Key Thermo-Physical Properties of Light Crude Oils
Jayanthi Vijay Sarathy, M.E, CEng, MIChemE, Chartered Chemical Engineer, IChemE, UK
Process facilities are equipped with
protection measures, such as pressure safety
valves (PSV) & as a minimum, PSVs are sized
for a fire case. To do so for a pressure vessel
containing crude oil a key parameter is the
Latent heat of Vaporization [Hv].
For pure components, the Joback’s Method
can be employed which uses basic structural
information of the chemical molecule to
estimate thermo-physical data. However it
can be complex for equipment that contains
crude oil because the plus fractions [C7+] can
contain thousands of straight chain, cyclic &
functional groups. Therefore by splitting and
lumping the crude fractions, a smaller
number of components are arrived at, to
characterize and be able to apply Equation of
State (EoS) correlations to estimate the
fraction’s thermo-physical properties.
To estimate properties such as MW, Specific
gravity [], Critical Pressure [Pc], Critical
Temperature [Tc] and Latent heat of
Vaporization [Hv], the following article
provides few correlations applicable for light
crudes with boiling points < 4550C based on
D-86 Distillation curves.
General Notes
1. Latent heat of Vaporization [Hv], can be
estimated using critical properties of the
plus fractions in the hydrocarbon mixtures.
2. Oil fractions tend to decompose at ~6500F
(3440C) at 1 atm. As a result, it becomes
necessary to lower the pressure to as low
as 40mm Hg to obtain the True Boiling
Point (TBP) distillation curves. ASTM
methods can be used to convert the
resulting boiling point curve into TBP
curves using correlations from API
Technical Data Book – Petroleum Refining.
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3. The ASTM D-86 distillation of an oil
fraction is conducted in laboratory room
conditions at 1 atm and the D-86
distillation curve ends at ~6500F (3440C).
4. The ASTM D-1160 distillation of an oil
fraction is conducted at much lower
pressures, typically 10 mmHg for heavier
oils with high boiling points to prevent
decomposition of the oil sample. With this
method, oil fractions can be distilled upto
~9500F to ~10000F (5100C to 5380C),
reported on a 760mm Hg basis.
5. The boiling point of all compounds in a
crude mixture can be represented by a
single characteristic boiling point called
Volume Average Boiling Point [VABP].
Since the individual mole fractions of the
petroleum stream is not known, VABP is
calculated from standard distillation data
[ASTM D-86] followed by calculating the
mean average boiling point [MeABP].
6. The Molecular weight [MW], Specific
gravity [] & boiling point [Tb] are taken as
the key properties to define the makeup of
a petroleum fraction. In this article, the
Katz-Firoozabadi [1978], Riazi-Daubert
[1980, 1987] & Ahmed [1985] correlations
are shown to predict MW, specific gravity
[], Critical Pressure [Pc] & Critical
Temperature [Tc]. To estimate Hv, Riedel
correlation is employed to estimate the
Latent Heat of Vaporization [Hv,NBP] at
Normal Boiling Point [MeABP/NBP/Tb].
Watson relation is used to estimate HV,T at
desired temperature.
Selected Correlations
The below table gives a summary of the two
generalized correlations to estimate MW, Pc,
Tc and Hv of the petroleum fraction.
Table 1. Generalized Correlations for Pc, Tc and MW Kreglewski and Zwolinski [1961] generalized
Katz-Firozabaadi Correlation [1978] expression which is of the form,
𝑐 )]
𝐤𝐠 𝟔.𝟗𝟕𝟗𝟗𝟔−𝐥𝐧[𝟏𝟎𝟖𝟎−𝑻𝒃 ]
𝟑⁄
𝟐 𝜃 = 𝜃 − 𝑒 [𝑎−(𝑏×𝑀𝑊 (1)
𝐌𝐖 [𝐤𝐦𝐨𝐥] = [ ]
𝟎.𝟎𝟏𝟗𝟔𝟒
Where,  represents the properties such as
[𝟑.𝟓𝟔𝟎𝟕𝟑−(𝟐.𝟗𝟑𝟖𝟖𝟔×𝐌𝐖 𝟎.𝟏 )]
𝛄[−] = 𝟏. 𝟎𝟕 − 𝐞 Tb, , Pc and Tbr.

𝑷𝒄 [𝒃𝒂𝒓𝒂] = 𝐞[𝟔.𝟑𝟒𝟒𝟗𝟐−(𝟎.𝟕𝟐𝟑𝟗×𝐌𝐖
𝟎.𝟐𝟗𝟗 )]
The value of the constants, a, b, c in the above
expression is based on a tabulated set
𝟎.𝟓𝟓 )]
𝑻𝒃𝒓 [−] = 𝟏. 𝟐 − 𝐞[−𝟎.𝟑𝟒𝟕𝟒𝟐−(𝟎.𝟎𝟐𝟑𝟐𝟕×𝐌𝐖 generated from the physical properties of 26
condensates and crude oil systems. The value
𝐓𝐛
𝐓𝐜 [°𝐊] = of  based on MW in the Katz-Firoozabadi
𝐓𝐛𝐫

𝟑⁄
correlation predicts within 0.4% for straight
[𝟔.𝟗𝟗𝟓𝟓−𝐥𝐧(𝟏𝟎𝟗𝟎−𝑻𝒃 )] 𝟐
𝐍𝐜 [−] = [ ] chain numbers [SCN] groups from C6 to C50.
𝟎.𝟏𝟏𝟏𝟗𝟑
Similarly, the absolute average deviation
𝐓𝐛 = °𝐊
(AAD%) of the Kreglewski and Zwolinksi
Riazi-Daubert Extended Correlation [1980] [1961] correlation gives an AAD% of 0.4%,
𝐤𝐠 0.07%, 0.15% and 1% in the properties of Tb,
𝐌𝐖 [𝐤𝐦𝐨𝐥] = [𝟒𝟐. 𝟗𝟔𝟓 × 𝐓𝐛𝟏.𝟐𝟔𝟎𝟎𝟕 ×
, Tbr, Pc respectively between correlations
𝛄𝟒.𝟗𝟖𝟑𝟎𝟖 ] × and physical properties of the 26 condensates
𝐞[(𝟎.𝟎𝟎𝟎𝟐𝟎𝟗𝟕×𝐓𝐛)−(𝟕.𝟕𝟖𝟕𝟏𝟐×𝛄)+(𝟎.𝟎𝟎𝟐𝟎𝟖𝟒𝟕𝟔×𝐓𝐛×𝛄)] and crude oil systems.

𝐓𝐛 = °𝐊; 𝛄 = 𝐔𝐧𝐢𝐭𝐥𝐞𝐬𝐬 VABP and MeABP Calculation

For petroleum fractions usually, there would
Riazi-Daubert Correlation [1987]
be no information available about the weight,
𝑷𝒄 [𝒑𝒔𝒊𝒂] = [𝟒𝟓𝟐𝟎𝟑 × 𝑴𝑾−𝟎.𝟖𝟎𝟔𝟑 × mole or volume fractions considering the
𝜸𝟏.𝟔𝟎𝟏𝟓 ] × 𝒆[(−𝟎.𝟎𝟎𝟏𝟖𝟎𝟕𝟖×𝑴𝑾)+(−𝟎.𝟑𝟎𝟖𝟒×𝜸)] large number of compounds present. In such
cases, the ASTM based D-86 distillation data
𝐓𝐜 [°𝐑] = [𝟓𝟒𝟒. 𝟒 × 𝐌𝐖 𝟎.𝟐𝟗𝟗𝟖 × 𝛄𝟏.𝟎𝟓𝟓𝟓 ] × for light oils (API Gravity > 310API and D-86
𝐞[(−𝟎.𝟎𝟎𝟎𝟏𝟑𝟒𝟕𝟖×𝐌𝐖)+(−𝟎.𝟔𝟏𝟔𝟒𝟏×𝛄)] Temperatures < 4550C) can be used to
estimate the Volume Average Boiling Point
The Latent Heat of Vaporization [Hv] is
(VABP) and Mean Average Boiling Point
calculated as,
(MeABP) which can be calculated as follows,
Table 2. Riedel Correlation and Watson Relation
𝑇10% +𝑇30% +𝑇50% +𝑇70% +𝑇90%
Riedel Correlation 𝑉𝐴𝐵𝑃[℃] = (2)
5

1.092×8.3145×Tb ×[lnPc −1.013] It is to be noted that when the average boiling

Hv,NBP [kJ/mol] = T
[0.93− b ]×1000
Tc
point (ABP) of a crude sample is estimated
based on weight (W), moles (M) and volume
Pc = bara; Tc = °K ; Tb = °K
(V) basis, there would exist a difference in
Watson Relation each of these average boiling points. To relate
T −T 0.38 the different types of ABPs, the VABP value is
Hv [kJ/mol] = Hv,NBP × [T c−T ] corrected with a slope line and correction
c b

T = °K ; Tc = °K ; Tc = °K ; Hv = kJ/mol factor line to find other ABPs. The Slope Line

(S) is estimated as,
It is to be noted that, the Katz-Firoozabadi 𝑇90% −𝑇10%
𝑆[℃⁄% 𝑅𝑒𝑐𝑜𝑣𝑒𝑟𝑒𝑑 ] = (3)
[1978] correlation was originally based on 80

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With the S value, the correction factor, TMeA Or, 𝑇𝑏 ≅ 243℃ ≅ 516°𝐾 ≅ 929°𝑅 (11)
is estimated using the empirical expression, Applying the MeABP/Tb value, the critical
∆𝑇𝑀𝑒𝐴 = −1.53181 − [0.0128 × 𝑉𝐴𝐵𝑃0.6667 ] + properties,  and MW is estimated as follows,
[3.646064 × 𝑆 0.333 ] (4) kg
3
6.97996−ln[1080−516] ⁄2
MW [kmol] = [ ] = 188.4 (12)
Where, 0.01964
0.1 )]
VABP = Volume Average Boiling Point [0C] γ = 1.07 − e[3.56073−(2.93886×188.4 = 0.8238 (13)

With the correction factor, TMeA, the MeABP

141.5
API Gravity = 0.8238 − 131.5 = 40.26°𝐴𝑃𝐼 (14)
is estimated as, 0.299 )]
𝑃𝑐 = e[6.34492−(0.7239×188.4 = 17.8 𝑏𝑎𝑟𝑎 (15)
𝑀𝑒𝐴𝐵𝑃 [℃] = 𝑉𝐴𝐵𝑃 − ∆𝑇𝑀𝑒𝐴 (5) 0.55 )]
𝑇𝑏𝑟 = 1.2 − e[−0.34742−(0.02327×188.4 = 0.733 (16)
To estimate the critical properties, MW and
516
latent heat of vaporization [Hv], MeABP Tc = 0.7335 = 704°K (17)
becomes the normal boiling point, Tb. [6.9955−ln(1090−516)]
3⁄
2
Nc = [ ] = 13.78 (18)
Case Study 0.11193

Light Crude Oil is present in a process vessel Similarly applying Riazi-Daubert correlations
at 3250K [51.850C]. To size a PSV for fire case,
from Table 1 with =0.8238 and Tb = 5160K.
the latent heat of vaporization [Hv] value is
kg
required to be computed. The D-86 MW [kmol] = 189.8 (19)
distillation curves are as follows,
𝑃𝑐 = 266 psia = 18.3 𝑏𝑎𝑟𝑎 (20)
Table 3. ASTM D86 Vol% vs Temperature
Tc = 1,254°R = 697°K (21)
Vol% [ASTM D86] D86 Temperature [0C]

0 [IBP] 155.1 The Latent Heat of Vaporization [Hv,NBP]

based on Katz-Firoozabadi Pc, Tc, Tb data is,
10 179.1
30 222.4 Hv,NBP =
9.079434×516×[ln17.8−1.013] 𝑘𝐽
≅ 44.5 𝑚𝑜𝑙(22)
516
[0.93− ]×1000
704
50 260.3
70 289.0 At 3250K, Hv,T is,
90 315.7 704−325 0.38 𝑘𝐽
Hv,T = 44.49 × [704−516] = 59.23 𝑚𝑜𝑙 (23)
100 [FBP] 352.9
Similarly, using Riazi-Daubert Pc, Tc, Tb data,
With the available data, VABP is estimated as, 𝑘𝐽
Hv,NBP = 46.96 𝑚𝑜𝑙 (24)
179.1+222.4+260.3+289+315.7
𝑉𝐴𝐵𝑃[℃] = (6) 𝑘𝐽
5
At 3250K, Hv,T = 61.8 𝑚𝑜𝑙 (25)
𝑉𝐴𝐵𝑃[℃] = 253.3℃ (7)
Additional Correlation – Ahmed [1985]
The slope, S is estimated as,
Based on Ahmed [1985] correlation of the
𝑆 [℃⁄% 𝑅𝑒𝑐𝑜𝑣𝑒𝑟𝑒𝑑] =
315.7−179.1
= 1.7075 (8) Katz-Firoozabadi [1978], physical properties
80
are tabulated with the number of carbon
The correction factor TMeA becomes, atoms in petroleum fractions using a
∆𝑇𝑀𝑒𝐴 = −1.53181 − [0.0128 × 253.30.6667 ] + regression model of the form,
𝑎5
[3.646064 × 1.70790.333 ] = 10.1℃ (9) 𝜃 = 𝑎1 + 𝑎2 𝑛 + 𝑎3 𝑛2 + 𝑎4 𝑛3 + (26)
𝑛

The MeABP is estimated as, Where,

 = Tc, Pc
𝑀𝑒𝐴𝐵𝑃[℃] = 𝑇𝑏 = 253 − 10.1 ≅ 243℃ (10) n = number of carbon atoms
Page 3 of 5
a1, a2, a3, a4, a5 =coefficients Taking an average of the estimates made, the
Table 4. Ahmed [1985] Constants -  and MW critical properties, MW and Hv is estimated as,
Table 7. Average of Estimates
Property  MW
Average
Coefficients [-] [kg/kmol] Property
Properties

a1 0.86714949 -131.11375 MW [kg/kmol] 189.0

a2 0.00341434 24.96156  [-] 0.8242

a3 -0.00002840 -0.34079022 Pc [bara] 18.4

a4 2.4943308108 0.00249412 Tc [0K] 701

a5 -1.16279840 468.32575 Hv,NBP [kJ/mol] 46.05

Table 5. Ahmed [1985] Constants - Pc and Tc Hv,3250K [kJ/mol] 60.36

Property Pc Tc References
Coefficients [psia] [0R] 1. “Physical Properties of Heavy Petroleum
Fractions and Crude Oils”, Mohammad. R.
a1 275.56275 915.53747
Riazi, Taher A. Al-Sahhaf, Fluid Phase
a2 -12.522269 41.421337 Equilibria, 117 (1996) 217-224
a3 0.29926384 -0.7586859 2. “Equation of State and PVT Analysis”, Tarek
Ahmed, Gulf Publishing Company
a4 -0.00284521 0.00586754
3. “Petroleum Refinery Process Modelling:
a5 1711.7226 -1302.8779
Integrated Optimization Tools and
Based on Ahmed [1985] correlation, Applications”, Y.A. Liu, Ai-Fu Chang, Kiran
Pashikanti, First Edition, 2018 Wiley–VCH
MW[𝑘𝑔⁄𝑘𝑚𝑜𝑙 ] = 188.7 (27)
Verlag GmBH & Co.
𝑃𝑐 = 266 psia = 19.1 𝑏𝑎𝑟𝑎 (28) 4. “Evaluation of Different Correlation
Tc = 1,254°R = 702°K (29) Performance for the calculation of Critical
𝑘𝐽 Properties and Acentric Factor of Petroleum
Hv,NBP = 46.71 𝑚𝑜𝑙 (30)
Heavy Fractions”, Dacid B. L, Rafel B. S,
At 3250K, Hv,T = 61.15 𝑚𝑜𝑙
𝑘𝐽
(31) Andre P.C.M.V, Adolfo P. P, Viatcheslav I. P,
http://dx.doi.org/10.5772/intechopen.71166
Results
Summarizing the results,
Table 6. Results Summary
Katz- Riazi- Ahmed
Property
Firoozabadi Daubert [1985]
MW [kg/kmol] 188.4 189.8 188.7

 [-] 0.8238 - 0.8245

Pc [bara] 17.8 18.3 19.1

Tc [0K] 704 697 702

Hv [kJ/mol] 44.49 46.96 46.71

Hv,T [kJ/mol] 58.12 61.80 61.15

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 Appendix: MS-Excel Calculations

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