967
0.962
0.958
0.953
0.905
0.857
0.808
0.760
0.712
0.667
0.627
0.594
0.570
0.556
0.551
0.551
0.556
0.564
0.574
0.585
0.598
0.612
0.627
0.642
0.657
0.673
0.689
0.705
0.721
0.737
0.753
0.770
0.786
0.803
0.819

1.0

0.8

0.6
z factor [-]

0.4

0.2

0.0
0

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273.15

0.836
0.852
0.869
0.886
0.902
0.919
0.935
0.952
0.996
0.993
0.989
0.986
0.982
0.979
0.975
0.972
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0.965
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0.831
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0.771
0.745
0.722
0.703
0.688
0.677
0.669
0.666
0.665
0.667
0.671
0.677
0.685
0.694
0.703
0.714
0.725
0.737
0.749
0.762
0.775
0.788
0.801
0.815
0.828

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298.15

0.842
0.856
0.870
0.884
0.898
0.913
0.927
0.941
0.955
0.997
0.995
0.992
0.989
0.987
0.984
0.981
0.979
0.976
0.974
0.948
0.923
0.899
0.876
0.855
0.835
0.817
0.801
0.787
0.776
0.766
0.759
0.754
0.751
0.750
0.751
0.754
0.757
0.762
0.768
0.775
0.782
0.791
0.800
0.809
0.819
0.829
0.840
0.850

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0.862
0.873
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0.932
0.944
0.956
0.969
0.998
0.996
0.994
0.992
0.990
0.988
0.986
0.984
0.982
0.980
0.961
0.942
0.924
0.908
0.893
0.878
0.866
0.854
0.844
0.836
0.829
0.823
0.819
0.816
0.815
0.815
0.816
0.818
0.821
0.825
0.830
0.835
0.841
0.848
0.855
0.862
0.870
0.879

30000
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0.888
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0.945
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0.966
0.976
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CTOR

CHART

tps://firstprincipleseng.wordpress.com/category/excel/

1.2

1.0

0.8

0.6
z factor [-]

0.4
T=-25'C
T=0'C

0.2

T=25'C
T=50'C

0.0
0

5000

10000

15000

20000

25000

Pressure [kPa(A)]

30000

35000

40000

4500

T=-25'C
T=0'C
T=25'C
T=50'C
35000

40000

45000