© Kuch Latthias / Total

APPLIED THERMODYNAMICS
CHAPTER 2- AVERAGE CHARACTERISTICS AND PROPERTIES
OIL CUTS
A - CHARACTERIZATION FACTOR OF HYDROCARBONS AND OIL
CUTS (KUOP)

Nelson, Watson and Murphy from U.O.P. (Universal Oil Product) have sought
to establish a mathematical relationship linking density and boiling temperature
to obtain parametric curves that best overlap those of the different families.
This relationship is :

KUOP = 3√ T / Sp.gr60 60

where T is the boiling temperature expressed in °Rankine.

Applied Thermodynamics 2 ODJE/2018

 A - CHARACTERIZATION FACTOR OF HYDROCARBONS AND OIL
CUTS (KUOP)

The value of the KUOP parameter in these curves is characteristic of the chemical
families.
For example :
- if KUOP = 13 the characteristic curve corresponds to paraffinic hydrocarbons.
- if KUOP = 11 the parametric curve corresponds to naphthenic hydrocarbons
- if KUOP = 10 the parametric curve corresponds to the aromatic hydrocarbons

B - AVERAGE PROPERTIES OF OIL CUTS

1. Determining of boiling temperature of an oil cut.

In the case of an oil cut, the notion of boiling temperature is

meaningless because the vaporization carried out at constant
pressure takes place over a range of temperatures.

Applied Thermodynamics 3 ODJE/2018

B - AVERAGE PROPERTIES OF OIL CUTS
1. Determining of boiling temperature of an oil cut.

In order to be able to use the KUOP diagram in particular, a temperature has to

be defined. mean boiling point or t mean average (tmav) without any
physical significance but which allows to obtain results of correlations
consistent with direct measurements of section properties oil cuts.

J.B. Maxwell proposes statistically obtained correlations (Plate P1) allowing to

Determine the average boiling temperature from :

:- TBP distillation
- or ASTM distillation of oil cuts.

Thus, a fictitious pure hydrocarbon characterised by its average boiling temperature

tmav

tmav = [(ti + tf)TBP] / 2

Applied Thermodynamics 4 ODJE/2018

B - AVERAGE PROPERTIES OF OIL CUTS
1. Determining of boiling temperature of an oil cut.

Many correlations to determine the physical properties of petroleum mixtures use

reduced T and P:

- Tr = T / Tc
- Pr = P / Pc
2. Determination of pseudo-critical coordinates

In the case of a mixture whose constituents are known individually, the

true critical coordinates of pure hydrocarbons, according to the KAY rule (molar
weighting).

Tpc = ∑xi Tci Ppc = ∑xi Pci

Applied Thermodynamics 5 ODJE/2018

3. Specific gravity of liquid oil cuts

For commercial transactions, it is necessary to know the density or density at 15°C.

Official conversion tables are available to determine this value in the event that the
measurement was not taken at this temperature.

The order of magnitude of density variations can be estimated using the following
approximate linear formula

D4, θ = dt 4 + K (t – θ)

d4,15 0,60-0,7 0,7-0,76 0,76-0,8 0,8-0,85 0,85-0,88 0,88-0,9

K 0,0009 0,00085 0,0008 0,00075 0,00065 0,00062

The Plate H3 allows the estimation of density variations over a wider temperature range.
It is realised that the linear variation of density with temperature is only an approximation
and is no longer followed when the temperature of the product approaches its critical
temperature

Applied Thermodynamics 6 ODJE/2018

3. Specific gravity of liquid oil cuts

At high temperatures, the influence of pressure on the sp. gr of liquid oil cuts may no
longer become negligible.
Watson and Gamson propose an abacus which gives the expansion coefficient ω
according to the pseudo-reduced coordinates. This expansion coefficient is defined as
follows:

d1 / ω1 = d / ω

Applied Thermodynamics 7 ODJE/2018

 4. Specific heat (mass and molar)

Specific heat of hydrocarbons and liquid petroleum cuts

It can be seen from Plate D2 that, except for light hydrocarbons, the specific
heat in the liquid state varies almost linearly with temperature. It depends
essentially on the density in the liquid state and the chemical nature of the cut
through the KUOP.

Specific heat in the gas state

It depends on the same variables, but is also sensitive to pressure. Plate D3

provides at atmospheric pressure the specific heat of some pure hydrocarbons as
well as of certain gas.
Plate D4 provides the same data for the gas oil cuts identified by their KUOP.
Hydrogen is characterised by a very high specific heat as can be seen in the table
below

Applied Thermodynamics 8 ODJE/2018

 Temperature (°C) 0 100 200 300 400 500 600
kcal /kg°C 3,39 3,45 3,45 3,47 3,48 3,5 3,53
Specific heat
kJ/kg K 14,19 14,45 14,5 14,53 14,58 14,66 14,75

Plate D5 published by Hougen and Watson, established in pseudo-reduced

coordinates, allows the correction of the molar specific heat of gases under
pressures higher than the atmosphere.

Applied Thermodynamics 9 ODJE/2018

 5. Enthalpy of oil cuts

In the case of mixtures whose constituents are identified, enthalpic diagrams of the
pure substances and additivity rules proposed in the presentation of the "liquid-
vapour equilibria" (plates E1 to E6) are used.

For oil cuts, Shell Development Company has grouped the enthalpy values on a
single diagram (Plate E7) with the liquid density of cut as the main parameter.
Corrections are made with chemical nature (in case the KUOP is different from the
value 12) as well as the pressure for the enthalpy of the vapour.

Applied Thermodynamics 10 ODJE/2018

 6. Viscosities of hydrocarbons and oil cuts

a - Viscosity in the gas state

At atmospheric pressure the dynamic viscosity of the following gas: oxygen,

nitrogen, air, gas Carbon dioxide, water vapour, hydrogen is given as a function of
temperature on the Plate F1-1
The upper diagram on plate F1-2 allows the determination of the dynamic viscosity
at atmospheric pressure of gaseous hydrocarbons as a function of temperature. The
only parameter The molecular weight is the key factor in distinguishing between
hydrocarbons. We can see that these are the "light" gaseous hydrocarbons, which
are the most viscous and have the highest viscosity in the gas state increases with
temperature.
Pressure has a significant influence on gas viscosity. The lower part of plate F1-2
gives the value of µp/µ1 (ratio of viscosity to pressure) using the reduced
coordinates. P (µp) has the viscosity at atmospheric pressure (µ1) determined
previously)

Applied Thermodynamics 11 ODJE/2018

 6. Viscosities of hydrocarbons and oil cuts
b - Viscosity in the liquid state

Plate F2 gives the kinematic viscosity of the liquid paraffinic hydrocarbons as a

function of the number of carbon atoms, as well as that of some aromatic
hydrocarbons.
The viscosity of liquid hydrocarbons depends on their chemical nature and their molar
mass. Hougen and Watson propose a correlation (sheet P5) linking: tmav, KUOP,
density and viscosity to 50°C of liquid petroleum cuts. This correlation is very
approximate and is not a substitute for the result of a viscosity measurement

Applied Thermodynamics 12 ODJE/2018

 6. Viscosities of hydrocarbons and oil cuts
c - Viscosity variation of oil cuts with temperature

The viscosity of oil cuts in the liquid state decreases very sharply when the
temperature rises.
The viscometric diagram presented by the ASTM (Plate F4) gives a linear
representation of viscosity variations with temperature. This makes it possible to
characterise a section by two values of the viscosity measured at two different
temperatures.
It should be remembered that in the case of base oils, the viscosity index (VI) makes
it possible to assess the amplitude of the variation in viscosity of the product with
temperature (plate F7).

Applied Thermodynamics 13 ODJE/2018

 7 - True vapour pressure - reid vapour pressure

The vapour pressure of light oil cuts is measured indirectly by the Pressure test of
Reid steam (RVP). The value of the RVP measured at 37.8°c and expressed in
relative pressure is due to the air initially trapped in the device and the rest to the
fractions that are more volatiles from the oil cup that vaporized in the Reid bomb.

The Coordinating Research Council (C.R.C.) presents a correlation (Plate B4) linking
the RVP to the True Vapour Pressure (TVP) of the cut.

It can be noted that generally the value of the true vapour pressure (in absolute
pressure) is a slightly higher than the RVP (expressed as relative pressure). Generally
the TVP/RVP ratio is between 1 and 1.2.
Because of hydrocarbons, petrol have a substantially ideal behaviour in the bubble or
vapour pressure curves of the mixtures, we are entitled to represent by the straight
lines in the COX CHART (Plate B1).

Applied Thermodynamics 14 ODJE/2018